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overnight in air at room temperature. Finally, the solution (50/50 wt%) is used as the feed at
support tube is calcined at 550 C for 20 h. 75 C. The compositions of the feed and
Figure 2 shows scanning electron micrographs the permeate are determined by FID-gas chroma-
(SEM) of the surface and cross section of the tography (5MS capillary column). The perme-
CHA membrane on the a-alumina support ation flux and separation factor, a(H2O/
(Yamanaka et al. 2012). The high-silica CH3COOH), are calculated from the following
CHA-type zeolite membrane prepared on the equations:
a-alumina tube is connected with the stainless
steel tube using heat shrink tubing, and the tube Flux ðkg=m2 hÞ ¼
is subsequently set in the conventional batch-type
ðweight of permeate, kgÞ
pervaporation apparatus. An acetic acid aqueous
ðmembrane area, m2 Þ ðpermeation time, hÞ
(1)
Al2O3 support
5 µm 5 µm
CHA Zeolite Membrane 3
Product
Water
Membranes
reason, relaxation is used to control the fouling of microbial products (SMP) and bio-fouling in anaero-
these membranes (Le-Clech et al. 2006). Regard- bic membrane bioreactors. In: IWA specialized con-
ference on water environment
less of the membrane configuration, chemicals Hong SP, Bae TH, Tak TM, Hong S, Randall A (2002)
must be used at regular intervals to enhance phys- Fouling control in activated sludge submerged hollow
ical cleaning (Le-Clech et al. 2005). fiber membrane bioreactors. Desalination
143:219–228
Judd S (2005) Fouling control in submerged membrane
bioreactors. Water Sci Technol 51(6–7):27–34
Cross-References Judd S (2006) The MBR book: principles and applications
of membrane bioreactors in water and wastewater
▶ Anaerobic Membrane Bioreactor treatment. Elsevier Science, Oxford
Kang Y-T, Cho Y-H, Chung E-H (2007) Development of
▶ Attached Growth Membrane Bioreactor the wastewater reclamation and reusing system with a
▶ Backwashing submerged membrane bioreactor combined
▶ Backwashing Frequency bio-filtration. Desalination 202:68–76
▶ Biological Fouling Lawrence P, Adham S, Barro L (2002) Ensuring water
re-use projects succeed – institutional and technical
▶ Cake Layer issues for treated wastewater re-use. Desalination
▶ Inorganic Scaling 152:291–298
▶ Irreversible Fouling Le-Clech P, Fane A, Leslie G, Childress A (2005) MBR
▶ Membrane Bioreactor for Reuse focus: the operators’ perspective. Filtr Sep
42(5):20–23
▶ Membrane Bioreactor (MBR) Plants Le-Clech P, Chen V, Fane TAG (2006) Fouling in mem-
▶ Membrane Cleaning brane bioreactors used in wastewater treatment.
▶ Permeate J Membr Sci 284:17–53
▶ Potable Water Production Meng FG, Chae SR, Drews A, Kraume M, Shin HS, Yang
FL (2009) Recent advances in membrane bioreactors
▶ Reversible Fouling (MBRs): membrane fouling and membrane material.
▶ Submerged Membrane Bioreactor Water Res 43(6):1489–1512
▶ Ultrafiltration Psoch C, Schiewer S (2005) Critical flux aspect of air
▶ Wastewater Treatment in Membrane sparging and backflushing on membrane bioreactors.
Desalination 175:61–71
Bioreactors Psoch C, Schiewer S (2006) Resistance analysis for
enhanced wastewater membrane filtration. J Membr
Sci 280:284–297
References Smith PJ, Vigneswaran S, Ngo HH, Ben-Aim R, Nguyen H
(2005) Design of a generic control system for
optimising back flush durations in a submerged
Achilli A, Marchand EA, Childress AE membrane hybrid reactor. J Membr Sci 255:99–106
(2011) A performance evaluation of three membrane Stephenson T, Judd S, Jefferson B, Brindle K (2000)
bioreactor systems: aerobic, anaerobic, and attached- Membrane bioreactors for wastewater treatment.
growth. Water Sci Technol 63:2999–3005 IWA Publishing, London
Bouhabila EH, Ben-Aim R, Buisson H (2001) Fouling Wang ZW, Wu ZC (2009) A review of membrane fouling
characterisation in membrane bioreactors. Sep Purif in MBRs: characteristics and role of sludge cake
Technol 22–23:123–132 formed on membrane surfaces. Sep Sci Technol
Fane AG, Fane SA (2005) The role of membrane technol- 44(15):3571–3596
ogy in sustainable decentralized wastewater systems. Yang W, Cicek N, Ilg J (2006) State of the art of mem-
Water Sci Technol 51(10):317–325 brane bioreactors: worldwide research and commer-
Fawehinmi F, Lens P, Stephenson T, Rogalla F, Jefferson cial applications in north America. J Membr Sci
B (2005) The influence of operating conditions on 270:201–211
extracellular polymeric substances (EPS), soluble
A
Affinity Membranes, Table 1 Some commonly used activation agents for affinity membrane preparation
Activation agent Structure Functional groups of the basic membrane
Cyanogen bromide –OH
N C Br
Carbonyldiimidazole –OH, –NH2
O
N N
N N
2-Amino-4,6-trichloro-s-triazine –OH
Cl
N N
Cl N NH2
Glutaraldehyde –OH, –SH, –NH2
O O
Divinyl sulfone –OH, –SH
O CH2
S
H2C O
Epichlorohydrin –OH, NH2
O
Cl
functional groups required for the coupling of the biocompatibility. Like cellulose, it contains
ligands (such as –OH, –NH, –SH, –COOH). hydroxyl groups that can be easily activated.
The commercially available materials used for Polyamide and nylon have been also used for
affinity membrane preparation include organic the preparation of affinity membranes, thanks to
(natural or synthetic polymer), inorganic, and their good mechanical and chemical stability.
composite materials. Nylon membranes have a low concentration of
Among the first materials used for affinity amino groups to serve as functional groups for
membrane preparation, cellulose and its deriva- ligand coupling. Also, due to the hydrophobic
tives (regenerated cellulose, cellulose acetate) surface, the membrane presents a high
were the most common. These present a hydro- nonspecific adsorption of biomolecules during
philic and biocompatible surface, low affinity separation process. Therefore, the hydro-
nonspecific adsorption, and abundant reactive lysis of the membrane is generally performed to
hydroxyl groups that can be easily activated by increase the density of reactive groups and to
different strategies for the ligand coupling. To prevent electrostatic interaction with proteins.
improve the density of functional groups and To overcome these problems, composite nylon
increase the mechanical strength, composite cel- membranes have been also prepared.
lulose membranes have been also prepared by Other materials that have been used for affin-
chemical grafting with acrylic polymers. ity membranes are poly(methyl methacrylate),
Another suitable membrane material is poly- polysulfone and its derivative, polycaprolactam,
vinyl alcohol, thanks to its hydrophilicity and polyvinylidene difluoride, poly(ether-urethane-
urea), and inorganic materials such as glass.
Affinity Membranes 3
Affinity Membranes, Table 2 Some examples of the use of affinity membranes for isolation and purification of
biomolecules
Membrane Ligand Ligate Application
Cellulose and regenerated Cibacron Blue F3GA Alkaline phosphatase Purification
cellulose Protein A/G IgG Purification
Histidine Endotoxin Removal of
endotoxin
Poly(ethylene-co-vinyl Histidine IgG Purification
alcohol)
Nylon Cibacron Blue Glucose-6-phosphate Purification
dehydrogenase
Protein G IgG Purification
Histidine Endotoxin Removal of
endotoxin
Polyvinylidene difluoride Protein A IgG Purification
(PVDF)
Polysulfone (PS) Trypsin Trypsin inhibitor Purification
Iminodiacetic acid Histidine/tryptophan Purification
(IDA)
Glass IDA-Cu2+ Lysozyme, cytochrome c, Purification
ribonuclease A
Membrane Activation and Ligand Coupling specificity for only one complementary
If the basic membrane does not possess the func- biomolecule.
tional groups for ligand coupling, it can be Because of their selectivity, biomolecules
activated. have been the most widely used affinity ligands
In Table 1 are reported the commonly used on affinity membrane separation technology. One
activation agents with respect to the functional of the most common applications is the use of
groups present on the basic membrane. immobilized monoclonal antibodies for
The coupling of the ligand directly on the immunoaffinity separation. Another important
activated membranes may result in low binding example is membranes with covalently coupled
specificity due to the low steric availability protein A or protein G for immunoglobulin puri-
(in particular when the ligand is a small mole- fication from plasma, serum, or cell culture
cule). This problem is generally overcome by the supernatants.
introduction of a spacer molecule to the mem- Although the biospecific ligands possess high
brane prior to attaching the ligand, improving the specificity for proteins, they have some limitation
ligand accessibility for the molecule to be sepa- for large-scale application due to their poor sta-
rated. Spacer arms are bifunctional molecules bility and high price.
able to react with both the membrane and ligand. The alternative approach to biospecific
ligands involves the use of pseudo-biospecific
ligands. These are usually molecules with higher
chemical and physical stability than biomole-
Affinity Ligands
cules. Pseudo-biospecific ligands can be distin-
guished by biological (amino acids, specially
Affinity ligands can be classified into biospecific
histidine, lysine, tryptophan) or non-biological
and pseudo-biospecific ligands (Klein 1991).
molecules (dyes, chelated metal ions).
Biospecific ligands are biomolecules such as anti-
The working principle of pseudo-biospecific
bodies, antigens, and proteins A and G that show
ligands relies on the complementarity of
4 Affinity Membranes
structural features of ligand and ligate rather than Applications of Affinity Membranes
on a biological function. Immobilized dyes have
been found to act as affinity ligands for a wide Affinity membranes are used for several different
variety of biological molecules. For example, applications such as purification of biomolecules,
triazine-linked dyes have been used to mimic removal of unwanted substances from biological
coenzymes that bind a number of dehydroge- fluids, and also small-scale analytical
nases, hexokinases, and alkaline phosphatases; separations.
the reactive triazine groups can be linked to any The most common application is the separa-
matrix containing hydroxyl groups by mixing the tion and purification of biomolecules and espe-
two together. Cibacron Blue F3GA (a textile dye) cially proteins for large-scale production.
has been employed as ligand in affinity mem- In Table 2 are reported some typical examples
branes for the purification of over 80 enzymes of their use for the separation and purification of
and proteins. biomolecules.
Another important example of pseudo-
biospecific affinity ligands is chelated metal
ions used for the purification of histidine-tagged
References
fusion proteins.
Klein E (ed) (1991) Affinity membranes: their chemistry
and performance in adsorptive separation processes.
Molecular Imprinted Membranes Wiley, New York
Klein E (2000) Affinity membranes: a 10-year review.
J Membr Sci 179:1–27
A different approach for the preparation of affin- Wilson ID, Poole CF (2009) Handbook of methods and
ity membranes is the use of molecularly instrumentation in separation science,
imprinted polymeric materials. These are pro- vol 1. Academic, Boston
duced by entrapping a template molecule (the Zou H, Luo Q, Zhou D (2001) Affinity membrane chro-
matography for the analysis and purification of pro-
molecule to be separated) in a polymer matrix teins. J Biochem Biophys Methods 49:199–240
during polymerization and subsequent extraction.
In this way, binding sites are introduced in the
polymer that are complementary in shape and
functionality to the target molecule.
A
Air Dehydration by Membrane Technology, Fig. 1 Removal of moisture from humid air through a membrane
WATER
VAPOR
LOW
HUMID
HUMIDITY
AIR
DEHUMIDIFICATION AIR
1 UNIT
2 3 CONDENSER 4
“COMPRESSOR”
5 NON-CONDENSABLE
VACUUM
PUMP GAS
LIQUID LIQUID
RESERVOIR PUMP
LIQUID
Air Dehydration by Membrane Technology, Fig. 2 Process flow diagram of a membrane dehumidification system
When humid air is at low or atmospheric pres- into environment. The condensed water is col-
sures, using ambient air as a sweep stream is no lected in a reservoir. Water in the reservoir may
longer practical, and pulling vacuum in the per- be discharged using a liquid pump, while residual
meate side becomes necessary. In this case, sev- air – noncondensable gas – is discharged into
eral other pieces of equipment in addition to the environment using a secondary vacuum pump.
membrane separator are required to make an
integrated dehumidification system (Fig. 2).
Such a membrane dehumidifier has been recently References
proposed and is still under development (Xing
et al. 2013). An array of membrane units can be Morgan WH, Bleikamp LK, Kalthod DG (1996) Hollow
fiber membrane dryer with internal sweep, US patent
assembled together that the permeate sides of all
no. 5,525,143
the membrane units are connected to one com- Xing R, Rao Y, TeGrotenhuis W, Canfield N, Zheng F,
mon vacuum line. The vacuum is generated by Winiarski DW, Liu W (2013) Advanced thin zeolite/
the use of a vacuum pump or gas compressor. The metal flat sheet membrane for energy efficient air
dehumidification and conditioning. Chem Eng Sci
permeated moisture is compressed to a pressure
104:596–609
above water dew point at environmental temper- Ye X, LeVan MD (2003) Water transport properties of
ature so that water vapor is condensed into liquid- Nafion membranes: part I. Single-tube membrane
phase water by rejecting heat of condensation module for air drying. J Membr Sci 221:147–161
A
Air Enrichment, by Polymeric are dried in 40 C for at least 2 days and then are
Magnetic Membranes stored in an exsiccator under the vacuum condi-
tions (p = 3 mmHg). Collection of permeation
Anna Strzelewicz quantities both for individual gases (O2, N2) and
Faculty of Chemistry, Silesian University of for their mixture (air 21 %O2/79 % N2) is mea-
Technology, Gliwice, Poland sured in experimental setup (Fig. 1).
The measurements are carried out in room
temperature for membranes with dispersed mag-
The idea of using magnetic membranes for netic powder before and after magnetization in a
enrichment of air by oxygen is based on the field magnet with magnetic induction about
observation that oxygen and nitrogen have quite 2.5 T. The setup furnished with a gas chromato-
different magnetic properties, i.e., oxygen is graph allows to measure the oxygen and the
paramagnetic whereas nitrogen nitrogen concentration in permeate. The main
diamagnetic. The oxygen molecule is paramag- part of the experimental setup is diffusive cham-
netic with a magnetic moment of ber, where the membrane is put in the form of
mO2 ¼ 2:73 1023 JT 1 : Magnetic susceptibil- disk. The setup is used for a low-pressure (from
ity of nitrogen is equal to w ¼ 150:8 106 0.1 to 1.0 MPa) analysis of gas permeation.
mol1 ¼ 2:5 1028 molecule1 which corre- Transport coefficients can be calculated using
sponds only to m ¼ 2:5 1028 JT 1 in a mag- flow rate data and percentage of air enrichment.
netic field of 1 T, a value five orders of magnitude The flow rate of the permeate can be recorded
smaller than the O2 magnetic moment (Morrish using a flowmeter. Integration of flux with
1965; Borys et al. 2011). respect to time allows to sketch a downstream
Magnetic membranes are polymeric mem- permeation curve. Typical plot of Qa(l,t) versus
branes (ethyl cellulose (EC) or poly time is presented in the Fig. 2.
(2,6-dimethyl-1,4-phenylene oxide) (PPO)) with Time-lag method and D1-D8 system allow to
dispersed magnetic powder (ferrite, praseodym- get some insight into the nature of the considered
ium, and neodymium). The membranes are made transport process. In papers (Strzelewicz and
by casting of appropriate polymer solution with Grzywna 2007, 2008; Rybak et al. 2009a, b,
dispersed magnetic powder in an external mag- 2012; Grzywna et al. 2010) a concept of magnetic
netic field of a specially designed coil (stable membranes for air enrichment is explained. The
magnetic field with range of induction authors observed an increase in the oxygen flux
0–40 mT). Removed from Petri dish membranes with respect to the nitrogen flux and the enrich-
ment in the oxygen content of the permeate up to
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_12-4
2 Air Enrichment, by Polymeric Magnetic Membranes
Air Enrichment, by
Polymeric Magnetic
Membranes,
Fig. 1 Scheme of the
experimental setup
Air Enrichment, by a
Q
Polymeric Magnetic point for checking
Membranes, oxygen content
stationary state
Fig. 2 Downstream
absorption permeation
curve
a
Q (I, t)
La(L) t
– C0 1
6
55.6 % for ethyl cellulose magnetic membranes. et al. 2011) of the magnetic membrane cross
Further permeation measurements done in section that the feed side of the membrane is
polyphenylene oxide (PPO) magnetic mem- composed of a pure polymer while the output
branes provided higher enrichments, up to side consists of the polymer with dispersed mag-
61.9 % (Table 1). netic granules. When the magnetic field is too
The transport of the molecules through the strong, then magnetic aggregates are created,
magnetic membranes can be modeled by a diffu- which influence the permeation of gases.
sion with a position-dependent diffusion coeffi- Detailed analysis of the available data and
cient. Such a diffusion coefficient reflects the microscopy images allowed to arrive four con-
changes in the membrane composition along the clusions (Borys et al. 2011):
permeation axis. One can observe on the scan-
ning electron microscope photograph (Borys
Air Enrichment, by Polymeric Magnetic Membranes 3
Air Enrichment, by Polymeric Magnetic Membranes, Table 1 Air enrichment for various membranes (Strzelewicz
and Grzywna 2007)
Membrane B[mT] Oxygen content in permeate [%]
EC + 1.38 g Nd 0.79 40.7 1.1
EC + 1.49 g Nd 1.25 43.8 1.1
PPO + 1.80 g Nd 1.70 54.1 1.4
PPO + 1.80 g Nd 2.70 61.9 1.5
1. There are magnetic channels formed around Grzywna ZJ, Rybak A, Strzelewicz A (2010) Air enrich-
the magnetic granules. ment by polymeric magnetic membrane. In:
Yampolskii Y, Freeman B (eds) Membrane gas sepa-
2. The channels provide high permeability ration. Wiley, Chichester, pp 159–182
“highways” for the diffusion of permeating Morrish AH (1965) The physical principles of magnetism,
molecules. 1st edn. Wiley, New York
3. The oxygen molecules, due to their paramag- Rybak A, Krasowska M, Strzelewicz A, Grzywna ZJ
(2009a) “Smoluchowski type” equations for modelling
netic properties, stick to these “highways” for of air separation by membranes with various structure.
a longer time than nitrogen, which is probably Acta Phys Pol B 40:1447–1454
based on the interaction with the Weiss molec- Rybak A, Grzywna ZJ, Kaszuwara W (2009b) On the air
ular field of the permanent magnet. enrichment by polymer magnetic membranes.
J Membr Sci 336:79–85
4. The magnetic field induces aggregation Rybak A, Strzelewicz A, Krasowska M, Dudek G,
between oxygen and nitrogen which enhances Grzywna ZJ (2012) On the air separation process by
the transport of both nitrogen and oxygen by magnetic membranes influence of various parameters.
prolonging their residence in the channel. Sep Sci Technol 47:1395–1404
Strzelewicz A, Grzywna ZJ (2007) Studies on the air
membrane separation in the presence of magnetic
The method of air enrichment by magnetic field. J Membr Sci 294:60–67
membranes seems to be effective and efficient. Strzelewicz A, Grzywna ZJ (2008) On the permeation
time lag for different transport equations by Frisch
method. J Membr Sci 322:460–465
References
Air Separation,
Pressurized Oxygen
Fig. 1 Schematic ½O 2 + 2e − → O2−
air feed depleted air
representation of the
oxygen transport in MIEC MIEC
ceramic membrane ceramic
O2 - e- O2- e-
membrane
Alamine 336,
Fig. 1 Schematic structure
of Alamine 336
N
review of its applications. J Chem Technol Biotechnol Sun PP, Lee MS (2011) Separation of Pt(IV) and Pd
85:2–10 (II) from the loaded Alamine 336 by stripping. Hydro-
Sayar NA, Filiz M, Sayar AA (2007) Extraction of Zn metallurgy 109:181–184
(II) from aqueous hydrochloric acid solutions into Tamada JA, Kertes AS, King CJ (1990) Extraction of
Alamine 336–m-xylene systems. Modeling consider- carboxylic acids with amine extractants. Ind Eng
ations to predict optimum operational conditions. Chem Res 29:1319–1326
Hydrometallurgy 86:27–36 Tasker PA, Plieger PG, West LC (2003) Metal complexes
Steele WV, Chirico RD, Knipmeyer SE, Nguyen A, Smith for hydrometallurgy and extraction. In: McCleverty
NK, Tasker IR (1996) Thermodynamic properties and JA, Meyer TJ (eds) Comprehensive coordination
ideal-gas enthalpies of formation for cyclohexene, chemistry II, vol 9. Elsevier: Oxford, UK,. pp 759–808
phthalan (2,5-dihydrobenzo-3,4-furan), isoxazole, Yordanov B, Boyadzhiev L (2004) Pertraction of citric
octylamine, dioctylamine, trioctylamine, phenyl acid by means of emulsion liquid membranes.
isocyanate, and 1,4,5,6-tetrahydropyrimidine. J Chem J Membr Sci 238:191–197
Eng Data 41:1269-1284 Zhu Y, Cao M, Ma X, Xu C, Wang X, Ren L, Hu C (2012)
Dalton Trans 41(10):2935–40
A
Alcohol and Water Separation pervaporation (PV) process through dense mem-
branes are based on the solution-diffusion mech-
Tadashi Uragami anism (Binding et al. 1961; Aptel et al. 1974).
Organization for Research and Development of Therefore, when it is required that ethanol mole-
Innovative Science and Technology (ORDIST), cules with larger molecular size preferentially
Kansai University, Suita, Osaka, Japan permeate from an aqueous ethanol solution, it
cannot be expected to be separated by the diffu-
sion process. Consequently, only a difference of
Cross-linked poly(vinyl alcohol) (PVA) compos- solubility selectivity in the solution process in
ite membranes have been used in commercial PV which both ethanol and water components are
plants for dehydration of ethanol beyond the dissolved can contribute to the separation.
azeotrope. However aqueous ethanol solutions Figure 1 shows the ethanol concentration in the
that can be produced by bio-fermentation are permeate through a poly(dimethylsiloxane)
dilute (about 10 wt.%). Therefore, if ethanol/ (PDMS) membrane during PV and that sorbed
water-selective membranes with high efficiency into a PDMS membrane. These results support
can be prepared, the distillation process in the the hypothesis that the difference in the solubility
first stage to obtain an azeotrope can be replaced of the permeants contributes to the ethanol/water
ethanol-/water-selective membrane which is very selectivity. PDMS membranes show high etha-
advantageous for reduction of energy cost. There nol/water selectivity, but their mechanical
are fewer reports on ethanol-/water-selective strength is weak, and it is difficult to prepare
membranes compared with those of water-/ thin membranes from PDMS. In order to obtain
ethanol-selective membranes. One reason why both ethanol/water selectivity and mechanical
the development of efficient high-performance strength, graft copolymers composed of PDMS
ethanol-/water-selective membranes is difficult macromonomer and vinyl monomers were
can be attributed to the fact that ethanol has a synthesized.
larger molecular size than water and must be Graft copolymer membranes, which were
preferentially permeated through the membrane. either ethanol or water selective, were prepared
In fact, permeation and separation in a by copolymerization of a dimethylsiloxane
100 100
ve
cur
ibrium
equl
id
or-liqu
vap
60 60
40 40
20 20
0
0 20 40 60 80 100
EtOH in feed solution (wt%)
Alcohol and Water Separation, Fig. 1 Permeation and Alcohol and Water Separation, Fig. 2 Effects of the
separation characteristics of aqueous ethanol solutions DMS content on the normalized permeation rate (○) and
through a PDMS membrane during PV separation factor (●) through the PMMA-g-PDMS mem-
brane during PV. Feed: aqueous solution of 10 wt.%
ethanol. Dashed line is the feed composition
(DMS) macromonomer with methyl methacry- the determination of the percolation transition of
late (MMA) (Miyata et al. 1995, 1996). Two the PDMS phase at a DMS content of about
glass transition temperatures (Tg) were observed 40 mol%. These results suggest that the continu-
at about 120 C and 127 C in the graft copol- ity of the PDMS phases in the microphase-
ymer membranes. Transmission electron separated PMMA-g-PDMS membranes directly
micrograph (TEM) demonstrated that the affects their ethanol/water selectivity for aqueous
PMMA-g-PDMS membranes showed ethanol solutions (Miyata et al. 1995, 1996).
microphase-separated structures. When an aque- In Table 1, the performance of the ethanol-/
ous solution of 10 wt.% ethanol was permeated water-selective polymer membranes is com-
through the PMMA-g-PDMS membranes by PV, pared. As can be seen in this Table, the addition
the ethanol concentration in the permeate and the of PFA-g-PDMS to the PTMSP membrane in PV
permeation rate increased drastically with the was very effective, the application of TDEV
DMS content in the copolymer. In particular, at method to the membrane separation technique
a DMS content of less than 40 mol%, water was also very interesting for the enhancement of
permeates preferentially from an aqueous solu- the ethanol/water selectivity for the ethanol/
tion of 10 wt.% ethanol, whereas membranes water mixtures, and in particular the application
with more than about 40 mol% of DMS are eth- of porous PDMS membrane to temperature-
anol/water selective, as shown in Fig. 2. The difference controlled evapomeation (TDEV)
change in the ethanol/water selectivity of the (Uragami 1998, 2005, 2006a, b, 2008, 2010,
PMMA-g-PDMS membranes can be explained 2011; Uragami and Shinomiya 1991, 1992;
by a microphase-separated polymer structure Uragami and Tanaka 1991, 1993, 1994; Uragami
using Maxwell’s model and a combined model et al. 2002; Uragami and Morikawa 1989) was a
consisting of both parallel and series expressions. very excellent performance for the ethanol/water
Furthermore, image processing of TEMs allowed mixtures.
Alcohol and Water Separation 3
Masuda T, Tang B-Z, Higashimura T (1986) Ethanol- Giorno L (eds) Comprehensive membrane science and
water separation by pervaporation through engineering, vol 2, Membrane operations in molecular
substituted-polyacetylene membranes. Polym J 18:565 separations. Elsevier, Amsterdam/Boston/Heidelberg/
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acteristics of permeation and separation for aqueous Francisco/Singapore/Sydney/Tokyo, pp 273–324
ethanol solutions through methyl methacrylate- Uragami T (2011) Concentration of bio-ethanol through
dimethylsiloxane graft copolymer membranes. cellulose ester membranes during temperature-
Macromol Chem Phys 196:1211 difference controlled evapomeation. Mater Sci Appl
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aqueous ethanol solutions. Macromolecules 29:7787 temperature-difference controlled evapomeation. 11th
Miyata T, Obata S, Uragami T (1999a) Morphological World Filtration Congress & Exhibition, p 313
effects of microphase separation on the Uragami T, Morikawa T (1989) Permeation of ethanol
permselectivity for aqueous ethanol solutions of through polydimethyl siloxane membranes using
block and graft copolymer membranes containing temperature-difference in membrane process of the
poly(dimethylsiloxane). Macromolecules 32:3712 evapomeation method. Makromol Chem Rapid
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Nagase Y, Mori S, Matsui K (1989) Chemical modifica- evapomeation. J Appl Polym Sci 44:2009
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membrane. J Appl Polym Sci 37:1259 Makromol Chem 192:2293
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solutions through polymer membranes. Desalination component from a solution containing two or more
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pp 1087–1122 Uragami T, Doi T, Miyata T (1999) Control of
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Material science of chitin and chitosan. KODANSHA, J Adhes Adhes 19:405
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pp 113–163 erty of surface modified poly[1-(trimethylsilyl)-
Uragami T (2006b) Polymer membranes for separation of 1propyne] membranes. In: Pinnau I, Freeman BD
organic liquid mixtures. In: Yampolskii Y, Pinau I, (eds) Membrane formation and modification, ACS
Freeman BD (eds) Materials science of membranes Symposium Series 744. American Chemical Society,
for gas and vapor separation. Wiley, Chichester, Washington, DC, pp 263–279
pp 355–372 Uragami T, Tanaka Y, Nishida S (2002) Permeation and
Uragami T (2008) Structural design of polymer mem- separation under high temperature and high pressure
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A
Alkaline Fuel Cells (AFCs) have been demonstrated (Cifrain and Kordesch
2003). Furthermore, alkaline conditions allow
Tanja Vidakovic-Koch application of nonprecious metal catalysts
Max Planck Institute for Dynamics of Complex which could reduce significantly the material
Technical Systems, Magdeburg, Germany costs of this fuel cell. One of major disadvantages
of AFC is its low CO2 tolerance due to formation
of carbonates according to:
Alkaline fuel cell (AFC) is a fuel cell type which
utilizes alkaline electrolyte, usually potassium CO2 þ 2OH ⇄ CO3 2 þ H2 O
hydroxide. It consumes hydrogen and oxygen
producing only water, heat, and electricity. The carbonates have low solubility in strong alka-
Depending on a concentration of potassium line environments forming crystals, capable of
hydroxide, AFC can operate at temperatures blocking of electrolyte pathways. The low CO2
between 60 C and 250 C. The fuel cell reactions tolerance and the application of liquid electrolyte
are as follows: are two main hurdles for the broader commercial-
ization of these systems. However, due to its high
Anode : H2 þ 2OH ⇄ 2H2 O þ 2e efficiency and high power density, AFC found
applications in aerospace industry, e.g., they
Cathode : 1⁄2 O2 þ 2e þ 2H2 O ⇄ 2OH were employed on the Apollo missions as well
as on the Space Shuttle orbitals. For other exam-
Overall reaction : H2 þ 1⁄2 O2 ⇄ H2 O ples of developed AFC systems, please see
Cifrain and Kordesch (2003) and G€ulzow (2012).
The main ionic charge carriers are OH ions Hydrogen and oxygen gases in the AFC are
which mitigate from the cathode to the anode. separated by a membrane. Usually permeable
Water is formed at the anode side and has to be membranes also called diaphragms have been
removed from the system in order to prevent used (G€ulzow 2012). A common diaphragm
KOH dilution. The AFC has improved cathode material up to 1980s was asbestos which due to
performance compared to acidic fuel cells due to health and environmental concerns is nowadays
more favorable oxygen reduction reaction kinet- abandoned. Alternative materials are different
ics. For this reason, AFC can achieve higher polymer materials like porous polyethylene
efficiency, i.e., higher voltage at comparable cur- plates, nonwoven polypropylene, and similar.
rent densities than other fuel cell types. It has Potassium hydroxide electrolyte wets the
very long operating life time, e.g., 15,000 h
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_17-4
2 Alkaline Fuel Cells (AFCs)
formed on the AEMs, the pore size of the mem- membrane pores with the medium molecular
brane decreases and the transport number of sul- weight ions. To alleviate the problem of organic
fate ions, which are bulky relative to chloride fouling, there are basically two methods on the
ions, decreases. membrane side: first, to increase the pore size of
Fouling of separation membranes is a com- the membrane to allow easy permeation of large
mon problem. AEMs are fouled by ionic mate- ionic materials and, second, to prevent penetra-
rials of medium molecular weight such as ionic tion of the materials into the membrane at the
surfactants having the charge opposite to the membrane surfaces. There are two methods to
fixed charged of the membrane. Almost all of prevent penetration of large organic materials
organic foulants in many effluent streams have into the membrane matrix: forming a thin
negative charges; hence, fouling of AEMs due to charged layer opposite in sign to the
deposition and/or adsorption of the foulants on/in ion-exchange groups of the membrane or forming
the AEM is one of the serious problems in their a very thin and dense layer on the membrane
applications. The pore size of the AEM is gener- surfaces.
ally recognized to be about 1 nm; therefore, ions
of medium molecular weight permeate with dif-
ficulty through the membrane. Consequently, the Reference
fouling can lead to an unacceptably high stack
resistance and replacement of membranes in an Sata T (2004) Ion exchange membrane. The Royal Society
of Chemistry, Cambridge
electrodialysis system due to clogging of the
A
Until the mid-nineteenth century, the prediction For a given pure component in a closed cell, it
of the saturated vapor pressure of a liquid mixture calculates the saturated vapor pressure P (mmHg)
or even of a pure liquid in relation with the with the temperature T ( C) as follows:
temperature was not accurate despite the phe-
nomena being studied long before the Middle log10 P ¼ A B=ðT þ CÞ (1)
ages. The Antoine equation, which solves this
problem for pure components, is due to a French with A, B, and C being the Antoine coefficients,
engineer (Louis Charles Antoine, 1825–1897) in mmHg and C units, which are component-
and was first published in “Annales de Physique specific constants; e.g., for water : A = 8.07131;
et de Chimie” in 1891 (Antoine 1891). Antoine B = 1730.63 and C = 233.426 in the tempera-
introduced an equation able to predict the vapor ture range 1–99 C.
pressure of pure liquids (vaporization) and solids Other forms of the Antoine equation can be
(sublimation). It is worth noting that this equation deduced:
is still widely used today because of its accuracy.
Wisniak (2001) has recently reviewed the histor- P ¼ 10ðAB=ðTþCÞÞ (2)
ical development of the vapor pressure equations
from Dalton to Antoine.
P mmHg
100000 200
80000 00
100
60000
40000
20000
0
0 100 200 300 400
T °C
This calculation has been done for water with the Antoine C (1891) Annales de Physique et de Chimie 22:
281; ibid, Annales de Physique et de Chimie
coefficients: A = 8.07131, B = 1730.63, and
(1892) 26: 426; Comptes Rendus Acad Sci (Paris)
C = 233.426. The temperature validity range is (1888) 107: 1143
from 1 C to100 C. Data banks of Antoine Coefficients (visited June 2013)
http://webbook.nist.gov/ – http://booksite.elsevier.
com/9780080966595/content/Appendices/Appendix
– At T = 50 C: log10 (P) = 8.07131–1730.63/
%20C.pdf (free download) – http://www.eqi.ethz.ch/
(50 + 233.426) = 1.9652 fmi/xsl/eqi/eqi_property_details_en.xsl?node_id=
– Hence, P(sat) H2O = 92 mmHg 983 (directory for Physical Properties Sources) – -
Vapor-Liquid Equilibrium Data Collection,
DECHEMA Chemistry Data Series, Jurgen Gmehling
The results shown in Fig. 1 and Table 1 corre- et al. (Frankfurt)
spond to water vapor pressure calculated with the Reid CE (1990) Chemical thermodynamics. McGraw-
respective sets of parameters of each domain with Hill, New York, p 73
the Eq. 1. The discontinuity at 100 C can be seen Wagner W (1973) New vapour pressure measurements for
argon and nitrogen and an new method for establishing
in the Table 1. rational vapour pressure equations. Cryogenics
13(8):470–482
Wisniak J (2001) Historical development of the vapor
Cross-References pressure equation from Dalton to Antoine. J Phase
Equilib 22–6:622–630. doi:10.1007/s11669-001-
0026-x1143
▶ August Equation
A
c
a
3. Amino functionalized
Aptamer
100 nm 10 nm HN
b 120 O
N
O
60
40
S
1. Thiol Addition
20 via silanization
0 Si
O O
150 160 170 180 190 200 210 220 O
Average Size (nm) Silica Surface
Aptamer Membrane Functionalization, Fig. 2 Mesoporous particles (a), their size distribution (b), and the
functionalization of mesoporous silica with an aptamer (c)
large would not result in any aptamer-modulated (Serrano-Santos et al. 2012). Hence, mesoporous
permeability, while pores too narrow would hin- structures with a pore diameter between 2 and
der the aptamer from freely changing its confor- 3 nm have been found to be a suitable base mate-
mation. It could be shown that the thickness rial for aptamer-functionalized particles and mem-
change of a DNA-aptamer hairpin film amounts branes (Özalp and Schäfer 2011).
up to about 2 nm upon interaction with the target
Aptamer Membrane Functionalization 3
Aptamer Membrane Functionalization, change upon target recognition (b), and function to release
Fig. 3 Sequence of a DNA-aptamer hairpin that binds in a reversible, specific, and concentration-dependent fash-
selectively to ATP (a), scheme of its conformational ion cargo molecules (c)
Aptamer Screening,
Library Design by regions
Fig. 1
fixed random fixed Cloning, Sequencing
and Bioinformatics
Library
Interaction
Library/Target
Target
iteration
Selection of Target
Binders
Removal of
no binders
Enrichment of
selected binders
life, demonstrating their central role in with other ions and molecules through the first
maintaining normal physiology of all organisms. part of the glomerulus, they have been investi-
The first member of this family, AQP1, was iden- gated for developing biohybrid membranes able
tified in erythrocytes in 1991. This discovery led to desalinate seawater. The biohybrid membranes
to homology cloning of hundreds of AQPs homo- containing aquaporins showed very high water
logues from throughout the animal and plant selectivity and permeability. Technological chal-
kingdoms, as well as from lower organisms. lenges for productive application include
In humans there have been identified biohybrid membrane preparation on a large
13 aquaporins (AQP0–12) with specific organ, scale, aquaporin stability under operating condi-
tissue, and cellular localization. Thus, different tions or during membrane module cleaning, and
members of the AQPs family are expected to maintenance operation. Development of syn-
function in virtually all physiological processes thetic water channels mimicking aquaporins is a
that involve water transport across the new strategy under investigation. Highly selec-
membrane. tive and permeable water channels are very inter-
The AQPs are expressed in many cell types esting for the development of seawater
involved in fluid transport, including epithelia desalination plant operating with very low energy
and endothelia in the kidney, lung, exocrine input.
glands, eyes, and gastrointestinal tract. However,
aquaporins are also expressed in cells that do not
have an obvious role in fluid transport, such as References
erythrocytes and some leukocytes, adipocytes,
and muscle. In addition, these are also expressed Di Giorgio J, Soto G, Alleva K, Jozefkowicz C,
Amodeo G, Muschietti JP, Ayub ND (2014) Prediction
in astrocytes throughout the central nervous sys-
of aquaporin function by integrating evolutionary and
tem and in supportive cells. Aquaporins have functional analyses. J Membr Biol 247:107–125
been linked to a number of pathological condi- Kreida S, Tornroth-Horsefield S (2015) Structural insights
tions, including brain edema, renal disease, obe- into aquaporin selectivity and regulation. Curr Opin
Struct Biol 33:126–134
sity, and cancer, raising their attractiveness as
Papadopoulos MC, Verkman AS (2013) Aquaporin water
drug targets. channels in the nervous system. Nat Rev Neurosci
Given the key role played by aquaporins in the 14:265–277
kidney, for recovering water permeated together
A
Atomic Force
Microscopy (AFM),
mm
Fig. 1 3D image of
0.20
cyclopore microfiltration
0.10
membrane and pore-size
0.00
distribution for same
membrane obtained by 3
AFM
2
mm
1
3
2
0 1 mm
0
25
20
15
% of pores
10
0
0.10 0.15 0.20 0.25 0.30 0.35
Pore size, µm
large number of expansions for AFM instruments to simulate any of a number of potential mem-
allowing many other modes allowing mapping of brane foulants allowing quantitative measure-
electrical and electrochemical, mechanical, adhe- ments of foulant rejection and attachment
sive, frictional and magnetic properties of sur- forces. This makes possible the direct quantifica-
faces of interest. tion of membrane fouling properties of different
As well as providing this information, the materials under a range of environmental condi-
AFM probe can be used as a force sensor by tions and with only a relatively small sample of
moving the probe into and out of contact with membrane needed.
the sample surface and monitoring deflection in
the microcantilever arm. Through careful calibra-
tion of the system this deflection can be converted
References
into force, directly measuring the interaction
force as a function of probe tip – sample separa- Bowen WR, Hilal N (eds) (2009) Atomic force micros-
tion distance (Gibson et al. 2004). This allows the copy in process engineering. Butterworth-Heineman,
detection of DLVO, hydrophobic, hydrostatic Oxford
Bowen WR, Hilal N et al (1996) Atomic force microscope
and steric interactions, membrane stiffness, and
studies of membranes: surface pore structures of
adhesion forces. The sharp tip may be replaced by cyclopore and anopore membranes. J Membr Sci
a colloidal particle, which may be functionalized 110(2):233–238
Atomic Force Microscopy (AFM) 3
Gibson CT, Johnson DJ et al (2004) Method to determine modelling and atomic force microscopy. Desalination
the spring constant of atomic force microscope canti- 170:281–308
levers. Rev Sci Instrum 75(2):565–567 Johnson DJ, Al-Malek SA et al (2012) Atomic force
Hilal N, Johnson DJ (2010) The use of atomic force microscopy of nanofiltration membranes: effect of
microscopy in membrane characterisation. In: imaging mode and environment. J Membr Sci
Drioli E, Giorno L (eds) Comprehensive membrane 389:486–498
science and engineering. Elsevier Science, Oxford, Kochkodan V, Johnson DJ et al (2013) Polymeric mem-
pp 521–538 branes: surface modification for minimizing (bio)col-
Hilal N, Al-Zoubi H et al (2004) A comprehensive review loidal fouling. Adv Colloid Interface Sci (in press).
of nanofiltration membranes: treatment, pretreatment, doi:10.1016/j.cis.2013.05.005
A
angles between bonds, angles between ! ! !
V nonbonded r 1 , r 2 , . . . , r N
planes, etc.
X ! XX ! !
The general form of the total potential of the ¼ v ri þ w r i, r j þ . . .
N-atom system describes types of interactions, i i j⊳i
bonded and non-bonded, and can be written as:
!
X The v r i term represents an externally applied
! ! ! !
V r 1 , r 2 , . .. , r N ¼ V 1 r i potential field and describes external force fields
X X (e.g., gravitational field) and external
! ! ! ! !
þ V2 r i, r j þ V3 r i, r j, r k þ . . . constraining fields (e.g., the “wall function” for
i, j⊳i i, j⊳i, k⊳j
particles in a chamber). The pair potential
! !
The part of the potential energy V representing w r i , r j ¼ w r ij neglect three-body (and
bonding interactions will include terms of the higher order) interactions.
following kind: The Lennard-Jones potential is the most com-
monly used form:
1X r 2
V intramolecular ¼ K r ij r eq
2 bonds ij1 s 12 s6
wLJ ðr Þ ¼ 4e
1 X y 2 r r
þ K ijk yijk yeq
2
bend
where s is the diameter and e is the depth of the
angles
potential energy well. If electrostatic charges are
1 X X f, m present, the appropriate Coulomb potentials are
þ K ijkl 1 þ cos mfijkl gm
2 m added:
torsion
angles
Q1 Q2
wCoulomb ðr Þ ¼
The “bonds” 4pe0 r
typically involve the separation
! !
r ij ¼ r i r j between adjacent pairs of atoms where Q1, Q2 are the charges and e0 the permit-
in a molecular framework, and a harmonic form tivity of the free space.
with specified equilibrium separation has been To be effective, an analytic potential energy
used, although this is not the only possible type. function must possess the following critical
The “bend angles” yijk are between successive properties:
! ! ! !
bond vectors such as r i r j and r j r k and
involve three atom coordinates. Usually this Flexibility: A potential energy function must be
bending term is quadratic in the angular displace- sufficiently flexible that it accommodates as
ment from the equilibrium value, although peri- wide a range as possible of fitting data.
odic functions are also used. The “torsion angles” Accuracy: A potential should be able to accu-
fijkl are defined in terms of three connected rately reproduce properties of interest as
bonds; hence four atomic coordinates are used. closely as possible.
The part of the potential energy V representing Transferability: A potential function should be
non-bonded interactions between atoms is tradi- able to study a variety of properties for
tionally split into one-body, two-body, three- which it was not fit.
body terms: Computational efficiency: Evaluation of the
function should be relatively efficient
depending on quantities such as system sizes
and timescales of interest, as well as available
computing resources.
Atomistic Simulations Methods 3
The major methods are molecular mechanics Allen MP, Tildesley DJ (1989) Computer simulation of
(MM), molecular dynamics (MD), Monte Carlo liquids. Clarendon Press, Oxford
Brenner DW (2000) The art and science of an analytic
(MC), and additionally, there is a whole range of potential. Phys Status Solidi B 217:23
hybrid techniques which combine features from Frenkel D, Smit B (2002) Understanding molecular sim-
both MD and MC methods. ulation: from algorithm to applications, 2nd edn. Aca-
demic, San Diego
Haile JM (1992) Molecular dynamics simulation. Wiley,
Chichester
Leach AR (2001) Molecular modelling: principles and
References
applications, 2nd edn. Prentice Hall, Harlow
Tocci E, Pullumbi P (2011) Chapter 1: Multi-scale molec-
Allen MP (2004) Introduction to molecular dynamics ular modeling approaches for designing/selecting
simulation computational soft matter: from synthetic polymers used for developing novel membranes. In:
polymers to proteins. In: Attig N, Binder K, Drioli E, Barbieri G (eds) Membrane engineering for
Grubmuller H, Kremer K (eds) Lecture notes, John the treatment of gases: gas-separation problems with
von Neumann Institute for computing, Julich, NIC membranes. The Royal Society of Chemistry, Cam-
series, vol 23, ISBN 3-00-012641-4, pp 1–28 bridge, UK, pp 1–28
A
Ternary
azeotrope
Benzene or
cyclohexane
+ Ternary azeotrope
+ ethanol Distillation
Water-ethanol
azeotrope
Ethanol
References
Bacteria and Spore Removal, Table 1 Comparison of cold sterilization results from various sources
Process conditions cross-flow/pressure, Log
Membrane type and flux UTP, back pulsing reduction Source
Ceramic 1.4 mm; 1.4•10 4
m/s 50 kPa, 7.2 m/s UTP, skim milk Above 3.5 Saboya and Maubois
2000
Reversed asymmetric 0.87 mm; 0.5–1 m/s; back pulsing frequency Between Guerra et al. 1997
1.4•10 4 m/s 0.2–1 s 1, skim milk 4 and 5
Microsieve 0.5 mm Dead-end filtration of spiked SMUF 6.6 Van Rijn and
Kromkamp 2001
Bactocatch: ceramic 6–8 m/s, skim milk, UTP Holm et al. 1989
membranes
Bacterial Biofilm Formation domains. Many industries suffer the ill effects of
biofilm growth of one type or another, which can
Lidietta Giorno and Napoleone D’Agostino result in heavy costs in cleaning and mainte-
Institute on Membrane Technology, National nance. Biofilms occurring in membrane systems
Research Council of Italy, ITM-CNR, University may cause severe loss performance and the use of
of Calabria, Rende (CS), Italy costly cleaning procedures to maintain output and
quality. The fouling is often so severe that accept-
able operation cannot be maintained and mem-
Synonyms brane replacements are needed. It is necessary to
understand the biofilm formation mechanism
Bacterial biofilm; Bacterial adhesion; Biofouling with the aim to propose a solution to contrast
Biofilms were observed as early as 1674, when this fouling.
Antonie van Leeuwenhoek used his primitive but Bacteria are capable of colonizing almost any
effective microscope to describe aggregates of surface and have been found at extreme condi-
“animalcules” that he scraped from human tooth tions such as temperatures from 12 C to 110 C
surface (Costerton 1999). Since then, more accu- and pH values between 0.5 and 13.
rate descriptions of biofilms are made. Bacteria Biofilm growth occurs by physical, chemical,
generally exist in one of two types of population: and biological processes. Fletcher described the
planktonic, freely existing in bulk solution, and accumulation of microorganisms on a collecting
sessile, as a unit attached to a surface or within surface as a process of three stages:
the confines of a biofilm (Garrett et al. 2008). (i) adsorption, or the accumulation of an organ-
Biofilm is a result of many complicated steps. ism on a collector surface, i.e., substrate
It includes the formation of a conditioning film on (deposition); (ii) attachment, or the consolidation
a material’s surface, the movement of bacteria, an of the interface between an organism and a col-
attachment process, the growth on material sur- lector, often involving the formation of polymer
faces, and the breakdown finally. For bacteria, the bridges between the organism and collector; and
advantages of biofilm formation are numerous. (iii) colonization, or growth and division of
These advantages include: protection from anti- organisms on the collector’s surface. Although
biotics (Godberg 2002), disinfectants (Peng et al. useful as a snapshot of biofilm growth, this type
2002), and dynamic environments (Chen et al. of profile is limited when considering the inti-
1998). mate processes of cell–substrate/cell–cell inter-
Over the past few decades, biofilm growth has action. Characklis and Marshal later described an
been observed in many industrial and domestic eight-step process which included the formation
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_42-1
2 Bacterial Biofilm Formation
of an initial conditioning layer, reversible and takes into consideration are hydrophobic–hy-
irreversible adhesion of bacteria, and the eventual drophilic and osmotic (Chang and Chang 2002)
detachment of cells from a mature biofilm for and have also been described in terms of thermo-
subsequent colonization. dynamic interaction (Gallardo-Moreno et al.
Anything that may be present within the bulk 2002).
fluid can through gravitational force or move- In real time, a number of the reversibly
ment of flow settle onto a substrate and become adsorbed cells remain immobilized and become
part of a conditioning layer. This layer modifies irreversibly adsorbed. It has been argued that the
substrata facilitating accessibility to bacteria. physical appendages of bacteria (flagella, fim-
Surface charge, potential, and tensions can be briae, and pili) overcome the physical repulsive
altered favorably by the interactions between forces of the electrical double layer (De Weger
the conditioning layer and substrate. The sub- 1987). Subsequently, the appendages make con-
strate provides anchorage and nutrients tact with the bulk lattice of the conditioning layer
augmenting growth of the bacterial community. stimulating chemical reactions such as oxidation
Initially, planktonic microbial cells are and hydration and consolidating the
transported from bulk liquid to the conditioned bacteria–surface bond. Some evidence has
surface either by physical forces or by bacterial shown that microbial adhesion strongly depends
appendages such as flagella. The reversible on the hydrophobic–hydrophilic properties of
adsorption of a fraction of the cells reaching the interacting surfaces (Liu et al. 2004).
surface normally occurs. Local environmental As the stationary cells divide (binary divi-
variables which contribute to bacterial adhesion sion), daughter cells spread outward and upward
are factors such as available energy, surface func- from the attachment point to form clusters. Typ-
tionality, bacterial orientation, temperature, and ically, such interactions and growth within the
pressure conditions. If repulsive forces are developing biofilm form into a mushroom-like
greater than the attractive forces, the bacteria structure. This structure is believed to allow the
will detach from the surface. The probability of passage of nutrients to bacteria deep within a
this phenomenon occurs is higher before the for- biofilm. After an initial stage, a rapid increase in
mation of the conditioning layer. The activation population is observed, otherwise described as
energy for desorption of bacteria is low and so it the exponential growth phase. This depends on
is likely to occur, underlining the weakness of the the nature of the environment, both physically
bonds. Physical forces associated to bacterial and chemically. The rapid growth occurs at the
adhesion include the van der Waals forces, steric expense of the surrounding nutrients from the
interactions, and electrostatic (double layer) bulk fluid and the substrate. At this stage the
interaction, collectively known as the DVLO physical and chemical contribution to the initial
(Derjaguin, Verwey, Landau, and Overbeek) attachment ends and the biological processes
forces, which originally described the interaction begin to dominate. Excretion of polysaccharide
of a colloidal particle with a surface (Rutter and intercellular adhesin (PIA) polymers and the
Vincent 1980). According to this theory, the total presence of divalent cations interact to form
interaction between a surface and a particle is the stronger bonding between cells (Dunne 2002).
summation of their van der Waals and Coulomb Differential gene expression between the two
interactions. Since the van der Waals attractive bacterial states (planktonic/sessile) is in part
force is dominant in the vicinity of a surface, associated to the adhesive needs of the popula-
particles adhere irreversibly because they cannot tion. For example, the production of surface
separate from the surface by Brownian motion. In appendages is inhibited in sessile species as
contrast, the Coulomb interaction becomes dom- motility is restricted and no longer necessary.
inant at a distance away from the surface because Simultaneously, expression of a number of
the van der Waals force decreases sharply with genes for the production of cell surface proteins
distance. Other interactions that DVLO theory and excretion products increases. Surface
Bacterial Biofilm Formation 3
proteins (porins), such as Opr C and Opr E, allow disinfectants used to kill bacteria. Bacteria pos-
the transport of extracellular products into the sess membrane-bound proton pumps which
cell and excretion materials out of the cell, e.g., extrude protons from the cytoplasm to generate
polysaccharides (Hancock et al. 1990). The struc- a transmembrane electrochemical gradient
ture of many Gram-negative bacterial polysac- (Rowland 2003), i.e., the proton motive force.
charides is relatively simple, comprising either The passive influx of protons in response to the
homopolysaccharides or heteropolysaccharides proton motive force can be a problem for cells
(Sutherland 2001). These molecules impart attempting to regulate their cytoplasmic pH
mechanical stability and are pivotal to biofilm (Booth 1985). Large variations in external pH
adhesion and cohesion and evasion from harsh can overwhelm such mechanisms and have a
dynamic environmental conditions. They consol- biocidal effect on the microorganisms. Bacteria
idate the biofilm structure. Hall-Stoodley and respond to changes in internal and external pH by
Stoodley identified the differences in gene adjusting the activity and synthesis of proteins
expression of planktonic and sessile cells, and associated with many different cellular processes
as many as 57 biofilm-associated proteins were (Olsen 1993). Studies have shown that a gradual
not found in the planktonic profile. increase in acidity increases the chances of cell
The stationary phase of growth describes a survival in comparison to a sudden increase by
phase where the rate of cell division equals the rapid addition of HCl (Li 2001). This suggests
rate of cell death. At high cell concentration, a that bacteria contain mechanisms in place which
series of cell signaling mechanisms are employed allow the bacterial population to adapt to small
by the biofilm, and this is collectively termed environmental changes in pH. However, there are
quorum sensing (Bassler 1999). Quorum sensing cellular processes which do not adapt to pH fluc-
describes a process where a number of tuations so easily. One such process is the excre-
autoinducers (chemical and peptide signals in tion of exopolymeric substances
high concentrations, e.g., homoserine lactones) (polysaccharides). Optimum pH for polysaccha-
are used to stimulate genetic expression of both ride production depends on the individual spe-
mechanical and enzymatic processors of algi- cies, but it is around pH 7 for most bacteria.
nates, which form a fundamental part of the extra- Both mixed species and pure culture biofilms
cellular matrix. The death phase sees the behave like viscoelastic fluids. Biofilms exhibit
breakdown of the biofilm. Enzymes are produced both irreversible viscous deformation and revers-
by the community itself which break down poly- ible elastic response and recoil (Ohashi and
saccharides holding the biofilm together, actively Harada 2004). Extracellular polymeric sub-
releasing surface bacteria for colonization of stances like alginate, xanthan, and gellan gum
fresh substrates. Alginate lyase produced by aggregate due to hydrogen bonding to form
Pseudomonas fluorescens and Pseudomonas highly hydrated viscoelastic gels (Stoodley et al.
aeruginosa, N-acetyl-heparosan lyase by 1999). The presence of acetylated uronic acids in
Escherichia coli, and hyaluronidase by Strepto- the bacterial alginate of P. aeruginosa biofilms
coccus equi are examples of the enzymes used in increases its hydration capacity. These properties
the breakdown of the biofilm matrix (Sutherland provide the biofilm with mechanical stability
1999). Simultaneously, the operons coding for (Stoodley et al. 2002).
flagella proteins are upregulated so that the The matrix formed by EPS responds to stress
organisms have the apparatus for motility and by exhibiting (i) elastic tension due to a combi-
the genes coding for a number of porins are nation of polymeric entanglement, entropic, and
downregulated, thus completing a genetic cycle weak hydrogen bonding forces; (ii) viscous
for biofilm adhesion and cohesion. damping due to polymeric friction and hydrogen
Changes in pH can have a marked effect on bond breakage; and (iii) alignment of the poly-
bacterial growth and as such are frequently mers in the shear direction (Klapper et al. 2002).
exploited in the production of detergents and Such properties change with increased
4 Bacterial Biofilm Formation
temperature. Increasing the temperature of poly- documented. The reports available describe fairly
saccharides produces a gel-like substance which radical effects of temperature on adhered bacte-
gradually increases in strength until a critical ria. Marion-Ferey et al. observed the effect of
point is reached. At the critical point the gel high temperatures (80–90 C) on the removal of
forms a solution (Villain-Simonnet et al. 2000). biofilms. It was discovered that these tempera-
Such behavior affects the viscosity of the poly- tures were not effective for biofilm removal due
saccharides which can affect biofilm adherence. to “baking effects” at high temperature, appar-
The optimum temperature for a microorganism is ently increasing the adherent nature of the biofilm
associated with an increase in nutrient intake to the surface.
resulting in a rapid formation of biofilm
(Stepanovic et al. 2003). Enzymes are responsi-
ble of nutrient metabolism; then the formation of
References
a biofilm is dependent on the presence and reac-
tion rates of enzymes. Temperature influences the Bassler BL (1999) How bacteria talk to each other: regu-
reaction rate of enzymes having an impact on the lation of gene expression by quorum sensing. Curr
development of the cells. Optimum temperatures Opin Microbiol 2:582–587
result in the healthy growth of bacterial Booth IR (1985) Regulation of cytoplasmic pH in bacteria.
Microbiol Rev 49:359–378
populations. Temperatures away from the opti- Chang YI, Chang PK (2002) The role of hydration force
mum negatively influence bacterial enzyme reac- on the stability of the suspension of Saccharomyces
tion rates, and a reduction of bacterial growth cerevisiae – application of the extended DLVO theory.
efficiency occurs. Fletcher reported the effect of Colloids Surf A Physicochem Eng Asp 211:67–77
Characklis WG, Marshal KC (1990) Biofilms. Wiley,
temperature on attachment of stationary phase New York
cells. Findings showed that a decrease in temper- Chen MJ, Zhang Z, Bott TR (1998) Direct measurement of
ature reduced the adhesive properties of a marine the adhesive strength of biofilms in pipes by microma-
Pseudomonad. It is believed that the effect was nipulation. Biotechnol Tech 12:875–880
Costerton JW (1999) Introduction to biofilm. Int
due to a decrease in the bacterial surface polymer J Antimicrob Agents 11:217–221
at lower temperatures as well as effects such as De Weger LA, van der Vlugt C, Wijfjes AHM et al (1987)
reduced surface area. However, Herald and Flagella of a plant-growth-stimulating Pseudomonas
Zottola observed that the presence of bacterial fluorescens strain are required for colonization of
potato roots. J Bacteriol 169:2769–2773
surface appendages was dependent on tempera- Dunne WM (2002) Bacterial adhesion: seen any good
ture. At 35 C cells were shown to have a single biofilms lately? Clin Microbiol Rev 15:155–166
flagellum, while at 21 C they had two to three Fletcher M (1977) The effects of culture concentration and
flagella, and at 10 C, cells exhibited several age, time, and temperature on bacterial attachment to
polystyrene. Can J Microbiol 23:1–6
flagella. This may suggest that the initial interac- Fletcher M (1980) Microbial adhesion to surfaces. Ellis
tion between the bacteria and substrate may Horwood, Chichester
increase with a lowering of temperature, increas- Gallardo-Moreno AM, Gonzalez-Martin ML, Perez-
ing the likelihood of adhesion. Perhaps the more Giraldo C et al (2002) The measurement temperature:
an important factor relating physicochemical and
uniform properties of polysaccharides at lower adhesive properties of yeast cells to biomaterials.
temperatures increase the possibility of biofilm J Colloid Interface Sci 271:351–358
adhesion, because many microbial polysaccha- Garrett TR, Bhakoo M, Zhang Z (2008) Bacterial adhe-
rides undergo transition from an ordered state at sion and biofilms on surfaces. Prog Nat Sci
18:1049–1056
lower temperatures and in the presence of ions to Godberg J (2002) Biofilms and antibiotic resistance: a
a disordered state at elevated temperature under genetic linkage. Trends Microbiol 10:264
low ionic environments (Nisbet et al. 1984). Hall-Stoodley L, Stoodley P (2002) Developmental regu-
Although there is plenty of information lation of microbial biofilms. Curr Opin Biotechnol
13:228–233
describing the effect of temperature on bacterial Hancock REW, Siehnel R, Martin N (1990) Outer mem-
growth in culture, the effect of temperature on the brane proteins of Pseudomonas. Mol Microbiol
removal of adhered microorganisms is not so well 4:1069–1075
Bacterial Biofilm Formation 5
Herald PJ, Zottola EA (1988) Attachment of Listeria Peng JS, Tsai WC, Chou CC (2002) Inactivation and
monocytogenes to stainless steel surfaces at various removal of Bacillus cereus by sanitizer and detergent.
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Hiemenz PC, Rajagopalan R (1997) Principles of colloid Rowland BM (2003) Bacterial contamination of dental
and surface chemistry. Marcel Dekker, New York unit waterlines: what is your dentist spraying into
Klapper I, Rupp CJ, Cargo R et al (2002) Viscoelastic fluid your mouth? Clin Microbiol Newsl 25:73–77
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Li Y (2001) Cell density modulates acid adaptation in Stepanovic S, Cirkovic I, Mijac V et al (2003) Influence of
Streptococcus mutans. J Bacteriol 183:6875–6884 the incubation temperature, atmosphere and dynamic
Liu Y, Yang S, Xu H et al (2004) The influence of cell and conditions on biofilm formation by Salmonella
substratum surface hydrophobicities on microbial spp. Food Microbiol 20:339–343
attachment. J Biotechnol 110:251–256 Stoodley P, Lewandowski Z, Boyle J et al (1999) Struc-
Marion-Ferey K, Pasmore M, Stoodley P et al (2002) Bio- tural deformation of bacterial biofilms caused by short-
film removal from silicone tubing: an assessment of term fluctuations in fluid shear: an in situ investigation
the efficacy of dialysis machine decontamination pro- of biofilm rheology. Biotechnol Bioeng 65:83–92
cedures using an in vitro model. J Hosp Infect Stoodley P, Cargo R, Rupp CJ et al (2002) Biofilm mate-
53:64–71 rial properties as related to shear-induced deformation
Marshall KC, Stout R, Mitchell R (1971) Mechanism of and detachment phenomena. J Ind Microbiol
the initial events in the sorption of marine bacteria to Biotechnol 29:361–367
surfaces. J Gen Microbiol 68:337–348 Sutherland IW (1999) Polysaccharases for microbial
Nisbet BA, Sutherland IW, Bradshaw IJ et al (1984) exopolysaccharides. Carbohydr Polym 38:319–328
XM-6: a new gel-forming bacterial polysaccharide. Sutherland IW (2001) Microbial polysaccharides from
Carbohydr Polym 4:377–394 Gram-negative bacteria. Int Dairy J 11:663–674
Ohashi A, Harada H (2004) Adhesion strength of biofilm Villain-Simonnet A, Milas M, Rinaudo MA (2000) New
developed in an attached-growth reactor. Water Sci bacterial exopolysaccharide (YAS34). II. Influence of
Technol 29:281–288 thermal treatments on the conformation and structure.
Olsen ER (1993) Influence of pH on bacterial gene expres- Int J Biol Macromol 27:77–87
sion. Mol Microbiol 8:5–14
S
where the CROH and CH2 O are the volume frac- membrane experiences the irregular stresses that
tions of alcohols and water, respectively. arise from a difference in the thermal expansion
Figure 2 shows scanning electron micrographs between the support and the silicalite crystals or
(SEM) of the outer surface and cross-section of from removal of volatile materials from the zeo-
the membrane on the stainless steel support (Sano lite framework, cracks are easily formed within
et al. 1994). The surface is formed of an aggre- the membrane during the treatment process.
gate of crystals of 10 30 mm and the growth on Therefore, pretreatment conditions of mem-
the support led to a randomly grown crystalline branes affect strongly the separation perfor-
layer. The average thickness of the silicalite layer mance. As listed in Table 1 (Sano et al. 1994),
was confirmed by Si line analysis using energy- the silicalite membrane after air-drying at 100 C
dispersive X-ray analysis (EDX). The organic (containing TPA+) shows a very low flux com-
amine used in the silicalite synthesis as a template bined with a low separation factor below 1, indi-
remains in the channels of silicalite crystals. In cating that there is no cracks and pores between
order to use the membrane as the separation silicalite grains within the membrane before the
membrane, the amine must be removed from the pretreatment. However, in the case of the mem-
channels by certain procedures. As the silicalite brane after the thermal treatment, the flux and the
separation factor increase with an increase in the
treatment temperature and period. The membrane
calcined at 500 C to remove the template
completely shows the high flux combined with
the higher separation factor. The membrane
changes from the water-selective membrane to
the ethanol-selective one by decreasing the
amount of TPA+ occluded in the zeolite frame-
work, and the separation of ethanol/water takes
place by transport through the zeolite channels.
Figure 3 displays effects of the feed temperature
on the separation factor and the flux for various
alcohol/water mixtures (Sano et al. 1994). The
high separation factor is obtained for 1-propanol/
Silicalite Membrane, Fig. 1 Framework structure of
silicalite (MFI) zeolite (IZA web. 2013) water mixture, although the flux is very low. On
Silicalite Membrane,
Fig. 2 SEM images of (a) a b
outer surface and (b) cross-
section of silicalite
membrane on stainless steel
support (Reproduced from
Sano et al. (1994) with the
permission of Elsevier)
25 μm 250 μm
Silicalite Membrane 3
Silicalite Membrane, Table 1 Influence of pretreatment conditions on pervaporation performance of silicate mem-
brane (Reproduced from Sano et al. (1994) with the permission of Elsevier)
Treatment condition Flux (kg/m2 h) Separation factor a (EtOH/H2O)
Air-drying 100 C 12 h 0.00303 0.38
In vacuum 300 C 6h 0.00840 0.58
In vacuum 380 C 6h 0.0394 7.8
Calcination 500 C 20 h 0.760 58
Feed temperature: 60 C
Feed ethanol concentration: 5 vol.%
2 100
MeOH
80 1-PrOH
1.5 Separation factor α (ROH/H2O)
Flux (kg/m2h)
60
EtOH
1
EtOH 2-PrOH
40
0.5
20 MeOH
2-PrOH
1-PrOH
0 0
20 30 40 50 60 70 20 30 40 50 60 70
Feed temperature (°C) Feed temperature (°C)
Silicalite Membrane, Fig. 3 Pervaporation flux and separation factor a for various alcohol/water mixtures
(Reproduced from Sano et al. (1994) with the permission of Elsevier). Feed alcohol concentration: 1 mol%
the other hand, the higher flux and the lower References
separation factor are obtained for methanol/
water mixture. This can be explained by the dif- International Zeolite Association Web site (2013) http://
www.iza-online.org/
ferences in the molecular size and the interaction
Sano T, Kiyozumi Y, Kawamura M, Mizukami F,
between alcohol and silicalite, methanol being Takaya H, Mouri T, Inaoka W, Toida Y,
the smallest and the most polar molecule in the Watanabe M, Toyoda K (1991) Preparation and char-
group of alcohols tested here. acterization of ZSM-5 zeolite film. Zeolites
11:842–845
Sano T, Hasegawa M, Kawakami Y, Kiyozumi Y,
Yanagishita H, Kitamoto D, Mizukami F (1994)
Potentials of silicalite membrane for the separation of
alcohol/water mixture. Stud Surf Sci Catal
84:1175–1182
B
Batch Diafiltration,
Diluant u(t)
Fig. 1 Schematic
representation of batch Retentate Permeate q(t)
diafiltration configuration
Feed
pre-concentration combined with variable- V represents the feed tank volume. This initial
volume diafiltration (CVVD), and dynamic- value problem describes the evolution in time of
volume diafiltration (DVD). the feed volume and the feed concentration of any
Diafiltration techniques differ in controlling solute under the assumption that the diluant is
the addition of the diluant in terms of quantity solute-free and the feed tank is well-mixed.
and duration. The differences between the vari- Note that the time-dependent variables (i.e., per-
ous operations are best described by the propor- meate flux and the solute rejections) are, in a
tionality factor a (i.e., the ratio of diluant flow d(t) general case, a function of feed concentrations
to permeate flow q(t)) as a function of operation and may vary with operation conditions
time (Foley 2006). For instance, TD process is (temperature, pressure, cross-flow velocity, etc.).
characterized with a sequence a(t) = {0, 1, 0} The unique feature of realizing both concen-
with two unknown switching times at the end of tration and fractionation puts membrane filtration
the first and of the second time interval. Simi- in an attractive position and compares favorably
larly, CVVD process has two phases with con- with other separation methods or even with a
stant a levels a(t) = {0, a1} and an unknown sequence of consecutive unit operations. In com-
switching time. Table 1 shows the diluant control parison with continuous processes, batch opera-
strategies applied in batch processing. Note that tions are especially suited to small-scale
the best time-varying profile of diluant addition operations, require less expensive automatic con-
needs not necessarily be one of the arbitrarily trols, and enable a reduced membrane area in
predefined profiles. The diafiltration process, order to reach the target (Baker 2004). Most
that is, designed by the evaluation of the optimal batch plants operate under constant mechanistic
time-varying profile of the diluant flow, is membrane pressure adjusted simply by the
referred to as dynamic-volume diafiltration retentate valve. There exist, however, other
(Paulen et al. 2012). types of process control strategies in engineering
The governing differential equations for a practice, such as constant flux or constant wall
generalized batch diafiltration process are given concentration control (van Reis et al. 1997).
as These are normally employed when unfavorable
side effects (e.g., enhanced fouling or product
dci ci q quality deterioration) occur that can be associated
¼ ðRi aÞ, ci ð0Þ ¼ ci0 , i ¼ 1, 2
dt V with the high concentration at the
dV
¼ ða 1Þq, V ð0Þ ¼ V 0 : membrane wall.
dt
Beer Clarification, Table 1 Comparison of key parameters of beer filtered with DE filtration and microfiltration
(Lipnizki 2005)
Beer before filtration Beer after DE filtration Beer after microfiltration
Original extract [%] 11.40 11.37 11.39
Alcohol [%] 3.84 3.83 3.84
Color [EBC] 7.20 6.70 7.00
Viscosity [MPas] 1.62 1.57 1.56
Turbidity at 0 C [EBC] 32.00 0.53 0.41
monomers 6FpDA and 4MPD was varied. The Binding RC, Lee RJ, Jennings JF, Mertic EC (1961) Sep-
PV experiments were performed at 60 C, using aration of liquid mixtures by pervaporation. Ind Eng
Chem 53:47
Bz/Chx mixtures with benzene concentrations Inui K, Miyata T, Uragami T (1997) Permeation and
covering the entire concentration range. All of separation of benzene/cyclohexane mixtures through
the cross-linked polymers had excellent chemical liquid-crystalline polymer membranes. J Polym Sci
and thermal stability in the PV experiments. In all Part B Polym Phys 35:699
Inui K, Miyata T, Uragami T (1998a) Effect of permeation
cases, conditioning of the membrane samples temperature on permeation and separation of a ben-
with pure benzene was a suitable pretreatment zene/cyclohexane mixture through liquid-crystalline
to enhance the permeation rate without decreas- polymer membranes. J Polym Sci Part B Polym Phys
ing the Bz/Chx selectivity significantly. For the 36:281
Inui K, Miyata T, Uragami T (1998b) Permeation and
most promising membrane material, 6FDA- separation of binary organic mixtures through a
4MPD/DABA of 4:1 cross-linked with ethylene liquid-crystalline polymer membrane. Macromol
glycol, the PV experiments were performed with Chem Phys 199:589
a benzene/cyclohexane feed mixture of 50/50 Inui K, Okazaki K, Miyata T, Uragami T (1998c) Effect of
mesogenic groups on characteristics of permeation and
(w/w) over a temperature range between 60 C separation for benzene/cyclohexane mixtures of side-
and 110 C to determine the effect of temperature chain liquid-crystalline polymer membranes. J Membr
on the separation characteristics. Sci 143:93
Ren J, Standt-Bickel C, Lichtenthaler R (2001) Separation
of aromatics/aliphatics with crosslinked 6FDA-based
copolyimides. Sep Purif Technol 22–3:31
Uragami T (2006) Polymer membranes for separation of
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B
Among the biodegradable polymers produced biodegradable films from the extracellular polysaccha-
by microbial fermentation, polysaccharides (e.g., ride produced by Pseudomonas oleovorans grown on
glycerol byproduct. Carbohydr Polym 83:1582–1590
pullulan, hyaluronan, gellan, GalactoPol, Armentano I, Dottori M, Fortunati E, Mattioli S, Kenny
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polyhydroxyalkanoates) have been applied in Polym Degrad Stab 95:2126–2146
Bettahalli N, Steg H, Wessling M, Stamatialis D (2011)
films and edible coatings (e.g., pullulan, gellan) Development of poly(L-lactic acid) hollow fiber mem-
(Nieto 2009; Alves et al. 2011). Both microbial branes for artificial vasculature in tissue engineering
polysaccharides and polyesters show a wide scaffolds. J Membr Sci 371:117–126
range of properties that may be tuned by manip- Chapman PD, Oliveira T, Livingston AG, Li K (2008)
Membranes for dehydration of solvents by
ulating the bioreaction conditions. Polyhydrox- pervaporation. J Membr Sci 318:5–37
yalkanoates show a wide range of applications, Eisenbart E (2007) Biomaterials for tissue engineering.
such as in industry (e.g., packaging, waterproof Adv Eng Mat 9:1051–1060
paperboard), medicine (e.g., bone plates, Freitas F, Alves VD, Reis MAM (2011) Advances in
bacterial exopolysaccharides: from production to bio-
osteosynthetic materials, surgical sutures, and technological applications. Trends Biotechnol
dressing materials for surgery), and agriculture 29:388–398
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The polymers recovered from natural products gum-based edible films and coatings. In: Embuscado
ME, Huber KC (eds) Edible films and coatings for food
generally used to produce biodegradable mem- applications. Springer, New York, pp 57–112
branes include polysaccharides (e.g., starch, cel- Philip S, Keshavarz T, Roy I (2007) Polyhydrox-
lulose, pectin, alginate, carrageenan, chitosan) yalkanoates: biodegradable polymers with a range of
and proteins (e.g., gelatin/collagen, soy protein, applications. J Chem Technol Biotechnol 82:233–247
Siracusa V, Rocculi P, Romani S, Rosa MD (2008) Biode-
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develop edible coatings for food products and Trends Food Sci Technol 19:634–643
biodegradable films intended for food packaging Yen C, He H, Lee LJ, Winston Ho WS (2009) Synthesis
(Nieto 2009). Chitosan, alginate, and collagen are and characterization of nanoporous polycaprolactone
membranes via thermally- and nonsolvent-induced
also referred to be applied in tissue engineering phase separations for biomedical device application.
(Eisenbarth 2007). J Membr Sci 343:180–188
Polysaccharide-based membranes, such as Yu L, Dean K, Li L (2006) Polymer blends and compos-
chitosan and sodium alginate, have received ites from renewable resources. Prog Polym Sci
31:576–602
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pervaporation, due to their good film-forming Esmailinezhad M, Drioli E (2010) Poly(lactic acid)/
properties, chemical resistance, and high poly(vinyl pyrrolidone) blend membranes: effect of
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of ethanol/cyclohexane mixture. J Membr Sci
Yu et al. 2006). 362:105–112
Zereshki S, Figoli A, Madaeni SS, Galiano F,
Esmailinezhad M, Drioli E (2011) Pervaporation sep-
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Alves VD, Ferreira AR, Costa N, Freitas F, Reis MAM,
Coelhoso IM (2011) Characterization of
B
Biodegradable
Polymers
Biopolymers Polymers
(renewable resources) (fossil resources)
PCL
Extracted from Biomonomer Produced by
Biomass Synthesis Microorganisms
PGA
Proteins Polysaccharides
Pullulan
Gluten Cellulose
polyesters), structural cell wall components (e.g., ranging from rheology modifiers to bioplastics,
chitin, b-glucans), and extracellular biopolymers which makes them useful in many industrial
(e.g., exopolysaccharides), often secreted as pro- applications (e.g., agro-food, cosmetics, pharma-
tective mechanisms in response to environmental ceutical, textile) (Rehm 2010).
conditions (Rehm 2010).
A wide range of agro-food and industrial
wastes/by-products have been proposed as alter- References
native substrates for the production of microbial
biopolymers, including molasses, cheese whey, Freitas F, Alves VD, Reis MAM (2011) Advances in
bacterial exopolysaccharides: from production to bio-
palm date syrup, olive mill wastewater (OMW),
technological applications. Trends Biotechnol
glycerol by-product from the biodiesel industry, 29(8):388–398
corn-steep liquor, spent malt grains, apple and Mensitieri G, Di Maio E, Buonocore G, Nedi I,
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and shelf life issues of selected food packaging mate-
oils, and several acid-hydrolysate wastes (e.g.,
rials and structures from renewable resources. Trends
melon, watermelon, cucumber, tomato, rice), Food Sci Technol 22:72–80
among others (Freitas et al. 2011; Verlinden Rehm BHA (2010) Bacterial polymers: biosynthesis,
et al. 2011). modifications and applications. Nat Rev Microbiol
8:578–592
The microbial biopolymers produced include
Verlinden RAJ, Hill DJ, Kenward MA, Williams CD,
polysaccharides, polyamides, polyesters, and Piotrowska-Seget Z, Radecka IK (2011) Production
polyanhydrides. Depending on their composition of polyhydroxyalkanoates from waste frying oil by
and molecular weight, they have properties Cupriavidus necator. AMB Express 2011:1–11
B
Hydrolysis
(Soluble OM)
Fermentation
(Fatty acids)
Acetate Methanogenesis H2 + C2
CH4 + CO2
production of biogas which is collected in a bio- cheap alternative energy. However, the presence
gas container. This gas is fed into an electric of incombustible and acid gases, like CO2, not
generator which produces electricity and heat. only reduces its calorific value, but their corro-
Biohydrogen generated in fermentation pro- sive nature restricts its transportation. One of the
cesses (e.g., anaerobic fermentation, photofer- many trace components includes silicone
mentation, dark fermentation) has hydrogen and containing compounds. Commonly occurring
carbon dioxide as major ingredients. On the other siloxanes in biogas are known as volatile methyl
hand, biomethane produced by anaerobic diges- siloxanes (VMS) that include cyclic tri-, tetra-,
tion of biological wastes has 38–40 % carbon and pentasiloxane, as well as linear di-, tri-,
dioxide with smaller amounts of hydrogen sulfide tetrasiloxane. After combustion, undesirable
along with trace amounts (ppm) of hydrogen, microcrystalline quartz and pentasiloxane are
nitrogen, oxygen, and volatiles with 55–60 % produced as they cause the wear & tear of engines
methane as a major part (Rasi et al. 2007). Biogas and turbines. Purified biogas can be used as a feed
has a calorific value of 35–44 kJ g 1, which is to fuel cells or for domestic applications and
comparatively higher than other energy resources power generation. Figure 2 represents the possi-
like petrol, diesel, or LPG and solid fuels like ble applications of biogas (Basu et al. 2010).
coal, charcoal wood, etc. Biogas is a potential
source of environmentally benign, clean, and
Biogas 3
Gasification
Bio Gas
Biogas, Fig. 2 Possible applications of biogas as energy resource (Modified from Basu et al. 2010)
Biogas Recovery in the natural gas grid. In this case, the gas must
be upgraded to natural gas standards, namely,
Ivo Vankelecom 98 % methane content (AEBIOM 2009).
Centre for Surface Chemistry and Catalysis, Although the composition of biogas varies
KU Leuven, Leuven (Heverlee), Belgium significantly depending on many factors such as
the type of digester, the average values are
reported to range between 50 % and 70 % meth-
The constant increase in energy demand, coupled ane and 30–50 % carbon dioxide, as well as
with the depletion of fossil fuels, is a concern that hydrogen sulfide, sulfur compounds, siloxanes,
cannot be ignored in the industrial and highly and aromatic and halogenated compounds (Rasi
populated world of today (Basu et al. 2010). Bio- et al. 2007). Upgrading (purification) of biogas is
gas production is a very promising source of highly beneficial in terms of increasing the
renewable energy that still offers further exploi- amount of methane per unit volume of biogas,
tation of its potential (Scholz et al. 2013). Essen- which equals an increase in its calorific value. In
tially, microbially controlled biogas production is addition to the obvious need for removal of car-
an already existing part of the global carbon bon dioxide as the major pollutant, the trace com-
cycle, releasing an estimated 590–800 million pounds have the potential to trigger ozone
tons of methane to the atmosphere (Bond and depletion and the greenhouse effect, reduce the
Templeton 2011). Current biogas recovery sys- quality of local air due to formation of volatile
tems seek to exploit these processes in order to organic compounds (VOCs), and so
produce energy from sewage wastewater, animal on. Moreover, sulfur compounds corrode pipe-
manure, crop straws, or mixed agricultural wastes lines and combustion engines, while silicon com-
(Chen et al. 2012; Rasi et al. 2011). Usually, a pounds oxidize and are deposited on engine parts
system for biogas recovery consists of four com- (Rasi et al. 2007). Currently, biogas upgrading is
ponents: a collection system which helps transfer largely achieved through amine scrubbing where
the biogas source to the anaerobic digester, the carbon dioxide is absorbed into an amine solu-
anaerobic digester in which the methane produc- tion, water scrubbing where carbon dioxide is
tion takes place, a biogas collection system pro- absorbed to water at elevated pressures, and pres-
viding piping of biogas to a combustion device, sure swing adsorption where pressure of the gas
and a gas use device where biogas is combusted mixture is changed to induce adsorption and
to produce heat or electricity (Agstar 2011). desorption of one gas species. These technologies
Alternatively, the produced biogas can be used are in general more energy intensive and pollut-
on site as fuel for automotives or can be injected ing than membrane technology (Basu et al. 2010;
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_55-3
2 Biogas Recovery
Biohybrid Artificial Liver (BAL) viability and function of cells. More efforts are
now underway in search for the best cell resource
Sabrina Morelli and best design of bioreactors.
National Research Council of Italy, Institute on Considering the several functions that the liver
Membrane Technology, ITM-CNR, Rende, CS, performs, the bioreactor for BAL devices has to
Italy ensure the rapid detoxification of neural and
hepatic toxins, the return of liver-specific
hepatotrophic factors, as well as liver-specific
A biohybrid artificial liver (BAL) is a bioartificial coagulation factors, back into patient’s blood,
device which consists of functional liver cells and the maintenance of liver cell detoxification
supported by an artificial cell culture material. It and synthetic functions until liver tissue regener-
incorporates hepatocytes into a bioreactor in ation or organ transplantation.
which the cells are immobilized, cultured, and One of the most promising bioreactors is the
induced to perform the hepatic functions by membrane bioreactor. Polymeric membranes in
processing the blood or plasma of liver failure flat and hollow fiber configuration with different
patients. BAL provides temporary support for morphology and chemical–physical properties
patients waiting for an allogeneic liver transplant, have been used in BAL devices (De Bartolo and
and since the liver can regenerate, the temporary Bader 2001; Kamlot et al., 1996; Kasuya and
support provided by BAL may allow time for Tanishita 2012). Most of the extracorporeal
liver regeneration. BALs have not only used cellulose and
The bioreactor is an important component of polysulfone derivatives but also native and mod-
BAL, because it determines the viability and ified polypropylene membranes. Morphological
function of the hepatocytes within it. A success- (e.g., pore size, pore size distribution, and rough-
ful and clinically effective bioreactor should ness) and physicochemical membrane properties
mimic the structure of the liver and provide an (e.g., surface charge, wettability, and surface free
in vivo-like microenvironment for the growth of energy) affect all the adhesion and metabolic
hepatocytes, thereby maintaining the cells’ via- functions of hepatocytes.
bility and function to the maximum extent. The Hepatocytes have been cultured in membrane
important issues are the choice of cell sources and bioreactors in different configurations: between
the design of the bioreactor (Ding and Shi 2011). flat sheet membranes in a sandwich configura-
The cell sources provide liver-specific functions, tion; in the lumen of hollow fiber membranes
such as detoxification, drug metabolism, and pro- entrapped in a collagen layer; in the shell of
tein synthesis, while the bioreactors maintain the hollow fiber membranes in monolayer,
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_56-3
2 Biohybrid Artificial Liver (BAL)
Biohybrid Artificial Liver (BAL) source, the type of culture system for the hepato-
Systems cytes, and the configuration of the bioreactor.
Several BAL systems have been evaluated
Sabrina Morelli preclinically in in vitro experiments and in large
National Research Council of Italy, Institute on animal models of liver failure (Morelli
Membrane Technology, ITM-CNR, Rende, et al. 2010). Currently, different types of BAL
CS, Italy devices are in various stages of clinical evalua-
tion, and some of them are listed in Table 1 (van
de Kerkhove et al. 2004).
A biohybrid artificial liver (BAL) system is an Many of these devices use hollow fiber mem-
artificial extracorporeal supportive device which branes (HFMs) as supports for the cultured hepa-
represents an important therapeutic strategy for tocytes and as immunoselective barriers between
patients with acute liver failure. the plasma of the patients and the hepatocytes
Generally, a BAL system consists of func- used in the bioreactor. Membranes also permit
tional liver cells supported by an artificial cell the transport of nutrients and metabolites to
culture material. In particular, it incorporates cells and the transport of catabolites and specific
hepatocytes into a bioreactor in which the cells metabolic products to the blood. In the membrane
are immobilized, cultured, and induced to per- bioreactors, mass transfer is determined by the
form the hepatic functions by processing the molecular weight cutoff (MWCO) or pore diam-
blood or plasma of liver failure patients. The eter of the membrane and occurs by diffusion
BAL system acts as a bridge for the patients and/or convection in response to existing trans-
until a donor organ is available for transplanta- membrane concentration or pressure gradients.
tion or until liver regeneration. The development Most of the bioreactors for BAL systems use
of a BAL system involves many design consider- membranes with MWCO ranging from 70 to
ations. It must provide (1) an adhesion support to 100 kDa that allow the transport of serum albu-
the cells; (2) adequate mass transfer of oxygen, min but exclude proteins with high MW such as
nutrients, and toxic substances from the blood or immunoglobulins and cells.
plasma of patients to the cell compartments and One of the first clinical devices using HFMs
proteins, catabolites, and other specific com- was developed by Sussman and coworkers,
pounds produced by cells from the cell compart- namely, the extracorporeal liver-assist device
ment to the blood or plasma; (ELAD) in which the human hepatocytes were
(3) immunoprotection of cells; and (4) biocom- located outside the hollow fiber and blood flows
patibility. BAL devices are classified by the cell through the lumen of the hollow fibers. This
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_57-3
2 Biohybrid Artificial Liver (BAL) Systems
Biohybrid Artificial Liver (BAL) Systems, Table 1 Membrane BAL systems in clinical evaluation
Bioreactor
BAL system configuration Membrane References
Kiil dialyzer bioartificial liver Plate Cellulose Matsumura
et al. (1987)
ELAD Hollow fiber Cellulose acetate Sussman
Amphioxus Cell Technology et al. (1992)
LLS Hollow fiber Polyamide Gerlach
Charite, Humboldt University, Polyethersulfone et al. (1994)
Germany Polypropylene
HepatAssist Hollow fiber Polysulfone Demetriou
Circe Biomedical et al. (1995)
AMC-BAL Spirally wound Nonwoven polyester matrix, Flendrig
University of Amsterdam polypropylene et al. (1997)
BLSS Hollow fiber Cellulose acetate Patzer et al. (2002)
Excorp Medical Inc.
BAL TECA Corp. Hollow fiber Polysulfone Ding et al. (2003)
Sussman NL, Chong MG, Koussayer T, He DE, Shang van de Kerkhove MP, Hoekstra R, Chamuleau RAFM,
TA, Whisennand HH, Kelly JH (1992) Reversal of van Gulik TM (2004) Clinical application of
fulminant hepatic failure using an extracorporeal bioartificial liver support systems. Ann Surg
liver assist device. Hepatology 16:60–65 240:216–230
B
concentration with both membranes. Even when Damasceno FRC, Cammarota MC, Freire DMG
increasing the metal ion content up to 50 mg.L 1, (2012) The combined use of a biosurfactant and an
enzyme preparation to treat an effluent with a high fat
the biosurfactant concentration could be adjusted content. Colloid Surf B 95:241–246
to enable their complete rejection, with a perme- Desai JD, Banat IM (1997) Microbial production of sur-
ate flux up to 200 L.h 1.m 2.bar 1. Hong factants and their commercial potential. Microbiol
et al. (1998) also reported the ultrafiltration of Mol Biol R 61:47–64
El Zeftawy MAM, Mulligan CN (2011) Use of
copper, zinc, cadmium, and nickel ions using a rhamnolipid to remove heavy metals from wastewater
polycarboxylic acid-type biosurfactant. The by micellar-enhanced ultrafiltration (MEUF). Sep
author used flat-sheet cellulose acetate mem- Purif Technol 77:120–127
branes with molecular weight cutoff of 1,000 Freire DMG, Araujo LV, Kronemberger FA, Nitschke
M (2009) Biosurfactants as emerging additives in
and 3,000, but the biosurfactant was not as effec- food processing. In: Passos ML, Ribeiro CP (eds)
tive as the rhamnolipid reported by El Zeftawy Innovation in food engineering: new techniques and
and Mulligan (2011), leading to lower rejection products, Contemporary Food Engineering Series.
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Hong J, Yang S, Lee C, Choi Y, Kajiuchi T (1998) Ultra-
Another interesting application of filtration of divalent metal cations from aqueous solu-
biosurfactant was reported by Qin et al. (2012). tion using polycarboxylic acid type biosurfactant.
These authors used rhamnolipid biosurfactants to J Colloid Interf Sci 202:63–73
enhance the frying oil degradation and to reduce Mukherjee AK, Das K (2010) Microbial surfactants and
their potential applications: an overview. In: Sen R -
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antifouling property of the biosurfactant was also Qin L, Zhang G, Meng Q, Zhang H, Xu L, Lv B (2012)
Enhanced submerged membrane bioreactor combined
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replace their chemically synthesized counterparts Bioresour Technol 126:314–320
in several other membrane processes, like the Ramani K, Chandan Jain S, Mandal AB, Sekaran G (2012)
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alcohols and in the emulsion liquid membranes, removal of metal ions from aqueous solution. Colloid
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lignosulfonate, and lactic acid. Vaz DA, Gudiña EJ, Alameda EJ, Teixeira JA, Rodrigues
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addition of methanol, the purified surfactin was fermentation broths for surfactin recovery. Sep Purif
recovered in the permeate. Chen et al. (2008b) Technol 62:47–55
Chen H, Chen Y, Juang R (2008b) Recovery of surfactin
also reported the surfactin recovery, but using from fermentation broths by a hybrid salting-out and
ammonium sulfate salting out, ultrafiltration, membrane filtration process. Sep Purif Technol
nanofiltration, and their hybrid process. The com- 59:244–252
bination of salting out and ultrafiltration was Coutte F, Lecouturier D, Yahia SA, Leclère V, Béchet M,
Jacques P, Dhulster P (2010) Production of surfactin
selected due to the reduction of the fouling in and fengycin by Bacillus subtilis in a bubbleless
the membranes used. membrane bioreactor. Appl Microbiol Biotechnol
Another point of view should be the whole 87:499–507
integrated production system supported by mem- Coutte F, Lecouturier D, Leclère V, Béchet M, Jacques P,
Dhulster P (2013) New integrated bioprocess for the
brane processes. A system described by Coutte continuous production, extraction and purification of
et al. (2013) comprises the nondispersive oxygen- lipopeptides produced by Bacillus subtilis in mem-
ation of a bioreactor for the production of brane bioreactor. Process Biochem 48:25–32
surfactin and the continuous cell removal and Gruber T, Chmiel H (1991) Aerobic production of
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product separation using microfiltration and Knackmuss HJ, Chmiel H, Gilles ED (eds) Biochem-
ultrafiltration modules, respectively. A pilot ical Engineering-Stuttgart. Fischer Verlag, Stuttgart,
scale system, designed for the production of pp. 212–215
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Recovery and purification of surfactin from fermenta-
useful volume was also described (Kronemberger tion broth by a two-step ultrafiltration process.
et al. 2012). It comprises microfiltration modules J Membr Sci 296:51–57
for fresh medium sterilization, nondispersive Kronemberger FA, Santa Anna LMM, Fernandes ACLB,
oxygenation, another set of microfiltration mod- Menezes RR, Borges CP, Freire DMG (2008) Oxygen-
controlled biosurfactant production in a bench scale
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a reverse osmosis unit used to concentrate the Kronemberger FA, Borges CP, Freire DMG (2010) -
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References LR (2012) Performance of a biosurfactant produced by
a Bacillus subtilis strain isolated from crude oil sam-
ples as compared to commercial chemical surfactants.
Chen H, Chen Y, Juang R (2008a) Flux decline and mem- Colloids Surf B 89:167–174
brane cleaning in cross-flow ultrafiltration of treated
E
Electrodialysis with Bipolar Membranes, cell unit consisting of a cation-exchange membrane (cm),
Fig. 1 Schematic drawing illustrating the principle of a bipolar membrane (bpm), and an anion-exchange mem-
the electrodialytic production of an acid and a base from brane (am)
the corresponding salt with bipolar membranes. Repeating
efficiency, and short membrane life. Neverthe- simplified model to determine trends. J Membr Sci
less, there are a number of smaller-scale applica- 112:199–208
Liu KJ, Chlanda FP, Nagasubramanian KJ (1977) Use of
tions in the chemical process industry, in bipolar membranes for generation of acid and base: an
biotechnology, in food processing, and in waste- engineering and economic analysis. J Membr Sci
water treatment. 2:109–124
Simons R (1993) Preparation of high performance bipolar
membranes. J Membr Sci 78:13–23
References
Blood Separation,
Fig. 1 Blood components a Blood contains
after centrifugation of 55% of plasma.
native blood (a) and before Plasma Concentration of plasma
and after centrifugation of protein is 7 - 8%
blood with Ficoll-Paque
solution (b) Platelets
Blood contains
Lymphocytes
45% of blood cells
(96% of red blood cell,
Red Blood cell 3% of leukocytes, and
1% of platelet)
b
Blood sample
Plasma, Platelets
Centrifugation
Lymphocytes
Ficoll-Paque
Ficoll-Paque
Red blood cells,
Granulocytes
Blood Separation, a b
Fig. 2 Schematic
mechanism of the
separation method of cells
by a magnetic cell selection
system
schematic mechanism of the separation method separation methods using FACS and MACS are
by an MACS. The magnetic beads attaching the not applicable if the antibodies to the specific
monoclonal antibody are separated by magnetic markers on the surface of the target cells have
force to collect the specific marked cells. The not been established.
MACS needs to use an expensive antibody con- Blood cell separation through membrane fil-
jugated with magnetic beads to bind to the target tration was recently reported by several
cells for the detection of the cells. Both cell researchers (Komai et al. 1998; Yasutake
Blood Separation 3
as a blending material. PVP shows relatively nonwoven fabric is based on the adsorption of
good hemocompatibility and the more important leukocytes, while that comprised of sponge mate-
fact is that PVP can be blended well with rials is based on the sieving effect and adsorption.
polysulfone. There are a lot of materials reported Filtration methods have several advantages
excellent biocompatibility. However, these bio- compared to other methods of removing leuko-
compatible materials cannot be used as blending cytes such as centrifugation. Virus contamination
materials in polysulfone dialysis membranes due is lower in blood components during the process
to low mixing with polysulfone. PVP is also used in the filtration method than in the centrifugation
as a porogen in dialysis membranes of method due to mild operation and the ease of
polysulfone. There is a recent demand for hemo- operation under sterilized conditions.
dialysis membranes that remove the Leukocyte removal filters were typically made
low-molecular-weight proteins such as b2- of polyurethane (PU) foaming membranes where
myoglobin (MW 11,500) and endotoxin the pore was made by salt leaching method and
(subunit of MW = 5,000–20,000) and useful nonwoven fabric. The pore structure of both fil-
albumin in the plasma should be recovered by ters is found to be completely different, although
the membranes. Polysulfone hollow fibers the pore size of those filters was almost the same
blended with PVP have been widely used as from capillary flow porometer measurements.
suitable hemodialysis membranes which satisfy The mechanism of leukocyte removal (i.e., sepa-
this requirement (Higuchi et al. 2002). ration of leukocyte from plasma and other blood
cells) in leukocyte removal filters is based on
leukocyte adsorption on the filters. The adsorp-
Leukocyte Removal Filter tion of leukocytes was affected significantly by
filter materials, pore structure, and pore size.
White blood cells (leukocytes) generate many
adverse reactions during blood-transfusion ther-
apy, which are graft-versus-host disease
Plasma Separation Membrane
(GVHD), platelet refractoriness, nonhemolytic
febrile transfusion reaction, and infection of
Plasma-exchange therapy has been increasingly
viruses, such as human T-lymphotropic virus
applied clinically over the past few years. Mem-
(HTLV), cytomegalovirus (CMV), and human
brane plasma separation has been used since
immunodeficient virus (HIV) (Higuchi 2010). It
1979, which is similar to hemodialysis and
was found that most of the viruses infect specific
hemofiltration. Plasma separation from whole
type of leukocytes, such as granulocytes, mono-
blood is now performed routinely. The materials
cytes, lymphocytes, lymphocytes-B, T helper cell
of plasma separation membranes are typically
(CD4+ cell), and T-cell suppressor/cytotoxic cells
made of nitrocellulose, polysulfone, and
(CD8+ cell). HTLV-1 and HIV mainly infect
polypropylene.
T helper cell, while CMV mainly infects
granulocytes, monocytes, and lymphocytes.
GVHD was mainly generated by T helper cell
and T-cell suppressor/cytotoxic cells (CD8+ Cross-References
cell) (Higuchi 2010). Therefore, removal of leu-
kocytes in RBC and platelet concentrates as well ▶ Blood Cell Origins
as whole blood component are essential to pre- ▶ Blood Filtration
vent the adverse effect of contaminated leuko- ▶ Blood Separation
cytes. Leukocytes can be removed using a filter ▶ Diafiltration
comprised of nonwoven fabric or sponge mate- ▶ Diffusion
rials as a filter medium. The mechanism of leu-
kocyte removal on the filters comprised of
Blood Treatment Membrane 3
more than the WHO guideline value. Conven- economically feasible option to reduce high con-
tional methods for water treatment do not signif- centrations of boron in water.
icantly remove boron. The methods proven to be
efficient in a reduction of boron content in waters
are either adsorption or membrane based. Cross-References
Adsorption-based methods for boron removal
include coagulation with metal hydroxides, ▶ Boron Removal by Electrodialysis
adsorption on clays, fly ashes, and activated car- ▶ Boron Removal by Reverse Osmosis
bon (WHO 2009). Also, successful boron reduc- ▶ Boron Removal with Ion-Exchange
tion with conventional anion exchange resins or Membranes
resins functionalized with N-methyl
D-glucamine (Chillon Arias et al. 2011) was
reported. Among the membrane-based methods, References
boron removal by reverse osmosis is reported
most commonly. Also some achievements in Chillon Arias MF, Valero i Bru L, Prats Rico D, Varo
Galvan P (2011) Comparison of ion exchange resins
boron removal with ion-exchange membranes as
used in reduction of boron in desalinated water for
well as boron removal by electrodialysis are human consumption. Desalination 278:244–249
presented. In addition, some hybrid systems, Hilal N, Kim GJ, Somerfield C (2011) Boron removal
which combine membrane filtration with sorp- from saline water: a comprehensive review. Desalina-
tion 273:23–35
tion, are proposed, e.g., the adsorption-membrane
Kabay N, Bryjak M, Schlosser S, Kits M, Avlonitis S,
filtration (AMF) system. In this system, Matejka Z, Al-Mutaz I, Yuksel M (2008) Adsorption-
microparticulate boron selective resin suspension membrane filtration (AMF) hybrid process for boron
is recirculated in the retentate. Boron species removal from sweater: an overview. Desalination
223:38–48
remains adsorbed on the resin, while the boron-
Kabay N, Guler E, Bryjak M (2010) Boron in seawater and
depleted water is continuously separated by methods for its separation – a review. Desalination
microfiltration. According to Kabay et al. 2008, 261:212–217
the main advantage of the AMF over other WHO (2009) Boron in drinking-water. Background docu-
ment for development of WHO guidelines for drinking-
methods of boron separation lies in the fast
water quality. World Health Organization. http://
removal of boron, ease of sorbent separation, whqlibdoc.who.int/hq/2009/WHO_HSE_WSH_09.01_
and low operating pressure. 2_eng.pdf. Accessed 17 June 2012
According to the WHO (2009), the WHO (2011) Guidelines for drinking-water quality,
4th edn. World Health Organization. http://whqlibdoc.
abovementioned methods for boron removal are
who.int/publications/2011/9789241548151_eng.pdf.
likely to be prohibitively expensive, and blending Accessed 17 June 2012
with waters of low boron content may be the only
B
Boron Removal by Electrodialysis across IEMs are so low that the possibility of
boric acid separation from ionic species, strong
Piotr Dydo acids (Melnik et al. 2005, 2007) and salts (Turek
Faculty of Chemistry, Silesian University of et al. 2005, 2007; Bandura-Zalska et al. 2009;
Technology, Gliwice, Poland Dydo 2012a), by the use of electrodialysis is
considered. Employing this method, ionic species
are effectively transported across IEMs while
As in the case of boron removal by reverse osmo- boric acid remains in the ion-depleted dilute
sis, the effectiveness of boron removal by elec- solution.
trodialysis (ED) is strongly affected by the The type of the membrane, the dilute boron
aqueous chemistry of the boron species. In aque- concentration, the presence of ions in the dilute,
ous solutions, boric acid may exist in the form of and the electric current density were shown to
boric acid, metaborate, and polyborates. Boric affect the rate of boric acid transport across IEM
acid as a weak electrolyte (pKa = 9.2) dominates to a great extent (Melnik et al. 1999; Yazicigil
in diluted aqueous solutions of a pH equal to or and Oztekin 2006; Kabay et al. 2008; Dydo
less than 9, while at higher pH borate ions dom- 2012a). The reported mechanism for boric acid
inate. Therefore, the effectiveness of boron trans- transport across IEMs is diffusion (Dydo 2012b);
port across ion-exchange membranes (IEM) in however, the flux of boric acid was found to
the electrodialysis process needs to be discussed increase with an increase in the flux of ionic
with regard to the type of the species that domi- species. This was suggested to be the result of a
nates in the dilute. kind of ion-coupled transport of boric acid across
IEMs. The effectiveness of such a transport was
found to decrease in the following ion series:
The Effectiveness of Boric Acid sulfate nitrate chloride. It was also reported
Transport in ED that most of the boric acid was transported across
anion-exchange membrane (AEM).
Boric acid, H3BO3, is a small and electrically Turek et al. 2008b reported high boron fluxes
neutral species. The reported boric acid removal and exceptionally high electric current efficien-
efficiencies and electric current efficiencies in cies of up to 220 % when boric acid was
ED are poor when compared to ionic species transported from ion-depleted, neutral or acidic,
(Melnik et al. 1999; Turek et al. 2005, 2007, dilute into the alkaline concentrate of pH >11.
2008a; Kabay et al. 2008; Banasiak and Schafer Such a behavior was identified to be the result of
2009; WHO 2009). In fact, boric acid fluxes Donnan dialysis, in which hydroxyl acts as a
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_75-4
2 Boron Removal by Electrodialysis
carrier for boric acid. However, in the light of (Yazicigil et al. 2006; Kabay et. al 2008; Turek
recent reports, simple boric acid diffusion should et al. 2008a). It is also agreed that boron (borate)
explain the results as well. is transported faster in the presence of chloride
Tentative results on boron removal by electro- ions than in the presence of sulfates (Yazicigil
dialysis units equipped with ion-exchange et al. 2006; Kabay et al. 2008) or nitrates.
spacers were also presented by Oren et al. in In 2005 and 2008a, Turek et al. analyzed the
2006. The possibility of up to an 80 % reduction effect of salinity on the electric current efficiency
of boron from water containing 4.5 mg/L was of boron (borate) transport. They found that the
reported. observed electric current efficiencies are low as
long as dilute salinity remains high. During the
initial part of the experiments, no, or almost no,
The Effectiveness of Borate Transport boron was transported from the dilute. Then, i.e.,
in ED when more than 90 % of the Cl was removed
from the dilute, a dramatic increase in boron
Melnik et al. (1999), Yazicigil et al. (2006), and (borate) electric current efficiency was observed.
Kabay et al. (2008) reported that as the pH of This increase was accompanied by an increase in
boron-containing water was brought up to just boron flux. Such an effect can be identified as the
above the value of 9, a significant increase in result of low borate mobility (diffusivity) when
the rate of boron transport across IEMs is compared to other ions present in the waters, i.e.,
observed. Moreover, Melnik et al. 1999 reported Cl . As long as there are ions of higher mobility
that in the case of heterogeneous membranes, an than borates in the dilute, boron (borate) flux
increase in the boron transport rate across anion- remains low. However, even in an ion-depleted
exchange membrane at pH >9 is accompanied by dilute, the electric current efficiency of boron
a decrease in the rate of boron transport across (borate) transport has not exceeded the value of
cation-exchange membrane (CEM). It is clear 30 %. The remaining percentage of the electric
that under these conditions (pH >9), borates are current was probably utilized for hydroxyl ion
the boron species that dominates and their trans- transport. A considerable drop in the pH of the
port across AEMs rather than CEMs should be dilute was reported afterwards. This resulted in a
discussed. The effectiveness of borate transport drop in dilute pH and in a consequent reduction in
across AEMs in ED systems was found to depend the flux of boron since all the borate present was
upon the pH of the dilute, the type of the mem- converted into boric acid. So the low electric
brane, dilute boron concentration, and the kind of current efficiency of borate transport in an ED
the ion cotransported across the membrane. system and the necessity for deep dilute demin-
Yazicigil et al. in 2006 reported that at a dilute eralization make the economic feasibility of
pH of approx. 9, there is a maximum boron trans- borate removal by ED questionable.
port rate, and at higher pH the rate of boron
transport decreases. These results are contradic-
tory to those presented by Melnik et al. (1999) Cross-References
(heterogeneous membranes), Turek et al. (2007),
and Kabay et al. (2008), according to which there ▶ Boron Reduction
is a continuous increase in the rate of boron ▶ Boron Removal by Electrodialysis
transport with dilute pH even when above 9.0. ▶ Boron Removal by Reverse Osmosis
However, the Yazicigil et al. (2006) results seem
to be justified by high boron concentration
(0.1 mol/L) in their experiments. Similar behav-
References
ior was observed by Ayyildiz and Kara in 2005. It
is agreed that an increase in dilute boron concen- Ayyildiz HF, Kara H (2005) Boron removal by ion
tration causes an increase in boron (borate) flux exchange membranes. Desalination 180:99–108
Boron Removal by Electrodialysis 3
Banasiak LJ, Schafer AI (2009) Removal of boron, fluo- technology for boron removal from natural and waste-
ride and nitrate by electrodialysis in the presence of waters. Desalination 205:206–213
organic matter. J Membr Sci 334:101–109 Oren Y, Linder C, Daltrophe N, Mirsky Y, Skorka J,
Bandura-Zalska B, Dydo P, Turek M (2009) Desalination Kedem O (2006) Boron removal from desalinated
of boron-containing wastewater at no boron transport. seawater and brackish water by improved electrodial-
Desalination 241:133–137 ysis. Desalination 199:52–54
Dydo P (2012a) The effect of process parameters on boric Turek M, Dydo P, Ciba J, Trojanowska J, Kluczka J,
acid transport during the electrodialytic desalination of Palka-Kupczak B (2005) Electrodialytic treatment of
aqueous solutions containing selected salts. Desalina- boron-containing wastewater with univalent
tion. In press. doi:10.1016/j.bbr.2011.03.031 permselective membranes. Desalination 185:139–145
Dydo P (2012b) The mechanism of boric acid transport Turek M, Dydo P, Trojanowska J, Bandura B (2007) Elec-
during an electrodialytic desalination process. trodialytic treatment of boron-containing wastewater.
J Membr Sci 407–408:202–210 Desalination 205:185–191
Kabay N, Arar O, Acara F, Ghazal A, Yuksel U, Yuksel Turek M, Bandura B, Dydo P (2008a) Electrodialytic
M (2008) Removal of boron from water by electrodi- boron removal from SWRO permeate. Desalination
alysis: effect of feed characteristics and interfering 223:17–22
ions. Desalination 223:63–72 Turek M, Bandura B, Dydo P (2008b) The influence of
Melnik L, Vysotskaja O, Kornilovich B (1999) Boron concentrate alkalinity on electrodialytic boron trans-
behavior during desalination of sea and underground port. Desalination 223:119–125
water by electrodialysis. Desalination 124:125–130 WHO (2009) Boron in drinking-water. Background
Melnik L, Goncharuk V, Butnyk I, Tsapiuk E (2005) document for development of WHO guidelines for
Boron removal from natural and wastewaters using drinking-water quality. World Health Organization.
combined sorption/membrane proces. Desalination http://whqlibdoc.who.int/hq/2009/WHO_HSE_WSH
185:147–157 _09.01_2_eng.pdf. Accessed 17 Jun 2012
Melnik L, Goncharuk V, Butnyk I, Tsapiuk E (2007) Yazicigil Z, Oztekin Y (2006) Boron removal by electro-
Development of the sorption-membrane “green” dialysis with anion-exchange membranes. Desalina-
tion 190:71–78
B
Boron Removal by Reverse Osmosis The effectiveness of boron removal from sea-
water by RO can be enhanced by adjusting the
Piotr Dydo feedwater pH to above the value of 9.25. The
Faculty of Chemistry, Silesian University of monoborate anion, which dominates in diluted
Technology, Gliwice, Poland solutions at pH > 9.5, was found to be rejected
more effectively than boric acid due to its larger
size and discrete charge (Kabay et al. 2010; Hilal
Reverse osmosis (RO) is a commonly applied et al. 2011). The reported boron rejection coeffi-
membrane technique of desalination capable of cients at pH = 11 exceeds 99 % in the case of
producing permeates of drinking-water quality. dense seawater reverse osmosis membranes.
In most cases, the boron content in the product Also, in the case of boron-rich geothermal waters
should not exceed the WHO 2009 and 2011 and industrial wastewaters, high boron rejection
guideline value of 2.4 mg/L. The effectiveness is observed only at pH > 10.5 (Koseoglu
of boron rejection by reverse osmosis membranes et al. 2010; Dydo et al. 2005). Furthermore, it
is, however, strongly affected by its concentra- was shown that the effectiveness of boron
tion in the feedwater and the aqueous chemistry removal can be further enhanced by creating
of boron specie (Kabay et al. 2010; Hilal borate complexes (esters) with polyhydroxyl
et al. 2011). In aqueous solutions, boric acid alcohols (Geffen et al. 2006; Dydo et al. 2012),
may exist in the form of boric acid, metaborates, although again, under alkaline conditions only.
and polyborates. Boric acid as a weak electrolyte The results of mechanistic studies on boron
(pKa = 9.2) dominates in diluted aqueous solu- rejection by reverse osmosis membranes
tions of a pH less than 9. Since the pH of most conducted by Sagiv and Semiat (2004), Hyung
naturally occurring waters is lower than 9, the and Kim (2006), Hun et al. (2009), and Tu
rate of boric acid transport determines the effec- et al. (2010) showed that permeabilities of boric
tiveness of boron removal by RO. acid are at least one order of magnitude larger
According to Kabay et al. 2010, the rejection than those of monoborate ion. It proves more
of boric acid by RO membranes is, however, low intensive diffusion of boric acid than of borate
due to its small size and lack of electric charge. across RO membranes. Also, the reflection coef-
The reported boron rejection coefficients range ficients for boric acid (<0.985) are considerably
from around 20 % in the case of old RO mem- lower than those specific for monoborate
branes to approx. 90 % in the case of modern RO (>0.995) as reported by Hyung and Kim (2006).
membranes (WHO 2009; Kabay et al. 2010; Hilal This, in turn, indicates strong boric acid–water
et al. 2011). interaction.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_76-11
2 Boron Removal by Reverse Osmosis
Feedwater pH is said to have a dominant means of nanofiltration and reverse osmosis. Desali-
impact on boron rejection by RO membranes nation 185:131–137
Dydo P, Nemś I, Turek M (2012) Boron removal and its
(Hilal et al. 2011). Among other RO parameters concentration by reverse osmosis in the presence of
that affect boron rejection are: operating pressure polyol compounds. Sep Purif Technol 89:171–180
(increase), feed temperature (decrease), Faigon M, Hefer D (2008) Boron rejection in SWRO at
feedwater salinity (decrease), and recovery high pH conditions versus cascade design. Desalina-
tion 223:10–16
(decrease). Geffen N, Semiat R, Eisen MS, Balazs Y, Katz I, Dosoretz
However, RO systems cannot be directly oper- CG (2006) Boron removal from water by complexa-
ated at high feedwater pH due to the possibility of tion with polyol compounds. J Membr Sci 286:45–51
membrane scaling with insoluble calcium and Hilal N, Kim GJ, Somerfield C (2011) Boron removal
from saline water: a comprehensive review. Desalina-
magnesium basic compounds. Therefore, several tion 273:23–35
modifications to the operation of RO and its Hun PVX, Cho S-H, Moon S-H (2009) Prediction of boron
design have been proposed. In general, a cascade transport through seawater reverse osmosis mem-
design for RO systems in which a fraction of the branes using solution-diffusion model. Desalination
247:33–44
first stage permeate is treated in the following RO Hyung H, Kim J-H (2006) A mechanistic study on boron
stages (if possible at elevated pH’s) and a blend- rejection by sea water reverse osmosis membranes.
ing of all the permeates produces water of the J Membr Sci 286:269–278
desired quality (Hilal et al. 2011; Faigon and Kabay N, Guler E, Bryjak M (2010) Boron in seawater and
methods for its separation – a review. Desalination
Hefer 2008). This design was successfully 261:212–217
applied, e.g., in the full-scale seawater treatment Koseoglu H, Harman BI, Yigit NO, Guler E, Kabay N,
plant in Eliat. Kitis M (2010) The effects of operating conditions on
boron removal from geotermal waters by membranes
processes. Desalination 258:72–78
Sagiv A, Semiat R (2004) Analysis of parameters affect-
Cross-References ing boron permeation through reverse osmosis mem-
branes. J Membr Sci 243:79–87
▶ Boron Reduction Tu KL, Nghiem LD, Chivas AR (2010) Boron removal by
reverse osmosis membranes in seawater desalination
▶ Boron Removal by Electrodialysis applications. Sep Purif Technol 75:87–101
▶ Boron Removal with Ion-Exchange WHO (2009) Boron in drinking-water. Background docu-
Membranes ment for development of WHO guidelines for drinking-
water quality. World Health Organization. http://
whqlibdoc.who.int/hq/2009/WHO_HSE_WSH_09.01_2_
eng.pdf. Accessed 17 June 2012
References WHO (2011) Guidelines for drinking-water quality,
4th edn. World Health Organization. http://whqlibdoc.
Dydo P, Turek M, Ciba J, Trojanowska J, Kluczka who.int/publications/2011/9789241548151_eng.pdf.
J (2005) Boron removal from landfill leachate by Accessed 17 June 2012
B
Boron Removal with Ion-Exchange and Kara in 2005 reported also that the pH of the
Membranes receiving phase affects boron flux with its maxi-
mum at around a pH of 9.5. Moreover, the boron-
Piotr Dydo accompanying anions, chlorides, bicarbonates,
Faculty of Chemistry, Silesian University of and sulfates, were found to affect the rate of
Technology, Gliwice, Poland boron transport in DD with a maximum observed
in the presence of bicarbonate. On the other hand,
the highest boron transport rates were observed
Apart from boron removal by electrodialysis, with sodium chloride in the receiving solution.
ion-exchange membranes are able to transport Neosepta AHA and AMH membranes produced
boron in the so-called Donnan dialysis (DD) or similar fluxes of boron, while the superiority of
diffusion dialysis processes (Fig. 1). AFN was clearly seen. In 2011, Kir et al. showed
Ayyildiz and Kara (2005) examined the effec- that plasma modification of the existing anion-
tiveness of boron transport across anion- exchange membranes may result in a significant
exchange membranes in a DD process. They enhancement of the rate of boron transport in a
found that boron flux depends upon the mem- DD process.
brane, concentration of boron in the feed solution, The mechanistic study on boric acid transport
pH of the feed and receiving solution, presence of across cation-exchange membranes (CEMs) in a
the accompanying ions in the feed solution, and DD process was presented by Goli et al. in 2010.
the type of the carrier anion in the receiving It was reported that the membrane diffusion coef-
solutions. The effect of pH of the feed solution ficients for boric acid depend not only upon the
was found to be complex. At high boron concen- manufacturer of the CEM but also upon the type
tration (0.1 mol/L), maximum boron flux was of the cation present in the membrane. The same
observed at around the pH of 9.5, while in the behavior is reported for arsenite. In general, in the
case of a diluted solution (0.001 mol/L), maxi- presence of monovalent cations in the membrane,
mum boron flux was observed at the maximum higher fluxes of boron were observed than in the
examined feedwater pH of 11.5. Such behavior presence of divalent cations. Such a behavior was
was explained by the formation of polyborate later confirmed by Dydo in 2012. The existing
ions at high boron concentrations and their differences in boric acid membrane diffusion
absence in diluted solutions. The maximum rate coefficients were rationalized by Goli
of boron transport at the pH of around 9.5 in the et al. (2010) as being the result of the change in
case of concentrated boron solution was later the mean viscosity of the solution confined in
confirmed by Yazicigil et al. in 2006. Ayyildiz membrane pores.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_77-5
2 Boron Removal with Ion-Exchange Membranes
Boron Removal with Ion-Exchange Membranes, Fig. 1 Boron Removal with Ion-Exchange Membranes
In 2007, Bryjak et al. proposed a Donnan the effectiveness of boron removal from water
dialysis-based method for the regeneration of nor its final concentration. It seems that a lot of
finely divided boron selective resin (BSR) work needs to be done to enhance the kinetics of
DOWEX XUS 43594.00. In this process, BSR the diffusive transport of borate during DD.
slurry with boron adsorbed on it is fed into the
DD feed compartment. It was assumed that there
are always some minute amounts of borate in the
Cross-References
feedwater at equilibrium with the BSR. These
amounts were subject to transport into the receiv-
▶ Boron Reduction
ing solution as a result of Donnan dialysis, which
▶ Boron Removal by Electrodialysis
should ultimately result in complete boron
▶ Boron Removal by Reverse Osmosis
removal from the BSR. The net effect of the
process would be a regenerated resin in the chlo-
ride form and boron (borate)-rich receiving solu-
tion. As reported by Bryjak et al. (2007), References
considerably high boron fluxes were observed
during the course of a DD regeneration of boron Ayyildiz HF, Kara H (2005) Boron removal by ion
exchange membranes. Desalination 180:99–108
containing BSR. Boron desorption was found to Bryjak M, Pozniak G, Kabay N (2007) Donnan dialysis of
be the phenomena that governs kinetics of the borate anions through anion exchange membranes: a
boron transport in the process. new method for regeneration of boron selective resins.
Unfortunately the tentative, mostly mechanis- React Funct Polym 67:1635–1642
Dydo P (2012) The mechanism of boric acid transport
tic report on DD boron removal presented in this during an electrodialytic desalination process.
chapter does not provide much information about J Membr Sci 407–408:202–210
Boron Removal with Ion-Exchange Membranes 3
Goli E, Hiemstra T, Van Riemsdijk WH, Rahnemaie R, unmodified anion-exchange membranes. Desalination
Malakouti MJ (2010) Diffusion of neutral and ionic 267: 114–177
species in charged membranes: boric acid, arsenite, Yazicigil Z, Oztekin Y (2006) Boron removal by electro-
and water. Anal Chem 82:8438–8445 dialysis with anion-exchange membranes. Desalina-
Kir E, Gurler B, Gulec A (n.d.) Boron removal from tion 190:71–78
aqueous solution by using plasma-modified and
B
continuous fermentation are less established but Chotani GK, Dodge TC, Gaertner AL, Arbige MV
have, nevertheless, the potential to become (2007) Industrial biotechnology: discovery to delivery.
In: Kent JA (ed) Kent and Riegel’s handbook of indus-
increasingly important. trial chemistry and biotechnology, 11th edn. Springer,
Berlin
Festel G, Knöll J, Götz H, Zinke H (2004) Der einfluss der
References biotechnologie auf produktionsverfahren in der
chemieindustrie. Chem Ing Technol 76:307–312
Axegård P (2005) The future pulp mill – a biorefinery?
Presentation at the 1st international biorefinery work-
shop, Washington, DC
B
Bulk Liquid Membrane, Fig. 1 Schematic transport models of a bulk organic hybrid liquid membrane (BOHLM)
system with a, d hydrophobic membranes and b, e hydrophilic or ion-exchange membranes
and MHS-PV techniques of the BOHLM pro- In recent years, integrated hybrid systems
cesses. Separation of ethylene, benzene, incorporating two or more functions in one mod-
propanol, olefin, and aromatic amines from ule, for example, biotransformation and separa-
organic liquid mixtures and of volatile organic tion, become of great interest to researchers. The
compounds (VOC) and phenol from wastewater BOHLM systems, integrating reaction, separa-
was investigated using a rotating film module, tion, and concentration functions in one appara-
spiral-type FLM, and hollow-fiber and layered tus (bioreactor) attracted great interest in the last
LM techniques. High separation factors few years. Bioreactors combine the use of spe-
(>1,000) in pilot- and industrial-scale experi- cific biocatalyst for the desired chemical reac-
ments were found. In the last two decades, tions, with repeated or continuous application of
BOHLM techniques were intensively used in it under very specific conditions. Such techniques
analytical chemistry for separation and were termed hybrid membrane reactors.
preconcentration of metals, organic acids,
organic, and pharmaceutical compounds.
BAHLM is a new technology and few studies References
are known up to date. In metal separations copper-
cadmium recovery from chloride aqueous solu- Kislik V (2010a) Bulk hybrid liquid membrane with organic
water-immiscible carriers: application to chemical, bio-
tions and cadmium, copper, and zinc separation
chemical, pharmaceutical, and gas separations. In:
from wet-process phosphoric acid are studied. Kislik V (ed) Liquid membranes principles and applica-
BAHLM systems were tested for the separation tions in chemical separations & wastewater treatment,
of carboxylic acids such as lactic, citric, and acetic 1st edn. Elsevier, Amsterdam, pp 201–276, Ch. 5
Kislik V (2010b) Bulk Aqueous Hybrid Liquid Membrane
or their anions. Continuous separation of different
(BAHLM) processes with water-soluble carriers:
isomeric mixtures of organic compounds has been application in chemical and biochemical separations.
studied by means of a hollow-fiber-contained liq- In: Kislik V (ed) Liquid membranes principles and
uid membrane, HFCLM. applications in chemical separations, 1st edn, Elsevier,
Ch. 6, pp 277–326
C
Capillary Flow r 2 DP
u¼
8m L
Andras Koris
Corvinus University of Budapest, Budapest, where DP is the total pressure drop along the
Hungary channel and m is the fluid viscosity.
In the general case of two immiscible fluids:
References
Possible Applications
Carbon Membrane,
Fig. 1 Comparing the
CO2/CH4 Robeson upper
bound for dense and
thermally rearranged
(TR) polymer membranes
to the carbon membranes
and the region for industrial
applicability – data for
CMS membranes and
industrial applicability
region added to the original
Robeson plot (see Hägg and
He 2011)
a b c
Carbon Membrane, Fig. 2 Schematic model of different ways of tailoring microporous carbon. The dashed line
shows the limit of an original slit-shaped pore (Lie and Hägg 2005)
carbon membranes are illustrated in Fig. 2 (Lie The supported carbon membranes will provide
and Hägg 2005). better mechanical strength than self-supported
Although showing excellent separation per- fibers but will naturally have lower packing den-
formance, the self-supported hollow fiber mem- sity. These types of carbon membranes have been
branes may be quite brittle, thus the scaling up especially studied for high-temperature applica-
and module making are challenging. The Norwe- tions (e.g., H2/CO2 separation and as carbon
gian company MemfoACT did successfully dem- membrane reactors). The special challenge of
onstrate on pilot scale the use of carbonized self- making these membranes is to obtain a defect-
supported cellulose hollow fibers for upgrading free carbon layer on the top of the
of biogas (CO2/CH4 separation) (Fig. 3). The support – compatibility between support and car-
scaling up to full-size commercial module has bon layer may also be a problem. Supported CMS
however not yet been reported (in 2015). membranes have been studied by several.
A method by using spin-coat technique was
Carbon Membrane 3
Carbon Membrane,
Fig. 3 Left: SEM picture
of a CMS fiber; wall
thickness is 16 mm. Right:
A bundle of CMS hollow
fibers ready for mounting in
a pilot module as illustrated
by the company
MemfoACT in 2013 on
their homepage
Carbon Nanotube Membranes (CNT perpendicular to the substrate surface have been
Membranes) already synthesized in which the transport occur
through the inner core of the CNTs (Majumder
Enrica Fontananova and Enrico Drioli et al. 2011). High permeability enhancement than
Institute on Membrane Technology, National predictions (>10 for gases and >1000 for liquids)
Research Council of Italy, ITM-CNR, University have been obtained with these membranes. How-
of Calabria, Rende(CS), Calabria, Italy ever, the small area (typically in the order of few
mm2), the long and complex fabrication process,
and the poor mechanical stability of these type of
Carbon nanotubes (CNTs) are allotropic forms of CNT membranes, limit the practical applicability
carbon that can be conceptually visualized as a of these interesting nanostructured systems. On
cylindrical nanostructure formed by rolling a the contrary, more easy is the scale up of CNT
graphene sheet along a lattice vectors (m,n) in membranes in which the CNTs are mixed with a
the graphene plane (Fig. 1). polymer in the form of mixed matrix membranes.
Depending from the number of concentric cyl- The main limitations of these membranes are
inders, it is possible to have: single-, double-, or related to the poor dispersion of the CNTs in the
multiwalled carbon nanotubes (SWCNTs, polymeric matrix and the moderate increase of the
DWCNTs, MWCNTs). The indices (m,n) deter- membrane performance.
mine the diameter and chirality (i.e., the chiral It is interesting to note that graphitic carbon
angle between hexagons and the tube axis) of the nanomaterials like CNTs are usually introduced at
CNTs (Dai 2002). The CNTs can be in the zigzag, lower content (2 wt%) in mixed matrix mem-
armchair, or chiral form with metallic or semicon- branes in comparison with three-dimensional
ducting properties (Table 1). inorganic nanofillers like TiO2 and ZrO2 (usually
CNTs, thanks to their diameter in the nanome- blended at loading 5 wt%, up to 60 wt%), thank
ter range and their atomically smooth surfaces, to their high specific surface, elevated aspect ratio,
offer unique systems for fast molecular transport and the intrinsic properties of graphitized struc-
(Hummer et al. 2001; Kalra et al. 2003). Molecu- ture. In addition, the relatively easy functiona-
lar dynamics (MD) simulations showed spontane- lization of the surface of carbon nanomaterials
ous and continuous filling of a CNT with a render them ideal candidate to tailor the poly-
one-dimensionally ordered chain of water mer/nanofiller interface.
molecules. CNTs were succesfully entrapped in mixed
Membranes made of ordered arrays of carbon matrix membranes made of various polymeric
nanotubes well aligned along the direction materials by several techniques including:
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_109-1
2 Carbon Nanotube Membranes (CNT Membranes)
Carbon Nanotube a
Membranes (CNT
Membranes),
Fig. 1 Schematic
honeycomb structure of a n
graphene sheet (sp2 m
hybridized carbon network)
(a) and image of single-,
double-, and multiwalled
carbon nanotubes
(SWCNTs, DWCNTs,
MWCNTs), (b)
dispersion in the casting solution and successive membrane mechanical strength relative to the PA
phase separation, entrapping in the membrane polymeric membranes.
pores using a polymer binder, in situ crosslinking Mixed matrix polyimide membranes were also
of a polymer matrix around oriented CNTs (Ismail prepared using functionalized MWCNTs
et al. 2009). The resulting mixed matrix CNT (aminated or oxidized). The MWCNTs functiona-
membranes offer, in many cases, relevant advan- lization improved their dispersion in the casting
tages in comparison with the polymeric samples. solution in comparison to pristine MWCNTs and,
Poly(vinyl alcohol) (PVA)/MWCNTs membranes as a consequence, in the formed membranes. The
were realized for pervaporation application, membranes containing functionalized MWCNTs
obtaining significant improvement in Young’s showed better performance in the rejection of
modulus and thermal stability, as compared to dyes (enhanced flux and reduced fouling, with
pure PVA membranes (Peng et al. 2007). The similar or higher rejection), with respect to refer-
entrapment of MWCNTs in polyethersulfone ence polymeric membranes (without MWCNTs).
