Scribd Logo
Încărcați

Bine ați venit la Scribd!

  • Euro Membrane 2009

    Încărcat de

    Leszek Jaszczak
    1K vizualizări548 pagini
    ARAMIS has developed a unique membrane expertise in order to meet customer requirements. ARAMIS is made up of experts from different fields such as microbiology, water sciences, membrane processes and chemical engineering. A range of tests are employed, which results in: >a precise membrane characterisation, specifically focused on new commercial membranes.

    Descriere originală:

    Drepturi de autor

    © Attribution Non-Commercial (BY-NC)

    Formate disponibile

    PDF, TXT sau citiți online pe Scribd

    Vi se pare util acest document?

    Este necorespunzător acest conținut?

    Raportați acest document
    ARAMIS has developed a unique membrane expertise in order to meet customer requirements. ARAMIS is made up of experts from different fields such as microbiology, water sciences, membrane processes and chemical engineering. A range of tests are employed, which results in: >a precise membrane characterisation, specifically focused on new commercial membranes.

    Drepturi de autor:

    Attribution Non-Commercial (BY-NC)
    Descărcați ca PDF, TXT sau citiți online pe Scribd
    Indicator pentru conținut neadecvat
    1K vizualizări548 pagini

    Euro Membrane 2009

    Încărcat de

    Leszek Jaszczak
    ARAMIS has developed a unique membrane expertise in order to meet customer requirements. ARAMIS is made up of experts from different fields such as microbiology, water sciences, membrane processes and chemical engineering. A range of tests are employed, which results in: >a precise membrane characterisation, specifically focused on new commercial membranes.

    Drepturi de autor:

    Attribution Non-Commercial (BY-NC)
    Descărcați ca PDF, TXT sau citiți online pe Scribd
    Indicator pentru conținut neadecvat
    din 548

    Anjou Recherche Advanced Membrane Investigation Services

    A.R.A.M.I.S Membrane Expertise Centre


    Anjou Recherche, the water R&D centre of
    Veolia Environnement, has set up ARAMIS,
    the membrane expertise centre of
    excellence, dedicated to membrane
    technologies and applications such as:
    >production of drinking, process and
    ultra-pure water,
    >municipal and industrial wastewater
    treatment,
    >desalination
    ARAMIS is made up of experts from
    different fields such as microbiology, water
    sciences, membrane processes and
    chemical engineering.
    Its overall objectives are to:
    >evaluate membrane performance:
    rejection rates, hydraulic and mechanical
    properties;
    >define optimal operating conditions to
    prevent membrane fouling, reduce energy
    consumption and water losses
    ARAMIS
    ARAMIS has developed a unique
    membrane expertise in order to meet
    customer requirements.
    This knowledge base is built upon:
    >the experience gained from operating
    numerous membrane plants,
    >complete independence from
    membrane manufacturers.
    A range of tests are employed, which results
    in:
    >a precise membrane characterisation,
    specifically focused on new commercial
    membranes;
    >detailed autopsies being performed on
    all types of membrane (micro, ultra,
    nanofiltration and reverse osmosis) in order
    to optimise operating conditions.
    |1|1|? |ll||1|l11
    www.cometas.dk
    - Pow Slllcon Carblde ls changlng Lhe membrane markeL place
    10 Llmes hlgher waLer flux Lhan oLher ceramlcs
    UF MEMBRANES
    TECHNOLOGIES
    AQUASOURCE
    20, avenue Didier Daurat
    31400 TOULOUSE - France
    Ph: 00 33 5 61 36 30 36
    www.aquasource-membrane.com
    UF Membranes
    UF Units
    Engineering support
    |mpasse de Pa|ayr
    51100 I0UL0USE
    I. +33 51 317 8
    contact_po|ymem.fr
    www.pelymem.lr
    Y/Y884d/
    ///I84I/0d
    5//C/4//5I
    0||n||nq ua|e|
    /|ocess ua|e|
    /a|e and a|||a a|e ua|e|
    0esa||na||on
    8|ac||s| ua|e|
    was|e ua|e|s
    Bellew #ber membrooes
    Y|c|o 8 u|||a/|||a||on
    5prol weuod membrooes
    dano/|||a||on
    8eie|se 0smos|s
    Medule rooye
    4C5 8 d5/ a|oied
    Cemplete systems desyo
    u||| oss|||e coa||nq o/
    u|||a/|||a||on 8 8eie|se 0smos|s
    o| u|||a/|||a||on 8 dano/|||a||on
    DESALINATION AND
    WATER TREATMENT
    Science and Engineering
    www.deswater.com
    Desalination Publications
    International Science Services
    Objectives
    Due to the galloping growth of the desalination feld to help supply
    water to an exploding active thirsty population, there has been a
    surge in the number of scientists and engineers involved in water
    desalting and waste-water reclamation.
    Following this growth, there has been a food of papers from scientists
    and engineers, academia, government and industry from all regions
    of the world recording results of work in the lab or from operation of
    plants fowing into the editorial offce from about 100 countries. This
    information needs to be disseminated promptly and widely to the
    expanding desalination and water community as it is constantly ad-
    vancing and changing. It is often presented at conferences attended
    by few. Peer-reviewed papers are conveyed through the journal.
    There is a need to extend the coverage to accommodate additional
    selected papers promptly. We are ready to meet this challenge with
    this new publication alongside the journal Desalination.
    Desalination and Water Treatment is dedicated to research and application of desalination technology, environment and energy
    considerations, integrated water management, water reuse, wastewater and related topics. We are turning to main players in the feld to
    support the venture by participating in the publication and subscribing to the new journal at an attractive price, mainly through multiple
    subscriptions.
    Impact Factor Desalination and Water Treatment journal is included in the Web of Science, SCI and Current Contents so that it will
    get an impact factor.
    Citations: View papers of published volumes in this journal through http://www.deswater.com/vol1.shtml. Find papers to cite.
    Editorial Board: A distinguished worldwide editorial board and associate editors guides, monitors and reviews the journal. For editorial
    matters, contact: dwt@deswater.com.
    Peer Review: All papers are peer reviewed by at least two referees. Papers presented at conferences are peer reviewed and selected
    with the same standards as individually submitted papers. They therefore have the same archival value.
    Copyright will be retained by authors who may place their papers on their personal or institutional websites (Harvard System). An
    electronic copy of the fnal paper will be provided to authors for such use.
    Electronic Submission: Manuscripts are submitted electronically at http://www.deswater.com/submission.php using an online manuscript
    submission and peer review system.
    Online Desalination Directory (www.desline.com)
    The Desalination Directory plays a central role in networking the desalination community and all those interested in the feld. The Directory
    includes geographical and subject indexes, a cumulative index of Desalination, a calendar of events, information about courses and
    other timely material. Desalination and Water Treatment will be included in the Directory. There are currently 27,400 entries of which
    22,400 are individual owners, suppliers, users, academic, government, and industrial researchers, engineers, operators, managers, sales
    representatives and consultants, and 5,000 are nstitutions, companies and associations.
    Abstracting: Desalination and Water Treatment is covered in the Web of Science as well as in appropriate abstracting services.
    Contact:
    Editorial:
    Tel. +39 348 8848 406; eFax +1 928 5433066; email: dwt@deswater.com, web: www.deswater.com
    Subscriptions/Advertisements:
    OSC Associates, 29, rue Politzer, 94100 Saint Maur, France
    Tel. +33 1 70 71 63 84; Fax +33 1 77 72 27 59; email: contact@osc-edition.com
    Every organ in our body has a particular function.
    The kidneys, for example, perform the critical task of purifying
    our blood. If our kidneys fail, there is no simple solution.
    The best treatment is dialysis, i.e. artificial purification of the
    blood. Used in conjunction with a number of other remedies,
    it aims to restore everyday quality of life for patients.
    This is why we have brought together our expertise in the
    various aspects of dialysis and constantly strive to optimise
    our products through innovation. Around 1,100 patents and
    associated applications bear testimony to the strength of our
    innovation and this is undoubtedly one of the reasons why we
    are the global market leader in dialysis. If you would like to
    know more: www.fmc-ag.com
    1,100 patents.
    Because there is no simple
    solution to kidney failure.
    Up to 15,000 Fresenius Polysulfone

    hollow fibres each with a wall thickness


    of just 0.04 mm in every Fresenius Medical Care haemodialysis filter ensure that
    patients blood is purified and their quality of life enhanced.
    Heat Waves
    The unique Carbolite MRF 16/22
    employs CMAT Microwave Assist
    Technology to combine radiant
    heating & direct microwave
    heating of samples.
    Reaching
    temperatures of
    up to 1600C
    under fully
    flexible
    programmable
    control.
    Carbolite
    Parsons Lane Hope Hope Valley S33 6RB United Kingdom
    Tel: +44 (0)1433 620011 Email: info@carbolite.com
    Web: www.carbolite.com
    Publisher of the Euromembrane 2009
    Abstracts Book
    TABLE OF CONTENTS
    PLENARY LECTURES 1
    PL.1 Molecular, nano and microIabrication oI membranes
    M. Wessling
    2
    PL.2 Biological membranes on supports: Physical models oI cell surIaces and smart materials
    M. Tanaka
    2
    PL.3 HalI a Century Later - The Impact oI Membranes in Water and Wastewater Management Schemes
    H. Buisson
    3
    PL.4 Closing technology gaps to enable energy eIIicient membrane-based separations
    W. Koros
    3
    ORAL COMMUNICATIONS 5
    A - Materials 6
    A.1. Hybrid and polymeric membranes
    OA.1.1 Polymer-zeolite-additive three-component mixed matrix composite membrane Ior CO
    2
    /CH
    4
    separation
    E. Erpek, B. A. O:kale, S. Halitoglu, C. Atalav-Oral, M. G. Ahunbav, S. B. Tantekin-Ersolma:
    6
    OA.1.2 Mixed matrix membranes with high surIace area nanoporous materials Ior gas separation
    P. Gorgofo, S. Uriel, C. Telle:, J. Coronas
    6
    OA.1.3 Gas transport properties oI a novel copolymer oI vinylidene Iluoride
    G. Golemme, M. G. Buonomenna, F. Mikes, Y. Okamoto, J. C. Jansen
    7
    OA.1.4 Organic/inorganic hybrid nanocomposite membrane on the basis oI poly(4-methyl-2-pentyne) and TiO
    2
    S. Shishatskiv, W. Yave, J. Abet:, S. Matson, E. Litvinova, J. Khotimskiv, K.-J. Peinemann
    8
    OA.1.5 Dynameric membranes: toward an adaptive constitutional transport
    M. Barboiu
    9
    OA.1.6 EIIect oI preparation parameters on perIormance oI polyethersulIone based mixed matrix gas
    separation membranes
    E. Karatav, H. Kalipilar, L. Yilma:
    9
    OA.1.7 Sorption and diIIusion oI organic vapours in poly-trimethyl-silyl-norbornene: experimental
    characterization and comparison with NELF model predictions
    M. Gali:ia, M.G. De Angelis, G.C. Sarti
    10
    OA.1.8 DiIIerences in mass transport oI C
    1
    -C
    6
    alkanes and alcohols through perIluorinated membranes
    K. Friess, J.C. Jansen, B. Cernochova, J. Hvnek, O. Jopicka, M. Zgaar, M. Sipek
    11
    OA.1.9 Preparation oI super-hydrophobic PVDF membranes organized in a hierarchical manner
    C. L. Li, A. Deratani, D. M. Wang, D. Quemener, D. Bouve, J. Y. Lai
    12
    OA.1.10 Chain conIiguration, nanostructure oI Iree volume and Iunctional properties oI high permeable 1,2-
    disubstituted polyacetylenes
    S. Matson, E. Litvinova, E. Sultanov, J. Khotimskiv, S. Shishatskiv, W. Yave, K.-J. Peinemann, K.
    Raet:ke
    12
    A.2. Composite membranes
    OA.2.1 Characterization and modeling oI the organic vapor transport in TeIlon AF/Iumed silica mixed matrix
    membranes
    M. C. Ferrari, M. Gali:ia, M. G. De Angelis, G. C. Sarti
    13
    OA.2.2 Ultra thin Iilm composite membrane Ior CO
    2
    separation
    A. Car, W. Yave, J. Wind, K. J. Peinemann
    13
    OA.2.3 Azo-polymers containing EVAL membranes with switchable wettability
    B. Tvlkowski, S. Peris , R. Garcia-Jalls, J. A. Reina, J. C. Ronda, M. Giamberini
    14
    A.3. Inorganic membranes : ceramic, metallic, zeolite
    OA.3.1 Structural Ieatures and unique ion interactions oI MFI type zeolites Ior membrane desalination
    B. Zhu, A. Forstmeier, S. Pas, A. Hill, J. Lin, M. Duke
    14
    OA.3.2 A new route to microporous silica-alumina membranes Ior high-temperature gas separation
    A. Cheraitia, A. Avral, A. Julbe, H. Satha
    15
    OA.3.3 Multi-layer ceramic hollow Iibres via wet-spinning
    I. Stru:vnska, N.E. Benes, L. Winnubst, M. Wessling, A. Nifmeifer
    16
    OA.3.4 MultiIunctional ceramic membranes with hierarchical porous structure and dispersed metal
    nanoparticles
    C. Yacou, A. Avral, A. Julbe
    16
    OA.3.5 Fabrication oI the Pd-Ag and Pd-Ag-Au alloy membranes supported on porous YSZ tube
    T. M. Su:uki, D. A. Pacheco Tanaka, Y. Wakui, K. Noda, M. Kafiwara, T. Makino
    17
    OA.3.6 Keynote: Ceramic membranes in clean energy delivery processes
    J.C.D. Da Costa
    18
    OA.3.7 Amorphous silicon carbonitride H
    2
    permselective membranes
    J. Rouessac, W. Kafrouni, C. Charmette, J. Durand, A. Julbe
    18
    OA.3.8 Structural diversity in ceramic hollow Iibre membranes
    B. F. K. Kingsburv, K. Li
    19
    OA.3.9 New clay-alumina capillaries Ior MF and UF applications
    S. Cerneaux,

    S. Sarkar, S. N. Rov, A. Larbot,

    S. Bandvopadhvav
    19
    OA.3.10 New ceramic membrane resistant to abrasion
    E. Papin, P. Lescoche, A. Grangeon, L. Pivier, G. Balduchi
    20
    A.4. Ion conducting membranes : proton and oxygen
    OA.4.1 Mixed ionic-electronic conductor capillary membranes Ior gas separation
    M. Zipperle, S. Schirrmeister, J. Caro, T. Hirth, T. Schiestel
    20
    OA.4.2 High-temperature sealing oI ceramic capillary membranes Ior oxygen separation
    M. Sabfan, M. Zipperle, T. Betker, J. Caro, S. Schirrmeister, C. Rssel, T. Schiestel
    21
    OA.4.3 Hydrogen Ilux through selected HTM membranes
    Y. Larring, R. Bredesen
    22
    OA.4.4 Perovskite capillaries/hollow Iibres Ior gas separation in sustainable energy production
    C. Buvsse, A. Buekenhoudt, F. Snifkers, A. Kavaleuski, J. Luvten, H. Beckers, W. Doven, B.
    Molenberghs, S. Lenaerts, J. Kret:schmar
    23
    OA.4.5 Phosphonic acid-Iunctionalized Iluoropolymers as Iuel cell membrane materials
    R. Tavouo, G. David, S. Roualdes, B. Ameduri
    23
    OA.4.6 Phosphonic acid containing Poly(Aryl Ether Ketone)s
    E. Chauveau, J. Martin, C. Marestin, R. Mercier, H. Waton
    24
    OA.4.7 Preparation and characterization oI composite membranes using blends oI SPEEK/PBI Ior high
    temperature PEMFC applications
    E.C. van de Jen, Z. Borneman, M. Wessling
    25
    OA.4.8 Thermal properties oI side-chain sulIonated poly(ether sulIone)s
    J. Meier-Haack, A. Ptschke, L. Fallant, W. Butwilowski, K. Schlenstedt, A. Quetschke, C. Jogel
    25
    A.5. Nanostructured materials and surIace modiIication Functionalization
    OA.5.1 SurIace activated oxygen transport membranes based on perovskitic La
    0.58
    Sr
    0.4
    Co
    0.2
    Fe
    0.8
    O
    3-delta
    S. Baumann, D. Schlehuber, W.A. Meulenberg, T. Markus, H.P. Buchkremer
    26
    OA.5.2 Nano tailored ceramic membranes on porous metal substrates
    D. Ulhmann, F. Hauler, K. Brands, S. Smart, M. Bram, W.A. Meulenberg, J.C. Dini: da Costa
    27
    OA.5.3 Manipulation oI the transport properties and selectivity oI porous anodic alumina membranes by
    controlling the pore structures and surIace chemistry
    L. Jelleman, J. G. Shapter, D. Losic
    28
    OA.5.4 Preparation oI catalytic hollow Iiber membranes containing metal nanoparticles by two surIace
    modiIication techniques
    J. Macanas, L. Ouvang, M.L. Bruening, M. Muo:, J-F. Lahitte, J-C. Remigv
    28
    OA.5.5 Gas separation properties oI polyurethane/epoxy nanocomposite membrane
    M. Sadeghi, M. A. Aravand, A. H. Saeidi Dehaghani, S. Khatti Di:abadi
    29
    OA.5.6 A general method Ior the direct Iunctionalization oI polyethersulIone membranes with small molecules
    A. Schul:e, B. Marquardt, R. Schubert, M. R. Buchmeiser
    30
    OA.5.7 Stimuli-responsive membranes obtained by nanopore Iunctionalization with a thermo-sensitive
    polymer
    H. Alem, A.-S. Duwe:, P. Lussis, P. Lipnik, A. M. Jonas, S. Demoustier-Champagne
    31
    OA.5.8 SurIace modiIication oI segmented polyurethane membrane graIted with anti-Iouling polymer brushes
    by ozone treatment Ior improving blood compatibility
    Y.-J. Shih, Y. Chang
    31
    OA.5.9 AntiIouling modiIication oI polypropylene micoIiltration membrane surIace via 'polymer entrapping
    H. Guo, M. Ulbricht
    32
    OA.5.10 Enzymatic membranes prepared by using polyelectrolyte multilayer immobilization. Role oI the
    enzyme location on the catalytic reaction
    S. Guedidi, A. Deratani, C. Innocent, P. Defardin, S. Roudesli , Y. Yurekli, S. Alsov Altinkava
    33
    OA.5.11 Control oI concentration polarization by modiIication oI ion-exchange membrane surIace
    N. Pismenskava, J. Nikonenko, E. Belova, G. Pourcellv, Ph. Sistat, Ch. Larchet
    33
    OA.5.12 Film-Iorming cellulose acetate graIt copolymers with nano-structured architectures: Synthesis and
    characterization
    A. Jonquieres, M. Billv, A. Ran:ani Da Costa, P. Lochon, R. Clement, M. Dresch, S. Etienne, J. M.
    Hiver, L. David
    34
    A.6. Molecular recognition and selI-assembly membranes: liquid, biomimetic and Iacilitated transport
    OA.6.1 Bio-inspired mineralization in water-treatment processes: the inIluence oI biopolymers and organic
    substances on scaling oI RO/NF membranes
    Z. Steiner, H. Rapaport, Y. Oren, R. Kasher
    35
    OA.6.2 SelI-organized supramolecular ionic-channels in bilayer and polymeric membranes
    Y. Leduc, L. Bosch, E. Mahon, Y. M. Legrand, A. van der Lee, S. Mihai, M. Barboiu
    36
    OA.6.3 Dynamic biomimetic membranes: toward adaptive neuroreceptors systems
    S. Mihai, Y. Leduc, M. Barboiu
    36
    OA.6.4 Keynote: Partially positively polarized surIace oI silver and gold nanoparticles by electron acceptor
    and its implication to Iacilitated oleIin transport
    Y.S. Kang, S.W. Kang, J. Won
    37
    A.7. New breakthrough approaches Ior membrane materials
    OA.7.1 Exploring the potential oI oligonucleic acids ('aptamers) Ior designing stimuli-responsive membranes
    T. Schfer, M. Schfer, C. O:alp
    37
    OA.7.2 Hollow Iillers in mixed matrix membranes Ior solvent resistant nanoIiltration
    K. Janherck, S. Aldea, A. Aerts, J. Martens, I. Jankelecom
    38
    OA.7.3 Gas separation using ionic liquid polymers
    R. D. Noble, D. L. Gin, J. E. Bara, B. Joss, A. Finotello, T. Carlisle
    39
    OA.7.4 Dynameric materials Ior CO
    2
    separation toward adaptive transport membranes
    G. Nasr, C. Charmette, J. Sanche:, M. Barboiu
    39
    OA.7.5 Constitutional selI-instructed dynamic membranes-toward adaptive ion-channel devices
    Y.-M. Legrand, A. Ca:acu, A. Pasc, G. Nasr, A. Jan der Lee, M. Barboiu
    40
    OA.7.6 Stable HybSi

    nanosieve membranes Ior dehydration oI alcohols and aprotic solvents


    R. Kreiter, H. M. van Jeen, M. D.A. Rietkerk, H. L. Castricum, J. E. ten Elshof

    , J. F. Jente
    41
    OA.7.7 Keynote: Carbon nanotube membranes; mimicking nature with dramatic mass transport and gate
    keeper activity
    B.J. Hinds
    41
    B - Characterization 42
    B.1. Material structure
    OB.1.1 Analysis oI the Iree volume distribution in HyIlon AD glassy perIluoropolymers by photochromic
    probes: comparison with other techniques
    J. C. Jansen, M. Macchione, E. Tocci, L. De Loren:o, Y. P. Yampolskii, J. P. Shantarovich, M.
    Heuchel, D. Hofmann, E. Drioli
    42
    OB.1.2 Polymer-solvent interaction as a Iactor inIluenced on properties and gas separation characteristics oI
    polymer Iilms
    J. Kostina, G. Bondarenko, A. Alentiev, Y. Yampolskii, I. Ronova
    43
    OB.1.3 Gas transport in glassy polymers Ior probing their supramolecular structure
    A. Alentiev, Y. Yampolskii, G. Bondarenko, J. Kostina, E. Antipov
    43
    OB.1.4 Structure and swelling oI an immersed NaIion membrane under compression
    N. Otmani, A. Morin, H. Mendil-Jakani, G. Gebel, S. Besse
    44
    OB.1.5 Keynote: SurIace-Iunctionalized membranes Ior low-Iouling micro- and ultraIiltration and selective
    membrane adsorber applications
    M. Ulbricht
    45
    B.2.Membrane perIormance
    OB.2.1 High perIormance wet air oxidation (WAO) oI organic pollutants using a catalytic membrane reactor
    M. Alame, A. Abusaloua, M. Pera-Titus, N. Guilhaume, S. Miachon, K. Fiatv, J-A. Dalmon
    45
    OB.2.2 Gas transport properties through PVDF membrane
    S. H. Choi, J. C. Jansen, F. Tasselli, G. Barbieri, E. Drioli
    46
    OB.2.3 Oily wastewater treatment by means oI -alumina nanoIiltration membrane
    Z. Sadeghian, F. Zamani, N. Ashrafi:adeh
    47
    OB.2.4 Determining the virus removal retention capabilities oI UF membranes during operation at pilot scale
    H. Humbert, C. Machinal, I. Labave, J. Jacquemet, P. Brisson, J.C. Schrotter
    47
    OB.2.5 Membranes Ior pressure retarded osmosis power plants
    T. Holt, E. Sivertsen, T. Thorsen
    48
    OB.2.6 PerIormances oI aquasource new ultraIiltration membranes
    L. Feriol, P. Sauvade
    49
    OB.2.7 Partially positively polarized surIace oI silver and gold nanoparticles by electron acceptor and its
    implication to Iacilitated oleIin transport
    Y.S. Kang, S. W. Kang, J. Won
    49
    OB.2.8 Atomic Iorce microscope characterization oI ceramic ultraIiltration membranes in diIIerent operational
    states
    J. Llanos, P. M. Williams, S.Y. Cheng, D. Rogers, C. Wright
    50
    OB.2.9 Volumetric properties and mass transIer oI sugars through a NF membrane: inIluence oI the ionic
    composition
    J. Bov, S. Galier, H. Roux-de Balmann
    50
    OB.2.10 Characterization oI polymer electrolyte membrane - Relationship between morphology and transport
    properties
    A. Ohira, N. Takimoto, H. F. M. Mohamed, K. Kidena, T. Ohkubo, Y. Kobavashi
    51
    B.3. Non-destructive and in-situ dynamic characterization
    OB.3.1 In situ characterisation oI membrane Iormation by phase inversion
    J. Mendret, P. Bacchin, J-C. Remigv
    52
    OB.3.2 Positron annihilation spectroscopy: a novel non-destructive characterization technique to probe the
    molecular level oI polyimide-based solvent resistant nanoIiltration membranes
    A. Cano-Odena, P. Jande:ande, K. Hendrix,

    R. Zaman, K. Mostafa, W. Egger, P. Sperr, J. De
    Baerdemaeker

    , I. F. J. Jankelecom
    53
    OB.3.3 In situ dynamic characterization oI water transport and proton mobility in NaIion by ATR-FTIR and
    micro-Raman spectroscopy
    S. Deabate, P. Huguet, P. Sistat, L. Grosmaire, A. Morin, G. Gebel
    54
    OB.3.4 Monitoring oI membrane processes using non-invasive Iluorescence techniques
    C. A. M. Portugal, J. G. Crespo
    55
    OB.3.5 Characterisation oI the properties and the sugar penetration in ion exchange membranes equilibrated in
    sugar aqueous solutions
    E. Jera, P. Sistat, P. Huguet, S. Deabate, S. Galier, H. Roux de Balmann
    55
    OB.3.6 Impact oI chemical treatments on NaIion sorption using
    1
    H NMR
    F. Xu, S. Leclerc, O. Lottin, D. Canet, J. Bedet
    56
    OB.3.7 Mass transIer analysis in polymer solutions prior to phase separation by near inIrared and Raman
    spectroscopy
    C. Pochat-Bohatier, W. Werapun, D. Bouver, E. Petit, P. Huguet, A. Deratani, J.-P. Desfours
    57
    OB.3.8 Keynote: Dynamic characterization oI membrane processes: the rear window paradigm
    J.G. Crespo
    58
    C - Modelling and Simulation 58
    C.1. Molecular modelling
    OC.1.1 Gas sorption in glassy polymers Comparative characterization using experimental and molecular
    modelling techniques
    M. Bhning, O. Hlck, M. Heuchel, D. Hofmann
    58
    OC.1.2 Study oI ion transport through nanopores
    J. Dweik, B. Coasne, F. Henn, J. Palmeri
    59
    OC.1.3 The role oI the hydrogen-bonding and weak interactions in competitive interacting processes
    inIluencing the polymeric membrane properties
    G. De Luca, A. Gugliu::a, E. Drioli
    60
    OC.1.4 Atomistic simulation oI gas sorption isotherms in a polymer oI intrinsic microporosity (PIM-1)
    M. Heuchel, O. Hlck, M. Bhning, D. Fritsch, D. Hofmann
    60
    OC.1.5 Keynote: Membrane structure and transport modelling across scales
    J.N. Burganos
    61
    C.2. Transport mechanisms
    OC.2.1 Modelling transport through integrally skinned asymmetric organic solvent nanoIiltration membranes.
    EIIect oI concentration polarisation and osmotic pressure
    L.G. Peeva, P. Silva, A.G. Livingston
    62
    OC.2.2 Transport properties oI nanoIiltration membranes with inhomogeneous charge distributions
    A. S:vmc:vk, H. Zhu, B. Balannec
    62
    OC.2.3 Predictive transport model Ior solvent permeation through organic and inorganic solvent resistant
    nanoIiltration membranes
    S. Darvishmanesh, A. Buekenhoudt, J. Degreve, B. Jan der Bruggen
    63
    OC.2.4 A simulation model Ior membrane aIIinity chromatography
    S. Dimartino, C. Boi, G.C. Sarti
    64
    OC.2.5 Rigorous modeling oI the solute transport in emulsion liquid membranes in hollow Iiber contactors
    E. Bringas, M.F. San Roman, I. Orti:
    64
    OC.2.6 Modeling oI coupled mass and heat transIer through venting membranes Ior automotive applications
    A. Barkallah, S. Druon Bocquet, J. Sanche:, J. Rivenc
    65
    OC.2.7 Numerical study oI the Iractionation oI two proteins with opposite charges by a hybrid membrane cell
    composed oI symmetrically charged membranes
    S.I.S. Pinto, J.M. Miranda, J.B.L.M. Campos
    66
    OC.2.8 Nano-scale approach to diIIusion in semi-crystalline polyoleIins
    H. Hafova, R. Pokornv, T. Gregor, L. Seda, J. Kosek
    66
    OC.2.9 Molecular investigations oI gas and vapors transport properties in a modiIied co-poly(amide-12-b-
    ethylene oxide) membrane
    L. De Loren:o, E. Tocci, A. Gugliu::a, M. Macchione, E. Drioli
    67
    OC.2.10 Simulation oI membrane Iiltration at microscopic scale
    Q. Derekx, D. Jevret, K. Glucina, P. Bacchin, P. Moulin
    68
    OC.2.11 Forced permeation transition in high molecular weight polymer cross-Ilow ultraIiltration
    L. Beguin, H. Duval, M. Rakib
    69
    OC.2.12 A heat-and-mass transIer correlation Ior sludge to optimize mass transIer in tubular airliIt membrane
    systems
    N. Rios, C.C.J. Chan, P.R. Berube, I. Nopens
    69
    OC.2.13 InIluence oI thermal eIIects on gas-liquid absorption in a hollow Iiber membrane contactor: case oI
    carbon dioxide in a MEA solution
    N. Boucif, D. Roi:ard, E. Favre
    70
    D - Processes 71
    D.1. Classical membrane operations: MF, UF, NF, RO, PV, ED.
    OD.1.1 Ionic strength impact in Iiltration oI skimmed milk: analysis oI casein micelles and cake properties
    G. Gesan-Gui:iou, A. Bouchoux, A. Jimene:-Lope:, F. Garnier-Lambrouin
    71
    OD.1.2 Separation oI -Lactalbumin and -Lactoglobulin Irom skim milk by dynamic Iiltration
    J. Espina, M. Y. Jaffrin, L.H. Ding
    72
    OD.1.3 Application oI nanoIiltration Ior swimming pool water treatment - potential and challenges
    A. M. Klpfel, T. Glauner, F. H. Frimmel
    73
    OD.1.4 NanoIiltration process in Iractionation oI galacto-oligosaccharides continuously produced in
    bioreactors
    J.A. Botelho-Cunha, M. Mateus, J.C.C. Petrus, M.N. de Pinho
    73
    OD.1.5 InIluence oI additive mineral salt on the puriIication perIormances oI glucose/sodium lactate solutions
    by nanoIiltration
    C. Umpuch, S. Galier, S. Kanchanatawee, H. Roux-de Balmann
    74
    OD.1.6 Permselectivity oI inorganic and organic ions by ion-exchange membranes: treatment oI RO-
    concentrate by electrodialysis
    Y. Zhang, B. Jan der Bruggen, L. Pinov, B. Meesschaert
    75
    OD.1.7 Ampholyte transIer in ion exchange membrane systems at underlimiting and overlimiting currents
    E. Belova, N. Pismenskava, J. Nikonenko, K. Lebedev, G. Pourcellv, Ph. Sistat
    76
    OD.1.8 Impact oI organic component on separation eIIiciency during hydrophilic pervaporation
    W. M. Kufawski
    76
    OD.1.9 Dehydration oI water/dichloromethane/n-butanol mixtures by pervaporation; optimisation and
    modelling by response surIace methodology
    J. Garcia, J. Landaburu-Aguirre, E. Pongrac:, P. Permki, R. L. Keiski
    77
    OD.1.10 Cost-EIIective Low Pressure Membrane Systems
    W. Sellerberg, L. Escobar-Ferrand, C. Liu, M. Farcv, A. Wachinski
    78
    OD.1.11 Fractionation oI Cyclodextrins mixture by Ultra and NanoIiltration
    F. Ellou:e, N. Ben Amar, A. Deratani, W. Zimmermann
    78
    OD.1.12 Process oI desalination oI low energy consumption. Magnetohydrodynamics desalination process
    J. Abad Garrido, P. Peas Ballester
    79
    OD.1.13 New membrane applications in oenology
    R. Ghidossi, A. Massot, C. Poupot, M. Mietton Peuchot
    79
    D.2. Membrane reactors: high/low temperature; catalytic /non catalytic; enzymatic or microbial.
    OD.2.1 Global model oI the ion exchange membrane bioreactor Ior removal oI anionic micropollutants Irom
    drinking water supplies
    A.R. Ricardo, R. Oliveira, S. Jeli:arov, M.A.M. Reis, J.G. Crespo
    80
    OD.2.2 Modelling oI a membrane bioreactor Ior wastewater treatment using 2D-Iluorescence spectroscopy as a
    complementary monitoring tool
    C. F. Galinha, C. Portugal, G. Carvalho, G. Guglielmi, D. Chiarani, G. Andreottola, R. Oliveira, M.
    A. M. Reis, J. G. Crespo
    81
    OD.2.3 Biocatalytic membrane reactors to guide and control bioconversion, isolation and stabilization oI water
    unstable intermediates
    R. Ma::ei, L. Giorno, E. Drioli
    82
    OD.2.4 Membrane assisted catalytic dehydrogenation oI ethane
    T. Giddings, L. Nossova, J. Galus:ka
    83
    OD.2.5 Mass transport in biocatalytic membrane reactors
    E. Nagv
    83
    OD.2.6 Theoretical investigation on the eIIect oI superIicial deIects over the membrane surIace oI Pd-based
    membrane reactors Ior methane steam reIorming
    A. Caravella, F.P. Di Maio, A. Di Ren:o
    84
    OD.2.7 Hydrogen production by dehydrogenating cyclohexane using membrane reactors with pore-size-
    controlled silica membranes
    Y. Ohta, K. Akamatsu, T. Sugawara, T. Hattori, S. Nakao
    85
    OD.2.8 Detailed process analysis oI a pervaporation membrane reactor Ior a heterogeneously catalysed
    esteriIication reaction
    T. Roth, S. Lauterbach, P. Kreis
    85
    OD.2.9 Ceramic membrane microreactors (CeMR)
    H.C. Aran, D. Salamon, R. Groote, J.M. Jani, J.K. Chinthaginfala, R.G.H. Lammertink, M. Wessling
    86
    OD.2.10 EIIect oI powdered activated carbon (PAC) on the microbial behavior in membrane bioreactor (MBR)
    R.C. Eusebio, H.G. Kim, H.S. Kim
    87
    OD.2.11 Keynote: Polymeric catalytic membranes
    E. Fontananova, E. Drioli
    87
    D.3. Membrane contactors: membrane distillation; crystallization; emulsiIication.
    OD.3.1 The inIluence oI concentration post sulphuric acid in the Ieed on HCl separation in membrane reactor
    by direct contact membrane distillation
    A. Lapin, M. Tomas:ewska
    88
    OD.3.2 Preparation and characterization oI PVDF hollow Iibre membranes Ior vacuum membrane distillation
    A. Criscuoli, A. Figoli, S. Simone, M.C. Carnevale, E. Drioli
    89
    OD.3.3 Concentration oI phenolic acids and Ilavonoids in aronia melanocarpa (choke berry) juice by osmotic
    membrane distillation
    L. Fferbaek Sotoft, K.J. Christensen, J.G. Horn, B. Norddahl
    90
    OD.3.4 Modeling aroma stripping under various Iorms oI membrane distillation processes
    G. Jonsson
    91
    OD.3.5 Microporous vs dense materials Ior hollow Iiber membrane contactors: A critical theoretical and
    experimental study
    P. Nguven, D. Roi:ard, E. Favre, N. Boucif
    91
    OD.3.6 SurIace modiIication Ior easier interIace stabilization in membrane contactors: application to
    Iractionation oI essential oils
    A. Dupuv, J. Athes, J. Schenk, U. Jenelten, I. Souchon
    92
    OD.3.7 Amino acid salt solutions as selective absorption liquids in gas-liquid membrane contactors Ior CO
    2
    capture
    K. Fischbein, H. Mengers, K. Nifmeifer, W. Brilman, M. Wessling
    93
    OD.3.8 EIIect oI membrane wetting on the process eIIiciency oI a hollow Iibre membrane contactor Ior gas
    recovery
    P. Luis, A. Garea, A. Irabien
    93
    OD.3.9 Membrane emulsiIication at high temperature to assist the preparation oI highly concentrated and
    stable solid lipid nano- micro-suspensions
    L. Giorno, F. Ba::arelli, E. Drioli
    94
    OD.3.10 Using membrane-aerated bioIilm reactor to remove ammonium Irom wastewater with simultaneous
    nitriIication and denitriIication
    C. Picard, J.C. Schrotter, J.C. Rouch, C. Albasi, J.C. Remigv
    95
    OD.3.11 Silica Scaling in Ilat-sheet and hollow Iiber DCMD modules
    Y. Ladi:hanskv, A. Dov, E. Korin, J. Gilron
    96
    OD.3.12 Antisolvent membrane crystallization oI organic molecules
    G. Di Profio, E. Curcio, E. Drioli
    96
    OD.3.13 Hydrophilic microporous media or membrane contactor Ior oxygen transIer in wines
    I. Chiciuc, E. Ascencios, R. Adoua, A. Devatine, M. Mietton Peuchot
    97
    D.4. AIIinity Membrane
    OD.4.1 Metal aIIinity chromatography Ior His
    6
    -tagged protein puriIication
    M.P. Dubois, C. L. Gifiu, M.P. Belleville, S. Druon-Bocquet, X. Santarelli, D. Paolucci-Jeanfean
    98
    OD.4.2 Permeation oI salicylic acid through a supported liquid membrane based on ionic liquids
    N. Kouki, R. Taveb, M. Dhahbi
    98
    D.5. Hybrid operations and process integration
    OD.5.1 Industrial scale experiences with pervaporation and vapour permeation
    E. M. Maus, A. Willenberg
    99
    OD.5.2 Process perIormance improvement by HybSi

    nanosieve membranes Ior dehydration by pervaporation


    H.M. van Jeen, A. Motelica, D.P. Shanahan, R. Kreiter, M.D.A. Rietkerk, H.L. Castricum,
    J.E. Ten Elshof , J. F. Jente
    100
    OD.5.3 Study on hybrid process including esteriIication reaction & pervaporation
    A. Penkova

    , G. Polotskava

    , A. Toikka
    100
    OD.5.4 Integration oI pervaporation and vapor permeation with an esteriIication reaction: Lactic acid reaction
    with ethanol
    E. Gon:ale:-Dia:, A. Willenberg, A. Hbner, N. Martin, E. Maus
    ,
    J.R. Alvare:, S. Luque
    101
    OD.5.5 Separation oI organic product streams Irom reactive distillation columns: Membrane material selection
    and process integration studies
    T. Brinkmann, H. Pingel, Th. Wolff, M. Dker, J. Gmehling
    102
    OD.5.6 Coagulant inIluence on the removal oI arsenic Irom drinking water by an anion exchange membrane-
    assisted process
    J. Llanos, A. Oehmen, J. Fradinho, M.A.M. Reis, S. Jeli:arov, J.G. Crespo
    102
    OD.5.7 Capillary electrochromatography and membrane technology: merging the advantages
    K. Kopec, D. Stamatialis, M. Wessling
    103
    D.6. Process intensiIication with membranes
    OD.6.1 Keep it natural! Adjusting the pH oI Iood products without chemical additives thanks to bipolar
    membrane electrodialysis
    F. Lutin
    104
    OD.6.2 Experimental and theoretical study oI pulse Iield electrodialysis
    B. Rui:, P. Sistat, P. Huguet, J. Nikonenko
    104
    OD.6.3 Process intensiIication using an inorganic membrane reactor - water removal through a sod membrane
    S. Khafavi, K. Jansen, F. Kapteifn
    105
    OD.6.4 Process design oI Iull scale membrane distillation plants Ior blackcurrant juice concentration on the
    basis oI laboratory and pilot scale tests
    L. Fferbaek, K.J. Christensen, R. Andresen, B. Norddahl
    106
    OD.6.5 Keynote: New Membranes Ior New Processes Advances in Organic Solvent NanoIiltration
    A.G. Livingston
    107
    E - Module Design and Engineering 108
    E.1. Fluid mechanics. Computational Iluid dynamics
    OE.1.1 Mathematical analysis oI the multiple-scale Ilow Iield in spiral wound membrane modules
    M. Kostoglou, A. J. Karabelas
    108
    OE.1.2 Gas-liquid contacting in ceramic membrane microreactor: Numerical and experimental study
    J.M. Jani, D. Salamon, H.C. Aran, R.G.H. Lammertink, M. Wessling
    108
    OE.1.3 Visualisation oI cake layer Iormation and liquid Ilow in a microIiltration process via nuclear magnetic
    resonance (NMR) tomography
    S. Buetehor, L. Utiu, M. Kueppers, B. Bluemich, T. Wintgens, T. Melin
    109
    OE.1.4 How spacer geometry can aIIect the thermo-Iluid dynamics oI a membrane distillation module
    A. Cipollina, A. Di Miceli, G. Micale, L. Ri::uti
    110
    E.2. Dynamic and design module operation
    OE.2.1 Challenges in designing a pressure retarded osmosis power plant
    E. Sivertsen, T. Holt, T. Thorsen
    110
    OE.2.2 Numerical and experimental methodology Ior the development oI a highly selective ceramic
    microIiltration membrane intended to bioprocesses
    F. Springer, E. Carretier, D. Jevret, D. Dhaler, P. Moulin
    111
    OE.2.3 Optimal control oI wash water utilization in batch diaIiltration
    Z. Kovacs, M. Ebrahimi, P. C:ermak
    112
    E.3. Microsystems and microtechnologies
    OE.3.1 Mass transIer enhancements in ultraIiltration membrane applications using new micro-engineered
    membrane spacers
    C. Frit:mann, H. Li, T. Melin
    113
    OE.3.2 Keynote: Dynamic micro Iractionation
    C.J.M. van Rifn, A. Nguven
    113
    E.4.Fouling
    OE.4.1 Membrane Iouling characterization by conIocal scanning laser microscopy in microIiltration processes
    M. Zator, M. Ferrando, F. Lope:, C. Gell
    114
    OE.4.2 MicroIluidic Iiltration
    I. Ngene, R. Lammertink, M. Wessling, W. Jan der Meer
    114
    OE.4.3 Membrane bioIouling eIIects oI antiscalants used in reverse osmosis
    T. Z. Re:ene, Y. Oren, M. Her:berg
    115
    OE.4.4 InIluence oI colloidal interactions on the microIiltration oI milk: a surIace energy approach
    W. Khnl, A. Pirv, T. Grein, S. Ripperger, U. Kulo:ik
    116
    OE.4.5 Filtration test cells: iI properly used, a helpIul tool Ior assessing Iouling propensity in MBR
    T. de la Torre, B. Lesfean, A. Drews, M. Kraume
    116
    OE.4.6 Relationship between types oI oscillating shear proIiles and membrane Iouling
    C.C.J. Chan, P.R. Berube, E.R. Hall
    117
    OE.4.7 The inIluence oI membrane characteristics on Iouling in an MBR
    P. van der Marel, A. Zwifnenburg, A. Kemperman, M. Wessling, H. Temmink, W. van der Meer
    118
    OE.4.8 Modeling the relation between the silt density index and the modiIied Iouling index
    A. Alhadidi, A. Kemperman, J. Schippers, M. Wessling, W. Jan der Meer
    119
    OE.4.9 Electrodialysis oI model salt solutions containing whey proteins : mineral Iouling investigations and
    enhancement by pulsed electric Iield and modiIied cell conIiguration
    C. Casademont, E. Avala-Bribiesca, P. Sistat, B. Rui:, G. Pourcellv, L. Ba:ine
    120
    OE.4.10 New water pretreatment combining clays and ultraIiltration membranes to limit cake Iouling
    M. Pontie, A. Thekkedath, J.B. Castaing, A. Masse, P. Jaouen
    120
    E.5.Pre-treatment and cleaning
    OE.5.1 Pre-treatment Ior drinking water membrane processes
    A. Barrios Martine:, P. Moulin
    121
    OE.5.2 Use oI degradation products oI milk and vegetal oil components Ior bio-cleaning oI membrane
    D. Delaunav, M. Rabiller-Baudrv, F. Piquet, L. Paugam
    122
    OE.5.3 Action oI oxidizing disinIectants on a partially-cleaned PES ultraIiltration membrane Iouled with milk
    proteins
    L. Paugam, D. Delaunav, M. Rabiller-Baudrv
    122
    OE.5.4 Industrializing continuous high Irequency back pulsing to maintain /enhance a high Ilux in a spiral
    wrap membrane element
    R. D. Sanderson, A. Elarbi
    123
    F - Applications 124
    F.1. Energy Fuel cells H
    2
    recovery
    OF.1.1 Determination oI water concentration proIile through NaIion

    membrane under Iuel cell operation by


    Small Angle Neutron Scattering (SANS)
    A. Morin, F. Xu, G. Gebe, O. Dia
    124
    OF.1.2 PFSA membrane degradation analysis through mechanical tensile tests
    S. Escribano, A. Morin, L. Rouillon, G. Gebel
    125
    OF.1.3 Improvements oI the long-term stability oI proton and anion conducting membranes Ior Iuel cell
    applications
    M. Gross, R. Grtner, H.-G. Her:, G. Maier
    125
    OF.1.4 InIluence oI modiIied mixed membranes on the direct ethanol Iuel cell perIormance
    K.S. Roelofs, C. Cremers, F. Jung, T. Hirth, T. Schiestel
    126
    OF.1.5 Plasma processes Ior the manuIacture oI original anion conducting membranes Ior solid alkaline
    membrane Iuel cells
    S. Roualdes, J. Frugier, J. Durand
    127
    OF.1.6 TECTONIC project: route to PCFC technology
    M. Marronv, P. Baranek, O. Joubert, E. Quare:, J.C. Grenier, F. Mauvv, P. Berger, L. Dessemond, N.
    Grunhaum, G. Taillades, M. Taillades-Jacquin, A. Thorel, R. Costa
    127
    OF.1.7 PCFCs : materials, single cells and stacks
    M.L. Fontaine, Y. Larring, S. Mei, R. Bredesen
    128
    OF.1.8 Water and proton incorporation under pressure and temperature into zirconate perovskites Ior hydrogen
    production: ionic conductivity and host Iramework behaviour
    O. Lacroix, A.K. Sirat, B. Sala, A. Slodc:vk, Ph. Colomban, S. Willemin, A. Jan der Lee, K. Rhamouni,
    H.Takenouti, B. Bendferiou
    129
    OF.1.9 New Iuel cell membranes Ior hydrogen puriIication and proton transport
    He Bai, W.S. Winston Ho
    130
    OF.1.10 Experimental study oI concentration polarization on the hydrogen Ilux through thin, highly selective
    palladium based membranes
    J. Catalano, M. G. Baschetti, G. C. Sarti
    131
    OF.1.11 MultiIunctional dense ceramic hollow Iibre membrane reactors Ior methane conversion
    Z.T. Wu, B. Wang, K. Li
    131
    OF.1.12 Vanadium-based, metal-metal composite membranes Ior hydrogen separation
    C. Nishimura, M. Komaki, K. Iwasa, M. Akiduki, S. Ogawa, H. Yoshinaga
    132
    OF.1.13 Thin Pd-23wAg membranes Ior hydrogen separation
    R. Bredesen, T.A. Peters, M. Stange
    133
    OF.1.14 Blue energy
    J. Jeerman, S.J. Met:, M. Saakes, G.J. Harmsen
    134
    F.2. Environment Waste treatments
    OF.2.1 Comparison oI the operational processes oI three diIIerent Iull-scale membrane bioreactors
    P. Kr:eminski, A. van Nieuwenhuif:en, J. van der Graaf
    134
    OF.2.2 EIIect oI the presence oI cytostatic drugs on the sludge oI a membrane bioreactor, consequence on the
    process
    L.F. Delgado, C. Dorendeu, B. Marion, J. Faucet-Marquis, A. Pfohl-Les:kowic:, S. Schetrite,
    S. Paranthoen, C. Albasi
    135
    OF.2.3 MBR long term experiment: toward a normalisation oI operating parameters
    J. Lebegue, M. Heran, A. Grasmick
    136
    OF.2.4 Flux enhancing chemicals in MBR: A 3 year comprehensive study
    J. Iversen, S. Hermann, A. Drews, B. Lesfean, M. Kraume
    136
    OF.2.5 EIIective Iouling control on a NF membrane module: a three year long case study
    M. Stoller
    137
    OF.2.6 The Iorward osmosis membrane bioreactor: a multi-barrier approach Ior water reuse
    A. Achilli, T.Y. Cath, E.A. Marchand, A.E. Childress
    138
    OF.2.7 Oil production water treatment with eletrodialysis
    I. Medina, A. Ramire:, A. Cardenas
    138
    OF.2.8 Demineralization oI saline waste waters containing phenol by electrodialysis
    F.J. Borges, R. Guardani, H. Roux-de Balmann
    139
    OF.2.9 Gas separation eIIectiveness oI supported ionic liquid membranes compared to non-porous membranes
    P. Cserfesi, N. Nemestothv, K. Belafi-Bako
    139
    OF.2.10 NanoIiltration oI eIIluents containing heavy metals: nanoIlux simulations as a descriptive and
    predictive tool Ior research and industry needs
    L. Schrive, J. Bonhoure, A. Deratani, J. Palmeri
    140
    OF.2.11 Treatment oI phenol eIIluents coupling Fenton`s oxidation and nanoIiltration
    X. Bernat, A. Fortunv, C. Bengoa, F. Stber, A. Fabregat, J. Font
    141
    OF.2.12 Old reverse osmosis modules in the Iuture : solutions oI reuse
    M. Pontie, E. Ould Mohamedou, J. Leparc, S. de la Puente Gon:ale:, P. Jaouen
    141
    OF.2.13 Reverse osmosis solutions Ior reuse applications
    E. Chaumien, R. Boda, L. Boutarin
    142
    OF.2.14 Cost eIIective treatment oI drinking water production wastes
    B. Bo:kava-Schrotter, C. Daines-Martine:, P. Breant, J. C. Schrotter
    142
    F.3. Drinking water Desalination
    OF.3.1 Coastal seawater testing oI an advanced microIiltration/reverse osmosis desalination demonstrator
    D. Nordham, J. Hein:el, B. Jarnava, M. Miller, I. Peek
    143
    OF.3.2 New ultraIiltration membrane integrity test monitoring by magnetic susceptibility seawater membranes
    Ior desalination
    H. Guo, Y. Wvart, J. Perot, F. Nauleau, P. Moulin
    144
    OF.3.3 Three-stage concentrate treatment Ior brackish water reverse osmosis
    L. Greenlee
    ,
    E. Barbot, D. Lawler, B. Freeman, B. Marrot, P. Moulin
    145
    OF.3.4 Study oI the eIIects oI deIects in ultraIiltration membranes on the log removal value (LRV) oI MS2 and
    the molecular weight cut-oII (MWCO)
    G. Pierre, A. Furiga, C. Roques, S. Rapenne, J.-C. Schrotter, P. Sauvade, O. Lorain, P. Aimar, C.
    Causserand
    146
    OF.3.5 Theoretical evaluation oI a thermopervaporation oI water vapor
    R. Noble, P. Aptel, J.-C. Remigv, P. Aimar
    147
    OF.3.6 Electrochemical detection oI original virus surrogates: a new method Ior the inline characterisation oI
    virus retention in membrane processes
    L. Soussan, C. Guigui, S. Alfenore, S. Mathe, C. Cabassud
    147
    OF.3.7 Removal oI norovirus by a coagulation-ceramic MF hybrid system
    T. Matsushita, N. Shirasaki, A. Oshiba, T. Urasaki, Y. Matsui, K, Ohno
    148
    OF.3.8 High perIormance seawater membranes Ior desalination
    L. Boutarin, R. Boda, E. Chaumien
    149
    F.4. Non aqueous membrane applications
    OF.4.1 Solvent resistant nanoIiltration: an eIIicient and sustainable strategy Ior product puriIication and
    recovery oI catalysts in click chemistry reactions
    A. Cano-Odena, P. Jande:ande, D. Fournier, W. Jan Camp, F. E. Du Pre:, I. F. J. Jankelecom
    149
    OF.4.2 Composite hollow Iibres membranes Ior organic solvent nanoIiltration (OSN)
    S.M. Dutc:ak, I. Stru:vnska, M.W.J. Luiten-Olieman, D. Stamatialis, L. Winnubst, M. Wessling
    150
    OF.4.3 Solvent Iiltration 'matrix: assessing the potential oI ceramic nanoIiltration membranes in solvent
    environments
    P. Jande:ande, K. Wvns, J. Mevnen, A. Buekenhoudt
    151
    OF.4.4 PEEKWC membranes Ior treatment oI organic solvent solutions
    M. G. Buonomenna, G. Golemme, J. C. Jansen, E. Drioli
    151
    OF.4.5 Batchwise and continuous organophilic nanoIiltration oI Grubbs type oleIin metathesis catalysts
    K. Ebert, K. Buhr
    152
    OF.4.6 Processing oI a-protic solvents with NF membranes
    F.P. Cuperus, I.M. Wienk
    153
    OF.4.7 Keynote: New materials and approaches Ior solvent resistant nanoIiltration (SRNF)
    I. Jankelecom
    153
    F.5. Gas separation Air treatment CO
    2
    recovery
    OF.5.1 CO
    2
    selective membranes Ior coal power plants
    S. Shishatskiv, J.R. Pauls, S.P. Nunes, K.-J. Peinemann
    154
    OF.5.2 Synthesis, characterization, and molecular simulation oI 6FDA/BTDA-pBAPS copolyimide membrane
    Ior CO
    2
    /CH
    4
    separation
    S. Halitoglu, O. Yilma:, C. Atalav-Oral, M. G. Ahunbav, S. B. Tantekin-Ersolma:
    155
    OF.5.3 High Ilux and selectivity SAPO-34 membranes Ior CO
    2
    /CH
    4
    separation
    S. Li, M. A. Carreon, J. L. Falconer, R. D. Noble
    155
    OF.5.4 Development oI cesium-incorporated carbon membranes Ior CO
    2
    separation under humid conditions
    T. Kai, S. Ka:ama, Y. Fufioka
    156
    OF.5.5 Membranes Ior dehydration and CO
    2
    capture oI Ilue gases
    K. Nifmeifer, J. Potreck, H. Sifbesma, S. Reiferkerk, K. Fischbein, M. Wessling
    156
    OF.5.6 Thin Iilm composite membranes Ior CO
    2
    /N
    2
    and O
    2
    /N
    2
    mixed gas separations using polymers oI
    intrinsic microporosity on poly (vinylidene Iluoride)
    L. Lavton, M. M. Dal-Cin, A. Kumar, N. Du, M. D. Guiver
    157
    OF.5.7 PEO based membranes Ior CO
    2
    capture Irom light gases using multi-component Ieed mixtures
    S. R. Reiferkerk, K. Nifmeifer, M. Wessling
    158
    OF.5.8 Reducing CO
    2
    Iootprint with hydrogen separation membranes
    E. Engwall, J. Saukaitis, G. Komplin, M. Joshi, A. Del Paggio
    158
    OF.5.9 LSCF hollow Iibre membranes Ior oxygen permeation
    B. Zvdorc:ak, K.Li
    159
    OF.5.10 Removal oI dioxins and gas mixture separations using supported ionic liquid membranes (SILMs)
    L. A. Neves, P. Kulkarni, C. Afonso,

    I. M. Coelhoso, J. G. Crespo
    160
    OF.5.11 New aspects oI empirical approaches Ior prediction oI gas permeability parameters oI polymers
    J. Teplvakov, O. Malvkh, E. Favre, I. Beckman
    161
    OF.5.12 OTM modules: materials, Ilux and stability in carbon-containing atmospheres
    P.I. Dahl, M.L. Fontaine, Y. Larring, R. Bredesen
    161
    OF.5.13 Preparation and characterization oI high perIomance hollow Iibre carbon membranes - discussion oI
    results and potential applications
    X. He, M.-B. Hgg
    162
    F.6. Food and packaging
    OF.6.1 Integration oI pervaporation / gas-liquid absorption: a new approach Ior the production oI stable aroma
    additives
    C. Bra:inha, J. D. Alves, R. M. C. Jiegas, J. G. Crespo
    163
    OF.6.2 Microcapsules based on a lightly crosslinked liquid crystalline polymer: a new smart material ?
    B. Tvlkowski, M. Pregowska, E. Jamowska, R. Garcia-Jalls, M. Giamberini
    163
    OF.6.3 Recovery oI polyphenols in bergamot juice by integrated membrane process
    A. Cassano, C. Conidi, E. Drioli
    164
    F.7. Pharmaceuticals and biotechnologies
    OF.7.1 PuriIication oI Ilavonoids Irom black currant juice by nanodiaIiltration
    M.B. Jensen, K.J. Christensen, B. Norddahl
    164
    OF.7.2 New materials Ior airborne viruses Iiltration
    L. Lebrun, G. Tilliket, D. Le Sage, Q. T. Nguven
    165
    OF.7.3 Preparation, characterization and testing oI adsorption membranes Ior chromatographic separation oI
    therapeutic plasmids
    L. Raiado-Pereira, D.M.F. Pra:eres, M. Mateus
    166
    OF.7.4 Viral clearance using size exclusion based membrane Iiltration: Dominant Iiltration mechanisms and
    strategies to attain higher throughput
    L. Jillain, J. Rico Pere:, J.-E. Dathe, M. Brger, I. Masselin, J. Thom, T. Scheper
    167
    OF.7.5 Supported liquid membranes with strip dispersion Ior the recovery oI cephalexin
    M.E. Jilt, W.S. Winston Ho
    167
    OF.7.6 Organic solvent nanoIiltration Ior the synthesis oI oligonucleotide monomers
    R. Jasconcelos, P. Blanc, I. Baptista, A.G. Livingston
    168
    OF.7.7 Production oI surIactin and Iengycin by Bacillus subtilis in a bubbleless membrane bioreactor
    F. Coutte, D. Lecouturier, J. Leclere, M. Bechet, P. Jacques, P. Dhulster

    169
    OF.7.8 Scale-up oI electrodialysis with ultraIiltration membranes: Iractionation oI an antihypertensive peptide
    Irom alIalIa white protein hydrolysate
    L. Firdaous, P. Dhulster, J. Amiot, D. Lecouturier, F. Lutin, L.-P. Je:ina, L. Ba:inet
    169
    OF.7.9 Membrane emulsiIication Ior the Iormulation oI stimuli responsive multiple emulsions containing
    labile bioactive molecules
    E. Piacentini, L. Giorno, E. Drioli
    170
    F.8. Health and artiIicial organs
    OF.8.1 Crossed hollow Iiber membrane bioreactor using human hepatocytes Ior in vitro study oI drugs and
    metabolic diseases
    L. De Bartolo, S. Salerno, E. Curcio, A. Piscioneri, M. Rende, S. Morelli, F. Tasselli, A. Bader,
    E. Drioli
    171
    OF.8.2 The inIluences oI the layer by layer deposition oI polyethylenimine and alginate on the transport rates
    and hemocompatibility oI PSF membranes
    F. Yasar Mahlicli, S. Alsov Altinkava
    171
    OF.8.3 Novel multi-layer scaIIolds Ior tissue engineering
    D. Stamatialis, B.J. Papenburg, I-J. de Jries, J. de Boer, C. van Blitterswifk, M. Wessling
    172
    OF.8.4 Keynote: Membranes Ior artiIicial organs
    J. Jienken
    173
    G - Out of the Lab-University-Industry Technology Transfer 174
    G.1. Case study assessments
    OG.1.1 CrossIlow microIiltration (0.1 m) oI skimmed milk. The role oI electrostatic interactions on the
    soluble protein transIer
    A.J.E. Jimene:-Lope:, F. Garnier-Lambrouin, F. Rousseau, G. Gesan-Gui:iou
    174
    OG.1.2 Scale-up oI a batch membrane process plant Ior the treatment oI an olive vegetaton waste water steam:
    A case study
    M. Stoller, A. Chianese
    174
    OG.1.3 Assessment oI a membrane process Ior regeneration oI secondary wastewater treatment plant (WWTP)
    eIIluents. Pilot plant operation
    G. Pere:, P. Gome:, A. Pla:a, R. Ibae:, A.M. Urtiaga, I. Orti:
    175
    OG.1.4 'Plug and clean membrane systems Ior small communities and villages
    D. Jial, J. Raktae-ngan, T. Wachinski, F. McKeever
    176
    OG.1.5 Keynote: Actual position oI electromembrane processes on the world desalination market
    L. Novak
    176
    POSTER COMMUNICATIONS 179
    A - Materials 180
    A.1.Hybrid and polymeric membranes
    PA.1.1 Active hybrid membranes : Irom in situ nanostructuration process to modulated Iunctional properties
    E. Espuche, S. Clemenson, L. David
    180
    PA.1.2 Phase separation microIabrication
    M. Bikel, R. G. H. Lammertink, M. Wessling
    180
    PA.1.3 Methods oI characterization oI heterogeneous ion-exchange membranes
    L. Bro:ova
    181
    PA.1.4 An AFM analysis oI the changes on the surIace oI several nanoIiltration membranes aIter the
    puriIication oI clavulanic acid solutions.
    A. L. Carvalho, A. Hernande:, L. Palacio, P. Pradanos, F. Maugeri
    182
    PA.1.5 MicroIiltration membranes via phase separations oI polymer solutions: control oI pore structure and
    hydrophilicity
    N. Stahra, H. Susanto, M. Ulbricht
    182
    PA.1.6 Solvent resistant nanoIiltration (SRNF) containing metal organic Irameworks
    S. Basu, M. Maes, A. Cano-Odena, L. Alaerts, D.E. De Jos, I.F.J. Jankelecom
    183
    PA.1.7 Novel cross-linkable copolymer membranes Ior organophilic ultra- and nanoIiltration
    Z. Pei, M. Ulbricht
    184
    PA.1.8 Study oI the perIormance oI selI-made polyethersulIone membranes relative to commercial
    ultraIiltration membranes Ior the Iractionation oI stevia-extracts
    J. Janneste, A. Sotto, J. Jan Craevveld, J. Jandeur, B. Jan der Bruggen
    185
    PA.1.9 Gas permeation properties oI rubbery poly(ether imide)/SiO
    2
    hybrid nanocomposite membranes
    J. Grignard, D. Roi:ard, E. Favre
    185
    PA.1.10 Symmetric porous PVDF-HFP membranes generated by a supercritical gel drying process
    S. Cardea, A. Gugliu::a, E. Drioli, E. Reverchon
    186
    PA.1.11 Preparation oI biodegradable chitosan membranes Ior tissue engineering applications
    C. Campana, A. Piscioneri, F. Tasselli, S. Salerno, E. Drioli, L. De Bartolo
    187
    PA.1.12 The role oI HCl on the transport oI tin through cation- and anion- exchange membranes
    M. Garcia-Gabaldon, J. Pere:-Herran:, J. Garcia-Anton, J.L. Guion
    187
    PA.1.13 StratiIied mixed matrix membranes based on polyimides Iilled by inorganic Iillers
    M. Frvcova, P. Svsel, L. Brabec, B. Bernauer, P. Hrabanek, M. Kocirik
    188
    PA.1.14 Green spherical building blocks Ior the Iabrication oI selI-standing polymeric membranes challenging
    anodic structures
    A. Gugliu::a, F. Trotta, E. Drioli
    189
    PA.1.15 Preparation oI ultrathin-skinned asymmetric polysulIone membranes by phase inversion and
    microwave plasma surIace treatment
    M. Etxeberria, S. Miguel, E. Fernande:-Gesalaga, P. Corengia, A. Garcia-Luis, D. Gon:ale:-
    Santamaria
    189
    PA.1.16 EIIect oI the nonsolvency oI coagulation on the nano-scale structure oI PVDF membrane
    C.L. Li, A. Deratani, D.M. Wang, D. Quemener, D. Bouver, J.Y. Lai
    190
    PA.1.17 New poly (ether imide) based ultraIiltration membrane with low Iouling properties obtained by surIace
    modiIication with poly (ethylene glycol)
    W. Chinpa, R. Jiraratananon, D. Quemener, A. Deratani
    191
    PA.1.18 A hybrid membrane with an extractive layer and reactive support matrix Ior the sequential sorption and
    degradation oI halogenated hydrocarbons in water
    G.M. Nisola, E. Cho, W.J. Chung
    191
    PA.1.19 Determination oI diIIusion coeIIicients Irom area expansion oI LDPE membrane immersed in organic
    liquids
    A. Randova, L. Bartovska, S. Hovorka, K. Friess, P. I:ak
    192
    PA.1.20 ClariIication oI cashew apple juice through micro and ultraIiltration laboratorial unit using polymeric
    membranes (PES, CEL, PVDF)
    M.U. Mivake, L.A. Jiotto
    193
    PA.1.21 Synthesis, morphology and membrane properties oI poly(1-trimethylsilyl-1-propyne)poly(4-methyl-2-
    pentyne) block copolymers
    E. Sultanov, J. Khotimskiv, A. E:hov
    193
    PA.1.22 Biodegradable hollow Iiber Ior tissue engineering application
    M.S. Bettahalli Narasimha, D. Stamatialis, M. Wessling
    194
    PA.1.23 CO
    2
    /CH
    4
    separation properties oI Ultem-SAPO-34 mixed matrix composite membranes
    A. Kertik, C. Atalav-Oral, S. B. Tantekin-Ersolma:
    194
    PA.1.24 Polymeric capsules prepared by phase inversion technique and their application in Iine chemistry
    M. G. Buonomenna, A. Figoli, R. Morelli, E. Drioli
    195
    PA.1.25 EIIicient Iacilitated transport oI lead and cadmium across a plasticized triacetate membrane mediated
    by D2EHPA and topo
    O. Arous, H. Kerdfoudf
    196
    PA.1.26 Preparation oI polyethylene (PE) and ethylene vinyl acetate (EVA) membranes Ior gas separation at
    diIIerent conditions
    S.A. Mousavi, M. Gholi:adeh, M. Pourafshari-Chenar, S. Sedghi, Z. Abdekhodaei
    197
    A.2. Composite membranes
    PA.2.1 Highly ordered thin Iilm composite membranes based on selI-assembled block copolymers
    X. Li, N. Lefevre, C. A. Fustin, J. F. Gohv, I. F.J. Jankelecom
    197
    PA.2.2 EIIect oI temperature on gas transport properties in mixed matrix membranes oI PVC-Sr
    2
    CoUO
    6
    M.G. Garcia, R. Pinacca, J.C. Pedregosa, N.A. Ochoa, J. Marchese
    198
    PA.2.3 Development oI Composite Membranes Ior the Concentration oI PFCs
    Y.I. Park, M.Y. Nam, B.S. Kim, H.K. Lee
    199
    PA.2.4 Templated growth oI aligned carbon nanotubes on porous supports and membranes
    E.C. Jermisoglou, G. Pilatos, C.M. Je:iri, G.N. Karanikolos, G.E. Romanos, J.W. Nolan, N.K. Kaki:is,
    N.K. Kanellopoulos
    199
    PA.2.5 Preliminary study on use oI Iunctionalized hydrocarbonic resins Ior obtaining polyelectrolytes
    membranes
    B.B.R. Silva, F.J.B. Brum, C. M. Branco, M.M.C. Forte
    200
    PA.2.6 EIIect oI temperature on gas transport properties in mixed matrix membranes oI PVC Sr
    2
    CoUO
    6
    M. G. Garcia, R. Pinacca, J. C. Pedregosa, N. A. Ochoa, J. Marchese
    201
    PA.2.7 Composite polymeric membranes Ior gas separation: plasma polymerization Irom
    hexamethyldisiloxane (HMDSO) and ethylene glycol monomethyl ether acetate (EGMEA)
    S. Miguel, M. Etxeberria, E. Fernande:-Gesalaga, P. Corengia, F.J. Fernande:-Carretero,
    A. Gutierre:
    201
    PA.2.8 Changes in the CO
    2
    /CH
    4
    selectivity and productivity oI the 6FDA-6FpDA polyimide by the addition oI
    Iunctionalized -alumina nanoparticles
    L. Fernndez, M. Snchez, A. Tena, L. Palacio, A.E. Lozano, A. Hernndez, P. Prdanos
    202
    PA.2.9 The development oI silica-Iilled thin Iilm poly(1-trimethylsilyl-1-propyne) membranes Ior organophilic
    pervaporation
    S. Claes, P. Jande:ande, S. Mullens, R. Levsen, R. Peeters, M. K. Jan Bael
    203
    PA.2.10 Composite membranes based on electrospun non-woven porous support Ior salt separation
    S. Kaur, G. Singh, T. Matsuura, S. Ramakrishna
    203
    PA.2.11 EIIect oI polymeric crosslinking agents on solvent stable organic solvent nanoIiltration membranes
    H. Siddique, Y. Bhole, M. Sairam, A.G. Livingston
    204
    PA.2.12 Elaboration oI chitosan-activated carbon composite materials Ior wound dressing applications:
    characterization oI the porous structure
    A. Jenault , S. Lagerge, C. Pochat, D. Bouver, L. Jachoud, C. Faur
    205
    A.3. Inorganic membranes : ceramic, metallic, zeolite
    PA.3.1 EIIect oI TEOS addition on preparation oI mesoporous silica thick coating by electrophoretic
    deposition
    A. Mivamoto, H. Negishi, A. Endo, K. Sakaki, T. Ohmori, H. Yanagishita, K. Watanabe
    206
    PA.3.2 Gas transport mechanism and separation properties oI membranes with nano-structured porosity based
    on exIoliated graphite Ioils
    D. A. Svrtsova, O. N. Shornikova, J. J. Avdeev, J. J. Teplvakov
    206
    PA.3.3 Pore size control oI microporous silica membranes with low temperature CVD/CVI modiIication
    methods
    D. Koutsonikolas, G. Pantoleontos, S. Kaldis, G.P. Sakellaropoulos
    207
    PA.3.4 Oily wastewater treatment by means oI -alumina nanoIiltration membrane
    Z. Sadeghian , F. Zamani, N. Ashrafi:adeh
    208
    PA.3.5 Factorial experiment design applied to the properties oI low-cost ceramic membranes
    S. Mestre, E. Sanche:, M. Lorente, P. Gingter
    208
    PA.3.6 Sintered metallic membranes with gradual structure produced by powders sedimentation
    I. Jida-Simiti, N. Jumate, N. Sechel
    209
    PA.3.7 Development oI low cost -Al
    2
    O
    3
    -clay composite ultraIiltration membrane Ior separation oI Bovine
    Serum Albumin (BSA)
    A. Mafhi, P. Monash, G. Puga:henthi
    210
    PA.3.8 Investigation oI permeation properties during the cyclic CVD treatment oI composite membranes with
    TEOS and TMOS in relation to the locality and morphology oI silica deposition
    A.I. Labropoulos, G.E. Romanos, G. Karanikolos, G.I. Pilatos, N.K. Kanellopoulos
    210
    PA.3.9 Preparation and characterization oI oriented zeolite MFI layers and membranes Ior separation oI light
    hydrocarbons
    P. Hrabanek, A. Zikanova, J. Drahokoupil, B. Bernauer, J. Fila, M. Kocirik
    211
    PA.3.10 Low temperature template removal Irom silicalite-1 membranes, Iilms and round boat shaped crystals
    I. Jirka, P. Hrabanek, A. Zikanova, L. Brabec, J. Fila, M. Kocirik
    212
    PA.3.11 Magnetron sputtering deposition and characterization oI Pd and Pd-Cu composite membranes Ior
    hydrogen separation
    E. Fernande:-Gesalaga, P. Corengia, S. Miguel, M. Etxeberria, M. Bri:uela, J. Calvio
    212
    PA.3.12 InIluence oI support characteristics on gas permeation oI Pd composite membranes
    P. Pinacci, M. Broglia
    213
    PA.3.13 Application oI MFI/TiO
    2
    and GIS/TiO
    2
    membranes in pervaporation
    K. C:echowska
    214
    PA.3.14 Nanocomposite MFI-alumina hollow-Iibre membranes: application to selective separation oI xylene
    isomeric mixtures
    Z. Deng, M. Pera-Titus, A. Giroir-Fendler, Y. Guo
    214
    PA.3.15 EIIect oI mid synthesis addition oI silica to the synthesis medium on the properties oI MFI type zeolite
    membranes
    B. Sovda, A. ulfa:, H. Kalipilar
    215
    PA.3.16 Study oI preparation oI Pd based membranes by electroless plating over PSS supports
    J.A. Calles, R. San:, D. Alique
    216
    PA.3.17 Electrophoretic deposition (EPD) oI small zeolite crystals as a membrane base
    L. Brabec, P. Hrabanek, M. Kocirik
    217
    PA.3.18 New ceramic ultraIiltration membrane Ior tangential Iiltration deposited on macroporous support Irom
    Moroccan apatite
    I. Barrouk, S.A. Younssi, M. Persin, A. Larbot, A. Kabbabi, J. Maghnouf
    217
    PA.3.19 Al
    2
    O
    3
    coatings on stainless steel porous supports as intermetallic diIIusion barrier Ior H
    2
    separative
    membranes
    A. Bottino, M. Broglia, G. Capannelli, A. Comite, P. Pinacci
    218
    PA.3.20 Elaboration oI supports Ior membranes Iiltration Irom kaolin and limestone
    A. Guechi, A. Harabi, S. Condom
    219
    PA.3.21 Synthesis by conventional and microwave-assisted methods oI Fe-MFI membranes Ior N
    2
    O
    decomposition
    J. Motu:as, A. Julbe
    219
    A.4. Ion conducting membranes : proton and oxygen
    PA.4.1 Preparation oI new composite membranes Ior proton transport based on inorganic anodisc and Liquid-
    crystalline compounds
    B. Tvlkowski, N. Castelao, B. Ferrer, M. Pregowska, R. Garcia-Jalls, T. Gumi
    ,
    J.A. Reina,
    M. Giamberini
    220
    PA.4.2 Proton conductive membranes based on polyvinyl alcohol and polystyrenesulIonic acid
    I. Stadniv, J. Konovalova, A. Burban
    220
    PA.4.3 BSCF hollow Iibers Ior oxygen separation
    A. Leo. S. Liu, J.C.D. da Costa
    221
    PA.4.4 Stability and permeation investigation oI Ba
    0,5
    Sr
    0,5
    Co
    0,8
    Fe
    0,2
    O
    3-o
    membranes Ior oxyIuel processes
    A. Ellett, D. Schlehuber, T. Markus, L. Singheiser
    222
    PA.4.5 Preliminary study on use oI Iunctionalized hydrocarbonic resins Ior obtaining polyelectrolytes
    membranes
    B.B.R. Silva, F.J.B. Brum, C. M. Branco, M.M.C. Forte
    222
    PA.4.6 InIluence oI ex situ ageing on NaIion membrane Iunctional properties
    E. Espuche, S. Naudv, F. Collette, F. Thominette, G. Gebel
    223
    PA.4.7 Conductive properties oI poly(ether-sulIone-ketone)s containing sulIonic and phosphonic acid groups
    C. Muo:, J.G. de la Campa, A.E. Lo:ano, J. de Abafo, J. Benavente
    224
    PA.4.8 New proton conducting interpenetrated polymer network membrane
    A. Morin, O. Fichet, L. Chikh, J. Delhorbe, B. Ameduri, M. Bathfield, R. Mercier, X. Thirv, S. Jidal,
    L. Augier, E. Espuche, G. Gebel
    224
    PA.4.9 Oxygen permeation study through new Iabricated tubular perovskite membrane
    N. Hafimohsen, M.R. Mehrnia, A. Barati, E. Ganfi
    225
    PA.4.10 Proton conductive membranes based on doped sulIonated polytriazole
    M. Boaventura, M. L. Ponce, D. Gomes, A. Mendes, S. P. Nunes
    226
    PA.4.11 On the course oI sulIonation oI poly(arylene ether sulIone)s
    J. Meier-Haack, P. Friedel, W. Butwilowski, C. Jogel
    226
    PA.4.12 EIIects oI nanostructuring in oxygen-permeable membrane materials on the base oI mixed conducting
    perovskites ABO
    3-x
    U.J. Ancharova, A.S. Ko:hemvachenko, N.Z. Lvakhov, A.P. Nemudrv, O.A. Savinskava, S.J. Tsvbulva
    227
    PA.4.13 New composite membranes Ior Iuel cells obtained by mixing sulIonated polysulIone and plasma treated
    Laponite. Elaboration and characterization
    C. Lixon-Buquet, D. Langevin
    ,

    E. Dargent, S. Marais, Q.T. Nguven, F. Poncin-Epaillard
    228
    PA.4.14 Morphological and electrical properties oI cermets as electrodes Ior ceramic membranes in solid-state
    electrolyser
    C. Deslouis, C. Hodebourg, M. Keddam, A. Pailleret, K. Rahmouni,

    H. Takenouti, S. Willemin, B. Sala
    228
    A.5. Nanostructured materials and surIace modiIication Functionalization
    PA.5.1 Microstructured hollow Iiber membranes Ior ultraIiltration
    P.Z. ulfa:, H.H.M., Rolevink, W.Nifdam, C. van Rifn, R.G.H. Lammertink, M. Wessling
    229
    PA.5.2 Synthesis and characterization oI crown ethers Iunctionalized carbon nanotubes
    G. Nechifor, S.I. Joicu, A.C. Nechifor, S. Mihai
    230
    PA.5.3 Immobilization and graIting oI poly(ethylene glycol) methacrylate onto ePTFE membrane by
    atmospheric pressure plasma jet
    T. C. Wei, Y. Chang, C. J. Chang, Y. J. Shih, Y. L. Liu
    231
    PA.5.4 Novel electrospun nanoIiber composed oI amphiphilic polyelectrolyte Ior salt rejection
    S. H. Cheng, L. T. Chen, W. Y. Chen, H. Shao, T. M. Liang, M. C. Chang
    231
    PA.5.5 Mass transIer in ED channels constituted by commercial heterogeneous membranes and membranes
    with modiIied surIace
    N. Melnik, E. Belova, N. Pismenskava, J. Nikonenko
    232
    PA.5.6 Metal-phosphorus-oxide nanostructures preparation on the surIace oI ceramic membranes by molecular
    layering deposition
    G. Tereshchenko, M. Ermilova, N. Orekhova, N. Basov, A. Malvgin, A. Malkov, S. Mikhailovskv
    233
    PA.5.7 Track-etched membranes with stimuli-responsive pores via surIace-initiated atom transIer radical
    polymerization
    F. Tomicki, M. Ulbricht
    233
    PA.5.8 Development oI photo-responsive membranes Ior Iractionation oI biomolecules
    F.R.P. Oliveira, C.A.M. Portugal, J.G. Crespo
    234
    PA.5.9 Porous membranes modiIied by polyelectrolytes
    J. Kochan, T. Wintgens, J. E. Wong, T. Melin
    235
    PA.5.10 Gas and vapour permeation through ODPA-ODA membranes with diIIerent content oI cucurbit|6|uril
    nanoIillers
    K. Friess, J.C. Jansen, A. Figoli, J. Sindelar, J. Svec, P. Svsel, J. Hvnek, O. Jopicka, M. Zgaar, M.
    Sipek
    236
    PA.5.11 Binary mixture transport through polyimide membranes with two diIIerent types oI CB6 nanoIillers
    K. Friess, J. Hvnek, O. Jopicka, M. Zgaar, M. Sipek, J.C. Jansen, A. Figoli, J. Sindelar, J. Svec,
    P. Svsel
    236
    PA.5.12 ModiIication oI ultra- and microIiltration membranes withtitanium dioxide
    M.T.P. de Amorim, A. Moro, S.M.S. Marques, C. Tavares, R. Bergamasco
    237
    PA.5.13 Preparation oI mono-dispersed chitosan microcapsules using SPG membrane emulsiIication technique
    K. Akamatsu, D. Kaneko, T. Sugawara, R. Kikuchi, S. Nakao
    238
    A.6. Molecular recognition and selI-assembly membranes: liquid, biomimetic and Iacilitated transport
    PA.6.1 Development oI a biomimetic scaIIold Ior transmembrane protein incorporation
    S. Ibragimova, J.S. Hansen, M. Perrv, T. Jissing, K.B. Stibius, J. Jogel, O. Geschke, J. Emneus, C.H.
    Nielsen
    238
    PA.6.2 Characterization oI a permselective structure Ior support/encapsulation oI speciIic substances
    L. Pelae:, S. Bifani, S. Escaler, M.I. Ja:que:, J. Benavente, S. Ibragimova, K.B. Stibius, C. Helix-
    Nielsen
    239
    PA.6.3 Facilitated transport oI CO
    2
    through carbonic anhydrase-immobilized poly(vinyl alcohol) beads
    G.N.B. Baroa, J. Kim, D.-E. Hong, B. Jung
    239
    PA.6.4 Properties oI the transport oI Cu(II) across aIIinity membranes containing the
    3-phenyl-4-benzoylisoxazol-5-one as carrier
    L. Mitiche, S. Tingrv, P. Seta, A. Sahmoune
    240
    PA.6.5 Toxic metallic ion extraction using polymer inclusion membranes (PIMs)
    O. Kebiche-Senhadfi, L. Mansouri, S. Tingrv, P. Seta, M. Benamor
    241
    A.7. New breakthrough approaches Ior membrane materials
    PA.7.1 Synthesis and electrochemical characteristics oI polysulIone-polyaniline-carbon nanotubes asymmetric
    composite membranes
    S.I. Joicu, A.C. Nechifor, D.I. Jaireanu, G. Nechifor
    241
    PA.7.2 'Smart perIormance oI hydrogel pore-Iilled stimuli-responsive membranes
    N. Adrus, M. Ulbricht
    242
    PA.7.3 Fabrication by PECVD oI super-hydrophobic surIace without Iluorine
    C.-H. Lo, J. Rouessac, K.-R. Lee, J.-Y. Lai
    242
    PA.7.4 Robust synthesis and perIormance oI a titania-based ultraIiltration membrane with photocatalytic
    properties
    L. Dfafer, A. Avral, A. Ouaged
    243
    PA.7.5 Vertically aligned single walled carbon nanotube arrays embedded within a covalently linked polymer
    network on a porous silicon substrate Ior molecular separation
    C. J. Shearer, K. T. Constantopoulos, N. H. Joelcker, J. G. Shapter, A. J. Ellis
    244
    PA.7.6 Antimicrobial peptides immobilized on reverse osmosis membranes as a new approach to reduce
    bioIouling
    E. Gershkovich, K. Berliner, E. Hershkovit:, Z. Ronen, R. Kasher
    245
    PA.7.7 Development oI smart composite membranes based on pH-responsive microgel particles and inert
    porous supports
    J. M. Olvera-Marque:, M. J. Ari:a
    245
    PA.7.8 Development oI inorganic layers in supercritical CO
    2
    media. An original approach to prepare silica
    based membranes
    J. Durand, J-C. Rui:, S. Sarrade, C. Gui:ard, A. Julbe
    246
    PA.7.9 Facilitated oleIin transport membranes using chemically activated copper nanoparticles by ionic liquids
    J. H. Lee, S. W. Kang, J. Kim, K. I. Han, Y. S. Kang
    247
    PA.7.10 Aerosol Iiltration as preparation a method oI asymmetric membranes Ior gas separation membranes
    F. Mever, B. J. Bladergroen
    248
    B - Characterization 249
    B.1. Material structure
    PB.1.1 High Resolution SEM to determine the pore size distribution oI Iiltration membranes
    Y. Wvart, R. Tamime, S. Nitsche, D. Chaudanson, K. Glucina, P. Moulin
    249
    PB.1.2 Study oI the working temperature inIluence on the mechanical properties oI polysulIone Iilms
    B. Pea, L. Ferre, R. Garcia-Jalls, F. Ferrando, T. Gumi
    249
    PB.1.3 Analysis oI the charge Iormation mechanisms in nanoIiltration membranes by tangential streaming
    potential measurements
    A. S:vmc:vk, L. Bruni, P. Fievet, S. Bandini
    250
    PB.1.4 Do macro-voids are induced by skin-deIects during wet phase inversion ?
    J. Mendret, Y. Medina-Gon:ale:, J-C. Remigv
    251
    PB.1.5 Water vapor stability oI zeolite molecular sieving membranes Ior the separation oI CO
    2
    Irom H
    2
    in
    humid atmospheres Ior pre-combustion Power Plant processes
    C. Chat:icharalampous, H. Richter, T. Markus
    252
    PB.1.6 Anomaly oI thermo-mechanical properties oI Ba
    0.5
    Sr
    0.5
    Co
    0.8
    Fe
    0.2
    O
    3-o
    at low temperatures
    B.X. Huang, J. Mal:bender, R. W. Steinbrech, S. Baumann, W. Meulenberg, A. Mbius, T. Markus, P.
    Grvchtol, C. M. Schneider, L. Singheiser
    252
    PB.1.7 Characterization oI new Moroccan clay, Ior the ceramic membrane conception
    N. Elharrak, A. Yaacoubi, A. Out:ourhit
    253
    PB.1.8 ManuIacture and characterization oI zirconia microIiltration membranes Ior separation oI oil-water
    emulsions
    R. Del Colle, C.A. Fortulan, S. R. Fontes
    253
    PB.1.9 Pore size distribution and MWCO estimations oI polymeric membranes by liquid-liquid displacement
    porosimetry
    J.I. Calvo, A. Bottino, G. Capannelli, A. Hernande:, R.I. Peinador, R. Firpo
    254
    PB.1.10 Polyimides with hydroxyl group in diamine Iragment: structure, thermochemical rearrangement and
    gas separation properties
    O. Rusakova, J. Kostina, G. Bondarenko, A. Alentiev, A.Yakimanskii
    255
    PB.1.11 Polynorbornenes: the structure identiIication and eIIect oI chemical structure on transport properties
    M. Moskvicheva, J. Kostina, G. Bondarenko, J. Yakovlev, K. Makovetskii, A. Alentiev
    255
    PB.1.12 Sorption and diIIusion in semi-crystalline polyoleIins
    L. Pechackova, A. Zubov, T. Gregor, L. Seda, J. Kosek
    256
    PB.1.13 The AFM study oI surIace morphology and relationship to organic solvent nanoIiltration membrane
    perIormance
    J. Stawikowska, A. Livingston
    257
    B.2. Membrane perIormance
    PB.2.1 Mechanical and chemical stabilities oI polymeric membranes
    C. Liu, T. Wachinski, M. Farcv, D. Jial
    258
    PB.2.2 Investigation in development and application oI new low-Iouling hydrogel composite ultraIiltration
    membranes
    P. Peeva, M. Ulbricht
    258
    PB.2.3 The eIIect oI amine degradation products on membrane gas absorption
    J. A. Franco, D. de Montignv, S. E. Kentish, G. W. Stevens,

    J. M. Perera
    259
    PB.2.4 Evaporative light scattering detector: toward a general molecular weight cut-oII characterization oI
    solvent resistent nanoIiltration membranes
    X. Li, F. Monsuur, B. Denoulet, A. Dobrak, P. Jande:ande, I. F. J. Jankelecom
    259
    PB.2.5 How room temperature ionic liquids swells polymeric Ilat membranes ?
    P. I:ak, S. Hovorka, T. Bartovskv, L. Bartovska, A. Randova, J.G. Crespo
    260
    PB.2.6 An AFM analysis oI the changes on the surIace oI several nanoIiltration membranes aIter the
    puriIication oI clavulanic acid solutions
    A. L. Carvalho, A. Hernande:, L. Palacio, P. Pradanos, F. Maugeri
    261
    PB.2.7 PerIormance and stability oI multi-channel MFI zeolite membranes detemplated by calcination and
    ozonication
    J. Kuhn, S. Sutanto, J. Gross, F. Kapteifn
    262
    PB.2.8 Rejection rate and retention capacity oI membrane Iilters
    S. Mori, M. Kanai
    262
    PB.2.9 Development oI mesoporous silica sphere-polysulIone hybrid membranes Ior gas separation
    B. Zorno:a, C. Telle:, J. Coronas
    263
    PB.2.10 InIluence oI concentration-polarization on salt permeability and ion transport numbers measured in a
    dead-end test cell
    J. Romero, J.D. Ramos, L. Pelae:, M.I. Ja:que:, J. Benavente
    264
    PB.2.11 DiIIusional permeability and ion transport across a bilayer membrane: correlation with single layers
    parameters
    J.D. Ramos, J. Romero, L. Pelae:, S. Bifani, M.I. Ja:que:, J. Benavente
    265
    PB.2.12 Characterisation oI the active layer oI a nanoIiltration membrane in contact with KCl and CaCl
    2
    solutions
    M.I. Ja:que:, J. Benavente
    265
    PB.2.13 Impact oI sodium hypochlorite on aromatic polyamide composite reverse osmosis membranes:
    identiIication oI appropriate methods Ior the characterization oI membrane degradation
    A. Ettori, E. Gaudichet-Maurin, J-C. Schrotter, P. Aimar, C. Causserand
    266
    PB.2.14 InIluence oI CO
    2
    on stability and permeation behaviour oI Ba
    0.50
    Sr
    0.50
    Co
    0.80
    Fe
    0.20
    O
    3-o
    membrane material
    A. Moebius, D. Schlehuber, T. Markus
    267
    PB.2.15 Investigation oI the charge Iormation mechanismsin polyamide nanoIiltration membranes by the
    adsorption-amphoteric model
    L. Bruni, S. Bandini
    267
    PB.2.16 Evaluation oI the perIormance oI a 1.2m commercial membrane impregnated with silver Ior bacteria
    retention during the crossIlow microIiltration process
    R. N. Haneda, Elson Longo, S. R. Fontes
    268
    PB.2.17 InIluence oI salts on the retention oI polyethyleneglycol by an NF organic membrane: pore swelling
    and salting-out eIIects
    A. Escoda, P. Fievet, S. Lakard, A. S:vmc:vk
    269
    PB.2.18 Impact oI TiO
    2
    nanoparticles on morphology and perIormance oI organic solvent highly stable
    polyimide nanoIiltration membranes
    I. Soroko, A. Livingston
    270
    PB.2.19 Irradiated polysulIone membranes by gamma ray
    M. A. Masuelli, N. A. Ochoa, J. Marchese, M. Grasselli
    270
    PB.2.20 Comparison oI electrochemical properties oI two diIIerent regenerated cellulose ultraIiltration
    membranes
    A. Pihlafamki, M. Kallioinen, M. Mnttri, R. Takagi
    271
    PB.2.21 NanoIiltration as pretreatment Ior scaling control in SWRO: a systematic study
    L. Llenas, X. Martine:-Llado, A. Yaroshchuk, M. Rovira, J. DePablo
    272
    PB.2.22 Permeability and bacteria rejection in third generation membranes. Application to cold sterilization oI
    Iood streams.
    L. Fernande: Garcia, F. A. Riera Rodrigue:, R. Alvare: Fernande:, S. Alvare: Blanco
    273
    PB.2.23 InIluence oI the ionic composition on the transIer oI sugars through ion-exchange membranes
    J. Savignac, E. Jera, S. Galier, P. Huguet, H. Roux-de Balmann
    274
    PB.2.24 Preparation and properties oI sulIonated polyvinilydene Iluoride porous membranes
    A. Bottino, G. Capannelli, A. Comite
    274
    PB.2.25 InIluence oI temperature and counter-ion nature on methanol permeation through ion-exchange
    membranes
    L. Chaabane, C. Mar-Diop, L. Dammak , C. Larchet
    275
    PB.2.26 Transport properties oI organic vapours in glassy perIluoropolymer membranes revealed by detailed
    analysis oI the transient behaviour in the permeation curve
    J. C. Jansen, K. Friess, E. Drioli
    275
    PB.2.27 Ion-exchange membrane resistivity measurement and model at DC
    L. Chaabane, L. Dammak, C. Larchet

    276
    PB.2.28 Ageing oI ion-exchange membranes: InIluence on the transport properties
    L. Dammak, D. Grande, C. Larchet
    277
    PB.2.29 Comparison between RO and NF perIormances in aqueous solutions oI phenolic compounds: InIluence
    oI hydroxyl, chloro and nitro substituents
    M. J. Lope:-Muo:, J. M. Arsuaga, L. Braeken, A. Sotto
    277
    PB.2.30 InIluence oI membrane and solute properties on the separation perIormance oI nanoIiltration and
    reverse osmosis membranes Ior phenol oxidation products
    J. M. Arsuaga, M. J. Lope:-Muo:, A. Sotto
    278
    PB.2.31 EIIect oI polymer swelling on the nanoIiltration perIormance oI poly(dimethylsiloxane)
    O. Farid, J.P. Robinson
    278
    PB.2.32 Organic Solvent NanoIiltration Thin Film Composite (TFC) membranes
    M. F. Jimene: Solomon, Y. Bhole, A. G. Livingston
    279
    PB.2.33 Characterization oI a commercial nanoIiltration membrane suitable Ior the recovery oI ionic liquids
    Irom aqueous solutions
    J.F. Fernande:, M.A. Rodrigue:, J. Thming
    279
    B.3. Non-destructive and in-situ dynamic characterization
    PB.3.1 Organic membrane characterizations by optical and microscopic methods: drinking water application
    R. Tamime, Y. Wvart, L. Sio:ade, I. Baudin, C. Deumie, K. Glucina, P. Moulin
    280
    PB.3.2 A new approach to the challenge oI measuring multi-component sorption properties in barrier
    materials: Example oI EVOH copolymers Ior Iuel tank applications
    A. Jonquieres, R. Clement, J. Zhao, C. Kanaan, B. Brule, H. Lenda, P. Lochon
    281
    PB.3.3 Residence time distribution method Ior the study oI hydrodynamics in the membrane apparatus
    A. Miskiewic:, A. Jaworska, G. Zakr:ewska-Tr:nadel, A. Dobrowolski, C. Cofocaru
    281
    PB.3.4 Innovative combinations oI 'in situ and 'ex-situ techniques as a tool Ior monitoring and controlling
    the evolution oI nanostructured membranes
    G. Pilatos, A.I. Labropoulos, E.C. Jermisoglou, Ch. Je:iri, G.E. Romanos, J.W. Nolan,
    G.N. Karanikolos, N.K. Kanellopoulos
    282
    PB.3.5 Membrane design and characterisation by incorporation oI room temperature ionic liquids Ior selective
    transport processes
    L. A. Neves,

    I. M. Coelhoso, J. G. Crespo
    283
    PB.3.6 Water sorption and proton conductivity oI various PEMFC membranes: inIluence oI temperature,
    relative humidity and interactions oI the adjacent layers in MEA
    L. Maldonado, F. Xu, O. Lottin
    283
    PB.3.7 Trace-ion method Ior the advanced characterization oI NF membranes
    A. Yaroshchuk
    ,
    X. Martine:-Llado, L. Llenas, M. Rovira, J. De Pablo
    284
    PB.3.8 In-situ analysis oI SNRF membrane swelling under relevant conditions
    H. van der Werf, N. E. Benes, M. Wessling, A. Nifmeifer
    285
    PB.3.9 FTIR-ATR study oI water distribution in HyIlon-Ion

    H membranes
    M. C. Ferrari, J. Catalano, M. Giacinti Baschetti, M. G. De Angelis, G. C. Sar
    285
    PB.3.10 Physicochemical study oI Poly(4-vinylpyridine)-based weak anion exchange membranes. Contribution
    oI in situ et operando techniques Ior the evaluation oI thermodynamic and kinetic properties.
    L. Franck-Laca:e, P. Huguet, P. Sistat, F. Lapicque
    286
    C - Modelling and Simulation 287
    C.1. Molecular modelling
    PC.1.1 Molecular dynamics simulations oI gas permeation through realistic polyimide membranes
    S. Nevert:, D. Brown
    287
    PC.1.2 Flux enhancement by bubbling: development oI a new integrated hydrodynamic and mass transIer
    model
    M. E. Jalentine, R. W. Field, Z. F. Cui
    288
    PC.1.3 Investigations on the mechanisms oI 5-Iluorouracil imprinting by a computational approach
    P. Cairo, E. Tocci, E. Drioli
    288
    PC.1.4 Understanding ligand-protein interactions in aIIinity membrane chromatography Ior antibody
    puriIication
    C. Boi, J. Busini, M. Salvalaglio, C. Cavallotti, G.C. Sarti
    289
    PC.1.5 Molecular simulation oI the sorption behavior oI gases in copolyimide membranes
    S. Halitoglu, M. G. Ahunbav, S. B. Tantekin-Ersolma:
    290
    C.2. Transport mechanisms
    PC.2.1 A zonal rate model Ior stacked membrane chromatography
    E. von Lieres, J. Wang, M. Ulbricht, P. Francis, C. Havnes
    290
    PC.2.2 Characterization oI electric and dielectric properties oI a nanoIiltration membrane: application to
    prediction oI salt rejection perIormances
    A. S:vmc:vk, J. Benavente, Y. Lanteri, P. Fievet
    291
    PC.2.3 Towards energy consumption reduction in separation processes: modelling oI pervaporation
    perIormance
    A. Jerhoef, E. De Ridder, B. Bettens, J. Degreve, B. Jan der Bruggen
    292
    PC.2.4 Gas separation transport modeling Ior PDMS coatings on PEI-PEG-IPN membranes
    K. Darcovich, M.M. Dal-Cin, S. Saimani, A. Kumar
    292
    PC.2.5 Bioseparation oI peptides and biogenic amines by nanoIiltration
    J. Labanda, J. Sabate, J. Llorens
    293
    PC.2.6 Modeling particle size in ultraIiltration
    A.K. Pavanasam, A. Abbas, J. Chen
    294
    PC.2.7 Anisotropic gas transIer phenomena in asymmetric membranes
    I. Kurchatov, A. Krukov, N. Laguntsov, J. Tronin, J. Jolkov
    295
    PC.2.8 Modeling mass and heat transIers during membrane Iormation numerical results and experimental
    validation
    D. Bouver, W. Werapun, C. Pochat-Bohatier, A. Deratani, J.P. Desfours
    295
    PC.2.9 New approach to the barrier properties oI polyamide 12/montmorillonite nanocomposites
    B. Alexandre, D. Langevin, T. Nguven, P. Mederic, T. Aubrv, S. Marais
    296
    PC.2.10 Modeling the inIluence oI urease immobilization on the perIormance oI hemodialysis membranes
    H. E. Abaci, S. Alsov Altinkava
    297
    PC.2.11 Modeling the perIormance oI enzyme immobilized membranes
    Y. Yurekli, S. Guedidi, S. Alsov Altinkava, A. Yemenicioglu, C. Innocent, A. Deratani, S. Roudesli
    297
    PC.2.12 Transport oI water ethanol mixtures through dense PIM-1 membranes
    A. A. Yushkin, S. E. Tsarkov, A. J. Jolkov, J. N. Tronin, P. M. Budd
    298
    PC.2.13 NH
    4
    Cl inIluence on Zn transport through a cation exchange membrane in a Zn-NH
    3
    -Cl system
    E. Ortega, P. Sistat, J. Pere:-Herran:, G. Pourcellv
    299
    PC.2.14 Polarization in hydrogen puriIication processes using Pd-based membranes
    A. Caravella, G. Barbieri, E. Drioli
    299
    PC.2.15 Dielectric exclusion in nanoIiltration. A comparison oI theoretical and experimental dependency oI the
    interaction energy with concentration
    J. Silva, J.A. Otero, G. Lena, P. Pradanos, J. Jillasante, A. Martin, F. Martine:, A. Hernande:
    300
    PC.2.16 Contributions to the electric potential appearing when a pressure drop is applied trough a nanoIiltration
    membrane
    J. Benavente, J. Silva, P. Pradanos, L. Palacio, A. Hernande:, G. Jonsson
    301
    PC.2.17 Mechanism oI Iacilitated cadmium(II) transport through FSSLM with Cyanex 923
    A.A. Leopold, N.S. Rathore, A. Fortunv, M.T. Coll, A.M. Sastre
    301
    PC.2.18 Transport properties oI a cation-exchange membrane under natural convection in contact with ZnSO
    4
    solutions
    I. Herrai:-Cardona, E. Ortega, J. Pere:-Herran:
    302
    PC.2.19 Simulation oI dynamic responses oI semi-open Wicke-Kallenbach cell with composite membranes oI
    the type silicalite-1-u-alumina
    J. Fila, P. Hrabanek, A. Zikanova, M. Kocirik, B. Bernauer, I. Jirka
    303
    PC.2.20 Rigorous modeling oI the solute transport in emulsion liquid membranes in hollow Iiber contactors
    E. Bringas, M.F. San Roman, I. Orti:
    303
    PC.2.21 NanoIiltration oI metal ions in concentrated phosphoric acid
    H. Diallo, B. Chaufer, M. Rabiller-Baudrv
    304
    PC.2.22 Fouling mechanism study and Ilux decrease modeling in crude corn oil miscella in laboratory scale
    M. S. Araki, L. A. G. Gonalves, L. A. Jiotto
    305
    PC.2.23 A SurIace response approach to canola crude oil degumming by polymeric membrane ultraIiltration
    L. A. Campos, M. C. Chiu, L. A. Jiotto, L. A. G. Gonalves
    305
    PC.2.24
    Diagnostics and eective stabilization oI currents in a Iuel cell stack
    H. Lustfeld, J. Hirschfeld, M. Reiel, B. Steffen
    306
    PC.2.25 Evaluation oI the diIIusion layer thickness by impedance and laser interIerometry methods
    A. Ko:mav, J. Nikonenko, N. Pismenskava, Ph. Sistat, J. Jasileva, J. Shaposhnik
    307
    PC.2.26 Predictive modeling oI ionic permselectivity oI porous media
    L. Seda, J. Kosek
    308
    PC.2.27 Modeling the perIormance oI enzyme immobilized membranes
    Y. Yurekli, S. Guedidi, S. Alsov Altinkava, A. Yemenicioglu, C. Innocent, A. Deratani, S. Roudesli
    308
    D - Processes 309
    D.1. Classical membrane operations: MF, UF, NF, RO, PV, ED.
    PD.1.1 Fabricating super-hydrophobe membrane via geometrical and chemical modiIication
    S.S. Madaeni, N. Ghaemi
    309
    PD.1.2 A new adsorption based model Ior bulk porosity tracing during membrane Iiltration
    E. Salehi, S.S. Madaeni
    309
    PD.1.3 PerIormance evaluation oI nanoIiltration membranes Ior diaIiltration oI dye/salt mixtures: experimental
    observations and model veriIication
    P. Mikulasek, J. Cuhorka
    310
    PD.1.4 Reverse osmosis Ior the ultrapuriIication oI aqueous hydrogen peroxide to electronic grade
    R. Abefon, A. Garea, A. Irabien
    310
    PD.1.5 InIluence oI porous stainless steel supports on pervaporation perIormance oI tubular silicalite
    membranes Ior concentrating bio-ethanol
    H. Negishi, H. Habe, T. Ikegami, K. Sakaki
    311
    PD.1.6 New high perIormance membranes Ior Iorward osmosis processes
    C. Hnel, C. Chaumette, G. Bisle, E. Walit:a, T. Schiestel
    312
    PD.1.7 The optimization Iactors Ior preparation oI heterogeneous reverse osmosis membranes
    T. Selimi, S. Gashi, N. Daci, F. Podvorica, B.S. Thai, A. Dvlhasi
    312
    PD.1.8 Dehydration oI ethanol with PVP composite membranes
    P. Rlling, C. Staudt
    313
    PD.1.9 Separation oI whey Iractions Irom Serpa cheese whey using a combination oI ultraIiltration and
    nanoIiltration, Irom
    A. Macedo, E. Duarte, M. Pinho
    313
    PD.1.10 Why do we need experiments to choose the right membrane?
    R. I. Orti:-Basurto, G. Pourcellv, T. Doco, P. Williams, M. Dornier, M.-P. Belleville
    314
    PD.1.11 Multilayered polyelectrolyte complexes as nanoIiltration membranes Ior anion separation
    P. Ahmadian Namini, X. Li, W. Govens, I. F.J. Jankelecom, B. Meesschaert
    315
    PD.1.12 New parameter Ior membrane cleaning eIIiciency determination
    C. Astudillo, J. Parra, S. Gon:ale:, B. Cancino
    315
    PD.1.13 Structural and Iunctional modiIications oI milk globular proteins induced by dead-end ultraIiltration
    M. Jan Audenhaege, F. Garnier-Lambrouin, S. Pe:ennec, G. Gesan-Gui:iou
    316
    PD.1.14 Membrane Iractionation oI red beet juice to obtain natural red colour extract
    B. Cancino, J.A. Parra
    317
    PD.1.15 Dehydration oI used solvents oI printing industry Ior reuse
    E. Bkoglu, H. Kalipilar, L. Yilma:
    317
    PD.1.16 PuriIication oI phosphoric acid by means oI membrane technology
    A. Kossir, K. Khaless
    318
    PD.1.17 EIIects oI oxidation states oI nickel (Ni), copper (Cu), palladium (Pd) and silver (Ag) on the rejection
    by nanoIiltration membranes
    T. J. Brooms, S. J. Modise, S. M. Nelana
    319
    PD.1.18 Electrodialysis as a useIul technique Ior glyceric acid separation Irom Iermentation broth
    H. Habe, Y. Shimada, T. Fukuoka, D. Kitamoto, M. Itagaki, K. Watanabe, H. Yanagishita, K. Sakaki
    319
    PD.1.19 Using microIiltration as an alternative Iresh water supply system Ior remote areas in the Amazon
    rainIorest
    M.J. Melo, B.R.S. Costa, A.S. Freitas, R.M. Caetano, C.K. Schul:, A.M.T. Louvisse, O.A. Pereira Jr
    320
    PD.1.20 Stability oI polymeric ultraIiltration membranes in alkaline conditions
    M. Kallioinen, M. Mnttri
    320
    PD.1.21 SurIactant Removal by a NanoIiltration/Photoelectrooxidation integrated process Irom a detergent
    industry wastewater
    C. Kor:enowski, A.F. Salvaterra, M.B.O. Martins, A.M.F. Silva, J.M.R. Tavares, A.M. Bernardes, J.Z.
    Ferreira, E.C.N.F. Duarte, M.N.C. Pinho
    321
    PD.1.22 EIIicient sunIlower oil degumming in cross-Ilow ultraIiltration by a PVDF membrane
    C. M. Coutinho, M. C. Chiu, L. A. Jiotto, L. A. G. Gonalves
    322
    PD.1.23 InIluence oI the operation parameters on the concentration oI apricot juice
    E. Fogarassv, A. Ko:ak, E. Bekassv-Molnar, G. Jatai
    322
    PD.1.24 Study oI the inIluence oI the enzymatic treatment in microIiltration oI aai pulp
    C.P. Bagagli, L.A. Jiotto
    323
    PD.1.25 The role oI surIactants Ior the recovery oI several bio-compounds using membrane technology
    M.O. Rui:, I. Escudero, J.M. Benito, J.L. Cabe:as, R.M. Geanta, B. Barriuso
    323
    PD.1.26 PerIormance oI micro and ultraIiltration membranes in wastewater treatment using membrane
    bioreactor
    S. Mafirad, M. H. Sarraf:adeh, M. R. Mehrnia
    324
    PD.1.27 Application oI nanoIiltration membranes in crude palm oil decoloration
    T. N. Queiro:, A. D. S. Machado, M. C. Chiu, L. A. Campos, L. A. Jiotto, L. A. G. Gonalves
    324
    PD.1.28 Separation oI oxygen with egg shell: Reverse pervaporation
    D. Krishnaiah, R. Sarbatlv
    325
    PD.1.29 PuriIication oI industrial phosphoric acid by nanoIiltration
    A. Charfi, N. Ben Amar
    325
    PD.1.30 Degradation kinetics oI nanoIiltration membranes in alkaline cleaning
    M. Mnttri, A. Pihlafamki, J. Lahti
    326
    PD.1.31 EIIects oI electrolytes on the noise in the over limiting current range: (Cation exchange membrane)
    K. Oulmi, K. E. Bouhidel
    326
    PD.1.32 Application oI membrane process in Vitamin C production - Plate & Irame membrane system Ior
    recovery oI 2-keto-L-gulonate
    J. Wei, L. Zhang, S. Wang
    327
    PD.1.33 Two-layer mass transIer rate`s equation Ioe separation by pervaporation oI dilute aqueous solution
    E. Nagv
    328
    PD.1.34 Application oI membrane technology at pilot plant scale to manuIacture concentrated colored
    polyphenolic water extracts Irom tropical vegetal biodiversity
    F. Adfe, W. Suttivattanavet, F. Guinle, C. Moquet, L. Meng, A. NDave, S.F. Wang, Y. Lo:ano
    328
    PD.1.35 Coupling oI membrane technology to add value to small-industrial scale micro-algae biomass
    production: a step toward sustainable development in the southern hemisphere
    K Mathis, Y. Lo:ano, S. Petitperrin, P. Lo:ano
    329
    PD.1.36 Preparation oI supports and membranes Ior micro-Iiltration using native raw materials
    A. Harabi, F. Zenikheri, F. Bou:erara, B. Boudaira, S. Condom
    330
    PD.1.37 Understanding the recovery oI ionic liquids by nanoIiltration: combining classical characterization
    methods with T-SAR approach
    J.F. Fernande:, R. Bartel, J. Thming
    330
    D.2. Membrane reactors: high/low temperature; catalytic /non catalytic; enzymatic or microbial.
    PD.2.1 Double-membrane reactor Ior gas phase hydroxylation oI aromatics: eIIect oI the catalytic properties oI
    the Pd-based membrane
    L. Bortolotto, R. Dittmever
    331
    PD.2.2 Enzyme-Iacilitated enantioselective transport oI (S)-lactic acid through a SLM based on ionic liquids
    E. Kulcsar, E. Nagv
    332
    PD.2.3 The enzymatic hydrolysis oI preparations oI potato starch in continuous recycle membrane reactor and
    adsorption characteristics oI the obtained products
    K. Prochaska, E. Konowal, J. Sulef, G. Lewandowic:
    332
    PD.2.4 Porous membrane catalytic systems Ior conversion oI bioorigin organics into hydrogen and syngas
    J. Zhmakin, A. Fedotov, D. Roi:ard, J. Korchak
    ,
    J. Uvarov, J. Teplvakov, M. Tsodikov
    333
    PD.2.5 Conception and study oI an enzymatic membrane reactor Ior the treatment oI eIIluents with phenolic
    compounds
    J. Chea, D. Paolucci-Jeanfean, J. Sanche:, M. P. Belleville
    334
    PD.2.6 Continuous membrane bioreactor system with submerged ceramic Ilat membranes Ior the production oI
    lactic acid
    T. Hahn, Z. Kovacs, S. Schieber, I. Hannemann, K. Grau, H.J. Schmidt, P. C:ermak
    334
    PD.2.7 Back-Ilush inIluence on microbial membrane bioreactor characteristics
    A. Noworvta, T. Grvgier
    335
    PD.2.8 Study oI the inIluence oI the components oI a microbial culture medium (micro-organisms and soluble
    compounds) on Iouling and species retention in a double membrane bioreactor
    J. Gnther, P. Loubiere, C. Lafforgue, C. Albasi
    336
    PD.2.9 Mathematical modeling oI enzymatic Iructooligosaccharide production in continuous membrane
    reactor
    Z. Kovacs, L. Engel, K. Grau, T. Hahn, M. Ebrahimi, P. C:ermak

    337
    PD.2.10 MF associated with an anaerobic Iluidized bed reactor. Part 1: Flux resistance evaluation
    L. L. Beal, M. Zeni, P. A. Boff, A. A. Lovatel
    337
    D.3. Membrane contactors: membrane distillation; crystallization; emulsiIication.
    PD.3.1 Experimental and Numerical Characterization oI mixing in a hollow Iiber membrane contactor by the
    iodide-iodate method
    N. Bakkar, R. Kieffer, C. Charcosset
    338
    PD.3.2 Treatment oI Olive Oil Mill Wastewater by an integrated membrane system
    E. Garcia-Castello, A. Cassano, A. Criscuoli, C. Conidi, E. Drioli
    339
    PD.3.3 Non dispersive solvent extraction oI alkali metal with calix|4|arene: modeling and process optimization
    Z. Albaraka :aher, J.M. Loureiro, M. Burgard, D. Trebouet
    339
    PD.3.4 Modeling and simulation oI HFMC Ior dispersion Iree liquid-liquid extraction oI copper
    M. Younas, S. Druon Bocquet, J. Sanche:
    340
    PD.3.5 Concentration oI duck Ieather keratin hydrolysate using direct contact membrane distillation
    K.J. Christensen, D. Bialas, D. Hfollund Jensen, P. Jensen
    341
    PD.3.6 Membrane-based Ripper method to accurate determination oI Iree and bonded sulIite content in red
    wine
    A. Pla:a, J. Romero, E. Morales, B. Pere:, W. Silva
    341
    PD.3.7 Near critical and supercritical Iluid extraction oI Cu
    2
    Irom aqueous solutions using hollow Iiber
    membrane contactors
    J. Romero, H. Jaldes, B. Pere:, F. Jalen:uela
    342
    PD.3.8 Thermally driven absorption chiller Ior residential cooling using membrane technology
    P. Schwerdt, C. Pollerberg, P. Schiffer
    344
    PD.3.9 Photosynthetic Iixation oI carbon dioxide into microalgae using gas-liquid membrane contacting
    process
    D.-E. Hong, B. Jung
    345
    PD.3.10 Concentration and modelling oI sucrose solution and apricot juice by mass transIer membrane
    processes
    A. Ko:ak, E. Fogarassv, G. Rac:, E. Bekassv-Molnar, G. Jatai
    345
    PD.3.11 Extractive ultraIiltration oI betaine using hollow Iiber contactors
    M.O. Rui:, I. Escudero, B. Martine:
    346
    PD.3.12 Seawater desalination by membrane distillation-crystallization: troubles at high recovery Iactors
    E. Curcio, J. Xiaosheng, G. Di Profio, S. Al-Obaidani, E. Drioli
    347
    PD.3.13 Sustainable processes based on the use oI selective liquid membranes Ior the recovery oI spent
    passivating baths
    R. Mediavilla, E. Bringas, I. Orti:, A. Urtiaga
    347
    D.4. AIIinity Membrane
    PD.4.1 Adsorption oI peptide binary mixtures by membrane chromatography
    J. Labanda, J. Sabate, J. Llorens
    348
    PD.4.2 Exploring liposome aIIinity chromatography Ior the separation oI plasmid DNA Vaccines
    L. Raiado-Pereira, D. M. F. Pra:eres, M. Mateus
    349
    PD.4.3 AIIinity membranes Ior antibody puriIication
    C. Boi, S. Dimartino, G.C. Sarti
    350
    D.5. Hybrid operations and process integration
    PD.5.1 Application oI integrated membrane photocatalytic reactor Ior the treatment oI synthetic dyes
    R. A. Damodar, H.-H. Chou, S.-J. You
    350
    PD.5.2 Increasing the water recovery in nanoIiltration by concentrate treatment: the Iouling potential oI humic
    acids aIter (per)ozonation
    S. Jan Geluwe, B. Jan der Bruggen, C. Jinckier, L. Braeken
    351
    PD.5.3 Evaluation oI the application oI chitosan as a coagulant/Ilocculatant in a microIiltration process oI
    natural water
    Flavia Jieira da Silva, Rosangela Bergamasco, Miria Hespanhol M. Reis, Christian Bouchard, Alvaro
    de Araufo, Maria Teresa Sousa Pessoa de Amorim
    352
    PD.5.4 Hydrophilic pervaporation Ior water control in the esteriIication reaction oI ethanol and acetic acid
    A. Hasanoglu, J. R. Alvare:, S. Luque
    352
    PD.5.5 EIIect oI superIicial gas velocity on gas holdup and circulation time in a novel hybrid membrane
    bioreactor
    F. P. Shariati, M. R. Mehrnia, M. H. Sarraf:adeh, M. Heran, C. Wisniewski
    353
    PD.5.6 Optimization oI the electrodeionization (EDI) process: comparison oI diIIerent resin bed conIigurations
    A. Lakehal, K.-E. Bouhidel
    354
    PD.5.7 Butanol recovery Irom aqueous solutions using pervaporation
    K. Sakaki, H. Negishi, H. Habe, T. Ikegami, H. Yanagishita
    354
    PD.5.8 Textile wastewater reclamation using electrocoagulation and nanoIiltration integrated system
    A. Aouni, C. Fersi, M. Ben Sik Ali, M. Dhahbi
    355
    PD.5.9 NaA zeolite membranes manuIactured by inocermic dewatering oI ethanol by vapour permeation in
    an industrial scale
    J.-Th. Khnert, E. Tusel, H. Brschke, H. Richter, M. Wevd, I. Joigt
    356
    PD.5.10 Reverse osmosis as a pre-concentration technology in the sugar industry
    S. Gul, A. Friedl, M. Harasek
    356
    PD.5.11 Comparison oI salt nature and evaluation oI the ionic electrochemical mobilities in electrodeionization
    (EDI)
    A. Lakehal, K.-E. Bouhidel
    357
    PD.5.12 SaponiIication and UF/NF separation oI value added tocopherols Irom crude palm oil
    K. Jachiraanan,

    J. Rattanapisit, P. Sridang
    358
    D.6. Process intensiIication with membranes
    PD.6.1 Enhanced separation oI suspended solids and polysaccharides during microIiltration oI pulp mill
    process water
    H. Krawc:vk, T. Persson, A.-S. Jnsson
    358
    PD.6.2 Production oI ultra pure water Irom sea water using H-SOD membranes
    S. Khafavi, K. Jansen, F. Kapteifn
    359
    PD.6.3 Integrated membrane system Ior biomethan ermentation
    N. Nemestothv, E. S:etgvrgvi, L. Gubic:a, K. Belafi-Bako
    360
    PD.6.4 Eco-design oI a membrane process Ior preparation oI milk protein Iractions: approach and Iirst results
    S. Omont, D. Froelich, P. Osset, F. Thueux, M. Rabiller-Baudrv, D. Beudon, L. Tregret, C. Buson, G.
    Gesan-Gui:iou
    360
    PD.6.5 EIIect oI pulsed electric Iield on the electrodialysis oI passion Iruit and naranjilla clariIied juices
    C. Sierra, E. Miguel, E. Jera, P. Sistat, P. Huguet
    361
    PD.6.6 EIIect oI coagulant on sludge thickening using Ilat sheet membrane
    R.C. Eusebio, H.G. Kim, H.S. Kim
    362
    E - Module Design and Engineering 362
    E.1. Fluid mechanics. Computational Iluid dynamics
    PE.1.1 Improvement oI the Ilow distribution in a laboratory membrane Iiltration cell by CFD study
    F. Cortes-Juan, B. Balannec, T. Renouard
    362
    PE.1.2 Experimental and numerical (CFD) investigation oI Ilow and concentration patterns in membrane
    modules with ladder-type spacers
    J.L.C. Santos, J. Geraldes, S. Jeli:arov, J.G. Crespo
    363
    PE.1.3 A Computational Fluid Dynamics study on droplet Iormation mechanism Irom membrane pore
    G. De Luca, A. Di Ren:o, F. P. Di Maio, E. Drioli
    364
    PE.1.4 Flow behaviour in a rectangular airliIt membrane bioreactor with diIIerent baIIle angles
    A. Khalili-Garakani, M. Mehrnia, N. Mostofi, M. H. Sarraf:adeh, F. Sadeghi
    364
    PE.1.5 Optical measurement oI dispersion in spacer-Iilled channels
    C. Baver, H. Breisig, M. Follmann, C. Frit:mann, T. Melin
    365
    E.2. Dynamic and design module operation
    PE.2.1 A new industrial concept Ior crossIlow Iiltration loops: the T.I.S.
    L. Grospellv, P. Lescoche, D. Girard
    366
    PE.2.2 Link between taylor bubble characteristics and Iibres bundle geometry: application to membrane
    bioreactors
    C. Bessiere, C. Guigui, A. Line, A. Ta:i-Pain
    366
    PE.2.3 Permeability analysis oI membranes Ior tangencial microIiltration
    M.D.M. Innocentini, R.J. Meloni, C. S. Silva, G. R. Youssef, C.O Hokka, M.Barbo:a
    367
    PE.2.4 Kinetic oI acetone absorption in hollow Iiber membrane contactor
    S:. Modelski, A. Witek-Krowiak
    368
    E.3. Microsystems and microtechnologies
    PE.3.1 Upstream preconcentration oI metal cations by way oI electrodialysis. Application to electrochemical
    detectors.
    S. Le-Than, P. Huguet, M. Cretin, Ph. Sistat, Ph. Da Costa
    368
    E.4. Fouling
    PE.4.1 Fouling oI the anion-exchange membranes during the electrodialysis oI aromatic amino acid solutions
    A. Bukhovets, T. Eliseeva, Y. Oren
    369
    PE.4.2 Experimental design Ior the evaluation oI the inIluence oI diIIerent variables on a submerged
    membrane bioreactor Ior the minimization oI Iouling phenomenon
    J. Etxebarria, D. Iturbe, A. Urkiaga
    370
    PE.4.3 EIIect oI Membrane Properties and Operational Condition oI MBR on BioIouling
    Sheng-Jie You, Shan-Shin Ou
    370
    PE.4.4 Modelling the EIIect oI packing density on Iiltration perIormance oI a hollow Iiber microIiltration
    module used in a speciIic membrane bioreactor.
    J. Gnther, P. Schmit:, C. Lafforgue, C. Albasi
    371
    PE.4.5 Application oI a dynamic model Ior wastewater treatment in submerged membrane bioreactors
    A. Zarragoitia, S. Schetrite, U. Jauregui-Ha:a, O. Lorain, C. Albasi
    372
    PE.4.6 Electroreduction oI milk and membrane Iouling
    J. Pericou, M. Arava-Farias, L. Ba:inet
    372
    PE.4.7 A comparative study oI Iouling-related properties oI bulking and normal sludge suspension during
    membrane Iiltration
    H. A:ami, M. R. Mehrnia, M. H. Sarraf:adeh, S. Amiri, S. S. Madaeni

    373
    PE.4.8 The eIIectiveness oI relaxation and backwashing on removing Iouling in a Ilat sheet MBR
    P. van der Marel, A. Zwifnenburg, A. Kemperman, M. Wessling, H. Temmink, W. van der Meer
    374
    PE.4.9 The inIluence oI membrane properties on the Silt Density Index
    A. Alhadidi, A. Kemperman, J Schippers, M. Wessling, W. Jan der Meer
    374
    PE.4.10 MicroIiltration oI pitanga juice: analysis oI membrane pore blocking models
    R. S. Ongaratto, I. C. N. Debien, L. A. Jiotto
    375
    PE.4.11 Experimental study oI velocity and transmembrane pressure proIiles in spiral membranes Irom the Iull
    mapping oI protein Iouling quantiIied by FTIR-ATR
    M. Rabiller-Baudrv, J. Belmefdoub, L. Paugam, B. Balannec
    376
    PE.4.12 UltraIiltration oI metalworking Iluids: eIIect oI a destabilization/centriIugation pretreatment stage on
    membrane Iouling
    D. Allende, D. Pando, J.M. Benito, C. Pa:os, J. Coca
    376
    PE.4.13 Protein external Iouling in microIiltration. EIIect oI protein-protein and protein-membrane electrostatic
    interactions
    C. Jelasco, J.I. Calvo, A. Martin, F. Martine:, A. Hernande:
    377
    PE.4.14 IdentiIication oI Ioulants elements in degumming by ultraIiltration (PVDF) oI miscella oI crude canola
    oil
    L. Ara Campos, M. C.h Chiu, L. A. Guaraldo Gonalves, L. A. Jiotto
    378
    PE.4.15 MF associated with an anaerobic Iluidized bed reactor. Part 2: MFI evaluation
    L. L. Beal, M. Zeni, P. A. Boff, A. A. Lovatel, S. J. Della Giustina
    378
    PE.4.16 Direct observation oI gypsum growth on RO membranes in the presence oI bioIilm
    R. Arbel, Y. Oren, M. Her:berg, J. Gilron
    379
    PE.4.17 Impact oI the biologically pretreatment groundwater on membrane Iouling
    A. Fuqaha, A.Friedl, M. Harasek
    380
    PE.4.18 Fouling understanding during rough non-alcoholic beer with ceramic membrane
    M. Ya:danshenas, S. A.R. Tabatabaee Ne:had, M. Soltanieh , L. Fillaudeau
    381
    E.5.Pre-treatment and cleaning
    PE.5.1 Using inIrasonic Irequency back pulsing to clean micro and ultra Iiltration membranes, Iouled with
    dextrin, yeast and alumina
    D. S. McLachlan, E. Shugman
    382
    PE.5.2 Ultrasonic cleaning oI oil-Iield produced water-Iouled ceramic membranes
    M. Ebrahimi, A. Wienold, P. Mund, P. C:ermak
    382
    PE.5.3 Cleaning oI Iouled membranes in oily water Iiltration, a statistical approach
    M. Hesampour, M. Jnsk, M. Mnttri, M. Nvstrm
    383
    PE.5.4 Study oI membrane ageing mechanisms by Iree radical species using electron paramagnetic resonance
    C. T. Matos, J. G. Crespo
    384
    F - Applications 384
    F.1. Energy Fuel cells H
    2
    recovery
    PF.1.1 InIluence oI membrane characteristics and operating conditions on power generation with pressure
    retarded osmosis
    A. Achilli, T.Y. Cath, A.E. Childress
    384
    PF.1.2 Permeability and selectivity to H
    2
    oI Pd membranes supported on porous stainless steel tubes
    J.M. Sanche:, M. Maroo, M.M. Barreiro
    385
    PF.1.3 Separation oI hydrogen issued Irom the decomposition oI hydriodic acid on supported MFI-type
    membrane
    A. Darwiche, J. De Lamare, M. Comte, J. Jaltchev
    386
    PF.1.4 Polymer membranes containing ionic liquids Ior Iuel cells
    J. Schauer, M. Paidar, P. Ma:ur, K. Bou:ek
    387
    PF.1.5 Impregnated membranes Ior direct methanol Iuel cells
    D. Stamatialis, M.H. Yildirim, A. Schwar:, M. Wessling
    388
    PF.1.6 Generating power utilizing PRO-membranes with a hierarchical structure
    C. Chaumette, C. Hnel, G. Bisle, E. Walit:a, T. Schiestel
    388
    PF.1.7 Ion-exchange membranes Ior Iuel cells based on vinylphosphonic acid copolymers doped with
    phosphoric acid
    J. Zitka, M. Bleha, J. Schauer, M. Paidar, M. Pliskova, J. Malis
    389
    PF.1.8 SulIonated poly(ether ether ketone) based MEA Ior Iuel cell optimization
    K.S. Roelofs, P. Wursthorn, T. Hirth, T. Schiestel
    390
    PF.1.9 Polyvinyl alcohol-Iumed silica nano-composites as polymer electrolyte Ior alkaline direct methanol
    Iuel cells
    S. Jessie Lue, J.-Y. Chen, W.-T. Wong
    390
    PF.1.10 PVA nanoIiber reinIorced NaIion membrane Ior DMFC application
    S. Molla, T. Leon Yu, E. Riande, J. Compa
    391
    PF.1.11 Resistance phenomena in ion exchange membranes at low salt concentrations
    P. Dlugolcki, K. Nifmeifer, S. Met:, M. Wessling
    392
    PF.1.12 A zeolite membrane reactor Ior glycerol exploitation as raw material
    L. Roldan, R. Mallada, J.M. Fraile, J.A. Mavoral, M. Menende:
    393
    PF.1.13 Mathematical model oI a membrane reactor combined with in-situ regeneration Ior methane
    aromatization
    A. Romeo, M. Menende:
    393
    PF.1.14 Poly(vinyl alcohol) based polymer electrolyte membrane Ior passive type direct methanol Iuel cell
    M. Higa, M. Sugita, S. I. Maesowa, N. Endo
    394
    PF.1.15 SelI-organized proton nanochannels in hybrid Iuel-cell membranes, exhibiting high ionic conductivity
    M. Michau, M. Barboiu
    395
    PF.1.16 Porous electrochemical contactors Ior a concentric bioIuel cell
    A. Habrioux, G. Merle, K. Servat, B. Kokoh, C. Innocent, M.Cretin, S. Tingrv
    396
    PF.1.17 Poly(diphenylsulIone-oxadiazole)s as materials Ior Iuel cells
    M. Schieda, I. Ternes, S. Nunes
    396
    PF.1.18 SulIonated poly(vinylidene Iluoride)-based composite Iilms with improved electrical conductivity Ior
    PEM Iuel cell application
    A. Lien Ong, A. Bottino, G. Capannelli, A. Comite
    397
    PF.1.19 Development oI plasma polymers as proton conducting membranes Ior Iuel cell cores
    A. Ennafdaoui, S. Roualdes, J. Durand, P. Brault, M. Cavarroc
    398
    PF.1.20 Bi-dimensional and numerical study oI heat transIer in planar SOFC single cell: chemical heat source
    models
    B. Zitouni, H. Ben moussa, K. Oulmi, H. Abdenebi
    398
    PF.1.21 Carbon black tail-gas separation using a Matrimid

    polymeric membrane
    O. C. Joinea, D. Gorri, I. Orti:, A. Urtiaga
    399
    PF.1.22 Preparation oI Pd/Ag composite membranes and simulative analysis oI transIer resistance Ior hydrogen
    separation
    M.I. Mohamed D:ahir, Z. Wu, K. Li
    399
    PF.1.23 Perovskite brazing on metals Ior steam electrolysis under pressure
    J. Loricourt, Y. Paranthoen, B. Sala, G. Pourcellv, M. Chavigneau, A.K. Sirat ,O. Lacroix
    400
    PF.1.24 Perovskite-based cermet electrode Ior steam electrolysis with proton conducting electrolyte
    F. Grasset, K. Rahmouni, S. Willemin, B. Sala, H. Takenouti, C. Deslouis, M. Keddam, A.K. Sirat, O.
    Lacroix
    401
    PF.1.25 Composite proton-exchange membranes based on sulIonated or phosphonated polymer-graIted silica
    particles
    F. Niepceron, T. Boucheteau, J. Bigarre, H. Galiano
    401
    PF.1.26 Rejuvenation oI hygrothermally aged NaIion

    F. Thominette, F. Collette, G. Gebel


    402
    F.2. Environment Waste treatments
    PF.2.1 EIIect oI presence oI humic substances on ultraIiltration oI xenobiotic compounds
    N. Ghaemi, S.S. Madaeni, M. De Nobili, A. Ali:adeh
    403
    PF.2.2 New membrane method Ior the regeneration oI activated carbon saturated with H
    2
    S
    N. Douiche
    ,
    H. Grib, H. Lounici, M.O. Mecherri, N. Ghaffour, N. Mamri
    403
    PF.2.3 Recycled water treatment, operation and costing using advanced MF and UF membranes
    S. Caothien, T. Wachinski, M. Farcv, D. Jial
    404
    PF.2.4 Challenge testing membrane Iiltration at a wastewater Iacility in the New York city watershed
    J.A. Habib, M. Farcv, D. Jial
    404
    PF.2.5 Treatment oI oilIield produced water with combined inorganic ultra- and nanoIiltration membranes
    M. Ebrahimi, D. Willershausen, L. Engel, P. Mund, P. Bolduan, P. C:ermak
    405
    PF.2.6 Treatment oI bleach plant eIIluents and separation oI lignin compounds via ceramic UF/NF membranes
    M. Ebrahimi, S. Kerker, A. Wienold, H. Neul, A. Ante, M. Hilpert, P. Mund, P. C:ermak
    406
    PF.2.7 Composting eIIluent treatment by membrane bioreactor
    J. Gagnaire, P. Moulin, L. Chapon, B. Marrot
    406
    PF.2.8 Treatment oI dyeing industry waste water by nanoIiltration and reverse osmosis
    E. Ellou:e, N. Khlif, P. Moulin, R. Ben Amar
    407
    PF.2.9 Treatment oI return liquors water by means oI reverse osmosis
    K. Koniec:nv, J. Cwikla
    407
    PF.2.10 PerIormances oI a MBR Ior the puriIication oI pretreated olive vegetation waste water
    M. Stoller, G. Farabegoli, M. Bravi
    408
    PF.2.11 Use oI reaction and ultraIiltration Ior the treatment oI contaminated soils by metallic or organic micro-
    pollutants
    A. Petitgirard, M. Dfehiche, J. Persello, M. Euvrard, P. Fievet, N. Fatin-Rouge
    409
    PF.2.12 Use oI PAUF Ior the removal oI chelated metal ions Irom industrial wastewaters
    D. Zamariotto, A. B. Akadar, P. Fievet, N. Fatin-Rouge
    409
    PF.2.13 Use oI reaction and ultraIiltration to decontaminate media
    A. Petitgirard, M. Dfehiche, D. Zamariotto, A. B. Akadar, J. Persello, M. Euvrard, P. Fievet, N. Fatin-
    Rouge
    410
    PF.2.14 Application oI membrane processes in manure treatment
    K. Koniec:nv, A. Kwiecinska, M. Bod:ek
    410
    PF.2.15 Waste water Irom mechanical pulping - a natural resource, not a waste
    T. Persson, H. Krawc:vk, A.-S. Jnsson
    411
    PF.2.16 Removal oI cobalt Irom water solutions by polymer assisted ultraIiltration
    L. Dambies, A. Jaworska, G. Zakr:ewska-Tr:nadel, B. Sartowska, A. Miskiewic:
    411
    PF.2.17 Treatment and recovery oI leather and cork processing industrial wastewaters by membrane hybrid
    processes
    C. Kor:enowski, K Streit, A. C. Santos, M. Minhalma, A. M. Bernardes, J. Z. Ferreira, M. N. C. Pinho
    412
    PF.2.18 Potato industry waste water management by enzymatic hydrolysis oI protein
    G. Lewandowic:, Z. Lubiewski, K. Lefa, W. Balcerek
    413
    PF.2.19 Iodine separation Irom well waters using liquid membrane
    M. E. Craciun, A. C. Nechifor, C. Luca, G. Nechifor
    414
    PF.2.20 Synthesis, morphologic analysis and water vapour Ilux through the cellulose triacetate asymmetric
    membranes Irom waste materials: newspaper and mango seed
    C.S. Meireles, M. Zeni, E.A.M. Ribeiro, M.F. Ferreira Junior, R.M.N. Assuno, G. Rodrigues Filho
    414
    PF.2.21 Interactions oI micropollutants, microorganisms and secondary treatment eIIluent matrix in RO and NF
    processes Ior wastewater reuse
    M. Jacob, C. Guigui, C. Cabassud, S. Masclet, L. Moulin, G. Lavison
    415
    PF.2.22 UltraIiltration membrane oI ZrO
    2
    deposited on porous ceramic support prepared Irom moroccan natural
    material: elaboration characterization and application
    H. Elkinani, A. Larbot, J. Benavente, S. Rakib, M. Sghvar
    416
    PF.2.23 Removal oI tributyltin compounds in a membrane bioreactor
    M. Aubenneau, J. Seira, C. Bancon-Montignv, C. Wisniewski
    416
    PF.2.24 Membrane process treatment Ior greywater recycling: investigations on direct tubular nanoIiltration
    F. Hourlier, A. Masse, P. Jaouen, A. Lakel, C. Gerente, C. Faur, P. Le Cloirec
    417
    PF.2.25 Treatment by membrane technology, oI press liquid Irom solid wastes generated during orange juice
    production
    E. Garcia-Castello, L. Mavor, A. Argelles, M.L. Gras, D. Jidal
    418
    PF.2.26 Cyclophosphamide removal by nanoIiltration and reverse osmosis membranes - EIIect oI water matrix
    properties
    L. Wang, C. Albasi, J. Faucet-Marquis, A. Pfohl-Les:kowic:, C. Dorandeu, B.Marion, C. Causserand
    418
    PF.2.27 PURATREAT: Optimized MBR wastewater treatment Ior the Mediterranean area
    H. Zwifnenberg, A. Kemperman, S. Savadi, T. Arnot, M. Ben Maklouf, M. Wade
    419
    PF.2.28 DiIIerent membrane approaches Ior the transport oI arsenic: advantages and limitations oI polymer
    inclusion, anion-exchange and supported liquid membranes
    R. Gell, C. Fontas, E. Antico, J. Salvado, S. Jeli:arov, J. Crespo
    420
    PF.2.29 Polymer inclusion membranes Ior As(V) transport and removal
    R. Gell, A. Parramon, E. Antico, J. Salvado, C. Fontas
    420
    PF.2.30 The Iate oI 14C-radiolabelled dicloIenac and 4`-hydroxydicloIenac in a laboratory scale MBR
    H. Boufu, G. Hommes, T. Wintgens, P. Corvini
    421
    PF.2.31 Processing solvent-rich water by nanoIiltration
    F.P. Cuperus, I.M. Wienk
    422
    PF.2.32 Simultaneous removal oI copper and cadmium by Micellar-Enhanced UltraIiltration using sodium
    deoxycholate
    J. Landaburu, E. Pongrac:, R. Keiski
    422
    PF.2.33 Hollow Iiber supported liquid membrane microextraction Ior the determination oI acidic
    pharmaceuticals in water samples
    E. Wdowiak, E. Sagrista, J. Salvado, P. Wiec:orek, M. Hidalgo
    423
    PF.2.34 Gas holdup and liquid circulation in an airliIt membrane bioreactor
    M. Ka:em:adeh Afshar, M. H. Sarraf:adeh, M. R. Mehrnia, S. Naseri, F. Pafoum Shariati
    423
    PF.2.35 Ammonia removal Irom salty water by direct contact membrane distillation
    R. Sarbatlv, D. Krishnaiah, C. K. Chiam
    424
    PF.2.36 Development oI membranes Ior the preconcentration oI Uranium(VI)
    A.M. Candela, P. Masque, C. Palet
    424
    PF.2.37 Studies on demulsiIication oI linseed oil/water emulsion by PVDF membrane
    L. Li, L. Ding, J.L. Lanoiselle, Z. Tu, D. Clausse
    425
    PF.2.38 Coupling adsorption/Iiltration process. Application to remove metallic cation Irom wastewater
    A. Soudani, F. Sinan, M. Persin, A. Larbot
    426
    PF.2.39 Practical applications oI membrane technology Ior liquid radioactive waste processing
    D.J. Adamovich, S.A.Dmitriev, J.I. Panteleev, J.M. Gelis, J.J. Milvutin
    426
    PF.2.40 Application oI liquid membranes to the chemical speciation oI silver in natural waters
    J. A. Lope:-Lope:, M. Garcia-Jargas, C. Moreno
    427
    PF.2.41 Reverse osmosis treatment oI condensate Irom distillery stillage concentration: inIluence oI operating
    conditions and preliminary design
    M. Gavach, C. Fargues, C. Sagne, M. Decloux, M.L. Lameloise
    427
    F.3. Drinking water Desalination
    PF.3.1 Preparation oI Ag nanoparticle coated cellulose acetate membrane Ior removal oI microorganisms
    S.S. Madaeni, T.A. Arbatan
    428
    PF.3.2 EIIect oI Ieed concentration on ion transIer using dialysis process
    Y. Mansourpanah, S.S. Madaeni
    428
    PF.3.3 Energy eIIiciency oI reverse osmosis associated to hydrostatic pressure plants Ior seawater desalination
    C. Charcosset, C. Falconet, M. Combe
    429
    PF.3.4 Comparison oI polymeric and ceramic ultraIiltration membranes Ior separation oI natural organic
    matter Irom water
    M. Kabsch-Korbutowic:, A. Urbanowska
    429
    PF.3.5 Fouling oI membranes during ultraIiltration oI surIace water
    M. Bod:ek, M. Rafca, A. Platkowska
    430
    PF.3.6 Photodegradation oI phenanthrene using TiO
    2
    suspensions
    M. Dfehiche, S. Menetrier, A. Petitgirard, J. Persello, M. Euvrard, P. Fievet, N. Fatin-Rouge
    431
    PF.3.7 A study oI the eIIect oI natural organic matter on herbicide retention by NF membrane
    K. J. Plakas, A. J. Karabelas
    432
    PF.3.8 EIIect oI membrane Iouling and scaling on phytoestrogens removal in reverse osmosis
    and nanoIiltration
    M. Bod:ek, M. Dud:iak
    432
    PF.3.9 Structural analysis oI polyamide 66 membranes prepared by phase inversion in ternary system
    water/cloridric acid/poliamide
    M. Zeni , J. Duarte, P. Poletto
    433
    PF.3.10 Comparison oI behaviors oI three bacteriophages MS2, Q and T4, during the ultraIiltration membrane
    process
    G. Pierre, A. Furiga, M. Berge, C. Roques, P. Aimar, C. Causserand
    434
    PF.3.11 Preparation and characterization oI anion-exchange membranes with semi-interpenetrating network
    structure oI poly(vinyl alcohol) and polycation
    M. Nishimura, S. Kuwada, E. Shimi:u, M. Higa
    435
    PF.3.12 PerIormance oI ultraIiltration plants in France, comparison with ultraIiltration plants Ior sea water RO
    pretreatment application
    A. Leroux, J. Banham, E. Chaumien, L. Boutarin
    435
    PF.3.13 EIIective removal oI virus by ceramic microIiltration with in-line coagulation pretreatment
    T. Matsushita, N. Shirasaki, M. Kobuke, Y. Matsui, K. Ohno
    436
    PF.3.14 ModiIication oI RO membranes via graIt polymerization oI methacrylate monomers that possess
    quaternary- ammonium groups
    M. J. Brami, S. Belfer, R. Kasher
    437
    PF.3.15 Renewable energy powered membrane systems: potential Ior inorganics removal Irom groundwaters
    L. A. Richards, B. S. Richards, A. I. Schfer
    438
    F.4. Non aqueous membrane applications
    PF.4.1 Development oI hexane-resistant membranes Ior solvent recovery Irom sunIlower oil/hexane mixture
    P. Martino, C. Pagliero, N. Ochoa, J. Marchese
    438
    PF.4.2 Film-Iorming cellulose acetate graIt copolymers with nano-structured architectures: Application to the
    puriIication oI bio-Iuels by pervaporation
    A. Jonquieres, M. Billv, A. Ran:ani Da Costa, P. Lochon, R. Clement, M. Dresch, S. Etienne
    439
    PF.4.3 PDMS membranes applicable in both nanoIiltration and pervaporation
    A. Dobrak, B. Jan der Bruggen, I. Jankelecom
    440
    PF.4.4 InIluence oI organic solvent properties on nanoIiltration membrane separation oI active pharmaceutical
    ingredient (API)
    F.W. Lim, M. Makowski, D. Ormerod, A. Horvath, A.G. Livingston, A.T. Boam
    440
    PF.4.5 Cross-linked 6FDA-based copolyimide membranes - Characterization method and perIormance in
    aromatic/aliphatic separation
    D. Katar:vnski, A. Mixa, P. Rlling, C. Staudt
    441
    PF.4.6 Valorisation oI a by-product Irom vegetable oil production by enzymatic reaction and membrane
    processing
    A.R.S. Teixeira, J.L.C. Santos, J.G. Crespo
    442
    PF.4.7 Combination oI organic solvent nanoIiltration and molecular engineering towards the eIIicient
    recycling oI oleIin metathesis catalysts
    T. Renouard, A. Keraani, C. Fischmeister, M. Rabiller-Baudrv
    442
    PF.4.8 High permeable OSN membranes based on glassy polymer with high Iree-volume Iraction
    A. J. Jolkov, J. J. Parashchuk, D. F. Stamatialis, E.G. Litvinova, J. S. Khotimskv, J. J. Jolkov,
    M. Wessling
    443
    PF.4.9 Electro-extraction applied to highly dilute hydro-organic solutions
    S. Lacour, Ph. Sistat, P. Huguet, S. Deabate, G. Pourcellv
    444
    F.5. Gas separation Air treatment - CO
    2
    recovery
    PF.5.1 A novel engineered high throughput equipment Ior membrane based gas separations
    A. L. Khan, S. Basu, A. Cano-Odena, I. F. J. Jankelecom
    445
    PF.5.2 Asymmetric PVTMS-membranes Ior membrane gas desorption: regeneration oI amine-based solvents
    S.E.Tsarkov, J. de Bruin, A.J.Jolkov, E.L.J. Goetheer, J.J. Jolkov
    446
    PF.5.3 Enhanced CO
    2
    solubility in aromatic and alkyl chain substituted imidazolium-based room temperature
    ionic liquids
    A. Finotello, J. E. Bara, S. Naravan, D. L. Gin, R. D. Noble
    446
    PF.5.4 CO2 separation properties oI a commerciable polysulIone hollow Iiber membrane
    H. Y. Hwang, M. J. Koh, H. C. Koh, S. Y. Ha, F. Scura, G. Barbieri, E. Drioli, S. Y. Nam
    447
    PF.5.5 Separation oI toluene, propylene and butadiene mixtures Irom air by a membrane process Ior emissions
    reduction
    G. Rebollar-Pere:, E. Carretier, N. Lesage, P. Moulin
    448
    PF.5.6 Supported ionic liquid ceramic membranes Ior gas separation
    J. Christel, T. Hirth, T. Schiestel
    448
    PF.5.7 Separation oI CO
    2
    /CH
    4
    binary mixtures through zeolite Iilled polyethersulIone based mixed matrix
    membranes
    . akal, H. Kalipilar, L. Yilma:
    449
    PF.5.8 Separation oI CO
    2
    and H
    2
    using palladium membranes (Ior integration in power generation with CO
    2
    capture)
    J.M. Sanche:, M. Maroo, M.M. Barreiro
    450
    PF.5.9 CO
    2
    Iacilitated transport membranes by ionic liquids in NaIion matrix
    S. Yoo, J. Won
    450
    PF.5.10 Semiinterpenetrating networks based on Matrimid

    and cyanurate ester resins Ior suppression oI CO


    2
    -
    plasticization
    M.L. Sanche:, E.M. Mava, A. Marcos, J.G. de la Campa, J. de Abafo
    451
    PF.5.11 Molecular dynamics simulation study oI carbon dioxide transport in 6FDA- based polyimides
    S. Pandivan, D. Brown, N. van der Jegt, S. Nevert:
    452
    PF.5.12 A novel multilayered membrane Ior the separation oI CO
    2
    Irom biogas and other permanent gas
    streams: Process investigations
    J. Wind, T. Brinkmann, C. Naderipour, T. Wolff
    453
    PF.5.13 InIluence oI porous support structure on perIormances oI high permeance composite hollow Iibres
    membranes
    M. Sandru, S. H. Haukebo, M.-B. Hgg
    453
    PF.5.14 ETS-10/chitosan composite membranes Ior CO
    2
    /N
    2
    gas separation
    C. Casado, C. Telle:, J. Coronas
    454
    PF.5.15 Analysis oI membrane perIormance in the treatment oI gas streams oI industrial interest
    P. Bernardo, G. Clari:ia
    455
    PF.5.16 Gas-liquid membrane contactors based on non-porous membranes Ior the recovery oI CO
    2
    Irom gas
    mixtures
    M. Shalvgin, R. Yastrebov, A. Golub, F. Beggel, J. Khotimskiv, J. Teplvakov
    455
    PF.5.17 Long-term perIormance investigation oI biogas upgrading systems applying gas permeation
    membranes
    M. Harasek, M. Miltner, A. Makaruk
    456
    PF.5.18 Gas permeation oI polyamide membranes supported on ceramic tubes
    K. Briceo, R. Garcia-Jalls, D. Montane
    457
    PF.5.19 Asymmetric hyIlon AD60X membranes entrapping ruthenium porphyrin complexes Ior gas separation
    M.G. Buonomenna, G. Golemme, E. Gallo, S. Fantau::i, E. Drioli
    457
    PF.5.20 Preparation and gas transport properties oI polysulIone nanocomposite membranes modiIied with
    additives
    S. Deni:, I. Gurkan, E. Okumus
    458
    PF.5.21 Gas permeation properties oI poly(ether imide) nanocomposite membranes based on surIace-treated
    silica
    S. Deni:, D. Kutsal, E. Okumus
    459
    PF.5.22 Membranes in biogas upgrading
    M. Afhar, S. Yuece, T. Melin
    460
    F.6. Food and packaging
    PF.6.1 The eIIect oI non-ionic surIactant on nanostructure oI polyethersulIone ultraIiltration membranes
    A. Rahimpour, S.S. Madaeni
    460
    PF.6.2 EIIect oI membrane length and membrane resistance on critical and limiting Ilux at the Iractionation oI
    milk proteins by microIiltration
    A. Pirv, W. Khnl, T. Grein, S. Ripperger, U. Kulo:ik
    461
    PF.6.3 Optimisation and integration oI membrane processes: recent developments in the starch and yeast
    industries
    F. Lipni:ki, M. Nilsson
    461
    PF.6.4 EIIect oI operational variables on Iouling at the clariIication oI orange juice
    C. Pagliero, L. Firman, N. Ochoa, J. Marchese
    462
    PF.6.5 Olive oil quality improvement by membrane processes
    J.P. Bonnet, J. Artaud, C. Ochs, P. Ochs, P. Moulin
    463
    PF.6.6 Use oI electrodialysis with ultraIiltration membranes Ior natural phenolic antioxidant enrichment oI
    cranberry juice
    L. Ba:inet, C. Cossec, H. Gaudreau, Y. Desfardins
    463
    PF.6.7 Caseinate based biodegradable Iilms Ior packaging applications
    J.-L. Audic, B. Chaufer
    464
    PF.6.8 EIIects oI operation parameters on permeate Ilux and Iouling resistances Ior ultraIiltration oI Radix
    Astragalus aqueous extracts
    M. Cai , H. Liang
    465
    PF.6.9 MicroIiltration Ior the reduction oI microorganisms in complex Iood systems: eIIect oI bacterial
    characteristics on Iiltration result
    J. Kaufmann, U. Kulo:ik
    465
    PF.6.10 Membrane Iouling during wine microIiltration
    Y. El Ravess, C. Albasi, P. Bacchin, P. Taillandier, J. Ravnal, M. Mietton-Peuchot, A. Devatine
    466
    PF.6.11 Characterization oI brine Irom a desalination plant Ior Iood process applications
    A. Argelles, E. Garcia-Castello, L. Mavor, M.L. Gras, D. Jidal
    466
    PF.6.12 EIIect oI low anode/cathode voltage diIIerence application on redox potential modulation during milk
    electroreduction and storage
    L. Ba:inet, A. Schrever, J. Lessard
    467
    PF.6.13 Protein concentration Irom salmon gelatin by ultraIiltration
    S. Gon:ale:, B. Cancino
    467
    PF.6.14 Enzymatic treatment eIIect on pitanga juice microIiltration
    R. S. Ongaratto, I. C. N. Debien, L. A. Jiotto
    468
    PF.6.15 InIluence oI some chemical additives and ultraIiltration operating conditions on puriIication
    characteristics and permeate Ilux oI thin sugar beet juice
    R. Nia:mand, M. Shahidi, S.M.A. Ra:avi
    469
    PF.6.16 Sugar reduction by nanoIiltration oI white musts prior to viniIication
    N. Garcia-Martin, L. Palacio, P. Pradanos, A. Hernande:, M. Ortega-Heras, S. Pere:-Magario, D.C.
    Gon:ale:-Huerta, ML Gon:ale:-San Jose, M. Mihnea
    469
    PF.6.17 Micro and ultraIiltration perIormance oI cellulose, PVDF and PES membranes in the green coconut
    water (Cocus nucifera) processing
    I. C. N. Debien, R. S. Ongaratto, L. A. Jiotto
    470
    PF.6.18 Screening oI organic microIiltration membranes to produce protein-stabilized oil-in-water emulsions by
    membrane emulsiIication
    A. Trentin, C. Gell, F. Lope:, M. Ferrando
    471
    PF.6.19 Premix membrane emulsiIication to produce protein-stabilized O/W emulsions with entrapped -
    carotene
    A. Trentin, C. Gell, F. Lope:, M. Ferrando
    472
    PF.6.20 Sugar reduction in grape juice using membrane Iractionation
    B. Cancino, R. Rubv
    472
    PF.6.21 Lycopene concentrated oI papaya pulp using polymeric membranes
    F. C.Silva, L.A. Jiotto
    473
    PF.6.22 Degumming oI canola crude oil by ultraIiltration with polymeric membranes
    L. Ara Campos, M. C. Chiu, L. A. Guaraldo Gonalves, L. A. Jiotto
    473
    PF.6.23 EIIect oI canola crude oil degumming by polymeric membrane ultraIiltration on tocopherol
    L. Ara Campos, M. C. Chiu, L. A. Jiotto, L. A. Guaraldo Gonalves
    474
    PF.6.24 Galacturonic acid recovery by electrodialysis
    E. Molnar, N. Nemestothv, K. Belafi-Bako
    474
    PF.6.25 Protein recovery in enzyme-assisted aqueous extraction processing oI soybeans
    J.M.L.N. de Moura, N.M. de Almeida, K. Campbell, C.E. Glat:, L.A. Johnson
    475
    F.7. Pharmaceuticals and biotechnologies
    PF.7.1 EIIect oI polyethylene glycol on morphology and perIormance oI polyvinyl alcohol hemodialysis
    membranes
    J. Bar:in, S.S. Madaeni, S. Pourmoghadasi
    475
    PF.7.2 Preparation, characterization and application oI a membrane microdevice
    H. Hassan, A. Cano-Odena, T. Gumi
    476
    PF.7.3 PuriIication oI a recombinant baculovirus by ion exchange membrane chromatography
    T. A. Grein, Z. Kovacs, R. Michalskv, P. C:ermak
    476
    PF.7.4 Preparation and characterization oI urease immobilized ultraIiltration membranes
    Y. Yurekli, S. Guedidi, S. Alsov Altinkava, A. Yemenicioglu, C. Innocent, A. Deratani, S. Roudesli
    477
    PF.7.5 Nexterion NC/UniSart slides: nitro cellulose coated substrates Ior optimal perIormance and high
    reproducibility in protein microarray applications
    U. Andag, M. Hollas, E. Jallerat, S. Drebing, K. Frit:, K. Pflan:, D. Mel:ner, A. Rees, R. Dietrich
    477
    PF.7.6 Novel membrane adsorbers Ior large scale downstream processing
    D. Mel:ner, R. Faber, W. Demmer, H.-H. Hrl
    478
    PF.7.7 Separation oI selected pharmaceuticals Irom waters by liquid membrane systems
    N. Pont, J. Salvado, C. Fontas
    478
    PF.7.8 Basics in Iormat development Ior immunoassays: comparison oI classical protein microarrays & lateral
    Ilow systems
    S. Beck, D. Husler, S. Dbel, F. Gessler, U. Andag, M. Hollas, K. Pflan:
    479
    PF.7.9 Dual membrane diaIiltration (DMD) process Ior pharmaceutical and nutraceutical puriIications
    I. Sereewatthanawut, F.W. Lim, M. Makowski, Y. Bhole, A.G. Livingston, A.T. Boam
    480
    PF.7.10 Fouling index in tangential membrane Iiltration applied Ior separation oI cephamycin C Irom
    Iermentation broths
    A. Baptista Neto, F. Pearubia, C.O. Hokka, M. Barbo:a
    480
    PF.7.11 Membrane-based technologies in the separation and puriIication oI whey proteins
    R. Ibae:, M.P. Mier, J. Dia:, I. Orti:
    481
    PF.7.12 Preparation, characterization and application oI molecularly imprinted membranes (MIM) Ior the
    separation oI DL-selenomethionine
    A. Conesa, T. Gumi, C. Palet
    482
    F.8. Health and artiIicial organs
    PF.8.1 Transport mechanism oI the polyamines through the supported liquid membranes, process optimization
    and possible medical applications.
    K. Pokafewic:, P.P. Wiec:orek
    483
    PF.8.2 Mixed matrix membranes Ior blood puriIication
    J. Sun, S. Saiful, Z. Borneman, D.F. Stamatialis, M. Wessling
    483
    PF.8.3 Modelling oI the dielectric properties in the biological and artiIicial membrane stimulates by electric
    circuit RC
    N. Nesralla , F. Hamdach,, S. Bahlouli, N. Benharrat
    484
    F.9.Sensors, actuators
    PF.9.1 All-solid-state taste sensor with lipid-polymer membranes Ior discrimination oI soIt drinks
    M. S:pakowska, E. Marfanska
    485
    PF.9.2 Selective sensor utilizing monocrystal-thin b-oriented silicalite-1 layer-Metglas assembly
    L. Gora, J. Kuhn, Th. Baimpos, J. Nikolakis, F. Kapteifn, E. M. Serwicka
    485
    PF.9.3 Composite membranes Ior carbon Iiber microelectrodes dedicated to health and environmental
    micropollutants analysis
    M. Pontie, E. Talla Feuhouo, T. Papp, S. Bourhis, P. Fokou, T. Feng
    486
    F.10. Textiles and napkins
    PF.10.1 InIluence oI pH on membrane Iouling and perIormance oI tubular ceramic membranes treating textile
    wastewater
    M.I. Alcaina-Miranda, S. Barredo-Damas, M.I. Iborra-Clar, J.A. Mendo:a-Roca
    486
    PF.10.2 Textile wastewater reuse by means oI sequencing batch reactor technology and nanoIiltration
    E. Zuriaga Agusti, J.A. Mendo:a Roca, M.I. Iborra Clar, M. Tancredi
    487
    G - Out of the Lab-University-Industry Technology Transfer 488
    G.1. Case study assessments
    PG.1.1 Preparation and characterization oI PSU-alumina hybrid membranes Ior use in Iiltration processes
    J. dos Santos, C. Z. Ma:utti, C. P. Bergmann, M. Zeni
    488
    PG.1.2 Valorisation oI cork boiling wastewaters by membrane processing
    A.R.S. Teixeira, J.L.C. Santos, J.G. Crespo
    488
    PG.1.3 Recovery oI an hydroxytyrosol-rich extract Irom olive mill residues by membrane technology
    J.L.C. Santos, J.G. Crespo
    489
    PS.1.1 Applied silicon carbide membrane applications
    Jens Husted Kfr, MsC Chemical Engineering
    490
    AUTHORS INDEX 491
    PLENARY LECTURES
    -1-
    PL.1
    Molecular, nano and microfabrication of membranes
    M. Wessling
    Universitv of Twente, Facultv of Science and Technologv, MESA Institute of Nanotechnologv, P.O. Box 217, 7500 AE
    Enschede.
    m.wesslingutwente.nl
    This presentation reIlects on strategies to design membranes. Design strategies can cover diIIerent length-scales: (a) the sub-
    nanometer empty space (Iree volume) in dense polymers, (b) the nanometer space oI interIaces, and (c) the micrometer space
    oI membrane porosity and geometry.
    On a molecular scale, one aims to tailor the material properties to improve permeability and selectivity oI the materials. The
    molecular design oI the membranes utilizes the extensive knowledge present in polymer and surIace chemistry. Molecular
    scale manipulation will be elucidated here through examples on the design and characterization oI segmented block-
    copolymers.
    Nanometer scale design is a terrain with a rich spectrum oI materials science strategies. OIten the strategies involve the use oI
    nanoparticles and to process those particles into a continuous phase being the membrane. Here, we present the use oI (a)
    dendritic macromolecules to tailor the permeability and selectivity oI polymers used in gas separation and (b) silver
    nanocluster to manipulate the transport oI gases through carbon membranes.
    Micrometer scale design can be realized by utilizing photolithography based replication processes. The presentation illustrates
    the preparation oI perIorated microsieves and microstructured hollow Iibers and Ilat sheet membranes. The purpose oI micro-
    structuring the surIace is to increase the speciIic surIace area available Ior permeation as well as inIluencing the hydrodynamic
    conditions.
    PL.2
    Biological membranes on supports: physical models of cell surfaces and smart
    materials
    M. Tanaka
    Institute of Phvsical Chemistrv and Center for quantitative Biologv (BIOQUANT), Universitv of Heidelberg, Germanv
    tanakauni-heidelberg.de
    Biological membranes are vital components oI all living systems, Iorming the outer boundary oI living cells or oI organelles.
    They consist largely oI a lipid bilayer that imparts a Iluid character. Proteins embedded in the bilayer and carbohydrates
    attached to its surIace Iacilitate communication and transport across the membrane. These Ieatures enable membranes to act as
    important Iilters: processes (some oI which may be incompatible) are conIined to the organelles they occur in and toxic
    substances are kept out oI the cell, while speciIic nutrients, wastes and metabolites can pass the membranes oI organelles and
    cells to reach their destination.
    Functional modiIication oI solid surIaces with plasma membrane models draws an increasing attention as a straightIorward
    strategy to bridge soIt biological materials and hard inorganic materials. Both artiIicial and native membranes can be deposited
    on ultrathin polymer supports that mimic the generic role oI extracellular matrix and glycocalix (polymer-supported
    membranes).
    The main part oI my talk provides a brieI overview oI various Iunctionalization methods, together with some strategies to
    physically model the membrane-substrate contact with such thin polymer interlayers. In the second part, I will introduce
    several strategies to apply polymer-supported membrane concepts with cell biology and semiconductor technology.
    -2-
    PL.3
    Half a century later - The impact of membranes in water and wastewater
    management schemes
    H. Buisson
    Jeolia Water Solutions and Technologies
    hpbuissonveoliawater.com
    As global population increases so does the need to develop better water management schemes, taking into account sanitation
    requirements, increasingly stringent discharge limits, and the need to Iind and supply good quality water to sustain growths
    locally.
    More than ever, today`s water experts are challenged to Iind new aIIordable solutions to meet the needs oI municipalities and
    industries. The problems posed are not always easy, but recent progresses in material sciences, analytical tools, sensors,
    computing and digital-based developments, provide opportunities to rethink and reengineer local water cycles, while
    integrating more and more energy, waste management and environmental impact considerations.
    Starting 50 years ago pioneering scientists developed man-made materials with interesting transport and separation properties:
    membranes. With the contribution oI great innovators, talented engineers, convincing salesmen and business visionaries
    worldwide, membranes have moved out oI labs starting in the early 60s-70s. Through various phases; with increasing volumes
    and related lower production costs, the development oI adapted and optimized designs, and better integrations with other water
    and wastewater unit treatment processes, membranes have now become a basic tool in our toolbox oI water and wastewater
    treatment solutions.
    Using various projects and market data the presentation will illustrate the impact oI membranes in water and wastewater
    treatment today.
    The 'membrane story is not over by Iar and many chapters remain to be written, as membranes will be an enabling Iactor to
    help us develop Iuture local water and wastewater treatment solutions. The presentation will also open a window on some
    novel developments and Iurther needs Ior development.
    PL.4
    Closing technology gaps to enable energy efficient membrane-based separations
    W. Koros
    School of Chemical & Biomolecular Engineering, Georgia Institute of Technologv, Atlanta, Georgia,30332, USA
    wjkchbe.gatech.edu
    Over the next several decades, escalating global demands Ior water, Iuel and chemical commodities will be driven by
    population growth and the desire Ior higher living standards in developing countries. Using conventional thermally-driven
    separation technology to meet these demands will greatly increase global energy consumption and carbon dioxide emissions.
    In principle, energy intensity and carbon dioxide emissions associated with separations to provide the above necessities could
    be reduced by a full order of magnitude via membrane separations. Many large scale energy intensive separations involve
    gases and non-aqueous Ieeds, which are not addressed adequately by existing membrane options. II capacity expansions take
    place using energy-ineIIicient conventional separation technologies, an opportunity will be missed, since subsequent
    displacement oI such installed capacity will be economically diIIicult to justiIy. This Iact makes it imperative to press Ior
    implementation oI realistic large scale membrane based approaches within the next decade. As will be discussed, membranes
    based on crosslinked polymers, inorganic-polymer hybrids, metals and pure inorganic or carbon materials show great potential
    to satisIy most oI the broad spectrum oI separation needs. UnIortunately, application oI such advanced materials in large scale
    membrane processes Iaces greater challenges than are generally acknowledged. Technology gaps preventing production oI
    economical large scale membrane modules based on advanced materials will be discussed. Nontechnical hurdles that seriously
    impede closure oI these technical gaps will also be considered. The most serious nontechnical hurdles include: (i) aversion to
    risk by industrial leaders, and (ii) inability oI governmental leaders to see industrial energy eIIiciency as a societal problem
    requiring signiIicant investment. Fortunately, a successIul example where these nontechnical hurdles were overcome is oIIered
    by reverse osmosis technology Ior water production where visionary leaders catalyzed change. Encouraging signs oI re-
    emergence oI a similar perspective are increasingly apparent. This new perspective is promoted by the need to reduce
    industry`s large carbon Iootprint as well as to save energy. Our community must seize this opportunity and eIIiciently close
    remaining technical gaps to enable introducing the next generation oI advanced membranes to promote global sustainability.
    -3-
    -4-
    ORAL COMMUNICATIONS
    -5-
    OA.1.1
    Polymer-zeolite-additive three-component mixed matrix composite membrane for
    CO
    2
    /CH
    4
    separation
    E. Erpek, B. A. Ozkale, S. Halitoglu, C. Atalay-Oral, M. G. Ahunbay, S. B. Tantekin-Ersolmaz
    Istanbul Technical Universitv, Department of Chemical Engineering, Maslak, Istanbul 34469, TURKEY
    ersolmazitu.edu.tr
    Polyimides are promising membrane materials in separation oI plasticizing and corrosive gas streams due to their outstanding
    chemical stability. Polyimide prepared Irom 4,4-hexaIluoro isopropylidene diphthalic anhydride (6FDA) and 2,4,6-trimethyl-
    m-phenylene diamine (DAM) is attractive due to its high permeability Ior many gases but its selectivity is much lower than the
    industrially relevant values Ior commercially important gas pairs. The incorporation oI a properly chosen zeolite into a
    polymeric matrix has been shown to be an eIIicient way Ior improving separation perIormance oI polymers. However, lack oI
    adhesion at the zeolite-polymer interIace due to the incompatibility oI the inorganic zeolite and organic polymer poses an
    important challenge Ior many zeolite-polymer pairs. The aim oI this work is to prepare mixed matrix composite (MMC)
    membranes Irom highly permeable 6FDA-DAM with improved selectivity. Use oI a low molecular weight additive as
    compatibilizers is chosen to enhance the adhesion at the zeolite-polymer interIace. Low molecular weight additives have been
    reported to cause a signiIicant reduction in the permebility oI polymers. 6FDA-DAM can aIIord a reduction in permeability in
    return Ior an enhancement in selectivity. The polymer-zeolite-additive three-componet system is used here to tailor the
    separation properties maximizing both permeability and selectivity Ior CO
    2
    /CH
    4
    separation.
    MMC 6FDA-DAM membranes are prepared using zeolites 4A and SAPO-34 as the dispersed phases. 2,4,6-
    Triaminopyrimidine (TAP) is used as the compatibilizing additive. 6FDA-DAM is synthesized by one-pot rule. ModiIied and
    unmodiIied polymer and MMC membranes with diIIerent compatibilizer content is characterized by DSC, TGA, and
    single/mixed gas permeation measurements at 35C. The morphology oI MMC membranes are examined by scanning electron
    microscopy (SEM). Mass uptake measurements are also carried out by using Intelligent Gravimetric Analyser (IGA). Sorption
    behavior oI the unIilled polymer is also estimated via molecular simulation methods. The simulations were carried out using
    the Accelrvs Materials Studio 4.1 simulation package and COMPASS Iorce Iield. A combination oI molecular dynamics and
    Monte Carlo methods were used to predict the sorption properties. Addition oI TAP has improved both the adhesion at the
    interIace and the selectivity oI 6FDA/DAM even at low concentrations due to its antiplasticization eIIect. Incorporation oI 4A
    and SAPO-34 has enhanced permselectivity oI TAP-modiIied 6FDA-DAM signiIicantly. A CO
    2
    permeability oI 8.3 Barrer and
    an ideal CO
    2
    /CH
    4
    selectivity oI 259 are obtained at 2 TAP and 20 SAPO-34 addition. The simulated sorption isotherms
    compare very well with the experimental data obtained Irom IGA measurements.
    Financial support Irom TUBITAK (Turkish ScientiIic and Technological Research Council) Grant No. 106M179 is grateIully
    acknowledged. SAPO-34 samples were kindly provided by Dr. H. Kalipilar at Middle East Technical University, Turkey.
    OA.1.2
    Mixed matrix membranes with high surface area nanoporous materials for gas
    separation
    P. Gorgojo
    1,2
    , S. Uriel
    1,3
    , C. Tellez
    1,2
    , J. Coronas
    1,2

    1
    Aragon Institute of Nanoscience, C/ Pedro Cerbuna 12, Zarago:a 50009, Spain.
    2
    Chemical Engineering Department, Universitv of Zarago:a, C/ Maria de Luna 3, Zarago:a 50018, Spain.
    3
    Organic Chemistrv Department, Universitv of Zarago:a, C/ Maria de Luna 3, Zarago:a 50018, Spain.
    pgorgojounizar.es
    Mixed matrix membranes (MMM`s) are a very interesting option Ior gas separation with the advantages oI working with both;
    an easy to process material, the polymer, and a very selective material, in terms oI molecular size, the nanoporous material, in
    this case a zeolite. The objectives oI this work are the synthesis and characterization oI the inorganic phase to be dispersed in
    the polymer and the preparation oI mixed matrix membranes out oI them. XRD, TGA, BET, SEM and TEM characterization
    leads to a better understanding oI the intrinsic properties oI the zeolitic materials and the role played by them once embedded
    into the polymers.
    A new, high aspect ratio inorganic Iiller obtained by the treatment oI precursor Nu-6(1) |1| with CTABr at pH 9 (buIIer
    solution oI DL-histidine) and 80C with a surIace area around 300 m
    2
    /g aIter calcination has been synthesized in order to
    -6-
    prepare MMM`s Ior gas separation (Figure 1). The X-ray diIIraction pattern is that oI the Nu-6(2) zeolite, although this zeolite
    as obtained using Corma`s recipe |1| has a surIace area oI only about 79 m
    2
    /g. The high surIace area obtained through a direct
    delamination process would help the contact oI the crystals with the polymer and thereIore improve the permselectivity
    properties oI the membranes in comparison with those made out oI regular Nu-6(2) crystals and Udel

    polysulIone or
    Matrimid

    polyimide previously published |2,3|.


    Flat membranes with a permeation area oI 15 cm
    2
    were Iabricated and placed inside a permeability module to achieve the
    separation oI the binary mixtures H
    2
    /CH
    4
    and N
    2
    /CO
    2
    . A given mass-Ilow controlled binary mixture was Ied into the retentate
    side oI the membrane at diIIerent pressures above the atmospheric one to create the necessary driving Iorce, while the
    permeate side was swept by a mass-Ilow controlled stream oI Ar or He and analyzed by an on-line gas microchromatograph
    Agilent as shown in Figure 2 .
    Figure1. Mixed matrix membrane scheme Figure 2. Permeation measurements setup
    Acknowledgements: Financial support Irom Spanish Ministry oI Science and Education (MAT2007-61028, PCI2005-A7-0348
    and FPU program).
    |1| A. Corma, V. Fornes and U. Diaz. Chem. Commun., 2001, 2642-2643.
    |2| P. Gorgojo, S. Uriel, C. Tellez and J. Coronas. Microporous and Mesoporous Materials, 115, 2008, 85-92.
    |3| P. Gorgojo, B. Zornoza, S. Uriel, C. Tellez and J. Coronas. Studies in SurIace Science and Catalysis, 174, 2008, 653-656.
    OA.1.3
    Gas transport properties of a novel copolymer of vinylidene fluoride
    G. Golemme
    1,2
    , M. G. Buonomenna
    1
    , F. Mikes
    3
    , Y. Okamoto
    3
    , J. C. Jansen
    2
    1
    Dipartimento di Ingegneria Chimica e dei Materiali, Universita della Calabria, and Consor:io INSTM, Jia Pietro Bucci
    45A, I-87030 Rende (CS), Italv
    2
    ITM-CNR, Istituto per la Tecnologia delle Membrane, Jia Pietro Bucci 17C, I-87030 Rende (CS), Italv
    c
    Polvmer Research Institute, Polvtechnic Universitv, 6 Metrotech Center, Brooklvn, 11201 NY, USA
    ggolemmeunical.it
    A novel glassy and amorphous copolymer oI vinylidene Iluoride and perIluoro-3-methylene-2,4-dioxabicyclo|3.3.0|octane
    (coVDF, Figure 1) was synthesized and used to prepare dense membranes. The diIIusion coeIIicient, the permeability and the
    solubility oI He, H
    2
    , N
    2
    , O
    2
    , CH
    4
    and CO
    2
    through coVDF were measured by means oI time-lag and steady state permeation
    measurements.
    The diIIerences in the mobility oI the diIIerent gases indicates that the coVDF matrix is size - selective, with a combination oI
    He permeability (176 Barrer) and He/H
    2
    separation Iactor (2.9), along the 2008 Robeson upper bound |1|. The permeability oI
    the six gases through coVDF is much higher than in PVDF |2|, and on average it is intermediate between those through HyIlon
    AD60 and Cytop |3|. The higher solubility oI CO
    2
    and CH
    4
    in coVDF than in HyIlon and Cytop might be the consequence oI
    the dipolar character oI the coVDF backbone, which interacts more strongly with condensable, quadrupolar and easily
    polarisable molecules.
    This work conIirms that the introduction oI bulky and rigid groups along the backbone oI a semicrystalline Iluoropolymer is a
    viable tool Ior obtaining amorphous glassy polymers with outstanding separation properties, as is the case oI TeIlon AF and
    HyIlon AD |3|.
    -7-
    Figure 1. Repeat units oI poly(vinylidene Iluoride-co-perIluoro-3-methylene-2,4-dioxabicyclo|3.3.0|octane) (coVDF)
    |1| L. M. Robeson, The upper bound revisited. J. Membrane Sci., 2008, 320, 390-400.
    |2| M. J. El Hibri, D. R. Paul, Gas transport in poly(vinylidene Iluoride): eIIects oI uniaxial drawing and processing
    temperature; J. Appl. Polym. Sci., 1986, 31, 2533-60.
    |3| T. C. Merkel, I. Pinnau, R. Prabhakar, B. D. Freeman; Gas and Vapor Transport Properties oI PerIluoropolymers; in Yu.
    Yampolskii, I. Pinnau, B. D. Freeman, Eds.; Material Science oI Membranes Ior Gas and Vapor Separation; Wiley: Chichester
    (UK), 2006; pp. 251-70.
    OA.1.4
    Organic/inorganic hybrid nanocomposite membrane on the basis of
    poly(4-methyl-2-pentyne) and TiO
    2
    S.Shishatskiy
    1
    , W.Yave
    1
    , V.Abetz
    1
    , S.Matson
    2
    , E.Litvinova
    2
    , V.Khotimskiy
    2
    , K.-V.Peinemann
    1

    1
    Institute of Polvmer Research, GKSS Research Centre Geesthacht GmbH, Max-Planck-Str. 1, 21502 Geesthacht, Germanv
    2
    A.J.Topchiev Institute of Petrochemical Svnthesis, Russian Academv of Sciences (TIPS RAS), Leninskv prospect, 29, 119991
    Moscow, Russia
    Sergey.Shishatskiygkss.de
    Creation oI sustainable membrane processes Ior separation oI hydrocarbon containing gas mixtures, e.g. natural gas, is
    alternative approach Ior reIinement oI diIIerent gas steams. Development oI novel polymeric and hybrid materials Ior
    membranes is a very topical challenge. Glassy polymers oI 1,2-disubstituted acetylenes that exhibit highest known gas and
    vapor permeability combined with good mechanical properties attract great attention.
    Opposite to conventional glassy polymers polyacetylenes such as the most permeable poly(1-trimethylsilyl-1-propyne)
    |PTMSP| and it`s analogues poly(1-trimethylgermyl-1-propyne) |PTMGP| and poly(4-imethyl-2-pentyne) |PMP| have higher
    permeability Ior condensable organic gases and vapours than Ior smaller permanent gases. This property is attributed to
    extremely high Iree volume oI the stiII main chain polymer having bulky substituents.
    Hydrocarbon polyacetylene PMP possesses high stability towards organic compounds and chemical resistance resulting Irom
    stable C-C bond (in comparison with C-Si). Furthermore, prospective availability oI monomer 4-methyl-2-pentyne, synthesis
    oI which can be realized with the use oI industrial products 4-methyl-2-pentene or methylisobutylketone, makes PMP much
    promising polymer Ior membrane application.
    In our work nanocomposite material Iormed Irom PMP and sol oI nanoparticles oI TiO
    2
    with enhanced permeability n-butane/
    methane selectivity is presented. Use oI TiO
    2
    nanoparticles in Iorm oI sol has allowed to prepare nanocomposite with uniIorm
    distribution oI nanoparticles in polymer matrix provided by coordination oI Ti to CC bond oI the polymer. The
    microstructure oI the PMP was taken into account Ior preparation oI nanocomposites with TiO
    2
    since trans- conIiguration oI
    the main chain is more accessible Ior coordination then cis- conIiguration. Trans-conIiguration reach samples oI PMP were
    synthesized and studied Ior gas transport properties in Iorm oI thick Iilms and composite membranes.
    Gas permeability tests Ior PMP/TiO
    2
    membrane in n-butane(1.6 mol.)/methane(98.4 mol.) show high n-butane
    permeability and n-butane/methane selectivity and indicating change oI Iree volume available Ior sorption oI butane without
    too large cavities Iormed that could promote non-selective gas Ilow.
    Composite Ilat-sheet membranes with the selective layer made oI PMP/TiO
    2
    were prepared on the pilot scale using porous
    PAN membrane as a support. Membrane envelopes were prepared and long-term tested Ior gas transport properties. All
    envelopes show high gas permeance and selectivity on the level oI thick Iilms indicating high processability oI the PMP/TiO
    2
    hybrid material.Results oI model gas mixture (n-butane/N
    2
    ) separation with 1.2 m
    2
    membrane module on the pilot closed loop
    Iacility will be discussed during the presentation.
    Acknowledgement. Funding Ior this research was provided by the European Commission (Project COMPOSE, NMP3-
    CT-2003-505633).
    -8-
    OA.1.5
    Dynameric membranes: toward an adaptive constitutional transport
    M. Barboiu
    Adaptive Supramolecular Nanosvstems Group, Institut Europeen des Membranes, (IEM), UMR-CNRS-5635 ENSCM, UM2,
    CNRS, Universite Montpellier II, Place Eugene Bataillon CC047, F-34095 Montpellier Cedex 5, France.
    Mihai.barboiuiemm.univ-montp2.Ir
    Numerous artiIicial transport systems utilizing carriers, channel-Iorming or selI-organized polymeric and hybrid
    superstructures able to orient, to select and to pump the ionic transport across membranes have been developed in the last
    decades.
    ArtiIicial membrane materials are the subject oI various investigations, oIIering great potentialities as well on the level oI their
    chemical composition or organization as to that oI the concerned applications. OI special interest is the structure-directed
    Iunction oI biomimetic and bioinspired membrane materials and control oI their build-up Irom suitable units by selI-
    organisation. The main interest Iocus on Iunctional biomimetic membranes in which the recognition-driven transport
    properties could be ensured by a well-deIined incorporation oI receptors oI speciIic molecular recognition and selI-
    organization Iunctions, incorporated in a hybrid dense or mesopourous materials. We are thereIore proposing to review the
    membrane transport properties oI such supramolecular membrane materials.
    The Iirst part begins with a survey oI diIIerent methods and processes which can be used Ior the generation oI molecular
    recognition-based hybrid materials.
    Then basic working principles oI selI-organized membranes are provided in order to better understand the requirements in
    material design Ior the generation oI Iunctional membrane materials.
    These results describe the simple synthetic hybrid biomaterials which successIully Iormed molecular recognition devices,
    transport patterns so as to enable eIIicient translocation events.
    Finally actual and potential applications oI such selI-organized systems presenting combined Ieatures oI structural adaptation
    in a speciIic nanospace will be presented. From the conceptual point oI view these membranes express a synergistic adaptative
    behaviour: the addition oI the Iittest solute (ions, molecules and gaz, etc) drives a constitutional evolution oI the membrane
    toward the selection and ampliIication oI a speciIic transporting superstructure in the presence oI the solute that promoted its
    generation in a Iirst time. This is the interesting example oI dynamic evolutive membranes 'dynameric membranes where a
    solute induces the upregulation oI (prepares itselI) its own selective membrane.
    This work was supported by Iunds Irom the Participating Organizations oI EURYI and the EC Sixth Framework Program
    |1| M. Barboiu, C. Luca, C. Guizard, N. Hovnanaian, L. Cot, J. Membrane Sci., 1997, 129, 197-207.
    |2| M. Barboiu, C. Guizard, J. Palmeri, C. Reibel, C. Luca, L. Cot, J. Membrane Sci. 2000, 172, 91-103.
    |3| M. Barboiu, G. Vaughan, A. van der Lee, Org. Lett. 2003, 5, 3073-3076.
    |4| M. Barboiu, S. Cerneaux, G. Vaughan, A. van der Lee, J. Am. Chem. Soc. 2004, 126 3545-3550.
    |5| A. Cazacu, A. van der Lee, T.M. Fyles, M. Barboiu, J. Am. Chem. Soc. 2006, 128(29), 9541-9548.
    |6| C. Arnal-Herault, M. Michau, M. Barboiu, Angew. Chem. Int. Ed. 2007, 46, 8409-8413.
    |7| C. Arnal-Herault, M. Barboiu, A. Pasc, M. Michau,

    A. van der Lee, Chem. Eur. J. 2007, 13, 6792
    |8| C. Arnal-Herault, A. Pasc-Banu, M. Barboiu Angew. Chem. Int. Ed. 2007, 46, 4268-4272.
    |9| M. Barboiu, P. Aimar, J.-M. Lehn, J. Memb. Sci., 2008, 321, 1-2; (b) J. Memb. Sci., 2008, 321, Special issue : From simple
    molecules to complex membrane systems
    OA.1.6
    Effect of preparation parameters on performance of polyethersulfone based mixed
    matrix gas separation membranes
    E. Karatay, H. Kalipilar, L. Yilmaz
    Department of Chemical Engineering, Middle East Technical Universitv 06531 Ankara TURKEY
    karataymetu.edu.tr
    The separation oI carbon dioxide Irom natural gas is essential to reduce pipeline corrosions induced by acidic CO
    2
    gas which
    makes natural gas puriIication an important industrial process. Removal oI CO
    2
    Irom CH
    4
    by membranes is a promising
    process among other techniques.
    -9-
    In this study, the gas separation perIormance oI polyethersulIone (PES) based mixed matrix membranes are investigated.
    Zeolite SAPO-34 is selected as the dispersed inorganic phase. Also various low molecular weight additives (LMWA) such as
    2-hydroxy 5-methyl aniline (HMA), p-nitroaniline (pNA), 4-amino 3-nitro phenol (ANP) are added to the membrane
    Iormulation. Pure PES, SAPO-34 containing PES, LMWA containing PES, both SAPO-34 and LMWA containing PES
    membranes are Iabricated Ior CO
    2
    /CH
    4
    separation. The membranes are prepared by solvent evaporation method using
    dimethylsulIoxide (DMSO) as solvent and annealed at 225
    o
    C which is above the glass transition temperature (T
    g
    ) oI PES in
    order to remove the residual solvent. As well as annealing above T
    g
    oI PES, the addition oI LMWA to the matrix is likely to
    enhance the adhesion at the interIace between the glassy polymer PES, and SAPO-34 crystals. Apart Irom that, LMWAs may
    aIIect the inherent properties oI the polymer matrix itselI.
    Single gas permeability measurements revealed that addition oI LMWAs decreased the permeability and increased the
    selectivity but 2-hydroxy 5-methyl aniline (HMA) being the most eIIective one among the others. With the addition oI 4 w/w
    oI HMA to the pure PES casting solution, the CO
    2
    permeability decreased to 1.78 Barrer Irom 3.42 Barrer, and CH
    4
    permeability decreased to 0.058 Barrer Irom 0.140 Barrer whereas the CO
    2
    /CH
    4
    ideal selectivity increased to 30.6 Irom 24.4
    The diIIerential scanning calorimeter (DSC) analysis showed that glass transition temperature oI the membranes decreases
    with the increasing concentration oI LMWAs. Scanning electron microscopy (SEM) images oI PES membranes containing
    SAPO-34 revealed the homogeneous dispersion oI zeolite crystals.
    OA.1.7
    Sorption and diffusion of organic vapours in poly-trimethyl-silyl-norbornene:
    experimental characterization and comparison with NELF model predictions
    M. Galizia, M.G. De Angelis, G.C. Sarti
    Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali, Universitv of Bologna, via U. Terracini 28,
    40131 Bologna, Italv.
    giulio.sartiunibo.it
    Addition-type poly(trimethyl silyl norbornene) (PTMSN) is a high Iree volume glassy polymer endowed with a rather high
    vapour solubility and permeability values, which makes it attractive Ior gas/vapor separation applications.
    In this work, experiments oI sorption oI n-alkanes (n-C
    4
    , n-C
    5
    , n-C
    6
    ) in PTMSN were perIormed at 35C, using a constant
    volume/variable pressure apparatus, and in parallel the matrix dilation was measured using a speciIic optical device. During the
    sorption experiments one can observe marked relaxation phenomena and very high values oI solubility, that are comparable to
    those observed in a vapour-selective material such as poly(trimethyl silyl propyne) (PTMSP). The diIIusion coeIIicients show
    a concentration dependence which is particularly pronounced Ior the larger penetrant (n-C
    6
    ), because its higher solubility
    induces in the polymeric matrix a plasticization eIIect more pronounced.
    The experimental solubility isotherms were successively compared with the NELF model calculations: the Lattice Fluid
    characteristic parameters Ior PTMSN were estimated by a collection oI inIinite dilution solubility data available in the
    literature |1|, thus obtaining the Iollowing values Ior the polymer characteristic parameters: T
    *
    405.98 K, p
    *
    359.82 MPa and

    *
    1.345 Kg/L. The corresponding model predictions Ior the solubility isotherms are in quite good agreement with the
    experimental data Ior all the penetrants and in entire pressure range inspected.
    The polymer shows a dilation behaviour characteristic oI the glassy state |2| and the experimental swelling coeIIicients agree
    satisIactorily with the values calculated using the NELF model.
    |1| L. Starannikova et al., Addition type polynorbornene with Si(CH
    3
    )
    3
    side groups : detailed study oI gas permeation and
    thermodynamic properties, J. Membrane Sci., 2008, 323, 134-143.
    |2| M.G. De Angelis et al., Gas sorption and dilation in poly-(2,2bis-(triIluoromethyl)-4,5-diIluoro-1,3-dioxole-co-
    tetraIluoroethylene): comparison oI experimental data with predictions oI Nonequilibrium Lattice Fluid Model,
    Macromolecules, 2002, 35, 1276-1288.
    -10-
    OA.1.8
    Differences in mass transport of C
    1
    -C
    6
    alkanes and alcohols
    through perfluorinated membranes
    K. Friess
    1
    , J.C. Jansen
    2
    , B. Cernochova
    1
    , V. Hynek
    1
    , O. Vopicka
    1
    , M. Zgazar
    1
    , M. Sipek
    1
    1
    Department of Phvsical Chemistrv, Institute of Chemical Technologv, Technicka 5, 166 28 Prague 6, C:ech Republic
    2
    Institute on Membrane Technologv, ITM-CNR, Jia P. Bucci 17/C, 87030 Rende (CS), Italv
    karel.Iriessvscht.cz
    Amorphous glassy perIluoropolymers (PFP) with high Iractional Iree volume are known Ior their excellent chemical and
    thermal properties, which make them interesting Ior speciIic gas-gas or organic-organic separations. However, their potential is
    not yet Iully explored and also the understanding oI their transport properties needs Iurther progress |1|. In the present work
    sorption experiments (C
    1
    -C
    6
    alcohols, pentane and hexane vapour activity Irom 0.1 to 0.9) were perIormed on Ilat membranes
    oI TeIlon

    AF, copolymers oI 2,2-bis(triIluoromethyl)-4,5-diIluoro-1,3-dioxole and tetraIluoroethylene (Fig. 1). Measurements


    were perIormed gravimetrically at 25C by a sorption apparatus equipped with the calibrated quartz (McBains) spiral balance
    |2|; the sorption isotherms were determined and the diIIusion coeIIicients oI the diIIerent vapours were obtained Irom the
    sorption kinetics |1,2|.
    In parallel the permeation oI C
    1
    , C
    4
    and C
    6
    alkanes and C
    1
    -C
    4
    alcohol vapours were carried out at 25C at appropriate Ieed
    pressures in a Iixed volume-pressure increase instrument. The diIIusion coeIIicients oI the penetrants were determined Irom
    the transient behaviour (time lag method) and the permeability was calculated Irom the steady state pressure increase rate.
    The diIIusion coeIIicients were correlated with the penetrant`s critical volume (V
    c
    ) in a plot oI log D vs. V
    c
    . Comparison oI the
    diIIusion coeIIicients oI the alkanes with those oI the corresponding alcohols revealed a dramatic inIluence oI the OH-group
    on the molecular transport. Fundamental diIIerences between the alkanes and the alcohols could be ascribed to intermolecular
    interactions (clustering).
    Figure 1. Chemical structure oI TeIlon AF

    2400 (Du Pont), where x 0.9.


    The authors are grateIul Ior the Iinancial support Irom the Ministry oI Education, Youth and Sports MSM (Grant No.
    6046137307), the Grant Agency oI the Czech Republic (Grant No.104/09/1357) and the EU 6
    th
    Iramework program Network
    oI Excellence NanoMemPro.
    |1| J. C. Jansen, K. Friess, E. Drioli, Transport oI alcohol vapours in amorphous glassy perIluoropolymer membranes with
    high Iractional Iree volume: evaluation oI clustering through time lag measurements (in preparation)
    |2| K. Friess, J. C. Jansen , O. Vopicka,

    A. Randova, V. Hynek,
    ,
    M. Sipek, L. Bartovska, P. Izak, M. Dingemans, Jo DewulI,
    H.Van Langenhove, E. Drioli: Comparative study oI sorption and permeation techniques Ior the determination oI heptane and
    toluene transport in polyethylene membranes. (Submitted into J. Membrane Sci. in November 2008)
    -11-
    OA.1.9
    Preparation of super-hydrophobic PVDF membranes organized in a hierarchical
    manner
    C. L. Li
    1,2,3
    , A. Deratani
    2
    , D. M. Wang
    1,4
    , D. Quemener
    2,3
    , D. Bouyer
    3
    , Y. Lai
    4
    1
    Department of Chemical Engineering, National Taiwan Universitv (NTU), Taipei 10617, Taiwan
    2
    Institute Europeen des Membranes (IEM), ENSCM, UM2, CNRS, Universite Montpellier II, CC 047, 2pl., Eugene Bataillon,
    34095 Montpellier, France
    3
    Universite de Montpellier II, CC 047, 2pl., Eugene Bataillon, 34095 Montpellier, France
    4
    Research and Development Center for Membrane Technologv, Chung Yuan Universitv, Chung Li 32023, Taiwan
    d94524001ntu.edu.tw; Chia-Ling.Liiemm.univ-montp2.Ir
    Super-hydrophobic surIaces with water contact angle higher than 150
    o
    have attracted a great interest Ior numerous
    applications. The wettability oI solid surIaces with water is inIluenced by their surIace chemistry and topography. According
    to the so-called lotus eIIect, the super-hydrophobicity oI the lotus leaves is mainly due to their hierarchical morphology
    organized Irom the nano to the micro scales. Being inspired by the lotus eIIect, this work presents how to prepare super-
    hydrophobic poly(vinylidene Iluoride) (PVDF) membranes by controlling its hierarchical topography. By combining the
    vapor-induced phase separation method (VIPS) and the wet immersion method, porous PVDF membranes with super-
    hydrophobic surIace (water contact angle~152
    o
    ) were obtained, without surIace modiIications or expensive equipments. As
    expected, the membranes possessed micro-andnano hierarchical structure. It was Iound that the micro-scale membrane
    structure can be tailored by adjusting the dissolution temperature to prepare the PVDF casting solution, the exposure time oI
    the casting Iilm to the humid air, and the solvency oI the coagulant used. In addition, the nano-scale structure can be tuned by
    using coagulants with diIIerent solvency to PVDF. Utilization oI the coagulant with strong nonsolvency to PVDF, such as
    water, membranes were prepared with water contact angle as high as 140
    o
    . However, only the coagulant with weak
    nonsolvency to PVDF, such as alcohol, can bring about the membranes with water contact angle higher than 150
    o
    . It is
    believed that the competition between phase separation and crystallization plays important roles in determining the
    organization oI the hierarchical structure. In conclusion, this work presents methods to tailor the micro and nano scale structure
    oI PVDF membranes; with suitable manipulation oI the hierarchical structure in these two scales, the membrane surIace
    hydrophobicity can be adjusted and membranes can be obtained with surIace water contact angle higher than 150
    o
    .
    OA.1.10
    Chain configuration, nanostructure of free volume and functional properties of high
    permeable 1,2-disubstituted polyacetylenes
    S.Matson
    1
    , E.Litvinova
    1
    , E.Sultanov
    1
    , V.Khotimskiy
    1
    , S.Shishatskiy
    2
    , W.Yave
    2
    , K.-V.Peinemann
    2
    , K.Raetzke
    3
    1
    A.J.Topchiev Institute of Petrochemical Svnthesis, Russian Academv of Sciences (TIPS RAS), Leninskv prospect, 29, 119991
    Moscow, Russia
    2
    Institute of Polvmer Research, GKSS Research Centre, Max-Planck-Str. 1, 21502 Geesthacht, Germanv
    3
    Technical Facultv, Universitv of Kiel, Kaiserstrae 2, 24143 Kiel, Germanv
    matsonips.ac.ru
    Development oI nanostructured polymeric materials Ior gas and vapor separation membranes is a challenging topic. Among
    materials which properties are determined by organization oI nanospace are glassy polymers oI 1,2-substituted acetylenes. The
    highest known gas and vapour permeability and higher permeability Ior large organic molecules than Ior smaller permanent
    gases in these disubstituted polyacetylenes are attributed to speciIic organization oI polymer, namely, extremely big and
    interconnected Iree volume elements resulting Irom stiII main chain and bulky substituents.
    For membrane application along with transport properties an important characteristic is stability towards components oI
    working environment. Detailed investigation oI synthesis oI high permeable disubstituted polyacetylenes showed the
    possibility oI regulation oI geometric structure by synthesis conditions and allowed establishing links between stability
    towards organic solvents as well as permeability and microstructure and submolecular structure oI polymer |1|.
    Our work is devoted to disubstituted polyacetylenes PTMSP and its Ge-containing analogue poly(1-trimethylgermyl-1-
    propyne) |PTMGP| with high content oI the same geometry units. Controlling oI geometric structure (determined by NMR
    13
    C
    spectra) was achieved by synthesis conditions such as: catalyst, co-catalyst, solvent and temperature oI polymerization process.
    PTMGP with high uniIormity has demonstrated high permeability and n-butane/methane selectivity in n-butane/methane
    -12-
    mixture and at the same time resistance towards aliphatic and aromatic hydrocarbons. The PALS investigations oI PTMSP and
    PTMGP with diIIerent microstructure have shown diIIerences in Iree volume and size distribution oI Iree volume elements
    correlating with gas transport properties oI polymer. The achieved data show that on the basis oI highly uniIorm
    polyacetylenes one can obtain membrane material with high transport properties and stability to organic compounds.
    |1| V.S. Khotimsky, M.V. Tchirkova, E.G. Litvinova, A.I. Rebrov, G.N. Bondarenko, Poly|1-(trimethylgermyl-1-propyne| and
    poly|1-(trimethylsilyl-1-propyne| with various geometries: their synthesis and properties, J. Polym. Sci, Part A: Polym.Chem.,
    2003, 41, 2133-2155.
    Acknowledgement. Funding Ior this research was provided by the European Commission (project COMPOSE, NMP3-
    CT-2003-505633) and Russian Foundation Ior Basic Research (project 07-03-00553).
    OA.2.1
    Characterization and modeling of the organic vapor transport in teflon AF/fumed
    silica mixed matrix membranes
    M. C. Ferrari, M. Galizia, M. G. De Angelis, G. C. Sarti
    Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali
    Universita degli Studi di Bologna, Jia Terracini 28, 40131 Bologna, Italv
    grazia.deangelis unibo.it
    The addition oI Iumed silica particles to high Iree volume glassy polymers such as amorphous TeIlon results in an
    enhancement oI gas solubility, diIIusivity and permeability: this behavior is not captured by traditional models Ior composites,
    which underestimate the gas transport parameters. In this work we consider that such phenomenon is due to the additional Iree
    volume induced by insertion oI Iumed silica nanoparticles in the polymeric phase.|1| In order to evaluate the exact value oI
    polymer Iree volume aIter the addition oI a certain amount oI Iiller, we model the experimental solubility oI one test penetrant
    in the polymeric phase oI the composite material with the NELF theory. |2| The Iractional Iree volume (FFV) calculated in this
    Iashion may then be used to estimate a priori the solubility oI other gases in the composite materials and to estimate with one
    adjustable parameter only the diIIusivity and permeability oI other gases in the mixed matrix materials, by means oI the Iree
    volume theory.
    This approach has been used to model the solubility, diIIusivity and permeability oI two model vapors (n-C
    4
    and n-C
    5
    ) in
    mixed matrix membranes based on TeIlon AF1600 and AF2400 and variable amounts oI Iumed silica: the model predictions
    are in good agreement with experimental data Ior both diIIusivity and solubility and the data Ior the two polymers lie on a
    single master curve. Moreover, swelling experiments were carried on, allowing to catch the eIIect oI silica addition on the
    polymer dilation, and the experimental values agree well with the predictions oI NELF model.
    |1| M.G. De Angelis, G.C. Sarti 'Solubility and diIIusivity oI gases in mixed matrix membranes containing hydrophobic
    Iumed silica: correlations and predictions based on the NELF model", Ind. Eng. Chem. Res.; 2008; 47(15); 5214-5226.
    |2| F. Doghieri, G.C. Sarti Non Equilibrium Lattice Fluids - A Predictive Model For The Solubility In Glassy Polymers
    Macromolecules, 29, 7885-7896, 1996
    OA.2.2
    Ultra thin film composite membrane for CO
    2
    separation
    A. Car, W. Yave, J. Wind, K. V. Peinemann
    Institute of Polvmer Research, GKSS-Research Centre Geesthacht GmbH, Max-Planck-Strasse 1, 21502 Geesthacht, Germanv
    Anja.Cargkss.de
    Ultra thin Iilm composite membranes (UTFC) Irom Polyactive

    copolymer were studied in the laboratory and then scaled-up.


    These membranes with an extreme improvement oI Ilux, which is higher than that reported by RITE institute (2.73 m3/m
    2
    h
    bar) |1| maintains high selectivity over N
    2
    , CH
    4
    and H
    2
    . The high CO
    2
    Ilux was achieved by minimization oI the thickness oI
    the selective thin layer. DiIIerent types oI composite structures were evaluated. Best perIormance was achieved with a
    multilayer structure, when the ultra thin selective layer was sandwiched between a gutter layer and a highly permeable
    -13-
    protective layer. The multilayer structure was manuIactured on a continuously running pilot machine. Membranes tested at
    high pressure (up to 20 bar) with single and mixed gas, and at diIIerent temperatures (up to 330K) have shown excellent
    perIormance. The outstanding UTFC membranes produced at large-scale presented the highest CO
    2
    Ilux reported till now (~3
    m
    3
    /m
    2
    h bar) with a selectivity over N
    2
    , CH
    4
    and H
    2
    higher than 50, 15 and 10, respectively.
    |1| S. Kazama, S. Morimoto, S. Tanaka, H. Mano, T.i Yashima, K. Yamada, K. Haraya, Greenhous Gas Control Technologies
    2005 7, 75.
    OA.2.3
    Azo-polymers containing EVAL membranes with switchable wettability
    B. Tylkowski
    1
    , S. Peris
    2
    , R. Garcia-Valls
    1
    , J. A. Reina
    2
    , J. C. Ronda
    2
    , M. Giamberini
    1
    1
    Departament dEnginveria Quimica, Universitat Rovira i Jirgili, Av. Pasos Catalans, 26, 43007 Tarragona Spain.
    2
    Departament de Quimica Analitica i Quimica Organica, Universitat Rovira i Jirgili, Carrer Marceli Domingo s/n, 43007
    Tarragona Spain.
    marta.giamberiniurv.net, bartosz.tylkowskiurv.net
    'Smart surIaces with reversibly switchable wettability have aroused great interest because oI their applications as biosensors,
    biomedical devices, intelligent membranes, data storage, light-powered molecular machines and so on |1|.
    This reversible switching can be obtained through an externally applied stimulus such as light irradiation, electrical potential,
    temperature, solvent and pH. Among these external stimuli-responsive materials, azobenzene compounds and its derivatives
    are known to exhibit big changes in both geometry and dipole moments as a result oI UV/visible irradiation because oI
    reversible photoisomerization between the Z and E conIigurations, which means that the wettability oI azobenzene-modiIied
    surIaces can be triggered by means oI UV/visible irradiation.|1, 2|
    In this paper we report the preparation oI new asymmetric Poly(vinyl)-co-ethylene (EVAL) composite membranes blended
    with very low concentration oI azobenzene polymers. The cross-sections and the surIace morphologies oI the EVAL or
    EVAL-azo containing membranes were characterized by Environmental Scanning Electron Microscopy. The changes in
    surIace morphology oI the membranes beIore and aIter UV irradiation were detected by Atomic Force Microscopy. The
    wettability oI the porous EVAL membrane and porous azo-composite membranes was studied by measuring the contact angle
    both beIore and aIter UV irradiation. Preliminary results show that a remarkable change in membrane surIace, as well as a 30
    o
    decrease in membrane contact angle are induced upon UV irradiation Ior 15 minutes.
    |1| Ho Sun Lim, Joong Tark Han, Donghoon Kwak, Meihua Jin, and Kilwon Cho, J. Am. Chem. Soc 2006, 128, 14458
    |2| L. Ding and T. P. Russel, Macromolecules 2007, 40, 2267
    OA.3.1
    Structural features and unique ion interactions of MFI type zeolites for
    membrane desalination
    B. Zhu
    1
    , A. Forstmeier
    1
    , S. Pas
    2
    , A. Hill
    2
    , J. Lin
    3
    , M. Duke
    1
    1
    Institute for Sustainabilitv and Innovation, Jictoria Universitv, PO Box 14428, Melbourne, JIC 8001, Australia
    2
    CSIRO Materials Science and Engineering, Private Bag 33, Clavton South, JIC 3169, Australia
    3
    Department of Chemical and Materials Engineering, Ari:ona State Universitv, Tempe, AZ 85287, USA
    bo.zhuvu.edu.au
    Seawater desalination is now commonly perIormed using membrane technology. However, the commercial polymer
    membranes have high Iouling tendency caused by the deposition oI contaminants such as natural organic matters (NOMs).
    Ceramic membranes have attracted great attention since they potentially oIIer many advantages over commercially available
    polymeric membranes, such as excellent chemical, thermal and mechanical stability, long reliable working liIetime, and high
    resistance to chlorine, oxidants, radiation and solvents. Membranes made Irom zeolites are oI great interest and have
    increasingly been studied |1-3| since Iirst literature appearance Ior desalination appeared as computational simulations carried
    out by Lin and Murad |4|. In this study, zeolites with MFI structure were developed by the standard hydrothermal process and
    zeolite membranes were produced using the standard template-Iree secondary growth method under hydrothermal conditions.
    -14-
    Unusual negative rejection oI salts, as high as -110 , occurred on membranes tested with seawater which could not be
    explained by Donnan mechanism indicating a potentially novel mechanism. This however stabilized to rejections oI at least
    70 aIter stabilization longer than one day. To better understand the unique interactions oI speciIic ions with the zeolite
    structure, XRD, adsorption and FTIR were carried out aIter exposure to salt solutions to observe slight structural changes over
    time. Also, cation exchange by the zeolite was measured using ICP-OES. By tailoring the structure using Si/Al ratio, the
    zeolite ion exchange capacity and structural properties can be tuned to meet the requirements oI ion-selective desalination.
    Positron annihilation liIetime spectroscopy data oI zeolites indicated that the size and quantity oI zeolite pores can be modiIied
    by Si/Al ratio. Further studies oI the mechanism oI negative rejection are necessary to better explain this unusual, but
    potentially beneIicial property.
    |1| Li, L., Dong, J., NenoII, T.M., et al., Desalination by reverse osmosis using MFI zeolite membranes. Journal oI Membrane
    Science 2004, 243 (1-2), 401-404.
    |2| Li, L., Dong, J., NenoII, T.M., et al., Reverse osmosis oI ionic aqueous solutions on a MFI zeolite membrane. Desalination
    2004, 170 (3), 309-316.
    |3| Li, L., Dong, J., and NenoII, T.M., Transport oI water and alkali metal ions through MFI zeolite membranes during reverse
    osmosis. Separation and PuriIication Technology 2007, 53 (1), 42-48.
    |4| Lin, J. and S. Murad, A computer simulation study oI the separation oI aqueous solutions using thin zeolite membranes.
    Molecular Physics 2001, 99(14), 1175-1181.
    OA.3.2
    A new route to microporous silica-alumina membranes for high-temperature gas
    separation
    A. Cheraitia
    1,2
    , A. Ayral
    1
    , A. Julbe
    1
    , H. Satha
    2
    1
    Institut Europeen des Membranes, CNRS-ENSCM-UM2, Universite Montpellier 2, CC047, Place Eugene Bataillon,
    34095Montpellier cedex 5, France.
    2
    Laboratoire dAnalvse Industrielle et de Genie des Materiaux, Departement Genie des Procedes, Universite de Guelma, BP
    401, Guelma, Algeria.
    andre.ayraliemm.univ-montp2.Ir
    The development oI high-perIormance microporous ceramic membranes is an important challenge Ior gas separation
    applications at high temperature. Microporous silica membranes can be easily prepared by the sol-gel process |1|. However the
    microporosity oI pure silica layers is rapidly altered at high temperature in steam atmosphere. Various strategies can be
    considered in order to improve the hydrothermal stability oI silica membranes. The insertion oI inorganic additives in the silica
    network, leading to mixed-oxide systems, is a promising approach.
    In this study, microporous silica-alumina membranes were prepared by a simple but original sol-gel method, involving a
    mixture oI tetraethoxysilane with an acidic alumina hydrosol. In this synthesis process, urea acts as a multiIunctional additive.
    It is used i) Ior preparing the alumina hydrosol, ii) Ior controlling the polycondensation oI the mixed-oxide network and Iinally
    iii) as porogen agent. Separative layers were deposited by slip-casting inside commercial mesoporous tubular alumina supports
    (Pall-Exekia- Al
    2
    O
    5
    -5nm).
    27
    Al NMR analyses showed that homogeneous silica-alumina mixed-oxides were obtained in a wide range oI composition and
    with Si/Al molar ratios up to 6/1. UniIorm and crack-Iree layers have been observed by scanning electron microscopy. The
    microporous structure oI the membranes has been evidenced by several techniques including N
    2
    adsorption and ethanol ellipso-
    porosimetry. Preliminary gas permeation experiments at room temperature conIirmed the absence oI macro-deIect in the
    membranes (no eIIect oI transmembrane pressure on permeance
    i
    ). As an example, a He/CO
    2
    ideal selectivity around 15 was
    measured associated with
    He
    8 10
    -8
    mol Pa
    -1
    s
    -1
    m
    -2
    at 25C. Experiments are in progress in order to study permeation at high
    temperature (500C) and the hydrothermal stability oI these microporous silica-alumina membranes.
    |1| 'Microporous silica membrane basic principles and recent advances, A. AYRAL, A. JULBE, V. ROUESSAC, S.
    ROUALDES, J. DURAND, in, R. Mallada and M. Menendez (Eds), Membrane Science and Technology Series vol. 13,
    Inorganic Membranes: Synthesis, Characterization and Applications, ISBN: 9780444530707, Elsevier, Amsterdam, 2008,
    Chapter 2, pp: 33-79.
    -15-
    OA.3.3
    Multi-layer ceramic hollow fibres via wet-spinning
    I. Struzynska, N.E. Benes, L. Winnubst, M. Wessling, A. Nijmeijer
    Inorganic Membranes/Membrane Technologv Group, Facultv of Science and Technologv, Mesa Institute for
    Nanotechnologv - Universitv of Twente - P.O. Box 217, 7500 AE Enschede, The Netherlands
    n.e.benesutwente.nl
    Ceramic membranes show good mechanical, chemical and thermal stability. However, high cost oI Iabrication, time
    consuming production as well as low surIace area per unit volume (A/V ratio) hamper their industrial application. The A/V
    ratio oI ceramic membranes is highest when they have a hollow Iibre geometry. Single layer ceramic hollow Iibers have been
    prepared by the wet-spinning technique. The corresponding Iibers do not directly display the selectivity required Ior most
    industrial applications. ModiIication oI the ceramic hollow Iibres via graIting |1| or (sol-gel, polymeric) coating |2, 3, 4| can
    be an option Ior achieving the desired selectivity. Another approach could be co-spinning/co-extrusion oI multiple layers in a
    single step, Iollowed by co-sintering |5|. Such a procedure requires a minimum number oI steps and allows Ior very
    convenient and cost eIIicient membrane Iabrication.
    Multiple layer ceramic hollow Iibres have been prepared by wet spinning oI polymer solutions loaded with alumina particles,
    Iollow by heat treatment. Several crucial parameters Ior obtaining good quality ceramic hollow Iibres have been identiIied,
    including the size (distribution) oI the ceramic particles, the amount oI viscosity modulator and the ratio oI polymer and
    ceramic powder. The inIluence oI these parameters on the morphology and the structure oI the Iibres as well as on the
    mechanical properties oI the Iibres is discussed.
    |1| S. Koonaphapdeelert, K. Li, J. Membrane Sci. 291 (2007) 70-76
    |2| T.A. Peters, J. Fontalvo, M.A.G. Vorstman, N.E. Benes, R.A. van Dam, Z.A.E.P.Vroon, E.L.J. van Soest-Vercammen,
    J.T.F. Keurentjes, J. Membrane Sci. 248 (2005) 73-80
    |3| S. Liu, W.K. Teo, X. Tan, K. Li, Separation and PuriIication Technology 46 (2005) 110-117
    |4| X.L. Pan, N. Stroh, H. Brunner, G.X. Xiong, S.S. Sheng, Separation and PuriIication Technology 32 (2003) 265-270
    |5| J. de Jong N.E. Benes, G.H. Koops, M. Wessling, J. Membrane Sci. 239 (2004) 265-269
    OA.3.4
    Multifunctional ceramic membranes with hierarchical porous structure and
    dispersed metal nanoparticles
    C. Yacou, A. Ayral, A. Julbe
    Institut Europeen des Membranes, UMR 5635 CNRS-ENSCM-UM2, Universite Montpellier 2, cc047, Place Eugene Bataillon,
    F-34095 Montpellier cedex 5, France.
    christelle.yacouiemm.univ-montp2.Ir
    Microporous ceramics membranes have received increasing interest during the past decade Ior many emerging applications
    such as gas separation under conditions where organic polymer membranes cannot be used. Indeed molecular-sieving oIIers
    potential advantages Ior separating gases either at elevated temperature or in the presence oI organic vapors, notably when the
    membrane exhibits speciIic Iunctionalities such as catalytic or adsorptive properties. In this context various strategies are
    actively studied in order to design innovative ceramic membranes meeting requirements Ior puriIication and treatment oI
    multicomponent gas streams |1, 2|.
    For instance supported membranes displaying both a multimodal porosity (isolated macropores and mesopores embedded in a
    microporous inorganic matrix) and an additional Iunctionality deserve a great deal oI attention. Such membranes prepared by
    scalable processing methods provide substantial simpliIication over conventional processes required Ior microporous
    membrane preparation. Indeed direct coating on a macroporous support is possible although a smooth mesoporous
    intermediate layer is usually needed. On the other hand, the additional non-connected macropores and mesopores, potentially
    embedding speciIic additives like catalysts or adsorbents, ensure a high permeability Ior the hierarchical porous membrane
    while the cut-oII value is Iixed by the microporous continuous solid phase. Furthermore the relatively high membrane
    thickness strongly limits the possible impacts oI top-surIace deIects.
    This original approach will be illustrated in the present work Ior SiO
    2
    and TiO
    2
    -SiO
    2
    membranes with embedded Pt or Rh
    nanoparticles, obtained by a very simple one-pot sol-gel method. A stable complex hybrid suspension was Iirst prepared by
    mixing alkoxide precursor(s) with organics porogen agents and a noble metal salt solution. Nanoparticles were generated in-
    -16-
    situ using a rapid microwave-assisted thermal treatment oI the Iinal suspension. Membranes were then deposited by slip-
    casting inside a macroporous u-alumina tubular substrate with 0.2 m internal layer pore size. Thermal removal oI organic
    compounds led to the Iormation oI a hierarchical porous structure in which most oI the nanoparticles were dispersed at the
    mesoscopic level.
    In this presentation the optimized synthesis protocol and the derived membrane properties will be described. Characterizations
    oI hierarchical porosity, mixed oxide lattice, location and size oI the dispersed metal nanoparticles will be more speciIically
    addressed. Gas permeation perIormance at low and high temperatures will be Iinally discussed.
    |1| A. Julbe, V. Rouessac, J. Durand and A. Ayral, J. Memb. Sci., 2008, 316 (1), 176.
    |2| C. Yacou, M.L Fontaine, A. Ayral, P. Lacroix-Desmazes, P.A Albouy and A. Julbe, J. Mater. Chem, 2008, 18, 4274-79.
    OA.3.5
    Fabrication of the Pd-Ag and Pd-Ag-Au alloy membranes supported on porous
    YSZ tube
    T. M. Suzuki
    1
    , D. A. Pacheco Tanaka
    1
    , Y. Wakui
    1
    , K. Noda
    2
    , M. Kajiwara
    3
    , T. Makino
    3
    1
    National Institute of Advanced Industrial Science and Technologv (AIST), 4-2-1, Nigatake, Mivagino-ku, Sendai 985-8551,
    Japan
    2
    NGK Insulators, LTD, New Products development Center, 2-56 Suda-cho, Mi:uho-ku, Nagova 467-8530, Japan
    3
    Iwatani Corporation, Hvdrogen Energv Department, 5-1, Katsube, 4-Chome, Morivama, Shiga, 524-0041, Japan
    tm-suzukiaist.go.jp
    Palladium membranes have advantages over other alternatives with respect to high Ilux and exclusive perm-selectivity Ior
    hydrogen due to the unique permeation mechanism. Pure palladium membranes are oIten damaged by hydrogen embrittlement
    caused by the - phase transition oI the palladium hydride at below the critical temperature (293C). It has been pointed out
    that this - phase transition is considerably suppressed by alloying with silver |1|. Thus alloying with silver leads to less
    distortion upon hydrogen adsorption and desorption cycles. In addition to the mechanical and thermal stability oI the palladium
    membrane layer, matching with the support materials is important Ior composite membrane. Zirconia (ZrO
    2
    ) shows better
    matching with palladium in terms oI thermal expansion coeIIicient. Long term thermal durability oI the composite palladium
    membranes is essentially important, particularly when the membranes are exposed at elevated temperature (~600C) like in the
    separation oI hydrogen Irom steam reIorming process oI hydrocarbons. A thermally stable phase structure oI zirconia can be
    obtained by doping with yttria |2|. In order to attain membrane durability in wide temperature range, Ior example Irom room
    temperature to 600C, we have attempted to Iabricate Pd-Ag alloy membrane over YSZ support. We present the Iabrication oI
    the Pd-Ag membrane on a tubular YSZ support by electroless plating process.
    We examined the simultaneous plating oI Pd and Ag on YSZ (10 x 100mm) by continuous addition oI Ag(I) to the electroless
    plating solution. CareIul control oI Ag(I) addition rate and plating bath composition allowed the synchronized deposition oI Pd
    and Ag having constant Pd/Ag composition Irom inner to outer oI the membrane layer. Since Pd and Ag particles distributes
    uniIormly by simultaneous deposition, the mutual atomic diIIusion takes place rapidly and alloying can be completed at rather
    moderate temperature (650C) and short time (3h). The Pg-Ag/YSZ membrane revealed a considerable durability upon long
    term H
    2
    and N
    2
    cyclic perm test (~2000 cycles, ~4000 h) at 600C by keeping the perm-selectivity over 500 (H
    2
    /N
    2
    ). We also
    have tried the scale up oI membrane tube size (30 x 320mm) and optimized the plating conditions.
    Ternary alloy membrane composed oI Pd-Ag-Au/YSZ have also been prepared by electroless plating using alkaline
    K|Au(CN)
    4
    | combined with hydrazine reduction and subsequent alloying.
    |1| Armor, J.N. Appl. Catal. 1989, 49, 1. b) Uemiya, S.; Matsuda, T.; Kikuchi, E. J. Membr. Sci. 1991, 56, 315.
    |2| J. Kim, Y. S. Lin, J. Membr. Sci., 139 (1998) 75.
    -17-
    OA.3.6
    Keynote : Ceramic membranes in clean energy delivery processes
    J.C.D. Da Costa
    FIMLab Films and Inorganic Membrane Laboratorv, Division of Chemical Engineering, The Universitv of Queensland,
    Brisbane Qld 4072, Australia.
    j.dacostauq.edu.au
    There is a large world concerted eIIort towards reducing greenhouse gas emissions, in particular with the announcements in
    2008 regarding the establishment oI the Global Carbon Capture Institute. Coal underpins the bulk majority oI Australia`s
    energy production and the development oI novel enabling technologies to meet carbon emission reduction is paramount. This
    work assesses clean energy delivery technologies Ior gas processing under R&D in the Australian program Ior low emission
    technologies. OI particular attention, integrated gasiIication combined cycle (IGCC) systems are seen as a potential candidate
    though several aspects oI IGCC`s gas processing are challenging. These include an air separation unit to supply O
    2
    to the coal
    gasiIier, syngas processing to separate H
    2
    Irom CO
    2
    , or to shiIt CO as a membrane reactor in the water gas shiIt reaction.
    In view oI its inherent properties, inorganic membranes have the capabilities to operate at high temperatures and improve
    process eIIiciencies, thus ideal as ancillary unit operations Ior clean energy delivery systems. This presentation Iocus on the
    work being carried out at the FIMLab under the Australian low emission technologies program, covering the Iollowing topics:
    1) Metal doped silica membranes Ior H
    2
    separation at high temperatures (up to 500
    o
    C).
    2) CO shiIting in membrane reactors Ior both low temperature and high temperature water gas shiIt reaction.
    3) Computational Fluid Dynamics oI gas separation membrane modules.
    4) O
    2
    separation using perovskite membranes.
    5) Scale up and multiple tubular membrane systems.
    OA.3.7
    Amorphous silicon carbonitride H
    2
    permselective membranes
    V. Rouessac, W KaIrouni, C. Charmette, J. Durand, A. Julbe
    IEM, ENSCM-UM2-CNRS UMR5635, Universite Montpellier 2, place Eugene Bataillon, 34095 Montpellier cedex 5, France
    vincent.rouessaciemm.univ-montp2.Ir
    H
    2
    permselective silica-based membranes oIIer attractive perIormance Ior H
    2
    separation at intermediate temperatures
    (400-600C), in spite oI their limited steam stability. These membranes are typically prepared by either sol-gel or CVD
    methods and various strategies are under study in order to maximize both the membrane perIormance (permeance,
    permselectivity) and their stability. In this work a new kind oI silica-based membrane material is developed by Plasma
    Enhanced Chemical Vapor Deposition, whose non-oxide Iormulation is more hydrophobic than silica.
    Thin amorphous carbonitride a-SiN
    X
    C
    Y
    :H membranes have been deposited on porous alumina supports by PECVD technique,
    starting Irom a gas mixture oI hexamethyldisilazane and ammonia (Figure 1).
    The derived 'inorganic-like hybrid material is stable under atmospheric air at 500C in terms oI both chemical composition
    and microstructure. Accurate choices oI both the ammonia/silazane ratio and the plasma electric power lead to promising a-
    SiC
    X
    N
    Y
    :H membranes with thickness less than 100 nm, helium permeance P(He) 10
    -6
    mol.m
    -2
    .s
    -1
    .Pa
    -1
    and He/N
    2
    ideal
    selectivity over 200 at 300C with a trans-membrane pressure P 10
    5
    Pa.
    Figure 1- Cross-section oI a-SiCN:H molecular sieve membrane deposited on -Al
    2
    O
    3
    .
    -18-
    These PECVD hybrid materials are more hydrophobic than sol-gel or CVD silica membranes. Permeances, single gas
    permselectivities and gas mixture separation Iactors beIore and aIter ageing, are currently studied as a Iunction oI temperature.
    Both the characteristics and perIormance oI these original membranes will be reported.
    OA.3.8
    Structural diversity in ceramic hollow fibre membranes
    B. F. K. Kingsbury, K. Li
    Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ, UK
    Kang.Liimperial.ac.uk
    Due to their high level oI chemical, thermal and mechanical resistance, ceramic membranes may Iind use in an extensive range
    oI applications ranging Irom solvent resistant nanoIiltration to membrane reactors and high temperature membrane contactors.
    When prepared in hollow Iibre Iorm, the extremely large surIace area to volume ratio coupled with the inherent stability oI
    ceramic membranes oIIer substantial advantages over conventional membrane conIigurations. However, the development and
    commercialization oI ceramic membranes has been greatly hindered by the expensive and time consuming preparation
    procedures and the limited membrane morphologies that are available using traditional preparation techniques.
    Using a combined phase inversion and sintering technique, membranes have been prepared with a variety oI structures.
    Ceramic hollow Iibres prepared in this way consist oI two principal morphologies i.e. Iinger-like macrovoids or a sponge-like
    structure. Finger-like voids result Irom hydrodynamically unstable viscous Iingering which occurs when a less viscous Iluid
    (non-solvent/coagulant) intrudes into a more viscous Iluid (powder suspension) and only takes place below a critical
    suspension viscosity. II the Iinger-like voids originate at the nascent Iibre surIace then they may Iorm the surIace pores which
    may vary in size depending on the spinning parameters and the composition oI the spinning suspension. However, iI viscous
    Iingering is initiated within the bulk oI the suspension Iilm then an isolated Iinger-like void is produced which does not
    contribute to surIace porosity. Conversely, a sponge-like structure results Irom phase inversion in the absence oI
    hydrodynamically unstable viscous Iingering and has properties which are largely determined by the spinning suspension
    composition and the sintering proIile. Whether the Iibre structure is composed oI Iinger-like voids or a sponge-like structure
    depends strongly on the relative rates oI Iinger-like void growth and polymer-binder precipitation and it has been shown that
    these rates can be controlled by using a non-solvent additive in the spinning suspension and by varying spinning parameters
    such as extrusion rate, air-gap and internal coagulant Ilow rate. The eIIect oI these parameters on Iibre morphology and pore
    size distribution has been studied using a bubble point method as well as mercury intrusion porosimetry. Analysis using these
    techniques has shown that a bimodal distribution exists, composed oI separate distributions Ior pores created by the sponge-
    like structure and pores Iormed by viscous Iingering and that the behavior oI these pores diIIers as the sintering temperature is
    increased.
    OA.3.9
    New clay-alumina capillaries for MF and UF applications
    S. Cerneaux
    1
    ,

    S. Sarkar
    2
    , S. N. Roy
    2
    , A. Larbot
    1
    ,

    S. Bandyopadhyay
    2
    1
    Institut Europeen des Membranes, 1919 route de Mende, 34293 Montpellier cedex 5, France
    2
    Central Glass and Ceramic Research Institute, 196, Rafa S. C. Mullick Road, Kolkata-700032, India
    cerneauxiemm.univ-montp2.Ir
    The preparation oI pure metal oxide porous membranes Ior microIiltration and ultraIiltration applications is currently made at
    high cost as a result oI the required high sintering temperature oI 1700C. ThereIore, lowering the manuIacturing cost oI these
    membranes with no alteration oI the mechanical strength represents a great challenge. In this work, clay was introduced in the
    Iormulation oI the alumina membrane preparation to yield new clay-alumina supports that can be sintered at a temperature
    lower than 1500C without any mechanical strength Iailure. Indeed, presence oI silica in the clay Iavours the sintering process
    oI the support by Iorming a low melting phase that strongly reduces the sintering temperature. In addition, the capillary
    morphology was developed to enhance the packing density oI membrane i.e. surIace area / volume. Depending on the initial
    clay-alumina paste Iormulation and processing parameters, new clay-alumina capillary supports with dimension oI 3.14/2.43
    mm (OD/ID). MF or UF membranes were deposited directly without intermediate layers on these new supports to give clay-
    alumina MF and UF membranes.
    -19-
    OA.3.10
    New ceramic membrane resistant to abrasion
    E. Papin, P. Lescoche, A. Grangeon, L. Pivier, G. Balduchi
    TAMI Industries, Z.A. Les Laurons, CS 65, 26111 Nvons Cedex - FRANCE
    epapintami-industries.com
    TAMI Industries is a major ceramic membrane developper and manuIacturer since 15 years. Inorganic membrane Ior cross
    Ilow Iiltration are widely used in Iood and beverage industries, bio-industries, water treatment, environment, chemical and oil
    industries.
    These membranes are particularly appreciated in severe applications, Ior their chemical resistance to acid and base (pH 0-14),
    to solvants, Ior the non chemical interaction with the Iluid, and Ior their long liIetime.
    TAMI Industries is very well known in this Iield Ior its innovations, among with :
    - highest Iiltration surIace area thanks to its non circular channels with constant active layer thickness
    - very strong and high Ilux Iull titania porous material
    - structural membranes like IsoIlux

    with non constant active layer thickness
    TAMI Industries has more recently developed a new inorganic membrane particularly dedicated to abrasive applications.
    Indeed, in some applications, like degreasing bath, membrane-bio-reactors, wastewater treatment, a signiIicant quantity oI
    metallic or mineral particles or aggregates are in the retentate. Because oI their size, their concentration and the speed oI the
    Iluid inside the tubular channels, these particles damage strongly the active layers. This reduces signiIicantly the separation
    quality, liIetime, and has a strong negative economic impact.
    Ceramic materials used Ior membrane manuIacturing are very hard materials and stand almost to all the most severe
    applications, but prepared in a very porous way, as required Ior good membrane layer perIormances, they keep sensitive to the
    most critical applications in term oI abrasion. Some improvements, like increasing the membrane layer thickness are already
    known and used, but in some cases it does not increase suIIiciently the liIetime.
    There is so a need Ior new membranes, very resistant to abrasion.
    Using technologies inspired oI our own IsoIlux technology, and using speciIic nanotechnologies, we managed to develop a
    new structure oI inorganic membrane. Abrasion resistance at lab scale, and at industrial scale have been tested, and proved a
    major improvement. LiIetime is doubled or more depending on the abrasive level, in such a way that no other existing
    membrane on the market have been Iound able to compete.
    OA.4.1
    Mixed ionic-electronic conductor capillary membranes for gas separation
    M. Zipperle
    1,2
    , S. Schirrmeister
    3
    , J. Caro
    4
    , T. Hirth
    1,2
    , T. Schiestel
    1
    1
    Fraunhofer Institute for Interfacial Engineering and Biotechnologv, Nobelstrae 12, 70569 Stuttgart, Germanv
    2
    Universitv of Stuttgart, Institute for Interfacial Engineering, Nobelstrae 12, 70569 Stuttgart, Germanv
    3
    Uhde GmbH, Friedrich-Uhde-Strae 15, 44141 Dortmund, Germanv
    4
    Universitv of Hannover, Institute of Phvsical Chem. and Electrochemistrv, Callinstrae 3-3A, 30167 Hanover, Germanv
    Marita.Zipperleigb.IraunhoIer.de
    Mixed ionic-electronic conductors (MIECs) with perovskite structure oIIer potential applications in gas separation
    technologies. Because oI their property to separate oxygen or hydrogen Irom gas mixtures MIECs can be used in processes
    where a constant supply or removal oI oxygen or hydrogen Ior eIIicient reactions is necessary |1|. Compared to conventional
    technologies membrane systems made oI MIECs have a much higher energy-eIIiciency combined with simpliIied operation.
    Inorganic capillary membranes made oI perovskite materials have been developed in our group with a very high packing
    density |2|.
    -20-
    The capillaries are made oI BaCo
    x
    Fe
    y
    Zr
    z
    O
    3-
    and are
    manuIactured by a phase inversion process. The ceramic
    powder is dispersed in a polymer solution and this slurry
    is spun through a spinneret into a precipitation bath. The
    geometry oI the capillaries can be controlled by a
    variation oI the dimensions oI the spinneret. Compared
    to other MIEC membranes our capillaries show a high
    oxygen permeation (Iig. 1) combined with a huge
    selectivity (O
    2
    /N
    2
    ~ 10.000).
    For industrial applications the membranes have to be
    stable under elevated temperatures over a long time.
    ThereIore we have examined the mechanical and thermal
    properties and the chemical stability oI the hollow Iibres
    when they are exposed to thermal and chemical
    gradients.
    Figure 1: permeation results oI diIIerent capillary geometries at
    diIIerent temperatures with p(O
    2)
    ) 30 kPa.
    |1| H.J.M. Bouwmeester, A.J. BurggraaI, Dense ceramic membranes Ior oxygen separation, in: A.J. BurggraaI, L. Cot (Eds.),
    Fundamentals oI Inorganic Membrane Science and Technology, Elsevier, Amsterdam, 1996, 435
    |2| T. Schiestel, M. Kilgus, S. Peter, K. Caspary, H. Wang, J. Caro, Hollow Iibre perovskite membranes Ior oxygen separation,
    J. Mem. Sci., 2005, 258, 1-4
    OA.4.2
    High-temperature sealing of ceramic capillary membranes for oxygen separation
    M. Sabjan
    1
    , M. Zipperle
    1
    , T. Betker
    1
    , J. Caro
    2
    , S. Schirrmeister
    3
    , C. Rssel
    4
    , T. Schiestel
    1
    1
    Fraunhofer Institute for Interfacial Engineering and Biotechnologv, Nobelstrasse 12, 70569 Stuttgart, Germanv
    2
    Universitv of Hanover, Inst. Phvsical Chem. and Electrochem., Callinstr.3-3A, 30167 Hanover, Germanv
    3
    Uhde GmbH, Friedrich-Uhde-Str. 15, 44 141 Dortmund, Germanv
    4
    Friedrich-Schiller-Universitv Jena, Otto-Schott-Institute for Glas chemistrv, Fraunhoferstr. 6, 07743 Jena, Germanv
    Thomas.Schiesteligb.IraunhoIer.de
    The demand Ior oxygen as a reactant in chemical industry is increasing recently. We have developed dense perovskite capillary
    membranes Ior the selective separation oI oxygen at high-temperatures |1|. It could be shown that such capillaries can be used
    Ior various applications like oxygen enriched air |2|, very pure oxygen |3|, syngas |4| or even hydrogen |5|. To transIer the
    high potential oI such membranes into an industrial application, the development oI suitable membrane modules is necessary.
    The thermal properties (e.g. expansion coeIIicient) oI the
    membranes material (BaCo
    x
    Fe
    y
    Zr
    z
    O
    3-
    ) determine the
    choice oI module materials. ThereIore a Ni-rich alloy with
    similar properties and a high stability under syngas
    conditions was choosen Ior the module housing. For the
    sealing oI the capillaries into that housing a glass ceramic
    material has been developed with tailor-made Ieatures
    (thermal and mechanical properties, adhesion to ceramic
    and metal surIaces, ..).
    With these materials capillary membrane modules have
    been built. Tests under high temperature conditions
    (850C, 6 bar, up to 1500 h) have shown that the leaking
    rate oI the modules is very low and the sealing is longterm
    stable. It was also possible to pass a couple oI temperature
    cycles without any loss oI tightness (Iig. 1).
    Figure 1: leaking rate at 800C and 6 bar determined
    by pressure decrease. Between each measurement the
    module was cooled down.
    |1| Schiestel T., Kilgus M., Peter S., Caspary K. J., Wang H., Caro J.: Hollow Iibre perovskite membranes Ior oxygen
    separation. J. Mem. Sci. 258 (1-2), 1-4 (2005).
    |2| Wang H., Werth S., Schiestel T., Caro J.: Perovskite Hollow Fiber Membranes Ior the Production oI O
    2
    -Enriched Air,
    Angew. Chem. 117/42, 7066-69 (2005).
    |3| Wang H., Klsch P., Schiestel T., Tablet C., Werth S., Caro J.: Production oI high-purity oxygen by perovskite hollow
    Iiber membranes swept with steam, J. Membr. Sci. 284 (2006) 5.
    -21-
    |4| Wang H., Tablet C., Schiestel T., Werth S., Caro J.: Partial oxidation oI methane to syngas in a perovskite hollow Iiber
    membrane reactor, Cat. Com. 7/11 (2006) 907-912.
    |5| Jiang H, Wang H., Werth S., Schiestel T., Caro J.: Simultaneous Production oI Hydrogen and Synthesis Gas by Combining
    Water Splitting with Partial Oxidation oI Methane in a Hollow-Fiber Membrane Reactor, Angew. Chem. Int. Ed. 47/48,
    9341-9344 (2008).
    OA.4.3
    Hydrogen flux through selected HTM membranes
    Y. Larring, R. Bredesen
    SINTEF Materials and Chemistrv, Post box 124 Blindern, NO-0314 Oslo, Norwav
    Yngve.LarringsinteI.no
    The STATOILHYDRO concept Ior CO
    2
    capture in natural gas Iired power plants (1) relies on ceramic Hydrogen Transport
    Membranes (HTM). The cycle eIIiciency penalty including CO
    2
    capture and compression to 150 bars is as low as 5-points.
    HTM should demonstrate a Ilux oI 5-10 mL.cm
    -2
    .min
    -1
    under operation and enabling process integration at 900-1000
    o
    C.
    Furthermore, HTM materials should exhibit a high stability towards the Iormation oI carbonates and hydroxides. The latter has
    so Iar been the main drawback Ior several oI the best perIorming reported proton conducting materials. This has triggered the
    search Ior new stable candidate materials.
    The present contribution Iocuses on screening new materials groups outside the commonly reported perovskite structure that
    could have high transport oI hydrogen. For stability issues, most oI the selected materials do not contain Sr and Ba cations,
    which are known to easily Iorm carbonates. Flux measurements have been perIormed in a test rig using gold rings as seals. The
    hydrogen Ilux was measured down in the temperature range 1000-600
    o
    C. The Iollowing materials were investigated: La
    6
    WO
    12
    ,
    Ln
    2
    Ti
    2
    O
    7
    and SrCe
    0.95
    Yb
    0.05
    O
    3
    under Iour diIIerent conditions (humidiIied He with 10 or 50 H
    2
    on the Ieed side combined
    with dry (DP) or humidiIied (WP) Ar on the permeate side). Several ambipolar conductivities were then calculated Irom the
    obtained Ilux data, in order to Iind an appropriate model describing the Ilux dependencies in the diIIerent gradients. These
    models are used to predict the expected Ilux under a given gradient and membrane thickness, provided that surIace reaction
    limitation and gas transport restrictions in the support can be ignored. They can also be used to predict the expected Ilux under
    process condition given that the model is valid outside the measured area.
    La
    6
    WO
    12
    showed a very high permeability, which was more than 0.001 ml/min.cm at above 890
    o
    C using 50 humidiIied H
    2
    on the Ieed side and humidiIied argon on the permeate side. This corresponds to a Ilux oI 1 ml/min.cm
    2
    Ior a 10 m thick
    membrane iI there is no restriction in surIace kinetics. SrCe
    0.95
    Yb
    0.05
    O
    3
    has slightly lower permeability. These values were
    compared to the ones Iound in the literature Ior diIIerent proton conductors. A permeability oI 0.00022 ml/min.cm and 0.00057
    ml/min.cm is reported Ior SrCe
    0.95
    Sm
    0.05
    O
    3
    and SrCe
    0.95
    Eu
    0.05
    O
    3
    , respectively, when using 4 H
    2
    on the Ieed side. Under the
    same conditions, our SrCe
    0.95
    Yb
    0.05
    O
    3
    membrane would have a Ilux oI 0.00018 ml/min.cm which is thus in the same range
    taking into account the diIIerent dopants.
    Er
    1.99
    Ca
    0.01
    Ti
    2
    O
    7
    and Nd
    1.95
    Ca
    0.05
    Ti
    2
    O
    7
    have lower permeability. Nevertheless, it is more likely that these materials would be
    more stable under real process conditions, as it will be discussed in this presentation.
    |1| K.Asen, B.Vigeland, T.Norby, Y.Larring, T.Mejdell, in E.S.Rubin, E.W.Keith, C.F.Gilboy (Eds.), 7th international
    conIerence on greenhouse gas control technologies (GHGT-7), Vancouver, Canada, Elsevier Science, OxIord, UK., 2004.
    -22-
    OA.4.4
    Perovskite capillaries/hollow fibres for gas separation in sustainable energy
    production
    C. Buysse
    1,2
    , A. Buekenhoudt
    1
    , F. Snijkers
    1
    , A. Kavaleuski
    1
    , J. Luyten
    1
    , H. Beckers
    1
    , W. Doyen
    1
    , B. Molenberghs
    1
    ,
    S. Lenaerts
    2
    , J. Kretzschmar
    2
    1
    JITO NJ (Flemish Institute for Technological Research), B-2400 Mol, Belgium
    2
    Department of Bioscience Engineering, Universitv of Antwerpen, CGB, Groenenborgerlaan 171, B-2020 Antwerpen, Belgium
    cedric.buyssevito.be
    Sustainable energy production out oI Iossil Iuels requires the use oI novel technologies Ior the removal and storage oI CO
    2
    .
    Gas separation membranes, which are associated with signiIicant lower eIIiciency losses compared to conventional gas
    separation technologies, can play an important role in achieving this mission. Promising membrane materials are dense
    oxygen-permeable perovskites with mixed ionic-electronic conducting properties. When these materials are exposed to an
    oxygen chemical potential gradient at high temperatures (~700C), they show an inIinitive oxygen selectivity, without the need
    Ior electrodes and external electrical loadings. Furthermore, their inherent stability at high temperatures allows the integration
    in high temperature combustion processes. ThereIore, these materials could be deployed in the separation oI oxygen Irom air
    which is needed in the oxy-Iuel and pre-combustion technologies Ior the capture oI CO
    2
    |1|. Since large-scale gas separation
    applications demand high surIace/volume ratios, membranes with capillary or hollow Iibre geometry have a distinct advantage
    over tubular and Ilat sheet membranes.
    In this work we present the Iabrication and perIormance oI Ba
    0.5
    Sr
    0.5
    Co
    0.8
    Fe
    0.2
    O
    3-o
    (BSCF) capillary membranes. The capillaries
    were made by a spinning technique based on phase inversion. The phase inversion technique is commonly used Ior the
    Iabrication oI polymeric membranes, but has been adapted by using a starting suspension loaded with a certain Iraction oI
    BSCF. Fabrication oI gas tight, macrovoid-Iree capillaries is desired. In addition, results on the modeling oI the oxygen
    permeation through BSCF capillaries and hollow Iibres will be shown. This work is perIormed in the light oI the MEM-
    BRAIN` project, aiming at the development oI gas separation membranes Ior zero-emission Iossil Iuel power plants.
    |1| R. Bredesen, K. Jordal, O. Bolland, High-temperature membranes in power generation with CO
    2
    capture, Chemical
    Engineering and Processing, 2004, 43, 1129-1158
    OA.4.5
    Phosphonic acid-functionalized fluoropolymers as fuel cell membrane materials
    R. Tayouo
    1
    , G. David
    1
    , S. Roualdes
    2
    , B. Ameduri
    1
    1
    Institut Charles Gerhardt - UMR (CNRS) 5253 , Ingenierie & Architectures Macromoleculaires - Ecole Nationale Superieure
    de Chimie de Montpellier- 8, Rue de lEcole Normale,34296 Montpellier Cedex 5
    2
    Institut Europeen des Membranes UMR 5635 (CNRS-ENSCM-UM2) , IEM / UM 2, Place Eugene BATAILLON 34095
    Montpellier - Cedex 5
    ghislain.davidenscm.Ir
    Traditionnally, perIluorosulIonic acid polymers are used as membranes Ior PEMFC. However, they show some limiting
    perIormances such as durability, reliability, and the cost oI the Iuel cell systems
    ||
    . Proton conductors based on phosphoric or
    phosphonic acid are considered very promising, due to their high charge carrier concentration, their high thermal stability and
    also to the high resistivity oI the protogenic group
    ||
    . Only Iew Iluorinated copolymers containing phosphonic acid Iunctions
    have been used Ior Iuel cell applications. The present study shows the synthesis oI new Iluorinated copolymers bearing
    phosphonic acid groups by radical copolymerization in solution oI vinyl ether (VE) and chlorotriIluoroethylene (CTFE).
    Alternated poly(VE-alt-CTFE) copolymers (Mn 20.000 g/mol) have been obtained, thanks to both the acceptor characters oI
    CTFE and the high donor character oI VE
    ||
    . Phosphonate Iluorinated copolymers were then obtained quantitatively according
    to Michaelis-Arbuzov reaction, and eIIiciently hydrolyzed by silylation, leading to the corresponding phosphonic acid-
    containing copolymer in 70 mol overall yield (scheme 1). This new Iluorinated polymer was perIectly characterized by
    means oI
    1
    H,
    19
    F and
    31
    P NMR and by FTIR spectroscopies, and showed a high thermal stability (up to 220 C) under air.
    Flexible and mechanically strong membranes were obtained by casting 27 wt solutions oI alternated Iluorinated phosphonic
    acid copolymers in DMSO at 90C. The proton conductivity was measured at room temperature and as a Iunction oI the
    concentration oI phosphonic acid groups. For the highest concentration oI phosphonic acid group (95 mol ), the conductivity
    -23-
    was 20 mS/cm at room temperature and 98 RH. The water uptake was showed to be highly depending on the concentration
    oI phosphonic acid groups.
    Scheme 1: Synthesis oI Iluorinated (co)polymer bearing phosphonic acid units
    |1| Wieser, C. Fuel Cells (Weinheim, Ger.) 2004, 4, 245-250.
    |2| Bock, T.; Moehwald, H.; Muelhaupt, R. Macro. Chem. Phys. 2007, 208, 1324-1340.
    |3| LaIitte, B.; Jannasch, P. Advances in Fuel Cells 2007, 1, 119-185.
    |4| Valade, D.; Dissertation. University oI Montpellier 2, 2007, Montpellier, France.
    OA.4.6
    Phosphonic acid containing poly(aryl ether ketone)s
    E. Chauveau
    1
    , V. Martin
    1
    , C. Marestin
    1
    , R. Mercier
    1
    , H. Waton
    2
    1
    LMOPS-CNRS-UMR 5041, Chemin du Canal - 69 360 Solai:e
    2
    SCA-CNRS-USR 59, , Chemin du Canal - 69 360 Solai:e
    marestinlmops.cnrs.Ir
    Amongst the diIIerent existing 'protogenicgroups, phosphonic acids have recently attracted a great interest Ior the elaboration
    oI proton conducting polymers
    (1,2,3)
    . In this work, the eIIect oI the incorporation oI phosphonic acid groups in SulIonated
    Poly(Aryl Ether Ketone)s will be discussed in regards to the development oI new high perIormance materials Ior Iuel cell
    application. A particular interest will be devoted to the synthesis oI such macromolecular structures.
    New phosphonate containing biphenols (as illustrated below) have been synthesized.
    A complete characterization oI these monomers will be presented. Based on such compounds, Poly (Aryl Ether Ketone)s
    containing phosphonate groups were synthesized by direct polycondensation. The phosphonic acid containing analogues were
    obtained by the cleavage oI ester groups, using acid conditions. A careIul characterization oI the diIIerent structures will be
    presented.
    Polymer blends involving both SulIonated Poly(Aryl Ether Ketone)s and phosphonic acid containing macromolecules were
    also elaborated and studied. Water uptake and ionic conductivity oI these diIIerent polymers were achieved Irom membrane
    materials. Preliminary Iuel cell tests were perIormed.
    |1| B. LaIitte, P. Jannasch, Advances in Fuel cells, (2007), 1, 119-185.
    |2| T. Bock, H. Mhwald, R. Mlhaupt, Macromolecular Chemistrv and Phvsics, (2007), 208, 1324-1340.
    |3| A. Rusanov, P. Kostoglodov, M. Abadie, V. Y. Voytekunas, D. Y. Likhachev, Advances in Polvmer Science, (2008), 216,
    125-155.
    -24-
    OA.4.7
    Preparation and characterization of composite membranes using blends of
    SPEEK/PBI for high temperature PEMFC applications
    E.C. van de Ven, Z. Borneman, M. Wessling
    Universitv of Twente, Institute of Mechanics, Process and Control Twente (IMPACT) Department of Science and Technologv,
    Membrane Technologv Group, P.O. Box 217, 7500 AE Enschede, The Netherlands
    z.bornemanutwente.nl
    The Polymer Electrolyte Membrane Fuel Cell (PEMFC) is becoming increasingly important as a candidate Ior
    environmentally Iriendly energy production. Present PEMFCs, however, have an upper temperature limit permitting operation
    only at moderated temperatures. For industrial applications PEMFCs operating at higher temperatures are more and more
    desired. BeneIits are reaction rate increase, CO tolerance increase, operating voltage reduction and possibilities Ior
    cogeneration.
    The development oI a PEMFC based on a new composite multiIunctional material based on synergic combination oI zeolites,
    ionic liquids and polymers capable Ior operation at T~ 80C is a challenging task. In this work membranes are manuIactured
    that can meet the requirements Ior this high temperature PEMFC. To aim Ior this high temperature resistant polymer poly
    benzimidazole (PBI) was blended with sulIonated poly ether ether ketone (SPEEK) and precipitated by inverse phase
    separation in deionized water |1,2|. The resulting porous membrane is mechanical stable, having a temperature resistance up to
    300C. To improve the proton conductivity the membrane is impregnated with ionic liquid. The resulting proton conductivity
    is comparable to NAFION

    ion exchange membranes (10mS/cm at 25C).
    The EU commission is acknowledged Ior the Iinancial support oI this project in the 7
    th
    Iramework program, theme 5 energy,
    Energy Topic 2007.1.1.1: Basic research Ior materials and processes Ior PEMFC`s. Project acronym ZEOCELL.
    |1| H. Lin, Y. Chen, C. Li, C. Cheng, T. Yu, Preparation oI PBI/PTFE composite membranes Irom PBI in N,N`-dimethyl
    acetamide solutions with various concentrations oI LiCl, Journal oI Power Sources 181 (2008) p. 228-236
    |2| A. Carollo, E. Quartarone, C. Tomasi, P.Mustarelli, F. Belotti, A. Magistris, F. Maestroni, M. Parachini, L. Garlaschelli,
    P.P. Righetti, Developments oI new proton conducting membranes based on diIIerent polybenzimidazole structures Ior Iuel
    cell applications, Journal oI Power Sources 160 (2006) p. 175-180
    OA.4.8
    Thermal properties of side-chain sulfonated poly(ether sulfone)s
    J. Meier-Haack, A. Ptschke, L. Fallant, W. Butwilowski, K. Schlenstedt, A. Quetschke, C. Vogel
    Leibni: Institute of Polvmer Research Dresden, Hohe Strasse 6, D-01069 Dresden, Germanv
    mhaackipIdd.de
    SulIonated aromatic polymers, in particular poly(arylene ether sulIone)s have gained much interest as ion-exchange
    membranes in Iuel cell applications in the past as Ior example outlined in |1| and literature cited therein. Although the base
    polymers possess high thermal, mechanical and chemical stabilities, these properties are altered by the introduction oI the
    sulIonic acid groups. The sulIonic acid groups make the polymer more brittle due to polar interactions (e.g. Iormation oI
    hydrogen bonds). On the other hand the hydrophilic character oI these groups results in the enhanced uptake oI water which
    acts as a plasticizer, hence lowering the glass transition temperature T
    g
    . Since the T
    g
    is an important number limiting the
    operation temperature oI a Iuel cell, e.g. Ior NaIion

    -based Iuel cells ca. 80 90C. Another point oI interest is the state oI
    water adsorbed in the membrane materials. As outlined by McGrath and coworkers, at least three diIIerent states oI water can
    be present ranging Irom non-Ireezable tightly bound, over Ireezable loosely bound showing a broad melting in the range Irom
    20C up to 20C to Iree water, melting at 0C |2|. While the Iirst state is responsible Ior the soItening, the third state is
    correlated to the proton transport in the membrane. Recently we reported on novel side-chain sulIonated poly(arylene ether
    sulIone)s as promising candidates Ior Iuel cell membranes |3 and Fig. 1|.
    -25-
    In this contribution we report on the properties oI
    these polymers Iocussing on the thermal properties
    such as T
    g
    and the state oI water inside the
    membrane. The non-sulIonated base polymers
    showed a T
    g
    around 190 230C, depending on the
    phenylhydroquinone content. On sulIonation the T
    g
    shiIted to higher values (230 245C). In the Iully
    hydrated state the membranes exhibited a T
    g
    oI
    around 120C. Furthermore the water dependence oI
    conductivity properties are discussed. As a result,
    blockcopolymers showed advantageous properties
    over random copolymers oI the molecular weight and
    IEC. Fig. 1: Structure oI sPAES under investigation
    |1| G. Maier, J. Meier-Haack, SulIonated Aromatic Polymers Ior Fuel Cell Membranes, Adv. Polym. Sci., 2008, 216, 1 62
    |2| Y. S. Kim, L. Dong, M. A. Hickner, T. E. Glass, V. Webb, J. E. McGrath, State oI Water in DisulIonated Poly(arylene
    ether sulIone) Copolymers and a PerIluorosulIonic Acid Copolymer (NaIion) and Its EIIect on Physical and Electrochemical
    Properties, Macromolecules, 2003, 36(17), 6281 - 6285
    |3| J. Meier-Haack, C. Vogel, W. Butwilowski, D. Lehmann, SulIonated poly(ether sulIone)s Ior Iuel cells by solvent-Iree
    polymerization, Pure Appl. Chem., 2007, 79(11), 2083 - 2093
    OA.5.1
    Surface activated oxygen transport membranes based on perovskitic
    La
    0.58
    Sr
    0.4
    Co
    0.2
    Fe
    0.8
    O
    3-delta
    S. Baumann
    1
    , D. Schlehuber
    2
    , W.A. Meulenberg
    1
    , T. Markus
    2
    , H.P. Buchkremer
    1
    Forschungs:entrum Jlich GmbH, Institute of Energv Research,
    1
    IEF-1 Materials Svnthesis and Processing
    2
    IEF-2 Microstructure and Properties of Materials
    Leo-Brandt-Strasse, D-52425 Jlich, Germanv
    s.baumannIz-juelich.de
    The OxyIuel technology is one possibility to reduce CO
    2
    emissions Irom point sources, e.g. Iossil Iuelled power plants, by
    Carbon Capture and Storage (CCS). This technology requires pure oxygen Ior combustion resulting in a highly pure (wet) CO
    2
    stream, which could be easily sequestered. A key technology is the development oI Oxygen Transport Membranes (OTM),
    which are associated with signiIicantly lower eIIiciency losses compared to cryogenic air liqueIaction. OTM consist oI gastight
    Mixed Ionic Electronic Conductors (MIEC), e.g. perovskites, which allow oxygen diIIusion through vacancies in the crystal
    lattice and simultaneous transport oI electrons in the opposite direction at elevated temperatures, e.g. 800-900C |1|. La
    1-
    x
    Sr
    x
    Co
    1-y
    Fe
    y
    O
    3-delta
    is a promising perovskitic membrane material due to its high oxygen permeation rates, which was primarily
    identiIied by Teraoka et al. |2|. La
    0.58
    Sr
    0.4
    Co
    0.2
    Fe
    0.8
    O
    3-delta
    (in the Iollowing: LSCF) is a known high perIormance cathode
    material Ior Solid Oxide Fuel Cells (SOFC) and potential candidate Ior OTM.
    In order to come to higher eIIiciencies an increase oI oxygen permeation rates are necessary. ThereIore, membrane thickness
    should be reduced. However, a sole thickness reduction below a characteristic thickness L
    c
    is not the way to success as surIace
    exchange kinetics becomes more and more rate limiting. In that case surIace activation is necessary by porous activating
    layers. These layers in a Iirst approach simply increase the surIace area. Additionally they can act as carrier Ior catalysts,
    which could be inIiltrated into these layers.
    Our work has been Iocused on the permeation
    measurements oI LSCF bulk membranes with 0.5 mm
    thickness and diIIerent porous activating layers oI the same
    material, Figure 1, or similar compositions containing
    Praseodymium as catalytic active element. Obtained results
    show that surIace exchange kinetics has a signiIicant
    inIluence on LSCF membranes already at relatively high
    thickness oI 0.5 mm. Since the inIluence is expected to be
    enhanced Ior thin Iilm membranes on porous supports
    (asymmetric membrane), the importance oI surIace
    activation is evident.
    Figure 1 LSCF bulk membrane with LSCF
    porous activation laver
    -26-
    |1| J. Sunarso, S. Baumann, J.M. Serra, W.A. Meulenberg, S. Liu, Y.S. Lin, J.C. Diniz da Costa, Mixed Ionic-Electronic
    Conducting (MIEC) ceramic-based membranes Ior oxygen separation, J. Membrane Science 320 (2008) 13-41
    |2| Y. Teraoka, H.M. Zhang, S. Furukawa, N. Yamazoe, Oxygen permeation through perovskite-type oxides, Chem. Lett. 14
    (1985) 1743-1746
    OA.5.2
    Nano tailored ceramic membranes on porous metal substrats
    D. Ulhmann
    1
    , F. Hauler
    2
    , K. Brands
    2
    , S. Smart
    1
    , M. Bram
    2
    , W.A. Meulenberg
    2
    , J.C. Diniz da Costa
    1
    1
    The Universitv of Queensland, FIMLab Films and Inorganic Membrane Laboratorv, Division of Chemical Engineering,
    Brisbane, Qld 4072, Australia.
    2
    Forschungs:entrum Juelich, Institute for Materials Svnthesis and Processing (IEF-1), Leo-Brandt-Strae, 52428 Juelich,
    Germanv
    j.dacostauq.edu.au
    Robust membrane technologies are required Ior industrial gas separation, which can be met by inorganic membranes. Many
    industrial processes operate at high pressures (40 MPa) and temperatures (700
    o
    C) which brings a new set oI challenges in
    membrane technology. In the case oI molecular sieve membranes, ceramic tubular substrates are envisaged Ior scale up and
    pilot trials. However, ceramic tubes are generally not robust enough Ior high temperature and pressures. To address this
    problem, the University oI Queensland (UQ) in Australia and the Forschungszentrum Juelich (FZJ) in Germany are jointly
    developing a new generation oI robust inorganic membranes Ior gas separation Ior clean coal energy delivery.
    The key concept in this work is the utilization oI porous metal substrates to attain industrial robustness. However, porous metal
    substrate surIaces are generally rough with large pore sizes. To overcome this problem, metallic and ceramic interlayers Ior
    Ilattening the surIace and bridging the pore size are applied. Furthermore, we are employing nano-structured ceramic
    intermediate Iilms based on zirconia, titania and alumina as shown in Figure 1(a), Iollowed by the application oI metal doped
    silica layer Ior gas separation. Figure (1b) shows the top view oI a membrane tested at a Ilue gas stream at the EnBW
    RheinhaIen Coal Power Station in Karlsruhe, Germany. A cake oI Ily ash was Iormed on the membrane containing mainly
    SiO
    2
    , Al
    2
    O
    3
    , CaO and CaSO
    4
    .2H
    2
    O. In addition, the gas separation layer, which is metal doped silica, shows in lab scale
    temperature dependency permeation (see Figure 1(c)), reIlecting the molecular sieve capability oI the membrane to separate
    gases. High selective values were achieved Ior He/N
    2
    (350) and H
    2
    /CO
    2
    (87) at 160
    o
    C
    (a) (b)
    (c)
    Figure 1(a) porous metal substrate (M) Iollowed by diIIerent interlayers, a nano-structured ceramic layer (N) and a top
    selective layer, (b) Ily ash cake on top oI the membrane, (c) metal doped silica membrane.
    -27-
    T
    N
    M
    Fly ash cake
    He
    H
    2
    N
    2
    CO
    2
    OA.5.3
    Manipulation of the transport properties and selectivity of porous anodic alumina
    membranes by controlling the pore structures and surface chemistry
    L. Velleman
    1
    , J. G. Shapter
    1
    , D. Losic
    2
    1
    Flinders Universitv, School of Chemistrv, Phvsics and Earth Science, Adelaide, SA 5042, Australia.
    2
    Universitv of South Australia, Ian Wark Research Institute, Mawson Lakes, Adelaide, SA 5095, Australia
    vell0019Ilinders.edu.au
    Porous anodic alumina membranes (AAO) Iabricated by electrochemical anodization oI aluminium are attractive materials Ior
    a diverse range oI applications including molecular separation, catalysis, energy storage, drug delivery, biosensing and
    template synthesis
    1-2
    . The pore diameter, inter pore distance, pore density and internal pore structures can be easily
    manipulated by anodization conditions which makes AAO membranes particularly attractive Ior nanoengineering oI advanced
    molecular sieving devices such as nanotube membranes.
    In this work we investigated the transport and selectivity oI AAO membranes by controlling their structural properties and
    surIace chemistry. Unique membrane structures were Iormed in which the diameters, inter pore distances and shape along the
    length oI the pores were varied using diIIerent combinations oI electrolytes and applied voltage/current signals during
    anodization
    3-4
    . Reduction oI the diameter oI AAO nanopores to obtain size selective membranes involved electroless gold
    deposition to prepare gold nanotube membranes with desired pore diameters
    1
    . Silanes and alkanethiol chemistry were used on
    the internal and external surIaces oI the unmodiIied AAO and gold modiIied AAO respectively to achieve chemical selectivity.
    Fabricated membranes were extensively characterized by a variety oI surIace characterization techniques including atomic
    Iorce microscopy (AFM), scanning tunneling microscopy (STM), energy dispersive x-ray analysis (EDAX), XPS, FTIR and
    RAMAN spectroscopy and contact angle measurements. The transport and selectivity properties oI Iabricated membranes were
    studied using several model dye molecules. Permeation experiments were perIormed in a permeation cell in which the
    membrane separates two halI-cells; the Ieed cell and the permeate cell. The diIIusion oI the molecules Irom the Ieed cell
    through the membrane and into the permeate cell was continuously monitored by UV-Vis to determine the transport and
    selectivity properties oI the membranes. The integration oI Iabricated AAO membranes with micro/nanoIluidic systems is
    proposed.
    Fig 1. Membranes with diIIerent pore geometries
    L. Velleman, D. Losic, J.G. Shapter, Gold nanotube membranes Iunctionalised with Iluorinated thiols Ior selective molecular
    transport, Journal oI Membrane Science, 2009, doi.10.1016/f.memsci.2008.11.055
    D. Losic, M. A. Cole, B. Dollmann, K. Vasilev, H. J. Griesser, SurIace modiIications oI nanoporous alumina membranes by
    plasma polymerisation, Nanotechnologv, 2008, 19, 245704 (7 pg)
    M. Lillo, D. Losic, Pore opening detection Ior controlled dissolution oI barrier oxide layer and Iabrication oI nanoporous
    alumina with through-hole morphology, Journal of Membrane Science, 2009, 327, 11-17
    D. Losic, M. Lillo, D. Losic Jnr., Porous alumina with shaped pore geometries and complex pore architectures Iabricated by
    cyclic anodization, Small, 2009, doi: 10.1002/smll.200801645 (in press)
    OA.5.4
    Preparation of catalytic hollow fiber membranes containing metal nanoparticles by
    two surface modification techniques
    J. Macanas
    1
    , L. Ouyang
    2
    , M.L. Bruening
    2
    , M. Muoz
    3
    , J-F. Lahitte
    1
    , J-C. Remigy
    1
    1
    Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 31062 Toulouse cedex 09, France
    2
    Department of Chemistrv, Michigan State Universitv, 48824 East Lansing, Michigan, USA.
    3
    Departament de Quimica, Universitat Autonoma de Barcelona, Campus UAB s/n, 08193 Bellaterra, Spain
    remigychimie.ups-tlse.Ir
    Metal Nanoparticles (MNPs) have unique physico-chemical properties which diIIer Irom bulk material (i.e. Au nanoparticles
    are much more reactive than bulk gold). Some oI these properties could be advantageous Ior catalytic applications |1|.
    -28-
    However, the main drawback oI MNPs, which still limits their wide application, is their insuIIicient stability with regard to a
    high trend Ior aggregation. To cope with this inconvenience, the stabilization oI MNPs in polymeric matrices oI diIIerent types
    has been tested, and current results show that this procedure could be one oI the most promising strategies to maintain catalytic
    properties |2|. ThereoI, the development oI catalytic membrane reactors (CMRs) containing MNPs can be envisaged. The
    advantageous catalytic properties oI nanomaterials can increase CMRs` perIormance whereas the integrity oI nanomaterials
    can be guaranteed inside the membrane polymeric matrices.
    Taking all this into account, the aim oI this work is the in situ synthesis oI polymer-stabilized MNPs inside Iunctionalized
    polymeric membranes in order to build catalytic membrane reactors. It is important to notice that Ior achieving this objective it
    is necessary that the polymeric support has Iunctional groups capable to retain nanoparticle precursors (i.e. sulIonic groups
    which bond metal ions). Once the precursor is immobilized, nanoparticles can grow inside the polymeric matrix by chemical
    reduction oI metal ions. This operation has been already tested Ior the development oI new electrochemical sensors.
    Two diIIerent strategies have been used in this work. Firstly, polysulIone ultraIiltration membranes were modiIied by UV-
    photograIting using sodium p-styrene sulIonate (NaSS) as a vinyl monomer |3|. This procedure yields covalent bonding
    between the charged polymer and the membrane substrate. Secondly, polyethersulIone microIiltration hollow Iibres have been
    successIully modiIied by applying polyelectrolyte multilayers |4|. The catalytic perIormance oI developed hollow Iibers has
    been evaluated by using the reduction oI nitrophenol to aminophenol by sodium borohydride as a model. This reaction does
    not take place in the absence oI catalyst, and it is quite simple to Iollow its kinetics by UV spectroscopy. Hollow Iibre modules
    containing 1 to 5 Iibres with Pd and/or Au MNPs have been tested in both dead-end and cross-Ilow Iiltration-reaction
    experiments giving as a result that complete nitrophenol degradation is possible depending on operation parameters such as
    applied pressure and permeate Ilux.
    |1| D. Astruc, F. Lu, J. Ruiz Aranzaes, Nanoparticles as Recyclable Catalysts: The Frontier between Homogeneous and
    Heterogeneous Catalysis, Angew. Chem. Int. Ed. 2005, 44, 7852-7872.
    |2| A.D. Pomogailo, V.N. Kestelman, Metallopolymer Nanocomposites (Springer-Verlag, 2005).
    |3| A. Akbari, S. Desclaux, J.C. Rouch, J.C. Remigy, Application oI nanoIiltration hollow Iibre membranes, developed by
    photograIting, to treatment oI anionic dye solutions, J. Membr. Sci. 297 (2007) 243252.
    |4| D.M. Dotzauer, J. Dai, L. Sun, M.L. Bruening, Catalytic Membranes Prepared Using Layer-by-Layer Adsorption oI
    Polyelectrolyte/Metal Nanoparticle Films in Porous Supports, Nano Letters, 2006, 6 (10), 2268-2272.
    OA.5.5
    Gas separation properties of polyurethane/epoxy nanocomposite membrane
    M. Sadeghi
    1
    , M. A. Aravand
    2
    , A. H. Saeidi Dehaghani
    2
    , S. Khatti Dizabadi
    1
    1
    Department of Chemical Engineering, Isfahan Universitv of Technologv, Isfahan 84156-8311, Iran
    2
    Department of Chemical Engineering, Facultv of Engineering, Tarbiat Modares Universitv, Tehran, Iran
    m-sadeghicc.iut.ac.ir
    Separation oI CO
    2
    gas Irom Ilue gases is an important task as Iar as the environmental problems in terms oI global warming
    issue are concerned. Utilizing high perIormance membranes in CO
    2
    /N
    2
    separation is one oI the most important methods in this
    regard. In addition to their good chemical and mechanical properties, Polyurethane membranes have shown a suitable
    perIormance in gas separation processes |1-2|.
    In some research studies, the addition oI proper Iillers has been suggested as an eIIective method to enhance the perIormance
    oI polymeric membranes in the separation oI CO
    2
    Irom mixed gases |3-4|.
    Our work has been Iocused on addition oI novel epoxy nano-particles to a polyurethane membrane in order to improve its
    perIormance in separation oI CO
    2
    Irom nitrogen and methane gases. Polyurethane was synthesized based on 2000 molecular
    weight Polypropylene-glycol (PPG 2000)/ hexamethylene diisocyanate (HDI)/ 1,4-Butane diol (BDO). Cured nano-epoxy
    spheres were also prepared via the so called Transitional Phase Inversion (TPI) method |5|. PU and PU-epoxy hybrid
    membranes were then prepared through Thermal Phase Inversion method. Scanning electron microscopy (SEM) and
    diIIerential scanning calorimetery (DSC) were employed in order to characterize the resulting membranes. The obtained SEM
    micrographs conIirmed the nano-scale distribution oI epoxy particles in the polymer matrix. Gas permeation experiments
    represented that the permeability oI the gases decreased upon increasing the epoxy content oI the nano-composite membranes.
    The permeability oI CO
    2
    was decreased Irom 186 barrer in pure PU to 134 barrer in the nano-composite membrane containing
    20 wt oI the epoxy particles. Furthermore, the selectivity oI CO
    2
    /N
    2
    in the corresponding membranes demonstrated an
    increase Irom 24 in pure PU to 60 in the composite membranes. The results obtained in this study, emphasize the outstanding
    perIormance oI a novel hybrid membrane in separation oI gases as being evident Irom Robeson upper line.

    |1| M. A. Semsarzadeh, M. Sadeghi , M. Barikani, H. Moadel, The EIIect oI Hard Segments on the Gas Separation Properties
    oI Polyurethane Membranes, Iran. Polym. J., 16 (2007) 819-827.
    -29-
    |2| M. A. Semsarzadeh, M. Sadeghi, M. Barikani, The eIIect oI Chain Extender Length on the Gas Permeation Properties oI
    Polyurethanes, Iran. Polym. J., 17 (2008) 431-440.
    |3| Morteza Sadeghi, G. Khanbabaei, A. Dehaghani, M. Aravand, S. Khatti, Gas permeation properties oI ethylene vinyl
    acetatesilica nanocomposite membranes, J. membr. Sci., 322 (2008) 423-428.
    |4| M. Sadeghi, M. A. Semsarzadeh, H. Moadel, Enhancement oI gas separation properties oI Polybenzimidazole membrane
    by incorporation oI silica nano particles, J. membr. sci., Doi. 10.1016/j.memsci.2008.12.073
    |5| J. L. Salager, A. Forgiarini, L. Marquez, A. Pea, A. Pizzino, M. P. Rodriguez and M. R. Gonzalez, Using emulsion
    inversion in industrial processes, Adv. in coll. and interI. sci., 108 (2004) 259-272.
    OA.5.6
    A general method for the direct functionalization of polyethersulfone membranes
    with small molecules
    A. Schulze, B. Marquardt, R. Schubert, M. R. Buchmeiser
    Leibni: Institute of Surface Modification, Permoserstr. 15, D-04318 Leip:ig, Germanv
    agnes.schulzeiom-leipzig.de
    Membrane separation systems have gained increasing importance Ior many diIIerent applications, e.g., in hemodialysis, water
    treatment, sterilizing Iiltration, or proton conduction in Iuel cells. Today, micro- and ultraIiltration membranes are
    predominantly Iabricated Irom synthetic membrane materials, such as polyethersulIone (PES), polysulIone (PSI),
    polyvinylidene Iluoride (PVDF), or polyacrylonitrile (PAN). These materials oIIer both chemical and physical stability
    towards a broad range oI conditions. The diverse applications necessitate the modiIication oI the polymer in order to avoid any
    Iouling oI the hydrophobic membrane surIaces or to achieve a Iunctionalized membrane Ior speciIic applications.
    Especially Ior the improvement oI the antiIouling properties oI micro- and ultraIiltration membranes, many approaches Ior the
    surIace modiIication have been proposed and the resulting membranes show promising antiIouling properties. However,
    commonly used hydrophilization methods are characterized by serious disadvantages as they risk the contamination oI the
    eluent by non-permanently immobilized compounds or by the initiators/catalysts used. Furthermore, they require a substantial
    number oI process steps (e.g. activation oI the scaIIold polymer Ior subsequent graIting and additional puriIication steps), and
    Iinally, the use oI harmIul or even toxic compounds.
    Here we present a method Ior the straight Iorward and permanent Iunctionalization oI PES membranes using small molecules
    bearing diverse hydrophilic Iunctionalities (Scheme 1). Our approach combines surIace activation oI the matrix polymer PES
    and the simultaneous immobilization oI small molecules by use oI low-energy electron-beam (EB) in an aqueous system.
    The new procedure guarantees Ior the permanent
    immobilization oI hydrophilic small molecules on
    a PES membrane matrix. It neither requires any
    preceding surIace Iunctionalization nor the use oI
    catalysts/photoinitiators or other toxic reagents. In
    addition, it avoids the synthesis oI hydrophilic
    monomers/polymers, thus avoiding additional
    synthetic and puriIication steps as well as the use
    oI organic solvents. Since the use oI EB
    activation allows Ior operating independently
    Irom speciIic Iunctionalities present at the matrix
    polymer`s surIace, the method can be adopted to a
    vast variety oI base membrane polymers, e.g.,
    PSI, PAN, and PVDF. Furthermore, in contrast to
    UV-irradiation, EB is capable oI interpenetrating
    polymeric membranes. This way, also the inner
    surIace oI the membrane is activated Ior the
    desired modiIication reactions.
    Scheme 1. Selected small molecules oIIering diverse Iunctionalities that
    have been used Ior the modiIication oI PES membranes.
    -30-
    OA.5.7
    Stimuli-responsive membranes obtained by nanopore functionalization with a
    thermo-sensitive polymer
    H. Alem
    1,2
    , A.-S. Duwez
    3
    , P. Lussis
    3
    , P. Lipnik
    2
    , A. M. Jonas
    2
    , S. Demoustier-Champagne
    2
    1
    Laboratoire de Chimie Phvsique Macromoleculaire, UMR CNRS-INPL 7568, ENSIC, 1 rue Grandville, BP 451, 54 001
    Nancv Cedex, France.
    2
    Universite catholique de Louvain, Laboratoire des Hauts Polvmeres, Place Croix du Sud, 1 B-1348 Louvain-la-Neuve,
    Belgium
    3
    Nanochemistrv and Molecular Svstems, Department of Chemistrv, Universitv of Liege, B6a Sart-Tilman, 4000 Liege, Belgium
    halima.alemensic.inpl-nancy.Ir
    Functionalizing the surIace oI membranes pores with polymers oI tunable properties provides an interesting approach Ior
    preparing stimuli-responsive membranes with potential applications in the Iields oI drug delivery, bioseparation, water
    treatment, chemical sensor or valve, and so on.
    In this context, our project aims at developing processes leading to the surIace modiIication oI the pore walls oI nanoporous
    membranes by various responsive polymers in order to get membranes with switchable solute permeability in response to
    variation in temperature, pH or ionic strength.
    This communication reports the surIace initiated radical polymerization (SIP) oI N-Isopropylacrylamide (NIPAM) Irom
    nanopore walls oI polyethyleneterephthalate (PET) membranes. Free Radical Polymerization (FRP) and Atom TransIer
    Radical Polymerization (ATRP) were used as polymerization processes. It was shown that graIting polymers Irom nanopore
    walls is an eIIicient route leading to Iunctional and switchable membranes (Fig 1). By playing on the polymerization time,
    PNIPAM brushes oI various thicknesses were obtained within nanopores with diIIerent pore size (4 ~ + 80 nm and 4 ~ + 300
    nm). The opening and closing characteristics oI the thermo-responsive membranes were investigated by measuring the ionic
    current able to Ilow through the graIted membranes as a Iunction oI temperature. Depending on the membrane pore size, two
    types oI permeation control mechanisms were observed. In large pore membranes (4 ~ + 300 nm), low temperature expanded
    PNIPAM chains conIormations resulted in reduced eIIective pore size and thereIore lower permeabilities relative to high
    temperature collapsed macromolecular conIormations. In contrast, in small pore membranes (4 + 80 nm), the low
    temperature expanded PNIPAM brush displayed a greater hydration degree and gave rise to higher permeability than the high
    temperature collapsed conIormations (Iig 2). In this situation, the pore surIace layer became completely rate-controlling; and
    the overall permeability was thus the same as that oI the corresponding hydrogel membrane.
    Fig 1 (leIt): TEM images oI (a) a virgin PET
    330 nm nanopore, PNIPAM-g-PET330 FRP24
    nanopore. The insets are the corresponding
    nitrogen mapping oI the nanopore recorded
    with the EELS detector.
    Fig 2 (right) : Conductancetemperature
    conductancetemperature curves oI PNIPAM-
    g-PET
    330
    (a) and PNIPAM-g-PET
    80
    (b). All
    curves were recorded in 10
    2
    MK
    2
    CO
    3
    .
    OA.5.8
    Surface modification of segmented polyurethane membrane grafted with anti-fouling
    polymer brushes by ozone treatment for improving blood compatibility
    Y.-J. Shih, Y. Chang
    R&D Center for Membrane Technologv and Department of Chemical Engineering, Chung Yuan Universitv, Jhong-Li,
    Taovuan 320, Taiwan
    ychangcycu.edu.tw
    This work describes a surIace modiIication approach oI segmented polyurethane (SPU) membranes graIted with nonionic
    poly(ethylene glycol) methacrylate (PEGMA) and zwitterionic polysulIobetaine methacrylate (PSBMA) via surIace-activated
    ozone treatment and surIace-initiated thermal polymerization Ior improving their blood compatibility. The chemical
    -31-
    composition and microstructure oI the surIace-modiIied SPU membranes were characterized by Fourier transIorm inIrared
    spectroscopy (FT-IR), contact angle and atomic Iorce microscopy (AFM) measurements. Blood compatibility oI the modiIied
    membranes was evaluated by the bioIouling property oI the platelet adhesion observed by scanning electron microscopy
    (SEM) and the plasma protein adsorption determined by an enzyme-linked immunosorbent assay (ELISA). The graIting
    density oI the copolymerized PEGMA and PSBMA polymer brushes on the surIace oI SPU membranes can be well controlled
    by the macromonomer concentration in the reaction solution. The hydration oI polymer brushes on the resulting SPU
    membranes can be controlled by the graIting density oI PEGMA and PSBMA on the membrane surIace. The relative protein
    adsorption was eIIectively reduced with increasing capacity oI the hydration Ior the polymer brushes graIted on the SPU
    membrane surIace. For the platelet adhesion test, a remarkable suppression oI the platelets adhered to the SPU membranes
    graIted with PEGMA and PSBMA polymer brushes was observed. This study not only determines the graIting quality with
    PEGMA and PSBMA, but also provides a Iundamental understanding oI various graIting density governing the eIIects on
    hydrophilicity, surIace morphology, plasma proteins adoption and platelets adhesion on the membrane surIaces.
    |1| Y. Chang, Y. J. Shih, R. C. Ruaan, A. Higuchi, W. Y. Chen, J. Y. Lai, Preparation oI Poly(vinylidene Iluoride)
    MicroIiltration Membrane with UniIorm SurIace-Copolymerized Poly(ethylene glycol) Methacrylate and Improvement oI
    Blood Compatibility, Journal of Membrane Science, 2008, 309, 165-174.
    |2| Y. Chang, S. C. Liao, A. Higuchi, R. C. Ruaan, C. W. Chu, W. Y. Chen, A Highly Stable NonbioIouling SurIace with
    Well-packed GraIted Zwitterionic PolysulIobetaine Ior Plasma Protein Repulsion, Langmuir, 2008, 24, 5453-5458.
    |3| Y. Chang, S. Chen, Q. Yu, Z. Zhang, M. Bernards, S. Y. Jiang, Development oI Biocompatible Interpenetrating Polymer
    Networks Containing a SulIobetaine-Based Polymer and a Segmented Polyurethane Ior Protein Resistance,
    Biomacromolecules, 2007, 8, 122-127.
    |4| Y. Chang, S. Chen, Z. Zhang, S. Y. Jiang, Highly Protein-Resistant Coatings Irom Well-DeIined Diblock Copolymers
    Containing SulIobetaines, Langmuir, 2006, 22, 2222-2227.
    OA.5.9
    Antifouling modification of polypropylene micofiltration membrane surface via
    ~polymer entrapping
    H. Guo, M. Ulbricht
    Lehrstuhl fr Technische Chemie II, Universitt Duisburg-Essen, 45141 Essen, Germanv
    haoIei.guostud.uni-due.de
    To increase the hydrophilicity and anti-Iouling properties oI polypropylene (PP) microIiltration membrane surIace, a novel
    physical process, the 'entrapment oI amphiphilic polymers during the reversible swelling oI the PP surIace region, had been
    proposed|1,2|. With octaethyleneglycol-monooctadecylether (C
    18
    E
    8
    ) as example, a detailed characterization oI modiIied
    membrane`s structure, surIace properties, Iiltration perIormance, anti-Iouling properties as well as the stability oI the modiIi-
    cation has been perIormed. The results showed that the entrapment technology was eIIective to incorporate C
    18
    E
    8
    into outer and
    inner membrane surIace with only weak inIluence on polymer and membrane structure, so that the modiIied PP obtained good
    hydrophilic and modest protein-resistant surIace properties. These properties were stable Ior at least 2 months in water at room
    temperature. In the next part oI this work it was attempted to use the reversible phase (hydrophilic/hydrophobic) and volume
    (swollen/deswollen) transition oI thermo-responsive poly(N-isopropylacrylamide) (PNIPAAm) near the lower critical solution
    temperature (LCST) to improve the antiIouling tendency oI PP membrane surIace. Especially the Iunction to 'selI-elute
    adsorbed protein with alternating temperature around LCST would be oI high interest. SurIace modiIications by 'entrapping
    were perIormed using an amphiphilic diblock copolymer oI poly (butyl acrylate) with PNIPAAm (PBA-b-PNIPAAm, M
    w
    ratio 1:1, M
    w
    ,
    total
    42 kg/mol). The hydrophilicity and antiIouling properties oI modiIied PP membranes increased and an
    abrupt change oI water permeability occured at the LCST, i.e. 32C. Additionally, protein adsorbed at higher temperature
    could be eluted when the temperature was switched to a value lower than LCST. Because this is the Iirst time that Iixation oI
    amphiphilic macromolecules into a nonpolar porous polymer substrate surIace has been reported, it is necessary to investigate
    the mechanism oI this entrapment process. Hence, in the last part oI this work, diIIerent polyethylene glycols (PEG), i.e. homo
    polymers with varied molar mass, a series oI amphiphilic PEG block copolymers (Pluronics