(PES) membranes reduced fouling problems in These results were attributed to the formation of
water treatment (Celik et al. 2011). Mixed matrix low-resistance pathways for solvent transport at
membranes consisting of sulfonated carbon the interface between the MWCNTs and the poly-
nanotubes (sCNTs) and sulfonated poly meric chains. Moreover, the MWCNTs reduced
(ethersulfone ether ketone ketone) (SPESEKK) the severe membrane fouling caused by the
were also fabricated via the solution casting absorption of the positively charged dye Safranine
method (Zhou et al. 2011). The proton conductiv- (used as a model of organic pollutant) with respect
ity of the SPESEKK membrane increased while the polymeric membrane, by a screening effect of
the methanol permeability decreased as the sCNTs the attractive electrical interactions between the
content increased. MWCNTs were covalently Safranine and the membrane surface character-
linked to aromatic polyamide (PA) membranes ized by a negative value of zeta potential
by a polymer grafting process (Shawky (Grosso et al. 2014).
et al. 2011). Measurements of mechanical proper- The presence of oxygen-containing polar
ties of this composite showed an increased groups on oxidized MWCNTs, resulted also in a
Carbon Nanotube Membranes (CNT Membranes) 3
Carbon Nanotube Membranes (CNT Membranes), Table 1 Different forms of a SWCNT and its electrical
properties
(n, m) Form Electrical conductivity
(n, 0) Zigzag Metallic when n is multiple of 3, otherwise, semiconducting
Hummer G, Rasaiah JC, Noworyta JP (2001) Water con- Peng F, Hu C, Jiang Z (2007) Novel ploy(vinyl alcohol)/
duction through the hydrophobic channel of a carbon carbon nanotube hybrid membranes for pervaporation
nanotube. Nature 414:188–190 separation of benzene/cyclohexane mixtures. J Membr
Ismail AF, Goh PS, Sanip SM, Aziz M (2009) Transport Sci 297:236–242
and separation properties of carbon nanotube-mixed Shawky HA, Chae S-R, Lin S, Wiesner MR (2011) Syn-
matrix membrane. Sep Purif Technol 70:12–26 thesis and characterization of a carbon nanotube/poly-
Kalra A, Garde S, Hummer G (2003) Osmotic water trans- mer nanocomposite membrane for water treatment.
port through carbon nanotube membranes. Proc Natl Desalination 272:46–50
Acad Sci U S A 100:10175–10180 Zhou W, Xiao J, Chen Y, Zeng R, Xiao S, Nie H, Li F, Song
Majumder M, Chopra N, Bruce JH (2011) Mass transport C (2011) Sulfonated carbon nanotubes/sulfonated poly
through carbon nanotube membranes in three different (ether sulfone ether ketone ketone) composites for
regimes: ionic diffusion and gas and liquid flow. ACS polymer electrolyte membranes. Polym Adv Technol
Nano 5:3867–3877 22:1747–1752
C
Carbon Porous
Membranes Modified
with Enzymes,
Fig. 1 Photography of
carbon tube (photo IEM)
Catalytic Membranes,
Fig. 1 Porous catalytic
membrane for wastewater
treatment (Reprinted with
permission from Raeder
2010)
sorbs into the membrane at the higher chemical membrane to be used, porous or dense, polymeric
potential side, diffuses through the membrane or inorganic, etc., depends on several factors,
subjected to the driving force gradient, and namely, the type of reaction. For example,
desorbs on the opposite side). These membranes dense polymeric catalytic membranes are used
are usually permselective. Concerning porous for low-temperature reactions where the
membranes, the total mass transport results from permselectivity is important for shifting the con-
different contributions, namely, a diffusive com- version beyond the thermodynamic equilibrium
ponent (activated, surface, Knudsen and bulk) value based on feed conditions (e.g., selective
and a viscous component (Poiseuille flow). The removal of water in esterification reactions) or
contribution of each one depends on the operating to enhance the reaction selectivity (e.g., hydra-
conditions and on the pore’s size. For pore radius tion, epoxidation, isomerization, and hydrogena-
between 1 and 50 nm, Knudsen diffusion is nor- tion reactions). Dense polymeric catalytic
mally the predominant mass transfer mechanism membranes can also be used as contactors for
(Knudsen diffusion is characterized by the mean- promoting reactions between two immiscible
free path of the traveling species being much phases with segregated feed (e.g., oxyfunctiona-
larger than the pore radius and is independent of lization of hydrocarbons with hydrogen peroxide
any pressure gradient along the pore), and the reactions) (Basile and Gallucci 2009).
membranes present some permselectivity, related Another type of reaction that has been studied
with the ratio of the species molar mass. For is the photocatalytic removal of contaminants
membranes with larger pores, namely, from water, either using porous or dense poly-
macroporous, the mass transfer mechanism is a meric catalytic membranes. The catalyst typi-
viscous flow if a total pressure gradient across the cally used is TiO2, occluded or coated, but also
porous membrane is present or bulk diffusion if occluded Fe in an H2O2 oxidant medium (photo-
not. Neither of these situations allows any Fenton process) has been considered (Basile and
permselectivity. When the membrane has micro- Nunes 2011).
pores and the species adsorb significantly, as in Catalytic nonpermselective porous mem-
the case of zeolites, surface diffusion has a rele- branes, polymeric or inorganic, can be used to
vant contribution. Also in these cases the mem- improve the contact between the reactants and the
branes are permselective (Basile and Nunes catalyst, in order to obtain higher reaction con-
2011). versions. Particularly in the case of triphasic
A catalytic membrane is used to carry out (gas/liquid/solid) reactions, usually limited by
different types of reactions, namely, chemical, the diffusion of the gaseous reactant, porous
biochemical, electrochemical, or photocatalytic, membrane reactors show conversion advantages.
in a so-called membrane reactor. The type of By controlling the pressure of the gas and liquid
Catalytic Membranes 3
flows, it is possible to shift the reactants to meet Gryaznov VM (1986) Hydrogen permeable palladium
the catalyst zone (Fig. 1). membrane catalysts. Platinum Met Rev 30:68
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of the reactants is important, namely, in the case Development and application of perovskite-based cat-
of very fast or highly exothermic reactions. alytic membrane reactors. Catal Lett 54:69
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in surface science and catalysis, Elsevier science &
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Chemistry. https://www.sintef.no/globalassets/
Basile A (ed) (2012) Handbook of membrane reactors. upload/materialer_kjemi/energikonvertering-og-
Woodhead, Cambridge, UK (in press) materialer/dokumenter/watercatox-screen.pdf
Basile A, Gallucci F (eds) (2009) Modeling and simula- Saracco G, Specchia V (2000) Catalytic combustion of
tion of membrane reactors. Nova, New York propane in a membrane reactor with separate feed of
Basile A, Gallucci F (eds) (2011) Membranes for mem- reactants. IV. Transition from the kinetics- to the trans-
brane reactors: preparation, optimization and selec- port-controlled regime. Chem Eng Sci 55:3979
tion. Wiley, New York van Dyk L, Miachon S, Lorenzen L, Torres M, Fiaty K,
Basile A, Nunes S (eds) (2011) Advanced membrane Dalmon JA (2003) Comparison of microporous MFI
science and technology for sustainable energy and and dense Pd membrane performances in an extractor-
environmental applications. Woodhead, Cambridge, type CMR. Catal Today 82:167–177
UK Westermann T, Melin T (2009) Flow-through catalytic
Dittmeyer R, Hollein V, Daub K (2001) Membrane reac- membrane reactors – principles and applications.
tors for hydrogenation and dehydrogenation processes Chem Eng Process 48:17–28
based on supported palladium. J Mol Catal A Chem
173:135–184
Fritsch D, Peinemann K-V (1995) Catalysis with homo-
Further Reading
geneous membranes loaded with nanoscale metallic
Seidel-Morgenstern A (ed) (2010) Membrane reactors:
clusters and their preparation. Catal Today
distributing reactants to improve selectivity and
25:277–283
yield. Wiley, New York
Gobina E, Hughes R (1994) Ethane dehydrogenation
using a high-temperature catalytic membrane reactor.
J Membr Sci 90:11
C
Catalytic Reactions, Membrane membrane and reactor are integrated in the same
Operations of housing (Marcano and Tsotsis 2002).
Membranes can be inorganic (metallic,
Adelio Mendes ceramic, carbon) or polymeric in their nature.
Faculty of Engineering, University of Porto, Membranes can be permselective or
Porto, Portugal non-permselective. Permselective membranes
are characterized by two important parameters:
permselectivity, which describes the ability of the
Catalytic reactions (chemical, biochemical, pho- membrane to transport the different components
tochemical, electrochemical, and photoelectro- of a mixture at different rates, and permeability,
chemical) are promoted or enhanced in their which quantifies the total amount permeated by
rate by a catalyst. Most of the chemical catalytic the membrane when subjected to specific opera-
reactions are heterogeneous; the catalyst is nor- tion conditions, normalized by the membrane
mally a solid, while reactants are in fluid phase. In thickness. The mass transport mechanism is
the petrochemical industry, for example, the cat- described by the sorption – diffusion models for
alyst is usually composed of micro- or dense and microporous membranes. For porous,
nanoclusters of a noble metal in a support, usually different contributions should be considered: dif-
a metal oxide. In the fine chemical and organic fusive (activated, surface, Knudsen, and bulk)
synthesis, on the other hand, it is common that the and viscous (Poiseuille flow). The contribution
reactions be homogeneous. of each one depends on the operating conditions,
Membrane is a permselective medium or inter- pore size, penetrant mass and size and the sur-
face between two fluid phases. Membrane pro- face, and penetrant nature (Basile and Gallucci
cesses can be synergistically combined with 2011).
catalytic reactors targeting conversion, selectivity, There are various potential industrial applica-
or safety enhancements. These effects may be tions that take advantage of combining a catalytic
obtained by selective product extraction and puri- reactor with a membrane process, integrated or
fication, normally originating conversion and not in the same device, operating either in liquid
selectivity enhancements, or by segregated or dis- and/or gas phases. One of the main membrane
tributed feed of reactants, aiming selectivity studied functions has been the selective removal
and/or safety enhancements. When a reactor is of components from the reaction medium.
synergistically combined with a membrane pro- Biorefining and biofuel production, for example,
cess, the unit is called membrane reactor. Usually, take advantage of process integration of a biore-
actor and a permselective membrane, as is the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_118-3
2 Catalytic Reactions, Membrane Operations of
case of bioethanol and acetic acid production: the hydrocarbon and oxygen feed, the reaction is
continuous removal of the main product from the carried on in much safer conditions, and the pos-
reaction medium decreases or even eliminates the sibility of thermal optimization and oxygen con-
potential reaction inhibition (Ma et al. 2009; He centration control along the reaction medium can
et al. 2012). Also the removal of fermentation be used to improve the selectivity for the inter-
inhibitors generated during the pretreatment pro- mediate desired oxygenated product. Though in
cess of lignocellulosic material for the second- less extension, also proton-conducting mem-
generation bioethanol production is important, branes have been considered as distributors for
because of the negative impact in the ethanol hydrogenation reactions (Marcano and Tsotsis
yield and productivity and in the cell growth 2002; Seidel-Morgenstern 2010).
inhibition (He et al. 2012). Still in the selective
removal of a reaction product from the reaction
medium, it can be referred to as the selective References
removal of water in esterification reactions and
the selective removal of hydrogen in dehydroge- Basile A, Gallucci F (eds) (2011) Membranes for mem-
brane reactors: preparation, optimization and selec-
nation and water-gas shift reactions for a conver-
tion. Wiley, New York
sion shifting beyond the thermodynamic Basile A, Nunes S (eds) (2011) Advanced membrane
equilibrium based on feed conditions. In case of science and technology for sustainable energy and
using palladium-silver membranes in the dehy- environmental applications. Woodhead Publishing
Limited, Cambridge
drogenation and water-gas shift reactions, high-
He Y, Bagley DM, Leung KT, Liss SN, Liao BQ
purity hydrogen can be obtained (Marcano and (2012) Recent advances in membrane technologies
Tsotsis 2002; Basile and Nunes 2011). for biorefining and bioenergy production. Biotechnol
The membrane can also play a role of a selec- Adv 30:817–858
Ma Y, Wang J, Tsuru T (2009) Pervaporation of water/
tive distributor, dosing a reactant along the reac-
ethanol mixtures through microporous silica mem-
tion medium. This approach has been extensively branes. Sep Purif Technol 66:479–485
used in consecutive-parallel reaction schemes, Marcano JS, Tsotsis TT (2002) Catalytic membranes and
especially in partial oxy-dehydrogenation or oxi- membrane reactors. Wiley-VCH Verlag GmbH,
Weinheim
dation of alkanes and oxidative coupling of meth-
Seidel-Morgenstern A (ed) (2010) Membrane reactors:
ane, using dense ceramic or metallic membranes distributing reactants to improve selectivity and
permselective to oxygen (silver, yttrium- yield. Wiley, New York
stabilized zirconia, perovskites and related
oxides, or composite membranes involving a Further Reading
mixture of ionic and electronic conducting mate- Basile A (ed) (in press) Handbook of membrane reactors.
Woodhead Publishing Limited, Cambridge
rials, usually oxides and metals). Separating the
I
Ion-Exchange
Membranes,
Fig. 1 Schematic drawing
illustrating the structure of
a cation-exchange
membrane showing fixed
negative ions and mobile
positive counterions in the
polymer matrix
used. The first procedure results in a homoge- electrolyte in low-temperature fuel cell consists
neous ion-exchange membrane structure and is of a polyfluorocarbon material. This membrane is
closely related to the preparation of ion-exchange often referred to as “Nafion ® membrane” which
resins. Homogeneous ion-exchange membranes is the trade name of DuPont. There are several
are produced by either a polymerization of mono- more ion-exchange membranes with special
mers that carry anionic or cationic moieties or by properties commercially available such as the
introducing these moieties into a polymer which bipolar membrane which is composed of an
may be in an appropriate solution or a solid anion- and a cation-exchange layer laminated
preformed film. The second widely used together (Simons 1993).
ion-exchange membrane preparation technique
which leads to a rather heterogeneous structure
is based on mixing an ion-exchange resin powder References
with a binder polymer, such as polyvinylchloride
or polyethylene, and extruding the mixture as a Bergsma F, Kruissink CH (1961) Ion-exchange mem-
branes. Fortschr Hochpolym Forsch 21:307–362
film at a temperature close to the melting point of
Molau GE (1981) Heterogeneous ion-exchange mem-
the polymer. branes. J Membr Sci 8:309–330
A cation-exchange membrane with excep- Simons R (1993) Preparation of high performance bipolar
tional good chemical and thermal stability membranes. J Membr Sci 78:13–23
Xu TW (2005) Ion-exchange membranes: state of their
which is widely used in the electrolytic
development and perspective. J Membr Sci 263:1–29
chlorine-alkaline production and as polymer
C
receptors, cytoskeletal rearrangements, and cell considered in the choice of material suitable for
spreading. In particular, immediately after the biomedical device.
biomaterial comes into contact with cell environ-
ment, protein adsorption to its surface occurs.
This happens within seconds, long before the
References
first cells reach the surface. Consequently, cells
almost never come into direct contact with the De Bartolo L, Morelli S, Bader A, Drioli E (2002)
material surface; they rather interact with the Evaluation of cell behaviour related to physico-
layer of adsorbed proteins. This layer mediates chemical properties of polymeric membranes to be
the cell adhesion and also provides signals to the used in bioartificial organs. Biomaterials
23(12):2485–2497
cell through the cell adhesion receptors. The De Bartolo L, Gugliuzza A, Morelli S, Cirillo B,
membrane properties (roughness, physicochemi- Gordano A, Drioli E (2004) Novel PEEK-WC mem-
cal, mechanical, and transport) especially the sur- branes with low plasma protein affinity related to sur-
face characteristics play an important role in the face free energy parameters. J Mater Sci Mater Med
15:877–883
adhesion process (De Bartolo et al. 2004, 2008). De Bartolo L, Rende M, Morelli S, Giusi G, Salerno S,
Surface free energy, electric charge, and mor- Piscioneri A, Gordano A, Di Vito A, Canonaco M,
phology might all affect cell attachment and its Drioli E (2008) Influence of membrane surface prop-
behavior either indirectly, e.g., by controlling erties on the growth of neuronal cells isolated form
hippocampus. J Membr Sci 325:139–149
adsorption of the proteins present in the culture Griffin L, Naughton G (2002) Tissue engineering – current
medium (or secreted by the cells), or directly, challenges and expanding opportunities. Science
e.g., by guiding cell spreading with suitable sur- 259:1009–1014
face topography (De Bartolo et al. 2002). Such Hynes RO (2002) Integrins: bidirectional, allosteric sig-
naling machines. Cell 10:673–687
properties resulted in being critical to
cell–substratum interaction and have to be
C
Cell Adhesion in Bio Artificial Organs receptors recognize and interact with either
other cell adhesion receptors on neighboring
Loredana De Bartolo cells or with proteins of the ECM. ECM proteins
Institute on Membrane Technology, ITM-CNR, are typically large glycoproteins, including the
National Research Council of Italy, Rende (CS), collagens, fibronectins, laminins, and proteogly-
Italy cans that assemble into fibrils or other complex
macromolecular arrays. Owing to their binding to
adhesion receptors, they can also be tightly asso-
Binding of cells to a surface, extracellular matrix, ciated with the cell surface. At the intracellular
or other cells in an artificial device is used to surface of the plasma membrane, cell adhesion
replace a nonfunctioning organ. Correct cellular receptors associate with cytoplasmic plaque or
adhesion is essential in maintaining multicellular peripheral membrane proteins. Cytoplasmic
structure and allows cells to interact dynamically plaque proteins serve to link the adhesion systems
with adjacent cells and the extracellular matrix. to the cytoskeleton, to regulate the functions of
In bio artificial organs the cell adhesion process the adhesion molecules, and to transmit signals
involves cell–cell and cell–natural or artificial initiated at the cell surface by the adhesion recep-
matrix/material that plays essential roles in over- tors. Several substrates different for the shape and
all tissue architecture and proper physiological physico-chemical properties are used for cell
functions of the device. adhesion in artificial devices. Natural substrates
The functional units of cell adhesion are typ- such as ECM proteins (collagen, fibronectin,
ically multiprotein complexes made up of three vitronectin, laminin) or polymers (chitosan,
general classes of proteins: the cell adhesion mol- polylactic acid, polylysine, etc.) and synthetic
ecules/adhesion receptors, the extracellular substrates such as polystyrene, polycarbonate in
matrix (ECM) proteins, and the cytoplasmic the shape of scaffolds, gels, sponge, and mem-
plaque/peripheral membrane proteins. The cell branes can be used in devices. Semipermeable
adhesion receptors are usually transmembrane membranes made from polyethersulfone,
glycoproteins that mediate binding interactions polysulfone, polycarbonate, polytetrafluor-
at the extracellular surface and determine the oethylene, modified polyetheretherketone,
specificity of cell–cell and cell–ECM recogni- chitosan, polycaprolactone, polylactic acid,
tion. They include members of the integrin, polyglycolic acid, and copolymers in flat and
cadherin, immunoglobulin, selectin, and proteo- hollow fiber configurations are used for adhesion
glycan (for example, syndecans) superfamilies. of different type of anchorage-dependent cells
At the extracellular surface, the cell adhesion (hepatocytes, endothelial cells, neuronal cells,
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_121-5
2 Cell Adhesion in Bio Artificial Organs
Separation of hepatocytes and fibroblasts has polyurethane membranes. J Biomed Mater Res
been realized through surface-modified polyure- A 71A(3):470–479
Higuchi A, Shindo Y, Gomei Y, Mori T, Uyama T,
thane membranes combining the filtration pro- Umezawa A (2005) Cell separation between mesen-
cess with the use of negatively charged chymal progenitor cells through porous polymeric
membranes (Higuchi and Tsukamoto 2004). membranes. J Biomed Mater Res B Appl Biomater
74(1):511–519
Orfao A, Ruiz-Arguelles A (1996) General concepts about
cell sorting techniques. Clin Biochem 29(1):5–9
References
CH4 recovery = 86 %
550 m² membrane area 4
690 kW (theoretical compression power)
stream 5 used as compressor fuel
stream 4 to flare
2
3
Nitrogen removal (8 to 15% N2 ) 1 2 3 4 5 6
(NitrosepTM, MTR Inc.)
Flow rate (103 Nm3/h) 12 9 ? ? 1,9 1,1
Pressure (bar) 70 14 ? ? ? 3.5 1 6
N2 15 4 8.7 50 65 26
Composition (% mol.)
CH4 85 96 81.3 50 35 74
CH4 recovery = 86 %
1,800 m² membrane area 4 5
1,860 kW (theoretical compression power)
stream 6 used as compressor fuel
stream 5 to flare
4
3
CH4 recovery = 96 %
3,500 m² membrane area
2,680 kW (theoretical compression power)
part of stream 1 used as compressor fuel
stream 2 to flare
2
CH4/N2 Separation, Fig. 1 Permeation-based nitrogen removal from natural gas (After Lokhandwala et al. 2010)
resulting process schemes were leading to signif- time of this type of installation was estimated to
icant extra cost due to the presence of two com- be 1 year.
pressors: the first compression unit was used to The first field test of these membranes was
pressurize the methane-enriched permeate pro- therefore conducted with a 40 in-long module
duced by the first membrane stage to the pipeline equipped with few m2 of methane-selective
pressure, while the second one was aiming at membranes for more than 1 year on a shut-in
boosting the pressure of the permeate stream gas well containing 15 % nitrogen operated by
issued from the second-stage in order to recycle Butcher Energy in Southern Ohio. The perfor-
it at the input of the first membrane stage. With mances of the spiral-wound module were very
this scenario, the total equipment investment cost similar to those observed at lab scale, and its
was in a 4–8 million US dollar range (in 2009), permeation properties remained unchanged for
while the required membrane area was approxi- the first 6-month period. After this proof of prin-
mately equal to 4,000 m2. This appears to be ciple, MTR Inc. designed different membrane-
acceptable by gas processors as the payback based nitrogen removal process schemes, trade-
CH4/N2 Separation 3
named Nitrosep™, with various module/compres- gas to a gas stream offering 10 % more heating
sor configurations depending on the nitrogen con- value (lowering thus the nitrogen content to
centration to be addressed (Fig. 1). 9 %). The membrane system involved three
Up till now, 12 Nitrosep™ units have been stages in series and allowed a methane recov-
installed in the industry. Few examples depicting ery yield of 95 % for pipeline delivery.
the applications addressed by this membranes
process are listed hereafter:
References
– A very small unit was installed in Southern
Kentucky in order to upgrade 200 Nm3/h of Baker RW, Lokhandwala K (2008) Natural gas processing
natural gas containing 7 % nitrogen. This with membranes: an overview. Ind Eng Chem Res
two-membrane module unit was able to 47:2109–2121
Lokhandwala KA, Pinnau I, He ZJ, Amo KD, DaCosta
recover 80 % of the natural gas with a nitrogen
AR, Wijmans JG, Baker RW (2010) Membrane sepa-
content of 3.8 %. Part of the residue gas was ration of nitrogen from natural gas: a case study from
used as compressor engine fuel, while the rest membrane synthesis to commercial deployment.
was vented. J Membr Sci 346:270–279
Mitariten M (2001) New technology improves nitrogen-
– A much larger unit was installed in Rio Vista,
removal economics. Oil Gas J 99:42–44
California (14,000 Nm3/h treatment capacity). Mitariten M (2004) Economic nitrogen removal.
The membrane operation was aiming at Hydrocarb Eng 9:53–57
upgrading a 16 % nitrogen containing natural
C
Charged Ultrafiltration Membrane, Fig. 1 Positively charged membrane provides high retention of positively
charged protein while allowing transmission of neutral proteins
Et2O, AlLiH4
N N
NH2
N
1 2
Chemical Binding of Biomolecules to Membranes, Fig. 1 Scheme of synthesis of amino propyl pyrrole
Chemical Binding
of Biomolecules
a
to Membranes, O O
Fig. 2 Laccase
immobilization on NH2
modified electrode with H2N laccase
polyaminopyrrole; (a)
nucleophilic attack on the
glutaraldehyde, (b)
reduction of imine function
(IEM picture)
b
N N laccase
N N laccase
H H
and von Gunten 2008). The established oxidative chlorine. The Orton rearrangement
chlorinating strength of these species is takes place only when amide linkage is directly
Cl2 ~ HOCl > OCl (Soice et al. 2003). connected with benzene ring. Generally, the chlo-
The amide nitrogen of the membrane is highly rine resistance increases in the order of PA syn-
vulnerable to chlorine attack because of electron- thesized from aromatic, cycloaliphatic, and
withdrawing effect of carbonyl group. Upon aliphatic diamines, respectively.
exposure to free chlorine, N-H group is chlori- Thus, the following modifications can be con-
nated to N-Cl group which can reversibly form sidered as potential strategies to enhance the
the initial amid by treatment with reducing chlorine resistance of PA membranes (Geise
agents. The aromatic rings are also susceptible et al. 2010):
to attack by chlorine because it is an electron-rich
region. Two possible chlorination mechanisms 1. Replacing chlorine-sensitive amidic hydrogen
are proposed for aromatic rings, i.e., direct chlo- on the amide linkages with other moieties,
rination of the aromatic ring and Orton e.g., methyl ( CH3) or phenyl ( C6H5)
rearrangement, which involves initial chlorina- 2. Replacing the aromatic ring bonded to the
tion of amid nitrogen followed by an amide nitrogen with aliphatic chain or cyclics
intermolecular rearrangement, forming various 3. Prevention of Orton rearrangement by adding
aromatic substitution products (Fig. 1) (Raval protective groups at the possible chlorination
et al. 2010). sites on the aromatic rings
According to the chlorination mechanisms,
chlorine resistance of PA membranes largely Other than PA, polysulfone has much better
depends on the chemical structures of the chlorine resistance as it has stronger chemical
diamine components used. Aliphatic PA revers- bonds. However, due to hydrophobic nature of
ibly reacts with chlorine to yield N-chlorinated polysulfone, introduction of controlled levels of
amide. Tertiary PAs are inactive towards hydrophilic groups, e.g., SO3H, while retaining
O O H H O O H H
Cl2
C C N N C C N N
Irreversible direct aromatic chlorination
n Cl n
Cl
Re 2,
HC e t
ve IO ibl en
rs
ibl an ers em
e d ev ng
ch Cl Irr ra
lor O- ar
ina re
tio ton
n Or
O O Cl H
C C N N
Citric Acid Recovery by (Bialey and Ollis 1986). In order to reduce this
Electrodialysis environmental impact, the design of alternative
production scheme was investigated. Extraction,
Gerald Pourcelly adsorption, and membrane technologies, like
Institut Europeen des Membranes, CC 047, electrodialysis (ED), were proposed to replace
Universite Montpellier II, Place Eugene precipitation (Novalic et al. 1995). A complete
Bataillon, Montpellier Cedex 5, France scheme for carboxylic acid recovery is depicted
in Fig. 1.
For EDC step of citric acid salts to the three
Citric Acid Recovery by Electrodialysis dissociation constants of citric acid, the conduc-
[G. Pourcelly] tivity is mainly influenced by the pH value and
the concentration. More ion dissociation leads to
Carboxylic acids such as lactic, succinic, formation of further citric-acid-charged com-
gluconic, citric, and tartaric are widely used in plexes in the solution which in turn causes elec-
food processing, detergent manufacture, and bio- trical resistance reduction of the solution. The
degradable plastic production (Bailly et al. 2001). maximum ion density and consequently the min-
Their production at the industrial scale is mainly imum electrical resistance of the solution is
achieved by mean of fermentation from molas- obtained at pH 8 (Novalic et al. 1995). The
ses, starch hydrolysates, or sugars. Traditional EDBM step, which is water splitting by mem-
processes to obtain these carboxylic acids consist brane electrodialysis, provides an attractive com-
on the precipitation of both the acids and their plement to the fermentation technology by
salts, so they can be isolated from the rest of the removing the product acid while simultaneously
components of the raw material. Then, they are providing an equivalent amount of base for use in
placed in an acid medium (sulfuric acid) to gen- adjusting the pH in the fermentor (Fig.1). More-
erate the acid form. A latter concentration step is over, the produced citric acid is usually at a
carried out by evaporation followed by a crystal- relatively high concentration (0.5 M) so that the
lization. This generates large volumes of efflu- subsequent purification via crystallization or
ents with high salt contents. For example, typical other techniques is relatively inexpensive
yields of 1 kg of citric acid are obtained per 2 kg (Xu and Yang 2002).
of gypsum which is very difficult to dispose
Composite Membrane a 2
with Inorganic Fillers:
Electrolyser Application,
Fig. 1 Polarization
1.8
measurements for a PEM
Terminal voltage / V
water electrolysis cell 80°C
based on conventional 90°C
Nafion 115 and composite 1.6 100°C
PFSA–SiO2 membrane at 110°C
Nafion 115 120°C
various temperature and
3.0 bar abs pressure 1.4
1.2
1
−0.2 0 0.2 0.4 0.6 0.8 1 1.2 1.4
Current density / A cm-2
b 2
1.8
Terminal voltage / V
80°C
90°C
1.6
100°C
110°C
1.4 Composite Membrane 120°C
1.2
1
−0.2 0.2 0.6 1 1.4 1.8 2.2
-2
Current density / A cm
a
3300 3550
surface OH groups stretching/ cm-1
3100 3450
3000 3400
2 3 4 5 6 7 8 9
pH filler slurry
b 1650
400
H2O bending vibration / cm-1
200
1630
100
1620 0
0 2 4 6 8 10
pH filler slurry
Composite Membrane with Inorganic Fillers: Fuel corresponding performance of a composite membrane-
Cell Application, Fig. 1 Relationships between water based direct methanol fuel cell at 145 C
adsorption characteristics of inorganic fillers and
Computational Fluid Dynamics (CFD) about the wall shear stress distribution at the
and Membranes surface of the membrane. The study of hydrody-
namics reveals the optimum operating conditions
Philippe Moulin and the most suitable geometry characteristics to
Laboratoire de Mécanique, Modélisation et determine a compromise between membrane
Procédés Propres (M2P2-UMR 7340), Equipe area, channel (geometry and number), and energy
Procédés Membranaires (EPM), Aix Marseille consumption to optimize membrane processes.
Université, AIX en PROVENCE, France A large number of studies relate to the diphasic
flows, to the turbulence promoters, and to the
geometries of membranes capable of generating
The increasing number of CFD membrane stud- secondary flows. Usually a good agreement is
ies is clearly related to the recent developments in obtained between CFD and experimental data
computer power and to the use of finer grid obtained for the transfer of solvent. Some recent
meshes in the vicinity of the membrane. Two studies consider turbulent flows and the signifi-
approaches have been particularly considered: cant number of turbulence models in numerical
the comprehension of the hydrodynamics and of simulations, and their comparison with experi-
the mass transfer. mental results in the case of membrane processes
The hydrodynamics allows the increase of the is not excellent, which limits the use of CFD in
shear stress near the wall or the transmembrane turbulent regime.
pressure thus allowing the enhancement of per- Fouling remains a major problem in mem-
meate flux and the membrane processes. CFD brane processes: this phenomenon limits the pro-
allows determining the hydrodynamics, i.e., the cess efficiency and is difficult to predict and
pressure and velocity fields, taking into account anticipate. These difficulties are linked to the
the geometry of the module and the membranes, complexity of this phenomenon which implies
the membrane permeability and compactness, as different interdependent mechanisms occurring
well as the operating entry values such as filtra- at pore scale. The relative importance of each
tion or backwash pressures, filtration mode, and fouling mechanism has been determined
gravity. For example, it is possible to determine according to the particle size, the pore size, and
the pressure and velocity fields in (i) a hollow the surface density of pores. By CFD progress it
fiber module containing more than 40,000 fibers is now possible (a) to pursue the description of
(small diameter (di = 0.93 mm) and large flow the different fouling mechanisms by integrating
rate (50 m3.h 1) or in (ii) ceramic multichannel the complexity of the real membrane structure in
membranes or module to obtain information the numerical simulation and (b) to simulate
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_142-1
2 Computational Fluid Dynamics (CFD) and Membranes
different kinds of experimental deposit structure. studies, the difficulties are to well describe parti-
The limitation is the membrane reconstruction cle/particle colloidal interactions and
technique limiting this description at the MF resuspension of particles after capture.
and UF membranes. The filtration in a cylindrical Thus, CFD is without any doubt an important
pore (i.e., microchannels) can be simulated for tool for understanding mass transfer in membrane
different sizes of particles or pores, tortuosities, processes, and opportunities for the development
and hydrodynamic conditions. For these CFD of new membrane geometries are numerous.
C
10–3
Phase distri.,
Morphologies,
Micro fluids. Micro
Lattice Bolztmanm
10–9
FFV,FAV, d-spa,Tg, Conformationa analysis,
Molecular and sorption diffusion in large
Nano system Semiempirical, Monte Carlo
Computer-Aided Methods and Tools, Fig. 1 Computational methods and achievable properties
Computer-Aided Methods and Tools, Table 1 Advantages and disadvantages of some computational methods
Method Advantages Disadvantages
Molecular Systems of thousands of atoms, low Experimental data or values from quantum
mechanics and computational costs mechanics, absence of bond breaking/
Monte Carlo forming. Noncovalent bonds are not well
dynamics described, less general
Semiempirical Less computational demand than quantum Experimental data or values from quantum
mechanics approaches, systems of hundreds mechanics, less general
of atoms
Ab initio, density Do not depend on experimental data, useful Computationally very expensive
functional theory for a broad range of molecules without Small systems
quantum mechanics available experimental data, general
the illustrated computational methods are sum- of macrosystems can be carried out using
marized with their advantages and disadvantages. methods based on classic mechanics or dynam-
The information provided by smaller scales ics. The differential equations describing these
can be utilized in mesoscale calculations: coarse physical systems are evaluated numerically by
grain MD or Lattice Boltzmann (LB) (Swift means of FEM or finite volume procedures (De
et al. 1996). In particular, LB is a powerful Luca et al. 2014). There is a notable number of
method for simulating fluid confined in codes implemented for each method just
microsystems, as may be precisely a membrane. described. These are divided into programs in
This method allows to solve the Navier-Stokes which a single methodology is implemented or
equations in a simple way and with a notable those in which several methods, radically differ-
reduction of computational time. LB allows an ent, can be found. Therefore, it is possible to find
easy description of the interfaces and especially codes in which only QM (based on different
without the use of adjustable parameters as made theories) or MD are implemented separately and
by the conventional finite elements methods others in which both the methodologies are pre-
(FEM). Finally, the description of the properties sent. Particular attention should be given to
Computer-Aided Methods and Tools 3
parallel algorithms since parallel supercomputers De Luca G, Bisignano F, Paone F, Curcio S (2014) Multi-
allow the use of huge number of processors (or scale modeling of protein fouling in ultrafiltration pro-
cess. J Membr Sci 452:400–414
computers interconnected by the net). These pos- Metropolis N, Ulam S (1949) The Monte Carlo method.
sibilities allow to perform complex calculations J Am Stat Assoc 44:335–341
in short computational time. Steinhauser MO (2008) Computational multiscale model-
ing of fluids and solids. Springer, Heidelberg
Swift MR, Orlandini E, Osborn WR, Yeomans JM
(1996) Lattice Boltzmann simulations of liquid-gas
References and binary fluid systems. Phys Rev E 54(5):5041–5052
Veszprémi T, Fehér M (1999) Quantum chemistry.
Allen MP, Tildesley DJ (2003) Computer simulation of Kluwer Academic/Plenum Publishing, New York
liquids. Oxford University Press, New York Wood WW (1986) Early history of computer simulations
Clementi E, Corongiu G (eds) (1995) Methods and tech- in statistical mechanics molecular dynamics simula-
niques in computational chemistry METECC-95. tion of statistical systems. Proceedings of the Enrico
STEF, Cagliari. ISBN 88-86327-02-1, Club Europeen Fermi Summer School. Varenna, pp 3–13
MOTECC
C
carefully tune as a function of the type of calcu- De Luca G, Drioli E (2006) Force balance conditions for
lation which is required to be done. Huge litera- droplet formation in cross-flow membrane emulsifica-
tions. Journal of Colloid and Interface Science
ture exists about studies on any kind of chemical 294:436–448
models (periodic surfaces, slabs, or clusters) and De Luca G, Di Maio FP, Di Renzo A, Drioli E (2008)
correlated computational procedures (periodic Droplet detachment in cross-flow membrane emulsifi-
calculations, embedded clusters, and quantum cation: Comparison among torque- and force-based
models. Chemical Engineering and Processing
mechanics/molecular mechanics methods, etc.). 47:1150–1158
Saxer S, Portmann C, Tosatti S, Gademann K, Zurcher S,
Textor M (2010) Surface assembly of catechol-
functionalized poly(L-lysine)-graft poly(ethylene
References glycol) copolymer on titanium exploiting combined
electrostatically driven self-organization and biomi-
Allen MP, Tildesley DJ (2003) Computer simulation of metic strong adhesion. Macromolecules 43:1050–1060
liquids. Oxford University Press, New York Z€
urcher S, Wackerlin D, Bethuel Y, Malisova B,
Gademann K, Bethuel Y, Locher HH, Hubschwerlen Textor M, Tosatti S, Gademann K (2006) Biomimetic
C (2007) Biomimetic total synthesis and antimicrobial surface modifications based on the cyanobacterial iron
evaluation of anachelin H. J Org Chem 72:8361–8370 chelator anachelin. J Am Chem Soc 128:1064–1065
C
Constant-Volume Retentate
Diafiltration, Diluant u(t)
Fig. 1 Schematic
representation of constant- Permeate q(t)
Membrane
volume diafiltration module
settings
Feed
diafiltration level
Feed tank
Constant-Volume 0
Diafiltration,
Fig. 2 Dependence of
Microsolute reduction in percentage [%]
R = 0.9
microsolute removal on
applied diavolumes in
constant-volume R = 0.8
diafiltration
R = 0.7
90
R = 0.6
R = 0.5
R = 0.4
R = 0.3
R = 0.2
R = 0 R = 0.1
99
0 1 2 3 4 5 6 7 8 9 10
Diavolumes [-]
concentration cf,i(t) assuming that the diluant however, the problem can be reduced to the fol-
consists of no component i and the feed tank is lowing algebraic expression:
well mixed.
In many applications, the flux and the rejec- cf , i ðtÞ
ln ¼ DðRi 1Þ% for i ¼ 1, 2, N
tions are concentration-(inter)dependent quanti- cf , i ð0Þ
ties (Kovács et al. 2009) and may vary with
operating conditions such as temperature, applied where D is the diafiltration factor (also called
pressure, and hydrodynamics. In such cases, no diavolume) that is defined as the ratio of applied
closed form solution of the set of resulting com- volume of diluant to feed volume. For applica-
plex differential algebraic equations exists; thus, tions where the objective is to reduce the
numerical techniques are required to solve the microsolute concentration by a fixed amount,
model equations. Under the simple assumptions the necessary diavolumes can be determined
of constant permeate flow and rejections, based on Eq.2 as illustrated in Fig. 2.
Constant-Volume Diafiltration 3
Contactor-Type Catalytic Membrane ways. If the membrane is not wetted, the opera-
Reactor tion principle is similar to that of a membrane
contactor. The gas is on the support side, and the
Juergen Caro liquid is pumped through the shell side. The gas-
Institute of Physical Chemistry and eous reactants enter the liquid phase at the
Electrochemistry, Leibniz University, Hannover, gas/liquid contact plane which is established at
Germany the pore mouth towards the external membrane
surface. The catalyst is deposited on this surface
and gets in contact with the reactants. On the
Synonyms contrary, if the membrane is wetted the gas and
not the liquid is at overpressure as described in
Catalytic diffuser; Pore-through-flow catalytic Dittmeyer and Caro (2008).
membrane Gas–liquid contactors without catalytic func-
tion can be used in gas adsorption. Examples are
The term “catalytic membrane contactor” refers carbon dioxide removal from gas mixtures using
to a device in which a membrane containing a monoethanolamine (Simons et al. 2009) or ionic
catalytically active phase is used to provide the liquids (Albo et al. 2010) as carbon dioxide
reaction zone for conversion of one or more reac- absorbing solutions.
tants from one or more fluid phases (Dittmeyer For liquid-liquid and gas-gas catalytic mem-
and Caro 2008). The membrane not always has a brane contactors, see Dittmeyer and Caro (2008)
separation function, it provides the surface-rich (Fig. 1).
reaction zone for a gas-liquid, but also for a Catalytic diffuser with wettable membrane:
gas-gas and a liquid-liquid reaction. Applications The active material is placed solely into the sur-
of membranes with built-in catalysts for face layer of an asymmetric membrane. By
gas-liquid reactions have been also reviewed in applying overpressure on the gas side, above the
Dittmeyer et al. (2004). bubble point pressure of the intermediate layer
The catalytic diffuser concept can be utilized but below that of the surface layer, the gas/liquid
for solid-catalyzed gas/liquid reactions in various contacting plane is established inside the
References
Giuseppe Barbieri The mass balance for the component i-th consid-
Institute on Membrane Technology, Italian ering a single reaction will be:
National Research Council, Rende (CS), Italy
NX
reactions
dN i
FInlet
i FOutlet
i þ ni, j r j V Reaction
CSTR ¼ (2)
j¼1
dt
Before introducing the continuous stirred tank
membrane reactor (CST-MR), it is useful/helpful Mass balances provide a set of ordinary differen-
to report about the continuous stirred tank reactor tial equations (ODEs), in which the number of
(CSTR). moles of component i-th is time dependent. In
The continuous stirred tank reactor (CSTR) is Eq. 2, FiInlet and FiOutlet are, respectively, the inlet
an ideal reactor model assuming perfect mixing, and outlet molar flow of the component i-th, ri is
with no spatial gradients of any variable such as the reaction rate, Ni is the number of moles, and
species concentration, temperature, pressure, V is the reactor/reaction volume.
etc. The effect of the perfect mixing is the same In steady-state condition, the mass balance
value for, e.g., concentration, temperature, etc., equations fall into algebraic equations:
in any point of the whole reactor volume; and
their values are equal to those of the stream NX
reactions
exiting the reactor. In addition, the reaction rate FInlet FOutlet þ ni, j r j V Reaction ¼0 (3)
i i CSTR
has the same value in any point of the reactor. j¼1
Therefore, this reactor model operating at the
lowest reactant concentration and the highest Equation 3 provides the design equation Eq. 4 for
product concentration results in the lowest reac- a CSTR in steady-state conditions:
tion rate. However, an important effect of perfect
mixing is an easy temperature and reaction rate FInlet FOutlet
control, which results quite simply. Figure 1 V Reaction
CSTR ¼ i i
(4)
NX
reactions
The generic mass balance (Eq. 1) is still valid FSweep FPermeate þ AMembrane J i Permeating
i i
and has to be written down for both reaction and
permeation even though another term has to be dN Permeate
¼ i
(7)
included: the one taking into account the perme- dt
ation through the membrane. Therefore, Eqs. 6
The mass balance equations for steady state have
and 7 include the permeating flow rate (AMembrane
an algebraic form:
JPermeating, the product of the membrane area and
Reaction side:
permeating flux). This term is negative (being
mass leaving the reaction volume) on the
retentate side and positive (entering the perme-
ation volume) on the permeate one.
Reaction side:
FFeed
i FRetentate
i AMembrane J i Permeating
NX
reactions
þ ni, j r j V Reaction
CSTMR
j¼1
dN Retentate
¼ i
(6)
dt
Permeation side:
NX
reactions
FFeed
i FRetentate
i A Membrane
Ji Permeating
þ ni, j r j V Reaction
CSTMR ¼ 0
j¼1
FFeed FRetentate AMembrane J i Permeating
V Reaction
CSTMR ¼ i i
(8)
NX
reactions
ni , j r j
j¼1
Cost-Effective Gas Separations, Table 1 Commercial therefore, they are not best suited to produce
applications of gas separation membranes high purity nitrogen. However, when a mem-
Nitrogen production from air brane air separation process is combined with an
Air-drying adsorption process, membrane separation pro-
H2/CO adjustment in synthesis gas duces 95–99 % nitrogen from which final traces
H2 recovery in ammonia synthesis of oxygen is removed by adsorption process
H2 recovery in petrochemical processes (Choe et al. 1987). The second application of
Acid gas removal from natural gas hybrid process is for the removal of acid gases
Recovery and recycle of olefins in olefin polymerization
from the natural gas. Here, a hybrid process
process
consisting of acid gas selective membrane
followed by an amine scrubbing process offers a
more economical process for natural gas
Cost-Effective Gas Lower foot print and
Separations, upgrading (Baker and Lokhandwala 2008).
weight
Table 2 Benefits of
No moving parts (except
membrane gas separation
for compressors)
process
Remote operation References
Easy turnup/turndown
Portability Agrawal R, Xu J (1996) Gas-separation membrane cas-
cades utilizing limited numbers of compressors.
No open flames
AIChE J 42:2141
Baker RW, Lokhandwala K (2008) Natural gas processing
with membranes: an overview. Ind Eng Chem Res
47(7):2109–2121
Choe JC et al (1987) Process for separating components of
a gas stream, US Patent 4,701,187
Hybrid processes consisting of a membrane
separation process with a conventional gas sepa- Further Reading
ration process sometimes offer a more cost- Drioli E, Barbieri G (eds) (2011). Membrane engineering
effective solution for gas separation. Two exam- for the treatment of gases, volume 1: gas-separation
ples of these processes which are commercially problems with membranes. RSC Publishing, Cam-
bridge, UK
used are in production of high purity nitrogen and Paul DR, Yampol’skii YP (1994) Polymer gas separation
in the treatment of natural gas. Air separation membranes. CRC Press, Boca Raton, Fl, USA
membranes have selectivity limitations;
C
O
H
O O N
H
O
OCH2COH
HN O
O O O O
NH
O O
O O O
O O
O O O O
O
HN O O
O O O
O NH
O
N O
H O
Crown Ethers, Fig. 1 Structural formulae of (a) a typical crown ether, (b) valinomycin, and (c) an ionizable lariat
crown ether
the large molar volume counter anions can make sheet supported liquid membranes: influence of the
the diffusion of the ion pair rather slow. extractant. Sep Sci Technol 30:435–448
Lamb JD, Izatt RM, Robertson PA, Christensen JJ
Appending an ionizable pendent arm to the (1980) Highly selective membrane transport of Pb2+
crown ether ring (the ligand is called an ionizable from aqueous metal ion mixtures using macrocyclic
lariat ether; see Fig. 1c) can eliminate the need for carriers. J Am Chem Soc 102:2452–2454
the counter anions making it a more efficient Paul D, Suzumura A, Sugimoto H, Teraoka J, Shinoda S,
Tsukube H (2003) Chemical activation of cytochrome
transport system (Strzelbicki et al. 1989). Other c proteins via crown ether complexation: cold-active
types of functionalization have been found to synzymes for enantiomer-selective sulfoxide oxida-
impart exotic properties to the receptors. For tion in methanol. J Am Chem Soc
example, crown ethers with suitable functional 2003(125):11478–11479
Pedersen CJ (1967) Cyclic polyethers and their complexes
groups based on redox-switched (Shinkai with metal salts. J Am Chem Soc 20:7017–7022
et al. 1985a), thermosensitive (Shinkai Raut DR, Mohapatra PK, Manchanda VK (2012) A highly
et al. 1985b), and photoresponsive (Shinkai efficient supported liquid membrane system for selec-
et al. 1981) properties have also been used for tive strontium separation leading to radioactive waste
remediation. J. Membr. Sci. 390–391: 76–83
the transport of receptors. Functionalized crown Shinkai S, Nakaji T, Ogawa T, Shigematsu K, Manabe
ether-type ligands with carboxylate groups have O (1981) Photoresponsive crown ethers.
been suggested for the recovery of U from sea- 2. Photocontrol of ion extraction and ion transport by
water which is yet another exotic application of a bis(crown ether) with a butterfly-like motion. J Am
Chem Soc 103:111–115
the crown ether-based membrane transport Shinkai S, Inuzuka K, Miyazaki O, Manabe O (1985a)
systems. Redox-switchable crown ethers. 3. Cyclic-acyclic
interconversion coupled with redox between dithiol
and disulfide and its application to membrane trans-
port. J Am Chem Soc 107:3950–3955
References Shinkai S, Nakamura S, Tachiki S, Manabe O, Kajiyama
T (1985b) Thermocontrol of ion permeation through
ternary composition membranes composed of poly-
Casnati A, Pochini A, Ungaro R, Ugozzoli F, Arnaud F,
mer/liquid crystal/amphiphilic crown ethers. J Am
Fanni S, Schwing MJ, Egberink RJM, De Jong F,
Chem Soc 107:3363–3365
Reinhoudt DN (1995) Synthesis, complexation and
Strzelbicki J, Charewicz WA, Liu Y, Bartsch RA
membrane transport studies of 1,3-alternate calix[4]
(1989) Solvent extraction and bulk liquid membrane
arene-crown-6 conformers: a new class of cesium
transport of Co(II) and Ni(II) ammine cations by
selective ionophores. J Am Chem Soc 117:2767–2777
proton-ionizable crown ethers. J Incl Phenom Mol
Dozol JF, Casas J (1994) Influence of the extractant on
Recognit Chem 7:349–361
strontium transport from reprocessing concentrate
Yamaguchi T, Nishimura K, Shinbo T, Sugiura M (1988)
solutions through flat-sheet supported liquid mem-
Amino acid transport through supported liquid mem-
branes. Sep Sci Technol 29:1999–2018
branes: mechanism and its application to enantiomeric
Dozol JF, Casas J, Sastre AM (1995) Transport of cesium
resolution. Bioelectrochem Bioenerg 20:109–123
from reprocessing concentrate solutions through flat-
C
0.2 30:323
Derazshamshir A, Baydemir G, Andaç M, Say R, Galaev
IY, Denizli A (2010) Molecularly imprinted PHEMA-
based cryogel for depletion of hemoglobin from
human blood. Macromol Chem Phys 211:657
0.1 Gun’ko VM, Savina IN, Mikhalovsky SV
(2013) Cryogels: morphological, structural and
adsorption characterization. Adv Colloid Interface
Sci 187–188:1
0.0 Lozinsky VI, Plieva FM, Galaev IY, Mattiasson B (2001)
0 100 200 300 400 The potential of polymeric cryogels in bioseparation.
Flow rate (cm/h) Bioseparation 10:163
Stela DE, Valentina DM (2013) Design, synthesis and
Cryogels, Fig. 2 Pressure drop at different flow rates interaction with Cu2+ ions of ice templated composite
hydrogels. Res J Chem Environ 17:4
Tamahkar E, Bereli N, Say R, Denizli A (2011) Molecu-
References larly imprinted supermacroporous cryogels for cyto-
chrome c recognition. J Sep Sci 34:3433
Bereli N, Andac M, Baydemir G, Say R, Galaev IY,
Denizli A (2008) Protein recognition via ion
D
a b T2 ≈ T1 Raffinate
T2 <T1 Liquid-phase
raffinate Water vapor-
Water- containing fluid
containing liquid
Membrane
T1
T1
Water vapor
Water vapor
Dehydration, Fig. 1 Common membrane dehydration processes. (a) Pervaporation. (b) Vapor-phase separation
Methanol is another commodity chemical with a described by the solute diffusion model. Most
large market. Water is miscible with a number of polymeric membrane materials fall into this cat-
solvents and chemicals, such as acetic acid, ace- egory, which include polyvinyl alcohol (PVA),
tone, and tetrahydrofuran. Dehydration of these chitosan, alginate, polysulfone (PSF),
solvents is involved in a range of industrial chem- polyimides, polyamides, polyaniline, and poly-
ical conversion processes. The presence of water electrolyte membranes such as cation-exchanged
in industrial gases is ubiquitous. Air dehumidifi- Nafion. Separation in a microporous membrane is
cation and natural gas dehydration are examples mostly achieved through molecular sieving based
of significant industrial gas drying processes. on molecular sizes and/or selective adsorption of
One salient feature for the membrane dehy- water at entrance of the membrane pore. Micro-
dration process is molecular separation functions porous zeolite, silica, and carbon are common
of the membrane. Removal of free water from membrane materials. Water molecule is often
slurry, i.e., separation of water from particulates, the smallest one in a mixture, and selective sep-
is typically referred as dewatering processes. The aration can be realized by making the membrane
membrane allows permeation of water molecules pore size small enough. However, the small pore
while blocking other molecules. Because of the size reduces molecule diffusion rates and may
molecular separation function, the membrane have a negative impact on flux. Molecular sieving
dehydration provides significant advantages based on selective water adsorption enables
over conventional evaporation and gas drying achievement of both high flux and selectivity
technologies. The vapor-phase membrane sepa- (Zhang and Liu 2011). Some of zeolite frame-
ration is a steady-state process operating under works, such as NaA, ZSM-5, and X-type and
constant temperature and pressure, as compared Y-type zeolite, have the pore size larger than
to periodic switches between adsorption that of water molecule but can be very selective
(or absorption) and regeneration required for the toward water adsorption over other molecules.
solid (or liquid) desiccating process. For separa- Permeation of the other molecules is blocked
tion of a water-miscible liquid, the membrane due to adsorption of water molecules at the
dehydration is not limited by thermodynamic entrance of the zeolite pore, although the pore
gas/liquid equilibrium such as co-boiling that can be permeable to the other molecules in the
often occurs in alcohol-water distillation pro- absence of moisture.
cesses. The membrane dehydration is considered The membrane dehydration performances are
as an energy-efficient and compact process. characterized by flux (Jw), permeance (Pw), and
A number of membrane materials have been separation factor (Sw/i), which can be calculated
studied, and some of them are commercially from experimental measurements as follows:
developed for the dehydration application. They
can be classified into two groups (Fig. 2): dense Dnw
Jw ¼
and microporous. The dense membrane provides Am Dt
selective absorption of water over other mole-
cules. The separation mechanism can be
Dehydration 3
Dehydration,
Fig. 2 Separation
mechanisms of dehydration
membrane. (a) Solute
diffusion in dense
membrane. (b) Molecular
sieving in microporous
membrane
Dehydrogenation ethane
Reactions,
Fig. 1 Principle of a 2-step
oxidative ethane C2H4, H2O
C2H6 ← C2H4 + H2
→ non-consumed C2H6
dehydrogenation in an
oxygen-transporting perowskite membrane
membrane reactor with a
perovkite membrane O2-depleted O2
air
air
100
literature
this work
80 air N2
propene selectivity / %
60
O2
40
C3 H8 C3 H6 + H2 C3 H6 + H2O
20
0
0 20 40 60 80 100
propane conversion / %
Dehydrogenation Reactions, Fig. 2 2-step oxidative propane dehydrogenation as described in Figure 1 for ethane
a
Diluant
Retentate
b
Diluant Retentate
Feed
Permeate Feed Permeate
Diafiltration, Fig. 1 Schematic flow diagram. (a) Batch diafiltration. (b) Continuous diafiltration
Diafiltration, Table 1 Comparison of batch and continuous diafiltration (Adopted from Lipnizki et al. 2002)
Batch Continuous
UF plant investment Low High
Batch tank investment High Low
Control investment Low High
Space requirement UF Low High
Space requirement tank High Low
Feed volume flexibility High Low
Antibiotic/protein concentration in permeate Variable Constant
Residence time High Low
Temperature flexibility Low High
Module efficiency Low High
Energy consumption High Low
(e.g., amino acids, antibiotics, organic acids, that an operation mode of a filtration process is
etc.) from fermentation broth considered.
• NF: desalination of dyes and optical bright- Membrane filtration plants are rarely designed
eners; partial demineralization of whey; pro- exclusively for microsolute removal. Most appli-
duction of desalted and concentrated cations require a simultaneous microsolute
antibiotics; desalination of gelatin for removal (i.e., macrosolute purification) and
improved color and whipping properties macrosolute concentration (i.e., feed volume
• RO: solvent replacement in herb extracts; beer reduction). In many cases, the term diafiltration
dealcoholization stands for a process that is designed to achieve
these dual objectives. In continuous processing,
Diafiltration is also called membrane filtration the different modes of operation (i.e., concentra-
in dilution mode in accordance with the terminol- tion and dilution modes) are assigned to different
ogy recommendation of the former European stages which are connected in series. In batch
Society of Membrane Science and Technology processing, the targeted twin aims of concentra-
(now known as the European Membrane Society) tion and fractionation are obtained either in con-
(Gekas 1988). Although the latter term is less secutive operational steps (e.g., in traditional
frequently used in the literature, it better reveals diafiltration, intermittent feed diafiltration,
sequential dilution diafiltration) or applying
Diafiltration 3
specific diluant utilization strategies (e.g., Jönsson AS, Trägårdh G (1990) Ultrafiltration applica-
variable-volume diafiltration, dynamic-volume tions. Desalination 77:135–179. doi:10.1016/0011-
9164(90)85024-5
diafiltration). Overall, these characteristics of Lipnizki F, Boelsmand J, Madsen RF (2002) Concepts of
diafiltration put it in a favorable position in com- industrial-scale diafiltration systems. Desalination
parison with other separation techniques and 144:179–184
even with a sequence of competitive unit opera-
tions (Jönsson and Trägårdh 1990). Further Reading
Beaton NC, Klinkowski PR (1983) Industrial ultrafiltra-
tion design and application of diafiltration processes.
J Sep Process Technol 4(2):1–10
References Dutré B, Trägárdh G (1994) Macrosolute-microsolute sep-
aration by ultrafiltration: a review of diafiltration pro-
Gekas V (1988) Terminology for pressure-driven membrane cesses and applications. Desalination 95:227–267
operations. Desalination 68(1):77–92. doi:10.1016/ Madsen RF (2001) Design of sanitary and sterile UF- and
0011-9164(88)80045-6. http://www.sciencedirect.com/ diafiltration plants. Sep Purif Technol 22–23:79–87
science/article/pii/0011916488800456
D
Flow
meter
Recovered
acid
Receiving Feed
solution solution
Direct Membrane Emulsification factor of 2–10 is found between pore size and
droplets size. Additional parameters have to be
Emma Piacentini1, Alessandra Imbrogno1 and considered to tune the production of an emulsion
Richard G. Holdich2 by DME:
1
Institute on Membrane Technology
(ITM-CNR), University of Calabria, Rende (CS), • Shear stress. Uniform and small droplets are
Italy obtained when the shear stress increases as a
2
Department of Chemical Engineering, consequence of their faster detachment at the
Loughborough University, Loughborough, membrane pore surface. In general, the mean
Leicestershire, UK droplet size decreases exponentially until it
reaches a size where it becomes, more or
less, independent of the applied shear. The
In the early 1990s, Nakashima and Shimizu shear stress can be produced: (i) by flowing
(1991) introduced membrane technology for the continuous phase tangentially to the mem-
emulsion preparation by the direct emulsification brane surface (cross-flow ME), (ii) by pulsat-
method (DME). In DME, the dispersed phase is ing the continuous phase in the lumen side of
directly fed through the membrane pores and the membrane (pulsed ME or pulsed back-
emulsion droplet formation takes place on the and-forward ME), (iii) by rotating or vibrating
other side of the membrane, which is in contact the membrane, and (iv) by inducing azimuthal
with the continuous phase (Fig. 1). Here, droplets oscillation of a tubular membrane.
can detach after reaching a critical dimension • Transmembrane pressure. The transmem-
either for spontaneous deformation (Static Mem- brane pressure needs to be higher than a crit-
brane Emulsification,) or as a consequence of the ical pressure (capillary pressure) in order to
shear stress generated by moving the membrane initiate dispersed phase intrusion in the pores.
or the continuous phase (Dynamic Membrane The dispersed phase flux increases with an
Emulsification. increase of the transmembrane pressure as
Usually, in the DME method, the membrane is more pores are gradually activated for droplet
wetted by the continuous phase, and hydrophilic production and the velocity increases in the
and hydrophobic membranes are used in the prep- pores. Larger droplets are produced at higher
aration of oil-in-water (O/W) and water-in-oil dispersed phase flux.
(W/O) emulsions, respectively. The mean emul- • Emulsifier. Droplet size decreases with lower
sion droplet size is controlled by the appropriate interfacial tension and, according to the time
selection of the pore size of the membrane, and a needed by the emulsifier, is dissolved in the
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_182-1
2 Direct Membrane Emulsification
Direct Methanol Fuel Cell (DMFC) (Ren et al. 1996), thereby reducing significantly
the fuel utilization efficiency of the device.
Antonino Salvatore Arico A scheme of the overall reaction process occur-
CNR-ITAE Institute, Messina, Italy ring in a DMFC equipped with a proton-
conducting electrolyte is outlined below:
The core of a direct methanol fuel cell is a polymer CH3 OH þ H2 O ! CO2 þ 6Hþ
electrolyte ion-exchange membrane. The elec- þ 6e ðanodeÞ (1)
trodes (anode and cathode) are in intimate contact
with the membrane faces. A scanning electron 3=2O2 þ 6 Hþ þ 6e ! 3H2 O ðcathodeÞ (2)
micrograph of a DMFC MEA is shown in Fig. 1
(Aricò et al. 2001). The electrodes usually consist CH3 OH þ 3=2 O2 ! CO2
of three layers: catalytic layer, diffusion layer, and þ 2H2 OðoverallÞ (3)
backing layer. The catalytic layer is composed of a
mixture of catalyst and ionomer, and it is charac- In the presence of an alkaline electrolyte, the
terized by a mixed electronic-ionic conductivity. process is outlined as follows:
The catalysts are often based on carbon-supported
or carbon-unsupported PtRu and Pt materials at CH3 OH þ 6 OH ! CO2 þ 5 H2 O
the anode and cathode, respectively. The mem- þ 6e ðanodeÞ (4)
brane as well as the ionomer consists, in most
cases, of a perfluorosulfonic acid polymer. The 3=2O2 þ 3H2 O þ 6e ! 6OH ðcathodeÞ (5)
package formed by electrodes and membrane is
called “membrane and electrode assembly” CH3 OH þ 3=2O2 ! CO2
(MEA). The overall thickness of this package is þ 2H2 OðoverallÞ (3’)
generally smaller than 1 mm. Each MEA forms a
cell. Several cells are usually connected in series The thermodynamic efficiency of the process is
to form a fuel cell stack that is integrated in a given by the ratio between the Gibbs free energy,
system which contains the auxiliaries allowing i.e., the maximum value of electrical work (DG )
stack operation and delivering of the electrical that can be obtained, and the total available energy
power to the external load. for the process, i.e., the enthalpy (DH ). Under
Typical perfluorosulfonic acid membranes standard conditions:
used in the present DMFCs, such as Nafion
(DuPont), are permeable to methanol transport
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_183-2
2 Direct Methanol Fuel Cell (DMFC)
0.2
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Current density / A cm–2
rev ¼ DG =DH ; reversible energy efficiency potential for methanol oxidation is 1.18 V (Aricò
(6) et al. 2001). It does not vary significantly in the
operating range 20 –130 C and 1–3 bar abs.
with pressure.
Usually, the open-circuit voltage of a polymer
DG ¼ DH ðT DS Þ (7) electrolyte direct methanol fuel cell is signifi-
cantly lower than the thermodynamic or reversible
and potential for the overall process (Fig. 2). This is
mainly due to methanol crossover that causes a
DG ¼ nF DErev (8) mixed potential at the cathode and to the irrevers-
ible adsorption of intermediate species at elec-
DErev is the electromotive force. At 25 C and trode potentials close to the reversible potential.
1 atm and with pure oxygen feed, the reversible Direct methanol fuel cells find application in
Direct Methanol Fuel Cell (DMFC) 3
portable power sources, assisted power units Dillon R, Srinivasan S, Aricò AS, Antonucci V (2004)
(APU), and electrotraction (Dillon et al. 2004). International activities in DMFC R&D: Status of tech-
nologies and potential applications. J Power Sources
127:112
Ren X, Wilson MS, Gottesfeld S (1996) High performance
References direct methanol polymer electrolyte fuel cells. J
Electrochem Soc 143:L12
Arico AS, Srinivasan S, Antonucci V (2001) DMFCs:
From fundamental aspects to technology development.
Fuel Cells 1:133
D
Direct Contact
Membrane Distillation
(DCMD), Fig. 1 Typical
DCMD schema
Direct Contact
Membrane Distillation Tf
(DCMD), Fig. 2 DCMD vapour
m
process Tf
Tpm
vapour
Tp
Direct Contact Membrane Distillation (DCMD) Appli- crystallization units operating on the brine from NF and/or
cations, Fig. 1 Scheme of sea water desalination plant RO stages (Based on Di Profio et al. (2010)).
using integrated membrane system containing membrane
Direct Contact Membrane Distillation (DCMD) Applications, Fig. 2 Schematic diagram of DCMD powered by
solar and wind energy (Reprinted from Susanto (2011), copyright (2011), with permission from Elsevier)
DCMD is less severe than in conventional desa- treatment, either to produce a permeate less haz-
lination processes (Khayet and Matsuura 2011). ardous to the environment or to obtain a retentate
DCMD can be operated with solutions of that contains high concentration of valuable
extremely high concentration of salts, even chemicals (Table 1) (Khayet and Matsuura
close to the supersaturated point, and the perme- 2011).
ate flux was satisfying. Therefore, DCMD has The main disadvantage of DCMD process is a
also been successfully applied to wastewater problem with membrane wetting, what limits the
Direct Contact Membrane Distillation (DCMD) Applications 3
Direct Contact Membrane Distillation (DCMD) Applications, Table 1 Examples of DCMD application in various
fields
Application area Examples of application
Water treatment Desalination of seawater and brackish water, removal of various contaminants (heavy metals,
arsenic, boron, humic acid) from surface and groundwater, production of high purity water,
removal of low concentrations of organics (ethanol, acetone, acetonitrile, n-butanol)
Wastewater Treatment of low- and medium-level radioactive wastewater, textile wastewater contaminated
treatment with dyes, oil-water emulsions, HCl removal from etching solutions from electrochemical
industry, separation of photocatalyst in the photocatalysis-DCMD system, reclamation in space
Medicine and Concentration of an extract of traditional Chinese medicine
biology Concentration of bovine plasma and bovine blood, bovine serum albumin, to ameliorate
treatment of uremia
Pharmacy Pharmaceutical wastewaters containing taurine
Food industry Concentration of fruit and juices, whey, sugarcane, etc.
Biotechnology Removal of toxic products from culture broth, production of ethanol in a bioreactor-DCMD
system
Chemical Concentration of acids, separation of a half-finished product (HCl) from the reaction mixture to
industry shift the reaction equilibrium in DCMD-chemical reactor system
Other Ethylene glycol removal from coolant liquids, breaking azeotropic mixtures HCl-water,
propionic acid-water, salt crystallization in DCMD/MCr
water
Hydrochloric acid
Metal objects
purified
Etching bath Rinsing objects
Concentration
Concentration of MD II
spent pickling
solution MD I
Crystallisation
HCl solution
salt
HCl concentration water
MD III
Direct Contact Membrane Distillation (DCMD) Appli- solution using DCMD (Reprinted from Tomaszewska
cations, Fig. 3 The flow – sheet diagram of integrated et al. 2001, copyright (2001) with permission from
processes of metal pickling with treatment of spent Elsevier)
concentration of organic compounds to diluted pilot scale to clean low- and medium-level radio-
aqueous solutions. The membranes used in MD active waste from a nuclear center.
are chemically resistant; thus, they can tolerate Moreover, DCMD found success in the treat-
harsh operating conditions. DCMD is a promis- ment of solutions containing substances sensitive
ing method for recovery of HCl from metal pick- to high temperature due to the risk of their deg-
ling solutions (Fig. 3) (Tomaszewska et al. 2001). radation, especially in biotechnology and food
The process was also successfully applied in a
4 Direct Contact Membrane Distillation (DCMD) Applications
Sulfuric acid
system: chemical reactor/ Retentate
DCMD (Based on
Tomaszewska and Mientka
2009) Permeate
Hydrochloric
CRYSTALLIZER acid
KHSO4
Solvent
Solvent DESALTING
recovery 2KHSO4 K2SO4+H2SO4
industry (fruit juices concentration) (Sotoft showing that DCMD can be economically attrac-
et al. 2012). tive especially when low-grade energy or alter-
Novel applications are bio- and chemical reac- native energy is used.
tors integrated with DCMD in which the volatile
products are continuously removed from the
reaction mixture to shift the equilibrium and References
improve productivity. It was found that a contin-
uous extraction of ethanol from broth using Di Profio G, Curcio E, Drioli E (2010) Membrane crystal-
lization technology. In: Drioli E, Giorno L (eds) Com-
DCMD resulted in an increase of its productivity
prehensive membrane science and engineering,
by 87 % (Khayet and Matsuura 2011). The mem- vol 4. Academic Press/Elsevier, Oxford, pp 21–46
brane reactor based on DCMD was applied in the Drioli E, Curcio E, Di Profio G (2005) Review paper: state
production of potassium sulfate for fertilizer of the art and recent progresses in membrane
contactors. Chem Eng Res Des 83(A3):223–233
industry (Tomaszewska and Mientka 2009). The
Drioli E, Stankiewicz AI, Macedonio F (2011) Membrane
concentration of the reaction mixture containing engineering in process intensification – an overview.
KCl and K2SO4 close to the saturated state in the J Membr Sci 380:1–8
membrane reactor resulted in periodical precipi- Khayet M, Matsuura T (2011) Membrane distillation.
Principles and applications. Elsevier, Amsterdam
tation of KHSO4, whereas HCl was continuously
Sotoft LF, Christensen KV, Andrésen R, Norddahl
removed from the reaction mixture to shift the B (2012) Full scale plant with membrane based con-
equilibrium of the conversion (Fig. 4). centration of blackcurrant juice on the basis of labora-
MD is generally recommended for special tory and pilot scale tests. Chem Eng Process 54:12–21
Susanto H (2011) Towards practical implementations of
purposes for which the application of other mem-
membrane distillation. Chem Eng Process 50:139–150
brane techniques was considered impossible. Tomaszewska M, Mientka A (2009) Conversion of KCl
Until now the DCMD process has been under into KHSO4 in membrane reactor: long-term experi-
development due to high energy consumption ments. Desalination 245:647–656
Tomaszewska M, Gryta M, Morawski AW (2001) Recov-
and problems with the membrane wettability dur-
ery of hydrochloric acid from metal pickling solutions
ing long-time operation. However, it should be by membrane distillation. Sep Purif Technol
pointed out that there are numerous calculations 22–23:591–600
D
better anchor into the dispersed phase and the increasing attention over the last 15 years. The
decrease of droplet size by improving methods technique is attractive given the low energy con-
of formation (Garti 1997). sumption, the better control of droplet size and
Double emulsion is generally prepared in a droplet size distribution and especially the mild-
two-step emulsification process using two surfac- ness of the process. Microchannel emulsification
tants of opposite solubility. To produce O/W/O is a novel method for producing monodisperse
emulsion, a W/O emulsion is first prepared with a emulsions. It is even more monodisperse than
large excess of hydrophobic surfactant (HLB usually obtained with membrane emulsification
<10), by strong homogenization, to form the (Graaf et al. 2005).
smallest possible droplets. In the second step a
W/O/W double emulsion is further formed by
gentle addition of the W/O (termed inner emul- References
sion) to water in which a hydrophilic one (HLB
>10) has been dissolved (Bibette et al. 1999). Bibette J, Calderon FL, Poulin P (1999) Emulsions: basic
principles. Rep Prog Phys 62:969–1033
The most important conventional emulsifica-
Garti N (1997) Double emulsions-scope, imitations and
tion devices are stirring apparatuses, rotor–stator new achievements. Colloid Surf A 123–124:233–246
systems, and high-pressure homogenizers. Mem- Graaf S, Schroën CGPH, Boom RM (2005) Preparation of
brane emulsification is a relatively new method double emulsions by membrane emulsification-a
review. J Membr Sci 251:7–15
for the production of emulsions that has received
D
emulsification is the low energy consumption. membranes pore size. At high porosities, it is
Also the better control of droplet size and distri- more likely for droplets to coalesce at the mem-
bution and the mildness of the process are highly brane surface before they detach. If the porosity is
attractive. Compared to conventional methods, a too low, the dispersed phase flux may be not
disadvantage of membrane emulsification is that sufficient for viable production of emulsions.
the flux of the dispersed phase through the mem- The thinner the membrane, the larger the flux
brane is fairly low. However, the flux of dispersed through the pores will be, which leads to a higher
phase could be increased by using a membrane droplet expansion rate. It has been observed that
with a low hydraulic resistance (e.g., hydrophilic membranes are fit for making O/W
microsieves). emulsions and hydrophobic membranes for W/O
The commonly used membranes for mem- emulsions. The droplet size decreases sharply as
brane emulsification are Shirasu porous glass the cross-flow velocity increases from rest and
(SPG) membranes, ceramic aluminum oxide reaches a size where it becomes more or less
(a-Al2O3) membranes, a-alumina- and zirconia- independent of the flow velocity. The permeating
coated membranes, macroporous silica glass flux is increased by increasing the transmem-
membranes, micro-fabricated metal membranes, brane pressure. Another important parameter
polytetrafluoroethylene (PTFE) membranes, and affecting the droplet size is the wall contact
hydrophobized silicon nitride microsieves. angle. Higher wall contact angle results in larger
For membrane emulsification two methods droplets and a more polydisperse emulsion.
of operation are used: cross-flow membrane
emulsification and premix membrane
emulsification. References
Generally, the important process controlling
parameters are membrane pore size, porosity, Graaf S et al (2005) Preparation of double emulsions by
membrane emulsification-a review. J Membr Sci
thickness, and surface type, the velocity of con-
251:7–15
tinuous phase, the transmembrane pressure, and Joscelyne SM, Tragardh G (2000) Membrane
wall contact angle. It has been found that it is a emulsification-a literature review. J Membr Sci
linear relationship between the droplet size and 169:107–117
D
Dynamic Membrane Emulsification, Table 1 Membrane emulsification techniques, shear stress profile, and forces acting on a forming droplet
Membrane emulsification based on moving the continuous phase
ME plant Forces acting on a drop at the pore level Shear stress profile
Dynamic Membrane Emulsification
Dynamic Membrane Emulsification
(continued)
3
4
membrane pores by using a pump or nitrogen gas In dynamic ME, the forces acting on a droplet
while stirring the continuous phase with a rotator at the membrane pore level include detaching
when a tube-shaped submerged membrane is used forces, driving droplets off the pore, and retaining
or with a paddle blade stirrer in the case of a flat- forces, holding droplets on the pore. Detaching
sheet membrane (Stillwell et al. 2007). Stirred ME forces are drag (FD), buoyancy (FBG), inertial
is useful for emulsion production at batch scale, in (FI), lift (FL), and static pressure (FSP) force,
the laboratory, and it is especially used to study the while the main retaining force is the interfacial
effect of different experimental conditions and tension (Fg). The drag force (FD) is created either
chemistry on the formulation properties. by moving the continuous phase parallel to the
In rotating ME, the dispersed phase is intro- membrane surface or by moving the membrane;
duced into the center of a rotating tubular porous the buoyancy force (FBG) is due to the density
membrane, and droplets are detached at the mem- difference between the continuous phase and the
brane wall in the radial direction into the station- dispersed phase; the inertial force (FI) is caused by
ary continuous phase (Vladisavljević and the dispersed phase flow moving out from the pore
Williams 2006). The pressure is generated in the outlet; the dynamic lift force (FL) results from the
membrane lumen by using nitrogen gas or a asymmetric velocity profile of the continuous
pump, while the membrane is rotated in the con- phase near the droplet; static pressure (FSP) force
tinuous phase by an overhead stirrer. Rotating is due to the pressure difference between the dis-
ME is particularly advantageous for the produc- persed phase and the continuous phase at the
tion of coarse emulsions and fragile structured membrane surface; the interfacial tension force
products in which the droplets and/or particles (Fg) represents the effect of dispersed phase adhe-
are subject to breakage during the pump sion around the edge of the pore opening. In the
recirculation. However, the use for large-scale case of “moving membrane” emulsification, addi-
production is limited due to the complicated and tional (or enhanced) forces have to be considered.
more expensive design and higher power con- For rotating membrane emulsification, com-
sumption compared to alternative designs. pared to a nonrotating system, the drag force cre-
The vibrating ME principle is similar to the ated by the membrane rotation (FDR) has to be
rotating ME except for the use of oscillation of taken into account, and the gravitational body
the membrane perpendicularly with respect to the force is replaced by the centrifugal force (FC)
dispersed phase injection direction (Holdich resulting from centrifugal acceleration and density
et al. 2010). The frequency and amplitude of the difference of the two phases. High centrifugal force
axial oscillation of the membrane was generated may be responsible for polydisperse emulsion pro-
by an electrically driven vertical oscillator and duction in the case of O/W emulsion due to defor-
could be controlled separately. mation of the emerging oil drops and induced flow
In azimuthally oscillating ME, a tubular mem- of oil drops toward the membrane surface causing
brane is periodically rotated back and forward in coalescence and wetting of the membrane.
a slowly cross-flowing continuous phase, while For an oscillating membrane system where the
the dispersed phase is radially injected in the membrane is axially excited, an additional drag
lumen side of the membrane using a pump force (FDE) and inertial force (FIE) appear in the
(Silva et al. 2015). The azimuthal (tangential) direction parallel to the membrane. This is due to
oscillation of the membrane is controlled by a a sudden change in the direction of the membrane
control panel which is connected to the oscillator which induces a velocity difference in the column
motor providing separate control over the fre- of liquid inside the membrane and localized high
quency and membrane displacement. Azimuth- pressure at the peak positions of the vertical
ally oscillating ME operates in a continuous oscillation (i.e., top and bottom of the
mode, and it is suitable for large-scale production membrane tube).
providing high production rates, facilitating easy In dynamic ME, the droplet breakup process is
process automation and reduced operation time. correlated with a dripping or jetting behavior
6 Dynamic Membrane Emulsification
wave is moving, for a regular wave form such as a industrial scale manufacture. Chem Eng Res Des
sine wave. 76(8):902–910
Piacentini E, Drioli E, Giorno L (2014) Pulsed back-and-
forward cross-flow batch membrane emulsification
with high productivity to obtain highly uniform and
concentrate emulsions. J Membr Sci 453:119–125
References Silva PS, Dragosavac MM, Vladisavljević GT,
Bandulasena HCH, Holdich RG, Stillwell M, Williams
Holdich RG, Dragosavac MM, Vladisavljevic GT B (2015) Azimuthally oscillating membrane emulsifi-
(2010) Membrane emulsification with oscillating and cation for controlled droplet production. AIChE
stationary membranes. Ind Eng Chem Res J. doi:10.1002/aic.14894
49(8):3810–3817 Stillwell MT, Holdich RG, Kosvintsev SR, Gasparini G,
Holdich RG, Dragosavac MM, Vladisavljevic GT, Cumming IW (2007) Stirred cell membrane emulsifi-
Piacentini E (2013) Continuous membrane emulsifica- cation and factors influencing dispersion drop size and
tion with pulsed (oscillatory) flow. Ind Eng Chem Res uniformity. Ind Eng Chem Res 46(3):965–972
52:507–515 Vladisavljević GT, Williams RA (2006) Manufacture of
Peng SJ, Fellow RAW (1998) Controlled production of large uniform droplets using rotating membrane emul-
emulsions using a crossflow membrane: part II: sification. J Colloid Interface Sci 299(1):396–402
E
adenine dinucleotide (NAD)), which are con- Another strategy is to add an additional mediator
sumed in the reaction (e.g., Eq. 1) and have to according to
be regenerated for a process to be economical:
NADþ þ Medred ⇄ NADH þ Medox þ (3)
þ
CO2 þ NADH þ H ⇄ HCOOH
þ NADþ (1) Medox þ þ Hþ þ 2e ⇄ Medred (4)
Electrofiltration,
Fig. 1 Schematic sketch of
electrofiltration principle,
Fw stands for driving force
due to the friction between
the particle and flowing
solvent molecules and Fe
stands for driving force
resulting from action of the
applied electric field E on
the particle carrying
electrical charge
E
Electromembrane, a
Fig. 1 (a) Cation-
exchange membrane with a Counter-ion pathway
homogeneous structure; (b)
ion-exchange membrane
with a heterogeneous
structure prepared from an
ion-exchange resin powder
in a binder polymer (From Counter-ion Co-ion Fixed ion
Strathmann 2010)
Polymer matrix
b
Counter-ion pathway
Electromembrane, Fig. 2 Principle of a bipolar membrane. Left hand: water dissociation under electrical field. Right
hand: the two ion-exchange layers bearing fixed anion- or cation- exchange groups
stability are on the market, and BPM with an Pourcelly G, Bazinet L (2009) Developments of BPM
industrial-scale lifetime (>20,000 h) is available. technology in food and bio-industries. In: Pabby AK,
Rizvi SSH, Sastre AM (eds) Handbook of membrane
separations, CRC Press, Boca Raton, pp 581–634
Strathmann H (ed) (2004) In: Ion exchange membrane
References separation processes. Membrane technologies series,
Elsevier, Amsterdam
Donnan FG (1911) Theory of membrane equilibrium and Strathmann H (2010) Electrodialysis: a mature technology
membrane potential in the presence of non-dialysing with a multitude of new applications. Desalination
electrolyte. Z Electrokem Angew Phys Chem 264:268–288
17:572–581
E
(Westermeier 2001). They are used for routine background. Nafion membrane electrophoresis
clinical analysis and related applications, as well is a potentially attractive technique for the sepa-
as for the analysis of molecules in physiological ration of small organic molecules like amino
fluids. These membranes have large pores and acids or ions.
therefore have a low sieving effect on molecules.
The electrophoretic separation is thus entirely
based on charge density. The matrix exerts little
Cross-References
effect on diffusion so that the separated zones are
relatively wide and the resolution and limit of
▶ Cellulose Acetate (CA) Membrane
detection area is low. For these reasons, cellulose
▶ Ion Exchange Membrane
acetate membranes are often replaced by gel
▶ Perfluorosulfonic Acid Polymer Membrane
electrophoresis.
Other supporting membranes for electropho-
resis include Nafion membranes, a type of
perfluorosulfonic acid membrane, and cation- References
exchange membranes, which are chemically
Ahuja S, Jimidar M (2008) Capillary electrophoresis
resistant and consist of a pore-structure cluster
methods for pharmaceutical analysis. Academic,
network (Fang et al. 2004). These membranes are Amsterdam
widely used in the field of chloralkali industry Fang C, Wu B, Zhou X (2004) Nafion membrane electro-
and in fuel cells. A Nafion membrane contains phoresis with direct and simplified end-column pulse
electrochemical detection of amino acids. Electropho-
hydrophilic pores (10–20 Å and 50–60 Å in size)
resis 25:375–380
acting as very narrow electrophoresis channels. Westermeier R (2001) Electrophoresis in practice,
The fixed-charge sites ( SO3 ) on the hydro- 3rd edn. Wiley-VCH, Weinheim
philic pore surface provide a strong charged
E
Electrophoretic a b
Deposition,
Fig. 1 Schematic of
electrophoretic deposition + − −
process. (a) Cathodic EPD +
and (b) anodic EPD + −
−
+ +
− −
+
−
+ + −
− + − +
The EPD technique is also used for the prep- ▶ Zeolite Membrane
aration of membrane electrode assembly for fuel
cell (Morikawa et al. 2004). A membrane elec-
trode assembly can be prepared by EPD process
References
onto a Nafion membrane. A suspension
consisting of ethanol, carbon powders with Pt Abdollahi M, Ashrafizadeh SN, Malekpour A (2007)
catalyst, and Nafion polymer is used to obtain a Preparation of zeolite ZSM-5 membrane by electro-
stable dispersed solution. The thickness of the phoretic deposition method. Microporous Mesoporous
prepared catalyst layer is controlled by EPD dura- Mater 106:192–200
Besra L, Liu M (2007) A review on fundamentals and
tion or concentration of suspension. The cell applications of electrophoretic deposition (EPD).
obtained may present a higher electrochemical Prog Mater Sci 52:1–61
performance compared with ordinary cells. Corni I, Ryan MP, Boccaccini AR (2008) Electrophoretic
deposition: from traditional ceramics to nanotechnol-
ogy. J Eur Ceram Soc 28:1353–1367
Morikawa H, Tsuihiji N, Mitsui T, Kanamura K (2004)
Cross-References Preparation of membrane electrode assembly for fuel
cell by using electrophoretic deposition process.
▶ Electrophoretic Painting J Electrochem Soc 151:A1733–A1737
▶ Fuel Cell Membrane
E
m¼
v where NA is the Avogadro’s constant (kmol1),
E I is the ionic strength (kmol m3), e is the permit-
tivity (J1 C2 m1), k is the Boltzmann’s constant
The electrophoretic velocity is the distance of (J K1), and is T the temperature. O’Brien and
migration divided by time, also called velocity White (1978) obtained a more rigorous solution
of migration. Mobilities are sometimes expressed to the equations describing the electrophoretic
with a negative sign, because migration of the mobility of a rigid spherical particle with a uni-
solutes or particles generally occurs in the direc- form charge density. The predictions of this
tion opposite to the electrophoretic field (which is model coincide with those of the Debye-H€uckel-
taken as reference). Henry theory for systems with zeta potentials less
than 25 mV.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_208-2
2 Electrophoretic Mobility
Embryonic Stem (ES) Cell growth factors and molecules, which trigger the
differentiation process.
Loredana De Bartolo ES cells for their ability of propagating them-
National Research Council of Italy, Institute on selves indefinitely represent a valuable tool for
Membrane Technology, ITM-CNR, Rende (CS), both research and regenerative medicine. They
Italy can serve as an unlimited source of any cell type
in the body; human ES cells could yield highly
effective in vitro models for use in drug discovery
Embryonic stem (ES) cell is a totipotent stem cell programs and provide a renewable source of cells
derived from an early stage embryo, which is for use in transplantation therapy. Cell therapies
called blastocyst. This stage is reached 4–5 days based on the use of ES cells have been proposed
after fertilization and contains from 64 to several for tissue replacement after injury or disease.
hundred cells organized in an outer shell, the Adult stem cells, isolatable from bone mar-
trophectoderm, and the inner cell mass (ICM). row, adipose tissue, tooth pulp, and many other
The ICM is the locus of pluripotent cells destined locations of the body, are capable of self-renewal
to yield all the tissues of the developed organism. and can be readily expanded ex vivo for several
In the process of obtaining embryonic stem cells, passages without losing their self-renewal capac-
the trophectoderm is removed by ity. Mesenchymal stem cells can differentiate
immunosurgery, and the ICM is disaggregated into multiple tissue-forming cell lineages such
and plated on feeder cells. Ethical issues surround as osteoblasts, chondrocytes, adipocytes,
the derivation of human ES cells from in vitro tenocytes, and myocytes. Recent work on the
fertilized blastocysts. differentiation of bone marrow-derived mesen-
Embryonic stem cells have pluripotency and chymal stem cells into neuron-like cells is
indefinite replication characteristics. These cells another demonstration of considerable plasticity
have the capacity to give rise to differentiated of adult mesenchymal stem cells. Stem cells are
progeny representative of all three embryonic often a preferred cell source for regeneration of
germ layers (ectoderm, endoderm, and meso- multiple cell lineage tissues. The ability to
derm). ES cells are able to differentiate in all expand stem cells is desired to generate cells for
cell types differently from adult stem cells that tissue engineering in clinical and pharmaceutical
can produce only a limited number of cell types. applications (Rahaman and Mao 2005). Conven-
It is possible to modulate the differentiation of tional methods for expanding stem cells or pro-
stem cells in a given phenotype by using specific genitor cells comprised polystyrene culture
dishes and component of extracellular matrix
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_210-4
2 Embryonic Stem (ES) Cell
such as collagen. Alternatively biocompatible to act as scaffolds to guide and improve 3D tissue
and biodegradable materials have been proposed formation, substrates to enhance cell culturing
to support cells and promote their differentiation techniques, vehicles for cell delivery, and sources
and proliferation toward the formation of a tissue of immobilized and/or time-released factors.
(Piscioneri et al. 2011). They can be applied to the regeneration of numer-
Advances in cell-based therapies would not ous tissue types, including the liver, pancreas,
have been possible without the innovative design bone, cartilage, skin, and nerves, and are being
and fabrication of several generations of bioma- used for the in vitro realization of physiological
terials. Novel biomaterials with distinct proper- models.
ties are necessary to accommodate the growth
and interactions of multiple cell lineages in com-
posite tissue constructs (Griffith 2000). Mem- References
brane systems provide the temporary structural
framework for tissue-forming cells to synthesize De Bartolo L, Bader A (2013) Biomaterials for stem cell
therapy: state of art and vision for the future. CRC
extracellular matrices and other functional com-
Press, Boca Raton
ponents in the intended shape and dimensions Griffith LG (2000) Polymeric biomaterials. Acta Mater
(De Bartolo and Bader 2013). They can respond 48:263–277
on the key demands for utilizing cell-based ther- Pavlica S, Piscioneri A, Peinemann F, Keller M,
Milosevic J, Staeudte A, Heilmann A, Schulz-
apies to engineer composite tissue constructs
Siegmund M, Laera S, Favia P, De Bartolo L, Bader
with a purposeful orientation toward anatomic A (2009) Rat embryonic liver cell expansion and dif-
structures that the tissue-engineered constructs ferentiation on NH3 plasma-grafted PEEK-WC-PU
are intended to regenerate. Development of new membranes. Biomaterials 30:6514–6521
Piscioneri A, Campana C, Salerno S, Morelli S, Bader A,
intelligent biomaterials in synergy with cell biol-
Giordano F, Drioli E, De Bartolo L (2011) Biodegrad-
ogy will advance stem cell-based clinical thera- able and synthetic membranes for the expansion and
peutics. Engineered membranes have the functional differentiation of rat embryonic liver cells.
potential to mimic and control the physical, Acta Biomater 7:171–179
Rahaman MN, Mao JJ (2005) Stem cell-based composite
chemical, and biological factors necessary for
tissue constructs for regenerative medicine.
guiding stem cell differentiation (Pavlica Biotechnol Bioeng 91(3):261–284
et al. 2009). They are currently being investigated
E
Emulsion Liquid Membrane (ELM) larger interfacial area, and scope of continuous
operation.
Vladimir S. Kislik Since an ELM is a thin film of liquid (oil or
Campus Givat Ram, Casali Institute of Applied aqueous) composed of surfactants and their sol-
Chemistry, The Hebrew University of Jerusalem, vents between a feed and a receiving phase, any
Jerusalem, Israel immiscible liquid can serve as a membrane
between two liquid or gas phases containing a
solute at different concentrations. If the solute is
Emulsion liquid membrane, ELM, is a system in soluble in the membrane phase and has a reason-
the form of double emulsions (for details, see able diffusivity through the membrane, then its
Chakraborty et al. 2010). It may be of two selective transport through the membrane from
types: water-in-oil emulsion dispersed in an higher to lower concentration can be achieved.
external aqueous phase and oil-in-water emulsion This type of permeation has simple mechanism
dispersed in an outer organic phase. The mem- and not of much technical importance.
brane phase in the water-in-oil-in-water (W/O/ At facilitated transport mechanism, liquid
W) type is the immiscible oil phase separating membrane incorporates a reactive component or
the aqueous phases, while in the O/W/O type, the carrier, reacting reversibly and selectively with
immiscible water phase separating the two species of interest to carry the formed complexes
organic phases acts as the LM. Hence, the liquid across the LM to the internal phase, and dissoci-
membrane serves here a dual purpose: ates, discharging the solute to the internal phase.
(a) permitting selective transfer of one or more The unchanged carrier then diffuses back to the
components through it from external phase to membrane-external phase interface (see Fig. 1).
internal droplets and vice versa a‘nd A small amount of carrier is required in the mem-
(b) preventing mixing of external and internal brane phase even for achieving a high degree of
phases. The emulsion is dispersed in the feed separation. At different proton concentrations in
solution, and mass transfer from the feed to the the aqueous phase or using another ions, ion
internal receiving phase takes place. ELMs were exchange processes between two LM surfaces
first used for separation of hydrocarbons from occur. This phenomenon is called coupled mass
wastewater with high separation efficiency. Com- transport. If the transports of these two different
pared to conventional processes, emulsion liquid species occur in the same direction, it is called
membrane (ELM) process has some attractive cotransport, while transport in opposite direction
features, for example, simple operation, high effi- is called countertransport. Evidently the process
ciency, extraction and stripping in one stage, leads to the transport of targeted ionic species
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_211-2
2 Emulsion Liquid Membrane (ELM)
Enhanced Oil Recovery (EOR) removal units such as membrane operations offer
much flexibility for such an operation (Table 1).
Arnaud Baudot The first large-scale EOR project operating
Physics and Analysis Division, IFP Energies membranes has been carried out in the Sacroc
nouvelles, Solaize, France oil field located in Western Texas. Carbon dioxide
injection was launched in 1972 (at a flow
range up to 240,000 Nm3/h). Three CO2 recovery
Enhanced oil recovery (EOR) aims at increasing units were initially installed: two hot potassium
the oil field’s recovery yield, thanks to high- carbonate-based absorption units (operated by
pressure injection of water or carbon dioxide. Sun Explo with a 190,000 Nm3/h capacity lead-
Injection of pressurized carbon dioxide leads to ing to a reduction of carbon dioxide from 24 % to
the maintenance of high pressures in the reservoir 0.5 % and Chevron, with a 54,000 Nm3/h lower-
and to an improvement of oil displacement, ing CO2 content down to 1 %) and an amine
thanks to several physical effects: decrease of (MEA)-based absorption unit (operated by
oil viscosity due to carbon dioxide solubilization, Monsanto, with a 20,000 Nm3/h capacity). At
stripping effects, and modification of multiphase the end of the 1970s, realizing that the level of
equilibria due to CO2 solubilization in the reser- CO2 was raising at a higher rate than expected,
voir aqueous phase. When the oil reaches the Chevron contacted Cynara in order to install and
surface, carbon dioxide is purged with the asso- operate two gas permeation units upstream of the
ciated gas. Since the volumes of concerned carbon hot potassium carbonate absorption columns. The
dioxide are very large – from 140 to 280 Nm3 par treatment capacities of the membrane units were,
extracted barrel (Mazur and Chan 1982) – it is respectively, 60,000 Nm3/h at 35 bar feed pres-
necessary to separate carbon dioxide from the sure prior to the Sun unit and 25,000 Nm3/h at
hydrocarbon gaseous phase in order to have it 33 bar feed pressure prior to the Chevron unit.
recycled to the reservoir (after pressurization). Cynara chose to operate a single-stage configura-
Since the quantity of CO2 dissolved in oil tion, the membrane module being installed in
varies over a large range of values during the parallel. The membrane operation proved to be
whole production of the reservoir (levels from highly flexible and reliable, as the membrane
40 % up to 90 % can be observed after a few modules remained in operation twice longer
years of production (Cooley and Dethloff 1985)), than the expected lifetime (more than 5 years
it is rather difficult to design a cost-effective CO2 instead of 2–3 years) without any selectivity
removal unit that could operate during the entire decrease. A slight decrease in membrane perme-
life of the reservoir. Therefore, modular CO2 ability has nevertheless been observed
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_218-2
2
Enhanced Oil Recovery (EOR), Table 1 Comparison of relative investment costs (CAPEX) and operating costs (OPEX) of membrane-based, solvent-based, and hybrid
processes for carbon dioxide capture (EOR applications)
CAPEX réf. Cryo.a Mem.
Operating conditions Study realized by Year OPEX réf. + Mem. Mem. +DEA DEA Cryo.a TEA KCO3 chaud
175.000 m3/h Amoco (Goddin 1982) 1982 47 M$ 1 2.2 1.56 1.48
90 % CO2, 20.4 M$/a 1 1.76 1.39 1.12
18 bar
118.000 m3/h Permea (Boustany et al. 1983) 1983 16.1 M$ 1.50 1 1.31
80 % CO2 6.5 M$/a 1.31 1 1.82
190.000 m3/h Fluor Engineering Schendel and Seymour 1985) 1984 1 0.63 0.63b
40 % CO2 1 0.56 0.68b
a
Cryo.: cryogenic distillation (Ryan-Holmes process (Kohl and Nielsen 1997))
b
Hot potassium carbonate + membrane
Enhanced Oil Recovery (EOR)
Enhanced Oil Recovery (EOR) 3
Enhanced Oil Recovery (EOR), Fig. 1 EOR example of permeation application (Spillman 1989)
throughout the operation, and it was necessary to Shell, Texas: Cynara membranes were used to
add more modules in order to maintain the pro- process 13,000 Nm3/h of gas containing
duction level of the membrane operation 70 % CO2 (Fig. 1).
(Marquez and Hamaker 1986).
Since then, other membrane companies have
seen their products involved in other EOR
References
projects:
Boustany K, Narayan RS, Stookey DJ (1983) Economics
– Kvaerner membrane systems (Chapel of removal of carbon dioxide from hydrocarbon gas
et al. 1999): mixtures. In: Abstracts 62nd Annual Gas Processors
Dallas Production Inc. (Texas) treated Association, San Francisco, CA, pp 146–149
Chapel DG, Mariz CL, Ernest J (1999) Recovery of CO2
200,000 Nm3 of gases containing up to from flue gases: commercial trends. In: Oral Presenta-
25 % of carbon dioxide in 1994 during a tion Canadian Society of Chemical Engineers Annual
feasibility study that lasted for 18 months. Meeting, Saskatoon, Sakatchewan, Canada.
After this test, the membrane unit was in Cooley TE, Dethloff WL (1985) Field-tests show mem-
brane processing attractive. Chem Eng Prog 81:45–50
operation treating 1200 Nm3/h. Goddin CS (1982) Comparison of processes for treating
Hydrocarbon Operating, Inc. (Texas) gases with high CO2 content. In: Abstracts 61st
processed 590 Nm3/h at 51 bar feed pres- Annual Gas Processors Association Convention, Dal-
sure in 1994 on a pilot skid composed of las, TX, pp 60–68
Kohl A, Nielsen R (1997) Gas purification, 5th edn. Gulf
two tubular membrane modules. Publishing Co, Houston, pp 1238–1295
– Medal: Marquez JJ, Hamaker RJ (1986) Development of mem-
A Medal membrane unit was operated at the brane performances during SACROC operations. In:
need of the 1990s to process 14,200 Nm3/h Oral presentation at AIChE Spring National Meeting
and Petro. Expo’86. New Orleans, LA
at 56 bar, 48 % CO2, reducing the retentate Mazur WH, Chan MC (1982) Membranes for natural-gas
CO2 concentration down to 6 %. sweetening and CO2 enrichment. Chem Eng Prog
– Cynara (Kohl and Nielsen 1995): 78:38–43
Amoco, Texas (1994): Cynara membranes Schendel RL, Seymour JD (1985) Take care in picking
membranes to combine with other processes for CO2
were used to process 35,000 up to removal. Oil Gas J 83:84–86
120,000 Nm3/h of gas containing 80 % CO2. Spillman RW (1989) Economics of gas separation mem-
Mobil, Salt Creek (1992): Cynara membranes branes. Chem Eng Prog 85:41–62
were used to process 76,000 up to
120,000 Nm3/h of containing 70 % CO2.
E
Enzymatic Ultrafiltration Membranes (Immobilization of Urease and Trypsin), Fig. 1 Scheme of layer-by-layer
adsorption of polyelectrolytes on membrane
References
The extraction index assumes a specific and more membrane reactors since a desired chemical can
interesting form when a chemical reaction takes be fed in it but also produced by reaction. In this
place inside the membrane unit such as in the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_221-1
2 Extraction Index
case, Eq. 1 has to take into account also the If the water-gas shift reaction is used as an exam-
production term: ple, the extraction index can be defined as the
ratio of the H2 permeated through the membrane
Extraction Indexi ¼ to that totally available in the feed stream both as
Permeate flow ratei H2 molecules and also obtainable from other
Feed flow ratei þ Production by Reaction for i th chemicals (e.g., CO) by reaction, to the mem-
(2) brane unit (Eq. 3):
Flow ratePermeate
H2
H2 Extraction Index ¼
Flow rateAvailable
H2
in the feed
Flow ratePermeate
H2
in the MR¼ (3)
Flow rateFeed
H2 þ a Flow rateFeed
CO
H2 O=CO feed molar ratio per H2 O=CO feed molar ratio < 1
a¼
1 per H2 O=CO feed molar ratio 1
The extraction index (Barbieri et al. 2008) takes extraction index is determined by the membrane
into account the hydrogen fed as H2 molecules properties, feed molar ratio, and CO conversion
and that is contained in the feed stream in other achieved in the membrane reactor, at set operat-
chemicals (e.g., H2O). The term (a flow rate CO ing conditions.
feed) of the Eq. 3 considers the maximum H2
extractable from the chemicals (other than hydro-
gen) present in the system. The coefficient References
(a) takes into account the defecting reactant
(CO or H2O) by means of the feed molar ratio Barbieri G, Brunetti A, Tricoli G, Drioli E (2008) An
innovative configuration of a Pd-based membrane
H2O/CO. It (a) is equal to the feed molar ratio if
reactor for the production of pure hydrogen. Experi-
the latter is lower than 1 (CO in defect with mental analysis of water gas shift. J Power Sources
respect to H2O). It (a) will be equal to 1 when 182(1):160–167. doi:10.1016/j.jpowsour.2008.03.086
the CO exceeds the H2O. As defined, the
F
Non-porous
membrane References
Van der Bruggen B (2010) Pervaporation membrane reac- Wu P, Brisdon BJ, England R, Field RW (2002) Prepara-
tors. In: Enrico D, Lidietta G (eds) Comprehensive tion of modified difunctional PDMS membranes and a
membrane science and egineering, vol 3. Academic, comparative evaluation of their performance for the
Oxford, pp 135–163 pervaporative recovery of p-cresol from aqueous solu-
tion. J Membr Sci 206:265–275
F
Fat Hydrolysis, Membrane that buoyancy effect leads to creaming at the top
Operations of of the container, but the process may be speeded
up by centrifugation or filtration. The major dis-
Angela C. Macedo1 and F. Xavier Malcata2 advantage of the latter is the difficulty in remov-
1
LEPABE - Laboratory of Engineering of ing the fat layer once formed – coupled with
Processes, Environment, Biotechnology and clogging of the membrane pores – which is par-
Energy, University of Porto, Porto, Portugal ticularly detrimental in the case of hydrophobic
2
DEQ – Department of Chemical Engineering & matrices. Milk is often homogenized by forcing it
LEPABE - Laboratory of Engineering of into a tiny nozzle under high pressure, so as to
Processes, Environment, Biotechnology and reduce the average globule size to less than 1 mm;
Energy, University of Porto, Porto, Portugal this creates a more uniform distribution of glob-
ules that improves kinetic stability of the emul-
sion (Fox and McSweeney 1998).
Lipids that are solid at room temperature are Hydrolysis of fats can be effected by lipases
termed fats. In nature, most fats are (and esterases, to a lesser extent), which require a
triglycerides – consisting of a glycerol backbone, fat/water interface be present; this type of inter-
to which three individual fatty acid moieties are facial reaction is thus promoted by high specific
attached. The variety of fats in nature and their areas, which may be attained at the expense of
diversity in terms of physicochemical properties addition of emulsifiers and vigorous stirring.
come from the number of combinations of the However, lipases are typically much more expen-
hundreds of existing fatty acid residues – which, sive than their fat substrates, so some form of
due to their underlying metabolic synthesis path- immobilization thereof is in order for economic
way, are characterized by an even number of feasibility; this approach is particularly simple
carbon atoms. because such enzymes do not require cofactors
In view of their insolubility and the relevance for catalytic activity, while possessing a rela-
to water-based life, fats often appear stabilized tively high hydrophobic nature that facilitates
via emulsification in aqueous media; this is nota- spontaneous adhesion to hydrophobic materials
ble in the case of milk fat, with globules via adsorption.
surrounded by a membrane containing proteins Several immobilized microbial lipases are
and phospholipids. Said native globules range in available from industrial suppliers, using, e.g.,
size from less than 1 mm to over 10 mm. The ion exchange resins and polymeric materials as
uneven size distribution provides larger globules supports; they have been applied to hydrolyze
with a tendency to float: under static conditions, fats in emulsified form, but show the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_223-2
2 Fat Hydrolysis, Membrane Operations of
disadvantage that the fat and enzyme particles Depending on the level of water in their vicin-
must collide for catalysis to occur. Porous mem- ity, membrane-immobilized lipases operating on
branes constitute an interesting alternative, a fat substrate may also perform ester synthesis,
because lipase can be immobilized inside their as well as interesterification – of the acidolysis,
pores – with water pumped along one side and alcoholysis, and transesterification
(melted) fat along the other. Besides low rates of types – depending on whether the aqueous sub-
fouling, said tangential membranes may offer strate is replaced by a fatty acid, an alcohol, or
high volumetric efficiencies – especially if they another fat, respectively. This process is rela-
are manufactured in hollow-fiber form – and per- tively easy to bring about, but suffers from two
mit the concentration of fat to remain at its max- major shortcomings: enzymes tend to deactivate
imum level ever by circumventing phase mixing. as time online elapses, thus calling for enzyme
Furthermore, immobilized lipase processes makeup; and product separation is often difficult,
offer fatty acid- and stereo-specificity advantages especially when only lipid phases are
over plain acid- or base-catalyzed hydrolysis of involved – and resorts to distillation (which
fats – which are intrinsically should be carried out at low pressure in the case
nonspecific. Considering the difference in metab- of heat-labile fats).
olism of fatty acids depending on their original
regiodistribution and chain length, lipases have
been largely applied to produce tailor-made References
derivatives of triacylglycerols with medium- or
short-chain fatty acid residues in external posi- Fox PF, McSweeney PLH (1998) Milk lipids. In: Fox PF,
McSweeney PLH (eds) Dairy chemistry and biochem-
tions (sn-1 and sn-3) and long-chain fatty acids in
istry. Blackie Academic and Professional Publishers,
the internal position (sn-2) (Willis et al. 1998); London, pp 67–146
these are in higher and higher demand for nutri- Willis W, Lencki E, Marangoni A (1998) Lipid modifica-
tional purposes. tion strategies in the production of nutritionally func-
tional fats and oils. Crit Rev Food Sci Nutr 38:639–674
F
Fat Processing, Membrane The basic operations in fat processing are wet
Operations of melting and dry rendering – or hybrid systems
thereof. Fat tissues are subjected to relatively
Angela C. Macedo1,2 and F. Xavier3 mild processing conditions to minimize their
1
ISMAI – University Institute of Maia, Avenida decay – but high-quality final products hinge
Carlos Oliveira Campos, Avioso S. Pedro, critically on the quality and source of the raw
Portugal materials. They are usually collected from
2
LEPABE - Laboratory of Engineering of slaughterhouses from animals slaughtered on
Processes, Environment, Biotechnology and the same day and undergo strict food safety
Energy, University of Porto, Porto, Portugal steps according to HACCP
3
Department of Chemical Engineering, methodology – including monitoring of environ-
University of Porto, Porto, Portugal mental contaminants, growth hormones, and vet-
erinary drugs. Membrane processing is possible,
but only on clean melted fat – and chiefly to
Fat processing is an active business, designed to deliver support for enzymes aimed at controlled
create added value from slaughter by-products chemical modifications of such fat, e.g.,
downstream the animal chain. It encompasses interesterification.
activities dealing with production of animal fats Fat interesterification can be carried out via
(and proteins) suitable for human consumption in chemical or enzymatic processes; the former
agreement with directive 77/99/EEC (EU 1997), require metal alkalis as catalysts, but produce
as well as processing of category 3 (formerly random interchange of acyl groups, lead to con-
labeled low risk) materials from animals tamination of the final product with residual cat-
approved for human consumption in agreement alyst, and allow formation of soaps – all of which
with regulation ABPR 1774/2002/EC (EU 2002). are viewed as drawbacks relative to their enzy-
Fat processing has historically been associated matic counterparts (Erickson 1995). Lipase-
with manufacture of high-grade animal fats for mediated interesterification with lipases is char-
specific markets, e.g., bakery industry, calf milk acterized by great versatility, reasonable sub-
replacers, and pet food – as well as commodities strate selectivity (including regio-and
for formulation in the oleo-chemical industry enantioselectivity), possibility of operation at
(e.g., manufacture of soaps) and cosmetics; it room temperature and pressure, and the absence
uses bovine tallow, porcine lard, and poultry fat of side reactions. To fully exploit the technical
as major feedstocks. advantages of such enzymes, economic feasibil-
ity recommends the use in immobilized form – to
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_224-3
2 Fat Processing, Membrane Operations of
extend their useful life, avoid product contami- the carrier is the basis of (effective) covalent
nation and consequent unstability, and circum- attachment. This is clearly the most efficient
vent the need for emulsification (James mode of immobilization – despite its being
et al. 2009). Lipase immobilization also facili- much more detrimental for enzyme activity, com-
tates product separation, enhances thermostabil- plex in terms of implementation, and heavily
ity, alleviates rate dependence on pH, and is more dependent on the properties of the carrier (Cao
flexible in terms of reactor configuration. 2005).
Unlike hydrolases at large that operate in plain Finally, entrapment involves capture of
aqueous phases, lipases are activated only in the enzyme within a polymeric matrix during the
presence of water/lipid interfaces – provided by polymerization process – whereas (the related)
the contacting surface between the immiscible microencapsulation entails confinement by a
aqueous and fat phases, which can be made to membrane-like physical barrier around the
coincide with a porous membrane. Techniques enzyme preparation; entrapped enzymes may be
that met with industrial success for immobiliza- further microencapsulated. Both processes
tion of lipases include adsorption, covalent bind- require simple equipment and relatively inexpen-
ing, and entrapment/microencapsulation sive reagents – and yield a better stability and an
(Knezevic et al. 2004). Note that the economic activity similar to adsorbed enzymes (Cao 2005).
feasibility is directly related to the volumetric
productivity on the long run, which depends in
turn not only on the operational stability of the References
enzyme but also on its actual activity – which is
normally lower than that of free enzyme, in addi- Cao L (2005) Carrier-bound immobilized enzymes. Prin-
ciples, application and design. Wiley-VCH, Weinheim
tion to mass transfer constraints (Vulfson 1994).
Erickson DR (1995) Practical handbook of soybean
Physical adsorption is the simplest method for processing and utilization. American Oil Chemists
lipase immobilization; binding occurs via hydro- Society, Champaign
gen bonds, salt linkages, and van der Waals EU (1997) Council Directive 77/99/EEC of 21 December
1976 on health problems affecting intra-community
forces. The process is carried out at mild condi-
trade in meat products. Off J Eur Commun L26
tions, without (or with a marginal) support acti- EU (2002) Regulation (EC) No. 1774/2002 of the Euro-
vation and in the absence of extraneous reagents; pean Parliament and of the Council laying down health
it is thus prone to preserving enzyme activity and rules concerning animal by-products not intended for
human consumption. Off J Eur Commun L273:1–95
specificity. The chemical nature of the carrier
James J, Simpson BK, Marshall MR (2009) Application of
(including the ratio of hydrophilic to hydrophobic enzymes in food processing. Crit Rev Food Sci Nutr
groups), the particle size and porosity, and the 36:437–463
surface area available determine the amount of Knezevic ZD, Siler-Marinkovic SS, Mojovic LV
(2004) Immobilized lipases as practical catalysts.
enzyme bound, as well as the enzyme behavior
APTEFF 35:1–280
following immobilization (Cao 2005). Vulfson EN (1994) Industrial applications of lipases. In:
Chemical reaction between activated amino Woolley P, Peterson SB (eds) Lipases: their structure,
acid residues far from the catalytic and binding biochemistry and application. Cambridge University
Press, Cambridge, UK, pp 271–288
site of the enzyme and active functionalities on
F
Fixed Bed Catalytic Reactor Often, a sweep gas can be used in the perme-
ation side of the membrane in order to keep the
Fausto Gallucci permeation hydrogen partial pressure as low as
Faculty of Chemical Engineering and Chemistry, possible for minimizing the membrane area
Eindhoven University of Technology, required for the hydrogen separation. This prac-
Eindhoven, The Netherlands tice is, for example, very useful if hydrogen for
ammonia plant is being produced, in which case
an amount of nitrogen can be used for sweeping
The fixed bed (or packed bed) membrane reactor the permeation side producing a synthesis stream
configuration is the first and most studied config- (N2/H2 = 1/3) ready for the final reaction step. If
uration for membrane reactors. This is because a sweep gas is used in the permeation side, then a
the first studies on membrane reactors focused on packed bed membrane reactor can be used in both
the effect of the gas permeation through mem- cocurrent or countercurrent modes.
branes on the reaction system (which is often a An interesting feature of packed bed mem-
conventional packed bed reactor). brane reactors is the possibility to operate them
In a packed bed membrane reactor, the cata- in a reverse flow mode, integrating the reaction
lyst is confined in fixed bed configuration, and it and separation with the recuperative heat
is in contact with a permselective membrane. The exchange inside the reactor. This operational
most used packed bed configuration is the tubular mode is quite interesting for partial oxidation of
one where the catalyst may be packed either in methane (POM) (Smit et al. 2005). In normal
the membrane tube or in the shell side, while the POM systems air and CH4 feed streams have to
permeation stream is collected in the other side of be preheated to the reaction temperature, while
the membrane (in the case of hydrogen-selective being POM reaction only slightly exothermic, the
membranes) or one reactant is feed on the other external heat transfer between feed and exhaust is
side of the membrane (in the case of oxygen- very expensive. Therefore, recuperative heat
selective membrane). exchange is preferably carried out inside the
For multitubular membrane reactor configura- reactor.
tions, the catalyst in tube configuration can be Although the tube in tube configuration is
preferred especially for construction reason and quite useful to work in lab scale and for proof of
for the extent of bed-to-wall mass and heat trans- principle of membrane reactors, for industrial
fer limitations which can be very detrimental in scale some other configurations need to be used
the catalyst in shell configuration. in order to increase the membrane area per vol-
ume of vessel used. In fact, the amount of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_230-2
2 Fixed Bed Catalytic Reactor
hydrogen produced is directly related to the important drawback has driven the research
amount of membrane area installed in the reactor. toward new reactor concepts such as micro-
Starting for the tube in tube configuration, a membrane reactors or fluidized bed membrane
straightforward way to increase the membrane reactors.
area in packed bed is the tube in shell configura-
tion (Buxbaum 2002; Tosti et al. 2008).
Although the packed bed configuration is very
References
advantageous and easy to operate, the production
of thin membranes brought under the spotlight Buxbaum RE (2002) Patent US20026461408
one of the disadvantages of fixed bed membrane Gallucci F, Van Sint Annaland M, Kuipers JAM
reactors: the influence of bed-to-wall mass trans- (2010) Theoretical comparison of packed bed and flu-
fer limitations on the membrane area required. idized bed membrane reactors for methane reforming.
Int J Hydrog Energy 35:7142–7150
Briefly, as long as the hydrogen flux through the Peters TA, Stange M, Klette H, Bredesen R (2008) High
membrane is a limiting step, the effect of external pressure performance of thin Pd-23%Ag/stainless steel
mass transfer limitations such as the limitations composite membranes in water gas shift gas mixtures;
to hydrogen transport between the bulk of the influence of dilution, mass transfer and surface effects
on the hydrogen flux. J Membr Sci 316(1–2):119–127
catalytic bed (where hydrogen is produced) and Smit J, Bekink GJ, Van Sint Annaland M, Kuipers JAM
the membrane wall (where hydrogen is recov- (2005) A reverse flow catalytic membrane reactor for
ered) can be neglected. However, by increasing the production of syngas: an experimental study. Int
the membrane flux, the external mass transfer J Chem React Eng 3
Tosti S, Basile A, Bettinali L, Borgognoni F, Gallucci F,
limitations became limiting and determine the Rizzello C (2008) Design and process study of Pd
extent of membrane area. This has been demon- membrane reactors. Int J Hydrog Energy
strated both experimentally (Peters et al. 2008) 33(19):5098–5105
and numerically (Gallucci et al. 2010). This
F
Cussler EL, Aris R, Bhown A (1989) On the limits of Koros WJ, Mahajan R (2000) Pushing the limits on possi-
facilitated diffusion. J Membr Sci 43:149–164 bilities for large scale gas separation: which strategies?
Kim TJ et al. (2013) Separation performance of PVAm J Membr Sci 175:181–196
composite membrane for CO2 capture at different pH Mulder M (2003) Basic principle of membrane technology.
levels, J. of Mem. Sci 428:218–224 Kluwer, Dordrecht
F
Fluidized Bed Membrane Reactors According to Deshmukh et al. (2007) the main
advantages of the MAFBR can be listed as
Fausto Gallucci follows:
Faculty of Chemical Engineering and Chemistry,
Eindhoven University of Technology, • Negligible pressure drop, which allows using
Eindhoven, The Netherlands small particle sizes resulting in limited inter-
nal mass and heat transfer limitations (higher
effectiveness factors)
A fluidized bed membrane reactor, also indicated • (Virtual) Isothermal conditions
as membrane-assisted fluidized bed (MAFBR), is • Flexibility in membrane and heat transfer sur-
an integrated reactor where membranes (in form face area and arrangement of the membrane
of tubes, hollow fibers, or planar modules) are bundles
immersed in a fluidized bed of catalyst particles. • Improved fluidization behavior as a result of:
Typical example of MAFBR for hydrogen pro- • Compartmentalization, i.e., reduced axial
duction is reported in (Gallucci et al. 2010a) and gas back-mixing.
consists in a bundle of hydrogen-selective mem-
branes immersed in a catalytic bed operated in Reduced average bubble size due to enhanced
bubbling regime. The use of fluidized bed mem- bubble breakage, resulting in improved bubble to
brane reactors makes possible the reduction of emulsion mass transfer.
bed-to-wall mass transfer limitations, but also MAFBR for hydrogen production also cir-
allows operating the reactor at a virtually isother- cumvent the bed-to-wall mass transfer limitations
mal condition (due to the movement of catalyst). affecting packed bed membrane reactors. It has
This possibility can be used for operating the been demonstrated that higher membrane fluxes
autothermal reforming of hydrocarbons inside (possible with nowadays membranes) will cause
the membrane reactor. In fact, as indicated by a significant increase of the concentration polar-
Tiemersma et al. (2006), the autothermal ization in packed bed membrane reactors, even in
reforming of methane in a packed bed membrane membrane tubes with a diameter as small as 1 cm.
reactor is quite difficult due to the hot spot at the By using the MAFBR, the membrane area
reactor inlet which can melt down the membrane. required for a fixed hydrogen flux can be
This problem is completely circumvented in flu- decreased by 50 % if compared with packed bed
idized bed membrane reactors. In this case both reactors (Gallucci et al. 2010a).
autothermal reforming and hydrogen recovery
can be performed in a single reactor.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_232-2
2 Fluidized Bed Membrane Reactors
Even though Rahimpour and coworkers often Gallucci F, Van Sint Annaland M, Kuipers JAM (2010a)
used fluidized bed membrane reactor for distrib- Theoretical comparison of packed bed and fluidized
bed membrane reactors for methane reforming. Int
utive hydrogen feeding in methanol reactors (see J Hydrog Energy 35:7142–7150
Rahimpour and Lotfinejad 2008), most of the Gallucci F, Van Sint Annaland M, Kuipers JAM (2010b)
literature has focused on pure hydrogen produc- Pure hydrogen production via autothermal reforming
tion through Pd-based membranes (see among of ethanol in a fluidized bed membrane reactor. Int
J Hydrog Energy 35:1659–1668
others Adris et al. 1991; Prasad and Elnashaie Grace JR, Li X, Lim CJ (2001) Equilibrium modelling of
2002) and on autothermal reforming reactions catalytic steam reforming of methane in membrane
(see a.o. Grace et al. 2001; Gallucci et al. 2010b). reactors with oxygen addition. Catal Today
64:141–149
Prasad P, Elnashaie SSEH (2002) Novel circulating
fluidized-bed membrane reformer for the efficient pro-
duction of ultraclean fuels from hydrocarbons. Ind Eng
References
Chem Res 41:6518–6527
Rahimpour MR, Lotfinejad M (2008) Co-current and
Adris AM, Elnashaie SSEH, Hughes R (1991) A fluidized countercurrent configurations for a membrane dual
bed reactor for steam reforming of methane. Can type methanol reactor. Chem Eng Technol
J Chem Eng 69:1061 31(1):38–57
Deshmukh SARK, Heinrich S, Mörl L, van Sint Tiemersma TP, Patil CS, Sint Annaland MV, Kuipers
Annaland M, Kuipers JAM (2007) Membrane assisted JAM (2006) Modelling of packed bed membrane reac-
fluidized bed reactors: potentials and hurdles. Chem tors for autothermal production of ultrapure hydrogen.
Eng Sci 62:416–436 Chem Eng Sci 61(5):1602–1616
F
viscosity, fouling, and concentration polarization relatively low hydraulic pressure and easy scale-
(Accomazzo et al. 1988). up (Sant’Anna et al. 2012).
Ultrafiltration resorts to membranes with pore Membrane contactors represent another
sizes in the range of 0.1–0.001 mm; it is typically approach to membrane operations in food
intended for removal of high molecular weight processing – where separation does not rely spe-
substances, colloidal materials, and polymeric cifically on the membrane acting as selective
molecules of organic or inorganic nature. Ultra- barrier, but is instead based on phase equilibria.
filtration is a cross-flow separation process – i.e., Hence, mass transfer between phases is promoted
the liquid feed flows tangentially along the mem- without dispersing one phase into the other, and
brane surface with a pressure drop across it, caus- such disadvantages as flooding at high flow rates,
ing part of that stream to percolate the membrane unloading at low flow rates, requirement for
(thus producing a permeate). The type and emulsified state and density differences, and
amount of species left in the remaining stream high interfacial area are dramatically alleviated.
(retentate) depend on the characteristics of the In principle, all traditional stripping, scrubbing,
membrane and the operating conditions, as well absorption, evaporation, distillation, crystalliza-
as the composition of the original feed. Optimum tion, emulsification and liquid-liquid extraction,
design and operation should take into account the as well as enzymatic catalysis can be carried out
flow velocity, the pressure drop, the power con- following this configuration. This type of
sumption, the rate of membrane fouling, and the contactor technology has found applications in
module cost. Since only high molecular weight purification of water, wine fermentation, protein
species are removed, the differential in osmotic extraction, and beverage carbonation (Stanojevíc
pressure across an ultrafiltration membrane is et al. 2003).
usually negligible (Accomazzo et al. 1988).
Nanofiltration is a ▶ cross-flow filtration tech-
nology, usually listed between ultrafiltration and References
reverse osmosis; the nominal pore size of the
membrane is typically ca. 1 nm, but the ▶ molec- Accomazzo M, Ganzi G, Kaiser R (1988) Deionized (di)
water filtration technology. In: Tolliver D -
ular weight cutoff – which is typically less than
(ed) Handbook of contamination control in
1,000 Da, rather than the nominal pore size – is to microelectronic. Noyes Publications, Park Ridge,
be used for a more meaningful characterization. pp 210–254
Transmembrane pressures can go up to 3 MPa, Drioli E, Stankiewicz A, Mecdonio F (2011) Membrane
engineering in process intensification – an overview.
which require powerful pumping equipment; fur-
J Membr Sci 380:1–8
thermore, nanofilter membranes are quite suscep- Marsh R, Angold R (2004) Sources of contamination in
tible to scaling and fouling, so such modifiers as the food chain. In: Edwards M (ed) Detecting foreign
antiscalants are often required. bodies in food. CRC Press, Boca Raton, pp 3–11
Petrotos K, Tsiadi A, Poirazis A, Papadopoulus D,
Finally, reverse osmosis goes one step further
Petropakis H, Gkoutsidis P (2010) A description of a
in filtration and allows separation of small flat geometry direct osmotic concentrator to concen-
dissolved molecules in the Angstrom range; this trate tomato juice at ambient temperature and low
includes salts, sugars, and organic acids. The only pressure. J Food Eng 97:235–242
Sant’Anna V, Marczacl L, Tessaro I (2012) Membrane
driving force for this process is the osmotic pres-
concentration of liquids foods by forward osmosis:
sure difference between the solutions lying on the process and quality view. J Food Eng 11:483–489
two sides of the permeable membrane. The cross- Stanojevíc M, Lazarevíc B, Radíc D (2003) Review of
flow configuration allows the membranes to self- membrane contactor designs and applications of dif-
ferent modules in industry. FME Trans 31:91–98
clean continually; further advantages encompass
F
Formulation by Membrane Emulsification, Fig. 2 Different ME systems used to control shear stress on membrane
surface (Vladisavljević and Williams 2005)
Formulation by Membrane Emulsification 3
association with negatively charged membrane Kukizaki M (2009) Shirasu porous glass (SPG) membrane
(such as SPG membrane and oxidized silicon emulsification in the absence of shear flow at the
membrane surface: influence of surfactant type and
microsieves) (Nakashima et al. 1993). The trans- concentration, viscosities of dispersed and continuous
membrane pressure should not exceed ten times phases, and transmembrane pressure. J Membr Sci
the capillary pressure and the shear stress on the 327:234–243
membrane surface is usually in the range from Nakashima T, Shimizu M, Kukizaki M (1991) Membrane
emulsification by microporous glass. Key Eng Mater
2 to 10 Pa (Vladisavljević et al. 2004). The drop- 61–62:513–516
let size is typically two to ten times higher than Nakashima T, Shimizu M, Kukizaki M (1993) Effect of
the pore size and decreases with increasing the surfactant on production of monodispersed O/W emul-
shear stress on the membrane surface. sion in membrane emulsification. Kag Kog Ronbunshu
19:991–997
Vladisavljević GT, Williams RA (2005) Recent develop-
ments in manufacturing emulsions and particulate
References products using membranes. Adv Colloid Interf Sci
113:1–20
Holdich RG, Dragosavac MM, Vladisavljević GT, Vladisavljević GT, Williams RA (2006) Manufacture of
Kosvintsev SR (2010) Membrane emulsification with large uniform droplets using rotating membrane emul-
oscillating and stationary membranes. Ind Eng Chem sification. J Colloid Interface Sci 299:396–402
Res 49:3810–3817 Vladisavljević GT, Lambrich U, Nakajima M, Schubert
Holdich RG, Dragosavac M, Vladisavljević GT, H (2004) Production of O/W emulsions using SPG
Piacentini, E (2013) Continuous membrane emulsifi- membranes, ceramic a-Al2O3 membranes,
cation with pulsed (oscillatory) flow. Ind Eng Chem microfluidizer and a microchannel plate: a compara-
Res 52:507–515 tive study. Colloid Surf A 232:199–207
F
0
2009 2010 2011
2012
2013
2014
Year
• Requires low/no hydraulic pressure since it is • Membrane fouling in FO is relatively low and
an osmotically driven process. more reversible and can be minimized by opti-
• Low energy consumption, thereby lowing mizing the hydrodynamics.
costs, if suitable draw solutes and their regen- • Numerous contaminants can be effectively
eration methods can be economically and rejected by the FO process.
technically developed. • Has the potential to help achieve high water
• Energy can be harvested from the mixing of recovery, which reduces the volume of desali-
freshwater and saline water by pressure- nation brine, a major environmental concern
retarded FO (PRO). for current desalination.
Forward Osmosis (FO) 3
• In the food and pharmaceutical processing, FO the osmotic driving force. In literature, various
can maintain color, taste, aroma, and nutrition names are given to this solution including: draw
of the feed. solution, osmotic agent, osmotic media, driving
• In the medical applications, FO can help in the solution, osmotic engine, sample solution, or
controlled release of drugs with low oral bio- brine (Cath et al. 2006). The main criterion for
availability in a controlled manner by osmotic selecting the type of draw solution (DS) is its
pumps. potential to create higher chemical potential
than the feed solution.
The DS and related osmotic pressures in the
FO Membranes, Membrane FO process are important factors influencing
Configurations, and Modeling overall process performance. Many researchers
Membrane Transport used salt solution as DS (Cartinella et al. 2006;
Cornelissen et al. 2008; Yong et al. 2012), while
Except for a few authors such as McCutcheon in some cases sugars or ammonia–carbon dioxide
et al. (2005) which used a thin-film composite (McCutcheon et al. 2005) solutions were used.
polyamide membrane, most publications are According to Lutchmiah et al. (2014), based on
based on cellulose or cellulose derivate (cellulose publication from 2005 to 2013, 40 % of the cases
acetate) membranes mainly from Hydration Tech- utilized NaCl as DS. This is mainly attributed by
nology Inc. In addition, in most cases reverse its high solubility (Cath et al. 2006), low cost
osmosis (RO) was used to reconcentrate the DS (Achilli et al. 2010), and relatively high osmotic
which gets diluted in the course of FO. potential. The same author indicated that 12 %
Of the different membrane modules, spiral used MgCl2, 8 % sugars, 10 % sulfates, and other
wound modules are one of the most common 7 % used magnetic nanoparticles, real wastewa-
packing configurations in the membrane industry. ter, carbonates, etc. In addition to these, seawater
However, it cannot be used in its current design has frequently been used as a DS (Cath
for FO because a liquid stream cannot be forced et al. 2010). However, its use was mostly affected
to flow on the support side (inside the envelope) by abundant presence of particles and microor-
(Cath et al. 2006). Hence, for a continuous FO ganisms which may foul the subsequent system
operation, flat-sheet membrane and specially used to reconcentrate the DS (in closed-loop sys-
designed spiral wound membrane are used. tems) or cause fouling/biofouling in the FO unit,
Although applied in limited number, tubular hampering performance.
membranes are also very suitable for continuous
FO processing since they are self-supported, can
be fabricated easily, and allow free flow of liquid Concentration Polarization
on both sides of the membrane. and Membrane Fouling
There are a number of papers discussing the
transport phenomena in FO process in particular Unlike pressure-driven membrane process, in FO
related to solution physicochemical properties, con- there are both dilutive and concentrative polari-
centration polarization, and membrane fouling. For zation effects that result in a lower-than-expected
detailed reading, the reader is referred to Tang water flux. Furthermore, the concentration polar-
et al. (2010), McCutcheon and Elimelech (2006), ization could be either external which occurs near
Tan and Ng (2008), and Zhao and Zou (2011). the surface of the active layer and the porous
support layer or internal which occurs inside the
substructure of porous support layer. As a result,
Draw Solutions the process is always accompanied by great
reduction from the bulk osmotic pressure (Dpbulk)
In FO process, a concentrated solution on the to the effective osmotic pressure (Dpeffective) as
permeate side of the membrane is the source of shown in Fig. 3b.
4 Forward Osmosis (FO)
FEED J
a b solute
Jw
ACTIVE LAYER
Δπ
Δπmembrane
Feed
DS
Δπbulk
POROUS SUPPORT
FO
Δπeffective
DRAW SOLUTION
Forward Osmosis (FO), Fig. 3 Water flows in FO sys- osmotic driving force reduction to effective osmotic driv-
tem where (a) water diffuses to the more saline side of the ing force due to concentration polarization phenomena
membrane due to osmotic driving force under approxi-
mately zero hydraulic pressure and (b) the course of bulk
External Concentration Polarization intermittent osmotic back flush has given the
When the process is in FO mode of operation, i.e., possibility to use a single FO membrane over
feed solution facing the active side of the mem- several cycles bringing the total membrane use
brane, there is accumulation of solute that is to 172 h, during the treatment of vegetation
rejected by the membrane. This will result in the wastewater (Gebreyohannes et al. 2015). This is
phenomena of concentrative external concentra- an important savings in lifetime, compared to the
tion polarization (ECP). At the same time, the DS complete performance loss observed in various
in contact with the permeate side of the mem- pressure-driven membrane operations. The FO
brane gets diluted by the permeating water at the fouling is generally more pronounced when the
permeate–membrane interface resulting in dilu- porous support layer is facing feed solution, since
tive external concentration polarization (ECP). this orientation is prone to sever internal pore
Due to these phenomena, the effective osmotic clogging.
driving force near the membrane is significantly
lower than the bulk (apparent) osmotic pressure Internal Concentration Polarization
(Cath et al. 2006). The asymmetric FO membrane consists of a
Interestingly, several studies have shown that dense active layer and a porous support layer,
fouling induced by ECP in FO in most part is which adds a more complex situation of concen-
reversible due to low foulant compaction as a tration polarization in FO. In FO applications,
result of the negligible hydraulic pressure gradi- where the active layer of the membrane faces
ent. Therefore, FO holds a great potential to treat the feed solution and the porous support layer
wastewater (Lutchmiah et al. 2014), including faces the DS, there is also dilutive internal con-
wastewater with high fouling propensity (Cicci centration polarization (ICP) within the porous
et al. 2013; Karaouzas et al. 2011). The main substructure. This phenomenon happens when
strategy utilized to reduce the effect of ECP is water diffuses through the active layer; the DS
increased turbulence or cross flow velocity. within the porous substructure becomes diluted,
Moreover, recovering FO membrane perfor- hence dramatically reduced effective osmotic
mance was possible using simple osmotic back driving force. Unlike the external concentration
flush, after it is fouled. For example, an polarization, playing with the hydrodynamic
Forward Osmosis (FO) 5
Forward Osmosis (FO), Table 1 Examples of industrial plants that employed FO process
Water Pollutant rejection
Stream Plant name/location recovery DS (%)
Landfill leachate (Osmotek Coffin Butte RO: DS NaCl 99
Inc. 2003) Landfill, Corvallis, and water
Oregon 92 %
Direct potable reuse for advanced DOC NASA long – NaCl Direct potable reuse
life-support systems (Beaudry mission life-support
et al. 1999) system
Concentration of digested sludge Truckee Meadows RO NaCl 87–99
liquids (Holloway et al. 2007) Water Reclamation
Facility, Reno,
Nevada
Hydration bags (Hydration Hydration – Edibles, e.g., Free of
Technologies Inc. n.d.) Technology Inc. sugar, beverage microorganism,
powder macromolecules, and
ions
condition will not alleviate the problem of ICP. of the recovered pharmaceutically interesting
Thus, an engineered solution for reduced internal compounds.
concentration polarization is optimization of the Table 1 gives summary of industrial practices
thickness, porosity, and tortuosity of the porous on the use of FO process in various fields. It is
substructure (Cornelissen et al. 2008). It is worth worth noting that in most wastewater treatment
noting that compared to ECP, ICP has a more applications, FO is used as a high-level
prominent effect in significantly reducing the pretreatment step before an ultimate purification
effective driving force across the dense layer step. An exception for this is a hydration bag,
from the bulk osmotic difference. which serves as a final treatment step to produce
potable water from wastewater.
energy for reconcentration, and must be easily wastewaters to stream macroinvertebrates and aquatic
separable from the product freshwater and ecosystems status. Water Res 45:6334–6346
Klaysom C, Cath TY, Depuydt T, Vankelecom IFJ
nonreactive with low or no toxicity. (2013) Forward and pressure retarded osmosis: poten-
tial solutions for global challenges in energy and water
supply. Chem Soc Rev 42:6959–6989
References Lutchmiah K, Verliefde ARD, Roest K, Rietveld LC,
Cornelissen ER (2014) Forward osmosis for applica-
tion in wastewater treatment: a review. Water Res
Achilli A, Cath TY, Childress AE (2010) Selection of 58:179–197
inorganic-based draw solutions for forward osmosis McCutcheon JR, Elimelech M (2006) Influence of con-
applications. J Membr Sci 364:233–241 centrative and dilutive internal concentration polariza-
Beaudry EG, Herron JR, Peterson SW (1999) Direct tion on flux behavior in forward osmosis. J Membr Sci
osmosis concentration of waste water: final report. 284:237–247
Osmotek, Corvallis McCutcheon JR, McGinnis RL, Elimelech M (2005)
Cartinella JL, Cath TY, Flynn MT, Miller GC, Hunter A novel ammonia—carbon dioxide forward (direct)
KW, Childress AE (2006) Removal of natural steroid osmosis desalination process. Desalination 174:1–11
hormones from wastewater using membrane contactor Osmotek Inc. (2003) Landfill leachate treatment http://
processes. Environ Sci Technol 40:7381–7386 www.rimnetics.com/osmotek.htm
Cath TY, Childress AE, Elimelech M (2006) Forward Petrotos KB, Quantick P, Petropakis H (1998) A study of
osmosis: principles, applications, and recent develop- the direct osmotic concentration of tomato juice in
ments. J Membr Sci 281:70–87 tubular membrane – module configuration. I. The
Cath TY, Hancock NT, Lundin CD, Hoppe-Jones C, effect of certain basic process parameters on the pro-
Drewes JE (2010) A multi-barrier osmotic dilution cess performance. J Membr Sci 150:99–110
process for simultaneous desalination and purification Tan CH, Ng HY (2008) Modified models to predict flux
of impaired water. J Membr Sci 362:417–426 behavior in forward osmosis in consideration of exter-
Cicci A, Stoller M, Bravi M (2013) Microalgal biomass nal and internal concentration polarizations. J Membr
production by using ultra- and nanofiltration mem- Sci 324:209–219
brane fractions of olive mill wastewater. Water Res Tang CY, She Q, Lay WCL, Wang R, Fane AG
47:4710–4718 (2010) Coupled effects of internal concentration polar-
Cornelissen ER, Harmsen D, de Korte KF, Ruiken CJ, Qin ization and fouling on flux behavior of forward osmo-
J-J, Oo H, Wessels LP (2008) Membrane fouling and sis membranes during humic acid filtration. J Membr
process performance of forward osmosis membranes Sci 354:123–133
on activated sludge. J Membr Sci 319:158–168 Yong JS, Phillip WA, Elimelech M (2012) Coupled
Gebreyohannes AY, Curcio E, Poerio T, Mazzei R, Di reverse draw solute permeation and water flux in for-
Profio G, Drioli E, Giorno L (2015) Treatment of olive ward osmosis with neutral draw solutes. J Membr Sci
mill wastewater by forward osmosis. Sep Purif 392–393:9–17
Technol 147:292–302 Zhang J, Loong WLC, Chou S, Tang C, Wang R, Fane AG
Holloway RW, Childress AE, Dennett KE, Cath TY (2012) Membrane biofouling and scaling in forward
(2007) Forward osmosis for concentration of anaero- osmosis membrane bioreactor. J Membr Sci
bic digester centrate. Water Res 41:4005–4014 403–404:8–14
Hydration Technologies Inc. (n.d.) Hydration bags- Zhao S, Zou L (2011) Relating solution physicochemical
technology overview: http://www.hydrationtech.com/ properties to internal concentration polarization in for-
merchant.mv?Screen=CTGY&StoreCode=MHTI& ward osmosis. J Membr Sci 379:459–467
CategoryCode=TECH-FO
Karaouzas I, Skoulikidis NT, Giannakou U, Albanis TA
(2011) Spatial and temporal effects of olive mill
F
for testing UF permeate, which is increasingly ultrafiltration (UF) membrane has been devel-
being used in desalination pretreatment; no linear oped. Boerlage et al. tested this MFI-UF as a
relation with colloidal/suspended matter; fouling function of molecular weight cutoff (MWCO,
potential of particles smaller than 0.45 mm is not 1–100 kDa) of the UF membranes and obtained
measured; and it is not based on any filtration values ranging from 2000 to 13,000 s/L2
mechanism. (as compared to MFI0.45 values of 1–5 s/L2).
To overcome these deficiencies, the Modified Higher values were linked to the retention of
Fouling Index using the same 0.45 mm membrane smaller colloids as well as cake filtration of the
filters (MFI0.45) was developed. The MFI0.45 can retained particles, although a correlation with the
achieve the linear relationship between concen- MWCO was not apparent. While other mem-
tration and flux decline, but still cannot accu- brane characteristics may be partly responsible
rately predict flux decline. Boerlage for those varied results, it is also important to note
et al. (2002) confirmed that this is due to the that fouling at such MWCOs is complex and
fact that in RO, fouling is caused by smaller cannot be solely attributed to particulates.
colloids that are not retained by the A 13 kDa membrane was established to be the
microfiltration membranes used in the MF- best membrane for such tests.
I. Seeing the above complexities of fouling mech- Boerlage et al. used a 13 kDa UF membrane
anisms, this is not unexpected. The MFI0.45 test is (estimated pore dimension 9 nm) to measure
similar to the SDI test (Schippers and Verdouw fouling potential and effectiveness of
1980), but the volume is recorded every 20 s for pretreatment and compare the results with the
20 min. It takes into account that initially pore SDI and the MFI0.45. MFI-UF can be operated
blocking occurs, followed by cake/gel filtration, in constant flow or pressure mode. The MFI-UF
and finally cake/gel blocking and/or enhanced values were in fact 400–1400 times higher than
compression occurs. The cake filtration can be the MFI0.45 due to the smaller particles captured.
identified by plotting t/V versus V, where t is the The MFI-UF can also be used to determine the
time and V is the volume. The slope in this region effectiveness of pretreatment with regard to
is the fouling index. The obtained MFI0.45 value reduction of fouling potential. Roorda and van
is corrected for temperature and pressure and der Graaf (2001) used the MFI-UF to determine
shows a linear relation with colloidal/suspended the fouling potential of UF membranes and con-
matter concentration. MFI is derived in Eq. 2, and firmed the dependence on membrane type. As a
it is defined as the slope of an inverse flow rate general evaluation, Reiss and Taylor compared
(1/Q) versus cumulative volume (V) curve: three parameters used to investigate fouling: the
Silt Density Index (SDI), the Modified Fouling
1 Index (MFI), and the linear correlation of the
¼ a þ MFI V (2)
Q water mass transfer coefficient (MTC). Three
different NF pilot systems were used with differ-
Predicting the rate of fouling in RO systems ent pretreatments including activated carbon and
based on the MFI0.45 is possible, assuming that MF. No correlation between the different param-
cake/gel filtration is the dominant mechanism. eters was obtained, indicating that the filtration
However, the predicted rate of fouling turns out laws on which the models are based might not be
to be very low for MFI of 1 s/L2 (equivalent to valid for NF. Hence, these parameters need to be
SDI15 1–3). A pressure increase of 1 bar is used with caution.
predicted to occur in more than 100 years with SDI and MFI seem to be difficult if there is
RO feed water with an MFI = 1 s/L2. more than one type of fouling mechanisms.
Both MFI0.45 and SDI underestimate the foul- Another approach to estimate fouling potential
ing observed in practice. due to various fouling mechanisms is attempted
As the SDI and the MFI0.45 do not include by combining MFI values measured using multi-
smaller colloid sizes, a new index using an ple test membranes. This method, which is
Fouling Index 3
Fractional Free Volume (FFV) Waals volumes of atoms that form this repeat
unit can lead to some inaccuracies. Since this
Yuri Yampolskii approach poorly takes into account the dead vol-
A.V. Topchiev Institute of Petrochemical ume which depends on conformations of the
Synthesis, Russian Academy of Sciences, chain and is different for different gases, quantum
Moscow, Russia chemical corrections are desirable. More reliable
results were reported by Ronova et al. (2003). So
FFV found in this way can be considered as a
Fractional free volume (FFV) is an empirical semiquantitative parameter suitable for compari-
dimensionless parameter that characterizes free son of series of polymers. Park and Paul (1997)
volume in polymers. FFV can be defined as the assumed that FFV can be considered not as a
ratio Vf/Vsp, where Vf (cm3/g) is the free volume universal property of polymers. Gases with dif-
andVsp (cm3/g) is the specific volume of the poly- ferent molecular dimensions can “feel” different
mer, the latter parameter being the reciprocal parts of the size distribution of free volume. So an
density r. The value of Vf can be calculated empirical method for calculation of occupied
using Bondi (1968) formula Vf = Vsp – Voc, volume specific for each gas was proposed. This
where Voc is the occupied volume, and it can be group contribution method allows better predic-
estimated as Voc = 1.3 Vw, where Vw is van der tions of the permeability coefficients based on
Waals volume of the repeat unit of the polymer. modified FFV.
Such an estimate gives the FFV values of most Positron annihilation lifetime spectroscopy
polymers in the range of 10–25 %. However there (PALS) also allows an estimation of fractional
are examples when FFV is as large as 35 % free volume as FFV = Nvf, where N is hole
(polytrimethylsilyl propyne). In spite of its wide number density (concentration of holes) and vf
usefulness, such definition of FFV has many dis- is the mean volume of the spherical hole with the
advantages and is being often criticized. In the radius R in the polymer or vf = 4/3 (pR3). The
case of glassy polymers, the density may depend FFV values found in this manner are usually
on prior history of the sample and, to some extent, smaller than FFV estimated via Bondi by a factor
on the method of determination. The coefficient 3–4. It is explained by the fact that a big fraction
1.3 in calculating Voc is estimated from packing of size distribution of free volume in polymers
density of molecular crystals at 0 K and cannot consists of holes with the radii inaccessible to
adequately describe polymers at room tempera- o-positronium having the size of 1.06 Å. This is
ture. In addition, calculation of Vw of a repeat confirmed by the calculations using molecular
unit as the sum of the increments of van der dynamics method (Hofmann et al. 2002):
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_243-4
2 Fractional Free Volume (FFV)
extrapolation of FFV to the zero radius of probe ultrahigh and lower free volume polymers: compari-
results in FFV values much greater than those son between molecular modeling and positron lifetime
studies. Macromolecules 35:2129–2140
found via PALS. Park JY, Paul DR (1997) Correlation and prediction of gas
permeability of glassy polymer membrane materials
via a modified free volume based group contribution
References method. J Membr Sci 125:23–39
Ronova I, Rozhkov E, Alentiev A, Yampolskii Y (2003)
Occupied and accessible volumes in glassy polymers
Bondi A (1968) Physical properties of molecular crystals, and their relation with gas permeation parameters.
liquids, and gases. Wiley, New York Macromol Theory Simul 12:425–439
Hofmann D, Heuchel M, Yampolskii Y, Khotimskii V,
Shantarovich V (2002) Free volume distribution in
F
a
0.3 kDa FPH
0.40 1 kDa
UF permeate
0.35 UF Retentate
0.30
0.25
AU
0.20
0.15 4 kDa
0.10 7 kDa
0.05
0.00
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00
Minutes
b
1.80 0.3 kDa
UF permeate
1.60 1 kDa
NF permeate
NF Retentate
1.40
1.20
1.00
AU
0.80
0.60
4 kDa
0.40
0.20
0.00
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00
Minutes
Fractionation of Fish Protein Hydrolysates, hydrolysate (FPH) (feed of the UF step) – (b) Comparison
Fig. 1 Molecular weight distribution of peptides obtained of permeate and retentate obtained by NF (NP010,
by enzymatic hydrolysis of tuna dark muscle – (a) Com- Microdyn Nadir) with the UF permeate (feed of the NF
parison of permeate and retentate obtained by UF com- step) (Superdex-peptide HR 10/300 – Eluant: Water/TFA/
bined with diafiltration (8 kDa ceramic membrane, (Inside ACN: 70/0.1/30)
CéRAMTM, Tami Industries)) with the raw fish protein
Fractionation of Milk by Membrane milks. The use of such milks permits a better
Operations process control of continuous cheese-making
processes and leads to a constant quality of prod-
Marie-Pierre Belleville ucts throughout the year. The use of intermediate-
Institut Européen des Membranes (IEM): UMR concentrated retentates (1.7 < VRF <5) and
CNRS 5635, Université de Montpellier II, high-concentrated retentates (VRF 5–7) permits
Montpellier, France the continuous production of numerous cheese
varieties (fresh unripened cheeses, soft and
semihard cheeses) with high yield and very little
Milk is a complex colloidal suspension whey drainage. All these cheese-making pro-
containing many classes of different size compo- cesses are derived from the famous worldwide
nents (salts, soluble proteins, casein micelles, fat process known as MMV process after the inves-
globules, microorganisms, etc. (see Table 1)) tigators Maubois, Mocquot, and Vassal (Gésan-
which can be well separated from others Guiziou 2010).
according to their size or charge, thanks to mem- Microfiltration (MF) is an alternative to cen-
brane techniques (Brans et al. 2004; Pouliot trifugation for the removal of bacteria and spores
2008; Gésan-Guiziou 2010). from skimmed milk in order to extend its shelf
Since the 1980s, ultrafiltration (UF) has been life without applying a time-temperature treat-
widely used in dairy industries in order to con- ment. MF is thus carried out with multichannel
centrate the protein fraction of milk without any ceramic membranes with a pore diameter of
denaturation. This operation is generally carried 1.4 mm at high tangential velocity (6–9 m s 1)
out on spiral wound polymer membranes or to a and low transmembrane pressure (TMP)
lesser extent on tubular ceramic membranes with (50 kPa). In order to limit the fouling phenomena,
molecular weight cutoff (MWCO) 10–50 kDa a uniform TMP is applied all along the mem-
and at a transmembrane pressure of brane, thanks to the circulation of the permeate
200–400 kPa. According to the concentration cocurrent of the retentate (Bactocatch system ®,
level, different types of concentrate can be dis- AlphaLaval; Invesys ® APV) or thanks to the use
tinguished. UF of skimmed milk with low vol- of ceramic membranes with linear hydraulic-
ume reduction factors (VRF up to 1.7 (the ratio resistance gradient (GP Membralox ® membrane
between either the volumes of feed and retentate Pall-Exekia; Isoflux ® membranes Tami-
in discontinuous mode or flow rates of feed and Industries). MF of skimmed milk on a 0.2 mm
retentate in continuous mode)) leads to the pro- ceramic membrane permits the concentration of
tein standardization of both drinking and cheese casein micelles. One hundred percent of the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_246-5
2 Fractionation of Milk by Membrane Operations
Fractionation of Milk by Membrane Operations, (WPI). Finally MF can be also used for the sep-
Table 1 Approximate composition of milk aration of milk fat into small (<3 mm) and large
Size (mm) or (>5 mm) globules. This operation is achieved
Concentration molecular weight with ceramic membranes with nominal pore size
Components (g L 1) (Da)
higher than 2 mm. The permeate which is
Water 870–875
enriched in small globule fraction leads to the
Fat 34–44 0.15–15 mm
production of cheeses with smoother and finer
Lactose 48–50 342 Da
Proteins 32–35
texture.
Caseins 25–28 50–500 mm
(micelles)
Soluble 5–7 14.2–150 kDa
proteins
References
Ashes 8–9
(mineral and Brans G, Schroën CGPH, van der Sman RGM, Boom RM
salts) (2004) Membrane fractionation of milk: state of the art
and challenges. J Membr Sci 243:263–272
Gésan-Guiziou G (2010) Separation technologies in dairy
and egg processing. In: Rizvi SSH (ed) Separation,
extraction and concentration processes in the food,
caseins are recovered in the retentate without any beverage and nutraceutical industries. Woodhead
Food Series, Oxford, pp 341–380
denaturation, while the permeate which is sterile Pouliot Y (2008) Membrane processes in dairy
and free of phage particles presents a composition technology – from a simple idea to worldwide pana-
close to that of whey. It can be used to prepare cea. Int Dairy J 18:735–740
whey protein concentrate (WPC) and isolate
F
Fractionation of Whey by Membrane (gelling, foaming, water binding, etc.), and phys-
Operations iological functionalities.
Whey protein concentrates (WPC) containing
Marie-Pierre Belleville 35–85 % protein are prepared by ultrafiltration
Institut Européen des Membranes (IEM): UMR (UF) with 10–20 kDa molecular weight cutoff
CNRS 5635, Université de Montpellier II, (MWCO) membranes. According to the concen-
Montpellier, France tration level, different types of concentrate can be
distinguished. For 35 % WPC, the volume reduc-
tion factor (VRF) – the ratio between either the
Whey is a coproduct of cheese-making and casein volumes of feed and retentate in discontinuous
manufacture in the dairy industry; it is the liquid mode, or flow rates of feed and retentate in con-
drained from the curd obtained after addition of tinuous mode – is about 4–7, whereas VRF of
rennet (chymosin) or mineral/organic, or the per- 13–50 are required to prepare 50–60 % WPC.
meate obtained during skimmed milk 75–85 % WPC are obtained owing UF (VRF
microfiltration (MF) in view of casein concentra- 30–35) combined with diafiltration in order to
tion. Whey contains many classes of different- remove minerals and lactose. Whey protein iso-
size components (salts, lactose, soluble proteins lates (WPI) containing more than 90 % of pro-
(mainly b-lactoglobulin and a-lactalbumin), teins are generally produced from the
residual casein, microorganisms, etc. (see microfiltration permeate of skimmed milk using
Table 1)), but its composition depends on the ion-exchange chromatography (IEC).
cheese-making process. The addition of enzyme Reverse osmosis (RO) permits the concentra-
or rennet milk leads to sweet whey (pH 6.2–6.4), tion of whey and its derivatives before dehydra-
whereas acid whey (pH 4.6–5) is obtained after tion. Compared to vacuum evaporation, the
acidic coagulation of milk. Considered as waste energy consumption is lower, however, the con-
for years, whey is now widely used as food ingre- centration level is limited to about 25–28 % dry
dients in many goods and infant and dietetic matter (VRF 4) due to the increase of osmotic
foods. Owing to chromatographic, electrodia- pressure and viscosity and in order to avoid salt
lytic, and membrane techniques which permit precipitation and lactose crystallization.
whey fractionation, it is possible to prepare valu- As the high salt content of whey decreases its
able proteins and peptides with high nutritional nutritional value and generates processing diffi-
qualities (high biological value (BV), amino acid culties, demineralization of whey is carried out
profile, etc.), interesting physical properties before drying. Electrodialysis (ED) and/or
ion-exchange chromatography (IEC) are
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_247-3
2 Fractionation of Whey by Membrane Operations
Fractionation of White
Wine Proteins by MWCO Colloids
Membrane Operations,
300 kDa
Fig. 1 Protein
fractionation by High MW macromolecules
ultrafiltration membranes
100 kDa
Intermediate MW macromolecules
30 kDa
Low MW macromolecules
10 kDa
Low MW compounds
their ultralow protein binding capacity. Although De Bruijn J, Martínez-Oyanedel J, Loyola C, Seiter J,
the purity of protein fractions improves during Lobos F, Pérez-Arias R (2011a) Fractionation of
Sauvignon wine macromolecules by ultrafiltration
membrane fractionation, a decrease of protein and diafiltration: impact of protein composition on
stability has been observed due to the retention white wine haze stability. Int J Food Sci Technol
of high macromolecular species (glycoproteins 46:1691–1698
superior of 100 kDa) by the ultrafiltration mem- De Bruijn J, Martínez-Oyanedel J, Loyola C, Lobos F,
Seiter J, Pérez R (2011b) Impact of white wine mac-
brane. This changing composition of the wine romolecules on fractionation performance of ultrafil-
matrix makes membrane fractionation a complex tration membranes. J Int Sci Vigne Vin 45:181–4188
process. Ferreira RB, Piçarra-Pereira MA, Monteiro S, Loureiro
VB, Teixeira AR (2002) The wine proteins. Trends
Food Sci Technol 12:230–239
Le Bourse D, Jégou S, Conreux A, Villaume S, Jeandet
References P (2010) Review of preparative and analytical proce-
dures for the study of proteins in grape juice and wine.
Abdallah Z, Aguié-Béghin V, Abou-Saleh K, Douillard R, Anal Chim Acta 667:33–42
Bliard C (2010) Isolation and analysis of macromolec-
ular fractions responsible for the surface properties in
native champagne wines. Food Res Int 43:982–987
F
Free Diffusion,
Fig. 1 Schematic draw of
free diffusion with two
solutions: a change of
concentration profile in
time given by Eq. 1 from
time t = 0 (left) to t = 1
(right)
Cross-References References
Free Volume Distribution (Heuchel et al. 2004) (see Fig. 1). For polymers
with greater gas permeability such as poly
Shantarovich Yuri Yampolskii (trimethylsilyl propyne) (PTMSP) or amorphous
A.V. Topchiev Institute of Petrochemical Teflon AF, according to MD, it is much wider and
Synthesis, Russian Academy of Sciences, extends up to microcavity radius 10–12 Å
Moscow, Russia (Hofmann et al. 2003) (see Fig. 2). Positron anni-
hilation lifetime spectroscopy (PALS) also indi-
cates widely distributed sizes of free volume in
Size distribution of free volume in glassy mem- highly permeable polymers. However, there are
brane materials is accessible to estimation by two interpretations of wide size distribution.
computer simulations (molecular dynamics, According to Shantarovich et al. (1993) and
MD) and to experimental studies by the probe Consolati et al. (1996), lifetime distribution can
methods. In low permeable and highly selective be represented by bimodal size distribution
conventional glassy polymers like polyimides, (Fig. 3), while Dlubek (2008) proposed to con-
size distribution of free volume elements sider monomodal size distribution with variable
(microcavities), according to MD, is located dispersion. Both approaches are consistent with
within the range of microcavity radius 1–5 Å the results of MD simulation.
and can be represented by the Gauss function
Free Volume
Distribution, Fig. 1 Size
distribution (MD) of free 0.03
volume in 6FDA-3MPD
polyimide accessible for
o-positronium probe
(Adopted from Heuchel 0.02
FFV
et al. (2004))
0.01
0
0 1 2 3 4 5 6 7 8
R, Å
Free Volume
Distribution, Fig. 2 Size 0.04
distribution (MD) of free
volume in PTMSP
accessible for
o-positronium probe 0.03
(Adopted from Hofmann
et al. (2003))
FFV
0.02
0.01
0
0 2 4 6 8 10 12
R, Å
Free Volume Distribution 3
f (R)
0.2
2 3 4 5 6 7 8
R, Å
in the range 1020–1021 cm 3. It is possible also to Dlubek G (2008) Positron annihilation spectroscopy. In:
calculate PALS-based FFV = N(4/3)pR3. Differ- Seidel A (ed) Encyclopedia of polymer science and
technology. Wiley, Hoboken
ent probe methods give the radii of microcavities Van Krevelen DW, te Nijenhuis K (2009) Properties of
in rather good agreement (Yampolskii 2007). polymers. Their correlation with chemical structure,
their numerical estimation and prediction from addi-
tive group contributions. Elsevier, Amsterdam
Yampolskii Y (2007) Methods for investigation of free
References volume in polymers. Russ Chem Rev 76:59–78
applications. Thus, a fundamental understanding Brunauer, Paul Emmett, and Edward Teller,
of adsorption is a prerequisite. who developed a new theoretical model for mul-
Adsorption equilibria using the Freundlich tilayer adsorption that became known as the BET
isotherm can also be used for membrane charac- model (as an acronym for Brunauer-Emmett-
terization. Ge et al. (2006) demonstrated that the Teller). Although more complex than the empir-
variation in membrane thickness and pore size ical Freundlich equation, it has the advantage of a
can be predicted by studying Freundlich iso- strong fundamental basis, which goes beyond the
therms. They found that when the variations simple approximation in the Freundlich model.
were larger, the time of total saturation is
delayed, the loading capacity at the point of
breakthrough decreases, the solute recovery effi- References
ciency and ligand utilization efficiency decrease,
and the thickness of unused membrane increases. Freundlich H (1909) Kapillarchemie: eine Darstellung der
Chemie der Kolloide und verwandter Gebiete.
The Freundlich isotherm is often used because
Akademische Verlagsgesellschaf, Leipzig
of its simplicity and wide applicability. However, Ge D, Shi W, Ren L, Zhang F, Zhang G, Zhang X, Zhang
other isotherms can also be used to describe Q (2006) Variation analysis of affinity-membrane
adsorption on membrane surfaces. The most model based on Freundlich adsorption. J Chromatogr
A 1114:40–44
commonly applied are the Langmuir isotherm
Kimura K, Amy G, Drewes J, Watanabe Y (2003) Adsorp-
and the BET equation. The Langmuir model tion of hydrophobic compounds onto NF/RO mem-
was derived theoretically by Irving Langmuir in branes: an artifact leading to overestimation of
1916 as a mathematical expression for monolayer rejection. J Membr Sci 221:89–101
McCallum EA, Hyung H, Do TA, Huang CH, Kim JH
adsorption onto a solid surface. Although this
(2008) Adsorption, desorption, and steady-state
model has a theoretical basis, its application is removal of 17b-estradiol by nanofiltration membranes.
limited to monolayers; in addition, the Langmuir J Membr Sci 319:38–43
model does not work well for rough surfaces, Van der Bruggen B, Braeken L, Vandecasteele C (2002)
Flux decline in nanofiltration due to adsorption of
which is often the case for membranes. The Lang-
organic compounds. Sep Purif Technol 29(1):23–31
muir model was extended in 1938 by Stephen
F
membranes relies in the barrier effect given by Aricò AS, Baglio V, Di Blasi A, Creti P, Antonucci PL,
the inorganic filler for methanol crossover (Ren Antonucci V (2003) Influence of the acid–base char-
acteristics of inorganic fillers on the high temperature
et al. 1996). performance of composite membranes in direct meth-
anol fuel cells. Solid State Ionics 161:251–265
Ren X, Wilson MS, Gottesfeld S (1996) High performance
direct methanol polymer electrolyte fuel cells.
References J Electrochem Soc 143:L12
Wang J, Wasmus S, Savinell RF (1995) Evaluation of
Aricò AS, Cretı̀ P, Antonucci PL, Antonucci V (1998) Ethanol, 1-Propanol, and 2-Propanol in a Direct Oxi-
Comparison of ethanol and methanol oxidation in a dation Polymer-Electrolyte Fuel Cell. J Electrochem
liquid-feed solid polymer electrolyte fuel cell at high Soc 142:4218
temperature. Electrochem Solid-State Lett 1:66–68 Watanabe M, Uchida H, Seki Y, Emori M, Stonehart
Arico AS, Srinivasan S, Antonucci V (2001) Fuel Cells P (1996) Self-humidifying polymer electrolyte mem-
1:133 branes for fuel cells. J Electrochem Soc 143:3847
G
Gas Permeation Unit (GPU) important parameter when comparing the separa-
tion suitability of membranes for mixed gases.
May-Britt Hägg A practical unit often used is GPU (gas perme-
Department of Chemical Engineering, ation unit) (see below).
Norwegian University of Science and Permeability:
Technology, Trondheim, Norway
1Barrer ¼ 1010 cm3 ðSTPÞcmcm2 s1 cmHg1
¼ 1, 33 1014 m3 ðSTPÞmm2 s1 kPa1
The intrinsic permeation property of a gas ¼ 2:99 1015 kmolmm2 s1 kPa1
through a membrane is characterized by the per-
meability coefficient P of a gas A, PA. Barrer was Permeance:
early introduced as a practical unit for this prop-
erty and made it easy to compare the suitability of 1GPU ¼ 106 cm3 ðSTPÞcm2 s1 cmHg1
materials to be used for membrane gas separa-
¼ 7:6 109 m3 ðSTPÞm2 s1 kPa1
tion. Barrer is also defined below.
Permeance is directly related to the thickness, ¼ 3:35 103 kmolm2 s1 kPa1
l, of the membrane and as such defined as
pressure-normalized steady-state flux, P/l. The (For conversions on membrane key parameters,
permeance will characterize the gas transport please refer to: Table according to Journal of
through the membrane. Permeance is an Membrane Science.)
Gas Separation,
Fig. 1 Schematic
representation of pressure
swing adsorption method
(PSA)
Gas Separation,
Fig. 2 Schematic
representation of cryogenic
distillation method
Gas Separation,
Fig. 4 An example of
Robeson plot, in this case
O2/N2 (Carta et al. 2013).
The black line represents
the 1991 (Robeson 1991)
upper bound, whereas the
red line is the current
(2008) upper bound
(Robeson 2008)
is allowed to diffuse into the second vessel under a confirmed that highly selective membranes gener-
pressure gradient which promotes the mass trans- ally exhibit low permeability and vice versa. The
port through the membrane separating the retentate most important outcome of this study is
(slower gas) from the permeate (faster gas). represented by the so-called Robeson upper
The use of membranes for gas separation bound, an empirical line which is drawn for every
offers several benefits, probably the most valu- gas pair plot that is meant to define how good a
able is the high cost efficiency (both for the material for gas separation is. In Fig. 4, there is a
mechanical simplicity of the system and for typical example (Carta et al. 2013) in which the red
low-energy regeneration). In fact, they do not line represents the 2008 upper bound for the gas
require thermal regeneration, a phase change, or pair O2/N2. Supposedly, if we plot the selectivity
active moving parts in their operation. aA/B versus permeability PA for a new membrane
Probably the greatest limitation of membranes and the data point fall close or go over the upper
for gas separation is derived from their trade-off bound, it is widely accepted that the material has an
relationship between permeability and selectivity excellent compromise between P (rate of separa-
for a required gas component. This means that high tion) and a (goodness of separation).
permeable membranes have low selectivity, requir-
ing several run for a good separation, and highly
selective membranes have low permeability, References
meaning long operational times. This trade-off
was well addressed by Robeson in two well- Carta M, Malpass-Evans R, Croad M, Rogan Y, Jansen
JC, Bernardo P, Bazzarelli F, McKeown NB (2013) An
known articles (Robeson 1991, 2008) in which he efficient polymer molecular sieve for membrane gas
studied the gas separation performance of several separations. Science 339(6117):303–307
membrane-forming materials in terms of perme- Robeson LM (1991) Correlation of separation factor ver-
ability of a particular species (PA) and selectivity sus permeability for polymeric membranes. J Membr
Sci 62(2):165–185
toward one component of a gas pair (aA/B = PA/
Yampolskii Y, Freeman B (eds) (2010) Membrane gas
PB), organizing the data in double logarithmic plots separation. Wiley, Chichester, UK, 370 pp
for a series of commercially selected important gas Robeson LM (2008) The upper bound revisited. J Membr
pairs such as H2/CH4, H2/CO2, and O2/N2. He Sci 320(1+2):390–400
G
Gas Separation by Membrane from nitrogen more than 30 years ago. Today, the
Operations production of nitrogen from air is the largest
application of membrane systems, owing to the
Mariolino Carta1 and Paola Bernardo2 demand for nitrogen to inert fuel tanks, also
1
School of Chemistry, University of Edinburgh, aboard aircrafts, and for blanketing chemical
Edinburgh, UK and liquefied gas shipments. Membrane systems
2
Research Institute on Membrane Technology, are also applied to enrich oxygen for medical
ITM-CNR, Rende (CS), Italy uses, for hydrogen recovery and purification in
refineries, for air and gas dehydration, and for
ratio adjustment of gas mixtures. Natural gas
The separation of mixtures of gases and vapors is processing represents an important emerging
required in manufacturing processes across vari- application field (Baker and Lokhandwala
ous industries. In the last years, membrane sys- 2008). The relatively low volume flow and the
tems are gaining a larger acceptance in industry relatively high inlet carbon dioxide content are
for gas separation and are recognized as a cost- strong drivers for the implementation of the
efficient separation able to compete with consol- membrane technology in the biogas upgrading
idated processes such as pressure swing absorp- that it is at a developing stage (Makaruk
tion and cryogenic distillation (Bernardo et al. 2010). The challenging olefin/paraffin sep-
et al. 2009; Sanders et al. 2013). Membrane pro- aration, not yet commercial, is attracting a lot of
cesses have several advantages over conventional interest from the scientific community (Rungta
separation techniques (e.g., distillation, extrac- et al. 2013).
tion, absorption, and adsorption), including mod- Membrane separation allows recovering and
ularity and compactness, operational flexibility, recycling valuable compounds, such as hydrogen
and no need for energy-intensive phase changes and light hydrocarbons (ethylene, propylene, and
or potentially expensive adsorbents and/or diffi- LPG), present in different off-gas streams (Baker
cult to handle solvents. The features of membrane et al. 1998). Polymeric membranes, cheap and
operations allow implementing the process inten- with an easy processability, are typically used in
sification strategy in different production cycles. the commercially available membrane system for
Their versatility represents a decisive factor to gas separation (Yampolskii 2012). Commercial
impose membrane processes in most gas separa- modules employ composite membranes (Pinnau
tion fields. et al. 1988), mainly in the form of compact hol-
The first membrane units were installed in low fibers. These membranes typically operate
ammonia plants for the separation of hydrogen the separation based on a solution-diffusion
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_262-1
2 Gas Separation by Membrane Operations
transport mechanism: sorption of the permeant mechanism (Huang et al. 2008). However, carrier
into the membrane, permeation by diffusion poisoning and short life span of the polymeric
through the membrane, and desorption at the membranes are typically reported (Rungta
low-pressure side of the membrane. et al. 2013). Ionic liquids were considered as
The experimentally observed upper bound, additives for facilitated transport membranes.
based on various polymeric membranes, was Indeed, their negligible vapor pressure avoids
reported by Robeson in 1991 and then updated solvent losses by evaporation, providing stability
in 2008 (Robeson 1991, 2008), thanks to the to the metallic cation dissolved inside, and acting
efforts to improve the gas separation performance as a medium for facilitated transport with mobile
of ultrahigh free volume and perfluoropolymers. carrier (Fallanza et al. 2013). Ionic liquid gel
Glassy polymers are chosen for their size- membranes based on conventional polymers
selective behavior (e.g., in O2/N2 or H2 separa- (Jansen et al. 2011) or on polymer ionic liquids
tions). However, when applied to mixtures and/or (Bara et al. 2008) were proposed to increase the
at high gas activities, these materials are prone to stability compared to supported liquid
plasticization, which causes swelling of the poly- membranes.
mer matrix and results in a higher permeability The key for new applications of membranes in
coupled with a loss of selectivity. Strategies to challenging and harsh environments (e.g., petro-
overcome plasticization include thermal curing chemistry) is the development of new tough,
and chemical cross-linking, which reduce the high-performance materials. In the field of inor-
polymer free volume (Wind et al. 2002). The ganic membranes, metal organic frameworks
addition of nanofillers to a polymer matrix repre- were recently considered for preparing mem-
sents an interesting solution to overcome the branes to be applied to the olefin/paraffin separa-
trade-off of the polymeric membranes and the tion (Bux et al. 2011) or as additive to a polymer
inherent brittleness issues of inorganic mem- matrix (Bushell et al. 2013).
branes (Goh et al. 2011). High free volume polymers have been inves-
Rubbery polymers, instead, present a tigated as gas separation membranes, combining
solubility-controlled permeation and preferen- their ease of processing and mechanical stability
tially allow the permeation of large gas or with the potential to surpass the polymeric upper
vapor molecules in a gaseous mixture containing bound for different gas pairs (Budd and
also smaller molecules (Grinevich et al. 2011). McKeown 2010). Novel PIMs, characterized by
Their permeability, much higher than in conven- a significant shape persistence, were developed,
tional glassy polymers, increases with the criti- showing interesting performance for the O2/N2
cal volume of the penetrant (Matteucci separation (Carta et al. 2013).
et al. 2006). These materials are applied to the Properly designed hybrid processes, combin-
separation of organic vapors from ing a membrane system with a conventional one
non-condensable gases, treating petrochemical (e.g., PSA or absorption), represent technically
vent and process streams to recover valuable and economically viable solutions, able to reduce
feedstocks (Baker 1999). energy consumption and total costs (Esteves and
An interesting new concept is the use of water- Mota 2007).
swollen thin film composite membranes for bio-
gas purification, taking advantage of the large
difference in solubility in water to become selec- References
tive for CO2 (Kárászová et al. 2012).
Facilitated transport membranes contain car- Baker R (1999) Recent developments in membrane
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gas component. Therefore, the reaction in the
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Bushell AF, Attfield MP, Mason CR, Budd PM, biogas upgrading processes for the production of nat-
Yampolskii YP, Starannikova L, Rebrov A, ural gas substitute. Sep Purif Technol 74:83–92
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Bux H, Chmelik C, Krishna R, Caro J (2011) Ethene/ (1988) Gas permeation through composite mem-
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Esteves IAAC, Mota JPB (2007) Gas separation by a based ethylene/ethane separation: the upper bound and
novel hybrid membrane/pressure swing adsorption beyond. AIChE J 59(9):3475–3489
process. Ind Eng Chem Res 46(17):5723–5733 Sanders D, Smith ZP, Guo R, Robeson LM, McGrath JE,
Fallanza M, Ortiz A, Gorri D, Ortiz I (2013) Paul DR, Freeman BD (2013) Energy-efficient poly-
Polymer–ionic liquid composite membranes for pro- meric gas separation membranes for a sustainable
pane/propylene separation by facilitated transport. future: a review. Polymer 54(4):729–4761
J Membr Sci 444:164–172 Wind JD, Staudt-Bickel C, Paul DR, Koros WJ (2002) The
Goh PS, Ismail AF, Sanip SM, Ng BC, Aziz M (2011) effects of crosslinking chemistry on CO2 plasticization
Recent advances of inorganic fillers in mixed matrix of polyimide gas separation membranes. Ind Eng
membrane for gas separation. Sep Purif Technol Chem Res 41(24):6139–6148
81:243–264 Yampolskii Y (2012) Polymeric gas separation mem-
Grinevich Yu, Starannikova L, Yampolskii Yu, branes. Macromolecules 45(8):3298–3311
Gringolts M, Finkelshtein E (2011) Solubility
G
dci
J i ¼ Di (1)
dx
Gas/Vapor Transport, Fig. 2 Concentration profiles in a sorption experiment (Relative feed concentration = 1)
flat sheet membrane (100 mm) calculated by Eq. 2, for D = Arrows represent the increasing time during the experi-
1012 m2 s-1 (Crank 1975) in the case of: (a) ideal time lag ment. Dashed lines represent the concentration profile in
permeation experiment (Relative feed time equal to permeation time lag (see below)
concentration = 1, permeate concentration = 0); (b) ideal
van’t Hoff relationships, respectively (Van species. In the extreme case of pervaporation (C),
Amerongen 1946; Costello and Koros 1992). the membrane is at one side in contact with a
liquid phase and at the downstream side it is in
D ¼ D0 eED =RT (8) contact with a gas phase. The type of separation
process dictates the possible operation conditions
S ¼ S0 eDHs =RT (9) and the choice of the membrane materials.
where DHs is the enthalpy of sorption of the (A) For simple gas/gas separations, for instance,
penetrant in the polymer, ED activation energy of O2/N2 separation from air for pure nitrogen
diffusion, and D0 and S0 are the preexponential production or for O2 enrichment, in principle
factors. many membrane materials can be safely used
Assuming solution-diffusion model (Eq. 3), (Baker and Low 2014). The choice depends
temperature dependency of permeability is: mainly on the need to achieve a high separa-
tion factor at relatively low flux or if a high
P ¼ P0 eEP =RT (10) flux is needed and the separation factor is less
important.
where P0 is preexponential factor and EP activa- (B) For gas/vapor separations, the transport prop-
tion energy of permeation which is equal to: erties of the different species vary widely.
Often the vapor consists of readily condens-
EP ¼ DH S þ ED (11) able large molecules, which have a high sol-
ubility in combination with a low diffusion
As a temperature-activated process, diffusion usu- coefficient, in contrast to the light gas, with a
ally accelerates with temperature. Dissolution of lower solubility and a high diffusion coeffi-
the gas can be considered as a two-step process of cient. In this case, the species in the mixture
condensation of the gas phase, followed by are likely to influence each other, directly via
mixing with the polymer matrix. For light gases, competitive sorption in the limited free vol-
the solubility therefore increases with increasing ume available and indirectly via plasticiza-
temperature, because the negative enthalpy of tion of the polymer matrix by the
condensation is negligible with respect to the pos- condensable species. The same situation
itive enthalpy of mixing. On the other hand, occurs in gas/gas separations, where one of
enthalpy of sorption of more condensable gases the two gases readily condenses at higher
and vapors is negative due to the high negative pressure, for instance, CO2. Typical examples
enthalpy of condensation and the solubility are volatile organic compounds (VOC)
decreases with increasing temperature. Tempera- removal from air (Leemann et al. 1996), or
ture dependency of diffusivity is usually stronger CO2 removal from natural gas (Adewole
than that of solubility, and therefore the perme- et al. 2013) or biogas, air dehydration,
ability usually increases with increasing tempera- etc. For such separations, it may be conve-
ture (Ghosal and Freeman 1994). nient to use rubbery membranes, which are
less prone to plasticization and which are
solubility selective rather than diffusivity
selective.
Gas/Gas, Gas/Vapor, and Vapor/Vapor (C) Pervaporation is the extreme case of vapor/
Separation vapor separation, with condensed vapors
(=liquid mixture) at the feed side of the mem-
The most important industrial applications of gas brane and gaseous species at the permeate
and vapor separations vary from (A) gas/gas sep- side, either by application of a vacuum or by
arations to (B) gas/vapor separations, where the the use of a sweeping gas (Mulder and Smol-
membrane is in contact with highly condensable ders 1991). Pervaporation is particularly
Gas/Vapor Transport 5
vm h a f
v¼ (19)
ð 1 f aÞ ð 1 f a þ h f aÞ
Transport in Heterogeneous
and Homogeneous Mixtures
lnPb ¼ f1 lnP1 þ f2 lnP2 (23) Gas/Vapor Transport, Fig. 6 O2/N2 1991 and 2008
upper bound curves for the selectivity versus permeability
trade-off relation (Robeson 1991, 2008) with the latest
in which f1 and f2 are the volume fractions of the upper bound suggested by Swaidan et al. (2015). The
two polymers, respectively, and P1 and P2 are oval represents the approximate cloud of experimental data
their permeabilities. It shows a linear trend when
the permeabilities are plotted on a logarithmic the current upper bound (Robeson et al. 2009).
scale and deviates from linearity in the case of This was confirmed by McKeown et al. with a
(partial) immiscibility of the two polymers novel polymer of intrinsic microporosity based on
(Jansen et al. 2013). Troger’s base and ethanoanthracene (Carta
et al. 2013) or benzotriptycene units (Rose
et al. 2015). Alentiev presented a similar approach
Overall Performance for the trade-off in diffusion coefficient and diffu-
sion selectivity (Alentiev and Yampolskii 2013).
Robeson Trade-Off Behavior
Although membrane separations may have many Effect of Physical Aging on the Transport
advantages compared to traditional separation Properties
processes such as distillation or pressure swing The global nonequilibrium state of glassy poly-
adsorption, a limitation is the trade-off behavior meric membranes tends to relax over time. This
between selectivity and permeability. This trend process, where no chemical changes occur, is
was firstly discussed by Robeson in 1991, who called physical aging (Struik 1978) and affects
suggested a linear so-called upper bound for many different properties of a polymer. One of these is
relevant gas pairs (Fig. 6) (Robeson 1991), which the free volume distribution, which, in turn, is
were subsequently updated and extended reflected in the gas transport properties of the
(Robeson et al. 1994; Robeson 2008). In 2015, a membrane. Physical aging therefore has a strong
new upper bound was set for O2/N2, H2/N2, and impact on the performance of amorphous glassy
H2/CH4, based on mostly the development of gas separation membranes (Pfromm 2006), and
polymers of intrinsic microporosity (Swaidan gas diffusion is a very sensitive method to probe
et al. 2015). Freeman discussed the basis of the changes in the free volume of a polymer mem-
upper bound (Freeman 1999) and concluded that a brane (Jansen et al. 2009). Different aging mech-
combination of high free volume and extreme anisms have been proposed. Harms claims that
rigidity of the polymer chains is needed to exceed free volume elements diffuse towards the surface
10 Gas/Vapor Transport
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G
Cliquid
Gas–Liquid Membrane Contactor, Fig. 3 (a) In a nonwetted porous membrane, the membrane transport occurs in
gas-filled pore. (b) In a wetted porous membrane, the membrane transport in liquid-filled pore is much slower
Noting one can define the gas transfer effi- of drawbacks due to phase dispersion such as
ciency Z = (CGin–CGout)/CGin, thus one can solvent loss, foaming, unknown specified area,
write: and column flooding. It is worth also to underline
that as polymer is the core of membrane
CGout contactors, one can get a strong reduction in
¼ 1 Z ¼ ek:a:L=ug (3)
CGin weight of the equipment compared to conven-
tional ones. At last one can note as well that a
It is worth noting that modeling the mass transfer membrane contactor can be installed horizontally
properties of a membrane contactor is even easier or vertically without problems and that its effi-
than with conventional contactors because the ciency is not dependent of roll and pitch marine.
gas/liquid contact area is well known and remains Note that liquid–liquid extraction can also be
constant whatever the gas or liquid flow rates. achieved using membrane contactors, hence
As shown in Fig. 3, the overall mass transfer avoiding any hazard of emulsion formation.
resistance is due to the successive resistances of All these advantages are linked to the mixing
the gas phase, of the membrane, and of the liquid nondispersive feature of a membrane contactor.
phase. Clearly the analogy can be made with On the other side, drawbacks can come from
electrical resistances, and the reciprocal of the the facts that the pores of a membrane do not have
overall mass transfer coefficient (kov) can be the same size, that pore fouling can occur and
written as the sum of the individual mass transfer block the transfer, and that the hydrophobic prop-
coefficients: erties of the surface can be altered inducing a
dramatic decrease of the breakthrough pressure.
1=kov ¼ 1=kgas þ 1=kmembrane þ H=kliquid (4)
10,000 m2/m3 that is up to 20-fold the interfacial As example of gas dissolution, one can cite
area of a structured packed column (Gabelman nitrogenation in the beverage industry or blood
and Hwang 1999; http://docnum.univ-lorraine.fr/ oxygenation. It is worth to note that blood oxy-
public/INPL/2011_NGUYEN_P_T.pdf6). Thus genation has been one of the very first examples
the factor k.a., which is one of the key parameters of using membrane contactors in 1975 (Esato and
predicting the mass transfer efficiency (Eq. 3), Eiseman 1975); currently the total annual market
indicates clearly that for a constant value of k, a is above €500 million.
strong intensification of the transfer can be Some examples of use of membrane
reached with membrane contactors. contactors are listed here:
This high value of area will be obtained with
fibers having very low inner diameter, typically – Liquid degassing: O2, CO2, and N2 removal
in the 50–100 mm range. Hence, a limit of the from liquids, used for carbonation (food and
transfer with membrane contactor can now be beverage industry), nitrogenation
foreseen: the increase of the specific area shall (microelectronics), deoxygenation, etc.
correspond to an increase of the pressure drop in – Bubble-free gas/liquid mass transfer primarily
the fibers of smaller diameter. This drawback will for ozonation of semiconductor cleaning
be amplified by using fluid of high viscosity. water
Thus the potential of intensification is also – Dehydration
strongly linked to the hydrodynamic conditions – Blood oxygenator (health sector)
prevailing in the contactor. This shall depend
merely on the nature of the fluid circulating in
the lumen of the fibers. Cross-References
▶ Gas Stripping
Applications ▶ Henry Law
Glass Transition Temperature (Tg), Table 1 Glass transition temperature of polymers -[-CH2CH(R)-]n- with the same
backbone and different substituents R (Brandrup et al. 1999)
Polymer R Tg
Polyethylene H 155
Polypropylene CH3 258–270
Poly(vinyl fluoride) F 314
Poly(vinyl chloride) Cl 354
Poly(vinyl alcohol) OH 358
Polystyrene C6H5 373
Poly(vinyl acetate) CH3COO 305
(styrene-co-4-Vinylpyridine). Thermochim Acta vapor separation, John Wiley & Sons, Ltd, Chichester,
483(1–2):49–54 UK. doi: 10.1002/047002903X.ch1
Matteucci S, Yampolskii Y, Freeman BD, Pinnau I (2006), McKeown NB, Budd PM (2010) Exploitation of intrinsic
Transport of gases and vapors in glassy and rubbery microporosity in polymer-based materials. Macromol-
polymers, In: Yampolskii Y, Pinnau I, Freeman BD ecules 43(12):5163–5176
(eds.) Materials science of membranes for gas and
G
Gold Recovery by Supported Liquid Gold, over its use in jewelry, also has a wide
Membranes use in various industries, thanks to its physical
and chemical properties. Thus, the recovery of
Argurio Pietro this metal from the different wastewater gener-
Department of Environmental and Chemical ated by these industries is also of growing interest
Engineering, University of Calabria, Arcavacata (Alguacil 2004).
di Rende (CS), Italy Gold can be recovered from different aqueous
solutions by various physicochemical separation
techniques as precipitation, ion exchange, carbon
Gold is the chemical element which symbol is Au adsorption, cementation, solvent extraction,
(from Latin aurum) and the atomic number is 79. etc. In the case of convectional solvent extrac-
The oxidation states in its compounds range from tion, metal ion-containing solution is placed in
1 to +5, and Au(III) is the most common. Typ- contact with a large amount of an appropriate
ical Au(I) complex is Au(CN)2 (in cyanide organic phase (Kargari et al. 2004). This extrac-
media) which is the soluble form of gold encoun- tion step is followed by a stripping one. The main
tered in mining, while in chloride media Au(III) drawback of solvent extraction is the large
complexes (Au2Cl6) are the typical ones. amount of solvent required when dilute solutions
Gold production by means of its extraction were processed, making this process not very
from mining can represent an important contri- cheap and safe, since the used solvents are often
bution to environmental pollution. Metal ores, chlorinated and sometimes carcinogenic.
which generally contain less than 1 ppm of Liquid membrane (LM)-based processes have
gold, are ground and mixed with sodium or potas- become an attractive alternative to conventional
sium cyanide for gold chemical extraction. Pre- techniques for selective separation and concen-
cious metal and heavy metal impurities such as tration of both organic and inorganic compounds
cadmium, lead, zinc, copper, nickel, and arsenic from dilute aqueous solutions since they combine
are usually present in an anionic form (i.e., cya- extraction and stripping into a single process,
nide salts) after their extraction from metal ores. thus reducing the solvent inventory requirement
These salts are toxic to the liver and kidneys and then cost significantly (Molinari and Argurio
because of both cyanide and metal content. 2011). They also allow the use of expensive and
Thus, it would be desirable to be able to selec- highly selective extractants, which otherwise
tively remove these complexes for the recovery would be uneconomic in solvent extractions.
of precious metals. LM systems include nonsupported liquid
membranes (bulk liquid membrane (BLM) and
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_272-6
2 Gold Recovery by Supported Liquid Membranes
emulsion liquid membrane (ELM)) and where the subscripts aq and org denote the spe-
supported liquid membrane (SLM). SLMs con- cies contained in the aqueous and organic phase,
sist of an organic LM phase impregnated in a thin respectively, and L represents the extractant.
hydrophobic microfiltration membrane. This LM In the case of gold(III), the extraction is
phase generally contains an extractant (carrier) governed by the following pH-dependent equi-
which binds very selectively the target compo- librium reaction:
nent in the donor phase (feed), transporting it into
the acceptor phase (strip), resulting in the Hþ aq þ AuCl4 þ nLorg , Hþ AuCl4 nLorg
so-called facilitated transport (Molinari
et al. 2009a, b). where n = 1, 2.
Referring to gold transport, SLM systems
have been tested in the separation of this precious
metal mainly from cyanide (Au(I)) or chloride References
(Au(III)) media. Highly acidic conditions are
required for the extraction and transport of Au Alguacil FJ (2004) Carrier-mediated gold transport in the
system Cyanex 921–HCl–Au(III). Hydrometallurgy
(III) because of its easily reducible nature.
71:363–369
Various carriers for Au transport across a SLM Alguacil FJ, Alonso M, Sastre AM (2005) Facilitated
were reported in literature. Among them, the supported liquid membrane transport of gold (I) and
commercially available extractant Cyanex ® gold (III) using Cyanex ® 921. J Membr Sci
252:237–244
921 has been applied in the carrier-facilitated
Kargari A, Kaghazchi T, Soleimani M (2004) Role of
transport of both gold(I) and gold(III) recovery emulsifier in the extraction of gold (III) ions from
from cyanide and chloride media, respectively aqueous solutions using the emulsion liquid membrane
(Alguacil et al. 2005). Gold(I) is transported technique. Desalination 162:237–247
Molinari R, Argurio P (2011) Recent progress in
from alkaline pH values (6–11). Gold
supported liquid membrane technology: stabilization
(I) extraction takes place in that pH range by the and feasible applications. Membr Water Treat
following equilibrium reaction: 2(4):207–223
Molinari R, Argurio P, Poerio T (2009a) Studies of various
Mþ þ AuðCNÞ2aq þ 3 Lorg
solid membrane supports to prepare stable sandwich
liquid membranes and testing copper(II) removal from
, Mþ AuðCNÞ2 3Lorg aqueous media. Sep Purif Technol 70:166–172
Molinari R, Argurio P, Poerio T (2009b) Flux enhance-
ment of stagnant sandwich compared to supported
liquid membrane systems in the removal of Gemfibro-
zil from waters. J Membr Sci 340:26–34
G
References
Feed Liquid membrane Strip and HCrO4 and H+ ions are released. The
so-regenerated carrier molecule diffuses back to
HCrO4− H2CrO4 TOPO HCrO4− the feed and the transport cycle begins again
(Fig. 1). This transport mechanism is the
so-called facilitated coupled co-transport, typical
when a basic carrier like amines or phosphates is
used to transport negatively charged species
H+ TOPO H+ (in this case HCrO4) and usually H+ as counter-
ion across the membrane in the same direction
HCrO4− HCrO4− (Fig. 1).
H+ H+ Cr(VI) complexes can be efficiently removed
from acidic chloride aqueous solutions by facili-
Hexavalent Chromium Separation by Supported
Liquid Membranes, Fig. 1 tated transport with TOA into a basic (NaOH
0.1 M) acceptor phase (Kozlowski and
Walkowiak 2002). In agreement with the trans-
hydrophobic microfiltration membrane, kept port mechanism that is similar to that one previ-
there by capillary forces. It combines the typical ously reported for TOPO, the permeability
advantages of liquid membrane with the mechan- coefficient and then initial flux values decrease
ical resistance of solid membranes. The transport linearly by increasing the feed pH. Cr
across a SLM is mediated by a mobile extractant (VI) concentration can be successfully reduced
(carrier) which binds very selectively the target in the feed phase from 1.0 to 0.0028 mg/L, thus
component in the donor phase (feed), respecting the World Health Organization’s
transporting it into the acceptor phase (strip), recommendations.
resulting in the so-called facilitated transport
(Molinari et al. 2009a, b). The selection of an
appropriate carrier provides higher selectivity References
and enrichment factor as compared to the other
separation methodologies. Hasan MA, Selim YT, Mohamed KM (2009) Removal of
chromium from aqueous waste solution using liquid
Despite of their advantages with respect to the emulsion membrane. J Hazard Mater 168:1537–1541
traditional separation techniques, SLM is not Kozlowski CA, Walkowiak W (2002) Removal of chro-
widely applied in treatment of chromium-bearing mium (VI) from aqueous solutions by polymer inclu-
wastewaters. Cr(VI) compounds could be sion membranes. Water Res 36:4870–4876
Kumbasar RA (2008) Studies on extraction of chromium
removed from dilute aqueous solutions by using (VI) from acidic solutions containing various metal
trioctylphosphine oxide (TOPO), Alamine ions by emulsion liquid membrane using Alamine
336, tri-n-octylamine (TOA), and tributyl phos- 336 as extractant. J Membr Sci 325:460–466
phate (TBP) as ionic carrier. Kumbasar RA (2009) Extraction of chromium (VI) from
multicomponent acidic solutions by emulsion liquid
The extraction of HCrO4 with TOPO from membranes using TOPO as extractant. J Hazard
acidic solutions could be expressed by the fol- Mater 167:1141–1147
lowing equation (Kumbasar 2009; Hasan Molinari R, Argurio P, Poerio T (2009a) Studies of various
et al. 2009): solid membrane supports to prepare stable sandwich
liquid membranes and testing copper(II) removal from
aqueous media. Sep Purif Technol 70:166–172
HCrO4 ðaqÞ þ Hþ ðaqÞ þ TOPOðorgÞ Molinari R, Argurio P, Poerio T (2009b) Flux enhance-
ment of stagnant sandwich compared to supported
, H2 CrO4 TOPOðorgÞ liquid membrane systems in the removal of Gemfibro-
zil from waters. J Membr Sci 340:26–34
The so-formed complex diffuses through the Rajasimman M, Karthic P (2010) Application of response
surface methodology for the extraction of chromium
membrane toward the stripping basic solution
(VI) by emulsion liquid membrane. J Taiwan Inst
where the de-complexation reaction takes place Chem Eng 41:105–110
H
Heterogeneous Ion-Exchange Membranes, Fig. 1 Schematic diagram of heterogeneous IEMs with various kinds
of shapes
References
http://www.astom-corp.jp/en/en-main2-edcore.html
Kiyono R, Koops GH, Wessling M, Strathmann H (2004)
Mixed matrix microporous hollow fibers with
ion-exchange functionality, J Membr Sci 231:
109–115
Sata T (2004) Ion exchangemembrane. The Royal Society
of Chemistry, Cambridge
Vermaas DA, Saakes M, Nijmeijer K (2011) Power
generation using profiled membranes in reverse elec-
trodialysis, J Membr Sci 385-386. 234-242
Heterogeneous Ion-Exchange Membranes,
Fig. 2 Tubular-type heterogeneous IEM, EDCORE
H
High Free Volume Polymer, Fig. 1 Molecular struc- (PTMSN), and a polymer of intrinsic microporosity
tures and fractional free volumes of poly(1-trimethylsilyl-1- prepared from 5,50 ,6,60 -tetrahydroxy-3,3,30 ,30 -tetramethyl-
propyne) (PTMSP), a copolymer of 2,2-bistrifluoromethyl- 1, 10 -spirobisindane and 1,4-dicyanotetrafluorobenzene
4,5-difluoro-1,3-dioxole and tetrafluoroethylene (Teflon (PIM-1)
AF2400), addition-type poly(trimethylsilyl norbornene)
centers in PIM-1) to force the backbone to twist volume but also on the size, distribution, and
and turn. connectivity of free volume elements. Computer
The polymers shown in Fig. 1 are soluble and simulation is useful for visualizing the free vol-
can readily be processed from solution to form ume distribution in amorphous polymers
membranes. However, there are other high free (Hofmann et al. 2002). A number of experimental
volume polymers which cannot be prepared in techniques, notably positron annihilation lifetime
soluble form. Sometimes, it is possible to form a spectroscopy (PALS), have been employed to
membrane from a soluble precursor and subse- obtain information about the size and distribution
quently convert it to the desired structure through of free volume elements. In a high free volume
chemical or thermal treatment. For example, polymer, there may be sufficient connectivity
polybenzoxazole structures can be prepared by between free volume elements for the polymer
thermal rearrangement from aromatic hydroxyl- to behave like a molecular sieve or microporous
containing polyimides (Park et al. 2007). material (pore size <2 nm) (Rutherford 2001), in
The permeation of gases and vapors through a which case the apparent micropore distribution
polymer depends not only on the amount of free
High Free Volume Polymer 3
can be determined from gas adsorption studies Pinnau I, Toy LG (1996) Gas and vapour transport prop-
(McKeown and Budd 2010). erties of amorphous perfluorinated copolymer mem-
branes based on 2,2-bistrifluoromethyl-4,5-difluoro-
1,3-dioxole/tetrafluoroethylene. J Membr Sci
109:125–133
References Rutherford SW (2001) Mechanism of sorption and diffu-
sion in a high free volume polymer. Ind Eng Chem Res
Budd PM, McKeown NB (2010) Highly permeable poly- 40:1370–1376
mers for gas separation membranes. Polym Chem Starannikova L, Pilipenko M, Belov N, Yampolskii Y,
1:63–68 Gringolts M, Finkelshtein E (2008) Addition-type
Hofmann D, Heuchel M, Yampolskii Y, Khotimskii V, polynorbornene with Si(CH3)3 side groups: detailed
Shantarovich V (2002) Free volume distributions in study of gas permeation and thermodynamic proper-
ultrahigh and lower free volume polymers: compari- ties. J Membr Sci 323:134–143
son between molecular modeling and positron lifetime Thomas S, Pinnau I, Du N, Guiver MD (2009) Pure and
studies. Macromolecules 35:2129–2140 mixed-gas permeation properties of a microporous
McKeown NB, Budd PM (2010) Exploitation of intrinsic spirobisindane-based ladder polymer (PIM-1).
microporosity in polymer-based materials. Macromol- J Membr Sci 333:125–131
ecules 43:5163–5176 Yampolskii Y (2012) Polymeric gas separation mem-
Park HB, Jung CH, Lee YM, Hill AJ, Pas SJ, Mudie ST, branes. Macromolecules 45:3298–3311
Van Wagner E, Freeman BD, Cookson DJ (2007) Poly-
mers with cavities tuned for fast selective transport of
small molecules and ions. Science 318:254–258
H
Higher (C3+) Hydrocarbon Removal very profitable for the recovery of high-value
monomer in petrochemical plants’ purge gases
Arnaud Baudot (Table 1). In the case of large polymerization
Physics and Analysis Division, IFP Energies facilities, the value of purge monomers can
nouvelles, Solaize, France reach amounts up to two million USD/year.
Higher (C3+) Hydrocarbon Removal, Table 1 Membrane-based olefin recovery from polymer resin degassing vent
(MTR Inc. membrane modules) Baker and Jacobs 1996; Baker et al. 2000
Application Feed composition Olefin flow rate recovered (recovery yield)
LLDPE/HDPE reactor purge Butene 36 % C2 = 145 kg/h (88 %)
Ethylene 41 % nC4 = 142 kg/h (98 %)
Ethane 1 %
Nitrogen 21 %
Hydrogen 1 %
HDPE resin degassing 1-butene 57 % iC4 = 1160 kg/h (97 %)
CO2/O2 2 %
Nitrogen 40 %
Water 1 %
Polypropylene resin degassing Propylene 14 % C3 = 500 kg/h (91 %)
Propane 0.3 %
Nitrogen 84.4 %
Hydrogen 1 %
Water 0.3 %
fouling studies of multiple membranes with high- Burman design, Taguchi’s method, response sur-
quality imaging and a high reproducibility face methodology, and fractional factorial design
(Vanysacker et al. 2013). Filter plate HT plat- are other DoE types already employed in mem-
forms were also applied together with photoin- brane technology.
duced graft polymerization or atmospheric The combination of HT technology with
pressure plasma-induced graft polymerization to appropriate DoE clearly leads to the acceleration
synthesize and screen antifouling membranes of acquiring output, hence, to a better understand-
(Zhou et al. 2009; Gu et al. 2013). An HT ionic ing of the effects of parameters and the properties
conductivity apparatus and an HT mechanical of new membrane materials and formulations. It
testing apparatus for thin membranes were also can thus generate a significant decrease in cost
reported (Zapata et al. 2009, 2010). and increase in efficiency during the discovery
When new HT devices are developed, their and optimization stages of membrane design and
performance should be evaluated based on development processes.
their reproducibility (of the same sample), inter-
changeability (of sample positions), and scalabil-
ity of the setup (compared to conventional Cross-References/Related Terms
methods) (Bilad et al. 2011).
Together with the application of HT technol- ▶ Combinatorial Strategies
ogy, the design of experiments (DoE) has ▶ Design of Experiments
become increasingly important. As membranes ▶ Optimization
can now be quickly synthesized and screened,
the implementation of appropriate experimental
design is crucial to obtain membranes with opti- References
mal performances. The aim is then to quickly
eliminate experimental areas in which limited Basu S, Cano-Odena A, Vankelecom IFJ (2011) -
MOF-containing mixed-matrix membranes for CO2/
successes are expected so combined experimen-
CH4 and CO2/N2 binary gas mixture separations. Sep
tation can be focused on potentially promising Purif Technol 81:31–40
areas. An efficient search strategy combined Bilad MR, Declerck P, Piasecka A, Vanysacker L, Yan X,
with HT technology can rapidly lead to an opti- Vankelecom IFJ (2011) Development and validation
of a high-throughput membrane bioreactor
mum in a large parameter space, in contrast to the
(HT-MBR). J Membr Sci 379:146–153
slower and less effective traditional parameter- Bulut M, Gevers LEM, Paul JS, Vankelecom IFJ, Jacobs
by-parameter approach. Two important aspects PA (2006) Directed development of high-performance
are the certainty of finding an optimum and a membranes via high-throughput and combinatorial
strategies. J Comb Chem 8:168–173
rapid progression of convergence toward the
Cano-Odena A, Spilliers M, Dedroog T, De Grave K,
optimal membrane performance. Ramon J, Vankelecom IFJ (2011) Optimization of
Several experimental design types were cellulose acetate nanofiltration membranes for
already applied in membrane technology. micropollutant removal via genetic algorithms and
high throughput experimentation. J Membr Sci
Among them are artificial neural networks
366:25–32
(ANNs) to predict membrane fouling and separa- Chang H, Hou W-C (2006) Optimization of membrane gas
tion performances in both liquid and gaseous separation systems using genetic algorithm. Chem Eng
environments (Soleimani et al. 2013; Shokrian Sci 61:5355–5368
Gu M, Vegas AJ, Anderson DG, Langer RS, Kilduff JE,
et al. 2010). Genetic algorithms (GAs) were
Belfort G (2013) Combinatorial synthesis with high
applied to obtain an optimum in membrane com- throughput discovery of protein-resistant membrane
position, separation modules and operating con- surfaces. Biomaterials 34:6133–6138
ditions, gas separation systems, and desalination Guria C, Bhattacharya PK, Gupta SK (2005) Multi-
objective optimization of reverse osmosis desalination
units (Bulut et al. 2006; Vandezande et al. 2009;
units using different adaptations of the non-dominated
Yuen et al. 2000; Chang and Hou 2006; Guria sorting genetic algorithm (NSGA). Comput Chem Eng
et al. 2005). Genetic programming, Plackett- 29:1977–1995
High-Throughput Membrane Technology 3
Khan AL, Basu S, Cano-Odena A, Vankelecom IFJ development of membranes and membrane processes.
(2010) Novel high throughput equipment for J Membr Sci 250:305–310
membrane-based gas separations. J Membr Sci Vandezande P, Gevers LEM, Weyens N, Vankelecom IFJ
354:32–39 (2009) Compositional optimization of polyimide-
Khan AL, Klaysom C, Gahlaut A, Khan AU, Vankelecom based SEPPI membranes using a genetic algorithm
IFJ (2013) Mixed matrix membranes comprising of and high-throughput techniques. J Comb Chem
Matrimid and -SO3H functionalized mesoporous 11:243–251
MCM-41 for gas separation. J Membr Sci 447:73–79 Vanysacker L, Declerck P, Vankelecom I (2013) Devel-
Shokrian M, Sadrzadeh M, Mohammadi T (2010) C3H8 opment of a high throughput cross-flow filtration sys-
separation from CH4 and H2 using a synthesized tem for detailed investigation of fouling processes.
PDMS membrane: Experimental and neural network J Membr Sci 442:168–176
modeling. J Membr Sci 346:59–70 Yuen CC, Aatmeeyata, Gupta SK, Ray AK (2000) Multi-
Soleimani R, Shoushtari NA, Mirza B, Salahi A (2013) objective optimization of membrane separation mod-
Experimental investigation, modeling and optimiza- ules using genetic algorithm. J Membr Sci
tion of membrane separation using artificial neural 176:177–196
network and multi-objective optimization using Zapata P, Basak P, Carson Meredith J (2009) High-
genetic algorithm. Chem Eng Res Des 91:883–903 throughput screening of ionic conductivity in polymer
Van Doorslaer C, Glas D, Peeters A, Cano Odena A, membranes. Electrochim Acta 54:3899–3909
Vankelecom I, Binnemans K, Mertens P, De Vos Zapata P, Mountz D, Meredith JC (2010) High-throughput
D (2010) Product recovery from ionic liquids by characterization of novel PVDF/acrylic polyelectro-
solvent-resistant nanofiltration: application to ozona- lyte semi-interpenetrated network proton exchange
tion of acetals and methyl oleate. Green Chem membranes. Macromolecules 43:7625–7636
12:1726–1733 Zhou M, Liu H, Kilduff JE, Langer R, Anderson DG,
Vandezande P, Gevers LEM, Paul JS, Vankelecom IFJ, Belfort G (2009) High-throughput membrane surface
Jacobs PA (2005) High throughput screening for rapid modification to control NOM fouling. Environ Sci
Technol 43:3865–3871
H
Hollow Fiber Liquid Membrane shown in Fig. 1a. The process is achieved by
packing thousands of microporous hollow fibers
Vladimir S. Kislik in a permeator shell filled with stationary liquid
Campus Givat Ram, Casali Institute of Applied membrane solution. The fibers are present in feed
Chemistry, The Hebrew University of Jerusalem, and strip sets very close to each other but with the
Jerusalem, Israel ends of each set being separated. If the fibers are
hydrophilic, the aqueous feed and strip flow
through the lumen side of the fibers and fill the
Hollow fiber (HF) supported liquid membrane is pores of the fiber; if fibers are hydrophobic, they
a three-phase liquid membrane system in which are wetted by organic LM phase (Fig. 1b). So,
the membrane phase (liquid) is held by capillary reader can see that this is a hybrid system with
forces in the pores of microporous polymeric or combination of modified SLM and BLM
inorganic hollow fibers. The design of the hollow configurations.
fiber SLM module consists of a certain number of Hollow fibers in tube pertractor (Schlosser
thin fibers, placed along the length of the shell. 2000) is another type of HF module (see Fig. 2)
The feed phase is pumped through the fibers; the “with parallel flow consisting of one or two
pores in the fibers are filled with the LM solution, intermixed U-shaped bundles of microporous
and the receiving (strip) phase is forced out polypropylene fibers, inserted into polysulfon
through the sides of the shell. HF SLMs are (or glass) tubes”. Pulsation of the LM phase
schematically presented in the Figs. 1, 2, and 3. along the fibers is used for better mixing.
Compact and modular hollow fiber devices can One more type of the HF modules is presented
be used with exceptionally high mass transfer schematically in Fig. 3. A crossflow with pulsa-
area per unit equipment volume. Very often tion perpendicularly to fibers was used here.
such HF systems are termed as contactor devices. Some plate and frame HF modules were pro-
Contactor devices are used as construction units posed. The module with “fiber in fiber” units
in many of the SLM, HFCLM, and BLM systems. and crossflow of one phase is described in Ref.
The theory of the HFLM transport was developed Schlosser and Sabolova (2002).
by Sirkar et al. (see in Sirkar 1996) and Schlosser A capillary membrane module was developed
et al. (see in Schlosser and Sabolova 2002). (Teramoto et al. 2003) for gas separation. The
Different hollow fiber modules can be classi- concept of a capillary membrane apparatus is
fied into several groups. One, termed as a “hollow shown in Fig. 4. Both a feed gas and a LM
fiber contained liquid membrane (HFCLM)” solution are supplied to the lumen side (high-
(Majumdar and Sirkar 1992) configuration, is pressure feed side) of the capillary ultrafiltration
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_283-2
2 Hollow Fiber Liquid Membrane
b Sweep out
a
F F F
S S S
S Feed Feed
out in
F F F
Pressure
source
S S
LM -
reservoir
Sweep in
Hollow Fiber Liquid Membrane, Fig. 1 Hollow fiber contained liquid membrane (HFCLM): (a) configuration of
permeator shell and (b) side view of the permeator
2 F
3
membrane module and flow upward. The LM One more example of hollow fiber LM sepa-
solution, which contains dissolved solute gas ration system is described as affinity dialysis
(CO2), flows to the permeate side (low-pressure (Devis et al. 1988) Water-soluble polymer
shell side), where the solution liberates dissolved (WSP) solutions as LM were immobilized into
gas to become a lean solution. The lean solution the pores of hollow fiber units (fibers of 5,000
is returned to the lumen of the capillary module molecular weight cutoff from Spectra/Por were
by a pump. In the shell side, dissolved gas is used). Selective separation and concentration of
stripped from the liquid flowing down on the both cations (Ca/Na, Cu/Zn) and anions
outer surface of the capillary and discharged (potassium chromate/sodium chloride) were
from a vacuum pump through a liquid reservoir. tested. 2.5 % w/v aqueous solution of poly
Hollow Fiber Liquid Membrane 3
E 2
5
Section AA:
A' 3
Section BB:
1 3 9 2
a b
exhaust gas exhaust gas
capillary
membrane
to pressure 30mm
gauge permeable
stripped gas section capillary
(165mm) membrane
to vacuum
liquid
pump
permeation capillary
enriched capillary membrane
impermeable
CO2 membrane coated with
section
opoxy (265mm) adhesive
adhesive to vacuum
capilarty mem exhaust gas pump distributor
vacuum module
absorbent feed gas absorbent feed gas
pump
CO2/N2 tee tee
carrier feed gas
solution (a) Module A (b) Module B
Hollow Fiber Liquid Membrane, Fig. 4 Schematic dioxide: (a) experimental capillary membrane apparatus
diagrams of facilitated transport of gas using capillary and (b) capillary membrane modules with permeation of
membrane module for removal and enrichment of carbon carrier solution (From Teramoto et al. 2003)
Natural Organic Matter (NOM) and temporally. One of the major groups in
NOM is humic substances (HS), which include
Tony Fane a complex mixture of organic compounds such as
UNSW, School of Chemical Engineering, The humic acids (HA), fulvic acids (FA), and other
University of New South Wales, Sydney, NSW, hydrophilic compounds. Typically, humic sub-
Australia stances have molecular weights from a few hun-
dreds to approximately 100,000 Da. They contain
both aromatic and aliphatic components with car-
Natural organic matter (NOM) is an organic boxylic and phenolic groups attached to the aro-
material from environmental origin and produced matic rings. As a result, humic substances can be
by biodegradation of organic substances (plants, negatively charged as well as having hydropho-
etc.). NOM gives surface waters a brownish color bic and hydrophilic components. The humic frac-
and is a problem in drinking water supply, not tion also has neutral components. The charge
because of its toxicity but because some of its character is important as it influences interactions
components can react with chlorine used as dis- with other pollutant species and the treatment
infectant. The reaction by-products include tri- process equipment (such as membrane surfaces).
halomethane, haloacetic acids, chlorophenols, The complexity of NOM makes characteriza-
etc. which are potentially carcinogenic. The tion difficult. A review of methods can be found
NOM components are known as trihalomethane in Leenheer and Croue 2003. Recently NOM
precursors (THMPs), and it is recognized that characterization has involved size exclusion
their removal prior to disinfection is important chromatography, combined with UV and online
for public health. Membrane technology is fre- DOC and organic nitrogen detection, in a system
quently used for treatment to remove NOM from called “liquid chromatography-organic carbon
surface waters (see ▶ NOM Removal and detection-organic nitrogen detection”
Fouling). (LC-OCD-OND) (Huber 2014). This instrument
Natural organic matter (NOM) has a broad provides a molecular weight distribution and also
spectrum of molecular weights and size distribu- identifies components (in descending size) as bio-
tions, functional groups, and substructures. The polymers, humics, building blocks, low MWt
term NOM covers the particulate colloids (POM), acids and humics, and neutrals. This measure-
“dissolved” colloids, and macrosolutes or ment technique is now widely used in membrane
dissolved organic matter (DOM) and the humics. applications to water and wastewater.
Since NOM is from environmental origin, its
composition is highly variable both spatially
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_286-1
2 Natural Organic Matter (NOM)
Natural Organic Matter, Removal areas where chemical dosing would be trouble-
and Fouling of some. This advantage of NF may be offset by
higher pressures and energy costs in some
Tony Fane applications.
School of Chemical Engineering, UNSW, The NOM fouling of membranes is complex with
University of New South Wales, Sydney, NSW, many influencing factors, including the variable
Australia nature of the raw water. It should be noted that no
one single component of NOM has been identi-
fied as the major cause for membrane fouling and
Natural organic matter (NOM) is present in sur- there are conflicting views in the literature. How-
face waters and its removal prior to disinfection is ever, some components are clearly implicated.
important to avoid formation of potentially car- The mechanisms of UF membrane fouling have
cinogenic trihalomethanes (see “▶ Natural been shown to be cake formation, pore restriction
Organic Matter”). With a size range from colloi- by adsorption, and pore plugging (see “▶ Irre-
dal to a few hundred Daltons the NOM species versible Fouling”). Both reversible and irrevers-
are well suited to removal by membranes, includ- ible fouling have been found in the membrane
ing removal of trihalomethane precursors treatment of surface waters. Thus, a fraction of
(THMPs). However, some of the components of NOM with molecular sizes smaller than the mem-
NOM are potential membrane foulants, as brane pores may adsorb and reduce the pore
discussed below. cross-sectional area for permeation and larger
Most typically, NOM removal involves fractions may plug pore entrances or contribute
microporous membranes (micro- or ultrafiltra- to cake formation.
tion), often in combination with a coagulant The hydrophobicity/hydrophilicity of NOM
(ferricsalts, polyaluminium chloride, etc). The has been found to be a factor influencing mem-
hybrid processes, combining membranes with brane fouling in natural water treatment. There is
chemical addition, give improved removals as evidence that the hydrophobic components in
seen in Table 1. The hybrid processes also pro- NOM tend to be responsible for the fouling of
vide better control of membrane fouling (see hydrophobic membranes due to hydrophobic
below). The disadvantage is the disposal of the interactions. However, there are contrary views.
waste sludge solids. Nanofiltration (NF), with In an Australian study, NOM was isolated into
pores in the 5–2 nm size range, is capable of four fractions: hydrophilic neutral, hydrophobic
high removals of NOM and is used extensively acids, transphilic acids, and hydrophilic charged.
in Norway and Scotland, particularly in remote The order of the fouling potential of the individual
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_287-1
2 Natural Organic Matter, Removal and Fouling of
Natural Organic Matter, Removal and Fouling of, Table 1 Typical removals of NOM by membranes
TOC/DOC THMP
Process Removal (%) Removal (%)
Microfiltration 10–40 15–20
MF + chemical ~80 ~60
Ultrafiltration ~50 ~40
UF+ chemical ~90 ~80
Nanofiltration 90–99 90–99
Sanchez C, Julian B, Belleville P, Popall M (2005) Appli- Singh AK, Singh P, Mishrab S, Shahi VK (2012) Anti-
cations of hybrid organic–inorganic nanocomposites. biofouling organic–inorganic hybrid membrane for
J Mater Chem 15:3559–3592 water treatment. J Mater Chem 22:1834–1844
H
several drawbacks: high investment costs, the diffusion coefficient of normal alkanes in MFI
sophisticated sequential operation (adsorption- zeolites is higher (Courthial et al. 2008) than the
desorption cycle), the use of large quantities of diffusion coefficient of their monobranched iso-
solvents (desorbants), and lack of modularity. mers. Moreover, these materials prove to be
Since the beginning of the 1990s, much atten- hardly permeable to dibranched paraffins. As an
tion has been paid to overcoming the drawbacks illustration, it was shown experimentally that a
of conventional zeolite adsorbents through the MFI zeolite membrane operated under close to
development of zeolite membranes that combine industrial operating conditions (2–4 bar feed pres-
the technical advantages of membranes sure, membrane temperature between 200 C and
(modularity, continuous operation) with the high 400 C) was able to produce a permeate composed
separation performances of zeolites (due to their of 95 % normal pentane and 5 % isopentane
sieving properties). Most of the published R&D from a vapor feed composed of 20 %
work on that topic was carried out at lab scale 2,2-dimethylbutane, 55 % isopentane, and only
mainly by academic laboratories, though a few 25 % normal pentane (Baudot and Bournay 2009).
companies, like ExxonMobil or NGK Insulators,
have also published results on that topic. One of
the most studied topics in this research field was
References
the separation of normal short (C4–C6) paraffins
from their branched isomers through MFI-type Arruebo M, Falconer JL, Noble RD (2006) Separation of
zeolite membranes (Arruebo et al. 2006; Bakker binary C-5 and C-6 hydrocarbon mixtures through
et al. 1996; Coronas et al. 1998). Indeed, MFI MF1 zeolite membranes. J Membr Sci 269:171–176
zeolites are crystalline aluminosilicates with a Bakker WJW, Kapteijn F, Poppe J, Moulijn JA (1996) Per-
meation characteristics of a metal-supported silicalite-
microporous structure that is composed of two 1 zeolite membrane. J Membr Sci 117:57–78
intricate micropore networks: elliptical straight Baudot A, Bournay L (2009) Integration of MFI zeolite
channels with openings of 0.51 0.55 nm and membranes in the light gasoline isomerisation process.
zigzag channels that are almost cylindrical with a Oil Gas Sci Technol 64:759–771
Coronas J, Noble RD, Falconer JL (1998) Separations of
diameter of 0.53 0.56 nm, as measured by C-4 and C-6 isomers in ZSM-5 tubular membranes.
X-ray diffraction at ambient temperature Ind Eng Chem Res 37:166–176
(Flanigen et al. 1978). In such a confined porous Courthial L, Baudot A, Tayakout-Fayolle M, Jallut C
system wherein the diameter of the micropores (2008) A transient permeation-based method for com-
posite zeolite membrane characterization. AIChE J
and the kinetic diameter of the diffusing mole- 54:2527–2538
cules are close, the higher the kinetic diameter of Flanigen EM, Bennett JM, Grose RW, Cohen JP, Patton
a permeating molecule, the higher the friction of RL, Kirchner RM, Smith JV (1978) Silicalite, a new
the molecule alongside the micropore wall and hydrophobic crystalline silica molecular-sieve. Nature
271:512–516
therefore the lower its diffusion coefficient inside
the microporosity of the MFI zeolite. Therefore,
H
O O O O O O O O O O
O O O O Co O O
Co Co
e O O
ac Support (metal oxide) Support (metal oxide) Support (metal oxide)
urf
cs scheme 1 scheme 9 scheme 13
idi
Ac
H2 O O O O O
C C CO2
H
CH3CH2O
C2H4 2 H2O H
O O OH OH O O O O O O O O
O O O O Co O O
Co Co
H H H H
Co O Support (metal oxide) O
Support (metal oxide) Support (metal oxide)
scheme 3 scheme 8 scheme 12
Support (metal oxide)
scheme 2 CH CHO
3
Route 1
CH4CHO CH3COCH3
H2 O O
HC
CH3CH2O
H H
Route 2
CH3CH O
OH OH OH OH OH + O O O O O
O O O O O Co O O
Co CH4 CO H2
Deactivation O O Support (metal oxide) O
Cx Cx C Support (metal oxide)
Cx
OC
x scheme 4 OH H3C OH + OH scheme 11
x
OH OH OH O O
x
Cx
O Co
C C
O
Co
H2 CO
Support (metal oxide) O H2
Support (metal oxide) O
H3CC
H2 scheme 7 O
scheme 6 H H-CHx
OC
OH O O OH OH OH OH OH + OH
O O O O O Co O O
Deficient oxygen Co
or Co site accessiblity Sufficient oxygen accessiblity
Support (metal oxide) O Support (metal oxide) O
scheme 5 scheme 10
Hydrogen from Bioethanol, Fig. 1 Proposed reaction mechanism for ethanol steam reforming over supported Co catalysts (Song 2012)
Hydrogen from Bioethanol
Hydrogen from Bioethanol 3
Water Air
Feed H2
FBR HT WGS LT WGS CO PROX H2Purification
(PSA)
Cooler Cooler Cooler
Hydrogen from Bioethanol, Fig. 2 High-purity hydrogen production in a conventional multistage system
Hydrogen from
Bioethanol, Fig. 3 High-
purity hydrogen production
in a membrane reactor with
a Pd-based membrane
CeO2), and the reaction conditions (Costa-Serra impurities present in the crude ethanol solution,
et al. 2010; Song 2012). especially high linear and branched alcohols
Besides the ethanol steam reforming main (Le Valant et al. 2011; Song 2012).
reaction referred above, the process follows a In the viewpoint of hydrogen production for
complex reaction system with several possible supplying polymer electrolyte membrane fuel
consecutive parallel reactions, such as partial cells (PEMFCs), the reformate stream, which
reforming to CO, water gas shift, methanation, comprises a complex mixture of compounds,
coke formation from intermediate products, needs a separation/purification, especially due to
Boudouard reaction, CO reduction, methane the maximum allowed CO concentration
cracking, dehydration/hydrogenation, and dehy- (0.2 ppm). A conventional steam reformer system
drogenation. In addition to H2 and CO2, refor- is composed by the reformer (fixed bed reactor
mate stream may contain also CO, methane, (FBR)), two water gas shift reactors (high- and
aldehydes, ketones, ethylene, ethane, and high low-temperature WGS), a CO partial oxidation
alcohols, among others (Vizcaíno et al. 2007; reactor (PROX), and pressure swing adsorption
Song 2012) (Fig. 1). (PSA) units (Fig. 2).
The main drawback of using bioethanol to This complex process may be replaced by a
produce hydrogen via steam reforming is the much simpler membrane reactor (MR) holding
high cost associated to the downstream distilla- hydrogen permselective membranes. This new
tion and purification steps of the crude ethanol reactor is able to perform both the steam
obtained from fermentation. Feeding directly the reforming of bioethanol and the separation/puri-
crude bioethanol to the reformer would reduce fication of the produced hydrogen in the same
drastically the costs of the produced hydrogen. device (Fig. 3).
Besides the unnecessary expensive distillation Moreover, this kind of MR makes possible the
process for water and other compounds elimina- in situ removal of hydrogen from the reaction side,
tion, the reforming of other oxygenated hydro- allowing the conversion to overcome the thermo-
carbons contained in the fermentation broth could dynamic equilibrium value (which is not possible
contribute to generate extra hydrogen. The main in the FBR). Furthermore, if Pd or Pd-based mem-
challenge for the implementation of this branes are used, a pure hydrogen stream is col-
approach at an industrial level remains in the lected in the permeate side, suitable for direct
tolerance and stability of the catalyst to the PEMFC supplying (Iulianelli and Basile 2011).
4 Hydrogen from Bioethanol
Hydroprocessor Purge Gases – Air Liquide with the MEDAL polyimide and
high selectivity polyaramide membranes.
A. Baudot
Physics and Analysis Division, IFP Energies All those membranes are based on glassy
nouvelles, Solaize, France polymers and offer a diffusion-based hydrogen
selectivity. Today’s membranes have high H2/
CH4 selectivities (from 35 to 200 at 80 C
The demand for hydrogen is constantly increas- (Roman et al. 2001)). For instance, Air Products
ing in refineries due to more and more stringent claims that a single-stage array of Prism ® mod-
sulfur content specifications for fuels (leading to ules is able to raise the concentration of gases
an increasing hydrogen consumption in from 10–30 % up to 70–90 % (Air Products
hydrodesulfurization processes) and a growing website), while MEDAL membranes are able to
heavy crude consumption, which results in a raise the concentration of a gas at 51 bar from
higher worldwide demand for highly hydrogen- 86 % in hydrogen up to 98 % with a permeate
consuming upgrading processes, such as hydro- pressure at 30 bar and a residue containing 52 %
cracking. In this changing landscape, permeation of hydrogen at 50 bar (Medal website).
membranes constitute an elegant option for the In 2003, it was reported that more than
recovery of hydrogen that is nowadays wasted in 400 hydrogen permeators were installed world-
an array of refinery off-gases, such as fuel gas, wide (Monereau 2003) while approximately
PSA tail gas, FCC gas, catalytic reformer 100 were operated in refineries (Baker 2002).
off-gases, or hydrocracker/hydrotreater As there are more than 500 refineries in the
off-gases. world, it is clear that the potential market for
Nowadays, three main membrane providers this type of membrane applications is far from
offer hydrogen purification permeators: saturated. Nevertheless, three main limits still
hinder the wide acceptance of permeation-based
– Air Products with the Prism ® silicon-coated hydrogen purification in the refining industry:
polysulfone membranes (issued from
Monsanto). Air Products claims that the life- – The purified hydrogen is recovered at low
time of the Prism ® modules can be more than pressure in the permeate side and requires
15 years. compression in order to feed it back to reac-
– Ube Industries with polyimide hollow fiber tors. As such, PSA (pressure swing adsorp-
membranes. tion) is a more attractive process, as the
Hydroprocessor Purge Gases, Table 1 Ube Industries membrane material compatibility against contaminants (Ube
Industries website)
Contaminants Maximum allowable content
Water vapor Up to saturation
H2S 3 % vol
NH3 and amines 100 ppm vol
Methanol 5 % vol
Methyl ether 5 % vol
Benzene 1 % vol
Toluene 2000 ppm vol
C5+ hydrocarbons Up to saturation
Hyperbranched
Polyimides,
Fig. 1 Architecture of
polymers
synthesized by AB2-type monomer, which has a since the early 2000s, and most of them are syn-
carboxylic acid ester and two amino groups in a thesized by A2- and B3-type monomers. The gas
molecule and a condensation agent. permeability of hyperbranched polyimides is
Hyperbranched polyimides are synthesized by almost equal to or higher than that of other glassy
chemical imidization of poly(amic acid ester) polymers such as polysulfone or polycarbonate.
(Yamanaka et al. 2000). Hyperbranched
polyimides can be synthesized by self-
polycondensation of ABx-type monomers with References
imide ring in the monomer framework. Thompson
et al. (1999) reported that hyperbranched Flory PJ (1952) Molecular size distribution in three-
dimensional polymers. VI. Branched polymer
polyetherimides are synthesized by thermal poly-
containing A-R-Bf-1-type units. J Am Chem Soc
condensation of AB2-type monomers with fluorine 74:2718–2723
(A functional group) and silylated phenolic Kim YH, Webster OW (1990) Water soluble
hydroxyl group (B functional group), which can hyperbranched polyphenylene: “a unimolecular
micelle”. J Am Chem Soc 112:4592–4593
be detached in a molecule. When A2- and B3-type
Kricheldorf HR, Zang QZ, Schwarz G (1982) New poly-
monomers are used as starting materials in poly- mer syntheses. 6. Linear and branched poly
merization, AB2-type monomers need not be syn- (3-hydroxybenzoates). Polymer 23:1821–1829
thesized. Various hyperbranched polyimides are Thompson DS, Markoski LJ, Moore JS (1999) Rapid syn-
thesis of hyperbranched aromatic polyetherimides.
synthesized because they can be obtained by poly-
Macromolecules 32:4764–4768
merization using a commercial A2-type monomer Yamanaka K, Jikei M, Kakimoto M (2000) Synthesis of
and synthesized B3-type monomer. hyperbranched aromatic polyimides via polyamic acid
Hyperbranched polyimides have attracted atten- methyl ester precursor. Macromolecules
33:1111–1114
tion as materials for gas separation membranes
I
Ideal Separation Factor where xi,p and xj,p are the fractions of components
i and j in the permeate and xi,f and xj,f are the
Johannes Carolus Jansen fractions of components i and j in the feed. The
Institute on Membrane Technology ITM-CNR, separation factor is not a material property, but it
Consiglio Nazionale delle Ricerche, Rende (CS), also depends on the conditions of the separation
Italy process. It depends both on the membrane prop-
erties and on the driving force, which in turn
depends on the pressure and on, for instance, the
The separation factor, SF, is a measure of the presence of concentration polarization phenom-
efficiency of the separation process and is deter- ena, nonideal behaviour such as plasticization,
mined from the ratio of the concentrations of the coupling effect, etc.
more permeable gas species i and the less perme- Analogously, the ideal separation factor is the
able gas species j in the permeate divided by the separation factor under ideal conditions. It can be
ratio of the same gases i and j in the feed stream: calculated from the pure gas permeabilities.
xi, p =xj, p
SF ¼ (1)
xi, f =xj, f
drop across the membranes is very low due to the with other planar and basic residues. J Proteome Res
large pore size. Owing to the continuous pore 2:255
Boi C, Busini V, Salvalaglio M, Cavallotti C, Sarti GC
structure, mass transport occurs by convection (2009) Understanding ligand-protein interactions in
rather than by diffusion. Chromatographic mem- affinity membrane chromatography for antibody puri-
branes are generally cost effective, and their fication. J Chromatogr A 1216:8687–8696
scale-up is easier than the packed-bed chroma- Bruce MP, Boyd V, Duch C, White JR (2002) Dialysis-
based bioreactor systems for the production of mono-
tography (Charcosset 1998). Membrane opera- clonal antibodies-alternatives to ascites production in
tions including ultrafiltration (Mohanty and mice. J Immunol Methods 264:59–68
Ghosh 2008; Rosenberg et al. 2009), dialysis Charcosset C (1998) Purification of proteins by membrane
(Bruce et al. 2002), and affinity membrane chro- chromatography. J Chem Technol Biotechnol 71:95
Denizli A, Pişkin E (2001) Dye-ligand affinity systems.
matography (Boi et al. 2009) have been demon- J Biochem Biophys Methods 49:391
strated for their potential for IgG purification. F€
uglistaller P (1989) Comparison of immunoglobulin
binding capacities and ligand leakage using eight dif-
ferent protein A affinity matrices. J Immunol Methods
124:171
References Low D, O’Leary R, Pujar NS (2007) Future of antibody
purification. J Chromatogr B 848:48
Altıntaş EB, Denizli A (2009) Monosize magnetic hydro- Mohanty K, Ghosh R (2008) Novel tangential-flow coun-
phobic beads for lysozyme purification under mag- tercurrent cascade ultrafiltration configuration for con-
netic field. Mater Sci Eng C 29:1627 tinuous purification of humanized monoclonal
Altıntaş EB, T€uzmen N, Uzun L, Denizli A (2007) antibody. J Membr Sci 307:117–125
Immobilized metal affinity adsorption for antibody Rosenberg E, Hepbildikler S, Kuhne W, Winter G (2009)
depletion from human serum with monosize beads. Ultrafiltration concentration of monoclonal antibody
Ind Eng Chem Res 46:7802 solutions: development of an optimized method mini-
Bakhspour M, Bereli N, Şenel S (2014) Preparation and mizing aggregation. J Membr Sci 342:50–59
characterization of thiophilic cryogels with 2- T€
urkmen D, Özt€ urk N, Elkak A, Akgöl S, Denizli
mercaptoethanol as the ligand for IgG purification. A (2008) Phenylalanine containing hydrophobic
Colloid Surf B 113:261 nanospheres for antibody purification. Biotechnol
Bhattacharyya R, Saha RP, Samana U, Chakrabarti Prog 24:1297
P (2003) Geometry of interaction of the histidine ring
I
man. In: Henry’s clinical diagnosis and management Terman DS, Stewart I, Hofmann A, Carr R, Harbeck
by laboratory methods. 21st edn, McPherson RA, R (1974) Specific removal of DNA antibody with an
Pincus AR (eds); Saunders-Elsevier publishes, Phila- immunoadsorbent. Experientia 30:1493
delphia pp. 876-893 Uzun L, Yavuz H, Osman B, Çelik H, Denizli A (2010)
Subramanian A (2002) Immunoaffinity chromatography. PHEMA based affinity membranes for in-vitro
Mol Biotechnol 20:41 removal of anti-dsDNA antibodies from SLE plasma.
Int J Biol Macromol 47:44
I
Imprinted Polysulfone-
Aldehyde Derivatized
Nanofiber Membranes,
Fig. 1 Chemical structures
of polysulfone with
aldehyde group (PSf-CHO)
and print molecule
(Z-D-Glu or Z-L-Glu) (Cited
from Sueyoshi et al. 2012
with permission. Copyright
2012 Elsevier Inc)
Imprinted Polysulfone-
Aldehyde Derivatized
Nanofiber Membranes,
Fig. 2 Schematic
illustration for the
fabrication of molecularly
imprinted nanofiber
membranes, where
PSf-CHO and Z-Glu were
simultaneously
electrosprayed
selectivity, permselectivity, and flux, were stud- applied as a print molecule to obtain molecularly
ied (Sueyoshi et al. 2012). imprinted nanofiber membranes and usual molec-
PSf-CHO with degree of substitution of 0.50 ularly imprinted membranes for optical resolu-
and 1.00 were adopted as candidate materials, tion (Figs. 1 and 2).
and the derivative of D- or L-glutamic acid was
Imprinted Polysulfone-Aldehyde Derivatized Nanofiber Membranes 3
2.0
D-Glu
L-Glu
L R
membrane
1.0
a L/D = 1.20
0.5
D-Glu
L-Glu
0
0 2.0 4.0 6.0 8.0 10.0
Time / h
Imprinted Polysulfone-Aldehyde Derivatized Imprinted Polysulfone-Aldehyde Derivatized
Nanofiber Membranes, Fig. 3 Adsorption isotherm of Nanofiber Membranes, Fig. 4 Time-transport curves
D-Glu and L-Glu in the nanofiber membrane molecularly
of racemic Glus through the nanofiber membrane molec-
imprinted by Z-D-Glu. (PSf-CHO-10 was adopted as a ularly imprinted by Z-D-Glu (PSf-CHO-10 was adopted as
candidate material) (Cited from Sueyoshi et al. 2012 a candidate material) (Cited from Sueyoshi et al. 2012
with permission. Copyright 2012 Elsevier Inc) with permission. Copyright 2012 Elsevier Inc)
Imprinted Polysulfone-Aldehyde Derivatized Nanofiber Membranes, Table 1 Results of chiral separation with
molecularly imprinted nanofiber (MINFM’s) and molecularly imprinted (MIPM’s) membranes
Z-D-Glu imprinted membrane Z-L-Glu imprinted membrane
Mmebrane aL/D u0 aD/L u0
MINFM-10a 1.24 1.15 10 9 (28) 1.20 1.67 10 9 (41)
MIPM-10a 1.20 4.20 10 11 (1) 1.20 4.10 10 11 (1)
MINFM-05b 1.12 7.00 10 9 (231) 1.20 2.20 10 9 (72)
MIPM-05b 1.25 6.64 10 11 (2.2) 1.16 3.05 10 11 (1)
a
Figures in parentheses are the relative values; the U Value for MIPM-10 imprinted by Z-L-Glu being set as unity
b
Figures in parentheses are the relative values; the U Value for MIPM-05 imprinted by Z-L-Glu being set as unity
c
U = (–J/C)/(dm/dx) [{(mol cm cm-2 h-1)/(mol cm-3)}/(J mol-1 cm-1) = mol cm cm-2 J-1 h-1].
(Cited from ref. Sueyoshi et al. 2012 with permission. Copyright 2012 Elsevier lnc.)
such membranes which although they incorpo- cases the term inert membrane has a somewhat
rate catalytic surface reactions, they are regarded different meaning than that related to the IMRs.
as inert membranes since the reaction is present
solely as a means of sustaining transport of the
gas molecule from one membrane side to the
References
other. Another example is inert membranes for
liquid separation applications, where surface Koros WJ, Ma YH, Shimidzu T (1996) Terminology for
hydrophilicity and hydrophobicity may membranes and membrane processes. Pure Appl
completely determine the membrane transport Chem 68:1479–1489
properties. The term inert membrane is rarely Mulder M (1996) Basic principles of membrane technol-
ogy. Kluwer Academic Publishers, Dordrecht, The
used for conventional membrane separation pro- Netherlands
cesses; however, one may find the term inert Sirman J (2006) The evolution of materials and architec-
membrane used in such phrases as “chemically ture for oxygen transport membranes. In: Sammells
inert membrane” or “bio-inert membrane.” These AF, Mundschau MV (eds) Nonporous inorganic mem-
branes. Wiley-VCH, Weinheim, pp 165–184
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membrane such as chemical stability or compat- behavior in palladium membranes. J Membr Sci
ibility in the case of chemical inertness or biolog- 153:211–231
ical inactivity in the case of bio-inertness. In these
I
Inert Membrane Reactors, Fig. 1 Inert membrane (a) with solid catalyst, (b) with liquid containing the catalyst, (c)
encapsulating solid catalyst, (d) encapsulating liquid containing the catalyst
Inert Membrane Reactors, Fig. 2 (a) Membrane extractor operation, (b) membrane distributor operation
IMR with packed catalyst bed for oxidative cou- number of challenges still exist with respect to
pling of methane to C2, or oxidative dehydroge- high temperature applications, and commercial
nation of hydrocarbons, by addition of oxygen use of IMRs is still a future prospect. To aid
and hydrogenation of alkenes by hydrogen addi- reaching this future prospect, mathematical
tion. For some oxidation reactions employing modeling and simulation is required to develop
IMRs, the separation of the bulk of the reactants IMR design and provide an understanding of the
by the membrane wall lowers the explosion optimal operating conditions.
potential (Coronas and Santamaria 1999).
As most membrane materials are inert, the
incorporation of many different types into IMRs
References
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are advantageous with respect to capital cost, Coronas J, Santamaria J (1999) Catalytic reactors based on
high packing density, and simple sealing technol- porous ceramic membranes. Catal Today 51:377–389
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temperature, typically less than 100 C, and lim- Ertl G, Knözinger H, Weitkamp J (eds) Handbook of
heterogeneous catalysis, vol 3. Wiley-VCH
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enable high temperature operation, but since sta- membrane reactors. In: Drioli E, Giorno L (eds) Com-
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Several decades of research have shown that a ideas. J Membr Sci 181:3–20
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Koros WJ, Ma YH, Shimidzu T (1996) Terminology for Van der Bruggen B (2010) Pervaporation membrane reac-
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F
a b
c
d e
Inorganic Catalytic Membrane, Fig. 1 Inherently catalytic (a) porous, (b) dense membrane. Inert membrane with
catalyst deposited (c) inside pores, on outer surface of (d) porous, and (e) dense membrane
Inorganic Catalytic Membrane, Fig. 2 Inorganic catalytic membrane in (a) extractor operation, (b) distributor
operation, (c) flow-through contactor operation, (d) liquid–gas contactor operation
membrane and catalyst properties. Common reactions in catalyst powder beds (Westermann
examples of applications include hydrocarbon and Melin 2009). Additionally, higher selectivity
dehydrogenation, hydrocarbon reforming, and may be achieved due to the short and well-
hydrogenation of alkenes for which hydrogen defined contact time between reactants and mem-
selective inorganic catalytic membranes can be brane catalyst. Yet in another contactor mode, the
used (Sanchez Marcano and Tsotsis 2002). Com- porous inorganic catalytic membrane provides a
bination of endothermic (e.g., water splitting to defined catalytic region for reaction and controls
produce hydrogen) and exothermic (e.g., partial transport of reactants from both sides of the mem-
oxidation of methane) reactions for integrated brane. For example, in liquid–gas catalytic
mass and heat transport has been demonstrated contactors, both hydrogenation and oxidative
by using catalytically active oxygen permeable reactions have been demonstrated.
membranes (Caro 2010). By feeding oxygen in a
controlled manner, partial oxidation of hydrocar-
bons to form synthesis gas, oxidative coupling of
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methane, and oxidative dehydrogenation reac-
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I
Ion Exchange Membrane for Fuel Nafion type have shown similar levels of perfor-
Cells mance. One critical aspect is related to the fact
that the presence of water is a requirement of
Antonino Salvatore Arico low-temperature PEMFCs and DMFCs for the
CNR-ITAE Institute, Messina, Italy occurrence of the electrochemical reactions and
to promote ion conductivity (water-assisted con-
ductivity mechanism). High ionic conductivities
Low-temperature fuel cells can be equipped with are often associated to the presence of large water
a proton or anion exchange membrane in alterna- uptake by the membrane, but this property often
tive to liquid electrolytes (Aricò et al. 2001). The causes poor mechanical characteristics such as
core of a polymer electrolyte fuel cell (PEMFC) large swelling and relevant crossover (especially
is the ion exchange membrane. The electrodes methanol). Phosphoric acid-doped polybenzoi-
(anode and cathode) are in intimate contact with midazole membranes use a Grotthus mechanism
the membrane faces. The membrane determines of proton transport and do not require water
the fuel cell resistance and the fuel permeation (Wang et al.1995). These membranes operate at
rate, and it influences the reaction rate. It is well about 180–200 C. Whereas composite perfluor-
known that the use of non-noble metal catalysts is osulfonic acid membranes or sulfonated hydro-
possible in the presence of alkaline electrolytes. carbon including inorganic fillers such as silica
Protons conducting electrolytes have been pre- rely on the water-assisted mechanism, they can
ferred to alkaline electrolytes for several decades operate up to 145 C, under particular conditions
for practical reasons, e.g., to avoid carbonation. (3 bar abs pressure), due to the enhanced water
The standard electrolyte membrane is usually a retention of the filler (Aricò et al. 2003).
perfluorosulfonic acid membrane such as Nafion. Composite recast Nafion® membranes
Most of the electrolytes alternative to Nafion both containing inorganic fillers have been employed
proton conducting and alkaline type, e.g., hydro- in high temperature (150 C) direct alcohol
carbon type, are significantly cheaper, and in (Aricò et al. 1998) and H2-air fuel cells
some cases, they are also characterized by (Watanabe et al.1996). These composite mem-
smaller hydrogen and methanol crossover. How- branes were originally developed for reduced
ever, lifetime characteristics similar to those humidification operation in polymer electrolyte
shown by Nafion-type membranes in fuel cells fuel cells (Watanabe et al.1996) due to the
have not yet been demonstrated for the alterna- enhanced water retention inside the membrane
tive membranes. Concerning with the conductiv- by the effect of the inorganic filler (Aricò
ity, only recently, membrane alternative to et al. 1998). A further advantage of composite
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_326-2
2 Ion Exchange Membrane for Fuel Cells
membranes relies in the barrier effect given by Aricò AS, Baglio V, Di Blasi A, Creti P, Antonucci PL,
the inorganic filler for methanol crossover (Ren Antonucci V (2003) Influence of the acid–base char-
acteristics of inorganic fillers on the high temperature
et al. 1996). performance of composite membranes in direct meth-
anol fuel cells. Solid State Ionics 161:251–265
Ren X, Wilson MS, Gottesfeld S (1996) High performance
References direct methanol polymer electrolyte fuel cells. J
Electrochem Soc 143:L12
Wang J, Wasmus S, Savinell RF (1995) Evaluation of
Aricò AS, Cretı̀ P, Antonucci PL, Antonucci V (1998) ethanol, 1-propanol, and 2-propanol in a direct oxida-
Comparison of ethanol and methanol oxidation in a tion polymer-electrolyte fuel cell. J ElectrochemSoc
liquid-feed solid polymer electrolyte fuel cell at high 142:4218
temperature. Electrochem Solid-State Lett 1:66–68 Watanabe M, Uchida H, Seki Y, Emori M, Stonehart P
Aricò AS, Srinivasan S, Antonucci V (2001) DMFCs: (1996) Self-humidifying polymer electrolyte mem-
from fundamental aspects to technology development. branes for fuel cells. J Electrochem Soc 143:3847
Fuel Cells 1:133
I
Irreversible Flux Decline decline (given by the change in J/DP), and this
can be used for both constant pressure and con-
Tony Fane stant flux operation. However, it is important to
School of Chemical Engineering, The University note that fouling is flux driven. As a result it is
of New South Wales, UNSW, Sydney, NSW, more appropriate to compare membranes at the
Australia same initial flux for constant pressure tests. Fig-
Singapore Membrane Technology Centre, ure 1a illustrates two membranes, M1 and M2,
Nanyang Technological University, Singapore, where M1 has an initially higher permeability
Singapore and starts at a higher flux. Fluxes for M1 and
M2 both decline due to the increasing fouling
resistance (see ▶ Irreversible Fouling Resis-
Membranes are either operated at constant pres- tance), and both membranes asymptote to similar
sure (P) or constant flux (J); the former is more declined fluxes. This is due to the eventual dom-
typical of lab scale studies and the latter of com- inance of the fouling resistance (RF) over the
mercial operation. Fouling leads to flux decline membrane resistance (Rm) (see Eqs. 1 and 2 in
under constant pressure or a rise in the required ▶ Irreversible Fouling Resistance). If membranes
transmembrane pressure DP for constant flux. M1 and M2 were tested at the same constant flux,
These trends are illustrated in Fig. 1. It should it would be easier to identify if one was intrinsi-
be noted that fouling under constant pressure cally less prone to fouling.
becomes self-limiting; the lower the flux, the
slower the fouling. For constant flux operation,
the fouling can be self-accelerating, often leading
References
to a sudden rise in TMP (DP) as shown for case
(ii) in Fig. 1b. This “TMP jump” could be asso- Fane AG, Chong TH, Le-Clech P (2009) Fouling in mem-
ciated with a critical consolidation of the fouling brane processes, Chapter 6. In: Drioli E, Giorno
layer and rapid rise in fouling resistance. Irrevers- L (eds) Membrane operations, innovative separations
ible flux decline is the drop in flux due to irre- and transformations. Wiley-VCH, Weinheim. ISBN
978-3-527-32038-7
versible fouling. The effect of irreversible fouling
can also be expressed as irreversible permeability
a b
M1
FLUX
TMP
(i)
M2 (ii)
Time Time
Flux vs time for Constant Pressure operation Pressure vs time for Constant Flux operation
Irreversible Flux Decline, Fig. 1 Constant pressure and constant flux operation: fouling trends
I
Irreversible Fouling a CB b CB
Resistance, Fig. 1 (a)
Concentration
polarization – clean
membrane. (b) Cake-
enhanced concentration
Shear
polarization – fouled Cake
membrane
CW1 CW2
Membrane
CP1 CP2
Hybrid Regenerated Cellulose/ The LNPs used in this study were prepared by
Loaded Lipid Nanoparticle the ultrasound method (Feng and Huang 2001)
Membranes: Preparation using L-a-phosphatidylcholine and Tween ® 80 as
and Characterization surfactants and glyceryl tristearate as the main
lipid component, while sunscreen DHB
Juana Benavente1 and Juan Manuel López- (2,4-dihydroxybenzophenone) was the active
Romero2 organic component. The hybrid membrane was
1
Departamento de Fisica Aplicada I, Universidad obtained by embedding the DHBLNPs in a dense
de Malaga, Facultad de Ciencias, Malaga, Spain highly hydrophilic regenerated cellulose
2
Departamento de Quimica Organica, (RC) support by immersion in a water dispersion
Universidad de Malaga, Facultad de Ciencias, of DHBLNPs (membrane RC/DHBLNPs). The
Malaga, Spain incorporation of the loaded LNPs was character-
ized by AFM, brilliant field microscopy (Fig. 1a),
TEM (Fig. 1b), and Raman spectroscopy
New membrane systems related to medical appli- (Vázquez et al. 2011; Hierrezuelo et al. 2012).
cations (drug-release devices, mimetic mem- Reductions in material characteristic parameters
branes, or patches) are receiving great attention (conductivity and dielectric constant) for dry
(M€ uller et al. 2000). Among them, lipid RC/DHBLNP samples when compared with the
nanoparticles (LNPs) prepared using biocompat- original RC and changes associated to thermal
ible components and with tunable properties are effects were also obtained.
of significant interest (Gupta and Kompella 2006; The stability of the hybrid membrane as a
Huynh et al. 2009); although, their use is still result of both contact time with NaCl solutions
limited due to stability problems during contact and osmotic pressure gradients was established
with biological fluids, storage, or administration by comparing diffusional permeability (Ps) for
(Korting and Schäfer–Korting 2010). To over- original RC and RC/LNP membranes (Vázquez
come these limitations, polymeric nanosphere et al. 2011; Hierrezuelo et al. 2012). The presence
gels were proposed for topical delivery of lipo- of the DHBLNPs reduces in approximately 20 %
philic molecules (Martins et al. 2007). In this Ps values for the whole interval of feed concen-
context, the inclusion of functionalized lipid trations studied (0.001 Cf(M) 0.4), and a
nanoparticles (FLNPs) in support to biocompati- constancy in the NaCl flow for at least 20 h was
ble membranes (such as regenerated cellulose also observed. The cellulose structure also
membranes) offers an attractive route for con-
trolled release of pharmacologic agents.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_338-3
2 Hybrid Regenerated Cellulose/Loaded Lipid Nanoparticle Membranes
reduces the DHB delivery from the loaded LNPs, Huynh NT, Passirani C, Saulnier P, Benoit JP (2009) Lipid
being the value for the hybrid membrane 5 % of nanocapsules: a new platform for nanomedicine. Int
J Pharm 379:201–219
that for the DHBLNPs (after 30 min). Korting HC, Schäfer–Korting M (2010) Carriers in the
topical treatment of skin disease. Handb Exp
Pharmacol 197:435–468
References Martins S, Sarmento B, Ferreira DC, Souto EB
(2007) Lipid–based colloidal carriers for peptide and
protein delivery–liposomes versus lipid nanoparticles.
Feng SS, Huang G (2001) Effects of emulsifiers on the Int J Nanomedicine 2:595–607
controlled release of paclitaxel (Taxol ®) from M€
uller RH, Mäder K, Gohla S (2000) Solid lipid
nanospheres of biodegradable polymers. J Control nanoparticles for controlled drug delivery – a review
Release 71:53–69 of the state of the art. Eur J Pharm Biopharm
Gupta RB, Kompella UB (2006) Nanoparticle technology 50:161–177
for drug delivery. Taylor and Francis/CRC Press, New Vázquez MI, Peláez L, Benavente J, López-Romero JM,
York Rico R, Hierrezuelo J, Guillén E, López-Ramı́rez MR
Hierrezuelo J, Benavente J, López–Romero JM, Martı́nez (2011) Functionalized lipid nanoparticles-cellophane
de Yuso MV, Rodrı́guez–Castellón E (2012) Prepara- hybrid films for molecular delivery. J Pharm Sci
tion, chemical and electrical characterizations of lipid 100:4815–4822
nanoparticles loaded with dihydroxybenzophenone.
Med Chem 8:541–548
L
Liquid Membrane
Separation, Fig. 1 Three BLM
configurations of liquid
membrane systems: bulk
(BLM), supported R
F E
(immobilized) (SLM or
ILM), and emulsion
(ELM). F is the source or Porous
Porous
feed phase, E is the liquid Support
Support
membrane, and R is the
receiving phase
SLM
E
F
R
Porous
Support
ELM
E R
F F
a pressure difference, an electric field, or temper- first two types are the modifications of the SLM,
ature considerably intensifies the process. and the third is the modification of BLM.
There are several different directions in LM According to the transport mechanisms, the LM
separation classifications: according to module techniques may be divided into simple transport,
design configurations (see ▶ SLM, ▶ ELM, facilitated or carrier-mediated transport, coupled
▶ BLM entries), according to transport mecha- counter- or cotransport, and active transport.
nisms (see ▶ LM Transport Mechanisms), According to applications, the LM techniques
according to applications, according to carrier may be divided into (1) metal separation-
type, and according to membrane support type. concentration, (2) biotechnological product
Below, these types of classifications are recovery-separation, (3) pharmaceutical product
described and discussed briefly. recovery-separation, (4) organic compound sep-
According to configuration definition, three aration and organic pollutant recovery from
groups of liquid membranes are usually consid- wastewaters, (5) gas separations, (6) fermentation
ered (see Fig. 1): bulk (BLM), supported or or enzymatic conversion-recovery-separation
immobilized (SLM or ILM), and emulsion (bioreactors), (7) analytical applications, and (8)
(ELM) liquid membrane transport. Some authors wastewater treatment including biodegradation-
add to these definitions polymeric inclusion separation techniques.
membranes, gel membranes, and dual-module Classification according to carrier type is as
hollow-fiber membranes, but, to my opinion, the follows: (1) water-immiscible, organic carriers,
Liquid Membrane Separation 3
(2) water-soluble polymers, (3) electrostatic, Module design configurations are used as a
ion-exchange carriers, and (4) neutral, but polar- rule as basic classification.
izable carriers. Practically, there are a lot of opportunities for
Classification according to membrane support liquid membrane separation processes in many
type is as follows: (1) neutral hydrophobic, areas of industry. The most interesting develop-
hydrophilic membranes, (2) charged ments for industrial membrane technologies are
(ion-exchange) membranes, (3) flat sheet, spiral related to the possibility of integrating various
module membranes, (4) hollow-fiber membranes, membrane operations in the same industrial
and (5) capillary hollow-fiber membranes. cycle, with overall important benefits in terms
of product quality and plant compactness.
M
dead-end
cross-flow with optimum
surface renewal
0,00E+00
0 100 200 300
TIME [s]
References
Manganese Removal by Liquid and alkaline earth metals are powerful oxidizers,
Membranes so that they are used as a bactericide and algaecide
in water treatment and as an oxidant in organic
Argurio Pietro chemical synthesis. Since manganese is used in
Depatment of Environmental and Chemical these and other different industrial processes, its
Engineering, University of Calabria, Arcavacata separation and/or recovery from the various liquid
di Rende (CS), Italy effluents or wastewater is of practical value.
A variety of separation processes for metal ions
have been developed for industrial needs, includ-
Manganese is the chemical element having the ing precipitation, inorganic and polymeric adsorp-
symbol Mn and atomic number 25. It is an essen- tion, evaporation, and reverse osmosis. Such
tial trace nutrient in all forms of life: it serves as a techniques produce water within international
necessary constituent of metalloproteins includ- health standards but entail some drawbacks.
ing enzymes since it optimize enzyme and mem- Solvent extraction procedures have proven to
brane transport function. Although the toxicity of be very useful in the separation and/or recovery of
manganese compounds is lower than those of metal ions from aqueous media, but they involve
other widespread metals, such as nickel and cop- high capital and operating costs due to large
per, both its excess and deficiency in the body can inventory of solvent, especially in the case of
cause serious impairment of vital physiological dilute solutions. Thus liquid membrane has been
and biochemical processes. Excessive manganese proven to be a very powerful technology.
intake is most frequently associated with the A liquid membrane (LM) is a layer of an
so-called manganism, a rare central nervous sys- organic phase (the so-called LM phase) that sep-
tem disorder, characterized by symptoms similar arates two aqueous solutions. An extractant
to Parkinson’s disease (weakness, monotone and (carrier), promoting the so-called facilitated trans-
slowed speech, tremor, disorientation, memory port from the donor phase (feed) to the acceptor
impairment, anxiety, and hallucinations). phase (strip), may be dissolved in the organic
Manganese compounds, in which it has vari- phase (Molinari et al. 2009a, b). LM-based pro-
ous oxidation states, are widely used in the indus- cesses offer a technology with a lot of advantages
try. Manganese dioxide is used in dry cell batteries over conventional separation techniques. The
as a depolarizer and in glassmaking as a drying main advantages are (i) combination of extraction
agent. Depending on their oxidation state, manga- and stripping processes in a single stage, resulting
nese ions have various colors and are used indus- in a low solvent consumption; (ii) uphill transport
trially as pigments. The permanganates of alkali against concentration gradient; and (iii) small
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_347-7
2 Manganese Removal by Liquid Membranes
amounts of extractant needed, resulting in the Considering the very low concentration of trace
possibility to use very selective carriers, which elements (manganese in our case) in these fluids, a
sometimes are not very cheap. pre-concentration step before analysis is required.
A widely used important acidic extractant in According to results from a recent study (Soko
hydrometallurgy in metal separation and/or recov- et al. 2003), the D2EHPA-based supported liquid
ery is di(2-ethylhexyl)phosphoric acid membrane technique can be used to extract and
(D2EHPA). It is extensively used also in the pre-concentrate Mn(II) from water, milk, and
extraction and recovery of manganese from neu- blood serum.
tral and weakly acidic solutions using supported
liquid membrane and emulsion liquid membrane
(Mohapatra and Kanungo 1992). Some studies
References
(Yongtao et al. 1992) considered the simultaneous
extraction and concentration of cadmium and Mohapatra R, Kanungo SB (1992) Kinetics of Mn
manganese from aqueous solutions obtaining (II) transport from aqueous sulphate solution through
recoveries of cadmium and manganese in the a supported liquid membrane containing di
range of 92–100 %. Recently a novel method for (2-ethylhexyl) phosphoric acid in kerosene. Sep Sci
Technol 27:1759–1773
Mn(II) extraction from sulfuric acid solutions has Molinari R, Argurio P, Poerio T (2009a) Studies of various
been proposed (Sadyrbaeva 2011) which involves solid membrane supports to prepare stable sandwich
electrodialysis and a bulk liquid membrane liquid membranes and testing copper(II) removal from
containing D2EHPA as the carrier. To accelerate aqueous media. Sep Purif Technol 70:166–172
Molinari R, Argurio P, Poerio T (2009b) Flux enhancement
the ion transfer through the liquid ion-exchange of stagnant sandwich compared to supported liquid
membrane, an electric field was applied. Operat- membrane systems in the removal of Gemfibrozil
ing in this way, the electrodialytic process from waters. J Membr Sci 340:26–34
(unselective) was coupled with the liquid Sadyrbaeva TZ (2011) Hybrid liquid
membrane – electrodialysis process for extraction of
membrane-based process, which provides greater manganese(II). Desalination 274:220–225
selectivity and permeability with respect to the Soko L, Chimuka L, Cukrowska E, Pole S (2003) Extrac-
traditional solid ion-exchange membrane. Com- tion and preconcentration of manganese(II) from bio-
plete removal of Mn(II) from a feed solution logical fluids (water, milk and blood serum) using
supported liquid membrane and membrane probe
containing 0.01 mol/L of MnSO4 and a maximum methods. Anal Chim Acta 485:25–35
extraction degree of 88 % was obtained under Yongtao L, Aixia W, Van Loon JC, Barefoot RR
optimized conditions. (1992) Extraction and enrichment of cadmium and
manganese from aqueous solution using a liquid mem-
brane. Talanta 39:1337–1341
Matrimid ® Membranes, Table 1 Typical permeation properties of Matrimid 5218 (David et al. 2011)
Permeability of pure gases (Barrera) Ideal selectivity
Po2 PN2 O2/N2
1.32–1.34b 0.185b 7.2b
1 Barrer = 1010 cm3 (STP) cm cm2 S1 cmHg1 = 7.5 1018 m3 (STP) m m2 S1 Pa1,
a
O O
O
C C CH3
C
N N
C C n
H3C CH3
O O
properties that are strongly affected by the gas modifications were conducted on the Matrimid
separation operating conditions such as pressure membrane including the incorporation of
and temperature that are likely relied to the mesoporous silica molecular sieve (Kenneth
changes in density, and consequently in the free et al. 2002), bromination (Guiver et al. 2002;
volume, of the polymer itself (Rowe et al. 2009; Xiao et al. 2005), blending with other polymers
David et al. 2011). Hence, the presence of minor (Chung et al. 2003), thermal treatment
components in the feed flow, such as impurities (Krol et al. 2001), and chemical cross-linking
or water vapor, can strongly affect the gas trans- (Tin et al. 2003).
port mechanism, thus altering the separation per- Due to the excellent properties shown by
formances (Chen et al. 2011). Moreover, its Matrimid membrane, which is desirable for gas
glassy nature may lead to plasticization phenom- separation process, therefore it is worth to accel-
ena at high fugacity of gases and vapors and to erate relevant modifications on this promising
aging phenomena that decrease the performances membrane for better separation performance.
upon time (Tin et al. 2003). These shortcomings
limit the Matrimid membrane application partic-
ularly in gas separation processes. Due to this
References
awareness, numbers of modification have been
reported by researchers to improve the Matrimid Aziz F, Ismail AF (2010) Preparation and characterization
membrane properties in order to fulfill the gas of cross-linked Matrimid ® membranes using para-
separation performance requirement particularly phenylenediamine for O2/N2 separation. Sep Purif
to surpass the Robeson boundary line (Basu Technol 73:421–428
Basu S, Cano-Odena A, Vankelecom IFJ (2010) Asym-
et al. 2010). The idea to modify the Matrimid metric Matrimid ®/[Cu3(BTC)2] mixed-matrix mem-
membrane was initiated by the good processabil- branes for gas separations. J Membr Sci 362:478–487
ity of the polymer itself owing to its carbonyl Chen QG, Scholes CA, Qiao GG, Kentish SE
functional groups (see Fig. 1) that may lead to the (2011) Water vapor permeation in polyimide mem-
branes. J Membr Sci 379:479–487
donation of electrons to form good interaction with Chung TS, Chan SS, Wang R, Lu Z, He C (2003)
certain electron acceptors (Chung et al. 2003). The Characterization of Permeability and Sorption in
Matrimid ® Membranes 3
Matrimid/C60 Mixed Matrix Membranes. J Membr isopropanol through pervaporation process. Chem Eng
Sci 211:91–99 Res Des 90:433–441
David OC, Gorri D, Urtiaga A, Ortiz I (2011) Mixed gas Nistor C, Shishatskiy S, Popa M, Nunes SP (2008) Com-
separation study for the hydrogen recovery from H2/ posite membranes with cross-linked matrimid selec-
CO/N2/CO2 post combustion mixtures using a tive layer for gas separation. Environ Eng Manag
Matrimid membrane. J Membr Sci 378:359–368 J7:653–659
Ding X, Cao Y, Zhao H, Wang L, Yuan (2008) Fabrication Rowe BR, Freeman BD, Paul DR (2009) Physical aging of
of high performance Matrimid/polysulfone dual-layer ultrathin glassy polymer films tracked by gas perme-
hollow fiber membranes for O2/N2 separation. ability. Polymer 50:5565–5575
J Membr Sci 323:352–361 Shishatskiy S, Nistor C, Popa M, Nunes SP, Peinemann
Dong G, Li H, Chen V (2011) Plasticization mechanisms KV (2006) Comparison of asymmetric and thin-film
and effects of thermal annealing of Matrimid hollow composite membranes having Matrimid 5218 selec-
fiber membranes for CO2 removal. J Membr Sci tive layer. Desalination 199:193–194
369:206–220 Sridhar S, Veerapur RS, Patil MB, Gudasi KB,
Guiver MD, Thi NL, Robertson GP (2002) Composite Gas Aminabhavi TM (2007) Matrimid polyimide mem-
Separation Membranes. U S Patent 20020062737. branes for the separation of carbon dioxide from meth-
Jiang L, Chung TS, Li DF, Cao C, Kulprathipanj S (2004) ane. J Appl Polym Sci 106:1585–1594
Fabrication of Matrimid/polyethersulfone dual-layer Tin PS, Liu Y, Wang R, Liu SL, Pramoda KP
hollow fiber membranes for gas separation. J Membr (2003) Effects of cross-linking modification on gas
Sci 240:91–103 separation performance of Matrimid membranes.
Kenneth J, Balkus Jr, Cattanach K, Musselman IH, J Membr Sci 225:77–90
Ferraris JP (2002) Selective matrimid membranes Wind JD (2002) Improving polyimide membrane resis-
containing mesoporous molecular sieves. MRS tance to carbon dioxide plasticization in natural gas
Proc. doi:10.1557/PROC-752-AA4.3. Accessed 2011 separations. PhD Thesis, The University of Texas at
Krol JJ, Boerrigter M, Koops GH (2001) Polyimide hol- Austin
low fiber gas separation membranes: preparation and www.ciba.com
the suppression of plasticization in propane/propylene www.huntsman.com
environments. J Membr Sci 184:275–286 Xiao Y, Dai Y, Chung T-S, Guiver MD (2005) Effects of
Mosleh S, Khosravi T, Bakhtiari O, Mohammadi T (2012) brominating matrimid polyimide on the physical and
Zeolite filled polyimide membranes for dehydration of gas transport properties of derived carbon membranes.
Macromolecules 38:10042–10049
M
Membrane Artificial Organs, Fig. 1 Comparison of hemodialysis polyethersulfone membrane (a) with glomerular
membrane (b)
membranes with respect to the clearance of “mid- membrane. (b) Spiral oxygenators utilized silicon
dle” molecules like b2-microglobulin that is membranes that are rolled around a central axis.
known to be associated with many dialysis- (c) Hollow fiber oxygenators are manufactured
related disorders. A variety of synthetic polymers with microporous polypropylene membranes,
and modified cellulosic materials including constituted by hollow fibers or capillary. This is
polysulfone (PSF), polyethersulfone (PES), poly- the most common type of oxygenator used
amide (PA), polyacrylonitrile (PAN), cellulose currently.
triacetate (CTA), and hemophan (HP) have been The most common membranes for blood oxy-
used for preparing hemodialysis membranes genator have been engineered in order to have
(Humes et al. 2006; Su et al. 2008). morphology close to the pulmonary alveoli. For
Extracorporeal blood oxygenators are used to example oxygenator polypropylene membranes
oxygenate the blood during open-heart surgery. have massive reticulated surfaces deployed as
Today, the vast majority of these blood oxygen- fine, porous, open-cell foams, which remind the
ators use hydrophobic microporous hollow fiber saccular form of the alveoli and the very thin
membranes to separate the blood and gas phases. alveoli septa (Fig. 2). In the natural lung, blood
Oxygen diffuses from the gas phase through the flows through fine capillaries in the alveoli and
gas-filled membrane pores into the blood. Oxy- exchanges O2 and CO2 across a barrier made up
gen in the blood plasma binds to hemoglobin of capillary endothelial cells; in oxygenators
present in the red blood cells. Consequently the blood flows on the outside of a large bore fiber,
rate of oxygen transfer is enhanced compared to with diameter of 300 mm, and exchanges respira-
the oxygenation of water where the oxygen does tory gases across a meniscus that forms across the
not react in the liquid phase (Lewandowski membrane pore at the interface of blood and gas.