    ) with varied molar mass and


    hydrophilic/phobic balance, PEG400 distearate and C
    18
    E
    8
    , have been studied as modiIiers Ior 'polymer entrapping in PP.
    Finally, it was conIirmed that only those amphiphilic block polymers, which had similar chain lengths oI the two hydrophilic
    and hydrophobic blocks so that they can Iorm reverse micelles in an apolar solvent, were eIIicient Ior successIul surIace
    modiIication by 'polymer entrapment.
    |1| N. P. Desai, J. A. Hubbell, SurIace physical interpenetrating networks oI poly(ethylene terephthalate) and poly(ethylene
    oxide) with biomedical applications, Macromolecules, 1992 (25): 226-232.
    |2| H. F. Guo, SurIace Iunctional modiIication and properties oI polyoleIin Iilms and porous membranes, Master thesis,
    Nanjing Univeristy oI Technology, 2006.
    -32-
    OA.5.10
    Enzymatic membranes prepared by using polyelectrolyte multilayer immobilization.
    Role of the enzyme location on the catalytic reaction
    S. Guedidi
    1,2
    , A. Deratani
    1
    , C. Innocent
    1
    , P. Dejardin
    1
    , S. Roudesli
    2
    , Y. Yurekli
    1,3
    , S. Alsoy Altinkaya
    3
    1
    Institut Europeen des Membranes/ Place Eugene Bataillon, CC 047, 34095 Montpellier, Cedex 5, France.
    2
    Laboratoire des Polvmeres-Biopolvmeres Materiaux Organiques, Faculte des Sciences de Monastir/ Avenue de
    lEnvironnement 5019, Monastir. Tunisie.
    3
    I:mir Institute of Technologv, Department of Chemical Engineering, Gulbahce Kovu, 35430, Urla I:mir, Turkev
    sadika.guedidiiemm.univ-montp2.Ir
    The purpose here is to integrate both Iunctions (biocatalysis and separation) in the membrane structure by direct enzyme
    immobilization on synthetic ultraIiltration membranes. The layer-by-layer technique, which has been introduced by Decher |1|,
    is proposed Ior Iabrication oI enzyme reactive membranes.
    Polyacrylonitrile based membranes having negatively and positively charged surIace (PAN and PAN-PEI) were used to
    immobilize enzymes. In order to investigate the inIluence oI enzyme loading and accessibility, trypsin and urease were studied
    that can be adsorbed inside the pores and only at the surIace, respectively (Fig. 1). Adsorption isotherm and enzymatic activity
    Ior corresponding speciIic substrates were determined. It was Iound that the storage stability is considerably enhanced using
    polyelectrolyte immobilization compared to physisorption.
    a. b.
    Fig.1. Enzyme immobilized in multilayer assemblies (a. case oI trypsin; b. case oI urease)
    Transport experiments through these catalytic materials were carried out in an ultraIiltration cell. It was thus showed that
    enzyme immobilization using the technique oI polyelectrolyte multilayer does not signiIicantly modiIy the permeability
    perIormances oI the obtained materials. Reactivity was showed to vary with the Ilux depending on the loading and location oI
    enzyme. Mechanism oI catalytic action is proposed to take into account the observed results.
    The immobilization oI enzymes on polymeric membrane has become an good approach Ior enhancing their utility in
    biotechnology. The layer-by-layer assembly technique proposed Ior surIace modiIication seems to be versatile and its main
    advantage consists oI its simplicity and the stability oI the obtained membranes.
    The authors would like to thank the French Ministry oI Foreign AIIairs Ior partial Iunding (IFC) and the Gambro-Hospal
    company (France) Ior the giIt oI membranes.
    |1| G. Decher, J.D. Hong, Macromol. Chem. Macromol. Symp., 46 (1991) 321-327.
    OA.5.11
    Control of concentration polarization by modification of ion-exchange membrane
    surface
    N. Pismenskaya
    1
    , V. Nikonenko
    1
    , E. Belova
    1
    , G. Pourcelly
    2
    , Ph. Sistat
    2
    , Ch. Larchet
    3
    1
    Membrane Institute of Kuban State Universitv, 149 Stavropolskava str., 350040 Krasnodar, Russia
    2
    Institute Europeen des Membranes (IEM), ENSCM, UM2, CNRS, Universite Montpellier 2, CC047, Place Eugene Batallon,
    34095 Montpellier, France
    3
    Universite Paris Jal de Marne Paris 12, av. General de Gaulle, 94000 Creteil, France
    npismenmail.ru
    In electrodialysis oI dilute solutions realized in overlimiting current mode, electrical conductivity and diIIusion permeability oI
    ion exchange membranes no longer play a decisive role. At the IoreIront are the properties oI the membrane to control the
    -33-

    degree oI development oI concentration polarization and coupled eIIects. The impact oI these eIIects on the mass transIer oI
    salt ions and their interaction to each other are presented in Figure 1.
    Figure 1: EIIect oI coupled eIIects oI concentration polarization on the mass transIer
    It Iollows Irom the analysis oI the results oI mathematical modeling and experiments that the development oI
    electroconvection withdraws partially diIIusion limitations and increases the mass transIer in the intense current regimes.
    Generation oI H , OH-ions on the membrane / solution interIace suppresses this eIIect. The surIace hydrophobization
    Iacilitates the beginning oI microconvection Ilows. Changing hydrophilic - hydrophobic balance, the catalytic activity oI
    ionogenic groups on the surIace membrane and its level oI heterogeneity (micro-, nano-scale), you can control the degree oI
    development oI concentration polarization in membrane system. Moreover, not only the properties oI individual membranes
    are important, but the ratio oI these properties between the cation- and anion exchange membranes oI desalination channel.
    Russian Found oI Basic Researches (07-08-00533, 08-08-01047) and CNRS are acknowledged Ior granting the work
    OA.5.12
    Film-forming cellulose acetate graft copolymers with nano-structured architectures:
    synthesis and characterization
    A. Jonquieres
    1
    , M. Billy
    1
    , A. Ranzani Da Costa
    1
    , P. Lochon
    1
    , R. Clement
    1
    , M. Dresch
    2
    ,
    S. Etienne
    3
    , J. M. Hiver
    3
    , L. David
    4
    1
    Laboratoire de Chimie Phvsique Macromoleculaire, UMR CNRS-INPL 7568,
    Nancv Universite, ENSIC, 1 rue Grandville, BP 20451, 54 001 Nancv Cedex, France
    2
    ADEME, 20 avenue du Gresille, BP 90406, 49 004 Angers Cedex, France.
    3
    Laboratoire de Phvsique des Materiaux, UMR CNRS 7556, Ecole Nationale Superieure des Mines, Nancv Universite, Parc de
    Saurupt 54 042, Nancv, France
    4
    Laboratoire des Materiaux Polvmeres et des Biomateriaux, Universite de Lvon, Universite Lvon 1, UMR 5223 IMP, Bat.
    ISTIL, 15, bvd Latarfet 69 622 Jilleurbanne Cedex, France
    Anne.Jonquieresensic.inpl-nancy.Ir
    Cellulose acetate is a very good Iilm-Iorming material Ior aqueous membrane applications. It has also been reported Ior the
    challenging separation oI purely organic mixtures by pervaporation with outstanding selectivity Ior the puriIication oI alkyl-
    tert-butyl ether Iuel octane enhancers. Nevertheless, its Ilux was much too low to allow any Iurther development Ior the latter
    applications. Following a Iew works having shown the true potential oI cellulose acetate plasticizing in this context |1, 2|,
    cellulose acetate was graIted with methyl diethylene glycol methacrylate (MDEGMA) Irom brominated macroinitiators by
    Atom TransIer Radical Polymerization (ATRP) in two steps:
    The Iirst step consisted oI introducing ATRP initiator groups on cellulose acetate. The copolymerization oI MDEGMA was
    then carried out in the second step by graIting Irom the Iormer ATRP initiator groups. The copolymerization scaling-up up to
    ca. 5 g oI copolymer samples was successIully achieved and two Iamilies oI graIt copolymers with nano-structured
    -34-
    architectures were eventually obtained. The graIting Irom a Iirst macroinitiator containing 6 initiator groups Ior 100 glucosidic
    cycles led to a Iirst Iamily oI graIt copolymers with a high number oI poly(MDEGMA) short graIts. A second macroinitiator
    with 1 initiator group Ior 100 glucosidic cycles then enabled to obtain a second Iamily oI copolymers with almost the same
    graIt weight Iractions but with a low number oI long graIts. The morphology oI the graIt copolymers was investigated by
    synchrotron X-ray scattering. The phase segregation typically increased with the copolymer graIt content and the length oI the
    poly(MDEGMA) graIts. Eventually, the copolymer with 44 wt oI long graIts showed a Iully segregated morphology with
    sharp interIaces and a radius oI gyration oI 11.5 nm was estimated Ior the corresponding nano-domains. These copolymers
    were very good Iilm-Iorming materials with potential application in membrane separation processes.
    |1| Q.-T. Nguyen, C. Leger, P. Billard, and P. Lochon, Novel membranes made Irom a semi-interpenetrating polymer network
    Ior ethanol-ETBE separation by pervaporation, Polymers Ior Advanced Technologies, 8 (1997) 487.
    |2| Q.-T. Nguyen, R. Clement, I. Noezar, and P. Lochon, PerIormances oI poly(vinylpyrrolidone-co-vinyl acetate)-cellulose
    acetate blend membranes in the pervaporation oI ethanol-ethyl tert-butyl ether mixtures. SimpliIied model Ior Ilux prediction,
    Separation and PuriIication Technology, 13 (1998) 237.
    OA.6.1
    Bio-inspired mineralization in water-treatment processes: the influence of
    biopolymers and organic substances on scaling of RO/NF membranes
    Z. Steiner
    1
    , H. Rapaport
    2
    , Y. Oren
    1
    , R. Kasher
    1
    1
    Department of Desalination and Water Treatment, Zuckerberg Institute for Water Research, Blaustein Institutes for Desert
    Research, Ben-Gurion Universitv of the Negev, POBox 653, Beer-Sheva, 84105, Israel
    2
    Department of Biotechnologv Engineering, Ben-Gurion Universitv of the Negev, POBox 653, Beer-Sheva 84105, Israel
    yoramobgu.ac.il
    The Iouling oI membranes in reverse osmosis (RO) and nanoIiltration (NF) processes is a complex phenomenon that usually
    involves numerous chemical components, such as sparingly soluble inorganic salts, colloids, and organic macromolecules.
    Despite the vast activity aiming at better understanding membrane Iouling, not much is yet known on the ways bioIouling and
    organic Iouling on membranes aIIect scaling and the precipitation oI sparingly soluble minerals in water treatment systems.
    The present study aims at understanding how bioIilm-derived substances and organic substances aIIect mineralization oI
    hydroxyapatite and other phosphate minerals on membrane surIace, and how they aIIect the resulting crystal morphology. Bio-
    inspired mineralization oI apatite and other calcium minerals in living organisms may help deciphering some molecular
    characteristics oI the interactions oI biopolymers and inorganic minerals.
    Initially, we developed well-deIined model systems Ior crystallization processes in secondary eIIluents oI domestic
    wastewater. The mineralization oI calcium minerals, especially phosphates was monitored using the Iollowing methods: 1.
    Crystallization Irom solutions on solid surIaces having selI-assembled monolayers (SAMs) with unique chemical groups as a
    mimetic oI membrane surIace containing biomolecules; The SAMs were prepared in our laboratory by coating gold surIaces
    with long-chain alkyl-thiols having the desired chemical Iunctionalities such as carboxyl, hydroxyl, phospholipids, and alkyl.
    2. Inserting model compounds Ior biological materials such as Iatty acids, polysaccharides and phospholipids into organic thin
    Iilms on the water-air interIace oI a studied solution. Langmuir-Blodget isotherms were used to determine the extent and
    nature oI precipitations that occurred on these Iilms.
    Various analytical tools were employed, including ATR-FTIR analysis oI the growing minerals, quartz crystal microbalance
    with dissipation monitoring (QCM-D), powder X-ray diIIraction, and HR-SEM. It was Iound that thin Iilms containing
    carboxylic acids such as Iatty acids, as well as phospho-lipid groups, promote precipitation, when compared to Iilms with
    hydroxyl or alkyl groups. QCM-D analysis oI surIaces coated by SAMs oI diIIerent chemistries showed a slightly less clear
    inIluence, where hydroxyapatite precipitation was too sensitive to variations in ionic strength oI the solution, thereIore we
    could hardly observe an eIIect by the series oI coatings.
    The authors are not aware oI studies aimed at elucidating, on the molecular level the eIIect oI bioIouling components on
    mineralization on membranes Ior water treatment. This study is a Iirst step towards better understanding oI bioIouling-induced
    mineralization that will enable the development oI more eIIicient ways to tackle the scaling and Iouling problem in water
    treatment processes.
    -35-
    OA.6.2
    Self-organized supramolecular ionic-channels in bilayer and polymeric membranes
    Y. Leduc, L. Bosch, E. Mahon, Y. M. Legrand, A. van der Lee, S. Mihai, M. Barboiu
    Adaptive Supramolecular Nanosvstems Group, Institut Europeen des Membranes, (IEM), UMR-CNRS-5635 ENSCM, UM2,
    CNRS, Universite Montpellier II, Place Eugene Bataillon CC047, F-34095 Montpellier Cedex 5, France.
    yann.leduciemm.univ-montp2.Ir
    SelI-assembly is an attractive strategy Ior building synthetic ion channels.|1| Solid-state structures, when combined with
    Iunctional data, can provide clues about how selI-assembly regulates transmembrane ion transport. A variety oI natural and
    synthetic compounds are known to selI-assemble to give transmembrane ion channels.|2-4|.
    We Iound that a noncovalent assembly oI bis-
    triazole derivatives monomers could selI-
    organize to give a 'unimolecular tubular array
    that can transport alkaline ions across lipid
    membranes. In a mean time it has been shown
    that ditopic monomers with guanine end groups
    Iorm supramolecular polymers in cation-
    templated processes.|5a| OI relevance was our
    demonstration that Na

    and K

    could be
    transported across Iilms made Irom G
    4
    -quartet
    polymers.|5b|
    This work was supported by Iunds Irom the Participating Organizations oI EURYI and the EC Sixth Framework Program
    |1| For reviews oI synthetic ion channels, see: S. Matile, A. Som, N. Sorde, Tetrahedron 2004, 60, 6405; U. Koert, L. Al-
    Momani, J. R. PIeeiIer, Synthesis 2004, 1129.
    |2| (a) Fyles, T. M. Chem. Soc. Rev. 2007, 36, 335-347. (b) Sakai, N.; Mareda, J.; Matile, S. Mol. BioSyst. 2007, 3, 658-666.
    (c) A. Cazacu, A. van der Lee, T.M. Fyles, M. Barboiu, J. Am. Chem. Soc. 2006, 128(29), 9541-9548.
    |3| (a) Bhosale, S.; Sisson, A. L.; Sakai, N.; Matile, S. Org. Biomol. Chem. (2006, 4, 3031-3039. (b) Davis, J. T.; Spada, G. P.
    Chem. Soc. Rev. 2007, 36, 296-313. (c) Davis, J. T. Angew. Chem. Int. Ed. 2004, 43, 668- 698.
    |4| M. Barboiu, P. Aimar, J.-M. Lehn, J. Memb. Sci., 2008, 321, 1-2; (b) J. Memb. Sci., 2008, 321, Special issue : From simple
    molecules to complex membrane systems
    |5| (a) Ghoussob, A.; Lehn, J.-M. Chem. Commun. 2005, 5763-5765. (b) Arnal-Herault, C.; Pasc, A.; Michau., M.; Cot, D.;
    Petit, E.; Barboiu, M. Angew. Chem., Int. Ed. 2007, 46, 8409-8413.
    OA.6.3
    Dynamic biomimetic membranes: toward adaptive neuroreceptors systems
    S. Mihai, Y. Leduc, M. Barboiu
    Adaptive Supramolecular Nanosvstems Group, Institut Europeen des Membranes, (IEM), UMR-CNRS-5635 ENSCM, UM2,
    CNRS, Universite Montpellier II, Place Eugene Bataillon CC047, F-34095 Montpellier Cedex 5, France.
    Simona.Mihaiiemm.univ-montp2.Ir
    Numerous artiIicial transport systems utilizing carriers, channel-Iorming or selI-organized polymeric superstructures able to
    orient, to select and to pump the ionic transport across membranes have been developed in the last decades.
    Constitutional selI-instructed membranes were developed and used Ior mimicking the adaptive structural Iunctionality oI
    natural neuroreceptor systems. These membranes are based on dynamic hybrid materials in which the Iunctional selI-organized
    amino-acid- or acetylcholine-based molecules are reversibly connected with the inorganic silica through hydrophobic non-
    covalent interactions. Supramolecular architectures conIined within scaIIolding silica hydrophobic mesopores can be
    structurally determined and morphologically tuned by neurotransmitter salts templating.
    From the conceptual point oI view these membranes express a synergistic adaptive behavior: the addition oI the Iittest
    molecules like serotonin, acetylcholine and nicotine drives a constitutional evolution oI the membrane toward the selection and
    ampliIication oI the speciIic transporting superstructures within the membrane in the presence oI the molecule that promoted
    -36-
    its generation in the Iirst place. This is a nice example oI dynamic 'trained membranes where a solute (neurotransmitter)
    induces the upregulation (prepare itselI) oI its own selective membrane.
    This work was supported by Iunds Irom the Participating Organizations oI EURYI and the EC Sixth Framework Program
    |1| C. Arnal-Herault, A. Pasc-Banu, M. Barboiu Angew. Chem. Int. Ed. 2007, 46, 4268-4272.
    |2| M. Barboiu, P. Aimar, J.-M. Lehn, J. Memb. Sci., 2008, 321, 1-2; (b) J. Memb. Sci., 2008, 321, Special issue : From simple
    molecules to complex membrane systems
    OA.6.4
    Keynote: Partially positively polarized surface of silver and gold nanoparticles by
    electron acceptor and its implication to facilitated olefin transport
    Y.S. Kang
    1
    , S.W. Kang
    2
    , J. Won
    3
    1
    Department of Chemical Engineering, Hanvang Universitv, Seou1, South Korea.
    2
    School of Chemical and Biological Engineering, Seoul National Universitv, Seoul, South Korea.
    3
    Department of Applied Chemistrv, Sefong Universitv, Seoul, South Korea.
    kangyshanyang.ac.kr
    A new application oI metallic silver and gold nanoparticles as a novel oleIin carrier Ior Iacilitated oleIin transport membranes
    was explored. Silver and gold nanoparticles were chemically activated by suitable electron acceptors such as ionic liquids
    (ILs), p-benzoquinone, or 4-dimethylaminopyridine (DMAP) to enhance speciIic interactions with oleIin molecules. |1-4|
    Facilitated oleIin transport membranes containing chemically activated metal nanoparticles showed good separation
    perIormance in both selectivity and mixed gas permeance.
    It was shown that the introduction oI suitable electron acceptors caused the surIace oI the metallic nanoparticles to become
    positively polarized as evidenced by X-ray photoelectron spectroscopy, resulting in enhanced carrier activity oI metal
    nanoparticles toward oleIin molecules, and consequently Iacilitated oleIin transport.
    It was Iound that the surIace charge density seemed to be strongly correlated with the carrier activity oI the metallic
    nanoparticles. ThereIore the correlation between the charge density oI metallic nanoparticles and the Iacilitated oleIin transport
    was investigated systematically by varying three diIIerent ionic liquids. As a result, we Iound that as the polarity oI the metallic
    nanoparticles was changed upon the addition oI the diIIerent ionic liquids, and that the separation perIormance Ior
    propylene/propane mixtures was also markedly increased with the surIace charge density.
    This work was supported by Energy Technology R&D program (2006-E-ID11-P-13) under the Ministry oI Knowledge
    Economics oI Korea.
    |1| Y. S. Kang,

    S. W. Kang, H. Kim, J. H. Kim, J. Won, C. K. Kim, K. Char, Adv. Mater., 2007, 19, 475.
    |2| S. W. Kang, K. Char, Y. S. Kang, Chem. Mater., 2008, 20, 1308.
    |3| S. W. Kang, D. H. Lee, J. H. Park, K. Char, J. H. Kim, J. Won, Y. S. Kang, J. Membr. Sci., 2008, 322, 281.
    |4| S. W. Kang, J. Hong, J. H. Park, S. H. Mun, J. H. Kim, J. Cho, K. Char, Y. S. Kang, J. Membr. Sci., 2008, 321, 90.
    OA.7.1
    Exploring the potential of oligonucleic acids (~aptamers) for designing stimuli-
    responsive membranes
    T. SchIer
    1
    , M. SchIer
    1
    , C. zalp
    3
    1
    Dept. Chemical Engineering, Universitat Rovira i Jirgili, Av. Pasos Catalans 26, 43007 Tarragona, Spain
    2
    Biochemistrv and Molecular Biologv, Svddansk Universitet,Campusvef 55, 5230 Odense, Denmark
    thomas.schaIerurv.cat
    This work explores the Ieasibility oI designing selective and tunable interIaces Ior sensors and membrane separations based on
    oligonucleic acids which are to be employed in downstream processing and monitoring. Oligonucleic acids ('aptamers) are
    -37-
    biomolecules that can be designed to speciIically interact with in principle any kind oI target molecule, similarly to what is
    known Irom antibodies. Contrary to the latter, however, the chemical stability oI oligonucleic acids is Iar greater, and the
    screening Ior the aptamer with a desired selectivity toward a particular target can be done by an automated in vitro selection
    procedure |1|. As a consequence, interIaces based on these selective compounds should allow reducing the costs oI production
    signiIicantly compared to antibodies, while maintaining a high selectivity.
    An important asset oI oligonucleic acids is the Iact that upon speciIic binding, their spatial conIormation may change
    drastically, allowing in principle their use Ior stimuli-responsive sensing or separations, with the stimulus being actually target
    compounds rather than conventional stimuli such as pH, light and/or temperature.
    In this study particular attention is given to the potential oI using oligonucleic acids to selectively interact with small
    molecules, which has hardly been explored until today |2|. Using surIace plasmon resonance, circular dichroism and nuclear
    magnetic resonance measurements it is shown how aptamers may speciIically interact with targets as small as ethanol amine, a
    low molecular weight carcinogenic compound, as well as adenosine triphosphate. However, possible pitIalls in the application
    oI oligonucleic acids in separations will also be stressed clearly, mainly related to the Iact that being complex biomolecules
    their changes in spatial conIormation may not be independent oI the Ieed composition.
    It will be demonstrated that target-speciIic oligonucleic acids can nevertheless be a promising alternative to existing methods
    oI creating selective, stimuli-responsive interIaces, particularly with respect to their versatility and their potential to be
    designed Ior virtually any target molecule.
    A starting-grant Irom the European Research Council (no. 209842-MATRIX) is grateIully acknowledged.
    |1| O. Thum, S. Jger and M. Famulok, Functionalized DNA: A New Replicable Biopolymer, Angew. Chem. Int. Ed., 40
    (2001) 3990
    |2| T. SchIer, M. SchIer C. zalp, Oligonucleotides Ior designing separation barriers responsive to small molecules,
    submitted
    OA.7.2
    Hollow fillers in mixed matrix membranes for solvent resistant nanofiltration
    K. Vanherck, S. Aldea, A. Aerts, J. Martens, I. Vankelecom
    Centre for Surface Chemistrv and Catalvsis,Department of Microbial and Molecular Svstems,Katholieke Universiteit Leuven,
    Kasteelpark Arenberg 23, 3001 Heverlee, Belgium
    Ivo.vankelecombiw.kuleuven.be
    Mixed matrix membranes (MMMs), consisting oI an organic polymer (bulk) and an inorganic particle (dispersed) phase, have the
    potential to combine high selectivities with high membrane Iluxes. SpeciIically in gas separation and pervaporation processes,
    MMMs have meant an important progress (1, 2). Mixed matrix membranes (MMMs) with a polydimethylsiloxane (PDMS)
    matrix and zeolite Iillers have already been applied successIully in solvent resistant nanoIiltration (3). PDMS, a chemically and
    thermally stable polymer, is known to swell excessively in solvents such as toluene and DCM. The incorporation oI zeolites
    reduces PDMS swelling via extra cross-linking, without lowering the intrinsic Iluxes (3, 4). However, due to the micrometer size
    oI the Iillers, a zeolite-Iilled PDMS top layer requires a certain minimal thickness to remain Iree oI deIects, which limits the
    maximum obtainable Ilux.
    Micron-sized hollow spheres (HS) with a shell consisting oI nano-sized zeolite crystals can be used as an alternative Iiller. The
    zeolite shell should act as a barrier and a crosslinker, while the hollow interior would allow the solvent to pass quickly through
    the membrane.Four types oI composite PAN/PDMS membranes were prepared by dipcoating, using the PERVAP
    polyacrylonitril support (provided by Sulzer Chemtech Gmbh). One membrane had a toplayer consisting oI pure PDMS (A).
    The other three were MMMs with the PDMS toplayer containing respectively ZSM-5 crystals (1m, B), silicalite-1 crystals
    (100nm, C) and silicalite-based HS (1-5m, D). Their perIormance was compared in dead-end SRNF at 15bar with diIIerent
    solvents (isopropanol, methanol, aceton, ethylacetate, hexane, toluene and tetrahydroIuran) and rose Bengal as a test solute
    (1017g/mol).The MMMs showed an increased Ilux (normalized to a top layer thickness oI 3 micron) with isopropanol and
    Bengal rose (D 2,13 l/m bar h) compared to the zeolite Iilled PDMS (B,C 0,12- 0,67 l/m bar h) and unIilled PDMS (A
    0,25 l/m bar h) without loss oI rejection (99). Higher Iluxes were also obtained Ior the methanol and ethanol experiments.
    The other Iiltrations are on-going. Applications in pervaporation and gas separation are being researched.
    |1| Chung et al., Progress in Polymer Science, 32(4), 2007, 483-507
    |2| Shao and Huang, Journal oI Membrane Science 287, 2007, 162179
    |3| Gevers et al., Journal oI Membrane Science 278, 2006, 199204
    |4| Gevers et al., Journal oI Membrane Science 281, 2006, 741746
    -38-
    OA.7.3
    Gas separation using ionic liquid polymers
    R. D. Noble, D. L. Gin, J. E. Bara, B. Voss, A. Finotello, T. Carlisle
    Universitv of Colorado, Chem. & Biol. Eng. Dept., Boulder, CO 80309, USA
    noblercolorado.edu
    The objectives oI this research are to Iabricate new membrane structures based on polymerizable ionic liquids; and characterize
    their Iundamental gas and vapor transport properties. Room temperature ionic liquids (RTILs) with polymerizable groups can
    be readily converted into solid-state, poly(RTILs) Ior use as gas separation membranes.
    The membranes will be Iabricated Irom ILs (which will act as the active component to provide high selectivity Ior the target
    agents) and polymerizable ILs (which can be Iormed directly into solid, mechanically stable and tunable polymeric solids). The
    use oI polymerizable lyotropic liquid crystals (LLCs) as a blendable additive to these IL materials provides a means to obtain
    speciIic nanoporous morphologies that provide the potential Ior enhanced sorption capacity in the resulting Iilms or particles.
    LLC systems have the ability to Iorm ordered, phase-segregated nanoporous structures and incorporate the IL into the ordered
    hydrophilic regions to generate very high surIace area materials. Separately, the addition oI inorganic NPs to IL-based sorbent
    systems will allow Iormation oI solid-state materials, and provide additional surIace area and adsorption capacity Ior the target
    agents.
    Regular solution theory has been shown to accurately predict the solubility oI various gases and vapors in ionic liquids and
    polymers. The IL solubility parameter can be tailored to minimize the diIIerence between the target agent and IL solubility
    parameters which maximizes the solubility. A Iunctional group contribution method to determine the solubility parameter can
    be used to guide the detailed molecular design oI the ionic liquid. This method provides a theoretical Iramework to interIace
    with the material synthesis and characterization.
    Polymerizable ILs have already been shown to have properties that exceed the upper bound on a Robeson plot Ior CO
    2
    /N
    2
    separation. The use oI various additives can Iurther enhance the permeation while maintaining the high selectivity. Results
    will be shown Ior a variety oI materials.
    OA.7.4
    Dynameric materials for CO
    2
    separation - toward adaptive transport membranes
    G. Nasr
    1
    , C. Charmette
    2
    , J. Sanchez
    2
    , M. Barboiu
    1
    1
    Adaptive Supramolecular Nanosvstems,
    2
    Chemical Engineering and Membrane Processes
    Institut Europeen des Membranes, (IEM), UMR-CNRS-5635 ENSCM, UM2, CNRS, Universite Montpellier II, Place Eugene
    Bataillon CC047, F-34095 Montpellier Cedex 5, France.
    gihane.nasriemm.univ-montp2.Ir
    Functional dynamic polymers are used to design new dynameric membrane materials. Our eIIorts involve the synthesis and the
    Iabrication oI dynamic thin-layer selI supported membrane Iilms Ior optimized gaz separation perIormances.
    Dynamic polymers 'dvnamers are capable oI undergoing dynamic exchange, incorporation or decorporation oI their
    monomeric subunits, linked together by labile non-covalent interactions or reversible covalent bonds. Compared with a
    physical mixture oI classical polymers, the mixtures oI dynamers give access to new homogenous species presenting
    controllable modulation oI their structure at molecular level in response to external stimuli or experimental conditions. For all
    these reasons, Iunctional dynamic polymers may be used to optimally conceive diIIerent sets oI 'dynameric membranes. Our
    eIIorts involved the synthesis and the Iabrication oI 'dynameric thin-layer selI-supported solid membrane Iilms, varying the
    internal composition oI the membrane.
    A complete screening oI the membrane composition has been realized by mixing linear and 3D star macromonomers and metal
    ions. Then, their CO
    2
    transport perIormances (permeability, selectivity and partition coeIIicients) are evaluated.We have
    demonstrated that the dynamic reversible covalent exchange processes between the constituent dynameric sub-components
    during the membrane synthesis results in the rapid optimization oI the appropriate membrane composition, leading to
    promising CO
    2
    transport perIormances.
    -39-
    This work was supported by Iunds Irom the Participating Organizations oI EURYI and the EC Sixth Framework Program
    |1| J.-M. Lehn, Prog.Polvm.Sci. 2005, 30, 814.
    |2| G. Nasr, M. Barboiu, T. Ono, S. Fujii, J.M. Lehn, J. Membrane Sci. 2008, 321 (1) 8-14.
    |3| (a) M. Barboiu, P. Aimar, J.-M. Lehn, J. Membrene Sci., 2008, 321, 1-2; (b) J. Membrane Sci., 2008, 321, Special issue :
    From simple molecules to complex membrane systems.
    OA.7.5
    Constitutional self-instructed dynamic membranes-toward adaptive ion-channel
    devices
    Y.-M. Legrand, A. Cazacu, A. Pasc, G. Nasr, A. Van der Lee, M. Barboiu
    Adaptive Supramolecular Nanosystems Group, Institut Europeen des Membranes, (IEM), UMR-CNRS-5635 ENSCM, UM2,
    CNRS, Universite Montpellier II, Place Eugene Bataillon CC047, F-34095 Montpellier Cedex 5, France.
    yves-marie.legrandiemm.univ-montp2.Ir
    Constitutional selI-instructed|1| dynamic membranes were developed and used Ior mimicking the adaptive structural
    Iunctionality oI natural ion-channel systems. These membranes are based on hydrophobic silica mesopores uniIormly oriented
    within alumina macroscopic membranes.
    Supramolecular ion-channel-type
    architectures oI dynamic selI-organized
    macrocycles|2| generated within
    scaIIolding mesopores, can be structurally
    determined and morphologically tuned by
    alkali salts templating.|3| From the
    conceptual point oI view these
    membranes express a synergistic adaptive
    behaviour: the addition oI the Iittest alkali
    ion drives a constitutional evolution oI
    the membrane toward the selection and
    ampliIication oI the speciIic transporting
    crown-ether superstructures in the
    presence oI the cation that promoted its
    generation in the Iirst place. This is the
    Iirst example oI dynamic 'smart
    membranes where a solute induces
    reorganization towards its own selective
    membrane.|4|
    This work was supported by Iunds Irom the Participating Organizations oI EURYI and the EC Sixth Framework Program
    |1| Self-sorting of equilibrating metallosupramolecular DCLs via constitutional crvstal engineering,

    M. Barboiu, F. Dumitru
    Y.-M. Legrand, E. Petit, A. van der Lee, Chem. Comm. 2009 accepted
    |2| AmpliIication and transcription oI the dynamic supramolecular chirality oI the G-quadruplex C. Arnal-Herault, M. Michau,
    A. Pasc-Banu, M. Barboiu, Angew. Chem. Int. Ed. 46, 4268-4272 (2007)
    |3| Columnar SelI-Assembled Ureidocrown-ethers an Example oI Ion-channel Organization in Lipid Bilayers A. Cazacu, C.
    Tong, A. van der Lee,

    T. M. Fyles,

    M. Barboiu, J. Am. Chem. Soc. 128, 9541-9548 (2006).
    |4| Hvbrid crown-ether functionali:ed MCM41-tvpe materials as constitutional self-instructed dvnamic membranes A. Cazacu,
    Y.-M. Legrand, A. Pasc, G. Nasr, A. van der Lee and M. Barboiu, submitted PNAS.
    -40-
    OA.7.6
    Stable hybSi

    nanosieve membranes for dehydration of alcohols and aprotic solvents


    R. Kreiter
    1
    , H. M. van Veen
    1
    , M. D.A. Rietkerk
    1
    , H. L. Castricum
    1,3
    , J. E. ten ElshoI
    2
    , J. F. Vente
    1

    1
    Energv research Centre of the Netherlands, Efficiencv and Infrastructure, Molecular Separation Technologv, PO Box 1,
    1755ZG Petten, The Netherlands.
    2
    Inorganic Materials Science, MESA Institute for Nanotechnologv, Department of Science and Technologv, Universitv of
    Twente.
    3
    Jan t Hoff Institute for Molecular Sciences Facultv of Science, Universitv of Amsterdam
    venteecn.nl
    The key objective oI the International Energy Agency (IEA) Ior Iuture energy technologies is to reduce CO
    2
    emissions with
    ~50Gt/yr by 2050. Carbon-neutral bio-based Iuels such as ethanol, butanol, and bio-diesel are promising candidates Ior
    transportation purposes. However, eIIective and energy-eIIicient separation technologies to dehydrate the wet Iuels or the
    methanol recycle stream in bio-diesel production

    are major hurdles Ior large scale application. It is widely accepted that
    molecular separation membranes will play a crucial role in this transition to sustainable transportation Iuels.
    Pervaporation or hybrid distillation-pervaporation separation processes using membranes are commonly considered options Ior
    the energy eIIicient dehydration oI organics. One oI the typical examples is the dehydration oI bio-ethanol originating Irom
    Iermentation mixtures. Commonly available membranes based on polymers, zeolites, and silica share a limited stability in the
    presence oI acids or under hydrothermal conditions.
    We recently explored the use oI organic-inorganic hybrid silica Ior microporous membranes. Membranes based on a mixture
    oI 1,2-bis(triethoxysilyl)ethane (BTESE) and methyltriethoxysilane (MTES) or only BTESE have unprecedented liIe times oI
    at least 2 years in the dewatering oI n-butanol at 150 C.
    1
    Here, we report the breakthrough perIormance and acid resistance oI
    such organic-inorganic hybrid silica membranes (HybSi

    ) in the dehydration oI alcohols and aprotic organic solvents. We


    aimed to Iurther enhance the selectivity Ior water and tailor the average pore size by also using bis(triethoxysilyl)methane
    (BTESM), having a single CH
    2
    bridging group.
    2
    The behavior oI the diIIerent HybSi

    membranes in dewatering oI lower


    alcohols will be compared.
    |1| H. L. Castricum, A. Sah, R. Kreiter, D. H. A. Blank, J. F. Vente, J. E. ten ElshoI, Chem. Commun. 2008, 1103-1105
    |2| H. L. Castricum, R. Kreiter, H. M. van Veen, D. H. A. Blank, J. F. Vente, J. E. ten ElshoI, J. Membr. Sci. 2008, 324,
    111-118.
    |3| R. Kreiter, M. D. A. Rietkerk, H. L. Castricum, H. M. van Veen, J. E. ten ElshoI, J. F. Vente, ChemSusChem 2009, in
    press.
    OA.7.7
    Keynote: Carbon nanotube membranes; mimicking nature with dramatic mass
    transport and gate keeper activity
    B.J. Hinds
    Dept. of Chemical and Materials Eng., Universitv of Kentuckv, Lexington KY USA 40506-0046.
    bjhindsengr.uky.edu
    Carbon nanotubes have three key attributes that make them oI great interest Ior novel membrane applications 1) atomically
    Ilat graphite surIace allows Ior ideal Iluid slip boundary conditions 2) the cutting process to open CNTs inherently places
    Iunctional chemistry at CNT core entrance and 3) CNT are electrically conductive allowing Ior electrochemical reactions and
    application oI electric Iields gradients at CNT tips.
    To explore the hypothesis oI Gatekeeper` membrane selectivity, the entrances to CNT`s cores were Iunctionalized with
    aliphatic amines oI diIIerent lengths, charged dye molecule and poly-peptides. Anionic charged Iunctional groups are seen to
    sharply increase Ilux oI cationic permeates. This eIIect is reduced at higher solution ionic strength consistent with shorter
    Debye screening length screening attractive charge at the CNT core entrance. A hindered diIIusion model with a geometry oI
    CNT tip Iunctionalization, not along the length oI CNT core, was consistent with the experimentally observed selectivities.
    Bio-chemical gating oI CNTs is also seen by tethering desthiobiotin to CNT tips with the reversible binding to streptavidin.
    The complete ATP cycle (phosphylation/dephosphylation) can be perIormed on CNT tips with corresponding modulation oI
    Ilux across CNT membrane. The Iunctional density oI tethered charge molecules can be substantially increased by the use oI
    electrochemical graIting oI diazonium salts. Functionality can be Iorced to occur at the CNT tip entrances by Iast Iluid Ilow oI
    -41-
    an inert solvent through the core during electrochemical Iunctionalization. Changes in the Ilux and selectivity support a model
    where charged tethered molecules at the tips are drawn into the CNT core at positive bias hindering/gating Ilux across the
    membrane. Highly eIIicient electro-osmosis is seen in small diameter CNTs. Applications towards controlled transdermal
    drug delivery are discussed.
    In general, the transport mechanisms through CNT membrane are a) ionic diIIusion is near bulk expectation with no
    enhancement Irom CNT b) gas Ilow is enhanced by ~1-2 order oI magnitude due to specular reIlection oII oI Ilat graphitic
    surIace c) and pressure driven Ilux oI a variety oI solvents (H
    2
    O, hexane, decane ethanol, methanol) are 4-5 ORDERS OF
    MAGNITUDE FASTER than conventional Newtonian Ilow due to atomically Ilat graphite planes inducing nearly ideal slip
    conditions.
    |1| 'Experimental Observation oI Enhanced Liquid Flow through Aligned Carbon Nanotube Membranes Majumder, M.;
    Chopra, N.; Andrews, R; Hinds, B.J * Nature 2005, 438, 44
    |2| 'Voltage Gated Carbon Nanotube Membranes Majumder, M.; Zhan, X; Andrews, R; Hinds, B.J * Langmuir 2007 23,
    8624-8631
    |3| 'Aligned Multiwalled Carbon Nanotube Membrane Hinds, B.J.*; Chopra, N.; Andrews, R.; Gavalas, V.; Bachas L.
    Science 2004 303 62-65.
    OB.1.1
    Analysis of the free volume distribution in hyflon AD glassy perfluoropolymers by
    photochromic probes: comparison with other techniques
    J. C. Jansen
    1
    , M. Macchione
    1
    , E. Tocci
    1
    , L. De Lorenzo
    1
    , Y. P. Yampolskii
    2
    , V. P. Shantarovich
    3
    , M. Heuchel
    4
    ,
    D. HoImann
    4
    , E. Drioli
    1,5
    1
    Institute on Membrane Technologv, ITM-CNR, Jia P. Bucci 17/C, 87030 Rende (CS), Italv
    2
    A.J. Topchiev Institute of Petrochemical Svnthesis, 29 Leninskv Prospect, 119991, Moscow, Russian Federation.
    3
    N. N. Semenov Institute of Chemical Phvsics, Russian Academv of Sciences, 4 Kosvgina Str., 117334, Moscow
    4
    GKSS Research Center, Institute of Chemistrv, Kantstrasse 55, D-14513, Teltow, Germanv
    5
    Universitv of Calabria, Department of Chemical Engineering and Materials, Jia P. Bucci 44/A, 87030 Rende (CS), Italv.
    jc.jansenitm.cnr.it
    The Iree volume (FV) plays a Iundamental role in the diIIusion-controlled mass transport in polymeric materials. Knowledge
    oI the FV is thereIore oI great importance Ior the understanding oI the gas transport phenomena in dense polymeric
    membranes. Nowadays, one oI the most commonly used methods Ior the analysis oI FV is Positron Annihilation LiIetime
    Spectroscopy (PALS) but several alternative techniques exist, each oI them having its speciIic limits and advantages |1|.
    The present paper describes the successIul application oI the photochromic probe technique Ior the determination oI the Iree
    volume distribution (FVD) in amorphous glassy perIluoropolymers, in particular in two grades oI HyIlon

    AD (Solvay-
    Solexis) with a diIIerent copolymer composition |2|. In this method the degree oI photoisomerization oI appropriate probe
    molecules in the glassy polymer matrix is measured as a Iunction oI the volume required Ior the isomerization reaction |3|. Six
    diIIerent azobenzene- and stilbene based probes were used, with isomerization volumes ranging Irom 271A
    3
    to 574A
    3
    .
    Results reveal that HyIlon AD80X membranes possess bigger Iree volume elements (FVE) than HyIlon AD60X. This was
    conIirmed by PALS studies, indicating Iurthermore that the higher FVE size in HyIlon AD80X was accompanied by a lower
    FVE concentration. The same trend was observed Ior solution cast samples in comparison with melt-pressed samples, the latter
    having FVEs with a smaller size but at a higher concentration.
    Molecular dynamics (MD) simulation studies were carried out and detailed atomistic packing models were obtained Ior both
    HyIlon polymers. The packing models were used to analyze the amount and size distribution oI the FVEs. The simulation
    studies conIirm the higher Iree volume oI HyIlon AD80X in comparison to AD60X. The experimental and modelling results
    were Iurther compared with literature data Irom
    129
    Xe NMR spectroscopy. Finally the Iree volume distribution was correlated
    with the gas transport properties oI HyIlon AD membranes. This is the most complete comparative study oI diIIerent FV
    analysis and modelling techniques on perIluorinated polymers reported so Iar.
    The Iinancial support Irom the EU 6
    th
    Framework Program Project MultiMatDesign is grateIully acknowledged.
    |1| Yu.P. Yampolskii, Methods Ior investigation oI the Iree volume in polymers, Russ. Chem. Rev. 76 (2007) 59-78.
    |2| J.C. Jansen, M. Macchione, E. Tocci, L. De Lorenzo, Yu.P. Yampolskii, V.P. Shantarovich, M. Heuchel, D. HoImann, E.
    Drioli, submitted.
    |3| J.G. Victor, J.M. Torkelson, On measuring the distribution oI local Iree volume in glassy polymers by photochromic and
    Iluorescence techniques, Macromolecules, 20 (1987) 2241-2250.
    -42-
    OB.1.2
    Polymer-solvent interaction as a factor influenced on properties and gas separation
    characteristics of polymer films
    J. Kostina
    1
    , G. Bondarenko
    1
    , A. Alentiev
    1,2
    , Y. Yampolskii
    1
    , I. Ronova
    3
    1
    A.J.Topchiev Institute of Petrochemical Svnthesis, 29 Leninskv Pr., 119991, Moscow, Russia
    2
    M.J.Lomonosov Moscow State Universitv, Chemistrv department, Leninskie Gorv, 1, 119991, Moscow, Russia

    3
    A.N.Nesmevanov Institute of Elementoorganic Compounds Russian Academv of Sciences, Javilova st. 28, Moscow, Russia,
    119991
    juliaips.ac.ru
    The inIluence oI solvent on glassy polymers properties is one oI the Iundamental problems oI polymer and membrane material
    science because polymer membranes are Iormed Irom solvent mixtures. The interaction oI polymer Iunctional groups with
    solvent in solution inIluences on thin Iilm Iormation process. The presence oI residual solvent and the way oI its removing
    Irom Iilm inIluences on polymer chain packing in material and thereIore on gas separation properties. Recent years this
    problem has been investigated actively |1-3|. So gas separation and mechanical properties oI polyetherimides (PEI) could be
    extremely modiIied by changing oI solvent and the way oI Iilm Iormation |35|. The similar changes were observed not only
    Ior PEI but also Ior polycarbonates |6|, cardo polyimides |5|, PIM1 |7|. The investigation oI interaction oI diIIerent chemical
    structure polymers (PEI, polyimides (PI), PIM) with solvents (chloroIorm, THF, DMF, DMA, N-MP) and alcohols and their
    inIluence on polymer properties has been carried out. The conIormation modiIications in polymer elementary unit have been
    controlled FTIR by using oI high-temperature cell (Bruker). The experiment results have been explained by means oI
    quantum-chemical calculations (Gaussian03). It has been shown that solvent having ability to hydrogen bonding with polymer
    heteroatoms promoted the shiIt and reduction oI absorption bands quantity oI Iunctional groups in IR spectrum oI polymers.
    Theoretical calculations oI such models show increase oI barriers oI rotation and chain rigidity, Iormation oI chain
    conIormational uniIormity. It deIines the packing density during Iilm Iormation and residual solvent desorption and inIluences
    on material gas separation characteristics. The proposed approach gives an opportunity to predict and to control oI polymer
    material property changing that is the important step to new membrane preparation.
    |1| C. Joly, D. Le CerI , C. Chappey, D. Langevin, G. Muller, Separation and PuriIication Technology 16 (1999) 4754
    |2| R. Recio, L. Palacio, P. Pradanos, A. Hernandez, A. E. Lozano, A.Marcos, J. G. de la Campa, J. de Abajo.J oI Membr. Sci,
    293.(2007). I. 1-2. P. 22
    |3| Kostina J., Bondarenko G., Alentiev A., Rusanov A. Book oI abstract: 8
    th
    Internetional Symposium on Polyimides & high
    PerIomance Materials (STEPI 8), 0911.07.2008. Montpellier, P. 73.
    |4| Yu. V. Kostina, G. N. Bondarenko, A. Yu. Alent`ev, Yu. P. Yampol`skii, Polymer Sci. A.(2007) N 1. P.77
    |5| A. P. Korikov, Ya. S. Vygodskii, Yu. P. Yampol`skii. Polymer Science. A. 2001. V. 43. N 6. P. 638
    |6| P. Hacarlioglu,1 L. Toppare,2 L. Yilmaz, J. App. Pol. Sci, V. 90, 776785 (2003)
    |7| Peter M. Budd, Neil B. McKeown, Bader S. Ghanem, Kadhum J. Msayib, Detlev Fritsch, Ludmila Starannikova, Nikolai
    Belov, Olga SanIirova, Yuri Yampolskii, Victor Shantarovich, J. oI Membr. Sci, V.325. I. 2. 1 December 2008. P. 851-860
    OB.1.3
    Gas transport in glassy polymers for probing their supramolecular structure
    A. Alentiev
    1,2
    , Y. Yampolskii
    1
    , G. Bondarenko
    1
    , J. Kostina
    1
    , E. Antipov
    1
    1
    A.J.Topchiev Institute of Petrochemical Svnthesis, 29 Leninskv Pr., 119991, Moscow, Russia
    2
    M.J.Lomonosov Moscow State Universitv, Chemistrv department, 1, Leninskie Gorv, Moscow, Russia

    119991
    alentiev1963mail.ru
    A study oI chain packing in glassy polymers is one oI the Iundamental problem oI polymer and membrane materials science.
    The variation oI the chemical structure oI the repeat units, the chain conIormation set and supramolecular structure that deIines
    the chain packing can result in signiIicant changes oI Iree volume and the transport parameters that depend on it. The results oI
    contemporary experimental and simulation methods Ior study oI amorphous polymers, such as positron annihilation liIetime
    spectroscopy (PALS), inverse gas chromatography, and other probe methods, as well as the molecular dynamics gave
    evidences oI microheterogeneous structure oI the amorphous phase. It can be envisaged that Iree volume in glassy polymers
    has a wide, possibly multimodal size distribution, the microcavities (Iree volume elements) being distributed in more densely
    packed matrix oI the polymer. It is important that the number density oI Iree volume elements in polymers oI diIIerent nature
    -43-
    is more or less constant and amounts 10
    20
    10
    21
    cm
    -3
    according to the data oI PALS as well as the results oI the analysis oI
    diIIusion activation energies (so-called 'hole-wall model |1,2|). A conclusion can be made that the permeability and diIIusion
    coeIIicients mainly depend on the average size oI Iree volume element, while the permselectivity is aIIected by the structure
    and ordering oI chains in the dense polymer matrix, i.e. 'walls. Thus, varying the structure oI 'holes and 'walls may be
    used Ior control oI the gas separation processes. In the present work we analyzed the transport parameters, Iree volume, IR
    spectra and the X-ray data Ior more than 25 polymers that belong to the classes oI polyimides, polyetherimides and
    polyphenylquinoxalines. It was shown that there exists an optimal chain stiIIness which provides the most ordered
    supramolecular structure having the highest selectivity oI gas separation. Such structure also can be reached by special
    conditioning oI the polymers in contact with diIIerent solvents, by annealing, multi-axis orientation, and using other physical
    and mechanical methods during the process oI membrane preparation. Using the X-ray method it was shown that the structure
    oI the most selective polymers having 'optimal stiIIness and high order oI the chains in the 'walls can be ascribed as
    aperiodic smectic. Thus, it was demonstrated that the selectivity oI gas separation is a parameter sensitive to the ordering oI
    chains in 'walls. Both chemical modiIication in the process oI the synthesis and directed physical modiIication while
    preparing the membrane can inIluence the chain packaging and, hence, control the permselectivity oI the membrane material.
    Directed thermo-chemical modiIication oI polymers leads to enlargement oI the 'holes and, thereIore, to increases in gas
    permeability not in expenses in permselectivity |3|, that is, does not aIIect the ordering in the 'walls.
    |1| Yampolskii Yu.P., Russ. Chem. Rev., 76, 59 (2007)
    |2| Alentiev A.Yu., Yampolskii Yu.P., J. Membr. Sci., 206, 291 (2002)
    |3| Young Moo Lee, ICOM 2008 July 12-18, 2008, Hawaii
    OB.1.4
    Structure and swelling of an immersed Nafion membrane under compression
    N. Otmani
    1
    , A. Morin
    1
    , H. Mendil-Jakani
    2
    , G. Gebel
    2
    , S. Besse
    3
    1
    CEA Grenoble, DRT/Liten/DTH/LCPEM, 17 avenue des Martvrs, 38054 Grenoble cedex 9, France
    2
    CEA Grenoble, DSM/INAC/SPrAM, 17 avenue des Martvrs, 38054 Grenoble cedex 9, France
    3
    Helion, Batiment Jules Jernes, avenue Louis Philibert, 13100 Aix-en-Provence, France
    nassim.otmanicea.Ir
    For a Iew years it appears that the mechanical considerations in proton exchange membrane (PEMFC) are a subject oI growing
    interest. Indeed, there is a large inIluence oI the mechanical stresses on the electrochemical perIormance oI the PEMFCs and
    on the degradation oI their components, and especially the membrane |1,2|. For example, during on/oII cycling, the membrane
    consecutively absorbs and desorbs water which can lead to a mechanical Iatigue.
    There are many results on the mechanical properties oI
    NaIion membranes under tensile tests |1,2|.
    However, no study on the behaviour oI these
    membranes under compressive stresses has been
    reported in the literature whereas the membranes
    experience compression in a PEMFC stack. We
    investigated the structure and the swelling oI the
    NaIion NRE212-CS membrane under diIIerent
    compressive stresses at ambient temperature using
    microIocus small angle X-ray scattering (SAXS). For
    this purpose, a device with the same geometry than the
    bipolar plate Ilow Iield and which allows to control the
    compressive stress has been designed. Our results
    show that the membrane, iI swelled Iirst, becomes
    anisotropic and could desorb beyond a pressure oI
    5 MPa. When the membrane is Iirst compressed beIore
    immersion in water, its swelling ability is reduced
    beyond 5 MPa.
    Figure 1 : Picture oI the device simulating ribs and channels
    (a) (b)
    Figure 2 : SAXS spectra in the membrane immersed and then
    compressed under the ribs ; a) at 1MPa and b) at 15MPa
    |1| S. Kundu L. C. Simon, M. Fowler, Stephen Grot, Mechanical properties oI NaIion electrolyte membranes under hydrated
    conditions, Polymer, 2005, 46(25), 11707-11715
    |2| Y. Tang, A. M. Karlsson, M. H. Santare, M. Gilbert, S. Cleghorn, W. B. Johnson, An experimental investigation oI
    humidity and temperature eIIects on the mechanical properties oI perIluorosulIonic acid membrane, Materials Science and
    Engineering: Part A, 2006, 425(1-2), 297-304
    -44-
    OB.1.5
    Keynote: Surface-functionalized membranes for low-fouling micro- and
    ultrafiltration and selective membrane adsorber applications
    M. Ulbricht
    Lehrstuhl fr Technische Chemie II, Universitt Duisburg-Essen, Universittsstrasse 5, D-45141Essen, Germanv.
    mathias.ulbrichtuni-due.de
    Applications oI membrane separations increase rapidly in terms oI number and size. However, in many cases, the state-oI-the-
    art membrane materials do not IulIill all requirements, Ior instance with respect to separation selectivity or to long-term
    stability oI membrane perIormance, in particular, Iouling resistance. ThereIore, surIace Iunctionalization oI membranes has
    become a very active Iield within membrane technologies |1|. A detailed characterization oI the obtained Iunctionalized
    membranes is the precondition to correlate the respective changes oI chemical and porous structure with changes in separation
    perIormance. Nowadays, a wide range oI spectroscopic and microscopic analytical methods has been or is being adapted to
    membrane characterization.
    In this presentation, we will discuss this by Iocusing on three diIIerent approaches towards surIace-Iunctionalized membranes
    which are currently studied in our group:
    - low-Iouling microIiltration membranes with regular pore structure, prepared via combination oI non-solvent induced
    phase separation with evaporation-induced phase separation oI blends oI membrane polymers (e.g., polyethersulIone)
    with tailored additives (e.g., amphiphilic block copolymers) |2,3|,
    - thin-Iilm hydrogel composite membranes Ior ultraIiltration with low-Iouling properties and adjustable separation curve,
    prepared via UV-initiated heterogeneous graIt copolymerization oI hydrophilic acrylates |4,5|,
    - macroporous membrane adsorbers with high dynamic binding capacity or with tailored binding selectivity, prepared via
    UV-initiated heterogeneous graIt copolymerization using either ion-exchange monomers or monomers with speciIic
    binding motives, respectively, in combination with suited comonomer compositions |6-9|.
    |1| M. Ulbricht, Polvmer 2006, 47, 2217-2262.
    |2| H. Susanto, M. Ulbricht, J. Membr. Sci. 2009, 327, 125-135.
    |3| H. Susanto, N. Stahra, M. Ulbricht, High perIormance polyethersulIone microIiltration membranes having high Ilux and
    stable hydrophilic property, 2009, submitted.
    |4| H. Susanto, M. Ulbricht, Langmuir 2007, 23, 7818-7830.
    |5| H. Susanto, H. AraIat, E. M. L. Janssen, M. Ulbricht, Separ. Purif. Techn. 2008, 63, 558-565.
    |6| J. Wang, F. Dismer, J. Hubbuch, M. Ulbricht, J. Membr. Sci. 2008, 320, 456-467.
    |7| A. H. M. YusoI, M. Ulbricht, J. Membr. Sci. 2008, 311, 294-305.
    |8| J. Wang, R. Faber, M. Ulbricht, InIluence oI pore structure and architecture oI photo-graIted Iunctional layers on separation
    perIormance oI cellulose-based macroporous membrane adsorbers, 2009, submitted.
    |9| D. M. He, W. Sun, T. Schrader, M. Ulbricht, J. Mater. Chem. 2009, 19, 253-260.
    OB.2.1
    High performance wet air oxidation (WAO) of organic pollutants using a catalytic
    membrane reactor
    M. Alame
    1
    , A. Abusaloua
    1
    , M. Pera-Titus
    1
    , N. Guilhaume
    1
    , S. Miachon
    1
    , K. Fiaty
    2
    , J-A. Dalmon
    1
    1
    Institut de Recherches sur la Catalvse et lEnvironnement de Lvon (IRCELYON), UMR5256 CNRS/Universite de Lvon, 2
    avenue A. Einstein, 69629 Jilleurbanne Cedex, France
    2
    Laboratoire dAutomatique et de Genie des Procedes (LAGEP), UMR5007 CNRS, CPE Lvon, Bat 308 G, Universite de Lvon,
    43 Bd du 11 novembre 1918, 69622 Jilleurbanne cedex, France
    mohamad.alameircelyon.univ-lyon1.Ir
    Catalytic membrane reactors (CMRs) appear as an attractive technology Ior the oxydation oI eIIluents where the concentration
    oI organics is too low Ior incineration and when biological treatment is not suitable due to toxicity or other limitations. In this
    concept, relying on the same principles as in catalytic wet air oxidation (CWAO), a metal catalyst is Iixed to an asymmetric
    and porous ceramic membrane in a catalytic membrane reactor oI the contactor type (CMR-C). Wastewater is pumped along
    the contactor on the catalytic layer side, while air or pure oxygen Ilows along the other side. The gas liquid interIace is located
    -45-
    within the membrane wall by means oI a transmembrane diIIerential pressure compensating the gas/liquid capillary pressure.
    This conIiguration Iavours three-phase (gas-liquid-solid) contact, leading to a better accessibility oI the reactants to the
    catalyst, improving thereIore the conversion rates. Besides the experimental conditions, the perIormance oI the interIacial
    catalytic contactor depends on a series oI critical parameters, like the respective positions oI the catalyst zone and the gas
    liquid interIace |1|.
    A series oI mono- and multicatalytic membranes (membrane containing more than one type oI catalyst particles, respectively)
    prepared on our premises have been used to remove pollutants oI model dilute solutions oI Iormic acid, acetic acid, and Oxalic
    acid. The catalytic results reveal that the catalytic perIormance oI the membranes prepared in this work depends strongly on
    how the membrane is wetted prior the catalytic tests. The bubble point pressure in ethanol using N
    2
    gas has been measured on
    several membranes using two diIIerent wetting methods: normal wetting and wetting under vacuum. Normal wetting consists
    oI setting down the membrane on a thin ethanol layer (that is not more than 1-mm height) and let the solvent Iill the pores by
    capillarity. The second wetting method is similar in concept to the Iormer, but now the liquid is Iorced into the porous network
    oI the membrane using primary vacuum. Our results reIlect that wetting under vacuum leads to much higher bubble point
    results, reducing thereIore the apparent` largest passing-through pores oI the support. These results translate into an activity
    aIter wetting under vacuum by Iive to eleven times higher than aIter normal wetting. We have also observed that the results
    obtained under pure O
    2
    are approximately two times better than that obtained under air.
    [1] E.E. Iojoiu, J.C. Walmsley, H. Rder, S. Miachon, J.-A. Dalmon, Catal. Today 104 (2005) 329.
    OB.2.2
    Gas transport properties through PVDF membrane
    S.H. Choi
    1
    , J. C. Jansen
    1
    , F. Tasselli
    1
    , G. Barbieri
    1
    , E. Drioli
    1,2
    1
    National Research Council - Institute on Membrane Technologv (ITMCNR) Jia Pietro BUCCI, c/o The Universitv of
    Calabria, cubo 17C, 87030 Rende CS, Italv
    2
    The Universitv of Calabria - Department of Chemical Engineering and Materials, cubo 44A Jia Pietro BUCCI, 87030 Rende
    CS, Italv
    sh.choiitm.cnr.it
    Poly(vinylidene Iluoride) is widely used as a membrane material Ior its good chemical and mechanical resistance. Its main use
    is in microIiltration and ultraIiltration processes. Because oI its very hydrophobic character also its application in membrane
    contactors has been suggested. All these applications concern porous membranes, where transport takes place through the
    pores in the membranes.
    Due to its semi-crystalline character, PVDF has a relatively low permeability oI the dense matrix and thereIore only Iew papers
    on the use oI PVDF as gas separation membranes |1| or pervaporation membranes |2| have been reported in the literature.
    Nevertheless, the chemical structure with high Iluorine content and the presence oI highly polarized C-F bonds gives this
    polymer some particular properties. For instance it has a higher He/H
    2
    selectivity (~3) than corresponding hydrocarbon
    polymers. In general Iluorinated polymers, among which the amorphous perIluoropolymers TeIlon AF

    and HyIlon AD

    are
    receiving increasing attention Irom the membrane community nowadays because oI their interesting gas and vapor transport
    properties.
    In the present paper we studied the gas transport oI dense asymmetric hollow Iiber membranes prepared by dry-wet and/or wet
    spinning technique. The experimental results oI permeation test were compared with those oI dense PVDF Iilms prepared by
    extrusion. The relation between the Iiber morphology and the spinning conditions also discussed. Particular attention was paid
    to the reduction oI the skin thickness in order to obtain a suIIiciently high permeance, in spite oI the intrinsically low
    permeability coeIIicient oI PVDF.
    The transport properties were determined via time-lag measurements and were discussed in terms oI diIIusion, solution and
    permeability coeIIicients and selectivity Ior various permanent gases. The results will contribute to a better understanding oI
    the transport phenomena in Iluorinated polymers.
    |1| M. J. El-Hibri, and D. R. Paul, "Gas transport in poly(vinylidene Iluoride): EIIects on uniaxial drawing and processing
    temperature", J. Appl. Polvm. Sci., 31 (1986) 2533-2560.
    |2| K. Jian, and P. N. Pintauro, "Asymmetric PVDF hollow-Iiber membranes Ior organic/water pervaporation separations", J.
    Membr. Sci., 135 (1997) 41-53.
    The Italian Ministrv of Education, Universitv and Research, Progetto 'FIRBCAMERE RBNE03JCR5 Nuove membrane
    catalitiche e reattori catalitici a membrana per reazioni selettive come sistemi avanzati per uno sviluppo sostenibile is
    grateIully acknoledged Ior co-Iunding this work.
    -46-
    OB.2.3
    Oily wastewater treatment by means of y-alumina nanofiltration membrane
    Z. Sadeghian
    1
    , F. Zamani
    2
    , N. AshraIizadeh
    2
    1
    Gas Research Division, Research Institute of Petroleum Industrv (RIPI), Tehran, P.O. Box. 148573311
    2
    Chemical Engineering Department, Iran Universitv of Science & Technologv (IUST), Tehran, P.O. Box. 16765163
    sadeghianzripi.ir
    NanoIiltration (NF) has proven to be a very eIIective method Ior the removal oI a wide variety oI organic compounds Irom
    aqueous solution |1|. NF operations normally produce a higher water Ilux and can oIten operate at lower pressures, which
    reduce energy consumption |2|. OilIield wastewater known as produced water is generated in large quantities in onshore and
    oIIshore oil exploitation |3|. Wastewaters Irom oilIields produced during many stages oI crude oil production, recovery and
    transportation represent a major environmental and processing problem Ior the petroleum industry |4|.
    In the present work the nanoporous y-alumina membranes
    have prepared with an average pore size oI 2 nm (Fig.1).
    Oily wastewater treatment has been studied by the cross-
    Ilow nanoIiltration processes using above membranes. The
    eIIect oI operating parameters on treatment oI
    nanoIilotratioin process was studied. The inIluence oI
    parameters such as transmembrane pressure (TMP),cross
    Ilow velocity (CFV) and oil concentration in Ieed on the
    separation behaviors were investigated by the
    measurements oI permeate Ilux, total organic carbon
    (TOC) removal eIIiciency. The TOC removal eIIiciencies
    higher than 90 were achieved under all experimental
    conditions.
    Fig.1. SEM picture oI nanoporous y-alumina membrane
    |1| P. Berg, G. Hagmeyer, R. Gimbel, Removal oI pesticides and other micropollutants by nanoIiltration, Desalination, 1997,
    113 (2/3), 205208.
    |2| R. Haddad, E. Ferjani, M.S. Roudesli, A. Deratani, Properties oI cellulose acetate nanoIiltration membranes. Application to
    brackish water desalination, Desalination 2004, 167, 403409.
    |3| K. Shams Ashaghi1, M. Ebrahimi and P. Czermak, Ceramic Ultra- and NanoIiltration Membranes Ior OilIield Produced
    Water Treatment: A Mini Review The Open Environmental Journal, 2007, 1, 1-8.
    |4| Q. Li, C. Kang, C. Zhang, Waste water produced Irom an oilIield and continuous treatment with an oil-degrading
    bacterium. Proc Biochem, 2005, 40, 873-877.
    OB.2.4
    Determining the virus removal retention capabilities of UF membranes during
    operation at pilot scale
    H. Humbert, C. Machinal, I. Labaye, V. Jacquemet, P. Brisson, J.C. Schrotter
    Water Research Center Jeolia Environnement, chemin de la digue, 78600 Maisons-Laffitte, France
    hugues.humbertveolia.com
    The determination oI the virus retention capabilities oI UF units during operation is essential Ior the operators oI drinking
    water treatment Iacilities in order to guarantee an eIIicient and stable removal oI viruses through time. In previous studies, an
    eIIective method (MS2-phage challenge tests) was developed by the Water Research Center oI Veolia Environnement Ior the
    measurement oI the virus retention rates (Log Removal Rate, LRV) oI commercially available hollow Iiber membranes at lab
    scale |1, 2|. In the present work, the protocol Ior monitoring membrane perIormance was transIerred Irom lab scale to pilot
    scale. Membrane perIormances were evaluated all along the pilot trial and compared to the results obtained at lab scale with
    Iibers taken Irom the pilot modules. Cell culture is a reliable but expensive and time-consuming method. As a consequence,
    PFU method was compared to RT-PCR method Ior the calculation oI LRV in both cases. Preliminary tests at lab scale showed
    that both methods can be used indiIIerently (Figure 1). As shown on Figure 2, Ior tests conducted on virgin membrane, a good
    consistency was observed between lab and pilot scale results with the 2 methods tested. This work intends to show that a
    -47-
    reliable determination oI the membranes perIormances based on RT-PCR analytical method can be achieved during the
    operation oI the UF units.
    Figure 1 : Log removal value obtained by RT-PCR method
    (x-axis) and PFU method (y-axis)
    Figure 2 : Log removal value oI virgin membrane at lab scale
    and pilot scale with PFU and RT-PCR methods
    |1| Jacangelo J. G., Adham S. S. and al (1995), Mechanism oI cryptosporidium, giardia, and MS2 virus removal by MF and
    UF, J Am Water Work Assoc 107-121.
    |2| Langlet J., Ogorzaly L., Schrotter J.C., Machinal C., Gaboriaud F., Duval J. F. L. and Gantzer C. (2009). EIIiciency oI
    MS2 phage and Q phage removal by membrane Iiltration in water treatment: Applicability oI a real-time RT-PCR method.
    Journal oI Membrane Science, 326, 111-116.
    |3| Schrotter J.C., Rapenne S., Machinal C., Arnal C., Jacob P., Delabre K., (2008), Toward a deeper understanding and
    characterization oI membrane in water treatment. IWA Moscow 2008
    OB.2.5
    Membranes for pressure retarded osmosis power plants
    T. Holt
    1
    , E. Sivertsen
    2
    , T. Thorsen
    2
    1
    SINTEF Petroleum Research , Seismic and Reservoir Technologv, NO-7465 Trondheim, Norwav
    2
    SINTEF Building and Infrastructure, Water and Environment, NO-7465 Trondheim, Norwav
    TorleiI.HoltsinteI.no
    Salinity power is a renewable and sustainable energy resource with a signiIicant potential world-wide which has lead to
    increasing attention in the recent years. Pressure retarded osmosis (PRO) is one oI the technical Ieasible processes which can
    be used to extract some oI the mixing energy that is otherwise lost when Iresh water is mixed with sea water outside river
    mouths.
    EIIective utilisation oI mixing energy by PRO requires membranes with diIIerent properties than available commercial reverse
    osmosis membranes have today. The new membranes must have high water permeability (A), low salt permeability (B) and
    short eIIective diIIusion length in the support structure (a parameter called S). The importance oI the three parameters A, B and
    S Ior the eIIiciency oI osmotic processes will be discussed by use oI a transport model that includes concentration polarisation
    on the membrane surIaces. The validity oI the model will be substantiated through modelling oI laboratory experiments done
    with both cellulose acetate and thin Iilm composite membranes.
    By use oI the transport model it will be shown which values oI the parameters A, B and S that are needed in order to obtain
    given values Ior the speciIic power (W/m
    2
    ) Ior Iresh water/sea water PRO, and the importance oI a low value oI S will be
    stressed. The perIormance oI membranes Ior other Iluid pairs with higher diIIerences in osmotic pressures will also be shown.
    The eIIect oI a possible coupling oI water and solute in the membrane skin will be discussed.
    Results Irom laboratory testing oI both commercial and development membranes in osmosis and PRO modes will be
    presented. For many membranes the observed perIormance was low and this can oIten be related to large values oI the
    structure parameter, S.
    Large values oI S may be related to incomplete wetting oI water in the support membrane and/or due to disproportionate
    resistance in the reinIorcement. In some cases it appears as the reinIorcement seals oII some oI the support membrane Ior mass
    transport. These possible causes will be discussed with basis in osmotic Ilow experiments.
    Compression oI the support structure is another Iactor that may impair the perIormance oI a membrane in PRO. The presence
    oI this phenomenon and its links to the Iactors above will be discussed.
    The requirements Ior a support structure suitable Ior PRO membranes will Iinally be summarised.
    -48-
    OB.2.6
    Performances of aquasource new ultrafiltration membranes
    L. Feriol - Technical Director, P. Sauvade - R&D Engineer
    Aquasource - 20, avenue Didier Daurat - 31029 TOULOUSE CEDEX 4 - Tel . 0033 (0)5 61 36 30 36 - Fax . 0033 (0)5 61 36
    30 60
    patrick.sauvadeaquasource.Ir
    In this study, we propose to present and discuss about several characterizations oI cellulose triacetate and hydrophilic
    polysulIone membranes and their high operating behavior. These membranes are the latest high perIormances membranes
    developed by Aquasource.
    The triacetate cellulose membrane, naturally hydrophilic and is thereIore less subject to clogging. This membrane his
    especially adapted Ior drinking water applications.
    The hydrophilic polysulIone membrane has been developed in order to ensure high perIormances with high Ilux oI operation,
    especially Ior settled water, reuse and reclaim oI waste water.
    The main characteristics oI these membranes are their high productivity, their mechanical resistance and their high selectivity.
    In order to illustrate these points, we Iirstly present global mechanical and hydraulical properties included water permeability,
    mechanical ageing, cut oII curves with artiIicial tracers (dextrans) and LRV values with MS2 viruses. In a second way, we
    present and discuss about operated curves included assessment oI nominal / maximum Iiltration Ilux, stabilized permeability,
    backwash regime and chemical cleaning Irequency in addition to the typical water quality perIormance parameters oI these
    membranes on their application. The triacetate cellulose membranes on karstic water and hydrophilic polysulIone membranes
    applied to reuse oI wastewater.
    OB.2.7
    Partially positively polarized surface of silver and gold nanoparticles by electron
    acceptor and its implication to facilitated olefin transport
    Y.S. Kang
    1
    , S. W. Kang
    2
    , J. Won
    3
    1
    Department of Chemical Engineering, Hanvang Universitv, Seou1, South Korea
    2
    School of Chemical and Biological Engineering, Seoul National Universitv, Seoul, South Korea
    3
    Department of Applied Chemistrv, Sefong Universitv, Seoul, South Korea
    kangyshanyang.ac.kr
    A new application oI metallic silver and gold nanoparticles as a novel oleIin carrier Ior Iacilitated oleIin transport membranes
    was explored. Silver and gold nanoparticles were chemically activated by suitable electron acceptors such as ionic liquids
    (ILs), p-benzoquinone, or 4-dimethylaminopyridine (DMAP) to enhance speciIic interactions with oleIin molecules. |1-4|
    Facilitated oleIin transport membranes containing chemically activated metal nanoparticles showed good separation
    perIormance in both selectivity and mixed gas permeance.
    It was shown that the introduction oI suitable electron acceptors caused the surIace oI the metallic nanoparticles to become
    positively polarized as evidenced by X-ray photoelectron spectroscopy, resulting in enhanced carrier activity oI metal
    nanoparticles toward oleIin molecules, and consequently Iacilitated oleIin transport.
    It was Iound that the surIace charge density seemed to be strongly correlated with the carrier activity oI the metallic
    nanoparticles. ThereIore the correlation between the charge density oI metallic nanoparticles and the Iacilitated oleIin transport
    was investigated systematically by varying three diIIerent ionic liquids. As a result, we Iound that as the polarity oI the metallic
    nanoparticles was changed upon the addition oI the diIIerent ionic liquids, and that the separation perIormance Ior
    propylene/propane mixtures was also markedly increased with the surIace charge density.
    This work was supported by Energy Technology R&D program (2006-E-ID11-P-13) under the Ministry oI Knowledge
    Economics oI Korea.
    |1| Y. S. Kang,

    S. W. Kang, H. Kim, J. H. Kim, J. Won, C. K. Kim, K. Char, Adv. Mater., 2007, 19, 475.
    |2| S. W. Kang, K. Char, Y. S. Kang, Chem. Mater., 2008, 20, 1308.
    |3| S. W. Kang, D. H. Lee, J. H. Park, K. Char, J. H. Kim, J. Won, Y. S. Kang, J. Membr. Sci., 2008, 322, 281.
    |4| S. W. Kang, J. Hong, J. H. Park, S. H. Mun, J. H. Kim, J. Cho, K. Char, Y. S. Kang, J. Membr. Sci., 2008, 321, 90.
    -49-
    OB.2.8
    Atomic force microscope characterization of ceramic ultrafiltration membranes in
    different operational states
    J.Llanos
    1
    , A. Perez
    1
    , P. M. Williams
    2
    , S.Y. Cheng
    2
    , D. Rogers
    2
    , C. Wright
    2
    1
    Chemical Engineering Department, Facultv of Chemical Sciences, Universitv of Castilla-La Mancha, Avda. Camilo Jose Cela
    12, 13005 Ciudad Real, Spain.
    2
    Department of Chemical and Biological Process Engineering, Centre for Complex Fluids Processing,Universitv of Wales
    Swansea, Singleton Park, Swansea SA2 8PP, UK
    jgcdq.Ict.unl.pt, javier.llanosuclm.es
    Atomic Force Microscope (AFM) can be used to obtain topographical images by scanning a sharp tip over a target surIace.
    This technique has been applied to the study oI both nanoIiltration and ultraIiltration membranes as it gives important and
    useIul inIormation about surIace morphology, surIace pore size distribution and surIace porosity |1|.
    On the other hand, Polymer Supported UltraIiltration (PSU) is a membrane separation process that has been extensively used
    to treat water eIIluents with heavy metal ions. In this technique, a water-soluble polymer reacts with a target metal ion to Iorm
    a macromolecular complex that is retained by an ultraIiltration membrane. The presence oI the polymer causes a permeate Ilux
    decrease due to either Iouling or concentration polarization, both phenomena caused by a polymer-membrane interaction. This
    interaction is inIluenced by the polymer Iunctional groups and the solution pH |2|.
    In the present study, the Atomic Force Microscope technique has been used to characterise a Carbosep M5 ceramic membrane
    (MWCO 10 KDa, TiO
    2
    -ZrO
    2
    active layer). This membrane was
    previously used in a PSU process to recover copper, using partially
    ethoxylated polyethylenimine as water-soluble polymer |3|.
    The membrane was characterized in three diIIerent operational
    states: new, Iouled in a PSU stage and cleaned aIter a PSU stage.
    The inIluence oI the membrane state on surIace pore size
    distribution, porosity and roughness was studied. Furthermore, phase
    angle distributions were also analyzed to indicate the Ioulant
    distribution on the membrane surIace. As an example, Fig. 1 shows
    an AFM image oI a 500 x 500 nm area Ior the new CARBOSEP M5
    membrane.
    Moreover, AFM was used to measure the inIluence oI pH on the
    adhesion Iorces between a silica probe and the membrane active
    layer. These results can be related to the Ilux evolution vs. pH in
    PSU experiments.
    |1| W. R. Bowen, S. Y. Cheng, T. A. Doneva, D. L. Oatley, ManuIacture and characterisation oI polyetherimide/sulIonated
    poly(ether ether ketone) blend membranes, J. Membr. Sci., 250 (2005) 1-10.
    |2| P. Caizares, A. de Lucas, A. Perez and R. Camarillo, EIIect oI polymer nature and hydrodynamic conditions on a process
    oI polymer enhanced ultraIiltration, J. Membrane Sci., 253 (2005) 149.
    |3| J. Llanos, A. Perez, P. Caizares, Copper recovery by polymer enhanced ultraIiltration (PEUF) and electrochemical
    regeneration, J. Membr. Sci., 323 (2008) 28-36.
    OB.2.9
    Volumetric properties and mass transfer of sugars through a NF membrane:
    influence of the ionic composition
    V. Boy
    1

    ,2
    , S. Galier
    1,2
    , H. Roux-de Balmann
    1,2
    1
    Universite de Toulouse , INPT, UPS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    2
    CNRS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    galierchimie.ups-tlse.Ir
    Recent studies have shown that unexpected perIormances can be obtained with nanoIiltration membranes, when applied to the
    treatment oI solutions containing signiIicant amount oI salt. The inIluence oI the salts on the transIer oI neutral organic solutes,
    -50-
    Fig. 1. AFM image oI a new Carbosep M5
    membrane.
    like polysaccharides and organic acids, was thus pointed out
    1,2
    . More precisely, it was observed that, in diIIerent situations, the
    transIer oI organic solutes can be increased by the addition oI salt. It was also reported that this increase depends on the salt
    concentration and on the salt nature. It was suggested that the improvement oI the transIer oI the neutral specie could result
    Irom a modiIication oI its hydration, which is expected to vary with the ionic composition
    2
    . Indeed, iI less hydrated because oI
    a preIerential hydration oI the salt, the organic solute could have a lower size and thus transIer more easily through the
    membrane.
    In any case, the understanding oI the mechanisms governing the mass transIer oI organic solutes through membrane separators,
    and specially their dependence on the ionic composition, is thus a target Ior a better prediction oI the perIormances oI the
    processes in which these membranes are to be used.
    The methodology developed in this study consists to determine relevant physicochemical parameters to characterize the
    hydration state oI neutral solutes and to investigate their mass transIer through NF membranes in solutions oI diIIerent ion
    compositions.
    On one hand, volumetric properties are considered since they are expected to provide useIul inIormations concerning the
    hydration state oI neutral solutes with respect to the ionic composition. Among the diIIerent methods than can be considered to
    reach such characteristics, the measurement oI the density is investigated in present work. Such measurements were previously
    used in the case oI sugar/sodium chloride solutions to get the molar volumes oI the sugars and it was demonstrated that this
    volume is aIIected by the presence oI salt
    3
    .
    One the other hand, the mass transIer oI the organic solutes through a NF membrane (45 Filmtec) is studied in a diIIusion
    regime, i.e. in such conditions where it is Iorced by a concentration gradient created on both sides oI the membrane. Sugars oI
    increasing molecular weights (xylose, glucose and saccharose) are used as organic species. DiIIerent electrolytes (NaCl, CaCl
    2
    ,
    Na
    2
    SO
    4
    .) are chosen with respect to their valence, since it is linked to the hydration level. It is observed that the transIer oI
    the organic solute increases in the presence oI salt and the corresponding increase is more important Ior sugar oI increasing
    molecular weight.
    Finally, these results are put in parallel with the volumetric properties which characterize the hydration state oI the solute.
    |1| G. Bargeman, J.M. Vollenbroek, J. Straatsma, C.G.P.H. Schroen, R.M. Boom, NanoIiltration oI multi-component Ieeds.
    Interactions between neutral and charged components and their eIIect on retention, J. Membrane Sci., 2005,247, 11-20
    |2| A. Bouchoux, H. Roux-de Balmann, NanoIiltration oI glucose and sodium lactate solutions. Variations oI retention
    between single- and mixed-solute solutions, J. Membrane Sci., 2005, 258, 123-132
    |3| K. Zhuo, J. Wang, Y. Yue, H. Wang, Volumetric properties Ior the monosaccharide (D-xylose, D-arabinose, dglucose, D-
    galactose)-NaCl-water systems at 298.15 K, Carbohydrate Research, 2000, 328, 383-391
    OB.2.10
    Characterization of polymer electrolyte membrane -relationship between
    morphology and transport properties-
    A. Ohira
    1
    , N. Takimoto
    1
    , H. F. M. Mohamed
    1
    , K. Kidena
    1
    , T. Ohkubo
    1
    , Y. Kobayashi
    2
    1
    Polvmer Electrolvte Fuel Cell Cutting-edge Research Center (FC-Cubic), National Institute of Advanced Industrial Science
    and Technologv, 2-41-6 Aomi, Koto-ku, Tokvo 135-0064, Japan
    2
    NMIJ, National Institute of Advanced Industrial Science and Technologv,Tsukuba, Ibaraki 305-8565, Japan
    a-oohiraaist.go.jp
    Polymer Electrolyte Membrane (PEM) is one oI the most
    important components Ior a Polymer Electrolyte Membrane Fuel
    Cell (PEFC). PEM is required various characteristics such as
    high proton conductivity with low humidity, gas barrier, physical
    and chemical stability. We have conducted characterization oI
    structural dependence oI transport properties such as proton
    conduction, water diIIusion and gas permeation, on PEMs by
    various analytical methods. To investigate the relationship
    between morphology and proton conduction, AC-mode Atomic
    Force Microscopy coupled with electrochemical technique (E-
    AFM) which we have newly developed was used as shown Figure
    1.|1|
    For investigation oI the relationship between morphology and gas
    permeation, Positron Annihilation LiIetime Spectroscopy (PALS)
    technique was used to analysis the microstructures oI polymers,
    -51-
    Figure 1. Comparison oI morphologies between NaIion


    and SPES.
    in particular, sub-nanometer sized Iree volume holes.|2| We have demonstrated the diIIerence on morphology related to proton
    conduction and gas permeation
    between perIluorinated and hydrocarbon ionomer membranes.
    Ministry oI Economy, Trade and Industry (METI), Japan and New Energy and Industrial technology Development
    Organization (NEDO) are acknowledged Ior granting the work.
    |1| N. Takimoto, L. Wu, A. Ohira, Y. Takeoka, M. Rikukawa, Polymer, 2009, 50, 534-540.
    |2| M. F. M. Hamdy, K. Ito, K. Kobayashi, N. Takimoto, Y. Takeoka, A. Ohira, Polymer, 2008, 49, 3091-3097.
    OB.3.1
    In situ characterisation of membrane formation by phase inversion
    J. Mendret
    1, 2
    , P. Bacchin
    1, 2
    , J-C. Remigy
    1, 2
    1
    Universite de Toulouse , INPT, UPS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    2
    CNRS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09,France
    mendretchimie.ups-tlse.Ir
    Phase inversion process is a common method to produce polymeric membranes. Usually, a dope solution which consists oI a
    polymer and a solvent, is Iormed into the desired shape (Ilat-sheet, hollow Iibre.).Then the dope solution is contacted with a
    non-solvent bath (usually water), the dope solution composition will change due to exchange oI solvent and non-solvent
    between non-solvent bath and polymer Iilm. This mass-transIer oI the three components, combined to the thermodynamic
    equilibrium, leads to phase inversion: a polymer rich phase and a polymer lean phase are obtained. The polymer rich phase will
    gel and give the membrane structure while the polymer lean phase will evolve through coalescence step into the membrane
    pores. The Iinal structure oI the membrane depends on the mass transIer (diIIusion coeIIicient, gradient concentration) and
    thermodynamics equilibrium between the polymer, the solvent and the non solvent but also on the presence oI the nascent skin
    which leads to an heterogeneous diIIusion.
    In this study, in situ observations oI the phase inversion are proposed. A Iilm oI dope solution was placed between two
    microscope slides. The precipitant was either introduced near the edge by liquid water (wet phase inversion) or by the air
    humidity (vapour induced inversion). The phenomena was then observed under an optical microscope and recorded by a
    camera. This approach enable a link between the operating parameters (process oI elaboration, polymer concentration...) and
    the Iinal structure to be established. It was possible to understand how well-known structures are obtained: sponge like
    structure (Iig. 1), Iinger like structure (Iig. 1). Other observations under an artiIicial skin were also perIormed.
    In parallel, a model was developed in order to
    simulate the heterogeneous diIIusion through the
    nascent skin oI the membrane. In this model,
    diIIusion coeIIicient are Iunction oI the
    concentration in polymer, solvent and non solvent.
    In particular, a law describing the diIIusion
    coeIIicient oI the polymer was established. It takes
    into account the decrease to zero oI the diIIusion
    coeIIicient oI the polymer when approaching the
    spinodal curve. This theoretical approach enables the
    role oI the nascent skin to be understood.
    Figure 1:leIt: Formation oI a Iinger like structure; right: Formation oI
    a sponge like structure.
    |1| H. Strathmann, K. Kock, P. Amar, R.W. baker, Desalination, 1975, 16, 179-203.
    |2| S. Kuiper, C.J.M.van Rijn, W. Nijdam, M.C. Elwenspoek, J. Mbr. sci, 1998, 150, 1-8.
    -52-
    OB.3.2
    Positron annihilation spectroscopy: a novel non-destructive characterization
    technique to probe the molecular level of polyimide-based solvent resistant
    nanofiltration membranes
    A. Cano-Odena
    1
    , P. Vandezande
    12
    , K. Hendrix
    1
    ,

    R. Zaman
    1
    , K. MostaIa
    3
    , W. Egger
    4
    , P. Sperr
    4
    ,
    J. De Baerdemaeker
    35
    , I.F. J. Vankelecom
    1
    1
    Centre for Surface Chemistrv and Catalvsis, Facultv of Bioscience Engineering, Katholieke Universiteit Leuven, Kasteelpark
    Arenberg 23 box 2461, B-3001 Leuven, Belgium
    2
    Present address. Flemish Institute for Technological Research (JITO), Boeretang 200, B-2400 Mol, Belgium
    3
    NUMAT (Nuclear Methods in Materials Science), Dept. Subatomic and Radiation Phvsics, Ghent Universitv, Proeftuinstraat
    86, B-9000 Gent, Belgium
    4
    LRT2,Werner-Heisenberg-Weg39,Universitt der Bundeswehr Mnchen, D-85577Neubiberg,Germanv
    5
    Present address.NJ Bekaert SA, Bekaertstraat 2, B-8550 Zwevegem
    ivo.vankelecombiw.kuleuven.be
    Positron annihilation spectroscopy (PAS) is a non-destructive technique based on the analysis oI the -ray radiation emitted in
    the interaction oI the electrons with their anti-particles, the positrons. In polymeric material, positrons can capture an electron
    Irom the surroundings to Iorm positroniums (Ps).
    A proper selection oI the energy oI the positron beam enables to study the characteristic annihilation oI the positronium Irom
    the surIace down to a depht oI a couple oI micron and thus obtain a depth proIile oI the porosity. PAS has been used to probe
    structures at an atomic scale in semiconductors, metals, dielectrics, clays polymers. In membrane technology it has been
    applied to characterize commercial pervaporation, gas separation, ultraIiltration and reverse osmosis membranes and to study
    the Iree-volume depth proIile oI SRNF and RO membranes |1, 2|.
    In the present work, it has been applied to link Iundamental material properties at atomic scale with to membrane perIormance,
    in speciIic Ior asymmetric polyimide PI (P84)-based solvent-resistant nanoIiltration membranes (SRNF) prepared via phase-
    inversion.
    SRNF is widely applied in Iood, (Iine-)chemical, pharmaceutical and petrochemical industries. Lately, it has received
    enhanced attention since it oIIers a sustainable alternative Ior conventional energy-intensive and waste-generating separations
    |3|. A better understanding oI the membrane structure can provide with a better interpretation oI the experimental perIormance
    and prediction oI the utility oI a certain membrane Ior a given separation problem. Getting such structural inIormation about
    the selective top-layer oI SRNF-membranes is extremely diIIicult. Probing the porosity oI an SRNF-membrane is not possible
    with common techniques, like nitrogen adsorption or SEM. Results with laboratory-made membranes with well-known
    properties showed the potential oI PAS to add a level oI understanding to the current knowledge about membrane structure and
    its link with Iiltration perIormance. A diIIerent evolution oI the porosity across the depth regions could be related to the
    perIormance results Irom Iiltration experiments. This knowledge has been also applied to probe the structure oI commercial PI-
    based Starmem
    TM
    -membranes, where unknown chemical compositions make the interpretation oI PAL(S)-parameters more
    diIIicult.
    |1|K. Boussu at al. ChemPhvsChem 2007, 8, 370.
    |2|H. Chen et al. Macromolecules 2007, 40, 7542.
    |3|P. Vandezande et al. Chem. Soc. Rev. 2008, 37, 365.
    -53-
    OB.3.3
    In situ dynamic characterization of water transport and proton mobility in Nafion by
    ATR-FTIR and micro-Raman spectroscopy
    S. Deabate
    1
    , P. Huguet
    1
    , P. Sistat
    1
    , L. Grosmaire
    1
    , A. Morin
    2
    , G. Gebel
    3
    1
    Institut Europeen des Membranes (IEM), ENSCM, UM2, CNRS, Universite de Montpellier II, CC 047, Place Eugene
    Bataillon, 34095 Montpellier, France
    2
    Laboratoire dInnovations pour les Technologies des Energies et Nanomateriaux/Departement des Technologies de
    lHvdrogene/Laboratoire de Composants pour Piles a Electrolvtes Membranaire, CEA-Grenoble, 17 avenue des Martvrs,
    38054 Grenoble cedex 9, France
    3
    Unite Mixte de Recherche Structure et Proprietes dArchitecture Moleculaire (SPrAM) 5819, CEA, CNRS, UJF, CEA-
    Grenoble, 17 avenue des Martvrs, 38054 Grenoble cedex 9, France
    steIano.deabateiemm.univ-montp2.Ir
    Water management is one oI the most critical and widely studied issues in proton exchange membrane Iuel cells (PEMFCs).
    PEMFCs perIormances are directly related to the proton conductivity oI the polymer electrolyte and, consequently, to the
    membrane ion and water content. The recent trend is to operate PEMFCs under low humidity conditions while still
    maintaining an adequate conductivity oI the electrolyte membrane. Obviously, such low humidity operating strategies are not
    likely to be achieved without a good Iundamental understanding oI the mechanisms governing water/proton generation and
    transport inside the PEMFC and, namely, the separator material.
    In situ -Raman spectroscopy has been successIully used to probe, at the -meter scale, the heterogeneous distribution oI
    water inside NaIion under cross-transport conditions (Fig. 1). In order to gain maximum inIormation about true concentrations
    proIiles oI solvents progressing through the membrane thickness, enhancement oI the concentration proIile imaging has been
    carried out by taking into account the experimental spreading Iunction oI the optical set-up. Comparison between the
    concentration ratios at the solution-membrane interIace and the real concentration gradients within the membrane medium
    show that internal gradients diIIer considerably Irom those that can be estimated Irom methods measuring external
    concentrations.
    In order to obtain Iurther insights about relationships between the local water content and the macroscopic conductivity oI the
    membrane, the hydration process oI NaIion has been investigated by in situ ATR-FTIR spectroscopy. The evolution oI the IR
    spectra obtained at increasing relative humidity values (Fig. 2) illustrates the dissociation state oI the protogenic groups with
    hydration. Once Iree charge carriers (hydrated H

    ) have been Iormed, the structure oI water segregated inside the polymer
    network keeps on changing with the hydration state and, thus, the H

    diIIusion mechanism i.e. mobility.


    Figure 1. Spectral intensity proIiles oI water through
    NaIion 112 separating water-methanol solutions (solution
    1), with diIIerent methanol molar , Irom liquid water
    (solution 2): (A) 0, (B) 25, (C) 50, (D) 75 and (E)
    100.
    Figure 2. EIIect oI H
    2
    O adsorption on the ATR-FTIR spectra oI
    selI-supporting Iilms oI NaIion 112. The inset is a
    magniIication oI the spectral range containing the stretching
    vibration oI the undissociated sulIonate group and the bending
    modes related to water and hydronium ion.
    -54-
    OB.3.4
    Monitoring of membrane processes using non-invasive fluorescence techniques
    C. A.M. Portugal
    1
    , J. G. Crespo
    2
    1
    Cebal Rua Pedro Soares, Apartado 6158, 7801-908 Befa, Portugal (present adress)
    2
    Requimte-CQFB, FCT-Universidade Nova de Lisboa, Campus da Caparica 2825-516 Caparica, Portugal
    carla.portugalcebal.pt
    One oI the main requisites Ior sustainable process implementation is to guarantee the development oI stable and long-term
    perIormance, high process eIIiciency and product quality. In membrane processes short time perIormance stability appears
    mainly as a consequence oI membrane Iouling at the membrane surIace, which leads to changes oI physico-chemical and
    structural characteristic oI the membrane, with a negative impact on rejection and/or transport properties.
    The need Ior development oI in situ, non-invasive and real-time inIormation concerning process status is essential to achieve
    high process perIormance and productivity. While meeting these characteristics, Iluorescence spectroscopy is a highly
    sensitive technique capable oI membrane process monitoring based on the intrinsic or natural Iluorescence properties oI the
    system components.
    Its high sensitivity lays on the Iact that Iluorescence response depends not only on Iluorophore emission but also on the
    presence oI other interacting chemical species in the surroundings oI the Iluorophore (other Iluorophores or Iluorescence
    quenchers). ThereIore, Iluorescence emission signals (single emission scans or excitation-emission maps) enclose inIormation
    about the interaction oI Iluorophores with other species in complex media, such as interaction oI a molecule/complex media
    with a membrane or interactions between the complex media components. For this reason Iluorescence response is regarded as
    representing a Iingerprint oI the processing or molecule status.
    The deconvolution oI such complex inIormation either contained in single emission scans or in excitation-emission
    Iluorescence maps (resulting Irom 2D-Iluorometry) require the use oI adequate mathematical tools, which make possible an
    eIIective on-line and non-invasive monitoring and process control.
    Steady-state Fluorescence data may also be combined with data obtained Irom other Iluorescence techniques, such as
    Fluorescence Anisotropy, revealing inIormation about the Iree mobility oI a Iluorophore, and Time Resolved Fluorescence
    which allows Ior discriminating the individual contribution oI the Iluorophores to the overall Iluorescence response oI the
    system.
    This work aims at elucidating about the potential oI using Steady-state Fluorescence (single and 2D Iluorimetry) when used
    alone or in complementary mode with Fluorescence Anisotropy and Time Resolved Fluorescence, their advantages and
    limitations. This discussion will be done through presentation oI illustrative examples (e.g. monitoring membrane processing
    oI proteins |1|, monitoring oI membrane bioreactors Ior water treatment processes |2|) showing how these techniques may be
    used Ior monitoring oI membrane processes.
    |1| Carla A. M. Portugal, J. C. Lima, Joo G. Crespo. Probing the change oI enzymatic activity oI horseradish peroxidase
    induced by membrane permeation using tryptophan Iluorescence. J. Membr. Sci., 284 (2006) 180-192.
    |2| G. WolI, J. S. Almeida, C. Pinheiro, Vasco Correia, C. Rodrigues, M. A. M. Reis, J. G. Crespo. Two-Dimensional
    Fluorometry Coupled with ArtiIicial Neural Networks: A Novel Method Ior On-Line Monitoring oI Complex Biological
    Processes. Biotechnol. Bioeng. 72 ( 2001) 297-306.
    OB.3.5
    Characterisation of the properties and the sugar penetration in ion exchange
    membranes equilibrated in sugar aqueous solutions
    E. Vera
    1
    , P. Sistat
    1
    , P. Huguet
    1
    , S. Deabate, S. Galier
    2,3
    , H. Roux de Balmann
    2,3
    1
    Institut Europeen des Membranes (IEM),, Universite Montpellier II,ENSCM, CNRS, CC047, Place Eugene Bataillon, 34095
    Montpellier, France
    2
    Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, F-31062 Toulouse cedex 09, France
    3
    CNRS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    philippe.sistatiemm.univ-montp2.Ir
    The presence oI organic sugars in the electrodialysis oI Iood liquids is very common; however there is not a clear
    comprehension about how these compounds could aIIect the membrane properties and iI sugars could penetrate inside the
    membrane.
    -55-
    CMX and AMX membranes Irom Astom Corp., stabilised according to |1|, were equilibrated in diIIerent sugar aqueous
    solutions oI xylose, Iructose, glucose and sucrose at concentrations between 0.01 M and 4.0 M. Then, measurements oI
    impedance spectra in a mercury cell |2,3| were made to asses the inIluence oI sugar on the electrical properties oI the
    membrane; besides measurements oI IR spectra and Raman cartographies |4| were made to determine iI there was penetration
    oI sugar inside the membrane.
    The impedance oI the membranes had great variations when the
    concentration oI sugar was superior to 1.0 M. This behaviour was similar to
    the variation oI viscosity oI solutions, indicating a big change on the
    membrane properties or the presence oI sugar solution layers near the
    membrane. Besides, the impedance oI new membranes was 10 to 30
    lower than the impedance oI membranes equilibrated in sugar solutions. The
    IR spectra showed that there were changes in the characteristics peak
    maximums, which could be caused by interactions between the membrane
    and the sugar. The Raman cartographies indicated that the sugar did not
    signiIicantly penetrate inside the membrane even at high concentrations
    (Figure 1). These Iirst results showed that sugars did not modiIy the intrinsic
    properties oI membranes, but they strongly modiIy its environment.
    |1| AFNOR, Norme Franaise: Separation d`ions en phase liquide. Membranes polymeres echangeuses d`ions
    (Chapitre: Stabilisation des echantillons ou des eprouvettes), 1995, pp.10-11.
    |2| C. Gavach, G. amboutzoglou, M. Neyalkov, G. Pourcelly, AC impedance investigation oI the kinetics oI ion transport in
    Nation perIluorosulphonic membranes, J. Membrane Sci., 1989, 45, 37-53.
    |3| G. Pourcelly, A. Oikonomou, C. Gavach, InIluence oI the water content on the kinetics oI counter-ion transport in
    perIluorosulIonic membranes. J. Electroanal. Chem., 1990, 287, 43-59.
    |4| S. Deabate, R. Fatnassi, P. Sistat, Patrice Huguet, In situ conIocal-Raman measurement oI water and methanol
    concentration proIiles in NaIion membrane under cross-transport conditions, Journal oI power sources, 2008, 176, 39-45
    OB.3.6
    Impact of chemical treatments on Nafion sorption using
    1
    H NMR
    F. Xu
    1
    , S. Leclerc
    1
    , O. Lottin
    1
    , D. Canet
    2
    , J. Bedet
    1,2
    1
    Laboratoire dEnergetique et de Mecanique Theorique et Appliquee (LEMTA), Nancv-Universite, CNRS, 2 avenue de la
    Fort de Have, B.P.160, 54504 Jandoeuvre les Nancv Cedex, France
    2
    Methodologie RMN CRM2, Nancv-Universite, CNRS, boulevard des aiguillettes, BP 239, 54506 Jandoeuvre les Nancv
    Cedex, France
    Feina.Xuensem.inpl-nancy.Ir
    NaIion

    is the most studied ionomer membrane since it exhibits a good perIormance in a large number oI applications like
    demineralisation processes or Proton Exchange Membrane Fuel Cells (PEMFC) |1,2|. Although this membrane is well known,
    data are still needed to model accurately its behaviour in the usual operating conditions oI PEMFCs because its thermal,
    mechanical and chemical history aIIects its perIormance. Among the parameters that must be studied, the coeIIicient oI selI-
    diIIusion oI water plays a key role in water management in PEMFC.
    NMR is a powerIul technique Ior measuring this parameter in various conditions. However, many treatment methods are
    proposed in the literature to clean membranes prior to NMR measurements |3,4,5|, among which a choice has to be made. For
    instance, to increase the relaxation rate, some authors |3| propose to equilibrate the samples in EDTA solutions in order to
    remove metallic cations. However, this treatment could aIIect the water sorption in NaIion, either by a possible chemical
    contamination or more probably by a change oI the cation Iorm oI NaIion.
    This study Iocuses on the understanding oI the eIIects oI chemical treatments on NaIion sorption (which can be modiIied by
    chemical contaminants) using NMR techniques |6|. The eIIiciency oI chemical cleaning will be discussed Irom water dynamic
    inIormation at micro (1s 1ms) to intermediary (10s 1 ns) scales.
    |1| K. A. Mauritz, R. B. Moore, State oI understanding oI NaIion, Chemical Reviews, 2004, 104(10), 4535-4585
    |2| P. Costamagna, S. Srinivasan, Quantum jumps in the PEMFC science and technology Irom the 1960s to the year 2000 :
    Part I. Fundamental scientiIic aspects, Journal oI Power Sources, 2001, 102(1-2), 242-252
    |3| B. MacMillan, A. R. Sharp, R. L. Armstrong, An N.M.R. investigation oI the dynamical characteristics oI water absorbed
    in NaIion, Polymer, 1999, 40 (10), 2471-2480
    |4| I. Nicotera, T. Zhang, A. Bocarsly, S. Greenbaum, NMR characterisation oI composite polymer membranes Ior low-
    humidity PEM Iuel cells, Journal oI the Electrochemical Society, 2007, 154 (5), B466-B473
    -56-
    Figure 1. Raman cartography oI the AMX
    membrane equilibrated in 4.0 M xylose
    aqueous solution.
    |5| A. Y. Nosaka, Y. Nosaka, Slow morphological change oI perIluorinated ionomer as deduced Irom 1H spectra oI conIined
    water, Journal oI Power Sources, 2008, 180(2), 733-737
    |6| E. O. Stejskal, J. E. Tanner, Spin-diIIusion measurements: spin-echoes in the presence oI a time-dependent Iield gradient,
    Journal oI Chemical Physics, 1965, 42, 288-292
    OB.3.7
    Mass transfer analysis in polymer solutions prior to phase separation by near
    infrared and Raman spectroscopy
    C. Pochat-Bohatier
    1
    , W. Werapun
    1
    , D. Bouyer
    1
    , E. Petit
    2
    , P. Huguet
    2
    , A. Deratani
    2
    , J.-P. DesIours
    1
    1
    Laboratoire de Genie des Procedes Eau et Bioproduits, UMR CIRAD/UMII/UMI 016, Universite Montpellier , cc05, 2 place
    Bataillon, 34095 Montpellier cedex 05, France.
    2
    Institut Europeen des Membranes, UMR CNRS/ENSCM/UMII 5635, Universite Montpellier 2, 2 place Bataillon 34095
    Montpellier, France.
    celine.pochatuniv-montp2.Ir
    Polymeric membranes are mainly manuIactured using processing based on phase separation techniques. The control oI a
    temperature or composition change in a homogeneous polymer solution leads to the demixing oI the solution in two phases,
    one polymer-rich and one polymer lean-phase, giving rise to the membrane structure Iormation. Depending on the process
    parameters, the morphology can be tailored to the separation perIormances desired. Water vapor sorption by a polymer
    solution can lead to phase separation owing to its poor solvency properties. Depending on the thermodynamic and kinetic
    parameters at this stage, the demixing process oI the homogeneous polymer solution dramatically inIluences the morphology
    oI the Iinal material. Several studies gave already experimental evidence oI the relationships between the resulting membrane
    morphology and the mass transIer phenomena occurring during the Vapor Induced Phase Separation (VIPS) process |1-2|.
    Actually, mass transIer analysis in polymer solutions during elaboration mechanisms can been really achieved only prior to
    phase separation, because (i) aIter the demixing process analytical determination oI the composition are nearly impossible
    because oI the Iormation oI nuclei and the polymer precipitation; (ii) the mathematical models developed to describe the mass
    transIers are only valid until the onset oI phase separation. Moreover, analytical measurements on Ilat-sheet or hollow Iiber
    membranes during membrane preparation are diIIicult to achieve because oI the low thickness oI the polymer solution,
    generally in the range 100-500 m, and the promptness oI mass transIer phenomena.
    For these reasons, our work has been Iocused on the analysis oI the polymer composition by near inIrared and Raman
    spectroscopy by increasing both space and time scales to promote convenient in-situ dynamic characterization. The
    methodology involved allowed us to set up proIile concentrations and mass transIer kinetics in polymer solution prior to phase
    separation. The composition paths on the ternary phase diagram were determined Ior diIIerent polymer/solvent/non-solvent
    systems (PEI/NMP/water, PEI/DMAc/water, PES/NMP/water, PES/DMF/water). Finally, the obtained experimental data
    enable the validation oI modeling description based on mass transport phenomena and Flory-Huggins theory.
    |1| Z. Chen, M. Deng, Y. Chen, G. He, M. Wu and J. Wang, Preparation and perIormance oI cellulose
    acetate/polyethyleneimine blend microIiltration membranes and their applications, J. Membr. Sci., 235 (2004) 73.
    |2| H.J. Lee, B. Jung, Y.S. Kang and H. Lee, Phase separation oI polymer casting solution by nonsolvent vapor , J. Membr.
    Sci., 245 (2004) 103.
    -57-
    OB.3.8
    Keynote: Dynamic characterization of membrane processes: the rear window
    paradigm
    J.G. Crespo
    CQFB/REQUIMTE, FCT-Universidade Nova de Lisboa, Campus da Caparica, 2829-516 Caparica, Portugal.
    jgc.Ict.unl.pt
    The dynamic characterization oI membrane processes has evolved signiIicantly in recent years, due to the need Ior monitoring
    in-situ, in a non-invasive way and in real-time. These Ieatures are necessary Ior development oI eIIective tools Ior process
    optimization and control.
    Additionally, in a signiIicant number oI situations, the dynamic characterization oI membrane processes requires inIormation
    at a nano-scale, or even at a molecular scale. One oI the main challenges is the acquisition oI such inIormation without
    disturbing the obfect oI observation.
    This presentation will discuss the use oI diIIerent spectroscopic and microscopic techniques aiming at characterizing
    membrane processes in a non-invasive way (iI that is possible at all.). The use oI molecular probes, either extrinsic or
    intrinsic, will be also discussed with a particular emphasis on the use oI Iluorescence and magnetic responsive probes.
    OC.1.1
    Gas sorption in glassy polymers - Comparative characterization using experimental
    and molecular modeling techniques
    M. Bhning
    1
    , O. Hlck
    1
    , M. Heuchel
    2
    , D. HoImann
    2
    1
    Federal Institute for Materials Research and Testing (BAM), Unter den Eichen 87, 12205 Berlin, Germanv
    2
    Center for Biomaterial Development, Institute of Polvmer Research, GKSS Research Center, Kantstrae 55, 14513 Teltow,
    Germanv

    current address. Micro Materials Centre Berlin, Fraunhofer Institute for Reliabilitv and Microintegration IZM,
    Jolmerstrasse 9B, 12489 Berlin, Germanv
    Martin.Boehningbam.de
    In order to control the sorption and swelling behavior oI glassy polymer/gas systems, especially Ior membrane applications, a
    deeper understanding oI these phenomena on the molecular level is necessary. In the presented study we make an attempt to
    combine experimental characterization with detailed atomistic molecular dynamic simulations. Obtained results may also
    constitute a basis Ior interpretation in the Iramework oI established phenomenological models.
    Our approach |1-3| consists oI investigations oI three diIIerent glassy polymers: (1) polysulIone as a conventional polymer, (2)
    a 6FDA-polyimide as a high perIormance membrane material and a PIM (polymer oI intrinsic microporosity) as a high Iree
    volume material; as gases CO
    2
    and CH
    4
    were considered. Experimental characterization comprises gravimetric gas sorption as
    well as gas-induced dilation behavior at pressures up to 5 MPa, including a thorough analysis oI the kinetics oI both processes.
    Molecular modeling |4,5| using primarily detailed atomistic MD and
    GCMC techniques addresses the analysis oI packing models oI unswollen
    and selected swollen states oI the polymer/gas-systems under investigation
    with respect to structural and dynamic Ieatures. So the analysis in regard to
    the Iree volume distribution reveals characteristics oI changes induced by
    the swelling process as well as Ieatures oI the investigated glassy polymers
    which diIIer distinctly with respect to Iractional Iree volume, chain-
    stiIIness and molecular mobility. Besides a more detailed examination oI
    the matrix dilation in experiments and packing models |6|, a Iirst
    assumption Ior a linear pressure (or concentration) dependence oI the
    polymer allows a reasonable description oI gas sorption over a broad
    pressure range using GCMC calculations oI unswollen and pre-swollen
    models.
    Fig.1: Fractional Iree volume oI unswollen and
    swollen PSU; distribution oI Iree volume
    elements considered as spheres with equivalent
    volume
    |1| O. Hlck, 'Gas Sorption and Swelling in Glassy Polymers - Combining Experiment, Phenomenological Models and
    Detailed Atomistic Molecular Modeling, PhD thesis, TU-Berlin 2008
    -58-
    http://opus.kobv.de/tuberlin/volltexte/2008/1771.
    |2| M. Heuchel, M. Bhning, O. Hlck et al., J. Polym. Sci. Part B: Polym. Phys. 2006, 44(13) 1874.
    |3| O.Hlck, M.R.Siegert, M.Heuchel, M.Bhning, Macromolecules 2006, 39(26), 9590.
    |4| M.Heuchel, D.HoImann, P.Pullumbi, Macromolecules 2004, 37(1), 201.
    |5| D.HoImann, L. Fritz, J.Ulbrich, C.Schepers, M.Bhning, Macromol. Theor. Sim. 2000, 9(6), 293.
    |6| O.Hlck, M. Bhning, M. Heuchel, D. HoImann, J. Polym. Sci. Part B: Polym. Phys. 2008, 46(1), 59
    OC.1.2
    Study of ion transport through nanopores
    J. Dweik
    1
    , B. Coasne
    2
    , F. Henn
    2
    , J. Palmeri
    3
    1
    Institut Europeen des Membranes (IEM), ENSCM, UM2, CNRS , UMR 5635, Universite Montpellier II, CC 047, Place
    Eugene Bataillon, F-34095 Cedex 5, Montpellier, France.
    2
    Institut Charles Gerhardt Montpellier, CNRS UMR 5253, Universite Montpellier II, ENSCM, Montpellier, France.
    3
    Laboratoire de Phvsique Theorique, Universite Paul Sabatier, Toulouse, CNRS, Toulouse, France.
    jalal.dweikiemm.univ-montp2.Ir
    The aim oI this work is to better understand the physical and physicochemical phenomena involved in nano-conIined aqueous
    solutions, especially the role oI "solute-solute" and "solute-interIace" interactions within nanopores. By a Iundamental
    approach based on the meso-macroscopic physics oI Iluids, we study the ionic transport across the membrane pores using the
    'space charge model |1,2|. This model based on the nonlinear Poisson-Boltzmann 'mean Iield theory, takes into account the
    electrostatic interactions between the membrane and ions in solution. Understanding oI ionic transport and selectivity across
    nanoIiltration membranes is only partial at this level oI description. We thereIore go beyond the meso and macroscopic
    approaches by perIorming "Molecular Dynamics" simulations using the AMBER9 program package, a method particularly
    well adapted to the nanoscale. We Iocus on a study oI 'water/nanopore systems, more particularly eIIects due to the speciIic
    characteristics oI molecules and ions: size, charge, polarizability and the nature oI the surIace (hydrophobic/philic) |3|. We
    study the distribution oI ions and water molecules and their correlations/Iluctuations (Figure 1). Our simulations reveal the
    important role played by atomic and ionic polarizability on the distribution oI ions in aqueous solutions near interIaces and in
    nanopores. This eIIect may be at the origin oI the Iiltration selectivity oI nanoporous membranes Ior ions oI the same charge
    valence and thereIore must be better understood beIore being reliably integrated into mesoscopic theories oI membrane
    transport.
    Figure 1. (a) Snapshot oI a simulation oI 1M NaI in polarizable (Pol3) water showing the nanochannel and hydrophilic
    membrane structure. (b) concentration, C(Z) , oI water oxygen atoms and ions plotted vs. distance normal to the interIace (z),
    normalized by the bulk concentrations.
    |1| J. Dweik and J. Palmeri 'Conductivity oI a single salt in a cylindrical nanochannel: numerical and analytical approaches to
    the mean-Iield space-charge model(submitted to Phys. Rev. E).
    |2| J. Dweik and J. Palmeri. 'Ion transport Ior a single salt in a cylindrical nanochannel: the extended homogeneous
    approximation to the space-charge model( submitted to Phys. Rev. E).
    |3| D. Horinek, R. Netz, Phys. Rev. Lett. 99, 226104 (2007).
    -59-
    OC.1.3
    The role of the hydrogen-bonding and weak interactions in competitive interacting
    processes influencing the polymeric membrane properties
    G. De Luca
    1
    , A. Gugliuzza
    1
    , E. Drioli
    1,2
    1
    Research Institute on Membrane Technologv (ITM-CNR), Jia P. Bucci, 17/C, I-87030 Rende (CS), Italv
    2
    Department of Chemical Engineering and Materials, Universitv of Calabria,Jia P. Bucci 45 /C, I-87030 Rende (CS), Italv
    g.delucaitm.cnr.it
    Hydrogen-bonding and weak linkages in competitive interacting processes appear oI crucial importance Ior the interpretation
    oI many phenomena involving membranes. Hydrogen-bonding can be determinant in adsorption oI polar molecules on
    polymeric membranes |1-2|. Aging, swelling phenomena, selI-assembled structures involve also competitive hydrogen-
    bonding and/or weak intermolecular interactions. The quantum mechanics calculation represents a powerIul tool to investigate
    the mentioned phenomena, since it provides useIul inIormation diIIicult or sometimes impossible to obtain experimentally.
    This presentation deals with two 'cases study, where the quantum mechanics has provided useIul and complementary
    inIormation about the role oI hydrogen-bonding and/or weak interactions in phenomena occurring in membrane processes.
    Firstly, hydrogen-bonding interactions involving an amphiphilic modiIier (guest) and the polar Iunctional groups oI a block
    (ether/amide) polymer (host) have been analysed. Calculations oI interaction energies in solvent and vacuum have been
    evaluated, showing competition between the host-host (Fig. 1a,b) and guest-host no covalent interactions (Fig. 1c,d). This
    competition has been demonstrated to be responsible Ior an increase oI the availability oI polar Iunctional groups and,
    thereIore, oI hydrophilicity oI the membrane. The macroscopic result was the change in the sorption and transport oI polar and
    polarizable molecules through the matrixes.
    a b c d
    Figure 1
    The second case-study analysed is related to no covalent interactions, which address swelling phenomena in membranes
    contacting liquid streams. Interactions controlling the reversible swelling oI Iluorinated membranes in ethanol solutions have
    been examined |3|. SpeciIically, the uptake oI the liquid into the polymer chains has been modelled, analysing the eIIects oI no
    covalent interactions between water/ethanol and the segments oI the Iluorinated polymer. The eIIects oI the enveloped solvents
    on the polymer packing density chains have been computationally investigated.
    The authors are grateIul to INSTM/CINECA Ior the computational support.
    |1| A Gugliuzza, G. De Luca, E. Tocci, L. De Lorenzo, E. Drioli, J. Phys. Chem B 2007, 111, 8868 -8878.
    |2| G. De Luca, A Gugliuzza, E. Drioli, J. Phys. Chem B submitted.
    |3| A. Gugliuzza, E. Drioli, J. Membr. Sci. 300 (2007) 5162.
    OC.1.4
    Atomistic simulation of gas sorption isotherms in a polymer of intrinsic
    microporosity (PIM-1)
    M. Heuchel
    1
    , O. Hlck
    2
    , M. Bhning
    2
    , D. Fritsch
    3
    , D. HoImann
    1
    1
    GKSS Research Center, Institute of Polvmer Research, Kantstr. 55, D-14513 Teltow, Germanv
    2
    Federal Institute for Materials Research and Testing (BAM), Unter den Eichen 87, 12205 Berlin, Germanv
    3
    GKSS Research Center, Institute of Polvmer Research, Max-Planck-Str. 1, D-21502 Geesthacht, Germanv

    current address. Micro Materials Centre Berlin, Fraunhofer Institute for Reliabilitv and Microintegration IZM,
    Jolmerstrasse 9B, 12489 Berlin, Germanv
    matthias.heuchelgkss.de
    Recently, so-called polymers with intrinsic microporosity (PIMs) evoked speciIic interest in the membrane community |1|
    because respectively prepared membranes display both, very high gas permeability and good selectivity simultaneously, in
    -60-
    contrast to the normal trade-oII behavior oI many traditional thermoplastic polymers. The 'microporosity, i.e. high Iree
    volume and high internal surIace area oI the solid materials, are the result oI a reduced packing eIIiciency oI randomly
    contorted rigid backbone chains.
    We have built atomistic packing models Ior the ladder polymer PIM-1, (Fig. 1, leIt). The models obtained by Iorce Iield-based
    molecular mechanics and molecular dynamics methods have a allowed a prediction oI permeation properties oI small gasses
    and also revealed a certain, unexpected Ilexibility oI plane segments between the spiro-centres |2|. Here, we use single
    representative reIerence states Irom experimental data and construct atomistic packing models (Fig. 1, center) according to
    these speciIications. Gas sorption oI CO
    2
    (Fig. 1, right) and CH
    4
    was successIully calculated, at 308 K and pressures up to 50
    bar.
    Figure 1 left. Structure oI PIM-1; center. Representative slices oI nonswollen and swollen packing models oI PIM-1; right.
    Sorption isotherms Ior PIM-1/ CO
    2
    calculated Ior the nonswollen (PIM;) and swollen (PIM206m,) packing models; exp.
    data (); dual mode sorption Iits () and linearly weighted average oI the latter (). (The exp. reIerence Ior the swollen state is
    marked by a circle)
    |1| e.g., session 'Nanostructured Membranes I at ICOM 2008, July 14, 2008, Honolulu, Hawaii USA
    http://www.icom2008.org/viewsessioninIo.cIm?ID344
    |2| M. Heuchel, D. Fritsch, P.M. Budd, N.B, McKeown, D. HoImann, Atomistic packing model and Iree volume distribution
    oI a polymer with intrinsic microporosity (PIM-1), J. Membrane Sci. 2008, 318, 84-99
    OC.1.5
    Keynote: Membrane structure and transport modelling across scales
    V.N. Burganos
    Institute of Chemical Engineering and High Temperature Processes - Foundation for Research and Technologv, Hellas
    Stadiou street, Platani, Patras 26500, Greece.
    vburiceht.Iorth.gr
    The design oI new nanomaterials and the improvement oI existing ones rest signiIicantly on the suIIicient understanding oI the
    mechanisms that govern their perIormance during operation. Notable examples oI such applications include membrane-based
    separation, hydrogen storage, Iuel cells, etc. In turn, these mechanisms, in many instances, depend heavily on the internal
    morphology or, more generally, on the spatial distribution oI the chemical and physical constituents oI the nanomaterial at the
    atomic scale. It is exactly this interrelationship between structure and transport that several advanced modeling and simulation
    eIIorts are nowadays Iocused on.
    A particular diIIiculty that is encountered when dealing with nanomaterials is the great number oI scales that are needed to
    bridge the gap between the scales oI microscopic simulations and the process one. To partly remedy this, multiscale models
    and simulators have been developed that either attempt to climb up a Iew scales through the so-called coarse graining approach
    or deal with each distinct-scale domain separately (domain decomposition) with a hand-shaking procedure at the boundaries.
    Because oI the tremendous signiIicance oI the internal structure oI membranes on their perIormance, several eIIorts have been
    made to develop models and simulators oI the membrane structure itselI. Both microscopic and mesoscopic models will be
    discussed Iollowed by a presentation oI hybrid techniques that attempt to bridge the gap between nanoscale representations to
    grain/pore mesoscopic ones. In addition, a modiIied lattice-Boltzmann technique is developed that can simulate Ilow at
    elevated Knudsen numbers, which is typically the case in several types oI membrane processes. The results will be compared
    to those Irom a Direct Simulation Monte Carlo method Ior pore sizes in the range oI a Iew tens oI nanometers. Even smaller
    scales are handled by molecular dynamics or Monte Carlo techniques using a Iorce-Iield type oI approach. Finally, the
    application oI a two-phase lattice-Boltzmann method to multiple size-scale Ieatures in membrane materials will be presented.
    -61-
    OC.2.1
    Modelling transport through integrally skinned asymmetric organic solvent
    nanofiltration membranes. Effect of concentration polarisation and osmotic pressure
    L.G. Peeva, P. Silva, A.G. Livingston
    Department of Chemical Engineering, Imperial College London, Exhibition Road, London SW7 2AZ, UK
    l.peevaimperial.ac.uk
    The separation oI molecules present in organic solvents by nanoIiltration has potential application in many industries, ranging
    Irom reIining to Iine chemical and pharmaceutical synthesis |1|. In the last two decades the Iirst practical membranes have
    become available, and organic solvent nanoIiltration (OSN) is currently an area oI intensive investigation. However, previous
    work has mainly been carried out with dilute solutions (1wt solute in solvent), whereas in actual applications, solutes will
    be more concentrated (~5wt) and phenomena such as concentration polarisation and osmotic pressure may contribute
    substantially to the solvent Ilux, as in aqueous systems.
    In order to improve our understanding oI organic solvent nanoIiltration phenomena, experiments were perIormed in a cross
    Ilow rig in which OSN was carried out in a continuous mode. Solvent resistant nanoIiltration membranes Irom the
    STARMEM
    TM
    122 series (nominal molecular weight cut-oII oI 220 Da), and two diIIerent large organic molecules tetraoctyl
    ammonium bromide (TOABr, MW546Da) and docosane (MW310Da) as toluene solutions oI diIIerent concentrations (up to
    20 wt) were used. It was observed that the Ilux through the membrane is aIIected by the cross Ilow velocity, indicating that
    at these high concentrations, concentration polarisation becomes signiIicant. Mathematical description oI the experimental
    data, including solute rejection, was perIormed using the solution diIIusion model Ior membrane transport and the Iilm theory
    Ior liquid mass transIer eIIects. The results show that the organic systems cannot always be described by a simple osmotic
    pressure model. Special attention was paid to the role oI the activity coeIIicients oI the solute and the solvent, which seem to
    markedly aIIect the permeate Ilux. The Iit between the model and the experimental data could be obtained only by allowing the
    activities oI the solution components to vary, indicating that these systems are non-ideal |2|.
    The study was extended Iurther to a pilot plant apparatus using a spiral-wound STARMEM
    TM
    122 module over prolonged
    periods oI time, with 0-25 wt solutions oI tetraoctylammonium bromide (TOABr) in toluene. The binary system
    toluene/TOABr, was investigated again in order to establish a comparisons with the Ilat-sheet cross-Ilow nanoIiltration results.
    The experimental Ilux and rejection Ior the spiral-wound element were successIully described using the above mentioned
    modiIied solution-diIIusion model (with activity coeIIicients included) combined with Iilm theory Ior the liquid mass-transIer
    |2|. It was Iound that membrane transport parameters determined Irom Ilat sheet membrane tests can be used to accurately
    predict spiral-wound element perIormance. In our knowledge this is the Iirst study presented on OSN in spiral-wound
    membrane modules.
    |1| P. Vandezande, L.E. M. Gevers, I.F.J. Vankelecom, Chemical Society Reviews 37, 2008, 365.
    |2| L. G. Peeva et al, J. Membrane Science 236, 2004, 121.
    OC.2.2
    Transport properties of nanofiltration membranes with inhomogeneous charge
    distributions
    A. Szymczyk, H. Zhu, B. Balannec
    Chimie et Ingenierie des Procedes, UMR 6226 CNRS-Universite de Rennes 1-ENSCR, 263 Avenue du General Leclerc, CS
    74205, 35042 Rennes Cedex, France
    Universite Europeenne de Bretagne
    anthony.szymczykuniv-rennes1.Ir
    Due to the increasing interest Ior nanoIiltration (NF), numerous works have Iocused on the development oI models that are
    likely to describe the separation properties oI NF membranes |1-3|. The combination oI pore diameters around a Iew
    nanometers with electrically charged materials implies that solute exclusion results Irom a complex mechanism involving
    several phenomena. Modern transport models are based on the Poisson-Nernst-Planck Iormalism to account Ior electrostatic
    interactions and ionic transport through membrane pores. Because oI the strong overlap oI electrical double layers inside pores
    oI NF membranes, the radial variation oI the electrostatic potential is small and the so-called homogeneous approximation is
    commonly used. This latter has the great advantage to simpliIy considerably the numerical treatment and to require much less
    -62-
    computational eIIorts. Within the scope oI the homogeneous approximation, the Poisson-Boltzmann equation is replaced by
    modiIied Donnan equations (including in some cases steric hindrance and/or dielectric eIIects |3, 4|) combined with a local
    electroneutrality condition involving the membrane volume charge density. It has been recently demonstrated by Transmission
    Electron Microscopy observations that the Iixed charge across the active layer oI polyamide thin-Iilm composite membranes
    (i.e. the main type oI membranes used in NF) is distributed in a highly non-uniIorm Iashion |5|. However, all current models
    used to investigate salt rejection properties oI NF membranes are based on the assumption that the membrane charge is
    homogeneously distributed over the pore surIace. Otherwise stated, the membrane volume charge density is considered to be
    independent oI the axial position inside pores and thus, the dependence oI the membrane charge with the local ion
    concentration is disregarded. We have dropped this assumption in order to investigate the inIluence oI spatially
    inhomogeneous Iixed charge distributions on ion transport through NF membranes. A comprehensive set oI 1D distributions
    have been considered and analyzed on the basis oI extended Nernst-Planck equations. It has been shown that asymmetric Iixed
    charge distributions may signiIicantly aIIect the rejection properties oI NF membranes. The comparison between various kinds
    oI charge distributions leading to identical average volume charge densities shows that membrane perIormances may be
    signiIicantly modiIied by the inhomogeneous distribution oI the Iixed charges inside pores.
    |1| Bowen, W.R; Mohammad, A.W.; Hilal, N. (1997) J. Membr. Sci. 126, 91-105.
    |2| Palmeri, J.; Blanc, P.; Larbot, A. ; David, P. (1999) J. Membr. Sci. 160, 141-170.
    |3| Szymczyk, A.; Fievet, P. (2005) J. Membr. Sci. 252, 77-88.
    |4| Yaroshchuk, A.E. (2000) Adv. Colloid Interface Sci. 85, 193-230.
    |5| Freger, V. (2003) Langmuir 19, 4791-4797.
    OC.2.3
    Predictive transport model for solvent permeation through organic and inorganic
    solvent resistant nanofiltration membranes
    S. Darvishmanesh
    1
    , A. Buekenhoudt
    2
    , J. Degreve
    1
    , B. Van der Bruggen
    1
    1
    Department of Chemical Engineering, Laboratorv for Applied Phvsical Chemistrv and Environmental Technologv,Katholieke
    Universiteit Leuven, W. de Crovlaan 46, B-3001 Heverlee, Belgium
    2
    Process Technologv, Flemish Institute for Technilogical Research (JITO), Boeretang 200, 2400 Mol, Belgium
    siavash.darvishmaneshstudent.kuleuven.be
    DiIIusion oI solvent through swollen membranes has been Iound to be coupled with convection . Starting Irom this
    observation, a novel semi-empirical based on the solution diIIusion with imperIection theory has been developed. In the newly
    developed model solvent permeation was Iound to be dependent on viscosity, and two new deIined non dimensional
    parameters. These parameters illustrate the eIIect oI surIace tension and the dielectric constant on transport properties and Ilux
    oI solvents. To validate the model, permeation oI a homologous series oI six primary alcohols through hydrophobic polymeric
    membrane (Solsep-030505) has been measured in dead-end Iiltration module Ior pressure oI 10 bar. The result oI the model
    Iitting was well satisIactory. The model was also tried out Ior a broad range oI solvents using additional Iiltration experiments.
    The permeation oI various solvents Irom diIIerent chemical Iamilies through a hydrophobic polymeric membrane (MPF 50)
    and a hydrophilic ceramic membrane (HITK 275) has been measured Ior same pressure in dead-end and cross-Ilow mode
    respectively. The permeability values calculated with the new model showed a very high correlation (maximum error oI 5)
    over the entire range oI solvents used. The modeling results conIirm the assumption oI convective-diIIusive nature oI transport
    in solvent resistant nanoIiltration (SRNF).
    |1| Bhanushali, D., S. Kloos, and D. Bhattacharyya, Solute transport in solvent-resistant nanofiltration membranes for non-
    aqueous svstems. experimental results and the role of solute-solvent coupling. Journal oI Membrane Science, 2002. 208(1-2):
    p. 343-359.
    |2| Sherwood, T.K., P.L.T. Brian, and R.E. Fisher, Desalination bv reverse osmosis. I&EC Fundam, 1967. 6: p. 2.
    -63-
    OC.2.4
    A simulation model for membrane affinity chromatography
    S. Dimartino, C. Boi, G.C. Sarti
    Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali, Alma Mater Studiorum Universita di
    Bologna,via Terracini 28, 40131 Bologna, Italv
    giulio.sartimail.ing.unibo.it
    Chromatography represents one oI the most important and widely used unit operation in the biotechnology industry. However
    this technique suIIers Irom several limitations such as high pressure drop, slow mass transIer through the diIIusive pores and
    strong dependence oI the binding capacity on Ilow rate. One oI the alternatives that are receiving increasing attention is
    represented by membrane chromatography, Ior which it is imperative to develop a reliable simulation model able to describe
    the process perIormance in a predictive way.
    In the present work a novel model is proposed that can describe all the chromatographic steps involved in the membrane
    aIIinity chromatography process Ior protein puriIication. The mathematical description is based on the species continuity
    equation coupled with a proper binding kinetic equation, and suitable to describe adequately the dispersion phenomena
    occurring both in the micro-porous membranes as well as in the extra-column devices used in the system. The model considers
    speciIically all the diIIerent chromatographic steps, namely adsorption, washing and elution.
    Model validation is achieved by comparing simulation results with an extensive set oI experimental data which have been
    obtained Ior the puriIication oI immunoglobulin G Irom a cell culture supernatant, using several diIIerent innovative aIIinity
    membranes and using a broad spectrum oI operating conditions.
    The Iew relevant Iitting parameters oI the model were derived Irom a calibration with experimental aIIinity cycles perIormed
    with pure IgG solutions, then the model is used to describe experimental data obtained in chromatographic cycles carried out
    with complex Ieeds as the cell culture supernatant.
    Simulations reveal a good agreement with experimental data in all the chromatography steps, both in the case oI pure IgG
    solutions and Ior the cell culture supernatant considered.
    This work has been perIormed as part oI the 'Advanced Interactive Materials by Design (AIMs) project, supported by the
    Sixth Research Framework Programme oI the European Union (NMP3-CT-2004-500160).
    OC.2.5
    Rigorous modeling of the solute transport in emulsion liquid membranes in hollow
    fiber contactors
    E. Bringas, M.F. San Roman, I. Ortiz
    Department of Chemical Engineering and Inorganic Chemistrv, Universitv of Cantabria, ETSIIvT, Avda. Los Castros s/n,
    39005, Santander, Spain.
    ortiziunican.es
    The application oI a new technology requires a reliable mathematical model and parameters that serve Ior design and
    optimization purposes allowing to accurate scale-up processes |1|. Progress in knowledge about membrane-based solvent
    extraction has led to the development oI attractive alternatives that maximise the separation rate oI the solute mass transport
    process. Emulsion Pertraction Technology (EPT) carried out in hollow Iiber contactors (HFC) is a good example oI intensiIied
    liquid membrane processes that achieves a maximum driving Iorce in the separation process aIter combination oI the
    advantages oI emulsion liquid membranes and non-dispersive solvent extraction |2|. In this conIiguration an emulsion phase
    comprising oI an extractant agent and a back-extraction agent, Ilows through the shell side oI one single HFC while the
    aqueous Ieed phase, which contains the target species that selectively reacts with the extractant, Ilows through the inner side oI
    the microporous Iibers oI the module |3|.
    Solute mass transport through reactive liquid membranes is basically described by the principles oI Iacilitated transport that
    combines reaction and diIIusion steps, and is considered to take place through several in-series steps: (i) solute diIIusion
    through the Ieed phase stagnant layer to the interIace with the membrane, (ii) interIacial reaction between the solute and the
    selective extractant to Iorm organic complex species, (iii) diIIusion through the liquid membrane, iv) diIIusion through the
    organic phase stagnant layer to the interIace with the droplets containing the back-extraction solution and, (v) chemical
    reaction between the organic complexes and the back-extraction agent |3|. However, the rigorous description oI a membrane
    contactor comprises not only the characterization oI mass transIer phenomena and interIacial chemical reactions, but also the
    -64-
    mathematical modeling oI the Iluid Ilow on either side oI the membrane (tube and shell sides) by the development oI the
    appropriate conservation and continuity equations.
    This work proposes the guidelines Ior the rigorous mathematical modeling oI membrane contactors as an essential tool Ior the
    optimal design oI EPT separation systems that requires the simultaneous integration oI the extraction and stripping rates.
    Finally, the methodology is illustrated by its application to a selected case study that deals with the removal and recovery oI
    zinc Irom eIIluents coming Irom diIIerent steps oI a hot-dip galvanizing process.
    Financial support Irom projects CTQ2008-00690/PPQ and CTQ2008-05545 (MCI, Spain) is grateIully acknowledged.
    |1| J. de Gyves, E. Rodriguez de San Miguel, Metal ion separations by supported liquid membranes, Ind. Eng. Chem. Res.,
    1999, 38, 2182-2202.
    |2| J.M. Wiencek, S. Hu, Emulsion liquid membrane extraction in a hollow-Iiber-contactor. Chem. Eng. Technol., 2000, 23,
    551-553.
    |3| J.A. Carrera, E. Bringas, M.F. San Roman, I. Ortiz, Selective membrane alternative to the recovery oI zinc Irom hot-dip
    galvanizing eIIluents, J. Memb. Sci., 2009, 326, 672-680.
    OC.2.6
    Modeling of coupled mass and heat transfer through venting membranes for
    automotive applications
    A. Barkallah
    1,2
    , S. Druon Bocquet
    1
    , J. Sanchez
    1
    , J. Rivenc
    2
    1
    Institut Europeen des Membranes (IEM). ENSCM, UM2, CNRS - Universite de Montpellier II, CC 047 , Place Eugene
    Bataillon - 34095 Montpellier, France.
    2
    Technocentre Renault, 1 Avenue du Golf, 78288 Guvancourt Cedex, France
    sancheziemm.univ-montp2.Ir
    Automotive electronic devices or electronic control units (ECU) are usually placed inside a hermetically sealed box in order to
    protect it Irom the surrounding Iluids (liquids and gases). The limitation oI this solution are the pressure changes in the box
    which are essentially the result oI temperature changes due to normal electronic working conditions or external heat sources
    such as engine heat dissipation, solar energy accumulation etc. In Iact, these phenomena lead to mechanical strains on the
    sealing and on the box material itselI, leading to a possible loss oI reliability. The use oI hydrophobic macroporous
    membranes, which can let air pass and prevent all liquids Irom passing through, is a solution to this problem. Nevertheless,
    these membranes are not selective to water vapor transIer and their use can lead to water condensation in the case oI rapid
    temperature decrease aIter a long exposition to high values oI relative humidity.
    For the reasons exposed above, it is very important to have a good knowledge oI the evolution oI mass and heat transIers
    inside such ECU in order to quantiIy the impact oI a membrane under normal or extreme environmental conditions. For this
    purpose, the development oI models coupling mass and heat transIers is necessary to understand the evolution oI internal
    parameters, such as temperature, pressure and relative humidity variation during a car typical use conditions.
    The main objective oI this work was to build up a model |1| oI mass and heat transIer in an enclosure which has a part oI its
    surIace covered with a macroporous and hydrophobic membrane. This enclosure or electronics housing is placed in
    environmental conditions which are representative oI automotive working conditions with variations oI temperature, relative
    humidity, total pressure and partial water vapor pressure. The housing contains also a printed circuit board (PCB) that includes
    a source oI heat.
    This work starts with the characterization oI diIIerent commercial macroporous and hydrophobic membranes in order to
    determine the main relationships between the membrane structure and mass transport parameters used as modeling inputs. A
    model was then established, starting Irom general heat and mass transport equations and coupling them by taking into account
    their reciprocal dependences. Simulations were carried Ior diIIerent environmental conditions and the results were compared
    to the experimental data obtained with two diIIerent enclosures in order to validate the model.
    Finally, we theoretically studied the impact oI some parameters oI the system on heat and mass transIer Iluxes in order to
    choose the best parameters related to both, membrane structure and housing design.
    |1| Modeling oI coupled mass and heat transIer through venting membranes Ior automotive applications. A. Barkallah, J.
    Mree, J. Sanchez, S. Druon Bocquet, J. Rivenc. AIChE Journal, 2008, in press.
    -65-
    OC.2.7
    Numerical study of the fractionation of two proteins with opposite charges by a
    hybrid membrane cell composed of symmetrically charged membranes
    S.I.S. Pinto
    1
    , J.M. Miranda
    2
    , J.B.L.M. Campos
    1
    1
    Centro de Estudos de Fenomenos de Transporte, Departamento de Engenharia Quimica, Faculdade de Engenharia da
    Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
    2
    Universidade Lusofona do Porto, Rua Augusto Rosa, n24, 4000-098 Porto, Portugal
    deq06006Ie.up.pt
    Hybrid membrane cells combine two types oI membranes with diIIerent properties alternating in series |1|. By careIully
    selecting the membrane properties, it is possible to develop innovative methods to Iractionate proteins. For example, Pinto et
    al. developed a process, in a hybrid membrane cell, to separate proteins by diIIerential diIIusion |2|. Hybrid membrane cells
    can also be used to reduce concentration polarization and to increase the apparent selectivity oI protein Iractionation |1|. This
    higher selectivity is mainly due to the cleaning oI the polarized boundary layer |1|. In this work a new Iractionation process in
    a hybrid membrane cell is explored. The hybrid membrane is composed oI positively and negatively charged membranes
    alternating in series (Figure 1). When electric interactions between the membrane and the proteins are more important than
    steric eIIects, each membrane preIerentially rejects the proteins with the same charge and transmits the proteins with the
    opposite charge |3|. By selecting operating conditions (crossIlow velocity, pressure, ionic strength and pH) and membrane
    properties (pore sizes and electric charge) we seek to develop systems in which the protein that polarizes a membrane due to
    electric repulsion is transmitted through the subsequent membrane (Figure 1). This mechanism reduces polarization and
    increases selectivity. The positively charged protein is transmitted through the negatively charged membrane and negatively
    charged protein through the positively charged membrane (Figure 1). The process is studied by solving the Poisson-
    Boltzmann, the Navier-Stokes and the Nernst-Planck equations by Iinite diIIerence methods. The eIIect oI the electric charge
    oI the membranes in protein transmission and selectivity is studied in detail.
    Figure 1 Hybrid membrane cell composed oI positively and negatively charged membranes.
    |1| J. M. Miranda and J. B. L. M. Campos, Chemical Engineering Science, 62 (2007), 1215 1229.
    |2| S.I.S. Pinto, T.M.G.T. Rocha, J.M. Miranda, J.B.L.M. Campos, Desalination 241 (2009), 372-387.
    |3| R. van Reis, J. M. Brake, J. Charkoudian, D. B. Burns and A. L. Zydney, Journal oI Membrane Science 159 (1999),
    133-142.
    OC.2.8
    Nano-scale approach to diffusion in semi-crystalline polyolefins
    H. Hajova, R. Pokorny, T. Gregor, L. Seda, J. Kosek
    Institute of Chemical Technologv, Department of Chemical Engineering, Technicka 5, 166 28 Prague 6, C:ech Republic
    Juraj.Kosekvscht.cz
    Many commercially important polymers have semi-crystalline structure, that is, they consist oI amorphous and crystalline
    phases. Crystalline phase is oIten organized in lamellae oI characteristics thickness oI 10 nm. Lateral growth oI lamellae Irom
    nucleation center, their branching, twisting and stacking creates spherulites oI characteristic size 100 nm to 10 microns.
    -66-
    DiIIusion oI penetrants in semi-crystalline polymers is important in manuIacturing, in packaging applications and in
    membranes.
    This contribution reports on our progress in experimental characterization oI semi-crystalline morphology oI polyethylene.
    Samples oI polyethylene are microtomed, their surIace is selectively etched by oxygen plasma and lamellar morphology is
    visualized by AFM. Various statistical descriptors are employed to characterize lamellar morphology. DiIIusion in semi-
    crystalline polymers is measured gravimetrically in the apparatus utilizing magnetic suspension balance and mass
    spectrometer, so that co-diIIusion measurements oI several species are also possible. Another apparatus allows measuring the
    diIIusion in polymer melt, so that obstruction eIIect oI semi-crystalline structure can be determined.
    We demonstrate the developed modelling tools capable oI mapping between the semi-crystalline morphology and transport oI
    penetrants. We reconstruct spatially 3D structures oI spherulites consisting oI lamellae, calculate eIIective diIIusivity oI the
    reconstructed semi-crystalline structure and compare the results to our experimental data oI diIIusion in compact Iilms, Iibers
    and particles. We demonstrate why polyethylene materials with the same crystallinity oIten exhibit widely diIIerent
    diIIusivities.

    |1| J. Kosek, F. Stepanek, M. Marek: Modeling oI Transport and TransIormation Processes in Porous and Multiphase Bodies,
    in Advances in Chemical Engineering, 2005, Vol. 30, 137-203.
    |2| A. Novak, M. Bobak, J. Kosek, B.J. Banaszak. D. Lo, T. Widya, W.H. Ray, J.J. de Pablo, Ethylene and 1-hexene sorption
    in LLDPE under typical gas-phase reactor conditions: experiment, J. Appl. Polym. Sci. 2006, 100, 1124-1136.
    |3| M. Bobak, T. Gregor, J. Kosek, B. Bachman, Estimation oI morphology characteristics oI porous polypropylene particles
    Irom degassing measurements, Macromolecular Reaction Engineering 2008, 2, 176-189.
    OC.2.9
    Molecular investigations of gas and vapors transport properties in a modified co-
    poly(amide-12-b-ethylene oxide) membrane
    L. De Lorenzo
    1
    , E. Tocci
    2
    , A. Gugliuzza
    2
    , M. Macchione
    2
    , E. Drioli
    2
    1
    Department of Chemical Engineering and Materials, Universitv of Calabria, 87030 Rende (CS), Italv
    2
    Institute on Membrane Technologv ITM-CNR, Universitv of Calabria, 87030 Rende (CS), Italv
    ldeloreunical.it
    A combined experimental and theoretical study has been used to investigate gas diIIusion and solubility in a modiIied
    PEBAX

    2533 block copolymer membrane.


    Elastomeric block co-polyamides and polyurethanes have gained a unique position in many industrial applications Ior diIIerent
    reasons, mainly related to their good physical properties such as high processability, notable strength and interesting
    permselectivities both to gases and vapours |1,2|.
    Over the last 20 years, detailed atomistic molecular modeling has been successIully used to provide a deeper knowledge oI the
    correlations between small penetrants transport properties and structural Ieatures oI the polymeric membranes materials |3,4|.
    The aim oI this work is to investigate the gas and vapour transport properties oI PEBAX2533 block copolymer membrane
    when diIIerent concentrations oI an aromatic sulphonamide (KET) are added.
    Bulk assembled models oI PEBAX/KET with diIIerent copolymer/additive composition have been assembled and analyzed to
    evaluate gas solubility and diIIusivity: Gusev-Suter Transition State Theory (TST) and Monte Carlo methods are used Ior
    simulating the transport oI Iive permanent gases (He, H
    2
    , N
    2
    , O
    2
    , CO
    2
    , CH
    4
    ).
    -67-
    Figure 1. AFM phase image oI polyethylene sample shallow-
    etched by plasma, lamellar morphology.
    Figure 2. Digitally reconstructed spherulite particle with
    brached, stacked and twisted lamellae.
    Permeation experiments through modiIied Pebax membranes at diIIerent additivies composition have been perIormed Ior
    permanent gases and vapors at diIIerent operating conditions. The theoretical data have been compared with experimental ones
    in order to validate the investigative approach.
    This work has been supported by the European Commission 6th Framework Program Project MULTIMATDESIGN Computer
    aided molecular design oI multiIunctional materials with controlled permeability properties, Contract Number: NMP3-
    CT-2005-013644. The authors are grateIully to INSTM/CINECA Ior computational support (Superprogetto di calcolo 2006).
    |1| A. Gugliuzza and E. Drioli, Eur. Polvm. J., 40, (10) 2004, 2381.
    |2| A. Gugliuzza, G. De Luca, E. Tocci, L. De Lorenzo, E. Drioli , J. Phvs. Chem. B 111, 2007, 8868.
    |3| D. HoImann, L. Fritz, J. Ulbrich, C. Schepers, M. Bhning Macromol. Theorv Simul. 9, 2000, 293.
    |4| E. Tocci, A. Gugliuzza, L. De Lorenzo, M. Macchione, G. De Luca, E. Drioli J. Membr. Science, 323, 2008, 316.
    OC.2.10
    Simulation of membrane filtration at microscopic scale
    Q. Derekx
    1
    , D. Veyret
    3
    , K. Glucina
    4
    , P. Bacchin
    1
    , P. Moulin
    2
    1
    Laboratoire de Genie Chimique (UMR 5503), Universite Paul Sabatier 31062 Toulouse Cedex 9, France
    2
    Universite Paul Ce:anne Aix Marseille, Laboratoire de Mecanique, Modelisation et Procedes Propres (M2P2 UMR-CNRS
    6181), Europole de lArbois, BP. 80, Batiment Laennec, Hall C, 13545 Aix en Provence Cedex 04, France
    3
    POLYTECH Marseille, (CNRS-UMR 6595) Technopole de Chateau-Gombert, 5 rue Enrico Fermi, 13453 Marseille Cedex 3,
    France
    4
    Sue: Environnement, CIRSEE, Pole Qualite Eau, 38, rue du President Wilson, 78230 Le Pecq, France
    philippe.moulinuniv-cezanne.Ir
    The description oI the diIIerent mechanisms involved in Iouling phenomena is important to understand the membrane
    separation processes. However, these Iouling phenomena results Irom a complex interplay between physico-chemical
    properties and hydrodynamics occurring at a microscopic scale where the membrane and the dispersion exhibit complicated
    properties. Some authors have simulated Iouling phenomena in a simple geometry like Tung |1|. More oIten, the studies
    represent the membrane with a homogeneous permeability coeIIicient in a Darcy`s law |2-3|. In these conditions, it is oIten
    diIIicult to reach reliable data both Irom experiments and Irom numerical simulations. Our work concerns the simulation at the
    microscopic scale oI the behavior oI particles Ilowing through the 3D structure oI a membrane. The three-dimensional porous
    media is built either randomly (but by keeping the same macro-characteristics - porosity, permeability, pore size - than the
    membrane) or reconstructed Irom visual experiments (like 3D tomography). These simulations are made to represent an
    experiment oI a bentonite Iiltration at constant pressure. The Iiltered particles are taken spherical and divided in several classes
    depending on their size and on their capacity to stick to the membrane surIace which is considered by using the Hamaker
    theory. The Ilow Iield is solved together with the particle motion. The eIIect oI captured particles on hydrodynamics is
    accounted. The results yield the evolution oI the membrane characteristics, notably the permeability and the Iiltration Ilux,
    over time. The study allows simulating the diIIerent mechanisms oI pore blocking and cake Iormation. The transition between
    these mechanisms will be analyzed and the dependence to the physico-chemical properties, the hydrodynamics and the 3D
    structure will be discussed. The comparison oI these results with experimental data will be presented and interpreted through
    predominant Iouling mechanisms. The interest oI this study stays in the possibilities to have a better understanding oI the
    Iouling mechanisms at pore scale, oI the transitions between the diIIerent Iouling rate and oI the motors behind each
    mechanism. This study allows then an improvement oI the empiric models oI the Iouling and so an enhancement oI the
    process.
    |1| Tung, K.-L. (2006) "EIIect oI calendering oI Iilter cloth on transient characteristics oI cake Iiltration." Separation and
    PuriIication Technology 48: 1-15.
    |2| Bessiere, Y. (2008) "Numerical simulation oI colloid dead-end Iiltration: EIIect oI membrane characteristics and operating
    conditions on matter accumulation." Journal oI Membrane Science 313: 52-59.
    |3| Wiley, D. E. (2003) "Techniques Ior computational Iluid dynamics modelling oI Ilow in membrane channels." Journal oI
    Membrane Science 211: 127-137.
    -68-
    OC.2.11
    Forced permeation transition in high molecular weight polymer cross-flow
    ultrafiltration
    L. Beguin, H. Duval, M. Rakib
    Laboratoire de Genie des Procedes et Materiaux, Ecole Centrale Paris, Grande Joie des Jignes, F-92295 Chatenav-Malabrv,
    France
    herve.duvalecp.Ir
    Cross-Ilow ultraIiltration oI Ilexible linear high molecular weight polymers has been investigated Ior polymer hydrodynamic
    radius greater than membrane pore radius.
    Experiments have been perIormed in a 'model device with track-etch membranes (narrow pore distribution with mean pore
    radius equal to 23 nm and 35 nm) and high molecular weight polyethylene oxide (PEO molar mass equal to 10
    6
    g.mol
    -1
    and
    polydispersity index equal to 1.6). Experimental results show that the observed polymer retention ratio decreases as the
    permeate Ilux across the membrane increases.
    In order to distinguish concentration polarization Irom polymer distortion eIIects (because both oI them could be responsible
    Ior the decrease oI the observed retention ratio), the convection-diIIusion mass transIer coeIIicient oI the polymer toward the
    membrane has been determined. It is Iound that it increases as the permeate Ilux increases, according to De and Bhattacharya
    |1| relation. Finally, the intrinsic retention ratio has been derived. Its variations show that the polymer chains were able to
    penetrate the pores oI the membrane by distorting themselves when the permeate Ilux is higher than a critical Ilux: this
    situation corresponds to the so-called Iorced permeation regime.
    A good agreement between the experimental permeation threshold and Daoudi and Brochard |2| theory is obtained when the
    hydrodynamic radius and the Zimm relaxation time are taken as polymer characteristic length and relaxation time,
    respectively. However, it must be noticed that the transition Irom total retention to Iorced permeation regime is not as steep as
    scaling laws predict.
    |1| S. De and P.K. Bhattacharya, Prediction oI mass-transIer coeIIicient with suction in the applications oI reverse osmosis and
    ultraIiltration, Journal oI Membrane Science, 128, 1997, 119-131
    |2| S. Daoudi and F. Brochard, Flows oI Ilexible polymer solutions in pores, Macromolecules, 11, 1978, 751-758
    OC.2.12
    A heat-and-mass transfer correlation for sludge to optimize mass transfer in tubular
    airlift membrane systems
    N. Rios
    1
    , C.C.V. Chan
    2
    , P.R. Berube
    2
    , I. Nopens
    1
    1
    BIOMATH - Department of Applied Mathematics, Biometrics and Process Control, Ghent Universitv, Coupure Links 653,
    B-9000, Ghent, Belgium.
    2
    Department of Civil Engineering, The Universitv of British Columbia, 6250 Applied Science Lane, Jancouver, BC, J6T 1Z4,
    Canada
    nriosratbiomath.ugent.be
    Bearing in mind the more stringent eIIluent quality standards imposed by the EU Water Framework Directive (EU-WFD),
    treatment eIIiciencies need to be improved. These improvements can be achieved both in terms oI biological removal
    eIIiciency as well as in the sludge-water separation step with Membrane Bioreactors (MBR). However, a common problem
    encountered with MBR systems is Iouling oI the membrane |1|. Literature has shown that the hydrodynamics near the
    membrane surIace play an important role. To reduce the Iouling near the membrane oIten air is introduced in the activated
    sludge Ilow to create a gas-liquid two-phase cross-Ilow along membrane surIaces. This is done to increase the mass transIer
    coeIIicient between the cake layer and the bulk region to remove Ioulants that are already attached. During the Iiltration
    process, the separation between the sludge and the solute occurs at the membrane, giving an increase in the solute
    concentration near the membrane surIace. This is called concentration polarization |2|. The permeate Ilux ( J ) depends on the
    -69-
    mass transIer coeIIicient ( k ) and the concentrations near the membrane
    m
    C and in the bulk
    b
    C . Assuming that the
    membrane completely rejects the solute the Ilux is given by:
    ]
    ]
    ]
    ,

    ,

    b
    m
    C
    C
    k J ln (1)
    The mass transIer coeIIicient is correlated with the Sherwood number |3|. In this contribution, the objective is to determine the
    mass transIer coeIIicient Ior a two-phase Ilow in an airliIt side-stream MBR. Due to the complexity involved in mass transIer
    measurements Ior two-phase Ilows, there are some studies that Iocus on developing correlations between heat and mass
    transIer |4|. These kinds oI analogies are commonly used in cases where it is easier to obtain heat transIer data than mass
    transIer data. For the present study, a Plexiglas tube, similar in geometry to the airliIt tubular membranes oI interest, was used.
    The tube has a length oI 2 m with an inner diameter oI 9.9 mm. In the middle oI the tube (1 m) a Ilow cell is present which
    contains 2 electrochemical shear probes |5| which are capable to measure the shear stress and correlate to the mass transIer. 15
    diIIerent Ilow rates combinations oI water-gas (i.e. N
    2
    ) maintained at 20C, corresponding to the expected operating range in
    Iull-scale airliIt tubular membrane systems, were investigated. In this paper, a simple heat-and-mass transIer correlation that
    can be used with sludge |6| is presented. It is based on the mass transIer measurements that can be obtained Irom the shear
    probes using a correlation between voltage and shear stress. This correlation can be used to determine the best operational
    regime (Ilow rates or sludge-air) that will increase the mass transIer coeIIicient and decrease Iouling on the membrane.
    |1| Judd, S. (2006) The MBR book., Elsevier.
    |2| Mulder, M. (1998) Basic Principles oI Membrane Technology., Springer.
    |3| Ranjan, R., DasGupta, S., and De, S. (2004) Mass transIer coeIIicient with suction Ior laminar non-Newtonian Ilow in
    application to membrane separations. Journal oI Food Engineering 64 (1), 53-61
    |4| Shirazi, Siamack A., Al-Adsani, Ebrahin, Shadley, John R., and Rybicki, Edmund F. A mechanistic model Ior predicting
    heat and mass transIer in vertical two-phase Ilow. Proceedings oI the ASME Heat TransIer/Fluids Engineering Summer
    ConIerence 2004, HT/FED 2004, Jul 11-15 2004. 3, 685-693. 2004. Charlotte, NC, United States
    |5| Zheng, D. and Che, D. (2006) Experimental study on hydrodynamic characteristics oI upward gas-liquid slug Ilow.
    International Journal oI Multiphase Flow 32 (10-11), 1191-1218.
    |6| Kim, D., Ghajar, A.J., and Dougherty, R.L. (2000) Robust heat transIer correlation Ior turbulent gas-liquid Ilow in vertical
    pipes. Journal oI Thermophysics and Heat TransIer 14 (4), 574-578.
    OC.2.13
    Influence of thermal effects on gas-liquid absorption in a hollow fiber membrane
    contactor: case of carbon dioxide in a MEA solution
    N. BouciI
    12
    , D. Roizard
    1
    , E. Favre
    1
    1
    Laboratoire des Sciences du Genie Chimique (UPR 6811-Nancv Universite), ENSIC-BP 451 1, rue Grandville, F-54001
    Nancv Cedex- France
    2
    On sabbatical leave from the Departement de Chimie Industrielle et LPQ3M, Faculte des Sciences de lingenieur, Universite
    de Mascara, Mascara 29000, Algerie.
    Eric.Favreensic.inpl-nancy.Ir
    The mass transIer rates in gas-liquid absorption accompanied by chemical reaction can be signiIicantly inIluenced by thermal
    eIIects, which result Irom reaction and solution enthalpies. Nevertheless, non isothermal eIIects remain almost unexplored Ior
    gas absorption with chemical reaction in membrane contactors.
    This study intends to evaluate the incidence oI non isothermal eIIects in membrane contactors, based on a case study. A
    rigorous mathematical model was developed based on the conservation laws oI the absorption oI carbon dioxide in aqueous
    monoethanolamine solution to predict the carbon dioxide removal eIIiciency. The nonisothermal absorption is taking place in a
    hollow Iiber membrane contactor considering diIIusion oI the gas Iollowed by an exothermic and reversible second order
    reaction. The liquid solution is Ilown in the hollow Iiber bore and the gas in the shell side in a counter-current Ilow pattern.
    The model consists oI a set oI coupled partial and ordinary diIIerential equations Ior mass and heat transIer Ior all the species
    involved in the process. The numerical simulation involves dimensionless parameters such as the Graetz Ior heat and mass
    transport, the Sherwood, the Damkhler, and the Nusselt numbers oI various module temperature entrances.
    Finally, the deviations Irom the classical isothermal situation can be systematically predicted and it is shown that the carbon
    dioxide and solvent extents are considerably aIIected by the temperature increase as well as by gas to liquid ratios G/L.
    -70-
    OD.1.1
    Ionic strength impact in filtration of skimmed milk: analysis of casein micelles and
    cake properties
    G. Gesan-Guiziou
    1, 2
    , A. Bouchoux
    1, 2
    , A. Jimenez-Lopez
    1, 2, 3
    , F. Garnier-Lambrouin
    1,2
    1
    INRA UMR1253 Science et Technologie du Lait et de luf, 65 rue de saint Brieuc, F-35000 Rennes, France
    2
    Agrocampus Ouest UMR1253 F-35000 Rennes, France
    3
    Soredab SAS, La Tremblave, F-78125 la Boissiere Ecole, France
    genevieve.gesan-guiziourennes.inra.Ir
    CrossIlow Iiltration is widely used in the dairy industry as tools Ior the separation and the Iractionation oI speciIic solutes and
    proteins in milk. For instance, the microIiltration oI skimmilk using a 0.1 m mean pore membrane separates the "naturally
    aggregated" proteins oI milk (the casein micelles) Irom the whey components (lactose, minerals and small molecular weight
    proteins) in a single operation. Both concentrate and permeate are oI great interest either Ior cheese making or protein
    Iractionation.
    The perIormance (permeability and selectivity) oI skimmed milk microIiltration are mainly ruled by the Iormation oI a cake
    layer at the membrane surIace during the course oI Iiltration. Understanding the properties oI this cake layer and the
    mechanisms involved in its Iormation is oI major importance Ior developing strategies to improve membrane-based processes
    in the dairy industry. Casein micelles were shown to be the main components oI the Iouling layer developing over the
    membrane. They are complex colloidal entities with a mean diameter oI roughly 150 nm and are in dynamic equilibrium with
    the solvent phase oI milk. Some studies, based on the variation oI the cake resistance with milk physicochemical parameters
    (pH; ionic strength, I), show the direct relation between the electrophoretic mobility oI the casein micelles and the degree oI
    Iouling. However, the impact oI I on both the cake properties and the characteristics oI micelles dispersions has not been
    exhaustively analyzed until now.
    The eIIect oI ionic strength on the cake properties is deeply investigated in the present work. Filtrations oI skimmed milk and
    casein micelles dispersions were perIormed in dead-end and crossIlow modes with ultra (100 kg mol
    -1
    MWCO) and
    microIiltration (0.1 m) membranes. The cakes Iormed upon dead-end Iiltrations were analyzed in terms oI average speciIic
    resistance by Iollowing the permeate volume with time. The actual deposited mass, the cake dry matter content, as well as the
    absolute remaining cake resistance were also determined aIter Iiltration and rinsing oI the cell. In crossIlow Iiltration, an
    original methodology based on step by step shear stress variation at constant permeation Ilux was used to determine deposit
    conditions oI Iormation and reversibility. Size, electrophoretic mobility, hydration and osmotic pressure oI the casein micelles
    dispersions, which reIlects the balance oI all interactions in the system and inIorms on sol-gel transition range, were measured.
    Regardless oI the Iiltration modes, the increase in I enabled an easier set-up oI micelles deposit and induced a more cohesive
    and irreversible cake. In particular, the average speciIic resistances reported in dead-end Iiltrations were high compared to
    resistances obtained with non modiIied milk. The osmotic pressure measurements conIirmed the high compression resistance
    oI casein micelles dispersions obtained with addition oI NaCl in concentrated regime: the dispersions oI casein micelles with
    300 mM oI added salt had a compression resistance that was nearly twice as high as that oI 'native dispersions. Moreover
    when increasing ionic strength, there was a slight shiIt oI the Iluid-solid transition to lower pressures and volume Iractions, and
    a remarkable increase in gel cohesion.
    The perIormances oI Iiltration could be explained considering: i) a closer contact between casein micelles due to the decrease
    oI casein micelles electrophoretic mobility (as the micelle sizes do not change signiIicantly with ionic strength); ii) more
    accessible hydrophobic groups that may be protected by the -casein brush at low ionic strength that is partially collapsed at
    high ionic strength; iii) higher water aIIinity oI the casein micelle due to a high ionic content in the core oI the system. All the
    Iiltration observations were discussed based on the known characteristics oI the casein micelle (micelle electrophoretic
    mobility, "soItness", hydration...) and help to understand the involved mechanisms in Iiltration oI skimmed milk.
    -71-
    OD.1.2
    Separation of -Lactalbumin and -Lactoglobulin from skim milk by dynamic
    filtration
    V. Espina
    1
    , M. Y. JaIIrin
    2
    , L.H. Ding
    1
    Technological Universitv of Compiegne.
    1
    EA 4297 TIMR, 60205 Compiegne, France.
    2
    UMR 6600, BP 20529, 60205
    Compiegne, France.
    michel.jaIIrinutc.Ir
    The Iractionation and puriIication oI whey proteins present a signiIicant commercial interest Ior the dairy industry because oI
    their pharmaceutical and nutritional applications. This work describes a two-stage membrane Iiltration process Ior extracting
    and separating u-Lactalbumin (u-La) and -Lactoglobulin (-Lg), Irom UHT skim milk, using dynamic (or shear-enhanced)
    Iiltration. The 1
    st
    stage separates casein
    micelles in retentate Irom whey proteins in permeate with 0.2m pores 9-
    cm diameter ceramic membranes rotating at 1930 rpm and mounted in a
    MSD pilot |1|. The 2
    nd
    stage consisted in an ultraIiltration oI the previous
    permeate with a 15-cm diameter metal disk rotating at 2000 rpm near a
    Iixed 50 kDa PES membrane, in order to concentrate -Lg in retentate,
    while collecting u-La in permeate. In MF, casein rejection was excellent
    with a permeate turbidity 50 NTU, while u-La and -Lg transmissions
    remained between 0.8 and 0.9 and permeate Ilux at 40C decayed Irom
    105 to
    40 Lh
    -1
    m
    -2
    at a volume reduction ratio (VRR) oI 4. In UF, the Ilux
    remained at 200 Lh
    -1
    m
    -2
    until VRR3.3. Whey protein transmissions are
    shown in Fig.1 and gave a maximum selectivity oI 8 at the maximum
    VRR. The u-La yields in The Iractionation and puriIication oI whey
    proteins present a signiIicant commercial interest Ior the dairy industry because oI their pharmaceutical and nutritional
    applications. This work describes a two-stage membrane Iiltration process Ior extracting and separating u-Lactalbumin (u-La)
    and -Lactoglobulin (-Lg), Irom UHT skim milk, using dynamic (or shear-enhanced) Iiltration. The 1
    st
    stage separates casein
    micelles in retentate Irom whey proteins in permeate with 0.2m pores 9-cm diameter ceramic membranes rotating at 1930
    rpm and mounted in a MSD pilot |1|. The 2
    nd
    stage consisted in an ultraIiltration oI the previous permeate with a 15-cm
    diameter metal disk rotating at 2000 rpm near a Iixed 50 kDa PES membrane, in order to concentrate -Lg in retentate, while
    collecting u-La in permeate. In MF, casein rejection was excellent with a permeate turbidity 50 NTU, while u-La and -Lg
    transmissions remained between 0.8 and 0.9 and permeate Ilux at 40C decayed Irom 105 to 40 Lh
    -1
    m
    -2
    at a volume reduction
    ratio (VRR) oI 4. In UF, the Ilux remained at 200 Lh
    -1
    m
    -2
    until VRR3.3. Whey protein transmissions are shown in Fig.1 and
    gave a maximum selectivity oI 8 at the maximum VRR. The u-La yields in permeate were 0.59 in MF and 0.22 in UF.
    Conclusion. This process has not been yet optimized, but our data compare Iavourably with those oI literature. In Iuture tests, it
    will be important to use higher initial volumes and to replace ultraIiltration by diaIiltration, in order to raise the u-La yield in
    permeate.
    V. Espina has been supported by a scholarship N E06D101610CL oI the Alban European Union Program Ior Latin America.
    The authors thank WestIalia Separator Ior the loan oI a MSD pilot.
    |1| V.S. Espina, M.Y. JaIIrin, M. Frappart, L.H. Ding, Separation oI casein micelles Irom whey proteins by high shear
    microIiltration oI skim milk using rotating ceramic membranes and organic membranes in a rotating disk module. J. Membr.
    Sci 2008, 325,872-879
    -72-
    Fig.1. u-La and -Lg transmissions vs VRR in UF
    OD.1.3
    Application of nanofiltration for swimming pool water treatment - potential and
    challenges
    A. M. KlpIel, T. Glauner, F. H. Frimmel
    Engler-Bunte-Institute, Chair of Water Chemistrv, Engler-Bunte-Ring 1, 76131 Karlsruhe, Germanv
    angela.kluepIelebi-wasser.uni-karlsruhe.de

    Due to the constant water recirculation and to the alternating number oI visitors, high demands are made on swimming pool
    water treatment. In recent studies concerning the time dependent concentrations oI dissolved organic carbon (DOC) and
    disinIection by-products (DBPs) in public swimming pools, classical treatment processes (i. e. Ilocculation sand Iiltration
    chlorination) were Iound to not eIIiciently remove the dissolved organic matter in periods oI high bather load and hence to
    Iacilitate the Iormation oI potentially irritating or toxic DBPs |1|. The application oI advanced treatment technologies might
    enhance the pool water quality while simultaneously reducing chemical (especially chlorine), water and energy costs (heating
    oI the Iresh water). According to recent studies |2-4|, nanoIiltration (NF) can be considered as a promising technique Ior
    considerable DBP and DBP precursor elimination. However, to the authors knowledge there have been no Iurther studies on
    the perIormance oI NF membranes in swimming pool water treatment yet.
    Batch experiments have been conducted in a bench scale plant consisting oI eight Ilat sheet modules operated in parallel.
    Commercially available nanoIiltration membranes oI diIIerent materials, manuIacturers and molecular weight cut oII (MWCO)
    have been investigated concerning their DOC and DBP removal potential. A model was developed based on a DOC mass
    balance Ior the treatment cycle in order to estimate the possible savings in terms oI operating costs Ior the combination oI
    ultraIiltration (UF) and NF (the latter in a variable split Ilow treatment depending on the bather load). Model validation was
    perIormed via DOC on-line measurements (4 weeks) Ior a public indoor swimming pool with a classical water treatment
    system. During the NF experiments the concentrations oI DOC, AOX (adsorbable organic halogens) as well as the maximal
    AOX- and THM (trihalomethanes) Iormations could be signiIicantly reduced (e. g. 90, 94, 86 and 83 Ior NF 90 (PA, DOW,
    MWCO 100 g/mol) and 63, 54, 53 and 58 Ior NP 030 (PES, Microdyn-Nadir, MWCO 1500 g/mol at 10 bar)).
    Calculations concerning the expected Iresh water consumption at a given water quality Ior diIIerent treatment scenarios
    resulted in a signiIicantly reduced Iresh water consumption Ior the combination oI UF and NF (NP 030 in variable split Ilow
    treatment) with backwash water treatment in comparison to a classical treatment system. Further nanoIiltration experiments in
    by-pass to the treatment system in a public indoor swimming pool are in progress and will show the long term perIormance oI
    diIIerent chlorine resistant NF membranes during pool water treatment.
    The authors would like to thank the Water Chemical Societv (Division of the German Chemical Societv) and the German
    Technical and Scientific Association for Gas and Water (DJGW) for financial support.
    |1| C. Zwiener, S. D. Richardson, D. M. De Marini, T. Grummt, T. Glauner, F. H. Frimmel, Environ. Sci. Technol., 2007, 41,
    363-372.
    |2| T. Glauner, P. Waldmann, F. H. Frimmel, C. Zwiener, Water Res., 2005, 39, 4494-4502.
    |3| A. de la Rubia, M. Rodriguez, V. M. Leon, D. Prats, Water Res., 2008, 42, 714-722.
    |4| F. H. Frimmel, F. Saravia, A. GorenIlo, Water Sci. Technol., 2004, 4(4), 165-174.
    OD.1.4
    Nanofiltration process in fractionation of galacto-oligosaccharides continuously
    produced in bioreactors
    V.A. Botelho-Cunha
    1,2
    , M. Mateus
    3
    , J.C.C. Petrus
    2
    , M.N. de Pinho
    1
    1
    Chemical and Biological Engineering Department, Instituto Superior Tecnico, 1049-001 Lisboa, Portugal
    2
    Chemical Engineering & Food Engineering Department, Centro Tecnologico, Universidade Federal de Santa Catarina,
    88040-900 Florianopolis, SC-Bra:il
    3
    IBB - Institute for Biotechnologv and Bioengineering, Centre for Biological and Chemical Engineering, Instituto Superior
    Tecnico, Lisbon, Portugal
    vanessalbresyahoo.com
    Several beneIicial eIIects are claimed on the consumption oI galacto-oligosaccharides (GOS) that are considered prebiotics
    since humans do not digest them and stimulate the growth and/or activity oI bacterial Ilora. Enzymes can synthesize GOS Irom
    -73-
    lactose, but the reaction equilibrium is shiIted to Iavor hydrolysis over synthesis in aqueous systems, which leads to a low yield
    in GOS production at lower lactose concentration in solution due to the high values oI values oI water activity |1|.
    Bioprocessing with concentrated substrate solutions should thereIore be Iavored. The separation oI GOS Irom substrate is also
    important to prevent their hydrolysis |2|. NanoIiltration appears to be a potential industrial scale method Ior puriIication and
    concentration oI oligosaccharides mixtures at higher sugars concentration |3;4| and more studies are need Ior a critical
    evaluation. Recently, we have studied the Iractionation ability oI laboratory-made cellulose acetate nanoIiltration membranes
    towards GOS that were continuously produced in high concentration lactose solutions using an immobilized -galactosidase
    Irom Kluvveromvces lactis |3|. Experiments have shown that monosaccharides (glucose and galactose, indistinctly)
    transmission through the membrane is dependent on applied pressure, the observed rejection (R
    obs
    ) increasing Irom 40 to
    82 with pressure increase (0.5-13 bar oI eIIective transmembrane pressure), and much less dependent with changes in total
    sugars concentration (150 and 300 g/L) and in temperature (25C and 40C). Conversely, transmissions oI lactose and oI other
    galacto-disaccharides (-galactosidase converted) were reasonably diIIerent Irom one another in the range oI operating
    conditions studied, mainly at higher sugar concentration, showing that the transport oI simple sugars through nanoIiltration
    membranes can be conIormation dependent. The Iraction oI galacto-trisaccharides was totally retained within the pressure
    range oI study when total sugar concentration was 150 g/L was nanoIiltered. A two-Iold increase in sugars concentration in the
    Ieed led to the observation oI trisaccharides transmission through the membrane (R
    obs
    ranging Irom 85 to 90).
    The objectives oI the present work are (i) the comparison oI Iormer continuous GOS production and Iractionation data, with
    bead-immobilized -galactosidase, to those obtained with Iree enzyme in a membrane reactor, and (ii) the evaluation oI the
    impact on the sugar nanoIiltration Iractionation by the integration oI bioreaction with downstream processing.
    This research project is supported by Alan Programme, the European Union Programme oI High Level Scholarships Ior Latin
    America, scholarship n E07D402537BR.
    Goulas, A., Tzortziz, G., Gibson, G.R. Development oI a process Ior the production and puriIication oI - and -
    galactooligosaccharides Irom Bifidobacterium bifidum NCIMB 41171. Int. Dairv J. , 17, 648-656 (2007)
    Boon, M.A., van`t Riet, K., Janssen, A.E.M. Enzymatic synthesis oI oligosaccharides: product removal during a kinetically
    controlled reaction. Biotechnol Bioeng., 70, 411-420 (2000)
    Botelho-Cunha, V.A., Mateus, M., Petrus, J.C.C., de Pinho M.N. Tailoring nanoIiltration parameters Ior the Iractionation and
    synthesis oI galacto-oligosaccharides with bead-adsorbed -galactosidase. Biotechnol Prog. (submitted)
    Sjman, E., Mnttri, M., Nystrm, M., Koivikko, H., Heikkil, H. Separation oI xylose Irom glucose by nanoIiltration Irom
    concentrated monosaccharides solutions. J Membr Sci., 292, 106-115 (2007)
    OD.1.5
    Influence of additive mineral salt on the purification performances of glucose/sodium
    lactate solutions by nanofiltration
    C. Umpuch
    1,2,3
    , S. Galier
    1,2
    , S. Kanchanatawee
    3
    , H. Roux-de Balmann
    1,2
    1
    Universite de Toulouse , INPT, UPS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    2
    CNRS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    3
    School of biothechnologv, Suranaree Universitv of Technologv, 111 Universitv Avenue, Muang, Nakhon Ratchasima
    3000Thailand
    galierchimie.ups-tlse.Ir
    NanoIiltration is expected to be adapted to the separation oI neutral solutes, like sugars, Irom charged ones, like organic acid
    salts depending on their molecular weight. The present work Iocuses on the study oI a nanoIiltration step to puriIy solutions
    containing sodium lactate and glucose. For instance, such solutions are representative oI those that can be encountered during
    the puriIication stages in the lactic acid production.
    The experimental study was carried out with an NF Desal DK membrane and solutions oI increasing complexity, i.e. single
    solutions oI glucose or sodium lactate on one hand and mixed ones, containing both solutes, on the other hand. A good
    selectivity was expected Irom single solute solutions, since the retention oI glucose is higher than that oI sodium lactate.
    However, it was observed that the retention oI glucose in mixed solution was signiIicantly decreased. As a result, whilst good
    separation was expected Irom results obtained with single solute solutions, the NF selectivity achieved with mixed solutions
    was Iinally very poor. Such an eIIect oI the presence oI charged species on the retention oI neutral ones was reported in
    diIIerent situations, with organic as well as inorganic membranes and with diIIerent kind oI solutes, like organic acid
    1,2
    salts
    and PEG
    3
    Ior instance.
    On the other hand, it was demonstrated that the addition oI a charged solute can change signiIicantly the retention oI the ones
    either neutral or charged.
    -74-
    The aim oI this study is to investigate to what extend the ionic composition can be changed to improve the selectivity oI the
    glucose/sodium lactate separation by NF by adding diIIerent mineral salts, like NaCl (0.1-1M) and Na
    2
    SO
    4
    (0.1-0.5M). The
    results show that, in the lower Ilux region, where the transIer is limited by the diIIusion, the selectivity can be signiIicantly
    improved by the addition oI a salt. Consequently, it depends on the nature and concentration oI the added ions as well as on the
    sodium lactate concentration. This improvement is more important as the retention oI the added ion increased.
    |1| G. Bargeman, J.M. Vollenbroek, J. Straatsma, C.G.P.H. Schroen, R.M. Boom, NanoIiltration oI multi-component Ieeds.
    Interactions between neutral and charged components and their eIIect on retention, J. Membrane Sci., 2005,247, 11-20
    |2| A. Bouchoux, H. Roux-de Balmann, NanoIiltration oI glucose and sodium lactate solutions. Variations oI retention
    between single- and mixed-solute solutions, J. Membrane Sci., 2005, 258, 123-132
    |3| S. Bouranene, A. Szymczyk, P. Fievet, A. Vidonne, InIluence oI inorganic electrolytes on the retention oI
    polyethyleneglycol by nanoIiltration ceramic membrane, J. Membrane Sci., 2007, 290, 216-221
    OD.1.6
    Permselectivity of inorganic and organic ions by ion-exchange membranes:
    treatment of RO-concentrate by electrodialysis
    Y. Zhang
    1
    , B. Van der Bruggen
    1
    , L. Pinoy
    2,4
    , B. Meesschaert
    3,4
    1
    Department of Chemical Engineering, Laboratorv for Applied Phvsical Chemistrv and Environmental Technologv,
    Katholieke Universiteit Leuven, W. de Crovlaan 46, B-3001 Leuven, Belgium
    2
    Department of Industrial Engineering, Laboratorv for Chemical Process Technologv, KaHo St.-Lieven, Associated to the
    Katholieke Universiteit Leuven as Facultv of Industrial Sciences, Technologie campus, Gebroeders Desmetstraat 1, B-9000
    Gent, Belgium and M
    2
    S, KUL Association, K.U.Leuven
    3
    Department of Industrial Sciences and Technologv, Katholieke Hogeschool Brugge-Oostende, Associated to the Katholieke
    Universiteit Leuven as Facultv of Industrial Sciences, Zeedifk 101, B-8400 Oostende, Belgium
    4
    Department of Molecular and Microbial Sciences, Katholieke Universiteit Leuven, Arenberg Park 20, B-3001 Leuven,
    Belgium
    Bart.vanderbruggencit.kuleuven.be
    The production oI a saline and eutrophic content (e.g. organic compounds, phosphate and nitrate) concentrate is one oI the
    major drawbacks Ior the application oI reverse osmosis (RO). To improve water and nutrient recovery Irom RO concentrates
    Irom a Iood industry plant, separation oI salts Irom the organic Iraction and Irom nutrient anions is required. In this paper, the
    use oI ion-exchange membranes in electrodialysis was investigated to this purpose. Various types oI selective and non-
    selective anion exchange membranes were investigated in bench scale experiments. DiIIerent approaches including lowering
    the initial current density and increasing the initial pH were studied. The transport properties oI diIIerent anions and diIIerent
    small charged organic compounds through ion exchange membranes were discussed. The separation eIIiciency, which
    represents the selectivity, was compared under diIIerent conditions. The results show that separation oI non-nutrient anions
    Irom nitrate and phosphate was diIIicult, whereas separation oI salts Irom the organic Iraction was Ieasible, which proves that
    the organic Iractions in the RO concentrates are similar to uncharged test solutes used in the experiments. Furthermore, it was
    shown that a higher molar mass oI the organic solute has a positive eIIect on the separation. Lowering the current density can
    increase the separation eIIiciency oI monovalent to multivalent anions with either the non-selective membranes or the
    monovalent selective membranes. When the initial pH was increased, the separation eIIiciency oI monovalent to multivalent
    anions can be improved Ior monovalent selective membranes, however, no obvious change was Iound Ior the non-selective
    membranes. Furthermore, experiments on real RO concentrates proved that the separation oI salts Irom organics by
    electrodialysis is similar to the separation oI salts Irom uncharged solutes and thereIore Ieasible. Finally, pilot scale studies
    were carried out to examine the results Irom the bench scale experiments.
    -75-
    OD.1.7
    Ampholyte transfer in ion exchange membrane systems at underlimiting and
    overlimiting currents
    E. Belova
    1
    , N. Pismenskaya
    1
    , V. Nikonenko
    1
    , K. Lebedev
    1
    , G. Pourcelly
    2
    , Ph. Sistat
    2
    1
    Membrane Institute, Kuban State Universitv, 149 Stavropolskava str., 350040 Krasnodar, Russia
    2
    Institut Europeen des Membranes, ENSCM, UM2, CNRS, Universite Montpellier 2, CC047, Place Eugene Bataillon, 34095
    Montpellier Cedex 5, France
    belova.elenainbox.ru
    Comparative analysis oI mass transIer mechanisms in membrane systems with NaCl, CH
    3
    COONa and LysHCl, NaHCO
    3
    ,
    Na
    2
    CO
    3
    , NaH
    2
    PO
    4
    , Na
    2
    HPO
    4
    , Na
    3
    PO
    4
    . solutions is IulIilled by using mathematical modeling as well as data oI voltammetry
    (CVC) and chronopotentiometry (ChP). It is shown that in imposed electric Iield organic and non-organic ampholyte transIer is
    determined by current-induced hydrolysis reactions running due to variation oI pH with coordinate. A jump oI pH occurs at
    solution/membrane interIace. The character oI pH variation, as well as the kind and the rate oI hydrolysis reactions depend on
    ionization constants related to diIIerent Iorms oI ampholyte. The pH value oI internal solution in membrane is controlled as
    well by chemical equilibriums involving H

    and OH

    ions. Thus, in the case oI anion exchange membrane, the H

    ions are
    partly excluded Irom the membrane as co-ions (Donnan exclusion), that leads to an increase in internal solution pH. During
    electrodialysis oI a NaH
    2
    PO
    4
    solution, H
    2
    PO
    4

    ions enter the membrane and get into a milieu with increased pH. This leads to
    the loss oI a part oI H

    ions and their return to the depleted diIIusion layer. The HPO
    4
    2
    ions Iormed in this reaction continue
    their Ilow through the membrane. ThereIor, the membrane/solution boundary becomes generator oI H

    ions beIore reaching
    limiting current. At overlimiting currents, the rate oI H

    (OH

    ) generation increases, the mechanism oI hydrolysis reactions


    depending on rate constants Ior diIIerent stages oI these reactions. In some cases, two-wave ChP and CVC are observed as it is
    shown in Figure 1.
    Figure 1 : Chronopotentiograms oI an AMX membrane in 0.1 M
    solution oI diIIerent electrolytes
    Figure 2 : DiIIerential Iorms oI the chronopotentiograms
    shown in Figure 1
    Russian Foundation Ior Basic Research (09-08-96523) and CNRS are acknowledged Ior granting the work.
    OD.1.8
    Impact of organic component on separation efficiency during hydrophilic
    pervaporation
    W. M. Kujawski
    Membrane Separation Processes Group, Facultv of Chemistrv, Nicolaus Copernicus Universitv, 7, Gagarina Str., 87-100
    Torun, Poland
    kujawskichem.umk.pl
    Hydrophilic pervaporation is a membrane separation operation, which is used to dehydration oI organic liquid mixtures |1|. In
    this technique the Ieed is placed in contact with one side oI a hydrophilic membrane (polymeric or ceramic) whereas permeate
    -76-
    is removed in the vapor state Irom the opposite side, kept either under the vacuum (vacuum pervaporation) or under a stream
    oI an inert gas (sweeping gas pervaporation). The eIIiciency oI dehydration by pervaporation depends on composition and
    morphology oI the membranes, but also on the physicochemical properties oI organic components |2|.
    The aim oI this presentation is to discuss the impact oI diIIerent organic components on the eIIiciency oI dehydration by
    pervaporation. The results oI pervaporation experiments perIormed to dehydration oI diIIerent binary and multicomponent
    aqueous-organic mixtures are presented. During experiments various types oI hydrophilic membranes are used, e.g. PVA, ion-
    exchange and inorganic (modiIied silica) ones. The organic components are characterized by their hydrophobicity, expressed
    in terms oI dielectric constant (), Hansen's solubility parameter () and/or the partition coeIIicient between octanol and water
    (Kow).
    It was Iound that the eIIiciency oI pervaporative dehydration is dependent not only on the membrane material but also on the
    kind oI the organic component. The results obtained can be Iurther used Ior a case-based reasoning approach that supports the
    design oI the best pervaporation separation system Ior a given mixture |3,4|.
    |1| W.Kujawski Application oI pervaporation and vapor permeation in the environmental protection, Polish Journal oI
    Environmental Studies, 2000, 9, 13-26.
    |2| W.Kujawski, G.Pozniak, Transport Properties oI Ion-Exchange Membranes during Pervaporation oI Water-Alcohol
    Mixtures, Sep. Pur. Technol., 2005, 40, 2277-2295.
    |3| T.Koiranen, A.Kraslawski, L.Nystrom, Knowledge-based System Ior the Preliminary Design oI Mixing Equipment, Ind.
    Eng. Chem. Res., 1995, 34, 3059-3067.
    |4| T.Seuranen, E.Pajula, M.Hurme, Synthesis oI Azeotropic Separation Systems by Case-Based Reasoning, Computer-Aided
    Chemical Engineering, 2002, 10, 343-348.
    OD.1.9
    Dehydration of water/dichloromethane/n-butanol mixtures by pervaporation;
    optimisation and modelling by response surface methodology
    V. Garcia
    1
    , J. Landaburu-Aguirre
    1
    , E. Pongracz
    1,2
    P. Permki
    3
    , R. L. Keiski
    1
    1
    Mass and Heat Transfer Process Laboratorv, Department of Process and Environmental Engineering, FI-90014, Universitv
    of Oulu, P.O.Box 4300, Oulu, Finland.
    2
    Thule Institute, Centre of Northern Environmental Technologv, FI-90014 Universitv of Oulu, P.O.Box 7300,Oulu, Finland
    3
    Department of Chemistrv, P.O. Box 3000, FI-90014 Universitv of Oulu, Oulu, Finland
    veronica.garciaoulu.Ii
    The recovery oI volatile organic compounds (VOCs) such as dichloromethane and n-butanol Irom aquatic systems is oI great
    importance due to their hazardous nature and the threat they pose to the environment and human health. Pervaporation (PV) is
    a promising energy-saving membrane separation process Ior VOCs recovery. PV driving Iorce is achieved by keeping the
    pressure oI the downstream side much lower than the saturation pressure oI the permeating components. As a consequence, the
    selective compounds Irom the liquid mixtures are removed as vapour through a non-porous perm selective membrane. |1| In
    this research, PV oI waterDCMn-butanol ternary systems is conducted at diIIerent Ieed concentrations and temperatures
    using a composite hydrophilic membrane. The eIIect oI experimental variables, temperature and Ieed concentration, on PV
    perIormance is investigated to Iind the optimum conditions. To determine the optimum operating conditions applying
    Response SurIace Methodology (RSM) is a promising approach. By using RSM, the number oI experiments needed Ior the
    analysis oI the main eIIects and interactions between Iactors is reduced compared to the one variable at a time approach.
    ThereIore, the use oI time, raw material, costs oI experimentation and natural resources would also decrease. RSM has been
    used successIully in some membrane applications |2|. However, literature regarding the applicability to PV studies is very
    limited |3|. The main purpose oI this study is the dehydration oI the n-butanolDCM mixture by PV. The aim is also to Iind a
    suitable approximating Iunction that describes the PV process in order to predict and determine the Iuture response. Finally,
    the paper will report on the use oI RSM in PV.
    The Academy oI Finland (project no. 111416), the Maj and Tor Nessling Ioundation (project number 2008394) and the Thule
    Institute are acknowledged Ior their Iinancial support. Further, GKSS Forschungszentrum Ior generously supplying the
    membranes used in this study.
    |1| B. Smitha, D. Suhanya, S. Sridhar, M. Ramakrishna Separation oI organicorganic mixtures by pervaporationa review, J.
    Membr. Sci., 241 (2004) 1-21.
    |2| R. Malaisamy, G. Annadurai, D. Mohan, PerIormance optimization oI polysulIone ultraIiltration membranes Ior riboIlavin
    separation using design experiments, Bioprocess Eng., 22 (2000) 227232.
    -77-
    |3| A. Idris, A.F. Ismail, M.Y. Noordin, S.J. Shilton, Optimization oI cellulose acetate hollow Iiber reverse osmosis membrane
    production using Taguchi method, J. Membr. Sci., 205 (2002) 223237.
    OD.1.10
    Cost-effective low pressure membrane systems
    W. Sellerberg, L. Escobar-Ferrand, C. Liu, M. Farcy, A. Wachinski
    Pall Corporation, 25 Harbor Park drive, Port Washington, NY 11050, USA
    williamsellerbergpall.com
    The use oI low-pressure (microIiltration and ultraIiltration) membrane systems to produce potable water has become
    increasingly more common over the last 15 years. Low-pressure membrane Iiltration consistently provides high quality water
    regardless oI raw water quality. Low-pressure membrane Iiltration is very eIIective to remove microbial pathogens such as
    protozoa, bacteria, and virus. When coupling with traditional pretreatment processes such as coagulation, it is also able to
    remove a signiIicant amount oI disinIection-by-product (DBP) precursors. These technological advantages make low-pressure
    membrane Iiltration an excellent treatment option to meet the increasingly stringent drinking water regulations. As a result, the
    pace oI adopting low-pressure membrane Iiltration in the drinking water industry has been exponential in last decade.
    One recent advance in low-pressure membrane Iiltration is the adoption oI the Enhanced Flux Maintenance (EFM) cycle. This
    is an automatic procedure that is built into the membrane system that can be enabled upon either pre-determined schedule
    (time, volume oI production water, or trans-membrane pressure setting point), or operator`s command. By adopting EFM,
    membrane Ilux can be increased signiIicantly. EFM also stabilizes membrane perIormance, even with varying raw water
    quality. As a result, EFM would have signiIicant impact on the capital and O & M costs.
    This paper presents three case studies on low-pressure membrane Iiltration systems. Coagulation and enhanced Ilux
    maintenance (EFM) result in higher design Iluxes and lower capital costs. TOC removal, coagulant doses and process data
    Irom each study are presented.
    OD.1.11
    Fractionation of cyclodextrins mixture by ultra and nanofiltration
    F. Ellouze
    1, 2
    , N. Ben Amar
    1
    , A. Deratani
    2
    , W. Zimmermann
    3
    1
    Institut National des Sciences Appliquees et de Technologie, B.P 676 1080 Tunis cedex, Tunisie (nihel.benamarinsat.rnu.tn)
    Laboratoire de Modelisation Mathematique et Numerique dans les Sciences de lIngenieur, ENIT.
    2
    Institut Europeen des Membranes, UMR 5635 CNRS/ENSCM/UMII, Universite Montpellier II, cc 47, 2 Place E.Bataillon,
    34095 Montpellier cedex 5, France.
    3
    Institut fr Biochemie Mikrobiologie und Bioverfahrenstechnik, Universitt Leip:ig, Johannisallee 21-23, D-04103 Leip:ig,
    Germanv
    Fatma.Ellouzeiemm.univ-monpt2.Ir
    Cyclodextrins CDs are produced by enzymatic degradation oI starch by an enzyme called CycloglucanotransIerase (CGTase).
    CDs are cyclic oligosaccharides containing Irom 6 to more than 60 glucose units (CD6 to CD60). The particularity oI CDs is
    their remarkable ability to complex organic molecules in their hydrophobic inner cavity. The main CDs, u-CD, -CD and -
    CD, with polymerisation degrees oI 6, 7 and 8 are separated by selective precipitation and have multiple applications in the
    Iood, pharmaceutical, cosmetic, agricultural and chemical industries. CDs with larger ring (LR) Irom 9 (CD
    9
    ) to 60 (CD
    60
    )
    glucose units could Iind applications as novel host compounds Ior large molecules thanks to their high solubility and their
    structure which are distinct Irom the small CD. The main bottleneck Ior developing LR CD is that convenient techniques oI
    separation have not been developed yet. Some researchers have isolated and characterized LR CD by preparative
    chromatography but the process is tedious and can not be easily applied in industrial scale. In this study we investigated the
    Ieasibility oI using membrane process Ior Iractionation and enrichment oI a CDs mixture containing glucose (8), u-CD, -
    CD, -CD (17) and LR CDs ranging Irom CD9 to CD60 (75).
    Three commercial membranes (tight UF and NF) with diIIerent pores size (HL, GH and GK) were characterized in terms oI
    molecular weight cut oII determined Irom PEG measurements and oI rejection oI glucose and -CD (models molecules). A
    mathematical simulation predicting the composition oI the CD mixture aIter diaIiltration Ior each membrane was then applied
    to select the process Iiltration that might lead to an optimal separation. The best compromise between productivity and
    -78-
    puriIication degree was to use a cascade oI the three membranes Irom the smallest (HL membrane) to the largest one (GK
    membrane). Fractionation oI LR CDs and enrichment into CD9 CD21 and CD22 CD60 Iractions can then obtained.
    OD.1.12
    Process of desalination of low energy consumption. Magnetohydrodynamics
    desalination process
    J. Abad Garrido, P. Peas Ballester
    Calle Escuelas 17 30162-Santa Cru: (Murcia) Spain
    pedro.penasbcoiirm.es
    This document shows the theoretical justiIication oI a new process oI desalination with lower energy consumption than reverse
    osmosi. The minimum energy consumption (ideal behaviour) is aprox. 0,4 kWh/m
    3
    oI sea water desalinated. We expect a real
    consumption near oI 1,5 kWh/m3 oI sea water desalinated. The best reverse osmosis consumption is 2,7 kWh/m3. The
    theoretical data oI this process oI desalination have been discussed in the department oI electrochemistry oI the University oI
    Alicante.(Spain). There is a constructive Iorm to prevent that the losses with the use oI an intensity oI electrons. This
    constructive Iorm consists oI the use oI a geometrical conIiguration that does not have cells in the ends. This conIiguration is
    not compatible with a Iorce due to an electric Iield. We can not use de electric Iield term oI the Lorentz Iorce but we can use
    the second term oI the Lorentz Iorce. This term is developed in called science Magnetohydrodynamics. With this geometrical
    conIiguration and a suitable magnetic Iield is possible to carry out the desalination oI the sea water with the electrodialysis
    membranes without the same energetic losses. The power consumption oI this new process oI desalination can be modelized
    with the Nernst`s equation together MHD equation. In electrochemistry, the Nernst equation is an equation which can be used
    (in conjunction with other inIormation) to determine the equilibrium reduction potential oI a halI-cell in an electrochemical
    cell. It can also be used to determine the total voltage (electromotive Iorce) Ior a Iull electrochemical cell.
    Energy q * V (q electric charge).
    Magnetic Iield. One oI the main technological goals oI this process oI desalination is the use oI strong magnetic Iields. The
    magnetic Iields must be oI the order oI 5 Tesla. In order to get this magnetic Iield we may use superconductivity dipole.The
    Ciemat, Research centre Energetics, Environmental and Technological oI Spain, already has realised predesigns Ior the
    construction oI one magnetic dipole adapted to this process oI desalination oI sea water.
    Electromagnetic stimulation oI electric mass transIer in the Ilow electrochemical system.
    N.S. Demidova
    Moscow State Institute oI Aviation, Volokolamskoe sh. 4, Moscow, 125080 Russia
    Received July 6, 1993; in Iinal Iorm, March, 1998.
    Reducing power losses caused by ionic shortcut currents in reverse electrodialysis stacks by a validated model
    J. Veerman a, J.W. Post a,c, M. Saakes a, S.J. Metza,, G.J. Harmsenb
    Flow Control oI Seawater With a Diverging Duct by MHD Separation Method
    Minoru Takeda, Naotaka Tomomori, Teruhiko Akazawa, Kazu Nishigaki, and Akira Iwata
    Fundamental Studies oI Helical-Type Seawater MHD Generation System
    Minoru Takeda, Yasuaki Okuji, Teruhiko Akazawa, Xiaojun Liu, and Tsukasa Kiyoshi
    OD.1.13
    New membrane applications in oenology
    R. Ghidossi, A. Massot, C. Poupot, M. Mietton Peuchot
    Universite de Bordeaux, ISJJ, UMR nologie, Faculte dnologie 210 Chemin de Levsotte, CS 50008, 33882 Jillenave
    dOrnon cedex
    martine.mietton-peuchotu-bordeaux2.Ir
    Membrane Iiltration has been applied to wine Ior a long time. At present, the clariIication cartridges are integrated in all
    bottling units. Subsequently, in a cross-Ilow Iiltration mode, microIiltration membranes were the Iirst to be applied Ior wine
    clariIication. Today, cross-Ilow microIiltration is largely used in oenology Ior must, lees and wine Iiltration at diIIerent
    -79-
    membrane cut-oII, Irom 0.2 to 1.2 m. The development oI reverse osmosis application in must concentration was practically
    done in parallel with that oI microIiltration in clariIication |1|.
    The paper is an overview oI the application oI membrane processes to wine making. The aim is to present both the application
    oI membrane processes in winemaking and a general philosophy oI their development Irom a process engineering point oI
    view. Several examples illustrate this approach; in particular, applications oI nanoIiltration and reverse osmosis membranes,
    but the other techniques such as microIiltration, ultraIiltration and electrodialysis are also mentioned. Reduction oI alcohol
    content is studied with diIIerent techniques (nanoIiltration evaporation, nanoIiltration membrane contactor, decrease oI
    sugar content, .) |2|. The volatile acidity or malic acid reduction could also be done by coupling two stages oI reverse
    osmosis. Since the Iree acids are poorly retained by the membrane, the permeate aIter the Iirst stage Iiltration contains Iree
    acids, salts, esters and other small molecules. Once the permeate is neutralized with pH oI the targeted acid, it will be retained
    by the second stage membrane in a salty Iorm. The other components passing through are re-injected in the initial must or
    wine. The potassium hydroxide is used Ior neutralisation.
    The principal condition Ior Iurther development oI membrane processes in winemaking is a good understanding oI membrane
    techniques, separation techniques and characterization oI the membrane itselI and the product (must or wine) to be Iiltered.
    The second constrain, given the complexity and variability oI must and wine composition is not trivial and needs a
    considerable eIIort at both industrial and research levels. For the same reasons, the coupling oI the membrane and other
    physical-chemical treatments appears to be a promising research domain. However, the legislative problem slows their
    developments.
    |1| M. Mietton-Peuchot, V. Milisic and P. Noilet, Grape must concentration by using reverse osmosis. Comparison with
    chaptalization, Desalination, 148 (2002) 125129
    |2| N. Diban, V. Athes, M. Bes, I. Souchon, Ethanol and aroma compounds transIer study Ior partial dealcoholization oI wine
    using membrane contactor, Journal oI Membrane Science, Volume 311, Issues 1-2 (2008) 136-146
    OD.2.1
    Global model of the ion exchange membrane bioreactor for removal of anionic
    micropollutants from drinking water supplies
    A.R. Ricardo, R. Oliveira, S. Velizarov, M.A.M. Reis, J.G. Crespo
    REQUIMTE / CQFB, FCT-Universidade Nova de Lisboa, Campus da Caparica, 2829-516 Caparica, Portugal
    arrdq.Ict.unl.pt
    The Ion Exchange Membrane Bioreactor (IEMB) is a patented process that combines transport through an ion exchange
    membrane and biological reduction |1|. This process was successIully applied Ior the removal oI ionic compounds (either
    anionic or cationic) Irom drinking water supplies. The system has two compartments physically separated by a dense ion-
    exchange membrane, thus avoiding secondary contamination oI the treated water. AIter the transport oI pollutants across the
    membrane, they are converted by a suitable microbial culture to innocuous species.
    This study is Iocused on optimizing the IEMB operating conditions Ior the removal oI nitrate and perchlorate Irom drinking
    water supplies. To IulIill this goal a global model was developed combining the transport across the membrane and the
    biological reaction. Considering the complexity oI the metabolic kinetics and transport phenomena, the modeling oI the IEMB
    can be rather complex. To overcome this problem the modeling strategy developed consists oI a hybrid semi-parametric
    model, combining mechanistic and statistically based modelling.
    In this strategy, the two main stages oI the process are modeled: the transport across the membrane and the consumption oI
    nutrients in the biocompartment according to the structure show in Figure 1.
    -80-
    For the membrane transport
    process, a knowledge based
    modular network was design in
    order to compensate the
    mechanistic model inaccuracies.
    This network allows Ior capturing
    the best inIormation Irom each
    model using a gating system that
    takes into account the initial
    conditions.
    The dynamic material balances oI
    the biological compartment
    accounts Ior the biological reaction
    kinetics and the transport kinetics
    contributions. This global model
    can be used to predict the process
    perIormance and, moreover, to
    support the integrated optimization
    oI the operating parameters in the
    two IEMB compartments.
    Figure 1: Hybrid model structure (c
    w
    : ion concentration in water, c: ion concentration in
    the biocompartment)
    |1| J.G. Crespo, M.A.M. Reis, Treatment oI aqueous media containing electrically charged compounds, 2003, Patent
    EP1246778
    OD.2.2
    Modelling of a membrane bioreactor for wastewater treatment using 2D-fluorescence
    spectroscopy as a complementary monitoring tool
    C. F. Galinha
    1
    , C. Portugal
    1,2
    , G. Carvalho
    1,3
    , G. Guglielmi
    4
    , D. Chiarani
    4
    , G. Andreottola
    4
    , R. Oliveira
    1
    ,
    M. A. M. Reis
    1
    , J. G. Crespo
    1
    1
    REQUIMTE/CQFB, FCT-Universidade Nova de Lisboa, Campus da Caparica, 2829-516 Caparica, Portugal
    2
    CEBAL, R. Pedro Soares, Apt. 6158, 7801-908 Befa, Portugal
    3
    IBET/ITQB, Q.ta do Marqus, Apt. 12, 2781-901 Oeiras, Portugal
    4
    Department of Civil and Environmental Engineering, Universitv of Trento, Jia Mesiano, 77, 38050 Trento, Italv
    claudia.galinhadq.Ict.unl.pt
    Membrane bioreactors (MBR) are widely applied Ior wastewater treatment. However, the progressive membrane Iouling due
    to deposition oI cells and cell products on the membranes reduces the permeability oI the system, resulting in substantial
    maintenance costs and shortening the membrane liIe span. The major bioIouling agents in MBRs are Extracellular Polymeric
    Substances (EPS), and thus EPS monitoring and control in MBR operation are essential.
    Since EPS contain large amounts oI proteins and other natural Iluorophores, the Iluorescence excitation-emission matrices
    (EEMs) obtained by scanning the spectra wavelengths can correspond to a Iingerprint oI the physiological activity oI a
    biological culture. Using statistically based modelling, EEMs can be correlated with key operational and perIormance
    parameters oI the studied system. Through the application oI statistically based modelling techniques, Iluorescence spectra are
    viewed as multivariate descriptors oI perIormance and treated with statistical approaches such as Principal Component
    Analysis (PCA) and Projection to Latent Structures (PLS). The statistical models are obtained by this approach using and their
    corresponding process perIormance parameters measured Ior diIIerent operating conditions. Through these calibrated models,
    the EEMs obtained on-line can be used to monitor the status oI the process, as well as Ior process control, allowing rapid
    correction oI operational parameters Ior process improvement.
    In this study, 2D-Iluorescence was applied to monitor a pilot scale MBR Ior domestic wastewater treatment located in a
    wastewater treatment plant in Lavis, Italy, by acquiring Iluorescence matrices oI the inIluent wastewater, the bioreactor mixed
    liquor and the permeate. Simultaneously, physical-chemical analyses were perIormed while the MBR was operated under
    controlled permeate Ilux.
    Operating conditions, wastewater characteristics and EEM were used as inputs oI the models. Permeate characteristics, sludge
    characteristics and transmembrane pressure were the parameters predicted by these models (outputs). The model description oI
    the output variables, with and without the integration oI Iluorescence EEMs, was compared in order to assess the relevance oI
    using 2D-Iluorescence Ior monitoring oI such complex systems.
    -81-
    A statistical approach using PLS proved to be able to model selected perIormance outputs Ior the MBR system, such as the
    carbon removal and the transmembrane pressure. It was also demonstrated that the additional inIormation provided by the
    EEM about the state oI the biological system enhanced MBR modelling and perIormance prediction. Thus, this approach
    enabled the development oI improved and more robust models when the correlations between the operating parameters and
    traditional analytical results were not robust enough to accurately predict the output variables. PLS modelling also
    demonstrated to be a powerIul tool Ior a better understanding oI the relationship between inputs and outputs through analysis
    oI the model coeIIicients, which can ultimately be applied Ior process optimisation.
    OD.2.3
    Biocatalytic membrane reactors to guide and control bioconversion, isolation and
    stabilization of water unstable intermediates
    R. Mazzei, L. Giorno, E. Drioli
    Institute on Membrane Technologv, National Research Council, ITM-CNR, Universitv of Calabria, Jia P. Bucci 17/C, 87030,
    Rende (CS), Italv
    l.giornoitm.cnr.it
    Biocatalytic membrane reactors using immobilized -glucosidase have been applied to implement the valorization oI phenolic
    by-products, such as oleuropein, coming Irom olive oil processing.
    The hydrolysis oI oleuropein gives high added value compounds pharmacologically active, i.e. the oleuropein aglycon,
    hydroxytyrosol and dialdehydes. These molecules are, Ior example, involved in the plant deIense against pathogens
    (glutaraldeide-like action towards esogen protein); they are strong antioxidant and have antimicrobial action.
    In the Iirst step oI oleuropein hydrolysis, catalyzed by -glucosidase, only the oleuropein aglycon, together with a glucose
    molecule, is obtained. Due to its low water stability, this phenolic compound is Iastly rearranged into hydrophilic molecules.
    Even iI the pharmacological properties oI oleuropein aglycon are well known, it is not yet commercially available as pure and
    stable compound.
    A biocatalytic membrane system was designed and tested in order to create the appropriate conditions Ior carrying out the
    oleuropein hydrolysis by heterogenized -glucosidase and to simultaneously isolate the water unstable aglycon into an organic
    phase.
    The -glucosidase was immobilized by physical entrapment on polysulphone membrane. The enzymatic hydrolysis was
    carried in aqueous monophasic environment and the product was separated into an organic phase soon aIter the reaction. Both
    steps were carried out in a single unit, under convective mass transport regime. The contact oI the aqueous phase with the
    organic phase permitted the partition oI the hydrophobic molecule (aglycon) into the organic phase and the hydrophilic ones
    (glucose) in the aqueous phase.
    The perIormance oI -glucosidase used in the biocatalytic membrane was studied and compared with the Iree enzyme used in a
    stirred batch reactor. Results showed that the kinetic parameters oI immobilized enzyme remained unchanged compared to the
    native enzyme. This conIirms that the common observation oI inverse relationship between activity decrease and stability
    increase Ior immobilized enzymes is not a general rule.
    The biocatalytic membrane system was used either in absence or presence oI organic phase. In both cases, the reaction
    perIormance was the same, since reaction always occurred in water phase. On the other hand, when the organic phase was
    present, the aglycon could be isolated and stabilised.
    The biocatalytic membrane system, thanks to the membrane operation Ilexibility, can be extended to other cases presenting
    similar physical chemical properties.
    -82-
    OD.2.4
    Membrane assisted catalytic dehydrogenation of ethane
    T. Giddings, L. Nossova, J. Galuszka
    Natural Resources Canada, CanmetENERGY, 1 Haanel Drive, Ottawa, Ontario, Canada K1M 1M1
    galuszkaNRCan.gc.ca
    There is a substantial incentive to replace the current energy intensive ethylene production technology with a cleaner and more
    eIIicient process. Membrane assisted catalytic dehydrogenation oI ethane has been studied since the early nineties and a
    commercial Ieasibility oI this process has been increasing steadily.
    In a previous study |1| we demonstrated that a conventional dehydrogenation catalyst in a novel membrane reactor Iairly
    enhanced ethane conversion to ethylene. We attributed the only moderate improvements oI ethane conversion to the lack oI
    compatibility between our catalyst and membrane. Consequently, in the current study we tested a membrane assisted
    dehydrogenation oI ethane to ethylene using a commercial dehydrogenation catalyst having a diIIerent Iormulation.
    Catalytic dehydrogenation oI ethane was studied in a Iully automated, Iixed-bed conventional (CR) and a tube and shell
    hydrogen membrane (H-membrane) reactor (MR) |1|. Membrane inIluence on conversion and product distribution Ior
    dehydrogenation was assessed at 555
    o
    C and 600
    o
    C with GHSV oI 84 h
    -1
    and 160 h
    -1
    . Improved conversions and yields were
    observed in comparison to our previous study. Ethane conversions at 555C and 600C Ior the MR were about 10 greater
    than the CR. Maximum yields were approximately 8 greater Ior MR than Ior the CR at both temperatures. Catalyst
    deactivation was observed to be more rapid at 600C than at 555C. At 555
    o
    C ethane conversion at a GHSV oI 84h
    -1
    was
    relatively stable, whereas the conversion Ior the GHSV oI 160h
    -1
    Iell to equilibrium conversion aIter about 6 h. The ethylene
    selectivities decreased at low space velocity where hydrogen removal by the membrane was higher. It seems that carrying the
    process at lower temperature with a membrane reactor having a large membrane surIace area may provide the optimal
    conditions Ior the membrane reactor assistance to ethane dehydrogenation.
    |1| Galuszka, J., Giddings, T. and Clelland, I., Inorganic Membranes Ior Energy and Environmental Applications, (ed. A.C.
    Bose), Springer New York, 2009, pp.299-311.
    OD.2.5
    Mass transport in biocatalytic membrane reactors
    E. Nagy
    Universitv of Pannonia, Research Institute of Chemical and Process Engineering, P.O.Box 158, 8201 Jes:prem, Hungarv,
    Tel..00-36-624040, Fax. 00-36-624038
    nagyemik.uni-pannon.hu; nagymukki.richem.hu
    Membrane reactors using biological catalyst can be applied in production, processing, transIormation, valorization oI raw
    materials, treatment operations, etc. In the biochemical points oI view it is an important task to describe the mass transport
    process in order to be able to predict the mass transIer rates and the concentration distribution in the membrane Ior the scaling
    up oI the process as well as to avoid the limiting concentration oI the oxygen or other nutrient, which can be oIten critical
    scale-limiting Iactor. In order to increase oI the substrate concentration in the membrane bioreactor, suIIicient diIIusion rate
    and/or convective Ilow has to be provided through the lumen, in axial direction, and through the membrane layer, in radial
    direction, oI the hollow Iiber. In the reality, the speciIic biomass concentration (and enzyme concentration) can vary as a
    Iunction oI space coordinate, namely, e.g. the activity oI cells can be much higher at higher substrate concentration, that is
    close the Ieed membrane interIace. Thus, it is necessary to take into account variable diIIusion coeIIicient, convective velocity
    and biochemical reaction rate constants in the prediction.
    Taking into account the convective and the diIIusive Ilows in both the layers as well as the biochemical reaction in the
    membrane layer, exact mass transIer equations have been developed and will be discussed. As a membrane an asymmetric one
    with immobilization oI microorganism/enzyme in its porous support layer has been concerned.
    Applying the solution, the Iollowing applications will be demonstrated:
    1
    )
    Analyitical solution will be given Ior Iirst-order and zero-order biochemical reactions; an analytical approach Ior the general
    Michaelis-menten kinetics will also be demonstrated. This solution will also be applied to calculate the process in the case oI
    cylindrical coordinate used Ior a hollow Iiber bioreactor as well as processes with variable transport parameters; 2)
    Substituting the mass transIer rates into the lumen side and/or shell side mass balance equations, the concentration distribution
    -83-
    is calculated by means oI the general solution. The above results obtained Ior a single capillary tube can be simply adapted Ior
    large membrane module as will be shown.
    As case studies the kinetic resolution oI ibuproIen ester |2| as well as the eIIect oI the asymmetric cell growth around the
    capillary membrane |3| will be shown. It will also be shown how the model prediction can be used Ior scaling up oI a
    membrane bioprocess.
    |1| E. Nagy, J.Membrane Sci., 274, (2006) 159-168.
    |2| S.W. Long, S.Bhatia, A. Kamaruddin, J. Membrane Sci., 219, (2003) 151-161.
    |3| C.A. Sardonini, D. DiBiaso, Biotechnol. Bioeng., 40, (1992) 1233-1242.
    OD.2.6
    Theoretical investigation on the effect of superficial defects over the membrane
    surface of Pd-based membrane reactors for methane steam reforming
    A. Caravella
    1
    , F.P. Di Maio
    2
    , A. Di Renzo
    2
    1
    Institute on Membrane Technologv - National Research Council, ITM-CNR, c/o Universitv of Calabria, Jia Pietro Bucci,
    Cubo 17/C, 87036, Rende (CS), Italv.
    2
    Department. of Chemical and Materials Engineering, Universitv of Calabria, Jia Pietro Bucci, Cubo 44/A, 87036, Rende
    (CS) Italv.
    alessio.caravellaunical.it
    The aim oI this analysis is quantiIy the inIluence oI superIicial deIects (pinholes) over the surIace oI a selective Pd-based layer
    in a membrane reactor to produce hydrogen by methane steam reIorming. The design equations modelling the membrane
    reactors take into account mass, energy and momentum transIer along the axial direction. In the so-obtained 1-D model, whose
    validity has already been conIirmed elsewhere |1|, the presence oI the superIicial deIects is introduced by making the
    Iollowing hypothesis: the transport oI hydrogen and other species through the pinholes occurs by Knudsen-wise mechanism,
    whilst in the remaining deIect-Iree surIace membrane only hydrogen is able to pass by a solution-diIIusion mechanism, whose
    permeation law is got Irom an experimental work oI literature |2|. The combination oI these two mechanisms provides an
    overall permeation law oI the species involved in the process, which in turn determines a Iinite membrane perm-selectivity oI
    these species with respect to hydrogen. The eIIect oI both pinhole mean pore diameter and amount oI deIected Iractional area
    is investigated, showing that in some conditions only a very small part oI deIected membrane (0.1 ca.) is suIIicient to make
    the reactor perIormance (methane conversion, hydrogen recovery yield and downstream purity) decrease signiIicantly. This is
    shown to be due to the large diIIerence between the solution-diIIusion permeance and the Knudsen one, which is three orders
    oI magnitude higher than the Iirst one.
    Acknowledgments: The project 'FIRB-CAMERE (RBNE03JCR5) co-Iunded by the "Ministero dell`Universita e della
    Ricerca" (MiUR, Italy) is grateIully acknowledged Ior Iunding this research.
    |1| Caravella A., Di Maio F.P. and Di Renzo A, 2008. Optimization oI membrane area and catalyst distribution in a
    permeative-stage membrane reactor Ior methane steam reIorming. J. Mem. Sci., 321: 209-221.
    |2| Tong J., Matsumura Y., Suda H. and Haraya K., 2005. Experimental study oI steam reIorming oI methane in a thin (6 m)
    Pd-based membrane reactor. Ind. Eng. Chem. Res., 44: 1454-1465.
    -84-
    OD.2.7
    Hydrogen production by dehydrogenating cyclohexane using membrane reactors
    with pore-size-controlled silica membranes
    Y. Ohta
    1
    , K. Akamatsu
    1
    , T. Sugawara
    1
    , T. Hattori
    2
    , S. Nakao
    1
    1
    Department of Chemical Svstem Engineering, The Universitv of Tokvo, 7-3-1 Hongo, Bunkvo-ku, Tokvo 113-8656, Japan
    2
    Nagova Industrial Science Research Institute, 1-13 Yotsuva-dori, Chikusa, Nagova 464-0819, Japan
    makuchemsys.t.u-tokyo.ac.jp
    Membrane reactors have been successIully developed using hydrogen-selective pore-size-controlled silica membranes Ior
    producing high-purity hydrogen that can be directly supplied to a Iuel cell. The silica membranes were prepared by chemical
    vapor deposition method with tetramethoxysilane (TMOS) or dimethoxydiphenylsilane (DMDPS) |1|. Both the membranes
    had hydrogen-permselective propery. And both the membrane reactors produced hydrogen with higher conversion than the
    equilibrium, and the membrane reactor with DMDPS-derived membrane achieved higher conversion than that with TMOS-
    derived one because hydrogen-extraction eIIect was larger in the DMDPS-derived membrane case |2|. Furthermore, we have
    also succeeded in operating a membrane reactor with DMDPS membrane by Ieeding neat pressurized cyclohexane and
    producing hydrogen under atmospheric pressure with above 99 purity |3|.
    |1| Y. Ohta, K. Akamatsu, T. Sugawara, A. Nakao, A. Miyoshi, S. Nakao, Development oI pore-size-controlled silica
    membranes Ior gas separation by chemical vapor deposition, J. Membrane Sci., 2008, 315(1-2), 93-99.
    |2| K. Akamatsu, Y. Ohta, T. Sugawara, T. Hattori, S. Nakao, Production oI hydrogen by dehydrogenation oI cyclohexane in
    high-pressure (1-8 atm) membrane reactors using amorphous silica membranes with controlled pore sizes, Ind. Eng. Chem.
    Res., 2008, 47(24), 9842-9847.
    |3| K. Akamatsu, Y. Ohta, T. Sugawara, N. Kanno, K. Tonokura, T. Hattori, S. Nakao, Stable high-purity hydrogen production
    by dehydrogenation oI cyclohexane using a membrane reactor with neither carrier gas nor sweep gas, J. Membrane Sci., in
    press.
    OD.2.8
    Detailed process analysis of a pervaporation membrane reactor for a heterogeneously
    catalysed esterification reaction
    T. Roth
    1
    , S. Lauterbach
    2
    , P. Kreis
    1
    1
    Laboratorv of Fluid Separations, TU Dortmund Universitv Department of Biochemical and Chemical Engineering, Emil
    Figge Str. 70 44227 Dortmund Germanv
    2
    Ineos Kln GmbH Germanv
    tim.rothbci.tu-dortmund.de
    In this work a pervaporation assisted esteriIication reaction is investigated Ior the propyl propionate synthesis. The batch
    reactor and pervaporation module are combined in loop conIiguration and 1-propanol reacts heterogeneously catalysed with
    propionic acid to propyl-propionate and water. The commercial available hydrophilic membrane PERVAP

    2201D Irom
    Sulzer Chemtech (membrane area: 0.5 m) is applied. For the theoretical investigations a sophisticated mathematical model Ior
    the membrane separation is combined with a dynamic CSTR model. Relevant model parameters Ior an accurate description oI
    the reaction kinetics |1| and the transmembrane Ilux |2| have been determined by experiments in previous works.
    In this study the optimal modeling depth has been determined and detailed parameter studies have been perIormed to identiIy
    the optimal operating and structural parameter. The membrane area, reactor holdup, amount oI catalyst, initial alcohol/acid
    ratio, temperature, Ieed mass Ilow, initial amount oI water and start time oI the membrane separation have been varied.
    -85-
    For example, the batch time Ior a given yield can be reduced
    signiIicantly by increasing the speciIic membrane area, which is
    deIined as the ratio between membrane area and reactor holdup. At
    higher speciIic membrane areas no Iurther time reduction is obtained
    because oI low water concentrations and thereIore low driving Iorces
    Ior the transmembrane Ilux.
    Additionally a Ied-batch operation is investigated. In this case study a
    constant amount oI propionic acid is Ied in deIined times into the
    reactor. Thus the reaction rate is decreasing because oI lower acid
    concentration. However the strong reduction oI acid concentration
    with increasing Ieed time (Figure 1) can lead to an improvement in
    membrane liIetime.
    Finally two puriIication sequences have been developed. For the Iirst
    sequence the process is stopped at a short batch time (1 hour; 90
    yield) and Ior the second aIter attaining a high yield (6.5 hours;
    99,4 yield).
    Figure 1: mass Iraction propionic acid over batch
    time Ior diIIerent Ieed times
    |1| Duarte, C.; Buchaly, C.; Kreis, P.; Loureiro, J. Esterification of propionic acid with n-propanol catalvtic and noncatalvtic
    kinetic studv Inzynieria Chemiczna i Procesowa 27 (2006) p. 273-86.
    |2| Lauterbach, S.; Kreis, P. Experimental and theoretical investigation of a pervaporation membrane reactor for a
    heterogeneouslv catalvsed esterification Euromembrane 2006 (2006)
    OD.2.9
    Ceramic membrane microreactors (CeMR)
    H.C. Aran
    1
    , D. Salamon
    1
    , R. Groote
    1
    , J.M. Jani
    1
    , J.K. Chinthaginjala
    2
    , R.G.H. Lammertink
    1
    , M. Wessling
    1
    1
    Membrane Science and Technologv, Facultv of Science and Technologv, Universitv of Twente, P.O. Box 217, 7500AE
    Enschede, The Netherlands
    2
    Catalvtic Processes and Materials, Facultv of Science and Technologv, Universitv of Twente, P.O. Box 217, 7500AE
    Enschede, The Netherlands
    h.c.arantnw.utwente.nl
    Microreactors are suitable Ior exploring and perIorming highly exothermic and Iast reactions. Due to the reduced length scales,
    enhanced mass and heat transIer is obtained. Use oI ceramics as microreactor material provides optimal stability at high
    temperatures, pressures, and aggressive media.
    We aim to integrate membrane Iunctionality into microIluidic devices, economically Iabricate new ceramic microreactors and
    explore new concepts Ior gas-liquid (-solid) reactions inside these reactors. The gas- liquid contacting Ior reaction purposes is
    achieved using membrane technology by permeating the gas reactant through a porous ceramic membrane, reaching the liquid
    reactant Ilowing in the microchannels (Figure 1). This will reduce the mass transIer limitations in the gas-liquid-solid reaction
    processes.
    Microstructuring and Iabrication oI the ceramic microreactors are realized via simple replication and sintering processes. The
    channel surIaces are hydrophobized with a surIace modiIication step, so wetting is prevented. According to the Iinal
    application also catalyst is immobilized on the microchannel walls.
    Using the above described Iabrication techniques we have Iabricated multichannel and multilayer ceramic microIluidic devices
    (Figure 2). With the surIace modiIication step we could prevent wetting oI the originally hydrophilic porous membrane
    material by the liquid stream in order to achieve a stabilized gas-liquid interIace.
    Two model reaction systems have been investigated Ior validation: reactive absorption oI carbon dioxide in water and the
    hydrogenation oI nitrite in water. We have demonstrated good agreement between our simulations and experimental data. With
    -86-
    Figure 1:
    Novel gas / liquid
    contacting concept
    inside microreactors
    Figure 2:
    Fabricated stack oI
    microchannels with
    multilayer Iunctionality
    the latter reaction system we veriIied our catalyst immobilization techniques and in the preliminary experiments we have
    observed promising catalytic conversion.
    OD.2.10
    Effect of powdered activated carbon (PAC) on the microbial behavior in membrane
    bioreactor (MBR)
    R.C. Eusebio
    1
    , H.G. Kim
    2
    , H.S. Kim
    1
    1
    Department of Environmental Engineering and Biotechnologv, Mvongfi Universitv, San 38-2 Namdong, Cheoin-Gu, Yongin,
    Kvonggi-Do 449-728, South Korea
    2
    Institute of Construction Technologv, KUMHO Engineering and Construction, =668-2 Daedae-Ri, Yangfi-Mvun, Cheoin-Gu,
    Yongin, Kvonggi-Do 449-820, South Korea
    rceusebiogmail.com
    Biological activity is one oI the major considerations in the optimization oI MBR process. The eIIect oI PAC addition in the
    microbial community inside the reactor was evaluated. The MBR system is consisted oI Iour sections under anoxic, anaerobic,
    anoxic and aerobic conditions. Two separate systems were run in parallel; in the tested system, PAC was added at the Iirst
    compartment, while none at the control. Two PVDF Ilat sheet membranes having a pore size oI 0.08 m each were submerged
    in the aerobic reactor and continuously aerated. Biological activity was sustained on its ideal condition by monitoring the
    temperature, pH and dissolved oxygen (DO) inside the reactors. Initial permeate Ilux oI 0.5 m
    3
    /m
    2
    d was observed to decrease
    through time due to membrane Iouling, consequently, transmembrane pressure (TMP) kept on increasing. Carbohydrate and
    protein content oI extracellular polymeric substances (EPS) and soluble microbial products (SMP) aIIect the Iouling
    mechanism by accumulating and Iorming a thin layer in the surIace oI the membrane. Particle size distribution (PSD) analysis
    showed that addition oI PAC increased the size oI particles Iorming larger Ilocs. During Ilocculation, portion oI SMP was
    incorporated decreasing the concentration oI microbial products in the bulk phase. Also, the amount oI small particles was
    reduced through adsorption during Iloc`s Iormation. ConIocal laser scanning microscopy (CLSM) was also conducted to
    examine the Iouling mechanism in the membrane`s surIace. Higher porosity was observed in the system with PAC resulting to
    a larger surIace area Ior the water to pass through, hence increasing the permeability oI the membrane. In general, deposition
    oI small particles that cause membrane Iouling was decreased by the addition oI PAC, thus preventing rapid decline in
    Iiltration Ilux and abrupt increase in TMP.
    This project was supported by the Korean Research Foundation Grant Iunded by Korean Government (MOEHRD)
    KRF-2007-331-D00496
    |1| R. Liu, X. Huang, J. Xi, Y. Qian, Microbial Behaviour in a Membrane Bioreactor with Complete Sludge Retention, Process
    Biochemistry 40 (2005) 3165-3170
    |2| Y.Z. Li, Y.L. He, Y.H. Liu, S.C. Yang, G.J. Zhang, Comparison oI the Filtration Characteristics Between Biological
    Powdered Activated Carbon Sludge and Activated Sludge in Submerged Membrane Bioreactors, Desalination 174 (2005)
    305-314
    |3| B.K. Hwang, W.N. Lee, P.K. Park, C.H. Lee, I.S. Chang, EIIect oI Membrane Fouling Reducer on Cake Structure and
    Membrane Permeability in Membrane Bioreactor, Journal oI Membrane Science 288 (2007) 149-156
    OD.2.11
    Keynote: Polymeric catalytic membranes
    E. Fontananova, E. Drioli
    Department of Chemical Engineering and Materials, Universitv of Calabria, Jia P. Bucci, 44/A, Rende (CS), Italv.
    Institute on Membrane Technologv (ITM-CNR), c/o Universitv of Calabria, Jia P. Bucci, 17/C, 87030, Rende (CS), Italv.
    e.Iontananovaunical.it
    Catalytic membrane reactors (CMRs) are systems in which membrane based separation and catalytic conversion are combined
    in one device. In a CMR the membrane can be catalytically active (catalyst entrapped in the membrane, or membrane made oI
    an intrinsically catalytic material), or can serve to compartmentalize the catalyst in the reaction environment. In particular the
    -87-
    most interesting opportunities in order to realize innovative multiIunctional catalysts, are oIIered in the Iirst case (catalytically
    active membranes). Membranes represent in Iact one oI the most interesting examples oI molecular design oI the
    Iunctionalities. It is well know that both catalyst activity and stability can be positively inIluenced by the environment in which
    the catalytic system is conIined. The membrane Iunction in a CMR can be also the selective supply oI the reagents and/or
    removal oI the products, in order to increase reaction selectivity and/or yield.
    This presentation will Iocus on the strategies Iollowed Ior the design and development oI polymeric catalytic membranes
    active in reactions oI high interest. As key example we can consider oxidation reactions carried out by polyoxometalates,
    polyanionic metal oxide clusters oI early transition metals, dispersed on nanometric scale in polymeric membranes, Ior
    applications in Iine chemistry and wastewater treatments.
    The stability oI the catalytic system under reaction conditions and the Iirm immobilization oI the catalyst are key issue in
    catalyst heterogenization. The use oI an hydrophobic membrane material (e.g. PVDF, HyIlon) results particularly appropriate
    to carry out oxidation reactions oI organic substrates in water, because the high aIIinity that can be realized between the
    polymeric matrix and the substrates.
    An appropriate aIIinity between the polymer used Ior membrane preparation and the catalyst, is also Iundamental to realize a
    good adhesion between the two systems, in order to avoid the catalyst leaching and to allow its Iine dispersion on the
    polymeric matrix.
    A promising approach Ior increase the membrane/catalyst aIIinity relies on the chemical modiIication oI the second one.
    Moreover the tailored Iunctionalization oI the polymeric membrane material or membrane surIace, can be used Ior the
    selective catalysts recognition and immobilization.
    |1| E. Drioli, E. Fontananova, Membrane Reactors, published in: Advanced Membrane Technology and Applications. Edited
    by N. N. Li, W. S. Winston Ho, A. G. Fane, and T. Matsuura. Copyright John Wiley & Sons, Inc. (2008)
    OD.3.1
    The influence of concentration post sulphuric acid in the feed on HCl separation in
    membrane reactor by direct contact membrane distillation
    A. Lapin, M.Tomaszewska
    West Pomeranian Universitv of Technologv, S:c:ecin, Institute of Chemical and Environment Engineering, ul. Pulaskiego 10,
    70-322 S:c:ecin, tel. (48)914494367, fax (48)914494686 Poland
    agnieszka229wp.pl
    Potassium sulphate is produced in substantial quantities in Europe by means oI the Mannheim process Irom KCl and H
    2
    SO
    4
    .
    K
    2
    SO
    4
    can be also obtained in lower temperature. In the Iirst step KHSO
    4
    and HCl are Iormed Irom KCl by acidulation using
    sulphuric acid. In the second step K
    2
    SO
    4
    can be obtained Irom potassium bisulIate by desalting using alcohol solution.
    The aim oI this work was to study the HCl separation and eIIectiveness oI KHSO
    4
    production Irom a solution oI KCl-H
    2
    SO
    4
    using MD. The studies oI the conversion were perIormed using a membrane reactor integrated with direct contact membrane
    distillation (DCMD). The experiments were perIormed with the use oI a capillary membrane module (prepared Irom
    polypropylene). The temperatures oI the reaction mixture in the Ieed tank amounted to 343 K. The inlet temperature oI the
    distillate was equal to 293 K. The studies were perIormed using the sulphuric acid Iormed during TiO
    2
    production. The
    concentration oI the acid is about 25 wt. The post hydrolytic acid contains also salts oI Fe, Al and Mg. The initial
    concentrations oI a Ieed were as Iollows: 1series - 1.25M H
    2
    SO
    4
    and 1M KCl or 2 series - 2M H
    2
    SO
    4
    and 1M KCl. The
    reaction mixtures were concentrated close to the saturated state, when crystals were precipitated Irom the solution aIter
    cooling. AIter separation oI the precipitate the mother liquor was again concentrated.
    During the conversion oI KCl with H
    2
    SO
    4,
    HCl is also Iormed. The volatile HCl and the water vapour were transported Irom
    the reaction mixture through the PP membrane and dissolved in water on a permeate side. The inIluence oI a composition oI
    reaction mixture on the HCl Ilux through the hydrophobic membrane in MD module was studied. The ions present in the
    solution, such as K

    , SO
    4
    2-
    , Fe
    2
    and other present in the sulphuric acid were completely retained. This means that H
    2
    SO
    4
    and
    salts were retained on a Ieed side and were concentrated continuously. At initial concentration oI a Ieed containing about 1M
    KCl and 1.25M H
    2
    SO
    4
    , hydrochloric acid Ilux across the membrane achieved 258 mol HCl/m
    2
    d. The XRD analysis conIirmed
    that the precipitate separated Irom the reaction mixture was pure KHSO
    4
    or contained small amounts salts oI Fe(II), Mg
    2
    or
    Al
    3
    . From 223.65 g KCl and 1837g H
    2
    SO
    4
    during the conversion process 406g KHSO
    4
    was obtained and a mother solution
    which can be proceeded. The inIluence oI the mother solution composition (2M H
    2
    SO
    4
    and 1M KCl) on the conversion process
    oI KCl with post hydrolytic sulphuric acid will be also discussed.
    Praca naukowa wspolIinansowana przez Uni Europejska w ramach Europejskiego Funduszu Spolecznego i Budzetu Panstwa,
    Programu Operacvfnego Kapital Lud:ki Priorvtetu JIII, D:ialanie 8.2 Transfer wied:v Podd:ialanie 8.2.2 'Regionalne
    -88-
    Strategie Innowacfi, projektu systemowego realizowanego przez Wojewodzki Urzad Pracy w Szczecinie 'Inwestycja w
    wiedz motorem rozwoju innowacyjnosci w regionie (polish version).
    OD.3.2
    Preparation and characterization of PVDF hollow fibre membranes for vacuum
    membrane distillation
    A. Criscuoli
    1
    , A. Figoli
    1
    , S. Simone
    2
    , M.C. Carnevale
    2
    , E. Drioli
    1,2
    1
    Institute on Membrane Technologv, ITM-CNR, c/o Universitv of Calabria, Jia P. Bucci CUBO 17/C, 87036, Rende (CS),
    Italv
    2
    Department of Chemical Engineering and Materials, Universitv of Calabria, Jia P. Bucci Cubo 42/A, 87036, Rende
    (CS) Italv
    a.criscuoliitm.cnr.it
    PVDF hollow Iibres were prepared by the non-solvent induced phase inversion technique (NIPS). The inIluence oI several
    parameters, such as the composition oI the polymer solution (concentration, additives, etc.), composition oI the bore liquid, the
    air-gap beIore immersion in the coagulation bath, were investigated. Poly(vinyl pyrrolidone) (PVP) and water were used as
    additives in the dope while DMF/water (Irom 0 to 40 v/v) and ethanol (Irom 0 to 30 v/v) were employed as bore Iluid. The
    produced hollow Iibres were treated with NaClO in order to remove PVP and ensure hydrophobicity.
    The membrane morphology was characterized by Scanning Electron Microscopy (SEM), and mechanical tests, bubble point
    and contact angle were also perIormed. Asymmetric membranes were produced with a pore size oI the active layer ranging
    Irom 0.1 to 0.2 micron and a porosity oI about 80.
    Fibres were, then, tested in a vacuum membrane distillation (VMD) plant, using distilled water as Ieed. The eIIect oI both
    membrane properties and operating conditions on the water Iluxes was investigated. In particular, the measured Iluxes ranged
    between 5 and 24 kg/m
    2
    h at 50 C.
    The main problem encountered during the VMD runs was the decay oI Ilux with time, thereIore, diIIerent strategies were
    successIully tested to obtain a constant Ilux, such as thermal post-treatment and proper storage oI the Iibres.
    The authors acknowledge the Iinancial support oI the European Commission within the 6
    th
    Framework Program Ior the grant to
    the Membrane-Based Desalination. An Integrated Approach project (acronym MEDINA). Project no.: 036997.
    -89-
    OD.3.3
    Concentration of phenolic acids and flavonoids in aronia melanocarpa (choke berry)
    juice by osmotic membrane distillation
    L. Fjerbaek SotoIt
    1
    ; K.V. Christensen
    1
    , V.G. Horn
    2
    , B. Norddahl
    1
    1
    Institute of Chemical Engineering, Biotechnologv and Environmental Technologv, Universitv of Southern Denmark, Denmark
    2
    Palsgaard A/S, Juelsminde, Denmark
    lIjkbm.sdu.dk
    Membrane distillation (MD) has been tested as a low
    temperature replacement oI traditional Ialling Iilm
    evaporators Ior juice concentration. Compared to other
    membrane processes, MD is non-pressure driven
    perIorming a high degree oI concentration in the same
    versatile installation|1|.
    Aronia melanocarpa is among the red Iruits with the
    highest content oI antioxidants |2| and has gained must
    interest due to the content oI phenolic acids, procyanidins
    and polyphenolic compounds as anthocyanins |3|.
    In this study, osmotic membrane distillation (OMD) has
    been tested Ior the concentration oI not only sugars, but in
    particular potentially bioactive components such as
    phenolic acids and Ilavonoids.
    OMD is carried out on 37 kg aronia juice at 30C and the
    juice is concentrated Irom 12 wt to 74 wt dry matter.
    The juice is Iiltered to remove kernels, peel residues etc
    beIore concentration by OMD.
    Figure 1: OMD setup
    Analysis oI 14 speciIic phenolic acids and Ilavonoids such as neochlorogenic acid
    and quercitin during concentration show complete retention oI the bioactive
    compounds in the juice. The produced concentrate is a product with great market
    potential due to the high nutritional value.
    |1| V. Calabro, B. L. Jiao, E. Drioli, Industrial & Engineering Chemistry Research 1994, 33, 1803-1808.
    |2| B. Koroknai, Z. Csanadi, L. Gubicza, K. BelaIi-Bako, Preservation oI antioxidant capacity and Ilux enhancement in
    concentration oI red Iruit juices by membrane processes, Desal., 2008, 228, 295-301.
    |3| S.E. Kulling, R. M. Harshadai, Chokeberry (Aronia melanocarpa) - A Review on the Characteristic Components and
    Potential Health EIIects, Planta Med. 2008, 74(13), 16251634.
    -90-
    Figure 2. Aronia melanocarpa
    OD.3.4
    Modeling aroma stripping under various forms of membrane distillation processes
    G. Jonsson
    Department of Chemical and Biochemical Engineering, Technical Universitv of Denmark (DTU), Building 229, DK-2800 Kgs.
    Lvngbv, Denmark
    gjkt.dtu.dk
    Concentration oI Iruit juices by membrane distillation is an interesting process as it can be done at low temperature giving a
    gentle concentration process with little deterioration oI the juices. Since the juices contains many diIIerent aroma compounds
    with a wide range oI chemical properties such as volatility, activity coeIIicient and vapor pressure, it is important to know how
    these aroma compounds will eventually pass through the membrane.
    Experiments have been made on an aroma model solution and on black currant juice in a lab scale membrane distillation set up
    which can be operated in various types oI MD conIigurations: Vacuum Membrane Distillation , Sweeping Gas Membrane
    Distillation , Direct Contact Membrane Distillation and Osmotic Membrane Distillation. The inIluence oI Ieed temperature
    and Ieed Ilow rate on the permeate Ilux and concentration Iactor Ior diIIerent types oI aroma compounds have been measured
    Ior these MD conIigurations.
    A general transport model Ior the Ilux oI water and aroma compounds have been derived and compared with the experimental
    data. A reasonable agreement between the modelling and the experiments could be obtained. From the modelling it was
    possible to explain the large diIIerent in permeate Ilux and concentration Iactor that was observed Ior the diIIerent MD
    conIigurations. This is highly related to the heat and mass transIer resistances in the membrane as well as in the boundary
    layers adjacent to the membrane surIace and how the driving Iorce develops along the length oI the membrane.
    OD.3.5
    Microporous vs dense materials for hollow fiber membrane contactors: a critical
    theoretical and experimental study
    P. Nguyen
    1
    , D. Roizard
    1
    , E. Favre
    1
    , N. BouciI
    2
    1
    Laboratoire des Sciences du Genie Chimique (CNRS UPR 6811) ENSIC-Nancv Universites, 1 rue Grandville, 54 001 Nancv,
    FRANCE
    2
    Departement de Chimie Industrielle et LPQ3M, Faculte des Sciences de lingenieur, Universite de Mascara, Mascara 29000,
    ALGERIA
    pnguyenensic.inpl-nancy.Ir
    Hollow Iiber membrane contactors (HFMC) are already used at an industrial scale Ior intensiIied gas-liquid absorption or
    solvent degassing, and they appear to be a promising technology Ior crystallization or other separation applications. Up to now,
    the numerous studies that have been reported on HFMC Ior gas-liquid operations are almost exclusively based on microporous
    hydrophobic membrane materials. This strategy demands the criterion oI non wetting conditions oI the membrane material to
    hold, in order to ensure stable process perIormances over time. UnIortunately, gradual wetting oI the membrane material can
    occur, such as reported Ior CO
    2
    absorption in chemical solvents Ior instance |1|. The occurrence oI this detrimental wetting
    eIIect with time, which has been seldom investigated, addresses a generic potential problem oI HFMC.
    This study explores a tentative strategy in order to circumvent this problem, which has remained almost unreported up to now
    |2|. The key issue is to use a thin, dense membrane material in place oI a hydrophobic microporous one, Ior gas absorption
    applications.
    A rational evaluation oI microporous vs dense membrane materials Ior HFMC, both Irom the experimental and theoretical
    point oI view, will be reported. A case study based on CO
    2
    absorption Irom a gaseous mixture in an aqueous solution oI MEA
    has been perIormed and a microporous polypropylene HFMC is compared to a dense silicone rubber membrane HFMC over a
    broad range oI operating conditions. Based on a modeling oI the hydrodynamic and mass transIer mechanisms, a simulation oI
    the two processes has been achieved and a systematic parametric study is shown. The target perIormances oI dense membrane
    materials (thickness and associated intrinsic permeability) which can potentially compete with microporous membranes in
    terms oI mass transIer have been computed.
    The potential interest oI dense membrane HFMC and the possibility to achieve the target characteristics are Iinally discussed
    Ior diIIerent applications.
    -91-
    |1| R. Wang, InIluence oI the membrane wetting on CO
    2
    capture in microporous hollow Iiber membrane contactors,
    Separation and Purification Technologv 46 (2005) 33-40
    |2| H.B. Al-SaIIar, A comparison oI porous and non-porous gas-liquid membrane contactors Ior gas separation. Trans
    IChemE, (1997) 75, Part A.
    OD.3.6
    Surface modification for easier interface stabilization in membrane contactors:
    application to fractionation of essential oils
    A. Dupuy
    1
    , V. Athes
    1
    , J. Schenk
    2
    , U. Jenelten
    2
    , I. Souchon
    1
    1
    Laboratoire de Genie et Microbiologie des Procedes Alimentaires (LGMPA), UMR 782 INRA AgroParisTech, CBAI, 78 850
    Thiverval Grignon, France
    2
    Process Science Group, Corporate R&D Division, Firmenich S.A., Geneva, Swit:erland
    aurelie.dupuygrignon.inra.Ir
    Membrane contactors are cost-eIIective devices that enable considerable intensiIication oI liquid-liquid extractions, chieIly
    when emulsions Irequently occur. In such systems, phases are not mixed, which eliminates the need Ior phase separation, while
    mass transIer is achieved through the large speciIic interIace area provided by the highly porous membrane and the Iollow-
    Iiber geometry. However, Ior some phases, interIace stabilization (regulated by transmembrane pressure) is a challenging issue
    and undermines the robustness oI the process. To overcome this obstacle, membrane materials have to be chosen careIully and
    surIace modiIication appears to be an eIIicient tailor-made solution.
    Our research has been Iocused on the selective extraction oI oxygenated terpenes Irom citrus essential oils using water-ethanol
    mixtures as stripping solutions. Even iI polypropylene (PP) is very interesting because commercial hollow-Iiber modules are
    available (LiquiCel

    ), we observed that very low critical transmembrane pressures AP


    cr
    (0,05 Bar) prevent them Irom being
    used in industrial applications and alternative solutions must be obtained to reach AP
    cr
    _0,5 Bar. For this purpose, a Ilat-sheet
    module was designed and manuIactured to test organic, inorganic and surIace modiIied membranes (Figures 1 and 2).
    Moreover, contact angle measurements were carried out to assess membrane stability aIter immersion in essential oil.
    It appears that the only suitable polymeric membrane Ior interIace stabilization is made up oI PTFE (AP
    cr
    ~0,8 Bar Ior the best
    membrane) but there are no commercial hollow-Iiber modules. For inorganic membranes, surIace modiIication by covalent
    bonding oI Iluorinated compounds gives a signiIicant increase (0,25 Bar) oI interIace stability and the objective oI AP
    cr
    0,5
    Bar has been reached. SurIace modiIication oI inorganic membranes turns out to be much more eIIicient than the use oI
    conventional polymeric membranes in PP. A commercial hollow-Iiber module (Al
    2
    O
    3
    ) has been Iunctionalized and Iirst tests
    show very good perIormance Ior interIace stabilization and mass transIer rates.
    By modiIying the surIace oI membrane contactors, it is possible to increase the interIace stability which i) makes it possible to
    recover target molecules Irom complex systems such as essential oils, ii) broadens the range oI solvents that can be used and
    iii) makes process control much easier and more robust.
    Figure 1: water drop on a ceramic surIace Al
    2
    O
    3
    (0 47) Figure 2: water drop on a Iunctionalized ceramic surIace
    surIace Al
    2
    O
    3
    (0 125)
    -92-
    OD.3.7
    Amino acid salt solutions as selective absorption liquids in gas-liquid membrane
    contactors for CO
    2
    capture
    K. Fischbein
    1
    , H. Mengers
    1
    , K. Nijmeijer
    1
    , W. Brilman
    2
    , M. Wessling
    1
    1
    Membrane Technologv Group, Institute of Mechanics, Processes and Control Twente (IMPACT), Universitv of Twente, P.O.
    Box 217, 7500 AE Enschede, The Netherlands
    2
    Thermo-Chemical Conversion of Biomass Group, Institute of Mechanics, Processes and Control Twente (IMPACT),
    Universitv of Twente, P.O. Box 217, 7500 AE Enschede, The Netherlands
    k.Iischbeinutwente.nl
    CO
    2
    is one oI the major contributors to the greenhouse eIIect and the power and industrial sectors combined, account Ior about
    60 oI global CO
    2
    emissions |1|. The traditional method to separate CO
    2
    Irom other gases is amine scrubbing. Although high
    product yields and purities can be obtained, it has high energy consumptions and high liquid losses due to evaporation oI the
    solvent. Membrane technology is an attractive alternative Ior conventional absorption processes because oI its high energy
    eIIiciency, ease to scale-up, and its high area-to-volume ratio |2|. In the present work, we combine the advantages oI
    absorption processes with those oI membrane technology in a membrane contactor Ior the separation oI CO
    2
    Irom natural gas.
    In a membrane contactor, the gas Ieed and the absorption liquid are brought into contact through a membrane. Desorption
    occurs in a second membrane contactor. Gas-liquid membrane contactors oIIer a unique way to perIorm gas-liquid absorption
    processes in a controlled way. They have a high operational Ilexibility because the gas and the liquid stream can be controlled
    independently.
    Conventional amine based absorption liquids have several drawbacks (corrosive, unstable in the presence oI oxygen). In this
    work we investigate the potential oI amino acid salt solutions (potassium salt oI sarcosine) as new absorption liquids in a
    membrane contactor. Amino acids, such as sarcosine, have the same Iunctionality as alkanolamines (e.g. MEA), but in contrast
    to MEA they exhibit a high oxidative stability. In addition, they can be made non-volatile by adding a salt Iunctionality, which
    signiIicantly reduces the liquid loss. The use oI amino acid salt solutions in a membrane contactor requires knowledge on
    reaction kinetics between the amino acid salt and CO
    2
    , mass transIer coeIIicients, solubility values, and physicochemical
    properties, which were determined in this work as well and used to evaluate the membrane contactor experiments.
    Membrane contactor experiments show that even without temperature diIIerence between absorber and desorber, a CO
    2
    /CH
    4
    selectivity oI over 70 could be achieved with sarcosine as absorption liquid. This selectivity reaches values oI even 120 at a
    temperature diIIerence between absorber and desorber oI 35C (compared to a value oI only 60 Ior MEA under the same
    conditions), due to the more eIIective desorption process at higher temperatures. Although the CO
    2
    permeability is somewhat
    lower than the values obtained with MEA, the results clearly show the potential oI amino acid salt solutions as promising
    absorption liquid Ior the energy eIIicient removal oI CO
    2
    .
    OD.3.8
    Effect of membrane wetting on the process efficiency of a hollow fibre membrane
    contactor for gas recovery
    P. Luis, A. Garea, A. Irabien
    Departamento de Ingenieria Quimica v Quimica Inorganica, Universidad de Cantabria, Avda. Los Castros, s/n, 39005
    Santander, Spain
    luispunican.es
    Membrane processes have great interest in recovery oI target compounds Irom a gas stream due to widespread advantages |1|:
    controlled interIacial area, independent control oI gas and liquid Ilow rates and it avoids drops dragging, which is a key Iactor
    because oI environmental and economic considerations. In previous works |2,3|, intensiIication oI sulIur dioxide recovery was
    experimentally perIormed by means oI a ceramic hollow Iibre membrane contactor and N,N-dimethylaniline as the absorption
    liquid due to its high aIIinity and reversible interaction with sulIur dioxide. Under speciIic experimental conditions, the process
    eIIiciency ranged between 0.4 and 0.5.
    -93-
    Non-wetted mode has been demonstrated |4,5| to be the best operating mode because membrane pores are completely Iilled
    with gas, which leads to a mass transIer resistance several orders oI magnitude smaller than that oI liquid. A mathematical
    description oI the mass transIer in the hollow
    Iibre contactor is developed in this work in order
    to speciIy the eIIect that partial wetting has on
    the process eIIiciency. The dimensionless model
    equations as a Iunction oI the Graetz (G:) and
    Sherwood (Sh) numbers were solved in the radial
    and axial directions by a numerical method. The
    Sh number is related to the wetting ratio (x)
    according to this equation:
    l m g m
    Sh
    H x
    Sh
    x
    Sh
    , ,
    ) (
    +

    1 1
    where Sh
    m,g
    and Sh
    m,l
    are the Sherwood numbers
    iI the membrane was completely Iilled with gas
    and liquid, respectively; and H is the Henry`s law
    coeIIicient. Figure 1 shows the process eIIiciency
    Ior the non-wetted mode and the wetted mode
    considering diIIerent Sh values. Experimental
    results |2,3| establish that total or partial wetting
    could be assumed depending oI the H value
    considered.
    This research has been Iunded by the Spanish Ministry oI Science and Technology (Project CTM2006-00317).
    |1| A. Gabelman, S. Hwang, Hollow Iiber membrane contactors, J. Membrane Sci., 1999, 159, 61 106.
    |2| Luis, P., A. Garea, A. Irabien. SulIur dioxide non-dispersive absorption in N,N-dimethylaniline using a ceramic hollow
    Iibre membrane contactor, J. Chem. Technol. Biot., 2008, 83, 1570 1577.
    |3| P. Luis, A. Garea, A. Irabien, Zero solvent emission process Ior sulIur dioxide recovery using a membrane contactor and
    ionic liquids, J. Membrane Sci., 2008, doi: 10.1016/j.memsci.2008.12.046.
    |4| P. Luis, I. Ortiz, R. Aldaco, A. Garea, A. Irabien. Recovery oI sulIur dioxide using non-dispersive absorption, Int. J. Chem.
    React. Eng., 2007, 5, art. no. A52.
    |5| M. Mavroudi, S.P. Kaldis, G.P. Sakellaropoulos, A study oI mass transIer resistance in membrane gas-liquid contacting
    processes, J. Membrane Sci., 2006, 272, 103 115.
    OD.3.9
    Membrane emulsification at high temperature to assist the preparation of highly
    concentrated and stable solid lipid nano- micro-suspensions
    L. Giorno
    1
    , F. Bazzarelli
    1
    , E. Drioli
    1,2
    1
    Institute on Membrane Technologv, National Research Council, ITM-CNR, at Unical, Jia P. Bucci 17/C, 87036 Rende (CS),
    Italv
    2
    Department of Chemical Engineering and Materials, Universitv of Calabria, Jia P. Bucci 42/A, Rende (CS), Italv
    l.giornoitm.cnr.it
    Cross-Ilow membrane emulsiIication perIormance has been investigated Ior the preparation oI solid lipid nano- and micro-
    suspensions. Lipids were liqueIied at temperature between 50 80 C and pressed to permeate through tubular membranes
    Irom shell to lumen. Temperatures oI the disperse phase, membrane thickness and continuous phase were key conditions to
    achieve target particles size and stable suspensions. Commercial inorganic membranes with pore size Irom 1 m down to 20
    nm and diIIerent surIace roughness have been tested. While pore geometry and size control particle size during the droplet
    Iormation mechanism, membrane surIace roughness aIIects droplet stability aIter its Iormation. The inIluence oI axial velocity
    and permeate Ilux on droplet size distribution have been also investigated. The particles have been studied in terms oI both size
    distribution and stability as a Iunction oI time and mechanical stress. In addition to the suspension properties, the attention has
    been Iocused also on the eIIects oI temperature on membrane modules eIIiciency. For example, due to the high temperature,
    appropriate glue to seal the membrane edge has to be used in order to avoid poisoning oI the process through the non selective
    membrane support thickness. The type oI pumps used to circulate the continuous phase may also inIluence the Iinal product
    properties.
    -94-
    Figure 1. InIluence oI membrane wetting on the process eIIiciency.
    Experimental eIIiciency Ior the operation conditions (G:
    ext
    1.6210
    -2
    ;
    G:
    int
    82.02)) is shown in the vertical line. G:
    ext
    and G:
    int
    are reIerred to
    gas and liquid phases, respectively.
    Membrane emulsiIication permitted to control the preparation oI particles with target properties. For example, the preparation
    oI suspensions with narrow particles size distribution (span 1), Sauter mean diameters between 5 and 0.5 m, and solid lipid
    concentration higher than 35 have been obtained. Strategies Ior improving process productivity will be discussed, including
    chemical physical oI liquid phases properties, hydrophobic/hydrophilic membranes properties, Iluid dynamics oI the
    continuous phase. Challenging membrane properties and process perIormance needs will be outlined.
    OD.3.10
    Using membrane-aerated biofilm reactor to remove ammonium from wastewater
    with simultaneous nitrification and denitrification
    C. Picard
    1, 2, 3
    , J.C. Schrotter
    3
    , J.C. Rouch
    1, 2
    , C. Albasi
    4
    , J.C. Remigy
    1, 2
    1
    Universite de Toulouse , INPT, UPS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    2
    CNRS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    3
    Anfou Recherche, Jeolia Environnement, Chemin de la Digue, B.P. 76 , 78603 Maisons-Laffitte cedex, France
    4
    Universite de Toulouse , CNRS , Laboratoire de Genie Chimique , 6 allee Monso , 31029 Toulouse, France
    charlotte.picardveolia.com
    In this study, we use a membrane-aerated bioIilm reactor to remove ammonium Irom wastewater with simultaneous
    nitriIication and denitriIication. First, in this reactor, a hydrophobic membrane acts as a membrane contactor: it separates a
    gaseous Irom a liquid phase. Second, the membrane is a support to the development oI a bioIilm which grows on the liquid
    phase. Third, oxygen diIIuses Irom the gaseous phase through the membrane to the base oI the bioIilm. Contrary to oxygen,
    substrates (ammonium and organic carbon) diIIuse Irom the liquid phase towards the bioIilm; oxygen and substrates are in
    counter-diIIusion inside the bioIilm.
    In this conIiguration we create two areas: the bottom part oI the bioIilm is aerobic, due to oxygen diIIusion through the
    membrane (oxygen is consumed by bacteria) and its upper layer is anoxic. NitriIication occurs at the bottom oI the bioIilm
    (ammonium in presence oI oxygen is converted in nitrites and nitrates). Organic carbon is consumed in the upper layer by
    denitriIication (organic carbon and nitrates are converted in carbon dioxide and nitrogen gas) (Iigure 1).
    Simultaneous nitriIication and denitriIication with membrane-aerated bioIilms has previously been observed
    experimentally |1, 2|.
    This work is Iocused on the study oI the eIIects oI hydrodynamics on the bioIilm. Sloughing oI the bioIilm is studied under
    various shear stress conditions and the diIIerent resistances to gas transIer (gas, membrane, bioIilm and liquid) are quantiIied.
    BioIilm resistance is determined using a tracer gas which is not consumed by the bioIilm.
    Figure 1: Schematic diagram oI a membrane-aerated
    bioIilm able to do simultaneous nitriIication and
    denitriIication. The bigger arrows are Ior reactions oI
    nitriIication and denitriIication. COD: Chemical Oxygen
    Demand. ModiIied Irom |3|.
    Acknowledgment: The authors wish to thank Anjou Recherche Ior Iunding this work and allows the publication oI it.
    |1| K. Hibiya, A. Terada, S. Tsuneda, A. Hirata, J. Biotechnol., 2003, 100(1), 23-32
    |2| A. C. Cole, M. J. Semmens, T.M. LaPara, App. Environ. Microbio., 2004, 70(4), 1982-1989
    |3| S. Matsumoto, A. Terada, S. Tsuneda, Biochem. Eng. J., 2007, 37(1), 98-107
    -95-
    OD.3.11
    Silica Scaling in flat-sheet and hollow fiber DCMD modules
    Y. Ladizhansky
    1
    , A. Dov.
    1
    , E. Korin
    1
    , J. Gilron
    2

    1
    Dept. of Chemical Engineering,
    2
    Zuckerberg Institute for Water Research, Ben Gurion Univ., P.O.B. 653, Beer Sheva Israel 84105
    jgilronbgu.ac.i
    A number oI recent studies by Sirkar's group |1-2| have shown that hollow Iiber direct contact membrane distillation (DCMD)
    modules are Iairly resistant to calcium sulIate and calcium carbonate Iouling Ilux decline, even though the calcium salts indeed
    precipitate. Another common sparingly soluble mineral oIten Iound in brackish water Ieeds is silica. Because oI its normal
    solubility silica should stay stable to higher concentrations than at room temperature and this should allow Iurther water
    recovery and volume reduction oI brackish water RO brines by membrane distillation.
    We report here on a series oI experiments conducted with hollow Iiber and Ilat sheet DCMD modules with silica solutions with
    saturation indices oI 1.8 and higher at temperatures oI 65-75 C. The hollow Iiber modules similar to those used iI reI. 1-2, had
    eIIective pore size oI 0.5-0.6 micron but the pore mouths were 5-10 micron in diameter. The Ilat sheet membrane had
    eIIective pore size oI 1.2 micron. We Iound that unlike the work on other scalants, silica Iouling causes signiIicant Ilux
    decline aIter 2-7 hours induction time, causing Ilux declines oI up to 70 (see Figure 1). In Ilat sheet modules, the induction
    time Ior 400 mg/L silica solutions at 75 C was independent with initial Ilux ranging Irom 30-45 kg/m
    2
    -h, implying very
    diIIerent supersaturations at the membrane surIace. It is hypothesized that the Iouling occurs by deposition oI colloidal silica
    in the pore mouths blocking the pathways Ior vapor transport, and not by local crystal growth. SEM micrographs will be
    presented to veriIy this.
    Figure 1: Flat sheet DCMD run on solution oI 400 mg/L oI silica at brine entance temperature oI 75 C.
    [1] Fei He, Jack Gilron, Hanyong Lee, Liming Song, and Kamalesh K. Sirkar (2008), Potential Ior scaling by sparingly soluble
    salts in crossIlow DCMD, J. Membrane Science, 311, 68-80.
    |2| Fei He, Kamalesh K Sirkar, Jack Gilron, (2009), Studies on Scaling oI Membranes in Desalination by Direct Contact
    Membrane Distillation:CaCO3 and Mixed CaCO3/CaSO4 Systems, Chemical Engineering Science, accepted Ior publication.
    OD.3.12
    Antisolvent membrane crystallization of organic molecules
    G. Di ProIio, E. Curcio, E. Drioli
    1
    Institute on Membrane Technologv (ITM-CNR), Rende, ITALY.
    2
    Department of Chemical and Materials Engineering, Universitv of Calabria, Rende, ITALY
    g.diproIioitm.cnr.it
    A modiIied version oI the conventional membrane crystallization technique, in which a membrane is used to dose the
    solvent/antisolvent composition inside a crystallizing solution to generate supersaturation, has been developed. Two operative
    conIigurations are proposed: (a) solvent/antisolvent demixing crystallization, where the solvent is removed at higher Ilow rate
    than the antisolvent so that phase inversion promotes supersaturation and (b) antisolvent addition, in which the antisolvent is
    -96-
    dosed into the crystallizing drug solution. For both the solvent/antisolvent demixing and antisolvent addition conIigurations,
    antisolvent migration between the two sides oI the membrane was easily modulated by acting on the operative process
    parameters. Experiments demonstrated that accurate control oI solution composition at the crystallization point allowed a Iine
    control oI the supersaturated environment where glycine and paracetamol crystals with adjustable properties were grown.
    The two operative conditions allow a wide range oI applications Ior the crystallization oI organic molecules showing diIIerent
    aIIinities Ior hydrophilic solvents. Demixing conIiguration would be especially useIul Ior solutes poorly soluble in water and
    more soluble in hydrophilic solvents with higher vapor pressure, as alcohols or other organic solvents. As small temperature
    gradients are suIIicient to create a steady driving Iorce, Ieed temperature as low as 25-30 C generates trans-membrane Iluxes
    in the order oI 1 L m
    -2
    h
    -1
    or more. Antisolvent addition technique is an easy and Ieasible process where the only requirement is
    that solvent and antisolvent must be miscible. Moreover, because the crystallizing solution is kept at lower temperature than
    the distillate, thermo-labile species can be successIully crystallized without detrimental eIIects.
    As drowning-out crystallization is getting increasing involvement in pharmaceutical industry, the proposed systems represents
    a Iurther improvement oI the technique iI considering that a membrane acts as an adjustable gate Ior antisolvent dosing, and
    hence supersaturation control, inside the crystallizing solutions. Moreover, this technology, although tested Ior hydrophilic
    solutions, is theoretically exploitable also Ior the crystallization oI substances soluble in organic hydrophobic media, by
    employing hydrophilic membranes, thus extending the range oI applicability in pharmaceutical and other high-tech Iields like
    e.g. single crystal organic semiconductors.
    |1| Di ProIio G, Tucci S, Curcio E, Drioli E 2007. Selective glycine polymorph crystallization by using microporous
    membranes. Cryst Growth Des 7:526-530.
    |2| Di ProIio G, Tucci S, Curcio E, Drioli E 2007. Controlling polymorphism with membrane-based crystallizers: application
    to Iorm I and II oI paracetamol. Chem Mat 19:2386-2388.
    OD.3.13
    Hydrophilic microporous media or membrane contactor for oxygen transfer in wines
    I. Chiciuc, E. Ascencios, R. Adoua, A. Devatine, M. Mietton Peuchot
    Universite de Bordeaux, ISJJ, UMR nologie, Faculte dnologie, 210 Chemin de Levsotte, CS 50008, 33882 Jillenave
    dOrnon cedex
    igor.chiciucetu.u-bordeaux1.Ir
    All along wine making and ageing, as well as during ageing oI the bottled wine, oxygen is a major actor in the wine
    transIormation. It has a beneIicial role in many steps oI the wine elaboration (increase oI the yeast population, colour
    stabilization.), but oxygen may also be detrimental when present during speciIic steps (oxidation, growth oI
    microorganisms.). So, micro-oxygenation techniques, allowing mastered oxygen input, are nowadays well accepted Ior their
    stabilising eIIect |1|. The basic principle oI micro-oxygenation technique is to continuously deliver to the wine, stored in tanks,
    oxygen quantities always smaller than the chemical or biological demand, to avoid any accumulation oI dissolved oxygen.
    This oxygen input is done by micro-bubbling oI pure gaseous oxygen in the wine and this technique is now accepted practice
    in wine manuIacturing. Up to now, this input is only monitored by tasting and implementation oI chemical engineering
    concepts to these microoxygenation techniques should allow understanding and modelling mass transIer phenomena between
    gaseous oxygen and the liquid phase. The major diIIiculty oI micro-oxygenation with hydrophilic microporous membranes is
    the control oI the dimension oI the bubbles and the variability oI the yield oI transIer depending on the dimension oI the tanks,
    Ior example. So, the research concerns the comparison oI oxygen mass transIer by micro-oxygenation (convection) and
    membrane contactor (diIIusion). Membrane contactor is already proposed in beverage processes Ior carbonation oI sparkling
    wines or removal oI alcohol |2|. In a Iirst step, all the micro-porous systems (stainless, ceramic, HDPE membranes) are
    characterized by gas-liquid porometry to obtain the pore size distribution. Depending on the media, the mean pore size varies
    Irom 11m to 0.3m. The determination oI the bubbles sizes with the hydrophilic membranes has been evaluated with the
    Spaytec equipment (Malvern). The speciIic area oI the bubbles and the local mass transIer coeIIicient are calculated. In
    alcoholic model solution, the bubble size seems to be similar (200m) and the transIer does not depend on the micro-porous
    media. DiIIerent Ilow rates and types oI wines (red, white, rose) are tested. The bubble sizes and the transIer depend on the
    physical-chemical characteristics oI the wines. The membrane contactor (Liquid-Cel

    MiniModule) has been characterised


    with various hydro-alcoholic model solutions and Ior diIIerent shear stresses on the membrane. The mass transIer coeIIicient is
    higher with the increase oI the Ilow rates (oxygen and solution). Knowing the porosity and the surIace oI the membrane, the
    local mass transIer is calculated and compared with the micro-oxygenation technique. The transIer oI oxygen is easier to
    control with membrane contactor and could be calibrated and monitored using diIIerent Ilow rates.
    |1| A. Devatine, I. Chiciuc, C. Poupot, M. Mietton-Peuchot, Micro-oxygenation oI wine in presence oI dissolved carbon
    dioxide, Chemical Engineering Science, Volume 62, Issue 17, September 2007, Pages 4579-4588
    -97-
    |2| N. Diban, V. Athes, M. Bes, I. Souchon, Ethanol and aroma compounds transIer study Ior partial dealcoholization oI wine
    using membrane contactor, Journal oI Membrane Science, Volume 311, Issues 1-2, 20 March 2008, Pages 136-146
    OD.4.1
    Metal affinity chromatography for His
    6
    -tagged protein purification
    M.P. Dubois
    1
    , C. L. Gijiu
    1
    , M.P. Belleville
    1
    , S. Druon-Bocquet
    1
    , X. Santarelli
    2
    , D. Paolucci-Jeanjean
    1
    1
    Institut Europeen des Membranes (IEM). ENSCM, UM2, CNRS - Universite de Montpellier 2, CC 047, Place Eugene
    Bataillon - 34095 Montpellier, France.
    2
    EA 4135, ESTBB, Universite de Bordeaux, 146 rue Leo Saignat, 33076 Bordeaux cedex, France
    delphine.paolucciiemm.univ-montp2.Ir
    Membrane chromatography is an attractive alternative to column chromatography. It presents some advantages such as no
    intraparticle diIIusion, short axial-diIIusion path, low pressure drop, no bed compaction, and easier scale up. Consequently,
    membrane chromatography is a promising large-scale separation process Ior the isolation, puriIication, and recovery oI
    proteins.
    In this study, the puriIication oI His-tag enhanced green Iluorescent protein by membrane chromatography was investigated.
    An original organic-inorganic membrane was developed. The elaboration consists in 4 steps: i) deposition oI a polyvinyl
    alcohol layer on a ceramic membrane in order to Iunctionalize it, ii) cross-linking with bisoxirane to stabilise the polymer layer
    and to enable the graIting, iii) iminodiacetic acid graIting, iv) Cu
    2
    adsorption.
    Three aspects were studied. First, the elaboration procedure was optimized by acting on key parameters in order to maximize
    the Cu
    2
    adsorption and the highest value obtained (800 mg.m
    -2
    ) is higher than the highest reported in the literature Ior organic
    membranes |1| and than the value obtained with a chitosane-based aIIinity membrane |2|. Then, this membrane was used to
    carry out the puriIication oI His-tag enhanced green Iluorescent protein. The retention capacity oI the aIIinity membrane was
    Iound equal to 200 mg.m
    -2
    . Finally, the chromatographic process was modelled and the model was validated in order to be used
    Ior the membrane design.
    The authors acknowledge the French ANR (Agence Nationale pour la Recherche) Ior the Iinancial support (Project ANR JC05
    - 47316)
    |1| C.Y. Wu, S.Y. Suen, S.C. Chen and J.H. Tzeng, Analysis oI protein adsorption on regenerated cellulose-based immobilized
    copper ion aIIinity membranes, Journal oI Chromatography A, 2003, 996, 53.
    |2| C.J. Muvdi Nova, D. Paolucci-Jeanjean, M.P. Belleville, M. Barboiu, M. Rivallin, G. Rios, Elaboration, characterization
    and study oI a new hybrid chitosan/ceramic membrane Ior aIIinity membrane chromatography, Journal oI Membrane Science,
    2008, 321, 81-89.
    OD.4.2
    Permeation of salicylic acid through a supported liquid membrane based on ionic
    liquids
    N. Kouki, R. Tayeb, M. Dhahbi
    Laboratoire Eau et Technologies Membranaires, Centre de Recherches et des Technologies des Eaux, Technopole de Borf
    Cedria, BP 273, Soliman 8020, Tunisia.
    raIik.tayebcerte.rnrt.tn
    Supported liquid membranes (MLSs) have received a growing attention during recent years Ior the treatment oI liquid matrices
    containing metal ions and organic molecules. Among their numerous advantages is the Iact that the amount oI solvent needed
    in SLM process is minimal. Nevertheless, their industrial application is still limited, mainly due to concerns about SLM
    stability. SLMs with conventional solvents eventually deteriorate vaporization and dissolution into contacting phase. Ionic
    liquids (ILs) have recently been revealed as interesting clean alternatives to classical organic solvents. The use oI these new
    solvents as a liquid membrane phase results in the stabilization oI the SLMs.
    The aim oI this work was to deIine the optimal parameters Ior the extraction oI salicylic acid by a SLM based on the
    hexaIluorophosphate oI 1-n-hexyl-3-methyl imidazolium (C
    6
    C
    1
    -imPF
    6
    ) or based on the ethyl ammonium nitrate (EAN).
    -98-
    Firstly, the extraction oI salicylic acid was studied using the C
    6
    C
    1
    -imPF
    6
    . It has been observed that the transport eIIiciency
    decreases with increasing pH, indicating that the undissociated Iorm oI salicylic acid is mainly extracted. Despite the use oI
    diIIerent stripping solutions (NaCl, NaOH and Na
    2
    CO
    3
    ), uphill Iacilitated transport was not observed |1|.
    Secondly, the extraction oI salicylic acid was studied using the EAN. In this case, the ionic dissociated Iorm oI salicylic acid is
    extracted via the anion exchange mechanism between nitrate and salicylate anions. In Iact, the transport eIIiciency increases
    when Ieed aqueous pH increases |2|. Low concentration NaCl solution seems to be the most eIIicient stripping solution. As in
    the case oI C
    6
    C
    1
    -imPF
    6
    , uphill Iacilitated transport was not observed. By comparing the transport eIIiciency between the two
    used ILs, EAN appears to be more eIIicient than C
    6
    C
    1
    -imPF
    6
    .
    The non observation oI Iacilitated transport phenomenon can be explained by the Iormation oI water microenvironments as
    revered micelles in the ionic liquid membrane, and back transport oI water becomes the dominant mechanism |3|.
    |1| M. Matsumoto, T. Ohtani, K. Kondo, Comparison oI solvent extraction and supported liquid membrane permeation using
    an ionic liquid Ior concentrating penicillin G, J. Membr. Sci., 2007, 289, 92-96.
    |2| V.M. Egorov, S.V. Smirnova, I.V. Pletnev, Highly eIIicient extraction oI phenols and aromatic amines into novel ionic
    liquids incorporating quaternary ammonium cation, Sep. PuriI. Technol., 2008, 63, 710-715.
    |3| J. Martak, S. Scholosser, S. Vlckova, Pertraction oI lactic acid through supported liquid membranes containing
    phosphonium ionic liquid, J. Membr. Sci., 2008, 318, 298-310.
    OD.5.1
    Industrial scale experiences with pervaporation and vapour permeation
    E. M. Maus, A. Willenberg
    Sul:er Chemtech Ltd Membrane Technologv, Sul:er-Allee 48, CH-8404 Winterthur, Swit:erland
    eva.maussulzer.com
    Pervaporation as thermal separation technology has been established as state-oI-the-art technology to selectively remove water
    and/or methanol Irom (less polar) solvents and their mixtures, Iinding its application where conventional separation processes
    like (simple) distillation reach their limits or where they become quite expensive. The systems are executed as stand-alone
    units or hybrid systems in combination with distillation and/or reaction systems.
    The exceptional Ieature oI pervaporation is that the separation
    does not depend on vapour-liquid equilibria and thus even allows
    breaking azeotropes.
    It is e.g. possible to use a pervaporation in plants which use a two
    pressure distillation to get past the azeotrope between the solvent
    and water or methanol. Existing distillation plants Ior methyl ethyl
    ketone (MEK), acetonitrile (AcNi) or tetrahydroIurane (THF) can
    be combined with a pervaporation unit between the two
    distillation towers. As Ior isopropanol this conIiguration can either
    serve to reduce the overall energy consumption oI the plant or to
    increase the capacity. For THF Ior example capacity increase oI
    more than 50 oI existing plants can be reached without having to
    change the distillation towers and related equipment such as
    reboilers and condensers.
    Fig. 1. Examples oI the combination oI pervaporation
    and distillation (Ieed below azeotrope) |1|
    The presentation shows an overview oI diIIerent process options and pervaporation processes to remove water and/or methanol
    Irom less polar organic components on industrial scale.
    |1| Maus, E. M. and Brueschke, H. E. A. (2003). Hybrid Processes by Coupling Distillation and Pervaporation/ Vapour
    Permeation. 27
    th
    International Exhibition-Congress on Chemical Engineering, Environmental Protection and Biotechnology -
    ACHEMA 2003
    -99-
    OD.5.2
    Process performance improvement by HybSi

    nanosieve membranes for dehydration


    by pervaporation
    H.M. van Veen
    1
    , A. Motelica
    1
    , D.P. Shanahan
    1
    , R.Kreiter
    1
    , M.D.A. Rietkerk
    1
    , H.L. Castricum
    2,3
    , J.E. ten ElshoI
    2
    ,
    J. F. Vente
    1
    1
    Energv research Centre of the Netherlands, Efficiencv and Infrastructure, Molecular Separation Technologv, PO Box 1,
    1755ZG Petten, The Netherlands.
    2
    Inorganic Materials Science, MESA Institute for Nanotechnologv, Department of Science and Technologv, Universitv of
    Twente.
    3
    Jan t Hoff Institute for Molecular Sciences Facultv of Science, Universitv of Amsterdam.
    vanveenecn.nl
    The key objective oI the International Energy Agency (IEA) Ior Iuture energy technologies is to reduce CO
    2
    emissions with
    ~50Gt/yr by 2050. The 27 EU states decided a 20 boost overall in renewable Iuel use by 2020. In another key measure EU
    leaders decided to cut carbon dioxide emissions by 20 Irom 1990 levels by 2020. Carbon-neutral bio-based Iuels such as
    ethanol, butanol, and bio-diesel are promising candidates Ior transportation purposes. EIIective and energy-eIIicient separation
    technologies to dehydrate the wet Iuels are needed

    Ior large scale application. It is widely accepted that molecular separation
    membranes will play a crucial role in this transition to sustainable transportation Iuels. Furthermore these membranes can be
    used in the energy eIIicient dehydration oI all kinds oI chemicals.
    Pervaporation or hybrid distillation-pervaporation separation processes using membranes are commonly considered options Ior
    the energy eIIicient dehydration oI organics. We recently explored the use oI organic-inorganic hybrid silica Ior microporous
    membranes. These membranes have unprecedented liIe times oI at least 2 years in the dewatering oI n-butanol at 150C.
    1
    These membranes have a good perIormance in the dehydration oI ethanol as well, both under pervaporation and vapor
    permeation conditions
    2
    . Here, we report on the optimization oI industrial processes using these new membranes. By process
    simulation and Ilow sheeting Ior example the bio-ethanol production process via Iermentation has been calculated, new
    process schemes have been made and the process has been optimized. Calculations show that an important improvement in the
    energy consumption can be obtained, meeting the Iuture environmental criteria but also leading to important cost price
    reductions.
    |1| H. L. Castricum, A. Sah, R. Kreiter, D. H. A. Blank, J. F. Vente, J. E. ten ElshoI, Chem. Commun. 2008, 1103-1105
    |2| H. L. Castricum, R. Kreiter, H. M. van Veen, D. H. A. Blank, J. F. Vente, J. E. ten ElshoI, J. Membr. Sci. 2008, 324,
    111-118.
    |3| R. Kreiter, M. D. A. Rietkerk, H. L. Castricum, H. M. van Veen, J. E. ten ElshoI, J. F. Vente, ChemSusChem 2009, in
    press.
    OD.5.3
    Study on hybrid process including esterification reaction & pervaporation
    A. Penkova
    1
    , G. Polotskaya
    2
    , A. Toikka
    1
    1
    Saint-Petersburg State Universitv, Department of Chemical Thermodvnamics & Kinetics, Universitetskv pr. 26, Petrodvoret:,
    Saint-Petersburg, 198504, Russia
    2
    Institute of Macromolecular Compounds, Russian Academv of Sciences, Bolshov pr. 31, Saint-Petersburg, 199004, Russia
    stasya84gmail.com
    The use oI membrane reactors in hybrid processes is the object oI numerous investigations because oI the possibility to
    combine synthesis and molecular separation oI components at the same stage. Present work is Iocused on the reversible
    reaction oI esteriIication:
    Ester Water Alcohol Acid + +

    The esteriIication is terminated when the chemical equilibrium is reached. To continue the reaction, the equilibrium should be
    shiIted, Ior example, by removing one oI the reaction products. In the majority oI works the water removing by hydrophilic
    membranes are used whereas the ester removing is more promising action because ester is the target product that widely used
    in industry. In our previous work it was Iound that poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) is selective with respect to
    esters |1|. In the present work composite membranes consisting oI PPO thin layer and hydrophobic Iluorocarbon polymer
    -100-
    support were used Ior pervaporation separation oI quaternary mixtures oI esteriIication reaction. Syntheses both oI
    methylacetate and ethylacetate were under consideration. The work also concerned the problem oI thermodynamic modeling oI
    mass-transIer in the pervaporation process.
    Transport properties oI membranes depend on interactions between components oI the Ieed solution and the polymers oI the
    membrane. To estimate the interaction, swelling experiments oI PPO and Iluorocarbon polymer membranes in alcohols, acetic
    acid, water, and esters were made. Study on the kinetics oI sorption and desorption allowed the determination oI polymer
    swelling degrees, diIIusion coeIIicients, and Flory-Huggins parameters oI polymerpenetrant interaction. These parameters
    were used in analysis oI pervaporation data. It was established that the employment oI composite membranes results in a
    considerable increase in productivity oI membranes.
    Acknowledgment: This research supported by Russian Foundation Ior Basic Research (grant 09-03-00812).
    |1| G.A. Polotskaya; A.V. Penkova; A.M. Toikka; Z. Pientka; L. Brozova; M. Bleha, Transport oI small molecules through
    polyphenylene oxide membranes modiIied by Iullerene, Separation Science and Technology, 2007, 42(2), 333
    OD.5.4
    Integration of pervaporation and vapor permeation with an esterification reaction:
    lactic acid reaction with ethanol
    E. Gonzalez-Diaz
    1,2
    , A. Willenberg
    2
    , A. Hbner
    2
    , N. Martin
    2
    , E. Maus
    2
    ,
    J.R. Alvarez
    1
    , S. Luque
    1
    1
    Department of Chemical and Environmental Engineering, Universitv of Oviedo, 33071 Oviedo, Spain
    2
    Sul:er Chemtech Membrane Technologv, 66540 Neunkircken, Germanv
    elena.gonzalezsulzer.com
    EsteriIication oI lactic acid with ethanol has been studied, including the optimization oI the biocatalyzed reaction conditions,
    the integration with pervaporation (PV) Ior selective water removal, and the simulation oI an industrial plant oI the integrated
    system with either pervaporation or vapor permeation.
    Reaction conditions were Iirst optimized in batch runs: water content, pH, lactic oligomers content, acid:alcohol and
    subtrate:biocatalyst (lipase Irom Candida antartica B) ratios were assessed.
    Then, a PV membrane was selected based on its perIormance with synthetic reaction mixtures. AIter a preliminary membrane
    screening, three PV membranes were selected: PERVAP 1131, PERVAP 3100 and PERVAP 2216. For all oI them,
    water content in permeate was over 90, while lactic acid and ethyl lactate permeation were negligible. The PERVAP 1131
    membrane was selected aIter Iurther testing, as it provided good selectivity at reasonable Iluxes at the system temperature.
    Should the overall system be operating at higher temperatures, the PERVAP 2216 would also be a suitable alternative.
    One oI the challenges that pervaporation Iaces is the intake oI lactic acid in the membrane support, as the membrane absorbs it
    Since lactic acid has such low vapor pressure, it crystallizes (Figure 1).
    In order to prove the eIIiciency oI pervaporation Ior this reaction system, the enzyme was placed in a packed bed reactor and
    the reactor was coupled to a pervaporative system. This system allows reaching a higher conversion than that obtain when no
    dehydration system is employed (Figure 2). Moreover, the pervaporation is capable oI preconditioning the reactants to the
    optimal moisture content oI the reaction. The latter is important at industrial scale, since it makes possible the use oI cheaper
    raw materials, like azeotropic ethanol or concentrated aqueous lactic acid solutions. Following scale up calculations, a
    simulation oI a Iull-scale system was perIormed, including a comparison with vapor permeation, which would avoid lactic acid
    crystallization inside the membrane.
    Figure 1. Conversion oI the integrated pervaporative system
    () and the packed bed reactor alone (A).
    Figure 2. SEM picture oI crystals oI lactic acid in the support
    oI the membrane.
    -101-
    OD.5.5
    Separation of organic product streams from reactive distillation columns: membrane
    material selection and process integration studies
    T. Brinkmann
    1
    , H. Pingel
    1
    , Th. WolII
    1
    , M. Dker
    2
    , J. Gmehling
    2
    1
    GKSS Research Centre Geesthacht GmbH, Insitute of Polvmer Research, Department of Process Engineering, Max-Planck-
    Strae 1, 21502 Geesthacht, Germanv
    2
    Carl von Ossiet:kv Universitv of Oldenburg, Department of Industrial Chemistrv,P.O. Box 25 03, 26111 Oldenburg,
    Germanv
    torsten.brinkmanngkss.de
    Hybrid processes consisting oI conventional unit operations as distillation and membrane processes as pervaporation and
    vapour permeation are being discussed Ior a substantial time now. However, most applications aim at the separation oI water
    Irom organic solvents. The separation oI purely organic mixtures is hampered by the availability and diIIicult selection oI
    appropriate membrane materials. Within the scope oI a project Iunded by the German ArbeitsgemeinschaIt industrieller
    Forschungsvereinigungen (AiF), the University oI Oldenburg and GKSS investigated the transesterIication oI n-butanol and
    methylacetate to n-butylacetate and methanol. The reaction was conducted in a reactive distillation column (Figure 1). The top
    product oI this column consisted oI methanol and methylacetate in azeotropic composition.
    In order to separate this mixture, diIIerent process
    alternatives were investigated. One oI those was
    vapour permeation. In order to devise such a
    process, six diIIerent membrane materials were
    screened in a vapour permeation pilot plant
    operating at temperatures up to 110C and
    pressures up to 4 bar whilst maintaining a
    permeate pressure oI 10 mbar. The experimental
    results can be represented as Ilux curves and
    permeate compositions. OI the investigated
    materials, commercially developed membranes
    showed the highest Iluxes whilst one GKSS
    material showed the highest selecitivities.
    Considering the hybrid process shown in Figure 1
    a high selectivity might be advantageous since it
    allows Ior minimized recycle Ilowrates and hence
    a more economic process. The results oI the
    membrane material investigations as well as the
    design analysis oI the hybrid process using
    process simulation tools will be presented.
    Figure 1: Hybrid process Ior the transesterIication oI n-Butanol and
    Methylacetate to n-Butylacetate and Methanol with integrated product
    separation
    The authors grateIully acknowledge the ArbeitsgemeinschaIt industrieller Forschungsvereinigungen (AiF Nr. 14515) Ior
    Iunding the project and Sulzer Chemtech GmbH, Membrantechnik and PolyAn GmbH Ior the supply oI membrane samples.
    OD.5.6
    Coagulant influence on the removal of arsenic from drinking water by an anion
    exchange membrane-assisted process
    J. Llanos
    1
    , A. Oehmen
    2
    , J. Fradinho
    2
    , M.A.M. Reis
    2
    , S. Velizarov
    2
    , J.G. Crespo
    2

    1
    Chemical Engineering Department, Facultv of Chemical Sciences, Universitv of Castilla-La Mancha, Avda. Camilo Jose Cela
    12, 13005 Ciudad Real, Spain.
    2
    REQUIMTE/CQFB, Chemistrv Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.
    jgcdq.Ict.unl.pt
    Arsenic is a well-known toxic compound that is present in numerous drinking water systems due to industrial pollution sources
    or natural geochemical activity. Coagulation, membrane separation techniques, adsorption upon activated alumina or ion
    -102-
    exchange resins have been used to treat arsenic-containing waters. These techniques present some drawbacks, such as the onset
    oI secondary contamination oI the treated water (e.g. by coagulants) and/or diIIiculties in the disposal oI the associated brine
    solution (e.g. adsorbent regeneration or the retentate Irom membrane separation).
    In this study, we have tested a hybrid membrane process Ior the removal oI arsenic (As) Irom drinking water supplies. This
    process consists oI coupling an ion-exchange membrane and a simultaneous coagulation treatment. The contaminated drinking
    water is separated Irom the coagulant (added to a stripping compartment) by an anion-exchange membrane. Then, anionic
    arsenic (arsenate, arsenite) can be exchanged by a suitable counter-ion (e.g. chloride) and be precipitated in the stripping
    compartment, thus avoiding secondary contamination oI the drinking water.
    Two coagulants have been used Ior this purpose, FeCl
    3
    and AlCl
    3
    . These chemicals were selected not only because they are
    well-known coagulants, but also because both provide a suitable counterion (chloride) to be exchanged with the anionic
    arsenic. The inIluence oI the stripping solution chloride concentration, drinking water Ieed Ilow rate and operational time on
    the arsenic removal eIIiciency has been studied.
    Upon direct comparison oI both precipitants, FeCl
    3
    presented the best behaviour initially. When iron was added to the stripping
    compartment, the arsenic concentration was maintained below the detection limit (0.5 ppb) throughout the entire experiment,
    which was not the case with AlCl
    3
    . Moreover, the treated water concentration during the initial portion oI the tests was lower
    when FeCl
    3
    is used. However, AlCl
    3
    seemed to perIorm better during long-term operation, reaching a removal oI 80 oI the
    total arsenic concentration oI 100 ppb in the Ieed stream at a Feed Ilow rate/Area ratio oI 40 L h
    -1
    m
    -2
    , as compared to the 50
    removal achieved by FeCl
    3
    under similar conditions. The perIormance with AlCl
    3
    was maintained during the experiments and
    was not negatively aIIected by the Iormation oI aluminium precipitates. On the contrary, when FeCl
    3
    was used, there was a
    time threshold aIter which the arsenic concentration began to rise, probably due to the creation oI an additional transport
    resistance by the precipitate layer adsorbed upon the membrane surIace. This contrasting behaviour could be related to
    diIIerences in the charge and the apparent density oI both precipitates. With respect to the aluminium and iron concentration in
    the treated water, they were always maintained below their EU parametric values oI 200 ppm |1|, showing that the process was
    eIIective towards preventing secondary contamination oI the drinking water.
    |1| Council Directive 98/83/EC on the quality oI water intended Ior human consumption. L 330, 05/12/1998, pp. 3254.
    The Iinancial support by Fundao para a Cincia e a Tecnologia (FCT), Portugal through Project PPCDT/AMB/57356/2004
    is grateIully acknowledged.
    OD.5.7
    Capillary electrochromatography and membrane technology: merging the
    advantages
    K. Kopec, D. Stamatialis, M. Wessling
    Membrane Technologv Group, Universitv of Twente, Drienerlolaan 5, 7522 ND Enschede, The Netherlands
    K.K.Kopectnw.utwente.nl
    Capillary ElectroChromatography (CEC) is a separation technique which is a hybrid oI capillary electrophoresis (CE) and high
    perIormance liquid chromatography (HPLC) . The Ilow oI mobile phase is driven through a capillary by an electric Iield (a
    phenomenon known as electroosmosis) generated by applying a high voltage across the column. Application oI electrical
    current, rather than pressure, and presence oI a stationary phase result together in Iast separations that combine the eIIiciency
    oI capillary electrophoresis and the selectivity oI liquid chromatography. CEC with its precision, accuracy and possibility oI
    separation oI complex mixtures is very good technique Ior dealing with biomolecules (proteins, peptides) and pharmaceuticals
    Currently three types oI columns are used in CEC. In each case, the stationary phase is incorporated into Iused silica capillary
    and manuIacture oI CEC column is time consuming and expensive.
    Figure 1. Cross section oI a P84/S-PEEK Iiber Figure 2. CEC separation oI bovine serum albumin (BSA);
    buIIer: 20mM TEAP/60 ACN pH4.0
    -103-
    In this work, we use novel porous polymer Iibers as stationary phase Ior CEC. In Iact, small bore-Iibers are manuIactured via
    phase inversion by immersion precipitation spinning (Figure 1).
    The Iibres are prepared by either blending oI polymers (one polymer is charged) or Irom a single polymer while the second,
    charged polymer, is dissolved in the bore liquid. The Iunctional groups oI the charged polymer are ionized over a wide range
    oI pH and generate high electroosmotic Ilow. The perIormance oI Iibers is analyzed and compared with commercially
    available CEC columns in a home-built CEC set-up enabling testing oI Iibers with various diameters and lengths.
    Figure 2 presents separation oI bovine serum albumin (BSA) with polyimide P84/sulphonated poly ether ether ketone (S-
    PEEK) Iiber.
    OD.6.1
    Keep it natural ! Adjusting the pH of food products without chemical additives
    thanks to bipolar membrane electrodialysis
    F. Lutin
    EURODIA INDUSTRIE S.A., Parc dAffaires SILIC 7, Rue du Jura BP 30527 Wissous 94633 Rungis Cedex - France
    Tel . 33(0)1 56 30 16 40
    Ilorence.lutineurodia.com ; processeurodia.com
    One oI the attractive Ieatures oI Bipolar Membrane Electrodialysis is the possibility oI increasing or decreasing the pH oI
    aqueous solutions without the addition oI a base or oI an acid. For the production oI Iood and drink products or ingredients,
    this technology can be used in the processing oI liquids when it is necessary to change the pH to improve quality, taste, shelI
    liIe, etc. In addition to chemical savings, the main advantage is the elimination oI an added ingredient to preserve the 'natural
    character oI the product. A valuable acid or base by-product solution can be generated as an additional beneIit. Eurodia
    Industrie has worked on several applications oI this new technique Ior pH adjustment and this presentation will Iocus on
    practical examples in the production oI orange and grape juices, wines, vegetal or milk proteins, Iood-grade salt, etc.
    OD.6.2
    Experimental and theoretical study of pulse field electrodialysis
    B. Ruiz
    1
    , P. Sistat
    1
    , P. Huguet
    1
    , V. Nikonenko
    2
    1
    Institut Europeen des Membranes (IEM),, Universite Montpellier II,ENSCM, CNRS, CC047, Place Eugene Bataillon, 34095
    Montpellier, France
    2
    Kuban State Universitv, 149 Rue Stavropolskava 350040 KRASNODAR - Russia
    philippe.sistatiemm.univ-montp2.Ir
    These last years, the interest to lead electrodialysis in pulsed electric mode was shown |1-3|. The pulsed mode can make it
    possible to decrease the membrane Iouling by organic species. Scaling can also be reduced. Lastly, a notable gain on the
    transIerred electric charge was observed during desalination by pulsed electrodialysis at high Irequencies. However, the
    precise mechanisms which are at the origin oI these eIIects are not all clearly identiIied. For this purpose, a transport modelling
    study within the diIIusion boundary layers in pulsed mode was undertaken and correlated with the experimental data. The
    model used is particular Irom its boundary conditions because it must reIlect the speciIic mixed control mode oI the current
    and potential in pulsed mode. These conditions taken into account, the simulation can be done Ior a simple 1D geometry or a
    2D electrodialyser channel. The intensiIication oI electrodialysis in pulsed mode can then be explained by regeneration oI the
    diIIusion boundary layer content by diIIusion during switch oII time, regeneration oI the channel content by convection Ior
    low Irequency mode. The importance oI the channel design on the pulse Irequency appears through a pinch eIIect on the
    current density Ior too long pulse periods.
    -104-
    Average current during a pulse Iield electrodialysis run as a
    Iunction oI Irenquency and duty cycle.
    |1| Ruiz, B., Sistat, P., Huguet, P., Pourcelly, G., Aray-
    Farias, M. and Bazinet, L. EIIect oI pulsed electric Iield
    on anion-exchange membrane Iouling during
    electrodialysis oI a casein solution. Desalination,
    200(1-3):208-209, 2006.
    |2| Ruiz, B., Sistat, P., Huguet, P., Pourcelly, G., Araya-
    Farias, M. and Bazinet, L. Application oI relaxation
    periods during electrodialysis oI a casein solution: Impact
    on anion-exchange membrane Iouling. Journal oI
    Membrane Science, 287(1):41 - 50, 5/1/2007.
    |3| Casademont, C., Sistat, P., Ruiz, B., Pourcelly, G. and
    Bazinet, L. Electrodialysis oI model salt solution
    containing whey proteins: Enhancement by pulsed electric
    Iield and modiIied cell conIiguration. Journal oI
    Membrane Science, 2008
    OD.6.3
    Process intensification using an inorganic membrane reactor - water removal
    through a sod membrane
    S. Khajavi, K. Jansen, F. Kapteijn
    Ceramic Membrane Centre 'The Pore`, DelftChemTech, Delft Universitv of Technologv, Julianalaan 136, 2628 BL Delft, The
    Netherlands
    s.khajavitudelIt.nl
    The chemical and engineering community are paying signiIicant attention to the quest Ior technologies that would lead to the
    goal oI technological sustainability. A promising example with a lot oI interest by process engineers is process intensiIication.
    One oI the means oI implementing this strategy is the continuous growth oI modern membrane engineering whose basic
    aspects satisIy the requirements oI process intensiIication. Membrane operations, with their intrinsic characteristics oI
    eIIiciency and operational simplicity, high selectivity and permeability, good stability under operating conditions and
    environment compatibility represent an interesting answer Ior the rationalization oI chemical productions.
    Here, the Iocus is put on the development oI such membrane systems Ior the intensiIication oI reaction and separation units
    and their process capabilities. The experimental case examples are the esteriIication reactions oI ethanol and acetic acid, and
    butanol and acetic acid, both being limited in conversion by the thermodynamic equilibrium. A schematic presentation oI the
    reaction/separation systems is given in Fig. 1. In both reactions, water was selectively removed by means oI a zeolitic
    membrane, namely Hydroxy Sodalite |1-4|. The reactions were carried out in equimolar solutions, using Amberlyst 15 as the
    catalyst. While, the membrane showed excellent selectivity towards water (~1,000,000), the water removal led to a nearly
    complete conversion oI the alcohol to the ester, with the water Ilux being well compatible with the catalytic reaction rate in the
    reactor. The reaction conversion was increased by 30 in case oI ethanol esteriIication reaching almost 100 conversion. In
    case oI butanol esteriIication, conversion increased by 20 reaching above 90. Moreover, in the course oI the reactions, the
    membrane showed excellent stability under the acidic conditions, making it a promising candidate Ior in-situ water removal
    under harsh conditions.
    -105-
    |1| S. Khajavi, F. Kapteijn, J.C. Jansen , J.Mem.Sci., 299, 2007, 63.
    |2| S. Khajavi, F. Kapteijn, J.C. Jansen , Stud. Surf. Sci. Cat., 170, 2007, 1028.
    |3| M. Rhode, G. Schaub, S. Khajavi, F. Kapteijn, J.C. Jansen, Mirop. Mesop. Mat. 115, 2008, 123.
    |4| S. Khajavi, F. Kapteijn, J.C. Jansen , J.Mem.Sci., 326, 2009, 153.
    OD.6.4
    Process design of full scale membrane distillation plants for blackcurrant juice
    concentration on the basis of laboratory and pilot scale tests
    L. Fjerbaek
    1
    , K.V. Christensen
    1
    , R. Andresen
    2
    , B. Norddahl
    1
    1
    Institute of Chem. Eng., Bio-, and Environmental Engineering, Univ. Southern Denmark,
    2
    StatoilHvdro, Kalundborg, DK
    bnokbm.sdu.dk
    A conceptual process design with the use oI integrated membrane processes is prepared Ior blackcurrant juice concentrate
    (BCJC) production to replace traditional multiple step evaporators and aroma recovery. The combination oI membrane
    processes includes aroma recovery with vacuum membrane distillation and water removal by reverse osmosis, nanoIiltration
    and direct contact membrane distillation and has been combined with optimization oI membrane perIormance and juice quality
    in mind. A simple simulation based on results Irom experimental studies perIormed by external laboratories is combined with
    laboratory and pilot scale trials perIormed internally at the institute Iorms the basis Ior the economical calculation.
    The annual production scale used in the simulation is 14,800 tonnes oI 68Brix out oI single strength juice. The operation cost
    obtained in the simulation is 0.20 EUR/kg BCJ, which compared to costs normally linked to juice production is very
    Iavourable.
    |1| U.FAS, Market and Trade Data, United States Department oI Agriculture Foreign Agricultural Service, 2008.
    |2| V.D.Alves and I.M.Coelhoso, Orange juice concentration by osmotic evaporation and membrane distillation: A
    comparative study, Journal oI Food Engineering, 74(2006) 125-133.
    |3| C.Varming, M.L.Andersen, and L.Poll, InIluence oI thermal treatment on black currant (Ribes nigrum L.) juice aroma,
    Journal oI Agricultural and Food Chemistry, 52(2004) 7628-7636.
    |4| V.Calabro, B.L.Jiao, and E.Drioli, Theoretical and Experimental-Study on Membrane Distillation in the Concentration oI
    Orange Juice, Industrial & Engineering Chemistry Research, 33(1994) 1803-1808.
    |5| S.Cross, Membrane Concentration oI Orange Juice, Proceedings oI the Florida State Horticultural Society, 102(1989)
    146-152.
    |6| G.DauIin, J.P.Escudier, H.Carrere, S.Berot, L.Fillaudeau, and M.Decloux, Recent and emerging applications oI membrane
    processes in the Iood and dairy industry, Food and Bioproducts Processing, 79(2001) 89-102.
    |7| V.Gekas, G.Baralla, and V.Flores, Applications oI membrane technology in the Iood industry, Food Science and
    Technology International, 4(1998) 311-328.
    |8| Y.H.Hui, Handbook oI Fruits and Fruit Processing, Blackwell Publishing, Ames, Iowa, USA, 2006.
    |9| K.B.Petrotos and H.N.Lazarides, Osmotic concentration oI liquid Ioods, Journal oI Food Engineering, 49(2001) 201-206.
    |10| I.Vincze, E.SteIanovits-Banyai, and G.Vatai, Using nanoIiltration and reverse osmosis Ior the concentration oI
    seabuckthorn (Hippophae rhamnoides L.) juice, Desalination, 200(2006) 528-530.
    |11| S.Banvolgyi, S.Horvath, E.Bekassy-Molnar, and G.Vatai, Concentration oI blackcurrant (Ribes nigrum L.) juice with
    nanoIiltration, Desalination, 200(2006) 535-536.
    |12| J.Warczok, M.Ferrando, F.Lopez, and C.Guell, Concentration oI apple and pear juices by nanoIiltration at low pressures,
    Journal oI Food Engineering, 63(2004) 63-70.
    |13| A.Versari, R.Ferrarini, G.P.Parpinello, and S.Galassi, Concentration oI grape must by nanoIiltration membranes, Food
    and Bioproducts Processing, 81(2003) 275-278.
    |14| B.Jiao, A.Cassano, and E.Drioli, Recent advances on membrane processes Ior the concentration oI Iruit juices: a review,
    Journal oI Food Engineering, 63(2004) 303-324.
    |15| A.V.Bui and H.M.Nguyen, Scaling Up oI Osmotic Distillation Irom Laboratory to Pilot Plant Ior Concentration oI Fruit
    Juices, International Journal oI Food Engineering, 1(2005) 1-18. H.A.C.Thijssen and N.S.M.Oyen, Analysis and Economic
    Evaluation oI Concentration alternatives Ior Liquid Foods - Quality Aspects and Costs oI Concentration, Journal oI Food
    Process Engineering, 1(1977) 215-240.
    |16| C.C.Pereira, C.P.Ribeiro, R.Nobrega, and C.P.Borges, Pervaporative recovery oI volatile aroma compounds Irom Iruit
    juices, Journal oI Membrane Science, 274(2006) 1-23.
    |17| R.S.Ramteke, N.I.Singh, M.N.Rekha, and W.E.Eipeson, Methods Ior Concentration oI Fruit Juices - A Critical-
    Evaluation, Journal oI Food Science and Technology-Mysore, 30(1993) 391-402.
    |18| D.Sulc, FruchtsIte und IruchtsaItkonzentrate, (1991) 209-227.
    -106-
    |19| A.Isci, S.Sahin, and G.Sumnu, Recovery oI strawberry aroma compounds by pervaporation, Journal oI Food Engineering,
    75(2006) 36-42.
    OD.6.5
    Keynote: New membranes for new processes - Advances in organic solvent
    nanofiltration
    A.G. Livingston
    Department of Chemical Engineering and Chemical Technologv, Imperial College London, Exhibition Road, London, UK
    SW7 2AZ
    a.livingstonimperial.ac.uk
    Organic Solvent NanoIiltration (OSN) is a new and rapidly growing area oI membrane technology. In OSN, a pressure
    gradient is applied across a solvent stable nanoporous Iilm, inducing transport oI liquid across the Iilm. Depending on relative
    permeation rates, molecular species in a Ieed liquid stream can be separated. OSN has already reached large scale application
    in the reIining industry, and this is promoting a rising volume oI research and development into new membranes, transport
    mechanisms, and applications across several industries. This presentation will brieIly discuss OSN membrane characterisation
    and transport through these membranes, production oI new types oI solvent stable membranes and modules, and applications
    to processes where molecular separations have been achieved by OSN.
    Characterising which molecular separations a membrane can achieve, and elucidating the physical structure oI the membrane
    itselI so that it may be better engineered, are important challenges in OSN. Consistent experimental data which can be repeated
    in diIIerent research groups is scarce. The presentation will discuss new methods and results Ior the characterisation oI
    membranes |1|. The implications oI the experimental Iindings Ior modelling transport will be highlighted.
    Another challenge Ior OSN technology has been the lack oI membranes with wide solvent resistance, and which retain their
    nanostructure with exposure to aggressive liquids such as dipolar aprotic solvents (DMF, DMSO, THF). This problem has
    been solved through recent advances including post-Iormation crosslinking oI polyimide |2| and new polyaniline |3|
    membranes. Through careIul selection oI preparation conditions, membranes with controlled permeation properties |4| have
    been produced. These Iundamental advances have been rapidly translated to industrial innovation through scale up oI
    membrane manuIacture, and development oI spiral wound membrane elements which are stable in aggressive solvents, and the
    resulting new membrane series (DuraMemTM) will be described.
    The Iirst applications oI OSN were to reIining. New applications to processes in Iine chemicals and pharmaceuticals |5| will be
    discussed, including puriIications and biopolymer synthesis. PuriIications can comprise removing smaller reagents Irom larger
    products to avoid undesirable subsequent reactions, or removal oI larger oligomeric or colour bodies Irom post reaction
    mixtures. These new processes reveal the power oI OSN over other, traditional separation techniques.
    |1| See-Toh YH, et al. J.Mem.Sci 291 (2007) 120-125
    |2| See-Toh YH et al. J.Mem.Sci. 301,( 2007), 3-10
    |3| X.X. Loh et al. J.Mem.Sci 326, ( 2009), 635-642
    |4| See-Toh YH et al. J.Mem.Sci. 324, (2008), 220-232
    |5| Nasso, M; et al. CHIMICA OGGI-CHEMISTRY TODAY: 26 (2008) 62-66
    -107-
    OE.1.1
    Mathematical analysis of the multiple-scale flow field in spiral wound membrane
    modules
    M. Kostoglou
    1
    , A. J. Karabelas
    2


    1
    Division of Chemical Technologv, Department of Chemistrv, Aristotle Universitv, Thessaloniki
    2
    Chemical Process Engineering Research Institute, Center for Research and Technologv Hellas, P. O. Box 60361, GR 570 01,
    Thermi-Thessaloniki, Greece
    karabajcperi.certh.gr
    The design oI RO/NF membrane plants, aimed at minimization oI cost and energy expenditure, critically depends on
    optimization oI spiral wound module (SWM) perIormance, which is aIIected by many Iactors. Mathematical models oI SWM
    operation are necessary tools Ior this task. Despite progress made in recent years in understanding basic phenomena
    occurring in RO/NF operations, their quantitative description, in an integrated manner, is hindered by the great geometrical
    complexity oI SWM, which leads to two (coupled) 3-D Ilow compartments. A notable Ieature oI this problem is the existence
    oI several Ilow length scales, Irom the pores oI the permeate-side Iiller to the macroscopic dimensions oI the module, with
    the most important size scales being those associated with the spacers in the retentate channels.
    Modeling eIIorts so Iar vary between the extremes oI detailed description oI transport phenomena at small scale to
    oversimpliIied simulation oI the entire separation process, thus missing the eIIect oI essential Iactors. A popular and IruitIul
    approach (dealing with the meso-scale problem) is based on a periodic unit cell, where the Ilow simulation is restricted to a
    small part oI the module (including the geometric details oI Ieed-side spacer), permitting a detailed description oI the 3-D
    Iield. Commercial Computational Fluid Dynamics codes are commonly used Ior this type oI modeling.
    Although practically all the elements required Ior comprehensive simulation oI spiral wound modules can be Iound in the
    literature, they are quite dispersed among models oI diIIerent scales and diIIerent degrees oI approximation. The scope oI this
    work is to describe the hydrodynamics oI SWM, starting Irom Iirst principles, to explain some realistic approximations and
    their origin, and to present an integrated model where linking oI the various length scales is an essential Ieature. This eIIort
    has resulted in an eIIicient numerical algorithm, allowing predictions oI the spatial distribution oI pressure, permeation and
    cross-Ilow velocities throughout the membrane leaves. In this eIIort, all possible analytical solutions have been derived which
    Iacilitate the simulation algorithm. Typical examples oI predicted Ilow distributions will be presented.
    OE.1.2
    Gas-liquid contacting in ceramic membrane microreactor: numerical and
    experimental study
    J.M. Jani , D. Salamon, H.C. Aran, R.G.H. Lammertink, M. Wessling
    Membrane Science and Technologv, Facultv of Science and Technologv, Universitv of Twente, P.O. Box 217, 7500AE
    Enschede, The Netherlands
    j.m.janitnw.utwente.nl
    Microreactors have submilimeter dimensions that provide high surIace to volume ratio and also provide enhanced heat/mass
    transIer rates Ior desired reactions. Membrane microreactor involving multiphase reaction in microchannels suits industrially
    important chemical processes e.g. gas-liquid hydrogenation and immiscible liquid-liquid nitration. The development oI
    Iundamental models describing chemical, physical phenomena in membrane microreactors attracts considerable interest in
    recent years.
    Ceramics oIIer excellent thermal and mechanical stability particularly at extreme conditions i.e. high temperature and pressure.
    The research Iocuses on benchmarking oI gas-liquid contacting methods Ior diIIerent microreactor designs. Two pathways are
    to Iollow in Iabrication oI ceramic membrane microreactor: planer and hollow Iiber geometry. To aid in the design special
    emphasis will be given to Iluid dynamics behavior inside porous structure. Hydrodynamics play a very important role in the
    microreactor design and operation. With known component properties, a good prediction with respect to mixing, reaction and
    heat generation can be obtained. The enhancement in mixing and mass transIer oI the hollow Iibre geometry has been
    predicted numerically. This phenomenon is observed due to secondary Ilow induced by curvature. The experiment analysing
    hydrodynamics and mass transIer inside helical hollow Iibre channel will be carried out in order to Iurther investigate the
    perIormance oI the microreactor.
    -108-

    Figure1. Porous Ceramic Microreactor concept Figure 2. Mixing in helical structures
    OE.1.3
    Visualisation of cake layer formation and liquid flow in a microfiltration process via
    nuclear magnetic resonance (NMR) tomography
    S. Buetehorn
    1
    , L. Utiu
    2
    , M. Kueppers
    2
    , B. Bluemich
    2
    , T. Wintgens
    1
    , T. Melin
    1
    1
    Chemical Process Engineering, AJT, RWTH Aachen Universitv, Turmstr. 46, 52056 Aachen, Germanv
    2
    Chair of Macromolecular Chemistrv, ITMC, RWTH Aachen Universitv, Worringer Weg 1, 52056 Aachen, Germanv
    SteIIen.Buetehornavt.rwth-aachen.de
    In pressure-driven microIiltration processes, a liquid-solid phase separation is Iacilitated by means oI a size exclusion
    mechanism. Hence, dispersed solids oI the Ieed stream are rejected according to their size in relation to the nominal pore
    diameter oI the membrane. The convective mass transport through the pore structure and the lumen side oI the membrane are
    signiIicantly aIIected by a number oI process parameters such as cross-Ilow velocity and permeate Ilux. Furthermore,
    characteristics like pore size and permeability distribution along the membrane as well as particle size distribution and
    rheology oI the model suspension are oI importance to Iurther understand the Iiltration behaviour.
    In the Iramework oI this study, a submerged microIiltration process using a polymeric hollow-
    Iibre membrane and silica suspensions oI diIIerent solids concentration is investigated. The
    overall objective is to (i) determine the thickness oI the layer oI deposited matter continuously
    Iormed on the surIace oI the membrane and (ii) to evaluate the permeability distribution along the
    Iibre. For this purpose, a nuclear magnetic resonance (NMR) technique is used, which is based on
    the excitation and relaxation oI protons in a specimen under the inIluence oI an external magnetic
    Iield |1|. While the cake height was visualised and thereIore determined directly (see Fig. 1, top),
    the permeability distribution was estimated by a measurement oI the average vertical Ilow velocity
    which is linked to the local permeate production via the continuity equation (see Fig. 1, bottom).
    To date, the model suspension has been characterised by means oI rheological measurements and
    preliminary cross-Ilow respectively submerged Iiltration studies have been perIormed. It was
    shown that the permeate Ilux respectively transmembrane pressure evolution is consistent with
    published Iiltration theories |2|. Subsequently, the NMR test protocol was Iurther improved and a
    comprehensive test series was initiated. On the basis oI these experimental results, eIIorts will be
    made to Iurther understand the impact oI operating parameters, membrane properties and
    characteristics oI the model suspension on the overall Iiltration perIormance.
    Financial support oI the European Commission and the German Research Foundation are
    acknowledged.
    Figure 1: Cake height
    (top) and Ilow velocity
    (bottom) measurements.
    |1| V. Chen, H. Li, A.G. Fane. Journal oI Membrane Science 241 (2004) 23-44.
    |2| S. Buetehorn, F. Carstensen, T. Wintgens, T. Melin D. Volmering, K. Vossenkaul. Desalination (submitted).
    -109-
    OE.1.4
    How spacer geometry can affect the thermo-fluid dynamics of a membrane
    distillation module
    A. Cipollina, A. Di Miceli, G. Micale, L. Rizzuti
    Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Jiale delle Scien:e, Ed.6, 90128
    Palermo (Italv)
    cipollinadicpm.unipa.it
    In membrane distillation modules, as in all membrane processes, the module geometry can be a crucial matter, as the choice oI
    proper channel shape and dimension can dramatically aIIect the perIormance oI the process. In particular, temperature
    polarization phenomena and pressure drops along the channels are Iundamental parameters Ior the control oI separation
    eIIiciency on one side and pressures distribution, module mechanical resistance and pumping costs on the other.
    Relevant literature reports several works on the Iluid dynamic characterization oI spacers used in Reverse Osmosis modules,
    but only Iew works deal with the problem oI channel optimization oI MD modules. The typical approach adopted is that oI
    Computational Fluid Dynamics simulations oI portions oI channel, oIten Iorced to a periodicity which does not always
    distinguish the commonly adopted spacers. Moreover, lack oI experimental data reduces the possibility oI validating CFD
    results by direct comparison with experiments.
    In the present work the thermo-Iluid dynamic behaviour oI diIIerent types oI spacer geometries oI MD modules has been
    analyzed using CFD tools coupled to an experimental investigation carried out on a purposely built bench scale apparatus. The
    commercial CFD code CFX11.0 has been used Ior predicting the eIIects oI the spacer shape, dimension and orientation on the
    operating conditions oI a portion oI a typical Membrane Distillation module channel. The behaviour oI several spacers`
    geometry was simulated and compared with experimental observation. Finally, CFD results were used to characterize velocity
    Iields, pressure distribution and temperature polarization in the channel, thus providing precious inIormation on the potentially
    'optimal Ieatures oI an MD channel spacer.
    OE.2.1
    Challenges in designing a pressure retarded osmosis power plant
    E. Sivertsen
    1
    , T. Holt
    2
    , T. Thorsen
    1
    1
    SINTEF Building and Infrastructure, Water and Environment, NO-7465 Trondheim, Norwav
    2
    SINTEF Petroleum Research , Seismic and Reservoir Technologv, NO-7465 Trondheim, Norwav
    edvard.sivertsensinteI.no
    Salinity power is a renewable and sustainable energy resource with a signiIicant potential world-wide which has lead to
    increasing attention in recent years. The principle is to use the mixing entropy when mixing Iresh water with sea water.
    Osmotic power is one class oI salinity power where pressure retarded osmosis (PRO) is one oI the technical Ieasible processes
    which can be used to extract this energy. In PRO Iresh water and sea water are separated by a membrane allowing only water
    -110-
    to be transported Irom the Iresh water side to the sea water side oI the membrane due to diIIerence in osmotic pressure. The
    increased pressure on the sea water side can run a turbine.
    One oI the major concerns with PRO is the relatively low speciIic power (W/m
    2
    ) implying that a power plant needs a large
    membrane area and that the energy loss throughout the process is kept as low as possible. In order to study the power plant
    eIIiciency a general PRO power plant model is developed including all necessary unit operations and energy losses in a power
    plant. Figure 1 shows a sketch oI the PRO power plant and its main components including inlet pumps, pre-Iiltration, pressure
    exchanger, booster pump, membrane module and turbine.
    The model has a large number oI variables categorized into plant layout and piping variables, eIIiciencies, membrane and
    membrane module variables. At present two diIIerent membrane modules are integrated into the power plant model, a
    modiIied spiral module with cross Ilow on each side oI the membrane and a Iiber module with longitudinal Ilow on both sides
    oI the Iiber. A presentation will be given that addresses the use oI diIIerent kinds oI membrane modules, and other alternative
    uses oI components in the PRO system. In addition the presentation will address some oI the critical areas oI development Ior
    securing the Iuture success oI a commercial PRO system.
    Figure 1. A sketch of the PRO power plant.
    OE.2.2
    Numerical and experimental methodology for the development of a highly selective
    ceramic microfiltration membrane intended to bioprocesses
    F. Springer
    1
    , E. Carretier
    1
    , D. Veyret
    2
    , D. Dhaler
    3
    , P. Moulin
    1
    1
    Universite Paul Ce:anne Aix Marseille, Laboratoire de Mecanique, Modelisation et Procedes Propres (M2P2 UMR-CNRS
    6181), Europole de lArbois, BP. 80, Batiment Laennec, Hall C, 13545 Aix en Provence Cedex 04, France
    2
    POLYTECH Marseille, (CNRS-UMR 6595) Technopole de Chateau-Gombert, 5 rue Enrico Fermi, 13453 Marseille Cedex 3,
    France
    3
    NOJASEP APPLEXION SAS, Site Saint Maurice de Bevnost, 5 Chemin du Pilon, 01708 Miribel, France
    The need oI high quality separation in bio-process industries underlies a huge part oI the current membrane processes
    developments. In this Iield, potential applications oI such processes keep on expanding, rising with them new technological
    and scientiIic problematic. This study Iocused on tubular ceramic microIiltration membrane Ior highly selective separations.
    The milk was studied as an example, involved in treatment processes like casein separation or bacteria and spores removal.
    The main scientiIic stumbling blocks are due to a strong Iouling which impacts the permeation Ilux and also leads to a bad
    selectivity. These perIormances are linked to a non uniIorm transmembrane pressure along the length oI the tubular membrane.
    However, the Iouling apparition and accumulation aIIect the product quality when a long duration process because the
    production Ilux slowly decreases during the Iiltration and the Iiltration cake modiIies the process selectivity. The purpose oI
    this study is to better control the Iiltration cake build-up, by maintaining the transmembrane pressure (TMP) as steady as
    possible along the membrane, with the aim oI remaining the process perIormances stable. The production Ilux is controlled by
    the membrane external surIace. This external surIace is covered with thoroughly impermeable coating and one or several
    permeation Ilues are generated to maintain a constant TMP as low as possible.
    The Iirst part oI this work consisted in a numerical approach in order to study the TMP and permeate Ilux proIiles along the
    membrane and to predict the production Iluxes oI the designed prototypes. Several parameters were modelled and studied: the
    operating parameters (tangential velocity, inlet and permeate pressures), the permeation surIace that is generated on each
    membrane prototype (taking into account the number, the distribution and the width oI the engraved Ilues). The results oI this
    numerical study are then compared to experimental results obtained with water Iiltration. Furthermore, those Iirst experimental
    results lead to the modelling results conIirmation. We have obtained a value oI 2.3 L.h
    -1
    .bar
    -1
    Ior each permeation Ilue
    whatever the position, and the Ilue number on the membrane.
    AIterwards it was necessary to launch a milk experimental campaign. The complex phenomena indeed engendered during milk
    Iiltration make this liquid much more diIIicult to be modelled with the CFD tool. The milk Iiltration experiments demonstrated
    the results reproducibility and enabled us to establish an expectable value oI milk production per Ilue and per local TMP unity
    (considered in the Ilue location). Whereas the obtained Ilux values are steady, the permeate quality shows a behaviour
    -111-
    depending on the local PTM during the process, the Ilue locations and the Iiltration duration. Minimal milk permeability and
    protein transmission rate values oI respectively 100 L.h
    -1
    .m
    -2
    .bar
    -1
    and 85 are obtained. Moreover, the hydrodynamic eIIects
    at the inlet and outlet oI the membrane are taken into account to determine the design oI the membrane. This study brought the
    solutions Ior the Iinal industrial prototypes.
    OE.2.3
    Optimal control of wash water utilization in batch diafiltration
    Z. Kovacs
    1
    , M. Ebrahimi
    1
    , P. Czermak
    1, 2
    1
    Universitv of Applied Sciences Giessen-Friedberg, Institute of Biopharmaceutical Technologv, Wiesenstrasse 14, 35390
    Giessen, Germanv
    2
    Department of Chemical Engineering, Kansas State Universitv, Manhattan, Kansas, 66506, U.S.A.
    Kovacs.Zoltantg.Ih-giessen.de
    There exist several concepts oI wash water utilization in diaIiltration processes. The traditional diaIiltration (TD) process may
    involve three steps: (i) pre-concentration step; (ii) constant volume diaIiltration step, to reduce microsolute concentration; and
    (iii) post-concentration step, which is used to concentrate the macrosolute. In contrary with that, variable volume diaIiltration
    (VVD) is an operation mode in which Iresh water is continuously added to the Ieed tank at a rate that is less than the permeate
    Ilow. This causes a simultaneous concentration oI macrosolute and reduction oI microsolute. In this study, a mathematical
    Irame Ior modeling various diaIiltration modes is provided. The approach Iollowed in this work hands separately the design
    equations oI the system conIiguration and the models oI mass transIer through the membrane. Previous studies have shown the
    advantages oI this concept |1,2|. The numerical solution oI the proposed set oI ordinary diIIerential equations allows the
    prediction oI the dynamic behaviour oI diaIiltration systems (Fig.1). The presented simulation technique is a useIul tool Ior
    evaluating the optimal system design, operation, and control. The purpose oI the optimization is to Iind the set oI operational
    parameters which result in the most economical process and satisIy the given technological demands oI the Iinal product. The
    diIIerent diaIiltration operations are compared in respect to total operation time, total product loss, and wash water utilization.

    Fig.1. Optimal proIile oI permeate Ilux (leIt side) and microsolute concentration (right side) over the operation time Ior TD
    and VVD processes.
    |1| Z. Kovacs, M. Discacciati,W. Samhaber, Modeling oI batch and semi-batch membrane Iiltration processes, J. Membr. Sci.
    327 (2009) 164173
    |2| Z. Kovacs, M. Discacciati,W. Samhaber, Numerical simulation and optimization oI multi-step batch membrane processes,
    J. Membr. Sci. 324 (2008) 50
    -112-
    OE.3.1
    Mass transfer enhancements in ultrafiltration membrane applications using new
    micro-engineered membrane spacers
    C. Fritzmann, H. Li, T. Melin
    Aachener Jerfahrenstechnik (AJT), Chemical Process Engineering, RWTH Aachen Universitv, Turmstr. 46, D-52056 Aachen,
    Germanv
    clemens.Iritzmannavt.rwth-aachen.de
    The eIIiciency oI membrane processes like ultraIiltration (UF), nanoIiltration,
    reverse osmosis or electrodialysis to a great extent depends on optimized Ilow
    conditions within the membrane module. Mass transport to the membranes as
    well as Iouling propensity is determined by mixing conditions within the Ieed
    compartment oI the membrane module. Eddy mixing induced by spacers placed
    into the Ieed compartment greatly inIluences Iouling rate and enhances mass
    transport by reducing concentration polarization |1||2|.
    In this work a new micro-engineered spacer design is investigated, which
    promises Iurther advances in mass transport and higher energy eIIiciency oI the
    overall process. The new spacer displays a constant cross sectional area in the
    main direction oI Ilow resulting in low Ieed side pressure losses, while at the
    same time high mixing rates at the membrane surIace are ensured by the speciIic
    shape oI the spacer Iilaments (cI. Fig 1).
    Prototypes oI the membrane spacers are manuIactured using rapid prototyping
    technology and are implemented in a Ilat sheet membrane test cell applying 200
    kDA UF membranes Ior experimental investigation. Membrane Ilux as well as
    pressure loss within the Ieed channel is measured within a relevant range oI cross
    Ilow velocities, i.e. Re number range, and compared to Iiltration without any
    membrane spacer or application oI commercially available net type membrane
    spacers. In addition molecular weight cut-oII (MWCO) oI well-deIined dextran
    solutions depending on cross Ilow velocity is determined using HPLC
    measurements to analyze MWCO shiIt caused by application oI the new
    membrane spacer.
    Implementation oI the new spacer type shows signiIicant mass transIer enhancements; permeate Ilux increases between 3 to 4
    Iold, depending on TMP and cross Ilow velocity, at similar energy requirements compared to mass transport in an undisturbed
    Ilow Iield. In addition strong MWCO shiIts are observed to signiIicantly lower molecular weights when applying the new
    membrane spacers.
    |1| A.R. Da Costa, A.G. Fane, Ind Eng Chem Res 33 (1994) 1845-1851
    |2| P.R. Neal, H. Li, A.G. Fane, D.E. Wiley, J Membr Sci 214 (2003) 165-178
    OE.3.2
    Keynote: dynamic micro fractionation
    C.J.M. van Rijn, A. Nguyen
    Wageningen Universitv, Laboratorv of Organic Chemistrv, Dreifenplein 8, Building 316, 6703 HB Wageningen, The
    Netherlands.
    ceesvanrijnaquamarijn.nl
    MicroIractionation oI biological samples with membranes is constituted by a number oI Iactors, such as membrane structure
    itselI, Ieasibility oI process, and physical chemistry properties oI membrane surIace. We have been Iocusing on development
    oI new microsieve structures, which challenges signiIicant alternative Ior new insight oI membrane engineering. Concurrently,
    the module design and test set-up with an incorporation oI advanced piezo devices has been studied. Prototypes oI
    micromachined membrane modules in combination with microIractionation set-up oI advanced piezo have been pursued.
    Preliminary results show that piezo driven membranes enhance eIIectively the microIractionation process. Additionally,
    -113-
    advanced surIace modiIication techniques oI microsieve membranes have been applied to enhance selI-cleaning properties oI
    the system. The promising results oI integrated microIractionation system open a new prospect to micro/nano separation
    applications.
    |1| C.J.M. van Rijn, Nano and micro engineered membrane technology`, Elsevier Amsterdam (2004), ISBN 0444-51489 9
    OE.4.1
    Membrane fouling characterization by confocal scanning laser microscopy in
    microfiltration processes
    M. Zator, M. Ferrando, F. Lopez, C. Gell
    Departament dEnginveria Quimica, ETSEQ, Universitat Rovira i Jirgili, 26 Avda. Pasos Catalans, 43007 Tarragona, Spain
    carme.guellurv.cat
    The main goal oI the study is centered in the use oI conIocal scanning laser microscopy (CSLM) to characterize membrane
    Iouling caused during microIiltration oI biological solutions. Protocols developed Ior oII-line and on-line characterization oI
    protein Iouling by CSLM are presented. These protocols describe in detail the preparation and analysis oI the membrane
    samples by CSLM (image acquisition), and the use oI image analysis soItware and 3D reconstruction soItware to obtain
    qualitative and quantitative inIormation Irom the image stacks gathered by CSLM. The results show that CSLM can be used
    to locate and visualize protein Iouling, and to obtain quantitative data on the presence oI the proteins inside the pores using a
    parameter specially deIined Ior this purpose (P
    s
    , Iraction oI pore surIace where the protein is detected). The developed
    protocols were applied to characterize membrane Iouling during Iiltration oI protein/dextran and protein/dextran/polyphenol
    solutions, and also to study the extend oI membrane cleaning (water permeate Ilux recovery) using a commercial enzymatic
    agent. The results Ior the binary solutions oI 0.5 g/L BSA/dextran show internal Iouling as the prevailing mechanism, mainly
    attributed to higher presence oI BSA throughout the membrane depth. For the ternary solutions oI BSA/dextran/tannic acid it
    was clearly seen that the presence oI tannic acid resulted in extensive external Iouling. Three-D reconstructions oI CSLM
    image stacks oI the cake showed more dextran close to the membrane surIace, independently oI the tannic acid concentration
    in the solution. Chemical cleaning oI Iouled membranes was also characterized using CSLM images, which show that no
    dextran and/or protein were leIt inside the membrane (up to the analyzed depths) aIter the cleaning cycle. A critical
    assessment oI CSLM limitations in membrane Iouling characterization shows that visualization oI the pores is possible just
    Ior microIiltration membranes, that the Iluorophore labeling may aIIect Iouling under certain experimental conditions and the
    main limitation Ior on-line visualization is related with the lack oI suitable, commercially available objectives.
    OE.4.2
    Microfluidic filtration
    I. Ngene
    1
    , R. Lammertink
    1
    , M. Wessling
    1
    , W. Van der Meer
    2
    1
    Membrane Process Technologv, MESA Institute of Nanotechnologv, Universitv of Twente, P.O. Box 217, 7500 AE
    Enschede, The Netherlands
    2
    Jitens Water Technologv, 8901 BE Leeuwarden, The Netherlands
    i.s.ngeneutwente.nl
    Fouling adversely aIIects the perIormance oI membrane Iiltration systems. Various non invasive methods have been
    employed in the study oI the mechanisms oI Iouling build up. This study investigates the Ilow oI liquids in, along and through
    the porous walls oI microIluidic chips using direct visual observation technique. It monitors the development oI Iouling in
    scaled down membrane Iiltration systems. MicroIiltration membranes with channel structures are prepared using phase
    separation micro molding (PSM). The channels are separated by a porous structure which mimics the Iiltration membrane
    (Fig 1). The Ilow pattern oI liquids along the walls oI the channel is traced using polystyrene latex particles oI size 3-10 m.
    Permeation oI the liquid is observed through the Ieed channel wall into the adjacent channel with a deposition oI the particles
    on the surIace oI the Ieed membrane wall. Particle deposition occurs on a surIace which is observed in cross section. It has
    been observed that initially, the particles preIerentially deposit closer to the exit oI the channel. However, due to increasing
    local resistance, the hydrodynamics changes leading to cake growth in the channel entrance. This gives us the ability to
    monitor visually the local Ilux and cake properties in combination with the global Ilux/pressure.
    -114-
    Figure 1 Chip showing channels, Ilow directions and active membrane
    OE.4.3
    Membrane biofouling effects of antiscalants used in reverse osmosis
    T. Z. Rezene, Y. Oren, M. Herzberg
    Ben Gurion Universitv of the Negev, Department for Desalination and Water Treatment, Zuckerberg Institute for Water
    Research, Midreshet Ben Gurion, 84990, ISRAEL
    herzbergbgu.ac.il
    Antiscalants aIIect bioIouling oI reverse osmosis (RO) membranes along with bioIilm Iormation stages that include cell
    deposition and attachment Iollowed by growth oI the sessile culture. Our Iirst working hypothesis is that antiscalants, which
    are mainly polyelectrolytes (either polyacrylates or polyphosphonates) can adsorb to the polyamide active layer and alter either
    the charge density or the hydrophobicity or both, on the RO membrane surIace. These changes may strongly aIIect bacterial
    deposition and attachment to the membrane. Our second working hypothesis is that antiscalants can serve as nutrients Ior
    microbial growth, especially in oligotrophic environments such as desalination systems Ior brackish water where the dissolved
    organic carbon and phosphorous concentrations can be limiting nutrients Ior bacterial growth. Antiscalants are added in
    concentrations oI Iew mg/l to the RO Ieed water. As a result, the dissolved organic carbon concentration and the available
    phosphorous Ior microbial growth may signiIicantly increase. Pseudomonas fluorescence F113 tagged with a green Iluorescent
    protein (GFP) was used as a model strain Ior delineating the eIIect oI antiscalants on bacterial deposition. Exposure oI high
    Ilux ESPA2 membrane (Hydranautics/Nitto-Denko, Oceanside, CA) coupons to polyacrylate based antiscalants, PC510, in
    brackish water (collected Irom K'tziot desalination plant Ieed water) caused a higher extent oI cells attached membrane
    surIace, with a corresponding deposition coeIIicient (deposition rate, cellsec
    -1
    , normalized to cell concentration and area) oI
    3.5310
    -9
    + 6.8410
    -10
    m/s compared to 1.3410
    -9
    + 4.8810
    -10
    m/s Ior the pristine membrane. In the presence oI
    polyposphonate, PC191 antiscalant, the diIIerence Irom the case oI a pristine membrane was smaller, with a corresponding
    deposition coeIIicient oI 1.87 10
    -9
    + 4.0110
    -10
    m/s. Using the same brackish water, both types oI antiscalants showed similar
    impact on the surIace hydrophibicity oI the membrane, namely, contact angle oI a DI water drop increased Irom 21.2 + 5.8
    o
    to
    49.5 + 1.3
    o
    and 48 + 4.9
    o
    in the cases oI PC191 and PC510, respectively. Moreover, membrane surIace zeta potential
    increased Irom -21.0 + 1.5 mV Ior the pristine membrane to -7.9 + -1.4 mV and 79.7 + 2.8 mV Ior membrane samples
    exposed to PC191 and P510, respectively. It should be mentioned that neither hydrophobicity nor the zeta potential oI the
    bacteria was changed due to exposure to both oI the antisaclants. In contrast to the eIIect oI PC510 increasing cell deposition
    on the membrane by altering surIace charge and hydrophobicity, PC191 is shown to enhance bioIilm oxidative growth and
    activity due to supplement oI available phosphorous Irom antiscalant backbone. A wise selection oI antiscalant Ior scaling
    control should take into account their contribution to membrane bioIouling propensity. DiIIerent stages oI microbial bioIilm
    Iormation on RO membranes are shown to be aIIected by antiscalants: while polyacrylates increase bacterial deposition and
    attachment by altering membrane physico-chemical properties, polyphosphonate increase bioIilm growth under phosphorous
    limiting conditions.
    -115-
    OE.4.4
    Influence of colloidal interactions on the microfiltration of milk: a surface energy
    approach
    W. Khnl
    1
    , A. Piry
    1
    , T. Grein
    2
    , S. Ripperger
    2
    , U. Kulozik
    1,3
    1
    Chair of Food Process Engineering and Dairv Technologv, Technische Universitt Mnchen, 85354 Freising-
    Weihenstephan, Germanv
    2
    Chair for Mechanical Engineering, Technische Universitt Kaiserslautern, 67663 Kaiserslautern, Germanv
    3
    ZIEL Research Center for Nutrition and Food Science, Technologv Section, Technische Universitt Mnchen, 85354
    Freising-Weihenstephan, Germanv
    WolIgang.Kuehnlwzw.tum.de
    Fouling is the major drawback in membrane (micro-)Iiltration oI milk and other protein containing solutions. It reduces the
    Ilux and alters the retention characteristics oI the Iiltration unit. Apart Irom the hydrodynamic conditions in the membrane
    channel colloidal substrate-membrane and protein-protein interaction inIluence the Iormation and the characteristics oI a
    deposit layer.
    Models exist explaining the deposition oI proteins on the membrane as a Iunction oI hydrodynamic Iorces. But the description
    oI the deposit layer structure (porosity, thickness) as a concurrence oI intermolecular interactions between the deposit layer
    Iorming proteins and the compression Iorce oI Iiltrate Ilow is oIten not possible. The lack oI understanding oI colloidal
    interactions between complex protein structures and the use oI oversimpliIied models lead oIten to results, which are
    inconsistent with experimental observations. Formally, electrostatic interactions and Van-der-Waals-Iorces (classical DLVO
    modelling) were used to explain the colloidal behaviour oI casein micelles, which are the major constituent oI deposit layers
    Iormed during membrane Iouling at the MF oI milk.
    In this paper it will be shown that due to the high ion strength oI milk serum the DLVO-Iorces can not be used as an
    explanation Ior milk deposit layer structure e.g. as a Iunction oI pH. A new interaction model Ior casein micelles based on the
    measurement oI surIace energies oI milk proteins is presented which integrates van-der-Waals and electrostatic Iorces as well
    as hydrophilic and hydrophobic interactions. With this model, the inIluence oI colloidal interactions on deposit layer build-up,
    structure, Ilux and whey protein permeation along ceramic MF membranes can be explained. The model is experimentally
    validated by a variation oI environmental conditions (pH). By measuring the length-dependent distribution oI Ilux and protein
    permeation, the inIluence oI the inhomogeneous Iiltration conditions along a membrane on deposit-layer characteristics could
    be assessed.
    The integration oI surIace energies oI proteins into an interaction model can be transIerred to other proteins besides casein to
    reveal valuable inIormation about colloidal interactions during Iiltrations oI protein solutions. This knowledge Iacilitates the
    optimal alignment oI process and membrane properties to the Iiltration task.
    OE.4.5
    Filtration test cells: if properly used, a helpful tool for assessing fouling propensity in
    MBR
    T. de la Torre
    1
    , B. Lesjean
    1
    , A. Drews, M. Kraume
    3
    1
    Berlin Centre of Competence for Water, Cicerostr. 24, 10709 Berlin, Germanv
    Universitv of Oxford, Dept. of Engineering Science, Parks Road Oxford OX1 3PJ, UK
    3
    Chair of Chem. Engineering, TU Berlin, Strae des 17. Juni 136, 10623 Berlin, Germanv
    teresa.delatorrekompetenz-wasser.de
    The use oI dead-end Iiltration parameters Irom the conventional activated sludge technology (CAS) like capillary suction time
    (CST), time to Iilter (TTF) or sludge volume index (SVI) are oIten extrapolated to the membrane bioreactor (MBR) technology
    as Iilterability assessment tools. This article evaluates critically the applicability oI these methods Ior that purpose and
    proposes the use oI properly done lab-scale Iiltration test cells as a more relevant alternative to quantiIy Iouling propensity oI
    the activated
    sludge. These systems allow having an external membrane Iilterability measurement which is independent both oI the
    membrane characteristics (material, pore size and age) and the hydrodynamics oI the investigated MBR system. This way, as
    the working conditions are Iixed, the results Irom the activated sludge Irom diIIerent MBR can be quantiIied and compared. A
    wide variety oI test cells and protocols have long since been in use, however, oIten with contradictory or unrepresentative
    -116-
    outcomes. Thus, the article will also provide recommendations Ior the use oI these tools like the use in situ (test cell submerged
    in the activated sludge tank) so that the tested mixed liquor conserves its properties.
    Figure 1. Scheme oI the in-situ BFM test cell
    Fig. 1 shows one example oI an in situ Iiltration test cell, the Berlin Filtration Method (BFM) |1|, which has successIully been
    used in Berlin Ior the investigation oI diIIerent MBR units. The article will discuss the advantages oI this Iiltration test cell
    method as well as other proposed Iilterability evaluation methods. From this review, it will be concluded that all these tools
    can give similar and valuable inIormation about short-term Iouling propensity oI activated sludge, and in some instance even
    on long-term Iouling propensity. With this inIormation, operating parameters like aeration rate or Ilux can virtually be
    controlled and optimized, resulting in lower energy and thereIore lower operating costs.
    |1| T. de la Torre, V. Iversen, A. Moreau, J. Stber, Filtration characterization Methods in MBR: a practical comparison.
    MCIW08 Proceedings, Toulouse, 20-22 October 2008
    OE.4.6
    Relationship between types of oscillating shear profiles and membrane fouling
    C.C.V. Chan, P.R. Berube, E.R. Hall
    Department of Civil Engineering, Universitv of British Columbia, 6250 Applied Science Lane, Jancouver, British Columbia,
    Canada
    chanccivil.ubc.ca
    Shear stresses have been recognized as an important parameter in controlling particle back-transport Irom membrane surIaces
    |1|. Hydrodynamic conditions inside submerged gas-sparged hollow Iiber membrane systems are characterized by non-
    repeating oscillating Ilows which generate highly variable and transient shear conditions at membrane surIaces |2|.
    Depending on the membrane conIiguration and the Iluid Ilow properties, diIIerent types oI oscillating shear proIiles are
    encountered during gas sparging inside a submerged hollow Iiber membrane module, as seen in Figures 1a and 1b |2|. To date,
    it is not known whether these diIIerent shear proIiles result in diIIerent Iouling control.
    The overall objective oI this study is to investigate whether diIIerent types oI oscillating shear proIiles aIIect Iouling control,
    and to identiIy the shear proIile that produces the greatest beneIicial eIIect on minimizing reversible surIace Iouling. Shear
    proIiles typically seen in gas-sparged submerged hollow Iiber modules were recreated. Filtration experiments were perIormed
    under these controlled shear conditions. As shown in Figure 2, it was Iound that the shear proIile with peak values oI
    relatively long duration (i.e. Figure 1a) were more eIIective at controlling surIace Iouling than the Irequent short shear proIile
    (i.e. Figure 1b), even though both shear proIiles were similar in magnitude. Knowledge oI Iouling under diIIerent shear
    conditions is essential to optimally design sparging approaches and membrane module conIigurations.

    -117-

    Figure 1a. Shear proIile with peak values oI relatively long duration. Figure 1b. Shear proIile with peak value oI short duration
    1. Cui, Z.F., S. Chang, and A.G. Fane, Journal of Membrane Science, 2003. 221(1-2): p. 1-35
    2. Chan, C.C.V., Berube, P.R., Hall, E.R., Journal of Membrane Science, 2007. 297(1-2): p. 104-120
    OE.4.7
    The influence of membrane characteristics on fouling in an MBR
    P. van der Marel
    1,2
    , A. Zwijnenburg
    2
    , A. Kemperman
    1
    , M. Wessling
    1
    , H. Temmink
    3
    , W. van der Meer
    1,2
    1
    Membrane Technologv Group, Institute of Mechanics, Processes and Control Twente (IMPACT), Facultv of Science and
    Technologv, Universitv of Twente, P.O. Box 217, NL-7500AE Enschede, The Netherlands
    2
    Wetsus, Centre for Sustainable Water Technologv, P.O Box 113, NL-8900 CC Leeuwarden, The Netherlands
    3
    Department of Environmental Technologv, Wageningen Universitv, P.O. Box 8129, NL-6700 EJ Wageningen, The
    Netherlands
    a.j.b.kempermantnw.utwente.nl
    Membrane Iouling hampers Iull-scale applications oI a membrane bioreactor (MBR) despite several advantages above
    conventional systems. Membrane Iouling is inIluenced by operational conditions, Ieed properties, and membrane properties.
    The main objective oI this study was to elucidate the inIluence oI various membrane characteristics on membrane Iouling in
    MBR.
    Five diIIerent Ilat sheet membrane materials varying in pore size (Fig. 1), surIace porosity, pore morphology, and
    hydrophobicity were investigated Ior Iouling using an improved Ilux-step method (IFSM) . This method not only reveals the
    total Iouling rate (F
    total
    ) and the critical Ilux (J
    C
    ), but also the irreversible Iouling rate (F
    irr
    ) and the critical Ilux Ior irreversibility
    (J
    Ci
    ). Two Ieed sources were used: activated sludge Irom a pilot MBR Ied with municipal wastewater, and activated sludge
    Irom a Iull-scale MBR (Varsseveld, the Netherlands). Long term experiments were perIormed to veriIy the results Irom the
    short term IFSM.
    Results showed a clear inIluence oI the membrane characteristics on membrane Iouling in an MBR. Fouling was more severe
    Ior the activated sludge Irom the MBR in Varsseveld revealing a clear inIluence oI the Ieed properties. For both activated
    -118-
    sludge mixtures however, a hydrophilic membrane with a complete anisotropic, interconnected pore morphology and a
    relatively large pore size oIIered the best membrane characteristics showing the largest J
    C
    and J
    Ci
    .
    Long term sustainable Iiltration was hampered by gel layer Iormation. A membrane with the largest J
    C
    and J
    Ci
    oIIered the
    longest sustainable time and much larger Iluxes could be applied in a sustainable way. Operating an MBR at increased Iluxes
    (~ 25 L.m
    -2
    .h
    -1
    ) will reduce the necessary membrane area. As a result air scouring the most energy consuming aspect oI
    submerged MBR can be reduced substantially by using a membrane with optimized characteristics.
    Figure 1: SurIace oI PVDF membrane with three pore sizes at equal magniIication
    |1|. Chang, I.S., et al., Membrane Iouling in membrane bioreactors Ior wastewater treatment, J. Environmental Eng., 2002, 128
    (11), 1018-1029
    |2|. Van der Marel, P., et al., An improved Ilux-step method to determine the critical Ilux and critical Ilux Ior irreversibility in
    a membrane bioreactor. J. Membrane Sci., 2009, accepted Ior publication
    OE.4.8
    Modeling the relation between the silt density index and the modified fouling index
    A. Alhadidi
    1
    , A. Kemperman
    1
    , J. Schippers
    2
    , M. Wessling
    1
    , W. Van der Meer
    1
    1
    Membrane Technologv Group, IMPACT, Facultv of Science and Technologv, Universitv of Twente, PO Box 217, 7500 AE
    Enschede, The Netherlands, Tel 31 53 489 2961 fax 31 53 489 4611
    2
    UNESCO-IHE Delft, Westvest7, P.O. Box 3015, 2601DA Delft, the Netherlands
    a.m.m.al-hadiditnw.utwente.nl
    Deposit oI solutes or colloidal on the membrane surIace or into its pores, causes membrane Iouling. This is the main reason oI
    permeate Ilux decline and loss oI product quality in reverse osmosis (RO) Systems. To predict Iouling behavior oI RO Ieed
    water, Iouling indexes are used. The Silt Density Index SDI and the ModiIied Fouling Index (MFI) are the most popular
    Iouling indexes. The ASTM produced a standard protocol Ior measuring the SDI s a standard method to determine the Iouling
    potential, which nowadays is a widely applied method. From a practical point oI view, the SDI oI RO Ieed water preIerably
    should be lower than 3. However, the SDI has several disadvantages making it an unreliable test . The MFI is based on the
    cake Iiltration model, and can be corrected Ior pressure and temperature. ThereIore, the MFI is introduced as a promising
    Iouling index. Nevertheless, the procedure oI measuring an MFI is more diIIicult and not directly suitable Ior carrying out in
    the Iield`. The objective oI this study thereIore is to determine a
    theoretical relationship between SDI and MFI, and to investigate the
    inIluence oI membrane and testing parameters on MFI and SDI. First
    result oI this model will be presented here.
    In order to calculate the SDI, the times t
    1
    and t
    2
    Ior collecting the Iirst
    and second samples were predicted using the measured MFI value and
    the MFI deIinition:
    J MFI
    A dP
    R
    J
    t
    m
    m
    +


    Where:
    R
    m
    membrane resistance
    water viscosity
    dP the applied pressure
    A
    m
    the membrane area
    V Iiltrated volume Figure1. SDI versus MFI Ior diIIerent R
    m
    -119-
    Figure 1 shows the relation between SDI and MFI Ior diIIerent membrane resistances. An important conclusion is that Ior the
    same Ieed water the SDI can vary depending on the resistance oI the membrane used in the test.
    OE.4.9
    Electrodialysis of model salt solutions containing whey proteins: mineral fouling
    investigations and enhancement by pulsed electric field and modified cell
    configuration
    C. Casademont
    1
    , E. Ayala-Bribiesca
    1
    , P. Sistat
    2
    , B. Ruiz
    2
    , G. Pourcelly
    2
    , L. Bazinet
    1
    1
    Institute of Nutraceuticals and Functional Foods (INAF) and Dairv Research Center (STELA), Department of Food Sciences
    and Nutrition, Pavillon Comtois, Universite Laval, Sainte-Fov (Qc), G1K 7P4, Canada
    2
    Institut Europeen des Membranes, Universite Montpellier 2, ENSCM, CNRS, CC047, 34095 Montpellier Cedex 5, France
    Laurent.BazinetIsaa.ulaval.ca
    Applied to milk eIIluent, electrodialysis (ED) process is limited by mineral and protein Ioulings oI ion-exchange membranes
    (IEM) |1|. It was recently established that magnesium directly inIluences the deposit oI CaCO
    3
    on IEM Ior calcium and
    carbonate high-concentration solutions |2|. It was also demonstrated that pH conditions inIluence the membrane Iouling
    (protein and mineral deposits in acidic and basic conditions, respectively) |3|. The present work was carried-out to complete
    investigations on mineral Iouling and to enhance ED process Ior complex solution containing Whey Protein Isolates and salts
    (CaCl
    2
    , MgCl
    2
    ). In order to determine iI diIIerent layers were Iormed and/or iI nuclei or germs oI growth oriented the mineral
    deposit, a model salt solution was Iirst treated by electrodialysis (3 consecutive repetitions). The membrane Iouling was
    analyzed aIter each ED by electron microscopy photographs, elemental and X-Ray diIIraction analyses. The results obtained
    Ior mineral Iouling investigations showed that amorphous Mg(OH)
    2
    progressively covers CaCO
    3
    , Ca(OH)
    2
    and Mg(OH)
    2
    (crystallized) and that CaCO
    3
    crystallization needs supersaturated concentration to occur. In a second part, the Ieasibility oI
    using pulsed electrical Iield and a new ED conIiguration was tested to prevent IEM Iouling. The results showed that a pulsed
    electric Iield coupled to a separated Ieed oI the concentrate compartments led to the best demineralization rate (79.5) without
    membrane Iouling and excessive energy consumption. This study also showed that the pulsed electrical Iield applied to
    conventional ED conIiguration decreased the mineral Iouling in basic conditions (16 Ior Ca and 24 Ior Mg) and the protein
    deposit in acidic condition (18).
    |1| L. Bazinet, D. Montpetit, D. Ippersiel, J. Amiot, F. Lamarche,

    IdentiIication oI skim milk electroacidiIication Iouling,
    Journal oI Colloid and InterIace Science
    ,
    237, 2001, 62-69
    |2| C. Casademont, G. Pourcelly, L. Bazinet, EIIect oI Magnesium/Calcium ratios in solutions subjected to electrodialysis:
    characterization oI cation-exchange membrane Iouling. Journal oI Colloid and InterIace Science, 315, 2007, 544-554
    |3| E. Ayala-Bribiesca, M. Araya-Farias, G. Pourcelly, L. Bazinet, EIIect oI concentrate solution pH and mineral composition
    oI a whey protein diluate solution on membrane Iouling during conventional electrodialysis, Journal oI Membrane Science,
    2006, 280, 790-801
    OE.4.10
    New water pretreatment combining clays and ultrafiltration membranes to limit cake
    fouling
    M. Pontie
    1,2
    , A. Thekkedath
    1
    , J.B. Castaing
    2
    , A. Masse
    2
    , P. Jaouen
    2
    1
    Laboratoire GEPEA UMR CNRS 6144, Angers Universitv, UFR Sciences, Group Analvsis and Processes (GA&P), 2 Bd.
    Lavoisier, 49045 Angers cedex 01, France
    2
    Laboratoire GEPEA UMR CNRS 6144, 37 bd de luniversite, CRTT BP 406, 44602 Saint-Na:aire, France
    maxime.pontieuniv-angers.Ir
    The present work proposes the use oI a modiIied bentonite material (denoted Mont-CTAB) to remove Irom seawater low
    molecular weight organic matter in order to develop a novel seawater pre-treatment beIore reverse osmosis (RO) in order to
    limit cake Iouling deseases.
    -120-
    Filtration oI humic acid solution with and without bentonite particules at a constant trans-membrane pressure oI 2 bar was
    conducted on 10 and 100 kDa UF regenerated cellulose membranes in order to study the pre-treatment eIIiciency oI bentonite
    presence. It was shown that in presence oI bentonite, the cake resistance have considerably reduced comparing to the value oI
    cake resistance inpresence oI HA alone. In the case oI HA solution, cake resistance was the dominant Iactor oI the total
    resistance, but with HA bentonite, cake resistance was Iound to be even lower than the membrane resistance, R
    m
    .
    Furthermore, a novel analytical approach based on the determination oI the Iractal dimension oI the cake with and without
    clays particles permit to conIirm the cake resistances results showing a more open cake layer in presence oI clays (1).
    This result opens interesting perspectives to the utilization oI UF coupled with bentonite to limit Iouling deseases in
    ultraIiltration operations. The application oI such Iundamental approach is the pre-treatment oI seawater beIore desalination by
    reverse osmosis.
    |1| A. Thekkedath, PhD thesis, Dec. 07, Angers university (see the Iollowing website to attained a Iree integral copy oI the
    thesis : http://www.inIo.univ-angers.Ir/pub/gh/Tools/gap/gap.htm)
    OE.5.1
    Pre-treatment for drinking water membrane processes
    A. Barrios Martinez, P. Moulin
    Universite Paul Ce:anne Aix Marseille, Laboratoire de Mecanique, Modelisation et Procedes Propres (M2P2 UMR-CNRS
    6181), Europole de lArbois, BP. 80, Batiment Laennec, Hall C, 13545 Aix en Provence Cedex 04, France
    abarriosmhotmail.com
    Currently, the drinking water production by a desalination process (thermal or by membrane Iiltration) constitutes 0.1 to 3
    oI Iresh water global needs according to the sources (Michelle en 2008, Singh 2008). In the process oI membrane Iiltration by
    Reverse Osmosis (RO), the pretreatment oI seawater by the coagulation-Ilocculation allows the achievement oI a major
    decrease oI turbidity, organic matter as well as SDI
    15
    (Silt density Index). The coagulation-Ilocculation pretreatment can be
    divided into two processes: Iirst oI all there is a reaction phase, which consists in destabilization oI colloids and the Iormation
    oI Ilocs; and then a separation phase occurs where the Ilocs are separated Irom the water. This phenomenon allows the
    maintain oI the membranes eIIiciency and increases their liIetime; it also keeps the reverse osmosis plant more eIIicient
    (Bonnelve 2004 , Mitrovli 2008 , Ma 2007). The results oI pretreatment testing are presented in this work. Various
    experiments oI pretreatment with natural water and seawater have been conducted by adding to it some coagulants such as:
    Al
    2
    (SO
    4
    ) and FeCl
    3
    coupled to organic polymer under various operating conditions (coagulant type, pH, concentration and
    salinity). InIluences oI the operating conditions and water quality on Iilterability given Ior the SDI were thus studied. The Iirst
    study was realized based on the variation oI coagulant concentration (Irom 0 to 50 mg.L
    -1
    ). Later, a second study was made to
    diIIerent pH units values (Irom 5 to 8). The table 1 shows the variation ranges oI seawater and natural water quality
    parameters. By adding Al
    2
    (SO
    4
    ) in natural water, the experiments showed that optimal perIormance was achieved at a
    concentration oI 40 mg.L
    -1
    and a pH 8. The results show a 99 decrease oI turbidity, a removal oI organic matter oI 70 and a
    reduction oI 3 SDI
    15
    units (Irom 6 to 3). On the other hand, concerning the seawater, the evaluation oI the same parameters
    does not show any major decreases: the turbidity increases a little, the or ganic matter value remains rather constant and the
    SDI
    15
    value decreases by only one unit (Irom 4 to 3). By adding FeCl
    3
    , the same results were obtained Ior natural water but a
    diIIerent optimal concentration at 20 mg.L
    -1
    and ph 7 to 8 was obtained. However a lower puriIication Ior seawater was
    obtained. In this case, we have obtained a removal oI turbidity (75), organic matter (50) and SDI
    15
    units (Irom 5 to 3).
    Finally, the addition oI an organic coagulant in seawater does not give any eIIect on turbidity and the organic matter; however
    a reduction oI one SDI
    15
    unit (Irom 3 to 2) is obtained.
    Table 1. Seawater and natural water quality`s
    Parameters Sea
    Mediterranean
    Cassis
    Natural water
    Marseille
    Temperature, C 15,5-22 13-18
    pH 7,5-8,35 8,27-8,4
    Turbidity, NTU 0,39-0,5 8-12
    SDI 3,2-6,3 5,2-6,37
    Conductivity, mS.cm
    -1
    20C 43,7-51,5 0,375-0,41
    UV254, m
    1
    0,008-0,101 0,043-0,05
    |1| V. Bonnelye et al., Desalination, Jolume 167, 15 August 2004.
    |2| W. Ma et al. Desalination, Jolume 203, Issues 1-3, 5 Februarv 2007.
    -121-
    |3| M. K. Wittholz et al. Desalination, Jolume 229, Issues 1-3, 15 September 2008.
    |4| S.T. Mitrouli et al. Desalination, Jolume 222, Issues 1-3, 1 March 2008.
    |5| R. Singh. Desalination, Jolume 227, Issues 1-3, 30 Julv 2008.
    OE.5.2
    Use of degradation products of milk and vegetal oil components for bio-cleaning of
    membrane
    D. Delaunay, M. Rabiller-Baudry, F. Piquet, L. Paugam
    Universite Rennes 1, UMR 6226 'Sciences Chimiques de Rennes`, CNRS equipe Chimie et Ingenierie des Procedes, CS
    74205, case 1011, 35042 Rennes cedex
    murielle.rabiller-baudryuniv-rennes1.Ir
    Membrane Iiltration processes are known to be clean, sober and saIe. Nevertheless the associated cleaning step oIten appears
    as a bottleneck Ior sustainable production. This step is water, energy and chemicals consumer; having a strong incidence on the
    produced eIIluents and Iurther treatments or possible reuse.
    Skim milk UF is widely used in dairy industries to standardize the milk protein content beIore cheese making. The high
    resulting Iouling reduces Iluxes, limits then the productivity and needs thus daily cleaning operations (2-3 h). The irreversible
    Iouling in this application was previously identiIied as protein deposit that is then the cleaning target. The commercial
    Iormulated detergent solutions usually used Ior this purpose are based on surIactants derived Irom the petroleum chemistry. In
    this study, a proposal Ior bio-cleaning is made, using degradation products oI milk components (proteins, butter, cream, skim
    milk and raw milk) and vegetal oil ((olive oil, 'savon de Marseille soap) as renewable resources.
    The physico-chemical analysis oI residual Iouling appears essential to avoid misleading eIIiciency interpretation obtained Irom
    Ilux recovery as we have shown that water Ilux increase can also evidenced surIactant adsorption on the membrane or on the
    protein Iouling. The quantiIication oI residual proteins was thereIore realised on the membrane by FTIR-ATR.
    The cleaning eIIiciency was studied at pH 11.5 with a polyethersulIone UF membrane (HFK 131 - Koch, 70 oI the market
    Ior this application) Iouled by skim milk. The results show that alkaline detergents Irom hydrolysis oI dairy products or oil
    increase up to 75 the amount oI removed proteins when a simple soda solution only rises 52 in same conditions oI pH
    (11.5) and temperature (50C).
    This study includes also results aIter three consecutive cycles oI skim milk UF and cleaning steps with on renewable
    surIactants and a commercial detergent (P3-Ultrasil 10 Irom Ecolab), both on a PES spiral membrane (6.5 m
    2
    ). Cleaning
    eIIiciency (based on Ilux) and Iollowing Ilux in skim milk appear similar.
    This builds up promising perspectives Ior these bio-cleaning products, both on an environmental and economical point oI
    view.
    OE.5.3
    Action of oxidizing disinfectants on a partially-cleaned PES ultrafiltration membrane
    fouled with milk proteins
    L. Paugam, D. Delaunay, M. Rabiller-Baudry
    Universite Rennes 1, UMR 6226 'Sciences Chimiques de Rennes`, CNRS equipe Chimie et Ingenierie des Procedes, CS
    74205, case 1011, 35042 Rennes cedex
    lydie.paugamuniv-rennes1.Ir
    The cleaning oI membranes is a key step, particularly in Iood industry. It aims at eliminating the Iouling originated by the
    product Iiltration to restore membrane perIormances and to prevent microbial development. The cleaning is perIormed semi-
    empirically by Iluxes measurements. FTIR-ATR analyse oI both Iouled and cleaned membranes has shown, in previous
    results, that some usually-used cleaning products (surIactants, nitric acid) sometimes can lead to a misleading increase oI
    Iluxes. This gives the illusion oI a well-done cleaning whereas a deposit remains on the membrane. The cleansers adsorption
    don`t increase Iurther product Iluxes. On the contrary, it Iacilitates an irretrievable Iouling on the membrane. Moreover it can
    have consequences on the action and the eIIiciency oI the disinIecting step. In this work, we study the impact oI the
    -122-
    disinIectant choice on a PES membrane (HFK 131, Koch) Iouled with skim milk and only partially cleaned. In this application,
    the residual Iouling is identiIied as only due to proteins.
    We Iirst study a hypochlorite solution (Irom bleach, 200 ppm, pH 11.5) that is commonly used as disinIectant aIter the
    cleaning Ior this application. We estimate the part that plays this product to achieve the cleaning when it is used alone, aIter a
    partial cleaning with soda (pH 11.5) or aIter a standard industrial cleaning with P3-Ultrasil 10 (Ecolab, pH 11.5). The active
    chloride consumption reveals a residual Iouling or cleaning products adsorbed on the membrane beIore the disinIection
    properly. This is a good cleanser: in right conditions it allows a total protein removal as industrial cleansers. Nevertheless, iI
    the disinIecting product quantity is not suIIicient to achieve the cleaning, it leads to particularly reduced Iollowing milk Ilux
    (up to -13) compared with the same partially-cleaned membrane without any active Cl
    2
    contact. The active Cl
    2
    consumption
    has to be well controlled to ensure the eIIiciency oI the disinIection and products Iluxes. Various other oxidative solutions are
    then studied on a Iouled membrane: sodium perborate (pH 10.0), Oxonia (Ecolab, hydrogen peroxide, 10 , pH 4.7), Oxonia
    active (Ecolab, hydrogen peroxide peracetic acid, 1 , pH 3.2) and PVP-iodine (pH 4.6). Oxonia lead to a strong decrease oI
    water Iluxes (Irom-34 up to -47 ) whereas the sodium perborate, also based on hydrogen peroxide, allows 40 oI protein
    removal. The PVP-iodine, a halogen oxidising reagent like the hypochlorite, doesn`t show any protein removal. More than the
    product type, the results diIIerence appears to provide Irom the working pH range. At acidic pH, the amine groups would be
    preIerentially oxidise whereas at basic pH the reaction would concern SH groups oI cysteine. These results show the impact on
    a protein Iouling oI an oxidising solution used a priori as a disinIectant. Depending oI the state (nature, quantity) oI the
    residual Iouling aIter cleaning, on the nature oI the oxidising agent and on its conditions oI use (particularly the pH), the
    disinIectant can strongly aIIect or enhance the product Ilux. Moreover, impact on membrane ageing will also be shown. As a
    conclusion, cleaning and disinIecting steps can not be studied distinctly.
    OE.5.4
    Industrializing continuous high frequency back pulsing to maintain/enhance a high
    flux in a spiral wrap membrane element
    R. D. Sanderson, A. Elarbi
    UNESCO Associated Center for Macromolecules and Materials, Department of Chemistrv and Polvmer Science, Universitv of
    Stellenbosch, Matieland 7602, South Africa
    rdssun.ac.za
    Polymer membranes provide a good solution Ior obtaining potable water, but as membranes always Ioul during the water
    puriIication, the Ilux drops with time. Physical cleaning methods, which do not require the plant to be shut down Ior lengthy
    periods (iI at all), are very attractive Ior this purpose and also they do not generate any waste Iluids. In this paper rapid,
    continuous back pulsing into the permeate space is Iound to be very eIIective in enhancing the Ilux Irom and the cleaning oI a
    spiral wrap element.
    A standard plant with an Alpha Laval GR40PP 100000 MWCO spiral wrap element was used. In all experiments, the Iouling
    solution was 500gm/1000lt oI Dextrin in Reverse Osmosis water. Unless otherwise indicated the Ieed pressure was 100 kPa
    and the Ilow rate 1000 lt/hr.
    The back pulses which were obtained using a Iast acting solenoid valve connected to a pressure reservoir, containing permeate
    water at pressures between 100 and 150 kPa, were applied directly to the permeate output port. The system was operated using
    a LABview program. A square wave which was used with a width oI between 0.1 and 0.5 seconds and a cycle period oI
    between 1 and 15 seconds was generated by the computer and connected to a control terminal oI a solid state relay. The actual
    current that went through the relay and operated the solenoid came Irom two 12 volt batteries.
    The procedure Ior all experiments, as can be seen in the Ilux time plots to be presented, was as Iollows. First the membrane
    was conditioned with RO water Ior 30 minutes and the clean water Ilux measured. The back pulsing was then started and the
    diIIerence in the Ilux due to water Ilowing in the reverse direction noted over the next 30 minutes. AIter this the Iouling
    solution was introduced Ior a period oI 240 minutes and the change in Ilux was recorded. At this point the Ieed was changed
    back to RO water with the pulsing still on (back pulse cleaning). AIter another 30 minutes the pulsing was switched oII to see
    iI there was any change due to washing the membrane over a 30 minute period.
    The Iirst sets oI experiments were to optimize the pulse shape Ior using the dextrin solution. To do this data was taken Ior a
    series oI Iixed pulse widths (0.1 to 0.5 secs) and variable pulse periods (1 to 15 secs). From this data the two options oI Iirstly
    the optimum pulse shape (0.1 sec width) and the pulse period ( 3 sec period) were chosen Ior Iurther experiments. The
    procedure was repeated with peak pulse pressures oI 100,125 and 150 kPa, with a Ilow rate oI 1000lt/hr and the best results
    were with a peak pressure oI 150 kPa. .The last set oI experiments was again with the optimum pulse shapes but with Ilow
    rates oI 500, 1000,and 1500lt/hr at peak pressure oI 150 kPa. The best results here were Ior a Ilow rate oI 1500lt/hr.
    The clean water Ilux was close to 260 lt/hr.m
    3
    and a Iouled membrane gave a Ilux oI 25 to 28 lt/hr.m
    3
    . The best sustainable
    (aIter 240 mins) Ilux was 105 lt/hr.m
    3
    but some combinations gave as low as 60 lt/hr.m
    3
    .
    Similar results were obtained using Kaolin clay, which is a more inert Ioulant.
    -123-
    OF.1.1
    Determination of water concentration profile through Nafion

    membrane under fuel


    cell operation by small angle neutron scattering (SANS)
    A. Morin
    1
    , F. Xu
    2
    , G. Gebel
    3
    , O. Diat
    4
    1
    CEA, Liten, LCPEM, 17 rue des Martvrs, F-38054 Grenoble Cedex 9, France
    2
    UMR LEMTA 7563, F-54504 Jandoeuvre-les-Nancv cedex, France
    3
    CEA-SPrAM/PCI, CEA-Grenoble, 17 rue des Martvrs, F-38054 Grenoble Cedex 9, France
    4
    UMR ICSM CEA-Marcoule, BP 17171, F-30207 Bagnols sur Ce:e Cedex, France
    arnaud.morincea.Ir
    Proton Exchange Membrane Fuel Cell (PEMFC) is a competitive and potentially cleaner alternative to thermal combustion
    engine as an energy conversion device. Although PEMFC technology has been signiIicantly improved over the past decade,
    the requirements in term oI perIormance, stability, reliability and cost Ior mass commercialisation are yet to be achieved. The
    water management, which is a balance between Ilooding oI electrodes and membrane hydration, is a key point that has to be
    understood and improved to reach these targets.
    In PEMFC, the water transport is governed by three driving Iorces: the electro-osmotic drag Irom the anode to the cathode, that
    is to say water molecules carried with the Ilow oI proton, and the diIIusion and convection caused by the water concentration
    gradient between the two electrodes.
    There are diIIerent techniques to measure the transport number oI water in the membrane such as open-circuit potential,
    weighting and direct methanol Iuel cell analysis, but none allows to determine the transverse water proIile inside the
    membrane.
    In this work, we report a measurement method which allows to measure the transverse water concentration proIile within a
    perIluorosulIonated membrane, that is to say through its thickness, in a running Iuel cell by Small-Angle Neutron Scattering
    (SANS) (Figure 1). Our method allows to study this proIile at the middle, the inlet and the outlet oI a single cell test Iixture
    whatever test conditions (Figure 2). This technique is used to Iollow its evolution aIter a change oI the working parameters.
    Results show that water distribution inside the membrane is heterogeneous and depends on the design oI the Iuel cell`s gas
    Ilow channels. It is now possible to measure and to Iollow directly the eIIects oI electro-osmosis and back-diIIusion on water
    concentration proIile Ior diIIerent membrane thicknesses.

    0%
    5%
    10%
    15%
    20%
    25%
    30%
    35%
    40%
    0 0,2 0,4 0,6 0,8 1
    Fraction paisseur N117
    T
    e
    n
    e
    u
    r

    e
    n

    e
    a
    u

    (
    v
    o
    I
    %
    )

    Sortie
    MiIieu
    Entre
    80C, 3 bars
    H
    2
    /O
    2
    -0/100%HR-St. 5/5
    400 mA/cm
    OutIet
    MiddIe
    InIet
    Membrane thickness fraction
    W
    a
    t
    e
    r

    c
    o
    n
    t
    e
    n
    t

    (
    v
    o
    I
    %
    )
    Figure 1: SANS spectra recorded during Iuel cell operation Figure 2: Water proIile through NaIion membrane thickness
    determined Irom the SANS spectra
    -124-
    OF.1.2
    PFSA membrane degradation analysis through mechanical tensile tests
    S. Escribano
    1
    , A. Morin
    1
    , L. Rouillon
    1
    , G. Gebel
    2
    1
    CEA, Liten, LCPEM, 17 rue des Martvrs, F-38054 Grenoble Cedex 9, France
    2
    INAC-SPrAM, UMR 5819 CNRS/CEA/UJF, CEA-Grenoble, 17 rue des Martvrs, F-38054 Grenoble Cedex 9, France
    sylvie.escribanocea.Ir
    Increasing Proton Exchange Membrane Fuel Cells (PEMFC) systems durability has become a point oI major concern Ior the
    end users. Understanding Membrane Electrode Assembly (MEA) components degradation is the Iirst step towards this long
    liIetime objective.
    Considering that the rupture oI the thin electrolyte membrane is the ultimate step beIore Iuel cell system Iailure, we have
    Iocused our degradation studies on the mechanical strength oI this component.
    MEA with diIIerent PFSA membranes have been aged Iollowing diIIerent protocols, including in-situ ageing tests, applied in
    representative conditions (60C to 80C, relative humidity oI 0 to 100, stationary operation or on/oII cycles) and in-situ
    hydrothermal cycles, deIined so as to simulate the dry/wet cycles caused by the operation. For the Iuel cell tests, the MEA
    perIormance and electrochemical properties have been measured in-situ beIore and aIter ageing to be related to the evolution
    oI the components, particularly oI the membrane.
    Particular mechanical tensile tests have been developed in order to allow local membrane samples analysis. The idea was
    indeed to study the eIIect oI the general ageing conditions applied, but also to enable evaluating the eIIect oI the local
    hydration conditions caused by the Iuel cell operation (typically the diIIerence between the drier cell inlet and the more
    hydrated or even Ilooded cell outlet). Electrochemical results show an important accelerating eIIect oI the temperature
    increase, particularly when the ageing mode includes oII steps, with as major cause Ior perIormance degradation a strong
    increase oI reactant gases cross-over through the membranes.
    MEA with diIIerent NaIion

    membranes (extruded N112, recast NRE212 and NRE211) have shown diIIerent ageing
    behaviours consistent with diIIerent mechanical behaviours.
    Tensile tests have been conIirmed as relevant diagnoses oI membranes
    degradation showing the impact oI the membranes structure and thickness and
    oI the local conditions; enabling the detection oI the membrane degradation
    previous to perIormance degradation; allowing to evaluate a degradation rate
    (CI. Figure) and accelerating parameters, related to the membrane structure or
    to the hydrothermal conditions.
    Mechanical stress-strain behaviour is modiIied during ageing with diIIerent
    phenomena observed: early Iailure can occur at cell inlet caused by a
    mechanical mechanism related to drying; ageing leads to a plasticizing eIIect
    Ior extruded membranes whereas recast membranes show a strong reduction oI
    the stress and strain at break (CI. Figure), leading Ior these membranes to an
    increased degradation, accelerated at higher temperature and at lower relative
    humidity.
    OF.1.3
    Improvements of the long-term stability of proton and anion conducting membranes
    for fuel cell applications
    M. Gross, R. Grtner, H.-G. Herz, G. Maier
    Polvmaterials AG, Innovapark 20, D-87600 Kaufbeuren, Germanv
    m.grosspolymaterials.de
    Polymaterials, a provider oI R&D services in the Iield oI plastic materials, currently develops alternative ion-conducting
    membranes which are aimed to improve both conductivity and long-term stability. For our client General Motors Corp. a
    cheap, mechanically and chemically durable proton conducting membrane which ensures high conductivity at low levels oI
    humidity is oI uttermost importance Ior their automobile application. In contrast, our second project deals with the
    development oI an anion conducting membrane Ior direct methanol Iuel cells on behalI oI BASF. The challenge here is to
    signiIicantly improve the chemical stability oI the ionomer in the alkaline environment. In this paper, the objective, the
    procedure, and the results oI both projects will be presented.
    -125-
    0%
    20%
    40%
    60%
    80%
    100%
    120%
    90 200 800 1800
    t (h)
    %

    o
    f

    i
    n
    i
    t
    i
    a
    I

    (
    n
    o
    n

    a
    g
    e
    d
    )

    s
    t
    r
    a
    i
    n
    Averaged decrease of the
    strain at break of a NRE212
    membrane after On/Off CycIes
    at 80C & 0/100%RH
    In one project novel hydrocarbon based proton conducting membranes have been developed. Block copolymers have been
    utilized in order to tune proton conductivity, swelling behavior, and durability by adjusting the nanoscale morphology oI the
    membranes. For example, the proton conductivity shows a signiIicant dependence on the morphology. Despite having the
    same IEC, the lowest conductivity oI 0.7 mS/cm at 80 C and 50 RH was measured Ior a spherical morphology. The best
    conductivity oI 4.6 mS/cm was measured Ior the membrane having a lamellar nanostructure and a short-range order. This is
    signiIicantly higher than the 3.2 mS/cm oI the membrane with the long-range order lamellae. Furthermore, an impact oI the
    nanostructure on the endurance oI the membrane when exposed to cyclic changing humidity conditions at elevated temperature
    can be observed. Under these conditions the most robust membrane is the one with the short range ordered morphology |1|.
    Fuel cells based on hydroxyl conducting membranes, which were the subject oI the other project, instead oI proton conducting
    membranes have the potential to operate with platinum-Iree catalysts due to the more Iavorable reaction kinetics at the
    electrodes. This provides an immense cost advantage over conventional Iuel cells with proton conducting membranes.
    However, the chemical stability oI simple cationic polyelectrolytes under operating conditions (very high pH, temperatures up
    to 60 C or more) is not suIIicient. Typically, degradation leads to Iailure within a Iew 100 h. We have developed a hydroxyl
    containing membrane based on a cationic polyelectrolyte with optimized structure oI the cations and improved stability.
    Polymaterials` material does not show degradation up to 5000 h (conditions: 60 C, 1 mol/L OH
    -
    , H
    2
    O/CH
    3
    OH 80/20). Its
    hydroxyl conductivity is 28 mS/cm at an IEC oI 1 meq/g and 50 mS/cm at an IEC oI 2 meq/g. Water uptake is less than 200
    at 80 C.
    |1| M. Gross, G. Maier, T. Fuller, S MacKinnon, C. Gittleman, in Handbook oI Fuel Cell, Vol. 5, W. Vielstich, H. A.
    Gasteiger, and H. Yokokawa (Editors), Wiley-VCH, (2009).
    OF.1.4
    Influence of modified mixed membranes on the direct ethanol fuel cell performance
    K.S. RoeloIs
    1,2
    , C. Cremers
    3
    , F. Jung
    3
    , T. Hirth
    1,2
    , T. Schiestel
    1
    1
    Fraunhofer Institute for Interfacial Engineering and Biotechnologv, Nobelstr. 12, 70569, Stuttgart, Germanv
    2
    Universitv of Stuttgart, Institute for Interfacial Engineering, Nobelstr. 12, 70569, Stuttgart, Germanv
    3
    Fraunhofer Institute for Chemical Technologv, Joseph von Fraunhoferstr. 7, 76327, Pfin:tal, Germanv
    Kimball.RoeloIsigb.IraunhoIer.de
    The direct alcohol Iuel cell (DAFC) as a portable energy source is a promising and Iast growing technology in the development
    oI eIIicient energy sources. Nowadays the Iocus lies on methanol whereas ethanol has some evident advantages like
    environmental compatibility, lower toxicity and the existing inIrastructure Ior distribution. Moreover ethanol contains a high
    energy density and it is a generally known and accepted substance. The objective oI this study is to prepare, characterise and
    compare a) inorganic/organic composites and b) modiIied inorganic/organic composites Ior possible usage as a membrane in
    he direct ethanol Iuel cell (DEFC).
    In this work, we propose the Iormation oI an interconnected inorganic
    network in a non-Iluorinated polymeric network. The polymeric matrix
    is sulIonated poly(ether ether ketone) (sPEEK) which is studied in . The
    inorganic phase consists oI hydrophilic Iumed silica particles (Aerosil

    380, Evonik Degussa) which are connected by partially condensed
    tetraethoxysilane (TEOS). In addition the inorganic phase is modiIied
    with Iunctional silanes carrying basic groups to induce stability and
    proton conductivity. The characterization methods are described in .
    Silica in the nanocomposites exhibited a barrier Iunction which is
    quantiIied by means oI reduced ethanol permeability. The proton Ilow,
    expressed in proton diIIusion coeIIicient, was relatively similar Ior
    membranes with inorganic content varying between 10 40.
    ModiIication oI the inorganic network with silanes bearing basic groups
    resulted in stable membranes with low swelling behavior and low
    ethanol permeation (Iigure 1) in ethanol-water systems. Highest increase
    obtained Ior the selectivity oI proton diIIusion coeIIicient to ethanol
    permeability coeIIicient was Iactor seven Ior modiIied composite
    membranes in comparison with polymeric matrix. Direct ethanol Iuel
    cell tests are carried out and Iirst results show an improvement on
    perIormance at room temperature in comparison to commercial
    perIluorinated membranes
    Figure 1: Ethanol permeability coeIIicients
    determined with pervaporation (C
    ethanol
    ,
    Ieed
    2 M;
    T
    Ieed
    40 C; p
    permeate
    15 mbar)
    -126-
    OF.1.5
    Plasma processes for the manufacture of original anion conducting membranes for
    solid alkaline membrane fuel cells
    S. Roualdes, J. Frugier, J. Durand
    Institut Europeen des Membranes (IEM), ENSCM, UM2, CNRS , Universite Montpellier 2, CC047, Place Eugene Bataillon,
    34095 Montpellier cedex 5, France
    stephanie.roualdesiemm.univ-montp2.Ir
    In the Iield oI low temperature Iuel cells, Solid Alkaline Membrane Fuel Cells (SAMFCs), which oIIer the opportunity to use
    liquid Iuels and non-precious metal catalysts, appear as a very promising new Iuel cell technology. Membranes suitable Ior
    SAMFCs are commonly made up oI ionomer-type polymers Iunctionalized with quaternary ammonium groups (-NR
    3

    , with R
    being an alkyl group or H). The commercial Morgan ADP

    by Solvay, initially developed Ior other applications, seems to be


    quite promising Ior SAMFCs but suIIers Irom some limitations (especially low retention to Iuel and water); other currently
    developed membranes Ior SAMFCs have not proved their competitiveness yet. So the need oI innovating membranes in this
    Iield is great.
    Our study deals with the implementation oI plasma processes Ior the modiIication oI the commercial Morgan ADP

    membrane
    or the synthesis oI integral plasma membranes. As a Iirst approach, plasma treatment using argon as gaseous phase has been
    perIormed in order to etch the surIace and change the cross-linking degree oI the Morgan ADP

    membrane. As a second
    approach, a thin Iilm has been deposited onto the Morgan ADP

    membrane by plasma polymerization. Plasma polymerization


    is a powerIul method Ior depositing thin and uniIorm polymer Iilms whose micro-structural properties can be tailored by
    modiIying the main deposition parameters. The main advantages oI plasma-polymerized Iilms are their highly cross-linked
    chemical structure, which gives them strong chemical and thermal stabilities and low permeability to gases and vapours, and
    their very low thickness (a Iew microns), which enables them to perIectly Iit to the surIace oI their support. Starting Irom a
    monomer containing tertiary amine groups (triallylamine), the membrane synthesis has consisted oI two steps. In the Iirst step,
    the monomer vapour has been plasma-polymerized on the Iorm oI a polyethylene-type plasma Iilm partially composed oI
    primary, secondary and tertiary amine Iunctions; in the second step, the methylation oI the amine Iunctions into quaternary
    ammonium groups has been perIormed by immersion oI the plasma Iilm into a methyliodide solution. Both approaches have
    enable to enhance the retention to Iuel oI the Morgan ADP

    membrane without making decrease its hydroxyl conductivity.


    The deposition oI an anion conducting plasma-polymerized Iilm can also be realized on Iuel cell electrodes instead oI a
    membrane. In this case, the plasma Iilm constitutes an integral membrane which has the big advantages to be very thin (well
    suitable Ior micro Iuel cells) and highly adherent to the electrodes. Although much less intrinsically conductive than
    conventional membranes, integral plasma membranes have similar speciIic ionic resistance thanks to their very small
    thickness. Their stability and retention to Iuel are much better than conventional polymers.
    Water transport characterization and Iuel cell tests on these original promising membranes are in progress.
    French National Research Agency and CNRS are acknowledged Ior granting the study.
    OF.1.6
    TECTONIC project: route to PCFC technology
    M. Marrony
    1
    , P. Baranek
    1
    , O. Joubert, E. Quarez, J.C. Grenier
    3
    , F. Mauvy
    3
    , P. Berger
    4
    , L. Dessemond
    5
    , N.
    Grunhaum
    5
    , G. Taillades
    6
    , M. Taillades-Jacquin
    6
    , A. Thorel
    7
    , R. Costa
    7
    1
    EIfER Institute- Electricite de France, Emmv-Noether Str. 11, D-76131 Karlsruhe (Germanv)
    2
    IMN Universitv of Nantes, 2 rue de la Houssiniere, BP 32229, 44322 Nantes cedex02 (France)
    3
    ICMCB Universitv of Bordeaux, 87 Av. Dr. Schweit:er, 33608 Pessac Cedex (France)
    4
    Pierre Se Laboratorv CEA Saclav, 91191 Gif sur Yvette cedex (France)
    5
    LEPMI-INPG, 1130 rue de la piscine, 38402 St Martin dHeres cedex (France)
    6
    ICG-AIME, Universitv of Montpellier II, Place Eugene Bataillon, 34095 Montpellier (France)
    7
    ENSMP-ARMINES, 60 Bd. St Michel, 75272 Paris cedex 06 (France)
    mmarronyeiIer.org
    TECTONIC project (2005-2008) objectives were to develop and demonstrate the Ieasibility oI a complete cell using proton
    conducting ceramic material (denoted PCFC). It was Iinancially supported by French Government under the French National
    Research Agency (ANR) Program Irom 2005. This concept oI PCFC cell operates at temperatures 400-650C. At this level,
    -127-
    non precious metal catalyst and oxide-type catalyst supports as electrode materials can be used. Besides, the problem oI
    thermal ageing oI SOFC components would be avoided to some extent. In order to lead this study, a strict collaboration
    between French academic and industrial partners has beenmade. The work consisted on:
    - The development oI advanced proton conducting electrolyte materials and highly perIormant electrodes with optimized
    synthesis and working processes oI materials.
    - The physico-chemical and electrochemical characterizations oI materials between 400 and 600C oI operating temperature
    range. Especially, the CO
    2
    tolerance and sintering properties oI cell were studied.
    - The integration oI such materials into a complete PCFC cell manuIacturing.
    Thus, button advanced PCFC cells based on perovskite rare earth doped barium cerate have been made under speciIic
    operating conditions. Preliminary cell perIormances Irom 50 mW/cm to 135 mW/cm have been validated between 550 to
    650C oI operating temperature during Iew hundred hours in static mode (see Iigure).
    Figure: Polarization curves and power density oI TECTONIC PCFC cell 550, 600 and 650C, respectively
    |1|
    |1| G. Taillades, J. Dailly, M. Taillades-Jacquin, F. Mauvy, A. Essouhmi, M. Marrony, C. Lalanne, D.J. Jones, J.C. Grenier, J.
    Roziere. To be submitted 'Electrochemical performances of anode supported single cell with a proton conducting electrolvte
    and Pr
    2
    NiO
    4
    as cathode material`
    OF.1.7
    PCFCs: materials, single cells and stacks
    M.L. Fontaine, Y. Larring, S. Mei, R. Bredesen
    SINTEF Materials and Chemistrv, Post box 124 Blindern, NO-0314 Oslo, Norwav
    Marie-Laure.FontainesinteI.no
    For breakthrough development in high temperature proton conducting solid oxide Iuel cells (PCFC), novel cell architectures
    integrating better perIorming materials must be produced by means oI cost-eIIective manuIacturing processes with potential
    Ior mass production. The present contribution addresses these issues on the basis oI the recent discovery oI acceptor doped
    orthoniobate LnNbO
    4
    proton conductors and the development oI a versatile manuIacturing process enabling the Iabrication oI
    Ilat single cells with 5 cm x 5 cm dimension (Figure 1a,d). La
    0.995
    Sr
    0.005
    NbO
    4
    (LSNb)/Ni graded anodes are produced by water-
    based tape-casting and their porosity is tuned by addition oI a pyrolyzable pore Iormer. LSNb electrolytes are spin-coated
    using colloidal ceramic suspensions and sintered at 1300 C. Monitoring the ceramic solid loading in suspension yields an
    electrolyte thickness ranging Irom 4 m to 26 m aIter sintering. Screen-printed cathode architectures are engineered to match
    thermal expansion and avoid chemical reaction at the cathode/electrolyte interIace while promoting Iast electrode kinetics.
    Several mixed oxide ion and electron conducting oxides are investigated Ior this purpose, including perovskite related
    materials such as CaTi
    0.9
    Fe
    0.1
    O
    3
    , La
    2
    NiO
    4
    and La
    4
    Ni
    3
    O
    10
    .
    -128-
    Figure 1: Flat sintered single cell (a) with thin LSNb
    electrolyte and compatible seal (d); interconnect
    materials Ior square and button cells (b and c).
    The development oI PCFC stacks is pursued through the design oI advanced modules along with the investigation oI
    compatible interconnect and seal materials. The Iormer are inexpensive alloys coated with a protective layer oI (Mn,Co)
    3
    O
    4
    spinel oxides at the alloy/electrode interIaces securing low resistance and long liIe time (Figure 1 b,c). The latter are glass
    ceramic materials whose compositions are tuned to match the thermal expansion oI the Iuel cell materials (Figure 1d).
    All Iunctional materials and complete cells are thoroughly characterized at all length scales with respect to their structure,
    composition, microstructure and speciIic properties. Results oI this work will be reported in this presentation.
    OF.1.8
    Water and proton incorporation under pressure and temperature into zirconate
    perovskites for hydrogen production: ionic conductivity and host framework
    behaviour
    O. Lacroix
    1
    , A.K. Sirat
    1
    , B. Sala
    1
    , A. Slodczyk
    2
    , Ph. Colomban
    2
    , S. Willemin
    1
    , A. Van der Lee
    3
    ,
    K. Rhamouni
    4
    , H.Takenouti
    4
    , B. Bendjeriou
    5
    1
    AREJA detached at IEM, Place Eugene Bataillon, 34095 Montpellier, France
    2
    LADIR UMR 7075 CNRS & Universite P. et M. Curie, 2 rue Henrv Dunant, 94320 Thiais, France
    3
    IEM, UMR 5635 CNRS, Place Eugene Bataillon, 34095 Montpellier, France
    4
    LISE, UPR15, CNRS, Universite P. et M. Curie ,4 Place Jussieu, 75252 Paris Cedex 05, France
    5
    ENSM-SE , 158 Cours Fauriel 42023 St Etienne, France
    olivier.lacroixiemm.univ-montp2.Ir
    Thanks to their relative low Iunctioning temperature, protonic conductors are the most promising electrolytes Ior Iuel cell and
    electrolyser applications. In contrast to oxide-ion conductors, H

    systems could operate below 650C, the critical temperature


    Ior resistance oI commercial alloys, especially, in an electrolyser plant.
    In perovskites with a Iormula ABO
    3
    , the presence oI protonic charge carrier is not intrinsic. ModiIication oI the Perovskite host
    Iramework is required to get the appropriate protons conduction.
    Steam incorporation and water removal is studied by Raman spectroscopy, impedance spectroscopy, thermal expansion and
    thermogravimetric measurements and compared to previous neutrons measurements. Water incorporation into perovskite
    Iramework is managed by the vacancy content |1|, crystallographic structure, densiIication rate, hydration pressure and
    temperature using. The eIIect oI pressure and hydration temperature on proton conductivity |2| and Iramework behaviour is
    discussed. Towards neutron diIIraction results, the eIIect oI change oI symmetry observed between 450 and 650C Ior
    zirconates and titanates structure |3| is evaluated on water uptake and correlated with the impedance spectroscopy
    measurements where transitions in conductivity behaviour could be observed.
    Steam and proton incorporation is also studied on dynamic mode during hydrogen production with perovskite electrolyte
    membrane and noble metal electrodes. The inIluences oI steam pressure vs. applied current is evaluated and discussed in order
    to prevent a dehydration oI electrolyte as already observed by Kobayashi |4|.
    On mechanical point oI view, the behaviour oI perovskite skeleton towards symmetry change with temperature and steam
    incorporation is also seen by dilatometric studies. The reversibility oI the two phenomena, very important in point oI view oI
    application, will be evaluated (cycling needed Ior plant maintenance).
    Thanks to G. Andre Irom LLB Ior is collaboration in neutron diIIraction and SCT (Societe des Ceramiques Techniques de
    Tarbes) Ior perovskite brasing and electrical contacts in the electrolyser cell.
    |1| O. Lacroix, B. Sala, K. Rahmouni, H. Takenouti, M. Keddam, C. Deslouis, S. Willemin, G. Pourcelly, J.P. Py, S. De
    Perthuis, electrochemistry and solid state letters, submitted
    -129-
    |2| B. Sala, O. Lacroix, S. Willemin, K. Rahmouni, H. Takenouti, A. Van Der Lee, P. Colomban, P. Goeuriot, B.
    Benjeriou,Patent WO2008152317
    |3| A. Slodczyk, Ph. Colomban, D. Lamago, M.-H. Limage, F. Romain, B. Sala, S. Willemin, Ionics 14 (2008) 215-222; A.
    Slodczyk, Ph. Colomban, S. Willemin, O. Lacroix, B. Sala, J. Raman Spectrosc. 40 (2009) doi:10.1002/jrs.2157
    |4| T. Kobayashi, K. Abe, Y. Ukyo and H. Matsumoto, Solid State Ionics 138 (2001), pp. 243251.
    OF.1.9
    New fuel cell membranes for hydrogen purification and proton transport
    H. Bai, W.S. Winston Ho
    Department of Chemical and Biomolecular Engineering and Department of Materials Science and Engineering, The Ohio
    State Universitv - 2041 College Road, Columbus, OH 43210-1178, USA
    hochbmeng.ohio-state.edu
    This presentation covers two types oI new membranes Ior Iuel cells: (1) carbon dioxide-selective membranes Ior hydrogen
    puriIication and (2) proton-exchange membranes (PEMs). On hydrogen puriIication Ior Iuel cells, the membranes have been
    synthesized by incorporating amino groups into crosslinked polyvinylalcohol and newly polymerized sulIonated
    polybenzimidazole (SPBI) copolymer matrixes |1|. These membranes are selective to carbon dioxide and hydrogen sulIide
    preIerentially versus hydrogen since the acid gases permeate through the amine-containing membranes via the Iacilitated
    transport mechanism due to their reversible reactions with the amine. The membranes synthesized have shown high carbon
    dioxide and hydrogen sulIide permeabilities and selectivities vs. hydrogen up to 170
    o
    C. Using the membrane synthesized, we
    have obtained 10 ppm carbon monoxide in the hydrogen product in water gas shiIt membrane reactor experiments via carbon
    dioxide removal. The data have been in good agreement with modeling prediction. We also removed carbon dioxide Irom a
    syngas containing 17 carbon dioxide to 30 ppm and obtained ~99 carbon dioxide in the acid gas stream |2|. Since
    hydrogen sulIide reacts with the amine via proton transIer whereas carbon dioxide reacts via carbamate Iormation mainly, the
    Iormer has a much higher reaction rate with the amine than the latter. Due to a higher amine reaction rate with hydrogen
    sulIide than with carbon dioxide, hydrogen sulIide can permeate through the membrane much Iaster than carbon dioxide. Our
    data showed hydrogen sulIide with approximately 3 times permeability oI carbon dioxide. Our initial experiments have shown
    a nearly complete removal oI hydrogen sulIide Irom 50 ppm in the synthesis gas Ieed to about 10 ppb in the hydrogen product,
    which is good Ior Iuel cell applications.
    PEMs to operate at high temperatures (above 100
    o
    C) and low humidities (below 50 relative humidity) are needed to increase
    anode`s tolerance to carbon monoxide poisoning and to eliminate the water Ilooding problem at the cathode. For the PEMs,
    we have synthesized sulIonated polyimide copolymers containing hydrophilic soIt segments to increase the water retention oI
    the membranes at high temperatures and low humidities |3|. In Iuel cell perIormance testing, the new membrane showed
    similar perIormance as NaIion

    112 at 70
    o
    C and 80 RH, but much better perIormance than NaIion

    112 at 120
    o
    C and 50
    RH. Recently, we have also synthesized new SPBI-based membranes. The membrane has exhibited a very high conductivity
    (~ 0.1 S/cm) at high temperatures (~ 120
    o
    C) and low humidities (even anhydrous), which could essentially meet or exceed the
    US Department oI Energy targets Ior PEM materials. In addition, this membrane has possessed excellent thermal, oxidative,
    chemical and hydrolytic stabilities even at high temperatures. Thus, it has the great potential Ior the PEM Iuel cell application
    at high temperatures and low humidities. All oI these new membranes should be much more cost-eIIective since the starting
    materials are more than two orders oI magnitude less expensive than those Ior NaIion

    membranes.
    |1| H. Bai and W. S. W. Ho, 'New Carbon Dioxide-Selective Membranes Based on SulIonated Polybenzimidazole (SPBI)
    Copolymer Matrix Ior Fuel Cell Applications, Ind. Eng. Chem. Res., ACS ASAP 10.1021/ie800507r (2008).
    |2| J. Huang, J. Zou, and W. S. W. Ho, 'Carbon Dioxide Capture Using a CO
    2
    -Selective Facilitated Transport Membrane,
    Ind. Eng. Chem. Res., 47 (4), 1261-1267 (2008).
    |3| H. Bai and W. S. W. Ho, 'New Poly(ethylene oxide) SoIt Segment-Containing SulIonated Polyimide Copolymers Ior High
    Temperature Proton-Exchange Membrane Fuel Cells, J. Membr. Sci., 313 (12), 75-85 (2008).
    -130-
    OF.1.10
    Experimental study of concentration polarization on the hydrogen flux through thin,
    highly selective palladium based membranes
    J. Catalano, M. G. Baschetti, G. C. Sarti
    Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali, Universita degli Studi di Bologna, Jia
    Terracini 28, 40131 Bologna, Italv
    giulio.sartiunibo.it
    The behavior oI a palladium-based membrane module Ior hydrogen separation has been studied experimentally and
    mathematically modeled. These metallic membranes may have rather high hydrogen permeation rates and extremely high
    selectivity, and both aspects can lead to an accumulation oI the non permeable gases and a depletion oI hydrogen in the
    boundary layer close to the membrane |1-3|. In this work several tests have been perIormed using Pd based membranes Iormed
    by a 2.5m Pd-Ag layer (about 20 wt Ag) deposited onto a porous ceramic support. The concentration polarization
    phenomenon was studied by measuring hydrogen permeance at diIIerent Ieed compositions (using both binary and ternary
    mixtures containing hydrogen, nitrogen and methane), Ieed Ilow rates, pressures (with total trans-membrane pressure
    diIIerences between 0.5 and 6 bar), and temperatures (between 673 K and 773 K). The results obtained with mixture Ieeds
    have then been compared with pure hydrogen data.
    The membranes used exhibit excellent behaviour, maintaining high Iluxes and a virtually inIinite selectivity throughout the
    relatively long testing period which lasted over 3000 hours overall. The pure gas permeation behaviour is accurately described
    by Sieverts' law conIirming that diIIusion in metallic coating is controlling the process kinetics. On the contrary, the use gas
    mixtures in the Ieed deIinitely reduces H
    2
    permeance, and also leads to hydrogen Iluxes with signiIicant deviations Irom
    Sieverts` law. With gas mixtures in the Ieed, the permeate Ilux deIinitely increases by increasing both Ieed Ilowrate and Ieed
    hydrogen concentration. Such experimental Iindings document the eIIects oI concentration polarization and the role oI the
    mass transport resistance in the gas phase. The latter has been accounted Ior by a suitable mathematical model; the use oI the
    gas phase mass transport coeIIicient allowed to obtain a very good representation oI the experimental results and led to
    Sherwood numbers which Iollow a boundary layer type relationship as a Iunction oI Reynolds and Schmidt numbers.
    A new rigorous procedure, based on the sensitivity oI the hydrogen Ilux on membrane permeance and gas phase mass transport
    coeIIicient, is also presented to properly compare the two resistances endowed with diIIerent physical dimensions. The
    analysis leads to the introduction oI a new dimensionless number (concentration polarization number Ior hydrogen), which
    enables us to establish the relative role oI membrane and gas phase resistances; its eIIective value contains only process
    variables and membrane permeance to hydrogen, and oIIers relevant inIormation without requiring model simulations. This
    analysis shows that the experimental data collected span the range oI operating conditions Irom the case in which the leading
    resistance Ior hydrogen Ilux is in the membrane to the case in which the controlling resistance is in the gas phase.
    |1| Ldtke, O., Concentration polari:ation in gas permeation, Journal oI Membrane Science, 1998. 146: p 145.
    |2| He, G., Theoretical studv on concentration polari:ation in gas separation membrane processes, Journal oI Membrane
    Science, 1999. 153:p 243.
    |3| Zhang, J., et al., Experimental and simulation studies on concentration polari:ation in H2 enrichment bv highlv permeable
    and selective Pd membranes, Journal oI Membrane Science, 2006. 274: p 83.
    OF.1.11
    Multifunctional dense ceramic hollow fibre membrane reactors for methane
    conversion
    Z.T. Wu, B. Wang, K. Li
    Department of Chemical Engineering, Imperial College London, London, SW7 2AZ, U.K.
    kang.liimperial.ac.uk
    Ceramic hollow Iibre membranes have shown many advantages over their traditional disc/Ilat sheet and tubular counterparts in
    Iluid separation/reaction. Employment oI these types oI membranes modiIied with catalytic Iunctions is promising Ior greatly
    improving perIormance variables, such as the surIace area/volume ratio oI the unit, the conversion and the yield oI the reaction
    and the volume productivity oI the reactor etc., as long as a proper design and preparation methodology Ior the multiIunctional
    hollow Iibre membrane reactors can be realized.
    -131-
    Our work has Iocused on the development oI a highly compact multiIunctional dense ceramic hollow Iibre membrane, which
    consists oI a thin and Iully dense outer oxygen separation layer and a highly porous inner support layer. A dry-wet co-
    spinning/co-sintering technique schematically shown in Figure 1 is employed in the Iabrication oI the multiIunctional hollow
    Iibre membranes with a dual-layer structure, signiIicantly simpliIying the preparation process and contributing to overcome a
    number oI challenges in the development oI thin oxygen permselective membranes. Besides providing good mechanical
    strength, the inner support layer is catalytically active in a number oI high temperature chemical reactions such as steam
    reIorming oI methane (SRM) and the partial oxidation oI methane (POM) to syngas. Figure 2 presents the results oI the
    catalytic activity measurement oI the inner support layer material Ior the POM reaction, using methane (9.5) and oxygen
    (4.75) as the reactants. As can be seen, high methane conversion as well as CO selectivity up to around 80 has been
    achieved between 1073 K and 1223 K. Moreover, the value oI the H
    2
    /CO ratio in the product stream is kept at approximately
    2, demonstrating the Ieasibility oI developing a highly compact multiIunctional dense ceramic hollow Iibre membrane reactor
    Ior methane conversion.
    Figure 1 Schematic diagram oI the dry-wet co-spinning oI the
    dual-layer ceramic hollow Iibre membranes
    Figure 2 Catalytic activity measurement oI the inner
    support layer material Ior POM reaction
    By adjusting the composition oI the inner support layer, which changes the catalytic activity oI the layer, the current design oI
    the hollow Iibre membrane reactor can be employed in other high temperature catalytic reactions using oxygen as the reactant.
    Furthermore, the related preparation methodology demonstrated in this study can also be applied to the development oI
    advanced high temperature solid oxide Iuel cells (SOFC).
    OF.1.12
    Vanadium-based, metal-metal composite membranes for hydrogen separation
    C. Nishimura
    1
    , M. Komaki
    1
    , K. Iwasa
    2
    , M. Akiduki
    2
    , S. Ogawa
    2
    , H. Yoshinaga
    3
    1
    Fuel Cell Materials Center, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan
    2
    Department of Mechanical Science and Engineering, Chiba Institute of Technologv, 2-17-1 Tsudanuma, Narashino, Chiba
    275-0016, Japan
    3
    Taivo Koko Corporation Ltd., 1603-1 Higashioki, Nakahiro-a:a, Ako, Hvogo 678-0232, Japan
    NISHIMURA.Chikashinims.go.jp
    The production oI high purity hydrogen is an important technical issue, which is related to Iuture energy and environmental
    problems. Membranes oI palladium alloys have been used commercially Ior decades to provide high purity hydrogen mainly
    Ior laboratory use and semiconductor manuIacture. However, palladium alloys are too costly Ior large-scale production oI high
    purity hydrogen. Keeping such situations in mind, we have developed some vanadium-based alloys Ior membrane materials to
    puriIy hydrogen gas to replace palladium|1-2|. Our membranes have acheived a high hydrogen permeation Ilux and the
    absolute separation coeIIicient, at the same time.
    The vanadium alloys need thin palladium or palladium alloy Iilms on surIaces to protect Irom oxidation and to give catalytic
    activity to decompose hydrogen gas molecules into atoms to permeate the alloys. So, our membranes have a sandwich-type
    structure, which can be sometimes called metal-metal composite membranes. The membranes contain interIaces between bulk
    alloys and surIace Iilms. For the use at high temperatures such as 823 K, which is a typical operation temperature oI membrane
    reactors Ior methane reIorming, interdiIIusion oI bulk alloys and surIace Iilms can be a big problem. It is a common challenge
    Ior non-palladium based membranes to be overcome Ior hydrogen puriIication/separation. In this study, LASER irradiation
    treatment was attempted to modiIy the microstructure oI surIace Iilms to suppress the interdiIIusion. Also, the eIIects oI crystal
    -132-
    grain orientation oI vanadium alloy substrate were investigated. The long term permeation tests at 673 K clearly revealed the
    beneIicial eIIect oI the LASER treatment. Crystal grain orientations strongly aIIected the interdiIIusion oI vanadium substrate
    and paladium overlayer, suggesting a possible mitigation oI interdiIIuion at higher temperatures.
    |1| C. Nishimura, M. Komaki, S. Hwang and M. Amano, J. Alloys Comp., 330-332, 902 (2002).
    |2| J. Y. Yang, M. Komaki and C. Nishimura, Int. J. Hydrogen Energy, 32, 1820 (2007).
    OF.1.13
    Thin Pd-23wAg membranes for hydrogen separation
    R. Bredesen, T.A. Peters, M. Stange
    SINTEF Materials Technologv, P.O. Box 124 Blindern, N-0314, Oslo, Norwav
    Rune.bredesensinteI.no
    Hydrogen selective membranes are interesting candidates to be applied in hydrogen and energy technology. In water gas shiIt
    membrane reactors, Ior example, the membranes can be used to achieve CO
    2
    capture in pre-combustion decarbonisation cycles
    Ior large-scale power generation or hydrogen production. The current commercial availability oI hydrogen selective palladium
    membranes and their utilization, however, are limited due to an unIavorable cost-perIormance combination. These
    commercially available membranes are available in the Iorm oI tubes or Ioils, which are relatively thick (20 m or more). The
    hydrogen Ilux, being inversely proportional to the thickness oI the membrane, is thereIore too low Ior most applications. For
    practical use, it is thereIore necessary to develop membranes with a reduced thickness oI the Pd layer. An aIIordable, robust
    and selective hydrogen-separating membrane could signiIicantly reduce this cost.
    SINTEF has developed a technique Ior the manuIacturing oI palladium-based hydrogen separation membranes based on a two
    step process allowing a reduction in the membrane thickness making palladium membranes economically viable. First, a
    deIect Iree Pd/Ag alloy membrane is prepared by magnetron sputtering onto the perIect surIace` oI a silicon waIer. In a
    second step the membrane is removed Irom the waIer and transIerred to a porous stainless steel support. This allows the
    preparation oI very thin (approximately 2-3 m) deIect Iree high-Ilux membranes supported on macroporous substrates, which
    can be operated at elevated pressures.
    In the present work the hydrogen permeation and stability oI these tubular palladium alloy (Pd/Ag23) composite membranes
    have been investigated at elevated temperatures and pressures. In our analysis we diIIerentiate between dilution oI hydrogen by
    other gas components, hydrogen depletion along the membrane length, concentration polarization adjacent to the membrane
    surIace, and eIIects due to surIace adsorption on the hydrogen Ilux. Without pre-treatment oI the membrane, a maximum H
    2
    Ilux oI 1223 mLmin
    -1
    cm
    -2
    was obtained at 400C and 26 bar hydrogen Ieed pressure. A good linear relationship was Iound
    between hydrogen Ilux and pressure as predicted Ior rate controlling bulk diIIusion. In a mixture oI 50 H
    2
    50 N
    2
    a
    maximum H
    2
    Ilux oI 230 mLmin
    -1
    cm
    -2
    and separation Iactor oI 1400 were achieved at 26 bar. The large reduction in hydrogen
    Ilux is mainly caused by the build-up oI a hydrogen-depleted concentration polarization layer adjacent to the membrane due to
    insuIIicient mass transport in the gas phase. Substituting N
    2
    with CO
    2
    results in Iurther reduction oI Ilux, but not as large as Ior
    CO where surIace adsorption prevail as the dominating Ilux controlling Iactor. In WGS conditions (57.5 H
    2
    , 18.7 CO
    2
    ,
    3.8 CO, 1.2 CH
    4
    and 18.7 steam), a H
    2
    permeance oI 1.110
    -3
    molm
    -2
    s
    -1
    Pa
    -0.5
    was Iound at 400C and 26 bar Ieed
    pressure. Operating the membrane Ior more than one year under various conditions (WGS and H
    2
    N
    2
    mixtures) at 10 bars
    indicated no membrane Iailure. A membrane liIe time oI several (2-3) years (T _ 425C) is assessed Ior the employed
    experimental conditions based on long-term stability tests. Post-process characterisation shows a considerable grain growth
    and oI micro-strain relaxation in the Pd-23Ag membrane aIter the prolonged permeation experiment. Changes in surIace area
    are relatively small. In addition, segregation oI Ag to the membrane surIaces is observed. The Iormation oI pinholes is
    identiIied as the main source Ior the increased N
    2
    leakage during testing at higher temperature.
    This research is Iinanced by the European Union, the CO
    2
    Capture Project (CCP), and the Research Council oI Norway (RCN)
    through the Iollowing programs, CCP/RCN-Renergi 2004/2005 (Contract No: C04043 and 5299775), RCN-Nanomat
    (Contract no: 158516/S10), and the EU-6FP CACHET project, (Contract no.: 019972) (www.cachetco2.eu). We would
    thankIully acknowledge Pall Corp. Ior providing the membrane supports.
    -133-
    OF.1.14
    Blue energy
    J. Veerman
    1,2
    , S.J. Metz
    1
    , M. Saakes
    1
    , G.J. Harmsen
    3
    1
    Wetsus, Centre of Excellence for Sustainable Water Technologv, P.O. Box 1113, 8900 CC Leeuwarden, The Netherlands
    2
    Noordelifke Hogeschool Leeuwarden, department of Life Sciences and Technologv, Agora 1, 8934CJ Leeuwarden, The
    Netherlands
    3
    State Universitv Groningen, Nifenborg 4, 9747 AG Groningen, The Netherlands
    joost.veermanwetsus.nl
    Salt gradient energy` is in principle clean, sustainable and gives no thermal pollution or CO
    2
    exhaust and thereIore also called
    Blue Energy`. The total global salinity power is estimated to be 2.6 TW, which is suIIicient to supply the global electricity
    demand (2 TW) or 16 oI the total present energy consumption.
    There are diIIerent methods to extract energy Irom the mixing oI sea and river water, the most important being reverse
    electrodialysis (RED) and pressure retarded osmosis (PRO). Post et al. |1| showed that in the case oI sea water and river water,
    RED is a very promising technique. In principle, RED is a seemingly simple technique. Nevertheless, only 8 groups have
    published in scientiIic journals on their experimental results with RED operating on sea and river water during a period
    encompassing more than 50 years. In these papers RED has been proven on lab scale. However, the reported power densities
    were relatively low and the eIIiciency oI the process (Iuel eIIiciency) was not taken into account. Meanwhile, the knowledge
    oI ion exchange membranes has increased and many ion exchange membranes with good properties have been developed.
    Furthermore, energy demand, and therewith also the problems concerning chemical and thermal pollution as well as
    greenhouse problems caused by CO
    2
    exhaust, has grown enormously. The investigation oI this technique using state oI the art
    membranes and the improvement oI the operational properties oI the process is aimed at providing a solution to these
    problems.
    We developed an accurate experimental set-up Ior the measurement oI the perIormance oI a RED stack at various process
    conditions. Furthermore we modiIied the design oI a stack and obtained the highest power density reported in literature. We
    also quantiIied the eIIect oI osmosis, electro-osmosis, pressure losses etc. on the perIormance (power density, thermodynamic
    exergy eIIiciency and Iuel eIIiciency) oI a RED stack. We tested diIIerent pairs oI membranes and are able to describe the
    processes with the Maxwell-SteIan theory.
    At this moment we have a research RED stack (Fig. 1) with the possibility to change Ieed modes, electricity harvesting etc.
    We investigated diIIerent aspects oI the RED process: shortcut currents |2 |, process parameters and multi stage operation |3|.
    A number oI parameters are determined, necessary Ior Iurther upscaling. Results on the use oI diIIerent membranes, various
    electrode systems ad modeling are published in the near Iuture
    |1| W. Post, J. Veerman, H.V.M. Hamelers, G.J.W. Euverink, S.J. Metz, K. Nymeijer, C.J.N. Buisman. Salinitvgradient
    power. Evaluation of pressureretarded osmosis and reverse electrodialvsis. J. Membr. Sci. 288 (2007) 218230
    |2| J. Veerman, J. W. Post, S.J. Metz, M. Saakes, G.J. Harmsen, Reducing power losses caused bv ionic shortcut currents in
    reverse electrodialvsis stacks bv a validated model. J. Membr. Sci. 310 (2008) 418-430
    |3| J. Veerman, M. Saakes, S.J. Metz and G.J. Harmsen, Reverse electrodialysis: perIormance oI a laboratory device with 50
    cells (2008) J Membr Sci doi:10.1016/j.memsci.2008.11.015
    OF.2.1
    Comparison of the operational processes of three different full-scale membrane
    bioreactors
    P. Krzeminski
    1
    , A. van Nieuwenhuijzen
    2
    , J. van der GraaI
    2
    1
    Delft Universitv of Technologv, Stevinweg 1, 2628 CN Delft, The Netherlands
    2
    Delft Universitv of Technologv / WitteveenBos Consulting Engineers, P.O. Box 233, 7400AE, Deventer, The Netherlands
    p.krzeminskitudelIt.nl
    To Iacilitate Iurther development and optimisation oI membrane bioreactor (MBR) technology advanced research programme
    has been worked out with the special interest in comparison and optimisation oI the Iull-scale plants, i.e. the cost and energy
    reduction. The main objective oI this work is to compare operational process perIormances oI three Iull-scale membrane
    bioreactors in the Netherlands. Filterability and its relationship to plants operational parameters will be under investigation.
    These data will be worked out in a database to compare perIormance on Iull scale and to identiIy the correlations between
    -134-
    those parameters. This should provide inIormation on eIIects oI diIIerent membrane bioreactors conIigurations and may give
    insight into operational issues and eIIiciency oI the plants. Moreover, extensive research on energy consumption within the
    MBRs is scheduled. This operational aspect comparison should lead to the optimization oI the costs, energy demand and
    chemical addition.
    For the purpose oI this research the DelIt Filtration Characterisation method (DFCm), described in detail by Evenblij (2005),
    was used. This Iiltration unit was developed by DelIt University oI Technology speciIically Ior Iiltration characterisation and
    membrane Iouling research. The DFCm consists oI a small-scale Iiltration unit and is operated on the basis oI a measuring
    protocol. The DFCm Iacilitates the measuring and characterization oI diIIerent samples oI activated sludge under the same
    conditions and directly on the MBR site.
    A measurement campaign includes Iilterability tests during summer and winter period at each location. Filterability oI the
    sludge in diIIerent compartments oI the MBR was monitored with DFCm experiments. Parallel to the DFCm tests operational
    data were collected Ior their Iurther extensive analyses and MBRs comparison. Filtration characteristics were measured in
    order to compare Iilterability results and then correlate with the plants operational data. Furthermore analytical and statistical
    tools will be implemented Ior the comparison study in order to explain all the various relations and the importance oI the
    speciIic operational parameters. Moreover, all energy users within the MBRs will be identiIied and consumption oI each unit
    careIully investigated. Based on those inIormation most promising, in terms oI energy saving, modules will be determined.
    Detailed description and comparison oI the investigated Iull-scale MBRs together with their operational data will be presented.
    Experimental results obtained during sludge Iilterability monitoring will be discussed. Our work will discuss relation between
    operational parameters and Iilterability oI activated sludge Ior the membrane bioreactors optimization studies based on case oI
    three diIIerent Iull-scale Dutch MBRs.
    The author likes to thank the European Commission Ior its Iinancial support through the MBR-Train project (Marie Curie Host
    Fellowship Ior Early Stage Research Training supported under the 6th Framework Programme).
    Evenblij, H., Geilvoet, S.P., Van der GraaI, J.H.J.M., Van der Roest, H.F. (2005). Filtration characterisation Ior assessing
    MBR perIormance: three cases compared. Desalination, 178, pp 115-124.
    OF.2.2
    Effect of the presence of cytostatic drugs on the sludge of a membrane bioreactor,
    consequence on the process
    L.F. Delgado
    1
    , C. Dorendeu
    2
    , B. Marion
    2
    , V. Faucet-Marquis
    1
    , A. PIohl-Leszkowicz
    1
    ,
    S. Schetrite
    1
    , S. Paranthoen
    3
    , C. Albasi
    1
    1
    Laboratoire de Genie Chimique, CNRS - Universite de Toulouse, 6 allee Monso, 31029 Toulouse, France.
    2
    Laboratoire de biophvsique et bio-analvse, faculte de pharmacie, universite de Montpellier, BP 14491, 15, avenue Charles-
    Flahault, 34093 Montpellier, France
    3
    Pall Industrial, B.P.1 - 65460 Bazet
    claire.albasiensiacet.Ir
    Some pharmaceuticals are not completely eliminated in the municipal WWTPs and are discharged as contaminants into
    receiving waters. The alkylating antineoplastic drug Cyclophosphamide (CP) is one oI the oldest known cytostatics and is one
    oI the most Irequently used agents in cancer chemotherapy. Besides its cytotoxic eIIects, CP possesses teratogenic and
    mutagenic properties and is a known human carcinogen. CP is a prodrug that requires biotransIormation to become cytotoxic.
    It is transIormed via hepatic and intracellular enzymes to active alkylating metabolites, 4-hydroxycyclophophosphamide,
    aldophosphamide, acrolein and phosphoramide mustard. CP could be detected in concentrations ranging Irom 20ng/L to 4.5
    g/L in hospital sewage. The application oI membrane bioreactor (MBR) technology is investigated here with the aim oI
    evaluating its potential Ior cytostatic drug bioremoval
    Two identical lab-scale crossIlow MBR were run in parallel. One oI them is used as a controller (MBR2-Control), whereas
    Cyclophosphamide and its main metabolites (Acrolein, Phosphoramide Mustard, 4-ketocyclophosphamide (4-Keto CP),
    Nitrogen Mustard) were continuously added to the other (MBR1-CP). Each reactor was inoculated with activated sludge Irom
    a municipal sewage treatment plant (dry weight, 3g/L). The CP removal is observed at a range oI 75 and 80 Ior 4-KetoCP.
    TransIormation oI CP via metabolite 4-keto CP is also visible Irom changes in the 4-ketoCP concentrations, higher than in
    Ieed.
    The removal eIIiciencies oI COD and TN were almost identical in both MBRs, indicating that addition oI pharmaceuticals has
    negligible eIIect on the global eIIiciency oI the treatment perIormance. However, it induces a modiIication oI the biological
    suspended solids and so a modiIication on the membrane Iouling. COD removal in the system was attributable to two Iactors,
    one was biological removal by micro-organisms and the other was physical retention by the membrane. Considering the COD
    concentration in the supernatant (greater in the MBR1-CP than in the MBR2-Control), it points out the role oI the membrane in
    -135-
    the quality oI permeate. Fouling was then Iaster in MBR 1. The change oI membrane (clean instead oI Iouled one) did not
    change anything in the pressure. The quality oI the sludge, its mechanical resistance which is weakening by the cytostatic, its
    supernatant EPS content, governs the Iouling phenomena in MBR1-CP.
    Simultaneously, the toxicity removal is assessed Irom biomarkers tests and related to the choice oI the reactor operating
    conditions, more specially the sludge retention time. Periodical estimation oI the activity oI sludge by respirometric measures
    was perIormed. Face to such pollution evidence has been made about the use oI MBR. The results oI this study prooIed that
    advances wastewater treatment using a MBR provides a suitable process Ior lowering CP concentrations beIore discharge into
    the aqueous environment.
    OF.2.3
    MBR long term experiment: toward a normalisation of operating parameters
    J. Lebegue, M. Heran, A. Grasmick
    Laboratoire de Genie des Procedes . Eaux et Bioproduits LGPEB, UMR-CIRAD 016, Universitv of Montpellier II, CC005,
    Place Eugene Bataillon, 34095, Montpellier Cedex 05, France.
    heranuniv-montp2.Ir
    Membrane bioreactors (MBR) is a promising technology in wastewater treatment, coupling a biological treatment and a
    physical separation. Membrane Iouling is the main Iactor which limits the Iull development oI MBR, promising technology in
    wastewater treatment. On oI the most common strategy to reduce and control the Iouling is to increase the shear stress close to
    the membrane by air injection. However, according to the literature data, aeration can represent up to 50 oI MBR
    Iunctioning costs |1|.
    The aim oI the study is to optimize and to adjust the membrane aeration rate with the view oI minimize membrane Iouling
    when the MBR Iunctions under unsteady state Iiltration conditions. The paper will present some results in term oI membrane
    perIormances and membrane aeration rate regulation with permeate Ilux.
    In order to keep advantages oI immersed membrane system (low energy requirement) and to Iavour unit maintenance, a side
    stream system was developed where the suspension circulation (local turbulence closed to the membrane) is induced by air
    injection at the bottom oI membrane module. Nevertheless, even with tangential Ilow due to gas injection, the radial axis oI
    Iiltration throughout a hollow Iiber bundle induces a radial distribution oI the suspension characteristics inside bundle (Figure
    1). So, the intensity oI air membrane must be suIIicient to induce high degree oI Ilow circulation throughout the bundle in
    order to limit sludge deposit on the membrane.
    Long term experiments on lab scale pilot with diIIerent operating condition (sludge concentration, permeat Iluxes, and
    membrane aeration) point out some conditions oI sludging control. These experiments and short visual observation allow
    diIIerent Iouling phenomena description. On the other hand, iI hydrodynamics generated by aeration must be in accordance
    with the Iiltration intensity, it is diIIicult to underline the impact oI each variable on the sustainable Iiltration condition.
    The analysis oI the system, according to dimensionless numbers, allows the deIinition oI comparison criteria. Results underline
    a minimal energy requirement to keep sustainable Iiltration condition over time. Then, the representation oI these numbers
    versus the amount oI Iiltrated water draws diIIerent Iiltration response and tendency.
    |1| Z.F. Cui, S.Changb, A.G. Fane. The use oI gas bubbling to enhance membrane processes, J. Membrane Sci., (2003), 221,
    135.
    OF.2.4
    Flux enhancing chemicals in MBR: a 3 year comprehensive study
    V. Iversen
    1
    , S. Hermann
    1
    , A. Drews
    1,2
    , B. Lesjean
    3
    , M. Kraume
    1
    1
    TU Berlin, Chair on Chemical Engineering, Ma 5-7, Str. des 17. Juni 135, 10623 Berlin, Germanv
    2
    Universitv of Oxford, Dept. of Engineering Science, Parks Road, Oxford OX1 3PJ, UK
    3
    Berlin Centre of Competence for Water, Cicerostr. 24, 10709 Berlin, Germanv
    vera.e.iversentu-berlin.de
    Membrane Iouling still is the major drawback oI MBR technology. The new and promising method oI adding certain
    chemicals like natural and synthetic polymers, metal salts, activated carbons to the MBR mixed liquor is being investigated at
    -136-
    TU Berlin. These additives modiIy the mixed liquor and may thus aIIect the structure oI the Iilter cake through the Iormation
    oI larger Ilocs |1, 2| but can also entrap the potential Iouling culprit SMP |3|. A comprehensive and systematic comparison oI
    diIIerent chemicals, considering also side eIIects, has been accomplished within the EU project AMEDEUS. A large number
    oI substances was screened in lab tests considering their impact on SMP removal, particle size distribution and Iouling
    propensity oI the sludge, but also their biotoxic impact and optimum concentrations were studied. The most promising
    chemicals were investigated in long term trials in two identical parallel pilot MBRs (1.6m and 22m membrane module by A3
    Water Solutions, Germany, each) Ied on real municipal sewage. While Ilocculants were dosed into one system, the other
    served as a reIerence.
    Several oI the 30 initially screened substances were able to eIIectively reduce SMP concentration in mixed liquor supernatant
    |3|. Batch tests showed that most oI the substances did not inhibit oxygen uptake, nitriIication and denitriIication |4|. Only
    polyaluminium chloride and one powdered activated carbon strongly inIluenced these biological parameters. It could also be
    shown that the biopolymer chitosan is highly biodegradable and thus not interesting Ior Ilux enhancing in MBR. On the other
    hand it strongly increased the particle size distribution as well as all the synthetic polymers |2|. In Iiltration test cell
    experiments, it was Iound that especially the synthetic polymers strongly enhanced the Iiltration, while the metal salts and
    natural polymers did not change the critical Ilux much |3|. As already assumed Irom the particle size measurements, most
    polymers decreased the Iilter cake resistance, but also the internal Iouling. Two synthetic polymers and a starch were then
    tested in the parallel pilots. As expected Irom the jar tests, these additives did not disturb the biological perIormance. While the
    synthetic polymers enhanced the Iilterability, the natural polymer starch worsened the Iiltration perIormance. This was not
    expected as starch showed good results in the test cell experiments. From this 3 year comprehensive screening it can be
    concluded that especially synthetic polymers are eIIective Ior Ilux enhancement.
    The study was perIormed within the FP6 project 'AMEDEUS (contract n 018328). The authors acknowledge the EC Ior the
    Iinancial support and the chemicals producers Ior Iree supply oI samples.
    |1| B-K Hwang, W-N Lee, P-K Park, C-H Lee, I-S Chang, J Membr Sci 288, 2007, 149-156.
    |2| V Iversen, J Villwock, T de la Torre Garcia, A Drews, M Kraume, MDWT 2008, Toulouse.
    |3| H Koseoglu, NO Yigit, V Iversen, A Drews, M Kitis, B Lesjean, M Kraume, J Membr Sci, 2008, 57-64.
    |4| V Iversen, H Koseoglu, NO Yigit, A Drews, M Kitis, B Lesjean, M Kraume,Water Res, in press.
    OF.2.5
    Effective fouling control on a NF membrane module: a three year long case study
    M. Stoller
    Universitv of Rome "La Sapien:a" Department of Chemical Engineering, Jia Eudossiana 18, 00184 Rome, Italv
    stolleringchim.ing.uniroma1.it
    The continuous operation Ior three years oI a spiral wound NF membrane Ior olive vegetation waste water treatment will be
    discussed. The membrane module was Iirstly used at the beginning oI year 2006, and aIter that continuously operated Ior
    critical Ilux studies on a 100 litre batch system Ior the puriIication oI olive vegetation waste water.
    The olive vegetation waste water is a waste stream produced by the olive oil mill Iactories, characterized by a very high
    organic matter (COD values equal to 50-150 g/l).
    Without Iouling control, membranes would reach zero-Ilux condition very Iast, within days. This was not the case oI the
    analyzed NF membrane module, which was successIully operated Ior three years within the continuous Laboratory work oI
    many diIIerent Students at the Department oI Chemical Engineering. This result can be reached only by proper Iouling control,
    which relays on both critical Ilux measurements and optimized operation methods previously developed by the Author |1,2|.
    Since Iouling control especially on real waste water stream does not mean necessarily that the membrane perIormances didn`t
    change at all, the present work aims to review the collected data on the pure water permeability, the COD and polyphenols
    rejection and the critical Ilux values oI this NF module. The changes oI these key parameters throughout the years will be
    discussed, and moreover how Iouling control may (or not) maintain satisIying separation perIormances.
    Nowadays, the NF module is still used in Laboratory works since it has still Ilux values above the sustainable Ilux and
    rejection values compatible to waste water puriIication purposes, and thus represent the best possible validation Ior the adopted
    Iouling control methods.
    |1| M. Stoller, A. Chianese: 'Technical optimization oI a batch olive wash wastewater treatment membrane plant, 2006,
    Desalination 200(2006) pp 734-736. DOI. 10.1016/f.desal.2006.03.501
    |2| M. Stoller, A. Chianese: InIluence oI the adopted pretreatment process on the critical Ilux value oI batch membrane
    processes, 2007, Ind. Eng. Chem. Res. 8(46), pp 2249-2253, DOI: 10.1021/ie060964k
    -137-
    OF.2.6
    The forward osmosis membrane bioreactor: a multi-barrier approach for water
    reuse
    A. Achilli
    1
    , T.Y. Cath
    2
    , E.A. Marchand
    1
    , A.E. Childress
    1
    1
    Department of Civil and Environmental Engineering, Universitv of Nevada Reno, Reno, NJ 89557, United States
    2
    Division of Environmental Science and Engineering, Colorado School of Mines, Golden, CO 80401, United States
    aachilliunr.edu
    A novel MBR system that utilizes a submerged Iorward osmosis (FO) membrane in the bioreactor is investigated in the current
    study. In FO, water diIIuses across a selectively permeable membrane Irom a solution oI higher water chemical potential
    (lower osmotic pressure) to a solution oI lower water chemical potential (higher osmotic pressure); in the current application,
    water diIIuses Irom the bioreactor into a controlled draw solution (DS). The FO membrane acts as a barrier to solute transport
    and provides high rejection oI contaminants present in the wastewater stream. The diluted DS is reconcentrated using reverse
    osmosis (RO) or distillation. The reconcentrated DS is being reused in the FO process and the RO permeate is a high-quality
    product water. Thus, in most wastewater treatment applications, FO is not the ultimate process but rather a high-level
    pretreatment step beIore an ultimate reconcentration/desalination process.
    Compared to the microIiltration or ultraIiltration process in a conventional MBR, the FO process in the osmotic membrane
    bioreactor (OsMBR) oIIers the advantages oI much higher rejection (semi-permeable membrane versus microporous
    membrane) without the need oI applying pressure to withdraw the permeate. FO membranes are also likely to have lower
    Iouling propensity compared to high pressure membranes .
    Results Irom experiments conducted with a Ilat-sheet cellulose triacetate FO membrane and an NaCl draw solution
    demonstrated high sustainable water Ilux (Figure 1). Membrane Iouling was minimal and was controlled with osmotic
    backwashing. The FO membrane was Iound to reject 98 oI organic carbon and 90 oI ammonia; the OsMBR process
    (membrane biological process) was Iound to remove 99.8 oI organic carbon and 97.7 oI ammonia. The overall system
    (OsMBR RO) was Iound to remove over 99 oI both constituents.
    OF.2.7
    Oil production water treatment with eletrodialysis
    I. Medina, A. Ramirez, A. Cardenas
    Laboratorio de Me:clado, Separacion v Sintesis Industrial, Escuela de Ingenieria Quimica, Universidad de Los Andes
    Merida Jene:uela
    antoniocula.ve
    When crude oil is produced, some water normally comes associated with it. In Venezuela some oilIields produce around
    100.000,00 barrels per day oI associated water. This water has to be treated to reuse it or to discard into the environment iI it is
    not reinyected in the oilIield. One oI the problems oI some oI the oil production waters is its high chloride content and to
    -138-
    reduce it, electrodialysis is one possible alternative. In this work, water produced at the Victoria oilIield, in southern Venezuela
    was treated using an Asahi Glass CH-0 electrodializer. The water was obtained aIter some treatment that ended in an API
    separator. BeIore introducing the oil produced water into the electrodializer it was Iurther treated by passing it through a sand
    Iilter, to reduce its solid contents. The sand Iilter improves the turbidity Irom 20 NTU to 11 NTU. The initial chloride content
    is around 3000 ppm and it should be reduced to less than 1000 ppm which is the limit placed by environment regulations. The
    test made proved that the chloride reduction can be higher than 95 at diIIerent operating conditions when the oil production
    water was treated Ior a 15 minute period and that at a constant voltage oI 30 V the time required to meet the environmental
    regulations (1000 ppm) is oI around 4 minutes Ior 2 L oI oil produced water. By using this method, one stream (dilute stream)
    can be rejected to the environment or reused as irrigation or industrial water and the other can be Iurther concentrated and the
    salt discarded, or could be used in drilling Iluids Iormulation.
    OF.2.8
    Demineralization of saline waste waters containing phenol by electrodialysis
    F.J. Borges
    3
    , R. Guardani
    3
    , H. Roux-de Balmann
    1,2
    1
    Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, F-31062 Toulouse cedex 09, France
    2
    CNRS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    3
    Chemical Engineering Department, Universitv of So Paulo, Av. Luciano Gualberto, travessa 3, 380 CEP. 05508-900 -
    So Paulo SP- Bra:il
    savignacchimie.ups-tlse.Ir
    Recalcitrant organic pollutants, like phenol and phenolic compounds, common contaminants in industrial wastewater, have
    been recognized as an issue oI growing importance in recent years. Since conventional wastewater treatments are hardly
    capable oI removing such pollutants, oxidation processes are generally used Ior their degradation. However, such processes
    can be inhibited by ionic compounds, like sodium chloride, normally associated with these pollutants in wastewater.
    In order to Iit with the salt content acceptable Ior the oxidation treatment oI the organic matter, electrodialysis can be used to
    demineralize the waste water. The objective is then to decrease the salt content until reaching a given value while minimizing
    the transIer oI the organic pollutant to keep it as much as possible in the desalted stream to be Iurther treated by oxidation.
    An experimental study was carried out in which the inIluence oI the process variables on the phenol loss and sodium chloride
    removal was investigated. A pilot plant equipped with AMX and CMX membranes was used. Experiments were also
    perIormed without current, in order to determine the possible phenol transIer due to diIIusion. The phenol and salt
    concentration variations in the ED compartments were measured over time, using dedicated procedures and an experimental
    design to determine the global characteristic parameters.
    A phenomenological approach was used to relate the phenol, salt and water Iluxes with the driving Iorces (concentration and
    electric potential gradients).
    The transIer oI phenol was Iound to be increased in ED conditions. A convective contribution was thus pointed out in addition
    to the expected one, much lower, coming Irom diIIusion. This convective contribution, that increases the phenol loss during
    the desalting process, was correlated to the water Ilux due to electroosmosis related to the migration oI salts.
    Nevertheless, it was demonstrated that high demineralisation Iactors can be reached while maintaining the phenol yield at a
    reasonable level Ior Iurther treatment by oxidation. ED is then an interesting means to treat saline waste waters polluted by
    phenol prior to the chemical treatment.
    OF.2.9
    Gas separation effectiveness of supported ionic liquid membranes compared to non-
    porous membranes
    P. Cserjesi, N. Nemestothy, K. BelaIi-Bako
    Institute of Chemical and Process Engineering, Pannon Universitv, 10. Egvetem ut, 8200, Jes:prem, Hungarv
    cserjesimukki.richem.hu
    Membrane gas separation is considered as one oI the most important separation processes oI the Iuture since it is not only
    environmentally sound but it is also able to produce high purity gases. ThereIore the continuous improvement oI membranes is
    indispensable.
    -139-
    The aim oI this work was to prepare several supported liquid membranes using ionic liquids and to compare their eIIectiveness
    with each other and with those oI non-porous membranes. Twelve diIIerent types oI ionic liquids were tested Ior the
    preparation oI supported ionic liquid membranes and three kinds oI non-porous membranes were applied. Their permeability
    and ideal selectivity were measured using H
    2
    , N
    2
    , CO
    2
    and CH
    4
    gases. Since CO
    2
    can cause unIavourable changes in the
    mechanical and chemical properties oI the PVDF membranes used as the supporting phase |1| the stability oI the membranes
    was studied by measuring decrease in H
    2
    permeability aIter the permeation oI CO
    2
    .
    It was Iound that some oI the ionic liquids tested were not suitable Ior membrane preparation because they destroyed the
    supporting membrane material. The membranes prepared with the rest oI the ionic liquids showed adequate permeabilities and
    high CO
    2
    /H
    2
    , CO
    2
    /N
    2
    and CO
    2
    /CH
    4
    ideal selectivity. Compared to non-porous membranes some oI the supported ionic liquid
    membranes had higher permeabilities and selectivities.
    The results oI the experiments concerning stability showed that CO
    2
    had an eIIect both on supported ionic liquid membranes
    and non-porous membranes. However, the extent oI the eIIect was diIIerent in all cases.
    It can be stated that supported ionic liquid membranes have adequate an in some cases higher permeabilities and higher
    selectivities than those oI the non-porous membranes studied.
    |1| J.H. Kim, W.J. Koros, D.R. Paul, Journal oI Membrane Science, 2006, 282, 32-43
    OF.2.10
    Nanofiltration of effluents containing heavy metals: nanoflux simulations as a
    descriptive and predictive tool for research and industry needs
    L. Schrive
    1
    , V. Bonhoure
    1
    , A. Deratani
    2
    , J. Palmeri
    2
    1
    CEA, DEN, Marcoule, BP 17171 - 30207 Bagnols-sur-Ce:e Cedex France
    2
    Institut Europeen des Membranes (IEM), UMR 5635 CNRS , Universite de Montpellier II , F-34095 Montpellier Cedex 5,
    France
    luc.schrivecea.Ir
    Heavy metals are poisons Ior the environment as they accumulate in sediments and enter into trophic chain.
    For eIIluents containing heavy metals a remediation step is required either Ior water re-use or release in the middle oI the
    process. The surIace treatment industry is concerned with such problems and has commissioned a two year study to evaluate
    the Ieasibility oI meeting the goal oI zero discharge.
    The nanoIiltration step aims at reducing salt content by roughly 90 at low energy cost when compared with reverse osmosis
    or evaporation. In our approach, we used NanoIlux simulations in order to better understand transport phenomena and then
    predict the perIormance oI commercial membranes, the goal being to suggest a Ilow chart. Either Ior synthetic or complex
    solutions, simulations can reliably describe membrane rejection perIormance. By changing the inputted pH value, simulated
    concentration characteristics or membrane perIormance helps us to predict the best operating conditions.
    Thanks to the NanoIlux soItware and its internal data base, we were able to predict that the ceramic membranes initially
    proposed were not well adapted because oI poor steric retention (electric repulsion, however, could be oI interest at very low
    concentration).
    For a typical industrial eIIluent rich in zinc and nickel salts and containing numerous secondary compounds, NanoIlux
    simulations helped us to select a suitable organic membrane Ior processing in a single step.
    Our current objective is to account Ior the particularities oI heavy metal ions, such as salt precipitation, that interIere with
    membrane perIormance.
    Wang, Z., Liu, G., Fan, Z., Yang, X., Wang, J., Wang, S. (2007). Experimental study on treatment oI electroplating wastewater
    by nanoIiltration. Journal oI membrane science. 305:185-195
    Palmeri, J., LeIebvre X. et al (2003). NanoIiltration Modeling using NanoIlux. Membrane News 61 :11-14
    -140-
    OF.2.11
    Treatment of phenol effluents coupling Fenton`s oxidation and nanofiltration
    X. Bernat
    1
    , A. Fortuny
    2
    , C. Bengoa
    1
    , F. Stber
    1
    , A. Fabregat
    1
    , J. Font
    1
    1
    Departament dEnginveria Quimica, ETSEQ, Universitat Rovira i Jirgili, Av. Pasos Catalans, 26, 43007 Tarragona,
    Catalunva, Spain.
    2
    Departament dEnginveria Quimica, EPSEJG, Universitat Politecnica de Catalunva, Av. Jictor Balaguer s/n, 08800
    Jilanova i la Geltru, Barcelona, Catalunva, Spain.
    xavier.bernaturv.cat
    Polluted waters are nowadays a major concern due to the necessity Ior preserving water as an essential Iactor Ior human
    development. Biological wastewater treatment plants (BWWTP`s) are Irequently used Ior treating polluted waters.
    Nevertheless, industrial eIIluents usually contain bioreIractory substances that cannot be directly treated in BWWTP`s. Thus, a
    pre-treatment has to be implemented to amend the polluted water so it can be subsequently sent to the BWWTP without
    causing operational problems. The Fenton process has shown to be an eIIicient way Ior partially oxidising phenol, a
    bioreIractory compound usually Iound in industrial wastewaters. The Fenton process is based on the Iormation oI hydroxyl
    radicals using both hydrogen peroxide (oxidant) and Ierrous ions (homogeneous catalyst). However, as iron ions continuously
    leave the reactor with the treated eIIluent, they enter the BWWTP and Iinally appear in the excess sludge. Thus, continuous
    addition oI iron ions causes an extra cost. Moreover, according to the legislation, it is mandatory to decrease the level oI iron
    dissolved in the eIIluent Irom the reactor to avoid problems in the biological treatment. In addition to these two drawbacks, as
    the goal oI Fenton process is not the total mineralisation oI the organic matter present in the initial wastewater, partial
    oxidation products are produced during the Fenton treatment. Some oI the phenol oxidation by-products, such as quinone-like
    compounds, have been Iound to be even more reIractory than the phenol itselI. Due to the above operating, environmental and
    economical problems, technical solutions must be designed to improve the overall treatment. The use oI nanoIiltration aIter the
    Fenton`s reaction is investigated Ior oxidising 2500 mg/L phenol solutions. Both Fenton`s oxidation and membrane separation
    perIormance are presented. On one hand, the eIIect oI the Fenton`s oxidation variables (oxidant and catalyst concentration) on
    the phenol oxidation eIIiciency, Total Organic Carbon (TOC) conversion and concentration oI oxidation by-products is
    examined. On the other hand, three commercial nanoIiltration membranes (NF, NF90 and NF270, manuIactured by Dow
    Filmtec) have been tested to Iilter the Fenton`s eIIluents in crossIlow continuous operating mode at 6 bar oI transmembrane
    pressure. The most eIIicient membrane was Iound to be NF90, which was then selected Ior perIorming the studies concerning
    the eIIect oI the Fenton`s operating variables on the membrane eIIiciency. Membrane eIIiciency was evaluated in terms oI
    phenol, iron, by-products and color retention as well as oI permeate Ilux decrease and Iouling. To test the membrane re-
    usability, Iour successive nanoIiltration runs were perIormed by using the same membrane and conditions, with a cleaning step
    using EDTA between Iiltration runs. The results demonstrate that membrane separation eIIiciency was not aIIected with use
    and permeate Ilux was restored aIter the cleaning steps or, which is the same, Iouling was eliminated.
    OF.2.12
    Old reverse osmosis modules in the future: solutions of reuse
    M. Pontie
    1,2
    , E. Ould Mohamedou
    3
    , J. Leparc
    4
    , S. de la Puente Gonzalez
    5
    , P. Jaouen
    2
    1
    GEPEA, UMR CNRS 6144, 2 Bd. Lavoisier, 49045 Angers cedex 01, France
    2
    GEPEA, UMR CNRS 6144, 37 Bd. de luniversite, CRTT BP406, 44602 Saint-Na:aire France
    3
    CRAER, Facultv of Science and Technologv , B.P. 5026, Nouakchott, Mauritania
    4
    JEOLIA WATER, Anfou-Recherche, Chemin de la Digue, BP 76, 78603, Maisons-Laffitte, France
    5
    CIT, Cebridn, 3, E-35003 Las Palmas de Gran Canaria, Canarv Islands, Spain
    maxime.pontieuniv-angers.Ir
    Water desalination processes have contributed to a better standard oI living in a number oI countries during the second halI oI
    the 20
    th
    century, Iollowing an increase in water demand Ior drinking purposes as well as industrial and agricultural uses.
    Membrane Iouling is a Irequent problem in most seawater reverse osmosis units, particularly when raw water is drawn Irom an
    open sea intake. Membranes tend to Ioul slowly, which makes it necessary to perIorm periodic cleanings with physical and
    chemical products, which in turn produce a decrease in the useIul liIetime oI the membranes.
    Actually the behaviour oI old reverses osmosis (RO) membranes Irom desalination seawater units are burned at the end oI their
    liIe. Tomorrow the main Iollowing way should be to reuse those RO membranes as nanoIiltration (NF) or ultraIiltration (UF)
    membranes, depending on the level oI their degradation. To evaluate the level oI degradation autopsy analysis were conducted,
    -141-
    as previously reported (Veza et al. 2003, Pontie et al., 2005). Old RO membranes came Irom the desalination plants oI Iwik
    and Teichitt in Mauritania. To supplement previously studies the presents work have put Iorward that the ageing oI the
    membrane was characterized by an increase oI hydraulic permeability and a Iall oI the retention oI salts. Our goal in the
    present work was to demonstrate Ior the Iirst time that a old RO membrane became a new nanoIiltration ones. Furthermore we
    studied the modiIication oI mass transIer beIore and aIter ageing, showing the apparition oI a convective part in the mass
    transIer. A preliminary study shows also an heterogeneous wear oI the membrane (the most important in the center), we
    chooses to spread this study in the complete module by comparing wear oI every membranes constituting the module. Thus we
    have showed that ageing was not only heterogeneous within the membrane but also within the module.
    Furthermore we developed a new and original approach to propose diIIerent applications oI the old materials constituting the
    old RO module Ior personal use at home i.e. geotextile and plant wall.
    Veza Jose M., Rodriguez-Gonzalez Juan J., 2003, Desalination 157, 65-72
    Pontie M., Rapenne S., Thekkedath A., Leparc J., Suty H., 2005, Desalination 181, 75-90
    Ould Mohamedou E., Pontie M, Jaouen P., 2009, Revue des Sciences de leau,, submitted
    OF.2.13
    Reverse osmosis solutions for reuse applications
    E. Chaumien, R. Boda, L. Boutarin
    Hvdranautics A Nitto Denko Companv, Nitto France, ZI de la Muette, 1 boulevard de la Muette, 95145 Garges-les-Gonesse
    (France)
    echaumienhydranautics.es
    The water resources are unIortunately shortening while the demand keeps rising. This is driving the water industry into Iinding
    new solutions to provide Ireshwater to always more numerous populations and industries. Fortunately solutions exist: one oI
    many is the wastewater reuse, where the eIIluent is treated with a high level oI perIormance in order to be reclaimed. Among
    other technological solutions, to 'clean this wastewater, come the membrane processes. The wastewater treatment with
    membranes is a challenge as this eIIluent presents most oI the time a high Iouling potential. The membrane industry needs to
    propose eIIicient processes, while limiting the Iouling potential oI the membranes.
    Reverse osmosis can cost-eIIectively reduce total dissolved solids, heavy metals, organics pollutants and others dissolved
    contaminants to the levels required by drinking or industry standards, nevertheless a consequent pre-treatment is most oI the
    time required prior wastewater RO.
    Hydranautics, one oI the world-leader in the membrane industry, has developed Ior many years membranes that are answering
    the demand Ior wastewater reclamation. Hydranautics` Low Fouling Composite (LFC) and Energy Saving PolyAmide (ESPA)
    technology is oIIering state oI the art membrane solutions Ior these applications, with both 'conventional (biology,
    decantation.) or membrane (MF,UF) pre-treatment oI the inIluent.
    This paper will present perIormance data results Irom existing installation equipped with such processes and will also present
    latest membranes development Ior such application.
    OF.2.14
    Cost effective treatment of drinking water production wastes
    B. Bozkaya-Schrotter, C. Daines-Martinez, P. Breant, J.C. Schrotter
    Water Research Centre of Jeolia, Chemin de la Digue, 78600 Maisons Laffitte, France
    jean-christophe.schrotterveolia.com
    Drinking water demand increases everyday with the increasing population oI the world. Naturally, this leads to an
    augmentation in the number oI drinking water production sites. At the same time, water scarcity is very real and with the
    global warming threats the need oI the protection oI the existing drinking water resources is more obvious than ever. In recent
    years, there has been an orientation to cheaper and greener processes. Water treatment market continuously seeks Ior processes
    that can produce high quality water with lower Iixed and operational costs and less waste production. NanoIiltration is one oI
    the techniques that can meet these multiple objectives. It is becoming a common technique Ior surIace water treatment Ior
    -142-
    drinking water production purposes. The waste oI these systems, so called 'concentrates that is the 15 to 25 oI the Ieed, is
    discharged back into the source or when it is possible, waste integration techniques apply, e.g. used as gray or irrigation water.
    Concentrate generally is composed oI the nanoIiltration Ieed components and anti-scaling agents and acids injected prior to
    Iiltration process to provide optimum operational conditions. It contains natural organic matter (NOM), micropollutants, e.g.
    pesticides, phosphonates and various salts typically 5 to 6 times more concentrated than in its Ieed. Hence, in order to protect
    existing drinking water resources, it is necessary to reduce the concentrations oI these components to keep the ecological
    balance oI the aquatic systems intact. The objective oI this project was to obtain a concentrate composition similar to
    nanoIiltration Ieed water quality by removing 75 to 85 oI pesticides, NOM and its alkalinity level. The eIIiciencies oI the
    cost eIIective processes were investigated Ior this purpose.
    The project Iirstly Iocused on pesticide elimination by conventional water treatment techniques|1|, i.e. adsorption, coagulation,
    ozonation - and the combination oI ozonation and adsorption processes carbozone`|2|. NOM elimination was then studied in
    the same system Iollowing the optimization oI the operational parameters. With combined adsorption (100 mg/L powdered
    activated carbon) and ozonation (6 mg/L ozone), between 90 and 100 pesticide and 45 COD elimination was achieved
    with 5 minute contact time. BiIoltration process was studied by using a laboratory scale continuous Iixed bed column.
    Alkalinity reduction was also investigated by combining conventional processes with basiIication.
    Previously, Ieasibility oI implementing a treatment scheme to improve the recovery Iactor and to reduce the concentrate
    volume was demonstrated. Following this idea, concentrate was Iurther concentrated by employing an additional nanoIiltration
    system. Treatment oI these Iinal solutions, 'concentrated concentrate samples, was then studied by testing aIorementioned
    techniques. Cost analysis was carried out Ior each process Ior similar component removal yield. Results oI this comparative
    study will be presented together with the cost analysis.
    1. Bozkaya-Schrotter, B.; Daines, C.; Lescourret, A.S.; Bignon, A.; Breant, P.; Schrotter, J.-C. (2008) Treatment oI Trace
    Organics in Membrane Concentrates I: Pesticide Elimination Water Sci. & Tech.: Water Supply, 8, 223-230.
    2. Jans, U.; Hoigne(1998) Activated carbon and carbon black catalyzed transIormation oI aqueous ozone into OH-radicals J.
    Ozone: Science and Engineering, 20, 67-90.
    OF.3.1
    Coastal seawater testing of an advanced microfiltration/reverse osmosis desalination
    demonstrator
    D. Nordham
    1
    , J. Heinzel
    1
    , B. Varnava
    2
    , M. Miller
    3
    , I. Peek
    1
    1
    Naval Surface Warfare Center, Carderock Division, Philadelphia. 5001 S. Broad St., Philadelphia, PA 19112 USA
    2
    Naval Facilities Engineering Service Center, 1100 23rd Street, Port Hueneme, CA 93043 USA
    3
    US Armv TARDEC, 1100 23rd Street, Port Hueneme, CA 93043 USA
    john.heinzelnavy.mil
    Under the OIIice oI Naval Research (ONR) Expeditionary Unit Water PuriIication (EUWP) Program, a reverse osmosis (RO)
    desalination demonstration plant was designed with Iuture operational considerations in mind primarily with increased
    operational capability as well as lower speciIic energy oI desalination and reduced size and weight compared to existing
    shipboard RO plants. Unlike current shipboard plants, this demonstration plant was designed to reliably operate in littoral and
    coastal seawaters with an advanced microIiltration membrane pretreatment system. Advanced RO membranes and energy
    recovery devices allowed production oI Ireshwater at 70 less cost and in a more compact unit than comparable shipboard RO
    plants. An endurance test was conducted on the demonstration plant with coastal seawater in which the advanced
    microIiltration system successIully ran Ior over 2,400 operating hours with minimal maintenance actions. The RO system
    produced superior quality product water Ior the entire test period. The development and testing oI this demonstration plant
    conducted under the EUWP Program will aid in Iuture Navy shipboard desalination system designs to be completed under an
    ONR Advanced Shipboard Desalination Future Naval Capability Program.
    -143-
    EUWP Generation 2 demonstration plant installed at NFESC, Port Hueneme, CA.
    OF.3.2
    New ultrafiltration membrane integrity test monitoring by magnetic susceptibility
    seawater membranes for desalination
    H. Guo
    1
    , Y. Wyart
    1
    , J. Perot
    2
    , F. Nauleau
    2
    and P. Moulin
    1
    1
    Universite Paul Ce:anne Aix Marseille, Laboratoire de Mecanique, Modelisation et Procedes Propres (M2P2 UMR-CNRS
    6181), Europole de lArbois, BP. 80, Batiment Laennec, Hall C, 13545 Aix en Provence Cedex 04, France
    2
    SAUR, 1 avenue Eugene Frevssinet, 78064 Saint Quentin En Yvelines Cedex
    yvan.wyartuniv-cezanne.Ir
    UltraIiltration membrane systems are widely used in drinking water treatment plants as an eIIective barrier against
    contaminants such as inorganic and organic particulates, bacteria, colloidal macromolecules, viruses, and so on. For this
    reason, membrane integrity monitoring is a very important issue Ior drinking water production, in addition to reachable Ilux,
    membrane retention and membrane permeability recovery. Current membrane integrity tests
    |1-3|
    (e.g. pressure decay test
    (PDT), diIIusive air Ilow (DAF) test particle counting, turbidity monitoring, ect.) are usually undertaken oII-line and are not
    suIIiciently sensitive to detect nanometric scale breaches. So it is very important to develop an alternative on-line detection test
    Ior quick, simple, and relatively inexpensive evaluation oI the UF membrane integrity Ior drinking water plant. Here, a new
    ultraIiltration membrane integrity test
    |4|
    is presented, based on the use oI magnetic particles (Fe
    3
    O
    4
    ) and measurement oI
    magnetic susceptibility. The advantages oI this new test are: on line during the Iiltration step, high sensibility (Dilution Iactor
    500 000), no inIluence oI MES or coagulant on the measurement, very low inIluence on membrane Iouling. Fe
    3
    O
    4
    magnetic
    particles were prepared by the coprecipitation oI Fe
    2
    and Fe
    3
    using ammonium hydroxide (NH
    4
    OH) as precipitating agent

    and
    then stabilized by the use oI meso-2, 3-Dimercapto-succinic acid (DMSA). The particles obtained were characterized by means
    oI granulometer and magnetic susceptibility meter. The size oI the particles is around 35 nm but can be controlled and Iixed
    between 20-200 nm with a good disparity. The Fe
    3
    O
    4
    concentration oI stabilized solution is around 1.2 g.L
    -1
    . A Norit
    membrane module oI 100 Iibers, whose cut-oII is 150 kDa, was used and a series oI pilot-scale experiments were implemented
    under the transmembrane pressure oI 0.2-0.3 bar. The results showed that the magnetic particles were completely retained by a
    perIect membrane whatever the Iiltration type: dead end or cross Ilow Iiltrations and no magnetic susceptibility was detected in
    the permeate. AIter a backwash the permeability oI the membrane was closed to the initial permeability. However, when even
    one Iiber was destroyed or broken in the module, magnetic susceptibility oI permeate could be detected instantaneously even at
    Ieed solution concentration as low as about 1.2 ppm, indicating that particles passed through the membrane due to damage
    (Figure 1). Whatever the time during the Iiltration step, this detection is validated. All these results imply that application oI
    magnetic particles as probes Ior monitoring membrane integrity and quickly detectable magnetic susceptibility will provide a
    reliable basis Ior developing a new eIIective on-line test Ior removal oI nano-scale particles, thus making it possible Ior
    membrane system to better satisIy regulatory requirements oI drinking water industry.
    -144-
    Figure 1: Variation oI the permeate Ilux and the magnetic susceptibility oI the permeate during the Iiltration step |dead end
    Iiltration, 1 oI Iiber broken|
    |1| W.T.Johnson, Desalination 113 (1997) 303-307
    |2| J.Naismith, Desalination 179 (2005) 25-30
    |3| S.Panglisch, U.Deiner, W.Dautzenberg, O.Kiepke, R.Gimbel, Desalination 119 (1998) 65-72
    |4| P. Moulin. Patent Number(s): FR2901607-A1; EP1862791-A2
    OF.3.3
    Three-stage concentrate treatment for brackish water reverse osmosis
    L. Greenlee
    1
    ,
    E. Barbot
    3
    , D. Lawler
    2
    , B. Freeman
    1
    , B. Marrot
    3
    , P. Moulin
    3

    1
    The Universitv of Texas at Austin, Department of Chemical Engineering, 1 Universitv, Station C0400 Austin, TX 78712, USA
    2
    The Universitv of Texas at Austin, Department of Civil Engineering, Universitv Station C1786 Austin, TX 78712, USA
    3
    Universite Paul Ce:anne Aix Marseille, Laboratoire de Mecanique, Modelisation et Procedes Propres (M2P2 UMR-CNRS
    6181), Europole de lArbois, BP. 80, Batiment Laennec, Hall C, 13545 Aix en Provence Cedex 04, France
    philippe.moulinuniv-cezanne.Ir
    Many regions lack suIIicient Iresh water resources and are turning to alternate resources, such as seawater or brackish water to
    sustain water needs. In particular, a growing number oI inland communities have both insuIIicient Iresh water and unused
    brackish water (500 10,000 mg.L
    -1
    total dissolved solids) resources. A key Iinancial and technical limitation to inland RO
    desalination is disposal oI the waste stream (concentrate); typically, 10 25 oI the inIluent volume becomes the RO
    concentrate stream. This waste volume is large when compared to the waste volume produced by traditional Iresh water
    treatment (less than 1). To decrease concentrate volume, the product recovery (volume oI product water per volume oI Ieed
    water) must be increased. However, salt precipitation occurs when recovery is increased; chemicals called antiscalants are
    dosed to the RO Ieed to help prevent precipitation, but antiscalants work within a limited range oI salt supersaturation. As
    recovery is increased, eventually precipitation will occur. This research Iocuses on the development oI a novel approach to
    increasing brackish water RO recovery: a process to treat the RO concentrate and increase overall recovery. The concentrate
    treatment process includes three stages: antiscalant degradation by ozonation, salt precipitation, and solid/liquid separation.
    This process was Iirst tested on synthetic brackish water, a simpliIied concentrate containing only Na

    , Cl
    -
    , HCO
    3
    -
    and Ca
    2
    .
    The eIIects oI other ions, such as Mg
    2
    , SO
    4
    2-
    , NO
    3
    -
    , Ba
    2
    and Fe
    3
    , on the treatment process were also investigated.

    Several
    oxidation parameters, such as ozonation time and antiscalant concentration, were varied. Ozonation times oI 1, 10, and 30
    minutes were tested. For the Iirst antiscalant tested (amino tri(methylene phosphonic acid), or AMPA) and the simpliIied
    concentrate, results show increased calcium precipitation Ior all ozonation times and all antiscalant concentrations (4 85
    mg.L
    -1
    ). The simpliIied concentrate with 85 mg.L
    -1
    AMPA, treated with only 1 minute oI ozonation and subsequent
    precipitation at pH 10.5 Ior 1 hour, had a Iinal dissolved calcium concentration oI 5.2 mg.L
    -1
    Ca
    2
    . In comparison, the same
    precipitated solution with no antiscalant resulted in a Iinal dissolved calcium concentration oI 3.7 mg.L
    -1
    , while the same
    precipitated solution with 85 mg.L
    -1
    AMPA and no prior ozonation resulted in a Iinal dissolved calcium concentration oI 77
    mg.L
    -1
    . Salt precipitation was perIormed using model synthetic concentrates and several antiscalant types to evaluate the
    precipitation oI calcium carbonate. The model concentrate is based on data Irom a groundwater source in Arizona, assuming an
    80 recovery and 100 ion retention. First, the precipitation oI calcium carbonate as a Iunction oI pH was determined Ior
    solutions with a phosphonate antiscalant and with no antiscalant. For the model concentrate used (at pH 10.5), samples without
    antiscalant resulted in 87 calcium precipitation, while, as expected, samples with antiscalant showed 0 calcium
    precipitation. This result corresponds to the recommended SI limit Ior successIul precipitation prevention by an antiscalant.
    -145-
    Subsequent experiments with varied water composition showed a decrease in calcium precipitation with the addition oI
    magnesium and sulIate. The eIIect oI antiscalants on CaCO
    3
    precipitation was also evaluated through particle size and particle
    number distributions using a laser particle counter. Finally, dead end Iiltration (MWCO 0.1 micrometers, Millipore
    nitrocellulose membranes) was perIormed to compare the Iouling potential oI the precipitated solutions as a Iunction oI water
    composition, antiscalant type, and antiscalant concentration. The simpliIied concentrate, containing NaCl, NaHCO
    3
    , and
    CaCl
    2
    *2H
    2
    O was Iirst tested. The water composition was then changed by separately adding MgCl
    2
    *6H
    2
    O and Na
    2
    SO
    4
    . Results
    revealed diIIerences between antiscalants and water compositions. Two antiscalants showed Ilux decreases oI approximately
    30 over a period oI 7 minutes Ior the simpliIied concentrate, while the same two antiscalants showed only a 19 Ilux
    decrease when magnesium was added to the simpliIied concentrate. For the Iour antiscalants tested, there was no consistent
    relationship between antiscalant concentration and membrane Ilux. For all antiscalants tested, while a greater antiscalant
    concentration resulted in less calcium precipitated, a greater antiscalant concentration did not result in reduced permeate Ilux
    decline. Subsequent tests on solutions containing only antiscalant and deionized water indicated membrane Iouling occurred, at
    least in part, through antiscalant adsorption onto the membrane surIace.
    OF.3.4
    Study of the effects of defects in ultrafiltration membranes on the log removal value
    (LRV) of MS2 and the molecular weight cut-off (MWCO)
    G. Pierre
    1
    , A. Furiga
    2
    , C. Roques
    2
    , S. Rapenne
    3
    , J.-C. Schrotter
    3
    , P. Sauvade
    4
    , O. Lorain
    5
    , P. Aimar
    1
    ,
    C. Causserand
    1
    1
    Laboratoire de Genie Chimique (UMR 5503), Universite de Toulouse, Universite Paul Sabatier, 31062 Toulouse cedex 09,
    France
    2
    Equipe Adhesion Bacterienne et Formation de Biofilms (EA 3036 - IFR 31), Universite Paul Sabatier, Toulouse, France
    3
    Jeolia Environnement - Anfou Recherche, Chemin de la Digue, BP 76, 78603 Maisons-Laffitte Cedex - France
    4
    Degremont Technologies Aquasource, 20 avenue Didier Daurat, BP 64050, 31029 Toulouse - France
    5
    Polvmem, Impasse de Palavre, 31100 Toulouse - France
    causserachimie.ups-tlse.Ir
    The aim oI this study was to evaluate how deIects in a membrane surIace can aIIect the log removal value (LRV) oI MS2
    bacteriophage and the molecular weight cut-oII (MWCO) deduced Irom measurement oI retention oI synthetic polymers
    (tracers). These two parameters are important criteria Ior the selection oI ultraIiltration membranes with regard to selectivity
    and microorganisms rejection capacity.
    Tests were conducted with ultraIiltration hollow Iiber membranes. The selected membranes are made oI polyethersulIone or
    cellulose acetate with internal/ external conIiguration and various molecular weight cut-oIIs, respectively oI 200 and 100 KD.
    Experiments were conducted Iirst with virgin membrane, secondly with deIect membrane on which a hole oI 25 m in
    diameter has been voluntary done by Iemto second laser to test the sensitivity oI the method to the presence oI a deIect. Both
    series were perIormed in cross Ilow Iiltration conditions.
    To determine the log removal value, the virus selected is the bacteriophage MS2 oIten chosen by membrane manuIacturers to
    challenge membranes . A Ieed suspension oI viruses at a concentration 10
    8
    PFU/mL was used in various media (PBS, Milli-Q
    water). The suspension was sampled in permeate and retentate and a counting carried out in order to determine the virus
    concentrations using two diIIerent methods: by plaque Iorming unit (PFU) method, which can reveal only inIectious viruses
    and by real-time RT-PCR method which detects the total number oI viruses regardless oI their inIectivity.
    To determine the apparent MWCO, a mixture oI dextran molecules is used. The determination oI the concentrations necessary
    to the calculation oI the rate oI retention is carried out by steric chromatography oI exclusion (SEC) Iollowed by an analysis by
    reIractometry. The characteristic retention curve is obtained by plotting Ior each tracer molecule the partial rejection
    coeIIicient. The molecular weight cut-oII is then deduced Irom this curve at 90 retention.
    The results obtained in term oI log removal value (LRV) and oI molecular weight cut-oII (MWCO) were compared beIore and
    aIter the membrane integrity was altered by perIorating its surIace. This study provides guidelines to see whether the
    parameters classically used to characterize membranes are sensitive to the presence oI deIects in the membrane surIace.
    -146-
    OF.3.5
    Theoretical evaluation of a thermopervaporation of water vapor
    R. Noble
    1
    , P. Aptel
    2,3
    , J.-C. Remigy
    2,3
    , P. Aimar
    2,3
    1
    Universitv of Colorado, Chemical Engineering, Dept.UCB 424, Boulder, CO 8030, USA
    2
    Universite de Toulouse , INPT, UPS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    3
    CNRS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    aimarchimie.ups-tlse.Ir
    One approach to improve polymeric membrane Ilux and selectivity is the use oI additional driving Iorces. For water separation
    and puriIication, traditional membrane separation methods such as reverse osmosis or ultraIiltration use a pressure gradient.
    Pervaporation, which is based on dense membranes, utilizes an activity gradient. This gradient is created using a pressure
    gradient combined with a phase change to enhance perIormance. In this case, the permeate is at vacuum and must be
    condensed at low temperature Ior recovery.
    An alternative that would allow the permeate to be recovered at ambient temperature is the use oI a temperature gradient as the
    main driving Iorce instead oI a pressure gradient. The Ieed is heated and the thermal diIIerence provides the additional driving
    Iorce. The advantage is that the permeate is recovered at ambient temperature.
    In order to assess the potential oI such a concept Ior the production oI drinking water, a model describing mass and heat
    transIers in a system is required. Using vapor permeabilities oI membranes Iound in the literature, and thermal conductances oI
    materials, we identiIy the major transIer resistances, the modeling should be suIIiciently detailed to identiIy the major transIer
    resistances.
    In a second step, we give an estimation oI the potential improvements, thanks to the technical changes should let us predict the
    capability oI such a system in terms oI drinking water production. The incorporation oI the important membrane properties
    allows one to select the best membrane material and membrane stack Ior a given application and operating conditions.
    This approach will be outlined in this presentation. Initial results will be provided.
    OF.3.6
    Electrochemical detection of original virus surrogates: a new method for the inline
    characterisation of virus retention in membrane processes
    L. Soussan, C. Guigui, S. AlIenore, S. Mathe, C. Cabassud
    Universite de Toulouse, INSA, LISBP, 135 Avenue de Rangueil, F-31077 Toulouse, France
    INRA, UMR792 Ingenierie des Svstemes Biologiques et des Procedes, F-31400 Toulouse, France
    CNRS, UMR5504, F-31400 Toulouse, France
    Laurence.Soussaninsa-toulouse.Ir
    Membrane processes have been developed in drinking water production Ior their ability to remove particles and
    microorganisms, notably viruses. However in some cases (ageing, damage or Iouling oI the membranes), some viruses might
    not be retained and pass through the membranes. A key problem Ior water end-users and Ior membrane manuIacturers lies thus
    in the inline detection oI viruses during the Iiltration process.
    Viruses can be quantiIied in the permeate by current methods (like direct enumeration by plate counting, quantitative PCR,
    Ilow cytometry.) that are not suIIiciently rapid and/or applicable inline and/or representative oI the Iiltered volumes to study
    virus retention dynamics during the Iiltration process. In this work, a new method allowing to detect virus surrogates more
    easily and rapidly (in one step) has been developed. This original method is based on the use oI new virus surrogates that can
    be detected by amperometry.
    These virus surrogates are modiIied bacteriophages obtained by conjugation oI enzymatic probes to MS2 bacteriophages
    (which are among the smallest non-pathogenic bacteria viruses). These new virus surrogates used as tracers were developed in
    order to have a similar Iiltration behaviour than real viruses. In this context, both size (average diameter), biochemical
    properties and density are comparable to these oI native viruses. The reproducibility oI the synthesis protocol and the
    quantitative characterisation oI these new tracers have been studied.
    The major interest oI these new tracers lies in the easy and rapid detection oI their enzymatic activity that can be made in one
    step by spectrophotometric, Iluorimetric and amperometric techniques. The amperometric detection was chosen Ior its higher
    sensitivity and its better representativeness oI the analysed volumes (more than a Iactor 100). In this context, the
    amperometric quantitation oI tracers requires less than 20 minutes Ior analysis, which makes possible dynamic and inline
    studies. The development oI this electrochemical method was Iirst validated by measuring the enzymatic activity oI the
    -147-
    enzyme alone by colorimetry and amperometry. This amperometric detection was also validated Ior high tracer concentrations
    and will be used in a smaller concentration area.
    First Iiltration experiments were conducted on a MF/UF Ilat sheet membrane to characterise the retention by injecting by step
    tracers in a clean water Ieed, then analysing both the concentrate and the permeate. In particular, this study allowed to check
    the reproducibility oI the method in given Iiltration operating conditions. A 4 log tracer removal was observed. The method is
    now available and will be used to characterise the retention variations oI membrane systems as a Iunction oI Iouling state and
    Iiltration conditions.
    The French Agence Nationale de la Recherche is acknowledged Ior supporting this study in the Irame oI the PRECOOD
    program.
    OF.3.7
    Removal of norovirus by a coagulation-ceramic MF hybrid system
    T. Matsushita , N. Shirasaki, A. Oshiba, T. Urasaki, Y. Matsui, K, Ohno
    Graduate School of Engineering, Hokkaido Universitv, N13W8, Sapporo 060-8628, Japan
    taku-meng.hokudai.ac.jp
    Background
    Norovirus is responsible Ior large part oI all nonbacterial acute epidemic outbreaks oI gastroenteritis in humans. Because the
    norovirus does not grow in cell or organ culture, it is impossible to conduct the removal experiments by dosing artiIicially
    propagated virus to laboratory-scale plants, which is one oI widely-accepted methods when using bacteriophages as a model
    virus. Accordingly, the removal oI norovirus during the drinking water treatment process still remains unclear, even though its
    behavior in the process is socially oI great importance.
    In the present study, we applied the artiIicially-expressed capsid protein oI norovirus to the investigation oI virus removal
    during a coagulation-ceramic MF hybrid system. The capsid protein oI norovirus spontaneously selI-assembles into virus like
    particles (VLPs) when expressed in insect cells inIected with a recombinant baculovirus containing the gene encoding the
    capsid protein. Because the norovirus VLPs (NV-VLPs) are the similar to native norovirus particles morphologically and
    antigenically, the NV-VLPs are expected to behave equally as the native norovirus during the treatment process. This is the
    Iirst attempt to apply the NV-VLPs Ior investigating the removal oI norovirus in drinking water treatment.
    Materials and methods
    Subgenomic cDNA Iragments oI norovirus (AB042808, GI/4, Chiba407/87/JP) genome were artiIicially synthesized. The
    Iragments contained the entire second and third open reading Irame oI the norovirus genome. The cDNA was subcloned into a
    baculovirus transIer vector, and then the vector was transIected into silkworm cells. The expressed NV-VLPs were separated
    Irom the cell lysate by centriIugation and dialysis.
    River water spiked with NV-VLPs (10
    10
    VLPs/mL) as well as bacteriophages Q and MS2 (10
    8
    pIu/mL) was treated with
    PACl (polyaluminum chloride, dosing rate: 0.54, 1.08 and 1.62 mg-Al/L) Ior a coagulation process, and then continuously
    Iiltered through a ceramic MF (nominal pore size, 0.1 m) Ior 2 h in dead-end mode without any backwashing. NV-VLPs and
    bacteriophages were quantiIied with ELISA method and RT-PCR method with Iiltration time, respectively.
    Results and ongoing research
    Concentrations oI NV-VLPs in MF permeate were less than the detection limit when the system was operated with more than
    1.08 mg-Al/L oI PACl dosing, indicating that more than 3-log reduction was achieved Ior NV-VLPs. It was the Iirst time that
    the removal perIormance oI norovirus during the coagulation-MF hybrid system was experimentally evaluated. Two-log
    reduction was observed Ior NV-VLPs when the system was operated with 0.54 mg-Al/L oI PACl dosing, which was larger
    than that oI bacteriophages Q and MS2. This means that these bacteriophages may be a possible indicator Ior norovirus
    during this system. Now we are trying to detect lower level oI NV-VLPs by concentrating samples or achieving more sensitive
    ELISA method, which will enable us to ensure more than 4-log reduction oI NV-VLPs during the coagulation-MF hybrid
    system (i.e. US EPA recommendation). Experiments with alum, Ierric chloride and polysilicato iron as a coagulant are also
    now being conducted. These additional up-to-date results will be presented at the conIerence.
    -148-
    OF.3.8
    High performance seawater membranes for desalination
    L. Boutarin, R. Boda, E. Chaumien
    Hvdranautics A Nitto Denko Companv, 401 Jones Road, Oceanside, CA 92058, United States
    www.membranes.com
    lboutarinhydranautics.es
    Desalination oI seawater using Reverse Osmosis (RO) membranes is now used worldwide to provide Ireshwater in locations
    where conventional resources are under stress. With increasing seawater desalination market, end-users are expecting Irom
    new desalination plants to be energy-eIIicient in order to reduce as much as possible the environmental Iootprint oI membrane
    desalination process.
    ThereIore, the RO membranes manuIacturers are challenged in developing new membranes allowing high salt rejection, high
    permeate Ilux and lower operating pressure requirements. Being present in the RO industry since 1970, Hydranautics has
    developed its latest seawater RO membrane elements which are designed to combine superior salts rejection, high permeate
    Ilow and low operating pressures. Several desalination projects were awarded recently to Hydranautics thanks to application oI
    newly developed Seawater Composite (SWC) elements. This paper intends to present perIormance data oI new SWC elements
    and the beneIits they bring to the desalination industry. It will also Iocus on the latest technologic improvements applied on the
    last generation oI membranes which are currently being installed in many new desalination plants around the world. Paper will
    also review the latest development in SW membranes technology.
    OF.4.1
    Solvent resistant nanofiltration: an efficient and sustainable strategy for product
    purification and recovery of catalysts in click chemistry reactions
    A. Cano-Odena
    1
    , P. Vandezande
    1,2
    , D. Fournier
    3,4
    , W. Van Camp
    3
    , F. E. Du Prez
    3
    , I. F. J. Vankelecom
    1

    1
    Centre for Surface Chemistrv and Catalvsis, Facultv BIW, K.U.Leuven, Kasteelpark Arenberg 23 box 2461, B-3001 Leuven,
    Belgium
    2
    Flemish Institute for Technological Research (JITO), Boeretang 200, B-2400 Mol, Belgium
    3
    Department of Organic Chemistrv, Polvmer Chemistrv Research Group, Ghent Universitv, Krifgslaan 281 S4, B-9000 Gent,
    Belgium
    4
    Laboratoire de Chimie Organique et Macromoleculaire (UMR 8009), Universite des Sciences et Technologies de Lille,
    Batiment C6, 59655 Jilleneuve dAscq Cedex
    ivo.vankelecombiw.kuleuven.be
    Cu(I) catalyzed Huisgen 1,3 dipolar cycloadditions oI azides and terminal alkynes, resulting in the Iormation oI molecules
    through heteroatom C-X-C links |1|, also known as "click chemistry reactions, have received increased attention as they
    provide an easy synthetic tool to couple two compounds Ior many existing and emerging Iields (macromolecular engineering
    and synthesis oI biopolymer hybrids). Due to their intrinsic Ieatures (high selectivity, Iunctional group tolerance, applicability
    under mild reaction conditions, quantitative yields) they have a wide range oI applications in polymer science (end-
    Iunctionalization, block copolymers, hyperbranched and dendritic macromolecules, star shaped polymers) |2|. However, it is
    essential to separate the products Irom the ligand-stabilized Cu (I) catalysts. The presence oI Cu(I) catalyst aIter reaction is a
    disadvantage in order to IullIill the required speciIications Ior their application in e.g. the pharmaceutical industry. Currently
    used post-puriIication methods Ior catalyst separation comprise the extraction with aqueous solutions oI complexating agents,
    the use oI ion-exchange resins, or percolation oI product solutions through silica or alumina columns. The use oI
    heterogeneous catalysts results in slower reaction rates because these ligands do not match the optimum steric and electronic
    requirements Ior ligands applied in homogeneous click reactions |3|.
    Solvent Resistant NanoIiltration (SRNF), appears as a Ieasible and promising alternative permitting the use oI homogeneous
    catalysts and solving the problems oI the presence oI the catalyst aIter reaction. The good long-term chemical stability and
    perIormance oI the membrane is a crucial issue because many click reactions are carried out in high-boiling, polar aprotic
    solvents such as DMF or THF. Crosslinked Polyimide-based membranes |4| are excellent candidates Ior this study, since it is
    possible to Iine tune their MWCO by changing the membrane synthesis parameters. These membranes have been used
    successIully, by carrying out 5 diaIiltrations, in the separation oI the Cu (I) catalyst Irom the click product decreasing the level
    oI Cu (I) below 5 ppm. In contrast to earlier SRNF/catalysis studies where the catalyst was always retained |5|, in the present
    -149-
    work, product puriIication and the permeation oI the catalyst through a membrane has been possible, resulting in the successIul
    simultaneous re-utilization oI the catalyst and puriIication oI the product.
    |1| H. C. Kolb et al. Angew. Chem. Int. Ed. 2001, 40, 2004.
    |2| D. Fournier et al. Chem Soc. Rev., 2007, 36, 1369.
    |3| L. Bonami et al. DOI 10.1002/marc.200800607.
    |4| K. Vanherck et al. J. Membr. Sci. 2008, 320, 468.
    |5| P. Vandezande et al, Chem. Soc. Rev. 2008, 37, 365.
    OF.4.2
    Composite hollow fibres membranes for organic solvent nanofiltration (OSN)
    S.M. Dutczak
    1
    , I. Struzynska
    2
    , M.W.J. Luiten-Olieman
    2
    , D. Stamatialis
    1
    , L. Winnubst
    2
    , M. Wessling
    1

    1
    Membrane Technologv Group (MTG), Facultv of Science and Technologv, Mesa Institute, Universitv of Twente P.O. Box
    217, 7500 AE Enschede, The Netherlands
    2
    Inorganic Membranes/Membrane Technologv Group, Facultv of Science and Technologv, Mesa Institute, IMPACT
    Universitv of Twente, P.O. Box 217, 7500 AE Enschede, The Netherlands
    s.m.dutczaktnw.utwente.nl
    Organic solvent nanoIiltration (OSN) is an energy-eIIicient separation process with high potential in many industries, ranging
    Irom petro-chemistry to pharmaceuticals. Until now research and industrial applications oI NF have been mainly Iocused on
    water systems. Most oI commercial OSN modules are based on polymeric membranes which are exclusively in a Ilat sheet
    Iormat. Moreover, in strong organic solvents they oIten have swelling problems, leading to loss oI selectivity .
    In this work, we prepare and study hollow Iibre membranes made oI various materials with better chemical stability, higher
    eIIiciency and easiness oI scaling up.
    Figure 1 Polymeric OSN hollow Iibre membranes. Figure 2 Composite OSN hollow Iibre membrane.
    Two approaches to obtain stable NF hollow Iibre membranes are investigated:
    E.1.Integrally skinned polymeric HF membrane based on polyimide polymers (Fig.1).
    E.2.Composite HF membrane comprising oI an inorganic support and selective polymeric top layer (Fig. 2).
    All membranes are systematically investigated including: permeation experiments (permeance / MWCO) using a high pressure
    set-up ; study oI morphology using SEM imaging and study oI their mechanical properties (tensile strength tests). With both
    approaches; we obtain HF membranes with excellent stability in various organic solvents such as toluene, ethanol, DMSO,
    hexane or DMF and good separation perIormance.
    We would like to acknowledge STW Ior Iinancial support oI this project.
    -150-
    OF.4.3
    Solvent filtration ~matrix: assessing the potential of ceramic nanofiltration
    membranes in solvent environments
    P. Vandezande, K. Wyns, V. Meynen, A. Buekenhoudt
    Flemish Institute for Technological Research (JITO), Unit Separation and Conversion Technologv, Boeretang 200, B-2400
    Mol, Belgium
    pieter.vandezandevito.be
    Solvent resistant nanoIiltration (SRNF) is a relatively new, emerging technology that allows to separate non-aqueous mixtures
    on a molecular level by simply applying a pressure gradient over a selective membrane |1|. Environmental concerns and rising
    energy prices, new technical achievements and the availability oI more and better solvent-stable membranes explain the
    steadily increasing interest oI process engineers in SRNF as a sustainable alternative Ior conventional energy-intensive,
    solvent-consuming or waste-generating separation processes. SRNF particularly holds an enormous potential in the process
    industry where organic solvents are widely applied. With a molecular weight cut-oII (MWCO) between 200 and 1000 Da, a
    range covering a large number oI industrially relevant molecules, SRNF membranes can Ior example be applied to transIer
    active pharmaceutical compounds Irom one solvent to another, recuperate and recycle homogeneous catalysts, puriIy edible
    oils, separate oligomer/polymer mixtures, remove metals Irom solvent waste streams, or Iractionate reIinery streams. Despite
    this huge potential and the clear ecological/economical beneIits, SRNF can not be considered as proven technology yet.
    Several important challenges remain, such as the small number oI commercial membranes and modules and the lack oI
    straightIorward membrane selection guidelines. In view oI the expected market growth, a clear need exists to develop more
    robust and well-characterized high-perIormance membranes with broad solvent stability.
    The complex and application-speciIic interactions between membrane, solvent and solute (i.e. membrane swelling, solute
    adsorption, solvent-dependent solute properties), the lack oI a universal solvent/solute-independent MWCO characterization
    method, and the poorly understood SRNF transport mechanism make it diIIicult to select a proper membrane Ior a speciIic
    application and predict its perIormance. ThereIore, we set up a solvent Iiltration 'matrix in which several (commercial as well
    as in house Iunctionalized/hydrophobized) ceramic SRNF membranes were systematically screened in a series oI Ieed
    mixtures comprising model solutes (polyethylene glycols, polystyrene oligomers, trialkylamines, etc.) in a broad range oI
    industrially relevant solvents (EtOH, ethyl acetate, acetonitrile, THF, DMF, DCM, toluene, heptane, etc.). Thanks to their
    chemical, physical and mechanical stability, the use oI ceramic membranes in solvent streams is obviously advantageous. The
    membranes were tested at diIIerent pressures and temperatures in a cross-Ilow Iiltration set-up. Fluxes were automatically
    recorded, while retentions were uniIormly determined using a laboratory-developed gel permeation chromatography based
    analysis method. The tendencies in the 'matrix will be tentatively interpreted in terms oI physico-chemical parameters, while
    the sizeable dataset will also be modeled to describe the transport through the tested membranes.
    |1| P. Vandezande, L.E.M. Gevers, I.F.J. Vankelecom, Solvent resistant nanoIiltration: separating on a molecular level, Chem.
    Soc. Rev., 2008, 37, 365-405.
    OF.4.4
    PEEKWC membranes for treatment of organic solvent solutions
    M. G. Buonomenna
    1
    , G. Golemme
    1,2
    , J. C. Jansen
    2
    , E. Drioli
    1,2
    1
    Dipartimento di Ingegneria Chimica e dei Materiali, Universita della Calabria, and Consor:io INSTM, Jia Pietro Bucci
    45A, I-87030 Rende (CS), Italv
    2
    ITM-CNR, Istituto per la Tecnologia delle Membrane, Jia Pietro Bucci 17C, I-87030 Rende (CS), Italv
    mg.buonomennaitm.cnr.it
    Separation processes are oI utmost importance Ior the pharmaceutical industry: organic syntheses involve products with high
    added value that have to be separated Irom organic solvents |1|. The use oI polymeric membranes Ior separations in organic
    solvents has been suggested by a growing number oI authors |2|.
    In this work we report on the use oI PEEKWC Ilat membranes Ior retention oI compounds soluble in organic solvents with
    MW in the range oI 300-1100 Da. PEEKWC is a thermally stable polymer with solvent resistance and excellent mechanical
    properties. Isopropanol (IPA) has been chosen as organic solvent because it one oI most Irequently used solvents Ior
    pharmaceutical processes. The membranes have been prepared by means oI dry-wet phase inversion |3|.
    -151-
    For a Iirst screening, two organic compounds, diIIerent in molecular weight and charge, both soluble in IPA, have been
    selected. They are Rose Bengal (MW 1017 Da) and SaIranine (MW 350 Da), negatively and positively charged, respectively.
    The solute rejection and the solvent Ilux Ior diIIerent PEEKWC membranes characterized by isotropic macrovoids-Iree
    morphology have been investigated. Two Iactors have been Iound crucial Ior the observed retention: swelling oI the polymeric
    matrix and charge (positive or negative) oI the compound.
    In Iigure 1, the retentions in IPA and water (as reIerence) Ior both Rose Bengal and SaIranine have been reported operating at
    8 bar oI transmembrane pressure using membrane M1. It is evident a nearly complete rejection Ior negatively charged Rose
    Bengal in IPA (99.8 ) higher than that observed in water (86). This diIIerence in retentions is due to the swelling oI the
    polymeric matrix which occurs in IPA (
    PEEKWC
    20.8 (MPa)
    1/2
    ,
    IPA
    23.5 (MPa)
    1/2
    ,
    H2O
    47.9 (MPa)
    1/2
    ), decreasing the
    membrane pore size. An opposite relation has been Iound with the smaller SaIranine: retentions in water and IPA were 71
    and 52, respectively. In this case, repulsion between the positively charged molecule and the polymeric matrix occurs,
    phenomenon which becomes important in water, better than IPA to stabilize ionic species.
    Figure 1-Retention oI Rose Bengal and SaIranine in IPA and H
    2
    O by using membrane M1
    |1| J. Geens, B. De Witte, B. Van de Bruggen, Sep. Sci. and Technol., 2007, 42, 243549.
    |2| A.I. SchIer, A.G. Fane, T.D. Waite. NanoIiltration-Principles and Applications. Elsevier: Amsterdam (NL), 2004.
    |3| M.G. Buonomenna, A.Gordano, E.Drioli, Eur. Polym. J., 2008, 44, 20519.
    OF.4.5
    Batchwise and continuous organophilic nanofiltration of Grubbs type olefin
    metathesis catalysts
    K. Ebert, K. Buhr
    GKSS Research Centre Geesthacht GmbH, Institute of Polvmer Research, Max-Planck-Str. 1, 21502 Geesthacht (Germanv)
    katrin.ebertgkss.de
    OleIin metathesis is a very important synthetic transIormation, unIortunately it oIten requires high catalyst loadings resulting
    in considerable ruthenium (Ru) contamination oI the reaction products. Apart Irom the obvious economic disadvantages
    associated with this, low thresholds Ior the contamination oI organic products with toxic metals may require elaborate
    puriIication techniques to meet the speciIied limits.
    In our approach we have studied the retention oI Grubbs type oleIin metathesis catalysts by solvent resistant nanoIiltration.
    The catalysts used in this study are characterised by a combination oI high activity and increased molecular mass oI the Ru
    complex in order to enable eIIicient separation oI the catalysts Irom the reaction products. The membranes used Ior the
    nanoIiltration experiments are composite membranes consisting oI a porous poly(acrylonitrile) support coated with a thin
    dense layer oI chemically and radiationally crosslinked poly(dimethyl siloxane).
    In all batch experiments virtually quantitative conversion (~99 ) oI the reactants to the desired products was observed.
    Following the Iull conversion oI the reactants, the reaction mixture underwent nanoIiltration, the permeate solvent was
    evaporated and the remaining product analyzed Ior Ru with ICP-OES. For all batch Iiltration experiments the catalyst retention
    exceeds 99 - 99.5 . The amount oI Ru in the permeate always remains below the ICP-OES detection limit.
    In the continuous mode three samples were taken, Ior each oI them the Ieed during 45 minutes was collected and analysed with
    ICP-OES. The total amount oI Ru retained by the membranes during the Iull duration oI the experiment was Iound to be
    97.6 .
    -152-
    The conversion in the membrane reactor reached a maximum oI approximately 37 aIter about 120 minutes. AIter that time
    the conversion decreased to a Iinal value oI about 6 aIter 500 minutes. The reason Ior the shape oI the conversion curve is
    not clear yet, but it is likely the the increasing ethene concentration in the reaction volume leads to a slow down oI the catalytic
    conversion. Nonetheless the total turnover number during the Iirst 500 minutes is 866 mol product per mol catalyst.
    OF.4.6
    Processing of a-protic solvents with NF membranes
    F.P. Cuperus, I.M. Wienk
    SolSep B.J., St. Eustatius 65, 7333 NW Apeldoorn, The Netherlands
    cuperussolsep.com
    In many chemical processes strong solvents like chlorinated solvents or a-protic solvents play an important role. Despite
    eIIorts to substitute these media by more environment-Iriendly alternatives they oIten cannot be replaced straigthIorwardly or
    at least not without altering the (down-stream) process. Implementation oI membrane technology provides new approaches to
    the use oI solvents. Re-use, also oI highly boiling solvents, becomes technically and economically Ieasible. The main
    premisses are solvent resistance oI the membranes and robustness oI the elements.
    We will discuss work on nanoIiltration oI strong aprotics (THF, NMP) and chlorinated solvent reclaim and re-use using newly
    developed polymeric Solsep membranes.
    Fig. 1 : SolSep Robust Membrane Element
    OF.4.7
    Keynote: New materials and approaches for solvent resistant nanofiltration (SRNF)
    I. Vankelecom
    Centrum voor Oppervlaktechemie en Katalvse (COK), Dept. MS, Faculteit Bio-ingenieurswetenschappen, K.U.Leuven,
    Postbus 2461, Kasteelpark Arenberg 23, 3001 Leuven, Belgium.
    Ivo.Vankelecombiw.kuleuven.be
    SRNF allows to separate organic mixture down to the molecular level. Molecular weight cut-oII (MWCO) values vary
    between 200-1000 Da and thus allow Ior instance the removal oI homogeneous catalysts Irom their reaction mixture, isolation
    oI triglycerides Irom their extraction solvents, Iractionation oI oligomers and so on. Within less than a decade, the technique
    has Iound its way into several industrial processes already. This presentation will Iocus on both new materials and new
    approaches that were recently developed at the COK.
    Based on the large impact in other research Iields, like semi-conductors or catalysts, high-throughput techniques were
    introduced in membrane technologies. New equipment was designed to allow synthesis, casting and testing oI several
    membranes at the same time. This was not only time saving, but also gave access to combinatorial synthesis oI membranes. In
    combinatorial synthesis, search algorithms are typically applied to optimize the composition oI a membrane Ior a given
    separation. Several SRNF-membranes were already prepared that way, clearly outperIorming the currently existing
    membranes.
    In an attempt to Iind a uniIorm method to characterize SRNF-membranes, an HPLC-ELSD-method (evaporative light
    scattering detector) was developed to allow accurate determination oI retention oI a set oI oligomers Irom a variety oI Ieed
    solvents and translate them into a MWCO-value.
    Among the new membranes developed at COK, several aimed at increasing the stability oI SRNF-membranes to allow
    applications in more challenging conditions, like in aprotic or strongly swelling solvents. For that purpose, zeolites and metal
    -153-
    organic Irameworks have been incorporated in silicone rubber membranes. By creating hollow spheres with a zeolite-like shell,
    Iluxes through these mixed matrix membranes could be increased drastically, while keeping the selectivity intact.
    Several types oI selI-assembly membranes were also developed and successIully tested in SRNF. They include polyelectrolyte
    complexes, which create a very thin (tens oI nanometers), but stable and highly charged membrane material, thus retaining
    charged solutes well.
    Another type oI membrane is based on the use oI diblock-copolymers (typically polystyrene-polyethylene oxide), which selI-
    assemble under the appropriate conditions into a biphasic polymer structure with well-deIined pores consisting oI one polymer
    and a continuous phase consisting oI the other polymer. The continuous polystyrene phase could be easily crosslinked with
    UV, leaving an SRNF-membrane stable in all solvents.
    OF.5.1
    CO
    2
    selective membranes for coal power plants
    S. Shishatskiy, J.R. Pauls, S.P. Nunes, K.-V. Peinemann
    Institute of Polvmer Research, GKSS Research Centre Geesthacht GmbH, Max-Planck-Str. 1, 21502 Geesthacht, Germanv
    Sergey.Shishatskiygkss.de
    The separation oI carbon dioxide Irom industrial gas streams is currently a very important topic with environmental and
    economical implications. In the modernization oI coal power plants membrane technology can be applied in diIIerent steps.
    Polymeric membranes can be useIul Ior the CO
    2
    removal Irom the oII-gases (postcombustion) and Ior the CO
    2
    /H
    2
    separation in
    the precombustion processes.
    The separation oI CO
    2
    Irom other gases using polymeric membranes is rather based on solubility than diIIusivity selectivity.
    Materials Ior this separation can be Iound among rubbery polymers or materials able to swell at the separation conditions, what
    signiIicantly reduces the CO
    2
    /N
    2
    (main components oI the oII-gas) diIIusivity selectivity.
    Quaternary ammonium compounds are reported to have extremely high solubility oI CO
    2
    leading to high separation Iactors oI
    CO
    2
    over other permanent gases. However low molecular weight ammonium salts are not easily integrated in the manuIacture
    oI stable membranes.
    In the current work the preparation and characterization oI membranes based on new quaternary ammonium materials will be
    reported. Organically modiIied silanes containing quaternary ammonium (N

    ) groups were synthesized and used in the


    membrane manuIacture. By blending with PEBAX, transparent and mechanically stable thick Iilms could be obtained even
    with rather low molecular weight N

    compounds.
    Measurements carried out using an equipment with high vacuum constant volume and variable pressure conIirmed high
    solubility coeIIicients oI CO
    2
    (up to 0.3 cm
    3
    (STP) cm
    -3
    cmHg
    -1
    ) and high CO
    2
    /N
    2
    solubility selectivity values (up to 1500). As
    long as these experiments were conducted with completely dry material in a water Iree environment the diIIusion selectivity
    and resulting permeability selectivity were poor. An important observation oI the CO
    2
    time-lag hysteresis at low temperatures
    was done indicating active interaction oI the CO
    2
    molecules with N

    compound. At low temperatures CO


    2
    is irreversibly
    absorbed on the N

    sites and can be released only aIter heating to temperatures higher then 60C. This temperature is attractive
    Ior the oII-gas separation, since the gas is usually hotter than 60C.
    When water is introduced into the gas stream, the membrane swells and the gas transport through diIIusivity increases
    signiIicantly. Measurements done at 90 relative humidity conIirmed more than 20 times increase oI membrane permeability.
    The behavior oI the N containing membranes at diIIerent temperatures in the presence oI water vapor will be reported.
    Acknowledgement: The work was perIormed in the Irame oI the MEM-BRAIN project, supported by the Helmholtz
    Association
    -154-
    OF.5.2
    Synthesis, characterization, and molecular simulation of 6FDA/BTDA-pBAPS
    copolyimide membrane for CO
    2
    /CH
    4
    separation
    S. Halitoglu, O. Yilmaz, C. Atalay-Oral, M. G. Ahunbay, S. B. Tantekin-Ersolmaz
    Istanbul Technical Universitv, Department of Chemical Engineering, Maslak, Istanbul 34469, TURKEY
    halitogluitu.edu.tr, ersolmazitu.edu.tr
    Aromatic polyimides are a promising group oI polymers due to their outstanding thermal and chemical stability. Preparation oI
    polyimide membranes with high permselectivity is important Ior membrane based gas separation. Polyimides are synthesized
    by the reaction oI a dianhydride and a diamine in a solvent and by dehydration oI the resultant polyamic acid by imidization.
    Copolyimides allow us to optimize the separation properties by using diIIerent dianhydride and diamine combinations.
    Hundreds oI diIIerent copolyimide structures can be proposed, however, the experimental analysis oI the separation properties
    oI all these structures is a tedious and time-consuming task. In a previous study |1|, we have estimated the permeability
    coeIIicients oI several gases Ior more than 2200 possible copolyimide structures using the group contribution method oI
    Alentiev et al. |2|. The objective oI this study is to synthesize and characterize 6FDA/BTDA-pBAPS (3:1), one oI the
    proposed copolyimide structures predicted in the above mentioned study, as a potential candidate to prepare membranes with
    better separation properties. The predicted permselectivity oI the above mentioned copolyimide is located above the upper
    bound oI Robeson diagram Ior CO
    2
    /CH
    4
    separation. This work is the Iirst to synthesize 6FDA/BTDA-pBAPS structure to the
    best oI our knowledge. The synthesis is carried out by one-pot rule. Dimethyl acetamide is used as solvent and 1,2-
    dichlorobenzene is used as azeotrop agent to remove H
    2
    O during imidization step. Imidization is determined by FTIR analysis
    oI polyamic acid and polyimide. The copolyimide is characterized by NMR, GPC, DSC, DMA, and wide angle XRD. The CO
    2
    and CH
    4
    permeability coeIIicients oI 6FDA/BTDA-pBAPS Iilms are measured at 35C. We also compare our experimental
    results on structural, mechanical and separation properties with those estimated via molecular simulation methods. The
    simulations were carried out using the Accelrvs Materials Studio 4.1 simulation package and COMPASS Iorce Iield. A
    combination oI molecular dynamics and Monte Carlo methods were used to predict the properties oI interest.
    Abbreviations: 4,4-HexaIluoro isopropylidene diphthalicanhydride (6FDA); 3,3-4,4-Benzophenone tetracarboxyclic
    dianhydride (BTDA); Bis |4-(4-aminophenoxy) phenyl| sulIone (pBAPS)
    This work is supported in part by TUBITAK (Turkish ScientiIic and Technological Research Council) through Grant No.
    106M339.
    |1| S. Halitoglu, S.B. Tantekin Ersolmaz, Prediction oI gas permeability coeIIicients oI copolyimides by group contribution
    methods, presented at the NAMS meeting, May 12-16, 2007, Orlando, Florida.
    |2| A.Y. Alentiev, K.A. Loza, Y. Yampolski, Development oI the methods Ior prediction oI gas permeation parameters oI
    glassy polymers: polyimides as alternating co-polymers, J. Memb. Sci., 2000, 167, 91-106.
    OF.5.3
    High Flux and Selectivity SAPO-34 Membranes for CO
    2
    /CH
    4
    Separation
    S. Li, M. A. Carreon, J. L. Falconer, R. D. Noble
    Universitv of Colorado, Chem. & Biol. Eng. Dept., Boulder, CO 80309, USA
    noblercolorado.edu
    SAPO-34 membranes were prepared by seeding the support surIace with SAPO-34 crystals on porous stainless steel tubes (5-
    cm axial length, 7.8-cm
    2
    permeate area). These membranes had a CO
    2
    /CH
    4
    separation selectivity oI 115 and a CO
    2
    permeance
    oI 4.0 10
    -7
    mol/m
    2
    sPa at 295 K and a pressure drop oI 140 kPa. The membranes separated CO
    2
    /CH
    4
    mixtures at Ieed
    pressures up to 7 MPa with selectivities higher than 55, indicating that SAPO-34 membrane can be used at high CO
    2
    partial
    pressure where polymeric membranes have limitations. The SAPO-34 membranes also eIIectively separated CO
    2
    /N
    2
    , N
    2
    /CH
    4
    .
    H
    2
    /CH
    4
    , and CO
    2
    /H
    2
    mixtures. At 295 K and a pressure drop oI 4.9 MPa (permeate pressure: 84 kPa), a membrane had a CO
    2
    /
    H
    2
    selectivity oI 22. The CO
    2
    permeance was 2 10
    -7
    mol/m
    2
    sPa. The membrane tubes have also been scaled up Irom 5-cm
    long to 25-cm long. At 295 K and a pressure drop oI 138 kPa, the CO
    2
    /CH
    4
    selectivity was 90 and the CO
    2
    permeance was 2.3
    10
    -7
    mol/m
    2
    sPa Ior a 25-cm long membrane.
    -155-
    OF.5.4
    Development of cesium-incorporated carbon membranes for CO
    2
    separation under
    humid conditions
    T. Kai, S. Kazama, Y. Fujioka
    Research Institute of Innovative Technologv for the Earth (RITE), 9-2 Ki:ugawadai, Ki:ugawa-Shi, Kvoto, 619-0292 Japan
    kazamamvc.biglobe.ne.jp
    Carbon capture and storage (CCS) is seen as a promising means to mitigate carbon dioxide emissions and has great promise in
    the near Iuture Irom both technological and economic standpoints. One problem with CCS is the cost oI recovering CO
    2
    Irom
    emissions. One promising means oI lowering the cost oI CO
    2
    separation is the development oI new, high-perIormance CO
    2
    separation membranes Ior CO
    2
    recovery.
    It is well known that carbon membranes have high perIormances Ior gas separation, including CO
    2
    separation Irom CO
    2
    /N
    2
    gas
    mixture. However, one oI the signiIicant drawbacks oI using carbon membranes is the negative eIIect oI water vapor in the
    Ieed gas on separation perIormance |1|. In this research, cesium (Cs)-incorporated carbon membranes were developed Ior CO
    2
    separation under humid conditions. A cardo-type polyimide was chosen as the precursor Ior carbon membranes. Cesium
    carbonate (Cs
    2
    CO
    3
    ) was chosen as a Cs source and blended with precursor solution. Precursor-coated membranes or precursor
    Iree-standing Iilms were carbonized at 600 C Ior 3 hours under N
    2
    atmosphere. Analyses by atomic absorption spectrometry,
    inductively coupled plasma mass spectrometry and electron probe microanalysis revealed that Cs was incorporated into the
    carbon uniIormly and that the concentration oI the incorporated Cs could be controlled by the concentration oI Cs
    2
    CO
    3
    in the
    precursor.
    The separation perIormance was evaluated using a CO
    2
    /N
    2
    gas mixture with controlled relative humidity at 40C. The original
    carbon membrane without Cs had a lower CO
    2
    permeance and CO
    2
    /N
    2
    separation Iactor under humid conditions than it did
    under dry conditions. On the other hand, Cs-incorporated carbon membrane had a higher CO
    2
    permeance and separation Iactor
    under humid conditions. The CO
    2
    permeance (Q
    CO2
    ) and separation Iactor (
    CO2/N2
    ) using a CO
    2
    /N
    2
    gas mixture (CO
    2
    /N
    2

    5/95) at 100 RH Ior Cs-incorporated carbon membranes (Cs
    2
    CO
    3
    concentration in precursor: 1.4 wt) were ca. 2.2 10
    -10
    m
    3
    (STP) m
    -2
    s
    -1
    Pa
    -1
    and 44, respectively, and were greater than values Ior the original carbon membrane (Q
    CO2
    2.4 10
    -11
    m
    3
    (STP) m
    -2
    s
    -1
    Pa
    -1
    ,
    CO2/N2
    11). It was demonstrated that the incorporation oI Cs into carbon membranes could overcome the
    problem oI low separation perIormance under humid conditions. It was revealed by water vapor sorption and
    nanopermporometry that carbon pores became hydrophilic to some extent and that pore size distribution was shiIted to greater
    pore size by adding controlled amount oI Cs
    2
    CO
    3
    in precursor. It was suggested that the change in pore size and pore surIace
    property played an important role to improve CO
    2
    separation perIormance under humid condition.
    |1| C.W. Jones and W.J. Koros, Characterization oI ultramicroporous carbon membranes with humidiIied Ieeds, Ind. Eng.
    Chem. Res., 34 (1995) 158.
    OF.5.5
    Membranes for dehydration and CO
    2
    capture of flue gases
    K. Nijmeijer, J. Potreck, H. Sijbesma, S. Reijerkerk, K. Fischbein, M. Wessling
    Membrane Science & Technologv, Institute of Mechanics, Processes and Control Twente (IMPACT), Universitv of Twente,
    P.O. Box 217, 7500 AE Enschede, The Netherlands.
    d.c.nijmeijerutwente.nl
    In the present work we analyze the sorption, diIIusion and permeation behavior oI two diIIerent types oI highly water
    permeable, hydrophilic membranes Ior the dehydration and/or capture oI CO
    2
    Irom Ilue gases:
    - PEBAX

    1074, which shows molecular transport through a soIt rubbery phase based on polyethylene oxide
    - S-PEEK, which shows transport through an amorphous glassy phase with ionic groups present which will
    preIerentially hydrate over the apolar matrix.
    The Iundamental understanding oI water vapor and gas transport phenomena through these materials is particularly interesting
    since both materials are diIIerent in their chemistry and physical state and both systems may vary strongly in relation to
    polymer/vapor interactions, relaxation phenomena, and separation perIormance oI the membranes.
    Water vapor sorption isotherms in PEBAX

    1074 represent Flory-Huggins type oI sorption, while water sorption in SPEEK
    shows dual mode and Flory-Huggins type oI sorption. The highly hydrophilic nature oI the polymers results in extremely high
    -156-
    amounts oI absorbed water. Thermodynamic analysis shows that Ior both polymers water sorption is driven by a Iavorable
    water sorption enthalpy. The results suggest that in PEBAX

    additional sorbed water molecules experience a water-like


    environment, whereas in S-PEEK the polymer-water interactions prevail. This observation is supported with results Irom
    cluster analysis. The results prooI the occurrence oI both Fickian sorption behavior and relaxational phenomena in SPEEK
    already at very low water concentrations in the polymer. The Fickian diIIusion coeIIicient changes over three orders oI
    magnitude in SPEEK and over two orders oI magnitude in PEBAX

    1074.
    Gas permeation measurements with binary mixtures oI H
    2
    O/N
    2
    and H
    2
    O/CO
    2
    reveal that especially Ior SPEEK extremely high
    water vapor permeabilities (P
    H2O
    ~410
    6
    Barrer) and selectivities (
    H2O/N2
    ~10
    7
    ) can be obtained, especially at high activities.
    Measurements with ternary gas mixtures (H
    2
    O/N
    2
    /CO
    2
    ) show that the presence oI only 10 CO
    2
    induces a severe increase in
    N
    2
    permeability in SPEEK. This results in a three Iold decrease in the selectivity with ternary mixtures compared to the ideal,
    hypothetical value obtained Irom binary mixtures with either H
    2
    O/N
    2
    or H
    2
    O/CO
    2
    . Nevertheless CO
    2
    /N
    2
    selectivity values as
    high as 80 at a CO
    2
    permeability oI ~20 Barrer can be obtained when using ternary mixtures. Permeability and selectivity
    values in PEBAX

    1074 are almost unaIIected by the presence oI CO
    2
    as third component. The water vapor permeability
    increases with increasing water vapor activity, whereas the permeability oI the gases slightly decreases with increasing
    activity. CO
    2
    permeabilities ranging Irom 150-180 Barrer and CO
    2
    /N
    2
    selectivities oI ~30 can be obtained.
    The results not only show the high potential oI these polymers Ior dehydration purposes, they also show that these polymers
    oIIer attractive routes to the integration oI dehydration and CO
    2
    capture using membrane technology.
    This research is supported with a grant oI the Dutch Program EET (Economy, Ecology, Technology), a joint initiative oI the
    Ministery oI economic AIIairs, Education, Culture and Sciences, and oI Housing, Spacial Planning and the Environment, and
    run by the EET program oIIice SenterNovem. In addition it is Iinanced by the European Union as part oI the FP6 project
    NanoGLOWA (NMP 3-CT-1007-026735).
    OF.5.6
    Thin film composite membranes for CO
    2
    /N
    2
    and O
    2
    /N
    2
    mixed gas separations using
    polymers of intrinsic microporosity on poly (vinylidene fluoride)
    L. Layton, M. M. Dal-Cin, A. Kumar, N. Du, M. D. Guiver
    ICPET, National Research Council of Canada, 1200 Montreal Rd., Ottawa, ON, K1A 0R6, CANADA
    mauro.dal-cinnrc-cnrc.gc.ca
    Thin Film Composite (TFC) membranes oI Polymers oI Intrinsic Porosity (PIM-1) |1| on a poly (vinylidene Iluoride) (PVDF)
    were produced under various conditions to optimize their perIormance with respect to CO
    2
    capture and subsequent
    sequestration Ior mitigation oI green house gases.
    The perIormance oI the TFCs is compared to theoretical benchmarks based on the dense Iilm selectivity and permeability oI
    PIM1 Irom the literature. The pure gas selectivity was taken as the primary criterion Ior having made a deIect Iree TFC.
    TFCs made Irom several coating conditions achieved and even surpassed the literature pure gas selectivity oI 25 Ior CO
    2
    /N
    2
    ,
    even though the O
    2
    /N
    2
    selectivity oI 4 was rarely achieved. The selectivity with mixed gases (10, 20, 30 and 40 CO
    2
    ) was
    typically below the pure gas selectivity at 10 and increased beyond the pure gas selectivity at 40 CO
    2
    in the Ieed. The CO
    2
    permeance IordeIect-Iree TFCs were in the range expected values Ior PIM-1 coating thicknesses oI 300-600 nanometers,
    Figure 1, and surIace porosity corrections oI 5-10. Several samples with
    CO2/N2
    ~25 had a CO
    2
    permeance ~ 400 GPU.

    Figure 1. Angled view oI PIM-1 on PVDF TFC showing light diIIraction patterns, leIt. SEM cross section showing a PIM-1
    thickness oI approximately 400 nm.
    -157-
    |1| Peter M. Budd, Kadhum J. Msayib, Carin E. Tattershall, Bader S. Ghanem, Kevin J. Reynolds, B. Neil Mckeown, Detlev
    Fritsch, Gas separation membranes Irom polymers oI intrinsic microporosity, J. Membr. Sci. 251 (2005) 263.
    OF.5.7
    PEO based membranes for CO
    2
    capture from light gases using multi-component feed
    mixtures
    S. R. Reijerkerk, K. Nijmeijer, M. Wessling
    Universitv of Twente, Institute of Mechanics, Processes and Control Twente (IMPACT), Membrane Science & Technologv,
    P.O. Box 217, 7500 AE Enschede, The Netherlands
    d.c.nijmeijerutwente.nl
    The removal oI CO
    2
    Irom light gas mixtures such as H
    2
    , N
    2
    and CH
    4
    is an important application in industry, Ior instance in
    synthesis gas, Ilue gas and natural gas processing. Materials based on ethylene oxide (EO) units have been studied extensively
    as membrane material Ior these CO
    2
    /light gas separations as the ether oxygen linkages exhibit Iavorable interactions with the
    quadrupolar CO
    2
    . Especially the removal oI CO
    2
    Irom Ilue gas is a challenging Iield as Ilue gas contains many diIIerent
    components (besides CO
    2
    and N
    2
    ) oI which the most important are H
    2
    O, O
    2
    , SO
    2
    and HCl/HF , although most researchers only
    report the CO
    2
    separation perIormance using pure, dry gas measurements as recently reviewed by Powell et al.
    In this work we investigate the membrane perIormance under more realistic process conditions. Hence, we extensively studied
    the inIluence oI pure, binary (CO
    2
    /N
    2
    , CO
    2
    /H
    2
    and CO
    2
    /CH
    4
    ) and ternary (CO
    2
    /N
    2
    /H
    2
    O) Ieed mixtures on the CO
    2
    separation
    eIIiciency, using novel PEO based block copolymers. The PEO soIt segment length in our system was varied between 1.000
    10.000 g/mol enabling PEO concentrations as high as 88-wt.
    In this system, based on rubbery, solubility selective, block copolymers, no noticeable diIIerence at low Ieed pressure (_ 4 bar)
    has been observed between the pure and mixed gas experiments. High pressure (P
    CO2,max
    25 bar) CO
    2
    /H
    2
    and CO
    2
    /CH
    4
    mixed
    gas experiments perIormed at temperatures between -10C and 35C showed a distinct diIIerence between ideal and mixed gas
    selectivity. This diIIerence increased with increasing CO
    2
    partial pressure and with decreasing temperature. Pure and mixed
    gas sorption experiments revealed that this diIIerence scales linearly with the concentration oI CO
    2
    within the polymer.
    Furthermore, membrane perIormance using more realistic Ilue gas conditions has been tested using a ternary system. Mixed
    gas permeability has been measured at 50C varying the relative humidity (RH) between 0 and 98 using a 10/90 (v/v)
    mixture oI CO
    2
    /N
    2
    . Remarkably, the ternary system showed a decrease in gas permeability upon increasing water vapor
    activity, while the CO
    2
    /N
    2
    mixed gas selectivity shows a slight increase ( 10) with water vapor activity.
    This signiIies that the investigation oI gas separation perIormance under realistic process conditions is oI major importance to
    understand actual membrane behavior and assess its applicability in real liIe.
    This research was Iinancially supported by the European Union (FP6 Integrated project NanoGLOWA (NMP3-
    CT-2007-026735)).
    OF.5.8
    Reducing CO
    2
    footprint with hydrogen separation membranes
    E. Engwall
    1
    , J. Saukaitis
    2
    , G. Komplin
    2
    , M. Joshi
    1
    , A. Del Paggio
    3
    , A. Nijmeijer
    4
    1
    Shell International Exploration and Production, 3333 Highwav 6 South, Houston, TX 77082 (USA)
    2
    Shell Global Solutions US Inc., 3333 Highwav 6 South, Houston, TX 77082 (USA)
    3
    CRI/Criterion Inc., PO Box 4489, Houston TX 77210-4489 (USA)
    4
    Shell Global Solutions International BJ, P.O. Box 38000, 1030 BN Amsterdam (The Netherlands)
    Erik.EngwallShell.com
    Integration oI Pd or Pd alloy membranes with reIorming or WGS reactors, Ior pre-combustion Iuel de-carbonization, is
    attractive Ior the reduction in CO
    2
    emissions. Recovery oI CO
    2
    at high pressure and high purity (~90 mol) as well as carbon
    conversions in excess oI equilibrium limits may be achieved using various process schemes |1,2|. CRI/Criterion is in the
    process oI commercializing Pd and Pd-alloy membranes on sintered porous metal supports. The scope oI the CRI/Criterion
    eIIort includes the development oI membranes Ior sale to third parties in addition to the support oI the Shell process
    development eIIorts. SuccessIul evaluations oI CRI/Criterion H
    2
    separation membranes in membrane steam reIormers and as
    -158-
    high temperature membrane separators have been perIormed by CRI/Criterion |3|, and by third parties |4|. Figure 1 shows H
    2
    output vs CO partial pressure Ior a CRI Pd membrane (15cm L x 2.5cm OD). The Ieed had similar composition to the output
    Irom a WGS reactor. As CO Ieed was increased, a portion oI the CO
    2
    Ieed was subtracted to keep a constant gas velocity
    proIile. These data show that the CRI/Criterion membrane had no CO inhibition at 430
    o
    C and process conditions relevant to
    many Iuel decarbonization applications.
    CRI/Criterion has produced membranes oI this type as large as
    2"OD by 48"L, by welding two separate 24"L sections. These
    membranes can be produced with a hydrogen permeance in the
    range oI 50-70 |Nm
    3
    /m
    2
    .h.bar
    0.5
    |. Both the hydrogen Ilux and the
    separation selectivity are stable at temperatures oI 300-500
    o
    C and
    diIIerential pressures oI 26-42 Bar. H
    2
    purity oI ~99 has been
    demonstrated Ior periods exceeding 2000 hrs in high temperature
    gas separations.
    |1| Matzakos, A.N.; Wellington, S.L.; Mikus, T.; Ward, J.M.. U.S.
    Patent 6,821,501 B2, Nov. 23, 2004.
    |2| Clomburg et al.. U.S. Patent Application, US 2008/0179569
    A1.
    |3| Engwall, E.; Saukaitis, J.; Joshi, M.; Matzakos, A.; Del
    Paggio, A.. Membrane steam reIorming Ior H
    2
    production, AIChE
    National Meeting, November 2007.
    |4| Sanchez, J.M; Marono, M.; Barreiro, M.M.. Separation oI CO
    2
    and H
    2
    using palladium membranes (Ior integration in power
    generation with CO
    2
    capture). EUROMEMBRANE ConIerence
    2009.
    OF.5.9
    LSCF hollow fibre membranes for oxygen permeation
    B. Zydorczak, K.Li
    Department of Chemical Engineering, Imperial College London , Exhibition Road, South Kensington SW7 2AZ London
    United Kingdom
    Barbara.Zydorczak07imperial.ac.uk
    The overall objective oI our research is to conceive, design, Iabricate and characterise stable mixed-conducting LSCF hollow-
    Iibre membranes Ior long-term oxygen production as well as to enhance the oxygen permeation Ilux. DiIIerent structures oI the
    LSCF hollow Iibre membranes were Iabricated by phase inversion/sintering method and their oxygen permeabilities were
    tested and compared. The LSCF hollow Iibre membranes possessing the highest oxygen permeability were spun Irom the
    starting suspension containing 70.20 wt LSCF powder, 23.57 wt N-methyl-2-pyrrolidinone (NMP), 6.12 wt
    polyethersulIone (PESI) and 0.11 wt dispersant and then sintered at 1260
    0
    C. In order to extend the length oI macrovoids and
    reduce the thickness oI the skin layer, in the spinning process a mixture oI 89 N-methyl-2-pyrrolidinone (NMP) and 11
    deionised water was used as an internal coagulant. According to SEM images (Fig 1) it can be seen that the inner surIace
    exhibited high porosity and the thickness oI the membrane was reduced, greatly improving the oxygen permeation rate.
    Oxygen permeation measurements were conducted using sweep gas as an operating mode. Figure 2 shows the oxygen
    permeation rate comparison between diIIerent structures oI the membranes. Sandwich-like, symmetric and asymmetric (with
    short Iingers) structures exhibit similar oxygen permeation rates due to the same dense downstream surIace whereas Ior the
    highly asymmetric hollow Iibre membrane due to its porous downstream surIace the oxygen permeation rate is greatly
    improved.
    .
    Fig 1.SEM images oI highly asymmetric LSCF hollow Iibre membrane:
    a) whole cross section b) long Iingers c) porous downstream surIace
    -159-
    Figure 1. CR membrane H
    2
    flux vs
    P
    CO
    for syngas feed at 430
    o
    C
    0
    100
    200
    300
    400
    0 20 40 60 80
    P
    CO
    [kPa]
    H
    2

    [
    S
    L
    P
    H
    ]
    Fig 2. Oxygen permeation rate data (operating conditions: sweep gas Ilow rate 16.79 ml/min)
    OF.5.10
    Removal of dioxins and gas mixture separations using supported ionic liquid
    membranes (SILMs)
    L. A. Neves
    1
    , P. Kulkarni
    2
    , C. AIonso
    2
    ,

    I. M. Coelhoso
    1
    , J. G. Crespo
    1
    1
    REQUIMTE/CQFB, FCT Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal
    2
    CQFM, Department of Chemical Engineering, Instituto Superior Tecnico, 1409-001 Lisboa, Portugal
    luisa.nevesdq.Ict.unl.pt
    This work explores the use oI Room Temperature Ionic Liquids (RTILs) as membrane materials Ior two diIIerent applications,
    the removal oI dioxins Irom gaseous streams and the Iractionation oI gas mixtures.
    In a supported ionic liquid membrane (SILM), an Ionic Liquid (IL) is immobilized inside the porous structure oI a polymeric
    or ceramic membrane. Due to a large variety oI properties oI RTILs such as a negligible vapour pressure, and their selective
    aIIinity towards diIIerent kinds oI molecules, it is particularly interesting the use oI a RTIL as an immobilized phase in order to
    obtain stable membranes Ior speciIic applications.
    Due to the ability oI RTILs to absorb dangerous dioxin compounds Irom a vapour phase above room temperature, and due to
    their negligible vapour pressure, the concept oI immobilizing RTILs in porous supports is expected to be an eIIicient process
    Ior recovering toxic compounds Irom eIIluents by vapour permeation at high temperatures (above 200 C). In order to evaluate
    the eIIiciency oI this concept, RTILs were immobilized in the porous structure oI ceramic membranes which are stable at high
    temperatures. Stability studies were perIormed and it was demonstrated that the tested ceramic membranes eIIectively retain
    the immobilized RTIL, resulting in a very stable membrane. Preliminary results also show that a signiIicant amount oI dioxins
    is captured by the SILM at high temperatures (200 C). Ongoing work is Iocused on the process oI recovering the dioxins Irom
    the RTIL medium and comparing it with competing processes.
    In order to study the application oI SILMs Ior separation oI gaseous mixtures, RTILs were immobilized inside the porous
    structure oI polymeric membranes. Stability studies were also perIormed and it is demonstrated that these SILMs eIIectively
    retain the immobilized RTIL in a very stable mode. The permeability towards diIIerent gases, such as N
    2
    , O
    2
    , CH
    4
    , CO
    2
    and H
    2
    ,
    was measured. These measurements were perIormed at 30 C. It was observed that the selectivity oI Supported Ionic Liquid
    Membranes towards CO
    2
    was very high when compared to that oI N
    2
    (selectivity values in the range oI 7-35), and when
    compared to CH
    4
    (selectivity values in the range oI 8-570), with no loss oI RTIL. These results suggest the potential use oI
    Supported Ionic Liquid Membranes in gas mixtures separations.
    -160-
    OF.5.11
    New aspects of empirical approaches for prediction of gas permeability parameters
    of polymers
    V. Teplyakov
    1,2
    , O. Malykh
    1,2
    , E. Favre
    3
    , I. Beckman
    2
    1
    A. J. Topchiev Institute of Petrochemical Svnthesis (TIPS), Russian Academv of Sciences, Leninskiv prospect 29, GSP-1,
    119991 Moscow, Russia
    2
    M. J. Lomonosov Moscow State Universitv (MSU), Leninskie Gorv 1, GSP-3, 119899 Moscow, Russia
    3
    Groupe LSGC UPR CNRS 6811, ENSIC INPL, Rue Grandville 1, BP 451, 54001 Nancv, France
    teplips.ac.ru
    The assemblage oI gas permeability data Ior polymers is drastically increased during last decades. Thus, there is opportunity to
    consider the more general regularities based on representative polymer selection including diIIerent polymeric materials such
    as homopolymers (polyimides, polyamides, polysulIones, polycarbonates, silicon-containing polymers, polyoleIins,
    polyphosphasenes, etc.), copolymers, composite membrane materials and surIace-modiIied membranes. In spite oI
    accumulated data Ior more than 2000 polymers only a Iew oI them are using at present as membrane gas separation materials.
    One oI the reasons is problem oI preliminary estimation oI gas permeability parameters oI polymeric material in relation to
    desired set oI penetrants (permanent gases, lower hydrocarbons and toxic gaseous components). This task can be carried out by
    systematic study oI empirical regularities and comparison with some existing models |1| oI gas diIIusion by using
    DATABASE containing oI the most published gas permeability data. Paper presents the Iirst step oI this study including the
    DATABASE (more than 1400 polymers) organization algorithm, results oI empirical statistical treatment oI these data and
    consideration oI the most understandable correlations between gas permeability parameters (permeability, diIIusivity and
    solubility coeIIicients) oI polymeric materials and key physical chemical properties oI diIIusing molecules. As a result the
    'empty spaces oI DATABASE Ior permanent gases were Iilled. Based on diIIusing molecule conIigurations and their
    Lennard-Johnes potentials consideration the approach to the preliminary estimation oI polymeric materials permeability in
    relation to permanent gases based on limited experimental data is considered. Particularity oI estimation Ior lower
    hydrocarbons and toxic gaseous components permeability are discussed.
    |1| V.V.Teplyakov, P.Meares, Correlation aspects oI the selective gas permeabilities oI polymeric materials and membranes,
    Gas Separation and PuriIication, 4 (1990) 66-74.
    This work is partially supported by FP6 IP n019825-(SES6) 'HYVOLUTION, Grants RFBR No. 07-03-00752, No.
    08-03-92495
    OF.5.12
    OTM modules: materials, flux and stability in carbon-containing atmospheres
    P.I. Dahl, M.L. Fontaine, Y. Larring, R. Bredesen
    SINTEF Materials and Chemistrv, Post box 124 Blindern, NO-0314 Oslo, Norwav
    Paul.inge.dahlsinteI.no
    Mixed oxide ion and electron conducting membranes (OTM) operate at high temperature, typically ranging Irom 800 C to
    1000 C. This operation temperature is interesting Ior integration in power cycles with CO
    2
    capture, as the oxy-Iuel processes.
    The possibility oI managing heat and mass integration at high temperature makes such concepts Ior oxygen production very
    competitive compared to more energy consuming cryogenic distillation. The current status oI OTM indicates that materials
    with long-liIe perIormance Ior such stringent operating conditions, and highly compact membrane conIigurations in housings
    are necessary to develop Iurther beIore commercial deployment. For the membrane, it is necessary to combined long term
    stability and suIIiciently high Ilux (~10 mL.cm
    -2
    .min
    -1
    in operation), properties that oIten contradict each other.
    The present contribution addresses these issues on the basis oI the investigation oI perovskite related materials, such as
    CaTi
    0.9
    Fe
    0.1
    O
    3
    oxides. These materials are alternative candidates relative to state-oI-the-art Co- and Fe- containing perovskites,
    and exhibit high chemical stability and low thermal expansion coeIIicient. In this work, asymmetric membranes are prepared
    as thin dense Iilms coated onto porous supports and integrated in planar and tubular modules. The structure, composition,
    microstructure, surIaces and interIaces oI OTM are thoroughly investigated by several techniques, including diIIraction (XRD,
    EDX) and microscopy (SEM, TEM, EMPA), etc. Flux oI OTMs is investigated using a Probostat rig enabling high
    temperature and high pressure measurements. Oxygen permeation rates are evaluated as a Iunction oI OTM thickness down to
    -161-
    8 m, temperature Irom 800 C to 1050 C and oxygen partial pressure gradient. This study enabled us to elucidate transport
    mechanisms and determine rate limiting step as a Iunction oI the processing conditions and OTM module designs.
    Stability oI OTM in carbon containing atmosphere at high temperature was investigated by cycling gas permeation
    measurements under H
    2
    O, CO and CO
    2
    gas mixtures. Post mortem analyses oI the OTM were carried out to investigate
    potential eIIects on the microstructure and the composition oI the tested membranes. It was shown that CaTi
    0.9
    Fe
    0.1
    O
    3
    OTM
    perIormance remains unaIIected aIter testing in carbon containing atmosphere and no degradation oI the membrane was
    observed. The Ilux oI the thinner membrane reached ca. 3.5 mL.cm
    -2
    .min
    -1
    at 1050 C and Iurther improvement oI perIormance
    is expected by reducing the membrane thickness and/or using pressurized Ieed gas.
    All these results will be presented in the present contribution.
    OF.5.13
    Preparation and characterization of high perfomance hollow fibre carbon
    membranes - discussion of results and potential applications
    X. He, M.-B. Hgg
    Department of Chemical Engineering, Norwegian Universitv of Science and Technologv, N-7491 Trondheim, Norwav
    may-britt.haggchemeng.ntnu.no
    Our work was mainly Iocused on the choice oI precursor and optimization the carbonization condition with systematical
    investigation. The cellulosic-based hollow Iibre membranes were spun by dry-wet spinning process and pretreated with
    deacetylation Ior the precursors oI HFCMs. A multi-dwell carbonization protocol was used as the carbonization procedure.
    The carbonization parameters like purge gas, heating rate, Iinal thermal temperature and soak time were systematically
    investigated based on the orthogonal experimental design (OED) method. The high perIormance HFCMs were prepared under
    the optimal carbonization protocol. The structure, morphology and properties oI the prepared HFCMs were characterized by
    TGA, FTIR and SEM in Fig. 1.
    The HFCMs were mounted into the in-house designed module and tested with pure gases oI N
    2
    and CO
    2
    and gas mixture
    10CO
    2
    -90N
    2
    using a gas permeation test setup. The pure gas tests oI the HFCMs were run Ior all proIiles oI OED at the
    same Ieed temperature and pressure (30C and 2bar). The permeability and ideal selectivity were used Ior conjoint analysis oI
    OED results by SPSS soItware. The inIluence importance Ior these Iactors and optimal carbonization procedure were obtained.
    The relationship between the permeability Ior pure gas and temperature can be expressed by Arrhenius equation, and the
    apparent transport activation energy Ior CO
    2
    and N
    2
    were 7.9 and 20.3 kJ/mol, respectively. Moreover, the gas mixture tests
    were carried out with various stage-cuts (0, 0-20). The experiment results showed that the permeance values Ior CO
    2
    decreases with the increase oI stage-cut, but increases Ior N
    2
    , which caused the decrease the selectivity oI CO
    2
    /N
    2
    as shown in
    Fig. 2. Thus, the purity oI CO
    2
    decreased with the increase oI stage-cut Ior a given membrane area. The implications oI the
    presented results on perIomance and hence potential applications will be discussed.
    Prepare hollow Iibre carbon membranes (HFCMs) with high separation perIormance is a very challenging task. In this area,
    new precursors and optimal carbonization protocol are required.