2000). The diffusion of these gases inside the oxy-
Membrane oxygenators in current use utilize genator depends on the type of material of the
microporous, silicon, or polypropylene mem- membrane and on its thickness and porosity, but
branes. Currently, there are three principal types it is also influenced by the thickness of the layer
of oxygenator: (a) Plaque oxygenators are built of blood in contact with the membrane and by the
with microporous membranes of expanded poly- characteristics of the blood flow
propylene, folded in a Z shape. In these appara- (Wickramasinghe et al. 2005).
tuses, blood and gas flow in opposite sides of the
Membrane Artificial Organs 3
Membrane Artificial Organs, Fig. 2 Comparison of oxygenator polypropylene membrane (a) with pulmonary alveoli (b)
surface. Therefore, the response of the cell behav- of a physiological environment requires the use
ior depends on the surface properties of the used of membranes with specific physicochemical,
membrane (Morelli et al. 2010). For this reason, morphological, and transport properties on the
membranes should be chosen not only on the basis of the targeted tissue or organ (De Bartolo
basis of their separation properties but also on et al. 2012).
the basis of physicochemical and morphological
surface properties. Membrane bioartificial organs
are engineered to be used as extracorporeal
References
devices or implantable systems. These devices
can be distinguished on the basis of membrane De Bartolo L, Leindlein A, Hofmann D, Bader A, de
material configuration, molecular weight cutoff Grey A, Curcio E, Drioli E (2012) Bio-hybrid organs
or pore size, and cell culture technique. Cells can and tissues for patient therapy: a future vision for 2030.
be compartmentalized in the lumen or shell of Chem Eng Process: Proc Intensif 51:79–87
Drioli E, De Bartolo L (2006) Membrane bioreactor for
hollow fiber membranes (HFMs) or between flat- cell tissues and organoids. Artif Organs
sheet membranes, in a network of HF mem- 30(10):793–802
branes, spirally wound module, encapsulated or Jagur-Grodzinski J (2006) Polymer for tissue engineering,
attached to microcarriers. medical devices and regenerative medicine. Concise
general review of recent studies Polym. Adv Technol
The most common membranes used in the 17:395–418
membrane bioartificial organs are hydrophilic Morelli S, Salerno S, Piscioneri A, Campana C, Drioli E,
membranes with molecular weight cutoff ranging De Bartolo L (2010) Membrane bioreactors for regen-
from 20,000 to 120,000 daltons, which are chosen erative medicine: an example of the bioartificial liver.
Asia Pac J Chem Eng 5(1):146–159
on the basis of the molecules that have to provide
to the cells and removed from them. The creation
M
When membranes are used in bioartificial sys- cytocompatibility of the membrane can be
tems (bioartificial organs and tissues), it is impor- increased by modulating its surface free energy
tant to consider the cytocompatibility of and roughness (De Bartolo et al. 2002). It has
membrane on which depends the response of the been shown a significant enhancement of the
biological components. In bioartificial systems, hepatocyte adhesion and metabolic functions on
cells come into contact with the membrane sur- membrane with high value of surface free energy
face. Therefore, their morphological and func- base parameters.
tional response depends on the surface and
transport membrane properties. Physicochemical
properties, including surface composition,
References
charge, energy, and morphology, may affect cell
adhesion and behavior. In vivo cells are De Bartolo L, Morelli S, Bader A, Drioli E (2002) Eval-
surrounded by the extracellular matrix (ECM) uation of cell behaviour related to physico-chemical
that provides physical architecture and mechani- properties of polymeric membranes to be used in
cal strength to the tissue. The native ECM bioartificial organs. Biomaterials 23(12):2485–2497
De Bartolo L, Gugliuzza A, Morelli S, Cirillo B,
exhibits from macro- to nanoscale patterns of Gordano A, Drioli E (2004) Novel PEEK-WC mem-
chemistry and topography. For this reason, the branes with low plasma protein affinity related to sur-
cells can respond to various chemically and/or face free energy parameters. J Mater Sci Mater Med
topographically patterned features. When cells 15:877–883
De Bartolo L, Morelli S, Lopez L, Giorno L, Campana C,
are cultured in vitro, they receive very different Salerno S, Rende M, Favia P, Detomaso L, Gristina R,
physical, chemical, and mechanical stimuli from d’Agostino R, Drioli E (2005) Biotransformation and
the unfamiliar surrounding environment. Micro- liver specific functions of human hepatocytes in cul-
and nanoscale mechanical properties of the mem- ture on RGD-immobilised plasma-processed mem-
branes. Biomaterials 26(21):4432–4441
branes are critical because the cells not only De Bartolo L, Morelli S, Rende M, Salerno S, Giorno L,
adhere to the surface but also pull on the surface Lopez LC, Favia P, d’Agostino R, Drioli E (2006)
substrate and on adjacent cells. The surface Galactose derivative immobilized glow discharge
chemistry of the membrane affects the adhesion processed PES membranes maintain the metabolic
activity of human and pig liver cells. J Nanosci
of cells through the ECM protein adsorption and Nanotechnol 6:2344–2353
stereospecific chemical interactions. Several Salerno S, Piscioneri A, Laera S, Morelli S, Favia P,
approaches have been undertaken to improve Bader A, Drioli E, De Bartolo L (2009) Improved
the cytocompatibility of membranes by increas- functions of human hepatocytes on NH3
Plasma–grafted PEEK-WC-PU membranes. Biomate-
ing the wettability or by surface modification rials 30:4348–4356
through grafting of functional groups or immobi- Ulhenbusch I, Bonnie-Schorn E, Grassmann A, Vienken
lization of peptides, and proteins, which interact J (2004) Understanding membranes and dialysers.
with the cell receptors (De Bartolo et al. 2005, Pabst Science Publishers, Lengerich
2006, Salerno et al. 2009). It is known that the
S
Solubility, Table 1 Units used for solubility C of fluids vapor/liquid saturation point of the pure solute at
in membranes. 1 solute, 2 solvent the same temperature:
g1/g2
g1/cm3a
2
mol1/mol2
f i ðT, p, yi Þ low pyi
mol1/g2 ai ¼ ! (1)
f 0i T, pi, SAT ðT Þ pressure pi, SAT ðT Þ
mol1/cm3a
2
cm31(STP)/cm32
STP standard temperature and pressure, 1 atm and 25 C, For pure liquid solute phases, the solubility, as
1 cm3(STP) = 4.461 105 mol many other liquid-state properties, is to all prac-
a
Usually cm3 of pure solvent tical purposes a weak function of pressure, and its
value can be assumed unique at a fixed
temperature.
For multicomponent liquid solute phases, the
the original solute phase, which can be expressed activity ai can be used, being gi the activity
with different quantities depending on the state of coefficient:
aggregation of such phase. Some examples are
given below.
ideal mixture
For a gaseous solute phase, the fugacity fi or ai ¼ x i g i xi (2)
the partial pressure pi, if the gas phase is ideal,
is used. References
For a vapor solute phase, the activity (ai) is
preferentially used, i.e., the ratio between the Czichos H, Saito T, Smith L (2006) Experimental
measurement of gas and vapor sorption. In: Springer
fugacity in the current state and the fugacity in a
handbook of materials measurement methods.
reference state, that is usually chosen to be the Springer, Berlin, pp 381–385
M
Membrane Biosorption, Table 2 The isotherms of biosorption equilibrium (Pagnanelli et al. 2003)
Isotherm Equation
Langmuir q ¼ qmax 1þbC
bC
1
Freundlich q ¼ k Cn
1
Langmuir–Freundlich q ¼ qmax bCn
1
1þbCn
1 1 1
Radke and Prausnitz q ¼ aC þ bCn
Reddlich–Peterson q ¼ 1þbC
aC
n
(Koltuniewicz and Bezak 2002). The membranes next part shows the equations needed to calculate
allow for easy concentration of finely ground the membrane biosorption process.
biosorbents (Fig. 1) or cells (Fig. 2), which is
impossible in the thick layer of packed columns.
Very fine grinding is desirable because of the
Calculations of Membrane Biosorption
possibility of increasing the surface of sorption
Process
and shortening of the diffusion paths to active
sites. This increases the efficiency of sorption,
The obvious drawback of membrane biosorption
even in dilute suspensions. However, the costs of
is the quick saturation of the thin layer of
milling and additional operations such as drying,
biosorbent on membrane surface is rapidly
sorting, etc. should always be taken into account.
progressing with time, until equilibrium is
So in order to make real use of biosorption, the
reached. The equations describing the equilibrium
calculations must be performed in any case. The
and kinetics for biosorption process can be
Membrane Biosorption 3
Membrane Biosorption, a
Fig. 1 Equilibrium
adsorption of copper ions to
the pine sawdust (a). Effect
of temperature (b) and pH
(C). (A) Photomicrograph
of pine sawdust used for the
biosorption of copper ions.
(B) Effect of temperature on
biosorption of copper ions
on the sawdust. (C) Effect
of pH on biosorption of
copper ions on the sawdust
b 24
22
20
18
16
14
q [mg/g]
12
10
8
6
4 T = 20
T = 30
2 T = 40
0
0 20 40 60 80 100
C [mg/I]
c 24
22
20
18
16
14
q [mg/g]
12
10
4 pH = 5.0
pH = 4.0
2 pH = 3.0
0
0 20 40 60 80 100
C [mg/I]
4 Membrane Biosorption
Membrane Biosorption, Table 3 Kinetic equation of the biosorption (Pagnanelli et al. 2003)
Reaction type Equation
First-order reaction qðtÞ ¼ q 1 ekt
1
Pseudo-second order reaction q ð tÞ ¼ 1
þt
kq q
Membrane Biosorption, Table 4 Experimentally determined constants m and n in correlation between rate of surface
renewal and average cross-flow velocity in different types of modules (Koltuniewicz 1995)
Module type Constant – m Constant – n
Plate and frame (slot 0.15 0.001 m) 0.00074 0.75
Tubular ceramic (Membralox ® 19 tubes) 0.0020 0.80
Capillary (Romicon ®, d = 1 mm) 0.0035 0.66
determined on the basis of experimental data (see permeates flow results in a superposition of two
Tables 1, 2, 3, and 4 in Fig. 1). effects: (1) the tendency to reduce the concentra-
The concentration in the biosorbent (q) tion of xenobiotic in the permeate due to its
varies with time, due to its saturation with solute biosorption and (2) the tendency to increase the
(i.e., xenobiotic), which can be expressed in the concentration as a result of inflow of xenobiotic,
formula: with the liquid. Thus, the relationship has a min-
imum of the xenobiotic concentration in the per-
qðtÞ ¼ q ðq0 q Þ ekt meate after biosorption:
Where:
2 3
ðkþsÞtp ðdJ þsÞtp
61 e 1e 7 k X m d ð q qR Þ s
P ¼ CR 4
Cm 5
kþs J Jkd 1 estp
þs
d
6 Membrane Biosorption
1,50E–04
dead-end
cross-flow with optimum surface renewal
0,00E+00
0 100 200 300
TIME [S]
Membrane Biosorption, Fig. 3 Purity of permeate after the process of membrane biosorption in dead-end and cross-
flow modes of operation
Membrane Contactor a b
(MC), Fig. 1 Interface in a
hydrophobic (a) and
hydrophilic (b) membrane
contactor and transport of
the species i through the i i
membrane micropore
Membrane Contactor (MC), Table 1 Main advantages and drawbacks of membrane contactors
Main advantages Main drawbacks
High compactness Membrane resistance to the mass transport
Known and stable interfacial area Membrane fouling and loss of membrane properties (like
hydrophobicity)
No need of units downstream for phases Operating pressures dependent on the breakthrough pressure value
separation
Flexibility and modularity
Membrane Distillation (MD) system (Fig. 2). The driving force of the process
is linked to the vapor-pressure gradient between
Francesca Macedonio the two membrane sides.
Institute on Membrane Technology, National The documented and expected benefits
Research Council of Italy, ITM-CNR, University resulting from MD are as follows:
of Calabria, Renede (CS), Italy
– The nature of the driving force and the hydro-
repellent character of the membrane allow the
Membrane distillation (MD) is a thermal mem- theoretically complete rejection of nonvolatile
brane operation known for more than 50 years components such as macromolecules, colloi-
(first patent was filed by Bodell on 3 June 1963 dal species, and ions.
(Findley 1967); first MD paper was published – Lower temperatures with respect to those usu-
4 years later by Findley (Bodell 1963)). During ally used in conventional distillation column
the last years, the number of papers published on are sufficient to establish interesting trans-
MD and the research groups focusing on MD membrane flux, with consequent reduction of
studies have been increasing (Fig. 1). energy costs, thus allowing the efficient recy-
MD has great potential as a concentration pro- cle of low-grade waste heat streams as well as
cess at low temperature and energy with respect the use of alternative energy sources (solar,
to conventional processes, such as distillation and wind, or geothermal).
reverse osmosis (RO). MD allows the separation – Lower pressures with respect to those usually
of volatile components from solutions. If the utilized in RO because the required operating
solutions contain nonvolatile components, it is pressures are of the order of few hundred kPa.
possible to remove solvent by concentrating the Lower operating pressure translates to lower
solutions. equipment costs, increased process safety, and
In MD, one side (feed side) of a hydrophobic possibility of using plastic equipment, thus
membrane is brought into contact with a heated, reducing or avoiding erosion problems.
aqueous feed solution. The hydrophobic nature of – If compared to RO process, MD permeate flux
the membrane prevents penetration of the aque- is only slightly affected by the concentration
ous solution into the pores, resulting in a of the feedwater, and thus, productivity and
vapor–liquid interface at each pore entrance. performance remain roughly the same for high
Here, volatile compounds evaporate, diffuse concentration feedwaters. This means that
and/or convect across the pores, and are con- MD can be preferentially employed whenever
densed on the opposite side (permeate) of the elevated permeate recovery factors or high
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_361-2
2 Membrane Distillation (MD)
25
Number of article on MD published in Journal
20
of membrane Science
15
10
0
1987
1989
1991
1993
1995
1997
1999
2001
2003
2005
2007
2009
2011
Year
Membrane Distillation (MD), Fig. 1 Number of the papers published in Journal of Membrane Science on MD field
each year up to September 2011 (Drioli et al. 2012)
Membrane Distillation
(MD), Fig. 2 General
scheme of the MD process:
aqueous solution on feed
side whereas four different
solutions can be realized on
permeate side (aqueous
solution or air gap or
vacuum or sweeping gas)
(Lawson and Lloyd 1997)
Membrane Distillation
(MD), Fig. 3 Heat transfer
resistances in MD
1/hms
1/hmg
1/hf 1/hp
1/hV
Tf Tfm Tpm Tp
characteristic increases membrane life. New In MD process both heat and mass transfer
amorphous perfluoro polymers (e.g., Hyflon, phenomena occur through the membrane. Fig-
Teflon) can be also utilized neglecting their ure 3 illustrates the possible heat transfer resis-
still high costs. On the other hand, MD perfor- tances in MD with an electrical analogy.
mance (in particular the transmembrane flux Heat is first transferred from the heated feed
and the heat loss by conduction through the solution of uniform temperature Tf, across the
membrane) is intrinsically affected by the thermal boundary layer to the membrane surface
structure of the membrane in terms of thick- at a rate Q = hf ∙ DTf. At the surface of the
ness, porosity, mean pore size, pore distribu- membrane, liquid is vaporized and heat is trans-
tion, and geometry. ferred across the membrane at a rate QV = hV ∙
– Membrane fouling is less problematic in MD DTm = N ∙ DHV (where N is the rate of mass
than in other membrane separations because transfer and DHV is the heat of vaporization).
(i) the pores are relatively large compared to Additionally, heat is conducted through the mem-
RO/UF pores; (ii) the process liquid cannot brane material and the vapor that fills the pores at
wet the membrane – therefore, fouling layers a rate Qm = hm ∙ DTm where
can be deposited only on the membrane sur- hm ¼ e hmg þ ð1 eÞhms (e is the membrane
face but not in the membrane pores; and (iii) porosity; hmg and hms represent the heat transfer
due to the low operating pressure of the pro- coefficients of the vapor within the membrane
cess, the deposition of aggregates on the mem- pores and the solid membrane material, respec-
brane surface would be less compact and only tively). Conduction is considered a heat loss
slightly affect the transport resistance. mechanism because no corresponding mass
– On the contrary, one problem that can arise in transfer takes place. Total heat transfer across
MD is the membrane wetting which occurs the membrane is Q = QV + Qm. Finally, as
when the liquid penetrates into the membrane vapor condenses at the vapor–liquid interface,
pores. Once a pore has been penetrated, it is heat is removed from the cold-side membrane
said to be “wetted” and the membrane must be surface through the thermal boundary layer at a
completely dried and cleaned before the wet- rate Q = hp ∙ DTp.
ted pores can once again support a The overall heat transfer coefficient of the MD
vapor–liquid interface. process is given by
4 Membrane Distillation (MD)
Membrane Distillation
(MD), Fig. 4 Mass transfer
resistances in MD
viscous
surface
• Sarti correlation for laminar liquid flow in The resistances shown in Fig. 4 are arranged as
circular tubes with constant wall temperature: described by the dusty gas model (DGM), which
is a general model for mass transport in porous
media.
0:067 Gz
Nu ¼ 3:66 þ where
1 þ 0:04 Gz2=3 • Mass transfer across boundary layers
_ p
mc
Gz ¼ T A mass balance across the feed side bound-
K L ary layer yields the relationship between
(5) molar flux N, the mass transfer coefficient kx,
and the solute concentrations cm and cb at the
where Gz is the Graetz number, m_ is the mass flow
interface and in the bulk, respectively (Curcio
rate, cp is the liquid heat capacity, KT is the liquid
and Drioli 2005; Mya Tun et al. 2005):
thermal conductivity, and L is the length of the
tubes.
N cm
However, several empirical correlations exist ¼ kx ln (6)
r cb
which allow to estimate the boundary layer heat
transfer coefficients for other geometries and heat
where r is the solution density.
transfer mechanisms.
The method that is used in literature to
The heat transfer across the membrane has
determine the mass transfer coefficient is to
been already described. For what concerns the
employ an analogy between heat and mass
heat transferred by convection within the mem-
transfer. Therefore, Eqs. 4 and 5 can be used
brane pores, this can be also considered but is
to estimate boundary layer mass transfer coef-
negligible because convection accounts for, at
ficients by substituting the Sherwood number
most, 6 % of the total heat lost through the mem-
for the Nusselt number, the Schmidt for the
brane and only 0.6 % of the total heat transferred
Prandtl, and the mass transfer Graetz number
across the membrane (Lawson and Lloyd 1997).
for its heat transfer form. In general, the used
Regarding mass transfer, Fig. 4 illustrates the
correlations are as follows:
possible mass transfer resistances in MD using an
electrical analogy.
6 Membrane Distillation (MD)
Membrane Distillation
(MD), Fig. 5 Common Feed in permeate out Feed in Coolant out
configurations of the
Air gap
membrane distillation
Membrane
process that may be utilized Membrane
to establish the required
driving force (El-Bourawi
et al. 2006) Condensing plate
Sweep gas
Feed in out Feed in Vacuum
Permeate Permeate
Membrane Distillation
distillate channel
distillate channel
(MD), Fig. 6 Basic hydrophobic membrane condenser foil
channel arrangement and
membrane
condenser
temperature profile for TH
PGMD (Winter et al. 2011)
T1
coolant
hot feed
evaporator
P1 T0
TC
P0
distillate
– Direct contact MD (DCMD), in which the Some new configurations with improved
permeate is in liquid phase and, therefore, the energy efficiency, better permeation flux, or
membrane is on both sides directly in contact smaller footprint have been proposed such as
with aqueous solutions material gap membrane distillation, multi-effect
– Vacuum MD (VMD), in which the vaporized membrane distillation, multi-effect vacuum
solvent is recovered by vacuum and con- membrane distillation, permeate gap membrane
densed, if needed, in a separate device distillation, and hollow fiber multi-effect mem-
– Air gap MD (AGMD), in which an air gap is brane distillation.
interposed between the membrane and a con- Permeate gap membrane distillation (PGMD)
densation surface is an enhancement of DCMD in which a third
– Sweeping gas MD (SGMD), in which a strip- channel is introduced by an additional
ping gas is used as a carrier for the removal of non-permeable foil (Fig. 6).
the produced vapor (Fig. 5) One significant advantage of PGMD is the
separation of the distillate from the coolant.
The type of employed MD depends upon per- Therefore the coolant can be any other liquid,
meate composition, flux, and volatility: such as cold feedwater. This offers the opportu-
nity to integrate an efficient heat recovery system.
• SGMD and VMD are typically used to remove Multi-effect membrane distillation (MEMD)
volatile organic or dissolved gas from an aque- is based on the concepts of multi-stage and
ous solution. multi-effect distillation for seawater desalination.
• Because AGMD and DCMD do not need an The cold feed solution is placed beneath the con-
external condenser, they are best suited for densation surface as a coolant to condense the
applications where water is the permeated vapors as well as to gain heat at the
permeating flux. same time. The pre-heated feed solution is further
• The DCMD configuration, which requires the heated before it enters the feed channel.
least equipment and is simplest to operate, is Vacuum-multi-effect membrane distillation
best suited for applications such as desalina- (V-MEMD) is a modified form of VMD that
tion or the concentration of aqueous solutions integrates the concept of multi-effect distillation
(orange juice), in which water is the major into the VMD. As a general principle of the
permeate component. process, the vapors produced in each stage are
• AGMD, which is the most versatile MD con- condensed during the subsequent stages. Vapors
figuration, can be applied to almost any are generated in steam raiser working under vac-
applications. uum by exchanging the heat provided by external
source. The vapors are introduced in first stage
Membrane Distillation (MD) 9
where these are condensed by exchanging the availability of better membranes and to the pos-
heat with feed via a foil. The vapors generated sibility to utilize alternative energy sources in
in first stage are transported through the mem- niche applications.
brane and collected on the foil in the second
stage. It has been claimed that these modules
have excellent gained to output ratio which is
References
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hydrophobic membrane separates two aqueous tion 356:56–84
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appropriate for applications in the agro-food membrane distillation: modeling and concentration
experiments. J Membr Sci 166:1–11
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alternative and efficient approach to the tradi- R (2005) Membrane distillation crystallization of con-
centrated salts – flux and crystal formation. J Membr
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information can be found in Drioli et al. (2006), transfer mechanisms and transport resistances in direct
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277:186–194
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the recent and growing extensive research activ- distillation (V-MEMD) module. Desalination
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M
Membrane Distillation Applications, Table 1 Applications of MD mentioned in different recent studies (Reprinted
with permission from Drioli et al. 2015, Elsevier)
MD
Feed Target Used membranes configuration References
Seawater Boron removal PVDF DCMD Hou et al. (2013)
Simulated water Chromium removal PTFE DCMD Bhattacharya
et al. (2014)
Produced water Desalination PTFE DCMD Singh and Sirkar
(2012)
Aqueous solution of Concentration of PP VMD Shao et al. (2014)
N-methyl-2-pyrrolidone N-methyl-2-pyrrolidone
solution
Cooling tower blow-down Desalination FS PP DCMD Yu et al. (2013)
water
Aqueous ammonia solution Removal of ammonia PVDF capillary DCMD and Qu et al. (2013)
MDCMD
Olive oil waste mill water Concentration of FS PTEF DCMD Xie et al. (2013)
phenolic compounds
Produced water Desalination FS PTFE AGMD Alkhudhiri
et al. (2013)
Model lactose solution Ethanol production PP capillary DCMD Tomaszewska
membrane and Białończyk
(2013)
Synthetic solution of trace Removal of complex FS PTFE DCMD Wijekoon
OC trace organic et al. (2014)
compounds
Aqueous H2SO4 solution Concentration of H2SO4 PP hollow fiber Multi-effect Li et al. (2012)
solution MD
Retentate of NF and RO Improvement of water PVDF hollow DCMD Tun and Groth
RF and salt fibers (2011)
crystallization
Water from Great Salt Lake Recovery of minerals FS PTFE and PP DCMD Hickenbottom
and Cath (2014)
Zabłocka Thermal Brine Brine concentration PP hollow fiber DCMD Gryta (2013)
accrual
Glycerol fermentation broth Separation of acetic Accurel PP hollow DCMD Gryta
acid from the broth fiber et al. (2013)
Synthetic radioactive Removal of radioactive Hydrophobically DCMD Khayet (2013)
wastewater elements modified FS PS or
PES
Wastewater containing Removal of arsenic PP and PVDF FS VMD Criscuoli
arsenic in different et al. (2013)
concentrations
the concentration of acids (Tomaszewska 1993; (MDBR) for the treatment of industrial and
Tomaszewska et al. 1995; Tang et al. 2003). municipal used waters, in order to retain effec-
A list of innovative and potential uses of MD for tively small size and persistent contaminants
various applications mentioned in the recent liter- (Phattaranawik et al. 2008). The possibility to
ature is provided in Table 1. combine MD with the production of high-quality
More recently membrane distillation has been crystals extracted from the brine of nanofiltration
also used in membrane bioreactor configuration (NF) and reverse osmosis (RO) is particularly
Membrane Distillation Applications 3
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et al. (2011), Macedonio et al. (2007), and dilute ethanol separation from aqueous streams.
J Membr Sci 163:333–348
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in Japan and in the SeaHero project (Kim J 43(2):398–408
Bhattacharya M, Dutta SK, Sikder J, Mandal MK
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MD and PRO units have been proposed for the lation. J Membr Sci 450:447–456
extraction of valuable resources from the brine, Criscuoli A, Bafaro P, Drioli E (2013) Vacuum membrane
distillation for purifying waters containing
the minimization of the environmental impact of arsenic. Desalination 323:17–21
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branes in membrane distillation. Pure Appl Chem
58(12):1657–1662
Drioli E, Criscuoli A, Macedonio F (eds)
List of Symbols (2011) Membrane-based Desalination: an Integrated
Approach (MEDINA). Iwa Publishing, London
Drioli E, Ali A, Macedonio F (2015) Membrane distilla-
AGMD Air gap membrane distillation tion: recent developments and perspectives. Desalina-
DCMD Direct contact membrane distillation tion 356:56–84. doi:10.1016/j.desal.2014.10.028
FS PP Flat sheet polypropylene Duan SH, Ito A, Ohkawa A (2001) Removal of trichloro-
ethylene from water by aeration, pervaporation and
FS PS or PES Flat sheet polysulfone or
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recovery from hypersaline solutions. J Membr Sci
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Hou D, Dai G, Wang J, Fan H, Luan Z, Fu C (2013) Boron
treatment: application of air gap membrane distilla-
removal and desalination from seawater by PVDF flat-
tion. Desalination 309:46–51
sheet membrane through direct contact membrane dis-
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tillation. Desalination 326:115–124
acetone–butanol–ethanol (ABE) solvents from aque-
Khayet M (2013) Treatment of radioactive wastewater
ous solutions via membrane distillation. Bioprocess
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Eng 23(6):643–649
using surface modified membranes. Desalination
Banat FA, Simandl J (1996) Removal of benzene traces
321:60–66
from contaminated water by vacuum membrane distil-
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4 Membrane Distillation Applications
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157:297–305 C (2014) Experimental and theoretical research on
Khayet M, Mengual JI, Zakrzewska-Trznadel G (2006) N-methyl-2-pyrrolidone concentration by vacuum
Direct contact membrane distillation for nuclear desa- membrane distillation using polypropylene hollow
lination Part II. Experiments with radioactive solu- fiber membrane. J Membr Sci 452:157–164
tions. Int J Nucl Desalinat (IJND) 56:56–73 Singh D, Sirkar KK (2012) Desalination of brine and
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Kim S, Oh BS, Hwang M-H, Hong S, Kim JH, Lee S, Kim Effects of thermal and concentration boundary layers
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M
Membrane Distillation Bioreactor low molecular weight molecules do not leave the
(MDBR) reactor through the membrane, as they would
through MF or UF membranes in the conven-
Tony Fane tional MBR. This means that the organic reten-
School of Chemical Engineering, UNSW, The tion time (ORT) in the MDBR can be
University of New South Wales, Sydney, NSW, significantly longer than the hydraulic retention
Australia time (HRT) and recalcitrant organics are given
Singapore Membrane Technology Centre, longer to degrade. In contrast the conventional
Nanyang Technological University, Singapore MBR has ORT equal to HRT. The MDBR, in
common with other MBRs, typically has a small
“bleed”, or wastage, stream to maintain a steady-
The Membrane Distillation Bioreactor (MDBR) state concentration of mixed liquor suspended
combines a wastewater bioreactor with mem- solids (MLSS). The proportion wasted daily
brane distillation (MD) (Fane et al. 2012). It is determines the “sludge retention time” (SRT);
shown schematically in Fig. 1. The MDBR is a for example 5 % removal per day gives SRT of
member of the Membrane Bioreactor (MBR) 20 days, 10 % removal gives SRT of 10 days
family but with important differences from the etc. The accumulation of nonvolatile and
conventional MBR. The conventional MBR uses nonbiodegradable species in the reactor is deter-
microporous membranes, either microfiltration mined by the ratio of SRT/HRT, which represents
(MF) or ultrafiltration (UF), to retain biomass, the concentration factor and could exceed 20x.
or mixed liquor, within the reactor. The MDBR Retained salts can reach significant levels, but
employs a MD membrane to retain the mixed with acclimatization the biomass can cope.
liquor and provide the treated wastewater. The The MDBR can provide a high-quality treated
MDBR membranes can be either submerged in water, suitable for reuse. This is due to the unique
the bioreactor or located in a sidestream. An separation properties of the typical MD mem-
elevated temperature, typically 50–60 C, is brane. In common with other membrane pro-
used to drive water across the membrane and cesses, the MDBR can experience fouling, and
this means that thermophilic biomass are this can be controlled by bubbling and occasional
required. In addition the hydrophobic membrane cleaning. Experience indicates that the fouling is
retains nonvolatile salts that accumulate in the usually a combination of inorganic scale
reactor. Therefore the MDBR biomass need to (calcium salts) and biofouling. Fluxes of the
be salt tolerant (halotolerant). The MDBR con- order of 10 l/m2h can be sustained.
cept provides a “high retention” MBR, wherein
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_363-1
2 Membrane Distillation Bioreactor (MDBR)
W/Water
Negligible
TOC
Waste or Solar QIN
Heat QOUT
Biomass
(thermophilic) MD
Module
FS or HF
S Air
flux
illustrating the difference
between the flux decline
due to concentration concentration polarization
polarization and due to
membrane fouling
membrane fouling
time
hydrodynamic conditions (axial velocity) porous and thus permeable for aqueous solutions
(Bromley et al. 2002; Chen 1998; Ingmar as some inorganic precipitants or highly imper-
et al. 1999; Belfort et al. 1994). meable as some films of mineral oils or hydro-
When operating below the critical flux, it is phobic surfactants. The fouling mechanism
possible to observe a linear correlation between depends also on the membrane process. In elec-
flux and transmembrane pressure. Above it, fur- trodialysis fouling is caused mainly by the pre-
ther increase in transmembrane pressures lead to cipitation of polyelectrolytes or sparingly soluble
additional layer deposit on the membrane sur- salts such as CaSO4 or CaCO3. Membrane foul-
face, until a point where the deposit fully com- ing in electrodialysis affects mainly the anion-
pensates the increase in pressure drop. At this exchange membranes because most of the colloi-
stage the liming flux is reached, which represents dal and macromolecular polyelectrolytes present
the maximum stationary permeation flux. After in natural waters such as humic acids or proteins
operating above the critical flux value, decreasing are negatively charged. In ultra- and
the transmembrane pressure will not lead to the microfiltration of biological solutions, but also
previous flux behavior. in reverse osmosis of sea water, biological foul-
However, experimental evidences show that, ing is a severe problem affecting the economics
although operating at subcritical flux, gradual of the processes. In biomedical applications pro-
fouling develops in membrane materials, and it tein adsorption and protein denaturation at the
proves to be hydraulically irreversible after a membrane surface is often impairing the perfor-
long period experimentation (Ognier et al. 2004). mance of the membranes. In membrane distilla-
The formation of a gel or cake layer is one tion, adsorption of molecules can change surface
cause for membrane fouling. Gel or cake layer energy and hydrophobic properties.
formation may be caused by a variety of materials The difference between concentration polari-
including inorganic precipitates such as CaSO4, zation and membrane fouling or scaling is illus-
Fe(OH), and other metal hydroxides; organic trated schematically in Fig. 1.
materials such as proteins, humic acids, and Concentration polarization is a reversible pro-
other macromolecular materials; and biological cess based on diffusion and takes place over a few
components such as microorganisms and prod- seconds; it can be described adequately by a
ucts of their metabolism (biofouling). Membrane simple mathematical model and easily be con-
fouling may also occur without concentration trolled by the proper process design. Fouling is
polarization, i.e., a direct transport to the mem- generally irreversible and the flux decline takes
brane surface. The attachment of the substances place over many minutes, hours, or even days.
to the membrane surface may be caused by A constant flux is generally not reached at all.
adsorption due to hydrophobic interactions, van Membrane fouling is more difficult to describe
der Waals force attractions, or electrostatic and to control by experimental means. Membrane
forces. The fouling layer itself may be rather fouling is determined by a variety of different
Fouling 3
parameters including the feed solution constitu- instance, in hollow fiber modules, the elimination
ents and their concentration, membrane material, of all particulate materials is of great importance
and the fluid dynamic system design. Membrane for the proper function of the membrane.
fouling can be caused by simple precipitation of Membrane surface modifications include the
insoluble materials or reversible and irreversible introduction of hydrophilic moieties or charged
adsorption of components at the membrane sur- groups in the membrane surface by chemical
face and within the membrane pores. means or plasma deposition.
The means of preventing or at least controlling Increasing the shear rate imposed by the feed
membrane fouling effects are as heterogeneous as solution on the membrane surface will in many
the different material and mechanisms causing cases reduce the membrane fouling. High feed
the fouling (Ridgway et al. 1983; Nilson 1998). flow velocities and the proper module design are
The main procedures to avoid or control concen- efficient tools in controlling membrane fouling
tration polarization and fouling involve: (Fig. 3).
When in spite of an adequate membrane and
• Pretreatment of the feed solution module design the membrane flux is decreasing
• Membrane surface modifications with operation time to an unacceptable low value,
• Hydrodynamic optimization of the membrane it is necessary to clean the membrane to restore
module the flux in part or completely. Typical cleaning
• Membrane cleaning with the proper chemical agents are acids and bases, such as HNO3 and
agents NaOH, complexing agents, enzymes, and deter-
gents. Another very effective method to mini-
A list of various methods to reduce concentra- mize the effects of membrane fouling in
tion polarization is reported in Fig. 2. microfiltration is backflushing (Fig. 4). In
A pretreatment of the feed solution may backflushing, the applied pressure is reversed
include chemical precipitation, prefiltration, pH and the permeate is pushed through the mem-
adjustment, chlorination, or carbon adsorption. In brane, lifting off fouling material that had been
some membrane module, design concepts as, for precipitated on the feed side membrane surface
and washing it out of the filtration device.
4 Fouling
Fouling,
Fig. 4 Backflushing
method to reduce fouling Suspension Suspension
Backflushing
Jv
With
backflushing
Without
backflushing
t
Backflushing is done in certain time intervals for ultrafiltration: cause, consequences and control tech-
a couple of seconds. niques. In: Flinn JE (ed) Membrane science and tech-
nology. Plenum Press, New York, pp 47–97
Brian PTL (1966) Mass transport in reverse osmosis. In:
Merten U (ed) Desalination by reverse osmosis. MIT
Press, Cambridge, MA, p 161
References Bromley AJ, Holdich RG, Cumming IW (2002) Particulate
fouling of surface microfilters with slotted and circular
Bacchin P (2004) A possible link between critical and pore geometry. J Membr Sci 196:27
limiting flux for colloidal systems: consideration of Chen V (1998) Performance of partially permeable
critical deposit formation along a membrane. microfiltration membranes under low fouling condi-
J Membr Sci 235:111–122 tions. J Membr Sci 147:265
Belfort G, Davis RH, Zydney AL (1994) The behaviour of Cornelissen ER, Harmsen D, de Korte KF, Ruiken CJ, Qin
suspensions and macromolecular solution in crossflow J-J, Oo H, Wessels LP (2004) Membrane fouling and
microfiltration. J Membr Sci 98:1–58 process performance of forward osmosis membranes
Bian R, Yamamoto K, Watanabe Y (2000) The effect of on activated sludge. J Membr Sci 319:158–168
shear rate on controlling the concentration polarization Field RW, Wu D, Howell JA, Gupta BB (1995) Critical
and membrane fouling. Desalination 131:225–236 flux concept for microfiltration fouling. J Membr Sci
Blatt WF, Dravid A, Michaels AS, Nelsen LM (1970) Sol- 100:259
ute polarization and cake formation in membrane
Fouling 5
Hoek EMV, Elimelech M (2003) Cake-enhanced concen- Nilson JL (1998) Fouling of an ultrafiltration membrane
tration polarization: a new fouling mechanism for salt- by dissolved whey protein concentrate. J Membr Sci
rejecting membranes. Environ Sci Technol 36:147
24:5581–5588 Ognier S, Wisniewski C, Grasmick A (2004) Membrane
Howell J (1995) Subcritical flux operation of bioreactor fouling in sub-critical filtration conditions:
microfiltration. J Membr Sci 107:165 a local critical flux concept. J Membr Sci 229:171
Ingmar HH, Eert V, Gun T, Christian T (1999) The influ- Ridgway HF, Justice C, Kelly A, Olson BH (1983) Micro-
ence of the membrane zeta potential on the critical flux bial fouling of reverse osmosis membranes used in
for crossflow microfiltration of particle suspensions. advanced wastewater treatment technology: chemical,
J Membr Sci 156:153 bacteriological and ultrastructural analyses. Appl
Jonsson G, Boesen CE (1984) Polarization phenomena in Environ Microbiol 45:1066
membrane process. In: Belfort G (ed) Synthetic mem-
brane processes. Academic, New York
M
Membrane Reactor Equilibrium Conversion, Table 1 Thermodynamics table for water gas shift reaction (CO +
H2O = CO2 + H2) in an MR. Both reaction and permeating equilibrium are taken into account
Reaction CO H2O CO2 H2
Initial state n0 m n0 m1 n0 m2 n0
Reaction conversion x n0 x n0 x n0 x n0
Reactive equilibrium state n0 (1x) n0 (mx) n0 (m1 + x) n0 (m2 + x)
Permeation – – – z [n0 (m2 + x)]
Reactive and permeative equilibrium state n0 (1x) n0 (mx) n0 (m1 + x) n0[(m2 + x) (1z)]
Total mole number n0[1 + m + m1 + m2 z (m2 + x)]
Where, m > =x; x = MREC; z permeate hydrogen fraction
m, m1, and m2 are the feed molar ratio with respect to CO of H2O, CO2, and H2, respectively
volume. These variables have also to be taken This is the permeation equilibrium expressed as
into account for evaluating the equilibrium of an the equality of the chemical potentials (e.g., par-
MR. Nevertheless, another constrain is required tial pressures for a gas phase reaction) (Barbieri
for the equilibrium of an MR in addition to the et al. 2001, 2005; Marigliano et al. 2003) on both
one defined by Eq. 1 for the traditional reactor. membrane sides of any permeable species Eq. 2.
ChemicalPotentialEquilibrium
i ¼ ChemicalPotentialReaction
i ¼ ChemicalPotentialPermeation
i
Equilibrium (2)
Pressurei ¼ Pressurei
Reaction
¼ Pressurei
Permeation
8 permeable species
This condition is independent from the mem- the reaction(s) adding to it the terms related to
brane type and permeation rate. As chemical the permeative equilibrium.
equilibrium in a conventional reactor, and in an
MR as well, is independent from the reaction CO þ H2 O ¼ CO2 þ H2 DH0298
path, similarly the MR equilibrium is indepen-
¼ 41 kJ mol1
dent from permeation rate.
The hydrogen permeates Pd-based mem-
branes following the Sieverts law. Even though, Table 1 reports the thermodynamics table for
the membrane characteristics (e.g., Pd, Pd-Ag, calculating the equilibrium conversion of the
thickness, etc.) influence the permeation rate water gas shift reaction in a Pd-based MR, all
and hence the time necessary to reach the equi- the figures are in moles. The procedure for calcu-
librium, the value of these parameters does not lating the number of moles at the equilibrium is
affect the MR equilibrium. the one known since long time from chemistry as
The equilibrium depends on the extraction the fourth row “reactive equilibrium state” of
capacity of the membrane system which is a Table 1 shows. In fact, in absence of a membrane
function of the temperature, pressure, and com- this conversion is the one of a traditional reactor
position of the MR permeate volume that directly and here is identified as TREC. The presence of a
gives the condition of Eq. 2. selective membrane contributes to product
The MREC (Membrane Reactor Equilibrium (hydrogen) removal and hence to increase the
Conversion) can be easily calculated using the equilibrium conversion because of the mass law
constrains of Eqs. 1 and 2. MREC can be also effect or the Le Ch^atelier–Braun principle.
calculated using the thermodynamics table for Therefore, the equilibrium conversion of a
Membrane Reactor Equilibrium Conversion 3
Membrane Reactor Equilibrium Conversion, Table 2 Number of moles determination at reactive and permeative
equilibrium in a membrane reactor
Moles n-butane n-butene Isobutene Hydrogen
Initial state n0 – – –
Reactive state of reaction 1 n0 x n0x – n0 x
Reactive state of reaction 2 n0 x w n0 x w
Permeation state – – – n0 x z
Permeative and reactive equilibrium state n 0 ð 1 xÞ n0 x ð 1 w Þ n0 x w n0 x ð1 zÞ
Total number of moles n0 ð1 þ x xzÞ
Where, x = MREC for reaction 1, w = MREC for reaction 2, z permeate hydrogen fraction
The initial concentration of n-butene, isobutene, and hydrogen was chosen as zero
reactor conversion (here named MREC) is The other, permeative constrain Eq. 2 for the
always higher than TREC. MREC is equal to hydrogen, the only permeating species is
TREC in absence of any permeation.
The fifth row includes the term (z) for hydro- PEquilibrium
H2 ¼
gen permeation through a Pd-based membrane, n0 ½ðm2 þ xÞð1 zÞ
whereas the sixth row reports the moles present in PReaction
n0 ½1 þ m þ m1 þ m2 zðm2 xÞ
the reaction volume under the reactive and per-
meative equilibrium condition. CO conversion and the hydrogen fraction perme-
The total mole number in an MR owing to ate the membrane are calculated resolving this set
permeation is lowered by the reducing term of two equation in two unknowns: the conversion
{z [n0 (m2 + x)]} with respect to traditional (MREC) and the hydrogen permeated the
reactor. membrane.
The equilibrium constant of the reaction Another example of using thermodynamics
(reactive constrain, see Eq. 1) for WGS reaction table is reported for the n-butane dehydroisome-
considering the reactive and permeative equilib- rization (Al-Megren et al. 2013). This reaction
rium terms can be expressed as (reaction 3) involves the dehydrogenation of
n-butane (reaction 1) and successive isomeriza-
ðm1 þ xÞ½ðm2 þ xÞð1 zÞ tion to isobutene (reaction 2). The main products
KP ¼
ð1 x Þðm x Þ measured were normal butenes, isobutane, and
isobutene.
From the thermodynamics table (Table 2), after reaction 1 and reaction 2 and the permeation
some algebra, the equilibrium constants for equilibrium condition are:
4 Membrane Reactor Equilibrium Conversion
(3)
The concept of wettability (S) is referred to the
ability of a liquid to wet a surface (Hsu pffiffiffiffiffiffiffiffiffiffi
gAB
s ¼ 2 gþs gs
þ (4)
et al. 2011). The degree of wettability, also
known as a wetting or spreading, is controlled where the Lifshitz–van der Waals forces
by interfacial forces established between a liquid gLW[mJ/m2], polar gAB[mJ/m2], acid (electron
(L), solid (S), and vapor (V) phase at the mini- acceptor) g+[mJ/m2], and base (electron donor)
mum equilibrium distance. These interaction g[mJ/m2] are the components of the surface free
types are usually expressed as surface tensions energy g [mJ/m2] and can be calculated from
(g) and can be correlated to the wettability coef- mean values of the apparent contact angle (ya),
ficient by a mathematical equation: expressed in a somewhat simplified form by the
Young’s equation:
S ¼ gSV ðgSL þ gLV Þ (1)
gSV gSL
The surface tension, expressed as a force per unit cos ðYa Þ ¼ (5)
gLV
length [N/m] or energy per unit surface area
[J/m2], is a direct measurement of the cohesive It is a convention to consider y = 90 as a bound-
energy required for minimizing the free surface ary value between hydrophilicity and hydropho-
area at the interface, where the number of similar bicity. Values less than 90 indicate hydrophilic
species is more restricted than bulk and attractive membrane surfaces with a positive liquid spread-
forces are unequal and unbalanced in all direc- ing, whereas angle values higher than 90 are
tions (Fig. 1). measured on hydrophobic membrane surfaces
This parameter and related polar and nonpolar with negative spreading values (Fig. 2). Rolling
components can be estimated by a set of mathe- water droplets can be observed on super-
matical equations (Good and Van Oss 1992): hydrophobic surfaces with y > 150 and S<<0.
Substrate
Attractive forces
Membrane Wettability, Fig. 2 Water droplets on wettable (a), non-wettable (b), and super-hydrophobic surfaces
In all cases, the apparent contact angle can be In the Wenzel model, the surface grooves are
regarded as the result of combined morphological completely filled by the liquid and the contact
(i.e., tailed and loopy polymer segments, angle is determined by
grooves, and pores) and chemical (i.e., functional
binding or nonbinding sites) elements. Both two g gSL
cos ðYw Þ ¼ R SV (6)
contributions can go to the same or opposite gLV
direction, depending on the nature of the chemi-
cal and physical forces established at the inter- Combining this equation with the Young’s one, a
face. Normally, large membrane surface affinity simplified relation can be achieved:
toward a liquid produces extensive spreading,
while higher surface roughness minimizes cos ðYw Þ ¼ R cos ðYa Þ (7)
it. The roughness factor or rugosity (R) is associ-
ated with an irregularity of the membrane surface Instead, in the Cassie–Baxter model, grooves as
and can reduce the adhesion between liquid and well as pores are filled by air, which reduces the
substrate, causing an increase in the apparent adhesion line between liquid and substrate,
contact angle (Thomas 1999). In this respect, resulting in higher contact angle values:
Wenzel and Cassie–Baxter equations describe
the wettability better than Young’s equation, cos ðYCB Þ ¼ f s cos ðYa Þ þ f v cos ðYv Þ (8)
which is considered valid for ideal surfaces only
(Fig. 3).
Membrane Wettability 3
a b c
gLV Droplet
Droplet
gSV gSL Droplet qa qa
qa
d Zigzag profile
Membrane Wettability, Fig. 3 Effects of the roughness surface described by Wenzel equation, (c) a pillar surface
factor on the contact line between droplet and surface: (a) described by Cassie–Baxter equation, and (d) zigzag pro-
a flat surface described by Young’s equation, (b) a rough file section responsible for increased surface roughness
where ya is the angle measured on the flat surface, constantly pumped into (advancing mode, yadv)
whereas fs and fv are the fractions of the solid and and out (receding mode, yrec) a droplet in contact
vapor on the surface, respectively. with the membrane. The advancing contact angle
Some authors have proposed a “zigzag” geo- gives indirect indication about hydrophobic
metric model that corrects for roughness factor domains distributed throughout the surface; the
for contact angle measurements, thereby making receding one reveals the ability of local chemical
possible an evaluation of the surface chemistry moieties to rearrange when coming in contact
effects (Taniguchi and Belfort 2002). with the liquid phase. The hysteresis expresses
Contact angle measurements are powerful the difference between two plateau values, due to
tools able to reveal variations of the supramolec- chemical and morphological effects at the
ular chemistry owing to adsorption, fouling, liquid–surface interface.
affinity, or dry–wet switch taking place on the
membrane surfaces during separation processes.
In this respect, useful indication can be obtained
References
about the opportunity to put in contact mem-
branes with chemical streams without damages Good RJ, Van Oss CJ (1992) In: Schrader ME, Loeb GL
and/or special treatments. Cleaning against dirty (eds) Modern approaches to wettability. Plenum Press,
or chemical contaminations can be monitored as New York
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water vapor transport through block co-poly (amide/
order to detect the nature of the interfacial forces ether) membranes: effects on surface and bulk polymer
that control adhesion processes. Also, swelling properties. Eur Polym J 40/10:2381–2389
along with wetting and dewetting phenomena Gugliuzza A, Drioli E (2007) PVDF and HYFLON AD
can be studied under the action of specific trig- membranes: ideal interfaces for contactor applications.
J Membr Sci 300:51–62
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take the advantage of investigating all these E (2006) Study of the surface character as responsible
supramolecular changes in real time (Gugliuzza for controlling interfacial forces at membrane–feed
and Drioli 2007; Gugliuzza and Drioli 2004, interface. J Colloid Interface Sci 303(2):388–403
Gugliuzza A, Fabiano R, Garavaglia MG, Spisso A, Drioli
Gugliuzza et al. 2006, 2007). In static mode, a E (2007) Corrigendum to study of the surface character
predetermined volume of liquid is placed on the as responsible for controlling interfacial forces at
membrane surface and changes against time can membrane-feed interface. J Colloid Interface Sci
be monitored. In dynamic mode, the liquid is 306(1):192–193, vol 303, pg 388, 2006
4 Membrane Wettability
Hsu S-H, Woana K, Sigmund W (2011) Biologically Taniguchi M, Belfort G (2002) Correcting for surface
inspired hairy structures for superhydrophobicity. roughness: advancing and receding contact angles.
Mater Sci Eng R Rep 72/10:189–201 Langmuir 18:6465–6467
Thomas TR (1999) Rough surfaces, 2nd edn. Imperial
College Press, London
M
a b
Synthesis
Metal-Organic Frameworks (MOFs), Fig. 1 (a) Sche- Dr. Christian J. Doonan (University of Adelaide)). (b)
matic representation of how an extended MOF structure is Representative scanning electron micrograph of NH2-
built upon the assembly of metal (oxide) nodes and MIL-53 (Al) MOF crystals
organic linkers (Adapted from image courtesy of
Metal-Organic Frameworks (MOFs), Fig. 2 (a) Cross- focused ion beam, of a mixed matrix membrane. MOF
sectional scanning electron micrograph of a membrane crystals appear as lighter objects on the darker gray back-
incorporating a thin film of MOF crystals on a porous ground corresponding to the polymer matrix (Adapted
a-Al2O3 substrate (Adapted with permission from Ranjan from Rodenas et al. (2014)). The bottom-left inset shows
and Tsapatsis (2009), copyright (2009) American Chem- a close-up detail where the different components and
ical Society). (b) Scanning electron micrograph of an boundary voids have been labeled
internal cross section, exposed upon milling with a
efficient strategy for pest control results. Many product, by retaining flavors that would otherwise
varieties of oral and injected pharmaceutical for- evaporate and be readily lost.
mulations are microencapsulated as well – not Finally, when the core substances should be
only to effect release of the active component released only in certain circumstances (e.g., when
(s) over a longer period of time but also to guar- pH or temperature changes or when exposed to
antee release only at certain locations in the body. mechanical forces), smart membranes are
One example is aspirin, which can cause peptic selected. Successful examples are
ulcers and bleeding if doses are introduced all at microencapsulated fragrances that operate on
once: slow release decreases its detrimental risks the principle of scratch and sniff for release and
on the stomachal mucosa (Arshady 1993). some flavorings that must be protected from oxi-
Impermeable membranes have the active dation caused by exposure to light – so they
component encapsulated inside the membrane; should not be released prior to mastication
the chief purpose is to prevent release and thus (Obeidat 2009).
assure complete isolation from the environment.
This solution has been proven useful for phase
change materials targeted at textile and building References
industries: the said materials absorb or release
heat in response to changes in environmental Arshadi R (1993) Microcapsules for food.
temperatures – when temperatures rise, they J Microencapsul 10:413–435
Jackson LS, Lee K (1991) Microencapsulation and the
melt thus absorbing excess heat and causing a
food industry. Lebensm Wiss Technol 24:289–297
sensation of cool; conversely, as temperatures Jyothi NVN, Prasanna M, Prabha S, Ramaiah PS,
fall, phase change materials release heat as they Srawan G, Sakarkar SN (2009) Microencapsulation
solidify, thus providing a sensation of warmth. techniques. Internet J Nanotechnol 3. doi:10.5580/
27bb
This unique property of microencapsulated phase
Marini JO, Mendes RW, Rekhi GS, Jambhekar SS
change materials can be harnessed to increase the (1991) Some factors affecting the release of drug
comfort level of users of sports equipment and from membrane coated slow release tablets. Drug
military clothing; they have even been used in Dev Ind Pharm 17:865–877
Obeidat WM (2009) Recent patents review in microen-
NASA-patented thermal protection systems for
capsulation of pharmaceuticals using the emulsion
spacecraft. Additionally, the use of impermeable solvent removal methods. Recent Pat Drug Deliv
membranes is useful in retaining volatile flavors: Formul 3:178–192
encapsulation extends the shelf life of the food
M
Phase separation is generally grouped with Centrifugal extrusion processes generally lead
other chemical encapsulation techniques, despite to microcapsules of a larger size, typically from
realization that no actual chemical reaction is 250 mm up to a few mm. The core and membrane
usually involved in the process. It utilizes two materials (which are supposed to be immiscible)
polymers soluble in a common solvent, but are pushed through a spinning two-fluid nozzle;
which do not mix with each other in solution; this procedure forms an unbroken rope that natu-
hence, they form two separate phases – one rich rally splits into round droplets directly after clear-
in the polymer intended to form the membrane, ing the nozzle. The continuous walls of these
and the other rich in the incompatible polymer droplets are solidified either via cooling or by a
meant to induce phase separation. The latter will gelling bath depending on the composition and
not be a part of the finished microcapsule mem- features of the coating material.
brane, except for traces caught inside the capsule When applying the rotational suspension sep-
as impurities. aration (or spinning disk) method, the internal
During spray drying, an emulsion is prepared phase is dispersed into the liquid wall
by dispersing the core material (usually an oil or material – and the mixture is admitted onto a
active ingredient immiscible with water) into a turning disk. Droplets of pure membrane material
concentrated solution of membrane material until are thrown off of the rim of that disk – along with
the desired size of drops is attained. This emul- discrete particles of core material enclosed in a
sion is then atomized into a spray of droplets by skin of wall material. After solidification by
pumping the slurry through a rotating disk into cooling, the microcapsules are collected sepa-
the heated compartment of a spray drier: the rately from the particles of membrane material.
water portion of the emulsion consequently evap-
orates, thus yielding dried microcapsules of var-
iable shape and containing scattered droplets of
References
core material. The microcapsules are finally col-
lected via continuous discharge from the spray- Chabala M, Duckova K, Vitkova M (1978) Microcapsules
drying chamber. and micro-coated compressed tablets. I. Names, defi-
Fluid bed coating is restricted to encapsulation nitions and preparation methods of microcapsules.
Farm Obz 47:449–458
of solid core materials, including liquids
Jun-xia X, Hai-yan Y, Jian Y (2011) Microencapsulation
absorbed into porous solids. Such particles are of sweet orange oil by complex coacervation with
suspended on a jet of air and then covered by a soybean protein/gum Arabic. Food Chem
spray of liquid coating material; the microcap- 125:1267–1272
Klaassen R, Jansen AE (2001) The membrane contactor.
sules are then moved to an area to allow solidifi-
Environmental applications and possibilities. Environ
cation of their membranes via cooling or solvent Prog 20:37–43
vaporization. The process of suspending, Ocak B, G€ ul€
umser G, Baloğlu E (2011) Microencapsula-
spraying, and cooling may be iterated until the tion of Melaleuca alternifolia (tea tree) oil by using
simple coacervation method. J Essent Oil Res 2:58–65
walls attain the intended thickness. When the
Prasad R, Sarkar KK (1992) Membrane-based solvent
spray nozzle is located at the bottom of the fluid- extraction. In: Ho WSW, Sirkar KK (eds) Membrane
ized bed of particles, the process is usually known handbook. van Nostrand Reinhold, New York
as the Wurster process.
M
Continuous
terrace phase
dispersed phase
Glass plate
MC
Glass plate
Oil
Continuous
phase
Oil
Stagnant Continuous phase
Microchannel Emulsification, Fig. 1 Grooved-type MC plates for MC emulsification (Published with permission
from Vladisavljević et al. 2012)
Microchannel Emulsification, Fig. 2 Straight-through MC plates for MC emulsification (Published with permission
from Vladisavljević et al. 2012)
asymmetric structure. Symmetric MCs (Fig. 2a) size uniformity than circular MCs, and an aspect
are of the same size and shape (e.g., circular or ratio of the slots should be at least 3 (Kobayashi
rectangular) along the whole cross section of the et al. 2004). Asymmetric MC plate has circular
plate. Rectangular MCs provide higher droplet channels on the upstream (bottom) side and slots
Microchannel Emulsification 3
on the downstream (top) side (Fig. 2b). Asym- Kobayashi I, Mukataka S, Nakajima M (2004) Effect of
metric plate is useful when the dispersed phase slot aspect ratio on droplet formation from silicon
straight-through microchannels. J Colloid Interface
viscosity is less than 1 mPa s, e.g., when the Sci 279:277–280
dispersed phase is a volatile hydrocarbon Kobayashi I, Mukataka S, Nakajima M (2005) Novel
(Kobayashi et al. 2005). Straight-through asymmetric through-hole array microfabricated on a
micronozzle (MN) array (Fig. 2c) are used to silicon plate for formulating monodisperse emulsions.
Langmuir 21:7629–7632
increase the velocity of continuous phase around Kobayashi I, Wada Y, Uemura K, Nakajima M (2010)
the growing droplets during detachment, because Microchannel emulsification for mass production of
the channel outlets are above the plate surface, uniform fine droplets: integration of microchannel
which could be useful if the viscosity of the arrays on a chip. Microfluid Nanofluid 8:255–262
Sugiura S, Nakajima M, Kumazawa N, Iwamoto S, Seki
dispersed phase is high (Sugiura et al. 2005). M (2002) Characterization of spontaneous
transformation-based droplet formation during
microchannel emulsification. J Phys Chem
References B 106:9405–9409
Sugiura S, Oda T, Izumida Y, Aoyagi Y, Satake M,
Ochiali A, Ohkohchi N, Nakajima M (2005) Size
Kikuchi Y, Sate K, Ohki H, Kaneko T (1992) Optically control of calcium alginate beads containing living
accessible microchannels formed in a single-crystal cells using micro-nozzle array. Biomaterials
silicon substrate for studies of blood rheology. 26:3327–3331
Microvasc Res 44:226–240 Vladisavljević GT, Kobayashi I, Nakajima M (2012) Pro-
Kobayashi I, Nakajima M, Chun K, Kikuchi Y, Fujita duction of uniform droplets using membrane,
H (2002) Silicon array of elongated through-holes for microchannel and microfluidic emulsification devices.
monodisperse emulsion droplets. AIChE Microfluid Nanofluid 13:151–178
J 48:1639–1644
M
products. Owing to their chemical selectivity and impart a range of effects on the sensory profiles of
stereoselectivity, lipases may generate high foods: at very low addition levels, a sensation of
added-value products that are not readily avail- richness is obtained without any detectable acid-
able in natural feedstocks. ity; as addition levels increase, the resulting
The essential manufacturing steps of hydro- flavors resemble cream or butter; and when addi-
lyzed (or lipolyzed) milk fat include: preparation tion levels are even higher, the outcome flavor
of condensed milk or butter oil, preparation of suggests cheese.
standardized lipase system in water, combination
of milk fat substrate and lipase system, homoge-
nization to form a stable emulsion (thereby pro- References
moting maximum interfacial enzyme activity),
incubation at controlled temperature (until a Fox PF, McSweeney PLH (1998) Milk lipids. In: Fox PF,
McSweeney PLH (eds) Dairy chemistry and biochem-
specified degree of hydrolysis has been
istry. Blackie Academic/Professional Publishers, Lon-
achieved), pasteurization (to completely inacti- don, pp 67–146
vate residual lipase), and final standardization, Walstra P, Geurts TJ, Noomen A, Jellema A, van Boekel
spray drying (or alternative formulation), and MAJS (1999) Dairy technology, principles of milk
properties and processes. Marcel Dekker, New York
packaging.
Controlled enzymatic hydrolysis of milk fat
has been a common practice in the dairy industry Further Reading
Balcão VM, Paiva AL, Malcata FX (1996) Bioreactors
to produce butter- or cheese-like products and with immobilized lipases: state of-the-art. Enzyme
flavor additives (Walstra et al. 1999). The intrin- Microb Technol 18:392–416
sic composition of lipolyzed milk fat can indeed
M
Mixed Conducting Membranes solid oxide fuel cell (SOFC), the membrane
material such as Ce0.8Gd0.2O2-d (CGO) shows
Juergen Caro only oxygen ionic conductivity and no electronic
Institute of Physical Chemistry and conductivity, and the electrons have to go there-
Electrochemistry, Leibniz University Hannover, fore an outer circuit, whereas the oxygen ions
Hannover, Germany move through the CGO. In the case of the poly-
mer electrolyte membrane (PEM) fuel cell, the
membrane material Nafion shows also only pro-
Synonyms ton conductivity (Grotthuss mechanism) but no
electronic conductivity, and also here the elec-
Electronic and ionic conductivity trons have to go an outer circuit, whereas the
A mixed conducting membrane can transport protons can diffuse through the hydrated Nafion
both electrons and ions as shown in the scheme pores.
below (Fig. 1); in most cases the ionic conductiv- Therefore, mixed conducting materials are
ity is based on oxygen ions or protons, but in often called materials with an inner shortcut
principle also other ions like halogenide or chal- since oxygen ions and electrons or protons and
cogenide anions are mobile and can be electrons move through the material.
transported. Perovskites with the crystallographic In the scheme below (Fig. 1), the phenomenon
structure ABO3 (derived from the mineral perov- of mixed conductivity is illustrated for a perov-
skite CaTiO3) are a prominent example for a skite membrane. On the membrane side with a
materials class with mixed conductivity: Oxygen high oxygen partial pressure (e.g., air), molecular
ions can be transported via vacancies in the oxy- oxygen is split at the surface into atoms, the
gen lattice (denoted as oxygen deficiency d in the atoms become ionized, and the oxygen ions
perovskite structure ABO3-d ), and electrons can occupy empty oxygen ion positions in the oxygen
be transported via redox cycles of the cations if lattice (vacancy) and become transported by a
they can occur in different oxidation states (e.g., diffusion mechanism to the membrane side with
Fen+, Con+, Tin+). The concentration of vacancies a lower oxygen partial pressure (vacuum, sweep
in the oxygen lattice can be engineered by bring- gas) where they back-transform into molecular
ing cations with a low valency on the position of oxygen. For most perovskites, the electronic con-
high-valency cations (Sunarso et al. 2008). ductivity is orders of magnitude higher than the
In contrast to mixed conducting membranes, ionic one.
the membranes used in fuel cells for electricity
generation show only ionic conductivity: In the
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_388-1
2 Mixed Conducting Membranes
Mixed Conducting Membranes, Fig. 1 Schema of place: The oxygen ions decompose into atomic surface
oxygen transport through a perovskite membrane with oxygen O* and electrons, and the latter diffuse to the air
mixed conductivity (copyright Caro, Uni Hannover): side where they are consumed in the oxygen ionization.
Molecular oxygen is split at the membrane side with The surface oxygen species O* dimerize and form molec-
high oxygen partial pressure (normally air) into atomic ular oxygen which is desorbed into the gas face. To keep
oxygen species O* which are adsorbed at the surface. the oxygen partial pressure low on the permeate side
After ionization, the oxygen ions O2 enter the mixed (driving force for permeation), the molecular oxygen has
conducting membrane material. By a diffusional hopping to be removed by pumping or a sweep gas; it can be
process among the vacancies in the oxygen lattice, the also consumed in a chemical oxidation reaction
oxygen ions can enter the membrane side facing a low (Shao et al. 2001)
oxygen partial pressure. Here the reverse process takes
O O
R
R HN O Cellulose
O OH
Cellulose Cellulose
O R
R H O
R NCO
O
O
OH O R
COONa X
OH R
TEMPO/NaBr/NaClO O HO
O Cellulose
Cellulose O
HO OH O
OH n
O O
HX R1 O R2
HNO3
O
X O R1(R2)
Cellulose Cellulose
NO2
O
Cellulose
Modified Cellulose, Fig. 1 Chemical modifications of cellulose for membrane science and technology
Mosaic Membranes, Fig. 1 Schematic draw of struc- exchange domains in anion-exchange matrix (middle),
ture of mosaic membrane configurations: cation- and and anion-exchange domains in cation-exchange matrix
anion-exchange domains in neutral matrix (left), cation- (right)
desalination – development to date and future poten- Nunes SP, Peinemann KV (2006) Membrane technology
tial. J Membr Sci 370:1–22 in the chemical industry. Wiley-VCH, Weinheim
Livazocic S, Behzad AR, Peinemann K-V, Nunes SP Petersen RJ (1993) Composite reverse osmosis and
(2015) Cellulose multilayer membranes manufacture nanofiltration. J Membr Sci 83:81–150
with ionic liquid. J Membr Sci 490:282–293
N
aggregate and improve their dispersion in poly- monomers, and then the monomers are polymer-
mer matrices. The main defects at the polymer- ized. There are often some functional groups such
particle interface, including interfacial voids or as hydroxyl or carboxyl on the surface of the
sieves-in-a-cage, rigidified polymer layer around inorganic particles, which can generate initiating
the particles and finally the particle pore block- radicals, cations or anions under high-energy
age. Surface modification of inorganic particles is radiation, plasma, or other circumstances to ini-
a popular technique because it produces excellent tiate the polymerization of the monomers on their
integration and an improved interface between surface.
inorganic filler and the polymer matrix. There In the phase inversion method, the preparation
are two main approaches for modification of the of nanocomposite membranes can be grouped by
surface of the nanoparticles: modification of the the following general procedure:
surface of the inorganic particles by chemical
treatment and grafting of functional polymeric • Separate preparation of a polymer solution
molecules to the hydroxyl groups existing on and a suspension of inorganic material.
the particles (Hong and Chen 2015). Basically • Mixing of both resulting in a mixed matrix
there are three general ways to prepare solution.
nanocomposite membranes, including: sol-gel • Casting solution is cast as film (or spinning)
process, in situ/interfacial polymerization and followed by phase inversion process. It can be
phase inversion method (Souza and Quadri induced by evaporation of solvent, immersion
2013). precipitation using nonsolvent, or by thermal
The sol-gel technique is the method most precipitation.
applied for the preparation of polymer-inorganic
nanocomposite membranes with highly homoge- The development of nanocomposite mem-
neous and controlled morphology. In this branes finds applications in different fields such
method, organic monomers, oligomers, or poly- as gas separation, pervaporation, fuel cell, pack-
mers and inorganic nanoparticle precursors are aging, and water and wastewater treatment. In
mixed together in the solution. The inorganic addition, nanocomposite membranes are of huge
precursors then hydrolyze and condense into interest to biomedical technologies such as con-
well-dispersed nanoparticles in the polymer trolled drug delivery, tissue engineering, dental
matrix. applications, and bone replacement/repair. In
In in situ/interfacial polymerization, the Table 1 are reported some types of
nanoparticles are well mixed with organic nanocomposite membrane and their applications.
Nanocomposite Membranes 3
Natural Gas Sweetening et al. 2001; White et al. 1995; Baker and
Lokhandwala 2008).
A. Baudot Several studies have been carried out since the
Physics and Analysis Division, IFP Energies adoption of membranes by natural gas operators,
Nouvelles, Solaize, France aiming at comparing membrane-based carbon
dioxide removal operations with conventional
absorption operations. Several trends can be
Introduction issued from these studies, depending on the var-
ious considered gas treatment scenari:
Though raw natural gas is mainly composed of
methane (generally from 75 % to 90 %), it also – Moderate natural gas flows (lower than
contains undesired components such as acid gas- 25,000–30,000 Nm3/h (Chapel and Mariz
eous impurities such as carbon dioxide or hydro- 1999; Mckee et al. 1991)) containing high
gen sulfide that should be removed in order to carbon dioxide concentrations: it appears that
prevent pipeline corrosion. membranes are more profitable than absorp-
tion processes. In 1995, it was shown that
commercial permeation membranes were
more competitive than DEA/MDEA-based
Permeation Membrane-Based CO2
absorption when the carbon dioxide content
Removal
was higher than 20 % (Meyer and Gamez
1995). Another study realized by Kelloggs &
Gas permeation constitutes the latest carbon
Co. sets this limit at approximately 16 % for a
dioxide extraction technology applied to natural
gas price of 1.5 USD/MMBtu (Mckee
gas treatment. Membranes offer several strong
et al. 1991).
advantages over conventional solvent columns:
– High natural gas flows with low carbon diox-
compacity (which makes membranes particularly
ide concentrations: absorption processes
well-suited for offshore operations (Cooley and
prove to be more profitable than gas perme-
Dethloff 1985)), low investment costs, low main-
ation modules.
tenance costs, and at least with single-stage con-
– High natural gas flows combined with high
figurations that do not operate compressors. The
carbon dioxide content: an association of
current level of commercial membranes CO2/
membranes and absorption seems to be the
CH4 selectivity is comprised between 12 and
most profitable option (McKee et al. 1991).
25 in field conditions (Baker 2002; Roman
Membrane modules, located before the
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_405-1
2 Natural Gas Sweetening
absorption column, carry out a bulk removal scale than at lab (Chatterjee et al. 1997; Orme
of carbon dioxide, while the absorption col- and Stewart 2005).
umns allow the final polishing of the
natural gas.
Membranes with a Selective Layer Made
of Block Polymers
This type of membrane materials has been prin-
Permeation Membrane-Based cipally studied by MTR Inc. which has developed
Hydrogen Sulfide Removal commercial spiral-wound membranes with a
selective layer made of various polyether block
Three main types of polymer membrane have amides (commercialized under the trademark
®
been only tested at lab scale or pilot scale in PEBAX by Arkema). Tests under industrial con-
order to remove hydrogen sulfide from ditions were conducted on production facilities
natural gas. operated by Shell and located in West Texas
(Amo et al. 1998). It was shown that the
®
PEBAX -based membranes/sulfatreat process
Membranes Based on Rubbery Polymer
association was leading to significant operation
Selective Layers
costs (from 20 % to 40 %) over amine process
This type of polymer materials generally offer
alone for flow gases containing few percents of
very high permeability values for low molecular
H2S and lower than 140,000 Nm3/h while a
weight components. The selectivity of this type ®
PEBAX membrane/amine coupling was more
of polymer is then essentially based on the affin-
valuable than a stand-alone amine process for
ity (i.e., the sorption coefficient) difference
gas flows containing more than 5 % H2S and
between several components to be separated. In
higher than 23,000 Nm3/h.
the literature, three main polymer families can be
identified:
Membranes with a Selective Layer Made
• Apolar rubbery polymers, such as silicones of Glassy Polymers
(PDMS and PTMSP). As a general rule, the Those stiff polymeric materials, used mainly for
H2S/CH4 selectivity of these materials is commercial carbon dioxide removal applications
rather modest, as methane diffuses more rap- (polyimides, cellulose acetate, polysulfones),
idly than hydrogen sulfide (Merkel have their selectivity mainly based on molecular
et al. 2001). sieving effects. Despite their affinity for polar
• Apolar rubbery polymers impregnated with compounds (those membranes are also
polar solvents: two patents have been issued recommended by membrane manufacturers for
by UOP in the mid-1980s about the use of gas dehydration applications), it appears that
PEG- or glycerol-impregnated silicone mem- those membrane materials have rather low H2S/
branes. The addition of polar solvent, which CH4 selectivities (Hao et al. 2008; Bhide
displays a high affinity for hydrogen sulfide, et al. 1998). This can be mainly attributed to the
leads to a very significant increase of the selec- fact that the kinetic diameters of hydrogen sulfide
tivity of these membrane materials toward and methane are rather close, resulting in close
hydrogen sulfide (Kulprathipanja and Sudhir values of their respective diffusion coefficients
1985; Kulprathipanja 1985). through glassy polymer-based selective layers.
• Polar rubbery polymers: these types of poly-
mer have mainly been studied by academic
teams and display high values of H2S/CH4
References
selectivities associated with high H2S perme-
abilities. To the authors’ knowledge, though, Amo K, Baker RW, Helm VD, Hofman T,
those materials have not been studied on larger Lokhandwala K, Pinnau I, Ringer M, Su TT, Toy L,
Natural Gas Sweetening 3
Wijmans JG (1998) Low-quality gas sulfur removal/ Kulprathipanja S (1985) Separation of gases from non
recovery.DOE final report DE-AC21-92MC28133-01 polar gases. US Patent 4,606,740
Baker RW (2002) Future directions of membrane gas Kulprathipanja S, Sudhir SS (1985) Separation of polar
separation technology. Ind Eng Chem Res gases from non polar gases. US Patent 4,608,860
41:1393–1411 Mckee RL, Changela MK, Reading GJ (1991) CO2
Baker RW, Lokhandwala K (2008) Natural gas processing removal – membrane plus amine. Hydrocarb Process
with membranes: an overview. Ind Eng Chem Res 47 70:63–65
(7):2109–2121 Merkel TC, Gupta RP, Turk BS, Freeman BD
Bhide BD, Voskericyan A, Stern SA (1998) Hybrid pro- (2001) Mixed-gas permeation of syngas components
cesses for the removal of acid gases from natural gas. in poly(dimethylsiloxane) and poly(1-trimethylsilyl-1-
J Membr Sci 140:27–49 propyne) at elevated temperatures. J Membr Sci
Chapel DG, Mariz CL (1999) In: Ernest J Recovery of 191:85–94
CO2 from flue gases: commercial trends. Oral Presen- Meyer HS, Gamez JP (1995) Gas separation membranes:
tation Canadian Society of Chemical Engineers coming of age for carbon dioxide removal from natural
Annual Meeting, Saskatoon, Sakatchewan, Canada, gas. Abstract of the 45th Laurence Reid gas condition-
October 4-6 1999 ing conference, pp 284–306
Chatterjee G, Houde AA, Stern SA (1997) Poly(ether Orme CJ, Stewart FF (2005) Mixed gas hydrogen sulfide
urethane) and poly(ether urethane urea) membranes permeability and separation using supported
with high H2S/CH4 selectivity. J Membr Sci polyphosphazene membranes. J Membr Sci
135:99–106 253:243–249
Cooley TE, Dethloff WL (1985) Field-tests show mem- Roman IC, Ubersax RW, Fleming GK (2001) New direc-
brane processing attractive. Chem Eng Prog 81:45–50 tions in membrane for gas separation. Chim Ind 83:1–3
Hao J, Rice PA, Stern SA (2008) Upgrading low-quality White LS, Blinka TA, Kloczewski HA, Wang IF
natural gas with H2S- and CO2-selective polymer (1995) Properties of a polyimide gas separation mem-
membranes – Part II. Process design, economics, and brane in natural-gas streams. J Membr Sci 103:73–82
sensitivity study of membrane stages with recycle
streams. J Membr Sci 320:108–122
n
NELF Model, Table 1 List of symbols and properties used in the NELF model
Symbol Name Definition/property
Pure component ri* Characteristic density of pure component i
i pi* Characteristic pressure of pure component i
Ti* Characteristic temperature of pure component i
ri0 Number of lattice sites occupied by a mole of pure component i r 0i ¼ rM vi
i i
i
pi
e* Characteristic energy e ¼ Tk
v* Average close-packed mer molar volume in the mixture v ¼ RT
p
e
r Dimensionless density e
r ¼ rr
T~ Dimensionless temperature T~ ¼ TT
p~ Dimensionless pressure p~ ¼ pp
Eq " #
A Total equilibrium Helmholtz free energy NXp þ1
AEq 1 1 fi
rNRT ¼ e
r þ T~ 1 lnð1 e
r Þ þ r lnðerÞ þ lnðfi Þ
er ri
i¼1
polymers are obtained from volumetric data one obtains solubility isotherms for pure pene-
above the glass transition temperature (Doghieri trants (Doghieri and Sarti 1996, 1998; Sarti and
and Sarti 1996; Sarti and Doghieri 1998); alter- Doghieri 1998; Giacinti Baschetti et al. 2001; De
native techniques have been proposed for the Angelis et al. 2007) as well as for mixed gases
polymers degrading before glass transition is (Doghieri et al. 2004b; Minelli et al. 2011), in
reached (Galizia et al. 2012). The pure compo- pure glassy polymers, in polymer blends (Grassia
nent parameters for gases are obtained from vol- et al. 2004), as well as in glassy-mixed matrices
umetric data; for vapors and liquids, vapor (Maria Grazia De and Sarti 2008; Maria-Chiara
pressure data are also used. et al. 2010). The model is also suitable to calcu-
A collection of pure component parameters late the solubility of liquids in glassy polymers
for polymers of interest in membrane separations (Sarti and De Angelis 2012).
is reported in Table 2, while for relevant pene- Whenever the binary interaction parameters
trants, pure component parameters are reported in are known from data above the glass transition
Table 3. The binary interaction parameters are temperature, and polymer density is known, the
generally used as fitting quantities, even though model is entirely predictive (Doghieri and Sarti
a predictive method has been proposed (Rodgers 1996; Sarti and Doghieri 1998). Under
and Sanchez 1993), and often the first order non-swelling conditions the polymer density
approximation of kij = 0 is also acceptable. remains equal to the value of the pure
Remarkably, the nonequilibrium model, using unpenetrated polymer (Doghieri and Sarti 1998;
T and rpol as input, is much less sensitive to the Giacinti Baschetti et al. 2001). At high pressures
binary parameter than the corresponding equilib- and for swelling penetrants, volume dilation of
rium model, using temperature and pressure as the polymers is required, e.g., through the use of a
input. swelling coefficient (Giacinti Baschetti
The phase equilibrium (or more properly et al. 2001). Remarkably, the model also shows
pseudo-equilibrium) conditions between the that in all cases, both at low and high free volume,
glassy nonequilibrium phase and an external it is sufficient to consider only molecules
fluid phase, either gaseous or liquid, are dissolved in the glassy phase, without the need
represented as usual: of an arbitrary differentiation between hypothet-
ically different populations of penetrant
ð SÞ ðexternal fluidÞ molecules.
mi ¼ mi (2)
The interested users can freely download the
By using Eq. 1 for the chemical potential of code for the solubility isotherms of binary mix-
species i dissolved in the glassy phase and usual tures (http://serwebdicma.ing.unibo.it/polymers/
equilibrium expression for the chemical potential index.htm).
of species i in the external fluid phase, from Eq. 2
NELF Model 5
NELF Model, Table 2 NELF model pure component parameters for different polymers
Symbol/ T* p* r*
acronym Name [K] [MPa] [g/cm3] Source
PC Poly(carbonate) 755 534 1.275 (Doghieri and
Sarti 1996)
TMPC Tetramethyl poly(carbonate) 761.6 446.4 1.174 (Doghieri and
Sarti 1998)
PMMA Poly(methyl methacrylate) 695 560 1.27 (Doghieri and
Sarti 1998)
PEMA Poly(ethyl methacrylate) 602 567.5 1.221 (Giacinti
Baschetti
et al. 2005a)
PPO Poly(2,6-dimethyl-1,4-phenylene oxide) 739 479 1.177 (Doghieri and
Sarti 1998)
PSF Poly(sulfone) 830 600 1.31 (Doghieri and
Sarti 1998)
PVAC Poly(vinyl acetate) 592 510 1.284 (Doghieri and
Sarti 1998)
PVC Poly(vinyl chloride) 736 415 1.458 (Doghieri and
Sarti 1998)
HFPC Hexafluoro poly(carbonate) 716.5 446 1.618 (Sarti and
Doghieri 1998)
AF1600 Tetrafluoroethylene (TFE) – 2,2-bis 575 280 2.16 (De Angelis
(trifluoromethyl)-4,5-difluoro-1,3-dioxole (BDD) et al. 2002)
(25–65 mol)
AF2400 Tetrafluoroethylene (TFE) – 2,2-bis 624 250 2.13 (De Angelis
(trifluoromethyl)-4,5-difluoro-1,3-dioxole (BDD) et al. 2002)
(13–87 mol)
PTFE Poly(tetrafluoroethylene) 618 371 2.25 (De Angelis
et al. 2002)
PS Poly(styrene) 750 360 1.099 (Sarti and
Doghieri 1998)
PEUT Poly(ether urethane) 550 450 1.132 (Giacinti
Baschetti
et al. 2003)
PTMSP Poly(trimethylsilyl propyne) 610 380 1.125 (Giacinti
Baschetti
et al. 2005b)
TMSP/ 1-trimethylsilyl-1-propyne/1-trimethylsilyl-1-n- 515 580 1.25 (Giacinti
TMSE hexyne 70/30 copolymer Baschetti
70/30 et al. 2005b)
TFE/ Tetrafluoroethylene – perfluoromethyl vinyl ether 509 395 2.244 (Prabhakar
PMVE49 (50.7–49.3 mol) et al. 2005)
PTMSN Addition type poly(trimethylsilyl norbornene) 406 360 1.345 (Galizia
et al. 2012)
LDPE Low density poly(ethylene) 693 400 0.883 (Giacinti
Baschetti
et al. 2005a)
6 NELF Model
NELF Model, Table 3 NELF model pure component parameters for different solutes
Symbol/acronym Name T* [K] p* [MPa] r* [g/cm3] Source
H2 Hydrogen 46 37 0.078 (Doghieri and Sarti 1998)
O2 Oxygen 180 214 1.25 (De Angelis et al. 1999)
N2 Nitrogen 145 160 0.943 (Doghieri and Sarti 1998)
He Helium 9.3 4 0.148 (De Angelis et al. 2007)
Ar Argon 190 180 1.31 (De Angelis et al. 2006)
Xe Xenon 304 351 3.36 (De Angelis et al. 2007)
CH4 Methane 215 250 0.5 (Doghieri and Sarti 1998)
CO2 Carbon dioxide 300 630 1.515 (Doghieri and Sarti 1998)
SO2 Sulfur dioxide 430 630 1.734 (De Angelis et al. 2006)
N2O Nitrous oxide 319 524 1.408 (De Angelis et al. 2007)
H2O Water 670 2,400 1.05 (De Angelis et al. 2007)
CH3OH Methanol 510 1,080 0.9 (De Angelis et al. 2007)
C2H5OH Ethanol 470 880 0.915 (De Angelis et al. 2007)
C3H7OH 1-propanol 500 700 0.913 (Galizia et al. 2012)
(CH3)2CO Acetone 484 533 0.92 (De Angelis et al. 2007)
CH3CN Acetonitrile 505 910 0.855 (Giacinti Baschetti et al. 2003)
VCM Vinyl chloride 450 390 1.115 (Doghieri and Sarti 1998)
CF4 Tetrafluoromethane 230 265 1.92 (De Angelis et al. 1999)
C2F6 Perfluoroethane 296 227 1.95 (De Angelis et al. 1999)
C3F8 Perfluoropropane 335 225 2.05 (De Angelis et al. 1999)
C6H6 Benzene 523 444 0.994 (De Angelis et al. 2007)
C7H8 Toluene 543 402 0.966 (Giacinti Baschetti et al. 2005a)
C2H4 Ethylene 295 365 0.68 (Doghieri and Sarti 1998)
C2H6 Ethane 320 330 0.64 (De Angelis et al. 1999)
C3H8 Propane 375 320 0.69 (De Angelis et al. 1999)
n-C4H10 n-Butane 430 290 0.72 (De Angelis et al. 2002)
n-C5H12 n-Pentane 451 304 0.752 (Prabhakar et al. 2005)
n-C6H14 n-Hexane 476 298 0.77 (Prabhakar et al. 2005)
c-C5H12 c-Pentane 478 389 0.88 (Prabhakar et al. 2005)
c-C6H14 c-Hexane 497 383 0.902 (Prabhakar et al. 2005)
n-C7H16 n-Heptane 498 295 0.780 (Galizia et al. 2012)
n-C8H18 n-Octane 502 308 0.815 (Sanchez and Lacombe 1976)
n-C9H20 n-Nonane 517 307 0.828 (Sanchez and Lacombe 1976)
n-C10H22 n-Decane 530 304 0.837 (Sanchez and Lacombe 1976)
n-C11H24 n-Undecane 542 303 0.846 (Sanchez and Lacombe 1976)
n-C12H26 n-Dodecane 552 301 0.854 (Sanchez and Lacombe 1976)
solubility and critical temperature in glassy polymers during sorption using FTIR-ATR spectroscopy. Mac-
based on the NE-LF model. Desalination 199:466–468 romolecules 36(25):9574–9584
De Angelis MG, Sarti GC, Doghieri F (2007) NELF model Giacinti Baschetti M, De Angelis MG, Doghieri F, Sarti
prediction of the infinite dilution gas solubility in GC (2005a) Solubility of gases in polymeric mem-
glassy polymers. J Membr Sci 289:106–122 branes. In: Galan MA, Martin del Valle E (eds) Chem-
Doghieri F, Sarti GC (1996) Nonequilibrium lattice fluids: ical engineering: trends and developments. Wiley,
a predictive model for the solubility in glassy poly- Chichester, pp 41–61
mers. Macromolecules 29:7885–7896 Giacinti Baschetti M, Ghisellini M, Quinzi M, Doghieri F,
Doghieri F, Sarti GC (1998) Predicting the low pressure Stagnaro P, Costa G, Sarti GC (2005b) Effects on
solubility of gases and vapors in glassy polymers by sorption and diffusion in PTMSP and TMSP/TMSE
the NELF model. J Membr Sci 147:73–86 copolymers of free volume changes due to polymer
Doghieri F, Quinzi M, Rethwisch DG, Sarti GC (2004a) ageing. J Mol Struct 739:75–86
Predicting gas solubility in glassy polymers through Grassia F, Giacinti Baschetti M, Doghieri F, Sarti GC
non-equilibrium EOS. In: Pinnau I, Freeman BD (eds) (2004) Solubility of gases and vapors in glassy poly-
Advanced materials for membrane separations, ACS mer blends. In: Pinnau I, Freeman BD (eds) Advanced
symposium series, vol 876. ACS, Washington, DC, materials for membrane separations, ACS symposium
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Doghieri F, Canova M, Sarti GC (2004b) Solubility of Lacombe RH, Sanchez IC (1976) Statistical thermody-
gaseous mixtures in glassy polymers: NELF predic- namics of fluid mixtures. J Phys Chem 80:2568–2580
tions. In: ACS Symposium Series, vol 733 (1999). Minelli M, Campagnoli S, De Angelis MG, Doghieri F,
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non-equilibrium EOS. In: Yampolskii Y, Pinnau I, Prabhakar RS, De Angelis MG, Sarti GC, Freeman BD,
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for gas and vapor separations. Wiley, New York, ation, and diffusion in poly(tetrafluoroethylene-co-
pp 137–158 perfluoromethyl vinyl ether). Macromolecules
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(2010) Gas and vapor transport in mixed matrix mem- Rodgers PA, Sanchez IC (1993) Improvement to the
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AF2400 and fumed silica. Ind Eng Chem Res liquids. J Polym Sci Polym Phys Educ 31:273
49:11920–11935 Sanchez IC, Lacombe RH (1976) An elementary molecu-
Galizia M, De Angelis MG, Sarti GC (2012) Sorption of lar theory of classical fluids. Pure fluids. J Phys Chem
hydrocarbons and alcohols in addition-type poly 80:2352–2362
(trimethyl silyl norbornene) and other high free vol- Sanchez IC, Lacombe RH (1978) Statistical thermody-
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(2003) Quantitative analysis of polymer dilation Chem Eng Sci 53:3435–3447
N
factors of the axon growth. After a trauma or an using stem cells. Neural stem cells (NSC) are
injury, the production of neuroprotective factors available from the hippocampus, spinal cord,
is quite limited and eventually not enough to fetal brain, and neural retina and due to the ability
oppose the two main mechanisms occurring in to self-renew can differentiate in neurons, astro-
the central nervous system. First, the apoptotic cytes, and oligodendrocytes in order to substitute
phenomena affecting the surrounding of the dam- cells lost in the injury. Amyotrophic lateral scle-
aged area over a great distance, due to the secre- rosis (ALS), spinal muscular atrophy (SMA),
tion of members of the transforming growth main motor neuron disorders, and Parkinson’s
factor family (TGF) that largely promote cell disease (PD) are the focus of the neural stem
death. Secondly, the proliferation of glial cells cell strategies. NSC not only can be integrated
in quiescent state and the consequent formation into host nervous system but also have been
of a glial scar acting as physical barrier for the engineered to act as delivery vehicle for
axonal regeneration. Astrocytes actually produce neuroprotective growth factors like the GDNF
and secrete specific factors, such as NOGO pro- and IGF-1, resulting in an increase of the spinal
teins, NI-35, chondroitin sulfate proteoglycans, motor and the dopaminergic neuron survival
and keratan sulfate proteoglycans, known to be (Tysseling and Kessler 2011). Pluripotent stem
inhibitors of the remyelination and axon repair cells have been also successfully used as strategy
(Steward et al. 2013; Allodi et al. 2012). Then, for the neuronal regeneration. They represent a
the modulation of the regenerative process in the perfect in vitro system for developmental studies
nervous system lies on different approaches and can be not only differentiated in neurons but
depending on the site and the extension of the reprogrammed to form stem cells facilitating the
injured area. Independently on the causes, an replacement of degenerated neurons from autol-
injury affects the nervous system with the inabil- ogous sources avoiding grafts rejection in the
ity of neuronal cells to transmit impulses to spe- patients (Steward et al. 2013).
cific regions of the nervous system. In order to Drug Delivery. Many natural and synthetic
restore the functionalization, one of the three molecules have shown to possess neuroprotective
specific repair mechanisms must occur: the and neurogenerative properties. The administra-
regrowth of the neuronal damaged axons, the tion of neurotrophic factors demonstrated an
recovery of the axonal function, or the substitu- improvement of the regenerative process in both
tion of the neurons that have been lost through the the central and the peripheral nervous systems.
generation of new neuronal cells. Each one of The intact blood-spinal cord barrier represents an
these regenerative methods stands as alternative obstacle in reaching the brain and the spinal cord,
to the gold standard treatments, represented by but generally after injuries or degenerative pro-
the coaptation and the nerve graft implantation. cesses, several parts result to be compromised;
The first one consists in the surgical reparation of therefore, neurotrophins and drugs administered
small nerve gap (<8 mm) resulting after an can overcome the barrier reaching the site of
injury, and the second one consists in the implan- action. Carrier, microcarrier, microspheres, lipo-
tation of grafts regardless the size of the gaps. somes, and hydrogels are the devices available
Generally autografts, which have no risk of for the controlled release, and synthetic or natural
immune reactions, are the first choice in the polymers, extracellular matrix derived biomate-
nerve injury treatment, but allografts and xeno- rials, carbon nanoparticles, and ions complexes
grafts are also available. Therefore, none of them represent only a few of the biomaterials usable
allow to reach a full functional recovery and for their preparations (Tysseling and Kessler
many drawbacks are possible. 2011; Gu et al. 2014). Moreover, not only spinal
Cell Replacement or Cell Therapy. When a cord and nerve regeneration have been achieved,
wide area of the nervous system has been dam- but due to this strategy central diseases such as
aged by a trauma or a degenerative pathology, a Parkinson’s and Alzheimer’s are possible. In fact,
replacement of the neuronal cells can be obtained the controlled release of dopamine and b-amiloid
Neuronal Regeneration 3
inhibitors represents today the best treatment order to induce the neurite outgrowth and axonal
available for the neurodegenerative pathologies regeneration in the insulated area. On similar
in combination with the cell transplantation. lines of the drug delivery, growth factors and
Moreover, in order to avoid multiple drug injec- neuroprotective agents are encapsulated in the
tions and to increase the delivery time in the scaffolds or incorporated in the biomaterials and
selected area, mini-pumps are available and sur- then let diffuse towards the severed site. This new
gically implantable in patients for the treatment approach increases the neural regeneration guid-
of the chronic pain and the degenerative diseases. ing the axonal growth in both the central and
Nerve Conduit, Scaffolds, and Channels. The peripheral nervous systems.
protection of the injured site from inhibitor fac- Despite the autografts still remain the gold
tors and apoptotic/inflammatory phenomena is of standard for the treatment of the nervous system
main importance in order to increase the regen- injuries, the promising results recorded in the
erative process in the nervous system. This is the biomaterials field represent the best alternative
reason why scaffolds, channels, and conduits in the development of new regenerative
have been purposely made to protect the severed approaches, based on the controlled drugs and
areas during the regeneration and tested in factors release, the guidance of the axonal
in vitro and in vivo studies. With the aim of regrowth, and the transplantation of cells in the
recreating a permissive environment for the selected area.
neurite and axonal growth, these synthetic
devices consisting of polymers and hydrogels in
form of tubes or fibers possess morphological, References
chemical-physical, and mechanical specific prop-
erties. Topography, mechanical strength, biodeg- Allodi I, Udina E, Navarro X (2012) Specificity of periph-
radation, porosity, and dimensions are necessary eral nerve regeneration- interactions at the axon level.
Prog Neurobiol 98:16–37
to induce cell adhesion, proliferation and differ-
Gu X, Ding F, Williams DF (2014) Neural tissue engi-
entiation, to allow the nutrient and growth factor neering for peripheral nerve regeneration. Biomate-
supply, to remove the metabolites and inhibitors, rials 35:6143–6156
and to avoid the device collapsing during the Morelli S, Salerno S, Piscioneri A, Papenburg BJ, Di
Vito A, Giusi G, Canonaco M, Stamatialis D,
regenerative process after the implantation
Drioli E, De Bartolo L (2010) Influence of
(Sedaghati et al. 2014; Morelli et al. 2010). Col- micropatterned PLLA membranes on the outgrowth
lagen, laminin, fibronectin, polycaprolactone, and orientation of hippocampal neuritis. Biomaterials
polylactic acid, and chitosan tubes are allowed 31:7000–7011
Sedaghati T, Jell G, Seifalian M (2014) Nerve regenera-
to build high-quality guides for the neural repair.
tion and bioengineering. In: Orlando G -
In addition, in the last decade, the nerve conduits (ed) Regenerative medicine applications in organ
have been further developed and leveled up transplantation. Elsevier, Waltham, pp 799–810
through the combination with supportive cells Steward MM, Sridhar A, Meyer JS (2013) Neural regen-
eration. Curr Top Microbiol Immunol 367:163–191
and the growth factors incorporation. Alterna-
Tysseling VM, Kessler JA (2011) Biomaterials for central
tively, neural stem cells and pluripotent cells are nervous system regeneration. Tissue Eng Neurol
seeded in the lumen of the tubes, and they stim- Neurosurg 533:455–466
ulate the release of diffusible growth factors in
N
techniques. Thanks to these characteristic, the LM phase, the pH of the feed phase, the
LM-based techniques permit to obtain the recov- stripping solution concentration (i.e., pH), the
ery of heavy metal ions and the production of flow rates of feed and stripping solution, and the
water with good quality, resulting into both envi- volumetric ratio of feed to stripping solutions
ronmental and economic benefits. represent the most important parameters affect-
The selective separation of nickel from vari- ing system selectivity (Lothongkum et al. 2009).
ous aqueous media containing nickel and cobalt, Two or more HFSLM modules can be placed in
that is, an important problem in hydrometallurgy, series, obtaining satisfactory nickel recovery and
can be carried out by using ELM (Longquan an aqueous effluent with concentration within the
et al. 1997; Kumbasar and Tutkun 2008). Ni and common permissible limits.
Co possess aqueous similar chemical behavior,
because they are metal of the transition series
adjacent in the periodic table, but some differ-
References
ences exist. In ammoniacal environment
(Kumbasar 2009) the complex Co(NH3)2+ is G€
uell R, Anticó E, Salvadó V, Fontàs C (2008) Efficient
readily oxidized to Co(NH3)3+ with addition of hollow fiber supported liquid membrane system for the
hydrogen peroxide, while the nickel complex Ni removal and preconcentration of Cr(VI) at trace levels.
(NH3)2+ is not oxidized. In these conditions the Sep Purif Technol 62:389–393
Hassaine-Sadi F, Graiche M, Boudaa A, Bouchabou
nickel ammine complex can be selectively H (2012) Purification-concentration process of Zn
extracted using an acidic extractant (e.g., (II), Ni(II) and Cd(II) using liquid membrane with
5,7-dibromo-8-hydroxyquinoline (DBHQ)) by different carriers. Proc Eng 33:351–356
the following reversible pH-dependent reaction: Kumbasar RA (2009) Selective extraction of nickel from
ammoniacal solutions containing nickel and cobalt by
emulsion liquid membrane using 5,7-dibromo-8-
NiðNH3 Þ2þ ðaqÞ þ 2 HRorg ¼ NiðNH3 ÞR2 þ 2 Hþ hydroxyquinoline (DBHQ) as extractant. Miner Eng
22:530–536
Kumbasar RA, Tutkun O (2008) Separation of cobalt and
The concentration of complexing agent (e.g., nickel from acidic leach solutions by emulsion liquid
ammonia) in the feed phase, the pH of the feed membranes using Alamine 300 (TOA) as a mobile
and of the strip aqueous phases, the composition carrier. Desalination 224:201–208
Longquan L, Cheng W, Yadong L (1997) Separation of
of the LM phase (extractant concentration, sur- cobalt and nickel by emulsion liquid membranes with
factant concentration, modifier concentration), the use of EDTA as masking agent. J Membr Sci
the mixing speed of feed solution, the presence 135:173–177
of complexing agent and its concentration in the Lothongkum AW, Khemglad Y, Usomboon N,
Pancharoen U (2009) Selective recovery of nickel
strip phase, and the feed/strip volumetric ratio are ions from wastewater of stainless steel industry via
the most important operating variables influenc- HFSLM. J Alloy Compd 476:940–949
ing the permeation of nickel across a LM and then Molinari R, Argurio P, Poerio T (2009) Studies of various
membrane selectivity. solid membrane supports to prepare stable sandwich
liquid membranes and testing copper (II) removal from
The selective recovery of nickel ions from aqueous media. Sep Purif Technol 70:166–172
wastewater of stainless steel manufacturing Walkowiak W, Kozlowski CA (2009) Macrocycle carriers
plants can be efficiently carried out by hollow for separation of metal ions in liquid membrane
fiber supported liquid membranes (HFSLM). processes – a review. Desalination 240:186–197
The type of extractant and its concentration in
N
Radoslav Paulen and thus the problem boils down to solving the set
Department of Biochemical and Chemical of nonlinear equations. For solving this type of
Engineering, Technische Universität Dortmund, problems, one may use well-established algo-
Dortmund, Germany rithms such as steepest descent method and New-
ton or quasi-Newton methods.
However, in practice, any optimization prob-
Problems of nonlinear programming (NLP) arise lem involves constraints naturally. To treat
in many engineering applications. These involve constrained NLPs analytically, one may exploit
(complex) process simulations, optimal experi- Karush-Kuhn-Tucker (KKT) conditions which
ment design for estimation of parameters, param- are based on the theory of Lagrange multipliers
eter estimation, optimal process design, optimal (Bazaraa et al. 1993). For practical purposes, one
process control, and so on. In general, usually relies on using numerical methods. These
constrained NLP problems can be mathemati- are based on approximation of original problems
cally stated as (Bertsekas 1999) into an unconstrained form (penalty, barrier, and
interior point methods) or generating sequences
min f ðxÞ (1a) of simpler but closely related subproblems (SQP
x and active set methods).
Nucleation Stage Crystal Growth and other defects, which act as growth points
and catalysts for structural transformation and
Bart Van der Bruggen long-range order formation (Frank 1949).
Department of Chemical Engineering, Process Nucleation stage crystal growth can be
Engineering for Sustainable Systems (ProcESS), described by the self-consistent theory of nucle-
KU Leuven, Leuven, Belgium ation (Girshick and Chiu 1990). According to the
self-consistent theory, the Gibbs free energy DG
needed for nucleation can be written as:
Nucleation is the initial stage of crystal growth
and can be either homogeneous nucleation or DG ¼ 4pr 2 s s ðn 1Þ kB Tln S
heterogeneous, surface-catalyzed nucleation
(Cahn 1960). The nucleation stage can be in which kB is the Boltzmann constant, S is the
surpassed when a seed material is used, on supersaturation, and s is the surface area of a
which crystallization can take place by addition monomer. From this, the nucleation rate can be
of new atoms, ions, or polymers. This is typically calculated as:
applied in reactors for precipitation such as the
pellet reactor for water softening. This is hetero- ss
geneous precipitation, for which a moderately exp
kB T
supersaturated solution is needed (with stability I SCT ¼ I
S
index SI = 1–2). Heterogeneous precipitation is
easier than homogeneous precipitation, since in which I is the rate calculated from the classical
there is no need to create a new surface (and to nucleation theory. The exponential coefficient in
supply the energy needed for this). This also the equation takes the surface energy of the mono-
allows a better control of the crystallization. mer into account.
Homogeneous nucleation sets off with the cre- Nucleation is an important phenomenon in
ation of a small nucleus, which contains the newly membrane synthesis, mainly applied for synthesis
forming crystal. This stage in the process is rela- of inorganic membranes. For example, Lin
tively slow, because the initial crystal components et al. (2001) prepared silicalite membranes by a
have to arrange in the correct orientation and single hydrothermal synthesis on nanoscale-
position to adhere and form the crystal. Therefore, silicalite-seeded porous tubular supports. An
a larger oversaturation is needed (SI = 3–4). incompact crystal layer was obtained, especially
Once a nucleus is formed, crystals may grow on the unseeded support. Silicalite crystals
more rapidly because they contain dislocations
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_417-1
2 Nucleation Stage Crystal Growth
preferentially grew onto the support tubes seeded system was further optimized by increasing solu-
with silicalite powders with size below 4 mm. The tion velocity to a maximum.
silicalite seed particles mainly provided nucle-
ation sites (heterogeneous nucleation) and
enhanced silicalite crystal growth in all directions Cross-References
onto the support, resulting in the formation of a
thin and dense crystal layer. ▶ Membrane Crystallization
For polymeric membranes, the nucleation ▶ Membrane Distillation
stage is typically fast, and homogeneous nucle- ▶ Membrane Synthesis
ation is usually applied. ▶ Supersaturated Solution
A direct application of nucleation for crystalli-
zation is encountered in membrane crystallization
(Curcio et al. 2001). In a membrane crystallizer, a References
solution is concentrated by, e.g., membrane distil-
lation, so that a supersaturated solution is obtained Cahn J (1960) Theory of crystal growth and interface
motion in crystalline materials. Acta Metall
(Curcio and Driolo 2005). Subsequently, the
8(8):554–562
supersaturated solution is crystallized in a second Curcio E, Drioli E (2005) Membrane distillation and
unit, which yields crystals with extraordinary related operations—a review. Sep Purif Rev
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Curcio E, Criscuoli A, Drioli E (2001) Membrane crystal-
due to the presence of a membrane surface acting
lizers. Ind Eng Chem Res 40(12):2679–2684
as growth points. Thus, the membrane is used as Di Profio G, Curcio E, Cassetta A, Lamba D, Drioli
an active surface to promote heterogeneous nucle- E (2003) Membrane crystallization of lysozyme:
ation, but also for mass transfer. This allows a kinetic aspects. J Cryst Growth 257(3–4):359–369
Di Profio G, Perrone G, Curcio E, Cassetta A, Lamba D,
good process control and fast crystallization;
Drioli E (2005) Preparation of enzyme crystals with
membrane-assisted crystallization is in that sense tunable morphology in membrane crystallizers. Ind
superior to other crystallization methods. For Eng Chem Res 44(26):10005–10012
these reasons, membrane crystallization is a Frank FC (1949) The influence of dislocations on crystal
growth. Discuss Faraday Soc 5:48–54
promising process not only for inorganic salts
Girshick SL, Chiu CP (1990) Kinetic nucleation theory: a
(Van der Bruggen et al. 2004) but also for proteins new expression for the rate of homogeneous nucleation
with substantial added value (Di Profio from an ideal supersaturated vapor. J Chem Phys
et al. 2003). A high uniformity in size was 93(2):1273–1277
Lin X, Kita H, Okamoto KI (2001) Silicalite membrane
obtained for crystallization of trypsins in a mem-
preparation, characterization, and separation perfor-
brane crystallizer (Di Profio et al. 2005), with mance. Ind Eng Chem Res 40(19):4069–4078
crystals produced in forced solution flow found Van der Bruggen b, Curcio E, Drioli E (2004) Process
to be more uniform than those obtained in a qui- intensification in the textile industry: the role of mem-
brane technology. J Environ Manag 73(3):267–274
escent membrane system. The crystallization
O
model, permeants dissolve in the membrane with the ability of the oxide membrane to conduct
material and then diffuse through the membrane both ions and electrons (Leo et al. 2009).
down a concentration gradient. Polyimide, poly- Oxygen-enriched air at various concentrations
carbonate, polysulfone, polyethersulfone, and can be achieved in polymeric membrane,
other aromatic polymers are commonly used as whereas ion transfer membranes can give purities
polymeric membrane-based devices for gas sep- of close to 100 %. However, until now both
aration. Mixed matrix membrane (MMM) is a membranes have not been built for large-scale
combination of polymer matrix with molecular gas separations (Burdyny and Struchtrup 2010).
sieve materials. Separation of gases through
molecular sieving materials depends on the dif-
ferences in molecular size of the gases. By com- References
bining the polymer matrix and molecular sieve
materials, MMM with enhanced performance, Burdyny T, Struchtrup H (2010) Hybrid membrane/cryo-
genic separation of oxygen from air for use in the
heat, and chemical resistance can be developed.
oxy-fuel process. Energy 35:1884–1897
Other types of membranes that foreseen as the Hashim SS, Mohamed AR, Bhatia S (2011) Oxygen sep-
promising technology to replace cryogenic sepa- aration from air using ceramic-based membrane tech-
ration for high purity and bulky supply of O2 from nology for sustainable fuel production and power
generation. Renew Sust Energ Rev 15:1284–1293
air separation are ion transfer membranes. Ion
Jeazet HBT, Staudt C, Janiak C (2012) A method for
transfer membranes are solid inorganic oxide increasing permeability in O2/N2 separation with
ceramic materials with complex crystalline struc- mixed-matrix membranes made of water-stable
tures. These dense membranes allow oxygen ions MIL-101 and polysulfone. Chem Commun
48:2140–2142
to diffuse in the direction of decreasing O2 partial
Leo A, Liu S, Diniz da Costa JC (2009) Development of
pressure given an adequate electronic conductiv- mixed conducting membranes for clean coal energy
ity that allows the counter migration of electrons delivery. Int J Greenh Gas Control 3:357–367
(Steeneveldt et al. 2006). The movement of O2 Rufford TE, Smart S, Watson GCY, Graham BF, Boxall J,
Diniz da Costa JC, May EF (2012) The removal of
ions down the membrane is charge compensated
CO2 and N2 from natural gas: a review of conven-
by the opposite movement of electrons. Then, the tional and emerging process technologies. J Pet Sci
oxygen ions release their electrons and recom- Eng 94–95:123–154
bine to form molecular oxygen at the low partial Steeneveldt R, Berger B, Torp TA (2006) CO2 capture and
storage: closing the knowing-doing gap. Chem Eng
pressure end. Therefore, the separation of oxygen
Res Des 84(A9):739–763
via ion transfer membrane concept is achieved
O
Off-Gas from Catalytic Reforming hydrogen feed flows (up to 1000 Nm3 ∙ h 1) and
medium hydrogen purities (between 90 % and
A. Baudot 98 % molar) are required, gas permeation proves
Physics and Analysis Division, IFP Energies economically viable at the industrial scale.
nouvelles, Solaize, France Nowadays, three main membrane providers
offer hydrogen purification permeators:
The largest source of hydrogen in the refinery is – Air Products with the Prism ® silicon-coated
the off-gas of the catalytic reforming unit. Cata- polysulfone membranes (issued from
lytic reforming is a reaction using precious metal Monsanto). Air Products claims that the life-
(platinum or rhenium)-based catalysts that con- time of the Prism ® modules can be more than
verts alkane-containing naphta into two main 15 years.
products: aromatics and hydrogen. The produced – Ube Industries with polyimide hollow fiber
hydrogen generally contains from 10 % to 30 % membranes.
of cracked hydrocarbons ranging from C1 to C6+ – Air Liquide with the MEDAL polyimide and
as well as traces (at the ppmv level) of HCl and high-selectivity polyaramide membranes.
aromatics (Yampulski and Freeman 2010).
As a general rule the hydrogen produced in the All those membranes are based on glassy
catalytic reforming is purified via a PSA polymers and offer a diffusion-based hydrogen
(pressure-swing adsorption) unit prior to being selectivity. Today’s membranes have high H2/
reintroduced in other hydrogen-consuming units CH4 selectivities (from 35 to 200 at 80 C
of the refinery such as hydrotreatments or hydro- (Roman et al. 1991)). For instance, Air Products
cracking units. PSA proves to be a very profitable claims that a single-stage array of Prism ® mod-
unit for such an application, as this technology ules is able to raise the concentration of gases
allows to reach very high purities in hydrogen from 10 % to 30 % up to 70–90 % (Air Products
(>99 % molar) and high yield as the tail gas website), while Medal membranes are able to
flow of the adsorber, mainly composed of the raise the concentration of a gas at 51 bar from
hydrocarbon part of the reformer off-gas, is very 86 % in hydrogen up to 98 % with a permeate
small compared to the feed gas flow. Membrane- pressure at 30 bar and a residue containing 52 %
based gas permeation unit is sometimes used to of hydrogen at 50 bar (Medal Internet website).
purify the hydrogen contained in the off-gas of
the catalytic reformer; especially it is necessary
to regenerate the catalyst. In this case, when small
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_419-1
2 Off-Gas from Catalytic Reforming
uðtÞ ¼ f ðyðtÞÞ
Cross-References
uðtÞ ¼ f ðyðtÞÞ where f() represents a function ▶ Process Control in Membrane Operations
which can take various forms and can be designed
using analytical or numerical methods in order to
yk +1
Np
yk1+1
yk yk
0 1 yk yk0+1
ykN–1 2 ykN
yk0–1 p p
yk1–1
Δx k –1 Δx k Δx k +1
x k0 –1 x k0 x k0 +1 x k0 +2
Oxidative Steam Reforming hydrogen during the reaction shifts the equilib-
rium reactions toward completion at moderate
Fausto Gallucci temperatures, and thus the extent of oxidation
Faculty of Chemical Engineering and Chemistry, reaction to achieve autothermal reforming is
Eindhoven University of Technology, moderate.
Eindhoven, The Netherlands One of the problems of autothermal reforming
carried out in membrane reactors is the mismatch
between the oxidation reaction rate and the
Autothermal reforming or oxidative steam reforming reaction rate. The oxidation is often
reforming is a combination of conventional much faster than the reforming, and for this rea-
steam reforming of the fuel (endothermic reac- son, in packed bed membrane reactors, a high
tion) with the partial oxidation of a small amount temperature region is obtained at the beginning
of the fuel (exothermic reaction) in order to of the bed followed by a low temperature region
achieve an autothermal reaction that proceeds at the end of the bed. This could cause problems
without external input of energy. to the membranes that could be damaged by high
The most studied autothermal reforming is the temperatures while does not work properly (low
conversion of methane to hydrogen. The overall flux – see Richardson equation) at lower
chemical reactions taking place in the temperatures.
autothermal reforming of methane include To circumvent these problems, fluidized bed
steam reforming (Eq. 1), water-gas shift (Eq. 2), membrane reactors are often proposed for this
and total oxidation (Eq. 3). The energy generated kind of reaction system, as the solid circulation
by the oxidation reaction and WGS is used for the inside the reactor allows a virtually isothermal
SMR: condition even in case of highly exothermic
reactions.
CH4 þ H2 O ¼ CO þ 3H2 (1) Examples of autothermal reforming (ATR)
(or oxidative steam reforming) reactions also
CO þ H2 O ¼ CO2 þ H2 (2) include the ATR of ethanol and methanol or the
ATR of naphtha. All these reactions have been
CH4 þ 2O2 ¼> CO2 þ 2H2 O (3) successfully tested in membrane reactors for pure
hydrogen production.
This reaction system can be carried out efficiently
in a membrane reactor as the extraction of
However, the few pilot plants evaluating the combustion, and 5,500 h of carbon dioxide plant
feasibility of the oxyfuel concept use oxygen operation. Since the usual oxygen purity of
production by cryogenic air separation after 99.5 % as obtained in the Linde technique is not
Linde (Callide Oxyfuel Project; Callide Oxyfuel necessary for oxyfuel, the Linde technology can
Pilot Project; CCS Vattenfall Pilot Oxyfuel Pro- produce oxygen with 95 % purity in a cost-
ject). In 2006 in the Schwarze Pumpe industrial effective way which is competing with the
area in East Germany, construction work started ceramic membrane technology. Organic polymer
on the world’s first “carbon-dioxide free” power membrane permeation is not competitive since it
station testing the oxyfuel concept on a pilote cannot produce the necessary oxygen purity of
scale. However, the owner Vattenfall stopped 95 % purity in a single step.
carbon capture R&D at the plant in 2014 because
“its costs and the energy it requires makes the
technology unviable” (http:www.thelocal.se/
References
20140507/vattenfall-abondons-research-on-co2-
storage). In the Callide oxyfuel project, carbon Callide Oxyfuel pilot project, Cubillos del Sil, Spain
dioxide capture started in Dec. 2012. In March Callide Oxyfuel project, Queensland, Australia
2015, the Callide Oxyfuel Project demonstration CCS Vattenfall pilot Oxyfuel project, Schwarze Pumpe,
phase comes to a close after 2 years and 9 months Germany
successfully proving 10,000 h of oxyfuel
O
Oxygen Separation, Fig. 1 Photo and scheme of the oxygen lattice to the core side of the one-end-sealed BSCF
three-tube oxygen production demonstration unit at Leib- tubes where it is released into the gas phase. To have a
niz University of Hannover (copyright Caro, Univ. Han- high-oxygen partial pressure difference over the mem-
nover). Oxygen from surrounding air enters the BCFZ brane, the permeated oxygen is removed by vacuum
material on the shell side, diffuses via vacancies in the pumping
Packed Bed Membrane Reactor Often, a sweep gas can be used in the perme-
ation side of the membrane in order to keep the
Fausto Gallucci permeation hydrogen partial pressure as low as
Faculty of Chemical Engineering and Chemistry, possible for minimizing the membrane area
Eindhoven University of Technology, required for the hydrogen separation. This prac-
Eindhoven, The Netherlands tice is, for example, very useful if hydrogen for
ammonia plant is being produced, in which case
an amount of nitrogen can be used for sweeping
The fixed bed (or packed bed) membrane reactor the permeation side producing a synthesis stream
configuration is the first and most studied config- (N2/H2 = 1/3) ready for the final reaction step. If
uration for membrane reactors. This is because a sweep gas is used in the permeation side, then a
the first studies on membrane reactors focused on packed bed membrane reactor can be used in both
the effect of the gas permeation through mem- cocurrent or countercurrent modes.
branes on the reaction system (which is often a An interesting feature of packed bed mem-
conventional packed bed reactor). brane reactors is the possibility to operate them
In a packed bed membrane reactor, the cata- in a reverse flow mode, integrating the reaction
lyst is confined in fixed bed configuration, and it and separation with the recuperative heat
is in contact with a permselective membrane. The exchange inside the reactor. This operational
most used packed bed configuration is the tubular mode is quite interesting for partial oxidation of
one where the catalyst may be packed either in methane (POM) (Smit et al. 2005). In normal
the membrane tube or in the shell side, while the POM systems, air and CH4 feed streams have to
permeation stream is collected in the other side of be preheated to the reaction temperature, while
the membrane (in case of hydrogen-selective POM reaction being only slightly exothermic, the
membranes) or one reactant is feed on the other external heat transfer between feed and exhaust is
side of the membrane (in case of oxygen- very expensive. Therefore, recuperative heat
selective membrane). exchange is preferably carried out inside the
For multi-tubular membrane reactor configu- reactor.
rations, the catalyst in tube configuration can be Although the tube in tube configuration is
preferred especially for construction reason and quite useful to work in lab scale and for proof of
for the extent of bed-to-wall mass and heat trans- principle of membrane reactors, for industrial
fer limitations which can be very detrimental in scale some other configurations need to be used
the catalyst in shell configuration. in order to increase the membrane area per vol-
ume of vessel used. In fact, the amount of
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_436-1
2 Packed Bed Membrane Reactor
hydrogen produced is directly related to the important drawback has driven the research
amount of membrane area installed in the reactor. toward new reactor concepts such as
Starting for the tube in tube configuration, a micromembrane reactors or fluidized bed mem-
straightforward way to increase the membrane brane reactors.
area in packed bed is the tube in shell configura-
tion (Buxbaum 2002; Tosti et al. 2008).
Although the packed bed configuration is very References
advantageous and easy to operate, the production
of thin membranes brought under the spotlight Buxbaum RE (2002) Patent US 6,461,408
Gallucci F, Van Sint Annaland M, Kuipers JAM
one of the disadvantages of fixed bed membrane
(2010) Theoretical comparison of packed bed and flu-
reactors: the influence of bed-to-wall mass trans- idized bed membrane reactors for methane reforming.
fer limitations on the membrane area required. Int J Hydrog Energy 35:7142–7150
Briefly, as long as the hydrogen flux through the Peters TA, Stange M, Klette H, Bredesen R (2008) High
pressure performance of thin Pd-23%Ag/stainless steel
membrane is a limiting step, the effect of external
composite membranes in water gas shift gas mixtures;
mass transfer limitations such as the limitations influence of dilution, mass transfer and surface effects
to hydrogen transport between the bulk of the on the hydrogen flux. J Membrane Sci
catalytic bed (where hydrogen is produced) and 316(1–2):119–127
Smit J, Bekink GJ, Van Sint Annaland M, Kuipers JAM
the membrane wall (where hydrogen is recov-
(2005) A reverse flow catalytic membrane reactor for
ered) can be neglected. However, by increasing the production of syngas: an experimental study. Int
the membrane flux, the external mass transfer J Chem React Eng 3:1
limitations became limiting and determine the Tosti S, Basile A, Bettinali L, Borgognoni F, Gallucci F,
Rizzello C (2008) Design and process study of Pd
extent of membrane area. This has been demon-
membrane reactors. Int J Hydrog Energy
strated both experimentally (Peters et al. 2008) 33(19):5098–5105
and numerically (Gallucci et al. 2010). This
P
Q Feed Q Retentate
Permeating
JH2
Q Permeate Q Sweep
P Permeation Membrane
SS-Shell
P Reaction Catalyst
(cylindrical symmetry, no radial and axial diffu- transfer is more efficient (Marigliano
sions) of a plug flow reactor on reaction side; this et al. 2001) if the reaction takes place in the
condition is also valid for the permeate volume. annular space since the resistance in this case is
This membrane reactor (MR) model is mathemat- concentrated in the external tube and in the gas
ically described by a first-order ODE set. The two films around it. In the other case, the overall heat
streams in the reaction and permeate volumes can transfer coefficient is lower since the energy has
be in co- or, as shown in the next figure, counter- to be transported through the permeation
current configurations. The permeation driving volume too.
force, the difference between the square root of Different reactor configurations and geome-
hydrogen partial pressure on reaction and perme- tries also including radial and axial diffusions
ation sides, of a co-current tubular MR is the are often operated also at lab scale for analyzing
highest at the entrance and it reduces along the the effect related to the mass and energy diffusive
reactor length; if the reactor is really long, this transport. The following Eq. 2 shows the com-
difference becomes null. The permeation driving plexity of PDE set of a two-dimensional second-
force of a countercurrent tubular MR is more order mathematical model written down for a
distributed along the reactor length (Barbieri tubular MR operating in steady state:
and Di Maio 1997). Therefore, countercurrent
flow configuration results in a higher perfor- @ 2 PReactionSide
i
Diffusivityi, z
mance in terms of, e.g., reaction conversion and @z2
hydrogen recovery. The countercurrent configu- @ 2 PReactionSide
þDiffusivityi, r i
þ Rgas T ReactionSide
r, z
ration requires a shooting method for the numer- @r2
ical solution of the ODEs set. Equation 1 shows
an example of an ODE system for an MR oper- !
@N ReactionSide
i, z
ating in steady state (Fig. 1): þ ½Generation by reactionr, z ¼0
@z
dFi (2)
þ ½Generation by reaction
dz
Models for more complex reactor configurations
½Permeation through the membrane
¼0 (1) and geometries also including radial and axial
diffusions are reported in (Barbieri et al. 2008a)
and characterized by first- and second-order
The choice about the reaction volume as the one
PDE set.
inside the core of the membrane or in the annular
Two more aspects have to be discussed for an
space between the two tubes depends on several
MR: the concentration gradients, more known as
factors, e.g., contact between the catalyst and
concentration polarization, and the permeation
membrane (can damage the membrane since
reduction owing to the presence of some gases
this is a few microns thin) and heat transfer
since both reduce the membrane performance.
from the energy source and reaction. The heat
Pd-Based Tubular Membrane Reactor 3
The permeation is a mass transport happening Inorganic membranes: synthesis, characterization and
at a surface – the one delimited by the applications, vol 13 Series membrane science and
technology. Elsevier B.V., Amsterdam/The Nether-
membrane – and when it is selective creates a lands, pp 325–400. ISBN 978 0 444 53070
variation in the composition of species in the film 7. doi:10.1016/S0927-5193(07)13009-6
close to the membrane itself. This variation will Barbieri G, Scura F, Lentini F, De Luca G, Drioli
spread with a finite – not infinite – velocity; this E (2008b) A novel model equation for the permeation
of hydrogen in mixture with carbon-monoxide through
means a concentration profile is created in the Pd-Ag membranes. Sep Purif Technol 61(2):217–224.
orthogonal direction at the membrane surface. doi:10.1016/j.seppur.2007.10.010
The concentration profile is physiological in any Barbieri G, Caravella A, Drioli E (2011) Polarization and
membrane separation and its breadth depends on CO inhibition in Pd-based membranes, Chapter 14. In:
Drioli E, Barbieri,G (eds) Membrane engineering for
membrane selectivity and permeance. The higher the treatment of gases, vol 2 Gas-separation problems
the selectivity and permeance, the higher the combined with membrane reactors. The Royal Society
concentration profile (Caravella et al. 2008, of Chemistry, Cambridge, MA, pp 137–161. ISBN
2009; Boeltken et al. 2013). The presence of a 978-1-84973-239-0. http://pubs.rsc.org/en/content/
ebook/978-1-84973-239-0; doi:10.1039/
concentration gradient reduces significantly the 9781849733489-00137
driving force for the permeation, that is, function Boeltken T, Belimov M, Pfeifer P, Peters TA, Bredesen R,
of the partial pressure at the membrane surface Dittmeyer R (2013) Fabrication and testing of a planar
and not the one in the bulk of the reaction and microstructured concept module with integrated palla-
dium membranes. Chem Eng Process 67:136–147
permeation phases. Braun F, Miller JB, Gellman AJ, Tarditi AM, Fleutot B,
The adsorption of some species such as CO Kondratyuk P, Cornaglia LM (2012) PdAgAu alloy
and H2S (Gade et al. 2011; Morreale et al. 2004; with high resistance to corrosion H2S. Int J Hydrog
Kulprathipanja et al. 2005; Braun et al. 2012; Energy 37:18547–18555
Caravella A, Barbieri G, Drioli E (2008) Modelling and
Kajiwara et al. 1999; Gabitto and Tsouris 2009; simulation of hydrogen permeation through supported
Chen and Ma 2010; Iyoha et al. 2007) on the Pd-alloy membranes with a multicomponent approach.
membrane surface causing the reduction in the Chem Eng Sci 63(8):2149–2160. doi:10.1016/j.
number of metal surface sites for hydrogen ces.2008.01.009
Caravella A, Barbieri G, Drioli E (2009) Concentration
adsorption is a fundamental step for hydrogen polarization analysis in self-supported Pd-based mem-
permeation. This phenomenon, known in cataly- branes. Sep Purif Technol 66:613–624. doi:10.1016/j.
sis as poisoning of catalysts, follows the same seppur.2009.01.008
adsorption laws, e.g., the Langmuir one Caravella A, Scura F, Barbieri G, Drioli E (2010) Inhibi-
tion by CO and polarization in Pd-based membranes: a
(Barbieri et al. 2008b). It results in a significant novel permeance reduction coefficient. J Phys Chem
increase of permeation resistance and similar B 114:12264–12276. doi:10.1021/jp104767q
permeance reduction (Caravella et al. 2010). Caravella A, Scura F, Barbieri G, Drioli E, Hara S (2011)
Both concentration gradients and inhibition by On the role of the coupled effect of inhibition by CO
and concentration polarization on hydrogen perme-
chemical species have to be taken into account ation through Pd-based membranes. Trans Mater Res
for a proper evaluation of hydrogen permeation Soc Jpn 36:225–228. doi:10.14723/tmrsj.36.225
(Caravella et al. 2010, 2011; Barbieri et al. 2011) Chen C-H, Ma YH (2010) The effect of H2S on the
and hence membrane reactors performance. performance of Pd and Pd/Au composite membrane.
J Membr Sci 362:535–544
Gabitto JF, Tsouris C (2009) Sulfur poisoning of metal
membranes for hydrogen separation. Int Rew Chem
Eng 1(5):394–411
References Gade SK, De Voss SJ, Coulter KE, Paglieri SN, Alptekin
GO, Way JD (2011) Palladium–gold membranes in
Barbieri G, Di Maio FP (1997) Simulation of methane mixed gas streams with hydrogen sulfide: effect of
steam reforming process in a catalytic Pd–membrane alloy content and fabrication technique. J Membr Sci
reactor. Ind Eng Chem Res 36(6):2121–2127. 378(1–2):35–41
doi:10.1021/ie9601615 Iyoha O, Enrik R, Killmeyer R, Morreale B (2007) The
Barbieri G, Scura F, Brunetti A (2008a) influence of hydrogen sulfide-to-hydrogen partial
Chapter 9 – Mathematical modelling of Pd-alloy mem-
brane reactors. In: Mallada R, Menendez M (eds)
4 Pd-Based Tubular Membrane Reactor
pressure ratio on the sulfidization of Pd and 70 mol% Marigliano G, Barbieri G, Drioli E (2001) Effect of energy
Pd–Cu membranes. J Membr Sci 305:77–92 transport in a palladium based membrane reactor for
Kajiwara M, Uemiya S, Kojima T (1999) Stability and methane steam reforming process. Catal Today
hydrogen permeation behavior of supported platinum 67(1–3):85–99. doi:10.1016/S0920-5861(01)00268-1
membranes in presence of hydrogen sulfide. Int Morreale BD, Ciocco MV, Howard BH, Killmeyer RP,
J Hydrog Energy 24:839–844 Cugini AV, Enick RM (2004) Effect of hydrogen-
Kulprathipanja A, Alptekin GO, Falconer JL, Way JD sulfide on the hydrogen permeance of
(2005) Pd and Pd–Cu membranes: inhibition of H2 palladium–copper alloys at elevated temperatures.
permeation by H2S. J Membr Sci 254:49–62 J Membr Sci 241:219–224
P
permeation driving force; thus, the following or L m2 s1 Pa1 , or etc:Þ
equation defines the flux of each permeating spe-
cies (ith) as the product of permeance and driving
force:
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_445-1
2 Permeance
Permeate Gap
Membrane Distillation
(PGMD), Fig. 1 Basic
channel arrangement and
temperature profile for
PGMD (Winter et al. 2011)
Permeate Gap Membrane Distillation (PGMD), Fig. 2 Principle channel arrangement of a spiral wound PGMD
module (Winter et al. 2011)
The PGMD channel arrangement is transferred Hausmann A, Sanciolo P, Vasiljevic T, Weeks M, Duke
into a compact spiral package. Full-scale mod- M (2011) Membrane distillation in the dairy industry:
process integration and membrane performance. In:
ules of this type were developed and fabricated at Proceedings of the international workshop on mem-
Fraunhofer ISE (Winter et al. 2011). The total brane distillation and related technologies, Ravello
membrane area is 5–15 m2. The module concept Raluy RG, Schwantes R, Subiela VJ, Peñate B, Melián G,
goes back to a patent of W. L. Gore from 1985 Betancort JR (2012) Operational experience of a solar
membrane distillation demonstration plant in Pozo
(Gore et al. 1985). Izquierdo-Gran Canaria Island (Spain). Desalination
This type of module is quite suitable to follow 290:1–13
the transient behavior of thermal energy input Winter D, Koschikowski J, Wieghaus M (2011) Desalina-
from renewable sources. Thus, an integration to tion using membrane distillation: experimental studies
on full scale spiral wound modules. J Membr Sci
solar thermal collectors or waste heat is easily 375:104–112
applicable. Various demonstration plants for
desalination using PGMD spiral wound modules Further Reading
have already been tested in the field (Raluy Cipollina A, Micale G, Rizzuti L (2009) Seawater desali-
et al. 2012). nation. Springer, Heidelberg
Khayet M, Matsuura T (eds) (2011) Membrane distilla-
tion. Elsevier, Amersterdam
Koschikowski J (2011) Entwicklung von Energieautark
References arbeitenden Wasserentsalzungsanlagen auf Basis der
Membrandestillation. PhD thesis, Fraunhofer ISE,
Gore WL et al. (1985) US Patent 4,545,862, United States, Fraunhofer, Universität Kassel
Patent and trademark office
P
All the species permeating a membrane generate Permeating Fluxi ¼ Molar Fractioni Permeating Flux
a stream passing through the membrane, a stream
characterized by a flow rate according to the The permeating flux can be defined for each ele-
actual operating conditions. A permeating flux mentary membrane area element or for the whole
is defined for this stream as the ratio of the per- membrane area. In the first case, it is a function of
meating flow rate and the membrane area. the spatial coordinates such as, for instance, the
membrane length. In the latter case, the permeat-
Permeating Flow Rate
Permeating Flux ¼ ing flux corresponds to the integration of the
Membrane Area permeating flow rate on the whole membrane
area of the elementary one divided for the whole
The permeating flux can be defined as well for ith
membrane area.
species as the ratio of the flow rate of the referred
species and the membrane area.
The permeation number expresses (Brunetti For the ith species, it is given by the equation
et al. 2010), for each species, a comparison
It is a dimensionless number to be used in sizing The pressure ratio is the ratio of the feed to the
the permeation unit. A low value means a low permeate pressures.
fraction of the referred ith species can pass
through the membrane; vice versa, a high value
means a large fraction of i will be in the permeate
References
stream.
A value of zero means no membrane separa- Brunetti A, Scura F, Barbieri G, Drioli E (2010) Mem-
tion, that is, permeance equals to zero or equiva- brane technologies for CO2 separation. J Membr Sci
lently no membrane area available for 359:115–125. doi:10.1016/j.memsci.2009.11.040
permeation.
Permeate
Condensor
Feed
can be used) or ceramic membranes. Hydropho- permeation, in contrast to the liquid feed in
bic pervaporation makes use of polymeric mem- pervaporation.
branes (hydrophobic, such as
polydimethylsiloxane or PDMS) with preferen-
tial transport of nonpolar solvents, which can be Cross-References
used to remove organics from an aqueous matrix.