    Fig. 1 SEM Ior HFCM Fig. 2 Dependence oI permeance and selectivity on stage-cut
    Acknowledgement is given to the Nanoglowa-project, Iinancing the work within the FWP6.
    -162-
    -2 0 2 4 6 8 10 12 14 16 18
    2.0x10
    -4
    2.5x10
    -4
    3.0x10
    -4
    2.5x10
    -2
    3.0x10
    -2
    3.5x10
    -2
    4.0x10
    -2
    4.5x10
    -2

    CO
    2
    N
    2
    Selectivity
    Stage-cut ( ), %
    P
    e
    r
    m
    e
    a
    n
    c
    e
    ,

    m
    3
    (
    S
    T
    P
    )
    /
    (
    m
    2
    .
    h
    .
    b
    a
    r
    )
    80
    100
    120
    140
    160
    180
    200
    S
    e
    le
    c
    t
    iv
    it
    y

    o
    f

    C
    O
    2
    /
    N
    2
    OF.6.1
    Integration of pervaporation/gas-liquid absorption: a new approach for the
    production of stable aroma additives
    C. Brazinha, V. D. Alves, R. M. C. Viegas, J. G. Crespo
    REQUIMTE / CQFB, FCT-Universidade Nova de Lisboa, Campus da Caparica, P-2829-516 Caparica, Portugal
    carla.brazinhadq.Ict.unl.pt
    An innovating way oI obtaining natural aroma compounds is conceived and studied. The proposed process combines the
    advantages oI organophilic sweeping gas pervaporation with non-dispersive gas-liquid absorption in membrane contactors.
    This process allows Ior a selective recovery oI natural aroma compounds in typically highly diluted aqueous media and it also
    avoids the need oI vacuum conditions and condensation steps Ior aroma recovery, which has an important impact on the
    reduction oI the energy intensity oI the process. This approach may also open new opportunities Ior the recovery oI valuable
    aroma compounds Irom the headspace and oII-gas streams oI Iermentative processes.
    The integration oI a sweeping gas pervaporation unit with a gas-liquid membrane contactor was achieved successIully,
    allowing Ior capturing the aroma compounds present in the vapour permeate stream by absorption in a membrane contactor.
    This process has the additional advantage oI stabilizing the target aroma compounds aIter being captured in a liquid adsorbent,
    a common additive in cosmetic and/or Iood products. AIter solubilization in the selected absorbent, the aromas may be
    delivered and released in the Iinal cosmetic/Iood product.
    In order to optimize the integrated process, its key Iactors were selected, particularly the sweep gas linear velocity and the type
    oI absorbent. Optimization oI the sweeping gas velocity aimed at maximizing the concentrations oI the recovered aromas in the
    sweeping gas stream and the residence time in the membrane contactor. Among the additives and the aroma compounds
    studied, PEG 300 was the best choice due to generally higher partitions and higher rates oI absorption oI the aroma compounds
    to this additive and due to a suitable wettability oI the polypropylene membrane used in the membrane contactor unit.
    Additionally, high partitions oI the aroma compounds to PEG 300 were observed, specially in the case oI the more
    hydrophobic esters to PEG 300 which is advantageous Ior a better Iractionation oI the target aroma compounds.
    Finally, it was also studied and better understood the importance oI regulating the mass transIer conditions in the membrane
    absorption contactor. Particularly, the eIIect oI the Iluid dynamic conditions in the membrane contactor was studied and the
    mass transIer coeIIicients were calculated through a model consisting oI a non-linear Iitting oI the experimental aroma
    concentrations in the liquid phase over time. The calculated overall mass transIer coeIIicients were relatively low, which is
    mainly explained by the impact that the high viscosity oI the selected absorbent, PEG 300, has on the mass-transIer process.
    OF.6.2
    Microcapsules based on a lightly crosslinked liquid crystalline polymer: a new smart
    material?
    B. Tylkowski, M. Pregowska, E. Jamowska, R. Garcia-Valls, M. Giamberini
    Universitv Rovira i Jirgili,, Department of Chemical Engineering, Av. Pasos Catalans, 26 43007 Tarragona Spain
    bartosz.tylkowskiurv.net
    Nowadays the microencapsulation technology is promising Ior new applications in the Iields oI intelligent microstructures and
    microsystems |1|, as well as in the Iield oI phase change materials |2| and in selI-healing composites |3|.
    Films based on a new liquid crystalline lightly crosslinked polyamide, the state oI order oI which can be triggered by means oI
    external stimuli, such as temperature and light, were prepared by interIacial polymerization. This polymer exhibited a nematic
    phase up to 166
    o
    C and it started to decompose at 340
    o
    C; morphological variations oI the Iilm were observed by Scanning
    Electron Microscopy in correspondence to the clearing temperature; moreover, by continuous irradiation with UV light at
    room temperature, the polymer underwent E-Z photoisomerization. Microcapsules were prepared, which shell was constituted
    by this LC polymer, containing either toluene, or concentrated solutions oI naphthalene or beta-carotene, as the core. To the
    authors` knowledge, this is the Iirst example oI microcapsules whose shell is completely constituted by a liquid crystalline
    lightly crosslinked polymer. Release experiments oI beta-carotene were perIormed in water and in tetrahydroIuran. Beta-
    carotene release in water at 20C was strongly inIluenced by UV irradiation: in the absence oI irradiation, it was practically
    negligible while, when microcapsules were submitted to continuous irradiation with UV light, beta-carotene was quickly
    released and reached 100 release aIter 5 minutes. Preliminary experiments concerning the eIIect oI temperature and oI a
    swelling solvent, such as THF, on release, were also perIormed.
    -163-
    |1| EhrIeld W. Electrochim. Acta, 2003: 48; 2857.
    |2| Zhang X, Tao X, Yick K and Wang X. Colloid Polym. Sci., 2004: 282; 330.
    |3| White SR, Sottos NR, Geubelle PH, Moore JS, Kessler MR, Spiram SR, Brown EN and Viswanathan S. Nature, 2001:
    409; 794.
    OF.6.3
    Recovery of polyphenols in bergamot juice by integrated membrane process
    A. Cassano
    1
    , C. Conidi
    2
    , A. Liguori
    2
    , E. Drioli
    1
    1
    Institute on Membrane Technologv, ITM-CNR c/o Universitv of Calabria, via P. Bucci, 17/C, I-87030 Rende (Cosen:a), Italv
    2
    Department of Pharmaceutical Sciences, Universitv of Calabria, via P. Bucci, I-87030 Rende (Cosen:a), Italv
    a.cassanoitm.cnr.it
    Bergamot Iruit (Citrus Bergamia risso) is a natural hybrid Iruit derived Irom bitter orange and lemon; it is produced almost
    exclusively in the Ionic area oI Calabria (Italy), where soil characteristics and pH (6.5-7.5) are particularly suitable Ior its
    cultivation |1|. Bergamot is essentially used Ior the production oI essential oil, while the juice is considered a waste oI the
    essential oil production. ThereIore, it is interesting to investigate all possible uses oI the juice in order to take advantage oI the
    large amount oI this discarded product, considering the potentialities oI its health promoting substances, especially in terms oI
    polyphenols. Common extraction methods Ior separating polyphenols Irom Iruit waste involve organic solvents which are
    more expensive than aqueous processing; besides, the extracts may contain residual solvents which make them unsuitable Ior
    Iood aims. Alternatively, the extraction with hydrophilic solvents is limited by the co-extraction oI sugars Irom the Iruit.
    ThereIore, technologies able to separate sugars Irom polyphenols are needed in order to concentrate the polyphenolic Iraction
    Ior nutraceutical uses |3|.
    The aim oI this work was to analyse the potentiality oI an integrated membrane process Ior the separation and concentration oI
    polyphenols in bergamot juice in order to develop a natural product which can be used as Iunctional ingredient Ior IortiIied
    Ioods and beverages.
    In particular, the depectinised juice was preliminary submitted to an ultraIiltration (UF) treatment devoted to the removal oI
    suspended solids. The clariIied juice was then submitted to a Iractionation step, by using nanoIiltration (NF) membranes in
    order to separate phenolic Iractions Irom sugars and organic acids.
    The eIIect oI various operating parameters (such as trans-membrane pressure, Ieed pH, Ieed Ilow-rate and Ieed concentration)
    on rejection and Iouling oI polyphenols was investigated.
    Permeate and retentate streams coming Irom membrane operations were analysed Ior their content in total polyphenols,
    Ilavonoids, organic acids, total soluble solids and antioxidant activity in order to evaluate the eIIect oI the membrane
    treatments on the quality and compositions oI the juice.
    |1| R. Pernice, G. Borriello, R. Ferracane, R. Borrelli, F. Cennamo, A. Ritieni, Bergamot: A source oI natural antioxidants Ior
    Iunctionalized Iruit juices, Food Chemistrv, 112 (2009) 545-550.
    |2| N. Miceli, M.R. Mondello, M.T. MonIorte, V. SdraIkakis, P. Dugo, M.L. Crupi, M.F. Traviano, R. De Pasquale, A.
    Trovato, Hypolipidemic eIIect oI Citrus bergamia Risso et Poiteau Juice in Rats Fed a Hypercholesterolemic Diet, Journal of
    Agricultural and Food Chemistrv, 55 (2007) 10671-10677.
    |3| H. Nawaz, J. Shi, G. S. Mittal, Y. Kakuda, Extraction oI polyphenols Irom grape seeds and concentration by ultraIiltration,
    Separation and Purification Technologv, 48 (2006) 176-181.
    OF.7.1
    Purification of flavonoids from black currant juice by nanodiafiltration
    M.B. Jensen, K.V. Christensen, B. Norddahl
    Institute of Chemical Engineering, Biotechnologv and Environmental Technologv, Facultv of Engineering, Universitv of
    Southern Denmark, Niels Bohrs Alle 1, DK-5230 Odense M, Denmark.
    mobjkbm.sdu.dk
    Various compounds oI the Ilavonoid group have been reported to possess therapeutic eIIects towards cancer |1|. Thus there is
    a large potential in identiIying, puriIying and quantiIying Ilavonoids Irom diIIerent natural sources in order to screen the
    -164-
    pharmaceutical values oI these. The Ilavonoids are normally present in much smaller quantities than other solutes such as
    sugars and organic acids. This may state a problem in analysis as some oI the Ilavonoids are present in very minute amounts
    and concentration is limited by the major solutes. This study seeks to separate the sugars and organic acids Irom the Ilavonoids
    in order to Iacilitate better analysis. In the current study, the major solutes in black currant juice are Iructose
    (32 + 3 g/l), glucose (22 + 3 g/l), sucrose (1.6 + 0.2 g/l) and organic acids (28.9 + 0.1 g/l). The Ilavonoids in black currant juice
    are mainly (97) comprised by the glucosides and rutinosides oI cyanidin and delphinidin |2|. The content oI these Ilavonoids
    in black currant juice is measured to (1.5 + 0.1 g/l). The separation process consists oI nanodiaIiltration on Ilat sheet
    membranes with a nominal molecular weight cut oII oI 1,000 Da. The separation process was monitored by comparing
    concentrations oI the Iour Ilavonoids and the sugars and acids in permeate and retentate. The Ilavonoids in the juice have a
    molecular weight between 449 and 611 Da and should be able to pass the pores oI the membrane. However this study shows
    that the Ilavonoids is mainly kept in the retentate where as Iructose (180 Da), glucose (180 Da) and sucrose (342 Da) are
    gradually Ilushed out into the permeate. By diaIiltration, it was possible to remove almost all glucose and Iructose Irom the
    juice. The weight percentage oI the Ilavonoids on dry weight basis increased Irom 1 to 44 during the separation process.
    |1| F. Teillet, A. Boumendjel, J. Boutonnat, X. Ronot, Flavonoids as RTK Inhibitors and Potential Anticancer Agents,
    Medicinal Research Reviews, 2008, 28(5), 715-745
    |2| M.J. Anttonen, R.O. Karjalainen, High-PerIormance Liquid Chromatography Analysis oI Black Currant (Ribes nigrum L.)
    Fruit Phenolics Grown either Conventionally or Organically, Journal oI Agricultural and Food Chemistry, 2006, 54,
    7530-7538
    OF.7.2
    New materials for airborne viruses filtration
    L. Lebrun, G. Tilliket, D. Le Sage, Q. T. Nguyen
    FRE 3101 CNRS -Universite de Rouen, 76821 Mont-Saint-Aignan Cedex, France.
    Laurent.lebrununiv-rouen.Ir
    Removal oI viruses Irom air is today an important concern oI public health Ior the protection oI people Irom viral epidemics.
    For example, the recent viral epidemics in Asia and Europe (H5N1 avian inIluenza, SARS) showed that there is a real need Ior
    protection against viral attacks. Today, vaccination is not eIIective, because oI the Iast changes oI the viruses as well as their
    Iulgurating multiplication and propagation. Conventional methods Ior protection involve Iacial gas masks. However, these
    Iilter materials are not useIul Ior removing viruses Irom air because the pores size is too large Ior this purpose.
    The present study consists in the chemical modiIication oI Iilters in order to give them antiviral properties. Commercial
    cellulosic non-woven layers (Freudenberg, Kimberly Clark.) and non-woven layers extracted Irom commercial medical mask
    (Propre.) were used as Iilters. In order to bring the desired antiviral properties, the non woven layers were dipped in a
    poly(ethyleneimine) (PEI) solution. We used as virus test the bacteriophage T4 oI Escherichia coli. The Iiltration experiments
    were perIormed Ior 1 h (or 2 h) with an aerial suspension oI bacteriophage T4 (around 6 10
    10
    PFU) using a sterilized
    experimental set-up developed in our laboratory. The air Ilow was 8 L/min (respiratory Ilow).
    The Iirst objective oI this work was to optimize the coating oI the non-woven Iibers by PEI. The eIIiciency oI the treatment on
    the layer depends on the pH oI the PEI solution because it inIluences the electrostatic Iixation oI PEI on the support. The best
    results were obtained at pH 5. The concentration oI the solution oI PEI, its ionic strength, the time oI contact between Iibre and
    solution were optimized |1|.
    The best virus retention ratio f (f deIined as the ratio oI upstream virus content to downstream virus content) was obtained with
    2 layers oI Kim Wipes (Irom Kimberly Clark) previously Iunctionalised by PEI (4.4 w/v) Ior 15 min (f 3 10
    5
    ). We
    checked that PEI remained on the support in an air Ilow (8 L/min) aIter 5 h oI use. When these 2 layers were placed inside a
    commercial medical mask instead oI its cellulosic layers (Propre M24001 mask) (f 3.5 10
    4
    ), the f ratio reached 1.8 10
    7
    Ior 1h
    oI Iiltration. Higher Iiltration time decreased the retention: f 5.9 10
    5
    .
    The system under study was tested with respect to an airborne virus responsible Ior the avian inIluenza (A/H5N2) in protected
    L3 laboratory (FRE 3011 CNRS / University oI Lyon I "Virology and Human Pathogenesis" (Pr Lina). 100 ml oI an aerial
    suspension (250

    viruses / ml) was sprayed towards the Iilters Ior 45 min. No virus was detected downstream Irom the Iilter.
    Each layer oI the Iilter stopped 6000 alive viruses / ml. However, the pores oI the Iilters were blocked aIter 30 min oI
    experiment.
    The same system was tested Ior actions against Pseudomonas aeruginosa bacteria (MIC 230 g/ mL). We are also testing
    other antiviral polymers oI the same chemical class.
    Future studies concern tests on non-woven materials oI various compositions (cellulose, poly(ester), poly(acrylonitrile)). These
    experiments may allow us to consider other Iields oI applications Ior the system (puriIiers Ior interior air, wiping tissues,
    protection clothes.).
    -165-
    |1| L. Lebrun, Q. T. Nguyen. Filtre antiviral et son utilisation dans un puriIicateur d`air, climatiseur ou humidiIicateur. French
    patent FR06/06591 (Published on January 25, 2008).
    OF.7.3
    Preparation, characterization and testing of adsorption membranes
    for chromatographic separation of therapeutic plasmids
    L. Raiado-Pereira, D.M.F. Prazeres, M. Mateus
    IBB - Institute for Biotechnologv and Bioengineering, Centre for Biological and Chemical Engineering, Instituto Superior
    Tecnico, Lisbon, Portugal.
    luis.raiadoist.utl.pt
    Today, plasmid DNA (pDNA) is becoming increasingly important as the next generation oI biotechnology products (gene
    medicines and DNA vaccines) make their way into clinical trials, and eventually into the pharmaceutical marketplace. The use
    oI pDNA, as a vector Ior therapeutic gene transIerence has become relevant since saIety concerns with viral vectors, attributed
    to immunological reactions, were raised. However, pDNA application is being held back due to its poor immunogenicity.
    1
    To
    overcome these problems high amounts oI pDNA in its supercoiled topological Iorm are required Ior a Iull treatment and thus
    scalable puriIication processes are essential Ior providing large amounts oI pDNA oI pharmaceutical-grade quality at
    reasonable costs.
    2
    The diversity oI biomolecules present in pDNA containing extracts and the structural and chemical
    similarities between pDNA and impurities are some oI the main challenges when improving or designing novel puriIication
    procedures. Most DNA Iractionation methods rely on standard chromatographic ion-exchange columns (poorly selective
    towards plasmid DNA isoIorms and impurities, like high Mr RNA)
    3
    .
    This work outlines the latest
    improvements upon an hydrophobic
    interaction membrane
    chromatography process that was
    previously developed in our research
    group Ior the Iinal puriIication step
    oI pDNA. The membranes are
    attained by chemical modiIication oI
    pre-activated aIIinity membranes
    Iollowing an in house protocol.
    Characterization regarding
    hydrodynamics, density oI Iunctional
    groups, and selective adsorption
    capacities towards plasmid DNA and
    its usual contaminants was
    perIormed. The HIC membrane was
    able to separate impurities Irom
    clariIied Escherichia coli cell lysates
    speciIically RNA impurities with
    high resolution

    using an optimized 2-
    step elution proIile.
    |1| Brave, A et al. Vaccine delivery methods using viral vectors. Mol. Pharm. 4, 1832 (2007)
    |2| Sousa, F, Prazeres, DMF, Queiroz, J. AIIinity chromatography approaches to overcome the challenges oI puriIying plasmid
    DNA. Trends Biotechnol., 26, 518-525 (2008)
    |3| Diogo, MM, Queiroz, JA, Prazeres, DMF. Chromatography oI plasmid DNA. J. Chromatogr. A, 1069, 3-22 (2005)
    |4| Brave, A et al. Vaccine delivery methods using viral vectors. Mol. Pharm. 4, 1832 (2007)
    |5| Sousa, F, Prazeres, DMF, Queiroz, J. AIIinity chromatography approaches to overcome the challenges oI puriIying plasmid
    DNA. Trends Biotechnol., 26, 518-525 (2008)
    |6| Diogo, MM, Queiroz, JA, Prazeres, DMF. Chromatography oI plasmid DNA. J. Chromatogr. A, 1069, 3-22 (2005)
    -166-
    Figure - Chromat ographic puriIicat ion oI 500l clariIied E. coli lysat e cont aining
    20.5mg/mL oI plasmid DNA wit h a purit y oI 10. Membrane area oI 7.4cm
    2.
    .
    Adsorpt ion buIIer - Tris 10mM pH8, 1.8M (NH
    4
    )
    2
    SO
    4
    . Elut ion buIIer -Tris 10mM
    pH7.4; 10 mL long gradient up t o 40 Iollowed by st ep gradient up t o 100 at 0.5 mL/
    min Ilowrat e. t 55min.
    , g )
    pDNA RNA impurities
    OF.7.4
    Viral clearance using size exclusion based membrane filtration: dominant filtration
    mechanisms and strategies to attain higher throughput
    L. Villain
    1
    , V. Rico Perez
    2
    , J.-E. Dathe
    2
    , M. Brger
    2
    , I. Masselin
    2
    , V. Thom
    2
    , T. Scheper
    1
    1
    Institute of technical chemistrv, Leibni: Universitv Hannover, Germanv.
    2
    Membrane R&D, Sartorius-Stedim Biotech GmbH, Gttingen ,Germanv.
    Louis.villainsartorius-stedim.com
    Size exclusion based virus Iiltration is a robust virus clearance technology Ior biotech- and plasma derived therapeutics. The
    Iilters allow the passage oI molecules up to 8-12 nm in diameter and are especially eIIective in the removal oI small non-
    enveloped viruses oI about 20 nm in diameter, that are resistant to heat and solvent or detergent based inactivation methods |1|.
    However, the Iine porous membrane structure, required to permit high resolution protein/virus separation, makes the method
    highly sensitive to impurities and solute/membrane interactions. This is especially true Ior demanding streams like e.g. plasma
    derived therapeutics Ior intravenous administration, containing pooled IgG oI over thousand oI blood donors, whose Iiltration
    is oIten observed to be throughput limited.
    This paper elucidates the mechanisms governing membrane Iouling by correlating membrane-solute binding to the respective
    Iilterability oI diIIerent solute Iractions generated by hydrophobic interaction chromatography. We illustrated that a small
    subset oI hydrophobic monomeric IgG can dramatically impact the Iilterability oI the whole pooled IgG mixture.
    In a second part, strategies to overcome these limitations are presented. Innovative automated high throughput methods Ior
    perIormance testing were developed to allow the parallel characterization and optimization oI a large variety oI materials and
    operating conditions. The generated data could enhance the development oI a new generation virus Iilter with adequate
    structure and surIace properties that can prevent such hydrophobic solutes/membrane interactions, while maintaining high
    virus reduction values.
    |1| Kreil, T., et al., Removal of small non enveloped viruses bv antibodv-enhanced nanofiltration during the manufacture of
    plasma derivatives. TransIusion, 2006. 46: p1143-1151
    OF.7.5
    Supported liquid membranes with strip dispersion for the recovery of cephalexin
    M.E. Vilt
    1
    , W.S. Winston Ho
    1,2
    1
    Department of Chemical and Biomolecular Engineering, The Ohio State Universitv, 140 West 19th Avenue, Columbus, OH
    43210-1180, USA.
    2
    Department of Materials Science and Engineering, The Ohio State Universitv, 2041 College Road, Columbus, OH
    43210-1178, USA.
    viltchbmeng.ohio-state.edu
    Cephalexin is an important and widely used semi-synthetic cephalosporin. The enzymatic synthesis oI Cephalexin oIIers
    several advantages over the traditional organic synthesis, but results in an aqueous reaction mixture that is diIIicult to separate.
    Liquid membranes, in particular supported liquid membranes (SLMs), are a promising solution to the separation. SLMs are not
    used commercially, as they are still plagued with problem oI long term instability. SLM with strip dispersion has been a recent
    development to solve the issue oI stability.
    SLMs with strip dispersion are Iormed when an aqueous strip solution is dispersed in an organic membrane solution by a
    mixer, and passed on one side oI a membrane support. When a microporous hydrophobic support is used, the organic phase oI
    the dispersion becomes imbedded in the pores oI the support, Iorming a stable SLM. Stability is maintained by having a
    constant supply oI organic membrane solution to the pores. An aqueous Ieed solution is passed on the other side oI the
    membrane support and the target species is extracted into the organic solution by a selective carrier. The target species is then
    stripped by the aqueous strip solution. For Iinal recovery oI the target species, the mixer is turned oII and the dispersion
    quickly separates.
    In this study, Cephalexin has been separated and concentrated Irom an aqueous solution using SLMs with strip dispersion. The
    Iollowing key parameters were investigated: Ieed and strip dispersion Ilowrate, strip dispersion mixing rate, carrier
    concentration, counter ion concentration, pH, and volume oI aqueous strip solution. Experiments used a Liqui-Cel hollow
    Iiber module as a microporous support. The organic membrane solution oI the SLM consisted oI Aliquat 336, Isopar L
    (isoparaIIinic hydrocarbon solvent), and 1-decanol. The aqueous strip solution was composed oI potassium chloride and
    -167-
    citrate buIIer. An enrichment Iactor oI 3.2 was observed in the aqueous strip solution while achieving over 99 extraction and
    96.2 total recovery. In this case, the aqueous Ieed solution oI 5500 ppm (15 mM) was lowered to 30 ppm when using an
    organic membrane solution containing 2.5 Aliquat 336. The resulting overall mass transIer coeIIicient was 1.6 x 10
    -5
    cm/sec.
    The mass Ilux oI Cephalexin Ior this system was Iound to be independent oI aqueous Ieed and strip dispersion Ilowrates,
    suggesting a major mass transIer resistance due to chemical reaction kinetics, which is supported by calculated individual mass
    transIer resistances. The pH oI the aqueous strip phase was Iound to play a more signiIicant role when trying to achieve higher
    enrichment ratios. It was observed that the highest stripping eIIiciency occurs when the pH oI the aqueous strip phase is
    between the values oI 5 and 6.
    OF.7.6
    Organic solvent nanofiltration for the synthesis of oligonucleotide monomers
    R. Vasconcelos, P. Blanc, I. Baptista, A.G. Livingston
    Department of Chemical Engineering and Chemical Technologv, Imperial College London, Exhibition Road, London SW7
    2AZ, UK.
    a.livingstonimperial.ac.uk
    Several oligonucleotide candidate drugs are currently undergoing clinical trials. Eventual commercial success means that
    demand will likely increase, leading to the need Ior economical, Iast, large scale production processes |1,2|. Currently, the
    preIerred method Ior the synthesis oI oligonucleotides is solid phase synthesis, using nucleoside phosphoramidites as
    monomers, which synthesis can account Ior over 33 oI total raw material cost in oligonucleotide synthesis |1|. The synthesis
    oI these monomers is challenging, as it uses scale-limited, lengthy and laborious puriIication methods, such as column
    chromatography and solvent exchange |1,2|. Organic solvent nanoIiltration (OSN) has been proposed Ior this application |3|.
    However, the use oI membranes commercially available at the time prevented its use in typical reaction solvents (MeCN,
    DCM, DMF), requiring an additional solvent exchange step. Recently, work perIormed in our research group in collaboration
    with Membrane Extraction Technology, Ltd led to the development oI cross-linked polyimide membranes DuraMem
    TM

    with the potential to be used in harsh solvent environments |3|. In this work, we have prepared diIIerent cross-linked
    polyimide membranes, and screened their separation perIormance in a typical nucleoside phosphoramidite reaction system
    (Figure 1). The goal was to separate product 4 Irom excess reactants 2 and 3 and by-products, such as diisopropylammonium
    salts and pyridine in a simple one-step OSN process. In this presentation we will Iocus on the membrane selection process and
    present initial results (product 4 with process yields oI 61) that show the Ieasibility and the emerging potential oI the
    application oI OSN this rapidly growing and high-value pharmaceutical Sector.
    O
    P
    N
    NC
    N
    O
    OH
    DmtO
    T
    1, 544 gmol
    -1
    2, 301 gmol
    -1
    O
    O
    P
    DmtO
    N
    O
    NC
    T
    4, 744 gmol
    -1
    PyTFA
    3, 193 gmol
    -1
    MeCN
    Figure 1 Synthesis oI phosphoramidites |1|.
    R.Vasconcelos would like to acknowledge Fundao para a Cincia e a Tecnologia (FCT) Ior granting this work.
    |1| Y.S. Sanghvi, Z.Q. Guo, H.M. PIundheller, A.Converso, Improved process Ior the preparation oI nucleosidic
    phosphoramidites using a saIer and cheaper activator, Organic Process Research & Development, 2000, 4, 175-181.
    |2| C. Xie, M.A. Staszak, J.T. Quatroche, C.D. Sturgill, V.V. Khau, M.J. Martinelli, Nucleosidic phosphoramidite synthesis
    via phosphitylation: activator selection and process development, Organic Process Research & Development, 2005, 9, 730-737
    |3| A.T. Boam, A.G. Livingston, D. Nair, P. MsCormac, S. Hargreaves, US2006/0135760A1, 2006.
    |4| Y.H. See Toh, F.W. Lim, A.G. Livingston, Polymeric membranes Ior nanoIiltration in polar aprotic solvents, Journal oI
    Mebrane Science, 2007, 301, 3-10.
    -168-
    OF.7.7
    Production of surfactin and fengycin by Bacillus subtilis in a bubbleless membrane
    bioreactor
    F. Coutte, D. Lecouturier, V. Leclere, M. Bechet, P. Jacques, P. Dhulster

    Laboratoire de Procedes Biologiques, Genies En:vmatique et Microbien (ProBioGEM, EA 1026), PolvtechLille, Bd Paul
    Langevin, F-59655 Jilleneuve dAscq Cedex, France.
    Didier.lecouturieruniv-lille1.Ir
    SurIactin and Iengycin are lipopeptides produced by Bacillus subtilis. During lipopeptide production in bioreactors, and
    particularly during surIactin production, the combination oI both vigorous stirring and gas sparging causes a large Ioaming
    which makes the pilot or process scale production Iastidious. A bubbleless bioreactor was used Ior the Iirst time Ior the
    production oI surIactin and Iengycin by B. subtilis ATCC21332 with culture aeration by a hollow Iiber membrane air-liquid
    contactor. Membranes oI various natures (polyethersulIone and polypropylene) and several conIigurations (external and
    submerged membranes) were tested. Bacterial growths, volumetric oxygen transIer rate and lipopeptides production were
    monitored in the bioreactors. For all the tested membranes, the bioreactors were Iound to readily support bacterial growth and
    lipopeptide production. With external hollow Iiber aeration modules, the amounts oI surIactin obtained were 772 mg and 674
    mg with the 0.65 m pore size polyethersulIone membrane and the 0.2 m pore size polypropylene membrane respectively.
    An interesting Iengycin production oI 982 mg was obtained with the submerged polypropylene membrane oI 0.05 m pore
    size simultaneously to the production oI 469 mg oI surIactin. This result seemed in relation to the membrane composition. The
    results showed the interesting potential oI bubbleless membrane aeration Ior lipopeptide production under well-controlled
    conditions compared to an usual Ioaming Iermentation process. During the cultures, the concentration oI surIactin in the
    medium remained quite low. Most produced surIactin was adsorbed on the membranes. The adsorption oI the surIactin on each
    membrane and its eIIect on the volumetric oxygen mass transIer coeIIicient were studied.
    OF.7.8
    ScaIe-up of eIectrodIaIysIs wIth uItrafIItratIon membranes: fractIonatIon of an
    antIhypertensIve peptIde from aIfaIfa whIte proteIn hydroIysate
    L. Firdaous
    1
    , P. Dhulster
    2
    , J. Amiot
    1
    , D. Lecouturier
    2
    , F. Lutin
    4
    , L.-P. Vezina
    5
    , L. Bazinet
    1
    1
    Institut des Nutraceutiques et des Aliments Fonctionnels (INAF), Departement des sciences des aliments et de nutrition,
    Universite Laval, Quebec, Canada G1K 7P4.
    2
    Laboratoire des Procedes Biologiques, Genie En:vmatique et Microbien, ProBioGEM UPRES-EA 1026, PolvtechLille, Aile
    C, 59655 Jilleneuve dAscq, France.
    3
    Eurodia industrie SA, B.P. 300527, Wissous, 94633 Rungis Cedex, France.
    4
    Medicago Inc., Quebec, Canada G1J 3J9.
    Laurent.BazinetIsaa.ulaval.ca
    In our study, we investigated the Iractionation and puriIication oI an antihypertensive peptide (VW) Irom an industrial AlIalIa
    White Protein Concentrate (AWPC), by a novel membrane technology, electrodialysis with ultraIiltration membranes (EDUF)
    |1|. This technology, based on the separation mechanisms oI conventional membrane Iiltration (size) and electrophoresis
    (electrical charge), is suitable Ior the large-scale Iractionation oI valuable molecules Irom complex Ieedstocks |1|. In the Iirst
    set oI experiments, the Iractionation was carried-out with an eIIective membrane area oI 100 cm
    2
    . Two ultraIiltration
    membranes were stacked in an electrodialysis cell to allow a conIiguration with two electrode rinsing compartments, one Ieed
    compartment and two recovery compartments: KCl 1 (towards the anode) and KCl 2 (towards the cathode). Results showed
    that EDUF is a selective method oI separation with a transport rate Ior charged peptides oI 7.3 g/m
    2
    .h. Among a total oI 70
    peptides contained in the AWPC hydrolysate, only 8 peptides were Iound in the separated adjacent solutions (KCl 1 and KCl
    2). Amongst these 8 migrating peptides, the target anti-hypertensive peptide VW was recovered in KCl 2 at pH 3 with a Iinal
    transmission rate oI 1.67 and in KCl 1 at pH 9 with a Iinal migration rate oI 0.88. This weak recovering yield was
    explained by the pH oI the recovery compartments (KCl 1 and KCl 2) close to its pI resulting in its weak migration |2|. These
    observations and results obtained Irom the Ieasibility investigation were used in a second set oI experiments carried-out on a
    semi-industrial pilot plant. The eIIective membrane area was ranging between 0.1 and 0.14 m
    2
    and pH in the recovering
    solutions was kept constant. DiIIerent conIigurations were tested with stacking oI UF membranes Ior the separation oI anionic
    or cationic peptides (one recovery compartment) as well as stacking oI UF membranes Ior the simultaneous separation oI
    -169-
    anionic and cationic peptides (two recovery compartments). At the end oI the 2 hour-treatment, according to the conditions and
    cell conIigurations used, Iinal peptide concentrations oI 700 mg/L were obtained in the recovery compartments as well as
    transmission rates Ior the VW peptide up to 50.
    |1| Bazinet, L. ; Amiot, J.; Poulin, J.-F; Tremblay, A. ., Labbe, D. Process and system Ior separation oI organic charged
    compounds. Demande de Brevet PCT/CA2005/000337.
    |2| Firdaous, L.; Dhulster, P.; Amiot, J.; Gaudreau, A.; Lecouturier, D.; Kapel, R.; Lutin, F.; Vezina, L.-P.; Bazinet, L. 2009.
    Concentration and selective separation oI bioactive peptides Irom an alIalIa white protein hydrolysate by electrodialysis with
    ultraIiltration membranes. Journal oI Membrane Science, In Press.
    OF.7.9
    Membrane emulsification for the formulation of stimuli responsive multiple
    emulsions containing labile bioactive molecules
    E. Piacentini
    1,2
    , L. Giorno
    1
    , E. Drioli
    1,2
    1
    Institute on Membrane Technologv, CNR-ITM, Universitv of Calabria, Jia P. Bucci 17 C, 87036 Rende (CS), Italv.
    2
    Department of Chemical Engineering and Materials, Universitv of Calabria, Jia P. Bucci 42/A, 87030, Rende (CS), Italv.
    l.giornoitm.cnr.it
    The aim oI this work was to prepare microstructured dispersed systems having release properties activated by external stimuli.
    The idea was to Iunctionalize the interIace oI droplets emulsion with biosensing molecules acting as receptors towards target
    compounds. When receptor-stimulus interaction occurred, the release oI bioactive molecules contained within the droplets was
    activated.
    Membrane emulsiIication was used to build up such microstructured multiIunctional droplets. In particular, the process was
    tested with a selI-regulated insulin delivery system based on glucose-sensitive multiple W/O/W droplets. This glucose-
    sensitive deliverv svstem has been used as model study case.
    Concanavalin A (Conc A) was used as glucose sensor. The Conc A is a protein having high aIIinity Ior glucose. The presence
    oI hydrophilic and hydrophobic sites in the molecule structure suggested the use oI Conc A also as emulsiIier. The interaction
    oI Conc A with glucose determines a change oI its interIacial properties, so that the release oI molecules contained within the
    droplets can be activated by means oI Conc A displacement Irom emulsion interIace. A common amino acid was used as
    'indicator molecule contained within the droplets to easily monitor the controlled release.
    Two diIIerent membrane emulsiIication processes were applied. W/O emulsion was prepared by cross-Ilow membrane
    emulsiIication using Conc A as emulsiIier dissolved in the dispersed phase. Hydrophobic Shirasu Porous Glass (SPG) tubular
    membrane with pore diameter (D
    p
    ) oI 0.4 m was used. The indicator was dissolved in the dispersed phase.
    This W/O emulsion was used as dispersed phase in the W/O/W emulsion preparation. Stirred membrane emulsiIication was
    applied. Hydrophilic metallic disc membrane with pore diameter (D
    p
    ) oI 10 m was used. The optimal operating conditions
    (shear stress at membrane surIace, dispersed phase Ilux, emulsiIier types and concentration) were evaluated in order to a)
    preserve the property oI the W/O interIace produced during the Iirst step and b) control droplets size distribution and stability
    to obtain targeted particles. Conc A with other surIactants (i.e. Tween 80) were used as emulsiIier in the preparation oI W/O/W
    emulsion.
    The release oI the indicator Irom multiple emulsion was evaluated as Iunction oI the time both in presence and absence oI
    glucose. The release oI the indicator was controlled by the presence, concentration and subsequent injection oI glucose in the
    external solution oI the W/O/W emulsion.
    Results showed that Conc A acted as glucose sensor at W/O/W emulsion interIace, speciIically recognizing glucose in solution
    and activating the release oI molecules contained within the droplets in a highly controlled way. Membrane emulsiIication is
    conIirmed as a unique methodology to aIIord the Iormulation oI complexes microstructures with speciIic properties, especially
    Ior applications in pharmaceutical, biomedicine, biotechnology and Iood Iields.
    -170-
    OF.8.1
    Crossed hollow fiber membrane bioreactor using human hepatocytes for in vitro
    study of drugs and metabolic diseases
    L. De Bartolo
    1
    , S. Salerno
    1
    , E. Curcio
    2
    , A. Piscioneri
    1,3
    , M. Rende
    1,2
    , S. Morelli
    1
    , F. Tasselli
    1
    , A. Bader
    4
    , E. Drioli
    1,2
    1
    Institute on Membrane Technologv, National Research Council of Italv, ITM-CNR, c/o Universitv of Calabria, via P. Bucci
    cubo 17/C, I-87030 Rende (CS) Italv
    2
    Department of Chemical Engineering and Materials Universitv of Calabria, via P. Bucci, I-87030 Rende (CS) Italv
    3
    Department of Cell Biologv, Universitv of Calabria, via P. Bucci, 87030 Rende (CS), Italv
    4
    Biomedical-Biotechnological Center, BBZ, Universitv of Leip:ig, Germanv
    l.debartoloitm.cnr.it
    Liver tissue constructs consisting oI Iunctional cells and artiIicial materials are being greatly studied Ior their applications in
    the clinical Iield Ior organ replacement and in the in vitro studies Ior drug development and metabolic diseases. The
    development oI bioartiIicial systems that are able to Iavour the liver reconstruction and to modulate liver cell behaviour is an
    important challenge in liver tissue engineering |1,2|.
    Isolated hepatocytes that are able to perIorm the Iull range oI known in vivo biotransIormation, synthetic and detoxiIication
    Iunctions rapidly lose their liver speciIic Iunctions when maintained under standard in vitro culture conditions. A crossed
    hollow Iiber membrane bioreactor was developed to support the long-term maintenance and diIIerentiation oI human
    hepatocytes. The bioreactor consists oI two types oI hollow Iiber (HF) membranes with diIIerent molecular weight (MW) cut-
    oII and physico-chemical properties cross assembled in alternating manner: PEEK-WC and polyethersulIone (PES), used Ior
    the medium inIlow and outIlow, respectively. The combination oI these two Iiber set produces an extracapillary network Ior
    the adhesion oI cells and a high mass exchange through the cross Ilow oI culture medium. The transport oI liver speciIic
    products such as albumin and urea together with the transport oI drug such as diazepam was modelled and compared with the
    experimental metabolic data. The theoretical metabolite concentration diIIered 7.5 Ior albumin and 5 Ior urea with respect
    to experimental data. The optimised perIusion conditions oI the bioreactor allowed the maintenance oI liver Iunctions in terms
    oI urea synthesis, albumin secretion and diazepam biotransIormation up to 18 days oI culture. In particular the good
    perIormance oI the bioreactor was conIirmed by the high rate oI urea synthesis (28.7 g/h 10
    6
    cells) and diazepam
    biotransIormation. Diazepam was completely metabolised as occur in vivo where each oI metabolites is Iinally converted to
    oxazepam. In the bioreactor human hepatocytes expressed at high levels the individual cytochrome P450 isoenzymes involved
    in the diazepam metabolism. The results demonstrated that crossed HF membrane bioreactor is able to support the maintenance
    oI primary human hepatocytes preserving their liver speciIic Iunctions Ior all investigated period. This device may be a
    potential tool in the liver tissue engineering Ior drug metabolism/toxicity testing and study oI disease pathogenesis
    alternatively to animal experimentation.
    |1| E. Drioli and L. De Bartolo. Membrane bioreactor Ior cell tissues and organoids. Artificial Organs 2006; 30(10):793-802.
    |2| L. De Bartolo, S. Morelli, A. Piscioneri, L.C. Lopez, P. Favia, R. d`Agostino, E. Drioli. Novel Membranes and surIace
    modiIication able to activate speciIic cellular responses. Biomolecular Engineering 2007, 24:23-26.
    OF.8.2
    The influences of the layer by layer deposition of polyethylenimine and alginate
    on the transport rates and hemocompatibility of PSF membranes
    F. Yasar Mahlicli, S. Alsoy Altinkaya
    Department of Chemical Engineering, I:mir Institute of Technologv, Gulbahe Kovu, 35430, Urla, I:mir, Turkev
    Iilizyasariyte.edu.tr
    Most oI the hemodialysis membrane materials are hydrophobic in nature and allow protein adsorption on the surIace easily
    which causes reductions in solutes permeation characteristics and the activation oI diIIerent deIense systems in blood |1|.
    SurIace modiIication is a commonly used approach to create surIaces oI biomedical devices which resist to protein adsorption.
    Numerous surIace modiIication methods have been suggested which can be summarized as blending hydrophilic polymers into
    the membrane Iorming solution; graIting hydrophilic groups by UV-irradiation or low temperature plasma technique; graIt
    copolymerization oI monomers; coating with hydrophilic polymers or copolymers |1| and polyelectrolyte multilayers
    immobilization |2|. Recently, the layer by layer selI-assembly (LBL) technique has emerged as an eIIicient and easy surIace
    -171-
    modiIication technique in biomedical engineering |2|. The method depends on the sequential deposition oI polycations and
    polyanions on a polymeric surIace upon immersing the membrane into an aqueous solution oI oppositely charged
    polyelectrolytes |2|.
    The main purpose oI this study is to improve the clearing perIormance and hemocompatibility oI the polysulIone (PSF) based
    hemodialysis membranes. PolysulIone is a commonly used synthetic polymer material Ior Iabrication oI membranes due to its
    excellent properties such as chemical inertness, thermal stability, and mechanical strength. However, the hydrophobic nature oI
    PSF is undesirable in hemodialysis applications |3|. To improve the hydrophilicity and hemocompatibility oI PSF membranes,
    we developed polyethylenimine (PEI) and alginate (ALG) selI-assembled multilayers on sulIonated PSF membrane through
    LBL technique. Conventional PSF has no Iunctional groups and charges, thus, it was Iirst modiIied by sulIonation to induce
    negatively charged groups (SO
    3
    -
    ) beIore preparing the support membrane |4|. Polyethylenimine (PEI) was chosen as the
    polycationic macromolecule Ior anchoring to the negatively charged membrane surIace due to its availability, strong base
    character, thus, easy prototanation and well-controlled quality. Alginate was selected as negatively charged polyelectrolyte
    since it was described as a hydrophilic, biocompatible, bioadhesive, economic and strong polyanion |5|. The Iabricated PSF
    membranes were characterized in terms oI toxic solute permeation rate, amount oI adsorbed protein, blood compatibility as
    well as structural and mechanical properties.
    |1| S. Sun, Y. Yue, X. Huang, D. Meng, Protein adsorption on blood-contact membranes, Journal oI Membrane Science, 2003,
    222, 3-18.
    |2| D.G. Yu, C.H. Jou, W.C. Lin, M.C. Yang, SurIace modiIication oI poly(tetramethylene adipate-co-terephthalate)
    membrane via layer-by-layer assembly oI chitosan and dextran sulIate polyelectrolyte multiplayer, Colloids and SurIaces B:
    BiointerIaces, 2007, 54, 222229.
    |3| J. Wang, Y. Xu, L. Zhu, J. Li, B. Zhu, Amphiphilic ABA copolymers used Ior surIace modiIication oI polysulIone
    membranes, Part 1: Molecular design, synthesis, and characterization, Polymer, 2008, 49, 32563264.
    |4| J. F. Blanco, Q. T. Nguyen, P. Schaetzel, SulIonation oI PolysulIones: Suitability oI the SulIonated Materials Ior
    Asymmetric Membrane Preparation, Journal oI Applied Polymer Science, 2002, 84, 24612473.
    |5| M. George, T.E. Abraham, Polyionic hydrocolloids Ior the intestinal delivery oI protein drugs: Alginate and chitosan,
    Journal oI Controlled Release, 2006, 114, 114.
    OF.8.3
    Novel multi-layer scaffolds for tissue engineering
    D. Stamatialis
    1
    , B.J. Papenburg
    1
    , I-J. de Vries
    1
    , J. de Boer
    2
    , C. van Blitterswijk
    2
    , M. Wessling
    1
    1
    Membrane Science and Technologv, Institute for Biomedical Technologv, Facultv of Science and Technologv, Universitv of
    Twente,P.O.Box 217, 7500 AE Enschede, The Netherlands
    2
    Department of Tissue Regeneration, same address
    d.stamatialisutwente.nl
    In tissue engineering (TE), two major issues are extensively studied: eIIicient nutrient supply and optimal cell organization.
    Through optimal scaIIold design, both issues can be addressed using: (I) scaIIold porosity Ior nutrient diIIusion and (II)
    micropatterning to induce cell organization (Figure 1a) |1, 2|.
    In this work we present the development oI 3D scaIIolds by stacking multi-layered porous Poly (l-lactic acid) (PLLA) sheets
    Ieaturing microchannels (see Figure 1b). The cells distribute well within the scaIIold as seeding / attaching oI cells occurs on
    individual layers that are stacked subsequently. The microchannels oI the sheets, Iabricated by phase separation micromolding
    (PSM), allow besides cell organization also nutrient perIusion throughout the scaIIold; whereas inner-porosity oI the sheets
    guarantees diIIusion between the layers. Under static culture conditions, cell proliIeration is inhibited due to nutrient
    limitations. Under dynamic conditions, perIusion occurs throughout the scaIIold leading to higher cell proliIeration on all
    layers compared to static culture.
    -172-
    (a) (b)
    Figure 1. (a) ConIocal Iluorescence microscopy images oI C2C12 pre-myoblast cells cultured on porous PLLA sheets
    Ieaturing 30 m wide channels (MagniIication 63x, cytoskeleton labeled in green and nucleus labeled in blue). (b) Schematic
    illustration oI cell culturing on stacked micro-patterned sheets (adapted Irom |2|).
    This project is Iinancially supported by BMTi, Institute Ior Biomedical Technology and the Dutch Program Ior Tissue
    Engineering (DPTE).
    |1| B. J. Papenburg, L. Vogelaar, L. Bolhuis Versteeg, R.G.H. Lammertink, D. F. Stamatialis and M. Wessling, One step
    Iabrication oI porous micropatterned scaIIolds to control cell behaviour, Biomaterials 28 (2007) 1998-2009.
    |2| D. F Stamatialis, B. J. Papenburg, M. Girones, S.SaiIul, N.M.S. Bettahalli, S. Schmitmeier and M. Wessling, Medical
    applications oI membranes, Drug delivery, artiIicial organs and tissue engineering, J. Membr. Sci., 308 (2008) 1-34.
    OF.8.4
    Keynote: Membranes for artificial organs
    J. Vienken
    BioSciences Department, Fresenius Medical Care, Bad Homburg, Germanv.
    joerg.vienkenImc-ag.com
    Membranes are the key elements oI detoxiIication devices applied Ior artiIicial kidneys, liver support devices and oxygenators.
    PuriIication oI blood during the therapy oI kidney or liver Iailure is achieved through Iilters with capillary membrane. In the
    case oI dialysis and liver Iailure therapy, they are usually made Irom hydrophilic polymers or Irom hydrophilic polymer
    blends. In contrast, in oxygenators, capillary membranes are made Irom hydrophobic polymers to provide an easy passage
    oI.oxygen and carbondioxide.
    These membranes represent one oI the success stories oI medical device application in recent years. When John Abel in the
    United States and Georg Hass in Germany started to investigate the application oI membranes Ior the treatment oI kidney
    patients at the beginning oI the 20. century, they would have never dreamt that nearly a hundred years later in 2009 about 1,5
    million kidney patients owe their lives to dialysers oI which more than 180 million pieces containing capillary membranes
    including about 450 million km oI capillary membranes have been sold in 2007. Modern capillary membranes Ior the use in
    dialysers and Ior liver Iailure therapy are currently Iabricated mainly Irom so-called synthetic polymers, such as polysulIone
    (PSu), polyamide (PA), poly-methylmethacrylate (PMMA) or polyacrylonitrile (PAN). Modern oxygenator membranes in
    early days Iabricated Irom silicon rubber, are now made Irom polyoleIines, polymethylpentene or polyvinylidenIluoride. A
    reproducible high quality in order to guarantee both, the patients saIety and a reasonable cost oI production, have been the
    targets oI eIIorts oI scientists, engineers and managers.
    Polymers used Ior dialysis membranes should allow Ior a membrane Iormation process to achieve low- and high-Ilux
    conIigurations, such that all modern treatment modalities (HD, HDF, HF) can be perIormed. Following the investigations oI
    the last decades, a membrane polymer must also show a series oI biocompatibility pattern with regard to blood coagulation,
    cell stimulation and vasoactive properties. Due to the typical chronic and longterm application oI biomaterials used mainly in
    dialysis, the amount oI extractables (oligomers, sterilants, etc) must be reduced to the lowest acceptable limit and, iI not
    avoidable, should not induce adverse acute (allergic) reactions. As there is still no general guarantee Ior rinsing Iluids void oI
    exo- and endotoxins, e.g. in dialysis, those polymers should be preIerred which oIIer a considerable adsorptive capacity Ior
    such impurities.
    -173-
    OG.1.1
    Crossflow microfiltration (0.1 m) of skimmed milk
    The role of electrostatic interactions on the soluble protein transfer
    A.J.E. Jimenez-Lopez
    1,2,3
    , F. Garnier-Lambrouin
    2,3
    , F. Rousseau
    2,3
    , G. Gesan-Guiziou
    2,3
    1
    Soredab SAS, La Tremblave, F-78125 la Boissiere Ecole, France.
    2
    INRA UMR1253 Science et Technologie du Lait et de luf, 65 rue de saint Brieuc, F-35000 Rennes, France.
    3
    Agrocampus Ouest UMR1253 F-35000 Rennes, France.
    anne.jimenezrennes.inra.Ir
    CrossIlow microIiltration (MF 0.1 m) oI skimmed milk is widely used in the dairy industry to separate casein micelles
    (negatively charged proteins assumed as spherical colloids with a mean diameter oI about 200 nm) Irom soluble proteins
    (molecules with various diameters 10 nm and charges). During this process, the accumulation oI casein micelles at the
    membrane surIace depends on the hydrodynamic conditions and altered the soluble protein transIer. Sharp modiIications oI the
    protein transIer were especially observed in critical hydrodynamic conditions ((J/t
    w
    )
    crit
    with J permeation Ilux and
    w
    shear
    stress at the membrane surIace) corresponding to the set-up oI an irreversible casein micelles deposit (Jimenez-Lopez et al.,
    2008). Few studies have previously Iocused on the soluble protein transIer during milk MF, but any oI them has explained this
    transIer considering simultaneously the individual characteristics oI the proteins, the possible interactions with casein micelles
    and the hydrodynamic conditions.
    Hence, this work studies the soluble protein transIer during the skimmed milk MF, as Iunction oI the physico-chemical
    characteristics oI the proteins and the hydrodynamic conditions, especially the critical ones. For that aim, the transmission oI
    the Iive major soluble proteins oI milk presenting diIIerences in charge and diameter was Iollowed in the presence and in
    absence oI casein micelles, using an original methodology oI Iiltration based on step by step variation oI
    w
    at constant J.
    Some experiments were perIormed with an increase oI ionic strength in order to lead to screen protein charges and hence
    decrease electrostatic interactions between proteins.
    The present work was conducted on thermised skimmed milk. MF was operated with a pilot equipped with the uniIorm
    transmembrane pressure system and with a 0.1 m tubular ceramic membrane, Kerasep (Novasep, France). The operating
    conditions were: 48C; volume reduction ratio2; constant permeate Ilux J 50 L h
    -1
    m
    -2
    and wall shear stress
    w
    , ranging Irom
    120 Pa to 55 Pa. The ionic strength was increased by adding NaCl up to 300 mM.
    In the presence oI the casein micelle deposit, the transIer oI negative charge soluble proteins is decreased by 30. This
    decrease was shown not to be the Iact oI steric repulsion phenomenon, but could mainly be attributed to electrostatic
    interactions: the deposit created a high density oI negative charges at the membrane surIace that induces electrostatic
    repulsions between accumulated casein micelles and soluble proteins. In the case oI the positively charged protein (lactoIerrin),
    the only presence oI casein micelles at the membrane surIace decreased its transmission by 50 . LactoIerrin was shown to be
    entrapped in the casein micelles network accumulated at the membrane surIace. Attractive electrostatic interactions between
    casein micelles and lactoIerrin seem to be the major phenomenon controlling this transIer. The increase oI ionic strength
    permitted to strongly increase lactoIerrin transmission with a linear correlation between transmission and ionic strength.
    Understanding the transIer oI soluble proteins as a Iunction oI the accumulated matter is essential Ior developing strategies to
    improve membrane-based processes and better control the composition oI the dairy products.
    A.J.E Jimenez-Lopez, N. Leconte, O. Dehainault, C. Geneste, L. Fromont, G. Gesan-Guiziou, Sep. Pur. Technol. 61 (2008)
    33-43
    OG.1.2
    Scale-up of a batch membrane process plant for the treatment of an olive vegetaton
    waste water steam: A case study
    M. Stoller, A. Chianese
    Universitv of Rome ,La Sapien:a', Department of Chemical Engineering, Jia Eudossiana 18, 00184 Rome, Italv.
    stolleringchim.ing.uniroma1.it
    The olive vegetation waste water is a waste stream produced by the olive oil mill Iactories, characterized by a very high
    organic matter (COD values equal to 50-150 g/l).
    -174-
    Without Iouling control, membranes would reach zero-Ilux condition very Iast, within days. This result can be reached only by
    proper Iouling control, which relays on both critical Ilux measurements and optimized operation methods previously developed
    by the Authors |1|. The preliminary studies perIormed on a 100 liter batch membrane plant were successIully completed and
    validated.
    Critical Ilux depends among others Irom hydrodynamic conditions. This parameter can change sensibly during scale-up, as
    perIormed during this work. A 2m
    3
    /day batch membrane near-to-industrial sized plant was constructed on an olive mill site and
    used Ior one olive oil campaign. The plant puriIies the waste water stream by means oI bioIermentation, Ilocculation,
    ultraIiltration, nanoIiltration and reverse osmosis. These process steps were chosen since they appeared promising in previous
    studies |2,3|.
    Critical Iluxes oI all involved membrane process steps were measured in order to apply the optimization method which was
    aIterwards validated.
    A comparison oI the critical Iluxes obtained on the pilot plant and the bigger one demonstrates that this parameter is useIul not
    only Ior Iouling issues but also Ior scale-up purposes.
    |1| M. Stoller, A. Chianese: 'Technical optimization oI a batch olive wash wastewater treatment membrane plant, 2006,
    Desalination 200(2006) pp 734-736. DOI. 10.1016/f.desal.2006.03.
    |2| M. Stoller: 'Technical optimization oI a dual ultraIiltration and nanoIiltration pilot plant in batch operation by means oI the
    critical Ilux theory: a case study, 2007, Chemical Engineering & Processing Journal Vol 47/7 (2008), pp 1165-1170, DOI.
    10.1016/f.cep.2007.07.012
    |3| K. Movassaghi, M. Stoller, L. Miranda, A. Chianese: 'Olive vegetation wastewater treatment by means oI diIIerent nano-
    TiO2 powders and photoreactor setup, 2008, Proceedings SPEA5, OP5.7 , Palermo, Italy.
    OG.1.3
    Assessment of a membrane process for regeneration of secondary wastewater
    treatment plant (WWTP) effluents. Pilot plant operation
    G. Perez, P. Gomez, A. Plaza, R. Ibaez, A.M. Urtiaga, I. Ortiz
    Department of Chemical Engineering, Universitv of Cantabria Avda. Los Castros s/n 39005 Santander, Spain.
    urtiagaunican.es
    Water scarcity problem and stringent environmental legislation turn the interest to non-conventional water sources, such as
    reclaimed water. When considering the reuse oI water Ior industrial purposes, the quality requirements are highly dependant on
    the speciIic Iinal use. The most stringent quality limits are related to the production oI water Ior boiler make-up. A Iew studies
    show that that the cost oI producing water Ior power generation plants can be remarkably decreased by using reclaimed water
    Iorm a secondary wastewater treatment plant, instead oI the traditional surIace water source. In the Iield oI water treatment,
    most oI the membrane research is Iocused to the treatment oI surIace water, as well as in the application oI MBR technology to
    the treatment oI sewage water. More recently, NF and RO are being investigated Ior the removal oI emerging micropollutants,
    namely endocrine disrupting and pharmaceutically active compounds.
    In this work and advanced water treatment process is investigated at pilot plant scale. The study is perIormed in collaboration
    with the regional water authority. A combination oI dead-end UF, RO and Electrochemical Oxidation is considered. The pilot
    plant testing is perIormed on-site at the WWTP oI Vuelta Ostrera (Cantabria, Spain), located in a highly industrialized area.
    The UF unit employs two hollow Iiber membrane modules, AquaFlex (NORIT), 40 m
    2
    each one and operates in a continuous
    mode with a maximum Ilow-rate oI 3 m
    3
    /h. Total removal oI suspended solids, turbidity and E. Coli is attained. In a period oI
    continuous operation oI 1 month, the Iiltration properties are maintained by back-Ilushing and chemical cleaning. At present,
    the eIIect oI the coagulant dose is under study, so the operation costs can be minimized.
    Reverse osmosis is aimed at the reduction oI conductivity, organic matter and emerging micropollutants. A Iirst part oI the
    study has been perIormed at laboratory scale (Sepa CF Membrane Cell System, Osmonics) using the membrane BW30 DOW,
    and retentate reIlux up to 80 recovery. AIter an extensive analytical characterization in which more than 80 micropollutants
    were quantiIied in the eIIluent oI the WWTP, a group oI eight compounds was selected among the most abundant:
    carbamazepine, caIIeine, ketorolac, antipyrine, sulIamethoxazole, isoproturon, dicloIenac, and ibuproIen. UltraIiltrated water
    was spiked with pharmaceuticals to rise their initial concentration to 5 g/L. Reverse osmosis provided a rejection higher than
    98.5 Ior all the micropollutants. The quality oI the permeate was also high in terms oI conductivity, that was maintained
    lower than 25 S/cm. Finally, the treatment oI the concentrate obtained in the reverse osmosis unit was perIormed by
    electrochemical oxidation, using boron doped diamond anodes. AIter 1 hour oI electrochemical oxidation treatment, more than
    90 oI the micropollutants content was eliminated, while in a 5 hours period, 100 oI elimination was attained. At present,
    pilot plant testing oI RO (hydranautics, LFC1,) and electrooxidation (1 m
    2
    anode area unit) has started. The results will permit
    the evaluation oI the water regeneration process under the requirements oI the surrounding industrial users.
    -175-
    Financial support oI projects Consolider CSD2006-44, 062/SGTB/2007/3.1 and PET20070431 is grateIully acknowledged.
    MARE S.A. collaboration is also acknowledged.
    Judd, S. JeIIerson, B., Membranes Ior industrial water recovery and reuse. Elsevier, 2003.
    Ternes, T. A. and Joss, A. (2006). Human Pharmaceuticals, Hormones and Fragances. The challenge oI micropollutants in
    urban water management. IWA Publishing, London.
    OG.1.4
    ~Plug and clean membrane systems for small communities and villages
    D. Vial
    1
    , V. Raktae-ngan
    2
    , T. Wachinski
    3
    , F. McKeever
    2
    1
    Pall Corporation, 3 rue des Gaudines, 78100 Saint-Germain-en-Lave, France
    2
    Pall Corporation, Unit 2501 Rasa Tower 25th Floor, 555 Phaholvothin Road, Chatuchak, 10900 Bangkok, Thailand
    3
    Pall Corporation, 25 Harbor Park Drive, Port Washington, NY 11050, USA
    denisvialeurope.pall.com
    Membrane based systems (microIiltration, ultraIiltration, nanoIiltration and reverse osmosis) are now largely widespread Ior
    the puriIication oI water oI any origin in order to produce drinking water or industrial water.
    This paper introduces these Iour Iamilies oI membranes and their scopes oI application. It describes how these technologies
    can be advantageously adapted to provide drinking water in the isolated villages and rural areas using Pall Aria AX systems.
    These compact cost eIIective 'plug and clean systems are equipped with modules containing organic hollow Iibres made oI
    PVDF and operating in an out-to-in mode under pressure.
    Results oI long term operation are presented to support the advantages and beneIits oI the Pall Aria AX system. Microbial
    analyses conIirm the membrane Iiltration system's ability to completely remove amoebas, parasites, cysts oI Giardia and
    oocysts oI Crvptosporidium while producing treated water with turbidity always below 0.1 NTU even during Ieed water high
    turbidity events oI over 100 NTU.
    The paper also demonstrates that chemical addition up-stream oI the membranes can Iurther improve water quality where
    dissolved compounds such as arsenic are present. Case studies Irom isolated villages in rural areas are presented.
    OG.1.5
    Keynote: Actual position of electromembrane processes on the world desalination
    market
    L. Novak
    MEGA a.s., Pod Jinici 83, 471 27 Stra pod Ralskem, C:ech Republic.
    lnovakmega.cz
    Although all water desalination technologies remain an expensive alternatives to existing water sources, world installed
    capacity has grown rapidly in recent years. Largest growth contribution lies in rising water demand caused by population
    growth in scarce water regions (GulI, Spain, southwest oI the USA).
    Pressure membrane processes, thermal processes and electromembrane processes are used today Ior water desalination.
    Pressure membrane processes (reverse osmosis and nanoIiltration) are the most universal technology applied on more than one
    halI oI the market. Advantage oI reverse osmosis inheres in high rejection, nanoIiltration is chosen Ior its low energy demand.
    Thermal processes (multi stage Ilash, multiple eIIect distribution and vapour compression) gain their position in the
    desalination oI highly salted wastewaters and seawaters oI the GulI region, because oI low dependence oI thermal process
    economy on rising salt concentration. Market share oI electromembrane processes is relatively small in compare with pressure
    and thermal ones. Electrodialysis is successIul in low salinity brackish water, river water and wastewater desalination and
    treatment oI diIIicult to treat waters like nitrates removal Irom wastewater or Iluorides Irom groundwater. Advantage oI
    electrodialysis is high water recovery, caused by higher salt supersaturation, and lower Iouling susceptibility, which allow
    using simpler water pre-treatment. Electrodialysis is also very important process Ior separation oI ionic and non-ionic
    molecules with large applications in Iood industry (dairy, wine), electroplating industry and pharmacy. Electrodeionization is
    gaining its position in pure water market being and alternative to reverse osmosis and ion exchange without any chemical
    needs. Electrophoresis is used Ior regeneration oI paint coating baths.
    -176-
    Advantages oI all desalination technologies are pulled together in hybrid processes. Water treatment process with the recovery
    oI electrodialysis, rejection oI reverse osmosis, product quality oI electrodeionization and concentrate salinity oI thermal
    process can be realized by combination oI all desalination processes. The way leads us through complex mathematical models
    oI joint technology, thorough laboratory and pilot scale experimentation and economical evaluation oI every alternative design
    oI hybrid technology. High level oI knowledge oI hybrid technology is necessary to be able to design desalination plants today,
    when sizes and capital costs oI new desalination project are rising sharply to cut operating costs.
    The19th IDA Worldwide Desalting Plant Inventory, 2006
    Desalination Markets 2005-2015, 2004
    Desalination Markets 2007: A Global Industry Forecast
    -177-
    -178-
    POSTER COMMUNICATIONS
    -179-
    PA.1.1
    Active hybrid membranes: from in situ nanostructuration process to modulated
    functional properties
    E. Espuche, S. Clemenson, L. David
    Universite de Lvon, F-69003, Lvon, Universite Lvon 1, F-69622 Jilleurbanne, France, CNRS, UMR5223, Ingenierie des
    Materiaux Polvmeres, Laboratoire des Materiaux Polvmeres et des Biomateriaux
    eliane.espucheuniv-lyon1.Ir
    During the last Iew years, the preparation oI hybrid organic-inorganic nanocomposite membranes by in situ methods has been
    a subject oI growing interest in the Iield oI active membranes. Indeed it generally allows to obtain homogeneous dispersions oI
    nanometer size Iillers within the membrane and to achieve Iunctional properties|1,2|. The aim oI this work is to prepare
    palladium/polymer nanocomposites membranes with diIIerent morphologies and modulated Iunctional properties.
    Dense Iilms were prepared by cast process Irom palladium acetate and polyetherimide. The Iilms were annealed according to
    diIIerent cure cycles. A nanostructuration process leading to the Iormation oI crystalline palladium nanoparticles within the
    Iilm occurred during the thermal treatments. The particles were homogeneously dispersed Ior Pd amount lower than 15wt.
    For higher palladium content, a surIace layer composed oI Pd particles was obtained in addition to an homogeneous dispersion
    oI nanoparticles in the bulk Ior some curing conditions. The eIIects oI the nanoparticle dispersion state were studied on the
    membrane activity. Enhanced eIIects were observed as the total amount oI particles increased and particularly as the particles
    were mainly located at the Iilm surIace. In order to promote the palladium particles accessibility, asymmetric porous hybrid
    Iilms were prepared. As Ior dense Iilms, palladium crystalline nanoparticles were Iormed aIter thermal annealing. These
    particles were mainly located at the Iilm surIace oI the dense polymer layer and on the walls oI the pores (Figure 1).
    Figure 1 : porous nanocomposite Iilms a) at the SEM scale and b)at the TEM scale on an ultra-microtomed slice.
    |1| S.S. Ozdemir, M.G. Buonomenna, E. Drioli, Catalytic polymeric membranes : preparation and application, Applied
    Catalysis A: General, 2006, 307,167-183
    |2| K. Ebert, G. Bengtson, R. Just, M. Oehring, D. Fritsch, Catalytically active poly(amideimide) nanoIibre mats with high
    activity tested in the hydrogenation oI methyl-cis-9-octadecenoate, Applied Catalysis A: General, 2008, 346, 72-78
    |3| J.M.Compton, D.W. Thompson, D.E. Kranbuehl, S. Ohl, O. Gain, L. David, E. Espuche, Hybrid Iilms oI polyimide
    containing in situ generated silver or palladium nanoparticles : eIIect oI the particle precursor and oI the processing conditions
    on the morphology and the gas permeability, Polymer, 2006, 47(15),5303-5313
    PA.1.2
    Phase separation microfabrication
    M. Bikel, R.G.H. Lammertink, M. Wessling
    Membrane Science and Technologv Group, Facultv of Science and Technologv, Universitv of Twente MESA Institute of
    NanotechnologvPO BOX 217 7500AE Enschede The Netherlands
    r.g.h.lammertinkutwente.nl
    PSF entails the phase separation oI polymer solutions that are cast onto structured supports which serve as molds . In this
    way, microstructured membranes can be obtained without the use oI cleanroom technology (Fig 1). The replication oI the
    pattern on the mold extends the Iunctionality oI these membranes into new and existing applications. Many kinds oI Ieatures
    can be replicated down to the micron range, even with high aspect ratios. With small adaptations, this process is extendable to
    the structuring oI hollow Iibers, whether be it Ior structuring the outside oI the Iiber, its lumen or both.
    -180-
    b
    By means oI introducing diIIerent Ieatures on the molds, the phase separation mechanism could be studied and changed. The
    presence oI a small amount oI Ieatures allowed us to study the process by observing the eIIect oI the Iinal morphology on the
    replication oI the Ieatures. Several types oI distortion were observed when the polymeric matrix shrunk away Irom the mold
    walls. An increase in the number or total area oI the Ieatures decreased the deIormation oI the replicas to a minimum. In this
    case, the pattern has an eIIect on the morphology.
    Coagulation baths with increasing NMP to water ratios were tried, Iinding minimum values Ior macrovoid suppression. Their
    eIIect on the solidiIication oI the membrane was also assessed. The inclusion oI a vapor bath beIore immersion precipitation
    was studied Ior creating a skin that slowed down the exchange oI solvent and non-solvent.
    Tunability oI the porosity oI the membrane is an interesting Ieature since the inner structure oI the membrane is also oI high
    importance Ior the diIIerent applications. ThereIore, a methodical study oI the PES/PVP/NMP/water system was carried out.
    Variations in the compositions oI both the casting solution and the coagulation bath were tested Ior inIluence on the thickness,
    extent oI shrinkage and porosity oI the Iinal membrane.
    Fig 1. PolyethersulIone membrane with a line
    pattern
    PA.1.3
    Methods of characterization of heterogeneous ion-exchange membranes
    L. Brozova
    Institute of Macromolecular Chemistrv of the AS CR v.v.i, Hevrovskv Sq. 2, 162 00 Prague 6, C:ech Republic
    brozovaimc.cas.cz
    Heterogeneous ion-exchanges membranes contain micron-size ion-exchange particles embedded in an inert binder and they are
    very oIten reinIorced by textile. They are used in electrodialysis, electrophoresis and electrodeionozation, thereIore they must
    be chemical stable and exhibit good mechanical and electrochemical properties.
    They are prepared in three main steps:
    a) Grinding oI the ion-exchange resin into small particles
    b) Blending oI particles with the inert binder at temperature above the melting point oI the binder
    c) Moulding oI the Ilat membrane
    The morphology and accompanying properties oI the resulting membranes depend on the type oI the ion-exchange resin and
    the binder, their concentration in the mixture and on conditions oI the membrane preparation. Due to the diIIerent preparation,
    membranes with the same composition can diIIer in morphology and, consequently, in electrochemical properties.
    The morphology, ion-exchange capacity, chemical properties (R
    A
    , R
    S,
    permselectivity, transport numbers), rheology,
    mechanical properties, gas permeability and porosity oI the heterogeneous ion-exchange membranes were studied.
    Methods oI membrane properties characterization allow display and solve problems which could occur on technological scale
    and to optimize technology oI ion-exchange membrane preparation.
    Acknowledgements: This study was supported by the Grant Agency oI the Czech Republic (project 203/08/0465) and Ministry
    oI Industry and Trade oI the Czech Republic (project FT-TA4/116)
    -181-
    PA.1.4
    An AFM analysis of the changes on the surface of several nanofiltrationmembranes
    after the purification of clavulanic acid solutions
    A. L. Carvalho
    1
    , A. Hernandez
    2
    , L. Palacio
    2
    , P. Pradanos
    2
    , F. Maugeri
    1
    1
    Departament of Food Engineering, Facultv of Food Engineering, P. O. Box 6121, Universitv of Campinas UNICAMP,
    CEP. 13083-862, Campinas, SP, Bra:il
    2
    Depto. de Termodinamica v Fisica Aplicada, Fac. de Ciencias, Universidad de Jalladolid, Real de Burgos s/n, 47071
    Jalladolid, Spain
    limoeiroIea.unicamp.br
    The membrane morphology, its pore density and its pore size distribution determine its
    perIormance in a separation process. AFM gives topographic images at an atomic
    resolution which makes it an interesting technique to study the surIace properties oI
    nanoIiltration membranes |1|. Here we will study Iour commercial nanoIiltration
    membranes: NF90 (polyamide) and NF (polypiperazine amide) Irom Filmtec
    TM
    and
    NP010 and NP030 (polysulIone) Irom Microdyn Nadir

    . This procedure showed that the


    NF90 membrane has an irregular structure with circular and slit pores, the membrane
    NF presents a pure granular structure, and the membranes NP010 and NP030 have a
    peculiar granular structure somehow similar to a string oI beads.
    These membranes were used to puriIy a synthetic solution oI clavulanic acid at a
    concentration oI 750 mg/L. Filtration was perIormed at 25C, at a pH oI 6.2, at a
    transmembrane pressure oI 2x10
    6
    Pa and at a stirring Irequency oI 600 rpm. The
    morphology oI these membranes was studied by AFM aIter their use to Iilter the
    clavulanic acid. The NF90 membrane presented a similar structure beIore and aIter its
    use. In both cases the surIace was rough and it did not change what seems to indicate the
    appearance oI a very thin layer oI adsorption. Examples oI the NF90 membrane beIore
    and aIter its use can be seen in Figure 1. The NF membrane showed a relatively smooth
    structure with similar granular structures both beIore and aIter the Iiltration oI the
    clavulanic acid. In this case, nothing can be concluded on the adsorption as Iar as it
    could be high but uniIorm what should lead to very slight changes in the morphology oI
    the surIace. The NP010 membrane presented a totally diIIerent structure aIter its use
    with a disappearance oI the original topology and the Iormation oI a highly rugged
    morphology, with a twoIold roughness. Finally, the NP030 membrane changed its
    structure Irom extremely smooth beIore the Iiltration to highly rough aIter its use what
    indicates a high adsorption. It seems that the NF90 and possibly the NF membranes are
    less Iouled by the clavulanic acid that should interact less with the amide groups that
    with the sulIonic groups.
    |1| N. Hilal, H. Al-zoubi, N. A. Darwish, A. W. Mohammad, M. Abu Arabi, A comprehensive review oI nanoIiltration
    membranes: treatment, pretreatment, modeling, and atomic Iorce microscopy, Desalination, 2004, 170, 281-308
    Acknowledgements: The authors acknowledge the Iinancial support Irom Coordenao de AperIeioamento de Pessoal de
    Nivel Superior (CAPES).
    PA.1.5
    Microfiltration membranes via phase separations of polymer solutions: control of
    pore structure and hydrophilicity
    N. Stahra, H. Susanto, M. Ulbricht
    Lehrstuhl fr Technische Chemie II, Universitt Duisburg-Essen, 45117 Essen, Germanv
    nico.stahrauni-due.de
    MicroIiltration (MF) has increasingly been accepted as promising technology in a wide range oI applications including water
    and wastewater treatments, dairy, biotechnological and pharmaceutical industries, Iood and beverage processing, and medical
    -182-
    Fig 1: AFM image Ior the NF90
    membrane
    applications. Along with its many successes, signiIicant loss oI perIormance with respect to Ilux and oIten selectivity attributed
    to Iouling is recognized as the biggest problem in its applications. ThereIore, preparation oI low Iouling MF membranes is
    very important. The process oI the non-solvent induced phase separation (NIPS) has a special relevance in production oI
    polymeric membranes. By variation oI the main components like polymer, solvent and non-solvent it is possible to achieve a
    broad spectrum oI pore structures. Many Iurther parameters such as mixtures oI solvents or non-solvents, temperature,
    exposure time oI the polymeric Iilm beIore coagulation, etc. have inIluence on the resulting membrane structure. For instance,
    the combination oI NIPS and vapor induced phase separation (VIPS) could produce a Iinal morphology that is more open and
    has larger pores at the upper surIace oI the Iilm |1|.
    The aim oI this work was to produce MF membranes Irom polyethersulIone (PES) having high Ilux and hydrophilic property.
    VIPS was introduced beIore NIPS process to obtain high Ilux whereas an amphiphilic block copolymer, poly(ethyleneoxide)-
    b-poly(propyleneoxide)-b-poly(ethyleneoxide) (Pluronic

    ), was used as additive to the casting solution to increase


    hydrophilicity. The resulting membranes were characterized with respect to hydraulic permeability, pore size distribution (by
    gas Ilow / pore dewetting permporometry), chemical composition (by ATR-IR spectroscopy), surIace wettability (by contact
    angle) and morphology (by SEM). The membrane perIormance was examined by static adsorption and microIiltration
    experiments with proteins. Indeed, the membrane characteristics and perIormance could be controlled by adjusting the non-
    solvent triethyleneglycol (TEG) content in the casting solution, the exposure time in humid air beIore coagulation and the
    Pluronic content. To achieve membranes with regular 'sponge-like structure it was necessary to have a high amount oI non-
    solvent (~60 TEG) in the polymer solution and enough exposure time in humid air. The absorption oI water Irom air led to
    larger pores and higher Ilux.
    The membrane hydrophilicity was proportionally inIluenced by the Pluronic content. The perIormance test showed that much
    lower protein during static adsorption and higher Ilux during microIiltration could be obtained. The stability oI hydrophilic
    property obtained Irom addition oI Pluronic was quite high.
    |1| V.P. Khare, A.R. Greenberg, W.B. Krantz, Vapor-induced phase separation eIIect oI the humid air exposure step on
    membrane morphology. Part I. Insight Irom mathematical modeling, J. Membr. Sci. 2005, 258, 140-156.
    PA.1.6
    Solvent resistant nanofiltration (SRNF) containing metal organic frameworks
    S. Basu, M. Maes, A. Cano-Odena, L. Alaerts, D.E. De Vos, I.F.J. Vankelecom
    Centre for Surface Chemistrv and Catalvsis, Facultv of Bioengineering Sciences, Katholieke Universiteit Leuven, Kasteelpark
    Arenberg 23, 3001 Leuven, Post Box 2461, Belgium
    ivo.vankelecombiw.kuleuven.be
    Mixed matrix membranes (MMMs) with suitable polymer/metal organic Iramework (MOFs) mixing have received recent
    interest in the Iield oI gas separations |1, 2|. The present study aims to Iind the Iirst application oI MOF-Iilled membranes Ior
    SRNF. More in particular, MOFs were incorporated in PDMS (polydimethylsiloxane) membranes.
    MOFs are a new class oI crystalline porous materials, composed oI metal ions joined by organic ligands. MOFs were selected
    based on their pore morphology (pore diameter and volume), stability at room temperature, ease oI synthesis or commercial
    availability. Membranes were studied Ior the separation oI a dye (Rose Bengal, RB, 1017Da) Irom isopropanol (IPA).
    ModiIication oI the MOF outer wall with N-methyl-N(trimethylsilyl) triIluroacetamide (MSTFA) was Iound crucial to allow
    synthesis oI deIect- Iree MMMs (Figure 1). The resulting membranes gave good SRNF perIormance with enhanced RB
    retention and an IPA Ilux similar to that oI unIilled PDMS, due to a combined eIIect oI reduced polymer swelling and solute
    exclusion Irom the Iiller pores.
    Figure 1: SEM picture oI deIect-Iree MMMs
    -183-
    MIP (Milieu- & Energietechnologie InnovatieplatIorm, Berchem, Belgium), DURSI, Generalitat de Catalunva, FWO
    Vlaanderen (Research Foundation-Flanders) are acknowledged Ior granting the work.
    |1| A. Cara, C Stropnika and K. V Peinemann, Hybrid membrane materials with diIIerent metalorganic Irameworks (MOFs)
    Ior gas separation, Desalination, 2006, 200 (1-3) 424.
    |2| Y. Zhang, I. H. Musselman, J.P. Ferraris and K. J. Balkus., Gas permeability properties oI Matrimid membranes
    containing the metal-organic Iramework CuBPYHFS, J. oI Memb. Sci., 2008, 313 (1-2) 170.
    PA.1.7
    Novel cross-linkable copolymer membranes for organophilic
    ultra- and nanofiltration
    Z. Pei, M. Ulbricht
    Lehrstuhl fr Technische Chemie II, Universitt Duisburg-Essen, 45141 Essen, Germanv
    zhaoqing.peiuni-due.de
    The major contaminations in industrial wastewater and ground water are volatile organic compounds, particularly chlorinated
    and aromatic hydrocarbons. Organophilic naniIiltration is both technically and economically viable Ior removing organic
    contaminations, but Iavorable anti-Iouling properties are required Ior the membranes. Furthermore, Ior attractive applications
    oI nanoIiltration in completely organic systems, there is still a great demand in highly permeable, selective and stable
    polymeric membranes |1|.
    Copolymerization is one oI the chemical modiIying approaches which is widely used to increase the hydrophilicity and anti-
    Iouling properties oI polyacrylonitrile porous membranes. It has been reported in some papers about the monomers
    copolymerized with acrylonitrile and the process |2-4|.
    In this work, novel polyacrylonitrile-poly-(ethylene glycol) (PAN-PEG) block copolymers were synthesized by water-phase
    precipitation copolymerization, using ceric ammonium nitrate and PEG as the initiator system. The variation oI the amount oI
    the initiator, the PEG molecular weight and the PEG weight content in the copolymer were used to obtain copolymers with
    distinctly diIIerent properties. The structure and the composition oI the block copolymers were characterized by FT-IR, NMR,
    and elemental analysis; the molecular weight was measured by Gel Permeation Chromatography (GPC).
    Nonsolvent induced phase separation method was used to prepare anisotropic porous membranes Irom the novel block
    copolymers. By using transmission electron micrographs, the pore morphologies oI the membranes were examined, and the
    ultraIiltration properties in aqueous systems (Ilux and separation curve) were analysed.
    In the next step, the modiIication oI the novel copolymer membranes was investigated with the aim to enhance the mechanical
    properties and also the solvent stability. Chemical cross-linking was introduced with the agent terephthaloyl chloride. Solvent
    stability and swelling experiments were perIormed in oder to evaluate suited reaction conditions. Filtration experiments with
    organic solvents were then perIormed to evaluate the perIormance as a organophilic separation membrane and as support Ior
    nanoIiltration composite membranes.
    |1| Vankelecom I, Gevers L, Vandezande P. Solvent resistant nanoIiltration: separating on a molecular level. Chem Soc Rev,
    2008, 37, 365-405
    |2| Wang H Y, Kobayashi T, Fujii N. Molecular imprint membranes prepared by the phase inversion precipitation technique.
    Langmuir, 1996, 12, 4850-4856.
    |3| Yoshikawa M, Fujimoto K, Kinugawa H et al. Selective permeation oI carbon dioxide through synthetic polymeric
    membranes having amine moiety. Chem Lett, 1994, 243-246.
    |4| Pekel N, Guven O. Separation oI uranyl ions with amidoximated poly (acrylonitrile/ N-vinylimidazole) complexing
    sorbents. Colloids SurI A, 2003, 212, 55-161
    -184-
    PA.1.8
    Study of the performance of self-made polyethersulfone membranes relative to
    commercial ultrafiltration membranes for the fractionation of stevia-extracts
    J. Vanneste
    1
    , A. Sotto
    2
    , V. Van Craeyveld
    3
    , J. Vandeur
    1
    , B. Van der Bruggen
    1
    1
    Laboratorv of Applied Phvsical Chemistrv and Environmental Technologv, Department of Chemical Engineering,
    K.U.Leuven, W. de Crovlaan 46, B-3001 Leuven, Belgium
    2
    Department of Chemical and Environmental Technologv, Universitv Rev Juan Carlos, Tulipan s/n, 28933-Mostoles, Madrid,
    Spain
    3
    Laboratorv of Food Chemistrv and Biochemistrv, Leuven Food Science and Nutrition Research Centre (LFoRCe), Katholieke
    Universiteit Leuven, Kasteelpark Arenberg 20 bus 2463, B-3001 Leuven, Belgium
    johan.vannestecit.kuleuven.be
    Membrane processes are becoming increasingly competitive compared to traditional Iractionation techniques such as
    chromatography |1|. Beside the development oI new membrane materials and manuIacturing techniques, a new strategy to
    improve the selectivity oI membrane processes is the integration oI membranes with moderate selectivity into membrane
    cascades |2|. The potential oI these cascades Ior enhancing the separation is ideally studied with membranes with known
    characteristics as is the case with selI-made membranes. In this study polyethersulIone membranes were prepared using the
    DIPS technique (diIIusion induced phase inversion). Three parameters were varied to study the eIIect on permeability and
    selectivity: the polymer concentration, composition oI the non-solvent bath (water-isopropanol (IPA) mixture) and mixture oI
    solvents (dimethylIormamide (DMF)) or N-methyl-pyrrolidone (NMP)). The selectivity was studied Ior a mixture oI
    polyethylene glycol (PEG MW1500), stevioside (MW 804) and rebaudioside-A (MW 967). The two Iormer are steviol
    glycosides, low-calorie natural sweeteners obtained Irom a plant extract. PEG 1500 was added as a model impurity.
    Permeability increased by a Iactor thirty and selectivity more than tripled iI polymer concentration is lowered Irom 33 to 27
    . Addition oI IPA reduced permeability and selectivity. Addition oI DMF reduced permeability and did not aIIect selectivity.
    The perIormance oI the selI-made membranes was compared with that oI commercial Ilat sheet membranes in cross-Ilow
    Iiltration (GE Osmonics: GK (2 kD), GM (4 kD), PT (5 kD), PW (10 kD) and Microdyn-Nadir: UH (4 kD), UP (5 kD), UC (5
    kD)) and one tubular membrane (BerghoI 5 kD). Most prepared membranes have a lower selectivity and similar permeability.
    Only membranes prepared with low polymer concentrations (27 ) combine a high selectivity with a high permeability.
    Although the selectivity remains 36 below that oI the commercial membrane with the highest selectivity (UH), the
    permeability oI the selI-made membrane is 36 higher.
    IWT Vlaanderen (Institute Ior the Promotion oI Innovation by Science and Technology in Flanders) is acknowledged Ior
    granting this research.
    |1| A. Andersson, T. Perrson, G. Zacchi, H. Stlbrand, A. Jnsson, Comparison oI DiaIiltration and Size-Exclusion
    Chromatography to Recover Hemicelluloses From Process Water From Thermomechanical Pulping oI Spruce, Applied
    Biochemistry and Biotechnology, 137, 971-983.
    |2| S.S. Gunderson, W.S. Brower, J.L. O`Dell, E.N. LightIoot. Design oI Membrane Cascades. Separation Science and
    Technology, 42, 21212142.
    PA.1.9
    Gas permeation properties of rubbery poly(ether imide)/SiO
    2
    hybrid nanocomposite
    membranes
    J. Grignard, D. Roizard, E. Favre
    Laboratoire des Sciences du Genie Chimique (LSGC) (UPR 6811, Nancv Universite), Groupe ENSIC BP 20451 1, rue
    Grandville, 54001 Nancv Cedex, France
    Jacques.Grignardensic.inpl-nancy.Ir
    To meet the current societal challenges associated with new energy carriers, i.e. H
    2
    , CH
    4
    , and the reduction oI emissions oI
    greenhouse gas (Kyoto Protocol), the study oI new and intensiIied processes is a necessity that must be closely associated with
    the development oI advanced materials. ThereIore, the preparation and application oI mixed matrix membranes (MMM) have
    -185-
    quickly become an expansive area. In our case we Iocused on MMM preparation Irom polyalkyletherimide (PEI). Indeed,
    polyimides are known to have high materials properties, good chemical resistance and a CO
    2
    permselectivity |1-3|.
    Starting Irom the polyamic acid hybrid Iorm in DMF solutions, a series oI hybrid copolyether-imide nanocomposite
    membranes was prepared with various amounts oI silica phase ranging Irom 1 to 15 wt using either SiO
    2
    nanoparticles or
    organic silica precursors, i.e. TMOS and TEOS, by in situ sol-gel method.
    We report the characterization oI the physical and physical-chemical properties oI the obtained PEI/SiO
    2
    MMM and the related
    morphologies by scanning and transmission electronic microscopies to study the relations between structures and properties.
    Gas permeation parameters oI these membranes were then studied by time-lag experiments Ior several in gases (N
    2
    , CO
    2
    , O
    2
    ,
    CH
    4
    , H
    2
    and H
    e
    ) at diIIerent temperatures, varying Irom 5 to 45 C.
    It was shown that the obtained MMM structures were markedly diIIerent when silica nanoparticules or when sol-gel method
    was used. In the last case the nanoparticules were distributed more homogenously into the PEI matrix. The permeation
    properties oI the MMM will be discussed with respected to the preparation method used and to the Iiller content. At last a
    comparison with the literature data oI polyimides will be given.
    |1| D. Wilson, H.D. Stenzenberger, P.M. Hergenrother, Polyimide, Blackie, Glasgow (1999).
    |2| T.C. Merkel, B.D. Freeman, R.J. Spontak, Z. He, I. Pinnau, P. Meakin, A.J. Hill, Science 296 (2002), p. 519.
    |3| D. Ayala, A.E. Lozano, J. de Abajo, C. Garcia-Perez, J.G. de la Campa, K.-V. Peinemann, B.D. Freeman, R. Prabhakar, J.
    Membr. Sci. 215 (2003), p. 61.
    PA.1.10
    Symmetric porous PVDF-HFP membranes generated by a supercritical
    gel drying process
    S. Cardea
    1
    , A. Gugliuzza
    2
    , E. Drioli
    2,3
    , E. Reverchon
    1
    1
    Department of Chemical and Food Engineering, Universitv of Salerno, Jia Ponte Don Melillo 1, 84084, Fisciano, Italv
    2
    Research Institute on Membrane Technologv, ITM-CNRJia P. Bucci, 17C c/o Universitv of Calabria, 87036 Rende (CS),
    Italv
    3
    Department of Chemical Engineering and Materials, Universitv of Calabria,Jia Pietro Bucci 17/C,I-87030 Rende, Italv
    scardeaunisa.it
    In the last decades, many eIIorts have been done Ior the implementation oI new eco-Iriendly membrane manuIacturing
    techniques. The Iormation oI nanostructured aerogels by supercritical CO
    2
    -assisted drying process appears a strategically
    innovative and eco-sustainable approach, since highly porous Iilms working as membranes can be achieved at high quality-low
    cost ratio. In this work, PVDF-HFP gels have been prepared Irom polymer-acetone solutions adding various amount oI
    ethanol. Series oI supercritical drying experiments have been perIormed at diIIerent pressures (Irom 100 to 200 bar) and
    temperatures (Irom 35 to 45C), and at various polymer concentrations (Irom 5 to 12 wt.). The eIIects oI the process
    conditions on the membrane morphology have been evaluated and structure-properties relationships have been Iound. In all
    cases, the membranes exhibit interconnected structures with nano-sized pores and high porosity (Figure 1), leading to reduced
    resistance to the gas mass transIer and high hydrophobic character oI the surIaces. These membrane-like aerogels promise to
    Iorm a new class oI highly hydrophobic porous interIaces, potentially suitable to be used in membrane operations based.
    Figure 1: SEM picture oI PVDF-HFP membrane-like aerogel
    -186-
    PA.1.11
    Preparation of biodegradable chitosan membranes for tissue engineering
    applications
    C. Campana
    1,2
    , A. Piscioneri
    1,3
    , F. Tasselli
    1
    , S. Salerno
    1
    , E. Drioli
    1
    , L. De Bartolo
    1
    1
    Institute on Membrane Technologv, National Research Council of Italv, ITM-CNR, c/o, Universitv of Calabria,Jia P. Bucci,
    cubo 17/C, Rende (CS), Italv
    2
    Department of Chemical Engineering and materials Jia P.Bucci 87030 Rende (CS) Italv.
    3
    Department of Cell Biologv, Universitv of Calabria, Jia P.Bucci 87030 Rende (CS) Italv
    c.campanaitm.cnr.it
    A large number oI biodegradable polymers have been explored Ior tissue engineering applications: these materials include
    natural polymers such as chitosan. Chitosan (CHT) has been Iound a Iascinating candidate in a broad spectrum oI applications
    along with unique biological properties including biocompatibility, biodegradability to harmless products, nontoxicity,
    physiological inertess, remarkable aIIinity to proteins. CHT is a linear polysaccharides composed oI glucosamine and N- acetyl
    glucosamine units linked by (1,4) glycosidic bonds. Low solubility oI chitosan in both water and organic solvents resulted in
    many studies aimed at making water soluble derivatives oI chitosan using chemical modiIication techniques. Polymer blends
    are also attractive as biomaterials because their properties can be easily adjusted by varying the ratio and nature oI the
    components. They also have the advantage oI being easily produced by simple technique. Blends oI a natural and a synthetic
    polymer can modiIied the range oI physicochemical and mechanical as well as the biocompatibility and biological interactions.
    CHT has been oIten blended with other water soluble polymers. Poly (ethyleneglycol)(PEG) |1| and polycaprolactone (PCL)
    |2| are recognized as material supporting CHT to obtain a material with suIIicient mechanical strength Irom which Iilms have
    been prepared. PEG is a neutral, water soluble and non toxic polymer which has been employed Ior pharmaceutical and
    biomedical applications.The new membrane was prepared by phase inversion technique, with a casting solution constituted oI
    4 (wt/wt) oI chitosan dissolved in 2 (v/v) oI acetic acid solution. The PEG was added in ratio 4:1 to improve the tensile
    properties.
    Blends oI PCL and CHT were prepared by casting Irom solution. CHT and PCL were dissolved by using acetic acid/water
    mixtures, containing 4 by weight oI CHT.
    Once the blend Iilm is Iormed, the distribution oI CHT, PEG and PCL domains aIIects the physical properties oI the materials
    such as static contact angle, spectroscopy, thermodynamic attributes and scanning electron microscopy to get a picture oI the
    microstructure oI these blends.
    This work was aimed at the development and optimization oI biodegradable membranes to be used Ior the adhesion and
    proliIeration oI liver progenitor cells.
    |1| M.Zhang, X.H.Li, Y. D.Gong, N.M. Zhao, X.F. Zhang, Properties and biocompatibility oI chitosan Iilms modiIied by
    blending with PEG. Biomaterials 23 (2002) 2641-2648.
    |2| D. M. Garcia Cruz, J.L. Gomez Ribelles, M.S. Sanchez; Blending polysaccharides with biodegradable polymers. I.
    Properties oI chitosan/polycaprolactone blends; J. Biomed. Mat. Res. B: Appl. Biomat., vol 85B(2): 303-313 (2008).
    PA.1.12
    The role of HCl on the transport of tin through cation- and anion- exchange
    membranes
    M. Garcia-Gabaldon, V. Perez-Herranz, J. Garcia-Anton, J.L. Guion
    Dpto. Ingenieria Quimica v Nuclear. Universidad Politecnica de Jalencia. C/ Camino de Jera s/n. Jalencia, Spain.
    mongargaiqn.upv.es
    Ion exchange processes have been suggested as promising possibilities Ior the removal oI metals such as tin and other
    inorganic toxic substances generated in electroplating processes. In our particular case, the use oI a separator is justiIied in
    order to prevent the oxidation oI Sn(II) at the anode, however, its presence introduces an ohmic drop that has to be minimised.
    The present work evaluates the inIluence oI the concentration oI HCl on the transport properties oI tin through cation- and
    anion-exchange membranes Ior a concentration range oI HCl similar to that occurring in the concentrated and diluted baths oI
    the plating oI polymers industry. The chronopotentiometry, which measures the electric potential response oI a system to an
    imposed current, is the electrochemical method selected to carried out the present study.
    -187-
    The chronopotentiograms obtained in the cation-exchange membrane (CEM) Ior 0.01M SnCl
    4
    and low HCl concentration
    show an increase oI the membrane potential (E
    m
    ) at high applied currents as observed in Fig. 1. The H

    ions Iormed due to


    water splitting at those high currents cross the membrane and the OH
    -
    ions remain in the anodic side oI the CEM leading to a
    pH increase, which enhances the Iormation oI a Sn(IV) gelatinous species that can polymerise and remain adhered to the
    membrane surIace, causing the increase oI E
    m
    observed in Fig. 1 Ior an applied current oI 220mA. When the HCl concentration
    increases the Sn(IV) gelatinous species can be redisolved causing the decrease oI E
    m
    observed in Fig. 2.
    Fig. 1. Chronopotentiometric curves obtained in the CEM at
    diIIerent applied currents Ior an electrolyte concentration oI
    0.01M SnCl
    4
    and 10
    -2
    M HCl
    Fig. 2. Chronopotentiometric curves obtained in the CEM at
    diIIerent applied currents Ior an electrolyte concentration oI
    0.01M SnCl
    4
    and 10
    -1
    M HCl
    PA.1.13
    Stratified mixed matrix membranes based on polyimides filled by inorganic fillers
    M. Frycova
    1,2,3
    , P. Sysel
    2
    , L. Brabec
    1
    , B. Bernauer
    3
    , P. Hrabanek
    1
    , M. Kocirik
    1
    1
    J. Hevrovskv Institute of Phvsical Chemistrv of the ASCR, v.v.i., Dolefskova 2155/3, 18223 Prague 8, C:ech Republic
    2
    Institute of Chemical Technologv Prague, Department of Polvmers, Technicka 3, 16628 Prague 6 Defvice, C:ech Republic
    3
    Institute of Chemical Technologv Prague, Department of Inorganic Technologv, Technicka 5, 16628 Prague 6 Defvice, C:ech
    Republic
    milan.kocirikjh-inst.cas.cz
    ModiIication oI PIs based on application oI coupling agent 3-aminopropyltriethoxysilane (APTES) was used to prepare mixed
    matrix membranes with a good interIacial adhesion between PI matrix and Iiller particles. Membranes were prepared by
    casting the polymer precursor solutions or the dispersion oI Iiller in the precursor solution on a TeIlon support and subsequent
    heating. Starting materials Ior the PIs were polyamic acids endcapped by APTES synthesized Irom appropriate monomers. The
    Iillers used were inorganic microporous, mesoporous and non-porous materials based prevailingly on pure silica. He and N
    2
    were selected as the test penetrant species. The dependences oI permeability oI helium on content
    d
    oI Iiller were then
    compared with theoretical models by Maxwell, Hennepe and Bruggeman. It was Iound that experimental permeability versus

    d
    dependences exhibited considerable deviations Irom the corresponding theoretical ones. SEM analysis oI the composites
    revealed a stratiIied texture oI composites consisting oI three layers: (i) thin top layer oI pure PI, (ii) middle layer represented
    by composite PI Iiller Iree oI macrovoid and (iii) a bottom layer consisting oI network oI macropores between agglomerated
    particles oI Iiller. A lamellar model oI composite membranes was elaborated which explained all types oI discrepancies
    between permeation experiments and the Bruggeman model.
    The Iinancial support by the Czech Science Foundation via grant No. 203/09/1353 is grateIully acknowledged.
    -188-
    PA.1.14
    Green spherical building blocks for the fabrication of self-standing polymeric
    membranes challenging anodic structures
    A. Gugliuzza
    1
    , F. Trotta
    2
    , E. Drioli
    1,3
    1
    Research Institute on Membrane Technologv- National Research Council (ITM-CNR), Jia P. Bucci, Cubo 17/C, I-87030
    Rende (CS), Italv
    2
    Department of Chemistrv I.F.M, Universitv of Turin Jia Giuria 7, I-10125 Turin, Italv
    3
    Department of Chemic al Engineering and Materials, Universitv of Calabria, Via Pietro Bucci 45A, I-87030 Rende, Italy
    a.gugliuzzaitm.cnr.it
    The use oI traditional techniques has brought to the Iabrication oI numerous polymeric membranes with various structural
    connotations. However, well-deIined structures characterized by high porosity and uniIorm pore distribution have rarely been
    achieved by means oI usual manuIacturing approaches
    1
    .
    Here, a greener and reIined technique is proposed Ior the creation oI well-patterned polymeric architectures working as ideal
    interIaces in contactors
    2
    . Three-dimensional porous networks with regular channels have easily been Iabricated by using no
    toxic spherical templates such as water droplets. SelI-standing layers with hexagonally packed structures have been generated
    in only one step, Iollowing the ordered arrangement oI simple and easily removable green building blocks like water droplets.
    The latter leIt pores with size and shape comparable to those oI the spheres. No coalescence but almost lithographic sequence
    and reproducible inter-distance characterize the Iilms, resembling the traditional anodic structures. This approach is
    signiIicantly more cost-eIIectiveness, time-saving and eco-sustainable than traditional methods. These membranes can be
    considered potential next interIaces Ior advanced contactor operations and attractive scaIIolds Ior bio-technological
    applications.
    Figure.1 Honeycomb lattice oI a selI-standing membrane
    Acknowledgement: This work has been carried out within the Irame oI the research project: European Network oI Excellence
    on Nanoscale-based Membrane Technologies (NoE NANOMEMPRO N.500623-2-26-7-2004).
    |1| Gugliuzza A., Drioli E., PVDF and HYFLON AD membranes: Ideal interIaces Ior contactor applications, J. oI Membr. Sci.
    (2007) 300, 5162.
    |2| Gugliuzza A., Aceto M.C., Macedonio F., Drioli E., Water droplets as template Ior next generation selI-assembled poly-
    (etherether)ketone with Cardo membranes, J. Phys. Chem. B (2008) 112 (34), 10483-10496.
    PA.1.15
    Preparation of ultrathin-skinned asymmetric polysulfone membranes by phase
    inversion and microwave plasma surface treatment
    M. Etxeberria, S. Miguel, E. Fernandez-Gesalaga, P. Corengia, A. Garcia-Luis, D. Gonzalez-Santamaria
    INASMET-Tecnalia, Mikeletegi Pasealekua, 2, (20009) San Sebastian, Spain
    miren.etxeberriainasmet.es
    Gas separation membrane systems have received a lot oI attention Irom both industry and academia. This is due to the Iact that
    there is belieI that membrane separation processes may oIIer more capital and energy eIIiciency when compared to the
    -189-
    conventional separation processes in some applications. In order to accomplish this objective, membrane materials with
    superior permeability and selectivity, and advanced Iabrication technologies to yield membranes with high permeability and
    selectivity, are the primary Iocuses Ior most membrane scientists in the last two decades. Casting by phase inversion and
    surIace modiIication using plasma techniques has attracted interest in polymeric membrane-based separation oI gases and
    vapors. Plasma crosslinked polymer selective layers oIIer advantages as membranes, particularly in terms oI mechanical and
    chemical stability. Without crosslinking the material will tend to swell when exposed to certain gas mixtures, and hence
    separation properties are aIIected.
    Development oI ultrathin-skinned asymmetric membranes Irom highly selective polymers has been a challenge in gas
    separation processes. Although thousand oI polymers exhibit permselective properties Ior gas mixtures, only a Iew glassy
    polymers are useIul in making asymmetric gas separation membranes, particularly, polysulIone (PSI), polyethersulIone
    (PESI), polyetherimide (PEI) and polyimide (PI) |2|
    In this work, phase inversion technique has been used Ior producing deIect-Iree and ultrathin-skinned asymmetric polymeric
    Ilat sheet membranes Ior the separation oI H
    2
    /CH
    4
    , H
    2
    /CO
    2
    , CO
    2
    /CH
    4
    , CO
    2
    /N
    2
    and O
    2
    /N
    2
    gas mixtures. Polymeric gas
    separation membranes were prepared by the dry/wet phase inversion method using diIIerent casting solutions Irom
    PSI/DMAc,THF/EtOH and PSI/NMP,THF/EtOH, where the polysulIone content and the solvent-ratio have been varied |1|.
    AIter casting, the synthesized membranes have been surIace modiIied using microwave plasma reactor using diIIerent process
    conditions.
    The manuIactured membranes have been characterized by Scanning Electron Microscopy (SEM) (morphology), Fourier
    TransIorm InIrared Spectroscopy (FTIR) (chemical structure), and Energy Dispersive X-ray Spectroscopy (EDS) (chemical
    analysis). Permeability oI H
    2
    , CO
    2
    , CH
    4
    , N
    2
    and O
    2
    , and ideal selectivity oI diIIerent pair oI gasses have been investigated
    beIore and aIter the plasma treatment using time-lag method. The correlations between the Iinal membrane
    structure/permeation properties and the process conditions used (casting and plasma surIace treatment) are discussed
    extensively.
    |1| S.C. Pesek and W.J. Koros, Aqueous quenched asymmetric polysulIone membranes prepared by dry/wet phase separation,
    J. Membrane Sci., 81 (1993) 71-88.
    |2| Dongliang Wang, W.K. Teo, K. Li, Preparation and characterization oI high-Ilux polysulIone hollow Iibre gas separation
    membranes, J. Membrane Sci., 204 (2002) 247-256.
    PA.1.16
    Effect of the nonsolvency of coagulation on the nano-scale structure of PVDF
    membrane
    C.L. Li
    1,2,3
    , A. Deratani
    2
    , D.M. Wang
    1,4
    , D. Quemener
    2,3
    , D. Bouyer
    3
    , J.Y. Lai
    4
    1
    Department of Chemical Engineering, National Taiwan Universitv (NTU), Taipei 10617, Taiwan
    2
    Institute Europeen des Membranes (IEM), ENSCM, UM2, CNRS, Universite Montpellier II, CC 047, 2pl., Eugene Bataillon,
    34095 Montpellier, France
    3
    Universite de Montpellier II, CC 047, 2pl., Eugene Bataillon, 34095 Montpellier, France
    4
    Research and Development Center for Membrane Technologv, Chung Yuan Universitv, Chung Li 32023, Taiwan
    d94524001ntu.edu.tw or Chia-Ling.Liiemm.univ-montp2.Ir
    Super- hydrophobic surIaces whose water contact angle is larger than 150
    o
    have attracted a great interest Ior numerous
    applications. The wettability oI solid surIaces with water is inIluenced by surIace chemistry and surIace topography.
    According to the so-called lotus eIIect, the biomaterials are highly organized in a hierarchical manner Irom molecular level to
    the nano and micro scales. Being inspired by the lotus eIIect, this work presents how to prepare super-hydrophobic
    poly(vinylidene Iluoride) (PVDF) membranes by controlling its hierarchical topography. DiIIerent conIigurations oI phase
    separation process and nonsolvency oI coagulation bath were considered. Porous PVDF membrane with super-hydrophobic
    surIace (water contact angle ~ 152
    o
    ) was obtained by combining vapour-induced phase separation method (VIPS) and wet
    immersion method without surIace modiIications or expensive equipments. As expected, the membranes possessed micro-and-
    nano hierarchical structure. It was Iound that the micro-scale membrane structure can be tailored by adjusting the dissolution
    temperature to prepare the PVDF casting solution, the exposure time oI the casting Iilm to the humid air, and the solvency oI
    the coagulant used. In addition, the nano-scale structure can be tuned by using coagulants with diIIerent solvency to PVDF.
    Utilization oI the coagulant with strong nonsolvency to PVDF, such as water, membranes were prepared with water contact
    angle as high as 140
    o
    . However, only the coagulant with weak nonsolvency to PVDF, such as alcohol, can bring about the
    membranes with water contact angle higher than 150
    o
    . It is believed that the competition between phase separation and
    crystallization plays important roles in determining the organization oI the hierarchical structure. In conclusion, this work
    presents methods to tailor the micro and nano scale structure oI PVDF membranes; with suitable manipulation oI the
    -190-
    hierarchical structure in these two scales, the membrane surIace hydrophobicity can be adjusted and membranes can be
    obtained with surIace water contact angle higher than 150
    o
    .
    PA.1.17
    New poly (ether imide) based ultrafiltration membrane with low fouling properties
    obtained by surface modification with poly (ethylene glycol)
    W. Chinpa
    1
    , R. Jiraratananon
    2
    , D. Quemener
    3
    , A. Deratani
    3
    1
    Polvmer Science Program, Facultv of Science, Prince of Songkla Universitv, Hat-Yai, Songkhla, Thailand
    2
    Department of Chemical Engineering, King Mongkuts Universitv of Technologv Thonburi, Bangkok, Thailand
    3
    Institut Europeen des Membranes, Universite Montpellier II, Montpellier, France
    cwatchanyahoo.com
    The surIace activity oI ultraIiltration poly(ether imide) (PEI) membrane was tuned by using wet-chemical treatment in order to
    obtain low Iouling material. Poly (propylene oxide)/poly(ethylene oxide) monoamine (PEG-amine, JeIamine

    , M-2070) was
    used as surIace modiIier. The amine group is expected to react with the imide group oI PEI and the PEG block oI PEG-amine
    to ensure a good hydrophilicity to the membrane surIace. The eIIect oI the modiIication time on the morphology (SEM,
    AFM), wettability (contact angle measurement) and water permeability oI membrane were investigated. The chemical
    structure change during the modiIication process was monitored by FTIR-ATR, which conIirmed that imide groups were
    turned to amide groups during this process. Water contact angle measurement demonstrated that treatment with PEG-amine
    resulted in a better wettabilty oI PEI membrane and an increase in water permeability compared to parent PEI membrane.
    These characteristics oIIer a lower Iouling to protein (BSA) and make this procedure useIul Ior Iabrication oI ultraIiltration
    membranes.
    PA.1.18
    A hybrid membrane with an extractive layer and reactive support matrix for the
    sequential sorption and degradation of halogenated hydrocarbons in water
    G.M. Nisola, E. Cho, W.J. Chung
    Department of Environmental Engineering and Biotechnologv, Mvongfi Universitv, Yongin Campus, San 38-2 Namdong,
    Gveonggi-Do, South Korea (449-728)
    wjc0828gmail.com
    In order to remove trace levels oI halogenated compounds Irom water, a novel hybrid membrane was developed. The
    membrane is composed oI 2 layers: (1) an extracting layer Ior the selective permeation oI the target compounds (i.e.
    trihalomethanes) and (2) a reactive support matrix Ior the degradation oI the permeated solutes. The mechanism oI this
    membrane is to initially extract the solutes through the dense hydrophobic layer Iollowed by a surIace mediated Ienton-like
    system which takes place at the permeate side, within the vicinity oI the highly porous hydrophilic support membrane. The
    extractive layer contains a hydrophobic surIace modiIying macromolecules (SMM) while the reactive support membrane is
    embedded with in-situ nucleated Fe
    o
    nanoparticles with diameters ranging between 50- and 100 A |1, 2|.
    The membrane can be prepared either by one-pot synthesis (combination oI SMM product with Fe
    o
    precursor |Fe(CO)
    5
    | and
    polymer material Ior the support membrane in an Fe(CO)
    5
    thermolysis reaction) or by coating an SMM layer (in dilute PDMS
    solution) on a pre-prepared reactive support matrix |2, 3|.
    Batch sorption (hydrophobic dense Iilms) test revealed high partition (K
    p
    ) coeIIicient values oI trihalomethanes with the
    extractive layer (minimum value K
    p
    ~20). The kinetics oI degradation (support membrane only) experiments has also revealed
    the conversion oI trihalomethanes through dehalogenation (t
    1/2
    115 mins), undergoing experiments aim to reduce the halI liIe
    decay time oI the target compounds by varying Fe
    o
    content oI the support layer.
    Under continuous operation, parameters under investigation include Ieed concentration, pH and Ilow rate, permeate side
    oxygen content, pH and peroxide dosage.
    This work was supported by The Korean Science and Engineering Foundation (KOSEF) grant, Iunded by the Korean
    Government (MEST): project no. ROI-2008-000-20630-0.
    -191-
    |1| D. E. Suk, T. Matsuura, H.B. Park, Y.M. Lee, Synthesis oI a new type oI surIace modiIying macromolecules (nSMM) and
    characterization and testing oI nSMM blended membranes Ior membrane distillation, Journal oI Membrane Science, 2008,
    277, 177185.
    |2| T.W. Smith and D. Wychick, Colloidal iron dispersions prepared via polymer-catalyzed decomposition oI Iron
    pentacarbonyl, Journal oI Physical Chemistry, 1980, 84, 1621-1629.
    |3| Y. Yang, H. Zhang, P. Wang, Q. Zheng, J. Li, The inIluence oI nano-sized TiO
    2
    Iillers on the morphologies and properties
    oI PSF UF membrane, Journal oI Membrane Science, 2007, 288, 231-238.
    PA.1.19
    Determination of diffusion coefficients from area expansion of LDPE membrane
    immersed in organic liquids
    A. Randova
    1
    , L. Bartovska
    1
    , S. Hovorka
    1
    , K. Friess
    1
    , P. Izak
    2
    1
    Department of Phvsical Chemistrv, Institute of Chemical Technologv, Technicka 5, 166 28 Prague 6, C:ech Republic
    2
    Institute of Chemical Process Fundamentals, Ro:vofova 135, 165 02 Prague 6, C:ech Republic
    karel.Iriessvscht.cz
    The dilatation oI the Ilat low density polyethylene membrane BRALEN FB2-30 immersed in liquid medium was measured
    using an optical method |1|. Obtained results, expressed as relative area expansion (P), were used to evaluate the diIIusion
    coeIIicient (D) according to the equation
    ( )
    ( )
    2
    2
    2 2 2
    0
    2 1
    8 1
    1 exp
    2 1
    n
    m
    n
    n t
    P
    D
    P L
    n

    , ] j \
    +
    , ] , (

    , ( , ]
    +
    ( , ]

    where P is relative area expansion in time t, P


    m
    relative area expansion in the equilibrium and L thickness oI the membrane.
    The experiments with six liquid penetrans (cyclohexane, methylcyclohexane,
    ethylcyclohexane, benzene, methylbenzene, ethylbenzene) were perIormed at Iour temperatures, 10, 15, 20, and 25C.
    Determined trends oI temperature dependence oI diIIusion
    coeIIicients and the eIIect oI methyl- and ethyl- groups are shown
    in Figure 1. Higher diIIusion coeIIicients oI aromatic compounds
    in comparison with non-aromatics are in agreement with our
    previous
    Iindings when experiments were perIormed gravimetrically |2,3|.
    Authors are thankIul Ior the Iinancial support oI the Czech
    Ministry oI Education, Youth and Sports (MSMT grant No.
    6046137307).
    Figure 1. Values oI diIIusion coeIIicients oI studied
    liquids in LDPE at diIIerent temperatures.
    |1| P. Izak; S. Hovorka; T. Bartovsky; L. Bartovska; J.G. Crespo, Swelling oI polymeric membranes in room temperature ionic
    liquids. Journal oI Membrane Science (2007), 296(1-2), 131-138.
    |2| K. Friess, M. Sipek, V. Hynek, P. Sysel, K. Bohata, P. Izak, Comparison oI permeability coeIIicients oI organic vapors
    through non-porous polymer membranes by two diIIerent experimental techniques, Journal oI Membrane Science (2004), 240,
    179-185.
    |3| K. Friess, J. C. Jansen , O. Vopicka,

    A. Randova, V. Hynek,
    ,
    M. Sipek, L. Bartovska, P. Izak, M. Dingemans, Jo DewulI,
    H.Van Langenhove, E. Drioli, Comparative study oI sorption and permeation techniques Ior the determination oI heptane and
    toluene transport in polyethylene membranes. (Submitted into J. Membrane Sci. in November 2008).
    -192-
    PA.1.20
    Clarification of cashew apple juice through micro and ultrafiltration laboratorial
    unit using polymeric membranes (PES, CEL, PVDF)
    M.U. Miyake, L.A. Viotto
    Laboratorio de Medidas Fisicas (LAMEFI), Departamento de Engenharia de Alimentos (DEA), Faculdade de Engenharia de
    Alimentos (FEA), Universidade Estadual de Campinas (UNICAMP), 80 Monteiro Lobato Street, Campinas, Bra:il
    mayramiyakeyahoo.com.br
    Cashew Apple has been widely industrialized in Brazil. But one oI the main hurdles to increase internal and external
    consumption is the natural occurrence oI tannins, responsible Ior juice astringency |1|. Obtaining clariIied juices using
    membranes is a Iavorable alternative Ior producing isotonic drinks or Ilavored water. In addiction, membrane technology is a
    very attractive method Ior juice clariIication since it allows concentrating, Iracionate and/or puriIying Iluids, decreasing the
    loss oI compounds |2|. In this study, membranes oI micro and ultraIiltration Irom the Iollowing materials and molecular
    weight were used: cellulose 10kDa and 30kDa, polyethersulIone 150kDa and polyvinylidene diIluoride 150kDa, Irom the
    brand NADIR. The experiments were carried out in a stainless steel laboratorial cell, with a capacity oI 800ml, connected to a
    nitrogen cylinder Ior adjusting the trasmembrane pressure. The pressure used was 2 bar Ior microIiltration and 3 bar Ior
    ultraIiltration and the temperature Ior all oI them was 50C.
    The Ieed consisted oI 400g oI diluted cashew apple pulp (proportion 1:2, pulp:water), concentrated until FC2. The permeate
    Ilow rate observed were in a range oI 24,9 to 71,3 kg/m.h, and polyethersulIone 150kDa provided the higher Ilux. From the
    physical-chemical analysis results, it was veriIied tannins with more than 75 reduction. The permeate obtained Irom the Iour
    membranes studied was a liquid with viscosity similar to water, clear and slightly yellow and the retentate was characterized
    by high viscosity, yellow color and turbid appearance. Such results proved the eIIiciency oI Iiltration Ior clariIication oI
    cashew apple juice.
    |1| CAMPOS, D. C. P
    a
    .; SANTOS, A. S.; WOLKOFF, D. B.; MATTA, V. M.; CABRAL, L. M. C.; COURI, S. Cashew apple
    juice stabilization by microIiltration. Desalination, v. 148, p. 61-65, 2002.
    |2| GIRARD, B.; FUKUMOTO, L. R. Membrane processing oI Iruit juices and beverages: a review. Critical Reviews in Food
    Science and Nutrition, v. 40, n. 2, p. 91-157, 2000.
    PA.1.21
    Synthesis, morphology and membrane properties of poly(1-trimethylsilyl-1-
    propyne)-poly(4-methyl-2-pentyne) block copolymers
    E. Sultanov
    1
    , V. Khotimskiy
    1
    , A. Ezhov
    1,2
    1
    A.J.Topchiev Institute of Petrochemical Svnthesis, Russian Academv of Sciences (TIPS RAS), Leninskv prospect, 29, 119991
    Moscow, Russia
    2
    M.J.Lomonosov Moscow State Universitv, GSP-2, Leninskie Gorv, 119992, Moscow, Russia
    sultanovips.ac.ru
    Poly(1-trimethylsilyl-1-propyne) (PTMSP) has the highest gas permeability among all known polymers |1| and high selectivity
    oI recovery oI condensable hydrocarbons Irom mixtures with noncondensable gases. Solubility in higher hydrocarbons is a
    disadvantage oI PTMSP which limits its usage Ior membrane applications. That is why investigations aimed at development oI
    methods to improve resistance to hydrocarbons oI PTMSP are important challenges. One oI such methods is synthesis oI block
    copolymers oI 1-trimethylsilyl-1-propyne. As second monomer it is preIerable to use the one which Iorms high permeable and
    resistant to hydrocarbons homopolymer, like poly(4-methyl-2-pentyne) (PMP) |2|.
    Our work has been Iocused on synthesis oI PTMSP-PMP block copolymers and study oI their properties. Block copolymers
    were synthesized by sequential living polymerization oI monomers on catalytic systems based on niobium pentachloride. It
    was possible to obtain polymers with diIIerent permeability parameters and resistance to hydrocarbons by varying quantitative
    composition oI PTMSP-PMP block copolymers. Some oI them combine properties attractive Ior membrane materials.
    Permeability oI various gases (N
    2
    , O
    2
    , CO
    2
    , CH
    4
    , C
    4
    H
    10
    ), solubility in organic solvents and morphology oI Iilms Irom PTMSP-
    PMP block copolymers were investigated. Study oI morphology oI block copolymers showed that densely packed PMP blocks
    are distributed in PTMSP matrix. In this case PMP blocks may perIorm as physical cross-links responsible Ior resistance oI
    polymer to organic substances and presence oI PTMSP blocks with high Iree volume may provide high level oI gas
    permeability.
    -193-
    Funding Ior this research was provided by the Russian Foundation oI Basic Research, project 07-03-00553-a.
    |1| K. Nagai, T. Masuda, T. Higashimura, B.D. Freeman, I. Pinnau, Poly(1-trimethylsilyl-1-propyne) and related polymers:
    synthesis, properties and Iunctions, Prog. In Polym. Sci., 26 (2001), 721-798
    |2| V.S. Khotimsky, S.M. Matson, E.G. Litvinova, G.N. Bondarenko, A.I. Rebrov, Synthesis oI poly(4-methyl-2-pentyne) with
    various conIigurations oI macromolecular chains, Polym. Sci. Ser. A, 45 (2003), 740-746
    PA.1.22
    Biodegradable hollow fiber for tissue engineering application
    M.S. Bettahalli Narasimha, D. Stamatialis, M. Wessling
    Membrane Science and Technologv, Facultv of science and technologv, Universitv of Twente, P.O.Box 217, 7500AE
    Enschede, The Netherlands
    m.s.bettahallitnw.utwente.nl
    In Tissue Engineering (TE) cells are seeded on to a support (called scaIIold) to Iorm tissue used to replace damaged and/or
    worn-out tissue. The major problem in such constructs is the nutrient supply to the core, as the growing (proliIerating) cells
    themselves acts as barrier Ior mass transIer |1|. In this work, to address this problem scaIIolds with porous hollow Iibers are
    engineered. These hollow Iibers mimic the arterial circulatory system Ior the in-vitro cultured tissue by supplying nutrients
    through the hollow Iiber lumen at the inlet and removing waste at the outlet. As the Iiber wall acts as a permeable barrier
    between the cell and the nutrient, relatively high Ieed rate can be applied without shear damage to the cells.
    In this work, we develop biocompatible and bio-degradable Poly l-lactide (PLLA) hollow Iibers using phase inversion. Various
    Iiber spinning parameters are studied to develop optimum Iiber structures with optimum permeation properties (Figure 1).
    Experiments Ior nutrient diIIusion through the Iiber with diIIerent porous morphology are also evaluated. In-vitro cell culture
    experiments are carried out to asses the cell attachment and proliIeration.

    (a) (b) (c)
    |1| T.B.F.WoodIield, C.A. van Blitterswijk,j.De Wijn, T.J.Sims, A.P.Hollander, and J.Riesle,. Tissue engineering vol.11, nr
    9/10, 12971311, 2005
    Acknowledgement: This project is Iinancially sponsored by STW (Project number TKG. 6716)
    PA.1.23
    CO
    2
    /CH
    4
    separation properties of Ultem-SAPO-34 mixed matrix composite
    membranes
    A. Kertik, C. Atalay-Oral, S. B. Tantekin-Ersolmaz
    Istanbul Technical Universitv, Department of Chemical Engineering, Maslak, Istanbul 34469, TURKEY
    kertikaitu.edu.tr, cigdemoitu.edu.tr, ersolmazitu.edu.tr
    Polymeric membranes have been studied in detail Ior many gas separation applications Ior the past two-decades. However, the
    current polymeric membranes are still inadequate to Iully supply the demand oI high permselectivity. Inorganic materials such
    -194-
    Figure 1: SEM picture oI PLLA hollow Iiber (a) Iiber wall (b) Iiber surIace (c) Cell cultured on Iiber
    as zeolites can also eIIectively separate many gases. Although these materials have much higher potential separation eIIiciency
    than polymers, diIIiculties in their preparation in the Iorm oI large surIace area modules and their cost have made them less
    attractive. The mixed matrix composite (MMC) membranes constituting a continuous polymeric phase and a dispersed zeolite
    phase oIIer a great potential by combining the processability oI the polymers with superior gas separation properties oI
    zeolites. This requires a selection oI compatible polymer-zeolite pair and elimination oI possible interIacial detachment
    between the two phases.
    This work Iocuses on the development oI polymer/zeolite MMC membranes Ior CO
    2
    /CH
    4
    separation. Polyetherimide
    (ULTEM 1000) was chosen as the polymeric phase due to its potential to exceed the 'Robeson upper-bound trade-oII
    curve. SAPO-34 was chosen due to its high CO
    2
    /CH
    4
    selectivity. SAPO-34 is a small-pore, chabazite-structure
    silicaaluminaphosphate, with a pore size oI 3.8 A. MMC membranes are prepared by incorporating 20 nano-sized (100 nm)
    and micro-sized (1 m) SAPO-34 particles into polymeric phase. Zeolite particles were treated by a priming protocol beIore
    membrane preparation to improve adhesion oI the two phases. The priming protocol is optimized through evaluation oI Iactors
    such as choice oI solvent, type oI mixing, and rate oI drying. Morphological characterization oI MMC membranes were carried
    out using SEM. Their thermal and mechanical behavior was analyzed via DSC, DMA, and TGA. Sorption capacities oI the
    zeolites and the composite Iilms were measured on Intelligent Gravimetric Analyzer (IGA). Single and mixed gas permeability
    coeIIicients oI mixed matrix membranes were measured using a constant volume/variable pressure permeation system. SEM
    images showed good contact between polymer and zeolite phases. MMC membranes displayed improved gas separation
    properties.
    Financial support Irom TUBITAK (Turkish ScientiIic and Technological Research Council) Grant No. 106M179 is grateIully
    acknowledged. Nano- and micro-sized SAPO-34 zeolites were kindly provided by Dr. H. Kalipilar at Middle East Technical
    University, Turkey.
    PA.1.24
    Polymeric capsules prepared by phase inversion technique and their application in
    fine chemistry
    M.G. Buonomenna
    1
    , A. Figoli
    2
    , R. Morelli
    2
    , E. Drioli
    1,2
    1
    Department of Chemical Engineering and Materials, Universitv of Calabria
    2
    ITM-CNR c/o Universitv of Calabria
    Jia P.Bucci 87030 Rende (CS)
    mg.buonomennaitm.cnr
    Polymeric microcapsules are largely applied in various industrial Iields, such as cosmetic, pharmaceutical, chemical, textile
    and Iood packaging. Common techniques Ior producing micro-capsules, having a dense or porous layer, include interIacial
    polymerisation, and precipitation, in situ polymerisation, etc. However, the micro-capsules preparation with a tailored
    morphology is still an important challenge |1,2|. In this communication, we will report on the Iabrication oI asymmetric
    capsules based on PVDF, PES and PEEKWC with diIIerent morphologies exploiting the advantages oI two well established
    technologies, such as membrane emulsiIication and phase inversion. The capsule morphology and dimension can be tailored
    changing Iew Iundamental processes, ingredients parameters, shape and size oI the monopore |2|. In all cases, the cross-
    section oI the prepared capsules presented a central cavity and an asymmetric (Iinger type) structure with a porous or dense
    skin layer at the shell side depending on the coagulant employed. The diameters oI the obtained microcapsules were ranging
    Irom 650 to 2200 microns. The PVDF, PES and PEEKWC microcapsules have been loaded with catalyst ammonium
    molybdate tetrahydrate Ior the selective oxidation oI benzyl alcohols to benzaldehydes to study the eIIect oI diIIerent
    polymeric materials on the conversion and selectivity.
    ProoI oI successIul entrapment oI catalyst inside polymeric matrix was given by EDX, BSE analyses oI Mo based catalyst.
    Additional prooI was given by the diIIerent colorimetric reactions between the catalytic microcapsules and the oxidant
    (hydrogen peroxide) (Figure 1).
    -195-
    Figure 1-Pictures oI catalytic microcapsules in contact with reaction reagents
    PreIerential interaction oI aromatic alcohols with the polymeric membrane (mutual aIIinity) promotes the oxidation Iavouring
    the sorption equilibria and leading to an enrichment oI the substrate concentration on the catalytic surIace, close to the catalytic
    sites. This Iact is also consistent with the increased selectivities (~98) compared to homogeneous reIerences.
    |1| A. Figoli, G. De Luca, E. Longavita, E. Drioli, Sep. Sci. Technol. 2007, 42, 2809.
    |2| M.G. Buonomenna, A. Figoli, I. Spezzano, R. Morelli and E. Drioli J. Phys. Chem. B 2008, 112(36), 11264
    PA.1.25
    Efficient facilitated transport of lead and cadmium across a plasticized triacetate
    membrane mediated by D2EHPA and topo
    O. Arous
    1, 2
    , H. Kerdjoudj
    1
    1
    Laboratorv of Hvdrometallurgv and Inorganic Molecular Chemistrv, U.S.T.H.B- Facultv of Chemistrv, POBOX 32 El Alia,
    16111 Bab E::ouar, Algeria. Fax.213.21.247311,
    2
    Center of Research in Phvsical and Chemical analvsis CRAPC, POBOX 248 Algiers RP 16004, Algiers, ALGERIA.
    The stability oI polymer inclusion membranes (PIMs) relative to other liquid membranes is amongst the major reasons Ior the
    recent resurgence oI interest in carrier-mediated transport Ior selective separation and recovery oI metal ions as well as
    numerous organic solutes |1-4|. This is reIlected by an increasing number oI PIM investigations reported in the literature over
    the last two decades. In this work, we have developed a novel class oI plasticized cellulose triacetate membranes modiIied by
    organo-phosphoric carrier`s incorporation that are selectively permeable to lead and cadmium cations.
    Transport oI Lead and Cadmium ions through a plasticized cellulose triacetate membrane (CTA) containing organo-phosphoric
    carriers (D2EHPA) or (TOPO) and plasticizers 2- nitro phenyl octyl ether (NPOE) or tris ethylhexyl phosphate (TEHP) has
    been investigated. The membrane Polymer Plasticizer Carrier was characterised using chemical techniques as well as
    Fourier TransIorm InIra Red ( FTIR), X ray DiIIraction , DiIIerential Scanning Calorimetry ( DSC ) and Scanning
    electron microscopy ( SEM ).
    |1| O. Arous, H. Kerdjoudj, P. Seta. J. Membr. Sci. 241, (2004), 177.
    |2| A. Gherrou, H. Kerdjoudj, R. Molinari, P. Seta, E. Drioli, J. Membr. Sci., 228, (2004),249.
    |3| M. Sugiura, M. Kikkawa, S. Urita, J. Membr. Sci. 42, (1989), 47.
    |4| O. Arous, M. Amara and H. Kerdjoudj, J. Applied Polymer Sci. 93, (2004), 1401.
    -196-
    PA.1.26
    Preparation of polyethylene (PE) and ethylene vinyl acetate (EVA) membranes for
    gas separation at different conditions
    S.A. Mousavi
    1
    , M. Gholizadeh
    1,2
    , M. PouraIshari-Chenar
    3
    , S. Sedghi
    1
    , Z. Abdekhodaei
    3
    1
    Department of Chemical and Petroleum Engineering, Sharif Universitv of Technologv, Tehran, I.R. Iran.
    2
    Department of Agriculture Engineering,Universitv of Tabri:, Tabri:, I.R. Iran.
    3
    Department of Chemical Engineering, Facultv of Engineering, Ferdowsi Universitv of Mashhad, Mashhad, I.R. Iran.
    musavishariI.ir
    Many attempts have also been taken to learn the relationship between polymer structure and gas permeability. It is generally
    considered that the chain mobility and inter-chain packaging are strongly related to the gas permeability |1|. DiIIusitive jumps
    occur within the polymer matrix when the thermal motions oI polymer chain segments generate transient gaps which are called
    Iree volumes |2|. The increase in Iree volume usually promotes the gas permeation but subsequently allows the passage oI
    larger molecules. Recent studies have been devoted to reducing the packing density and limiting the segmental mobility in
    order to improve gas permeability, but retain the selectivity |1, 2|. Such an approach assumes that the diIIusivity oI a gas
    molecule dominates the gas transport and ignores the possible contribution oI gas sorption. In this study, the eIIect oI Iilm
    preparation conditions on the gas permeation properties oI polyethylene (PE) and ethylene vinyl acetate (EVA) Iilms
    (containing 18 & 28 wt vinyl acetate) was investigated. Film blowing and phase inversion methods were applied to produce
    PE and EVA Iilms, respectively.
    The permeation oI pure oxygen and carbon dioxide gases at room
    temperature were examined. The results indicated that with the
    increase oI Iilm thickness oI PE Iilm, permeability and solubility
    oI gases (O
    2
    and CO
    2
    ) in this polymer decreased; but diIIusivities
    oI gases through PE Iilm increased. In addition, in the case oI
    EVA copolymers, by increasing the content oI vinyl acetate, the
    permeability oI CO
    2
    increased. The rate oI increase in CO
    2
    permeability was diIIerent Ior samples having diIIerent
    preparation conditions.
    Figure 1: SEM micrograph oI EVA membrane
    For example, the samples prepared using chloroIorm as a solvent instead oI THF resulted in lower CO
    2
    permeability.
    Morphological studying oI Iilm structure showed that the higher CO
    2
    permeability Ior the samples made Irom THF solvent is
    due to the existing oI higher porosity in the under layer polymer area. Also scanning electron microscopy (SEM) micrograph
    (Figure-1) showed that with the usage oI phase inversion method, there will be a thin dense layer close to the glass substrate.
    |1| A. Thran, G. Kroll, F. Faupel, Correlation between Iractional Iree volume and diIIusivity oI gas molecules in glassy
    polymers, Journal oI Polymer Science Part B: Polymer Physics, 1999, 37, 3344-3358.
    |2| R.E. Kesting, A.K. Fritzsche, Polymeric gas separation membranes, 1994, John Wiley& Sons, New York.
    PA.2.1
    Highly ordered thin film composite membranes based on self-assembled block
    copolymers
    X. Li
    1
    , N. LeIevre
    2
    , C. A. Fustin
    2
    , J. F. Gohy
    2
    , I. F.J. Vankelecom
    1

    1
    Centre for Surface Chemistrv and Catalvsis, Facultv of Bioscience Engineering, Katholieke Universiteit Leuven
    (K.U.Leuven), Kasteelpark Arenberg 23 Box 2461, B-3001 Leuven, Belgium.
    2
    Unite POLY and CeRMiN, Universite catholique de Louvain, Place Croix du Sud 1, 1348 Louvain-la-Neuve, Belgium
    ivo.vankelecombiw.kuleuven.be
    Membranes are powerIul tools to separate mixtures in an economic, energy eIIicient and environmentally benign way.
    Membrane based technology has already been impressively shown in diIIerent industrial Iields like water puriIication, Iood
    industry, etc. Membranes oIten are prepared by the 'phase inversion process, which can induce porous structures hence
    provide the membranes with certain Ilux and selectivity. A major problem in most porous membranes is the lack oI long-range
    order in the nanopores array.
    -197-
    Block copolymers are composed oI two or more chemically distinct, and Irequently immiscible, polymer blocks covalently
    bound together. Well-ordered arrays oI nanoscopic domains Irom spheres or cylinders to lamellae and co-continuous
    interpenetrating network-like structures can be Iormed depending on the diIIerent volume Iractions oI the components. The
    size oI the domains is deIined by the molecular weight oI the copolymer chains which opens pathways to multi-length scale
    ordering and hence hierarchical ordering. Block copolymers thus are one oI the most versatile materials Ior generating
    Iunctional nanoscopic structures.
    This paper reports highly ordered membranes based on diblock polymers. The highly tunable permeation properties, combined
    with a high chemical and mechanical stability and the use oI very small amounts oI diblock material (due to the use oI
    supports) opens up a signiIicant application potential. Well ordered thin Iilms Irom diblock polymers were thus cast on porous
    supports.
    A second (hydrophilic) polymer could be added to the system to induce the Iormation oI cylinder phase separation structures
    instead oI time consuming thermal or solvent annealing method. AIterwards, ordered porous structures with smaller pores
    could be Iormed by removing this polymer Irom inside the cylinders. The membrane separation properties in NF and SRNF
    were investigated. The results show that this method is really simple and versatile to prepare highly ordered NF nanostructural
    membranes with good separation perIormance.
    1. Yang, S. Y; Ryu, I.; Kim, H. Y.; Kim, J.K.; Jang, S. K.; Russel,l T. P. ; Adv. Mater. 2006, 18, 709712
    2. Peinemann, K.V.; Abetz, V.; Simon, P. F. W.; Nature Mater. 2007, 6, 992-996
    PA.2.2
    Effect of temperature on gas transport properties in mixed matrix membranes of
    PVC-Sr
    2
    CoUO
    6
    M.G. Garcia
    1
    , R. Pinacca
    2
    , J.C. Pedregosa
    2
    , N.A. Ochoa
    1
    , J. Marchese
    1

    1
    Instituto de Fisica Aplicada-INFAP, Universidad Nacional de San Luis-CONICET, Chacabuco 917 5700 San Luis, Argentina
    2
    Area de Quimica General e Inorganica 'Dr. Gabino F. Puelles`, Departamento de Quimica, Facultad de Quimica,
    Bioquimica v Farmacia, Universidad Nacional de San Luis, Chacabuco 917 5700 San Luis, Argentina
    aochoaunsl.edu.ar
    Membranes remain attractive opportunities Ior many gas separation industries (natural gas processing, landIill gas recovery,
    oleIin/paraIIin separation, air separation, hydrogen recovery, etc.). Because oI the economic competitiveness oI the existing
    separation technologies and the present challenges oI aggressive environments Ior membranes, many applications seek more
    robust membrane materials having higher selectivities and permeabilities |1|. In this sense, mixed matrix membranes oIIers the
    potential oI combining the polymers' processability with good gas separation properties oI rigid inorganic materials.
    This work examines the gas transport properties oI a mixed matrix membrane as a Iuncion oI temperature. Commercial
    polyvinyl chloride (PVC) polymer was used as the polymer matrix and Sr
    2
    CoUO
    6
    double perovskite was selected as inorganic
    Iiller. The prepared membranes were characterized by X-Ray diIIraction and mechanical properties measurements.
    Permeability, diIIusion and sorption coeIIicients oI H
    2
    , N
    2
    , CH
    4
    and CO
    2
    in PVC membranes were determined at temperatures
    oI 30 and 50 C and pressure oI 3 atm. A thorough analysis oI the eIIect oI temperature on the permeation, diIIusion and
    soption coeIicients oI gases and selective properties oI the PVC-Perovskite composite membranes was done |2, 3|. The mixed
    matrix membranes showed a decrease oI
    H2/N2
    and
    CO2/CH4
    selectivities respect to pure polymer. The same behavior was
    observed Ior the solubility coeIicients, while a increase oI D
    H2/N2
    and D
    CO2/CH4
    Iactors was showed when an increasing oI
    temperature was done.
    |1| De Q. Vu, William J. Koros, Stephen J. Miller, Mixed matrix membranes using carbon molecular sieves I. Preparation and
    experimental results, Journal oI Membrane Science, 2003, 211, 311-334.
    |2| J. Marchese, E. Garis, M. Anson, N. A. Ochoa, C. Pagliero, Gas sorption, permeation and separation oI ABS copolymer
    membrane, Journal oI Membrane Science, 2003, 221, 185-197.
    |3| J. Marchese, E. Garis, M. Anson, N. A. Ochoa, C. Pagliero, ABS-copolymer activated carbon mixed matrix membranes Ior
    CO
    2
    /CH
    4
    separation, Journal oI Membrane Science, 2004, 243, 19-28.
    -198-
    PA.2.3
    Development of composite membranes for the concentration of PFCs
    Y.I. Park
    1
    , M.Y. Nam
    1
    , B.S. Kim
    1
    , H.K. Lee
    2
    1
    Environment & Resources Research Center, Korea Research Institute of Chemical Technologv, P.O. Box 107, Sinseongno 19,
    Yuseong-Gu, Daefeon 305-600, Korea
    2
    Kael Co., Ltd., 1690-2 Shinil-Dong, Daeduk-Gu, Daefeon 306-230, Korea
    yiparkkrict.re.kr
    PerIluorocompounds (PFCs) emitted Irom semiconductor or LCD industry are recently being concerned about non-CO
    2
    greenhouse gases with their long halI-lives and high global warming potential (GWP). For the eIIicient treatment oI PFCs in a
    scrubbing process, gas separation technologies using membrane are advantageous in that the highly concentrated PFCs can be
    obtained under low pressure. ThereIore, the membranes Ieasible Ior the PFCs concentration system are required to be
    selectively permeable Ior light gases such as N
    2
    and O
    2
    .
    In this study, composite membranes were prepared by coating several types oI polymers, poly(dimethyl-siloxane) (PDMS),
    poly(amide-6-b-ethylene oxide) (PEBAX2533, 4033), as separating layer materials on the asymmetric porous polyethersulIone
    (PES) support. To enhance the permselectivity oI the composite membranes, mixed matrix membranes (MMMs) were also
    prepared with adding inorganic Iillers to the separating layers. The structures oI the prepared membranes were characterized
    with SEM. To investigate the permeation properties, the membranes were tested with Air, N
    2
    , CF
    4
    , and SF
    6
    at various
    operating conditions, and their gas permeabilities were compared with PDMS and PEBAX dense membranes. Since Air and N
    2
    have smaller molecule size than that oI CF
    4
    and SF
    6
    , the permeability coeIIicients oI these gases (Air and N
    2
    ) through all
    membranes were Iound to be considerably high. For dense membranes, PDMS membrane exhibited the highest permeability
    Ior Air oI all the tested gases while PEBAX4033 membrane showed the highest selectivity oI CF
    4
    to Air. MMMs with the
    introduction oI the zeolite 5A were less permeable than the composite membranes without the inorganic Iiller, but they showed
    a little increase in gas selectivity.
    Fig. 1. Cross-sectional view oI PDMS-
    zeolite/PES composite membrane.
    Fig. 2. Cross-sectional view oI PEBAX2533-
    zeolite/PES composite membrane.
    Fig. 3. Cross-sectional view oI PEBAX4033-
    zeolite/PES composite membrane.
    This subfect is supported bv Korea Energv Management Corporation (KEMCO) as an Energv Resources Technologv
    Development Profect.
    |1| J. Kim, Y. Lee, Gas permeation properties oI poly(amide-6-b-ethylene oxide)-silica hybrid membranes, J. Membr. Sci.,
    2001, 193, 209-225
    |2| Y. Li, H. Guan, T. Chung, S. Kulprathipanja, EIIects oI novel silane modiIication oI zeolite surIace on polymer chain
    rigidiIication and partial pore blockage in poyethersulIone (PES)-zeolite A mixed matrix membranes, J. Membr. Sci., 2006,
    275, 17-28
    PA.2.4
    Templated growth of aligned carbon nanotubes on porous
    supports and membranes
    E.C. Vermisoglou, G. Pilatos, C.M. Veziri, G.N. Karanikolos, G.E. Romanos, J.W. Nolan, N.K. Kakizis,
    N.K. Kanellopoulos
    Institute of Phvsical Chemistrv, National Center for Scientific Research Demokritos, Ag. Paraskevi, Athens 153 10, Greece
    karanikoloschem.demokritos.gr
    Templated growth oI aligned carbon nanotubes inside the one-dimensional, straight pores oI anodized alumina using
    IerroIluid, a colloidal suspension oI surIactant-coated Ierrous nanoparticles, as catalyst and carbon source is presented. A
    -199-
    specially-designed CVD system was used, in which ethylene was Iorced to Ilow through the pores oI the template, thus
    assisting nanotube Iormation and alignment. Fine dispersion oI the IerroIluid along the pores was achieved by ion exchange
    using NH
    4
    NO
    3
    . On-line measurement oI the diIIerential pressure between the two sides oI the alumina template allowed
    continuous monitoring oI the evolution oI nanotube growth. Based on the diIIerential pressure data, the process can be divided
    into three stages, carbon source decomposition, nanotube Iormation, and amorphous carbon deposition, and was optimized by
    adjusting the conditions (gas Ilowrate, reaction duration) appropriately. Use oI excess oI IerroIluid allowed loading oI the
    nanotubes with paramagnetic iron oxide particles upon synthesis, with a particle density that depends upon the IerroIluid
    concentration, producing one-dimensional nanotube arrays that are promising building nanostructures Ior Iabrication oI
    magnetic Iield-responsive devices. Results Irom experiments using additional porous supports, namely activated carbon, heat-
    treated macroporous polymeric beads, and microporous aluminophosphate molecular sieves will also be discussed.
    PA.2.5
    Preliminary study on use of functionalized hydrocarbonic resins for obtaining
    polyelectrolytes membranes
    B.B.R. Silva, F.J.B. Brum, C. M. Branco, M.M.C. Forte
    Universitv of Rio Grande do Sul (UFRGS), Av. Bento Gonalves, 9500, Setor IJ, Predio 74, Campus do Jale, 91501-970 -
    Porto Alegre-RS - Brasil
    mmcIorteuIrgs.br
    One oI the key challenges in advancing the polymer electrolyte membrane Iuel cell (PEMFC) technology lies presently in the
    development oI new durable membranes that allow operation in a broad temperature window, at low humidiIication with water
    vapor or with no humidiIication at all |1|. The state-oI-the-art oI PEMFC technology is based on perIluorosulIonic acid
    (PFSA) polymer membranes operating at a typical temperature oI 80 C and only exhibit suIIicient proton conductivity at high
    degrees oI hydration. The proton conducting membranes employed in PEMFCs are today typically based on polymers with
    hydrated sulIonic acid units. Various eIIorts to substitute the water with less volatile proton conducting compounds have been
    made and membranes doped with phosphoric acid have perhaps been most extensively studied in this respect |2-4|. This work
    discusses an alternatively use oI sulIonated hydrocarbon resins (SR) and poly(vinyl alcohol) (PVA) blends with addiction oI
    antimonic acid (AAc) and phosphonated hydrocarbon resins (PR) to improve the mechanical and conductivity properties. The
    PVA, a water soluble polymer, was reticulated with glutaraldehyde and the membranes were obtained with diIIerent ratio oI
    AAc and PR. The Iunctionalized resins were characterized by FTIR spectroscopy and the membranes (SR/PVA/PR and
    SR/PVA/AAc) were characterized by water uptake measurements, ionic exchange capacity, thermogravimetric analysis (TGA)
    and the conductivity were assessed by impedance spectroscopy.
    |1| J. Parvole, P. Jannasch, PolysulIones GraIted with Poly(vinylphosphonic acid) Ior Highly Proton Conducting Fuel Cell
    Membranes in the Hydrated and Nominally Dry State, Macromolecules, 2008, 41, 3893-3903.
    |2| Q. Li, R. He, J.O. Jensen, N.J. Bjerrum, Approaches and Recent Development oI Polymer Electrolyte Membranes Ior Fuel
    Cells Operating above 100C, Chemistry oI materials, 2003, 15(26) 4896-4915
    |3| J. Roziere, D.J. Jones, Non-Iluorinated Polymaterials Ior Proton Exchange Membrane Cells, Annual Review oI Materials
    Research, 2003, 33, 503-555.
    |4| J.M. Amarilla, R.M. Rojas, J.M. Rojo, M.J. Cubillo, A. Linares, J.L. Costa, Antimonic acid and sulIonated polystyrene
    proton-conducting polymeric composites, Solid State Ionics, 2000, 127, 133-139.
    -200-
    PA.2.6
    Effect of temperature on gas transport properties in mixed matrix membranes of
    PVC-Sr
    2
    CoUO
    6
    M. G. Garcia
    1
    , R. Pinacca
    2
    , J. C. Pedregosa
    2
    , N. A. Ochoa
    1
    , J. Marchese
    1
    1
    Instituto de Fisica Aplicada-INFAP, Universidad Nacional de San Luis-CONICET, Chacabuco 917 5700 San Luis, Argentina
    2
    Area de Quimica General e Inorganica 'Dr. Gabino F. Puelles`, Departamento de Quimica, Facultad de Quimica,
    Bioquimica v Farmacia, Universidad Nacional de San Luis, Chacabuco 917 5700 San Luis, Argentina
    aochoaunsl.edu.ar
    Membranes remain attractive opportunities Ior many gas separation industries (natural gas processing, landIill gas recovery,
    oleIin/paraIIin separation, air separation, hydrogen recovery, etc.). Because oI the economic competitiveness oI the existing
    separation technologies and the present challenges oI aggressive environments Ior membranes, many applications seek more
    robust membrane materials having higher selectivities and permeabilities |1|. In this sense, mixed matrix membranes oIIers the
    potential oI combining the polymers' processability with good gas separation properties oI rigid inorganic materials.
    This work examines the gas transport properties oI a mixed matrix membrane as a Iuncion oI temperature. Commercial
    polyvinyl chloride (PVC) polymer was used as the polymer matrix and Sr
    2
    CoUO
    6
    double perovskite was selected as inorganic
    Iiller. The prepared membranes were characterized by X-Ray diIIraction and mechanical properties measurements.
    Permeability, diIIusion and sorption coeIIicients oI H
    2
    , N
    2
    , CH
    4
    and CO
    2
    in PVC membranes were determined at temperatures
    oI 30 and 50 C and pressure oI 3 atm. A thorough analysis oI the eIIect oI temperature on the permeation, diIIusion and
    soption coeIicients oI gases and selective properties oI the PVC-Perovskite composite membranes was done |2, 3|. The mixed
    matrix membranes showed a decrease oI
    H2/N2
    and
    CO2/CH4
    selectivities respect to pure polymer. The same behavior was
    observed Ior the solubility coeIicients, while a increase oI D
    H2/N2
    and D
    CO2/CH4
    Iactors was showed when an increasing oI
    temperature was done.
    |1| De Q. Vu, William J. Koros, Stephen J. Miller, Mixed matrix membranes using carbon molecular sieves I. Preparation and
    experimental results, Journal oI Membrane Science, 2003, 211, 311-334.
    |2| J. Marchese, E. Garis, M. Anson, N. A. Ochoa, C. Pagliero, Gas sorption, permeation and separation oI ABS copolymer
    membrane, Journal oI Membrane Science, 2003, 221, 185-197.
    |3| J. Marchese, E. Garis, M. Anson, N. A. Ochoa, C. Pagliero, ABS-copolymer activated carbon mixed matrix membranes Ior
    CO
    2
    /CH
    4
    separation, Journal oI Membrane Science, 2004, 243, 19-28.
    PA.2.7
    Composite polymeric membranes for gas separation: plasma polymerization from
    hexamethyldisiloxane (HMDSO) and ethylene glycol monomethyl ether acetate
    (EGMEA)
    S. Miguel
    1
    , M. Etxeberria
    1
    , E. Fernandez-Gesalaga
    1
    , P. Corengia
    1
    , F.J. Fernandez-Carretero
    1
    , A. Gutierrez
    2
    1
    INASMET-Tecnalia, Paseo de Mikeletegi 2, E-20009 San Sebastian, Spain
    2
    Naturgas Energia, Pla:a Pio Barofa 3, Planta 2, 48001 Bilbao, Spain
    sara.miguelinasmet.es
    Commercial gas separation applying membranes is a dynamic and rapidly growing Iield. In the last 20 years; the study oI gas
    permeability and permselectivity oI polymer membranes has increasingly become a subject oI intense, world wide research
    both in academia and industry. In order to develop new polymers with improved properties it is required to use new
    manuIacture techniques and understand the structure-properties relationship oI polymer structure and gas permeation.
    Plasma polymerization Ior membrane preparation is a very promising Iield Ior producing pinhole Iree very thin highly cross-
    linked polymeric Iilms (thin Iilms give higher Iluxes), and with good permselectivities |1|. The gas permeation perIormances
    oI plasma polymers are related to their chemical composition and structural properties. These properties depend on the
    precursor (monomer) and on the polymerization process conditions.
    In this work, the Ion Gun Inverse Magnetron (IGIM) plasma polymerization technique has been used to produce composite
    polymeric Ilat sheet membranes Ior the separation oI H
    2
    /CH
    4
    , H
    2
    /CO
    2
    , CO
    2
    /CH
    4
    , CH
    4
    /N
    2
    and O
    2
    /N
    2
    gas mixtures. Plasma
    polymers prepared Irom hexamethyldisiloxane (HMDSO) and Irom ethylene glycol monomethyl ether acetate (EGMEA) have
    -201-
    been deposited onto diIIerent polysulIone supports. The gas separation membranes have been prepared using diIIerent plasma
    conditions: power (30W, 40W and 50W) |2| and exposures (3 hours and 5 hours).
    The developed plasma polymerized gas separation membranes have been characterized by Scanning Electron Microscopy
    (SEM), Fourier TransIorm InIrared Spectroscopy (FTIR), and Energy Dispersive X-ray Spectroscopy (EDS). Gas separation
    and permeation properties Ior H
    2
    , CH
    4
    , CO
    2
    , O
    2
    and N
    2
    gases through the plasma polymerized membranes have been
    investigated in detail as a Iunction oI pressure, precursor and support type using a time-lag method, and related to the
    morphology oI the membranes.
    |1| Sae-Joong Oh, W.P. Zurawsky, Gas permeation through poly(dimethylsiloxane)-plasma polymer composite membranes,
    Journal oI Membrane Science 120 (1996) 89-99.
    |2| K. Li, J. Meichsner, Gas-separating properties oI membranes coated by HMDSO plasma polymer, SurIace and Coatings
    Technology 116-119 (1999) 841-847.
    PA.2.8
    Changes in the CO
    2
    /CH
    4
    selectivity and productivity of the 6FDA-6FpDA polyimide
    by the addition of functionalized -alumina nanoparticles
    L. Fernandez
    1
    , M. Sanchez
    1
    , A. Tena
    2,4
    , L. Palacio
    2,4
    , A.E. Lozano
    3,4
    , A. Hernandez
    2,4
    , P. Pradanos
    2,4
    1
    Dpto de Quimica, Facultad de Ingenieria, Universidad Nacional del Comahue, Buenos Aires 1400, Neuquen. Argentina
    2
    Dpto. de Termodinamica v Fisica Aplicada, Fac. de Ciencias, Universidad de Jalladolid, Jalladolid, Spain
    3
    Instituto de Ciencia v Tecnologia de Polimeros, CSIC, Juan de la Cierva 3, 28006 Madrid. Espaa.
    4
    Surface and Porous Materials (SMAP), UA-CSIC-UJA, R&D Building, Campus Miguel Delibes. Jalladolid. Espaa.
    albtenatermo.uva.es
    The gas sweetening process by membrane technology is an economically Ieasible method to puriIy gas mixtures when high
    selectivity values are reached and the most permeable gas is the gas to be rejected, that means that a low loss oI pressure in the
    valuable gas stream is achieved. Nowadays, neat polymeric membranes are widely used in this process due to their separation
    properties. Nevertheless, many other possibilities can be tested in order to improve the perIormances oI gas separation
    membranes to be used in the separation oI acid gases. One oI this ways consists oI increasing substantially the selectivity by
    using the so called mixed matrix membranes. These membranes are composed oI a polymeric matrix Iilled with nanometric
    inorganic particles. In this approach, the main drawback is how to circumvent the lack oI compatibility between the organic
    and inorganic phases.
    In this work, a high molecular weight Iluorinated aromatic polymer, 6FDA-6FpDA with an intrinsic viscosity oI 0.62 dL/g has
    been used as the polymeric matrix. This polymer has a relatively high Iree volume Iraction. The inorganic phase consisted oI -
    alumina particles with 50 nm mean diameter. The compatibility between these phases has been enhanced by means oI a
    modiIication oI the surIace oI the inorganic particles. Thus, the composite includes the polymer material with a 1 oI -
    alumina particles: a) neat nanoparticles with no surIace modiIication. b) silanized surIace particles c) particles coated with a
    thin layer oI polyvinylpyrrolidone (PVP).
    The gas separation properties, permeability and selectivity, oI the membrane without any Iilling and the three composite
    membranes, obtained by adding the -alumina particles, were analyzed Ior diIIerent gases. Here, the main target oI our
    research was the separation oI the CO
    2
    /CH
    4
    gas pair. The obtained results have shown that all the mixed matrix membranes had
    both much better permeabilities and selectivities that that oI the 6FDA-6FpDA membranes without any inorganic phase.
    In this way, the membranes with uncoated particles, and also those with PVP coated ones, showed simultaneously an important
    increase oI CO
    2
    permeability and CO
    2
    /CH
    4
    selectivity. On the other hand, the material with silanized -alumina particles gave a
    membrane with a very improved selectivity whereas the enhancement in permeability was much lower than that observed Ior
    the other composite membranes.
    These results have been interpreted in terms oI changes oI the Iree volume Iraction and also by assuming that there are acid-
    base interactions oI CO
    2
    with the nanoparticles.
    -202-
    PA.2.9
    The development of silica-filled thin film poly(1-trimethylsilyl-1-propyne)
    membranes for organophilic pervaporation
    S. Claes
    1

    ,2
    , P. Vandezande
    1
    , S. Mullens
    1
    , R. Leysen
    1
    , R. Peeters
    3
    , M. K. Van Bael
    2
    1
    JITO, Flemish Institute for Technological Research, Boeretang 200, B-2400 Mol, Belgium
    2
    UHasselt, Inorganic & Phvsical Chemistrv, Agoralaan building D, 3590 Diepenbeek, Belgium
    3
    XIOS, eXpertise centrum voor Industrie, Onderwifs en Samenleving, Agoralaan building H, 3590 Diepenbeek, Belgium

    stan.claesvito.be
    Poly(1-trimethylsilyl-1-propyne) (PTMSP) is a substituted polyacetylene that exhibits the highest oxygen permeability oI all
    known synthetic polymers. The high permeability can be attributed to the extremely high Iree volume oI the polymer matrix,
    which can be Iurther increased by incorporation oI silica nano-particles|1|. In this work the potential oI PTMSP based
    membranes in organophilic pervaporation (PV) and solvent-resistant nanoIiltration (SRNF) will be discussed. A thin silica-
    Iilled PTMSP Iilm is coated onto a support membrane, which has to be highly porous, may not negatively inIluence the
    selectivity and should provide mechanical stability to the PTMSP toplayer.
    A Iirst part oI this work consisted oI the characterization oI two diIIerent support membranes based on polyacrylonitril (PAN)
    and polyvinylidene Iluoride (PVDF). Clean water Ilux, molecular weight cut-oII, contact-angle, surIace roughness, scanning
    electron microscopy and capillary Ilow analysis are some oI the tests that were perIormed. PVDF displayed superior properties
    and was thereIore used in this work. A second part oI this study Iocused on the characterization oI the polymer and to deIine
    the desired membrane properties Ior PV and SRNF. DiIIerent PTMSP batches were characterized Ior molecular weight,
    chemical structure, dope rheology and purity. Positron Annihilation LiIetime Spectroscopy (PALS) measurements were
    perIormed to quantiIy the Iree volume oI the diIIerent batches.
    Initial PV tests on a 10/90 wt ethanol/water Ieed resulted in Iluxes up to 3.7 + 1.3 kg/m.h and selectivities oI 12 + 2 Ior the
    thin Iilm silica-Iilled composite PTMSP/PVDF membranes.
    Due to PTMSP`s poor chemical stability in many solvents, the membranes need to be crosslinked. This was realized here by
    adding 3,3`-diazidodiphenylsulIone to the casting solution and treating the Iinal membrane at elevated temperatures|2|. The
    inIluence oI the crosslinks on the solvent stability and separation characteristics in PV and SRNF was investigated.
    |1| K. De Sitter, Preparation and characterization oI organic-mineral membranes by the incorporation oI nanoparticles in high
    Iree volume polymers, PhD thesis K.U. Leuven, October 2007
    |2| S. D. Kelman, S. Matteucci, C. W. Bielwaski and B. D. Freeman, Crosslinking poly(1-trimethylsilyl-1-propyne) and its
    eIIect on solvent resistance and transport properties, Polymer 48 (2007), 6881-6892
    PA.2.10
    Composite membranes based on electrospun non-woven porous support for salt
    separation
    S. Kaur
    1
    , G. Singh
    1
    , T. Matsuura
    2
    , S. Ramakrishna
    1
    1
    National Universitv of Singapore, Nanoscience and Nanotechnologv Initiative, Facultv of Engineering, Blk E3=05-12
    Nanobioengineering Lab, 2 Engineering Drive 3, Spore 117576
    2
    Industrial Membrane Research Laboratorv, Department of Chemical Engineering, Universitv of Ottawa, 161 Louis Pasteur
    Street, P.O. Box 450, Station A, Ottawa Ont., K1N 6N5, Canada
    nnisknus.edu.sg
    Poly(1-trimethylsilyl-1-propyne) (PTMSP) is a substituted polyacetylene that exhibits the highest oxygen permeability oI all
    known synthetic polymers. The high permeability can be attributed to the extremely high Iree volume oI the polymer matrix,
    which can be Iurther increased by incorporation oI silica nano-particles|1|. In this work the potential oI PTMSP based
    membranes in organophilic pervaporation (PV) and solvent-resistant nanoIiltration (SRNF) will be discussed. A thin silica-
    Iilled PTMSP Iilm is coated onto a support membrane, which has to be highly porous, may not negatively inIluence the
    selectivity and should provide mechanical stability to the PTMSP toplayer.
    A Iirst part oI this work consisted oI the characterization oI two diIIerent support membranes based on polyacrylonitril (PAN)
    and polyvinylidene Iluoride (PVDF). Clean water Ilux, molecular weight cut-oII, contact-angle, surIace roughness, scanning
    electron microscopy and capillary Ilow analysis are some oI the tests that were perIormed. PVDF displayed superior properties
    -203-
    and was thereIore used in this work. A second part oI this study Iocused on the characterization oI the polymer and to deIine
    the desired membrane properties Ior PV and SRNF. DiIIerent PTMSP batches were characterized Ior molecular weight,
    chemical structure, dope rheology and purity. Positron Annihilation LiIetime Spectroscopy (PALS) measurements were
    perIormed to quantiIy the Iree volume oI the diIIerent batches.
    Initial PV tests on a 10/90 wt ethanol/water Ieed resulted in Iluxes up to 3.7 + 1.3 kg/m.h and selectivities oI 12 + 2 Ior the
    thin Iilm silica-Iilled composite PTMSP/PVDF membranes.
    Due to PTMSP`s poor chemical stability in many solvents, the membranes need to be crosslinked. This was realized here by
    adding 3,3`-diazidodiphenylsulIone to the casting solution and treating the Iinal membrane at elevated temperatures|2|. The
    inIluence oI the crosslinks on the solvent stability and separation characteristics in PV and SRNF was investigated.
    |1| K. De Sitter, Preparation and characterization oI organic-mineral membranes by the incorporation oI nanoparticles in high
    Iree volume polymers, PhD thesis K.U. Leuven, October 2007
    |2| S. D. Kelman, S. Matteucci, C. W. Bielwaski and B. D. Freeman, Crosslinking poly(1-trimethylsilyl-1-propyne) and its
    eIIect on solvent resistance and transport properties, Polymer 48 (2007), 6881-6892
    PA.2.11
    Effect of Polymeric crosslinking agents on solvent stable organic solvent
    nanofiltration membranes
    H. Siddique, Y. Bhole, M. Sairam, A.G. Livingston
    Department of Chemical Engineering and Chemical Technologv, Imperial College, South Kensington Campus, Exhibition
    Road, London, SW72AZ
    a.livingstonimperial.ac.uk
    In Organic Solvent NanoIiltration (OSN), polymeric membranes are subjected to crosslinking to make them resistant to
    organic solvents. In literature, HDA (1,6-hexanediamine), PDA (1,3-propanediamine), etc have been reported to crosslink
    polyimide membranes |1, 2|, which are corrosive in nature. In this study, we report nanoIiltration perIormance oI polyimide
    membranes crosslinked with a polymeric crosslinking agent. Asymmetric composite OSN membranes oI P84 polyimide were
    prepared by phase inversion technique. Membranes were chemically crosslinked using a polymeric crosslinker. Crsosslinked
    membranes were dried at room temperature and also at 75C Ior 19 h. The nanoIiltration perIormance oI these membranes was
    evaluated in solvents such as DMF, acetone, tetrahydroIuran and toluene. The molecular weight cut-oII (MWCO) oI the
    membrane in acetone was around 300 g.mol
    -1
    (Figure 1). The OSN perIormance oI membranes crosslinked with polymeric
    crosslinking agents will be discussed
    The author wish to acknowledge University oI Engineering and Technology, Lahore, Pakistan Ior Iinancial assistance.
    |1|. Y.H.See-Toh, M.Silva, A.G.Livingston, Controlling molecular weight cut-oII curves Ior highly solvent stable organic
    solvent nanoIiltration (OSN) membranes, Journal oI Membrane Science 324 (2008) 220232.
    -204-
    |2|. Y.H.See-Toh, F.W.Lim, A.G.Livingston, Polymeric membranes Ior nanoIiltration in polar aprotic solvents, Journal oI
    membrane science 301 (2007) 3-10.
    PA.2.12
    Elaboration of chitosan-activated carbon composite materials for wound dressing
    applications: characterization of the porous structure
    A. Venault


    1
    , S. Lagerge
    2
    , C. Pochat
    1
    , D. Bouyer
    1
    , L. Vachoud
    3
    , C. Faur
    1

    1
    UMR Cirad 016 Genie des Procedes Eau Bioproduits, Universite de Montpellier 2, place Eugene Bataillon, 34095
    Montpellier Cedex 5
    2
    Institut Charles Gerhardt, Institut de Chimie Moleculaire et des Materiaux de Montpellier, CNRS UMR 5253, Universite de
    Montpellier 2, place Eugene Bataillon, 34095 Montpellier Cedex 5
    3
    UMR Cirad 016 Genie des Procedes Eau Bioproduits, UFR Sciences Pharmaceutiques et Biologiques, 15 avenue
    Charles Flahault, BP 14491, 34093 Montpellier Cedex 5
    avenaultuniv-montp2.Ir
    catherine.Iauruniv-montp2.Ir
    Composite hydrogel made oI chitosan (biological properties) and activated carbon (adsorption properties) were prepared using
    the Vapor Induced Phase Separation process (VIPS) which permits to slow down mass transIers compared to classical
    elaboration processes, in order to get the Iinal suitable porous structure in relationship with the targeted medical applications
    1
    .
    The optimal porous structure has to be asymmetrical with a porous layer, above the wound, to permit a control oI the relative
    humidity whereas an external dense layer should prevent a possible bacterial inIection, but enable oxygen exchanges needed
    Ior healing.
    Although membranes can be directly characterized by Environmental Scanning Electronic Microscopy (ESEM), hydrogels (97
    oI water) need to be previously dehydrated with a process allowing a low shrinkage and as a consequence a low
    destructuring. In this work, a drying under supercritical CO
    2
    conditions was perIormed
    2
    , leading to aerogels. Though a slight
    shrinkage was obtained, this is the best technique, to the best oI our knowledge, to obtain aerogels with structure as close as
    possible oI the hydrogels one. The structure oI the elaborated material could thus be correlated with the process parameters.
    ESEM results (Iig. 1) show the polymeric matrix is composed oI cellular pores (diameter 20 m). These pores should allow a
    control oI the relative humidity above the skin, which is indispensible to an eIIicient healing. In addition, activated carbon
    seems to be homogeneously distributed within the composite, permitting to avoid breaking points responsible Ior a low
    mechanical strength oI the composites. Major inIluent parameters on the Iinal structure seem to be the polymer concentration,
    the non-solvent vapor pressure and the exposure time to vapors. Further drying works are being perIormed, to get the desired
    asymmetrical structure by adding a dense layer above the porous one.
    Figure 1: ESEM pictures oI chitosan-AC composites. a. SurIace observation, |chitosane| 4 (w:v), |AC| 1.3 (w/v); b.
    SurIace observation, |chitosane| 4 (w:v), |AC| 3.4 (w/v); c. Cross section observation, |chitosane| 4 (w:v), |AC|
    1.3 (w/v); d. Cross section observation, |chitosane| 4 (w:v), |AC| 3.4 (w/v).
    |1| Mi F.-L., Wu Y.-B., Shyu S.-S., Chao A.-C., Lai J.-Y., Su C.-C., Asymmetric chitosan membranes prepared by dry/wet
    phase separation: a new type oI wound dressing Ior controlled antibacterial release, Journal oI Membrane Science (2003) 212,
    p.237-254.
    |2| Quignard F., Valentin R., Di Renzo F., Aerogel materials Irom marine polysaccharides, New Journal oI Chemistry (2008)
    32, p.1300-1310.
    -205-
    d)
    PA.3.1
    Effect of TEOS addition on preparation of mesoporous silica thick coating by
    electrophoretic deposition
    A. Miyamoto
    1, 2
    , H. Negishi
    2
    , A. Endo
    2
    , K. Sakaki
    2
    , T. Ohmori
    2
    , H. Yanagishita
    2
    , K. Watanabe
    1
    1
    Department of Pure and Applied Chemistrv, Facultv of Science and Technologv, Tokvo Universitv of Science (TUS), 2641
    Yama:aki, Noda, Chiba 278-8510, Japan,
    2
    Bio-Chemical Group, Research Institute for Innovation in Sustainable Chemistrv, National Institute of Advanced
    Industrial Science and Technologv (AIST) ,AIST Central 5-2, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
    h-negishiaist.go.jp
    Ordered mesoporous materials have potential applications in, Ior example, catalysis, membranes and adsorbents |1| because oI
    their orderly and uniIorm mesopores, large speciIic surIace area and pore volume. Ordered mesoporous silica (MPS) is
    expected as an adsorbent Ior the energy-eIIicient desiccant cooling systems, because it can be recovered by using low-
    temperature exhaust heat at less than 60 C. For practical use, it is important to Iix ordered MPS onto substrates that do not
    degrade their porous structure or adsorption properties. We have reported the preparation oI MPS coatings on stainless steel
    tubes using electrophoretic deposition (EPD) method |2|. However, we haven`t obtained the MPS coating with a good
    strength Ior practical use. In this study, we investigated the eIIect oI the binder addition to the EPD bath on preparation oI
    MPS thick coatings Ior increasing the strength oI MPS coating. Tetraethoxysilane (TEOS) was used as a binder. The EPD
    bath was prepared by dispersing MPS particles (Taiyo kagaku Co., Ltd.) in acetone. TEOS was added to the EPD bath.
    Aluminum plates were used as deposition substrates. Two stainless steel plates were used as the counter electrodes. A DC
    voltage was applied using a DC power supply between the substrate and the counter electrode. The strength oI MPS coating
    was evaluated by three-point bending test. Though a constant pressure was applied to the MPS coating, the MPS coating
    prepared with TEOS addition adhered to substrates, whereas the MPS coating without TEOS addition became unstuck. It was
    Iound that adhesion oI MPS coating increased by binder addition. It was considered that the Si-O bonds were Iormed between
    MPS particles. The obtained MPS thick coating had almost the same porous structure and adsorption properties with respect to
    nitrogen and water vapor as the parent MPS powder, suggesting that no signiIicant change in the porous structure oI MPS
    occurred by the addition oI the binder to EPD bath.
    This study was supported by the Industrial Technology Research Grant Program in 2006 oI the New Energy and Industrial
    Technology Development Organization (NEDO) oI Japan.
    |1| Chunyan Liu, Liqiu Wang, Wanzhong Ren, Zhihong Rong, Xiaoqing Wang, Zhihong Rong, Xiaoqing Wang and Jinqu
    Wang, Synthesis and characterization oI a mesoporous silica (MCM-48) membrane on a large-pore -Al
    2
    O
    3
    ceramic tube,
    Microporous and Mesoporous Materials, 2007, 106, 35-39
    |2| H. Negishi, A. Endo, T. Ohmori and K. Sakaki, Fabrication oI mesoporous silica coating by electrophoretic deposition,
    Industrial & Engineering Chemistry Research, 2008, 47, 7236-7241
    PA.3.2
    Gas transport mechanism and separation properties of membranes with nano-
    structured porosity based on exfoliated graphite foils
    D.A. Syrtsova
    1
    , O.N. Shornikova
    2
    , V.V. Avdeev
    2
    , V.V. Teplyakov
    1,2
    1
    A.J. Topchiev Petrochemical Svnthesis Institute of RAS, Leniski pr., 29, Moscow, Russian Federation
    2
    M.J.Lomonosov Moscow State Universitv, Leninskie gorv 1, Moscow, Russian Federation
    dashaips.ac.ru
    The modern requirements oI membrane gas separation processes stimulate the search oI new membranes that provide better
    separation perIormance with high thermal and chemical stability. One oI most interesting directions is the development oI new
    inorganic membrane materials with nano-structured porosity providing high gas selectivity, particularly Ioils based on
    exIoliated graphite. This material demonstrates increased H
    2
    /CO
    2
    selectivity in comparison with most industry produced
    polymeric and inorganic membranes at high H
    2
    Ilux |1|. This paper presents the gas permeability data to study mechanisms oI
    the selectivity increase. Previously, it was Iound |2| that gas Ilux through such materials strongly depends oI macrostructure oI
    -206-
    exIoliated graphite, particularly, density and structure anisotropy. The gas selective properties oI graphite based membranes Ior
    diIIerent gas Ilow directions through the Ioils at wide range density were studied in this paper.
    The permeability oI H
    2
    , N
    2
    , O
    2
    , CO
    2
    and CH
    4
    was measured by gas chromatography technique (diIIerential permeability
    method) at temperature 23-95
    o
    C.
    It was Iound that contribution oI Langmuir sorption and surIace Ilow to CO
    2
    selective gas transport through the membrane are
    very important. The comparison oI gas permeance and selectivity Ior parallel and normal to membrane surIace gas Ilow shows
    that gas permeance Ior parallel Ilux is higher than Ior normal mode. This Ieature strongly depends on Ioil density. It is
    interesting to note that Ior parallel mode experiments the value oI H
    2
    /CO
    2
    selectivity is closed to Knudsen one and selectivity
    maximum obtained Ior normal Ilax is not achieved. The results can be connected with inIluence oI diIIerent membrane
    tortuosity on gas Ilow through nano-structure porous matrix.
    It is shown that selective gas Ilow through exIoliated graphite is deIined by gas-matrix sorption and membrane macrostructure
    including anisotropy eIIect. Obtained results can be eIIectively used Ior the development oI new graphite based membranes Ior
    H
    2
    /CO
    2
    separation in Iuel cells application and other gas separation processes.
    This work is partially supported by Grant RFBR No 08-03-92503
    |1| D.A.Syrtsova, E.A.EIimova, E.N.Sorokina, V.V.Teplyakov, A.V.Avdeev, Patent RF N 2007134089
    |2| Celzard A., Marche J.F., Furdin G. Modelling oI exIoliated graphite, Progress in polymer science, 2005, v. 50, pp. 93-179
    PA.3.3
    Pore size control of microporous silica membranes with low temperature CVD/CVI
    modification methods
    D. Koutsonikolas
    1
    , G. Pantoleontos
    3
    , S. Kaldis
    2
    , G.P. Sakellaropoulos
    1,2,3
    1
    Chemical Process Engineering Laboratorv, Department of Chemical Engineering, Aristotle Universitv of Thessaloniki, P.O.
    1520, 54006, Thessaloniki, Greece
    2
    Chemical Process Engineering Research Institute, Centre for Research and Technologv Hellas, 6
    th
    Km Harilaou-Thermis,
    P.O. 361, 57001, Thermi, Thessaloniki, Greece
    3
    Institute for Solid Fuel Technologv and Applications, Centre for Research and Technologv Hellas, 4
    th
    Km Ptolemaidas-
    Ko:anis, P.O. 95, 50200, Ptolemaida, Greece
    dkoutsonvergina.eng.auth.gr
    The last two decades microporous silica membranes have attracted much interest Ior high temperature gas separations. These
    membranes show high Iluxes Ior small gas molecules, such as He and H
    2
    and considerable selectivities Ior these gases with
    respect to larger ones |1|. The sol-gel method is Irequently adopted in silica membrane synthesis because oI its simplicity,
    controllability and homogeneity |2|. Nevertheless, the uncertainty in producing deIect-Iree supported membranes with the sol-
    gel method is still a major problem which deters the commercialization oI these membranes. The presence oI a small amount
    oI deIects, even in the nm range, on the silica layer can reduce the selectivity oI the membranes dramatically |3|.
    In this study we examine the application oI low temperature vapor phase modiIication methods Ior pore size control and deIect
    repairing oI sol-gel silica membranes. SpeciIically, CVD/CVI modiIication methods with TEOS/O
    2
    and TEOS/O
    3
    as reactants
    were conducted at 300
    o
    C and 250
    o
    C respectively. The separation perIormance oI the membranes was evaluated with single
    gas permeation experiments beIore and aIter the modiIications. The results revealed a signiIicant increase in the
    permselectivity oI the membranes aIter the modiIications.
    A non-steady-state mathematical model was also conducted in order to describe the pore radius changes and the reactants
    concentrations with respect to time and axial position, which takes into account the diIIusive Ilux through the membrane pores
    and the Iormation rate oI the solid product.
    |1| Y.S. Lin, Microporous and dense inorganic membranes: current status and prospective, Sep. PuriI. Tech.,2001, 25, 39-55.
    |2| B. Nair, T. Yamaguchi, T. Okubo, H. Suematsu, K. Keizer, S.-I. Nakao, Sol-gel synthesis oI molecular sieving silica
    membranes, J. Membrane Sci.,1997, 135, 237-243.
    |3| R. Bredesen, K. Jordal, O. Bolland, High temperature membranes in power generation with CO
    2
    capture, Chem. Eng. Proc.,
    2004, 43, 1129-1158.
    -207-
    PA.3.4
    Oily wastewater treatment by means of y-alumina nanofiltration membrane
    Z. Sadeghian
    1
    , F. Zamani
    2
    , N. AshraIizadeh
    2
    1
    Gas Research Division, Research Institute of Petroleum Industrv (RIPI), Tehran, P.O. Box. 148573311
    2
    Chemical Engineering Department, Iran Universitv of Science & Technologv (IUST), Tehran, P.O. Box. 16765163
    sadeghianzripi.ir
    NanoIiltration (NF) has proven to be a very eIIective method Ior the removal oI a wide variety oI organic compounds Irom
    aqueous solution |1|. NF operations normally produce a higher water Ilux and can oIten operate at lower pressures, which
    reduce energy consumption |2|. OilIield wastewater known as produced water is generated in large quantities in onshore and
    oIIshore oil exploitation |3|. Wastewaters Irom oilIields produced during many stages oI crude oil production, recovery and
    transportation represent a major environmental and processing problem Ior the petroleum industry |4|.
    In the present work the nanoporous y-alumina membranes have prepared with an average pore size oI 2 nm (Fig.1). Oily
    wastewater treatment has been studied by the cross-Ilow nanoIiltration processes using above membranes. The eIIect oI
    operating parameters on treatment oI nanoIilotratioin process was studied. The inIluence oI parameters such as transmembrane
    pressure (TMP),cross Ilow velocity (CFV) and oil concentration in Ieed on the separation behaviors were investigated by the
    measurements oI permeate Ilux, total organic carbon (TOC) removal eIIiciency. The TOC removal eIIiciencies higher than
    90 were achieved under all experimental conditions.
    |1| P. Berg, G. Hagmeyer, R. Gimbel, Removal oI pesticides and other micropollutants by nanoIiltration, Desalination, 1997,
    113 (2/3), 205208.
    |2| R. Haddad, E. Ferjani, M.S. Roudesli, A. Deratani, Properties oI cellulose acetate nanoIiltration membranes. Application to
    brackish water desalination, Desalination 2004, 167, 403409.
    |3| K. Shams Ashaghi1, M. Ebrahimi and P. Czermak, Ceramic Ultra- and NanoIiltration Membranes Ior OilIield Produced
    Water Treatment: A Mini Review The Open Environmental Journal, 2007, 1, 1-8.
    PA.3.5
    Factorial experiment design applied to the properties of low-cost ceramic membranes
    S. Mestre
    1
    , E. Sanchez
    1
    , M. Lorente
    1
    , P. Gingter
    2
    1
    Instituto de Tecnologia Ceramica (ITC). Asociacion de Investigacion de las Industrias Ceramicas (AICE)-Universitat Jaume
    I. Avda. Jicent Sos Bavnat s/n 12006, Castellon. Spain.
    2
    Rheinisch-Westfaelische Technische Hochschule, Aachen Universitv. Templergraben 55, 52056 Aachen, Germanv.
    sergio.mestreitc.uji.es
    The relations between the properties oI ceramic membranes and the operational conditions during their synthesis were studied
    with a replicated Iactorial experimental design, and the results were analysed by the ANOVA technique. The membranes were
    obtained Irom mixtures oI kaolin and alumina, mixed by wet ball milling, shaped as disks by uniaxial dry pressing oI the
    powder and sintered in an electric kiln. The three Iactors studied were the ratio oI kaolin and alumina in the powder, the
    maximum temperature and the soaking time oI the sintering treatment.
    The crystalline phases present in the membranes were corundum, quartz and mullite, and cristobalite in some oI them. The
    most signiIicant eIIect Ior the amount oI corundum was the composition oI the starting mixture, but Ior the other three phases
    the most signiIicant eIIect was the maximum temperature oI the sintering treatment.
    -208-
    Fig.1. SEM picture oI nanoporous
    y-alumina membrane
    The main eIIects oI maximum temperature and composition oI the powder, and two interactions, soaking time with maximum
    temperature and composition with maximum temperature were the signiIicant eIIects Ior the water permeability oI the
    membrane.
    The parameters obtained by mercury porosimetry oI the membranes showed diIIerent relations with the Iactors. The main
    eIIects oI maximum temperature and soaking time, and also the interaction oI both Iactors, were signiIicant Ior the mean pore
    diameter (d
    50
    ). By contrast, Ior the total porosity, the composition and the maximum temperature, and the interaction oI both
    were the signiIicant eIIects.
    These results indicate the most signiIicant Iactors related to the operational conditions suitable Ior obtaining economic ceramic
    membranes with tailored porosity and water permeability.
    The Ministerio de Ciencia e Innovacion (project reI. CTQ2008-06750-C02-02/PPQ), is acknowledged Ior the Iinancial
    support.
    PA.3.6
    Sintered metallic membranes with gradual structure produced by powders
    sedimentation
    I. Vida-Simiti, N. Jumate, N. Sechel
    Technical Universitv of Cluf-Napoca, Bd. Muncii, no.103-105, Cluf Napoca, 400641, Romania
    Vida.Simitistm.utcluj.ro
    The possibility oI obtaining by sedimentation permeable sintered membranes Irom metallic powders is investigated. The
    technique consisting oI sedimentation oI powders in suspension may lead to the elaboration oI membranes with size pores
    gradient. Superalloy (NiCrSiB) powders with various particle sizes were used. The macro-porous structure substrates were
    obtained using the method oI spreading the powder (60-125 m) into the sintering die. The size oI the powder particles used
    Ior the sedimentation oI the active microIiltration layer was oI less than 30 m. The obtained samples were sintered in vacuum
    Iurnace (410
    -3
    torr) at diIIerent temperatures and durations.
    The method that was used to obtain thin porous layers with structural gradient was the deposition by sedimentation on
    previously sintered macro-porous substrates. The SEM images oI the porous structures provide data on the powder particles
    shape and oI the pores size on the width oI each layer (Figure 1). The particles size in the layer deposited by sedimentation
    increases Irom the surIace towards the macro-porous layer. The top part oI the deposited layer is constituted oI the smallest
    powder particles in the suspension, that had settled with the lowest rate (Figure 1 b, c).

    a. b. c.
    Figure 1. SEM images oI sintered porous structures.
    a cross-section, b, c top surIace layer.
    Figure 2. Integral and diIIerential pores
    size distribution.
    In Figure 2 one can notice the existence oI two types oI pores with diIIerent size, originating Irom the layer and substrate, the
    curve suggests a bimodal distribution. Most oI the pores are 16.3 m in size (in the substrate layer), and among the small
    pores, the majority are 6.0 m in size (in the layer deposited by sedimentation), according to the two peaks on the diIIerential
    curve.
    |1| R.W. Baker, Membrane Technology and Apllications, John Wiley&Sons Ltd., 2nd ed., 2006, 538 p.
    |2| K.S. Chou, K.B. Kao, C.D. Huang, C.Y. Chen, Coating and Characterization oI Titania Membrane on Porous Ceramic
    Supports, J. Porous Mater., 6, 1999, p. 217-225.
    |3| J. Simonet, G. Kapelski, D. Bouvard, A sedimentation Ior the Iabrication oI solide oxide Iuel cell cathodes graded
    composition, J. oI. the European Ceramic Society, 27 (2007), 3113-3116.
    |4| W. J. Tseng, C. H. Wu, Sedimentation, Rheology and Particle-Packing Structure oI Aqueous Al
    2
    O
    3
    suspension, Ceram.
    Int., 29, 2003, p. 821-828.
    -209-
    PA.3.7
    Development of low cost -Al
    2
    O
    3
    -clay composite ultrafiltration membrane for
    separation of bovine serum albumin (BSA)
    A. Majhi, P. Monash, G. Pugazhenthi
    Department of Chemical Engineering, - Indian Institute of Technologv Guwahati, - Guwahati - 781039, India.
    pugaliitg.ernet.in
    Majority oI the reported -Al
    2
    O
    3
    membranes were derived Irom the expensive aluminium alkoxide |1-3|. UnIortunately, these
    membranes are too expensive to consider economic applications in industry. So, researchers are now being Iocused to search
    Ior alternative membrane materials that can reduce the synthesis cost oI the membrane. The extensive literature review reveals
    that the use oI natural clay materials Ior Iabrication oI the membrane support to reduce the overall cost oI the synthesis is now
    oI growing interest. Our main aim is to prepare a low cost -Al
    2
    O
    3
    composite membrane on a microporous clay support
    synthesized using locally available cheaper natural clay materials by dip-coating method. To synthesis -Al
    2
    O
    3
    top layer on the
    support, a stable boehmite sol is prepared using inexpensive aluminium chloride salt as a starting material instead oI expensive
    aluminium alkoxides by sol-gel route. The structural properties oI the composite membrane as well as -Al
    2
    O
    3
    powder is
    carried out using scanning electron microscopy (SEM), X-ray diIIraction (XRD), Fourier transIorm inIrared analysis (FT-IR)
    and dynamic light scattering (DLS) analysis. The mean particle size oI the boehmite sol used Ior coating is Iound to be 30.9
    nm. The pore size distribution oI the -Al
    2
    O
    3
    -clay composite membrane is Iound to be in the range oI 5.4-13.6 nm. Separation
    perIormance oI the membrane in terms oI Ilux and rejection oI BSA as a Iunction oI pH, initial Ieed concentration and applied
    pressure is also studied. With increase in applied pressure, rejection oI protein also increases and higher rejection oI BSA is
    observed at acidic pH. The rejection oI proteins increases with increase in Ieed concentration depending upon the adsorption
    characteristic oI the protein solution onto the membrane surIace. The maximum rejection oI BSA protein is Iound to be 95.
    These results indicate the possibility oI the preparation oI low cost clay composite membrane Ior separation oI BSA with
    higher yield.
    |1| X. Changrong, W. Feng, M. Zhaojing, L. Fanqing, P. Dingkun, M. Guangyao, Boehmite sol properties and preparation oI
    two-layer alumina membrane by a sol-gel process, J. Membr. Sci., 1996, 116 (1), 9-16.
    |2| J. Schaep, C. Vandecasteele, B. Peeters, J. Luyten, C. Dotremont, D. Roels, Characteristics and retention properties oI a
    mesoporous -Al
    2
    O
    3
    membrane Ior nanoIiltration, J. Membr. Sci., 1999, 163 (2), 229-237.
    |3| S. Alami-Younssi, A. Larbot, M. Persin, J. Sarrazin, L. Cot, Rejection oI mineral salts on a gamma alumina nanoIiltration
    membrane: Application to environmental process, J. Membr. Sci., 1995, 102, 123-129.
    PA.3.8
    Investigation of permeation properties during the cyclic CVD treatment of composite
    membranes with TEOS and TMOS in relation to the locality and morphology of
    silica deposition
    A.I. Labropoulos, G.E. Romanos, G. Karanikolos, G.I. Pilatos, N.K. Kanellopoulos
    NCSR 'Demokritos`, Institute of Phvsical Chemistrv, 153 10 Aghia Paraskevi Attikis, Greece
    kanelchem.demokritos.gr
    Commercial silica membranes oI 1 nm nominal pore size were post-treated by application oI a cyclic chemical vapor
    deposition (C-CVD) method at 573 K with the system TEOS/O
    3
    . Equal number oI cycles and identical conditions were applied
    Ior two oI the membranes to examine deposition reproducibility. A third membrane was modiIied under similar CVD
    conditions but Ior intermediate sorption/reaction periods and diIIerent number oI cycles with the intention to thoroughly study
    perIormance evolution during treatment. DiIIusion characteristics were attained aIter each cycle, by examining alterations oI
    He and N
    2
    'apparent (sorption contributed) activation energy. For the similarly modiIied membranes, He/N
    2
    permselectivity
    at 573 K reached its maximum value, Irom 10 to 107, aIter a total oI 3.5 hours exposure to organic precursor and oxidant. At
    this stage oI the procedure the 'apparent activation energy oI helium increased Irom 12 to 30 kJ/ mol, while its permeance
    dropped to 70 oI the initial value. On the other hand N
    2
    permeance values gave a negative slope in the Arrhenius plot,
    revealing that N
    2
    surIace Ilow contribution is still signiIicant. Further post-treatment, had no remarkable eIIect either on the
    activation energy or on the permeance oI Helium, whereas He/N
    2
    permselectivity decreased continuously with successive CVD
    cycles, reaching a limit value oI 32. This unexpected tendency was attributed to the observed transition oI Nitrogen transport
    -210-
    Irom sorption to micropore diIIusion dependent and was thoroughly explained considering the analysis oI adsorption potentials
    in microporous materials. The calculated 'apparent activation energies oI Nitrogen rose Irom 1.0 to 2.5 kJ/ mol Ior 4.5 to 8
    hours oI total treatment.
    Monitoring and controlling structure evolution oI nanoporous materials during their synthesis or modiIication can be achieved
    by innovative combinations oI in-situ and ex-situ techniques applied in consecutive or real-time modes. In the present study,
    tailoring oI the pore size oI silica membranes was achieved by applying combinations oI in-situ gas permeability with mercury
    porosimetry, SEM and EDAX, during the membrane modiIication using two CVD modes: in the normal cyclic mode, a
    sequential exposure to silica precursor vapors and O
    3
    was perIormed whereas in the pressure-pulsed mode, the exposure to
    silica precursor was accompanied by pressure pulses oI the order oI 400 kPa. The membranes were treated with tetramethyl
    orthosilicate (TMOS) in both modes under diIIerent CVD durations. The aim was to examine eIIects in the pore narrowing
    rate, deposition proIiles and membrane perIormance characteristics that are induced due to the diIIerent physicochemical
    properties oI the involved precursors, as well as due to the diIIerent CVD conditions. A common observation Ior all cases
    studied was that the He/N
    2
    permselectivity at 573K, starting Irom 15, presents a maximum value oI about 100 when interpreted
    as a Iunction oI the organosilane exposure period and then drops upon Iurther treatment. The Iact that this maximum appeared
    at shorter exposure periods in the case oI the TMOS treated membranes and especially in the case oI the pressure pulsed mode
    reveals the increased degree oI penetration oI the smaller tetramethoxysilane molecule inside the surIace pores oI the
    separation layer, the Iaster rate oI its polymerization on the pore surIace and the higher eIIiciency oI the pressure-pulsed mode.
    Furthermore, EDAX analysis in conjunction with mercury intrusion was applied to determine the proIiles oI silica deposition
    and elucidate the origin oI the diIIerent pore blocking rates and corresponding membrane perIormance.
    PA.3.9
    Preparation and characterization of oriented zeolite MFI layers and membranes for
    separation of light hydrocarbons
    P. Hrabanek
    1
    , A. Zikanova
    1
    , J. Drahokoupil
    2
    , B. Bernauer
    3
    , V. Fila
    3
    , M. Kocirik
    1
    1
    J. Hevrovskv Institute of Phvsical Chemistrv of the ASCR, v.v.i., Dolefskova 2155/3, 18223 Prague 8, C:ech Republic
    2
    Institute of Phvsics of the ASCR, v.v.i., Na Slovance 2, 18221 Prague 8, C:ech Republic
    3
    Institute of Chemical Technologv Prague, Technicka 5, 16628 Prague 6 Defvice, C:ech Republic
    milan.kocirikjh-inst.cas.cz
    Oriented zeolite layers Iree oI intercrystal pores may oIIer advantages to optimize the permeation and separation eIIiciency oI
    composite membranes |1-2|. This is due to MFI zeolite crystals anisotropy, which exhibits higher Iluxes along crystallographic
    axis b as compared to other crystallographic directions. Thus, mastering the control oI crystal morphology and their orientation
    in a zeolitic layer opens a route to preparation oI membranes oI high throughput via optimum utilization oI straight channels in
    silicalite-1 phase. The present study is Iocused on the preparation oI b-oriented zeolite MFI layers using a simple direct in situ
    crystallization method. The optimized synthesis procedures were based on the modiIication oI synthesis procedure developed
    by Wang |3|. The synthesis experiments were perIormed on porous stainless steel supports (Trumem
    TM
    ), (i) uncoated or (ii)
    coated by Iine layers oI TiO
    2
    , TiO
    2
    /ZrO
    2
    or Al
    2
    O
    3
    /SiO
    2
    /TiO
    2
    . The nature oI coating showed a crucial impact on the degree oI
    the layer b-orientation. The highest degree oI preIerred b-orientation was achieved Ior uncoated stainless steel and that coated
    with Al
    2
    O
    3
    /SiO
    2
    /TiO
    2
    layer. The orientation and morphology oI synthesized silicalite-1 layers were characterized by electron
    microscopy techniques and XRD. A criterion oI silicalite-1 layer b-orientation was introduced based on speciIic intensities oI
    layer XRD peaks. The synthesis procedures were optimized and separation eIIiciency oI composite zeolite membranes was
    tested using model mixture oI butane isomers.
    The Iinancial support by the Czech Science Foundation via grant No. 203/07/1443 and the Grant Agency oI ASCR via grant
    KAN 400720701 is grateIully acknowledged.
    |1| Z. Lai, G. Bonilla, I. Diaz, J.G. Nery, K. Sujaoti, M.A. Amat, E. Kokkoli, O. Terasaki, R.W. Thompson, M. Tsapatsis, D.G.
    Vlachos, Microstructural optimization oI a zeolite membrane Ior organic vapor separation, Science, 2003, 100, 456-460.
    |2| F.Z. Zhang, M.Fuji, M. Takahashi, In situ growth oI continuous b-oriented MFI zeolite membranes on porous u-alumina
    substrates precoated with a mesoporous silica sublayer, Chem. Mater., 2005, 17, 1167-1173.
    |3| Z. Wang, Y. Yan, Oriented zeolite MFI monolayer Iilms on metal substrates by in situ crystallization, Micropor. Mesopor.
    Mat., 2001, 48, 229-238.
    -211-
    PA.3.10
    Low temperature template removal from silicalite-1 membranes, films and round
    boat shaped crystals
    I. Jirka
    1
    , P. Hrabanek
    1
    , A. Zikanova
    1
    , L. Brabec
    1
    , V. Fila
    2
    , M. Kocirik
    1
    1
    J. Hevrovskv Institute of Phvsical Chemistrv of the ASCR, v.v.i., Dolefskova 2155/3, 18223 Prague 8, C:ech Republic
    2
    Institute of Chemical Technologv Prague, Technicka 5, 16628 Prague 6 Defvice, C:ech Republic
    milan.kocirikjh-inst.cas.cz
    Our previous study oI template removal Irom large silicalite-1 crystals suggested a transIormation oI TPA

    to mobile species
    deep below 300C |1, 2|. The present study meets general requirements on decreasing calcination temperature oI membranes.
    It involves pyrolytic and oxidative treatment oI the silicalite-1-u-alumina membranes, b-oriented silicalite-1 Iilms and round
    boat shaped crystals between 220 and 450C. Zeolitic phase was studied by elemental analysis, XPS and UV vis spectroscopy.
    The membranes were also tested by permeation oI gases (N
    2
    and N
    2
    CH
    4
    under counter-diIIusion conditions). Pressure
    responses oI Wicke-Kallenbach cell to stepwise composition oI Ieed gas exhibited considerable broadening which could not be
    described by the model based on parallel transport resistances oI zeolitic phase and intercrystalline deIects |3|. This can be
    explained by carbonaceous species deposited in the interIacial crystal region which block the layer deIects but also plug the
    zeolite channel entrances and thus introduce additional mass transport resistance. The mechanism oI TPA

    degradation in the
    interIacial crystal region was studied on layers oI round boat-shaped silicalite-1 crystals. Much greater extent oI TPA

    degradation was observed in the temperature region 250C-330C Ior oxidatively activated sample in comparison with
    pyrolytically activated one. This enhancement was caused by appearance oI the both, HoImann elimination reaction oI TPA

    and subsequent -elimination reactions in the oxidatively activated samples. The latter elimination reactions were absent in
    pyrolytically activated ones.
    The Iinancial support by the Grant Agency oI the ASCR via grants No. IAA400400625 and No. IAA400400909 is grateIully
    acknowledged.
    |1| O. Pachtova, M. Kocirik, A. Zikanova, B. Bernauer, S. Miachon, J.A. Dalmon, A comparative study oI template removal
    Irom silicalite-1 crystals in pyrolytic and oxidizing regimes, Micropor. Mesopor. Mater., 2002, 55, 285-296.
    |2| I. Jirka, O. Pachtova, P. Novak, M. Kocirik, On the removal oI template Irom silicalite-1 90 degrees intergrowths. A study
    by X-ray photoelectron spectroscopy, Langmuir, 2002, 18, 1702-1706.
    |3| V. Fila, P. Hrabanek, M. Kocirik, V. Navara, B. Bernauer, A. Zikanova, I. Jirka, Mathematical modelling oI
    multicomponent transport in composite all-ceramic membranes containing a zeolitic phase, Stud. SurI. Sci. Catal., 2008, 174,
    737-740.
    PA.3.11
    Magnetron sputtering deposition and characterization of Pd and Pd-Cu composite
    membranes for hydrogen separation
    E. Fernandez-Gesalaga
    1
    , P. Corengia
    1
    , S. Miguel
    1
    , M. Etxeberria
    1
    , M. Brizuela
    1
    , J. Calvio
    2

    1
    INASMET-Tecnalia, Paseo de Mikeletegi 2, E-20009 San Sebastian, Spain
    2
    Guascor, Parque Tecnologico de Alava, 01510 Miano, Spain
    ekain.Iernandezinasmet.es
    Due to the increasing demand Ior H
    2
    as an energy carrier in Iuel cells and internal combustion engines, eIIicient and
    economical methods Ior high-purity H
    2
    production are being assessed. Currently, the most eIIective ways to produce high
    purity gas are based in the use oI hydrogen-selective membranes; notably palladium membranes, which have gained an
    increasingly interest due to their excellent hydrogen permselectivity.
    However, pure Pd membranes suIIer Irom embrittlement, and poisoning by H
    2
    S. Several studies have been addressed to solve
    these limitations by alloying the Pd membrane mainly with Cu or Ag.
    A variety oI techniques to manuIacture Pd and Pd-Cu selective layers are being used, such as, electroless plating, chemical
    vapour deposition, sputtering, etc. Nowadays, the most common used technique is electroless plating. However, Iilm
    deposition by this method presents many problems, such as control oI thickness and chemical composition, purity oI the
    deposits, and the possibility oI decomposition in the bath, which may induce costly losses oI palladium. On the other hand,
    -212-
    Physical Vapour Deposition (PVD) is less laborious, provides Ior Iaster deposition rates and allows better control oI the Iilm
    thickness (Irom the nano to micro range), and also is an eco-Iriendly dry process.
    In this work, composite Pd and Pd-Cu membranes were deposited by PVD-magnetron sputtering on the outside oI
    commercially available tubular porous austenitic stainless steels supports. The composite Pd and Pd-Cu membranes were
    produced by d.c. magnetron sputtering Irom Pd and Cu targets in an Ar atmosphere. Targets power and deposition time were
    varied in order to get the desire composition and thickness (10 to 30 m).
    Prior to the deposition oI Pd and Pd-Cu Iilms, a study oI diIIusion barrier Iilms was carried out in order to prevent intermetallic
    diIIusion between the stainless steel support and the Pd or Pd-Cu Iilm. The manuIactured membranes have been characterized
    by optical microscopy (OM), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and X-
    Ray diIIraction (XRD) beIore and aIter permeation tests. In addition, the adhesion oI the Pd-based Iilm onto the metallic
    support was evaluated.
    Gas separation and permeation properties Ior pure N
    2
    , CO
    2
    , H
    2
    gases through the Pd-based membranes have been investigated
    in detail as a Iunction oI diIIerential pressure Ieed-permeate (100 to 500 KPa), time exposure (up to 100 h), and temperature
    (300 to 600C) using helium as sweep gas.
    Finally, the results oI permeability and selectivity oI N
    2
    , CO
    2
    , H
    2
    on Pd-based membranes have been discussed, analyzed, and
    compared with the DOE hydrogen perIormance target goals Ior the pure hydrogen and perIormance results obtained using
    conventional wet chemical methods (electroless plating).
    PA.3.12
    Influence of support characteristics on gas permeation of Pd composite membranes
    P. Pinacci, M. Broglia
    CESI RICERCA, Jia Rubattino 54, 2013,4 Milano, Italv
    pietro.pinaccicesiricerca.it
    Palladium alloy membranes are widely studied Ior CO
    2
    capture and hydrogen separation Irom synthesis gas in membrane
    reactors. Due to the considerable cost oI palladium, eIIorts have been made to obtain low thickness deposits on cheaper
    materials, such as macro-porous metals, by various techniques, including electroless plating |1|. However, high operating
    temperatures (~350-400C) and long exposure times can determine the diIIusion oI substrate metals (e.g. iron) into the
    palladium layer and, subsequently, a signiIicant decrease oI hydrogen permeance and selectivity. To avoid this problem, the
    support should be modiIied, introducing a suitable barrier layer such as a grown-on oxide obtained by a proper thermal
    treatment. The characteristics oI the modiIied support, including pore size distribution and surIace rugosity, strongly aIIect the
    thickness oI the palladium layer that should be deposited in order to obtain a dense and stable membrane |2|.
    The objective oI this work is, thereIore, to optimize the surIace characteristics oI commercial metallic supports in order to
    minimize the thickness oI the deposited palladium layer.
    Investigated supports are tubular AISI 316L supports, with a nominal pore size oI 0.1 micron, supplied by two diIIerent
    manuIacturers. Supports have been machine polished with a diamond paste in order to reduce surIace rugosity. Supports have
    been then oxidized by a proper thermal treatment and, thereaIter, palladium has been deposited by electroless plating in
    successive baths. At the end oI each bath, the helium permeance oI the membranes at room temperature has been determined.
    Membranes have been considered as dense and, consequently, palladium deposition stopped, when helium permeance has been
    reduced below 10
    -9
    mol/sec/m
    2
    /Pa. Finally membrane permeation tests in single gases (He and H
    2
    ) have been perIormed in the
    300-450C temperature range, in order to check their perIormances (permeance and selectivity) and stability.
    Experimental allowed to optimize the preparation procedure oI the membrane. The surIace rugosity oI the support was
    decreased oI a Iactor up to six without signiIicantly aIIecting its mass transIer resistance and, at the same time, the Pd layer
    thickness has been reduced more than a Iactor 2 (Irom 25 down to 11 microns) while maintaining good stability and
    perIormances at temperature,
    |1| S.K. Gade, M. K. Keeling, D.K. Steele, J. D.. Way P.M. Thoen, High Ilux Pd membranes deposited on stainless steel by
    electroless plating, Proc. oI ICIM 9, Lillehammer (No), June 25-29, 2006
    |2| Y.H. Ma, Pd-Based Hydrogen Separation Membranes Status and Prospective, Proc. oI ICIM 9, Lillehammer (No), June
    25-29, 2006
    This work has been Iinanced by the Research Fund Ior the Italian Electrical System under the Contract Agreement between
    CESI RICERCA and the Ministry oI Economic Development General Directorate Ior Energy and Mining Resources
    stipulated on June 21, 2007 in compliance with the Decree n. 73 oI June 18, 2007.
    -213-
    PA.3.13
    Application of MFI/TiO
    2
    and GIS/TiO
    2
    membranes in pervaporation
    K. Czechowska
    Institute of Glass, Ceramics, Refractorv and Construction Material- Refractorv Materials Branch/
    ul. Tos:ecka 99, 44-100 Gliwice, Poland
    kingaimo.gliwice.pl
    Inorganic zeolite membranes, having the equal, molecular size oI pores, in most cases are chemically stable over wide range oI
    pH. These advantages make possible the application oI zeolite membranes in alternative techniques oI mixture separation
    especially, when conventional methods oI separation are not aIIective.
    Zeolite membranes may be also used Ior separation oI liquid mixtures in pervaporation process e.g Ior azeotropes, components
    oI similar boiling point or sensitive on (elevated) temperature impact.
    In the present work the preparation procedure oI the zeolite layers oI the MFI type and GIS on commercial, tubular TiO
    2
    support (used in milk industry) was presented. The results oI application tests Ior prepared membranes used Ior separation oI
    water-isopropanol mixtures were also given.
    Zeolite layers type MFI were prepared by deposition oI zeolite seeds Irom water suspensions and subsequent hydrothermal
    treatment leading to zeolite layers crystallization-,,seeding and crystallization growth method.
    Zeolite layers type GIS were prepared Irom synthesis solution ,,in situ method. Receptions oI these layers composition were
    borrowed Irom dates published in papers by Y.S. Lin & co |1,2|
    MFI samples Ior separation tests were prepared using 0,5 i 1h oI deposition time Ior suspension with pH ab. 3 and ab. 10
    respectively. The crystallization process oI the deposited zeolite layers was carried out Ior 4h in 180
    0
    C and 160
    0
    C, and Ior 6h
    in 180
    0
    C. The crystallization GIS sample Irom solution was carried Ior ab 12h in 100
    o
    C, twice.
    The best results oI separation tests were obtained Ior the MFI membrane deposited Ior 1h using water suspension with pH ab.
    10, where crystallization conditions were 160
    0
    C and 4h. For the Ieed containing ab. 7wt oI water and ab. 93wt. oI
    isopropanol the average content oI water and isopropanol in obtained permeate were 97,7wt and 2,3wt. respectively. The
    calculated average permeate Ilux were ab. 0,2 kg/m
    2
    h.
    In the case membrane type GIS, Ior Ieed containing ab.5wt. oI water and ab.95wt. oI isopropanol, the average content oI
    water and isopropanol in obtained permeate were 20,1wt. and 79,9wt. respectively. The calculated average permeate Ilux
    were ab. 1,6kg/m
    2
    h.
    The obtained results were related to the composition and microstructure oI zeolite layers.
    |1|.M. Pan, Y.S. Lin, Template Iree secondary growth synthesis oI MFI type zeolite membranes, Microporous and
    Mesoporous Materials, 2001, 43, 319-327.
    |2|. Junhang Dong, Y. S. Lin, In-situ Synthesis oI P-Type Zeolite Membranes on Porous u-Alumina Supports, Ind. Eng.
    Chem. Res., 1998, 37, 2404-2409.
    PA.3.14
    Nanocomposite MFI-alumina hollow-fibre membranes: application to selective
    separation of xylene isomeric mixtures
    Z. Deng
    1,2
    , M. Pera-Titus
    2
    , A. Giroir-Fendler
    2
    , Y. Guo
    1
    1
    Laboratorv for Advanced Materials, Research Institute of Industrial Catalvsis, East China Universitv of Science and
    Technologv, 200237 Shanghai, China
    2
    Universite de Lvon, IRCELvon, UMR 5256 CNRS - Universite Lvon 1, 2, Av. A. Einstein, F-69626 Jilleurbanne cedex,
    France
    anne.giroir-Iendlerircelyon.univ-lyon1.Ir, ylguoecust.edu.cn
    Zeolite membranes have attracted great attention, especially MFI membranes. Until now most papers have Iocused on tubular
    or planar ceramic and stainless steel supports, with low surIace-to-volume ratios. How to achieve more compact systems?
    Ceramic hollow Iibres could be one alternative. Furthermore, compared to conventional Iilm-like membranes, nanocomposite
    architectures have some potential advantages, such as |1,2|: (1) the thermal expansion mismatch between support and zeolite
    have little or no eIIects, (2) the membrane can be scaled-up more easily, and (3) the zeolite material is protected against
    abrasion and shocks, Iacilitating membrane handling and module assembling. Our group has reported recently on the
    -214-
    application oI this concept in hollow Iibres Ior CO
    2
    separation |3|. This communication provides more details about the
    synthesis and characterization oI this kind oI materials thin and uniIorm nanocomposite MFI-ceramic hollow Iibres membrane
    (see Figure 1). The inIluence oI support quality and pretreatment have been studied. The Iibres here prepared have been
    explored Ior xylene isomer mixture separation as an alternative processes to classical Iractional distillation, crystallization and
    adsorption/desorption techniques. This kind oI material appears also promising Ior catalytic membrane reactor applications Ior
    isomerization reactions.
    Zhiyong Deng greatly acknowledges the China Scholarship Council (CSC) Ior Iinancial support to pursue his studies in France
    as a joint Ph.D. student.
    |1| S. Miachon, I. Kumakiri, P. Ciavarella, L. van Dyk, K. Fiaty, Y.Schuurman, J.-A. Dalmon, Nanocomposite MFI-alumina
    membranes via pore-plugging synthesis: SpeciIic transport and separation properties, J. Membr. Sci. 298 (2007) 71-79.
    |2| S. Miachon, E. Landrivon, M. Aouine, Y. Sun, I. Kumakiri, Y. Li, O. Pachtova Prokopova, N. Guilhaume, A. Giroir-
    Fendler, H. Mozzanega, J.-A. Dalmon, Nanocomposite MFI-alumina membranes via pore-plugging synthesis. Preparation and
    morphological characterisation, J. Membr. Sci. 281 (2006) 228-238.
    |3| A. Alshebani, M. Pera-Titus, E. Landrivon, Th. Schiestel, S. Miachon1, J.-A. Dalmon, Nanocomposite MFI ceramic
    hollow Iibres: prospects Ior CO2 separation, Micropor. Mesopor. Mater. 115 (2008) 197205.
    PA.3.15
    Effect of mid synthesis addition of silica to the synthesis medium on the properties of
    MFI type zeolite membranes
    B. Soydas, A. ulIaz, H. Kalipilar
    Department of Chemical Engineering, Middle East Technical Universitv, 06531, Ankara, Turkev
    soydasmetu.edu.tr
    Zeolite membranes are attractive materials to separate gas and liquid mixtures |1|. MFI is a widely studied zeolite type due to
    its ease oI preparation and comparable pore size with many substances |2|. MFI type membranes are typically synthesized in
    batch systems in autoclaves Irom hydrogels or clear solutions. The synthesis conditions such as synthesis temperature and
    solution composition inIluence the permeation and separation properties oI the membranes. The overall composition oI the
    synthesis medium is kept constant during the crystallization oI membranes in autoclaves. However, it would be possible to
    aIIect the rates oI nucleation and crystal growth to obtain better quality membranes by changing the overall composition oI the
    medium during the membrane synthesis.
    In this study the composition oI the synthesis solution was changed by adding silica to the synthesis solution during the course
    oI crystallization. The silica/TPAOH ratio inIluences the rate oI crystallization, average crystal size, and consequently the
    thickness oI the membranes |3|. The membranes were synthesized in a recirculating Ilow system operating at atmospheric
    pressure |4|. This system allows the addition oI chemicals to change the composition oI synthesis solution without
    interrupting the crystallization. The synthesis began in a clear solution with a molar composition oI 80SiO
    2
    :30TPAOH:
    1536H
    2
    O. AIter 24 h (membrane M1), 48 h (membrane M2), and 72 h (membrane M3) the overall composition oI the
    synthesis solution in the container was changed to 80SiO
    2
    :9TPAOH:1536H
    2
    O and the crystallization was continued Ior an
    additional 72 h. All syntheses were perIormed on u-Al
    2
    O
    3
    discs (Inocermic) in the Ilow system at 95C. The Ilow rate oI the
    synthesis solution was 6 ml/min.
    The XRD patterns oI the membanes showed that all membranes are composed oI MFI type zeolite crystals. The thicknesses oI
    the membranes were about 1.5-2 m. The sizes oI the crystals Iorming the membranes M1, M2 and M3 are 0.41 m, 0.22 m,
    and 0.38 m, respectively. The change oI composition during the synthesis aIIects the growth rate and size oI the crystals. The
    -215-
    Figure 1. hollow Iibres mounted into their
    mechanical support tube
    n-C
    4
    H
    10
    permeances oI M1 and M2 at 25C are 7.2x10
    -9
    and 1.5x10
    -7
    mol/m
    2
    sPa, respectively. The n-C
    4
    H
    10
    /CH
    4
    and n-C
    4
    H
    10
    /
    N
    2
    separation selectivities oI M1 membrane are 41 and 27 at 25C, respectively. On the other hand the n-C
    4
    H
    10
    /CH
    4
    separation
    selectivities oI M2 and M3 membranes are nearly 2.4 and 1.0, respectively. These results indicate that changing the
    composition at early stages improves the membrane selectivity at the expense oI reduced permeance.
    |1| J. Caro, M. Noack, P. Klsch, R. SchIer, Zeolite membranes-state oI their development and perspective, Micropor.
    Mesopor. Mater., 2000, 38, 3-24.
    |2| H.H. Funke, M.G. Kovalchick, J.L. Falconer, and R.D. Noble, Separation oI hydrocarbon isomer vapors with silicalite
    zeolite membranes, Ind. Eng. Chem.Res., 1996, 35, 1575-1582.
    |3| Z. Wang, and Y. Yan, Controlling crystal orientation in zeolite MFI thin Iilms by direst in situ crystallization, Chem.
    Mater., 2001, 13 , 1101-1107.
    |4| P. Z. ulIaz, A. ulIaz, and H. Kalipilar, Preparation oI MFI type zeolite membranes in a Ilow system with circulation oI
    the synthesis solution, Micropor. Mesopor. Mater., 2006, 92, 134-144.
    PA.3.16
    Study of preparation of Pd based membranes by electroless plating over
    PSS supports
    J.A. Calles, R. Sanz, D. Alique
    Department of Chemical and Environmental Technologv, Universidad Rev Juan Carlos, C/Tulipan s/n, 28933 Mostoles,
    Madrid, Spain
    david.aliqueurjc.es
    Nowadays, the global warming due to the massive CO
    2
    emmisions is a very important problem Ior the Iuture oI our planet and
    many eIIorts are being driving to use hydrogen as clean energy vector |1|. In this way, one important target is the design oI an
    eIIective membrane reactor Ior simultaneous H
    2
    synthesis and puriIication. Despite the huge research activity in this Iield, the
    optimization oI materials and preparation methods oI Pd and Pd alloys membranes, which are extremly selective to H
    2
    |2|, is
    still an open issue.
    This work have been Iocused on the study oI metal electroless plating Ior achieving a thin membrane over porous stainless
    steel supports (purchased Irom Mott Metallurgical with a porosity oI ca. 20 and
    media grade oI 0.2 m). These supports have been initially cleaned by sequential
    washing with HCl, NaOH and ethanol solutions under ultrasonic irradiation at 333
    K. The activation oI the external surIace has been carried out by successive
    immersions in acidic Sn and Pd solutions Iollowed by washing with distillated
    water. Metal deposition over the activated supports has been carried out by
    electroless plating (ELP) with hydrazine as reducing agent |3|. The conditions oI
    these processes, such number oI cycles in activation, Pd nuclei generation without
    Sn compounds, ELP bath composition, concentration and dosage oI reducing
    agent, time and temperature oI plating stage were optimized. The inIluence oI all
    these parameters was analyzed by SEM, EDX, DRX, ICP-AES and gravimetric
    analysis.
    Table 1 shows the surIace composition oI activated supports aIter consecutive Sn-
    Pd immersions in the activation bath. As it can be seen, the loading oI Pd nuclei
    over the surIace increases with the number oI cycles carried out, while the Sn
    content decreases. Six cycles have been chosen as the optimal value to obtain an
    uniIorm Pd plating and absence oI Sn over the surIace.
    Related to the optimization oI ELP stage, Figure 1 shows the inIluence oI the procedure in the hydrazine addition to the ELP
    bath. Thus, in all experiments, a total amount oI hydrazine was kept constant but measuring out in several doses. As can be
    seen in the Iigure, the quality oI the plating is clearly inIluenced by this parameter. When hydrazine was added in several
    times, the Pd grain size decreased and the Pd coating become more compact. ThereIore, six doses have been selected Ior the
    reducing agent addition.
    The authors acknowledge Iinancial support received Irom the Ministry oI Education and Science oI Spain through projects
    ENE2004-07758-C02-02, and ENE2007-66958.
    |1| Marban G., Valdes-Solis T.; Int. J. Hvdrog. Energv 32, (2007), 1625-1637.
    |2| Pagliari S. N., Way J. D.; Sep. and Pur. Methods 31 (1), (2002), 1-169
    -216-
    |3| Rothenberger K.S., Cugini A.V., Howard B.H., Killmeyer R.P., Ciocco M.V., Morreale B.D., Enick R.M., Bustamante F.,
    Mardilovich I.P., Ma Y.H.; J. Membr. Sci. 244, (2004), 55-68.
    PA.3.17
    Electrophoretic deposition (EPD) of small zeolite crystals as a membrane base
    L. Brabec, P. Hrabanek, M. Kocirik
    J. Hevrovskv Institute of Phvsical Chemistrv of the ASCR, v.v.i., Dolefskova 2155/3, 18223 Prague 8, C:ech Republic
    libor.brabecjh-inst.cas.cz
    In order to build a uniIorm layer oI zeolite seeds on stainless steel supports Ior subsequent synthesis oI zeolitic
    membranes/Iilms, EPD experiments were perIormed with small silicalite-1 crystals oI two diIIerent types and also with small
    ZSM-5 and NH
    4
    Y crystals. Because the present EPD techniques are rather oI an empirical character, two key questions must
    be solved: (i) an optimal EPD cell geometry and (ii) an optimal dispersion medium Ior crystals to ensure their migration in the
    electric Iield and their steady deposition on the desired membrane support. These optimization steps were perIormed with
    silicalite-1 crystals-twins oI spheric shape and ca 1 m in size produced by Zeolyst (USA). The Iirst EPD cell was a glass
    cylinder with vertical parallel Pt sheets as electrodes inside. In this arrangement an electrosettling process interIered with EPD.
    ThereIore a glass cell was constructed with horizontal electrodes. The top electrode was chosen as anode because the crystals
    are mostly negatively charged against the liquid phase |1-2|. Thus, the crystals were attracted upward to the anode which
    enabled a better control oI the layer deposition than in the case oI the opposite polarity. Prior to EPD the crystals were
    dispersed by ultrasound in an appropriate liquid phase. The Iollowing organic solvents were used as dispersion medium:
    ethanol 96 or 100, acetone, i-propanol, tetraethoxysilane and mixtures oI them. Organic liquids were preIerred to water
    because oI a higher electric Iield strength between electrodes and lower extend oI electrochemical reactions. To obtain a well-
    adhered crystal layer, parameters as crystal concentration, ageing oI the system, viscosity, electrical conductivity, permitivity
    and electric Iield strength were taken into account. Finally a slow drying process is important not to damage the obtained layer.
    AIter Iinding proper EPD conditions Ior spheric crystals, small tabular round-shaped monocrystals 1 m in length were used to
    study a possibility oI their deposition on a polished support exclusively in b-orientation. A monolayer oI these tabular crystals
    were used as a seed base Ior consequent synthesizing a complete b-oriented zeolitic membrane.
    The Iinancial support by the Czech Science Foundation via grant No. 203/07/1443 and the Grant Agency oI ASCR via grant
    KAN 400720701 is grateIully acknowledged.
    |1| H. Negishi, T. Imura, D. Kitamoto, T. Ikegami, H. Yanagashita, M. Okamoto, Y. Idemoto, N. Koura, T. Sano, Preparation
    oI tubular silicalite membranes by hydrothermal synthesis with EPD as a seeding technique, J. Am. Ceram. Soc., 2006,
    89, 124-130.
    |2| W. Shan, Y. Zhang, W. Yang, C. Ke, Z. Gao, Y. Ye, Y. Tang, EPD oI nanosized zeolites in non-aqueous medium and its
    application in Iabricating thin zeolite membranes, Micropor. Mesopor. Mater., 2004, 69, 35-42.
    PA.3.18
    New ceramic ultrafiltration membrane for tangential filtration deposited on
    macroporous support from Moroccan apatite
    I. Barrouk
    1
    , S.A. Younssi
    1
    , M. Persin
    3
    , A. Larbot
    3
    , A. Kabbabi
    2
    , J. Maghnouj
    3

    1
    Laboratoire des Materiaux, Catalvse et Environnement, Faculte des Sciences et Techniques, Universite Hassan II. B.P 146.
    Avenue Hassan II, C.P.20 650, Mohammedia, Maroc.
    2
    Centre dEtude et de Recherche des Phosphates Mineraux (CERPHOS), 73 Boulevard Moulav-Ismail. Casablanca, Maroc.
    3
    lnstitut Europeen des Membranes, 1919 Route de Mende, 34293 Montpellier, Cedex 5, France
    michel.persinuniv-montp2.Ir
    This study is devoted to the development oI ceramic membrane with a tubular conIiguration. The preparation and
    characterization oI microIiltration and ultraIiltration layers are described in this work.
    Porous tubular supports and microIiltration membranes were prepared with lixiviated phosphate obtained Irom moroccan
    natural phosphate. UltraIiltration membranes were elaborated with potassium titanyl phosphate KTiOPO4 prepared by sol-gel
    -217-
    process. MicroIiltration and ultraIiltration layers were obtained by slip casting and the conditions oI their preparation were
    optimized (temperature oI sintering, time Ior casting, percentage oI mineral and additives).
    The support Iired at 1000 C showed an average pore diameters measured by mercury porosimetry centred near 10 m and a
    porosity oI about 43 . Water permeability measured Ior microIiltration membrane with pore diameter oI 0.35 m and a
    thickness oI 10 m is 800 l.h
    -1
    m
    -2
    bar
    -1
    and 80 l.h
    -1
    m
    -2
    bar
    -1
    Ior ultraIiltration membrane with pore diameter 10 nm and a
    thickness oI 0.7 m. The perIormances oI these UF membranes were tested Ior the Iiltration oI industrials wastewater, good
    retention are obtained Ior salts and alumina hydroxides suspensions.
    PA.3.19
    Al
    2
    O
    3
    coatings on stainless steel porous supports as intermetallic diffusion
    barrier for H
    2
    separative membranes
    A. Bottino
    1
    , M. Broglia
    2
    , G. Capannelli
    1
    , A. Comite
    1
    , P. Pinacci
    2
    1
    Department of Chemistrv and Industrial Chemistrv, Universitv of Genoa, Jia Dodecaneso 31, 16146 Genoa, Italv
    2
    CESIRICERCA S.p.A., Jia Rubattino 54, 20152 Milan, Italv
    a.comitechimica.unige.it
    Palladium and some oI its alloys (e.g. Pd/Cu, Pd/Ag) are suitable materials Ior the preparation oI H
    2
    separation membranes due
    to their high H
    2
    solubility, permeability and selectivity. The synthesis oI thin, deIect Iree, stable and with suIIicient liIetime Pd-
    based membranes is still a challenging task. Thin layers oI Pd having a thickness below 20 m can be grown on a porous
    support using diIIerent techniques (e.g. electrochemical or electroless deposition). Ceramic supports are commercially
    available in a variety oI materials, pore structure and quality but unIortunately the assembly oI the Pd-based ceramic
    membranes into modules is still a not solved problem due to their brittle nature and to the signiIicant leakages Irom the seals,
    which lower the H
    2
    separation selectivity. ThereIore a large attention is also devoted to porous metal supports (e.g. sintered
    porous stainless steel) which can be easily assembled into modules by welding. Although Pd-based layers can be grown
    directly on porous stainless steel (PSS) supports, at the high working temperatures the migration oI elements Irom the support
    to the Pd-based layer (known as intermetallic diIIusion) can take place decreasing H
    2
    permeability and membrane liIetime |1|.
    Moreover commercial PSS supports have still large nominal pore size and a high average rugosity which does not consent to
    deposit very thin (less than 10 m) and deIect-Iree Pd-based layers. The deposition oI a non-metallic barrier between the
    support and the Pd layer would prevent the intermetallic diIIusion phenomena and improve the support characteristics |2|.
    In this work the deposition oI Al
    2
    O
    3
    coatings on PSS supports was carried out using the sol gel technique. The PSS supports
    were used as received Irom the manuIacturer and aIter a mechanical treatment to reduce their average rugosity. PSS supports
    were dip-coated using boehmite sols containing organic additives (namely polyvinyl alcohol and glycerin). The composition
    and viscosity oI the sols were investigated in order to obtain homogeneous and deIect-Iree Al
    2
    O
    3
    layers. A Iurther coating oI
    Pd/Al
    2
    O
    3
    was deposited on the Al
    2
    O
    3
    coated PSS supports to create an activated layer where to grow the Pd layer through the
    electroless plating technique. The morphology and thickness oI the deposited layers was investigated by SEM and the gas
    permeance at various stages oI membrane synthesis was measured at both room (using He and N
    2
    ) and high temperature (with
    He and H
    2
    ).
    |1| M. E. Ayturk, E. E. Engwall, Y. H. Ma, Microstructure Analysis oI the intermetallic diIIusion-induced alloy phases in
    composite Pd/Ag/porous stainless steel membranes, Ind. Eng. Chem. Res. 2007, 46, 4295-4306
    |2| Y. Huang, R. Dittmeyer, Preparation and characterization oI composite palladium membranes on sinter-metal supports with
    a ceramic barrier against intermetallic diIIusion, J. Membr. Sci., 2006, 282, 296310
    -218-
    PA.3.20
    Elaboration of supports for membranes filtration from kaolin and limestone
    A. Guechi
    1,2
    , A. Harabi
    2
    , S. Condom
    3
    1
    Phvsics Department, Mhamed Bougara Universitv, 35000 Boumerdes, Algeria.
    2
    Ceramics Lab., Phvsics Department, Mentouri Universitv, 25000 Constantine, Algeria.
    3
    Institut Europeen des Membranes (IEM), ENSCM, UM2, CRNS, 1919, route de Mende 34293 Montpellier Cedex 5, France.
    guechia yahoo.Ir
    Up to now, the production oI industrial membranes uses a limited choice oI materials. As a consequence, the price oI ceramic
    membranes is high and a signiIicant eIIort was provided in these last years in membrane technology Iield in order to Iind out
    new porous ceramic materials using clays and kaolin. These materials are in abundance and need sintering temperature lower
    than those oI metal oxide materials |1-3|.
    In this work, the support Ior membranes (MF and UF) was manuIactured Irom raw kaolin and lime extracted Irom limestone.
    The eIIect oI the relatively lower sintering temperature, ranging Irom 800 to 1100C, on the porosity, average pore size, pore
    size distribution and strength oI supports has been investigated. It has been Iound that the average pore size, measured by
    mercury porosimetry, was about 8 m while the pore volume was 47 Ior supports sintered at 1000C with a Ilexural strength
    oI about 30 MPa. Moreover, the X-Ray DiIIraction showed that the phase oI this support is anorthite (CaO.Al
    2
    O
    3
    .2SiO
    2
    ).
    |1| F. Bouzrara, A. Harabi, S. Achour, A. Larbot, Porous ceramic supports Ior membranes prepared Irom kaolin and doloma
    mixtures, J. Euro. Ceram. Soc.26 (2006) 1663-1671.
    |2| S. Khemakham, R. Ben Amar, A. Larbot, A. Ben Salah, L. Cot, Fabrication oI mineral supports oI membranes Ior
    microIiltration/ultraIiltration Irom Tunisian clay, Ann. Chim. Soc. Mater. 31(2) (2006) 169-181.
    |3| S. Masmoudi, A. Larbot, H. El Feki, R. Ben Amar, Elaboration and characterisation oI apatite based mineral supports Ior
    microIiltration and ultraIiltration membranes, Ceram. Int. 33 (2007) 337-344.
    PA.3.21
    Synthesis by conventional and microwave-assisted methods of
    Fe-MFI membranes for N
    2
    O decomposition
    J. Motuzas, A. Julbe
    Institut Europeen des Membranes, UMR 5635-CNRS-ENSCM-UM2, Universite Montpellier 2, CC 047 Place Eugene
    Bataillon 34095 Montpellier Cedex 5, France
    Julius.Motuzasiemm.univ-montp2.Ir
    DiIIerent nitrogen oxides are present in waste gases emitted by power stations and by industry. Nitrous oxide is a by-product in
    many industrial processes such as adipic acid and nitric acid production |1|. Considering its contribution in greenhouse eIIect
    and potentially in ozone layer depletion, the decomposition oI nitrous oxide (N
    2
    O) was extensively investigated. Cu-modiIied
    MFI zeolites have been largely studied as catalysts Ior nitrous and nitric oxides decomposition, but revealed very sensitive to
    steam and SO
    x
    . Iron modiIied MFI (Fe-ZSM-5) resulted in more resistant catalysts whose catalytic activity depends both on
    iron cations concentration (directly related to the Si/Al ratio in case oI ion exchange) and on the synthesis procedure.
    Various catalysts applied in packed bed reactors to 'capture or decompose NO
    x
    or N
    2
    O to O
    2
    and N
    2
    . Metal containing zeolite
    powders (e.g. MFI, BEA, FAU with Ni, Fe, Co, Rh) are still investigated in order to better understand the N
    2
    O decomposition
    mechanisms |2,3|. The interest oI membranes able to perIorm N
    2
    O decomposition continuously and on site is an attractive
    option which deserves consideration.
    In this work, Fe-S-1 and Fe-ZSM-5 membranes have been prepared by both MW-assisted and conventional methods, using a
    secondary growth strategy Irom S-1 seeds. Several characterization methods (FESEM, EDX, XRD, Raman and FT-IR
    spectroscopies) were used Ior analyzing the synthesized powders and membranes. The quality oI the membranes prepared by
    conventional and MW-assisted heating methods, and with various iron concentrations in the mother sol were compared on the
    basis oI single gas permeation tests at room temperature. Finally the catalytic activity oI the best membranes Ior N
    2
    O
    decomposition was studied up to 500C.
    |1| F. Kapteijn et al., Heterogeneous catalytic decomposition oI nitrous oxide, Appl. Catal. B: Environ. 9 (1996) 25
    |2| Kondratenko, E.V., et al., Mechanistic origin oI the diIIerent activity oI Rh-ZSM-5 and Fe-ZSM-5 in N2O decomposition.
    J. Catal. 256 (2) (2008) 248-258
    -219-
    |3| Pantu, P., et al., Nanocavity eIIects on N2O decomposition on diIIerent types oI Fe-zeolites (Fe-FER, Fe-BEA, Fe-ZSM-5
    and Fe-FAU): a combined theoretical and experimental study. Chemical Engin. Commun. 195 (11) (2008) 1477-1485
    PA.4.1
    Preparation of new composite membranes for proton transport based on inorganic
    anodisc and liquid-crystalline compounds
    B. Tylkowski
    1
    , N. Castelao
    1
    , B. Ferrer
    1
    , M. Pregowska
    2
    , R. Garcia-Valls
    1
    , T. Gumi
    1
    ,
    J.A. Reina
    2
    ,
    M. Giamberini
    1
    1
    Departament dEnginveria Quimica, Universitat Rovira i Jirgili, Av. Pasos Catalans, 26, 43007 Tarragona Spain.
    2
    Departament de Quimica Analitica i Quimica Organica, Universitat Rovira i Jirgili, Carrer Marceli Domingo s/n, 43007
    Tarragona Spain.
    marta.giamberiniurv.net
    In this paper we present preliminary results oI preparation oI new proton exchange composite membranes based on selI-
    assembling side-chain liquid-crystalline polymers which are able to Iorm biomimetic ion-channels. These proton exchange
    membranes are oI great interest Ior the construction oI methanol Iuel cells.
    In biological systems, transport mainly occurs by means oI three diIIerent mechanism: carriers, channels and doors. Among
    them, proteic channels are the most commonly used systems to transport ions through the membranes in the cells. However,
    although proteic channels are very eIIective in ion transport through a cell membrane, they are inadequate Ior technological
    applications, both because these proteins are too diIIicult to puriIy and because their structure is too complex to be chemically
    modiIied to get tailor-made systems.
    In this work the composite membranes were obtained by Iilling an anodic porous alumina disc with selI-assembling
    supramolecular columnar liquid crystalline structures. The cross-sections and the surIace morphologies oI the composite
    membranes were characterized by Environmental Scanning Electron Microscopy. The proton conductivity was measured by
    home-made cell connected with Ph-metry.
    PA.4.2
    Proton conductive membranes based on polyvinyl alcohol and polystyrenesulfonic
    acid
    I. Stadniy, V. Konovalova, A. Burban
    Membrane Research Centre, National Universitv of Kiev-Mohvla Academv, 2, Skovoroda str., Kiev, 04070, Ukraine
    vitaukma.kiev.ua
    Among various types oI developed and commercialized Iuel cells direct methanol cells stand out as a very simple and,
    thereIore, likely to be cheaply produced. They do not need neither the expensive storage systems associated with hydrogen Iuel
    cells, nor the complex reIormers oI indirect methanol Iuel cells. This theoretical beneIit is hampered by numerous practical
    drawbacks, Ior example high methanol permeability oI most commercially successIul proton-conducting membranes.
    An obvious way to decrease methanol permeability would be to use a mass-produced material, which has already proved to
    posses all the necessary properties, such as polyvinyl alcohol (PVA) a widely used polymer Ior pervaporation membranes in
    alcohol separation. Other beneIits oI PVA include low cost due to mass-production and ease oI modiIication due to numerous
    alcohol groups.
    PVA is nonproton-conducting polymer, thereIore an additional component would be necessary to build proton-conducting
    channels in membranes. PolystyrenesulIonic acid (PSSA) seems a reasonable choice oI proton-conducting polymer. The third
    component necessary to give membranes mechanical rigidity and prevent them Irom dissolving in water is gluteraldehyde
    (GA) a bi-Iunctional cross-linking agent.
    The inIluence oI concentrations oI these three components on Iinal membrane proton-conductivity, exchange capacity,
    methanol retention and thermal stability was investigated.
    We have shown, through thermogravimetric analysis, that these membranes retain their bound water up to the temperature oI
    80
    0
    C, i.e. they will be able to work under thermal conditions typical Ior DMFCs. As cross-linking density was increased (by
    increasing initial PVA and GA concentrations) membranes exhibit decreased swelling in water, restricted availability on
    -220-
    sulphuric acid Ior ion exchange and decreased exchange capacity. On the other hand membranes become less permeable to
    methanol.
    Proton conductivity was Iound, unsurprisingly, to increase with increased concentrations oI PSSA in Iormation solutions and
    to change very little with changes in PVA cross-linking density. The best conductivity and lowest methanol permeability
    1,110
    -7
    cm
    2
    /s were shown by densely cross-linked membranes with a high exchange capacity oI 0,92 mg-equiv/g. We
    thereIore see PVAPSSA-based blend membranes as promising candidates Ior use in direct methanol Iuel cells.
    PA.4.3
    BSCF Hollow Fibers for Oxygen Separation
    A. Leo
    1
    . S. Liu
    2
    , J.C.D. Da Costa
    1

    1
    FIMLab Films and Inorganic Membrane Laboratorv, Division of Chemical Engineering, The Universitv of Queensland,
    Brisbane Qld 4072, Australia.
    2
    Department of Chemical Engineering, Curtin Universitv of Technologv, Perth, WA 6845, Australia
    j.dacostauq.edu.au
    Ba
    0.5
    Sr
    0.5
    Co
    0.8
    Fe
    0.2
    O
    3o
    (BSCF) hollow Iibers depicted in Figure 1 were Iabricated using a phase inversion/sintering method. The
    BSCF powders used Ior the synthesis oI hollow Iiber were derived Irom a combined EDTA-Citrate complexation method |1|.
    As oxygen permeation oI BSCF hollow Iibers is controlled by the rate surIace exchange kinetics, the surIace layer
    modiIication with a metal catalyst proved to be beneIicial to improve oxygen Iluxes |2|. In this work, Ag particles were coated
    on both inner and outer surIaces oI the hollow Iibers using a chemical deposition method. The Ag coated BSCF membrane
    delivered Iluxes Irom 0.88 to 4.00 ml.min
    -1
    .cm
    -2
    at 700 and 950
    o
    C, respectively. The Ag catalyst coating resulted in up to 72
    increase in oxygen permeation below 850C compared with unmodiIied BSCF hollow Iibers, whilst above 850
    o
    C
    improvements decreased and were not signiIicant at 950C.

    Fig 1 (leIt) inorganic hollow Iibre showing porous substrate, (middle) synthesised perovskite hollow Iibres, and (right) dense
    layer oI perovkite hollow Iibres.
    |1| Liu, S. and G.R. Gavalas, Oxygen selective ceramic hollow Iiber membranes. Journal oI Membrane Science, 246 (2005)
    103-108.
    |2| A. Leo, S. Liu, J.C. Diniz da Costa, Z. Shao, Oxygen Permeation Through Perovskite Membranes and the Improvement oI
    Oxygen Flux by SurIace ModiIication, Science and Technology oI Advanced Materials, 7 (2007) 819-825.
    -221-
    PA.4.4
    Stability and permeation investigation of Ba
    0,5
    Sr
    0,5
    Co
    0,8
    Fe
    0,2
    O
    3-
    membranes for
    oxyfuel processes
    A. Ellett, D. Schlehuber, T. Markus, L. Singheiser
    Forschungs:entrum Jlich GmbH - IEF-2, Leo-Brandt Strasse - D-52425 Jlich Germanv
    a.ellettIz-juelich.de
    Gas separation membranes are considered to be an eIIicient technology Ior the Iuture generation oI zero CO
    2
    -emission power
    plants. The oxyIuel process consists in the burning oI coal in an oxygen-rich atmosphere to produce a Ilue gas highly
    concentrated in CO
    2
    . Membranes will be used to separate oxygen Irom air in order to produce this combustion gas highly
    concentrated in oxygen. Ba
    0,5
    Sr
    0,5
    Co
    0,8
    Fe
    0,2
    O
    3-o
    is a mixed ionic-electronic conducting material (MIEC) with the perovskite
    structure. It was selected among studied MIEC membrane materials since it exhibits the highest oxygen permeation Iluxes (up
    to 3 ml cm
    -2
    min
    -1
    )
    1, 2
    .
    In the oxyIuel process, the Ilue gas will be recycled to sweep the permeate side oI the membrane, exposing it to high
    concentrations oI CO
    2
    and also water. ThereIore, the Ba
    0,5
    Sr
    0,5
    Co
    0,8
    Fe
    0,2
    O
    3-o
    membrane, operating at high temperatures, has to
    be stable in the gaseous atmosphere oI the Ilue gas. The stability and the permeation oI Ba
    0,5
    Sr
    0,5
    Co
    0,8
    Fe
    0,2
    O
    3-o
    are both a crucial
    Iactor in the selection oI this material Ior membrane technology in the oxy-Iuel process. In this work, the oxygen permeation oI
    Ba
    0,5
    Sr
    0,5
    Co
    0,8
    Fe
    0,2
    O
    3-o
    -based membranes was investigated as a Iunction oI temperature. Moreover, annealing experiments were
    perIormed to ensure that these materials will withstand the high temperature conditions and the gases present in the emissions
    oI a coal power plant. The samples were exposed to CO
    2
    , water vapour, N
    2
    and O
    2
    to check the stability oI
    Ba
    0,5
    Sr
    0,5
    Co
    0,8
    Fe
    0,2
    O
    3-o
    in an atmosphere close to the one in operational conditions. The degradation oI the microstructure oI the
    Ba
    0,5
    Sr
    0,5
    Co
    0,8
    Fe
    0,2
    O
    3-o
    pellets was investigated with Scanning Electron Microscopy (SEM), Electron Dispersive Spectroscopy
    (EDS) and X-Ray DiIIraction (XRD).
    |1| H. Wang et al., Oxygen permeation study in a tubular Ba
    0,5
    Sr
    0,5
    Co
    0,8
    Fe
    0,2
    O
    3-o
    oxygen permeable membrane", Journal oI
    Membrane Science, 210, 259-271 (2002).
    |2| J.F. Vente et al., PerIormance oI Iunctional perovskite membranes Ior oxygen production, ECN-RX-05-201 (Energy
    eIIiciency in industry Separation technology report), November 2005
    PA.4.5
    Preliminary study on use of functionalized hydrocarbonic resins for obtaining
    polyelectrolytes membranes
    B.B.R. Silva, F.J.B. Brum, C. M. Branco, M.M.C. Forte
    Federal Universitv of Rio Grande do Sul (UFRGS), Av. Bento Gonalves, 9500, Setor IJ, Predio 74, Campus do Jale,
    91501-970 - Porto Alegre-RS - Brasil
    mmcIorteuIrgs.br
    One oI the key challenges in advancing the polymer electrolyte membrane Iuel cell (PEMFC) technology lies presently in the
    development oI new durable membranes that allow operation in a broad temperature window, at low humidiIication with water
    vapor or with no humidiIication at all |1|. The state-oI-the-art oI PEMFC technology is based on perIluorosulIonic acid
    (PFSA) polymer membranes operating at a typical temperature oI 80 C and only exhibit suIIicient proton conductivity at high
    degrees oI hydration. The proton conducting membranes employed in PEMFCs are today typically based on polymers with
    hydrated sulIonic acid units. Various eIIorts to substitute the water with less volatile proton conducting compounds have been
    made and membranes doped with phosphoric acid have perhaps been most extensively studied in this respect |2-4|. This work
    discusses an alternatively use oI sulIonated hydrocarbon resins (SR) and poly(vinyl alcohol) (PVA) blends with addiction oI
    antimonic acid (AAc) and phosphonated hydrocarbon resins (PR) to improve the mechanical and conductivity properties. The
    PVA, a water soluble polymer, was reticulated with glutaraldehyde and the membranes were obtained with diIIerent ratio oI
    AAc and PR. The Iunctionalized resins were characterized by FTIR spectroscopy and the membranes (SR/PVA/PR and
    SR/PVA/AAc) were characterized by water uptake measurements, ionic exchange capacity, thermogravimetric analysis (TGA)
    and the conductivity were assessed by impedance spectroscopy.
    -222-
    [1| J. Parvole, P. Jannasch, PolysulIones GraIted with Poly(vinylphosphonic acid) Ior Highly Proton Conducting Fuel Cell
    Membranes in the Hydrated and Nominally Dry State, Macromolecules, 2008, 41, 3893-3903
    |2| Q. Li, R. He, J.O. Jensen, N.J. Bjerrum, Approaches and Recent Development oI Polymer Electrolyte Membranes Ior Fuel
    Cells Operating above 100C, Chemistry oI materials, 2003, 15(26) 4896-4915
    |3| J. Roziere, D.J. Jones, Non-Iluorinated Polymaterials Ior Proton Exchange Membrane Cells, Annual Review oI Materials
    Research, 2003, 33, 503-555
    |4| J.M. Amarilla, R.M. Rojas, J.M. Rojo, M.J. Cubillo, A. Linares, J.L. Costa, Antimonic acid and sulIonated polystyrene
    proton-conducting polymeric composites, Solid State Ionics, 2000, 127, 133-139
    PA.4.6
    Influence of ex situ ageing on Nafion membrane functional properties
    E. Espuche
    1
    , S. Naudy
    1
    , F. Collette
    2
    , F. Thominette
    2
    , G. Gebel
    3
    1
    Universite de Lvon, F-69003, Lvon, Universite Lvon 1, F-69622 Jilleurbanne, France, CNRS, UMR5223, Ingenierie des
    Materiaux Polvmeres, Laboratoire des Materiaux Polvmeres et des Biomateriaux
    2
    LIM, CNRS,UMR8006, 151 Bd de lhopital, 75013 Paris, France
    3
    Groupe Polvmeres Conducteurs Ioniques, SPrAM UMR 5819 CEA-CNRS-UJF, INAC, CEA-Grenoble, 17 rue des Martvrs,
    38054 Grenoble Cedex 9, France
    eliane.espucheuniv-lyon1.Ir
    The sorption and transport oI water in polymer membranes plays, as well as the gas transport properties, an essential role in the
    operation oI polymer electrolyte membrane (PEM) Iuel cells. The sorption and diIIusion oI water in the membrane are
    determining Iactors Ior the distribution oI water throughout the Iuel cell and Ior the local proton conductivity. PEM has also to
    act as a gas separator between the cathode and the anode in order to avoid gas crossover phenomenon. The liIetime oI Iuel cell
    depends then strongly on the PEM initial properties but also on the evolution oI these properties all along the Iuel cell
    operation.
    The aim oI this work is to study the inIluence oI ex situ ageing on NaIion which is the most common polymer membrane
    material used in PEMFC. The ageing parameters have been chosen with respect to the most usual Iuel cell operation
    conditions : the ageing temperature has been Iixed to 80C and the relative humidity was 80 or 95.
    Water vapour sorption as well as water vapour, hydrogen and oxygen permeability coeIIicients have been determined Ior the
    entire range oI water activity on pristine NaIion

    212 and aged NaIion

    212 membranes, respectively. A high decrease oI


    NaIion hydrophilicity, as well as a high decrease oI both water permeability and gas permeability at hydrated state were
    observed as a Iunction oI ageing (Figures 1a and 1b). The evolution oI NaIion transport properties was related to a chemical
    modiIication oI the sulIonated groups upon ageing |1|.

    Figure 1: a ) NaIion water sorption isotherms aIter diIIerent ageing conditions b) Oxygen permeability oI NaIion determined at
    diIIerent relative humidity aIter diIIerent ageing times at 80C and 95RH
    National Research Agency is acknowledged Ior supporting the work.
    |1| F. Collette, C. Lorentz, G. Gebel, F. Thominette, Hygrothermal aging oI NaIion

    , Journal of Membrane Science, to be


    published
    -223-
    PA.4.7
    Conductive properties of poly(ether-sulfone-ketone)s containing sulfonic and
    phosphonic acid groups
    C. Muoz
    1
    , J.G. de la Campa
    1
    , A.E. Lozano
    1
    , J. de Abajo
    1
    , J. Benavente
    2
    1
    Instituto de Ciencia v Tecnologia de Polimeros, CSIC. Madrid. Spain
    2
    Departamento de Fisica Aplicada, Universidad de Malaga. Spain
    deabajoictp.csic.es
    Proton exchange membranes oI the NaIion

    -type do not posses suIIicient properties Ior all Iuel cell conditions, particularly at
    temperature over 80-90
    o
    C, thereIore there is a great interest in alternative polyelectrolyte membranes. It has been
    demonstrated that arylphosphonic groups are more stable than arylsulIonic groups, so that polyarylates containing phosphonic
    groups are being investigated Ior these applications.
    The work presented here is a Iirst evaluation oI the conductive properties oI new copolymers (terpolymers) based in polyether-
    sulIone-ketones with a varied concentration oI sulIonic and phosphonic groups. Two copolymers containing 30/15 (S30-
    P15) and 15/30 (S15/P30) oI SO
    3
    H and PO
    3
    H
    2
    groups respectively have been evaluated by their ionic conductivity.
    Membrane conductivity was obtained Irom electrochemical impedance spectroscopy measurements (EIS) carried out with the
    membranes in contact with HCl solutions at diIIerent concentrations (10
    -4
    c(M) 10
    -2
    ). A Irequency analyzer (Solartron
    1260) was used and Irequencies ranging between 1 Hz and 10 MHz were applied, which allows measuring the separate
    contribution oI membrane and electrolyte solution between the electrodes and the membrane surIaces (100 kHz Ielectrolyte
    10 MHz). Membrane electrical resistance was obtained Irom the impedance plots by using equivalent circuits as models.
    Results showed an increase oI membrane conductivity with the increase oI external solution concentration Ior both samples,
    which was more signiIicant Ior S30-P15 membrane. The extrapolation oI conductivity results gave the Iollowing values Ior
    both membranes at 1 M HCl solution: 3,6x10
    -2
    (ohm.m
    -1
    ) Ior S30-P15 and 5,9x10
    -3
    (ohm.m
    -1
    ) Ior S15-P30. The results
    indicated a good conductivity, and were in agreement with the diIIerent acid strength oI sulIonic and phosphonic groups.
    PA.4.8
    New proton conducting interpenetrated polymer network membrane
    A. Morin
    1
    , O. Fichet
    2
    , L. Chikh
    2
    , V. Delhorbe
    2
    , B. Ameduri
    3
    , M. BathIield
    3
    , R. Mercier
    4
    , X. Thiry
    4
    , S. Vidal
    5
    ,
    L. Augier
    5
    , E. Espuche
    6
    , G. Gebel
    7
    1
    CEA, Liten, LCPEM, 17 rue des Martvrs, F-38054 Grenoble Cedex 9, France
    2
    Universite Cergv-Pontoise LPPI, 5 mail Gav-Lussac, F-95031 Cergv-Pontoise, France
    3
    Institut Charles Gerhardt -IAM, 8 rue de lEcole Normale, F-34296 Montpellier, France
    4
    CNRS-LMOPS, Chemin du canal, F-69390 Jernaison, France
    5
    ERAS Labo, 222 RN90, F-38330 Saint Na:aire les Evmes.
    6
    Universite Claude Bernard Lvon 1-IMP/LMPB, 43 boulevard du 11 novembre 1918, F-69622 Jilleurbanne, France
    7
    INAC-SPrAM, UMR 5819 CNRS/CEA/UJF, CEA-Grenoble, 17 rue des Martvrs, F-38054 Grenoble Cedex 9, France
    arnaud.morincea.Ir
    Although improvements have been done these past years on the perIormances and durability oI proton exchange membrane
    Iuel cells (PEMFC), they do meet all the requirements oI power source Ior automotive applications yet |1|. The proton
    conducting polymer membranes used in PEMFC are the main cause oI perIormance and liIetime limitations |2|, especially at
    high temperature (T~90C) and low relative humidity (RH50).
    In the Irame oI the French national project AMEIRICC Iunded by National Research Agency, original proton conducting
    interpenetrating polymer networks (IPNs) are investigated in order to increase the perIormance and durability oI PEMFC,
    especially Ior these hard operating conditions.
    IPNs are deIined as a combination oI two or more polymer networks synthesized in juxtaposition. The general aim oI these
    types oI polymer associations is to obtain materials with better mechanical properties, increased resistance to degradation and a
    possible improved combination oI the properties oI their components. Especially, the entanglement oI two cross-linked
    polymers leads to Iorced miscibility` compared with usual blends and the resulting materials exhibit good dimensional
    stability.
    IPNs have been studied Ior diIIerent applications, such as medicine |3|, but only Iew attempts have been reported in the literature
    concerning proton conducting interpenetrating polymer network membranes Ior Iuel cell application |4-6|. However, these last
    -224-
    materials are oIten semi-IPN, i.e. a polymer network containing an entrapped linear polymer. In addition, they are generally
    developed Ior DMFC and are made with sulIonic acid-containing 2-acrylamido-2-methylpropanesulIonic acid (AMPS) or
    sulIonated polystyrene (PSSA) and polyvinylalcohol (PVA) which are known to show poor chemical stability in Iuel cell
    operating conditions.
    The original approach in this project is to design IPN membranes with a Iluorinated polymer network and a sulIonated
    aromatic polymer network so as to dissociate the two main Iunctions oI the polymer membrane used in PEMFC, that is to say
    electrolyte and gas separator |7|. We expect to obtain membranes with good chemical stability and mechanical properties
    thanks to the Iirst network as well as high proton conductivity thanks to the second one.
    The preliminary results relative to morphology, proton conductivity, water swelling, chemical stability, mechanical and
    hydrogen permeability properties oI these new IPN membranes will be presented as well as Iuel cell tests perIormed with
    membrane electrode assemblies (MEA) manuIactured with commercial gas diIIusion electrodes.
    |1| F.A. de Bruijn, V.A.T. Dam, G.J.M. Janssen, Fuel Cells 8 (2008) 3.
    |2| R. Borup, J. Meyers, B. Pivovar, Chem. Rev. 107 (2007) 3904.
    |3| A. Lendlein et al., Patent n7,037,984 B2 (2006).
    |4| C.W. Lin, Y.F. Huanga, A.M. Kannan, J. Power Sources 164 (2007) 449.
    |5| G.K. S. Prakash, M. C. Smart, Q.-J. Wang, J. Fluorine Chemistrv 125 (2004) 1217.
    |6| C.W. Walker, J. Electrochem. Soc. 151 (2004) A1797.
    |7| B. Ameduri, L. Chikh, O. Fichet, G. Gebel, R. Mercier, A. Morin, French Patent n08 06890 (2008).
    PA.4.9
    Oxygen permeation study through new fabricated tubular perovskite membrane
    N. Hajimohsen
    1
    , M.R. Mehrnia
    1
    , A. Barati
    2
    , E. Ganji
    3
    1
    School of Chemical Engineering, College of Engineering, Universitv of Tehran, P.O. Box 11155-4563, Tehran, Iran
    2
    Department of chemical engineering ,Arak Universitv, Arak, Iran
    3
    Iranian Research Institute of petroleum industrv, P.O. Box 18745-4163, Tehran, Iran
    mmehrniaut.ac.ir
    Mixed ionic and electronic conducting (MIEC) oxides because oI their latent use in oxygen separation Irom air and the
    oxidation oI light hydrocarbons to syngas and other value-added products have attracted extensive attention all over the
    world. Improving the synthesis and Iormation method oI perovskite type MIEC membranes is a challenging task.
    Since yet no experiment has been Iound on gelcasting technique Iormation oI perovskite tubular membranes. Our work has
    been Iocused on Ba
    0.5
    Sr
    0.5
    Co
    0.8
    Fe
    0.2
    O
    3d
    tubular membranes Iormation based on gelcasting technique. The BSCFO membranes
    were Iormed successIully in tubular geometry by this method and the analysis revealed they have high relative density and the
    permeation experiments show a good Ilux oI oxygen through the Iormed membranes.
    Fig 1:SEM photograph oI outer surIace oI the Iormed membrane
    |1| J. Tong, W. Yang , R. Cai, B. Zhu, L. Lin , "Titanium-based perovskite-type mixed conducting ceramic membranes Ior
    oxygen permeation" , Materials Letters , 56 (2002) 958962 ,2002.
    |2| M. Kokabi , A.A. Babaluo, A. Barati, "Gelation process in low-toxic gelcasting systems" , Journal oI the European
    Ceramic Society, 26 (2006), 3083-3090,2006.
    -225-
    PA.4.10
    Proton Conductive Membranes Based on Doped Sulfonated Polytriazole
    M. Boaventura
    1
    , M. L. Ponce
    2
    , D. Gomes
    2
    , A. Mendes
    1
    , S. P. Nunes
    2
    1
    LEPAE - Laboratorio de Engenharia de Processos Ambiente e Energia, Faculdade de Engenharia da Universidade do Porto,
    Rua Dr. Roberto Frias s/n, 4200-465, Porto, Portugal
    2
    GKSS Research Centre Geesthacht GmbH, Max Planck Str. 1, D-21502, Geesthacht, Germanv
    marta.boaventuraIe.up.pt
    PEMFC operating at temperatures above 100 C have received increased attention. The increase oI the operation temperature
    will improve reaction kinetics, water and heat management and catalyst CO tolerance. Among possible approaches to obtain
    membranes Ior intermediate temperature operation in PEMFC (100-200 C), there is the use oI polymers that exhibit intrinsic
    proton conductivity such as polymers based on Sulphonated Polytriazole. Sulphonated Polytriazole has acidic (-SO
    3
    H group)
    and basic sites (basic nitrogen) in the repeating unit and thereIore it can oIIer the possibility oI Iorming a hydrogen bonding
    network and promoting proton conduction. Besides, it can be doped in order to increase ionic conductivity trough hydrogen
    bond Iormation or by proton acceptor-donor interaction.
    Sulphonated polytriazole was doped with benzimidazole sulIonic acid and phosphoric acid to improve the proton conductivity.
    It has been demonstrated that nitrogen-containing heterocycles such as imidazole or benzimidazole can be used as proton
    carriers |1, 2|. The basic nitrogen acts as proton acceptor to the proton oI the sulIonic acid group Irom the polymer matrix,
    Iorming carriers charge Ior protons |3|. Phosphoric acid is well known as proton donor and increases the proton conductivity.
    The resulting membranes were characterized as conductors at diIIerent temperatures (80 C, 100 C, 120 C and 150 C). Also,
    thermal and mechanical characterizations were perIormed.
    Results show that doped sulphonated polytriazole has potential as proton conducting membrane Ior Iuel cell applications, in
    particular at high temperature and low humidity conditions. PerIormance tests are being carried out.
    |1| K. D. Kreuer, A. Fuchs, M. Ise, M. Spaeth, J. Maier, Electrochimi. Acta 1998, 43, 1281.
    |2| W. Munch, K. D. Kreuer, W. Silvestri, J. Maier, and G. SeiIert, Solid State Ion. 2001, 145, 437.
    |3| Yulin Ma, The Fundamental Studies oI Polybenzimidazole/Phosphoric Acid Polymer, PhD thesis, 2004, Case Western
    Reserve University.
    The work oI M. Boaventura was supported by FCT (Grant SFRH/BD/28187/2006). The present work was also partially
    supported by FCT project PTDC/EQU-EQU/70574/2006 and the Helmholtz Virtual Institute 'Asymmetric Structures Ior
    Polymer Electrolyte Fuel Cell.
    PA.4.11
    On the course of sulfonation of poly(arylene ether sulfone)s
    J. Meier-Haack, P. Friedel, W. Butwilowski, C. Vogel
    Leibni: Institute of Polvmer Research Dresden, Hohe Strasse 6, D-01069 Dresden, Germanv
    mhaackipIdd.de
    SulIonated aromatic polymers such as poly(arylene ether)s (PAEs) are oI strong interest Ior membrane applications, in
    particular as ion-exchange membrane in Iuel cells. In general there are two ways oI obtaining such materials; Iirstly the use oI
    already sulIonated monomers in the polymerization step or, secondly postsulIonation oI commercially available polymers.
    While the Iirst method is limited by the number oI sulIonated monomers, the second method is simple to perIorm but it is not
    that easy to control position, number and distribution oI sulIonic acid groups along the polymer chain. Recently we reported on
    poly(arylene ether sulIone)s having a phenyl ring in the side-chain, which was intended to be sulIonated selectively |1|.
    However, NMR spectra revealed that the sulIonation occurred at both sites, the main chain as well at the side chain.
    Surprisingly poly(arylene ether ketone)s with a similar composition were sulIonated only in the side-chain |1,2|. From the
    above mentioned results the question arises, why these two polymers, which diIIer only in the Iunctional group in the main
    chain (keto or sulIone), show this diIIerent behavior on sulIuric acid treatment? This contribution aims at giving an answer to
    that question. Both types oI polymer, the poly(ether ether ketone) (PEEK) and the poly(ether ether sulIone)
    -226-
    (PEES) are protonated in the sulIonating agent
    conc. sulIuric acid, meaning that a positive charge
    is introduced into the polymer chain. As revealed
    by SCF calculations and by UVvis spectroscopic
    investigations, the ketogroup in the PEEK sample
    is able to distribute the positive charge over
    several centers oI the polymer main chain by the
    Iormation oI a quinoidic electron system while the
    sulIone group is not (Iig. 1). Hence the sulIonation
    oI the PEEK can only take place at the pendant
    phenyl substituent while in the case oI the PEES
    sample both phenylrings oI the biphenyl moiety
    are susceptible to the sulIonation reaction.
    |1| J. Meier-Haack, H. Komber, C. Vogel, W. Butwilowski, K. Schlenstedt, D. Lehmann, Side-Chain SulIonated Poly(arylene
    ether)s Ior Fuel Cell Applications, Macromol. Symp. 2007, 254, 322 328
    |2| B. Liu, G. P. Robertson, D.-S. Kim, M. D. Guiver, W. Hu, Z. Jiang, Aromatic Poly(ether ketone)s with Pendant SulIonic
    Acid Phenyl Groups Prepared by a Mild SulIonation Method Ior Proton Exchange Membranes, Macromolecules, 2007, 40,
    1934 1944
    PA.4.12
    Effects of nanostructuring in oxygen-permeable membrane materials on the base of
    mixed conducting perovskites ABO
    3-x
    U.V. Ancharova
    1,2
    , A.S. Kozhemyachenko
    1
    , N.Z. Lyakhov
    1
    , A.P. Nemudry
    1
    , O.A. Savinskaya
    1
    ,
    S.V. Tsybulya
    3
    1
    Institute of Solid State Chemistrv and Mechanochemistrv SB RAS, Kutatelad:e 18, Novosibirsk, 630128, Russia
    2
    G.I. Budker Institute of Nuclear Phvsics SB RAS, Lavrentveva str. 11, Novosibirsk, 630090, Russia
    3
    G.K. Boreskov Institute of Catalvsis SB RAS, Lavrentveva str. 5, Novosibirsk, 630090, Russia
    ancharovagmail.com
    Non-stoichiometric mixed conducting oxides ABO
    3-x
    having high oxygen mobility, are used as oxygen-permeable membranes
    and electrodes Ior solid-state Iuel cells.
    By combined use oI methods oI synchrotron radiation diIIraction, small-angle scattering, electron microscopy and diIIraction,
    moessbauer spectroscopy and methods oI computer simulating, various models oI deIects-ordering in non-stoichiometric
    mixed conducting perovskites are considered. That is illustrated by the experimental data oI compounds SrCo
    0.8
    Fe
    0.2
    O
    3-x
    (doped
    by cations La, Ca in A-position and Al, Nb on B-position oI perovskite ABO
    3-x
    -system) and SrFeO
    3-x
    (doped by cations Mo, W
    in B-position oI perovskite ABO
    3-x
    -system) with various degree oI oxygen deIiciency 0x0.5.
    In this work models oI ordering on nano-level in the structure oI given compounds are proposed, that is determinative Iactor in
    improvement oI Iunctional properties oI membranes and approaches to understanding oI oxygen transport mechanism.
    Shown that nonstoichiometric perovskites can have partial ordering, that is related to microtwinning taking place at Ierroelastic
    phase transitions. The most evident model oI deIect ordering is superposition oI coherent stacking browmillerite domains with
    partial remaining oI long-range order symmetry in such way to "cubic" structure with superstructure peaks appear at the X-Ray
    diIIraction pattern.
    The consequence oI the partial ordering is the presence oI high concentration oI extended deIects (domain walls, twinning
    boundaries etc.). That aIIects on the Iunctional properties oI membranes, allows to increase mechanical, thermal and chemical
    stability and obtains the increasing oI oxygen-ionic transport properties, since deIects in structure are channels Ior Iast oxygen
    diIIusion.
    The work has been carried out on the equipment oI Syberian Synchrotron Radiation Center, BINP SB RAS, Novosibirsk,
    Russia; Kurchatov Synchrotron Radiation Center , KIAE RAS, Moscow, Russia.
    -227-
    O O C
    O
    O O C
    O
    H
    O O C
    O
    H
    +H
    +
    Fig. 1: Formation oI a
    quinoidic system on
    protonation oI PEEK
    PA.4.13
    New composite membranes for fuel cells obtained by mixing sulfonated polysulfone
    and plasma treated Laponite. Elaboration and characterization
    C. Lixon-Buquet
    1
    , D. Langevin
    1

    ,

    E. Dargent
    1
    , S. Marais
    1
    , Q.T. Nguyen
    1
    , F. Poncin-Epaillard
    2
    1
    Laboratoire PBS, FRE 3101, Universite de Rouen-CNRS, Faculte des Sciences et Techniques, Bd Maurice de Broglie, 76821
    Mont Saint Aignan, France.
    2
    Laboratoire Polvmeres, Collodes, Interfaces UMR CNRS 6120, Universite du Maine.
    dominique.langevinuniv-rouen.Ir
    Hydrogen turns out to be a very serious candidate to replace Iossil energy sources such as oil. That`s why hydrogen Iuel cells,
    and more particularly the proton exchange membrane which is at the heart, are the object oI so numerous studies all around the
    world.
    Eventually, a lot oI researches have been carried out to Iind new membranes |1| |3|, more successIul, to replace the NaIion
    membrane oI Dupont de Nemours, the Iuel cell reIerence.
    In this work, our aim is to elaborate a new membrane able to answer at best to Iuel cell speciIications. PolysulIone (PSU) was
    chosen as the membrane polymer component Ior its good thermal and mechanical properties, Ior its low price and commercial
    availability.
    In the Iirst time, we have mixed in solution PSU with Laponite particles containing sulIonic acid groups bonded to surIace (via
    plasma activation). Water pervaporation and water vapour sorption have showed that the addition oI the inorganic compounds
    to PSU improves the water retention oI the composite membrane |6|. The permeability coeIIicient decreases and the quantity
    oI sorbed water increases with the introduction oI sulIonated clay.
    However, the sulIonic acid groups on the Laponite are not suIIicient to allow the proton transport through the PSU membrane,
    so the sulIonation oI the polymer matrix appears as necessary in order to obtain conductivity.
    In the second time, sulIonated polysulIone (SPSU) have been prepared with diIIerent sulIonation rates. In order to argue on the
    presence oI sulIonic groups on the polymer chains, we have characterized the diIIerent SPSU with inIrared spectra, Ion
    Exchange Capacity (IEC) (meq/g), proton conductivity (S/cm) and water uptake content (). We have showed that the proton
    conductivity, like water uptake content, varies with the IEC |2|. We can explain this behaviour, usual with the ion exchangers,
    since, Ior weak graIting ratios, the membrane have the properties oI a slightly conducting diluted acid (RSO
    3
    -
    ,H

    ). Unlike, Ior
    high graIting ratios, the membrane behaves as a concentrated strong acid with a high conductivity.
    In view oI Iurther investigations, we Iound a compromise between a good conduction, that`s to say superior or equal to 10
    -2
    S.cm
    -1
    , and a weak water uptake content : inIerior or equal to 30. That`s why we have chosen, in our sulIonated SPSU series,
    the SPSU numbered 6 which presents a proton conductivity oI 0.094 S.cm
    -1
    (60C) and a water uptake oI 30.
    The conductive membranes obtained by incorporating the sulIonated Laponite to the SPSU 6, in order to increase the retention
    oI water and the proton conductivity |4, 5|, are now under investigations.
    |1| R. Naim, A.F. Ismail, H. Saidi, E. Saison, in 'Development oI sulIonated PSU membranes as a material Ior PEM.
    |2| H.B. Park, H.S. Shin, Y.M. Lee, J.W.Rhim, J. Membr. Sci., 247 (2005) 103-110.
    |3| B. Smitha, S. Sridhar, A.A. Khan, J. Membr. Sci., 225 (2003) 63-76.
    |4| P. Bebin, M. Caravanier, H. Galiano, J. Membr. Sci., 278 (2006) 35-42.
    |5| H. Munakata, H. Chiba, K. Kanamura, Solid State Ionics, 176 (2005) 2245-2450.
    PA.4.14
    Morphological and electrical properties of cermets as electrodes for ceramic
    membranes in solid-state electrolyser
    C. Deslouis
    1
    , C. Hodebourg
    1
    , M. Keddam
    1
    , A. Pailleret
    1
    , K. Rahmouni
    1
    ,

    H. Takenouti
    1
    , S. Willemin
    2
    , B. Sala
    2
    1
    LISE, CNRS, UPMC, Case 133, 4 Place Jussieu, 75252 Paris Cedex 05, France
    2
    AREJA NP, IEM, Place Eugene Bataillon, 34095 Montpellier Cedex 5, France
    Claude.deslouisupmc.Ir
    In the Irame oI the ANR Pan-H program, water steam electrolysis was intended Ior hydrogen production with new perovskite
    based ceramic |1|. As part oI this program, elaboration oI cathodic cermet electrodes represents a key issue which requires
    several characterization methods pointing to among others morphological as well as surIace electrical properties oI these
    -228-
    materials. DiIIerent candidates have been tested and in this work we report on a cermet Iormed as a composite oI perovskite
    sintered with 40 oI metals in weight. The electrical as well as morphological characteristics are necessary so as to optimize
    the so-called triple points representing the ideal coincidence oI electronic conductor ensuring percolation Ior collecting
    electrons in the external circuit, oI ionic conductor Ior protons transport and their contact Ior catalyzing the electrochemical
    reaction, and Iinally oI the gas input and output at these particular boundaries without hindrance eIIects.
    These characterizations have been carried out using AFM in the contact mode and in the current-sensing mode (CS-AFM) with
    conducting tips.
    Figure 1 displays the two images (2m2m) showing the
    morphology (leIt) and the local superIicial electronic conductivity
    (right). In the leIt Iigure, white spots are protruding zones while black
    ones are hollow parts. In the conductivity mapping three zones appear
    in shaded tones, the white one being highly conductive presumably
    metallic, the brown one being poorly conductive likely semiconducting
    layer and the black one being insulating (ceramic). These three zones
    could be likely assigned to metal, metal oxide and perovskite
    respectively. In addition, obvious correlations are observed in the x-y
    plane, and in particular, highly conductive zones (metal) correspond to
    the protruding ones. Conductivity curve in Fig. 1 was obtained by
    imposing a 4.5 V voltage bias between the tip and the substrate.
    Changing the bias modiIies the aspect and extension oI the diIIerent
    shaded tones. However, the aspect oI the I-V plots that can be obtained by changing the bias at Iixed points on the substrate are
    qualitatively diIIerent and in particular, these plots on the brown zones assigned to metal oxide, show the characteristic aspects
    generally Iound on semiconducting materials.
    This measuring technique appears as well appropriate Ior characterizing and possibly optimizing the cermet with respect to the
    distribution oI the ionic and electronic conductors.
    |1| CELEVA ANR project 06-PANH-005-03.
    PA.5.1
    Microstructured hollow fiber membranes for ultrafiltration
    P.Z. ulIaz
    1
    , H.H.M., Rolevink
    2
    , W.Nijdam
    3
    , C. van Rijn
    3
    , R.G.H. Lammertink
    1
    , M. Wessling
    1
    1
    Membrane Technologv Group, Facultv of Science, Universitv of Twente, PB 217, 7500AE, Enschede, The Netherlands
    2
    European Membrane Institute, Membrane Technologv Group, Universitv of Twente, PB 217, 7500AE, Enschede, The
    Netherlands
    3
    Aquamarifn BJ, Berkelkade 11, 7201JE, Zutphen, The Netherlands
    p.z.culIazutwente.nl
    Hollow Iibers are used in many membrane processes ranging Irom
    gas separation to microIiltration. The Iibers are most commonly made
    by the solution spinning method and have a round shape. Through the
    use oI silicon micromachining technology, the spinnerets used Ior
    spinning hollow Iibers can be modiIied to produce microstructured
    Iibers with convolutions |1|. This is done by placing inside the
    spinneret a silicon insert with a structured opening in the middle, so
    that the polymer solution Ilows through this structured annulus
    instead oI a circular annuloleIin transport and are expected to be more
    durable with time.as an oleIin carrier Ior the Iacilitated oleIin
    transport. It is concluded that copper nanoparticles can also be used as
    oleIin carrier Ior Iacilitated oleIin transport and are expected to be
    more durable with time.
    The increased surIace area oI the Iibers is expected to result in
    increased permeation per Iiber length iI the selective layer is oI
    comparable thickness, porosity and pore size distribution. Convoluted
    membranes are also suggested to cause turbulence around the
    convolutions, which may decrease Iouling and Iacilitate cleaning oI
    the membranes |2|.
    -229-
    (b)

    Fig. 1: Morphology and conductivity oI 40 metals
    perovskite cermet using CS-AFM
    (b)
    Figure 1. Fibers spun with (a) structured and
    (b) round inserts
    (a)
    (a)
    Figure 2. Fibers spun with pulling speeds oI
    (a) 3 m/min and (b) 23 m/min
    In this study, ultraIiltration Iibers oI a PES-PVP blend were made using a dry-wet spinning process. The Iibers were made
    using a structured insert as well as a round insert Ior comparison. The clean water Iluxes were measured to compare the
    permeation rate through the Iibers. The molecular weight cut-oIIs were measured by Iiltering a mixture oI dextranes and the
    pore size distributions were determined using permporometry.
    Structured Iibers with 60 enhanced surIace area per volume were spun using an air gap oI 5 mm (Figure 1.a). These Iibers
    have 80 higher surIace area compared to round Iibers spun under the same conditions (Figure 1.b) and show 100+10
    enhancement in water permeation per unit length oI Iiber. The two Iibers have similar molecular weight cut-oII oI 15+5 kDa
    and also similar pore size distribution.
    Structured Iibers were spun varying polymer dopes, the air gap Iorward osmosis Irom chemically modiIied polybenzimidazole
    (PBI) nanoIiltration hollow Iiber membranes with a thin wty oI Melbourne, Victoria, 3010, Australia
    |1| Nijdam, W., De Jong, J., Van Rijn, C.J.M., Visser, T., Versteeg, L., Kapantaidakis, G., Koops, G.-H., Wessling, M., 2005,
    Journal oI Membrane Science 283, p. 209-215.
    |2| Scott, K., Mahmood, A.J., Jachuck, R.J., Hu, B., 2000, Journal oI Membrane Science 173, p. 1-16.
    PA.5.2
    Synthesis and characterization of crown ethers functionalized carbon nanotubes
    G. NechiIor
    1
    , S.I. Voicu
    1
    , A.C. NechiIor
    1
    , S. Mihai
    2
    1
    Universitv POLITEHNICA of Bucharest, Facultv of Applied Chemistrv and Materials Sciences, Str. Gheorghe Poli:u 1-7
    011061 Bucharest, Romania
    2
    Institut Europeen des Membranes (IEM), ENSCM, UM2, CNRS, Universite Montpellier 2, CC047, Place Eugene bataillon,
    34095 Montpellier, France
    doru.nechiIoryahoo.com
    Increasing the selectivity oI carbon nanotubes represents a continuously attention Ior microelectronics and separations
    applications |1, 2|. This work presents the results obtained Ior synthesis oI crown ethers Iunctionalized carbon nanotubes using
    cyanuric chloride as spacer. The synthesis route is presented in Fig. 1.
    O
    O O
    O O
    NH
    N
    N
    N
    Cl
    Cl
    O
    O O
    O O
    NH
    2
    N
    N
    N
    Cl
    Cl
    Cl

    O
    O O
    O O
    NH
    N
    N
    N
    Cl
    Cl
    NH
    2
    NH
    O
    O O
    O O
    NH
    N
    N
    N
    Cl
    CHCl
    3
    N(Et)
    3

    in CHCl
    3
    Fig.1 Synthetic route Ior crown ethers Iunctionalized carbon nanotubes
    Aminobenzo-18-crown-6 ether and aminobenzo-15-crown-5 are Iunctionalized with cyanuric chloride in chloroIorm in the
    presence oI triethylamine. The Iunctionalization with amino carbon nanotubes was perIormed in a tank immersed into an
    ultrasonic bath with thermostat, in the presence oI a small amount oI pyridine Ior in situ generated hydrochloric acid
    neutralization. Finally, the product crown ether carbon nanotubes molecules are obtained and are separated Irom mass
    reaction through a polyamide membrane via an ultraIiltration process. Functionalization degree was determined by thermal
    analysis, FT-IR, NMR.
    |1| B.Bhushan (Ed.), Springer Handbook oI Nanotechnology, Springer-Verlag 2004
    |2| G. NechiIor, S.I. Voicu, A.C. NechiIor, S. Garea, Nanostructured hybrid membrane polysulIone-carbon nanotubes Ior
    hemodyalisis, Desalination, in press.
    -230-
    PA.5.3
    Immobilization and grafting of poly(ethylene glycol) methacrylate onto ePTFE
    membrane by atmospheric pressure plasma jet
    T. C. Wei, Y. Chang, C. J. Chang, Y. J. Shih, Y. L. Liu
    R&D Center for Membrane Technologv and Department of Chemical Engineering, Chung-Yuan Universitv, Jhongli, Taiwan
    tcweicycu.edu.tw
    In general, it is a challenge to graIt Iunctional organic material onto the chemically inert TeIlon-based membrane surIace.
    Traditional method necessitates plasma surIace modiIication and subsequent thermal-induced graIt copolymerization. It
    requires complicated procedures, extended processing time and extensive use oI organic chemicals. This work describes a Iast
    and simple method to graIt poly(ethylene glycol) methacrylate (PEGMA) macromonomer onto expanded
    poly(tetraIluoroethylene) (ePTFE) membranes by atmospheric pressure plasma jet (APPJ). In this approach the ePTFE is Iirst
    immersed in monomer solution beIore placed in APPJ Ior direct exposure. The APPJ will activate the membrane surIace and
    induce immobilization/graIt-polymerization at the same time. The graIting yield can be controlled by monomer concentration
    and plasma parameters. The chemical composition and microstructure oI the surIace-modiIied ePTFE membranes were
    characterized by Xray Photoelectron Spectroscopy (XPS), Fourier transIorm inIrared spectroscopy (FT-IR), and atomic Iorce
    microscopy (AFM). BioIouling property oI the modiIied membranes was evaluated by the measurements oI the Fibrinogen
    adsorption determined using an enzyme-linked immunosorbent assay (ELISA).
    The experimental results show that the graIting yield oI PEGMA exceeds 0.8 mg/cm
    2
    with 20 seconds oI APPJ exposure. The
    graIted material preserves the monomer`s Iunctional structure. The highly hydrated PEGMA chain on the resulting ePTFE
    membranes was Iound to reduce signiIicantly the relative Fibrinogen adsorption to about 10 . The hydrophilicity oI the
    modiIied ePTFE membranes increases with increasing the graIting yield oI the copolymerized PEGMA controlled by APPJ
    exposure time. However, longer plasma exposure results in the cross-linking oI PEG side chain, which reduces moderately the
    bio-Iouling resistance oI the modiIied ePTFE membrane.
    PA.5.4
    Novel electrospun nanofiber composed of amphiphilic polyelectrolyte for salt
    rejection
    S. H. Cheng
    1
    , L. T. Chen
    2
    , W. Y. Chen
    1
    , H. Shao
    3
    , T. M. Liang
    3
    , M. C. Chang
    3
    1
    Material & Chemical Research Laboratories, Industrial Technologv Research Institute
    2
    Industrial Technologv Research Institute
    3
    Energv and Environment Research Laboratories, Industrial Technologv Research Institute 321 Section 2, Kuang Fu Road,
    Hsinchu TAIWAN
    Tel.886-3-5732636 Fax.886-3-5732349
    minchaochangitri.org.tw
    Polyelectrolyte was widely used as gel material Ior gel-Iilled membrane obtained by anchoring charged gels within the pores
    oI a microporous support. The good salt rejection ability oI this gel-Iilled membrane leads to its usage Ior desalination oI
    aqueous salt solutions under reverse osmosis conditions or water soItening by many authors |1|. In addition, generation oI
    nanoIiber Irom electrospinning oI polyelectrolyte was also reported Ior some workers |2|. Hence a novel nanoIiber composed
    oI an amphiphilic polyelectrolyte having good salt rejection ability could be expected and studied in this paper. It was prepared
    Irom electrospinning oI amphiphilic polyelectrolyte homogeneous solution. Amphiphilic polyelectrolyte was a copolymer oI 4-
    styrenesulIonic acid sodium salt (SSA), 4-vinyl pyridine (VP) and styrene (ST). To the best oI our knowledge, there are no
    data about the preparation and salt rejection ability study Ior this type oI polyelectrolyte nanoIiber. Our preliminary results
    indicated that non-woven Iibrous mats composed oI such nanoIibers had good initial salt rejection ability, as shown in Fig.1.
    Fig.2 shows the time proIile oI NaCl rejection Ior this type oI polyelectrolyte nanoIiber with diIIerent weight basis. It can be
    seen that salt rejection behavior was weight basis dependent. In this paper, we will report the nanoIiber preparation process
    including copolymer composition, electrospinning condition and its corresponding salt rejection behavior. Eventually we hope
    to develop a process Ior preparation Iibrous mats having good seawater salt rejection and water soItening ability Irom this type
    oI polyelectrolyte nanoIiber.
    -231-


    |1| A. Toutianoush, W. Jin, H. Delig z, B. Tieke,Polyelectrolyte multilayer membranes Ior desalination oI aqueous salt
    solutions and seawater under reverse osmosis conditions , Appl. SurI. Sci.., 2005, 246, 437-443
    |2| H. Penchev, D. Paneva, N. Manolova, I. Rashkov, Novel electrospun nanoIibers composed oI polyelecrolyte complexes,
    Macromol. Rapid Commun.., 2008, 29, 677-681
    PA.5.5
    Mass transfer in ED channels constituted by commercial heterogeneous membranes
    and membranes with modified surface
    N. Melnik, E. Belova, N. Pismenskaya, V. Nikonenko
    Membrane Institute, Kuban State Universitv, 149 Stavropolskava St., 350040 Krasnodar, Russia
    melniknadezhdainbox.ru
    ModiIication oI ion-exchange membranes surIace widens the possibilities in use oI electrodialysis (ED). Figure 1 shows that
    substitution oI secondary and tertiary amines by quaternary ones using modiIication oI membrane surIace by strong
    polyelectrolyte (membrane MA-40M) and homogenization oI cation-exchange membrane surIace by the Iilm oI strong
    polyelectrolyte with Iixed sulIonate groups (MK-40F) results in increasing mass transIer in comparison with initial
    membranes (MA-40 and MK-40). The observed eIIect is mainly due to increasing electroconvection, coupled with the
    reduction oI H

    /OH
    -
    ions
    generation at the surIace oI modiIied membranes. The
    reduction oI water splitting is revealed by pH measurement
    in desalination channel (DC) during electrodialysis
    electrical Iield applied. It is Iound that pH oI desalted
    solution in MK-40F//MA-40M system is basic, whereas in
    the DC constituted by commercial membranes
    (MK-40//MA-40) the solution becomes acidic. For both
    investigated systems, the mass transIer coeIIicient increases
    with diluting Ieed solution and growing, the potential drop
    over DC.
    Study is realized using the modiIied HittorI method |1| with
    a DC oI 10 cm length; the spacing between membranes is 1
    mm and the potential drops over DC 2.5 V, 4 V and 6 V.
    The NaCl solution Ilow velocity was 2.5 cm/s. In all cases
    membranes a separator (S) with the 4 mm square meshes
    oriented at 45
    0
    to solution stream was used.
    DC
    = 6 V
    0
    0,5
    1
    1,5
    2
    2,5
    3
    3,5
    0 0,005 0,01 0,015 0,02
    C
    inIet
    , M
    k

    C
    I ,

    d
    m
    /
    h
    MA-40//MK-40
    MA-40M//MK-40+F
    Figure 1: Concentration dependence oI mass transIer
    coeIIicient Ior Cl
    -
    ions
    The work is perIormed with Iinancial contribution oI RFBR, grants ## 07-08-00533, 08-08-01047, 09-08-96529.
    |1| E.V. Laktionov, N.D. Pismenskaya, V.V. Nikonenko, V.I Zabolotsky, Method oI electrodialysis stack testing with the Ieed
    solution concentration regulation, Desalination, 2002, 151, 101116.
    -232-
    Fig 2. The time proIile oI NaCl rejection Ior polyelectrolyte
    nanoIiber with diIIerent weight basis(A:12g/m
    2
    , B:24 g/m
    2
    , C:
    29 g/m
    2
    , control: PAN nanoIiber 29g/m
    2
    ) at same calendering
    condition.
    0
    20
    40
    60
    80
    100
    0 50 100 150 200
    Time (min)
    N
    a
    C
    l

    R
    e
    j
    e
    c
    t
    i
    o
    n

    (
    %
    )
    A
    B
    C
    control
    Fig. 1 SEM micrographs oI Iibrous mats Irom
    polyelyectrolyte nanoIiber
    PA.5.6
    Metal-phosphorus-oxide nanostructures preparation on the surface of ceramic
    membranes by molecular layering deposition
    G. Tereshchenko
    1
    , M. Ermilova
    1
    , N. Orekhova
    1
    , N. Basov
    1
    , A. Malygin
    2
    , A. Malkov
    2
    , S. Mikhailovsky
    2
    1
    Institute of Petrochemical Svnthesis RAS, 29, Leninskv av., Moscow, 119991, Russia
    2
    St.Petersburg Technical Universitv, 26, Moskowskv av., St.Petersburg, 190013, Russia
    ermilovaips.ac.ru
    The inorganic catalytic membrane reactors with composite membranes combine usually the advantages oI membrane
    contactor and catalytic membrane reactors |1|. The clue question in such composites synthesis is a proper method oI chemical
    modiIication oI membrane pores and surIace to prepare an active and selective membrane catalyst. One oI the most promising
    methods oI an inert membrane modiIication on the atomic scale is the method oI molecular layering (ML) |2|, based on the
    irreversible interaction between oI low-molecular reagents and Iunctional groups oI a solid substrate surIace under the
    conditions oI continuous reagent input and removing the Iormed gaseous
    products.
    The purpose oI the given research was a development oI the methods oI
    vanadium- or chromium-phosphorus oxides` nanostructures obtaining on a
    surIace oI the inert asymmetric alumina membranes and the studies the
    catalytic properties oI composite membranes prepared in methanol oxidative
    dehydrogenation. To improve the selectivity oI gas permeability oI inert
    membranes their pore structure was preliminary modiIied by ML deposition oI
    titania at the variation oI number oI ML cycles. Methanol conversion and
    Iormaldehyde Iormation selectivity oI the Iormed membrane catalyst was
    shown to depend on the nature and the composition oI metal-phosphorus-
    oxide structures deposited on the surIace oI inert asymmetric ceramic
    membrane (Figure 1). The IR-study oI the surIace oI dispersed -Al
    2
    O
    3
    particles, modiIied by diIIerent number and sequence oI ML

    deposition oI V-
    O-P structures, Iormed on the surIace, revealed their inIluence on the quality
    and concentration oI species.
    This work was supported by the Program oI the Russian Academy oI Science
    (project no.27).
    |1|. L. Paturzo,; A. Basile, E. Drioli, High temperature membrane reactors and integrated membrane operations. Rev. Chem.
    Eng., 2002, 18, 511-551.
    |2| A.A.Malygin, Nanotechnology oI molecular layering, Russian Nanotechnologies, 2007, 2(3-4), 87-100.
    PA.5.7
    Track-etched membranes with stimuli-responsive pores via surface-initiated atom
    transfer radical polymerization
    F. Tomicki, M. Ulbricht
    Lehrstuhl fr Technische Chemie II, Universitt Duisburg-Essen, 45117 Essen, Germanv
    Ialk.tomickiuni-due.de
    Track-etched membranes (TEM) made Irom poly(ethylene terephthalate) (PET) have been investigated as starting material Ior
    multiple surIace Iunctionalization purposes because oI their uniIorm pore structure, narrow pore size distribution and robust,
    but moderately reactive structure |1|. SurIace-initiated Atom TransIer Radical Polymerization (ATRP) has been proven to be
    versatile in terms oI adjustment oI generated layer thickness, graIting density and monomer selection |2-4|. Stimuli-responsive
    polymers are promising materials in drug delivery and controlled release applications |5|. Our group has successIully
    Iunctionalized PET TEM with homopolymers consisting oI poly(N-isopropylacrylamide) (PNIPAAm). The temperature-
    -233-
    240 260 280 300 320 340 360 380 400
    0
    10
    20
    30
    40
    50
    60
    70
    80
    90
    100
    2
    2
    1
    1
    X
    ,

    S

    (
    %
    )
    Temperature (C)
    Fig.1. Methanol conversion (open symbols)
    and Iormaldehyde Iormation selectivity (solid
    symbols) versus temperature Ior membrane
    catalysts Al
    2
    O
    3
    /TiO
    2
    -CrO (curves 1) and
    Al
    2
    O
    3
    /TiO
    2
    -CrOP (curve 2) structures
    responsive PNIPAAm layer (polymer density in the swollen state ~0,4 g/cm) with a brush structure showed
    swelling/deswelling ratios oI about 3, and the ratio could be increased by decreasing the graIt density |4|.
    Here we report about recent investigations on surIace Iunctionalized
    PET TEM with N,N-dimethylaminoethyl methacrylate (DMAEMA)
    layers under stationary and streaming conditions leading to dually
    stimuli-responsive (pH, T) poly(N,N-dimethylaminoethyl methacrylate)
    (PDMAEMA). InIluences oI pore diameter, graIting density and chain
    length were studied. Also systematic investigations on surIace
    Iunctionalization have been accomplished in order to study the impact
    oI reaction parameters on surIace-initiated ATRP such as reaction time,
    monomer concentration and Iunctional group density. In our attempt to
    utilize and combine diIIerent surIace Iunctionalization techniques such
    as UV-graIting and ATRP we modiIied PET TEM bearing now both
    initiators on the membrane surIace. Both initiators could be widely
    indepently used Ior surIace Iunctionalization leading to more complex
    architectures and possible applications as tailored materials Ior
    controlled release devices, advanced separations and molecularly
    imprinted membrane surIaces.
    |1| M. Ulbricht, Polvmer, 47, 2006, 2217.
    |2| K. Matyjaszewski, J. Xia, Chem. Rev., 101, 2001, 2921.
    |3| Z. Bao, M. L. Bruening, G. L. Baker, Macromolecules, 39, 2006, 5851.
    |4| A. Friebe, M. Ulbricht, Langmuir, 23, 2007, 10316.
    |5| S. Kankane, S. Bhanu, S. K. Shukla, A. K. Bajpai, Prog. Polv. Sci., 33, 2008, 1088.
    PA.5.8
    Development of photo-responsive membranes for fractionation of
    biomolecules
    F.R.P. Oliveira
    1
    , C.A.M. Portugal
    1,2
    , J.G. Crespo
    1
    1
    Requimte-CQFB, FCT-Universidade Nova de Lisboa, Campos da Caparica 2829-516 Caparica (Portugal)
    2
    CEBAL Centro de Biotecnologia Agricola e Agro-Alimentar do Baixo Alentefo e Litoral, 7801-908 Befa (Portugal)
    paraiso.Iabiodq.Ict.unl.pt
    Membrane Iouling and low process selectivity caused by aggregation oI biomolecules represents an important setback to a
    wider use oI membrane processes in industry.
    Many studies have been perIormed evaluating possible methods to avoid these limitations |1,2|. One oI the studied approaches
    consists in the development oI stimuli-responsive membranes, which are capable oI changing their structural and chemical
    characteristics in response to external stimuli, allowing not only a Iouling reduction, but also the use oI tailor-made membranes
    Ior speciIic processes.
    This work is Iocused in the development oI photo-responsive membranes, using as starting material commercial
    polyethersulIone membranes which are then graIted with photocromic compounds such as azobenzenes (Figure 1) |3|, using a
    UV-graIting technique |1,2|. A reversible response oI the membrane to light is expected, allowing a control oI its
    physicochemical and morphological characteristics in a non-invasive way.
    Studies regarding the membrane selectivity, permeability, physicochemical and morphologial changes, as well as, Iouling will
    be discussed. Several membrane characterisation techniques - atomic Iorce microscopy (AFM), dynamic contact angle
    measurements and FTIR-ATR among others are used in order to obtain a deep knowledge oI the eIIect oI membrane graIting
    -234-
    Fig. 1. Resulting hydrodynamic layer thickness oI
    PDMAEMA on PET TEM dependant on degree oI
    graIting
    UV light
    Vis light/
    /dark
    9