The third type of applications is organic-organic ▶ Dense Membrane
separations, which require special membranes ▶ Microporous Membrane
allowing to distinguish between different organic ▶ Polymeric Membrane
solvents; an example is PTMSP (Claes ▶ Solution-Diffusion
et al. 2011). The most important industrial appli- ▶ Vapor Permeation
cation is the dehydration of alcohols, although
research efforts also indicate a great potential in
the water and wastewater treatment sector, in the References
food and biotechnology industry, and in the
chemical industry. Binning RC, Lee RJ, Jennings JF, Martin EC (1961) Sep-
With regard to large-scale industrial applica- aration of liquid mixtures by permeation. Ind Eng
Chem 53:45–50
tion, the earliest mention of an operating pilot Claes S, Vandezande P, Mullens S, Van Bael MK, Maurer
plant dates back to 1982 as a demonstration unit FHJ (2011) Enhanced performance in pervaporation of
for alcohol dehydration was designed to produce supercritical carbon dioxide treated poly1-
1,200 l per day of 99.2 wt.% ethanol. This unit (trimethylsilyl)-1-propyne pervaporation membranes.
J Membr Sci 382:177–185
clearly demonstrated the low energy consump- Feng X, Huang RYM (1997) Liquid separation by mem-
tion of pervaporation compared with that of con- brane pervaporation: a review. Ind Eng Chem Res
ventional dehydration of ternary azeotropic 36:1048–1066
distillation after addition of benzene (Feng and Jonquières A, Clément R, Lochon P, Néel J, Dresch M,
Chrétien B (2002) Industrial state-of-the-art of
Huang 1997; Kujawski 2000; Jonquières pervaporation and vapour permeation in the western
et al. 2002). countries. J Membr Sci 206:87–117
A membrane separation process closely Kujawski W (2000) Application of pervaporation and
related to pervaporation is vapor permeation. vapour permeation in environmental protection.
J Environ Study 9:13–26
The only difference concerns the feed, which is Lipnizki F, Trägårdh G (2001) Modelling of
a mixture of vapors or vapors and gases in vapor pervaporation: models to analyze and predict the
mass transport in pervaporation. Sep Purif Method
30(1):49–125
Pervaporation (PV) 3
Okada T, Matsuura T (1991) A new transport model for component permeation. Sep Sci Technol
pervaporation. J Membr Sci 59:133–149 33(6):767–785
Shieh JJ, Huang RYM (1998a) A pseudophase-change Shieh JJ, Huang RYM (1998b) A pseudophase-change
solution-diffusion model for pervaporation. I. Single solution-diffusion model for pervaporation. II. Binary
mixture permeation. Sep Sci Technol 33(7):933–957
P
Cross-References
▶ Pervaporation
P
Pervaporation Hybrid System type and reaction-type hybrid processes. The lat-
ter are denoted as R-type hybrid systems; the
Bart Van der Bruggen pervaporation unit can remove either the desired
Department of Chemical Engineering, Process reaction product from the reactor or from a recy-
Engineering for Sustainable Systems (ProcESS), cle loop (R1-type hybrid system) or a side prod-
KU Leuven, Leuven, Belgium uct (R2-type hybrid system), which is often
water. This is shown in Fig. 1 (Lipnizki
et al. 1999). R-type hybrid systems with a
Synonyms pervaporation unit for separation are also referred
to as pervaporation membrane reactors. R1-type
Pervaporation-based hybrid system hybrid systems are typical (but not exclusive) for
bioconversions, in which the conversion can be
A hybrid system based on pervaporation refers to enhanced by removal of the conversion product.
an integrated entity comprising a pervaporation For example, in the production of bioethanol, the
unit for separation and a second unit in which product ethanol acts as an inhibitor for bacterial
either a reaction is carried out or a separation with activity when the concentration becomes too
a different method than pervaporation. The inte- high. Removal of ethanol allows for continuous
gration by recycling one stream from the biological activity, which enhances the yield of
pervaporation unit and another stream from the ethanol significantly. R2-type pervaporation
second unit to the pervaporation unit is an essen- hybrid systems are typical for equilibrium reac-
tial aspect of the hybridization (without a recycle tions, in which the yield is enhanced by the
stream, the system would rather be a separation- removal of a by-product of the reaction.
separation or reaction-separation sequence) (Van According to the principle of Le Ch^atelier-
der Bruggen 2010). A hybrid system should have Braun, the reaction equilibrium would then shift
a performance superior to the performance of the toward a higher conversion; the net result is that
sum of the individual processes, which should not the yield of the desired product is substantially
be able to carry out the overall process as a stand- higher, allowing even for full conversion. The
alone system (although this is usually understood most studied examples are esterification reac-
in the sense that none of the individual processes tions, in which an ester is produced from the
is able to carry out the overall process in an reaction of an acid with an alcohol. The side
economical way). product in these reactions is water, which can be
Lipnizki et al. (1999) categorize pervaporation easily removed from the reaction medium by a
hybrid systems into two types, i.e., separation- hydrophilic pervaporation membrane.
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_453-1
2 Pervaporation Hybrid System
Pervaporation Hybrid a b
System, Fig. 1 R-type
(reaction) hybrid processes:
(a) type R1 (removal of
reactor product) and (b) reactor reactor
type R2 (removal of
by-product) (Lipnizki
et al. 1999)
PV PV
Product By-Product
Pervaporation Hybrid System, Fig. 2 Integration of pervaporation and distillation in different hybrid configurations
Esterification reactions are often carried out with integration of pervaporation with a distillation
acetic acid (Van der Bruggen 2010). column are shown in Fig. 2 (Van der Bruggen
Pervaporation-assisted esterification of ethanol 2010).
and acetic acid is often studied, but many other The most common difficulties in separations
reactions are similar. The principle was patented are azeotropic points in distillation, which require
in 1995 (Datta and Tsai 1995) for the esterifica- complex and energy-intensive solutions when
tion of lactic acid, propionic acid, butyric acid, using distillation alone, but are easy in a hybrid
acetic acid, and succinic acid (and combinations setup in which pervaporation is used to overcome
thereof) with an alcohol, including the reaction of the azeotrope. A typical example is the produc-
acetic acid and ethanol, aided by the use of a tion of ethanol from ethanol-water mixtures. The
pervaporation membrane. azeotrope at a concentration of ethanol of
The separation-type hybrid systems based on ca. 96 % can be overcome by distilling to, e.g.,
pervaporation typically combine pervaporation 90 % and continuing with pervaporation for puri-
with distillation. Both processes can in principle fication of the distillate (and recycling the water-
be used for the same kind of separations, but the richer retentate back to the distillation column).
separation mechanisms are totally different Various hybrid pervaporation systems can be
(based on a difference in volatility for distillation developed, with a (smaller) distillation column
and on a difference in membrane affinity for for the final ethanol purification, or a second,
pervaporation), so that a combination is logical more selective pervaporation membrane
to overcome difficult points in the individual separation.
processes. Different configurations based on
Pervaporation Hybrid System 3
A general problem for the stability of a mem- linear polymers), the more the membrane swells
brane in pervaporation is the effect of the vacuum at the feed side. This causes an asymmetric struc-
applied at the permeate side. The vacuum is ture (swollen/unswollen), which causes mechan-
needed to obtain a sufficient difference in partial ical stress that might lead to cracking. Swelling
pressure. In such conditions, the membrane is not can be avoided by crosslinking of the polymer,
swollen. In contrast, the membrane is in contact but a balance is needed because crosslinking usu-
with the liquid feed mixture at the feed side, ally has a negative impact on fluxes.
which causes swelling by uptake of solvent. The
more flexible the polymeric chains are (e.g.,
Pervaporation Membrane 3
and new technique for separation of aqueous alcoholic pervaporation of water/alcohol mixtures. J Phys Chem
solutions through alginic acid membranes. Sep Sci 99:13193–13197
Technol 24:541–554 Villaluenga JPG, Mohammadi T (2000) A review on the
Van Baelen D, Reyniers A, Van der Bruggen B, separation of benzene/cyclohexane mixtures by
Vandecasteele C, Degrève J (2004) Pervaporation of pervaporation. J Membr Sci 169(2):159–174
binary and ternary mixtures of water with methanol Ying C, Kita H, Okamoto KI (2004) Zeolite T membrane:
and/or ethanol. Sep Sci Technol 39(3):563–580 preparation, characterization, pervaporation of water/
Van Veen HM, Van Delft YC, Engelen CWR, Pex PPAC organic liquid mixtures and acid stability. J Membr Sci
(2001) Dewatering of organics by pervaporation with 236:17–27
silica membranes. Sep Purif Technol 22–23:361–366 Yoshida W, Cohen Y (2003) Ceramic-supported polymer
Vankelecom IFJ, Depre D, De Beukelaer S, Uytterhoeven membranes for pervaporation of binary organic/
JB (1995) Influence of zeolites in PDMS membranes: organic mixtures. J Membr Sci 213:145–157
P
A pervaporation membrane reactor (PMR) is an The most simple esterification reaction is the
integrated reaction-separation system, in which reaction of ethanol with acetic acid to yield
one or more components from a reaction medium ethyl acetate and water. To enhance the yield of
is selectively removed in order to increase the RCOOR’ (ethyl acetate in the example), H2O can
yield of the reaction (Van der Bruggen 2010). be removed by a hydrophilic pervaporation mem-
The component removed by pervaporation can brane (Datta and Tsai 1995; Waldburger and
be the product (type 1 PMR) or a by-product Widmer 1996). The membrane to be used should
(type 2 PMR). This is schematically shown in be hydrophilic, often based on polyvinyl alcohol
Fig. 1 (Lipnizki et al. 1999). (PVA). Other materials include polyvinylacohol/
Pervaporation membrane reactors can be used polyacrylonitrile (PVA/PAN), polyetherimide
for bioconversions (type 1 PMR), such as the (PEI), and 4,40 -oxydiphenylene pyromellitimide
production of bioethanol and bio-butanol, and (POPMI) (Van der Bruggen 2010). Ceramic
for the extraction of aroma components from a pervaporation membranes have specific advan-
fermentation broth. Vane (2005) describes a tages (more robust and higher fluxes, although
pervaporation-bioreactor hybrid process for eth- more expensive). For this application, a
anol fermentation and further ethanol purification pervaporation membrane reactor is an alternative
by dehydration (Fig. 2). A hydrophobic mem- to the more conventional (and more energy-
brane is needed for ethanol extraction consuming) reactive distillation.
(polydimethylsiloxane membranes are typical Pervaporation membrane reactors can be even
for this application), followed by a hydrophilic more integrated by using a catalytically active
membrane for obtaining a sufficient ethanol inorganic pervaporation membrane, which acts
purity. both as catalyst and separator. An acid zeolite,
Another type of applications is in conversion H-ZSM-5, was used in what was called an “active
reactions limited by the chemical equilibrium. zeolite membrane reactor (AZMR).” Gao
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_455-1
2 Pervaporation Membrane Reactor
Pervaporation a b
Membrane Reactor,
Fig. 1 (a) Type R1 PMR
(removal of reactor
product) and (b) type R2 reactor reactor
PMR (removal of
by-product) (Lipnizki
et al. 1999)
PV PV
Product By-Product
Water enriched
Retentate Ethanol permeate
feed
enriched
microfiltration permeate
fermentation Hydrophobic PV
et al. (1996) and Tanaka et al. (2001) studied the conditions (in particular with methanol selectiv-
esterification of acetic acid and alcohol, catalyzed ity) have been reported and can be used (Bhat and
by an exchange resin, using a zeolite A-PVA Pangarkar 2000; Ray et al. 1999). The use of
composite membrane, and a zeolite pervaporation membrane reactors for transester-
T membrane, respectively. ifications in comparison with reactive distillation
In spite of many applications already studied, has also been described by Brinkmann
transesterification reactions have not yet been et al. (2009).
extensively considered. Many esters are made
using transesterification, because the milder con-
ditions prevailing permit the reaction of compo-
Cross-References
nents containing additional functional groups. In
alcoholysis, a complex alcohol is reacted with a
▶ Pervaporation
methyl ester, forming a complex ester and meth-
▶ Pervaporation Membrane
anol. These reactions are all equilibrium limited
and are therefore candidates for use in a
pervaporation membrane reactor. However,
pervaporation membranes needed for this type References
of PMR should be organophilic, which is more
challenging than classical solvent-water separa- Bhat AA, Pangarkar VG (2000) Methanol-selective mem-
branes for the pervaporative separation of
tions. Nevertheless, membranes for specific
Pervaporation Membrane Reactor 3
α=1
40 40
20 20
distillation
azeotropic point
0 0
0 20 40 60 80 100
Feed [wt.% H2O]
of component A in the permeate to the fraction of the highest reported separation factors for
component A in the feed: ethanol-water separation are in the order of mag-
nitude of 20 (Claes et al. 2011).
yA Flux and selectivity are strongly influenced by
bA ¼
xA the specific characteristics of the components in
the feed, the membrane, and the process-
Usually, there is a trade-off between the perme- operating parameters. These factors include per-
ation flux and selectivity; i.e., when one factor meate pressure, process temperature, feed com-
increases, the other decreases. As both of them position and concentration, feed turbulence,
are important numbers in the separation process, membrane thickness, concentration polarization,
a pervaporation separation index (PSI) can be temperature polarization, and the membrane
defined as a measure of the separation ability of material.
a membrane (Sommer and Melin 2005):
Kujawski W (2000) Application of pervaporation and Sommer S, Melin T (2005) Performance evaluation of
vapour permeation in environmental protection. microporous inorganic membranes in the dehydration
J Environ Stud 9:13–26 of industrial solvents. Chem Eng Proc
Mulder MHV (1996) Basic principles of membrane tech- 44(10):1138–1156
nology, 2nd edn. Kluwer, Dordrecht
P
process photocatalysis -MD was conducted in a applied (0.5 g TiO2/dm3). The increase of the
simultaneous mode. After 5 L of permeate the reaction temperature from 313 to 333 K resulted
model dye was removed completely, whereas in an increase of the photodegradation rate of
total organic carbon (TOC) concentration was AY36. After 5 h of the hybrid process, the effec-
lowered down to 20 % of the initial value. tiveness of dye degradation calculated on a basis
Mozia et al. (2007) investigated on the possi- of AY36 mass in a feed solution amounted to
bility of coupling photocatalysis and direct con- 31 %, 36 %, and 42 % at reaction temperatures
tact membrane distillation (DCMD, MD) for 313–333 K. Similar results were obtained when
degradation of azo dyes (Acid Red 18, Acid Yel- photocatalysis was conducted in the MD installa-
low 36, and Direct Green 99) in aqueous solution. tion but with the MD module disconnected. An
TiO2 Aeroxide (R) P25 (Degussa, Germany) was improvement of AY36 photodegradation was
used as the photocatalyst. It was found that the achieved by decreasing the initial dye concentra-
addition of TiO2 P25 to the feed did not affect the tion. The best configuration seemed to be the
distillate flux, regardless of the catalyst concen- PMR one by taking into account the rate of azo
tration applied. The MD process was very effec- dye degradation and the quality of the product.
tive in separation of photocatalyst particles. After The investigations on the photodegradation of
5 h of the experiment, the turbidity of distillate a nonsteroidal anti-inflammatory drug ibuprofen
was similar to that measured for ultrapure water, sodium salt (IBU) in a photocatalytic membrane
regardless of the TiO2 loading used. The highest reactor (PMR) coupling photocatalysis using
effectiveness of photodecomposition was suspended TiO2 and direct contact membrane
obtained in case of Acid Red 18, whereas Acid distillation was also described by Mozia
Yellow 36, which has the lowest molecular et al. (2012). The influence of solution composi-
weight among the dyes used, was degraded with tion in terms of (i) pH (pH 3, pH 6.5, and pH 10),
high difficulty. The composition of the feed solu- (ii) presence of inorganic salts (NaCl, Na2SO4,
tion slightly influenced the quality of distillate. NaHCO3, NaNO3, and Na3PO4), and (iii) turbid-
Among the volatile compounds that passed ity (bentonite, 13.5–103 NTU) on the effective-
through the membrane, some organic compounds ness of IBU removal was especially investigated.
were present as indicated by the measurements of The highest effectiveness of IBU
TOC concentration. photodegradation was obtained at pH 6.5. No
An anatase-phase TiO2 was applied for degra- influence of the presence of NaCl, NaNO3, and
dation of Acid Yellow 36 (AY36) in the PMR Na2SO4 on the effectiveness of degradation and
coupling photocatalysis and direct contact mem- mineralization of IBU was found. NaHCO3 and
brane distillation (DCMD) by Mozia Na3PO4 did not affect the effectiveness of degra-
et al. (2009). The effect of different process dation of IBU; however, the efficiency of miner-
parameters such as dye concentration, reaction alization decreased significantly. The increased
temperature, and photocatalyst loading on the turbidity of feed solution did not affect IBU
effectiveness of degradation of AY36 was inves- removal in the PMR.
tigated. Moreover, in order to compare the effec-
tiveness of AY36 photodegradation during
photocatalysis alone and the hybrid process,
References
additional experiments without application of
the membrane distillation (MD) were conducted. Loddo V, Augugliaro V, Palmisano L (2009)
The addition of TiO2 to a feed did not affect the Photocatalytic membrane reactors: case studies and
permeate flux, regardless of the process condi- perspectives. Asia Pac J Chem Eng 4:380–384
tions applied. The latter remained constant during Mozia S, Tomaszewska M, Morawski AW (2005) A new
photocatalytic membrane reactor (PMR) for removal
about 400 h of experiments. The highest decolor- of azo-dye Acid Red 18 from water. Appl Catal
ization of AY36 solution during hybrid process B Environ 59:131–137
was observed at the highest photocatalyst loading
Photocatalysis with Membrane Distillation 3
induce some photo-reduction reactions, as for molecules and on the experimental conditions
instance H2 production from H2O (Chiarello used, as for instance the presence of water vapor.
et al. 2011). Other oxides as for instance ZnO,
WO3, MoO3, Fe2O3, ZrO2, sulfides as ZnS, CdS,
MoS2, or polyoxometalates as the heteropolyacid References
H3PW12O40 have been also successfully tested as
photocatalysts (Di Paola et al. 2012). They have Augugliaro V, Loddo V, Palmisano G, Palmisano L,
Pagliaro M (2010) Clean by light irradiation. Practical
been also mixed with or supported on SiO2 or
applications of supported TiO2. RSC Publishing,
Al2O3 with the aim to increase the surface area Cambridge
and to have the possibility to improve adsorption Braslavsky SA, Braun AM, Cassano AE, Emeline AV,
of the reacting species before their chemical Litter M, Palmisano L, Parmon VN, Serpone N (2011)
Glossary of terms used in photocatalysis and radiation
transformation on photoactive sites of adjacent
catalysis (IUPAC recommendations 2011). Pure Appl
particles of the semiconductor photocatalyst. Chem 83:931–1014
They have been also used in combination with Chiarello GL, Di Paola A, Palmisano L, Selli E (2011)
membranes forming devices called Effect of titanium dioxide crystalline structure on the
photocatalytic production of hydrogen. Photochem
“photocatalytic membrane reactors” (Molinari
Photobiol Sci 10:355–360
et al. 2010). Di Paola A, García-López E, Marcı̀ G, Palmisano L (2012)
Some photocatalysts are not (photo)stable in A survey of photocatalytic materials for environmental
liquid–solid systems, especially in aqueous envi- remediation. J Hazard Mater 211–212:3–29
Molinari R, Caruso A, Palmisano L (2010) Photocatalytic
ronments and the extent of this instability
processes in membrane reactors. In: Drioli E, Giorno
strongly depends on the pH conditions. For L (eds) Comprehensive membrane science and engi-
instance, (i) anodic photocorrosion is observed neering, vol 3. Elsevier-AP, Amsterdam, pp 165–193
for ZnO and various sulfides and (ii) the recovery Voı̈nov M, Augustynski J (1997) Introduction to the phys-
ics of semiconductor photocatalyst. In: Schiavello M -
of polyoxometalates from the reacting medium is
(ed) Heterogeneous photocatalysis, vol 3, Wiley series
problematic, due to their high solubility. The in photoscience and photoengineering. Wiley, Baffin
above phenomena generally are not observed Lane, pp 1–34
when the photoreactions are carried out in Wang C, Li J, Mele G, Duan M, L€ u X, Palmisano L,
Vasapollo G, Zhang F (2010) The photocatalytic activ-
gas-solid systems, although in the latter system
ity of novel, substituted porphyrin/TiO2-based com-
deactivation of photocatalyst has been sometimes posites. Dyes Pigments 84:183–189
observed, depending on the type of reagent
P
TiO2 and Ag-TiO2 catalysts were supported in TiO2 dispersed in polyester acrylate mem-
the form of thin layers by a dip-coating procedure branes was tested as a photocatalyst in the phenol
on quartz substrate by Herrmann et al. (1997). mineralization reaction in the presence of O2 by
The resulting materials were characterized by D’Arienzo et al. (2010). A kinetic study indicated
SEM/EDX, XRD, XPS, and UV–Vis absorption that the embedded oxide maintains significant
spectroscopy. The immobilized catalysts were catalytic activity, and the result was first attrib-
tested in the photocatalytic degradation of malic uted to the homogeneous dispersion inside the
acid and the increase of the photocatalytic activ- polymeric host of TiO2 nanocrystals. Further-
ity can be explained by the enhanced more, an investigation of the photogenerated
electron–hole pair separation efficiency due to charge carriers in the photocatalyst indicated
trapping of electrons by metallic Ag. that electrons are trapped on Ti3+ centers, while
A novel chemistry method for the fabrication holes are trapped on C-centered species of the
of robust nanostructured TiO2 photocatalysts was polymer matrix. In the presence of O2, the
developed by Choi et al. (2006). Such materials C-centered radicals of the polymer transform
can be applied for developing efficient into peroxy radicals, improving the charge sepa-
photocatalytic systems to be used for water treat- ration in the polymer-embedded oxide with
ment. The mesoporous photocatalytic TiO2 mem- respect to the powder. The positive interference
branes were synthesized via a simple method that of the polymer matrix is responsible for the
involves dip-coating of appropriate substrates enhanced photoactivity of the embedded TiO2.
into an organic/inorganic sol composed of Kim et al. (2003) proposed a hybrid thin-film-
isopropanol, acetic acid, titanium tetraiso- composite (TFC) membrane consisting of self-
propoxide, and polyoxyethylene sorbitan assembly of TiO2 nanoparticles with
monooleate surfactant (Tween 80) followed by photocatalytic destructive capability on microor-
calcination of the coating at 500 C. Controlled ganisms as a novel mean to reduce membrane
hydrolysis and condensation reactions were biofouling. Microbial biofouling does not allow
achieved through in-taking of water molecules to realize high permeability over a prolonged
released from the esterification reaction of acetic period of reverse osmosis operation. The anti-
acid with isopropanol. The subsequent stable fouling and fouling mitigation on the actual com-
incorporation of Ti-O-Ti network onto self- mercialized TFC was verified. TiO2 anatase
assembled surfactants resulted in TiO2 nanoparticles (10 nm) were prepared from the
photocatalysts with enhanced structural and cat- controlled hydrolysis of titanium tetraiso-
alytic properties. The properties included high propoxide and characterized by X-ray diffraction
surface area (147 m2/g) and porosity (46 %), nar- (XRD) analysis and transmission electron
row pore size distribution ranging from 2 to 8 nm, microscopy (TEM). TFC membrane was pre-
homogeneity without cracks and pinholes, active pared by self-assembly of the TiO2 nanoparticles
anatase crystal phase, and small crystallite size through coordination and H-bonding interaction
(9 nm). These TiO2 photocatalysts were highly with the COOH functional group of aromatic
efficient for the destruction of methylene blue polyamide thin-film layer. The hybrid membrane
and creatinine in water. High water permeability was shown to possess photobactericidal effect on
and sharp polyethylene glycol retention of the Escherichia coli (E. coli) under UV light illumi-
prepared photocatalytic TiO2/Al2O3 composite nation. Introduction of TiO2 nanoparticles on the
membranes evidenced the good structural prop- actual commercial TFC membrane and applica-
erties of TiO2 films. In addition, the multi-coating tion of reverse osmosis field test after exposure to
procedure enabled to control the physical prop- microbial cells indicated the occurrence of a sub-
erties of TiO2 layer such as the coating thickness, stantial prevention against the microbial fouling
amount of TiO2, photocatalytic activity, water showing a less loss of reverse osmosis
permeability, and organic retention. permeability.
Photocatalytic Membrane 3
ultrafiltrating TiO2 suspensions showed an opti- driving force for humic acids to pass through
mal layer density slightly >2.04 mg TiO2 per the membrane. When photocatalytic reactions
square cm of membrane surface area. Results took place with UV illumination, UV254
obtained from membrane reactor studies indi- removal efficiencies of the permeate were
cated that the observed initial rate constants for improved markedly, and also the permeate flux
the degradation of 4-NP were almost independent was kept at a constant level without any sign of
on the amount of TiO2 employed over the range fouling. Although humic acids were not
0.76–4.08 mg/cm2. A 50 % weight degradation of completely mineralized by photocatalysis, the
4-NP after 5 h of irradiation in the presence of air degradation of the humic acids helped to enhance
was obtained. Instead, an almost complete deg- the UF flux, as they were transformed into less
radation of 4-NP was observed in the presence of absorbable compounds.
TiO2 suspended in the solution and pure oxygen. The photodegradation of different pharmaceu-
The permeate deriving from the membrane ticals [furosemide, ranitidine (hydrochloride),
photoreactor was clear, and 4-NP concentration ofloxacin, phenazone, naproxen, carbamazepine,
was approximately equal to that found in the and clofibric acid] in aqueous medium at various
retentate. The possibility of the continuous reuse pHs by using a batch photoreactor and a
of the photocatalyst and the continuous separa- photocatalytic membrane reactor working in
tion of products from the reaction medium gives recirculation regime was carried out by Molinari
some advantages over traditional approaches. et al. (2006). Polycrystalline TiO2 was used as the
The ability of cross-flow ultrafiltration photocatalyst, and different membranes (NTR
(UF) combined with photocatalytic reactions to 7410, PAN GKSS HV3/T, N 30 F, NF PES 10)
separate TiO2 photocatalysts from treated water were tested. A different adsorption of the sub-
in photocatalytic drinking water treatment was strates onto the catalyst surface was observed
studied by Lee et al. (2001). The effect of natural owing to the hydrophilic/hydrophobic character
organic matter (i.e., humic acids) and cross-flow of the catalyst, depending on the pH. The
velocities on UF fluxes and organic removal was photodegradation of the seven molecules in the
explored with and without UV irradiation in the batch reactor was successfully carried out, and
photocatalytic reactor. The interaction between the behavior was in accordance with pseudo-first-
the two solutes in the system, humic acids and order kinetics. Furosemide and ranitidine were
TiO2 photocatalysts, played a significant role in selected to carry out the study of rejection and
the formation of dense cake layers at the mem- photodegradation in the hybrid membrane sys-
brane surface, leading to a greater flux decline tem. The permeate flux of the treated water was
during ultrafiltration of TiO2 particles. According in the 31.5–60.0 L/(h m2) range for NTR 7410
to visual observations of the used membranes and membrane, whereas rejection values in the range
the estimation of back-transport velocities of the 10–60 % for furosemide and 5–30 % for raniti-
solutes, a substantial amount of TiO2 deposited dine in the dark (without photoreaction) were
on the membrane induces more humic acids to found. The degradation in the hybrid membrane
accumulate at the membrane through the adsorp- photoreactor showed that the photocatalyst was
tion of humic acids onto TiO2 particles. The retained by the membrane in the reaction ambi-
humic acid-laden TiO2 particles offered more ent, while the membrane rejection toward the
than four times higher specific cake resistance pollutants was not very satisfactory. A net
with a substantially increased compressibility decrease of the rejection down to 0 was observed
coefficient than TiO2 particles alone. The higher in the contemporary presence of light,
the cross-flow velocities, the greater the UV254 photocatalyst, and oxygen.
removal achieved. This was because the rise of A batch-recirculated photoreactor was com-
cross-flow velocities contributed to the reduction bined with a hollow fiber membrane ultrafiltra-
of concentration polarization at the membrane tion (UF) unit for heterogeneous photocatalysis
surface, thereby resulting in a decrease of the applications (Sopajaree et al. 1999). The
Photocatalytic Membrane Reactor 3
operation and modeling of the UF process com- transformation products were formed during
ponent and the performance of the integrated treatment. Additionally, the unit was operated in
photoreactor-UF process assembly were studied. photolytic mode (UV only) and photolytic plus
Methylene blue and titanium dioxide (Degussa H2O2 mode (UV/H2O2) to determine the relative
P-25) were used as the test pollutant and amount of energy required. Based on the electri-
photocatalyst, respectively. The influence of cal energy per order (EEO), the unit achieved the
cross-flow velocity, transmembrane pressure, greatest efficiency when operated in photolytic
and TiO2 dose on the permeate flux through the plus H2O2 mode for the conditions tested.
hollow fiber membrane was described. These
data are modeled on the basis of concentration
polarization and gel layer formation at the mem- References
brane surface/feed slurry boundary. The opera-
tion of the integrated photoreactor-UF assembly Benotti MJ, Stanford BD, Wert EC, Snyder SA
(2009) Evaluation of a photocatalytic reactor mem-
over ten repeated cycles was experimented.
brane pilot system for the removal of pharmaceuticals
Photocatalyst separation was complete as gauged and endocrine disrupting compounds from water.
by nephelometric turbidity measurements. How- Water Res 43:1513–1522
ever, a systematic degradation in the Lee SA, Choo KH, Lee CH, Lee HI, Hyeon T, Choi W,
Kwon HH (2001) Use of ultrafiltration membranes for
photocatalyst performance was noted with each
the separation of TiO2 photocatalysts in drinking water
repeated cycle. Dynamic laser light-scattering treatment. Ind Eng Chem Res 40:1712–1719
data were consistent with agglomeration of the Molinari R, Mungari M, Drioli E, Di Paola A, Loddo V,
TiO2 particles as a result of the UF process and Palmisano L, Schiavello M (2000) Study on a
photocatalytic membrane reactor for water purifica-
suggest a possible factor in the degraded
tion. Catal Today 55:71–78
photocatalytic activity. Molinari R, Palmisano L, Drioli E, Schiavello M (2002)
A photocatalytic reactor membrane pilot sys- Studies on various reactor configurations for coupling
tem, employing UV/TiO2 photocatalysis, was photocatalysis and membrane processes in water puri-
fication. J Membr Sci 206:399–415
evaluated by Benotti et al. (2009) for its ability
Molinari R, Pirillo F, Loddo V, Palmisano L (2006) Het-
to remove 32 pharmaceuticals, endocrine- erogeneous photocatalytic degradation of pharmaceu-
disrupting compounds, and estrogenic activity ticals in water by using polycrystalline TiO2 and a
from water. Twenty-nine of the targeted com- nanofiltration membrane reactor. Catal Today
118:205–213
pounds in addition to total estrogenic activity
Sopajaree K, Qasim SA, Basak S, Rajeshwar K (1999) An
were greater than 70 % removed, while only integrated flow reactor-membrane filtration system for
three compounds were less than 50 % removed heterogeneous photocatalysis. Part II: experiments on
following the highest level of treatment the ultrafiltration unit and combined operation. J Appl
Electrochem 29:1111–1118
(4.24 kWh/m3). No estrogenically active
P
Photocatalytic Process,
Fig. 1 Photocatalytic Reduction
Process Conduction band
e− Adsorption
hn
EG
Adsorption
h+
detection of CO2 soon after the starting of Molinari R, Caruso A, Palmisano L (2009) Photocatalytic
irradiation. membrane reactors in the conversion or degradation of
organic compounds. In: Drioli E, Giorno L (eds) Mem-
Heterogeneous photocatalytic processes have brane operations, innovative separations and transfor-
been more recently addressed also toward the mations. Wiley-VCH, Weinheim, pp 335–361
selective production of high-value molecules in Palmisano G, Garcı́a-López E, Marcı̀ G, Loddo V,
mild experimental conditions by using suitable Yurdakal S, Augugliaro V, Palmisano L (2010)
Advances in selective conversion by heterogeneous
photocatalysts, solvent and starting substrates photocatalysis. Chem Commun 46:7074–7089
(Palmisano et al. 2010; Augugliaro and Serpone N, Emeline AV (2005) Modelling heterogeneous
Palmisano 2010), and, in some cases, also mem- photocatalysis by metal-oxide nanostructured semi-
branes (Molinari et al. 2009). conductor and insulator materials: factors that affect
the activity and selectivity of photocatalysts. Res
Chem Intermed 31:391–432
References
comes into play. Materials with nanoscopic • The top-down approach – starting with the
dimensions may exhibit quantized conductance bulk material and carving the way down to
(Landauer 1989) which not only has potential the nanoscale, and
technological applications in various areas but • The bottom-up approach – starting at the
also is of fundamental interest. molecular level and fabricating up the material
It has been approximately five decades since through the small cluster level to the nanopar-
researchers first began exposing materials like ticle and the assembly of nanoparticles.
polymers to ionizing radiation and reporting the
occurrence of cross-linking and other useful Nanotechnology provides the ability to fabri-
effects. Today, a substantial commercial industry cate structures with nanometric precision that is
is in place based on processing of polymers with of fundamental importance. The potential of
radiation. Innovation in this field has by no means combining radiation effects with nanomaterials
ended; important new products made possible has been recognized from the very early stages of
through radiation technology continue to enter nanoscience research. In the many uses of
the marketplace, and exciting new innovations nanostructures, and nanoparticles in particular,
in the application of radiation to macromolecular from catalysis, bio-sensing, nano-electronics,
materials are under exploration at research insti- magnetic applications including separations,
tutions around the world. mechano-chemical conversion, and to molecular
This entry reviews the technique – the “tem- computing radiation can play a significant role.
plate synthesis” (TS) – involving the porous Many nanostructured systems, like metal sul-
membranes (specific reference is made to track- fide semiconductors of nanometric matrices,
etch membranes) which are spin-off from the PC-controlled biochips for programmed release
radiation-matter interaction and are used as systems, nano-ordered hydrogels based on natu-
tools in the development of nano/micromaterials, ral polymers, development of polysaccharides,
structures, and devices. The recent past has emerge out from the use of radiation (UV beam,
witnessed the keen interest being generated on electron beam, or focused ion beam) techniques
the use of innovative technologies like TS in the which offer unmatched reproducibility and very
production of nanomaterials’ fabrication involv- narrow size distribution. The relative advantages
ing materials like metals, nonmetals like semi- and deficiencies of each of them are still to be
conductors, magnetic multilayered nanowires, clarified as the technology advances. However,
conducting polymers, glasses, nanotubules, whether UV or electron beam will lead to the
wires, whiskers, etc., reported from various highest resolution is still debated.
authors and from our lab (See refs in The studies on natural rubber-clay composites
(Chakarvarti and Vetter 1998; Martin 1996; and thermoplastic natural rubber-clay composites
Brumlik et al. 1994; Chakarvarti and Vetter have given interesting results. Nanomaterials
1993; Kumar et al. 2004a, b, c, d, e, f; Sekhon with high abrasion and high scratch resistance
et al. 2004; Kumar et al. 2005; Chakarvarti will find industrial application.
et al. 2005a; Kumar and Chakarvarti 2005; The formation of microporous and
Chaudhri et al. 2006a; Singh and Chakarvarti nanoporous membranes having highly uniform
2008a; Chakarvarti 2007a; Kumar and geometry and precisely determined structures is
Chakarvarti 2007a; Chakarvarti 2007b; Kumar an exciting example of industrial application of
et al. 2007a, b; Chaudhri and Chakarvarti ionizing radiation. These materials, called track-
2008a; Kumar et al. 2008a)). etch membranes (TEMs) were first made by irra-
diation of polymeric sheets, micas, and glasses
Nano Synthesis Approaches with fragments from the fission of heavy nuclei
All the conventional and available nanosynthesis such as californium or uranium (nuclear track-
techniques can be categorized into two comple- etch method). This technique presents a great
mentary approaches: limitation due to contamination of the foil with
Track-Etch Membranes as Tools for Template Synthesis 3
radioactive products so that “cooling” of the irra- consists of filling a host porous medium with
diated material, before using, is needed; this usu- one or more desired materials. Three main pro-
ally takes a few months. The second method cesses are used for the synthesis of various com-
makes use of heavy ion beams, usually of energy binations of polymers and/or metals:
on the order of several MeV, from accelerators
and presents quite a few advantages over the (a) electrodeposition, where one side of the tem-
former one which are: (a) no induced radioactiv- plate coated with a metallic layer, or the tem-
ity in the irradiated material when ion energy is plate support itself, is used as a cathode for
below the Coulomb barrier; (b) all tracks show electroplating; (b) chemical polymerization
the same etching properties; (c) deeper penetra- where a solution of the desired monomer and
tion in the material owing to higher energy of initiator, in which the template membrane is
particles; (d) higher density (even >109 cm 2 dipped, is left to diffuse through the pores of
for smaller pores) track arrays; and (e) easier the templates leading to a polymerization
control of the impact angle and production of reaction in these pores; (c) electroless plating
arrays of parallel tracks. A heavy ion beam with where a catalyst to the pore walls is applied
acceleration energy of more than 1 MeV/n which facilitates the deposition of metal on the
deposits its energy to a substrate in a region activated pores of the template. The micro- or
<10 nm in diameter (an ion track); the depth of nanomaterials, which are produced in this
the affected region can be regulated by changing way, take the form of wires or tubules. Mag-
the energy or replacing species of ion particles. netic, conducting, and superconducting
Widely used polymers for ion track membranes nanowires and nanotubules in array or isolated
are polyethylene terephthalate (PET) and poly- mode possessing special properties have been
carbonate (PC). By bombarding PET or PC films manufactured in this way.
with swift heavy ions (e.g., Ar+, N+, or Xe+) latent
radiation damage linear tracks are created There are two distinct nano-fabrication pro-
through the samples. cesses using heavy ion beams; one is nano-hole
According to the following sensitization and formation due to the damage of ion beam path, and
etching with an alkali solution (NaOH for the other is nanowire formation due to cross-
instance), uniform cylindrical, conical, tunnel- linking of polysilane, which is also caused by
like, or cigar-like pores have been obtained. heavy ion beams. Potential applications in devices
Pore sizes or dimensions depend upon various such as microwave filters for shielding microwave
factors, viz., the nature and energy of incident ovens and mobile phones, or in chemical detectors
particles, the target material, etch conditions, and biosensors with conductive polymer
e.g., temperature, nature of etchant, pre-etch stor- nanotubules are also being seriously considered.
age conditions, etc., and are controllable. The fabrication of ion track membranes made
Cylindrical channel 0.02–5.0 mm in diameter of PET has been reported to develop selective
with lengths of 10–50 mm, membranes containing membranes for the separation of toxic metal
anywhere from a single pore up to 109 pores/ ions, biomolecules, and biological cells because
cm 2 have been produced, and thin film polymer of the advantages to control the pore size and the
membranes having highly uniform pore size and properties of the internal surfaces of the pores.
a wide variety of porosities in well-distributed
areas of the template (patterning) are already
commercially available. A number of modifica- Methodology
tion methods have been devised for creating
TEMs with special properties and functions. Track-Etch Membranes (TEMs)
These isoporous membranes are used as tem- The most widely used materials in manufacturing
plate materials for the synthesis of micro- and TEMs are polymers, micas, and rarely this glass
nanostructures. The template-base method sheets. TEMs, also known as nuclear track filters
4 Track-Etch Membranes as Tools for Template Synthesis
(NTFs), have emerged as spin-off from solid state has been discussed in details (see for example,
nuclear track detectors (SSNTDs) – solid dielec- (Possin 1970; Williams and Giordano 1984;
tric materials capable of storing damage trails of Klien et al. 1993); etc.). Handled adequately and
energetic heavily ionizing ions which can subse- properly, these TEMs can enable wires, tubules,
quently be chemically amplified for observation solid cylinders, conical or tapered needles, etc.,
as pores either through, say SEM or optical with a well-controlled dimension and shape
microscope. The art and science used in crafting besides a large aspect ratio. The dimensional
of TEMs as templates involves two parameters can vary from 10 nm to several micro-
steps – irradiation of an SSNTD foil or a film by meters with aspect ratio as high as 10–1000. The
heavy energetic ion beam creating damage trails, pores can be “drilled” with alignment in any
also called as latent tracks and, followed by a direction depending upon the angle of incidence
controlled chemical etching of these latent tracks of the beam with the target. The synthesized
so as to produce see-through pores in the host members may either be left within the pores as
material. The size and dimensions of the etched embedded or can be removed either by dissolving
pores can be controlled conveniently through or removing the host or pulling out mechanically
parametric control over the nature and energy of but carefully of the host matrix. Figure 1 shows
the intruding ions, the host material as target to be schematically the process of producing TEM and
developed as template, chemical etch conditions, its use as template, and Fig. 2 shows SEM pho-
viz., nature, concentration, temperature, agita- tograph of a processed polycarbonate (Makrofol)
tion, etc., besides preirradiation and NTF with monodisperse pores.
postirradiation storage conditions of the target
material. The etched pores can have diameter Template Synthesis: A Technique
ranging from few nm to mm. NTFs have been The template approach has been extensively
put to numerous other applications besides their investigated in the synthesis of various
use as templates. There exists a wealth of litera- nanostructures. For example, mesoporous oxides
ture on SSNTDs and related topics. As discussed with well defined and ordered porous structure
already, a large number of materials are used in can be readily synthesized using surfactant or
manufacturing of NTFs which include mainly copolymer micelles as templates through sol–gel
polymeric sheets, micas, glasses, etc. The particle processing. However, template-based synthesis is
track-etch technique, therefore, enables the gen- most commonly and widely used to prepare free
eration of definite shaped pores which can either standing, nonoriented and oriented nanowires, or
be used individually in the form of single particle nanorods or nanotubes; the latter is also referred
track or collectively in the form of pore arrays to as nanorod or nanowire or nanotube arrays.
constituting many pores – distributed either sto- The most commonly used and commercially
chastically (pore density as high as 1010/cm2), or available templates are anodized alumina mem-
in a well-defined spatial geometry through the brane (AAM) and radiation track-etched polycar-
control of the drilling particle beam used in bonate (PC) membranes. Other membranes have
“write mode.” Areal dispersion usually lies also been used, such as nanochannel array on
between 2 % and 20 % and a 10 MeV/nucleon glass, radiation track-etched mica, mesoporous
heavy ion (say, for example, various projectiles materials, porous silicon by electrochemical
used are collimated beam of fission fragments, etching of silicon wafer, zeolites (Ozin 1992),
heavy energetic ions like U, Pb, Ag, Si, Bi, etc., and carbon nanotubes. Bio-templates are also
whose range in the target material is far greater explored for the growth of nanowires and
than the thickness of the target) has a range of the nanotubes such as Cu, Ni, Co, and Au nanowires.
order of 10 mm in many polymers (Williams and The commonly used alumina membranes with
Giordano 1984). The custom made NTFs are uniform and parallel pores are made by anodic
available in a wide variety of pore size and poros- oxidation of aluminum sheet in solutions of sul-
ities. The crafting of TEM templates through ions furic, oxalic, or phosphoric acids. The pores can
Track-Etch Membranes as Tools for Template Synthesis 5
at elevated temperatures, but the flexibility of PC and Bera et al. (Bera et al. 2004) used this tech-
is more prone to distortion during the heating nique for generating conductive metal oxide
process, and the removal of the template would (MoOx) at the step-edges of HOPG, which after
occur before complete densification of the reduction in appropriate environment could yield
nanorods. These factors would result in broken metallic Mo nanowires.
and deformed nanorods. The advantage of using When electrodeposition is carried out, the
AAM as the template is its rigidity and resistance nucleation of nanostructures on the electrode sub-
to high temperatures, allowing for the nanorods strate via template pores during electrodeposition
to densify completely before removal. This is influenced by the crystal structure of the sub-
would result in a larger surface area of fairly strate, specific free energy, and other factors like
free-standing and unidirectionally aligned adhesion energy; orientation of the lattice of the
nanorod arrays. The problem with AAM is the substrate; etc., and the final size distribution of
complete removal of the template after nanorod electrodeposits is strongly dependent upon the
growth, which has so far been unsuccessful using growth and nucleation kinetics (Bera
wet-chemical etching. et al. 2004). Template-assisted electrodeposition
The technique of TS (Ozin 1992) may be clas- process can be divided into two categories: active
sified into three categories depending upon the template-assisted process which results from
mode of use of templates (Huixin): the negative growth of nuclei that essentially nucleate at the
template method, positive template method, and pores and defects of the substrate, while the other
surface step-edge template method. The negative is known as restrictive template-based electrode-
template method which is the most popular and position used mostly in the synthesis of metallic
widely used techniques of TS allows the use of nanowires, involves deposition of metal into the
prefabricated nanopores in solid templates, and prefabricated and designed pores within an inert,
the material is deposited into these pores normally insulator membrane or template. PTEMs, porous
using electrochemical techniques. After removing alumina, conductive polymers, carbon, etc., have
(say by way of dissolving) the host template, free- been used as templates which fall under this cat-
standing elements as wires, cylinders, or conical egory (Bera et al. 2004).
structures can be obtained. The method has been
regarded as “brute-force” method as the synthe- Negative Template Synthesis
sized ensemble structure depicts the true replica- The basic and underlying principle of negative
tion of the morphology of the pores (Foss 2002). TS is similar to that of producing materials
The fabrication of such templates involves many through the use of replication, e.g., die-casting
techniques including heavy ion irradiation of solid or molding like making ice candies. There are
insulating materials like polymeric foils, micas, many methods used in practice for preparing
glasses, etc., producing so-called TEMs. More nanomaterials right from milling to lithographic
details would follow later. The positive template techniques (Hhadjipanayis and Siegle 1994).
methods use wire-like substrates like DNA (size These techniques suffer from the problems like
ca. 2 nm) (Braun et al. 1998), carbon nanotubes little control over the final morphology of the
(Fullam et al. 2000), etc., on the outer surface of resulting nanoproducts, ensembles, and mate-
which the material is deposited to the desired rials. The TS has in turn edge in this regard. It
dimensions. The removal of templates can pro- enables the synthesis of a variety of materials
duce wire-like or tube-like structures. Other posi- ranging from micro- to nanodimensions, high
tive templates have been discussed by Huixin He aspect ratio, and of desired morphology and
and Nongjian J.Tao (Huixin). The surface step- geometry – the single unique attribute which
edge templates, also known as “step-edges deco- makes this route as most acceptable and econom-
ration,” use the fact that there is preferential or ical too. A template, in a general sense, may be
selective deposition of many materials initiating defined as a predesigned structure within which a
on the defect sites. Zach et al. (Zach et al. 2000) network exists, which can be utilized for further
Track-Etch Membranes as Tools for Template Synthesis 7
use. Thus, for example, a membrane with followed by Possin (Possin 1970) who utilized
prefabricated cavities or pores of known mor- electrodeposition technique in the fabrication of
phology, number, distribution, and configuration thin wires as small as 400 Å using mica with
may also act as a template; the pores of which can etched pores as templates for synthesis of such
facilitate replication by any suitable means. elements of the nanostructures. Williams and
Removal of the host template would lead to the Giordano (Williams and Giordano 1984) claimed
presentation of ensembles whose morphological to have reduced the size down to 80 Å after
and stereo-chemical features and traits might rep- effecting some refinements to the technique.
licate the original cavities or pores in the tem- Penner and Martin (Penner and Martin 1987)
plate. Here in this technique, materials can be reported on the generation and characterization
deposited within the cavities or pores or any of ultra-microelectrodes with radii as small as
other dimensional structures, by various methods 1000 Å. Klien et al. (Klien et al. 1993) reported
like electrochemical or chemical reduction on the fabrication of graded CdSe/CdTe hetero-
(electroless) of the appropriate ion. Depending structures and development of chemistry for fab-
upon the template geometries and the controlling ricating II-VI chalcogenide semiconductors
factors, functional procedure, and related param- CdSe and CdTe within the template membranes
eters, the generated structures can be monodis- producing micro-diode arrays consisting of
perse homogeneous or heterogeneous, micro-cylinders retinal rod cells – the photore-
multilayered, short, squat fibrils, long needles, ceptors in the human eye – and having ca. five
hollow tubules, tapered conical (single or double times smaller diameter than that of photorecep-
cones) elements, etc., depending upon the tem- tors. Team led by Prof. Charles Martin at Colo-
plate factors stated above. The interesting aspect rado State University, USA, has been actively
is that one can have complete control over the engaged in exploring and exploiting the TS for
aspect ratio (length and diameter ratio). Metallic its full potential and a large number of reports are
as well as nonmetallic tubules can be obtained by available (see refs in (Huczko 2000)).
chemically derivating the pore/cavity walls by Researchers at GSI at Darmstadt, Germany
providing molecular anchors so that the (where this author has had also his first hands-
electrodeposited metal deposits preferentially on on experience with the technique of TS for a short
the walls layer by layer, leading to hollow tubules duration during early 1990s), have also many
when the process is terminated at a preestimated reports to their credit for developing the tech-
time interval (Martin et al. 1990). The synthe- nique further and generating nano-/
sized structures can remain either inside the host microstructures (see, for example, ref. (Spohr
structures in the templates or they can be ren- 1990)). A large bulk of literature since then has
dered free, and collected as ensemble. Alterna- been published on the negative TS and its appli-
tively, an ensemble of nano-/microstructures that cations (see refs in (Chakarvarti and Vetter 1998;
protrude from a surface like the bristles of a brush Huczko 2000; Martin 1994)). This lab has also
can be produced. The technique is blessed with been reporting from time to time on the synthesis
simplicity and nano-/microstructures with of nano-/microstructures, devices, and tubules
extraordinary low dimensions have been reported using TEMs as templates (see refs.(Chakarvarti
to be produced (see refs in Parthasarthy and Vetter 1998; Martin 1996; Brumlik
et al. 1995; Schonenberger et al. 1997; Sima et al. 1994; Chakarvarti and Vetter 1993; Kumar
et al. 2004) which are otherwise difficult to man- et al. 2004a, b, c, d, e, f; Sekhon et al. 2004;
ufacture using lithographic methods. Kumar et al. 2005; Chakarvarti et al. 2005a;
Kumar and Chakarvarti 2005; Chaudhri
History and Development of Negative Template et al. 2006a)). Almost simultaneously, the TS
Synthesis also included porous alumina (Al2O3) mem-
Bean (Bean 1969) first demonstrated the art of branes, which are prepared electrochemically
filling the pores of a membrane with silver from aluminum (the fabrication method of anodic
8 Track-Etch Membranes as Tools for Template Synthesis
porous alumina started as early as 1950s), and technique (Linkot et al. 1999) and references
have usually high pore density (as high as 1011/ therein (Bercu et al. 2004). The underlying prin-
cm2) with pores as small as ca.5 nm, arranged in ciple is to create nucleation centers on the pore
hexagonal arrays (Despic and Parkhutik 1989). walls and then precipitate the desired material on
Here in the present review, detailed discussion these nucleation centers. Through controlled
has further been carried only on negative tem- manipulations, one can synthesize hollow as
plate synthesis using TEMs as templates for syn- well as solid tubules. Metals like Cu, Ni, Au,
thesis of nano-/micromaterials. etc. or chalcogenides are dissolved in suitable
solvents and precipitation can be facilitated on
the pore walls. Martin (1996) using chemical
Materials reactions, say, by permitting two reagents meet
within the pores and react, produced precipitates,
While sieving properties of porous membranes followed by drying process and their retrieval
have been used from as early as some thousands (Kumar et al. 2004d). The necessary prerequisite
of years, but it is relatively only recently that a is that the penetrants acting as reactants must be
technological application like TS of nano-/ hydrophilic otherwise one would require to apply
microstructures has been brought to this hydrostatic pressure to forcibly inject them into
process – almost a by-product having no relation the pores. In case of two gases (or one as gas and
with sieving properties. Until recently where the other participant as liquid) as reactants entering
use of positive template synthesis has started, from both the faces of the template, the reaction
most of the work had been carried out using can be accomplished within the pores. For more
negative template synthesis involving mainly details, see references in Ferain and
two types of membranes: TEMs and porous alu- Legras (2003).
mina (Al2O3). Others include nanochannel array In the proceeding paragraphs, more details of
glasses, xeolites, proteins, etc. A wide variety of galvanic synthesis only are being provided. As
other nanoporous solids that can be used as tem- mentioned, the technique is based upon the ear-
plates are cited elsewhere (see, for example, ref. lier work of Bean (Bean 1969), Possin (Possin
Martin 1994). 1970), Spohr (1982), Williams and Giordano
(Williams and Giordano 1984) and, Penner and
Template Synthesis of Low Dimensional Martin (1987). The simple underlying concept of
Structures and Devices electrodeposition of metals through
The strategy for embedding matter of interest electroplating is described as an electrochemical
within the etched pores or channels in the tem- process in which metallic ions in supporting solu-
plate is the material’s placement through some tion are reduced to the metallic state at the cath-
suitable mechanism at the desired places, viz., ode, which, if closely covered by an NTF as a
pores. This can be accomplished in four ways. template and as an overlay, would lead to the
(Huixin) Using the capillary action of the pores/ formation of growth of plated film as the embodi-
channels and enabling the solution of the ment of micro- or nanostructure. The pores of the
dissolved material entering into the pores, NTF used would act as template (see Fig. 1).
followed by slow evaporation of the solvent.
This will lead to growth of supersaturated struc- Electrochemical Cells and Electrodeposition
tural elements (Landauer 1989) using electro- A scientific treatment of galvanic process is in
chemical (galvanic) technique which is widely fact complicated, and development of optimum
practiced. Here, electrodeposition of the desired plating conditions may be obtained through one’s
metal ions is carried out either using personal experience obtained through repeated
two-electrode or three-electrodes electroplating trials under the given inputs. The age and condi-
cell (Bera et al. 2004;(Chakarvarti and Vetter tion of electrolyte, viz., temperature, pH, concen-
1998) using electroless (nongalvanic) deposition tration, agitation rate, purity of solvent as well as
Track-Etch Membranes as Tools for Template Synthesis 9
Track-Etch Membranes as Tools for Template Synthesis of Nano-/Microstructures and Devices, Fig. 7
(a) Polypyrrole microtubules (Kumar et al. 2004e). (b) Thin walled polypyrrole tubules (Kumar et al. 2004e)
Track-Etch Membranes as Tools for Template Synthesis of Nano-/Microstructures and Devices, Fig. 8
(a) Se microtubules (Chakarvarti and Vetter 1993) (b) Se microtubules (Chakarvarti and Vetter 1993)
membranes with 3 % H2SO4 followed by distilled Dobrev et al. 1994) which offer a low ohmic
water and absolute ethyl alcohol would facilitate voltage drop across the electrodes even when
the galvanic process in the case of metals like the cell is filled with a poorly conducting electro-
zinc, indium, etc. (Possin 1970). Presoaking of lyte. There are various cell designs available: two
the cleaned and washed template with the given electrodes and three electrode cells. The cell
electrolyte is also helpful (Chakarvarti and Vetter designed by Dobrev et al. (1994) has the provi-
1991). Many detailed studies of the electrochem- sion for mechanical stirring besides a thermostat
ical fabrication process for nanostructures have for maintaining the desired temperature of the
been reported by many workers (Schonenberger water contained in a jacket surrounding the cell
et al. 1997; Whitney et al. 1993). as constant.
For electrodeposition of metals, some special Electrodeposition is accomplished by simply
types of electroplating cells are used (Penner and coating one face of the overlaid template with a
Martin 1987; Chakarvarti and Vetter 1991; metal film (preferably gold) to serve as a working
Track-Etch Membranes as Tools for Template Synthesis 11
Track-Etch Membranes
as Tools for Template
Synthesis of Nano-/
Microstructures
and Devices, Fig. 9 Cu-Se
junctions (Chakarvarti and
Vetter 1993)
Track-Etch Membranes as Tools for Template Syn- Track-Etch Membranes as Tools for Template Syn-
thesis of Nano-/Microstructures and Devices, thesis of Nano-/Microstructures and Devices,
Fig. 10 Cu-Se nano-RTDs (Chakarvarti and Vetter 1991) Fig. 11 Zn-Se nano-RTDs
12 Track-Etch Membranes as Tools for Template Synthesis
nanowires, see reference Piraux et al. (1994)) having pores with different shapes (some cylin-
with varying frequencies have been used for bet- drical and others conical). The Makrofol foils
ter results, increased crystallinity and homogene- were got irradiated at Gesellschaft fur Schwerio-
ity (Yin et al. 2001). Nielsch et al. (2000) used nenforschung (GSI), Darmstadt, Germany. Also
pulsed electrodeposition method and demon- some polycarbonate foils were obtained from
strated that it suits for uniform deposition of Whatman. More details and descriptions can be
porous alumina with almost 100 % (Nielsch found from the references quoted.
et al. 2000). From our experience, we have Some of the nano-/microdevices synthesized
found that initial high voltage for short duration were resonant tunneling diodes (RTDs) made
followed by low values (the process is called from heterojunctions of metal-semiconductors
“striking”) produces good results. Chakarvarti (Cu-Se,Zn-Se,Cd-Te systems, see refs. (Kumar
and Vetter (Chakarvarti and Vetter 1998) have et al. 2005, 2008a)) besides field-ion emitters
suggested a formula in order to calculate an (Kumar et al. 2004g, 2007b) using metallic
approximate optimum current for satisfactory nano/micro-tipped cylinders of copper and silver.
results. It is of interest to note that the template For filling up the template pores, the electrode-
synthesized materials (metals as well as semicon- position was carried out from one face and the
ductors) in the form of solid cylinders, wires, or process was interrupted when the pores were
whiskers can be crystalline (Dobrev et al. 1994; filled half-way through. The electrolyte was
Chakarvarti et al. 1996). replaced by another one with different metal/
semiconductor material composition, and the
Synthesized Structures and Devices: Some Results deposition was further carried out till the pores
Some of the metallic, nonmetallic homogeneous are filled up to the brim. Figure 15 shows typical
and heterogeneous structures and devices synthe- I-V characteristics of nano-RTDs synthesized
sized in this lab are shown in the Figs. 3, 4, 5, 6, 7, from Zn-Se deposition in Makrofol PTEMs,
8, 9, 10, 11, 12, 13, and 14. The template used in confirming the fact that nature manifests identical
all cases were TEMs of Makrofol polycarbonate both in small scale and macro scale as well.
Track-Etch Membranes
as Tools for Template Diameter of RTDs = 900
Synthesis of Nano-/ 25 nm
Microstructures
and Devices, 20 Diameter of RTDs = 450
Fig. 15 Collective nm
current–voltage (I–V) 15
characteristics of Zn-Se
RTDs with average 10
diameters of 900 nm and
450 nm 5
0
−2 −1.5 −1 −0.5 0 0.5 1 1.5 2
−5
−10
−15
−20
−25
14 Track-Etch Membranes as Tools for Template Synthesis
Figure 14 shows a floral display as a by-product Chaudhri M, Vohra A, Chakarvarti SK, Kumar R (2006a)
of template synthesis process. Mater Sci 17(3):189–192
Chaudhri M, Vohra A, Chakarvarti SK, Kumar R (2006b)
More results on the effect of size as well as J Mater Sci 17(12):993–998
temperature of the synthesized RTDs of II-VI Chaudhri M, Vohra AK, Chakarvarti SK
materials, modeling of RTDs, and other aspects (2010) J Commun Netw 2:73–78
of template synthesis of variety of materials have Despic A, Parkhutik V (1989) In: Bockris JO, White RE,
Conway BE (eds) Modern aspects of electrochemistry.
been reported (Kumar et al. 2005, 2007a, b, c, Plenum, New York
2008a, b, c, d, 2009, 2010a, b, 2011a, b, c, d, Dobrev D, Vetter J, Angert N (1994) GSI Sci Rep, Darm-
2012a, b, c, d, e, 2013; Chakarvarti 2007a; stadt, Germany, 1995
Kumar and Chakarvarti 2006, 2007a, b, c, d, Ferain E, Legras R (2003) Nucl Instr Meth in Phys Res
B 208:115
2010, 2012; Chaudhri et al. 2006b, 2010; Fischer BE, Spohr R (1983) Rev Mod Phys 55(4):907
Chaudhri and Chakarvarti 2008b, c; Chakarvarti Fleischer RL, Price PB, Walker RM (1975) Nuclear tracks
et al. 2005b; Kaur et al. 2005, 2006, 2007a, b, c, d, in solids: principles and applications. University of
2009a, b, 2011a, b, c; Verma et al. 2005; Singh California Press, Berkeley
Foss CAJ (2002) Metal nanoparticles synthesis, charac-
et al. 2006, 2008, 2013; Singh and Chakarvarti terization and applications. Marcel Dekker, New York
2008b; Chakarvarti 2009, 2010; Sekhon Fullam S, Cottel D, Rensmo H, Fitzmaurice D (2000) Adv
et al. 2011; Gehlawat et al. 2012; Rani Mater 12:1430
et al. 2013a, b). Gehlawat D, Chauhan RP, Sonkawde RG, Chakarvarti SK
(2012) Appl Physics A Mater Sci Process
106:157–164
Hhadjipanayis GC, Siegle RW (1994) Nanophase mate-
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Materials (CDDM). Kurukshetra University, J Nanomater Biostruct 4(4):729–737
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B 149:7–11
Track-Etch Membranes as Tools for Template Synthesis 15
Kumar S, Chakarvarti SK (2006) Dig J Nanomater Kumar S, Kundu V, Vohra A, Chakarvarti SK (2011d)
Biostruct 1(4):139–143 J Mater Sci Mater Electron 22:995–999. doi:10.1007/
Kumar S, Chakarvarti SK (2007a) J Optoelectron Adv s10854-010-0249-x
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Kumar S, Chakarvarti SK (2007b) Optoelectron Adv 0(2):1250012
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Kumar S, Chakarvarti SK (2007c) J Attidella “Fondazione doi:10.1007/s10854-012-0664-2
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Kumar S, Chakarvarti SK (2007d) Optoelectron Adv doi:10.1007/s10854-011-0615-3
Mater Res Commun 1(7):342–343 Kumar S, Vohra A, Chakarvarti SK (2012d) Nanomater
Kumar S, Chakarvarti SK (2010) J Exp Nanosci Nanotechnol 2:1–8
5:126–133 Kumar S, Vohra A, Chakarvarti SK (2012e) J Mater Sci.
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J Mater Sci Lett 39:6137 12:582
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J Optoelectron Adv Mater 9(10):3191–3193 Price PB (2005) Rad Meas 40:146
Kumar S, Sharma N, Verma NK, Chakarvarti SK (2007b) Prieto AL, Sander MS, Martin-Gonzalez MS, Gronsky R,
J Adv Mater Opto Electron 1(12):677–682 Sands T, Stay AM (2001) J Am Chem Soc 123:7160
Kumar R, Chaudhary M, Chakarvarti SK (2007c) J Mater Rani M, Kumar R, Kumar R, Singh R, Chakarvarti SK
Lett 61(7):1580–1582 (2013a) Chalcogenide Lett 10(3):99–104
Kumar S, Kumar V, Chakarvarti SK (2008a) Rani M, Kumar R, Kumar R, Chauhan RP, Chakarvarti SK
J Superlattices Microstruct 43(4):324–329 (2013b) J Exp Nanosci.. doi:10.1080/
Kumar S, Yousaf Khan P, Verma NK, Chakarvarti SK 17458080.2013.803614
(2008b) Chalcogenide Lett 5(7):143–152 Schonenberger C, vander Zande BMI, Fokkink LGJ,
Kumar S, Kumar S, Verma NK, Chakarvarti SK, Sharma Henny M, Schmid C, Kruger M, Bachtold A,
JK (2008c) Dig J Nanomater Biostruct 3(4):199–202 Huber R, Birk H, Staufer U (1997) J Phys Chem
Kumar S, Verma NK, Chakarvarti SK, Sharma JK, Bhatti B 101:5407
HS (2008d) Chalcogenide Lett 5(12):339–344 Sekhon GS, Verma NK, Chakarvarti SK, Kumar S (2004)
Kumar S, Kumar S, Verma NK, Sharma JK, Chakarvarti Atti Della “Fondazione Giorgio Ronchi” 59(4):529
SK (2009) J Optoelectron Adv Mater-Rapid Commun Sekhon GS, Kumar S, Kaur C, Verma NK, Lu CH,
3(1):33–35 Chakarvarti SK (2011) J Mater Sci 22:1725–1729
Kumar S, Kundu V, Vohra A, Chakarvarti SK (2010a) Sima M, Enculescu I, Trautmann C, Neumann R (2004)
J Mater Sci 22(8):995–999 J Optoelectron Adv Mater 6:121
Kumar S, Kumar V, Sharma SK, Sharma SK, Chakarvarti Singh R, Chakarvarti SK (2008a) J Phys Educ
SK (2010b) Superlattices Microstruct 48:66–71 40(3):591–593
Kumar S, Kumar S, Verma NK, Chakarvarti SK (2011a) Singh R, Chakarvarti SK (2008b) J Phys E 40(3):591–593
J Mater Sci 22:1456–1459 Singh R, Kumar R, Sharma SK, Chakarvarti SK
Kumar S, Kumar S, Verma NK, Chakarvarti SK (2011b) (2006) Dig J Nanomater Biostruct 1(4):149–154
J Mater Sci 22:523–526 Singh R, Kumar R, Chakarvarti SK (2008) J Mater Lett
Kumar V, Kumar S, Kumar S, Chakarvarti SK (2011c) (UK) Mater Lett 62(6–7, 15):874–877
J Mater Sci 22:335–338
16 Track-Etch Membranes as Tools for Template Synthesis
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P
affected the commercialization of polymer elec- low for polyethylene membranes and the rate of
trolyte membrane fuel cells, and consequently the diffusion of chemicals is dependent not only on
focus has shifted toward development of anion the molecular mass of the chemical species but
exchange membranes (AEMs) for anion also on the solubility in lipids [8].
exchange membrane fuel cells (AEMFCs).
AEMFCs are low cost and use non-noble metal
catalyst as cathode material (Sherazi et al. 2013).
References
Recent reports have indicated the use of poly
(vinylbenzyl chloride) grafted on ultrahigh Amada K, Sato T, Takekawa S, Hirata M (1994) Mem-
molecular weight polyethylene (UHMWPE) brane properties of polyethylene films photografted
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in AEMFCs. Ultrahigh molecular weight poly- binding properties of surface-modified porous polyeth-
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when irradiated with gamma radiations, and is a ification of ultra-high molecular weight polyethylene
membranes using underwater plasma polymerization.
low-cost material. Surface-modified UHMWPE Plasma Chem Plasma Process. doi:10.1007/s11090-
membranes have been used as biocompatible 013-9476-2
materials for use in many biomedical applica- Matsuyama H, Okafuji M, Maki T, Teramoto M, Kubota
tions. Surface modification of UHMWPE is N (2003) Preparation of polyethylene hollow fiber
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done using underwater plasma polymerization J Membr Sci 223:119–126
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functional groups which make it relatively easier Polyethylene-based radiation grafted anion-exchange
to introduce polar groups by plasma processes membranes for alkaline fuel cells. J Membr Sci
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thereby attributing biocompatibility (Joshi Uehara H, Kakiage M, Sekiya M, Sakuma D,
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24–84 times higher chemical uptake capacity as polyethylene membranes by an integral permeation
compared to the cellulose membrane. However, it method. J Appl Polym Sci 82:3013–3021
is also known that the solvent retention time is
P
Emulsifier,
Fig. 1 Emulsifier structure EMULSIFIER
and emulsifier distribution
at water-in-oil and oil-in- Hydrophilic Head
water emulsion interface
Hydrophobic Tail
and characterization of iron oxides–polymer book. In: Yampolskii Y, Freeman B (eds) Membrane
composite membranes is given in Dudek gas separation. Wiley, Chichester, pp 159–182
Rybak A, Grzywna ZJ, Kaszuwara W (2009a) On the air
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Rybak A, Krasowska M, Strzelewicz A, Grzywna ZJ
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P
Premix Membrane Emulsification vice versa (Suzuki et al. 1999). The main advan-
tage of PME with phase inversion is that a fine
Goran T. Vladisavljević and Richard G. Holdich emulsion with high disperse phase concentration
Chemical Engineering Department, (over 80 vol.%) can be produced from a
Loughborough University, Leicestershire, UK low-concentration premix. Using a membrane
wetted by the middle phase of the multiple emul-
sion, W/O/W and O/W/O emulsion can be
Premix membrane emulsification (PME) is a inverted into a W/O or O/W emulsion, respec-
homogenization process based on passing tively. In the case of inversion of W/O/W emul-
coarsely emulsified mixture of two immiscible sion (Fig. 2), a lamellar structure is formed inside
liquids (pre-emulsion) through a microporous the pores consisting of surfactant bilayers sepa-
membrane (Suzuki et al. 1996) or porous bed of rated by aqueous films. The aqueous films are
particles (Yasuda et al. 2010). In conventional ruptured at the pore outlets forming reversed
PME (Fig. 1a), the dispersed phase does not wet micelles stabilized by mixed surfactants. This
the membrane surface (y>90 ), and thus, hydro- W/O emulsion can be redispersed into an aqueous
philic and hydrophobic membranes are needed to surfactant solution to form a redispersed W/O/W
manufacture oil-in-water (O/W) and water-in-oil emulsion containing more uniform internal drop-
(W/O) emulsion, respectively. If the pressure dif- lets than the original W/O/W emulsion (Hino
ference is lower than the capillary pressure in a et al. 2000).
pore (Fig. 1c), the droplets are retained by the In order to achieve additional droplet size
membrane, which leads to emulsion separation reduction and improve droplet size uniformity,
rather than homogenization (Koltuniewicz emulsion can repeatedly be passed through the
et al. 1995). same membrane (Vladisavljević et al. 2004).
If the membrane surface is wetted by the dis- Repeated membrane homogenization was origi-
persed phase of the original emulsion (y<90 ) nally developed for homogenization of large lipid
and suitable surfactants are present in both liquid vesicles using track-etch polycarbonate filters
phases, a phase inversion may occur during (Olson et al. 1979). The advantages of premix
homogenization (Fig. 1b), leading to the forma- over direct membrane emulsification are in
tion of W/O emulsion from an O/W premix or smaller droplet sizes and higher droplet
Premix Membrane Emulsification, Fig. 1 Pressure- (c) Phase separation (DP<Pcap, y>90 ) (Koltuniewicz
driven membrane processes with oil-in-water et al. 1995). y is the contact angle at which a dispersed-
pre-emulsion: (a) PME without phase inversion phase/continuous-phase interface meets the membrane
(DP>Pcap, y>90 ) (Suzuki et al. 1996). (b) PME with surface
phase inversion (DP>Pcap, y<90 ) (Suzuki et al. 1999).
Premix Membrane
Emulsification,
Fig. 2 Phase inversion of
W/O/W emulsion into W/O
emulsion using
hydrophobic polycarbonate
membrane. The original
W/O/W emulsion consisted
of liquid paraffin (middle
phase), Span
80 (a hydrophobic
surfactant), and Tween
20 (a hydrophilic
surfactant), and a pore size
was 3 or 8 mm (Hino
et al. 2000)
throughputs that can be achieved for the given small membrane pore sizes, high transmembrane
pore size but at the expense of lower degree of fluxes, and low interfacial tensions between the
monodispersity. dispersed and continuous phase (Vladisavljević
The droplet size in premix ME is determined et al. 2004, 2006). The membranes used in PME
by the membrane pore size, transmembrane flux, are shirasu porous glass (SPG) membrane
physical properties of the dispersed and continu- (Fig. 3), polymeric microporous membranes
ous phase and emulsion formulation. Small drop- (Hino et al. 2000), and microsieves (Nazir
let size in the product emulsion is favored by et al. 2011).
Premix Membrane Emulsification 3
Premix Membrane Emulsification, Fig. 3 PME using SPG membrane. The droplet size in the product emulsion was
9 mm and the membrane pore size was 10.7 mm (Vladisavljević et al. 2004)
WATERWHEEL
PRESSURE
HEAD
PRESSURE CHAMBER
P GENERATOR
FRESH SEA
WATER WATER
MEMBRANE
PUMP
FLUSHING FLOW
b
Brackish water
PRESSURE
EXCHANGER
Power
WATER
FILTER
MEMBRANE MODULES
Sea water TURBINE
Brackish water
Fresh water
WATER
FILTER
bleed
Fresh water
Pressure-Retarded Osmosis, Fig. 1 Schematicdiagram the first prototype PRO, designed and operated by
of (a) the first osmotic salination energy converter, Statkraft (Oslo, Norway) (Skilhagen et al. 2008)
proposed by Norman in 1974 (Norman 1974), and (b)
a Operating pressure in
JW osmotic processes b RO c PRO d FO
Hydraulic Pressure Hydraulic Pressure
(ΔP> Δπ) (ΔP< Δπ) No Hydraulic
Pressure applied
Wmax RO
0
ΔP= Δπ/2 ΔP= Δπ ΔP Salt flux Salt flux Salt flux
PRO
Water flux(JW) Water flux(JW) Water flux(JW)
FO
Pressure-Retarded Osmosis, Fig. 2 (a) Illustration of the magnitude of the operating pressure and water flux of a
membrane in the ideal case and direction of water and salt flux for (b) RO, (c) PRO, and (d) FO process
I. t is clear that the power generated by PRO is a Achilli A, Childress AE (2010) Pressure retarded osmosis:
from the vision of Sidney Loeb to the first prototype
parabolic function of in which the maximum installation – review. Desalination 261:205–211
value is estimated to be at DP ¼ Dp=2 . Thus, Norman RS (1974) Water salination: a source of energy.
the maximum power generated from PRO Science 186:350–352
ðW max ¼ ADp2 =4Þ is proportional to the water Pattle RE (1954) Production of electric power by mixing
fresh and salt water in the hydroelectric pile. Nature
permeability constant and the square of the 174(4431):660
osmotic pressure difference. Skilhagen SE, Dugstad JE, Aaberg RJ (2008) Osmotic
power – power production based on the osmotic pres-
sure difference between waters with varying salt
gradients. Desalination 220(1–3):476–482
P
Propolis Extract Nanofiltration constituents from propolis at low cost. Other sol-
vents as water and propylene glycol are also
Beatriz Mello studied.
UFSCar, Federal University of Sao Carlos, Buri, The excess of solvents in extracts can be
SP, Brazil responsible for some limitation in industrial pro-
cess, causing some variation in the final product,
so it is necessary to concentrate it before use. The
Propolis is a mixture of beeswax and resins col- most traditional methods are lyophilization
lected by the honeybee from plants, particularly (freeze-drying), vacuum distillation, evaporation,
from flowers and leaf buds. Its composition and distillation. These methods require a high
depends on the type of plants accessible to the energy consumption and in some cases high tem-
bees. There are changes in color, odor, and prob- peratures that can degrade some functional com-
ably medicinal characteristics according to pounds. To avoid these drawbacks, the method of
source and the season of the year. The major nanofiltration has been studied for propolis
compounds are resins composed of flavonoids concentration.
and phenolic acids or their esters, which often Nanofiltration membranes are the same as
form up to 50 % of all ingredients. The variation reverse osmosis membranes; only the network
in beeswax content also influences the chemical structure is more open, causing a lower retention
analysis. More than 500 different compounds of monovalent salts (Mulder 1996). It has been
from propolis through several regions were iso- widely used in concentration process where the
lated, being impossible to determine their com- objective is to retain functional compounds with
position without first analysis. low molecular weight, especially phenolic
Propolis composition is responsible for a lot of compounds.
studies relating antimicrobial, antioxidant, Propolis nanofiltration has been studied for
anticarcinogenic and antifungal activities, some authors recently, and the process showed a
among other health benefits. Thanks to these high efficiency in retaining flavonoids and phe-
characteristics, a great interest exists to use prop- nolic compounds, which are of major importance
olis for human consumption as being incorpo- to propolis quality, reaching more than 95 %
rated in drugs, cosmetics, and foods. rejection in concentration factor of 3.0 and 4.0.
The most usual way to manipulate propolis is Moreover, the process had low fouling and con-
by its extract. Ethanol is the most common sol- centration polarization, phenomena that can
vent used once it can extract the major make the whole process inviable through flux
decay (Tylkowski et al. 2010; Mello et al. 2010).
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_503-2
2 Propolis Extract Nanofiltration
Propolis Extract Nanofiltration, Fig. 1 Differences between conventional (a) and tangencial filtration (b)
Propolis Extract Nanofiltration, Fig. 2 Schematic diagram of propolis extracts nanofiltration process
Application of this technology could increase technology for medicine and nutritional additive
the use of propolis in many industrial applica- production based on propolis extracts (Fig. 1).
tions, in new research projects, and in the devel-
opment of new products with functional
properties. Furthermore, this process allows
References
removal of the solvent from the extract, reducing
the disadvantages associated with using alcoholic Mello BCBS, Petrus JCC, Hubinger MD (2010) Concen-
extractions, and being feasible the use of another tration of flavonoids and phenolic compounds in aque-
solvent during extraction procedure. In the mem- ous and ethanolic propolis extracts through
brane process, the product is not submitted to nanofiltration. J Food Eng 96:533–539
Mulder M (1996) Basic principles of membrane technol-
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energy saving.
Cross-flow nanofiltration experiments showed
that the nanofiltration process can be feasible
P
Purification of Plasma from useful HDL and other plasma proteins. Conven-
Cholesterol by Immunoaffinity tional gel-bead columns have certain limitations
Membranes especially when studying with viscous media
such as human blood. Alternative carriers such
Nilay Bereli, Handan Yavuz and Adil Denizli as membranes, monoliths, and cryogels are
Department of Chemistry, Biochemistry designed to solve drawbacks of gel-beads such
Division, Hacettepe University, Ankara, Turkey as high-pressure drop and flow rate limitations
that limit efficiency of applications (Bereli
et al. 2011). In random immobilization of anti-
Coronary heart diseases are responsible for the bodies, they can bind to the polymer surface at
4.3 million deaths in all of Europe and also can many different points (Denizli 2002; Yavuz and
cause lifetime disability. The annual economic Denizli 2003, 2005). This generally results in
cost is estimated to be 192 billion with a substan- decrease in the antigen-binding capacity because
tial increase (Harland 2012). Together with the the accessibility of the antigen-binding sites is
high blood pressure, LDL cholesterol is widely prevented in most cases. Anti-LDL immobiliza-
recognized as one of the major risk factors in the tion onto the polymeric carriers can be performed
development of coronary heart diseases because in an oriented mode to leave its antigen-binding
of its ability to build up in the lining of arteries to fragments free. It can be done by either using Fc
form atheromas and fatty acid deposits (Bruckert receptor proteins such as Protein A and Protein G,
1999; Thompson 2003). In the case where dietary by using carbohydrate binding polymer in order
and drug therapy is insufficient to set safe blood to bind through the carbohydrate moiety, or by
cholesterol level, extracorporeal cholesterol using artificial or digestion product Fab frag-
removal techniques with different selectivity ments. Immunoaffinity adsorbent obtained by
and specificity have been used. Plasmapheresis, oriented immobilization of anti-LDL onto the
cascade filtration, heparin induced LDL precipi- biocompatible PHEMA cryogel membranes
tation (HELP), thermofiltration, dextran induced show better LDL adsorption capacity (129 mg
LDL precipitation, and direct adsorption of lipo- LDL/g) from hypercholesterolemic human
proteins are the examples (Blaha 2003). The most plasma than random anti-LDL immobilized
selective removal of LDL has been achieved by adsorbent (111 mg LDL/g) while the amount of
the use of monoclonal antibodies against the anti-LDL bound in an oriented mode was the one
apoB100, the main protein component of LDL, third of the random immobilized. Nonspecific
as a ligand (Kane et al. 1975). This allows adsorption of other lipoproteins was very low in
removal of harmful LDL without decreasing both cases. It has been also shown that these
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_513-1
2 Purification of Plasma from Cholesterol by Immunoaffinity Membranes
adsorbents can be used many times without sig- Denizli A (2002) Preparation of immunoaffinity mem-
nificant decrease in the adsorption capacity branes for cholesterol removal from human plasma.
J Chromatogr B 772:357
(Bereli et al. 2011). Harland JI (2012) Food combinations for cholesterol low-
ering. Nutr Res Rev 25:249–266
Kane JP, Sata T, Hamilton RL, Havel RJ
References (1975) Apoprotein composition of very low density
lipoproteins of human serum. J Clin Invest
56:1622–1634
Bereli N, Şener G, Yavuz H, Denizli A (2011) Oriented Thompson GR (2003) LDL apheresis. Atherosclerosis
immobilized anti-LDL antibody carrying poly 167:1
(hydroxyethyl methacrylate) cryogel for cholesterol Yavuz H, Denizli A (2003) Immunoaffinity beads for
removal from human plasma. Mater Sci Eng selective removal of cholesterol from human plasma.
C 31:1078–1083 J Biomater Sci Polym Ed 14:395
Blaha M (2003) Extracorporeal LDL-cholesterol elimina- Yavuz H, Denizli A (2005) Immunoadsorption of choles-
tion in the treatment of severe familial hypercholester- terol on protein A oriented beads. Macromol Biosci
olemia. Acta Med 46:3 5:39–48
Bruckert E (1999) LDL apheresis: questions for the future.
Transfus Sci 20:43
P
PVA-Based Anion-
Exchange Membranes,
Fig. 1 Scheme of OH O O
chemical cross-linking of
OH OH OH CHO CH
poly(vinyl alcohol) (PVA) H+
using glutaraldehyde (GA) + CH2 CH2
(Higa et al. 2012) 3 −2H2O 3
OH OH OH CHO CH
OH O O
PVA chains GA
Cross-linked PVA
Chemical cross-linking
point with GA
PVA-Based Anion-Exchange Membranes, Fig. 2 Schematic diagram of membrane structure of an AEM with IPN
structure
radiation
P ! P •
P • þ M ! PM • References
▶ Application of Electrodialysis
R
Reverse Electrodialysis in High gypsum seeds were used to increase the rate of
Supersaturation Mode gypsum nucleation and significantly reduce the
level of CaSO4 supersaturation in the EDR con-
Piotr Dydo and Marian Turek centrate (Korngold et al. 2005). It was found that
Faculty of Chemistry, Silesian University of antiscalant diminished the seeding effect on gyp-
Technology, Gliwice, Poland sum crystallization and increased the onset of
crystallization time. Thus, it was demonstrated
that the ED process combined with continuous
Synonyms CaSO4 precipitation (in a separate precipitator)
may be successfully carried out under a reverse
Electrodialysis reversal in high supersaturation polarity operation regime.
mode In a novel EDR design (Turek et al. 2006),
different diluate and concentrate linear velocity
The supersaturation level with sparingly soluble values are applied instead of recirculation of con-
salts, mainly calcium carbonate and calcium centrate. Thus, the concentrate’s linear flow veloc-
sulfate, and resulting product water recovery in ity is several times lower than the diluate’s, so a
the classical electrodialysis reversal with certain diluate concentration decrement results in
recycling of ED concentrate are limited by a a several times higher increment in the concentrate
relatively long mean residence time in the con- salt concentration. At the same time, low resi-
centrate loop (Myint et al. 2011). A substantial dence time is gained due to a single-pass mode.
increase in scale-free operation at a high super- The ED process with different diluate and concen-
saturation level may be gained in a single-pass trate flow velocities may be carried only when
mode of operation only. In this case, the mean applying a thin, e.g., 0.19 mm, net spacer with
residence time (favorably accompanied by low high strand density that protects the membrane
variance of residence time distribution (RTD)) against bulging. The intermembrane distance
should be small when compared to nucleation also influences the rate of both diluate and con-
time of crystallization of the sparingly soluble centrate salt content changes along the ED mem-
salt in question (Turek et al. 2006). brane. The amount of salt passing a certain
Electrodialysis was carried out in a single-pass membrane surface in a certain period of time
mode with symmetric reversed polarity every results from the current density value. When
6–10 h. The problem of CaSO4 precipitation added to a small volume of the solution, being
was prevented by continuous removal of gypsum inversely proportional to the intermembrane dis-
from the brine in a separate precipitator, in which tance, it would increase its concentration to a large
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_520-4
2 Reverse Electrodialysis in High Supersaturation Mode
The hydrogen permeation at constant temper- where P0H2, Ea, R, and T are the pre-exponential
ature through a dense palladium membrane is factor, the apparent activation energy, the univer-
described by the following general expression: sal gas constant, and the absolute temperature,
respectively. Consequently, when n is 0.5, the
pnH2 , upstream pnH2 , downstream hydrogen flux can be written in terms of the
J H 2 ¼ PH 2 so-called Richardson equation:
t
pn
H 2 , upstream pH 2 , downstream
n
where J H2 is the hydrogen flux through the mem- Ea
J H2 ¼ P0H2 exp :
brane, PH2 the hydrogen permeability, t the mem- RT t
brane thickness, p the hydrogen partial pressure,
and n the dependence factor of the hydrogen flux References
on the hydrogen partial pressure, experimentally
determined in the range 0.5–1 (Dittmeyer Dittmeyer R, Höllein V, Daub K (2001) Membrane reac-
tors for hydrogenation and dehydrogenation processes
et al. 2001). When n is 0.5, the hydrogen flux based on supported palladium. J Mol Catal A Chem
follows the so-called Sieverts’ law. 173:135–184
The hydrogen permeation through membranes Gallucci F, De Falco M, Tosti S, Marrelli L, Basile
is an activated process ruled by an Arrhenius law: A (2007) The effect of the hydrogen flux pressure
and temperature dependence factors on the membrane
reactor performances. Int J Hydrog Energy
Ea 32(16):4052–4058
PH 2 ¼ P0H2 exp
RT
S
G p~ 1
Sanchez and Lacombe Theory r þ þ T~
¼ e 1 lnð1 e
rÞ
rNRT e
r e
r
#
Giulio C. Sarti 1 Xf
Department of Chemical Engineering, Mining þ lnðe
rÞ þ i
lnðfi Þ : (1)
r i
r i
and Environmental Technology, University of
Bologna, Bologna, Italy
and by the expression of the volumetric equation
of state:
This is a molecular theory for classical fluids,
~ 1
based on a compressible lattice fluid (LF) model e þ p~ þ T lnð1 e
r2
rÞ þ 1 e r ¼ 0 (2)
for the representation of the microstates of pure r
components and mixtures. Each molecular spe-
cies is considered decomposed in a sequence of Equation 1 has been written for the common case
contiguous segments (r-mers). The lattice cells in which the number of configurations available
are either empty or occupied by a molecular for each ri-mer in the close-packed pure state is
segment of the components in the mixture. The unity. The quantities used by the model are
volume of the cells is allowed to vary with com- defined in Table 1. The model expressions con-
position. Statistical arguments are used to calcu- tain pure component parameters and one binary
late the number of configurations available for a interaction parameter for each couple of compo-
system of N molecules with given configurational nents in the mixture.
energy and volume; the partition function is cal- The pure component parameters for a series of
culated from statistical mechanics results as a classical fluids are available (Sanchez and
function of temperature and pressure, in a mean Lacombe 1976, 1978; Sanchez and Panayiotou
field approximation, and finally, a simple expres- 1994). The model can describe the liquid-vapor
sion for the total Gibbs free energy is obtained for equilibrium conditions for pure components rea-
pure species (Sanchez and Lacombe 1976) and sonably below the critical point (Sanchez and
for mixtures (Lacombe and Sanchez 1976). In the Lacombe 1976), as well as the phase equilibrium
derivation, the flexibility parameter of the r-mers properties of different binary mixtures of simple
and the close-packed volume of a molecule are classical fluids (Lacombe and Sanchez 1976),
assumed independent of temperature and based on a single value of the binary interaction
pressure. parameter; the latter value can be obtained from
Relevant results of the theory are represented different experimental data for the mixture, i.e.,
by the expression of Gibbs free energy: from azeotropic temperature, change in volume
Sanchez and Lacombe Theory, Table 1 List of symbols and properties used in the lattice fluid theory by Sanchez
and Lacombe
Symbol Name Definition/property
Pure ri* Characteristic
component density of pure
i component i
pi* Characteristic
pressure of pure
component i
Ti* Characteristic
temperature of
pure component i
ri0 Number of lattice r 0i ¼ rM vi
i i
sites occupied by a
mole of pure
component i
vi * RT i
Volume occupied vi ¼ pi
by a mole of lattice
sites of pure
substance
ei* T i
Characteristic ei ¼ k
energy of pure
component i
Mixtures N Total number of
moles
T Temperature
p Pressure
r Density
ri Density of species i ri ¼ oi r
oi Mass fraction, oi ¼ rri
i=1,2,. . .,Nt
fi Volume fraction fi ¼ X i i
o =r
oi =ri
i
X oi
r* Characteristic 1
¼
r ri
density of the i
mixture
X X X
p* Characteristic p ¼ fi pi 12 fi fj Dpij
pressure of the i i j6¼i
mixture
pffiffiffiffiffiffiffiffiffiffiffiffi
ffi
Dpij Binary parameter Dpij ¼ pi þ pj 2 1 kij pi pj
kij, Cij Dimensionless Cij ¼ 1 kij
binary parameter
X
r Molar average r¼ xi r i
number of lattice i
sites occupied by a
molecule in the
mixture
T* Characteristic X T i
T ¼ pr xi r 0i ¼ p Rv
temperature of the
i
pi
mixture
e* Characteristic e ¼ Tk
energy
(continued)
Sanchez and Lacombe Theory 3
Volumetric r 2 þ p~ þ T~ lnð1 e
e r Þ þ 1 1r e
r ¼0
equation of state
" #
A Total Helmholtz XNt
fi
free energy
A
r þ T~
¼ e 1
1 lnð1 e
rÞ þ e
r lnðr Þ
1
þ lnðfi Þ
rNRT er r
i¼1 i
" #
G Total Gibbs free XNt
fi
energy
G
¼ e
r þ p~ þ T~ 1
1 lnð1 e
rÞ þ e
r lnðr Þ
1
þ lnðfi Þ
rNRT er er r
i¼1 i
Introduction
Filter Comparison
Sand filters are employed as primary treatment in Sand Depth
a water/wastewater industry. Raw water with Media Single Three
various particle sizes of colloidals need to be Bed usage 1–3 % 90 %
coagulated/flocculated with coagulants and floc- Service rate 2–4 gpm/ft2 7–10 gpm/ft2
culants. The filter is filled with media such as Backwash 15 gpm/ft2 15 gpm/ft2
garnet, sand of varying sizes, and anthracite. Removal 40 m 10 m
These filters could be dual-media or multimedia
based on the raw water characteristics. A very
high degree of clarity is achieved in the filtered
water on account of finer particles of garnet at the
bottom which trap finer turbidity particles. Tur-
Types of Sand filter
bidity is trapped and held throughout the entire
bed depth, rather than the top 1 or 2 in.
Filtration is used in addition to regular coagula-
Mechanical filtration will remove almost all
tion and sedimentation for removal of solids from
forms of turbidity. In many cases, filters
surface water or wastewater. This prepares the
containing specially graded and sized gravel and
water for use as a portable boiler or cooling
sand are effective in screening out turbid parti-
makeup. Filtration is a simple mechanical pro-
cles. With such units, a periodic backwashing to
cess involving mechanisms of adsorption
remove the filtered material is all the mainte-
(physical and chemical), straining, sedimenta-
nance necessary.
tion, interception, diffusion, and inertial
Zeta Potential: This is a commonly used term
compaction.
in filtration. An increase or decrease of zeta
potential along with pH is an important criterion • Dual-media filter
in particle adhesion during the filtration process. • Multimedia filter
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_525-2
2 Sand Filter
The sand in a pool sand filter (# 20 silica sand; also more dense (less space between particles),
45–55 mm) is specially graded to trap particles in they remain at the bottom. Even after high-rate
the 20–100 m range. The size and shape of the filter backwashings, the layers remain in their proper
media affect the efficiency of the solids removal. location in the mixed media filter bed.
Sharp, angular media form large voids and remove The table below lists four media used in mul-
less-than-rounded media of equivalent size. Though timedia filtration. The use of too many different
most suspended solids are trapped at the surface or media combinations causes severe backwashing
in the first 1–2 in. of bed depth, some penetration is difficulties. High wash rates expand the magne-
essential to prevent a sharp increase in pressure tite layer which might wash away the anthracite
drop. As a sand filter collects dirt, its efficiency from the filter necessitating high wash water.
increases, trapping more dirt. The media need to Media in multimedia filters:
be sufficiently coarse to allow solids to penetrate
the bed for 2–4 in.. It is time to backwash the Effective size, mm Specific
Media (in.) gravity
captured dirt out of the filter. They need the lowest
Anthracite 0.7–1.7 (0.03–0.07) 1.4
maintenance of the three types of pool filters. You
Sand 0.3–0.7 (0.01–0.03) 2.6
may need to open up the tank every 5 years or
Garnet 0.4–0.6 (0.016–0.024) 3.8
so. Sand filters are the easiest to operate and main- Magnetite 0.3–0.5 (0.01–0.02) 4.9
tain. If your sand filter requires frequent
backwashing every week or two, the sand bed may
be “mothballed,” or it may be “channeled.” It may
calcify with calcium deposits. A properly sized sand Slow Sand Filtration (SSF)
filter could go over 10 years between sand changes.
The major advantages of dual media filtration Slow sand filtration technology is especially ideal
are higher rates and the longer runs. for small communities required to use filtration to
Soft swim require annual cleaning of the filter comply with new regulations.
sand to prevent it from “gumming up.” High
amounts of bather oils can gum up a sand bed.
How SSF Works
proven effective when used carefully; however, 10 % or less of the rates that are possible in rapid
they are relatively expensive and present safety filtration.
issues to the handlers and the environment.
A disadvantage of the SSF is the large amount
of land required, a consequence of the slow rates Sand Specifications
of water filtration that are possible, typically only
Sand is characterized by the diameter of the indi-
vidual sand grain (0.15–0.35 mm) and the effec-
tive size of the composite sand, ES or d10. d10 is
defined as the sieve size in mm that permits
passage of 10 % by weight of the sand. The
uniformity coefficient (UC) of sand is defined as
d60/d10. Effective size (ES) is such that approx-
imately 10 % of the total grains by weight are
smaller and 90 % are larger. ES is the minimum
size of most of the particles. Uniformity is mea-
sured by comparison of effective size to the size
at which 60 % of the grains by weight are smaller
and 40 % are larger. This latter size, divided by
the ES, is called the uniformity coefficient – the
smaller the UC, the more uniform the media
particle size.
It is recommended to use fine-grade sand
(0.15–0.35 mm), uniformity coefficient
Sand Filter, Fig. 1 A typical sand filter configuration (UC) always <3, preferably <2 and be washed
free of clay, loam, and organic matter. Fine
Sand Filter, Fig. 2 A typical slow sand filter for water purification
4 Sand Filter
particles will quickly clog the filters and frequent of organic sediment left in the sand filter are eaten
cleaning will be required. Sand that is not uni- by bacteria and protozoans which “stick” in the
form will also settle in volume, reducing the layers of slime that form around the sand parti-
porosity and slowing the passage of water. cles, and the clean water which passes through
the filter is safe to drink. Provided that the grain
size is around 0.1 mm in diameter, a sand filter
Biological Activity can remove all fecal coliforms (bacteria that orig-
inate from feces) and virtually all viruses.
Microbial activity builds up very quickly in
greenhouse nutrient solutions, and slow sand fil-
ters become active in biological suppression Conclusion
without any special inoculation. Safe drinking
water is a high priority for people without main Sand filters serve as the major equipment of fil-
facilities. tration in every area of daily use – from swim-
Slow gravity sand filters remove bacteria and ming pools to household and water treatment
other small particles from drinking water, making plants. This primary treatment shall reduce the
it safe to drink. Sand filters cannot cope with load on subsequent pressure filtration. Best engi-
heavy metals or other excessive pollutants. neering practices are advocated in the design of
Their prime purpose is to remove bacteria and sand filters and operation thereafter for clear
particles. If the source of raw water has a high water suitable for downstream hygienic use.
level of contamination, locate a new one. Even Clarifier effluents of 2–10 NTU may be improved
spring water or very clean water is to be checked to 0.1–1.0 NTU by conventional sand filtration.
for undesirable contaminants. If the water con-
tains sediment, it should be passed through an
initial settling tank before it gets into the sand References
filter.
Colorado State University, CH2M Hill Engineers, Denver
(CO) Water Department
http://www.gewater.com/handbook/ext_treatment/ch_6_
How the Filter Works filteration.jsp
http://www.poolcenter.com/sand-pool-filter-information.
The water passes through the sand from top to html
Manual of design for slow sand filtration
bottom. Any larger suspended particles are left
The Davnor BioSand Water Filter
behind in the top layers of sand. Smaller particles
S
Saturated and Supersaturated Solutions, Table 1 Pretreatment methods and their effect on scaling in reverse
osmosis (Baker 2001) (XX highly effective, X moderately effective)
Pretreatment method CaCO3 CaSO4 SiO2
Acid dosage XX
Antiscalant dosage X XX
Softening/ion exchange XX XX
Preventive cleansing X X
Adjustment of process parameters X XX
Quick filtration X
Flocculation X
Micro- and ultrafiltration XX
Candle filters X
Solutions to prevent scaling include the use of The membrane process in which the highest
antiscalants or acids such as hydrochloric acid risk for scaling is encountered is reverse osmosis,
(HCl) and sulfuric acid (H2SO4). The use of because ions present in sparingly soluble salts are
acids is an effective solution, since the solubility rejected by reverse osmosis membranes. Other
of salts increases significantly at lower processes related to salt removal or transport,
pH. Sulfuric acid is the most commonly used such as electrodialysis and nanofiltration (and to
acid for this purpose. However, the trend is to a lesser extent, forward osmosis), are also at risk.
use more hydrochloric acid, because sulfuric acid Supersaturation of salts is also crucial – and in
can negatively influence the fouling speed of a this case a desired phenomenon – in the mem-
membrane by the addition of sulfate ions, which brane crystallizers. It has been shown that in a
can stimulate precipitation of e.g., gypsum membrane contactor producing supersaturated
(CaSO4). solutions, crystals with extremely high purity
A separate unit for removal of the scalant prior can be obtained, as shown in Fig. 1 for NaCl
to the membrane separation might be necessary (Drioli et al. 2004). Similar results can be
(Bremere et al. 1998), especially when going obtained for CaCO3 and MgSO4 7H2O as solid
from high to very high feed recoveries (very products. Crystal growth generally starts at solute
high permeate to feed ratio). Some pretreatment concentrations at which the nucleation occurs;
methods and their effect on scaling are summa- the growth rate, depending on the supersaturation
rized in Table 1 (Baker 2001). However, a higher degree, is determined by a combination of the
recovery shifts the problem to scaling of other nature of the growing crystal surface and the
salts with lower initial concentrations, which are diffusional rate (Curcio et al. 2001). Direct con-
not removed in advance. In any case, diagnosis, tact membrane distillation can be employed to
prediction, prevention, and control of scaling are reach the supersaturation required for
important in any membrane application with crystallization.
scaling potential (Vrouwenvelder et al. 2003).
Saturated and Supersaturated Solutions 3
Saturated
and Supersaturated
Solutions, Fig. 1 High-
purity NaCl salts obtained
in a membrane crystallizer
(Drioli et al. 2004, used
with permission of
Elsevier)
CaCO3 CCPP >900 (LSI >2.8) The following categories of information must
CaSO4 3.0 Ksp be present on the MSDS:
BaSO4 105 Ksp
SrSO4 20 Ksp • Product information – product identifier
CaF 1,000 Ksp (name), manufacturer and suppliers names,
SiO2 120 ppm addresses, and emergency phone numbers
• Hazardous ingredients
The available antiscalants are highly effective • Physical data
at low dose rates in a wide range of feed water • Fire or explosion hazard data
types and pH ranges. They provide both scale • Reactivity data: information on the chemical
and inorganic fouling control while compatible instability of a product and the substances it
with all membrane configuration and types. may react with
CCPP: calcium carbonate precipitation • Toxicological properties: health effects
potential. http://www.awwa.org/Resources/ • Preventive measures
RTWCorrosivityCalc • First aid measures
Saturation-level formulas for common scale- • Preparation information: who is responsible
forming species for preparation and date of preparing the
MSDS
Calcium carbonate (Ca)(CO3)/KSP CaCO3
Barium carbonate (Ba)(CO3)/Ksp BaCO3
Calcium sulfate (Ca)(SO4)/Ksp CaSO4 Scale Prediction and Saturation
Barium sulfate (Ba) (SO4)/Ksp BaSO4 Water is said to be saturated with a compound
Amorphous silica H4 SiO4/(H20)2 x Ksp SiO2 such as calcium carbonate if it will not precipitate
Calcium fluoride (Ca) (F)2/KspCaF2 the said compound or dissolve any of the solid
Strontium carbonate (Sr)(CO3)/Ksp SrCO3 phase of the compound when left undisturbed,
Strontium sulfate (Sr) (SO4)/Ksp SrSO4 under the same conditions, for an infinite period
Magnesium hydroxide (Mg) (OH)2/KSP Mg(OH)2 of time. Water that will not precipitate or dissolve
Tricalcium phosphate (Mg) (OH)2/Ksp Mg(OH)2 a compound is at equilibrium for that compound.
The amount of a chemical compound that can
Material Safety Data Sheet (MSDS) be dissolved in water and remain in solution for
A Material Safety Data Sheet is a document that this infinite period of time is described by the
contains information on the potential hazards solubility product (Ksp). In the case of calcium
(health, fire, reactivity, and environmental) and carbonate, solubility product is defined by
how to work safely with the chemical product and relationship:
an essential starting point for the development of
a complete health and safety program. It also ðCaÞðCO3 Þ ¼ KSP ;
contains information on the use, storage, han-
dling, and emergency procedures related to the where (Ca) is the activity of sodium.
hazards of the material. The MSDS contains (CO3) is the carbonate activity.
much more information about the material than KSP is the solubility product for calcium carbon-
the label. MSDSs are prepared by the supplier or ate at the temperature.
manufacturer of the material. It is intended to tell
what the hazards of the product are, how to use In a more generalized sense, the term (Ca)
the product safely, what to expect if the recom- (CO3) can be called the ion activity product
mendations are not followed, what to do if acci- (IAP) and the equilibrium condition described
dents occur, how to recognize symptoms of by the relationship IAP = Ksp.
overexposure, and what to do if such incidents Scale indices developed are derived from the
occur. basic concept of saturation:
4 Scale Inhibitor
Scale Inhibitor, Table 1 Antiscalant consumption inevitable by extending induction time (Ferguson
Consumption (kg/h) without second-pass brine 1984, Ferguson et al. 2011; Gill et al. 1983;
recirculation Tomson et al. 2002; Amjad and Masler 1985).
First-pass RO 13.3 Time selected is the residence time the
Second-pass front/rear 3.2/3.8 inhibited water will be in the system. The inhib-
Total 20.3 itor must prevent scale formation or growth until
Consumption with recirculation the water has passed through the system and been
First pass 9.5 discharged.
Second-pass front/rear 3.2/0.6
Temperature affects the rate constant for the
Total 13.3
induction time relationship. As in any kinetic
Consumption in conventional RO design
formula, the temperature has a great effect on
First pass 7.0
reactants collision frequency. This effect is inde-
Second pass 7.0
pendent of the effect of temperature on
Total 14.0
saturation-level calculations. A basic chemistry
concept is that reaction rates increase with tem-
perature. The rates approximately double for
• If a water is undersaturated with a compound, every 10 C increase in temperature.
IAP<Ksp. It will tend to dissolve the pH affects saturation level, but it also affects
compound. the dissociation state and stereochemistry of the
• If a water is supersaturated with a compound, inhibitors (Tomson et al. 2002). By virtue of its
IAP>Ksp. It tends to precipitate the impact on the charge and shape of an inhibitor
compound. molecule, inhibitor effectiveness can be a func-
• If a water is at equilibrium with a compound, tion of pH, but may not always be significant in
IAP =Ksp. It tends not to dissolve or precipi- the pH range of interest (6.5–9.5). Acid
tate the compound. dosage and consequently the pH of the medium
IAP = ion activity product; have a significant bearing on the antiscalant
Ksp = solubility product. dosage in a membrane-based treatment plant.
Few BWRO (Brackish Water Reverse Osmosis)
units can run without scale inhibitor.
Table 1 summarizes the overall results of
antiscalant consumption at 300-ML/day of Ade-
Concentration Polarization
laide (Southern Australia) Desalination Plant
Concentration polarization is a phenomenon in
(ADP). It has been estimated that the antiscalant
which ion concentrations in a membrane’s
dose at this facility shall be 5 % lower than for a
boundary layer are projected to be higher than
conventional RO design due to brine
those of the bulk water. The amount of boundary
recirculation of the second pass ahead of the RO
layer concentration can vary from 1.12 to 1.4
process.
that of the bulk water for clean membranes
(Byrne 2002). Higher concentrations have been
Dosage Optimization reported for fouled systems due to “cake-
Induction time. Reactions do not occur instanta- enhanced” concentration polarization.
neously. A time delay occurs when all reactants Concentration polarization can affect all
are combined. They must come together in the concentration-dependent calculations, including:
reaction media to allow the reaction to occur.
Thermodynamic evaluations of a water scale • pH
potential predict what will happen if water is • Brine ion concentrations
allowed to sit undisturbed under the same condi- • Recovery limits
tions for an infinite period of time. Scale inhibi- • Maximum recovery based on antiscalant
tors do not prevent precipitation; they delay the saturation-level maximum
Scale Inhibitor 5
• Dosage References
Spontak RJ, Patel NP (2000) Thermoplastic elastomers: Thomas S, Visakh P. M (2011) Handbook of engineering
fundamentals and applications. Curr Opin Colloid and specialty thermoplastics, Scrivener Publishing
Interface Sci 5:333–340 van der Schuur MJ, Gaymans RJ (2007) Influence of
Subiman G, Khastgir, Bhowmick AK (1998) Effect of morphology on the properties of segmented block
block molecular weight on the mechanical and copolymers. Polymer 48:1998–2006
dynamic mechanical properties of segmented polyam-
ide. Polymer 39:3967–3975
S
Serum Proteins, Table 1 Concentrations and sizes of proteins present in milk (Walstra et al. 1999)
Concentration in whole milk (g/l) Average molecular size or weight
Total serum proteins 0.7 3–6 nm
a-Lactalbumin 0.12 14 kD
B-Lactoglobulin 0.32 18 kD
BSA 0.04 66 kD
Proteose-peptone 0.08 4–40 kD
Immunoglobulins 0.08 150–900 kD
Lactoferrin 0.01 86 kD
Transferrin 0.01 76 kD
Others 0.04
that are known to contain bioactive components. and organo-mineral membranes for use in ultrafiltra-
Since hydrolysates are much smaller as the pro- tion. J Membr Sci 113:247
Krstic DM, Tekic MN, Caric MD, Milanovic DS
teins, they can be easily removed through with (2002) The effect of turbulence promoter on cross-
ultrafiltration. Separating the whole protein from flow microfiltration of skim milk. J Membr Sci
a mixture is still a challenge; a-lactalbumin may, 208:303
for example, first be thermally aggregated, prior Pouliot M, Pouliot Y, Britten M (1996) On the conven-
tional cross-flow microfiltration of skim milk for the
to membrane ultrafiltration; alternatively also production of native phosphocaseinate. Int Dairy
adjustment of pH and salt concentration can be J 6:105
used to influence electrostatic and steric interac- Punidadas P, Rizvi SSH (1998) Separation of milk pro-
tion and in this way enhance the selectivity of teins into fractions rich in casein or whey proteins by
cross flow filtration. Food Res Int 31:265
ultrafiltration as described in, e.g., Cheang and Vadi PK, Rizvi SSH (2001) Experimental evaluation of a
Zydney (2003). uniform transmembrane pressure crossflow
microfiltration unit for the concentration of micellar
casein from skim milk. J Membr Sci 189:69
Van der Horst HC, Timmer JMK, Robbertsen T, Leenders
References J (1995) Use of nanofiltration for concentration and
demineralization in the dairy industry: model for mass
Cheang B, Zydney AL (2003) Separation of a-lactalbumin transport. J Membr Sci 104:205
and b-lactoglobulin using membrane ultrafiltration. Walstra P, Geurts TJ, Noomen A, Jellema A, van Boekel
Biotechnol Bioeng 83:201 MAJS (1999) Dairy technology: principles of milk
Doyen W, Adriansens W, Molenberghs B, Leysen properties and processes. Marcel Dekker, New York
R (1996) A comparison between polysulfone, zirconia
S
Silica DDR Membrane, Fig. 1 SEM images of the section (Tomita et al. 2004). Reprinted with permission
microstructure of a DDR type zeolite membrane formed from ref. Tomita et al. 2004. Copyright 2016, Elsevier
on a porous alumina substrate, (a) surface and (b) cross-
Silver Recovery by Bulk Liquid (ii) production of a large amount of toxic chem-
Membrane (BLM) ical sludge in which disposal/treatment is a very
costly affair and it is not eco-friendly; (iii) poor
Argurio Pietro process selectivity, thus metal recovery is not
Department of Environmental and Chemical achieved; (iv) adsorption-based processes are
Engineering, University of Calabria, Arcavacata not continuous, requiring regeneration steps that
di Rende (CS), Italy negatively affect process economy.
Carrier-mediated transport through liquid
membrane (LM) has been recently considered
The occurrence of silver in the natural water as one of the most powerful technology to con-
environment is of great relevance owing to its centrate, separate, and recover metal ions from
toxicity to aquatic plants and animals even at diluted solutions. LM-based separation tech-
very low concentration, particularly when it is niques combine extraction and stripping into a
in the free ion form (Ag+). Silver content into one-step process, thus having great potential for
the aquatic environment has increased in the last reducing the solvent inventory requirement and
years owing to its increasing use in the medical also allowing the use of expensive and highly
and photographic-imaging industry and in the selective extractant (Molinari and Argurio
manufacturing of electronics, silverware, and 2009). The lower capital and operating costs,
jewelry. An estimated amount of 150 tons of the low energy consumed, and the high selectiv-
silver is released into the aquatic environment ity are the main advantages of LM systems.
every year. As a result, separation and recovery Thanks to these characteristics, LM-based tech-
of silver from industrial wastewaters is of great niques permit to obtain the recovery of heavy
importance (Altin et al. 2010). metal ions and the production of water with
Conventional separation process includes pro- good quality, resulting into both environmental
cesses like solvent extraction, chemical precipi- and economic benefits.
tation, adsorption, and membrane filtration. LM-based process includes bulk liquid mem-
These techniques efficiently remove metal ions brane (BLM), emulsion liquid membrane (ELM),
producing water within international health stan- and supported liquid membrane (SLM). BLM
dards, but present some limitations: (i) large usually consists of two aqueous phase (feed and
amount of solvent required when dilute solutions strip) separated by a water-immiscible liquid
were processed, making solvent extraction not membrane phase (Molinari and Argurio 2011).
very cheap and safe, since the used solvents are Usually the organic solvents, employed as LM
often chlorinated and sometimes carcinogenic; phase, are pre-saturated with water by shaking a
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_538-6
2 Silver Recovery by Bulk Liquid Membrane (BLM)
Rounaghi GH, Kazemi MS, Sadeghian H (2008) Trans- Rounaghi GH, Hosseiny MS, Chamsaz M (2011) Study of
port of silver ion through bulk liquid membrane using competitive transport of metal cations through bulk
macrocyclic and acyclic ligands as carriers in organic liquid membrane using 40-nitrobenzo-18-crown-6
solvents. J Incl Phenom Macro 60:79–83 and diaza-18-crown-6. J Incl Phenom Macro
69:221–229
S
Solvent-Resistant Nanofiltration, Table 1 Suppliers of commercial SRNF membranes and their products (as in
October 2012)
Company Membrane Material Stability range MWCO
Evonik DuraMem ® Lenzing P84® Acetone, ethanol, methanol, 150–900 Da
(Germany)a polyimide tetrahydrofuran, dimethylformamide*,
(*cross- dimethyl sulfoxide*,
linked) dimethylacetamide*, isopropanol,
acetonitrile, methyl ethyl ketone, ethyl
acetate, and more
PuraMem ® Lenzing P84® Toluene, heptane, hexane, methyl ethyl 280–600 Da
polyimide ketone, methyl isobutyl ketone, ethyl
acetate, and more
SolSep BV (the SolSep UF Diverse Alcohols, aromatics, esters, ketones, 10,000–20,000 Da
Netherlands)b (unspecified) chlorinated solvents
SolSep NF Diverse Methanol, ethanol, propanol, acetone, 300–750 Da
(unspecified) ethyl acetate, hexane, toluene,
chlorobenzene
Borsig GMT-oNF PDMS-based Alkanes, alcohols, aromatics, ethers, Unspecified
Membrane composites esters, ketones
Technology
(Germany)c
Inopor ® Inopor ® TiO2, SiO2 Unspecified 450–750 Da
(Germany)d nano
a
http://duramem.evonik.com/product/duramem-puramem/en/Pages/default.aspx
b
http://www.solsep.com/
c
http://mt.borsig.de/
d
http://www.inopor.com/en/index.html
Transport through SRNF membranes is com- SolSep, and Borsig offer polymeric membranes
plex due to the interactions between solvent, sol- in flat sheet form or spiral-wound modules. Inopor
ute, and membrane (e.g., swelling). Two models supplies ceramic mono- and multichannel tubes.
are often applied to describe the transport mech-
anism but also the combination of both appears.
For loose SRNF membranes, the pore-flow model Cross-References
is used while the solution-diffusion model is
applied for dense SRNF membranes. Both take ▶ Organic Solvent Nanofiltration
into account membrane properties, which can vary ▶ Organic Solvent Nanofiltration Technique
depending on the feed characteristics. This implies ▶ Organic Solvent-Resistant (OSR) Membrane
that the same membrane can behave as loose in ▶ Solvent Filtration
one solvent and as dense in another solvent.
Currently, only a limited number of compa-
nies supply commercial SRNF membranes (listed References
in Table 1). In the past, Koch Membrane Systems
(USA) was another producer of SRNF mem- Peeva LG, Sairam M, Livingston AG
(2010) Nanofiltration operations in nonaqueous sys-
branes (MPF series), but they ceased their
tems. In: Drioli E, Giorna L (eds) Comprehensive
SRNF production. Together with StarMem membrane science and engineering, vol 2, 1st edn.
(MET-Evonik, previously Membrane Extraction Elsevier, Oxford, pp 91–113
Technology), the MPF membranes were the first Vandezande P, Gevers LEM, Vankelecom IFJ (2008) Sol-
vent resistant nanofiltration: separating on a molecular
commercially available SRNF membranes, mak-
level. Chem Soc Rev 37(2):365–405
ing them the subject of many studies. Evonik,
S
Flame Spray
References
Flame spray uses combustion of gases to melt
powder, wire, or rod material and propels the Pawlowski L (2009) Suspension and solution thermal
molten droplets onto a surface to create a coating. spray coatings. Surf Coat Technol 203:2807–2829
Seiji K, Jin K, Makoto W, Hiroshi K (2008) Warm
Flame coatings are commonly used for materials
spraying–a novel coating process based on high-
requiring good wear resistance and excellent velocity impact of solid particles. Sci Technol Adv
impact resistance such as agricultural harvesting Mater 9(3):033002 (17pp)
components, oil-drilling parts, etc.
S
Static Membrane Emulsification between the two liquid phases. During the
droplet formation process, the surfactant mol-
Emma Piacentini1, Alessandra Imbrogno1 and ecules adsorb to the newly formed oil-water
Richard G. Holdich2 interface reducing the interfacial tension and
1
Institute on Membrane Technology facilitating droplet formation. The transfer
(ITM-CNR), University of Calabria, Rende (CS), rate of the surfactant molecules from bulk
Italy solution to the newly formed oil-water inter-
2
Department of Chemical Engineering, face is mainly determined by their diffusional
Loughborough University, Loughborough, transfer because of the absence of continuous-
Leicestershire, UK phase flow.
• The buoyancy force (FBG) due to the density
difference between continuous phase (rc) and
Static membrane emulsification (ME) refers to dispersed phase (rd) and influenced by the
the formation of emulsion droplets by extruding volume of droplet (Vd). It is a detaching
the dispersed phase through the membrane pores force which counteracts the interfacial tension
into the continuous phase in the absence of sur- force or capillary force.
face shear (Fig. 1). • “Push-off” or “push-to-detach” force (G), that
In the absence of shear flow at the membrane is, an additional detaching force applicable
surface, the main forces acting on the droplets when there are a large number of drops at the
forming at the membrane pore level are (see membrane surface causing drops to deform
Fig. 2): from their thermodynamically more stable
spherical shape. The contribution of this addi-
• The interfacial tension (or capillary) force (Fg) tional force is likely to be more noticeable
(retaining force) that represents the effect of with a regular array membrane, such as
the dispersed phase adhesion on the pore micro-sieve metallic membrane with highly
opening. It is a function of the dynamic inter- uniform pore spacing and pore size compared
facial tension g(t). This force is typically to conventional membranes such as the
assumed to be determined by the Young- Shirasu porous glass (SPG) type.
Laplace equation with the continuous phase
assumed to fully “wet” the membrane surface. The dispersed phase flux has a great influence
Surfactant type and concentration greatly on the spontaneous droplet formation behavior
influence the adsorption kinetics of the surfac- and depends on the viscosities of disperse and
tant and thus the dynamic interfacial tension
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_553-1
2 Static Membrane Emulsification
Static Membrane
Emulsification,
Fig. 1 Static membrane
emulsification
continuous phases and flow velocity of the dis- drops, the push-off force is zero and final drop
perse phase through the membrane pore. The size is defined only by an equilibrium of buoy-
push-off force occurs when a critical injection ancy and capillary forces (interfacial tension). At
rate is exceeded and all, or nearly all, of the increasing injection rate, more and more pores
membrane pores become active. In this condition, will be activated and the push-off force becomes
a large number of drops grow simultaneously at significant (Kosvintsev et al. 2008).
the membrane surface, and the drop diameter is Another parameter affecting the droplet
bigger than the distance between the pores, so detachment from the pore openings is the shape
that the drops push each other off at the mem- of the pore openings: noncircular pore openings
brane surface. In the limiting case, when only encouraging the spontaneous detachment of
relatively few pores are active and the distance droplets. During droplet formation from tortuous
between those pores is bigger than the size of the pores with a noncircular cross section, the
distorted dispersed phase is spontaneously
transformed into spherical droplets by interfacial
tension at the membrane surface because of the
minimization of the interfacial free energy of the
system. This phenomenon has been observed
with SPG membranes (Sugiura et al. 2001;
Christov et al. 2002).
The static ME has several advantages over
dynamic ME:
mechanisms in membrane emulsification: oil-in-water Sugiura S, Nakajima M, Iwamoto S, Seki M (2001) Inter-
emulsions stabilized by tween 20 and milk proteins. facial tension driven monodispersed droplet formation
Colloids Surf A 209:83–104 from microfabricated channel array. Langmuir
Kosvintsev SR, Gasparin G, Holdich RG (2008) Mem- 17:5562–5566
brane emulsification: droplet size and uniformity in the
absence of surface shear. J Membr Sci 313:182–189
S
Strip Dispersion Supported Liquid high selectivity, low carrier and solvent con-
Membrane sumption, high degree of concentration enrich-
ment, and so on. Despite the abovementioned
Argurio Pietro advantages, SLMs are not currently used on a
Department of Chemical and Environmental large scale in the industry, since membrane sta-
Enginnering, University of Calabria, Arcavacata bility or lifetime is, in general, far too low to
di Rende (CS), Italy assure good commercial applications. Instability
of SLMs is due to the loss of carrier and/or mem-
brane solvent from the membrane phase which
A liquid membrane (LM) is a thin liquid film that has an influence on both flux and selectivity of the
separates two other liquid phases with which it is membrane (Kemperman et al. 1996). In addition,
immiscible. There are three basic forms of LM the flux of solute through SLM is lower because
processes: bulk liquid membrane (BLM), emul- of the higher resistance of mass transfer from the
sion liquid membrane (ELM), and supported liq- presence of static membrane solution filled in
uid membrane (SLM) (Molinari and Argurio microporous supports.
2009). The small membrane surface area per For solving the above difficulties and
unit volume represents the most important draw- obtaining LM system with high efficiency, new
back of BLMs, making them not attractive by a configurations have been proposed. Ho (2002)
technological point of view. ELMs are character- and Teramoto et al. (2000) proposed a combined
ized by a large surface area per unit source phase SLM/strip dispersion process (i.e., the strip solu-
volume, which enhances the transport rate. One tion was dispersed in the membrane organic
disadvantage of ELMs is the low emulsion sta- phase) for the removal and recovery of target
bility, so that if for any reason the membrane does species from a feed solution. This new LM con-
not remain intact during operation, the separation figuration has several advantages: (i) increased
achieved to that point is destroyed. SLMs usually stability, (ii) reduced costs, (iii) increased sim-
consist of an organic solvent impregnated in the plicity of operation, (iv) extremely efficient strip-
pores of a hydrophobic microfiltration membrane ping of the target species from the organic phase,
(Molinari and Argurio 2011). SLM combines and (v) high flux and a high concentration of the
extraction and stripping processes into one single recovered target species in the aqueous strip solu-
step, which provides the maximum driving force tion. An important limitation of SLM with strip
for the separation of a target species. SLM has dispersion system is represented by impossibility
many advantages over traditional separation to avoid the pollution of the aqueous solutions
technologies such as solvent extraction including with membrane solution due to its dissolution in
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_556-5
2 Strip Dispersion Supported Liquid Membrane
Feed phase
Strip phase
Phase Mixer
(organic + strip)
Organic phase
Dispersed droplets of
strip phase Strip pump
Feed pump
Strip Dispersion Supported Liquid Membrane, Fig. 1 Schematization of the combined supported liquid mem-
brane/strip dispersion system (elaborated from He et al. (2006))
both aqueous feed and strip solutions. In this evidenced that this new configuration of LM is
context, the choice of membrane solution with applicable in the separation and recovery of sol-
water-insoluble components is a key step. utes from aqueous solutions.
The combined SLM/strip dispersion system The same LM configuration, called strip dis-
can be schematized as reported in Fig. 1: a micro- persion hybrid liquid membrane (SDHLM), was
porous hydrophobic support (e.g., polypropyl- studied by Gu et al. (2006) for the transport and
ene) acts as the liquid membrane support. The separation of Cd(II) from Zn(II) ions from aque-
strip dispersion is a mixture of an aqueous strip ous media. The results evidenced that cadmium
phase, containing a stripping agent, and an (II) can be effectively transported into the strip-
organic phase containing an extractant. During ping solution from the feed phase by the
the extraction process, the dispersion flows SDHLM using tri-n-octylamine-secondary
through one side of the SLM. A feed solution octanol in kerosene as carrier. The proposed
containing the target species is passed on the system has superiority over SLMs and ELMs in
other side of the SLM. terms of: (i) transport rate, since the efficient
In 2006, He et al. studied the recovery of Zn contact area between organic and stripping solu-
(II) ions by using the SLM/strip dispersion sys- tion results in an extra mass transfer surface;
tem. The influence of various experimental (ii) permeability coefficient and extraction or
parameters on the separation of binary Zn recovery percentage of Cd(II); (iii) efficiency
(II) and Cu(II) ions, that is, system of great of uphill transport; (iv) membrane stability;
importance to hydrometallurgy and environmen- and (v) no usage of high active surfactant and
tal protection, was investigated. Obtained results demulsification device.
Strip Dispersion Supported Liquid Membrane 3
Styrene-Grafted Film,
Scheme 1 Styrene
grafting onto polymer
copolymer (PFA) (Cardona et al. 2002), Gubler L, Gursel SA, Scherer GG (2005) Radiation
polyvinylidene fluoride (PVDF) (Elomaa grafted membranes for polymer electrolyte fuel cells.
Fuel Cells 5:317–335
et al. 2000), ethylene-tetrafluoroethylene copoly- Hwang DS, Sherazi TA, Sohn JY, Chang NY, Park CH,
mer (ETFE) (Scott et al. 2000), polychlorotri- Guiver MD, Lee YM (2015) Anisotropic radio-chem-
fluoroethylene (PCTFE) (Zhao and Jin 1988), ically pore-filled anion exchange membranes for Solid
etc., were reported to be used for grafting with alkaline fuel cell (SAFC), J Membr Sci, 495:206–215
Ismail AF, Zubir N, Nasef MM, Dahlan KM, Hassan AR
styrene. Styrene-grafted films have also been (2005) Physico-chemical study of sulfonated polysty-
developed using polyethylene (Sherazi rene pore-filled electrolyte membranes by electrons
et al. 2008, 2009, 2013) as base polymer. induced grafting. J Membr Sci 254:189–196
Styrene-grafted and sulfonated poly(ethylene Nasef MM, Saidi H, Nor HM (2000) Proton exchange
membranes prepare d by simultaneous radiation
terephthalate) films were also studied as bioactive grafting of styrene onto poly(tetrafluoroethylene-co-
polymers to produce a “biointegrable” artificial hexafluoropropylene) films. I. Effect of grafting con-
anterior cruciate ligament (ACL) (Ciobanu ditions. J Appl Polym Sci 76:220–227
et al. 2006). The scheme of styrene grafting Saneto A, Fumihiro M, Shogo I, Li J, Takaharu M,
Akihiro O, Yosuke K, Masakazu W (2005) Fabrication
onto polymer to produce styrene-grafted film of PEFC membrane based on PTFE/FEP polymer-
can be represented by Scheme 1. alloy using radiation-grafting. Nucl Instrum Methods
Grafting can be initiated by various methods B 236(437):442
including chemical initiator, radiation technique, Scott K, Taama WM, Argyropoulos P (2000) Performance
of the direct methanol fuel cell with radiation-grafted
etc. (see graft polymerization). polymer membranes. J Membr Sci 171:119–130
Sherazi TA, Ahmad S, Kashmiri MA, Guiver MD
(2008) Radiation induced grafting of styrene onto
References ultra-high molecular weight polyethylene powder and
subsequent film fabrication for application as polymer
electrolyte membranes. I: influence of grafting condi-
Cardona F, George GA, Hill DJT, Aasoul FR, Maeji tions. J Membr Sci 325:964–972
J (2002) Copolymers obtained by the radiation- Sherazi TA, Ahmad S, Kashmiri MA, Kim DS, Guiver
induced grafting of styrene onto poly MD (2009) Radiation induced grafting of styrene onto
(tetrafluoroethylene-co-perfluoropropylvinyl ether) ultra-high molecular weight polyethylene powder and
substrates. 1. Preparation and structural investigation. subsequent film fabrication for application as polymer
Macromolecules 35:355–364 electrolyte membrane. II: sulfonation and characteri-
Ciobanu M, Siove A, Gueguen V, Gamble LJ, Castner zation. J Membr Sci 333:59–67
DG, Migonney V (2006) Radical graft polymerization Sherazi TA, Sohn JY, Guiver MD, Lee YM (2013) Poly-
of styrene sulfonate on poly(ethylene terephthalate) ethylene based anionic exchange membranes for solid
films for ACL applications: “grafting from” and chem- alkaline fuel cells (SAFC). J Membr Sci 441:148–157
ical characterization. Biomacromolecules Varcoe JR, Slade RCT (2005) Prospects for alkaline
7(3):755–760 anion-exchange membranes in low temperature fuel
Elomaa M, Hietala S, Paronen M, Walsby N, Jokela K, cells. Fuel Cells 5:187–200
Serimaa R, Torkkeli M, Lehtinen T, Sundholm G, Zhao XZ, Jin JL (1988) Study of radiation graft styrene
Sundholm F (2000) The state of water and the nature onto pre-irradiated poly-chlorotrifluoroethylene films.
of ion clusters in crosslinked proton conducting mem- Radiat Phys Chem 31:805–808
branes of styrene grafted and sulfonated poly(vinyli-
dene fluoride). J Mater Chem 10:2678–2684
S
Submerged Membrane,
Fig. 1 Submerged
membranes
microfiltration process, the gas sparging gently (expansion and modification) of existing systems.
moves the membranes which cause crushing of Thanks to its numerous advantages, submerged
the filter cake layer. In individual cases, where membranes found itself since its inauguration
possible, it is used in addition to other methods of popularity in the following areas:
cleaning the membranes, such as flushing of the
liquid phase (penetration) or gas phase and chem- • Food industry (beverages, alcohols, dairy)
ical cleaning of various intensities. Thus, the best • Chemical industry
adapted strategies for cleaning the submerged • Electronic
membranes should be adapted for the specific • Mechanics
case. The chemically supported backflushing is • Laundries
used daily, chemical cleaning of high concentra- • Bathing
tion once per week, or intensive chemical • Photo
cleaning annually. • Medicine
The main advantages of SM system should • Agriculture (livestock and aquaculture)
therefore be low investment costs, which result • Wastewater treatment
from a simple and reliable design, easy installa-
tion, and compact size (small footprints). Low
operating costs result from the low power con-
References
sumption, low maintenance costs, and ease of use
and repairs, through continuous monitoring. In Koltuniewicz AB (2010) Integrated Membrane Opera-
addition to these economic advantages, sub- tions in various Industrial Sectors. In: Drioli E and
merged membrane also features high perfor- Giorno L (eds) Membrane Science and Engineering.
mance and high efficiency. Submerged Elsevier 4(1):109–154
membranes can be easily used for retrofitting
S
Submerged Membrane Bioreactor the following: (1) legislation, (2) local water
scarcity, (3) return on investments, (4) environ-
A. B. Koltuniewicz mental impact, and (5) public and politician
Faculty of Chemical and Process Engineering, acceptance (Judd 2011).
Biotechnology and Bioprocess Engineering Flat plate or capillary membranes are usually
Division, Warsaw University of Technology, immersed vertically in a tank where feed is deliv-
Warsaw, Poland ered. The capillary membranes can also be
arranged horizontally (see Table 1). The perme-
ate is discharged by means of collectors on the
Synonyms outside of the tank under hydrostatic pressure or
light vacuum using a pump. The integration of
Immersed Membrane Bioreactor (IMBR) membrane and reactor introduces well-known
benefits, such as accelerating the kinetics of the
Submerged membrane bioreactors (SMBs) are process and increasing its efficiency. Continuous
a type of membrane bioreactor MBR, where two removal of the products from the reaction space
processes, i.e., the chemical reaction and separa- and the retention of the substrates shifts the equi-
tion, took place simultaneously to produce a syn- librium to the right (toward product), thus
ergistic effect. The first idea of membrane reactor increasing the efficiency of the process. In this
connection was founded at Rensselaer Polytech- case, the membrane also helps to avoid adverse
nic Institute, Troy, New York (Smith et al. 1969). reactions, which can lead to transient products.