    A
    5
    .
    5

    A
    Planar Non planar
    Figure 1 -Trans-cis isomerization oI azobenzene, inducing changes in the dipole
    moment and molecular length.
    and its Iinal structural characteristics and perIormance. These studies aim Ior the optimization oI the graIting methodology,
    thus leading to a more eIIicient membrane response.
    Fabio R. P. Oliveira acknowledges Fundao para a Cincia e a Tecnologia, Portugal, for the PhD scholarship.
    |1| H. Susanto, M. Balakrishnan, M. Ulbricht. Via surIace Iunctionalization by photograIt copolymerization to low-Iouling
    polyethersulIone-based ultraIiltration membranes. J. Membr. Sci 288 (2007) 157-167.
    |2| M. Taniguchi, G. BelIort. Low protein Iouling synthetic membranes by UV-assisted surIace graIting modiIication: varying
    monomer type. J. Membr. Sci 231 (2004)147-157.
    |3| M. Moniruzzaman, Christopher J. Sabey, Gerard F. Fernando. Synthesis oI azobenzene-based polymers and the in-situ
    characterization oI their photoviscosity eIIects. Macromolecules 2004, 37,2572-2577.
    PA.5.9
    Porous membranes modified by polyelectrolytes
    J. Kochan
    1
    , T. Wintgens
    1,2
    , J. E. Wong
    3
    , T. Melin
    1
    1
    Aachener Jerfahrenstechnik, Lehrstuhl fr Chemische Jerfahrenstechnik, RWTH Aachen Universitv, Turmstr. 46, 52056
    Aachen, Germanv
    2
    Fachhochschule Nordwestschwei:, Hochschule fr Life Sciences, Institut fr Ecopreneurship, Grndenstrasse 40, 4132
    Mutten:, Swit:erland
    3
    Institute of Phvsical Chemistrv, RWTH Aachen Universitv, Landoltweg 2, 52056 Aachen, Germanv
    jozeI.kochanavt.rwth-aachen.de
    The layer-by-layer selI-assembly oI polyelectrolytes (LBL) has recently attracted attention Ior the preparation oI thin Iilms due
    to the versatility oI the build-up process |1-2|. However, most oI the studies devote only to LBL build-up and parameters
    aIIecting its properties. Less work has been carried out on the investigation oI stability and separation perIormance.
    In this study layers Iormed oI strong polyelectrolytes such as branched poly ethylenimine (PEI) and poly
    diallyldimethylammonium chloride (PDADMAC) as well as a weak polyelectrolyte poly allylamine chloride (PAH) on various
    materials have been investigated in order to observe modiIication Ieasibility oI this technique Ior membrane application.
    Common membrane characterization methods such as permeability measurement, contact angle, molecular weight cut-oII
    (MWCO), X- ray photo spectroscopy have been applied to prove presence oI layers on the surIace. Moreover, short term
    Iiltration tests with water and sodium hypochlorite solution reveal layer stability during Iiltration and chemical backwashing.
    Figure 1: Fouling rates and TOC retentions oI unmodiIied and PDADMAC modiIied membranes
    Furthermore, poly styrenesulIone (PSS) is used to enable building up two and three layers polyelectrolyte complexes, PEI/PSS,
    PDADMAC/PSS, PEI/PSS/PDADMAC have been created on the polyethersulIone membrane surIace by the layer by layer
    technique. AIter modiIication, sludge supernatant has been used as a Ieed Ior Iiltration and its permeation through mono-, bi-,
    and three-layer polyelectrolyte systems on membranes has been measured and characterized. Lowered MWCO values along
    with enhanced total organic carbon rejection and high perIormance size exclusion chromatography results conIirm improved
    separation perIormance oI polyelectrolyte-modiIied membranes.
    |1| R. Schach, H. Hommel, H. van Damme, P. Dejardin, C. Amsterdamsky, Formation oI weak polyelectrolyte multilayers
    studied by spin labelling, Langmuir 20 (2004) 3173-3179.
    |2| N. G. Hoogeveen, M. A. Cohen Stuart, G. J. Fleer, M. R. Bhmer, Formation and stability oI multilayers oI polyelectrolytes,
    Langmuir 12 (1996) 3675-3681.
    -235-
    PA.5.10
    Gas and vapour permeation through ODPA-ODA membranes with different
    content of cucurbit6]uril nanofillers
    K. Friess
    1
    , J.C. Jansen
    2
    , A. Figoli
    2
    , V. Sindelar
    3
    , J. Svec
    3
    , P. Sysel
    4
    , V. Hynek
    1
    , O. Vopicka
    1
    ,
    M. Zgazar
    1
    , M. Sipek
    1
    1
    Department of Phvsical Chemistrv, Institute of Chemical Technologv, Technicka 5, 166 28 Prague 6, C:ech Republic
    2
    Institute for Membrane Technologv, ITM-CNR, Jia P. Bucci 17/C, 87030 Rende (CS), Italv
    3
    Department of Chemistrv, Masarvk Universitv, Kamenice 5, 625 00 Brno, C:ech Republic
    4
    Department of Polvmers, Institute of Chemical Technologv, Technicka 5, 166 28 Prague 6, C:ech Republic
    karel.Iriessvscht.cz
    Studied membranes were prepared Irom 4,4-Oxybisphthalic anhydride}(ODPA) which was heated overnight in vacuum
    beIore use and Irom 4,4-Oxydianiline (ODA) which was used as received. The polyimide precursor, polyamic acid (PAA),
    with uncontrolled number-average molecular mass was synthesized by the reaction oI equimolar amounts oI ODPA and ODA
    in Methyl-2-pyrrolidone (NMP) solution (content 10 wt.) at room temperature Ior 24 h. The membranes were prepared by
    dispersion oI the Iiller (additive) in NMP solution oI PAA by stirring Ior at least 2 h and subsequent casting the mixture on a
    glass substrate and heated 60/12, 100/1, 150/1, 200/2 and, Iinally, 230
    o
    C/1 h. The content oI two types oI cucurbit|6|uril
    nanoIillers in the Iilm was 5 -15 wt..
    Permeation experiments of single gases were carried out in a fixed volume-pressure increase instrument [1].
    Circular membranes with an effective exposed area of 11.30 cm
    2
    , the measurements were carried out at 25C and
    with feed pressures about 1 bar. For permeation of organic vapours the differential flow apparatus with carrier gas
    H2 was used [2]. From experimental data the permeation and diffusion coefficients were evaluated.
    O
    N N
    O
    O O
    O
    n

    O
    Figure 1. Schematic draw oI ODPA-ODA structure
    The authors are grateIul Ior the Iinancial support Irom the Ministry oI Education, Youth and Sports MSM (Grant No.
    6046137307 and 6046137302) and the Grant Agency oI the Czech Republic (Grant No. 104/09/1357 and GACR
    203/07/P382).
    |1| M. Macchione, J.C. Jansen, G. De Luca, E. Tocci, M. Longeri and E. Drioli, Experimental analysis and simulation oI the
    gas transport in dense HyIlon

    AD60X membranes: InIluence oI residual solvent, Polymer, 48 (2007) 2619.


    |2| K. Friess, M. Sipek, V. Hynek, P. Sysel, K. Bohata and P. Izak, Comparison oI permeability coeIIicients oI organic vapors
    through non-porous polymer membranes by two diIIerent experimental techniques, J.Membr.Sci., 240 (2004) 179.
    PA.5.11
    Binary mixture transport through polyimide membranes with two different types
    of CB6 nanofillers
    K. Friess
    1
    , V. Hynek
    1
    , O. Vopicka
    1
    , M. Zgazar
    1
    , M. Sipek
    1
    , J.C. Jansen
    2
    , A. Figoli
    2
    , V. Sindelar
    3
    ,
    J. Svec
    3
    , P. Sysel
    4
    1
    Department of Phvsical Chemistrv, Institute of Chemical Technologv, Technicka 5, 166 28 Prague 6, C:ech Republic
    2
    Institute for Membrane Technologv, ITM-CNR, Jia P. Bucci 17/C, 87030 Rende (CS), Italv
    3
    Department of Chemistrv, Masarvk Universitv, Kamenice 5, 625 00 Brno, C:ech Republic
    4
    Department of Polvmers, Institute of Chemical Technologv, Technicka 5, 166 28 Prague 6, C:ech Republic
    karel.Iriessvscht.cz
    Two diIIerent type oI nanoIillers were prepared and imbedded (5 -15 wt. ) into ODPA-ODA membrane structure. The Iirst
    type, cucurbit|6|uril(CB6), was prepared according known procedure reported previously |1|. The second type the complex
    oI CB6 and hexa-methylene ammonium chloride (HMDA)- was prepared by adding oI CB6 into the solution oI
    -236-
    hexamethylenediamine in water. Few drops oI diluted HCl were added to bring pH oI the solution between 2 and 3. AIter
    stirring Ior 1 h at room temperature, undissolved CB was Iiltered oII. Addition oI acetone to the solution produced a
    precipitate, which was Iiltered and dried in the oven. The
    1
    H NMR analysis proved that the obtained compound is inclusion
    complex CB6HMDA with structure presented on Figure 1.
    The binary mixture transport oI methanol MTBE, methanol toluene and methanol ethanol through ODPA-ODA
    membranes with both types oI CB6 nanoIillers were studied by vapour permeation |2| and pervaporation |3|. PerIorming such
    experiments in liquid and vapour phases enabled to reveal the eIIect oI each nanoIiller on membrane transport properties at
    diIIerent phase conditions.
    N
    N N
    O
    O
    CH
    2
    N
    CH
    2
    H H
    H
    3
    N
    NH
    3
    H
    3
    N
    NH
    3
    6
    +
    +
    +
    CB6
    HMDA
    CB6@HMDA
    +
    Figure 1. Schematic draw oI CB6HMDA complex
    The authors are grateIul Ior the Iinancial support Irom the Ministry oI Education, Youth and Sports - MSMT (Grant No.
    6046137307 and 6046137302) and the Grant Agency oI the Czech Republic (Grant No. 104/09/1357 and GACR
    203/07/P382).
    |1| P. Sysel, K. Friess, V. Sindelar, T. Koptikova, V. Hynek, M. Sipek, Polyimides based on xylylene-diamines containing
    cucurbit|6|uril. Polvmer Preprints, 2007, vol. 2007, no. 48, 312.
    |2| K. Friess, J. C. Jansen , O. Vopicka,

    A. Randova, V. Hynek,
    ,
    M. Sipek, L. Bartovska, P. Izak, M. Dingemans, Jo DewulI,
    H.Van Langenhove, E. Drioli: Comparative study oI sorption and permeation techniques Ior the determination oI heptane and
    toluene transport in polyethylene membranes. (Submitted into J. Membrane Sci. in November 2008).
    |3| B.Van der Bruggen, J.C. Jansen, A. Figoli, J. Geens, K. Boussu, E. Drioli, A universal` membrane suitable Ior gas
    separation, pervaporation and nanoIiltration applications, Journal of Phvsical Chemistrv B 110 (28), (2006) 13799-13803.
    PA.5.12
    Modification of ultra- and microfiltration membranes with titanium dioxide
    M.T.P. de Amorim
    1
    , A. Moro
    2
    , S.M.S. Marques
    3
    , C. Tavares
    3
    , R. Bergamasco
    4
    1
    Department of Textile Engineering, Minho Universitv, Campus de A:urem, 4800-058 Guimare, Portugal
    2
    CICS-Department of Health Sciences, Universitv of Beira Interior, 6201, Covilh, Portugal
    3
    Department of Phvsics, Minho Universitv, Campus de A:urem, 4800-058 Guimare, Portugal
    4
    Department of Chemical Engineering, Av. Colombo., 5790, State Universitv of Maringa, Maringa, Bra:il.
    mtamorimdet.uminho.pt
    The separation processes with membranes has been commonly applied in the recycling and treatment oI wastewaters Irom the
    textile industry. Nevertheless, the high concentration oI organic pollutants in theretentate stream Iorces the implantation oI
    some other processes oI puriIication. The immobilization oI titanium dioxide onto membranes, allows to obtained a hybrid
    process which reconcile the photocatalytic oxidation oI the semiconductor with the separation oI the membranes would
    eliminate the need oI a post wastewater treatment.
    This paper compares the permeability and rejection oI the original microIiltration membranes oI cellulose acetate and
    polyethersulIone ultraIiltration membranes with those obtained aIter deposition oI dioxide oI titanium Iilms at room
    temperature by pulsed-Irequency reactive magnetron sputtering Irom a high putity Ti target in an Ar/O
    2
    atmosphere.
    The hydraulic permeability oI the treated and untreated membranes, the adsorption and rejection oI dyestuIIs were
    accomplished. They were equally submitted to wash tests and Iiltration to veriIy the losses oI the activity oI the semiconductor
    with the time.
    In the experiments oI adsorption and dye rejection was used solutions oI methylene blue and a commercial dye the Remazol
    Blue Brilliant R Special. The results oI water permeability show an increase oI the Ilux with the membranes treated with
    dioxide oI titanium, 25 with the microIiltration membrane and 100 Ior the microIiltration membranes. The experiments oI
    static adsorption with the membranes when in presence oI the solutions oI the dyes show a smaller adsorption with the treated
    membranes. SigniIicant water Ilux reductions were observed aIter static adsorption Ior the UF membranes, original and treated
    with titania. (9.5 and 25.4 respectively). Similar behaviour was observed with the MF membranes. The study oI the
    -237-
    photocatalytic eIIect was obtained by exhibition oI the membranes with the adsorbed dye to the solar radiation, in both cases
    the discoloration oI the membranes is observed, being the degradation speed in the membranes treated about oI 20 times
    greater than oI the membranes without titanium dioxide Iilms.
    PA.5.13
    Preparation of mono-dispersed chitosan microcapsules using SPG membrane
    emulsification technique
    K. Akamatsu, D. Kaneko, T. Sugawara, R. Kikuchi, S. Nakao
    Department of Chemical Svstem Engineering, The Universitv of Tokvo, 7-3-1 Hongo, Bunkvo-ku, Tokvo 113-8656, Japan
    akamatsuchemsys.t.u-tokyo.ac.jp
    Mono-dispersed and size-controlled chitosan microcapsules were successIully prepared using SPG membrane emulsiIication
    technique. In this study, three methods were employed to prepare chitosan microcapsules; (1) cross-linking with
    glutaraldehyde, (2) interaction with alginate, and (3) in-liquid drying using aqueous sodium hydroxide. In all cases, the
    microcapsules were mono-dispersed, and the average diameters oI the microcapsules could be controlled by the concentration
    oI chitosan and the pore size oI SPG membranes. In addition, the reaction mechanisms oI the Iorming oI chitosan
    microcapsules were also elucidated under various experimental conditions.
    PA.6.1
    Development of a biomimetic scaffold for transmembrane protein incorporation
    S. Ibragimova
    1,2
    , J.S. Hansen
    1,3
    , M. Perry
    1
    , T. Vissing
    1
    , K.B. Stibius
    1,2
    , J. Vogel
    1,3
    ,
    O. Geschke
    3
    , J. Emneus
    3
    , C.H. Nielsen
    1,2
    1
    Aquaporin A/S, Diplomvef 377, DK-2800 Kgs. Lvngbv, Denmark
    2
    Quantum Protein Centre, DTU Phvsics, Technical Universitv of Denmark, DK-2800 Kgs. Lvngbv, Denmark
    3
    DTU Nanotech, Technical Universitv of Denmark, DK-2800 Kgs. Lvngbv, Denmark
    claus.nielsenIysik.dtu.dk
    Transmembrane proteins have many Iunctions in biological systems, acting as Ior example channels, receptors or transporters.
    Aquaporin, a highly selective transmembrane water channel Iound in all living organisms |1, 2|, is oI special interest due to its
    rapid turn-over oI water which makes it very attractive Ior industrial water Iiltration applications. To study aquaporin or any
    transmembrane protein, the protein must be in its native conIormation and thereIore needs to be incorporated into a matrix that
    resembles the proteins in vivo environment. We report the development oI a biomimetic scaIIold Ior the incorporation oI
    transmembrane proteins, comprising selI-assembled lipid bilayers suspended in multi-aperture hydrophobic partitions made by
    laser ablation in a Iilm oI ethylene tetraIluoroethylene (ETFE). PerIoration oI hydrophobic ETFE partitions with 8x8
    rectangular arrays oI 301+5m aperture diameter was routinely done using a carbon dioxide laser. We also report an
    automation technique developed in our group, known as the AutoPaintedMembrane (APM) technique. It is used Ior
    establishing black lipid membranes across multi-aperture arrays in ETFE Iilms. The lipid membranes are supported by a
    microporous hydrophilic material, e.g. cellulose. An amphiphile/hydrocarbon solution is used to pre-coat the ETFE partition
    surIace with amphiphiles and the solvent is evaporated. Membrane assembly is carried out by raising a layer oI
    amphiphile/hydrocarbon solution past the pre-coated apertures thereby Iorming amphiphilic layers across the apertures .
    Membrane Iormation and membrane characteristics were monitored using electrophysiological measurements. Lipid
    membranes could be Iormed in the 8x8 aperture arrays in the ETFE partitions. Success rates Ior establishment oI cellulose-
    supported BLMs across multi-aperture arrays were above 95 and the membranes showed liIetimes oI up to two weeks. The
    ionophoric peptide valinomycin was incorporated into the membrane arrays, resulting in increased membrane conductance due
    to ionic currents. The addition oI tetraethylammonium blocked the valinomycin channels and resulted in decreased membrane
    conductance. Incorporated valinomycin in lipid bilayers showed that membranes were established in the multi-aperture array
    and that it was possible to incorporate membrane-spanning molecules in the Iormed membranes.
    |1| Tajkhorshid, E., Nollert, P., Jensen, M., Miercke, L., OConnell, J., Stroud, R., and Schulten, K., Control of the selectivitv
    of the aquaporin water channel familv bv global orientational tuning. Science, 2002. 296(5567): pp. 525-530.
    |2| Pohl, P., Combined transport of water and ions through membrane channels, Biol. Chem., 2004. 385(10): pp. 921-926.
    -238-
    |3| Hansen, J.S., Perry, M.E., Vogel, J., Vissing, T., Hansen, C. R., Geschke, O., Emneus, J., and Nielsen, C.H., Development
    of an automation technique for the establishment of functional lipid bilaver arravs. J. Micromech. Microeng., in press.
    PA.6.2
    Characterization of a permselective structure for support/encapsulation of specific
    substances
    L. Pelaez
    1
    , S. Bijani
    1
    , S. Escaler
    1
    , M.I. Vazquez
    1
    , J. Benavente
    1
    , S. Ibragimova
    2,3
    , K.B. Stibius
    2,3
    , C. Helix-Nielsen
    2,3

    1
    Dept. Fisica Aplicada I. Ftd. de Ciencias, Universidad de Mala,. E-29071 Malaga, Spain
    2
    Aquaporin A/S, Diplomvef 377, DK2800 Lvngbv, Denmark
    3
    DTU Phvsics, Building 309 Technical Universitv of Denmark, DK2800, Lvngbv, Denmark
    chnaquaporin.dk
    Membrane systems Ior new and emerging applications mostly consist oI composite materials. These may contain particular
    substances conIerring speciIic permselectivity to the membrane device Ior e.g. sensor, diIIusion release, encapsulation, and
    energy conversion applications. The choice oI the support, partitioning or encapsulation systems (materials and structures) is
    crucial Ior the stability and optimization oI the membrane process. It is thereIore necessary to consider the diIIerent structures
    involved in the process. Hydrogels are oI particular interest. They are cross-linked hydrophilic polymers swollen in
    water/aqueous solutions and their structure is oIten described as a mesh, with the spaces between the polymer chains Iilled by
    water.
    This work presents the results obtained in the characterization oI a preliminary composite-membrane structure Ior
    incorporation oI a protein (aquaporin) Ior water puriIication purposes. The composite consists oI a regenerated cellulose (RC)
    membrane (support), a teIlon layer with 8x8 small holes Ior mass/charge transport (partitioning) plus a hydrogel (Gel) placed
    between these two sublayers (RCGelTeIlon system). The hydrogel studied in this work was obtained by radical
    polymerisation oI an acrylate-based monomer using photoinitiation.
    Transport characterization was perIormed by determining salt and water diIIusivities, ion transport numbers and electrical
    resistance, which were obtained Irom NaCl and titrated water diIIusion experiments, membrane potentials and electrochemical
    impedance spectroscopy (EIS) measurements, respectively. The inIluence oI gel on transport parameters was obtaining by
    comparing the results obtained Ior the RCGelTeIlon and RCTeIlon systems. As expected, the presence oI the gel reduces
    water and salt permeabilities, but it hardly modiIies the cation (Na

    ) transport number. In addition according to EIS data the


    presence oI the hydrogel reduce the hydrophobicity oI the TeIlon layer, and as a result oI this substantial diIIerences in the
    electrical resistance were obtained.
    PA.6.3
    Facilitated transport of CO
    2
    through carbonic anhydrase-immobilized
    poly(vinyl alcohol) beads
    G.N.B. Baroa, J. Kim, D.-E. Hong, B. Jung
    Laboratorv of Environmental and Energv Materials, Department of Environmental Engineering & Biotechnologv, Mvongfi
    Universitv, San 38-2 Namdong, Yongin, Gveonggido 449-728 Republic of Korea
    gbaronamju.ac.kr
    Carbonic anhydrase (CA), the most powerIul catalyst known to catalyze the transIormation oI CO
    2
    to bicarbonate ion,

    can
    hydrate at least 1.4 x 10
    6
    molecules oI CO
    2
    per second |1-3|. With its great CO2-sequestration potential, carbonic anhydrase
    was immobilized into PVA-sodium alginate beads through covalent binding with cyanogen bromide (CNBr) (Fig. 1) |4|.
    DiIIerent immobilized CA concentrations were controlled by immersing the activated polymer beads into diIIerent
    concentrations oI CA suspended solution. The enzyme activity and permeability were evaluated using a bead reactor at
    diIIerent conditions such as applied CO
    2
    concentration, pH oI the medium, and temperature.
    -239-
    |1| S.J. Dodgson, R.E. Tashian, G. Gros, N.D. Carter, Eds., The Carbonic Anhydrases: A Cellular Physiology and Molecular
    Genetics, Plenum Press: New York, 1991.
    |2| Y. Pocker, Enzymatic and Model Carboxylation and Reduction Reactions Ior Carbon Dioxide Utilization, NATO ASI
    Series, Series C: Mathematical and Physical Sciences, M. Aresta, J.V. Schloss, Eds., Kluwer Academic Publishers: Dordecht,
    1990, Vol. 314, pp. 129-143.
    |3| R.G. KhaliIah, D.N. Silverman, The Carbonic Anhydrases: Cellular Physiology and Molecular Genetics, S.J. Dodgson,
    R.E. Tashian, G. Gros, N.D. Carter, Eds., Plenum Press: New York, 1991, pp. 49-70.
    |4| R. Alex, Chemical Iixation oI enzymes to cyanogen halide activated polysaccharide carriers, Eur. J. Biochem., 18 (1971)
    351-360.
    PA.6.4
    Properties of the transport of Cu(II) across affinity membranes containing the
    3-phenyl-4-benzoylisoxazol-5-one as carrier
    L. Mitiche
    1
    , S. Tingry
    2
    , P. Seta
    2
    , A. Sahmoune
    1

    1
    Laboratoire de Recherche sur lEau, Universite Mouloud Mammeri, BP 17, 15000 Ti:i-Ou:ou, Algeria
    2
    Institut Europeen des Membranes, UMR 5635, ENSCM-CNRS-UM2, Place Eugene Bataillon, CC 047, 34095 Montpellier,
    cedex 5, France
    asahmouneyahoo.Ir
    The transport oI Cu (II) metal ions Irom aqueous nitrate solutions was studied by supported liquid membrane (SLM) using the
    carrier 3-phenyl-4-benzoylisoxazol-5-one (HPBI) in the solvents chloroIorm, 2-nitro phenyl octyl ether (NPOE) and dodecyl
    nitro phenyl ether (DNPE). The eIIiciency oI the transport was optimized as a Iunction oI the aqueous components (pH, T,
    carrier concentration) and the membrane composition |1|. The higher copper Ilux value was obtained with the solvent oI lower
    dielectric constant, it Iollows the order CHCl
    3
    ~ DNPE ~ NPOE. A maximum oI 60 oI Cu (II) was extracted by the
    membrane in one day. The transport mechanism consists oI the diIIusion oI Cu(PBI)
    2
    complex in the membrane and the
    copper transport was better enhanced in SLM than in PPM containing HPBI. A comparative transport oI Cu (II), Zn(II) and Cd
    (II) ions by SLM was also studied. It is Iound that HPBI carries these metal ions in the sequence Zn
    2
    ~Cu
    2
    ~Cd
    2
    .
    |1| L. Mitiche, S. Tingry, P. Seta, A. Sahmoune, J. Memb. Sci., 325 (2008) 605.
    -240-
    Fig.1. Schematic method Ior enzymatic
    CA coupling reactions
    PA.6.5
    Toxic metallic ion extraction using polymer inclusion membranes (PIMs)
    O. Kebiche-Senhadji
    1
    , L. Mansouri
    1
    , S. Tingry
    2
    , P. Seta
    2
    , M. Benamor
    1
    1
    Laboratoire des Materiaux Organiques, Universite de Befaia, DZ-06000, Befaia (Algeria)
    2
    Institut Europeen des Membranes, UMR 5635, ENSCM-CNRS-UM2, Place Eugene Bataillon, CC 047, 34095 Montpellier,
    cedex 5, France
    kebicheanissayahoo.Ir
    The need oI more speciIic practical systems Ior recovery oI dilute metal species in liquid media, Irom both ecological and
    economic aspects, has led to the development oI new separation techniques |1|. Current techniques oI metal ion recovery use
    solvent extraction separations, consuming large amounts oI energy and reactants that impose both environmental and health
    hazards. However, the recent development oI a novel type oI liquid membrane, commonly called Polymer Inclusion
    Membranes (PIMs), can be seen as an environmentally conservative alternative to the current methods available Ior separation
    and recovery oI metal ions |2|. PIMs designed Ior Iacilitated transport oI metallic ions consist oI the three main components: a
    polymer, a plasticizer and a carrier. A delicate balance exists between the components oI the PIMs that governs the
    perIormance oI the membrane during its use in extracting metallic ions.
    This study aims to optimise the extraction perIormance oI toxic metallic ions (Cd(II), Cr(VI)) by PIMs consisting oI CTA or
    PVC as the base polymers, 2-NPOE as the plasticizer and Aliquat 336 as the carrier. The Iractions oI base polymers and oI the
    carrier Aliquat 336 were varied to determine the optimum composition with respect to extraction capability oI the membranes.
    PIMs have shown a very good stability in the case oI the Iacilitated transport oI (Cd II) ions |3|. Concerning the transport oI
    the Cr (VI) the CTA/PIM based is more stable than the PVC/PIM based.
    PA.7.1
    Synthesis and electrochemical characteristics of polysulfone-polyaniline-carbon
    nanotubes asymmetric composite membranes
    S.I. Voicu, A.C. NechiIor, D.I. Vaireanu, G. NechiIor
    Universitv POLITEHNICA of Bucharest, Facultv of Applied Chemistrv and Materials Sciences, Str. Gheorghe Poli:u 1-7
    011061 Bucharest, Romania
    svoicugmail.com
    In order to combine the advantages oI polysulIone (PSI) as a membrane material (high thermal resistance, chemical resistance
    over the entire pH range, inert behaviour in oxidative environments, increased mechanical resistance oI the Iilms subjected to
    Iracture, Ilexure, torsion tests, moderate reactivity in aromatic electrophile substitutions reactions) to that oI polyaniline as a
    conductive polymer (inexpensive, Iairly good charge conductivity and controllable electrochemical processability) and carbon
    nanotubes as highly conductive molecules with special properties (high mechanical and thermal resistance, very good
    electronic conductivity), one has attempted to obtain novel polysulIone-polyaniline-carbon nanotubes composite membranes
    by a newly improved technique comparing to the existing ones. The strong point oI this technique consists in a phase
    inversion by immersion precipitation accompanying by chemical reaction. PSI-aniline system was studied to membrane
    Iormation through phase inversion by immersion precipitation (into a coagulation bath containing cyclohexanol) combined
    with a chemical oxidation reaction oI aniline (in the presence oI ammonium peroxydisulIate in acidic solution), process that
    leads to the Iormation oI polysulIone-polyaniline composite membranes. The above synthesized membranes were structurally
    characterized using SEM, TEM, FT-IR spectroscopy, thermal analysis. The ionic conductivity was also determined by
    Electrochemical Impedance Spectroscopy using a novel electrochemical cell that allows the precise determination oI
    membrane thickness during the measurements in order to minimize the determination error that may appear when one
    considers the presumed or dry membrane thickness instead oI the actual activated membrane. The evaluated properties indicate
    diIIerent possible applications Ior this material like micro-capacitors, support Ior diIIerent sensor devices, electronic and optic
    use solvents puriIication, colorants and proteins nanoIiltration.
    -241-
    PA.7.2
    ~Smart performance of hydrogel pore-filled stimuli-responsive membranes
    N. Adrus
    1,2
    , M. Ulbricht
    1
    1
    Lehrstuhl fr Technische Chemie II, Universitt Duisburg-Essen, Universittsstrasse 5, Essen, 45141, Germanv
    2
    Polvmer Engineering Department, Facultv of Chemical & Natural Resources Engineering, Universiti Teknologi Malavsia,
    UTM Skudai, Johor 81310, Malavsia
    nadia.adrusstud.uni-due.de
    Functional pore-Iilled composite membranes (FPFCM) were
    successIully prepared via in situ photoinitiated crosslinking
    copolymerization. In our recent work |1|, we have demonstrated that: (i)
    poly(N-isopropylacrylamide) (PNIPAAm) hydrogel was proven to be
    evenly and tightly Iilled in the pore oI polyethylene terephthalate track-
    etched membranes (5.0 m nominal pore diameter), and (ii) the transport
    through these FPFCM was regulated by the action oI the temperature
    responsive PNIPAAm hydrogel.
    In this paper, the 'smart Ieatures oI hydrogel FPFCM under ultraIiltration and diIIusion conditions are Iurther explored. For
    that purpose, 'conventional PNIPAAm hydrogels (prepared in pure water) with various crosslinking density were synthesized
    in the membrane pores. The preparation oI FPFCM also has been extended to 'porous PNIPAAm hydrogels (prepared in the
    presence oI polyethylene glycol, inducing phase separation during crosslinking copolymerization). The hydrogel FPFCM
    exhibit size selective transport oI solutes due to sieving properties oI the gel network (as a Iunction oI crosslinking density) and
    also because oI the stimuli-responsiveness oI the PNIPAAm. The barrier pores oI the FPFCM can be enlarged or shrunk as the
    crosslinked PNIPAAm swells or deswells in the vicinity oI its lower critical solution temperature (LCST~ 32C) (cI. |2|). As a
    result, the permeability measured below LCST was signiIicantly reduced compared to permeability above LCST. By increasing
    degree oI crosslinking, we supposed a Iurther decrease in permeability. In addition, the structure heterogeneity and Iaster
    response rate imposed by the porous hydrogels (cI. |3|) Iacilitated the transport through the FPFCM and their response to
    temperature change. Finally, the pre-Iunctionalization step by graIting linear PNIPAAm chains to membrane pore wall was
    perIormed. This step was able to avoid the hydrogels structure Irom delamination during measurement either above the LCST
    oI the hydrogels or at a higher transmembrane pressure. In brieI, the novel hydrogel FPFCM show 'smart separation
    perIormance.
    |1| N. Adrus, M. Ulbricht, Development oI Pore-Filling Stimuli-Responsive Membranes with Polymer Hydrogel Systems,
    Regional ConIerence on Materials, Malaysia, February 2009.
    |2| L.Y. Chu, T. Nitsuma, T. Yamaguchi, S.I. Nakao, Thermoresponsive Transport through Porous Membranes with GraIted
    PNIPAM Gates, AIChe J., 2003, 49, 896-909.
    |3| X.Z. Zhang, X.D. Xu, S.X. Cheng, R.X. Zhuo, Strategies to improve the response rate oI thermo-sensitive PNIPAAm
    hydrogels, SoIt Matter, 2008, 4, 385-391.
    PA.7.3
    Fabrication by PECVD of super-hydrophobic surface without fluorine
    C.-H. Lo
    1,2
    , V. Rouessac
    1
    , K.-R. Lee
    2
    , J.-Y. Lai
    2
    1
    IEM, ENSCM-UM2-CNRS UMR5635, Universite Montpellier 2, place Eugene Bataillon, 34095 Montpellier cedex 5, France
    2
    CMT, Chung Yuan Universitv, 493 Sin Chung Pei Rd., Chung Li, Taiwan, 32083, R.O.C.
    vincent.rouessaciemm.univ-montp2.Ir
    In daily liIe, various industrial products require not only hydrophilicity but also hydrophobicity. Currently, a surIace with a
    water contact angle above 150 (deIined as a super-hydrophobic surIace) have been considered as a technological potential Ior
    many practical applications such as water repellence, Iog condensation, and selI-cleaning, because oI their extreme water-
    repellent properties. The contact angle strongly depends on surIace energy and surIace microstructure |1-2|. However, the
    surIace energy is an intrinsic property oI materials. When the eIIects oI surIace structure can be ignored, surIace could attain
    the maximum oI water contact angle merely by lowering the surIace energy, about 120 |1|.A suitable surIace morphology is
    necessary to produce super-hydrophobic surIace. Up to now, many methods have been developed to produce rough surIaces,
    including etching |3|, plasma-enhanced chemical vapor deposition (PECVD) |4-5|, phase separation |6|, and sol-gel |7|. But
    -242-
    Figure 1: Stimuli-responsive features of
    hydrogel FPFCM


    most oI them use Iluorine-contained precursors and are multi-step processes.In this study, super-hydrophobic thin Iilms were
    successIully prepared by low Irequency capacitively coupled PECVD reactor in a single step process using precursor without
    Iluorine, i.e. hexamethyldisiloxane (HMDSO). The water contact angle oI plasma polymerized Iilms (PP-Iilms) prepared on
    the power-driven electrode increase with HMDSO ratio in the Ieed and total pressure. However, super-hydrophobic surIace
    was concentrated on electrode position close to the precursor inlet, whereas this surIace shows powder type and high
    roughness. It was also Iound that water contact angle on the PP-Iilms changed with the droplet volume. Water droplet volume
    larger than 8l showed a high water contact angle because oI deIormation oI droplet due to gravity eIIect. Compared with
    continuous plasma, pulsed plasma can reduce not only the Iragmentation oI HMDSO (showed a higher intensity ratio I
    2958
    (-
    CH
    3
    )/I
    1041
    (Si-O-Si) in FT-IR analysis) but also the eIIect oI ion bombardment on the electrode, indicating that more
    hydrocarbons can be kept on PP-Iilms. However, low Iragmentation means low gas nucleation reaction and low deposition rate
    in plasma region. It would result in production oI a smooth surIace and lower water contact angle (~ 100). PP-Iilms with
    diIIerent structures are obtained on diIIerent position oI the electrode. PP-Films are also produced out oI the electrodes gap.
    Their surIace displayed a particle-type and water contact angle reached to 170.
    |1| A. Nakajima, K. Hashimoto, T. Watanabe, MonatsheIte Ir Chemie, 132 (2001) 31.
    |2| L. Feng, S. Li, Y. Li, H. Li, L. Zhang, J. Zhai, Y. Song, B. Liu, L. Jiang, D. Zhu, Adv. Mater., 14 (2002) 1857.
    |3| Y. Zhou, X. Song, M. Yu, B. Wang, H. Yan, SurI. Rev. Lett. 13 (2006) 117.
    |4| A. Barranco, J. Cotrino, F. Yubero, J.P. Espinos, L. Contreras, A.R. Gonzalez-Elipe, Chem. Vap. Deposition, 10 (2004) 17.
    |5| M. Lejeune, L.M. Lacroix, F. Bretagnol, A. Valsesia, P. Colpo, F. Rossi, Langmuir, 22 (2006) 3057.
    |6| N. Zhao, J. Xu, Q. Xie, L. Weng, X. Guo, X. Zhang, L. Shi, Macromol. Rapid Comm., 26 (2005) 1075.
    |7| H.M. Shang, Y. Wang, S.J. Limmer, T.P. Chou, K. Takahashi, G.Z. Cao, Thin Solid Films, 472 (2005) 37.
    PA.7.4
    Robust synthesis and performance of a titania-based ultrafiltration membrane with
    photocatalytic properties
    L. DjaIer
    1,2
    , A. Ayral
    1
    , A. Ouaged
    2
    1
    Institut Europeen des Membranes, CNRS-ENSCM-UM2, CC047, Universite Montpellier 2, Place Eugene Bataillon,
    34095Montpellier cedex 5, France.
    2
    Laboratoire Eau Environnement, Universite Hassiba Ben Bouali, BP 151. 02000, Chlef, Algeria.
    andre.ayraliemm.univ-montp2.Ir
    Membrane technology takes an increasing role in water treatment processes Ior both the production oI tap water and the
    treatment and recycling oI waste water. Fouling phenomenon and diIIiculty with retention oI small organic molecules are
    however two important limitations. Direct coupling oI membrane separation and photocatalytic degradation by using
    photocatalytic membranes is an attractive way to overcome such limitations |1, 2|. In Iact, the probability Ior an organic
    pollutant to be in contact with the photoactive walls is very high Ior nanoporous photocatalytic membranes. On the other hand,
    titania is the reIerence material in term oI photocatalytic eIIiciency and also exhibits a very good chemical stability as ceramic
    membrane.
    This study deals with the development oI a robust synthesis oI a titania-based ultraIiltration membrane. Its perIormance in term
    oI separation and photocatalytic activity are investigated. The photocatalytic separative layer is prepared Irom a commercial
    titania sol (Millenium Inorganic Chemicals) deposited on a commercial macroporous alumina support (Pall-Exekia-
    Al
    2
    O
    5
    -200nm). DeIect-Iree layers with a thickness oI about 3 m are observed by scanning electron microscopy (SEM)
    (Figure 1). The pure water permeance is ~ 150 L h
    -1
    m
    -2
    bar
    -1
    and the measured cut-oII is around ~ 50 kDa corresponding to an
    ultraIiltration membrane. The photocatalytic eIIiciency is tested by photooxydation under UV irradiation oI a reIerence organic
    dye (methylene blue) Ior comparison with reIerence titania photocatalysts, and also with phenol as typical organic pollutant in
    water. This presentation will detail the synthesis procedure and will discuss the characterization results.
    -243-
    Figure 1. SEM cross-section image oI the titania layer deposited on the macroporous alumina support.
    |1| F. Bosc, A. Ayral, C. Guizard, J. Memb. Sci. 265 (2005) 13-19.
    |2| L. Naszalyi, F. Bosc, A. El Mansouri, A. van der Lee, D. Cot, Z. Horvolgyi, A. Ayral, Separation and PuriIication
    Technology 59 (2008) 304-309.
    PA.7.5
    Vertically aligned single walled carbon nanotube arrays embedded within a
    covalently linked polymer network on a porous silicon substrate for molecular
    separation
    C. J. Shearer, K. T. Constantopoulos, N. H. Voelcker, J. G. Shapter, A. V. Ellis
    Flinders Universitv, School of Chemistrv, Phvsics and Earth Sciences, Adelaide, SA 5042, Australia
    Cameron.shearerIlinders.edu.au
    The small diameter oI single walled carbon nanotubes (SWCNTs), as well as the recent discovery oI remarkably Iast water
    transport properties, has promoted interest in incorporating vertically aligned SWCNTs (VA-SWCNT) into a membrane Ior
    water Iiltration and Iluid Ilux experiments. Here, we describe the chemical attachment oI carboxylated SWCNTs to an amine-
    terminated silane layer on a porous silicon substrate via a simple selI-assembly method to produce VA-SWCNTs Ior molecular
    separations (see Figure 1). We then impregnated the CNTs by Iirst derivatising the unattached carboxyl groups on the side-
    walls and tops oI the SWCNTs to bis-dithioester chain transIer agents which enabled subsequent surIace initiated reversible
    addition-Iragmentation chain transIer (RAFT) polymerization oI styrene . In this manner, SWCNTs were embedded in a water-
    impermeable covalently attached polymer matrix preventing Iluid Ilow down the outside oI the SWCNTs. An oxygen plasma
    etching technique was then used to remove any excess polymer and open the tops oI the SWCNTs at the membrane surIace
    Iacilitating water transport within the SWCNTs. The Iluid Ilow through the membrane and the separation oI various analytes
    were investigated Ior the CNT membrane and compared with that oI conventional microIiltration membranes.
    Figure 1: Schematic oI preparation oI membrane incorporating vertically aligned carbon nanotubes (VA-CNTs) showing (a)
    porous silicon base, (b) VA-CNT array on porous silicon base (side view in (b`)) and, (c) side view showing embedded
    polystyrene matrix
    -244-
    PA.7.6
    Antimicrobial peptides immobilized on reverse osmosis membranes as a new
    approach to reduce biofouling
    E. Gershkovich
    1
    , K. Berliner
    1
    , E. Hershkovitz
    1
    , Z. Ronen
    2
    , R. Kasher
    1
    1
    Department of Desalination & Water Treatment, Zuckerberg Institute for Water Research, The Blaustein Institutes for Desert
    Research, Ben-Gurion Universitv of the Negev, Midreshet Ben-Gurion 84990, Isreal
    2
    Department of Hvdrologv & Environmental Microbiologv, Zuckerberg Institute for Water Research, The Blaustein Institutes
    for Desert Research, Ben-Gurion Universitv of the Negev, Midreshet Ben-Gurion 84990, Isreal
    kasherbgu.ac.il
    A major problem in nanoIiltration (NF) and in reverse osmosis (RO) processes is bioIouling, caused by adhesion and growth oI
    bacteria to Iorm bioIilm on the membrane surIace. Here we describe the development oI a new approach to reduce bioIilm
    Iormation on RO membranes that is based on covalent attachment oI antimicrobial peptides (AMPs) onto the membrane
    surIace while preserving the peptides antimicrobial activity. AMPs are proposed as they combine highly desired merits: they
    are toxic against a broad range oI bacteria, bacteria do not acquire resistance to it, and they are non toxic to humans. Initially,
    we examined the bactericide activity oI numerous AMPs in conditions that simulate seawater desalinaiton. A bioassay was
    developed based on growing bioIilm-Iorming bacteria in a multi-well microtiter plate and screening peptides activity in normal
    vs. high salinity conditions. The peptides were prepared in our laboratory by solid phase peptide synthesis (SPPS) using Fmoc-
    chemistry. Most peptides lost their activity in high salinity conditions; yet, Iew peptides possessed their bactericide activity and
    were used in subsequent experiments. The next stage was searching Ior mode oI binding oI the AMPs to the membrane surIace
    while retaining the peptide bactericide activity. Tether molecules that are based on polyethylene glycol chains were prepared,
    as well as other small linker molecules such as 6-aminohexanoic acid. We prepared the AMPs modiIied on their amino-
    terminal by such tethers and evaluated peptide-linker bactericide activity in solution. Finally, peptide-linkers that retained the
    bactericide activity were selected and used Ior modiIication oI RO polyamide membranes. The mode oI binding, as well as
    bactericide activity and RO-salt rejection and Ilux properties oI the modiIied membranes will be described. This study may
    establish the Iirst step towards a more general approach to obtain RO and NF membranes which are less susceptible to bioIilm
    growth and bioIouling.
    PA.7.7
    Development of smart composite membranes based on pH-responsive microgel
    particles and inert porous supports
    J. M. Olvera-Marquez, M. J. Ariza
    Complex Fluid Phvsics Group, Department of Applied Phvsics, CITE II-A, Universitv of Almeria, Almeria, Spain
    mjarizaual.es
    In this work, we have tried diIIerent commercial polymeric membranes to entrap microgel nanoparticles responsive to pH by
    Iiltration processes. This strategy has been used with the aim oI developing membranes oI controllable ionic transport
    properties depending on the pH conditions, so called smart membranes. Inert porous supports oI diIIerent polymeric materials
    (polysulIone, polyamide and cellulose) and diIIerent pore sizes have been tried. The selected pH-responsive material has been
    aqueous suspension oI poly(2-vinyl pyridine) (p-2VP) colloidal particles (about 200 nm diameter). Microstructure oI both
    porous supports and composite membranes was studied by scanning electron microscopy. Figure 1 shows the inner surIace oI a
    polyamide (leIt) and polysulIone (right) support covered or loaded with responsive microgel particles. Salt permeability (P
    s
    ) oI
    the developed membranes was determined by diIIusion experiments under ionic concentration gradients. This transport
    parameter has been used to check the inIluence oI the pH-responsive particles on the ionic transport across the composite
    membranes. The P
    s
    results reveal that the ionic and water transport depends on pH and salt concentration, which can be
    interpreted in terms oI the variation oI the microgel swelling state depending on the environmental conditions.
    -245-
    Figure 1: SEM images oI the inner surIace oI a (p-2VP)/polyamide (leIt) and (p-2VP)/polysulIone (right) composite
    membranes. Both membranes behave as smart membranes which ionic transport depends on the media pH
    This work has been Iinanced by Junta de Andalucia under project P06-FQM-01869.
    PA.7.8
    Development of inorganic layers in supercritical CO
    2
    media. An original approach to
    prepare silica based membranes
    V. Durand
    1
    , J-C. Ruiz
    1
    , S. Sarrade
    2
    , C. Guizard
    3
    , A. Julbe
    4
    1
    CEA Marcoule DEN/DTCD/SPDE/Laboratoire des Fluides Supercritiques et Membranes, BP 17171 30207 Bagnols sur
    Ce:e, France
    2
    CEA Marcoule DEN/DTCD/SPDE/DIR, BP 17171 30207 Bagnols sur Ce:e, France
    3
    Laboratoire de Svnthese et Fonctionnalisation des Ceramiques, (UMR 3080) CNRS / SAINT-GOBAIN C.R.E.E. 550 Avenue
    Alphonse Jauffret 84306 Cavaillon, France
    4
    Institut Europeen des Membranes, (UMR 5635) CNRS-ENSCM-UM2, Universite Montpellier 2, cc047, Place Eugene
    Bataillon 34095 Montpellier, France
    veronique-j.durandcea.Ir
    Because it is non-toxic, non-Ilammable and low cost, supercritical carbon dioxide (SC-CO
    2
    ) is an interesting media Ior the
    development oI both sustainable chemistry and new green processes. Moreover, its critical parameters (Tc 31C, Pc 7.3
    MPa) are easily accessible and compatible with a large range oI applications. Since the beginning oI the 1990s, the use oI
    supercritical Iluids as solvent became a credible alternative media Ior the synthesis oI materials.
    The most important speciIicity oI supercritical Iluids is related to their original properties intermediate between those oI gases
    and liquids. Actually, they have a liquid-like density and gas-like viscosity and diIIusivity. These properties are continuously
    adjustable Irom gas to liquid by small variations oI pressure and/or temperature |1|.
    Ceramic processing in SC-CO
    2
    is investigated in our group Ior creating homogeneous nanocrystalline ceramic powders with
    simple or complex Iormulations Irom a variety oI precursors including alkoxides and metal organic compounds. Processing oI
    ceramic precursors by a SC-CO
    2
    assisted sol-gel method has been investigated as a suitable synthesis pathway yielding SiO
    2
    Iibers, TiO
    2
    powders, doped ceria, lanthanum gallates, nanophase zirconia and more recently PMMA-encapsulated yttria-
    stabilized zirconia particles |2-4|. The porous texture, morphology, crystalline structure and size distribution oI these powders
    can be controlled by adjusting the synthesis parameters. Furthermore, the ceramic powders synthesized by this method do not
    require any Iurther drying steps, and their crystallization temperature is generally lower compared to usual processes (e.g.
    conventional sol-gel process). Also, the speciIic area oI these materials is generally very high and ensures a high reactivity
    (e.g. Ior powder sintering, adsorption or catalytic reactions). These compounds are developed in view oI several applications
    like nanomaterials Ior Iuel cells electrolyte, inorganic UV Iilters, nanostructured layers on macroporous substrates (monolith,
    Ioam) Ior catalytic or membrane related applications. In this work, an original approach to develop inorganic membranes in
    supercritical media will be reported. It is namely studied Ior preparing silica-based membranes in/on tubular substrates. The
    relation between the synthesis process parameters and the membrane characteristics will be reported.
    |1| CANSELL, F. and AYMONIER, C., The Journal oI Supercritical Fluids Vol. 47, 2009, p. 508-516.
    |2| SARRADE, S., SCHRIVE, L., GUIZARD, C., and JULBE, A., METHOD FOR MAKING SINGLE OR MIXED METAL
    OXIDES OR SILICON OXIDE. 2002 PATENT n EP0225785.
    |3| GUIZARD, C., JULBE, A., ROBBE, O., and SARRADE, S., Catalysis Today, Vol. 104, 2005, p. 120-125.
    -246-
    |4| HERTZ, A., SARRADE, S., GUIZARD, C., and JULBE, A., Journal oI the European Ceramic Society, Vol. 26, 2006, p.
    1195-1203.
    PA.7.9
    Facilitated olefin transport membranes using chemically activated copper
    nanoparticles by ionic liquids
    J. H. Lee
    1
    , S. W. Kang
    2
    , J. Kim
    1
    , K. I. Han
    1
    , Y. S. Kang
    1f
    1
    Department of Chemical Engineering, Hanvang Universitv,Seoul 133-791, South Korea
    2
    School of Chemical & Biological Engineering, Seoul National Universitv, Seoul 151-744, South Korea
    junghyun27hanyang.ac.kr
    In last decades, nanochemistry has been intensively investigated because oI the attractiveness oI nanomaterials showing novel
    properties and applications. Especially, nano-scaled copper has played a role as p-type semiconductor with promising
    applications and also has been interested in solar energy conversion and catalysis.
    1-3
    Recently, we Iound that partially positively charged silver nanoparticles activated by an electron acceptor oI 1-butyl-3-methyl
    imidazolium tetraIluoroborate (BMIM

    BF
    4
    -
    ) or 1-butyl-3-methyl imidazolium nitrate (BMIM

    NO
    3
    -
    ) acted as a new oleIin
    carrier Ior Iacilitated transport membrane.
    4
    Partially positively charged silver nanoparticles at the surIace interact with oleIin
    reversibly, and can thus act as an oleIin carrier Ior Iacilitated oleIin transport.
    4, 5
    In this work, we suggest that copper nanoparticles, having similar chemical properties to silver ones, can also be used as an
    oleIin carrier. SpeciIically, the Iacilitated transport phenomenon utilizing copper nanoparticles chemically activated by BMIM

    BF
    4
    -
    was investigated. The BMIM

    BF4
    -
    /Cu composite membranes showed the selectivity oI propylene/propane and the
    mixed gas permeance were about 10 and 5.5 GPU, respectively. This is mostly due to the reversible interactions between
    propylene and the positively charged surIace oI copper nanoparticles. The positively charged surIace was Iormed due to the
    loosen interactions between the cationic BMIM

    and its counteranion BF4


    -
    by the interactions oI the surIace oI copper with
    BF4
    -
    . Interactions between Cu nanoparticles and BF4
    -
    ions in BMIM

    BF4
    -
    /Cu nanocomposites were investigated by FT-
    Raman spectroscopy. The Raman spectra suggested that neat BMIM

    BF4
    -
    existed mostly as ion pairs and ion aggregates, but
    the addition oI Cu nanoparticles into the BMIM

    BF4
    -
    caused the interactions between BMIM

    and BF4
    -
    to be loosened by
    interactions between surIace oI Cu nanoparticles and counteranions. The surIace positive charge on the copper nanoparticles is
    expected to be Iormed because oI their potential interactions with the ionic liquid as conIirmed by XPS.
    For these reasons, copper nanoparticles chemically activated by the ionic liquid played a role as a carrier Ior Iacilitated oleIin
    transport. The ionic liquids can induce the surIace oI copper nanoparticles to be partially positively charged. High mixed gas
    selectivity oI propylene/propane mixtures indicated that the positively charged surIace oI the copper nanoparticles by ionic
    liquids was able to act as an oleIin carrier Ior the Iacilitated oleIin transport. It is concluded that copper nanoparticles can also
    be used as oleIin carrier Ior Iacilitated oleIin transport and are expected to be more durable with time.
    |1| T. J. Huang, D. H. Tsai, Catal. Lett., 87, 173 (2003)
    |2| Z. Yang, C-K. Chiang and H-T. Chang, Nanotechnologv, 19, 2, 025604 (2008).
    |3| C. J. Murphy, T. K Sau, A. M. Gole, C. J. OrendorII, J. Gao, L. Gou, S. E. Hunyadi and T. Le., J. Phvs. Chem. B, 109,
    13857 (2005)
    |4| S. W. Kang, K. H. Char, and Y. S. Kang, Chem. Mater., 20, 4 (2008)
    |5| S. W. Kang, D. H. Lee, J. H. Park, K. H. Char, J. H. Kim, J. O. Won and Y. S. Kang, J. Membr. Sci., 322, 281, (2008)
    -247-
    PA.7.10
    Aerosol filtration as preparation a method of asymmetric membranes for gas
    separation membranes
    F. Meyer, B.J. Bladergroen
    South African Institute for Advanced Materials Chemistrv, Universitv of the Western Cape, Private Bag X17, Bellville 7535,
    Cape Town, South Africa
    2116439uwc.ac.za
    Membrane technology has been identiIied as a gas separation technology with great commercial potential. Asymmetric
    membranes are generally desired to meet the required permeance, selectivity and mechanical stability. There are various
    methods oI producing asymmetric membranes such as, electroplating, solution casting, and phase inversion |1|. The current
    work shows how aerosol Iiltration can be used as a novel preparation technique Ior the production oI asymmetric membranes.
    The aerosol Iiltration technique introduces solid matter to the support using a gas as a transport medium rather than a liquid.
    This oIIers important advantages on particle size control
    |2|
    and increases the operating temperature window. Using aerosol
    Iiltration, seamless asymmetric membranes can be produced by selective deposition oI particles with controlled particle size
    The aerosol Iiltration system operates by initially aerosolizing the precursor solution with an ultrasonic nebulizer. A carrier gas
    directs the aerosol droplets through a tube Iurnace where solid particles are produced upon evaporation oI the solvent. The dry
    particles are directed towards a support under the inIluence oI a pressure gradient (vacuum behind the support) and the
    particles accumulate on the surIace oI the support. Upon continuous dilution oI the precursor solution, particles with reduced
    particle size are generated which can be used to produce a seamless asymmetric membrane. In the initial study cellulose
    acetate particles have been prepared and deposited onto a support purely as a prooI oI concept. Later research will Iocus on
    inorganic membrane production.
    The SEM images oI particles deposited onto Anopore supports revealed that porous cellulose acetate Iilm was Iormed
    consisting oI spherical cellulose acetate particles. The size oI these particles appeared to be a Iunction oI the precursor
    concentration as illustrated in Iigure 1.
    This work shows that aerosol Iiltration can be used as a method to produce Asymmetric membranes. This method oIIers a
    great potential Ior membrane manuIacturing since a wide range oI process parameters can be used to control the size oI
    deposited particles in a continuous process.
    Figure 1: Particle size as a Iunction oI particle size
    |1| M. Mulder, Basic Principle oI membrane technology, 2
    nd
    edition, Centre oI Membrane science and technology, 136
    |2| Yeung K.L, Aravind R, Szegner J., Varma A, Metal composite membranes:synthesis, characterization and reaction studies,
    Stud. SurI. Sci.Catal. 101 (1996) 1349.
    |3| Yeung K.L, Aravind R, Szegner J., Varma A, Metal composite membranes:synthesis, characterization and reaction studies,
    Stud. SurI. Sci.Catal. 101 (1996) 1349.
    -248-
    PB.1.1
    High resolution SEM to determine the pore size distribution of filtration membranes
    Y. Wyart
    1
    , R. Tamime
    1
    , S. Nitsche
    2
    , D. Chaudanson
    2
    , K. Glucina
    3
    , P. Moulin
    1
    1
    Universite Paul Ce:anne, Laboratoire de Mecanique, Modelisation et Procedes Propres (M2P2-UMR 6181), Europole de
    lArbois, 13545 Aix en Provence cedex 04, France
    2
    Centre Interdisciplinaire de Nanoscience de Marseille (CINaM-UPR 3138), Campus de Luminv, 13288 Marseille Cedex 09,
    France
    3
    Sue: Environnement, CIRSEE, Pole Qualite Eau, 38, rue du President-Wilson, 78230 Le Pecq, France
    yvan.wyartuniv-cezanne.Ir
    The parameters studied to characterise the membrane structure are many and can roughly be classiIied into porosity,
    roughness, pore size, pore shape and pore size distribution. Only membrane structure parameters will be considered in this
    paper and more especially pore size distribution. Advances in the study oI membrane structure have been made possible thanks
    to microscopic techniques such as Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), near-
    Iield microscopy (Atomic Force Microscopy, (AFM) and Scanning Tunnelling Microscopy (STM)). Among these various
    techniques, the most widely used are SEM and AFM. The SEM applications are varied and Iocus on membrane structure
    characterization, hollow Iiber membrane Iabrication and the study oI the Iouling process. Hwang and Lin |1| used observations
    made using SEM to qualiIy the nature oI the pores oI 3 microIiltration membranes with a cut-oII oI 0.1 m. The major
    drawback oI this technique is the sample preparation by metallization, which entails a less accurate pore size determination.
    The aim oI this study is to propose a technique allowing the surIace observation oI organic and ceramic membranes, using a
    controlled metallization step, in order to determine cartography oI pore size thanks to an image processing. JEOL JMS-6320F
    is a high resolution scanning electron microscope with a cold Iield emission source and an in lens detection. It can be used
    Irom 0.5 kV to 30 kV with a resolution oI 1.2 nm at 15 kV and 2.5 nm at 1 kV. High resolutions at low accelerating voltages
    are possible with this instrument thanks to its objective lens design. A secondary electron detector is integrated into the bore oI
    the lens and the specimen can be brought up into the lens Iield. Working distances (WD) oI as short as 5 mm are possible. The
    microscope is also Iitted with a Bruker EDX system with a light element X-ray detector (15 mm WD) and a back scatter
    detector. There is also a second conventional secondary electron detector below the lens, which gives more topographic
    images. MagniIications oI 25x to 650,000x (at 5 mm WD) are possible. Leica QWin is a highly versatile image analysis and
    processing soItware Ior quantitative microscopic observations. The modular and scaleable nature oI Leica QWin is such that its
    capability ranges Irom simple interactive image measurements to automatic, multi parameter measurements oI numerous
    Ieatures. The studied membranes are new organic and ceramic membranes with Ilat sheet, hollow Iibre and tubular geometry.
    The studied cut-oIIs are superior or equal to 10 kDa. For hollow Iibres with an inner skin oI 150 kDa, the pore distribution as a
    Iunction oI their size has been established and the obtained Iilling rate (7) is in agreement with the manuIacturer data. This
    new technique, developed as quality control technique, is an essential tool Ior membrane manuIacturers in order to characterise
    perIectly the membranes aIter manuIacture. Experimentations are in progress in order to study membranes ageing and their
    Iouling by various materials.
    |1| K.J. Hwang and T.T. Lin, EIIect oI morphology oI polymeric membrane on the perIormance oI cross-Ilow microIiltration,
    Journal oI Membrane Science, 199, (2002), 41-52
    PB.1.2
    Study of the working temperature influence on the mechanical properties of
    polysulfone films
    B. Pea, L. Ferre, R. Garcia-Valls, F. Ferrando, T. Gumi
    Departament dEnginveria Quimica, Escola Tecnica Superior dEnginveria Quimica, Universitat Rovira i Jirgili, Av. Pasos
    Catalans, 26, 43007 Tarragona, Spain.
    brisamarisol.penaestudiants.urv.cat
    Encapsulation is deIined as a process in which particles are surrounded by a coating. It can be used to remove, protect,
    preserve and disseminate many substances |1|. To know the behaviour oI capsules material, in several conditions, is very
    important Ior the encapsulation process and Ior the Iinally application oI the capsules. For this purpose determining the
    -249-
    mechanical properties oI the capsule coatings seems a good option Ior capsule material characterization. However, as capsule
    conIiguration does not allow perIorming this study, membrane Iilms were used.
    PolysulIone Iilms were obtained by phase inversion precipitation |2|, using polysulIone as polymer, dimethyl Iormamide as
    solvent and vanillin (with the objective oI simulate de capsules composition). For preparing the membrane Iilms, a coating
    machine was employed. The Iilm dimensions were 20 X 20 cm.
    Morphological characterization oI the external surIaces and oI the internal porous structures oI Iilms was carried out using the
    scanning electron microscopy (SEM) |3|.
    The mechanical properties oI the Iilms were determined using the American Society Ior Testing Materials standard ASTM - D
    5748-95 (Protrusion Puncture Resistance oI Stretch Wrap Film), obtaining the break Iorce and the energy oI the break.
    To evaluate the inIluence oI the working temperature, on the Iilm mechanical properties, ten Iilms need to be exposing Ior Iive
    days in a solution with 6000 ppm oI DMF, at diIIerent temperatures (55, 70, 90 C). AIterwards they will be characterizing as
    aIorementioned. Table 1 shows some results obtained.
    Table 1 Mechanical properties oI polysulIone Iilms
    Sample Break Iorce
    (N)
    Energy
    (J)
    Membrane thickness
    (m)
    Without treatment 14.1 0.8 0.12 0.011 98 3.5
    At 55 C and in a
    DMF solution. 13.81 1.58 0.084 0.017 92.83 2.93
    |1| Pea, B.; Casals, M.; Torras, C.; Gumi, T.; Garcia-Valls, R. Janillin release from polvsulfone macrocapsules, accepted Ior
    publication in Industrial & Engineering Chemistry Research.
    |2| Mulder, M., Basic Principles of Membrane Technologv, Kluwer Academic Publishers, Dordrecht, 1997.
    |3| Torras, C.; Pitol-Filho, L.; Garcia-Valls, R. Two methods Ior morphological characterization oI internal microcapsule
    structure. Journal of Membrane Science 305 (2007) 1-4.
    PB.1.3
    Analysis of the charge formation mechanisms in nanofiltration membranes by
    tangential streaming potential measurements
    A. Szymczyk
    1
    , L. Bruni
    3
    , P. Fievet
    2
    , S. Bandini
    3

    1
    Chimie et Ingenierie des Procedes, UMR CNRS 6226, Universite de Rennes 1 / ENSCR, 263 Avenue du General Leclerc,
    Batiment 10 A, CS 74205, 35042 Rennes Cedex, France
    2
    Institut UTINAM, UMR CNRS 6213, Universite de Franche-Comte, 16 route de Grav, Besanon Cedex 25030, France
    3
    Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali, Universitv of Bologna, Jia U.Terracini, 28,
    I-40131, Bologna, Italv
    serena.bandinimail.ing.unibo.it
    It is experimentally recognized that nanoIiltration membranes show a diIIerent behaviour oI separation perIormances
    depending on the type oI electrolytes. Amphoteric behavior is Irequently observed as a consequence oI the presence oI a
    surIace charge which is related to the membrane material, to the ionic strength and to the pH conditions oI the solutions in
    contact with the membrane |1|. The development oI reliable techniques providing inIormation about the surIace electrical
    properties oI membrane materials is a necessary step to understand and control the Iiltration eIIiciency oI membranes |2|.
    Tangential streaming potential measurements are perIormed through Desal DK membranes (polyamide-thin Iilm composite) in
    contact with dilute aqueous solutions containing NaCl or CaCl
    2
    at pH3 and 6; salt concentrations in the range Irom 0.1 to 10
    mol/m
    3
    are investigated. The corresponding volumetric membrane charge values are calculated basing on relationships derived
    Irom the Gouy-Chapman theory oI Ilat interIaces and accounting oI a pore slit-like geometry. The results obtained show a very
    interesting behaviour. At pH3 and pH6 the total membrane charge is positive and negative, respectively; however at very
    low salt concentrations it appears as an unimodal Iunction oI the equivalent concentration: Ior both NaCl and CaCl
    2
    solutions,
    at pH3, the membrane charge shows a maximum point close to 1 mol/m
    3
    , whereas Ior NaCl solutions at pH6 it shows a
    minimum point close to 0.5 mol/m
    3
    . With regards to NaCl solutions, the results are remarkably in agreement with the
    behaviours obtained in |1|, in which the membrane charge values were calculated as Iitting parameters by the elaboration oI
    experimental rejections with a transport-partitioning model (based on the extended Nernst-Planck equation, Donnan
    equilibrium, steric hindrance, Debye-Huckel theory and dielectric exclusion related on the image Iorces).
    The similarities between NaCl and CaCl
    2
    results put in evidence that quite similar mechanisms are involved in the membrane
    charge Iormation. By using the Adsorption-Amphoteric model |1| (in which the charge Iormation mechanism is described
    according to acid/base dissociation oI the hydrophilic sites oI the membrane, to counter-ions site-binding onto the dissociated
    -250-
    sites as well as to competitive adsorption oI ions on the hydrophobic sites oI the membrane), the data show that the membrane
    charge is the result oI opposite eIIects between a) counter-ion site binding on the dissociated hydrophilic sites and b) co-ion
    adsorption on hydrophobic sites as well as site-binding oI co-ion on the dissociated hydrophilic sites.
    |1| L.Bruni, S.Bandini, The role oI the electrolyte on the mechanism oI charge Iormation in polyamide nanoIiltration
    membranes, J. Membrane Sci. 308 (2008) 136-151.
    |2| P.Fievet, M.Sba, A. Szymczyk, A. Vidonne, Determining the zeta potential oI plane membranes Irom tangential streaming
    potential measurements: eIIect oI the membrane body conductance, J. Membrane Sci. 226 (2003) 227-236.
    PB.1.4
    Do macro-voids are induced by skin-defects during wet phase inversion ?
    J. Mendret
    1, 2
    , Y. Medina-Gonzalez
    1, 2
    , J-C. Remigy
    1, 2
    1
    Universite de Toulouse , INPT, UPS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    2
    CNRS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    mendretchimie.ups-tlse.Ir
    Phase inversion process is a common method to produce polymeric membranes. Usually, a dope solution which consists oI a
    polymer and a solvent, is Iormed into the desired shape (Ilat-sheet, hollow Iibre.). Then the dope solution is contacted with a
    non-solvent bath (usually water), the dope solution composition will change due to exchange oI solvent and non-solvent
    between non-solvent bath and polymer Iilm. This mass-transIer oI the three components, combined to the thermodynamic
    equilibrium, leads to phase inversion: the homogeneous solution is converted into two phases: a polymer rich phase and a
    polymer lean phase. The polymer rich phase will gel and give the membrane structure while the polymer lean phase will
    evolve through coalescence step into the membrane pores. The Iinal structure oI the membrane depends on the mass transIer
    (diIIusion coeIIicient, gradient concentration) and thermodynamics equilibrium between the polymer, the solvent and the non
    solvent.
    The substructure oI the membrane depends also oI the nascent skin which leads to a heterogeneous diIIusion as the Ilux will be
    higher in the skin pore than in the dense parts. Indeed, a deIect on the top layer oI the membrane (i.e. a pore larger than the
    mean pore diameter) could be a start point oI macrovoid Iormation |1|. It would then be possible to control the membrane
    structure by using a porous material, intercalated between the polymer solution and solvent, which could generate macrovoid.
    The structure oI the porous material will then induce the structure oI the membrane.
    The aim oI this study is to experimentally veriIy this possibility. Tests were conducted with polysulIone, N-methyl-2-
    pyrrolidinone as the solvent and water as a non-solvent. To initiate the Iormation oI macro-voids, we used capillary pore
    membranes with a controlled pore size distribution and density.
    Those membranes, soaked beIorehand with NMP, were put on the dope Iilm beIore addition oI non-solvent. Several pore sizes
    were tested (0.4, 1 and 10m). The results show that the structure oI the membrane present large macrovoid connected to the
    skin surIace (deIined as the side oI the dope solution exposed to water) (Iig. 1)
    Figure 1: membrane obtained by using a 5m capillary pore membrane: leIt; cross-section, right; surIace
    Tests, under way, are conducted with microsieves (similar to the one described in Kuiper et al. |2|) in order to control the pore
    spatial patterns. Several patterns were tested and compared. All results will be discussed in relation to the membrane
    Iormation.
    |1| H. Strathmann, K. Kock, P. Amar, R.W. baker, Desalination, 1975, 16, 179-203.
    |2| S. Kuiper, C.J.M.van Rijn, W. Nijdam, M.C. Elwenspoek, J. Mbr. sci, 1998, 150, 1-8.
    -251-
    PB.1.5
    Water vapor stability of Zeolite molecular sieving membranes for the separation
    of CO
    2
    from H
    2
    in humid atmospheres for pre-combustion power plant processes
    C. Chatzicharalampous
    1
    , H. Richter
    2
    , T. Markus
    1
    1
    Institute of Energv Research,

    Forschungs:entrum Juelich GmbH, Leo-Brandt Strae, D-52425 Jlich, Germanv
    2
    Hermsdorfer Institut fuer Technische Keramik e.J. (HITK), Michael-Faradav Strae, D-07629, Hermsdorf, Germanv
    c.chatzicharalampousIz-juelich.de
    For CO
    2
    -emission Power Plants, gas separation membranes are considered to be the most eIIicient technology. Methods Ior the
    capture oI carbon dioxide Irom Power Plants with help oI gas separation membranes are the oxyIuel process as well as post-
    and pre-combustion processes. In the latter case gas separation membranes have to remove CO
    2
    and Irom hydrogen in
    atmospheres containing remarkable amounts oI water vapor.
    Materials with good potential Ior pre-combustion capture are zeolites. Zeolites with an opening window between 2 A and 5 A
    are good candidates Ior molecular sieving membranes Ior CO
    2
    separation Irom a CO
    2
    /H
    2
    gas mixture. The zeolites that have
    been used are NaA with a window opening oI 4 A, ITQ-29 with a hydrophobic character because oI its high Si/Al ratio, H-
    SOD with a window opening oI 2.65 A such as modiIication like S-SOD and Si-SOD. Considering the kinetic diameter oI CO
    2
    at 3.7 A and the H
    2
    at 2.9 A one demanded property is the steam stability because the present oI water vapor in the gas mixture
    that may eIIect the stability oI the Zeolites. To investigate this, annealing experiments were carried out as well as DiIIerential
    Thermal Analysis (DTA) measurements under a gas mixture oI CO
    2
    /H
    2
    in presence oI water vapor at diIIerent temperatures. In
    order to investigate the structure stability oI the Zeolites aIter the measurements we used Scanning Electron Microscopy
    (SEM), Energy Dispersive X-Ray Spectroscopy (EDX) and X-Ray DiIIraction (XRD).
    PB.1.6
    Anomaly of thermo-mechanical properties of Ba
    0.5
    Sr
    0.5
    Co
    0.8
    Fe
    0.2
    O
    3-
    at low
    temperatures
    B.X. Huang
    1
    , J. Malzbender
    1
    , R. W. Steinbrech
    1
    , S. Baumann
    2
    , W. Meulenberg
    2
    , A. Mbius
    1
    , T. Markus
    1
    ,
    P. Grychtol
    3
    , C. M. Schneider
    3
    , L. Singheiser
    1
    1
    Forschungs:entrum Jlich, IEF-2, 52425 Jlich, Germanv
    2
    Forschungs:entrum Jlich, IEF-1, 52425 Jlich, Germanv
    3
    Forschungs:entrum Jlich, IFF, 52425 Jlich, Germanv
    j.malzbenderIz-juelich.de
    Thermo-mechanical properties oI Ba
    0.5
    Sr
    0.5
    Co
    0.8
    Fe
    0.2
    O
    3-o
    were measured with ring-on-ring test and depth-sensitive micro-
    indentation. The material displayed anomalies in the mechanical properties at low temperatures. In particular the stiIIness
    decreases strongly Irom RT to 200C, and recovers to a stable value Irom 300C. Correspondingly, the Iracture stress and
    toughness show a similar behavior. However, the Iracture stress Iurther decreases slightly to 400C, and recovers Irom 500C.
    Since BSCF keeps cubic structure Irom RT up to 1000C, the anomalies were attributed to the association/dissociation oI point
    deIects and the transition oI spin states
    -252-
    PB.1.7
    Characterization of new Moroccan clay, for the ceramic membrane conception
    N. Elharrak, A. Yaacoubi, A. Outzourhit
    Facultv of Sciences Semlalia, Universitv Cadi Avvad, B.P. 2390, Marrakech, MOROCO
    elharraknadayahoo.Ir
    Membranes technologies, like Reverse Osmosis, Iound wider acceptance in recent years. However, membrane treatment is still
    more expensive than conventional water treatment technologies (e.g : coagulation).The quality oI the Ieed water supply is the
    single most important Iactor to be considered in ensuring the technical and economic viability oI an Reverse Osmosis
    desalination plant.
    Scaling causes the nominal Ilux to decrease. The consequences are a higher energy use, an increase oI the cleaning Irequency
    and a shorter liIe span oI the membranes. This will cause the membrane water treatment process to become much more
    expensive. Proper pretreatment, is one oI the most critical Iactors Ior the success Reverse osmosis units, long term and
    perIormance.
    In an eIIort to reduce the costs oI RO pretreatment step, and the valorization oI local and natural materials, the aim oI this work
    is to study the removal oI the principal scaling Iactors, in brackish water desalination units. To Iight against this phenomenon,
    several Moroccan clays ware tested.
    In this communication, we shall present in one hand, the characterization oI the diIIerent clays tested in using: the X
    diIIraction, thermal analysis and scanning electron microscopy and in the other hand, The experimental results oI the diIIerent
    adsorption tested realised.
    PB.1.8
    Manufacture and characterization of zirconia microfiltration membranes for
    separation of oil-water emulsions
    R. Del Colle, C.A. Fortulan, S. R. Fontes
    Engineering School of Sao Carlos (EESC), Department of Mechanical Engineering, Universitv of Sao Paulo (USP), Av.
    Trabalhador So-carlense,400, So Carlos, Bra:il.
    betasc.usp.br
    The selection oI raw material Ior the manuIacture oI membranes is Iundamental in processes whose perIormance depends on
    the aIIinity between the porous medium and the Iluid. The manuIacturing conditions are also important as they determine the
    membrane`s morphology. Such morphology strongly inIluences the transport properties hence the membrane`s perIormance.
    In this context, this work aims to develop tubular asymmetric zirconia membranes by isostatic pressing which will be
    applicable to microIiltration processes Ior the oil-water emulsions separation. For such a purpose, a rigorous control was
    realized on the distribution and size oI pores. Suspensions at 30 vol. oI solids (zirconia

    or alumina

    Iine powder and sucrose)
    and 70 vol. oI liquids (isopropyl alcohol and PVB) were prepared in a mill oI jars varying the time oI milling and the
    particles size oI sucrose (previously classiIied in bolters), according to the pores size expected. AIter that process, the
    barbotine was dried and granulated to obtain the ceramic dust used in the manuIacture oI the membranes. For the manuIacture
    oI the supported zirconia membranes, a thin layer oI suspension was deposited onto the nucleus (a part belonging to the mould)
    Ior the Iormation oI zirconia top-layer, beIore Iilling the mould with ceramic dust (Al
    2
    O
    3
    or ZrO
    2
    ). Next, the mould was
    subjected to isostatic pressing Ior the conIormation oI the zirconia membranes. Those membranes underwent a thermal
    treatment (Ior a partial burning oI sucrose) and were sintered until 1500C. They were characterized by SEM, porosimetry by
    mercury intrusion, measurements oI weight by immersion (Ior the determination oI the apparent porosity and density) and
    water and air permeability tests. The morphologic characterization oI membranes veriIied the Iormation oI a porous ZrO
    2
    membrane, an asymmetric ZrO
    2
    membrane (zirconia top-layer on the porous zirconia support) and a supported ZrO
    2
    /Al
    2
    O
    3
    composite membrane. The results oI porosimetry analysis by mercury intrusion presented a mean pore size oI 1,8m, Ior the
    porous ZrO
    2
    membrane and the other membranes, 0,03 and 1,8m, respectively, Ior the top-layer and support. The porous ZrO
    2
    membrane presented an apparent porosity oI 17, while the other membranes obtained porosity between 30 and 21. All
    membranes achieved a total porosity oI about 50, which characterizes them as microIiltration membranes |1|. The air
    permeability tests showed that the manuIactured zirconia membranes achieved higher permeability than the porous alumina
    membranes tested in another study |2|. The water permeability tests showed that the zirconia membranes presented, as a rule, a
    smaller transmembrane Ilow in comparison to the porous alumina membranes. Such membranes were applied to oil-water
    -253-
    emulsions separation and presented good perIormance and high retention oI oil phase (about 99). The zirconia membranes
    prepared in this work were also employed to separate oil-water emulsion and they were eIIicacious.
    |1| H.J. Veringa, R.A. Terpstra and A.P. Philipse, Applications and design oI porous ceramic structures. In: Designing with
    structural ceramics, Elsevier Applied Science, London, 1990.
    |2| R. Del Colle et al., ManuIacture oI ceramic membranes Ior application in demulsiIication process Ior cross-Ilow
    microIiltration, Proceedings of Engineering With Membranes 2008, Algarve, 2008, pp. 206-207.
    PB.1.9
    Pore size distribution and MWCO estimations of polymeric membranes by liquid-
    liquid displacement porosimetry
    J.I. Calvo
    1
    , A. Bottino
    2
    , G. Capannelli
    2
    , A. Hernandez
    1
    , R.I. Peinador
    1
    , R. Firpo
    2
    ,
    1
    Depto. Fisica Aplicada, Facultad de Ciencias, Universidad de Jalladolid, 47071 Jalladolid, Spain, Real de Burgos,s/n,
    47071Jalladolid (Spain).
    2
    Dipto. Chimica e Chimica Industriale, Universita di Genova, Jia Dodecaneso 31, 16141 Genova, Italv
    jicalvotermo.uva.es
    Two polymeric (polysulIone) UF membranes Irom AlIa-Laval (GR61PP and GR70PE) have been studied by various
    characterization techniques. FTIR spectroscopy has been used to analyse membrane material. FESEM have been employed to
    obtain detailed inIormation on the structure and morphology oI membrane skin layer oI both membranes. Finally LLDP
    porosimetry has been used to determine the whole pore size distribution oI the active pores |1|. Main results oI LLDP
    characterization as independently measured in both labs are shown in Table 1. Pore size distribution has been used to estimate
    the molecular weight cut-oII (MWCO) oI the membranes, matching the size oI the 90 biggest pores with the molecular
    weight oI the corresponding dextran molecule with the same Stokes radius. The data reported in Table 1 show not only a nice
    agreement between mean pore size determined by the two both labs but also between the estimated MWCO and MWCO
    reported in the literature Ior both membranes |2|.
    Mean radius
    (1)
    / nm Mean radius
    (2)
    / nm MWCO / Da
    GR61PP
    Valladolid 2.84 + 0.27 2.42 + 0.35 19556 + 2000
    Genova 2.90 + 0.14 2.03 + 0.05 21160 + 3000
    GR70PE
    Valladolid 6.52 + 0.03 3.24 + 0.05 27703 + 1000
    Genova 11.72 + 4.5 3.28 + 0.83 25596 + 5000
    Table 1. Results oI mean pore size:
    (1)
    Irom pore permeability,
    (2)
    Irom pore number
    distribution; along with the MWCO estimations.
    AlIa-Laval Membranes is acknowledged Ior supplying the membrane samples.
    |1| J. M. Sanz, D. Jardines Garcia, A. Bottino, G. Capannelli, A. Hernandez, J. I. Calvo, Liquidliquid porometry Ior an
    accurate membrane characterization, Desalination, 200 (2006) 195197.
    |2| A. F. Vikbjerg, G. Jonsson, H. Mu, X. Xu, Application oI ultraIiltration membranes Ior puriIication oI structured
    phospholipids produced by lipase-catalyzed acidolysis, Sep. PuriI. Tech. 50 (2006) 184191.
    -254-
    PB.1.10
    Polyimides with hydroxyl group in diamine fragment: structure, thermochemical
    rearrangement and gas separation properties
    O. Rusakova
    1
    , J. Kostina
    1
    , G. Bondarenko
    1
    , A. Alentiev
    1,2
    , A.Yakimanskii
    3
    1
    A.J.Topchiev Institute of Petrochemical Svnthesis, 29 Leninskv Pr., 119991, Moscow, Russia
    2
    M.J.Lomonosov Moscow State Universitv, Chemistrv department, 1, Leninskie Gorv, Moscow, Russia

    119991
    3
    Institute of Macromolecular Compounds 31, Bolshoi pr., St. Petersburg, Russia, 199004
    OlgaRusakovaips.ac.ru
    The study oI structure-properties relationship oI thermostable polymers Ior gas separation membranes is the important problem
    oI membrane material science. The chemical structure modiIication oI chain Iragments in polymers leads to chain rigidity
    changing, which inIluences on chain packing, and, thus, gas separation properties oI polymer material.
    In this work new polyimides containing hydroxyl groups in diamine Iragment have been studied. Generally these polymers
    have high permselectivity belong close to Robeson 'upper bound |1| but low permeability because oI interchain hydrogen
    bonds Iormation |2|. Besides studied polymers have a tendency to physical aging, which leads to still more decrease oI
    permeability and increase oI permselectivity. However there is the way to increase permeability oI polyimides containing
    hydroxyl groups in diamine Iragment almost without permselectivity loss |3|. The thermochemical rearrangement leads to new
    polymer with benzoxazole cycles Iormation |45| with more rigid structure and, thus, with larger Iree volume, which was
    accompanied by permeability increase almost without ideal separation Iactor loss |3|.
    It has been determined Ior studied polyimides heated above 400
    o
    C that thermochemical reactions were observed, however the
    chemical structure oI products were essentially diIIerent Irom proposed in |35|. The mechanism oI reaction depend on
    diamine and dianhydride Iragment structure which is shown by combination oI theoretical (quantum chemistry) and
    experimental (FTIR) methods. The structure oI polymers Iormed by thermal treatment oI polyimides containing hydroxyl
    groups in diamine Iragment has been proved. The FTIR analysis oI heat-treated polymers in combination with quantum-
    chemical simulation allowed to suppose the new mechanism oI thermal rearrangement oI these polyimides.
    |1| Alentiev A. Yu., Yampolskii Yu. P., Vidyakin M. N. Lazareva Yu. N.// Polymer Science Vol. 48, No. 10, Series A, 2006 P.
    1120.
    |2| Rusakova O.Y., Alentiev A.Yu., Yakimansky A.V. // The XV International student, postgraduate and young scientist
    conIerence Lomonosov-2008, 811 April 2008, Chemistry M.: OOO "Knijny dom "Universitet", 2008 P.191
    |3| Young Moo Lee Thermally Rearranged Polymer Membranes with Cavities Tuned Ior Fast Transport oI Small Molecules
    ICOM 2008 July 12-18, 2008, Hawaii
    |4| Kardash I.E., Pravednikov A.N. // Vysokomol. Soyed. B.9. 1967 P. 873
    |5| Gordon L. Tullos, Jason M. Powers, Stacy J. Jeskey, and Lon J. Mathias // Macromolecules, Vol. 32, No. 11, 1999
    PB.1.11
    Polynorbornenes: the structure identification and effect of chemical structure on
    transport properties
    M. Moskvicheva
    1
    , J. Kostina
    1
    , G. Bondarenko
    1
    , V. Yakovlev
    1
    , K. Makovetskii
    1
    , A. Alentiev
    1,2
    1
    A.J.Topchiev Institute of Petrochemical Svnthesis, 29 Leninskv Pr., 119991, Moscow, Russia
    2
    M.J.Lomonosov Moscow State Universitv, Chemistrv department, Leninskie Gorv, 1, 119991, Moscow, Russia
    MariaMoskvichevaips.ac.ru
    Polynorbornenes (PNB) synthesized by additive polymerization are shown an interesting properties (chemical and thermal
    stability, transparency, low double reIraction etc.) what generates interest in their optoelectronic application. PNBs with
    trimethylsilyl substituents are perspective materials Ior membrane gas separation because oI their high permeability (P(O
    2
    )
    8001000 Barrer, ideal separation Iactor Ior O
    2
    /N
    2
    2,6 |1|). The synthesis oI norbornene additive polymerization product
    with 2,7-connection oI monomer units in polymer chain has been described previously |3|. However until now there is the
    problem oI polymers identiIication with 2,3- and 2,7-connection. The methods presented in literature don`t give a single-
    valued answer to the presence oI one or another isomer in investigated sample. Quantum-chemical calculation oI PNB-2,3
    monomer unit |4| and its theoretical spectrum calculation is not suIIiciently correlate with experimental one.
    -255-
    PNB various solubility have been synthesized on diIIerent Ni- and Pd-containing catalytic systems in TIPS RAS. The FTIR-
    spectra oI these polymers have been registered and characteristic spectral diIIerences Ior each isomer have been Iound. The
    quantum-chemical calculations oI trimer models oI 2,3- and 2,7- PNB with theoretical spectrum calculations oI these models
    have been carried out. It has been shown that theoretical spectrum oI 2,3-PNB model was good correlated with experimental
    FTIR-spectrum oI PNB obtained on Ni-containing catalyst. Theoretical spectrum oI 2,7-PNB model described all experimental
    spectral characteristics oI PNB synthesized on Pd-containing catalysts. The Iilms have been obtained Irom PNB-2,3 and
    PNB-2,7 cyclohexane solutions. The absence oI residual solvent in these Iilms has been controlled by FTIR. The transport
    properties oI individual PNB-2,3 n PNB-2,7 Iilms have been measured. The diIIerences in transport properties oI PNB
    depending on their structure have been observed. The combination oI experimental (IR-spectroscopy) and theoretical
    (quantum-chemical calculation) methods oI is promising Ior investigation oI PNB polymerization regioselectivity and
    synthesis oI new polymer materials Ior gas separation membranes.
    |1|. L.Starannikova, M.Pilipenko, N.Belov, Yu.Yampolskii, M.Gringolts, E.Finkelshtein, J. Membr. Sci. 2008. V. 323, I. 1. P.
    134-143
    |2|. Database 'Gas Separation Parameters oI Glassy Polymers, InIormregistr RF, 1998, No. 3585.
    |3|. N.G. Gaylord, B.M. Mandal, M. Martan. J. Polym. Sci.: Polym. Lett. Ed. 1976. V. 14, P. 555-559
    |4|. KaraIilidis C., Holger Hermann, RuIiska A., Gabor B., Mynott R.J., Breitenbruch G., Weidenthaler C., Rust J., Joppek W.,
    Brookhart M.S., Thiel W., Fink G. Angew. Chem. Int. Ed. 2004. V.43. P.2444 2446
    PB.1.12
    Sorption and diffusion in semi-crystalline polyolefins
    L. Pechackova, A. Zubov, T. Gregor, L. Seda, J. Kosek
    Institute of Chemical Technologv, Department of Chemical Engineering, Technicka 5, 166 28 Prague 6, C:ech Republic
    Juraj.Kosekvscht.cz
    In this contribution we illustrate several experimental and modelling tools applicable to porous and polymeric membranes.
    First, we present results oI sorption measurements oI ethylene, propylene and 1-hexene in polyethylene and polypropylene
    samples. Theoretical predictions oI solubility oI gases in the amorphous polymer phase oI semi-crystalline polymer based on
    advanced equations oI state (e.g., SAFT or PC-SAFT) or on molecular dynamics Iail to describe the dependence oI solubility
    on temperature. The cause oI this discrepancy is the omission oI the elastic constraining eIIect; a Iraction oI amorphous
    segments is elastically constrained. Introduction oI elastic constraints into PC-SAFT equation oI state can solve this
    discrepancy between experiments and models.
    Results oI our co-sorption measurements oI ethylene and 1-hexene in polyethylene are compared with theoretical predictions.
    We Iound that ethylene acts as anti-solvent, i.e., it is reducing the solubility oI 1-hexene, while 1-hexene acts as co-solvent
    enhancing the ethylene solubility. Usually overlooked eIIects oI polydispersity oI polymer chains can have a surprisingly
    strong eIIect on sorption in semi-crystalline polymers. We present convincing video-microscopy evidence oI polydispersity
    eIIects.
    In the second part oI our contribution we describe our experience with roentgen micro-tomography with the laboratory source
    oI X-rays and with the resolution oI voxel size around 1 micron. We demonstrate spatially 3D calculation oI diIIusion in
    porous polymer specimens with diIIusion taking place both in pores and in polymer. These calculations are carried out not only
    in the case oI stationary diIIusion with a constant concentration diIIerence applied among the opposite walls but also in the
    dynamic case oI evolving concentrations.
    Figure 1. Porous polyethylene reconstructed Irom X-ray
    microtomography images.
    Figure 2. Concentration proIile oI species diIIusing both in
    pores and polymer.
    -256-
    |1| A. Novak, M. Bobak, J. Kosek, B.J. Banaszak. D. Lo, T. Widya, W.H. Ray, J.J. de Pablo, J. Appl. Polym. Sci. 2006, 100,
    1124-1136.
    |2| L. Seda, A. Zubov, M. Bobak, J. Kosek, A. Kantzas, Macromolecular Reaction Engineering 2008, 2, 495-512.
    |3| B.J. Banaszak, D. Lo, T. Widya, W.H. Ray, J.J. de Pablo, A. Novak., J. Kosek, Macromolecules 2004, 37, 9139-9150.
    PB.1.13
    The AFM study of surface morphology and relationship to organic solvent
    nanofiltration membrane performance
    J. Stawikowska, A. Livingston
    Department of Chemical Engineering and Chemical Technologv, Imperial College London, South Kensington Campus,
    London SW7 2AZ, UK
    a.livingstonimperial.ac.uk
    Atomic Iorce microscopy (AFM) has been used to characterize nanoIiltration membranes used in aqueous systems . However,
    these membranes are generally made by interIacial polymerization, resulting in a thin-Iilm composite structure. Polyimide
    membranes Iormed by phase inversion and used in Organic Solvent NanoIiltration (OSN) have not yet been examined in
    detail. These represent an interesting class oI problems, since it is possible to manipulate the dope solution and casting
    conditions so as to obtain a range oI membranes having molecular weight cut-oII (MWCO) values in a range oI 200 to 800
    g.mol
    -1
    . It is also possible to crosslink the polyimide membranes through amine containing compounds and to add
    nanoparticles to reduce void Iormation. This presents the opportunity to use AFM to investigate whether any oI the physically
    measurable properties under AFM correlate with the Ilux and rejection characteristics oI the series oI membranes produced.
    Pore size distribution, porosity, surIace globular morphology and roughness were quantiIied. Scanning was perIormed using
    intermittent tapping mode in air and liquid mediums in order to compare morphology oI dry and wet membranes. In addition,
    phase shiIting analyses were perIormed to evaluate the hydrophilic/hydrophobic pattern on the membrane surIace. High-
    resolution images were Iiltered to overcome tip convolution eIIects and low Irequency noise (Fig.1A). In order to obtain the
    2D pattern oI surIace globules and pores (Fig.1B), the images were processed in the wavelet Iunction mode. The points below
    and above the roughness median were detected to distinguish hills` and holes`. It has been Iound that the size and shape oI
    pores and globules, porosity and roughness is strictly related to the membrane composition, processing methods, and hence the
    nanoIiltration characteristics. The membranes were tested in a continuous cross Ilow system in various solvents Ior evaluation
    oI Iluxes and MWCO curves. Interestingly the nanoIiltration results, besides the porosity and pore size, are also related to the
    shape oI pores and polymeric globules. The research shows that applying AFM helps to explain the mass transIer through a
    particular membrane at the molecular level.
    -257-
    20nm
    B
    6.31 nm
    0.00 nm
    20nm
    A
    Fig.1 A) Tapping mode AFM image
    oI nanoIiltration polyimide
    membrane, B) Pattern oI pores
    (white) and globules (black) on the
    membrane surIace.
    PB.2.1
    Mechanical and chemical stabilities of polymeric membranes
    C. Liu
    1
    , T. Wachinski
    1
    , M. Farcy, D. Vial
    2
    1
    Pall Corporation, 25 Harbor Park Drive, Port Washington, NY 11050, USA
    2
    Pall Corporation, 3 rue des Gaudines, 78100 Saint-Germain-en-Lave, France
    charlesliupall.com
    Membrane plants Ior drinking water Iiltration are typically designed Ior 20 years oI liIe with one or more
    Low-pressure membranes (microIiltration and ultraIiltration) are increasingly replacing conventional water treatment
    processes as the result oI more stringent regulation and greatly improved competitive pricing. One important but less certain
    Iactor in determination oI the total costs oI low-pressure membrane plants is membrane replacement costs. Low-pressure
    membranes have to experience mechanical and chemical stresses during their service liIe. There are many Iactors contributing
    to the membrane liIe. Among them, mechanical and chemical stabilities oI membranes play important roles.
    Mechanical behavior oI polymeric membranes is more complex than elastic solids. The Iactors contributing to mechanical
    stability include medium composition, architecture, morphology, and membrane construction, as well as the nature oI stress.
    Membranes with high mechanical stability have high mechanical strength while being suIIiciently elastic to allow the stress to
    disperse. Composite membranes experience both tangential and shearing stress on the interIace oI diIIerent media that may
    lead to delaminating. Chemical stability oI polymeric membranes strongly relates to the molecular weight and crystallinity oI
    the membrane medium. High crystallinity would limit the diIIusion oI molecules oI the attaching chemicals within the
    medium, thus retarding chemical degradation.
    Fatigue tests oI polymeric membranes are the useIul tool Ior assessing both mechanical and chemical stabilities. For
    mechanical Iatigue test, it needs to emulate the conditions that are applied in the actual backwash operations with an increased
    Irequency to shorten the length oI the test. SigniIicant increase in elasticity modulus indicates a tendency oI Iracture. For
    chemical Iatigue test, a simpler approach would be to design the test on conservative conditions to ensure the actual exposure
    oI membranes during service liIe within the regime covered by testing conditions.
    Membrane plants Ior drinking water Iiltration are typically designed Ior 20 years oI liIe with one or more membrane
    replacements. The membrane replacement can be a very signiIicant Iactor in determining the economics oI membrane plants.
    There are many Iactors contributing to the membrane liIe. Among them, mechanical and chemical stability oI membranes
    play important roles. Adequately assessing mechanical and chemical stabilities is critical to ensure the service liIe oI
    membranes meeting expectation.
    PB.2.2
    Investigation in development and application of new low-fouling hydrogel composite
    ultrafiltration membranes
    P. Peeva, M. Ulbricht
    Lehrstuhl Ir Technische Chemie II, Universitt Duisburg-Essen, Universitaetsstr. 5, D-45117 Essen
    polina.peevauni-due.de
    Separation processes with ultraIiltration (UF) membranes are successIully used in areas such as Iood processing, waste water
    treatment, and other process stream separations. Disadvantages oI this process are the high costs caused by limited membrane
    liIe time and necessary pre- and post-treatment steps; and Ilux decline via Iouling is the main reason. One possible solution to
    reduce this problem is a controlled surIace modiIication with hydrophilic polymers so that low-Iouling thin-layer hydrogel
    composite membranes are obtained. Earlier work had indicated that photo-initiated graIt copolymerization may be an easy and
    Iast method Ior such surIace modiIication reducing the Iouling tendency oI the base membrane |1|.
    Aim oI this work is the perIormance comparison between unmodiIied and composite UF membranes with a wider range oI cut-
    oII values. PolyethersulIone (PES) UF membranes are chosen as base membranes. The monomer poly(ethylene glycol)(400)
    methacrylate (PEGMA) (well-known as precursor oI non-Iouling materials) is the modiIier used in combination with
    methylene bisacrylamide as a crosslinker monomer. The composite membranes, synthesized by UV-initiated graIting, are
    characterized with respect to membrane perIormance using water permeability as well as static adsorption and Iiltration oI
    macromolecular test substances (proteins and polyphenolic compounds). SurIace wettability (measured by contact angle),
    surIace charge (Irom zetapotential), surIace morphology (Irom atomic Iorce and scanning electron microscopies) and surIace
    chemistry are important characteristics Ior the comparison between base and composite membrane.
    -258-
    Conducted studies (see figure 1) showed an increasing in the Iouling
    resistance oI the new composite membranes compared with virgin membranes
    with similar perIormance (Ilux, cut-oII). Addition oI the crosslinker monomer
    to PEGMA during photograIting allows the control oI hydrogel structure,
    perIormance properties (cut-oII) and could protect the membrane surIace Irom
    deposition oI Iouling substances with low molar mass via a tightly cross-
    linked hydrogel layer.
    Scaling up is an important step to apply such new membranes in industry.
    ThereIore, developing robust methods Ior Iunctionalization oI larger
    membrane area Ior UF tests in pilot scale is a Iocus oI our Iurther research.
    For this reason, investigations oI the impact oI UV-irradiation time (as a
    limiting Iactor during modiIication) and monomer composition on the
    composite membrane perIormance are perIormed. The application oI these
    new thin-Iilm composite membranes would reduce the material costs and duration oI the separation process, leading high
    quality products.
    |1| H. Susanto, M. Ulbricht, PhotograIted Thin Polymer Hydrogel Layers on PES UltraIiltration Membranes: Characterization,
    Stability, and InIluence on Separation PerIormance, Langmuir, 23, 2007, 7818-7830.
    PB.2.3
    The effect of amine degradation products on membrane gas absorption
    J. A. Franco
    1,2
    , D. de Montigny
    3
    , S. E. Kentish
    1,2
    , G. W. Stevens
    1,2
    ,

    J. M. Perera
    1
    1
    Department of Chemical & Biomolecular Engineering, The Universitv of Melbourne, Jictoria, 3010, Australia
    2
    CO2CRC, The Universitv of Melbourne, Jictoria, 3010, Australia
    3
    The International Test Centre for Carbon Dioxide Capture, Facultv of Engineering, Universitv of Regina, Saskatchewan, S4S
    0A2, Canada
    jilskaunimelb.edu.au
    The presence oI monoethanolamine (MEA) degradation products on membrane hollow Iibres was investigated using untreated
    polypropylene (PP). Common amine oxidative degradation products were added to MEA to simulate a degraded solution. The
    eIIect oI these degradation products on the membrane gas absorption process using a PP hollow Iibre membrane module was
    quantiIied. It was Iound that the presence oI oxalic acid reduced the mass transIer rate oI CO
    2
    in MEA most signiIicantly
    Iollowed by Iormic acid and then acetic acid. These acids are believed to adsorb into the polypropylene, altering the surIace
    properties and reducing the hydrophobicity oI the membrane. This in turn increases the degree oI wetting oI the membrane
    pores. SEM images and XPS spectra oI exposed PP membrane indicate that the wetting may be due to both morphological and
    chemical changes in the membrane due to contact with the solvent. This study highlights the need to consider reductions in the
    mass transIer rate oI membrane gas absorption processes associated with inevitable changes in the solvent composition that
    comes with prolonged use.
    PB.2.4
    Evaporative light scattering detector: toward a general molecular weight cut-off
    characterization of solvent resistent nanofiltration membranes
    X. Li
    1
    , F. Monsuur
    2
    , B. Denoulet
    2
    , A. Dobrak
    1
    , P. Vandezande
    1
    , I. F. J. Vankelecom
    1

    1
    Centre for Surface Chemistrv and Catalvsis, Facultv of Bioscience Engineering Katholieke Universiteit Leuven, Kasteelpark
    Arenberg 23 Box 2461, 3001 Leuven, Belgium, Tel. 32-16-32.15.94, Fax. 32-16-32.19.98
    2
    Alltech a Grace Companv, Grace Davison Discoverv Science, Tel. 32-9-340 65 65, Fax. 32-9-340 65 60
    ivo.vankelecombiw.kuleuven.be (I.F.J. Vankelecom)
    NanoIiltration (NF) is a pressure driven membrane process involving pressures between 5 and 20 bars with molecular weight
    cut-oIIs (MWCO, deIined as the MW oI a compound that is retained Ior 90 by the membrane) between 200 and 1000 Da.
    Large-scale NF-applications currently already exist in water treatment, while separations in organic solvents (solvent resistant
    -259-
    Figure 1. Fouling resistance after
    static adsorption with BSA.
    NF, or SRNF) are despite their huge potential only starting to become exploited. One oI the reasons is the diIIiculty to
    select the right membrane Ior a given application. In addition to the solvent dependent permeability oI an SRNF-membrane,
    the correct characterization oI its selectivity is extremely diIIicult. Indeed, the membrane selectivity, as expressed in a MWCO-
    curve plotting solute MW as a Iunction oI retention, is aIIected by many Iactors, including the diIIerent properties oI solutes
    and solvents, as well as the conditions oI Iiltration and even oI the analytical method. As a consequence, the data reported in
    literature lack uniIormity, rendering accurate comparison oI membranes impossible. It also limits progress in understanding
    membrane transport Iundamentally. Although diIIerent analytical techniques have already used Ior MWCO characterization,
    these analysis techniques limit the possible number oI screenable compounds, hence no general analysis is available to
    determine MWCO curves oI SRNF membranes. Moreover the speciIic Iunctional groups needed on the probe solutes Ior these
    types oI analysis, might cause speciIic interaction with the membranes during Iiltration.
    Evaporative light scattering detector (ELSD) coupled with HPLC was used Ior the Iirst time to characterize membranes.
    Polydispersed PEG-200, 600 and 1000 were selected as probe molecules to study the dependence oI membrane retention on
    molecular weight via a gradient eluted HPLC separation coupled to an ELSD detection. The results show that HPLC/ELSD is
    a really general and powerIul technique to study the nanoIiltration (NF) process since it does not require any special properties
    Ior the solutes (chromospheres or Iluorophores) and possesses the required sensitivity. Especially in solvent resistant NF
    (SRNF), where a wide range oI organic solvents is used, the ELSD detector was not aIIected by the interaction between
    solvent and solutes, which is a critical issue compared to other more common detectors.
    1. Rissler, K.; J. Chromatogr. A, 1997, 786, 85-89.
    2. Li, X F; Monsuur, F; Denoulet, B; Dobrak, A; Vandezande, P; Vankelecom, I F J; Analvtical Chemistrv (Revised Ior
    publication).
    PB.2.5
    How room temperature ionic liquids swells polymeric flat membranes ?
    P. Izak
    1
    , S. Hovorka
    2
    , T. Bartovsky
    2
    , L. Bartovska
    2
    , A. Randova
    2
    , J.G. Crespo
    3
    1
    Institute of Chemical Process Fundamentals, Ro:vofova 135, 165 02 Prague 6, C:ech Republic
    2
    Department of Phvsical Chemistrv, Institute of Chemical Technologv, Technicka 5, 166 28 Prague 6, C:ech Republic
    3
    REQUIMTE/CQFB, Dept. de Quimica, FCT, Universidade Nova de Lisboa, P-2829-516 Caparica, Portugal
    izakicpI.cas.cz
    This work demonstrates that the equipment designed and constructed Ior measurement oI membrane swelling is a reliable and
    powerIul tool to Iollow the kinetics and equilibrium oI solute/solvent uptake by Ilat membranes |1|. This technique reveals to
    be particularly adequate Ior studying situations where anisotropic swelling occurs; other techniques based on the over all
    volume or mass change are not able to account Ior this eIIect and to quantiIy it. The results obtained, when studying the
    swelling oI NaIion membranes, show also how the process oI molecular solubilisation and swelling can be inIluenced by the
    Iabrication conditions used during the manuIacturing process. This aspect is particularly important iI we take into
    consideration that the swelling process itselI may also reIlect on the transport properties oI the polymer. When considering the
    NaIion membranes under study, with applications in low resistance devices such as Iuel cells and transducers, their transport
    properties are obviously oI high importance and may determine their perIormance under operating conditions |2,3|. The
    understanding oI the swelling behaviour oI thin Iilms is thereIore essential Ior a comprehensive design oI membrane processes,
    Irom a better control oI the nanoscale properties oI materials towards membrane macroscale applications.
    This research was supported by the Czech Science Foundation grant No. 104/08/0600, by the Grant Agency oI the Czech
    Republic (grant No. 203/08/0465) and the post-doc grant (SFRH/BPD/9470/2002) Irom Fundacao para a Ciencia e a
    Tecnologia (FCT), Portugal.
    |1| P. Izak, S. Hovorka, T. Bartovsky, L. Bartovska, J. G. Crespo; Swelling kinetics oI polymeric membranes in ionic liquids,
    Journal of Membrane Science, 296 (2007) 131138
    |2| K.A. Mauritz, R.B. Moore, State oI understanding oI NaIion, Chem. Rev. 104 (2004) 4535.
    |3| S. Cleghorn, J. Kolde, W. Liu, Handbook oI FuelCells Fundamentals Technology and Application, vol. 3, 2003, p. 566.
    -260-
    PB.2.6
    An AFM analysis of the changes on the surface of several nanofiltration membranes
    after the purification of clavulanic acid solutions
    A. L. Carvalho
    1
    , A. Hernandez
    2
    , L. Palacio
    2
    , P. Pradanos
    2
    , F. Maugeri
    1
    1
    Departament of Food Engineering, Facultv of Food Engineering, P. O. Box 6121, Universitv of Campinas UNICAMP,
    CEP. 13083-862, Campinas, SP, Bra:il
    2
    Depto. de Termodinamica v Fisica Aplicada, Fac. de Ciencias, Universidad de Jalladolid, Real de Burgos s/n, 47071
    Jalladolid, Spain
    limoeiroIea.unicamp.br
    The membrane morphology, its pore density and its pore size distribution determine its
    perIormance in a separation process. AFM gives topographic images at an atomic
    resolution which makes it an interesting technique to study the surIace properties oI
    nanoIiltration membranes |1|. Here we will study Iour commercial nanoIiltration
    membranes: NF90 (polyamide) and NF (polypiperazine amide) Irom Filmtec
    TM
    and
    NP010 and NP030 (polysulIone) Irom Microdyn Nadir

    . This procedure showed that


    the NF90 membrane has an irregular structure with circular and slit pores, the
    membrane NF presents a pure granular structure, and the membranes NP010 and NP030
    have a peculiar granular structure somehow similar to a string oI beads.
    These membranes were used to puriIy a synthetic solution oI clavulanic acid at a
    concentration oI 750 mg/L. Filtration was perIormed at 25C, at a pH oI 6.2, at a
    transmembrane pressure oI 2x10
    6
    Pa and at a stirring Irequency oI 600 rpm. The
    morphology oI these membranes was studied by AFM aIter their use to Iilter the
    clavulanic acid. The NF90 membrane presented a similar structure beIore and aIter its
    use. In both cases the surIace was rough and it did not change what seems to indicate the
    appearance oI a very thin layer oI adsorption. Examples oI the NF90 membrane beIore
    and aIter its use can be seen in Figure 1. The NF membrane showed a relatively smooth
    structure with similar granular structures both beIore and aIter the Iiltration oI the
    clavulanic acid. In this case, nothing can be concluded on the adsorption as Iar as it
    could be high but uniIorm what should lead to very slight changes in the morphology oI
    the surIace. The NP010 membrane presented a totally diIIerent structure aIter its use
    with a disappearance oI the original topology and the Iormation oI a highly rugged
    morphology, with a twoIold roughness. Finally, the NP030 membrane changed its
    structure Irom extremely smooth beIore the Iiltration to highly rough aIter its use what
    indicates a high adsorption. It seems that the NF90 and possibly the NF membranes are
    less Iouled by the clavulanic acid that should interact less with the amide groups that
    with the sulIonic groups.
    |1| N. Hilal, H. Al-zoubi, N. A. Darwish, A. W. Mohammad, M. Abu Arabi, A comprehensive review oI nanoIiltration
    membranes: treatment, pretreatment, modeling, and atomic Iorce microscopy, Desalination, 2004, 170, 281-308
    Acknowledgements: The authors acknowledge the Iinancial support Irom Coordenao de AperIeioamento de Pessoal de
    Nivel Superior (CAPES).
    -261-
    Fig 1: AFM image Ior the NF90
    membrane
    PB.2.7
    Performance and stability of multi-channel MFI zeolite membranes detemplated by
    calcination and ozonication
    J. Kuhn
    1
    , S. Sutanto
    1
    , J. Gross
    1
    , F. Kapteijn
    2
    1
    Delft Universitv of Technologv, Process & Energv Department, Leeghwaterstraat 44, 2628 CA Delft, The Netherlands
    2
    Delft Universitv of Technologv, DelftChemTech, Catalvsis Engineering, Ceramic Membrane Center, The Pore, Julianalaan
    136, 2628 BL Delft, The Netherlands
    J.KuhnTUDelIt.nl
    Two multi-channel high-silica MFI membranes have been tested Ior the removal oI ethanol Irom a 7 and 3 mol aqueous
    solution under pervaporation conditions. One membrane is detemplated by calcination at 773 K, and one is ozonicated at 473
    K. The Ilux and ethanol separation Iactor were determined at 348 K, 360 K, and 373 K. The ethanol separation Iactors oI both
    membranes were similar and ranged Irom ~20 at 373 K to ~40 at
    348 K. The ethanol and water Iluxes through both membranes in
    this temperature range are proportional to the component
    Iugacity diIIerence over the membranes. The calcined membrane
    showed an 80 higher Ilux than the ozonicated membrane,
    showing the ozonication could not completely remove the
    template. AIter the ozonicated membrane was calcined at 723 K,
    the Ilux increased to a similar value as the initially calcined
    membrane, while the separation Iactor did not change. Both
    membranes showed an increase in Ilux by a Iactor oI two aIter a
    subsequent calcination at 823 K, also without aIIecting the
    separation Iactor. The high calcination temperature required Ior
    complete detemplation indicates the presence oI aluminum in the
    zeolite Iramework oI the membrane. The membrane stability
    was monitored Ior 40 h and 177 h oI operation Ior the initially
    calcined and ozonicated membrane, respectively. At 348 K the
    membranes showed stable perIormance, but the stability oI the
    membranes at elevated temperatures is limited, showing a decrease in both Ilux and selectivity during operation at 373 K. The
    eIIect oI the exposure to a water/ethanol mixture on the zeolite membrane is investigated by diIIuse reIlectance inIrared
    Fourier transIorm (DRIFT) spectroscopy, magic angle spinning nuclear magnetic resonance (MAS NMR), Thermogravimetric
    analysis (TGA), and nitrogen adsorption experiments using several MFI-type zeolite powders. The most plausible mechanism
    causing the instability oI the membrane is related to ethoxy Iormation oI the ethanol with the silanol groups and Bronsted acid
    sites in the zeolite Iramework, possibly combined with hydrolysis.
    PB.2.8
    Rejection rate and retention capacity of membrane filters
    S. Mori
    1
    , M. Kanai
    2
    1
    Kubota Corporation, 1-1-1 Hama, Amagasaki, Hvogo, 661-8567, Japan
    2
    Kubota Membrane Europe, 8 Hanover Street, London, W1S 1YE, United Kingdom
    sgy-morikubota.co.jp ; kanaikubotalon.co.uk
    The rejection rate is one oI the main characteristics oI the Iilter sheet Ior the Membrane Bioreactor (MBR).|1| The rejection
    rate is usually analysed as Iollows: A known amount oI latex spheres are dispersed into distilled water. The latex solution is
    then Iiltered by a Iilter media. The rate oI residual spheres is calculated by measuring the amount oI Iiltered spheres employing
    the total carbon analysis. Standardisation oI analytical conditions Ior measuring the rejection rate is underway |2| and still not
    authorized. This we believe is because the rejection rate itselI is greatly inIluenced by the adopted analytical conditions, e.g.,
    the loading amount oI spheres used Ior the analysis.
    In this study, two types oI membranes, i.e. depth Iilter and screen Iilter, are compared. We obtained the Iollowing results.
    -262-
    Figure 1: Multi-channel MFI membrane and module.
    (1) The rejection rate Ior both types oI Iilters was 100 at low
    latex load and decreased as the latex load increased. However,
    aIter a certain load, the rejection rate began to increase gradually
    up to 100.
    (2) Less latex spheres loading gave the screen Iilter the rejection
    rate decrease Irom 100. The initial 100 rejection period
    corresponds to the adsorption oI latex spheres to the inner
    surIace oI membrane pores. Accordingly, the onset oI the
    rejection rate decrease oI the depth Iilter required greater latex
    spheres loading because it has larger adsorption area than that oI
    the screen Iilter.
    (3) When all the adsorption sites were Iilled with the spheres, the
    spheres began to spill out resulting in the decrease oI the
    rejection rate.
    (4) However, aIter the membranes experienced a certain amount
    oI latex load, the rejection rate increased due to the accumulation
    oI the spheres onto the membrane surIace layer.
    (5) ThereIore, the rejection-ability oI the membrane Iilter itselI should be evaluated by the curve in Figure 1, more
    conveniently by both the amount oI spheres loaded at the onset oI the rejection rate decrease and the rejection rate at the curve
    valley. The Iormer should be called 'Retention Capacity oI the Iilter.
    (6) When we compare the rejection-ability oI Iilters daringly by way oI the conventional rejection rate measurements, we
    should bear in mind that there is no unique analytical condition that applies to both depth Iilters and screen Iilters.
    |1| For example, Simon Judd, 'THE MBR BOOK, Elsevier, OxIord (2006).
    |2| CEN/WS/34 N 47, Submerged Membrane Bioreactor (MBR) Technology (2008).
    PB.2.9
    Development of mesoporous silica sphere-polysulfone hybrid membranes for gas
    separation
    B. Zornoza, C. Tellez, J. Coronas
    Nanoscience Institute of Aragon (INA) and Department of Chemical and Environmental Engineering, Universitv of Zarago:a,
    Maria de Luna 3, 50018, Zarago:a, Spain
    ctellezunizar.es
    Membrane processes have been recognized as a promising technology Ior gas separation and puriIication. During last decade
    various polymers have been modiIied with the incorporation oI inorganic Iillers (such as zeolites, carbon nanotubes, ordered
    silica, etc.) to produce mixed matrix membranes (MMMs). The idea oI mixing these phases could lead to an enhancement in
    gas permselectivity eIIiciency relative to Robeson's upper bound
    |1|
    since they combine the superior gas transport properties
    and thermal resistance oI the Iillers with the desirable mechanical properties, good processability and low price oI polymers
    |2|
    .
    The aim oI this work is to characterize and evaluate the gas separation perIormance oI MMMs composed oI mesoporous silica
    spheres (MSS) dispersed in a polysulIone matrix (Udel

    ). Due to the rigid chain mobility oI this glassy polymer weak


    interaction between microporous Iillers may result
    |2|
    .
    Figure 1. SEM images oI 8 wt.MSS-MMM.
    Thus, the synthesis oI spherical mesoporous particles with narrow particle size distribution could improve the interIacial
    properties in the preparation oI highly homogeneous MMMs. SEM images (Iigure 1) suggest an optimum contact between
    phases based on the penetration oI the polymer chains into the mesoporosity. Hydrogen puriIication Irom a 50 H
    2
    -CH
    4
    -263-
    Figure 1: Rejection rate as a Iunction oI loading amount
    oI 0.03um-dia latex spheres
    mixture Ior 0-32 wt. MSS-PolysulIone MMMs are shown in Iigure 2. Although H
    2
    and CH
    4
    permeabilities continuously
    increase with loading, an optimum oI selectivity was Iound. Loadings lower than 8 wt. MSS do not seem to alter
    signiIicantly MMMs transport properties while higher would create nonselective by-passing channels connecting surrounded
    voids between silica particles as observed by transmission electron microscopy (not shown).
    0
    1
    2
    3
    20
    40
    60
    80
    100
    120
    0,00 0,04 0,08 0,12 0,16 0,32
    0
    1
    2
    3
    20
    40
    60
    80
    100
    120
    H
    2
    /
    C
    H
    4

    S
    e
    I
    e
    c
    t
    i
    v
    i
    t
    y

    P
    e
    r
    m
    e
    a
    b
    i
    I
    i
    t
    y

    (
    b
    a
    r
    r
    e
    r
    )

    MSS mass fraction
    CH4 Permeability
    H2 Permeability
    H2/CH4 Selectivity
    Figure 2. Gas separation results Ior H
    2
    /CH
    4
    mixture at 35C and AP175 kPa.
    Financing Irom Spanish Ministry oI Education and Science (MAT2007-61028 and FPU program) is grateIully acknowledged.
    |1| L. M. Robeson, Journal oI Membrane Science, 2008, 320, 390-400
    |2| R. Mahajan, W. J. Koros, Industrial & Engineering Chemistry Research, 2000, 39, 2692-2696
    PB.2.10
    Influence of concentration-polarization on salt permeability and ion transport
    numbers measured in a dead-end test cell
    V. Romero, J.D. Ramos, L. Pelaez, M.I. Vazquez, J. Benavente
    Grupo de Caracteri:acion Electrocinetica v de Transporte en Membranas e Interfases, Departamento de Fisica Aplicada I,
    Facultad Ciencias. Universidad de Malaga. E-29071 Malaga, Spain.
    JBenaventeuma.es
    The increase oI solute concentration in the solution layer nearest to the membrane surIace is a phenomenon directly related to
    the barrier eIIect oI membranes. Solution stirring at a given velocity is the usual way to carry out measurements to reduce
    concentration-polarization in the dead-end test cells normally used at laboratory scale, but they do not allow the estimation oI
    polarization eIIects on the values oI determined transport parameters. This work studies the eIIect oI solution stirring in the
    determination oI two basic parameters Ior membrane characterization such as salt permeability and ion transport numbers
    across regenerated cellulose (RC) membranes with diIIerent structures (dense but highly swollen, porous paper-supported and
    dense with polypropylene reinIorcement) in contact with electrolyte solutions at diIIerent concentrations, which allows the
    correlation oI transport parameter-membrane structure with characteristic oI the stagnant layer such as thickness and solution
    concentration.
    Membrane system salt permeability (P
    ms
    ) was determined Irom diIIusion measurements carried out at a constant Ieed
    concentration (c
    I
    0.01 eq/l) and diIIerent solutions stirring rates (200 (rpm) 1000), while cation transport number was
    obtained Irom membrane potentials (
    mb
    ) at diIIerent concentration ratio (0.01/c
    v
    , 0.002 c
    v
    (eq/l) 0.1) and two solution
    stirring rates ( 550 rpm and 0). The eIIective salt permeability in the membrane (P
    s
    ) can be obtained by [1|: P
    ms
    [P
    s
    (1
    )|/(1 2[P
    s
    /P
    s
    o
    ]). Depending on the membrane structure P
    ms
    values at 550 rpm are 50 or 80 oI the corresponding
    P
    s
    , indicating the higher oI lower eIIect oI concentration-polarization. With respect to membrane potential measurements,
    solution concentration on the membrane surIace (c
    m
    ) might be estimated by comparing stirred and non-stirred values (
    mb
    and
    mb
    *, respectively):
    mb
    *
    mb

    diI
    o
    , where
    diI
    o
    represents the solution diIIusion potential in the stagnant layer.
    Spanish Science and Technology Ministry (CYCIT project MAT2007/65065) is acknowledged Ior Iinancial support.
    [1| M. V. Barragan, C. Ruiz-Bauza, Membrane potential and electrolyte permeation in a cation-exchange memrbane, J.
    Membr. Sci., 1999,154, 261-270.
    -264-
    PB.2.11
    Diffusional permeability and ion transport across a bilayer membrane: correlation
    with single layers parameters
    J.D. Ramos, V. Romero, L. Pelaez, S. Bijani, M.I. Vazquez, J. Benavente
    Grupo de Caracteri:acion Electrica en Membranas e Interfases, Departamento de. Fisica Aplicada I, Facultad Ciencias.
    Universidad de Malaga. E-29071 Malaga, Spain.
    JBenaventeuma.es
    Characterization oI bilayer membranes has an increasing interest due to their wide spread applications, which includes typical
    composite membranes Ior high pressure Iiltrations (NanoIiltration and Reverse Osmosis), but also Ior new applications such as
    release diIIusion systems, sensors, membranes with modiIied surIaces and bipolar membranes. These systems basically consist
    oI a series array oI layers Irom diIIerent materials and with diverse structures, which exhibit diIIerent solute or ions transport
    characteristic, being the two-layer membrane the simples system |1-2|. Due to the diIIerent structures and physicochemical
    properties oI each sublayer, linearity oI pressure, concentration and electrical potential gradients across the whole composite
    membrane do not exist, and other assumptions have to be made Ior membrane characterization based on total membrane
    measurements.
    In this work, Iour regenerated cellulose (RC) based membranes with diIIerent structures, two dense but highly hydrophilic
    samples (RC-3 and RC-6), a dense RC membrane with polypropylene reinIorcement (RC70PP) and a porous paper-supported
    membrane (P-RC), were independently characterized by determining salt permeability and ion transport numbers, which were
    obtained Irom salt diIIusion and membrane potential measurements carried out with NaCl solutions, respectively. Two
    diIIerent bi-layer structures (BLs) were obtained by combining the single membranes (RC-6/P-RC and RC-3/RC70PP), which
    allows the comparison oI transport parameters across the BLs structure with those determined Ior each single layer in order to
    establish diIIerences/correlations transport-structure. The degree oI asymmetry Ior diIIusional permeability across both BLs
    was quantiIied by determining the salt Ilux ratio Ior both opposite orientations, while the eIIect oI concentration polarization
    on ion transport was determined Irom membrane potential measured at two diIIerent solution stirring rates.
    Acknowledgements: To CICYT (Project MAT2007-65065, Spain) Ior Iinancial support.
    |1| O. Kedem, A. Katchalsky, The permeability oI membranes, Trans. Faraday Soc., 1963, 59, 1941-1952.
    |2| G. Jonsson, J. Benavente, Determination oI some transport coeIIicients Ior the skin and porous layers oI a composite
    membrane, J. Membr. Sci., 1992, 69, 29-42.
    PB.2.12
    Characterisation of the active layer of a nanofiltration membrane in contact with
    KCl and CaCl
    2
    solutions
    M.I. Vazquez, J. Benavente
    Grupo de Caracteri:acion Electrocinetica v de Transporte en Membranas e Interfases, Departamento de Fisica Aplicada I,
    Facultad de Ciencias, Universidad de Malaga, E-29071 Malaga (Spain).
    mvazquezuma.es
    Characterization oI composite membranes Ior NanoIiltration processes is normally carried out by determining transport,
    electrical and structural parameters Ior the dense active layer, which is considered responsible oI membrane perIormance since
    porous sublayer contribution is usually neglected.
    Chemical surIace characterization and values oI salt rejection, electrochemical surIace charge density, active layer electrical
    resistance and capacitance Ior a commercial nanoIiltration polyamide/polysulIone membrane in contact with KCl and CaCl
    2
    solutions are presented in this paper.
    Salt rejection, hydrodynamic permeability and electrical surIace parameters (zeta potential and electrokinetic surIace charge
    density) were obtained Irom Iiltration and tangential streaming potential (TSP) measurements, respectively. Electrochemical
    impedance spectroscopy (EIS) measurements were carried out in order to obtain and independent determination oI active layer
    and porous sublayer electrical resistance by using equivalent circuits (EC) as models |1-2|. For the studied membrane a
    (RaCa)-(RpWp) equivalent circuit was obtained, which indicates charge adsorption on the dense active layer but a diIIusion
    process Ior the porous support |3|, which allows morphological inIormation on the active layer determined Irom average
    -265-
    capacitance value. Comparison oI the corresponding results obtained with KCl and CaCl
    2
    solutions gives inIormation on the
    inIluence oI the type oI electrolyte and the external solution concentration dependence on the studied parameters.
    |1| K. Asaka, Dielectric properties oI cellulose acetate reverse osmosis membranes in aqueous salt solutions, J. Membr. Sci.,
    1990, 50, 153-161.
    |2| M.Oleinikova, M.Muoz, J.Benavente, M.Valiente, Evaluation oI structural properties oI novel activated composite
    membranes containing organophosphorous extractants as carriers, Langmuir, 2000, 16(2), 716 -721.
    |3| A. Caas, M.J. Ariza, J. Benavente, Characterization oI actives and porous sublayers oI a composite reverse osmosis
    membrane by impedance spectroscopy, streaming and membrane potentials, salt diIIusion and X-ray photoelectron
    spectroscopy measurements, J. Membr. Sci., 2001, 183, 135-146.
    PB.2.13
    Impact of sodium hypochlorite on aromatic polyamide composite reverse osmosis
    membranes: identification of appropriate methods for the characterization of
    membrane degradation
    A. Ettori
    1,2
    , E. Gaudichet-Maurin
    2
    , J-C. Schrotter
    2
    , P. Aimar
    1
    , C. Causserand
    1
    1
    Universite de Toulouse , INPT, UPS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    2
    Centre de Recherche sur lEau, Jeolia Environnement , Chemin de la digue BP76, 78603 Maisons-Laffitte cedex, France
    causserachimie.ups-tlse.Ir
    Membrane ageing phenomena and degradation oI membrane perIormances when exposed to oxidizing chemicals, used in
    water disinIection and Ior membrane cleaning in drinking water plants, such as bleach solutions are a major concern Ior
    membrane manuIacturers and end-users. Membrane deterioration mechanisms and the correlation between changes in
    properties oI the membrane surIace and alterations oI membrane perIormance are not Iully comprehended. Explanations vary
    with the membrane surIace polymer type (Iunctional groups, cross-linking) |1, 2, 3|. Commercially available composite
    polyamide reverse osmosis membranes (RO) are selected Ior the present study. Scope oI this work includes evaluating the
    impact oI chemical stress Iactors on the chemical properties oI the polyamide skin layer (active Ior Iiltration), and on the
    hydraulic perIormances oI the membrane. Samples extracted Irom an 8 spiral wound RO module (Dow FILMTEC) are
    exposed to sodium hypochlorite solutions in severe conditions, i.e at known degrading concentration and exposure time, pH,
    by immersion and by Iiltration. DiIIerent analytical tools are assessed Ior a multiscale investigation oI membrane ageing |1, 2,
    3, 4, 5| : FTIR-ATR and XPS Ior surIace molecular composition, interIerometer and tensiometer Ior surIace roughness and
    hydrophilicity, and sodium chloride retention trials Ior membrane hydraulic perIormance. A number oI these analytical
    techniques, selected Ior their relevance, are used Ior the characterization oI membranes sampled Irom desalination plants, with
    controlled inIormation on Iiltration and chemical cleaning operating conditions and on the occurrence oI events or incidents.
    The corresponding results will be discussed. Given that on-site aged membranes are degraded in less extreme conditions than
    those during accelerated trials perIormed at the lab scale, such an approach allows Ior the most relevant tool to be chosen. A
    discussion on the identiIication oI an appropriate indicator Ior the prediction oI the residual liIetime oI membranes used in
    drinking water plants |4| will concluded the presentation.
    Veolia Environnement is grateIully acknowledged Ior Iunding this work
    |1| J. Glater, S-K. Hong, M. Elimelech, The search Ior a chlorine-resistant reverse osmosis membrane, Desalination, 1994, 95,
    325-345
    |2| Y-N. Kwon, J. Leckie, Hypochlorite degradation oI crosslinked polyamide membranes, I. Changes in
    chemical/morphological properties, Journal oI Membrane Science, 2006, 283, 21-26
    |3| Y-N. Kwon, J. Leckie, Hypochlorite degradation oI crosslinked polyamide membranes, II. Changes in hydrogen bonding
    behaviour and perIormance, Journal oI Membrane Science, 2006, 282, 456-464
    |4| E. Gaudichet-Maurin, F. Thominette, Ageing oI polysulIone ultraIiltration membranes in contact with bleach solutions,
    Journal oI Membrane Science, 2006, 282, 198-204
    |5| S. Rouaix, C. Causserand, P. Aimar, Experimental study oI the eIIects oI hypochlorite on polysulIone membrane
    properties, Journal oI Membrane Science, 2006, 277, 137-147
    -266-
    PB.2.14
    Influence of CO
    2
    on stability and permeation behaviour of Ba
    0.50
    Sr
    0.50
    Co
    0.80
    Fe
    0.20
    O
    3-
    membrane material
    A. Moebius, D. Schlehuber, T. Markus
    Institute of Energv Research, Forschungs:entrum Juelich GmbH, D-52425 Juelich, Germanv
    a.moebiusIz-juelich.de
    Gas separation membranes are considered to be an eIIicient technology Ior the Iuture generation oI zero CO
    2
    -emission power
    plants. In the oxyIuel combustion process the membrane will be used to separate oxygen Irom air in order to produce a
    combustion gas highly concentrated in O
    2
    .
    The perovskite-type material Ba
    0.50
    Sr
    0.50
    Co
    0.80
    Fe
    0.20
    O
    3-o
    is a mixed ionic and electronic conductor which could be used to
    separate oxygen Irom air. Due to the high oxygen Iluxes which could be reached, this material is a promising candidate Ior gas
    separation membranes in the oxyIuel process.
    The stability and the permeation behaviour oI membrane materials are both a crucial Iactor in the selection oI the material Ior
    membrane technology. In this work the degradation in CO
    2
    -containing atmosphere and the permeation behaviour oI
    Ba
    0.50
    Sr
    0.50
    Co
    0.80
    Fe
    0.20
    O
    3-o
    are investigated.
    Annealing experiments in CO
    2
    -containing atmosphere are conducted to investigate the Iormation oI carbonates on the
    membrane surIace. It is known Irom literature that Ba
    0.50
    Sr
    0.50
    Co
    0.80
    Fe
    0.20
    O
    3-o
    Iorms (Ba,Sr)CO
    3
    iI it is annealed in CO
    2
    -
    containing atmospheres at elevated temperatures |1|. Furthermore, the tendency oI Ba
    0.50
    Sr
    0.50
    Co
    0.80
    Fe
    0.20
    O
    3-o
    to react with CO
    2
    and the reversibility oI the Iormation oI carbonates is investigated using DiIIerential Thermal Analysis. The reversibility oI the
    carbonate Iormation is also checked by annealing experiments. XRD, SEM and EDX measurements are conducted to check the
    changes in structure and composition oI the annealed material.
    The permeation behaviour oI Ba
    0.50
    Sr
    0.50
    Co
    0.80
    Fe
    0.20
    O
    3-o
    is investigated in presence and absence oI CO
    2
    in the sweep gas. The
    oxygen Ilux decreases rapidly iI the sweep gas is switched Irom pure argon to a CO
    2
    -containing gas mixture. However, iI the
    sweep gas is shiIted back to pure argon similar oxygen Iluxes are obtained.
    M. Arnold, H. Wang, and A. FeldhoII, InIluence oI CO
    2
    on the oxygen permeation perIormance and the microstructure oI
    perovskite-type (Ba
    0.5
    Sr
    0.5
    )(Co
    0.8
    Fe
    0.2
    )O
    3o
    membranes, Journal of Membrane Science, 293 (2007) 4452.
    PB.2.15
    Investigation of the charge formation mechanismsin polyamide nanofiltration
    membranes by the adsorption-amphoteric model
    L. Bruni, S. Bandini
    Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali, Universitv of Bologna, Jia U.Terracini, 28,
    I-40131, Bologna, Italv
    serena.bandinimail.ing.unibo.it , jgcdq.Ict.unl.pt
    Membrane charge is remarkable in determining separation perIormances oI nanoIiltration membranes. Basically, the charge oI
    NF membranes is induced by the acidic characteristics oI the electrolyte solutions kept in contact with the membrane itselI, as
    well as by type and concentration oI ionic species |1|. Understanding the phenomena which determine the mechanisms oI
    charge Iormation is thereIore essential to get a correct description oI the volumetric membrane charge.
    The adsorption-amphoteric model (ADS-AMF) |1,2| is applied to describe the membrane charge behaviour oI two polyamide
    thin Iilm composite membranes, Desal DK and CSM NE70, operating in NF processes with aqueous solutions containing
    NaCl, CaCl
    2
    or Na
    2
    SO
    4
    , as well as mixtures oI them, at various Ieed pH values. Key point oI the ADS-AMF model is the site-
    representation oI the membrane as the sum oI hydrophobic as well as oI hydrophilic Iunctional groups which can support
    charges derived Irom various chemical and physical mechanisms. The prevailing phenomena considered are acid/base
    dissociation oI the hydrophilic Iunctional groups, counter-ions site binding on the dissociated sites and competitive adsorption
    oI ions on the hydrophobic Iunctional groups.
    The study is based on the elaboration oI volumetric membrane charge values which are calculated as adjustable parameters by
    Iitting experimental rejections with the Donnan Steric Pore and Dielectric Exclusion model |3|, also accounting oI
    concentration polarization phenomena in the Ieed side.
    -267-
    In the cases investigated, the membranes show quite similar behaviours Ior the same electrolytes. With NaCl-water solutions,
    at concentrations higher than 5 mol/m
    3
    , a monotone behaviour is observed Ior the membrane charge as a Iunction oI salt
    concentration; in this case the ionic competitive adsorption on hydrophobic sites according to a Langmuir-type mechanism is
    dominant with respect to the eIIects oI counter-ion site binding. With non-symmetric electrolytes, on the contrary, in the case
    in which the divalent ion is the counter-ion, the membrane charge appears as an unimodal Iunction oI salt concentration and
    both the membranes show an amphoteric behaviour which greatly depends on the salt concentration. The membrane charge is
    the result oI the competition between co-ion adsorption on the hydrophobic sites and counter-ion site-binding on the
    dissociated hydrophilic sites.
    Finally, the ADS-AMF model is applied to the case oI multicomponent mixtures and suitable mixing rules are deIined between
    the membrane charge values oI the corresponding single salts solutions.
    |1| L.Bruni, S.Bandini, J. Membrane Sci. 308 (2008)136-151.
    |2| S.Bandini, L.Bruni, in "SurIace Electrical Phenomena in Membranes and Microchannels", A. Szymczyk (Ed), Transworld
    Research Network (2008) 1-30.
    |3| S. Bandini, D. Vezzani, Chemical Engineering Science, 58 (2003) 3303-3326.
    PB.2.16
    Evaluation of the performance of a 1.2m commercial membrane impregnated with
    silver for bacteria retention during the crossflow microfiltration process
    R. N. Haneda
    1
    , Elson Longo
    2
    , S. R. Fontes
    1
    1
    Universitv of So Paulo (USP), School of Engineering of So Carlos, Department of Mechanical Engineering, Avenue
    Trabalhador So-carlense, 400, 13566-590, So Carlos, So Paulo
    2
    Federal Universitv of So Carlos (UFSCAR), Interdisciplinarv Laboratorv of Electrochemistrv and Ceramics (ILEC),
    Highwav Washington Luis, km 235, 13565-905, So Carlos, So Paulo
    rnhsc.usp.br/ srIsc.usp.br
    Membranes operate predominantly in crossIlow Iiltration mode and are utilized within the production process, Ior clariIying
    and concentration, and also as a means oI treating the wastewaters produced by several industrial processes with reuse oI
    water. In the Iruit juice and syrup industry, where permeate rather than retentate is the product, UF membranes are widely used
    to clariIy apple, pear, orange, grape, cranberry, blackcurrant and pineapple juices by removing impurities such as yeast,
    moulds, bacteria, pyrogens, colloids and solids |1|. However, the removal oI proteins, polysaccharides, tannis and polyphenols
    also occurs, while the permeate Ilux decreases dramatically during the Iiltration due to the adsorption oI solutes on the outer
    membrane and inner pore surIace, blocking oI pores by rejected solutes or Iormation oI a thick cake layer oI precipitated
    solutes on top oI the membrane |2|. Li et al. (2007) aIIirm that the minimization oI membrane Iouling is essential Ior an
    economical membrane process and a detailed understanding oI causes oI Ilux decline. ThereIore their relative contribution is
    essential to reduce the polarization phenomenon |3|. In this context, this work presents preliminary experimental results oI the
    crossIlow microIiltration process applied to retaining bacteria and clariIying the aai juice, using a commercial membrane oI u-
    alumina (Al
    2
    O
    3
    ), with average pore size oI 1.2m. This pore size was utilized in an attempt to reduce the Iouling and improve
    the permeate Ilux without utilizing the usual enzymatic treatment. However, this pore size was not enough to block the bacteria
    totally, and thereIore, the membrane was impregnated with bactericide material by a methodology developed in the
    Interdisciplinary Laboratory oI Electrochemistry and Ceramics (ILEC/UFSCar/Brazil) |4|. It must be emphasized that the
    bacteria retention analysis was standardized, and all the tests were realized with the same initial bacteria counting (CFU/ml),
    which was perIormed Iollowing the oIIicial method Irom AOAC (Association oI OIIicial Analytical Chemists) included in
    Chapter 7 Irom 4
    th
    Edition oI the Compendium oI Methods Ior the Examination oI Dairy Products |5|. Scanning Electron
    Microscopy (SEM) was utilized as an essential tool to characterize the morphology and composition oI this micro porous
    ceramic structure, and also to evaluate the cake-layer developed during the processing on the Iilter surIace.
    |1| R. Skelton, Membrane Filtration Applications in the Food Industry, Filtration and Separation, 2000, 37(3), 28-30.
    |2| Y. Wang, S. Tang, J. Zhang, et al., ClariIication oI soy sauce by the inorganic ceramic membrane ultraIiltration, China
    Condiment (Chinese), 2004, 1, 140-143.
    |3| M. Li, Y. Zhao, S. Zhou, W. Xing, F. Wong, Resistance analysis Ior ceramic membrane microIiltration oI raw soy sauce,
    Journal Membrane Science, 2007, 299, 122-129.
    |4| R. Haneda, R. Ikegami, C. A. Fortulan, et al., MicroIiltration with chemistry treating oI commercial membranes and
    microporous tubes Ior retention oI bacteria E. coli on processing oI wastewater oI dairy products, Desalination, 2006, 199,
    313-315.
    -268-
    |5| D. T. Laird, S.A. Gambrel-Lenarz, F. M. Scher et al., Microbiological count methods. In: H. M. Wehr & Frank, J.F (Eds),
    Standard Methods for the Examination of Dairv Products, 17
    th
    ed. American Public Health Association, Washington, D. C.,
    2004, Chapter 6, 537-550.
    PB.2.17
    Influence of salts on the retention of polyethyleneglycol by an NF organic membrane:
    pore swelling and salting-out effects
    A. Escoda
    1
    , P. Fievet
    1
    , S. Lakard
    1
    , A. Szymczyk
    2
    1
    Institut UTINAM, UMR CNRS 6213, Universite de Franche-Comte, 16 route de Grav, 25030 Besanon Cedex, France
    2
    Chimie et Ingenierie des Procedes, UMR 6226 CNRS-Universite de Rennes 1-ENSCR, 263 Avenue du General Leclerc, CS
    74205, 35042 Rennes Cedex, France
    patrick.Iievetuniv-Icomte.Ir
    In the context oI process intensiIication, membrane processes are increasingly evolving towards the application oI Iluids oI
    greater complexity, containing both mineral and organic compounds. Among the membrane processes, nanoIiltration (NF) has
    attracted increasing attention over the recent years with the aim to develop new applications, such as the production oI organic
    acids by the puriIication oI a Iermentation broth or treatment oI liquid wastes containing organic pollutants and mineral salts.
    However, several studies have shown that the transIer oI an organic solute increases with salt concentration and that such
    increase also depends on the salts nature |1,2,3|. As a result, selectivity can be very poor as compared to the one expected.
    In the present work, retention properties oI an NF organic membrane were investigated with single polyethyleneglycol (PEG)
    solutions and mixed PEG/inorganic salt solutions. The retention rate oI PEGs was Iound to decrease in the presence oI salts
    (KCl, LiCl, K
    2
    SO
    4
    and MgCl
    2
    ), the salt eIIect on the retention oI neutral solutes being more pronounced at high salt
    concentrations. It should be noted that the same Iiltration tests (i.e. using the same mixed-solute solutions) had been conducted
    with an NF ceramic membrane in a previous work |3|. It was Iound that the lowering oI PEG retention rates Iollowed the
    HoImeister series. Two main hypotheses have been postulated in the literature to explain the retention lowering phenomenon.
    The Iirst one is that the decrease in the rejection rate oI neutral solutes could result Irom pore swelling, i.e. an increase in the
    mean pore size due to the repulsion Iorces between counterions in the electrical double layer at the pore walls |1,2|. The
    second hypothesis is that ions might decrease the eIIective size oI the neutral species, because water would rather solvate ions
    (salting-out eIIect) |3|.
    The aim oI this work was to evaluate the signiIicance oI these two eIIects in the case oI an NF organic membrane. To this end,
    the experimental data oI rejection rates obtained with the organic membrane were used to compute the variation in the mean
    pore radius in the presence oI the various salts, the Stokes radius oI PEG molecules in the presence oI the various salts having
    been determined Irom rejection rates obtained with the ceramic membrane. The results obtained show that the eIIective pore
    size increases with salt concentration, varying Irom 6 to 18 in the case oI decimolar solutions and Irom 30 to 50 in the
    case oI molar solutions, depending on the salt used. The pore swelling phenomenon was conIirmed by surIace charge
    measurements: the more the membrane surIace charge increases, the higher the eIIective pore size becomes.
    |1| Bouchoux A., Roux-de Balmann H. and Lutin F., Journal oI Membrane Science, 258 (2005) 123-132.
    |2| Bargeman G., Vollenbroek J. M., Straatsma J., Schroen C. G. P. H. and Boom R. M., Journal oI membrane science, 247
    (2005) 11-20.
    |3| Bouranene S., Szymczyk A., Fievet P. and Vidonne A., Journal oI Membrane Science, 290 (2007) 216-221.
    -269-
    PB.2.18
    Impact of TiO
    2
    nanoparticles on morphology and performance of organic solvent
    highly stable polyimide nanofiltration membranes
    I. Soroko, A. Livingston
    Department of Chemical Engineering and Chemical Technologv, Imperial College London, Exhibition Road, London SW7
    2AZ, United Kingdom
    a.livingstonimperial.ac.uk
    Organic solvent nanoIiltration (OSN) has drawn increasing interest among both academic and industrial researchers and it has
    been successIully applied in a variety oI chemical processes |1|. Chemically crosslinked PI membranes |2| can withstand
    aggressive solvents and thus have been used Ior Iabrication oI OSN membranes. It has been reported that control over
    molecular weight cut oII oI PI nanoIiltration membranes can be achieved by varying oI the ratio oI the solvent to the volatile
    co-solvent |3|. Increasing solvent concentration in the dope solution yields membranes with increasing MWCO and enhanced
    permeability, but with the drawback oI an increasing number oI macrovoids in the sublayer |3|. This work Iocuses on
    investigating the inIluence oI inorganic Iillers addition on membrane morphology and perIormance through cross-Ilow
    Iiltration tests in solvents with diIIerent polarities. SEM pictures oI cross-sections oI PI/TiO
    2
    membranes show dramatically
    changed morphology oI the composite membranes compared to reIerence membranes with no TiO
    2
    addition (Figure 1).
    Figure 1: A: PI membrane with no TiO
    2
    ; B: PI membrane with 5 wt.
    TiO
    2
    .
    However, while the macrovoids were suppressed by the presence oI TiO
    2
    , perhaps surprisingly it was Iound that perIormance
    measured in terms oI compaction, Ilux and molecular weight cutoII was not altered to a major extent. In summary, Irom
    obtained data it can be concluded that addition oI TiO
    2
    signiIicantly changed membrane matrix morphology, but had little
    eIIect on membranes selectivity and only a small inIluence on compaction resistance and hydrophilicity. This indicates that
    skin layer determinates to a great extent selectivity and permeability oI PI membranes used in organic solvent nanoIiltration,
    with the sublayer having a minor eIIect.
    |1| P. Vandezande , L.E.M. Gevers , I.F.J. Vankelecom. Solvent resistant nanoIiltration: separating on a molecular level.
    Chemical Society Reviews 2007; 37, 365-405.
    |2| Y.H. See-Toh, F.W. Lim, A.G. Livingston. Polymeric membranes Ior nanoIiltration in polar aprotic solvents. Journal oI
    Membrane Science 2007; 301, 3-10.
    |3| Y.H. See-Toh, M. Silva, A.G. Livingston. Controlling molecular weight cut-oII curves Ior highly solvent stable organic
    solvent nanoIiltration (OSN) membranes. Journal oI Membrane Science 2008; 324, 220-232.
    PB.2.19
    Irradiated polysulfone membranes by gamma ray
    M. A. Masuelli
    1
    , N. A. Ochoa
    1
    , J. Marchese
    1
    , M. Grasselli
    2
    1
    Instituto de Fisica Aplicada -CONICET-FONCvT, Universidad Nacional de San Luis. Chacabuco 917, San Luis (5700),
    Argentina.
    2
    Depto. de Ciencia v Tecnologia. Universidad Nacional de Quilmes, CONICET R.Saen: Pea 352 (B1876BXD), Bernal,
    Quilmes, Provincia de Buenos Aires. Argentina
    masuelliunsl.edu.ar
    PolysulIone (PSI) membranes with two diIIerent pore size were irradiated by -ray, Ior obtain hydrophilic membranes |1|.
    Svnthesis. PSI (Udel 3500P) 10 and 15 p/p respect to solvent were dissolved in N,N-DimethylIormamide (Sigma). Then they
    were mixed with 10 oI polyvinylpyrrolidone (85kDa, Stanton) and casting on support (FO2430, Fraudemberg). Finally, the
    casting solutions were coagulated in water at 25C.
    -270-
    Irradiation. A heterogeneous solution oI methanol/water (1/1 in vol.) were prepared. Then a portion oI Membrane (aprox. 374
    cm
    2
    oI area), was inmersed into these solution and all system was degassed with N
    2
    . The membranes were irradiated to 25C in
    irradiation cell (GammaCell de
    60
    Co, Centro Atomico Ezeiza, CONEA), with a dose oI 6.92 kGy, and rate oI 0.906 kGy/hs.
    AIter irradiation, the membranes were washed with methanol/ water solution, pure methanol and Iinally dry at 40C during 24
    hs |2|.
    Characteri:ation. The membranes were characterized by liquid-liquid displacement porosimetry (ISCO-500D syringe pump),
    contact angle measurement (Micromeritics Anglometer) and hydraulic permeability (Minitan S cell and Millipore peristaltic
    pump) |3|.
    Discussion. The increment oI PSI content on casting solution decreased the pore size. Radii pore distribution (Iig.1) evidence a
    increment oI mean pore size when the membranes were irradiated. The same behaivour was observed when hydraulic
    permeability measurements (m/sPa) was done on both no modiIied and modiIied membranes (10PSI10 11.76x10
    -10
    , 15PSI10
    9.91x10
    -10
    and 10PSI10Irr 57.17x10
    -10
    , 15PSI10Irr 14.80x10
    -10
    , respectively). Contac angle oI PSI was 78 degree, while
    10PSI10Irr and 15PSI10Irr membranes shown contact angles about oI 75 and 74 degree, respectively.
    Conclusion. This membranes present high hydrophilicity and great pore size. The irradiation process drive to rupture oI bonds
    via Iree radicals, generating pore more great and Iunctional group with aIinty to water like -COOH,-SO
    3
    H.
    |1| Effect of hvdrophilicitv on fouling of an emulsified oil wastewater with PJDF/PMMA membranes. N. Ochoa, M. Masuelli,
    J. Marchese. Journal oI Membrane Science 226(2003)203-211.
    |2| Immobili:ed metal ion affinitv hollow-fiber membranes obtained bv the direct grafting technique. Mariano Grasselli,
    Agustin A. Navarro del Caizo, Silvia A. Camperi, Federico J. Wolman, Eduardo E. Smolko, Osvaldo Cascone. Radiation
    Physics and Chemistry 55 (1999) 203-208.
    |3| SPC/PJDF membranes for emulsified oilv wastewater treatment. Martin Masuelli, Jose Marchese, Nelio A. Ochoa. Journal
    oI Membrane Science 326 (2009) 688693.
    PB.2.20
    Comparison of electrochemical properties of two different regenerated cellulose
    ultrafiltration membranes
    A. Pihlajamki
    1
    , M. Kallioinen
    1
    , M. Mnttri
    1
    , R. Takagi
    2
    1
    Laboratorv of Membrane Technologv and Technical Polvmer Chemistrv, Lappeenranta Universitv of Technologv, POBox 20,
    FI-53851 Lappeenranta, Finland
    2
    Shukugawa Gakuin College, 6-58 Koshikiiwa-cho, Nishinomiva 662-855, Japan
    Arto.Pihlajamakilut.Ii
    In this study two regenerated cellulose (RC) ultraIiltration (UF) membranes were compared. The membranes were UC030T
    (Microdyn-Nadir GmbH) and C30V (JSC STC Vladipor). Both membranes are highly hydrophilic. Their cut-oII values and
    pure water permeabilities should be in the same range. They diIIer, however, Irom their electrochemical properties as it can be
    seen in Fig. 1. The FTIR ATR spectra showed some diIIerences in the RC chemical compositions oI the membranes top layers.
    The membrane potential measurements also revealed that both membranes acquire their charge by adsorbing anions Irom
    surrounding solutions but the C30V membrane adsorb the anions three times more (the saturated amount oI anions oI the
    C30V membrane is about 0.586 mol/m
    3
    and about 0.179 mol/m
    3
    oI the UC030T membrane). This diIIerence was not Iound to
    play any signiIicant role in the retention oI uncharged molecule (polyethylene glycol, PEG). The retentions oI 6 kg/mol PEG
    were between 50 and 60 with the UC030T membrane and between 40 and 50 with the C30V membrane in diIIerent
    conditions. However, this diIIerence should be important when Iiltering charged molecules like proteins and could be used as
    advantage in case oI the C30V membrane.
    -271-
    C30V through
    0

    m
    M

    K
    2
    S
    O
    4
    1

    m
    M

    K
    2
    S
    O
    4
    3

    m
    M

    K
    2
    S
    O
    4
    1
    0

    m
    M

    K
    2
    S
    O
    4
    -30
    -25
    -20
    -15
    -10
    -5
    0
    A
    p
    p
    a
    r
    e
    n
    t

    Z
    e
    t
    a

    p
    o
    t
    e
    n
    t
    i
    a
    I
    ,

    m
    V
    C30V aIong
    0

    m
    M

    K
    2
    S
    O
    4
    1

    m
    M

    K
    2
    S
    O
    4
    3

    m
    M

    K
    2
    S
    O
    4
    1
    0

    m
    M

    K
    2
    S
    O
    4
    -30
    -25
    -20
    -15
    -10
    -5
    0
    A
    p
    p
    a
    r
    e
    n
    t

    Z
    e
    t
    a

    p
    o
    t
    e
    n
    t
    i
    a
    I
    ,

    m
    V
    UC030T aIong
    0

    m
    M

    K
    2
    S
    O
    4
    1

    m
    M

    K
    2
    S
    O
    4
    3

    m
    M

    K
    2
    S
    O
    4
    1
    0

    m
    M

    K
    2
    S
    O
    4
    -30
    -25
    -20
    -15
    -10
    -5
    0
    A
    p
    p
    a
    r
    e
    n
    t

    Z
    e
    t
    a

    p
    o
    t
    e
    n
    t
    i
    a
    I
    ,

    m
    V
    UC030T through
    0

    m
    M

    K
    2
    S
    O
    4
    1

    m
    M

    K
    2
    S
    O
    4
    3

    m
    M

    K
    2
    S
    O
    4
    1
    0

    m
    M

    K
    2
    S
    O
    4
    -30
    -25
    -20
    -15
    -10
    -5
    0
    A
    p
    p
    a
    r
    e
    n
    t

    Z
    e
    t
    a

    p
    o
    t
    e
    n
    t
    i
    a
    I
    ,

    m
    V
    FIG. 1. SurIace charges calculated Irom streaming potential data on the pore walls and on top oI the membranes when
    potassium sulphate concentration increases in the electrolyte solution. Background electrolyte was 1 mM KCl in all
    measurements. T25C, pH6.5.
    PB.2.21
    Nanofiltration as pretreatment for scaling control in SWRO: a systematic study
    L. Llenas
    1
    , X. Martinez-Llado
    1
    , A. Yaroshchuk
    2
    , M. Rovira
    1
    , J. DePablo
    1
    1
    CTM Centre Tecnologic, av.Bases de Manresa 1, 08242 Manresa, Spain
    2
    ICREA and Department of Chemical Engineering, Polvtechnic Universitv of Catalonia, av.Diagonal 647, 08028 Barcelona,
    Spain
    laia.llenasctm.com.es
    Seawater contains high concentrations oI sparingly soluble salts which can cause scaling oI membrane surIace, limiting the
    productivity and water recovery oI seawater reverse osmosis (SWRO). NanoIiltration (NF) pretreatment oI seawater, prevents
    scaling via preIerential removal oI scale-Iorming ions |1|.
    Several studies have shown that the rejection oI scale-Iorming ions is not the same Ior various membranes |2|. The main
    objective oI this study was to test a number oI commercially available NF membranes with synthetic seawater in order to
    compare their perIormance and identiIy optimum membranes and operational conditions Ior shiIting solubility equilibrium oI
    compounds susceptible to cause scaling due to salt precipitation (CaSO
    4 (s)
    , MgSO
    4 (s)
    , CaCO
    3 (s)
    , etc.).
    The experimental setup used consists oI SEPA CF II cell (Osmonics). The trans-membrane pressure diIIerence and cross-Ilow
    velocity were monitored and controlled automatically, pH and conductivity were also monitored.
    Synthetic seawater was prepared in the laboratory Iollowing the procedure described elsewhere |3|. During the study, eleven
    diIIerent nanoIiltration membranes, supplied by several manuIacturers, were tested at various trans-membrane pressure
    diIIerences and cross-Ilow velocities.
    Permeates obtained in the tests were analyzed in the laboratory by using the Iollowing analytical methods: Total Inorganic
    Carbon Analysis, Ionic Chromatography and ICP-MS.
    For the majority oI membranes, the sulIate rejection was superior to 90, which may be very important in view oI scaling
    prevention.
    The rejection oI monovalent ions, was essentially lower. For example, Ior chloride and sodium, the rejection was about
    30-40. However, the scaling is not related to these ions, and they will are removed in the SWRO process.
    At the same time, it has been Iound that nanoIiltration membranes can hardly reject boron.
    Depending on the membrane used, there were signiIicant diIIerences between the rejections oI various ions, but the most
    important diIIerence between membranes was their productivities. It is well known that the membrane rejection is basically
    controlled by the trans-membrane volume Ilow. That is why the comparative studies with diIIerent membranes have been
    carried out at the same permeate Ilows and not at the same trans-membrane pressure diIIerences.
    Proceeding Irom the obtained results, an optimal pre-treatment Ior the scaling prevention in seawater desalination can be
    suggested.
    -272-
    This study was Iinancially supported by Sociedad General de Aguas de Barcelona (AGBAR) within the scope oI CENIT
    project 'Desarrollos tecnologicos hacia un ciclo del agua urbano auto-sostenible (SOSTAQUA).
    |1| N. Hilal, H. Al-Zoubi, N.A. Darwish, A.W. Mohammad, M. Abu Arabi; A comprehensive review oI nanoIiltration
    membranes: treatment, pretreatment, modelling and atomic Iorce microscopy; Desalination 170 (2004) 281-308
    |2| A.M. Hassan, A. Farooque, A. Jamaluddin, A. A1- Amoudi, M. A1-SoIi, A. AI-Rubaian, N. Kither, I. Al-Tisan and A.
    Rowaili, A demonstration plant based on the new NF-SWRO process, Desalination, 131 (2000) 157-171
    |3| Kester, D. R., Duedall, I. W., Connors, D. N. and Pytkowicz, R. M. (1967). Preparation oI ArtiIicial Seawater. Limnologv
    & Oceanographv 12, 176179.
    PB.2.22
    Permeability and bacteria rejection in third generation membranes. Application to
    cold sterilization of food streams.
    L. Fernandez Garcia
    1
    , F. A. Riera Rodriguez
    1
    , R. Alvarez Fernandez
    1
    , S. Alvarez Blanco
    2
    1
    Chemical Engineering and Environmental Technologv Department. Facultv of Chemistrv. Universitv of Oviedo. C/Julian
    Claveria 8, 33006 Oviedo (Spain)
    2
    Chemical and Nuclear Engineering Department. Polvtechnic Universitv of Jalencia. Camino de Jera, s/n 46022 Jalencia
    (Spain)
    leticiaIernandeziqgmail.com
    MicroIiltration is a well-known membrane technology used in Iood industries to puriIy and Iractionate valuable compounds.
    Concentration polarization and progressive membrane Iouling are the main drawbacks oI this technology when applied at
    industrial scale.
    Third generation ceramic membranes developed in the last years open new opportunities to this technology in debacterization
    oI Iood streams. STERILOX

    GP developed by SCT (Societe des Ceramiques Techniques), incorporates a progressive


    increase in the porosity oI the support matrix along the length oI the membrane. A similar concept has been employed by Tami
    Ior ISOFLUX

    membrane where the thickness oI the selective layer is decreased along the membrane length to give a uniIorm
    permeation rate, what contributes to solve the main problems associated to constant transmembrane pressure systems used to
    reduce bacteria content in milk and derivatives (cold sterilization).
    In this work, an original design has been built with an open carter and a PVC pipe divided into several compartments. The pipe
    divides the membrane in nine parts along its lenght and it allows the measurement oI the permeate Ilux along the membrane
    lenght.
    The experiments will be carried out using Iood solutions. Results about permeability along the membrane lenght and bacteria
    rejection will be presented. Samples taken along the compartments will be used to modelize the permeation and transmission
    properties oI diIIerent membranes tested. These mathematical models will help to optimize the microIiltration conditions to
    achieve the best membrane perIormance at industrial scale.
    M. W. ELWELL; D. M. BARBANO; Use oI MicroIiltration to Improve Fluid Milk Quality. Journal oI Dairy Science 89:E20-
    E30 (2006)
    G. L. BARUAH; A. NAYAK; G. BELFORT; Scale-up Irom laboratory microIiltration to a ceramic pilot plant: Design and
    perIormance. Journal oI Membrane Science 274 5663(2006)
    A. PIRY; W. KHNL; T. GREIN; A. TOLKACH; S. RIPPERGER; U. KULOZIK; Length dependency oI Ilux and protein
    permeation in crossIlow microIiltration oI skimmed milk. Journal oI Membrane Science 325 887894 (2008)
    -273-
    PB.2.23
    Influence of the ionic composition on the transfer of sugars through ion-exchange
    membranes
    J. Savignac
    1,2
    , E.Vera
    3
    , S. Galier
    1,2
    , P. Huguet
    3
    , H. Roux-de Balmann
    1,2
    1
    Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, F-31062 Toulouse cedex 09, France
    2
    CNRS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    3
    Institut Europeen des Membranes (IEM), Universite Montpellier II, ENSCM, CNRS, CC047, Place Eugene Bataillon, 34095
    Montpellier, France
    savignacchimie.ups-tlse.Ir
    Ion-Exchange Membranes (IEM) are used in a lot oI processes like dialysis, electrodialysis, Iuel cell. The characterisation oI
    such membranes has been investigated these last years in order to improve the understanding oI the membrane structure and oI
    its relationship with the transIer mechanisms |1|.
    In some situations, it was observed that the ionic composition oI the electrolyte solution has an inIluence on the membrane
    characteristics, like the water content Ior instance |2|. Such a membrane swelling can modiIy to a certain extent, the transIer oI
    the solutes and thus aIIect the perIormances oI the membrane process.
    This work presents the results oI an experimental study carried out with standard ion-exchange membranes, AMX and CMX,
    used in electrodialysis. The inIluence oI the ionic composition on the transIer oI neutral organic solutes is investigated.
    The experiments are carried out in a diIIusion mode, where the transIer is Iorced by a concentration gradient created on both
    sides oI the membrane. Sugars oI various molecular weights (Xylose, Glucose, and Saccharose) and diIIerent electrolytes
    (NaCl, CaCl
    2
    , Na
    2
    SO
    4
    .) are considered.
    The membranes are Iirst soaked until equilibrium in the corresponding solution oI electrolyte in order to dissociate both eIIects
    that could be due to a possible change oI the properties oI the membrane material or to the modiIications oI the properties oI
    the sugar.
    It is shown that the sugar transIer can vary up to a Iactor oI 5, depending on the electrolyte composition, the sugar and the type
    oI membrane considered. It is Iurther concluded that Ior the experimental conditions investigated, such variations with the
    ionic composition are mainly due to the resulting change oI the properties oI the membrane.
    |1| Dammak L., et al., Determination of the diffusion coefficients of ions in cation-exchange membranes, supposed to be
    homogeneous, from the electrical membrane conductivitv and the equilibrium quantitv of absorbed electrolvte. Electrochimica
    Acta, 2001. 47(3): p. 451-457
    |2| Tuan, L.X. and C. Buess-Herman, Studv of water content and microheterogeneitv of CMS cation exchange membrane.
    Chemical Physics Letters, 2007. 434(1-3): p. 49-55
    PB.2.24
    Preparation and properties of sulfonated polyvinilydene fluoride porous membranes
    A. Bottino, G. Capannelli, A. Comite
    Dipartimento di Chimica e Chimica Industriale, via Dodecaneso 31, 16146 Genova, Italv
    bottinochimica.unige.it
    This paper deals with the preparation and properties oI sulIonated polyvinylideneIluoride (PVDFS) membranes obtained by
    changing evaporation conditions oI cast solutions beIore immersion into a water bath. PVDFS (2 SO3H) was obtained by
    heterogeneous phase sulphonation with oleum oI a commercial PVDF |1|. Casting solutions with diIIerent polymer
    concentration (16 to 32 PVDFS in N,N-dimethylIormamide) were Iirst cast onto a glass plate to Iorm a thin Iilm in a
    controlled room (20 C, 60 humidity) plate and then immediately placed into a oven with a turbulent Ilow oI air at
    temperature ranging Irom 20 to 135 C, Ior a proper exposure time prior to immersion in water at 5 C. The structure oI cold
    Iractured cross section was investigated by scanning electron microscopy. Pore size and pore size distribution were determined
    trough a liquid-liquid displacement porometer. UltraIiltration perIormance was evaluated with an aqueous Dextran with
    nominal average molecular mass 40 kDa.
    All membrane properties were signiIicantly aIIected by exposure conditions oI the casting solutions. At high temperature the
    rapid solvent evaporation causes an increase oI the polymer concentration at the air-solution interIace that Iavours the
    Iormation oI a less porous and permeable skin top layer. At room temperature the rate oI solvent evaporation is low and
    -274-
    absorption oI water vapour Irom the atmosphere Iavours a very slow polymer precipitation beIore water immersion that leads
    to symmetric structure with poor dextran retention.
    |1| S. Munari, F. Vigo, G. Capannelli, C. Uliana, A. Bottino, Method Ior the preparation oI asymmetrical membranes, US
    4,188,354 (1980).
    PB.2.25
    Influence of temperature and counter-ion nature on methanol permeation through
    ion-exchange membranes
    L. Chaabane
    1
    , C. Mar-Diop
    2
    , L. Dammak
    1
    , C. Larchet
    1

    1
    Svstemes Polvmeres Complexes Institut de Chimie et des Materiaux Paris-Est. 2, rue Henri Dunant. 94320 Thiais, France.
    Tel. 33 1 45 17 17 86 , Fax. 33 1 45 17 17 21
    2
    Laboratoire dElectrochimie et des Procedes Membranaires, Ecole Superieure Polvtechnique, Universite Cheikh Anta DIOP
    de Dakar-5085 Fann - Senegal.
    larchetuniv-paris12.Ir
    The diIIusion behaviour oI two ion-exchange membranes, NaIion

    117 and CM2, Ior mixed solvent are compared. Each


    membrane separates a water-methanol electrolyte solution Irom pure water. The measurements oI methanol diIIusion
    permeability were carried out at diIIerent temperatures using diIIerent electrolyte solutions in which the membranes were
    preliminary equilibrated. Four cases were studied: three 0.1 M solutions (HCl, LiCl or NaCl), and pure water. In the last case
    the membranes were in H

    Iorm. It was Iound that membrane permeability to methanol decreases in the same order as
    membrane swelling in water-methanol solutions:
    (H

    Iorm oI membrane in pure water) ~ (0.1 M HCl) ~ (0.1 M LiCl) ~ (0.1 M NaCl)
    The activation energy (E
    Activ.
    ) oI methanol diIIusion varies in the same order Ior the studied equilibrating solutions: E
    Activ.
    (H

    ) ~
    E
    Activ .
    (Li

    ) ~ E
    Activ .
    (Na

    ).
    However, in the case oI membranes equilibrated with pure water, the activation energy was the lowest. This behaviour was
    related to the amount oI water swelling the membrane, which increases with decreasing the solute concentration and with
    increasing the radius oI the solvated counter-ion. It was also Iound that NaIion

    117 is more permeable to methanol and the


    activation energy oI methanol diIIusion is lower Ior this membrane compared with CM2.
    PB.2.26
    Transport properties of organic vapours in glassy perfluoropolymer membranes
    revealed by detailed analysis of the transient behaviour in the permeation curve
    J. C. Jansen
    1
    , K. Friess
    2
    , E. Drioli
    1,3
    1
    Institute on Membrane Technologv, ITM-CNR, Jia P. Bucci 17/C, 87030 Rende (CS), Italv
    2
    Department of Phvsical Chemistrv, Institute of Chemical Technologv, Technicka 5, 166 28 Prague 6, C:ech Republic
    3
    Universitv of Calabria, Department of Chemical Engineering and Materials, Jia P. Bucci 44/A, 87030 Rende (CS), Italv.
    jc.jansenitm.cnr.it
    The exceptional combination oI high thermal and chemical stability, resistance to swelling and moderate to high permeability
    makes amorphous glassy perIluoropolymers (PFPs) such as TeIlon AF and HyIlon AD oI great interest Ior use as
    membrane materials. For this reason they are receiving considerable attention lately Ior the application in gas and vapour
    separation membranes |1|.
    The diIIusion coeIIicient, D, in dense membranes is oIten calculated Irom the time lag, , through the Iollowing well-known
    relation based on the penetration theory:
    D l
    2
    /6,
    where l is the membrane thickness. The time lag is usually determined Irom the intercept between the tangents to the
    permeation curve beIore and aIter the transient zone, beIore the onset oI permeation and aIter reaching the steady state,
    respectively (Figure 1).
    -275-
    It was observed that the permeation curve oI some polar organic
    vapours in glassy PFPs has an unusual shape. In particular, the
    transient zone is very wide and aIter the onset oI permeation it
    takes a long time to reach the steady state |2|.
    In this paper we will describe a method to analyze the transient
    behaviour by Iitting the entire permeation curve, rather than by
    using the tangents to determine the time lag the diIIusion
    coeIIicient. It will be shown that a good Iit can only be obtained
    iI an equation with multiple time lags is used and it is
    hypothesized that this is related to the presence oI clusters oI
    diIIerent size, each with their own speciIic diIIusion rate.

    205.3
    0.0
    0.1
    0.2
    0.3
    0.4
    0.5
    0.6
    0.7
    0.8
    0.9
    1.0
    0 200 400 600 800 1000 1200
    time (s)
    P
    e
    r
    m
    e
    a
    t
    e

    p
    r
    e
    s
    s
    u
    r
    e

    (
    m
    b
    a
    Figure 1. Methanol vapour permeation curve in a dense
    HyIlon AD membrane, using the barometric method.
    Financial support Irom the EU 6
    th
    Framework Program Project MultiMatDesign and Network oI Excellence NanoMemPro is
    grateIully acknowledged
    |1| T.C. Merkel, I. Pinnau, R. Prabhakar, B.D. Freeman, Gas and vapor transport properties oI perIluorpolymers, in
    Yampolskii Yu, Pinnau I and Freeman BD (Eds.), Materials science oI membranes Ior gas and vapor separation, Chichester,
    England, John Wiley & Sons, 2006 (Ch. 9).
    |2| J.C. Jansen, K. Friess, E. Drioli, in preparation.
    PB.2.27
    Ion-exchange membrane resistivity measurement and model at DC
    L. Chaabane, L. Dammak, C. Larchet

    Svstemes Polvmeres Complexes Institut de Chimie et des Materiaux Paris-Est, 2, rue Henri Dunan, 94320 Thiais
    larchetuniv-paris12.Ir
    This contribution is concerned with a method Ior measuring the electrical resistance oI an ion-exchange membrane, R
    M
    , with
    the GUILLOU`s cell. The method is based on the application oI a direct current and on the analysis oI the potential jump (PJ)
    through the membrane, subsequent to the application oI this current and just beIore the beginning oI the Iormation oI the
    diIIusion boundary layers. This jump corresponds to the pure ohmic behavior oI the membrane-solution system. Two methods
    Ior the determination oI the PJ values have been tested: The Iirst one consists in taking the Iirst value oI AV measured aIter the
    injection oI the electrical current, and the second method consists in plotting the curve ( )
    0
    t t I AV where t
    0
    is the
    starting injection time. The PJ is determined by the extrapolation oI the potential diIIerence to the initial time.
    On the one hand, experimental results obtained with three homogeneous commercial ion-exchange membranes (CM1, CM2
    and CMx) show that the shape oI the curves R
    M
    versus the concentration oI the equilibrating solution, measured at DC, is the
    same than that obtained at AC, and, on the other hand, Ior all the membrane/solution systems, membrane resistance is higher at
    AC than that at DC (the general shape oI the obtained curves is explained on the basis oI the microheterogeneous model
    developed by GNUSIN et al.). The diIIerence is explained by the presence oI two phenomena when we applied DC: electro-
    osmosis and concentration polarization on the level oI the gel-intergel interIace. The eIIects oI these two phenomena are
    opposite. It appears that the eIIect oI electro-osmosis is much more important than that oI the internal polarization oI the
    concentration. This is expected owing to the Iact that the three membranes used are oIten regarded as homogeneous.
    -276-
    PB.2.28
    Ageing of ion-exchange membranes: influence on the transport properties
    L. Dammak, D. Grande, C. Larchet
    Svstemes Polvmeres Complexes Institut de Chimie et des Materiaux Paris-Est, 2, rue Henri Dunan, 94320 Thiais
    dammakuniv-paris12.Ir
    In electrodialysis processes, membranes tend to lose some transport properties aIter a certain period oI utilization. Two ion-
    exchange membranes, namely a homogeneous anion-exchange membrane (MX) and a heterogeneous cation-exchange
    membrane (MK-40), were used to investigate the ageing phenomenon and to highlight the characteristic parameters oI these
    membranes which evolved most quickly with ageing. An artiIicial ageing was carried out under oxidizing conditions on both
    membranes. It showed an increase in conductivity and swelling rate, implying a modiIication oI the polymer chain structure
    with time, and excluded a signiIicant deterioration oI the Iunctional groups since the exchange capacity remained almost
    constant. The membrane behaviour was then studied in an electrochemical system by perIorming voltamperometric and
    chronopotentiometric analyses which conIirmed the modiIication oI the polymer chain structure.
    PB.2.29
    Comparison between RO and NF performances in aqueous solutions of phenolic
    compounds: Influence of hydroxyl, chloro and nitro substituents
    M. J. Lopez-Muoz
    1
    , J. M. Arsuaga
    1
    , L. Braeken
    2
    , A. Sotto
    1
    1
    Department of Chemical and Environmental Technologv, Rev Juan Carlos Universitv
    28933-Mostoles, Madrid, Spain
    2
    Laboratorv for Applied Phvsical Chemistrv and Enviromental Technologv,Department of Chemical Engineerin, Facultv of
    Applied Sciences, Katholieke Universiteit Leuven, W. de Crovlaan 46, 3001 Heverlee, Belgium
    arcadio.sottourjc.es
    The relative Ilux and retention oI phenolic compounds in organic aqueous solutions by three reverse osmosis and nanoIiltration
    commercial membranes (TFC HR, BW 30 and NF 90) were investigated. The inIluence on the membrane perIormance oI the
    type and position oI the substituted Iunctional groups in the benzene ring was studied. The inIluence oI membrane and solutes
    properties upon Ilux decline and organic retention was also evaluated. The higher Ilux decline was observed Ior the more
    hydrophobic membranes, NF 90 and BW 30. A signiIicant decrease in relative Ilux was obtained as the Iunctional groups
    changed in this order: hydroxylchloronitro. A regular increase in retention was observed as the position oI the diIIerent
    Iunctional groups in the aromatic ring changed according to paramethaortho, Ior the NF90 membrane. A direct relation
    between solute permeation and molecular hydrophobicity caused by the organic adsorption on the membrane surIace could be
    concluded.
    Figure 1. Retention oI the phenolic compounds as a Iunction
    oI the substituted groups in the benzene ring.
    This work was supported by Ministry oI Education and Science oI Spain under the CTQ2006-04720/PPQ and Consolider-
    Ingenio 2010 (CSD2006-44) research projects and Regional Government oI Madrid provided through project
    REMTAVARES. The authors wish to thank Genesys Membrane Product, S.L. Ior its valuable contribution to this work.
    -277-
    PB.2.30
    Influence of membrane and solute properties on the separation performance of
    nanofiltration and reverse osmosis membranes for phenol oxidation products
    J. M. Arsuaga, M. J. Lopez-Muoz, A. Sotto
    Department of Chemical and Environmental Technologv, Rev Juan Carlos Universitv 28933-Mostoles, Madrid, Spain
    jesusmaria.arsuagaurjc.es
    Membrane physical characterization oI reverse osmosis and nanoIiltration commercial membranes (TFC HR and NF 90) was
    perIormed. In addition to the molecular weight cut-oII and average pore size Ior NF 90, the membrane surIace was
    characterized Ior hydrophobicity and roughness.The solute separation oI initial phenolic compounds (phenol, catechol,
    hydroquinone and resorcinol) and Iour carboxylic acids (malonic, oxalic, acetic and Iormic acids) Iormed as intermediates oI
    chemical oxidation oI phenol was investigated. The inIluence oI membrane and solutes properties on the organic retention and
    Ilux decline was evaluated. Retention selectivity Ior aromatic solutes and carboxylic acids was higher Ior NF 90 than Iound Ior
    TFC HR. For the tested compounds, the size exclusion mechanism may be an important Iactor but is not suIIicient Ior
    explaining the rejection perIormance oI NF 90 membrane. The molecular hydrophobicity was the most important descriptor Ior
    the Ilux decline and organic rejection.
    HOOCH
    O
    O
    O O
    HO OH
    HO OH
    OH
    OH
    OH
    H
    2
    C CH COOH
    H
    3
    C COOH
    HOOC H
    2
    C COOH
    COOH HOOC
    CH
    2
    CH
    3
    COOH
    COOH
    COOH
    HOOC
    COOH
    COOH
    COOH
    Figure 1. SimpliIied route oI advanced oxidation oI phenol
    This work was supported by Ministry oI Education and Science oI Spain under the CTQ2006-04720/PPQ and Consolider-
    Ingenio 2010 (CSD2006-44) research projects and Regional Government oI Madrid provided through project
    REMTAVARES. The authors wish to thank Genesys Membrane Product, S.L. Ior its valuable contribution to this work.
    PB.2.31
    Effect of polymer swelling on the nanofiltration performance of
    poly(dimethylsiloxane)
    O. Farid, J.P. Robinson
    Department of Chemical and Environmental Engineering, Universitv of Nottingham, Nottingham, NG7 2RD, UK.
    enxoI2nottingham.ac.uk
    Membrane nanoIiltration is oI growing industrial importance and much research has Iocused on understanding the selectivity
    oI the separation process. NanoIiltration and Pervaporation have been widely investigated Ior separating organic/aqueous
    systems as the energy requirements are potentially much lower than conventional chemical engineering unit operations,
    leading to signiIicant cost savings. NanoIiltration theory is relatively well understood, with the separation determined by the
    sorption and diIIusion characteristics oI each component in the selective layer. The sorption or solubility step governs the
    degree oI separation that can be attained, and this can be characterised by studying the swelling oI the selective polymer layer.
    This work investigated the swelling oI Poly(dimethylsiloxane) (PDMS) in alkane- alcohol solutions, and aims to quantiIy the
    selectivity oI the polymer across a range oI alcohol concentrations.
    -278-
    This work has shown that swelling equilibrium oI mixtures with PDMS are strongly dependent on the mixture composition and
    nature oI the organic compound. It is shown that transitions occur whereby PDMS changes Irom being alcohol-selective to
    alkane-selective, and the signiIicance oI this phenomena Ior nanoIiltration processes is discussed.
    PB.2.32
    Organic solvent nanofiltration thin film composite (TFC) membranes
    M. F. Jimenez Solomon, Y. Bhole, A. G. Livingston
    Department of Chemical Engineering and Chemical Technologv, Imperial College, Exhibition Road, London SW7 2AZ,
    United Kingdom
    a.livingstonimperial.ac.uk
    Organic Solvent NanoIiltration (OSN) is an emerging technology Ior conventional separation and puriIication processes. A
    challenge in nanoIiltration and reverse osmosis is to broaden the applications Irom aqueous to organic Ieeds. This requires
    solvent-resistant membranes that preserve their separation characteristics under a large range oI solvents, as well as with Iree-
    deIects morphology and controlled MWCOs.
    Thin Iilm composite membranes (TFC) are typically prepared using interIacial polymerization (IP) on a support-layer (an
    asymmetric UF membrane)
    1
    . TFC membranes are very Ilexible as the chemistry and perIormance on both barrier-layer and
    porous substrate can be independently optimized to maximize the overall membrane perIormance
    2
    . Furthermore, the thin
    barrier layer can be Iormed oI a large variety oI chemical compositions, including both linear and crosslinked polymers;
    whereas asymmetric integrally skinned membrane Iormation process is quite limited to linear, soluble polymers
    2
    .
    The support-layer oI OSN TFC membranes should be solvent resistant. Furthermore, the perIormance, composition and
    morphology oI TFC membranes depends on many parameters used on the Iormation oI the barrier top-layer, such as the
    concentration oI the reactants and their overall diIIusion rates, the use oI possible additives, and post-reaction treatment. TFC
    membranes characteristically show a trade-oII between permeability and solute rejection, which can be overcome by careIully
    choosing these parameters
    3
    .
    Polyimides (PI) have been used as polymers Ior solvent resistant nanoIiltration
    4, 5
    and ultraIiltration
    6
    membranes. These
    polymers present high resistance against a wide range oI organic solvents, high temperature durability, and high mechanical
    properties which make them one oI the most suitable polymers Ior the development oI OSN membranes. In previous work
    6
    ,
    using thermal imidization, asymmetric polyimide-based UF membranes with exceptional solvent resistance and high
    permeabilities have been obtained. These membranes can be used as supports Ior TFC membranes applicable in OSN.
    In this work, PI UF membranes were used as the support Ior the Iormation oI organic solvent nanoIiltration TFC membranes.
    Initial promising results have been obtained by varying diIIerent parameters on the Iormation oI the top-layer, enhancing
    solvent Ilux and solute rejection.
    |1| US Pat., 4,277,344, 1981.
    |2| R. J. Petersen, J. Membr. Sci., 83, 81, 1993.
    |3| P. Vandezande, et al., J. Chem. Soc. Rev, 37, 365, 2008.
    |4| Y. H. See Toh, F. W. Lim and A. G. Livingston, J. Membr. Sci., 301, 3, 2007.
    |5| Y. H. See-Toh, F. C. Ferreira and A. G. Livingston, Desalination, 199, 242 .2006.
    |6| US Pat. , 5 725 769, 1998.
    PB.2.33
    Characterization of a commercial nanofiltration membrane suitable for the recovery
    of ionic liquids from aqueous solutions
    J.F. Fernandez
    1,2
    , M.A. Rodriguez
    2
    , J. Thming
    1
    1
    UFT- Centre for Environmental Research and Sustainable Technologies, Universitv of Bremen, 28359 Bremen, Germanv
    2
    Chemical Engineering School, Central Universitv of Jene:uela, 1040 Caracas, Jene:uela
    joIeuni-bremen.de
    NanoIiltration could be used to recover ionic liquids Irom aqueous solutions, avoiding their entrance into the environment and
    providing a useIul contribution in the Iields oI ionic liquids reuse and recycling. Several commercial membranes have been
    -279-
    tested with diIIerent ionic liquids and it was possible to obtain a high retention oI ionic liquids, no matter their chemical
    structure, with one oI the membrane used |1|.
    A Iirst approach Ior a characterization study concerning morphology, charge and separation parameters oI this membrane was
    already done |2|. However, there are still some unclear aspects in order to understand the role oI the membrane in the selective
    separation oI ionic liquids. Further research is needed to take advantage oI the high perIormance it has shown, thinking in
    terms oI the development oI new materials Ior some speciIic applications.
    In this work, some new relations between membrane perIormance (expressed as retention and permeate Ilux) and membrane
    charge and morphological properties were developed by various measurement methods. Characteristics related with
    hydrophobicity, pore size and/or porosity, chemical composition, zeta potential, and interactions between selected molecules
    and the membrane surIace are presented.
    |1| J.F. Fernandez, E. Chilyumova, D. Waterkamp, J. Thming, Ionic liquid recovery Irom aqueous solutions by cross-Ilow
    nanoIiltration, Proceedings oI the 10
    th
    World Filtration Congress, 2008, Volume II, 528-532.
    |2| G. Artug, I. Roosmasari, K. Richau, J. Hapke, A comprehensive characterization oI commercial nanoIiltration membranes,
    Separation Science and Technology, 2007, 42, 2947-2986.
    PB.3.1
    Organic membrane characterizations by optical and microscopic methods: drinking
    water application
    R. Tamime
    1
    , Y. Wyart
    1
    , L. Siozade
    2
    , I. Baudin
    3
    , C. Deumie
    2
    , K. Glucina
    3
    , P. Moulin
    1
    1
    Universite Paul Ce:anne, Laboratoire de Mecanique, Modelisation et Procedes Propres (M2P2-UMR 6181), Europole de
    lArbois, 13545 Aix en Provence cedex 04, France
    2
    Institut FRESNEL (UMR 6133), Universite Paul Ce:anne Aix Marseille, Domaine Universitaire de St Jerome, 13397
    Marseille cedex 20, France
    3
    Sue: Environnement, CIRSEE, Pole Eau Potable, 38, rue du President-Wilson, 78230 Le Pecq, France
    yvan.wyartuniv-cezanne.Ir
    Nowadays, with an annual growth oI more than 12 (20 Ior water Iield), membrane processes are the industrial processes
    which have the more rapid expansion. They are increasingly applied in many domains such as the chemical industry, the
    pharmaceutical industry, petrochemistry, and water treatment. Nevertheless the membrane Iouling, the main disadvantage oI
    membrane processes must be more understood in order to increase the impact oI membrane separations in industrial Iield. The
    structural properties oI membranes (roughness, porosity.) have an impact on Iouling phenomenon and must be characterised
    to develop a Iouling control method. In this work, several optical methods are used to characterise organic membranes: Iirst
    virgin and secondly Iouled membranes.
    In this work, three optical techniques are used in order to study organic ulraIiltration membranes at diIIerent scales and to
    obtain inIormation about the surIace and the internal volume oI the membranes: Ilat sheet membranes (10, 30, 100 and 300
    kDa) and hollow Iibers. An optical proIilometer (White Light InterIerometry (WLI)) and an Atomic Force Microscopy (AFM)
    are used in order to assess the surIace state oI membranes (roughness spectrum). With the Iirst one, windows oI 360 x 360 m
    and 900 x 900 m with 1024 points can be reached. Moreover, the second technique is used on surIaces oI 50 x 50 m with
    512 x 512 points. A technique based on the measurement and the analysis oI the light scattering is also used. A laser multi-rays
    scatterometer allows to study both surIace and volume oI membranes.
    In this study, microscopy and optical techniques were applied to Iour virgin organics Ilat sheet ultraIiltration membranes (10
    kDa, 30 kDa, 100 kDa and 300 kDa membrane cut-oII). The results obtained by WLI and AFM show that the determination oI
    the membrane roughness depends on the observation scale. The roughness oI a membrane increases markedly with the
    observation scale. However, there is continuity between the diIIerent scan sizes and techniques Ior the determination oI the
    RMS roughnesses. This is oI interest Ior the study oI the membrane Iouling phenomenon, where smaller scan sizes are
    required to characterize roughness oI the Iiltration cake at diIIerent scales. The high angular resolution ellipsometric
    measurements allowed us to obtain the signature oI each cut-oII and the origin oI the scattering was identiIied. Using this non-
    destructive optical technique Ior membrane characterization is an innovative approach Ior organic membranes applied to the
    drinking water production, which gives promising results.
    In this work, the results were obtained Ior membrane cut-oIIs ranged Irom 10 to 300 kDa. They show that the diIIerent
    techniques used are also suited to the study oI hollow Iibres used Ior drinking water production Ior which UF membrane cut-
    oII are ranged Irom 100 to 150 kDa.
    The next step oI this work is to complete data in order to better improve the understanding oI Iouling phenomenon occurring
    during drinking water production.
    -280-
    PB.3.2
    A new approach to the challenge of measuring multi-component sorption properties
    in barrier materials: example of EVOH copolymers for fuel tank applications
    A. Jonquieres
    1
    , R. Clement
    1
    , J. Zhao
    1
    , C. Kanaan
    1
    , B. Brule
    2
    , H. Lenda
    1
    , P. Lochon
    1
    1
    Laboratoire de Chimie Phvsique Macromoleculaire, UMR CNRS-INPL 7568,
    Nancv Universite, ENSIC, 1 rue Grandville, BP 20451, 54 001 Nancv Cedex, France
    2
    ARKEMA, Cerdato, 27 470 Serquignv, France.
    Anne.Jonquieresensic.inpl-nancy.Ir
    Ethylene vinyl alcohol (EVOH) copolymers are leading barrier materials Ior multi-layer Iuel tank applications. Owing to
    ever more demanding environmental regulations, the permeability oI Iuel tanks has been constantly decreasing Ior the past ten
    years and its measurement becomes more and more time-consuming, the time Ior reaching the permeation steady state being
    usually oI almost one year. Within this highly challenging context, it would be extremely interesting to develop speciIic
    models to predict the permeability oI Iuel tanks Irom the properties oI the corresponding polymer mono-layers. According to
    the well known sorption-diIIusion model, the determination oI their sorption properties is a Iirst key step towards this goal. In
    this work developed in collaboration with the chemical worldwide company Arkema, a new semi-automated desorption
    experimental set-up was thus developed for characterizing the sorption properties of barrier polymer materials in contact with
    model fuel mixtures [1,2]. By a proper optimization oI the measurement conditions in real time, a very high sensitivity (0.1
    microgram) was easily obtained Ior the measured weights. Figure 1 shows that this very high sensitivity eventually enabled to
    determine partial sorption data diIIering by three orders oI magnitude Ior the same experiment which, to the best oI our
    knowledge, has never been reported so Iar. The whole set oI sorption data showed that EVOH displayed a very strong aIIinity
    towards ethanol during the sorption oI Iuel mixtures ethanol/i-octane/toluene Ior a wide range oI compositions typical Ior the
    various types oI Iuels. Another striking Iact was that EVOH copolymers showed very diIIerent aIIinities Ior both hydrocarbons
    with a preIerential sorption oI toluene owing to its strong polarizability, in very good agreement with Iormer observations
    made Ior related permeability measurements |3|.
    [1] R. Clment, C. Kanaan, B. Brul, H. Lenda, P. Lochon, A. Jonquires, Journal of Membrane Science 302 (2007) 95-101.
    [2] A. Jonquires, R. Clment, C. Kanaan, B. Brul, H. Lenda, P. Lochon, "New developments in the measurement of multi-
    component sorption in barrier polymer materials : a key step towards the modelling of fuel tank permeability", invited Keynote
    Lecture, International Congress on Membranes and Membrane Processes, ICOM 2008, July 12-18, 2008, Honolulu, Hawaii,
    USA.
    [3] M. Nulman, A. Olejnik, M. Samus, E. Fead, and G. Rossi, Society of Automotive Engineers, Special Publication, SP-1365
    (1998) 41-48.
    PB.3.3
    Residence time distribution method for the study of hydrodynamics in the membrane
    apparatus
    A. Miskiewicz
    1
    , A. Jaworska
    1
    , G. Zakrzewska-Trznadel
    1
    , A. Dobrowolski
    1
    , C. Cojocaru
    2
    1
    Institute of Nuclear Chemistrv and Technologv, Department of Nuclear Methods in Process Engineering, Dorodna 16,
    03-195 Warsaw, Poland
    2
    Department of Environmental Engineering and Management, Facultv of Chemical Engineering, Gh. Asachi Technical
    Universitv, 71 Mangeron Blvd.,700050 Iasi, Romania
    amiskiewiczichtj.waw.pl
    gzakrzewichtj.waw.pl
    Study oI processes proceeded inside the membrane apparatus is diIIicult because oI construction oI membrane modules which
    are closed systems. Inaccessibility oI the membrane placed inside the tubular module hinders the examination oI the
    phenomena occurred in the boundary layer. Application oI tracers can deliver inIormation not only about mean residence times
    in the apparatus, the hydrodynamics oI the Ilow and mixing phenomena, but also about the transport oI the material in the
    membrane vicinity.
    -281-
    In the paper the possibility oI application oI radiotracers Ior determination oI eIIectiveness oI the separation process, the rate oI
    the decontamination and accumulation oI separated particles on the membrane and inside the membrane matrix, to examine
    membrane Iouling was described.
    UltraIiltration module with movable part creating helical Taylor-Couette Ilow (CTF) inside the tubular membrane apparatus
    was used in the experiments. CTF is a combination oI the axial Poiseuille Ilow and rotating Couette Ilow with axisymmetric
    Taylor vortices. The eIIect oI departure Irom idealized Ilow behavior and the perIormance oI the apparatus was studied by
    means oI RTD analysis. This method allows determining the mean residence time in the apparatus and by calculating the
    Peclet number, to judge what kind oI Ilow above the membrane we are dealing with. Two diIIerent tracers: Iluorescein and
    radioactive
    99m
    Tc were used to determine RTD Iunctions. The tracer studies were supplemented by modelling. For studied
    apparatus the model oI retentate Ilow consisting oI two axial dispersion models: open-open and open-closed channel,
    connected in, series was developed. The inIluence oI process parameters: transmembrane pressure (P), retentate Ilow rate (Q
    R
    )
    and rotation Irequency oI the inner cylinder (O) on mean residence time (MRT) and dimensionless variance oI residence time
    (vard) has been evaluated. The results obtained have shown strong reduction oI vard with the rise oI all considered process
    parameters. With the rise oI retentate Ilow and transmembrane pressure the MRT decreased. The retentate Ilow structure Ior
    open-open model was close to the plug Ilow and it was expressed by high value oI Peclet number. There was no signiIicant
    change oI Peclet number Ior the open-closed model.
    Response surIace methodology with central composite orthogonal design Ior modelling oI hydrodynamic conditions in the
    apparatus and Ior studying the interactions oI the process variables was applied. The optimal process parameters determined
    by. were as Iollows: P0.81 bar, Q
    R
    105.37 l/h, O2661.25 rpm. Under these conditions the retentate Ilow structure was
    very close to the plug Ilow.
    Pressure characteristics Ior the studied membrane module also was made. For developing oI mathematical, empirical model to
    predict permeate Ilux oI pure water the DoE (Design oI Experiment) was accomplished in accordance with Iull Iactorial design
    (FFD) oI 2
    3
    type. The eIIect oI applied pressure was the most signiIicant being linear and positive. The retentate Ilow rate had
    the reduced eIIect upon the permeate Ilux oI water.
    PB.3.4
    Innovative combinations of ~in situ and ~ex-situ techniques as a tool for
    monitoring and controlling the evolution of nanostructured membranes
    G. Pilatos, A.I. Labropoulos, E.C. Vermisoglou, Ch. Veziri, G.E. Romanos, J.W. Nolan, G.N. Karanikolos,
    N.K Kanellopoulos
    Institute of Phvsical Chemistrv, National Center for Scientific Research Demokritos, Ag. Paraskevi, Athens 153 10, Greece
    karanikoloschem.demokritos.gr
    kanelchem.demokritos.gr
    Nanoporous membranes play an important role in chemical processing, as in many cases they can successIully replace
    traditional, pollution-prone, and energy-consuming separation processes. The complete characterization oI porous membranes
    however still remains a diIIicult and Irequently controversial problem, and this is mainly due to the great diIIiculty in
    accurately representing the complex morphology oI the pore matrix. To this end, the application oI the innovative approach
    established by the European Network oI Excellence INSIDE-PORES, oI combining in-situ and ex-situ techniques (gas relative
    permeability, diIIerential permeability, neutron diIIraction etc) is oI major importance as it is considered one oI the most
    powerIul methodologies currently available.
    On the other hand, no matter how thorough and complete the characterization is, it is quite meaningless iI it is not related to the
    process under consideration, since one oI the most important parameters in any application is the material's ability to retain
    their properties over a certain period oI time. The "changes" induced on membranes during both their synthesis and utilization
    in speciIic applications are highly relevant and moreover crucial Ior the economic viability. In this context, the application oI
    the innovative combinations oI 'in situ and 'ex-situ techniques as a tool to monitor and control the evolution oI
    nanostructure with the accuracy oI a Iraction oI nanometer during CVD growth oI nanoporous ceramic and carbon nanotube
    membranes will be presented.
    -282-
    PB.3.5
    Membrane design and characterisation by incorporation of room temperature ionic
    liquids for selective transport processes
    L. A. Neves, I. M. Coelhoso, J. G. Crespo
    REQUIMTE/CQFB, FCT Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal
    luisa.nevesdq.Ict.unl.pt
    NaIion membranes are widely used as a reIerence material in electrochemical applications such as polymer electrolyte
    membrane Iuel cells (PEMFCs), actuators and transducers due to their high mechanical, thermal and chemical stability |1|.
    Room Temperature ionic Liquids (RTILs) exhibit a large variety oI properties, such as negligible vapour pressure, a good
    electrical conductivity, a high ionic mobility and good thermal and chemical stabilities.
    Through an ion exchange-process between the counter cation oI the NaIion membrane and the RTIL cation, it was proved that
    it is possible to incorporate diIIerent RTILs cations inside the membrane |2|. In this way, it is possible to design 'tailor-made
    membranes with a deIined selectivity Ior target applications, by controlling the degree oI selected RTIL cations incorporated.
    This work aims the design and characterization oI new membranes by the incorporation oI RTILs in NaIion, in order to obtain
    membranes with modiIied electric properties while maintaining attractive properties Ior electrochemical applications.
    Additionally, methanol transport studies were perIormed in order to understand the impact oI RTILs incorporation on the
    crossover oI these species.
    The distribution oI RTILs inside NaIion membranes was determined by ConIocal Raman Spectroscopy and X-ray
    photoelectron spectroscopy (XPS), and both characterisation techniques allow Ior concluding that the RTIL cation is uniIormly
    distributed inside the membrane. The electric properties oI the NaIion-RTIL membranes were studied by Electrochemical
    Impedance Spectroscopy (EIS). Also, the eIIect oI diIIerent degrees oI concentration oI RTIL introduced in NaIion, in the
    proton mobility and the way water is organized inside the modiIied membrane, was evaluated by Solid State NMR.
    Finally, methanol transport studies were perIormed and when comparing to NaIion in the protonated Iorm, a signiIicant
    reduction in methanol permeability was achieved. This reduction in the methanol crossover, associated with good electrical
    transport properties oI the membranes, suggests their potential use in DMFCs.
    |1| K. A. Mauritz, R. B. Moore, State of Understanding of Nafion, Chemical Reviews, 104 (2004) 4535
    |2| T. SchaIer, R. E. Di Paolo, R. Franco, J. G. Crespo, Elucidating interactions of ionic liquids with polvmer films using
    confocal Raman spectroscopv, Chemical Communications (2005) 2594
    PB.3.6
    Water sorption and proton conductivity of various PEMFC membranes: influence of
    temperature, relative humidity and interactions of the adjacent layers in MEA
    L. Maldonado, F. Xu, O. Lottin
    Laboratoire dEnergetique et de Mecanique Theorique et Appliquee (LEMTA), Nancv-Universitv, CNRS 2 avenue de la Fort
    de Have, B.P.160, 54504 Jandoeuvre les Nancv Cedex, France.
    Libeth.Maldonadoensem.inpl-nancy.Ir
    PerIluorinated membranes are widely used in Proton Exchange Membrane Fuel Cells (PEMFCs) because oI their high proton
    conductivity when properly hydrated and oI their chemical, thermal and mechanical stability. However, water management in
    PEMFC remains one oI the major issues and Ior modeling purposes, accurate data are needed about the membranes water
    uptake over the usual temperature and relative humidity ranges. As a consequence, there are also some diIIiculties in
    estimating the membrane local ionic conductivity, despites several methods make it possible to estimate water distribution
    within the Iuel cell, like neutron scattering |1, 2| or NMR techniques |3|.
    This work concerns the systematic measurement oI membranes sorption properties and ionic conductivity. The Iirst part oI the
    presentation is a discussion about weighing techniques and protocols |4, 5|. In the second part, various sets oI membrane
    sorption curves are presented and discussed, as well as the corresponding values oI the ionic conductivity. Finally, results
    obtained with conventional membranes are compared to those obtained with commercial Membrane Electrode Assemblies
    (MEA) in order to evaluate the eIIects oI the adjacent layers (active layer, micro-porous layer, gas diIIusion layer) and making
    process on the membranes water sorption properties.
    -283-
    |1| F. Xu, O. Diat, G. Gebel, A. Morin, Determination oI transverse water concentration proIile through MEA in a Iuel cell,
    using Neutron Scattering, Journal oI the Electrochemical Society, 2007, 154(2), B1389-B1398
    |2| D. Kramer, J. Zhang, R. Shimoi, E. Lehmann, A. Wokaun, K. Shinohara, G. G. Scherer, In situ diagnostic oI two-phase
    phenomena in polymer electrolyte Iuel cells by neutron imaging Part A. Experimental, data treatment, and quantiIication,
    Electrochemical Acta, 2005, 50 (13), 2603-2614
    |3| J. Bedet, G. Maranzana, S. Leclerc, O. Lottin, C. Moyne, D. Stemmelen, P. Mutzenhardt, D. Canet, Magnetic resonance
    imaging oI water distribution and production in a 6 cm2 PEMFC under operation, International Journal oI Hydrogen Energy,
    2008, 33(12), 3146-3149.
    |4| T. A. Zawodzinski, Jr., T. E. Springer, J. Davey, R. Jestel, C. Lopez, J. Valerio and S. GottesIeld, A comparative study oI
    water uptake by and transport through ionomeric Iuel cell membranes, Journal oI the Electrochemical Society, 1993, 140(7),
    1981-1985.
    |5| J. T. Hinatsu, M. Mizuhata, H. Takenaka, Water uptake oI PerIluorosulIonic Acid Membranes Irom Liquid Water and
    Water Vapour, Journal oI the Electrochemical Society, 1994, 141(6), 1493-1498
    PB.3.7
    Trace-ion method for the advanced characterization of NF membranes
    A. Yaroshchuk
    1
    , X. Martinez-Llado
    2
    , L. Llenas
    2
    , M. Rovira
    2
    , J. De Pablo
    2
    1
    ICREA and Department of Chemical Engineering, Polvtechnic Universitv of Catalonia, av.Diagonal 647, 08028 Barcelona,
    Spain
    2
    CTM Centre Tecnologic, av.Bases de Manresa 1, 08242 Manresa, Spain
    andriy.yaroshchukupc.edu
    Real waters are usually complex mixtures oI predominantly ionic solutes. Modelling membrane perIormance in electrolyte
    mixtures requires the knowledge oI membrane transport properties with respect to single ions. In the properties obtainable
    Irom the measurements oI rejection oI single salts, the membrane transport properties with respect to cations and anions are
    'entangled due to the spontaneously arising electric Iields.
    The underlying observation oI the approach oI trace ions is that the eIIect oI these Iields on the trans-membrane transIer oI
    traces is much more directly visible than in the rejection oI single salts. On the other hand, when the trace-ion concentrations
    are suIIiciently low, the membrane properties are unaIIected by the presence oI traces. ThereIore, the latter can be considered a
    kind oI non-interIering probes Ior the studies oI mechanisms oI transIer oI dominant ions |1|.
    In |2|, it was shown that the dependence oI rejection oI various single salts on the trans-membrane volume Ilow can be quite
    well described by the solution-diIIusion-Iilm model. Moreover, it was shown that this model can easily explain the
    experimentally observed high rejections oI sulIates Irom concentrated electrolyte solutions (seawater, brines) whereas the
    commonly used 'nano-porous model cannot. Within the scope oI solution-diIIusion model, the reIlection coeIIicients oI all
    solutes are considered to be equal to one (no convective coupling between the volume and solute transIers). This makes
    possible a very simple description oI trans-membrane solute transIer and the development oI eIIicient procedures oI obtaining
    membrane transport properties Irom experimental data.
    In this communication, the solution-diIIusion-Iilm model will be generalized to include the trace ions. A very simple analytical
    Iormula Ior the intrinsic rejection oI traces vs. trans-membrane volume Ilow will be obtained. A procedure will also be
    presented to relate the intrinsic rejections to the observable ones by using inIormation on the extent oI concentration
    polarization obtainable Irom the theoretical treatment oI rejection oI dominant salt.
    This novel approach will be applied to the interpretation oI experimental data on the rejection oI dominant salts and traces in
    NaCl/CaCl
    2
    and NaCl/Na
    2
    SO
    4
    mixtures by a commercially available NF membrane (NF270, Dow Chemical). In this way, we
    shall determine separately the membrane permeabilities to cations and anions oI dominant salts as well as to the traces. By
    using the two limiting compositions oI a mixture (e.g., NaCl as dominant salt, Na
    2
    SO
    4
    as the trace and vice versa), we shall
    demonstrate, in particular, in what way the membrane permeability to the common ion (in this example, Cl
    -
    ) depends on the
    dominant counter-ion. Proceeding Irom this, we shall also discuss the ways to use this inIormation Ior the prediction oI
    membrane perIormance in mixtures oI arbitrary composition.
    This study was Iinancially supported by Sociedad General de Aguas de Barcelona (Agbar) within the scope oI CENIT project
    'Desarrollos tecnologicos hacia un ciclo del agua urbano auto-sostenible (SOSTAQUA).
    |1| A.Yaroshchuk, V.Ribitsch, J.Membr.Sci. 201 (2002) 85-94
    |2| A.Yaroshchuk, X.Martinez-Llado, L.Llenas, M.Rovira, J.de Pablo, J.Flores, P.Rubio, Ext.Abstr.Int.ConI. 'Membranes in
    Drinking Water Production and Wastewater Treatment, Toulouse (France), Oct.20-22, 2008, paper 111.
    -284-
    PB.3.8
    In-situ analysis of SNRF membrane swelling under relevant conditions
    H. van der WerI, N. E. Benes, M. Wessling, A. Nijmeijer
    Inorganic Membranes/Membrane Technologv Group, Facultv of Science and Technologv, Institute of Mechanics, Processes
    and Control-Twente and Mesa

    Institute for Nanotechnologv, Universitv of Twente, P.O. Box 217, 7500 AE Enschede, The
    Netherlands
    n.e.benesutwente.nl
    A nondestructive method is presented Ior in-situ analysis oI solvent induced membrane swelling. The method is based on
    spectroscopic ellipsometry and allows the simultaneous measurement oI membrane Iilm thickness and solvent sorption. The
    attainable experimental conditions are only limited by the test-cell (_ 200 C, _ 200 bar) and by Iar exceed those encountered
    in typical SRNF applications. A systematic study is presented Ior thin (500 1000 nm) PDMS Iilms on glass substrates in
    hexane. The eIIects oI cross-linking degree, temperature, and pressure have been studied.
    The wavelength dependent optical properties oI the swollen PDMS Iilms could be described by the Bruggeman eIIective
    medium approach, leaving only the hexane Iraction and Iilm thickness as Iitting parameters. At ambient conditions the Iraction
    hexane and dilatation are typically 0.60 0.65 and ~170 , respectively. The eIIect oI temperature could be described
    adequately by the Flory-Huggins theory. To the best oI our knowledge, swelling oI PDMS Iilms in a pressurized solvent has
    not been studied previously. In the range 1 100 bar the extent oI swelling and the Iraction oI sorbed hexane are not
    signiIicantly aIIected by the pressure. These observations are contrary to studies in which a mechanical Iorce is applied to the
    swollen polymer, at ambient pressure. Our data suggest that the molar volume J
    i
    oI hexane does not change upon sorption in
    PDMS, and hence the change in chemical potential oI the solvent due to pressurization (J
    i
    p) is similar Ior the pure and sorbed
    liquid. This conIirms that Ior PDMS even at high pressures solvent permeation can be independent oI pressure.
    The presented method can be applied Ior analysis oI SRNF membranes, with a thin selective Iilm on a support, under relevant
    conditions.
    PB.3.9
    FTIR-ATR study of water distribution in Hyflon-Ion

    H membranes
    M. C. Ferrari, J. Catalano, M. Giacinti Baschetti, M. G. De Angelis, G. C. Sarti
    Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali, Universita degli Studi di Bologna, Jia
    Terracini 28, 40131 Bologna, Italv
    grazia.deangelis unibo.it
    HyIlon-Ion

    H is a short-side-chain perIluorosulphonic acid ionomer (PFSI) membrane that can be used as electrolyte in
    Proton Exchange Membranes Fuel Cells (PEMFCs). The material consists oI a hydrophobic poly(tetraIluoroethylene)
    backbone with perIluorovinyl ether short side chains terminated by sulphonic acid (SO
    3
    H) groups and has a rather low
    equivalent weight (800 g(pol)/mol(SO
    3
    H)) .
    The water sorption isotherm at 30C Ior an extruded membrane was measured with a Time-Resolved Fourier TransIorm
    InIrared-Attenuated TOTAL ReIlectance (FTIR-ATR) spectrometer that has been already applied to the study oI water
    transport in another type oI PFSI membranes (NaIion

    117) . The FTIR-ATR technique can provide a deeper insight into the
    process oI water diIIusion and absorption into PFSI membranes, because it allows to distinguish among diIIerent classes oI
    water based on the extent oI their hydrogen bond interactions with the sulphonic groups, and to monitor simultaneously the
    concentration oI the diIIerent populations over time. The total water uptake determined with the FTIR-ATR method is in good
    agreement with previous data obtained on the same membrane with a manometric method. Furthermore, the water solubility
    isotherm was decomposed into the various contributions corresponding to the diIIerent populations oI water. Four diIIerent
    species can be identiIied in the portion oI IR spectrum oI the polymer related to the stretching oI hydrogen bonds (Figure 1)
    and their concentration was monitored as a Iunction oI time and activity. The sorption behaviour can be modelled invoking a
    scheme oI equilibrium acid dissociation reactions.
    -285-
    Figure 1: FTIR-ATR spectra oI HyIlon-Ion

    H beIore (below) and aIter equilibration with water vapor at 5 RH


    PB.3.10
    Physicochemical study of Poly(4-vinylpyridine)-based weak anion exchange
    membranes. Contribution of in situ et operando techniques for the evaluation of
    thermodynamic and kinetic properties.
    L. Franck-Lacaze
    1
    , P. Huguet
    1
    , P. Sistat
    1
    , F. Lapicque
    2
    1
    Institut Europeen des Membranes (IEM),, Universite Montpellier II,ENSCM, CNRS, CC047, Place Eugene Bataillon, 34095
    Montpellier, France
    2
    Laboratoire des Sciences du Genie Chimique, CNRS-Nancv Universite, 1 rue Grandville, F54042 Nancv, France.
    philippe.sistatiemm.univ-montp2.Ir
    The proton leakage through anion exchange membrane is a limiting Iactor Ior acid reconcentration. The internal acidity
    constant has been determined locally by conIocal Raman microspectroscopy |1|. The diIIerence between the value obtained by
    this method and classical titration methods has been explained by a thermodynamic model taking into account the Donnan
    potential. Indeed, the computation oI the chemical composition oI the membrane in equilibrium with the acidic solutions
    revealed that the aqueous phase inside the membrane is Iar less acidic than the external equilibrating solution. Depending on
    the pH oI the equilibrating solution the electrical conductivity and water content has also been measured. The correlation
    between the internal dissociation state oI the ionisable groups and the later value shows that there exists a quasi-linear
    relationship between the water content, the conductivity and the dissociation rate oI the exchanging sites.
    The kinetic oI acid diIIusion and protonation oI the membranes has been studied by using microscopic Raman spectroscopy. A
    miniaturized cell with a microIluidic conIiguration has been designed with this goal to be achieved. Concentration proIiles oI
    protonated and non-protonated sites in the membrane were recorded along time, depending on the membrane grade and the
    nature oI the acid transported. In parallel, diIIusion kinetics was investigated macroscopically in a conventional dialysis cell.
    The diIIusion coeIIicient obtained by both methods are compared and interpreted through a protonation/diIIusion model Ior
    this kind oI membrane.
    |1| L. Franck-Lacaze, P. Sistat, P. Huguet, Determination oI the pKa oI poly(4-vinylpyridine)-based weak anion-exchange
    membranes Ior the investigation oI the side proton leakage, Journal oI Membrane Science, 326 (2009) 650.
    -286-
    Computed chemical composition oI the membrane content as
    a Iunction oI the membrane internal pH.
    PC.1.1
    Molecular dynamics simulations of gas permeation through realistic polyimide
    membranes
    S. Neyertz, D. Brown
    LMOPS-UMR CNRS 5041, Universitv of Savoie, Bat. IUT, 73376 Le Bourget du Lac Cedex, France
    Sylvie.Neyertzuniv-savoie.Ir
    Glassy polyimides are oI great interest as dense membranes Ior gas separation, since they combine excellent mechanical,
    thermal, and chemical stabilities with a large range oI penetrant selectivities. Their permeabilities with respect to, Ior example,
    oxygen are partially governed by the chain chemical structures, which can be derived Irom a large variety oI aromatic or
    alicyclic dianhydride and diamine motives.1 However, the chemical structure is only one oI the Iactors underlying the
    transport properties,2 and it is well-known that many other parameters will inIluence diIIusion and selectivity over the entire
    processing stage. Among those, the so-called 'skin-eIIects are related to the diIIerences between the surIace layers and the
    core oI a membrane.
    We have designed a procedure, loosely based on the experimental solvent-casting process, in order to create realistic glassy
    polymer models containing actual surIaces. It was used to prepare Iully-atomistic ODPA-ODA polyimide membranes with Iull
    excluded-volume and electrostatic nonbonded interactions.3-6 The resulting model membranes exhibited the typical Ieatures oI
    surIace layers, i.e. Ilattened chain conIigurations, lower density, surIace roughness, and increased mobility at the interIaces.
    Calculations related to gas permeation were initially restricted to very small and highly mobile helium-like probes.3-5 More
    recently, oxygen penetration and diIIusion through an ODPA-ODA membrane was Iollowed using a realistic Iorce-Iield.6
    Results associated to the solubility and mobility oI small gas molecules at the vicinity oI polymer interIacial structures will be
    presented and compared to those in the corresponding bulk phases.7 The eIIects oI external gas pressure on the transport
    through the surIace layers oI glassy polymer membranes will be addressed. We will also present new results obtained on
    Iluorinated 6FDA-6FpDA membranes.
    |1| Yampolskii, Y.; Pinnau, I.; Freeman, B. D., Materials Science oI Membranes. John Wiley & Sons Ltd.: Chichester, 2006.
    |2| Pandey, P.; Chauhan, R. S. Prog. Polym. Sci. 2001, 26, 853-893.
    |3| Neyertz, S.; Douanne, A.; Brown, D. Macromolecules 2005, 38 (24), 10286-10298.
    |4| Neyertz, S.; Douanne, A.; Brown, D. J. Membrane Science 2006, 280, 517-529.
    |5| Neyertz, S. SoIt Materials 2007, 4 (1), 15-83.
    |6| Neyertz, S.; Brown, D. Macromolecules 2008, 41 (7), 2711-2721.
    |7| Neyertz, S. Macromol. Theory Simul. 2007, 16, 513-524.
    -287-
    PC.1.2
    Flux enhancement by bubbling: development of a new integrated hydrodynamic and
    mass transfer model
    M. E. Valentine, R. W. Field, Z. F. Cui
    Department of Engineering Science, Universitv of Oxford, Parks Road, Oxford, OX1 3PJ,UK
    mark.valentineeng.ox.ac.uk
    The addition oI a gas-phase by bubbling to membrane systems has been shown to improve Ilux. The bubbles help to mix the
    suspended solids and create a cross Ilow along the membrane surIace reducing the build up oI solids there. Modeling this Ilux
    enhancement has principally employed the 1-D stagnant Iilm model. The gas-liquid hydrodynamics are calculated using
    computational Iluid dynamics (CFD) Irom which the shear is used to calculate the mass transIer coeIIicient |1|. However, this
    method does not account Ior the 3-D properties oI the Ilow and assumes steady shear rates which are not present in the system.
    An improved model is derived which combines the gas-liquid hydrodynamics with the global mass transIer Ior the suspended
    particles. CFD is used to solve the Navier-Stokes equations Ior a single bubble in the membrane giving the bubble shape and
    velocity Ilow Iield. These velocity components are then used in the solution oI the 3-D mass transIer convection-diIIusion
    equation. Previous solutions with this method have been limited to single phase Ilow |2|. The solution to this equation provides
    the concentration oI the suspended particles throughout the system in response to the bubble. The concentration oI particles
    normal to the membrane surIace is then used to calculate the external Iouling and the resistance to Ilow in this direction. The
    Ilux is then calculated using the resistance model. The secondary Ilow induced by the bubble decreases the external cake
    resistance, yielding higher Iluxes. As a result the enhancement due to bubbling is Iound.
    |1| T. Taha, Z. F. Cui, CFD modelling oI gas-sparged ultraIiltration in tubular membranes, Journal oI Membrane Science,
    2002, 210, 13-27
    |2| Y. Lee, M. Clark, Modelling oI Ilux decline during crossIlow ultraIiltration oI colloidal suspensions, Journal oI Membrane
    Science, 1998, 149, 181-202
    PC.1.3
    Investigations on the mechanisms of 5-fluorouracil imprinting by a computational
    approach
    P. Cairo
    1,2
    , E. Tocci
    2
    , E. Drioli
    1,2
    1
    Dip. di Ingegneria Chimica e dei Materiali, Universita della Calabria, via P. Bucci, Arcavacata, Rende, 87036 (CS) - ITALY
    2
    ITM-CNR c/o Universita della Calabria, via P. Bucci 17/C, Arcavacata, Rende, 87036 (CS) - ITALY
    pacairounical.it
    Computational tools were used Ior the understanding oI the intermolecular interactions in molecular imprinting oI 5-
    Iluorouracil (5-FU), an anticancer agent widely used in the clinical treatment oI several solid cancers, such as breast,
    colorectal, liver and brain cancer |1|.The aim oI this work was to investigate the aIIinity oI Molecularly Imprinted Polymers
    (MIPs) based on methacrylic acid (MAA) as Iunctional monomers, Ior the 5-FU to control the release oI the drug.
    Molecular imprinting is an eIIicient technique Ior the introduction oI regions with highly speciIic molecular arrangements into
    polymeric matrices |2|. The technique to produce MIPs, using the non-covalent approach, involves the arrangement oI
    Iunctional monomers around a templating ligand.
    The capacity oI the polymer to recognize and to bind the template was evaluated. Molecular mechanics (MM), molecular
    dynamics (MD) and docking simulations were carried out in order to predict the interaction energies, the closest approach
    distances and the active site groups between the MAA monomers and the drug |3|. The minimized structures oI 5-FU and
    MAA monomer were obtained with the use oI molecular mechanics approach.
    -288-

    5-Iluorouracil MIP cavity Ior 5-Iluorouracil
    |1| K. Yoneda, T. Yamamoto, E. Ueta, T. Osaki, Cancer Lett., 1999, 137, 17-25.
    |2| E. Caro, R.M. Marce, P.A.G. Cormack, D.C. Sherrington, F. Borrull, J. Chromatogr. A, 2003, 995, 233-238.
    |3| D. Pavel, J. Lagowski, Polymer, 2005, 46, 7543-7556.
    PC.1.4
    Understanding ligand-protein interactions in affinity membrane chromatography for
    antibody purification
    C. Boi
    1
    , V. Busini
    2
    , M. Salvalaglio
    2
    , C. Cavallotti
    2
    , G.C. Sarti
    1
    1
    Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali, Universita di Bologna, via Terracini 28
    40131 Bologna, Italv.
    2
    Dipartimento di Chimica, Materiali e Ingegneria Chimica G. Natta, Politecnico di Milano, via Mancinelli 7 20131 Milano,
    Italv.
    cristiana.boiunibo.it
    AIIinity chromatography with Protein A beads is the current standard Ior the primary capture oI monoclonal antibodies. The
    high cost oI Protein A activated supports, ligand leakage and the limited production capabilities oI the bead-based
    chromatographic process are at the origin oI the current research eIIorts towards Ieasible alternatives. Synthetic ligands, that
    mimic the interaction between Protein A and the Fc portion oI immunoglobulins, have been immobilized on membrane
    supports. In this work, regenerated cellulose membranes with immobilized synthetic A2P have been characterized and tested
    Ior binding and elution perIormance using pure polyclonal human IgG solutions as a Ieed and several buIIers Ior the elution
    step. A2P is a synthetic ligand obtained Irom a triazine scaIIold, which binds the Fc region oI the antibody. The eIIects oI the
    membrane support and oI the spacer arm on the ligand-ligate interaction have been studied in detail.
    The experimental results have been interpreted on the basis oI molecular dynamics simulation oI the interaction between IgG
    and the supported ligand. Molecular models oIIer in Iact the possibility to investigate the nature oI the interaction between
    protein and ligand Irom an atomistic standpoint, thus supplying inIormation that can be hardly accessed Iollowing
    experimental procedures. MD simulations were perIormed in explicit water, modelling the membrane as a matrix oI
    overlapped glucopyranose units. Electrostatic charges oI the ligand and spacer considered were calculated through ab initio
    methods to complete the Iorce Iield used to model the membrane. The simulations enabled to elucidate how the conjunct
    interactions oI surIace, spacer and ligand with IgG contribute to the Iormation oI the bond between protein and aIIinity
    membrane.
    Acknowledgement: This work has been perIormed as part oI the 'Advanced Interactive Materials by Design (AIMs) project,
    supported by the Sixth Research Framework Programme oI the European Union (NMP3-CT-2004-500160).
    -289-
    PC.1.5
    Molecular simulation of the sorption behavior of gases in copolyimide membranes
    S. Halitoglu, M. G. Ahunbay, S. B. Tantekin-Ersolmaz
    Istanbul Technical Universitv, Department of Chemical Engineering, Maslak, Istanbul 34469, Turkev
    halitogluitu.edu.tr
    The development oI structure-property relationships Ior polyimides may provide a guideline Ior designing membranes having
    desirable end-use properties. The objective oI this work is to predict the sorption behavior oI 6FDA based copolyimides via
    molecular simulation methods. In our previous studies |1|, sorption coeIIicients oI small gases and hydrocarbons in 6FDA-
    DAM and 6FDA-ODA polyimide membranes were estimated via molecular simulation methods and the diIIerence between
    the experimental and simulated adsorption coeIIicients was Iound to correspond to a Iactor oI 2 or less. In this study, we
    extend this procedure to copolyimides, namely 6FDA/BTDA-DABA(3:1), 6FDA/BTDA-pBAPS(3:1), 6FDA-
    pBAPS/DAM(3:1), and 6FDA-pBAPS/DABA(3:1). The selection oI the copolyimide structures was based on our previous
    study |2| in which the permeability coeIIicients oI H
    2
    , O
    2
    , He, CO
    2
    , N
    2
    , and CH
    4
    gases Ior more than 2200 possible
    copolyimide structures were estimated by the group contribution method oI Alentiev et al. |3|. The predicted permselectivities
    oI the above mentioned copolyimides were located well above the upper bound oI Robeson diagrams Ior CO
    2
    /CH
    4
    and O
    2
    /N
    2
    separation applications. The simulations were carried out using the Accelrvs Materials Studio 4.1 simulation package and
    COMPASS Iorce Iield. The unitcells were constructed Irom 60 or 80 repeat units and equilibrated by applying a combination
    oI molecular dynamics runs and simulated annealing steps. Then Grand Canonical Monte Carlo simulations were applied to
    estimate the sorption coeIIicient oI CO
    2
    , CH
    4
    , O
    2,
    and N
    2
    gases. The predicted ideal sorption selectivity Ior O
    2
    /N
    2
    in
    6FDA/BTDA-DABA(3:1) is nearly twice larger than that oI the others whereas the selectivity oI CO
    2
    /CH
    4
    in all copolyimides
    are almost same.
    Abbreviations: 4,4-HexaIluoro isopropylidene diphthalicanhydride (6FDA); 4,4-Oxydianiline (ODA); 3,5-Diamino benzoic
    acid (DABA); 3,3-4,4-Benzophenone tetracarboxyclic dianhydride (BTDA); 2,4,6-Trimethyl-m-phenylene diamine (DAM);
    Bis |4-(4-aminophenoxy) phenyl| sulIone (pBAPS)
    Financial support Irom TUBITAK (Turkish ScientiIic and Technological Research Council) Grant No. 106M339 is grateIully
    acknowledged.
    |1| S. Halitoglu, M.G. Ahunbay, S.B. Tantekin Ersolmaz, Molecular simulation oI the sorption behavior oI gases in polyimide
    membranes, Proceedings oI Engineering with Membranes 2008, pp. 279-281, May 25-28, 2008, Algarve, Portugal.
    |2| S. Halitoglu, S.B. Tantekin Ersolmaz, Prediction oI gas permeability coeIIicients oI copolyimides by group contribution
    methods, presented at the NAMS meeting, May 12-16, 2007, Orlando, Florida.
    |3| A.Y. Alentiev, K.A. Loza, Y. Yampolski, Development oI the methods Ior prediction oI gas permeation parameters oI
    glassy polymers: polyimides as alternating co-polymers, J. Memb. Sci., 2000, 167, 91-106.
    PC.2.1
    A zonal rate model for stacked membrane chromatography
    E. von Lieres
    1
    , J. Wang
    2
    , M. Ulbricht
    2
    , P. Francis
    3
    , C. Haynes
    3
    1
    Institute of Biotechnologv 2, Research Centre Jlich, 52425 Jlich, Germanv
    2
    Chair of Technical Chemistrv II, Universitv of Duisburg-Essen, 45141 Essen, Germanv
    3
    Michael Smith Laboratories, Universitv of British Columbia, Jancouver, Canada
    e.von.lieresIz-juelich.de
    We have developed a novel zonal rate model (ZRM) Ior stacked membrane chromatography. The model accounts Ior
    inhomogeneous radial Ilow distributions as illustrated in Figure 1: Several zones with diIIerent residence times can be Iormed
    in the distributors oI the chromatography module and cause inhomogeneous loading oI the membrane stack over time. The
    model is implemented Ior various zone geometries and diIIerent kinetic and isotherm models Ior adsorption and desorption in
    the membrane stack.
    -290-
    Figure 1: Schematic diagram oI the zonal rate model (ZRM).
    The ZRM has proven useIul in analyses oI diIIerent stacked membrane chromatography modules. Breakthrough curves have
    been measured at varied Ilow rates and binding conditions. Figure 2 shows typical non-binding data Irom a Mustang XT 5
    module that a model with two zones and symmetric dead volumes on both sides oI the membrane stack describes signiIicantly
    better than a model with just one zone. The zonal rate model allows quantitative characterization not only oI Ilow distributions
    but also oI binding mechanisms.
    Figure 2: Experimental breakthrough curves (black) and ZRM simulations with a) one zone (blue) and b) two zones (red).
    PC.2.2
    Characterization of electric and dielectric properties of a nanofiltration membrane:
    application to prediction of salt rejection performances
    A. Szymczyk
    1
    , J. Benavente
    2
    , Y. Lanteri
    3
    , P. Fievet
    3
    1
    Chimie et Ingenierie des Procedes, UMR 6226 CNRS-Universite de Rennes 1-ENSCR
    263 Avenue du General Leclerc, CS 74205, 35042 Rennes Cedex, France
    2
    Departamento de Fisica Aplicada 1, Facultad de Ciencias, Universidad de Malaga E-29071 Malaga, Spain
    3
    Institut UTINAM, UMR CNRS 6213, Universite de Franche-Comte, 16 route de Grav, 25030 Besanon Cedex, France
    anthony.szymczykuniv-rennes1.Ir
    Due to its real potentialities Ior the separation or puriIication oI liquid mixtures, nanoIiltration (NF) has Iound applications in
    various industrial sectors like industrial eIIluent treatment, water soItening, drinking water production. Consequently,
    researchers have engaged in the development oI transport models and characterization techniques with the aim oI identiIying
    and understanding the physical phenomena involved in solute separation by NF membranes.
    The signiIicant role oI the membrane Iixed charge in the separation perIormances oI NF membranes is now well-recognized
    and some recent works have pointed out the relevance oI dielectric eIIects |1-3|. These dielectric eIIects also aIIect the
    membrane potential that arises through a membrane separating two solutions oI the same electrolyte at the same hydrostatic
    pressure but diIIerent concentrations |4|.
    The dielectric properties oI the active layer oI a polyamide NF membrane were determined Irom impedance spectroscopy
    experiments carried out with CaCl
    2
    solutions. Measurements were carried out Ior various salt concentrations. Results oI
    impedance spectroscopy were combined with membrane potential measurements in order to determine the membrane volume
    charge density. This latter was computed numerically by means oI a modiIied TMS theory including steric hindrance and
    dielectric eIIects |4|.
    The dielectric properties oI the active layer and the membrane volume charge densities were Iurther used to compute the
    rejection rate oI the various CaCl
    2
    solutions by the NF membrane by means oI the recently developed SEDE (Steric, Electric
    and Dielectric Exclusion) model |2|. It was then possible to evaluate the predictive abilities oI the model since this latter was
    -291-
    used without any adjustable parameter. Model predictions were Iound to be in relatively good agreement with experimental
    rejection rates measured at various permeate volume Iluxes.
    |1| Yaroshchuk, A.E. (2000) Adv. Colloid Interface Sci. 85, 193-230.
    |2| Szymczyk, A.; Fievet, P. (2005) J. Membr. Sci. 252, 77-88.
    |3| Szymczyk, A.; Sba, M.; Fievet, P. (2006) Langmuir 22, 3910-3919.
    |4| Lanteri, Y.; Szymczyk, A.; Fievet, P. (2008) Langmuir 24, 7955-7962.
    PC.2.3
    Towards energy consumption reduction in separation processes: modelling of
    pervaporation performance
    A. VerhoeI, E. De Ridder, B. Bettens, J. Degreve, B. Van der Bruggen
    Division of Applied Phvsical Chemistrv and Environmental Engineering - Department of Chemical Engineering - Katholieke
    Universiteit Leuven, W. de Crovlaan 46, 3001 Heverlee, Belgium
    adrian.verhoeIcit.kuleuven.be
    To improve energy-consuming separation processes, membrane processes become more and more important. For instance,
    Irom an economical point oI view, pervaporation oIIers a good alternative Ior distillation. The unit can either be implemented
    solely, or in a hybrid process |1|.
    Industrial use oI pervaporation is limited however, because oI a lack oI good process perIormance prediction tools. This paper
    describes the development oI a numerical program Ior simulation oI the pervaporation process. Such a program can predict
    necessary membrane properties, eIIiciencies or economical aspects |2|, and stimulates application oI pervaporation in industry.
    With help oI the Maxwell-SteIan model the multicomponent mass transport through the membrane is simulated. To avoid the
    unknown membrane molar mass during the calculations, a conversion to mass Iractions is perIormed. The implications oI this
    conversion, the structure oI the total program and the determination oI input parameters are shown in this paper. Also the
    possible use to innovate energy-consuming processes in industry is described, showing the options oI the program.
    |1| Veerle Van HooI, Liesbet Van den Abeele, Anita Buekenhoudt, Chris Dotremont and Roger Leysen (2004), Economic
    comparison between azeotropic distillation and diIIerent hybrid systems combining distillation with pervaporation Ior the
    dehydration oI isopropanol, Separation and PuriIication Technology 37(1), 33-49
    |2| Adrian VerhoeI, Jan Degreve, Bart Huybrechs, Henk van Veen, Paul Pex and Bart Van der Bruggen (2008), Simulation oI
    a hybrid pervaporation-distillation process, Computers and Chemical Engineering 32(6), 1143-1154
    PC.2.4
    Gas separation transport modeling for PDMS coatings on PEI-PEG-IPN membranes
    K. Darcovich, M.M. Dal-Cin, S. Saimani, A. Kumar
    National Research Council of Canada, Institute for Chemical Process and Environmental Technologv, Ottawa, Ontario,
    Canada, K1A 0R6
    ken.darcovichnrc-cnrc.gc.ca
    The use oI PDMS (polydimethylsiloxane) as a caulking material on non-deIect Iree asymmetric polymer membranes Ior gas
    separations is widespread. It has been observed that the pure gas selectivity oI a caulked (polyetherimide-polyethylene glycol
    interpenetrating network) membrane can achieve its intrinsic value. However, Ior various Ieed compositions oI CO
    2
    and N
    2
    , the
    mixed gas selectivity oI the caulked membrane approached that oI the PDMS coating. Classical resistance models |1| predict
    PDMS selectivity Ior pure gases when caulking layers are very thick, ie; 8mm. Present mixed gas studies show the selectivity
    approaching intrinsic PDMS values arising at much smaller PDMS thicknesses. In this work we postulate that the PDMS layer
    acts to limit the mass transIer oI CO
    2
    and N
    2
    when diIIusing in a mixed system, an eIIect which may not be apparent
    considering only pure gases.
    -292-
    Fig. 1 : Schematic oI physical system modeled.
    Theoretical treatment oI this two-layer gas separation
    system was advanced on both the micro and macro levels.
    The problem considered is depicted schematically in Fig.
    1. The solution-diIIusion model |2| was used to determine
    steady state mass transport rates on the micro-level, based
    on Fickian diIIusion oI gases in dense solids, namely,
    0
    2

    i i
    c D
    . At the macro-level, models explored
    solubility constraints and system operating parameters,
    correlating experimentally observed permeabilities with
    system parameters, per |3|,
    p
    x
    x
    c
    D P
    i
    i i

    .
    Feed pressure, composition and the Iilm thicknesses oI
    both the PDMS and PEI-PEG-IPN layers were system
    variables in this study. On the micro-level, Iield solutions
    oI the mixed gas diIIusion problem were obtained in the
    interior oI the adjoining PDMS and PEI-PEG-IPN layers,
    allowing novel observations oI characteristics oI the
    component concentration proIiles, component Iluxes, the
    role oI gas solubility, as well as the nature oI the pressure distribution proIile across the solid layers required to produce
    plausible results Ior this coupled system. Field solutions, in view oI system constraints also allow Ior comments on the nature
    oI the component activity coeIIicients in the solubilized state.
    |1| J.M.S. Henis and M.K. Tripodi, Composite hollow Iiber membranes Ior gas separation: The resistance model approach, J.
    Membrane Sci., 8 (1981) 233-246.
    |2| J.G. Wijmans and R.W. Baker, The Solution-DiIIusion Model: A UniIied Approach to Membrane Permeation, in Materials
    Science oI Membranes Ior Gas and Vapor Separation, Y. Yampolskii, I. Pinnau and B.D. Freeman (Eds.), 2006, John Wiley
    and Sons, Ch.5, pp 159-189.
    |3| D.R. Paul, ReIormulation oI the solution-diIIusion theory oI reverse osmosis, J. Membrane Sci., 241 (2004) 371-386.
    PC.2.5
    Bioseparation of peptides and biogenic amines by nanofiltration
    J. Labanda
    1
    , J. Sabate
    2
    , J. Llorens
    1
    1
    Department of Chemical Engineering, Universitv of Barcelona, Marti i Franques 1, 08028 Barcelona, Spain
    2
    Departament dEnginveria Agroalimentaria i Biotecnologia, Universitat Politecnica de Catalunva, Edifici ESAB, Avinguda
    del Canal Olimpic s/n, 08860-Castelldefels, Spain
    jlabandaub.edu
    Many biological products (as Iood, medicaments or cosmetics) need to be puriIied beIore use. Peptides and amines are present
    in a wide range oI biotechnology products and they usually present similar molecular weights, making diIIicult their
    puriIication. NanoIiltration is a pressure-driven membrane technology that can be very useIul Ior the separation or retention oI
    small biomolecules with similar molecular weights but diIIerent electrical charge |1-3|.
    NanoIiltration membranes are usually electrically charged because oI their terminal Iunctional groups and this electrical charge
    can depend on the Ieed composition and pH. NanoIiltration membranes are usually negatively charged in neutral or alkaline
    conditions and positively charged in highly acidic conditions. ThereIore, the more accepted mechanisms oI solute retention are
    the size exclusion and electrical charge eIIects.
    In this work, we study the retention and separation oI peptides and biogenic amines with a nanoIiltration membrane as a
    Iunction oI biomolecule concentrations and pH. The experimental results were adjusted according to the extended Nernst-
    Planck model, coupled with the steric hindrance and the Donnan equilibrium with dielectric exclusion.
    The results were discussed in terms oI the changes that pH produces on the electrical charge oI both membrane and amines,
    and consequently on the membranesolute interactions. Good correlation between experimental and calculated rejection Iactor
    has been obtained. The electrostatic interaction between membrane and biomolecules was the dominant mechanism governing
    the separation process.
    The authors are grateIul to the Spanish 'Ministerio de Ciencia y Tecnologia (project CTQ2005-08346-C02-01/PPQ) Ior Iunds
    received to carry out this study.
    -293-
    |1| J. Sabate, J. Labanda, J. Llorens, J. Membrane Sci., 310 (2008) 594.
    |2| A. Saxena, B.P. Tripathi, M. Kumar, V.K. Shahi, Adv. Colloid InterIace Sci., 145 (2009) 1.
    |3| X.-L. Wang, W.-J. Shang, D.-X. Wang, L. Wu, C.-H. Tu, Desalination, 236 (2009) 316.
    PC.2.6
    Modeling particle size in ultrafiltration
    A.K. Pavanasam
    1
    , A. Abbas
    2
    , V. Chen
    1
    1
    UNESCO Centre for Membrane Science and Technologv, School of Chemical Sciences and Engineering, Universitv of New
    South Wales SYDNEY 2052 Australia
    2
    School of Chemical and Biomolecular Engineering, Universitv of Svdnev SYDNEY 2006 Australia
    aliausyd.edu.au
    Knowledge oI particle behavior in Iiltration is growing continuously but the passage oI particles across a membrane is still not
    completely understood. Particle size inIluences the mobility/movement and passage oI particles across a membrane. Though
    particle size has a great inIluence on the Iinal outcome oI the Iiltered product |1|, not much attention is given to it in
    comparison with the Ilux and Iouling studies. Experimental investigations that track the particle size state can reveal
    inIormation about size-dependent Iiltration kinetics. Such inIormation is crucial in developing models that predict particle size
    changes in the Iiltration products.
    In this paper, a population balance model (PBM) is Iormulated to describe the discrete particle size oI the permeate/retentate
    streams Ior the tangential Ilow ultraIiltration process. The parameters oI a kinetic sub-model are estimated using data gathered
    Irom a bench-top experimental Iacility under varying transmembrane pressures (TMP) and Ieed concentrations. This sub-
    model is then incorporated with the population balance equation beIore being validated Ior particle size prediction under new
    experimental conditions. The model can predict the particle size distribution while considering the eIIect on Iiltration
    eIIiciency determined as log reduction value (LRV).
    Silica particles (Figure 1) are chosen Ior this study as surrogate virus particles and also because they could be exploited in
    water puriIication processes |2|. Experimental results clearly indicate that the particle size and their distribution is a key Iactor
    in the eIIiciency and the permeate quality (Figure 2). The eIIect oI particle size is more prominent when the particles are
    relatively smaller than the pore size; the bigger the particles the easier it is to achieve the required LRV values. Preliminary
    modeling results are promising indicating that the mechanics oI the PBM, which are to a large extent statistical in nature, are
    close to the region oI the experimental data.

    Fig 1: TEM micrograph oI Ieed particles. Fig 2: Particle size distribution oI retained silica particles.
    |1| Binbing Han, S Akeprathumchai, S R Wickramasinghe. Flocculation oI Biological Cells: Experiment vs Theory, AIChE
    Journal, 49:1687-1701, 2003
    |2| S H K Oh, S Takizawa, S Ohgaki, H Katayama, K Oguma, M J Yu. Removal oI organics and viruses using hybrid ceramic
    MF system without draining PAC, Desalination, 202:191198, 2007
    -294-
    PC.2.7
    Anisotropic gas transfer phenomena in asymmetric membranes
    I. Kurchatov
    1,3
    , A. Krukov
    1
    , N. Laguntsov
    2
    , V. Tronin
    2
    , V. Volkov
    3
    1
    JSC 'Aquaservice`, Russia, Moscow, Kashirskoe sh., 31
    2
    Moscow Engineering Phvsics Institute (State Universitv), 115409, Russia, Moscow, Kashirskoe sh., 31
    3
    J.Topchiev Institute of Petrochemical Svnthesis, Russian Academv of Sciences, 119991, Moscow, Leninskv prospekt, 29
    aquaservmail.ru
    In the last years the eIIects oI asymmetric gas transIer in membranes that have gradient porosity have been discovered -
    anisotropy oI gas permeability, anisotropy oI catalytic activity and "hysteresis" oI permeability |1,2|. Anisotropy oI gas
    permeability, i.e. dependence oI permeability on a direction oI gas supply through membrane, was observed both on polymeric
    asymmetric membranes, and on composite ceramic membranes. On a composite ceramic membrane made by the method oI
    selI-propagating high-temperature synthesis with nanoporous layer put on it, it was revealed that the amount oI permeability in
    case oI supply on the porous layer was smaller than in case oI supply on non-porous surIace (direct anisotropy). On the
    industrial gasseparation asymmetric PVTMS membrane both direct and opposite anisotropy oI permeability were observed Ior
    diIIerent samples oI membrane. It was caused by diIIerences in porous structure oI investigated membranes.
    These eIIects are observed in a Iree-molecular Ilow regime, that makes it possible to consider that these eIIects are caused by
    interaction oI gas molecules with the inner surIace oI a porous media. With the use oI methods oI stochastic dynamics, models
    oI speciIic interaction oI gas molecules with the surIace have been developed. At such interaction, distribution oI molecules by
    directions oI movement inside the membrane channels becomes nonisotropic, and the most probable direction oI movement is
    perpendicular to the surIace. Similar movement oI molecules oI gas leads to increase in time oI a liIe oI a molecule in the
    channel that allows to explain eIIect oI "permeability hysteresis.
    For the description oI a gas Ilow through a composite membrane the system oI the equations describing a current oI gas in
    layers oI a membrane taking into account not isotropic distribution has been written down. With use oI this system it was
    possible to explain and describe observable anisotropic gas transIer phenomena.
    Work supported by grant oI Russian Foundation Ior Basic Researches # 07-08-00461-a
    |1| I.M. Kurchatov, N.I. Laguntsov, V.N. Tronin, V.I. Uvarov and I.P. Borovinskaya, Doklady Physics, 2008, 53(3), 118.
    |2| I. M. Kurchatov, N. I. Laguntsov, M. V. Tsodikov, A. S. Fedotov and I. I. Moiseev, The Nature oI Permeability Anisotropy
    and Catalytic Activity, Kinetics and Catalysis, 2008, Vol. 49, No. 1, pp. 121126.
    PC.2.8
    Modeling mass and heat transfers during membrane formation - numerical results
    and experimental validation
    D. Bouyer
    1
    , W. Werapun
    1
    , C. Pochat-Bohatier
    1
    , A. Deratani
    2
    , J.P. DesIours
    1
    1
    Laboratoire de Genie des Procedes Eau et Bioproduits, UMR CIRAD/UMII/UMI 016, Universite Montpellier 2, cc05 2 place
    Bataillon, 34095 Montpellier cedex 05, France.
    2
    Institut Europeen des Membranes, UMR CNRS/ENSCM/UMII 5635, Universite Montpellier 2, 2 place Bataillon 34095
    Montpellier, France.
    denis.bouyeruniv-montp2.Ir
    Modeling mass and heat transIer phenomena involved during the membrane Iormation has a great importance since it could
    help predicting the Iinal membrane morphology, depending on the Iormulation and the process parameters. The Vapor Induced
    Phase Separation (VIPS) process was considered in this study, using diIIerent polymer/solvent/non-solvent systems
    (PEI/NMP/water, PEI/DMAc/water, PES/NMP/water, PES/DMF/water). The modeling approach consists in taking into
    account (i) the thermodynamics oI the polymeric system (Flory-Huggins theory) in order to determine the activity coeIIicient
    oI the diIIerent components within the solution, (ii) the external mass and heat transIer kinetics involving natural or Iorced
    convection, (iii) the internal mass transport within the polymer solution beIore phase separation (diIIusion phenomena) |1,2|.
    Initial and boundary conditions must be speciIied and the whole equations system can be resolved Ior one-dimension geometry
    and using Iinite element soItware (Comsol Multiphysics). On a second part, the simulated results were validated using
    experimental data. Gravimetric measurements perIormed in-line during the process gave inIormation on the global mass
    transIer between the membrane-Iorming system and the external environment. Furthermore, in-situ measurements were
    -295-
    conducted within the polymer solution during the process using near inIrared spectroscopy analysis. The local concentration
    beneath the surIace could also be obtained and compared to the numerical results. Once the simulated results were validated by
    experimental data, they can be used to predict and/or explain morphological properties oI the Iinal membranes. For example,
    Ior the PEI/NMP/water system, a local pore size gradient near the top surIace was observed in the cross-section (Fig. 1) at
    12-wt PEI (initial polymer concentration), when VIPS was perIormed at 40C and 75 RH. This pore size gradient could be
    explained by a polymer concentration gradient in this region, due to the rapid water penetration at the solution/air interIace.
    FIG 1: Membrane morphology Ior a PEI/NMP/water system (12-wt PEI), 40C, 75RH compared to simulated polymer
    concentration proIiles
    |1| Y. Yip, A.J. McHugh, Modeling and simulation oI nonsolvent vapor-induced phase separation, Journal oI Membrane
    Science 271 (2006) 163176
    |2| V.P. Khare, A.R. Greenberg, W.B. Krantz, Vapor-induced phase separationeIIect oI the humid air exposure step on
    membrane morphology Part I. Insights Irom mathematical modelling, Journal oI Membrane Science 258 (2005) 140156
    PC.2.9
    New approach to the barrier properties of polyamide 12/montmorillonite
    nanocomposites
    B. Alexandre
    1
    , D. Langevin
    1
    , T. Nguyen
    1
    , P. Mederic
    2
    , T. Aubry
    2
    , S. Marais
    1

    1
    Universite de Rouen, Laboratoire Polvmeres, Biopolvmeres, Surfaces , FRE 3101 CNRS & FR 3038 76821 Mont-Saint-
    Aignan Cedex, France
    2
    Equipe de Rheologie du LIMATB EA4250, Universite de Bretagne Occidentale, 6 Av. Le Gorgeu, C.S. 93837, 29238 Brest
    Cedex 3, France
    Stephane.maraisuniv-rouen.Ir
    The aim oI this work is to study the transport oI small molecules into the hybrid systems polyamide 12
    (PA12)/montmorillonite made by melt blending method with two blending conditions |1|. The addition oI Cloisite

    Na

    into
    the PA12 leads to microcomposites, whereas the addition oI Cloisite

    30B Iorms nanocomposites. The transport mechanisms


    were investigated by using three molecules: nitrogen, water and toluene. While the barrier eIIect is obtained to nitrogen, Ior
    water the barrier eIIect changes with the amount oI Iillers and disappears Ior toluene. The reduction oI permeability Ior
    nitrogen is due to the tortuosity and the molecular mobility reduction around the polymer-Iiller interIace. For water and
    toluene, the permeation and sorption kinetics reveal many concomitant phenomena responsible oI the permeation behaviour.
    The water and toluene molecules interact diIIerently with Iillers according to their hydrophilic/hydrophobic character.
    Moreover, the plasticization phenomena oI matrix by water and toluene molecules are correctly described by the law DD
    0
    e
    C
    .
    On the basis oI the Nielsen`s tortuosity concept, we suggested a new approach oI the relative permeability simulation based on,
    not only the geometrical parameters (aspect ratio, orientation, recovery) and molecular mobility (rigidity), but also by
    considering phenomenological parameters which result Irom structural characterisation and permeation kinetics.
    |1| Water barrier properties oI polyamide 12/montmorillonite nanocomposite membranes: Structure and volume Iraction
    eIIects, Journal oI Membrane Science (in press).
    -296-
    PC.2.10
    Modeling the influence of urease immobilization on the performance of hemodialysis
    membranes
    H.E. Abaci
    1
    , S. Alsoy Altinkaya
    2
    1
    Johns Hopkins Universitv, Department of Chemical and Biomolecular Engineering, 221 Marvland Hall 3400 North Charles
    Street, Baltimore, MD 21218, USA.
    2
    I:mir Institute of Technologv, Department of Chemical Engineering, Urla I:mir, 35430 Trkive
    sacidealsoyiyte.edu.tr
    Patients suIIering Irom chronic renal Iailure are mostly treated with hemodialysis due to limited number oI donors available
    Ior kidney transplantation. Modeling oI hemodialysis operation is required Ior evaluating new module designs and optimizing
    diIIerent Iorms oI the therapy both oI which determine the eIIiciency oI the process. In this study, urease enzyme
    immobilization on hemodialysis membranes is proposed as an eIIective way oI increasing the overall perIormance oI the
    process in terms oI enhanced urea removal by enzymatic reaction and reduced protein Iouling on the membranes. To evaluate
    the Ieasibility oI this proposal, a theoretical model was developed and the solute concentrations both in patient`s blood and at
    the dialyzer outlet were predicted. The model takes into account simultaneous mass and momentum transIer on the blood side
    both in radial and axial directions as well as the protein adsorption on the surIace oI the membrane. The extent oI protein
    Iouling was determined with molecular simulations in which the molecular interaction energies are considered.
    Model predictions have shown that, urea clearances are increased signiIicantly in the case oI urease immobilization due to
    enzymatic reaction on the surIace. On the other hand, molecular simulations have shown that, protein adsorption capacity oI
    hemodialysis membranes strongly depends on the electrical potential oI the surIace. Urease immobilized on hydrophobic
    membranes are Iound to give a higher resistance to protein Iouling than plain membranes and expected to be more
    biocompatible in comparison with highly hydrophilic commercial membranes such as AN69. The accuracy oI the model
    predictions has been tested with two diIIerent sets oI experimental data collected with commercial plain hemodialysis
    membranes. The model is Iully predictive and general in nature, thus, can be applied to any type oI membrane material as long
    as the structural properties oI the membrane and transport parameters oI the solutes through the membrane are known.
    PC.2.11
    Modeling the performance of enzyme immobilized membranes
    Y. Yurekli
    1
    , S. Guedidi
    3,4
    , S. Alsoy Altinkaya
    1
    , A. Yemenicioglu
    2
    , C. Innocent
    3
    , A. Deratani
    3
    , S. Roudesli
    4
    1
    I:mir Institute of Technologv, Department of Chemical Engineering, Gulbahce Kovu, 35430, Urla I:mir, Turkev.
    2
    I:mir Institute of Technologv, Department of Food Engineering, Gulbahce Kovu, 35430, Urla I:mir, Turkev.
    3
    Institut Europeen des Membranes, Place Eugene Bataillon, CC 047, 34095 Montpellier, Cedex 5, France.
    4
    Laboratoire des Polvmeres-Biopolvmeres Materiaux Organiques, Faculte des Sciences de Monastir/ Avenue de
    lEnvironnement 5019, Monastir. Tunisie.
    sacidealsoyiyte.edu.tr
    Enzyme immobilized membrane acts as a separation and catalytic unit and can be used in production, processing and treatment
    operations. Selective mass transport with a biological reaction Iollowed by the selective removal oI products Irom the reaction
    site can eliminate product inhibition eIIects on the catalytic activity oI the enzyme, thus, can increase the conversion oI the
    reactions. Enzyme can be entrapped within the pores oI the membrane or can be bound on the surIace oI the membrane. The
    conversion oI the substrate depends not only on the enzyme kinetics but also mass transport conditions. Various parameters
    such as the type and structural properties oI the membrane and operating conditions inIluence the activity decay proIile and
    the rate oI mass transport. To achieve desirable productions or removals with the enzyme immobilized membranes, modeling
    the operation within a selected geometry could provide useIul guidelines Ior optimizing operating conditions or Ior designing
    the membrane structures.
    In the present study, the behavior oI a dead-end stirred cell Iiltration system has been modeled. The model assumes that
    enzyme is immobilized on both surIaces oI the membrane and Iorms a porous gel layer. The model takes into account mass
    transIer resistances on the retentate and permeate sides and one dimensional mass transIer through the membrane and porous
    enzyme layers. In addition, the deactivation oI enzyme during the process has been considered. The model equations have been
    solved numerically using Iinite diIIerence method and the contribution oI most signiIicant transport mechanisms has been
    determined. The theoretical predictions have been compared with the experimental data collected Ior the decomposition oI
    urea by urease enzyme immobilized on commercial poly-(acrylonitrile-co-sodium methallyl sulIonate) copolymers (AN69)
    -297-
    ultraIiltration membrane. The mathematical model is general in nature and can be used to describe the perIormance oI
    diIIerent enzyme immobilized membrane by knowing the rate expression, structural parameters oI the membrane and the
    transport parameters oI the substrate.
    Acknowlegment: The authors would like to thank The ScientiIic and Technical Research Council oI Turkey and The Ministry
    oI Foreign AIIairs oI the Republic oI France Ior partial Iunding (IFC) and the Gambro-Hospal, Lyon, France Ior kindly
    providing the membranes.
    PC.2.12
    Transport of water ethanol mixtures through dense PIM-1 membranes
    A.A. Yushkin
    1
    , S.E. Tsarkov
    1
    , A.V. Volkov
    1
    , V.N. Tronin
    2
    , P.M. Budd
    3
    1
    A.J.Topchiev Institute of Petrochemical Svnthesis RAS, Moscow, Russia
    2
    Moscow Engineering Phvsics Institute, Moscow, Russia
    3
    School of Chemistrv, The Universitv of Manchester, Manchester, M13 9PL, UK
    avolkovips.ac.ru
    Recently, a new glassy polymer with intrinsic microporosity (PIM-1) that has extremely high Iree-volume Iraction up to 22
    was synthesized by reaction oI 5,5`,6,6`-tetrahydroxy-3,3,3`,3`-tetramethyl-1,1`-spirobisindane with tetraIluoro-phthalonitrile
    (acronym PIM-1). The aim oI this work is the study oI permeation oI wetting/-non-wetting mixtures through dense PIM-1
    membranes.
    Since PIM-1 is a hydrophobic polymer, ethanol and water were used as wetting and non-wetting components, respectively.
    The Iiltration was carried out in a dead-end cell at 20 bar and room temperature. A number oI approaches were used to
    describe the transport through PIM-1 membranes
    |1-5|.
    As shown in Fig.1, the permeability (P) as a
    Iunction oI Ieed composition has a threshold
    character. Below a threshold Ieed concentration
    (C
    EtOH
    _40), no Ilux through the membrane was
    experimentally observed during at least 7 days oI
    continuous measurements. Further increasing oI
    ethanol content in the Ieed leads to increasing oI
    overall permeability through the PIM-1. Such
    transport behavior can be explained in the
    Iramework oI percolation theory, when the Iilling
    oI 'pores (Iree volume elements) with a non-
    wetting liquid can be represented as a process oI
    the Iormation and growth oI Iractal clusters and
    the Iormation oI an inIinite cluster across the
    membrane. The model |1| based on the percolation
    theory principals can describe the experimental
    data (see Fig.1).
    |1| C.Chen, B.Han, J.Li, T.Shang, J.Zou, W.Jiang. J. Membr. Sci., 187 (2001), 109.
    |2| J.L.C.Santos, A.M.Hidalgo, R.Oliveira, at all J. Membr. Sci., 300 (2007), 191.
    |3| D.Bhanushali, S.Kloos, C.Kurth, D.Bhattacharyya. J. Membr. Sci., 189 (2001), 1.
    |4| D.R.Machado, D.Hasson, R.Semiat. J. Membr. Sci. 166 (2000), 63.
    |5| J.Geens, B.V.d.Bruggen, C.Vandecasteele. Sep. Purif. Technol., 48 (2006), 255.
    -298-

    0
    1
    2
    3
    4
    5
    0 20 40 60 80 100
    C(EtOH/H
    2
    O),
    P
    d
    ,

    1
    0
    -
    7

    k
    g

    m
    /
    m
    2

    h

    b
    a
    r
    Experimental data
    Percolation theory based model |1|
    S-D model (total permeability) |2|
    Bhanushali equation |3|
    Machado equation |4|
    Geens equation |5|
    Fig. 1. Ethanol-water mixture permeability through PIM-1 (20 bar).
    PC.2.13
    NH
    4
    Cl influence on Zn transport through a cation exchange membrane in a
    Zn-NH
    3-
    Cl system
    E. Ortega
    1
    , P. Sistat
    2
    , V. Perez-Herranz
    1
    , G. Pourcelly
    2
    1
    Dpto. Ingenieria Quimica v Nuclear, Universidad Politecnica de Jalencia, P.O.Box 22012 E-46071 Jalencia, Spain
    2
    Institut Europeen des Membranes (IEM), ENSCM, UM2, CNRS, Universite Montpellier 2, CC047, Place Eugene Bataillon,
    34095 Montpellier, France
    eortegaiqn.upv.es
    Electrodialysis is widely used Ior separation oI ions and molecular solutions, and nowadays it is becoming a suitable
    alternative Ior wastewater treatment in plating industries, such as rinsewaters Irom zinc chloride plating industries.
    The main components oI zinc chloride plating baths are ZnCl
    2
    and NH
    4
    Cl. In rinsewaters, these components are in the same
    proportion and lower concentrations than in the plating baths. These solutions Iorm a Zn-NH
    3
    -Cl system. In a Zn-NH
    3
    -Cl
    system Zn-NH
    3
    , Zn-Cl, Zn-NH
    3
    ,-Cl and Zn-OH complexes can be Iormed |1,2|. At the solution pH (ca. 7) Zn-OH complexes
    have no quantitative signiIicance.
    In this work the inIluence oI NH
    4
    Cl content on the Zn transport through a Selemion CMV cation-exchange membrane
    separating two identical solutions oI ZnCl
    2
    and NH
    4
    Cl under natural convection has been evaluated by Chronopotentiometry
    and Electrochemical Impedance Spectroscopy.
    For a cation exchange membrane separating two identical solutions oI two cations, in the current range lower than the limiting
    one (where no polarization phenomenon takes place) an equivalent circuit oI two parallel impedances can be proposed, where
    each impedance element is related with the individual transport oI one oI the cations present in the mixture.
    For ZnCl
    2
    0.01M and NH
    4
    Cl concentrations oI 0.001M and 0.01M, a good agreement between the experimental data and the
    values predicted by the model is observed. However, Ior ZnCl
    2
    0.01M and NH
    4
    Cl 0.1M, the experimental data are more
    similar to the obtained Ior NH
    4
    Cl 0.1M than the predicted by the model. This behavior can be due to the Iormation oI Zn-Cl
    and Zn-NH
    3
    complexes, which make Zn
    2
    concentration be lower than 0.01M and thereIore mainly NH
    4

    is transported through
    the cation exchange membrane.
    Dr. E. Ortega wants to express her gratitude Ior the grant no. PR2006-0279 to MEC (Spain).
    |1| J.L. Limpo, A. Luis, Solubility oI zinc chloride in ammoniacal ammonium chloride solutions, Hydrometallurgy, 1993, 32,
    247-260
    |2| S-H Yang, M-T Tang, Thermodynamics oI Zn (II)NH3NH4ClH2O system, Trans. NonIerrous Met. Soc. China, 2000,
    10(6), 830-833
    PC.2.14
    Polarization in hydrogen purification processes using Pd-based membranes
    A. Caravella
    1
    , G. Barbieri
    1
    , E. Drioli
    1,2
    1
    National Research Council - Institute on Membrane Technologv (ITM-CNR), c/o Universitv of Calabria, Jia Pietro Bucci,
    Cubo 17/C, 87036, Rende (CS), Italv
    2
    Department. of Chemical and Materials Engineering, Universitv of Calabria, Jia Pietro Bucci, Cubo 44/A, 87036, Rende
    (CS) Italv.
    alessio.caravellaunical.it
    The aim oI this analysis is determining the eIIects oI the concentration polarization on the perIormances oI Pd-alloy
    membranes Ior hydrogen puriIication processes. The investigation is perIormed by means oI a permeation model using a
    multicomponent approach already introduced and validated elsewhere |1, 2|. Several diIIerent operating conditions are taken
    into account (up-stream hydrogen molar Iraction, total pressure oI up-and down-stream, temperature and membrane thickness)
    considering a multicomponent gaseous mixture in the upstream (Ieed) side. The polarization level is evaluated by means an
    appropriately deIined Concentration Polarization CoeIIicient (CPC), which is represented in some diagrams opportunely called
    "polari:ation maps" being useIul to choose the best working conditions to improve the puriIication process. An important
    result is that, in some conditions, the concentration polarization can be relevant not only when using very thin membranes ( 5
    m ca.), but also thicker ones (50 m ca.). In particular, the perIormance loss oI the membrane is measured in terms oI a
    -299-
    decrease oI the bulk permeance, showing that, sometimes, the concentration polarization produces a high resistance, so that the
    external mass transIer becomes the rate determining step oI the whole permeation process.
    Acknowledgments: The project 'FIRB-CAMERE (RBNE03JCR5) co-Iunded by the "Ministero dell`Universita e della
    Ricerca" (MiUR, Italy) is grateIully acknowledged Ior Iinancial support.
    |1| Caravella A., Barbieri G. and Drioli E., 2008. Modelling and simulation oI hydrogen permeation through supported Pd-
    based membranes with a multicomponent approach. Chem. Eng. Sci.. 63: 2149-2160.
    |2| Caravella A., Barbieri G. and Drioli E., 2009. Concentration polarization analysis in selI-supported Pd-based membranes.
    Sep. Pur. Tech.. In press. doi: 10.1016/j.seppur.2009.01.008.
    PC.2.15
    Dielectric exclusion in nanofiltration. A comparison of theoretical and experimental
    dependency of the interaction energy with concentration
    V. Silva
    1,2
    , J.A. Otero
    3
    , G. Lena
    3
    , P. Pradanos
    3
    , J. Villasante
    1,2
    , A. Martin, F. Martinez
    1,2
    , A. Hernandez
    1,2
    1
    Depto. de Termodinamica v Fisica Aplicada, Fac. de Ciencias, Universidad de Jalladolid, 47071 Jalladolid, Spain
    2
    Surface and Porous Materials (SMAP), UA-CSIC-UJA, R&D Building, Campus Miguel Delibes. 47071 Jalladolid. Spain.
    3
    Grupo de Ingenieria de Procesos de Filtracion con Membranas (IPFM), Depto.de Ingenieria Quimica v Quimica Inorganica.
    E.T.S. de Ingenieros Industriales v Telecomunicacion. Universidad de Cantabria, 39005 Santander, Spain
    vsilvatermo.uva.es
    Several mechanisms are involved in salt nanoIiltration. These mechanisms include diIIusive, convective, electrostatic and
    dielectic phenomena, whereas Ior the separation oI organic solvents only the two Iirst mechanism should be considered.
    Some models are oI the typical black box character usual in thermodynamics. Nevertheless we use those based on the Nernst-
    Planck extended equation that should lead to a better understanding oI the actual phenomena that are determining the
    transport. The last modiIication oI such these models, the so called SEDE model, has been used. The model gives the true
    retention versus volume Ilow in terms oI Iour parameters. One oI them, the active layer thickness divided by the porosity, can
    be eliminated Irom the calculation as Iar as it is correlated with the water permeability by the Hagen-Poiseuille equation
    where water viscosity has to be corrected Ior its substantial increase within small pores. This leaves: the pore radius, the pore
    charge density and the dielectric constant inside the pores,
    p
    , (iI the dielectric constant oI the membrane material is assumed
    to be known) as the only parameters to be Iitted.
    There are two contributions to the dielectric exclusion that are customarily taken into account. These include: (a) the Born
    contribution that takes into account the change in the solvation energy oI the ions when entering the pores and (b) the eIIect
    oI the image charges induced in the membrane material inside the pores including the eIIect oI the solvent and the rest oI the
    ions. Nevertheless, when these eIIects are taken into account many problems have been Iound.
    Here we determined the surIace charge density Irom measurements oI streaming potential on an ad hoc channel on the
    external surIace oI the membrane Ior diIIerent concentrations. This isotherm can be assumed to be valid also Ior the
    membrane surIaces inside the pores. II this is so done another oI the parameters is taken out oI the Iitting procedure; the pore
    charge density. This leaves the water dielectric constant as the only parameter to be Iitted once the pore size has been
    determined by AFM, retention oI uncharged solutes and the liquid-liquid displacement method. This is the case Ior the
    membrane we used; the AFC-40 membrane made by PCI. In order to avoid theoretical contamination we used the overall
    dielectric exclusion energy as the directly Iitted parameter and evaluated it Ior diIIerent concentrations.
    The dielectric exclusion energy W
    exp
    appears to increase with concentration, while the theoretical predictions Ior constant
    water dielectric constant decrease with concentration. For high enough concentrations both the experimental and theoretical
    W remain almost constant in such a way that the W
    exp
    crosses the iso-
    p
    curves corresponding to decreasing
    p
    values
    below the bulk water one. Nevertheless Ior low enough concentrations the iso-
    p
    curves crossed should correspond to values
    over that Ior the pure bulk water. This is, oI course, very diIIicult to accept, thus leading to conclude that the theoretical Irame
    to study dielectric exclusion should be revised Ior low concentrations and/or it should be accepted that the charge isotherm
    changes Ior these low concentrations inside the pores.
    -300-
    PC.2.16
    Contributions to the Electric Potential appearing when a Pressure Drop
    is applied trough a Nanofiltration Membrane
    J. Benavente
    1
    , V. Silva
    2,3
    , P. Pradanos
    2,3
    , L. Palacio
    2,3
    , A. Hernandez
    2,3
    , G. Jonsson
    3
    1
    Departamento de Fisica Aplicada I, Facultad de Ciencias. Universidad de Malaga, 29071 Malaga, Spain.
    2
    Departamento de Fisica Aplicada, Facultad de Ciencias. Universidad de Jalladolid, 29047 Jalladolid, Spain.
    3
    Surface and Porous Materials (SMAP), UA-CSIC-UJA, R&D Building, Campus Miguel Delibes. Jalladolid. Espaa
    4
    Chemical Engineering Department. Technical Universitv of Denmark. DK-2900 Lvngbv, Denmark.
    pradanostermo.uva.es
    Volume Ilow and observed salt rejection have been measured as a Iunction oI pressure Ior a commercial composite polyamide/
    polysulIone nanoIiltration membrane, NF45 by FilmTec. KCl solutions at Iive diIIerent concentrations (10-3 _ C(M) _
    2x10-2) were measured by using a tangential test-cell, with applied pressure ranging between 1 atm and 6 atm. These values
    were used to determine active layer porous size and surIace charge density by means oI the Donnan Steric Pore Model
    (DSPM) Ior charged membranes.
    On the other hand pressure-induced electric potential diIIerence across the membrane was also measured in the described
    operation conditions. This electric potential gives an alternative method to obtain the charge density on the pore-surIace oI
    nanoIiltration membranes by determining the zeta potential, which can be evaluated Irom the streaming potential.
    Nevertheless, it is clear that the measured electric potential contains the streaming potential but also some other contributions
    as the diIIusion potentials through the membrane and the concentration polarization layer and the Donnan potentials appearing
    in the Ieed and the permeate membrane-solution interIaces.
    All the contributions to the total electric potential drop across the membrane system can be modelled once the charge isotherm
    and the concentration proIile are determined by the retention model. Then the transport numbers in the bulk solution and
    across the membrane can be Iitted. The so obtained transport numbers Iairly agree with those indicated in the literature Ior the
    bulk solution and with those obtained Irom membrane potential (electric potential appearing when only a concentration
    gradient is applied through the membrane) measurements Ior the membrane.
    PC.2.17
    Mechanism of facilitated cadmium(II) transport through FSSLM with Cyanex 923
    A.A. Leopold
    1
    , N.S. Rathore
    3
    , A. Fortuny
    1
    , M.T. Coll
    1
    , A.M. Sastre
    2
    1
    Department of Chemical Engineering, Universitat Politecnica de Catalunva, EPSEJG, Av. Jictor Balaguer s/n, 08800
    Jilanova i la Geltru, Spain
    2
    Department of Chemical Engineering, Universitat Politecnica de Catalunva, ETSEIB, Av. Diagonal 647, 08028 Barcelona,
    Spain
    3
    Bhabha Atomic Research Centre, Tarapur, India
    agnieszka.leopoldupc.edu
    The Iacilitated transport oI cadmium(II) Irom neutral chloride medium through Ilat sheet supported liquid membrane
    incorporating the solvating extractant Cyanex 923 was studied. Modelling a metal transport through FSSLM is a combination
    -301-
    oI the knowledge oI the equilibrium, thus the stoichiometry and equilibrium description oI the extraction and reextraction
    reactions between the metal and the carrier at membrane interIaces, and the kinetic parameters, thus mass transIer coeIIicients.
    The second ones can be integrated in the overall mass transIer coeIIicient oI cadmium(II) transport and reIer to the three
    diIIusion resistances that take place in FSSLM system, namely: the cadmium diIIusion through the stagnant layer oI the Ieed
    solution (D
    I
    ), the cadmium-complex diIIusion through the membrane phase (D
    m
    ), and the cadmium diIIusion through the
    stagnant layer oI the stripping solution (D
    s
    ). The mechanism oI metal transport consists oI the diIIusion oI metal species Irom
    the bulk oI the Ieed phase to the aqueous boundary layer at the Ieed-membrane interIace, the interIacial solvation reaction
    between the metal species and the extractant at the Ieed-membrane interIace, diIIusion oI metal-carrier complexes Irom the
    Ieed-membrane interIace to the membrane-stripping interIace, decomplexation reaction oI carrier-metal complexes at the
    membrane-stripping interIace, and Iinally the diIIusion oI metal species Irom the membrane-stripping interIace to the bulk oI
    the stripping phase. The diIIusion processes can be described by Fick`s Iirst law, while the reactions at the interIaces oI the
    liquid membrane can be considered as governed by the equilibrium state. All other particular steps that can be involved in the
    metal transport model are supposed to be neglected. Many scientiIic works reporting transport rate modeling oI metal ions
    through FSSLM claims that the rate limiting step is diIIusion through the membrane. Accordingly, these technical reports
    present that at steady-state conditions the experimental values oI parameters such as metal permeation P and diIIusion
    coeIIicient D can be computed by the commonly used relation: Pt(-A/V)ln(|Mt/M0|). The present work validates that in the
    case oI cadmium(II) transport Irom neutral chloride medium with Cyanex 923 this equation is no applicable as Ior every set oI
    experiments done in FSSLM system under study this relation gives diIIerent values oI D, and then P. As a response to this, the
    metal transport model is derived considering the diIIusion resistances in the Ieed phase boundary layer and in the membrane,
    and also the instantaneous reactions oI metal species extraction and stripping on the interIaces oI the liquid membrane. By
    introducing the hypothetical constants oI the diIIusion coeIIicients in the aqueous boundary layer (D
    I
    ) and in the membrane
    (D
    m
    ), and also the thickness oI the Ieed phase stagnant layer (o
    I
    ), the proposed metal transport model gives uniIorm values oI D
    and P Ior every experiment carried out Ior the studied system. The permeability through the membrane is described well with
    this model and the accordance between the experimental points and the theoretical values justiIies the validity oI the Iound out
    variables.
    PC.2.18
    Transport properties of a cation-exchange membrane under natural convection in
    contact with ZnSO
    4
    solutions
    I. Herraiz-Cardona, E. Ortega, V. Perez-Herranz
    Dpto. Ingenieria Quimica v Nuclear, Universidad Politecnica de Jalencia, P.O.Box 22012 E-46071 Jalencia, Spain
    ishercardoctor.upv.es
    Nowadays, zinc sulphate baths are considered a good alternative to cyanide zinc plating baths due to its relatively low cost and
    eco-Iriendliness. Electrodialysis process is a promising technique Ior the treatment oI the rinse-water Irom zinc sulphate
    plating industries, replacing the traditional methods.
    In this work the inIluence oI ZnSO
    4
    bulk solution concentration on the Zn
    2
    transport properties through a IONICS 67-
    HMR-412 cation-exchange membrane under natural convection has been evaluated by means oI Chronopotentiometry. For this
    purpose, diIIerent ZnSO
    4
    solutions between 0.050 and 0.200 M has been tested.
    A potential model has been proposed to evaluate the eIIect oI
    zinc concentration on the zinc transport number through the
    membrane.
    The concentration inIluence on the DBL thickness Iollows the
    Levich equation, in which the kinematic viscosity was calculated
    as a Iunction oI zinc concentration |1, 2|.
    Taking into consideration the concentration inIluence on the
    transport number through the membrane and on the DBL
    thickness, the eIIect oI zinc concentration on the limiting current
    density was well modelled, as it is shown in Figure 1, with a
    relative error value lower than 3.1.
    |1| M. I. Alkatsev, I. Kh. Kabisov. Electric conductivity,
    viscosity, and density oI zinc electrolytes. Soviet Non-Ferrous
    Metals Research 1981; 9:30-34.
    |2| G. W. Barton, A. C. Scott. A Validated Mathematical-Model Ior A Zinc Electrowinning Cell Journal oI Applied
    Electrochemistry 1992; 22:104-115.
    -302-
    Figure 1. Limiting current density as a Iunction oI bulk
    ZnSO
    4
    concentration Ior the IONICS 67-HMR-412
    membrane
    PC.2.19
    Simulation of dynamic responses of semi-open Wicke-Kallenbach cell with composite
    membranes of the type silicalite-1-o-alumina
    V. Fila
    1
    , P. Hrabanek
    2
    , A. Zikanova
    2
    , M. Kocirik
    2
    , B. Bernauer
    1
    , I. Jirka
    2
    1
    Institute of Chemical Technologv Prague, Technicka 5, 16628 Prague 6 Defvice, C:ech Republic
    2
    J. Hevrovskv Institute of Phvsical Chemistrv of the ASCR, v.v.i., Dolefskova 2155/3, 18223 Prague 8, C:ech Republic
    milan.kocirikjh-inst.cas.cz
    The elaborated model oI the composite membrane involves mass transport in zeolitic phase described by Generalized Maxwell
    SteIan (GMS) approach. This transport is accompanied by a parallel transport in deIects oI zeolitic layer which is described by
    Dusty Gas Model (DGM) comprising diIIusion in transition region between Knudsen and bulk diIIusion superimposed on
    convective Ilow. DiIIerent level oI interactions between diIIusing molecules in deIects (macropores, mesopores) and in
    microporous phase is considered: (i) no interaction exists along the deIect pore between molecules in deIects and those in
    microporous phase and (ii) Iull interaction along deIect pore exists assuming the instantaneous adsorption equilibrium between
    the adsorbed molecules in microporous phase and those in deIect pores. Corrected MS diIIusion coeIIicients oI single
    component species are considered to be dependent on loading: (i) power law empirical Iormula Ior dependence oI MS
    diIIusion coeIIicients on loading is used and (ii) Reed-Ehrlich approach is applied |1|. Also mass transport resistance oI the
    support is considered and it is described by DGM. Modelling is exempliIied on dynamics oI a semi-open Wicke-Kallenbach
    (W-K) cell operated with a Ilat silicalite-1-u-Al
    2
    O
    3
    membrane using a CH
    4
    /N
    2
    mixture.
    The Iinancial support by the Grant Agency oI the ASCR via grants No. IAA400400625 and No. IAA400400909 and by the
    Czech Science Foundation via grant No. 203/07/1443 is grateIully acknowledged.
    |1| D.A. Reed, G. Ehrlich, SurIace-diIIusion, atomic jump rates and thermodynamics, SurI. Sci., 1981, 102, 588-609.
    PC.2.20
    Rigorous modeling of the solute transport in emulsion liquid membranes in hollow
    fiber contactors
    E. Bringas, M.F. San Roman, I. Ortiz
    Department of Chemical Engineering and Inorganic Chemistrv, Universitv of Cantabria, ETSIIvT, Avda. Los Castros s/n,
    39005, Santander, Spain.
    ortiziunican.es
    The application oI a new technology requires a reliable mathematical model and parameters that serve Ior design and
    optimization purposes allowing to accurate scale-up processes |1|. Progress in knowledge about membrane-based solvent
    extraction has led to the development oI attractive alternatives that maximise the separation rate oI the solute mass transport
    process. Emulsion Pertraction Technology (EPT) carried out in hollow Iiber contactors (HFC) is a good example oI intensiIied
    liquid membrane processes that achieves a maximum driving Iorce in the separation process aIter combination oI the
    advantages oI emulsion liquid membranes and non-dispersive solvent extraction |2|. In this conIiguration an emulsion phase
    comprising oI an extractant agent and a back-extraction agent, Ilows through the shell side oI one single HFC while the
    aqueous Ieed phase, which contains the target species that selectively reacts with the extractant, Ilows through the inner side oI
    the microporous Iibers oI the module |3|.
    Solute mass transport through reactive liquid membranes is basically described by the principles oI Iacilitated transport that
    combines reaction and diIIusion steps, and is considered to take place through several in-series steps: (i) solute diIIusion
    through the Ieed phase stagnant layer to the interIace with the membrane, (ii) interIacial reaction between the solute and the
    selective extractant to Iorm organic complex species, (iii) diIIusion through the liquid membrane, iv) diIIusion through the
    organic phase stagnant layer to the interIace with the droplets containing the back-extraction solution and, (v) chemical
    reaction between the organic complexes and the back-extraction agent |3|. However, the rigorous description oI a membrane
    contactor comprises not only the characterization oI mass transIer phenomena and interIacial chemical reactions, but also the
    mathematical modeling oI the Iluid Ilow on either side oI the membrane (tube and shell sides) by the development oI the
    appropriate conservation and continuity equations.
    -303-
    This work proposes the guidelines Ior the rigorous mathematical modeling oI membrane contactors as an essential tool Ior the
    optimal design oI EPT separation systems that requires the simultaneous integration oI the extraction and stripping rates.
    Finally, the methodology is illustrated by its application to a selected case study that deals with the removal and recovery oI
    zinc Irom eIIluents coming Irom diIIerent steps oI a hot-dip galvanizing process.
    Financial support Irom projects CTQ2008-00690/PPQ and CTQ2008-05545 (MCI, Spain) is grateIully acknowledged.
    |1| J. de Gyves, E. Rodriguez de San Miguel, Metal ion separations by supported liquid membranes, Ind. Eng. Chem. Res.,
    1999, 38, 2182-2202.
    |2| J.M. Wiencek, S. Hu, Emulsion liquid membrane extraction in a hollow-Iiber-contactor. Chem. Eng. Technol., 2000, 23,
    551-553.
    |3| J.A. Carrera, E. Bringas, M.F. San Roman, I. Ortiz, Selective membrane alternative to the recovery oI zinc Irom hot-dip
    galvanizing eIIluents, J. Memb. Sci., 2009, 326, 672-680.
    PC.2.21
    Nanofiltration of metal ions in concentrated phosphoric acid
    H. Diallo, B. ChauIer, M. Rabiller-Baudry
    Universite Rennes 1, UMR 6226 'Sciences Chimiques de Rennes` CNRS equipe Chimie et Ingenierie des Procedes, CS
    74205, case 1011, 35042 Rennes cedex
    bernard.chauIeruniv-rennes1.Ir
    Phosphoric acid is the second produced mineral acid in the world. Wet process is the most used for its less expansive cost.
    Unfortunately, the acid is obtained with contaminant traces which are a bottleneck for some uses. Metal ions such as, Al, Fe,
    Cr, V, Cu... are uptaken with more or less specific purification steps. Nanofiltration, NF, is a promising alternative way for
    selective separation based on charge difference. Retention of contaminants in raw phosphoric acid and model solutions were
    compared for evaluation of the efficiency of the membrane step and the relevant mode of separation.
    The first drawback of NF membrane was the stability in concentrated phosphoric acid. Although recommended in dilute acid,
    only, the following membranes MP34 (Koch, 300 g mol
    -1
    MWCO) and 2 PES-based membranes (Nadir, 300 and 1000 g mol
    -1
    MWCO, respectively) were used.
    Raw 5.5M phosphoric acid solution proceeded from wet process was used for NF runs. Retentions of metal ions with low cut-
    off 300 g mol
    -1
    membranes were significantly better than very poor performances of 1000 g mol
    -1
    membrane. Membrane
    permeation fluxes were too low for a competitive and sustainable step production. Combinations of both satisfactory retentions
    and fluxes were achieved with a 1000 g mol
    -1
    membrane through the use of additive in raw acid; the polymer additive targets
    were enhanced retentions without severe flux drop.
    For membranes oI low cut-oII and /or use oI polymer additive, retentions oI metals were in the valency order : Na Cu Fe,
    in close accordance with Donnan separation mode. However, Fe (III) retention was not so high as expected. Metal species are
    not well-known in phosphoric acid media.
    In-depth study with single Fe (III) and Cu (II) model solutions was perIormed by NF with additional titrations Ior a better
    understanding. From spectroscopic UV data, in dilute metal solutions it was shown that predominant specie was a divalent Fe
    H
    2
    PO
    4
    complex in 0.12 to 5.9 M media and a monovalent Fe HPO
    4
    between 0.001 M and below 0.120 M media.
    Due to model solution results, it has been checked that electrostatic interactions are involved in NF transIer in 5.9 M
    phosphoric acid but the selectivity is due to species which are likely one phosphato metal ion Ior the most simple case (ie Cu)
    and a mixture oI valences Ior some metal ions. In Iact, retention oI metal contaminants oI raw phosphoric acid does not
    involve hydrated ions. Fe
    3
    and Cu
    2
    are oversimpliIied species Ior NF selectivity prediction applied to wet process oI
    phosphoric acid.
    -304-
    PC.2.22
    Fouling mechanism study and flux decrease modeling in crude corn oil miscella in
    laboratory scale
    M. S. Araki, L. A. G. Gonalves, L. A. Viotto
    Facultv of Food Engineering State Universitv of Campinas -UNICAMP, Cidade Universitaria "Zeferino Ja:", s/n C.P. 6041,
    13083-970, Campinas, SP, Bra:il.
    viottoIea.unicamp.br
    Among various modeling studies, Wu et al. (1991) have used protein model solutions and Koltuniewicz (1992) and Field et al.
    (1995) oil emulsion in water in order to test and validate many diIIerent considerations taken into account to elucidate models
    that describe permeate Ilux decrease. In this work, these models will be applied to model permeate curves oI crude corn oil
    miscella degumming using ultraIiltration (UF). The chemical composition oI this crude corn oil miscella is very diIIerent Irom
    a model solution due to the diversity and quantity oI components present in human nutrition. Besides that while UF there are
    composition changes on retentate and components distribution in membranes interIace. ThereIore, this study Iocus on
    modeling Ilux decrease and Iouling mechanisms. Data used reIer to UF degumming oI crude corn oil miscella in laboratory
    scale with six polymeric membranes (PVDF 30 e 50 kDa, CME 0,025 e 0,05 m, PC 0,05 m e PES 10 kDa), under constant
    pressure at 50C. The best data adjustment was Iound with Field et al. (1995) model with R averaging 97,5. General
    equation is (dJ/dt)k
    J
    (JJ*)
    (2n)
    , where n depends on the Iouling mechanism and J* is Ilux on equilibrium state. The dominant
    mechanism Iound was the incomplete pore blockage (n1) to Iive oI the membranes and complete pore blockage (n2) to PC
    0,05 m membrane. Wu model presented 95,2 average adjustment while Koltuniewicz value was 93,8 , because it assumes
    only Iiltration cake mechanism.
    |1| Field, R, W., Wu, D., Howel, J. A., Gupta, B. B., Critical Ilux concept Ior microIiltration Iouling, Journal oI Membrane
    Science, 1995, 100, 250-272.
    |2| Koltuniewicz, A.B., Predicting permeate Ilux in ultraIiltration on the basis oI surIace renewal concept, Journal oI
    Membrane Science. 1992, 68, 107118.
    |3| Wu, D., Howell, J.A., Turner, N.M., A new method Ior modelling the time-dependence oI permeation Ilux in ultraIiltration,
    Food and Bioprotucts Processing. 1991, 69, 7782.
    PC.2.23
    A surface response approach to canola crude oil degumming by polymeric
    membrane ultrafiltration
    L. A. Campos, M. C. Chiu, L. A. Viotto, L. A. G. Gonalves
    Facultv of Food Engineering FEA, State Universitv of Campinas UNICAMP, P.O. Box 6121, CE 3083-862, Campinas,
    So Paulo, Bra:il
    viottoIea.unicamp.br
    Phospholipids are present in crude vegetable oils and must be removed other wise they compromise the quality oI Iinal product
    due their emulsiIying action |1|. The removal oI phospholipids by ultraIiltration have been studied in order to replace the
    conventional degumming with the advantage oI reduce reIining lost, minimize costs and preserve compounds oI interest |2|.
    One important parameter on this study that justiIy the industrial application oI this technique is permeate Ilux (J). On this work
    it was done an orthogonal experimental design with two independent variables, velocity and pressure, perIorming 12
    experiments at pilot unit in order to degumming miscella 30 (m/m) oI oil, 40C, using PVDF 30 kDa membrane. It was
    observed the eIIect oI each variable on Ilux and it was Iound Ior the prediction model value oI R
    2
    as 0,96. On the limits oI
    studied conditions, (Figure 1) was Iound that pressure has great inIluence on Flux and observed results above Ilux J 162 L
    m
    -2
    h
    -1
    a very attractive value Ior industrial applications.
    -305-

    Figure (1) Flux (J) Contour plots as Iunction Figure (2) Response SurIace Ior Flux as
    oI v (m/s) and P (bar) Iunction oI v (m/s) and P (bar)
    |1| I.C. Kim, et AL; Phospholipids separation (degumming) Irom crude vegetable oil by polyimide ultraIiltration membrane.
    Journal oI membrane science, v. 205, p. 13-123, 2002
    |2| M. Cheryan; Membrane technology in the vegetable oil industry. Membrane Technology, February, p.5 7, 2005
    |3| T. N. Indira, et al; Water degumming oI rice bran oil a response surIace approach, journal oI Iood engineering, v. 43, p. 83-
    90, 2000.
    PC.2.24
    Diagnostics and eective stabilization of currents in a fuel cell stack
    H. LustIeld
    1
    , J. HirschIeld
    1
    , M. Reiel
    2
    , B. SteIIen
    3
    1
    Forschungs:entrum Juelich, IFF-1, 52425 Juelich, Germanv
    2
    Fachhochschule Aachen, Abteilung Juelich, 52428 Juelich, Germanv
    3
    Forschungs:entrum Juelich, JSC, 52425 Juelich, Germanv
    h.lustIeldIz-juelich.de
    We suggest a novel scheme Ior detecting and stabilizing inhomogeneous internal currents in a Iuel cell stack. In this paper the
    scheme is investigated Ior the case that the fow feld plates in use consist oI graphite. Then plates oI high conductivity, e.g.
    aluminum between the fow feld plates together with small slits in these plates have the eects|1,2,3|:
    a) Whenever a local inhomogeneity oI the electric current occurs at a particular cell in the stack this will induce a surIace
    current close to that cell perpendicular to the averaged current. This current can be detected.
    b) The high conductivity oI the small plates completely prevents the inhomogeneities Irom spreading to neighboring cells.
    c) Even at the particular cell the inhomogeneity is distributed equally over the MEA oI that cell as Iar as possible. Thus this
    scheme leads to much better diagnostic possibilities and at the same time reduces electric instabilities. Slightly modifed it can
    even prevent the breakdown oI the Iuel cell stack in many cases.
    |1| H. LustIeld, M. Reiel, B. SteIIen: Patent application DE: 102007061642.4-35 (2007)
    |2| J. HirschIeld, H. LustIeld, M. Reiel and B. SteIIen, paper submitted to J. Fuel Cell Sci. Technol.
    |3| J. HirschIeld: Tomographic problems in the diagnostics oI Iuel cell stacks, diploma thesis (University oI Duisburg-Essen,
    Germany, 2008)
    -306-
    PC.2.25
    Evaluation of the diffusion layer thickness by impedance and laser interferometry
    methods
    A. Kozmay
    1
    , V. Nikonenko
    1
    , N. Pismenskaya
    1
    , Ph. Sistat
    2
    , V. Vasileva
    3
    , V. Shaposhnik
    3
    1
    Membrane Institute, Kuban State Universitv, 149 Stavropolskava St., 350040 Krasnodar, Russia
    2
    Institut Europeen des Membranes, Universite de Montpellier 2, ENSCM, CNRS, CC047, Place Eugene Bataillon, 34095
    Montpellier Cedex 5, France
    3
    Jorone:h State Universitv, 1 Universitetskava St., 394006, Jorone:h, Russia
    VNikonenkomail.ru
    The evaluation oI diIIusion layer thickness at ion exchange membrane/solution interIace as a Iunction oI current density is
    carried out by using:
    - a one-dimensional mathematical model oI impedance |1|;
    - convection-diIIusion model |2|;
    - the method oI laser interIerometry |3|.
    Figure 1 shows that the dependencies obtained by those
    three methods are similar, i.e. at current densities, i, lower than the
    limiting current density, i
    lim
    ; the total thickness oI diIIusion layer
    (
    tot
    ) increases, while the thickness oI the Nernst diIIusion layer (
    N
    )
    is increasing only slightly. However at overlimiting current densities,

    N
    decreases, as shown by the impedance and the laser
    interIerometry.
    N
    is determined by the point oI tangents intersection
    to the concentration proIile;
    tot
    is deIined as the layer where 99 oI
    the concentration variation occurs.
    The increase in
    tot
    is explained by the Iact that the expansion oI
    concentration changes near the membrane is caused by the current,
    hence this expansion increases with the current.
    N
    increases with
    increasing current at ii
    lim
    , Iollowing i
    tot
    . At i~i
    lim
    ,
    N
    decreases due to
    electroconvection, while
    tot
    continue to increase as the
    electroconvective microvortices enlarge the region where
    concentration changes occur. The third value,
    impedance
    , is close to
    N
    ,
    however, there is a tendency in its growth, similar to that oI
    tot
    .
    The study is supported by Russian Foundation oI Basic Research
    (RFBR) 07-08-00533-a and 08-08-01047a grants.
    |1| Ph. Sistat, A. Kozmai, N. Pismenskaya, Ch. Larchet, G.
    Pourcelly, V. Nikonenko, Low-Irequency impedance oI an ion-
    exchange membrane system, Electrochim. Acta, 2008, 53, 6380
    |2| N.P. Gnusin, V.I. Zabolotskii, V.V. Nikonenko, M.Kh. Urtenov,
    Sov. Electrochem., 1986, 22, 273
    |3| V.I. Vasil`eva, V.A. Shaposhnik, O.V. Grigorchuk, Y.P.
    Petrunya, The membrane-solution interIace current regimes oI
    electrodialysis by means oI laser interIerometry, Desalination, 2006,
    192, 408
    -307-
    Figure 1: the Nernst and total thickness oI the
    depleted DBL near an ion-exchange membrane vs.
    the current density applied.
    a) an anion-exchange AMX membrane in a cell
    with a CMX cation exchange membrane, and the
    Iollowing characteristics: the inlet concentration
    C
    0
    0.02M NaCl, average solution velocity
    V0.126 cm/s, the intermembrane spacing h 0.15
    cm, and the distance Irom the entrance y 1.1 cm;
    b) a MK-40 membrane in a cell with a MA-40
    membrane: C
    0
    0.01M NaCl , V0.126 cm/s
    spacing h 0.15 cm , y 1.1 cm.
    PC.2.26
    Predictive modeling of ionic permselectivity of porous media
    L. Seda, J. Kosek
    Institute of Chemical Technologv, Department of Chemical Engineering, Technicka 5, 166 28 Prague 6, C:ech Republic
    Juraj.Kosekvscht.cz
    Porous media with Iixed surIace charge are involved in many practical applications which utilize externally applied electric
    Iield or where the induced electric Iield is important, e.g., capillary electrochromatography, electrodialysis, nanoIiltration and
    other membrane separation processes. We have developed the soItware which allows to predict the transport and separation
    properties oI porous medium (e.g., perIusion Ilow and ionic permselectivity) in dependence on: (i) the spatially 3D porous
    micro-structure, (ii) type and distribution oI the Iixed charge, and (iii) type and concentration oI the electrolyte |1|.
    SoItware capabilities are illustrated on case studies oI systems where the Debye length is either comparable or negligible with
    respect to the characteristic pore size. The concept oI the reconstructed porous medium has been employed to represent the
    morphology |2|. The concentration proIiles oI ionic species in the spatially 2D porous domains and the electric current
    distribution in the spatially 3D domains packed with porous particles are presented. The eIIects oI the Iixed charge
    immobilized on the surIace, the concentration oI electrolyte and the structure oI porous media on the ionic permselectivity are
    evaluated.
    Figure 1. Ionic permselectivity: concentration oI co-ions c

    in
    granular medium with Iixed charge 0.001 C/m
    2
    , bulk
    concentration is c
    bulk
    0.07 mol/m
    3
    .
    Figure 2. Ionic selectivity (J

    /J

    ) Ior various types oI porous


    medium and bulk electrolyte concentration.
    |1| L. Seda, J. Kosek, Predictive modeling oI ionic permselectivity oI porous media, Computers and Chemical Engineering,
    2008, 32, 125-134.
    |2| J. Kosek, F. Stepanek, M. Marek: Modeling oI Transport and TransIormation Processes in Porous and Multiphase Bodies,
    in Advances in Chemical Engineering, 2005, Vol. 30, 137-203.
    |3| M. Paces, J. Kosek, M. Marek, U. Tallarek, A. Seidel-Morgenstern, Mathematical modeling oI adsorption and transport
    processes in capillary electrochromatography: Open-tubular geometry, Electrophoresis 2003, 24, 380-389.
    PC.2.27
    Modeling the performance of enzyme immobilized membranes
    Y. Yurekli
    1
    , S. Guedidi
    3,4
    , S. Alsoy Altinkaya
    1
    , A. Yemenicioglu
    2
    , C. Innocent
    3
    , A. Deratani
    3
    , S. Roudesli
    4


    1
    I:mir Institute of Technologv, Department of Chemical Engineering, Gulbahce Kovu, 35430, Urla I:mir, Turkev.
    2
    I:mir Institute of Technologv, Department of Food Engineering, Gulbahce Kovu, 35430, Urla I:mir, Turkev.
    3
    Institut Europeen des Membranes, Place Eugene Bataillon, CC 047, 34095 Montpellier, Cedex 5, France.
    4
    Laboratoire des Polvmeres-Biopolvmeres Materiaux Organiques, Faculte des Sciences de Monastir/ Avenue de
    lEnvironnement 5019, Monastir. Tunisie.
    sacidealsoyiyte.edu.tr
    Enzyme immobilized membrane acts as a separation and catalytic unit and can be used in production, processing and
    treatment operations. Selective mass transport with a biological reaction Iollowed by the selective removal oI products Irom
    -308-

    the reaction site can eliminate product inhibition eIIects on the catalytic activity oI the enzyme, thus, can increase the
    conversion oI the reactions. Enzyme can be entrapped within the pores oI the membrane or can be bound on the surIace oI the
    membrane. The conversion oI the substrate depends not only on the enzyme kinetics but also mass transport conditions.
    Various parameters such as the type and structural properties oI the membrane and operating conditions inIluence the activity
    decay proIile and the rate oI mass transport. To achieve desirable productions or removals with the enzyme immobilized
    membranes, modeling the operation within a selected geometry could provide useIul guidelines Ior optimizing operating
    conditions or Ior designing the membrane structures.
    In the present study, the behavior oI a dead-end stirred cell Iiltration system has been modeled. The model assumes that
    enzyme is immobilized on both surIaces oI the membrane and Iorms a porous gel layer. The model takes into account mass
    transIer resistances on the retentate and permeate sides and one dimensional mass transIer through the membrane and porous
    enzyme layers. In addition, the deactivation oI enzyme during the process has been considered. The model equations have been
    solved numerically using Iinite diIIerence method and the contribution oI most signiIicant transport mechanisms has been
    determined. The theoretical predictions have been compared with the experimental data collected Ior the decomposition oI
    urea by urease enzyme immobilized on commercial poly-(acrylonitrile-co-sodium methallyl sulIonate) copolymers (AN69)
    ultraIiltration membrane. The mathematical model is general in nature and can be used to describe the perIormance oI
    diIIerent enzyme immobilized membrane by knowing the rate expression, structural parameters oI the membrane and the
    transport parameters oI the substrate.
    Acknowlegment The authors would like to thank The ScientiIic and Technical Research Council oI Turkey and The Ministry
    oI Foreign AIIairs oI the Republic oI France Ior partial Iunding (IFC) and the Gambro-Hospal, Lyon, France Ior kindly
    providing the membranes.
    PD.1.1
    Fabricating super-hydrophobe membrane via geometrical and chemical modification
    S.S. Madaeni, N. Ghaemi
    Chemical Engineering Department, Ra:i Universitv, Kermanshah, Iran
    smadaeniyahoo.com
    Both the chemical and structural properties oI a surIace determine the contact angle. For the Iormation oI super-hydrophobic
    surIaces, modiIication oI surIace chemistry must be always combined with surIace roughness enhancement. In this study a
    simple and cost eIIective technique was employed to transIorm a hydrophile membrane into a super-hydrophobe. In order to
    geometrically modiIy the membrane surIace, the required needle-like rugosities were created by boiling the membrane in
    water. The chemical modiIication oI the roughened surIace was carried out by the chemical adsorption oI stearic acid
    monolayer on the polymer oI the membrane surIace. Finally, by controlling the surIace roughness and duration oI reaction
    time, a super-hydrophobe membrane with the contact angle oI 120

    was prepared.
    PD.1.2
    A new adsorption based model for bulk porosity tracing during membrane filtration
    E. Salehi, S.S. Madaeni
    Chemical Engineering Department, Ra:i Universitv, Kermanshah, Iran
    smadaeniyahoo.com
    A novel simple model is presented Ior prediction oI the bulk porosity decline during Iiltration oI a salty solution through PVD
    nanoIiltration membrane. This model was developed on the basis oI the adsorption oI the cations available in the Ieed onto the
    membrane. Three adsorption isotherms were tested and Iitted to the equilibrium adsorption data. The Freundlich was the
    isotherm oI choice. The porosity model contains two adjustable parameters which can be determined theoretically and
    experimentally. Adsorption isotherms were combined Ior determination oI the Iirst parameter and a new method called 'Ilux
    test was developed Ior determination oI the second parameter. A good agreement was Iound between experimental and model
    predicted porosities. The model`s estimation capability is reduced at higher pressures due to the existence oI unIavorable
    equilibrium adsorption condition and deviation oI the isotherm`s parameters Irom equilibrium.
    -309-
    PD.1.3
    Performance evaluation of nanofiltration membranes for diafiltration of dye/salt
    mixtures: experimental observations and model verification
    P. Mikulasek, J. Cuhorka
    Institute of Environmental and Chemical Engineering, Facultv of Chemical Technologv, Universitv of Pardubice, Studentska
    573, 532 10 Pardubice 2, C:ech Republic
    petr.mikulasekupce.cz
    NanoIiltration (NF) is becoming widely accepted in the dyestuIIs industry, in particular Ior reactive, acid and direct dyes, as a
    way oI producing high quality products, maximizing yields and capacity, and saving materials. NanoIiltration is used Ior both
    desalting and concentration and is currently one oI the biggest applications Ior NF |1|. In the manuIacture oI liquid dyes,
    almost complete desalting, which helps to improve the stability oI the product, enhances the solubility oI the dye. DiaIiltration
    is used to allow a high level oI desalting to be achieved. However, the success oI the application oI NF Ior the desalting is
    related, among other Iactors, with magnitude oI the permeate Iluxes decline |2,3|. Here we show that the dye and salt
    concentration, the salt rejection and pressure applied are responsible Ior the decrease oI Ilux values as well as Ior desalting
    purposes. We Iound in the process oI desalination oI aqueous dye-salt solutions by polymeric NF membranes (Esna 1, Desal
    5DK, NF 70, NF 90, NF 270 and TR 60) that cake layer Iormation oI dye molecules on membrane surIace, especially at low
    salt concentrations, was the principal cause oI Ilux decline. Furthermore, we Iound that Irom the solution-diIIusion model, the
    intrinsic rejection coeIIicient can be predicted as Iunction oI Ieed dye concentration.
    Our results demonstrate (Figure 1) how the mathematical modelling oI NF and description oI discontinuous diaIiltration by
    periodically adding solvent at constant pressure
    diIIerence can be important Ior prediction oI the
    diaIiltration process in the manuIacture oI liquid dyes.
    We anticipate our results to be a starting point Ior more
    precise models oI desalination process.
    This work was Iinancially supported by the Ministry oI
    Education, Youth and Sports oI the Czech Republic,
    Project MSM0021627502.
    |1| C. Crossley, Filtration&Separation, 2002, 39(5),
    36-38
    |2| I. Koyncu, D. Topacik, M.R. Wiesner, Water
    Research, 2004, 38, 432-440
    |3| I. Petrinic, I., N.P.R. Andersen, S. Sostar-Turk,
    A.M. Marechal, Dyes and Pigments, 2007, 74, 512-518
    PD.1.4
    Reverse osmosis for the ultrapurification of aqueous hydrogen peroxide to electronic
    grade
    R. Abejon, A. Garea, A. Irabien
    Departamento de Ingenieria Quimica v Quimica Inorganica, Universidad de Cantabria, Avenida Los Castros s/n, 39005
    Santander, Espaa.
    abejonrunican.es
    Hydrogen peroxide has a variety oI uses: as a bleaching agent Ior Iibre, cellulose and paper, as a deodorant in waste treatment,
    as an antiseptic and disinIectant Ior medical or packaging purposes, and as a key chemical in the manuIacturing process oI
    semiconductors. This latter industry requires the highest level oI purity Ior hydrogen peroxide, because its use Ior cleaning
    waIer surIaces oI Ioreign contaminants or removing photoresists implies direct contact between silicon and chemical.
    Typically, the sub-ppb range Ior metals is needed, as indicated by widely accepted standards Ior electronic grade hydrogen
    peroxide such as SEMI C30-1101.
    -310-
    Figure 1: Comparison of experimental and model diafiltration data
    (membrane Desal 5 DK)
    The ultrapuriIication technologies Ior hydrogen peroxide lead to the integration oI membrane separation and/or resin
    adsorption processes Ior puriIying industrial grade hydrogen peroxide; being reported in the literature, in terms oI patents, the
    application oI reverse osmosis |1|, ultraIiltration |2| and ion exchange |3| techniques. Previous studies oI the research group
    report the use oI ion exchange |4| and reverse osmosis |5| Ior the ultrapuriIication oI another electronic chemical: aqueous
    hydroIluoric acid.
    This work is Iocused to study reverse osmosis in order to achieve electronic grade hydrogen peroxide, speciIically SEMI
    Grade 3 (metals impurities limited to 1 ppb), and to advance the process Iundamentals, taking into account that there is a lack
    oI previously published papers concerning this topic. A Ilat-sheet membrane unit Ior reverse osmosis at laboratory scale
    (SEPA CF II, GE Osmonics) is employed Ior a viability study oI diIIerent commercial membranes which are preselected
    according to their properties and patents reIerenced: CE and AD (Osmonics), BE and CRM (Woongjin Chemical), SW30HR
    (Filmtec) and UTC 80 B (Toray). The hydrogen peroxide Ilux and ionic metal impurities rejections are evaluated, paying
    attention to the assessment oI the permeation parameters oI the membranes according to diIIerent models.
    The Spanish Ministry oI Science and Technology is acknowledged Ior the Iinancial support to this research (Project
    CTM2006-00317).
    |1| U.P. Bianchi, U. Leone, M. Lucci, Process Ior the industrial production oI high purity hydrogen peroxide, US Patent n
    6333018 B2, 2001.
    |2| J.M. Dhalluin, J.J. Wawrzyniak, H. Ledon, Process Ior the puriIication oI hydrogen peroxide, US Patent 6113798 A, 2000.
    |3| F. Tanaka, S. Sugawara, T. Adachi, K. Mine, Process Ior producing a puriIied aqueous hydrogen peroxide solution, US
    Patent 6896867, 2005.
    |4| I. Fernandez-Olmo, J.L. Fernandez, A. Irabien, PuriIication oI dilute hydroIluoric acid by commercial ion exchange resins,
    Sep. & PuriI. Tech., 2007, 56(1), 118-125.
    |5| A. Garea, P. Portilla, A. Irabien, Membrane processes in the puriIication oI electronic grade chemicals, 6
    th
    European
    Congress oI Chemical Engineering (Copenhagen, Denmark), 2007.
    PD.1.5
    Influence of porous stainless steel supports on pervaporation performance of
    tubular silicalite membranes for concentrating bio-ethanol
    H. Negishi, H. Habe, T. Ikegami, K. Sakaki
    Bio-Chemical Group, Research Institute for Innovation in Sustainable Chemistrv, National Institute of Advanced Industrial
    Science and Technologv (AIST) / 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
    h-negishiaist.go.jp
    Recently, inorganic membranes have attracted great attention as new Iields which require thermal resistance, chemical stability
    and mechanical strength |1|. Silicalite as one oI zeolite is expected as an ethanol-selective membrane because it is more
    hydrophobic than any other zeolite. We reported the preparation oI silicalite membranes on the porous support stainless steel
    tube Ior concentrating bioethanol by hydrothermal synthesis with electrophoretic deposition (EPD) as a seeding technique |2|.
    In this study, we investigated the inIluence oI morphology oI the surIace oI the porous stainless steel support on membrane
    separation perIormance. In the EPD process, silicalite crystal seeds were dispersed and charged in a solvent and migrated to an
    electrode substrate with a DC voltage. The crystal seeds could be seeded on the porous stainless steel tubular support by using
    EPD, and the amount oI seeding could be controlled with applied voltage and time. AIter seeding, the crystal seeds were
    grown by hydrothermal synthesis in the solvent which consisted oI SiO
    2
    , tetra-n-propylammonium bromide, NaOH and H
    2
    O at
    170 C Ior 72 hours and tubular silicalite membrane was obtained. When the pore ratio on the surIace oI the substrate was
    20.6 , the membrane showed the separation Iactor oI 63 with a total Ilux oI 1.18 kg/m
    2
    h at 60 C. On the other hand, when
    the pore ratio on the surIace oI the substrate was 26.0 , the membrane showed the separation Iactor oI 71 with a total Ilux oI
    1.98 kg/m
    2
    h at 60 C. As a result, it was Iound that the substrate which has higher pore ration on its surIace attains higher
    membrane perIormance.
    New Energy and Industrial Technology Development Organization (NEDO) oI Japan are acknowledged Ior granting the
    works.
    |1| T. Sano, S. Ejiri, K. Yamada, Y. Kawakami, H. Yanagishita, Separation oI acetic acid-water mixtures by pervaporation
    through silicalite membrane, J. Membrane. Sci., 123, (1997), 225-233
    |2| H. Negishi, M. Okamoto, T. Imura, D. Kitamoto, T. Ikegami, Y. Idemoto, N. Koura, T. Sano and H. Yanagishita,
    Preparation oI Tubular Silicalite Membrane by Hydrothermal Synthesis with Electrophoretic Deposition as a Seeding
    Technique, J. Am. Ceram. Soc., 89 (2006), 124-130
    -311-
    PD.1.6
    New high performance membranes for forward osmosis processes
    C. Hnel, C. Chaumette, G. Bisle, E. Walitza, T. Schiestel
    Fraunhofer Institute for Interfacial Engineering and Biotechnologv, Nobelstr. 12, 70569, Stuttgart, Germanv
    Thomas.Schiesteligb.IraunhoIer.de
    Background:
    Forward osmosis applications use the concentration diIIerence oI dissolved solutes as a driving Iorce. ThereIore a system oI
    two water compartments, one with a high and one with a low concentration, is separated by a semi-permeable membrane.
    Water transIers Irom the low concentration side to the high concentration side while dissolved solutes are blocked. Polluted
    water can be cleaned when it is transIerred Irom the pollution side to a compartment oI higher osmotic pressure (e.g. with a
    high sugar concentration) while slush, pathogenic germ or urea could not pass the membrane. By this process drinking water
    can be produced in exceptional situations in aerospace or extreme outdoor activities.
    Results:
    In our lab high perIorming Iorward osmosis membranes with open support and a very thin selective layer have been developed.
    Pore Iorming agents called templates are used to create an asymmetric membrane structure. The membrane can be produced
    either in one step by phase inversion or in two steps (phase inversion with subsequent coating), which oIIers a high degree oI
    Ireedom Ior the control oI membrane properties. Water Iluxes and salt retention are measured in a pressure cell (10 to 50 bars)
    and a Iorward osmosis setup (0 to 25 bars). The structure is checked via SEM. In osmosis our membranes show water Iluxes oI
    about 3.5 g/(s m) and high salt retention. VeriIied simulation data shows potential to improve the membrane perIormance with
    thinner substructures.