The first use of MBR to the activated sludge in Submerged membrane bioreactors are much
wastewater treatment plants has been done by more cost-effective when compared to conven-
Dörr-Oliver, Inc., Milford, Connecticut, USA tional cross-flow membrane modules (see
(Hardt et al. 1970). After several years this idea Table 1).
was popularized in Japan and developed by The role of the costly cross-flow has been
Yamamoto et al. (1989) and the company replaced in SMB by mild hydrodynamic condi-
KUBOTA, which introduced further integration tions, where gas sparging is often used (see
in the form of flat sheet membranes immersed Fig. 2). For this purpose, the gas is supplied
directly in the reactor tank. The first application from the bottom so as to flow over the surface
of submerged membrane reactor is the sewage of the membrane. The role of gas sparging in
system, which is considerably simplified compar- submerged membrane bioreactors is twofold,
ing to conventional (see Fig. 1). The rapid devel- i.e., hydrodynamics and mass transfer enhance-
opment of SMB applications has been caused by ment. The gas flow increases the turbulence and
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_559-4
2 Submerged Membrane Bioreactor
a
sand pretreat- sand
grids aeration settler disinfection
wastewater filtration ment filtration
effluent
sludge to disposal
b Membrane
Aeration
Bioconversion
Sedimentation
SMB
sand
wastewater grids
filter
pretreatment effluent
gas sparging
sludge to disposal
Submerged Membrane Bioreactor, Fig. 1 Comparison between (a) conventional wastewater plant and (b) SMB
wastewater plant
Submerged Membrane Bioreactor, Table 1 Comparison of two types of membrane bioreactors manufactured by
ZENON ®, i.e., sidestream tubular MBR and submerged SMB (Cote and Thompson 2000)
Membrane bioreactor MBR Submerged membrane bioreactor SMB
Model Permaflow Z-8 ZeeWeed ZW-500
Surface area [m2] 2 46
Permeate flux [l/m2h = LMH] 50–100 20–50
Pressure [bar] 4 0,2–0,5
Airflow rate [m3/h] – 40
Energy [kWh/m3] 4–12 0,3–0,6
produces smooth movements which help to (Yimaza et al. 2006), as well as waters for irriga-
remove the filter cake from the membrane surface tion. Industrial sectors that use the SMB are food
during microfiltration and reduces the concentra- and beverages, where high loads of chemical
tion polarization layer during the ultrafiltration. oxygen demand must be reduced. Other sectors
In the case of aerobic bioreactor, the gas may of the industrial wastewater treatment plants are
simply be air. In the case of anaerobic bioreac- in the textile, electronics, pharmaceutical, chem-
tors, inert gas is used to assist desorption of gas- ical, metal finishing, automotive, petrochemical,
eous products from the liquid. and pulp and paper. SMB reactors are also used
The SMB is most often used to remove xeno- on offshore oil and gas platforms and on barges,
biotic and various biological nutrients, i.e., sub- ships, boats, and yachts (Table 2).
stances such as carbon, nitrogen, and phosphorus, SMB has a lot of advantages compared with
for the treatment of municipal, industrial waste- conventional systems, in particular activated
water, water treatment, and recycling of different sludge (ASB Yilmaz et al. 2006). The use of
process waters. SMB is also used for the purifi- microorganisms floating freely allows for easier
cation of groundwater and surface waters access to the substrate (a few microns) and thus a
Submerged Membrane Bioreactor 3
faster bioconversion compared with ASB which is much faster compared to mass transport
(several hundred microns of flocks in activated in the activated sludge. Thus, using SMB is cheap
sludge). SMB can operate effectively in all dilute and easy, because it helps minimize capital and
solutions even below threshold values for ASB operating expenses. Low energy costs are associ-
that is 0.01 kg COD/(m3 day). This is because the ated with the use of energy-efficient method of
kinetics of bioconversion in the SMB is faster removing a filter cake (in MF) or a polarizing film
since it is limited only by chemical reaction, (in UF) from the surface of the membrane, such
as gas sparging in moderate hydrodynamic con-
ditions. Low capital cost based on a simple and
very compact design, which consists of closely
arranged membranes directly immersed in the
tank bioreactor design with compact stacked
membranes that are placed directly in the reactor.
In addition, the SMB does not require settlers,
thus occupying less space (footprint) in sewage
treatment plants, which, in case of conventional
solutions, can be very burdensome to the envi-
ronment, particularly in the open air. Using SMB
ensures greater bioconversion kinetics and shows
better flexibility and versatility of bioconversion.
SMB bioreactor has many other important fea-
tures such as high-performance density and ease
of membrane replacement and disposal of waste,
ease of automation, and ease of design and scale-
up. SMB systems are easy to operate and main-
tain, allow for remote monitoring and control,
and are much easier to control by the operator.
These characteristics predestine the SMB to
development and retrofitting existing facilities.
The global market is growing rapidly at a 20 %
annual rate value that is estimated to exceed 1bln
$ in 2012 (Judd 2011).
The main suppliers of bioreactors with sub-
Submerged Membrane Bioreactor, Fig. 2 Gas sparg- merged membranes are:
ing around the capillary membranes in the laboratory
stand
Submerged Membrane Bioreactor, Table 2 Comparison of main different SMBs (Yang et al. 2006)
Manufacturer KUBOTA ® MITSUBISHI RAYON ® ZENON ®
Membrane type Flat sheet Hollow fiber Hollow fiber
Membrane pore size [mm] 0,4 0,1–0,4 0,04
Membrane material PE (chlorinated) PE PVDF
Membrane configuration Vertical Horizontal Vertical
Surface area in module [m2] 0,8 105 31,6
Industrial plants 400 204 127
Municipal plants 1138 170 204
4 Submerged Membrane Bioreactor
Several variations of SAP based membranes often separation of sulfonated polymer from the
such as sulfonated poly (ether ether) ketones reaction mixtures poses a challenge. The choice
(SPEEK), sulfonated polyphenylsulfones of the approach is dictated by the properties and
(SPPSU), sulfonated polyethersulfone (SPES), functionality desired in the SAP membranes
etc., to name a few, have been investigated as (Vona and Knauth 2013; Meyer and Schrickel
polymer electrolyte membrane in polymer fuel 2013; Zaidi 2003; Tohidian et al. 2013).
cells. Of these, the most studied and highly prom- Sulfonation can be accomplished using a vari-
ising SAP is the polymer based on poly (ether ety of sulfonating agents such as fuming sulfuric
ether ketones) or PEEK. Sulfonated PEEK acid, concentrated sulfuric acid, chlorosulfonic
(or SPEEK) is known to have high proton con- acids, and sulfur trioxide (both in liquid and gas-
ductivity and high thermal and mechanical sta- eous forms) (Vona and Knauth 2013; Meyer and
bility. High level of sulfonation makes polymer Schrickel 2013; Zaidi 2003). These agents are
membranes amorphous and reduces its mechani- classified as strong and mild agents and conse-
cal strength, making membranes brittle (Zaidi quently affect the final yield and extent of sulfo-
2003; Tohidian et al. 2013). Structures of some nation. As with any organic reaction, sulfonation
common sulfonated aromatic polymers are process is also marred with unwanted side reac-
shown in Fig. 1. tions, cleavage of chain to mention a few if not
Sulfonation of aromatic polymer membranes properly carried out especially with fuming sul-
can be achieved by two different approaches furic acid (Meyer and Schrickel 2013; Zaidi
namely postsulfonation approach and direct sul- 2003). Each of these sulfonating agents has
fonation of the aromatic polymers. In this some adverse effect on the sulfonation process.
method, the aromatic polymer is first sulfonated Use of fuming sulfuric acid generates lots of
to the desired degree and then membranes are water as a by-product thereby promoting the
fabricated from it. In the other approach, the reverse reaction, i.e., desulfonation. The genera-
membranes are first fabricated and then sulfona- tion of HCl as a by-product limits the use of
tion is carried out on the membrane. In this case cholorosulfonic acid as a sulfonation agent as
the surface of the membrane is modified, while in the generated acid must be neutralized. Some
the other case the whole of the polymer is mod- milder forms of sulfonating agents are
ified by sulfonation (See also ▶ postsulfonation trimethylsilyl chlorosulfonate, acetylsulfate, or a
membrane). However, the latter approach is most complex of SO3 with amine or trialkyl phos-
commonly used than the former for a variety of phates also commonly used (Meyer and Schrickel
reasons. Each of the two approaches has its own 2013; Zaidi 2003). Choice of the sulfonating
advantages and disadvantages. In post- agent depends on the kind and type of the aro-
sulfonation, it is difficult to control and is limited matic polymer and its molecular weight. Utmost
by the solubility of the polymer as it is carried out care should be taken when sulfonation reaction is
in homogeneous medium, whereas direct sulfo- carried out to avoid these side reactions.
nation consumes large quantity of solvent and
Sulfonated Aromatic Polymer 3
Sulfonated Block Copolymer Membrane, Fig. 1 Typical coupling pattern in a block copolymer
SO3H
O O O O
C C N O N C C N N
H H H H
Y
X
Z
Sulfonated Block Copolymer Membrane, Fig. 2 General structure of a typical multiblock copolymer: sulfonated
polyaramide multiblock copolymer
Takamuku S, Jannasch P (2012) Multiblock copolymers Yeo J, Kim SY, Kim S, Ryu DY, Kim T-H, Park MJ
with highly sulfonated blocks containing di- and (2012) Mechanically and structurally robust
tetrasulfonated arylene sulfone segments for proton sulfonated block copolymer membranes for water
exchange membrane fuel cell applications. Adv purification applications. Nanotechnology 12:11
Energy Mater 2:129–140
S
Supported Liquid
Membrane,
Fig. 1 Scheme of a
supported liquid membrane
the solution of polymer and plasticizer (solvent problems, have resulted in their application in
characterized by high viscosity) to form a thin, many sometimes very different fields where
flexible, and stable film. All these technologies selective and efficient separation methods are
are considered as modifications of the SLMs. necessary: in hydrometallurgy, biotechnology,
SLM can also be formed by immobilizing the wastewater treatment, the capture of greenhouse
membrane phase between two nonporous films gases, analytical and environmental chemistry,
which are permeable to transported substances and in the pharmaceutical industry.
and usually nonselective. The latter is much SLM separation systems can be classified into
more stable but is less suitable due to a higher several different groups, according to their
mass transfer resistance. preparation methods, types of membrane support
Successful applications of SLMs are possible and membrane liquids, module types used, and
due to their advantages compared to other sepa- their application (for details, see Dzygiel and
ration methods. The main advantages of SLMs Wieczorek 2010).
are the small amounts of organic phase and
extractant (carrier) used, one-step mass transfer,
the possibility of achieving high separation fac-
References
tors, concentration of extracted compound
(s) during separation, and low separation costs. Dzygiel P, Wieczorek P (2010) Supported liquid mem-
SLMs have been used to solve an increasing brane and their modifications:definition, classifica-
number of separation problems, including metal tions, theory, stability, applications and perspectives.
In: Kislik V (ed) Liquid membranes principles and
and organic compound separation and the resolu-
applications in chemical separations and Wastewater
tion of stereoisomers. The unique flexibility and treatment, 1st edn. Elsevier, Amsterdam, The Nether-
ease of preparation of SLMs in various configu- lands, Ch. 3 pp 73–140
rations, despite some stability and lifetime
T
Hot feed
Heat with
permeate
Vapor
Cold
Pf
Pp
Boundary Membrane
layer
Temperature Polarization Y ¼ T fm T pm = T f T p
Coefficient (TPC) ¼ 1 H=h where 1=h ¼ 1=hf 1=hp
of MD is decreased by both temperature polari- negligible. In this case TPC depends on the heat
zation and concentration polarization. Therefore, transfer coefficient in feed boundary layer and
they can be combined in one coefficient called the increases with a membrane permeability (pore
vapor pressure polarization coefficient (Khayet size and porosity).
2011).
TPC defined and calculated for DCMD can be
also applied to other MD configurations. In sweep
References
gas membrane distillation (SGMD) and air gap
membrane distillation, the heat transfer coeffi- Khayet M (2011) Membranes and theoretical modeling of
cient on the permeate side is much smaller than membrane distillation: a review. Adv Colloid Interf
that on the liquid side. Therefore, in SGMD the Sci 164:56–88
flow rate of sweeping gas controls the process. In Khayet M, Matsuura T (2011) Membrane distillation.
Principles and applications. Elsevier, Amsterdam
vacuum membrane distillation, the boundary
layer resistance on the permeate side is
T
Thermo-responsive
Membrane Surfaces,
Fig. 1 Schematic
illustration of thermo-
responsive membrane
surfaces grafted with
responsive materials
possessing thermo-induced
shrinking (a–c) and
thermo-induced swelling
behaviors (d). (a) Surface-
covering model, (b, d)
pore-covering model, and
(c) pore-filling model
One approach to address the cost and mem- zeolite membrane typically occurs in a strong
brane area problems is to make zeolite mem- basic solution at temperatures ranging from
branes like polymeric membrane sheets. Spiral 60 C to 180 C. After growth, posttreatment
wound polymeric membranes are made at fairly sometimes is needed for the removal of templates
low costs and used in large-scale seawater desa- and opening of zeolite pores. The possible
lination. The design concept of thin-sheet zeolite posttreatment methods are oxidation in an O2
membranes is illustrated in Fig. 1. One critical gas environment at high temperatures, oxidation
challenge is the support structure. Thinness of the in plasma or ozone gas environment at moderate
support sheet is necessary to reduce material con- or low temperatures, and solvent extraction. Hav-
sumption, membrane weight, and transport resis- ing a uniform surface pore structure at micro- and
tance. Thin sheets also enable package of large sub-micrometer levels is necessary for deposition
membrane areas in a given volume, i.e., obtaining of a thin, continuous zeolite membrane layer on
high membrane area packing density. the support. It is obvious that a continuous zeolite
As general requirements of a membrane sup- membrane less than 10 mm thick cannot be
port, the support sheet needs to be highly perme- formed on a support surface of pores or defects
able so that mass transport through the support larger than 10 mm. The zeolite membrane can
would not present a significant resistance for work under separation conditions that could be
most separation applications, and the support problematic to polymeric materials, such as in
sheet needs to be sufficiently strong to provide hydrocarbon and organic solvent media and at
the mechanical strength for the membrane sheet high temperatures (relative to environment).
to withstand a pressure gradient under separation Thus, the support sheet needs to be stable under
conditions for a long time. The specific require- separation conditions so that application and per-
ments pertinent to zeolite membrane preparation formances of the zeolite membrane would not be
are (i) stability under zeolite membrane growth compromised by the support. Finally, the support
and preparation conditions, (ii) uniform surface sheet needs to be low costs.
pore structures at micro- and sub-micrometer No commercially available materials could be
levels, and (iii) stability under the zeolite mem- found yet when the above criteria were applied to
brane separation conditions. The growth of a the selection of a suitable support sheet. Porous
Thin-Sheet Zeolite Membranes 3
Surface
texture
Zeolite membrane
surface texture
Thin-Sheet Zeolite Membranes, Fig. 2 NaA zeolite membrane grown on 50 mm-thick porous Ni sheet support
ceramic disks work well as a zeolite membrane by secondary growth methods (Liu et al. 2011b).
support but have not been made as thin, strong, The secondary growth consists of two basic pro-
inexpensive sheets yet. Sintered metal plates cess steps: seeding and growth. The support sur-
meet the requirements of mechanical strength face is first coated with a layer of small crystals of
and chemical and thermal stability. But they are targeted zeolite framework that act as a seed for
too thick and too expensive. On the other hand, zeolite crystal growth. The seed coating also
metal foams and metal meshes have the pore helps smoothening of the support surface. Then,
opening too large to be deposited with a thin, a continuous layer of intergrown zeolite crystals
continuous zeolite membrane layer. Micro- and is formed by hydrothermal growth of the seeded
ultrafiltration polymeric membranes have ade- support under suitable conditions. Thin-sheet
quate surface pore structures but fall short of zeolite membranes grown on such a support are
chemical and thermal stability. No report on for- illustrated with a NaA membrane in Fig. 2. The
mation of high-performance zeolite membranes 50 mm-thick porous Ni alloy sheet is strong
on a polymeric support has been found yet. enough to be self-supported and flexible enough
Thin porous metallic sheets have recently to bend and shows uniform surface pore struc-
been developed that can meet all the above tures. After membrane growth, the sheet surface
criteria (Liu et al. 2011a; Liu and Canfield changes its color from metallic gray to darken
2012). The thin-metal sheets made of Ni, Ni glassy luster. A dense and continuous membrane
alloys, and steels possess the physical and chem- layer comprising intergrown zeolite crystals is
ical properties of those metallic materials and formed on the metallic support surface. No cracks
provide suitable pore structures for the prepara- and pinholes are seen. Although there are differ-
tion of a thin layer of zeolite membranes. These ent sizes and shapes of crystals on the membrane,
metal sheets are made of inexpensive metal oxide a pure NaA crystal phase is confirmed by X-ray
raw materials and have large potential for mass diffraction analysis. It is worth noting that the
production at low costs. As a reference, steel zeolite membrane shows excellent adhesion
sheets and plates are produced at a price as low onto the support, which is largely attributed to
as $1/kg. It was demonstrated that zeolite mem- the thinness of the zeolite membrane layer. The
branes can be directly prepared on such supports zeolite membrane is so thin that the membrane-
4 Thin-Sheet Zeolite Membranes
Process
A stack of 13cm x
stream in
13cm x 55 µm Sweep
zeolite membrane stream in
sheets
Membrane Process
core stream out
Sweep +
permeate out
Thin-Sheet Zeolite Membranes, Fig. 3 Package of thin membrane sheets into a working module for cross-flow
separation and mass transfer
grown sheet behaves similar to the bare metal membrane sheet and flow in perpendicular direc-
sheet, strong and flexible. tions. The membrane surface per unit volume
The thin-sheet design paves the way for mass (SAV) of the stack for this module design can be
production of zeolite membranes at competitive estimated by the following equation:
cost. Materials used to make the metal sheet
support and prepare zeolite membranes are typi- 1
SAV ¼
cally inexpensive commodity products. By mak- 0:5LP þ 0:5LF þ Lm
ing thin-sheet membranes, the raw materials
become a minor cost factor. The membrane cost where Lp, LF, and Lm are permeate (or sweep)
will be largely determined by the preparation channel spacing, feed (or process) channel spac-
process costs. Current planar sheet or plate prod- ing, and membrane thickness, respectively. If
ucts, such as papers, metal foils, glass, and poly- Lp = 1 mm, LF = 1 mm, and Lm = 0.05 mm,
meric membranes, are manufactured in large bulk SAv can be 952 m2/m3. Using small channel spac-
quantities at fairly low costs. It is expected that ing reduces the mass transfer resistance from bulk
the thin-sheet zeolite membrane can be mass to membrane surfaces and increases the mem-
produced by utilizing automated, high- brane area packing density.
throughput sheet-to-sheet-type manufacturing In summary, zeolite membranes supported on
processes. a thin porous metal sheet are compared to other
The thin sheet enables fabrication of mem- membrane materials and products in Table 1.
brane modules or membrane separation equip- This hybrid membrane technology is expected
ment with maximum membrane area and/or to preserve unique properties possessed by the
minimal mass transfer resistance from bulk to zeolite and metallic materials and eliminate
membrane surface. A cross-flow planar module their shortcomings at the same time. Thus, the
(Fig. 3) is used to illustrate the making of a hybrid thin-sheet membrane can provide perfor-
separation device with the thin-sheet zeolite mance and cost advantages that are not achiev-
membrane. An array of membrane sheets is pack- able using individual materials alone. There is a
aged together to form respective feed and perme- great opportunity to further develop this mem-
ate channels by the use of proper backing and brane technology for various applications and to
spacing materials. The sweep (or permeate) and expand the design concept to other material
feed (or process) streams are separated by the systems.
Thin-Sheet Zeolite Membranes 5
Thin-Sheet Zeolite Membranes, Table 1 Comparison of thin-sheet zeolite membranes to other membrane products
Material Application Cost Characteristics
Polymer Various commercial products from microfiltration, Fair Working well in water medium
Hollow fiber ultrafiltration, and nanofiltration to molecular at ambient or room
Sheet separation temperatures
~$10 billion/year global market Stability issues at high
temperatures and in organic
solvents or oil
Ceramic Some specialized applications High Tolerance to organics
Excellent thermal stability
Tube A few hundred million $/year market Fragile
Monolith
Metal Some specialized applications with limited market High Ductile and strong
penetration Tolerant to organics
Tube Fair thermal stability
Thin-sheet Porous metal sheet as micro- and ultrafiltration Fair Advantages of metal and zeolite
zeolite/metal membrane materials
membrane Zeolite membranes for a number of important Module package like polymeric
molecular separation processes sheets
feed volume and the initial feed concentration of considering process models with constant (i.e.,
the solute i. This initial value problem describes concentration-independent) flux and rejections
the evolution in time of the feed volume and the and a few dealing with concentration-dependent
feed concentration of any solute under the membrane response models (e.g., Bowen and
assumption that the diluant is free of component Mohammad (1998); Kovács et al. 2008). The
i, and the feed tank is well mixed. Note that the simplifying assumptions, when their appropriate-
time-dependent variables (i.e., permeate flux and ness is not carefully checked for the given sepa-
the solute rejections) are, in a general case, a ration process, can easily result in suboptimal
function of feed concentrations and may vary process control.
with operation conditions (temperature, pressure, Optimization procedures may consider differ-
cross-flow velocity, etc.). ent objective functions, such as minimization of
Assuming constant rejections and flux, the operational time, diluant consumption, or a com-
differential equations can be reduced to simple plex economic index. This latter involves the
algebraic equations. The resulting exact solutions costs of utilized diluant and pump operation and
are: incorporates macrosolute loss-related costs. The
optimal solution is case specific varying with the
• For concentration mode, the actual concentra- complexity of the permeation model (i.e., rejec-
tion of component i at any time instant gives tion and flux behavior), the initial and final
ci ¼ ci0 nRi where n is the volume concen- values, and the constraints involved in the model.
tration factor defined as the ratio of initial feed
volume to actual feed volume.
• And for constant-volume dilution mode, it
References
holds: ci ¼ ci0 eDðRi 1Þ where D is the dilution
factor given as the ratio of applied diluant Beaton NC, Klinkowski PR (1983) Industrial ultrafiltra-
volume to feed volume. tion design and application of diafiltration processes.
J Sep Process Technol 4(2):1–10
Bowen WR, Mohammad AW (1998) Diafiltration by
The subject of optimization procedures is a nanofiltration: prediction and optimization. AIChE
TD process that aims at increasing the J 44(8):1799–1812
macrosolute concentration from c10 to c1f and Dutré B, Trägárdh G (1994) Macrosolute-microsolute sep-
reducing the microsolute concentration from c20 aration by ultrafiltration: a review of diafiltration pro-
cesses and applications. Desalination 95:227–267
to c2f (e.g., Beaton and Klinkowski 1983; Dutré Foley G (1999) Minimisation of process time in ultrafil-
and Trägárdh 1994; Foley 1999; Wang tration and continuous diafiltration: the effect of
et al. 2007; Paulen et al. 2012). TD is character- incomplete macrosolute rejection. J Membr Sci
ized with a sequence a(t) = {0, 1, 0} with two 163:349–355
Kovács Z, Discacciati M, Samhaber W (2008) Numerical
unknown switching times at the end of the first simulation and optimization of multi-step batch mem-
and of the second process steps. In engineering brane processes. J Membr Sci 324(1–2):50–58
practice, process optimization is usually aimed at Paulen R, Fikar M, Foley G, Kovács Z, Czermak P (2012)
finding optimum values for n and D. Note that it Optimal feeding strategy of diafiltration buffer in batch
membrane processes. J Membr Sci 411–412:160–172
poses a mathematically analogous problem to Wang L, Yang G, Xing W, Xu N (2007) Mathematic
finding switching times. The problem of deter- model of the yield for diafiltration processes. Sep
mining optimum switching times for a given Purif Technol 59:206–213. doi:10.1016/j.
technological objective has been the subject of seppur.2007.06.007
many optimization studies, most of them
T
Heinonen KB, Ward JE, Holohan BA (2007) Production Thornton DCO (2004) Formation of transparent
of transparent exopolymer particles (TEP) by benthic exopolymeric particles (TEP) from macroalgal detri-
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Ecol 341:184–195 Thornton DCO, Fejes EM, DiMarco SF, Clancy KM
Kennedy MD, Muñoz-Tobar FP, Amy GL, Schippers JC (2007) Measurement of acid polysaccharides in
(2009) Transparent exopolymer particle (TEP) fouling marine and freshwater samples using alcian blue.
of ultrafiltration membrane systems. Desalination Limnol Oceanogr: Methods 5:73–87
Water Treat 6(1–3):169–176 Verdugo P, Alldredge AL, Azam F, Kirchman DL,
McKee MP, Ward JE, MacDonald BA, Holohan BA Passow U, Santschi PH (2004) The oceanic gel
(2005) Production of transparent exopolymer particles phase: a bridge in the DOM–POM continuum. Mar
by the eastern oyster Crassostrea virginica. Mar Ecol Chem 92(1–4):67–85
Prog Ser 183:59–71 Villacorte LO, Kennedy MD, Amy G, Schippers JC
Mopper K, Zhou J, Ramana KS, Passow U, Dam HG, (2009a) Measuring transparent exopolymer particles
Drapeau DT (1995) The role of surface-active carbo- (TEP) as indicator of the (bio)fouling potential of RO
hydrates in the flocculation of a diatom bloom in a feed water. Desalination Water Treat 5:207–212
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Passow U (2000) Formation of transparent exopolymer (2009b) The fate of transparent exopolymer particles
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Ecol Prog Ser 192:1–11 through pretreatment processes and deposition on
Passow U (2002a) Transparent exopolymer particles reverse osmosis membranes. Water Res
(TEP) in aquatic environments. Prog Oceanogr 43(20):5039–5052
55(3):287–333 Villacorte LO, Schurer R, Kennedy MD, Amy G,
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the spectrophotometric measurement of transparent Schippers JC (2010b) The fate of transparent
exopolymer particles (TEP). Limnol Oceanogr exopolymer particles in integrated membrane systems:
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T
c
a b
F E R
F E R F E R
SE A–
A–
S
S S S S S
E
SA
SA S S
A–
A– A–
2H+ 2EH 2H+ E 2A– E 2A–
S2+ S+ S2+
2H+ A– 2A–
Transport Mechanisms with Liquid Membranes, anions cotransported, E is liquid membrane, F is feed
Fig. 1 Schematic mechanisms of solute transport through solution, R is stripping solution, red is reduction, ox is
the liquid membranes. S is solute to be separated, A are oxidation
diffusion steps is slow enough to control the rate resistances in the liquid phases. (3) The overall
of the overall transport. So, analysis of mecha- mass-transfer resistance at steady state is the sum
nisms and kinetics of the chemical and diffusion of individual mass-transfer resistances at diffu-
steps of the overall LM transport system is sional regime through the boundary films and
needed to find the rate-controlling ones. chemical reactions resistances at the phases’
A universal model for all these types of transport interface. (4) Membrane supports have uniform
does not exist, and the available knowledge pore size and wetting characteristics throughout
concerning the specific interfacial processes membrane. Hydrophobic membrane pore is
should be taken into account in the description completely wetted by organic phase; hydrophilic
of real membrane process. or ion-exchange membrane pore is completely
The basic idea of the chemical kinetics- filled with aqueous phase. (5) Thermodynamic
diffusion method is that the solute presented in local equilibrium at the uptake (feed-LM) and
the different phases is considered as different release (LM-strip) interfaces. (6) The aqueous
chemical species obeying the laws of chemical or organic stagnant boundary films diffusion
kinetics. The general assumptions of the transport resistances may be combined with the diffusion
may be formulated as: (1) Steady-state conditions resistances of the same liquid films (aqueous
of the solute transport through the phase inter- or organic) inside the membrane pores
faces: all fluxes are necessarily the same. (2) The (taking into account the membrane porosity and
overall mass-transfer rate of solute can be con- tortuosity) in one-dimensional series of diffusion
trolled by any of the chemical reaction–diffusion resistances.
Transport Mechanisms with Liquid Membranes 3
In all configurations (BLM, SLM, ELM) we (decomplexation). All these steps have mathe-
have: (1) diffusion steps in aqueous feed and strip matical descriptions. (For details see BLM,
stagnant boundary layers, (2) diffusion of the SLM, and ELM entries and Kislik 2010).
complex solute-carrier in the LM phase and/or
interdiffusion (diffusion in the filled membrane
support pores), (3) partitions between aqueous References
feed and organic LM phases at feed-LM interface
(forward extraction) and between LM and aque- Kislik V (2010) Carrier-facilitated coupled transport
through liquid membranes: general theoretical consid-
ous strip phases at LM-strip interface (backward
erations and influencing parameters, Chapter 2. In:
extraction), and (4) kinetics of chemical interac- Kislik V (ed) Liquid membranes: principles and appli-
tions with formation of solute-carrier complex cations in chemical separations & wastewater treat-
(complexation) and destruction of complex ment, 1st edn. Elsevier, Amsterdam, pp 17–72
U
Variable Volume Diafiltration c2 ð0Þ c1 t f
R1 ln þ R2 ln
c2 t f c 1 ð 0Þ
a¼
Zoltán Kovács c1 t f c 2 ð 0Þ
ln þ ln
Department of Food Engineering, Institue of c1 ð0Þ c2 tf
Bioengineering and Process Engineering, Szent
Istvan University, Budapest, Hungary where R1 and R2 are the rejection of macrosolute
and microsolute, respectively, and are assumed to
be constants throughout the filtration process.
Variable volume diafiltration (VVD) is a type of Variable volume diafiltration has been origi-
batch diafiltration process in which fresh diluant nally proposed by Jaffrin and Charrier (1994) for
is continuously added to the feed tank at a rate a UF/DF process for albumin production from
that is proportional but less than the permeate human plasma. The proposed technique, how-
flow. This causes a gradually diminishing feed ever, has found to be suboptimal for that particu-
volume and a simultaneous concentration of lar application as concluded by an in-depth
macrosolute and removal of microsolute. Thus, mathematical analysis based on optimal control
this technique is more than a simple diafiltration theory (Paulen et al. 2011).
in its strict and traditional sense since it is not Although variable volume diafiltration could
designed only to wash out the microsolutes but offer substantial advantages over constant vol-
also enables the concentration of the process ume diafiltration in terms of water usage (Krstić
liquor within a single-step operation. et al. 2004), it compares unfavorable with an
The process is controlled by measuring the optimally run traditional diafiltration process
permeate flow and adjusting the diluant flow (Foley 2006a). As a further improvement, Foley
accordingly with a control valve. The proportion- (2006b) has suggested that the performance of
ality factor a, that is, the ratio of diluant flow d(t) variable volume diafiltration under certain cir-
to permeate flow q(t), is then kept constant such cumstances can be enhanced in terms of diluant
that 0 < a < 1. consumption and operational time by including a
For a given process, in which the macrosolute pre-concentration step.
concentration is to be increased from c1(0) to Variable volume diafiltration is a relatively
c1(tf), while the microsolute concentration is to new concept, and only a few experimental inves-
be reduced from c2(0) to c2(tf), the proportionality tigations on its performance are available in the
factor a can be calculated by the following for- literature. These include, for example, ethanol
mula (Tekić et al. 2002): removal from albumin (Jaffrin and Charrier
VOC Recovery, Table 1 Typical VOCs nitrogen was also investigated under various
Acetaldehyde BFC-134a operating conditions (e.g., feed concentration,
Acetone Hexane operating temperature). The PEBA/PVF2 com-
Acetonitrile Methanol posite hollow fiber membranes were effective
Carbon tetrachloride Methyl chloroform for the separation of hydrocarbon vapors from
CFC-11 Methyl isobutyl ketone nitrogen.
CFC-12 Methylene chloride PDMSvi was prepared from divinyl-
CFC-113 Propylene oxide terminated poly(dimethylsiloxane), platinum-
Chlorine Styrene divinyltetramethylsiloxane complex,
Chloroform Toluene oligosilylstyrene, and hexane. PDMSvi–Al2O3
Ethylene dichloride Trichloroethylene
composite hollow fiber membrane was developed
Ethylene oxide Vinyl chloride
by coating a PDMSvi-oligo film on the outer
HCFC-123 Xylenes
surface of an Al2O3 hollow fiber porous substrate.
Microstructures of the composite membranes
were examined using scanning electron micros-
material because of its excellent thermal and copy (SEM), displaying a uniform PDMSvi-oligo
chemical stabilities and good mechanical coating layer, free of defects with a thickness of
strength, and PEBA was selected as the active around 15 mm. Such composite hollow fiber
separating layer because of its good membranes are suitable for VOC recovery from
permselectivity and film forming properties. waste gas streams because of their high chemical
The membranes were tested for the recovery of stability. The separation performances of the
representative VOCs including hexane, heptane, PDMSvi–Al2O3 composite hollow fiber mem-
and cyclohexane, which are the main components brane were studied using chloroform in N2 as a
of gasoline, and dimethyl carbonate, ethanol, test vapor mixture. By analyzing the experimen-
methanol, and methyl t-butyl ether that are the tal data obtained at various conditions with a
oxygenates and octane number enhancers of gas- mathematical model derived, the permeabilities
oline. The separation of gasoline vapor from of chloroform and nitrogen in the PDMSvi
VOC Recovery 3
Volatile Organic Compounds of chemicals, some of which may have short- and
long-term adverse health effects. Concentrations
Tadashi Uragami of many VOCs are consistently higher indoors
Organization for Research and Development of (up to ten times higher) than outdoors. VOCs
Innovative Science and Technology (ORDIST), are emitted by a wide array of products number-
Kansai University, Suita, Osaka, Japan ing in the thousands. Examples include paints and
lacquers, paint strippers, cleaning supplies, pesti-
cides, building materials and furnishings, office
Volatile organic compounds (VOCs) are organic equipment such as copiers and printers, correc-
chemicals that have a high vapor pressure at tion fluids and carbonless copy paper, graphics
ordinary, room-temperature conditions. Their and craft materials including glues and adhesives,
high vapor pressure results from a low boiling permanent markers, and photographic solutions.
point, which causes large numbers of molecules Organic chemicals are widely used as ingredients
to evaporate or sublimate from the liquid or solid in household products. Paints, varnishes, and wax
form of the compound and enter the surrounding all contain organic solvents, as do many cleaning,
air. Many VOCs are dangerous to human health disinfecting, cosmetic, degreasing, and hobby
or cause harm to the environment. VOCs are products. Fuels are made up of organic
numerous, varied, and ubiquitous. They include chemicals. All of these products can release
both human-made and naturally occurring chem- organic compounds while you are using them
ical compounds. VOCs play an important role in and, to some degree, when they are stored. Table 1
communication between plants. Volatile organic is listed some VOCs in WHO.
compounds (VOCs) are emitted as gases from
certain solids or liquids. VOCs include a variety
Encyclopedia of Industrial Chemistry & 5th (Marigliano et al. 2003). Therefore, the use of a
Completely Revised Edition 1995; Amadeo membrane reactor allows obtaining a higher con-
and Laborde 1995) or CuO-CeO2-based cata- version also at higher temperature where the ther-
lysts and takes advantage of the low tempera- modynamic conversion is low, acting positively
tures displacing the equilibrium, since the on the kinetics. Consequently, the amount of
exothermic character of the WGS reaction. catalyst necessary for a given conversion can be
significantly reduced (Barbieri et al. 2011). In
H2O/CO feed molar ratio typically ranges fact, one membrane reactor operating at high
from 2 to 5 for shifting the thermodynamic equi- temperature was demonstrated replacing the two
librium conversion and increases the reaction rate reactors of the traditional process (Fig. 1), giving
and thus hydrogen yield. The WGS is often the same final conversion or higher.
followed by a further step of remaining CO elim- Among the several membrane types, the
ination since CO is a poison for many industrial Pd-alloy membranes are the most used for the
catalysts. Thus, this H2-rich stream is usually selective removal of hydrogen in applications
directed to a CO selective/preferential oxidation such as dehydrogenation reactions, thanks to
reactor and then to a pressure swing adsorption their infinite H2 selectivity. An important aspect
unit for separating H2 from the other gases. in the use of Pd-alloy MR is the good exploitation
For providing a better exploitation of raw of whole the available membrane area, which
materials together with the reduction of the reac- allows the improvement of the global perfor-
tion/separation/purification stages and related mance, with higher CO conversion and more H2
loads, the use of membrane reactors (MRs) is a recovered in the permeate side (Barbieri
promising approach, as they combine the reaction et al. 2008).
and the H2 separation by means of a selective Currently, self-supported Pd-Ag membranes
membrane (Brunetti et al. 2012a; Shu are produced at commercial level, and, when
et al. 1991; Uemiya et al. 1991; Dittmeyer used to investigate experimentally the WGS reac-
et al. 2001; Brunetti et al. 2012b). tion at a laboratory scale, they showed a high
The presence of the membrane allows the durability and performance stability for more
recovery of a hydrogen-rich/pure stream which than 2 years operating at 330 C and up to
does not require any additional separation. More- 10 bar (Barbieri et al. 2008).
over, the removal of the hydrogen, which is a The results obtained at a laboratory scale con-
product, from the reaction volume shifts the reac- cretized in some cases in various patents. For
tion toward a further conversion. example, United Technologies Corp. patented
The removal of hydrogen by a membrane the use of a WGS MR, comprising a WGS reac-
gives many advantages: the reverse reaction rate tion region a permeate volume, separated by an
is depleted owing to the lower H2 concentration; H2-separation membrane which allows H2
the residence time of reactants is increased; the formed over a catalyst in the reaction region to
thermodynamic equilibrium of a membrane reac- be passed selectively to the permeate region
tor exceeds that of a traditional reactor; the pres- (Gummalla et al. 2010).
sure has a positive effect on conversion in a
membrane reactor, even if no variation in the
number of mole is involved in the WGS reaction
Water Gas Shift (WGS) 3
440 °C
440 °C
Pure hydrogen
-1
GHSV = 20 000 h
No sweep gas
a Traditional process
210 °C
Second stage LT-WGS
GHSV = 3 000 h-1 Feed (e.g., reformer down-stream)
LT-WGS Heat exchanger
First stage 300 °C
HT-WGS
GHSV = 20 000 h-1
LT-WGS
ca. 10 GHSV
380 °C
Converted stream
Containing Hydrogen
260 °C
Water Gas Shift (WGS), Fig. 1 Schemes of “Pd-based membrane reactor” and “traditional process” for WGS reaction
(Marigliano et al. 2003)
Dependence of the temperature and pressure. Chem Uemiya S, Sato N, Inoue H, Ando H, Kikuchi E (1991)
Eng Process 42:231–236. doi:10.1016/S0255- The water–gas shift reaction assisted by palladium
2701(02)00092-2 membrane reactor. Ind Eng Chem Res 30:585–589
Shu J, Grandjean BPA, Van Neste A, Kaliaguine S (1991)
Catalytic palladium-based membrane reactors: a
review. Can J Chem Eng 69:1036–1048
W
Vacuum
Cooling
Wine
Permeate
Wine Aroma Enhancement, Membrane Operations of, Table 1 Solute rejection by RO and NF membranes
(Labanda et al. 2009)
Compound Rejection (%)
Osmonics – SE Toray – UB70 Osmonics – DK
Diethyl succinate 99 96 97
2-Phenyl-ethanol 97 95 95
cis-3-Hexenol 80 77 85
Isovaleric acid 86 76 65
Wine Clarification by Microfiltration the feed solution flowing parallel to the mem-
brane surface may sweep deposited particles
Johannes De Bruijn toward the retentate side, and so the deposited
Department of Agroindustry, Food Engineering layer of particles and colloids remains relatively
Group, Universidad de Concepcion, Chillan, thin (Fig. 1).
Chile The correct choice of operating conditions and
membrane plays a key role to minimize mem-
brane fouling. Microfiltration performance is
Wine clarification – Crude wine is a complex governed by colloids and small particles, where
medium with a turbid aspect. This latter is not these constituents result into a sharp initial flux
well accepted by the consumer, and wine needs to decline related to both internal and external foul-
be clarified removing particles such as microor- ing. Therefore wine filtration should be done
ganisms (yeast and bacteria), cell debris, colloi- below critical flux above which an irreversible
dal aggregates (tannin, pectin, and deposit appears at the membrane surface.
mannoprotein), and potassium tartrate crystals Applied pressure should be smaller than the crit-
by microfiltration. Thus, the key roles of clarifi- ical pressure, where the particles brought to the
cation are to provide limpidity and microbiolog- membrane surface by the permeate flow are
ical stabilization of wines. transported back into the bulk suspension by dif-
Microfiltration – Cross-flow microfiltration fusion and flow out of the membrane. Transmem-
could be an alternative for traditional solid–liquid brane pressure is generally in the range between
separation technologies such as centrifugation, 1 and 3 bars. Moreover, cross-flow velocity
filtration on sheets, diatomaceous earth filtration, affects mass transport of particles nearby mem-
and the use of exogenous additives during wine brane surface by increasing shear stress and shear
making. It offers several advantages such as no induced diffusion. A cross-flow velocity of 2 m/s
health and environmental problems because of is usually applied, which insures sufficient shear
the elimination of diatomaceous earth use, as stress and preserves wine quality. A major prob-
well as the combination of clarification, stabili- lem of increasing cross-flow velocity is the rise of
zation, and sterile filtration in one single contin- wine temperature. Temperature should not
uous unit operation without significantly exceed 25 C in order to not modify sensorial
modifying sensory quality of wines. The wine to characteristics of wine. Furthermore, organic
be filtered flows parallel to the membrane surface membranes of cellulose acetate, polypropylene,
and solutes and salts pass through the membrane polyethersulfone, and polyvinylidene difluoride
by mean of a pressure drop. The shear exerted by and ceramic membranes of zirconium oxide,
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_601-2
2 Wine Clarification by Microfiltration
References
Permeate
References
Zeolite Membrane,
Fig. 1 MFI zeolite
membrane obtained by
secondary growth on a
porous a-Al2O3 support
(Motuzas et al. 2006)
Zosen in Japan as well as Mitsubishi Chemical Julbe A (2007) Zeolite membranes—synthesis, character-
Corporation, also developed zeolite-based ization and applications. In: van Bekkum H, Cejka J,
Corma A, Schuth F (eds) Introduction to zeolite sci-
pervaporation or vapor permeation dehydration ence and practice, studies in surface science and catal-
systems (Pina et al. 2011). Recently, upscaling of ysis. Elsevier, Amsterdam, pp 181–219
SAPO-34 (Li et al. 2010) and all-silica DDR Kondo M, Komoriki M, Kita H, Okamoto KI
membranes (Makiko and Kenji 2012) has been (1997) Tubular-type pervaporation module with zeo-
lite NaA membrane. J Membr Sci 133:133–141
considered, respectively, by Shell and NGK Insu- Li S, Carreon MA, Zhang Y, Funke HH, Noble RD,
lators Ltd. for CO2/CH4 separation. Other types Falconer JL (2010) Scale-up of SAPO-34 membranes
of zeolite membranes, including MFI, FAU for CO2/CH4 separation. J Membr Sci 352:7–13
(NaX, NaY), MOR, and T-type membranes, are Makiko N, Kenji Y (2012) Process for the production of
DDR-type zeolite membranes. US Patent 8,497,223
considered for various applications of high indus- Motuzas J, Julbe A, Noble RD, van der Lee A,
trial impact. Bussan Nanotech Research Institute Beresnevicius ZJ (2006) Rapid synthesis of oriented
Inc., namely, reported on mass production of silicalite-1 membranes by microwave-assisted hydro-
tubular NaY zeolite membranes for ethanol dehy- thermal treatment. Microporous Mesoporous Mater
92:259–269
dration (Sato et al. 2008). Pina P, Mallada R, Arruebo M, Urbiztondo M,
Navascués N, de la Iglesia O, Santamaria J (2011)
Zeolite films and membranes. Emerging applications.
References Microporous Mesoporous Mater 144:19–27
Sato K, Sugimoto K, Nakane T (2008) Mass-production of
tubular NaY zeolite membranes for industrial purpose
Caro J, Noack M (2008) Zeolite membranes – recent and their application to ethanol dehydration by vapor
developments and progress. Microporous Mesoporous permeation. J Membr Sci 319:244–255
Mater 115:215–233
International Zeolite Association. http://www.iza-online.
org. Accessed December 2015
Z
Zeolite T Type, Fig. 1 (a) The erionite-type zeolite, (b) the offretite-type zeolite – view along [001] direction
(International zeolite association (IZA))
References
References
References
# Crown 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_612-1
2 Zeta Potential
References
Slipping plane
Dukhin AS, Goetz PJ (2002) Ultrasound for characteriz-
ing colloids. Elsevier
Particle with negative Dukhin SS, Semenikhin NM (1970) Theory of double
surface charge layer polarization and its effect on the electrokinetic
and electrooptical phenoma and the dielectric constant
of dispersed systems. Kolloidn Zh 32:360–368
Hunter RJ (1981) Zeta potential in colloid science: prin-
ciples and applications. Academic, London
Hunter RJ (1989) Foundations of colloid science,
vol 1. Oxford University Press, Oxford
Stern layer Diffuse layer
Malvern Instruments Ltd (2001) Zeta potential—an intro-
−100 duction in 30 minutes (technical note MRK654-01).
Surface potential Zetasizer Nano series technical note
Stern potential O’Brien RW, White LR (1978) Electrophoretic mobility
mV of a spherical colloidal particle. J Chem Soc Faraday
Zeta potential
Trans 2(74):1607–1626
von Smoluchowski M (1903) Contribution to the theory of
0 electro-osmosis and related phenomena. Bull Int Acad
Distance from particle surface Sci Cracovie 3:184–199
References
Tg
Glassy Since gas separation membranes must have a
State very thin, thicknesses 100 nm, skin or separat-
ing layer to achieve high fluxes, they are expected
to exhibit similar effects when the polymer is
Equilibrium State glassy. This may be manifested as a decline in
productivity over the lifetime of the module. Of
course, much of this aging may have already
occurred prior to the membrane being put into
service. Even so, this means that the actual per-
Temperature meability of the active layer may be much lower
than estimated by thick film (tens of microns in
Membrane Aging, Fig. 1 Illustration of the specific
volume versus temperature above (rubbery state) and thickness) tests.
below (glassy state) the glass transition temperature of a
polymer. The arrow indicates the path of slow densifica-
tion of the glass over time
(Reproduced with
permission of Elsevier
(Copyright 2004)) `=
1.8
61.2 µm
35.6 µm
1.6 8.50 µm
3.60 µm
1.4 1.85 µm
0.99 µm
0.72 µm
1.2
0.41 µm
1.0
1 10 100 1000 10000
Aging time (hr)
Membrane Aging 3
Air Gap Membrane Distillation reduction of the heat loss and the value of the
(AGMD) permeate flux.
Since in AGMD the permeate is condensed on
Maria Tomaszewska the cold surface, the liquid permeate is separated
Faculty of Chemical Technology and from the membrane surface, which prevents the
Engineering, West Pomeranian University of membrane wetting. Thus an important advantage
Technology, Szczecin, Szczecin, Poland of the process is the ability to remove the organic
compounds from aqueous solutions.
The permeate flux in AGMD can vary from
AGMD is a configuration of membrane distilla- ca. 0.3 to 26 kg/m2h, depending on the operating
tion (MD) in which an air layer is interposed conditions and feed composition. The rejection
between a porous hydrophobic membrane and coefficient of nonvolatile species, e.g., NaCl,
the condensation surface (Fig. 1). In the process, usually amounts close to 100 %. Generally, in
volatile compounds (including water) present in a AGMD the nonvolatile species present in a feed
warm feed evaporate at the liquid/vapor interface are almost completely retained, whereas volatile
formed at the membrane surface. The vapor is compounds are partially transferred through the
transferred through the membrane pores and the membrane. The separation of compounds present
gas gap and finally condenses on a cold surface in aqueous solutions using AGMD is based not
inside the membrane module. The driving force only on the vapor/liquid equilibrium, but also the
of the mass transfer in AGMD is the difference in diffusion rate of the feed components through the
vapor pressure on both sides of the membrane gas filling the membrane pores and the air gap
The air gap significantly reduces the heat loss between the membrane and the condensation
by the membrane material, therefore the perme- surface.
ate flux could increase. On the other hand air gap The air entrapped within the membrane pores
forms a barrier for the vapor, and due to the mass and in the air gap can be considered as a stagnant
transfer resistance the permeate flux decreases film, thus the mass transfer in AGMD is generally
with an increase of the air gap width (Table 1) described according to the ordinary molecular
(Alkhudhiri et al. 2012). When the gap width is diffusion including both the air and
changed, the mechanism of heat transfer may be noncondensable gases in the membrane pores
changed from pure conduction and diffusion to and in the air gap. The air gap width is usually
natural convection. The optimum of air gap width 10–100 times greater than the membrane thick-
should be determined to achieve the best perfor- ness; therefore the membrane characteristics are
mance of the AGMD system taking into account a usually neglected. In AGMD, the heat transfer
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_623-2
2 Air Gap Membrane Distillation (AGMD)
includes the heat transfer through the feed bound- volatile compounds present in a feed. Thus, the
ary layer, through the membrane and the gas gap, total permeate flux Jt (a sum of the water vapor
condensation at the cold surface, and heat transfer flux Jw and the volatile compounds flux Jv)
through the condensate liquid boundary layer and increases, but the selectivity of volatile solutes
to the cooling water. To optimize the AGMD decreases with a feed temperature. The heat loss
systems, the effects of operating parameters by conduction through the membrane material is
should be taken into account (Khayet and lower at higher feed temperature which also
Matsuura 2011). explains the higher permeate flux.
The feed temperature strongly affects the per- An increase in the concentration of nonvola-
meate flux. Since the vapor pressure of aqueous tile compounds in a feed reduces the Jt due to a
solutions grows exponentially with temperature, decrease in the Jw. In the case of an increase of
the driving force increases for both water and concentration of volatile compounds in a feed,
the Jt and Jv increase, whereas the Jw decreases. It
Feed Tf,in is associated with changes of the partial pressure
vapor of dissolved species and water. The selectivity of
volatile compounds can be different depending
on their properties and concentration in the feed
Tf,m Tc
Important condition: and can be improved by an increase of their
Tf,m > Tc partial pressure by salt addition into a feed. Gen-
air gap
Air Gap Membrane Distillation (AGMD), Table 1 Air gap effect on the permeate flux (reprinted from Alkhudhiri
et al. (2012), copyright (2012) with permission from Elsevier)
Membrane Pore size Tin Air gap Permeate flux
Ref material (mm) Feed ( C) (mm) kg/m2.h
[5] PVDF 0.45 Artificial seawater 60 1.9–9.9 5–2.1
[6] PTFE 0.2 Isopropanol 50 1.62–0.55 5.1–6.3
[108] PVDF 0.22 Sucrose 25.8 1–4 1.7–0.8 l/m2h
[18] PTFE 0.2 NaCl (3.8 %) 60 0.3–9 19–1.5
[120] PTFE 0.22 HNO3 (4 M) 80 0.5–2 5.3–4.25 l/m2h
[123] PTFE 0.45 HCl/water 60 4–7 3.7–2.4
[123] PTFE 0.2 Propionic acid/ 60 4–7 7.4–4.6
water
Comments – the references can be found in the original paper
Air Gap Membrane Distillation (AGMD) 3
Air Gap Membrane Distillation membrane, so the effect of air inside the mem-
(AGMD), Applications of brane can be neglected. AGMD creates the
opportunity for the separation of species forming
Maria Tomaszewska the azeotropic solutions. It is attributed to the
Faculty of Chemical Technology and difference in the diffusion coefficients of volatile
Engineering, West Pomeranian University of compounds present in a feed through the gas gap
Technology, Szczecin, Poland (Khayet and Matsuura 2011). Thus, AGMD can
find the application in water and wastewater
treatment, biotechnology, food industry,
The separation using AGMD is based not only on etc. (Table 1).
vapor/liquid equilibrium but also on the diffusion The plate and frame, tubular, capillary, and
rates of the feed components through the gas very frequently spiral wound modules equipped
trapped in the membrane pores and the air gap with porous hydrophobic membranes are used
between the membrane and the condensation sur- in AGMD.
face. Nonvolatile compounds are rejected by a The main area of AGMD application is desa-
membrane in almost 100 %. Therefore, AGMD lination. The desalination pilot plants combining
can be applied for desalination and production of AGMD with solar energy collectors were devel-
high-purity water. A permeate with electrical oped, especially for operation in arid and semi-
conductivity as low as 4 mS/cm can be obtained arid remote regions with a lack of electricity and
from a solution with composition similar to sea- drinkable water but with high solar radiation
water. Moreover, AGMD can be applied for the (Table 2). The production of potable water, e.g.,
separation of volatile compounds. Since the from plants installed in Jordan was of 100 L/day
vapor is condensed on the cold surface and the (utilizing brackish water) and 1 m3/day (Fig. 1)
liquid permeate does not come into contact with a (utilizing untreated seawater from the Red Sea).
hydrophobic membrane, even the organic solutes The installations were equipped with AGMD spi-
can be separated without a risk of the membrane ral wound modules with area of 10–40 m2,
wetting. The air gas reduces considerably the heat respectively. Long-term experiments have dem-
loss and the temperature polarization which onstrated that the average salt rejection was 98 %
improve the separation efficiency of AGMD; (Qtaishat and Banat 2012; Khayet and Matsuura
however, this leads simultaneously to a signifi- 2011). Distillate conductivity of 3–5 mS/cm can
cant decrease in the permeate flux. The decrease be obtained for brackish water feeding. Despite
depends strongly on the width of the air gap. The the advantages such as the ability to desalinate
air gap is about 10–100 times thicker than the high saline feedwater, fitness for intermittent
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_624-2
2 Air Gap Membrane Distillation (AGMD), Applications of
Air Gap Membrane Distillation (AGMD), Applications of, Table 1 Application of air gap membrane distillation
Area Membrane material Application
Desalination PTFE, PVDF Water and wastewater treatment, production of pure water,
Modified ZrO2, modified Al2O3, solar-powered desalination, geothermal wastewater
modified TiO2, modified treatment
aluminosilicate
Food industry PVDF, PTFE Fruit and vegetable juice concentration, milk
concentration, sugar and gelatine solution concentration,
ethanol concentration
Biotechnology PTFE, PVDF Ethanol separation from a broth
Others PTFE, PVDF Methanol, isopropanol concentration, separation of
azeotropic mixtures HCl/water, propionic acid/water,
formic acid/water, separation of radioisotopes 18O and 18F,
concentration of wastewater containing isotopes, HI and
H2SO4 concentration
Separation/removal of HNO3, HCl, formic acid, acetic
acid, propanone from aqueous solutions
PTFE polytetrafluoroethylene, PVDF polyvinylidene fluoride
energy supply, and the ability to use direct solar without a risk of the membrane wetting. It was
heat without heat storage, the plants have not found that a salt addition into diluted ethanol
been commercialized or implemented in a large increases alcohol selectivity (Khayet and
scale. This is mainly because reverse osmosis Matsuura 2011).
(RO) is considered as more economical and AGMD can be useful in breaking the
energy-efficient desalination process (Saffarini azeotropic mixtures of water and hydrochloric
et al. 2012). However, the AGMD/solar energy or propionic acids. This phenomenon was asso-
systems are still in progress and find a growing ciated with the differences in the acid-air and
interest. water-air diffusion rates in the air gap. In
Another field of AGMD application is food AGMD the hydrochloric acid/water azeotrope
processing. Figure 2 presents the possibility of was shifted to higher acid concentration, and the
juice concentration by AGMD to achieve much azeotrope was eliminated in the propionic acid/
higher feed concentration than using RO. Low water system. It was found that the heavy gases
processing temperature allows to concentrate such as SF6 help more in eliminating the
the solutions sensitive to high temperature and azeotropic point than the lighter ones as air or
provides a good quality of juice concentrate He (Khayet and Matsuura 2011).
(Kimura and Nakao 1987). The concentration of AGMD was successfully used for the concen-
milk demonstrated that the membranes were eas- tration of a mixture of HI and H2SO4, compounds
ily fouled by milk fat and the permeate flux of great interest for H2 generation in thermo-
decreased very fast (Khayet and Matsuura 2011). chemical water-splitting cycle (Khayet and
Ethanol preferentially vaporizes from the Matsuura 2011). AGMD has also a great potential
aqueous feed and is concentrated in the permeate. in the application in the environment protection
Since in AGMD the liquid ethanol does not come area. Therefore, this technique requires more
into contact with a membrane, it can be separated studies, devoted especially to a long-term perfor-
from a fermentation broth and concentrated mance and membrane life.
Air Gap Membrane Distillation (AGMD), Applications of 3
Air Gap Membrane Distillation (AGMD), Applications of, Table 2 Timeline of solar-powered membrane distil-
lation systems and their general features (Adapted from Saffarini et al. 2012)
Energy system type Solar
Membrane Feedwater collector
Year Location MD type type/material type Thermal Electrical type
1991 New South DCMD Hollow fiber/ N/A Solar Grid N/A
Whales, N/A collector
Australia
1995 New South AGMD Spiral wound/ N/A Solar Grid VPC
Wales, Australia PTFE collector
1997 Tokyo, Japan N/A N/A/N/A N/A Solar PV N/A
collector
1999 Texas, USA AGMD N/A/N/A N/A Solar Grid N/A
pond
1999 Irbid, Jordan DCMD N/A/PTFE Brackish Solar Grid N/A
still
2003 Freiburg, AGMD Spiral wound/ Freshwater Solar Grid FPC
Germany PTFE collector
2004 Texas, USA AGMD N/A/N/A NaCl Solar Grid N/A
solution pond
2007 Irbid, Jordan AGMD Spiral wound/ Brackish Solar PV FPC
PTFE collector
2007 Aqaba, Jordan AGMD Spiral wound/ Seawater Solar PV FPC
PTFE collector
2008 Alexandria, AGMD Spiral wound/ Brackish Solar PV FPC
Egypt PTFE collector
2008 Mexico DCMD Hollow fiber/ N/A Solar Grid FPC
N/A collector
2009 Almeria, Spain AGMD Flat sheet/ Seawater Solar Grid CPC
PTFE collector
2009 Hangzhou, VDM Hollow fiber/ Brackish Solar Grid N/A
China PP collector
2009 Nevada, Reno, Vacuum N/A/N/A N/A Solar N/A N/A
USA enhanced pond
DCMD
2009 Gran Canaria, AGMD Spiral wound/ Seawater Solar PV Double
Spain PTFE collector glass FPC
2011 Marina Barrage, VMEMD Flat sheet/ Seawater Solar PV N/A
Singapore PTFE collector
DCMD direct contact membrane distillation, VMD vacuum membrane distillation, PP polypropylene, N/A not available,
PV photovoltaic panels, VPC vacuum plate collector, FPC flat plate collector, CPC concentrated parabolic collectors,
VMEMD vacuum multi-effect membrane distillation
4 Air Gap Membrane Distillation (AGMD), Applications of
Solar
irradiation Brine
Collector
feild
Feed
Storage pump
tank
Heat
exchanger
Distillate MD modules
Battery PV
Expansion
vessel
Control
unit DC PV
AC
PV array
Air Gap Membrane Distillation (AGMD), Applica- powdered (Reprinted from Qtaishat and Banat (2012),
tions of, Fig. 1 Schema of the large system (two-loop copyright (2012) with permission from Elsevier)
desalination system) of desalination using AGMD solar
150
100
1 1.5 2 2.5 3
Concentration ratio, CV
VENT TO AIR
ATMOSPHERE
COMPRESSOR WASTE GAS
NITROGEN
ELECTRIC NITROGEN TO
HEATER CUSTOMER
OXYGEN NITROGEN
CONDENSATE ANALYSER BUFFER
NITROGEN VESSEL
PRODUCTION
X
MEMBRANE
Air Products, Fig. 1 Schematic of nitrogen generation system (Reproduced with permission from Air Products)
Purging Valve
Purging Air
Drain Filter
Compressor Cooler
Separetor Product
Dry Air
SUNSEP-WTM Dryer
Drain
Air Products, Fig. 2 Typical air drying system (Courtesy: AGC Chemicals Americas)
a b
Solubility
Solubility
C
θ0 θ
Fugacity f Fugacity
c
Solubility
Solubility Coefficient (S), Fig. 1 Graphical determination of the solubility coefficient from the solubility isotherm:
(a) infinite dilution solubility coefficient, (b) solubility coefficient, (c) average solubility coefficient
figure, the case of a concave down solubility temperature. A convenient measure of the pene-
isotherm has been taken as an example to repre- trant condensability is the critical temperature,
sent the graphical meaning of S (here and in the and empirical correlations of the following kind
following the pedix i is omitted for simplicity have been proposed in the literature for data
sake). relative to an homologous set of penetrants in a
given polymer at fixed temperature (Bondar
et al. 1999; Stern et al. 1969):
Correlations for the Solubility
lnðS0 Þ ¼ a þ bT C at constant temperature (6)
Coefficient
lnðS0 Þ ¼ a0 þ b0 T 2C at constant temperature (7)
The sorption of a gas in a membrane requires
condensation of the gas, followed by mixing
with the membrane molecules. Therefore, the lnðS0 Þ ¼ M þ N ðT C =T Þ2 (8)
higher the condesability of the membrane and
its compatibility with the membrane material, For rubbery polymers, the above correlation can
the larger its solubility in the membrane at fixed be retrieved using Flory-Huggins theory and a
Solubility Coefficient (S) 3
Solubility Coefficient (S), Table 1 Experimental and predicted values of correlation coefficients for the solubility
coefficient of gases in glassy membranes (De Angelis et al. 2007)
lnðS0 Þ ¼ a þ bT C , S0 in cm3gas ðSTPÞ= cm3pol atm
Experimental value Predicted, NELF model
35 C a b a b
PC 0.0192 4.0994 0.0226 5.0123
PSf 0.0209 4.2394 0.0215 4.5165
PPO 0.0238 3.6305 0.0242 4.0788
PMMA 0.0212 5.0132 0.0219 4.8131
a 1.6 b 1.E+04
1.2
S0 psat (cm3(STP))/(cm3pol)
log10 So (cm3/ (cm3 atm))
C3H8
0.8
1.E+03
C2H6
0.4
0 CO2
CH4 C3F8
1.E+02
–0.4
O2
C2F6 Experimental data, AF2400
–0.8 N2 Experimental data, PTMSP
CF4 Experimental data, PTMSN
NELF model
–1.2 1.E+01
100 150 200 250 300 350 400
0.E+00 1.E+05 2.E+05 3.E+05 4.E+05 5.E+05
TC (K)
TC2 (K2)
Solubility Coefficient (S), Fig. 2 Solubility coefficient et al. 1999). (b) Activity-based solubility coefficient of
of gases in: (a) rubbery PDMS membrane – fluorocarbon vapors in membranes can follow different trends with the
penetrants follow a different trend with respect to the other vapor critical temperature: increasing, constant, or
ones due to lower solubility (Adapted from De Angelis decreasing (Adapted from Galizia et al. 2012)
few assumptions (Gee 1947). For glassy poly- lower interaction with the polymer (De Angelis
mers, the correlation can be reproduced effi- et al. 1999) (Fig. 2a).
ciently by the NELF model (De Angelis The activity-based solubility coefficient of
et al. 2007), as it can be seen in Table 1. gases can increase or decrease with critical tem-
Other authors correlate the values of S0 to perature (Galizia et al. 2012) (see Fig. 2b)
other condensability-related parameters, such as because, being normalized for the different
the Lennard-Jones parameter (Van Krevelen condensability of penetrants, accounts only for
1990), critical volume, surface area (Yampolskii the mixing effects, which can be positive or neg-
et al. 2000), etc. It must be noticed that, when ative depending on the gas-polymer interactions.
different series of penetrants are considered, the
solubility data may fall on separate correlating
lines. This is the case of fluorocarbon penetrants
in PDMS which show lower solubility than the
other gases of similar critical temperature, due to
4 Solubility Coefficient (S)
0.1
0.0015 0.0020 0.0025 0.0030 0.0035
1/ T (K–1)
The sorption of a gas or vapor into a solid mem- Bondar VI, Freeman BD, Yampol’skii Yu P (1999) Sorp-
tion of gases and vapors in an amorphous glassy
brane is usually an exothermic process in which
perfluorodioxole copolymer. Macromolecules
the most important thermal effect is the negative 32:6163–6171
heat of condensation of the fluid in the membrane De Angelis MG, Merkel TC, Bondar VI, Freeman BD,
phase. In addition, there is a mixing term which Doghieri F, Sarti GC (1999) Hydrocarbon and fluoro-
carbon solubility and dilation in poly(dimethyl-
can be positive or negative depending on the
siloxane): comparison of experimental data with
solute-membrane couple, but is usually lower, predictions of the Sanchez-Lacombe Equation of
in absolute value, than the condensation term. State. J Polym Sci B 37:3011–3026
Therefore, the solubility coefficient values for De Angelis MG, Sarti GC, Doghieri F (2007) NELF model
prediction of the infinite dilution gas solubility in
gases and vapors in polymer membranes decrease
glassy polymers. J Membr Sci 289:106–122
with temperature, usually according to an Arrhe- Galizia M, De Angelis MG, Sarti GC (2012) Sorption of
nius type of dependence, as follows: hydrocarbons and alcohols in addition-type poly
(trimethyl silyl norbornene) and other high free
volume glassy polymers. II: NELF model predictions.
DH S
S ¼ SðT 0 Þexp (9) J Membr Sci 405-406: 201–211
RT Gee G (1947) Some thermodynamic properties of high
polymers and their molecular interpretation. Q Rev
The heat of sorption assumes a different value for (Lond) 1:265–298
Giacinti Baschetti M, De Angelis MG, Doghieri F, Sarti
the rubbery and glassy state; in particular the GC (2005) Solubility of gases in polymeric mem-
higher value is observed in the glassy phase of branes. In: Galan MA, Martin Del Valle E (eds) Chem-
the same amorphous polymer. This behavior can ical engineering – trends and developments. Wiley,
be seen, for instance, by reporting S0 values as a Chichester, pp 41–62
Stern SA, Mullhaupt JT, Gareis PJ (1969) The effect of
function of 1/T (Fig. 3): the change of slope pressure on the permeation of gases and vapors
occurs at the membrane glass transition through polyethylene. Usefulness of the corresponding
temperature. states principle. AIChE J 15:64–73
For liquid solutes, there is no condensation van Krevelen DW (1990) Properties of polymers: their
correlation with chemical structure; their numerical
term and the thermal effect associated to sorption estimation and prediction from Additive Group Con-
in the membrane can be positive or negative. tributions, 3rd edn. Elsevier, Amsterdam
Solubility Coefficient (S) 5
Yampolskii Yu P, Wiley D, Maher C (2000) Novel corre- molecular surface area of gases. J Appl Polym Sci
lation for solubility of gases in polymers: effect of 76:552–556
C
requirements, pretreatment chemicals, and sys- For difficult-to-remove foulants – silicates and
tem design and operation. During normal opera- organics – cleaning should be performed when
tion over a period of time, RO membrane the normalized permeate flow decline is
elements are subject to fouling by suspended or 10–15 %. In many cases, commercial membrane
sparingly soluble materials in the feed water. cleaners are required but they increase OPEX.
According to the type of foulants, five categories
of membrane fouling are presented. Inorganic Fouling/Scaling
Inorganic fouling or scaling is caused by the
• Inorganic fouling/scaling accumulation of inorganic precipitates such as
• Particle/colloid fouling metal hydroxides and “scales” on membrane sur-
• Biological fouling (bacterial bioslime, algae, face or within pore structure. Precipitates are
mold, or fungi) formed when the concentration of chemical spe-
• Organic fouling cies exceeds their saturation limits. Scaling is a
• Sulfate scale of calcium, barium, or strontium major concern for reverse osmosis (RO) and
nanofiltration (NF) membrane processes. RO
Generally RO membrane suppliers recom- and NF membranes reject inorganic species.
mend membrane cleaning when: These species, if allowed to build up, form a
concentrated layer of concentration polarization.
• Normalized permeate flow declines by 10 % For microfiltration (MF) and ultrafiltration (UF),
• Pressure drop declines by 10 % inorganic fouling due to concentration polariza-
• Normalized salt passage increases by 10 % tion is much less; however, they can exist due to
interactions between ions and foulants (organic
Well-designed, well-operated RO systems are polymers) via chemical bonding. Coagulation
usually cleaned one to four times per year. Irre- and oxidation, if not designed or operated prop-
versible membrane element performance decline erly, might introduce metal hydroxides on mem-
such as membrane compaction and intrusion con- brane surface or within pore structure. Inorganic
tributes to the 0.7 flow factor. Based on this fouling and scaling can be a significant problem
permeate flow profile, the system’s stabilized for makeup water of caustic solution used for
performance is a flow factor of 0.7. Cleaning chemical cleaning.
criteria should be based on actual stabilized
membrane element performance. The typical Particulate/Colloidal Fouling
cleaning criteria (10 % normalized permeate Accumulation of particulate material (dirt, sand)
flow decline or 0.9 flow factor) are not applicable, on the membrane surface – plugging – leads to
because true membrane element performance is a particulate fouling. Algae, bacteria, and certain
permeate flow factor of 0.7. Cleaning performed natural organic matters fall into this category.
at a 0.7 flow factor has no effect but increases the However, they are different from inert particles
OPEX (operating expenses). and colloids such as silts and clays. In most cases,
Therefore, RO system cleaning criteria must particles and colloids do not really foul the mem-
be customized to actual stabilized element per- brane because the flux decline is largely revers-
formance. The criteria can be customized to site ible by hydraulic cleaning measures such as
conditions. For instance, calcium carbonate is a backwash and air scrubbing.
foulant that can be easily and effectively removed
with a hydrochloric acid solution at pH 2. For Microbial/Biological Fouling
sites with low energy costs, cleaning may be Microbial fouling is a result of formation of
carried out when the normalized permeate flow biofilms on the membrane surface. Once bacteria
decline is 20 %. get attached to the membrane, they start to multiply
and produce extracellular polymeric substances
(EPS) to form a viscous, slimy, hydrated gel. The
Chemical Cleaning of Membranes 3
4d 8d 16d 32d
a
Feed flow
Silica inhibitors can retard the polymerization membrane manufacturer will remove polymer-
of silica, which exceeded its solubility, i.e., ized silica scales but it will take many hours to
phosphonate-based chemicals. Dispersants can remove a silica scale. Colloidal silica and partic-
work by placing a surface charge on the polymer- ulate silica coating, not associated with either
ized silica and cause repulsion and dispersion of metal hydroxides or organic matter, can be
these polymerized structures into water phase removed from membrane surface by physical
(Dudley and Baker 1999). flushing.
Polymerization of dissolved silica (i.e., super- MF and UF membranes can be of organic
saturation and catalyzed by hardness) can be dif- polymers or inorganic materials, whereas NF
ficult to remove. This type of silica fouling is and RO membranes are all organic
different from colloidal and particulate silica, polymers only.
which may be associated with either metal
hydroxides or organic matter. It might be difficult
to remove polymerized silica by typical chemical
Membrane Cleaning Chemicals
cleaning process. However, polymerized silica
scales removed with a high pH cleaning solution
Selection and Use of Cleaning Chemicals
(pH of 10–11) were reported. Caustic (sodium
The first time cleaning is performed, it is
hydroxide) at maximum pH allowed by the
recommended to contact the manufacturer of the
Chemical Cleaning of Membranes 5
equipment, the RO element manufacturer, and restore the membrane flux. Chemicals commonly
service supplier. The cleaning chemicals can be used for cleaning MF and UF membranes in
generic or proprietary. water industry fall into five categories, as shown
It is not unusual to use a number of different in Table 2.
cleaning chemicals in a specific sequence to
achieve optimum cleaning. A high pH cleaning Caustic
is used to remove foulants like mineral scale or Caustic is used to clean membranes fouled by
metal hydroxides/oxides. The order of high and organic and microbial foulants. The function of
low pH cleaning solution could be reversed or caustic is twofold: (1) hydrolysis and (2) solubili-
only one solution is required under the situation. zation. There are a number of organic materials
Detergents are added to aid in the removal of including polysaccharides, and proteins that can
heavy biological and organic matter, while other be hydrolyzed by caustic. Cellulose-based mem-
foulants need a chelating agent like EDTA for the branes based on polysaccharides hydrolyze;
removal of colloidal material, organic and bio- hence, such membranes are to be used in a limited
logical material, and sulfate scale. An improper pH range. This is due to the hydrolysis of
selection of cleaning chemical or the protocol cellulose – a simple polysaccharide – consisting
thereof can make the entire cleaning exercise of thousands of glucose linked by 1,4–bglucoside
worse. bonds . Fats and oils also react with caustic
Iron deposits and scaling require a simple low through saponification, generating water-soluble
pH cleaning. For most complex fouling, the soap micelles.
sequence below may be followed: An important function of caustic is to increase
negative charges of humic substances. Hence,
• Flushing with permeate and with nonoxidizing they are easier to be removed from membranes.
biocide at the end of flushing Humic substances contain functional groups that
• High pH CIP (clean-in-place) with tempera- are organic acids. Their acidity ranges from pKa
ture versus pH (negative logarithm of the dissociation constant)
• Flushing with permeate till pH on the brine of 1.2 (oxalic) to 13 (phenol), with an average
side <8.5 pKa of 4.2 (Thurman 1985). During caustic
• Low pH CIP (clean-in-place) cleaning, pH of cleaning solution can be as high
• Acid flushing with permeate and nonoxidizing as 13.
biocide
Acids and Chelating
Once the cause of membrane fouling is iden- Acids are used primarily for removing scales and
tified, various cleaning chemicals can be used to metal dioxides from fouling layers. When mem-
remove foulants from the membrane and to brane is fouled by iron oxides, citric acid is quite
effective because it not only dissolves iron oxide
6 Chemical Cleaning of Membranes
precipitates but also forms complex with iron. of cleaning period, and hydrodynamic conditions
The removal of divalent cations by either acids affect the efficiency of cleaning.
or chelating reagent such as EDTA improves the When selecting cleaning conditions, ensure
cleaning of membranes fouled by organic the compatibility of cleaning chemicals with
foulants. membrane media and filters and systems. Chem-
ical compatibility of membrane and filter compo-
nents limits the type and the maximum allowable
Surfactants
concentration of a chemical to be used during
Surfactants are compounds that have both hydro-
cleaning.
philic and hydrophobic structures. They can form
Concentration of cleaning chemicals can
micelles with fat, oil, and proteins in water and
affect both the equilibrium and the rate of reac-
help to clean the membranes fouled by these
tion. The concentration profile of cleaning
materials. One interesting but less clear aspect is
chemicals within the fouling layer is a function
how surfactants affect membrane fouling domi-
of the concentration of cleaning chemicals in the
nated by NOM (natural organic matter). As the
bulk liquid phase. Therefore, the concentration of
surfactant is nonionic, the interaction between the
cleaning chemicals not only need to maintain the
membrane and the surfactant is dominated by
reasonable reaction rate (kinetics need) but also
hydrophilic and hydrophobic reaction. Since the
need to overcome mass transfer barrier imposed
membrane is hydrophobic, hydrophilic tail of the
by the fouling layer. In practice, the concentra-
surfactant is preferably adhered to the membrane
tions of cleaning chemicals are usually high
surface and hydrophilic head is orientated toward
enough to satisfy the kinetic need. It is the mass
aquatic phase. Soaking in surfactant has been
transfer that sets the lower boundary for the con-
used as a method for surface modification to
centration of cleaning chemicals.
improve hydrophilicity or wettability of certain
Temperature can affect membrane cleaning
membranes.
by:
costs, and chemical costs. Establish a cleaning ▶ Fouling Control in Drinking Water Membrane
strategy that is most effective and well tested; Filtration
analyze the foulants followed by an autopsy pro- ▶ Fouling Index
tocol. Selection of an appropriate pretreatment ▶ Fouling in Membranes
with good operation and maintenance practices ▶ Fouling Release
will lead to cost-effective cleaning regime. The ▶ Fouling Release Membranes
cleaning efficiency depends on the type of ▶ Membrane Cleaning
cleaning agent and its concentration. The net ▶ Natural Organic Matter Removal and Fouling
effect is that the efficiency increases with increas-
ing chemical concentration. Operating parame-
ters such as cross-flow velocity, turbulence in Further Readings
the vicinity of membrane surface, temperature,
pH, and duration of cleaning affect the cleaning Baker, J.S; Dudley, L.Y (1999) Biofouling in membrane
systems: a review. Water supply 17(1):173–81
process. Analyze the right cleaning strategy on a
Hijos G, Artal J, Gogeascoa IA, Bidaurrazaga JA
case-by-case basis. It is recommended that the (2012) Adelaide desalination plant process design:
MSDS (Material Safety Data Sheet) of the energy use optimization. IDA J 4(2):52–56
cleaning chemicals be procured from the chemi- Johnson J, Mercer G (2012) Seawater desalination plant
optimization based on membrane replacement and
cal supplier and knowledge be applied in the
cleaning. Desalination Water Reuse 4(2):34–38
handling and storage of the chemicals. Liu C, Caothein S, Hayes J, Caothuy T (2012) Membrane
chemical cleaning: from art to science. http://www.
membranecleaning.com/pdf
Nghiem LD, Schaefer AI (2006) Fouling autopsy of
Cross-References hollow-fibre MF membranes in wastewater reclama-
tion. Desalination 188:113–121
Technical Services Bulletin 107.20. Selection and use of
▶ Cleaning Cycles of Fouled Membranes cleaning chemicals. Resource document.
▶ Cleaning Effectiveness Hydranautics. http://www.membranes.com.pdf.
▶ Cleaning Efficiency Accessed 6 July 2010.
C
Apart from the improvement of the catalyst, With this aim, catalytic Pt-loaded zeolite
new reactor concepts are being studied. Mono- membranes were utilized as an effective device
liths present different advantages over particulate for CO selective oxidation in a single-stage mem-
catalysts, including pressure drop reduction, ease brane reactor operating in a continuous flow-
of handling, structural robustness, and possibly through configuration at ca. 200 C and a low
increased heat transfer. Interesting new engineer- feed molar ratio O2/CO = 1 and 1.5 (Bernardo
ing devices such as catalytic membranes and et al. 2008). This new model reactor design leads
catalytic membrane reactors were investigated to improved and really interesting performance in
in a few papers for CO selective oxidation terms of CO conversion and limited hydrogen
(Hasegawa et al. 2001, 2002; Bernardo consumption.
et al. 2006). The concept of using Pt in zeolite
catalysts was applied for this reaction by
Watanabe et al. (1995; Igarashi et al. 1997). In a
References
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Avgouropoulos G, Ioannides T (2006) Effect of synthesis
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(2002) A comparative study of Pt/g-Al2O3, Au/-
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C
a b
Retentate Retentate
Diluant Diluant
Booster
pump
Continuous Diafiltration: Cocurrent and Countercurrent Modes, Fig. 1 (a) Single-pass continuous diafiltration
and (b) continuous diafiltration with partial retentate recycle (feed and bleed)
Diluant
Feed Retentate
Stage 1 Stage 2 Stage i Stage N
Permeate
Diluant
Feed Retentate
Stage 1 Stage 2 Stage i Stage N
Permeate
Continuous Diafiltration: Cocurrent and Countercurrent Modes, Fig. 2 Simplified flow diagram of multistage
cocurrent (top) and countercurrent (bottom) continuous diafiltration
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7388(02)00375-7
E
Membrane
Vacuum a 10 100
5 50
Membrane ( II )
25
10 50
surroundings was changed is summarized. As can
be seen from Table 1, the permeant having a
lower freezing point in the feed mixture is selec- 5 25
tively permeated. In addition, when the mem-
brane has a stronger affinity to the preferentially
permeating mixture component, an increase in 0 0
–20 10 20 40
selectivity can result in TDEV.
Temperature of membrane soroudings (⬚C)
Figure 2 shows the effect of the temperature of
the membrane surroundings on the permeation Temperature-Difference-Controlled Evapomeation
rate and the ethanol concentration in the permeate (TDEV), Fig. 2 Comparison of the permeation and sepa-
for an aqueous solution of 10 wt% ethanol ration characteristics for an aqueous solution of 10 wt%
ethanol of a dense PDMS membrane (a) and a porous
through a dense PDMS membrane (a) and a PDMS membrane (b) in TDEV. Feed liquid is aqueous
porous PDMS membrane (b) in TDEV. In solution of 10 wt.% ethanol (40 C)
Fig. 2, the temperature of the feed solution is
kept constant at 40 C, and the temperature of i.e., the permeation rates in a porous PDMS mem-
the membrane surroundings was changed. As brane were higher by three orders of magnitude
shown in Fig. 2a, b, the tendency of the decrease than those of a dense PDMS membrane.
in the permeation rate decreased, and the increase A remarkable difference in the permeation
in the ethanol/water selectivity with lowering rate between dense and porous PDMS mem-
temperature of the membrane surroundings branes can be attributed to the fact that the per-
through these two PDMS membranes was very meation through a dense PDMS membrane is due
similar. In spite of the fact that the ethanol/water to the solution-diffusion model (Binding
selectivity in these PDMS membranes was et al. 1961; Aptel et al. 1974) and that through a
almost equal, the permeation rates through these porous PDMS membrane is pore flow based on,
PDMS membranes were remarkably different, as shown in Fig. 3.
Temperature-Difference-Controlled Evapomeation (TDEV) 3
Temperature-Difference-Controlled Evapomeation (TDEV), Table 1 Effect of the freezing point on the selectiv-
ity of the permeant in the organic liquid mixtures through polymer membranes in TDEV
Membrane Chitosan PVC PDMS
Freezing point of (CH3)2SO/H2O 18.5 C CH3COOH/H2O 16.7 C C2H5OH/H2O 114.4 C
permeant > 0 C > 0 C < 0 C
Selectivity H2O H2O C2H5OH
Uragami T, Tanaka Y (1991) Method of separating liquid alcoholic solutions by pervaporation and new
component from a solution containing two or more evapomeation methods through chitosan membranes.
liquid component. European Patent 0346739 Makromol Chem Rapid Commun 9:361
Uragami T, Tanaka Y (1993) Method of separating liquid Uragami T, Tanaka Y, Nishida S (2002) Permeation and
component from a solution containing two or more separation under high temperature and high pressure
liquid component. US Patent 5,271,846 for ethanol/water vapors through cross-linked
Uragami T, Tanaka Y (1994) Separation method for quaternized chitosan composite membranes. Desalina-
mixed solutions. Japanese Patent 1,906,854 tion 147:449
Uragami T, Saito M, Takigawa K (1988) Comparison of
permeation and separation characteristics for aqueous
C
Central Nervous System in Relation the axons occurs, and in the spinal cord, cell death
to Membranes is recorded in high extent due to the lost electro-
lytic homeostasis and the accumulation of free
Loredana De Bartolo and Antonietta Messina radicals and toxic factors that stimulate apoptotic
Institute on Membrane Technology, ITM-CNR, events. While the peripheral nervous system
National Research Council of Italy, Rende (CS), (PNS) consists of a particular glial cell population
Italy able to proliferate and produce specific factors
(BDNF, CNTF, GDNF) involved in the axonal
regeneration across the area of injury, the oligo-
The central nervous system (CNS) is the most dendrocytes constituting the main part of the
complex organ in the human body. It consists of central glia are not able to provide similar support
two components, the brain and the spinal cord. after damage. In the injury site of the central
The spinal cord attends the communication path- nervous system, they secrete numerous inhibitor
way between the brain and the periphery, and like factors for the axonal regeneration, including
the brain, it is made of a gray matter, constituted NOGO proteins, NI-35, chondroitin sulfate pro-
by the bodies of the neurons, and a white matter, teoglycans (NG2), and keratan sulfate proteogly-
constituted by their myelinated axons, serving the cans. The produced signaling factors that play
impulse transmission. Moreover, a special blood- neuroprotective and regenerative roles appear,
spinal cord barrier made of endothelial cells and then, to be not enough to oppose this inhibition
astrocytes protects the spinal cord from the bio- and the inflammatory events occurring after the
logical and chemical changes coming from the damage. Furthermore, astrocytes, another com-
periphery. It was long believed that regenerative ponent of the central glia, became proliferative.
processes in the CNS were completely absent, In order to protect the severed site from external
then after an injury, the recovering of the axonal molecules and the spreading of apoptotic events,
function was impossible (Kandel et al. 2000). In they form a tight network called a glial scar,
the early 1980s, therefore, it was discovered that which obstruct the axonal regeneration, creating
CNS retinal neurons were able to regenerate in a wall that axons and neurogenerative factors
bioengineered devices of peripheral nerves, cannot overtake (Horner and Gage 2002). Thus,
highlighting that the nearly absent ability to manipulation of the chemical and biological
regenerate the central neurons does not lies in environment around the injured site represents
the cells themselves but in their surrounding envi- the key of the treatment of the CNS damages.
ronment. After physical trauma, hypoxic events, Specifically, in order to promote the axonal
and degenerative pathologies, a rapid severing of regeneration of the central neurons, the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_642-1
2 Central Nervous System in Relation to Membranes
neurogenerative and neuroprotective factor and the cell therapy. All of them are categorized
levels should increase (Recknor and as membrane system devices due to their mass
Mallapragada 2006). Nowadays, it is well transport properties they allow the diffusion,
known how neural cells respond to their micro- release, and removal of the different factors
environment, enhancing adhesion, proliferation, involved after an injury.
and migration along the regenerating site. The entubulation strategy consists in the trans-
Smooth surfaces, patterned supports, and struc- plantation of tubular scaffolds purposely made to
tures with high mass transport properties are the mimic the peripheral nerve tissue. Considering
main characteristics allowing the neural regener- that the PNS is characterized by a regenerative
ation both in vivo and in vitro systems (Morelli ability due to proliferation of glial cells and the
et al. 2012). Since decades ago, the gold standard secretion of neuroprotective and
of the nervous system injury treatment is the neuroregenerative factors, many devices have
transplantation of nerve grafts able to substitute been developed with the aim of entrapping the
the malfunctioning or lost areas of the system. central axons in a protect environment, where
Despite the implantation of nerve grafts allowed inhibitor factors are not allowed to pass through
to reach important results in the recovery of and neuroregenerative signals are enhanced.
movement and sensibility of the PNS, the central These bioartificial tubular nerve grafts are
nervous system is hard to be treated, particularly meant to ensure a correct diffusion of nutrients
when inner regions of the brain are severed, then and oxygen and purposely designed with specific
new approaches appeared to be necessary for the thickness, mechanical strength, dimension, and
treatment of the CNS injury. Due to the develop- porosity degree. Tubular nerve grafts made of
ment of biomaterials and new processing PLLA, PCL and PGA, and collagen and chitosan
methods for the scaffold design, tissue engineer- already extensively used for peripheral nerve
ing and chemotherapeutic strategies are the main regeneration are nowadays applied for the treat-
approaches for the development of regenerative ment of CNS injury models, alone or in conjunc-
strategies able to guide axonal outgrowth. A wide tion with brain-derived neurotrophic factor
range of natural and synthetic biomaterials is (BDNF) to promote the axonal regeneration
available to prepare neural scaffolds and releas- (Recknor and Mallapragada 2006; Morelli
ing devices (Tysseling and Kessler 2011). Differ- et al. 2012). Cell-adhesive proteins such as colla-
ent classes of biodegradable polymers are gen, laminin, and fibronectin, which bind
available, including polycaprolactone, polyure- strongly the integrin receptors on the cell sur-
thanes, polylactic derived, polyglicolic acid, faces, assist the nerve regeneration. They are
chitosan, agarose, polysaccharides, collagen and often used to coat the lumen of the bioartificial
various ECM proteins derived. Due to their con- channels or to modify the biomaterial used for the
trolled bioerosion, these materials allow the device preparation in order to enhance the cell
design of different bioengineered devices, with response and the regenerative process. The pat-
different shapes and configuration purposely terning of polymeric tubular membranes with
made for bridging the nerve growth or the factors’ short oligopeptides derived from ECM proteins
release. Any biomaterial used to prepare neural is another way to increase the neurite outgrowth
scaffolds possess, in addition to biocompatibility, and the cytoskeleton organization in the
an appropriate range of permeability, porosity, regenerating neural tissue. Along similar lines,
and biomechanical properties serving to avoid the incorporation of hydrogels into the nerve
the compression of the regenerating nerves or tubes have been evaluated with encouraging
the sudden collapse of the device in the treated results for CNS applications. Collagen,
site. Actually, three different strategies are avail- hyaluronic acid, agarose, alginate, chitosan,
able for the treatment of the CNS injury: the methyl cellulose, xyloglucan, matrigel, fibrin,
entubulation models, the drug delivery systems, polysia-based hydrogels, peptide hydrogels, as
Central Nervous System in Relation to Membranes 3
well as synthetic hydrogels, such as polyacryl- routes for the spinal cord regeneration.
amide and polyethylene glycol hydrogels, Hydrogels, liposomes, fibrin, collagen-based,
revealed to be the best alternative to the classical and other polymeric delivery devices obtained
polymeric nerve guidance grafts. Bioengineered from natural and synthetic biomaterials have
tubular scaffolds have been combined also with been implanted subcutaneously near the spinal
cells providing a promising new approach for the cord’s injured site, allowing the continuous
CNS injury treatment. Since 1998, it is well release of the neuroprotective and
known that remyelination of central axons can neurogenerative agents and the partial recovery
be promoted by using Schwann and olfactory of the axonal functionality (Zhong and
glial cells entubulated in bioartificial scaffolds, Bellamkonda 2008). Cell therapy. The drug/bio-
and moreover, Schwann cells, when seeded in logical delivery strategies are easy with respect to
combination with neurotrophic factors or hor- the entubulation methods, but in truth, they have
mones, facilitated the axon regeneration. There- one disadvantage: the constant drug dose is
fore, the strategy is to entubulate neural stem cells achievable only with reinjection of new delivery
(NSC), which possess the ability to differentiate devices. The cell therapy, instead, relies on a
into neurons, astrocytes, or oligodendrocytes in longer production of the therapeutic factors
presence of specific growth factors and appropri- through the cell stimulation in the injured site or
ate chemical environment. Despite the risk of the transplantation of autologous, allogenic, or
uncontrolled proliferation and some problems in xenogenic cells. Generally, the cell therapy is
the maintenance of cell viability, the use of the used for the treatment of the neurodegenerative
neural stem cells in membrane systems is still the pathologies and of the chronic pain. In order to
most promising approach. Drug delivery strat- implant the cells in the interested site, specific
egy. When a nerve guide or other bioartificial polymeric carriers are available. A few trial
implants are not appropriate due to the impossi- models suggested that this kind of approach
bility to reach the severed central nervous area, could enhance the chances of the patient to
the delivery system of neurogenerative and recover partially the neuronal functionality,
neuroprotective factors represent the alternative opposing the symptoms and the cognitional prob-
strategy. A few molecules of natural and syn- lems. Polymeric membranes ensure a consistent
thetic origin showed to promote the neural regen- advantage for that kind of application, which
eration. Steroids, minocycline, interleukin consists in the chance to control cell viability
10, erythropoietin, and neurotrophins, like NGF, and the diffusion of nutrients and at the same
BDNF, and CNTF, are just some of the time, the protection of the cellular population
neuroprotective agents implied in the inhibition from the immunological reaction of the body.
of the inflammatory response, microglial activa- Genetically engineered cells encapsulated into
tion, and apoptotic event after a central injury hollow fiber membranes are able to produce and
(Kandel et al. 2000). Induction of the release ciliary neurotrophic factor (CNTF) in
regeneration-associated genes expression patients affected by amyotrophic lateral sclerosis.
(RAGs) or the Rho-Rock pathway inhibition is Parkinson’s disease is another degenerative
some of the neurogenerative properties of the pathology treatable with the cell transplantation.
neurotrophins. Moreover, they promote their In this case, dopamine-producing cells, dispersed
remyelination, the sprouting and growth of new also in different hollow fiber membranes of algi-
neurons with functional recovery. Whether the nate, showed an increase of the recovery and an
factors possess neuroprotective or analgesic effect in the patient (Cho and Borgens
neurogenerative ability, the delivery strategies 2012; Morelli et al. 2012). Therefore, the low
are the same. Growth factors, proteins, and percentage of cells surviving after implantation
drugs are encapsulated into the devices made of and the host rejection and the inflammatory
polymer, hydrogels, or proteins and injected in response represent the main disadvantages of
the spinal cord through epidural and intrathecal the cell therapy strategies. For this reason, despite
4 Central Nervous System in Relation to Membranes
the encouraging results available, the complexity science, 4th edn. McGraw-Hill Medical, New York,
of the central nervous system made the regener- pp 1087–1114
Morelli S, Piscioneri A, Salerno S, Rende M, Campana C,
ative strategies always promising and not conclu- Tasselli F, di Vito A, Giusi G, Canonaco M, Drioli E,
sive at the same time, and further investigation De Bartolo L (2012) Flat and tubular membrane sys-
must be done in order to ensure a safe and func- tems for the reconstruction of hippocampal neuronal
tional approach for the recovery after an injury. network. J Tissue Eng Regen Med 6:299–313
Recknor JB, Mallapragada SK (2006) Nerve regeneration:
tissue engineering strategies. In: Bronzino JD, Peter-
son DR (eds) The biomedical engineering handbook:
References tissue engineering and artificial organs. Taylor &
Francis, New York
Cho Y, Borgens RB (2012) Polymer and nano-technology Tysseling VM, Kessler JA (2011) Biomaterials for central
applications for repair and reconstruction of the central nervous system regeneration. Tissue Eng Neurolog
nervous system. Exp Neurol 233:126–144 Neurosurg 533:455–466
Horner PJ, Gage FH (2002) Regeneration in the adult and Zhong Y, Bellamkonda RV (2008) Biomaterials for the
aging brain. Arch Neurol 59:1717–1720 central nervous system. J R Soc Interface 5: 957–975
Kandel E, Schwartz J, Jessell T (2000) Formation and
regeneration of synapsis. In: Principles of neuronal
M
Molecular Dynamics in Membranes are considered that are typically cubic volume
elements of a few nanometers side length that
Elena Tocci represent a part cut out of the interior of a poly-
Institute on Membrane Technology ITM-CNR, mer membrane. On the other hand, interface
University of Calabria, Rende (CS), Italy models are utilized, for example, for the interface
between a liquid feed mixture and a membrane
surface or between a membrane surface and an
Over the last 30 years, detailed atomistic molec- inorganic filler. The quality of atomistic packing
ular modeling techniques, namely, the molecular models is typically validated via comparisons
dynamics (MD) and the Monte Carlo (MC), have between measured and simulated properties like
become a widely used method for the investiga- wide-angle X-ray scattering (WAXS) curves,
tion of the molecular structure of membrane densities, etc.
materials and transport properties in various
membrane operations (Binder 1995; Gubbins
and Moore 2010; Hofmann and Tocci 2009; Example: Free-Volume Distribution
Maginn and Elliot 2010; Theodorou 2006, 2010;
Razmus and Hall 1991; Harmandaris and The free-volume distribution in amorphous poly-
Mavrantzas 2004). mers is of paramount importance for their trans-
Molecular dynamics simulations have been port behavior toward small- and medium-sized
used to build or modify membranes and to inves- penetrant molecules. Atomistic molecular
tigate the physical and surface properties of modeling utilizing bulk models on the other
membranes used in gas separation and water hand can provide additional even more detailed
treatment processes. The molecular modeling of information on the magnitude, the spatial distri-
polymer-based membrane materials generally bution, and the connectivity of accessible volume
starts with the construction of typically rectangu- within an amorphous polymer matrix (Theodorou
lar packing models (Hofmann and Tocci 2009). 2010).
There, the related chain segments of the respec- The accessible volume for a given penetrant
tive polymer are arranged in a realistic, that is, molecule is the volume of the volume domain
statistically possible, way. The limited lateral composed of points that can be occupied by the
dimensions of packing models of just several center of mass of the penetrant without any over-
nanometers make it impossible to simulate com- lap between the van der Waals spheres of the
plete membranes or other polymer-based sam- penetrant and those of the polymer atoms. For
ples. Therefore, on the one hand, bulk models most polymer–penetrant pairs of practical
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_643-1
2 Molecular Dynamics in Membranes
chemical structure, like poly(dimethylsiloxane) Fried JR (2006) Molecular simulation of gas and vapor in
(PDMS) (Hofmann et al. 2000), poly(isobutyl- highly permeable polymers and references therein. In:
Yampolskii Y, Pinnau I, Freeman B (eds) Materials
ene) (PIB) (Hofmann et al. 2000), polyethylene science of membranes for gas and vapor separation.
(PE) (Hofmann et al. 2000), and polypropylene Wiley, Chichester, pp 95–127
(PP) (Hofmann et al. 2000), to stiff polymers with Greenfield ML (2004) Sorption and diffusion of small
detailed chemical structure, like polyamides molecules using Transition State theory and references
therein. In: Kotelyanskii M, Theodorou DN (eds) Sim-
(Heuchel et al. 2004), PIMs (Larsen et al. 2011), ulation methods for polymers. Marcel Dekker, New
Tr-PBO (Park et al. 2014) membranes, and on York, pp 425–490
polyelectrolytes (Dobrynin 2004). Gubbins KE, Moore JD (2010) Molecular modeling of
The predicted self-diffusion coefficients matter: impact and prospects in engineering. Ind Eng
Chem Res 49:3026–3046
depend principally on the quality of the force Gusev AA, Suter UW, Moll DJ (1995) Relationship
fields used to model the interactions not only between helium transport and molecular motions in
between the penetrant and polymer matrix but glassy polycarbonate. Macromolecules 28:2582–2584
also by intramolecular interactions between poly- Harmandaris VA, Mavrantzas VG (2004) Chapter 6.
Molecular dynamics simulations of polymers. In:
mer chains. MD simulation of gas diffusion in Kotelyanskii M, Theodorou DN (eds) Simulation
polymer membranes generates a wealth of infor- methods for polymers. Marcel Dekker, New York,
mation on the mechanism of gas transport but its pp 177–222
use is limited to high free-volume rubber matri- Heuchel M, Hofmann D, Pullumbi P (2004) Molecular
modeling of small-molecule permeation in polyimides
ces and small gas molecules due to prohibitive and its correlation to free-volume distributions. Mac-
CPU times for diffusion coefficients smaller than romolecules 37(1):201–214
108 cm2 s1. For this reason, today, the tech- Hofmann D, Tocci E (2009) Chapter 1. Molecular model-
nique is not adequate for systematic screening of ing. A tool for the knowledge-based design of
polymer-based membrane materials. In: Drioli E,
a large number of polymer candidates and gener- Giorno L (eds) Membrane operations: innovative sep-
ating data to be used in a materials design arations and transformations. Wiley-VCH Verlag
approach. GmbH %26 Co. KGaA, Weinheim, pp 253–255, and
The slowness of MD is an obstacle to the study references therein
Hofmann D, Fritz L, Ulbrich J, Schepers C, Bӧhning
of polymer properties, but not a barrier. This is M (2000) Detailed-atomistic molecular modeling of
especially true when the properties of interest are small molecule diffusion and solution processes in
localized, as in the case of glass transition or polymeric membrane materials. Macromol Theory
diffusivity of small molecules through a polymer Simul 9:293–327, and references therein
Jansen JC, Macchione M, Tocci E, De Lorenzo L,
matrix. At the far end of what can be achieved, Yampolskii YP, Sanfirova O, Shantarovich VP,
MD can also be applied to study polymer dynam- Heuchel M, Hofmann D, Drioli E (2009) Comparative
ics on the time and length scales of polymer study of different probing techniques for the analysis
entanglement. For current applications, we of the free volume distribution in amorphous glassy
perfluoropolymers. Macromolecules 42:7589–7604
focus on methods that have been illustrated with Larsen GS, Lin P, Siperstein FR, Colina CM (2011) Meth-
several polymers and are on the verge of being ane adsorption in PIM-1. Adsorption 17(1):21–26, and
competitive with existing empirical methods. references therein
Maginn EJ, Elliot JR (2010) Historical perspective and
current outlook for molecular dynamics as a chemical
engineering tool. Ind Eng Chem Res 49:3059–3078
References Park CH, Tocci E, Kim S, Kumar A, Lee YM, Drioli
E (2014) A simulation study on OH-containing
polyimide (HPI) and thermally rearranged
Binder K (ed) (1995) Monte Carlo and molecular dynam- polybenzoxazoles (TR-PBO): relationship between
ics simulations in polymer science. Oxford University gas transport properties and free volume morphology.
Press, New York J Phys Chem B 118:2746–275
Dobrynin AV (2004) Chapter 8. Molecular simulations of Razmus DM, Hall CK (1991) Prediction of gas adsorption
charged polymers. In: Kotelyanskii M, Theodorou DN in 5 Å zeolites using Monte Carlo simulation. AIChE
(eds) Simulation methods for polymers. Marcel Dek- J 37:769–779
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4 Molecular Dynamics in Membranes
Theodorou DN (2006) Chapter 2. Principles of molecular Theodorou DN (2010) Progress and outlook in Monte
simulation of gas transport in polymers. In: Carlo simulations. Ind Eng Chem Res 49:3047–3058
Yampolskii Y, Pinnau I, Freeman B (eds) Materials Widom B (1963) Some topics in the theory of fluids.
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Wiley, Chichester, pp 49–89
B
kCounts
500
1 4
400
300
200
5
2
100 3
25 50 75 100 minutes
Bilberry Aroma Recovery by Pervaporation, (4) trans-Hex-2-en-1-ol, and (5) 1-hexadecanol (Adapted
Fig. 1 GC-MS chromatogram of the crushed bilberry: from (Garcia et al. 2008))
(1) trans-hexenal, (2) 2-butyl-1-octanol, (3) 1-hexanol,
simplicity and versatility for the evaluation of Fig. 2. As expected, ethanol flux, JEtOH,
different membrane materials. However, the hol- increased linearly with higher ethanol con-
low fibers membrane (HFM) module configura- tent in the feed, while in contrast, aroma
tion presents important advantages, such as compound partial flux, JHex, remained inde-
higher contact area per unit volume of membrane pendent on ethanol concentration but
module and thus higher compactness of the presented a linear dependency with its own
equipment and easier operation at industrial concentration in the feed solution. The major
scale (Urtiaga et al. 1999, 2002; Tasselli component flux, water, was independent on
et al. 2007). both ethanol and aroma compound composi-
tion. The enrichment factors found for the
Influence of Process Variables aroma compound, bHex, varied from 98 to
Using a model ternary solution (water/ethanol/ 201.
trans-Hex-2-en-1-ol), the process variables that (ii) The feed temperature, studied in the range
exerted an important influence on the PV perfor- 35 C < T < 50 C. The components’ par-
mance of the impact aroma compound (trans- tial fluxes (water, ethanol, and trans-Hex-2-
Hex-2-en-1-ol) when using a PDMS HFM mod- en-1-ol) were found to follow an Arrhenius
ule with the characteristics presented at (Garcia dependency with temperature as plotted in
et al. 2008) were: Fig. 3.
(i) The feed composition (ethanol and aroma In the present application and working under
compound). The results are presented in laminar flow rate conditions, 203<Re<772, the
Bilberry Aroma Recovery by Pervaporation 3
[Hex] (kg.m–3)
a b 0 0.1 0.2 0.3
20 2.00 1.8
18 1.80 1.6
16 1.60 1.4
JEtOH (g.m–2.h–1)
JHex (g.m–2.h–1)
JHex (g.m–2.h–1)
14 1.40
1.2
12 1.20
1.0
10 1.00
8 0.80 0.8
6 0.60 0.6
4 0.40 0.4
2 0.20 0.2
0 0.00 0.0
0 2 4 6 0 5 10
[EtOH] (%v/v)
XHex g Hex P0 Hex (Pa)
Bilberry Aroma Recovery by Pervaporation, [Hex] = 0.1 kg.m 3, T = 50 C and Re = 772. (b) Effect
Fig. 2 (a) Effect of ethanol concentration in the feed on of trans-hex-2-en-1-ol partial pressure in the feed on its
the permeation flux of the ethanol in (■) binary water/ permeation flux at 50 C, Re = 772, and [EtOH] = 1%v/v
ethanol and (◊) ternary water/ethanol/Hex mixtures, and (Adapted from (Garcia et al. 2008))
(~) flux of trans-hex-2-en-1-ol in ternary mixtures
1.5 Water
from (García et al. 2008))
1.0
0.5
0.0
–0.5
–1.0
3.05 3.10 3.15 3.20 3.25 3.30
1000/T(K–1)
Bilberry Aroma Recovery by Pervaporation, Table 1 Feed composition (found in Hirvi and Honkanen 1983), and
simulation results of the permeate composition, enrichment factors, and partial fluxes in the bilberry multicomponent
system after PV with a PDMS HFM module at 30 C and a membrane area Am = 0.0056 m2 (Diban et al. 2008)
Feed composition, CFi Permeate composition, CPi
Component (mg.kg 1) (mg.kg 1) bi Ji (g.m 2
h 1)
Trans-Hex-2-en-1-ol 0.01 1.21 120.6 3.78 10 5
n-Hexanol 0.02 4.74 236.9 14.9 10 5
Trans-Hex-2-en-1-al 0.06 2.78 46.3 8.70 10 5
Linalool 0.004 0.20 49.3 0.62 10 5
Phenyl acetaldehyde 0.003 0.02 5.5 0.05 10 5
Benzyl alcohol 0.08 0.33 4.2 1.05 10 5
Cis-Hex-3-en-1-ol 0.06 1.64 27.4 5.15 10 5
Ethanol 7800 106,934 13.7 2.51
Water 992,200 893,057 0.9 20.9
7.00E-05 180
160
6.00E-05
140
JHex(g m–2 h–1)
5.00E-05
120
4.00E-05 100
bHex
3.00E-05 80
2.00E-05 60
40
1.00E-05
20
0.00E-00 0
0 5 10 15 20 0 5 10 15 20
δ ¥ 104 (m) δ¥ 104 (m)
aroma compound enrichment factors with the compounds in the food industry. Part I: simulation
minimum flux reduction, such as POMS. and performance. J Food Eng 54:183–195
Lipnizki F, Olsson J, Trägårdh G (2002b) Scale-up of
pervaporation for the recovery of natural aroma com-
pounds in the food industry. Part II: optimization and
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Sci Technol 33:1629–1652 compounds. Lebensm Wiss Technol 2:78–81
Lipnizki F, Hausmanns S, Ten PK, Field RW, Laufenberg Willemsen JHA, Dijkink BH, Togtema A (2004)
G (1999) Organophilic pervaporation: prospects and Organophilic pervaporation for aroma isolation-
performance. Chem Eng J 73:113–129 industrial and commercial prospects. Membr Technol
Lipnizki F, Olsson J, Trägårdh G (2002a) Scale-up of 2:5–10
pervaporation for the recovery of natural aroma
C
Chromium Transport Through Ion based on the use of selective liquid membranes,
Exchange Membranes especially emulsion liquid membranes (ELMs)
(Salazar et al. 1992) supported liquid membranes
Eugenio Bringas and Immaculada Ortiz (SLMs) (Kentish and Stevens 2001),
Department of Chemical and Biomolecular non-dispersive solvent extraction (NDSX)
Engineering, University of Cantabria, Santander, (Bringas et al. 2012), and the emulsion
Cantabria, Spain pertraction technology (EPT) (Bringas
et al. 2006a).
Chromium Transport −2 −1 0 1 2 3 4 5 6 7 8 9 10
Through Ion Exchange 2
Membranes,
Fig. 1 Speciation diagram 1 Cr2O72-
of Cr6+ in aqueous solution
−2
−3
−4
−2 −1 0 1 2 3 4 5 6 7 8 9 10
pH
1.FUNDAMENTALS
Problem Statement Selection of Extraction (EX) and Back-Extraction (BEX) MBSX Technology Selection
Agents
- Effluent characterisation - Proposal of EX and BEX reactions - Process configuration
- Objectives - Kinetic or equilibrium Patten - Operational conditions
- Obtention of the equilibrium/kinetic parameters
2. TECHNICAL EVALUATION
Kinetic Analysis of the Separation - Concentration Process Mathematical Modeling of the Separation - Concentration Process
- Analysis of the influence of the operation variables on the EX - Solute mass balances in the different fluid phases
and BEX kinetics - Mass transfer coefficients
- Model validation
- Removal and recovery requirements (Constrains) Detailed cost evaluation of the selected alternative
- Preliminary capital cost definition (Objective Function) - Capital cost evaluation
- Proposal of design alternatives (Network Superestructures) - Operation cost evaluation
- Mathematical modeling of the network superestructures - Analysis of the investment recovery
(Opimization Model)
- Application of the mathematical optimization techniques to select
the alternative with minimum total cost
Chromium Transport Through Ion Exchange Membranes, Fig. 2 Design methodology of selective liquid
membrane processes
the shore. The process should be designed to the guidelines reported in Fig. 2. In general,
(i) reduce the chromium concentration in the extraction systems involving ionic species are
polluted water below the disposal limit (0.5 mg generally thought to reach chemical equilibrium
L1) and (ii) obtain a concentrated chromium at the interface, and thus equilibrium models of
solution (>20 g L1) with negligible concentra- the chemical reactions are proposed. Table 1
tions of sulfate and chloride anions. The design reported the extraction mechanism and the equi-
methodology is briefly illustrated in Fig. 2. librium parameters for the multicomponent sys-
Synthetic solutions that simulate the anionic tem, Alamine 336/chromium/sulfate/chloride.
composition of the real groundwater The emulsion pertraction technology (EPT)
6+
[Cr ] = 500–1,300 mg L1, which combines the advantages of ELM, i.e.,
[SO42] = 900–3,000 mg L1 and high efficiency due to large surface area for
[Cl] = 300–1,000 mg L1, were employed as mass transfer, and SLM, i.e., extraction and strip-
feed solutions. The pH of the feed solution was ping are performed in one step without dispersion
adjusted to 1.5 using H2SO4. The organic solution of the organic phase into the aqueous feed phase,
was formulated as follows: 10 % (v/v) of Alamine was selected as the most suitable configuration of
336 as the anionic extractant, 3 % (v/v) of the selective liquid membrane technology. More
Pluronic PE 3100 as surfactant, and Isopar details about the technology can be found else-
L fluid as solvent. The emulsion was prepared where (Bringas et al. 2006a; Bringas and Ortiz
by dispersing the stripping solution (NaOH 2014). Kinetic experiments were performed in a
3–6 mol L1) in the organic phase at a volume laboratory experimental setup containing a mem-
ratio organic/stripping = 4/1. brane contactor Liqui-Cel ® Extra–Flow 2.5 8
After defining the separation system, the with fiber X-30 that provides an effective mem-
experimental and theoretical description of the brane area of 1.4 m2. Figure 3 shows the evolu-
extraction equilibria was performed following tion with time of the chromium concentration in
4 Chromium Transport Through Ion Exchange Membranes
Chromium Transport Through Ion Exchange Membranes, Table 1 Extraction mechanism and equilibrium
parameters
Extraction reaction Equilibrium parameter
HCrO þ
4 þ H þ R3 N , ðR3 NH ÞHCrO4
K1 = 4.83 mol2 m6
þ
7 þ 2H þ 2R3 N , ðR3 NH Þ2 Cr 2 O7
Cr 2 O2 K2 = 0.741 mol4 m12
HSO þ
4 þ H þ R3 N , ðR3 NH ÞHSO4
K3 = 1.37 103 mol2 m6
ðR3 NH ÞHSO4 þ Cl , ðR3 NH ÞCl þ HSO
4
K4 = 1.52
2 100
Aqueous
[Cr+6](mol/m3) stripping
80 Phase
1,5 Aqueous
[Cr+6](mol/m3)
0 0
0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6
t (h)
Feed Organic Stripping
Chromium Transport Through Ion Exchange Membranes, Fig. 3 Qualitative and quantitative evolution of the
chromium concentration in the fluid phases (Feed solution: flows in continuous mode; Emulsion: recirculated)
the different fluid phases (feed, organic, and strip- reason the selectivity had to be controlled in the
ping) and a photograph of the fluid phases at the extraction step.
end of the experiment. Similar extraction and The kinetic analysis was completed with the
back-extraction results were reported for sulfate proposal of the multicomponent separation math-
and chloride anions (Bringas et al. 2006a). ematical model of the EPT process with the
The kinetic results confirmed the high selec- corresponding design parameters: (i) mass trans-
tivity of the carrier Alamine336 toward chro- port coefficients in the aqueous feed phase
mium species. The total chromium boundary layer (kL), in the membrane (km), and
concentration decreased from 500 mg L1 at the in the organic phase stagnant layer (koAv) for the
module inlet to 0.8 mg L1 at the module outlet in different species involved in the separation-
one pass when the residence time in the module is concentration process (see Fig. 4) and (ii) the
0.014 h. The chromium concentration in the strip- equilibrium parameters of the extraction reac-
ping phase reached an average value of 14.6 g tions reported in Table 1. The model described
L1 after 1.3 h, and thus, a concentration factor of satisfactorily the kinetics and selectivity of the
18,733 was reached before depletion of the strip- separation-concentration EPT process under a
ping reagent. From the analysis of the results wide range of operational conditions and served
obtained for the competitive species, it was con- as a tool to perform the optimal design of the
cluded that the back-extraction process was not separation process (Bringas et al. 2006a).
selective because all the species were totally Finally, a novel design methodology based on
back-extracted from the organic phase. For this the application of mathematical optimization was
developed in order to determine the optimal EPT
Chromium Transport Through Ion Exchange Membranes 5
(kLi)
KL,Chloride 0.317 . (Q1/3
2
)(m/h) Calculated
2,5 m3/h 3
2,5 m /h
2,5 m3/h 0,041 mol/m3 0,01 mol/m3
2
7,7mol/m3
A total = 591 m m3a A3=150 m2
S4a
3 3
1,09 m /h 1,09 m /h
3
7,7 mol/m3 2 0,041 mol/m
A2=193 m
a 3 a 3
Q = 2,5 m /h Q = 2,5 m /h
3 3
[Chromium(VI)] in = 7,7 mol/m [Chromium(VI)] out ≤ 0,01 mol/m
Chromium Transport Through Ion Exchange Membranes, Fig. 5 Optimal process configuration for the aqueous
feed solution
process configuration able to achieve, at mini- known flow rate of 2.5 m3 h1 and a chromium
mum cost, the separation and concentration concentration of 400 mg L1 (7.7 mol m3).
objectives, (i) the contaminant removal up to the Comparison of the results obtained from the anal-
required concentration level ([Cr6+] <0.5 mg ysis of the different design alternatives concluded
L1) and, (ii) the selective contaminant recovery that a network configuration with three treatment
to obtain a concentrated solution that can be modules combined in series and parallel and with
reused elsewhere ([Cr6+] 20 g L1). The different a total membrane area of 591 m2 was the most
design alternatives were represented by means of suitable process configuration to comply, at min-
network superstructures that were modeled imum cost, with the concentration specifications
through the developed EPT mathematical in the outlet streams. Figures 5 and 6 show the
model, generating optimization problems that optimal networks for the aqueous feed solution
were solved following global optimization tech- and the emulsion phase, respectively.
niques (Bringas et al. 2007).
The procedure was illustrated for the treat-
ment of an incoming groundwater stream with a
6 Chromium Transport Through Ion Exchange Membranes
3
0,13 m /h
Co =0,002 mol/m3
3
Cg = 0,1 mol/m
2
A1 = 248 m
3 3
0,24 m /h 0,13 m /h
Co = 0,002 mol/m3 Co = 0,42 mol/m
3
3
Cg = 0,1 mol/m Cg = 400 mol/m
3
e
S4
0,11m3/h 0,24 m3/h
3
Co = 0,002 mol/m Co = 0,002 mol/m3
3
Cg = 0,1 mol/m Cg = 400 mol/m
3
0,048 m3/h
Cg = 400 mol/m3
Chromium Transport Through Ion Exchange Membranes, Fig. 6 Optimal process configuration for the emulsion
phase
Nickel and Welding, Environmental and Experimental Pagilla KR, Canter LW (1999) Laboratory studies on
Data. IARC, Lyon remediation of chromium contaminated soils.
Kentish SE, Stevens GW (2001) Innovations in separa- J Environ Eng 125:243
tions technology for the recycling and re-use of liquid Rengeraj S, Yeon KH, Moon SH (2001) Removal of
waste streams. Chem Eng J 84:149 chromium from water and wastewater by
Kimbrough DE, Cohen Y, Winer AM, Creelman L, ion-exchange resins. J Hazard Mater B87:273
Mabuni C (1999) A critical assessment of chromium Rivero MJ, Primo O, Ortiz MI (2004) Modellins of Cr
in the environment. Crit Rev Environ Sci Technol 29:1 (VI) removal from polluted groundwaters by ion
Lin C (2002) The chemical transformations of chromium exchange. J Chem Technol Biotechnol 79:822
in natural waters-A model study. Water Air Soil Pollut Salazar E, Ortiz MI, Urtiaga AM (1992) Kinetics of the
139:137 separation of chromium(VI) with emulsion liquid
Mohan D, Pittman CU (2006) Activated carbons and low membranes. Ind Eng Chem Res 31:1523
cost adsorbents for remediation of tri- and hexavalent Venkateswaran P, Palanivelu K (2005) Studies on recov-
chromium from water. J Hazard Mater 137:762 ery of hexavalent chromium from plating wastewater
by supported liquid membrane using tri-n butyl phos-
phate as carrier. Hydrometallurgy 78:107
E
The emulsion pertraction technology (EPT) is a Recovery of Zinc from Liquid Wastes by
separation process that combines the ability of EPT
liquid membranes to promote the uphill transport
of target species by the coupling between mass Zinc’s electropositive nature makes it well-suited
transfer and chemical reaction and the benefits of for use as a coating for protecting iron and steel
using membrane contactors, namely, large inter- products from corrosion. For this reason, the sur-
facial area, nondispersive contact, and indepen- face treatment industry accounts for almost half
dent flow of the fluid phases. Figure 1 shows the zinc modern-day demand. The processes
flow diagram of the EPT process that comprises involved in the surface treatment of components
two essential process units: a microporous hollow are predominantly water-based, and thus the gen-
fiber membrane contactor (see Fig. 2) and the eration and management of complex liquid
emulsion vessel that contains a pseudo-emulsion wastes is an issue of concern (Bringas
consisting of the organic phase formulated with a et al. 2012). EPT has been proven to be an effi-
selective organic carrier and the dispersed strip- cient technology to perform both the selective
ping solution. The target solute is chemically removal and recovery of zinc from different
transferred from the aqueous feed to the organic wastes produced in the context of surface treat-
phase that is embedded in the pores of the hollow ment industry: (i) spent pickling acids (SPA)
fibers due to their hydrophobic character. Next, generated in the hot-dip galvanizing process
the solute-carrier complex diffuses to the inter- (see composition in Table 1) and (ii) spent
face between the organic and the droplet of strip- chromium-based passivation baths (SPB)
ping phase where the back-extraction reaction employed in zinc electroplating operations (see
occurs. The solute is recovered from the internal composition in Table 1).
Back-extraction
Extraction
— —
A + C ↔ AC
— Emulsion
Concentrate AC
Pore —
C
Emulsion Tank
Feed A
Solution Hollowfiber
Stripping Emulsion
droplet
Emulsion Pertraction Technology for Zinc Recovery, Fig. 1 Performance of the EPT process
Figures 3 and 4 depict the separation and extraction (BEX) percentages of zinc and iron,
recovery objectives to be achieved by the appli- when steady state conditions (regarding zinc
cation of EPT to the treatment of SPA and SPB. kinetics) are reached, are respectively, 79 %
Under the usual composition of SPA, zinc (EX Zn), 98 % (BEX Zn), 23 % (EX Fe), and
forms anionic chlorocomplexes (ZnCl42 and 38 % (BEX Fe). Under these operation condi-
ZnCl3 ) while iron is present in the form of tions, the maximum value of selectivity of zinc
neutral or cationic compounds (Regel over iron in the stripping solution is 15 kg of
et al. 2001). Tributyl phosphate (TBP) and Zn/kg of iron (Ortiz et al. 2004; Samaniego
water are reported as the most suitable extraction et al. 2006; Samaniego et al. 2007; Carrera
and back extraction reagents enabling the selec- et al. 2009; Bringas et al. 2012). On the other
tive separation and concentration of zinc with hand, the efficiency of the EPT process to carry
minimum iron extraction (Cierpezewski out the regeneration of real passivation baths is
et al. 2002). On the other hand, the information demonstrated in Fig. 7 which shows reductions in
provided by the equilibrium isotherms depicted the zinc and iron contents higher than 80 % after
in Fig. 5 confirms the commercial selective car- 3 h of experimental running with an almost neg-
rier bis(2,4,4- trimethylpenthyl) phosphinic acid ligible variation of the chromium concentration.
(Cyanex272) as a suitable reagent to formulate Furthermore, zinc is selectively recovered in the
the liquid membrane due to its capacity to selec- stripping solution (concentration >35 kg/m3)
tively separate Fe3+ and Zn2+ (tramp ions) from being the concentrations of iron (<0.45 kg/m3)
chromium under the typical pH conditions and chromium (<0.003 kg/m3) almost negligible
(1.8–2.5) of the passivation baths. Sulphuric (Urtiaga et al. 2010; Bringas et al. 2011; Diban
acid is selected as stripping agent (Urtiaga et al. 2011; Bringas et al. 2012).
et al. 2010). Therefore, these results confirm the EPT pro-
Figure 6 shows the kinetic results obtained cess as a suitable alternative to perform the treat-
with the SPA-TBP-water and the EPT process. ment of spent pickling acids and spent
It is concluded that the extraction (EX) and back- passivation baths allowing at the same time the
Emulsion Pertraction Technology for Zinc Recovery 3
Emulsion Pertraction
Technology for Zinc
Recovery,
Fig. 2 Characteristics of
hollow fiber contactors for
a bench scale EPT process
Parameter/Characteristic Value/Description
Thickness 30 μm
Porosity 40%
Emulsion Pertraction Technology for Zinc Recovery, Table 1 Physical-chemical properties of spent pickling acids
(SPA) and spent chromium-based passivation baths (SPB)
SPA SPB
Parameter Value Parameter Value
pH 0 pH 1.8–2.5
Zn2+ (mg/L) 122,000 Zn2+ (mg/L) 2500–11,780
Fe2+ (mg/L) 100,000 Fe3+ (mg/L) 20–90
Cl (mg/l) 300,000 Cr3+ (mg/L) 4500–9350
Free acidity, H+ (mol/L) 1 NO3 (mg/L) 67,520
Electrolytic
recovery of zinc
Stripping solution
Service (ZnCl2, HCl)
water Galvanizing
process
Emulsion Pertraction Technology for Zinc Recovery, Fig. 3 Treatment of spent pickling acids by EPT with zinc
recovery
Electrolytic
recovery of zinc
Stripping solution
(ZnSO4)
H2SO4 Cyanex272 Electroplating
process
Emulsion Pertraction Technology for Zinc Recovery, Fig. 4 Regeneration of chromium-based passivation baths by
EPT with zinc recovery
1. Determination of the optimal operational con- 2. Analysis of the long-term performance of the
ditions to: (i) maximize the extraction and separation process to evaluate the stability of
back-extraction kinetics and (ii) achieve max- the selective carrier which guarantees the pro-
imum values of selectivity which permit the cess’ economic viability.
exploitation of the different process streams
generated after the application of the EPT
process.
Emulsion Pertraction Technology for Zinc Recovery 5
Emulsion Pertraction
Technology for Zinc Selective separation
Recovery,
Fig. 5 Extraction 100
iron
isotherms of iron, zinc, and
chromium with Cyanex272
75
% Extraction
50
25
chromium
zinc
0
0 1 2 3 4 5 6 7
Equilibrium pH
0
0 30 60 90 120 150 180
t (min)
6 Emulsion Pertraction Technology for Zinc Recovery
% Extraction
concentrations in the
stripping solution after 3 h 60
of EPT regeneration of SPB
using Cyanex272 as 40
selective extractant
0.43 kg m−3
20 0.003 kg m−3
0
[Zn] [Fe] [Cr]
Heavy Metal Recovery by Membrane cheaper. At the same time, a clean permeate that
Operations meets the applicable effluent guidelines is
obtained. That can be achieved with high effi-
Jose Sabate ciency using various membrane technologies:
Department d’Enginyeria Agroalimentaria i ultrafiltration (UF), nanofiltration (NF), reverse
Biotecnologia, Universitat Politecnica de osmosis (RO), and electrodialysis (ED)
Catalunya, Castelldefels, Spain (Coman et al. 2013; Fu and Wang 2011;
Kurniawan et al. 2006).
UF membranes reject macromolecules, but
Several industries such as metal plating facilities, their pores are not small enough to retain heavy
mining operations, fertilizer industries, tanneries, metal ions such as Cd2+, Cu2+, Hg2+, Ni2+, Ni3+,
batteries, paper industries, pesticides, etc., pro- etc. Nevertheless, they can be concentrated with
duce heavy metal (Cd, Cr, Cu, Hg, Ni, Pb, Zn) the addition of a soluble polymer or surfactant
wastewaters. Heavy metals are not biodegradable that binds the metal ions. Those processes are
and persist in the environment: waters, soils, sed- named polymer-enhanced ultrafiltration (PEUF)
iments, etc. Further, their recovery could be and surfactant-enhanced ultrafiltration (SEUF)
attractive from the economical perspective, and (Coman et al. 2013; Fu and Wang 2011;
several technologies have been studied and pro- Kurniawan et al. 2006). At low pH, metal ions
posed to carry it out: chemical precipitation, ion are released from the polymer and a new ultrafil-
exchange, adsorption, membrane filtration, tration operation allows one to separate them.
coagulation-flocculation, flotation, and electro- The polymer can be regenerated by alkali addi-
chemical methods (Coman et al. 2013; Fu and tion and reused.
Wang 2011; Kurniawan et al. 2006). Membrane RO is used to remove almost everything from
separation technologies yield a high efficiency the water which includes small molecules and
and allow continuous operation. However, to pre- ions. It can produce drinking water from brackish
vent membrane clog, a pretreatment of the pol- water or seawater. Therefore, it has been shown
luted effluent to achieve a clean feed is required. to concentrate heavy metal ions such Cd2+, Cu2+,
Further, they need careful operation and periodic and Ni2+. However, compared to other membrane
washing to prevent membrane damages and technologies, RO requires the highest pressure
fouling. and energy cost.
Membrane separations can reduce the volume Nanofiltration (NF) is the intermediate process
of contaminated water, making the next pro- between UF and RO (Soldenhoff et al. 2005). NF
cesses necessary to full recovery easier and membranes usually have an electrical charge,
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_649-1
2 Heavy Metal Recovery by Membrane Operations
Heavy Metal Recovery by Polymer- natural polymers (chitosan, humic acids, etc.) and
Enhanced UF polymers anchored on the membrane represents
growing alternatives.
Jose Sabate A suitable polymer should have a high affinity
Department d’Enginyeria Agroalimentaria i for target ions and should be able to be recycled in
Biotecnologia, Universitat Politecnica de order to make the process economically feasible.
Catalunya, Castelldefels, Spain It should be biodegradable to prevent new envi-
ronmental problems, but it cannot have a very
short half-life in working conditions. As commer-
Polymer-enhanced ultrafiltration (PEUF) is one cial or natural polymers have a molecular weight
of the membrane operations that can be used to distribution, they must previously undergo a
separate or concentrate heavy metal from liquid diafiltration process to remove short chains,
streams. It is also called polymer-assisted ultra- which would bind heavy metals but would leak
filtration (PAF), complexation-ultrafiltration pro- through the UF membrane. Further, its interac-
cess (CUFP), or polymer-supported ultrafiltration tions with membrane materials should be consid-
(PSU) (Rivas et al. 2009). ered to minimize fouling.
Ultrafiltration membranes reject macromole- Modeling PEUF has usually been carried out
cules, but their pores are not small enough to through the classic complexation (or exchange
retain heavy metal ions such as Cd2+, Cu2+, Ni2+, ions) equilibrium reactions. For instance, the
Ni3+, Hg2+, etc. Nevertheless, if a soluble polymer union between a heavy metal ion, Mm+, and a
able of binding polyvalent cations is added to a neutral ligand group of the polymer, L, can be
solution containing heavy metal ions (F), the represented by the following chemical equilibri-
resulting metal-polymer complex will be retained ums and their respective constants:
by UF membranes. Then, a clean permeate
(P) can be obtained and the heavy metals will Mmþ þ nL ⇆ MLn mþ bn (1)
be concentrated in the retentate stream (R).
See figure 1. For n=1, 2, 3. . .
The polymers contain functional groups such The protonation of the L group is described
as amine, carboxylated, phosphonic, or sulfonate by:
which link to metals either through ionic or che-
lating bonds. The most used synthetic polymers
are polyacrylic acid (PAA) and polyethy-
leneimine (PEI) (Rivas et al. 2009). The use of
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_650-1
2 Heavy Metal Recovery by Polymer-Enhanced UF
polluted P
water
Mm+
P
H3C CH3
OH
Cross-References Nie CY, Zhan YK, Pan LK, Li HB, Sun Z (2011)
Electrosorption of different cations and anions with
membrane capacitive deionization based on carbon
▶ Membrane Capacitive Deionization nanotube/nanofiber electrodes and ion-exchange
membranes. Desalination Water Treat 30:266–271
Nikonenko VV et al (2010) Intensive current transfer in
References membrane systems: modelling, mechanisms and appli-
cation in electrodialysis. Adv Colloid Interface Sci
160:101–123
Andersen MB et al (2012) Current-induced membrane Sonin AA, Probstein RF (1968) A hydrodynamic theory of
discharge. Phys Rev Lett 109:108301 desalination by electrodialysis. Desalination
Biesheuvel PM, Zhao R, Porada S, van der Wal A (2011) 5:293–329
Theory of membrane capacitive deionization includ- Strathmann H (2010) Electrodialysis, a mature technology
ing the effect of the electrode pore space. J Colloid with a multitude of new applications. Desalination
Interface Sci 360:239–248 264:268–288
Lee J-B, Park K-K, Eum H-M, Lee C-W (2006) Desalina- Zhao R, Biesheuvel PM, Van der Wal A (2012) Energy
tion of a thermal power plant wastewater by membrane consumption and constant current operation in mem-
capacitive deionization. Desalination 196:125–134 brane capacitive deionization. Energy Environ Sci
Li HB, Zou L (2011) Ion-exchange membrane capacitive 5:9520–9527
deionization: a new strategy for brackish water desali-
nation. Desalination 275:62–66
D
Diffusion in Membranes,
Fig. 1 Motion of a carbon
dioxide molecule in a
6FDA-4PDA polymer
Cavity
matrix (Reprinted from size
Smit et al. (1992).