    Figure 1. SEM Example of sponge structure Figure 2. SEM Example of template made pores
    PD.1.7
    The optimization factors for preparation of heterogeneous reverse osmosis
    membranes
    T. Selimi, S. Gashi, N. Daci, F. Podvorica, B.S. Thai, A. Dylhasi
    Department of Chemistrv, Facultv of Natural Sciences, Universitv of Prishtina, Rr. Nna Tere:e nr. 5, 10 000 Prishtin,
    Republic of Kosova
    salihtgyahoo.com
    The aim oI this work is to study the optimization Iactors Ior preparation oI cellulose acetate-coal heterogeneous reverse
    osmosis.
    This approach is the extension oI an earlier investigation oI ours on the cellulose acetate coal, acetone, magnesium perchlorate
    water casting solution system, with particular reIerence to the eIIect oI changes in casting solution composition and solvent
    evaporation rate during Iilm Iormation and shrinkage temperature proIile.
    In this study two types oI membranes have been studied. The Iirst type oI membranes batches 316-K were made Irom a blend
    oI cellulose acetate and powdered Kosova`s basin coal with the same casing solvent solution. The proportions oI the blend by
    weight is as Iollows (10:15),(10:17.5), and (10:20) oI cellulose acetate coal were tested.
    The second type oI membranes batches 317-K were made in the same ratios and casting solutions, temperature and gelation
    medium with modiIied coal with aryldiazonium salts in acetonitril, HCl and H
    3
    PO
    2
    mediums. The results oI modiIication time
    oI coal in Iirst two mediums oI resulting membranes are already published.
    4
    -312-
    The membranes oI best perIormances oI both types were tested at the evaporation period oI time 0,30, 60 and 90s.
    The membrane perIormance data were obtained Irom/Ior conditions oI Ieed concentration 6.86x10
    -3
    moldm
    -3,
    with the Ieed
    Ilow rate oI 450 cm
    3
    /min, corresponding to a mass transIer coeIIicient k oI 45x10
    -4
    cm /s applied on the high pressure side oI
    the membrane at 17x10
    5
    Pa.
    From the results oI membrane perIormance described above, the Iollowing conclusions were drawn:
    a) The best product rate was achieved with casting solution composition cellulose acetate coal with weight (10:15) and
    (10:17.5).
    b) At the same solute separation, the membranes made with modiIied coal showed a better perIormance than those made
    with unmodiIied coal.
    c) In regard to membrane productivity it was proven that the membrane obtained with evaporation time oI 60s, showed
    best perIormance out oI all types oI tested membranes.
    |1| S. Gashi, N. Daci, T. Selimi, S. Berisha, Envir. Protect. Eng. 26(4), (2000)29-37
    |2| J. Pinson and F. Podvorica, Chem.Soc.Rev., 34 (5)(2005) 429-439,
    |3| B.Kunst,S.Sourirajan,J.Appl.Polym.Sci,14,(1970)1983-1996
    |4| S. Gashi,at al ; Desalination, Accepted 25 December 2007,(2009)1-8
    PD.1.8
    Dehydration of ethanol with PVP composite membranes
    P. Rlling, C. Staudt
    Department of Organic and Macromolecular Chemistrv, Universitv of Dsseldorf, Universittsstrasse 1, 40225 Dsseldorf,
    Germanv
    patrick.roellinguni-duesseldorI.de
    The demand oI ethanol as Iuel has increased signiIicantly over the recent years throughout the world |1|. Accompanied by the
    soaring ethanol market a lot oI scientists are working on the improvement oI bioethanol production concepts. Enhancing the
    energy eIIiciency oI current and Iuture bioethanol plants is subject oI research in many working groups. For instance energy
    savings can be realized by integrating membrane devices into the production circuit |2|. Our group is engaged in the
    dewatering oI ethanol by means oI vapour permeation and pervaporation. We are Iocused on the development oI novel
    hydrophilic composite membranes.
    In this regard diIIerent PVP composite membranes will be Iabricated and investigated by
    microscopic, spectroscopic and thermodynamic methods. In addition the separation
    characteristics will be described and compared with commercial membranes, e.g.
    established PVA membranes. Recently produced high-molecular PVP composite
    membranes showed good chemical stability and high Iluxes .
    |1| F.O. Licht, World Ethanol 2008: Ethanol in 2008/09 - Light at the end oI the tunnel?
    |2| F. Lipnizki, Membrane process opportunities and challenges in the bioethanol industry,
    Aachener Membran Kolloquium, 2008
    PD.1.9
    Separation of whey fractions from Serpa cheese whey using a combination of
    ultrafiltration and nanofiltration, from
    A. Macedo
    1
    , E. Duarte
    2
    , M. Pinho
    3
    1
    Instituto Politecnico de Befa Escola Superior Agraria, Rua Pedro Soares, Apartado 6158, 7801-908 Befa, Portugal
    2
    Instituto Superior de Agronomia, Tapada da Afuda, 1349-017 Lisboa, Portugal
    3
    Instituto Superior Tecnico, Av. Rovisco Pais, 1, 1049-001 Lisboa, Portugal
    ateresamacedogmail.com
    Whey is a liquid by-product that results Irom cheese making process. In a dry basis, it contains 70-80 oI lactose, 9 oI
    proteins, 8-20 oI minerals and also other minor components, such as some hydrolysed peptides oI k-casein, lipids and
    -313-
    Figure 1: PVA composite
    membrane
    bacteria (DauIin et al., 1998). The most usual process Ior separation oI this protein Iraction is ultraIiltration (UF). The whey
    ultraIiltration permeate contains, together with lactose and salts, a nitrogenous Iraction mainly composed oI peptides, Iree
    amino acids, creatine, nucleotides, urea, etc. (Moatsou et al., 2003). The recover oI this permeate is also indispensable because
    lactose, present in large amounts, contribute Ior its high COD. Besides, nowadays there is a growing interest in whey peptides
    because they have been reported to possess biological activity, being suitable Ior use in baby Iood due to their lack oI
    allergenicity (Butylina et al., 2006). In this work, to evaluate ovine whey, resulting Irom Serpa cheese making, we have
    perIormed the separation oI the Iollowing whey Iractions: a protein Iraction by ultraIiltration, using a membrane with a cut-oII
    oI 10 kDa; a nitrogenous Iraction, that contains whey peptides, whose molar masses are in the range 1-2 kg/mol, by
    ultraIiltration oI the whey permeate and using membranes with a suitable cut-oII (1 kDa) and, at last, a nanoIiltration oI the
    resulting permeate to recover lactose together with salts. AIter Iirst UF, apparent rejections were estimated. Whey proteins
    were completely rejected in the Iirst ultraIiltration and, as expected, lactose, salts (mainly monovalent salts) and a nitrogenous
    Iraction get through membrane pores, towards to permeate. In the second UF, apparent rejections oI total nitrogen, lactose and
    salts were estimated. Nitrogenous Iraction was totally recovered, being permeate mainly composed oI lactose and salts.
    NanoIiltration membranes have rejected all the lactose and mostly bivalents salts. The combination oI these operations (UF oI
    10 kDa, Iollowed by UF oI 1 kDa and nanoIiltration) allowed the total separation oI three Iractions: protein Iraction,
    nitrogenous Iraction and lactose. These Iractions are being studied in more detail.
    DauIin G., Rene F., Aimar P. (1998). Les separations par membrane dans les procedes de lindustrie alimentaire, Collection
    Sciences et Techniques Agroalimentaires, Paris.
    Butylina S., Luque S., Nystrm M.(2006). Fractionation oI whey-derived peptides using a combination oI ultraIiltration and
    nanoIiltration, J. oI Membrane Sci. (280) 418.
    Moatsou G., Hatzinaki A., Kandarakis I., AniIantakis E. (2003). Nitrogenous Iractions during the manuIacture oI whey protein
    concentrates Irom Feta cheese whey, Food Chemistry, (81) 209.
    PD.1.10
    Why do we need experiments to choose the right membrane?
    R. I. Ortiz-Basurto
    1,4
    , G. Pourcelly
    1
    , T. Doco
    2
    , P. Williams
    2
    , M. Dornier
    3
    , M.-P. Belleville
    1

    1
    Institut Europeen des Membranes (IEM). ENSCM, UM2, CNRS - Universite de Montpellier II, CC 047, Place Eugene
    Bataillon - 34095 Montpellier, France.
    2
    UMR 1083 Sciences pour lnologie INRA, SupAgro, UM1, 2 place Jiala F-34060 Cedex Montpellier, France
    3
    UMR 95 Qualisud, CIRAD, Montpellier SupAgro, 73 rue Jean-Franois Breton, TA B-95/16, 34398 Montpellier Cedex 5,
    France
    4
    Universidad Tecnologica de Tecamachalco, Av. Universidad Tecnologica No.1, Tecamachalco Puebla, Mexico
    marie-pierre.bellevilleiemm.univ-montp2.Ir
    UltraIiltration (UF) is a relatively inexpensive, versatile, expedient, simple, nondestructive, and reagent-Iree technique Ior
    Iractionating biological solutions in order to puriIy and concentrate high added value compounds. However its practical use
    appears to be somewhere limited. To account Ior this Iact, it is oIten reIerred to various problems oI membrane Iouling,
    investment costs..But the Iirst problem encountered is the choice oI the right membrane!
    In order to prepare diIIerent Iractions oI Iructo oligosaccharides (FOS) Irom Agave tequilana juice, 9 diIIerent membranes
    with molecular weigh cut oII (MWCO) between 5 and 10 kDa were selected and tested in dead-end Iiltration cell. The results
    were then expressed in terms oI Ilux and retention rates.
    First it is important to note that membranes prepared Irom the same polymer (polyethersulIone (PES)) with the same MWCO
    lead to very diIIerent perIormances which cannot be explained by membrane structure. The membrane which showed the more
    porous structure by SEM observation presented the lowest Ilux. Its poor perIormances are related to a high Iouling index which
    cannot be estimated without any experiment.
    However, thanks to an appropriate experimental procedure, it was possible with only Iew experiments to select the best
    membrane allowing the total retention oI Iructo oligosaccharides with degree oI polymerization (DP) higher than 40.
    Furthermore the results obtained in dead-end Iiltration cell were conIirmed in a tangential Iiltration device.
    This work was supported by the Programme Alan, the European Union Programme oI High Level Scholarships Ior Latin
    America (Scholarship E04D032803MX).
    -314-
    PD.1.11
    Multilayered polyelectrolyte complexes as nanofiltration membranes for anion
    separation
    P. Ahmadian Namini, X. Li, W. Goyens, I. F.J. Vankelecom
    ,
    B. Meesschaert
    Centre for Surface Chemistrv and Catalvsis, Facultv of Bioengineering Sciences, Katholieke Universiteit Leuven, Kasteelpark
    Arenberg 23, P.O. 2461, 3001 Leuven, Belgium
    ivo.vankelecombiw.kuleuven.be
    The layer-by-layer (LBL) deposition oI polyelectrolytes (PE) has emerged as a versatile and inexpensive method Ior the
    construction oI polymeric thin Iilms, oIten with nanometer-scale control over the spatial distribution oI ionized species within
    the Iilm. This is normally done via the alternating exposure oI a charged substrate to solutions oI positive or negative PEs.
    Films prepared via this method are in particular attractive materials Ior membrane separation Ior several reasons: (1) Iilm
    thickness can be controlled to the nanometer scale simply by varying the number oI deposited bilayers, and (2) nearly any PE
    can Iorm these Iilms, enabling easy tuning Ior a given separation through proper selection oI the bilayer constituents.
    In the present work, alternating deposition oI oppositely charged PEs was used to prepare nanoIiltration membranes to separate
    anions. A new combination oI PEs, poly(diallyldimethylammonium chloride) (PDDA) and sulIonated poly(ether ether ketone)
    (SPEEK), is reported Irom which supported membranes consisting oI 5, 10, 15, and 20 bilayers were prepared via the layer-by-
    layer method at diIIerent salt concentrations. The morphology oI the membranes was studied in detail by SEM and AFM,
    showing rougher membrane surIaces with increasing bilayer number. PE complex based membranes were applied in anion
    separation and the eIIects oI bilayers number and salt concentration on perIormance oI membranes were studied. Prepared
    membranes showed retentions in range oI 10-40 Ior chloride and 70-95 Ior sulIate and phosphate, conIirming the potential
    oI anion separation.
    |1| G. Decher, Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites, Science, 1997, 277, 1232-1237.
    |2| X. Li, S. De Feyter, D. Chen, S. Aldea, P. Vandezande, F. Du Prez, I. F. J. Vankelecom, Solvent-Resistant NanoIiltration
    Membranes Based on Multilayered Polyelectrolyte Complexes, Chem. Mater., 2008, 20, 38763883.
    PD.1.12
    New parameter for membrane cleaning efficiency determination
    C. Astudillo
    1,2
    , J. Parra
    2
    , S. Gonzalez
    2
    , B. Cancino
    2,3
    1
    PhD Programm of Biochemical Engineering. Pontificia Universidad Catolica de Jalparaiso (PUCJ).
    General Cru: 34, Jalparaiso, Chile.
    2
    School of Food Engineering, PUCJ, Jalparaiso, Chile.email. beatri:.cancinoucv.cl
    3
    Regional Centre for Healthv Foods (CREAS)
    carolina.astudilloucv.cl

    In membrane processes the cleaning is an important step, because has a large eIIect on process productivity. For cleaning
    eIIiciency evaluation normally two kinds oI parameters are used. Ones compare only Iluxes and the others compare only
    resistances between new and clean membrane. This creates some reIlexions: Which ones are better than others? Is the
    conclusion about the cleaning eIIiciency independent oI the parameter used? To bring more elements to this discussions, this
    work present two examples oI cleaning eIIiciency. The aim oI this paper is to compare the most used parameters Ior membrane
    cleaning; those are the Ilux recovery (FR) and the resistance recovery (RC) and, also propose a new one called: membrane
    performance recoverv (MPR). MPR it was deIined as the ratio between the average membrane Ilux aIter cleaning and the
    original membrane Ilux. This parameter uses the slope and intercept oI the Ilux-transmembrane pressure (TMP) curves Ior the
    original and clean membranes, comparing the complete curves and it is valid Ior all transmembrane pressure range. The MPR
    was applied in two cases as examples: First, the cleaning oI ceramic membrane Iouled with milk by Ultrasil

    11 (US11) and
    second, the cleaning oI polymeric membrane Iouled with beetroot by Ultrasil

    10 (US10). In the Table the results Ior RC and


    FR are shown.
    Parameter After US10 After US11
    Membrane resistance 2.64 10
    13
    m
    -1
    9.88 10
    11
    m
    -1
    RC 13.9 . 25.9 .
    FR at 90 kPa 99.4 90.0
    FR at 170 kPa 89.6 85.2
    For FR the supplier GE Healthcare (1) indicates that should be
    up 90 aIter cleaning, but they did not mention about TMP
    Ior evaluating this parameter. In other hand, Gan et al. (12)
    mention RC must be lower than 15 and DauIin et al. (3)
    preIer RC4.8.
    -315-
    By using these criteria each membrane sometimes is considered cleaning and others is still dirty.
    Nevertheless, the MPR value was 84.2 (cleaning by US11). For that, the conclusion must be the cleaning was not enough
    (FR90) and so, another cleaning cycle must be done. In the other case, Ior cleaning by US10, the MPR value was 92.0
    and that means the membrane could be considered clean Ior all TMP. Finally, this parameter allows obtaining a unique
    conclusion Ior each membrane cleaning treatment and can be useIul Ior the cleaning membrane assessment.
    Acknowledgement: FONDEF Proyect D07I1136, "Diseo, produccion y evaluacion de jugos de uvas con propiedades
    Iuncionales que contribuyan a la promocion de la salud de la poblacion".
    1- GE Healthcare, Cleaning oI cross Ilow Iiltration membranes, Technical BrieI 18-1171-72 AA Membrane devices, 2005.
    2- Q. Gan, J.A. Howell, R.W. Field, R. England, M.R. Bird and M.T. McKechinie, Synergetic cleaning procedure Ior a
    ceramic membrane Iouled by beer microIiltration, J. Membrane Sci., 155 (1999) 277-289.
    3- G. DauIin, U. Merin, J. Labbe, A. Quemerais and F. Kerherve, Cleaning oI inorganic membranes aIter whey and milk
    ultraIiltration, Biotechnol. Bioeng, 38 (1991) 82-89.
    PD.1.13
    Structural and functional modifications of milk globular proteins induced by dead-
    end ultrafiltration
    M. Van Audenhaege
    1
    , F. Garnier-Lambrouin
    2,3
    , S. Pezennec
    2,3
    , G. Gesan-Guiziou
    2,3
    1
    SOREDAB S.A.S, La Tremblave, 78125 La Boissiere Ecole, France
    2
    INRA, UMR1253 STLO, 65 rue de St Brieuc, 35000 Rennes, France
    3
    Agrocampus Ouest, UMR1253 STLO, 35000 Rennes, France
    genevieve.gesan-guiziourennes.inra.Ir
    Chromatography is the reIerence technology Ior the puriIication oI whey proteins at the industrial scale but the membrane
    process alternative is considered with more and more interest. Several studies have previously Iocused on the improvement oI
    membrane selectivity and Iouling during protein Iractionation however hardly any work has been considering the Iunctionality
    oI protein Iractions obtained Irom this technology. The goal oI this work is to study the impact oI Iiltration on the structural
    and Iunctional characteristics oI milk globular proteins oI high nutritional, biological and technological properties (u-
    lactalbumin and -lactoglobulin).
    Dead-end Iiltration experiments (protein concentration: 1g/L, temperature: 25C, transmembrane pressure: 1.5 10
    5
    Pa) were
    conducted on puriIied protein solutions using organic membranes oI diIIerent materials and molecular weight cut-oII. The
    composition oI Iractions (permeate and retentate) was monitored by reversed-phase liquid chromatography and atomic
    absorption spectrometry. The structural changes oI proteins were evaluated by circular dichroism and intrinsic Iluorescence
    and the Iunctionality oI Iractions by the measurement oI the pH-dependent solubility and the protein surIace hydrophobicity.
    It has been shown Ior u-lactalbumin that regardless oI the membrane used, Iunctional properties oI permeate and retentate were
    modiIied and this, despite small pH and ionic strength variations. The protein surIace hydrophobicity was slightly increased in
    the retentate but drastically decreased in the permeate. The solubility oI proteins, higher than 95 Ior the initial solution
    regardless oI the pH, decreased Ior the retentate and was stretched to a larger range around the isoelectric point oI the protein.
    On the contrary, the solubility oI the proteins recovered in the permeate was improved on the whole pH range. The change oI
    the ionic composition induced by Iiltration could be partially responsible Ior some observed modiIications.
    Considering our results, the techniques used are shown to be sensitive to Iunctional modiIications oI proteins induced by dead-
    end ultraIiltration. Mechanisms subtending such Iunctional changes will be approached at the molecular scale by a structural
    analysis oI Iractions.
    This work was carried out with the Iinancial support oI the ANR- Agence Nationale de la Recherche The French National
    Research Agency under the Programme National de Recherche en Alimentation et nutrition humaine , project ANR-06-
    PNRA-015 .
    -316-
    PD.1.14
    Membrane fractionation of red beet juice to obtain natural red colour extract
    B. Cancino
    1,2
    , J.A. Parra
    1
    1
    School of Food Engineering, Pontificia Universidad Catolica de Jalparaiso, Waddington 716, Jalparaiso, CHILE. email.
    beatri:.cancinoucv.cl
    2
    Regional Centre for Healthv Foods (CREAS)
    beatriz.cancinoucv.cl
    In Iood, the utilization oI synthetic colorants, especially oI the red ones has been leIt out because oI the risk Ior human health.
    ThereIore, the use oI pigments and colors as ingredients Ior Iood Iormulation has been enhanced during the last years. One oI
    the red pigments is the betalain contained in red beets (beta vulgaris) |1|. In this work the Iractionation oI red beet (beta
    vulgaris) juice is presented using membrane processes in order to obtain a concentrated pigment solution. Cooked red beets
    were used Ior the pigment extraction. The juice extraction method is not presented in this work but it was also investigated.
    The juice obtained Irom the red beets was Iiltered using a 0.2 m multitubular microIiltration (MF) ceramic membrane with a
    0.0232 m
    2
    total area. The Rm (membrane resistance) was 5.37E11 m
    -1
    . The permeate was collected and then nanoIiltrated
    using a Ilat-sheet AlIa-Laval membrane (NF99HF) with a 0.01018 m
    2
    total area, inside oI a continuous Ilat cell equipment and
    using a positive displacement pump. The Rm was 2.539 E13 m
    -1
    . The permeate obtained Irom the nanoIiltration (NF) process
    was colorless. Table 1 shows the results oI those Ilows and processes. For the comparison among diIIerent color intensities a
    Shimatzu UV 1603 spectrometer was used. The color was compared using the CIELAB color space |2| by means oI a Minolta
    CR-200b colorimeter. The solution obtained Irom the NF concentration process was compared with a commercial pigment; the
    results show that Ior the same red color intensity, the concentrated solution obtained Irom NF was thirty three times more
    concentrated than the commercial pigment solution.
    Volume ratio (VR) is deIined as the ratio between the initial volume oI the Ieeding solution and the Iinal volume oI the
    concentrate. RT is the ratio between the turbidity oI the Ieeding solution and the permeate solution, both in NTU.
    Table 1. Results Ior MF and NF membranes
    Membrane
    Parameters
    Transmembrane Pressure (bar) Temperature (C) VR RT
    MF 0.95 27 2360/560 4.2 750/24 31.25
    NF 99HF 10.8 26 1650/750 2.2 26/151 0.172
    Acknowledgement: to Dr. Frank Lipnizky Irom AlIa-Laval Company Ior supplying the NF membranes.
    |1| Fennema , O.R. (2002). Food chemistry. 3 Edicion. Marcel Dekker..
    |2| Ohno, Y., 2000; 'CIE Fundamentals Ior Color Measurements. Paper Ior IS&T NIP16 ConIerence, Vancouver, Canada,
    Oct. 16-20.
    PD.1.15
    Dehydration of used solvents of printing industry for reuse
    E. Bksoglu, H. Kalipilar, L. Yilmaz
    Department of Chemical Engineering, Middle East Technical Universitv, 06531 Ankara, Turkev
    bukusoglmetu.edu.tr
    Pervaporation is an attracted process Ior the separation oI liquid mixtures because oI its low energy consumption and simple
    application with respect to the other liquid separation techniques.|1| It is Irequently applied in the dehydration oI the solvents
    that Iorm azeotrope with water.|2|
    In printing industry, production cost can be signiIicantly reduced by recycling solvents used in the process. The recycled
    solvents are desired to be water-Iree to increase their economical value.
    In the solvent recovery process oI a local printing company, a stream containing ethanol, isopropanol and water is obtained.
    This work is aimed to dehydrate this water containing alcohol solution by pervaporation. The solvent solution has a
    -317-
    composition oI 58, 28 and 14 by mass, respectively. The behavior oI the membrane perIormance at diIIerent process
    parameters, temperature, pressure and varying Ieed compositions will be studied.
    Pervaporation experiments were done with a laboratory scale pervaporation setup using commercial hydrophilic membranes
    Pervap 2211 and Pervap 2210 oI Sulzer Chem-tech. Samples were taken in one hour period until steady state with a
    membrane module having 64 cm
    2
    membrane area. Then, three samples were taken and the composition analyses on these
    samples were made with Hewlett Packard 5890 Series 11 Gas Chromatograph with Porapak Q packed column. In addition, it is
    decided to use two types oI membrane modules with varying geometries and areas in order to observe the eIIect oI Ilow pattern
    on the perIormance oI the membranes.
    It is observed that increasing the temperature Irom 30C to 60C at a permeate side pressure oI below 10 mmHg and a Ieed
    rate oI 1 L/min, Ilux increased Irom 19 g/m
    2
    .h to 96 g/m
    2
    .h exponentially whereas the composition oI water in permeate
    remained nearly constant about 95 .
    |1| Atra, R., Vatai, G., Bekassy-Molnar, E., Isopropanol Dehydration by Pervaporation, Chemical Engineering and Processing
    38 (1999) 149 155
    |2| CzeIalvay, E., Szitkai, Z., Mizsey, P., Fonyo, Z., Experimental data based modeling and simulation oI isopropanol
    dehydration by pervaporation, Desalination 229 (2008) 94-108.
    PD.1.16
    Purification of phosphoric acid by means of membrane technology
    A.Kossir, K.Khaless
    CERPHOS-OCP, 73 Bd Moulav Ismail, roches noires, 20 300 Casablanca
    a.kossirocpgroup.ma, k.khalessocpgroup.ma
    The phosphoric acid is an important medium in making Iertilizers and in the elaboration oI pure products meant Ior Iood
    industry and surIace treatments. Our main objective is to use the membrane process Ior phosphoric acid puriIication bearing in
    mind that it is generally produced by humid / moist tract and contains a large variety oI impurities such as Fe, Cd, V.
    These impurities have negative eIIects on the process oI manuIacturing and on the quality oI the acid obtained.
    Various processing ways were used to puriIy the phosphoric acid: precipitation, crystallization, liquid-liquid extraction and
    exchange oI ions. There are only a Iew Known studies on the inverse osmosis and the nanoIiltration |1, 2|.
    For the very concentrated phosphoric acid solutions (considering the PH conditions and the temperature), the number oI
    membranes capable to resist Ior a suIIicient period is very limited. Our choice was then made on the PES1 0 (Nadir) organic
    membrane, MPS 36 (Koch International, Roissy, France) resistant to pH varying
    From 0 to 14, and also on Desal 5-DL (Osmonics).
    Impurity reduction, respectively 30 Ior the trivalent ions (Al, Fe.) and 20 Ior the divalent ions (Cd, Cu.) in industrial
    solutions, were achieved in tangential mode by using MPS-36 and PES 10 membranes.
    The Desal 5-DL membrane (the pH chemical stability oI which is insuIIicient according to the manuIacturer) was tested Ior a
    comparison selection. This membrane Iits better Ior the separation oI phosphoric acid and impurities: Strong retention oI 95
    oI major impurities (Fe, Al, Cr, ..)
    For the 3 membranes examined, we can note that the nanoIiltration doesn`t permit to puriIy the arsenic solutions, Iluorine or
    sulIates. These ions are completely or nearly retained because they are probably in neutral or univalent Iorms.
    The reduction oI major and minor impurities was improved by using a second stage in a discontinuous chain.
    |1| M.P GONZALEZ, R. NAVARRO, I. SAUCEDO, M. AVILA, J. REVILLA, CH. BOUCHARD.PuriIication oI
    phosphoric acid solutions by reverse osmosis and nanoIiltration``J. Desalination. 147, 315-320, (2002).
    |2| H.SKIDMORE, K. HUTTER, 'Methods oI puriIying phosphoric acid Brevet de Simplot Co JR |VS|, USP 594 500
    (1999)
    -318-
    PD.1.17
    Effects of oxidation states of nickel (Ni), copper (Cu), palladium (Pd) and silver (Ag)
    on the rejection by nanofiltration membranes
    T.J. Brooms, S.J. Modise, S.M. Nelana
    Department of Chemistrv, Facultv of Applied and Computer Sciences, P/Bag X021,Jaal Universitv of Technologv,
    Janderbiflpark, 1900, RSA
    thabobvut.ac.za
    Mining industry area comprises oI many commodities and diIIerent production processes (YongFeng, 2005). Waste Irom the
    mine sector originates Irom mining operational discharge oI metals (Copper, Nickel, Palladium and Silver) in solution Irom
    reIinery plants into the river or nearby dams. Membranes have been used in the past Ior the recovery oI metal in waste water
    eIIluents. Van der Merwe (1998) used the NF membranes and conIirmed that the Cu
    2
    and Ni
    2
    large positively charged ions
    are rejected based on the molecular weight cut-oII (MWCO) oI approximately 150-250 Daltons.
    The current study is aimed at evaluating the perIormance oI nanoIiltration (NF) membranes Ior the removal/recovery oI
    transition metals and the use oI Donnan Exclusion mechanism Ior the ion separation Irom electrostatic interaction oI cation
    metal. Flat sheets membranes (NF90, NF270 and NF-) are used Ior evaluation and rejection oI cation on the surIace layer oI
    polymer material with the application oI pressure as the driving Iorce at 25C. In this study, the varying pH is a priority Ior the
    characterization oI membrane perIormance with regards to surIace charge density. Conductivity was measured Ior
    concentration oI solution and the ion content oI the solution. AAS, ICP and IC instrumentations are used Ior quantiIication oI
    ion species Ior both Ieed and the permeate. SEM was also used Ior membrane surIace morphology. Membrane eIIective charge
    was considered. Among the NF membrane elements used, NF- was Iound to be the one that rejected the most compared to
    NF90 and NF270, with the order NF270~NF90~NF- due to their pore size and negative nature oI the membrane. At pH 2.0,
    the rejection oI Cu
    2
    ion was ~90 Ior NF, while Ior NF270 and NF90 it was 90 at pressure oI 20 bar. This implies that the
    rejection is not only charge and pressure dependent but also concentration dependent.
    1. N. YongIeng, Source, Type, Amount and eIIect oI mining waste, Tsinghua University, (2005), 1-20.
    2. I.W, Van der Merwe, Application oI nanoIiltration in metal recovery. Journal of the South African Institute of Mining and
    Metallurgv.(1998), 339-342.
    PD.1.18
    Electrodialysis as a useful technique for glyceric acid separation from fermentation
    broth
    H . Habe
    1
    , Y. Shimada
    2
    , T. Fukuoka
    1
    , D. Kitamoto
    1
    , M. Itagaki
    2
    , K. Watanabe
    2
    , H. Yanagishita
    1
    , K. Sakaki
    1
    1
    Research Institute for Innovations in Sustainable Chemistrv, National Institute of Advanced Industrial Science and
    Technologv (AIST), Tsukuba Central 5-2, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
    2
    Department of Chemical Industrv, Science Universitv of Tokvo, Noda, Chiba 278-8510, Japan
    hiroshi.habeaist.go.jp
    Recently, much attention has been Iocused on the bioreIinery, which is a new manuIacturing concept Ior converting renewable
    biomass to valuable Iuels and products. Among such biomass-derived products, organic acids have been widely used in Ioods,
    beverages, plastics, resins, pharmaceuticals, cosmetics, and so on, and thereIore have a close relationship with human's daily
    liIe. Usurally, organic acids can be produced by Iermentation or chemical synthesis, however, the Iormer is preIerred Irom the
    viewpoint oI sustainable development. In the production oI organic acids via Iermentation, their separation, concentration, and
    puriIication Irom Iermentation broth having various ingredients are very important, and one oI membrane separation
    technologies, electrodialysis (ED), is thought to be the key innovation. ED has been already applied to the production oI
    various organic acids |1|.
    Our study has been Iocused on the glyceric acid (GA) recovery Irom Iermentation broth by using ED. GA is produced by the
    bioconversion oI glycerol, which is Iormed as a by-product in the growing biodiesel production and oleochemical industry |2|.
    As a Iirst step, we demonstrated the GA recovery with a desalting electrodialysis unit (MICRO ACILYZER S1, ASTOM Co.)
    equipped with commercial membrane cartridge Ior anion recovery (AC-122-10, SUN ACTIS Co.; eIIective membrane area, 10
    cm
    2
    ). The inIluence oI several impurities in glycerate model solutions on the process perIormance was investigated, and as a
    result, more than 93 oI glycerol added in the model solutions (50 -150 g/l) were excluded. Also, the addition oI 25 g/l
    -319-
    polypepton or yeast extract did not exhibited signiIicant adverse eIIects on the whole electrodialysis process. Using culture
    broth oI Acetobacter tropicalis containing 14.6 g/l D-GA, the D-GA recovery and the energy consumption were 99.4 and
    0.24 kWh/kg, respectively |3|. Based on the results, the subsequent scale-up studies were also carried out on a two-stage
    electrodialysis process, which consisted oI desalting ED and water-splitting ED, with a desalting electrodialysis unit
    (ACILYZER EX3B, ASTOM Co.) equipped with membrane cartridge (eIIective membrane area, 550 cm
    2
    ).
    This work was supported by the Industrial Technology Research Grant Program in 08A26202c Irom the New Energy and
    Industrial Technology Development Organization (NEDO) oI Japan.
    |1| C. Huang, T. Xu, Y. Zhang, Y. Xue, G. Chen, Application oI Electrodialysis to the Production oI Organic Acids: State-oI
    the-art and recent developments. J. Membr. Sci., 2007, 288, 1-12
    |2| H. Habe, T. Fukuoka, D. Kitamoto, K. Sakaki, BiotransIormation oI Glycerol to D-Glyceric Acid by Acetobacter
    tropicalis. Appl. Microbiol. Biotechnol., 2009, 81(6), 1033-1039
    |3| H. Habe, T. Fukuoka, D. Kitamoto, K. Sakaki, Application oI Electrodialysis to Glycerate Recovery Irom a Glycerol-
    containing Model Solution and Culture Broth. J. Biosci. Bioeng., 2009, 107(4), in press
    PD.1.19
    Using microfiltration as an alternative fresh water supply system for remote areas in
    the Amazon rainforest
    M.V. Melo, B.R.S. Costa, A.S. Freitas, R.M. Caetano, C.K. Schulz, A.M.T. Louvisse, O.A. Pereira Jr
    PETROBRAS Research and Development Center, Av. Jequitiba 950, Cidade Universitaria - Rio de Janeiro, Bra:il
    mvmelopetrobras.com.br
    Located 650 km Irom Manaus, the capital oI the Brazilian state oI Amazonas, the oil-rich province oI Urucu includes the
    Geologist Pedro Moura Operations Base, the Arara Industrial Complex, and two ports on the Urucu River the ports oI Urucu
    and Evandro. There is also a residue park, the Iirst well to be drilled (RUC-1), an aerodrome Ior light aircraIt, a natural gas
    station Ior Iuelling vehicles, a nursery Ior seedling reproduction, an orchidarium, and 120 km oI roads, 71 km oI which are
    paved. Within this huge complex, however, all the operations are rigorously monitored and administered to minimize any
    damage to the environment and to contribute to the sustainable development oI the Amazon region.
    Oil exploration and production in the Amazon region involves diIIerent operational challenges related to the location oI some
    installations such as Evandro port concerning Iresh water supply. At the moment, all the Iresh water supply Ior this port is
    made by bottles, which comes Irom the Operation Base aIter a long way by boat along the Urucu river.
    In order to propose an alternative Iresh water supply system Ior remote areas using as Ieed water the Urucu river, the
    PETROBRAS Research and Development Center technicians proposed a system based on the microIiltration technology. The
    aim oI this work is to present the results obtained oI a small scale microIiltration system installed at the province oI Urucu in
    order to evaluate its perIormance using a high humic acid content water (Uruc river) as Ieed water.
    PD.1.20
    Stability of polymeric ultrafiltration membranes in alkaline conditions
    M. Kallioinen, M. Mnttri
    Laboratorv of Membrane Technologv and Technical Polvmer Chemistrv, Lappeenranta Universitv of Technologv, POBox 20,
    FI-53851 Lappeenranta, Finland
    mari.kallioinenlut.Ii
    The growing need to protect the environment and an interest in producing high-value chemicals Irom compounds present in
    process streams will probably lead to an increase in the use oI membranes in the Iuture. In several possible separation
    applications, Ior instance in the separation oI hemicelluloses Irom cooking liquors in pulp mills, the prevailing process
    conditions are challenging Ior a polymeric membrane, Ior instance extremely alkaline or acidic. Thus, inIormation about the
    stability oI the commercial membranes in extreme conditions is needed and the aim oI this study was to increase knowledge oI
    the stability oI polymeric ultraIiltration membranes in alkaline conditions.
    -320-
    The study was divided into two parts. The aim oI the Iirst part was to Iind out the inIluence oI the alkaline conditions on the
    membrane samples. Samples oI six diIIerent ultraIiltration membranes, PES 20, PES 10, PES 5 and PAN 10 Irom Sepro
    and UH030P and UH050P Irom Microdyn Nadir GmBH, were kept in alkaline solutions in decanters at 50 C Ior one week.
    Two diIIerent alkaline solutions were used. The other contained 0.6 g/L NaOH and the other 20 g/L oI NaOH. AIter the week
    the membranes were rinsed with water and thicknesses and ATR-FTIR spectra oI the membrane samples were measured. The
    membranes, oI which resistances against the alkaline conditions were the best, were chosen to the Iiltration experiments oI the
    second part oI the study. The aim oI the Iiltration experiments was to examine the eIIect oI the exposure to alkaline conditions
    on retention and Ilux oI the membranes.
    The exposure to the solution containing 0.6 g/L oI NaOH did not reveal signiIicant diIIerences between the membrane
    stabilities while the resistances oI the membranes to the strongly alkaline solution (20 g/L NaOH) diIIered clearly Irom each
    other. The membrane PAN 10 was totally destroyed and the thicknesses oI the membranes PES 20, PES 10 and PES 5 were
    signiIicantly decreased. Furthermore, the chemical structures oI these membranes were clearly changed due to the one week
    exposure to the strongly alkaline solution. The membranes UH030P and UH050P withstood the strongly alkaline conditions
    clearly better compared to the other tested membranes, and thus, they were chosen to the Iiltration experiments. The one week
    exposure to the solution containing 0.6 g/L NaOH did not cause signiIicant changes in the retention or Ilux oI the membrane
    UH030P (measured with PEG 10 kg/mol solution) but the exposure to the strongly alkaline conditions decreased clearly the
    Ilux and increased retention. Likewise, the Ilux and retention oI the membrane UH050P changed due to the exposure to the
    alkaline solution containing 20 g/L oI NaOH (measured with the PEG 20 kg/mol solution).
    PD.1.21
    Surfactant Removal by a Nanofiltration/Photoelectrooxidation integrated process
    from a detergent industry wastewater
    C. Korzenowski
    1,3
    , A.F. Salvaterra
    1
    , M.B.O. Martins
    2
    , A.M.F. Silva
    2
    , J.M.R. Tavares
    2
    , A.M. Bernardes
    3
    ,
    J.Z. Ferreira
    3
    , E.C.N.F. Duarte
    2
    ,

    M.N.C. Pinho
    1
    1
    Instituto Superior Tecnico, (IST), Universidade Tecnica de Lisboa, Av. Rovisco Pais,1049-001, Lisbon, Portugal.
    2
    Instituto Superior de Agronomia, (ISA), Universidade Tecnica de Lisboa, Tapada da Afuda, 1349-017, Lisbon, Portugal.
    3
    Universidade federal do Rio Grande do Sul (UFRGS/PPGEM) ), Porto Alegre, RS, Bra:il.
    ckorzenowskigmail.com
    In recent years, considerable attention has been Iocused on Household Cleaning Products (HP) and Body Care (BC) and
    environmental risks associated with their manuIacturing, use and disposal. Furthermore, detergent products are complex
    mixtures in which ingredients tend to biodegrade and undergo partition at diIIerent rates. Membrane technologies are an
    important asset in the removal oI surIactants in wastewater |1-3|. Among these technologies, pressure-driven membrane
    processes, nanoIiltration/reverse osmosis, are important and attractive alternatives Ior puriIication oI wastewaters, since they
    achieve high removal eIIiciencies and allow the reuse oI process water and sub-products recovery |4|. This work is Iocused on
    nanoIiltration (NF) oI surIactants oI industrial wastewaters. The NF experiments are carried out with representative model
    solutions in a DSS plate-and-Irame Lab-Unit M20, equipped with NF-270 membranes (FilmTec Corp., Minneapolis, MN). The
    present work envisages the investigation oI NF as a technique generating a permeate stream, that can be reused as process
    water, and a surIactant concentrated stream. The NF concentrated stream is Iurther treated by photoelectrooxidation (PEO), an
    advanced oxidation process, consisting oI a combination oI electrolysis and heterogeneous photocatalyses, using oxide coated
    electrodes |5|. The experiments are carried out in a photolytic reactor, where the employed anode and cathode are DSA
    (70TiO
    2
    /30RuO
    2
    and Ti/TiO
    2
    , respectively). The UV sources oI radiation used are medium/high-pressure mercury vapor lamp
    oI 250 and 400 W power. The NF/PEO integrated process is optimized in terms oI the NF recovery rates and PEO eIIiciencies
    Ior maximal water recycling and surIactant destruction.
    |1| CESIO,2002.(Council oI European SurIactants Producers Statistics).
    http://www.ceIic.be/Iiles/Publications/cesio02010903.xls
    |2| S.Gonzalez, M.Petrovic, D.Barcelo. Removal oI a broad range oI surIactants Irom municipal wastewater Comparison
    between membrane bioreactor and conventional activated sludge treatment. Chemosphere 67 (2007), 335-343.
    |3| P. Van der Meeren,W. Verstraete, SurIactants in relation to bioremediation and wastewater treatment, Curr. Opin. Colloid
    In. 1 (1996) 624634.
    |4| E.A. Duarte, M. Martins, R. Fragoso, I.B. Reis, J. Laranjeira. How the Planning and EIIicient Management Can Answer to
    the New Environmental Challenges? A Detergent Industry Practical Experience. III International ConIerence on the EIIicient
    Use and Management oI Urban Water. Santiago, Chile (2005), 78-84.
    |5| M.A.S. Rodrigues, F.D.R. Amado, J.L.N. Xavier, K.F. Streit, A.M. Bernardes, J.Z. Ferreira. Application oI
    photoelectrochemical-electrodialysis treatment Ior the recovery and reuse oI water Irom tannery eIIluents. Journal oI Cleaner
    Production 16 (2008) 605-611
    -321-
    PD.1.22
    Efficient sunflower oil degumming in cross-flow ultrafiltration by a PVDF membrane
    C. M. Coutinho
    1
    , M. C. Chiu
    1
    , L. A. Viotto
    2
    , L. A. G. Gonalves
    1
    1
    State Universitv of Campinas, Department of Food Technologv, Laboratorv of Fats & Oils (LOG), Caixa Postal 6091, CEP
    13083-970, Campinas, SP, Bra:il
    2
    State Universitv of Campinas, Department of Food Engineering, Laboratorv of Process Engineering (LEP), Campinas, SP,
    Bra:il
    cm.coutinhouol.com.br
    The application oI membrane technology as a method oI separation, concentration and puriIication oI compounds is widely
    known in industrial processes, including in the Iood industry. Up to the present moment, the use oI membranes in oil
    technology has not been completely established. However, this technology shows great potential Ior reIining vegetable oils and
    oIIers many advantages when compared with conventional processes |1,2|. Thus, the use oI membrane technology provides
    high quality vegetable oils, according to market demands and ecologically correct and environmentally Iriendly, with reduced
    eIIluent production and signiIicant water-savings |3|.The results showed that the membrane was not aIIected by hexane and
    that cross-Ilow Iiltration in an ultraIiltration pilot module provided the best degumming eIIiciency Ior crude sunIlower oil. The
    permeate Ilow rate increased signiIicantly with the rise in operational pressure, without loss oI the phosphorous retention
    levels.
    CAPES, CNPq, FAPESP are acknowledged Ior Iinancial support.
    |1| PORTER, M.C. Handbook oI Industrial Membrane Technology. New Jersey: Noyes Publications, 1990.
    |2| CHERYAN, M. UltraIiltration and MicroIiltration Handbook. Lancaster: Technomic Publ. Co., Illinois, 1998, 526p.
    |3| MOURA, J.M.L.N.; GONALVES, L.A.G.; PETRUS, J.C.C.; VIOTTO, L.A. Degumming oI vegetable oil by
    microporous membrane. Journal oI Food Engineering. Essex, v. 70, p. 473 478, 2005.
    PD.1.23
    Influence of the operation parameters on the concentration of apricot juice
    E. Fogarassy, A. Kozak, E. Bekassy-Molnar, G. Vatai
    Corvinus Universitv of Budapest, Department of Food Engineering, Menesi ut 44. Budapest H-1118 Hungarv
    eszter.Iogarassyuni-corvinus.hu
    The apricot (Prunus armeniaca) is a very popular, tasty Iruit with many valuable components useIul Ior the human health. It is
    prevalent in Europe; in the temperate zone it becomes ripe in June and July. The conservation oI the Iruit is necessary to make
    it available Ior the consumers during the whole year the main products prepared Irom apricot are jams, parched Iruit, stringy
    juice and alcoholic drinks. The Iiltered, clear juice is not current yet.
    Using combined membrane Iiltration it is possible to produce concentrated clear apricot juice with high dry matter content at
    low temperature; this product can be stored at room temperature without any additives and can be the row material oI diIIerent
    soIt drinks.
    Hungarian Gonczi apricot was used Ior the experiments. AIter washing and taking out the seeds an enzyme treatment was
    applied to destroy the pectin. The proper enzyme, enzyme-concentration, temperature and elaboration time was worked out to
    reach a high proportion oI Iresh juice.
    Membrane Iiltration was used to clear, sterilize (MF, UF) than to concentrate (NF, RO) the juice. A membrane screening was
    applied using diIIerent temperatures, pressures and recycle Ilow rates. The Iurther concentration was solved by MD |1,2|.
    The inIluence oI the operation parameters on the permeate Ilux, membrane resistance, polarization resistance, osmotic pressure
    and juice concentration was determined and modeled.
    |1| Aron Kazak, Szilvia Banvolgyi, Ivetta Vincze, Istvan Kiss, Erika Bekassy-Molnar, Gyula Vatai: Comparison oI integrated
    large scale and laboratory scale membrane processes Ior the production oI black currant juice concentrate, Chemical
    Engineering and Processing: Process IntensiIication, Volume 47 (2008) 1171-1177
    |2| M.S. El-Bourawi, Z. Ding, R. Maa, M. Khayet: A Iramework Ior better understanding membrane distillation separation
    process, Journal oI Membrane Science 285 (2006) 4-29
    The author expresses her acknowledgement to the Jedlik Anyos (OM0034/2007) and the OTKA Foundations (T049850) Ior
    the Iinancial support.
    -322-
    PD.1.24
    Study of the influence of the enzymatic treatment in microfiltration of aai pulp
    C.P. Bagagli, L.A. Viotto
    Facultv of Food Engineering, State Universitv of Campinas, P.O. Box 6121, 13083-862 Campinas, SP, Bra:il
    cpbIea.unicamp.br
    The aai Iruit (Euterpe Oleracea Mart.) is native Irom the Amazon region and it is rich in anthocyanins and other antioxidant
    compounds, lipids, proteins, vitamins, minerals and Iiber, including pectin and cellulose |1|. The objective oI this work was to
    study the inIluence oI enzymatic treatment on the permeate Ilux during microIiltration oI aai pulp. The pectinase and cellulase
    enzymes were used, alone (0.1 m/m) and in combination (0.05 m/m each), and also the Ilat polymeric membrane oI PVDF
    (Polyvinylidene Fluoride) with 0,2 m pore diameter. All experiments were perIormed under the same experimental conditions
    (2 bar, 500 rpm and 25 C) in a laboratory cell with capacity oI 800mL, using 350mL until concentration Iactor (CF) equal to
    3,2. There was positive inIluence oI using the cellulase enzyme, reaching up initial Ilux oI 23 kg/h.m
    2
    and 6 kg/h.m
    2
    in the CF
    equal to 3.2, on the other hand using the aai pulp without enzymatic treatment were achieved initial Ilux and in CF3.2 equal
    to 18 kg/h.m
    2
    and 5 kg/h.m
    2
    , respectively. The combination oI the two enzymes resulted in Ilux oI 15 kg/h.m
    2
    to 7 kg/h.m
    2
    .
    The use oI pectinase enzyme exerted negative inIluence on the permeate Ilux, it was less than 1 kg/h.m
    2
    . The permeated and
    retained Iractions were analyzed Ior physical-chemical characterization.
    |1| H. Rogez, Aai: preparo, composiao e melhoramento da conservao, Phd thesis, Chemical Engineering Departament,
    Federal University oI Para, Brazil, 2000.
    PD.1.25
    The role of surfactants for the recovery of several bio-compounds using membrane
    technology
    M.O. Ruiz, I. Escudero, J.M. Benito, J.L. Cabezas, R.M. Geanta, B. Barriuso
    Department of Chemical Engineering, Universitv of Burgos, Pla:a Misael Bauelos s/n, 09001Burgos, Spain
    moruizubu.es
    Due to their special properties as surIace active agents, surIactants play a key role in several industries, such as in detergents,
    paints, dyestuIIs, paper coatings, inks, plastics, Iibres, toiletries, cosmetics, agrochemicals, pharmaceuticals, Iood processing,
    oil industries, etc. Above the critical micelle concentration (CMC), surIactant monomers selI-assemble into micelles or
    vesicles: the surIactant hydrophilic groups are oriented towards the bulk aqueous phase whilst hydrophobic groups remain
    inside the aggregate. Several ions or molecules can be linked to the micelles by electrostatic or Van der Waals Iorces. As a
    result, surIactants can be used as extraction agents Ior the incorporation or solubilization oI several molecules into these
    aggregates, usually oI colloidal size, that can be subsequently separated by ultraIiltration. This technique, named micellar-
    enhanced ultraIiltration (MEUF) has been proposed Ior the recovery oI pollutants, metals or organic compounds. In the MEUF
    process, micelles are retained by the membrane, while surIactant monomers with concentrations below CMC will pass through
    the membrane pores. Micelles are in dynamic equilibrium and the exchange rate between the monomer and the micelle
    depends on the structure oI the surIactant molecule, medium conditions, membrane characteristics and operating conditions.
    In this work, we have studied a MEUF process Ior the recovery oI bio-compounds that can be present in Iermentation broths,
    such as betaine and carboxylic acids (citric and lactic acids). Betaine (N,N,N-trimethylglycine) is present in waste streams
    Irom sugar beet processing plants, in concentrations oI up to 8 wt. in beet molasses and around 4 wt. in vinasses (aIter
    molasses Iermentation). Citric and lactic acids are usually present in lower concentrations. Their recovery would be highly
    proIitable since they may have applications in several industries. CentriIugal ultraIiltration experiments using 3 and 5 kDa
    organic membranes were carried out in order to select the most suitable surIactant and medium conditions Ior the recovery oI
    individual bio-compounds. Equilibrium distribution constant (K
    S
    ) was quantiIied as an indicator oI the aIIinity oI the bio-
    compound Ior the micelles. Finally, crossIlow ultraIiltration experiments oI aqueous solutions with the selected surIactant
    containing betaine or individual carboxylic acids were carried out using a 5 kDa cut-oII TiO
    2
    tubular ceramic membrane under
    diIIerent process conditions and operation modes. The composition oI the permeate agrees with the calculated Irom K
    S
    values,
    assuming a complete rejection oI the micelles by the membrane.
    This work was supported by the Ministerio de Educacion y Ciencia (MEC, Spain) and the European Commission through
    European Regional Development Fund by grant CTQ2006-03032. Funds received Irom Junta de Castilla y Leon through grant
    BU017A06 are also grateIully acknowledged.
    -323-
    PD.1.26
    Performance of micro and ultrafiltration membranes in wastewater treatment using
    membrane bioreactor
    S. MaIirad, M. H. SarraIzadeh, M. R. Mehrnia
    Biotechnologv Group, School of Chemical Engineering, College of Engineering, Universitv of Tehran, P.O.Box 11155-4563,
    Tehran, Iran
    sarraIzdhut.ac.ir
    Membrane bioreactors (MBRs), a combination oI the conventional activated sludge process and MF/UF membrane separation,
    have been increasingly attractive Ior wastewater treatment. Some studies show the eIIect oI membrane characteristics on MBR
    perIormance |1, 2|. In this study, wastewater treatment eIIiciency oI MBRs with micro and ultraIiltration membranes was
    compared. A laboratory scale submerged membrane bioreactor (sMBR) system with a Ilat sheet membrane module was used in
    the study Ior treatment oI oily wastewater. The synthetic wastewater was included oI oily pollutant with concentration oI 1000
    ppm. The mixed liquor suspended solid oI the bioreactor was approximately 6000 mg/L. The changes in pollutant
    concentration in inIluent, supernatant and eIIluent oI the bioreactor were evaluated by measurement oI chemical oxygen
    demand. Reduction oI membrane permeability due to membrane Iouling was also measured |1|. The results showed that in
    spite oI high diIIerence between initial permeability oI MF and UF membranes due to their diIIerent pore sizes, the
    permeability oI MF membrane will reduce to the permeability oI UF membrane. This behaviour was related to adsorption and
    settling oI bioparticles on membrane surIace and pores which cause membrane Iouling. ThereIore in long-term operation MF
    membranes will have as permeability as UF membranes because oI its pores narrowing and blocking due to bioIouling. Also
    the comparison oI permeate quality oI both MF and UF membranes had the same COD removal eIIiciency oI more than 91.
    |1| J. Zhang, H.C. Chua, A.G. Fane, Factors AIIecting the Membrane PerIormance in Submerged Membrane Bioreactor,
    Journal oI Membrane Science 284 (2006) 54-66.
    |2| P.L. Clech, A. Tony, G. Fane, Fouling in Membrane Bioreactors Used in Wastewater Treatment, Journal oI Membrane
    Science 284 (2006) 17-53.
    PD.1.27
    Application of nanofiltration membranes in crude palm oil decoloration
    T. N. Queiroz
    1
    , A. D. S. Machado
    1
    , M. C. Chiu
    1
    , L. A. Campos
    1
    , L. A. Viotto
    2
    , L. A. G. Gonalves
    1
    1
    State Universitv of Campinas, Department of Food Technologv, Laboratorv of Fats & Oils (LOG), Caixa Postal 6091, CEP
    13083-970, Campinas, SP, Bra:il
    2
    State Universitv of Campinas, Department of Food Engineering, Laboratorv of Process Engineering (LEP), Campinas, SP,
    Bra:il
    chiumingIea.unicamp.br
    Palm oil is oxidatively stable due to a Iatty acid composition with low polyunsaturation and a high antioxidant content. While
    most vegetable oils provide mainly u- or -tocopherol, palm oil is unique in that it contains relatively large concentrations oI
    homologue tocotrienols (u, , and o), which together account Ior 72-80 oI the total tocopherol and tocotrienol content oI
    palm oil (600-1000 ppm). Moreover, palm oil is one oI the richest sources oI u - and -carotene ( -C) (400-3500 ppm) |1,2|.
    Carotenoids are a class oI natural pigments widely distributed in vegetables and Iruits and also added as additives, being
    responsible Ior the yellow-reddish color oI many Ioods. Apart Irom their colorant properties, the carotenoids are related to
    important Iunctions and physiological actions, provitamin A activity being the most known one. In addition, a positive
    correlation has been observed between ingestion oI vegetables and Iruits containing carotenoids and prevention oI several
    chronic-degenerative diseases, such as cancer, inIlammation, cardiovascular disease, cataract, and age-related macular
    degeneration, among others |3|.
    The membrane process is a remarkably simple process oIIering many advantages over the conventional processes, namely low
    energy consumption, ambient temperature operation, no addition oI chemicals, and retention oI nutrients and other desirable
    components |4| The results showed that the nanoIiltration membranes had lower Ilux with ethanol and higher Ilux with water
    in a dead-end Iiltration mode. Both membranes presented a eIIicient separation oI carotenoids Irom the palm oil, representing
    high retention values oI this compound.
    CAPES, CNPq, FAPESP are acknowledged Ior Iinancial support.
    -324-
    |1| C. K. Ooi, Minor components oI palm oil. PORIM Bull. 1999, 38, 29-32.
    |2| M. T. Schroeder, E. M. Becker, L. H. Skibsted, Molecular Mechanism oI Antioxidant Synergism oI Tocotrienols and
    Carotenoids in Palm Oil, J. Agric. Food Chem. 2006, 54, 3445-3453.
    |3| V. Rosso, A. Z. Mercadante, IdentiIication and quantiIication oI carotenoids, by HPLC-PDA-MS/MS, Irom amazonian
    Iruits, J. Agric. Food Chem. 2007, 55, 5062-5072
    |4| R. Subramanian, K. S. M. S. Raghavarao, H. Nabetani, M. Nakajima, T. Kimura, T. Maekawa , DiIIerential permeation oI
    oil constituents in nonporous denser polymeric membranes J. Membr. Sci. 2001, 187, 101108.
    PD.1.28
    Separation of oxygen with egg shell: Reverse pervaporation
    D. Krishnaiah, R. Sarbatly
    Advanced membrane research group, Chemical Engineering Program, School of Engineering and Information Technologv,
    Universitv Malavsia Sabah, 88999 Kota Kinabalu, Sabah, Malavsia
    krishnaums.edu.my
    Membrane separation process has become one oI the emerging technologies in the recent years. Pervaporation is one oI the
    membrane separation processes that have gained increasing interest in the chemical and allied industries in which a gas
    component Irom the liquid is separated by membrane(1,2). On the other hand separation oI gas into liquid through membrane
    is not yet established which has several advantages. In this investigation, transIer oI oxygen into water using egg shell and its
    suitability was carried out.
    In the normal pervaporation process, the permeation is occurring in the direction oI liquid to the vapor. The reverse
    pervaporation, is a new concept that reversing the direction oI material transIer Irom gas to the liquid. This direction will give a
    new means in the Iield oI gas separation, where unwanted gas component permeates into the liquid through the membrane as
    alternative to direct gas liquid contact method.
    The perIormance oI eggshell as a ceramic membrane is evaluated. It was Iound that the egg shell membrane allows oxygen
    transIer only. 60 oI dissolved oxygen was achieved in 1 hour duration. The eIIect oI Ilow rate and temperature on the
    transIer oI oxygen Irom air was investigated.
    1. R.W. Baker, J.G. Wijmans, A.L. Athayde, R. Daniels, J.H. Ly and M. Le, Separation oI Volatile Organic Compounds Irom
    Water by Pervaporation, J. Membr. Sci. 137, 159 (1998).
    2.N. Tanihara, N. Umeo, T. Kawabata, K. Tanaka, H. Kita and K. Okamoto, Pervaporation oI Organic Liquids Through
    Poly(etherimide) Segmented Copolymer Membranes, J. Membr. Sci. 104, 181 (1995).
    PD.1.29
    Purification of industrial phosphoric acid by nanofiltration
    A. CharIi
    1
    , N. Ben Amar
    1,2
    1
    Laboratoire de Modelisation Mathematique et Numerique dans les Sciences de lIngenieur, Ecole Nationale des Ingenieurs de
    Tunis, Campus Universitaire, B.P 37 Le Belvedere 1002, Tunis.
    2
    Institut National des Sciences Appliquees et de Technologie, B.P 676, 1080 Tunis cedex, Tunisie
    nihel.benamarinsat.rnu.tn
    Industrial phosphoric acid produced by the wet process contains diIIerent impurities (Fe, Al, Mg, V, Zn, Cd, Cu, Cr, Ni, Mn).
    In this work, we present the puriIication oI a wet-process phosphoric acid by NanoIiltration. In an attempt to work under
    similar conditions to that used in industrial plant, the experiments were realized with a 27 P
    2
    O
    5
    acid concentration and at a
    high temperature (55C). The experiments were conducted in a stainless steel dead end cell with agitation at 526 rpm and
    under the pressure oI an inert gas (N
    2
    ). The phosphoric acid was pre-treated by 20 m Iiltration step to prevent membrane
    Iouling; the turbidity achieved is 1.26 NTU. Two membranes speciIic to acid use were tested: KH (GE-Osmonics) and MPF34
    (Koch).
    The preliminary results conIirm Gonzalez et al. work conclusion |1| concerning the capability oI the NanoIiltration in the
    puriIication oI phosphoric acid. Results show that a very good acid permeation is achieved with both membranes (~98)
    preserving the acid concentration to 27 P
    2
    O
    5
    (Table.1). The eIIect oI pressure on acid permeation was tested Irom 20 to 35
    -325-
    bar and show a high constant value (98). NanoIiltration at 35 bar, give higher permeate Iluxes with the membrane MPF34 (5
    L/hm
    2
    ) comparing to KH membrane (0.6 L/hm
    2
    ). However, the puriIication with KH is more eIIicient than with MPF34. Table.
    1 resumes the impurities concentrations beIore and aIter the NanoIiltration. With KH, we note the high elimination
    perIormance oI Al (84,5), Fe (86), Mg (84), Cr (85) and low rejection oI Zn (39), Cu (66), Ni (73), Mn (77)
    and V (74 ).
    concentration
    ( P
    2
    O
    5
    )
    Fe
    (ppm)
    Al
    (ppm)
    Mg
    (ppm)
    Cr
    (ppm)
    Zn
    (ppm)
    Cd
    (ppm)
    Cu
    (ppm)
    Ni
    (ppm)
    Mn
    (ppm)
    V
    (ppm)
    Ieed 27 1565 1700 4778 143 105 12 5 13 23 39
    KH
    permeat
    27,8 231 303 752 25 70 12 1 4 6 12
    MPF34
    permeat
    27 1286 1343 3690 119 90 10 4 10 18 32
    |1| M.P. Gonzalez, R. Navarro, I. Saucedo, M. Avila, J. Revilla, Ch. Bouchard, PuriIication oI phosphoric acid by reverse
    osmosis and nanoIiltration, Desalination 147 (2002) 315-320.
    PD.1.30
    Degradation kinetics of nanofiltration membranes in alkaline cleaning
    M. Mnttri, A. Pihlajamki, J. Lahti
    Laboratorv of Membrane Technologv and Technical Polvmer Chemistrv, Lappeenranta Universitv of Technologv, POBox 20,
    FI-53851 Lappeenranta, Finland
    Mika.Manttarilut.Ii
    NanoIiltration is expanding its application areas Irom water treatment to Iractionation oI industrial solutions in waters or
    organic solvents. In the sugar industry and in the pulp and paper industry the process liquors to be Iiltered have a high
    temperature and also a pH Iar Irom neutral. For instance, liquors Irom pulping processes might have a pH around 12 and a
    temperature above 70 C. In addition, the cleaning oI membranes is usually done using alkaline cleaning agents when organic
    Ioulants are the major problem. Temperature has a signiIicant eIIect on the cleaning eIIiciency but, unIortunately, a high
    temperature Irequently aIIect the membrane properties detrimentally.
    In this paper cleaning oI three NF membranes at alkaline conditions is studied. The experiments were made by exposing
    membranes to cleaning solution at diIIerent stages Ior long periods oI time. The condition oI the membranes is monitored by
    measuring pure water Ilux and retention oI salt and sugar between the cleaning stages. The kinetics oI the changes in retention
    and Ilux are Iitted with Arrhenius equation which reasonably models the degradation processes. The results showed a potential
    tool to estimate the membrane retention and Ilux at extreme conditions as a Iunction oI total cleaning time. These results can
    be used to predict the changes oI membrane properties in industrial processes when cleaning is made at extreme conditions.
    PD.1.31
    Effects of electrolytes on the noise in the over limiting current range: (Cation
    exchange membrane)
    K. Oulmi, K.E. Bouhidel
    Laboratorv of Chemistrv and Environmental Chemistrv LCCE, Dpt.of Chemistrv Universitv of Batna ALGERIA
    bouhidellycos.com
    Introduction: This research work investigates the i-v curve, particularly the eIIect oI the counter ion nature on the noise in the
    over-limiting current Iov.
    The overlimiting current is always accompanied by aa neat electrical noise. It is a well accepted experimental phenomenon
    |1,2,3,4|.The study oI this may contribute to a better understanding oI the Iov.
    This research work presents original Iinding:
    -326-
    The electrical noise depends directly on the counter ion nature. The noise intensity decreases according to the HoIImeister
    serie: Li

    > Na

    >K

    . (Figure 1 a b).
    We explain this by the hydration number oI the counter-ion.
    NH
    4

    presents a singular behaviour; the noise is minimal (Figure 1.c).


    |1| M.E.Green and M.YaIuso,J.Phy.Chem 72,12(1968)
    |2| S.H.stern and M.E.Green, J.Phy.Chem 77,12(1973);
    |3|F.Maletzki,H;W.Rosler and E.Staude;J.Memb.Scie. 71(1992) 105.
    |4| J.H.Choi, J.S.Park and S.H.Moon, J.oI colloid and InterIace science 251(2002)311.
    PD.1.32
    Application of membrane process in Vitamin C production - Plate & frame
    membrane system for recovery of 2-keto-L-gulonate
    J. Wei
    1
    , L. Zhang
    2
    , S. Wang
    3
    1
    Alfa Laval Nakskov A/S, Stavangervef 10, DK-4900 Nakskov, Denmark
    2
    Northeast General Pharmaceutical Factorv, Shenvang 110026, China
    3
    Alfa Laval (Shanghai) Technologies Co., Ltd. 98 Huai Hai Road M., Shanghai, China
    jiang.weialIalaval.com
    UltraIiltration with plate & Irame membrane system is used Ior the recovery oI 2-keto-L-gulonate (2KLG), an important
    intermediate oI vitamin C in Northeast General Pharmaceutical Factory, China. UltraIiltration is a new process to remove
    proteins and bacterial debris in the Iermentation broth and the membrane process shows advantages over other processes, e.g.
    precipitation or Ilocculation. Results oI ultraIiltration with two diIIerent membrane modules, AlIa Laval M38 and M39 are
    presented and compared with respect to the characteristics oI the two modules. This work shows that Iermentation broth
    without pre-treatment (e.g. centriIugation) can be Iiltered with the latest module M39. The membrane process has been
    operating in the production line Ior more than 10 years in Northeast General Pharmaceutical Factory, and the operational
    experience is summarized in the paper.
    -327-
    0.000 0.001 0.002 0.003 0.004 0.005 0.006
    -1000
    0
    1000
    2000
    3000
    4000
    5000
    6000
    7000
    D
    e
    r
    i
    v

    e

    (

    -
    V
    )
    Current(A)
    B'2(NH4)
    2
    SO
    4
    F'1Na
    2
    SO
    4
    H'K
    2
    SO
    4
    E'Li
    2
    SO
    4
    (a)
    0.0022
    0.000 0.001 0.002 0.003 0.004 0.005 0.006
    -1000
    0
    1000
    2000
    3000
    4000
    5000
    d

    r
    i
    v

    e

    courant(A)
    E'Li
    +
    (b)
    0.00369
    0.00585
    0.000 0.001 0.002 0.003 0.004 0.005 0.006
    0
    1000
    2000
    3000
    4000
    5000
    6000
    d

    /
    d
    V
    courant(A)
    B'1NH
    4
    +
    (c)
    Figure 1: The instantaneous diIIerential ddp tranmembranaire/I at a given current. (Iour
    electrode cell, Free convection , AutolabPGSTAT30)
    PD.1.33
    Two-layer mass transfer rate`s equation foe separation by pervaporation of dilute
    aqueous solution
    E. Nagy
    Universitv of Pannonia, Research Institute of Chemical and Process Engineering, P.O.Box 158, 8201 Jes:prem, Hungarv,
    Tel..00-36-624040, Fax. 00-36-624038
    nagyemik.uni-pannon.hu; nagymukki.richem.hu
    The negative eIIect oI the stagnant concentration boundary layer on the mass transport through a membrane has been
    investigated Ior a long time. It was proved that this layer can be a major limiting Iactor in various membrane separation
    processes as e.g. gas separation, pervaporation, etc. The well know polarization equation (C
    m
    -C
    p
    )/(C
    b
    -C
    p
    )exp(Pe), e.g. |1|}
    does not give, however, any inIormation how the mass transport parameters oI the membrane matrix, e.g. the solubility
    coeIIicient, membrane Peclet number, can aIIect the concentration proIile oI the boundary layer, and consequently, the
    separation eIIiciency. Question to be answered is how the C
    p
    value (concentration in permeate) is aIIected by the mass
    transport properties oI the membrane layer in presence oI the concentration polarization layer containing convective Ilow, as
    well. This is not investigated in detail yet. This paper gives the suitable mathematical expressions, in order to predict the well
    known parameters as polarization modulus, enrichment Iactors, etc., taking into account the transport parameters Ior both the
    concentration boundary and the membrane layers, and discusses the concentration distribution and the polarization modulus. It
    will also be deIined the mass transIer rate as a Iunction on the mass transport properties oI the both layer which IulIill J
    L
    C
    p
    boundary condition. The equations developed enable us to calculate the mass transIer by means oI mass transIer properties oI
    the layers without knowing the outlet or membrane interIace concentrations. It will be shown how the transport properties oI
    the membrane layer aIIect the concentration proIiles oI the boundary layer and thus, the polarization modulus, enrichment
    Iactors, etc., as well. As a case study pervaporation oI dilute organic components will be discussed.
    |1| R.W. Baker, J.G. Wijmans, A.L. Athayde, R. Daniels, J.H., Ly, M.Le, The eIIect oI concentration polarization on the
    separation oI volatile organic compounds Irom water by pervaporation, J. Membrane Sci., 137 (1997) 159-172
    PD.1.34
    Application of membrane technology at pilot plant scale to manufacture
    concentrated colored polyphenolic water extracts from tropical vegetal biodiversity
    F. Adje
    1
    , W. Suttivattanavet
    2
    , F. Guinle
    1
    , C. Moquet
    1
    , L. Meng
    3
    , A. N`Daye
    4
    , S.F. Wang
    5
    , Y. Lozano
    1
    1
    CIRAD, UMR GPEB, Genie des Procedes, Eau, Bioproduits, TA 40/16, 73 avenue J.F. Breton, 34398 Montpellier cedex 5,
    France.
    2
    Thailand Institute of Scientific and Technological Research (TISTR), 35 Moo 3 Technopolis, Tambon Klong 5, Amphoe Klong
    Luang Pathumthani 12120, Thailand.
    3
    South China Agricultural Universitv (SCAU), 483 Wushan Road, 510642 Guang:hou, China.
    4
    Institut de Technologie Agroalimentaire (ITA), route des Peres Maristes, Dakar, Senegal
    5
    Fufian Subtropical Horticultural Botanv Research Centre (FSHBRC), East Shengli Road, 363000 Zhang:hou, China.
    yves.lozanocirad.Ir
    Various plants Irom the tropical biodiversity are traditionally used to produce ingredients locally used in medicinal,
    pharmaceutical, cosmetic and beverage preparations. Tree leaves and Ilower petals are soaked in cold or hot water, at home
    scale, to prepare colored (generally red) and active (antioxidant) natural extracts, containing mainly polyphenolic compounds.
    Coupled Membrane separation technology, including Cross Flow MicroIiltration (CFM) and Reverse Osmosis (RO) was used
    to scale up such traditional extraction processes. At pilot plant scale, Iresh or dry vegetal were processed to produce, Ior local
    marketing, liquid concentrates oI natural water-soluble biomolecules including anthocyanins, Ilavones and acid-phenols.
    Membranes used in these pilot plant units were oI industrial types: a multi-channel ceramic membrane Ior CFM and a Iolded
    polymeric membrane Ior RO.
    Large volume oI tap water was used (250L) to extract, at one time, dried or Iresh material in a ratio oI 1/100 (w/w). Vegetal
    Iirstly macerated overnight to allow soluble biomolecules to diIIuse in water. CFM was conducted in a second step using a
    single P19-60 membrane oI 0.2m pore size and 0.304m
    2
    total Iiltration surIace. The operating transmembrane pressure (TMP)
    was maintained at 0.6b during the whole Iiltration step conducted at room temperature (25-30C). The Iiltration Iluxes were
    regularly recorded until the end oI the CFM steps (5-11h) Ior every material processed. A dead volume (10L) was generally
    -328-
    leIt unIiltered in the pilot plant unit. In a third step, the microIiltrated extracts were concentrated by RO using a SW30 type
    membrane (2m
    2
    ) at TMP40b and at 25-30C maintained by an on-line exchanger. The Volume Reduction Factor (VRF) oI
    the microIiltrated extracts achieved by RO was generally raised up to 100, resulting oI the Iixed ratio between the concentrate
    dead volume in the RO pilot plant (2L) and the initial CFM volume processed at once (200L).
    Petals Irom various Hibiscus sabdariffa Ilower cultivars, harvested in Thailand or in AIrica, were extracted with tap water, and
    Carapa Procera tree leaves and Delonix regia tree Ilowers, originated Irom Ivory Coast, were soaked in water, acidiIied with
    sulIuric or citric acid 0.05N that lead to diIIerent polyphenol extraction yields. For Hibiscus extracts, CFM Iluxes started at
    600 and stabilized Ior 2.5h at 200L.h
    -1
    .m
    -2
    .b
    -1
    , 2.5h aIter CFM start. For Carapa and Delonix extracts, stabilized Iluxes
    obtained were both around 100L.h
    -1
    .m
    -2
    .b
    -1
    , using the same CFM conditions. RO concentration steps showed water elimination
    Iluxes oI 20, 16 and 17L.h
    -1
    .m
    -2
    respectively, leading to concentrated extracts oI only 15, 11.7 and 9.6 dry matter, compared
    to the 0.3 Ior the CFM extracts obtained Irom the 3 plants processed. Recovered pure water (~200L) can be recycled in the
    process and the extracted vegetal returned to the Iields. The concentrated extracts showed low microbial loads.
    Membrane technology was shown to have new eco-Iriendly applications Ior manuIacturing added-value extracts Irom plants oI
    the tropical biodiversity. Small-scale or industrial level pilot plants can operate even in low technical environments generally
    Iound in southern developing countries. Process perIormances were oI good levels to manuIacture marketable concentrated
    water-extracts oI polyphenols Irom various local plants, traditionally used by village communities.
    PD.1.35
    Coupling of membrane technology to add value to small-industrial scale micro-algae
    biomass production: a step toward sustainable development in the southern
    hemisphere
    K Mathis
    1
    , Y. Lozano
    1
    , S. Petitperrin
    1,2
    , P. Lozano
    1
    1
    CIRAD, UMR GPEB, Genie des Procedes, Eau, Bioproduits, TA 40/16, 73 avenue J.F. Breton, 34398 Montpellier cedex 5,
    France.
    2
    ISUA, Domaine de Montroche, 30900, Nimes, France.
    yves.lozanocirad.Ir
    Today micro-algae is receiving considerable interest due to it great potential as an alternative source oI biomass which can
    provide intermediates Ior agroIood, pharmacy, cosmetic and energy sectors. Three major inputs are necessary to grow micro-
    algae: light, heat and water. The two Iirst are Ireely available in tropical countries, making micro-algae an excellent potential
    source oI biomass, as long as the water resources are managed.
    Despite the potential oI micro-algae there are a number oI technical issues, not least de-watering. When harvested the dry
    matter is generally low typically (~1g/L), thereIore large quantities oI water have to be removed or recycled. In our study we
    produced the algal biomass, using diIIerent Ieed ingredients: pure chemical mixtures or more ecological/natural substrates
    extracted Irom local vegetal. Biomass was grown either in a conventional plastic tubes (100L/unit) or in innovative bioreactors
    (75L) developed in house so as to accommodate small industrial scale production adapted to conditions in Developing
    Countries (DC).
    We have demonstrated the use oI membrane technology, at pilot plant level, to concentrate microalgae biomass or/and to
    recover and concentrate water-soluble metabolites produced during the production cycle. Coupled Membrane Separation
    Technology (CMST), including Cross Flow MicroIiltration (CFM) and Reverse Osmosis (RO) was used to scale up the
    process. Membranes used in these pilot plant units were oI industrial types: a multi-channel ceramic membrane Ior CFM
    (P19-60 membrane, 0.2m pore size, S0.304m
    2
    Iiltration surIace) and a Iolded polymeric membrane Ior RO (SW30
    membrane, S2m
    2
    ).
    To illustrate the Ilexibility oI the system a range oI microalgae i.e.Porphvridium cruentum, Arthrospira platensis and
    Odontella aurita were produced at a scale oI 5-10m
    3
    /batch. Biomass was harvested using this CMST and water-soluble
    metabolites were been extracted. From biomass concentration, water elimination Iluxes were generally stabilized, just 1h aIter
    CFM start, until the end oI the process (4-7H) at 100-200L.h
    -1
    .m
    -2
    .b
    -1
    (TMP0.8-1b, T25-30C), depending oI the nature oI
    the micro-algae biomass processed. The dry matter oI the biomass was concentrated 15-20 times, limited by the total volume
    oI the biomass generally processed at one time (200-500L) and the Iixed dead volume oI the CFM pilot plant (10L). The
    clariIied water obtained by CFM was then processed by RO to concentrate valuable metabolites, such as phycocyanin,
    phycoerythrin, etc. CFM concentrated biomass and RO concentrated metabolite solutions were then turned into powder by
    direct spray-drying. The study demonstrates the utility oI membrane technology as part oI micro-algae exploitation.
    |1| M.T. Hung, J.C. Liu, MicroIiltration Ior separation oI green algae Irom water, Colloids and SurIaces B: BiointerIaces,
    2006, 51, 157-164.
    |2| G. Beccera, H. Desmourieux, S. Brianon, S. Khenniche, J. Albiol, Culture et sechage de la spiruline par atomisation,
    Recents Progres en Genie des Procedes, 2005, 92, 10 Congres de la SFGP, Toulouse 2005.
    -329-
    |3| P. Jaouen, B. Lepine, N. Rossignol, R. Royer, F. Quemeneur, ClariIication and concentration with membrane technology oI
    a phycocyanin solution extracted Irom Spirulina platensis, Biotechnology Techniques, 1999,13, 877-881.
    PD.1.36
    Preparation of supports and membranes for micro-filtration using native raw
    materials
    A. Harabi
    1
    , F. Zenikheri
    1
    , F. Bouzerara
    2
    , B. Boudaira
    1
    , S. Condom
    3
    1
    Constantine Ceramics Laboratorv, Mentouri Universitv, Constantine 25000, Algeria.
    2
    Laboratoire detude des materiaux, Universite de Jifel, Jifel 18000, Algerie.
    3
    Institut Europeenne des Membranes, UMR 5635 CNRS ENSCM UMII, 1919 Route de Mende, 34293 Montpellier Cedex 5,
    France.
    Harabi52gmail.com
    Considering water as a source oI liIe, water pollution has been Ior a long time, one oI the primary subjects oI scientiIic
    researches and studies.
    Water is becoming more and more rare in nature, and taking into account its great importance as a liIe depending matter and as
    an essential Iactor in industrial Iields, many researches are oriented to Iind out new techniques that able people making hard
    and waste water beneIicial. One oI these techniques is the puriIication oI water using ceramic Iilters or what is called the
    membranes technique. This technique is based on Iilters containing membranes used in the micro-Iiltration and the ultra-
    Iiltration oI water.
    The Iirst and main step in the process, is the preparation oI membranes supports, using local raw materials: Kaolin DD3 and
    calcium carbonates CaCO
    3
    extracted Irom Djebbel Debbagh (Guelma) and Constantine regions, respectively. These supports
    are shaped by using two pressure techniques in order to get supports in the Iorm oI disks and tubular ones which were sintered
    aIterwards at diIIerent temperatures .
    A preliminary study is carried out on supports having small dimensions R21 mm, so that a small amount oI raw materials is
    used. The major task oI this work is to Iind out the appropriate amount oI CaCO
    3
    in the Iinal mixture. That is why CaCO
    3
    is
    added in diIIerent proportions (10, 15, 20, 25, 28, 30 wt) into the kaolin DD3, then the mixture is sintered at a given
    temperature (1300C). According to the obtained results, it has been Iound that the pore sizes distributions are almost
    homogeneous (mono-modal type).
    By Iollowing the same steps but using the technique oI extraction, tubular supports are made.
    As a last step, membranes elaborated Irom titanium oxide are placed on the supports using slip casting technique. Those
    specimens were subsequently sintered at 1100C. The microstructure, porosity as well as the permeability have been also
    studied.
    It has been Iound that the average pore size is about 0.45 m , a layer thickness - 22.7 m and a permeability coeIIicient
    K520 l/hm
    2
    . These obtained membranes are selected to be used in the micro-Iiltration.
    A Iurther important application in this work is waste and hard waters puriIication using membranes technique. In Iact, this new
    technique gives the opportunity to human beings to maintain nature.
    PD.1.37
    Understanding the recovery of ionic liquids by nanofiltration: combining classical
    characterization methods with T-SAR approach
    J.F. Fernandez
    1,2
    , R. Bartel
    1
    , J. Thming
    1
    1
    UFT- Centre for Environmental Research and Sustainable Technologies, Universitv of Bremen, 28359 Bremen, Germanv
    Phone. 49 (0)421 21863373, Fax. 49 (0)421 2188297
    2
    Chemical Engineering School, Central Universitv of Jene:uela, 1040 Caracas, Jene:uela
    Ieuni-bremen.de
    NanoIiltration (NF) membranes could be applied Ior the recovery oI ionic liquids Irom aqueous solutions, avoiding their
    entrance into the environment and providing a useIul contribution in the Iields oI ionic liquids reuse and recycling |1|. Ionic
    liquids consist typically oI organic cations (imidazolium, pyridinium, pyrrolidinium, ammonium or phosphonium) and mostly
    -330-
    inorganic anions, and it is well known that the separation process in nanoIiltration is strongly inIluenced by both charge and
    size interactions.
    However, there are still many unclear aspects about the role oI the NF-membranes in the selective separation oI ionic liquids,
    in which the interactions between the membrane and the ionic liquid structures are determining Iactors. Fortunately, a
    comprehensive characterization concerning morphology, charge and separation parameters oI several commercially available
    NF-membranes was recently done |2,3|.
    In this work, we took advantage oI the results provided Ior classical methods oI membrane characterization and combined it
    with a theoretical approach T-SAR (Thinking in terms oI Structure Activity Relationships) in order to predict the perIormance
    oI several commercially available membranes Ior the recovery oI ionic liquids. Additionally, the expected perIormance Ior
    each membrane was evaluated with experimental data. This approach appears as a powerIul tool Ior the selection oI the
    appropriate membrane between a pool oI existing options, as well as a design guideline Ior the development oI new
    membranes Ior a speciIic application.
    |1| J.F. Fernandez, E. Chilyumova, D. Waterkamp, J. Thming, Ionic liquid recovery Irom aqueous solutions by cross-Ilow
    nanoIiltration, Proceedings oI the 10
    th
    World Filtration Congress, 2008, Volume II, 528-532.
    |2| C.Y. Tang, Y.N. Kwon, J.O. Leckie, EIIect oI membrane chemistry and coating layer on physiochemical properties oI thin
    Iilm composite polyamide RO and NF membranes I. FTIR and XPS characterization oI polyamide and coating layer
    chemistry, Desalination, 2009, 242, 149-167.
    |3| C.Y. Tang, Y.N. Kwon, J.O. Leckie, EIIect oI membrane chemistry and coating layer on physiochemical properties oI thin
    Iilm composite polyamide RO and NF membranes II. Membrane physiochemical properties and their dependence on
    polyamide and coating layers, Desalination, 2009, 242, 168-182.
    PD.2.1
    Double-membrane reactor for gas phase hydroxylation of aromatics: effect of the
    catalytic properties of the Pd-based membrane
    L. Bortolotto, R. Dittmeyer
    DECHEMA e.J., Karl-Winnacker-Institute, Frankfurt am Main, Germanv
    bortolottodechema.de
    A microstructured double-membrane reactor was developed Ior the study oI the direct hydroxylation oI aromatic compounds in
    the gas phase. Direct hydroxylation oI aromatics in a Pd membrane reactor has been investigated in several places since 2002,
    with deviating results |1-5|, raising interest in Iurther analysis. The study is Iocused on the gas phase conversion oI benzene to
    phenol, with dosage oI H
    2
    and O
    2
    in the reactor via 2 separate membranes (see Fig. 1) Ior improved control oI the H
    2
    /O
    2
    concentration ratio along the reaction channel. A Pd-based membrane allows Ior diIIusion and dissociation oI hydrogen
    molecules in the system while an Ag membrane supplies oxygen Ior the Iormation oI active species on the surIace oI the Pd
    membrane.
    Fig. 1: Microstructured reactor Ior benzene hydroxylation with separate dosage oI oxygen and hydrogen
    In line with Iinding reported by Vulpescu et al. |5|, we Iound CO
    2
    as the dominant product in the system, together with water.
    The best phenol selectivity obtained so Iar is 9.6 at 150C using membrane Ioils. The O
    2
    dosage via a 2
    nd
    membrane led to a
    5 times higher phenol selectivity than in O
    2
    co-Ieed together with benzene at the reactor entrance under the same conditions,
    proving the success oI the basic idea behind the reactor design.
    In current investigations, the surIace properties oI the Pd-based membrane are modiIied, with the aim oI increasing the phenol
    selectivity. DiIIerent active systems will be applied by magnetron sputtering oI catalytic elements, like intermetallic species or
    oxide-supported metallic particles. The eIIect oI these systems on the phenol production will be discussed, as well as the role
    oI the membranes in the control oI the gas composition in the reactor.
    -331-
    |1| S. Niwa, M. Eswaramoorthy, J. Nair, N. Itoh, H. Shoji, T. Namba, F. Mizukami, Science 295 (2002) 105.
    |2| N. Itoh, S. Niwa, F. Mizukami, T. Inoue, A. Igarashi, T. Namba, Catal. Comm. 4 (2003) 243.
    |3| K. Sato, S. Niwa, T.a. Hanaoka, K. Komura, T. Namba, F. Mizukami, Catal. Letters 96 (2004) 107.
    |4| K. Sato, T. Hanaoka, S. Niwa, C. SteIan, T. Namba, F. Mizukami, Catal. Today 104 (2005) 260.
    |5| G.D. Vulpescu, M. Ruitenbeek, L.L. van Lieshout, L.A. Correia, D. Meyer, P.P.A.C. Pex, Catal. Comm. 5 (2004) 347.
    PD.2.2
    Enzyme-facilitated enantioselective transport of (S)-lactic acid through a SLM based
    on ionic liquids
    E. Kulcsar, E. Nagy
    Research Institute for Chemical and Process Engineering Universitv of Pannonia H-8200 Jes:prem Egvetem u. 2 Hungarv
    kulcsaredinaIreemail.hu
    The signiIicance oI lactic acid arises Irom its utility as a monomer Ior biodegradable solvents and polymers in which the
    hydroxyl and the carboxyl Iunctional groups permit it to participate in a wide variety oI chemical reactions Lactic acid esters
    are nontoxic and biodegradable materials having excellent solvent properties and could potentially replace toxic and
    halogenated solvents Ior a wide range oI industrial and consumer uses.
    Our work has been Iocused on enantioselective transport oI the (S)-enantiomer Irom racemic lactic acid through a lipase-
    Iacilitated SLM based on ionic liquids.
    (S)- lactic acid is selectively esteriIied by Candida antarctica in the Ieed phase, and the resulting ester dissolves into the ionic
    liquid phase oI the SLM and diIIuses across the SLM. In the receiving phase PPL catalyses the ester hydrolysis to produce the
    initial lactic acid and ethanol. Finally, the (S)-lactic acid is selectively transported through the SLM.
    PD.2.3
    The enzymatic hydrolysis of preparations of potato starch in continuous recycle
    membrane reactor and adsorption characteristics of the obtained products
    K. Prochaska
    1
    , E. Konowal
    1
    , J. Sulej
    1
    , G. Lewandowicz
    2
    1
    Institute of Chemical Technologv and Engineering, Po:nan Universitv of Technologv, Pl. M. Sklodowskief Curie 2, 60-965
    Po:nan, Poland
    2
    Department of Biotechnologv and Food Microbiologv, Po:nan Universitv of Life Sciences, ul. Wofska Polskiego 48,
    60-627Po:nan, Poland
    krystyna.prochaskaput.poznan.pl
    The enzymatic hydrolysis oI starch is traditionally perIormed in large volume batch reactors using soluble enzyme Iollowing a
    two-step procedure including the liqueIaction and sacchariIication. Batch processes entail a great number oI disadvantages
    such as low eIIiciency, batch to batch variations, and most oI all, the high enzyme cost due to necessity oI its inactivation and
    separation Irom the Iinal product. The introduction oI membrane reactors brings the possibility oI a continuous operation in
    lower volume reactors in shorter reaction time.
    In the presented work we studied the possibility oI the application oI continuous recycle membrane reactor (CRMR) Ior the
    enzymatic hydrolysis oI chemically modiIied starches. Moreover, the surIace properties oI the obtained hydrolyses were
    considered. Several Iood grade modiIied starches, which were successIul at Polish market, due to its miscellaneous Iunctional
    properties, were investigated.
    The hydrolysis process was carried out in a CRMR equipped with ultraIiltration module containing ceramic membrane oI
    tubular conIiguration. The membrane process was perIormed over a period oI 180 minutes at the temperature oI 60C, at the
    transmembrane pressure oI 0.3 MPa and with the 0.3 ml oI enzyme preparation BAN 480 L per 1 kg oI starch. The Iiltrate
    Iraction was collected while the retentate were recycled back. The constant level oI volume oI the reaction mixture was
    controlled. The loss oI the reaction mixture volume was supplemented with starch solution.
    AIter completion oI the process, the collected permeate and retentate Iractions were dried with spray dryer. The surIace
    tension Ior obtained products oI hydrolysis were measured by the du Noy ring method with a KRSS K12 tensiometer
    (Germany) and the experimentally determined surIace/interIace tension isotherms were interpreted.
    -332-
    It was Iound that the susceptibility to enzymatic hydrolysis oI modiIied starches is aIIected by the type oI modiIying groups as
    well as the degree oI substitution. The hydrodynamic properties oI applied CRMR were determined mainly by the rheological
    properties oI the Ieed and retentate Iractions.
    Moreover, it was shown that the hydrolysis oI modiIied derivatives oI potato starch leads to obtain the products which reveal
    the adsorption properties and reduced surIace/interIace tension in air/water and oil/water systems. The eIIiciency and
    eIIectiveness oI adsorption oI investigated hydrocolloids were aIIected by the type oI modiIication as well as the degree oI
    substitution oI starch macromolecules.
    PD.2.4
    Porous membrane catalytic systems for conversion of bioorigin organics into
    hydrogen and syngas
    V. Zhmakin
    1
    , A. Fedotov
    1
    , D. Roizard
    2
    , V. Korchak
    3
    ,
    V. Uvarov
    4
    , V. Teplyakov
    1
    , M. Tsodikov
    1
    1
    A.J. Topchiev Institute of Petrochemical Svnthesis RAS, 29 Leninskiv prospect, 119991, Moscow, Russia
    2
    Groupe ENSIC-LSGC, 1 Grandville, BP 451, 54001 Nancv, France
    3
    N.N. Semenov Institute of Chemical Phvsics RAS,4 Kosvgina st, 119991, Moscow, Russia
    4
    Institute of Structural Macrokinetics and Materals Science RAS, Chernogolovka, 142432, Moscow region, Russia
    Zhmakinips.ac.ru
    Hydrogen and other valuable substances generation by using oI bioorigin organics is important Ior energy and chemical
    industry. Accumulation oI Iundamental knowledge and perspective applied aspects in this Iield can be connected with porous
    membrane catalytic systems which can be considered as 'ensemble oI catalytic microreactors. In this case several general
    advantages oI microreactors can be noted: compactness oI industrial installations, easy scaling up oI membrane unit and good
    control oI the process operation. The most prospective trends in this area are the processes oI methane conversion into
    hydrogen and syngas as well as the steam reIorming oI other bioproducts such as ethanol, acetic acid, etc.
    For this purpose several types oI catalytic ceramic membranes, which are active in this reaction were synthesized. Set oI
    experiments showed that methane conversion occurred intensively already at 400
    o
    C and reaction oI above steam reIorming
    runs about 250
    o
    C, which is much lower then in traditional reactor with a loaded layer oI catalyst. We believe that this
    diIIerence is because oI heat and mass transIer, which is better in microporous membrane as well as numerity oI molecule
    collisions in membrane channels is deIinitely higher. In our experiments catalysts were placed to the membrane channel walls.
    We studied membranes themselves and modiIied ones in above mentioned catalytic reactions. All studied membranes had
    diIIerent composition and activity in processes oI methane conversion and steam reIorming but practical interest Ior dry
    reIorming oI methane represented Ni-Al membranes modiIied by La-Ce and Pd-Mn catalysts. As to steam reIorming the most
    promising membranes were ones modiIied by Pd-based catalysts. It was shown that La-Ce on Ni-Al has higher activity in dry
    methane reIorming than Ni-Al/Pd-Mn (Ni-Al/La-Ce: p
    syngas
    -4000 l/dm
    3
    reactor
    h; Ni-Al/Pd-Mn: p
    syngas
    -3300 l/dm
    3
    reactor
    h;
    conditions: T600
    o
    C, W
    Ieedstock
    40 l/h, CH
    4
    /CO
    2
    1). In the same time the H
    2
    /CO ratio in product is also diIIerent (at T600
    o
    C it
    is 1.25 on Ni-Al/Pd-Mn, it is 0.63 on Ni-Al/La-Ce). By using oI the setup equipped by highly sensitive balance and mass-
    spectrometer direct and side reactions carrying out in methane dry reIorming process were studied in order to explain the
    selectivity oI the process. As to steam reIorming the highest productivity during conversion oI acetic acid was obtained Ior Pd/
    Ni-Al membrane (up to 600 l/dm
    3
    h), but the highest conversion was observed Ior Pd-Co/Ni-Al (up to 100) membrane. It
    was shown that the highest conversion oI ethanol was also up to 100 on Pd-Co and Pd-Zn membranes. The conditions oI all
    steam reIorming experiments were Iollowing: W
    liquid Ieed
    0,5 ml/min, W
    carrier gas
    10 l/h, composition oI liquid Ieed was 1:13
    ethanol (or acetic acid respectively):water. Particularities and prospects oI catalytic membrane microreactors studied are
    considered.
    This work is partially supported by Grant RFBR No 08-03-92496
    -333-
    PD.2.5
    Conception and study of an enzymatic membrane reactor for the treatment of
    effluents with phenolic compounds
    V. Chea, D. Paolucci-Jeanjean, J. Sanchez, M.P. Belleville
    Institut Europeen des Membranes (IEM). ENSCM, UM2, CNRS - Universite de Montpellier II, CC 047 , Place Eugene
    Bataillon - 34095 Montpellier, France.
    marie-pierre.bellevilleiemm.univ-montp2.Ir
    Phenolic compounds present in some industrial and domestic eIIluents are generally toxic and need to be treated beIore being
    rejecting in the environment. Biological treatments involving micro-organisms can only be used iI phenol concentrations are
    relatively low due to phenol toxicity. At high phenol concentrations enzymatic degradation oI such compounds can be an
    interesting alternative to microbial one |1|. Actually, laccases, which are oxidative enzymes, transIorm phenolic compounds
    into Iree radicals. Then these radicals react together Iorming polymers which can be easily eliminated Irom eIIluents.
    In this work, an enzymatic membrane reactor is used Ior the removal oI phenolic compounds Irom an aqueous solution. The
    enzymatic membrane was prepared by coating a ceramic porous support with a gelatine layer. Laccase was then covalently
    attached to amine groups oI the gelatine via glutaraldehyde as described in a previous work |2|. Using such graIting method,
    biocatalysts is immobilized onto the surIace oI the ceramic grains Iorming the membrane and the reaction takes place on the
    surIace and inside the membrane porosity where the catalyst is located allowing high conversion. In addition, the Iormation oI
    polymers occurs aIter the transIer across the membrane thus limiting membrane Iouling.
    The perIormances oI the enzymatic membrane reactor were Iirst evaluated in batch mode (retentate and permeate were
    recycled into the Ieed tank) and phenolic compounds degradation was Iollowed-up along the time by HPLC analysis. The
    results obtained conIirmed the eIIiciency oI the active membrane. Among the diIIerent substrates tested (4-chlorophenol,
    guaiacol and 2,6-dimethoxyphenol), only the 2,6-dimethoxyphenol was completely degradated aIter less than 60 minutes and
    then was chosen Ior Iurther experiments.
    In the second part oI the study, reactions were carried out on continuous dead-end Iiltration mode and the eIIect oI the Ieed
    Ilow rate and oI the addition oI copper ions were evaluated.
    |1| N. Duran, E. Esposito, Potential applications oI oxidative enzymes and phenoloxidase-like compounds in wastewater and
    soil treatment: a review, Applied Catalysis B: Environmental, (2000) 28, 83-99.
    |2| M. P. Belleville, P. Lozano, J. L. Iborra, G. M. Rios, Preparation oI hybrid membranes Ior enzymatic reaction, Separation
    and PuriIication Technology, (2001) 25, 229-233.
    PD.2.6
    Continuous membrane bioreactor system with submerged ceramic flat membranes
    for the production of lactic acid
    T. Hahn
    1
    , Z. Kovacs
    1
    , S. Schieber
    1
    , I. Hannemann
    1
    , K. Grau
    1
    , H.J. Schmidt
    3
    , P. Czermak
    1,2
    1
    Institute of Biopharmaceutical Technologv, Universitv of Applied Sciences Giessen-Friedberg, Wiesenstrasse 14, 35390
    Giessen, Germanv (infoibpt.de, http.//www.ibpt.de)
    2
    Department of Chemical Engineering, Kansas State Universitv, Durland Hall 105, Manhattan KS, USA
    3
    Membrane engineering GmbH, 88682 Salem, Germanv hf.schmidtmembrane-engineering.de
    Tobias.Hahntg.Ih-giessen.de
    Most oI the organic acids, such as citric and lactic acid, are commercially produced by Iermentation in bioreactors. A major
    objective oI Iermentation in industry and research is to maximize the volumetric productivity. Membrane bioreactors (MBR)
    give the possibility Ior continuous process with cell recycle to obtain high cell concentration and thereIore high volumetric
    productivity. In this device the biocatalyst, enzymes or whole cells are retained by means oI membrane. Recycle systems
    normally used are installed in an external loop including tubular polymeric membranes. In this work, ceramic Ilat membranes
    were submerged in the reactor Ior achieving a high cell concentration with low product inhibition (Fig. 1). The active layer oI
    the membrane is directly Iaced with the Iermentation broth. Minimizing clogging and bioIouling eIIects, Iluid dynamic
    impacts, back-Ilushing and potential bubble input were investigated in this aqueous-two-phase-system and compared to an
    external cell recycle conIiguration (tubular ceramic membrane).
    -334-
    The eIIiciency oI this continuous process using two diIIerent bacillus strains regarding to the biomass concentration, medium
    properties and the control oI bioIouling was examined.
    Figure 1 leIt: ceramic Ilat membranes; right: Ilow sheet
    PD.2.7
    Back-flush influence on microbial membrane bioreactor characteristics
    A. Noworyta, T. Grygier
    Wroclaw Universitv of Technologv, Facultv of Chemistrv, Division of Chemical and Biochemical Processes, Wvbr:e:e
    Wvspianskiego 27, 50-370 Wroclaw
    andrzej.noworytapwr.wroc.pl
    The model oI the membrane bioreactor with cells deposition on the membrane and the back-Ilushing was presented in the
    paper. The microbial transIormations with inhibition were taken into special consideration. Possible microorganisms behaviour
    on the membrane was discussed. Models describing phenomena connected with cells deposition are oIten considerably
    complex |1|, what makes the prediction oI the overall apparatus perIormance diIIicult. Especially in the case oI highly
    dynamical system i.e. membrane bioreactor with back-Ilushing. Incorporating these phenomena into balance equations is then
    legitimate. The model was Iormulated and several numerical experiments were carried out. The possible behaviour oI the
    system ranges Irom the wash out or
    excess concentration to repeatable
    concentration proIiles. The last one being
    in Iact pseudo-stationary state stands Ior
    the main object oI investigations
    presented in the paper (Iig.1). In the
    discussed system there are de Iacto two
    reaction zones Iirst in the main vessel
    volume and the second in the
    dynamically Iormed bioIilm. The system
    behaviour is determined by constituents
    distribution between these two zones.
    Some interesting phenomena may by
    observed Ior reactions with inhibition
    especially in addition to the Iact that
    kinetics in both regions oIten diIIer |2|.
    Incorporating some simpliIications in the
    overall model equations makes
    obtaining analytical solutions possible.
    ThereIore the discussion may be
    supported by simple mathematical
    Iormulas allowing the assessment oI the
    optimal back-Ilush Irequency. Presenting
    obtained results the authors made an
    -335-
    Fig. 1. Sample concentration proIiles Ior a singe reactor switched between two
    operating modes visible obtained pseudo-stationary state.
    Biomass concent rat ion |g/dm
    3
    |
    u - Conversion Iact or
    Subst rat e concent rat ion
    No cells deposition nor
    back-Ilushing
    Both cells deposition and
    back-Ilushing pseudo-
    stationary state
    time |h|
    u
    eIIort to characterize primary reasons Ior observed phenomena and to Iormulate practical conclusions regarding proper
    selection oI the membrane bioreactor operating parameters.
    |1| H. Beyenal, Z. Lewandowski, Modeling mass transport and microbial activity in stratiIied bioIilms, Chemical Engineering
    Science, 2005, 60, 4337-4348
    |2| C. A. Kumamoto, Candida bioIilms, Current Opinion in Microbiology, 2002, 5, 608-611.
    PD.2.8
    Study of the influence of the components of a microbial culture medium (micro-
    organisms and soluble compounds) on fouling and species retention in a double
    membrane bioreactor
    J. Gnther
    1, 2
    , P. Loubiere
    2
    , C. LaIIorgue
    2
    , C. Albasi
    1
    1
    Laboratoire de Genie Chimique, UMR CNRS 5503, 5 rue Paulin Talabot, BP 1301, 31106 Toulouse cedex 01, France
    2
    Laboratoire dingenierie des Svstemes Biologiques et des Procedes, UMR INSA CNRS 5504, UMR INSA INRA 792, 135
    avenue de Rangueil, 31077 Toulouse cedex 04, France
    Most oI microbiological processes used to implement microbial consortia. Their perIormances strongly depend on
    microorganism`s interaction phenomena. Thus, numerous works try to analyze these complex mechanisms between the
    microbial species. A speciIic bioreactor has been previously designed in order to study microbial interactions (Albasi et al
    1998): a physical separation oI the species in two tanks is realized thanks to a microIiltration membrane. The homogeneity oI
    the culture medium between the two compartments is allowed by a periodic inversion oI the permeate Ilow, driven by a
    sequential gas compression (Salgado 1999, Salgado et al. 2000). The resulting Ilow creates an auto-cleaning process. In order
    to guarantee cultivation conditions similar than those that could be obtained in a single reactor, two criteria have to be
    respected (i) the mixing velocity should not be restrictive to biological kinetics (ii) the molecular compounds involved in the
    microbial metabolism must cross the membrane.
    However, it can be assumed that the reversibility oI the Iouling cake on the membrane depends not only on the operating
    conditions (exchanged volume and compression level) but also on the speciIic properties oI the culture medium. The
    perIormances oI the microIiltration, under diIIerent trans-membrane pressure, were Iirst investigated Ior model media, BSA
    solution (2 g.l
    -1
    ), yeast suspension (8 g.l
    -1
    , dry mass) and mixture oI both. The net permeat Iluxes Ior the mixture were
    proportional to the applied transmembrane pressure but were less than those obtained with osmosis water showing that, in spite
    oI a periodical backwash, a small part oI irreversible Iouling remained. It could be due to both an internal Iouling by protein
    and an external Iouling by a residual cake. Moreover, the net permeate Ilux obtained with the mixture was higher than that
    with the BSA alone: a small yeast cake could act as a primary Iiltration layer, protecting the polysulphone membrane against
    protein Iouling
    This bioreactor will be applied to the study oI 'bacteria/yeast interaction phenomena in a simpliIied dairy media in the case oI
    the model microorganisms . Lactococcus lactis and Yarowia lipolvtica
    ALBASI C., RIBA J.P., MONNA J.P., ESPENAN J.M, 1998, Procede et appareil pour l`homogeneisation de deux milieux
    liquides contenant des composants solides ou dissous et/ou des micro-organismes, brevet depose le 27 juillet 1998, N
    98.09563.
    SALGADO E., 1999, Conception et mise en ouvre d`un bioreacteur a membranes pour l`etude de la dynamique de
    populations mixtes de micro-organismes These INPT
    SALGADO MANJARREZ E., C. ALBASI, J.P. RIBA, 2000, A two reservoirs hollow Iiber bioreactor Ior the study oI mixed
    populations dynamics : design aspect and validation oI the approach, Biotechnology Bioengineering, vol. 69 (4) 401-408
    -336-
    PD.2.9
    Mathematical modeling of enzymatic fructooligosaccharide production in continuous
    membrane reactor
    Z. Kovacs
    1
    , L. Engel
    1
    , K. Grau
    1
    , T. Hahn
    1
    , M. Ebrahimi
    1
    , P. Czermak
    1, 2
    1
    Universitv of Applied Sciences Giessen-Friedberg, Institute of Biopharmaceutical Technologv, Wiesenstrasse 14, 35390
    Giessen, Germanv,
    2
    Department of Chemical Engineering, Kansas State Universitv, Manhattan, Kansas, 66506, U.S.A.
    Kovacs.Zoltantg.Ih-giessen.de
    Fructooligosaccharides (FOS) are considered to be physiologically Iavourable Iunctional Iood ingredients. FOS can be
    produced Irom sucrose by enzymatic catalysis with Iree enzymes compartmentalized in continuous membrane bioreactors
    (CMBR). The synthesis is a complex process involving a multitude oI sequential reactions leading to the Iinal products. The
    resulting FOS structures are mainly 1-kestose (GF2), nystose (GF3) and 1I-IructoIuranosyl nystose (GF4), where, G and F
    mean glucosyl and Iructosyl mioeties oI the sucrose molecule, respectively. The by-product oI the conversion is glucose that
    has been reported to be the main Iactor lowering yield during FOS synthesis. Moreover, hydrolysis reactions oI FOS also occur
    resulting lower grades oI polymerisation. The amount and nature oI FOS Iormed in the CMBR depends upon several Iactors
    including the enzyme source, the concentration and nature oI the substrate, the degree oI conversion oI the substrate and the
    operation conditions. In this study, a mathematical Irame Ior modeling CMBR processes is provided. The approach Iollowed in
    this work uses the design equations oI the membrane reactor conIiguration and the coupled equations describing the enzyme
    kinetics as a basis Ior calculations. The kinetic parameters are obtained Irom data in the literature and through well-designed
    experimentation using various enzyme sources. The simultaneous numerical solution oI the proposed set oI ordinary
    diIIerential equations allows the prediction oI the dynamic behaviour oI FOS production in CMBR systems. The presented
    simulation technique is a useIul tool Ior obtaining high yield and high purity oI FOS by evaluating the optimal system design,
    operation, and control.
    PD.2.10
    MF associated with an anaerobic fluidized bed reactor. Part 1: Flux resistance
    evaluation
    L. L. Beal, M. Zeni, P. A. BoII, A. A. Lovatel
    Universitv of Caxias do Sul, Francisco Getulio Jargas, 1130, Caxias do Sul, Bra:il
    llbealucs.br
    The Ilux resistance promoted by biomass oI bioreactors can be considered one oI the main parameters in the MBR design. The
    main goal oI this paper is evaluate the resistance behaviour and the eIIects oI chemical cleaning as well as water cleaning in a
    MF membrane associated with anaerobic Iluidized bed reactor. The membrane used was PVDF, supplied by KOCH and the
    transmembrane pressure applied was 400.57+ 39.81kPa. The experiment was monitored Ior 1,200 hours, and aIter 480 hours
    the chemical process cleaning was completed. The results show that the maximum Ilux resistance value was 23.53 times larger
    than the membrane resistance (Rm) beIore the chemical cleaning. The correlation coeIIicient between Ilux and resistance (r
    -0.77 beIore chemical cleaning and r-0.79 aIter) shows that the increase oI resistance has been the main Iactor to reduce the
    Ilux values.
    -337-
    Figure 1: Long term Ilux and resistance behaviour.
    AIter the chemical process cleaning, the membrane resistance (Rm`) showed a value oI 3.81 x 10
    13
    m
    -1
    This value increased to
    1.23 x 10
    15
    m
    -1
    immediately beIore water cleaning. When the Iirst water cleaning was perIormed the membrane resistance value
    decreased to 1.05 x 10
    14
    m
    -1
    (91) and aIter the second water cleaning this value was 1.23 x 10
    14
    m
    -1
    (87.9). These values are
    very close and indicate that despite the Iact that water cleaning is less eIIective than chemical cleaning; it is a quicker, more
    economical and saIer method to promote the removal oI the compounds settled on the membrane surIace, reestablishing a
    better permeate Ilux. This strategy is shown to be adequate to do cleanings between short operational periods oI time in
    membrane systems.
    P. Le-Clech, V. Chen, T. A. G. Fane, Fouling in membrane bioreactors used in wastewater treatment Journal oI Membrane
    Science, 2006 p. 17-53
    S. F. G. Boerlage, M. D. Kennedy, M. R., Dickson, D. E. Y. El-Hodali, J. C. Schippers. The modiIied Iouling index using
    ultraIiltration membranes (MFI-UF): characterization, Iiltration mechanisms and proposed reIerence membranes. Journal oI
    Membrane Science, 2002, v. 197, p. 1-21.
    PD.3.1
    Experimental and numerical characterization of mixing in a hollow fiber membrane
    contactor by the iodide-iodate method
    N. Bakkar, R. KieIIer, C. Charcosset
    1
    Universite de Lvon, 43 Bd du 11 novembre 1918, 69622 Jilleurbanne cedex, France
    2
    Universite Lvon 1, 43 Bd du 11 novembre 1918, 69622 Jilleurbanne cedex, France

    3
    CNRS, UMR 5007, Laboratoire dAutomatique et de Genie des Procedes, 43 Bd du 11 novembre 1918, 69622 Jilleurbanne
    cedex, France
    4
    ESCPE-Lvon, 43 Bd du 11 novembre 1918, 69622 Jilleurbanne cedex, France
    charcossetlagep.univ-lyon1.Ir
    This paper presents numerical simulations and experimental data oI the iodide-iodate reaction in a hollow Iiber membrane
    device. Mixing/reaction in a hollow Iiber membrane device occur as Iollows: component A Ilows through the inlet oI the
    lumen side and component B comes Irom the membrane pores (shell side). Components A and B then mix and react inside the
    lumen side |1|. The purpose oI this work is to study numerically and experimentally mixing in these devices.
    The iodide-iodate method is based on a competitive parallel reactions system. The reaction oI iodate and iodide to iodine (also
    named the 'Dushman reaction) is Iast, in the same range oI the micromixing process, but is much slower than the
    neutralisation oI dihydroborate ions. The iodine
    2
    I Iormed can Iurther react with iodide ions

    I to yield

    3
    I ions according
    to a quasi-instantaneous equilibrium. The segregation index, X
    s
    , may be calculated Irom the ratio oI the acid mole number
    consumed by the slow reaction (the creation oI iodine
    2
    I and

    3
    I ) and the total acid mole number.
    In this study, experimental measurements oI the segregation index were carried out Ior various experimental conditions and Ior
    diIIerent hollow Iibers devices. The numerical and experimental segregation indexes, X
    s
    , were Iound in the range
    3 2
    10 - 10

    ,
    indicating eIIective mixing. The numerical simulations showed that

    3
    I ions were produced mainly in the Iirst part oI the
    -338-
    lumen side oI the hollow Iiber. This conIirmed our previous results on precipitation which showed that high supersaturation
    data and experimental Iouling are obtained in this part oI the hollow Iibers |2|.
    |1| KieIIer R., Charcosset C., Puel F., Mangin D., Numerical simulation oI mass transIer in a liquid-liquid membrane contactor
    Ior laminar Ilow conditions, Comput. Chem. Eng. 32 (2008) 1333-1341;
    |2| KieIIer R., Mangin D., Puel F., Charcosset C., Precipitation oI barium sulphate in a hollow Iibers membrane contactor: Part
    I Investigation oI Iouling, submitted (2008).
    PD.3.2
    Treatment of olive oil mill wastewater by an integrated membrane system
    E. Garcia-Castello
    1
    , A. Cassano
    2
    , A. Criscuoli
    2
    , C. Conidi
    2
    , E. Drioli
    2,3
    1
    Institute of Food Engineering for Development. Polvtechnic Universitv of Jalencia, Camino de Jera, s/n, 46022, Jalencia,
    Spain.
    2
    Institute on Membrane Technologv, ITM-CNR c/o Universitv of Calabria, cubo 17/C, 87030 Rende, CS, Italv.
    3
    Department of Chemical Engineering and Materials, The Universitv of Calabria, cubo 44/A 87030 Rende, CS, Italv
    egarcia1iqn.upv.es
    The purpose oI this work was to analyse the potentialities oI an integrated membrane system Ior the recovery, puriIication and
    concentration oI polyphenols Irom olive mill wastewater (OMW). The proposed system included some well-known membrane
    operations such as microIiltration (MF) and nanoIiltration (NF) as well as others not yet investigated Ior this speciIic
    application such as osmotic distillation (OD) and vacuum membrane distillation (VMD).
    The OMW was directly submitted to a MF operation without preliminary centriIugation. This step allowed to achieve a 91
    and 26 reduction oI suspended solids and total organic carbon (TOC), respectively. Moreover, 78 oI the initial content oI
    polyphenols was recovered in the permeate stream.
    The MF permeate was then submitted to a NF treatment. Almost all polyphenols were recovered in the produced permeate
    solution, while TOC was reduced Irom 15 g/l to 5.6 g/l.
    A concentrated solution enriched in polyphenols was obtained by treating the NF permeate by OD. In particular, a solution
    containing about 0.5 g/l oI Iree low molecular weight polyphenols, with hydroxytyrosol representing 56 oI the total, was
    produced by using a 60 w/w calcium chloride dehydrate solution as brine. The concentrated solution could be used Ior
    obtaining Iormulations oI interest in the Iood and pharmaceutical industry.
    Besides the OD process, VMD was applied as another way Ior concentrating the NF permeate and the perIormance oI both
    processes was compared in terms oI evaporation Iluxes.
    PD.3.3
    Non dispersive solvent extraction of alkali metal with calix4]arene: modeling and
    process optimization
    Z. Albaraka zaher
    1
    , J.M. Loureiro
    2
    , M. Burgard
    1
    , D. Trebouet
    1
    Laboratoire des Procedes de Separation, UMR CNRS 7512, ECPM, 25 rue Becquerel 67087 Strasbourg Cedex 2, France.
    2
    Laboratorv of Separation and Reaction Engineering, Universidade do Porto, Faculdade de Engenharia, Rua Dr Roberto
    Frias, 4200-465 Porto, Portugal.
    zaher.al-barakaulp.u-strasbg.Ir
    In the last years, the non dispersive solvent extraction with hollow Iibers contactor have received a growing attention in some
    speciIic Iields as the hydrometallurgy wastewater treatment |1|, the nuclear Iuel reprocessing separation |2| and the
    biomolecules puriIication |3|. The use oI hollow Iiber contactor provides some advantages as a large contact area per unit
    equipment volume. The association membrane contactor and selective extractant macrocycle as calixarene can increase even
    more the attraction oI this process and can be a response to the growing demands imposed by extraction processes that cannot
    be carried out economically using extraction conventional technologies. Indeed, the macrocycle extractants improves the
    extraction selectivity and the solute distribution coeIIicient, H, between the organic and the aqueous phase.
    In this study, the non dispersive solvent extraction oI the alkali picrates with the bis-crown-6-calix|4|arene (a good complexing
    agent oI cesium) in toluene (95 ) decanol (5) is presented. The experimental data enable to show that the closed
    -339-
    extraction system operates in unsteady state until the equilibrium is reached. The extraction yields are 98 , 90 and 40
    Ior the cesium, rubidium and potassium respectively, according the cavity size oI macrocycle. A dynamic model describing
    successIully the mass transIer kinetics is used to calculate the global mass transIer coeIIicient between the aqueous and organic
    phases |4|. This model is used as a tool to investigate and to simulate the inIluence oI the module capacity Iactor (represents
    the ratio between the solute amounts in the organic and in the aqueous phases at equilibrium) and the residence time ratio in
    the module (between the residence times in the shell side and inside the hollow Iiber lumen). This investigation enables to
    optimize the conIiguration oI membrane extractor.
    |1| B. Galan, D. Castaeda and I. Ortiz, Integration oI ion exchange and non-dispersive solvent extraction processes Ior the
    separation and concentration oI Cr(VI) Irom ground waters, Journal oI Hazardous Materials, 2008, 152 (2), 795-804.
    |2| C.B. Patil, P.K. Mohapatra, V.K. Manchanda, Transport oI thorium Irom nitric acid solution by non dispersive solvent
    extraction using a hollow Iibre contactor, Desalination, 2008, 232, 272 280.
    |3| W. Rield, T. Raiser, Membrane-supported extraction oI biomolecules with aqueous two-phase systems, desalination, 2008,
    224 (1-3), 160-167.
    |4| Z. Albaraka, D. Trebouet, M. Tuna, J.M. Loureiro, M. Burgard, SFGP 2007 - An analysis oI the mass transIer in a non-
    dispersive solvent extraction closed system. International Journal oI Chemical Reactor Engineering 2008, 6, A13.
    PD.3.4
    Modeling and simulation of HFMC for dispersion free liquid-liquid extraction of
    copper
    M. Younas, S. Druon Bocquet, J. Sanchez
    Institut Europeen des Membranes (IEM) ENSCM, UM2, CNRS , Universite Montpellier 2, CC047, Place Eugene Bataillon,
    34095 Montpellier, France
    younasiemm.univ-montp2.Ir
    Dispersion Iree liquid-liquid extraction is aimed to apply on Hollow Fiber Membrane Contactor (HFMC) Ior extraction oI
    copper Irom aqueous streams with LIX 84-I (2-hydroxy-5-nonylacetephenone oxime) diluted in n-heptane. Environmental
    concerns, increasing cost, scarcity oI water, decreasing price oI membranes and their commercialization switch the tedious or
    time consuming traditional solvent extraction technique over the membrane separations. On the other hand heavy metal
    bearing water pollution was being a worldwide concern Ior the last Iew decades.
    AIter perIorming the batch experiments to identiIy the extraction kinetics and to measure the partition coeIIicient oI copper
    aqueous-organic phase system, both phases are interacted in a mini baIIleless HFMC liquid-Cel module with recycled based
    continuous Ilow system. A mass transIer model oI HFMC based on axial and radial approach, Irom resistance in series
    concept, is achieved to gain the module exit concentrations. The dynamic model developed in previous work |1| has been used
    to calculate the copper concentration within the storage tank. The integrated mathematical model oI the recycled based pilot
    plant was scripted in Matlab7.4 R(b).The model has been validated with the experimental data at various operating
    conditions. Simulation is run Ior a range oI diIIerent operating and membrane parameters to determine optimum conditions.
    |1| M. Younas, S. Druon Bocquet, J. Sanchez, Extraction oI aroma compounds in a HFMC : Dynamic modelling and
    simulation, J. Memb. Sc., 2008, 323(2), 386-394.
    -340-
    PD.3.5
    Concentration of duck feather keratin hydrolysate using direct contact membrane
    distillation
    K.V. Christensen
    1
    , D. Bialas
    1
    , D. Hjollund Jensen
    2
    , P. Jensen
    3
    1
    Institute of Chemical Engineering, Biotechnologv and Environmental Technologv, Universitv of Southern Denmark, Niels
    Bohrs Alle 1, DK5210 Odense NJ, Denmark
    2
    Tetra Pak Filtration Svstems, Soren Nvmarksvef 13,DK8270 Hofbferg, Denmark
    3
    Department of Conservation, The Danish National Museum, IC Modewegsvef Brede, DK2800 Kgs. Lvngbv, Denmark
    kvckbm.sdu.dk
    Conservation oI waterlogged wood Irom archeological Iinds are currently being preserved using i.e. polyglycerols. This
    process requires Iirst submerging the item to be preserved in low concentration solutions Ior 6 month to 10 years. Following
    this impregnation and strengthening process the items are Ireeze dried Ior between three and Iive month. This conservation
    method yields good results but is expensive and laboriously. R. Endo et al |1,2,3| suggests using a hydrolyzed duck Ieather
    keratin (HDFK) solution instead. In this method the impregnation solution consists oI a 10 weight- HDFK-water solution
    which is increased during the impregnation process to 40 weight-. This was claimed to yield results superior to standard
    conservation procedures aIter stepwise impregnation in 10, 20, 30 and 40 HDFK solutions Ior 20 days at 60 C Iollowed by
    air drying. This seems in many ways a more ecology-conscious
    method using renewable materials and much less energy consuming
    as Ireeze drying might be avoided.
    The Danish National Museum wished both to test the conservation
    method and to know iI a simple, easily controllable methods Ior
    slowly increasing the HDFK concentration with out having to add
    HDFK during the process could be developed. As a response to this
    last request a method based on direct contact membrane distillation
    (DCMD) was developed.
    The result oI the DCMD experiments Ior concentrating HDFK and
    a model which can also be used Ior a priori prediction oI DCMD
    Iluxes Ior other protein solutions is what is presented here.
    As seen Irom Iigure 1 it was possible to concentrate the keratin
    Irom a 10 to 40 solution without any problems while the
    prediction model based on a 'dusty gas model combined with heat
    and mass transIer limitations near the membrane surIace predicts
    the experimental results well.
    |1| R. Endo; K. Kamel; I. Iida; Y. Kawahara Dimensional Stability oI Waterlogged Wood Treated with Hydrolyzed Feather
    Keratin. Journal oI Archeological Science. 2008 (35) pp. 1240-1246.
    |2| R. Endo; Y. Kawahara Research Activities Using Duck Feather Hydrolysate Ior Archeological Waterlogged Woods.
    WOAM Newsletters. 2005 (33)
    |3| Y. Kawahara; R. Endo; K. Kimura Conservation oI Archeological Waterlogged Woods using Keratin Irom Waste Down.
    Journal oI Textile Engineering 2002 (48) PP. 107-110.
    PD.3.6
    Membrane-based ripper method to accurate determination of free and bonded sulfite
    content in red wine
    A. Plaza, J. Romero, E. Morales, B. Perez, W. Silva
    Laboratorv of Membrane Separation Processes (Labprosem), Department of Chemical Engineering, Universitv of Santiago de
    Chile (USACH) Av. Lib. Bdo. OHiggins 3363, Estacion Central, Santiago, Chile
    julio.romerousach.cl
    SO
    2
    has been used as a preservative agent in wine because it has several Iunctions in wine conservation. Although neither
    carcinogenicity nor mutagenic eIIect was Iound in SO
    2
    , this compound can, however, have an inIluence on human health due
    to its allergic eIIect |1|.
    -341-
    1
    1.5
    2
    2.5
    3
    3.5
    4
    4.5
    5
    0 10 20 30 40
    Keratin Weight-]
    F
    l
    u
    x

    k
    g
    /
    m
    2
    /
    h
    ]
    Figure 1 + Experimental data.
    - Full model
    -- Dusty gas model without transIer limitations
    The Ripper method Ior sulIur dioxide, which is more than one hundred years old, uses standard iodine to titrate the Iree or total
    SO
    2
    in a sample, the procedure is so simple that it is the most common method employed in the wineries. However, it is
    universally recognized that this method is somewhat inaccurate in red wines. In this work, a modiIied methodology based on
    the Ripper method is proposed to determine the sulIite content in red wines using a membrane contactor system.
    A hydrophobic macroporous membrane has been used to separate red wine and an extraction solution. The extraction solution
    used in this method is an aqueous NaOH solution. Both solutions have been circulated in countercurrent conIiguration through
    independent circuits on each side oI the membrane. SO
    2
    is desorbed Irom the wine aIter a pH modiIication (acidiIication), and
    adsorbed in the colorless extraction solution, where SO
    2
    is stabilized as SO
    3
    2-
    , which can be quantiIied by electrochemical or
    colorimetric methods. An outline oI this process is showed in Iigure 1.
    Determination oI Iree sulIite content was done aIter acidiIication oI the red wine sample at pH 1.0. Free SO
    2
    is transIerred
    through a hollow Iiber membrane contactor and absorbed in the extraction solution. Experiments carried out using model
    solutions oI sulIite with a known
    concentration allow estimating an extraction
    percentage oI 97.25 oI Iree SO
    2
    aIter 8
    min. Classical Ripper method was applied
    on the colorless extraction solution obtained
    Irom the membrane extraction veriIying the
    sulIite content in the model solution with a
    1.03 oI variance. Experiments with Iour
    diIIerent brands oI Cabernet Sauvignon
    wines show similar results with 0.96 oI
    average variance.
    Total SO
    2
    content was estimated Ior the
    same wines using the method previously
    described, but the wine samples was
    pretreated with a NaOH solution 1 N and
    acidiIied at pH 1.0, obtaining 1.22 oI
    average variance. The procedure described
    in this work could be implemented in
    wineries in order to determine the accurate
    concentration oI sulIites Ior an important
    number oI samples.
    CONICYT Chile (Project Anillo-Bicentenario ACT 24) is acknowledged Ior granting this work.
    |1| T. Garde-Cerdan and C.Ancin-Azpilicueta, EIIect oI SO
    2
    on the Iormation and evolution oI volatile compounds in wines,
    Food Control, 18 (2007), 15011506.
    PD.3.7
    Near critical and supercritical fluid extraction of Cu
    2+
    from aqueous solutions using
    hollow fiber membrane contactors
    J. Romero
    1
    , H. Valdes
    1
    , B. Perez
    1
    , F. Valenzuela
    2
    1
    Laboratorv of Membrane of Separation Processes (Labprosem), Department of Chemical Engineering, Universitv of Santiago
    of Chile (USACH) - Av.. Lib. Bdo. OHiggins 3363, Estacion Central, Santiago, Chile.
    2
    Department of Food Science and Chemical Technologv, Facultv of Chemical and Pharmaceutical Sciences, Universitv of
    Chile Jicua Mackenna 20 , Santiago, Chile.
    julio.romerousach.cl
    The aim oI this work is the experimental characterization and the theoretical analysis oI the membrane-based near critical and
    supercritical Iluid extraction oI metals Irom aqueous solutions using a hollow Iiber contactor.
    The system analyzed is a hollow Iiber membrane contactor process Ior extraction oI Cu
    2
    Irom aqueous solutions. The
    extraction solvent used in this work is near critical or supercritical carbon dioxide containing 1,1,1-triIluoro-2,4-pentanedione
    (TFA) as chelating agent |1|. The contactor used in this work is a single Iiber membrane module. The principle oI this process
    and the mass transIer through the membrane is presented in Iigure 1.
    -342-
    Fig. 1. Outline oI the membrane-based Ripper method applied to red wine.
    Experimental setup was
    operated under steady-state
    condition at 40C with
    pressures between 70 and
    100 bar. The liquid Ieed
    solutions used in this study
    were acid solutions oI
    CuSO
    4
    (500 ppm), which
    were circulated in the
    lumenside using an
    isocratic pump with
    circulation rates between
    0.1 and 1.0 ml/min.
    Pressurized CO
    2
    containing
    the chelating agent was
    circulated countercurrently
    through the contactor by
    means a syringe pump with
    volumetric Ilow rates
    between 0.7 and 1.0
    ml/min.
    Concentration oI Cu
    2
    in the raIIinate was determined by atomic absorption spectroscopy. The extraction percentage calculated
    Irom the experimental results show values between 7 and 41, which are close to the equilibrium data reported by Erkey |1|.
    A resistance-in-series model was developed to describe the mass transIer and to evaluate the individual resistances in the
    proximities oI the membrane. Local mass transIer resistances oI the aqueous boundary layer, the membrane porosity and the
    gas boundary layer represent between 40 to 50, 10 to 14 and 38 to 50 oI the total mass transIer resistance, respectively.
    CONICYT Chile (Project FONDECYT 1070062) is acknowledged Ior granting this work.
    |1| Erkey, C., Supercritical carbon dioxide extraction oI metal ions Irom aqueous solutions: a review, Journal oI Supercritical
    Fluids 17, (2000), 259-287.
    -343-
    Fig. 1. Outline oI the hollow Iiber membrane contactor studied in this project: a) circulation oI
    the solutions inside and outside the Iiber, and b) schematic representation oI the mass transIer oI
    metal M (Cu
    2
    ) through the membrane. A is the extractant agent (TFA) and M(A)
    z
    is the
    complex Iormed at the interIace between Cu
    2
    and TFA.
    PD.3.8
    Thermally driven absorption chiller for residential cooling using membrane
    technology
    P. Schwerdt, C. Pollerberg, P. SchiIIer
    Fraunhofer Institute for Environmental, Safetv and Energv Technologv UMSICHT, Osterfelder Strasse 3, D-46047
    Oberhausen, Germanv
    peter.schwerdtumsicht.IraunhoIer.de
    By introducing membrane technology to modiIy the key
    components oI absorption cooling and heating cycles, the
    unit size could be signiIicantly reduced, thus Iacilitating a
    broader use oI thermally driven cycles in heating and air
    conditioning.
    Flat microporous, hydrophobic, eg. PTFE membranes, allow
    very thin liquid Iilms and vapor channels, providing a large
    contact surIace Ior heat and mass exchange in a small
    volume when being assembled to stacks. The stack design is
    similar to Iuel cell stacks or plate type heat exchangers
    (Figure 1). This technique could be applied both to the
    absorber and the desorber, e.g. oI lithiumbromide/water
    absorption chillers.
    Our work includes both computational modeling oI
    membrane transport processes |1| as well as experimental
    membrane characterization, showing excellent accordance.
    Recently a Iirst membrane absorber single cell module was
    built and experimentally tested. The results are in line with
    the theoretical model.
    The search Ior hydrophobic membranes with higher water
    vapor capacity is continued. Further Iocus is on the design oI
    real absorber and desorber stacks and the integration oI a
    chiller prototype providing 5 kW oI cooling power.
    |1| Ali, A.; Schwerdt, P., Characteristics oI the Membrane
    utilized in a Compact Absorber Ior Lithiumbromide/Water
    Absorption Chillers, Proceedings oI the IEA Heat Pump
    ConIerence, Zuerich 2008

    cooling
    water
    LiBr
    solution
    Refrigerant
    vapor
    Fig. 1 : Design study oI a membrane absorber cell module in
    an solar driven absorption chiller

    s
    v
    m

    s
    T

    v
    T
    v
    P
    s m
    p
    ,

    s
    p

    s
    X

    s m
    T
    ,

    v m
    Membrane
    active support
    layer layer
    Mass flux
    sup
    out s
    m
    ,

    out s
    T
    ,
    ,
    out s
    X
    ,
    in s
    m
    ,


    in s
    T
    ,
    ,
    in s
    X
    ,
    s v
    T
    , int,
    s v
    X
    , int,
    Fig. 2 : mass transIer oI water vapor (reIrigerant) through a
    semi-permeable membrane into the LiBr-H
    2
    O solution
    (absorption Iluid)
    -344-
    PD.3.9
    Photosynthetic fixation of carbon dioxide into microalgae using gas-liquid membrane
    contacting process
    D.-E. Hong, B. Jung
    Department. of Environmental Engineering and Biotechnologv, Mvongfi Universitv, San 38-2, Nam-dong, Yongin, Kveonggi-
    do 449-728, Republic of Korea
    bjungmju.ac.kr
    With increased concerns about global warming and greenhouse gas emissions, there have been several approaches proposed
    Ior managing the levels oI CO
    2
    emitted into the atmosphere. One oI the most understudied methods Ior CO
    2
    mitigation is the
    use oI biomass process in a direct CO
    2
    to biomass conversion Irom point source emissions oI CO
    2
    in engineered system such as
    photo bioreactors |1|.
    Microalgae are more eIIicient at using CO
    2
    Ior photosynthesis and
    have higher proliIeration rate. The rate oI CO
    2
    absorption is a
    limiting Iactor in the process, thereIore the mass transIer
    coeIIicient is very important parameter in production oI microalgae
    |2|. The principal advantages oI gas-liquid membrane contactors
    are operational Ilexibility, high mass transIer rate and easy linear
    scale up. The absorption rate oI CO
    2
    into the media depends on the
    interIacial area Ior the gas-liquid contact and mass transIer
    coeIIicient. This research describes the chemical mechanism oI
    CO2 in photosynthesis oI microalgae at diIIerent K
    L
    a values. In
    addition, this study oIIers design methodology oI photo bioreactor
    (Fig. 1).
    |1| JE KeIIer, GT Kleinheinz, Use oI chlorella vulgaris Ior CO
    2
    mitigation in a photobioreactor, Journal oI Industrial Microbiology
    & Biotechnology (2002) 29, 275-280.
    |2| C-G Lee, BO Palsson, Light emitting diode-based algal
    photobioreactor with external gas exchange, J. Ferment. Bioeng.,
    (1995) 79, 257-263.
    PD.3.10
    Concentration and modelling of sucrose solution and apricot juice by mass transfer
    membrane processes
    A. Kozak, E. Fogarassy, G. Racz, E. Bekassy-Molnar, G. Vatai
    Corvinus Universitv of Budapest, Department of Food Engineering, Menesi ut 44. Budapest H-1118 Hungarv
    aron.kozakuni-corvinus.hu
    The mass transport membrane processes such as pervaporation (PV), membrane distillation (MD) and osmotic distillation
    (OD) could be applied to numerous Iields oI chemical and Iood industry. The applicability oI these processes Ior concentration
    oI liquid Ioods was investigated by many researchers in the last Iew decades. These techniques have disadvantages in many
    ways, they do not Iully satisIy the manuIacturers and the customers, and the relatively high operation costs keeps within limits
    the widely industrial adaptations.
    The results oI the early experiments showed that these methods could be suitable Ior the concentration oI e.g. Iruit juices up to
    high total soluble solid content (TSS). It is generally recognised that during the concentration oI Iruit juices up to 6070 TSS
    a signiIicant amount oI water is removed, thereIore a signiIicant reduction in transport, packaging, and storage cost can be
    reached, with much greater stability oI the products. Although the operation costs are high, these costs could be reduced
    signiIicantly by the application oI the right operation parameters and with using recently developed mass and heat transport
    models |1, 2|.
    -345-
    Fig. 1. Membrane contactor set-up.
    The aim oI this study was to investigate the applicability and eIIiciency oI two mass transIer membrane processes, the OD and
    MD by the concentration oI apricot juice up to high TSS and set up a model which deIines the eIIects oI the operation
    parameters by using various model (sucrose) solutions.
    The experimental results proved the applicability oI OD and MD Ior the concentration oI the apricot juice and model sugar
    solution Ior comparison. On the basis oI experimental results with the juice and the model solutions mass transport-, heat
    transport- and operation cost models were calculated.
    The authors would like to acknowledge Ior the Iinancial support oI the Jedlik Anyos (OM0034/2007) and the OTKA
    Foundations (T049850).
    |1| R. Thanedgunbaworn, R. Jiraratananon, M.H. Nguyen, Mass and heat transIer analysis in Iructose concentration by
    osmotic distillation process using hollow Iibre module, Journal oI Food Engineering 78 (2007) 126135
    |2| M. Qtaishat, T. Matsuura, B. Kruczek, M. Khayet, Heat and mass transIer analysis in direct contact membrane distillation,
    Desalination 219 (2008) 272-292
    PD.3.11
    Extractive ultrafiltration of betaine using hollow fiber contactors
    M.O. Ruiz, I. Escudero, B. Martinez
    Department of Chemical Engineering, Universitv of Burgos, Pla:a Misael Bauelos s/n, 09001Burgos, Spain
    moruizubu.es
    Betaine (N,N,N-trimethylglycine) is extensively used in cosmetic, animal Ieedstock, pharmaceutical and health industries.
    Betaine plays a role in reducing blood levels oI homocysteine and it is also used as a digestive aid Ior people with insuIIicient
    acid production in the stomach and as a nutritional supplement to protect against chemical damage to the liver. Furthermore,
    the daily use oI topical products containing olive oil, betaine and xylitol is saIe and eIIective in relieving symptoms oI dry
    mouth. Apart Irom these applications, betaine has also technical uses as surIactant Ior cosmetics and toiletries, especially Ior
    mild shampoos, Ioam baths, bath products and liquid handsoaps. Betaine is present in waste streams Irom sugar beet
    processing plants, in concentrations oI up to 8 wt. in beet molasses and around 4 wt. in vinasses (aIter molasses
    Iermentation). Betaine recovery Irom beet molasses by ion exchange cationic resins and by chromatographic techniques has
    been proposed. Extractive ultraIiltration using membrane contactors in connection with the reactive liquid-liquid extraction are
    been used as a competitive hybrid membrane process Ior the recovery oI many bio-compounds. This technique avoids many oI
    the shortcomings associated with solvent extraction in conventional processes and is considered as a clean technology, because
    it has the advantages oI large-scale continuous separation, energy-saving technique and easy operation oI the process
    The aim oI this work was to study and optimize the recovery oI betaine Irom aqueous solutions by an integrated membrane-
    based extraction and coextraction process using two Celgard X-50 hollow-Iiber membrane contactors. Organic solutions oI
    dinonylnaphthalenesulIonic acid (DNNSA) in heptane and aqueous NaOH solutions were used as solvent and stripping phases,
    respectively. This integrated extraction-stripping membrane process allows the organic phase regeneration and the amino acid
    concentration in the stripping phase. The eIIect oI the hydrodynamic conditions on the mass-transIer rate was analyzed. The
    inIluence oI betaine concentration and pH in the Ieed, DNNSA concentration in the organic phase, temperature and
    composition oI the stripping solution on the extractive ultraIiltration perIormance were studied. An easy predictive
    mathematical model that considers the reactive extraction oI betaine with the DNNSA has been developed to estimate the
    overall mass transIer coeIIicients and simulate the concentration proIiles oI the three phases.
    This work was supported by the Ministerio de Educacion y Ciencia (MEC, Spain) and the European Commission through
    European Regional Development Fund by grant CTQ2006-03032. Fund received Irom Junta de Castilla y Leon, through grant
    BU017A06 is also grateIully acknowledged.
    -346-
    PD.3.12
    Seawater desalination by membrane distillation-crystallization: troubles at high
    recovery factors
    E. Curcio
    1,2
    , J. Xiaosheng
    1
    , G. Di ProIio
    1
    , S. Al-Obaidani
    1,2
    , E. Drioli
    1,2
    1
    Department of Chemical Engineering and Materials, Universitv of Calabria, via P. Bucci CUBO 44A 87030 Rende (CS)
    Italv
    2
    Institute on Membrane technologv ITM-CNR, via P. Bucci CUBO 17C 87030 Rende (CS)
    3
    Department of Mechanical and Industrial Engineering, Sultan Qaboos Universitv, P.O. Box 33Al-Khod, P.C. 123, Oman
    e.curciounical.it
    Membrane Distillation-Crystallization (MDC) is recently increasing its appeal as a desalination unit able to approach Zero
    Liquid Discharge goal|1|. This work investigates problems in MDC operated at high recovery Iactors. While studies in
    literature only Iocus on the chemistry oI solutions, in our work
    the kinetics oI scaling (investigated by Dynamic Light
    Scattering) was correlated to physico-chemical properties oI the
    membrane (i.e. contact angle and porosity ). For instance, a
    comparison between CaCO
    3
    crystals suggested that the ratio oI
    their surIace tensions (when nucleated in presence/in absence oI
    the membrane), obtained by induction time data (Figure 1), well
    agree with the predicted ratio oI Gibbs energy barriers to the
    Iormation oI critical nuclei Ior heterogeneous nucleation on
    microporous membranes|2|:
    ( )( )
    ( )
    ( )
    3
    2
    2
    2
    *
    hom
    *
    cos 1
    cos 1
    1 cos 1 cos 2
    4
    1
    ]
    ]
    ]
    ,

    +
    +


    G
    G
    het
    (1)
    In addition, experimental tests carried out in a 100L MDC semi-
    pilot plant showed that, although soItening by soda ash reduced
    scaling problem, HA/divalent-metal ions complexes deteriorated
    the hydrophobic character oI the membrane and promoted the
    occurrence oI Iouling.
    |1| S. Al-Obaidani, E. Curcio, F. Macedonio, G. Di ProIio, H.
    Al-Hinai, E. Drioli, Potential oI Membrane Distillation in
    Seawater Desalination: Thermal eIIiciency, sensitivity study and
    cost estimation, J. Membrane Sci. 2008, 323, 85-98
    |2| E. Curcio, E. Fontananova, G. Di ProIio, E. Drioli, InIluence
    oI the Structural Properties oI Poly(vinylidene Iluoride)
    Membranes on the Heterogeneous Nucleation Rate oI Protein
    Crystals, J. Phys. Chem B, 2006, 110, 8917- 8920
    PD.3.13
    Sustainable processes based on the use of selective liquid membranes for the
    recovery of spent passivating baths
    R. Mediavilla, E. Bringas, I. Ortiz, A. Urtiaga
    Department of Chemical Engineering, Universitv of Cantabria. Avda. Los Castros s/n 39005 Santander, Spain.
    urtiagaunican.es
    In this work, Emulsion pertraction technology is employed Ior the regeneration oI galvanic baths. During the production
    process, passivating baths based on chromium (III) are contaminated by iron and zinc, thereIore decreasing the eIIiciency oI
    the surIace treatment. Liquid membranes allow the selective separation oI Zn and Fe, while maintaining Cr in the passivating
    bath. The use oI membrane contactors prevents the direct mixture oI the organic extractant phase and the galvanic bath, thus
    allowing the integration oI the membrane regeneration process in the continuous passivating operation.
    -347-
    0.17 0.18 0.19 0.2
    ln
    -1
    S
    0
    1
    2
    3
    4
    l
    n
    (
    t
    i
    n
    d
    )
    HETEROGENEOUS
    NUCLEATON
    HOMOGENEOUS
    NUCLEATON
    Membrane/no HA
    Membrane/HA
    Figure 1: Induction time versus supersaturation
    oI CaCO
    3
    crystals grown on polypropylene
    membrane.
    In the EPT process the hollow Iiber microporous membranes create the interIace between the aqueous bath and a pseudo-
    emulsion Iormed by the organic extractant and the stripping agent. The research and development oI the EPT process Ior the
    regeneration oI passivating baths requires: i) the selection oI the organic extractant that enables the selective extraction oI iron
    and zinc, at the operation acidic pH oI the passivating baths; ii) the experimental assessment oI the viability oI the EPT
    process, showing the stability oI the liquid membrane and the resistance oI the membrane and module materials; iii) the
    mathematical modelling, including the evaluation oI the mass transIer parameters; iv) the integration oI the EPT process in the
    passivating bath operation, including the optimization oI the whole process that will permit the selection oI the best operation
    condition.
    In the present work, real passivating baths provided by a local galvanic industry have been tested Ior regeneration. The initial
    concentrations oI the metals under study in these baths are Zn: 3000-7000 mg/l; Fe: 20-40 mg/l; Cr: 5000-6000 mg/l.
    Polypropylene hollow Iiber modules (LiquiCel) are employed as membrane contactors. The emulsion is Iormed by the organic
    extractant based on phosphinic acids, and an aqueous acid solution as stripping agent. The experimental study includes the
    study oI the eIIect oI pH oI the baths, the concentration oI metals in the Ieed bath, the Ilow-rates oI the Iluid phases and the
    type and concentration oI the acid used as stripping phase. Mass balances based in dynamic diIIerential equations are solved
    using Aspen Custom Modeler, and the unknown mass transIer parameters were estimated by comparison oI experimental data
    and simulated results, thus providing the design tool that will enable the scale-up oI the EPT process according to the needs oI
    the passivating process.
    The emulsion pertraction process meets the requirements to become a best available technology Ior the European galvanic
    industry, that requires oI technical improvements with regards to the IPPC directive. The beneIits oI EPT, based in membrane
    contactors, will contribute to extent the liIetime oI the passivating baths, to reduce the amount oI generated wastes as spent
    baths, and to improve the quality oI the passivating operation.
    Acknowledgments: Financial support oI the Spanish Ministry oI Environment under project A542/2007/2 11.1 is grateIully
    acknowledged.
    |1| Mediavilla, R., I. Ortiz, A. Urtiaga. (2008). Selective extraction oI zinc and iron Irom passivating baths. 12th Aachener
    Membran Kolloquium. Germany.
    |2| Ortiz I., M.F. San Roman, S.M. Corvalan, A.M. Eliceche (2003). Modeling and Optimization oI an Emulsion Pertraction
    Process Ior Removal and Concentration oI Cr(VI). Ind. Eng. Chem. Res. 42 (23), pp. 5891-5899.
    |3| Urtiaga A., M. Abellan, A. Irabien, I. Ortiz (2005). Membrane contactors Ior the recovery oI metallic compounds
    Modelling oI copper recovery Irom WPO processes. J. Membr. Sci. 257, pp. 161-170.
    PD.4.1
    Adsorption of peptide binary mixtures by membrane chromatography
    J. Labanda
    1
    , J. Sabate
    2
    , J. Llorens
    1
    1
    Department of Chemical Engineering, Universitv of Barcelona, Marti i Franques 1, 08028 Barcelona, Spain
    2
    Departament dEnginveria Agroalimentaria i Biotecnologia, Universitat Politecnica de Catalunva, Edifici ESAB, Avinguda
    del Canal Olimpic s/n, 08860-Castelldefels, Spain
    jlabandaub.edu
    Membrane chromatography has been studied as an alternative to conventional resin-based column chromatography Ior the
    isolation and puriIication oI macromolecules. Membrane chromatography operates in convective mode, which can
    signiIicantly reduce diIIusion and pressure drop limitations commonly encountered in column chromatography |1|. Membrane
    chromatography combines the advantages oI conventional chromatography columns in terms oI separation power and capacity
    with membrane technology regarding mass transIer, high throughput and robustness. In literatures, the adsorption oI a single
    biomolecule has been described experimental and theoretically |2-3|.
    In this study, we propose a generalized mathematical model Ior study the adsorption oI peptide binary mixtures. The
    generalized mathematical model makes use oI dimensionless variables deIined in terms oI characteristic times Ior the diIIerent
    mechanisms that take place during the process (convection, dispersion, adsorption and desorption characteristic times). The
    movement and the adsorption oI peptides through the membrane adsorber are described by Iive independent dimensionless
    parameters Ior each peptide.
    -348-
    The validity oI the generalized model has been
    conducted by the adsorption oI binary mixtures oI
    two tripeptides (gly-gly-gly and gly-his-gly)
    through an ion-exchange membrane adsorber.
    Figure 1 shows the breakthrough curve Ior the
    50 binary mixture oI gly-gly-gly and gly-his-
    gly. Good correlation between Iitted and
    experimental breakthrough curves was obtained.
    The separation between both peptides is possible
    during 40 mL, when gly-his-gly is detected in the
    output stream.
    0
    0.5
    1
    1.5
    2
    0 100 200 300 400 500 600
    ( - )
    C

    (

    -

    )
    gly-gly-gly
    gly-his-gly
    Figure 1: Breakthrough curves.
    The authors are grateIul to the Spanish Ministerio de Ciencia y Tecnologia (project CTQ2005-08346-C02-01/PPQ) Ior Iunds
    received to carry out this study.
    |1| R. Ghosh, J. Chromatogr. A 952 (2002) 13.
    |2| W. Shi, F. Zhang, G. Zhang, J. Chromatogr. A 1081 (2006) 156.
    |3| C. Boi, S. Dimartino, G.C. Sarti, J. Chromatogr. A 1162 (2006) 24.
    PD.4.2
    Exploring liposome affinity chromatography for the separation of plasmid DNA
    vaccines
    L. Raiado-Pereira, D. M. F. Prazeres, M. Mateus
    IBB - Institute for Biotechnologv and Bioengineering, Center for Biological and Chemical Engineering, Instituto Superior
    Tecnico, Lisbon, Portugal
    luis.raiadoist.utl.pt
    AIter an initial demonstration oI the Ieasibility oI membrane hydrophobic interaction chromatography (HIC) Ior the
    puriIication oI plasmid DNA molecules (pDNA) - the therapeutic agents in DNA vaccines and gene medicines - Irom cell
    lysates
    1
    , our group aimed at developing membrane adsorbers Ior immobilized liposome chromatography (ILC).
    The HIC membrane was able to separate impurities, speciIically RNA, Irom clariIied Escherichia coli cell lysates with high
    resolution. With the purpose oI increasing puriIication levels we proposed ourselves to study the impact oI lipid monolayers
    covalently bound to aIIinity membranes and their ability to discriminate between plasmid DNA isoIorms, rendering a high
    resolution hydrophobic interaction chromatography media. ILC may also be used Ior membrane-oligonucleotide interaction
    analysis
    2
    and has the potential Ior aIIinity membrane chromatography oI therapeutic pDNA
    3
    .
    The conception oI the ILC membranes was accomplished by chemical modiIication oI pre-activated aIIinity membranes.
    Characterization oI these aIIinity membrane adsorbers was perIormed regarding hydrodynamics, density oI Iunctional groups,
    selective adsorption capacities towards plasmid DNA and its contaminants, and immobilized liposome membrane stability.
    1
    Raiado-Pereira, L, Prazeres, DMF, Mateus M. Preparation, characterization and testing oI adsorption membranes Ior
    chromatographic separation oI therapeutic plasmids. Proceedings oI Euromembrane 2009, 6-10 September, Montpellier,
    France
    2
    Lundquist, A, Engvall, C, Buija, E et al. Interactions oI drugs and oligonucleotide with charged membranes analysed by
    immobilized liposome chromatography. Biomed. Chromatogr., 20, 83-87 (2006)
    3
    Madeira, C, Loura, L, Prieto, M, Fedorov, A, Aires-Barros, MR. Liposome complexation eIIiciency monitored by FRET:
    eIIect oI charge ratio, helper lipid and plasmid size. Eur. Biophys. J., 36, 609-620 (2007)
    -349-
    PD.4.3
    Affinity membranes for antibody purification
    C. Boi, S. Dimartino, G.C. Sarti
    Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali, Universita di Bologna, via Terracini 28
    40131 Bologna, Italv.
    cristiana.boiunibo.it
    The use oI membrane adsorbers Ior the polishing step in protein therapeutics manuIacture has evolved into a Ieasible choice
    Ior the biopharmaceutical industry while aIIinity membrane chromatography Ior the primary capture is still not implemented
    due to the limited binding capacity oI membranes with respect to chromatography beads. In this work, aIIinity membranes with
    improved capacity have been considered as an alternative technology Ior the capturing step in antibody manuIacturing.
    To this aim aIIinity membranes have been prepared starting Irom diIIerent membrane supports. Several aIIinity ligands have
    been utilized like Protein A |1|, the natural ligand oI choice Ior antibodies, as well as synthetic ligands that exhibit aIIinity Ior
    the Fc portion oI antibodies |2, 3|. The membranes have been characterized in detail: binding and elution perIormance were
    evaluated in batch experiments using pure protein solutions and in particular human IgG, murine IgG and human IgM, while
    membrane selectivity was evaluated using complex solutions like cell culture supernatant or human and mouse sera.
    The most promising aIIinity membranes were extensively tested in dynamic experiments. The eIIects oI operating parameters
    like Ieed concentration and Ilow rate on separation perIormance like binding capacity, selectivity and process yield have been
    studied in detail in order to Iind the optimal conditions Ior binding and elution steps. The membranes have been used over
    several complete chromatographic cycles to evaluate the eIIects oI ageing and oI membrane regeneration on dynamic binding
    capacity.
    1. C. Boi, S. Dimartino and G.C. Sarti, 2007,

    Advances in membrane aIIinity chromatography Ior the recovery oI antibodies,
    Biotechnol. Prog. 2008, 24, 640-647
    2. C. Boi, G.C. Sarti, Development and characterisation oI aIIinity membranes Ior immunoglobulin puriIication. Sep. Sci.
    Technol., 2007, 42, 2987.
    3. C. Boi, C. Algeri, G.C. Sarti, Preparation and characterization oI polysulIone aIIinity membranes bearing a synthetic peptide
    ligand Ior the separation oI murine immunoglobulins, Biotechnol. Prog. 2008, 24, 1304-1313.
    PD.5.1
    Application of integrated membrane photocatalytic reactor for the treatment of
    synthetic dyes
    R. A. Damodar
    1
    , H.-H. Chou
    2
    , S.-J. You
    3

    1
    Department of Bioenvironmental Engineering and R&D Center for Membrane Technologv, Chung Yuan Christian Universitv,
    200 Chung Pei Road, Chung Li, Taiwan 32023, R.O.C
    2
    Department of Civil Engineering, Chung Yuan Christian Universitv, 200 Chung Pei Road, Chung Li, Taiwan 32023, R.O.C
    3
    Department of Bioenvironmental Engineering and R&D Center for Membrane Technologv, Chung Yuan Christian Universitv,
    200 Chung Pei Road, Chung Li, Taiwan 32023, R.O.C
    sjyoucycu.edu.tw
    Synthetic dyes are major cause oI water pollution and are responsible Ior a variety oI adverse environmental impacts and
    health eIIects, which is mainly due to its color and toxicity. ThereIore the removal oI color and degradation oI the dyes is an
    important requirement in environmental protection. Heterogeneous photocatalysis, a new technique belonging to the class oI
    advanced oxidation process (AOPs), have been intensively investigated in the last two decades has proved to be an eIIective
    treatment method Ior removal oI complex organic pollutants Irom industrial wastewaters owing to its ability to convert them
    into innocuous end products such as CO
    2
    , H
    2
    O and mineral acids. In photocatalysis, titanium dioxide (TiO
    2
    ) catalyst used to
    generate hydroxyl radicals in the presence oI ultraviolet light which attacks organic pollutants present in wastewater. A critical
    need Ior wider, practical application oI this novel technique is to develop more photon eIIicient reactors
    Among the various photocatalytic reactors, slurry types oI reactor showed Iaster degradation as compared to immobilized
    types because it provides high catalyst surIace area. By integrating membrane separation with TiO
    2
    -photocatalysis can resolve
    the slurry separation problem; also process will become ecologically and economically Ieasible. This study was Iocused on to
    evaluate the long term perIormance oI slurry photoreactor Ior RB5 dye removal using submerged membrane Iiltration Ior
    catalyst (TiO
    2
    Deegussa P25) recycle and reuse. Experiment were carried out in a reactor (Vol- 3lit) consisting oI UV-C lamps
    -350-
    and one polytetraIluoroethylene (PTFE) Ilat membrane (0.22m pore size, 0.0151m
    2
    Iiltration area) provided by the R&D
    Center Ior Membrane Technology oI Chung Yuan Christian University, Taiwan.
    Batch study result showed that the rate oI color removal was Iaster than rate oI degradation oI aromatic Iragments. Nearly
    8-10 oI color removed observed in dark due to adsorption oI dye by catalyst and 95 oI color removal was achieved with in
    90min where as Ior aromatic Iragments removal required about 180min. The result suggests that the action oI the OH. radicals
    Iirst attack color giving azo groups and open the NN bonds. The elimination oI azo group leads to Iormation oI some
    aromatic intermediates which was observed at 254nm. It was observed that nearly 75-80 TOC and COD removal was
    achieved in 3hrs oI operation. The sulIate and Iormate ion have been identiIied as mineralize products.
    The catalyst must be recycled and reused without its loss oI activity so long term experiments were Iurther perIormed using
    continuous mode oI operation. The result showed that the perIormance oI dye degradation was observed similar to batch study
    and it was constant during Iirst 40 hrs then slight decrease observed in aromatic Iragment (4 in 180 hrs) and color removal
    (2 in 280 hrs). The permeate Ilux (49 l/m
    2
    .h) and TMP (1 in Hg) was remained constant throughout the experiment which
    indicates no Iouling oI membrane occurs and novel PTFE membrane was able to separate catalyst eIIectively.
    PD.5.2
    Increasing the water recovery in nanofiltration by concentrate treatment: the fouling
    potential of humic acids after (per)ozonation
    S. Van Geluwe
    1
    , B. Van der Bruggen
    1
    , C. Vinckier
    2
    , L. Braeken
    1
    1
    Laboratorv of Phvsical Chemistrv and Environmental Technologv, K.U. Leuven, W. de Crovlaan 46, 3001 Heverlee, Belgium
    2
    Laboratorv of Molecular Design and Svnthesis, K.U. Leuven, Celestifnenlaan 200F, 3001 Heverlee, Belgium
    steven.vangeluwecit.kuleuven.be
    NanoIiltration is an attractive technology to treat surIace water Ior the production oI drinking water. Due to scaling and Iouling
    oI the membrane, the water recovery in nanoIiltration is generally limited to about 80. In this study, a concept is elaborated
    where the concentrate, aIter treatment, returns to the Ieed side oI the membrane in order to reduce the water loss. The Iocus in
    this paper is on the oxidative remediation oI the concentrate in view oI reducing the organic Iouling potential in nanoIiltration.
    Hydrophobic humic acids present in surIace water (and thus in the concentrate) may cause severe membrane Iouling,
    especially the high molecular weight Iraction. The eIIiciency oI ozonation and perozonation Ior the treatment oI concentrated
    humic acid solutions (~ 100 mg/L COD) is evaluated. Laboratory batch scale experiments are carried out as a Iunction oI
    ozone and hydrogen peroxide dosage and reaction time to study the removal kinetics. The degree oI mineralisation, the change
    oI chemical structure (especially the hydrophobicity), the molecular weight distribution and the membrane rejection oI the
    reaction products are analysed. The results are promising because ozone preIerentially oxidizes electron-rich aromatic rings to
    more hydrophilic groups and is able to break down high molecular weight chains into smaller Iragments. However, these
    hydrophilic reaction products are saturated and react typically very ineIIiciently with ozone, so they are not mineralised into
    carbon dioxide and water. The addition oI hydrogen peroxide can Iurther break down these saturated compounds and thus
    decrease the residual COD. Hydrogen peroxide also improves the degradation oI high molecular weight chains signiIicantly.
    -351-
    PD.5.3
    Evaluation of the application of chitosan as a coagulant/flocculatant in a
    microfiltration process of natural water
    Flavia Vieira da Silva
    1
    , Rosngela Bergamasco
    1
    , Miria Hespanhol M. Reis
    2
    , Christian Bouchard
    3
    , Alvaro de
    Araujo
    4
    , Maria Teresa Sousa Pessoa de Amorim
    5
    1
    Department of Chemical Engineering, Av. Colombo., 5790, State Universitv of Maringa, Maringa, Bra:il.
    2
    Department of Chemical Engineering, Av. Engenheiro Dini:, 1178, Federal Universitv of Uberlandia, Uberlandia, Bra:il.
    3
    Departement Genie Civil, Pavillon Pouliot Universite Laval Saint-Fov G1K 7P4, France.
    4
    Department of Food Engineering, Av. Marechal Rondon, s/n, Federal Universitv of Sergipe, Sergipe, Bra:il.
    5
    Department of Textile Engineering, Minho Universitv, Guimares, Portugal.
    Ilaviaeqyahoo.com.br
    In this work, an application oI chitosan as a coagulant/Ilocculant in a microIiltration process oI natural water has been
    evaluated. In order to study Iouling eIIects, the permeation velocity variation oI demineralized water was measured at the
    beginning and at the end oI each microIiltration experiment. The experiments were perIormed at two diIIerent permeation
    velocities, 45 and 90 L h
    -1
    m
    -2
    . At permeation velocity oI 45 L h
    -1
    m
    -2
    microIiltration led to reductions oI UV254 compounds up
    to 33 and 9 oI TOC and 65 oI iron, respectively, while the coagulation-microIiltration process resulted in a reduction up
    to 70, 47 and 100, respectively. However, increased Iouling eIIects were detected Ior the second process. Similar results
    were observed at velocity value oI 90 L h
    -1
    m
    -2
    . Although coagulation caused an increase in Iouling, the treated water quality
    was higher comparatively to the simple microIiltration process. This Iact was evaluated as an important argument Ior the
    application oI the pre-treatment procedure.
    PD.5.4
    Hydrophilic pervaporation for water control in the esterification reaction of ethanol
    and acetic acid
    A. Hasanoglu
    1
    , J. R. Alvarez
    2
    , S. Luque
    2
    1
    Yildi: Technical Universitv, Department of Chemical Engineering, Davutpasa Campuse, 34210, Istanbul, Turkev
    2
    Universitv of Oviedo, Department of Chemical and Environmental Engineering, 33071, Oviedo, Spain
    aycamericyahoo.com
    Pervaporation membrane reactors are the systems in which the separation and reaction are carried out simultaneously in order
    to increase conversions by removing one or more oI the products Iormed in the equilibrium reactions. In this study
    esteriIication reaction oI acetic acid and ethanol producing ethyl acetate and water was investigated using a batch recycle
    reactor. The water Iormed in the reaction was controllably removed by a hydrophilic membrane.
    The membrane used in this work was a PVA based commercial PERVAP 2216 membrane oI Sulzer. Experiments were carried
    out in batch reactors with membrane (PMR) and without using a membrane at 70C to determine the eIIect oI the membrane
    on conversions. SulIuric acid was used as the catalyst. Initial molar ratios oI ethanol/acetic acid were choosen as 8 and 10.
    Conversions increased with increasing molar ratios oI reactants. The ratio oI membrane area/Ieed mixture volume (S/V) used
    was in the range oI 0.99-1.37 cm
    -1
    . The eIIect oI the S/V on the conversions was investigated using diIIerent values oI Ieed
    volumes, and the conversions were Iound to increase by increasing this ratio. The water Iluxes oI the membrane were in the
    range oI 30-60 g/m
    2
    h depending on the water concentrations oI the Ieed. Altough the Iluxes were relatively low, almost
    complete conversions were attained by increasing the ratios oI S/V.
    The concentration oI water in the reactor was reduced more rapidly when the membrane area per unit reaction volume was
    larger. Hence, it is experimantally shown that in a membrane reactor design low permeability oI a membrane could be
    compensated by increasing the membrane area per unit reaction volume to be treated. With the use oI an optimum value oI the
    S/V the reaction mixture can also contact with the membrane surIace more Iully, this could reduce the concentration
    polarization and beneIited the pervaporation |1,2|.
    This work was perIormed at the department oI Chemical and Environmental Engineering oI the University oI Oviedo, in
    Oviedo, Spain.
    -352-
    |1| X.Feng and R.Y.M.Huang, Studies oI a Membrane Reactor:EsteriIication Facilitated By Pervaporation, Chemical
    Engineering Science,1996, 52( 20), 4673-4679.
    |2| M.O.David, R.GreI, T.Q. Nyugen, J. Neel, Pervaporation- EsteriIication Coupling: Part II Modelling oI the inIluence oI
    diIIerent operating parameters, 1991, 69(A), 341-346.
    PD.5.5
    Effect of superficial gas velocity on gas holdup and circulation time in a novel hybrid
    membrane bioreactor
    F. P. Shariati
    1,2
    , M. R. Mehrnia
    1
    , M. H. SarraIzadeh
    1
    , M. Heran
    2
    , C. Wisniewski
    2
    1
    School of Chemical Engineering, College of Engineering, Universitv of Tehran, P.O. Box 11155-4563, Tehran, Iran
    2
    Laboratoire de Genie des Procedes, Eau et Bioproduits, Universite Montpellier 1et 2,
    F-34095 Montpellier, France
    mmehrniaut.ac.ir
    In this work, the eIIects oI superIicial gas velocity on total and riser gas holdup are studied in a novel hybrid membrane
    bioreactor. The system is combination oI three parts: airliIt pump, channel oI oxidation and a membrane. AirliIt pump is used
    Ior circulation oI liquid and includes two baIIle plates that divide the bioreactor in one riser zone and one down-comer zone
    (Figure. 1).
    Experiments are carried out at diIIerent gas superIicial velocity in the range oI 0.008-0.022 m.s
    -1
    at ambient temperature. Total
    gas holdup increases with increasing superIicial gas velocity. On the other hand, riser gas hold up increases with increasing
    superIicial gas velocity until 0.018 m.s
    -1
    but remains constant Ior superIicial gas velocities higher than 0.018 m.s
    -1
    . Similar
    trend is obtained Ior circulation times. It can be seen that, at the lower range oI the air rates studied, riser gas holdup and
    circulation time are strongly dependant oI the superfcial gas velocity, whereas with increasing superfcial gas velocities higher
    that 0.018 m.s
    -1
    , the eIIect oI superfcial gas velocity on both oI them diminishes. However, total gas hold up increases with
    increasing superIicial gas velocity (Figure. 2).

    Figure 1. Schematic oI the hybrid Figure 2. Riser and total gas holdup versus superIicial
    membrane bioreactor gas holdup in a hybrid membrane bioreactor.
    Also, correlations Ior the prediction oI total gas holdup have been developed with superIicial gas velocities that Iound to be in
    good agreement with available data.
    -353-
    PD.5.6
    Optimization of the electrodeionization (EDI) process: comparison of different resin
    bed configurations
    A. Lakehal, K.-E. Bouhidel
    Chemistrv and Environmental Chemistrv Laboratorv (Team of water Chemistrv, Desalination and Environment) Department
    of Chemistrv, Facultv of Science, Universitv of Batna, 05000 Batna, ALGERIA
    Lakehalaichayahoo.Ir
    Introduction
    The optimization oI the EDI resin bed has been and
    remains a serious challenge Ior the design |1, 2...|. What
    is the best design? Thin or thick cell, Single or mixed
    bed.This research work deals with this optimization
    problem. It is based on the comparison oI Iive diIIerent
    conIigurations.
    Experimental
    We have used a three compartments cell with Iour
    electrodes. Two luggin probes measure the trans-bed
    voltage. The basic cell is described elsewhere |3|. The
    experiments are based on the comparison oI I-V or
    eIIiciency-voltage curves oI the Iollowing
    conIigurations: homogenous/mixed, cationic, anionic,
    inert and two layers ordered bipolar beds.
    Results and Discussion
    The Iollowing Iigure illustrates our results which are
    summarized by this eIIiciency order: Two layers ordered
    bipolar bed ~ homogenous mixed bed ~ (cationic,
    anionic, inert) bed. This is particularly due to the bipolar
    eIIect between resin layers and the polarization decrease
    at the CEM and AEM surIaces.
    |1| Thate,S.,N. Specogna, G. Eigenberger,
    Ultrapure water,October 1999.
    |2|C.Larchet et al, Desalination 222 (2008) 489-496.
    |3|K-E. Bouhidel, A. Lakehal, Desalination 193 (2006)411-421.
    PD.5.7
    Butanol recovery from aqueous solutions using pervaporation
    K. Sakaki, H. Negishi, H. Habe, T. Ikegami, H. Yanagishita
    Institute for Innovation in Sustainable Chemistrv, National Institute of Advanced Industrial Science and Technologv (AIST) /
    1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
    k.sakakiaist.go.jp
    In this study, pervaporation (PV) was applied to the recovery oI butanol Irom diluted aqueous solutions. A tubular silicalite
    membrane showed high selectivity toward butanol, and it showed the separation Iactor oI 110 Ior 1 wt butanol aqueous
    solution at 333 K.
    Figure 1 shows a Ilow diagram oI butanol recovery process Irom 1 wt butanol solution using PV. In the process, a silicalite
    membrane is used Ior the separation oI butanol Irom 1 wt butanol solution. The permeate oI the silicalite membrane Iorms
    two phases aIter condensation, and the butanol-rich phase is dehydrated by PV using a hydrophilic zeolite membrane. On the
    other hand, the water-rich phase is Ied to a PV system using a silicone membrane to recover butanol in the aqueous phase. A
    silicone membrane is used here, because it shows the higher separation Iactor than a silicalite membrane in the range oI higher
    butanol concentrations. Considering the heat oI vaporization oI the permeates in each PV process and the electricity oI chillers
    -354-
    Current-applied voltage curve oI continuous EDI. Cell thickness
    2mm; concentration inlet oI NaCl solution: 6.10
    -3
    M.
    Ior condensation oI the permeates in PV, the total energy requirement Ior the butanol separation process shown in Figure 1 was
    estimated to be 7450 kJ/kg-butanol. This value corresponds to about 20 oI the heating value oI butanol.
    Figure 1 Flow diagram oI butanol separation process using pervaporation. Feed: 1 wt butanol solution, product: 100 wt
    butanol at the Ilow rate oI 1 kg/h.
    This study was supported by New Energy and Industrial Technology Development Organization (NEDO).
    PD.5.8
    Textile wastewater reclamation using electrocoagulation and nanofiltration
    integrated system
    A. Aouni, C. Fersi, M. Ben Sik Ali, M. Dhahbi
    Water and membrane technologies laboratorv, CERTE, BP 273 Soliman 8020, Tunisia, Tel 216(71)430044 ,
    Fax 216(71)430934,
    mahmoud.dhahbicerte.rnrt.tn
    Untreated eIIluents Irom textile industries are usually highly coloured and contain a considerable amount oI contaminants and
    pollutants. Stringent environmental regulation Ior the control oI textile eIIluents is enIorced in several countries.
    Previous studies showed that many techniques have been used Ior treatment oI textile wastewater, such as adsorption,
    biological treatment, oxidation, coagulation and/or Ilocculation, among them coagulation is one oI the most commonly used
    technique.
    Electrocoagulation is a process consisting in creating metallic hydroxide Ilocks within the wastewater by electrodissolution oI
    soluble anodes, usually made oI iron or aluminum. This method has been practiced Ior most oI the 20th century with limited
    success. In recent years, however, it started to regain importance with progress oI the electrochemical processes and the
    increase in environmental restrictions in eIIluent wastewater.
    This paper examines the use oI electrocoagulation treatment process Iollowed by nanoIiltration process oI a textile eIIluent
    sample.
    The electrocoagulation process was studied under several conditions such as various current densities and eIIect oI
    experimental tense. EIIiciencies oI COD and turbidity reductions and colour removal were studied Ior each experiment. The
    electrochemical treatment was indented primarily to remove colour and COD oI wastewater while nanoIiltration was used to
    Iurther improve the removal eIIiciency oI the colour, COD, conductivity, alkalinity and total dissolved solids (TDS).
    The experimental results, throughout the present study, have indicated that electrocoagulation treatment Iollowed by
    nanoIiltration processes were very eIIective and were capable oI elevating quality oI the treated textile wastewater eIIluent.
    -355-
    Condensation
    1863 g/h
    54wt%
    1190 g/h
    80wt%
    Phase
    Sep.
    1000 g/h
    100wt%
    250 g/h
    Water
    Dehydration
    PV with
    Silicalite
    membr.
    (d=110)
    673 g/h
    8wt%
    613 g/h
    1wt%
    PV with Silicone
    membr.
    86 g/h
    58wt% 60 g/h
    80wt%
    26 g/h
    8wt%
    Product: BuOH
    1 wt%BuOH
    PD.5.9
    NaA zeolite membranes manufactured by inocermic - dewatering of ethanol by
    vapour permeation in an industrial scale
    J.-Th. Khnert
    1
    , E. Tusel
    2
    , H. Brschke
    2
    , H. Richter
    3
    , M. Weyd
    3
    , I. Voigt
    3
    1
    inocermic GmbH, Hermsdorf, Germanv
    2
    GFT Membrane Svstems GmbH, Homburg/Saar, Germanv
    3
    Hermsdorfer Institut fr Technische Keramik e.J., Hermsdorf, Germanv
    marcus.weydhitk.de
    In order to increase the energy eIIiciency oI bio Iuel all production steps have to be optimised. In bio ethanol production the
    dewatering oI the distilled azeotropic ethanol is a very energy consuming process.
    As an alternative to the conventionally used processes oI azeotropic distillation or pressure swing adsorption (PSA)
    membranes can be used in a very energy eIIicient way. Vapour permeation (VP) with NaA zeolite membranes is the best
    method to dewater ethanol above the azeotropic point.
    The German company inocermic GmbH (inocermic) is producing NaA zeolite membranes
    (Fig. 1) inside oI a Iour channel geometry in an industrial scale. These membranes show high
    Ilux and high selectivity in ethanol dewatering by pervaporation or vapour permeation. AIter
    extended lab-scale tests now the inocermic NaA zeolite membranes proved their good
    perIormance under production conditions with realistic Ieed mixtures in a demonstration plant.
    Stable membrane perIormance at temperatures up to 145C has been demonstrated in industrial
    bioethanol production Irom grain Iermentation since installation in November 2007.
    These convincing separation properties oI the
    membranes led to the construction oI an
    industrial plant with strongly enlarged membrane
    area (Fig. 2). In the meantime several industrial
    plants with 30,000 l/day, 60,000 l/day, 80,000
    l/day, 100,000 l/day and 200,000 l/day bio
    ethanol production with inocermic NaA zeolite
    membranes have been built or are under
    construction by GFT.
    A very important Iactor Ior the overall economy is the correct combination oI
    distillation, rectiIication and dehydration. Optimally combined distillation,
    rectiIication and membrane dehydration systems can reduce the steam
    consumption Ior the whole ethanol concentration to less than 1 kg oI steam per
    1 litre oI dry ethanol. In combination with mechanical vapour compression
    system it is also possible to operate the whole ethanol concentration process
    only with electricity (0.15 KW(e) oI electricity per 1 litre oI dry ethanol) and eliminating in the same time the need Ior cooling
    water. The potential oI energy recovery and optimization oI the separation process is reducing the cost Ior bio ethanol
    production considerably.
    PD.5.10
    Reverse osmosis as a pre-concentration technology in the sugar industry
    S. Gul, A. Friedl, M. Harasek
    Institute of Chemical Engineering, Jienna Universitv of Technologv, Getreidemarkt 9 / 166, A-1060 Jienna, Austria
    sgulmail.zserv.tuwien.ac.at
    Evaporation is one oI the most energy intensive unit operations in sugar Iactories |1|. It has two main drawbacks. Firstly, it
    consumes a huge amount oI energy due to high latent heat oI water and secondly, heating may decompose the sugar molecules
    resulting in low quality and dark coloured sugar |2|. The potential oI developing reverse osmosis (RO) process as a
    concentration technique to remove water Irom Iruit juices has been oI interest to the Iruit juice industry Ior about 30 years.
    Reverse osmosis has shown good results as a pre-concentrator in agro-Iood productions. The advantages oI RO process over
    traditional evaporation are in lower thermal damage to product, increase in aroma retention, less energy consumption and
    lower equipment costs. One main disadvantage oI RO is its inability to reach the concentration oI standard products produced
    -356-
    Fig. 2. Installed vapor permeation membrane modules
    in an industrial bio ethanol plant (6 modules a 20 m)
    Fig. 1. Installation of inocermic
    NaA :eolite membranes into lab-
    scale modules
    by evaporation because oI high osmotic pressure limitation |3|. Reverse osmosis can be used as a pre-concentrator prior to
    conventional evaporation. In this work RO has been investigated Ior use in sugar industry beIore the multiple-eIIect
    evaporators as a pre-concentrator to reduce the load on the multiple-eIIect evaporator or to increase the capacity oI the
    evaporation step and produce high quality sugar. Four diIIerent types oI membranes BW-30(DOW), TFC-SR3 (KOCH), TFC-
    SR2 (KOCH) and UTC-60(Toray) have been investigated Ior concentrating reIined sugar juice Irom 15 to 23w.The observed
    Ilux oI the membranes ranges Irom12-20 kg/m
    2
    h at p3 MPa and T298 K and the rejection Irom 97-99.50. Investigations
    Ior using loose membranes are in progress and the result will be presented in the conIerence. Furthermore, a two stage process
    using a combination oI reverse osmosis and nanoIilotration is suggested which reduces the thermal duty oI the evaporator in
    excess oI 50.
    Film Tec Corporation (DOW) and KOCH Membrane Systems are acknowledged Ior providing membrane samples.
    |1| S.S. Madaeni, S. Zereshki, Reverse osmosis alternative: Energy implication Ior sugar industry, Chem. Eng. Process. 47
    (2008), 1075-1080
    |2| S.S. Madaeni, K. Tahmasebi and S.H. Kerendi, Sugar syrup concentration using reverse osmosis membranes, Eng. LiIe
    Sci., 4 (2004) 187-190.
    |3| B. Jiao, A. Cassano and E. Drioli, Recent advances on membrane processes Ior the concentration oI Iruit juices: a review,
    Journal oI Food Engineering 63 (2004), pp. 303324
    PD.5.11
    Comparison of salt nature and evaluation of the ionic electrochemical mobilities in
    electrodeionization (EDI)
    A. Lakehal, K.-E. Bouhidel
    Chemistrv and Environmental Chemistrv Laboratorv (Team of water Chemistrv, Desalination and Environment) Department
    of Chemistrv, Facultv of Science, Universitv of Batna, 05000 Batna, ALGERIA
    Lakehalaichayahoo.Ir
    Introduction
    EDI is used widely today Ior the production oI high purity water, especially in the semiconductor industry. In spite oI its rapid
    development, there are not established theories, design equations nor clear mechanisms oI regeneration and transport |1|. The
    aim oI this work is to improve the equation J KQ
    n
    in EDI. In previous study |2| we have investigated the eIIects oI voltage
    and Ilow rate. Today we present the eIIect oI salt nature on K value. The slope oI the Iollowing Iigure helps to determine this
    eIIect.
    Experimental
    We have used a three compartments cell with Iour electrodes monitored
    by an AUTOLAB PGSTAT30.
    The basic cell is described elsewhere |2|.
    Results and Discussion
    Various studied salts (Iig1) obey to the equation described in |2|
    (J KQ
    n
    ).
    A sample masse balance and the application oI the Nernst Planck
    migration equation give directly the numerical value oI the average
    ionic mobility. The mobilities in the mixed bed resin reach unexpected
    values.
    Conclusion
    We have improved the equation oI J KQ
    n
    .
    -357-
    PD.5.12
    Saponification and UF/NF separation of value added tocopherols from crude palm
    oil
    K. Vachiraanan
    1
    ,

    J. Rattanapisit
    2
    , P. Sridang
    3
    1
    Department of Chemical Engineering, Prince of Songkla Universitv (PSU), Songkhla 90112,Thailand Tel 00-66-74-287286,
    Fax 00-66-74-21289
    2
    Department of Chemical Engineering, Rafamangala Universitv of Technologv Thanvaburi (RMUTT), Thanvaburi Pathum
    Thani 12110, Thailand. Tel 00-66-2-5494614
    3
    Department of Civil Engineering, Prince of Songkla Universitv (PSU), Songkhla 90112, Thailand Tel 00-66-74-287138, Fax
    00-66-74-212891
    kanja.vhotmail.com
    Crude vegetable oils are constituted mainly oI triglycerides but contain some minor components such as phospholipids, FFAs,
    coloring pigments and phytonutrients as carotenes, vitamin E (tocol; tocopherols and tocotrienols), and sterols |1|. It was
    reported that crude palm oil consists oI 1 phytonutrients with a tocopherol content oI 300-1000 ppm. In comparing these
    phytonutrient groups it has been Iound that vitamin E is value added and is the product Ior which there are increasing demands
    all over the world. Vitamin E is a natural antioxidant that plays signiIicant roles in Iood preservation and disease prevention
    |2-4|. The saponiIication method was used to extract crude palm oil under various conditions in a lab scale unit. In
    saponiIication part, the alcoholic KOH concentration plays the most signiIicant in u-tocopherol loss compared compared to
    time and temperature. The optimum condition oI the saponiIication sample at alcoholic KOH 10 is at T70
    o
    C and time30
    min. However this condition can not remove all triglycerides even it provides a high yield oI u-tocopherols. This comes Irom
    the nature oI components in crude palm oil itselI, in that crude palm oil is constituted oI about 95 triglycerides. ThereIore, it
    is diIIicult to separate tocopherols directly Irom crude palm oil. This research work was to study the integrated processes Ior
    extraction and separation oI tocopherols Irom crude palm oil. UltraIiltration membrane (PVDF400) was used in the next step
    to remove triglyceride Irom crude palm oil aIter the optimum conditions oI reaction step oI saponiIication instead oI
    evaporated organic solvent (hexane) Ior rejecting the residue oI saponiIied substances. In addition, nanoIiltration membrane
    (NF2-GPET) was selected as advanced step to puriIy tocopherols remaining in the Iilterated oI ultraIiltration. The perIormance
    and eIIiciency oI ultraIiltration and nanoIiltration were investigated under consideration oI the optimized condition based on u-
    tocopherol yield. The results pointed out that ultraIiltration could remove most oI the residual triglycerides and phospholipids
    contained in unsponiIiables at a TMP oI 0.5-2.0 bars. The removal oI up to 70 oI triglycerides and phospholipids was
    reached when the mixture was Iiltered by ultraIiltration. The optimum pressure Ior ultraIiltration was in the range oI 0.5 to 1
    bar under the consideration oI yield oI tocopherols, removal oI triglyceride and Ilux decline. It was Iound that tocopherols
    yield loosed about 7 increased aIter passing ultraIiltration. Moreover, nanoIiltration could retain tocopherols in ultraIiltered
    about 80 oI yield at TMP 11.0-12.0 bars.
    |1| Juliana M.L.N. de Moura, Lireny A.G. Goncalves. 2005. Degumming oI vegetable oil by microporous membrane. J. Food
    Eng. 70: 473478.
    |2| Olcott, H. S., Emerson, O.H. 1973. Antioxidants and the autoxidation oI Iats IX: the antioxidant properties oI tocopherols.
    J. American Oil Chemist`s Society 59: 10081009.
    |3| J. BauernIeind in, L. J. Machlin. 1980. Vitamin E A Comprehensive Treatise, Marcel Dekker, New York.
    |4| Burton, G. W. and Ingold, K. U. 1981. Antioxidant activity oI vitamin E and related chain-breaking phenolic antioxidants
    in vitro. J. American Chemist`s Society 103: 6472 - 6477.
    PD.6.1
    Enhanced separation of suspended solids and polysaccharides during microfiltration
    of pulp mill process water
    H. Krawczyk, T. Persson, A.S. Jnsson
    Department of Chemical Engineering, Lund Universitv, BOX 124, SE-221 00 Lund, Sweden
    holger.krawczykchemeng.lth.se
    The increasing scarcity in Iossil resources makes it necessary to use renewable raw materials as energy or chemical raw
    material sources. However, a sustainable exploitation oI wood and agricultural resources requires that we take Iull advantage
    -358-
    oI all Ieedstock components. This implies utilization oI what today is regarded as waste. In mechanical pulp mills Iiber
    residues, hemicelluloses and lignin are discharged, a total amount oI about 50 kg per ton pulp produced. Recovering these
    components would reduce the cost oI waste water treatment; decrease the Iresh water consumption and some components as
    Ior example hemicelluloses could be used in high-value added chemicals.
    Cost eIIicient separation methods are needed to realize a more sustainable pulp production. UltraIiltration (UF) is one method
    to recover hemicelluloses Irom process water Irom thermo-mechanical pulp mills. However the hemicellulose concentration in
    such process water is low (about 1 g/l) and thus to achieve a concentration oI 30 g/l in the Iinal product, the process water has
    to be ultraIiltered until a volume reduction oI 97 (iI the retention is 100 ). This means that inexpensive equipment i.e.
    spiral-wound membranes are needed. To prevent blockage oI the Ieed channels in the membranes the Ieed solution has to be
    pre-treated. Initial experiments have shown that pre-treatment in a drum Iilter is not suIIicient. MicroIiltration (MF) is
    required. The implementation oI the MF stage represents a big challenge since suspended matter tends to Iorm a Iilter cake on
    the membrane that retains hemicelluloses even iI their molecular sizes are much smaller than the pore size oI the membrane.
    The lower hemicellulose concentration in the MF permeate results in increased costs Ior the UF stage as a greater volume oI
    water needs to be separated in order to achieve a predetermined concentration oI hemicelluloses.
    In this work separation oI suspended solids and hemicelluloses in process streams Irom pulp mills was studied using MF. The
    aim was to develop a method Ior removal oI suspended matter without retaining hemicelluloses. The membrane equipments
    evaluated were a tubular module equipped with ceramic membranes (pore sizes oI 0.2, 0.4 and 0.8 m) and a cross-rotational
    membrane module equipped with polymeric membranes (pore sizes oI 0.2, 0.5 and 1.0 m). MF was perIormed at varying
    operating conditions (T 80 C, TMP 0.3 2 bar, v
    cross-Ilow
    2 4 m/s). The process water treated contained 1 g/l suspended
    solids and had a hemicellulose concentration oI about 1 g/l. Suspended solids were removed totally by MF. The transmission
    oI hemicelluloses varied depending on the operating conditions but was about 40 higher using ceramic membranes than
    using polymeric membranes.
    PD.6.2
    Production of ultra pure water from sea water using H-SOD membranes
    S. Khajavi, K. Jansen, F. Kapteijn
    Ceramic Membrane Centre 'The Pore`, DelftChemTech, Delft Universitv of Technologv, Julianalaan 136, 2628 BL Delft, The
    Netherlands
    s.khajavitudelIt.nl
    Hydroxy sodalite (H-SOD) is a zeolite-like material, consisting oI sodalite cages only. Consequently, the material porosity is
    zero dimensional, having no distinct pores or channels, but an array oI cages connected to each other through 4- and 6-rings.
    Although the 4-rings are too small to allow permeation oI any molecule, the diameter oI the 6-rings is large enough (0.27 nm)
    to only allow very small molecules such as helium, ammonia, and water (kinetic diameter: 0.26 nm, 0.255 nm, and 0.265 nm
    respectively) to pass through. Recently, we have reported the synthesis and characterization oI thin, closed Iilms oI hydroxy
    sodalite. Owing to the unique window diameter oI the material, absolute separation oI water Irom hydrogen streams and
    various industrial solvents has been achieved |1-3|.
    Hydroxy sodalite membranes have been utilised as highly water selective membranes in desalination oI Iresh sea water (origin:
    North Sea coast oI The Netherlands). The experiments were carried out at 2.2 MPa cross-membrane pressure and over a wide
    temperature range oI 303-473 K. The membrane was tested over 144 hours oI continuous operation. The collected permeate
    was analysed using Inductively Coupled Plasma (ICP) spectrometry Ior the presence oI Na, K, Li, Ca, Cd, Co, Cu, Fe, Mn, Ni,
    Pb, and Zn.
    The water Ilux exhibited a strong temperature dependency suggesting activated diIIusion. In comparison with water Ilux
    through a system oI demineralised water (2.2 kg/m`2/h at 473 K), the Ilux Irom the desalination experiments was as high as
    3.5 kg/m`2/h at the same conditions. This is attributed to the eIIect oI salts and minerals in the latter case, which increase the
    activity coeIIicient oI water and hence its driving Iorce Ior permeation through the membrane. The ICP measurements showed
    that the water obtained Irom the desalination experiments contained less than 0.02 ppm oI the metal ions originally Iound in
    various amounts in Iresh sea water. In addition, the membrane showed excellent stability in desalinating sea water over a
    course oI 6 days with hardly any variations in Ilux or selectivity.
    This membrane could Iind application in the production oI ultra pure water.
    |1| M. Rhode, G. Schaub, S. Khajavi, F. Kapteijn, J.C. Jansen, Mirop. Mesop. Mat. 115, 2008, 123.
    |2| S. Khajavi, F. Kapteijn, J.C. Jansen , J.Mem.Sci., 299, 2007, 63.
    |3| S. Khajavi, F. Kapteijn, J.C. Jansen , J.Mem.Sci., 326, 2009, 153.
    -359-
    PD.6.3
    Integrated membrane system for biomethan fermentation
    N. Nemestothy, E. Szetgyrgyi, L. Gubicza, K. BelaIi-Bako
    Research Institute of Chemical and Process Engineering, Pannon Engineering, Pannon Universitv, Egvetem u. 10. P.O. Box
    125, H-8200 Jes:prem, Hungarv
    nemesmukki.richem.hu
    Anaerobic membrane bioreactors (AnMBR) have been used in waste water treatment mainly to produce biogas Irom
    renewable resources |1|. In biogas production the AnMBR technology can be combined with gas separation in order to obtain
    biomethane (methane rich biogas) which is more valuable than common biogas |2|.
    In this work Iirstly one-stage lab size batch bioreactors were built and tested to produce biogas Irom various agro wastes
    (stillage, and cellulolitic energy corps). The biogas quality was continuously checked by GC while other parameters (BOD,
    COD, TSS, TP, TS, TN) were measured beIore and aIter the 40 days Iermentation.
    In a high pressure membrane test unit (UWATECH 3DTA), UF and MF membranes were tested, to treat eIIluent oI the batch
    Iermentations. Optimal process conditions and eIIiciency oI COD removal were determined. Moreover gas separation
    membranes (UBE) Ior CO
    2
    removal Irom biogas were studied.
    Based on these results an AnMBR system integrated with gas separation membrane module was designed and constructed. Our
    Iinal product was dehydrated biomethane having less than 5 carbon dioxide content.
    This work was supported by the Hungarian National ScientiIic Foundation Ior Fundamental Research (OTKA PD 72738) and
    by the Hungarian National OIIice Ior Research and Technology in Program Jedlik Anyos grant BIODDFPE.
    |1| F. Meng, S. Chae, A. Drews, M. Kraume, H.-S. Shin, F. Yang Recent advances in membrane bioreactors (MBRs):
    membrane Iouling and membrane material, Water Research, In Press, 3 January 2009
    |2| S.A. Stern, B. Krshnakumar, S.G. Charati, W.S. Amato, A.A. Friedman and D.J. Fuess, PerIormance oI a bench scale
    membrane pilot plant Ior the upgrading oI biogas in a wastewater treatment plant, J. Membr. Sci. 151 (1998) 63-69
    PD.6.4
    Eco-design of a membrane process for preparation of milk protein fractions:
    approach and first results
    S. Omont
    1
    , D. Froelich
    2
    , P. Osset
    3
    , F. Thueux
    3
    , M. Rabiller-Baudry
    4
    , D. Beudon
    5
    , L. Tregret
    6
    , C. Buson
    7
    ,
    G. Gesan-Guiziou
    8
    1
    SERAM, laboratoire MAPIE, 75375 Le Bourget-du-Lac, France
    2
    ENSAM, laboratoire MAPIE, 75375 Le Bourget-du-Lac, France
    3
    ECOBILAN SA, 92208 Neuillv sur Seine, France
    4
    Universite Rennes 1, UMR 6226 Sciences Chimiques de Rennes CNRS, 35042 Rennes, France
    5
    SOREDAB SA, 78125 La Boissiere Ecole, France
    6
    Applexion SAS, Novasep Process, Saint Maurice de Bevnost, 01708 Miribel
    7
    GES, 35530 Noval sur Jilaine, France
    8
    INRA, Agrocampus Ouest, UMR STLO,35000 Rennes, France
    sophie.omontensam.eu; daniel.Iroelichensam.eu ; murielle.rabiller-baudryuniv-rennes1.Ir
    genevieve.gesan-guiziourennes.inra.Ir
    Among the separation operations used in Iood industry, membrane techniques are remarkably appropriate Ior the Iractionation
    oI molecules and are attractive Ior their low environmental impact and their relatively small investment and operating costs.
    These techniques could thereIore represent a good alternative or complement to more polluting and costly chromatographic
    operation, which is commonly used Ior the Iractionation oI speciIic compounds. However, in order to propose innovative
    membrane operations with the purpose oI designing more eIIicient and environmental Iriendly Iractionation processes, it is
    essential to give new insights into the actual environmental impacts oI such operations.
    The goal oI this work is to design a membrane process to prepare milk protein Iractions with target Iunctionality (Iunctional
    Ioods, mainly based on -lactalbumin and -lactoglobulin enriched Iractions) and to compare this process with a
    chromatographic one in order to help to do the better choice Irom both an economical and ecological points oI view by using
    the way oI LiIe Cycle Thinking. The originality oI this project is mainly due to two Iactors: i) the eco-design approach
    -360-
    developed here concerns a process and not a product as it is mainly classically done; ii) the approach is proposed at the initial
    step oI the process proposal in order to choose the better cascade oI membrane operations, including production steps, cleaning
    and recycling oI Iluids. This paper mainly presents the results obtained in terms oI methods based on LiIe Cycle Analysis,
    LCA, related to the Iirst part oI the process. This part oI the process is composed oI all the treatments (heat exchanger,
    microIiltration, ultraIiltration,.) applied to the milk Irom its entrance to the plant to the production oI milk protein
    concentrates. The milk production was chosen not to be included in the study. The second part oI the process describes the
    production oI enriched -lactalbumin and -lactoglobulin Iractions Irom the protein concentrates, the detailed Ilow sheet oI
    which was established with various scenarios, but will not be presented here.
    A simpliIied LCA oI the operations oI the Iirst process subsystem has been carried out, in order to give a global vision oI the
    processes` environmental burden beIore entering in details in the Iurther steps oI the analysis. The results allow us to estimate
    that the greatest impacts come Irom energy consumption mainly by heating processes (up to 50C) and to a lesser extent by
    cooling processes (up to 8C). These processes are chosen in order to either Iavored high membrane Iluxes or control the
    bacteriological behavior oI the valuable Iluids and thus to control Iood saIety. Membrane operations during production
    generate only low impacts in comparison with heating/cooling operations but this conclusion is only partial as cleaning steps
    have not been taken into account yet. We believe that the methodology developed in this project could, in the long run,
    constitute a reIerence Ior eco-design oI other Iood processes.
    This project is carried out with the Iinancial support oI the 'ANR Agence Nationale de la Recherche The French national
    Research agency under the programme National de Recherche en Alimentation et Nutrition humaine (Project ANR-06-
    PNRA-015)
    PD.6.5
    Effect of pulsed electric field on the electrodialysis of passion fruit and naranjilla
    clarified juices
    C. Sierra
    1
    , E. Miguel
    1
    , E. Vera
    1,2
    , P. Sistat
    2
    , P. Huguet
    2
    1
    Escuela Politecnica Nacional (EPN), Departamento de Ciencia de Alimentos v Biotecnologia, P.O.Box 17-02-2759,
    Quito- Ecuador.
    2
    Institut Europeen des Membranes (IEM), Universite Montpellier II, ENSCM, CNRS , CC047, Place Eugene Bataillon, 34095
    Montpellier, France.
    edwin.veraepn.edu.ec
    Several studies have demonstrated that the use oI pulsed electric Iields (PEF) during the electrodialysis (ED) oI solutions
    containing organic compounds, helps to Iouling mitigation and increases the perIormances oI the process |1-3|, which could be
    particularly interesting Ior the treatment oI Iood products. In this work, an evaluation oI the deacidiIication oI passion Iruit and
    naranjilla clariIied juices using conventional and PEF ED has been perIormed.
    Fruit juices were clariIied using a microIiltration module with a membrane oI 0.2 m oI pore size. The ED process was
    perIormed in a cell with an active membrane surIace oI 40 cm, using the solutions and conIigurations as described in |4|. The
    Iollowing operation conditions have been tested: current density oI 300 and 600 A.m
    -2
    , Irequencies between 0.5 to 50 Hz with
    symmetric and asymmetric square waves. The physico-chemical and sensorial properties oI the juices treated with
    conventional and PEF ED were also compared.
    The results showed that the Irequency oI the PEF has an inIluence when employing a density current oI 300 A.m
    -2
    , obtaining
    the best results at low Irequencies. An asymmetric wave with a time relation t
    on
    / t
    oII
    3 improved the deacidiIication time
    without increasing the energy consumption. When comparing conventional and PEF ED, the Iirst had the highest
    deacidiIication rates, however when employing 600 A.m
    -2
    , a decrease on the energy consumption was observed when
    employing PEF, probably due to a Iouling reduction |1-3| . Regarding the juice properties, any diIIerence was observed
    between the conventional or PEF ED.
    |1| J. Park, H. Lee, S. Moon, Determination oI an optimum Irequency oI square wave power Ior Iouling mitigation in desalting
    electrodialysis in the presence oI humate, Separation and PuriIication Technology, 2003, 30, 101-112
    |2| B. Ruiz, P. Sistat, P. Huguet, G. Pourcelly, M. Araya-Farias, L. Bazinet, Application oI relaxation periods during
    electrodialysis oI a casein solution: Impact on anion-exchange membrane Iouling, J. Membrane Sci., 2007, 287, 41-50.
    |3| C. Casademonta, P. Sistat, B. Ruiz, G. Pourcelly, L. Bazinet, Electrodialysis oI model salt solution containing whey
    proteins: Enhancement by pulsed electric Iield and modiIied cell conIiguration, J. Membrane Sci., Article in press.
    |4| E. Vera, J. Sandeaux, F. Persin, G. Pourcelly, M. Dornier, J. Ruales, DeacidiIication oI clariIied tropical Iruit juices by
    electrodialysis. Part I. InIluence oI operating conditions on the process perIormances, J. Food Eng., 2007, 78(4), 1427-1438.
    -361-
    PD.6.6
    Effect of coagulant on sludge thickening using flat sheet membrane
    R.C. Eusebio
    1
    , H.G. Kim
    2
    , H.S. Kim
    1
    1
    Department of Environmental Engineering and Biotechnologv, Mvongfi Universitv, San 38-2 Namdong, Cheoin-Gu, Yongin,
    Kvonggi-Do 449-728, South Korea
    2
    Institute of Construction Technologv, KUMHO Engineering and Construction, =668-2 Daedae-Ri, Yangfi-Mvun, Cheoin-Gu,
    Yongin, Kvonggi-Do 449-820, South Korea
    rceusebiogmail.com
    The eIIect oI adding coagulant in a Sludge Reduction System Ior thickening sludge is presented. Various parameters that
    inIluence the concentration oI thickened sludge were evaluated to assess the eIIectiveness oI membrane as alternative tool Ior
    sludge reduction. In this study, a PVDF Ilat sheet membrane Iabricated by TORAY was used in the experiment with pore size
    oI 0.08m. One system was added with coagulant while the other serves as the control. The membrane was submerged in the
    reactor with a working volume oI 2 liters and continuously aerated at 5 L/min. Experiment was conducted with hydraulic
    retention time (HRT) oI 4 hours and the Ilux was set to 0.3 m
    3
    /m
    2
    d. Transmembrane pressure (TMP) was monitored Ior the
    entire operation and the result showed that the TMP increased with an increase in Ilux. Sludge concentration was determined
    by measuring the amount oI suspended solids and volatile components oI mixed liquor. Extracellular polymeric substances
    (EPS) and soluble microbial product (SMP) were also analyzed by measuring the protein and carbohydrate content oI the
    sludge. Viscosity oI the Iresh sludge was compared with the Iinal viscosity to determine the thickening process eIIiciency. Due
    to the increasing concentration oI suspended solids, the PVDF membrane was easily Iouled causing the TMP to increase. High
    concentration oI EPS in the inIluent sludge increases TMP and decreases Iiltration volume. These microbial products aIIect the
    Iouling mechanism by accumulating and Iorming a thin layer in the membrane`s surIace that greatly contributes in membrane
    Iouling. Addition oI coagulant increases the size oI the particles preventing small particles to deposit in the pores oI the
    membrane that signiIicantly decreases Iiltration perIormance. In the system without coagulant, it is observed that as the pH oI
    the system decreases, the concentration oI microbial products increases, which in turn increases the TMP. With coagulant
    addition, Ilux decline and TMP increase will be minimized.
    This project was supported by the Korean Research Foundation Grant Iunded by Korean Government (MOEHRD)
    KRF-2007-331-D00496
    |1| Wang, Z. et. al. (2007) Application oI Ilat-sheet membrane to thickening and digestion oI waste activated sludge (WAS), J.
    Hazard. Mater., doi; 10.1016/j.jhazmat.2007.10.057
    |2| Meng,F. and F. Yang (2007) Fouling mechanisms oI deIlocculated sludge, normal sludge, and bulking sludge in membrane
    bioreactor, J. Membr. Sci., doi:10.1016/j.memsci.2007.07.038
    |3| Wu, Z. et al. (2007) IdentiIication oI sustainable Ilux in the process oI using Ilat-sheet membrane Ior simultaneous
    thickening and digestion oI waste activated sludge, J. Membr. Sci., doi:10.1016/j.memsci.2008.06.020
    |4| Raszka, A. et. al. (2006) The role and signiIicance oI extracellular polymers in activated sludge. Part I: Literature review,
    hydrobiol, doi:10.1002/aheh.200500640
    PE.1.1
    Improvement of the flow distribution in a laboratory membrane filtration cell by
    CFD study
    F. Cortes-Juan
    1,2
    , B. Balannec
    2,3
    , T. Renouard
    3,4
    1
    Universidad Politecnica de Jalencia. C/ Camino de Jera s/n. 46022. Jalencia Spain
    2
    Ecole Nationale Superieure de Chimie de Rennes, Universite de Rennes 1, CNRS, UMR 6226, Avenue du General Leclerc, CS
    50837, 35708 Rennes Cedex 7, France
    3
    Universite europeenne de Bretagne
    4
    Universite de Rennes 1, CNRS, UMR 6226, 263 Avenue du General Leclerc, CS 74205, 35042 Rennes Cedex, France
    beatrice.balannecuniv-rennes1.Ir
    In the membrane separation Iield, Ieasibility studies are generally Iirst carried out with small laboratory membrane Iiltration
    cells. These bench-scale cells also allow to evaluate the inIluence oI operational parameters and the membrane perIormances.
    Nevertheless, Ior the accurate interpretation oI Iiltration experiments, the knowledge oI the Ilow Iield in the Iiltration cell is
    -362-
    required. This Ilow is usually considered to be unidirectional with uniIorm velocity, but this assumption oI similar Ilow
    conditions is Iar Irom reality in most Iiltration cells |1|. Smart design oI the cell geometry may improve the Ilow distribution
    and consequently the membrane Iiltration perIormances by increasing shear stress and reducing Iouling.
    So, the aim oI this CFD study was to simulate the Ieed Ilow in
    a Ilat circular cell (HP Filter Holder Irom Millipore, membrane
    surIace area 9.6 cm
    2
    ) with cylindrical inlet/outlet pipes
    (Figure 1). DiIIerent geometries, with a detailed 3D
    description, were compared corresponding to several
    improvements suggestions. The study Iocused mainly on the
    inIluence oI the Ieed chamber thickness, the number and
    location oI the inlet/outlet pipes and the modiIication oI the cell
    top surIace.
    Figure 1: Flow distribution in a Iiltration cell
    The CFD simulations show that the velocity and the shear stress can be increased and that the Ilow distribution can be
    improved by lowering recirculation zones. To validate the results, the nanoIiltration oI a model alkane (C
    20
    , molecular
    mass 282 g mol
    -1
    ) using a polyimide membrane (Starmem

    228 Irom MET, MWCO 280 g mol


    -1
    ) will be perIormed with
    the original and a modiIied cell.
    |1| B. Balannec, J.M. Gozalvez-ZaIrilla, D. Delaunay, M. Rabiller-Baudry, CFD simulation oI a Ilat membrane module as a
    tool to explain Iouling distribution, 10 thWorld Filtration Congress, 14-18 April 2008, Leipzig, Germany, Vol II, 467-471
    PE.1.2
    Experimental and numerical (CFD) investigation of flow and concentration patterns
    in membrane modules with ladder-type spacers
    J.L.C. Santos
    1
    , V. Geraldes
    2
    , S. Velizarov
    1
    , J.G. Crespo
    1
    1
    Requimte/CQFB, FCT - Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal
    2
    Chemical Engineering Department, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
    jose.santosdq.Ict.unl.pt
    Experimental and numerical (CFD) results, obtained Ior twelve diIIerent ladder-type spacer structures under diIIerent
    hydrodynamic conditions, were investigated in order to gain insight into the Ilow and mass transIer proIiles inside the channels
    oI membrane modules |1|. The CFD results were analysed in terms oI shear stress and mass transIer at the walls. A modiIied
    Iriction Iactor was introduced to investigate the eIIect oI the hydrodynamic conditions in the channel on the shear stress at the
    walls.
    The continuity, momentum and mass transport equations with cyclic inlet and outlet boundary conditions were solved with the
    open-source OpenFOAM CFD soItware package |2|. The computational grid was generated using OpenFOAM grid generation
    utilities. The grid is a block-structured hexahedral grid with 500,000 grid points, that was obtained aIter a grid-independence
    study at the highest Reynolds number investigated. The simulations were processed in parallel in a 8 node cluster (SuSE Linux
    9.3, OpenFOAM 1.3, 1.9 GHz CPU, 512 MB RAM/CPU). The total simulation time Ior each case was always higher than 20
    h. The CFD simulations were perIormed Ior water at 25C. The calculations were perIormed Ior Reynolds number values oI
    67, 112, 134, 224 and 336. A Schmidt number oI 600, typical oI a dilute solution oI sodium chloride, was considered in the
    calculation oI the concentration Iield.
    The experimental results showed that the transition between laminar and transitional Ilow regime could be rigorously
    determined Ior the spacers under study. The excellent agreement between the CFD and experimental results suggests that the
    cyclic inlet and outlet boundary condition can be applied with high conIidence. Additionally, it was Iound that the Ilow
    structure is determined, Ior all cases studied, mainly by the transverse Iilaments. The presence oI longitudinal Iilaments in the
    channel was shown to not signiIicantly aIIect the Ilow structure. Finally, mass transIer results demonstrated that the modiIied
    Iriction Iactor could be used Ior selecting the best spacer in terms oI mass transIer eIIiciency.
    |1| J.L.C. Santos, V. Geraldes, S. Velizarov and J.G. Crespo, Investigation oI Ilow patterns and mass transIer in membrane
    module channels Iilled with Ilow-aligned spacers using Computational Fluid Dynamics (CFD), Journal oI Membrane Science,
    305, 2007, 103-117.
    |2| OpenFOAM, OpenCFD Ltd, www.openIoam.org.
    -363-
    PE.1.3
    A computational fluid dynamics study on droplet formation mechanism from
    membrane pore
    G. De Luca
    1
    , A. Di Renzo
    2
    , F. P. Di Maio
    2
    , E. Drioli
    1,2
    1
    Research Institute on Membrane Technologv (ITM-CNR), Jia P. Bucci, 17/C, I-87030 Rende (CS), Italv
    2
    Department of Chemical and Materials Engineering, Universitv of Calabria, Jia P. Bucci 44 /A, I-87030 Rende (CS), Italv
    g.delucaitm.cnr.it
    In last years, the Iormation oI droplet Irom a membrane pore has been largely investigated because inIormation on droplet
    detachment is important to model Direct Membrane EmulsiIication (DME) processes. The production oI water/oil or oil/water
    emulsions using DME has many advantages with respect traditional methods such as: the accurate control oI droplet sizes, the
    low use oI energy and raw materials. From a computational point oI view, diIIerent procedures were used to simulate the
    Iormation oI drops Irom pores, such as Lattice Boltzmann, Computational Fluid Dynamics (CFD) and global Force Balance
    Model (FBM) |1-4|. In this work, oil drop Iormation Irom a circular pore in an aqueous continuous phase has been modelled
    using Iinite-element CFD with Level-Set method to track the moving droplet interIace. The main purpose oI this work is to
    veriIy iI Iorce balance models could predict the detachment oI droplet during a DME process. This is particularly important
    because it allows to deIine simple computational procedures avoiding time-consuming calculations. The CFD simulations have
    shown that interIacial Iorce deIined as Iunction oI pore diameter is not accurate because during the droplet Iormation the oil
    markedly spreads around the pore opening. The simulations show also that the point oI mechanical instability is not located on
    the membrane surIace due to the Iormation oI a neck beIore the complete drop detachment. The last observation is in
    agreement with FBM oI V. 'Schrder et al` |5| and J.D.H Kelder et al. |4|, where the interIacial Iorce is deIined in terms oI
    the neck diameter. In the Schrder et al. model the neck diameter depends on the ratio between droplet and pore size, whereas
    in the J.D.H Kelder et al. model the neck size is equal to the pore diameter but only when the drop is completelv leaned against
    the membrane surIace. Simulations show that, in quiescence oI the continuous phase or with low cross-Ilow velocity, the
    Schrder et al model is more reliable. The analysis oI parameters which characterize the growth oI the droplet neck (Iunction
    used in the J. Schrder et al model) was also carried out.
    |1| S.J. Peng, R. A. Williams, Controlled production oI emulsions using a crossIlow membrane, Trans IChemE, 1998, 76,
    894-901
    |2| G De Luca and E. Drioli, Force balance conditions Ior droplet Iormation in cross-Ilow membrane emulsiIications, Journal
    oI Colloid and InterIace Science, 2006, 294, 436448
    |3| G. De Luca, F. P. Di Maio, A. Di Renzo, E. Drioli, Droplet detachment in cross-Ilow membrane emulsiIication:
    Comparison among torque- and Iorce-based models, Chemical Engineering and Processing, 2008, 47, 11501158
    |4| J.D.H. Kelder, J.J.M. Janssen, R.M. Boom, Membrane emulsiIication with vibrating membranes: A numerical study,
    Journal oI Membrane Science, 2007, 304, 5059
    |5| V. Schrder, O. Behrend, H. Schubert, Journal oI Colloid and InterIace Science, 1998, 202, 334-340.
    PE.1.4
    Flow behaviour in a rectangular airlift membrane bioreactor with different baffle
    Angles
    A. Khalili-Garakani, M. Mehrnia, N. MostoIi, M. H. SarraIzadeh, F. Sadeghi
    School of Chemical Engineering, College of Engineering, Universitv of Tehran, P.O.Box. 11155-4563, Tehran, Iran.
    mmehrniaut.ac.ir
    Membrane bioreactor (MBR) is an eIIicient technology Ior wastewater treatment and reuse. This reliable and eIIicient
    technology has become an acceptable alternative to conventional activated sludge processes and an option oI choice Ior many
    domestic and industrial applications |1,2|. In this study, Ilow behaviour in a rectangular airliIt MBR with 0.7 m height, 0.24 m
    width and 0.18 m depth has been studied. Two baIIles with diIIerent angle (90,87.5,85,82.5 degree) have been used Ior
    increasing liquid velocity on the membrane and decreasing membrane Iouling. In this paper, the inIluence oI baIIle angle on
    Ilow behavior was investigated with water and air in the bioreactor. In CFD simulation, the Eulerian-Eulerian two-Iluid model
    was used to simulate dispersed gas-liquid Ilow in an immersed membrane bioreactor. The standard k-c model oI turbulence
    seems to perIorm satisIactorily. The role oI unsteady two-phase Ilow in diIIerent angles oI baIIles was studied. The schematic
    -364-
    diagram oI the system used in this study and the computational mesh with diIIerent angles shown in Figure.1. The geometry
    used Ior the simulations was identical to that used Ior the experiments with the exception that Ior the simulations only halI oI
    the tank was created with the membrane plane used as a symmetry plane (Figure.1b). The results showed the importance oI the
    gap size between baIIles and the membrane in improving air distribution and mixing in Ilat sheet submerged membrane
    bioreactors (Figure.1c).
    Figure 1. (a) Schematic oI the MBR system; (b) Computational domains with simulation grid oI 1,409,095 cells in diIIerent
    angles; (c) LeIt: air distribution, Right: liquid mixing.
    |1| Stephenson, T., Judd, S., JeIIerson, B. and Brindle, K. (2000). Membrane bioreactors Ior wastewater treatment, IWA Pub.,
    London, UK.
    |2| Yang, W.B., Cicek, N. and Ilg, J. (2006). State-oI-the-art oI membrane bioreactors: Worldwide research and commercial
    application in North America. Journal oI Membrane Science, 270(1-2), 201-211.
    PE.1.5
    Optical measurement of dispersion in spacer-filled channels
    C. Bayer, H. Breisig, M. Follmann, C. Fritzmann, T. Melin
    AJT / Chemical Process Engineering, RWTH Aachen Universitv, Germanv
    christoph.bayeravt.rwth-aachen.de
    Coated Ilat-sheet contacting devices are currently under development Ior a variety oI applications, e.g. in air conditioning |1|,
    in the removal oI CO
    2
    Irom Iuel gases oI biological origin |2| or in the elimination oI trace organics Irom wastewater.
    Generally, the relative take-up capacity oI the stripping Iluids is very large leading to low cross-Ilow velocities in the permeate
    channel. This undesirable consequence broadens the residence time distribution so that the stripping Iluid is loaded unevenly.
    However, its eIIect can be reduced by enhancing lateral mixing. To quantiIy the mixing eIIects oI spacers at diIIerent hydraulic
    conditions, this paper presents a suitable measurement method Ior lateral dispersion in spacer-Iilled channels.
    The measuring concept is based on mixing an acidic and an
    alkaline stream, both marked with a pH indicator. The points in
    space where the pH indicator shiIts its color are directly observed
    by photometric analysis. This way, any disturbance caused by
    measuring instruments is avoided. The resulting image is
    interpreted by transIorming the axial space coordinate to a time
    coordinate, so that an analytical solution to Fick's Second Law
    can be Iitted to the color-change Iront (Iigure 1). The dispersion
    coeIIicient, which is a measure Ior lateral mixing in the spacer-
    Iilled channel, can be therewith obtained directly. First
    measurements indicate that the magnitude oI dispersion is
    comparable to results obtained Ior packed beds |3|.
    Fig. 1: Image oI the Ilow Iield
    This study is part oI the EU Innowatech project (Contract No. 036882), which has been Iinancially supported by the EU
    Commission within the thematic priority Global Change and Ecosystems oI the Sixth Framework Program (FP6-2005-Global-
    SUSTDEV-2005-3.II.3.2).
    -365-
    (b)
    (a)
    (c)
    (90) (87.5)
    (90) (87.5) (90) (87.5)
    |1| V.V. Usachov, V.V. Teplyakov, A.Yu. Okunev, N.I. Laguntsov, Membrane contactor air conditioning system: Experience
    and prospects, Sep. PuriI. Technol., 2007, 57(3), 502-506.
    |2| L.G. Gassanova, A.I. Netrusov, V.V. Teplyakov, M. Modigell, Fuel gases Irom organic wastes using membrane
    bioreactors, Desalination, 2006, 198(1-3), 56-66
    |3| O. Levenspiel, Chemical Reaction Engineering, 3rd Ed., Wiley, 1999, 311
    PE.2.1
    A new industrial concept for crossflow filtration loops: the T.I.S.
    L. Grospelly, P. Lescoche, D. Girard
    SIJA CS65 ZA les Laurons F 26110 NYONS
    dgirardsiva-unit.com
    The TIS is a new Iiltration system concept, which originality comes Irom the integration oI the circulation loop inside the
    housing. T.I.S. meaning Tangential Integrated System.
    Schematically, the membranes are split in two crowns, with each a similar number oI membranes. A crown allows the
    circulation oI the Iluid to be treated in a direction and the other crown in the opposite one. A circulation pump is placed at the
    top oI the housing and sucks the Iluid Irom one part oI the membranes and delivers it back into the other one.
    The originality is thereIore to use the membranes instead oI the stainless steel pipes that make up a standard system. The TIS
    can thereIore be considered as a small system that can be duplicated in order to obtain larger Iiltration areas.
    The advantages coming Irom this concept are the Iollowing:
    E.1.A great modularity.
    E.2.To reduce considerably the internal volume oI the loop oI the industrial unit (reduction by a Iactor 3).
    E.3.To implement the installation in non-speciIic places because oI its compactness.
    E.4.A reduction oI the energy consumption because oI the suppression oI the pressure drops coming Irom the stainless steel
    pipes making-up the circulation loop. From what a smaller quantity oI calories is generated by the circulating pump.
    PE.2.2
    Link between taylor bubble characteristics and fibres bundle geometry: application
    to membrane bioreactors
    C. Bessiere
    1
    , C. Guigui
    1
    , A. Line
    1
    , A. Tazi-Pain
    2
    1
    Universite de Toulouse, INSA, UPS, INP, LISBP, 135 Avenue de Rangueil, F-31077 Toulouse, France
    INRA, UMR792 Ingenierie des Svstemes Biologiques et des Procedes, F-31400 Toulouse, France
    CNRS, UMR5504, F-31400 Toulouse, France
    2
    Centre de Recherche de Jeolia-Eau, Anfou Recherche, Chemin de la digue, 78603 Maisons-Laffitte
    charlotte.bessiereinsa-toulouse.Ir
    Aeration oI hollow Iibres (HFs) bundles is admitted to enhance outside-in Iiltration perIormances and to Iace Iouling. When
    large bubbles like Taylor Bubble (TB) are injected below and through HFs module, Iibres density and Iibres bundle design
    may induce diIIerent deIormation even until the break up oI large bubbles in such conIined systems. Literature reveals little
    knowledge on inIluence oI bundle geometry on large bubbles characteristics in conIined conIigurations.
    The aim oI this study is providing inIormation as shape deIormation and velocity oI a single TB through the junction oI a
    cylindrical vertical pipe and vertical plates; an original set up was built and allows generating single TB without liquid
    superIicial velocity. Both experiments based on high speed camera pictures and an analytical study validate the shape and
    velocity oI a single TB in vertical pipe where slug Ilow is at stake. Moreover, the deIormation and velocity oI the TB through
    the singularity are considered with image analysis and show drastic diIIerences whether plates are spaced Irom pipe exit or not.
    In the latter conIiguration, it clearly appears that the bubble breaks up, and shows smaller velocity contrary to the Iirst
    conIiguration. In any case, velocities are smaller compared to those Ior Iree rising oI cap spherical bubble in a stagnant liquid
    and some assumptions are exposed to explain this phenomenon. Computational Fluid Dynamics (CFD) modeling using
    Volume oI Fluid (VOF) model is undertaken to simulate TB shape and deIormation in diIIerent conIigurations. This study
    leads to new results that could apply in membrane module design.
    Veolia Environment and ADEME are acknowledged Ior granting this work
    -366-
    |1| Cui Z. F., Chang S., Fane A.G., Review: the use oI gas bubbling to enhance membrane processes, 2003, Journal oI
    membrane Science, 221, pages 1-35, doi: 10.1016/S0376-7388(03)00246-1
    |2| Martinelli L., Guigui C., Line A., Characterisation oI hydrodynamics induced by air injection related to membrane Iouling
    behaviour, Proceedings oI Membranes in Drinking Water Production and Wastewater Treatment, 20-22 October 2008,
    Toulouse France.
    |3| Essemiani K., Ducom G., Cabassud C., Line A., Spherical cap bubbles in a Ilat sheet nanoIiltration module: experiments
    and numerical simulation, 2001, Chemical Engineering Science, 56, pages 6321-6327
    |4| Lu Y., Ding Z., Liu L., Wang Z., Ma R., The inIluence oI bubble characteristics on the perIormance oI submerged hollow
    Iiber membrane module used in microIiltration, 2008, Separation and PuriIication Technology, 61, pages 89-95, DOI:
    10.1016/j.seppur.2007.09.019
    |5| Phattaranik J., Fane A. G., Pasquier A. C. S., Wu Bing, Membrane Bioreactor with Bubble-Size TransIormer: Design and
    Fouling Control, 2007, AIChE, 53 (1), pages 243-248, DOI 10.1002/aic.11040
    PE.2.3
    Permeability analysis of membranes for tangencial microfiltration
    M.D.M. Innocentini
    1
    , R.V. Meloni
    1
    , C. S. Silva
    2
    , G. R. YousseI
    2
    , C.O Hokka
    2
    , M.Barboza
    2
    1
    Course of Chemical Engineering Universitv of Ribeiro Preto UNAERP, Av. Costabile Romano, 2201, 14096 Ribeirao
    Preto SP Bra:il
    2
    Department of Chemical Engineering Federal Universitv of So Carlos, Jia Washington Lui:, km 235, 13565-905 So
    Carlos SP Bra:il
    marleiuIscar.br
    The use oI pressure-driven membrane Iiltration Ior various Iood processing, biotechnological and environmental applications
    has become a well-established technology in various industries |1-2|. Membranes can be classiIied under three general
    categories according to the sizes oI the particle that they can retain. Reverse osmosis (RO) membranes are capable oI rejecting
    salt ions while ultraIiltration (UF) membranes are oIten used to retain macromolecules. On the other hand, microIiltration
    (MF) or cross-Ilow Iiltration (CFF) membranes are used to Iilter out particles greater than 0.1 micron |3|. The main concern oI
    this work is the analysis oI the microIiltration and ultraIiltration process. A brieI discussion oI the theory is presented and the
    assumption that Ilux is linearly proportional to the pressure gradient across the membrane is veriIied through experiments with
    water and other Newtonian Iluids in tangential Ilow process. Commercial polymeric membranes were used in the experiments.
    The validity oI Darcy`s law to represent the membrane resistance is experimentally checked and conIronted with permeability
    data Iitted Irom Forchheimer`s equation |4|. The causes oI discrepancies and technical and economic implications oI the
    deviations are discussed based in practical examples.
    |1| H.H.P. Fang, X. Shi, Pore Iouling oI microIiltration membranes by activate slugde, Journal oI Membrane Science 264
    (2005) 161-166.
    |2| S.J. Skerlos, N. Rajagopalan, R.E. DeVor, S.G. Kapoor, V.D. Angspatt, MicroIiltration oI polyoxyalkylene metalworking
    Iluid lubricant additives using aluminum oxide membranes, Journal oI ManuIacturing Science and Engineering, 123 (2001)
    693-699.
    |3| K.J. Hwang, T.T. Lin, EIIect oI morphology oI polymeric membrane on the perIormance oI cross-Ilow microIiltration,
    Journal oI Membrane Science 199 (2002) 41.
    |4| M.D.M. Innocentini, P. Sepulveda, F. Ortega, Permeability, in: M. ScheIIler, P. Colombo (Eds.), Cellular Ceramics:
    Structure, ManuIacturing, Properties and Applications, (2005) 313340.
    -367-
    PE.2.4
    Kinetic of acetone absorption in hollow fiber membrane contactor
    Sz. Modelski, A. Witek-Krowiak
    Instiute of Chemical Engineering and Processes, Wroclaw Universitv of Technologv, 50-373 Wroclaw ul. C. Norwida 4/6,
    Poland
    szymon.modelskipwr.wroc.pl
    1.Introduction
    The aim oI this work were experimental studies oI acetone absorption in water with use oI hollow-Iiber membrane contactor.
    The 'resistance in series' model was used to describe mass transIer process. The experiments were made in batch system in
    laminar and transient Ilow region. Results were approximated by model based on diIIerential equations. The kinetic model
    enables to calculate two parameters: the equilibrium constant and mass transIer coeIIicient. In Iurther analysis the Wilson
    method was used.
    Four series oI experiments, eight runs each, were made Ior accurate approximation oI membrane resistance and gas /liquid
    mass transIer coeIIicients.
    2.Experiments
    The installation worked with Iull recirculation oI water and acetone/N2 mixture. The Iluids were thermostated with /- 1C
    precision. The membrane module used in experiments contained Iive polypropylene Iibers, an area oI the membrane was 0.025
    |m
    2
    |. The in-time determination oI acetone concentration in gas was made with use oI gas chromatograph (FID detector). An
    experiment last 2-3 hours, 9-15 samples were analyzed in this time. The samples were taken automatically. The concentration
    oI acetone in nitrogen at the beginning oI each experiment was ~2.7 |v/v|. The mass balance was checked aIter experiment
    by chromatography analysis oI water/acetone sample. The balance errors were less then 10. BeIore each run the installation
    was dried with hot air Ior 30 minutes and then purged with nitrogen.
    3.Results and Conclusions
    The model and methodology proposed in this studies gives interesting results. The equilibrium constant calculated Ior each
    experiment vary Irom 1.66e-3 to 1.84e-3 comparing to values that can be Iound in literature 1.3e-3 to 2.0e-3. The use oI
    kinetic model might be very useIul Ior systems where the Henry's (equilibrium) constant is unknown. Moreover a batch
    installation does not need as much Iluid volume as continuous one.
    The gas transIer resistance is relevant comparing to liquid and membrane mass transIer resistance. Membrane resistance is not
    dominating in the experimental Ilow range. The proposed correlations Ior gas and liquid mass transIer coeIIicient calculation
    are in good agreement with heat transIer analogy.
    PE.3.1
    Upstream preconcentration of metal cations by way of electrodialysis. Application to
    electrochemical detectors
    S. Le-Than, P. Huguet, M. Cretin, Ph. Sistat, Ph. Da Costa
    Institut Europeen des Membranes (IEM),, Universite Montpellier II,ENSCM, CNRS, CC047, Place Eugene Bataillon, 34095
    Montpellier, France
    philippe.sistatiemm.univ-montp2.Ir
    The metal cations are components oI all water but their presence above a certain concentration is not desirable, in particular Ior
    the heavy species. The speciIic detection oI the heavy cations in the diluted media can require a stage oI concentration in order
    to lower the detection threshold oI the electrochemical sensors. In addition, this stage oI preconcentration must be carried out
    in continuous mode in order to allow water monitoring oI lakes or rivers.
    A speciIic miniaturized electrodialyser has been designed in this aim allowing the handling oI very low solution Ilow and with
    very small dead volume. The Ilow ratio between the diluate and concentrate compartments directly determines the
    concentration Iactor f (ratio oI the outlet concentration to the inlet concentration). Investigation on the inIluence oI the current
    density, and linear speed within the channel has been carried out as well as the importance oI the Ieeding mode (continuous,
    semi-continuous, etc.). The most important Iact is that the diluate outlet concentration must be as close to zero to achieve a
    quantitative preconcentration without losses. Presently a f Iactor oI greater than 50 has been reached with this kind oI cell.
    Attention was Iocused on the cell geometry especially on the concentrate channel conIiguration to optimize the Peclet number.
    As a consequence the electrodialyser channels are very thin (about 100 m) making the electrodialyser a microIluidic device
    by nature. Lastly, an inline electrochemical detector Iollows the concentrate outlet Ior characterization oI the solution.
    -368-
    Minute electrodialvser for cation preconcentration.
    PE.4.1
    Fouling of the anion-exchange membranes during the electrodialysis of aromatic
    amino acid solutions
    A. Bukhovets
    1
    , T. Eliseeva
    1
    , Y. Oren
    2
    1
    Department of Analvtical Chemistrv, Jorone:h State Universitv, 394006 Jorone:h, Russia
    2
    Department for Desalination and Water Treatment, Zuckerberg Institute for Water Research, Ben Gurion Universitv
    POBox 653, 84105 Beer-Sheva, Israel
    bukhovetsinbox.ru
    Electrodialysis (ED) has many advantages (economical and ecological) Ior the demineralization oI amino acids solutions.
    However, the industrial application oI ED Ior such purpose may be hindered by the tendency oI amino acids, especially those
    containing phenyl-groups, to Ioul the anion exchange membranes.
    Build-up oI Iouling causes an increase in resistance, which deteriorates the perIormance oI the process and can eventually lead
    to membranes integrity Iailure |1|.
    This study Iocuses on Iouling oI diIIerent commercial anion-exchange membranes (homogeneous and heterogeneous) in the
    ED with model solutions containing neutral amino acid phenylalanine and sodium chloride. The experiments have been
    carried out in a seven-compartment electrodialysis cell using batch mode at various constant current density values.
    Time dependence oI voltage across the anion-exchange membranes has been obtained Ior all types oI studied membranes in
    sodium chloride (0.02M) solutions and sodium chloride (0.02M) phenylalanine (0.02M) solutions. In addition, membrane
    samples were checked Ior variations in electrical conductivity, ATR-FTIR spectra, contact angle and zeta potential to veriIy
    the extent oI Iouling aIter equilibration in the above solutions and aIter applying electrical currents in the ED unit. Clear
    indications oI strong adsorption oI phenylalanine onto the membrane could be observed.
    The results will be discussed in the light oI the chemical and morphological structure oI the anion exchange membranes used
    in this study.
    |1| E. Ayala-Bribiesca, M. Araya-Farias, G. Pourcelly, L. Bazinet, EIIect oI concentrate solution pH and mineral composition
    oI a whey protein diluate solution on membrane Iouling Iormation during conventional electrodialysis, Journal oI Membrane
    Science, 280 (2006), 790801
    -369-
    PE.4.2
    Experimental design for the evaluation of the influence of different variables on a
    submerged membrane bioreactor for the minimization of fouling phenomenon
    J. Etxebarria, D. Iturbe, A. Urkiaga
    GAIKER Technological Centre, Parque Tecnologico, Edificio 202, 48100 Zamudio, Spain
    etxebarriagaiker.es
    Membrane bioreactors (MBR) Ior wastewater treatment are becoming increasingly popular. Nevertheless, this application is
    still restricted by membrane Iouling which reduces membrane permeability |1, 2|. This Iouling phenomenon during
    ultraIiltration is due to the interaction between the membrane material and the mixed liquor components. In Iact, the process is
    strongly inIluenced by three Iactors: biomass and wastewater characteristics, operational conditions and membrane
    characteristics |3|.
    In this work, a design oI experiments was carried out so as to optimize a submerged membrane bioreactor process. For that, the
    sludge retention time (SRT), mixed liquor suspended solids (MLSS) and the ratio oI soluble COD and particulate COD in the
    inIluent were studied as well as the inIluence they have in the membrane Iouling as a result oI the interaction between them.
    Table 1 shows the working range Ior each variable. As a response oI all these experiments, the concentration oI extracellular
    polymeric substances (EPS) and the permeate Ilux were measured. EPS concentrations were determined as carbohydrate and
    protein, both measured colorimetrically by the methods oI Dubois and Lowry respectively |4|.
    Table 1. Working range oI variables like
    SRT, MLSS and CODs/CODp.
    Variable Working Range
    SRT, d Low-high
    MLSS, mg/L 8000-15000
    CODs/CODp 1; ~1
    All the experiments were perIormed with PVDF hollow Iibre membranes which have an area oI 1m
    2
    and a pore diameter oI
    0.4 m. A synthetic wastewater was prepared to be used as Ieed throughout this study, depending on the ratio oI soluble COD
    and particulate COD.
    Finally, aIter gathering all the inIormation, it was perIormed a statistical analysis in order to determine which variables or
    interaction oI variables were the most signiIicant in the membrane Iouling.
    |1| Chang, I.S.; Bag, S.O.; Lee, C.H. EIIects oI membrane Iouling on solute rejection during membrane Iiltration oI activated
    sludge. Process biochemistry 2001; 36:855-860.
    |2| Kim, J.S.; Lee, C.H.; Chang, I.S. EIIect oI pump shear on the perIormance oI a crossIlow membrane bioreactor, Wat. Res.
    2001; 35:2137-2144.
    |3| Le-Clech, P.; Chen, V.; Fane, A.G. Fouling in membrane bioreactors used Ior wastewater treatment-A review. Journal oI
    Membrane Science 2006; 284:17-53.
    |4| Trussell, R.S.; Merlo, R.P.; Hermanowicz, S.W.; Jenkins, D. The eIIect oI organic loading on membrane Iouling in a
    submerged membrane bioreactor treating municipal wastewater. WEFTEC 2004.
    PE.4.3
    Effect of membrane properties and operational condition of MBR on biofouling
    Sheng-Jie You
    1
    , Shan-Shin Ou
    2

    1
    Department of Bioenvironmental Engineering and R&D Center for Membrane Technologv, Chung Yuan Christian Universitv,
    200 Chung Pei Road, Chung Li, Taiwan 32023, R.O.C
    2
    Department of Civil Engineering, Chung Yuan Christian Universitv, 200 Chung Pei Road, Chung Li, Taiwan 32023, R.O.C
    sjyoucycu.edu.tw
    BioIouling is the major problem need to be conIronted in the membrane bioreactor (MBR) process. Many investigations
    showed that the physical and chemical properties oI mixed liquid suspended solid greatly inIluences the MBR operation
    perIormance and these properties also changes with the sludge composition at particular operating conditions. Inevitably
    -370-
    Iouling requires physical and chemical cleaning oI the membrane. The membrane conIiguration as well as membrane material
    and its properties showed diIIerent Iouling rate. The membrane surIace and its liIespan were also aIIected by type oI physical
    and chemical cleaning used Ior bioIouling removal.
    In this study, a novel polytetraIluoroethylene (PTFE) Ilat membranes with diIIerent hydrophobicity (contact angle, CA70,
    90, 130) and having a pore size oI 0.22m and a Iiltration area oI 0.1515m
    2
    provided by R&D Center Ior Membrane
    Technology, (Chung Yuan Christian University, Taiwan) were used. The long-term MBR pilot plant was installed with three
    PTFE membranes and operated under diIIerent sludge retention time (SRT) which was 2, 5, 10, 30 days, respectively. The
    composition oI wastewater was simulated similar to the Nahu Municipal Wastewater Treatment Plant, Taipei. The permeate
    withdraw at intermittent suction mode with a cycle oI 5 min-pause and 10 min-run. The characteristics oI sludge were also
    monitored to identiIy its interrelation with Ilux, transmembrane pressure (TMP), extracellular polymer substrates (EPS)
    concentration.
    The results revealed that at low SRT (2day), the Ilux productivities oI three diIIerent hydrophobic membranes were similar but
    the variation oI TMP was signiIicant. The increment oI TMP was observed to be Iaster Ior the membrane having higher
    hydrophobicity. However, such inIluence oI membrane hydrophobicity was not signiIicant at higher SRT. It was also observed
    that the Ilux declination and TMP rise was Iaster at intermediate SRT. As Ior the operation oI at higher SRT, there were no
    obvious variations oI the high Ilux and low TMP were observed as compared to low SRT. The Iurther analysis oI sludge, EPS
    concentration and cake resistance revealed that the Iormation oI cake layer and its resistances are closely related to sludge
    properties which caused the disappearance oI the hydrophobic eIIect at higher SRT. As SRT increases (2 to 30days), the
    MLSS concentration increases (Irom 670 to 3900 mg/l) and the sludge became more mature which leads to Iorm higher Iloc
    size (Irom 57.06 to 86.94m), also EPS concentration (Irom 196.5 to 140.6) and P/C ratio (Irom 2.25 to 1.43) decreases which
    results in enhancement oI the membrane perIormance at higher SRT. Thus, it indicates that the variation oI operational
    condition greatly inIluences the changes in sludge characteristics and the Iouling which in turn aIIect the membrane
    perIormance.
    PE.4.4
    Modelling the Effect of packing density on filtration performance of a hollow fiber
    microfiltration module used in a specific membrane bioreactor.
    J. Gnther
    1,2
    , P. Schmitz
    2
    , C. LaIIorgue
    2
    , C. Albasi
    1
    1
    Laboratoire de Genie Chimique, UMR CNRS 5503, 5 rue Paulin Talabot, BP 1301, 31106 Toulouse cedex 01, France
    2
    Laboratoire dingenierie des Svstemes Biologiques et des Procedes, UMR INSA CNRS 5504, UMR INSA INRA 792, 135
    avenue de Rangueil, 31077 Toulouse cedex 04, France
    A practical method to obtain design parameters oI hollow Iiber module was demonstrated to show the eIIect oI packing density
    on Iiltration perIormance Ior a speciIic membrane bioreactor. Indeed a speciIic bioreactor has been previously designed in
    order to study microbial interactions (Albasi et al 1998, Salgado et al 2000): a physical separation oI the species in two tanks is
    obtained thanks to a microIiltration membrane. To ensure cultivation conditions similar than the ones in a same reactor,
    Iiltration stage should not be restrictive Ior biological kinetics and the module have to be optimized. Our research Iocused on
    packing density which could be deIined as the total surIace area oI membrane per cross sectional area oI a module. Since high
    Iiber density results in a worse inter-Iibre hydrodynamic environment (Chang 2000), optimization oI Iiber density may be
    important Ior improvement oI the perIormance oI this submerged system.
    In a Iirst part, this study Iocused on Iiltration perIormances with Iluid without particles. Then a two dimensional model was
    designed to simulate the variations in Ilow and Iiltration velocity along a single Iiber oI the microIiltration module. In this
    simpliIied approach a circular tube oI Iluid surrounding the Iiber is considered to account Ior the packing density oI the
    module. 3 D model was then designed to better take into account the eIIect oI packing density on the Iiltration perIormance.
    Finally a 2 dimensional model was realized which allow to show the eIIect oI a heterogeneity oI the packing density at the
    module scale.
    In a second part oI the study a two dimensional model was realized to take into account the deposit along one Iiber and the
    eIIect oI the packing density on the spatial disposition oI the cake. Experimental measurements oI the deposit along Iibers are
    under progress. These results should be examined beside the numerical data. This comparison may be also reported as
    experimental validation.
    All the models used in this study were designed using COMSOL multiphysics soItware. The COMSOL computer code is
    particularly suited to address this problem coupling Navier Stokes model (Iluid domain) and Darcy Brinkman model (porous
    domain).
    ALBASI C., RIBA J.P., MONNA J.P., ESPENAN J.M, 1998, Procede et appareil pour l`homogeneisation de deux milieux
    liquides contenant des composants solides ou dissous et/ou des micro-organismes, brevet depose le 27 juillet 1998, N
    98.09563.
    -371-
    SALGADO MANJARREZ E., C. ALBASI, J.P. RIBA, 2000, A two reservoirs hollow Iiber bioreactor Ior the study oI mixed
    populations dynamics : design aspect and validation oI the approach, Biotechnology Bioengineering, vol. 69 (4) 401-408
    CHANG S., FANE A.G., 2001, The eIIect oI Iiber diameter on Iiltration and Ilux distribution relevance to submerged hollow
    Iibres modules, Journal oI membrane science, 184 (2001), 221-231
    PE.4.5
    Application of a dynamic model for wastewater treatment in submerged membrane
    bioreactors
    A. Zarragoitia
    1,2
    , S. Schetrite
    1
    , U. Jauregui-Haza
    3
    , O. Lorain
    4
    , C. Albasi
    1