Copyright Elsevier
(permission pending))
Jump length λ
25
From Smit et al. (1992)
Jump
20
Movement in cavity
Position (Å)
15 Movement in cavity
10
Jump length
5 Cavity size
0
0 20 40 60 80 100 120 140 160 180 200
Simulation time (picoseconds)
diameter of 3.72 Å, while the molecule of carbon where DEa is the activation energy for diffusion,
dioxide is an oblate ellipsoid 5.25 Å long, but D* is a preexponential factor often related to as
with the diameter of only 3.03 Å. Consequently, the entropy of activation and the average jump
as carbon dioxide molecule bounces around in a length, and R and T are the universal gas constant
cavity it occasionally becomes oriented in such a and the absolute temperature, respectively. Dif-
way that it can jump through a gap between the fusion process in which D follows Eq. 2 is
polymer chains as small as 3.03 Å. Such a small referred to as an activated diffusion. The activa-
gap would not permit jumping of the methane tion energy for diffusion in polymeric mem-
molecule (Baker 2012). branes is positive; thus, the greater the DEa the
As temperature increases, the thermal motions smaller the D; also it indicates that D increases
of polymer chains allowing the molecule to jump with T, which is consistent with molecular
from one cavity to the other become more fre- dynamics simulations. In turn, DEa is directly
quent, and also the molecule bounces faster with proportional to a cohesive energy density
a cavity, which means that once a transient open- (CED), which is indicative of strength of attrac-
ing of appropriate size becomes available, it will tive forces between adjacent polymer chains. The
more likely jump into the adjacent cavity. Exper- CED increases when polar and hydrogen bond
imentally observed dependence of D in poly- groups are present in polymer chains (Koros and
meric membranes on temperature follows the Fleming 1993).
Arrhenius relationship (Burggraaf 1996):
DEa
D ¼ D exp (2) Diffusion in Microporous Membranes
RT
Microporous membranes have permanent path-
ways (pores) for transport of molecules. They are
Diffusion in Membranes 3
generally made from inorganic materials such as carbon pore from outside environment, in which
zeolites, carbonized polymers, and amorphous Eout = 0. The pore diameter corresponding to
silica; however, organic membranes made from W = 0 is referred to as a minimum pore size
polymers with intrinsic microporosity (PIM), (dmin), while the pore diameter corresponding to
such as polytrimethylsilylpropyne (PTMSP), are W = RT represents Knudsen diameter (dK). Acti-
also considered as microporous (Baker 2012). vated diffusion occurs when d < dmin, surface
The three most common diffusion mecha- diffusion dominates when dmin < d < dK, while
nisms in microporous membranes, shown in Knudsen diffusion dominates when d > dK.
Fig. 2, include activated diffusion (small pores), Table 1 summarizes dmin and dK for different
surface diffusion (intermediate pores), and Knud- gases in carbon and silica pores with two different
sen diffusion (large pores). The exact pore size pore geometries.
ranges for a given diffusion mechanism are deter-
mined based on the difference (W) between the
potential energy outside the pore (Eout) and the
Activated Diffusion Versus Surface
potential energy within the pore (Ein) (Thornton
Diffusion
et al. 2010).
As a molecule approaches a pore opening,
When transport is dominated by activated diffu-
each atom in the gas molecule interacts with
sion, there is no adsorption and membrane per-
every atom from the pore wall through van der
meability (P) is solely governed by the diffusion
Waals forces. The potential difference is also
coefficient, i.e.:
referred to as a suction energy; because a positive
W translates to a force sucking the molecule from
DEa jW j
outside to inside of the pore (adsorption), while a P ¼ P exp ¼ P exp (3)
RT RT
negative W results in a force repulsing the mole-
cule from the pore. The activated transport takes
where DEa is the activation energy for diffusion,
place when W < 0, and the activation energy for
which is identical to DEa in Eq. 2, which is equal
diffusion in Eq. 2 corresponds to DEa ¼ jW j
to the absolute value of the potential difference.
(Thornton et al. 2010).
On the other hand, when transport is dominated
Figure 3 presents an example of the potential
by surface diffusion, membrane permeability (Ps)
energy difference as function of pore size (d) for a
is governed by both the diffusion coefficient (Ds)
single oxygen molecule entering a cylindrical
and the solubility coefficient (Ss). The latter is a
4 Diffusion in Membranes
W (eV)
Sons. (permission 0.2
pending))
0.1
0
dmin dK
−0.1
−0.2
3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Pore size(Å)
Diffusion in Membranes, Table 1 Minimum pore size for the activated transport (dmin) and minimum pore size for
Knudsen diffusion (dK) at room temperature (298 K). All pore sizes are given as the PAS pore sizea (Adapted from
Thornton et al. 2010)
Pore geometry
Cylindrical pore Slit-shaped pore
Carbon Silica Carbon Silica
Gas dmin (Å) dK (Å) dmin (Å) dK (Å) dmin (Å) dK (Å) dmin (Å) dK (Å)
He 2.30 5.69 2.53 6.37 1.86 2.19 2.06 4.35
H2 2.57 8.82 2.79 9.79 2.10 6.52 2.31 7.22
CO2 2.95 12.30 3.17 13.35 2.46 9.27 2.65 10.12
O2 3.10 11.68 3.31 12.68 2.59 8.76 2.79 9.58
N2 3.27 11.49 3.48 14.46 2.75 8.60 2.94 9.39
CH4 3.49 13.74 3.69 14.84 2.95 10.43 3.13 11.32
CO 3.32 12.14 3.52 13.16 2.79 9.14 2.98 10.00
Ar 3.18 11.68 3.39 12.67 2.66 8.76 2.86 9.56
n-C5H12 5.27 23.51 5.45 25.04 4.59 18.33 4.75 19.57
C2H6 4.02 16.69 4.21 17.93 3.44 12.82 3.62 13.86
SF6 4.66 19.46 4.85 20.81 4.03 15.05 4.20 16.15
a
Positron annihilation spectroscopy (PAS) diameter d0 = d – dd, where dd is the electron cloud thickness surrounding
the surface atoms (dd = 3.32 Å)
q
thermodynamic factor that correlates the concen- Ss ¼ K o exp (4)
tration of molecules in the adsorbed phase to the RT
external pressure, which typically follow a Lang-
muir isotherm. At the same time, Ss follows where q (>0) is a heat of adsorption, which implies
Arrhenius relation: that Ss decreases with temperature. Surface diffu-
sion is an activated process, which depends on q:
Diffusion in Membranes 5
aq
Ds ¼ Ds exp (5) for activated diffusion in microporous
RT membranes.
The third diffusion mechanism, Knudsen dif-
where a is a proportionality constant (0 < a <1). fusion, is not an activated process. Although
The product aq is the activation energy for sur- Knudsen diffusion coefficient increases with
face diffusion, which represents the energy bar- temperature, it does not follow Arrhenius-type
rier separating two adjacent sorption sites relationship (Thornton et al. 2010).
(Thornton et al. 2010). Since Ps = DsSs, combin-
ing Eqs. 4 and 5 leads to:
References
ð1 aÞq
Ps ¼ Ps exp (6)
RT Baker RW (2012) Membrane technology and applica-
tions. Wiley, West Sussex
Burggraaf AJ (1996) Transport and separation properties
The term, (1 – a)q is positive; therefore, Ps,
of membranes with gases and vapours. In: Burggraaf
unlike P, decreases with temperature. In the AJ, Cot L (eds) Fundamentals of inorganic membrane
case of dense polymeric membranes, the perme- science and technology. Elsevier Science, Amsterdam,
ability coefficient is also a product of the diffu- pp 331–433
Koros WJ, Fleming GK (1993) Membrane-based gas sep-
sivity and the solubility coefficients, and the
aration. J Membr Sci 83:1–80
latter, similarly to the surface diffusion solubility Smit E, Mulder MHV, Smolders CA, Karrenbeld H, van
coefficient, decreases with temperature. On the Eerden J, Feil D (1992) Modeling of the diffusion of
other hand, the corresponding increase in diffu- carbon dioxide in polyimide matrices by computer
simulation. J Membr Sci 73:247–257
sivity overcompensates a decrease in solubility.
Thornton AW, Hill JM, Hill AJ (2010) Modelling gas
Thus, the permeability coefficient in dense poly- separation in porous membranes. In: Yuri
meric membranes follows Arrhenius-type rela- Yampolskii Y, Freeman B (eds) Membrane gas sepa-
tionship similar to the permeability coefficient ration. Wiley, Hoboken, pp 85–109
D
Dual Mode Sorption Model (PPO) 186 C for polysulfone (PSF) 100 C for
polystyrene.
Donald R. Paul The dual mode sorption model consists of the
Department of Chemical Engineering, Texas sum of Henry’s law term and a Langmuir term,
Materials Institute, Austin, TX, USA i.e.,
C0H bp
C ¼ kD p þ (1)
The dual mode sorption model is a convenient 1 þ bp
and commonly used equation for describing gas
sorption in polymers at temperatures below the where kD is Henry’s law coefficient, CH0 is the
glass transition temperature, Tg, of the polymer. Langmuir capacity term, and b is an affinity
Gas sorption in glassy polymers generally parameter. It appears that Barrer et al. (1958)
(a) exhibits nonlinear isotherms that are concave were the first to propose this now well-known
to the pressure axis, unlike the linear ones seen equation. Equation 1 provides a very good fit of
above Tg, (b) shows greater levels than for rub- data like that in Fig. 1 where the CH0 obtained by
bery polymers with the extent being larger the the fitting would increase as the polymer Tg
higher is the Tg, and (c) depends on the prior increases relative to the measurement
history of the sample and the details of the mea- temperature T, i.e., C0H Tg T, and is thought
surement protocol (Horn and Paul 2012). The first to be related to the unrelaxed volume of the glass;
two aspects are well illustrated in Fig. 1 that see Paul (2010) for a recent summary of the
shows the concentration of carbon dioxide, C, extensive literature in this area. The CH0 term
dissolved in five different polymers as a function would be zero for butyl rubber, i.e., Eq. 1 reduces
of the pressure, p, in the external carbon dioxide to Henry’s law, since it is not in the glassy state.
gas phase. Butyl rubber shows a linear isotherm, Petropoulos (1970) proposed that the Lang-
while all four of the glassy polymers show fea- muir population may have a finite, but different,
tures (a) and (b) mentioned above at this mea- mobility than Henry’s law population. Paul and
surement temperature, i.e., T = 35 C. The Koros (1976) extended this analysis to give
extent of carbon dioxide sorbed into these glassy expressions for the time lag and the following
materials increases the higher is the Tg; i.e., expression for the permeability coefficient, P,
their glass transition temperatures descend in for gases in glassy polymers:
the following order: 310 C for the polyimide
Matrimid 210 C for poly(phenylene oxide)
20 Polystyrene
References
10
Butyl Rubber Barrer RM, Barrie JA, Slater J (1958) Sorption and diffu-
0 sion in ethyl cellulose. III. Comparison between ethyl
0 5 10 15 20 25 cellulose and rubber. J Polym Sci 27:177–197
CO2 Pressure (atm) Horn NR, Paul DR (2012) Carbon dioxide sorption and
plasticization of thin glassy polymer films tracked by
optical methods. Macromolecules 45:2820–2834
Dual Mode Sorption Model, Fig. 1 Sorption isotherms
Paul DR (2010) Fundamentals of transport phenomena in
for CO2 in various polymers at 35 C (Reprinted with
polymer membranes. In: Drioli E, Giorno L (eds)
permission from Horn and Paul 2012. Copyright 2012
Comprehensive membrane science and engineering,
American Chemical Society)
vol 1. Academic, Oxford, pp 75–90
Paul DR, Koros WJ (1976) Effect of partially
C0H bDH immobilizing sorption on permeability and the diffu-
P ¼ kD DD þ (2) sion time lag. J Polym Sci Polym Phys Ed 14:675–685
1 þ bp2 Petropoulos JH (1970) Quantitative analysis of gaseous
diffusion in glassy polymers. J Polym Sci Part
where DD is the diffusion coefficient associated A-2(8):1797–1801
with Henry’s law population and DH is the
D
ð tf
JC ¼ k1 tf þ k2 c1 ½1 R1 ðtÞ qðtÞ dt
ð tf 0 References
þ k3 aðtÞqðtÞ dt
0 Fikar M, Kovács Z, Czermak P (2010) Dynamic optimiza-
tion of batch diafiltration processes. J Membr Sci
355(1–2):168–174. doi:10.1016/j.
where total cost is a sum of three terms that are the
memsci.2010.03.019
operational cost of the pump, cost of the valuable Lutz H (1997) Membrane filtration with optimized addi-
component loss, and the cost of the utilized dilu- tion of second liquid to maximize flux, United States
tion water. k1, k2, and k3, are the respective cost Patent 5,597,486. Assignee: Millipore Investment
Holdings Limited, Wilmington
factors.
Paulen R, Fikar M, Foley G, Kovács Z, Czermak P (2012)
This technique can be useful to evaluate opti- Optimal feeding strategy of diafiltration buffer in batch
mal operation of membrane filtration plants membrane processes. J Membr Sci 411–412:160–172
including reverse osmosis, ultrafiltration,
E
Ease of Expansion in Gas Separation reference technologies for gas separation, PSA
and absorption systems can also be expanded,
Adele Brunetti but it requires additional design considerations
National Research Council, Institute for and adds cost in the initial phase of the project.
Membrane Technology (ITM-CNR), The The cryogenic units cannot be expanded if it is
University of Calabria, Rende (CS), Italy not foreseen during the design phase. Generally
they can be over-dimensioned, and a capacity
increase is often obtained without modification
Quite often during the operation of a system for to the cold box itself through addition of a tail gas
the treatment of gases, it is necessary to expand it compressor.
for treating greater streams. In some cases, future
expansion is contemplated even during the initial
phase of a project. In other cases, it could be a
References
necessity not foreseen during system design
phase (Miller and Stöcker 1989; Brunetti Brunetti A, Bernardo P, Drioli E, Barbieri G (2010) Mem-
et al. 2010). brane engineering progresses and potentialities in gas
Membrane system expansion is very easy, separations. In: Yampolskii Y, Freeman B (eds) Mem-
since this only requires the addition of identical brane gas separation. Wiley, New York, pp 281–312
Miller GQ, Stöcker J (1989) Selection of a hydrogen
modules. This is the advantage offered by the separation process NPRA annual meeting, 19–21
modularity of membrane units and the reduced Mar, San Francisco
equipment and control systems required for oper-
ating it. In comparison, considering the other
Electrical Double Layer forms on one side of the phase interface. The
Fig. 1 provides a schematic sketch of the two
Karel Bouzek and Tomas Bystron mentioned cases. In the case of functionalized
Faculty of Chemical Technology, University of materials, the charge-carrying groups covalently
Chemistry and Technology Prague, Technicka 5, bound to the polymeric backbone are oriented
Prague 6, Czech Republic towards the void volume of the membrane inte-
rior, thus forming an electrically charged film
covering the phase interface on the side of the
An electrical double layer is usually considered solution. The charge of this film is compensated
to form at the phase interface between two elec- by that of the mobile ions present in the solution
trically conducting media. In such a case, on one and located close to the film (see Fig. 1a).
side of the interface, an excess of positive charge In the case of the non-functionalized mate-
exists, which is counterbalanced by an identical rials, the surface charge fixed to the surface of
excess of negative charge localized on the oppo- the solid phase is formed by specific adsorption of
site side of the interface. The overall system ions of one sign. Both the sign of the adsorbed
charge is thus equal to zero. In membrane sci- ions and the extent of the adsorption are deter-
ence, this definition has, to a certain degree, been mined by the properties of the membrane mate-
modified, the reason being that membranes can rial. In this case, too, the fixed charge is
be produced from a broad spectrum of materials, compensated by the charge of ions moving in
including (i) electronic conductors (e.g., metals), the system and located close to the absorbed
(ii) ionic conductors (e.g., O2 -conducting surface film (see Fig. 1b).
ceramics), (iii) functionalized polymers provi- An electrical double layer significantly influ-
ding ionic conductivity through the liquid filling ences the properties of the membrane, mainly
the void volume of the material (ion-selective with respect to its transport properties and behav-
membranes), and (iv) nonfunctionalized poly- ior under current load. In selected cases the sur-
meric or ceramic membranes. face of the membrane materials is modified to
Whereas, in the first two cases, the traditional achieve the preferred adsorption and thus the
definition is valid, in the last two, the situation is required transport and properties, including
different. This is due to the fact that the bulk selectivity.
membrane material is neither an electronic nor
an ionic conductor. Hence the double layer only
Electrical Interactions in Membranes and inorganic nature. These carriers interact with
the charge carriers fixed in the material of the
Karel Bouzek membrane (see also the electrical double layer).
Faculty of Chemical Technology, University of The charge fixed in the membrane material is, in
Chemistry and Technology, Prague, Technická 5, principle, of dual origin: (i) it comes from the
Prague 6, Czech Republic component introduced and incorporated during
its synthesis, and (ii) it is the result of the specific
adsorption of ions on the surface of the solid
In general electrical (electrostatic) interactions phase. Electrostatic interactions between fixed
arise as a result of the interaction of electrically and freely moving charge carriers are responsible
charged particles (charge carriers) with sur- not only for several phenomena characteristic of
rounding matter (electrically charged and neu- membrane separation processes, such as the exis-
tral) (Stuart 1989). In the case of membranes, tence of Donnan potential, the selectivity of mass
probably the most important interactions to con- transport, or mass transport enhancement under
sider are those between electrically charged current load by electroosmotic flux, but also for
bodies, such as ions dissolved in solution and the existence of life itself. These facts document
ion-conducting, functionalized, or even inert the importance of electrical interactions in mem-
membranes. In living systems the electrostatic brane materials with respect to their transport
interactions between the charged/polar and neu- properties.
tral/nonpolar side of a solute molecules with
each other and with a solvent are responsible
for the formation/assembly of monolayer and References
bilayer biological membranes and their
functioning. Stuart McLaughlin (1989) The Electrostatic Properties of
Membranes. Annu. Rev. Biophys. Biophys. Chem.
On the fluid side the charge carriers are typi-
18:113–136
cally mobile ions or colloidal particles of organic
Electrodialysis, Concentrate
Fig. 1 Schematic diagram
illustrating the principle of Diluate
electrodialysis A C A C C
+ – + – + – +
– + – +
– + – –
+ – + – –
Anode + + Cathode
+ + – – + + – – – –
– – –
+ +
+ –
+
+ – – –
+ – + – –
+ + – + – – + + – + – – + – –
+ – + – –
Electrode + – + – – Electrode
rinse + – + – – rinse
Feed
Repeating unit
Ion-exchange
Electrode membrane
cell
Concentrate
Diluate
Electrode
rinse solution
Feed solution
Feed solution
Electrodialysis, Fig. 2 Schematic drawing illustrating the construction of a sheet flow stack design
density, Cf and Cp are the feed and product water electrodialysis is the relatively high energy con-
concentrations, and x is an efficient term which is sumption when solutions with high salt concen-
generally close to 1. trations have to be processed. Thus,
Electrodialysis has advantages and limitations electrodialysis can only be cost-effectively
compared to other deionization processes such as applied in water desalination in a certain range
reverse osmosis. A main advantage of electrodi- of feed water salt concentration and required
alysis compared to reverse osmosis is that very product water (Strathmann 2010).
little feed pretreatment is required and higher
brine concentrations can be achieved.
A major disadvantage especially for the pro-
References
duction of potable water is the fact that only ions
are removed, while uncharged components such Katz WE (1979) The electrodialysis reversal process.
as microorganisms or organic contaminants will Desalination 28:31–40
not be eliminated. Another disadvantage of
Electrodialysis 3
Schaffer LH, Mintz MS (1966) Electrodialysis. In: Strathmann H (2010) Electrodialysis, a mature technology
Spiegler KS (ed) Principles of desalination. Academic, with a multitude of new applications. Desalination
New York, pp 3–20 264:268–288
E
CONCENTRATE (OUTLET)
DILUATE (OUTLET)
ELECTROLYTE
Na+ Na
+
Na
+
Na
+ +
Na Na
+
+ + + + +
Na Na Na Na Na
ANODE CATHODE
Cr Cr Cr Cr Cr
Cr Cr Cr Cr Cr Cr
D C D C D C D C D C D
DILUATE (INLET)
CONCENTRATE (INLET)
Electromembrane Processes, Fig. 1 Scheme of a conventional two-compartment electrodialysis stack (C): concen-
trate, (D): diluate compartments
alkali process, the cells are arranged in a similar membrane is a composite structure of sulfonated
way as in an electrodialysis stack but in two and carboxylated perfluorinated reinforced
different configurations using monopolar or bipo- polymers.
lar electrodes. Due to the severe operating condi- (iii): Ion-exchange membranes are used today
tions (80 C, 35 wt% NaOH, wet chlorine), the also as key components in energy storage and
Electromembrane Processes 3
conversion systems such as batteries and fuel anion exchange membranes. Desalin Water Treat
cells. A fuel cell is an electrochemical reactor in 35:158–163
Kobuchi Y, Motomura H, Noma Y, Hanada F (1987)
which energy is converted into electrical energy. Application of ion exchange membranes to recover
Generally fuel cells are fed with hydrogen which acids by diffusion dialysis. J Membr Sci 27:173–179
is transformed into protons at a catalytic anode Lucia U (2014) Overview on fuel cells. Renew Sustain
with electrons. Protons then migrate across a Energy Rev 30:164–169
Pletcher D, Walsh FC (1990) Industrial electrochemistry.
proton conducting membrane and combine with Chapman & Hall, London
oxygen to produce water at the catalytic cathode Pourcelly G, Bazinet L (2009) Developments of BPM
(Lucia 2014). technology in food and bio-industries. In: Pabby AK,
Rizvi SSH, Sastre AM (eds) Handbook of membrane
separations. CRC Press, Boca Raton, pp 581–634
Sata T (1991) Ion exchange membranes and separation
References processes with chemical reactions. J Appl Electrochem
21:283–294
Strathmann H (2004) In: Ion exchange membrane separa-
Kliber S, Wisnieskwi JA (2011) Removal of bromate and tion processes. Membrane technologies series.
associated anions from water by Donnan dialysis with Elsevier, Amsterdam
E
References
Affinity Separation
and Crystallization of Fc 450
Fragments, Fig. 1 FPLC
chromatogram of IgG after Fab
digestion with papain 350
Absorbance (m/U)
(Ert€urk et al. 2011)
250
Fc
150
50
–50
0 5 10 15 20 25
Time (min)
References Ert€
urk G, Bereli N, Uzun L, Tumer MA (2011) Affinity
separation and characterization of IgG subfragments
Aslıy€uce S, Uzun L, Say R, Denizli A (2013) Immuno- by fast protein liquid chromatography with HiTrap_r
globulin G recognition with Fab fragments imprinted Protein A column. Hacet J Biol Chem 39:133–138
monolithic cryogels: evaluation of the effects of metal- Haupt K, Mosbach K (1998) Plastic antibodies:
ion assisted-coordination of template molecule. React developments and applications. Tibtech November
Funct Polym 73:813–820 16, 468–475.
Beale D (1987) Molecular fragmentations. Some applica- Holt LJ, Herring C, Jespers LS, Woolven BP, Tomlinson
tions in immunology. Dev Comp Immunol IA (2003) Domain antibodies: proteins for therapy.
11:287–296 Trends Biotechnol 21:484–490
Bereli N, Ert€urk G, Tumer MA, Say R, Denizli A (2013) Luo Q, Mao X, Kong L, Huang X, Zou H (2002) High-
Oriented immobilized anti-hIgG via Fc fragment- performance affinity chromatography for characteriza-
imprinted PHEMA cryogel for IgG purification. tion of human immunoglobulin G digestion with
Biomed Chromatogr 27:599–607 papain. J Chromatogr B 776:139–147
Cortese R (1995) Identification of biologically active pep-
tides using random libraries displayed on phage. Curr
Opin Biotechnol 6:73–80
F
Flavanoids Separation,
Fig. 1 Examples of some
flavonoids. (a)
quercetin – flavonol, (b)
cyanidin – anthocyanin, (c)
hesperidin – flavanone
Fossil Fuels Processing by Membrane Operations, Table 1 Overview of global stationary CO2 sources larger than
0.1 million tons (Mt) of CO2/year
Process Number of sources Emissions (Mt CO2/year)
Fossil fuels Power 4,492 10,539
Iron and steel industry 269 646
Cement production 1,175 932
Refineries 638 798
Petrochemical industry 470 379
Oil and gas processing N/A 50
Other sources 90 33
Biomass Bioethanol and bioenergy 303 91
Total 7,887 13,468
(IPCC special report on CCS, working group III)
create sufficient partial pressure difference over (Jordal et al. 2004). An advantage is also that
the membrane. The recommended membrane CO2 is captured at high pressure, and less energy
solution in this case will be to use a membrane will be needed for sequestration. The main chal-
with very high flux and selectivity which can be lenge for this membrane solution is the module
achieved with a facilitated transport membrane construction at this high temperature and also
having a fixed or mobile carrier to enhance the potential poisoning of the membrane.
transport (Kim et al. 2004), or to use an innova- Oxyfuel combustion: This solution is very ele-
tive two-stage process solution where air is being gant, using a membrane to separate out pure
used as sweep on the second stage and fed to the oxygen. The air separating membrane is, how-
burner (Merkel et al. 2010). In both cases, energy ever, still not fully developed. These membranes
demand is minimized by using only a fan on the are suitable for advanced power generation
feed side and pulling vacuum on the permeate requiring pure oxygen for combustion or gasifi-
side. The membrane material will be cation and are based on zirconia and perovskite
polymeric. Impurities in the flue gas stream where oxygen is transported through the material
(SO2, NOx, particles) may be a challenge for as O2 . The materials are stable at very high
the membrane material. temperatures (>500 C) but again module design
Precombustion: When used in precombustion is very challenging at these high operating
the membrane will be an integrated solution with temperatures.
the gas turbine and CO2 may thus be removed at
higher pressure. After the shift reaction H2 and
CO2 will be in a mixture, with close to 40 mol%
Cross-References
CO2. The pressure will be in the range of
25–30 bar, and temperature around 300–350 C
▶ Oxyfuel by Jurgen Caro
unless there has been a sulfur removal unit up
▶ Oxygen Transport Ceramic Membranes:
front of the membrane. The high temperature,
Perovskite and Non-perovskite by Vesna
pressure, and concentration are very favorable
Middelkoop
for Palladium membranes which can achieve
extremely efficient separation of the two main
components, allowing hydrogen to permeate
Fossil Fuels Processing by Membrane Operations 3
Postcombustion N2
(PC) O2
Coal
Power & Heat CO2 Separation
Air
CO2
Precombustion
(IGCC)
Steam CO2
Air/O2
CO2
Coal Shift, Gas Cleanup H2 Power Compression
Gasification and
+ CO2 Separation & Heat
Dehydration
Air
Oxyfuel Combustion
Air N2
Air Separation
O2
Coal CO2
Power & Heat
2008). Here, typically membrane technology and while the MTBE and the n-C4 fraction are sepa-
amine scrubbing compete. The carbon dioxide rated in a distillation column. In the other pro-
content in the feed gas and the feed gas flow cess, the raw mixture is fed to a distillation
rate determine which separation technology column while the pervaporation module operates
should be applied. Interestingly, for high carbon at a side draw. This latter hybrid process out-
dioxide mole fractions and for high feed flow classes the conventional process, in which differ-
rates, the combination of membrane technology ent distillation columns are applied.
and amine absorption is the most efficient process
configuration.
The vapor recovery of gasoline vapors from References
storage tanks can be done by applying rubbery
gas permeation membranes and condensation Baker RW, Lokhandwala K (2008) Natural gas processing
equipment (Rautenbach et al. 1996). Here, the with membranes: an overview. Ind Eng Chem Res
47:2109–2121
bulk separation is done by condensation and the
Hömmerich U, Rautenbach R (1998) Design and optimi-
gas is subsequently polished in a gas permeation zation of combined pervaporation/distillation pro-
unit. Both, the recovery of gasoline and environ- cesses for the production of MTBE. J Membr Sci
mental standards for the exhaust gas, have to be 146:53–64
Melin T, Rautenbach R (2007) Membranverfahren-
considered in the design of such a plant.
Grundlagen der Modul-und Anlagenauslegung.
In the MTBE (methyl tert-butyl ether) produc- Springer, Berlin
tion methanol, MTBE and n-C4 have to be sepa- Rautenbach R, Knauf R, Struck A, Vier J (1996) Simula-
rated. The separation is complex due to the tion and design of membrane plants with Aspen Plus.
Chem Eng Technol 19:391–397
formation of azeotropes (Hömmerich and
Skiborowski M, Mhamdi A, Kraemer K, Marquardt
Rautenbach 1998). Two hybrid processes can be W (2012) Model-based structural optimization of sea-
applied: one in which the mixture is fed to a water desalination plants. Desalination 292:30–44
pervaporation module to remove the methanol
H
r
ba
MSR
increase in the number of moles. This reaction is
10
ar
thermodynamically limited and the selective
5b
ar
X CH (-)
1b
4
r
0.5 The development of ceramic and supported
ba
1
r metallic (e.g., palladium-based) membranes has
ba
5
r promoted the investigation of the membrane
I =10 1 0b
a
reformer for a high-temperature reaction. Dense
palladium–based membranes are characterized by
I = 0 (TR) infinite hydrogen selectivity which prevents the
0 permeation of other species through the metallic
200 400 600 structure of the palladium.
T (°C) The operating conditions (temperature, pres-
sure, flow rate, composition, etc.) have to be
Hydrogen Production by Membrane Reactors, completely rethought since the permeation signif-
Fig. 1 Equilibrium conversion of Methane as function of icantly affects the reforming process/reaction.
the temperature for both membrane and traditional reactors
Methane steam reforming can be operated at a
at differrent feed pressure values for H2O/CH4 initial ratio
of 3. For membrane reactor, the permeate pressure is 1 bar significantly lower temperature (400–500 C)
and the sweep contained in the permeate chamber is the since the reaction pressure favors hydrogen per-
times higher than the methane amount in the reaction meation. The higher the feed pressure, the higher
volume. (Marigliano et al. 2001, 2003)
the hydrogen removal and as a consequence the
methane conversion (see Fig. 1).
Steam reforming is the reaction between The stream produced by reformers and/or coal
hydrocarbons and water vapor. The steam gasification plants contains around 50 % molar of
reforming of methane is the best known of this hydrogen (on a dry basis) and between 40 % and
reaction class owing to its industrial importance in 45 % molar of CO, which is usually reduced in an
hydrogen and syngas production (Scholz 1993). upgrading stage producing more hydrogen at the
A methane steam reformer is industrially operated same time, by WGS reaction. The upgrading stage
at 700–1100 C and 20–30 bar over Ni-based of traditional processes consists of a multistage
catalyst; the main species and reactions involved CO-shift process based on two catalytic reactors:
are (Xu and Froment 1989a, b) the first operates at high temperatures (about
350–400 C) to take advantage of the faster reac-
CH4 þ H2 O ¼ CO þ 3 H2 DH298 tion rates, whereas the other operates at low tem-
¼ 206 kJ mol1 peratures (around 220–300 C) to refine the
carbon monoxide conversion, thus allowing a
lower final CO concentration (less than 1 %
CO þ H2 O ¼ CO2 þ H2 DH298
molar) (Raggio et al. 2005).
¼ 41 kJ mol1
CO þ H2 O ¼ CO2 þ H2
CH4 þ 2H2 O ¼ CO2 þ 4H2 DH298
DH0 298 ¼ 41 kJ mol1
1
¼ 165 kJ mol
The H2-rich stream coming out from the last reac-
tor is fed to a pressure swing adsorption (PSA)
Hydrogen Production by Membrane Reactors 3
unit for H2 separation from other gases. Most reduce the cost related to Pd (PachecoTanaka
often another reaction unit is added for oxidizing et al. 2005; Zhang et al. 2009).
CO to CO2, to meet the purity targets for fuel cell
uses (CO concentration lower than 10–20 ppm).
Additionally, the reduction of the percentage of References
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I
Intermittent Feed Diafiltration may be applied to achieve the required final vol-
ume. A mathematical analysis of intermittent
Zoltán Kovács feed diafiltration can be found in (Wang et al.
Department of Food Engineering, Institue of 2007).
Bioengineering and Process Engineering, Szent Note that the processing scheme of intermit-
Istvan University, Budapest, Hungary tent feed diafiltration is basically a slight modifi-
cation of the method employed by sequential
dilution diafiltration (also called discontinuous
Intermittent feed diafiltration is characterized diafiltration by sequential dilution).
as a batch diafiltration process in which the
processed liquor is first concentrated to a
predetermined volume and then diluted back to References
its original volume with a diluent. This
concentration-dilution sequence may be repeated Wang L, Yang G, Xing W, Xu N (2007) Mathematic
model of the yield for diafiltration processes. Sep
several times to obtain the desired degree of
Purif Technol 59:206–213. doi:10.1016/j.
separation of macrosolutes from microsolutes. seppur.2007.06.007
As a final step, an additional post-concentration
performed through the infusion of purified islets placed into the vessels, where adequate kinetic
into the portal vein of the liver, and 50 % of the properties allowed the insulin release straight into
receivers are able to regain the pancreatic func- the blood stream. Micro devices constituted by
tionality and recover from the systemic compli- single cluster of beta cells incorporate into semi-
cations in 1 year. However, the number of permeable polymeric membranes, and nano-
available and compatible donors is quite limited, devices are nowadays under investigation in a
and the lifetime immunosuppression therapy few animal models. They differ generally on the
exposes the patient to infections, diseases, and processing methods used for the encapsulation of
harmful side effects. Thus, new techniques the islets and both allow to increase the insulin
labeled as tissue engineering approaches have release rate and the oxygen exchange into the
been developed to overcome these disadvantages islets. The micro systems are processed in a
and foresee the use of polymeric membrane sys- spherical system of alginate hydrogels coated
tems to produce engineered device containing with poly-ornithine and polylysine or by cross-
islets of insulin-producing cells, to control the linking a thin hydrogel sheet onto an islet cluster
release of the cell products from the islets, their by the conformal coating methods, whereas the
sustainment, and their protection from the immu- nano-devices (1–100 mm) consist of islets encap-
noreactive species in the site of implantation. sulated by alternating charged polylysine,
Coordinated by local drug delivery systems, polyglutamic acid, and PEG-biotin polymers
consisting in boles of low-dose anti-rejection over the cell aggregate surface through the
drugs able to minimize the immune response as layer-by-layer method. The decreased thickness
well as any inflammatory effects at the site of of the capsules obtained by covering the islets
implantation, the encapsulation technique is the with a single sheet of molecules increases and
most promising method. The islets are wrapped improves the insulin release kinetics after
in a tight coating made of biocompatible poly- implantation and resulting as well in higher dif-
mers acting as a perm-selectivity membrane that fusion of nutrients in the core of the cell clusters.
serves to mimic the heterogeneous and safe envi- Independently on the size of the device, three
ronment where oxygen and nutrient perfusion is different encapsulated replacement strategies
provided continuously and appropriate space and are available for the implantation: All-In/
ECM-like physical and mechanical support, Biodegrade-Out replacement, made of biode-
essential for the correct insulin production and gradable components easily absorbed by the
secretion and the islets’ survival, are provided. body; All-In/All-Out replacement, designed to
Different classes of encapsulating devices are not react with the host tissues as the cytother-
available and classified depending on their size apeutics devices, the islet sheet medical devices,
in macro-, micro-, and nano-devices. Classified and the beta-O2 device; and Flush/Reload
as extravascular diffusion devices when placed replacement used for the macrodevices designed
subcutaneously or in the peritoneal cavity and in order to grow into the host to provide a vascu-
intravascular diffusion system, three lar interface (David and Marchetti 2014). New
macrodevices have been approved for the clinical cell sources. To overcome the shortage of donor
trials: the TheraCyte system, made up of two organs and the side effect linked to the autoim-
composite Teflon-based membranes in between mune destruction of the patient islets as for dia-
the islets are placed; the Islet Sheet device, con- betes type I, alternative sources of beta cells have
stituted by supported alginate sheets containing been researched. The adult stem cells or progen-
the pancreatic islets; and the Beta O2 device able itor cells appear to be the most promising.
to increase the oxygen exchange in the implanta- Through reprogramming cell strategy
tion site being made of oxygen-generating bio- (transdifferentiation), pancreatic precursor cells
material able to deliver locally the oxygen to the are reprogrammed in insulin-producing cells.
cells. Additional macrodevices consist of tubular Moreover, the own patients pancreas exocrine
porous membranes filled with islets generally cells and the skin cells that can undergo to the
Langerhans Islet 3
reprogrammation technique representing a prom- settled in preclinical trials and only one lead
ising new source for the beta cells supply, being research project has been presented in the last
not needed the immunosuppression therapy after years on baboons, 95 % of the patients who
the implant (Domı̀nguez-Bendala et al. 2013). received the capsule implantation resulted in con-
Therefore, another potential source of beta cells siderable improvements of the glucose metabo-
may be the xenotransplantation with pig pancreas lism with the reverse of the main diabetes side
cells. Interestingly, human and porcine insulin effects at 1 year and more than 80 % at 5 years
differ only for one amino acid, and insulin after implants opening new hopes in the further
extracted from porcine pancreas has been used improvement of new strategies for the diabetes
for the treatment of patients with diabetes before treatment in the nearest future.
the development of recombinant human insulin
technology. However, several problems need to
be overcome for porcine islet transplantation to
References
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L
Liquid Chromatography – Organic Carbon Detection (LC-OCD), Table 1 Characteristics of different constituents
of NOM identifiable by LC-OCD (www.doc-labor.de; Huber et al. 2011; Batsch et al. 2005)
NOM fraction Typical size (Da) Typical composition
Biopolymers >20,000 Polysaccharides, proteins, amino sugars, polypeptides, TEPs, EPS
Aquatic humics 1000 Humic and fulvic acids
Building blocks 300–450 Weathering and oxidation products of humics
LMW neutrals <350 Mono-oligosaccharides, alcohols, aldehydes, ketones, amino acids
LMW acids <350 All monoprotic organic acids
12
OCD: organic carbon detection
Building Blocks UVD: UV detection at l=254 nm
Acids and OND: organic nitrogen detection
Humics LMW Humics
10
8
rel. Signal Response
Biopolymers
LMW-Neutrals
6
OCD
4
Inorganic
Colloids
2
UVD
Nitrate
OND
0
20 30 40 50 60 70 80
Retention Time in Minutes
Liquid Chromatography – Organic Carbon Detection (LC-OCD), Fig. 1 Typical LC-OCD chromatogram of NOM
in surface water (DOC-Labor 2006)
times. In principle, the analysis technique is as DOC-Labor, Karlsruhe) to calculate organic car-
follows: (1) injection of buffered particle-free bon concentrations of biopolymers, humic sub-
water sample to a chromatographic column to stances, building blocks, low molecular weight
separate fractions of NOM, (2) nondestructive (LMW) acids, and neutrals fractions of NOM
UV detection at 254 nm wavelength, (3) organic based on area integration of the fractional peaks.
carbon detection based on high-sensitivity TOC The lower limit of detection of this technique was
analysis, and (4) simultaneous detection of reported to be in the low-ppb range for individual
organic nitrogen in bypassed samples after the fractions (Huber and Frimmel 1991). The typical
UV detector (see detailed specifications by size ranges and chromatograms of the different
Huber et al. 2011). The chromatogram data gen- NOM fractions detectable by LC-OCD are shown
erated by the three detectors are processed using a in Table 1 and Fig. 1, respectively.
customized software program (ChromCALC,
Liquid Chromatography – Organic Carbon Detection (LC-OCD) 3
porous membranes as air distributor is usu- science and engineering, vol 3. Elsevier, Amsterdam,
ally not combined with an oxygen pp 1–108
Dittmeyer R, Caro J (2008) Catalytic membrane reactors.
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Membrane Swelling,
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Solvent Polymer
x
Isotropically swollen system Original system Anisotropically swollen system
Membrane Swelling, Fig. 2 Isotropic and anisotropic expansion of 3D polymeric networks along three axes
(x, y, and z)
Oxygen-Enriched Air (OEA) than nitrogen and argon. This can be used
Production by Membrane Reactors to produce nitrogen as retentate on the high-
pressure side and an oxygen-enriched air on
Juergen Caro the low pressure permeate side. If the target
Institut f€
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Elektrochemie der Leibniz, Universität side, the oxygen-enriched permeate is called
Hannover, Hannover, Germany “waste gas.” It is estimated that for an oxy-
gen purity of 30 % and a capacity
<15,000 Nm3/h, the investment, operating,
Air with increased oxygen content has different and maintaining costs are two thirds to three
applications ranging from sub-aqua diving and fourths of cryogenic and PSA technology.
medical treatments to processes like waste burn- Often, the spiral wound geometry is pre-
ing, FCC catalyst regeneration, preparation of ferred and the pressure difference across the
synthesis gas for ammonia production, Claus membrane is maintained by a vacuum pump
plants, and high-temperature furnaces and kilns. on the permeate or a compressor/van on the
The reduction of the inert nitrogen as a ballast is feed side (Puri 2011).
of advantage in several processes. When increas- (ii) Recently, perovskite-type high-temperature
ing the oxygen content of air from 21 % to 30 %, ceramic membranes have been proposed for
there is 40 % less nitrogen per oxygen unit, and OEA production (Liang and Caro 2011).
membranes of modest selectivity (3–5) and Here the fee is slightly pressurized air of
higher oxygen flux are preferred. about 2 bar (O2 partial pressure 0.4 bar).
OEA can be produced by mixing air with pure As sweep gas, air of typically 1 bar (O2
oxygen from cryogenic air distillation after Linde partial pressure 0.2 bar) is applied.
or by pressure swing adsorption. Membranes can Because of the difference in oxygen partial
produce OEA in two different ways: pressure, there is an oxygen transport from
the feed to the permeate side until the O2
(i) There exists a variety of commercial organic partial pressure on the permeate side also
polymer membranes with a preferential oxy- reaches 0.4 bar, which is air with 40 % O2
gen transport. Since oxygen has a slightly at 1 bar (Wang et al. 2005; Hamel
smaller molecule size and it undergoes less et al. 2006).
interaction than the quadrupolar nitrogen,
oxygen (plus carbon dioxide + water vapor)
permeates faster through the polymer film
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_728-4
2 Oxygen-Enriched Air (OEA) Production by Membrane Reactors
W/O). Three basic methods of viscosity measure- emulsification and microchannel emulsification
ment are capillary tube methods, falling ball have received much attention. For membrane
methods, and rotational methods. It is important emulsification, two methods of operation are
to determinate the type of emulsion. Unfortu- used: cross-flow membrane emulsification and
nately, an unequivocal determination may not premix membrane emulsification. In cross-flow
always be possible, and deductive reasoning membrane emulsification, the emulsion is formed
based on the data obtained from several methods by pushing the to-be-dispersed phase through a
may be required. Desired information may be membrane into the cross-flowing continuous
obtained from five classic methods: dye solubility phase. Ideally, droplet size can be controlled pri-
method, phase dilution method, conductivity marily by the choice of the membrane, the cross-
method, fluorescence method, and wetting of fil- flow velocity, and the transmembrane pressure.
ter paper. In studies of the stability of emulsions, Contrary to cross-flow emulsification, premix
the change in the particle-size distribution with emulsification can be used to produce emulsions
time is often an important datum. There are, in with high dispersed phase fraction, albeit that the
general, four distinct methods by which this size of the droplets is not as monodisperse as for
information may be obtained, i.e., by microscopic cross-flow emulsification (Nazir et al. 2010).
observation, by various sedimentation tech-
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membrane materials is based on a reversible spe- fonic acid groups without decomposing the skel-
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certain metal ions, such as ionic silver, dissolved
in the polymer matrix, which results in facilitated
Zeolite Membranes
olefin transport of the ion-olefin coupling through
Several studies concerning the separation of pro-
the membrane. Though offering good olefin/par-
pylene from propane base on faujasite (FAU zeo-
affin separation performances at lab scale, those
lite) membranes (Nikolakis et al. 2001) or
materials were subject to a loss of solvent by
titanosilicate ETS (Tiscornia et al. 2008) have
evaporation, which resulted in dramatic fall of
been published recently. The olefin/paraffin
olefin/paraffin separation performances.
selectivity of all those materials was comparable
In the latter years, new attention was paid at
to glassy polymers and always below 10.
promising ionic silver-impregnated solid-state
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flowing liquid membrane using silver-nitrate as a car- Yoshino M, Nakamura S, Kita H, Okamoto K, Tanihara N,
rier. J Membr Sci 45:115–136 Kusuki Y (2003) Olefin paraffin separation perfor-
Tiscornia I, Irusta S, Tellez C, Coronas J, Santamaria mance of carbonized membranes derived from an
J (2008) Separation of propylene/propane mixtures asymmetric hollow fiber membrane of 6FDA/BPDA-
by titanosilicate ETS-10 membranes prepared in DDBT copolyimide. J Membr Sci 215:169–183
O
Oriented Immobilized Anti-hIgG via the Fc region. These are more efficient techniques
Fc Fragment-Imprinted Cryogels resulting to the oriented immobilization of anti-
bodies and thus giving rise to highly accessible
Nilay Bereli, Handan Yavuz and Adil Denizli antigen-binding sites on the antibody and
Department of Chemistry, Biochemistry increase in the activity of the immobilized anti-
Division, Hacettepe University, Ankara, Turkey body molecule (Hober et al. 2007). However,
despite their general use as effective ligands for
the oriented immobilization of antibodies, they
Antibodies exhibit unique binding properties, have some drawbacks in their economical value,
high affinity and specificity towards a wide reusability, and concerns over the clearance of
range of natural and synthetic targets. Because leached ligand (Low et al. 2007). Small antibody
of these properties, antibodies are utilized in fragments can be evaluated as simple, inexpen-
many applications including therapeutics, diag- sive, more stable, general purpose ligands to be
nostics, research in biology and biotechnology, an alternative to protein A or G. In combination
immunoaffinity chromatography, etc. (Huse with an oriented immobilization method, these
et al. 2002). For medical applications, immuno- small antibody fragments allow an increased
globulins (IgGs) have been purified using a com- degree of immobilization of well-oriented and
bination of various methods like precipitation and active antibodies per solid support surface area,
chromatographic techniques including hydropho- hence facilitating higher antibody–antigen com-
bic interaction, histidine affinity, ion exchange, plex formation (Bonroy et al. 2006). Fc fragment-
dye affinity, and metal-chelate affinity imprinted poly(hydroxyethyl methacrylate)
(Tishchenko et al. 2002; Yavuz and Denizli cryogel (MIP) can be used for the oriented immo-
2005; Denizli 2011). Antibody immobilization bilization of anti-hIgG for IgG purification from
is an important step in the preparation of chro- human plasma. Non-imprinted poly
matographic immunoaffinity column. The recog- (hydroxyethyl methacrylate) cryogel (NIP) can
nition part of the antibody has to be accessible to be also used for random immobilization of anti-
maintain the antibody’s functionality and to hIgG to compare the adsorption capacities of
detect the analyte molecule. Therefore, during oriented (MIP/anti-hIgG) and random (NIP/anti-
immobilization, the proper orientation of anti- hIgG) cryogel columns. IgG adsorption capacity
bodies on the surface of the solid support is cru- is found to be three times higher than the NIP/
cial (Batalla et al. 2008). There are some more anti-hIgG column (29.7 mg/g) for the MIP/anti-
specific techniques using immobilized protein hIgG column (86.9 mg/g) (Fig. 1). Higher IgG
A or G for the immobilization of antibodies by adsorption capacity was observed from human
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_732-1
2 Oriented Immobilized Anti-hIgG via Fc Fragment-Imprinted Cryogels
Oriented Immobilized
Anti-hIgG via Fc
Fragment-Imprinted
Cryogels, Fig. 1 IgG
adsorption amounts of
MIP/anti-hIgG (oriented)
and NIP/ anti-hIgG
(random) cryogel (Bereli
et al. 2013)
plasma (up to 106.4 mg/g) with the MIP/anti- Comparision of random oriented immobilisation of
hIgG cryogel column. The results obtained are antibody fragments on mixed self-assembled mono-
layers. J Immunol Methods 312:167–181
promising and show that Fc fragments of anti- Denizli A (2011) Purification of antibodies by affinity
bodies with an oriented immobilization method chromatography. Hacet J Biol Chem 39:1–18
can be considered as a potential candidate for IgG Hober S, Nord K, Linhult M (2007) Protein
purification human plasma (Bereli et al. 2013). A chromatography for antibody purification.
J Chromatogr B 848:40–47
Huse K, Böhme HJ, Scholz GH (2002) Purification of
antibodies by affinity chromatography. J Biochem
References Biophys Methods 51:217–231
Low D, O’Leary R, Pujar NS (2007) Future of antibody
Batalla P, Fuentes M, Mateo C, Grazu V, Fernandez- purification. J Chromatogr B 848:48–63
Lafuente R, Guisan JM (2008) Covalent immobiliza- Tishchenko G, Dybal J, Meszarosova K, Sedlakova Z,
tion of antibodies on finally inert support surfaces Bleha M (2002) Purification of the specific immuno-
through their surface regions having the highest den- globulin G1by immobilized metal ion affinity chroma-
sities in carboxyl groups. Biomacromolecules tography using nickel complexes of chelating porous
9:2230–2236 and nonporous polymeric sorbents based on poly
Bereli N, Ert€urk G, Tumer MA, Say R, Denizli A (2013) (methacrylic esters). Effect of polymer structure.
Oriented immobilized anti-hIgG via Fc fragment- J Chromatogr A 954:115–126
imprinted PHEMA cryogel for IgG purification. Yavuz H, Denizli A (2005) Immunoadsorption of choles-
Biomed Chromatogr 27:599–607 terol on protein A oriented beads. Macromol Biosci
Bonroy K, Frederix F, Reeksmans G, Dewolf E, Palma 5:39–48
RD, Borghs G, Declerck P, Goddeeris B (2006)
O
and estimation of model parameters using numerical polymers: parameter identification and nonlinear
techniques. J Membr Sci 236(1–2):1–16. doi:10.1016/ regression analysis. J Membr Sci 254(1–2):275–293.
j.memsci.2004.01.006, ISSN 0376-7388 doi:10.1016/j.memsci.2005.01.019, ISSN 0376-7388
Madyastha VK, Prasad V (2011) Joint state and parameter Selby JC, Shannon MA (2009) Inflation of a circular
estimation for a membrane bioreactor system. Asia elastomeric membrane into a horizontally semi-
Pac J Chem Eng 6(3):406–422. doi:10.1002/apj.578, infinite liquid reservoir of finite vertical depth: estima-
ISSN 1932-2143 tion of material parameters from volume–pressure
Scheichl R, Klopffer MH, Benjelloun-Dabaghi Z, data. Int J Eng Sci 47(5–6):718–734. doi:10.1016/j.
Flaconneche B (2005) Permeation of gases in ijengsci.2009.01.007, ISSN 0020-7225
P
Polyether Block Amide (PEBAX) at low temperatures, the value of which lies
between 30 C and 20 C mostly depending
Anja Car on its molecular weight of the sequences
Department of Chemistry, University of Basel, (Bailey and Koleske 1976). The glass-transition
Basel, Switzerland temperature (Tg) is about 50 C due to the
flexible segment (Patel and Spontak 2004).
Through a proper combination of the polyamide
®
Polyether block amide is a multiblock copoly- and the polyether blocks, a wide range of Pebax
mer with two types of segments, rigid polyamide grades with a variety of end-use characteristics
(PA) and flexible polyether known under the can be designed (Pebax ® Technical Data Sheets).
trade name Pebax ® (http://www.pebax.com/ In general, these polymers possess a broad range
sites/pebax/en/home.page). It is obtained by of flexibility without the use of additives while
polycondensation reaction (Fakirov 2005) of a maintaining high strength and toughness.
carboxylic acid polyamide (PA6, P11, P12) with Because of the thermoplastic qualities, it can be
an alcohol-terminated polyether either polytetra- easily processed, extruded, and shaped at ele-
methylene glycol (PTMG) or polyethylene glycol vated temperatures, and upon cooling, its elastic-
(PEG) with general chemical structure (Fig. 1): ity will allow it to return to its original length or
Pebax ® consists of a linear chain of polyamide shape after being stretched, compressed, or
and polyether segment (block) in an orderly pat- deformed. Depending on the nature and the rela-
tern and belongs to the group of thermoplastic tive content of both segments, certain grades of
elastomers (Holden et al. 1996). The combination Pebax ® copolymers have great film-forming abil-
of the rigid PA segment and the flexible polyether ity; thus, they attracted greater attention as a
segment yields a block copolymer that exhibits a promising membrane material (Blume
microphase-separated morphology (Bates 1991) et al. 1990). The material offers strong resistance
due to the polarity differences between them: a to a range of chemicals, and it is not affected by
crystalline PA and an amorphous polyether exposure to saline or sulfuric acid (Carson
phase. The crystalline phase allows the copoly- et al. 2010). It can be sterilized by a variety of
mer to behave as a thermoplastic and the amor- methods including gamma radiation and steam
phous phase imparts elastomer characteristics. autoclave. Pebax ® is considered as a high per-
The PA block melts in the range 130–200 C former among its thermoplastic elastomer peers
(Rulkens et al. 2012); the exact value depends because it is lightweight and because it offers a
on average molecular weight and content of the wider range of flexibility and hardness, a higher
PA in the copolymer. Polyether block crystallizes energy return, a greater resistance to fatigue, and
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_736-2
2 Polyether Block Amide (PEBAX)
better dimensional stability under physical and Fakirov S (2005) Handbook of condensation thermoplas-
thermal stress (McKeen et al. 2010). tic elastomers. Wiley-VCH Verlag GmbH & Co,
Weinheim
Holden G, Legge NR, Quirk RP, Schroeder HE
(1996) Thermoplastic elastomers. Hanser Publishers,
Munich
References McKeen LW (2010) Tribological properties of plastic and
elastomers, 2nd edn. Elsevier
Bailey JFE, Koleske JV (1976) Poly(ethylene oxide). Patel NP, Spontak RJ (2004) Mesoblends of polyether
Academic, New York block copolymers with Poly(ethylene glycol). Macro-
Bates FS (1991) Science polymer-polymer phase behav- molecules 37:1394–1402
ior. 251:898–905 Pebax ® Technical Data Sheets. http://www.matweb.com/
Blume I, Pinnau I (1990) Composite membrane, method search/GetMatlsByTradename.aspx?navletter=p&
of preparation and use. US Patent 4,963,165 tn=Pebax%C2%AE
Carson C, Sik R (2010) Laser machining polyether block Rulkens R (2012) Chemistry and technology of polyam-
amide tubing. Eur Med Device Technol ides. Polym Sci Compr Ref 5:431–467
P
based innovative approach was applied with the pH of the water (3.5, 7.0 and 10.0) and to the
purpose to develop composite TiO2 catalyst dose applied (100–600 gTiO2/m3). The
photocatalytic nanofiltration (NF) membranes. results indicated the efficiency of the
The method involved pyrolytic decomposition photocatalytic process for fulvic acid removal
of titanium tetraisopropoxide (TTIP) vapor and from water and the usefulness of the ultrafiltra-
formation of TiO2 nanoparticles through homo- tion membrane in the recovery of the catalyst
geneous gas-phase reactions and aggregation of used. The values of the reaction rate constant
the produced intermediate species. The grown and the halftime of fulvic acid degradation were
nanoparticles are diffused and deposited on the determined using a kinetic model based on a first-
surface of gamma-alumina NF membrane tubes. order reaction. Relations between rate constant,
The CVD reactor allowed for online monitoring pH, and photocatalyst concentration in the reac-
of the carrier gas permeability during the treat- tion environment were found.
ment, providing a first insight on the pore effi-
ciency and thickness of the formed photocatalytic
layers. In addition the thin TiO2 deposits were References
developed on both membrane sides without
sacrificing the high yield rates. Important inno- Azrague J, Puech-Costes E, Aimar P, Maurette MT,
Benoit-Marquie FB (2005) Membrane photoreactor
vation was also introduced in what concerns the
(MPR) for the mineralisation of organic pollutants
photocatalytic performance evaluation. from turbid effluents. J Membr Sci 258:71–77
Fulvic acids were removed from model solu- Molinari R, Argurio P, Poerio T, Bonaddio F (2007) Photo
tions by catalysis, photolysis, and photocatalysis, assisted Fenton in a batch and a membrane reactor for
degradation of drugs in water. Sep Sci Technol
as well as in the integrated process of
42:1597–1611
photocatalysis and ultrafiltration (Rajca et al. Rajca M, Bodzek M, Cichy J (2011) Kinetics of fulvic acid
2011). Experiments were carried out in the degradation in the integrated process photooxidation-
Heraeus reactor, where model water of an ultrafiltration. Ochrona Srodowiska 33:63–66
Romanos GE, Athanasekou CP, Katsaros FK,
approximately 10 g/m3 content of fulvic acids
Kanellopoulos NK, Dionysiou DD, Likodimos V,
was treated. TiO2 was used as a photocatalyst. Falaras P (2012) Double-side active TiO2-modified
The efficiency of fulvic acid oxidation, measured nanofiltration membranes in continuous flow
in terms of dissolved organic carbon content and photocatalytic reactors for effective water purification.
J Hazard Mater 211:304–316
UV absorbance (l = 254 nm), was related to the
P
membrane
anion
anode cb+ cathode
cm+
cation-selective
membrane
UF because the permeate flux is lower and the electrical potential difference (driving force)
mass transfer coefficients of salts are high. How- through an ion-selective membrane. Cations are
ever, an increase of salt concentration in the layer driven to cathode and anions to anode. For exam-
adjacent to the membrane results in their precip- ple, through a cation-selective membrane only
itation onto the membrane surface (scaling), cations can be transferred at the potential differ-
which contributes to a decrease of permeate flux ence. However, the transfer across the membrane
(Mulder 1991). is faster than in boundary layers on both sides of
Scaling is also a serious problem in the membrane. Thus, the concentration of cations
nanofiltration (NF). The CP in NF causes a will be lower at the membrane surface on the
reduction of a permeate flux mainly due to an anode side and higher at the membrane surface
increase of osmotic pressure of the retained on the cathode side (Fig. 2). Thus, CP appears on
salts. Moreover, similarly as in UF and MF, the both sides of the membrane. Moreover, a diffu-
accumulated organic molecules can form a gel sive flow occurs in the boundary layers (Mulder
layer (fouling or biofouling) (Schafer et al. 2005). 1991).
The concentration polarization also strongly The effect of CP on the membrane processes
limits the efficiency of electrodialysis (ED). The such as gas separation, pervaporation, and dialy-
transport of charged molecules is the result of an sis is low or very low (Table 1).
Polarization in Membrane Operations 3
Smith PJ, Vigneswaran S, Ngo HH, Ben-Aim R, Nguyen ultrafiltration process control. J Membr Sci
H (2005) Design of a generic control system for 130(1–2):123–140, ISSN 0376-7388
optimising back flush durations in a submerged mem- Yee KWK, Alexiadis A, Bao J, Wiley DE (2008) Effects
brane hybrid reactor. J Membr Sci 255(1–2):99–106. of multiple-stage membrane process designs on the
doi:10.1016/j.memsci.2005.01.026, ISSN 0376-7388 achievable performance of automatic control.
van Reis R, Goodrich EM, Yson CL, Frautschy LN, J Membr Sci 320(1–2):280–291. doi:10.1016/j.
Whiteley R, Zydney AL (1997) Constant Cwall memsci.2008.04.010, ISSN 0376-7388
P
Productivity and Footprint in Gas (Eq. 2). When the value of this ratio is higher than
Separation 1, membrane operations should be preferred,
whereas, for values lower than 1, traditional
Adele Brunetti units should be chosen.
National Research Council, Institute for
Membrane Technology (ITM-CNR), The Productivityi =Footprint
University of Calabria, Rende (CS), Italy Productivity
¼ (1)
Footprint occupied by the installation
The productivity to footprint compares the pro-
Productivity footprint ratio
ductivity of the separation system with respect to
the installation area occupied by the system itself ðProductivityi =FootprintÞMembranes
¼
(Eq. 1) (Criscuoli and Drioli 2007). Considering ðProductivityi =FootprintÞTraditional technology
the same area occupied by the units, this metric (2)
identifies the most productive scheme to get a set
target. Future plants should be characterized by References
high productivities and low sizes; therefore, a
high value of this index is highly desired. Criscuoli A, Drioli E (2007) New metrics for evaluating
To compare two different technologies that the performance of membrane operations in the logic
of process intensification. Ind Eng Chem Res
can be used for the same separation, the ratio
46:2268–2271
between the values of productivity/footprint
ratio obtained for each of them can be defined
Reliability in Gas Separation induce unscheduled shutdowns. The new PSA are
designed with alternate modes of operation, in
Adele Brunetti which 100 % of design capacity can be achieved
National Research Council, Institute for while bypassing any failed valve or instrument,
Membrane Technology (ITM-CNR), The with only a slight loss of recovery. Failures are
University of Calabria, Rende (CS), Italy automatically detected and bypassed by the
microprocessor-based control system. However,
stronger and periodic control cycles are required.
The reliability takes into account the on-stream The cryogenic process is considered by
factors which can cause unscheduled shutdowns. refiners to be less reliable than the PSA or mem-
It is an important project consideration, particu- brane processes; this is mainly due not to the
larly if the process is a primary source of make-up process itself but to the need for feed pretreat-
hydrogen to a hydroprocessor or other main- ments. Failure of the pretreatment system usually
stream refinery processes (Miller and Stöcker results in contaminants freezing in the cold box,
1989; Brunetti et al. 2010). leading to shutdown. In this case, a “thaw” is
Membrane systems are extremely reliable necessary prior to restart. The pretreatment sys-
with respect to the on-stream factor. The mem- tem itself is often more complex than the cryo-
brane separation process is continuous and has genic system.
few control components which can cause a shut-
down. Typically, the response to unscheduled
shutdowns is rapid. Absorption systems are mod- References
erately reliable. The large equipment associated
with the process for avoiding the formation of Brunetti A, Bernardo P, Drioli E, Barbieri G (2010) Mem-
brane engineering progresses and potentialities in gas
degradation and corrosion products and the pres-
separations. In: Yampolskii Y, Freeman B (eds) Mem-
ence of particles can cause unexpected brane gas separation. Wiley, New York, pp 281–312
shutdowns. Miller GQ, Stöcker J (1989) Selection of a hydrogen
PSA systems are also moderately reliable. The separation process NPRA Annual Meeting 19–21
Mar, San Francisco
numerous valves associated with the process can
Genotoxin Removal,
Fig. 1 Scheme of
genotoxin removal by OSN
with potential reverse
osmosis for solvent
recycling
2012), from post-reaction solutions. In the former UTC-20, and UTC-60 membranes was applied
case, the Suzuki post-reaction solution was for the removal of genotoxic atrazine – banned
subjected to OSN, and the palladium was retained as a total herbicide in Europe since 1991 – from
by the membrane, while the API was collected in different water matrices including distilled water,
the permeate. On the contrary, in the latter case, tap water, and river water (Zhang 2004).
the genotoxin was removed with the permeate,
while the API was retained. In both cases the
genotoxin levels were reduced further by using
References
commercially available adsorbents or tailor-
made molecularly imprinted polymers. Not only De Luca G, Donato L, Del Blanco SG, Tasselli F, Drioli
has the combination of molecular imprinting and E (2011) On the cause of controlling affinity to small
membrane technology provided an efficient molecules of imprinted polymeric membranes pre-
genotoxin removal process but their fusion as pared by noncovalent approach: a computational and
experimental investigation. J Phys Chem
well. Molecularly imprinted membranes (MIM) B 115:9345–9351
can also be used for API degenotoxification. Pink CJ, Wong H, Ferreira FC, Livingston AG
Potentially genotoxic 4,40 -methylenedianiline (2008) Organic solvent nanofiltration and adsorbents;
has been applied as a template for MIM adsor- a hybrid approach to achieve ultra low palladium con-
tamination of post coupling reaction products. Org
bents (De Luca 2011). Environmental and eco- Process Res Dev 12(4):589–595
nomic analysis proved the sustainability of API Székely GY, Bandarra J, Heggie W, Sellergren B, Ferreira
degenotoxification by membrane processes in FC (2011) Organic solvent nanofiltration: a platform
comparison with conventional API purification for removal of genotoxins from active pharmaceutical
ingredients. J Membr Sci 381(1–2):21–33
methodologies such as chromatography and Székely GY, Bandarra J, Heggie W, Sellergren B, Ferreira
recrystallization (Székely 2013). Besides phar- FC (2012) A hybrid approach to reach stringent low
maceutical purification, control of genotoxins is genotoxic impurity contents in active pharmaceutical
also an environmental concern. Nanofiltration ingredients: combining molecularly imprinted poly-
mers and organic solvent nanofiltration for removal
featuring DESAL 51 HL, DESAL 5 DL, of 1,3-diisopropylurea. Sep Purif Technol 86:79–87
Genotoxin Removal 3
Székely GY, Gil M, Sellergren B, Heggie W, Ferreira FC Zhang Y, Van der Bruggen B, Chena GX, Braeken L,
(2013) Environmental and economic analysis for Vandecasteele C (2004) Removal of pesticides by
selection and engineering sustainable API degenotox- nanofiltration: effect of the water matrix. Sep Purif
ification processes. Green Chem. doi:10.1039/ Technol 38:163–172
c2gc36239b
S
Seeding for Zeolite Membranes both the minimization or suppression of the crys-
tallization of undesired phases and limitation of
Anne Julbe and Martin Drobek support dissolution (support etching might alter
Institut Européen des Membranes, Université de both its mechanical integrity and zeolite compo-
Montpellier, Montpellier, France sition), while in some cases controlling the rate
and direction of crystal growth. However, since
the support is porous, uncontrolled infiltration of
The seeding process can be described as a method seeds in the pores might reduce membrane
in which a small piece of a single crystal/poly- permeance by creating longer effective diffusion
crystal (seed) is used to act as an active site paths through the zeolite material (Hedlund
(nuclei) for growing a larger crystal when et al. 2002). Controlled support seeding is there-
exposed to the effect of nutrients (liquids or gas) fore of great importance for growing uniform and
in a reaction system. The addition of seeds shifts good quality membranes, preferably with low
the equilibrium toward crystal formation and infiltration into the porous support (Fig. 1). Clas-
avoids the undesirable random nature of sponta- sical coating or seeding methods are dip coating,
neous nucleation. This procedure is typically slip casting, spin coating, rubbing, vacuum
applied for solutions during recrystallization pro- seeding, and spray coating. Specific methods for
cesses, thus eliminating the need for molecular attaching zeolite seeds onto porous supports
collision/interaction and decreasing significantly include either covalent linkage or electrostatic
the time required for nucleation. The seeding forces, using pH effects, cationic polymers, or
strategy is also largely applied for growing uni- silane coupling agents (Lai et al. 2004). Seeding
form zeolite membranes on porous supports, with either commercial or homemade seeds is
starting from a layer of closely packed seed crys- considered as one of the most attractive methods
tals which have been previously nucleated (Julbe for preparing a variety of zeolite (e.g., LTA, MFI,
2007). The decoupling of the nucleation step SOD, FAU, CHA, DDR) and zeolite-type (e.g.,
(at high supersaturation) from the crystal growth MCM, MOF) membranes. It confers improved
(at low supersaturation) makes the formation of a flexibility for controlling crystal growth and
zeolite membrane very rapid as compared to film microstructure with high reproducibility
direct growth without any seeds. As the concen- and scalability. In industry, the seeding process
tration needed for secondary growth is lower than is typically applied by Mitsui Engineering and
that for nucleation, further homogeneous nucle- Shipbuilding Co. Ltd. for the preparation of zeo-
ation is avoided and crystal growth occurs only lite membranes, including LTA (Morigami
on the existing seeds. Additional benefits include et al. 2001).
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_758-1
2 Seeding for Zeolite Membranes
References
Silica Gel for Membrane Preparation reaction is washed prior to the dehydration pro-
cess to produce colorless silica gel. Typically,
1,2 1,2
A. F. Ismail , M. H. D. Othman and M. A. cobalt chloride or ammonium tetrachloro-
Rahman1,2 cobaltate is added to silica gel to give a visible
1
Advanced Membrane Technology Research indication of its moisture content (Greenwood
Centre (AMTEC), Universiti Teknologi and Earnshaw 1997).
Malaysia, Skudai, Johor, Malaysia However, for membrane fabrication process,
2
Faculty of Chemical and Energy Engineering, silica gel can be synthesized using polyconden-
Universiti Teknologi Malaysia, Skudai, Johor, sation of hydrolyzed tetraethoxysilane (TEOS)
Malaysia under acidic conditions through a sol-gel
approach (Lavorgna et al. 2007; Mishra
et al. 2012). This method is more favorable
Silica Gel for Membrane Preparation because high-purity silicate glasses can be
obtained. Similar to other ceramic material, silica
Silica gel is composed of silicon oxide gel has hydroxyl group on its outer surface which
manufactured widely for moisture removal. It is enables anchoring process to be carried out effec-
typically in solid form and possesses high ability tively. This process is also known as functiona-
in water absorption. The used silica gel can be lization which is a crucial step in the fabrication
regenerated by heat treatment at temperature of membrane on the top of silica gel support
range of 100–120 C for several hours. In addi- which facilitates the intimidation between these
tion, it is also a stable material, nontoxic, and two layers.
easily available and inexpensive. Commercial Various organic chemicals are used to
silica gel typically has high surface area, large functionalize silica gel, and the method to obtain
total pore volume, and broad pore size distribu- chemical bridge between support and membrane
tion (Wang et al. 2012). These characteristics might be different among research group. How-
produce less resistance for gas/liquid to diffusion ever, there is a general consensus in the way of
into it and thus make this material potentially to functionalizing silica gel such as removal of
be used as a membrane material. moisture prior to functionalization process, stir-
Silica gel can be prepared via a chemical reac- ring and mixing process between precursor of
tion between sodium silicate with an acidic solu- chemical bridge and silica gel, and washing and
tion at constant pH (Greenwood and Earnshaw drying cycle using alcohol (Lavorgna et al. 2007).
1997). To produce silica gel for commercial uses, These preparation steps are rather simple without
a gelatinous precipitate obtained from the
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_760-2
2 Silica Gel for Membrane Preparation
the necessity of using complex methods and technique is rather scarce compared to ex situ
advance equipments. approach. Furthermore, the incorporation of
Silica gel has been recognized as a promising hydrophilic silica gel with a monomer obscures
additive material in polymeric membrane for fuel polymerization process causing a reduction in
cell application (Mishra et al. 2012). Due to its membrane molecular weight and the formation
high hydrophilicity in nature, it has been used to of undesirable cross-linking (Mishra et al. 2012).
increase proton conductivity of commercial fuel Therefore, the fabrication of commercial com-
cell electrolyte membrane, i.e., Nafion ®, and posite membrane for fuel cell application such
retain humidity when the membrane is used at as Nafion ® uses an ex situ approach due to its
temperature higher than 80 C (Mishra simplicity and controllability.
et al. 2012). The incorporation of silica gel into
polymeric membrane can be accomplished by
adding the silica gel into polymeric solution
References
prior to the casting step and the drying process
(Mishra et al. 2012; Seo et al. 2006). This Greenwood NN, Earnshaw A (1997) Chemistry of the
approach enables the silica gel to be homoge- elements, 2nd edn. Butterworth–Heinemann, Boston
neously dispersed across polymer matrix. How- Lavorgna M, Mascia L, Mensitieri G, Gilbert M,
ever, the functionalization of silica gel should be Scherillo G, Palomba B (2007) Hybridization of
Nafion membranes by the infusion of functionalized
carried out prior to this process. On the other siloxane precursors. J Membr Sci 294:159–168
hand, the silica-based composite membrane can Mahreni A, Mohamad AB, Kadhum AAH, Daud WRW,
be fabricated by impregnation process (Mishra Iyuke SE (2009) Nafion®/silicon oxide/
et al. 2012; Mahreni et al. 2009). This can be phosphotungstic acid nanocomposite membrane with
enhanced proton conductivity. J Membr Sci 327:32–40
achieved by soaking the membrane by silica sol Mishra AK, Bose S, Kuila T, Kim NH, Lee JH (2012) -
followed by functionalization process. These two Silicate-based polymer-nanocomposite membranes
approaches can be categorized as ex situ for polymer electrolyte membrane fuel cells. Prog
approach in producing composite membrane for Polym Sci 37:842–869
Seo WJ, Sung YT, Han SJ, Kim YH, Ryu OH, Lee HS,
fuel cell application. There is another approach Kim WN (2006) Synthesis and properties of polyure-
known as in situ technique which involves the thane/clay nanocomposite by clay modified with poly-
incorporation of either nanoparticles or their pre- meric methane diisocyanate. J Appl Polym Sci
cursors into monomer solution with low viscosity 101:2879–2883
Wang K, Shang H, Li L, Yan X, Yan Z, Liu C, Zha
(Mishra et al. 2012). This approach ensures better Q (2012) Efficient CO2 capture on low-cost silica gel
dispersion and physical properties but very little modified by polyethyleneimine. J Nat Gas Chem
information can be obtained from open literature 21:319–323
(Mishra et al. 2012). It is perhaps that this
S
Stack of Single Cells in influence of the electrical field cations will move
Electrodialysis across cation-exchange membrane and anions
across anion-exchange membrane, resulting in for-
Tanja Vidakovic-Koch mation of dilute. On the other hand, in compart-
Max Planck Institute for Dynamics of Complex ments 2, 4, 6, and 8 the anion- and cation-exchange
Technical Systems, Magdeburg, Germany membranes do not allow movement of ions in the
direction of electrical field, resulting in formation of
concentrate in this compartments. As in other elec-
Electrodialysis is an electrochemical process (see trochemical processes, ionic current will be finally
“▶ Electrochemical Processing, Electrochemis- transformed into electrical current by means of
try”) for separating an aqueous feed solution into electrochemical reactions taking place at the cath-
a concentrate or brine and dilute or desalted water ode and anode. The main application of electrodi-
by means of an electrical field and ion-selective alysis is the desalination of brackish water. Other
membranes. Electrodialysis takes place in an elec- applications include waste water treatment, separa-
trodialysis stack. A schematic representation of tion of salts, and some food industry applications.
such a stack with anion- (A) and cation- Typical ion-exchange membranes are made of
(C) exchange membranes arranged in an alternating polystyrene, containing fixed sulfonate –SO3
series pattern is shown in Fig. 1. For practical groups (cation-exchange membrane) or quater-
application, number of membranes in an electrodi- nary ammonium groups such as –NH3+
alysis stack is much higher than shown in Fig. 1. (anionucexchange membranes) (2008). The
For example, such stacks might contain up to thickness of the membranes is 0.2–0.5 mm and
600 pairs of membranes (a unit cell is a combina- they are reinforced to provide better mechanical
tion of one cation-exchange membrane and one stability. The membranes are wetted with water,
anion-exchange membrane) (Seader and Henley but due to the size of pore networks inside of
2006). The size of a membrane is usually between membranes water transport across the membrane
0.4 and 1.5 m2 and they are separated from each is largely prohibited. The selectivity of mem-
other by spacer gaskets. A typical voltage drop branes for an anion or cation is better than 90 %.
across the unit cell is 0.5–1.5 V and typical current
densities are in the range of 5–50 mA cm2. The
movement of ions in the electrodialysis stack is Stack of Fuel Cells in Electrodialysis
dictated by the direction of an electrical field and
allowance of a membrane for an ion transport. For Alkaline fuel cell (AFC) is a fuel cell type which
example, in compartments 3, 5, and 7 (Fig. 1) under utilizes alkaline electrolyte, usually potassium
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_763-2
2 Stack of Single Cells in Electrodialysis
Stack of Single Cells in Electrodialysis, Fig. 1 Schematic representation of the electrodialysis process. C cation-
exchange membrane, A anion-exchange membrane
hydroxide. It consumes hydrogen and oxygen costs of this fuel cell. One of the major disadvan-
producing only water, heat, and electricity. tages of AFC is its low CO2 tolerance due to
Depending on a concentration of potassium formation of carbonates according to:
hydroxide AFC can operate at temperatures
between 60 C and 250 C. The fuel cell reactions CO2 þ 2OH ⇄CO2 2 þ H2 O
are as follows:
The carbonates have low solubility in strong alka-
Anode : H2 þ 2OH ⇄2H2 O þ 2e line environments forming crystals, capable of
blocking of electrolyte pathways. The low CO2
Cathode : 1⁄2 O2 þ 2e þ 2H2 O⇄2OH tolerance and the application of liquid electrolyte
are two main hurdles for the broader commercial-
Overall reaction : H2 þ 1⁄2 O2 ⇄H2 O ization of these systems. However, due to its high
efficiency and high power density AFC found
The main ionic charge carriers are OH ions applications in aerospace industry, e.g., they
which mitigate from the cathode to the anode. were employed on the Appollo missions as well
Water is formed at the anode side and has to be as on the space shuttle orbitals. For other exam-
removed from the system in order to prevent ples of developed AFC systems please see
KOH dilution. The AFC has improved cathode (Seader and Henley 2006; Electroseparations,
performance compared to acidic fuel cells due to electrodialysis 2008).
more favorable oxygen reduction reaction kinet- Hydrogen and oxygen gases in the AFC are
ics. For this reason, AFC can achieve higher separated by a membrane. Usually permeable
efficiency, i.e., higher voltage at comparable cur- membranes also called diaphragms have been
rent densities than other fuel cell types. It has used (G€ulzow 2012). A common diaphragm
very long operating life time, e.g., 15,000 h material up to 1980s was asbestos which due to
have been demonstrated (Cifrain and Kordesch health and environmental concerns is nowadays
2003). Furthermore, alkaline conditions allow abandoned. Alternative materials are different
application of nonprecious metal catalysts polymer materials like porous polyethylene
which could reduce significantly the material plates, nonwoven polypropylene and similar.
Stack of Single Cells in Electrodialysis 3
Use of Streaming Potential where le, Z, e, and eo are the solution conductiv-
Measurements for Characterization ity, viscosity, membrane dielectric constant, and
of Both Membrane/Electrolyte vacuum permeability, respectively.
Interface and Protein Fouling Effect To show the potentiality of electrokinetic
characterization, z-potential results for clean
Juana Benavente and BSA-fouled porous membranes, polymeric
Departamento de Fisica Aplicada I, Facultad de (GR, polysulfone <rp> 0.1 mm) and ceramic
Ciencias, Universidad de Malaga, Malaga, Spain (Z100S, ZrO2/Al2O3 on stain steel support <rp>
0.06 mm), by transmembrane measurements at
different pHs (Lara and Benavente 2009), and
Electrical nature of external and internal (pore- tangential measurements changing NaCl concen-
wall) membrane surfaces is significant for salt tration for a dense regenerated cellulose
rejection and transport characterization of RO (RC) membrane are presented (Cañas
and NF membranes or for filtration of solutions et al. 2001).
containing macromolecules and colloids. Elec- Figure 1a shows the comparison of z values as
trokinetic measurements are usually performed a function of solution pH for GR and Z100S
for characterization of membrane/electrolyte membranes. Polysulfone GR membrane exhibits
interfaces and to estimate changes associated to electronegative character, but it is electropositive
membrane fouling as a result of cake layer for- for ceramic Z100S; moreover, z-potentials for
mation (external fouling) or pore narrowing/ GR membrane slightly vary due to BSA fouling,
plugging (internal fouling). but they significantly change for the ceramic
Zeta potential (z) is the stationary electrical sample (from positive to negative), and practi-
potential at the shear plane between fixed and cally the same isoelectric point (z = 0) was
mobile ions in the double layer associated to obtained with both fouled membranes, which
solid-liquid charged interfaces. For weakly corresponds to the BSA isoelectric point. These
charged walls or wide channels/pores, z-potential results indicate the BSA coverage of pore walls
is obtained from streaming potential coefficient for both fouled samples.
(Døst/DP)I = 0 by Helmholtz-Smoluchowski equa- Figure 1b shows z-potential dependence on
tion (Hunter 1988): solution concentration for clean GR (through
pores) and dense RC (along surface) membranes,
zH S ¼ ðle Zeo eÞðDøst=DPÞI¼0 (1) indicating absorption of Cl-ions on internal
(GR) or external (RC) membrane surfaces.
Use of Streaming Potential Measurements for Char- GM membranes, clean (□) and BSA-fouled (■) Z100S
acterization of Both Membrane/Electrolyte Interface membranes; (b) concentration for clean GM (D) and RC
and Protein Fouling Effect, Fig. 1 z-potential as a (◊) membranes
function of (a) pH for clean (D) and BSA-fouled (~)
Q Feed Q Retentate
J Permeating
H2
Q Permeate QSweep
P Permeation
Me m b r a ne
SS- She l l
P Reaction Ca t a l y s t
Sweep Gas in a Membrane Reactor, Fig. 1 Scheme of a membrane reactor showing the four inlet/outlet stream,
including the sweep gas one
Sweep Gas Membrane Distillation membrane distillation (DCMD) (using the same
(SGMD) membrane).
Membranes used in SGMD are porous and
Maria Tomaszewska hydrophobic, similarly as in other MD configu-
Faculty of Chemical Technology and rations. Air, humid air, or dry nitrogen can be
Engineering, West Pomeranian University of used as a sweep gas.
Technology, Szczecin, Poland The permeate flux obtained in SGMD can be
in the range from ca. 1 to 25 kg/m2h, depending
on the membrane type, feed composition, and
SGMD is a membrane distillation operating conditions (Khayet and Matsuura
(MD) configuration in which a stripping gas is 2011). Nonvolatile species present in an aqueous
used as a carrier for the vapor transferred from a solution are theoretically completely retained in
warm aqueous feed through a porous hydropho- the feed, whereas volatile organic substances are
bic membrane. The nature of the membrane pre- partially transferred through a membrane. The
vents from penetration of liquid into the pores; separation performance in SGMD is determined
therefore, the liquid/vapor interface is formed at by a vapor/liquid equilibrium and depends
each pore entrance. The volatile molecules evap- mainly on a difference in volatility of compo-
orate through the membrane pores, and a cold nents in a mixture. However, the differences in
inert gas flowing along the other side of the mem- the diffusion rates of components through the gas
brane sweeps the permeate carrying it away from in the membrane pores should be also taken into
the module. The condensation of the vapor occurs account.
in an external condenser (Fig. 1). The driving For the case when SGMD is applied for treat-
force for the mass transfer in SGMD is the dif- ment of an aqueous solution containing nonvola-
ference in the partial pressure of volatile sub- tile compounds and the permeate is swept away
stances on both sides of the membrane. Since in using air or any other neutral gas, the equations
MD heat is transferred from the feed side through describing mass (J) and heat (Q) transfer in
the membrane, thus the sweep gas temperature DCMD can be adapted (Khayet and Matsuura
increases considerably along a module. However, 2011):
SGMD combines a relatively low conductive
heat loss through the membrane with a reduced J w ¼ Bw p0w, f aw, f pw, p
mass transfer resistance. Hence, the resulting
high mass transfer coefficients provide higher
permeate flux than that in direct contact
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_769-2
2 Sweep Gas Membrane Distillation (SGMD)
where B is membrane permeability (depends on where gj, f, xj, f, and fj, p are the activity coefficient,
membrane properties, e.g., thickness, porosity, the mole fraction in the liquid and gas phase, and
pore size) under the SGMD conditions, p is par- the fugacity coefficient of species j, respectively.
tial pressure, and aw is water activity. The super- The subscript j refers to all volatile compounds
script 0 denotes pure water, and subscripts w, f, including water.
and p refer to water, feed, and permeate, respec- Various models were applied for description
tively. The p0w,f and aw, f depend on the feed tem- of mass transfer in SGMD. Nevertheless, it was
perature, whereas Pw, p depends on the gas usually concluded that the transport occurred
temperature at the membrane surface, according to a combined Knudsen/ordinary
respectively. molecular diffusion mechanism.
When volatile compounds are present in a The heat transfer in SGMD (Q) is described by
feed, both the water vapor and the molecules of the following steps: heat transfer through the
volatile compounds are transferred across a mem- liquid boundary layer on a feed side (Qf), heat
brane. The separation factor of volatile com- transfer through a membrane (Qm) (through a
pound i (ai) can be calculated as: membrane material and gas-filling pores (Qc)
and with permeate stream Qv), and heat transfer
yi, p = 1 yi, p through the gas boundary layer (Qp) (Fig. 2).
ai ¼
xi, f = 1 xi, f Value of the permeate flux depends on the
SGMD operation conditions, e.g., the inlet tem-
where yi, p and xi, f are molar fractions of i species peratures and the flow rates of both fluids, i.e.,
in the gaseous permeate and liquid feed, liquid feed and sweep gas, and membrane char-
respectively. acteristics. The permeate flux is strongly depen-
In this case the total SGMD permeate flux (J) dent on a feed temperature because of
(if coupling effects are not considered) can be exponential growth of vapor pressure with tem-
written as: perature. On the contrary, an increase in the
sweep gas temperature leads to a decrease of the
vapor pressure gradient thus the resultant perme-
ate flux is lower. The major disadvantage of
SGMD configuration is a very high increase of
the gas temperature along a module.
Sweep Gas Membrane Distillation (SGMD) 3
The permeate flux is practically independent 2011). It was found that the permeate flux is
on the feed flow rate. The sweep gas flow rate is a higher for membranes with larger pore size.
very important parameter. An increase in the
permeate flux with sweeping gas flow rate is
caused by improved hydrodynamic conditions References
on the permeate side and a reduction of temper-
ature polarization effect. The thermal efficiency Charfi K, Khayet M, Safi MJ (2010) Numerical simulation
and experimental studies on heat and mass transfer
of SGMD is higher than in DCMD because the
using sweeping gas membrane distillation. Desalina-
heat loss by conduction through a membrane is tion 259:84–96
lower (Charfi et al. 2010; Khayet and Matsuura Khayet M, Matsuura T (2011) Membrane distillation.
Principles and applications. Elsevier, Amsterdam
S
Sweep Gas Membrane Distillation DCMD cannot be used due to the risk of the
(SGMD) Applications membrane wetting.
Laboratory-scale studies have demonstrated a
Maria Tomaszewska high potential of SGMD for removal of organic
Faculty of Chemical Technology and volatile compounds such as ethanol, isopropanol
Engineering, West Pomeranian University of (IPA), and acetone from wastewater (Khayet and
Technology, Szczecin, Poland Matsuura 2011). A novel SGMD-based micro-
separator has been studied for the separation of
a mixture of methanol and water. A bioreactor
SGMD is the least frequently used configuration combined with SGMD for ethanol production
of membrane distillation (MD) because the exter- was also proposed, in order to enhance the etha-
nal condenser is required to collect the permeate. nol productivity as well as to eliminate the fer-
Moreover, a little amount of the permeate is col- mentation inhibitors. The produced ethanol was
lected by a large volume of a sweep gas. There- free of bacteria, nutrients, and metabolites
fore, the system design is complicated and rather (He et al. 2012).
expensive. SGMD was applied for treatment of IPA aque-
Similarly as the other MD configurations, the ous solutions (below 10 wt.%). The influence of
SGMD can be used to treat the solutions feed temperature on the selectivity and permeate
containing nonvolatile compounds, such as flux is presented in Fig. 1. It was found that the
salts. The salt rejection is practically 100 % and selectivity decreased with an increase of sweep
high-purity water can be obtained. However, gas flow rate and with IPA concentration in a
since the volatile species permeate through the feed. Moreover, MgCl2 addition to the feed
membrane, a more profitable application of increased significantly IPA selectivity, with
SGMD is the removal of volatile organic sub- small reduction of the total permeate flux (Lee
stances (esters, ethers, chlorinated hydrocarbons, and Hong 2001).
aromatic compounds) or dissolved gases from High effectiveness (97 %) of SGMD during
aqueous solutions. Thus, SGMD can be applied the removal of ammonia from synthetic industrial
in chemical and petrochemical industries, in bio- wastewater (100 mg/l, pH 11) was also found
technology, or in environmental engineering, (Fig. 2). At higher feed temperature, the permeate
where the organic substances have to be recov- flux significantly increased, but the selectivity of
ered/removed from very diluted solutions. More- ammonia was reduced. For membranes with
over, SGMD can be applied in the cases where smaller thickness and larger pore size, the mass
transfer coefficient of ammonia was higher,
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_770-2
2 Sweep Gas Membrane Distillation (SGMD) Applications
a 2 b 26
0.03 0.03
0.05
24 0.05
0.07 0.07
0.095 22 0.095
20
Flux(kg/m2hr)
18
Selectivity
1 16
14
12
Feed flow rate 12.9 kg/h 10 Feed flow rate 12.9 kg/h
Gas velocity 8.7 m/s Gas velocity 8.7 m/s
8
Gas temperature 25 °C Gas temperature 25 °C
0 6
15 20 25 30 35 40 45 50 15 20 25 30 35 40 45 50
Feed temperature (°C) Feed temperature (°C)
Sweep Gas Membrane Distillation (SGMD) Applica- concentrations (Reprinted from Lee and Hong 2001,
tions, Fig. 1 (a) SGMD flux and (b) IPA selectivity as a copyright (2001), with permission from Elsevier)
function of feed temperature at various feed
a 120 b 100
100
80
Ammonia removal (%)
Ammonia removal, %
80
60
60
40
40 0.4 L/min
50 °C 2 L/min
20
20 65 °C 3 L/min
Gas flow rate 2 L/min 75 °C Feed temp. 75 °C 5 L/min
0 0
0 50 100 150 200 0 50 100 150 200
Time (min) Time, min
Sweep Gas Membrane Distillation (SGMD) Applica- flow rate 250 mL/min (Reprinted from Xie et al. 2009,
tions, Fig. 2 (a) Effect of feed temperature and (b) flow copyright (2009), with permission from Elsevier)
rate of sweep gas on ammonia removal using SGMD, feed
whereas its selectivity was lower. The pH of was also used for the recovery of black currant
ammonia solution was very important for its sep- and cherry juice aroma compounds from a model
aration (Xie et al. 2009). solution and for the retention of anthocyanins in
Another SGMD application can be an indus- the juice. An increase in the feed temperature
trial fruit juice processing. Successful experi- improved the aroma flux; thus, their concentra-
ments were carried out using SGMD for the tion in the permeate was elevated. The highest
concentration of sucrose solutions as a model concentration factors for highly volatile aroma
fruit juice (Khayet and Matsuura 2011). SGMD compounds were in the range of 12.1–9.3 (black
Sweep Gas Membrane Distillation (SGMD) Applications 3
90 1,8-Clneole
1,8-clneole (exp.)
80 Ethyl butanoate
Ethyl butanoate (exp.)
Isoamyl acetate
70 Isoamyl acetate (exp.)
Recovered aroma (%)
4-Terplnenol
60 4-Terplnenol (exp.)
cls-3-Hexen-1-ol
50 cls-3-Hexen-1-ol (exp.)
40
30
20
10
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Feed volume reduction (%)
Sweep Gas Membrane Distillation (SGMD) Applica- (Reprinted from Bagger-Jørgensen et al. 2011, copyright
tions, Fig. 3 The experimental results and theoretically (2011), with permission from Elsevier)
predicted values of aroma fractions recovery by SGMD
currant juice) and 16.3–13.0 (model solution). In aroma compounds by membrane technology: sweep-
the case of a black currant juice, the amount of ing gas versus vacuum membrane distillation. Innov
Food Sci Emerg Technol 12:388–39
recovered aroma was 73–84 vol.% for the highly He Y et al (2012) Recent advances in membrane technolo-
volatile compounds (Fig. 3). However, during the gies for biorefining and bioenergy production.
concentration of juice, a part of anthocyanins and Biotechnol Adv. doi:10.1016/j.biotechadv.2012.01.015
polyphenols in black currant juice was lost due to Khayet M, Matsuura T (2011) Membrane distillation.
Principles and applications. Elsevier, Amsterdam
the degradation of anthocyanin by oxidation Lee CH, Hong WH (2001) Effect of operating variables on
(Bagger-Jørgensen et al. 2011). the flux and selectivity in sweep gas membrane distil-
lation for dilute aqueous isopropanol. J Membr Sci
188:79–86
Xie Z, Duong T, Hoang M, Nguyen C, Bolto B (2009)
References Ammonia removal by sweep gas membrane distilla-
tion. Water Res 43:1693–1699
Bagger-Jørgensen R, Meyer AS, Pinelo M, Varming C,
Jonsson G (2011) Recovery of volatile fruit juice
T
Qt ¼ DðC2 C1 Þt=l
Time Lag Method for Mass Transport 2l X
1
C2 cos np C1
Properties Evaluation in GS þ 2 1 exp Dn2 p2 t=l2
p 1 n2
4C0 l X
1
1 n o
þ 2 1 exp Dð2m þ 1Þ2 p2 t=l2
Donald R. Paul p 0 ð2m þ 1Þ 2
Turndown in Gas Separation Also PSA units can maintain both recovery
and product purity at throughputs of
Adele Brunetti ca. 30–100 % of design by adjustment of the
National Research Council, Institute for cycle time. Between 0 % and 30 % of design
Membrane Technology (ITM-CNR), The product rates, purity can be maintained, but
University of Calabria, Rende (CS), Italy recovery is reduced unless special provisions
are made in the design.
The turndown capability of cryogenic systems
Turndown is the capability of the system to oper- strongly depends on the design. Partial conden-
ate at reduced capacity (Miller and Söcker 1989). sation units can maintain product purity at
In gas separation, membrane systems are highly slightly reduced recovery at flows down to
capable of maintaining product purity even 30–50 % of design.
though the capacity is reduced down to 10 % of
the initial design. This is done by either reducing
feed pressure, increasing permeate pressure, or
References
by isolating modules from the system. The first
two methods can be used for short-term operation Brunetti A, Bernardo P, Drioli E, Barbieri G (2010)
and the latter when operating at significantly Membrane engineering progresses and potentialities
reduced capacity for extended periods. No pre- in gas separations. In: Yampolskii Y, Freeman
visions are required in the design phase. B (eds) Membrane gas separation. Wiley, New York,
pp 281–312
Absorption units can maintain both recovery Miller GQ, Stöcker J (1989) Selection of a hydrogen
and product purity at throughputs of separation process NPRA annual meeting 19–21 Mar,
ca. 30–100 % of design by adjustment of the gas San Francisco
streams and solvent flow rates.
Closed side
Water vapour and volatiles
Feed Vacuum
Feed tank
Vacuum pump
Vacuum Membrane Distillation (VMD), Fig. 2 A typical setup used for carrying out vacuum membrane distillation
tests
V
Vacuum Membrane Distillation VMD can be also used for the concentration of
(VMD), Applications of fruit/vegetable juices (Al-Asheh et al. 2006; Zhao
et al. 2008), again, with the aim of recovering
A. Criscuoli water as distillate while producing a high concen-
Institute on Membrane Technology (ITM-CNR), trated retentate that can be easily stored and
Rende (CS), Italy shipped.
Referring to the application of VMD to the
extraction of specific volatile compounds
Vacuum membrane distillation (VMD) can be contained in water streams, some examples are
applied to the treatment of aqueous streams for the removal of ethanol (Izquierdo-Gil and
recovering purified water or for extracting Jonsson 2003); the removal of ammonia
specific volatile compounds. Concerning the (El Bourawi et al. 2007) or VOCs from water,
first type of application, many studies have like toluene, benzene, etc. (Couffin et al. 1998);
demonstrated the efficiency of the technique for and the recovery of aroma compounds (Soni
liquid streams contaminated by nonvolatile et al. 2008; Diban et al. 2009).
species such as heavy metals or dyes discharged Table 1 summarizes the main applications of
by textile companies (Criscuoli et al. 2008): in all VMD.
cases, the distillate produced consists of purified
water (able to be reutilized inside the productive
plant or to be used for drinking/agriculture
purposes) with rejection values generally higher
Vacuum Membrane Distillation (VMD), Applications
than 99 %. Other positive performances are those of, Table 1 Main applications of VMD
related to the treatment of olive mill wastewaters
Recovery of purified water from aqueous streams
(Garcia-Castello et al. 2010) and the recovery of containing nonvolatile pollutants like heavy metals,
fully demineralized water starting from brackish dyes, etc.
waters, seawaters, and reverse osmosis brines Recovery of fully demineralized water from salty
(Li and Sirkar 2005; Safavi and Mohammadi solutions and concentration of reverse osmosis brine
2009; Méricq et al. 2011). In particular, for the Concentration of fruit and vegetable juices
application to salty solutions, two main benefits Recovery of volatile compounds like ethanol, ammonia,
VOCs, etc., from aqueous solutions
are claimed: the recovery of purified water and
the production of a highly concentrated brine,
with a consequent reduction of its volume and,
therefore, of costs associated to its disposal.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_777-2
2 Vacuum Membrane Distillation (VMD), Applications of
100 95%
Traditional Reactor
Volume Index, %
75%
60%
50 40%
[35]
25%
20%
0
Pd-alloy Membrane Reactor
200 400 600 800 1,000 1,500 3,000
Feed Pressure, kPa
Volume Index, Fig. 1 Volume index as a function of feed pressure for an equimolecular H2O:CO mixture. Furnace
temperature = 280 C. Set CO conversion 90 % of the TREC (Brunetti et al. 2007)
Wine Clarification
Process Integration
Wine turbidity is caused by suspended material
like yeast residues and macromolecular com-
This relatively new concept involves the coupling
pounds with colloidal behavior. The clarification
of two or more unit operations that provide a
operation to remove this material is traditionally
more efficient separation than each operation
performed by diatomaceous earth filtration and
alone. The integration of adsorption and cross-
membrane operations have been relatively
flow microfiltration may reduce unstable protein
restricted because of possible removal of poly-
concentration in white wine, increasing at the
saccharides and other macromolecules that may
same time the permeate flux of microfiltration
be of major relevance to wine quality.
due to less severe membrane fouling. After
adsorption using a packed column of zirconium
oxide pellets and cross-flow microfiltration using
Cross-Flow Microfiltration
a ceramic membrane of zirconium oxide with a
pore size of 0.2 mm, an increase of 15–20 % of the
This more recent operation uses a selective
permeate flux has been observed. About 47 % of
porous membrane that filters a wine in order to
the total protein concentration and 15 % of the
achieve its purification or clarification, resulting
total polyphenol concentration have been lost
into a clear appearance and making the wine
during the adsorption stage. Only the percentage
microbiologically stable. By creating a turbulent
of total, volatile, and fixed acidity of wine
stream on the surface of the membrane, settling of
decreased after using the hybrid process without
filtered particles on the membrane will be
changing the other physicochemical wine prop-
prevented. Two main types of membranes are
erties (Salazar et al. 2007).
currently available: organic membranes made
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_781-2
2 Wine Clarification by Membrane Operations
ß-Lactoglobulin and Alpha-Lactalbumin Separation, Table 1 Physical characteristics of major whey proteins
(From Zydney 1998)
Protein Concentration (g/L) Molecular weight (g/mol) Isoelectric pH
b-Lactoglobulin 2.7 18,362 5.2
a-Lactalbumin 1.2 14,147 4.5–4.8
Immunoglobulins 0.65 150,000–1,000,000 5.5–8.3
Bovine serum albumin 0.4 69,000 4.7–4.9
Lactoferrin 0.1 78,000 9.0
Lactoperoxidase 0.02 89,000 9.5
Glycomacropeptide 7
microorganism microorganism
microorganism
CO2
extracellular low-molecular
enzymes CH H2O
4
weight
intermediates metabolic
products
Biodegradation, Fig. 1 General mechanism of the bio- intermediates by the action of the secreted enzymes, and
degradation process: (1) secretion of extracellular (3) conversion of the intermediates into metabolic
enzymes by the microorganisms, (2) generation of short products
microbial culture originating, for example, from – Weight loss measurements: determination of
a wastewater treatment plant or (2) use of com- residual material after being exposed to the
plex materials collected from the environment biodegradation conditions.
(e.g., water, soil, compost) as the matrix for the – Changes in mechanical properties and
tests (Fig. 2). molar mass: properties, such as tensile
Some of the standard testing methods include strength, can be used as indicators of degrada-
(Shah et al. 2008): tion since they are related with the polymer’s
molar mass.
– Visual observations: macroscopic changes, – CO2 evolution or O2 consumption: under aer-
such as roughening of the surface, formation obic conditions, the microorganisms use O2
of hole or cracks, changes in color, etc., can be for carbon oxidation, generating CO2 as one
used as a first indication of microbial attack, of the major metabolic end product. Hence,
while more sophisticated observations using, CO2 evolution or O2 consumption are good
for example, scanning electron microscopy indicators of polymer degradation.
(SEM) or atomic force microscopy (AFM) – Radio labeling: materials containing a ran-
can be made to obtain more information domly distributed 14C marker can be exposed
about the degradation mechanism. to the microbial environment and the amount
Biodegradation 3
Corrosion and not another, but the reverse may be true for
another type of water. An excellent method for
C. V. Vedavyasan corrosion control in water heaters is cathodic
Desalination Process Specialist (Global), protection involving the use of a sacrificial
Department of Technology, Annamalai anode, usually composed of magnesium or alu-
University, Chidambaram, Tamil Nadu, India minum. Chemical control of corrosion attempts
to retard electrode reactions.
Introduction
The Mechanism and Chemistry of Corrosion
Reactions
Corrosion is the gradual process of wearing,
Corrosion reactions are electrochemical in
weaning away, and thinning down the metal sur-
nature. They involve the transfer of charged
face by the fluid with which it is in contact.
ions across the surface between a metal and the
Millions of dollars are lost every year due to
electrolyte in which the metal is immersed. There
corrosion of iron and steel. Other metals do cor-
are two types of electrode reaction occurring at
rode. The oxide formed by oxidation does not
the metal surface: anodic and cathodic.
firmly adhere to the surface of the metal and
Corrosion occurs in the presence of moisture.
flakes off easily causing “pitting”. Continued
When iron is exposed to moist air, it reacts with
pitting causes structural weakness and disintegra-
oxygen to form rust. The amount of water http://
tion of the metal. Metals such as aluminum form
www.corrosion.com, precisely the number of
a tough oxide coating onto the surface to prevent
molecules of water, present determines the color
corrosion.
of rust varying from black to yellow to orange
In some circles, corrosion has been described
brown. The formation of rust is a very complex
as the tendency of a metal to revert to its natural
process which begins with the oxidation of iron to
stable state as an ore. The process may involve a
ferrous (+2) ions.
second step in which an oxide, hydroxide, or
In an anodic reaction, electrons appear on the
carbonate of the metal may form and deposit at
right-hand side. An example is shown below:
the corrosion site. Thus, corrosion takes place
when a metal dissolves in or is disintegrated by
Fe > Feþ2 þ 2e :
water.
Different metals have different tendencies to
corrode or not to corrode in the same water.
A certain type of water may corrode one metal
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_785-3
2 Corrosion
Both water and oxygen are required for the that rusting occurs much more rapidly in moist
sequence of reactions. Iron (+2) ions are further environment as compared to dry one. The mecha-
oxidized to form ferric ions (iron+3) ions: nism of corrosion is shown in Fig. 1 below.
Corrosion,
Fig. 3 Isolation flanges to
prevent galvanic
• Avoid the use of widely dissimilar metals in deposit is cleaned away, tiny pits or holes can
direct contact. be seen in the surface. Passive metals such as
• When dissimilar metals must come into con- stainless steel resist corrosive media and can per-
tact, they should be separated by using form well over long periods of time. However, if
nonconductive barrier materials, a paint coat- corrosion does occur, it forms at random pits.
ing, or by plating. Pitting may be a serious type of corrosion because
• The anode should be as large as feasible in it tends to penetrate rapidly into the metal section.
relation to cathode. It is most likely to occur in the presence of chlo-
• Coat both the anode and the cathode with the ride ions, combined with such depolarizers as
same material. oxygen or oxidizing salts. Methods that can be
• Install fasteners that have been dipped in used to control pitting include maintaining clean
epoxy mastic coatings. surfaces, application of a protective coating, and
• Seal threaded inserts with epoxy mastic coat- use of inhibitors or cathodic protection for
ings prior to insertion into castings. immersion service.
• Avoid the use of lock or toothed washers over Sometimes pitting corrosion can be quite
plated or anodized surfaces. small on the surface and very large below the
surface. The figure below left shows this effect
The scuba tank above suffered galvanic corro- common on stainless steel and other film-
sion when the brass valve and the steel tank were protected metals. Pitting shown on the right
wetted by condensation. Electrical isolation (white arrow) led to the stress corrosion fracture
flanges (Fig. 3) like those shown on the right are shown by the black arrows (Fig. 4).
used to prevent galvanic corrosion. Insulating Pitting corrosion can lead to unexpected cata-
polymeric gaskets are inserted between the strophic system failure. The split tubing below
flanges, and insulating sleeves and washers iso- left was caused by pitting corrosion of stainless
late the bolted connections. steel. A typical pit on this tubing is shown below
right (Fig. 5).
Pitting Corrosion
The most common effect of corrosion on alumi- Stress Corrosion Cracking
num and magnesium alloys is pitting. First is Stress corrosion cracking (SCC) is caused by the
noticeable as a white or gray powder, similar to simultaneous effects of tensile stress and corro-
dust, which blotches the surface. When the sion. Stress may be internally or externally
Corrosion 5
applied. Internal stresses are produced by • Remove stress risers from counter bores,
nonuniform deformation during cold working, grooves, etc.
by an unequal cooling from high temperatures,
and by internal structural rearrangement involv-
Crevice Corrosion
ing volume changes. Stresses induced when a
Crevice or contact corrosion is produced at the
piece is deformed, those induced by press and
region of contact of metals with metals or metals
shrink fits, and those in rivets and bolts are inter-
with nonmetals. It may occur at washers, under
nal stresses. Concealed stress is more important
barnacles, at sand grains, under applied protec-
than design stress, especially because stress cor-
tive films, and at pockets formed by threaded
rosion is difficult to recognize before it has over-
joints. Whether or not stainless steels are free of
come the design factor. Few guidelines in
pit nuclei, they are always susceptible to this kind
avoiding the problem are:
of corrosion because a nucleus is not necessary.
Crevice corrosion may begin through the action
• Use metal alloys at no greater than 75 % of
of an oxygen concentration cell and continue to
their yield strength and use exotic materials
form pitting. Cleanliness, the proper use of seal-
only where they are actually required.
ants, and protective coatings are effective means
• Avoid assemblies where high-tensile loads are
of controlling this problem.
concentrated in a small area.
6 Corrosion
processing. Cleaning shall be accomplished in brush coat of primer prior to spray will assist
the following bath: in getting adequate coverage.
• Nuts and bolts. Premature coating failure and
1. Nitric acid (HNO3) (42 Baume) corrosion on nuts and bolt heads are common
225–375 kg/m3 and can be reduced by conscientious surface
2. Hydrofluoric acid (HF) or NH4HF2 preparation prior to application of a protective
9–52 kg/m3 coating. A brush coat of primer prior to spray
3. Temperature: room 60 C (140 F) will ensure adequate coverage.
4. Metal content, HF ratio = 1: 1.8 (replenish • Tube clamps. Carbon steel clamps for interior
bath when the metal concentration >1 part of applications are either zinc plated or painted.
metal to 1.8 parts of HF) Stainless clamps shall be used for all exterior
applications. Corrosion at the interface
Stainless Steel Alloys between the stainless steel tubing and the
Stainless steels owe their inherent corrosion clamp can occur due to dissimilar metal and
resistance to a condition known as passivity – as crevice corrosion. Corrosion at the interface
a result of the presence of their oxide films called between tubing and clamps is controlled by
“passive films.” Under favorable conditions, such application of protective coatings.
films are protective; however, unfavorable con- • Unistrut channels. Use of unistrut channels
ditions deficient in oxygen will destroy the films should be avoided in exterior locations. When
and leave the surface in an “active” state with the exterior use of unistrut cannot be avoided,
corrosion resistance comparable to carbon steel. selection of appropriate material shall be uti-
The presence of hygroscopic salt deposits, dirt, lized, such as stainless steel or fiber glass.
dust, and other foreign matter all serve to destroy Where corrosion is noted, mechanically clean
passivity. Underground exposure of bare stain- the member to remove corrosion products
less steel will result in unacceptable quality. followed by application of a zinc-rich coating.
Where localized corrosion occurs, rapid penetra-
tion (pitting) at the point of initiation can occur as Stainless Steel Components
an electrolytic cell is formed between the large
cathodic (passive) area and the small anodic area General Stainless steel, although very corrosion
under attack. This attack is particularly severe in resistant, is susceptible to localized corrosion
the presence of halide salts. Localized attack will (e.g., pitting, crevice corrosion, etc.) when
also occur in crevices, such as under sleeves on exposed to marine environment. A mistake fre-
tube fittings. quently made is to conclude that the corrosion
Superior resistance to pitting is attainable with noted on stainless steel tubing and bellows is only
type 904 L unified numbering system (UNS) superficial. This conclusion is improperly
N08904 stainless steel over other commonly reached when removal of external corrosion
used steels. However, this is only a matter of products leaves the surface in a condition that
degree and localized attack can still occur. appears almost like new except for what appears
Maintaining clean surfaces will greatly reduce to be a very tiny pit. A cross section taken through
the opportunity for corrosion, regardless of the such a typical pit frequently discloses a void
alloy employed. considerably greater in diameter than the surface
pit diameter. Failure to arrest the apparent super-
Typical Problem Areas ficial corrosion will result in ultimate penetration
• Sharp edges. Sharp edges of metal structures of thin wall members.
will often be deficient of proper coating thick-
ness; sharp edges should be rounded when Application of Protective Coatings
possible with the National Association of Cor- Stainless steel tubings shall be treated in the
rosion Engineers (NACE). A stripe coat or following way:
8 Corrosion
• Accumulated dirt and oil shall be removed by structures. A common application is in galva-
rinsing with water followed by rinsing with nized steel, in which a sacrificial coating of zinc
methyl ethyl ketone (MEK). on steel protects them from rust.
• Remove corrosion products by mechanical Cathodic protection can, in some cases, pre-
means, such as power tool cleaning or hand- vent stress corrosion cracking.
tool cleaning.
• Clean surfaces with methyl ethyl ketone using Applications Pipelines are routinely protected
clean rags. by a coating supplemented with cathodic protec-
• Apply by spraying, brushing, or dipping tion. An ICCP – impressed current cathodic
75 mm (3 mils) minimum of the coating protection – system for a pipeline would consist
Aerocoat AR-7 manufactured by B.F. of a DC power source, which is often an
Goodrich. AC-powered rectifier and an anode, or array of
anodes buried in the ground (the anode ground
Tubing assemblies shall be abrasive blasted. head)
When tubing assemblies are in close proximity to Ships: cathodic protection on ships is often
carbon steel structural members that are to be implemented by galvanic anodes attached to the
abrasive blasted and coated with inorganic zinc- hull, rather than using ICCP. Since ships are
rich primer, the tubing assemblies shall be simi- regularly removed from the water for inspections
larly treated. and maintenance, it is a simple task to replace the
galvanic anodes. Galvanic anodes are generally
• Using clean rags, accumulated dirt and oil shaped to reduced drag in the water and fitted
shall be removed with water followed by wip- flush to the hull to also try to minimize drag.
ing with methyl ethyl ketone.
• Apply a zinc-rich coating in accordance with How to Prevent Metal Corrosion
the manufacturer’s recommendations to a • Choose products that are made of
DFT (dry film thickness) of 100–150 mm noncorrosive metals like stainless steel and
(4–6 mils). aluminum.
• Maintain a dry environment using appropriate
moisture barriers.
Cathodic Protection
• Ensure the electrical connections are clean.
Cathodic protection (CP) is a technique used to
• On a car or truck, apply a thin coating of
control the corrosion of a metal surface by mak-
petroleum jelly after cleaning the terminal.
ing it the cathode of an electrochemical cell. CP is
• Coat metals with oil, paint, grease, or varnish
carried out by connecting the metal to be
because it can prevent corrosion.
protected with a piece of another more easily
• Make use of cleaning agents like soaps, sol-
corroded “sacrificial metal” to act as the anode
vents, emulsion compounds, and chemicals to
of the electrochemical cell. The sacrificial metal
efficiently get rid of oil, grease, dirt, and other
then corrodes instead of the protected metal. For
unwanted foreign deposits and follow the cor-
structures where passive galvanic CP is not ade-
rect procedures in applying them.
quate, like in long pipelines, an external DC
• A mixture of cola and baking soda paste will
electrical current is applied. Cathodic protection
remove metal corrosion on car batteries.
systems are used to protect a wide range of metal-
• To prevent soil corrosion, install correctly
lic structures in various environments. Common
copper or copper alloy plumbing under-
applications are steel water or fuel pipelines and
ground. The main causes of copper corrosion
storage tanks such as home water heaters, steel
are poor drainage and moisture. A loose layer
pier piles, ship and boat hulls, offshore oil plat-
of backfill such as limestone or pea level must
forms and onshore oil well casings, and metal
be put down in the trench before laying copper
reinforcement bars in concrete buildings and
pipes.
Corrosion 9
Summary
References
Corrosion is effectively controlled by cathodic
protection or by appropriate selection of inhibi- VIII- Met J Corros Prot
TM 584 Revision C. http://www.corrosioncontrol.com.
tors, provided the chemical and electrical condi- Accessed Nov 1994
tions are scientifically monitored. Understanding Corrosion Technology Laboratory – Galvanic corrosion.
of the mechanism is the key in handling the http://corrosion.ksc.nasa.gov/galcorr.htm. http://corro
condition of the metals and structures. Every sion.ksc.nasa.gov/pitcor.htm. http://corrosion.ksc.
nasa.gov/stresscor.htm. http://corrosion.ksc.nasa.gov/
scenario is site specific and needs to be addressed
crevcor.htm
on its associated factors of pH of the medium,
I
Synthesis of Removal by
Polymerizable Chemical Molecular
Print Molecule Polymerization Cleavage Recognition
Imprinting, Fig. 1 Schemes of the covalent and non-covalent molecular imprinting (Cited from Yoshikawa et al. 2011
with permission. Copyright 2012 Elsevier Inc.)
Step 2
Step 1 Removal of print molecule
Interaction between print
molecule and candidate
material
Step 4 Step 3
Recognition of print molecule Formation of recognition
(print molecule analogue) site and permeation path
Imprinting, Fig. 2 Scheme of the alternative molecular imprinting (Cited from Yoshikawa et al. 2011 with permission.
Copyright 2012 Elsevier Inc.)
This study is the first report on the alternative then, various molecularly imprinted membranes
molecular imprinting and the first application of were studied by adopting non-covalent molecular
molecularly imprinted polymeric membranes to imprinting. A wet phase inversion process was
membrane separation. Michaels’ paper is the applied to an alternative molecular imprinting to
commemorable paper in molecular imprinting prepare asymmetric membranes (Trotta
and membrane separation. In addition to this, et al. 2002).
molecularly imprinted polymeric membranes As described above, applying molecular
prepared by non-covalent molecular imprinting imprinting, such as conventional molecular
was reported in 1990 (Piletskii et al. 1990). Since imprinting or alternative molecular imprinting,
Imprinting 3
molecular recognition sites are easily introduced Arshady R, Mosbach K (1981) Synthesis of substrate-
into polymeric membranes (Ulbricht 2004). From selective polymers by host-guest polymerization.
Makromol Chem 182:687–692
this, it is easy to enhance permselectivity of a Komiyama M, Takeuchi T, Mukawa T, Asanuma
given membrane by applying those molecular H (2003) Molecular imprinting. Wiley-VCH,
imprinting techniques. The enhancement of flux Weinheim
without a reduction in permselectivity is indis- Michaels AS, Baddour RF, Bixler HJ, Choo CT (1962)
Conditioned polyethylene as a permselective mem-
pensable so that molecularly imprinted mem- brane. Separation of isomeric xylenes. Ind Eng
branes can be applicable to industries. Chem Process Des Dev 1:14–25
Molecularly imprinted membranes with a Piletskii SA, Dubei IY, Fedoryak DM, Kukhar VP (1990)
higher surface area and a higher porosity are Substrate-selective polymeric membranes Selective
transfer of nucleic acid components. Biopolim Kletka
required to give higher flux and permselectivity. 6:55–58
Electrospun nanofiber membranes with molecu- Sellergren B (ed) (2001) Molecularly imprinted polymers
lar recognition sites is a suitable or the best mem- man made mimics of anti bodies and their applications
brane morphology to attain high flux and high in analytical chemistry. Elsevier, Amsterdam
Trotta F, Drioli E, Baggiani C, Lacopo D (2002) J Membr
permselectivity. Possibility of the enhancement Sci 201:77–84
of flux without a concurrent reduction in Ulbricht M (2004) Membrane separations using molecu-
permselectivity was proved by molecularly larly imprinted polymers. J Chromatogr
imprinted nanofiber membranes, which were fab- B 804:113–125
Wulff G, Sarhan A (1972) The use of polymers with
ricated by simultaneously applying an enzyme-analogous structures for the resolution of
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References Yoshikawa M, Izumi J, Kitao T, Koya S, Sakamoto
S (1995) Molecularly imprinted polymeric membranes
Allexander C, Andersson HS, Andersson LI, Ansell RJ, for optical resolution. J Membr Sci 108:171–175
Kirsch N, Nicholls IA, O’Mahony J, Whitcombe MJ Yoshikawa M, Tanioka A, Matsumoto H (2011) Molecu-
(2006) Molecular imprinting science and technology: larly imprinted nanofiber membranes. Curr Opin
a survey of the literature for the years up to and includ- Chem Eng 1:18–26
ing 2003. J Mol Recognit 19:106–180
N
broad function ranging from environmental catalytic properties is a good candidate to revers-
remediation to smart product manufacturing. Par- ibly immobilize enzyme on the surface of a poly-
ticularly, the synergistic antifouling property and meric membrane to mimic hybrid protein-
improved permselectivity give the membrane a polymer biomimetic membranes.
big prospect to be utilized in water purification. Alternative to direct integration of the enzyme
NPSP-coated membranes, for example, have been within the polymer matrix, stimulus-responsive
used for effective removal of natural organic programmable layers on membrane can be
matter (Yao et al. 2009), arsenic (Sabbatini formed through the attraction of NPSP through
et al. 2010), and copper (Daraei et al. 2012) dur- reversible magnetic force. These biomimetic
ing water treatment. smart layers will enable development of adaptive
enzyme membrane reactors. For instance, once
an enzyme is immobilized on NPSP, they can be
Bioinspired Nanotechnology easily dispersed in a reaction medium in the
Membranes absence of an external magnetic field. However,
by applying an external magnetic field, it is pos-
Biomimetic nanostructured membranes are sible to relocate the bionanocomposites toward
formed either through directly embedding bio- the surface of a membrane using an external
molecule into synthetic materials or by using magnetic field. The method is promising to
functional molecules to modify synthetic mate- resolve pertinent issues related to the direct inte-
rials to impart specific biological property. These gration of enzyme within the polymeric matrix.
hybrid biomimetic membranes combine the accu- Overall, tuning reversible enzyme immobiliza-
rate structure of a biological pore with the dura- tion using NPSP helps in:
bility, robustness, and the possibility to control
the pore size and shape of solid-state nanopore 1. Easy recovery, recycling, and removal of
membrane (Shen et al. 2014). immobilized enzyme
2. Formation of dynamic layer between mem-
Biohybrid Magnetic-Responsive Membranes brane and feed preventing membrane-
Superparamagnetic nanoparticles (NPsSP) are pollutant interaction
most often superparamagnetic iron oxide with 3. Activation of the monolayer with biocatalyst
zero memory of their magnetic property in the to achieve biocatalysis at the membrane-
absence of an external magnetic field (Yeon solution interface
et al. 2009). Polymer coatings and the introduc- 4. Easy regeneration of membrane whenever the
tion of various surface functional groups facili- membrane is oversaturated with substrate
tate the anchorage of biomolecules on the surface
of these particles (Miguel-Sancho et al. 2012; This approach has recently been demonstrated
Brullot et al. 2012; Xiao-Ming and Wainer to form an enzyme membrane reactor
1993). The resulting bionanocomposites repre- (Gebreyohannes et al. 2015). The method is
sent an important material with a versatile appli- novel for it has used NPSP as a carrier to anchor-
cation in the biotechnology, fine chemicals, drug age various enzymes as well as nanofiller to form
delivery, cell transplantation, or cell immobiliza- magnetic-responsive hybrid membrane. When an
tion. These nano-sized particles exhibit biocom- external magnetic field has been applied to the
patibility, high surface-to-volume ratio which system, the magnetic-responsive polymeric
makes them a good candidate for enzyme immo- membrane gets magnetized. Subsequently, the
bilization to make biohybrids. The high surface- NPSP with the immobilized enzyme was dis-
to-volume ratio assists with higher enzyme load- persed in the upper stream. These particles were
ing capacity and enhanced mass transfer effi- then attracted toward the surface of the mem-
ciency. Hence this material with its excellent brane. The magnetic-responsive membrane acts
mechanical, optical, electrical, ionic, and as magnetic field actuators that eventually help
4 Nanotechnology Membrane
with uniform dispersion of the NPSP on the sur- permeability to diffusion permeability is the
face of the membrane. Hence it has potentially number of effective steps a water molecule shall
mimicked the micro-nanoarchitecture of the move in order to permeate through a channel.
direct integration of enzyme into the membrane. Since aquaporin channels have high water selec-
The method has shown an interesting perfor- tivity, a membrane with 75 % aquaporin coverage
mance when it was applied to treat a feed rich in is predicted to have an order of magnitude higher
polysaccharides. After depositing 1–2 g/m2 of water permeability compared to commercial sea-
pectinase activated NPSP with an average diame- water RO membranes (Kaufman et al. 2010).
ter of 8 nm, 40 % to 100 % reduction in the There already are interesting research activi-
pressure required to keep flux constant at 17 L/ ties on the inclusion of aquaporins in polymeric
m2 h was observed. Moreover, thanks to the easy membranes. For instance, the use of aquaporin-Z
recycling of enzyme, both membrane and from E. coli bacterial cells used to form a protein-
immobilized enzyme were used over several polymer membrane exhibited an order of magni-
cycles, adding a considerably extended lifetime tude higher water permeability as compared to a
to the membrane as well as the enzyme counterpure polymeric membrane. However,
(Gebreyohannes et al. 2015). practical application of these proteins is highly
Modulating reversible enzyme immobiliza- limited by lack of large quantities of protein
tion through combinatorial stimulus-responsive production. Nevertheless, with a continued
enzyme immobilization technique holds a great research and effort, techniques to simplify the
potential in bioseparations, antifouling surfaces, fabrication and production of mechanically
and creating self-cleaning membranes. Hence, sound membranes aquaporin-based biomimetic
the future innovations on the basis of stimulus- membranes are inevitable.
responsive enzyme immobilization holds a big-
ger prospect to “reengineer” membrane biocatal- Vertically Aligned Carbon Nanotubes
ysis that will lead to the design of more complex Carbon nanotubes (CNTs) exhibit the fast mass
membrane systems that are capable of mimicking transfer resemblance to aquaporin water channels
the nature. in which water transport is two to five times
higher than theoretically predicted by Hagen-
Aquaporin Membranes Poiseuille equation (Holt et al. 2006). Molecular
Aquaporins are the protein channels that control dynamic simulation studies attributed this out-
water flux across biological membranes. Water standing flow rate to atomic smoothness and
movement in aquaporins is mediated by selec- molecular ordering. In particular, water mole-
tive, rapid diffusion caused by osmotic gradients cules permeate through the CNTs in a
(Agre 2006; Meinild et al. 1998). According to one-dimensional single file resulting in very
Zhu et al. (nd), the two major factors that control small driving force use. Moreover, CNT-based
water transport are: membrane represents excellent mechanical prop-
erties that impart longer lifetime than conven-
(a) Osmotic permeability: molecular movement tional membrane materials.
due to concentration differences resulting in The most commonly utilized mechanism used
net mass transfer to produce uniformly aligned nanotube arrays is
(b) Diffusion permeability: random movement chemical vapor deposition (CVD). The CNTs are
of molecules with no net mass transfer adapted by fixing surface functional groups to
mimic aquaporin structure or by CVD and a
In the first case, the water molecules transport simultaneous solid-state reaction (Holt
in a single file through a narrow aquaporin chan- et al. 2006). The pore densities of the CNTs
nel, while in the second case, permeation occurs made by fixing negative surface functional
due to the movement of two molecules between groups are as high as 0.25*1012/cm2 while
opposite pools. Hence, the ratio of the osmotic representing three order of magnitude higher
Nanotechnology Membrane 5
water flux relative to what is predicted theoreti- Himstedt HH, Yang Q, Dasi LP, Qian X, Wickramasinghe
cally. However, CNTs’ alignment via CVD has a SR, Ulbricht M (2011) Magnetically activated
micromixers for separation membranes. Langmuir
number of limitations such as its costliness, sen- 27:5574–5581
sitivity, and difficulty for large-scale application. Holt JK, Park HG, Wang Y, Stadermann M, Artyukhin
Alternative to CVD, magnetic alignment, self- AB, Grigoropoulos CP, Noy A, Bakajin O (2006) Fast
assembly, and passing single-walled CNT sus- mass transport through sub-2-nanometer carbon
nanotubes. Science 312:1034–1037
pensions through polymeric filters are Huang Z-Q, Zheng F, Zhang Z, Xu H-T, Zhou K-M
approaches to form CNT-aligned membranes. (2012) The performance of the PVDF-Fe3O4 ultrafil-
Although CNT mimicked biological tration membrane and the effect of a parallel magnetic
aquaporin channels with a material producible field used during the membrane formation. Desalina-
tion 292:64–72
in large amount, no large-scale CNT-aligned Kaufman Y, Berman A, Freger V (2010) Supported lipid
membranes have been produced yet. However, bilayer membranes for water purification by reverse
one can resolve these challenges similar to the osmosis. Langmuir 26:7388–7395
challenges faced by reverse osmosis membranes Meinild AK, Klaerke DA, Zeuthen T (1998) Bidirectional
water fluxes and specificity for small hydrophilic mol-
50 years ago when performance improvements ecules in aquaporins 0–5. J Biol Chem
lead to the practical necessity of CNT-aligned 273:32446–32451
membrane application. Miguel-Sancho N, Bomati-Miguel O, Roca AG,
Martinez G, Arruebo M, Santamaria J (2012) Synthe-
sis of magnetic nanocrystals by thermal decomposition
in glycol media: effect of process variables and mech-
anistic study. Ind Eng Chem Res 51:8348–8357
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of separation selectivity. The permeability of He Kharitonov AP (2008) Direct fluorination of polymers.
and H2 is not practically changed after fluorina- Nova Science Publishers, New York
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References
have generated renewed interest in this technol- phenomena. As originally described, HPTFF
ogy. This is particularly true for flow-through devices are operated in the pressure-dependent
applications in which impurities are bound to regime at or below the “transition point” in a
the membrane while the product flows directly plot of filtrate flux versus transmembrane pres-
through the membrane (Zhou and Tressel 2006). sure. This minimizes membrane fouling and takes
This includes the removal of trace DNA, viruses, advantage of concentration polarization effects to
and endotoxins. Flow-through applications can increase performance (Zeman and Zydney,
take full advantage of the high linear velocities 1996). Further increases in selectivity are
possible with membranes. Single-use membrane obtained by using charged ultrafiltration mem-
adsorbers can be very attractive in these applica- branes and by adjusting the solution pH and
tions because of the small amount of impurities ionic strength to exploit differences in protein
that need to be captured. This eliminates the need charge between the product and impurity. High
for reuse studies at small scale and for regenera- degrees of purification and yield are obtained
tion and sanitization at large scale, both of which using a diafiltration process in which the impuri-
facilitate the development of flexible ties are washed through the membrane and away
manufacturing processes (van Reis and Zydney from the highly retained product. It is also possi-
2007). ble to collect the product in the permeate solution
High-performance tangential flow filtration with the impurities retained by the membrane.
(HPTFF) is an emerging technology that uses
ultrafiltration membranes for the separation of
proteins without limit to their relative size (van
References
Reis and Zydney 2007). This is in sharp contrast
to conventional ultrafiltration processes that are Ghosh R (2002) Protein separation using membrane chro-
generally thought to require a tenfold difference matography: opportunities and challenges.
in size between the product and impurity for J Chromatogr A 952:13–27
effective separation. HPTFF has been used to van Reis R, Zydney AL (2007) Bioprocess membrane
technology. J Membr Sci 297:16–50
separate monomers from oligomers based on Zeman LJ, Zydney AL (1996) Microfiltration and ultrafil-
their difference in size, protein variants differing tration: principles and applications. Marcel Dekker,
at only a single amino acid residue based on the New York
difference in charge, an antigen-binding frag- Zeng X, Ruckenstein E (1999) Membrane chromatogra-
phy: preparation and applications to protein separa-
ment from a similar size impurity, and a mono- tion. Biotechnol Prog 15:1003
clonal antibody from host cell proteins (van Reis Zhou JX, Tressel T (2006) Basic concepts in q membrane
and Zydney 2007). chromatography for large-scale antibody production.
The high selectivity in HPTFF processes is Biotechnol Prog 22:341
obtained by exploiting a number of different
P
Protein Separation by Charged UF Membranes, Table 1 Effect of membrane charge and solution pH on the
selectivity for separation of albumin and an antigen-binding fragment. Impurity and product refer to the less and more
retained proteins, respectively. Thus, selectivity is defined as Salbumin/SFab at pH 5 and as SFab/Salbumin at pH 8.4
Solution pH Negative membrane Positive membrane
5.0 3 120
8.4 200 5
Table adapted from Rohani and Zydney (2010)
Aquaporin-Incorporated
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Duong PHH, Chung TS, Jeyaseelan K, Armugam A,
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Polymer-based biomimetic membranes for
A
Air Bubbling in Membrane The TCM extract was heated to 43–62 C and
Distillation pumped to the module; another pump was used to
circulate the permeate water (maintained at
Chunrui Wu 25 C) at the permeate side of the membrane
State Key Laboratory of Hollow Fiber Membrane module. The velocity of the feed and permeate
Materials and Membrane Processes, Institute of flow in the membrane module ranged from 0.07
Biological and Chemical Engineering, Tianjin to 0.13 m/s. To mitigate membrane fouling, a fan
Polytechnic University, Tianjin, China was used to create gas bubbling at the feed side of
the membrane module. This fan was also utilized
to generate gas sparging at the permeate side for
Air bubbling is a common method that is used in gas backwashing of the membrane. The concen-
membrane separation process to alleviate mem- tration ratio (CR) was defined as the ratio of the
brane fouling and improve flux. It also is a kind of volume of initial extract to the volume of con-
membrane cleaning method. Till now, gas-liquid centrated extract to indicate the concentrating
two phase flow has been well studied and widely performance of the experiments.
used in microfiltration, ultrafiltration (Cabassud The result showed that a sharp flux decline
et al. 1997), membrane bioreactor (Psoch and right after the air was introduced into the feed
Schiewer 2005), and other traditional membrane circulation, and the flux remained at much lower
separation technologies. level when air was continuously injected. The
Based on the above advantages of air bub- explanation authors gave was that the bubbles
bling, it has been introduced into membrane dis- occupied part of the liquid-contacting area in
tillation (MD) process to alleviate membrane the membrane, thus reducing the effective mem-
fouling and improve the heat and mass transfer brane area, and when gas entered the membrane
efficiency. Researchers have introduced air bub- pores, this reduced the partial pressure of water
bling into MD process and developed several new vapor within the pores, thus reducing the driving
kinds of MD process. force. To reduce these effects, intermittent gas
The first application of air bubbling in MD sparging at the feed side at intervals of 20 min
process was firstly reported in 2008 (Ding and lasting only 2 min was applied.
et al. 2008) to concentrate the extract of tradi- The effect of gas bubbling on the DCMD
tional Chinese medicine (TCM). Air bubbling performance was shown in Fig. 2. It could be
was used in direct contact membrane distillation seen that flux declined rapidly in the beginning
(DCMD) and the flow sheet is shown in Fig. 1. of the experiment and then slowly as a result of
the very low-flux level at this time. The
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_813-1
2 Air Bubbling in Membrane Distillation
Air Bubbling
in Membrane 9
Distillation,
Fig. 1 Schematic of
DCMD apparatus. (1)
Thermostatic bath, (2) tank
of TCM extract, (3) gear
pump for extract
circulation, (4) chiller, (5)
gear pump for permeate, (6)
permeate tank, (7) electric
balance, (8) fan for gas
bubbling, and (9) flat sheet
membrane module
3 4 6 8
2 5
7
1
Air Bubbling 24
in Membrane C0 =1.35g/l, tf=60°C, u f=u p=0.102m/s
Distillation, 22 The gas bubbling lasted for 2 min every 20 min
Fig. 2 Performance of 20 1L/min gas flowrate
DCMD using gas bubbling 2L/min gas flowrate
on the feed side 18
without gas bubbling
16
N, kg/m2h
14
12
10
8
6
4
2
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
CR
introduction of gas bubbling at the feed side inlet of membrane module to form gas-liquid
resulted in a higher flux in the beginning of the two phase flow, as shown in Fig. 3.
experiment and a much slower flux decline. Very The results showed that the permeate flux
similar trends were observed with gas bubbling at increased with the air flow rate and/or feed tem-
1 and 2 L/min which meant that increasing the perature increasing. For the VMD process, the
gas flow rate did not result in further process permeate flux was 22 kg/(m2h) when tested at
enhancement. 75 C with a feed flow rate of 120 L/h and a
A novel air-bubbling vacuum membrane vacuum pressure of 0.0085 MPa. While, the flux
distillation (AVMD) process was constructed of AVMD process could reach 40 kg/(m2h) when
in 2011 (Wu et al. 2011) to investigate the gas was introduced into feed solution at the rate
enhancement effect of air bubbling on traditional of 60 L/h, as shown in Fig. 4. For the two pro-
VMD process. Compressed air was pressed into cesses, flux both declined gradually as the feed
the lumen side of the hollow fiber membranes concentration increased from 3.5 to 300 g/L, but
together with the hot feed solution just at the it was much slower for AVMD process. SEM
Air Bubbling in Membrane Distillation 3
Air Bubbling
in Membrane
Distillation,
Fig. 3 Theoretic diagram
of ABMD process Vacuum
Membrane Module
Hollow Fiber
Gas-Liquid two phase
flow
30
Re
3500
20
3000
10
0 2500
0 10 20 30 40 50 60 70
Gas flow rate (L/h)
pictures showed that membranes used in AVMD where Jgas and Jnogas are the permeate fluxes in
process had lighter fouling than that in VMD the DCMD process with and without bubbling,
process. respectively.