    1
    Laboratoire de Genie Chimique, CNRS - Universite de Toulouse, 6 allee Monso, 31029 Toulouse, France
    2
    Departamento de Desarrollo Tecnologico, Centro de Quimica Farmaceutica (CQF), Calle 200 v 21, Apdo. 16042, Atabev,
    Plava. La Habana, Cuba.
    3
    Instituto Superior de Tecnologias v Ciencias Aplicadas (INSTEC), Ave.Salvador Allende Luaces, Pla:a, Ciudad de la
    Habana, Cuba
    4
    Polvmem, Impasse de Palavre 31100 TOULOUSE
    claire.albasiensiacet.Ir
    A mathematical model was developed to simulate Iiltration process and aeration inIluence in Submerged Membrane Bioreactor
    (SMBR). The model development and simulation were Iocused on the description oI existing relationships among the more
    important system variables like Extracellular Polymeric Substances (EPS) concentration, Mixed Liquor Suspended Solids,
    Aeration, Transmembrane pressure, and the Iouling increase during the Iiltration process. A model was developed considering
    the uniIied theory oI Laspidou and Rittman that described the generation oI EPS. For the estimation oI the Iiltration cake
    development, the hypothesis oI two cake layers growth (one dynamic and the other stable) was considered. The biological
    process kinetics and the dynamics oI the sludge attachment and detachment Irom the membrane, in relation to the Iiltration and
    a strong intermittent aeration, were included in the model.
    The model was established in order to simulate and optimize the Iiltration process into SMBR, on the base oI experimental
    data perIormed on a laboratory scale bioreactor. A U-shaped, hollow-Iiber membrane module with an area oI 0.3 m
    2
    (provided
    by Polymem, Toulouse, France) was immersed in a bioreactor oI 10.5 l oI working volume. Hollow Iibers were made oI
    polysulIone with a pore size oI 0.1m, and internal/external diameter oI 0.4/0.7 mm. The SMBR was initially Iilled with
    activated sludge Irom the Brax wastewater treatment plant (2000 eq inhabitants, only domestic wastewater). The municipal
    wastewater was continuously introduced.
    The validity oI the model was checked: various operating conditions (idle-Iiltration time, aeration intensity, Solids Retention
    Time, Hydraulics Retention Time, and Total Suspended Solids concentration were tested. The results oI the numerical
    simulations Iit well the experimental data Irom studied SMBR. This new model provide an important tool Ior study the SMBR
    membrane Iouling problem, but also oIIers the possibility to improve the design conIiguration and operation strategies oI
    SMBR in wastewater treatment, as it is shown with its second application on a bigger pilot: diIIerent optimization criteria were
    considered, to minimize the transmembrane pressure and energy consumption, and to maximize Iiltrate Ilow. The pilot has the
    Iollowing characterisctics: Iour hollow-Iiber membrane modules with an area oI 2.5 m
    2
    (10 m
    2
    oI total Iiltration area) and a
    bioreactor tank oI 1 m
    3
    (Polymem, Labege, France). In this case diIIerent simulation were carried out in order to estimate the
    optimal values oI the operating conditions using the approach oI the experimental design.
    PE.4.6
    Electroreduction of milk and membrane fouling
    J. Pericou, M. Araya-Farias, L. Bazinet
    Institut des Nutraceutiques et Aliments Fonctionnels (INAF), Departement des Sciences des Aliments et de Nutrition, Pavillon
    Paul-Comtois, Universite Laval, Sainte-Fov (QC), Canada, G1J OA6
    monica.araya-IariasIsaa.ulaval.ca
    Omega-3 and probiotic enriched milks oIIer considerable appeal Ior a growing segment oI consumers wanting to eat healthy
    Iood with high Iunctional and nutritive values. However, the oxidoreduction potential (ORP) and the concentration oI
    dissolved oxygen (DO) are mainly responsible Ior the quality loss oI enriched milk |1|. Recent studies on electroreduction oI
    -372-
    milk by membrane electrolysis have shown that this electrochemical process, based on electrode redox reactions, was eIIicient
    to decrease the ORP oI milk |2|. The objectives oI the present study were to evaluate the eIIect oI Ilow rates and acid molarity
    on the eIIiciency oI electroreduction treatments and to study the evolution oI treated milk physico-chemicals parameters during
    storage. To achieve this, electroreduction treatments at Ilow rates oI 100 and 300 mL/min and at acid molarity oI 0.1 and 1.0M
    were carried out on pasteurized skim milk. Treated milk were stored 7 days at 4C in glass jars and under anaerobic conditions.
    Physico-chemical parameters oI milks were evaluated during treatments and storage period. Results obtained showed that ORP
    value decreased Irom a mean initial value oI 192 + 22 mV to a mean Iinal value oI -230 + 23 mV and it was possible to
    maintain a negative ORP in milk during whole storage. On the other hand, DO concentrations in electroreduced milk decreased
    oI 8.1 + 0.3 mg/l to 5.5 + 0.2 mg/l. However, Iouling is Iormed at the membrane surIace due to protein precipitation caused by
    acidic pH. Results obtained showed that ORP reduction was more important when a Ilow rate oI 300 ml/min was used in
    comparison with a Ilow rate oI 100 ml/min. Moreover, at the higher Ilow rate, less Iouling was observed on the membrane
    surIace than at 100 ml/min. This study also showed that storage oI electroreduced milks in glass jars and under anaerobic
    conditions allowed to maintain a negative oxidoreduction potential oI treated milk during 7 days.
    |1| Bolduc, M. P., Bazinet, L., Lessard, J., Chapuzet, J. M., & Vuillemard, J.-C. (2006). Electrochemical modiIication oI the
    redox potential oI pasteurized milk and its evolution during storage. Journal of Agricultural and Food Chemistrv, 54, 4651
    4657.
    |2| Schreyer, A., Britten, M., Chapuzet, J.-M., Lessard, J., & Bazinet, L. (2008). Electrochemical modiIication oI the redox
    potential oI diIIerent milk products and its evolution during storage. Innovative Food Sciences and Emerging Technologv, 9,
    255264
    PE.4.7
    A comparative study of fouling-related properties of bulking and normal sludge
    suspension during membrane filtration
    H. Azami
    1
    , M. R. Mehrnia
    1
    , M. H. SarraIzadeh
    1
    , S. Amiri
    1
    , S. S. Madaeni
    2
    1
    Biotechnologv group, Department of Chemical Engineering, College of Engineering, Universitv of Tehran, P.O. Box
    11155-4563, Tehran, Iran
    2
    Chemical Engineering Department, Ra:i Universitv, Kermanshah, Iran
    mmehrniaut.ac.ir
    Membrane bioreactor (MBR) is an important solidliquid separation technology employed widely in the wastewater treatment.
    However, membrane Iouling is the major problem that hinders the practical application oI membrane bioreactor (MBR)
    systems. A major obstacle Ior the application oI MBRs is the rapid decline oI the permeation Ilux as a result oI sludge bulking
    on the surIace oI membrane. In this paper a series oI membrane Iiltration tests were perIormed to evaluate the Iouling
    behaviors oI Iilamentous bulking sludge and normal sludge. In order to speciIy the Iouling mechanism oI bulking sludge, the
    Iloc morphology oI bulking sludge and normal sludge was studied based on Iractal theory and image analysis.
    The physical and biochemical properties oI activated sludge mixed liquor, including Iloc size distribution, relative
    hydrophobicity, and bound and unbound (soluble) extracellular polymeric substances (EPS), and sludge viscosity were
    examined in this study to evaluate their relationship to membrane Iouling. It was Iound that the Iloc size distribution, Iloc
    morphology and the amount oI soluble EPS in the mixed liquor were the most important properties that signiIicantly
    inIluenced the Iouling propensity oI sludge.
    The results showed that the sludge Ilocs had a good Iractal characteristic, and the boundary Iractal dimension oI bulking sludge
    Ilocs was much larger than that oI normal sludge. The Ilocs oI bulking sludge had more irregular shape than the Ilocs oI
    normal sludge. The irregular shape oI bulking sludge would do great harm to membrane Iiltration process. The higher EPS
    concentration, RH and sludge viscosity oI bulking sludge would speed up membrane Iouling Iurther.
    -373-
    PE.4.8
    The effectiveness of relaxation and backwashing on removing fouling in a flat sheet
    MBR
    P. van der Marel
    1,2
    , A. Zwijnenburg
    2
    , A. Kemperman
    1
    , M. Wessling
    1
    , H. Temmink
    3
    , W. van der Meer
    1,2
    1
    Membrane Technologv Group, Institute of Mechanics, Processes and Control Twente (IMPACT), Facultv of Science and
    Technologv, Universitv of Twente, P.O. Box 217, NL-7500AE Enschede, The Netherlands
    2
    Wetsus, Centre for Sustainable Water Technologv, P.O Box 113, NL-8900 CC Leeuwarden, The Netherlands
    3
    Department of Environmental Technologv, Wageningen Universitv, P.O. Box 8129, NL-6700 EJ Wageningen, The
    Netherlands
    a.j.b.kempermantnw.utwente.nl
    Membrane Iouling hampers Iull-scale applications oI submerged membrane bioreactors (sMBR), despite several advantages
    above conventional systems. Intermediate physical cleaning (backwashing or relaxation) can help to remove these Ioulants and
    to restore the Iiltration resistance. Backwashing may oIIer the advantage over relaxation that also internal Iouling (Fig.1) is
    (partly) removed. Submerged MBRs usually are operated with polymeric hollow Iiber or Ilat-sheet membranes. A major
    disadvantage oI polymeric Ilat sheet membranes is the Iact that they cannot be backwashed at high Iluxes. This lead to the
    development oI new Ilat-sheet polymeric membranes with a backwash capability |1, 2|. The main objective oI this study was
    to elucidate iI backwashing Ilat-sheet membranes is capable oI removing internal Iouling in MBR.
    A Iully automated lab-scale Iiltration set-up was used, applying intermediate
    backwash or relaxation at equal permeate yield: i.e. equal net Ilux |3|. Two
    Ilat-sheet membranes were operated in parallel in both physical cleaning
    modes. In total two types oI polymeric membranes and one type oI ceramic
    Ilat-sheet membrane were used. Activated sludge Ied with municipal
    wastewater was circulated between an MBR pilot and the lab-scale Iiltration
    set-up, enabling long term Iiltration runs (~100 hrs).
    Results showed that both cleaning strategies were well capable oI removing
    the reversible Iouling attributed to cake layer Iormation. Irreversible Iouling
    by internal Iouling occurred equally during operation at either backwashing or
    relaxation. It was thereIore concluded that backwashing was as eIIective in
    restoring the Iilterability oI Iouled Ilat-sheet membranes as relaxation. There
    was a clear diIIerence in irreversible Iouling behavior between the three types
    oI membranes used, which could be attributed primarily to diIIerences in pore morphology. Additionally, chemical cleaning
    was applied by means oI a chemical enhanced backwash with either oxidants or acids. The chemical cleaning showed the
    ability to partially remove the irreversible Iouling. The option oI applying a CEB was Iigured to be the only advantage oI the
    use oI backwashable Ilat-sheet membranes.
    |1| Lyko, M., Filtration & Separation, 2008, 1 (2), 16-19.
    |2| Doyen, W., et al., European Patent EP20050778312, 2005.
    |3| Wu, J., et al., J. Membrane Sci., 2008, 324, 26-32.
    PE.4.9
    The influence of membrane properties on the Silt Density Index
    A. Alhadidi
    1
    , A. Kemperman
    1
    , J Schippers
    2
    , M. Wessling
    1
    , W. Van der Meer
    1
    1
    Membrane Technologv Group, IMPACT, Facultv of Science and Technologv, Universitv of Twente, PO Box 217, 7500 AE
    Enschede, The Netherlands
    2
    UNESCO-IHE Delft, Westvest7, P.O. Box 3015, 2601DA Delft, the Netherlands
    a.m.m.al-hadiditnw.utwente.nl
    Membrane Iouling is deIined as the process in which solutes or particles deposit onto the membrane surIace or into membrane
    pores to such an extent that membrane perIormance is deteriorated. The production oI potable water by reverse osmosis (RO)
    suIIers directly and indirectly Irom the Iouling problem. Several Iouling indexes are commonly applied in RO to investigate
    the quality oI the Ieed water and minimize Iouling problems, such as the Silt Density Index (SDI) and the ModiIied Fouling
    Index (MFI).
    -374-
    Figure 1: Clean and internally Iouled surIace
    oI a Ilat-sheet membrane
    The SDI is the most widely applied Iouling index (standardized procedure as described in ASTM- D4189-07). From a practical
    point oI view, the SDI should be lower than 3 Ior RO Ieed water Ior a better perIormance. The SDI value, however, is
    dependent on the membrane used. In the ASTM standard, the test membrane should be a mixed cellulose nitrate or cellulose
    acetate (MCE) membrane with a pore size oI 0.45m and a diameter oI 47mm.
    In this work, the inIluence oI membrane properties on the SDI value is investigated. Six commercial membrane materials
    (made Irom PVDF, PTFE, acrylic copolymer, nitro cellulose, and cellulose acetate) Irom diIIerent companies were used to
    measure the SDI oI synthetic Ieed waters.
    Three samples were taken Irom each membrane (out oI the same lot), and several membrane properties were measured (pore
    size distribution, porosity, surIace charge, and surIace roughness). SDI values Ior several artiIicial Ieeds were determined. The
    characterization oI these membranes shows a clear variation between batches oI the same membrane type, and within a batch.
    The reproducibility oI the SDI measurements were aIIected by the operation conditions, operator`s experience and the
    membrane properties. This study clearly shows that there is a need Ior an improved Iiltration index taking the membrane
    properties into account.
    This work is Iinically supported by Vitens, Evides and X-Flow BV.
    PE.4.10
    Microfiltration of pitanga juice: analysis of membrane pore blocking models
    R. S. Ongaratto, I. C. N. Debien, L. A. Viotto
    LAMEFI, Department of Food Engineering (DEA), Facultv of Food Engineering (FEA), Universidade Estadual de Campinas
    (UNICAMP), Rua Monteiro Lobato, 80, PC6121, Cidade Universitario Zeferino Ja:, CEP13083-862, Campinas, Bra:il
    viottoIea.unicamp.br
    Hermia |2| developed Iour empirical models that correspond to Iour basic types oI Iouling: complete blocking, intermediate
    blocking, standard blocking and cake layer Iormation. The parameters considered by these models have a physical meaning
    and contribute to the comprehension oI the Iouling membrane mechanisms. These models were developed Ior dead-end
    Iiltration oI power law non-Newtonian Iluids based in constant pressure Iiltration. In this work Hermia`s models were used to
    investigate the Iouling mechanisms involved in the microIiltration oI pitanga juice. The experiments were perIormed using a
    polymeric membrane oI polyvinylidene Iluoride (PVDF) 0.2 m in a dead-end Iiltration unit. All experiments were carried out
    at 35C, 2bar and 500rpm until concentration Iactor (CF) 2 or 10. The juice used was Iirstly pretreatment with an enzymatic
    blend oI celulase (Cellubrix-L) and pectinase (Pectinex Ultra SP-L) (Novozymes, Denmark) (0.05 by weight oI each
    enzyme). The decline Ilux was well described by Hermia`s model. The results showed that the best Iit to experimental data
    corresponded to the cake layer Iormations, showing a regression coeIIicient (R
    2
    ) higher than 0.97, Iollowed by the intermediate
    blocking model (R
    2
    ~0.98) Ior both concentration Iactor tested. The standard blocking and complete blocking models showed
    the worst Iit with R
    2
    equal 0.96 and 0.92 Ior CF2 and 0.95 and 0.88 Ior CF10, respectively. Comparing the intermediate and
    complete blocking models, it was expected that the Iirst showed a better Iit to Ilux decline, because it considers that some
    molecules may deposit on other molecules previously settled |3|. It should be mentioned that Ilux decay may be caused by
    several Iouling mechanisms together, and the relative importance oI each one changes with time |1|. Despite all mechanisms
    are related with permeate Ilux decline, the cake layer Iormation was the main contribution to this phenomenon during pitanga
    juice microIiltration, independent oI concentration Iactor.
    The authors would like to acknowledge the Brazilian government Ior awarding the research grant which makes this work
    possible.
    |1| A. L. Lim, R. Bai, Membrane Iouling and cleaning in microIiltration oI activated sludge wastewater. J. Memb. Sci., 2003,
    216(1-2), 279-290
    |2| J. Hermia, Constant pressure blocking Iiltration laws application to power-law non-Newtonian Iluids, Tran. Ins. Chem.
    Eng., 1982, 60(2), 183-187
    |3| M. C. V. Vela, S. A. Blanco, J. L. Garcia, E. B. Rodriguez, Analysis oI membrane pore blocking models applied to the
    ultraIiltration oI PEG. Sep. PuriI. Technol., 2008, 62(3), 489-498
    -375-
    PE.4.11
    Experimental study of velocity and transmembrane pressure profiles in spiral
    membranes from the full mapping of protein fouling quantified by FTIR-ATR
    M. Rabiller-Baudry, J. Belmejdoub, L. Paugam, B. Balannec
    Universite Rennes 1, UMR 6226 'Sciences Chimiques de Rennes`, CNRS equipe Chimie et Ingenierie des Procedes, CS
    74205, case 1011, 35042 Rennes cedex
    murielle.rabiller-baudryuniv-rennes1.Ir
    Fluid velocity, shear stress and shear rate at membrane wall as well as transmembrane pressure (TMP) exhibit proIiles in
    complex geometry leading to more or less thick Iouling layer. According to a reverse approach, mapping oI Iouling can be
    used as indirect tracer oI these proIiles when transparency oI modules can not be used Ior understanding these proIiles as in
    spiral membranes and when CFD calculations are not suIIiciently developed according to the actual knowledge Ior answering
    such question.
    Regard to more or less important pressure drop when compared with the TMP, an a priori analysis oI the mapping oI Iouling
    in a spiral NF membrane would evidenced mainly velocity proIile whereas in UF spiral membrane it would be the result oI
    both TMP and velocity proIile.
    Proteins Iouling can be used Ior this purpose as we have already developed a method Ior their quantiIication directly on
    membrane using FTIR-ATR whatever the active layer iI polyethersulIone (PES) or polysulIone (PSU) enter in the composition
    oI the active layer and/or oI the intermediate layer, that is the case Ior the most widely used spiral membranes. This
    experimental approach was validated by CFD calculations Ior Ilat membranes inserted in plate and Irame and vibrating (VSep)
    modules.
    This study shows the Iull mapping oI an UF spiral membrane (6.5 m
    2
    ) and a NF spiral membrane (2.5 m
    2
    ) in relationship with
    Iiltration conditions and discuss the velocity and TMP proIiles that can be deduced Irom these experimental results.
    Such results would probably help then Ior the improvement oI the design oI spiral membrane module and spacers and Ior
    simpliIied approach in CFD calculations.
    PE.4.12
    Ultrafiltration of metalworking fluids: effect of a destabilization/centrifugation
    pretreatment stage on membrane fouling
    D. Allende
    1
    , D. Pando
    1
    , J.M. Benito
    2
    , C. Pazos
    1
    , J. Coca
    1
    1
    Department of Chemical and Environmental Engineering, Universitv of Oviedo, C/ Julian Claveria 8, 33006 Oviedo, Spain
    2
    Department of Chemical Engineering, Universitv of Burgos, Pla:a Misael Bauelos s/n, 09001 Burgos, Spain
    davidallendegmail.com
    The treatment oI waste metalworking Iluids (MWF`s), such as coolants and cutting Iluids, is rather diIIicult because oI their
    toxicity and very high chemical oxygen demand (COD). The complex chemical nature oI commercial MWF`s is an additional
    Iactor Ior an eIIective treatment. Current technologies, such as membrane Iiltration or chemical treatment |1-3|, are quite
    eIIective Ior COD reduction beIore disposal but oIten and hybrid process is needed to IulIill environmental discharge standards
    |4|. In this work, experiments were conducted using a two-step hybrid process: destabilization/centriIugation coupled with
    ultraIiltration (UF). The MWF was previously destabilized by addition oI a coagulant/Ilocculant Iollowed by a centriIugation
    stage, being the heavy phase collected and pumped into an UF unit. Two diIIerent cut-oII ZrO
    2
    Ilat ceramic membranes (50
    kDa and 300 kDa) were studied. The eIIect oI diIIerent coagulant salts (CaCl
    2
    , AlCl
    3
    ) and Nalco polymeric Ilocculants on the
    UF perIormance and membrane Iouling were examined.
    Financial support by the Ministerio de Educacion y Ciencia (MEC, Spain) and the European Commission (project
    CTQ2007-65348, European Regional Development Fund) is grateIully acknowledged. D. Allende was the recipient oI a pre-
    doctoral Iellowship Irom the University oI Oviedo.
    |1| A. Lobo, A. Cambiella, J. M. Benito, C. Pazos, J. Coca., EIIect oI a previous coagulation stage on the ultraIiltration oI a
    metalworking emulsion using ceramic membranes, Desalination, 2006, 200, 330-332
    |2| N. Hilal., G. Busca, F. Talens-Alesson, B. P. Atkin, Treatment oI waste coolants by coagulation and membrane Iiltration,
    Chem. Eng. Process., 2004, 43, 811-821
    -376-
    |3| D. Allende, A. Cambiella, J. M. Benito, C. Pazos, J. Coca, Destabilization-enhanced centriIugation oI metalworking oil-in-
    water emulsions: EIIect oI demulsiIying agents, Chem. Eng. Tech., 2008, 31, 1007-1014
    |4| E. Turano, S. Curcio, M. G. De Paola, V. Calabro, G. Iorio, An integrated centriIugation-ultraIiltration system in the
    treatment oI olive mill wastewater, J. Membr. Sci., 2002, 209, 519-531
    PE.4.13
    Protein external fouling in microfiltration. Effect of protein-protein and protein-
    membrane electrostatic interactions
    C. Velasco
    1,2
    , J.I. Calvo
    1,2
    , A. Martin
    1,2
    , F. Martinez
    1,2
    , A. Hernandez
    1

    ,2
    1
    Depto. de Fisica Aplicada, Fac. de Ciencias, Universidad de Jalladolid, C/Real de Burgos s/n, 47071 Jalladolid, Spain
    2
    Surface and Porous Materials (SMAP), UA-CSIC-UJA, R&D Building, Campus Miguel Delibes, 47071 Jalladolid, Spain.
    tonhgtermo.uva.es
    The Iouling oI a SB membrane due to BSA is analyzed when Iiltered through a positively charged microIiltration membrane,
    SB-6407 made Irom Polyethersulfone/copolymer with 0.45 m pores by Pall&Co under diIIerent pressures and at several
    pH values. In these conditions the Iouling is mainly external Iollowing the so called complete blocking mechanism according
    to the classiIication due to Hermia. Nevertheless a limit non-zero volume Ilux appear, J
    V
    *
    , leading to:
    ( )
    2 V
    * *u t V V V
    V V 0 V
    J J (J J ) e
    complete blocking 2
    * ( )
    dJ
    J J ( J )
    dt


    The constant is J
    0
    K
    A
    /A i.e. the initial volume Ilow per unit oI membrane area, J
    0
    /A times the blocked area per unit oI volume
    Ilown, K
    A
    . This parameter is analyzed in terms oI the interaction between the protein molecules and between those and the
    membrane surIaces.
    It seems clear that the external pore blockage is slightly stronger Ior higher applied pressures and increases when the protein
    and the membrane are strongly electrically repelled and the protein-protein repulsion is either very low or considerably high.
    -377-
    PE.4.14
    Identification of foulants elements in degumming by ultrafiltration (PVDF) of
    miscella of crude canola oil
    L. Ara Campos, M. C.h Chiu, L. A. Guaraldo Gonalves, L. A. Viotto
    Facultv of Food Engineering FEA, State Universitv of Campinas UNICAMP. P.O. Box 6121, CE 3083-862, Campinas,
    So Paulo, Bra:il
    viottoIea.unicamp.br
    Polyvinilidene Fluoride (PVDF) membranes are widely used in ultraIiltration (UF) due his excellent chemical resistance,
    controlled porosity and good thermal and mechanical properties |1|.
    Although oil deposits intent to Iorm a layer under membrane surIace
    since the membrane has a hydrophobic characteristics and their
    structural Iormula is similar to the oil, so they attract themselves,
    causing Iouling. This is the major reason Ior a relatively slow
    acceptance oI this technique in oils industry |1|. The biggest
    diIIiculty on Iull understanding oI Iouling mechanism is on
    identiIying the Ioulant compound that causes Ilux decline. Foulants
    could be present at very low level, but enough to cause irreversible
    Iouling and process unavailability.
    The SEM/EDS technique was used to identiIy possible Ioulant agent
    in PVDF 30kDa membrane (Iigure1) aIter 34h oI continue
    degumming by ultraIiltration oI canola crude oil miscella at pilot unit.
    The elements most Irequently identiIied were K, Fe, Na, Ca e S at 6
    measurements. Others elements such as Mg, Ti and Cu were
    identiIied too but with less Irequency and concentration. Figure (1) Foulant under PVDF membrane
    |1| M. Cheryan; UltraIiltration and MicroIiltration Handbook. Lancaster: Technomic Publ., 1998. 526p
    |2| G. S. Rice, et al; Analysis oI separation and Iouling behaviour during nanoIiltration oI dairy ultraIiltration permeates.
    Desalination, v. 236 p. 23-29 , 2009
    |3| N. A. Ochoa, M. Masuelli, J. Marchese ; EIIect oI hydrophilicity on Iouling oI an emulsiIied oil wastewater with
    PVDF/PMMA membranes. Journal oI membrane science, v. 226, p. 203-211, 2003
    |4| L. J. Zeman, L. Zdney; MicroIiltration and ultraIiltration: principles and applications. Marcel Dekker Inc, New York, 1996.
    PE.4.15
    MF associated with an anaerobic fluidized bed reactor. Part 2: MFI evaluation
    L. L. Beal
    1
    , M. Zeni
    1
    , P. A. BoII
    1
    , A. A. Lovatel
    1
    , S. V. Della Giustina
    2
    1
    Universitv of Caxias do Sul, Francisco Getulio Jargas, 1130, Caxias do Sul, Bra:il
    2
    Federal Universitv of Rio Grande do Sul, Avenida Bento Gonalves 9500,Porto Alegre, Bra:il
    llbealucs.br
    The main goal oI this paper is evaluate the MFI behaviour in a MF membrane associated with anaerobic Iluidized bed reactor
    treating sanitary landIill leachate. The membrane used was PVDF, supplied by KOCH and the transmembrane pressure applied
    was 400.57 + 39.81kPa. The pore diameter was 0.2 m and the Iiltration area was 0.11 m
    2
    . The Ieeding was the liquor which
    was a mixture oI leachate and biomass. The MFI values calculated in the Iirst seven hours shows a very close linear correlation
    between (t/V) and V like is shown in Figure 1. The MFI value was 2.5078 s.L
    -2
    (31,867 s.L
    -2
    when normalized to MFI
    0.45
    ), but
    when it was considered the instantaneous MFI the mean value was 2.494 + 0.588 s.L
    -2
    (31,692 + 6,175 s.L
    -2
    to MFI
    0.45
    ).
    -378-
    Figure1: (t/V) x V behaviour.
    The correlation coeIIicient between Ilux and MFI (r 0.387) shows that in this case the Ieeding characteristics has not been
    enough to explain Ilux variation. It could be inIluenced by others Iactors like pressure variation and cake compressibility. Also,
    it will be evaluated the eIIects oI the chemical cleaning and water cleaning on MFI and Ilux behaviours.
    S. F. G. Boerlage, M. D. Kennedy, M. P. Aniye, E. M. Abogrean, G. Galjaard, J. C. Schippers. Monitoring particulate Iouling
    in membrane systems. Desalination, 1998, v. 118, p.131-142.
    S. F. G. Boerlage, M. D. Kennedy, M. R., Dickson, D. E. Y. El-Hodali, J. C. Schippers. The modiIied Iouling index using
    ultraIiltration membranes (MFI-UF): characterization, Iiltration mechanisms and proposed reIerence membranes. Journal oI
    Membrane Science, 2002, v. 197, p. 1-21.
    PE.4.16
    Direct observation of gypsum growth on RO membranes in the presence of biofilm
    R. Arbel, Y. Oren, M. Herzberg, J. Gilron
    Zuckerberg Institute for Water Research, Ben Gurion Univ., P.O.B. 653, Beer Sheva Israel 84105
    jgilronbgu.ac.il
    The problem oI scaling and bioIouling in reverse osmosis can oIten occur together as bioIouling can lead to enhanced
    nucleation and scaling rates |1|. In an eIIort to elucidate the exact eIIects oI bioIilm on gypsum crystal growth, the authors
    have conducted direct in-situ observations on scale grown on a previously bioIouled membrane in a laminar slit Ilow RO cell
    using an EX-SOD device similar to that developed by Cohen and coworkers |2|. In experiments with an equimolar Ieed
    solution oI calcium chloride and calcium sulIate at just under saturation, measurements were obtained oI rates oI linear crystal
    growth as a Iunction oI position in the Ilow cell. We Iound that the rate oI crystal growth does not monotonically increase with
    distance Irom the channel entrance (table 1), as would be expected Ior crystal growth in a Ilat sheet in the absence oI
    bioIouling. This could be explained iI the bioIilm tends to have a stronger eIIect on concentration polarization and crystal
    growth than the developing boundary layer Irom slit Ilow. CLSM micrographs show strong indications that the crystals are
    embedded in the bioIilm (Figure 1), as bacteria (labeled red) can clearly be seen in plane above the crystals.
    -379-
    Distance from
    entrance
    Crystal growth
    rate
    mm
    m/h
    70.5 89.0
    63 128
    54.1 111
    Table 1: Crystal growth rate as Iunction
    oI distance Irom entrance, exit is 77 mm.
    Bulk gypsum concentration is 18 mM.
    Figure 2: CLSM oI gypsum crystals in bioIilm
    labeled with propidium iodide (cells) and
    concanavalin A (EPS)

    |1| Koren, O., Oren, Y. and J. Gilron, The eIIect oI bioIilm Iormation on scaling in RO membranes, Engineering with
    Membranes, 2008, Agarve, Portugal.
    |2| Michal Uchymiak, Anditya Rahardianto, Eric Lyster, Julius Glater, and Yoram Cohen, A Novel RO Ex-Situ Scale
    Observation Detector (EXSOD) Ior Mineral Scale Characterization and Early Detection, J. Membr. Sci., 291 (2007), 86-95.
    PE.4.17
    Impact of the biologically pretreatment groundwater on membrane fouling
    A. Fuqaha
    1
    , A.Friedl
    1
    , M. Harasek
    1
    1
    Institute of chemical engineering, Jienna Universitv of technologv, Getreidemarkt 9 / 166 - Jienna 1060,Austria
    aIuqahamail.zserv.tuwien.ac.at
    Multiple barriers treatment units in drinking water production are not desirable only to ensure additional removal saIety in case
    pre-barrier is not working optimally but also the perIormance oI any treatment unit can aIIect the eIIiciency oI downstream
    treatment units |1|. The main aim oI conventional granular media Iiltration as a preceding step in membrane water treatment is
    to protect the membrane Iouling, due to their ability to combine the physical, chemical, and biological process. Consequently,
    pathogens and biomass can still pass through the Iilters, which modiIy the membrane Iouling potential in its various Iorms
    (Colloidal, organic, scaling and bioIouling), due to the bioIilm detachment Irom the bioIilters backing materials. Still Iouling is
    inevitable in membrane water treatment processes, Iouling by colloidal particles and its combination with the natural organic
    matter (NOM) is one oI the major categories oI perIormance deterioration. |2|. Colloids cover a wide range oI size, Irom a Iew
    nanometres to micrometers. Many studies suggest that natural organic matter (NOM) is the most important Ioulant during
    drinking water processing |3|, The correlation oI NOM and the colloidal particles size on membrane Iouling have been
    investigated by many researches, some results had shown less Iouling occurred aIter a pre-Iiltration through membranes with
    MW oI 360 KD |4|, They proposed a mechanism Ior membrane Iouling which involves a combination oI adsorption oI small
    molecules on the membrane pore wall and pore blockage by colloidal organics. Other researchers had proven the opposite,
    where the major dominant contribution to membrane Iouling due to the particulate Iraction below 0.1 |5|.
    In this research we want to investigate the inIluence oI the
    realised particles Irom the biological Iilters on the down
    stream membrane process. Contaminated ground water with
    60 mg/l Nitrate had been treated biologically with bioIilters
    Iiled with diIIerent packing materials (Pall rings, Foamed
    plastic, Ziolit and sand) the eIIluent oI the bioIilters had been
    Iiltered in Ilat sheet MF, UF and NF membranes. The MF
    membranes pore size are (0.7, 0.45 and 0.22 m) while the
    UF membrane cutoII are (150 and 50 Dalton). The colloidal
    Iouling on the membrane surIaces had increased 10 times Ior
    the eIIluent oI the bioIilter with pall rings packing materials
    as in Iigure1, and Ior the other biological Iilter the Iouling had
    increased 4, 2.5 and 2 times, due to the concentration and size
    oI the realised particles.
    Figure1: the Iormed cake resistance.
    |1| Fuqaha.A, Harasek.M., Friedl.A.(2006) Review oI membrane biological reactor Ior drinking water production. 5
    th
    European meeting on chemical industry and environment, Vienna , Austria May 3-5 May, (117-125).
    |2| Noeon Park, Boksoon Kwon, Sang-Don Kim and Jaeweon Cho ,Characterizations oI the colloidal and microbial organic
    matters with respect to membrane Ioulants (2006); J. Membr. Sci. 275(1-2),29-36.
    |3| SchIer. A.I., Schwicker. U., Fischer. M.M., Fane. A.G., Waite. T.D. , MicroIiltration oI colloids and natural organic
    matter (2000); J. Membr. Sci. 171,151-171.
    |4| LianIa Song,Kai Loon Chen, Say Leong Ong, and Wun Jern Ng, A new normalization method Ior determination oI
    colloidal Iouling potential in membrane processes,(2004); J. Coll. Sci. 271, 426433.
    |5| Kerry. J. H. and Mark. M. C. (2002) Fouling oI MicroIiltration and UltraIiltration Membranes by Natural Waters. Environ.
    Sci. Technol., 36 (16), 3571 -3576.
    -380-
    PE.4.18
    Fouling understanding during rough non-alcoholic beer with ceramic membrane
    M. Yazdanshenas , S. A.R. Tabatabaee Nezhad
    1
    , M. Soltanieh
    2
    , L. Fillaudeau
    3
    1
    Department of Chemical Engineering of Sahand Universitv of Technologv, Tabri:, Iran.
    2
    Department of Chemical and Petroleum Engineering of Sharif Universitv of Technologv, Tehran, Iran.
    3
    Laboratoire dIngenierie des Svstemes Biologiques et des Procedes, CNRS UMR5504, INRA UMR792, Toulouse, France
    yazdnyahoo.com
    The membrane clariIication oI rough non alcoholic beer (RNAB) constitutes a scientiIic and technical challenges Ior brewing
    industry as an alternative to conventional dead-end Iiltration with Iilter-aid (Kieselguhr) |1-2|. RNAB clariIication has been
    investigated at pilot plant scale with tubular ceramic membranes (0.45m nominal pore diameter). The actual mean pore
    diameter has been determined to be 2.4m whereas RNAB particle size distribution gave a mean volume diameter, D 115m.
    During cross-Ilow microIiltration (CFMF), Ilux declined drastically with time due to the Iouling. The contributing resistances
    in Iouling and Ilux decline has been investigated on the basis oI evaluated resistance in Iinal steps oI operation, aIter water
    rinsing, aIter water backwashing and Iollowing chemical cleaning oI Iouled
    membranes. The reversible Iouling including gel and stationary cake layers
    represented more than 95 Iouling resistance; the remaining resistance was
    attributed to irreversible Iouling which is comprised oI blockage oI pores by
    particles and deposition oI macromolecules onto the internal pore walls. The in-
    pore Iouling has been evaluated by permeation oI clariIied non-alcoholic beer
    and in an other test by evaluating the resistance aIter scrubbing the Iould
    membrane. Both tests revealed that the in-pore Iouling is 5 oI irreversible
    resistance and 0.2 oI total resistance. SEM oI the cross section oI a Iouled
    membrane (Fig1) conIirmed the subsequent deposition oI big particles on the
    membrane surIace and Iorming a cake layer on it (deposit thickness estimated to
    30-40 m). No distinct in-pore Iouling has been Iound with comparision oI the
    SEM oI Iouled membrane body with the SEM oI a new one. These results are
    highly similar to Blanpain et al (1999) and Fillaudeau and Carrere (2002)
    researches with rough Lager beer |3, 4|.
    On the basis oI these Iacts it can be concluded that the Iormation oI the cake and dynamic Iiltration layer on outer surIace oI
    the membrane is the main reason oI Ilux reduction. Under this cake layer, there is a layer oI big particles blocking the entrance
    oI the pores which is permeable to the permeate and also adsorbed macromolecules on the pores walls causing very small
    resistance against permeation. ThereIore it can be predicted that Ior enhancement oI Ilux, hydrodynamic techniques may play a
    signiIicant role.
    Acknoledgements: Applied Research Project oI Ministry oI Industries and Mines oI I.R.Iran and Iran Behnoush Co. are
    acknowledged Ior granting this study.
    |1| Fillaudeau, L., Blanpain-Avet P., DauIin, G., Water, wastewater and waste management in brewing industries. Journal oI
    Cleaner Production, 2006. 14(5): p. 463-471.
    |2| Gan, Q., Beer clariIication by cross-Ilow microIiltration - eIIect oI surIace hydrodynamics and reversed membrane
    morphology. Chemical Engineering and Processing, 2001. 40(5): p. 413-419.
    |3| Fillaudeau, L., H. Carrere, Yeast cells, beer composition and mean pore diameter impacts on Iouling and retention during
    cross-Ilow Iiltration oI beer. J. oI Membrane Sci., 2002. 196(1): p. 39-57.
    |4| Blanpain-Avet, P., et al., The eIIect oI oscillatory Ilow on crossIlow microIiltration oI beer in a tubular mineral membrane
    system - Membrane Iouling resistance decrease and energetic considerations. J. oI Membrane Sci., 1999. 152(2): p. 151-174.
    -381-
    Fig1- SEM photo oI the cake layer in
    miroIiltration oI RNAB
    PE.5.1
    Using infrasonic frequency back pulsing to clean micro and ultra filtration
    membranes, fouled with dextrin, yeast and alumina
    D. S. McLachlan, E. Shugman
    UNESCO Associated Center for Macromolecules and Materials, Department of Chemistrv and Polvmer Science, Universitv of
    Stellenbosch, Matieland 7602, South Africa
    davidsmsun.ac.za
    The Iouling oI micro and ultra membrane Iilters during the Iiltration process necessitates that they be cleaned regularly. Back
    pulsing cleaning, as presented in this paper, has the advantage that the plant does not have to be shut down and that there are
    no soaps to dispose oI.
    In this paper Micro (PAL 0.2 and 0.45 m nylon) and Ultra (Alpha Laval polysulphone 0.1 micron and 100 000 MWCO)
    membranes are Iirst Iouled, using a Ieed pressure oI 100 kPa, in a Ilat test cell, with Dextrin, Yeast or Alumina. AIter this
    inIrasound back pulsing, directly into the permeate space, was used to clean the membrane. During the cleaning, the RO Ieed
    pressure remained at100 kPa and the cross Ilow rate at 45lt/hr. The back pulsing was done using permeate water and at peak
    pressures oI 90, 140 and 180 kPa, i.e. peak Trans Membrane Pressures oI 10, -40 and -80 kPa. In all cases, aIter conditioning,
    there was an initial rapid drop in the Ilux which could be resolved by the apparatus but the 'initial (near instantaneous) Ilux is
    taken to be the value at one minute. All membranes were conditioned using RO water and the value at the end oI the
    conditioning is taken as the clean water value
    At a peak pressure oI 180 kPa the diIIerent membrane/Ioulant combinations were cleaned to Irom 50 to 95 oI the clean
    water value. However, as this pressure is probably to high, to use in practice, a series oI back pulses using both RO water and
    soap solutions, at a peak pressure oI 140 kPa were carried out. Note both the RO water and the soap solutions Ilowed
    backwards through the membrane Ior that part oI the back pulse cycle where the TMP was negative.
    The results to be given in the presentation show that Ilux values oI between 65 and 98 oI the clean water value, can be
    restored by using this procedure. The results also showed little or no improvement when one oI the back pulsing cycles was
    made using a soap solution. In all cases the Iinal Ilux aIter cleaning was higher that the 'initial Ilux at one minute aIter Iouling
    commenced.
    Both SEM micrographs and ultrasonic measurements oI thickness oI the Iouling layer showed that while back pulsing
    eIIectively removed the Iouling layer there was some residual material on the membrane and/or in the pores.
    PE.5.2
    Ultrasonic cleaning of oil-field produced water-fouled ceramic membranes
    M. Ebrahimi
    1
    , A. Wienold
    1
    , P. Mund
    2
    , P. Czermak
    1, 3

    1
    IBPT-Research Group Biochemical Engineering and Membrane Technologv (IBPT), Universitv of Applied Sciences Giessen-
    Friedberg, Giessen, Germanv.
    2
    Atech innovations GmbH, Gladbeck, Germanv
    3
    Dept. of Chemical Engineering, Kansas State Universitv, Manhattan KS, USA
    peter.czermaktg.Ih-giessen.de
    mehrdad.ebrahimitg.Ih-giessen.de
    Fouling through suspended oil and grease, particles and colloids, salts and various other trace metals is one oI the most
    common problems and a major operational Iactor encountered in produced water treatment applications oI membranes.
    Fouling is generally characterized by a decline in permeate Ilux through the membrane over time usually as a result oI
    increased Ilow resistance due to pore blocking and cake Iormation. A signiIicant amount oI research has been done in the area
    oI membrane Iouling and methods to prevent membrane Iouling. Such methods include intermittent backIlushing, vibratory
    shear techniques, electrical Iield inducement among many others. In this study, eIIicient ultrasonic cleaning oI oil-Iield
    produced water-Iouled ceramic membranes was investigated. The membranes were Iouled in a cross-Ilow Iiltration cell and
    subsequently subjected to ultrasound at diIIerent Irequencies, power intensities and durations oI treatment.
    |1| Mikko O. Lamminen, Harold W. Walker, Linda K. Weavers, Mechanisms and Iactors inIluencing the ultrasonic cleaning
    oI particle-Iouled ceramic membranes, Journal oI Membrane Science 237 (2004) 213223
    |2| Dong Chen, Linda K. Weavers, Harold W. Walker, Ultrasonic control oI ceramic membrane Iouling by particles: EIIect oI
    ultrasonic Iactors, Ultrasonics Sonochemistry 13 (2006) 379387
    -382-
    |3| Takaomi Kobayashi, Tsuyoshi Kobayashi, Yoho Hosaka, Nobuyuki Fujii, Ultrasound-enhanced membrane-cleaning
    processes applied water treatments: inIluence oI sonic Irequency on Iiltration treatments, Ultrasonics 41 (2003) 185190
    |4| Shobha Muthukumaran, Sandra Kentish, Sharan Lalchandani et al, The optimisation oI ultrasonic cleaning procedures Ior
    dairy Iouled ultraIiltration membranes, Ultrasonics Sonochemistry 12 (2005) 2935
    PE.5.3
    Cleaning of fouled membranes in oily water filtration, a statistical approach
    M. Hesampour, M. Vnsk, M. Mnttri, M. Nystrm
    Laboratorv of Membrane Technologv and Technical Polvmer Chemistrv, Lappeenranta Universitv of Technologv, 53851
    Lappeenranta, Finland
    Mehrdad.hesampourlut.Ii
    In this study six Iactors including Ilow velocity, temperature, pressure, time oI cleaning, the concentration oI surIactant (SDS)
    and alkaline (NaOH) were studied using three diIIerent membranes (regenerated cellulose (C100H), polysulphone (PS100H)
    and polyvinylidene Iluoride (PVDF200)). These membranes were Iouled during the Iiltration oI a mixture oI cutting oil and
    CaCl
    2
    at pH 7. The minimum number oI experiments (18 trials) was achieved by experimental design using the Taguchi
    method. In each trial, the membranes were Iouled with the same solution but cleaned according to a varying trial condition
    protocol. Water permeabilities aIter Iouling, cleaning and washing with water were measured (Fig. 1). The optimum conditions
    and the contribution oI each Iactor were evaluated by using analysis oI variance (ANOVA). The contribution oI Iactors is
    shown in Fig. 2.
    The results show that the eIIiciency oI cleaning depends on the type oI membrane. The best Ilux recovery was achieved Ior
    regenerated cellulose membrane. The permeability oI this membrane was restored even with water Ilushing. The water
    permeability measurements aIter diIIerent stages showed that the permeability oI the membranes varied diIIerently, while in
    some trials it gradually increased with time in others it was constant.
    The signiIicances oI Iactors vary with membrane type while Ior semi hydrophilic membrane (PS100H) the SDS surIactant
    contributed the most, Ior hydrophobic membrane (PVDF200) the eIIect oI Ilow velocity was more obvious. Increasing pH
    (using NaOH) and pressure had no eIIect on the cleaning perIormance. Temperature was only signiIicant during cleaning oI
    the PVDF membrane.
    |1| J. Lindau, A-S. Jnsson, Cleaning oI ultraIiltration membranes aIter treatment oI oily waste water, J. Membr. Sci., 87
    (1994) 71-78
    |2| S.K.S. Al-Obeidani, H. Al-Hinai, M.F.A. Goosen, S. Sablani, Y. Taniguchi and H. Okamura, Chemical cleaning oI oil
    contaminated polyethylene hollow Iiber microIiltration membranes, J. Membr. Sci., 307 (2008) 299-308
    Fig. 1. Variation oI permeability during diIIerent stages, Trial 1 Fig. 2. The contribution oI diIIerent Iactors on the Ilux recovery
    -383-
    PE.5.4
    Study of membrane ageing mechanisms by free radical species using electron
    paramagnetic resonance
    C. T. Matos
    1,2
    , J. G. Crespo
    2
    1
    IBET Instituto de Biologia Experimental e Tecnologica, P-2781-901 Oeiras, Portugal
    2
    CQFB / REQUIMTE, FCT-Universidade Nova de Lisboa, Campus da Caparica, P-2829-516 Caparica, Portugal
    The ageing oI membranes used in the processing oI aqueous solutions is a major drawback, aIIecting signiIicantly the process
    economy and competitiveness. Membrane aging is caused by oxidation oI the membrane materials, which may be induced by
    diIIerent mechanisms, resulting in reduced membrane perIormance and liIetime. Membrane cleaning is crucial Ior removing
    organic and inorganic substances Irom the membrane surIace and pores, although it is known that Irequent chemical cleaning
    leads, eventually, to a deterioration oI membrane perIormance. The cleaning agents used to remove Ioulants are usually
    aggressive and their contact with the membrane materials plays an important role in membrane ageing. Additionally, in recent
    years there has been a growing interest in the development oI advanced oxidation technologies such as, ozonation,
    chloronation, UV radiation and boron-doped diamond anode oxidation, integrated with membrane processing. The
    combination oI these technologies with membrane systems, improves both the eIIiciency oI the oxidation process and the
    retention oI target compounds. However, the exposure oI membranes to Iree radical species produced by these advanced
    oxidation processes may contribute Ior membrane ageing, limiting the beneIit oI the combined processes.
    Most work published in the scientiIic literature about membrane ageing is Iocused on studying the deterioration oI membrane
    perIormance, and changes in the membrane polymer structure and morphology. Few studies reIer to the Iormation oI Iree
    radicals during membrane oxidation, as agents responsible Ior the ageing process. It seems clear that there is a lack oI
    understanding about the underlying mechanisms oI Iree radical Iormation and their eIIect on the polymer structure and
    morphology and, ultimately, on the membrane perIormance (Ilux and selectivity).
    The objective oI this work is to discuss the mechanisms responsible Ior membrane ageing during membrane cleaning and Ior
    integration with advanced oxidation processes, in order to develop methodologies capable oI minimizing membrane ageing. In
    this work, Electron Paramagnetic Resonance (EPR) was used to detect and quantiIy the Iormation oI Iree radicals produced
    during the above mentioned operations, and correlate them with the structural alterations that the membrane material suIIers.
    The alterations oI structure and morphology oI the membrane polymers, caused by the action oI the Iree radicals, can be
    observed by using diIIerent complementary techniques: Fourier TransIorm InIrared Spectroscopy (FTIR), X-Ray
    Photoelectron Spectroscopy (XPS), Dielectric Relaxation Spectroscopy (DRS), scanning electron microscope (SEM) and
    Atomic Force Microscopy. The knowledge acquired will be discussed aiming at identiIying strategies to minimise membrane
    ageing.
    Financial support Irom the EEA Financial Mechanism 2004-2009 (PT0012) is grateIully acknowledged.
    PF.1.1
    Influence of membrane characteristics and operating conditions on power generation
    with pressure retarded osmosis
    A. Achilli, T.Y. Cath, A.E. Childress
    Department of Civil and Environmental Engineering, Universitv of Nevada Reno, Reno, NJ 89557, United States
    Division of Environmental Science and Engineering, Colorado School of Mines, Golden, CO 80401, United States
    aachilliunr.edu
    In pressure retarded osmosis (PRO) systems, water Irom a low salinity Ieed solution (e.g., Iresh or impaired water) diIIuses
    through a membrane into a pressurized, high salinity brine/draw solution (e.g., seawater). Renewable energy can be generated
    by depressurizing a portion oI the diluted seawater through a hydro turbine |1-3|.
    The objective oI the investigation reported here was to evaluate the eIIects oI membrane characteristics and operating
    conditions on water Ilux and subsequently, on power density (i.e., the power generated per membrane area) under pressure
    retarded osmosis conditions. A predictive PRO model that considers the inIluences oI draw solution, Ieed solution,
    concentration polarization, and hydraulic pressure on water Ilux and power output was developed. The model was validated
    with experimental results. Experiments were conducted using current-generation Iorward osmosis membranes enclosed in a
    custom-made cross-Ilow test unit and an NaCl draw solution.
    -384-
    Water Ilux and power density results Irom experimental and mathematical model will be presented. The maximum hydraulic
    pressure diIIerential that could be achieved during the experiments was 970 kPa (140 psig). The experimental data closely
    Iollowed the model results. At a pressure oI 970 kPa, the water Iluxes achieved were between 1.810
    -6
    and 2.810
    -6
    m/s
    (6.5-10 LMH) Ior the 35-g/L NaCl draw solution and between 3.610
    -6
    and 5.210
    -6
    m/s (13-18.5 LMH) Ior the 60-g/L NaCl
    draw solution, depending on Ieed solution concentrations. These Ilux values are well above results previously reported in the
    literature, likely due to the improved membrane and membrane cell used in the current investigation. In the past |4-7|,
    researches used hydrophobic polymeric membranes in their investigations and hollow Iiber membrane modules that were not
    particularly suited Ior PRO applications.
    The mathematical model that was developed here provides guidelines on how to increase power density in PRO operations.
    Changing operating conditions such as increasing cross Ilow on the membrane, can only marginally improve power density by
    decreasing the eIIect oI external concentration polarization. Greater improvement could be achieved by modiIying the
    membrane structure. A substantial improvement in the power density output could be made by optimization oI the membrane
    support layer to reduce the severe internal concentration polarization that occurs: speciIically, the power density could be
    increased by up to 60 by reducing internal concentration polarization. Thus, development oI new membranes with thinner,
    less tortuous, and more porous support layers may be a key Iactor in successIul osmotic power development.
    |1| S. Loeb and R.S. Norman, Osmotic power plants, Science, 189 (1975) 654-655.
    |2| S. Loeb, Production oI energy Irom concentrated brines by pressure-retarded osmosis, I. Preliminary technical and
    economic correlations, Journal oI Membrane Science, 1 (1976) 49-63.
    |3| S. Loeb, Large-scale power production by pressure-retarded osmosis, using river water and sea water passing through spiral
    modules, Desalination, 143 (2002) 115-122.
    |4| G.D. Mehta and S. Loeb, Internal polarization in the porous substructure oI a semipermeable membrane under pressure-
    retarded osmosis, Journal oI Membrane Science, 4 (1978) 261-265.
    |5| G.D Mehta and S. Loeb, PerIormance oI permasep B-9 and B-10 membranes in various osmotic regions and at high
    osmotic pressures, Journal oI Membrane Science, 4 (1979) 335-349.
    |6| S. Loeb, F.Van Hessen and D. ShahaI, Production oI energy Irom concentrated brines by pressure-retarded osmosis, II.
    Experimental results and projected energy costs, Journal oI Membrane Science, 1 (1976) 249-269.
    |7| S. Loeb and G.D Mehta, A two coeIIicient water transport equation Ior pressure-retarded osmosis, Journal oI Membrane
    Science, 4 (1979) 351-362.
    PF.1.2
    Permeability and selectivity to H
    2
    of Pd membranes supported on porous stainless
    steel tubes
    J.M. Sanchez, M. Maroo, M.M. Barreiro
    CIEMAT, Combustion and Gasification Division, Avda. Complutense 22, 28040 Madrid, SPAIN.
    josemaria.sanchezciemat.es
    In recent years there have been strong developments in membrane technology, and particularly in membrane systems Ior
    hydrogen separation |1|. Palladium membranes are excellent candidates Ior hydrogen puriIication, and they are especially
    interesting when separation and reaction are conducted in a single stage in the so-called 'membrane reactors. CIEMAT is
    coordinating a research project HENRECA- whose objective is the development and testing oI a membrane catalytic
    reactor to upgrade hydrogen-lean gasiIication streams |2|. The work presented here Iocuses on the study oI the perIormance
    oI metallic membranes prepared by the other partner in the project, a Spanish University (University Rey Juan Carlos).
    Membranes studied consist oI a porous stainless steel tube (O.D. 12.7 mm; L80 mm), provided by Mott Metallurgical,
    which has a pore size oI 0.2 m and a porosity oI 20. The porosity oI the support was reduced by brushing and then the
    support was coated with a Pd Iilm by electroless plating.
    -385-
    R
    2
    = 0,9986
    R
    2
    = 0,9979
    0
    1
    2
    3
    4
    5
    6
    7
    8
    9
    10
    0 0,2 0,4 0,6 0,8 1
    Transmembrane pressure (bar)
    F
    I
    u
    x

    (
    m
    o
    I
    /
    m
    2
    s
    )
    X
    1
    0
    0
    N2
    H2

    Figure 1. Flux oI N
    2
    and H
    2
    vs. pressure (Temperature320C,
    Gas Ilow-rates 45 l/h)
    Figure 2. Microscopy image oI the membrane (outer rim)
    Permeability tests have been conducted in a bench scale plant located at CIEMAT, where up to 2 Nm
    3
    /h can be treated, at a
    temperature oI 500C and up to 20 bar. Permeability to N
    2
    and H
    2
    has been measured at diIIerent temperatures room T (Ior
    N
    2
    only), 320C and 380C- at trans-membrane pressure ranging Irom 0.2 to 1.3 bar. Permeate Ilow-rate decreased as
    temperature increased. Results show that Ilux oI H
    2
    ranges between 0.025 mol/m
    2
    s and 0.08 mol/m
    2
    s in the pressure range
    Irom 0.2 to 0.7 bar, while N
    2
    Ilux reached values Irom 0.006 to 0.025 moles /m
    2
    s Ior the same pressure range. H
    2
    to N
    2
    separation Iactor achieved was around 3.75. As Figure 1 shows, a good correlation between permeate Ilux and trans-
    membrane pressure was Iound. This means that Ior the developed membranes the prevailing separation mechanism was
    Knudsen diIIusion, instead oI the solution-diIIusion mechanism which should have been provided by a continuous dense Pd
    layer. Discontinuities in the Pd-layer have been conIirmed by microscopy analysis as shown in Figure 2.
    The Spanish Ministry oI Education and Science is acknowledged Ior granting the work (Project, ENE2004-07758-C02-01)
    |1| G.Q. Lu, J.C. Diniz da Costa, M. Duke, S. Giessler, R. Socolow, J. Coll.& InterI. Sci., 314 (2007), p. 589
    |2| Maroo, M., Sanchez, J.M., Calles, J. A., Sanz, R., 10
    th
    Mediterranean Congress oI Chemical Engineering, Book oI
    Abstracts, (2005) p. 128
    PF.1.3
    Separation of hydrogen issued from the decomposition of hydriodic acid on
    supported MFI-type membrane
    A. Darwiche,

    J. De Lamare, M. Comte, V. Valtchev
    Laboratoire de Reactivite des Surfaces et Interfaces, CEA/DEN/DANS/DPC/SCP, GIF-sur-Yvette/CEA Saclav 91191, France
    Laboratoire de Materiaux a Porosite Controlee, ENSCMu, Universite de Haute Alsace, CNRS UMR 7016, 3 rue Alfred
    Werner, 68093 Mulhouse Cedex, France
    ali.darwicheuha.Ir
    Various processes (extraction, distillation.) are used in industry to separate components Irom gas and liquid mixtures.
    However, the environmental demands and pending energy crisis require new technological solutions, namely the utilization oI
    membrane separation. Organic membranes were Iirst employed by the industry, as
    the majority oI them were manuIactured starting Irom organic polymers oI low
    thermal and chemical stability thus limiting their applications. In contrast, ceramic
    membranes oIIer great potential in separation processes where high temperature and
    pressure resistance is required. The employment oI zeolites in the preparation oI
    inorganic membranes made possible to work under extreme conditions oI
    temperature and chemical aggression, which opened new avenues in the separation
    technology. In addition, the zeolite-type materials are able to separate molecules
    with diIIerence in size less than 1 A and thus to combine unravelled selectivity with
    high resistance. The above Ieatures oI zeolite-containing membranes should be
    combined with high permeability in order to Iace the industrial requirements. The
    latter strongly depend on the quality oI the membrane, that is, thickness, crystal
    orientation and presence oI deIects.
    -386-
    Fig 1. SEM cross section view oI a
    silicalite-1/Al
    2
    O
    3
    membrane.
    The goal oI present work is the optimization oI zeolitic membranes Ior hydrogen separation Irom gas mixtures, in particular
    Irom the decomposition oI hydriodic acid. Membranes oI silicalite-1 (MFI-type) synthesized on Ilat u-Al
    2
    O
    3
    (3.9 mm diameter
    and 2 mm thickness) and on tubular TiO
    2
    substrate were prepared by secondary growth oI electrostatically adsorbed nanoseeds.
    The optimization oI the synthesis oI silicalite-1 membrane Ior hydrogen separation included the investigation oI the key
    parameters, such as the temperature and the duration oI the synthesis. ThereIore, the kinetics oI membrane growth at 100, 130,
    150 and 180 C was investigated. The set oI collected experimental data allowed to optimize the synthesis and to obtain
    uniIorm intergrown zeolite layers with thickness much below 1 m (Figure 1). The synthesized Iilms were characterized by
    scanning electronic microscopy (SEM) and grazing incidence X-Ray diIIraction (XRD).
    The obtained silicalite-1 membranes were careIully calcined and the permeance oI single gases (H
    2
    and Ar), binary (H
    2
    /H
    2
    O)
    and ternary (H
    2
    /HI/H
    2
    O) mixtures tested. Argon was used as sweep gas in the permeate side. For instance, the permeance oI
    hydrogen, water and hydriodic acid Ior a membrane prepared on tubular TiO
    2
    substrate at 140C Ior 5.5 h, are respectively 6.8
    x 10
    -7
    , 3 x 10
    -8
    and 2.5 x 10
    -8
    mol/s.m.Pa.
    The obtained permeation results will be discussed in details. In addition, the perIormances silicalite-1 membranes synthesized
    with tetrapropylammonium cation will be compared with those oI organic template Iree ZSM-5 counterpart. Data oI the
    decomposition oI hydriodic acid on platinum-modiIied MFI-type membranes will also be presented.
    |1| T. Tomita, K Nakayama and H.Sakai, Micropor. Mesopor. Mater. 68 (2004) 71
    |2| J. Caro, M. Noack, P. Klsch and R. SchIer, Micropor. Mesopor. Mater. 38 (2000) 3
    |3| S. Mintova, J. Hedlund, B. Schoeman, V. Valtchev and J. Sterte, Chem. Commun. (1997) 15
    PF.1.4
    Polymer membranes containing ionic liquids for fuel cells
    J. Schauer, M. Paidar, P. Mazur, K. Bouzek
    Institute of Macromolecular Chemistrv, Academv of Sciences of the C:ech Republic, Hevrovskv Sq.2, Prague 6, 162 06, C:ech
    Republic
    Institute of Chemical Technologv, Prague, C:ech Republic
    schauerimc.cas.cz
    The aim oI this work was the preparation oI the membranes containing an ionic liquid, which are ion-conducting in anhydrous
    environment at temperatures above 100 C. The membranes are intended Ior use in Iuel cells.
    The membranes were prepared by dissolving a polymer and an ionic liquid in one solvent, casting a membrane on a Nalgen
    dish and evaporating the solvent. Poly(vinyl alcohol) and poly(vinyl alcohol) crosslinked with maleic acid, polybenzimidazole
    and its derivatives, poly(vinylidene Iluoride-co-hexaIluoropropylene), NaIion and polysulIone were tested as matrix polymers
    while various protic and aprotic ionic liquids based on imidazolium and pyridinium cations were used as a conductive
    component.
    The decisive Iactor in the membrane preparation is the compatibility oI a polymer - ionic liquid system. The systems range
    Irom totally incompatible (e.g. polysulIone and 1-ethyl-3-methylimidazolium ethylsulIate) to Iully compatible ones (e.g.
    poly(vinylidene Iluoride-co-hexaIluoropropylene) and 1-butyl-3-methylimidazolium triIluoromethanesulIonate). Compatibility
    was studied using swelling measurements, electron microscopy and calorimetry.
    Membranes based on incompatible components did not show any ionic conductivity, those based on partially compatible
    components had the conductivity values up to 0.0024 S/cm at 160 C and those based on perIectly compatible ones up to
    0.016 S/cm at 160 C in an anhydrous environment. An addition oI a small amount oI water considerably increased these
    values.
    Some oI the prepared membranes were tested in a laboratory Iuel cell. The membrane was clamped between two electrodes
    HT GDE (E-TEK, Pt content 0.5 mg/cm
    2
    ) and then inserted into the cell. The hydrogen/oxygen cell was operated at
    temperatures up to 160 C in an anhydrous environment. So Iar, only some membranes containing an ionic liquid with
    dissociable hydrogen, such as 1-ethylimidazolium triIluoromethanesulIonate, were Iunctional at temperatures above 100 C.
    The reproducibility oI experiments was, however, rather poor. In successIul experiments, the electrodes were probably
    impregnated with the ionic liquid squeezed out oI the membrane during the electrode-membrane assembly preparation.
    Conclusions. It is possible to prepare a Iuel cell with a membrane containing an ionic liquid which can operate in anhydrous
    environment at temperatures above 100 C. Now, the main task is to prepare reproducibly a proton conductive electrode-
    membrane assembly.
    -387-
    PF.1.5
    Impregnated membranes for direct methanol fuel cells
    D. Stamatialis
    1
    , M.H. Yildirim
    1
    , A. Schwarz
    2
    , M. Wessling
    1
    1
    Institute of Mechanics, Process and Control Twente (IMPACT), Universitv of Twente, Facultv of Science and Technologv,
    Membrane Science and Technologv, P.O. Box 217, 7500 AE Enschede, The Netherlands
    2
    Department of Chemical Engineering, Universitv of Applied Sciences Muenster, Stegerwaldstrasse 39, 48565 Steinfurt,
    Germanv
    d.stamatialisutwente.nl
    High proton conductivity and low methanol cross-over are desired properties oI a good direct methanol Iuel cell (DMFC)
    membrane. NaIion, the current state oI the art polymeric membrane, has high proton conductivity but suIIers Irom high
    methanol cross-over which results in a loss oI Iuel and cathode voltage, decreased cell eIIiciency and liIetime. In this work; we
    use the impregnation concept to develop dimensionally stable and low methanol permeable membranes |1|. NaIion and
    sulIonated poly (phthalazinone ether ketone) (SPPEK) are impregnated into microporous polyethylene (PE) support (Figure 1).
    The impregnation causes reduction oI both methanol cross-over and proton conductivity in comparison to pure membranes.
    Low proton conductivity is oIten compensated by low methanol cross-over leading to better DMFC perIormance. Figure 1b
    shows that the maximum power density oI NaIion PE impregnated membrane (N-PE) is higher than NaIion 117 (N117) at
    various methanol concentrations whereas SPPEK1.4-PE impregnated membrane shows the best perIormance at 6M methanol
    concentration |2|.
    Figure 1. (a) SEM image oI cross-section oI N-PE composite
    membrane
    (b) maximum power density oI membranes at various
    methanol concentrations.
    |1| M.H. Yildirim, D. F. Stamatialis and M. Wessling, J. Membr. Sci., 321 (2008) 364-372.
    |2| M.H. Yildirim, A. Schwarz, D. F. Stamatialis and M. Wessling, J. Membr. Sci., (2009) in press, (doi:10.1016/j.memsci.
    2008.11.051).
    PF.1.6
    Generating power utilizing PRO-membranes with a hierarchical structure
    C. Chaumette, C. Hnel, G. Bisle, E. Walitza, T. Schiestel
    Fraunhofer Institute for Interfacial Engineering and Biotechnologv, Nobelstr. 12, 70569, Stuttgart, Germanv
    Christiane.Chaumetteigb.IraunhoIer.de
    Background :
    In an osmosis power plant two water Ilows with diIIerent salt contents are separated by a semi permeable membrane. Water is
    transIerred Irom the side with low salt content and pressure to the side with high salt content and pressure. The transIerred
    water can than be expanded by means oI a turbine in order to produce electrical energy. This principle known as PRO
    -388-
    1 2 3 4 5 6
    0
    50
    100
    150
    200
    250
    300

    M
    a
    x
    i
    m
    u
    m

    P
    o
    w
    e
    r

    D
    e
    n
    s
    i
    t
    y

    [
    m
    W
    /
    c
    m
    2
    ]
    Methanol Concentration [M]
    N-PE
    N117
    SPPEK1.4
    SPPEK1.4-PE
    (pressure retarded osmosis) was introduced in the 1970s |1|. But an economic use was not possible up to now due to the lack
    oI suitable membranes. SuIIering Irom excessive concentration polarisation reverse osmosis membranes do not perIorm.
    Results:
    A measuring device was built up which allows the testing oI
    membranes under realistic power plant conditions (pressure
    up to 25 bar). The best commercially available membranes
    (HTI, Albany, USA) tested so Iar, show an energy yield oI
    1,0 W/m
    2
    (32g/kg NaCl, 0,014 m/s surIace velocity,
    saltwater pressure 8 bar). Our simulation oI mass transIer in
    PRO modules, veriIied by and in good agreement with the
    data measured, shows room Ior Iurther signiIicant
    improvement by optimizing membrane geometry.
    Dense high perIorming PRO-membranes have been
    developed in our lab with diIIerent polymer and polymer-
    inorganic-hybrid systems consistently reaching 1,0 Watt/m
    2
    .
    According to our simulation the membrane perIormance can
    be improved by producing a very thin and open carrier
    structure. This geometry has been realized by a mixed
    template approach (combination oI pore Iorming agents and
    leachable templates, see Figure 1).
    The optimization oI membranes and modules is part oI an
    ongoing project with Voith Siemens Hydropower
    Generation.
    |1| Loeb, S (1975), Science 189: 654-655.
    Figure 1: SEM-Examples oI sub-layers structured with mixed
    templates
    PF.1.7
    Ion-exchange membranes for fuel cells based on vinylphosphonic acid copolymers
    doped with phosphoric acid
    J. Zitka
    1
    , M. Bleha
    1
    , J. Schauer
    1
    , M. Paidar
    2
    , M. Pliskova
    2
    , J. Malis
    2
    1
    Institute of Macromolecular Chemistrv, Academv of Sciences of the C:ech Republic, v.v.i., Hevrovskeho nam. 2, 162 06
    Praha 6, C:ech Republic
    2
    Institute of Chemical Technologv Prague, Technicka 5, 160 00, Praha 6, C:ech Republic
    zitkaimc.cas.cz
    Proton exchange membrane NaIion is now widely used in membrane Iuel cells |1|. A group oI sulIonated aromatic polymers
    Ior low temperature Iuel cells and polymeric membranes Ior intermediate temperature Iuel cells are investigated as potential
    replace oI NaIion |2|. Membranes based on sulIonated aromatic polymers have limited oxidation stability, and oIten poor
    mechanical properties, whereas sulIonated perIluorinated membranes are costly. ThereIore some other alternatives are
    investigated.
    Proton-exchange membranes Ior Iuel cells must possess high proton conductance, and excellent thermal and chemical stability.
    An alternative is the development oI proton conductive, non-Iluorinated aliphatic polymer membranes as they have excellent
    mechanical properties and a high thermal stability.
    A series oI vinylphosphonic acid copolymers with various contents oI vinylphosponic acid units were synthesized by radical
    polymerization using photoinitiation. All the polymer membranes were characterized by elemental analysis, ionic conductivity,
    water sorption, phosphoric acid sorption, TGA and oxidation stability. The resulting Iilms displayed good mechanical
    properties and ability to adsorb phosphoric acid. These membranes exhibited high ionic conductivity at 130C and very high
    oxidation stability thereIore Iilms based on vinylphosphonic acid copolymers doped with phosphoric acid seem to be very
    promising in proton exchange membranes Ior Iuel cells.
    Acknowledgement to the project oI Ministry oI Industry and Trade oI the Czech Republic No. MPO 2A-1TP1/116 Ior
    Iinancial support.
    |1| Q. Li, R. He, J. O. Jensen, N. J. Bjerrum, Approaches and recent development oI polymer electrolyte membranes Ior Iuel
    cells operating above 100 C, Chem. Mater. 15 (2003) 4896 - 4915.
    |2| J. A. Kerres, Development oI ionomer membranes Ior Iuel cells, J. Membr. Sci. 185 (2001) 3-27
    -389-
    PF.1.8
    Sulfonated poly(ether ether ketone) based MEA for fuel cell optimization
    K.S. RoeloIs
    1,2
    , P. Wursthorn
    2
    , T. Hirth
    1,2
    , T. Schiestel
    2
    1
    Fraunhofer Institute for Interfacial Engineering and Biotechnologv, Nobelstr. 12, 70569, Stuttgart, Germanv
    2
    Universitv of Stuttgart, Institute for Interfacial Engineering, Nobelstr. 12, 70569, Stuttgart, Germanv
    Kimball.RoeloIsigb.IraunhoIer.de
    The decreasing availability oI Iossil Iuels and the increasing impact oI greenhouse gases on the environment lead to an
    extensive development oI more eIIicient or renewable energy sources. The direct alcohol Iuel cell (DAFC) as a portable energy
    source is a promising and Iast growing technology which meets these demands. Extensive research is perIormed on component
    and system development Ior direct alcohol Iuel cells. Component development Iocuses mainly on the development oI polymer
    electrolyte membranes (low crossover, high proton conductivity) or catalyst (high activity, high selectivity). The heart oI the
    Iuel cell, the membrane electrode assembly (MEA), combines the membrane and the catalyst in a complex system. The catalyst
    layer should obtain an appropriate porosity Ior the supply and removal oI reactants and reaction products. The electrical
    resistance should be low and the polymeric binder should be proton conductive to transIer the protons to the membrane.
    Important is the low resistance at interIace between catalyst layer and membrane. Nowadays the binder material in catalyst
    layer is mainly based on NaIion

    . Next to the economical and environmental drawbacks, other problems arise Irom the
    incompatibility oI the membrane material and the polymeric electrode binder |1|.
    Our group Iocuses on the application oI nonIluorinated nanocomposite membranes in direct ethanol Iuel cells. The polymer
    used in the membrane and the binder in the catalytic ink is sulIonated poly(ether ether ketone). The catalytic ink is water based
    resulting in low toxicity in the preparation procedure. Macropores in the catalytic layer are produced by a template technique
    and micropores with a water soluble polymer. The electrode layers are applied on the membrane by means oI a screen-printing
    technique. The morphology oI the MEA is studied by SEM and electrochemical impedance spectroscopy is perIormed to
    investigate the layer attachment by means oI resistance and capacitance.
    The catalytic layers show good adhesion with the membrane and the catalyst loading is adjustable by varying the ink
    composition or thickness oI the layers (multiple prints). An electronic conductivity oI up to 5 S cm
    -2
    is obtained dependent on
    the layer thickness. Swelling in ethanol water system did not degrade the multiple layer system. Fuel cell tests will be carried
    out to show the improved MEA perIormance.
    |1| J.K. Lee, W. Li and A. Manthiram, SulIonated poly(ether ether ketone) as an ionomer Ior direct methanol Iuel cell
    electrodes, Journal oI Power Sources, 180 (2008) 56.
    PF.1.9
    Polyvinyl alcohol-fumed silica nano-composites as polymer electrolyte for alkaline
    direct methanol fuel cells
    S. Jessie Lue, J.-Y. Chen, W.-T. Wong
    Department of Chemical and Materials Engineering, Chang Gung Universitv, Kwei-shan, Taovuan, Taiwan 333
    jessiemail.cgu.edu.tw
    Direct methanol Iuel cells provide an alternative energy source Ior mobile devices. Proton-exchange membranes are oIten used
    but hydroxide-conducting electrolytes have been gained much attention in the last Iew years. We have prepared polyvinyl
    alcohol-Iumed silica (PVA-FS) nano-composites and reported its beneIicial characters. These advantages include better
    stability in aqueous solution, good mechanical strength |1|, higher water vapor diIIusivity due to the increased Iree-volume |2|,
    etc. AIter the nano- composites were immersed in KOH solution, the conductivity increased with the FS content in the
    composites (Fig.1). The cell perIormance oI the electrolyte containing 20 FS at room temperature is shown in Fig. 2. The
    PVA-FS oIIers a potential electrolyte material Ior alkaline direct methanol Iuel cell application.
    -390-
    Fig.1. Conductivity oI PVA-FS-KOH composites.
    Fig. 2. Cell perIormance oI PVA-FS-KOH electrolyte
    |1| S. J. Lue, J.Y. Chen, J. M. Yang, Crystallinity and stability oI poly(vinyl alcohol)-Iumed silica mixed matrix membranes, J.
    Macromol. Sci. Phys. 47 (2008) 39-51.
    |2| S. J. Lue, D.T. Lee, J.Y. Chen, C.H. Chiu, C.C. Hu, Y.C. Jean, J.Y. Lai, DiIIusivity enhancement oI water vapor in
    poly(vinyl alcohol)-Iumed silica nano-composite membranes: Correlation with polymer crystallinity and Iree-volume
    properties, J. Membr. Sci. 325 (2008) 831-839.
    PF.1.10
    PVA nanofiber reinforced Nafion membrane for DMFC application
    S. Molla
    1
    , T. Leon Yu
    2
    , E. Riande
    3
    , V. Compa
    1

    1
    Departamento de Termodinamica Aplicada, Escuela Tecnica Superior de Ingenieros Industriales, Universidad Politecnica de
    Jalencia, Camino de Jera s/n, 46022 Jalencia, Spain
    2
    Department of Chemical Engineering & Materials Science, Yuan Ze Universitv, Taovuan 32026, Taiwan
    vicommoter.upv.es
    Direct Methanol Fuel Cells are
    promising candidates as power
    generators Ior portable devices. Easy
    reIuelling and high energy storage
    capacity are their main advantages. On
    the other hand, power densities are much
    lower than those compared to hydrogen
    PEM Iuel cells due to the reduced
    electrochemical oxidation rate oI
    methanol at the anode and the high Iuel
    crossover through the membrane,
    typically NaIion |1,2|, which entails the
    use oI thicker membranes. Polyvinyl
    alcohol (PVA) has been proposed to be
    blended with NaIion in order to diminish
    its methanol crossover |3|. However, proton conductivity is simultaneously decreased in Iunction oI the PVA content.
    Our work has been Iocused on the preparation and characterisation oI a composite membrane Iabricated by inIiltrating NaIion
    117 into a porous PVA nanoIiber mat (Figure 1). The mat was obtained by electrospinning oI an aqueous solution oI PVA. The
    PVA nanoIibers, with diameters between 200-300 nm, were Iunctionalised on their external surIace with sulIonic acid groups
    in order to cooperate in the proton conductivity oI NaIion (Figure 2).
    First methanol permeability results oI the composite membrane show values oI 2,5310
    -6
    cm
    2
    /s, which are approximately 3
    times lower than those Iound in NaIion 117 prepared by casting in isopropanol based solvent (Figure 3).
    -391-
    Figure 1: SEM picture oI the
    composite membrane with PVA
    nanoIibers inIiltrated by NaIion.
    Figure 2: SEM picture oI the PVA
    nanoIiber mat aIter chemical
    Iunctionalisation.
    The proton conductivity oI the membrane reached 0.031 S/cm measured at
    70C and 95 RH by impedance spectroscopy. This value is interestingly
    above the conductivity measured in same conditions Ior a cast NaIion 117
    membrane, 0.018 S/cm.
    IMPIVA (Institute Ior Small and Medium Industry oI the Generalitat
    Valenciana) through the ITE (Electrical Technology Institute oI Valencia)
    are acknowledged Ior granting the works.
    |1| T.H. Kin, W.Y. Shieh, C.C. Yang, George Yu, J. Power Sources 161
    (2006) 1183-1186.
    |2| Zhigang Qi, A. KauIman, J. Power Sources 110 (2002) 177-185.
    |3| Nicholas W. DeLuca, YosseI A. Elabd, Journal oI Membrane Science
    282 (2006) 217224.
    PF.1.11
    Resistance phenomena in ion exchange membranes at low salt concentrations
    P. Dlugolcki
    1,2
    , K. Nijmeijer
    1
    , S. Metz
    2
    , M. Wessling
    1
    1
    Universitv of Twente, Facultv of Science and Technologv, Membrane Technologv Group, P.O. Box 217, 7500 AE Enschede,
    The Netherlands
    2
    Wetsus, Centre for Sustainable Water Technologv, P.O. Box 1113, 8900 CC Leeuwarden, The Netherlands
    d.c.nijmeijerutwente.nl
    Reverse electrodialysis (RED) is a non-polluting, sustainable method Ior energy generation. It converts the Iree energy oI
    mixing oI a concentrated (e.g. sea) and a diluted salt solution (e.g. river) into electrical energy through an alternating series oI
    anion and cation exchange membranes. Usually characteristics oI ion exchange membranes are determined at standard
    conditions i.e. in 0.5M NaCl solution. For many applications this is suIIicient, but Ior reverse electrodialysis, which typically
    operates in the low concentration range ( 0.5 M), this does not represent the practical condition |1|. In the present work we
    investigate the inIluence oI the solution concentration and the hydrodynamic conditions on resistance phenomena in diIIerent
    types oI commercially available ion exchange membranes. From direct current measurements we observe a strong
    concentration dependence oI the membrane resistance: The measured membrane resistance strongly increases with decreasing
    salt concentration, especially in the concentration range below 0.1 M NaCl. However, direct current measurements not only
    determine the pure membrane resistance, but also include double layer and diIIusion boundary layer resistance that occur at the
    membrane surIace. Direct current measurements do not allow discrimination between these diIIerent resistances and only
    provide an overall` resistance taking into account these diIIerent phenomena.
    Measurement oI the resistance using alternating current (electrochemical impedance spectroscopy (EIS)) oIIers a powerIul tool
    to discriminate between the individual resistances oI the membrane, the double layer and the diIIusion boundary layer. From
    EIS measurements we observed that at higher salt concentrations (0.5M NaCl) the membrane resistance is indeed the main
    resistance, although also the diIIusion boundary layer resistance signiIicantly contributes to the total resistance. At low
    (0.017M) NaCl concentration the diIIusion boundary layer resistance is the dominant resistance and signiIicantly exceeds the
    pure membrane resistance. This diIIusion boundary layer resistance decreases signiIicantly with increasing solution Ilow rate,
    because the diIIusion boundary layer thickness is in the micrometer scale (200-300m), which indicates that this layer can be
    aIIected by hydrodynamic conditions. Double layer resistance is small compared to the other resistances and its value is
    independent oI the solution Ilow rate, because the double layer thickness is in nanometer scale (the Debye length) at the
    membrane surIace and it can not be aIIected by hydrodynamic conditions.
    The results obtained Irom EIS measurements show the strong potential oI this technique and prove that especially in solutions
    with low salt concentrations the diIIusion boundary layer dominates the total resistance as measured with direct current
    methods. These results are oI major importance Ior applications like reverse electro dialysis and microbial Iuel cells, which
    operate in the low salt concentration range and put strong constraints on the design oI such systems.
    1. Dlugolecki, P., et al., Current status oI ion exchange membranes Ior power generation Irom salinity gradients, Journal oI
    Membrane Science, 2008. 319(1-2): p. 214-222.
    -392-
    0 7200 14400 21600 28800 36000
    time (sec)
    0
    0.004
    0.008
    0.012
    0.016
    0.02
    C
    B

    (
    g
    /
    g
    )
    Temp = 70C
    Nafion - nanoPVA (thickness 74 m
    Nafion 117 (thickness 172 m)

    Figure 3: Methanol permeability Ior a PVA
    nanoIiber reinIorced NaIion composite
    membrane () and Ior NaIion 117 (O).
    PF.1.12
    A zeolite membrane reactor for glycerol exploitation as raw material
    L. Roldan
    1
    , R. Mallada
    2
    , J.M. Fraile
    3
    , J.A. Mayoral
    3
    , M. Menendez
    1
    1
    Aragon Institute of Engineering Research (I3A). Univesitv of Zarago:a. Spai
    2
    Instituto de Nanociencia de Aragon (INA). Universitv of Zarago:a. Spain
    3
    Instituto de Ciencia de Materiales de Aragon and Instituto de Catalisis Homogenea. Universidad de Zarago:a - C.S.I.C.
    Spain
    miguel.menendezunizar.es
    The increasing production oI glycerol as a subproduct oI biodiesel manuIacture constitutes an opportunity to Iind new uses.
    One potential product with an increased value is solketal, a biodegradable solvent with a low vapor pressure. Solketal is
    obtained Irom glycerol by ketalization, by the Iollowing reaction
    The equilibrium conversion oI this reaction is quite low iI stoichiometric amounts oI reactants are employed, which makes
    necessary the use oI large amounts oI acetone to achieve suitable degree oI glycerol conversion. Since water is a product oI the
    reaction, the removal oI water by a suitable membrane could constitute a suitable means to increase the achievable conversion.
    In this work we describe the use oI a zeolite membrane reactor Ior the transIormation oI glycerol to solketal, using acid-treated
    montmorillonite K10 as catalyst.
    The experimental system was built is such way that the zeolite membrane only contacts with the vapors Iormed in the reaction,
    avoiding the damage that the contact with the liquid-solid suspension could cause to the zeolite layer. Since the chemical
    potential oI water is the same in the gas and in the liquid phase (assuming they are in equilibrium), the driving Iorce Ior
    permeation is the same as iI the membrane was submerged in the liquid.
    Two kinds oI zeolite membrane were tested, both made oI zeolite A, which is the most suitable Ior water removal: a)
    Synthesized in a continuous system |1|, b) Synthesized with a centriIugal system |2|. The perIormance oI the membranes was
    characterized by the pervaporation oI water/ethanol mixtures and it was Iound that the perIormance oI the membrane in the
    reactor closely related with the permeation Ilux achieved. The zeolite membrane reactor allows a higher conversion oI glycerol
    with a lower amount oI acetone.
    |1| Pina M.P., Arruebo M., Felipe M., Fleta F., Bernal M.P., Coronas J., Menendez M., Santamaria J., J. Membrane Sci., 2004;
    244-141
    |2| Tiscareo-Lechuga F., Tellez C., Menendez M., Santamaria J., J. Membr. Sci., 2003; 212:135
    PF.1.13
    Mathematical model of a membrane reactor combined with in-situ regeneration for
    methane aromatization
    A. Romeo, M. Menendez
    Aragon Institute of Engineering Research (I3A). Univesitv of Zarago:a. Spain
    miguel.menendezunizar.es
    Among the existing technologies Ior methane transIormation to liquid products (e.g. Fischer-Tropsch and a variety oI
    processes involving methanol as an intermediate step), dehydroaromatization oI methane appeared as a promising alternative
    |1|. This reaction not only allows to obtain a mixture liquid aromatic hydrocarbons (benzene, toluene and xylenes), but also
    produces hydrogen in signiIicant amounts.
    The two main drawbacks oI this reaction are the low conversion (equilibrium conversion is around 10) and the catalyst
    deactivation by coke.
    In this work an idea to solve these two drawback, based in the combination oI the two-zone Iluidized bed reactor with a
    membrane reactor, is explored with the help oI mathematical models describing several possibilities. The use oI a membrane
    reactor Ior methane aromatization has been proposed previously |2|, this membrane reactor is based on the removal oI
    -393-
    HO OH
    OH
    H
    3
    C
    O
    CH
    3
    H
    +
    O
    O
    CH
    3
    H
    3
    C
    OH
    H
    2
    O
    hydrogen with a membrane to displace the equilibrium; however, due to the lower hydrogen concentration the catalyst
    deactivation becomes even Iaster and thereIore a conventional membrane reactor is discarded. The two-zone Iluidized bed
    reactor has been tested in several previous works |3|, and is a suitable system to provide in situ regeneration Ior reactions that
    are deactivated by coke, including methane aromatization |4|.
    The mathematical models developed include the Iollowing cases:
    - Pd membrane reactor: allows exploring the potential oI the reactor using a Iully selective membrane, and provides
    inIormation about the additional requirements oI catalysts and the surIace area needed.
    - Knudsen membrane reactor: in this case the membrane has much smaller selectivity, but is more easily manuIactured
    and has higher Ilow.
    The two cases were simulated Ior two diIIerent assumptions:
    - An ideal catalyst with small coke Iormation, in such way that the yield to coke was negligible.
    - A conventional catalyst with a coke Iormation rate estimated Irom experimental data.
    The results Irom the simulations show that the perIormance can be improved over the limit given by the thermodynamic
    equilibrium even with a simple Knudsen membrane with low selectivity, but also show the advantages oI high selective
    membranes and oI catalysts with low tendency to coke Iormation.
    The basic idea presented in this work, i.e. to combine in a single reactor the increase oI conversion provided by a selective
    membrane and the 'in situ catalyst regeneration provided by the two zone Iluidized bed reactor, can easily be extended to
    many other reactions characterized by a conversion limited by the equilibrium, by the Iormation oI hydrogen and by catalyst
    deactivation by coke.
    |1| D. Wang, M.P. Rosynek and H. LunsIord. J. Catal. 169 (1997) 347
    |2| O. Rival, B. P. A. Grandjean, C. Guy, A. Sayari, F.Larachi, Ind. Eng. Chem. Res., 40 (2001) 2212
    |3| J. Herguido, M. Menendez, J. Santamaria, Catal. Todav 100 (2005) 181
    |4| M. Menendez, J. Herguido, C. Tellez, J. Soler, M. Gimeno, Spanish Patent Application 200801857 (2008)
    PF.1.14
    Poly(vinyl alcohol) based polymer electrolyte membrane for passive type direct
    methanol fuel cell
    M. Higa , M. Sugita, S.I. Maesowa, N. Endo
    Graduate School of Science and Engineering, Yamaguchi Universitv,
    2-16-1 Tokiwadai, Ube-citv, Yamaguch 755-8611, Japan
    mhigayamaguchi-u.ac.jp
    Direct methanol Iuel cell (DMFC) using polymer electrolyte membranes
    (PEM) are one oI the most attractive power sources. In this study, PEMs
    were prepared by casting mixed solution oI poly (vinyl alcohol) and
    poly(vinyl alcohol-co-2-acrylamido-2-methylpropane sulIonic acid)
    (AP-X, X2 or 4) shown Figure 1 on a acrylic plate and by drying it at
    50
    o
    C. The PEMs obtained were annealed at 180
    o
    C Ior 30 min, and then
    were cross-linked chemically by immersing them in a cross-linking
    solution changing its concentration, C
    GA,
    at 25
    o
    C Ior 24 h to control their
    water content. The proton conductivity, mechanical strength and
    methanol permeability oI the PEMs has been measured as a Iunction oI
    the water content and polyanion content.
    The proton conductivity at 25
    o
    C was determined by impedance
    spectroscopy using a chemical impedance meter. Permeation
    experiments at 25
    o
    C were perIormed by using an acrylic plastic cell oI
    two parts separated by a sample PEM. One chamber oI the cell was Iilled
    with 12 M methanol solution and the other chamber deionized water
    .
    The
    solution in the chamber at the low-concentration side was sampled to
    measure the concentration oI methanol using a high perIormance liquid
    chromatography.
    The water content oI the PEMs increases with polyelectrolyte contents
    because osmotic pressure in the PEMs increases with increasing the
    number oI the charged groups. The proton conductivity (o) and methanol
    permeability (P) oI the PEMs decrease with increasing concentration oI
    -394-
    Figure 1. Chemical structure oI
    polyelectrolyte, AP-X.
    98 / 2 AP-2
    96 / 4 AP-4
    C
    H
    2
    CH
    OH
    H
    2
    C CH
    C
    NH
    C CH
    3
    H
    3
    C
    CH
    2
    SO
    3
    H
    n
    O
    0
    20
    40
    60
    80
    100
    120
    140
    1.0 2.0 3.0 4.0 5.0

    / 10
    3
    Scm
    -
    3
    s
    C
    pa
    / moI %
    Figure 2. Proton permselectivity, ,as a
    function of polyanion content, C
    pa
    , in PEM.
    Cross-linker concentration, C
    GA
    :
    the cross-linker, C
    GA
    because the water content oI the PEM decreases with increasing C
    GA
    . Figure 2 shows the proton
    permselectivity () oI the PEMs, which is deIined as o/P, increases with increasing C
    GA
    because methanol permeability
    decreases more steeply than proton conductivity does with increasing C
    GA
    . The proton permselectivity oI the PEM shows a
    maximum value at C
    pa
    2.7 mol and C
    GA
    0.35 vol . The value is 13010
    3
    Scm
    -3
    s, and more than 3 times higher than that
    oI NaIion

    117. The result indicates that the PVA based PEMs have potential application to a DMFC system.
    PF.1.15
    Self-organized proton nanochannels in hybrid fuel-cell membranes, exhibiting high
    ionic conductivity
    M. Michau, M. Barboiu
    Adaptive Supramolecular Nanosvstems Group, Institut Europeen des Membranes, (IEM), UMR-CNRS-5635 ENSCM, UM2,
    CNRS, Universite Montpellier II, Place Eugene Bataillon CC047, F-34095 Montpellier Cedex 5, France
    mihai.barboiuiemm.univ-montp2.Ir
    These results provides new insights into the basic Ieatures that control the convergence oI supramolecular selI-organization
    with the proton conduction Iunction and suggest tools Ior developing the next generation oI PEMFC materials.
    Fuel cells have the potential to become an important energy conversion technology. Research eIIorts directed toward the
    electrochemical conversion oI energy using proton exchange membrane (PEM) Iuel cells have been enormously accelerated
    with the hope to promote them as an alternative power source Ior transport and portable applications. For a long time the
    comprehension oI the proton transport mechanisms and the structure oI the reIerence NaIion 117

    membrane have been


    uncertains. Recent results show that the selI-organization oI hydrated inverse-micelle cylindrical superstructures
    6
    is in direct
    relation with the excellent transport properties oI the NaIion 117

    . Concurrently, the structural design oI new polymeric


    membrane materials has attracted a great deal oI interest Ior optimal perIormances requiring a detailed knowledge oI chemical
    structure and nanoscale morphology. In this context, the supramolecular synthesis provides a powerIul tool Ior the controlled
    generation oI selI-organized Iunctional hybrid materials. We thereIore decided to address a new strategy employing a combined
    supramolecular and sol-gel synthetic route in order to control the Iormation oI hydrophilic proton nanochannels.
    Supramolecular controlled generation oI selI-organized channels Ior directional proton diIIusion is noteworthy and has yet to
    be realized as a straightIorward approach Ior the design oI a novel class oI PEMs. Herein we report new PEM hybrid
    membranes presenting long-range lamellar (hundreds oI nanometers) selI-organization. The PEM hybrid membranes are
    homogeneous, Ilexible and show both high thermal and chemical stabilities. They were surveyed Ior their ability to Iorm
    proton-nanochannels, reaching high ionic conductivities (up to eight times higher than the commercial NaIion 117

    at 25C
    and 100 relative humidity).
    1 M. Michau. et al., Chem. Eur. J. 14, 1776-1783 (2008).
    2. M. Michau, R. Caraballo, C. Arnal Herault, J. Membreane Sci. 2008, 321 (1) 22-30.
    2. M. Barboiu, P. Aimar, J.-M. Lehn, J. Memb. Sci., 2008, 321, 1-2; (b) J. Memb. Sci., 2008, 321, Special issue : From simple
    molecules to complex membrane systems
    This work was supported by Iunds Irom the Participating Organizations oI EURYI and the EC Sixth Framework Program
    -395-
    PF.1.16
    Porous electrochemical contactors for a concentric biofuel cell
    A. Habrioux
    1
    , G. Merle
    2
    , K. Servat
    1
    , B. Kokoh
    1
    , C. Innocent
    2
    , M. Cretin
    2
    , S. Tingry
    2
    1
    LACCO 'Equipe Electrocatalvse` UMR 6503 CNRS-Universite de Poitiers, 40 av. du Recteur Pineau 86022 Poitiers, France
    2
    Institut Europeen des Membranes, UMR 5635, ENSCM-CNRS-UM2, Place Eugene Bataillon, CC 047, 34095 Montpellier,
    cedex 5, France
    sophie.tingryiemm.univ-montp2.Ir
    A concentric glucose/O
    2
    bioIuel cell, delivering electrical power, has been developed based on porous electrochemical
    contactors. The device is constituted oI two carbon tubular electrodes, one in the other, and combines glucose
    electrooxidation at the anode and oxygen electroreduction at the cathode. The anodic catalyst is the glucose oxidase co-
    immobilized with the mediator 8-hydroxyquinoline-5-sulIonic acid hydrate, and the cathodic catalyst is the bilirubin oxidase
    co-immobilized with the mediator 2,2-azinobis(3-ethylbenzothiazoline-6-sulIonate) diammonium salt. Both enzymes and
    mediators are entrapped at the surIace oI the tubular electrodes by an electrogenerated polypyrrole polymer. The originality
    oI the concentric conIiguration is to compartmentalize the anode and cathode electrodes and to supply dissolved oxygen
    separate Irom the electrolyte in order to avoid secondary reactions.
    The dissolved oxygen circulates through the inside oI the cathode tube and diIIuses Irom the inner to the external surIace oI
    the contactor to react directly with the immobilized bilirubin oxidase. The assembled bioIuel cell is studied at 37 C in
    phosphate buIIer pH 7.4. The stability and the eIIiciency oI the device are evaluated by spectrophotometric and
    electrochemical methods. We show the inIluence oI the thickness oI the polypyrrole polymer on the electrochemical activity
    oI the biocathodes. We also demonstrate the eIIect oI the chemical reticulation oI the enzymes by glutaraldehyde within the
    polymer on the perIormances oI the bioelectrodes. The maximum power density delivered by the assembled glucose/O
    2
    bioIuel cell reaches 42 Wcm
    -2
    , evaluated Irom the geometric area oI the electrodes, at a cell voltage oI 0.30 V with 10 mM
    glucose. The results demonstrate that the concentric design oI the bioIuel cell based on compartmented electrodes is a
    promising architecture Ior Iurther development oI micro electronic devices.
    PF.1.17
    Poly(diphenylsulfone-oxadiazole)s as materials for fuel cells
    M. Schieda, I. Ternes, S. Nunes
    GKSS Research Centre Geesthacht GmbH, Institute of Polvmer Research, Max-Planck-Str. 1, 21502 Geesthacht, Germanv
    mauricio.schiedagkss.de
    Polymer Electrolyte Fuel Cells (PEMFCs) are a promising conversion technology with an impressive range oI applications. It
    has been shown that PEMFC operation at temperatures above 100C has several advantages, including improved cathode
    kinetics
    1
    , water management and gas transport
    2
    . NaIion is currently the standard proton conducting material used in PEMFC
    -396-
    Schematic configuration of the biofuel
    cell prototvpe

    +
    Glucose
    solution pH 7.4
    saturated O
    2
    solution
    +
    Glucose
    solution pH 7.4
    saturated O
    2
    solution
    glucose
    gluconolactone

    O
    2
    H
    2
    O
    manuIacture. However, the perIormance oI this commercial polymer decreases at temperatures higher than 80C. Thus, there is
    a great amount oI interest in research on proton conducting polymers with good thermal and mechanical properties at high
    temperatures.
    Both polyoxadiazoles and polyarylsulIones are high-perIormance polymers and, in sulIonated Iorm, they have been proposed
    3
    as components Ior PEMFCs. The current work consists oI the synthesis oI poly (diphenylsulIone-oxadiazole)s with diIIerent
    degrees oI sulIonation, and the characterization oI their properties aiming Iuel cell application.
    m
    S
    O
    O
    N N
    O
    n
    S
    O
    O
    N N
    O
    SO
    3
    H
    |1| Q. Li, R. He, J. O. Jensen, N. J. Bjerrum, 'Approaches and Recent Development oI Polymer Electrolyte Membranes Ior
    Fuel Cells Operating above 100 C, Chem. Mater., 2003, 15, 4896-4915
    |2| J. Zhang, Z. Xie, J. Zhang, Y. Tang, C. Songa, T. Navessin, Z. Shi, D. Songa, H. Wang, D. P. Wilkinson, Z-S. Liu, S.
    HoldcroIt, 'High temperature PEM Iuel cells, J. Power Sources, 2006, 160, 872-891
    |3| D. Gomes, S. P. Nunes, 'Fluorinated polyoxadiazole Ior high-temperature polymer electrolyte membrane Iuel cells, J.
    Membrane Sci., 2008, 321, 114-122
    PF.1.18
    Sulfonated poly(vinylidene fluoride)-based composite films with improved electrical
    conductivity for PEM fuel cell application
    A. Lien Ong, A. Bottino, G. Capannelli, A. Comite
    Dipartimento di Chimica e Chimica Industriale, via Dodecaneso 31, 16146 Genova, Italv
    bottinochimica.unige.it
    Innovative electrically conductive sulIonated polyvinylidene Iluoride (PVDFS) composite Iilms were investigated as
    microporous layer (MPL) Ior proton exchange membrane Iuel cell (PEMFC) application. As it is well known, MPL is usually
    coated on one side or both side oI a macroporous backing layer (carbon paper or carbon cloth), composed by an electrically
    conductive material, typically carbon black, and a hydrophobic binding agent, typically polytetraIluoroethylene (PTFE),
    Iorming gas diIIusion layer (GDL) oI a PEMFC. The role oI MPL is to enhance the GDL perIormance by minimizing
    electronic contact resistance, improving gas transport and reducing the water Ilooding |1|. Polyvinylidene Iluoride (PVDF) has
    been proposed to replace the more expensive and less processable PTFE, due to its chemical stability, thermal resistance and
    hydrophobic character. Cabasso et al. |2| Iirst developed GDL with a controlled porosity and pore size by coagulation in a non-
    solvent oI a mixture oI activated carbon and PVDF dissolved in an organic solvent. PVDF-based MPL with improved
    perIormance was then developed by Hitomi |3|. More recently we investigated the eIIect oI preparative parameters on the
    characteristics oI PVDF-based MPL prepared by phase inversion technique |4|. The obtained results motivate several
    subsequently related studies and investigations. In the present work, PVDFS |5| has been investigated as binding agent in order
    to obtain novel MPL with improved Iunctionalization Ior platinum catalyst deposition. The MPL was prepared by phase
    inversion using carbon black and carbon nanotubes as an electrically-conductive Iiller. Electrical resistance, through-plane air
    permeability and the resulting microstructure were careIully examinated. Improved electrical conductivity oI the investigated
    PVDFS nanocomposite MPL containing carbon nanotubes was obtained.
    |1| A.L. Ong, A. Bottino, G. Capannelli, A. Comite, EIIect oI preparative parameters on the characteristic oI poly(vinylidene
    Iluoride)-based microporous layer Ior proton exchange membrane Iuel cells, J. Power Sources 183 (2008) 62.
    |2| I. Cabasso, Y. Yuan, X. Xu, Gas diIIusion electrodes based on poly(vinylidene Iluoride) carbon blends, US 5,783,325
    (1998).
    |3| S. Hitomi, Electrode Ior Iuel cell and process Ior the preparation thereoI, US 2001/0,041,283 A1 (2001).
    |4| A. Bottino, G. Camera-Roda, G. Capannelli, S. Munari, The Iormation oI microporous polyvinylidene diIluoride
    membranes by phase separation, J. Membr. Sci. 57 (1997) 1.
    |5| S. Munari, F. Vigo, G. Capannelli, C. Uliana, A. Bottino, Method Ior the preparation oI asymmetrical membranes, US
    4,188,354 (1980).
    -397-
    PF.1.19
    Development of plasma polymers as proton conducting membranes for fuel cell cores
    A. Ennajdaoui
    1,2
    , S. Roualdes
    1
    , J. Durand
    1
    , P. Brault
    3
    , M. Cavarroc
    2
    1
    Institut Europeen des Membranes (IEM), ENSCM, UM2, CNRS , Universite Montpellier 2, CC047, Place Eugene Bataillon,
    34095 Montpellier cedex 5, France
    2
    MID Dreux Innovation, 4 rue Albert Caquot, 28500 Jernouillet, France
    3
    Groupe de Recherches sur lEnergetique des Milieux Ionises (GREMI), Universite dOrleans, BP 6744, 14 rue dIssoudun,
    45067 Orleans, France
    stephanie.roualdesiemm.univ-montp2.Ir
    In the Iield oI micro Iuel cells, intended to the market oI portable electronic devices, recent research eIIorts have Iocused on
    the development oI a new generation oI electrolyte membrane which has to meet the Iollowing requirements: high chemical
    and thermal stability, good ionic conduction level and low permeability to Iuel. The polymerization by plasma technology is an
    original method Ior the manuIacture oI competitive proton conducting membranes. Indeed, plasma polymerization is a
    powerIul method Ior depositing thin and uniIorm polymer Iilms whose micro-structural properties can be tailored by
    modiIying the main deposition parameters. The main advantages oI plasma-polymerized Iilms are their highly cross-linked
    chemical structure, which gives them strong chemical and thermal stabilities and low permeability to Iuel, and their very low
    thickness (a Iew microns), which enables them to perIectly Iit to the electrodes surIace and to adapt to miniaturized Iuel cells
    with very complex geometries.
    Promising proton conducting membranes containing sulIonic acid groups have been synthesized Irom a styrene /
    triIluoromethane sulIonic acid (CF
    3
    -SO
    3
    H) mixture in a radio-Irequency capacitively coupled plasma reactor. Styrene has been
    used as a monomer able to polymerize as a carbonaceous matrix with aromatic spacing groups and triIluoromethane sulIonic
    acid as a sulIonation agent to promote protonic conductivity |1,2|. Original membrane-electrodes assemblies (MEAs) using
    plasma co-sputtered platinum-carbon deposits as electrodes have been manuIactured in order to develop thick compact (~ 1
    mm) plasma Iuel cells cores. Recently, MEAs` integration has been improved using a linear industrial prototype which
    combines plasma polymerization Ior the membrane deposition and plasma sputtering Ior the electrodes deposition in a single
    device. First plasma Iuel cells preparations on such an industrial device are in progress.
    Communaute d`Agglomeration du Drouais, MHS Industry, ESF-European Union, French Ministry oI research, CNRS are
    acknowledged Ior granting the works.
    |1| A. Ennajdaoui, J. Larrieu, S. Roualdes, J. Durand, PECVD process Ior the preparation oI proton conducting membranes Ior
    micro Iuel cells. Impedance probe measurements and material characterizations, Eur. Phys. J. Appl. Phys. 42 (2008) 9-15.
    |2| P. Brault, J. Durand, S. Roualdes, A. Leclerc, Method Ior producing a thin-Iilm Iuel cell, Patents n WO 2007/063245 A1,
    published on 07.06.2007.
    PF.1.20
    Bi-dimensional and numerical study of heat transfer in planar SOFC single cell:
    chemical heat source models
    B. Zitouni, H. Ben moussa, K. Oulmi, H. Abdenebi
    Laboratoire detude des svstemes energetiques industriels (LESEI), Departement de Mecanique. Faculte des Ingenieurs,
    Universite de Batna, ALGERIE
    H2SOFCgmail.com
    A Solid Oxide Fuel Cell (SOFC) works at high temperatures. These high temperatures can be advantageous because released
    heat can be made proIitable Ior other thermal systems. However, the constraints resulting on the choice Irom the materials
    (aspects mechanical, chemical, etc...) limit the technological developments and involve high costs.
    The aim oI this work is to study the increasing temperature oI a SOFC single cell The results oI bi-dimensional and
    mathematical model show the increasing temperature in the solid side oI SOFC; anode, electrolyte, cathode and interconnector
    under several heat sources and under several chemical heat sources mathematic models. The maximum temperature value and
    its localization are analyzed Ior several geometric conIigurations and gas temperature value at the channels.
    -398-
    PF.1.21
    Carbon black tail-gas separation using a Matrimid

    polymeric membrane
    O. C. Voinea, D. Gorri, I. Ortiz, A. Urtiaga
    Department of Chemical Engineering. Universitv of Cantabria. Avda. de los Castros s/n, 39005 Santander, Spain
    urtiagaunican.es
    Among today`s multiple Iield developed applications oI gas separation technology like air dehumidiIication, nitrogen
    production, hydrogen recovery, natural gas sweetening and helium separation (1,2), it have emerged the treatment oI industrial
    Ilue gases like those oI coal Iired power plants (3) and carbon black manuIacturing process (this work). At this moment carbon
    black tail-gas is released to atmosphere and has a complex composition consisting mainly in 'diluting species like water,
    nitrogen and carbon dioxide, but also combustible gases like hydrogen and carbon monoxide. In order to study the possible
    wais oI valorization oI this tail-gas stream an experimental mixed gas separation set up was build and various thickness
    Matrimid

    5218 (Huntsman Advanced Polymers) membranes were manuIactured.


    The experimental results will show the inIluence oI the main operation parameters on the permeability and selectivity oI the
    separation process: Ieed side pressure, temperature, Ieed composition, membrane thickness and sweep gas Ilowrate.
    As an example, the results obtained in the study oI the inIluence
    oI temperature on hydrogen permeability are shown. We were
    able to predict a 13.5 kJ/mol activation energy oI permeation (
    P
    a
    E ) studying the temperature eIIect on the permeability oI a
    pure hydrogen stream at a constant pressure oI 4 bar and
    employing a 47.8 m membrane (Figure 1).
    The permeability is also slightly inIluence by the Ieed pressure.
    This tendency, according to Yampolskii (2006), is predicted by a
    dual-mode sorption and mobility model applied in the case oI
    glassy polymers membranes, as it is the case oI Matrimid (Figure
    2).
    Acknowledgements: Financial support oI project
    CTM2006-00317 is grateIully acknowledged
    |1| Zolandz R. R. and G. K. Fleming, Gas Permeation, Membrane
    Handbook (Eds.: W. S. W. Ho, K. K. Sirkar), Van Nostrand
    Reinhold, New York 1992.
    |2| Baker R. W., 'Future Directions oI Membrane Gas Separation
    Technology, Industrial Engineering Chemistry Research, 41,
    1393-1411, 2002
    |3| H. Sijbesma, K. Nymeijer, R Marwijk, R. Heijboer, J.
    Potreck, M. Wessling, 'Flue gas dehydration using polymer
    membranes Journal oI Membrane Science 313, 263276, 2008
    y -1624.4x 8.496
    R
    2
    0.9983
    3.2
    3.4
    3.6
    3.8
    4.0
    4.2
    2.6E-03 2.8E-03 3.0E-03 3.2E-03 3.4E-03
    1/T (K^-1)
    l
    n
    P
    Figure 1. H
    2
    permeability with temperature
    (a) Hydrogen permeabilit y
    16,0
    16,5
    17,0
    17,5
    18,0
    0 5 10
    Pressure (bar)
    P
    e
    r
    m
    e
    a
    b
    i
    l
    i
    t
    y

    (
    B
    a
    r
    r
    e
    r
    )
    Figure 2. H
    2
    permeability with Ieed pressure
    PF.1.22
    Preparation of Pd/Ag composite membranes and simulative analysis of transfer
    resistance for hydrogen separation
    M.I. Mohamed Dzahir, Z. Wu, K. Li
    Department of Chemical Engineering & Chemical Technologv, Imperial College, London, South Kensington, London SW7
    2AZ
    m.mohamed-dzahir07imperial.ac.uk
    Composite Pd/Ag membranes supported on alumina hollow Iibre membranes as substrate have been prepared by sequential
    electroless plating and the morphology oI the membranes has been examined by SEM and EDS analysis. The SEM micrograph
    -399-
    with corresponding EDS line scan revealed that the Pd/Ag alloy Iilm was Iormed on the substrate with control composition as
    well as thickness. Homogeneous alloy Iilms oI Pd/Ag were obtained by annealing the separate Pd and Ag deposited layers at
    temperatures higher than 600 C in inert atmosphere. A simulative analysis was carried out to investigate the eIIect oI diIIerent
    support resistance with regards to the overall perIormance oI the composite membranes.
    |1| R. Hughes , Composite palladium membranes Ior catalytic membrane reactors. Membr. Technol. March (2001), p. 9.
    |2| K. Hou and R. Hughes , The eIIect oI external mass transIer, competitive adsorption and coking on hydrogen permeation
    through thin Pd/Ag membranes. J. Membr. Sci. 206 (2002), p. 119.
    |3| C.H. Hermann, P. Quicker and R. Dittmeyer , Mathematical simulation oI catalytic dehydrogenation oI ethylbenzene to
    styrene in a composite Pd membrane reactor. J. Membr. Sci. 136 (1997), p. 161.
    PF.1.23
    Perovskite brazing on metals for steam electrolysis under pressure
    J. Loricourt
    1,2
    , Y. Paranthoen
    1
    , B. Sala
    1
    , G. Pourcelly
    2
    , M. Chavigneau
    1
    , A.K. Sirat
    3
    , O. Lacroix
    3
    1
    SCT, Societe des Ceramiques Techniques, 65 460 Ba:et
    2
    CNRS, IEM, UMR 5635, Place Eugene Bataillon, 34095 Montpellier, France
    3
    AREJA detached at IEM, Place Eugene Bataillon, 34095 Montpellier, France
    jloricourtsct-ceramics.com
    Uses oI protonic conductors as electrolytes Ior Iuel cell and electrolyser applications due to their relative low Iunctioning
    temperature is more interesting compare to oxide-ion conductors. H

    systems could operate below 650C, critical temperature


    Ior resistance oI usual alloys, especially, in an electrolyser plant.
    To become protonic conductor Perovskites (Iormula ABO
    3
    ) where protonic charge carrier isn`t intrinsic needed to be doped
    and hydrated |1|. To remind to the diIIiculties oI perovskite protonation, hydration needed to occur under steam pressure |2,3|.
    At the operating electrolysis conditions (around 600C, ~10 bars) it is impossible to consider a glass using seal to separate the
    two compartments: anodic (steam and oxygen atmosphere) and cathodic (pure hydrogen atmosphere) and also the tightness oI
    the pressure cell. Consequently, only a brazing process could be applied in these operating conditions.
    In this objective a screening oI several brazes are tested with perovskite. Firstly, the wettability oI braze alloys on perovskite is
    studied with contact angle measurements and surIace tension determination on temperature.
    High oxidative atmosphere on anodic compartment induces braze corrosion. Thermogravimetric measurements, leakage tests
    and post mortem analysis (SEM, RX, XPS, GDOS) aIter staying under 30 bars oI steam pressure at 430C allow to expertise
    the corrosion process.
    Basing these results on, a tight cell able to work with a diIIerential pressure closed to 20 bars between anodic and cathodic
    compartments in Iunctioning condition, is built.
    |1| 16th World Hydrogen Energy ConIerence (ProceedingOral presentation). June 2006, B. Sala, S. Willemin, O. Lacroix, Ph
    Colomban, K.Rahmouni, A. Julbe, H.Takenouti, J.P. Py
    |2| O. Lacroix, B. Sala, K. Rahmouni, H. Takenouti, M. Keddam, C. Deslouis, S. Willemin, G. Pourcelly, J.P. Py, S. De
    Perthuis, electrochemistry and solid state letters, submitted
    |3| B. Sala, O. Lacroix, S. Willemin, K. Rahmouni, H. Takenouti, A. Van Der Lee, P. Colomban, P. Goeuriot, B.
    Benjeriou,Patent WO2008152317
    -400-
    PF.1.24
    Perovskite-based cermet electrode for steam electrolysis with proton conducting
    electrolyte
    F. Grasset
    1
    , K. Rahmouni
    2
    , S. Willemin
    3
    , B. Sala
    3
    , H. Takenouti
    2
    , C. Deslouis
    2
    , M. Keddam
    2
    , A.K. Sirat
    3
    ,
    O. Lacroix
    3
    1
    CNRS, IEM, UMR 5635, Place Eugene Bataillon, 34095 Montpellier, France
    2
    LISE UPR15 & Universite P. et M. Curie, CC133, 4 place Jussieu, 75 252 Paris, France
    3
    AREJA detached at IEM, Place Eugene Bataillon, 34095 Montpellier, France
    beatrice.salaiemm.univ-montp2.Ir
    The decrease oI petroleum reserves and the increase oI greenhouse eIIect encourage strongly development oI some new
    technologies Ior providing green energy sources such as Hydrogen. Hydrogen production Irom steam electrolysis is becoming
    a challenge; this method ought to producing hydrogen in mass downstream a nuclear reactor with economical acceptance.
    Proton conductors are more promising electrolytes, since H

    systems could operate below 650C, a critical threshold


    temperature to use ordinary commercial alloys, especially in an electrolyser plant.
    Perovskites (ABO
    3
    ) has no intrinsic proton charge carrier. Consequently, doping and hydration under steam pressure oI
    ceramic is needed to generate proton charge carriers. Several studies have been launched on proton conducting electrolytes;
    however Iew studies are carried out yet on electrodes Ior proton conductor electrolysis cells.
    The cermet is synthesized by two methods: - wet chemistry or perovskite/metal powder mixing. The sintering atmosphere and
    temperature are optimised to maximise percolation Ior both ceramic and metal in cermet. The prepared cermet was
    characterized ex situ by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Hg Porosity, energy
    dispersive X-ray (EDX); and in situ by electrochemical measurements between 400 and 600 C in steam (anode) or in
    hydrogen (cathode) media in electrochemical cell.
    As shown in Figure 1 cermet samples presents a homogeneous particle size distribution. In the impedance spectra (Figure 2),
    the high Irequency loop exhibits the response oI the proton conduction through ceramic (described as bulk and grain boundary
    signatures) in parallel with the electronic conduction oI meal phase, while at low Irequencies the impedance spectrum
    corresponds to the interIacial reactions. It is observed that ceramic resistance decreases markedly with temperature increase.
    Figure 1.
    SEM micrographs
    of the sintered
    cermet
    Figure 2.
    EIS spectra of
    cermet under Ar/
    10H
    2
    0 5 10 15 20 25 30 35 40
    0
    5
    10
    15
    20
    25
    30
    525C
    400C
    475C
    10kHz
    0.1kHz
    1kHz
    ReaI part /
    -

    I
    m
    a
    g
    i
    n
    a
    r
    y

    p
    a
    r
    t

    /

    0,0 0,1 0,2 0,3 0,4 0,5 0,0


    0,1
    0,2
    0,3
    1MHz
    10KHz
    600C
    575C
    |1| T. Kobayashi, K. Abe, Y. Ukyo and H. Matsumoto, Solid State Ionics 138 (2001), pp. 243251.
    PF.1.25
    Composite proton-exchange membranes based on sulfonated or phosphonated
    polymer-grafted silica particles
    F. Niepceron
    1
    , T. Boucheteau
    2
    , J. Bigarre
    2
    , H. Galiano
    2
    1
    Laboratoire des Materiaux Macromoleculaires, INSA Lvon, Jilleurbanne, France
    2
    Commissariat a lEnergie Atomique, Department of Materials, Le Ripault, Monts, France
    thomas.boucheteaucea.Ir
    Fuel cells are important enabling technologies Ior the reduction oI green-house gases emissions, oIIering cleaner, more-
    eIIicient alternatives to combustion oI gasoline and other Iossil Iuels.|1| Current Polymer Electrolyte Membrane (PEM) Fuel
    -401-
    Cell systems predominantly use perIluorosulIonic acid based membranes, such as NaIion. However, NaIion membranes
    tend to signiIicantly dehydrate at high temperatures or at low relative humidity leading to low proton conductivity and poor
    PEMFC perIormance under these conditions. Thus, new proton exchange membrane (PEM) materials have been developed in
    order to increase the perIormance over a large temperature window and at low humidiIication.|2,3|
    In the last decade, several studies reported consistent improvements oI the perIormance oI PEMFCs at temperatures above
    80C when inorganic particles were inserted in the polymeric membrane.|4,5| Interestingly, a new Iamily oI PEM where the
    proton conductive characteristics rely exclusively on the inorganic phase gives promising results. In the present contribution, a
    report oI the incorporation oI original acid-Iunctionalized inorganic nanoparticles in inert PVDF-HFP-based membranes is
    given. Membranes with diIIerent amounts oI inorganic particles have been prepared by evaporation and recasting techniques.
    These membranes were tested Ior their proton conductivities and their morphologies have been investigated. Finally, the
    perIormances oI membrane-electrode assemblies using selected hybrid membranes were evaluated by single cell Iuel cell tests.
    Remarkably, such hybrid membrane systems exhibited up to 1.2 W/cm
    2
    , at 80 C using non-hydrated gas Ieeds.
    This work was carried within the Iramework oI a Pan-H program Iinanced by the Agence Nationale pour le Recherche and co-
    supported by the Commissariat a l`Energie Atomique and the Region Centre.
    |1| BCH. Steele, A. Heinzel, Nature 2001, 414, 345.
    |2| MA. Hickner, H. Ghassemi, YS. Kim, BR. Einsla, JE. McGrath, Chemical Reviews, 2004, 104, 4587.
    |3| J. Roziere, DJ. Jones, Annual Review of Materials Research, 2003, 33, 503.
    |4| G. Alberti, M. Casciola, Annual Review of Materials Research, 2003, 33, 129.
    |5| G. Alberti, M. Casciola, in Membrane Technology. Volume 2: Membranes Ior energy conversion, (Eds. K.V. Peinemann
    and S.P. Nunes), WILEY-VCH, Weinheim, 2008.
    PF.1.26
    Rejuvenation of hygrothermally aged Nafion

    F. Thominette
    1
    , F. Collette
    1
    , G. Gebel
    2
    1
    Laboratoire dIngenierie des materiaux, ENSAM, 151 Boulevard de lhopital, 75013 Paris, France
    2
    Laboratoire Structure et Proprietes des Architectures Moleculaires, UMR 5819 CEA-CNRS-UJF, 17 avenue des martvrs,
    38054 Grenoble, France
    Irancette.thominetteparis.ensam.Ir
    NaIion 112 and 212-CS stored Ior long periods at 80C and diIIerent relative humidities Irom 0RH to 95RH exhibit large
    modiIications oI their properties. The aging mechanism was shown to be a condensation oI the sulIonic acid end-groups into
    sulIonic anhydrides. However, this reaction does not occur when the samples are aged at 80C in liquid water indicating a
    condensation-hydrolysis equilibrium which depends oI the relative humidity. In this work, investigations were run on aged
    membranes exposed to acid solutions or vapours and to basic solutions in order to check the reversibility oI the condensation
    reaction. Indeed, in pure water the hydrolysis is slow and limited while it is Iast and complete in the presence oI acid or base.
    The native polymer chemical structure is recovered via the anhydride hydrolysis and the main membrane properties
    (mechanical properties, hydrophilicity.) are completely restored. This way leads to NaIion rejuvenation.
    0
    5
    10
    15
    20
    25
    30
    0 20 40 60 80 100 120 140 160 180 200
    Strain (%)
    S
    t
    r
    e
    s
    s

    (
    M
    P
    a
    )
    Nafion 212-CS aged 230 days at 80C, 95%RH
    Nafion 212-CS aged 230 days then immered in a hydrochloric acid solution 0,1M
    Pristine Nafion 212-CS
    Mechanical properties evolution Ior pristine NaIion

    212-CS,
    aged NaIion

    212-CS and oI aged NaIion



    212-CS aIter
    immersion in a hydrochloric acid solution 0,1 M
    -402-
    0
    2
    4
    6
    8
    10
    12
    14
    16
    0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
    p/po
    W
    a
    t
    e
    r

    u
    p
    t
    a
    k
    e
    (
    %
    )
    Pristine Nafion 212-CS Nafion 212-CS aged 230 days at 80C, 95%RH
    Nafion 212-CS aged 230 days at 80C, 95%RH then immersed in HCl 0,1M
    0
    2
    4
    6
    8
    10
    12
    14
    16
    0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
    p/po
    W
    a
    t
    e
    r

    u
    p
    t
    a
    k
    e
    (
    %
    )
    Pristine Nafion 212-CS Pristine Nafion 212-CS Nafion 212-CS aged 230 days at 80C, 95%RH Nafion 212-CS aged 230 days at 80C, 95%RH
    Nafion 212-CS aged 230 days at 80C, 95%RH then immersed in HCl 0,1M Nafion 212-CS aged 230 days at 80C, 95%RH then immersed in HCl 0,1M
    Water uptake evolution Ior pristine NaIion

    212-CS, aged
    NaIion

    212-CS and oI aged NaIion

    212-CS aIter
    immersion in a hydrochloric acid solution 0,1 M
    PF.2.1
    Effect of presence of humic substances on ultrafiltration of xenobiotic compounds
    N. Ghaemi
    1
    , S.S. Madaeni
    1
    , M. De Nobili
    2
    , A. Alizadeh
    3
    1
    Department of Chemical Engineering, Ra:i Universitv, Kermanshah, Iran
    2
    Dipartimento di Scien:e, Agrarie ed Ambientali, Universita di Udine, via delle Scien:e 208, 33100 Udine, Italv
    3
    Nanoscience and Nanotechnologv Research Centre, Department of Chemistrv, Ra:i Universitv, Kermanshah, Iran
    smadaeniyahoo.com
    The eIIect oI the presence oI pesticides, even at comparatively low concentrations, makes water unsuitable Ior direct municipal
    supply. In this research, series oI xenobiotic compounds (e.g. nitrophenols) as pesticides were selected as major pollutants oI
    drinking water. The eIIect oI their interaction with humic substances on ultraIiltration process was elucidated. In neutral
    condition (pH7), the rejection oI 3,5-dinitrosalicylic acid and 2,4-dinitro-6-methylphenol in the presence oI HA was increased
    during a certain period oI Iiltration in comparison with the absence oI HA in the solution. The behavior oI p-nitrophenol was
    diIIerent Irom other mentioned NPs. The presence oI HA in the solution containing p-nitrophenol resulted in rejection decline
    at the early stages oI the experiment. However rejection was increased during time. For ultraIiltration oI all nitrophenols in the
    presence oI HA, cake deposition is the dominant mechanism. Flux was not remarkably changed due to Iormation oI a cake
    with low porosity.
    PF.2.2
    New membrane method for the regeneration of activated carbon saturated with H
    2
    S
    N. Douiche
    1,2
    , H. Grib
    2
    , H. Lounici
    2
    , M.O. Mecherri
    2
    , N. GhaIIour
    3
    , N. Mamri
    2
    1
    Silicon Technologv Development Unit (UDTS), 2, Bd Frant: Fanon BP140, Alger 7 merveilles, 16200, Algerie
    2
    Laboratorv of Environmental Biotechnologies, Ecole Polvtechnique dAlger - 10, Avenue Pasteur El-Harrach, Algeria
    3
    Middle East Desalination Research Center P.O.Box21, P.C.133, Muscat, Sultanate of Oman
    nadjibdrouicheyahoo.Ir
    The main purpose oI the present work was to study the Ieasibility oI the regeneration oI granular activated carbon packed in
    beds saturated with H
    2
    S by utilizing three electrodialysis compartments equipped with a cation or an anion exchange
    membrane or a bipolar membrane. Three electrodialysis compartments were utilized under various experimental parameters to
    determine the optimum conditions oI recovery oI column particles saturated with H
    2
    S.
    Use oI the bipolar membrane makes it possible to regenerate the saturated adsorbent granules without adding chemical
    products. Since the only reagent was electricity, the projected economics are very attractive. Moreover the desulphurization
    operation is achieved with an electric current eIIiciency close to 90.
    -403-
    PF.2.3
    Recycled water treatment, operation and costing using advanced MF and UF
    membranes
    S. Caothien
    1
    , T. Wachinski
    2
    , M. Farcy, D. Vial
    3
    1
    Pall Corporation, 1630 Industrial Park Street, Covina, CA 91722-3419, USA
    2
    Pall Corporation, 25 Harbor Park Drive, Port Washington, NY 11050, USA
    3
    Pall Corporation, 3 rue des Gaudines, 78100
    3
    Saint-Germain-en-Lave, France
    scottcaothienpall.com
    Better advances in membrane design, cleaning and Ilux maintenance protocols are presented to show the versatility and
    Ilexibility oI membranes to meet changing and challenging wastewater sources. Physical properties oI membranes
    (microIiltration and ultraIiltration) are characterized and described to provide a better understanding oI their Iunctionalities.
    With variable Ieed sources, membranes can behave diIIerently depending upon their ability to resist or handle Iouling, which
    has a big impact on the economics oI the membrane plant. In addition, the conIiguration oI a membrane system, either
    pressurized membrane or immersed membrane, inherently plays an important role on membrane Ilux and power requirement.
    The number oI modules required, the number oI treatment trains, real estate Iootprint, the O&M costs, all depend on
    membrane design Ilux and conIiguration. ThereIore a standardized membrane design Ilux across various membrane platIorms
    can result in non-optimum membrane system and higher unit cost Ior treated water.
    Several examples oI optimized design during pilot-scale testing and Iull-scale installations with membrane design Iluxes
    ranging up to 110 l/h.m
    2
    (65 GFD) were achieved Ior a variety oI Ieed wastewaters. OI particular interest, design and
    perIormance criteria are detailed Ior New York Watershed Protection and state-oI the-art Australian recycled water
    installations with microIiltration (MF) and ultraIiltration (UF). Validation and challenge test data are also presented Ior Iull-
    scale installations with and without coagulation pretreatment.
    By using a modern and optimized Ilux approach, diIIerent membrane systems can be diIIerentiated based on the liIe cycle
    costs, number oI modules required and replacement costs. Optimized design will deliver the lowest cost oI treatment to the
    municipalities by savings on capital costs and operating expenses.
    PF.2.4
    Challenge testing membrane filtration at a wastewater facility in the New York city
    watershed
    J.A. Habib
    1
    , M. Farcy, D. Vial
    2
    1
    Pall Corporation, 25 Harbor Park Drive, Port Washington, NY 11050, USA
    2
    Pall Corporation, 3 rue des Gaudines, 78100 Saint-Germain-en-Lave, France
    josephhabibpall.com
    The Hobart Wastewater Treatment Plant (WWTP) underwent a discharge permit upgrade in 2002 pursuant to New York City
    (NYC) Watershed Rules and Regulations. The upgrade work incorporated the addition oI a tertiary treatment process, whereby
    secondary eIIluent Irom the extended air activated sludge process now undergoes rapid mix/Ilocculation, sand Iiltration,
    membrane Iiltration, and ultraviolet disinIection, beIore being discharged to the West Branch Delaware River.
    Sand Iiltration in series with the membrane Iiltration system makes Ior a reliable and robust process as required per NYC
    speciIications Ior upgraded WWTPs in the Watershed. The membrane system at Hobart was designed to treat the plant`s rated
    capacity oI 680 m
    3
    /d (0.18 MGD) with the upstream media Iilters online. However, the capacity oI the membrane system is
    generally understood to Iar exceed that Ior which it is designed under the NYC speciIications.
    The Hobart WWTP generally uses its Iull compliment oI membranes to process normal Ilows, which is typically a Iraction oI
    the design Ilow oI 28.5 m
    3
    /h (125 gpm). The plant does however experience periodic high Ilow conditions where Ilow can
    exceed 31.5 m
    3
    /h (140 gpm) particularly during periods oI wet weather. Historical data shows high Ilow events at the Hobart
    WWTP typically lasting 2-3 days.
    This study looks at the membrane system`s capability to handle design Ilow under simulated challenge conditions whereby the
    upstream pretreatment process upstream oI the membrane system was intentionally compromised.
    The membrane Iiltration system demonstrated its capability to handle Ilows in excess oI design Ilow during the simulated upset
    conditions. With the upstream media Iilters oIIline, membrane Iiltration alone suIIiciently produced eIIluent well within the
    plant`s permitted discharge limits Ior all constituents including phosphorous. As a result oI this study, New York City
    -404-
    Regulators are considering steps towards reIining membrane system speciIications to reIlect changes and improvements in the
    technology.
    PF.2.5
    Treatment of oilfield produced water with combined inorganic ultra- and
    nanofiltration membranes
    M. Ebrahimi
    1
    , D. Willershausen
    1
    , L. Engel
    1
    , P. Mund
    2
    , P. Bolduan
    2
    , P. Czermak
    1,3
    1
    Institute of Biopharmaceutical Technologv (IBPT), Universitv of Applied Sciences Giessen-Friedberg, Giessen, Germanv.
    2
    Atech innovations GmbH, Gladbeck, Germanv
    3
    Dept. of Chemical Engineering, Kansas State Universitv, Manhattan KS, USA
    peter.czermaktg.Ih-giessen.de
    In general, the production oI crude oil and natural gas is always associated with the co-production oI water. This water is
    termed 'produced-water. The quantity oI water produced per unit volume oI hydrocarbons varies greatly, but typically
    increases with the age oI the producing Iield. As well as Iree and emulsiIied hydrocarbons, this water may contain salts oI
    many kinds, Iine silts oI both silicon and clay compositions, and in some cases active biological materials.
    Produced-water is always cleaned to some extent; the level oI cleaning dependent upon the intended use and/or current
    discharge regulations. Current technologies used consist oI clariIiers, dissolved air Ilotation, hydrocyclones, and disposable
    Iilters/absorbers. The existing technologies are not typically capable oI reaching the new levels oI cleanliness demanded by
    regulations without using additional expensive chemicals Ior coagulation, settling and the like. This increases operating
    expenses and produces greater volumes oI hazardous wastes. To overcome these problems posed by the tighter regulations,
    operators have turned to membrane Iiltration schemes that have the potential to minimize these additional costs and disposal
    issues. Both polymeric and ceramic membranes have been tried under many Iield conditions. While these membranes do a
    good job separating the oils, emulsions, and silts, they are prone to Iouling by waxes and asphaltenes. The issues that need to
    be addressed are to prevent membrane Iouling by modiIying the waxes and asphaltenes to prevent their Iouling oI the
    membranes during operation and to provide an expedient, cost eIIective, and non-hazardous means oI cleaning the membranes
    when they become Iouled. The key technical obstacles Ior the integration oI UF/NF membrane Iiltration Ior the oilIield water
    treatment process are reviewed. In addition results Ior average Ilux rates, Ilux degradation, back Ilushing and cleaning are
    shown.
    |1| Ciarapica, F. E., G. Giacchetta, 2003. The treatment oI produced water in oIIshore rig: comparison between traditional
    installations and innovative systems. In Proceedings oI the FiIth International Membrane Science & Technology ConIerence,
    Nov. 2003, Sydney, Australia.
    |2| Shams Ashaghi K., M. Ebrahimi, P. Czermak: Ceramic Ultra- and NanoIiltration Membranes Ior OilIield Produced Water
    Treatment - A Mini Review. Open Env J 2007, 1:1-8
    |3| Ebrahimi M, K. Shams Ashaghi, L. Engel, P. Mund, P. Bolduan, P. Czermak: Investigations on the Use oI DiIIerent
    Ceramic Membranes For EIIicient Oil-Field Produced Water Treatment, Desalination submitted Ior publication 9/2008
    |4| Czermak P, M Ebrahimi, K Shams Ashaghi, L Engel, P Mund: Feasibility oI using ceramic ultra- and nanoIiltration
    membranes Ior eIIicient treatment oI produced water, Proceedings oI the 10th World Filtration Congress, Vol. 2, p. 140-144,
    April 14-18, 2008, Leipzig, Germany
    -405-
    PF.2.6
    Treatment of bleach plant effluents and separation of lignin compounds via ceramic
    UF/NF membranes
    M. Ebrahimi
    1
    , S. Kerker
    1
    , A. Wienold
    1
    , H. Neul
    2
    , A. Ante
    2
    , M. Hilpert
    3
    , P. Mund
    4
    , P. Czermak
    1,5
    1
    Institute of Biopharmaceutical Technologv (IBPT), Universitv of Applied Sciences Giessen-Friedberg, Giessen, Germanv.
    2
    Bamag GmbH, But:bach, Germanv
    3
    Sappi Fine Paper Europe, Ehingen, Germanv
    4
    Atech innovations GmbH, Gladbeck, Germanv.
    5
    Dept. of Chemical Engineering, Kansas State Universitv, Manhattan KS, USA
    Peter.czermaktg.Ih-giessen.de
    Lignin, the organic substance which, with cellulose, constitutes the essential part oI woody plant tissue, is typically obtained as
    a by-product oI pulping processes. The objective oI this work is to develop the combined membrane Iiltration processes
    Iocused on the treatment oI residual lignin Irom eIIluent out oI the bleaching stage oI pulp production. The present practice oI
    most oI the pulp and paper industries is to treat these eIIluents in an ineIIicient way (aeration, liming, etc.) and then disposing
    it oII to the nearby water system. This poses serious environmental problems with Ilouting oI environmental laws.
    In this study, the inIluence oI various process parameters such as diIIerent pore sizes oI the ceramic membranes used (pore size
    ranging Irom 20kDa to 0.75kDa), Ieed water characteristics, trans-membrane pressure (TMP), cross-Ilow velocity and
    temperature on the separation behavior oI ultraIiltration (UF) and nanoIiltration (NF) ceramic membranes was studied. The
    inIluence oI the lignin concentration and pH oI the mixture on the UF/NF processes is studied as well.
    Wallberg O., Linde M., Jnsson A.-S., Extraction oI lignin and hemicelluloses Irom kraIt black liquor, Desalination 199
    (2006) 413414.
    S. Bhattacharjee, S. Datta, C. Bhattacharjee, Studies on water quality parameters during ultraIiltration oI kraIt black liquor, IE
    (l) Journal-CH, 86 (2005) 1-7.
    DaIinov A., J. Font, R. Garcia-Valls, Processing oI black liquors by UF/NF ceramic membranes, Desalination 173 (2005) 83
    90.
    PF.2.7
    Composting effluent treatment by membrane bioreactor
    J. Gagnaire
    1
    , P. Moulin
    1
    , L. Chapon
    2
    , B. Marrot
    1
    1
    Universite Paul Ce:anne Aix Marseille, Departement de Procedes Propres et Environnement (DPPE UMR 6181), Europole
    de lArbois, BP. 80, Batiment Laennec, Hall C, 13545 Aix en Provence Cedex 04, France
    2
    Societe des Eaux de Marseille, 25 Rue Edouard Delanglade, 13006 Marseille
    Benoit.marrotuniv-cezanne.Ir
    Activated sludge in Waste Water Treatment Plants
    (WWTPs) can be composted by mixing with green
    wastes. The toxic eIIluent produced during active
    composting undergoes season variations. EIIluent
    can be characterized as biodegradable (ratio BOD/
    COD ~ 0.4). Nevertheless high ammonium and
    carbon loads (until 7,000 mgN.L
    -1
    and COD until
    42,000 mg.L
    -1
    ) required a controlled
    acclimatization step beIore treatment (Figure 1).
    The aim oI this work is to study the composting
    eIIluent treatment by an external membrane
    bioreactor (ceramic membranes oI 1 m
    2
    and
    MWCO 150 kDa). The semi-industrial unit is
    equipped with two tanks: nitriIication (5 m
    3
    ) and
    denitriIication (2 m
    3
    ). Implanted in a composting
    center, the MBR allows a permeate production oI 1
    m
    3
    .d
    -1
    . Hydraulic retention time (HRT) was
    -406-
    0
    1000
    2000
    3000
    4000
    5000
    6000
    7000
    8000
    9000
    25/10/2007 14/12/2007 02/02/2008 23/03/2008 12/05/2008 01/07/2008 20/08/2008 09/10/2008 28/11/2008
    Date
    N
    -
    N
    H
    4
    +

    (
    m
    g
    N
    .
    L
    -
    1
    )
    0
    5000
    10000
    15000
    20000
    25000
    30000
    35000
    40000
    45000
    C
    O
    D

    (
    m
    g
    .
    L
    -
    1
    )
    Ammonium
    COD
    Figure 1 : Load variations oI raw composting eIIluent
    maintained constant at 175 h. Pilot size was chosen to get closer to industrial conditions (pumps shear, aeration, temperature
    Iluctuations, tanks homogenization). Mixed liquor suspended solids (MLSS) are ranging between 10 and 15 g.L
    -1
    . AIter an
    acclimatization step to the composting eIIluent, MBR perIormances are studied by changing sludge retention time |SRT 30 d
    - |. During period with F/M ratios 0.5 kg
    DCO
    .kg
    MLSS
    -1
    .d
    -1
    and 0.03 kg
    N-NH4
    .kg
    MLSS
    -1
    .d
    -1
    and Ior SRT , COD and N-NH
    4

    removal reach 96 and 99 respectively. Permeate quality was in agreement with the French legislations standards Ior reject in
    a WWTP. The permeate Ilux is maintained constant at 40 L.h
    -1
    .m
    -2
    and the membrane regeneration is eIIective aIter the
    washing step.
    Determination oI ammonium degradation rates was used to compare the activated sludges acclimatization: (i) acclimatized to
    municipal wastewater (WWTP sludges) (ii) acclimatized to a landIill leachate and (iii) acclimatized to the composting eIIluent.
    During these experiments, the degradation rate was monitored with a speciIic sensor. For each one, 1.5 L oI sludge was used
    and real or synthetic substrate was added. Real substrate is the composting eIIluent and synthetic substrate is only composed
    by (NH
    4
    )
    2
    SO
    4
    and C
    6
    H
    12
    O
    6
    with similar concentrations in terms oI N-NH
    4

    and COD.
    PF.2.8
    Treatment of dyeing industry waste water by nanofiltration and reverse osmosis
    E. Ellouze
    1
    , N. KhliI
    1
    , P. Moulin
    2
    , R. Ben Amar
    1
    1
    Faculte des Sciences de Sfax, Laboratoire Sciences des Materiaux et Environnement Route de Soukra Km4, BP. Universite
    2
    Paul Ce:anne Aix Marseille, Laboratoire de Mecanique, Modelisation et Procedes Propres (M2P2 UMR-CNRS 6181),
    Europole de lArbois, BP. 80, Batiment Laennec, Hall C, 13545 Aix en Provence Cedex 04, France
    raja.rekikIss.rnu.tn
    Industrial textile processing comprises the operations oI pretreatment, dyeing, printing and Iinishing. These production
    processes are not only heavy consumers oI energy and water; they also produce a substantial amount oI chemical pollution. OI
    all dyed textile Iibres, cotton occupies the number-one position, and more than 50 oI its production is dyed with reactive
    dyes, owing to their technical characteristics. UnIortunately, this class oI dyes is also the most unIavorable one Irom the
    ecological point oI view, as the eIIluents produced are relatively heavily colored, contain high concentrations oI salt and
    exhibit high BOD/COD values. In this paper, experimental results obtained Irom the treatment by nanoIiltration (NF) and
    reverse osmosis (RO) oI reconstituted dyeing industry waste water using reactive dyes: 1gL
    -1
    oI Blue BezectiI (SGLD) and 15
    gL
    -1
    oI NaCl. are presented and compared. The results obtained Irom nanoIiltration perIormed at diIIerent pressures
    (7TMP13) (T25C) show that the permeate Ilux decreased Irom initial value oI 34 to 21 Lh
    -1
    m
    -2
    Ior a volumetric
    concentration Iactor (VCF) oI 4. A high quality oI treated eIIluent in term oI colour removal and desalination was obtained Ior
    a VCF oI 2: salinity retention rate (RR) 40 and decolourization almost 98 . While, the permeate Ilux obtained using RO at
    a diIIerent pressures 40TMP70 bars decreased Irom initial value oI 30 to 5 L.h
    -1
    m
    -2
    Ior a VCF oI 6 indicating an important
    Iouling. In this case, the osmotic pressure varied Irom 6.5 to 38 bars. The optimum salinity and colour retention rate (RR)
    were 96 and 97

    respectively obtained at a VCF oI 2. Some experiments with industrial eIIluents resulting directly Irom
    an industry oI dyeing are in progress to understand the eIIect oI organic matter on membrane process
    PF.2.9
    Treatment of return liquors water by means of reverse osmosis
    K. Konieczny
    1
    , J. Cwikla
    2
    1
    Silesian Universitv of Technologv, Institute of Water and Wastewater Engineering, Division of Environmental Chemistrv and
    Membrane Process, ul.Akademicka 2, 44-100 Gliwice, Poland
    2
    Pr:edsibiorstwo Wodocigow i Kanali:acfi Sp. : o.o., ul.Rvbnicka 47, 44-100 Gliwice, Poland
    krystyna.koniecznypolsl.pl
    In connection with sharpening requirements concerning eIIluent total nitrogen limits, which could be introduced into waters or
    ground, it is necessary to look Ior methods oI N-load reduction, right now in wastewater plants. The puriIication oI
    sedimentary water occurring during dehydration oI Iermented waste sludge seems to be promising, as these waters Ilow over
    20 oI biogenic compounds to the main treatment reactor |1, 2|. Typically, the sludge water is characterized by high content
    oI ammonia. In several municipal wastewater treatment plants, the unbalanced ratio oI COD/N in the inIluent wastewater
    makes it extremely diIIicult, and not very sustainable, to achieve a high heterotrophic denitriIication perIormance and needs to
    -407-
    introduce external, readily biodegradable carbon sources in anoxic phase. By a separate treatment oI the sludge water
    additional reliability and reduction oI the nitrogen load in the eIIluent may be achieved.
    In this article the research results oI return liquors treatment by reverse osmosis are described. The analysis was replicated
    three times, every time resulting in 95 reduction oI nitrogen and phosphorus components. It is important that this process is
    resistant to raw changes and can be started or interrupted at any time, which is unIeasible in a biological process. The
    application oI reverse osmosis to return liquors treatment seems to be a highly promising technology which aIIords to reduce
    the biogenic compounds level, directed towards the main plant reactor.
    Ammonia and dissolved reactive phosphorus in concentrate Irom RO can be reduced by Iorcing the precipitation oI struvite
    (MgNH
    4
    PO
    4
    6H
    2
    O). Magnesium can be supplemented as magnesium chloride. Magnesium ammonium phosphate hexahydrate
    is a crystalline salt which may be used either as a Iertilizer or as raw material Ior the production oI phosphorus.
    |1| T. Constantine, T. Shea, B. Johnson, Newer approaches Ior treating return liquors Irom anaerobic digestion, IWA
    Specialized ConIerence Nutrient Management in Wastewater treatment Processes and Recycle Streams, Krakow 2005, 455-
    464
    |2| S. CaIIaz, C. Lubello, R. Canziani, D. Santianni, Autotrophic nitrogen removal Irom anaerobic supernatant oI Florence`s
    WWTP digesters, Newer approaches Ior treating return liquors Irom anaerobic digestion, IWA Specialized ConIerence
    Nutrient Management in Wastewater treatment Processes and Recycle Streams, Krakow 2005, 397-406
    PF.2.10
    Performances of a MBR for the purification of pretreated olive vegetation waste
    water
    M. Stoller
    1
    , G. Farabegoli
    2
    , M. Bravi
    1
    1
    Universitv of Rome ,La Sapien:a', Department of Chemical Engineering, Jia Eudossiana 18, 00184 Rome, Italv
    2
    Universitv of Rome ,La Sapien:a', Department of Hvdraulic Transportation and Roads Engineering, Jia Eudossiana 18,
    00184 Rome, Italv
    stolleringchim.ing.uniroma1.it
    The olive vegetation waste water is a waste stream produced by the olive oil mill Iactories, characterized by a very high
    organic matter (COD values equal to 50-150 g/l).
    There are no single processes capable to perIorm the required puriIication oI this waste water stream to a quality compatible to
    the municipal sewer systems Ior easy discharge. ThereIore, more processes in series are required, each accounting Ior COD
    reductions.
    Membrane technology appears to be promising to meet the puriIication targets, but in this case Iouling is a big issue due to the
    suspended organic matter. Pretreatment processes oI the waste water stream are necessary.
    Many pretreatment processes were investigated by one Author |1-3|. Among others, biological treatment oI this waste water
    appears to be a possible choice, characterized by a certain diIIiculty to perIorm but very limited costs. In a previous study,
    biological treatment was perIormed beIore a batch membrane process step with good results |3|.
    In this work, a MBR with a submerged HF UF membrane module was used Ior the partial puriIication oI a olive vegetation
    waste water stream. The main drawback oI MBR is bioIouling.
    Although bioIouling is characterized by other dynamics than Iouling, critical Ilux values were determined and this inIormation
    was used to perIorm a process control optimization as suggested by one Author |4|. A adaption oI the method to bioIouling
    was necessary Ior implementation. The developed method was then validated.
    |1| M. Stoller: 'Critical Ilux analyses on a diIIerently pretreated olive vegetation waste water stream: some case studies, 2008,
    Proceedings CD-ROM MDIW08, nr.197, Toulouse, France.
    |2| M. Stoller: 'Technical optimization oI a dual ultraIiltration and nanoIiltration pilot plant in batch operation by means oI the
    critical Ilux theory: a case study, 2007, Chemical Engineering & Processing Journal Vol 47/7 (2008), pp 1165-1170, DOI.
    10.1016/f.cep.2007.07.012
    |3| K. Movassaghi, M. Stoller, L. Miranda, A. Chianese: 'Olive vegetation wastewater treatment by means oI diIIerent nano-
    TiO
    2
    powders and photoreactor setup, 2008, Proceedings SPEA5, OP5.7 , Palermo, Italy.
    [4] M. Stoller, A. Chianese. 'Technical optimi:ation of a batch olive wash wastewater treatment membrane plant`, 2006,
    Desalination 200(2006) pp 734-736. DOI. 10.1016/f.desal.2006.03.501
    -408-
    PF.2.11
    Use of reaction and ultrafiltration for the treatment of contaminated soils by metallic
    or organic micro-pollutants
    A. Petitgirard, M. Djehiche, J. Persello, M. Euvrard, P. Fievet, N. Fatin-Rouge
    Universitv of Franche-Comte, UTINAM, 25030 Besanon Cedex, France
    nicolas.Iatin-rougeuniv-Icomte.Ir
    Micro-pollutants are largely produced by human activities and are widespread in natural environment. Heavily contaminated
    soils are Irequent around industrial plants. Among these compounds, polycyclic aromatic hydrocarbons (PAHs) and metal ions
    are Irequent contaminants. They are oIten highly toxic and their adsorption onto terrestrial colloids can be very diIIerent. Their
    adsorption oIten strongly limits the eIIiciency oI remediation techniques. Washing techniques with aqueous solutions in noy
    well-developed and is oIten limited by the cost oI water decontamination. HereaIter, we present some examples where
    combination oI reactions and membrane ultraIiltration have been used to extract pollutants Irom contaminated soils and
    concentrate them in small volumes.
    In this work, we have evaluated the ability oI some carriers to decontaminate soils Irom representative micropollutants like
    phenanthrene, pyrene and metal ions (Cu
    2
    , Ni
    2
    , Pb
    2
    ). The principle is to use a same diluted aqueous solution at pH5-6, to
    extract quickly and eIIiciently pollutants Irom the soil with minimal side works. Pollutants were discharged and accumulated
    in an exchange UF reactor, allowing the washing solution to be regenerated and re-used. Kinetics and eIIiciency oI transIer are
    presented as well as loss oI carriers into the soil. Metal ions in the concentrate, were Iurther treated by electrolysis.
    Diluted aqueous solutions oI various carriers were able to decontaminate soils polluted by PAHs and metal ions in a Iew days
    at 85-98 level. There was no signiIicant loss oI carrier by adsorption during the circulation into the soil. The re-use oI a
    diluted washing aqueous solution has great economical and ecological interests: 1) It allows the decontamination oI a large
    amount oI soils. 2) It reduces the cost oI eIIicient extractants Ior pollutants. 3) It limits the danger oI a pollution by these
    ligands.
    PF.2.12
    Use of PAUF for the removal of chelated metal ions from industrial wastewaters
    D. Zamariotto, A. B. Akadar, P. Fievet, N. Fatin-Rouge
    Universitv of Franche-Comte, Laboratoire de Chimie des Materiaux et Interfaces, 25030 Besanon Cedex, France
    nicolas.Iatin-rougeuniv-Icomte.Ir
    Many industrial wastewaters, such as coming Irom electroplating plants, contain high levels oI metal chelates. Chelates are
    used to prevent metal precipitation and to improve the quality oI their deposition. Among chelatants, polyaminocarboxylates
    are a special class largely used |1|, because strong and soIt donor atoms in the same molecule give versatile metal complexes.
    However, the treatment oI these wastewater by metal precipitation with pH or classic cationic resins is ineIIicient. Separation
    methods such as evaporation, reverse osmosis or nanoIiltration to decontaminate this types oI wastewaters are very eIIicient,
    but their costs are oIten prohibitive. UltraIiltration can be used in combination with complexation with a polymer conIined in
    the retentate (PAUF). This retains speciIically a metal ion |2| and avoids high osmotic pressure to compensate.
    In this work, the binding oI Cu
    2
    and Ni
    2
    chelates with EDTA and NTA by polycations has been studied.
    The retention oI Cu
    2
    and Ni
    2
    chelates by polyethyleneimine (PEI) and chitosan has been investigated vs pH with Iris
    membranes. PEI is eIIicient to retain these metal ions in the pH range 4-8. Treated solutions easily pass the legal limit Ior
    rejection in the natural environment. PEI is a better metal adsorbant than Fe(III) or active charcoal. The mechanism oI metal
    retention can be oI covalent or electrostatic nature depending on the pH and speciation in solution. The metal retention
    increases as the stability oI the chelate decreases. At pH7, we notice a clear competition between the polymer and the
    polyaminocarboxylate to bind the metal ions. Retention oI copper can be carried out in a continuous mode by contrast to Ni-
    chelates which are too kinetically inert. Apparent metal retention in total recycling and in continuous addition oI pollutants
    modes has been carried out and interpreted with an chemical equilibria model. PEI was regenerated by metal electrolysis at
    pH2.
    The PAUF with PEI to retain Cu
    2
    and Ni
    2
    chelates with EDTA or NTA was eIIicient. However, we used a low molecular
    weight cut-oII Ior the membranes and this does not allow to obtain high permeate Iluxes.
    |1| Knepper, T. 2003. Trends Anal. Chem., 22(10), 708-724.
    |2| Molinari, R ; Poerio, T ; Argurio, P. 2007. J Memb. Sci., 295, 139-147.
    -409-
    PF.2.13
    Use of reaction and ultrafiltration to decontaminate media
    A. Petitgirard, M. Djehiche, D. Zamariotto, A. B. Akadar, J. Persello, M. Euvrard, P. Fievet, N. Fatin-Rouge
    Universitv of Franche-Comte, Laboratoire de Chimie des Materiaux et Interfaces,25030 Besanon Cedex, France
    nicolas.Iatin-rougeuniv-Icomte.Ir
    Micro-pollutants are largely produced and widespread in the environment. The strict levels oI environmental directives, as well
    as the limited disposal abilities and the need oI low energy-consumption techniques, require to develop strategies to
    decontaminate various media like soils, sludges and water. Membrane technologies oIIer high level oI pollutant removal Irom
    contaminated waste-waters, allowing treated water to be reused. ThereIore, desalination technologies like reverse osmosis or
    nanoIiltration are very eIIicient to remove micro-pollutants, however they are limited by their energy consumption and their
    lack oI robustness. Alternatively, water decontamination by reactive suspensions retained by a clariIication membrane such as
    an UF membrane, oIIers many advantages and is used in drinking water production plants |1|.
    This presentation deals with the combination oI reaction and ultraIiltration (RUF) to decontaminate soils and water Irom
    various pollutants. Practical cases oI membrane treatments are discussed and modeled. HereaIter we discuss advantages and
    drawbacks oI this strategy.
    Photodegradation oI representative water contaminants : PAHs and atrazine, assisted by TiO2 suspensions were carried out at
    pH6, in UF pilots with ceramic and organic membranes. Pollutants were degraded within 30 minutes. ThereIore in the case oI
    atrazine, cyanuric acid resulted as a stable metabolite, because oI its lack oI aIIinity Ior TiO2. The continuous treatment by
    photocatalysis and UF oI water polluted by phenanathrene was modelled and allowed to set boundaries in terms oI quality oI
    the treated water vs. relative Ilux.
    Metal ions (Cu2, Ni2) and their chelates with EDTA and NTA were removed in the pH range 4-8, by reaction with
    polyethyleneimine retained by an organic membrane. Electrostatic and chemical interactions were the main driving Iorces Ior
    the removal oI metal ion, depending on the pH. In contrast to Ni-complexes, the lability oI Cu-complexes allowed to treat the
    contaminated water in a continuous mode. The evolution oI Cu-concentration in permeates vs. the loading Iactor Cu-
    chelates/PEI at pH6, which displayed the retention capacity is in the order Cu > Cu-NTA > Cu-EDTA.
    Removal oI PAHs and metal ions (Cu
    2
    , Ni
    2
    , Pb
    2
    ) Irom contaminated soils by washing with reused water solutions at pH5-6,
    were carried out by RUF, liquid-liquid and liquid-solid extraction.
    |1| Memento technique de l`eau. 2005. Degremont
    PF.2.14
    Application of membrane processes in manure treatment
    K. Konieczny, A. Kwiecinska, M. Bodzek
    Silesian Universitv of Technologv, Facultv of Energv and Environmental Engineering, Institute of Water and Wastewater
    Engineering, Division of sanitarv chemistrv and membrane processes , Poland, 44-100 Gliwice, ul. Konarskiego 18
    krystyna.koniecznypolsl.pl
    Nowadays livestock Iarms produce huge amount oI manure, which is mostly treated as agricultural waste. However, manure
    can be, and even should be regarded as a source oI a valuable Iertilizer. Still it is obtained as a highly diluted, not-well
    balanced nutrient solution, and it requires special treatment to become a precious product Ior Iurther application.
    Membrane processes seem to be proper solution in manure treatment technology. They allow to concentrate nutrients
    contained in manure to a proper level, and also to recover water oI quite high quality which can be Iurther used on a Iarm.
    Such a solution appears to be optimal manure utilization process.
    MicroIiltration and ultraIiltration membranes are very eIIicient in solid-liquid separation. They can be used in isolation oI
    particles like phosphorus. The isolation oI smaller particles like ammonia and potassium can be obtained during nanoIiltration
    and reverse osmosis processes |1|.
    In the investigation crude manure was pretreated by centriIugation, and sedimentation. Such a prepared Ieed was introduced to
    Koch Laboratory Cell CF-1 equipped with membrane cell Ior Ilat sheet membranes. The process was run in a cross Ilow mode.
    DiIIerent types oI ultraIiltration membranes were tested in order to check the decree oI nutrients isolation and prepare the best
    Ieed Ior Iurther nanoIiltration or reverse osmosis process. PVDF membranes with cut oII 100 000 kDa and 30 000 kDa and
    PES membranes with cut oII 10 000 kDa and 5 000 kDa were used.
    -410-
    Feed and permeat standard parameters were investigated during the studies |2|. Parameters like COD, BOD, TOC, total
    nitrogen and ammoniacal nitrogen were checked beIore and aIter the process. It allowed to determine the level oI concentration
    oI nutrients as well as to choose Iurther treatment technique between nanoIiltration and reverse osmosis.
    L. Masse, D.I. Masse, Y. Pallerin, The use oI membranes Ior the treatment oI manure: a critical literature review, Biosystem
    Engineering 2008, 98, 371-380
    J.G.Pieters, G.G.J. Neukermans, M.B.A. Colanbeen, Farm-scale membrane Iiltration oI sow slurry, J.Agric.Engng.Res. 1999,
    73, 403-409
    PF.2.15
    Waste water from mechanical pulping - a natural resource, not a waste
    T. Persson, H. Krawczyk, A.-S. Jnsson
    Department of Chemical Engineering, Lund Universitv, P.O. Box 124, SE - 221 00, Lund, Sweden
    Tobias.Perssonchemeng.lth.se
    A potential means oI increasing yield in the pulp and paper industry is to one day produce chemicals and Iuels, such as
    hemicelluloses, Irom side streams. Currently in thermo-mechanical pulp mills, 95 oI the wood ends up in the paper while the
    remaining 5 is discharged. The yield loss is due to the Iact that hemicelluloses, lignin, extractives and Iines are dissolved into
    the waste water in the pulping process. II these compounds and particles can be isolated and separated Irom each other they
    could instead be used as high-value added chemicals and products. As an example, hemicelluloses could be used in the
    production oI barrier Iilms and hydrogels and Iines could be recirculated to the pulp mill and used to improve the yield and
    quality oI the pulp.
    A method to isolate these compounds and at the same time increase the water recirculation in the pulp mill has been developed.
    It consists oI Iour steps. The Iirst step is drum Iiltration that removes 90 oI the suspended matter, mainly Iines. The second
    step, microIiltration, removes the Iinal 10 oI suspended matter including more than 90 oI the extractives present in the
    waste water. The third step, ultraIiltration, isolates the hemicelluloses. The Iinal step, nanoIiltration, removes lignin and ions.
    The permeate Irom the nanoIiltration step has a conductivity below 200 S/cm and can be recirculated to the pulp mill and
    replace Iresh water.
    The overall economy oI the process has been estimated and compared to proIits Irom isolated compounds, decreased water
    consumption and decreased waste water treatment. The results show a great possibility to increase the cost eIIiciency and at the
    same time decrease the environmental impact by implementing this method in thermo-mechanical pulp mills.
    PF.2.16
    Removal of cobalt from water solutions by polymer assisted ultrafiltration
    L. Dambies
    1
    , A. Jaworska
    2
    , G. Zakrzewska-Trznadel
    2
    , B. Sartowska
    2
    , A. Miskiewicz
    2
    1
    Jisiting researcher to Institute of Nuclear Chemistrv and Technologv in the frames of Marie Curie Transfer of Knowledge
    profect AMERAC
    2
    Institute of Nuclear Chemistrv and Technologv, Dorodna 16, 03-195 Warsaw, Poland
    ajaworskaichtj.waw.pl
    In this study polymer assisted ultraIiltration (PAUF), also described as PEUF (polyelectrolyte-enhanced ultraIiltration) were
    presented. In principle, PAUF combines the ion exchange or chelating properties oI Iunctionalized water-soluble polymer with
    sieving power oI an ultraIiltration membrane. Because oI molecular cut oII oI the membrane being smaller than the metal-
    polymer complex, a separation can be achieved and the permeate, Iree oI metal, is collected.
    A series oI sulIonic acid water soluble polymers based on poly(vinyl alcohol) oI diIIerent molecular weights (10 000, 50 000
    and 100,000) were prepared and compared with commercially available poly(acrylic acid) Ior removal oI cobalt ions. The
    amount oI sulIonic groups bound by sulIonation oI PVA decreased with increase oI molecular weight oI the initial polymer
    applied. It was proven both by elemental X-ray analysis and ICP-OES technique that the number oI sulIonic groups in PVA-
    SO
    3
    10,000 MW was the highest that results in high bounding ability towards the cobalt ions present in the solution. In
    addition the acidic polymers oI high molecular weight and cross-linked structure have more rigid polymer chains in which
    accessibility oI Iunctional groups is hindered and the bounding capacity oI the material reduced.
    -411-
    UltraIiltration experiments showed that rejection rate oI Co
    2
    between pH 3 and 6 using sulIonated PVA (10,000 and 50,000
    MW) was higher than those determined Ior polyacrylic acid oI similar molecular weight. For sulIonated PVA 10,000 between
    pH 3 and 6 rejection rates obtains high, constant value, above 95 .
    SulIonated PVA oI molecular weight 10,000 was selected to test the possibility oI removal oI radioactive cobalt Irom water
    solution. The retention oI cobalt ions was high like in sorption experiments: R95-97. Simultaneously, high decontamination
    Ior
    60
    Co was observed: DF20; that means 20-Iold decrease oI the initial radioactivity oI the Ieed solution took place.
    The experiments showed that ultraIiltration combined with complexation by PVA-SO
    3
    proved its Ieasibility to remove
    eIIectively cobalt ions at pH 6. Strongly acidic water soluble polymer prepared Irom poly(vinyl alcohol) 10,000 MW can be
    applied in PAUF to decontaminate radioactive wastes containing
    60
    Co isotope, as well.
    PF.2.17
    Treatment and recovery of leather and cork processing industrial wastewaters by
    membrane hybrid processes
    C. Korzenowski
    1,3
    , K. Streit
    3
    , A. C. Santos
    2
    , M. Minhalma
    1,2
    , A. M. Bernardes
    3
    , J. Z. Ferreira
    3
    , M.N.C. Pinho
    1
    1
    Instituto Superior Tecnico, (IST/ICEMS), Universidade Tecnica de Lisboa, Av. Rovisco Pais, 1, 1049-001, Lisbon, Portugal.
    2
    Instituto Superior de Engenharia de Lisboa, (ISEL), Rua Conselheiro Emidio Navarro, 1, 1959-007, Lisbon, Portugal
    3
    Universidade Federal do Rio Grande do Sul (UFRGS/ PPGEM) , Av.Bento Gonalves 9500, Porto Alegre, RS, Bra:il
    ckorzenowskigmail.com
    Membrane technologies are nowadays crucial Ior the development oI sustainable and cleaner processes in industries that are
    water-intensive users, like leather and cork processing industries. The minimization oI water consumption is associated to the
    treatment oI the eIIluents in view oI water recycling and by-products recovery.
    In the Iirst targeted industry, the leather processing eIIluents are complex organic/inorganic mixtures, and besides the
    elimination oI the organic charge Ior pollution abattement, the reduction oI the salts content is necessary, when water recycling
    is envisaged. This two-Iold objective is obtained through the coupling oI nanoIiltration (NF) and electrodialysis (ED).
    In the cork industry, the nanoIiltration oI the wastewaters Irom the cork plancks boiling envisages both process water recycling
    and production oI tannin-rich concentrates |1, 2|. This is achieved throug the NF optimization in terms oI concentration Iactors
    and permeation Iluxes.
    In this work a model solution representative oI the leather industrial wastewaters was used. Regarding the cork processing
    wastewaters real eIIluent samples were studied. All ED experiments were perIormed on a lab scale and on a pilot plant
    Tecnoimpianti. Membranes supplied by Ionics were used. The NF system was a Lab 20 Unit Irom AlIa Laval with
    commercially available NF membranes, NF-270 (FilmTec Corp., Minneapolis, MN).
    The obtained results demonstrate that the use oI a membrane hybrid process, coupling NF and ED, allows the achievement oI
    process water that can be reused in leather industry.
    For the cork industry a technical economical analysis based on the optimized NF parameters is carried out in terms oI the
    tannin recovery and water reuse.
    |1| W. Scholz, M. Lucas, Techno-economic evaluation oI membrane Iiltration Ior the recovery and re-use oI tanning
    chemicals, Water Res. 37 (2003) 18591867.
    |2| M. Minhalma, C. Dias, M.N. Pinho. Membrane Fouling in UltraIiltration oI Cork Processing Wastewaters. Advances in
    Environmental Research, 3 (2000), 539-549.
    -412-
    PF.2.18
    Potato industry waste water management by enzymatic hydrolysis of protein
    G. Lewandowicz
    1
    , Z. Lubiewski
    1
    , K. Leja
    1
    , W. Balcerek
    2
    1
    Department of Biotechnologv and Food Microbiologv, Po:nan Universitv of Life Sciences, ul. Wofska Polskiego 4,
    60-627Po:nan, Poland
    2
    Potato Starch Enterprise WPPZ Lubon SA, ul. Armii Po:nan 30, 62-030 Lubon, Poland
    gralewup.poznan.pl
    Annually, our company generated over 100000 tons oI waste water which are used as a Iertilizer. Obligatory reduction oI COD
    in generated waste water consist in thermal coagulation oI protein as well as suspended solids removal. However the applied
    technology oI thermal coagulation oI potato protein enables elimination only about halI oI total organic nitrogen |1|. Potato
    Iruit juice, i.e. stream resulting aIter the extraction oI starch Irom the potato, contains up to 2.5 oI proteins and consequently
    puriIied waste water still reveals to high COD as well as to high biogenic elements (N and P). On the other hand, potato
    protein due to its amino acids composition is potentially valuable as a Iood product. UnIortunately, Iunctional properties oI
    thermally coagulated potato protein are very poor so it may be apply only as a Ieed. The aim oI a lot oI works was to improve
    its Iunctional properties. Attempt oI ultraIiltration and diaIiltration processes seems to be especially interesting |2|.
    Enzymatic hydrolysis oI proteins enables manuIacturing oI products with important Iunctional and biological properties,
    without deterioration in nutritional value. However, the majority oI works regarding this problem were accomplished using
    whey as a raw material |3|. Protein hydrolysates could be applied as a component oI seasonings similar to soya sauces
    traditionally manuIactured by Iermentation processes. The aim oI our work was application oI enzymatic membrane reactor Ior
    the hydrolysis oI proteins contained in potato Iruit juice as a Iirst step in Iormation oI Iood product.
    The hydrolysis process was carried out in a CRMR equipped with ultraIiltration module containing ceramic membrane oI
    tubular conIiguration. The Iiltrate Iraction was collected while the retentate were recycled. The loss oI raw material was
    supplemented by Iresh potato Iruit juice.
    It was stated that steady state process could be achieved over 2 hours and obtained product could be used as a component oI
    seasoning oI appropriate sensory properties.
    L. Mzynski, M. Maczynski, G. Urbaniak, Z. Kaliszan, A. Szymankiewicz, M. Otworowski, J. Koronkiewicz, Sposob
    odzyskiwania bialka z soku ziemniaczanego (A method Ior protein recovery Irom potato Iruit juice) in Polish 1985, Polish
    Patent No 126 333.
    H.J. Zwijnenberg, A.J.B. Kemperman, M.E. Boerrigter, M. Lotz, J.F. Dijksterhuis, P.E. Poulsen, G-H. Koops, Native protein
    recovery Irom potato juice by ultraIiltration, Desalination 2002, 144, 331-334.
    S.C. Cheison, Z. Wang, S-Y. Xu, Multivariate strategy in screening oI enzymes to be used Ior whey protein hydrolysis in an
    enzymatic membrane reactor, International Dairy Journal 2007, 17, 393-402.
    -413-
    PF.2.19
    Iodine separation from well waters using liquid membrane
    M. E. Craciun, A. C. NechiIor, C. Luca, G. NechiIor
    Politehnica Universitv of Bucharest, Department of Analvtical Chemistrv and Instrumental Analvsis, Poli:u Street no. 1- 7
    district 1, Bucharest, Romania
    mecraciunyahoo.com
    An important source oI iodine is well water oI oil industry. For
    concentrations below 20 mg/L I
    2
    and complex composition oI
    chloride, bromide, sodium, potassium, magnesium, calcium and
    sulIate ions, recovery processes with liquid membrane become
    competitive. The paper presents a comparative study oI iodine
    separation with liquid classical membrane |1| and with support oI
    polyetherketone.
    The iodine separation takes place by oxidation oI iodide ion (source
    phase) to molecular iodine and transIer through a membrane into
    the receiving phase by reducing the iodide ion with sodium
    thiosulIate (Figure 1). The parameters studied was the concentration
    oI oxidizing agent, transIer surIace oI the membrane, the Ilow rate
    oI aqueous phases and the inIluence oI crown ethers on the
    transport velocity oI I
    3
    -
    through membrane.
    In the Iirst case, a liquid membrane on PEEK support, in the
    presence oI variation oI the solvent nature and crown ether, has
    been used Ior separations. In the second case, double liquid jet
    membrane |2| was structured ranging the Ilow rate oI the source
    phase, shape, volume and area oI dispersed drops through
    membranes.
    receiving phase source phase
    membrane
    magnetic stirrer
    receiving phase source phase
    membrane
    magnetic stirrer
    Figure 1 Experimental Installation
    A. A. EnsaIi, H. Eskadari, Microchem. J., 2001, 69, 45.
    M.E. Craciun, O. Gales, A. C. G. NechiIor, Proceedings oI XXIII International Symposium on Physico-Chemical Methods oI
    Separation, ISBN 978-83-231-2208-1, Ars Separatoria, 6-9 July 2008, Torun, Poland, 243-246.
    PF.2.20
    Synthesis, morphologic analysis and water vapour flux through the cellulose
    triacetate asymmetric membranes from waste materials: newspaper and mango seed
    C.S. Meireles
    1
    , M. Zeni
    2
    , E.A.M. Ribeiro
    1
    , M.F. Ferreira Junior
    1
    , R.M.N. Assuno
    1
    , G. Rodrigues Filho
    1
    1
    Instituto de Quimica, Universidade Federal de Uberlandia, Uberlandia-MG, Bra:il
    2
    Departamento de Fisica e Quimica, Universidade de Caxias do Sul, Caxias do Sul-RS, Bra:il
    mzandraducs.br
    Asymmetric membranes may be used in a broad range oI applications, such as reverse osmosis, hemodyalisis, and organic
    mixture separation. In this paper, triacetate cellulose (CTA) asymmetric membranes were produced Irom waste materials oI
    biomass: newspaper and mango seed. The degree oI substitution oI CTA was 2.65 + 0,07. DiIIerent Iormulations were used to
    prepare the CTA membranes Irom newspaper and mango seed: CTA, dichloromethane and water with and without addition
    oI magnesium perchlorate. The results oI water vapour Ilux Ior the membranes produced with magnesium perchlorate were
    higher than those Ior the membranes produced without salt. Furthermore, the results oI Ilux Ior membranes produced with salt
    are close to the Ilux oI commercial membrane SG Osmonics |1|. The salt addition, apparently, acts on the porous Iormation in
    the membrane. The membranes were characterized by scanning electron microscopy (SEM) and classiIied as asymmetric by
    presence oI a dense skin layer and a porous support. The membranes were also characterized by diIIerential scanning
    calorimetry (DSC), thermogravimetric analysis (TGA) and pure water permeation rate and rejection to solutes.
    -414-
    |1| G. Rodrigues Filho, R.C. Silva, C.S. Meireles, R.M.N.Assuno, and H. Otaguro. Water Ilux through blends Irom waste
    materials: Cellulose acetate (Irom sugar cane bagasse) with polystyrene (Irom plastics cups J. Appl. Polym. Sci., 96,
    522(2005).
    PF.2.21
    Interactions of micropollutants, microorganisms and secondary treatment effluent
    matrix in RO and NF processes for wastewater reuse
    M. Jacob
    1
    , C. Guigui
    1
    , C. Cabassud
    1
    , S. Masclet
    2
    , L. Moulin
    3
    , G. Lavison
    3
    1
    Universite de Toulouse, INSA, UPS, INP, LISBP, 135 Avenue de Rangueil, F-31077 Toulouse, France
    INRA, UMR792 Ingenierie des Svstemes Biologiques et des Procedes, F-31400 Toulouse, France
    CNRS, UMR5504, F-31400 Toulouse, France
    2
    SAUR R&D Les Cvclades 1, rue Antoine Lavoisier 78064 Saint-Quentin-en-Yvelines - France
    3
    CRECEP - 144 avenue Paul Jaillant Couturier - 75014 Paris - France
    matthieu.jacobinsa-toulouse.Ir
    The combination oI membrane bioreactor (MBR) and reverse osmosis (RO) or nanoIiltration (NF) processes can reduce the
    presence oI pollutants (metals, pesticides, pharmaceutical by-products.) and micro-organisms which are not well treated in
    conventional domestic wastewater treatment plants. Many studies Iocus on retention perIormances oI RO and NF either with
    ultrapure water doped with micropollutants injected at very high concentration (over 1 mg/L) |1,2| or less Irequently with real
    eIIluent matrix |3|. Thus, the objective oI this study is to investigate Iiltration perIormances oI RO and NF in term oI retention
    capacities but also NF and RO Iouling velocities induced by the presence oI micropollutants. Micropollutants (Polycyclic
    aromatic hydrocarbon (PAH), triazins, metals and microorganisms) are injected in a real MBR permeate matrix at
    concentration close to reality (around 1 g/L).
    At Iirst, labscale Iiltrations underline the impact oI MBR permeate matrices without any doping on RO and NF membrane
    perIormances in term oI Iouling velocities. A variation oI 30 oI conductivity and 20 oI total organic carbon led to severe
    Iouling oI RO and NF membranes. In parallel, micropollutant retentions were investigated in ultrapure water matrix. RO shows
    retention capacities higher than 95 Ior microorganisms, PAHs and metals when triazins were retained between 35 and 98
    . NF membranes show globally lower retention capacities. Finally, Iollowing these preliminary studies, experiments were
    perIormed using a real MBR permeate matrix. RO shows better retention capacities when Iiltrating MBR permeate (mean
    retention oI 97 Ior triazins) doped with micropollutants than when Iiltrating ultrapure water doped with the same
    micropollutants (mean retention oI 90 Ior triazins). Furthermore, similar Ilux decline were observed Ior Iiltration oI MBR
    permeate matrix and the same matrix with micropollutants. Inversely, the presence oI micropollutants act on membrane Iouling
    with ultrapure water (0-30 Ilux decline diIIerence was observed). Each micropollutant Iamily acts diIIerently on RO or NF
    membrane causing concentration polarisation increase at the membrane surIace, precipitation, electrostatic repulsion.
    More experiments are underway concerning a retention measurement campaign run at pilot scale on micropollutant oI
    environmental interest. A peak oI pollutant is injected at the inlet oI the MBR and the becoming oI these pollutants all along
    MBR and RO processes is analysed.
    |1| C. Bellona, J.E. Drewes, P. Xu, G. Amy (2004) Factors aIIecting the rejection oI organic solutes during NF/RO treatment
    a literature review. Water Research 38 p 2795-2809
    |2| K. Kimura, G. Amy, J.E. Drewes, T. Heberer, T. Kim, Y. Watanabe (2003) Rejection oI organic micropollutants
    (disinIection by-products, endocrine disrupting compounds, and pharmaceutically active compounds) by NF/RO membranes.
    Journal oI Membrane Science 227(1-2): p. 113
    |3| A.M. Comerton, R. Andrews, D. Bagley, C. Hao (2008) The rejection oI endocrine disrupting and pharmaceutically active
    compounds by NF and RO membranes as a Iunction oI compound and water matrix properties. Journal oI Membrane Science.
    313(1-2): p. 323
    -415-
    PF.2.22
    Ultrafiltration membrane of ZrO
    2
    deposited on porous ceramic support prepared
    from moroccan natural material: elaboration characterization and application
    H. Elkinani
    1
    , A. Larbot
    2
    , J. Benavente
    3
    , S. Rakib
    1
    , M. Sghyar
    1
    1
    Laboratoire des Materiaux et Protection de lenvironnement. Faculte des Sciences Dhar El Mehra:, BP 1796, Universite de
    Fes, Morocco
    2
    Institut Europeen des Membranes de Montpellier, UMR 5635, CNRS- ENSCM-UMII, 1919 route de Mende, F-34293
    Montpellier Cedex 5, France
    3
    Departement de Phvsique Appliquee I, Faculte des Sciences, Universite de Malaga. E-2971 Malaga, Espagne
    kinanihahotmail.com
    In this work, the new ultraIiltration membranes A/ZrO
    2
    /ZrO
    2
    and S/ZrO
    2
    /ZrO
    2
    are prepared. These membranes have an
    asymmetric structure |1|. The bulk ceramic support was Iormed by the extrusion |2| oI a ceramic paste derived Irom a clay A
    or granitic sand S powders. Membrane Iired and characterised by mercury porosimetry showed pore diameters centred near 2,6
    m (1120C) Ior clay support and near 10,3 m (1060C) Ior granitic sand support. The intermediate layer, 0.32 m in pore
    diameters, deposited onto the supports, was obtained by using suspensions oI ZrO
    2
    powders. The water permeability
    determined Ior S/ZrO
    2
    and A/ZrO
    2
    membranes is respectively 2390 and 2050 l.h
    -1
    .m
    -2
    .bar
    -1
    . Both macroporous support and
    microIiltration layer will be considered as support Ior ultraIiltration layer. The suspended powder technique was used Ior
    elaborating the active layer ZrO
    2
    . The thickness is smaller than 4 m and the pore size is centred near 45 nm at the Iiring
    temperature oI 700C. The water permeability determined Ior S/ZrO
    2
    /ZrO
    2
    and A/ZrO
    2
    /ZrO
    2
    membranes is respectively 104
    and 94 l.h
    -1
    .m
    -2
    .bar
    -1
    . The Ilux and the rejection rate oI the Iiltration tests perIormed with ionic solutes (NaCl, CaSO
    4
    , CR
    (NO
    3
    )
    3
    , Cr2(SO
    4
    )
    3
    ) are determined |3|. The rejection rate Iound more important with Cr
    3
    and depends on the associate anion.
    It is higher Ior NO

    3
    70 than Ior SO
    2
    4
    60 . These composite membranes can be used Ior treatment oI wastewater
    containers oI the Chrome ions.
    |1| L. Cot, Inorganic Membranes: Academic Exercise or Industrial Reality, Proc. 5 th Intern. ConIerence on Inorganic
    Membranes, Nagoya, June 1998.
    |2| J.C. Ruiz, L. Broussous, A. Larbot, j. Charpin, P. Bergez and L. Cot, New anti-Fouling Tubular Membranes: Preparation
    and PerIormances, Proc. ICIM4, Gatlinburg, July 1996, p79.
    |3| H. Elkinani, These a l`Universite des Sciences Fes: Membranes de MicroIiltration et D`ultraIiltration a base de Zircone sur
    Supports d`Argile et d`Arene granitique: Elaboration et Caracterisation, 2006.
    PF.2.23
    Removal of tributyltin compounds in a membrane bioreactor
    M. Aubenneau
    1
    , J. Seira
    1,2
    , C. Bancon-Montigny
    2
    , C. Wisniewski
    1
    1
    UMR CIRAD 016 Genie des Procedes, Eau et Bioproduits (GPEB), UFR des Sciences Pharmaceutiques et Biologiques
    Universite de Montpellier 1, 15 Avenue Charles Flahault BP 14491, 34093 Montpellier Cedex 5, France.
    2
    UMR 5569 HvdroSciences Montpellier, Maison des Sciences de lEau Universite Montpellier II Place Eugene Bataillon - CC
    MSE, 34095 Montpellier Cedex 5
    wisniewsuniv-montp2.Ir
    Organotin compounds (OTs) are endocrine disrupters toxic to aquatic liIe at extremely low concentrations, i.e. a Iew ng/L.
    Tributyltin compounds (TBT) have been widely used in industrial applications because oI their thermoresistant and biocidal
    properties (antiIouling agents in ship paints). The toxicity oI OTs combined to their widespread use has lead then to be
    included in the priority list oI the EU water Iramework directive. Considered as priority hazardous substances in water, the
    maximum allowable concentration oI Tributyltin compounds is proposed to be Iixed at 0.0015 g/L in inland surIace waters.
    TBTs are suspected to enter rivers, streams and surIace waters through the eIIluents oI wastewater treatment plants (WWTPs).
    ThereIore, the development oI processes, or operating applied design criteria, showing a signiIicantly better removal oI these
    compounds is oI elementary interest. The membrane bioreactor is an emerging technology based on the use oI membranes in
    combination with a biological treatment. The eIIiciency oI MBRs to achieve Iurther removal oI micropollutants is linked with
    the potentiality to the system to operate with non conventional operational conditions (high sludge age, high biomass
    concentration.). Actually, operations at high sludge ages can Iavor the development oI slow growing bacteria, the presence oI
    -416-
    more diverse microbial communities with broader physiological capabilities and the adaptation oI these communities to
    degrade speciIic organic compounds.
    The aim oI this study is to demonstrate the eIIiciency oI membrane bioreactors to remove TBT compounds. The study is
    speciIically Iocused on the contribution oI adsorption and biodegradation to the overall removal.
    The experiments are based on two approaches. The Iirst one consists in respirometric activity measurements, with and without
    TBT, with the objectives to evaluate the potential toxicity oI TBT compounds on bacterial community present in conventional
    activated sludge. The second one consists in observing the removal oI the target compounds in a laboratory scale submerged
    membrane bioreactor, operating with high sludge age. The pilot is Ied by a synthetic wastewater containing ethanol, urea,
    KH
    2
    PO
    4
    , and is adjusted in TBT at a deIined concentration. TBT concentrations are measured in inIluent and eIIluent by high
    sensitive and selective hyphenated technique oI speciation (GC-ICP-MS) aIter derivatization and extraction in isooctane. This
    study is completed by sampling oI inIluent and eIIluent oI wastewater treatment plants (WWTP) Iunctioning with diIIerent
    kinds oI process (CAS, MBR, trickling Iilter.). The objective oI this chosen methodology is to compare the eIIiciency oI the
    diIIerent processes to eliminate the target compounds. In the second part oI this study, batch experiments are carried out to
    investigate the contribution oI the adsorption on the total removal. Parameters, like concentration and granulometry oI the total
    suspended solids are studied. The results are presented and discussed.
    |1| M. Clara, N. Kreuzinger, B. Strenn, O. Gans, H. Kroissn, The solids retention timea suitable design parameter to
    evaluate the capacity oI wastewater treatment plants to remove micropollutants, Water Research, 39, 1 (2005) 97-106.
    PF.2.24
    Membrane process treatment for greywater recycling: investigations on direct
    tubular nanofiltration
    F. Hourlier
    1,2
    , A. Masse
    2
    , P. Jaouen
    2
    , A. Lakel
    1
    , C. Gerente
    3
    , C. Faur
    4
    , P. Le Cloirec
    5,6
    1
    CSTB 11 rue Henri Picherit BP 82341 44323 Nantes Cedex 03 France
    2
    GEPEA UMR CNRS 6144 CRTT 37 boulevard de lUniversite BP 406 44602 Saint-Na:aire Cedex France
    3
    EMN GEPEA UMR CNRS 6144 4, rue Alfred Kastler BP 20722 44307 Nantes Cedex 3 France
    4
    Universite de Montpellier 2 UMR CIRAD 016 Genie des Procedes Eau - Bioproduits 2 place Eugene Bataillon 34095
    Montpellier Cedex 5 France
    5
    Ecole Nationale Superieure de Chimie de Rennes, CNRS, UMR 6226, Avenue du General Leclerc, CS 50837, 35708 Rennes
    Cedex 7, France
    6
    Universite europeenne de Bretagne, France
    Ianny.hourliercstb.Ir
    One oI the main ways to preserve water resource in urban areas is to recycle greywaters in-situ. Reclaimed water can be used
    Ior various applications (garden watering, toilet Ilushing.), so the potable water requirement is reduced. Direct membrane
    Iiltration is a promising technology to recycle greywater on-site. This study Iocuses on selecting a nanoIiltration tubular
    membrane and on deIining its operating conditions in order to recycle and reuse greywaters inside buildings.
    In order to carry out reproducible experiments, a synthetic greywater was reconstituted and consists in a mixture oI chemical
    products oI technical quality to simulate organic pollution, and oI septic eIIluent to simulate the microbiological
    contamination.
    Then, three tubular nanoIiltration membranes made oI a thin-Iilm composite polyamide / polyethersulIone provided by PCI
    Membrane Systems (Basingstoke, UK) were tested to recycle this synthetic greywater with a constant concentration at 25 C
    under two diIIerent pressures (20 and 35 bar). These three membranes have distinct molecular weight cut-oIIs and diIIerent
    operating pressures ranges (AFC30: 200 Da, 30 to 35 bar AFC40: 200 Da, 15 to 40 bar AFC80: tighter than 200 Da, 40 to
    45 bar).
    At 20 bar, no membrane gave satisIactory retention rates on organic matters, whereas at 35 bar, AFC80 produced a high-
    quality permeate. Retention rates oI 98 Ior BOD
    5
    and 95 Ior COD and anionic surIactants were observed, and neither
    Iaecal coliIorms nor Enterococcus were detected in the permeate. An acceptable permeation Ilux, close to 50 L.h
    -1
    .m
    -2
    , was
    obtained.
    The perIormances oI this membrane were also tested on a real greywater and compared to the retention rates and Ilux obtained
    on synthetic greywater. The lab experimental results are promising: the chemical and microbiological quality oI permeate was
    good, and retention rates and Iluxes were similar to those observed on synthetic greywater. These results validate the utilisation
    oI the synthetic greywater developed in this study Ior the evaluation oI membrane eIIiciency to treat greywaters, and this new
    tool will be a real asset Ior Iuture studies.
    These results also show the eIIectiveness oI direct nanoIiltration to recycle and reuse greywaters. This process can signiIicantly
    reduce the potable water requirement within a household without using any chemical products, except Ior membrane cleaning.
    It is saIe, as membranes constitute a physical barrier to any micro-organism, and this is a great asset considering that in small
    -417-
    installations, greywater composition is highly variable. So, direct nanoIiltration oI greywater in buildings seems to be a
    realistic solution, ensuring both saIety and environmental sustainability.
    PF.2.25
    Treatment by membrane technology, of press liquid from solid wastes generated
    during orange juice production
    E. Garcia-Castello, L. Mayor, A. Argelles, M.L. Gras, D. Vidal
    Institute of Food Engineering for Development. Polvtechnic Universitv of Jalencia, Camino de Jera, s/n, 46022, Jalencia,
    Spain.
    egarcia1iqn.upv.es
    During orange juice production, about 50 in weight oI orange Iruits is discarded as waste peels, membranes, juice vesicles
    and seeds.
    Orange peels and pulp (moisture content ca. 82 w.b.) contain several valuable compounds such as soluble sugars, insoluble
    carbohydrate Iibers, organic acids, essential oils, Ilavonoids, and carotenoids. These semi-solid wastes can be pressed to obtain
    a press liquid rich in soluble sugars that can be concentrated up to citrus molasses grade. On the other hand, a dry solid cake is
    also obtained and employed in animal Ieed.
    This work is Iocused on the press liquid stream and its concentration by both reverse osmosis and direct osmosis membrane
    technologies. Press liquid model solutions containing sucrose, glucose, Iructose, citric acid, ethanol, pectin and protein |1|
    have been used in the experiments. DiIIerent process conditions have been assayed in each case and a comparison between
    both systems has been done.
    |1| Braddock, Robert J. (1999) Handbook oI citrus by-products and processing technology. Ed.: John Wiley & Sons. New
    York
    PF.2.26
    Cyclophosphamide removal by nanofiltration and reverse osmosis membranes -
    Effect of water matrix properties
    L. Wang
    1
    , C. Albasi
    1
    , V. Faucet-Marquis
    1
    , A. PIohl-Leszkowicz
    1
    , C. Dorandeu
    3
    , B.Marion
    3
    , C. Causserand
    2
    1
    Laboratoire de Genie Chimique (UMR 5503), 5 rue Paulin Talabot, 31106 Toulouse,France
    2
    Laboratoire de Genie Chimique (UMR 5503), Universite de Toulouse, Universite Paul Sabatier, 31062 Toulouse cedex 09,
    France
    3
    Laboratoire de biophvsique et bio-analvse, faculte de pharmacie, Universite de Montpellier, BP 14491, 15 avenue Charles-
    Flahault, 34093 Montpellier, France
    causserachimie.ups-tlse.Ir
    In hospital or pharmaceutical discharges, but also in water treatment plants and more generally in water resources, numerous
    toxic pollutants have been identiIied. The consequences oI their presence in the environment are cancers, allergies, Iertility
    losses, thyroid diseases or teratogenic eIIects. These pollutants that can be present in water in their initial Iorm or metabolized
    lead to the problem oI the choice oI the process that could be eIIicient Ior their removal.
    In this purpose, we have investigated a membrane bioreactor (MBR) coupled to a nanoIiltration or reverse osmosis unit in
    order to eliminate, when necessary, the residual pollution. The target molecule chosen in this project: the alkylating
    antineoplastic drug Cyclophosphamide (CP) is mainly employed in therapies against cancer and exhibits genotoxic properties
    Ior any living organism. This molecule can be detected in concentrations ranging Irom 20 ng/L to 4.5 g/L in hospital sewage.
    At steady-state conditions, the MBR removal eIIiciency being equals to 75 Ior CP, nanoIiltration (or reverse osmosis) oI
    MBR permeate is then necessary. This second step is presented in the present paper.
    Experiments were carried out in a dead-end batch Iiltration cell in order to limit the volume oI solutions and the membrane
    surIace (a new sample oI membrane was used Ior each experiment). A Iirst series oI experiments was perIormed with simple
    solutions oI molecule in pure water in order to evaluate the removal eIIiciency oI CP by various membranes (nanoIiltration and
    reverse osmosis) and to select the most eIIicient. We have then investigated the Iactors inIluencing retention, such as
    -418-
    transmembrane pressure, Ieed composition (ionic strength, presence oI organic matter) and CP concentration, this last
    parameter being chosen in the range oI concentrations that are Iound in MBR permeate. This study conIirms that an accurate
    evaluation oI a given membrane in terms oI the retention oI a contaminant is not possible until the saturation oI the membrane
    with the component oI interest is accomplished. On the other hand, transmembrane pressure, CP initial concentration and ionic
    strength oI the Ieed solution have almost no eIIect on CP retention by NF and RO membranes.
    In a second series oI experiments, the permeate oI the membrane bioreactor was used as the background solution and the data
    compared to the previous mentioned. Water matrix exhibits a great inIluence: CP rejection rate by NF membrane was obvious
    enhanced when MBR eIIluent was used. Membrane Iouling and interactions between CP molecules and water matrix itselI
    appear to contribute to the higher rejection oI CP.
    The analysis methods used were HPLC-UV and HPLC-MS-MS Ior CP samples, depending on the concentration range.
    PF.2.27
    PURATREAT: Optimized MBR wastewater treatment for the Mediterranean area
    H. Zwijnenberg
    1
    , A. Kemperman
    1
    , S. Sayadi
    2
    , T. Arnot
    3
    , M. Ben MaklouI
    4
    , M. Wade
    5
    1
    Universitv of Twente,
    2
    Centre de Biotechnologie de Sfax,
    3
    Universitv of Bath,
    4
    lOffice National de lAssainissement de
    Tunisia,
    5
    Technologie Transfer Zentrum Bremerhaven,
    1
    European Membrane Institute Twente (E.M.I. Twente), Universitv of Twente, Facultv of Science and Technologv P.O. Box
    217, NL-7500 AE Enschede, the Netherland
    h.j.zwijnenbergutwente.nl
    Water scarcity is a problem Iaced by all the countries oI the Mediterranean area. In particular, the EU Water Initiative has
    identiIied the Southern Mediterranean as the area oI highest water stress in the world. Most wastewater produced in urban
    areas oI the region is ineIIiciently treated due to poor maintenance oI the equipment and high cost oI electricity (in Morocco
    Ior example, 60 oI activated sludge plants are out oI order |CSEC 2001|). In rural and remote areas, the population has
    practically no access to water sanitation, whereby wastewater is directly discharged into water bodies or re-used Ior irrigation
    without treatment, thus spreading water-borne diseases and causing eutrophication and water pollution.
    The majority oI the existing treatment plants in the area Iocus only on the reduction oI suspended matter and oxygen demand
    oI the discharged waters. They are not designed to remove pathogenic excreted micro-organisms. As a high drive exists to
    reuse the water Ior agricultural purposes the risk oI contamination oI crops and live stock with parasites should be reduced.
    Membrane bioreactor technology provides a successIul alternative to those conventional water treatments as membranes act as
    a barrier against bacteria and viruses. However, most membrane bioreactors currently in use are primarily designed to reduce
    BOD and nitrogen. As a consequence they have very high running costs because oI the high pressure drop and high air-
    Ilushing rate required Ior their operation. The operating conditions and demands Ior the Middle Eastern and North AIrican
    Countries are generally diIIerent Irom western countries in that respect that higher operating temperatures are used, up to 35C,
    and a reduction in nitrogen and phosphorus is not desirable. This sets new demands to MBR operation and open up
    possibilities Ior energy reduction.
    This project studies a new approach to the operation oI membrane bioreactors. It includes a comparison oI three leading MBR
    technologies using optimized operating procedures in order to yield low energy consumption and reduced maintenance costs.
    The initial results oI the three reactors show the perIormance oI the membrane bioreactors in equal conditions and gave a
    window Ior optimization. Further testing oI these characteristics provides optimized bioreactors Ior the peri-urban areas oI the
    Mediterranean basin to provide the region with pathogenic Iree irrigation water that contains a high amount oI plant nutrition.
    -419-
    PF.2.28
    Different membrane approaches for the transport of arsenic: advantages and
    limitations of polymer inclusion, anion-exchange and supported liquid membranes
    R. Gell
    1
    , C. Fontas
    1
    , E. Antico
    1
    , V. Salvado
    1
    , S. Velizarov
    2
    , J. Crespo
    2
    1
    Department of Chemistrv, Universitv of Girona, 17071 Girona, Spain
    2
    CQFB/REQUIMTE, Department of Chemistrv, FCT, Universidade Nova de Lisboa, P-2829-516 Caparica, Portugal
    claudia.Iontasudg.edu
    The membrane technology is viewed as a powerIul tool when highly sensitive and selective separation systems are demanded
    Ior medical, environmental and industrial purposes. Intense research eIIorts have been done in the last two decades developing
    diIIerent membrane systems to separate a number oI target species. Thus, the membrane technology can be used in many
    Iields, each one having its own needs and priorities, which can be as diIIerent as water treatment or a speciIic analytical
    application.
    In the present work, we present diIIerent membrane-based possibilities to deal with one oI the most serious environmental
    problems: the presence oI arsenic species in natural waters. Due to the high toxicity oI this semi-metal, it is oI great importance
    to develop separation systems Ior both the treatment oI polluted waters as well as to help in their monitoring in terms oI
    possible presence oI arsenic species. For that, we have investigated three diIIerent types oI membranes to achieve the same
    objective, the transport oI As Irom natural waters.
    On one hand, we have designed and studied a supported liquid membrane system based on Aliquat 336 (an anion exchange
    extractant) dissolved in dodecane, and the most important parameters aIIecting the Ieed and stripping compartments
    compositions have been optimized. On the other hand, the same carrier has been included in a polymer inclusion membrane
    made oI cellulose triacetate (CTA) and nitrophenyl octylether (NPOE) and its stability and possible applications have been
    investigated. Finally, two diIIerent anion-exchange membranes have been tested Ior the same purpose: a mono-anion perm-
    selective membrane (Neosepta ACS, manuIactured by Tokuyama Soda, Japan) versus a common anion-exchange membrane,
    (PS SA, produced by a PCA, Germany).
    Thus, the aim oI this work was to compare these three types oI membranes in terms oI their eIIiciency, stability and suitability
    Ior transport oI As between aqueous phases and to discuss their advantages and limitations, thus deIining the most relevant
    applications, in which the diIIerent membranes can better suit.
    Acknowledgements: The Iinancial support by Fundao para a Cincia e a Tecnologia (FCT), Portugal through Project
    PPCDT/AMB/57356/2004, and Ministerio de Ciencia e Inovacion through Project CTM2008-06847-C02-02/TECNO are
    grateIully acknowledged. R. Gell grateIully acknowledges a grant awarded by the University oI Girona (ReI. BR06/10) and a
    mobility grant by the University oI Girona
    PF.2.29
    Polymer inclusion membranes for As(V) transport and removal
    R. Gell, A. Parramon, E. Antico, V. Salvado, C. Fontas
    Department of Chemistrv, Universitv of Girona, 17071 Girona, Spain
    claudia.Iontasudg.edu
    Polymer inclusion membranes (PIMs) are regarded as one oI the solutions to overcome the instability oI supported liquid
    membranes (SLMs). PIMs are Iormed by casting a polymer, normally cellulose triacetate (CTA), Irom an organic solution
    containing also the carrier and a membrane plasticizer, which provides elasticity and constitutes the liquid phase in which the
    carrier molecules can diIIuse |1|. The Iact that the carrier is incorporated into a gel network oI a polymeric material increases
    the viscosity and, thus, prevents the loss oI the membrane phase to aqueous phases.
    In the present work, a PIM system has been developed Ior the transport oI arsenic contained in environmental samples. Arsenic
    is a naturally occurring metalloid that has become problematic in many areas in the world. Besides its natural sources, arsenic
    is introduced into water through anthropogenic activities such as dissolution oI mineral ores.
    Previous results using a SLM system demonstrated that the commercial extractant Aliquat 336 (a quaternary ammonium salt)
    was an eIIicient carrier Ior As transport. The compositions oI the aqueous phases were also investigated, and better results
    were obtained when using a Ieed phase at pH 7 and a stripping phase consisting oI a NaCl solution. From these results, PIMs
    were prepared incorporating Aliquat 336, and our eIIorts were Iocused on the membrane composition and its application. For
    -420-
    that, diIIerent polymers were investigated to Iorm the membrane such as CTA and PVC. Moreover, the eIIect oI the nature oI
    plasticizer was also studied and it was observed that NPOE Iormed stable membranes which eIIiciently transported As.
    Finally, the developed membrane system was applied to As(III)/As(V) separation as well as to remove As Iorm diIIerent
    natural sources such as groundwater and spiked tap and river water.
    |1| C. Fontas, R. Tayeb, M. Dhahbi, E. Gaudichet, F. Thominette, P. Roy, K. Steenkeste, M.P. Iontaine-Aupart, S. Tingry, E.
    Tronel-Peyroz, P. Seta, Polymer inclusion membranes: the concept oI the Iixed sites membranes revised, J. Membr. Sci., 2007,
    290, 62-72.
    The Iinancial support by Ministerio de Ciencia e Inovacion through Project CTM2008-06847-C02-02/TECNO is grateIully
    acknowledged.
    PF.2.30
    The fate of
    14
    C-radiolabelled diclofenac and 4`-hydroxydiclofenac in a laboratory
    scale MBR
    H. Bouju
    1
    , G. Hommes
    2
    , T. Wintgens
    2
    , P. Corvini
    2
    1
    Politecnico di Milano, DIIAR Sanitarv and Environmental Engineering Department, Pia::a Leonardo da Jinci 32, 20133
    Milano, Italv
    2
    Institute for Ecopreneurship, School of Life Sciences, Universitv of Applied Sciences Northwestern Swit:erland,
    Grndenstrasse 40, CH-4132 Mutten:, Swit:erland
    A better understanding oI persistent micropollutants, such as dicloIenac, removal pathway, as well as an improvement oI
    analytical methods accuracy is a current need to reduce their release to the environment.
    This work Iocuses on dicloIenac, which is one oI the most extensively used non-steroidal, anti-inIlammatory and non-
    prescribed drugs (NSAIDs), and its main metabolite excreted by humans. Indeed, dicloIenac concentration levels oI up to 15
    g.L
    -1
    were reported in water and wastewater samples |1|. By using
    14
    C-radiolabelled substances, it is expected to be easier to
    determine removal pathways, especially to distinguish between biodegradation, mineralization, adsorption and volatilization.
    Moreover, radio-tracing is the method oI choice Ior the detection oI any metabolites.
    For this purpose, studies have been carried out in a laboratory-scale membrane bioreactor (MBR) consisting oI a 1.15L glass
    reactor. The reactor was operated under perIectly mixed aerobic conditions at a sludge retention time oI 30 days and a
    hydraulic retention time oI 7.1 hours. The MBR was Ied with a sterilized synthetic wastewater prepared according to the
    OECD standards. In stable conditions, the total solids concentration was on average 10.5 g.L
    -1
    . The Iiltration unit consists oI 6
    PVDF Ilat sheet membranes oI 40 cm
    2
    (4x10) in parallel, with a nominal pore size oI 0.20 m. The whole system is sealed and
    oII-gas was trapped Ior Iurther analyses. AIter a stabilization period oI 2.5 times the SRT, a solution oI 142 g dicloIenac and
    52 g 4`-hydroxydicloIenac has been spiked in the reactor. It corresponds to a total oI 1.39 MBq. Radioactivity has been
    monitored Ior 16 days in the permeate, the MLSS, and the oII-gas. Every sample was analyzed by means oI Liquid
    Scintillation Counting (LSC), HPLC/LSC and HPLC/MS.
    First results showed that most oI the radioactivity leaves the reactor with the permeate. Indeed, the cumulative percentage oI
    total applied radioactivity collected in the eIIluent increased up to 87 in 48 hours, while a maximum oI 92.3 was reached
    aIter 16 days. Radioactivity concentrations in the various gas traps were low, hence, eIIects oI mineralization and/or stripping
    on dicloIenac and 4`-hydroxydicloIenac removal were negligible. In order to obtain a complete balance oI radioactivity, the
    membranes have also been combusted to determine whether some residues are sorbed to the Ilat sheet modules, however, this
    was also not signiIicant.
    |1| D. Stlten, S. Zhlke, M. LamshIt, M. Spiteller, Occurrence oI dicloIenac and selected metabolite in sewage eIIluents,
    2008, Science oI the Total Environment, 405(1-3), 310-316
    This work is supported by a Marie Curie Early Stage Research Fellowship oI the European Community`s Sixth Framework,
    within the MBR-TRAIN project, under the contract number MEST-CT-2005-021050.
    This project is also Iunded by the 'COST action 636 on 'Xenobiotics in the Urban Water Cycle
    -421-
    PF.2.31
    Processing solvent-rich water by nanofiltration
    F.P. Cuperus, I.M. Wienk
    SolSep B.J., St. Eustatius 65, 7333 NW Apeldoorn, The Netherlands
    cuperussolsep.com
    In many processes (waste) water is recycled using membranes, e.g. reverse osmosis or nanoIiltration. Current standard
    membranes and elements are very eIIective in terms oI productivity and costs. However, the tolerance oI these membranes
    towards relatively small content oI solvents is low. Apart Irom (m)ethanol, solvents like acetone, ethyl acetate and MEK
    inIluence the perIormance oI membranes very much by phenomena like swelling. The result at low solvent content is mostly a
    Iall in retention. Sometimes this can be regenerated when going back to standard water . At high solvent Iraction (~10)
    elements and membranes can be irreversible attacked and destroyed.
    Solsep has developed membranes that are stable in 100 organic solvents. However, these membranes can also be used in
    aqueous environments. The separation oI water and organic solvents can be done using NF or near RO. OI course, at high
    solvent content Iactors like osmotic pressure and concentration polarization play an important role. It will be shown that
    membranes can be crucial in making reclaim cost eIIective.
    PF.2.32
    Simultaneous removal of copper and cadmium by micellar-enhanced ultrafiltration
    using sodium deoxycholate
    J. Landaburu
    1
    , E. Pongracz
    1,2
    , R. Keiski
    1
    1
    Mass and Heat Transfer Process Laboratorv, Department of Process and Environmental Engineering, FIN-90014, Universitv
    of Oulu, Finland.
    2
    Centre of Northern Environmental Technologv, Thule Institute, FI-90014 Universitv of Oulu, P.O.Box 7300,Oulu, Finland
    Junkal.Landaburuoulu.Ii
    Heavy metals constitute a key portion oI the contaminants in chemical eIIluents. Further, due to their hazard to the
    environment and human health, heavy metals are targeted by international environmental legislation. Micellar-Enhanced
    UltraIiltration (MEUF) has been established as a viable membrane technology Ior the removal oI heavy metals Irom synthetic
    wastewaters |1|. In MEUF, the anionic surIactant Iorms large amphiphilic aggregate micelles when it is added to aqueous
    streams at a concentration higher than its critical micelle concentration (CMC). The heavy metal cations can be mostly trapped
    by the micelles due to electrostatic interaction and thus, retained by the ultraIiltration membrane. The metal cations not trapped
    by the micelles and the surIactant monomers will pass through the ultraIiltration membrane to the permeate. |2| To date, there
    has been Iew mention in the literature on the use oI biosurIactants Ior MEUF. BiosurIactants are considered environmentally
    Iriendly due to their low toxicity and biodegradability. An added advantanges oI biosurIactants is also their low CMC |3,4|.
    In this study, the simultaneous removal oI heavy metals such as copper and cadmium was conducted by Micellar-Enhanced
    UltraIiltration. The biosurIactant used was sodium deoxycholate (NaDC). The composition oI synthetic samples studied was
    based on a real waste water oI a Iertilizer company. Further, the use oI statistical experimental design was used Ior the
    evaluation oI Iive diIIerent Iactors aIIecting on the rejection coeIIicients oI the metals. The Iactors studied were Ieed
    concentration oI copper and cadmium, Ieed concentration oI the biosurIactant, pH and the presence oI phosphate anionic salts.
    The Academy oI Finland, Maj and Tor Neslling Ioundation and Thule Institute are acknowledged Ior their Iinancial support.
    |1| J. Landaburu, V. Garcia, E. POngracz and R.L Keiski, The removal oI zinc Irom synthetic wastewaters by micellar-
    enhanced ultarIiltration: Statistical design oI experiments, Desalination in press
    |2| B. R. Fillipi, L. W. Brant, J. F. Scamehorn and S. D. Christian, Use oI micellar-enhanced ultraIiltration at low surIactant
    concentrations and with anionic-nonionic surIactant mixtures, J. Colloid InterIace Sci., 1999, 213, 68-80
    |3| C. N Mulligan, Environmental applications Ior biosurIactants, Environ. Pollut., 2005, 133, 183-198
    |4| Y.-C. Huang, B. Batchelor and S.S. Koseoglu, CrossIlow surIactant-based ultraIiltration oI heavy metals Irom waste
    streams, Sep. Sci. Technol., 1994, 29 (15), 1979-1998
    -422-
    PF.2.33
    Hollow fiber supported liquid membrane microextraction for the determination of
    acidic pharmaceuticals in water samples
    E. Wdowiak
    1
    , E. Sagrista
    2
    , V. Salvado
    2
    , P. Wieczorek
    1
    , M. Hidalgo
    2
    1
    Institute of Chemistrv, Universitv of Opole, ul. Oleska 48, PL-45 052 Opole., Poland
    2
    Department of chemistrv, universitv of Girona, Campus Montilivi, 17071 Girona, Spain
    manuela.hidalgoudg.edu
    Pharmaceuticals have become important emerging contaminants due to their presence in environmental waters (Iollowing
    incomplete removal in wastewater treatment), threat to drinking water sources and concern about adverse eIIects oI both
    wildliIe and humans. Among these pharmaceuticals, non-steroidal anti-inIlammatory drugs (e.g. ibuproIen or dicloIenac) and
    lipid regulators are some oI the most commonly detected in concentrations ranging Irom the low ng/L up to the g/L level.
    Many pharmaceuticals are highly polar, which leads to LC as the technique oI choice Ior their determination. Despite the great
    instrumental advances achieved so Iar, matrix complexity and the Iact that these compounds must Irequently be monitored at
    very low concentrations, makes sample enrichment and cleanup indispensable steps. Solid phase extraction is the most
    commonly used technique Ior the extraction and enrichment oI pharmaceuticals Irom water samples. However, the
    determination oI pharmaceuticals in complex samples as untreated wastewater and some environmental waters is hampered by
    co-extracted organic interIerences. Supported liquid membrane (SLM) techniques are an alternative Ior the selective extraction
    and enrichment oI pollutants in water samples. SLM is based on a three-phase system with an organic phase between two
    aqueous phases. The organic phase is immobilized in a porous hydrophobic membrane.
    In this work, the applicability oI hollow Iiber supported liquid membrane (HFSLM) extraction Iollowed by HPLC-DAD Ior
    the determination oI acidic pharmaceuticals (naproxen, dicloIenac, cloIibric acid, and ibuproIen) in diIIerent water samples is
    evaluated. The target drugs were extracted Irom 1 L oI the aqueous sample with pH 2 into an organic solvent and Iinally back
    extracted into a basic aqueous solution located inside the lumen oI the Iiber. In order to obtain high extraction eIIiciency, the
    parameters aIIecting the HFSLM system perIormance, including organic solvent and extraction time were studied. Under the
    optimized conditions, enrichment Iactors up to 10000 were achieved, with relative standard deviations Irom 5 to 10. Limits
    oI detection (LODs) ranged between 2 ng/L and 10 ng/L. The method was applied to wastewater samples (treated and
    untreated) as well as river water and tap water.
    PF.2.34
    Gas holdup and liquid circulation in an airlift membrane bioreactor
    M. Kazemzadeh AIshar
    1
    , M. H. SarraIzadeh
    1
    , M. R. Mehrnia
    1
    , S. Naseri
    2
    , F. Pajoum Shariati
    1,3
    1
    School of Chemical Engineering, College of Engineering, Universitv of Tehran, P.O. Box 11155-4563, Tehran, Iran
    2
    Department of Environmental Health Engineering, School of Public Health and Center for Environmen Research (CER),
    Tehran Universitv of Medical Sciences, Tehran, Iran
    3
    Laboratoire de Genie des Procedes, Eau et Bioproduits, Universite Montpellier 1et 2, F-34095 Montpellier, France
    sarraIzdhut.ac.ir
    In this work, the eIIects oI superIicial gas velocity on total gas holdup and circulation time were studied in a laboratory scale
    airliIt membrane bioreactor at diIIerent gas Ilow rates. The gas phase was dispersed in the batch aqueous phase. Two baIIle
    plates divided the bioreactor into one riser zone and two down-comer zones. A Ilat sheet membrane module made oI
    Chlorinated polyethylene (KUBOTA Co. Ltd) was used in this study.
    Experiments were carried out at diIIerent gas superIicial velocity in the range oI 0.0008-0.0065 m/s at ambient temperature.
    Total gas holdup increases with increasing superIicial gas velocity. Also circulation times were measured experimentally using
    a color tracer method. It can be seen that, at the lower range oI the air rates studied, gas holdup and circulation time is a strong
    Iunction oI the superfcial gas velocity, whereas with increasing gas velocity, its eIIect on liquid circulation velocity
    diminishes.
    Also, correlations have been presented relating pertinent hydrodynamic in airliIt membrane bioreactor to superIicial gas
    velocity.
    -423-
    PF.2.35
    Ammonia removal from salty water by direct contact membrane distillation
    R. Sarbatly, D. Krishnaiah, C. K. Chiam
    Membrane Technologv Research Group (MTRG), School of Engineering and Information Technologv (SEIT), Universiti
    Malavsia Sabah (UMS), Locked Bag No. 2073, 88999 Kota Kinabalu, Sabah, Malavsia.
    rslamums.edu.my
    The Ilat sheet microporous membranes used in this study to remove the ammonia Irom salty water have been Iabricated Irom
    polyvinylidene Iluoride (PVDF), dimethylacetamide (DMAc) solvent and sodium chloride (NaCl) as the dope solution
    additive. The PVDF membranes were Iabricated by immersion precipitation oI phase inversion process in a distilled water
    coagulation bath. This study investigated the eIIect oI NaCl concentrations, namely 0, 4 and 6M, on the membranes
    perIormance in ammonia removal. The membranes have been dried in an oven beIore were characterized as well as applied in
    ammonia removal study. Direct contact membrane distillation (DCMD) was used to study the ammonia removal Irom the salty
    water oI 35ppt salinity. The experimental results showed that drying process has improved the hydrophobicity oI the PVDF
    membranes. The contact angles oI the membranes with NaCl additive, however, were reduced Irom 162
    o
    to 156
    o
    compared to
    that oI membranes without the additive. The average pore radius that eIIective to the water vapor oI the membrane, in contrast,
    has been increased with the increased oI the NaCl concentrations which were
    -4
    1.17x10
    ,
    -4
    1.33x10
    and
    -4
    1.41x10
    m,
    correspondingly. The mass transIer coeIIicient oI ammonia transIer and water vapor Ilux was higher as the membrane used
    was Iabricated Irom the higher concentration additive oI NaCl. The eIIective membrane area oI 56.40cm
    2
    that Iabricated Irom
    6M NaCl additive has achieved the highest ammonia removal eIIiciency oI 19.55 within 2 hours oI membrane distillation
    operation.
    PF.2.36
    Development of membranes for the preconcentration of Uranium(VI)
    A.M. Candela
    1
    , P. Masque
    2
    , C. Palet
    1
    1
    Centre Grup de Tecniques de Separacio en Quimica, Unitat de Quimica Analitica, Departament de Quimica, Universitat
    Autonoma de Barcelona, 08193-Bellaterra, Catalunva, Spain.
    2
    Laboratori de Radioactivitat Ambiental (LRA), Universitat Autonoma de Barcelona, Bellaterra Barcelona, Spain
    Cristina.Paletuab.es
    The objective oI our work is the pre-concentration oI Uranium(VI), Thorium(IV) and other radionucleides present in marine
    sediments and waters Ior Iuture dating oI samples. Firstly, the U(VI) is studied, which has previously been pre-concentrated
    using a variety oI techniques. |1| Based on studies oI liquid-liquid extraction oI U(VI), we have chosen an eIIective chemical
    system Ior its extraction using a kerosene solution oI di-(2-ethylhexil)phosphoric acid (D2EHPA) at 0.1M as extractant agent,
    with a 100 yield. We are now developing the pre-concentration oI this element using Polymeric Membrane (PM) systems
    prepared in our laboratories, and using Ior example Supported Liquid Membranes (SLM) or ModiIied Polymeric Membranes
    (MPM) conIigurations.
    The procedure used Ior the preparation oI all the Polymeric Membrane systems was the immersion precipitation technique. So,
    the PM were prepared at room temperature mixing a 10 or 15 polysulIone (PS) with dimethylIormamide (DMF), used as the
    casting solution. This mixture was stirred Ior 12 hours and aIter that a Iilm was properly Iormed, which was immersed in a
    bath oI water at 4C. |2,3|
    These Polymeric Membranes were impregnated with a kerosene solution oI 0.1M oI D2EHPA, used here as carrier, when
    working with SLM. In the case oI MPM, during the membrane preparation procedure, a 0.1M oI D2EHPA was added to the
    PSDMF casting mixture solution.
    Transport experiments were carried out in a permeation cell in which each membrane Iilm was clamped between two
    compartments. Volume oI Ieed and stripping phases were 200 cm3 and both aqueous solutions were stirred at 2600 rpm.|4|
    The uranium concentration in the initial Ieed phase was 0.1 mg L-1, in a nitric acid media (at pH3.6). The Iinal stripping
    solution consists oI citric acid solution 0.5M (a compromise between 0.1 and 1 M was here chosen).
    For sampling, a 0.5 mL oI Ieed and stripping solutions were periodically taken and the uranium concentration was determined
    by means oI ICP-MS measurement oI 238U(VI).
    Some results Ior membrane systems are collected in Figure 5. As seen, a 100 oI extraction by the SLM system was Iound,
    however a 60 was reached by the MPM. On the other hand, the obtained recovery has been proven quite low. Now, Iurther
    research is being Iocused to Iind better recovery solutions Ior the uranium case.
    -424-
    With these results we can conclude that using D2EHPA as carrier in the corresponding membrane systems, it has contributed
    to the transport de Uranium(VI), with a high yield in the extraction step, specially Ior SLM over MPM, even a 60 oI
    Uranium(VI) extraction is also considered good. On the other hand, the recovery oI Uranium(VI) Irom such membrane
    systems, is really low, so we are now searching to Iind better recovery aqueous systems. In this sense, the use oI modiIiers
    even in the membrane or the stripping phase is being evaluated.
    |1| Prasada, Rao., Metilda P and Mary Gladis J. Talanta 68 (2006).
    |2| Gumi, Tania.,Minguillon, Cristina; Palet, Cristina. Polymer,46 (2005).
    |3| Muoz, Maria., Oleinikova, Maria; Valiente, Manuel, Patente Inscription 200,000,536 (2000).
    |4| Gumi, T., Valiente, Manuel.,Palet, C. Journal oI Membrane Science 256 (2005) 150157.
    PF.2.37
    Studies on demulsification of linseed oil/water emulsion by PVDF membrane
    L. Li, L. Ding, J.L. Lanoiselle, Z. Tu, D. Clausse
    Unite Transformations Integrees de la Matiere Renouvelable EA 4297, Universite de Technologie de Compiegne, 60205
    Compiegne cedex, France
    luhui.dingutc.Ir
    The separation oI oil Irom O/W (oil in water) emulsion is a main problem in many technological processes.
    This study proposed a method oI demulsiIication using rotating disk Iiltration system |1, 2| with a hydrophilic membrane oI
    polyvinylidene diIluoride (PVDF) with average pore size oI 0.15 m. The inIluences oI transmembrane pressure (TMP), shear
    rate and disk types (smooth disk and disk with 6 mm vanes) on the permeate Ilux and oil recovery have been studied. The
    results showed that the rotating disk equipped with vanes could generate larger shear rates than smooth disk. For the disk with
    vanes, the Ilux reached a plateau at a TMP oI 250 kPa Ior all the speeds below 1500 rpm, at 300 kPa Ior 2000 rpm and at 350
    kPa Ior the speeds oI 2500 and 2750 rpm. This plateau increased Irom 36.3 L h
    -1
    m
    -2
    at 500 rpm to 131.7 L h
    -1
    m
    -2
    at 2750 rpm.
    The maximum permeate Ilux (131.7 L h
    -1
    m
    -2
    ) was obtained at 2750 rpm and a TMP oI 350 kPa, which was increased 40
    compared with that oI smooth disk at the same rotation speed. The permeate Ilux J in L h
    -1
    m
    -2
    was Iound to be given by J
    0.953
    max
    0.364
    and depended on shear rates. The results oI concentration tests were shown in Fig.1. With an oil concentration oI
    1.5 in 3 L Ieed, a volume reduction ratio oI 4.55 (with 650 ml oI dead volume) was obtained in 2.85 hours. For an initial oil
    mass oI 46.52 g, 35.22 g supernatant oil was separated due to the coalescence oI oil droplets. This supernatant oil represents a
    recovery oI 76 . The recovery could be increased with more volume oI Ieed.
    L. LI has been supported by China Scholarship Council. P. Paullier is acknowledged Ior his technical assistance.
    |1| R.Bouzerar, L. Ding, M.Y. JaIIrin, Local permeate Ilux-shear-pressure relationships in a rotating disk microIiltration
    module: implications Ior global perIormance, Journal oI Membrane Science, 2000, 170, 127-141
    |2| N.Moulai-MosteIa, A.Brou, Luhui Ding, M.Y.JaIIrin. UltraIiltration d`emulsions huile- eau et de microemulsions de
    cyclohexane par un systeme a disque rotatiI. Mecanique & Industries, 2005, 2, 203-210
    -425-
    Fig.1 Variation oI permeate Ilux with time at a rotating
    speed oI 2500 rpm
    PF.2.38
    Coupling adsorption/filtration process. Application to remove metallic cation from
    wastewater
    A. Soudani
    1
    , F. Sinan
    1
    , M. Persin
    2
    , A. Larbot
    2
    1
    Laboratoire de chimie phvsique, Universite Ibn Zohr BP 8106 Cite Dakhla Agadir, Morocco
    2
    lnstitut Europeen des Membranes, 1919 Route de Mende, 34293 Montpellier, Cedex 5, France
    michel.persinuniv-montp2.Ir
    A coupling process between ultraIiltration and adsorption oI undesirable chemical species (heavy metallic cations) on inert
    vegetal solid (carpobrotus edulis) is presented. The Iiltration experiments were perIormed my means oI ceramic tubular
    support with oI ZrO
    2
    microIiltration layer (pore size 0.2m). A suspension oI grinded natural vegetal was added to the solution
    beIore Iiltration at diIIerent pH, aIter Iiltration the observed cation (Cu
    2
    , Zn
    2
    , Pb
    2
    ) rejection depends mainly on the pH oI the
    treatment because the eIIiciency oI the adsorption is controlled by the pH. The best rejection are observed when the pH is
    increasing whereas low rejection occurs in acid condition, it depends also on the metallic cation considered. Theses results are
    in agreement with the adsorption properties oI the vegetal used determined in static conditions. The experiments were
    conducted in two ways: i) Static treatment oI the metal solution in presence oI the vegetal suspension Ior 2 hours and Iiltration
    oI the suspension on microIiltration membrane. ii) Filtration oI the vegetal suspension on microIiltration membrane, rinse oI
    the membrane, Iiltration oI the metallic solution without addition oI vegetal. The best results are obtained by the Iirst way but
    interesting rejection are ore also obtained by the second which proved the Iormation oI a dynamic layer at the surIace oI the
    microIiltration membrane during the circulation oI the vegetal suspension.
    PF.2.39
    Practical applications of membrane technology for liquid radioactive waste
    processing
    D.V. Adamovich
    1
    , S.A. Dmitriev
    1
    , V.I. Panteleev
    1
    , V.M. Gelis
    2
    , V.V. Milyutin
    2
    1
    State Unitarv Enterprise of the Moscow Citv SUE MosNPO 'Radon` , 2/14 7
    th
    Rostovskv Lane, 119121 Moscow, Russia
    2
    Frumkins Institute of Phvsical Chemistrv and Electrochemistrv of the Russian Academv of Sciences, 31 Leninskv avenue
    119991 Moscow, Russia
    radon-adamovichmtu-net.ru
    During the operation oI nuclear Iuel cycle enterprises and nuclear power Iacilities vast volume oI low- and intermediate-
    level liquid radioactive waste (LRW) is generated. Processing oI the above waste constitute an integral part oI the
    radioactive material handling. Earlier the decontamination oI LRW Irom radionuclides was perIormed by means oI sorption
    techniques using both organic ion exchange resins and diIIerent types oI inorganic sorbents. The application oI membrane
    technologies Ior processing LRW seems to be more promising due to the higher selectivity, high throughput values,
    operation reliability and elevated chemical and radiation stability |1-3|.
    In this paper practical examples oI the industrial Iull-scale and pilot scale application oI membrane technologies Ior processing
    LRW oI diIIerent radionuclide and physicochemical composition are reported.
    |1| D.V. Adamovich, S.A. Dmitriev, V. I. Panteleev, Electromembrane Technology Application Experience in SUE MosNPO
    'Radon Proceedings oI Int. ConI. PERMEA 2007, SioIok, Hungary, CD-ROM, 2007
    |2| F.A. LiIanov, V. I. Panteleev, D.V. Adamovich , Development oI electromembrane technology and equipment to process
    highly saline radioactive waste Proceedings oI Int. ConI. ECWATECH 2008, Moscow, Russia, CD-ROM, 2008
    |3| D.V.Adamovich, K.N.Kulikov. Device Ior liquid radioactive waste desalination. RF Patent No. 2275337, 04/27/2006.
    -426-
    PF.2.40
    Application of liquid membranes to the chemical speciation of silver in natural
    waters
    J. A. Lopez-Lopez, M. Garcia-Vargas, C. Moreno
    Department of Analvtical Chemistrv, Facultv of Environmental and Marine Science, Universitv of Cadi:, Republica Saharaui
    s/n, 11510 Puerto Real, Espaa
    carlos.morenouca.es
    Although normally Iound at very low concentration, silver is recognized as an important pollutant oI natural waters, and may
    present serious environmental problems due to its toxicity and bioavailability |1|. Besides, this element has been identiIied as a
    selective tracer oI the anthropogenic pollution related to sewage |2|.
    The understanding oI the environmental implications oI silver pollution needs to be based on the determination oI the
    concentration oI its bioavailable Iraction, which requires the application oI speciIic separation techniques. In this work, we
    have used liquid membranes, which provide an easy and handling-Iree tool Ior sample manipulation and preconcentration, and
    may be used to estimate both the total concentration oI silver and its labile Iraction in water samples.
    Bulk liquid membranes (BLMs) have been previously used Ior heavy metals transport in natural and seawater |3|. In this case,
    a beaker-in-a-beaker type cell has been selected, where silver transport takes place Irom the source solution to the receiving
    one through an organic membrane containing triisobutylphosphine sulIide (TIBPS) dissolved in toluene.
    First, univariate optimization oI both chemical variables and hydrodynamics was perIormed Ior total silver transport, based on
    the variations oI permeability coeIIicients Ior diIIerent BLM conditions. AIterwards, the inIluence oI inorganic and organic
    ligands in the perIormance oI the membrane transport was studied by adding diIIerent concentrations oI salts and humic acids.
    Besides, the correlation between the variations observed in preconcentration yields and the concentration oI diIIerent silver
    species was studied.
    Finally, the system was applied to the selective separation oI diIIerent species oI silver in water samples.
    This work has been supported by the Spanish Ministerio de Educacion v Ciencia (CTM2007-64678/TECNO) and the
    Andalusian Conseferia de Innovacion, Ciencia v Empresa (PAI05-RNM-0117.18INPR0437).
    |1| S.N. Luoma, Y.B. Ho, G.W. Bryan, Fate, bioavailability and toxicity oI silver in estuarine environments, Mar. Pollut. Bull.,
    1995, 31, 44-54.
    |2| S.A. Saudo-Wilhelmy, A.R. Flegal, Anthropogenic silver in the southern CaliIornia Bight: A new tracer oI sewage in
    coastal waters, Environ. Sci. Technol., 1992, 26, 2147-2151.
    |3| C. Mendiguchia, M. Garcia-Vargas, C. Moreno, Screening oI dissolved heavy metals (Cu, Zn, Mn, Al, Cd, Ni, Pb) in
    seawater by a liquid-membrane-ICP-MS approach, Anal. Bioanal. Chem., 2008, 391, 773-778.
    PF.2.41
    Reverse osmosis treatment of condensate from distillery stillage concentration:
    influence of operating conditions and preliminary design
    M. Gavach, C. Fargues, C. Sagne, M. Decloux, M.L. Lameloise
    AgroParisTech, UMR 1145 GENIAl, 1 av des Olvmpiades, F-91300 Massv, France
    Reverse osmosis (RO) is an interesting process to eliminate organic solutes (carboxylic acids and alcohols) Irom distillery
    condensates beIore recycling them into the Iermentation step. This work investigates the inIluence oI transmembrane pressure,
    pH and volume reduction Iactor (VRF) on the eIIiciency oI reverse osmosis treatment oI condensate Irom distillery stillage
    concentration at pilot scale using three pre-selected membranes (CPA2 and ESPA2 Irom Hydranautics, BW30 Irom Filmtec).
    PerIormances were assessed according to permeate Ilux, solutes rejection and abatement oI Iermentation inhibition.
    Transmembrane pressure increase leads to an increase oI these three parameters with a plateau Ior rejections and abatement at
    15 bar. However, as permeate Ilux is limited to 30 L h
    -1
    m
    -2
    according to membranes manuIacturers, a maximum pressure oI
    10 bar is recommended Ior CPA2 and ESPA2 membranes and 25 bar Ior BW30 membrane. pH increase leads whatever the
    membrane to a diminution oI permeate Ilux and an increase oI carboxylic acids rejection. Nevertheless, the permeate produced
    at pH 6 proved to be less Iermentable than the permeate produced at natural pH because oI an increase in the osmotic pressure.
    The VRF increase generates a decrease oI the permeate Ilux. Although local rejections are stable, the mean rejection assessed
    -427-
    with the raw condensate (Ieed) and the mean permeate decreases. However, the Iermentation inhibition remains under 10 up
    to a VRF oI 8. BW30 membrane exhibits the highest rejections and inhibition abatement.
    On the basis oI the pilot scale results with the BW30 membrane, a preliminary design is proposed Ior an industrial plant with
    100 m
    3
    h
    -1
    oI condensate Ilow rate and the optimized parameters.
    PF.3.1
    Preparation of Ag nanoparticle coated cellulose acetate membrane for removal of
    microorganisms
    S.S. Madaeni
    1
    , T.A. Arbatan
    2
    1
    Chemical Engineering Departmnet, Ra:i Universitv, Kermanshah, Iran
    2
    Chemistrv Department, Tarbiat Moalem Universitv, Tehran, Iran
    smadaeniyahoo.com

    A novel technique Ior membrane modiIication is described. Antibacterial Ag nanoparticles were introduced into the pores oI
    0.2 m cellulose acetate commercial membrane using template method. The modiIied membrane is shown to have the ability
    to remove 100 oI the microorganisms. FAM tests were perIormed to investigate the probable presence oI previously reported
    species such as Spirochetes, Hvlemonella gracilis, Betaproteobacteria, and Actinobacteria. The Iiltered samples were
    completely Iree Irom any oI the investigated microorganisms.
    PF.3.2
    Effect of feed concentration on ion transfer using dialysis process
    Y. Mansourpanah
    1,2
    , S.S. Madaeni
    2
    1
    Department of Chemistrv, Lorestan Universitv, Khorramabad, Iran
    2
    Chemical Engineering Department, Ra:i Universitv, Kermanshah, Irans
    smadaeniyahoo.com

    Polymeric ultraIiltration (PM30, PTHK) and microIiltration (Accurel, Celgard and GVHP) membranes were employed to
    separate zinc and magnesium ions in various initial Ieed concentrations via dialysis process. The passage oI ions through the
    membrane is governed by driving Iorce i.e. the diIIerence between Ieed and strip concentration. For all membranes, low initial
    Ieed concentration causes less passage oI ions through the membrane due to lower driving Iorce. In general, increasing the Ieed
    concentration causes higher transIer. For PM30 and PTHK membranes with small pore sizes, the passage oI zinc and
    magnesium ions is high but separation oI ions is not high enough. In higher concentration, the passage oI ions is reduced.
    Other membranes (Accurel, Celgard and GVHP) with larger pore sizes exhibit lower passage oI the Zn
    2
    and Mg
    2
    ions and
    higher separation oI ions.
    -428-
    PF.3.3
    Energy efficiency of reverse osmosis associated to hydrostatic pressure plants for
    seawater desalination
    C. Charcosset, C. Falconet, M. Combe
    1
    Universite de Lvon, 43 Bd du 11 novembre 1918, 69622 Jilleurbanne cedex, France
    2
    Universite Lvon 1, 43 Bd du 11 novembre 1918, 69622 Jilleurbanne cedex, France

    3
    CNRS, UMR 5007, Laboratoire dAutomatique et de Genie des Procedes, 43 Bd du 11 novembre 1918, 69622 Jilleurbanne
    cedex, France
    4
    ESCPE-Lvon, 43 Bd du 11 novembre 1918, 69622 Jilleurbanne cedex, France
    charcossetlagep.univ-lyon1.Ir
    Renewable energies (solar and wind energies) associated to reverse osmosis (RO) are gaining renewed interest Ior brackish
    and seawater desalination |1|. Another potential source oI energy is the hydrostatic pressure at a suIIicient operative depth to
    perIorm the RO process. This article provides a comparative economical study oI these various RO plants associated to
    hydraulic pressure Ior seawater desalination: underground, undersea, and adjacent mountain |2-4|. The energy eIIiciency
    calculation is based on the energy needed Ior each pump system, the overall pumping power being the sum oI the three
    contributions: seawater, Iresh water, and brine pumping power. For each pipe, the head loss is calculated Irom the Darcy-
    Weisbach equation.
    For submarine and underground plants, the required energy is equal to 2.98 and 3.54 kWh, respectively, Ior 1 m oI produced
    Iresh water. In case oI hydrostatic pressure generated by a column oI water due to a head diIIerence between the sea level and
    an adjacent mountain, the energy required is equal to 1.4 kWh. These energy eIIiciencies compare well with the usual energy
    requirement Ior desalination, between 3 to 10 kWh Ior 1 m oI produced Iresh water. The main drawback associated to
    hydrostatic pressure plants relates to their construction and their maintenance, which are expected to be more complicated and
    costly than Ior a ground plant. Future works are highly needed and speciIic experimental projects have to be implemented Ior a
    thorough clariIication oI the technical-economical Ieatures oI these hydrostatic pressure-RO plants.
    |1| C. Charcosset, A review on membrane processes and renewable energies Ior desalination, Desalination, in press (2008 or
    2009)
    |2| Colombo D., de Gerloni M., Reali M., An energy-eIIicient submarine desalination plant, Desalination, 122 (1999) 171-176
    |3| Reali M., de Gerloni M., Sampaolo A., Submarine and under ground reverse osmosis schemes Ior energy-eIIicient
    seawater desalination, Desalination 109 (1997) 269-275
    |4| Al Kharabsheh S., An innovative reverse osmosis desalination system using hydrostatic pressure, Desalination 196 (2006)
    210-214
    PF.3.4
    Comparison of polymeric and ceramic ultrafiltration membranes for separation of
    natural organic matter from water
    M. Kabsch-Korbutowicz, A. Urbanowska
    Wroclaw Universitv of Technologv, Institute of Environment Protection Engineering, Wvbr:e:e Wvspianskiego 27,
    50-370 Wroclaw, Poland
    malgorzata.kabsch-korbutowiczpwr.wroc.pl
    Introduction: UltraIiltration membranes have been widely used Ior separation oI natural organic matter Irom water intended Ior
    human consumption. More popular are membranes made oI polymeric material, however recently ceramic membranes, are
    Irequently applied in the production oI drinking water. Ceramic membranes are increasingly being used due to their high
    resistance to mechanical, chemical and thermal stresses ensuring membranes use Ior longer period. Moreover sharp decrease in
    ceramic membrane price make inorganic membranes competitive to commonly used organic membranes.
    The objective oI the study was to investigate the inIluence oI membrane type on the perIormance oI the UF process. The
    inIluence oI membrane material and its cut-oII on the membrane transport properties and NOM removal Irom surIace water
    was analyzed.
    Experimental: Membranes and experimental set-up: Flat regenerated cellulose membranes oI 5-, 10-, 30- and 100 kDa cut-oII
    (Microdyn Nadir) were Iitted in UF Amicon 8400 cell. Total Iiltration area was 45.2 cm
    2
    . 1 channel tubular ceramic
    -429-
    membranes oI 15-, 50- and 7-channel 300 kDa MWCO were supplied by Tami. The length oI the membranes amounted to 25
    cm. This yielded a total Iiltration area oI 40 cm
    2
    Ior 15- and 50 kDa membranes and 130 cm
    2
    Ior 300 kDa one. The
    experimental device was typical cross-Ilow UF equipment. In all experiments operating pressure amounted to 0.2 MPa.
    Feed water: Experiments were carried our on surIace water Irom Odra river (Poland).
    Results: On the basis oI the results obtained it might be stated that ceramic UF membranes have comparable separation
    properties to observed Ior regenerated cellulose membranes. For 10 kDa organic membrane 62.1 , colour retention was
    observed while Ior ceramic 15 kDa membrane it amounted to 50.1. For organic membranes the increase oI membrane cut-oII
    resulted in the decrease oI NOM retention, while, surprisingly, the opposite tendency was observed when ceramic membranes
    were used. For organic membranes the increase oI membrane cut-oII Irom 5- to 100 kDa caused the decrease oI colour
    retention Irom 70.2 to 53.3 , while Ior inorganic membranes the increase oI MWCO Irom 15- to 300 kDa resulted in
    increase oI retention coeIIicient Irom 50.1 to 91.9 .
    Analyzing transport properties oI investigated membranes one can say, that Ior all membranes the increase oI MWCO resulted
    in the increase oI water permeate Ilux, but much higher Iluxes were obtained Ior polymeric membranes. For example Ior 100
    kDa cellulose membrane water Ilux equaled to 13.12 m
    3
    /m
    2
    d while Ior 300 kDa ceramic membrane it amounted to 3.0 m
    3
    /m
    2
    d.
    It should be noted that membrane Iouling was more drastic in ceramic membranes than in polymeric, when membranes oI
    similar MWCO are considered.
    Acknowledgements: The work was partly supported by Polish Ministry oI Science and Higher Education, Grant NN 523 41 63
    35 (years 2008-2010).
    PF.3.5
    Fouling of membranes during ultrafiltration of surface water
    M. Bodzek, M. Rajca, A. Platkowska
    Silesian Universitv of Technologv, Facultv of Energv and Environmental Engineering, Institute of Water and Wastewater
    Engineering, Konarskiego 18, 44-100 Gliwice, Poland,
    Michal.Bodzekpolsl.pl
    In water treatment technology, membrane processes integrated with coagulation are become increasingly popular. Systems
    with coagulation allow improving the quality oI treated water and decreasing membrane Iouling caused by impurities present
    in raw water.
    The aim oI studies was to determine intensity oI membrane Iouling during treatment oI water containing natural organic matter
    (NOM) in diIIerent conIigurations oI the process: direct UF, integrated coagulation/sedimentation/ultraIiltration and hybrid in-
    line coagulation/ultraIiltration systems. The molecular weight oI NOM was determined in order to Iind, which molecular sizes
    oI compounds are responsible Ior Iouling. The inIluence oI hydrophilicity/hydrophobicity oI NOM on UF membrane blocking
    also was investigated.
    SurIace water Irom Smieszek lake (Silesia Region, Zory, Poland) contained organic substances in the amount oI around 14
    mgTOC/dm
    3
    , was used in the studies. Membrane Iiltration was conducted in the dead end mode using stirred ultraIiltration
    system (CDS 10), and with three types oI membranes: MF membrane made Irom poliethersulIone (0.22 m) Ior the removal
    oI part oI colloidal substances (~0.22 m) Irom water, UF membranes Irom cellulose (cut - oII 10 and 30 kDa), Ior the
    determination oI the inIluence oI hydrophilicity/hydrophobicity oI NOM on membrane Iouling, and UF membrane with cut-oII
    30 kDa in the proper treatment oI water. In coagulation process aluminum sulIate was applied (pH7.0, coagulant dose 4.9 mg
    Al/dm
    3
    ). NOM Iractionation (Iraction0.22 m), using Amberlite XAD-7HP and XAD-4 resins (Rohm&Haas Company),
    allowed obtaining hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) Iractions. Molecular weight distribution oI
    NOM was determined using high perIormance size exclusion chromatography (HPSEC).
    Application oI hybrid/integrated system in surIace water treatment allowed to obtain permeate oI better quality in comparison
    with direct UF and coagulation alone. Inline coagulation/UF process decreased membrane Iouling most eIIectively and
    improved membrane yield in the largest degree. Hydrophobic NOM Iraction caused greatest decrease oI permeate Ilux, while
    hydrophilic Iraction the lowest (Fig.1). Molecular weight distribution in analyzed water showed that particles oI size ~10 kDa
    were eIIectively separated in integrated/hybrid systems (Tab. 1). Probably those particles are responsible Ior membrane
    blocking as they deposit on membrane surIace and/or inside its pores.
    -430-
    PF.3.6
    Photodegradation of phenanthrene using TiO
    2
    suspensions
    M. Djehiche, S. Menetrier, A. Petitgirard, J. Persello, M. Euvrard, P. Fievet, N. Fatin-Rouge
    Universitv of Franche-Comte, UTINAM,25030 Besanon Cedex, France
    nicolas.Iatin-rougeuniv-Icomte.Ir
    Polycyclic aromatic hydrocarbons (PAHs) are toxic compounds, widespread in natural environment. They are Irequent aquatic
    contaminants oI waters. But their solubility in water is low and they adsorb strongly onto natural colloids. In surIace water,
    PAHs concentrations vary Irom 0.1 to 830 ng/L. But, their total concentration should be lower than 100 ng/L in drinking water
    (European directive 2455/2001/CE). Phenanthrene (phen) is oIten detected as contaminant in water.
    PuriIication techniques Ior polluted waters are various, however, they have limitations in terms oI cost or metabolite toxicity.
    Although PAHs can be degraded by photolysis with UV, this process is slow and phen is among the most resistant PAHs |1|.
    Photocatalytic degradation oI pollutants assisted by TiO2 has retained much attention, because oI its adaptability to industrial
    reactor system (Molinari et al., 2002), its high eIIiciency and low toxicity. PAHs can be rapidly mineralised in presence oI
    colloidal TiO
    2
    suspended in water (Zhang et al., 2008).
    Organic matter may interact with PAHs and increase signiIicantly their solubility in water. Actually, molecules like
    cyclodextrins (CD), that present a high aIIinity Ior PAHs, are considered in cleansing operations |2|. Among these compounds,
    methyl beta-CD (MBCD) is oI special interest. But, its use in soil treatments can carry along toxic compounds in waters and
    make traditional water treatments ineIIicient.
    In this work, we have evaluated the eIIectiveness oI the TiO
    2
    -assisted photodegradation oI phen and its combination with
    continuous membrane ultraIiltration Ior water treatment.
    We present the degradation oI phen by UV irradiation oI suspended TiO
    2
    . The inIluence oI parameters such as TiO
    2
    and phen
    concentrations have been studied at pH 6. Adsorption properties oI phen onto TiO
    2
    and its degradation kinetics give a better
    understanding oI the conditions Ior its eIIicient abatement. Phen degradation occurred near the TiO
    2
    surIace, where they
    reacted with redox species produced during the semiconductor irradiation. Adsorption measurements showed that phen has a
    high aIIinity Ior the TiO
    2
    surIace. The reaction was Iirst order and about 10
    3
    Iaster than Ior direct photolysis. In presence oI
    MBCD, the photocatalytic degradation oI phen and pyrene was inhibited. Finally, the continous treatment by photocatalysis
    and ultraIiltration oI water polluted by phen is presented and modelled. The modelling allows to set boundaries in terms oI
    quality oI the treated water vs. relative Ilux.
    |1| LackhoII, M., Niessner, R. 2002. Env. Sci. Tech. 36, 5342-5347.
    |2| Molinari, R., Palmisano, L., Drioli, E., Schiavello, M. 2002. J. Memb. Sci. 206, 399-415.
    |3| Brusseau, M., Boving, T., BlanIord, W., Klingel, E., Mc Cray, J. 2004. US6787038B2.
    -431-
    Tab. 1. Distribution oI NOM molecular weight in studied samples
    Apparent
    molecular
    weight |Da|
    Percent oI Iraction ||
    Dissolved
    Iraction
    Supernatant
    Permeate
    in-line
    Permeate
    on-line
    ~10000 38.70 13.69 8.87 8.92
    10000-5000 22.99 24.15 24.31 23.96
    5000-1000 25.20 39.46 42.68 42.14
    1000 13.12 22.70 24.14 24.98
    Fig. 1. Relative permeability change during Iiltration
    oI NOM Iractions through membrane with cut-oII
    30 kDa
    PF.3.7
    A study of the effect of natural organic matter on herbicide retention by NF
    membrane
    K. V. Plakas, A. J. Karabelas
    Department of Chemical Engineering, Aristotle Universitv of Thessaloniki, and Chemical Process Engineering Research
    Institute, Centre for Research and Technologv Hellas, P.O. Box 60361, 6
    th
    km Charilaou-Thermi Road, Thermi,
    Thessaloniki, Greece
    kplakascperi.certh.gr
    The presence oI natural organic matter in surIace and ground waters (humic and Iulvic acids, polysaccharides, etc) is known to
    signiIicantly aIIect the removal oI various groups oI pesticides, like herbicides, by means oI membrane nanoIiltration. Humic
    substances (HS) are a ubiquitous component oI natural water systems that may Iunction as an auxiliary phase to alter the
    speciation and transport behavior oI pesticides present in water. ThereIore, it is oI particular interest to study the relation
    between the characteristic physico-chemical properties oI well deIined HS and oI typical herbicides, Ior improved
    understanding oI mechanisms oI HS-pesticide retention by membranes.
    In this work, well characterized HS together with selected herbicide compounds (triazines) have been used in pressure-driven
    dead-end Iiltration tests. The results oI a series oI experiments have shown that the inIluence oI HS on retention oI herbicides
    by nanoIiltration membranes is rather complicated and involves combinations oI solutemembrane and solutesolute
    interactions. In summary, the retention oI triazines depends on the type oI the humic material present in the Ieed water. In most
    cases, the combined nanoIiltration oI triazines and naturally occurring HS Iacilitates the Iormation oI complexes with triazines
    which in turn enhance their removal by membrane Iiltration. This complexation appears to be related not to the characteristic
    acidity (phenolic, carboxylic) oI the HS used, but rather to their molecular conIormation. More speciIically, a preIerential
    binding is observed between triazines and low molecular weight Iractions oI humic compounds, which results in higher
    retention values.
    The removal oI the selected triazines is improved in the presence oI calcium which tends to enhance their interaction with the
    humic substances. Moreover, herbicide retention is increased with increasing HS concentration, to a degree depending on the
    type oI HS. Additionally, triazine retention is apparently also aIIected by the interactions between the organics and the
    membrane surIace, which in turn may alter triazine retention. The results illustrate the complexity oI the triazine adsorption
    and retention mechanisms in the presence oI humic substances. In order to distinguish the eIIect oI the HS-triazines
    interactions, Irom that oI membrane HS Iouling, on triazine removal by nanoIiltration, an extensive set oI tests was recently
    completed in the cross-Ilow mode oI operation. These recent results show that membrane Iouling exerts a very strong inIluence
    on the rejection oI herbicides, Ior all thin Iilm composite nanoIiltration membranes used.
    PF.3.8
    Effect of membrane fouling and scaling on phytoestrogens removal in reverse
    osmosis and nanofiltration
    M. Bodzek, M. Dudziak
    Silesian Universitv of Technologv, Institute of Water and Wastewater Engineering, Konarskiego 18, 44100 Gliwice, Poland
    michal.bodzekpolsl.pl
    Phytoestrogens are biologically active compounds which occur in plants and may aIIect a lot oI processes in animals and
    humans. They can be Iound in water reservoirs due to sewage discharge and plant decomposition. All this implies the need to
    investigate their removal by water treatment techniques, including membrane processes.
    Membrane Iouling and scaling are common processes that accompany membrane Iiltration and are caused by the presence oI
    organic and inorganic matter in water respectively. Apart Irom a reduction in membrane eIIiciency, they also change its
    morphology and surIace loading which may aIIect the removal oI lowmolecular weight organic micropollutants.
    In the study, deionized water that contained selected phytoestrogenic compounds (biochanin A, daidzein, genistein and
    coumestrol 5 g/dm3) was Iiltered through a new membrane and a one contaminated with organic and inorganic matter Ior
    comparison. Fouling was brought about by Iiltering deionized water with an addition oI 30 mg/dm3 oI humic acid (Aldrich)
    while scaling was caused by Iiltering a mixture oI salts (20 mM NaCl, 1 mM NaHCO3 and 1 mM CaCl2) until 50 oI the Ieed
    was recovered. The tests were carried out on two Osmonics membranes, DS3SE Ior reverse osmosis (RO) and DS5DK
    Ior nanoIiltration (NF). The membrane process was conducted in the deadend mode under a pressure oI 2.0 MPa.
    -432-
    The removal oI biochanin A, daidzein, genistein and coumestrol determined Ior the deionized water containing standards was
    97, 69, 92 and 86 Ior RO respectively while Ior NF it was 86, 68, 71 and 72 respectively (new membrane). During
    Iiltration oI organic and inorganic matter, the relative permeability oI the membranes () was much lower than 1, which
    proved the occurrence oI Iouling and scaling (Table 1). The retention oI the compounds Iound Ior the contaminated membrane
    was higher than that Ior the new one. This was observed Ior both Iouling and scaling.
    Table 1.Change in retention oI the phytoestrogens due to presence oI Iouling or scaling
    Compound
    Membrane
    Reverse osmosis (DS3SE) NanoIiltration (DS5DK)
    Mechanism oI blocking
    Fouling Scaling Fouling Scaling
    Bichanin (BioA) 0 1 14 13
    Daidzein (Daid) 24 27 26 14
    Genistein (Gen) 4 4 29 2
    Coumestrol (Coum) 3 8 17 4
    Parameter
    Relative permeability oI the membrane u
    1
    , 0.88 0.63 0.71 0.84
    1
    is the ratio oI volumetric permeate Ilux to the Ilux oI distilled water
    PF.3.9
    Structural analysis of polyamide 66 membranes prepared by phase inversion in
    ternary system water/cloridric acid/poliamide
    M. Zeni , J. Duarte, P. Poletto
    Science Technologv Center, Caxias do Sul- Universitv, 95.070-970 Caxias do Sul- Bra:il
    mzandraducs.br
    Structural characteristics in polyamide 6.6 membranes were studied to describe the eIIects oI morphologies Iormed by
    diIIusion induced phase separation process when prepared by phase inversion in the water/cloridric acid/polyamide 6.6 ternary
    system|1|. Polymer solutions oI 10, 15 and 20 wt oI polyamide 6.6 (PA 6.6) in cloridric acid (HCl 37) and poly(vinyl
    pyrrolidone) (PVP 1) used as porous Iorming agent were casting at room temperature on glass plate with a uniIorm thickness
    oI 40m. AIter casting, the glass plate was immersed in a coagulation bath containing destilled water at 25C. AIter polymer
    coagulation, the prepared membranes were transIerred to a second bath containing Iresh water and dried at room temperature.
    The morphology oI membranes was studied by scanning electron microscopy (SEM Shimadzu SS 550). The samples were
    Iractured in liquid N
    2
    and coated with gold. Binodal and spinodal curves oI the ternary phase diagram and the thermodynamic
    evaluation oI a membrane Iorming system were constructed by Flory-Huggins theory. The magnitude and concentration
    dependency oI the interaction parameters nonsolvent/solvent, solvent/polymer and nonsolvent/polymer have a large eIIect on
    the binodal, spinodal and critical point positions oI a phase diagram|2|. The cloud point curve was determined by usual
    titration method . Several conclusions would be described with the ternary system water/HCl/poliamida 6.6 because the water
    present in the cloridric acid. The membranes prepared by polyamide 6.6, HCl 37 and immersed in water bath have
    morphologies that can be described by precipitation courses. In contrast the membranes have a skinless, microporous
    character, change in crystallinity and oI a cellular structure|3| . In the SEM photo micrographs oI cross sections are showed
    the dopes .
    |1| M.Zeni, R.Riveros, J.F. Souza, K.Mello, C. Meirelles, G.F. Rodrigues, Morphologic analysis oI porous polyamide 6,6
    membranes prepared by phase inversion, Desalination, (2008), 221, 294-297.
    |2| I.M. Wienk, R.M. Boom, M.A.M. Beerlage, A.M.W. Bulte, C.A. Smolders, H. Strathmann, Recent advances in the
    Iormation oI phase inversion membranes made Irom amorphous or semi-crystalline polymers, J. Membrane Sci.,(1996), 113,
    361-371.
    |3| C-H. Shih, C.C. Gryte, L-P.Cheng,Morphology oI Membranes Formed by the Isothermal Precipitation oI Polyamide
    Solutions Irom Water/Formic Acid Systems, J. Appl. Polymer Sci., (2005), 96, 944-960
    -433-
    PF.3.10
    Comparison of behaviors of three bacteriophages MS2, Q and T4, during the
    ultrafiltration membrane process
    G. Pierre
    1
    , A. Furiga
    2
    , M. Berge
    2
    , C. Roques
    2
    , P. Aimar
    1
    , C. Causserand
    l
    1
    Laboratoire de Genie Chimique (UMR 5503), Universite de Toulouse, Universite Paul Sabatier, 31062 Toulouse cedex 09,
    France
    2
    Equipe Adhesion Bacterienne et Formation de Biofilms (EA 3036 - IFR 31), Universite Paul Sabatier, Toulouse, France
    causserachimie.ups-tlse.Ir
    The development oI a virus challenge test is a prerequisite to assess the integrity oI membrane processes used in drinking water
    production and waste waters treatment (Madaeni, Fane, and Grohmann). Bacteriophages are currently used as a surrogate to
    evaluate pathogenic virus removal eIIiciency oI Iiltration membrane during water treatment (Langlet et al.;HU.J.Y).
    In this study, we propose to present and discuss a series oI experiments that has been carried out to deIine the log removal
    value (LRV) oI diIIerent viruses using one ultraIiltration hollow Iiber membrane. The selected membrane is made oI cellulose
    acetate, with the conIiguration in/out. The viruses selected are bacteriophages MS2, Q-beta and T4 chosen by membrane
    manuIacturers to challenge membranes (Shirasaki et al.).
    Experiments were conducted over 2 hours with virgin membrane in cross Ilow Iiltration conditions. A Ieed suspension oI
    viruses at a concentration 10
    8
    PFU/mL was used in various media (PBS, Milli-Q water). The suspension was sampled in
    permeate and retentate and a counting carried out in order to determine the virus concentrations using two diIIerent methods:
    by plaque Iorming unit (PFU) method, which can reveal only inIectious viruses and by real-time RT-PCR method which
    detects the total (inIectious inactivated) number oI viruses regardless oI their inIectivity. The particle size and electrophoretic
    mobility oI these diIIerent bacteriophages are also studied in various media.
    This study provides guidelines to propose a protocol allowing the determination oI the "true" virus retention capacity oI
    membranes in 'worst conditions, namely here in absence oI Iouling. A comparison oI the mechanisms oI transmission oI
    micro-organisms in membrane processes is then proposed to determine the better surrogate to characterize membrane virus
    removal propensity in worst possible conditions.
    HU.J.Y, et al. "Removal oI MS2 bacteriophage using membrane technologies." Water Science and Technology (2003).
    Langlet, J, et al. "EIIiciency oI MS2 phage and Q|beta| phage removal by membrane Iiltration in water treatment:
    Applicability oI real-time RT-PCR method." Journal oI Membrane Science 326.1 (2009): 111-16.
    Madaeni, S. S., et al. "Virus removal Irom water and wastewater using membranes." Journal oI Membrane Science 102 (1995):
    65-75.
    Shirasaki, N., et al. "Comparison oI removal perIormance oI two surrogates Ior pathogenic waterborne viruses, bacteriophage
    Q|beta| and MS2, in a coagulation-ceramic microIiltration system." Journal oI Membrane Science In Press, Corrected ProoI.
    -434-
    PF.3.11
    Preparation and characterization of anion-exchange membranes with semi-
    interpenetrating network structure of poly(vinyl alcohol) and polycation
    M. Nishimura, S. Kuwada, E. Shimizu, M. Higa
    Graduate School of Science and Engineering, Yamaguchi Universitv, 2-16-1 Tokiwadai, Ube-citv, Yamaguchi 755-8611,
    Japan
    mhigayamaguchi-u.ac.jp
    Ion-exchange membranes have been applied to various industrial Iields
    |1-4|. Hydrophobic polymers such as a copolymer oI styrene and
    divinylbenzene and perIluorocarbon polymers have been used as their
    base materials. Recently, there have been many reports on preparing
    ion-exchange membranes using water-soluble polymers as a base
    material. Poly (vinyl alcohol) (PVA) has been one oI the most popular
    polymers as a membrane matrix. Because the water content oI PVA
    based membranes, which plays an important role in permselectivity in
    an ion-exchange membrane, can be easily controlled by annealing as-
    cast membranes and/or cross-linking them by using cross-linking
    agents such as glutaraldehyde (GA) |5|. In this work, anion exchange
    membranes with a semi-interpenetrating network structure were
    prepared by blending PVA and a polycation, poly(diallyl dimethyl
    ammonium chloride). The membranes obtained were physically cross-
    linked by annealing them at 160
    o
    C Ior 30 min and chemically cross-
    linked by reaction with glutaraldehyde aqueous solutions. The ion
    permselectivity between anions were measured using a Donnan
    dialysis system as shown in Figure 1. Figure 2 shows an example oI
    time-concentration curves oI Cl
    -
    ions and SO
    4
    2-
    ions through the anion
    exchange membranes. The concentration oI Cl
    -
    ions in Cell L increases
    with increasing time. On the other hand, the concentration oI SO
    4
    2-
    ions decreases with increasing time. This result indicates that the
    membranes in this study will be useIul Ior removing harmIul ions such
    as NO
    3
    -
    ions and F
    -
    ions Irom groundwater.
    (1) P. J. Moon, S. J. Parulekar and S. P. Tsai, J. Membr. Sci., 1998,
    141, 75.
    (2) T. Xu and W. Yang, J. Membr. Sci., 2001, 183, 193.
    (3) L. Melnik, O. Vysotskaja and B. Kornilovich, Desalination, 1999,
    124, 125.
    (4) K. Sato, J. Membr. Sci. 2002, 196, 211.
    (5) M. Nishimura, M. Higa, K. Akamine, S. Masudaya, Desalination,
    2008, 3, 165.
    PF.3.12
    Performance of ultrafiltration plants in France, comparison with ultrafiltration
    plants for sea water RO pretreatment application
    A. Leroux, J. Banham, E. Chaumien, L. Boutarin
    Hvdranautics A Nitto Denko Companv, 401 Jones Road, Oceanside, CA 92058, United States
    www.membranes.com
    alerouxhydranautics.nl
    The demand Ior high quality municipal potable water is booming all over the world, especially in France where there is an
    additional requirement Ior virus reduction that can be satisIied with the use oI ultraIiltration membranes but also in Middle
    -435-
    Magnetic
    Stirrer
    Magnetic
    Stirrer
    0.5M NaCl
    1.0 mM Na
    2
    SO
    4
    1.0 mM Na
    2
    SO
    4
    100ml
    400ml
    Cell L Cell R
    Membrane
    Figure 1: Apparatus Ior permeation experiment.
    The eIIective membrane area oI the cell is
    2.54cm
    2
    .
    0.0
    2.0
    4.0
    6.0
    8.0
    0 500 1000 1500
    time / min
    C
    C
    I

    /

    m

    m
    o
    I

    d
    m
    -
    3
    0.0
    0.2
    0.4
    0.6
    0.8
    1.0
    1.2
    C
    S
    O
    4

    /

    m

    m
    o
    I

    d
    m
    -
    3
    Figure 2: Time-concentration curves oI SO
    4
    2-
    and
    Cl
    -
    ions in the low-concentration side. Samples:
    open circles, SO
    4
    2-
    ; closed circles, Cl
    -
    .
    East where the demand oI water is continuously growing . In France many oI these advanced treatment plants have been
    awarded, and are using capillary UF membrane technology, such as the HYDRAcap UF membrane as part oI the treatment
    process. Plant output Irom these installations range Irom 1000 m
    3
    /d up to 150,000 m
    3
    /d and treat diIIerent types oI Ieed waters
    (mainly surIace waters and ground waters) with typically high turbidity values. Each oI these plants requires an appropriate
    pre-treatment process to reduce the solids loading on the UF membrane, which results in a reduced the number oI membranes
    and an optimized water recovery by the ultraIiltration plant.
    Capillary ultraIiltration is usually used a Iinal treatment step to successIully remove viruses, bacteria and the Iinest particles.
    The removal rating depends upon the pore size oI the active layer oI the membrane, which Ior HYDRAcap UF, is
    approximately 0.02 microns. In the case oI sea water RO pretreatment, the ultraIiltration membranes are not used as a Iinal
    step. The objective oI the treatment is to provide high quality water to allow high perIormance on sea water RO system.
    This paper will present the current and Iuture trend regarding the use oI ultraIiltration in treatment plants in France. In
    particular, detailed design and commissioning data Ior two diIIerent plants will be compared and contrasted. One site is a
    large-scale plant with under operation Ior potable water use. The high quality oI Ieed water enables the system to run at high
    Iluxes. Secondly, a small scale plant will be described; this plant can run at high Ilux and is subject to high concentrations oI
    iron in Ieed water, which requires Irequent cleanings at low pH. In both cases, UF perIormance data, including Ilux,
    transmembrane pressure, backIlush trends and Iiber integrity will be presented in order to have a clear picture oI the potential
    oI the plant.
    This paper will also present a comparative between the application we have in France and ultraIiltration plant in Middle East
    used as sea water RO pretreatment. In particular, the Ieed and raw water quality, the permeate quality and the operation
    conditions will be compared and contrasted.
    PF.3.13
    Effective removal of virus by ceramic microfiltration with in-line coagulation
    pretreatment
    T. Matsushita, N. Shirasaki, M. Kobuke, Y. Matsui, K. Ohno
    Graduate School of Engineering, Hokkaido Universitv, N13W8, Sapporo 060-8628, Japan
    taku-meng.hokudai.ac.jp
    Background
    Ceramic membranes have attracted attention in the Iield oI drinking water treatment in Japan because they are less breakable
    than membranes made oI other materials. However, in general, ceramic membranes are microIiltration (MF) devices, so their
    pore sizes are not small enough to exclude particles with diameters less than tens oI nanometers. Included among such small
    particles are some oI the pathogenic waterborne viruses that draw attention in drinking water treatment which are
    approximately 20 nm in diameter. ThereIore, these viruses cannot be excluded by ceramic membranes alone. In order to
    compensate Ior this disadvantage, coagulation pretreatment has been introduced in combination with ceramic MF.
    Two applications are available Ior actual treatment plants to employ the ceramic MF in combination with coagulation
    pretreatment: (1) installing MF to the existing conventional coagulation-sedimentation process, and (2) employing MF with an
    in-line coagulation process. In the present study, we evaluated the removal perIormance oI virus in these 2 systems, and then
    compared them.
    Materials and methods
    MF with conventional coagulation process: River water spiked with virus (Q or MS2) was introduced to a rapid mixing tank
    (G value, 200 s
    -1
    ; detention time, 5 min) where polyaluminum chloride (PACl) was injected at 1.08 mg-Al/L. A part oI the
    water was then pumped into the ceramic MF module (pore size, 0.1 m) at a constant Ilow rate (83 Lm
    -2
    h
    -1
    ) in dead-end mode.
    The other part was Iurther treated in a slow mixing tank (G value, 20 s
    -1
    ; detention time, 25 min) and in a sedimentation tank
    (detention time, 20 min), and then Ied into the ceramic MF module in the same manner. Filtration was perIormed Ior 4 h
    without backwashing. Virus concentrations in the raw water and in the MF permeate were measured by both PFU and PCR
    method.
    MF with in-line coagulation: River water spiked with the virus was Ied into the in-line coagulation-MF system at a constant
    Ilow rate by a peristaltic pump. PACl was injected to the water at 1.08 mg-Al/L, and then mixed well with an in-line static
    mixer (detention time, 1.8 s or 5 min).The water was Ied into the ceramic MF module at 83 Lm
    -2
    h
    -1
    in dead-end mode.
    Filtration was perIormed Ior 4 h without backwashing.
    Results and discussion
    MF with conventional coagulation process successIully removed the virus: approximately 8-log reduction in inIectious virus
    concentration (evaluated by PFU method) was achieved when the water was introduced to the MF both aIter rapid mixing and
    sedimentation process. This means that the size oI the aluminum Iloc which had enmeshed virus particles exceeded the pore
    size oI the MF even in the absence oI the sedimentation process. In contrast, when the in-line coagulation-MF system was
    operated with 1.8 s oI detention time, inIectious virus removal was much smaller than those in the MF with conventional
    -436-
    coagulation process: approximately 5-log. When the detention time was increased up to 5 min, however, the in-line
    coagulation-MF system could eIIectively remove the virus: the removal ratio was approximately 8-log. Removal oI total virus
    particles (evaluated by PCR method) was also in the similar trend. This means that the conventional coagulation-sedimentation
    process, which requires large Iootprint and energy, is not required as the pretreatment Ior the MF in terms oI virus removal.
    Installing the in-line coagulation with appropriate detention time as a pretreatment is enough Ior the MF process, which could
    save the space and energy.
    PF.3.14
    Modification of RO membranes via graft polymerization of methacrylate monomers
    that possess quaternary- ammonium groups
    M. V. Brami, S. BelIer, R. Kasher
    Department of Desalination & Water Treatment, Zuckerberg Institute for Water Research, Blaustein Institutes for Desert
    Research, Ben-Gurion Universitv of the Negev, Midreshet Ben-Gurion 84990, Israel
    bramimbgu.ac.il
    Organic Iouling and bio-Iouling are major problems in reverse osmosis and nanoIiltration processes, mainly due to the Iact that
    there is no eIIicient method to eliminate them that is suitable when using TFC membranes. Earlier works showed an inverse
    relation between hydrophilicity oI the membrane surIace and the adhesion oI organic materials and bioIilm Iormation |1|. Here
    we present the use oI redox-initiated graIt polymerization Ior surIace modiIication oI RO-membranes using methacrylate
    monomers that contain quaternary ammonium groups. The polymerization reaction is carried out in aqueous solutions at room
    temperature, as was previously described |2|. A quaternary ammonium group is known to have antimicrobial properties;
    hence, it could be used as a potential agent against bioIouling. In this study we used the monomers |2-Methacryloyloxyethyl|
    trimethylammonium (MOETMA), N-(3-SulIopropyl)-N-(Methacryloyloxyethyl)-N,N-dimethylammonium betaine (SPE),
    which was used previously by M. Ulbricht and coworkers in modiIication oI UF membranes |3|, and 2-
    methacryloylphosphorylcholine (MPC). MPC and SPE are attractive candidates Ior graIt-polymerization oI RO-membranes
    due to their zero-net charge and the presence oI quaternary ammonium group. The chemical modiIication was evaluated by
    attenuated total reIlection (ATR)-FTIR spectroscopy, by water-drop contact angle and by x-ray photoelectron spectroscopy.
    We have Iound that increasing the MOETMA concentration leads to a larger degree oI graIting in monomer range oI 0.1-1.0 M
    as evaluated by ATR-FTIR, and to the increasing hydrophilicity oI the membrane surIace (contact angle). RO-Membrane
    permeability tests oI membranes modiIied with MOETMA showed a decrease in water permeability as the monomer
    concentration increases. GraIt polymerization oI RO membranes by SPE was perIormed, and characterized successIully. MPC
    was synthesized based on a previously-published procedure |4|. This study may be used Ior development oI novel membranes
    that are less susceptible to organic- and bio-Iouling by using redox initiated graIt-polymerization techniques.
    |1| S. BelIer, J. Gilron, N. Daltrophe, Y. Oren, Comparative Study oI bioIouling oI NF modiIied membrane at SHAFDAN,
    Desalination, 2005, 184, 1321.
    |2| S. BelIer, Y. Purinson, R. Fainshtein, Y. Radchenko, O. Kedem, SurIace modiIication oI commercial composite polyamide
    reverse osmosis membranes, Journal oI Membrane Science, 1998, 139, 175-181.
    |3| H. Susanto, M. Ulbricht, PhotograIted Thin Polymer Hydrogel Layers on PES UltraIiltration
    Membranes: Characterization, Stability, and InIluence on Separation PerIormance, Langmuir, 2007, 23, 7818-7830.
    |4| K. Ishihara, T. Ueda, N. Nakabayashi, Preparation oI phospholipid polymers and their properties as polymer hydrogel
    membranes, Polymer Journal, 1990, 22(5), 355-360.
    -437-
    PF.3.15
    Renewable energy powered membrane systems: potential for inorganics removal
    from groundwaters
    L. A. Richards
    1
    , B. S. Richards
    1
    , A. I. SchIer
    2
    1
    School of Engineering and Phvsical Sciences, Heriot-Watt Universitv, Edinburgh, EH14 4AS, United Kingdom
    2
    School of Engineering, Universitv of Edinburgh, Edinburgh, EH9 3JL, United Kingdom.
    Lar7hw.ac.uk
    A photovoltaic powered hybrid membrane desalination system (PV-membrane) utilizing ultraIiltration and reverse
    osmosis/nanoIiltration (RO/NF) has been developed and tested with a number oI natural groundwaters |1|. The objective oI
    this study is to compare NF/RO retention oI inorganic contaminants in six remote Australian groundwaters using the PV-
    membrane system.
    Experiments were conducted to evaluate the speciIic impact oI solar radiation variation on inorganic retention. As solar
    radiation changes throughout the solar day, energy input to the pump also changes, leading to corresponding variations in both
    pressure and Ilow (and thus Ilux and retention). The relationship between pressure and retention is complex and involves
    interactions with regard to the hydrated size oI the contaminants, convective Iorces, and surIace Iorces within the membrane
    pore |2|. Additionally, it has been suggested that some ions may separate Irom their hydrated layer under certain conditions,
    thus passing through the membrane unretained |3|.
    The results in this study show that retention oI inorganic contaminants at each location typically increased with higher levels oI
    solar radiation, which is expected when convection/diIIusion play dominate retention. Discussion includes how removal
    mechanisms may be impacted by Iluctuating energy as well as saIe operating windows Ior reliable inorganic contaminant
    removal. Flux varied signiIicantly between groundwaters, as expected due to the diIIerent compositions, which can have
    implications on system cleaning requirements at the diIIerent locations. SpeciIic energy consumption was inversely
    proportional to Ilux at each location. The results obtained in this study highlight interesting variations in perIormance with
    both groundwater quality and solar radiation. Despite these variations, results indicate that the PV-membrane system reliably
    treats a variety oI groundwaters under diIIerent conditions.
    |1| SchIer, A. I.; Broeckmann, A.; Richards, B. S. Renewable Energy Powered Membrane Technology. 1. Development and
    Characterization oI a Photovoltaic Hybrid Membrane System. Environ. Sci. Technol. 2007, 41, 998-1003.
    |2| Paugam, L.; Taha, S.; Dorange, G.; Jaouen, P.; Quemeneur, F. Mechanism oI nitrate transIer in nanoIiltration depending on
    pressure, pH, concentration and medium concentration. J. Membr. Sci. 2004, 231, 37-46.
    |3| Tansel, B.; Sager, J.; Rector, T.; Garland, J.; Strayer, R.; LanIang, L.; Roberts, M.; Hummerick, M.; Bauer, J. SigniIicance
    oI hydrated radius and hydration shells on ionic permeability during nanoIiltration in dead end and cross Ilow modes. Sep.
    Purif. Technol. 2006, 51, 40-47.
    Spanish Science and Technology Ministry (CYCIT project MAT2007/65065) is acknowledged Ior Iinancial support.
    PF.4.1
    Development of hexane-resistant membranes for solvent recovery from sunflower oil/
    hexane mixture
    P. Martino
    1
    , C. Pagliero
    1
    , N. Ochoa
    2
    , J. Marchese
    2
    1
    Departamento de Tecnologia Quimica, Universidad Nacional de Rio Cuarto, CONICET, Ruta 36, Km 601, 5800 Rio Cuarto,
    Cordoba, Argentina
    2
    INFAP- CONICET UNSL, Chacabuco v Pedernera, 5700 San Luis, Argentina
    cpaglieroing.unrc.edu.ar
    Vegetable oil extraction, as perIormed by the oilseed crushing industry today, involves a solvent extraction step with an
    organic solvent, normally commercial. AIter this step, the vegetable oil/hexane mixture ('miscella) must be treated to
    separate its components by means oI a complex distillation procedure. Membrane separation technology could result in a
    better option provided that solvent resistant membranes with good permeation properties were available to replace the actual
    technology.
    -438-
    In this work, composite polymeric membranes prepared in our laboratory and a MPF-50 (polyimide/PDMS) commercial
    available membrane provide by Koch were used to treat a crude sunIlower oil-hexane mixture with dead end Iiltration cell.
    The synthesized composite membranes were made Irom PVDF as asymmetric support layer and silicone or cellulose acetate as
    coating layer. The permeation and separation characteristics oI these membranes at diIIerent Ieed miscella concentrations,
    temperature and trans-membrane pressures were studied. The results showed interesting stability and oil retention
    characteristics (R 43) Ior the synthesized membrane compared to the commercial one. The experimental transport data
    was interpreted using pore Ilow models.
    PF.4.2
    Film-forming cellulose acetate graft copolymers with nano-structured architectures:
    Application to the purification of bio-fuels by pervaporation
    A. Jonquieres
    1
    , M. Billy
    1
    , A. Ranzani Da Costa
    1
    , P. Lochon
    1
    , R. Clement
    1
    , M. Dresch
    2
    , S. Etienne
    3
    1
    Laboratoire de Chimie Phvsique Macromoleculaire, UMR CNRS-INPL 7568,
    Nancv Universite, ENSIC, 1 rue Grandville, BP 20451, 54 001 Nancv Cedex, France
    2
    ADEME, 20 avenue du Gresille, BP 90406, 49 004 Angers Cedex, France.
    3
    Laboratoire de Phvsique des Materiaux, UMR CNRS 7556, Ecole Nationale Superieure des Mines, Nancv Universite, Parc de
    Saurupt 54 042, Nancv
    Anne.Jonquieresensic.inpl-nancy.Ir
    Cellulose acetate (CA) is a very good Iilm-Iorming material Ior aqueous membrane applications. It has also been reported Ior
    the challenging separation oI purely organic mixtures by pervaporation with outstanding selectivity Ior the puriIication oI the
    ethyl-tert-butyl ether (ETBE) bio-Iuel. Nevertheless, its Ilux was much too low to allow any Iurther development Ior this
    application. Following a Iew works having shown the true potential oI CA plasticizing Ior this separation |1, 2|, CA-g-
    poly(methyl diethylene glycol methacrylate) copolymers were obtained by Atom TransIer Radical Polymerization (ATRP) by
    graIting Irom brominated macroinitiators. The copolymerization scaling-up up to ca. 5 g oI copolymer samples was
    successIully achieved and two Iamilies oI graIt copolymers with nano-structured architectures were eventually obtained. The
    graIting Irom a Iirst macroinitiator containing 6 initiator groups Ior 100 glucosidic cycles led to a Iirst Iamily oI graIt
    copolymers with a high number oI poly(MDEGMA) short graIts. A second macroinitiator with 1 initiator group Ior 100
    glucosidic cycles then enabled to obtain a second Iamily oI copolymers with almost the same graIt weight Iractions but with a
    low number oI long graIts.
    This paper Iocuses on the sorption and
    pervaporation properties oI both Iamilies
    oI graIt copolymers Ior the puriIication
    oI the ETBE bio-Iuel. As an example,
    the striking results displayed in Figure 1
    showed that the copolymer properties
    did not depend only upon their highly
    permeable graIt content but that their
    nano-structured architecture also played
    a key role in their separation behaviour.
    0.85
    0.87
    0.89
    0.91
    0.93
    0.95
    0.97
    0.99
    0.2 0.3 0.4 0.5
    CopoIymer graft weight fraction
    P
    e
    r
    v
    a
    p
    o
    r
    a
    t
    e

    e
    t
    h
    a
    n
    o
    I

    w
    e
    i
    g
    h
    t

    f
    r
    a
    c
    t
    i
    o
    n
    CopoIymers with short grafts
    CopoIymers with Iong grafts
    Figure 1. Example oI the pervaporate ethanol content Ior the separation oI the
    azeotropic mixture EtOH/ETBE (20/80 w/w ) with both Iamilies oI cellulose
    acetate graIt copolymers at 30C.
    |1| Q.-T. Nguyen, C. Leger, P. Billard, and P. Lochon, Polymers Ior Advanced Technologies, 8 (1997) 487.
    |2| Q.-T. Nguyen, R. Clement, I. Noezar, and P. Lochon, Separation and PuriIication Technology, 13 (1998) 237.
    -439-
    PF.4.3
    PDMS membranes applicable in both nanofiltration and pervaporation
    A. Dobrak
    1,2
    , B. Van der Bruggen
    1
    , I. Vankelecom
    2

    1
    Applied Phvsical Chemistrv and Environmental Technologv Section, Department of Chemical Engineering, K.U.Leuven, W.
    de Crovlaan 46, B-3001 Leuven, Belgium
    2
    Centre for Surface Chemistrv and Catalvsis, Department of Microbial and Molecular Svstems, K.U.Leuven, Kasteelpark
    Arenberg 23, B-3001 Leuven, Belgium.
    Ivo.Vankelecombiw.kuleuven.be
    Membranes applicable Ior both nanoIiltration and pervaporation were prepared by prepolymerization oI PDMS
    (polydimethylsiloxane) at 60
    0
    C Ior 0.5 h, Iollowed by coating oI the 15 PI (polyimide) support under an angle oI 60
    0
    to
    allow the polymer solution to Ilow down over the support.
    The highest solvent Iluxes (comparing methanol, ethanol, n-propanol, i-propanol, sec-butanol, hexanol, toluene/IPA mixtures)
    through PDMS membranes cast Irom 10 wt solutions were obtained Ior toluene/IPA mixtures, and increased with toluene
    concentration (19 kg m
    -2
    h
    -1
    at 60 vol. toluene; 4 kg m
    -2
    h
    -1
    at 20 vol toluene in isopropanol). This can be related to the
    high swelling degree oI PDMS (0.48 and 1.1 cm
    3
    /g, respectively). From the series oI solvents with less swelling, the highest
    Ilux was obtained Ior sec-butanol (2 kg m
    -2
    h
    -1
    ), which also can be related to the relatively high swelling. Fluxes oI ethanol and
    n-propanol were comparable (~ 1 kg m
    -2
    h
    -1
    ). The lowest Iluxes were obtained Ior methanol and hexanol (0.3 kg m
    -2
    h
    -1
    ). For
    methanol, the lowest swelling degree was observed, which explains the obtained result. On the other hand, the low hexanol
    Ilux could be linked to its high viscosity.
    Bengal rose (a negatively charged dye) and bromothymol blue (neutral dye) in the mixtures with isopropanol and n-propanol
    were used to measure retentions. The highest bengal rose retention (99 ) was Iound Ior the PDMS membrane prepared Irom
    a 10 wt coating solutions at 20 bar. The PDMS-membranes prepared Irom more dilute solutions (7.5 wt, 5 wt) gave
    lower retentions (86 and 76 , respectively). In case oI bromothymol blue, a slightly higher retention was obtained in IPA
    (93 ) than in n-propanol (89 ).
    A partially reversible PDMS membrane compaction was observed Ior the solvents used. Due to the applied pressure, the
    relatively swollen dense PDMS top-layer is being slowly squeezed till equilibrium. This creates a higher resistance Ior the
    migrating compounds. ThereIore, PDMS can be considered as a 'soaked sponge. Concentration polarization and membrane
    Iouling can be excluded as a side eIIect during Iiltrations with examined Ieeds.
    PDMS membranes cast Irom solutions with various polymer concentrations were also used in pervaporation experiments. 15
    unIilled PDMS-membrane coated on PI-support showed a lower Ilux but higher selectivity (4.3 and 3.8, respectively) than the
    one coated on PAN-support. Permeate Ilux decreased with the increase oI the polymer concentration in the top layer. For the
    commercial Pervap 1060 membrane, a higher Ilux but lower selectivity was obtained, which could be explained by a more
    hydrophilic PDMS material obtained by applying a diIIerent membrane preparation technique.
    PF.4.4
    Influence of organic solvent properties on nanofiltration membrane separation of
    active pharmaceutical ingredient (API)
    F.W. Lim
    1
    , M. Makowski
    1
    , D. Ormerod
    2
    , A. Horvath
    2
    , A.G. Livingston
    1,3
    , A.T. Boam
    1

    1
    Membrane Extraction Technologv Ltd., Unit 25 Talina Centre, Baglevs Lane, London SW6 2BW, UK.
    2
    Janssen Pharmaceutica NJ, Turnhoutseweg 30, B-2340 Beerse, Belgium.
    3
    Department of Chemical Engineering and Chemical Technologv, Imperial College London, Exhibition Road, London SW7
    2AZ, UK.
    atbmembrane-extraction-technology.com
    The use oI organic solvents is ubiquitous in the synthesis steps oI Active Pharmaceutical Ingredients (APIs) production in the
    pharmaceutical industry. The ability to carry out selective separations with organic solvent-containing solutions using
    nanoIiltration membranes would enable the recycling oI solvents and the puriIication oI APIs by removal oI excess
    reagents/by-products/impurities |1|. The use oI these Organic Solvent NanoIiltration (OSN) membranes as a replacement Ior
    conventional separation or puriIication processes (e.g. column chromatography, distillation) would be a signiIicant contributor
    to tackling the major separation problems encountered in the pharmaceutical industry. However, limited perIormance oI the
    commercially available membranes in polar and polar aprotic solvents has oIten been reported as a key reason behind the lack
    oI penetration oI OSN into industry |1|.
    -440-
    The recent breakthrough in OSN technology with the discovery oI the DuraMem
    TM
    membranes (diamine modiIied P84
    polyimide) has opened up possibilities Ior pharmaceutical OSN applications in a wide range oI organic solvents ranging Irom
    non-polar through polar to polar aprotic |2|. Testing work in a range oI solvents has shown that the separation perIormance oI
    DuraMem
    TM
    membranes is strongly inIluenced by organic solvent properties. Pure solvents and solute permeation studies were
    conducted to understand the mechanism oI their transport through these membranes. Five solvents (toluene, ethyl acetate,
    ethanol, tetrahydroIuran and acetone) and a series oI polystyrene oligomers with molecular weights oI 200 to 1,000 g.mol
    -1
    were used Ior the study.
    The relevance and importance oI this observed phenomenon has been investigated in a speciIic pharmaceutical separation to
    separate benzyl alcohol (BA), present as an impurity, Irom an API with molecular weight oI 278 g.mol
    -1
    . With THF as the
    process solvent, DuraMem
    TM
    membranes in spiral cartridge conIigurations have successIully puriIied starting materials Irom
    2.00 moles oI BA impurity to 1.00 mole oI API, to 0.02 moles oI BA impurity to 1.00 mole oI API, while recovering _ 90
    oI API.. Extended testing with the THF solution Ior over 60 operating days showed that the membranes and spiral cartridges
    have steady permeability and good separation perIormance.
    |1| P. Vandezande, L. E. M. Gevers and I. F. J. Vankelecom; Chem. Soc. Rev.; 2008, 37, 365 405.
    |2| Y.H. See-Toh, F.W. Lim and A.G. Livingston; Journal oI Membrane Science; 2007, 301, 3 - 10.
    PF.4.5
    Cross-linked 6FDA-based copolyimide membranes - Characterization method and
    performance in aromatic/aliphatic separation
    D. Katarzynski
    2
    , A. Mixa
    1
    , P. Rlling
    1
    , C. Staudt
    1
    1
    Institute of Organic and Macromolecular Chemistrv, Functional Materials, Heinrich-Heine Universitv, 40225 Duesseldorf,
    Germanv
    2
    Whatman GmbH (GE Healthcare), 37586 Dassel, Germanv
    staudtuni-duesseldorI.de
    6FDA-based copolyimides provide excellent chemical and physical characteristics like high stability against temperature, high
    chemical resistance, good mechanical properties, the ability to Iorm thin Iilms and modiIication possibilities. Due to these
    characteristics suitable membranes Ior pervaporation and gas permeation applications were gained Irom 6FDA-based
    copolyimides. Various application examples including the separation oI aromatic/aliphatic mixtures |1-3|, oleIin/paraIIin-
    mixtures |4|, process water |5,6|, gas pairs |7,8| etc. are described in literature.
    By providing cross-linkable groups in the polymer structure and covalent cross-linking the membrane, Staudt-Bickel and
    Koros |9| achieved chemically resistant membranes. These cross-linked membranes are insoluble in most oI the common
    solvents which causes problems in analyses. Acid number determination seems to be a promising method Ior the
    characterization oI the degree oI cross-linking.
    A challenging membrane application is the separation oI aromatic/aliphatic mixtures that accrue in the chemical and
    petrochemical industry Ior example during the extraction oI BTX-aromatics or during Iuel-mixture preparation. The high
    swelling potential oI aromatic components make the usage oI cross-linked membranes expedient. As an realistic example Ior
    an aromatic/aliphatic separation problem, pervaporation experiments were carried out with cross-linked 6FDA-4MPD/DABA
    m:n membranes and a mixture oI naphthalene as dinuclear, high-boiling aromatic component and n-decane as aliphatic
    component.
    |1| D. Katarzynski, F. Pithan, C. Staudt, Pervaporation oI multi component aromatic/aliphatic mixtures through copolyimide
    membranes, Separation Science and Technology 43 (2008) 59-70.
    |2| F. Pithan, C. Staudt-Bickel, S. Hess, R. N. Lichtenthaler, Polymeric membranes Ior aromatic/aliphatic separation processes,
    ChemPhysChem 3 (2002) 856-862.
    |3| W. Y. Xu, D. R. Paul, W. J. Koros, Carboxylic acid containing polyimides Ior pervaporation separations oI toluene/iso-
    octane mixtures, Journal oI Membrane Science 219 (2003) 89-102.
    |4| S. Hess, C. Staudt-Bickel, R. N. Lichtenthaler, Propene/propane separation with copolyimide membranes containing silver
    ions, Journal oI Membrane Science 275 (2006) 52-60.
    |5| F. Pithan, C. Staudt-Bickel, Crosslinked copolyimide membranes Ior phenol recovery Irom process water by pervaporation,
    ChemPhysChem 4 (2003) 967-973.
    |6| B. J. Chang, Y. H. Chang, D. K. Kim, J. H. Kim, S. B. Lee, New copolyimie membranes Ior the pervaporation oI
    trichloroethylene Irom water, Journal oI Membrane Science 248 (2005) 99-107.
    |7| S. Xiao, R. Y. M. Huang, X. Feng, Synthetic 6FDA-ODA copolyimide membranes Ior gas separation and pervaporation:
    Functonal groups and separation properties, Polymer 48 (2007) 5355-5368.
    -441-
    |8| L. Wang, Y. Cao, M. Zhou, Q. Liu, X. Ding, Q. Yuan, Gas transport properties oI 6FDA-TMPDA/MOCA copolyimides,
    Europ. Polym. J. 44 (2008) 225-232.
    |9| C. Staudt-Bickel, W. J. Koros, Improvement oI CO2/CH4 separation characteristics oI polyimides by chemical
    crosslinking, Journal oI Membrane Science 155 (1999) 145-154.
    PF.4.6
    Valorisation of a by-product from vegetable oil production by enzymatic reaction
    and membrane processing
    A.R.S. Teixeira, J.L.C. Santos, J.G. Crespo
    Requimte/CQFB, FCT - Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica
    andreia.teixeiradq.Ict.unl.pt
    Recent eIIorts Irom industry to achieve better and improved methods Ior recovery and puriIication oI phytosterols are related
    to growing oI the health Iood market, particularly due to the widespread dissemination oI Iunctional Ioods. Under this context,
    the deodorizer distillate, which is a complex by-product stream Irom vegetable oil production, presents a high potential Ior the
    recovery oI added value compounds such as sterols and tocopherols. These compounds were shown to be potentially
    interesting Ior the pharmaceutical industry, mainly due to their bioactivity and their role in the prevention oI cardiovascular
    diseases and cancer. However, the relatively small diIIerence in size between those compounds and the other constituents is
    too small to assure an eIIective Iractionation by pressure-driven membrane processes, based only on size exclusion.
    The production oI compounds with higher molecular size, maintaining or increasing the respective bioactivity is a concept
    widespread in the industry. Recent studies indicate that sterols in the esteriIied Iorm are more bioactive than the Iree Iorm
    |1,2|. Moreover, sterol esters are more soluble in the oil phase than Iree sterols, making easier their incorporation in Iat-based
    products. The production oI sterol esters may be perIormed by enzymatic esteriIication reaction between sterols and Iree Iatty
    acids (FFA) present in deodorizer distillates. The Iinal products can be subsequently Iractionated using solvent resistant
    ultraIiltration and nanoIiltration membranes. The success oI this project depends on the optimization oI the esterication
    reaction, and an adequate Iractionation oI the products. In particular, the separation and recovery oI sterols esters (700-800 Da)
    Irom others compounds with lower molecular weight (400 Da) is the main objective.
    This paper reports on the recovery oI bioactive micronutrients Irom the deodistillate resulting oI the oil production which due
    to its complexity cannot be used directly by the pharmaceutical industry without any previous treatment. The strategy Iollowed
    in this study was to develop a membrane based-process to valorise this residual stream by recovering added-value compounds
    which may be used as additives in the Iood, cosmetic and pharmaceutical industries.
    |1| Normen, L., Dutta, P., Lia, A. and Andersson, H., 2000. Soy sterol esters and b-sitostanol ester as inhibitors oI cholesterol
    absorption in the human small bowel. American Journal oI Clinical Nutrition 74, 908913.
    |2| Richelle, M., Enslen, M., Hager, C., Groux, M., Tavazzi, I., 2004. Both Iree and esteriIied plant sterols reduce cholesterol
    absorption and the biovailability oI beta-carotene and alpha-tocopherol in normocholesterolemic humans. American Journal oI
    Clinical Nutrition 80, 171-177.
    PF.4.7
    Combination of organic solvent nanofiltration and molecular engineering towards
    the efficient recycling of olefin metathesis catalysts
    T. Renouard
    1
    , A. Keraani
    1
    , C. Fischmeister
    2
    , M. Rabiller-Baudry
    1
    1
    Universite de Rennes 1 UMR Sciences Chimiques de Rennes CNRS (CIP),
    2
    CNRS UMR Sciences Chimiques de Rennes Universite de Rennes 1 (C&O)
    Campus de Beaulieu, 263 avenue du General Leclerc, CS 74205, 35045 Rennes - France
    thierry.renouarduniv-rennes1.Ir
    NanoIiltration is an innovative and promising technique Ior the recycling oI homogeneous catalysts.
    1
    This method is based on
    the rejection oI the dissolved bulky catalysts whereas the smaller reaction products are able to permeate through the membrane.
    Thus, this technique combines the advantages oI homogeneous and heterogeneous systems.
    -442-
    This study aimed at the combination oI this green process with molecular engineering to settle an eIIicient recycling oI oleIin
    metathesis catalysts. First, the commercial catalyst 1 was nanoIiltered in solution in toluene, using a Starmem

    228 membrane
    (MWCO 280 g.mol
    -1
    ) and a transmembrane pressure oI 25 bar, which resulted in a recovery oI 65. In order to improve the
    catalyst rejection, a strategy oI gradual increase oI the steric hindrance oI the catalyst was developed. By this way, catalysts 2
    and 3 were retained up to 82 and 92, respectively. However, the Iurther increase oI the size oI the catalyst showed the
    limitation oI this strategy, since catalyst 4 exhibited only 84 recovery. Such a result was attributed to the good aIIinity oI the
    polyimide membrane Ior aromatic groups, which Iavours the catalyst permeation.
    2
    Catalyst 3 was then engaged in a series oI
    metathesis reactions in dimethyl carbonate, an eco-Iriendly solvent that was recently successIully substituted to toluene.
    3
    Quantitative conversions oI the substrate were obtained Ior 5 consecutive cycles, starting Irom a single
    catalyst load.
    Ru
    O
    Cl
    Cl
    N N
    1 (627 g.mol
    -1
    )
    Ru
    O
    Cl
    Cl
    N N
    2 (717 g.mol
    -1
    )
    Ru
    O
    Cl
    Cl
    N N
    O
    3 (887 g.mol
    -1
    )
    Ru
    O
    Cl
    Cl
    N
    N
    Ru
    O
    Cl
    Cl
    N
    N
    Ru
    O
    N
    N
    Cl
    Cl
    4 (2195 g.mol
    -1
    )
    Figure 1: Commercial (1) and enlarged (2-4) oleIin metathesis catalysts.
    |1| H. P. Dijkstra, G. P. M. van Klink, G. van Koten; Acc. Chem. Res. 2002, 35, 798. P. Vandezande, L. E. M. Gevers, I. F. J.
    Vankelecom; Chem. Soc. Rev., 2008, 37, 365.
    |2| A. Keraani, T. Renouard, C. Fischmeister, C. Bruneau, M. Rabiller-Baudry; ChemSusChem, 2008, 1, 927.
    |3| X. Miao, C. Fischmeister, C. Bruneau, P. DixneuI; ChemSusChem 2008, 1, 813.
    PF.4.8
    High permeable OSN membranes based on glassy polymer with high free-volume
    fraction
    A. V. Volkov
    1
    , V. V. Parashchuk
    1
    , D. F. Stamatialis
    2
    , E.G. Litvinova
    1
    , V. S. Khotimsky
    1
    , V. V. Volkov
    1
    ,
    M. Wessling
    2
    1
    Topchiev Institute of Petrochemical Svnthesis RAS, Leninskv pr. 29, 119991, Moscow, Russia
    2
    IMPACT research institute, Facultv of Science and Technologv, Membrane Technologv Group, Universitv of Twente, P.O.
    Box 217, NL-7500 AE, Enschede, The Netherlands
    avolkovips.ac.ru
    Organic Solvent NanoIiltration (OSN) is a rapidly growing area oI membrane technology due to its great potential and
    advantages over the traditional separation methods. However, in contrast to the nanoIiltration oI aqueous systems that has
    many decades oI history, OSN membranes are still rather limited in number. Recently, we have proposed using like poly|1-
    (trimethylsilyl)-1-propyne| (PTMSP), as a material Ior OSN membranes |1|. The intrinsic nanoporous structure oI PTMSP
    (Iree violume Iraction (FVF) ~25) is naturally Iormed during casting oI polymeric solution and no subsequent treatment is
    required.
    In this work, a number oI composite PTMSP/PAN membranes by casting PTMSP solution on PAN-support (MWCO 55 kDa,
    kindly supplied by GKSS) are prepared and studied. The permeability oI various solvents through the PTMSP/PAN composite
    membranes with PTMSP layer oI about 0.9 m exceeds those oI various commercial membranes; while all membranes have
    high rejections oI two negatively charged dyes (see Table 1). Besides, the PTMSP/PAN composite membranes have quite
    good stability with slight decrease oI ethanol transport during operation period oI at least 230 hours.
    -443-
    Table 1. Solvent permeability |P, kg/m
    2
    hbar| and solute rejection |R, | oI membranes.
    Membranes P
    methanol
    R
    S1
    R
    S2
    P
    ethanol
    R
    S1
    R
    S2
    P
    acetone
    R
    S1
    R
    S2
    Desal-5-DK |2| 0.4 99 - 0.2 79 - - - -
    MPF-44 |2| 1.5 93 - 1.1 92 - 0.6 84 -
    MPF-50 |2| 2.0 97 - 0.9 92 - 1.7 93 -
    PTMSP/PAN 6.1 - 90 3.8 - 90 13.6 - 85
    S1 Erythrosine B (MW 880; negative); S2 Remazol Brilliant Blue R (MW 626.5; negative).
    Preliminary results oI transport oI methanol, ethanol and acetone through the composites show that the solvent viscosity and
    membrane swelling seem to be the most important Iactors aIIecting transport through the membranes.
    Acknowledgment. Alexey Volkov acknowledges to Russian Science Support Foundation.
    |1| A.V.Volkov, D.F.Stamatialis, V.S.Khotimsky, V.V.Volkov, M.Wessling and N.A.Plate. J. Membr. Sci. 281 (2006) 351
    357.
    |2| J.Geens, K.Boussu, C.Vandecasteele and B.Van der Bruggen. J. Membr. Sci. 281 (2006) 139148.
    PF.4.9
    Electro-extraction applied to highly dilute hydro-organic solutions
    S. Lacour, Ph. Sistat, P. Huguet, S. Deabate, G. Pourcelly
    Institut Europeen des Membranes, Universite Montpellier 2, CC 047, 34095 Montpellier Cedex 5, France
    stella.lacouriemm.univ-montp2.Ir
    Electrodialysis (ED) technique is used in a large variety oI Iields related to aqueous media (water desalination, acid/base
    production, by-product recovery Irom dairy industries, de-acidiIication oI Iruit juices, toxic compound removal Irom various
    industrial eIIluents). It is well known that in ED process, two kinds oI limitations exist: the problem Ior treating highly dilute
    solutions (energetic loss) and membrane Iouling and/or scaling (presence oI weakly soluble compounds). Today, most oI the
    research is devoted to improve the technicity oI ED through both Iundamental studies |1,2,3| (i.e. better ionic transport
    understanding across Ion Exchange Membrane (IEM), new IEM synthesis, modiIication and characterization) and applied ones
    |4,5| (i.e. pulsed Iield ED, combined processes with ion-exchange materials used as conducting spacers) in order to overcome
    those limitations.
    Recently, research on IEM applied to organic or hydro-organic media signiIicantly increase Ior energy production and storage
    (direct methanol Iuel cells |6|) and other innovative applications are proposed: electro-synthesis and production oI organic
    acids |7,8|. Ion transport behaviour across charged membranes |6,9|, IEM characterization and associated membrane process
    |6-10| is now better documented within those non conventional media. However, their application to the treatment oI dilute
    electrolyte organic or hydro-organic media has almost never been studied |10|.
    The Iocus oI the present work is to characterize both ion and solvent transport in electro-extraction process under extreme
    dilute electrolyte-hydro-organic solution conditions (10
    -4
    eq.L
    -1
    , various compositions oI water-ethanol mixtures). DiIIerent
    operating conditions (voltage/current applied, Ilow rate oI dilute and concentrate solutions, composition oI mixed water-
    ethanol solutions, solution circulation mode) and process conIigurations (conventional ED, electro-deionisation with ion
    exchange textiles used as conducting spacers) are tested in order to optimise electro-extraction yields oI anions (Cl
    -
    , I
    -
    ) and
    cations (Na

    , Ag

    ). Promising results could be achieved and new applications oI ED process could be expected Ior the
    treatment oI dilute mixed aqueous electrolyte-organic solutions: recovery and puriIication oI weakly soluble compounds,
    treatment oI mixed industrial waste-waters, demineralisation oI organic solutions, pre-concentration technique Ior weakly
    soluble species analysis.
    |1| L. Franck-Lacaze, P. Huguet, P. Sistat, Study oI ionic transport in anion-exchange membranes: relationship between
    structure and transport properties, Desalination, 2006, 200, 155-156.
    |2| T. Sata, T. Sata, W. Yang, Studies on cation-exchange membranes having permselectivity between cations in
    electrodialysis J. Memb. Sci., 2002, 206, 31-60.
    |3| T. Sata, Studies on anion-exchange membranes having permselectivity Ior speciIic anions in electrodialysis, J. Memb. Sci.,
    2000, 167, 1-31.
    |4| B. Ruiz, P. Sistat, G. Pourcelly, P. Huguet, Electromembrane process with pulsed electric Iield, Desalination, 2006, 199,
    62-63.
    -444-
    |5| S. Lacour, J. Sandeaux, Enhancing mass transIer in multi-electro-extraction technique using ion exchange graIted textiles,
    Desalination, 2006, 199, 57-58.
    |6| S. Deabate, R. Fatnassi, P. Sistat, P. Huguet, In situ conIocal-Raman measurement oI water and methanol concentration
    proIiles in NaIion membrane under cross-transport conditions, J. Pow. Sour., 2008, 176, 39-45.
    |7| F. Xu, C. Innocent, G. Pourcelly, Electrodialysis with ion exchange membranes in organic media, Sep. PuriI. Technol.,
    2005, 43, 17-24.
    |8| C. Huang, T. Xu, Y. Zhang, Y. Xue, G. Chen, Application oI electrodialysis to the production oI organic acids. State oI the
    art and recent developments, J. Membr. Sci., 2007, 288, 1-12.
    |9| J. Etheve, P. Huguet, C. Innocent, J.L. Bribes, G. Pourcelly, Electrochemical and Raman study oI a naIion
    perIluorosulIonic membrane in organic solvent- water mixtures, J. Phys. Chem. B, 2001, 105, 4151-4154.
    |10| M. Kameche M., F. Xu, C. Innocent, G. Pourcelly, Z. Derriche, Characterisation oI NaIion 117 membrane modiIied
    chemically with a conducting polymer: An application to the demineralisation oI sodium iodide organic solutions, Sep. PuriI.
    Technol., 2007, 52, 497-503.
    PF.5.1
    A novel engineered high throughput equipment for membrane based gas separations
    A. L. Khan, S. Basu, A. Cano-Odena, I. F. J. Vankelecom
    Centre for Surface Chemistrv and Catalvsis, Facultv of Bioscience Engineering, Katholieke Universiteit Leuven, Kasteelpark
    Arenberg 23 box 2461, B-3001 Leuven, Belgium
    Ivo.vankelecombiw.kuleuven.be
    High throughput (HT) screening techniques permit a rapid acquisition oI data and has proven to be extremely useIul to
    optimize time and material consumption. The development oI a worldwide unique platIorm oI HT-equipment Ior parallel
    synthesis and testing oI membranes in a single run was successIully introduced in membrane technology, so Iar only Ior liquid
    separations. |1|
    This study reports the development and Iirst application oI HT in gas separation (GS). A HT-GS system was designed,
    allowing simultaneous gas permeation and selectivity measurements oI 16 membranes in a very short interval oI time at
    diIIerent Ieed pressure and temperature.
    A variable temperature controller and adjustable upstream pressure controller are additional design Ieatures that permit
    measurements oI low-permeability membranes and evaluation oI temperature related phenomena. Samples carry over` in the
    tubes due to rapid switching between diIIerent membranes positions was avoided by using high Ieed pressure. Permeate Ilux
    was measured with increased permeate pressure as Iunction oI time in constant volume auxiliary cylinder. An online compact
    gas chromatograph was used Ior gas selectivity measurements.
    The potential oI the developed equipment and the HT-screening concept in general was validated by demonstrating the
    reproducibility (5) oI experimental Ilux and selectivity Ior commercial polyimide and lab-made polysulIone membranes at
    all 16 positions in O
    2
    /N
    2
    (50:50) gas mixtures. Results were compared with those obtained with a conventional single cell
    permeation module in order to check the reliability oI the equipment. The reproducibility and accuracy oI the data was highly
    encouraging, proving that this HT approach can be a useIul tool to rapidly screen a large array oI operational parameters in
    membrane processes and oI synthesis parameters in the development oI new high-perIorming membranes.
    Also diIIerent types oI new laboratory made mixed matrix membranes based on zeolites and MOFs were screened in H
    2
    /CO
    2
    and CH
    4
    /CO
    2
    separations. Specially very promising selectivity results were obtained with a new type oI mixed matrix
    polymeric membranes Ior this particular gas pair separation.
    |1| P. Vandezande, L.E.M. Gevers, J.S. Paul, I.F.J. Vankelecom, P.A. Jacobs, High throughput screening Ior rapid
    development oI membranes and membrane processes, J. Membr. Sci., 2005, 250, 305-310.
    -445-
    PF.5.2
    Asymmetric PVTMS-membranes for membrane gas desorption: regeneration of
    amine-based solvents
    S.E.Tsarkov
    1
    , J. de Bruin
    2
    , A.V.Volkov
    1
    , E.L.V. Goetheer
    2
    , V.V. Volkov
    1
    1
    A.J.Topchiev Institute of Petrochemical Svnthesis, Russian Academv of Sciences, Moscow, Russia.
    2
    TNO Science and Industrv, Delft, the Netherlands
    tsugurkaips.ac.ru
    Emission oI carbon dioxide, especially Irom the use oI Iossil Iuels is considered as one oI the major Iactors Ior the global
    climate change. One oI the ways to limit the emission oI CO
    2
    is to capture and store CO
    2
    Irom Ilue gas. Amine-based
    absorption process is the benchmark technology Ior CO
    2
    capture Irom Ilue gas. ThereIore, the development oI alternative
    techniques Ior post combustion CO
    2
    -removal based on well-known amine processes is highly required Ior reduction oI the cost
    Ior CO
    2
    capture. The aims oI this work are to investigate the potential oI Membrane Gas Desorption (MGD) processes Ior
    regeneration oI amine-based absorption liquids and usability oI PVTMS membranes Ior these processes.
    Asymmetric membranes based on poly(vinyltrimethylsilane) (PVTMS; selective layer thickness 0.1-0.2 m, membrane
    thickness 145 m) have been chosen Ior MGD experiments; 5M monoethanolamine (MEA) and 2M CORAL

    were used as
    absorption liquids. It was shown that PVTMS membranes have a good mechanical stability aIter exposure oI MEA at 110
    o
    C
    during 250 hours. No leakage oI 5M MEA and 2M CORAL

    aqueous solutions through PVTMS membranes was observed.


    The ratio oI CO
    2
    : water vapour Ior PVTMS membranes is much higher then Ior microporous membrane (PTFE). At the same
    time, the small top-layer provides relatively high CO
    2
    permeation in MGD process based on 5M MEA or 2M CORAL

    (Table
    1).
    ThereIore, it can be concluded that the direction oI using this type oI membrane can be oI high interest Ior the development oI
    economical Ieasible post combustion.
    Table 1: Membrane perIormance in MGD process: porous PTFE vs. asymmetric PVTMS.
    Flux, g/m
    2
    min
    CO
    2
    Condensate Total
    Ratio
    CO
    2
    /Solvent
    PTFE CORAL

    1.6-10.1 95.4-121.8 98.4-126.8 0.01-0.09


    PVTMSCORAL

    3.5-7.2 2.3-8.8 9.3-16.0 0.25-3.07


    PVTMSMEA 3.1-9.5 2.1-14.0 5.2-23.0 0.65-1.48
    This work has been done in the Irame work oI the project 'CO
    2
    Capture using amine processes: International cooperation and
    exchange (acronym 'CAPRICE; Sixth Framework Program).
    PF.5.3
    Enhanced CO
    2
    solubility in aromatic and alkyl chain substituted imidazolium-based
    room temperature ionic liquids
    A. Finotello, J. E. Bara, S. Narayan, D. L. Gin, R. D. Noble
    Department of Chemical and Biological Engineering, Universitv of Colorado at Boulder, Boulder, CO USA 80309-0424.
    Iinotellcolorado.edu
    Room-temperature ionic liquids (RTILs) are molten organic salts that possess a number oI desirable properties Ior gas
    separations applications, namely CO
    2
    capture. Their high thermal and chemical stability, negligible vapor pressures, and
    tunable chemistry make them great candidates to replace less environmentally Iriendly materials such as volatile organic
    compounds. The versatile Iunctionality oI RTILs allows Ior their potential usage Ior gas separations as a bulk Iluid, a
    supported liquid membrane, or as a polymerized RTIL solid membrane. Gas separations in these materials have been Iound to
    be driven by large solubility diIIerences between gases, rather than by diIIusion diIIerences. ThereIore, it is important to
    investigate the gas transport properties in RTILs to better understand their gas separation capabilities.
    -446-
    This study Iocuses on the solubility (S), diIIusivity (D), permeability (P), and selectivity behaviors oI CO
    2
    , CH
    4
    , and N
    2
    gases
    in bulk Iluid RTILs at constant temperature (22
    o
    C) and low pressure (~1 atm). The bulk Iluid RTILs tested are 1-methyl, 3-
    tolyl imidazolium bis(triIluoromethanesulIonyl)imide (C
    1
    ), 1-ethyl, 3-paraxylyl imidazolium
    bis(triIluoromethanesulIonyl)imide (C
    2
    ),1-butyl, 3-paraxylyl imidazolium bis(triIluoromethanesulIonyl)imide (C
    4
    ), 1-hexyl, 3
    paraxylyl imidazolium bis(triIluoromethanesulIonyl)imid (C
    6
    ), 1-octa, 3 paraxylyl imidazolium
    bis(triIluoromethanesulIonyl)imid (C
    8
    ), and 1-deca, 3 paraxylyl imidazolium bis(triIluoromethanesulIonyl)imid (C
    10
    ). Our
    initial results show that gas solubility increases, diIIusivity has a small variance, and permeability slightly increases with
    increasing alkyl chain length. Solubility and permeability selectivity decreases while diIIusion selectivity remains relatively
    unchanged with increasing chain length. The addition oI the aromatic ring substitution shows enhanced solubility over
    analogous alkyl-chain only substituted RTILs. Also, our work demonstrates that regular solution theory is valid Ior these
    RTILs.
    PF.5.4
    CO
    2
    separation properties of a commerciable polysulfone hollow fiber membrane
    H. Y. Hwang
    1
    , M. J. Koh
    1
    , H. C. Koh
    2
    , S. Y. Ha
    2
    , F. Scura
    3
    , G. Barbieri
    3
    , E. Drioli
    3
    , S. Y. Nam
    1
    1
    School of Materials Science and Engineering, Engineering Research Institute, i-Cube Center, Gveongsang National
    Universitv, Jinfu 660-701 Korea.
    2
    Airrane Co. Ltd, 217-2, Shinsung-dong, Yusung-gu, Daefeon 306-791 Korea.
    3
    National Research Council-Institute for Membrane Technologv (ITM CNR), Jia Pietro BUCCI, c/o The Universitv of
    Calabria, cubo 17/C, 87030 Rende CS, Italv.
    waldengnu.ac.kr
    Membrane-based gas separation oIIers great opportunities Ior bulk separation due to its low energy consumption, easy
    operation, and low maintenance comparing with chemical absorption or adsorption methods that requires regeneration oI
    sorbent. Moreover, the membrane process has the advantages oI modular design and lightweight, making it particularly
    suitable Ior retroIit into existing processes.
    In this study, pure and mixture gas separation tests were carried out using commercially available gas separation membrane
    supplied by Airrane co., Korea. The membrane showed stable CO
    2
    separation perIormance at high Ieed pressure without any
    CO
    2
    plasticization eIIect along with increasing CO
    2
    concentration. Although CO
    2
    selectivity oI the membrane was somewhat
    lower than that oI the Ube CO
    2
    separation membrane (Japan) which is the most commonly used membrane in this Iield, the
    separation perIormance data placed over the traditional gas separation upper limit. This result gives the possibility Ior
    commercialization, considering that membrane process can be easily combined with other separation methods such as
    chemical adsorption to raise the separation eIIiciency because oI its low purity oI produced gases.
    Figure 1. SEM images oI the commerciable polysulIone membrane
    |1| A. F. Ismail, W. Lorna, Suppression oI plasticization in polysulIone membranes Ior gas separations by heat-treatment
    technique, Separation and PuriIication Technology, 2003, 30, 37-46.
    |2| A. Bos, I. G. M. P nt, M. Wessling, H. Strathmann, CO
    2
    -induced plasticization phenomena in glassy polymers, J. Membr.
    Sci. 1999, 155,67-78.
    -447-
    PF.5.5
    Separation of toluene, propylene and butadiene mixtures from air by a membrane
    process for emissions reduction
    G. Rebollar-Perez
    1
    , E. Carretier
    1
    , N. Lesage
    2
    , P. Moulin
    1
    1
    Universite Paul Ce:anne Aix Marseille, Laboratoire de Mecanique, Modelisation et Procedes Propres (M2P2 UMR 6181)
    Departement en Procedes Propres et Environnement, Europole de lArbois, BP. 80, Batiment Laennec, Hall C
    13545 Aix en Provence Cedex 04, France
    2
    TOTAL Petrochemicals, Pole R&D Mont/Lacq, RN 117 - BP 47 - 64170 LACQ
    emilie.carretieruniv-cezanne.Ir
    Since the past decade, membrane processes have been used to treat atmospheric emissions, such as volatile organic compounds
    (VOC) Irom petroleum activities, though limited publications are reported |1,2|.
    The aim oI this study was to remove hydrocarbons Irom air by gas permeation. Toluene, propylene and 1,3-butadiene were
    chosen as model compounds, simulating gasoline composition. Limited studies oI permeation behavior involving 1,3-
    butadiene are reported |3|. A PDMS layer coated on a ceramic, tubular, porous support was chosen as membrane (55 cm
    2
    ). The
    results were obtained Irom a single-stage module without recycling. The membrane proved to be eIIicient in the separation oI
    binary toluene/air and butadiene/air mixtures. EIIects oI Ieed conditions (inlet concentration, pressure and Ieed Ilow) on the
    permeation Ilux, the permeability, the recovered Iraction and the enrichment Iactor were analyzed Ior binary and ternary
    mixtures. Several important results were obtained. For example, the permeability calculated Irom the experimental values Ior
    the binary mixture butadiene/air decreased with gas Ieed concentration when Ieeding the mixture at 0.06 Nm
    3
    h
    -1
    , whereas it
    remained unchanged at the lowest Ieed Ilow rate and it increased at the highest Ieed Ilow rate Ior the normalized temperature
    and pressure. Further studies will be needed to conIirm these results and deduce the transport mechanism Ior this composite
    membrane. In contrast, propylene permeability increased with increasing propylene Ieed concentration and with Ieed Ilow rate.
    The Iluxes oI permeated butadiene were higher than those Iound Ior propylene at the highest concentration tested. In terms oI
    hydrocarbon recovery using a single stage module venting the retentate to air, the percentage oI permeated propylene was
    inIerior to that oI butadiene. Also, the recovered hydrocarbon Iractions were minimal at the higher Ieed Ilow rates. These
    preliminary results are encouraging enough to propose a pilot conIiguration, with recycling oI the retentate and a several-stage
    module, which is likely to enhance hydrocarbon recovery. This pilot would be a valuable contribution to reducing hydrocarbon
    VOC emissions Irom chemical, petroleum and petrochemical activities.
    |1| Liu, Y., X. Feng, et coll. "Separation oI gasoline vapor Irom nitrogen by hollow Iiber composite membranes Ior VOC
    emission control." Journal oI Membrane Science, 2006, 271(1-2): 114-124
    |2| Ligang Lin, Ying Kong, Yuzhong Zhang. "Sorption and transport behavior oI gasoline components in polyethylene glycol
    membranes." Journal oI Membrane Science, 2008, 325 (1): 438-445
    |3| Okamoto, K., et col. 1997. "Permeation and separation properties oI polyimide membranes to 1,3-butadiene and n-butane."
    Journal oI Membrane Science 134:171-179
    PF.5.6
    Supported ionic liquid ceramic membranes for gas separation
    J. Christel
    1,2
    , T. Hirth
    1,2
    , T. Schiestel
    1
    1
    Fraunhofer Institute for Interfacial Engineering and Biotechnologv, Nobelstr. 12, 70569 Stuttgart, Germanv.
    2
    Universitv of Stuttgart, Institute of Interfacial Engineering, Nobelstr. 12, 70569 Stuttgart, Germanv.
    Jessica.Christeligb.IraunhoIer.de
    An ionic liquid (IL) is a salt with a melting point below 100C, mostly consisting oI a bulky organic cation and an inorganic
    respectively organic anion. These substances exhibit special properties like an extremely low vapor pressure and a high
    thermal stability compared to common organic solvents. The broad spectrum oI anion-cation combinations can be utilized to
    'design a customized ionic liquid with special desired Ieatures. Ilconich et al. |1| indicate that ionic liquids can be used to
    separate gas mixtures by using a membrane as a support. Consequently this system is called supported ionic liquid membrane
    (SILM). One Iield oI application Ior such SILM-systems is in electrochemical membrane sensors Ior combustion systems to
    improve the eIIiciency by measuring the CO and CO
    2
    -concentration and hence regulate the O
    2
    -inlet.
    Our aim is to develop a CO, CO
    2
    -selective SILM Ior gas separation at temperatures up to 300C, which can be used Ior
    instance in sensor applications. ThereIore we are Iocused on thermally stable ceramic membranes as support materials. In the
    -448-
    SILM the IL interacts with the support material as well as the gases. Our research implies both aspects. On the one hand
    pressure drop measurements are carried out to quantiIy the single gas absorption Ior CO and CO
    2
    oI various ionic liquids at
    high temperature (100 - 300C) and moderate pressure (up to 5 bar). The experiments are perIormed to get a Iurther insight in
    the correlation between the ionic structures and the gas solubility (Ior cations like imidazolium, piperidinium, pyridinium,
    pyrrolidinium, phosphonium and sulIonium as well as anions like bis(triIluoro-methylsulIonyl)imide, triIluoromethylsulIonate,
    dicyanamide and tris(pentaIluoroethyl)-triIluoro-phosphate). On the other hand the ionic liquid in the SILM-system is aIIected
    by the membrane material as well. For this reason experiments are carried out to investigate the wetting oI support material by
    ILs via contact angles. The SILMs tested so Iar indicate a high stability Ior a wide pressure (up to 6 bar) and temperature (up to
    200C) range. Furthermore permeation measurements Ior single gases as well as gas mixtures are planned to investigate the
    entire SILM-system. Hence the selectivity and the permeability will be determined to evaluate the combination oI the ionic
    liquid and the support.
    |1| Ilconich, J., C. Myers, et al. (2007). "Experimental investigation oI the permeability and selectivity oI supported ionic
    liquid membranes Ior CO2/He separation at temperatures up to 125 C." J. Membr. Sci. 298(1-2): 41-47.
    PF.5.7
    Separation of CO
    2
    /CH
    4
    binary mixtures through zeolite filled polyethersulfone based
    mixed matrix membranes
    . akal, H. Kalipilar, L. Yilmaz
    Department of Chemical Engineering, Middle East Technical Universitv, 06531 Ankara, Turkev
    e159633metu.edu.tr
    PuriIication oI natural gas by removing CO
    2
    is an important separation process because CO
    2
    decreases the heating value oI
    natural gas and corrodes pipelines. Membrane based technology used Ior CO
    2
    removal competes successIully with other
    commonly used technologies due to its advantages such as low energy costs and environmentally Iriendly operation |1|. Mixed
    matrix membranes (MMMs) composed oI glassy polymer and zeolites may improve the perIormance oI membrane in gas
    separation processes signiIicantly. Most MMMs are characterized by single gas permeation measurements. However,
    characterization oI membranes by binary gas mixtures is more attracted Ior industrial applications. Because the gas molecules
    in the mixture permeating through a membrane interact with each other and with membrane matrix in a diIIerent way than
    single gas molecules do.
    Hence, in this study, MMMs were prepared and the separation perIormances oI these membranes were investigated Ior
    separation oI CO
    2
    /CH
    4
    binary mixtures. The eIIect oI CO
    2
    Ieed composition on the membrane separation perIormance was also
    investigated. Membranes were prepared by solvent evaporation using the glassy polymer, polyethersulIone, SAPO-34 zeolite
    and low molecular weight additive (LMWA), 2-hydroxy 5-methyl aniline (HMA). DimethylIormamide (DMF) was used as the
    solvent. The perIormances oI the membranes were determined by using a constant volume-variable pressure technique at room
    temperature with a Ieed pressure oI 3.0 bar. The permeate was initially at 0.01 Torr (1.33*10
    -5
    bar). The percentage oI CO
    2
    in
    Ieed was changed between 10 and 50. The membranes were also characterized by scanning electron microscopy (SEM),
    diIIerential scanning calorimeter (DSC), thermogravimetric analysis (TGA).
    The permeabilities oI gas mixtures through PES/SAPO-34 membranes were higher than the permeabilities through PES/HMA
    membranes. On the other hand, with respect to CO
    2
    concentration in the Ieed, the permeabilities through both type oI the
    membranes showed a similar trend; an increase in CO
    2
    concentration in the Ieed resulted in an increase in the permeability.
    However, the selectivities Ior the PES/HMA membranes were more aIIected Irom the CO
    2
    concentration than the
    PES/SAPO-34 membranes. For PES/SAPO-34/HMA membranes, the permeabilities were higher than the permeabilities
    through the PES/HMA membranes, but lower than the PES/SAPO-34 membranes. The selectivities Ior the
    PES/SAPO-34/HMA membranes were the highest among the other type oI membranes. In conclusion, the choice oI the
    membrane type is likely to be determined Ior a particular application depending on the composition oI Ieed stream.
    |1| Y. Li, T.S. Chung, Highly selective sulIonated polethersulIone (SPES)-based membranes with transition metal counterions
    Ior hydrogen recovery and natural gas separation, J.Membr.Sci., 2008, 308, 128-135.
    -449-
    PF.5.8
    Separation of CO
    2
    and H
    2
    using palladium membranes (for integration in power
    generation with CO
    2
    capture)
    J.M. Sanchez, M. Maroo, M.M. Barreiro
    CIEMAT, Combustion and Gasification Division, Avda. Complutense 22, 28040 Madrid, Spain.
    josemaria.sanchezciemat.es
    CO
    2
    capture in power generation processes is currently one oI the most discussed issues. Pre-combustion Iuel decarbonisation
    Iocuses on producing a CO
    2
    and H
    2
    -rich gas through e.g. gasiIication, Iollowed by water gas shiIt (WGS). CO
    2
    is usually
    removed through chemical or physical solvents scrubbing |1|. For the Iuture, integrated high-temperature separation
    technologies Ior CO
    2
    capture are desirable. Palladium and Pd-alloy membranes are regarded as suitable Ior hydrogen
    separation at high temperature. II used aIter a WGS stage, Pd membranes could ideally split the CO
    2
    and H
    2
    -rich gas stream
    into a pure H
    2
    permeate stream and a pure CO
    2
    retentante stream.
    In this Iramework, CIEMAT is studying separation oI H
    2
    Irom CO
    2
    at bench scale using membranes. For comparison,
    separation oI H
    2
    Irom N
    2
    has also been studied.
    A 1 OD by 6 L Pd membrane Irom CRI
    Catalyst Co., U.S., was used in the experiments
    presented in this work. The membrane is
    housed in a 3-zone electric Iurnace with
    independent temperature control. H
    2
    , N
    2
    and
    CO
    2
    were Ied by means oI mass Ilow
    controllers. Permeate and retentate gas Ilow-
    rates were measured using a volumetric gas
    Ilow-meter.
    Permeability tests have been carried out Ior
    binary mixtures, H
    2
    /N
    2
    and H
    2
    /CO
    2
    . H
    2
    content
    in the mixture was 30 v/v. Gas Ilow rate (G)
    was set at 1,83 and 3,75 Nl/min. Two
    permeation temperatures were studied, 380C
    and 430C.
    0,0 0,5 1,0 1,5 2,0 2,5 3,0
    0,002
    0,004
    0,006
    0,008
    0,010
    0,012
    0,014
    0,016
    H
    y
    d
    r
    o
    g
    e
    n

    f
    l
    u
    x

    (
    m
    o
    l
    /
    m
    2
    s
    )
    P
    0.5
    1
    - P
    0.5
    2
    (kPa
    0.5
    )
    30% H
    2
    /N
    2
    30% H
    2
    /CO
    2
    Figure 1. EIIect oI gas mixture on H
    2
    Ilux (T380C, G1,83 Nl/min)
    Neither N
    2
    nor CO
    2
    were detected in the permeate stream. This means that the membrane shows inIinite selectivity to
    hydrogen. In this sense, preliminary results show that it would be Ieasible to separate H
    2
    Irom CO
    2
    using Pd-based membranes
    yielding a CO
    2
    rich stream at high pressure. However, results presented in Figure 1 show a reduction oI the H
    2
    Ilux in presence
    oI CO
    2
    compared to H
    2
    Ilux in H
    2
    /N2 mixtures. Further studies will be conducted to analyze why the presence oI CO
    2
    reduces
    hydrogen Ilux since interaction oI CO
    2
    with palladium surIaces has been observed by other authors |2|. An increase oI gas
    Ilow-rate had a positive eIIect on the hydrogen Ilux, although relative recovery (molH
    2
    permeate/molH
    2
    Ieed) was Iound to be
    independent oI gas Ilow-rate. Regarding the eIIect oI temperature, a decrease in the Ilux oI hydrogen that permeates through
    the membrane was observed Ior the H
    2
    /CO
    2
    mixture as temperature increases.
    This work has been Iunded by EU (FPVI Programme, CHRISGAS Project SES6-CT-2004-502587) and the Spanish Ministry
    oI Science & Innovation (PSE-120000-2008-29). CRI is grateIully acknowledged Ior providing CIEMAT with the evaluation
    membrane sample.
    |1| R. Bredesen, K. Jordal, O. Bolland, Chem. Eng. & Proc., 43 (2004), p. 1129
    |2| H. Li ; A. Goldbach; W. Li; H. Xu, J. Phys. Chem B (2008) 112 (39)
    PF.5.9
    CO
    2
    facilitated transport membranes by ionic liquids in Nafion matrix
    S. Yoo, J. Won
    Department of Chemistrv of Sefong Universitv, Gunfa ,Gwangfin, Seoul, Korea.
    jwonsejong.ac.kr
    Supported ionic liquid membranes have been widely studied in order to improve the stability oI the liquid membrane due to the
    negligible vaporization oI ionic liquids (ILs) |1|. In this study, we prepared CO
    2
    Iacilitated transport membranes by ILs in
    -450-
    NaIion matrix which has the interaction with IL as well as CO
    2
    . Three diIIerent ILs, 1-hexyl-3-methylimidazolium
    hexaIluorophosphate (|hmim||PF
    6
    |), 1-hexyl-3-methylimidazolium tetraIluoroborate (|hmim||BF
    4
    |)) and 1-hexyl-3-
    methylimidazolium bis(triIluoromethanesulIonyl)imide (|hmim||TI
    2
    N|), were used and polysulIone asymmetric membrane
    was used Ior a porous support. The CO
    2
    /N
    2
    ideal selectivity increased when ILs were mixed with NaIion and the selectivity
    reached to 83 and 90 Ior |hmim||BF
    4
    |/NaIion and |hmim||PF
    6
    |/NaIion, respectively. In order to improve the permeance oI the
    membrane, electrospun NaIion membranes on the polysulIone support were used. The structure oI IL/NaIion membranes was
    investigated by SAXS and the interaction between CO
    2
    and ILs (or NaIion) and IL/NaIion has been studied by the ab initio
    calculation.
    0
    10
    20
    30
    40
    50
    60
    70
    80
    90
    100
    110


    C
    O
    2
    /
    N
    2

    I
    d
    e
    a
    l

    S
    e
    l
    e
    c
    t
    i
    v
    i
    t
    y
    [hmim][Tf
    2
    N] [hmim][BF
    4
    ] [hmim][PF
    6
    ] Nafion [hmim][BF
    4
    ]/Nafion [hmim][PF
    6
    ]/Nafion

    Fig. 1 CO
    2
    /N
    2
    ideal selectivity oI IL, NaIion, and IL/NaIion membranes
    This work was supported by the Korean Research Foundation Grant Iunded by the Korean Government (MOEHRD)
    (KRF-2008-531-C00035)
    |1| JeIIery Ilconich, Christina Myers, Henry Pennline, David Luebke, Experimental investigation oI the permeability and
    selectivity oI supported ionic liquid membranes Ior CO
    2
    /He separation at temperatures up to 125 C 2007, 298, 41-47.
    PF.5.10
    Semiinterpenetrating networks based on Matrimid

    and cyanurate ester resins for


    suppression of CO
    2
    -plasticization
    M.L. Sanchez
    1
    , E.M. Maya
    1
    , A. Marcos
    2
    , J.G. de la Campa
    1
    , J. de Abajo
    1
    1
    Departamento de Quimica Macromolecular, Instituto de Ciencia v Tecnologia de Polimeros, CSIC, Juan de la Cierva 3,
    28006 Madrid, Spain
    2
    Departamento de Quimica v Tecnologia de Elastomeros, Instituto de Ciencia v Tecnologia de Polimeros, CSIC, Juan de la
    Cierva 3, 28006 Madrid, Spain
    evamayaictp.csic.es
    Polyimide membranes are used Ior gas separation because they have better permeability-selectivity balance than conventional
    glassy polymers. However, a disadvantage oI glassy polymers to perIorm separations involving CO
    2
    , such as gas natural
    upgrading or enhanced oil recovery, is their great tendency to plasticize at high CO
    2
    pressures. The plasticization produces an
    increase oI the permeability and a dramatic loss oI selectivity. Thus, plasticization should be suppressed to develop attractive
    polyimide membranes Ior high-pressure separations. One strategy scarcely explored to reduce plasticization is the Iormation oI
    semiinterpenetrating networks (SIPNs) |1|, which consist oI incorporating a thermoset into a thermoplastic matrix to rigidize
    the polyimide chain.
    In this work we report the preparation oI SIPNs using Matrimid

    (which has a CO
    2
    plasticization pressure oI about 12 atm), as
    a thermoplastic matrix, and a dicyanate ester derived Irom phenolphthalein (DC) (Figure 1), as cross-linkable monomer, in
    -451-
    diIIerent proportions (Irom 0.5 to 30). We have characterized the SIPNs and measured the CO
    2
    permeability using Ieed
    pressures ranging Irom 1 to 30 atm.
    SIPNs exhibited similar values oI CO
    2
    permeability (P(CO
    2
    )) Ior all Ieed pressures tested, even with very low DC percentage,
    thus indicating that plasticization was suppressed.
    The SIPN with the lowest DC percentage (0.5 ) exhibited the highest CO
    2
    permeability, around 4.5 barrers. Increasing the
    DC content to 1 and 3 involved a P(CO
    2
    ) decrease to 4 and 3.5 barrers respectively. SIPNs with 5 and 10 oI DC,
    exhibited CO
    2
    permeability values oI 3 and 2.5 respectively.
    Finally, SIPNs with higher DC content, 20 and 30, showed
    P(CO
    2
    ) coeIIicients lower than 2 barrers. These results clearly
    indicated that cross-linking caused a decrease oI the CO
    2
    permeability.
    Thus, we can conclude that the Iormation oI SIPNs with low
    contents oI the dicyanate ester (0.5-5) suppress the
    plasticization oI Matrimid

    , maintaining at the same time


    reasonable CO
    2
    permeability values, what makes them
    attractive materials Ior high-pressure separations oI CO
    2
    mixtures.
    O
    O
    OCN NCO
    Figure 1. Dicyanate ester derived
    Irom phenolphthalein (DC)
    |1| A. Bos, I.G.M. Pnt, M. Weesling, H. Strathmann, Suppresion oI CO
    2
    -plasticization by semiinterpenetrating polymer
    network Iormation, J. Polym. Sci. Part B, Polym. Chem., 1998, 36, 1547-1556
    PF.5.11
    Molecular dynamics simulation study of carbon dioxide transport in 6FDA- based
    polyimides
    S. Pandiyan
    1,2
    , D. Brown
    1
    , N. van der Vegt
    2
    , S. Neyertz
    1
    1
    Universitv of Savoie, Le Bourget du Lac Cedex, France
    2
    Max-Planck-Institute for Polvmer Research, Main:, Germanv,
    sylvie.neyertzuniv-savoie.Ir
    Carbon dioxide (CO
    2
    ) separation studies have become a major interest Ior researchers in the 21
    st
    century. Polymer membranes
    were known to have the potential to separate important gas mixtures long beIore, but during the last three decades, commercial
    gas separation membranes have become commercially available and several hundred new polymer materials have been
    reported
    1
    .
    In order to examine the relationship between the permeation properties oI CO
    2
    and polymer structure, we have selected three
    Iluorinated polyimides (6FDA-6FpDA, 6FDA-6FmDA and 6FDA-DAM) Ior our study. Indeed, Iluorinated polyimides have
    been identiIied as unusually good polymers with both high permeabilities and permselectivities
    2
    . In this work, molecular
    dynamics (MD) simulations are used to provide a detailed picture at the molecular level, which is compared to experimental
    evidence.
    Atomistic models oI the three selected Iluorinated polyimides were generated with the well-established hybrid Pivot Monte
    Carlo (PMC)-MD sampling technique
    3
    , and were subsequently simulated using MD. All the models were Iound to be in good
    agreement with the experimental densities, Iractional Iree volumes (FFV), Hildebrand solubility parameters and cohesive
    energies. As Iound in experiment, the diIIerences between the bulk properties oI 6FDA-6FpDA and 6FDA-6FmDA remain
    Iairly small in spite oI the Iact that they diIIer signiIicantly in their gas transport properties
    4
    . 6FDA-DAM has a signiIicantly
    lower density and more Iree volume. A realistic stepwise addition oI CO
    2
    was carried out in the pure polymer matrices and the
    CO
    2
    model sorption isotherms were Iound to be similar to experimental results
    5
    . Interestingly the Iluorine atoms seem to have
    no speciIic interactions with the CO
    2
    molecules. The presence oI highly electronegative Iluorine atoms prevents the eIIective
    packing oI polyimides and hence induces the high permeabilities and diIIusivities oI CO
    2
    . The volume swelling oI the
    polyimides (6FDA-DAM 6FDA-6FpDA 6FDA-6FmDA) is in reverse order oI the solubility. This phenomenon can be
    accounted Ior by taking into consideration the accessible Iractional Iree volume.
    |1| Baker, R.W. Ind. Eng. Chem. Res. 2002, 41, 1393-1411
    |2| Ghosh, M. K.; Mittal, K. L., Polyimides: Fundamentals and applications. Marcel Dekker Inc.: New york, 1996.
    |3| Neyertz, S. SoIt Materials 2006, 4, (1), 15 - 83.
    |4| Costello, L. M.; Koros, W. J. Journal oI Polymer Science Part B: Polymer Physics 1995, 33, (1), 135-146.
    |5| Vegt, N. F. A. v. d.; Briels, W. J.; Wessling, M.; Strathmann, H. The Journal oI Chemical Physics 1999, 110, (22),
    11061-11069.
    -452-
    PF.5.12
    A novel multilayered membrane for the separation of CO
    2
    from biogas and other
    permanent gas streams: Process investigations
    J. Wind, T. Brinkmann, C. Naderipour, T. WolII
    GKSS Research Centre Geesthacht GmbH, Insitute of Polvmer Research, Department of Process Engineering, Max-Planck-
    Strae 1, 21502 Geesthacht, Germanv
    jan.windgkss.de
    The removal oI CO
    2
    Irom permanent gas streams by means oI gas permeation is a separation task with ever increasing
    importance. Next to established applications in the conditioning oI natural gas other uses as separation oI CO
    2
    Irom biogas are
    currently under investigation. Aiming at the latter process a series oI investigations was conducted. A block copolymer having
    a high CO
    2
    /CH
    4
    selectivity was identiIied and a production process enabling the supply oI membrane material in m
    2
    -scale was
    developed. The resulting multilayer composite membrane showed homogenous quality Ior the 100 m Ilat sheet membrane
    material produced. It was tested in diIIerent laboratory and pilot scale units. As a Iirst step the single gas permeances oI this
    membrane were measured Ior a number oI diIIerent gases as e.g. CO
    2
    , CH
    4
    , N
    2
    , and O
    2
    . The varied parameters were
    temperature and pressure driving Iorce. At 20C the membrane showed a CO
    2
    -permeance oI 2.5 Nm
    3
    /(m
    2
    h bar) and a single
    gas selectivity oI 17.5 Ior the pair CO
    2
    /CH
    4
    . Subsequently, the membrane material was used to equip a GKSS-GS envelope
    type module. A membrane area oI 6.1 m
    2
    was installed. The module was tested in a gas permeation pilot plant using a synthetic
    gas mixture consisting oI CH
    4
    , CO
    2
    and N
    2
    . Since the pilot plant is equipped with a liquid ring compressor and liquid ring
    vacuum pump, both using water as service liquid, the Ieed gas was also saturated with water. A total oI 168 pilot plant
    experiments were conducted at varying Ieed compositions, Ieed and permeate pressures as well as Ieed Ilowrates. An example
    Ior the experimental results is shown in Figure 1. The CO
    2
    mole Iraction in the retentate was recorded as a Iunction oI varying
    permeate pressure and Ieed Ilowrate at
    constant Ieed pressure and composition. It is apparent
    that the membrane module shows the expected
    behaviour, i.e. increasing CO
    2
    mole Iraction in the
    retentate Ior increasing Ilowrate and increasing
    permeate pressure. The results oI the pilot plant could
    be well predicted using a simulation model developed
    Ior the GKSS-GS module employing the commercial
    process simulator Aspen Custom Modeler

    . The
    simulation employed the results oI the single gas
    measurements as the only experimental input. During
    the series oI pilot plant experiments the membrane
    showed no decline in operating perIormance. The high
    permeance oI the membrane material allows Ior the
    design oI compact plants suitable Ior decentralised
    biogas production Iacilities.
    0.0
    5.0
    10.0
    15.0
    20.0
    25.0
    0.0 10.0 20.0 30.0 40.0 50.0 60.0
    VoIumetric FIowrate Feed V
    F
    [Nm
    3
    /h]
    C
    O
    2

    M
    o
    I
    e

    F
    r
    a
    c
    t
    i
    o
    n

    R
    e
    t
    e
    n
    t
    a
    t
    e

    y
    R
    ,
    C
    O
    2

    [
    %
    ]
    Experimental data;
    Simulation;
    Experimental data;
    Simulation;
    Experimental data;
    Simulation;
    y
    F,CO2
    =30%, p
    F
    =4bar, p
    P
    =100mbar
    y
    F,CO2
    =30%, p
    F
    =4bar, p
    P
    =100mbar
    y
    F,CO2
    =30%, p
    F
    =4bar, p
    P
    =200mbar
    y
    F,CO2
    =30%, p
    F
    =4bar, p
    P
    =200mbar
    y
    F,CO2
    =30%, p
    F
    =4bar, p
    P
    =500mbar
    y
    F,CO2
    =30%, p
    F
    =4bar, p
    P
    =500mbar
    Figure 1: Pilot plant investigation results
    PF.5.13
    Influence of porous support structure on performances of high permeance composite
    hollow fibres membranes
    M. Sandru, S. H. Haukebo, M.-B. Hgg
    Department of Chemical Engineering, Norwegian Universitv of Science and Technologv (NTNU), Trondheim, Norwav
    may-britt.haggchemeng.ntnu.no
    Processing large volume oI gases Irom industrial sources requires a large membrane area with a minimal Ioot print. Hollow
    Iibre membrane geometry represents a solution due to the high ratio oI membrane area per volume. Polyvinyl amine (PVAm)
    composite membranes were prepared using hollow Iibres Irom polyphenylene oxide and polysulIone as porous support (Fig.1).
    Two procedures oI coating hollow Iibres outside and respective inside were investigated with respect to intrinsic PVAm
    polymeric solution properties, geometry and material oI hollow Iibres.
    -453-
    Polyphenylene oxide PolysulIone home made
    Fig.1 Cross section oI hollow Iibres used as porous support Ior membrane preparation
    Using similar operating conditions- humidiIied premixed gas (10 mol CO
    2
    , 90 mol N
    2
    ) and having a similar 1-1.5 m
    selective PVAm layer, the membrane selectivity ranged between 140 -200 being attributed mostly to the PVAm selective layer.
    In the same time the CO
    2
    permeance changed more than two order oI magnitude Irom 0.01 to 1.5 m
    3
    (STP)/(m
    2
    bar h) in direct
    correlation with CO
    2
    permeance oI individual porous supports used Ior membranes Iabrication. The diIIerence in CO
    2
    permeance is attributed to the geometry, material and the gas separation mechanism oI the porous support |1,2| correlated with
    the operating conditions.
    We acknowledge Norwegian Council Ior Research Ior the Iinancial support, BASF AG Ior kindly providing PVAm, Parker Ior
    providing PPO hollow Iibres and to Dr.Edel Sheridan (NTNU) Ior home made PSI hollow Iibres
    |1| U. Beuscher, C.H. Gooding, Characterization oI the porous support layer oI composite gas permeation membranes, J.
    Membr. Sci., 132, (1997), 213.
    |2| U. Beuscher, C. H. Gooding, The inIluence oI the porous support layer oI composite membranes on the separation oI
    binary gas mixtures, J. Membr. Sci., 152, (1999), 99.
    PF.5.14
    ETS-10/chitosan composite membranes for CO
    2
    /N
    2
    gas separation
    C. Casado, C. Tellez, J. Coronas
    Department of Chemical and Environmental Engineering, and Institute of Nanoscience of Aragon, Universitv of Zarago:a, c/
    Maria de Luna 3, 50018, Zarago:a (Spain)
    claraccunizar.es
    Carbon dioxide is considered one oI the major contributors to the global warming and worldwide eIIorts have been devoted to
    Iind means oI reducing CO
    2
    emission to the atmosphere. A promising way oI lowering the costs and improving the eIIiciency
    oI Ilue gas puriIication processes may be the development oI CO
    2
    -selective membranes. Polymeric |1| and inorganic |2|
    membranes have been reported regarding CO
    2
    /N
    2
    separation. More recently, hybrid and composite materials are being
    developed|3,4|.
    ETS-10 is a microporous titanosilicate built Irom TiO
    6
    octahedra and SiO
    4
    tetrahedra linked by corner-sharing oxygen atoms,
    Iorming a three-dimensional pore system with a considerable degree oI disorder. Each Ti atom in a six-coordinated state
    carries two negative charges, balanced by Na

    and K

    cations|5|. This makes ETS-10 particularly attractive in adsorption |6|,


    photochemistry, and catalysis and membrane separation processes|7,8|.
    Chitosan is a deacetylated derivative Irom chitin, an abundant natural polymer, cheap and obtained Irom renewable sources.
    Swollen chitosan membranes have been used Ior the separation oI CO
    2
    /N
    2
    |9|.
    In this work, ETS-10/chitosan nanocomposite materials have been prepared and characterized by several analytical techniques
    (N
    2
    adsorption, scanning and transmission electron microscopies, thermogravimetry, diIIerential calorimetry and vibrational
    spectroscopy, among others), showing a good interaction between ETS-10 and the polymer. CO
    2
    sorption experiments
    perIormed in ETS-10 and ETS-10/chitosan nanocomposites revealed potential on the CO
    2
    preIerential adsorption.
    ETS-10/chitosan membranes are also being prepared and tested on their CO
    2
    /N
    2
    gas separation perIormance.
    Acknowledgements: Financial support Irom the Spanish Ministry Ior Science and Innovation under project MAT2007-61028
    is grateIully acknowledged.
    |1| T. Kouketsu, S. Duan, T. Kai, S. Kazama, K. Yamada, J. Membr. Sci. 287 (2007) 51-59.
    |2| K. Kusakabe, T. Kuroda, S. Morooka, J. Membr. Sci. 148 (1998) 13-23.
    |3| S.N. Kim, W.J. Son, J.S. Choi, W.S. Ahn, Micropor. Mesopor. Mat. 115 (2008) 497-503.
    -454-
    |4| S. Himeno, T. Tomita, K. Suzuki, S. Yoshida, Micropor. Mesopor. Mat. 98 (2007) 62-69.
    |5| M.W. Anderson, O. Terasaki, T. Ohsuna, A. Philippou, S.P. Mackay, A. Fereira, J. Rocha, S. Lidin, Nature 367 (1994)
    347-367.
    |6| I. Tiscornia, S. Irusta, P. Pradanos, C. Tellez, J. Coronas, J. Santamaria, J. Phys. Chem. C 111 (2007) 4702-4709.
    |7| I. Tiscornia, S. Irusta, C. Tellez, J. Coronas, J. Santamaria, J. Membr. Sci. 311 (2008) 326-335.
    |9| L.A. El-Azzami, E.A. Grulke, J. Membr. Sci. 323 (2008) 225-234.
    PF.5.15
    Analysis of membrane performance in the treatment of gas streams of industrial
    interest
    P. Bernardo, G. Clarizia
    National Research Council - Institute for Membrane Technologv (ITMCNR) Jia P. Bucci, c/o Universitv of Calabria, cubo
    17/C, 87030 Arcavacata d Rende (CS), Italv
    g.clariziaitm.cnr.it
    Membrane separation oI gaseous mixtures is a technique which competes in various Iields (e.g. separation oI air components,
    separation and recovery oI CO
    2
    Irom natural gas and biogas, and oI H
    2
    Irom reIinery streams) with conventional unit
    operations on the basis oI overall economics, saIety, environmental and technical aspects.
    The recovery oI high value co-products Irom diIIerent industrial streams (e.g. organic vapours Irom oII-gas streams, helium
    Irom natural gas) is another interesting application, which created a new market Ior gas separation membranes, coupling
    environmental and economic beneIits.
    However, the presence oI some species at speciIic working conditions determines the occurring oI unIavourable phenomena
    such as plasticization that signiIicantly aIIect the membrane perIormance iI not taken into account in advance.
    In this Iramework, membrane systems with diIIerent transport properties in an appropriate range oI operating conditions will
    be investigated in order to meet the main requirements oI a process (purity, productivity and energy demand). An up to date
    review oI diIIerent membrane materials which could be applied (polymers, inorganic materials, nanocomposite membranes)
    will be critically discussed according to these targets.
    The relationships between process design (in order to minimize the energy requirement) and the type oI membrane needed will
    be addressed.
    Finally, this contribution intends to give an overview oI the diIIerent strategies which can be proposed to use gas separation
    membranes Ior the recovery oI speciIic components in an industrial context.
    PF.5.16
    Gas-liquid membrane contactors based on non-porous membranes for the recovery
    of CO
    2
    from gas mixtures
    M. Shalygin
    1
    , R. Yastrebov
    1
    , A. Golub
    1
    , F. Beggel
    2
    , V. Khotimskiy
    1
    , V. Teplyakov
    1
    1
    A.J.TOPCHIEJ Institute of Petrochemical Svnthesis, Russian Academv of Sciences (TIPS RAS), 29 Leninskiv prospekt,
    119991 Moscow, Russia
    2
    Aachener Jerfahrenstechnik (AJT) RWTH Aachen Universitv, 46 Turmstrasse, 52064 Aachen, Germanv
    mshalyginips.ac.ru
    The recovery oI CO
    2
    Irom diIIerent gas mixtures is important problem. CO
    2
    recovery is required in such processes as biogas
    separation, enrichment oI biohydrogen, post combustion capture oI CO
    2
    . High recovery degree and low losses oI target
    components should be achieved in these processes thereIore they should be highly selective and in addition low energy
    consumable. Separation system based on gas-liquid membrane contactor (MC) is proposed as a system which can satisIy both
    requirements. Gas-liquid MC is a device where mass exchange between gas and liquid phases takes place via a membrane. MC
    unites advantages oI absorption methods oI separation such as high selectivity and wide list oI known CO
    2
    absorbents with
    advantages oI membrane separation methods such as determined and constant area oI mass exchange and high speciIic area.
    In most cases porous membranes were utilized in investigated MC-modules. Suitable porous membranes are commercially
    available and provide low mass transIer resistance iI their pores are Iilled by the gas phase, thereIore they require very accurate
    -455-
    trans-membrane pressure drop control. Nevertheless even iI this requirement is satisIied a number oI studies have shown that
    liquid penetrates into membrane pores during the time. ThereIore utilization oI non-porous membranes is more preIerable iI
    they don`t introduce signiIicant mass transIer resistance. Wide application oI MCs based on non-porous membranes is limited
    due to the absence oI commercially available high permeable non-porous membranes which additionally have to be chemically
    resistant towards the traditional liquid absorbents oI CO
    2
    .
    This work represents the results oI the study oI CO
    2
    absorption in MCs with two diIIerent non-porous membranes based on
    poly-(vinyltrimethylsilane) and poly-(trimethylsilylpropyne). Additionally a mathematical model oI CO
    2
    transIer in MC was
    developed and expanded Ior the simulation oI CO
    2
    -containing gas mixture separation by recirculating system based on two
    MCs. Developed model was utilized Ior the theoretical investigation oI the system properties. Obtained results show that
    system provides high selectivity, high puriIication level and high recovery degree oI components. Characteristics oI the system
    have non-linear and extremal dependencies on liquid absorbent Ilow rate (which is a Iree parameter). This Ieature provides
    easy way Ior optimization and adjustment oI the system separation properties that is especially important Ior the application in
    biogas separation and enrichment oI biohydrogen since bioreactor productivity and gas mixture composition are non steady.
    This work is partially supported by FP6 IP no. 019825-(SES6) 'HYVOLUTION, Grant RFBR no. 07-03-00752a,
    Goscontract no. 02.526.11.6010. Authors kindly thank Dr. D. Syrtsova and Mr. G. Shalygin Ior their help during preparation
    oI composite membranes and Dr. E. Litvinova Ior preparing polymer samples.
    PF.5.17
    Long-term performance investigation of biogas upgrading systems applying gas
    permeation membranes
    M. Harasek, M. Miltner, A. Makaruk
    Institute of Chemical Engineering, Jienna Universitv of Technologv, Getreidemarkt 9 / 166, A-1060 Jienna, Austria
    michael.harasektuwien.ac.at
    Biogas is a promising renewable and sustainable energy source which can be utilized in numerous ways. It is produced in a
    large number oI biogas plants all over Europe Irom a maniIold oI substrates like energy crops, organic wastes or agricultural
    residues. Besides the minor contents oI malicious components like ammonia or hydrogen sulphide, biogas mainly contains
    methane (45 to 65 vol) and carbon dioxide. The common technology to use this energy source nowadays is the combustion
    in gas-engines and generating electric power with an eIIiciency oI 35 to 40. Because oI the rising prices oI energy and
    resources the ulitilzation oI engine waste heat is oI vital importance Ior an economically and ecologically eIIicient operation oI
    the biogas plant.
    Biogas upgrading is an upcoming alternative solution to the production oI electrical energy. Processed biogas can be used both
    as a natural gas substitute in households or industry and as a Iuel Ior transportation purposes (CNG engines). Depending on the
    local conditions, the most suitable product gas quality and upgrading technology has to be chosen. Either, an upgrading to
    natural gas quality together with the supply to a nearby natural gas grid |1|, or the upgrading to bio-CNG quality together with
    a local CNG Iuelling station is conceivable. Reduction oI CO
    2
    emissions and a contribution to more independence Irom Ioreign
    energy supplies is possible in both cases combined with the advantages oI an increased regional added value.
    Within this work, the long term perIormances oI two industrial scale biogas upgrading systems using gas permeation
    membranes Ior the upgrading oI 80 m/h and 180 m/h oI biogas, respectively, were investigated. Data Irom more than 10.000
    operating hours were available Irom Austria`s Iirst Bio-CNG Iuelling station which started its operation in Margarethen/Moos
    and Austria`s largest biogas upgrading installation Ieeding into the natural gas grid near Bruck/Leitha, both plants have been in
    operation since 2007 applying polyimide membranes Ior the simultaneous removal oI carbon dioxide and water Irom the
    biogas. The long-term perIormances oI both plants were compared with regard to energy demand, Ieed gas quality, operating
    conditions and biogas pre-treatment issues. Process dynamics were analyzed to develop process control optimization strategies
    and short start-up and shut-down procedures.
    |1| Miltner M., Makaruk A. and Harasek M., 2008, Application oI Gas Permeation Ior Biogas Upgrade - Operational
    Experiences oI Feeding Biomethane into the Austrian Gas Grid, Proceedings oI the 16th European Biomass ConIerence &
    Exhibition, Valencia, Spain, 2nd-6th June 2008, 1905-1911.
    -456-
    PF.5.18
    Gas permeation of polyamide membranes supported on ceramic tubes
    K. Briceo, R. Garcia-Valls, D. Montane
    Department of Chemical Engineering. Svstemic Group. Rovira i Jirgili Universitv. Av. Pasos Catalans, 26. 43007
    Tarragona, SPAIN
    kelly.bricenourv.cat
    Ceramic-supported polymer (CSP) membranes combine the good gas-separation properties oI high perIormance polymers with
    the mechanical stability oI the ceramic carrier. In tubular conIiguration, these hybrid membranes are suitable Ior scaling up
    towards industrial applications, being more competitive than commercial unsupported hollow Iiber membranes and polymer
    Iilms, specially under high pressure and temperature
    |1|
    . In this work, we have developed the obtention oI CSP membranes
    using Matrimid 5218
    |2|
    , a polyamide with excellent separation properties. Films oI around 30 m thickness have been Iormed
    on tubular ceramic supports (75 mm length, and 10 mm outer diameter). Supported and unsupported Matrimid 5218/N-
    methylpyrrolidone membranes have been characterized by electronic microscopy, DSC, TGA and FTIR in order to establish
    the relationship between structure and membrane properties, speciIically, gas permeation and selectivity oI separation in
    mixtures oI H
    2
    , CO
    2,
    CO and CH
    4
    . The inIluence oI the Iabrication conditions, the type oI support, the number oI consecutive
    coatings, and the curing temperature on the Iinal perIormance is reported. Permeation and selectivity towards a mixture oI
    gases is compared with other promising materials Ior this type oI separations
    |3|
    . Carbon molecular sieve (CMS) membranes
    supported on tubular ceramic carriers were obtained by chemical vapor deposition oI the pyrolysis products oI Matrimid at
    850C. The perIormances oI the polymeric membranes and the CMS membranes obtained Irom Matrimid are compared and
    discussed.
    |1| Kreiter R., WolIs D.P., Engelen Ch.W.R., Van Veen H.M., Vente J.F., High-temperature pervaporation perIormance oI
    ceramic-supported polyimide membranes in the dehydration oI alcohols, Journal oI Membrane Science 319 (2008) 126132
    |2| Shishatskiy S., Nistor C., Popa M., Pereira S., Peinemann K.V., Polyimide Asymmetric Membranes Ior Hydrogen
    Separation: InIluence oI Formation Conditions on Gas Transport Properties, Advanced Engineering Materials 8, n 5 (2006)
    390-397
    |3| SauIi S.M., Ismail A.F., Fabrication oI carbon membranes Ior gas separationa review, Carbon 42 (2004) 241259
    PF.5.19
    Asymmetric hyflon AD60X membranes entrapping ruthenium porphyrin complexes
    for gas separation
    M.G. Buonomenna
    1
    , G. Golemme
    1,2
    , E. Gallo
    3
    , S. Fantauzzi
    3
    , E. Drioli
    1,2
    1
    Dipartimento di Ingegneria Chimica e dei Materiali, Universita della Calabria, and Consor:io INSTM, Jia Pietro Bucci
    45A, I-87030 Rende (CS), Italv
    2
    ITM-CNR, Istituto per la Tecnologia delle Membrane, Jia Pietro Bucci 17C, I-87030 Rende (CS), Italv
    3
    Dipartimento di Chimica Inorganica, Metallorganica e Analitica, Universita degli Studi di Milano and ISTM-CNR, Jia
    Jene:ian 21, I-20133 Milano, Italv.
    mg.buonomennaitm.cnr.it

    Molecular engineering and molecular architecturing oI novel materials having superior characteristics and properties are
    rapidly growing technologies that will be pervasive in all Iields oI science and engineering |1|. In particular, in gas separation
    application, the incorporation oI transition metal complexes such as SchiII base oxygen carriers into polymeric membranes
    gave a signiIicant improvement in perIormance |2|. However, Ior diIIerent systems, diIIerent membrane perIormances have
    been observed.
    In this communication we will report on the preparation, characterization and gas transport oI new HyIlon AD60X membranes
    loaded with ruthenium porphyrin complex Ru(4-(CF
    3
    )TPP)CO (1) (TPP dianion oI tetraphenylporphyrin) (Figure 1). Aim oI
    the work was to improve HyIlon AD60 gas separation membranes increasing the solubility oI gases in the mixed polymeric
    matrix with (1): its addition conIerred microporous character to new membranes, which provides a high capacity Ior gas
    uptake, coupled with chemical Iunctionality that strengthens intermolecular interactions and encourages sorption.
    -457-
    Figure 1- The ruthenium porphyrin complex Ru(4-(CF
    3
    )TPP)CO (1) entrapped in an asymmetric HyIlonAD membrane.
    For commercial gas separations, very thin polymer Iilms are necessary, to maximise the Ilux through the membrane. ThereIore
    in this work, the membranes have been prepared by means oI nonsolvent induced phase inversion tuning the preparation
    conditions as type oI solvent, nonsolvent to obtain asymmetric membranes with a thin selective layer on a open macrovoid-Iree
    sublayer. The dispersion oI (1) on the membrane surIace and across cross section has been examined by means oI EDX
    topographical maps and XPS. These characterization showed: an uniIorm dispersion oI (1) on both membrane surIaces (top
    and bottom) due to its good compatibility with the polymeric matrix, owing to the introduction oI para CF
    3
    groups in the
    aromatic rings; a prevalence oI (1) in the membrane skin layer, due to solvent-nonsolvent mass transIer occurring during
    membrane preparation.
    The diIIusion coeIIicients, the permeability and the solubility oI He, H
    2
    , N
    2
    , O
    2
    , CH
    4
    and CO
    2
    through the new membranes
    were measured by means oI time-lag and steady state permeation measurements.
    |1| V. Balzani, A. Credi, F.M. Raymo, J.F. Stoddart, Angew. Chem. Int. Ed. 2000, 39, 3348.
    |2| J. Kurdi, A.Y. Tremblay, Polymer, 2003, 44, 4533.
    PF.5.20
    Preparation and gas transport properties of polysulfone nanocomposite membranes
    modified with additives
    S. Deniz
    1
    , I. Gurkan
    1
    , E. Okumus
    2
    1
    Yildi: Technical Universitv, Chemical Engineering Department, Davutpasa cd., Nr. 127, 34210 Esenler-Istanbul-Turkev
    2
    Scientific and Technological Research Council of Turkev (TUBITAK), Marmara Research Center, Energv Institute, Geb:e-
    Istanbul-Turkev.
    denizyildiz.edu.tr
    Membranes remain attractive opportunities Ior many gas separation industries (natural gas processing, landIill gas recovery,
    oleIin/paraIIin separation, air separation, hydrogen recovery, etc.) |1|. Because oI the economic competitiveness oI the existing
    separation technologies and the present challenges oI aggressive environments Ior membranes, many applications seek more
    robust membrane materials having higher selectivities and permeabilities. Not surprisingly, membrane materials development
    is an important research area to synthesize both higher perIormance and more durable membranes |2|. However, despite
    concentrated eIIorts to tailor polymer structure to aIIect separation properties; current polymeric membrane materials have
    seemingly reached a limit in the trade-oII between productivity and selectivity |3|. Because oI this limitation, much research is
    Iocused on Iorming and evaluating novel membranes, such as nanoporous molecular sieving materials (e.g. carbon molecular
    sieves (CMS), silica and zeolites). Polymer-inorganic nanocomposite materials, herein deIined as inorganic nanoIillers
    dispersed at a nanometer level in a polymer matrix, have been investigated Ior gas separation, and have the potential to provide
    a solution to the trade-oII problem oI polymeric membranes. The gas separation perIormance oI nanocomposite membranes
    can be Iurther enhanced by chemical modiIication. For instance, the introduction oI organic Iunctional groups on an inorganic
    Iiller surIace sometimes contributes to not only a better dispersion oI the inorganic material in the polymer membrane, but also
    a better absorption and transportation oI penetrants, which results in Iavorable selectivity and permeability |4|. The
    incorporation oI Iillers, blending with multiIunctional low molecular-weight additives (LMWA) and their combination are
    investigated as alternatives Ior modiIying the permselective properties oI polymeric gas separation membranes. The LMWAs
    are expected to be miscible and to interact with the polymer matrix to modiIy the chain characteristics |5|.
    This study examined the use oI silica nanoparticles as the disperse phase in nanocomposite membranes using continuous
    polysulIone matrices. Characterization oI the membranes and permeation properties Ior the O
    2
    /N
    2
    , H
    2
    /N
    2
    , CO
    2
    /N
    2
    , H
    2
    /CH
    4
    and
    CO
    2
    /CH
    4
    separations were discussed. Pure polysulIone (PSI), PSI/p-nitrophenol, (pNF), PSI/aminonitrophenol, (ANF),
    PSI/silica, PSI/pNF/silica and PSI/ANF/silica nanocomposite membranes were prepared by solvent-evaporation method using
    dichloromethane as solvent. Silica nanoparticles were the Iiller and pNF and ANF were the low molecular-weight additives
    -458-
    N
    N
    N
    N
    Ru
    CO
    F
    3
    C
    F
    3
    C
    CF
    3
    CF
    3
    (1)

    with multiIunctional groups. The concentrations oI pNF, ANF and silica were changed in the casting solution. Membranes
    were characterized by SEM, DSC and single gas permeability measurements oI O
    2
    , N
    2
    , H
    2
    , CO
    2
    and CH
    4
    .
    |1| S.A. Stern, Polymers Ior gas separations: the next decade, J. Membr. Sci., 1994, 94, 1-65.
    |2| W.J. Koros, R. Mahajan, Pushing the limits on possibilities Ior large scale gas separation: which strategies? J. Membr. Sci.,
    2000, 175, 181-196.
    |3| C.M. Zimmerman, A. Singh, W.J. Koros, Tailoring mixed matrix composite membranes Ior gas separations, J. Membr.
    Sci., 1997, 137, 145-154.
    |4| H. Cong, M. Radosz, B.F. Towler, Y. Shen, A Review: Polymer-inorganic nanocomposite membranes Ior gas separation,
    Sep. PuriI. Tech., 2007, 55, 281-291.
    |5| D. Sen, H. Kalipcilar, L. Yilmaz, Gas separation perIormance oI polycarbonate membranes modiIied with multiIunctional
    low molecular-weight additives, Sep. Sci. Tech., 2006, 41, 1813-1828.
    PF.5.21
    Gas permeation properties of poly(ether imide) nanocomposite membranes based on
    surface-treated silica
    S. Deniz
    1
    , D. Kutsal
    1
    , E. Okumus
    2
    1
    Yildi: Technical Universitv, Chemical Engineering Department, Davutpasa cd., Nr. 127, 34210, Esenler-Istanbul-Turkev.
    2
    Scientific and Technological Research Council of Turkev (TUBITAK), Marmara Research Center, Energv Institute, Geb:e-
    Istanbul-Turkev.
    denizyildiz.edu.tr
    There has been considerable interest in the addition oI nano-sized particles to polymer matrices to alter properties. Polymer
    composite membranes and barrier Iilms have attracted much interest in recent years; some oI the reasons can be easily
    understood in terms oI composite theory particularly Ior cases where the Iiller has a high aspect ratio. Composite theories
    assume that the properties oI each phase are the same as iI the other phase were not there; however, very near the surIace oI
    Iiller particles, the polymer chain packing and dynamics may be altered. This makes very little impact on overall perIormance
    when the particles are large. As the particles become much smaller, on the other hand, the amount oI surIace area increases and
    the distance between particles decreases. In this case, eIIects oI the interIace may become very important and the matrix phase
    eIIectively may not behave as it does in the bulk. The particles oI interest may be in the Iorm oI spheres, rods and platelets oI
    which Iumed silica, carbon nanotubes, and clays are examples. Another interesting case is where the particles are permeable
    but highly selective, like zeolites, and may improve the selectivity oI the composite, i.e., so-called 'mixed matrix membranes
    |1,2|; however, perIormance oI such composite membranes oIten seems to be compromised by the Iormation oI voids or
    deIects caused by dewetting oI the polymer at the surIace oI the zeolite particles |3-4|. These problems have hindered the
    development oI such membrane materials. Polymers Iilled with nanosized particles oIten show Iiller agglomeration and
    network Iormation in the polymer matrix. Agglomeration may make perIormance worse than that oI the matrix polymer. To
    resolve nanoparticle agglomeration or deIects and improve the Iiller particle dispersion in the matrix, a great deal oI attention
    has been devoted to modiIy the interIace between the Iiller and the matrix polymer |1-13|.
    The objective oI this research is to determine whether the presence oI nanosized particles changes the permeability and
    selectivity characteristics oI a glassy polymer matrix. In this work, nanocomposite membranes based on an amorphous, glassy
    poly(ether imide) were Iormed by incorporating two kinds oI hydrophobically treated Iumed silica by solution casting
    technique with or without chemical coupling. However, there is considerable evidence that these nanocomposites contain voids
    or deIects, probably at the polymer-particle interIace or within aggregates, that increase gas permeability and decrease
    selectivity. Thus, the primary Iocus oI this work is the relation between the extent oI voids Iormed in the nanocomposite and
    the permeation properties. In addition, it is to deal with techniques Ior dispersing nanosized particles, Iumed silica, in the
    polymer matrix, characterization oI morphology oI this mixture using TEM and SEM, and evaluation oI local properties based
    on gas permeation.
    |1| R. Mahajan, WJ. Koros, Mixed matrix membrane materials with glassy polymers. Part 1, Polym. Eng. Sci., 2002, 42,
    1420-1431.
    |2| C.M. Zimmerman, A. Singh, W.J. Koros, Tailoring mixed matrix composite membranes Ior gas separations, J. Membr.
    Sci., 1997, 137, 145-154.
    |3| T.T. Moore, R. Mahajan, D.Q. Vu, W.J. Koros, Hybrid membrane materials comprising organic polymers with rigid
    dispersed phases. AIChE J., 2004, 50, 311-321.
    |4| J.M. Duval, A.J.B. Kemperman, B. Folkers, M.H.V. Mulder, G. Desgrandchamps, C.A. Smolders, Preparation oI zeolite
    Iilled glassy polymer membranes, J. Appl. Polym. Sci., 1994, 54, 409-418.
    -459-
    |5| T.W. Pechar, M. Tsapatsis, E. Marand, R. Davis, Preparation and characterization oI a glassy Iluorinated polyimide zeolite-
    mixed matrix membrane, Desalination, 2002, 146, 3-9.
    |6| J.V. DeGroot, C.W. Macosko, Aging phenomena in silica-Iilled polydimethylsiloxane, J. Colloid InterIace Sci., 1999, 217,
    86-93.
    PF.5.22
    Membranes in biogas upgrading
    M. Ajhar, S. Yuece, T. Melin
    Aachener Jerfahrenstechnik, Chemical Process Engineering, RWTH Aachen Universitv, Turmstr. 46, 52056 Aachen,
    Germanv
    marc.ajharavt.rwth-aachen.de
    Apart Irom their use as adsorbents, polymers can be made into membranes, capable oI depleting trace gas components Irom
    biogas. The use oI membranes implies the principle oI gas permeation, where a partial pressure diIIerence over the membrane
    leads to an enrichment oI the more permeable gas species in the permeate.
    This work Iocuses on the separation perIormance oI elastomeric membranes used to deplete trace compounds in biogases,
    namely volatile organic silicon compounds. A selection oI elastomeric membranes have been prepared and tested on landIill
    gas over a period oI six weeks and their separation perIormance oI selected trace compounds was analysed with GC-MS.
    Based on these results, a pilot plant is in operation providing the prooI-oI-principle oI membrane-based biogas cleaning. In
    combination with CO
    2
    -removal and the introduction oI the cleaned biogas in the natural gas grid, membranes are competitive
    with state-oI-the-art upgrading technology.
    PF.6.1
    The effect of non-ionic surfactant on nanostructure of polyethersulfone
    ultrafiltration membranes
    A. Rahimpour, S.S. Madaeni
    Department of Chemical Engineering, Ra:i Universitv, Kermanshah, Iran
    smadaeniyahoo.com
    In this study, the eIIect oI Triton X-100 as non-ionic surIactant on nanostructure oI polyethersulIone membranes was
    investigated. Atomic Iorce microscopy (AFM) was employed to analyze the roughness and surIace morphology oI membranes.
    Average pore sizes oI membranes were obtained Irom height proIile oI AFM images using SPM soItware. Size oI each
    randomly chosen pore was calculated Irom the inIormation related to the height proIile and pore entrance. The membrane
    prepared without surIactant exhibited relatively large pores in selected surIace area and the Iormation oI nodules on membrane
    surIace was approximately reduced. It seems that the surIace pore density oI this membrane is very low. The membrane with
    typical nodular structure and interconnected cavity channels is Iormed when Triton X-100 is used as surIactant in the casting
    solution.
    -460-
    PF.6.2
    Effect of membrane length and membrane resistance on critical and limiting flux at
    the fractionation of milk proteins by microfiltration
    A. Piry
    1
    , W. Khnl
    1
    , T. Grein
    2
    , S. Ripperger
    2
    , U. Kulozik
    1
    1
    Technische Universitt Mnchen, Chair of Food Process Engineering and Dairv Technologv, D-85354 Freising-
    Weihenstephan
    Technische Universitt Kaiserslautern, Chair for Mechanical Process Engineering, 67663 Kaiserslautern
    alexander.pirywzw.tum.de
    Membrane Iiltration is well established Ior Iractionation and concentration tasks in the dairy industry. However, the problem oI
    membrane Iouling is still a limiting Iactor regarding operation times and sometimes dissatisIying yield or selectivity. In
    classical cross-Ilow Iiltration, the transmembrane pressure (Ap
    TM
    ) distribution along the membrane is inhomogeneous, which
    leads to a gradually decreasing Ilux Irom membrane inlet to membrane outlet. These eIIects promote the Iormation oI a non-
    uniIorm Ilux and, thereIore, a non-uniIorm deposit layer along the membrane, which causes a length dependent change in the
    Iractionation characteristics oI the membrane.
    Since adsorption phenomena and deposit layer Iormation are not uniIorm along a membrane, the investigation oI the eIIect oI
    membrane lengths should reveal a better understanding oI these phenomena. Flux and permeation characteristics oI the
    diIIerent membrane lengths (L0.3-1.2 m) were assessed during Iiltrations with diIIerent processing conditions (Ap
    TM
    , wall
    shear stress
    w
    ).
    The results oI this assessment will be analyzed in order to develop a novel perspective and modelling approach to describe the
    length dependency oI Iiltration processes. The Ilow path dependent assessment allow to diIIerentiate between those parts oI
    the membrane, which are run under membrane controlled conditions and those parts which are dominated by deposit layer
    Iormation. Based on this approach, a possible relationship between critical and limiting (maximum) Ilux as a Iunction oI
    membrane length will be presented. It will be shown that Ior the Iiltration oI milk, most parts oI a conventional membrane with
    an industrial length oI 1.2 m were controlled by a deposit layer even when high cross Ilow velocities and low transmembrane
    pressures are applied.
    As a result it can be concluded that Ior the Iractionation oI proteins it is necessary to operate the membrane below the critical
    Ilux. Otherwise proteins, which should pass through the membrane, are partially retained by the deposit layer. The only
    technical solution to solve the problem is to reduce the convective Ilow towards the membrane by increasing the hydraulic
    membrane resistance. Higher membrane resistances lead to lower membrane Iouling and, thereIore, to an improved
    transmission oI permeable substances.
    It will be shown that the membrane resistance and its corresponding initial permeate Ilux is oI paramount importance Ior the
    Iiltration perIormance. It will Iurther be shown that the membrane controlled and deposit layer controlled areas oI a membrane,
    respectively, can be calculated as a Iunction oI the processing conditions, the membrane resistance and the membrane length.
    This Iacilitates the optimization oI Iiltration processes, since the results obtained can be applied to industrial conditions.
    PF.6.3
    Optimisation and integration of membrane processes: recent developments in the
    starch and yeast industries
    F. Lipnizki, M. Nilsson
    Alfa Laval Business Centre Membranes, Alfa Laval Copenhagen, Maskinvef 5, DK-2860 Soborg, Denmark
    Irank.lipnizkialIalaval.com
    The starch and yeast industries are two key sectors oI the European Iood industry, with annual turnovers oI approx. t 4 billion
    and t 500 million, respectively, in Europe alone. The production processes in the starch and yeast industries are still dominated
    by conventional separation processes such as evaporators, separators and rotary vacuum Iilters (RVFs), and membrane
    processes are only rarely used. This presentation will show how membrane processes can be used to optimise the production
    process resulting in improved products produced in more economical and environmentally Iriendly ways.
    In the starch industry, the Iocus will be on (1) mud removal aIter saccariIication and (2) pyrogen removal in the starch-based
    sweetener production. Conventionally, RVFs with diatomaceous earth (kieselguhr) coating are used Ior removal oI the so-
    called mud phase consisting oI enzymes, proteins etc. aIter the saccariIication step. In a novel approach, a hybrid process
    consisting oI a two-phase decanter combined with ultraIiltration spiral wound modules is used Ior demudding. This approach
    -461-
    does not only overcome the disadvantages commonly linked to the use oI kieselguhr such as high disposal costs, sugar losses
    in the mud Iraction and saIety oI operators but also achieves higher colour removal and thus reduces the load on the
    subsequent ion-exchange columns. Further, ultraIiltration can be applied in the production oI pyrogen-Iree sweeteners with
    high purity replacing the cascades oI kieselguhr and cartridge Iilters conventionally used. In the ultraIiltration process, the Ieed
    stream is separated into a permeate stream oI puriIied sweeteners and a retentate stream containing the high molecular weight
    colour Iraction, germs and pyrogen resulting in high-quality products.
    In the yeast industry, the selected applications are related to the production oI yeast extract and highlight the use oI membrane
    processes Ior (1) optimisation and (2) concentration oI yeast extract, a Ilavour enhancer. In the yeast extract production, RVFs
    are used Ior polishing oI the yeast extract beIore Iinal concentration. UltraIiltration can be used to polish the yeast extract by
    removal oI suspended proteins, polysaccharides, bacteria, enzymes and yeast cells without the use oI kieselguhr. Hence, a
    higher product quality is achieved at lower environmental impact. Further, reverse osmosis can be used as pre-concentration
    step beIore evaporation, thus removing one oI the evaporator steps. This process synergy does not only provide a more gentle
    product handling at costs comparable to conventional straight-Iorward evaporation but also reduces the overall operating costs
    by lower energy consumption.
    In conclusion, as this presentation demonstrates, membrane processes improve the production oI yeast and starch products at
    the same time resulting in better products and thereIore contribute to a sustainable growth oI these industries.
    PF.6.4
    Effect of operational variables on fouling at the clarification of orange juice
    C. Pagliero
    1
    , L. Firman, N. Ochoa, J. Marchese
    2
    1
    Departamento de Tecnologia Quimica, Universidad Ncional de Rio Cuarto, CONICET, Ruta 36, Km 601, 5800 Rio Cuarto,
    Cordoba, Argentina
    2
    InFAp- CONICET UNSL, Chacabuco v Pedernera, 5700 San Luis, Argentina
    cpaglieroing.unrc.edu.ar
    ClariIication oI Iruit juice is a process oI great importance, as it allows to deliver the juice Ior its commercialization or to be
    undergone to a concentration process. The membrane technology allows perIorming this activity with high productivity and at
    a low cost without the product losing its properties.
    The main objective oI this work was Iormulating adequate membranes and determinate the optimal operating conditions Ior
    orange juice clariIication in order to obtain a reasonable amount oI permeate Ilux and preserve its organoleptics characteristic.
    The MF/UF membranes were prepared by inversion phase technique. Casting solution consisted oI PVDF, PMMA and PVP in
    dimethylIormamide solvent (DMF). The nascent membrane was immersed in bidistillated water coagulation bath and then
    transIerred to Iresh water Ior 24 h.
    The permeation experiments were carried out in a cross Ilow test cell with an eIIective membrane area A6.9 x 10
    -3
    m
    2
    . The
    membrane hydraulic permeability was calculated Irom Darcys law, measuring the permeate amount oI pure water as a
    Iunction oI transmembrane pressure. The distribution oI pore radius was measured by air-liquid displacement method.
    The orange juice was obtained Irom pressing oI the Iresh Iruits in a squeezing machine and then kept in a Ireezing chamber at
    18 C. In the experimental permeation test the Ieed juice solution was pumped continuously through the microIiltration unit
    by means oI a peristaltic pump at a predetermined cross Ilow velocity, v, and transmembrane pressure, P. Each test was
    carried out in a closed circuit Ior approximately 70 min, and it was perIormed with total recycling. The operating pressure was
    between 0.4 bars and 1 bar and the cross Ilow velocity ranged Irom 0.77 m/s to 1.25 m/s.
    For all the runs the permeate Ilux decrease during the Iirst several minutes oI operation and then it becomes constant Ior the
    remainder microIiltration operation (steady state). The main Iactors that contribute to the Ilux decay are the concentration
    polarization, adsorption and development oI a gel-layer at the membrane surIace. The results show that an increase in P does
    not alter the permeate characteristics. The best clariIication perIormance was obtained at v1.25 m/s and P1bar.
    -462-
    PF.6.5
    Olive oil quality improvement by membrane processes
    J.P. Bonnet
    1
    , J. Artaud
    2
    , C. Ochs
    3
    , P. Ochs
    3
    , P. Moulin
    1

    1
    Universite Paul Ce:anne Aix Marseille, Laboratoire de Mecanique, Modelisation et Procedes Propres (M2P2 UMR-CNRS
    6181), Europole de lArbois, BP. 80, Batiment Laennec, Hall C, 13545 Aix en Provence Cedex 04, France
    2
    Universite Paul Ce:anne, Institut des Sciences Moleculaires de Marseille, UMR-CNRS 6263, Europole de lArbois, BP. 80,
    13545 Aix en Provence Cedex 04, France
    3
    Moulin des Terroirs de Saint Laurent, Campagne Saint laurent, 84120 Beaumont de Pertuis, France
    philippe.moulinuniv-cezanne.Ir
    The aim oI this work was to enhance the production and the quality oI virgin olive oil. Two oils extracted Irom two olive Iruit
    varieties, Aglandau and Bouteillan, were studied. The main constraints Ior olive oil extraction concern the suspended matter
    concentration in the liquid collected Irom the press, the control oI the temperature, the minimization oI the Iluid transport Ior a
    better preservation oI the Iragrances. In order to take into account the variability oI the 2008 olive oil production (viscosity,
    concentration and nature oI the suspended matter), diIIerent oils covering the totality oI the production were used.
    The improvement in the oil quality due to the membrane Iiltration process was determined by K232 and K270 UV
    measurements, and the concentrations in phenols and suspended matter coupled with a sensory analysis. The inIluence oI the
    oil production method - continuous or traditional and oI the operating conditions oI the Iiltration process - cross-Ilow or
    dead-end Iiltration, cut-oIIs, concentration Iactors, TransMembrane Pressure (TMP)- was determined. The ceramic membranes
    were single or multi-channel membranes with Iiltration surIace areas ranging Irom 0.0075 to 0.08 m. The values oI the Ilux
    obtained with the membrane Iiltration process remained high over time. In most cases oI dead-end Iiltration (0.45 m and T
    21C), the permeate Ilux was about 15 kg.h
    -1
    .m
    -2
    Ior a TMP oI 2.5 bars. For similar operating conditions and an Aglandau oil,
    highly concentrated in suspended matters, the permeate Ilux was about 6.5 kg.h
    -1
    .m
    -2
    . The evolution with the Volumic
    Reduction Factor shows a slight decrease 25 - oI the permeate Ilow Ior a variation oI VRF between 1 to 60. Cross-Ilow
    Iiltration at low Ilow rate (0.5 m.s
    -1
    ) in order not to alter the quality oI the Aglandau oil provides a marked improvement in
    the permeate Ilux (x 2.5): 12 kg.h
    -1
    .m
    -2
    Ior similar PTM, VRF and temperature conditions. For all the membrane Iiltered oils,
    the permeates were obtained perIectly clear.
    Using microIiltration or ultraIiltration ceramic membranes makes it possible to totally eliminate the suspended matter present
    in the oil aIter the centriIugation step (separation oI olive oil and vegetation water). The oil thereby puriIied is less likely to be
    oxidized, and thus more likely to be oI better quality.
    Moreover, the results analysis shows that the characteristics oI permeates are very close to those oI oils that have been Iiltered
    traditionally, i.e. without using membranes. The results obtained show an increase in productivity. When the oil is Iiltered in
    various points on the production line, the useIulness oI the membrane Iiltration process is Iunction oI the water concentration.
    Finally, the membranes are totally regenerated thanks to a chemical washing. This regeneration step is taken into account in the
    production constraints to meet the requirements Ior organic certiIication. In view oI the results obtained, it is possible to
    consider, whatever the production method, the development oI an industrial unit to supply a readily marketable virgin olive oil.
    Acknowledgments: The authors would like to thank the Region PACA (France) Ior Iinancial and technical support
    PF.6.6
    Use of eIectrodIaIysIs wIth uItrafIItratIon membranes for naturaI phenoIIc
    antIoxIdant enrIchment of cranberry juIce
    L. Bazinet
    1
    , C. Cossec
    1
    H. Gaudreau
    1
    , Y. Desjardins
    2
    1
    Institute of Nutraceuticals and Functional Foods (INAF),
    1
    Department of Food Sciences and Nutrition, Universite Laval,
    Quebec, Canada, G1J 0A6
    2
    Department of Phvtologv, Universite Laval, Quebec, Canada, G1J 0A6
    Laurent.BazinetIsaa.ulaval.ca
    Cranberry Iruits are a rich source oI phenolic phytochemicals including phenolic acids, Ilavonoids and ellagic acids. Some oI
    the speciIic anthocyanins and proanthocyanidins in cranberry, which are phenolic antioxidants, have beneIits on human health
    and nutraceutical potential |1|. The enrichment oI cranberry products with phenolic antioxidants may improve their
    Iunctionality Ior enhancing health beneIits but this enrichment may be diIIicult due to the commercial rarity and diIIiculty oI
    puriIication oI these antioxidants. An enriched cranberry juice might be obtained by concentration oI this product. However,
    -463-
    this process has the disadvantage to also concentrate other components like sugars. The extraction oI proanthocyanidins and
    anthocyanins Irom cranberry juice may be used to enriched cranberry products with these phytochemicals. Membrane Iiltration
    technics are used Ior the isolation oI bioactive molecules Irom complex Ieeds and at a large scale, but they have too low
    selectivity. A new method named electrodialysis with ultraIiltration membrane (EDUF) has been developed to separate
    bioactive molecules |2|. The ultraIiltration membrane is stacked as a molecular barrier in an electrodialysis cell and the driving
    Iorce oI the process is an external electric Iield. The aim oI this work was to evaluate the Ieasibility oI the production oI a
    cranberry juice enriched with natural phenolic antioxidant compounds using an ultraIiltration (UF) membrane stacked in an
    electrodialysis (ED) cell. The total concentrations oI proanthocyanidins and anthocyanins increased oI 34.8 and 52.9
    respectively in cranberry juice treated with EDUF system. Moreover, a 18 increased oI the antioxidant capacity oI the
    enriched cranberry juice was obtained by the EDUF treatments and the taste oI the enriched cranberry juice seems to be
    improved in comparison with the non-treated juice. EDUF process could be directly integrated in the bottling process oI
    cranberry juice to produce antioxidant enriched-cranberry juices. This technology is a sustainable and environment Iriendly
    technology and appears to be a one step process. Then, EDUF process might be used Ior natural enrichment oI cranberry juice
    with antioxidant phenolics.
    |1| Leahy M., Roderick R., Brillant K., 2001. The cranberry- promising health beneIits, old and new. Nutrition today. 36:
    254-265.
    |2| Bazinet, L.; Amiot, J.; Poulin, J.-F; Tremblay, A. ., Labbe, D. Process and system Ior separation oI organic charged
    compounds. Demande de Brevet PCT/CA2005/000337.
    PF.6.7
    Caseinate based biodegradable films for packaging applications
    J.-L. Audic
    1,2
    , B. ChauIer
    2,3
    1
    Ecole Nationale Superieure de Chimie de Rennes, Universite de Rennes 1, CNRS, UMR 6226, Avenue du General Leclerc, CS
    50837, 35708 Rennes Cedex 7, France
    2
    Universite europeenne de Bretagne
    3
    Universite de Rennes 1, CNRS, UMR 6226, 263 Avenue du General Leclerc, CS 74205, 35042 Rennes Cedex, France
    jean-luc.audicuniv-rennes1.Ir
    Due to their renewable and biodegradable nature, proteins are attractive Ior innovative uses in the non Iood area. Caseinate
    presents thermoplastic and Iilm Iorming properties due its random coil nature and its ability to Iorm weak intermolecular
    interactions i.e. hydrogen, electrostatic and hydrophobic bonds. These properties make sodium caseinate interesting raw
    material Ior several applications in substitution oI traditional synthetic polymers
    1
    . Considering their transparency,
    biodegradability and good technical properties (high barrier Ior gases like O
    2
    )
    2
    , caseinate based Iilms can Iind many
    applications in packaging, in edible or protective Iilms and coatings or in mulching Iilms. However, some properties oI these
    materials need to be improved to Iind value added applications. Thus, mechanical properties are improved by plasticization
    with glycerol or triethanolamine and water resistance can be obtained by crosslinking with diIIerent techniques. SurIace
    properties oI such protein Iilms can also be strongly modiIied using surIace modiIying additives in small quantities, keeping
    the main properties oI the bulk material intact. Blending Iormulated proteins with other biodegradable polymers is also an
    interesting way to Iind new routes to innovative materials.
    |1| J. L. Audicand B. ChauIer, Eur. Polvm. J., 41, 1934-1942 (2005).
    |2| J. Chickand Z. Ustunol, J. Food Sci., 63, 1024-1027 (1998).
    -464-
    PF.6.8
    Effects of operation parameters on permeate flux and fouling resistances for
    ultrafiltration of Radix Astragalus aqueous extracts
    M. Cai , H. Liang
    Department of Applied Biologv and Chemical Technologv, The Hong Kong Polvtechnic Universitv, Hunghom, Kowloon, Hong
    Kong
    07901566rpolyu.edu.hk
    Polysaccharides are the major active constituents in Radix Astragalus (RA) aqueous extracts. EIIects oI operation parameters,
    namely temperature, transmembrane pressure (TMP) and molecular weight cut-oII (MWCO) oI membrane, on permeate Ilux
    and Iouling resistances Ior ultraIiltration (UF) oI RA aqueous extracts in were investigated. Resistance-in-series model was
    used to determinate the diIIerent resistances, including concentration polarization, cake layer and irreversible Iouling. Result
    showed that the Ilux enhanced by temperature was only about 15 higher when temperature increased Irom 20 to 50 C,
    indicating that the temperature within this range is not a signiIicant Iactor Ior consideration. Permeate Iluxes were enhanced
    about 40, 71 and 81 when the TMP increased Irom 0.4 to 0.8, 1.0 and 1.2 bar respectively, indicating TMP is a
    signiIicant Iactor in this UF process. However, about 60 and 65 Ilux reduction when UF oI 100 ml RA aqueous extracts
    were observed at TMP oI 0.4 and 1.2 bar respectively; while the contribution oI concentration polarization and cake layer
    resistances increased accordingly to 31.48 and 54.19, indicating that these two resistances were the main causes Ior Ilux
    reduction. Hence, it is not recommended to use very high TMP in the UF process Ior RA aqueous extracts. MWCO oI a
    membrane also plays an important role in the Ilux reduction. For 100k Da membrane, the Ilux declined sharply, nearly 70 in
    20 min. The resistance analysis showed that the irreversible Iouling, concentration polarization and cake layer contribute
    signiIicantly to the total resistance in this membrane. The Ilux in 1k Da membrane was small and showed negligible Ilux
    reduction as the intrinsic membrane resistance contributes signiIicantly to the total resistance. Membrane with MWCO oI 10k
    or 30k Da is suitable Ior UF oI RA aqueous extracts. SEM images showed clearly that the cake layer was Iormed on the
    membrane surIace and could be readily washed away by cleaning process.
    PF.6.9
    Microfiltration for the reduction of microorganisms in complex food systems: effect
    of bacterial characteristics on filtration result
    V. KauImann, U. Kulozik
    Technische Universitt Mnchen, Chair for Food Process Engineering and Dairv Technologv, Weihenstephaner Berg 1,
    85354 Freising, Germanv
    veronika.kauImannwzw.tum.de
    Membrane separation techniques can be used to reduce or eliminate microorganisms in Iluids. Especially to the dairy industry
    the mechanical separation oI bacteria and spores by microIiltration (MF) is becoming increasinlgy attractive, because it oIIers
    a product gentle alternative to heat treatment Ior debacterisation oI skim milk. The purpose oI applying MF in milk
    preservation thereIore is an eIIective reduction oI the bacterial load. But the main problem in using microIiltration Ior skim
    milk treatment is that the major protein Iraction (caseins) is in the same order oI magnitude as bacteria. Hence, to avoid rapid
    membrane Iouling and undesired retention oI protein, MF has to be applied using membranes with relativly large pore sizes
    (0,8-1,4 m) resulting in an incomplete removal oI microorganisms.
    This study thereIore aims at investigating the eIIects oI MF on the reduction oI microorganisms as a Iunction oI operating
    conditions (temperature, transmembrane pressure, wall shear stress), morphological and physiological characteristics oI
    bacteria and membrane/bacteria interactions (mainly adsorption and deposition). It is studied in detail and on a species basis
    which microorganims are preIerably retained or pass through the membrane. Besides the unavoidable passage oI bacteria
    through the membrane the behaviour oI the retained microorganisms on the retentate side is studied in order to assess the risk
    oI bioIouling, which could potentially worsen the microbial conditions and, thus, could have have a strong impact oI the
    overall target oI bacteria removal and product quality improvement.
    It could be shown that the retention oI microorganisms by MF depends on their (cellular) volume/size and shape. Apparently,
    iI Iiltration temperatures oI 50C are applied, in addition to the mechanical separation oI bacteria and spores, the bacterial
    reduction can be attributed to the thermal inactivation oI several (heat sensitive) microbes (e.g. Pseudomonas). ThereIore, the
    gram-properties also play a decisive role Ior the debacterisation eIIect. Moreover, considering the cell wall speciIity gram-
    -465-
    negative bacteria have a comparatively higher deIormability |1| leading to higher permeation rates (at transmembrane
    pressures oI more than 0,6 bar). In this context also the physico-chemical properties (charge and hydrophobicity) oI
    microorganisms |2| have to be mentioned resulting in speciIic interactions between the bacterial cell and the membrane
    surIace.
    |1| N. Lebleu, C. Roques, P. Aimar, C. Causserand, Role oI the cell-wall structure in the retention oI bacteria by
    microIiltration membranes, J. Membr.Sci., 2008, accepted manuscripte
    |2| R. Bos, H.C. van der Mei and H.J. Busscher, Physico-chemistry oI initial microbial adhesive interactions its mechanisms
    and methods Ior study, FEMS Microbiol. Rev., 1999, 23, 179-230
    PF.6.10
    Membrane fouling during wine microfiltration
    Y. El Rayess
    1,2
    , C. Albasi
    1,2
    , P. Bacchin
    3,4
    , P. Taillandier
    1,2
    , J. Raynal
    1,2
    , M. Mietton-Peuchot
    5
    , A. Devatine
    5
    1
    Universite de Toulouse , INPT, UPS , Laboratoire de Genie Chimique , 5 rue Paulin Talabot, BP1301, F-31106 Toulouse
    cedex 01, France
    2
    CNRS , Laboratoire de Genie Chimique , F-31106 Toulouse, France
    3
    Universite de Toulouse , INPT, UPS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    4
    CNRS , Laboratoire de Genie Chimique , F-31062 Toulouse cedex 09, France
    5
    Universite de Bordeaux, UMR 1219 Onologie, INRA, ISJJ, 210 Chemin de Levsotte, CS 50008,
    33 882 Jillenave dOrnon Cedex, France
    YousseI.elrayessensiacet.Ir
    Wine microIiltration is becoming widely extended in the recent past years in enology, mainly as a clariIication and
    microbiological stabilization process |1,2|. However, the development oI this process is hampered by membrane Iouling due to
    excessive retention oI some wine components |1,2|. The present study investigates the impact oI some speciIic wine
    constituents (phenolic compounds and proteins) as well as some physico-chemical parameters (pH) on a microIiltration
    membrane Iouling (cellulose acetate) in dead-end mode.
    The simultaneous presence oI the both species oI phenolic compounds (anthocyanins and tannins) in the synthetic wine was
    shown to be the main cause oI Iouling. An important decrease in the Ilow rates was also observed when yeast extract was
    added to the liquid. This yeast extract was shown to contain 300 mg/g oI proteins and to be Iree oI mannoproteins. The
    inIluence oI these proteins on Iouling was demonstrated while pre-treating the synthetic wine with bentonite, which was able
    to adsorb proteins. In this case, no Iouling was observed. It was also shown that, when decreasing the pH, the Ilow rate was
    enhanced. The experiments oI the actual red wine exhibited complete rapid Iouling oI the membrane, probably due to the
    presence oI high concentration oI phenolic compounds. For all experiments, the type oI Iouling (cake Iiltration or standard
    blocking) was determined to understand the behavior oI targeted molecules when Iiltrated.
    |1| P. Czekaj., F. Lopez, C. Guell: Membrane Iouling during microIiltration oI Iermented beverages. J. Membr. Sci., 2000,
    166, 199 212.
    |2| A.Vernhet, D. Cartalade, M. Moutounet: Contribution to the understanding oI Iouling build-up during microIiltration oI
    wines. J. Membr. Sci., 2003, 211, 357-370.
    PF.6.11
    Characterization of brine from a desalination plant for food process applications
    A. Argelles, E. Garcia-Castello, L. Mayor, M.L. Gras, D. Vidal
    Institute of Food Engineering for Development. Polvtechnic Universitv of Jalencia, Camino de Jera, s/n, 46022, Jalencia,
    Spain.
    anarIoital.upv.es
    Nowadays the concept oI resource has changed as consequence oI the increase in hydric requirements. In this context, the
    continuous population growth in some areas oI Spain has provoked the search oI alternative sources Ior water production such
    as sea water desalination.
    -466-
    Currently, the most employed desalination technique in Spain is Reverse Osmosis (87 oI all operational plants) due mainly
    to its low energy cost as well as its high process eIIiciency.
    However, independently Irom the used technique, the desalination process has an environmental impact as a result oI the
    concentrated salty residue generated during the depuration process, doubling salt concentration oI sea water.
    The current management oI the above mentioned wastewater stream is its return to the sea with the consistent risk Ior natural
    ecosystems.
    The aim oI the present work is two Iold: Iirst oI all, to characterize wastewater streams Irom a desalination plant in terms oI
    physical, chemical and biological properties; aIter that its potential use in Iood processing operations will be assessed based on
    the previous characterization.
    PF.6.12
    Effect of low anode/cathode voltage difference application on redox potential
    modulation during milk electroreduction and storage
    L. Bazinet
    1
    , A. Schreyer
    1
    , J. Lessard
    2
    1
    Institut des Nutraceutiques et Aliments Fonctionnels (INAF), Departement des Sciences des Aliments et de Nutrition, Pavillon
    Paul-Comtois, Universite Laval, Sainte-Fov (QC), G1J OA6, Canada
    2
    Laboratoire de svnthese et delectrosvnthese oragnique, Departement de chimie, Universite de Sherbrooke, Sherbrooke, J1K
    2R1, Canada
    laurent.bazinetIsaa.ulaval.ca
    Milk degradation during processing and storage is mainly due to oxidation-reduction reactions. Recently, electroreduction was
    applied to modulate the redox potential oI milk but on a very large range oI anode/cathode voltage (2, 4, 6, 8 and 10 V). The
    suggested value based on process eIIectiveness was 4 V. Our objectives in the present work were to 1) investigate the eIIect oI
    low anode/cathode voltage diIIerences on milk redox potential modulation during electroreduction, 2) optimize the process and
    3) compare storage oI a low-voltage electroreduced milk with a non electroreduced milk. It appeared Irom these results that
    electroreduction at anode/cathode voltage diIIerence oI 3 V was suIIicient to ensure a signiIicant decrease in ORP and DO.
    The application oI a 3V treatment instead oI the 4 V value would allow an energy saving oI 79. It appeared also that oxygen
    is an important parameter to consider during storage oI electroreduced milk. In Iact, during electroreduction up to 70 oI the
    dissolved oxygen was consumed. However, according to the conditions oI storage and the presence or not oI oxygen, its
    concentration can decrease constantly or stay stable during part oI the storage beIore decreasing. Hence, with opening daily
    during storage, samples started with negative values and presented positive values aIter only 3 days oI storage, while without
    opening, they presented negative values Ior a longer period. The rise in ORP during storage conIirms that the changes in redox
    state oI some milk species (mainly proteins) caused by the electroreduction treatments would be reversible and that the storage
    container material would be an important Iactor to consider when storing electroreduced milk to diminish or limit
    reincorporation oI oxygen due to a potential diIIusion through the wall oI the container.
    PF.6.13
    Protein concentration from salmon gelatin by ultrafiltration
    S. Gonzalez
    1
    , B. Cancino
    1,2
    1
    School of Food Engineering, Pontificia Universidad Catolica de Jalparaiso (PUCJ), Waddington 716, Valparaiso, Chile.
    2
    Regional Centre for the Studv of Healthv Foods (CREAS)
    beatriz.cancinoucv.cl
    Gelatin is an important protein with application particularly in pharmaceutical and Iood industries due to its chemical and
    physical properties and the ability to Iorm thermally reversible gels. Inside the process Ior obtain gelatin, the ultraIiltration
    could be successIul to concentrate gelatin solutions, as an alternative at the normal concentration process oI vacuum
    evaporators. |1,2|
    The objective oI this study was asses the Ieasibility oI concentrate gelatin protein by use oI ultraIiltration and compares the
    behavior oI two types oI gelatin: Gelatin 1 a mammalian gelatin and Gelatin 2 a salmon gelatin.
    UltraIiltration process was perIormed in a multitubular polyestersulIone membrane oI 30 kDa and 0.54 m
    2
    oI area, where the
    permeate solution was not returned at the Ieed tank. The concentration process with Gelatin 1, 5w/v initial solution at 32C
    -467-
    and 1.32 bar, showed two step in the permeate Ilux, the Iirst happened during the Iirst 50 min with a decrease in the permeate
    Ilux, while Irom aIter time there is a stability in the Ilux by the development oI a gel layer. The next concentration process with
    Gelatin 2, 2.7w/v initial concentration at 35C and 4.75 bar, lasted only 10 min, with a quickly decrease in the permeate Ilux.
    In both processes was possible the concentration oI protein with a colorless and liquid permeate solution, with a Retention
    Factor (RF) oI 2.0 and 4.3 Ior Gelatin 1 and 2 respectively, where RFC
    R
    /C
    F
    . C
    R
    is the Iinal protein concentration in the
    retentate and C
    F
    is the initial protein concentration in the Ieed tank. This behavior is explained due to the higher temperature
    used in the second process which inIluence in the viscosity oI the solution and the physical-chemical properties oI gelatins.
    Regarding the properties oI the gelatins, the contents oI hydroxiproline and proline stabilize the ordered conIormation in the
    gel network. In the case oI Iish gelatin the contents oI this imino acid are lower than mammalian collagens give a low gel
    modulus, low gelling and melting temperatures. Also, the extraction condition oI the gelatin may aIIect the hydrophobic amino
    acid composition and distribution, which inIluence the physical properties oI gelatin, even more than imino acid content.
    Furthermore, the type and contents oI chain inIluence the properties oI the gel, so gelatins containing more -chain show a
    higher gel strength and high Blomm value, which indicate the rigidity oI a gelatin Iilm, while Iish gelatin show a mix oI and
    -chain and thereIore low Blomm value |2|. -chain are two -chains covalently crosslinked, then could be interesting
    research the possibility oI gelatin Iractionation by membrane process and obtain diIIerent type oI gelatin Irom Iish.
    |1| A Simon, L. Vandanjon, G. Levesque, P. Bourseau, Concentration and desalination oI Iish gelatin by ultraIiltration and
    continuous diaIiltration processes, Desalination, 2008, 144:313-318.
    |2| A. Karim, R Bhat, Fish gelatin: properties, challenges, and prospects as an alternative to mammalian gelatins, Food
    Hydrocolloids, 2009, 23: 563-576
    PF.6.14
    Enzymatic treatment effect on pitanga juice microfiltration
    R. S. Ongaratto, I. C. N. Debien, L. A. Viotto
    LAMEFI, Department of Food Engineering (DEA), Facultv of Food Engineering (FEA), Universidade Estadual de Campinas
    (UNICAMP), Rua Monteiro Lobato, 80, PC6121, Campinas, Bra:il
    viottoIea.unicamp.br
    Pitanga is a Brazilian Iruit that is rich in lycopene, an important carotenoid to prevent prostate cancer and cardiovascular
    diseases |3|. Membrane process represents a technological answer to the problem oI the juices production with high nutritional
    and sensory quality |2|. One oI the major problems encountered in the preparation oI Iruit juices is cloudiness due primarily to
    the presence oI pectin. Pectinase hydrolyzes pectin and causes pectin protein complexes to Ilocculate. The enzymatic treatment
    results in lower amount oI pectin and reduced viscosity, which is advantageous Ior the subsequent membrane process |1|. The
    aim oI this work was to clariIy pitanga juice using a polymeric
    membrane oI polyvinylidene Iluoride (PVDF) and a tangential
    Iiltration pilot unit. The membrane poro size was 0.2 m and all
    experiments were carried out at 35C, 2bar and tangential
    velocity oI 1m/s, until concentration Iactor 2. It was evaluated
    the pretreatment with an enzymatic blend oI celulase (Cellubrix-
    L) and pectinase (Pectinex Ultra SP-L) (Novozymes, Denmark)
    (0.05 by weight oI each enzyme) with the objective to increase
    the permeate Ilux during pitanga juice microIiltration. The
    tannins retention Ior juice with and without enzymatic treatment
    was 27 and 42, respectively. In both cases there was 100
    carotenoids retention and 65 loss oI ascorbic acid. The average
    Ilux obtained Ior untreated juice was 24.71kg/m
    2
    h while Ior
    pretreated juice was 48.45kg/m
    2
    h, which represents a Ilux
    increase oI 96. It was Iound that the cake layer was the main
    permeate Ilux resistance and the total resistance was lower Ior
    the pretreated juice (Figure 1). The combination oI celulase and
    pectinase improved the permeate Ilux because oI the pectin
    content reduction caused by treatment.
    The authors would like to acknowledge the Brazilian government Ior awarding the research grant which makes this work
    possible.
    -468-
    Figure 1: Permeate Ilux resistance (CELPEC and PSTE
    mean juice with and without treatment; RP, RF and RM
    mean cake layer, Iouling and membrane resistance,
    respectively)
    |1| A. Abdullah, N. Sulaiman, M. Aroua, M. Megat. Response surIace optimization oI conditions Ior clariIication oI carambola
    Iruit juice using a commercial enzyme, J. Food Eng., 2007, 81(1), 65-71
    |2| A. Cassano, L. Donato, E. Drioli, UltraIiltration oI kiwiIruit juice: Operating parameters, juice quality and membrane
    Iouling, J. Food Eng., 2007, 79 (2), 613-621
    |3| A. Rao, L. Rao, Carotenoids and human health, Pharmacol. Res., 2007, 55(3), 207-216
    PF.6.15
    Influence of some chemical additives and ultrafiltration operating conditions on
    purification characteristics and permeate flux of thin sugar beet juice
    R. Niazmand
    1
    , M. Shahidi
    2
    , S.M.A. Razavi
    2
    1
    Islamic A:ad Universitv, Damghan branch, Iran
    2
    Ferdowsi Universitv of Mashhad, Department of Food Science & Technologv, Mashhad, Iran
    S.RazaviUM.ac.Ir
    The main objective in sugar industry is to remove the colorants and other non-sucrose compounds in order to obtain thin sugar
    juice with high purity and quality. In this study, the eIIect oI two chemical additives (ammonium sulphate and
    polyethylenglycol) and UF operating conditions including pressure (2, 3 and 4 bar) and temperature (30, 40 and 50
    o
    C) on
    color, turbidity, CaO content, soluble solids, purity percentage and permeate Ilux oI thin sugar beet juice were investigated. All
    experiments were perIormed using a dead-end stirred ultraIiltration cell and a polyethersulphone (PES) membrane with
    MWCO 5 kD. Absorbance spectra oI thin sugar beet juice and permeate in 420 and 720 nm showed a greater degree oI
    decolorization by PES membrane, especially when the ammonium sulphate was added. The membrane did not exhibit any
    appreciable selectivity towards CaO content. Chemical additives reduced purity percentage as well as permeate Ilux. However,
    increasing pressure and temperature resulted in higher permeate Ilux.
    |1| Shahidi, M. and Razavi, S.M.A., 2006, Improving thin sugar beet fuice qualitv through ultrafiltration, Desalination, 200,
    518-519.
    |2| Shahidi, M., Razavi, S.M.A., Behzad, Kh., Hakimzadeh, V., 2006, The effect of ultrafiltration process on puritv and de-
    colori:ation indexes of thin sugar beet fuice, Iranian Journal oI Food Science and Technology, 3(3), 31-38.
    |3| Shahidi, M., Razavi, S.M.A., Behzad, Kh., Hakimzadeh, V., 2006, The effect of operation parameters on ultrafiltration
    performance of thin sugar beet fuice, The Journal oI Agricultural Sciences & Technology, 20(5) 339-347, (pdI Iile).
    |4| Adikane, H.V., Thakar, D.M., Nene, S.N., 2004, Optimisation oI colour and sugar rejection oI black liquor using
    membranes, Serparation and puriIication technology, 36, 229-234.
    PF.6.16
    Sugar reduction by nanofiltration of white musts prior to vinification
    N. Garcia-Martin
    1

    ,2
    , L. Palacio
    1,2
    , P. Pradanos
    1,2
    , A. Hernandez
    1,2
    , M. Ortega-Heras
    3
    , S. Perez-Magario
    3
    ,
    D.C. Gonzalez-Huerta
    3
    , ML Gonzalez-San Jose
    4
    , M. Mihnea
    4
    1
    Depto. de Termodinamica v Fisica Aplicada, Fac. de Ciencias, Universidad de Jalladolid, Real de Burgos s/n, Jalladolid
    47071, Spain
    2
    Surface and Porous Materials (SMAP), UA-CSIC-UJA, R&D Building, Campus Miguel Delibes. Jalladolid 47071, Spain.
    3
    Estacion Enologica de Castilla v Leon, ITACYL, C/ Cristo 20, Rueda 47490, Spain.
    4
    Tecnologia de Alimentos, Facultad de Ciencias, Universidad de Burgos, P:a. Misael Bauelos s/n, Burgos 09001, Spain.
    nogamatermo.uva.es
    membranatermo.uva.es
    Last years have been warmer and dryer than usually. This has been attributed to the climate change induced by global
    warming. As a consequence oI that, an early ripening oI the grapes takes place which increases sugar content. This Iinally
    leads to alcoholic degrees higher than desired and associated to specially appreciated and characteristic wines. One oI the mild
    and highly speciIic technologies that could be used to reduce the undesired high degree in wine, involves the use oI
    nanoIiltration membranes.
    -469-
    We have tested the perIormances oI the NF-HL membrane made and commercialized by GE Water & Process Technologies.
    Musts proceding Irom the Verdejo variety oI wine grape, which are grown in the Rueda winegrowing region oI Spain, have
    been used.
    Two nanoIiltration steps were done thus leading to two retentates R1 and R2 and two permeates P1 and P2. Retentates and test
    unmodiIied must were Iermented along with the mixtures PATP2 and PB R1P2 in 'ad hoc proportions. It has been
    shown that the volatile proIile oI control wines (T) was largely diIIerent Irom that oI the wines obtained aIter modiIying the
    sugar levels oI the must.
    T PA PB R1 R2
    %

    C
    o
    m
    p
    o
    s
    i
    t
    i
    o
    n
    0
    5
    10
    15
    20
    25
    30
    35
    PT/10
    CATECHNES
    TANNES
    Tart. Esthers.
    FLAVONODS
    Abs. 420 100
    These results could be explained by the Iact that in the modiIied must the Iermentation process was less intensive than in the
    control must, so lower production oI Iermentation volatiles occurred. Similar results have been obtained Ior other relevant
    components oI wine as shown in the Iigure. PA and PB showed an increase in potassium and total tartrates, while the R wines
    showed a higher content in SO
    2
    and volatile acidity. These results agree with the taster`s comments who indicated that control
    wines showed more intense aroma, with higher Iloral and Iruity notes, whereas the lower alcohol wines were correct in colour
    and taste but slightly less intense in the olIactory phase. The resulting alcohol content was 12.7 Ior the T wine, 10.1 Ior
    PA, 9.3 Ior PB, 16.8 Ior R1 and 13.7 Ior R2.
    OI course some membrane based procedures have been described to directly treat the wines. Nevertheless, very dramatic loses
    oI the wine properties have been seen as Iar as wine is actually a very Iragile system which equilibrium is easily broken. This
    is why a treatment oI the must should be preIerred in order to reduce its sugar content. Moreover, an adequate control oI sugars
    in musts should be useIul to obtain low alcohol degree wines which are demanded by certain markets. On the other hand the
    byproducts oI the nanoIiltration could be used to elaborate high alcohol products or liquors.
    PF.6.17
    Micro and ultrafiltration performance of cellulose, PVDF and PES membranes in the
    green coconut water (Cocus nucifera) processing
    I. C. N. Debien, R. S. Ongaratto, L. A. Viotto
    LAMEFI, Departament of Food Engineering (DEA), Facultv of Food Engineering (FEA),Universidade Estadual de Campinas
    (UNICAMP), Rua Monteiro Lobato, n 80 PC 6121 Cidade Universitaria Zeferino Ja:, CEP13083862, Campinas/Bra:il
    isadebienyahoo.com
    In the last years, the consumption oI green coconut water (Cocus nucifera) has been growing both in the processed Iorm and in
    natura. The processing methods are used to inhibit the enzyme action and to ensure the microbiological stability aIter opening
    the Iruit, mantaining the original sensorial characteristics |1|. The membrane separation processes stand out as an alternative to
    conventional processes oI thermal treatment, acting as a selective permeable barrier to separate one or more solutes Irom a
    Iluid including microorganisms |3|. The aim oI this work was to evaluate the Cellulose 30 kDa, PVDF (Polyvilidene Iluoride)
    150 kDa and PES (PolyethersulIone) 150 kDa membranes perIormance on the permeate Ilux oI green coconut water and
    physico-chemical characterization oI raw material, retentate and permeate. The assays were conducted in a 800 mL laboratory
    cell at 25 C, submitted to pressures oI 0,5; 1,5; 2 bar Ior microIiltration membranes (PVDF and PES) and 2, 4 and 6 bar Ior
    ultraIiltration membrane (Cellulose), at 300 rpm using 400 mL oI raw material, being concentrated until a concentration Iactor
    (Fc) equal to 2. To inhibit the enzyme action beIore and during processing, ascorbic acid was added to green coconut water in
    the concentration oI 200 mg/L |2|. The physico-chemical analysis showed that there were not signiIicative diIIerence (p0,1)
    in the content oI total soluble solids, total solids, titratable total acidity and pH between retentate, permeate and raw material.
    The suspended solids were reduced in 88 and 90 , Ior the ultra and microIiltration, respectively, showing that there is not
    signiIicative diIIerence (p0,1). The enzyme retention was in the order oI 60 and 20 , Ior ultra and microIiltration,
    respectively. The permeate Ilux in all assays Ior cellulose membrane showed good results, which are Irom 95 to 145 kg.m
    -2
    .h
    -1
    ,
    and the highest occurred at 2 bar. Thus, there was a tendency oI Ilux decrease with pressure increase. Comparing PES with
    PVDF, PES membrane showed the best permeate Ilux, between 120 and 170 kg.m
    -2
    .h
    -1
    , while the PVDF was between 14
    and 70 kg.m
    -2
    .h
    -1
    . The increase oI pressure led to a permeate Ilux increase oI both materials. The permeates, as clariIicated
    -470-
    coconut water, showed transparent and mantained green coconut water Ilavor characteristics. ThereIore, the cellulose 30 kDa
    membrane (ultraIiltration) can be considered the membrane oI better perIormance, because it showed good permeate Ilux and
    better enzyme retention.
    |1| ARAGO, W. M. (Ed.) Coco. Pos-colheita. Aracaju: Embrapa Tabuleiros Costeiros, 2002. 76p.
    |2| CAMPOS, C. F.et al. Chemical composition, enzyme activity and eIIect oI enzyme inactivation oI Ilavor quality oI green
    coconut water. Journal oI Food Processing and Preservation, n.20, p.487-500, 1996.
    |3| GIRARD, B.; FUKUMOTO, L. R. Membrane Processing oI Fruit Juices and Beverages: A Review. Critical Reviews in
    Biotechnology, 20 (2): 109-175, 2000.
    PF.6.18
    Screening of organic microfiltration membranes to produce protein-stabilized oil-
    in-water emulsions by membrane emulsification
    A. Trentin, C. Gell, F. Lopez, M. Ferrando
    Departament dEnginveria Quimica, ETSEQ,, Universitat Rovira i Jirgili, Avda. Pasos Catalans, 26 43007 Tarragona,
    Spain
    montse.Ierrandourv.cat
    Membrane emulsiIication (ME) processes, direct or premix, have been reported to overcome some oI the main limits oI
    industrially applied emulsiIication techniques. With a low energy input, ME methods produce emulsions with a narrow droplet
    size distribution causing a minor damage to the shear stress sensitive molecules present in the emulsion, e.g. proteins. As in
    the case oI membrane separation, Iouling may be one oI the main limits to the industrial application oI ME, particularly when
    macromolecules such as proteins are used as emulsiIiers. In the case oI Premix ME, Iouling may have a major role because it
    is a two-step process, in which a pre-emulsion (with a wide droplet size distribution) passes through the pore structure oI the
    membrane. The Ilow oI the emulsion through the membrane pores disrupts the pre-emulsion droplets reducing the droplet size
    and its dispersion. Up today, ceramic membranes have been more extensively applied in ME than polymeric ones. However,
    the lower cost oI the polymeric membranes, recommends to investigate their potential use in ME with Iood purposes.
    The goal oI this work was to determine how the type oI organic membrane and the kind oI Iood grade protein aIIect the
    perIormance oI Premix ME processes. With this end, trans-membrane Ilux and droplet size distribution were determined
    during the production oI oil-in-water emulsions (O/W) by Premix ME.
    PolyethersulIone (PES), cellulose mixed esters (MEC) and Nylon membranes (0.8 m oI pore size) were used to obtain O/W
    emulsions (10 oI oil Iraction), while two proteins, bovine serum albumin (BSA) and whey proteins (WP), and a non ionic
    surIactant (Tween 20) were used as emulsiIiers. Transmembrane pressure (P) was set at 5 or 9 bar and the Premix step (pre-
    emulsion pressed through the membrane) was perIormed between 1 and 5 times (cycles).
    Although it was possible to produce stable emulsions with any oI the tested membranes, in the production oI O/W emulsions
    with 1 BSA, PES at 9 bar led to the highest trans-membrane Ilux (7.1+0.2 kg/m
    2
    s) Iollowed by that obtained with MEC. For
    O/W emulsions with 1 WP, MEC and Nylon membranes enable to obtain stable O/W emulsions with a P oI 9 bar.
    However, the highest trans-membrane Ilux was attained with MEC at 9 bar (3.6+0.2 kg/m
    2
    s). Regarding droplet size (d
    3,2
    ), the
    results clearly show that the pass oI the emulsion through the membrane decreased the droplet size between one halI and one
    third oI the coarse emulsion one, independently oI the membrane and/or emulsiIier. For the operating conditions that led to the
    highest trans-membrane Iluxes, the Iinal droplet size was between 3 and 4.6 m Ior the two proteins tested.
    -471-
    PF.6.19
    Premix membrane emulsification to produce protein-stabilized O/W emulsions with
    entrapped -carotene
    A. Trentin, C. Gell, F. Lopez, M. Ferrando
    Departament dEnginveria Quimica, ETSEQ, Universitat Rovira i Jirgili, Avda. Pasos Catalans, 26 43007 Tarragona, Spain
    montse.Ierrandourv.cat
    An enormous potential oI single and double emulsions in Iood, cosmetics, medicine and pharmaceutics is linked to their
    capability to improve biological availability, control release oI drugs, Iertilizers or pesticides and adsorb toxic compounds. For
    Iood applications, emulsions may oIIer some advantages related to their capacity to entrap bioactive compounds in the disperse
    phase. These emulsions act as carriers oI bioactive compounds which are non water-soluble but with high nutritional value,
    improving their use in Iormulated novel Ioods. In the present study, Premix membrane emulsiIication (ME) has been used to
    produce oil in water (O/W) emulsions with -carotene entrapped in the oil phase, using a protein as emulsiIier. Premix ME is a
    two-step process, in which a pre-emulsion (with a wide droplet size distribution) passes through the pore structure oI the
    membrane several times (cycles). As a result oI previous experience on the production oI O/W emulsions with Premix ME,
    two organic microIiltration membranes (cellulose mixed esters, MCE, and polyethersulIone, PES) were selected to produce O/
    W emulsions (10 oI oil Iraction) with entrapped -carotene. Two Iood-grade proteins (bovine serum albumin, BSA, and
    whey proteins, WP) and a non-ionic surIactant (Tween 20) were selected as Iood-grade emulsiIiers. An initial screening oI
    operational variables concluded that stable O/W emulsions, with 10 oil phase with -carotene can be obtained when using:
    1 BSA, 9 bar oI transmembrane pressure (TMP) and MCE and PES membranes; 2 Tween 20, 3-5 bar TMP and PES and
    MEC membranes; 1 WP, 9 bar TMP and MCE membrane. Emulsion and -carotene stability at three diIIerent temperatures
    (5, 20 and 35 C) during prolonged storage (up to three months) is being studied.
    PF.6.20
    Sugar reduction in grape juice using membrane fractionation
    B. Cancino
    1,2
    , R. Ruby
    1
    1
    School of Food Engineering, Pontificia Universidad Catolica de Jalparaiso, CHILE. Waddington 716, Jalparaiso, CHILE
    2
    CREAS. Regional Centre of Healthv Foods.
    Beatriz.cancinoucv.cl
    Grape juice presents a high contain oI phenolic compounds, very appreciated Ior its healthy properties|1|. In the other hands,
    the high contain oI sugar in the juice produces a reject specially because the increasing in the overweight oI the population in
    the last years. Because that this work pretend to reduce the sugar contain in the grape juice using a membrane Iractionation
    process, with MF, UF and NF. The membranes used were 0.2 m ceramic membrane with 0.02365 m
    2
    Ior MF, 10 kDa oI
    multitubular PES membrane Ior UF with 0.14044 m
    2
    and NF99HF AlIa Laval Ilat membrane oI 0.001018 m
    2
    Ior NF.
    The non clariIied grape juice with 17 Brix and pH 4.49 was MF reducing the turbidity in a 99.3 maintaining the sugar
    contain expresed in Brix, and pH very close to the Ieed juice. Permeate oI MF was UltraIiltrated removing the color in the
    juice where the permeate in the UF process was colorless. The sugar contain in the permeate was 15.3 Brix. That means the
    sugar passed through the UF membrane oI 10 kDa but not the poliphenol compounds. Permeate oI UF was NanoIiltred,
    removing the sugar and salts. 9.5 Brix was obtained in the permeate oI NF process, using 40C at 40 bar. This result indicates
    the sugar was partially removed using only one stage oI NF membranes. The sugar remotion could be complete using other NF
    membrane or doing a double stage NF process. Finally the low sugar grape juice was Iormulated using parts oI the diIIerent
    Iractions obtained in the Iractionation process as a Iirst approximation Ior the Iinal product. Two grape juices were Iormulated,
    one was cloudy and the second one was clariIied. Both were a reconstitution oI the diIIerent parts oI the Iractionation process,
    but cloudy juice was a mix using the original juice. For both Iormulated juices the sugar contain reduction was 31 expresed
    in Brix, respect to the original grape juice.
    Table 1. CIELAB parameters Ior the color in grape juice: L (Luminocity), a* and b* cromacity.
    L` a` b`
    Original grape juice 22.1 4.5 1.2
    Cloudy Iormulated juice 23.7 4.3 5.2
    ClariIied Iormulated juice 31.5 6.2 9.5
    The color parameters using CIELAB scale, are shows in the
    Table (Table 1). In the next works the Brix parameters will be
    compare with the real sugar contain, because the salts and others
    solids in the juice produce an inIluence in the Brix.
    -472-
    Acknowledgement: kind thanks to Dr. Frank Lipnizki oI AlIa Laval company Ior supply the NF membranes. This work was
    partial Iinanced with the FONDEF Project No. D07I1136. 'Diseo, produccion y evaluacion de jugos de uvas con propiedades
    Iuncionales que contribuyan a la promocion de la salud de la poblacion.
    |1| Balasundran N. K. Sundram & S. Samman. 2006. Phenolic compounds in plants and agri-industrial by-products:
    Antioxidant activity, occurrence, and potential uses. Food Chemistry, Vol 99: 191-203
    PF.6.21
    Lycopene concentrated of papaya pulp using polymeric membranes
    F. C.Silva, L.A. Viotto
    LAMEFI, Department of Food Engineering (DEA), Facultv Of Food Engineering (FEA), Universidade Estadual de Campinas
    (UNICAMP) Rua Monteiro Lobato, 80, Cidade Universitaria Zeferino Ja:, PC 6121, CEP 13083, Campinas , Bra:il
    viottoIea.unicamp.br
    The use oI processes with membranes to separate, clariIy, puriIy and concentrate represents one oI the most powerIul oI
    today's agribusiness, which is important in the concentration oI Iunctional compounds and nutraceuticals. The concentration oI
    lycopene in membrane processes is a viable process, since this carotenoid, despite oI the low molecular weight (300-600Da),
    remains in the retentate because it binds to other molecules such as proteins, pectin and lipid |1, 2|. The papaya has a
    considerable content oI lycopene ranging Irom 19 to 40 g/g oI Iruit in nature, depending oI the cultivar |3|. The aim oI this
    work was use the microIiltration process to obtain retentate rich in lycopene Irom papaya (Carica papaya L.). It was evaluated
    the perIormance oI polyvinylidene Iluoride membrane (PVDF, 0.2m) at 25 C under 2 bar and 300 rpm until the
    concentration Iactor 2, Ior: papaya juice, treated pulp with 0.1 pectinase; treated pulp with 0.1 cellulase and treated pulp
    with a enzymatic blend (0.05 cellulase and 0.05 pectinase). In the experiment where the papaya pulp was treated with
    pectinase showed low retention oI lycopene, probably due to release oI the carotenoid structure and enzyme action and the
    large membrane pore diameter. The best Ilux permeate was obtained with the papaya juice without enzymatic treatment, and
    ranged Irom 24.9 to 7.1 Kg.h
    -1
    .m
    -2
    , and the process showed 100 oI lycopene retention.
    |1| TASSELI, F.: CASSANO, A. DRIOLI, E. UltraIiltration oI KiwiIruit juice modiIield poly ether ketone) hollow Iiber
    membrane. Separation and puriIication technology, v.57, p-94 102, 2007.
    |2| HURST, W. J. Methods oI analysis Ior Iunctional Ioods and nutraceuticals-Functional Foods & Nutraceuticals series, EUA:
    CRC Press LLC, 2002.
    |3| RODRIGUEZ-AMAYA, D.B. Latin american Iood sources oI carotenoids. Archivos
    latinoamericanos de nutricion, v. 49, n.1, p. 74-84, 1999b.
    PF.6.22
    Degumming of canola crude oil by ultrafiltration with polymeric membranes
    L. Ara Campos, M. C. Chiu, L. A. Guaraldo Gonalves, L. A. Viotto
    Facultv of Food Engineering FEA, State Universitv of Campinas UNICAMP.P.O. Box 6121, CE 3083-862, Campinas, So
    Paulo, Bra:il
    viottoIea.unicamp.br
    Degumming crude vegetable oils process using membrane is normally perIormed at lower temperatures when compared with
    the conventional degumming. The membrane processes have the advantage oI preserving minors compounds, low energetic
    consume and reduce costs to process aids and residual water treatment. Several studies have been successIully perIormed using
    membrane technology to degumming miscella (oil hexane). On this technique it is necessary remove the solvent by
    evaporation on higher temperatures aIter the permeation. This work Iocuses on the study oI plane polymeric membrane to
    degumming canola crude oil searching Ior better Ilux and phospholipids retention. A sample oI crude canola oil with 405ppm
    phospholipids content and PES (10 kDa), CME (0,025m), PVDF (30kDa and 50kDa) membranes were selected to perIorm
    experiments at laboratory unit (dead end). The experiments were done until concentration Iactor 1.34 at 40C, 1 8 bar
    pressure. It was Iound Ilux Irom 6 to 38 L m
    -2
    h
    -1
    and 25 phospholipids rejection.
    -473-
    |1| R. Subramanian, M. Nakajima; Membrane Degumming oI crude soybean and rapeseed oils. JAOCS, v. 74, n 8 p. 971-975,
    (1997)
    |2| A. Koris, G Vatai; Dry degumming oI vegetable oils by membrane Iiltration. Desalination, v. 148, p. 149-153, 2002
    |3| A. Koris, E. Marki; Ceraic ultraIiltration membranes Ior non-solvent vegetable oil degumming (phospholipid removal).
    Desalination, v. 200, p. 537-539, 2006
    |4| M. Cheryan; Membrane technology in the vegetable oil industry. Membrane Technology, February, p.5 7, 2005.
    PF.6.23
    Effect of canola crude oil degumming by polymeric membrane ultrafiltration on
    tocopherol
    L. Ara Campos, M. C. Chiu, L. A. Viotto, L. A. Guaraldo Gonalves
    Facultv of Food Engineering FEA, State Universitv of Campinas UNICAMP.P.O. Box 6121, CE 3083-862, Campinas, So
    Paulo, Bra:il
    lirenyIea.unicamp.br
    The main interest on membrane technology application Ior vegetable oils processing is the costs reduction due to energy
    saving, lower consumption oI processing aids and minimization oI the residues. Another important beneIit Irom this
    technology is the preservation oI minor compounds. This process could be perIormed at lower temperature than traditional
    process |1|. The tocopherol is recognized as an eIIicient natural antioxidant and it is present at relatively high amounts on
    canola oil |2|. Usually it is expected up to 6 lost oI tocopherol in traditional reIining process, depending on the temperature
    and vacuum employed |3|. This work presents the residual tocopherol contents in degumming canola oils by both conventional
    process and polymeric membranes. The conventional degumming was perIormed at 80C and presented a 3,4 lost on
    tocopherol. Using ultraIiltration with PVDF 30kDa, 40
    o
    C, tocopherol was completely preserved Ior both raw materials
    employed: crude oil (FC 1.02) and miscella (FC 2.4). Due to the removal oI phospholipids, the centesimal composition oI
    permeate was modiIied, improving smoothly the absolute tocopherol content in the permeate (degummed oil), resulting in a
    higher quality oil.
    |1| M. Cheryan; Membrane technology in the vegetable oil industry. Membrane Technology, February, p. 5 7, 2005.
    |2| F. Shahidi; Bailey`s industrial oil & Iats products 6
    th
    ed, A Wiley Interscience publication, New York, v. 2, 2004.
    |3| M. Formo et al; Bailey`s industrial oil & Iats products 4
    th
    ed, A Wiley Interscience publication, New York, v. 1, 1979.
    PF.6.24
    Galacturonic acid recovery by electrodialysis
    E. Molnar, N. Nemestothy, K. BelaIi-Bako
    Research Institute of Chemical and Process Engineering, Pannon Universitv, Egvetem u. 10. P.O. Box 158, H-8200 Jes:prem,
    Hungarv
    bakomukki.richem.hu
    Galacturonic acid (GA) and derivates are valuable raw materials in Iood and cosmetic industries as acidic agents and Ior
    production oI vitamin C. Pectin rich agro wastes are good sources Ior manuIacture oI galacturonic acid. Pectin is a complex
    polysaccharide Iound in the primary cell walls and intercellular regions oI higher plants. Backbone oI pectin molecules is
    composed oI galacturonic acid as a monomer.
    Sugar beet pulp, apple pomace and other wastes (e.g. press cakes) Irom Iruit juice industry are pectin rich raw materials. To
    obtain galacturonic acid, pectin is extracted Irom raw materials then its enzymatic hydrolysis results in galacturonic acid (GA)
    in diluted aqueous solution.
    In this work the aim was to manuIacture galacturonic acid Irom various berries and sugar beet pulp. For this purpose Iirstly
    pectin was extracted with hot water Irom waste materials then enzymatic hydrolysis was carried out using Pectinex 100L
    enzyme preparation. The hydrolysate contains mainly carbohydrates (oligo- and monosaccharides) and galacturonic acid.
    Electrodialysis (ED) is considered as an eIIicient technology to separate charged compounds Irom an aquoeus solution. To
    remove galacturonic acid, ED seems a suitable process, because only galacturonic acid is present as a charged compound in the
    solution.
    -474-
    To obtain galacturonic acid Irom hydrolysate oI pectin two laboratory equipments were designed and built. Firstly a 2-step
    electrodialysis was used. In the Iirst step GA is removed Irom the hydrolysate by using an asymmetric ED cell containing
    cation and anion selective membranes and sodium galacturonate is obtained, then in the second step GA is recovered Irom its
    salt by an ED stack containing cation selective and bipolar membranes. Secondly an ED stack containing anion and cation
    selective and bipolar membranes was applied to obtain GA Irom hydrolysate.
    In our work sodium-galacturonate was used as model solution. Experiments with model solutions were carried out by the two
    set-ups to optimize parameters. EIIects oI voltage, electric current, concentrate oI solutions and temperature were studied.
    Then galacturonic acid was separated Irom hydrolysate oI pectin by optimized parameters. We Iound based on the
    experimental results that galacturonic acid could be eIIiciently recovered and concentrated Irom the hydrolysate oI pectins
    Irom various sources by using electrodialysis.
    PF.6.25
    Protein recovery in enzyme-assisted aqueous extraction processing of soybeans
    J.M.L.N. de Moura, N.M. de Almeida, K. Campbell, C.E. Glatz, L.A. Johnson
    Iowa State Universitv, Ames, IA, USA
    jnobregaiastate.edu
    Enzyme-assisted aqueous extraction processing (EAEP) oI soybeans produces a signiIicant amount oI protein-rich eIIluent
    (skim). In order to reduce eIIluent production, two-stage countercurrent EAEP was applied. Skims with diIIerent degrees oI
    proteolysis were produced: skim 1, where 0.5 protease (wt/g extruded Ilakes) was used in both extractions; skim 2, where
    enzyme was used in the 2
    nd
    extraction only; and skim 3, where no enzyme was used in either extraction. Protein extractions oI
    96, 90, and 65 were achieved when producing skims 1, 2 and 3, respectively. Protein recovery strategies using ultraIiltration
    (regenerated cellulose membrane) and upstream isoeletric precipitation were evaluated. Protein retentions oI 93.0 and 98.8
    and permeate Iluxes oI 1.1 and 0.3 kg/h.m
    2
    were achieved Ior skim 1 using 1 kDa and 500 Da membranes, respectively.
    Protein retentions oI 99.4 and 98.9 and permeate Iluxes up to 2.4 and 1.8 kg/h.m
    2
    were obtained in a double Iiltration (30
    kDa/500 Da) oI skims 2 and 3, respectively. Protein recoveries oI 28.0, 62.0, and 85.7 were obtained with isoeletric
    precipitation oI skims 1, 2, and 3, respectively. UltraIiltrations (500 Da) oI respective supernatants achieved protein retentions
    oI 98.3, 96.8, and 92.5 and permeate Iluxes oI 0.9, 1.3, and 1.5 kg/h.m
    2
    , respectively. High protein retentions were
    associated with low permeate Iluxes.
    PF.7.1
    Effect of polyethylene glycol on morphology and performance of polyvinyl alcohol
    hemodialysis membranes
    J. Barzin
    1
    , S.S. Madaeni
    2
    , S. Pourmoghadasi
    3
    1
    Biomaterials Department, Iran Polvmer and Petrochemical Institute, Tehran, Iran
    2
    Chemical Engineering Department, Ra:i Universitv, Kermanshah, Iran
    3
    Chemical Engineering Department, Tarbiat Modaress Universitv, Tehran, Iran
    smadaeniyahoo.com
    In hemodialysis devices, semi permeable membranes are the most important part to remove uremic toxin substances Irom
    blood oI kidney patients. Due to the superior permeability and blood compatibility, polyvinyl alcohol is used as a material Ior
    hemodialysis membranes. Flat-sheet hemodialysis membranes were prepared Irom polyvinyl alcohol with and without the
    addition oI polyethylene glycol using phase inversion process as the usual procedure Ior Iabrication oI asymmetric and
    symmetric polyvinyl alcohol Ilat-sheet and hollow Iiber membranes. Polymer solutions were prepared Irom polyvinyl alcohol
    (PVA) in distillated water as solvent with and without polyethylene glycol as additive. The coagulant bath solution was chosen
    the sodium sulIate and sodium hydroxide and Iinal Iixation oI membranes was carried out in sulIuric acid, sodium sulIate and
    glutaraldehyde aqueous solution. The removals oI uremic toxins (urea, uric acid, and creatinine) Irom human blood serum
    were measured Ior membrane perIormances estimation. EIIect oI increasing the polyethylene glycol on membrane morphology
    and dialysis perIormance was investigated and their relationships were correlated. The sponge structure oI the membranes
    prepared Irom PVA/water/NaOH and Na
    2
    SO
    4
    turns to dense structure when PVA concentration increases in the preparation
    -475-
    recipe resulting lower passage oI uremic toxins through the membranes. Addition oI a water-soluble pore Iormer polymer like
    PEG to the PVA solution leads to a porous sponge like structure and results in an improvement in removal oI uremic toxins.
    Key words: polyvinyl alcohole, phase inversion, membrane, uremic toxin, hemodialysis
    PF.7.2
    Preparation, characterization and application of a membrane microdevice
    H. Hassan
    1
    , A. Cano-Odena
    2
    , T. Gumi
    1
    1
    SYSTEMIC Research Group, Department of Chemical Engineering, Universitat Rovira i Jirgili, Avgda. Pasos Catalans 26,
    Tarragona 43007, Spain
    2
    Center for Surface Chemistrv and Catalvsis, Dept. MS, Faculteit Bio- ingenieurswetenschappen, K.U.Leuven, Kasteelpark
    Arenberg 23, Postbus 2461, B-3001 Leuven, Belgium
    hany.hassanestudiants.urv.cat
    Membranes are readily incorporated into microIluidic systems. Fabricating microstructure on chips is an approach to increase
    the surIace to volume ratio |1|. Due to the speciIic characteristics oI monolithic polymers, such as high crosslinking, rigidity oI
    their internal structure in the dry state, low mass transIer resistance, and the versatility oI introducing chemical Iunctionalities
    depending on the selection oI the monomer constituents, they have been used as separation media in HPLC application, solid
    phase interaction, gas chromatography and molecular recognition |2|.
    The aims oI our work are preparation oI a monolithic polymer-based micromembrane using monomers such as Hydroxymethyl
    methacrylate (HEMA) and Ethylene dimethacrylate (EDMA) |2| and incorporation oI the membrane into a microchip;
    characterization oI the micromembrane morphology and chemical properties (using various techniques: Scanning Electron
    Microscopy (SEM), image treatment, IR, etc.); and determination oI the inIluence oI chemical and physical parameters such as
    Ieed Ilowrate and concentration, working conditions, process reproducibility and system time oI liIe on a separation process
    perIormance, and consequently optimize it.
    |1| D. Peterson, Solid supports Ior micro analytical systems, Lab on a Chip, 2005, 5, 132-139
    |2| A. Cano, E. Moschou, S. Daunert, J. Coello, C. Palet, Optimization oI the xylan degradation activity oI monolithic
    enzymatic membranes as a Iunction oI their composition using design oI experiments, Bioprocess Biosyst. Eng., 2006,
    29:261-268
    PF.7.3
    Purification of a recombinant baculovirus by ion exchange membrane
    chromatography
    T. A. Grein
    1
    , Z. Kovacs
    1
    , R. Michalsky
    2
    , P. Czermak
    1, 2
    1
    Universitv of Applied Sciences Giessen-Friedberg, Institute of Biopharmaceutical Technologv, Wiesenstrasse 14, 35390
    Giessen, Germanv,
    2
    Department of Chemical Engineering, Kansas State Universitv, Manhattan, Kansas, 66506, U.S.A.
    Peter.Czermaktg.Ih-giessen.de
    Application oI viral vectors Ior gene delivery into mammalian cells requires the development oI eIIective techniques Ior the
    downstream processing oI viruses. The baculovirus Autographa caliIornica M nucleopolyhedrovirus (AcMNPV) is known as
    an insect biopesticide and potential vector Ior gene therapy. This virus is an enveloped virus that exists in two Iorms, budded
    virus (BV) and occluded virus (OV), but only the budded virus can penetrate into mammalian cells. For the production oI
    baculoviruses, Spodoptera Irugiperda ovarian cells (SF21-cells) were inIected with AcMNPV at a multiplicity oI inIection
    (MOI) oI 0.1 plaque Iorming units per cell (pIu/cell). The BV in the supernatant was harvested 5 days post inIection by
    centriIugation. This BV-suspension is consists oI cell Iragments and numerousness intracellular proteins oI the SF21-cells. In
    this work, the puriIication and concentration oI AcMNPV Irom the BV-Suspension is experimentally investigated applying ion
    exchange membrane chromatography (IEMC).The separation perIormances oI Iour diIIerent commercially available ion
    exchange membranes were tested. The puriIication oI AcMNPV by such adsoptive membrane based on speciIic interactions
    between the permeating compounds and the charges sites oI the membrane that can be controlled by pH adjustments. The virus
    -476-
    inIectivity was determined by TCID50 endpoint dilution method in the BV suspension, in the permeate and in the eluent. The
    puriIication degree oI the virus was analyzed by BradIord-Assay and a sodiumdodecylsulIate polyacrylamid gel
    electrophoresis. The puriIication oI the BV by IEMC is very complicated, because cell Iragments and BV-suspension have a
    similar isoelectric point. The observed separation behavior is discussed in respect to the applied pH oI the eluent, the charge
    and the binding capacity oI the diIIerent membranes.
    PF.7.4
    Preparation and characterization of urease immobilized ultrafiltration membranes
    Y. Yurekli
    1
    , S. Guedidi
    3,4
    , S. Alsoy Altinkaya
    1
    , A. Yemenicioglu
    2
    , C. Innocent
    3
    , A. Deratani
    3
    , S. Roudesli
    4
    1
    I:mir Institute of Technologv, Department of Chemical Engineering, Gulbahce Kovu, 35430, Urla I:mir, Turkev.
    2
    I:mir Institute of Technologv, Department of Food Engineering, Gulbahce Kovu, 35430, Urla I:mir, Turkev.
    3
    Institut Europeen des Membranes, Place Eugene Bataillon, CC 047, 34095 Montpellier, Cedex 5, France.
    4
    Laboratoire des Polvmeres-Biopolvmeres Materiaux Organiques, Faculte des Sciences de Monastir / Avenue de
    lEnvironnement 5019, Monastir, Tunisie.
    sacidealsoyiyte.edu.tr
    Immobilization oI enzymes on a solid support is absolutely among the most important problems in modern biotechnology.
    Activity, stability and selectivity oI the enzyme can be improved by immobilization. In addition, the reusability oI the
    immobilized enzyme in continuous processes becomes possible with eIIicient recycling and separation oI the components in
    the mixture can oIten be achieved by the enzyme immobilized support. In this study, urease was immobilized onto negatively
    charged polyacrylonitrile (PAN) and positively charged polyelectrolyte modiIied PAN with chitosan (PAN-CHI) and
    polyethyleneimine (PAN-PEI). The stability oI Iree and immobilized urease in long term storage as well as their optimum pH,
    temperature and kinetic parameters were determined. The results indicated that polyelectrolyte deposition did not considerably
    aIIect the amount oI urease immobilized onto PAN membranes. In contrast, maximum catalytic activity oI the PAN membrane
    increased with chitosan and PEI depositions. pH and temperature proIiles oI urease were not signiIicantly aIIected by
    polyelectrolyte deposition, however, its long term storage stability was improved. The 95 oI initial activity oI urease
    immobilized onto PAN membrane was lost in 5 days while the immobilized urease in PAN-CHI and PAN-PEI membranes
    maintained 9 and 26 oI its initial activity aIter 28 days cold storage, respectively. The contribution oI layer by layer selI
    assembly on the long term storage stability oI urease was also investigated. At the end oI 28 days oI cold storage, urease (U)
    immobilized between PEI (PAN-PEI-U-PEI) and chitosan layers (PAN-CHI-U-CHI) maintained 51 and 43 oI its initial
    activity , respectively. The results suggest that the immobilization oI enzymes on the layer oI polyelectrolytes can be a
    promising approach Ior enhancing the reactivity oI the membranes and their utility in biotechnology. Also, the layer-by-layer
    selI-assembly method seems to be versatile due to its simplicity and enhancing the storage stability oI the immobilized
    enzyme.
    Acknowlegment: The authors would like to thank The ScientiIic and Technical Research Council oI Turkey and The Ministry
    oI Foreign AIIairs oI the Republic oI France Ior partial Iunding (IFC) and the Gambro-Hospal, Lyon, France Ior kindly
    providing the membranes.
    PF.7.5
    Nexterion NC/UniSart slides: nitro cellulose coated substrates for optimal
    performance and high reproducibility in protein microarray applications
    U. Andag
    1
    , M. Hollas
    1
    , E. Jallerat
    1
    , S. Drebing
    1
    , K. Fritz
    1
    , K. PIlanz
    1
    , D. Melzner
    1
    , A. Rees
    2
    , R. Dietrich
    2
    1
    SARTORIUS STEDIM BIOTECH GmbH, August-Spindler-Strasse 11, D-37079 Goettingen, Germanv
    2
    SCHOTT JENAer GLAS GmbH, Otto-Schott-Str. 13, D-07745 Jena, Germanv
    uwe.andagsartorius-stedim.com
    Protein biochips have become an indispensable tool Ior many proteomic applications, and are now being developed Ior use in
    array-based clinical diagnostic tests. The ability to array multiple proteins as microscopic spots onto a slide surIace allows the
    simultaneously analysis oI numerous interactions. Another major advantage is that the sample and reagent volumes needed to
    -477-
    perIorm the assay are signiIicantly lower than Ior standard diagnostic tools, such as ELISA or Lateral Flow Immunoassays
    (LFIA).
    For several decades, nitrocellulose membranes have proved their worth in diagnostic lateral Ilow applications, and have been
    shown to give a superior and more reliable perIormance than synthetic porous materials. SARTORIUS STEDIM BIOTECH,
    in a close collaboration with SCHOTT, has recently developed a new nitrocellulose-based substrate Ior protein microarray
    applications. The Nexterion NC/UniSart slides are high quality glass slides coated with a speciIically developed thin 3-
    dimensional microporous nitrocellulose (NC) membrane. SARTORIUS STEDIM BIOTECH has optimized the structure,
    composition, and perIormance characteristics oI the nitrocellulose Ior protein microarray applications.
    A detailed description oI the slide characteristics, such as membrane structure as shown by scanning electron microscopy
    (SEM) analysis, non-speciIic background Iluorescence, wetting behavior, and protein binding capacity will be presented.
    Functional assay data on quantiIication oI human IgG antibodies Irom cell culture medium using Nexterion NC/UniSart slides
    will also be shown.
    In addition, a side-by-side comparison oI diIIerent 3-dimensional membrane slides vs. 2-dimensional nitro cellulose ('FILM)
    slides will illustrate the advantages and disadvantages oI each substrate/Iormat Ior the use in protein microarray applications.
    PF.7.6
    Novel membrane adsorbers for large scale downstream processing
    D. Melzner, R. Faber, W. Demmer, H.-H. Hrl
    JP Membrane Technologv, Sartorius Stedim Biotech GmbH, August-Spindler-Str. 11, 37079 Gttingen, Germanv.
    dieter.melznersartorius-stedim.com
    New membrane adsorbers were designed Ior use in membrane chromatography applications. A novel double-porous cellulose
    structure was developed to overcome the limitations oI prior art stationary phases. The hydrophilic stabilized regenerated
    cellulose membrane support possesses excellent mechanical and chemical stability. The binding capacities are in the range oI
    conventional chromatography resins even at signiIicantly higher Ilow rates.
    A new Sartobind

    Phenyl membrane adsorber was developed Ior large scale puriIication oI biomolecules based on
    hydrophobic interaction chromatography (HIC) principles. The new hydrophobic membrane adsorber combine the advantages
    oI membrane chromatography: having virtually no diIIusion limitation oI mass transIer, shorter processing time due to the
    open macroporous structure, and a ready-to-use disposable capsule Iormat that eliminates the need Ior re-use validation at large
    scale. The binding capacity Ior proteins is comparable to conventional HIC resins. These advantages make Sartobind Phenyl
    applicable Ior Ilow-through as well as bind-and-elute large scale applications.
    New membrane adsorbers (STIC) intended Ior contaminant removal in puriIication oI monoclonal antibodies were developed.
    The combination oI novel membrane structure and appropriate surIace chemistry results in improved tolerance to changes in
    process conditions Ior removal oI host cell proteins, DNA, viruses or endotoxins.
    Properties oI the new membrane support, HIC and STIC membrane adsorbers are presented.
    PF.7.7
    Separation of selected pharmaceuticals from waters by liquid membrane systems
    N. Pont, V. Salvado, C. Fontas
    Department of Chemistrv, Universitv of Girona, 17071 Girona, Spain
    claudia.Iontasudg.edu
    Tetracyclines (TCs) are a broad spectrum oI antibiotics which are widely used Ior both prevention and treatment oI bacterial
    inIections in both humans and animals. The widespread use oI TCs could lead to Iind their residues in surIace waters and
    animal based Ioods, and due to their potential adverse eIIects on environment and humans, it is critical to develop reliable
    analytical methods Ior routine monitoring oI TCs. Among the TCs commercially available, Iour are the most commonly
    applied to Iood-producing animals: tetracycline (TC), oxytetracycline (OTC), chlortetracycline (ClTC) and doxycycline (DC).
    These compounds are highly polar and may exist with diIIerent charges depending on the pH oI the sample.
    Their detection in environmental or Iood samples is diIIicult because the samples cannot be directly measured by analytical
    instrumentation due to complex matrices or low concentrations. ThereIore, beIore analysis, normally both sample cleanup, to
    remove most oI the matrix, and preconcentration, to obtain maximum measurement sensitivity, are required.
    -478-
    In this study, we present the development oI a supported liquid membrane (SLM) system as a sample pretreatment method to
    isolate TCs and thus, Iacilitating their analysis by conventional HPLC-UV instrumentation. For that, and taking into account
    that TCs are pH-dependent, we have investigated the possibility oI using the commercial anion-exchange extractant
    tricaprylmethylammonium chloride (Aliquat 336) as carrier Ior the Iour compounds. The inIluence oI the diIIerent chemical
    parameters aIIecting the transport oI TCs through the SLM has been investigated being the eIIect oI pH in the Ieed phase
    primordial. The best extraction conditions were achieved by adjusting the pH oI the aqueous Ieed phase to 12 and using as
    receiving phase a 10
    -2
    M HCl solution. Moreover, the composition oI the liquid membrane has also been optimized in terms oI
    carrier concentration and organic solvent. Better results were obtained when working with a 0.5 M Aliquat 336 in decaline
    solution.
    Finally, the designed SLM system has been applied to the separation oI TCs in several environmental samples.
    C. R. Anderson, H. S. Rupp, W-H. Wu, Complexities in tetracycline analysis-chemistry, matrix extraction, cleanup, and liquid
    chromatography, J. Chromatogr. A, 2005, 1075 23-32.
    S. Shariati, Y. Yamini, A. EsraIili, Carrier mediated hollow Iiber liquid phase microextraction combined with HPLC-UV Ior
    preconcentration and determination oI some tetracyclines antibiotics, J. Chromatogr. B, 2008, 877, 393-400.
    The Iinancial support by Ministerio de Ciencia e Inovacion through Project CTM2008-06847-C02-02/TECNO is grateIully
    acknowledged.
    PF.7.8
    Basics in format development for immunoassays: comparison of classical protein
    microarrays & lateral flow systems
    S. Beck
    1
    , D. Husler
    1
    , S. Dbel
    2
    , F. Gessler
    3
    , U. Andag
    1
    , M. Hollas
    1
    , K. PIlanz
    1

    1
    Sartorius Stedim Biotech, August-Spindler-Str. 11, D-37079 Goettingen, Germanv
    2
    Technical Universitv of Braunschweig, Institute for Biochemistrv and Biotechnologv, Spielmannstr. 7, D-38106
    Braunschweig, Germanv
    3
    Miprolab, Marie-Curie Str. 7, D-37079 Goettingen, Germanv
    Karl.pIlanzsartorius-stedim.com
    In this study, perIormance oI porous Cellulose Nitrate (CN) Protein Microarray substrates that are incubated in typical
    hybridisation chambers is compared to CN Iormats, where incubation and washing steps are driven by a Lateral Flow process
    through the 3-dimensional porous structure oI the substrate.
    Lateral Flow driven Diagnostic Immunochromatographic tests have gained widespread use. More than 3 Billion tests per year
    are currently used. Ease oI use, low time to signal, highly speciIic and sensitive results even at low target concentrations as
    well as the low costs per test ( 10 Euro/test) are driving Iactors Ior this success story. Most oI these tests are based on CN
    porous structures with pore size in the range oI 10 m and a membrane thickness ~ 100 m. Pore size as well as thickness are
    optimized Ior the speciIic application, taking into account the need Ior Iast lateral Ilow (typical wetting time is below 2 min,
    total test time including clearance 10 min) as well as the active surIace area resulting in the sensitivity. Test strips oI 2-5 mm
    width and several centimetre lengths consist oI sample and release pad, the porous CN membrane test area, where the
    Immunomarkers are linked and the adsorbent pad providing the driving Iorce Ior eIIicient sample Ilow. Typically such tests are
    limited to only one, in some cases up to Iive analytes that can be monitored simultaneously. In these multiplex test systems the
    diIIerent test zones are applied as lines behind each other in direction oI the lateral Ilow.
    Since recently, a certain need oI higher throughput in sample analysis oI the proteomic area, the multiplicity oI test Iormats
    have created a protein microarray market Iollowing the DNA array technology using very similar instrumentation. The
    microarray technology allows the simultaneous analysis oI hundreds oI immunoreactions by a single test system. Following
    DNA based technology the protein microarray systems typically use a slide Iormat, which Iits into respective instruments Ior
    sample/capture reagent spotting, hybridization and signal detection. In contrast to Ilat substrates Ior DNA microarray analysis,
    CN coated glass slides provide an optimized surIace Ior protein microarray applications due to higher speciIic active surIace
    and enormous unspeciIic protein binding capacity. At these classical microarray Iormats, all hybridization steps are perIormed
    Irom the top side oI the substrate. So Iar, optimal structures seemed to be similar to blotting membranes based on pore sizes in
    the range oI 0,2m and a layer thickness oI app 10 m.
    As given above both diagnostic Iormats, protein microarray and lateral Ilow assay, are based on the same immunological
    principle, both using a CN matrix. However, they diIIer signiIicantly in their mode oI application as well as the morphology
    (pore size/structure) oI the matrix. This study will highlight the diIIerences between these two set ups giving indications oI
    their limits as well as giving an outlook to an optimized new slide Iormat making use oI lateral Ilow principle.
    -479-
    PF.7.9
    Dual membrane diafiltration (DMD) process for pharmaceutical and nutraceutical
    purifications
    I. Sereewatthanawut
    1
    , F.W. Lim
    1
    , M. Makowski
    1
    , Y. Bhole
    2
    , A.G. Livingston
    2
    , A.T. Boam
    1
    1
    Membrane Extraction Technologv Ltd., Unit 25, Talina Centre, Baglevs Lane, Fulham, London SW6 2BW, UK
    2
    Department of Chemical Engineering and Chemical Technologv, Imperial College London, Exhibition Road, London, SW7
    2AZ, UK.
    ibsmembrane-extraction-technology.com
    Impurities are a hurdle in most pharmaceutical and nutraceutical production processes, as tiny amounts oI impurities can
    signiIicantly aIIect the end-product quality. Together with tight saIety regulations in these industries, the removal oI impurities
    is a major concern.|1| Apart Irom this issue, Ior the production oI pharmaceuticals and Iine chemicals, it is generally desirable
    to recover expensive species, e.g. catalysts, by-products, solvents and other high value unreacted materials. Current state-oI-
    the-art technologies include distillation, crystallisation and column chromatography. In recent years, membrane technology,
    particularly organic solvent nanoIiltration (OSN), has attracted a great deal oI attention as an alternative puriIication
    technology at the molecular level. The main advantage oI employing OSN Ior puriIication oI active pharmaceutical ingredients
    (APIs) or high value nutraceutical compounds (HVNCs) is that by selecting suitable molecular weight cut-oII (MWCO)
    membranes, this technology can be used to separate molecules oI similar molecular weight (e.g. in the 200 to 1000 Da range)
    and physical properties at a much lower operating temperature compared to conventional processing operations. In addition to
    the large savings in energy costs, APIs and HVNCs are oIten susceptible to thermal damage and thus the milder operating
    conditions oI a membrane process can minimise the active and/or nutritive value loss due to thermal degradation.
    This study reports the invention oI a novel Dual Membrane DiaIiltration (DMD) process which utilises the recently available
    highly stable Duramem
    TM
    membrane series Ior the puriIication oI organic compounds in key industrial solvents including
    tetrahydroIuran (THF) and dimethyl Iormamide (DMF).|2,3| In addition to the advantages mentioned earlier, the process also
    combines the puriIication unit with the solvent recovery unit thus minimizing the amount oI solvents used. In this study, to
    mimic typical industrial applications Ior pharmaceutical and nutraceutical production (e.g. puriIication oI dimers in
    downstream mixture or removal oI Iree Iatty acids Irom glycerides in natural oils), a pair oI small (MW200 to 300 Da) and
    large (MW600 to 800 Da) organic dyes were used as markers. DiIIerent series oI Duramem
    TM
    spiral-wound modules were
    employed to demonstrate the Ieasibility oI the process at pilot-scale.
    |1| Q3C(R3): Impurities: Guideline Ior Residual Solvents. International ConIerence on Harmonisation oI Technical
    Requirements Ior Registration oI Pharmaceuticals Ior Human Use (2005).
    |2| Y.H. See-Toh, F.W. Lim, and A. Livingston, Polymeric Membranes Ior NanoIiltration in Polar Aprotic Solvents, J.
    Membr. Sci., 301 (2007) 3.
    |3| Y.H. See-Toh, M. Silva, and A.G. Livingston, Controlling Molecular Weight Cut-OII Curves Ior Highly Solvent Stable
    Organic Solvent NanoIiltration (OSN) Membranes, J. Membr. Sci., 324 (2008) 220.
    PF.7.10
    Fouling index in tangential membrane filtration applied for separation of
    cephamycin C from fermentation broths
    A. Baptista Neto
    1
    , F. Pearubia
    1
    , C.O. Hokka
    1
    , M. Barboza
    1

    1
    Department of Chemical Engineering Federal Universitv of So Carlos, Jia Washington Lui:, km 235, 13565-905 So
    Carlos SP Bra:il
    marleiuIscar.br
    The design oI membranes Iiltration permits cross-flow or tangential Iiltration: retentate Ilows across the surIace oI the
    membrane, on the upstream side, while the permeate Ilows out oI the downstream surIace oI the membrane. Separation
    membranes are applied to a wide range oI tasks and these can be classiIied broadly as microIiltration (MF), ultraIiltration (UF)
    and nanoIiltration (NF). MF and UF are widely used as a Iirst step in the clariIication oI Iluids or recovery oI solutes. MF and
    UF appear to be a suitable alternative method Ior the separation oI biomass and proteins Irom antibiotics Iermentation broth, in
    view oI the Ilexibility oI such techniques |1|. However, the steady decline in the Ilux oI permeate during Iiltering has negative
    economic consequences and demands a diaIiltration stage, which in turn produces more diluted broths. InIormation on the
    -480-
    relation between the operating conditions and Iouling is important when these conditions are being deIined and may even play
    a part in deIining the composition oI the culture medium used in the production phase. Cephamycin C (CepC) is a -lactam
    compound Iirst isolated Irom Streptomvces clavuligerus as an inhibitor oI the synthesis oI the Gram-negative cell wall |3|. In
    view oI the potential advantages oI applying membranes techniques to the separation and puriIication oI antibiotics, the present
    study was elaborated in order to assess the inIluence oI temperature, hydrostatic pressure drop across the membrane (P
    TM
    ) and
    Ieed rate on the permeate Ilux and on the Iormation oI the gel layer that leads to membrane Iouling, in commercial membranes
    used Ior UF. CepC was measured biologically at each stage by assaying its activity against the bacterial strain, Escherichia
    coli ESS. The eIIiciency oI puriIication by ultraIiltration was measured by UV spectrophotometry. Regarding UF, it was Iound
    that raising P
    TM
    did not lead to a proportional rise in Ilux. UltraIiltrations, a rise in pressure leads in general to a greater Ilux oI
    permeate; however, this is not guaranteed, owing to the increased polarization oI the gel layer and greater membrane resistance
    that accompany a higher P
    TM
    .
    |1| A. M. Brites Alves, A. Moro, J. P. Cardoso, Isolation oI antibiotics Irom industrial Iermentation broths using membrane
    technology, Desalination 148 (2002) 181-186.
    |2| Charcosset, C.; Membrane process in biotechnology: An overview, Biotechnologv Advances; v. 24, p.482-492, 2006
    |3| Baggaley, K. H.; Brown, A. G. and SchoIield, C. J., Chemistry and biosynthesis oI clavulanic acid and another clavans,
    Natural Product Report, v.14, n
    o
    4 , (1997) 309-333.
    PF.7.11
    Membrane-based technologies in the separation and purification of whey proteins
    R. Ibaez, M.P. Mier, V. Diaz, I. Ortiz
    Dpto. Ingenieria Quimica v Quimica Inorganica, ETSIIvT - Universidad de Cantabria, Avda. de los Castros s/n 39005
    Santander, Spain.
    ibanezrunican.es
    Membrane-based processes are playing critical role in the Iield oI separation/puriIication oI biotechnological products. Due to
    the increasing market oI pure protein Iractions worldwide, the isolation oI these compounds is becoming one oI the most
    important applications in this Iield. Milk and whey proteins present an especial signiIicance because oI their exceptional
    biological value and science is Iinding increasing nutritional and Iunctional characteristics in this group |1-3|. A big number oI
    contributions can be Iound in literature concerning research and development oI membrane technologies in the Iiled oI milk
    protein separation such as UF, MF, electrodialysis with bipolar membranes (EDBM) or high perIormance tangential Ilow
    Iiltration (HPTFF) |1,6|.
    In this study, the separation oI bovine serum albumin (BSA) (69kDa - pI-4.8) and lactoIerrin (bLF) (78kDa - pI-8) has been
    selected as study case due to the increasing importance oI both proteins and the diIIiculty to obtain adequate separation with
    the use oI conventional processes. Taking into account the similitude between both proteins in size and weight the diIIerence in
    the pI value has been used as separation criteria by applying ultraIiltratrion by charged membranes. Two diIIerent membranes
    have been evaluated: a) commercial membrane: BIOMAX 100 and b) prototype Irom Millipore, 100 kDa positively charged
    |4,5|. The novelty oI these membranes is the Iact that they have a net charge either positive or negative. The use oI
    semipermeable membranes Ior the separation oI proteins without limit to their relative size is deIined as high-perIormance
    Tangential Ilow Iiltration (HPTFF) |6,7|.
    Employing synthetic solutions
    with BSA and bLF initial
    concentrations similar to those
    in whey solutions UF
    experiments have been carried
    out working with diIIerent pH
    values.
    Results have been expressed in
    terms oI selectivity (Iigure 1)
    Ior both membranes
    The use oI pH equals to the Ip oI any oI the proteins increases the selectivity. The best results, in both membranes, can be
    obtained when working at pH equal to bLF Ip.
    Acknowledgements: Financial support Irom Spanish Ministry oI Science and innovation, project CTQ2008-03225/PPQ is
    grateIully acknowledged M.P. Mier thanks the Ministry oI Education and Science Ior the F.P.U. Iellowship.
    -481-
    Figure 1. BSA /bLF separation selectivity Ior diIIerent pH.
    |1| A. Saxena, B. P. Tripathi, M. Kumar, V. K. Shahi, Membrane-based techniques Ior the separation and puriIication oI
    proteins: an overview, Advances in colloid and interIace Science 145 (2008) 1-22.
    |2| G. W. Smithhers, Whey and Whey proteins- Irom gutter-to-gold`. International dairy Journal 18 (2008) 695-704.
    |3| M.P. Mier, R. Ibaez, I. Ortiz, InIluence oI process variables on the separation oI casein Irom milk by Electrodialysis with
    Bipolar Membranes, Biochemical Engineering Journal 40 (2008) 304 - 311.
    |4| P. Mier, Contribution to research and development oI electrodialysis with bipolar membranes technology (2008). Doctoral
    Tesis. Universidad de Cantabria (Spain)
    |5| R. van Reis, S. Gadam, L.N. Frautschy, S. Orlando, E.M. Goodrich, S. Saksena, R. Kuriyel, C.M. Simpson, S. Pearl, A.L.
    Zydney, High perIormance tangential Ilow Iiltration, Biotechnology and Bioengineering 56 (1997) 71-82.
    |6| A.L. Zydney and R. Kuryel, High perIormance Tangential Flow Filtration Ior Protein Separation. In methods in
    Biotechnology. Vol 9:. (2000). Edited by: M.A: Desai. Humana press Inc. Totowa. NJ
    |7| R. van Reis, J.M. Brake, J. Charkoudian, D.B. Burns, A.L. Zydney, High-perIormance tangential Ilow Iiltration using
    charged membranes, Journal oI Membrane Science 159 (1999) 133-142.
    PF.7.12
    Preparation, characterization and application of molecularly imprinted membranes
    (MIM) for the separation of DL-selenomethionine
    A. Conesa
    1
    , T. Gumi
    2
    , C. Palet
    1

    1
    Centre Grup de Tecniques de Separacio en Quimica, Unitat de Quimica Analitica, Departament de Quimica, Universitat
    Autonoma de Barcelona, 08193-Bellaterra, Catalunva, Spain.
    2
    Departament dEnginveria Quimica, ETSEQ, Universitat Rovira i Jirgili, Av. Pasos Catalans 26, 43007-Tarragona,
    Catalunva, Spain.
    Cristina.Paletuab.es
    Selenium is an essential element Ior the human an animal heath. Selenomethionine and particularly L-selenomethionine is the
    majority specie oI selenium that we Iind in the natural Ioods. In consequence, the assimilation with the nutrition to create stock
    oI selenium in the body is less eIIective with selenite than with selenomethionine. |i| Besides, L-selenomethionine presents
    antioxidant eIIect and it is better retained in the corporal tissues. On account that the L-selenomethionine can not be
    synthesized by animals and humans the way to administrate the L-selenomethionine in the diet is by bioIortiIication oI yeast or
    wheat, or by the asymmetric synthesis route. An alternative may be the separation oI the racemic by membrane technology.
    Here we present the possibility to separate the chiral mixture oI DL-selenomethionine by Molecularly Imprinted Membranes
    (MIM). The molecular imprinting procedure is generally based on the linkage oI suitable monomers containing Iunctional
    groups to template molecules by covalent or non-covalent interactions. Subsequent copolymeritzation oI the resulting template
    monomer assembly with in the presence oI a porogenic solvent produces rigid macroporus polymers. Removal oI the template
    molecules leaves cavities determined by the structure oI the template molecules. |ii| Four types oI MIM were here prepared
    over an hydrophobic polyvinylidene Iluoride (PVDF-phob) support using 4-vinylpiridine (4VPY), methacrylic acid (MAA),
    acrylamide (AAM) or N,N-dimethyl-2-aminoethylmethacrylate (DMAEM) co-polymerized with the cross-linker glycol
    dimethacrylate (EDMA). Polymerization was perIormed in methanol solvent, employing benzoin ethyl ether (BEE) as initiator,
    |iii| and Iollowing the M. Ulbricht et. al. process. The separation was carried out in a dialysis membrane cell at diIIerent pH
    phases conveniently buIIered.
    DiIIerent techniques such as Scanning Electron Microscopy (SEM), Attenuated Total ReIlection/Fourier TransIorm InIrared
    (ATR/ FTIR) and
    13
    C solid Cross-Polarization Magic Angle Spinning (CP/MAS) Nuclear Magnetic Resonance (NMR) were
    used to ensure that the co-polymer deposition on the PVDF-phob supported. Besides, other types oI characterization such as
    degree oI modiIication or water Ilux were calculated.
    The best chiral separation between the racemic DL-selenomethionine was obtained in case oI the imprinted membrane
    synthesized with the monomer DMAEM. The optimum conditions was at pH 6 oI Ieed and stripping phases and the separation
    Iactor obtained was 1.75.
    |i| R. Abdulah, K. Miyazaki, M. Nakazawa and H. Koyama, Chemical Iorms oI selenium Ior cancer prevention, Journal oI
    trace Elements in Medicine and Biology, 19 (2-3) (2005) 141-150.
    |ii| B. Sellergren, Molecularly imprinted polymers. Man-made mimics oI antibodies and their applications in analytical
    chemistry, Iirst edition by elsevier, Netherlands 2001.
    |iii| V. Kochkodan, W. Weigel and M. Ulbricht, Thin layer moleculary imprinted microIiltration membranes by
    photoIunctionalization using a coated a-cleavage photoinitiator, Analyst, 126 (2001) 803-809.
    -482-
    PF.8.1
    Transport mechanism of the polyamines through the supported liquid membranes,
    process optimization and possible medical applications.
    K. Pokajewicz, P.P. Wieczorek
    Universitv of Opole, Facultv of Chemistrv, ul. Oleska 48, 45-052 Opole, Poland.
    piotr.wieczorekuni.opole.pl
    Polyamines are small, simple aliphatic amines with versatile and still not Iully revealed Iunctions. They gained international
    attention oI scientists since the discovery made by Russell who Iound out that elevated concentrations oI polyamines are
    present in blood and urine oI cancer patients |1|. Polyamines turned out to be cancer markers that can be used Ior monitoring
    oI the eIIicacy oI the applied treatment, prognosis and early detection oI tumor reoccurrence and metastasis |2-4|. Despite the
    Iact oI possible clinical useIulness polyamines are not used in clinical routine as their analysis is very time and labor
    consuming. Simple and commonly applied immunological techniques (ELISA or RIA) are not applicable Ior polyamines since
    they are to small to be speciIically targeted by antibody. ThereIore other techniques like high perIormance liquid
    chromatography or capillary electrophoresis have to be used. These techniques require rigorous sample pretreatment. The most
    popular technique used Ior polyamines is liquid-liquid extraction, which consumes large volumes oI organic solvents, is
    diIIicult to automation and oIten the emulsion Iormation makes it very problematic. The usage oI porous polymer membrane
    as a support Ior the organic liquid poses many advantages. The technique is called supported liquid membrane (SLM)
    extraction and enables to combine extraction oI analyte to organic phase and its reextraction to the aqueous phase in one
    process. The technique is cheap, leaves extremely little organic liquid waste, consumes little labor and time. It makes possible
    to clean up and concentrate the analytes to the levels detectable by analytical equipment. The supported liquid membrane
    extraction with anionic carrier D2EHPA was employed by us as a sample pretreatment technique Ior polyamine analysis.
    The transport mechanism was investigated by means oI equilibrium methods and NMR technique. The whole SLM extraction
    process was studied to optimize perIormance. DiIIerent extraction set ups were utilized and compared. The optimized method
    was applied Ior samples such as urine, plasma and tissue. The SLM extraction oIIers satisIactory extraction eIIiciency and very
    good enrichment oI polyamines that enables polyamines analysis Irom the studied medical samples.
    |1| D.H. Russell, Increased polyamine concentrations in the urine oI human cancer patients, Nat. New Biol., 1971, 144-145.
    |2| W.E. Criss, A review oI polyamines and cancer, Turk. J. Med. Sci., 2003, 33, 195-205
    |3| Russell, D.H., Clinical Relevance oI polyamines as biochemical markers oI tumor kinetics. Clin. Chem., 1977, 23(1),
    22-27.
    |4| D.H. Russell, S.D. Russell, Relative useIulness oI measuring polyamines in serum, plasma and urine as biochemical
    markers oI cancer, Clin. Chem., 1975, 21(7), 860-863.
    PF.8.2
    Mixed matrix membranes for blood purification
    J. Sun
    1,2
    , S. SaiIul
    2
    , Z. Borneman
    2
    , D.F. Stamatialis
    2
    , M. Wessling
    2
    1
    State Kev Laboratorv for modification of Chemical Fibers and Polvmer Materials, College of Material Science &
    Engineering, Donghua Universitv, North People Rd. 2999, Songfiang, Shanghai 201620, P.R.China
    2
    Membrane Technologv Group, Facultv of Science and Technologv, Universitv of Twente, P.O.Box 217, NL 7500 AE
    Enschede, The Netherlands
    d.stamatialisutwente.nl
    Chronic kidney Iailure requires the treatment using an artiIicial kidney called dialysis. UnIortunately, dialysis treatment is only
    partially successIul in the treatment oI patients. One oI the main reasons is that hemodialysis is not very eIIective in removing
    larger and protein-bound uremic toxins. This can be partially achieved when dialysis is combined with hemoperIusion (or
    plasmaperIusion).
    In this work, we develop a mixed matrix membrane (MMM) |1| Ior selective adsorption and removal oI toxins Irom blood
    combining diIIusion and absorption in one step. In our concept, integral mixed matrix double layer membranes consisting oI an
    active support and a separating layer are prepared by co-casting. The active support layer consists oI activated carbon (AC)
    particles embedded in macroporous polymer; the separating layer consists oI particles Iree oI polymer. The particle Iree top
    layer prevents blood contact with adsorbent particles (Fig. 1) |2|.
    -483-
    Figure 1. Scanning electron microscopy image oI double layer MMM containing activated carbon (AC).
    The MMM adsorber has been evaluated using model solution oI Bovine Serum Albumin (BSA) and Creatinin (Crt).
    Preliminary results show that the MMM is capable to selectively capture creatinin Irom the solution. The BSA retention by the
    membrane is very low and the total Ilux through the membrane is high at low transmembrane pressure |2|.
    |1| Avramescu, M.E., Girones, M., Borneman, Z. & Wessling, M. Preparation oI mixed matrix adsorber membranes Ior
    protein recovery. J . Memb. Sci., 218, 2003, 219-233.
    |2| SaiIul S, 'Mixed matrix membrane adsorbers Ior protein and blood puriIication, PhD thesis, University oI Twente (2007).
    ISBN: 978-90-365-2507-7.
    PF.8.3
    Modelling of the dielectric properties in the biological and artificial membrane
    stimulates by electric circuit RC
    N. Nesralla, F. Hamdach, S. Bahlouli, N. Benharrat
    Laboratoire de phvsique des plasmas et des materiaux conducteurs et leurs applications.U.S.T.O Faculte des Sciences,
    Departement de phvsique U.S.T.O et MNAOUR B.P.1505 Oran. (Algeria)
    nesrallahnhotmail.com Nnesrallahavl.sonatrach.dz
    According to the noble price oI 2003 in chemistry or structural biology , the Molecular modeling became oI a major interest to
    explain in a simple way the properties oI ionic transport in the plasmic membrane biological or artiIicial, it is the subject thus
    oI an increasing number oI research tasks and specialized scientiIic publications . In addition, the membranes present
    capacitive and resistive eIIects related to the more or less great Iacility oI the diIIusible movements oI ions generated by the
    installation oI the gradients oI potential and the gradients oI concentration. As well as the passage oI ions with through the
    membrane creates an electric potential this can transIorm electric messages Irom one cellular membrane to another. Because oI
    its bored insulating lipidic layer pores 'transmembrane protein which ensures certain conductivity by the means oI the ions
    presents in solution, the cellular membrane behaves locally like one imperIect condenser. This study enables us to deduce the
    channels dependent on the transmembrane potential Ior diIIerent cellular rays and to also study the permeability oI the ions Na
    , K, Cl
    -
    in the plasmic membrane Ior an electric Iield threshold oI the order 10
    2
    v/cm , we will study also the ionic
    phenomenon oI diIIusion on the surIace oI the cellular membrane oI spherical Iorm which leads to the appearance oI a dipole
    on the cellular scale by two Irequency bands characteristic ' low Irequency BF and high Irequency HF '. According to these
    two Irequencies, we will study the phenomenon oI polarization and the membrane permeability by skew oI the permittivity cm,
    and membrane conductivity om.
    We will discuss also the phenomenon oI the discharge or the polarization oI double-layered membrane, this translated oI the
    Iacility oI the membrane 'to accumulate loads enter the two low Irequency compartments. On the other hand high Irequency, it
    thus authorizes the circulation oI the ionic loads the depolarization oI double-layered membrane, it is where the role oI the
    capacitive reactance intervenes Cm in membrane transport and the power oI dissipation Pm. These discoveries on the molecular
    channels enable us 'to include/understand at the molecular level how, Ior example, the kidney withdraws the water oI the
    primary urine and how the electric signals emitted in our nervous cells appear and are propagated. This can prove oI great
    importance Ior the comprehension oI renal, cardiac, muscular diseases or aIIecting the nervous system.
    -484-
    PF.9.1
    All-solid-state taste sensor with lipid-polymer membranes for discrimination of soft
    drinks
    M. Szpakowska, E. Marjanska
    Commoditv Science Department, Facultv of Management and Economics, Gdansk Univeristv of Technologv, Narutowic:a
    11/12, 80-952 Gdansk, Poland.
    ewamzie.pg.gda.pl
    There is a need oI elaboration oI a cost-eIIective and an eIIicient method oI Iood quality assessment in Iood industry. Among
    many possibilities, quality can be deIined as a uniIormity around a target value |1|. A Iour channel taste sensor composed oI
    all-solid-state electrodes have been proposed |2,3|. This work presents all-solid-state sensor with Iour electrodes. Each all-
    solid-state electrode contains two polymeric membrane layers covering glassy carbon. First sub layer was composed oI
    electroactive polymer poly (3,4 ethylenedioxythiophene) doped with polystyrene sulIonate. The second outer layer oI the
    sensor was an ion selective lipophilic compound polymer membrane. There is no requirement oI special sample preparation
    beIore measurement. The raw taste sensor data include Iour electrodes potentials in response to various soIt drinks Irom
    diIIerent branches (tonics, orangeades, Coca-Cola, Pepsi). In order to distinguish among the analysed samples and discriminate
    their characteristic taste properties the Iollowing chemometric methods were applied: Principal Component Analysis, (PCA),
    Partial Least Squares (PLS), K-Nearest Neighbours (KNN), SoIt Independent Modelling oI Class Analogy (SIMCA).
    The application oI all-solid-state taste sensor Ior distinguishing oI soIt drinks and beers Irom diIIerent branches was discussed.
    |1| G. Taguchi, Taguchi on Robust Technologv Development, ASME Press, 1992, 68.
    |2| L. Lvova, A. Legin, Y. Vlasov, G. Sig Cha, H. Nam, Multicomponent analysis oI Korean green tea by means oI disposable
    all-solid-state potentiometric electronic tongue microsystem, Sensor & Actuators, B 2003, 95, 391.
    |3| M. Szpakowska, E. Marjanska, A. Lisowska-Oleksiak, Investigation oI sour substances by a set oI all-solid-state membrane
    electrodes, Desalination (in press).
    PF.9.2
    Selective sensor utilizing monocrystal-thin b-oriented silicalite-1 layer-Metglas
    assembly
    L. Gora
    1,3
    , J. Kuhn
    2,3
    , Th. Baimpos
    4
    , V. Nikolakis
    4
    , F. Kapteijn
    3
    , E. M. Serwicka
    1
    1
    Institute of Catalvsis and Surface Chemistrv, Polish Academv of Sciences, Nie:apominafek 8, 30-239 Krakow, Poland,
    2
    Process & Energv Laboratorv - Engineering Thermodvnamics, Delft Universitv of Technologv, Leeghwaterstraat 44, 2628
    CA Delft, The Netherlands
    3
    Catalvsis Engineering - The Pore, DelftChemTech, Delft Universitv of Technologv, Julianalaan 136, 2628BL Delft, The
    Netherlands
    4
    Foundation for Research and Technologv Hellas, Institute of Chemical Engineering and High Temperature Chemical
    Processes, P.O.Box 1414, Gr-26504 Patras, Greece
    l.gorasubmail.nl
    This report presents the development oI new selective gas sensors utilizing
    a monocrystalline, thin, b-oriented silicalite-1-layer-Metglas assembly
    (Iigure 1). The key principle Ior the operation oI these sensors is
    monitoring the changes in the resonance Irequency oI the Metglas strip in
    relation to concentration oI an analyte in the gas phase. This technique
    provides a simple wireless way Ior monitoring the eIIects oI the amount oI
    adsorbed gases in the silicalite-1 coating. The orientation oI the silicalite-1
    crystals in the b-direction means the straight channels are perpendicular to
    the sensor surIace. Due to molecular sieving and adsorption selectivity oI
    -485-
    Figure 1: SEM micrographs oI oriented
    silicalite-1/Metglas sensor.
    the zeolite layer, the sensor can discriminate between diIIerent gases. The thin zeolite coating ensures a Iast response time oI
    the sensor.
    The crystal orientations were determined by XRD analysis and supported by SEM images. Practically only (0k0) lines appear
    in XDR spectra, conIirming that only the b-axis is perpendicular to the substrate surIace. Zeolite crystals on the sensor are b-
    oriented Irom an early stage oI the synthesis. AIter two hours, the sensor was completely covered with a thin (800 nm)
    monolayer oI inter-grown, b-oriented silicalite-1 crystals. A longer synthesis time results in deposition oI additional randomly
    oriented silicalite-1 crystals, inIluencing overall crystal orientation. Ozone detemplation at mild thermal conditions (473 K)
    was successIully applied to remove the template Irom the zeolite coating oI the Metglas sensor. This technique allows
    detemplation oI silicalite-1 at temperatures below the Curie temperature oI the Metglas material.
    The sensor was able to repeatedly sense carbon dioxide in air and could discriminate between linear and branched
    hydrocarbons. The sensor was able to detect n-butane, while it did not respond to the presence oI iso-butane.
    PF.9.3
    Composite membranes for carbon fiber microelectrodes dedicated to health and
    environmental micropollutants analysis
    M. Pontie, E. Talla Feuhouo, T. Papp, S. Bourhis, P. Fokou, T. Feng
    Angers universitv, Group Analvsis and Processes (GA&P), GEPEA, UMR CNRS 6144, 2 Bd. Lavoisier 49045 Angers cedex
    01, France
    maxime.pontieuniv-angers.Ir
    A novel modiIied carbon Iiber microelectrode (MCFME) was obtained by combining tetrasulIonated phtalocyanine (p-
    NiTSPc) electrodeposited Iilm with paraphenylenediamine (p-PD) coating Ior the detection oI the methyl parathion (MPT) and
    its principal matabolites para-nitrophenol (p-NP) and para-aminophenol (p-AP). Square-wave and diIIerential pulse
    voltammetries were engaged Ior comparison and the optimized parameters Ior both technics determined (Irequency, initial
    scanning potential, scan increment, pulse height, pulse width) |1,2|.
    Our contribution shows the possibility oI higher sensitive detection oI p-NP and MPT on a poly-NiTSPc Iilm with a clear
    electrocatalytic activity towards both organophosphorous. Our contribution shows also the possibility oI a selective detection
    oI the metabolite p-NP in presence oI MPT due to the multilayer membranes elaboration deposited on the carbon Iiber.
    Roughness evolution oI the carbon Iibers during their modiIications were Iollowed by atomic Iorce microscopy and helped us
    to demonstrate the electrocatalytic activity vs geometrical eIIects.
    Furthermore, we developed a homemade microsensor dedicated to NO detection in biological media with the new approach
    based on the modiIication oI the carbon Iiber surIace by membranes electrodeposited or spin coated showing an increase in
    sensitivity and selectivity. The last part will be dedicated to the temptative to increase the sustainability oI the sensors by
    developing new and original antibioIoulig strategy |3|.
    References . |1| Sbai M., Pontie M. et al. (2007) Sensors and actuators B, 124 (2) 368-375; |2| Pontie M. et al. (2008)
    Electroanalvsis, submitted; |3| Lasquellec V., F. De Nardi, M. Pontie et al. (2007) Revue des Sciences de lEau 20(2) 175-183.
    PF.10.1
    Influence of pH on membrane fouling and performance of tubular ceramic
    membranes treating textile wastewater
    M.I. Alcaina-Miranda, S. Barredo-Damas, M.I. Iborra-Clar, J.A. Mendoza-Roca
    Dept. Of Chemical and Nuclear Engineering, Polvtechnic Universitv of Jalencia, Camino de Jera s/n, 46022 Jalencia, Spain
    serbardaisirym.upv.es
    Water shortage situations are becoming widespread, especially along the Mediterranean coast. The concern about this
    important issue has lead to more severe environmental laws; consequently, industrial expenditures have increased. Industrial
    sectors are aware oI the need oI new environmental policies such as water reclamation or water reuse in the diIIerent processes
    carried out in the industries. Textile industries are rated as the most polluting among all the industrial sectors due to its
    particular characteristics |1|.
    -486-
    Membrane technologies have been proved as a viable alternative in order to reuse these eIIluents |2|. However, one oI the
    major drawbacks presented by membrane technologies is the rapid Iouling oI the membrane surIace, which diminishes the
    process eIIiciency. As a consequence, eIIluents must be treated previously to the Iinal membrane stage. This previous
    treatment may be carried out by means oI several techniques where membrane technologies also provide some outstanding
    alternatives such as ceramic microIiltration or ultraIiltration.
    Previous studies proved the viability oI the ceramic ultraIiltration process as a pre-treatment Ior Iinal NF/RO stages. In this
    way, this work studies the perIormance oI ceramic ultraIiltration membranes treating eIIluents Irom a textile industry. In order
    to analyze the behavior oI this kind oI membranes, the eIIect oI pH on the permeate Ilux, as well as on the membrane Iouling
    along operating time, has been studied. Hence, essays were perIormed in a range oI pH values between 7 and 12. All oI the
    experiments were carried out in a pilot plant where three diIIerent tubular ceramic membranes (ZrO
    2
    -TiO
    2
    Inside Ceram
    Irom Tami industries) with an eIIective area oI 0.1 m
    2
    and MWCO oI 30, 50 and 150 kDa, respectively, were tested. This
    makes it possible to study the inIluence oI the molecular weight cut-oII, both in the permeate Ilux and in the water quality.
    The results pointed out that, at the highest pH values, almost negligible Ilux decline was observed along the operating time.
    Moreover, Ior these pH values, noticeable reductions in parameters such as COD (64-75), color (85-98) and turbidity
    (~99) were achieved.
    |1| I. Koyuncu and D. Topacik, EIIects oI operating conditions on the salt rejection oI NF membranes in reactive dye/salt
    mixtures, Separation and PuriIication Technology 33 (2003) 283-294.
    |2| G. Capar et al., Reclamation oI printing eIIluents oI a carpet manuIacturing industry by membrane processes, Journal oI
    Membrane Science 277 (2006) 120-128.
    PF.10.2
    Textile wastewater reuse by means of sequencing batch reactor technology and
    nanofiltration
    E. Zuriaga Agusti, J.A. Mendoza Roca, M.I. Iborra Clar, M. Tancredi
    Department of Chemical and Nuclear Engineering, Polvtechnic Universitv of Jalencia, Camino de Jera s/n, 46022, Jalencia,
    Spain
    elzuagetsii.upv.es
    Nowadays there is an increasing problem with water reservoirs, thereIore, actions must be taken in order to wastewater
    reclamation and reuse.
    Textile wastewaters are characterized by high organic matter concentration and color. The aim oI this study is to achieve the
    reuse oI textile wastewater as process water.
    The treatment proposed consists oI a laboratory scale sequencing batch reactor (SBR), Ied with synthetic wastewater Iollowed
    by nanoIiltration membranes. The SBR operates in cycles, each one has several phases: Iill, react (anaerobic and aerobic),
    settle and draw. In the aerobic stage the organic matter decreases and in the anaerobic stage the azo-dyes are degraded. The
    cycle length was 20 hours and the volume exchange ratio (volume Ied each cycle divided by the total volume) was 33.
    Dissolved oxygen, pH and conductivity were monitored. Every day were determined color removal by measuring the
    absorbance values oI the samples at three wavelengths (440, 520 and 600 nm) and the COD removal. NanoIiltration was
    carried out in a laboratory plant with a NF membrane element (NF 270 Irom Dow Chemical). AIter a previous study, the plant
    was operated at 10 bar and in a concentration mode. Thus the concentrated stream was stored in order to be pumped to the
    SBR and then evaluate the eIIect oI the salts concentration in the biological process.
    The time required Ior adapting the sludge Irom a municipal wastewater treatment plant with synthetic wastewater was 10 days.
    Color and COD removal yield was between 80 and 90 Ior both parameters. The maximal percentage oI membrane retentate
    in the SBR Ieeding volume was between 30 and 40. Higher ratios (membrane retentate/synthetic wastewater) drove to a
    diminution in the SBR yield.
    |1| A. Chiavola, G. Farabegoli, M. Naso, E. Rolle, Decolorization oI reactive red dye under anaerobic conditions in a
    Sequencing Batch Reactor, 2006
    |2| R. Ma. Melgoza, A. Cruz, G. Buitron, Anaerobic/aerobic treatment oI colorants presents in textile eIIluents, 2004, 50(2)
    149-155
    |3| Isolina Cabral, Susana Penha, Manuela Matos, Amelia Rute, Francisco Franco, Helena Pinheiro, Evaluation oI an
    integrated anaerobic/aerobic SBR system Ior the treatment oI wool dyeing eIIluents, 2005, 16: 81-89
    -487-
    PG.1.1
    Preparation and characterization of PSU-alumina hybrid membranes for use in
    filtration processes
    V. dos Santos
    1
    , C. Z. Mazutti
    1
    , C. P. Bergmann
    2
    , M. Zeni
    1
    1
    Science and Technologv Center, Universitv of Caxias do Sul, 95020-972, Caxias do Sul, RS, Bra:il
    2
    Laboratorv of Ceramic Materials (LACER),

    Departament of Materials, Engineering School, Federal Universitv of Rio
    Grande do Sul, Osvaldo Aranha, 99, 90035-190, Porto Alegre, RS, Bra:il
    vsantos2ucs.br
    The hybrid ceramic-polymer membranes incorporating characteristics oI ceramics and polymeric, where the ceramic support
    macroporous strength to microporous hybrid system Ieaturing low resistance to the Ilow oI permeate while the top layer
    polymer provides characteristics oI selectivity |1, 2|. In this work hybrid membrane were studied Ior aluminapolysulIone
    (PSU-alumina and PSU-alumina with diIIerent agents such as poly (vinyl pyrrolidone) (PVP) with the objective oI providing
    greater porosity to top layer and the glutaraldehyde with the Iunction oI promoting graIting polymer-ceramic. The hybrid
    membranes were produced Irom the deposition oI a top layer oI PSU under diIIerent concentrations. The supports Ior the
    membranes were obtained Irom the pressing oI Ilat circular plates oI u-alumina (Alcoa Aluminio) and subsequent heat
    treatment (1300 C). The ceramic support, aIter drying at 100 C Ior 12h, were immersed Ior 2 hours in a solution oI PSU
    (Sigma-Aldrich) 10 (w/w) in chloroIorm (Merck). The evaporation oI the solvent was perIormed in a vacuum oven at 30 C
    Ior 6h. The characterization was perIormed by: determining the content oI organic matter; absorption oI water; apparent
    porosity (ASTM C - 133/94); morphology by scanning electron microscopy (SEM) and permeation oI water. The content
    (w/w) oI immobilized PSU was 1.73 (+ 0.28) in the membrane. The evaluation oI the morphology oI ceramic membrane and
    the support was Ior SEM. It was observed that the alumina was impregnated with PSU probably by physical interaction
    between polymer-ceramic, with PSU in the top layer oI ceramic support, conIirmed by the analysis oI FT-IR with ATR. The
    incorporation oI PVP (1) to alumina membrane hybrid-PSU caused a 50 reduction in the Ilow oI water permeated while
    alumina membrane-PSU with glutaraldehyde (1) reduced 35 oI the Ilow on the macroporous support oI alumina with
    maximum pressure oI 176.5 kPa. Higher concentrations oI glutaraldehyde (6) showed no Ilow oI permeate. The results, we
    can propose that the hybrid membranes obtained in this work may be peculiarities oI micro and/or ultraIiltration, and this will
    be Iurther evaluated in treatment oI domestic eIIluent.
    |1| X. Liang, D. M. King, M. D. Groner, J. H. Blackson, J. D. Harris, S. M. George, A.W. Weimer, Barrier properties oI
    polymer/alumina nanocomposite membranes Iabricated by atomic layer deposition, J. Memb. Sci. 2008, 322, 105-112.
    |2| L.-Y. Chu, S. Wang, W.-M. Chen, SurIace modiIication oI ceramic-supported polyethersulIone membranes by interIacial
    polymerization Ior reduction membrane Iouling, Macromol. Chem. Phys. 2005, 206, 1934-1940.
    PG.1.2
    Valorisation of cork boiling wastewaters by membrane processing
    A.R.S. Teixeira, J.L.C. Santos, J.G. Crespo
    Requimte/CQFB, FCT - Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal.
    andreia.teixeiradq.Ict.unl.pt
    Nowadays, the valorization oI residual streams by generation oI a valuable product promotes not only the environmental
    sustainability but also constitutes an important competitiveness Iactor in the actual market. The high toxicity and organic
    pollutant content oI cork boiling wastewaters produced by the cork industry in large amounts (around 400L oI wastewaters per
    tonne oI cork) make conventional treatments ineIIicient, according to the stringent quality oI wastewaters to discharge in
    public water courses required by the EU directive 91/271/CEE |1|. The obligatory treatment oI these wastewaters represents an
    additional production cost and can compromise the cork industry`s viability. This study |2| proposes a membrane-based
    process Ior treatment and valorization oI cork wastewaters, producing a permeate suitable Ior reuse in cork processing,
    according to the International Code oI Cork Stopper ManuIacturing Practice, and a concentrate enriched in tannins, which is
    valuable to the leather tanning industry as a retanning agent. Experiments were perIormed at laboratory scale to select the
    adequate membranes. Four commercial polymeric membranes were selected and tested: NTR7450 (Hydranautics, USA),
    Desal-DK (GE Osmonics, USA), NF90 (Dow, USA) e NF270 (Dow, USA). The perIormance was evaluated determining the
    membrane permeability and rejection coeIIicients Ior the Iollowing indicators: total organic carbon (TOC), colour, absorbance
    at 254 nm and salt content. Two membranes were selected to perIorm pilot-scale studies, NF270 and NF90. The NF90
    -488-
    membrane shows best results since the high rejection values allows Ior permeate reuse (unlike the NF270 membrane
    (Figure 1)) leading to a 45 in volume oI water saving and, thus, a decrease in the overall production costs. The concentrates
    generated by both membranes were successIully tested in the tanning and retanning leather processes, and the higher retanning
    leather power was observed Ior the concentrate obtained with the NF90 membrane. A mass balance model was established and
    calibrated with experimental data, in order to provide a consistent description oI the transient variation oI TOC and salt
    concentration, as well as the permeate Ilux oI cork processing wastewaters by NF. Additionally, an economical evaluation
    study was perIormed, showing the viability oI the process to be industrially applied.
    (a) (b)
    Figure 1. Apparent rejection Iactor oI pollutant indicators as Iunction oI the volume reduction Iactor (VRF), during the cork
    wastewater concentration step at pilot scale, using NF90 (a) and NF270(b) membranes |2|.
    |1| European Directive, 91/271/CEE, Treatment oI public waste disposal
    |2| A.R.S. Teixeira, J.L.C. Santos, J.G. Crespo., Sustainable membrane-based process Ior valorisation oI cork boiling
    wastewaters, Separ. PuriI. Technol. (2009), available on line doi:10.1016
    PG.1.3
    Recovery of an hydroxytyrosol-rich extract from olive mill residues by membrane
    technology
    J.L.C. Santos, J.G. Crespo
    Requimte/CQFB, FCT - Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal.
    jose.santosdq.Ict.unl.pt
    Hydroxytyrosol is a polyphenol that has been identiIied as one oI the most potent antioxidant yet discovered, and has been
    proven to be very eIIective in the prevention oI diverse diseases. On the other hand, olive mill residues and wastewaters
    represent a burden Ior the olive oil industry due to their toxicity and high volumes processed.
    The present work reIers to a recently patented process to recover hydroxytyrosol-rich extracts Irom residues oI the olive tree
    using membrane technology |1|. These technologies comprise nanoIiltration and reverse osmosis which are used in an
    integrated mode. In this way, this process allows to recover compounds oI lower molecular weigth in the permeate stream,
    while rejecting compounds oI higher molecular weight, including pesticides and heavy metals.
    The Iirst step oI the procedure consists on the extraction/lixiviation oI the olive mill residues with water. The resulting extract
    is centriIuged to remove the suspended solids to avoid possible downstream problems during the membrane Iiltration step. The
    membrane Iiltration step is comprised oI nanoIiltration, to recover hydroxytyrosol Irom the raw extract, and reverse osmosis to
    concentrate the hydroxytyrosol-enriched permeate stream Irom the nanoIiltration step. The concentrate Irom the reverse
    osmosis step can be Iurther concentrated in a spray-dryer iI aiming to obtain the product in powder Iorm. The product obtained
    by the proposed process can be incorporated in Iunctional Ioods, used as a nutraceutical or cosmeceutical.
    This paper will present a technical and economical assessment oI this process, in particular in what concerns the design oI the
    nanoIiltration and reverse osmosis units, as well as an environmental analysis oI its impact.
    |1| J.L.C. Santos, A. Matias, A. Nunes, C. Duarte, J.G. Crespo, M. Nunes da Ponte, Method oI obtaining a natural
    hydroxytyrosol-rich concentrate Irom olive tree residues and subproducts using clean technologies, WO 2007/013032 A2
    -489-
    PS.1.1
    Applied silicon carbide membrane applications
    Jens Husted Kjr, MsC Chemical Engineering
    CoMeTas A/S, Lerhoef 10, 2880 Bagsvaerd, Denmark
    inIocometas.dk
    Strong global population growth, climate change, stricter global environmental regulations and a world running out oI
    drinkable water is on the agenda oI leaders all over the world.
    This creates a strong need Ior energy eIIicient Iiltration solutions and durable membranes to solve evident problems.
    The robust silicon carbide membrane has a high hydrophilicity and thereIore oIIer great beneIits in terms oI Ilux compared to
    other ceramic materials. The production technology enables manuIacturing oI speciIic geometries according to the speciIic
    application and also speciIic pore size - ranging Irom ultraIiltration to microIiltration.
    This paper describes 3 diIIerent applications with CoMeTas silicon carbide membranes:
    1. Filtration oI produced water which is a highly unwanted by-product in the oil industry.
    'When producing oil, water is also generated. Ultrafiltration membranes have show verv useful in reducing oil in water
    to well under 5mg/l. Todav high flux membranes have shown that both OPEX and CAPEX have become acceptable.`
    CoMeTas has conducted several pilot scale experiments regarding Iiltration oI produced water in order to decrease the
    amount oI dispersed oil. It has been shown that it is possible to achieve a reduction in the Iree oil content Irom 70000 ppm
    to below 10 ppm. This low oil content in the permeate could be reached regardless oI oil content in the Ieed, which shows
    that the amount oI oil in the permeate is virtually independent oI oil in the Ieed.
    2. Pool & Spa Iiltration with dead-end AquaSolution membranes.
    'Sand filters are traditional being used as filter in the Pool & Spa segment. Aqua Solution minimi:es footprint, saves
    water consumption with 88, saves energv consumption bv 76 and filters the water to higher standards compared to
    traditional sandfilters`
    3. Disk membranes: Filtration oI slurries Ior the mine industry.
    'Silicon Carbide is the second hardest material after diamond abrasive. Slurries can therefore be filtered with Silicon
    Carbide membranes. Tvpicallv, the silicon carbide disk membranes offer unique possibilities for easv cleaning and
    operation.`
    Other areas Ior using silicon carbide membranes are: Prefiltration of RO, MBR, replacement of sand filters, manure filtration
    and steam filtration.
    Keywords: Silicon Carbide membrane, high water Ilux, MF, UF, replacement Ior sand Iilters, MF, UF, produced water, disk
    membranes cross Ilow membrane, dead-end membrane, pool and spa.
    -490-
    AUTHORS INDEX
    -491-
    Abaci H.E. 297
    Abad Garrido J. 79
    Abbas A. 294
    Abdekhodaei Z. 197
    Abdenebi H. 398
    Abejon R. 310
    Abetz V. 8
    Abusaloua A. 45
    Achilli A. 138, 384
    Adamovich D.V. 426
    Adje F. 328
    Adoua R. 97
    Adrus N. 242
    Aerts A. 38
    AIonso C. 160
    Ahmadian Namini P. 315
    Ahunbay M.G. 6, 155, 290
    Aimar P. 146, 147, 266, 434
    Ajhar M. 460
    Akadar A.B. 409, 410
    Akamatsu K. 85, 238
    Akbarzadeh Arbatan T. 428
    Akiduki M. 132
    Al Obaidani S. 347
    Alaerts L. 183
    Alame M. 45
    Alami Younssi S. 217
    Albaraka Z. 339
    Albasi C. 95, 135, 336, 371, 372, 418,
    466
    Albasi C. 135
    Albasi C. 336
    Albasi C. 371
    Albasi C. 372
    Albasi C. 418
    Albasi C. 466
    Alcaina-Miranda M.I. 486
    Aldea S. 38
    Alem H. 31
    Alentiev A. 43, 255
    Alexandre B. 296
    AlIenore S. 147
    Alhadidi A. 119, 374
    Alique D. 216
    Alizadeh A. 403
    Allende D. 376
    Alsoy Altinkaya S. 33, 171, 297, 308, 477
    Alvarez Blanco S. 273
    Alvarez Fernandez R. 273
    Alvarez J.R. 101, 352
    Alves V.D. 163
    Ameduri B. 23, 224
    Amiot J. 169
    Amiri S. 373
    Ancharova U.V. 227
    Andag U. 477, 479
    Andreottola G. 81
    Andresen R. 106
    Ante A. 406
    Antico E. 420
    Antipov E. 43
    Aouni A. 355
    Aptel P. 147
    Araki M.S. 305
    Aran H.C. 86, 108
    Aravand M.A. 29
    Araya-Farias M. 372
    Arbel R. 379
    Argelles A. 418, 466
    Ariza M.J. 245
    Arnot T. 419
    Arous O. 196
    Arsuaga J.M. 277, 278
    Artaud J. 463
    Ascensios E. 97
    AshraIizadeh N. 47, 208
    Assunao R.A. 414
    Astudillo C. 315
    Atalay-Oral C. 6, 155, 194
    Athes V. 92
    Aubenneau M. 416
    Aubry T. 296
    Audic J.L. 464
    Augier L. 224
    Avdeev V.V. 206
    Ayala-Bribiesca E. 120
    Ayral A. 15, 16, 243
    Azami H. 373
    Baccar N. 338
    Bacchin P. 52, 68, 466
    Bader A. 171
    Bagagli C.P. 323
    Bahlouli S. 484
    Bai H. 130
    Baimpos T. 485
    Balannec B. 62, 362, 376
    Balcerek W. 413
    Balduchi G. 20
    Bancon-Montigny C. 416
    Bandini S. 250, 267
    Bandyopadhyay S. 19
    Banham J. 435
    Baptista I. 168
    Bara J.E. 39, 446
    Baranek P. 127
    Barati A. 225
    Barbieri G. 46, 299, 447
    Barboiu M. 9, 36, 39, 40, 395
    Barbot E. 145
    Barboza M. 367, 480
    Barkallah A. 65
    Barona G.N.B. 239
    Barredo-Damas S. 486
    Barreiro M.M. 385, 450
    Barrios martinez A. 121
    Barriuso B. 323
    Barrouk I. 217
    Bartel R. 330
    Bartovska L. 192, 260
    Bartovsky T. 260
    Barzin J. 475
    Basov N. 233
    Basu S. 183, 445
    BathIield M. 224
    Batista Neto A. 480
    Baudin I. 280
    -492-
    Baumann S. 26, 252
    Bayer C. 365
    Bazinet L. 120, 169, 372, 463, 467
    Bazzarelli F. 94
    Beal L.L. 337, 378
    Bechet M. 169
    Beck S. 479
    Beckers H. 23
    Beckman I. 161
    Bedet J. 56
    Beggel F. 455
    Beguin L. 69
    Bekassy-Molnar E. 322, 345
    BelaIi-Bako K. 139, 474, 360
    BelIer S. 437
    Belleville M.P. 98, 314, 334
    Belmejdoub J. 376
    Belova E. 33, 76, 232
    Ben Amar N. 78, 325
    Ben Amar R. 407
    Ben MaklouI M. 419
    Ben moussa H. 398
    Ben Sik Ali M. 355
    Benamor M. 241
    Benavente J. 224, 239, 264, 265, 291,
    301, 416
    Bendjeriou B. 129
    Benes N.E. 16, 285
    Bengoa C. 141
    Benharrat N. 484
    Benito J.M. 323, 376
    Bergamann C.P. 488
    Bergamasco R. 237, 352
    Berge M. 434
    Berger P. 127
    Berliner K. 245
    Bernardes A.M. 321, 412
    Bernardo P. 455
    Bernat X. 141
    Bernauer B. 188, 211, 303
    Berube P.R. 69, 117
    Besse S. 44
    Bessiere C. 366
    Betker T. 21
    Bettahalli Narasimha M.S. 194
    Bettens B. 292
    Beudon D. 360
    Bhole Y. 107, 204, 279, 480
    Biallas D. 341
    Bigarre J. 401
    Bijani S. 239, 265
    Bikel M. 180
    Billy M. 34, 439
    Bisle G. 312, 388
    Bismarck A. 107
    Bladergroen B.J. 248
    Blanc P. 168
    Bleha M. 389
    Bluemich B. 109
    Boam A.T. 440, 480
    Boaventura M. 226
    Bocquet-Druon S. 340
    Boda R. 142, 149
    Bodzek M. 410, 430, 432
    BoII P.A. 337, 378
    Bhning M. 58, 60
    Boi C. 64, 289, 350
    Bolduan P. 405
    Bondarenko G. 43, 255
    Bonhoure V. 140
    Bonnet J.P. 463
    Brger M. 167
    Borges F.J. 139
    Borneman Z. 25, 483
    Bortolotto L. 331
    Bosch L. 36
    Botelho-Cunha V.A. 73
    Bottino A. 218, 254, 274, 397
    Bouchard C. 352
    Boucheteau T. 401
    Bouchoux A. 71
    BouciI N. 70, 91
    Boudaira B. 330
    Bouhidel K.E. 326, 354, 357
    Bouju H. 421
    Bourhis S. 486
    Boutarin L. 142, 149, 435
    Bouyer D. 12, 57, 190, 205, 295
    Bouzek K. 387
    Bouzerara F. 330
    Boy V. 50
    Bozkaya-Schrotter B. 142
    Brabec L. 188, 212, 217
    Braeken L. 277, 351
    Bram M. 27
    Brami M.V. 437
    Branco C.M. 200, 222
    Brands K. 27
    Brault P. 398
    Bravi M. 408
    Brazinha C. 163
    Breant P. 142
    Bredesen R. 22, 128, 133, 161
    Breisig H. 365
    Briceo K. 457
    Brilman W. 93
    Bringas E. 64, 303, 347
    Brinkmann T. 102, 453
    Brisson P. 47
    Brizuela M. 212
    Broglia M. 213, 218
    Brooms T.J. 319
    Brown D. 287, 452
    Brozova L. 181
    Bruening M.L. 28
    Brule B. 281
    Brum F.J.B. 200, 222
    Bruni L. 250, 267
    Brschke H. 356
    Buchkremer H.P. 26
    Buchmeiser M.R. 30
    Budd P.M. 298
    Buekenhoudt A. 23, 63, 151
    Buetehorn S. 109
    Buhr K. 152
    Buisson H. 3
    -493-
    Bukhovets A. 369
    Bukusoglu E. 317
    Buonomenna M.G. 7, 151, 195, 457
    Burban A. 220
    Burganos V. 61
    Burgard M. 339
    Busini V. 289
    Buson C. 360
    Butwilowski W. 25, 226
    Buysse C. 23
    Cabassud C. 147, 415
    Cabezas J.L. 323
    Caetano R.M. 320
    Cai M. 465
    Cairo P. 288
    Cakal U. 449
    Calles J.A. 216
    Calvio J. 212
    Calvo J.I. 254, 377
    Campana C. 187
    Campbell K. 475
    Campos J.B.L.M. 66
    Campos L.A. 305, 324, 378, 473, 474
    Cancino B. 315, 317, 467, 472
    Candela A.M. 424
    Canet D. 56
    Cano-Odena A. 53, 149, 183, 445, 476
    Caothien S. 404
    Capanelli G. 274, 397
    Capannelli G. 218, 254
    Car A. 13
    Caravella A. 84, 299
    Cardea S. 186
    Cardenas A. 142
    Carlisle T. 39
    Carnevale M.C. 89
    Caro J. 20, 21
    Carreon M.A. 155
    Carretier E. 111, 448
    Carvalho A.L. 182, 261
    Carvalho G. 81
    Casademont C. 120
    Casado C. 454
    Cassano A. 164, 339
    Castaing J.B. 120
    Castelao N. 220
    Castricum H.L. 41, 100
    Catalano J. 131, 285
    Cath T.Y. 138, 384
    Causserand C. 146, 266, 418, 434
    Cavallotti C. 289
    Cavarroc M. 398
    Cazacu A. 40
    Cees Van rijn 113
    Cerneaux S. 19
    Cernochova B. 11
    Chaabane L. 275, 276
    Chan C.C.V. 69, 117
    Chandansson D. 249
    Chang C.J. 231
    Chang M.C. 231
    Chang Y. 31, 231
    Chapon L. 406
    Charcosset C. 338, 429
    CharIi A. 325
    Charmette C. 18, 39
    Chatzicharalampous C. 252
    ChauIer B. 304, 464
    Chaumette C. 312, 388
    Chaumien E. 142, 149, 435
    Chauveau E. 24
    Chavigneau M. 400
    Chea V. 334
    Chen J.Y. 390
    Chen L.T. 231
    Chen V. 294
    Chen W.Y. 231
    Cheng S.H. 231
    Cheng S.Y. 50
    Cheraitia A. 15
    Chiam C. 424
    Chianese A. 174
    Chiarani D. 81
    Chiciuc I. 97
    Chikh L. 224
    Childress A.E. 138, 384
    Chinpa W. 191
    Chinthaginjala J.K. 86
    Chiu M.C. 305, 322, 324, 378, 473,
    474
    Cho E.S. 191
    Choi S.H. 46
    Chou H.H. 350
    Christel J. 448
    Christensen K.V. 90, 106, 164, 341
    Chung W.J. 191
    Cipollina A. 110
    Claes S. 203
    Clarizia G. 455
    Clausse D. 425
    Clemenson S. 180
    Clement R. 34, 281, 439
    Coasne B. 59
    Coca J. 376
    Coelhoso I.M. 160, 283
    Cojocaru C. 281
    Coll M.T. 301
    Collette F. 223, 402
    Colomban P. 129
    Combe M. 429
    Comite A. 218, 274, 397
    Compa-Moreno V. 391
    Comte M. 386
    Condom S. 219, 330
    Conesa A. 482
    Conidi C. 164, 339
    Constantopoulos K.T. 244
    Corengia P. 189, 201, 212
    Coronas J. 6, 263, 454
    Cortes-Juan F. 362
    Corvini P. 421
    Cossec C. 463
    Costa B.R.S. 320
    Costa R. 127
    Coutinho C.M. 322
    Coutte F. 169
    -494-
    Craciun M.E. 414
    Cremers C. 126
    Crespo J.G. 55, 58, 80, 81, 102, 160,
    163, 234, 260, 283, 363,
    384, 420, 442, 488, 489
    Cretin M. 368, 396
    Criscuoli A. 89, 339
    Cserjesi P. 139
    Cuhorka J. 310
    Cui Z. 288
    CulIaz A. 215
    CulIaz P.Z. 229
    Cuperus F.P. 153, 422
    Curcio E. 96, 171, 347
    Cwikla J. 407
    Czechowska K. 214
    Czermak P. 112, 334, 337, 382, 405,
    406, 476
    Da Costa P. 368
    Daci N. 312
    Dahl P.I. 161
    Daines-Martinez C. 142
    Dal-Cin M.M. 157, 292
    Dalmon J.A. 45
    Dambies L. 411
    Dammak L. 275, 276, 277
    Damodar R.A. 350
    Darcovich K. 292
    Dargent E. 228
    Darvishmanesh S. 63
    Darwiche A. 386
    Dathe J.E. 167
    David G. 23
    David L. 34, 180
    De Abajo J. 224, 451
    De Almeida N.M. 475
    De Amorim M.T. 352
    De Angelis M.G. 10, 13, 285
    De Araujo A. 352
    De Baerdemaeker J. 53
    De Bartolo L. 171, 187
    de Boer J. 172
    de Bruin J. 446
    De la Campa J.G. 224, 451
    De la Puente Gonzalez S. 141
    De la Torre T. 116
    De Lamare J. 386
    De Lorenzo L. 42, 67
    De Luca G. 60, 364
    De Montigny D. 259
    De Moura J.M.L.N. 475
    De Nobili M. 403
    De Pablo J. 272, 284
    De Pinho M.N. 73
    De Ridder E. 292
    De Vos D.E. 183
    De Vries I.J. 172
    Deabate S. 54, 55, 444
    Debien I.C.N. 375, 468, 470
    Decloux M. 427
    Degreve J. 63, 292
    Dejardin P. 33
    Del Colle R. 253
    Del Paggio A. 158
    Delaunay D. 122
    Delgado L.F. 135
    Delhorbe V. 224
    Della Giustina S.V. 378
    Demmer W. 478
    Demoustier-Champagne S. 31
    Deng Z. 214
    Deniz S. 458, 459
    Denoulet B. 259
    Deratani A. 12, 33, 57, 78, 140, 190,
    191, 295, 297, 308, 477
    Derekx Q. 68
    DesIours J.P. 57, 295
    Desjardins Y. 463
    Deslouis C. 228, 401
    Dessemond L. 127
    Deumie C. 280
    Devatine A. 97, 466
    Dhahbi M. 98, 355
    Dhaler D. 111
    Dhulster P. 169
    Di Maio F.P. 84, 364
    Di Miceli A. 110
    Di ProIio G. 96, 347
    Di Renzo A. 84, 364
    Diallo H. 304
    Diat O. 124
    Diaz V. 481
    Dietrich R. 477
    Dimartino S. 64, 350
    Ding L. 425
    Ding L.H. 72
    Diniz da Costa J.C. 18, 27, 221
    Dittmeyer R. 331
    DjaIer L. 243
    Djehiche M. 409, 410, 431
    Dlugolecki P. 392
    Dmitriev S.A. 426
    Dobrak A. 259, 440
    Dobrowolski A. 281
    Doco T. 314
    Dker M. 102
    Dorandeu C. 135, 418
    Dornier M. 314
    Dos Santos V. 488
    Dov A. 96
    Doyen W. 23
    Drahokoupil J. 211
    Drebing S. 477
    Dresch M. 34, 439
    Drews A. 116, 136
    Drioli E. 42, 46, 60, 67, 82, 87, 89,
    94, 96, 151, 164, 170, 171,
    186, 187, 189, 195, 275,
    288, 299, 339, 347, 364,
    447, 457
    Drouiche N. 403
    Druon Bocquet S. 65, 98
    Du N. 157
    Du Prez F.E. 149
    Duarte E. 313
    Duarte E.C.N.F. 321
    -495-
    Duarte J. 433
    Dbel S. 479
    Dubois M.P. 98
    Dudziak M. 432
    Duke M. 14
    Dupuy A. 92
    Durand J. 18, 127, 398
    Durand V. 246
    Dutczak S.M. 150
    Duval H. 69
    Duwez A.S. 31
    Dweik J. 59
    Dylhasi A. 312
    Dzahir M.I.M. 399
    Ebert K. 152
    Ebrahimi M. 112, 337, 382, 405, 406
    Egger W. 53
    El Harrak N. 253
    El Rayess Y. 466
    Elarbi A. 123
    Eliseeva T. 369
    Elkinani H. 416
    Ellett A. 222
    Ellis A.V. 244
    Ellouze E. 407
    Ellouze F. 78
    Emneus J. 238
    Endo A. 206
    Endo N. 394
    Engel L. 337, 405
    Engwall E. 158
    Ennajdaoui A. 398
    Ermilova M. 233
    Erpek E. 6
    Escaler S. 239
    Escobar-Ferrand L. 78
    Escoda A. 269
    Escribano S. 125
    Escudero I. 323, 346
    Espina V. 72
    Espuche E. 180, 223, 224
    Etienne S. 34, 439
    Ettori A. 266
    Etxebarria J. 370
    Etxeberria M. 189, 201, 212
    Eusebio R.C. 87, 362
    Euvrard M. 409, 410, 431
    Ezhov A. 193
    Faber R. 478
    Fabregat A. 141
    Falconer J.L. 155
    Falconet C. 429
    Fallant L. 25
    Fantauzzi S. 457
    Farabegoli G. 408
    Farcy M. 78, 258, 404
    Fargues C. 427
    Farid O. 278
    Fatin-Rouge N. 409, 410, 431
    Faucet Marquis V. 135, 418
    Faur C. 205, 417
    Favre E. 70, 91, 161, 185
    Fedotov A. 333
    Feng T. 486
    Feriol L. 49
    Fernandez Garcia L. 273
    Fernandez J.F. 279, 330
    Fernandez L. 202
    Fernandez-Carretero F.J. 201
    Fernandez-Gesalaga E. 189, 201
    Fernandez-Gesalaga E. 201
    Ferrando F. 249
    Ferrando M. 114, 471, 472
    Ferrari M.C. 13, 285
    Ferre L. 249
    Ferreira J.Z. 321, 412
    Ferreira Junior M.F. 414
    Ferrer B. 220
    Fersi C. 355
    Fiaty K. 45
    Fichet O. 224
    Field R.W. 288
    Fievet P. 250, 269, 291, 409, 410,
    431
    Figoli A. 89, 195, 236
    Fila V. 211, 212, 303
    Fillaudeau L. 381
    Finotello A. 39, 446
    Firdaous L. 169
    Firman L. 462
    Firpo R. 254
    Fischbein K. 93, 156
    Fischmeister C. 442
    Fjaerbaerk L. 106
    Fjerbaek SotoIt L. 90
    Fogarassy E. 322, 345
    Fokou P. 486
    Follmann M. 365
    Font J. 141
    Fontaine M.L. 128, 161
    Fontananova E. 87
    Fontas C. 420, 478
    Fontes S.R. 253, 268
    Forstmeier A. 14
    Forte M.M.C 200, 222
    Fortulan C.A. 253
    Fortuny A. 141, 301
    Fournier D. 149
    Fradinho J. 102
    Fraile J.M. 393
    Francis P. 290
    Franck-Lacaze L. 286
    Franco J.A. 259
    Freeman B. 145
    Freitas A.S. 320
    Friedel P. 226
    Friedl A. 356, 380
    Friess K. 11, 192, 236, 275
    Frimmel F.H. 73
    Fritsch D. 60
    Fritz K. 477
    Fritzmann C. 113, 365
    Froelich D. 360
    Frugier J. 127
    Frycova M. 188
    Fujioka Y. 156
    -496-
    Fukuoka T. 319
    Fuqaha A. 380
    Furiga A. 146, 434
    Fustin C.A. 197
    Gagnaire J. 406
    Galiano H. 401
    Galier S. 50, 55, 74, 274
    Galinha C.F. 81
    Galizia M. 10, 13
    Gallo E. 457
    Galuszka J. 83
    Ganji E. 225
    Garcia - Valls R. 249
    Garcia M.G. 198, 201
    Garcia V. 77
    Garcia-Anton J. 187
    Garcia-Castello E. 339, 418, 466
    Garcia-Gabaldon M. 187
    Garcia-Lis A. 189
    Garcia-Martin N. 469
    Garcia-Valls R. 14, 163, 220, 457
    Garcia-Vargas M. 427
    Garea A. 93, 310
    Garnier-Lambrouin F. 71, 174, 316
    Grtner R. 125
    Gashi S. 312
    Gaudichet - Maurin E. 266
    Gaudreau H. 463
    Gavach M. 427
    Geanta R.M. 323
    Gebel G. 44, 54, 124, 125, 223, 224,
    402
    Gelis V.M. 426
    Geraldes V. 363
    Gerente C. 417
    Gershkovich E. 245
    Gesan-Guiziou G. 71, 174, 316, 360
    Geschke O. 238
    Gessler F. 479
    Ghaemi N. 309, 403
    GhaIIour N. 403
    Ghidossi R. 79
    Gholizadeh M. 197
    Giacinti Baschetti M. 131, 285
    Giamberini M. 14, 163, 220
    Giddings T. 83
    Gijiu C.L. 98
    Gilron J. 96, 379
    Gin D.L. 39, 446
    Gingter P. 208
    Giorno L. 82, 94, 170
    Girard D. 366
    Giroir-Fendler A. 214
    Glatz C. 475
    Glauner T. 73
    Glucina K. 68, 249, 280
    Gmehling J. 102
    Goetheer E.L.V. 446
    Gohy 197
    Golemme G. 7, 151, 457
    Golub A. 455
    Gomes D. 226
    Gomez P. 175
    Gonalves L.A.G. 305, 322, 324, 3783 473,
    474
    Gonzalez S. 315, 467
    Gonzalez-Huerta D.C. 469
    Gonzalez-San Jose M.L. 469
    Gonzalez-Santamaria D. 189
    Gora L. 485
    Gorgojo P. 6
    Gorri D. 399
    Gouzalez-Dias E. 101
    Goyens W. 315
    Grande D. 277
    Grangeon A. 20
    Gras M.L. 418, 466
    Grasmick A. 136
    Grasselli M. 270
    Grasset F. 401
    Grau K. 334, 337
    Greenlee L. 145
    Gregor T. 66, 256
    Grein T. 116, 461
    Grein T.A. 476
    Grenier J.C. 127
    Grib H. 403
    Grignard J. 185
    Groote R. 86
    Grosmaire L. 54
    Grospelly L. 366
    Gross M. 125, 262
    Grunhaum N. 127
    Grychtol P. 252
    Grygier T. 335
    Guardani R. 139
    Gubicza L. 360
    Guechi A. 219
    Guedidi S. 33, 297, 308, 477
    Gell C. 114, 471, 472
    Gell R. 420
    Gugliuzza A. 60, 67, 186, 189
    Guigui C. 147, 366, 415
    Guilhaume N. 45
    Guinle F. 328
    Guion J.L. 187
    Guiver M. 157
    Guizard C. 246
    Gul S. 356
    Gulgielmi G. 81
    Gumi T. 220, 249, 476, 482
    Gnther J. 336, 371
    Guo H. 32, 144
    Guo Y. 214
    Gurkan I. 458
    Gutierrez A. 201
    Ha S.Y. 447
    Habe H. 311, 319, 354
    Habib J.A. 404
    Habrioux A. 396
    Hgg M.B. 162, 453
    Hahn T. 334, 337
    Hajimohsen N. 225
    Hajova H. 66
    Hakan Yildirim M. 388
    Halitoglu S. 6, 155, 290
    -497-
    Hall E.R. 117
    Hamdach F. 484
    Han K.I. 247
    Haneda R.N. 268
    Hnel C. 312, 388
    Hannemann I. 334
    Hansen J.S. 238
    Harabi A. 219, 330
    Harasek M. 356, 380, 456
    Harmsen G.J. 134
    Hasanoglu A. 352
    Hassan H. 476
    Hattori T. 85
    Haukebo S.H. 453
    Hauler F. 27
    Husler D. 479
    Haynes C. 290
    He X. 162
    Heinzel J. 143
    Helix-Nielsen C. 239
    Hendrix K. 53
    Henn F. 59
    Heran M. 136, 353
    Hermann S. 136
    Hernandez A. 182, 202, 254, 261, 300,
    301, 377, 469
    Herraiz-Cardona I. 302
    Hershkovitz E. 245
    Herz H.G. 125
    Herzberg M. 115, 379
    Hesampour M. 383
    Heuchel M. 42, 58, 60
    Hidalgo M. 423
    Higa M. 394, 435
    Hill A. 14
    Hilpert M. 406
    Hinds B. 41
    HirschIeld J. 306
    Hirth T. 20, 126, 390, 448
    Hiver J.M. 34
    Hjollund Jensen D. 341
    Ho W.S.W. 167
    Hodebourg C. 228
    HoImann D. 42, 58, 60
    Hokka C.O. 367, 480
    Hlck O. 58, 60
    Hollas M. 477, 479
    Holt T. 48, 51, 110
    Hommes G. 421
    Hong D.E. 239, 345
    Hrl H.H. 478
    Horn V.G. 90
    Horvath A. 440
    Hourlier F. 417
    Hovorka S. 192, 260
    Hrabanek P. 188, 211, 212, 217, 303
    Huang B.X. 252
    Hbner A. 101
    Huguet P. 54, 55, 57, 104, 274, 286,
    361, 368, 444
    Humbert H. 47
    Hwang H.Y. 447
    Hynek V. 11, 236
    Ibaez R. 175, 481
    Iborra Clar M.I. 486, 487
    Ibragimova S. 238, 239
    Ikegami T. 311, 354
    Innocent C. 33, 297, 308, 396, 477
    Innocentini M.D.M. 367
    Irabien A. 93, 310
    Itagaki M. 319
    Iturbe D. 370
    Iversen V. 136
    Iwasa K. 132
    Izak P. 192, 260
    Jacob M. 415
    Jacquemet V. 47
    Jacques P. 169
    JaIIrin M.Y. 72
    Jallerat E. 477
    Jamowska E. 163
    Jani J.M. 86, 108
    Jansen J.C. 7, 11, 42, 46, 151, 236, 275
    Jansen K. 105, 359
    Jaouen P. 120, 141, 417
    Jauregui Haza U. 372
    Jaworska A. 281, 411
    Jenelten U. 92
    Jensen M.B. 164
    Jensen P. 341
    Jimenez Solomon M.F. 279
    Jimenez-Lopez A. 71
    Jimenez-Lopez A.J.E. 174
    Jiraratananon R. 191
    Jirka I. 212, 303
    Jonas A.M. 31
    Jonhson L.A. 475
    Jonquieres A. 34, 281, 439
    Jnsson A.S. 358, 411
    Jonsson G. 91, 301
    Joshi M. 158
    Joubert O. 127
    Julbe A. 15, 16, 18, 219, 246
    Jumate N. 209
    Jung B. 239, 345
    Jung F. 126
    Kabbabi A. 217
    Kabsch-Korbutowicz M. 429
    KaIrouni W. 18
    Kai T. 156
    Kajiwara N. 17
    Kakizis N.K. 199
    Kaldis S. 207
    Kalipcilar H. 9, 215, 317, 449
    Kallioinen M. 271, 320
    Kanaan C. 281
    Kanai M. 262
    Kanchantawee S. 74
    Kaneko D. 238
    Kanellopoulos N. 199
    Kanellopoulos N.K 210, 282
    Kang S.W. 37, 49, 247
    Kang Y.S. 37, 49, 247
    Kapteijn F. 105, 262, 359, 485
    Karabelas A.J. 108, 432
    Karanikolos G. 210
    -498-
    Karanikolos G.N. 199
    Karatay E. 9
    Karnikolos G.N. 282
    Kasher R. 35, 245, 437
    Katarzynski D. 441
    KauImann V. 465
    Kaur S. 203
    Kavaleuski A. 23
    Kazama S. 156
    Kazemzadeh AIshar M. 423
    Kebiche-Senhadji O. 241
    Keddam M. 228, 401
    Keiski R. 422
    Keiski R.L. 77
    Kemperman A. 115, 118, 119, 374, 419
    Kemperman A.J.P. 374
    Kentish S.E. 259
    Keraani A. 442
    Kerdjoudh H. 196
    Kerker S. 406
    Kertik A. 194
    Khajavi S. 105, 359
    Khaless K. 318
    Khalili-Garakani A. 364
    Khan A.L. 445
    Khatti Dizabadi S. 29
    KhliI N. 407
    Khotimskiy V. 8, 12, 193, 455
    Khotimskiy V.S. 443
    Kidena K. 51
    KieIIer R. 338
    Kikuchi R. 238
    Kim B.S. 199
    Kim H.G. 87, 362
    Kim H.S. 87, 362
    Kim J. 239, 247
    Kingsbury B.F.K. 19
    Kitamoto D. 319
    KlpIel A.M. 73
    Kobayashi Y. 51
    Kobuke M. 436
    Kochan J. 235
    Kocirik M. 188, 211, 212, 217, 303
    Koh H.C. 447
    Koh M.J. 447
    Kokoh B. 396
    Komaki M. 132
    Komplin G. 158
    Konieczny K. 407, 410
    Konovalova V. 220
    Konowal E. 332
    Kopec K. 103
    Korchak V. 333
    Korin E. 96
    Koros W. 3
    Korzenowski C. 321, 412
    Kosek J. 66, 256, 308
    Kossir A. 318
    Kostina J. 43, 255
    Kostoglou M. 108
    Kouki N. 98
    Koutsonikolas D. 207
    Kovacs Z. 112, 334, 337, 476
    Kozak A. 322, 345
    Kozhemyachenko A.S. 227
    Kozmay A. 307
    Kraume M. 116, 136
    Krawczyk H. 358, 411
    Kreis P. 85
    Kreiter R. 41, 100
    Kretzschmar J. 23
    Krishnaiah D. 325, 424
    Krukov A. 295
    Krzeminski P. 134
    Kueppers M. 109
    Kuhn J. 262, 485
    Khnert J.T. 356
    Khnl W. 116, 461
    Kujawski W.M. 76
    Kulcsar E. 332
    Kulkarni P. 160
    Kulozik U. 116, 461, 465
    Kumar A. 157, 292
    Kurchatov I. 295
    Kutasl D. 459
    Kuwada S 435
    Kwiecinska A. 410
    Labanda J. 293, 348
    Labaye I. 47
    Labropoulos A.I. 210, 282
    Lacour S. 444
    Lacroix O. 129, 400, 401
    Ladizhansky Y. 96
    LaIIorgue C. 336, 371
    Lagerge S. 205
    Laguntsov N. 295
    Lahitte J.F. 28
    Lahti J. 326
    Lai J.Y. 12, 190, 242
    Lakard S. 269
    Lakehal A. 354, 357
    Lakel A. 417
    Lameloise M.L. 427
    Lammertink R.G.H. 86, 108, 114, 180, 229
    Landaburu J. 422
    Landaburu-Aguirre 77
    Langevin D. 228, 296
    Lanoiselle J.L. 425
    Lanteri Y. 291
    Lapicque F. 286
    Lapin A. 88
    Larbot A. 19, 217, 416, 426
    Larchet C. 33, 275, 276, 277
    Larring Y. 22, 128, 161
    Lauterbach S. 85
    Lavison G. 415
    Lawler D. 145
    Layton L. 157
    Le Cloirec P. 417
    Le Duc Y. 36
    Le Sage D. 165
    Lebedev K. 76
    Lebegue J. 136
    Lebrun L. 165
    Leclerc S. 56
    Leclere V. 169
    -499-
    Lecouturier D. 169
    Leduc Y. 36
    Lee H.K. 199
    Lee J.H. 247
    Lee K.R. 242
    LeIevre N. 197
    Legrand Y.M. 36, 40
    Leja K. 413
    Lena G. 300
    Lenaerts S. 23
    Lenda H. 281
    Leo A. 221
    Leopold A.A. 301
    Leparc J. 141
    Leroux A. 435
    Lesage N. 448
    Lescoche P. 20, 366
    Lesjean B. 116, 136
    Lessard J. 467
    Le-Than S. 368
    Lewandowicz G. 332, 413
    Leysen R. 203
    Li C.L. 12, 190
    Li H. 113
    Li K. 19, 107, 131, 159, 399
    Li L. 425
    Li S. 155
    Li X. 197, 259, 315
    Liang H. 465
    Liang T.M. 231
    Lim F.W. 440, 480
    Lin J. 14
    Line A. 366
    Lipnik P. 31
    Lipnizki F. 461
    Litvinova E. 8, 12
    Litvinova E.G. 443
    Liu C. 78, 258
    Liu S. 221
    Liu Y.L. 231
    Livingston A. 257, 270
    Livingston A.G. 62, 107, 168, 204, 279, 440,
    480
    Lixon-Buquet C. 228
    Llanos J. 50, 102
    Llenas L. 272, 284
    Llorens J. 293, 348
    Lo C.H. 242
    Lochon P. 34, 281, 439
    Loh X.X. 107
    Longo E. 268
    Lopez F. 114, 471, 472
    Lopez-Lopez J.A. 427
    Lopez-Muoz M.J. 277, 278
    Lorain O. 146, 372
    Lorente M. 208
    Loricourt J. 400
    Losic D. 28
    Lottin O. 56, 283
    Loubiere P. 336
    Lounici H. 403
    Loureiro J.M. 339
    Louvisse A.M.T. 320
    Lovatel A.A. 337, 378
    Lozano A.E. 202, 224
    Lozano P. 329
    Lozano Y. 328, 329
    Lubiewski Z. 413
    Luca C. 414
    Lue S.J. 390
    Luis P. 93
    Luiten-Olieman M.W.J. 150
    Luque S. 101, 352
    Lussis P. 31
    LustIeld H. 306
    Lutin F. 104, 169
    Luyten J. 23
    Lyakhov N.Z. 227
    Macanas J. 28
    Macchione M. 42, 67
    Macedo A. 313
    Machado A.D.S. 324
    Machinal C. 47
    Madaeni S.S. 309, 373, 403, 428, 460,
    475
    Maes M. 183
    Maesowa S.I. 394
    MaIirad S. 324
    Maghnouj J. 217
    Mahon E. 36
    Maier G. 125
    Majhi A. 210
    Makaruk A. 456
    Makino T. 17
    Makovetskii K. 255
    Makowski M. 440, 480
    Maldonado L. 283
    Malis J. 389
    Malkov A. 233
    Mallada R. 393
    Malygin A. 233
    Malykh O. 161
    Malzbender J. 252
    Mameri N. 403
    Mansouri L. 241
    Mansourpanah Y. 428
    Mnttri M. 271, 320, 326, 383
    Marais S. 228, 296
    Marchand E.A. 138
    Marchese J. 198, 201, 270, 438, 462
    Marcos A. 451
    Mar-Diop C. 275
    Marestin C. 24
    Marion B. 135, 418
    Marjanska E. 485
    Markus T. 26, 222, 252, 267
    Marono M. 385, 450
    Marquardt B. 30
    Marques S.M.S. 237
    Marrony M. 127
    Marrot B. 145, 406
    Martens J. 38
    Martin A. 300, 377
    Martin N. 101
    Martin V. 24
    Martinez B. 346
    -500-
    Martinez F. 300, 377
    Martinez-Llado X. 272, 284
    Martino P. 438
    Martins M.B.O. 321
    Masclet S. 415
    Masque P. 424
    Masse A. 120, 417
    Masselin I. 167
    Massot A. 79
    Masuelli M. 270
    Mateus M. 73, 166, 349
    Mathe S. 147
    Mathis K. 329
    Matos C.T. 384
    Matson S. 8, 12
    Matsui Y. 148, 436
    Matsushita T. 148, 436
    Matsuura T. 203
    Maugeri F. 182, 261
    Maus E. 99, 101
    Mauvy F. 127
    Maya E.M. 451
    Mayor L. 418, 466
    Mayoral J.A. 393
    Mazur P. 387
    Mazutti C.M. 488
    Mazzei R. 82
    McKeever F. 176
    McLachlan D.S. 382
    Mecherri M.O. 403
    Mederic P. 296
    Mediavilla R. 347
    Medina I. 142
    Medina-Gonzalez Y. 251
    Meesschaert B. 75, 315
    Mehrnia M. 364
    Mehrnia M.R. 225, 324, 353, 373, 423
    Mei S. 128
    Meier-Haack J. 25, 226
    Meirelles C.S. 414
    Melin T. 109, 113, 235, 365, 460
    Melnik N. 232
    Melo M.V. 320
    Meloni R.V. 367
    Melzner D. 477, 478
    Mendes A. 226
    Mendil-Jakani H. 44
    Mendoza Roca J.A. 486, 486
    Mendret J. 52, 251
    Menendez M. 393
    Menetrier S. 431
    Meng L. 328
    Mengers H. 93
    Mercier R. 24, 224
    Merle G. 396
    Mestre S. 208
    Metz S. 392
    Metz S.J. 134
    Meulenberg W. 252
    Meulenberg W.A. 26, 27
    Meyer F. 248
    Meynen V. 151
    Miachon S. 45
    Micale G. 110
    Michalsky R. 476
    Michau M. 395
    Mier M.P. 481
    Mietton Peuchot M. 79, 97, 466
    Miguel E. 361
    Miguel S. 189, 201, 212
    Mihai S. 36, 230
    Mihnea M. 469
    Mikes F. 7
    Mikhailovsky S. 233
    Mikulasek P. 310
    Miller M. 143
    Miltner M. 456
    Milyutin V.V. 426
    Minhalma M. 412
    Miranda J.M. 66
    Miranda Reis M.A.M. 102
    Miskiewicz A. 281, 411
    Mitiche L. 240
    Mixa A. 441
    Miyake M. 193
    Miyamoto A. 206
    Mbius A. 252
    Modelski S. 368
    Modise S.J. 319
    Moebius A. 267
    Mohamed H.F.M. 51
    Molenberghs B. 23
    Molla S. 391
    Molnar E. 474
    Monash P. 210
    Monsuur F. 259
    Montane D. 457
    Moquet C. 328
    Moralez E. 341
    Moro A. 237
    Morelli R. 195
    Morelli S. 171
    Moreno C. 427
    Mori S. 262
    Morin A. 44, 54, 124, 125, 224
    Moskvicheva M. 255
    MostaIa K. 53
    MostoIi N. 364
    Motelica A. 100
    Motuzas J. 219
    Moulin L. 415
    Moulin P. 68, 111, 121, 144, 145, 249,
    280, 406, 407, 448, 463
    Mousavi S.A. 197
    Mullens S. 203
    Mund P. 382, 405, 406
    Muoz C. 224
    Muoz M. 28
    Naderipour C. 453
    Nagy E. 83, 328, 332
    Nakao S.I. 85, 238
    Nam M.Y. 199
    Nam S.Y. 447
    Narayan S. 446
    Naseri S. 423
    Nasr G. 39, 40
    -501-
    Naudy S. 223
    Nauleau F. 144
    N'Daye A. 328
    NechiIor A.C. 230, 241, 414
    NechiIor G. 230, 241, 414
    Negishi H. 206, 311, 354
    Nelana S.M. 319
    Nemestothy N. 139, 360, 474
    Nemudry A.P. 227
    Nesralla N. 484
    Neul H. 406
    Neves L.A. 160, 283
    Neyertz S. 287, 452
    Ngene I. 114
    Nguyen A. 113
    Nguyen P.T. 91
    Nguyen Q.T. 165, 228
    Nguyen T. 296
    Niazmand R. 469
    Nielsen C.H. 238
    Niepceron F. 401
    Nijdam W. 229
    Nijmeijer A. 16, 285
    Nijmeijer K. 93, 156, 158, 392
    Nikolakis V. 485
    Nikonenko V. 33, 76, 104, 232, 307
    Nilsson M. 461
    Nishimura C. 132
    Nishimura M. 435
    Nisola G.M. 191
    Nitsche S. 249
    Noble R. 147
    Noble R.D. 39, 155, 446
    Noda K.I. 17
    Nolan J.W. 199, 282
    Nopens I. 69
    Norddahl B. 90, 106, 164
    Nordham D. 143
    Nossova L. 83
    Novak L. 176
    Noworyta A. 335
    Nunes S. 396
    Nunes S.P. 154, 226
    Nystrm M. 383
    Ochoa N. 270, 438, 462
    Ochoa N.A. 198, 201
    Ochs C. 463
    Ochs P. 463
    Oehmen A. 102
    Ogawa S. 132
    Ohira A. 51
    Ohkubo T. 51
    Ohmori T. 206
    Ohno K. 148, 436
    Ohta Y. 85
    Okamoto Y. 7
    Okumus E. 458, 459
    Oliveira F.R.P. 234
    Oliveira R. 80, 81
    Olvera-Marquez J.M. 245
    Omont S. 360
    Ong A.L. 397
    Ongaratto R.S. 375, 468, 470
    Orekhova N. 233
    Oren Y. 35, 115, 369, 379
    Ormerod D. 440
    Ortega E. 299, 302
    Ortega-Heras M. 469
    Ortiz I. 64, 175, 303, 347, 399, 481
    Ortiz-Basurto R.I. 314
    Oshiba A. 148
    Osset P. 360
    Otero J.A. 300
    Otmani N. 44
    Ou S.S. 370
    Ouagued A. 243
    Ould Mohamedou E. 141
    Oulmi K. 326, 398
    Outzourhit A. 253
    Ouyang L. 28
    zalp C. 37
    Ozkale B.A. 6
    Pacheco Tanaka D.A. 17
    Pagliero C. 438, 462
    Paidar M. 387, 389
    Pailleret A. 228
    Pajoum Shariati F. 353, 423
    Palacio L. 182, 202, 261, 301, 469
    Palet C. 424, 482
    Palmeri J. 59, 140
    Pandiyan S. 452
    Pando D. 376
    Panteleev V.I. 426
    Pantoleontos G. 207
    Paolucci-Jeanjean D. 98, 334
    Papenburg B.J. 172
    Papin E. 20
    Papp T. 486
    Paranthoen S. 135
    Paranthoen Y. 400
    Parashchuk V.V. 443
    Park Y.I. 199
    Parra J. 315
    Parra J.A. 317
    Parramon A. 420
    Pas S. 14
    Pasc A. 40
    Paugam L. 122, 376
    Pauls J.R. 154
    Pavanasam A.K. 294
    Pazos C. 376
    Pechackova L. 256
    Pedregosa J.C. 198, 201
    Peek I. 143
    Peeters R. 203
    Peeva L.G. 62
    Peeva P. 258
    Pei Z. 184
    Peinador R.I. 254
    Peinemann K.V. 8, 12, 13, 154
    Pelaez L. 239, 264, 265
    Pea B. 249
    Pearubia F. 480
    Peas Ballester P. 79
    Penkova A. 100
    Permki P. 77
    -502-
    Pera-Titus M. 45
    Pereira Jr. O. 320
    Perera J.M. 259
    Perez B. 341, 342
    Perez G. 175
    Perez-Herranz V. 187, 299, 302
    Perez-Magario S. 469
    Pericou J. 372
    Peris S. 14
    Perot J. 144
    Perry M. 238
    Persello J. 409, 410, 431
    Persin M. 217, 426
    Persson T. 358, 411
    Pessoa de Amorim M.T. 237
    Peters T.A. 133
    Petit E. 57
    Petitgirard A. 409, 410, 431
    Petitperrin S. 329
    Petra-Titus M. 214
    Petrus J.C.C. 73
    Pezennec S. 316
    PIlanz K. 477, 479
    PIohl Leszkowicz A. 135, 418
    Piacentini E. 170
    Picard C. 95
    Pierre G. 146, 434
    Pihlajamki A. 271, 326
    Pilatos G. 199, 282
    Pilatos G.I. 210
    Pinacca R. 198, 201
    Pinacci P. 213, 218
    Pingel H. 102
    Pinho M. 313
    Pinho M.N.C. 321, 412
    Pinoy L. 75
    Pinto S.I.S. 66
    Piquet F. 122
    Piry A. 116, 461
    Piscioneri A. 171, 187
    Pismenskaya N. 33, 76, 232, 307
    Pivier L. 20
    Plakas K.V. 432
    Platkowska A. 430
    Plaza A. 175, 341
    Pliskova M. 389
    Pochat-Bohatier C. 57, 205, 295
    Podvorica F. 312
    Pokajewicz K. 483
    Pokorny R. 66
    Poletto P. 433
    Pollerberg C. 344
    Polotskaya G. 100
    Ponce M.L. 226
    Poncin-Epaillard F. 228
    Pongracz E. 77, 422
    Pont N. 478
    Pontie M. 120, 141, 486
    Portugal C. 81
    Portugal C.A.M. 55, 234
    Potreck J. 156
    Ptschke A. 25
    Poupot C. 79
    PouraIshari-Chenar M. 197
    Pourcelly G. 33, 76, 120, 299, 314, 400,
    444
    Pourmoghadasi S. 475
    Pradanos P. 182, 202, 261, 300, 301,
    469
    Prazeres D.M.F. 166, 349
    Pregowska M. 163, 220
    Prochaska K. 332
    Pugazhenthi G. 210
    Quarez E. 127
    Queiroz T.N. 324
    Quemener D. 12, 190, 191
    Quetschke A. 25
    Rabiller-Baudry M. 122, 304, 360, 376, 442
    Racz G. 345
    Raetzke K. 12
    Rahimpoour A. 460
    Rahmouni K. 228, 401
    Raiado-Pereira L. 166, 349
    Rajca M. 430
    Rakib M. 69
    Rakib S. 416
    Raktae-ngan V. 176
    Ramakrishna S. 203
    Ramirez A. 142
    Ramos J.D. 264, 265
    Randova A. 192, 260
    Ranzani Da Costa A. 34, 439
    Rapaport H. 35
    Rapenne S. 146
    Rathore N.S. 301
    Rattanapisit J. 358
    Raynal J. 466
    Razavi S.M.A. 469
    Rebollar Perez G. 448
    Rees A. 477
    Reijerkerk S. 156, 158
    Reina J.A. 14, 220
    Reis M.A.M. 80, 81
    Reis M.H.M. 352
    Reiel M. 306
    Remigy J.C. 28, 52, 95, 147, 251
    Rende M. 171
    Renouard T. 362, 442
    Reverchon E. 186
    Rhamouni K. 129
    Riande E. 391
    Ribeiro E.A.M. 414
    Ricardo A.R. 80
    Richards B.S. 438
    Richards L.A. 438
    Richter H. 252, 356
    Rico Perez V. 167
    Riera Rodriguez F. 273
    Rietkerk M.D.A. 41, 100
    Rios N. 69
    Ripperger S. 116, 461
    Rivenc J. 65
    Rizzuti L. 110
    Robinson J.P. 278
    Rodriguez Filho G. 414
    Rodriguez M.A. 279
    -503-
    RoeloIs K. 390
    RoeloIs K.S. 126
    Rogers D. 50
    Roizard D. 70, 91, 185, 333
    Roldan L. 393
    Rolevink H.H.M. 229
    Rlling P. 313, 441
    Romanos G.E. 199, 210, 282
    Romeo A. 393
    Romero J. 341, 342
    Romero V. 264, 265
    Ronda J.C. 14
    Ronen Z. 245
    Ronova I. 43
    Roques C. 146, 434
    Roth T. 85
    Roualdes S. 23, 127, 398
    Rouch J.C. 95
    Roudesli S. 33, 297, 308, 477
    Rouessac V. 18, 242
    Rouillon L. 125
    Rousseau F. 174
    Roux de Balmann H. 50, 55, 74, 139, 274
    Rovira M. 272, 284
    Roy S.N. 19
    Ruby R. 472
    Ruiz B. 104, 120
    Ruiz J.C. 246
    Ruiz M.O. 323, 346
    Rusakova O. 255
    Rssel C. 21
    Saaeidi dehaghani A.H. 29
    Saakes M. 134
    Sabate J. 293, 348
    Sabjan M. 21
    Sadeghi F. 364
    Sadeghi M. 29
    Sadeghian Z. 47, 208
    Sagne C. 427
    Sagrista E. 423
    Sahmoune A. 240
    SaiIul S. 483
    Saimani S. 292
    Sairam M. 107, 204
    Sakaki K. 206, 311, 319, 354
    Sakellaropoulos G.P. 207
    Sala B. 129, 228, 400, 401
    Salamon D. 86, 108
    Salehi E. 309
    Salerno S. 171, 187
    Salvado V. 420, 423, 478
    Salvalaglio M. 289
    Salvaterra A.F. 321
    San Roman M.F. 64, 303
    Sanchez E. 208
    Sanchez J. 39, 65, 334, 340
    Sanchez J.M. 385, 450
    Sanchez M. 202
    Sanchez M.L. 451
    Sanderson R.D. 123
    Sandru M. 453
    Santarelli X. 98
    Santos A.C. 412
    Santos J.L.C. 363, 442, 488, 489
    Sanz R. 216
    Sarbatly R. 325, 424
    Sarkar S. 19
    Sarrade S. 246
    SarraIzadeh M.H. 324, 353, 364, 373, 423
    Sarti G.C. 10, 13, 64, 131, 285, 289,
    350
    Sartowska B. 411
    Sastre A.M. 301
    Satha H. 15
    Saukaitis J. 158
    Sauvade P. 49, 146
    Savignac J. 274
    Savinskaya O.A. 227
    Sayadi S. 419
    SchIer A.I. 438
    SchIer M. 37
    SchIer T. 37
    Schauer J. 387, 389
    Schenk J. 92
    Scheper T. 167
    Schetrite S. 135, 372
    Schieber S. 334
    Schieda M. 396
    Schiestel T. 20, 21, 126, 312, 388, 390,
    448
    SchiIIer P. 344
    Schippers J. 119
    Schippers J.C. 374
    Schirrmeister S. 20, 21
    Schlehuber D. 26, 222, 267
    Schlenstedt K. 25
    Schmidt H.J. 334
    Schmitz P. 371
    Schneider C.M. 252
    Schreyer A. 467
    Schrive L. 140
    Schrotter J.C. 47, 95, 142, 146, 266
    Schubert R. 30
    Schulz C.K. 320
    Schulze A. 30
    Schwartz A. 388
    Schwerdt P. 344
    Scura F. 447
    Sechel N. 209
    Seda L. 66, 256, 308
    Sedghi S. 197
    Seira J. 416
    Selimi T. 312
    Sellerberg W. 78
    Sereewatthanawut I. 107, 480
    Servat K. 396
    Serwicka E.M. 485
    Seta P. 240, 241
    Sghyar M. 416
    Shahidi M. 469
    Shalygin M. 455
    Shanahan D.P. 100
    Shantarovich V.P. 42
    Shao H. 231
    Shaposhnik V. 307
    Shapter J.G. 28, 244
    -504-
    Shearer C.J. 244
    Shih Y.J. 31, 231
    Shimada Y. 319
    Shimizu E. 435
    Shirasaki N. 148, 436
    Shishatskiy S. 8, 12, 154
    Shornikova O. 206
    Shugman E. 382
    Siddique H. 204
    Sierra C. 361
    Sijbesma H. 156
    Silva A.M.F. 321
    Silva B.B.R. 200, 222
    Silva C.S. 367
    Silva F.C. 473
    Silva P. 62
    Silva V. 300, 301
    Silva W. 341
    Simone S. 89
    Sinan F. 426
    Sindelar V. 236
    Singh G. 203
    Singheiser L. 222, 252
    Siozade L. 280
    Sipek M. 11, 236
    Sirat A.K. 129, 400, 401
    Sistat P. 33, 54, 55, 76, 104, 120,
    286, 299, 307, 361, 368,
    444
    Sivertsen E. 48, 51, 110
    Slodczyk A. 129
    Smart S. 27
    Snijkers F. 23
    Soltanieh M. 381
    Soroko I. 270
    Sotto A. 185, 277, 278
    Souchon I. 92
    Soudani A. 426
    Soussan L. 147
    Soydas B. 215
    Sperr P. 53
    Springer F. 111
    Sridang P. 358
    Stadniy I. 220
    Stahra N. 182
    Stamatialis D. 103, 150, 172, 194, 388
    Stamatialis D.F. 443, 483
    Stange M. 133
    Staudt C. 313, 441
    Stawikowska J. 257
    SteIIen B. 306
    Steinbrech R.W. 252
    Steiner Z. 35
    Steinke J.H.G. 107
    Stevens G.W 259
    Stibius K.B. 238, 239
    Stoller M. 137, 174, 408
    Streit K. 412
    Struzynska I. 16, 150
    Stber F. 141
    Sugawara T. 85, 238
    Sugita M. 394
    Sulej J. 332
    Sultanov E. 12, 193
    Sun J. 483
    Susanto H. 182
    Sutanto S. 262
    Suttivattanavet W. 328
    Suzuki T.M. 17
    Svec J. 236
    Syrtsova D. 206
    Sysel P. 188, 236
    Szentgyrgyi E. 360
    Szpakowska M. 485
    Szymczyk A. 62, 250, 269, 291
    Tabatabaee Nezhad S.A.R. 381
    Taillades G. 127
    Taillades-Jacquin M. 127
    Taillandier P. 466
    Takagi R. 271
    Takenouti H. 129, 228, 401
    Takimoto N. 51
    Talla Feuhouo E. 486
    Tamime R. 249, 280
    Tanaka M. 2
    Tancredi M. 487
    Tantekin-Ersolmaz S.B. 6, 155, 194, 290
    Tasselli F. 46, 171, 187
    Tavares C. 237
    Tavares J.M.R. 321
    Tayeb R. 98
    Tayouo R. 23
    Tazi-Pain A. 366
    Teixeira A.R.S. 442, 488
    Tellez C. 6, 263, 454
    Temmink H. 115, 118, 374
    Ten ElshoI J.E. 41, 100
    Tena A. 202
    Teplyakov V. 161, 333, 455
    Teplyakov V.V. 206
    Tereshchenko G. 233
    Ternes I. 396
    Thai B.S. 312
    Thelledath A. 120
    Thiry X. 224
    Thom V. 167
    Thominette F. 223, 402
    Thming J. 279, 330
    Thorel A. 127
    Thorsen T. 48, 51, 110
    Thueux F. 360
    Tilliket G. 165
    Tingry S. 240, 241, 396
    Tocci E. 42, 67, 288
    Toikka A. 100
    Tomaszewska M. 88
    Tomicki F. 233
    Trebouet D. 339
    Tregret L. 360
    Trentin A. 471, 472
    Tronin V. 295
    Tronin V.N. 298
    Trotta F. 189
    Tsarkov S. 446
    Tsarkov S.E. 298
    Tsodikov M. 333
    -505-
    Tsybulya S.V. 227
    Tu Z. 425
    Tusel E. 356
    Tylkowski B. 14, 163, 220
    Uhlmann D. 27
    Ulbricht M. 32, 45, 182, 184, 233, 242,
    258, 290
    Umpuch C. 74
    Urasaki T. 148
    Urbanowska A. 429
    Uriel S. 6
    Urkiaga A. 370
    Urtiaga A. 347, 399
    Urtiaga A.M. 175
    Utiu L. 109
    Uvarov V. 333
    Vachiraanan K. 358
    Vachoud L. 205
    Vaireanu D.I. 241
    Valdes H. 342
    Valentine M. 288
    Valenzuela F. 342
    Valtchev V. 386
    Van Audenhaege M. 316
    Van Bael M. 203
    Van Blitterswijk C. 172
    Van Camp W. 149
    Van Craeyveld V. 185
    Van de Ven E.C. 25
    Van der Bruggen B. 63, 75, 185, 292, 651, 440
    Van der GraaI J. 134
    Van der Lee A. 36, 40, 129
    Van der Marel P. 115, 118, 374
    Van der Meer W. 115, 118, 374
    Van der Meer W.G.J. 114, 374
    Van der Vegt N. 452
    Van Der WerI H. 285
    Van Geluwe S. 351
    Van Nieuwenhuijzen A. 134
    Van Rijn C. 229
    Van Veen H.M. 41, 100
    Vandeur J. 185
    Vandezande P. 53, 149, 151, 203, 259
    Vanherck K. 38
    Vankelecom I.F.J. 38, 53, 149, 153, 183, 197,
    259, 315, 440, 445
    Vanneste J. 185
    Vnsk M. 383
    Varnava B. 143
    Vasconcelos R. 168
    Vasil eva V. 307
    Vatai G. 322, 345
    Vazquez M.I. 239, 264, 265
    Veerman J. 134
    Velasco C. 377
    Velizarov S. 80, 102, 363, 420
    Velleman L. 28
    Venault A. 205
    Vente J.F. 41
    Vente J.F. 100
    Vera E. 55, 274, 361
    VerhoeI A. 292
    Vermisoglou E.C. 199, 282
    Veyret D. 68, 111
    Vezina L.P. 169
    Veziri C. 199, 282
    Vial D. 176, 258, 404
    Vidal D. 418, 466
    Vidal S. 224
    Vida-Simiti I. 209
    Viegas R.M.C. 163
    Vieira da Silva F. 352
    Vienken J. 173
    Villain L. 167
    Villasante J. 300
    Vilt M.E. 167
    Vinckier C. 351
    Viotto L.A. 193, 305, 322, 323, 324,
    375, 378, 468, 470, 473,
    474
    Vissing T. 238
    Voelcker N.H. 244
    Vogel C. 25, 226
    Vogel J. 238
    Voicu S.I. 230, 241
    Voigt I. 356
    Voinea O.C. 399
    Volkov A.V. 298, 443, 446
    Volkov V. 295
    Volkov V.V. 443, 446
    Von Lieres E. 290
    Vopicka O. 11, 236
    Voss B. 39
    Wachinski A. 78
    Wachinski T. 176, 258, 404
    Wade M. 419
    Wakui Y. 17
    Walitza E. 312, 388
    Wang B. 131
    Wang D.M. 12, 190
    Wang J. 290
    Wang L. 418
    Wang S. 327
    Wang S.F. 328
    Watanabe K. 206, 319
    Waton H. 24
    Wdowiak E. 423
    Wei J. 327
    Wei T.C. 231
    Werapun W. 57, 295
    Wessling M. 2, 16, 25, 86, 93, 103, 108,
    114, 115, 118, 119, 150,
    156, 158, 172, 180, 194,
    229, 285, 374, 388, 392,
    443, 483
    Weyd M. 356
    Wieczorek P. 423
    Wieczorek P.P 483
    Wienk I.M. 153, 422
    Wienold A. 382, 406
    Willemin S. 129, 228, 401
    Willenberg A. 99, 101
    Willershausen P. 405
    Williams P. 314
    Williams P.M. 50
    Wind J. 13, 453
    -506-
    Winnubst L. 16, 150
    Winston Ho W.S. 130
    Wintgens T. 109, 235, 421
    Wisniewski C. 353, 416
    Witek-Krowiak A. 368
    WolII T. 102, 453
    Won J. 37, 49, 450
    Wong J.E. 235
    Wong W.T. 390
    Wright C. 50
    Wu Z. 399
    Wu Z.T. 131
    Wursthorn P. 390
    Wyart Y 144, 249, 280
    Wyns K. 151
    Xiaosheng J. 347
    Xu F. 56, 124, 283
    Yaacoubi A. 253
    Yacou C. 16
    Yakimanskii A. 255
    Yakovlev V. 255
    Yampolskii Y. 43
    Yampolskii Y.P. 42
    Yanagishita H. 206, 319, 354
    Yaroshchuk A. 272, 284
    Yasar Mahlicli F. 171
    Yastrebov R. 455
    Yave W. 8, 12, 13
    Yazdanshenas M. 381
    Yemenicioglu A. 297, 477, 308
    Yilmaz L. 9, 317, 449
    Yilmaz O. 155
    Yoo S. 450
    Yoshinaga H. 132
    You S.J. 350, 370
    Younas M. 340
    YousseI G.R. 367
    Yu T.L. 391
    Yce S. 460
    Yurekli Y. 33, 297, 308, 477
    Yushkin A. 298
    Zakrzewska-Trznadel G. 281, 411
    Zaman R. 53
    Zamani F. 47, 208
    Zamariotto D. 409, 410
    Zarragoitia A. 372
    Zator M. 114
    Zeni M. 337, 378, 414, 433, 488
    Zenikheri F. 330
    Zere Rezene T. 115
    Zgazar M. 11, 236
    Zhang L. 327
    Zhang Y. 75
    Zhao J. 281
    Zhmakin V. 333
    Zhu B.. 14
    Zhu H. 62
    Zikanova A. 211, 212, 303
    Zimmermann W. 78
    Zipperle M. 20, 21
    Zitka J. 389
    Zitouni B. 398
    Zornoza B. 263
    Zubov A. 256
    Zuriaga Agusti E. 487
    Zwijnenberg H. 419
    Zwijnenburg A. 115, 118, 374
    Zydorczak B. 159
    -507-
    Publisher of the Euromembrane 2009
    Abstracts Book
    Vot re dist ribut eur...

    ...pour t ous les produit s du laborat oire

    Des applications pour la:
    Biolechuologie
    Cullure cellulaire
    Chiuie
    Chroualographie
    ^ualyse de l'eau
    Microbiologie...


    uu choix couplel de.
    Cousouuables
    Equipeueuls
    Produils chiuiques el raclis
    Equipeueuls de prolecliou iudividuelle...
    VW8 InternaticnaI S.A.S Le Frigares - 8t 8 201, rue Carnct 94126 Fcntenay-scus-8cis cedex
    1eI: 0825 02 J0 J0 (0,156 11Clmin) Fax: 0 825 02 J0 J5 (0,156 11Clmin) MaiI: service.cIientsfr.vwr.ccm
    ht t p://f r.vwr.com
    WATER TREATMENT AND MODIFICATION
    We are well aware of a signicant importance of water for the life on Earth as well as the constantly increasing
    demands for its consumption, quality and environmental friendly processing in industry. We develop, design and
    deliver membrane technologies for treatment and desalination of water, offering alternative solution for industry
    and public distribution networks in the areas suffering from a lack of suitable water sources or allowing treatment
    and recycling of industrial waste water.
    water desalination -
    treatment of underground and surface sources of drinkable water -
    recycling and treatment of industrial waste water -
    nal treatment of pre-treated waste water -
    SPECIAL APPLICATIONS
    Special applications prove versatility of use of ion-exchange membranes Ralex with high expertness of our R&D
    staff and technologists looking for specic solutions. The result is utilization of our membrane technologies in
    purication processes in technologically and hygienically demanding production of biotechnological preparations
    for pharmaceutical industry, production of food supplements, in separation processes of chemical industry or in the
    sphere of galvanization.
    pharmaceutical industry -
    purication of organic substances -
    separation of inorganic and organic solutions -
    regeneration and recycling of galvanic baths -
    FOOD PROCESSING INDUSTRY
    Our priority are the spheres of dairy-farming and brewing production. With a help of the membrane technologies it
    is possible to achieve up to 90 % of demineralization of milk whey, as yet the underutilized waste product of cheese,
    casein and cottage cheese production. Demineralized milk whey may be used for production of traditional milk
    products, nutrition for babies, lactose or whey protein concentrates (WPC). We have also built a strong position in
    brewing industry with treatment of water for beer production. A unique taste of the Pilsen beer is the best reference
    of quality and professionalism of our services.
    milk whey demineralization -
    milk whey acidity control -
    treatment of water used for beer production -
    E-COAT
    A method of cataphoretic paint coating belongs amongst the most advanced technologies of metal surface nish.
    Our tubular and desk electrophoretic boxes because of their durability, easy operation and especially suitable
    mechanical and electrochemical parameters of ion-exchange membranes Ralex have been proving good in
    paint shops of world-class automotive manufacturers, especially because of their capacity to satisfy even the most
    demanding requirements on anti-corrosive resistance of car bodies and metal parts.
    automotive industry -
    agricultural equipment -
    production of radiators -
    consumer industry -
    MEGA a.s. is a company providing rst-class technology and complex services
    in elds of water treatment, material surface nishing and ecology.
    LEADER IN ELECTRO-MEMBRANE PROCESSES WITH OWN MEMBRANE PRODUCTION
    MEGA a.s. | Division of Membrane Processes
    Pod Vinici 87, 471 27 Straz pod Ralskem, Czech Republic | Tel: +420 487 888 300, Fax: +420 487 888 302 | E-mail: sales@mega.cz | www.mega.cz

    S-ar putea să vă placă și