For elevated salt concentrations in the feed Gas bubbling is supplied by an air pump. The
steam, gas bubbling was introduced into direct air inlet at the feed side entrance of the membrane
contact membrane distillation (DCMD) in 2013 module and the air nozzle for dispersing the air
(Chen et al. 2013) to examine its effect on the MD are shown in Fig. 5.
performance. In the paper, to characterize the The results showed that the introduction of gas
performance improvement achieved by gas bub- bubbling could effectively enhance MD flux, and
bling, the flux enhancement ratio F is defined: the flux enhancement ratio could reach 1.72 at an
optimized gas flow rate. When the condition was
J gas either a high feed operating temperature, low feed
F¼
J nogas and permeate Reynolds numbers, or a module
with 45 inclined orientation, shorter fiber length,
or lower packing density, a higher flux
4 Air Bubbling in Membrane Distillation
Air Bubbling a
in Membrane
Distillation, Fig. 5 (a)
Air inlet connected to the
membrane module; (b) Air
nozzle
Feed
Air
1.4
F
1.2
1.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Gas flowrate (L.min–1)
enhancement ratio could be achieved. Because rate was higher. Furthermore, the Ф value of the
air bubbling could enhance the turbulence of laminar condition was much higher than that of
feed solution, temperature polarization was the turbulent flow when other conditions were the
effectively reduced. However it was not that the same.
bigger the gas flow rate, the higher the enhance- In 2009, air bubbling was used in a hybrid
ment ratio. It was observed that beyond an opti- process combining membrane distillation in a
mal gas flow rate, the enhancement ratio fell, submerged membrane bioreactor (MDBR) to
possibly due to excessive flow bypassing. mitigate severe fouling and flux decline
The effect of gas flow rate on F in laminar and (Phattaranawik et al. 2009). The result showed
turbulent flows was shown in Fig. 6. In the figure, that adding two inlets for air sparging at 2.5 L/min
it was observed that these two F curves had a each near the potting at the center of the
similar trend. At first, F increased with increasing membrane bundle induced more turbulence at
gas flow rate in the range of 0 Qg 0.2 L min1 the membrane surface. Over 15 days, fluxes were
for the laminar flow and 0 Qg 0.5 L min1 for still relatively stable with an average value of
the turbulent flow, while F decreased when gas 5.16 L/(m2h).
Air Bubbling in Membrane Distillation 5
To sum up, air bubbling was an effective Chen GZ, Yang X, Wang R, Fane AG (2013) Performance
method in membrane distillation to enhance the enhancement and scaling control with gas bubbling in
direct contact membrane distillation. Desalination
performance of MD process. Due to the role of 2013(308):47–55
increasing turbulence of feed solution, air bub- Ding Z, Liu L, Yu J, Ma R, Yang Z (2008) Concentrating
bling could promote the agitation and mix of feed the extract of traditional Chinese medicine by direct
solution to decrease the temperature and concen- contact membrane distillation. J Membr Sci
310(1–2):539–549
tration polarization effect. In addition, the Jirachote P, Fane AG, Pasquier ACS, Wu B (2009) Exper-
enhancing surface shear rate increases the imental study and design of a submerged membrane
remove of foulant from membrane surface at the distillation bioreactor. Chem Eng Technol
feed side to inhibit the influence of membrane 32(1):38–44
Psoch C, Schiewer S (2005) Long-term study of an inter-
fouling. mittent air sparged MBR for synthetic wastewater
treatment. J Membr Sci 2005(260):56–65
Wu CR, Yue J, HuaYan C, Xuan W, QiJun G (2011) Study
References on air-bubbling strengthened membrane distillation
process. Desalination Water Treat 34(1–3):2–5
Cabassud C, Laborie S, Lainé JM (1997) How slug-flow
can improve ultrafiltration flux in organic hollow
fibres. J Membr Sci 128(1):93–101
H
Heat and Mass Transfer latent heat of vaporization. Third, heat transfer by
in Membrane Distillation the way of convection in the permeate boundary
layer. All types of MD contain the first two steps,
Chunrui Wu while for the third step, other types of MD do not
State Key Laboratory of Hollow Fiber Membrane contain it except DCMD.
Materials and Membrane Processes, Institute of At steady state, the overall heat transfer coef-
Biological and Chemical Engineering, Tianjin ficient (H) of the MD process can be expressed by
Polytechnic University, Tianjin, China a resistance in series model (M. Khayet
et al. 2000):
Vapour
Suction and
condenstation Porous membrane
Permeate
Aqueous solution (warm)
Qf ¼ hf T f T fm the MD process, except in AGMD (Curcio and
Drioli 2005).
The energy transfering across the membrane
is:
Mass Transfer
hm
Qm ¼ JDH þ T fm T pm
d The mass flux (J) in MD process is assumed to be
proportional to the vapor pressure difference
For the VMD process, the contribution of heat
across the membrane and is given by:
conduction in the membrane matrix can be
neglected due to the high vacuum degree in the
J ¼ C m Pf P p
vacuum side (Li and Sirkar 2005).
At steady state, the overall heat transfer flux
where Cm is the membrane coefficient, Pf and Pp
through the membrane is given by:
are the vapor pressure at the membrane feed and
permeate surfaces, which can be calculated from
Q ¼ Qf ¼ Qm ¼ Qp
the Antoine equation (Fig. 5). For different types
of MD processes, the obtainment of Cm is based
km
hf T f T f , m ¼ JDH þ T fm T pm on different models:
d
For DCMD process, mass transfer through the
¼ hp T p , m T p membrane can be divided into three models.
These models relate the mass transport with col-
Q ¼ H Tf Tp lisions between molecules, and/or molecules
with membrane. Knudsen diffusion takes place
It is worth pointing out that the heat conduc- when the pore size is too small, such that the
tion can be neglected for nonsported thin mem- collision between the molecules and the inside
brane and high operating temperature as well walls of the membrane suitably expresses the
(Phattaranawik and Jiraratananon 2001). More- mass transport and the collision between mole-
over, the heat transfer by convection is ignored in cules can be ignored (Zhongwei et al. 2003).
4 Heat and Mass Transfer in Membrane Distillation
Knudsen Molecular
Hollow Fiber Modules two large areas, the fabrication of highly perme-
for Desalination able membranes and designs of optimized mem-
brane modules.
Chunrui Wu Recently, many designs of hollow fiber mem-
State Key Laboratory of Hollow Fiber Membrane brane modules have been proposed in order to
Materials and Membrane Processes, Institute of suppress the undesirable temperature and con-
Biological and Chemical Engineering, Tianjin centration polarization phenomena. The perfor-
Polytechnic University, Tianjin, China mances of different polyvinylidene fluoride
(PVDF) hollow fiber membranes have been stud-
ied in different size modules (Fig. 1). The prop-
The desalination of brine is commercially erties of the laboratory modules made, which
implemented by reverse osmosis (RO), multi- depend on the experiment’s requirements, can
effect evaporation (MED), and multistage flash be changed. The modules of PVDF have a stable
(MSF) distillation. Although such conventional performance and can be used in reverse osmosis
processes are widely used, there is a need for drained wastewater treatment (Wu Chunrui
novel desalination techniques such as membrane et al. 2010). The study in comparison of three
distillation (MD) which may be much cheaper membrane distillation configurations and seawa-
and have other distinct advantages. The mem- ter desalination by vacuum membrane distillation
branes used in MD processes can be divided (VMD) showed that the shell-and-tube capillary
into two forms: flat sheet membrane and hollow membrane module had unique advantages such
fiber-based membrane. Most of the work on as flexible and changeable (Chen Huayan
hydrodynamic improvement in MD studies has et al. 2011).
focused on flat sheet membrane modules. They Li et al. designed a novel membrane device
have small membrane areas and thus are limited made of novel membranes. To enhance the brine
to laboratory research. In industry, hollow fiber- side heat transfer coefficient substantially, they
based membrane modules are preferable due to employed cross flow of hot brine over the outside
their lager membrane area per unit volume and surface of hollow fiber membranes. To achieve a
reduced vulnerability to temperature polariza- compact device, they designed a hollow fiber
tion. Based on the MD mechanism, the obtained device built in a rectangular cross flow mode for
flux depends both on the membrane permeation the hot brine to flow over the outside of the fibers
properties and the flow geometry in the mem- (Fig. 2) (Li and Sirkar 2005). Simplified models
brane modules. Therefore, the research on the have been developed to describe the observed
flux enhancement in MD can be divided into performance of the modules in different MD
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_815-1
2 Hollow Fiber Modules for Desalination
processes (Gilron et al. 2007). The MD experi- Different hollow fiber configurations with
ment’s results have shown that the modules’ per- wavy geometries (twisted and braided) for flux
formance was quite satisfactory and the design of enhancement in MD process have been devel-
module enhanced the heat transfer as well as oped by Teoh et al. in 2008 (Teoh et al. 2008).
mass transfer. The different module designs, such as baffles and
spacers, were incorporated during the module
Hollow Fiber Modules for Desalination 3
Hollow Fiber Modules for Desalination, Fig. 3 Different modules design and hollow fiber geometries
configurations
fabrication process, as illustrated in Fig. 3. A sin- conventional module, and the spacer-knitted
gle sieve spacer was placed about 7.5 cm away module had the best performance. Experiments
from both ends of the module in the spacer mod- reveal that improved fiber geometries or arrange-
ule designs. And the distance between each ments can provide a better flow distribution, thus
spacer for the two or three-sieve spacers config- much lower pumping energy cost and higher
urations was 5 or 3.75 cm. Similarly, the helical thermal efficiency could be accomplished
baffle introduced in the central of the module (Fig. 4).
which was surrounded by hollow fibers was In 2005, Liu et al. prepared some coiled hol-
placed 5 cm away from the both ends of the low fiber membrane modules and experimentally
membrane module. The results showed that the examined their mass transfer performances (Liu
application of baffles can increase the feed side et al. 2005). The research results showed that,
heat transfer coefficient. In addition, using compared with the conventional straight module,
spacers among the fibers may increase the effec- the mass transfer in both tube and shell side of the
tive membrane area 18–33 %. Lastly, the appli- coiled hollow fiber module could be remarkably
cation of different hollow fiber configurations enhanced. And the mass transfer coefficient of
with wavy geometries could lead to flux enhance- the coiled module at either side of membrane
ments as high as 36 % without inserting any was more than two times higher than that of the
external turbulent promoter. In overall, the goal straight module. The configurations of the coiled
of greater flux enhancements with modified hol- hollow fiber membrane module and the conven-
low fiber membranes modules was achieved. tional strait module are shown in Fig. 5. Different
Five types of novel hollow fiber module con- geometric coiled modules were employed to
figurations have been designed and constructed study the influences of the factors such as coiled
by Yang et al. for the direct contact membrane diameter, wind angle, and internal diameter of
distillation (DCMD) process in 2011 (Yanga fibers on mass transfer. It was found that wind
et al. 2011). The novel designs could be divided angle had an important influence on the fluid
into structured-straight fibers, curly fibers, central condition of the coiled module and its mass
tubing for feeding, spacer-wrapped fibers, and transfer.
spacer-knitted fibers. The test results showed Geng et al. developed a new air-gap mem-
that the vapor permeate flux could be enhanced brane distillation (AGMD) module with internal
from 53 % to 92 % compared with the latent heat recovery configuration (Geng
4 Hollow Fiber Modules for Desalination
Fig. 4 (continued)
Hollow Fiber Modules for Desalination 5
Hollow Fiber Modules for Desalination, Fig. 4 Novel module design and fabrication: (a) structured-straight
module; (b) curly-fiber module; (c) central-tubing module; (d) spacer-wrapped module; e spacer-knitted module
6 Hollow Fiber Modules for Desalination
Th
hollow fiber membrane
polypropylene net
heat exchange
hollow fiber Hot
Feed
Cold Cold
Feed Feed
Hollow Fiber Modules for Desalination, Fig. 6 Schematic presentation of the novel AGMD module
et al. 2014). The novel module is consisted of hot feed side in membrane. The model was used
parallel hollow fiber membranes and heat to calculate the temperature and the vapor per-
exchanged hollow fibers (Fig. 6). They investi- meate flux distributions along the hollow fiber
gated the influences of operating factors such as membrane. The performance of the AGMD mod-
feed flow rate, feed temperature, and feed initial ule was experimentally demonstrated under dif-
concentration on AGMD process. Simulta- ferent operating conditions, and the results
neously they established a theoretical model showed that the energy of AGMD process was
based on the energy and mass balances of the
Hollow Fiber Modules for Desalination 7
recycled effectively, simultaneously, a high Li B, Sirkar KK (2005) Novel membrane and device for
gained output ratio (GOR) of 5.7 was obtained. vacuum membrane distillation desalination process.
J Membr Sci 2005(257):60–75
Liying Liu, Lijun Li, Zhongwei Ding, Runyu Ma, Zurong
Yang (2005) Mass transfer enhancement in coiled
hollow fiber membrane modules. J Membr Sci
References 264:113–121.
Teoh MM, Bonyadi S, Chung T-S (2008) Investigation of
Hongxin Geng, HaoyunWu, Pingli Li, Qingfeng He different hollow fiber module designs for flux
(2014) Study on a new air-gap membrane distillation enhancement in the membrane distillation process.
module for desalination. Desalination 334:29–38 J Membr Sci 2008(311):371–379
Gilron J, Song L, Sirkar KK (2007) Design for cascade of Wu Chunrui, Jia Yue, Chen Huayan, Wang Xuan, Lu
cross flow direct contact membrane distillation. Ind Xiaolong (2010) Membrane distillation and novel inte-
Eng Chem Res 2007(46):2324–2334 grated membrane process for reverse osmosis drained
Chen Huayan, Wu Chunrui, Jia Yue, Wang Xuan, Lu wastewater treatment. Desalination Water Treat
Xiaolong (2011) Comparison of three membrane dis- 18:1–6
tillation configurations and seawater desalination by Yanga X, Wanga R, Fane AG (2011) Novel designs for
vacuum membrane distillation. Desalination Water improving the performance of hollow fiber membrane
Treat 28:321–327 distillation modules. J Membr Sci 2011(384):52–62
M
Multi-effect Membrane Distillation, Fig. 1 Two different modes of obtaining increased recovery by operating with a
series of cascades: (a) with interstage brine heating and (b) without interstage brine heating
The MEMD Processes with VMD Modules of MSF for the same condition. Additionally,
MSVMD has some advantages over MSF, such
By replacing the flash chambers of MSF desali- as operation at lower temperature, the use of low
nation systems with membrane distillation mod- temperature heat sources, and the use of inexpen-
ules, a small-scale and off-grid desalination sive polymer materials.
system (Fig. 2) can be built (Edward The memsys has developed a novel vacuum
et al. 2013). The results of model analysis showed multi-effect membrane distillation (V-MEMD)
that the multistage vacuum membrane distillation module (Zhao et al. 2013). The V-MEMD pro-
(MSVMD) system can achieve the performance cess is achieved by many single stages
Multi-effect Membrane Distillation 3
BRINE
decreasing Pp REJECT
MD MD
@ PP TO VAC @ PP TO VAC
· ∼0
m m· ∼ 0
Qin
CONDENSER CONDENSER
FEED IN
COOLER COOLER
PERMEATE
OUT
j=1 j=n
Multi-effect Membrane Distillation, Fig. 3 Schematic diagram of the integrated system of AGMD and HEN
Multi-effect Membrane
Distillation, external heater
Fig. 4 Schematic
presentation of hollow
fiber-based MEMD process
Th,i=90 °C Tc,o=85°C
vapor
dense-Wall fiber
porous fiber
retentate cold feed
Th,o=29 °C Tc,i=25°C
distillate
Td=26 °C
system that can keep high energy efficiency and organic acids from their respective dilute aqueous
improve the productive rate of the system. It also solutions. Using this MEMD process, Xiaojun Li
gives the optimal operating conditions and et al. studied the concentration of aqueous sulfu-
explicit stream data. The cost difference between ric acid solution (Xiaojun Li et al. 2012). The
HENs with and without the MD streams is con- GOR value obtained was much higher than that
sidered as the partial cost of pure water resulting in traditional and other modified membrane dis-
from the MD process. tillation processes. The maximum value of GOR
A heat recovery technology in AGMD process could reach 11.5. And in a long-term stability test
using a two hollow-fiber-set membrane module (lasting for more than 30 days), the MEMD mod-
has been developed. In the module, the hot brine ules were kept in good condition, which demon-
flows through a porous hydrophobic membrane, strated the stability of this MEMD process.
the vapor through the wall of the porous hydro- A conception of continuous-effect membrane
phobic membrane is condensed on the wall of distillation (CEMD) was proposed in 2013 Yao
dense wall fibers and warms up the cold brine et al. (2013). The CEMD process based on hollow
flow. The configuration of MEMD process is fiber AGMD module and the MEMD process
presented in Fig. 4, which includes the AGMD with an AGMD module are exactly the same.
module described before and an external heat However, the research studied two kinds of
exchanger. Enrichment experiment of semi- CEMD modules made from different membrane
volatile organic acids from aqueous solutions by fibers. The influences of operating conditions on
this MEMD process has been completed (Ban the performance of CEMD process have been
Rui et al. 2012). The influence of operating con- investigated. Within the studied experimental
ditions for the performance of MEMD process range, the maximum GOR value could reach
has been studied. The GOR of this experiment 13.8. The theoretical model successfully
can be 9.84 and the acid rejection rate can be predicted the possible ways to obtain a higher
99.93 %. The results present that the MEMD GOR value. And the experiment data showed
process can be potentially applied to enriching agreement with theoretical conclusions.
Multi-effect Membrane Distillation 5
Acid Gas: Effect on Membrane permeability and H2S/CO2 selectivity for a range
Properties of polymeric membranes. The study of porous
membranes for acidic gas removal is limited,
Colin A. Scholes even though both H2S and CO2 have smaller
Department of Chemical & Biomolecular kinetic diameters than CH4. In the natural gas
Engineering, The University of Melbourne, sweetening industry, both cellulose acetate- and
Parkville, Australia polyimide-based membranes have been
commercialized.
Prolonged exposure to both H2S and CO2 can
Acidic gas removal is the largest application of lead to plasticization and degradation of the poly-
gas separation membranes and a vital process in meric membrane over time. This is because the
the natural gas processing industry. Membranes acidic nature of the gases means they will readily
used in this process are designed to separate H2S interact with the polymeric chains, disrupting
and CO2, and this process is known as natural gas chain packing and lubricating polymer chain
sweetening. This is readily required for motion, resulting in more rubbery behavior.
low-quality natural gas reserves, which need to Membrane degradation by these gases is greatly
be processed to achieve pipeline specifications of enhanced if water is present, because of the weak
CO2 <2 mol% and H2S <4 ppm (Baker 2001). acidic dissociation of these gases (Scholes
The removal of acidic gases is also required for et al. 2009).
biogas and gasification, where H2S and CO2 are For inorganic and metallic membranes, H2S is
separated from CH4, CO, and H2. For natural gas of particular concern, because of the effect sulfur
sweetening, the membrane must exhibit high per- can have on the membrane material
meability for H2S and CO2, with a large selectiv- (Lu et al. 2007). A good example of this is in H2
ity relative to methane. separation with Pd-based membranes. The pres-
In general, nonporous polymeric membranes ence of H2S leads to membrane brittlement and
are applied in acidic gas removal, taking advan- performance degradation because of lattice
tage of the solution-diffusion mechanism and the expansion on the formation of Pd-S. Hence, in
high solubility of H2S and CO2, compared to applications such as gasification, it is necessary
CH4. Also polymeric membranes almost always for the gas to have H2S removed prior to the gas
demonstrate selectivity for H2S over CO2, again separation membrane, use sacrificial layers, or
because of the higher condensability of H2S com- add sulfur-resistant materials.
pared to CO2, as demonstrated by the difference
in critical temperature. Table 1 provides the H2S
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_817-3
2 Acid Gas: Effect on Membrane Properties
Acid Gas: Effect on Membrane Properties, Table 1 H2S permeabilities (barrier) and H2S/CO2 selectivity in a range
of polymeric membranes
H2S permeability H2S/CO2
Ethyl cellulose 320 3.8
Nylon 0.34 3.86
PDMS 5,100 1.6
Polyethylene 36 2.84
PTMSP 21,400 1.2
Carbon Capture and Storage (CCS) process occurs at lower pressures, low CO2 par-
tial pressures, and often around ambient temper-
Colin A. Scholes ature. Oxy-fuel combustion is pure oxygen firing
Department of Chemical & Biomolecular of the combustion process. This excludes N2 from
Engineering, The University of Melbourne, VIC, the combustion zone and produces a flue gas
Parkville, Australia consisting of CO2 and H2O. Carbon capture is
achieved through water removal. However, the
very high flame temperature often dictates flue
Carbon capture and storage (CCS) is a proposed gas recycling, and critically this strategy requires
strategy to separate carbon dioxide from indus- the separation of high purity O2 from air, which is
trial gases and store that carbon on a geological commonly achieved through cryogenic methods.
timescale. This is a response to the perceived Precombustion capture is the gasification of the
threat industrial carbon dioxide emissions have carbon-based fuel into synthetic gas, also called
in producing anthropogenic climate change syngas, consisting of CO and H2. This syngas is
(IPCC 2007). CCS is divided into three distinct an important industrial feed gas that is used in a
stages, the capture of the carbon dioxide from the wide range of processes, such as Fischer-Tropsch
emission source, the compression and transporta- synthesis. For power generation, H2 production is
tion of CO2 to the storage site, and the final often maximized through the water gas shift reac-
storage of CO2 for long periods of time (IPCC tion, resulting in high-pressure gas mixtures of
2005). CO2, CO, and H2. Separation of CO2 is achieved
The capturing of CO2 is predominately asso- before H2 undergoes combustion. This separation
ciated with large stationary point sources and in strategy takes advantage of the high pressure and
particular coal-fired power stations. The strate- CO2 partial pressure before combustion.
gies to capture carbon emissions from these Carbon capture has also been applied to other
sources can be classified into three distinct industrial applications, such as natural gas sweet-
approaches: post-combustion capture, oxy-fuel ening, for the removal of acidic gases to meet
combustion, and precombustion capture pipeline specifications, as well as in natural gas
(Table 1). reforming for ammonia production.
Post-combustion capture is the separation of A range of separation technologies have been
CO2 from flue gases after the combustion pro- applied to carbon capture, including solvent sep-
cess. This is primarily a separation of CO2 from aration, membrane gas separation, adsorption
N2, as well as water and other minor components, technology, cryogenic separation, and mineral
such as CO, SOx, and NOx. The separation carbonation. The current commercial technology
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_819-4
2 Carbon Capture and Storage (CCS)
Carbon Capture and Storage (CCS), Table 1 Carbon capture strategy conditions and gas compositions
Post-combustion Oxy-fuel combustion Precombustion
Pressure (bar) 1 1 30
Composition (mol. frac.)
CO2 0.11 0.87 0.40
N2 0.62 – –
H2 – – 0.55
O2 0.04 0.05 –
H2O 0.23 0.08 0.02
CO – – 0.03
of choice is physical and chemical solvent tech- above the reservoir that forms the necessary geo-
nology, with membrane gas separation having logical trap. Possible geological sites for CO2
been commercial proven in natural gas geosequestration include disused oil and gas
sweetening. fields, saline aquifers, as well as deep coal
Transportation of captured CO2 to the storage seams. Currently, CO2 is geosequestrated com-
site is undertaken through shipping (low temper- mercially as part of enhanced oil recovery
ature and low pressure) or pipelines (high pres- procedures.
sure and ambient temperature). The method of
transportation is dependent on distance and geog-
raphy between the source and storage sites.
References
Storage of carbon for extended periods of time
can be achieved through geosequestration, deep IPCC (2005) IPCC special report on carbon dioxide
ocean storage, or mineralization. capture and storage. Prepared by working group III
Geosequestration is the injection of supercritical of the Intergovernmental Panel on Climate Change.
CO2 into geological formations, generally sedi- Cambridge University Press, Cambridge, UK
IPCC (2007) IPCC the physical science bases. Contribu-
mentary basin, over a kilometer underground. tion of working group 1 to the fourth assessment report
Importantly, the geological formation must con- of the Intergovernmental Panel on Climate Change.
tain a suitable reservoir rock, with high perme- Cambridge University Press, Cambridge, UK
ability and porosity for CO2, as well as a seal rock
D
NOx Effect on Membrane Properties, Table 1 NO permeability (barrer) through glassy polymeric membranes
Polysulfone Matrimid 5218 6FDA-TMPDA
NO permeability (barrer) 3.1 0.6 3.7 0.6 168 16
have similar degradation performance on mem- and nitrogen dioxide through polytetrafluoroethylene.
branes as those observed for SOx. Macromolecules 3:366–371
Scholes CA, Kentish SE, Stevens GW (2009) Effect of
minor components in carbon dioxide capture using
polymeric gas separation membranes. Sep Purif Rev
References 38:1–44
SOx, Effect on Membrane Properties, Table 1 SO2 permeabilities (barrer) and SO2/CO2 selectivity in a range of
polymeric membranes
SO2 permeability SO2/CO2
Cellulose triacetate 270 48
Polyacrylate 1,700 41
Polyethylene glycol 4,100 44
Polyamide-6-b-ethylene oxide 1,000 7.6
Polytetrafluoroethylene-co-ethylene 2.6 1.32
Membrane Crystallization (MCr) gradient) Dusty Gas Model is applied; for thin
film composite membranes (mass transfer in liq-
Efrem Curcio uid phase under pressure or concentration gradi-
Department of Environmental and Chemical ent), Solution-Diffusion Model is employed.
Engineeering, University of Calabria, Rende Morphological and physicochemical parame-
(CS), Italy ters of the membranes, such as porosity, rough-
ness, or hydrophilic/hydrophobic character,
affect significantly the nucleation kinetics. In
Membrane operation is aimed at promoting the fact, the formation of a critical nucleus (having
formation of crystals from supersaturated solu- 50 % probability to growth or dissolve) is an
tions. The concept of membrane crystallization activate process that imposes the necessity to
combines the principles of mass and heat trans- overcome a Gibbs energy barrier DG* that, for
port through membranes with the theory of het- homogeneous nucleation occurring in the bulk of
erogeneous nucleation occurring at the interface the solution, is given (according to the Classical
with polymeric films (Drioli et al. 2005). Nucleation Theory (Drioli et al. 2015)) by:
Crystallization from solution is driven by
supersaturation S, defined as the ratio between 16 3 O 2
DGhomogeneous ¼ pgL (2a)
the actual solute concentration c and the equilib- 3 Dm
rium value c* (saturation):
where gL is the surface tension of the nucleus-
c
S¼ (1) liquid interface, O the molar volume of the solute,
c and Dm the chemical potential gradient between
the crystalline phase and the mother solution. The
The selective removal of solvent through appro- corresponding critical nucleus R* is given by:
priate membranes is used to increase the concen-
tration of the solute up to the required 2gL O
Rhomogeneous ¼ (2b)
supersaturation. Alternatively, membranes are Dm
used to selectively feed an antisolvent to induce
a demixing effect that generates supersaturation. Membrane surfaces act as a promoter of crystal-
Mass transport depends on the specific typol- lization by lowering the activation barrier to the
ogy of employed membranes: for microporous nucleation stage, thus allowing molecules to
hydrophobic membranes (mass transfer in vapor aggregate in conditions of supersaturation that
phase under temperature and/or concentration would not be adequate for the spontaneous
Membrane Crystallization (MCr), Table 1 Critical nucleus (R*) and Gibbs free energy ratio between heterogeneous
and homogeneous nucleation (DGheterogeneus/DGhomogeneous) as a function of physicochemical parameters of the
membrane
Parameter R* DGheterogeneus/DGhomogeneous
2gL O
1 3
2 4 cos y þ 4 cos y
Contact angle (y), ideal surface 1 3
Dm
h 2
i h i3
Porosity (e) 2OgL
1 e ðð1þ cos yÞ 2 ð1þ cos yÞ2
4 ð2 þ cos yÞ ð1 cos yÞ 1 e ð1 cos yÞ2
1
Dm 1 cos yÞ2
4 Y ð cos y 3 cos y þ 2Þ
Wenzel roughness (r) 2OgL 1 3 3
Dm Y
r cos y ð1þ cos yÞ2
Y¼ cos y ð1þ cos yÞ2
nucleation rate (lower DG*) results in a shorter poly(n-buthyl methacrylate) (P pu BMA) show-
induction time. This is particularly evident in the ing ester functionality, polyimide (PI) that
crystallization of proteins: macromolecules dis- includes both hydrogen-bond acceptor imide
play a rather asymmetric and weak bonding con- functionality and carbonyl groups, ethylene/
figuration at their surfaces and tend to aggregate acrylic acid (EAA) copolymer with only the car-
in n-mers that diversify the shape and size of boxyl moiety. Power X-ray Diffraction analysis
lattice units, thus making ordered attachment for showed the occurrence of preferred orientation
growing units less probable. (PO) depending on the strength of the
Experiments carried out on various hydro- intermolecular interactions occurring at the
soluble proteins (such as lysozyme, trypsin, polymer-crystal interface during nucleation:
b-glucosydase) showed the possibility to obtain from nonspecific adsorption (PDMS, PnBMA,
a crystalline product in shorted times with respect and PS) to oriented arrangement of molecules in
to those measured when using conventional the crystalline lattice (EAA, PI, and PVDF)
vapor diffusion techniques under the same super- (Curcio et al. 2014).
saturation level (Curcio et al. 2010). Moreover,
X-ray diffraction analysis by synchrotron radia-
tion confirmed a high structural order of crystals References
grown on microporous membranes (i.e., polypro-
pylene). Crystallization experiments on metals- Curcio E, Curcio V, Di Profio G, Fontananova E, Drioli
E (2010) Energetics of protein nucleation on rough
proteins have also resulted in a new orthorhombic
polymeric surfaces. J Phys Chem B 114:13650–13655
form P21212 of the complex Lysozyme-Co2+. Curcio E, López-Mejı́as V, Di Profio G, Fontananova E,
In order to understand the effect of the chem- Drioli E, Trout BL, Myerson AS (2014) Regulating
istry of surface on the heterogeneous nucleation, nucleation kinetics through molecular interactions at
the polymer–solute interface. Cryst Growth Des
Curcio et al. (2014) investigated the mechanisms
14(2):678–686
of acetaminophen (ACM) crystal formation due Drioli E, Criscuoli A, Curcio E (2005) Membrane
to specific solute-surface interactions on contactors. Fundamentals, potentialities and applica-
polydimethylsiloxane (PDMS) with siloxane tions. Elsevier, Amsterdam
Drioli E, Di Profio G, Curcio E (2012) Progress in mem-
functional groups Si O Si forming the back-
brane crystallization. Curr Opin Chem Eng
bone of silicones, partially fluorinated elastomer 1(2):178–182
polyvinylidenedifluoride (PVDF), polystyrene Drioli E, Di Profio G, Curcio E (2015) Membrane-assisted
(PS) having weak electron-donor phenyl rings, crystallization. Imperial College Press, London
A
In the case of a driving force generated by a Generally, in order to avoid wetting, hydro-
temperature gradient, the system is named ther- phobic membrane materials are preferred for
mal membrane crystallizer; when the driving aqueous feed solutions, while hydrophilic mem-
force is obtained by an activity gradient, gener- branes can be used for oleophilic solutions. In the
ated by a difference in ionic strength, the system most common arrangement, the distillate side of
is named osmotic (or isothermal) membrane the membrane consists in a condensing fluid,
crystallizer. often the pure solvent, at a lower temperature
Under the action of the driving force, solvent than the feed side in the case of thermal activation
molecules migrate, in vapor phase through the of the driving force, or in a stripping solution
porous membrane structure, from the site where consisting in a hypertonic solution of inert salts
their chemical potential is higher toward the (NaCl, MgCl2, CaCl2, etc.) in the case of the
lower chemical potential subsystem, thus gener- isothermal configuration.
ating supersaturation and, hence, nucleation and While for the crystallization of inorganic sub-
crystal growth in the crystallizing solution. The stances or low molecular weight organic com-
specific mechanism for mass transport depends pounds, the thermal system can be affectively
on the operational configuration of the membrane used, for the crystallization of heat-sensitive mol-
crystallizer. Two cases exist: (1) solvent evapo- ecules, like proteins, the osmotic configuration
ration membrane crystallizer (thermal or isother- appears more appropriate tank to its milder oper-
mal) in which solvent is removed in vapor phase ating conditions (Curcio et al. 2001).
from the crystallizing solution and (2) antisolvent
membrane crystallizer where an antisolvent is
dosed inside the crystallizing solution by means
References
of the membrane. Static (quiescent) and dynamic
process can be performed. In the first case, the Atkins PW (1998) Physical chemistry, 6th edn. Oxford
feed and the distillate solutions are quiescent, University Pres, Oxford
while in the second case, those two solutions are Curcio E, Criscuoli A, Drioli E (2001) Ind Eng Chem Res
circulated in forced solution flow environment, 40:2679–2684
generally in a condition of laminar flow.
P
nucleation will be enhanced by increasing the grow into crystals while the fractal clusters grow
surface area of the substrate. The nucleation into larger clusters. This simple mechanism can
work depends on two main parameters: the exter- be generalized to describe heterogeneous nucle-
nally controlled supersaturation ratio and the ation on irregular substrates such as porous sur-
material surface/solution composition-dependent faces. From a technological point of view, the
interfacial energy. Molecules dispersed in solu- control of surface porosity in producing mem-
tion are first adsorbed on the surface by means of branes can be easily achieved, so that specific
nonspecific attractive interactions. The irregular membrane nucleants, having the desired value
structure may physically block the lateral migra- of porosity which might be used to achieve the
tion of the adsorbed protein molecules into the desired heterogeneous/homogeneous activation
concaves, so that they are forced to be packed Gibbs energy ratio, can be produced.
into compact aggregates. The trapping of mole-
cules on the surface may result in a relatively
higher local supersaturation, which would
References
increase the possibility of nucleation compared
with that on an ideally flat surface. Here, nucle- Horbett TA (1992) In: Ahern TJ, Manning MC (eds)
ation will follow with the formation of critical Stability of protein pharmaceuticals, part 1. Plenum
clusters comprising molecules forming suitable Press, New York
Kornberg RD, Darst SA (1991) Curr Opin Struct Biol
bond angles with their neighbors, while the mol-
1:642–646
ecules in a randomly packed compact structure Simone S, Curcio E, Di Profio G, Ferraroni M, Drioli EJ
may form a fractal cluster, which cannot work as (2006) Memb Sci 283:123–132
a nucleus for crystal growth. Critical clusters then
M
generation rate will fix which form will effec- et al. 2007b). Accordingly, high control of the
tively be grown. When the rate of variation of membrane-based process provides the possibility
supersaturation is low, due to the low evaporation to induce polymorphic selection during crystalli-
rates through the membrane, if nuclei of the more zation by switching between a kinetic and a ther-
stable structure have time to grow at the expense modynamic control of the nucleation stage thus
of the less stable forms via solvent-mediated allowing the production of either a metastable or
transfer of solute, a “thermodynamic control” a stable structure (Di Profio et al. 2009).
and the more stable polymorph will selectively
(or prevalently) be obtained. However, for higher
evaporation rates, the increase in the metastable References
zone width induces nucleation at higher values of
supersaturation. In this situation, the conversion Di Profio G, Tucci S, Curcio E, Drioli E (2007a) Chem
Mater 19:2386–2388
from the metastable to the stable phase could not
Di Profio G, Tucci S, Curcio E, Drioli E (2007b) Cryst
be fast enough with respect to the growth of the Growth Des 7:526–530
former, so that the growth of the kinetically Di Profio G, Curcio E, Ferraro S, Stabile C, Drioli
favored form (metastable), which might be also E (2009) Cryst Growth Des 9:2179–2186
Kashchiev D (2001) Nucleation, basic theory with appli-
the first to appear according with the Ostwald rule
cations. Butterworth, Oxford
of stages, is observed. In this case the overall Ostwald WZ (1987) Phys Chem 22:289–330
process is “kinetically controlled” (Di Profio
H
sffiffiffiffiffiffiffiffiffi
co1 coshð#Y 1 Þ
k1 d2 1 vmax ¼
W¼ ; k1 ¼ co2 coshð#½1 Y 1 Þ
D YXO kMO2
pffiffiffiffiffiffiffiffi #2
cd
D o
k1 D o J¼ c þ c2 2c1 1 ½2Y 1 1 þ #
o o 2
J¼ c (3) d 1 2
tanh# cosh#
(7)
D 2 o
J¼ # c (4) with
d
with #2
co1 1 ½2Y 1 1
sffiffiffiffiffiffiffiffiffiffiffiffiffi 2
vmax d2 #2
#¼ ¼ c2 1 þ ½2Y 1 1 :
o
(8)
DY XO2 2
D o #2 The Y1 inflection point can be determined by
J¼ c cd (5)
d 2 Eq. 8 and then the mass transfer rate by Eq. 7 as
well. Detailed solution of Eq. 1 is published by
I. n order to overcome the diffusive mass transport Nagy (2011), recommended explicit expression
limitation of nutrients, especially of the sparingly for the mass transfer rate. The biofilm can involve
soluble oxygen, the substrate might be fed on several substrates with several parallel and/or
both sides of the biofilm applying oxygen perme- consecutive reactions as this is the case of aerobic
able support layer. The sum of the mass transfer wastewater treatment. System of the differential
rates for first- and zero-order reactions can be mass balance equations of the reactants should be
expressed by Eqs. 6 and 7, respectively. The solved in order to get their concentration distri-
substrate concentrations of the two sides of the butions and the mass transfer rates of the trans-
biofilm layer are co1 and co2. The substrate concen- ferring substrates.
tration curve has inflection point at Y = Y1 (Y =
y/d):
pffiffiffiffiffiffiffiffi References
k1 D 1
J¼ 1 co
tanh# cosh2 ð#Y 1 Þ 1 Gavin L, Gillian DL (2012) Microbial biofilms: current
research and application. Caister Academic Press,
1 Christchurch
þ 1 co (6) Nagy E (2011) Basic equations of the mass transport
cosh2 ð#½1 Y 1 Þ 2
through a membrane layer. Elsevier, Amsterdam
with
B
Biocatalytic Membrane Reactor, Mass Transport in, Table 1 Expressions of the important biocatalytic reactions
Substrate inhibition: Q ¼ KMi þcþc
rmax c
2 =K
c
are constant; and the process is steady state. Thus, Y
J ¼ b c0 cd
the mass balance equation can be given for a plain ePe=2 ½ðPe=2ÞsinhY þ YcoshY
membrane layer as follows, applying, e.g., the (3)
Michaelis-Menten (MM) kinetics (c denotes the
concentration): with (c = cd at y = d and c = c at y = 0;
Pe =nd/D)
d2 c dc vmax c
D u ¼0 (1)
dy2 dy K M þ c D ð½Pe=2tanhY þ YÞ
b¼
d tanhY
The source term can be different in biocatalytic
reactions; the most often applied equations are The mass transfer rates are given by Eqs. 4 and 5
listed in Table 1. The inhibited reaction can take for cases A and B, respectively, for zero-order
place in both the enzymatic and microbial reaction as limiting case of MM kinetics (k0
reactions. denotes the reaction rate constant):
Two important cases can be discussed, namely,
when the outlet (at y = d) diffusive flow is zero D 0 W2 1
(dc/dy = 0, no sweep phase on the permeate side, J ¼ c Pe 1 Pe (4)
d Pe e
case A) and dc/dy 6¼ 0 at y = d (there is sweep
phase on the permeate side, case B). The mass and
transfer rates are given by Eqs. 2 and 3 for cases
A and B, respectively, for first-order reaction as D Pe
limiting case of MM kinetics (Nagy 2011): J¼
d 2
2 ePe=2 ePe
Pe ð 1 TÞ c
0
cd (5)
þ Y tanhY þ PeY
2 sinhðPe=2Þ 1T
D 4
J¼ c0 (2)
d Pe with
tanhY þ Y
2
sffiffiffiffiffiffiffiffiffi
W2 k0 d2
with T ¼ 2 ePe ½1 þ Pe 1 ; W ¼
Pe Dc0
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffi
Pe2 k1 d2 The flow through this membrane is proportional
Y¼ þ W2 ; W ¼
4 D to the transmembrane pressure drop and inversely
proportional to the fluid viscosity (Darcy law,
Eq. 6) (k is the permeability and m is the fluid
viscosity):
Biocatalytic Membrane Reactor, Mass Transport in 3
Then, one can get from Eq. 6, for capillary mem- The axial pressure distribution is given in entry
brane, as: “Hollow Fiber Enzymatic Reactor, Modelling
of.”
1 @ @ ðruM Þ k1 @ @p
r r M ¼ 0 (7)
r @r @r m r @r @r
References
When Eq. 7 is integrated twice with respect to r
with boundary conditions, at r = ro then pM = pt Bird RB, Stewart E, Lightfoot EN (1960) Transport phe-
and at r = ro + d then pM = pe, one gets the nomena. Wiley, New York
radial pressure and velocity distributions (Nagy Drioli E, Giorno L (1999) Biocatalytic membrane reactor.
2011, pp. 178) within the membrane as: Taylor & Francis, London
Nagy E (2011) Basic equations of the mass transport
through a membrane layer. Elsevier, Amsterdam
pt ðzÞ pe ðzÞ r Seidel-Morgenstern A (2010) Membrane reactors. Wiley-
pM ðr, zÞ ¼ ln þ pt ðzÞ (8)
lnð1 þ d=ro Þ ro VCH, Weinheim
B
Mass Transport; Hollow Fibre Enzymatic Reac- (2011) for the general Michaeli-Menten kinetics
tor: Modelling”). or bioreactions with two substrates feeding on the
two sides of the membrane reactor. This method
d2 p t 8uo mB 1 can take into account the effect of the in-space
¼ 2 fcosh½lðL zÞ
dz 2 ro lð1 þ BÞsinhðlLÞ l2 and/or time variable or concentration dependent
parameters on the process.
h1 þ f ð1 þ BÞicoshðlzÞg (1)
Food Packaging, Membranes for particular, the properties of films produced from
biopolymers can be improved by well-developed
Alberto Figoli techniques as blending, use of plasticizers, and
The Institute on Membrane Technology loading with nanoparticles.
(CNR-ITM), Rende, CS, Italy MAP is frequently used in the case of fresh, or
minimally processed, respiring, products, like
vegetables and fruits. MAP aims at maintaining
Synonyms an optimum gas balance in the package head-
space. In particular, a selected ratio between car-
Food packaging; Membrane operations bon dioxide and oxygen is often required in order
to allow living vegetal tissues respiration and
Food packaging is often defined as a heteroge- survival, at the same time preventing aging and
neous group of boxes, envelops, papers, and coat- deterioration. The respiratory quotient
ings that are employed in order to increase (RQ) (Cameron et al. 1995) is defined as the
foodstuffs shelf life (European Council 1994). optimum balance between O2 and CO2 that
This means that any food packaging system should be maintained within the package; this
aims to avoid/slow down bacterial/fungal con- value is peculiar of each fruit or vegetable spec-
tamination and deterioration and, at the same imen. MAP requires films having specific
time, to ensure the maintenance of properties as permselectivity to gases, such as carbon dioxide
firmness, color, and flavor as long as possible. and oxygen, rather than impenetrable materials.
Nowadays, beside the traditional concept of In this case, gas separation membranes can be
packaging as impenetrable barrier, novel systems particularly useful, while membrane materials
are required, such as modified atmosphere pack- can be selected, in each case, on the basis of
aging (MAP) and active packaging (AP). Poly- their permselectivity to oxygen and carbon diox-
meric membranes, thanks to their unique ide. By varying the ratio between polymer and
properties of permselectivity and ability to sus- additive concentrations, dense membranes in
tain controlled delivery, can be successfully used modified polyether ether ketone (PEEK-WC)
for food packaging; indeed, their properties can and poly-alpha-pinene (PaP) were reported to
be exploited for such innovative packaging sys- match the values required by different products,
tems (Figoli et al. 2010), as also shown in Fig. 1. as apple, Brussels sprouts, carrot, green pepper,
Furthermore, the expertise of membranologists and turnip (Torchia et al. 2004).
could help to produce food packaging systems A wide range of CO2/O2 permselectivity
from biodegradable nonpolluting sources. In values can be obtained by using packaging
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_851-1
2 Food Packaging, Membranes for
Food Packaging,
Membranes for,
Fig. 1 Application of
membrane in traditional
food packaging, revised
from ref. (Figoli et al. 2010)
structures based on biopolymers. These are with use of biopolymers. Films based on starch,
defined as biodegradable materials that can be corn zein, and PLA can be used for delivery of
decomposed by microorganisms and enzymatic lysozyme, nisin, and natural antimicrobial com-
degradation. Starch, cellulose, chitosan, pounds (Torchia et al. 2004); literature reports
polycaprolactone (PCL), and polylactic acid several other interesting examples of
(PLA) are some examples of biopolymers suit- biopolymer-based films as active packaging sys-
able for food packaging (Mensitieri et al. 2011). tems (Atarés et al. 2011; Chana-Thaworn
In literature, several studies already demon- et al. 2011; Gemili et al. 2009; Sánchez-González
strated that biopolymers can compete with et al. 2011). Microencapsulation is another strat-
oil-derived plastics for packaging of different egy for controlled delivery. It has been shown
fruit and vegetable species (see for instance ref. that it can be used coupled to traditional packag-
Conte et al. 2009; Kantola and Helen 2001; ing materials or biopolymers for active packaging
Muratore et al. 2005; Srinivasa et al. 2002). How- systems releasing natural antimicrobials (Guarda
ever, hydrophilicity and poor mechanical proper- et al. 2011) or aroma compounds (Marcuzzo
ties are the main drawbacks for use of et al. 2010).
biopolymers as food packaging systems. Several
strategies, already developed in the field of mem-
brane science and technology, can be useful to
References
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(Torchia et al. 2004; Abdorreza et al. 2011), of sago starch films. Food Hydrocoll 25:56–60
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some antioxidants in the HPMC film properties and
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41:1393–1411
et al. 2011). Belbekhouche S, Bras J, Siqueira G, Chappey C,
Active releasing packaging systems are used Lebrun L, Khelifi B, Marais S, Dufresne A (2011)
to control the delivery of specific substances to Water sorption behavior and gas barrier properties of
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Polym 83:1740–1748
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entrapped in the polymeric matrix can be useful film permeability needs for modified-atmosphere
in this case, similar to what already developed in packaging of lightly processed fruits and vegetables.
the medical field (Baker 2002). Membranes can Hort Sci 30:25
Chana-Thaworn J, Chanthachum S, Wittaya T (2011)
be used to sustain the controlled delivery of anti- Properties and antimicrobial activity of edible films
microbial substances, such as allyl isothiocyanate incorporated with kiam wood (Cotyleobium
(AITC) (Lee et al. 2008) or oxalic acid (Figoli lanceotatum) extract. LWT Food Sci Technol
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P
References
However, catalytic membranes deserve spe- membrane, because permeation does not take
cial advantages that in many cases justify these place through the polymer matrix, but through
additional efforts. the membrane pores (Vankelecom 2002).
In the design of a catalytic membrane, major However, the membrane material is relevant
issues in the polymer selection are the mechani- for the membrane stability and surface properties,
cal, thermal, and chemical stability under reac- such as wettability and fouling tendency.
tion conditions. The membrane preparation conditions
What is fundamental is to realize a stable depend on the membrane material and the
catalyst immobilization in order to avoid its desired structure and morphology. In the case
leaching out from the membrane. Different of a catalytic membrane, the incorporation of
immobilization strategies can be used in order the catalyst complicates the process because
to achieve these goals: covalent bonds, electro- the catalyst should be firmly entrapped in the
static and weak interactions (van der Waals or membrane and the catalyst structure and activity
hydrogen bonds) of the catalyst with the mem- has to be preserved during the membrane prep-
brane, or catalyst encapsulation. aration procedure.
A good affinity for the catalyst is desirable in Moreover, the properties (including transport
order to avoid catalyst leaching and to have a properties) of the catalytic membrane are usually
good adhesion between the polymer and the cat- different than those of the reference membrane
alyst, with an optimal dispersion of the prepared in the same conditions but without the
second one. catalyst.
The affinity between a compound and a poly- Different techniques for membrane prepara-
meric material can be often anticipated by the tion are today available and can be opportunely
calculation of the affinity parameters (Van employed also to prepare catalytic membranes:
Krevelen 1990; Barton 1990). These parameters phase separation, coating, interfacial polymeriza-
reflect the ability to form hydrogen bond, polar, tion, sintering, stretching, and track etching are
and van der Waals interactions in condensed some examples (Strathmann et al. 2006).
phase. In some cases, the catalyst is entrapped in/on
The polymer/catalyst affinity can be also the membrane already formed, by covalent
improved by an appropriate chemical functiona- bonds, electrostatic interactions, absorption by
lization of one or both components. weak interactions, or physical entrapment. In
In the case of application in liquid phase, alternative, the catalyst immobilization can be
ideally, the solvent used for the reaction needs carried out in the same time of the membrane
to be a non-solvent for the catalyst, and the mem- formation, for example, by dispersing the cata-
brane has not to have an excessive swelling in it. lyst in the polymer casting solution and succes-
It is also possible in some cases to improve the sive phase separation (Drioli and Fontananova
catalyst retention in the membrane by the catalyst 2010).
enlargement as: dendrimers, hyperbranched
polymers, and catalyst bound to a soluble poly-
mer (Dioos et al. 2006).
References
Mass transfer of the reagents to the catalytic
sites, and of the products away from them, should Barton AFM (1990) Handbook of polymer-liquid interac-
be fast enough in order to not limit the reaction, tion parameters and solubility parameters. CRC Press,
but, at the same time, the contact time catalyst/ Boca Raton
reagent should be also appropriate. Dioos BML, Vankelecom IFJ, Jacobs PA (2006) Aspects
of immobilisation of catalysts on polymeric supports.
For a porous membrane, the choice of the Adv Synth Catal 348:1413–1446
polymer material is of less importance for trans- Drioli E, Fontananova E (2010) Catalytic membranes
port properties in comparison with a dense embedding selective catalysts: preparation and
Heterogenization or Immobilization of a Catalyst 3
applications. In: P. Barbaro and F. Liguori (eds.), Strathmann H, Giorno L, Drioli E (2006) An introduction
Heterogenized homogeneous catalysts for fine to membrane science and technology. Publisher CNR,
Chemicals Production, Catalysis by Metal Complexes Roma. ISBN 88-8080-063-9
33, Springer, Berlin Van Krevelen DW (1990) Properties of polymers, 3rd edn.
Gladysz JA (2001) Recoverable catalysts. Ultimate goals, Elsevier Science, Amsterdam
criteria of evaluation, and the green chemistry inter- Vankelecom IFJ (2002) Polymeric membranes in catalytic
face. Pure Appl Chem 73:1319–1324 reactors. Chem Rev 102:3779–3810
Hill CL (1999) Homogeneous catalysis. Controlled green
oxidation. Nature 401:436–437
H
Heteropolyacid
Composite Membranes, O
Fig. 1 Schematic view of
the interactions by S O –
hydrogen bonds between a O S
heteropoly acid (the Keggin –
O H2O H3O+ O
structure is represented) H3O+ O
with the sulfonic group of a
cation exchange H2O
membrane, the water H3O+ H2O
hydration molecules, and
dioxonium ions O H3O+
O–
S H2O
O
H3O+
H3O+ –O
H2O H3O+ S
O
H2O H2O
O
homogeneous catalyst dissolved in solution. of the polymeric matrix providing a better path-
Moreover, the catalytic membranes have given way for proton hopping (Ramani et al. 2005).
proof of their complete stability under photooxi- Composite membranes with higher glass tran-
dation condition and their good recycle. sition temperature (Tg) and higher stability of the
In numerous literature studies, it has been proton conductivity at high temperature have
reported that the HPAs can reduce the resistance been obtained by incorporation of 60 wt.% of
to the proton transport in PEMFCs. three different HPAs (H3PW12O40,
The reduction of the HPAs particles sizes and H3PMo12O40, Na2HPW12O40) in SPEEK mem-
their good dispersion inside the polymeric matrix branes with 70 %, 74 %, and 80 % degree of
resulted to be key factors in order to have a sulfonation (Zaidi et al. 2000).
positive effect on the proton conductivity because Hybrid membranes prepared from sulfonated
of the increase of the surface to volume ratio of polyetherketone (SPEK), heteropoly acids, and
the additives and the possibility to have a more an inorganic network of ZrO2 or RSiO3/2 have
efficient proton hopping (Ramani et al. 2005). been also prepared obtaining a higher proton
HPAs typically exist in hydrated phase with conductivity of the membranes (Ponce
the degree of hydration varying from 6 to 30 mol- et al. 2003).
ecules of water, depending on the temperature The HPAs have been also used to stabilize the
and the relative humidity (e.g., six molecules of proton conductivity of the Nafion membranes at
water are present in the H3PW12O40 structure up elevated temperature and low relative humidity.
to 175–230 C) (Mioč et al. 2005). In Keggin- For example, H3PW12O40, also exchanged with
type HPAs, hydrogen bonds exist between each larger cations such as Cs+, NH4+, Rb+, and Tl+,
acid proton and two water molecules, are also has been heterogenized in Nafion membranes
present between water molecules and the termi- observing better proton conductivity (Ramani
nal oxygen atoms of the HPAs, and moreover, et al. 2005).
involving different Keggin units (Moffat 1986). Tungstophosphoric acid, silicotungstic acid,
If the HPA sizes are in the order of a few and phosphomolybdic acid have been used as
nanometers and uniformly distributed in the pro- functional additives in composite membranes
ton exchange membrane, the water hydration made of the sulfonated derivative of an
molecules and/or dioxonium ions of the additive amorphous-modified polyetheretherketone,
can be used to better interconnect the ionic cluster called SPEEK-WC (Fontananova et al. 2010).
Heteropolyacid Composite Membranes 3
The embedding of the inorganic HPAs, in Kozhevnikov IV (2007) Sustainable heterogeneous acid
particular the H4SiW12O40, in SPEEK-WC mem- catalysis by heteropoly acids. J Mol Catal A Chem
262:86–92
branes, enhanced the proton conductivity Mioč UC, Todorović MR, Davidović M, Colomban P,
because the HPAs improved the interconnection Holclajtner-Antunović I (2005) Heteropoly
of the ionic clusters in the polymeric matrix pro- compounds – from proton conductors to biomedical
viding a preferential pathway for proton hopping agents. Solid State Ionics 176:3005–3017
Moffat JB (1986) Cation-anion effects in heteropoly com-
(Fig. 1). pounds with Keggin structures. Polyhedron 5:261–269
Norby T (1999) Solid-state protonic conductors: princi-
ples, properties, progress and prospects. Solid State
References Ionics 125:1–11
Ponce ML, Prado L, Richau K, Mohr R, Nunes SP
(2003) Reduction of methanol permeability in
Castanheiro JE, Ramos AM, Fonseca I, Vital J (2003) The polyetherketone-heteropolyacid membranes.
acid-catalysed reaction of a-pinene over J Membr Sci 217:5–15
molybdophosphoric acid immobilised in dense poly- Ramani V, Kunz HR, Fenton JM (2005) Effect of particle
meric membranes. Catal Today 82:187–193 size reduction on the conductivity of Nafion ®/
Fontananova E, Donato L, Drioli E, Lopez L, Favia P, phosphotungstic acid composite membranes.
d’Agostino R (2006) Heterogenization of J Membr Sci 266:110–114
polyoxometalates on the surface of plasma modified Zaidi SMJ, Mikhailenko SD, Robertson GP, Guiver MD,
polymeric membranes. Chem Mater 18:1561–1568 Kaliaguine S (2000) Proton conducting composite
Fontananova E, Trotta F, Jansen JC, Drioli E (2010) Prep- membranes from polyether ether ketone and
aration and characterization of new non-fluorinated heteropolyacids for fuel cell applications. J Membr
polymeric and composite membranes for PEMFCs. Sci 173:17–34
J Membr Sci 348:326–336
P
Polymer Electrolyte Membrane Fuel Cell (PEMFC), Table 1 Reactions occurring in hydrogen and direct methanol
polymer electrolyte membrane fuel cell (PEMFC)
H2-PEMFC Methanol-PEMFC
Anode H2 ! 2 H+ + 2 e CH3OH + H2O ! CO2 + 6H+ + 6e
Cathode 1
/2 O2 + 2 H+ + 2 e ! H2O 3
/2O2 + 6H+ + 6e ! 3H2O
Overall reaction 1
/2 O2 + H2 ! H2O CH3OH + 3/2O2 ! CO2 + 2H2O
channeling away wastewater and heat from the commercialization stage (Wee 2007), there are
reaction sites. still many issues to be addressed before large
Currently, the most commonly used PEMs for scale diffusion, including the high cost and lim-
applications in PEMFCs are made of perfluoro- ited durability of PEMs, the appropriate fuel pro-
sulfonic acid polymers, such as Nafion duction and storage.
membranes.
In the last decades, the development of new
PEMs with improved properties for long-term References
fuel cells operations has received relevant atten-
tion. Not only perfluoropolymers but also par- Drioli E, Fontananova E (2012) Membrane materials for
addressing energy and environmental challenges.
tially fluorinated and nonfluorinated
Annu Rev Chem Biomol Eng 3:395–420
hydrocarbon, nonfluorinated aromatic, mixed Hickner MA, Ghassemi H, Kim YS, Einsla BR, McGrath
matrix, and acid–base blend membranes, have JE (2004) Alternative polymer systems for proton
been investigated. Various reviews are available exchange membranes (PEMs). Chem Rev
104:4587–4612
which give an overview of the progress made in
Larmine J, Andrews D (2000) Fuel cell systems explained.
the development of proton-conducting polymer Wiley, Chichester
materials for PEMFCs (Roziere and Jones 2003; Roziere J, Jones DJ (2003) Non-fluorinated polymer mate-
Hickner et al. 2004; Smitha et al. 2005; Tripathi rials for proton exchange membrane fuel cells. Annu
Rev Mater Res 33:503–555
and Shahi 2011; Thiam et al. 2011; Drioli and
Smitha S, Sridhar S, Khan A (2005) Solid polymer elec-
Fontananova 2012). trolyte membranes for fuel cell applications – a review.
The properties required to the PEMs are: high J Membr Sci 259:10–26
proton conductivity; no electronic conductivity; Song C (2002) Fuel processing for low-temperature and
high-temperature fuel cells: challenges, and opportu-
low permeability to the reagent species; appro- nities for sustainable development in the 21st century.
priate chemical, thermal, and mechanical stabil- Catal Today 77:17–49
ity; and acceptable costs. Thiam HS, Daud WRW, Kamarudin SK, Mohammad AB,
The low operating temperatures (50–130 C) Kadhum AAH, Loh KS, Majlan EH (2011) Overview
on nanostructured membrane in fuel cell applications.
and the high power density (400–1000 W/Kg) of
Int J Hydrog Energy 36:3187–3205
the PEMFCs make them ideal for automotive Tripathi BP, Shahi VK (2011) Organic–inorganic
applications, distributed power generation, and nanocomposite polymer electrolyte membranes for
portable electronic devices (Larmine and fuel cell applications. Prog Polym Sci 36:945–979
Wee JH (2007) Applications of proton exchange mem-
Andrews 2000).
brane fuel cell systems. Renew Sust Energ Rev
Although PEMFCs have recently passed the 11:1720–1738
demonstration phases and have reached a partial
S
PEEK PEEK-WC
O O
O
O
O O
O O
SPEEK-WC
O O
O O
O O SO3H
O O O O
1-DS DS
Sulfonated PEEK-WC (SPEEK-WC), Fig. 1 Repetitive unit of the PEEK, PEEK-WC, and the SPEEK-WC (DS is the
degree of sulfonation)
SPEEK-WC membranes have been also mod- operating with SPEEK-WC membranes com-
ified by thermal annealing and chemical cross- pared to PEMFCs operating with Nafion.
linking with a diamine in order to improve their The lower permeability of the SPEEK-WC-
long-term durability (Fontananova et al 2013). based membranes was due to their lower diffu-
Various ex situ characterizations were carried sion coefficients, caused by the higher stiffness of
out on the modified and pristine SPEEK-WC the aromatic polymer chains of SPEEK-WC with
membranes, including ion exchange capacity, respect to Nafion.
proton conductivity, liquid water uptake, Functional additives were also heterogenized
counter-elastic index, chemical resistance in oxi- in SPEEK-WC membranes, in order to improve
dative conditions, and gas permeability. The their properties for applications in PEMFCs.
results indicated that the proposed methodologies Mixed matrix membranes were prepared
are able to increase hydrolytic and oxidative sta- dispersing amorphous zirconium phosphate
bility of the SPEEK-WC membranes. sulfophenylenphosphonate (Zr(HPO4)
SPEEK-WC membranes offer a higher resis- (O3PC6H4SO3H)), in the SPEEK-WC matrix
tance to water and methanol vapor transport than (Regina et al. 2006). The membranes obtained
commercial Nafion membranes (which until were characterized by a homogeneous distribu-
today are the most commonly used membranes tion of the inorganic filler. The membranes
for PEMFCs). Also, the H2 and O2 permeabilities exhibited a significantly lower swelling degree
of the SPEEK-WC membranes are lower in com- in water and methanol compared to the polymeric
parison with Nafion (Fontananova et al. 2010). membranes without the filler.
These results justify the conclusion that less Heteropoly acids (HPAs) have been also dis-
crossover problems may occur in the PEMFCs persed into the membrane dope solutions to
Sulfonated PEEK-WC (SPEEK-WC) 3
Impedance Spectroscopy, Membrane Characterization by, Fig. 1 Schematic view of the experimental setup used
for membrane characterization by impedance spectroscopy using two-probes (a) and four-probes configuration (b)
a b
Rct Rm+s Redl Rdbl
Rm
C C
ω
ω
Impedance Spectroscopy, Membrane Characteriza- equivalent circuit models are also shown. The resistor is
tion by, Fig. 2 Impedance spectra reported as imaginary indicated as R, the capacitor as C, and the constant phase
(Z00 ) versus real part of the impedance (Z0 ) for an ion element (a nonideal capacitor) as CPE. The subscript “m”
exchange membrane: pressed between two solid elec- is referring to the membrane, “ct” to the charge transfer
trodes (a) and separating two electrolyte solutions (b). between electrode and membrane, “m+s” to membrane
The spectra are registered respectively with the two- and plus solution, “edl” to the electrical double layer, and
four-probe configuration, and the corresponding “dbl” to the diffusion boundary layer
Polymeric Catalytic Membranes, Table 1 Selected examples of polymeric catalytic membranes used in membrane
reactors
Catalyst and membrane type Applications References
Metal or bimetal nanoparticles in porous membranes: Selective hydrogenation in gasa and a
Groschel
Pd in PAAa,b liquid phaseb et al. 2005
Au-Pd/PVP in PIc Oxidation of alcoholsc b
Schmidt
et al. 2005
c
Mertens 2008
Catalyst in dense membranes: Cyclohexane oxidationd d
Vankelecom
FePcY in PDMSd Enantioselective hydrogenation of et al. 1996
Transition metal complexes with bisphosphine ligands in methyl 2-acetamidoacrylatee e
Wolfson
PDMSe et al. 2002
Enzymes immobilized in UF membranes: (S)-Naproxen esters hydrolysisf f
Giorno
Lipase from Candida rugosa in PA capillary membranesf (-)MPGM resolution by Sepracor et al. 2007
g
Lipase from Serratia marcescens in hollow fibers reactor (industrial application) Shibatani
hydrophilic membranesg et al.2000
Acid membranes and/or membranes functionalized with Transesterification of soybean oilh h
Guerreiro
solid acid catalysts: Esterification reactioni et al. 2006
PVA/sulfosuccinic acidh; Nafionh; supported acid catalysts Dimerisation of isobutenei,j i
Bagnell
mixed with a polymeric binder on PAN/PDMSi,j et al. 1993
j
Fritsch
et al. 2004
k
Polyoxometalates immobilized in/on porous or dense Photooxidation of alcohols in Bonchio
membranes: waterk et al. 2003
Porous PVDFk,l; dense Hyflonm Phenol photodegradationl,n l
Drioli
Surface functionalized PVDFn membranes Photooxygenation of hydrocarbons m et al. 2008
m
Carraro
et al. 2006
n
Fontananova
et al. 2006
PAA polyacrylic acid, FePcY iron phthalocyanine in zeolite Y, PA polyamide, PVA polyvinyl alcohol, MPGM
(3-(4-methoxyphenyl)glycidic acid methyl ester), PVP polyvinylpyrrolidone, PAN polyacrylonitrile, PVDF
polyvinylidene fluoride
phase enzyme membrane reactor by immobilizing Shibatani T, Omori K, Akatsuka H, Kawai E, Matsumae
lipase in presence of emulsion. J Membr Sci H (2000) Enzymatic resolution of diltiazem interme-
295:95–101 diate by Serratia marcescens lipase: molecular mech-
Gröschel L, Haidar R, Beyer A, Cölfen H, Frank B, anism of lipase secretion and its industrial application.
Schomäcker R (2005) Hydrogenation of propyne in J Mol Catal B: Enzym 10:141–149
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soybean oil over sulfonic acid functionalised poly- Uytterhoeven JB, Jacobset PA (1996) Oxidation of
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Mertens PGN (2008) Membrane-occluded gold- polydimethylsiloxane membranes. J Catal
palladium nanoclusters as heterogeneous catalysts for 163:457–464
the selective oxidation of alcohols to carbonyl com- Westermann T, Melin T (2009) Flow-through catalytic
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Schmidt A, Haidar R, Schomäcker R (2005) Selectivity of Chem Eng Process 48:17–28
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E
particles move under an applied electric field in a encapsulated to last longer, as in chewing gum.
clear liquid encapsulated within a transparent Some food ingredients must be encapsulated to
capsule. be protected from oxidation or other degradation
Today’s textile industry makes use of reactions caused by exposure to light, moisture,
microencapsulated materials to enhance the prop- or oxygen. Microencapsulation preserves lactic
erties of finished goods. One application increas- acid bacteria, both starters and probiotics, in food
ingly utilized is the incorporation of and during the passage through the gastrointesti-
microencapsulated phase change materials nal tract, and may contribute to the development
(PCMs), such as paraffin wax. Phase change of new functional foods.
materials absorb and release heat in response to Many drug formulations for oral, intravenous,
changes in environmental temperatures. When ocular, and subcutaneous administration are
temperatures rise, the phase change material microencapsulated to achieve controlled,
melts, absorbing excess heat, and feels cool. Con- targeted, or triggered release of active ingredi-
versely, as temperatures fall, the PCM releases ents. Aspirin, for example, can cause peptic
heat as it solidifies, and feels warm. Microencap- ulcers and bleeding if doses are introduced all
sulation is also used in thermochromic and pho- at once.
tochromic fabrics, which change color with Microencapsulation of cells and enzymes is
changes in temperature or light, insect-repellent used to improve efficiency of bioreactors since
fabrics, which ward off mosquitoes, and scented very high volumetric productivity can be
fabrics, which release fragrance (Nelson 2002). achieved; encapsulated biocatalysts typically
Pesticides are encapsulated to be released over have greater thermal and operational stability
time, allowing farmers to apply the pesticides less and downstream processing is simplified, since
often rather than requiring very highly concen- the encapsulated biocatalyst can easily be recov-
trated and perhaps toxic initial applications ered and reused. In molecular biology, single-cell
followed by repeated applications to combat the encapsulation is used to achieve high-throughput
loss of efficacy due to leaching, evaporation, and screening in directed evolution experiments.
degradation.
Ingredients in foods are encapsulated for sev-
eral reasons (Gouin 2004). Most flavorings are
References
volatile; therefore, encapsulation of these com-
ponents extends the shelf life of products by Gouin S (2004) Microencapsulation: industrial appraisal
retaining the food flavors within that would oth- of existing technologies and trends. Trends Food Sci
erwise evaporate out and be lost. Some ingredi- Technol 15:330–347
Nelson G (2002) Application of microencapsulation in
ents are encapsulated to mask taste, such as
textiles. Int J Pharm 242:55–62
nutrients added to fortify a product without Yoshizawa H (2004) Trends in microencapsulation
compromising the product’s intended taste. research. KONA 22:23–31
Alternatively, flavors are sometimes
B
Buffer displacement involves the use of where Vb is the volume of buffer added while Vs
diafiltration to replace the solvent (non-product) is the (constant) volume of solution. Assuming
fraction of a macromolecular solution, with a that component, C, also has a rejection coefficient
buffer. The basis of the operation is that the of zero, its concentration in the retentate solution
solvent, including low molecular weight impuri- increases according to the expression
ties, passes through the membrane, while the
solute (product) is retained. Suppose the solution cc ¼ cc0 ð1 expðV b =V s ÞÞ
can be viewed as a mixture containing a macro-
molecular product, A, and a micromolecular where cc0 is the concentration of C in the buffer
impurity, B. Now suppose that the buffer contains tank. If the product, A, has a rejection coefficient
a desired component, C – a salt perhaps. Then, of 1.0, its concentration will remain unchanged.
buffer displacement involves the reduction in the
concentration of B while keeping the concentra-
tion of A constant and raising the concentration
References
of C to the desired level. This can be done using
constant volume (continuous) diafiltration, dis- Cheryan M (1998) Ultrafiltration and microfiltration,
continuous diafiltration by dilution, or discontin- 2nd edn. CRC Press, Boca Raton
uous diafiltration by volume reduction.
Buffer Flush in Diafiltration The greater the ratio of buffer volume (Vb) to
solution volume (Vs) (▶ Diafiltration Factor), the
Greg Foley greater will be the reduction in undesired impu-
School of Biotechnology, Dublin City rities. For example, if an impurity has a rejection
University, Dublin, Ireland coefficient of 0.2 and the diafiltration factor is
5, the reduction in impurity concentration is
given by (Foley 2013)
A buffer flush is simply the replacement of an
impure, product-containing solution with buffer c=c0 ¼ eð1sÞV b =V s ¼ e5ð10:2Þ ¼ 0:018
by subjecting it to ▶ diafiltration.
The most common way of performing a buffer References
flush, at least in a membrane context, is to use
constant volume (continuous) diafiltration in Foley G (2013) Membrane filtration – a problem solving
which a certain volume of buffer is added to a approach with MATLAB. Cambridge University
Press, Cambridge, UK
given volume of impure solution while that solu-
tion undergoes batch ▶ ultrafiltration, all the
while keeping the solution volume constant.
Closed-Loop Cascade Diafiltration the diluant of the first stage. A schematic is shown
below (Fig. 1).
Greg Foley The obvious advantage of this approach over
School of Biotechnology, Dublin City the open-loop configuration is the reduced
University, Dublin, Ireland requirement for a fresh diluant. In principle, the
product should have a low rejection coefficient in
the first stage and a high rejection coefficient in
Closed-loop cascade diafiltration (Charcosset the second stage.
2012) is used when the product to be recovered
appears in the permeate of the first stage of a
two-stage process. It is similar to ▶ open-loop References
cascade diafiltration but differs in that the perme-
ate from the second stage is recycled and used as Charcosset C (2012) Membrane processes in biotechnol-
ogy and pharmaceutics, 1st edn. Elsevier, Boston
Closed-Loop Cascade
Diafiltration,
Fig. 1 Closed-Loop
Cascade Diafiltration
Permeate Permeate
Diafiltration Ultrafiltration
D
Discontinuous diafiltration by the sequential dilu- For example, if the microsolute concentration is
tion method can be summarized in terms of the to be reduced by a factor of 10 (= b) and then if a
three steps shown below. The apparent rejection single stage is used, Vf/V0 = 10, while if three
coefficients are assumed to be 1.0 and 0 for stages are used, Vf/V0 = 101/3 = 2.15.
macrosolute and microsolute, respectively. The total volume of buffer used in this case is
given by
Step 1: Add buffer to increase solution volume
from V0 to Vf. Macrosolute (A) and
V b =V 0 ¼ n V f V 0 =V 0 ¼ n V f =V 0 1
microsolute (B) concentrations decrease.
Step 2: Use batch ultrafiltration to reduce solution ¼ n b1=n 1
volume back from Vf back to V0. Macrosolute
concentration returns to its initial value, For a single stage system, this ratio works out as
microsolute concentration remains 9, while for a three-stage system, it works out as
unchanged. (This follows from the rejection 3.46. Thus, the more stages that are used, the
coefficients of both solutes.) smaller the buffer consumption.
Step 3: Repeat steps 1 and 2 as required.
Step 1: Batch ultrafiltration from volume V0 to Vf. Thus, for a tenfold reduction in microsolute
Macrosolute concentration increases, concentration and a three-stage process, one
microsolute concentration remains the same gets V0/Vf = 101/3 = 2.15 in each
because it has a rejection coefficient of zero. step, while the buffer consumption works out as
Step 2: Replace lost permeate with diluant (pure Vb/V0=3(1101/3) = 1.607.
water or buffer). Macrosolute concentration If one stage had been used, one would have
returns to initial concentration, microsolute had V0/Vf = 10 and Vb/V0 = 1.0(1101) = 0.9.
concentration reduced. Thus, increasing the number of stages increases
Step 3: Repeat steps 1 and 2 as required. the amount of buffer required.
The single-stage approach is not always pos-
Consider a single “stage,” i.e., steps 1 and sible as too large a ▶ volume concentration factor
2 above. The concentration of the macrosolute (V0/Vf) might lead to unsustainably high solution
remains unchanged. A mass balance on the viscosities.
microsolute gives the following expression for
Open-Loop Cascade Diafiltration ery is maximized in the first stage using constant
volume diafiltration and concentrated in the sec-
Greg Foley ond stage by ultrafiltration. Ideally, the rejection
School of Biotechnology, Dublin City coefficient of the product is zero in the first stage
University, Dublin, Ireland and 1.0 in the second stage. In the closed-loop
configuration, the permeate from the second
stage is used as diluant for the first stage (Fig. 1).
The configuration for open-loop cascade
diafiltration is shown below. The product recov-
Open-Loop Cascade
Diafiltration,
Fig. 1 Open-Loop
Cascade Diafiltration
Diluant
Permeate Permeate
Diafitration Ultrafitration
Therefore,
The aim of any batch membrane filtration process
is to reduce the retentate volume, thus increasing cf ¼ c0 VCF
the concentration of a key molecular or particu-
late species. If the solute has an arbitrary and constant appar-
The volume concentration factor is simply the ent rejection coefficient of s, one gets
ratio of the initial solution volume to the final
solution volume, i.e., V0/Vf. It is usually denoted cf ¼ c0 VCFs
by the abbreviation VCF.
Blending Modification
of Membranes, Fig. 2 A
schematic representation of
the dependence of Tg on
composition in binary
polymer blends
KKW, q, and ai upon complexity of the polymer
blend and/or copolymers: T g ¼ x1 T g1 þ x2 T g2 þ x1 x2 : a0 þ a1 ð2x1 1Þ
x1 T g1 þ kKW x2 T g2 þa2 ð2x1 1Þ2 þ a3 ð2x1 1Þ3
Tg ¼ qx1 x2 (3)
x1 þ kKW x2 (4)
Blending Modification of Membranes 3
In all equations the index 2 is referred to the large number of uniform and regular pores
component with the highest Tg, whereas x2 is through the network.
1-x1. Finally, the blend is often preferred to provide
A good blend depends on the degree of inter- composites with mechanical, chemical, and ther-
action between the hosting matrix and the exter- mal properties beyond those observable for the
nal surface area of the dispersed phase and can be single elements. Enhanced tensile properties
regarded as the result of the buoyancy of van der along with reinforced resistance to high temper-
Waals forces and/or hydrogen bonds established atures and harsh environments can be obtained by
at their interface (De Luca et al. 2009). Chemical blending organic and inorganic materials in dif-
functionalization and/or compatibilizing agents ferent ratios.
are two viable routes for strengthening these
reciprocal interactions and dispersing the phases
in continuous volumetric spaces. This needs to References
promote desired events in every region of the
blend. Brostow W, Chiu R, Kalogeras IM, Vassilikou-Dova
A (2008) Prediction of glass transition temperatures:
In membranes, the blend is a common practice
binary blends and copolymers. Mater Lett
to reinforce or produce specific properties, 62:3152–3155
including transport, wetting, pores and mechan- De Lorenzo L, Tocci E, Gugliuzza A, Drioli E (2012) Pure
ics, and so many others. Transport properties can and modified co-poly (amide-12-b-ethylene oxide)
membranes for gas separation studied by molecular
be modified depending on the phase behavior and
investigations. Membranes 2(3):346–366
related morphology. Permeability, selectivity, or De Luca G, Gugliuzza A, Drioli E (2009) Competitive
conductivity can be varied with respect to the hydrogen-bonding interactions in modified polymer
upper bound relationship as a function of the membranes: a density functional theory investigation.
J Phys Chem B 113(16):5473–5477
orientation of the dispersed phase and/or the
Fox TG (1956) Influence of diluent and of copolymer
nature of the interface generated between the composition on the glass temperature of a polymer
various components (Robeson 2010). Indeed, system. Bull Am Phys Soc 1:123–125
the molecular separation can be addressed via Gordon M, Taylor JS (1952) Ideal copolymers and the
second-order transitions of synthetic rubbers.
diffusion or sorption events dependently on free
1. non-crystalline copolymers. J Appl Chem
volume distribution and/or binding sites density. 2(9):493–500
Similarly, the blending can give new solutions Gugliuzza A (2013) Nanocomposite membranes for mem-
to dry-wet membranes; changes in supramolecu- brane reactors. In: Basile A (ed) Handbook of mem-
brane reactors volume I: fundamental materials
lar chemistry can modulate the wettability, mak-
science, design and optimisation. Woodhead Publish-
ing the membrane usable for numerous times ing, Cambridge
without damages and/or special treatments. Gugliuzza A, Fabiano R, Garavaglia MG, Spisso A, Drioli
This approach is also preferred when pores E (2006) Study of the surface character as responsible
for controlling interfacial forces at membrane–feed
must be generated through polymer networks.
interface. J Coll Interf Sci 303(2):388–403
Pore-forming agents are often blended with poly- Gugliuzza A, De Luca G, Tocci E, De Lorenzo L, Drioli
mers and, then, removed by washing treatments. E (2007) Intermolecular interactions as controlling
This takes the advantage of generating empty factor for water sorption into polymer membranes.
J Phys Chem B 111(30):8868–8878
spaces inside dense polymer networks, but the
Kwei TK (1984) The effect of hydrogen bonding on the
major difficulty is often the complete removal glass transition temperatures of polymer mixtures.
of the filler from the matrix. In this respect, a J Polym Sci Lett 22(6):307–313
good compatibility between pore-forming agent Robeson LM (2010) Polymer blends in membrane trans-
port processes. Ind Eng Chem Res 49:11859–11865
and polymer matrix is necessary to produce a
D
Differential Scanning Calorimetry in Membrane Characterization, Table 1 Thermal transitions and related
parameters measurable by DSC
Event Phase transition Energy sign Parameter
Fusion sol!liq Endothermic l, DH
Crystallization liq!sol Exothermic l, DH
Evaporation liq!gas Endothermic l, DH
Condensation gas!liq Exothermic l, DH
Sublimation sol!gas Endothermic l, DH
Deposition gas!sol Exothermic l, DH
Glass transition Change of the baseline Cp
Chemical reactions Exothermic/endothermic DH
Differential Scanning
Calorimetry
in Membrane
Characterization,
Fig. 1 Main endothermic
and exothermic transitions
observable by DSC
baseline due to a variation of Cp of the polymer well. If the polymer forming the membrane is
forming the membrane. available to crystallize, a release of energy is
All amorphous polymers exhibit a Tg; below associated with a decrease in heat flow. The
this temperature value, the membrane becomes study of crystallization is often more useful than
glassy owing to the inability of the polymer seg- fusion, because it allows distinguishing peaks
ments to rotate and rearrange themselves. When that normally cannot be well visible in melting.
the membrane temperature is increased over its Phase separation, miscibility, and compatibil-
Tg, an increase in energy and free volume is ity of polymer binary blends, copolymers, and,
observed due to a broader mobility of the chains, more generally, composites are among the most
which enters the polymer in the rubbery region. interesting events to examine by DSC
Heating and cooling rates as well as chain relax- (De Lorenzo et al. 2012). In this case, the ability
ation can affect Tg value and shape, respectively. of the materials to interact and distribute them-
The fusion is another endothermic event selves in continuous and uniformly interlaced
involving crystalline domains distributed through spaces can be evaluated under different experi-
the membranes. The amount and extent of these mental conditions. Other interesting indication
ordered regions depends on the chemistry, about the membranes solidity can be achieved
molecular weight, and thermal history of the from the study of curing, aging, as well as degra-
samples. Polymorphism and crystalline features dation and oxygen stability. All these parameters
of the membranes can be examined in relation to can significantly affect the membrane transport
transport properties and mechanical stability as properties.
Differential Scanning Calorimetry in Membrane Characterization 3
Honeycomb Membrane Structure, Fig. 1 Representative mechanism for the formation of honeycomb membranes
membrane distillation, membrane crystallization, but also for handling the miniaturization of light-
and membrane emulsification (in particular pre- weight systems perceptively.
mix membrane emulsification), where large mass
transfer along with the establishment of durable
interfaces at the entrance of each single pore are References
in great demand. Moreover, the extraordinary
regularity and stability of 3D polymeric architec- Gugliuzza A, Aceto MC, Macedonio F, Drioli E (2008)
Water droplets as template for next generation self-
ture make these membranes suitable for working
assembled poly-(etheretherketone) with Cardo mem-
as molecular reservoirs, scaffolds for tissue engi- branes. J Phys Chem B 112(34):10483–10496
neering, and platforms for sensors. Gugliuzza A, Speranza V, Trotta F, Drioli E (2009)
Compared with traditional manufacturing pro- Bio-inspired membranes with well-defined channels.
Chem Eng Trans 17:1537–1542
cedures, the one-pot fabrication of micro- and
Speranza V, Trotta F, Drioli E, Gugliuzza A (2010) High-
nanostructured membranes, based on the self- definition polymeric membranes: construction of 3D
assembly of sacrificial natural building blocks, lithographed channel arrays through controlling natu-
is regarded as a novel, flexible, and eco-friendly ral building blocks dynamics. ACS Appl Mater Inter-
faces 2(2):459–466
technology. This approach is expected to open
Thomas JR (1999) Rough surfaces. Imperial College
new routes to fabricate a large variety of ordered Press, London
functional membranes for industrial applications,
T
The Principle of Reverse Osmosis describing the transport in reverse osmosis mem-
(RO) branes two approaches are described in the liter-
ature. One is the so-called solution-diffusion
Lidietta Giorno1, Enrico Drioli1 and model which neglects kinetic coupling of differ-
Heiner Strathmann2 ent fluxes (Merten 1966). The second is based on
1
Institute on Membrane Technology, National the phenomenological equation of the thermody-
Research Council of Italy, ITM-CNR, National namic of irreversible processes (Katchalsky and
Research Council of Italy, Rende(CS), Calabria, Curran 1967). This model does consider kinetic
Italy coupling between different fluxes. Both models
2
Universität Stuttgart, Institute of Chemical describe the transport in reverse osmosis mem-
Process Engineering Stuttgart, branes quite accurately indicating that kinetic
Baden-W€ urttemberg, Germany coupling is not of great importance in reverse
osmosis.
Synonyms
Reverse Osmosis Mass Transport
Mass transfer in Reverse Osmosis RO
Described by the Solution-Diffusion
Model
In reverse osmosis the driving force is also a
hydrostatic pressure difference. The principle of
In the solution-diffusion model, the flux of dif-
the process is illustrated in Fig. 1, which shows a
ferent components through a membrane is
solution containing a low molecular weight com-
assumed to be by diffusion only and can be
ponent separated by a membrane from the solvent
described by the product of its concentration
and a hydrostatic pressure difference applied
and mobility in the membrane matrix and the
across the membrane resulting in a flux of solvent
chemical potential gradient of the component in
from the solution into the pure solvent
the membrane. Furthermore, it is assumed that
(Strathmann et al. 2006).
there is no kinetic coupling between fluxes, that
The membrane used in reverse osmosis has an
the volume flux is approximately identical to the
asymmetric structure with a dense barrier layer at
flux of the solvent, and that the solute flux due to
the side facing the feed solution. It is assumed
the pressure gradient is negligibly small com-
that in this layer the individual components are
pared to the solute flux due to the activity
transported by diffusion and that viscous flow
gradient.
through pores or pinholes can be neglected. For
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_908-1
2 The Principle of Reverse Osmosis (RO)
Thus is:
and the solute flux to:
J s ¼ Ds m Cs dlnm Cs ¼ Ds dm Cs (3)
The Principle of Reverse Osmosis (RO) 3
Equation 7 shows that rejection of a component Here, J is the flux, m is the chemical potential, L is
in reverse osmosis is not only a function of the the phenomenological coefficient, the subscripts
membrane and feed solution properties it is also a w and s refer to the solvent which is assumed to be
function of the applied hydrostatic pressure. The water and the solute which is assumed to be salt,
rejection will increase with increasing applied the subscripts ws and sw refer to the coupling
hydrostatic pressure and approaches asymptoti- between the fluxes of water and salt and salt and
cally a maximum value. water.
The diagonal coefficients Lw and Ls are always
positive while coupling coefficients Lsw and Lws
Reverse Osmosis Transport Described can be positive or negative as can be seen from
by the Phenomenological Equations the dissipation function which describes the
entropy production in a process. The total number
In deriving Eqs. 5, 6, and 7 on the solution diffu- of coefficient in the phenomenological equations
sion model, a number of assumptions have been is reduced by the Onsager relation, which postu-
made including the neglecting of all kinetic cou- lates that the coupling coefficients Lsw and Lws are
pling between transported components and any identical (Onsager 1931a, b). However, Eqs. 9
viscous flow. A more comprehensive treatment of and 10 are not very useful to describe the trans-
the mass transport in reverse osmosis mem- port properties of a reverse osmosis membrane
branes, where kinetic coupling and convective because the coupling coefficients are difficult to
flow are taken into account, is based on phenom- determine in an independent measurement and
enological equations applied to the laws of the generally in reverse osmosis the total filtration
thermodynamic of irreversible processes. In a rate, i.e., the volume flux is of interest. However,
reverse osmosis system, which consists of a the coupling coefficient can be converted to more
membrane and a two component feed solution, easily measurable constants when the phenome-
i.e., a solvent and a solute, two independent fluxes nological equations are slightly modified by
will be obtained when the membrane is used as introducing the volume flux and a diffusive flux
frame of reference. These fluxes can be described (Kedem and Katchalsky 1961).
by: The dissipation function for the Eqs. 9 and 10
is given by:
X
Ji Lik Xk ði, k ¼ 1, 2, 3 . . . , nÞ (8)
k C ¼ J w dmw þ J s dms
¼ J w d V w p þ RT ln aw
Here, J is the flux of the different components,
L is the phenomenological coefficient, and X is þ J s d V s p þ RT ln as (11)
the driving force, the subscripts i and k refer to
different components. Here, c is the dissipation function, J is the flux, a,
Assuming a system without viscous flow com- m, and V are the activity, the chemical potential,
posed of a solute, a solvent, and a membrane as and the partial molar volume, and p is the hydro-
frame of reference there are two independent static pressure, the subscripts w and s refer to
fluxes: solvent and solute.
Assuming a linear relation for the chemical
potential gradients and introducing the osmotic
4 The Principle of Reverse Osmosis (RO)
pressure for the activities of the water and solute ðJ v ÞDp¼0 ¼ LpD Dp (19)
integration of Eq. 11 lead to:
Assuming that there is no osmotic pressure dif-
C ¼ J w V w þ J s V s Dp ference, i.e., Dp = 0, then the diffusive flux is
given by:
Js
þ J w V w Dp
Cs
ðJ D ÞDp¼0 ¼ LDp Dp (20)
¼ J v Dp þ J D Dp (12)
and the volume flux is given by:
Introducing a volume and a diffusion flux given
by: ðJ v ÞDp¼0 ¼ Lp Dp (21)
Js LpD
JD ¼ VwJw (14) ðDpÞjv ¼0 ¼ Dp¼sDp (22)
Cs Lp
into the dissipation function results in: Here, s is the so-called Staverman reflection
coefficient which is a measure for the
C ¼ J v Dp þ J D Dp (15) permselectivity of a membrane.
Equation 22 shows that in osmotic equilibrium
The first term in Eq. 15 describes the total volume the hydrostatic pressure difference between two
flux Jv as function of the applied pressure, and the solutions separated by a membrane is equal to the
second term describes the diffusion flux of the osmotic difference Lp = LpD and therefore s =1.
salt JD. This is only the case for a strictly semipermeable
The new set of phenomenological equations membrane. Usually, the Staverman reflection
is: coefficient has values between 0 and 1.
If the volume flux is 0, the ratio of salt flux to
J v ¼ Lp Dp þ LpD Dp (16) osmotic pressure difference is given by:
and
Js Cs Lp LD L2pD
¼ ¼o (23)
Dp J v ¼0 Lp
J D ¼ LD p Dp þ LD Dp þ LD Dp (17)
Aged Carbon Membrane the pores in the membrane and attenuate the
permeation of other species.
Miki Yoshimune In a study of the effects of air oxidation and
Research Institute for Chemical Process humidity at room temperature on the aging of
Technology, National Institute of Advanced carbon membranes, Menendez and Fuertes
Industrial Science and Technology (AIST), (2001) found the membrane stored in dry or
Tsukuba, Japan humid air underwent a rapid loss of permeability,
whereas membranes stored under propene or
nitrogen were protected from damage. The
If the use of high-performance carbon mem- researchers suggested that chemisorption of oxy-
branes in gas separations is to be commercial- gen rather than physisorption of water is princi-
ized, the aging characteristics of such pally responsible for the loss of permeability that
membranes will become important. Little work occurs when a fresh carbon membrane is exposed
has been done on studying this aspect of carbon to air.
membranes, but some researchers have pointed Jones and Koros (1994) found that carbon
out that there are significant problems related to membranes are highly vulnerable to adverse
the performance stability of carbon membranes effects of exposure to organic contaminants,
(Jones and Koros 1995a; Lagorsse et al. 2004, even at concentrations as low as 0.1 ppm.
2005; Saufi and Ismail 2004). Although they are Attempts to regenerate membranes after expo-
chemically and thermally resistant, carbon sure to hydrocarbons by high-temperature
membranes generally suffer deterioration in per- (363 K) treatment in a vacuum were unsuccess-
formance upon exposure to substances that ful. Jones and Koros (1995a) also studied the
become strongly adsorbed, such as water vapor effects of humidity on the O2/N2 selectivity and
or oxygen. As carbon membranes have a sharp permeability of a carbon membrane by using
pore-size distribution with a critical size ranging feeds with relative humidities of 23–85 %.
from 0.3 to 0.7 nm, small changes in the effec- Some losses in performance occurred at all
tive size of the pore structures can markedly humidity levels, but this problem could be alle-
affect their permeability toward adsorbing gas viated by rendering the surface of the membranes
molecules. In addition, constrictions in the pore hydrophobic by coating them with thin layers of
system can occur as a result of chemisorption of Teflon AF1600 or AF2400 (Jones and Koros
oxygen or by strong adsorption of species having 1995b). The resulting composite carbon mem-
very low diffusivity because of their branes were significantly protected from the
organophilic nature. Such species will block adverse effects of humidity.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_909-1
2 Aged Carbon Membrane
Lagorsse et al. (2008) made a thorough inves- exposed to air. The chemisorption of oxygen
tigation on the effects of exposure to air and leads to the formation of C–O surface groups,
humidity on the performance of commercialized thereby creating a more hydrophilic interface
carbon hollow fiber membranes, supplied by Car- that favors increased adsorption of water.
bon Membranes Ltd. (Israel). The production of Adsorbed species can reduce the pore size of the
these membranes involved pyrolysis followed by carbon over time, leading to decreases in the
chemical vapor deposition and an activation step permeability and selectivity of the membrane.
(Lagorsse et al. 2004). The researchers found that Therefore, studies on the stability of carbon
the membrane underwent a loss of permeability membranes will be an important aspect on
with time when exposed to pure oxygen or to air; research on such membranes in the future.
however, the performance of the membrane ulti-
mately stabilized after prolonged exposure.
Attempts to regenerate the membranes by expo- References
sure to flowing nitrogen at 343 K or by treatment
with propene and propyne as cleaning agents Jones CW, Koros WJ (1994) Carbon molecular sieve gas
separation membranes. II. Regeneration following
resulted in no significant recovery of permeabil-
organic exposure. Carbon 32:1427–1432
ity. However, no deterioration in permeability of Jones CW, Koros WJ (1995a) Characterization of
these membranes was observed when they were ultramicroporous carbon membranes with humidified
stored under nitrogen. The researchers therefore feed. Ind Eng Chem Res 34:158–163
Jones CW, Koros WJ (1995b) Carbon composite mem-
concluded that aging of carbon membranes is
branes: a solution to adverse humidity effects. Ind Eng
caused exclusively by chemisorption of oxygen Chem Res 34:164–167
from air. On the other hand, humidity adversely Lagorsse S, Magalhães FS, Mendes A (2004) Carbon
affects the performance of membranes in molecular sieve membranes: sorption, kinetic and
structural characterization. J Membr Sci 241:275–287
multicomponent separation processes because
Lagorsse S, Campo MC, Magalhães FD, Mendes A (2005)
water is strongly adsorbed, but diffuses relatively Water adsorption on carbon molecular sieve mem-
easily through the membranes. Heating under an branes. Experimental data and Isotherm model. Car-
atmosphere of hydrogen at 893 K to remove bon 43:2769–2779
Lagorsse S, Magalhães FD, Mendes A (2008) Aging study
surface oxygen groups had some effect on stable
of carbon molecular sieve membranes. J Membr Sci
surfaces protected from chemisorption of oxy- 310:494–502
gen. This treatment can be used to restore the Menendez I, Fuertes AB (2001) Aging of carbon mem-
permeation properties to those of fresh branes under different environments. Carbon
39:733–740
membranes.
Saufi SM, Ismail AF (2004) Fabrication of carbon mem-
These studies demonstrated that the effects of branes for gas separation—a review. Carbon
aging are more pronounced when membranes are 42:241–259
stored under a high-humidity atmosphere and are
P
Kiss K, Nemestothy N, Gubicza L, Belafi-Bako K (2009) Pilnik W, Voragen AGJ (1993) Pectic enzymes in fruit
Vacuum assisted membrane bioreactor for enzymatic juice and vegetable juice manufacture. In: Reeds G -
hydrolysis of pectin from various sources. Desalina- (ed) Food and science technology, enzymes in food
tion 241:29–33 processing. Academic, New York, pp 363–399
P
In a recent work, a membrane bioreactor was the substrate onto the membrane surface was
used with a hairy membrane layer (Bélafi-Bakó found to improve the efficiency of the process.
et al. 2006) that offered a special surface area for
simultaneous adsorption of the substrate and
enzyme. In this way the cellulose-cellulase layer References
formed provided a further advantage: diffusion
resistance between the substrate and enzyme was Bélafi-Bakó K, Koutinas A, Nemestóthy N, Gubicza L,
Webb C (2006) Continuous enzymatic cellulose
reduced. Since solid particles present might cause
hydrolysis in a tubular membrane bioreactor. Enzyme
troubles (fouling), it required special conditions Microb Technol 38:155–161
for the construction of the membrane reactor. To Drioli E, Giorno L (1999) Biocatalytic membrane reac-
avoid blockage, tubular type membrane module tors. Taylor and Francis Group, London
Mansfield SD, Mooney C, Saddler JN (1999) Substrate
was used in the experiments. The simultaneous,
and enzyme characteristics that limit cellulose hydro-
reversible immobilization of the biocatalyst and lysis. Biotechnol Prog 15:804–816
D
Dealcoholization by
Pervaporation,
Fig. 1 Dealcoholyzation
by a pervaporation process
In addition, membranes with performance that membrane by the plasticizing effect because of
can be set in bench-scale plants have not been membrane swelling, which significantly reduces
developed. Thus, the developments of alcohol- the selectivity to alcohol. To solve this problem,
selective permeable membranes are delayed the balance of hydrophobicity and affinity of the
compared with that of water-selective mem- membrane is examined by graft, copolymers,
branes. The cause is due to the larger molecular multiblock, blend, and three dimensional struc-
size of alcohol molecules, which are permeated tures by cross-link. In each case, there is a limit to
preferentially, compared with that of water mol- improvement in separation performance by pre-
ecules. When alcohol from alcohol aqueous solu- vious method because there is a discrepancy
tion is permeated preferentially, separation on the between affinity and swelling.
diffusion process cannot be expected in PV
method based on a solution-diffusion mecha-
nism. Thus, separation can be performed using References
the difference in the only solution process of both
components of the membrane. However, the Kober PA (1917) Pervaporation, perstillation and
membrane is excessively swelled by very high percrystallization. J Am Chem Soc 39:944–948
Nagai K (2010) Fundamentals and perspectives for
affinity to alcohol because it is in direct contact
pervaporation. In: Enrico D, Lidietta G (eds) Compre-
with the mixture solution to be separated in PV hensive membrane science and engineering, 1st edn.
method. Thus, permeability increases. However, Elsevier, Amsterdam, pp 243–271
the small molecular size of water enters the
A
Antioxidant Recovery by Membranes, Table 1 Membrane processes for separation/concentration of different types
of antioxidants
Driving force Membrane process Antioxidants References
Pressure-driven Microfiltration Tocopherols (de Souza et al. 2008)
membrane and
processes tocotrienols
Phenols (Russo 2007; Laorko et al. 2010)
Organic (Laorko et al. 2010)
acids
Ultrafiltration Phenols (Russo 2007; Laorko et al. 2010; El-Abbassi 2012;
Borneman et al. 2001; Cassano et al. 2008; Cissé
et al. 2011; Conidi et al. 2011; Nawaz et al. 2006; Li
et al. 2005)
Organic (Cassano et al. 2006)
acids
Peptides (Bouhallab and Touzé 1995; Lajoie et al. 2001;
Vandanjon et al. 2007)
Nanofiltration Tocopherols (Subramanian et al. 1998a, b, 2003)
Phenols (Cissé et al. 2011; Negrao Murakami et al. 2011; Mello
et al. 2010; Conidi et al. 2011)
Peptides (Vandanjon et al. 2007; Fenton-May et al. 1971;
Tessier et al. 2006b)
Electrically Electrodialysis Phenols (Bazinet et al. 2005)
driven membrane Organic (Vera Calle et al. 2003)
processes acids
Electrodialysis Organic (Vera Calle et al. 2002)
with bipolar acids
membranes
Electrodialysis Phenols (Labbé et al. 2005; Bazinet et al. 2009, 2012)
with filtration Organic (Bazinet et al. 2012)
membranes acids
Peptides (Langevin et al. 2012)
(RO). The solution properties, charges of ionic microorganism were completely removed. UF
species and the type of membrane used, affect the was studied on different sources such as olive
behavior and the efficiency of the separation mill wastewater (Russo 2007; El-Abbassi 2012),
method (Martin-Orue et al. 1998). Working at fruit juices (Borneman et al. 2001; Cassano
low concentration is preferable to avoid the for- et al. 2008; Laorko et al. 2010; Cissé
mation of a polarization layer which could affect et al. 2011; Conidi et al. 2011), grape seeds
selectivity of the membrane (Shahidi 2004). (Nawaz et al. 2006), and green tea
For the separation of tocopherols and (Li et al. 2005). NF was tested on roselle extract
tocotrienols, only MF (de Souza et al. 2008) (Cissé et al. 2011), on mate (Negrao Murakami
and NF (Subramanian et al. 1998a, b, 2003) et al. 2011), on aqueous propolis extract (Mello
were reported. For phenols recovery, MF was et al. 2010), and on bergamot juice (Conidi
used on vegetation waters (VW) (Russo 2007) et al. 2011). Organic acids such as Ascorbic,
and pineapple juice (Laorko et al. (2010). The isoascorbic, folic, and citric acids can also be
authors showed that MF did not affect signifi- recovered by filtration process. Hence, MF was
cantly the pH, reducing sugar and acidity of clar- used for the recovery of ascorbic acid (Laorko
ified juice whereas the suspended solids and et al. 2010), while UF was tested on kiwifruit
Antioxidant Recovery by Membranes 3
juice to recover folic, ascorbic, and citric acids having antioxidant properties,Vera Calle
(Cassano et al. 2006). Concerning antioxidant et al. (2003) were indirectly precursor in the use
peptides, they are separated into fractions using of ED for the recovery of citric acid. In all the
membranes in the range 1–10 kDa (Je et al. 2005; deacidified juices, a decrease in the citrate and
Jeon et al. 1999; Rajapakse et al. 2005). NF can malate concentrations was obtained. Vera Calle
be used to concentrate hydrolysates (Vandanjon et al. (2002) also tested the deacidification of
et al. 2007; Fenton-May et al. 1971; Tessier clarified passion fruit juice, by electrodialysis
et al. 2006b) whereas UF membranes with high with bipolar membrane (EDBM). Citric acid
MWCO (20–100 kDa) are adapted to the separa- was formed in the concentrate compartment by
tion of peptides and nonhydrolyzed proteins or citrate ions extracted from juice and protons pro-
proteolytic enzymes (Bouhallab and Touzé 1995; vided by the BM separating the concentrate and
Lajoie et al. 2001). On the other hand, UF mem- electrode compartments. This configuration
branes with intermediate molecular weight cut- allowed the production of citric acid with 89 %
offs (about 4000–8000 Da) allow hydrolysates to purity. During EDFM of cranberry juice, Bazinet
be fractionated with the result of enrichment in et al. (2012) observed that enriched juice concen-
some ranges of molecular weight (Vandanjon trations in citric and malic acids decreased
et al. 2007). The use of integrated membrane respectively of 7.3 % and 4.7 % resulting in a
system (UF/MF/RO, MF/NF, . . .) is becoming significant decrease of its sour taste intensity, a
another real alternative to recover, purify, or con- major problem for cranberry juice producer.
centrate antioxidants as it is established in some However, the concentration in the raw juice was
recent works (Paraskeva et al. 2007; Russo 2007; not significant due to the high ratio of raw juice/
Garcia-Castello et al. 2010; Conidi et al. 2011; enriched juice. Very recently, a combination of
Diaz-Reinoso et al. 2011). UF membrane stacked in an electrodialysis cell
was tested successfully for the selective separa-
Electrically Driven Membrane Processes tion of anionic and cationic antioxidant peptides
Electrically driven processes, like electrodialysis (Langevin et al. 2012). The results showed only a
(ED) and hybrid processes (ED with bipolar significant increase in the antioxidant capacity
membranes (EDBM) and ED with filtration for anionic peptide fractions recovered at pH 3
membranes (EDFM)), use ion-exchange mem- and pH 6 compared to the feed hydrolysate
branes and/or filtration membrane to separate (Langevin et al. 2012). In the comparative study
molecules (Bazinet 2005). The electric field is of Langevin et al. (2012), it was demonstrated
the main driving force involved in these pro- that NF was more efficient in terms of mass flux
cesses. Molecular transfer is mainly due to the than EDFM when compared on a same basis
charge of the molecule and the flux depends on (membrane area, process duration), but EDFM
the strength of the electric field (Poulin recovered larger range of peptide molecular
et al. 2007; Doyen et al. 2012). weights and amount of polar amino acids.
Conventional electrodialysis has been tested
as a mean of selectively extracting polyphenols
from aqueous tobacco extracts (Bazinet
References
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new electrically driven technology has been applications in the dairy industry: a review. Crit Rev
recently tested for the recovery of polyphenols. Food Sci Nutr 44:525–544
EDFM was used on green tea to perform selec- Bazinet L, Firdaous L (2013) Separation of bioactive
peptides by membrane processes: technologies and
tive extraction of catechins (Labbé et al. 2005) devices. Recent Pat Biotechnol 7 (1): 9–27
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its own natural phenolic antioxidant compounds Electromigration of tobacco polyphenols. Sep Purif
(Bazinet et al. 2009, 2012). For organic acids Technol 41:101–107
4 Antioxidant Recovery by Membranes
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fractionation and total recovery of polyphenols, water whiting peptide hydrolysates by membrane processes.
and organic substances from vegetation waters (VW). J Food Eng 83:581–589
J Membr Sci 288:239–246 Vandanjon L, Grignon M, Courois E, Bourseau P, Jaouen P
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69:146–149 Vera Calle E, Ruales J, Dornier M, Sandeaux J,
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C
extremely high sintering temperatures, as well as different purposes, such as dip coating and wash
the protecting atmosphere required for sintering. coating, sol–gel process, and chemical or physical
Dense ceramic membranes are used at high vapor deposition techniques.
temperatures, and these membranes normally are
made of ion-conductive materials or mixed ion
and electron-conductive materials. For the former
Applications
ones, an external circuit is needed to pass elec-
trons to compensate the charge of ionic species
Porous ceramic membranes have been commonly
when ions move from one side to the other side,
used in water and wastewater treatment, food and
and work can be done within the external circuit.
beverage processing, pharmaceuticals, and chem-
This is the principle of solid oxide fuel cells
ical processing. The most widely used membrane
(SOFCs), and the dense membrane acts as the
types are microfiltration and ultrafiltration mem-
electrolyte in a SOFC. For the later ones, electrons
branes, although the demand of nanofiltration
can pass the membrane directly, and separation of
ceramic membranes is also increasing in recent
gas species can be completed by its own. The
years.
most important category of ion-conductive mate-
Dense ceramic membranes have not really
rials is oxygen–ion conductor, for example, fluo-
found their industrial usages, but some pilot plants
rite type oxides including fully stabilized zirconia
of oxygen permeable ceramic membranes with a
and doped ceria, which are commonly used in
considerable scale are running in the USA and
SOFC, and perovskite type oxides that can be
Europe, and some commercial SOFC products
used alone to separate pure oxygen from air at
are also available in the market. Some key techni-
high temperatures. Another important category is
cal obstacles need to be addressed before these
proton conductor, which also have attracted wide
dense ceramic membranes and the membrane-
interests to use them in SOFC and high-
based technologies can enter into industrial
temperature hydrogen separation.
usages, such as high-temperature sealing and sys-
tem stability.
Membrane Structure and Fabrication
DuraMem™ Membrane, Fig. 1 A typical SEM micrograph of a cross section (left) and top separating layer (right) of
cross-linked PI membranes (Adapted from Toh et al. (2007))
M
Membrane Based Solvent Extraction from the liquid/liquid interface immobilized at the
pore mouth of the microporous membrane that is
Lidietta Giorno not wetted by one of the phases in contact. In this
Institute on Membrane Technology, National way, dispersion of the liquid phase into the other is
Research Council of Italy, ITM-CNR, National prevented. Microfiltration or ultrafiltration mem-
Research Council of Italy, Rende (CS), Calabria, branes are usually used as support to immobilize
Italy the interface between the two immiscible phases.
In membrane based solvent extraction the mem-
brane has no selective properties, it only serves as
Synonyms support for the immobilization of the interface.
Basic information on membrane based solvent
Liquid-liquid membrane extraction extraction are found in Prasad and Sirkar (1992),
Reed et al. (1995), Schlosser (2000, 2009).
In membrane based solvent extraction (MBSE) The solvent can be regenerated by
two immiscible phases are in contact with a re-extracting the solute in a stripping solution.
porous membrane. One of the two phases wets Figure 2 shows the schematic of a membrane
the membrane whilst the other does not wet it based solvent extraction and stripping using two
(Fig. 1). hollow fiber modules.
In membrane-based solvent extraction mass- Membrane based solvent extraction is often
transfer between two immiscible solvents occurs assisted by a carrier that reacts with the solute at
the interface immobilized on the first module and should be taken into account as it can play an
it is released at the interface of the second module. important role. The concentration dependence of
Figure 3 shows the case of extraction of lactic acid the distribution coefficient of solutes is another
by a quaternary amine. parameter to be taken into the account. The solute
In membrane based solvent extraction medi- distribution coefficient influences the concentra-
ated by carriers, kinetics of extraction reactions tion gradient and may result in the concentration
dependent overall mass-transfer coefficient.
FEED SOLVENT In the literature, studies using models consider-
ing the constant mass-transfer coefficient in MBSE
(Viegas et al. 1998), or variable distribution coef-
SW ficients (Escalante et al. 1998; González-Munoz
et al. 2004) are reported. Models taking into
account reaction kinetics of formation and decom-
position of the extractant-solute complex(es) in
extraction and stripping interfaces are also
discussed (Juang and Huang 1997; Juang
FIBER WALL
et al. 2000; Kubišova et al. 2004; Schlosser
F S
et al. 2001). The contribution of resistance based
on reaction kinetics to the overall resistance
depends on solute and carrier concentrations. It
may range between 30 % and 80 %.
Membrane Based Solvent Extraction,
Ionic liquids result very promising in the sol-
Fig. 1 Schematic of MBSE mechanism at membrane
level. F: feed, S: solvent, Sw: solvent in fiber wall. Here vent extraction of organics (Han and Armstrong
is shown the case where the membrane is wetted by the 2007; Pletnev et al. 2008). Ionic liquids (ILs) are
organic solvent composed of organic cations and organic or inor-
ganic anions that remain in liquid state over a wide
temperature range, including room temperature.
4 7 10
Mod 1 Mod 2
6 9
8
5
11 12 13
1 2 3
Membrane Based Solvent Extraction, Fig. 2 Membrane-based solvent extraction in hollow fibre membrane
contactors. 1–3 pums, 4–10 pressure gauges, 11–13 flowmeters
Membrane Based Solvent Extraction 3
H2O H2O
La-
La-
R3NH+La-
Membrane Membrane
module I module II
Membrane Based Solvent Extraction, Fig. 3 Mechanism separation of lactic acid by membrane-based solvent
extraction
The majority of works deals with ILs with pyrazinecarboxylic acid and co-transport of sulphuric
imidazoliumcations. A new promising group of acid in HF contactors. Desalination 163:27
Pletnev IV, Smirnova SV, Egorov VM
ILs based on phosphoniumcations (Bradaric (2008) Liquid–liquid extraction of organic compounds.
et al. 2003). In: Koel M (ed) Ionic liquids in chemical analysis. CRC
Press, Boca Raton, p 243
Prasad R, Sirkar KK (1992) Membrane based solvent
extraction. In: Ho WSW, Sirkar KK (eds) Membrane
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backextraction equilibrium and kinetic-parameters. Mulder M(eds) Integration of membrane processes
Sep Sci Technol 33:119 into bioconversions. Kluwer, New York, p 55
González-Munoz MJ, Luque S, Alvarez JR, Coca J (2004) Schlosser Š (2009) Extractive separations in contactors
Simulation of integrated extraction and stripping pro- with one and two immobilized L/L interfaces: applica-
cesses using membrane contactors. Desalination 163:1 tions and perspectives. In: Drioli E, Giorno L (eds)
Han X, Armstrong DW (2007) Ionic liquids in separations. Membrane operations. Innovative separations and
Acc Chem Res 40:1079 transformations. Wiley-VCH, Weinheim, p 513
Juang RS, Huang RH (1997) Kinetic-studies on lactic-acid Schlosser Š, Sabolová E, Kertész R, Kubišová Ľ
extraction with amine using a microporous membrane- (2001) Factors influencing transport through liquid
based stirred cell. J Membr Sci 129:185 membranes and membrane-based solvent-extraction.
Juang RS, Chen JD, Huan HC (2000) Dispersion-free J Sep Sci 24:509
membrane extraction case-studies of metal-ion and Viegas RMC, Rodriguez M, Luque S, Alvarez JR,
organic-acid extraction. J Membr Sci 165:59 Coelhoso IM, Crespo JPSG (1998) Mass-transfer cor-
Kubišova Ľ, Sabolová E, Schlosser Š, Marták J, Kertesz R relations in membrane extraction analysis of Wilson-
(2004) Mass-transfer in membrane based solvent plot methodology. J Membr Sci 145:129
extraction and stripping of 5-methyl-2-
H
Seed
synthesis
Membrane Seeding
synthesis
Porous support
Seeded Hydrothermal Synthesis for Zeolite Preparation, Fig. 1 Scheme of the hydrothermal synthesis of zeolite
membranes by separating the nucleation and the crystal growth steps
Seeded Hydrothermal Synthesis for Zeolite Preparation, Fig. 2 SEM analysis of silicalite membranes over
nonporous alumina substrates after 20 h of secondary growth synthesis conditions. Left: top view. Right: cross section
Seeded Hydrothermal Synthesis for Zeolite Preparation 3
Seeded Hydrothermal
Synthesis for Zeolite c
Preparation, {101}
Fig. 3 Schematic
orientation of c-oriented
MFI zeolite crystal
{100}
b
{001}
Hydrothermal Synthesis of Zeolite the highly alkaline synthesis gel and heated up in
the autoclave up to the selected temperature.
Reyes Mallada After an induction period crystalline zeolite
Department of Chemical and Environmental nuclei could be detected later, the nuclei start
Engineering and Aragon Nanoscience Institute, growing and finally all the amorphous material
Universidad de Zaragoza, Zaragoza, Spain is converted into zeolite. There are several mech-
anisms proposed for the hydrothermal synthesis
of zeolites (Cundy and Cox 2005), but in general
Zeolites are crystalline, hydrated aluminosili- they comprised the dissolution of the ionic spe-
cates having microporous, regular structures cies, organization of the aluminum and silicon
that occur naturally. The synthetic zeolites early tetraeda species around the structure-directing
developed by Barrer and Milton in the late 1940s agents forming initial primary building units,
(Cundy and Cox 2005) were prepared using a that result in secondary building units, that finally
hydrothermal treatment at high temperature and form the polyhedra that comprise the zeolite
pressure mimicking the conditions for the synthe- structure, see Fig. 1.
sis of these minerals in nature. There are more The most probable mechanistic pathways in
than 200 framework types, recognized by the zeolite formation are described in sequence:
International Zeolite Association (IZA, http:// induction period, nucleation, and crystal growth.
www.iza-structure.org), but only a few have The nucleation and crystal growth could be sep-
been synthesized as membranes being the most arated, giving rise to the ▶ seeded hydrothermal
important: MFI, LTA, FAU, CHA, and MOR. synthesis method of zeolite membranes.
A hydrothermal treatment implies the use of The composition of the synthesis gel influ-
an aqueous solution, synthesis gel, which is ences the crystallization and the zeolite formed.
heated in an autoclave at a certain temperature Firstly the Si/Al ratio will define the ion exchange
under autogenous pressure. The chemicals in the capacity, as one atom of Si is replaced by Al a
synthesis gel include the silicon and aluminum charge defect is created. Also the hydrophylicity
sources in the presence of a mineralizing agent of the zeolite increases as the Al content
commonly sodium hydroxide or alternatively increases, being zeolite A with a Si/Al = 1 the
fluoride ion and in some cases a structure- most hydrophilic and silicalite with Si/Al = 1
directing agent (SDA) that facilitates the synthe- the most hydrophobic. The solvent, as water (and
sis of the desired zeolite structure. sometimes alcohols) has a direct effect on the
In a conventional hydrothermal synthesis all concentration of reactants, and therefore on the
the reactants are mixed together and dissolved in nucleation and growth rates. Alcohols are often
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_953-1
2 Hydrothermal Synthesis of Zeolite
Gel
Depolimerization of aluminosilicate
chains
Primary Building
Units
Secondary Building
Units
Polyhedra
Zeolite
added to retard the hydrolysis of the silicon alk- important to mention that in the last decade the
oxide which allows controlling the crystal size by microwave hydrothermal assisted method (see
reducing the polymerization rate of the silica. The ▶ Microwave synthesis of zeolite membranes)
amount and nature of the solvent will also affect has contributed to shorten considerably synthesis
the viscosity of the synthesis gel, and therefore time of zeolites and zeolite membranes (Li and
the diffusion rates of reactants during synthesis. Yang 2008) due to a more efficient volumetric
The presence of the structure-directing agent heating compared to conventional heating.
(SDA), facilitates zeolite synthesis, but in zeolite
layers, and especially in membranes, may cause
complications associated to template removal.
References
The mineralizing agents – they also have a direct
effect on the synthesis dynamics and in the hydro- Cundy CS, Cox PA (2005) The hydrothermal synthesis of
philic/hydrophobic character of the resulting zeolites: precursors, intermediates and reaction mech-
membranes. anism. Microporous Mesoporous Mater 82:1–78
The synthesis time of zeolites could vary from Li Y, Yang W (2008) Microwave synthesis of zeolite
membranes: a review. J Membr Sci 316:3–17
several hours to days in conventional ovens at
temperatures ranging from 90 C to 200 C. It is
M
y
z
x
Mordenite Membrane, Fig. 1 Framework topology of MOR and pore size of the channels. IZA structure commission
Mordenite Membrane, Fig. 2 Mordenite crystal orientation on a cordierite monolithic structure (Reprinted with
permission from Ulla et al. (2004) Chem. Commun 528–529)
Mordenite Membrane 3
Mordenite Membrane, Fig. 3 Top view and cross section of mordenite membranes prepared by secondary growth
method (Reprinted with permission from Navajas et al (2007) J Membr. Sci, 299 (1–2), 166–173)
Acetic Acid Dehydration by stability after the exposure to this mixture at mild
Pervaporation Zeolite Membranes temperature around 70 C for several days.
Although the performance of these zeolites in
Reyes Mallada pervaporation for water dehydration are lower
Department of Chemical and Environmental compared to zeolite A (Arruebo et al. 2008), the
Engineering and Aragon Nanoscience Institute, acid stability of these zeolites is higher than that
Nanoporous Films and Particles Group, of zeolite A and makes them good candidates for
Zaragoza, Spain the separation of acid mixtures. The researchers
of Mitsubishi studied the technical feasibility
of mordenite membranes for dehydration of
The best performance in pervaporation for water acetic acid aqueous solution with a feed rate of
dehydration corresponds to zeolite A, which is the 1000 kg h 1. Their results suggested that the
zeolite with the lowest Si/Al ratio (equal to 1) and developed mordenite membrane deserved to the
therefore the highest hydrophilicity. However, the further technically developments of up-scale and
high aluminum content of this zeolite makes it mass-production (Sato et al. 2011). The mem-
unstable under acidic conditions and it dissolves brane performance in pervaporation was mea-
at low pH. sured in a feed mixture of water (50 wt.%)/AAc
The separation of water in the presence of acetic (50 wt.%) to be 10.9 kg m2/h for permeate flux
acid or other acids could be important in the case of and to be 0.77 10 6 mol m2/sPa for water
membrane reactors, active zeolite membrane reac- permeance with separation factor of 500 at
tors (AZMRs), for equilibrium displacement (see 130 C.
also Membrane reactor equilibrium conversion and
Pervaporation membrane reactor). The esterifica-
tion reaction using acid produces water that could References
be removed continuously using a water permeable
acid resistant membrane. Arruebo M, Mallada R, Pina MP (2008) Zeolite mem-
branes: synthesis, characterization, important applica-
The most promising results concerning separa-
tions, and recent advances, Chapter 10. In: Handbook of
tions in acid medium have been obtained with membrane separations, 1st edn. CRC Press, Boca
zeolites with a moderate Si/Al ratio such as zeolite Raton, pp 233–323
T with Si/Al = 4 or mordenite with Si/Al ratio Sato K, Sugimoto K, Kyotani T, Shimotsuma N, Kurata
T (2011) Synthesis, reproducibility, characterization,
from 7 to 20. Both zeolites have been tested in
pervaporation and technical feasibility of preferentially
water/acetic acid mixture (50/50 wt.%) showing b-oriented mordenite membranes for dehydration of
acetic acid solution. J Membr Sci 385–386:20–29
Dynamic Membrane
Microfiltration,
Fig. 1 Industrial VSEP
vibrating modules
(Courtesy of New Logic
Research)
The main drawbacks are higher costs of equip- They consist of a stack of circular organic mem-
ment and maintenance due to moving parts and branes in separate compartments oscillating azi-
more complex design and membrane area limita- muthally around a vertical shaft at a resonant
tions for some systems. The recent availability of frequency of about 60 Hz. The maximum mem-
30 cm diameter ceramic membrane disks has brane area is 150 m2 and the power spent in
permitted the development of systems with vibrations is only 9 kW (Fig 1). It can sustain
ceramic disks rotating around several parallel pressures of 40 bars and is used with a wide
shafts in a closed tank, with a total membrane choice of membranes from MF to RO
area exceeding 120 m2 which are cheaper to build Al-Akoum et al. (2002).
and to service than multicompartment modules
with metal disks rotating between fixed organic Single Shaft Rotating Disks Systems
membranes. Bokela GmbH (Karlsruhe, Germany) commer-
Rotating disks modules give a choice between cializes the Dyno with metal disks rotating
using high rotation speeds to maximize the flux between fixed circular membranes of 12 m2 for
and thus minimize membrane area and invest- MF and UF (Fig. 2).
ment cost, or to use moderate speeds to obtain Metso Paper (Raisio, Finland) manufactures
the same flux as with tubular membranes but the Optifilter CR with blades rotating between
saving more than 60 % of the energy spent per fixed membranes of 1 m diameter and up to
m3 of permeate with these membranes. 140 m2 membrane area with a 132 kW motor
(Fig.3).
Dynamic Membrane
Microfiltration,
Fig. 2 Dyno rotating disk
module (Bokela, Germany)
Dynamic Membrane
peripheral
Microfiltration, strip rotor
Fig. 3 Sketch of OptiFilter
CR, Metso paper Co,
Finland
support layer
clamp ring
support plate
membrane
concentrate
water out
feed filtrate
water in water out
4 Dynamic Membrane Microfiltration
Dynamic Membrane Microfiltration, Table 1 List of industrial dynamic filtration modules and their characteristics
(Jaffrin 2008)
Membrane Disk MaxTMP
Manufacturer Models Type area m2 Pore size diam, mm bar
Bokela Dyno Rotating disks 0.013–12 10 nm–1 mm 137–850 4
(Germany) organic
Andritz Kraus-M Membrane rotating 0.05–16.4 7 nm–2 mm 2
(Germany) DCF on two shafts ceramic
Novoflow SSDF Membrane rotating 1–25 7 nm–2 mm 152–500 2,5
(Germany) CRD on one shaft ceramic
Metso paper Optifilter Rotors between 15-84-140 MF-UF 550–1000 3–4
(Finland) CR membranes Organic
Spintek (US) ST Membr rot on 1 shaft 0.1–2.3 MF-UF 275
Org/ceram
New Logic VSEP 0.05–150 organic Organic MF-UF-NF- 300–500 40
Research, (US) RO
Conclusion References
Dynamic filtration is not intended for initial treat- Al-Akoum O, Jaffrin MY, Ding LH, Paullier P, Vanhoutte
C (2002) An hydrodynamic investigation of
ment of huge volumes of fluids, but it should be
microfiltration and ultrafiltration in a vibrating mem-
well adapted to “end of pipe treatment” when the brane module. J Membr Sci 197:37–52
goal is to reach high solid concentration in Jaffrin MY (2008) Dynamic shear-enhanced membrane
retentate or to extract valuable components in filtration: a review of rotating disks, rotating mem-
branes and vibrating systems. J Membr Sci 324:7–25
highly charged suspensions.
Lee SA, Russoti BG, Buckland B (1995) Microfiltration of
recombinant yeast cells using a rotating disk dynamic
filtration system. Biotechnol Bioeng 48:386–400
P
phenol-fed MBR indicated that the high-phenol- carried out at different phenol concentrations
acclimated and non-settling microbes had greater from 0.5 to 3 g L 1. Biological treatment showed
degradation activity than the rest of sludge to be economical and practical leading to a com-
microbes in the bioreactor. According to these plete removal of phenol. High concentrations of
findings, the role of membrane in the high- phenol were inhibitory for growth, so it was for
phenol-fed MBR was identified as the contain- the rates of substrate utilization that were greater at
ment of non-settling and biodegradative low initial concentrations. Haldane kinetics model
microbes in bioreactor, and in turn, the for single substrate was used to obtain maximum
membrane-driven increase of non-settling phenol specific growth rates (mm = 0.438 h 1), half satu-
degrading microbes enhanced phenol elimination ration (K = 29.54 mg L 1), and substrate inhibi-
in the high-phenol-fed MBR. tion constant (K i = 72.45 mg L 1). These results
A novel process to biodegrade phenol present were in agreement with those reported in the liter-
in an acidic (1 M HCl) and salty (5 % w/w NaCl) ature for phenol removal abilities in different sys-
synthetically concocted wastewater was studied tems, although the concentration in phenol was
by Livingston (1993). The process utilized a significant, and the Haldane model was acceptable.
membrane bioreactor, in which the phenol present
in the wastewater was separated from the inor-
ganic components by means of a silicone rubber
References
membrane. Transfer of the phenol from the waste-
water into a biological growth medium allowed Ahn S, Song I, Choung Y, Park J (2011) Improved phenol
biodegradation to proceed under controlled con- degradation in high-phenol-fed MBR by membrane-
ditions which were unaffected by the presence of driven containment of non-settling biodegradation
inorganic species in the synthetic wastewater. At microbes. Desalin Water Treat 31:320–325
Abargues MR, Robles A, Bouzas A, Seco A (2012)
a wastewater flow rate of 18 mL h 1 (contact time Micropollutants removal in an anaerobic membrane
6 h), 98.5 % of phenol present in the wastewater at bioreactor and in an aerobic conventional treatment
an inlet concentration of 1,000 mg L 1 was plant. Water Sci Technol 65:2242–2250
degraded; at a contact time of 1.9 h, 65 % of the Djafer L, Ayral A, Ouagued A (2010) Robust synthesis
and performance of a titania-based ultrafiltration mem-
phenol was degraded. Phenol degradation was brane with photocatalytic properties. Sep Purif
accompanied by growth of a biofilm on the mem- Technol 75:198–203
brane tubes and by conversion of approximately Livingston AG (1993) A novel membrane bioreactor for
80 % of the carbon entering the system to CO2 detoxifying industrial waste-water. 1. Biodegradation
of phenol in a synthetically concocted waste-water.
carbon. Analysis of the transport of phenol across Biotechnol Bioeng 41:915–926
the membrane revealed that the major resistance Marrot B, Barrios-Martinez A, Moulin P, Roche N (2006)
to mass transfer derived from the diffusion of Biodegradation of high phenol concentration by acti-
phenol across the silicone rubber membrane. vated sludge in an immersed membrane bioreactor.
Biochem Eng J 30:174–183
A mathematical model was used to describe the Sadeghi F, Mehrnia MR, Nabizadeh R, Sarrafzadeh MH
transfer of phenol across the membrane and the (2012) Treatment of synthetic olefin plant wastewater
subsequent diffusion and reaction of phenol in the at various salt concentrations in a membrane bioreac-
biofilm attached to the membrane tube. This anal- tor. Clean-Soil Air Water 40:416–421
Yang S, Gu JS, Yu HY, Zhou J, Li SF, Wu XM, Wang
ysis showed that (a) the attached biofilm signifi- L (2011) Polypropylene membrane surface modifica-
cantly lowers the mass transfer driving force for tion by RAFT grafting polymerization and TiO2
phenol across the membrane, and (b) oxygen con- photocatalysts immobilization for phenol decomposi-
centration limits the phenol degradation rate in tion in a photocatalytic membrane reactor. Sep Purif
Technol 83:157–165
the biofilm. These conclusions from the model Wang ZX, Xu XC, Gong Z, Yang FL (2012) Removal of
are consistent with the experimental results. COD, phenols and ammonium from Lurgi coal gasifi-
The effect of adaptation of mixed culture in the cation wastewater using A(2)O-MBR system.
phenol biodegradation was studied by Marrot J Hazard Mater 235:78–84
et al. (2006). The degradation experiments were
P
catalysts, duration of catalytic tests, and lifetime membrane-supported titania nanoparticles (TiO2-
of the membrane in terms of physical and chem- PVC) as catalyst was used by producing in situ
ical resistance. It was observed that by feeding hydroxyl radicals as oxidant. The reaction was
the oxidant by a micro pump, working in the monitored by gas chromatography–mass spec-
“bulk tube” mode, phenol yield, final phenol con- trometry (GC-MS). The reaction conditions
centration in the organic phase, phenol turnover were optimized and the performance of the
number, and system productivity increased, and microreactor was then compared with the con-
no tar was formed. Initial oxidation state of vana- ventional laboratory scale reaction which used
dium catalysts influenced system performance: hydrogen peroxide as oxidant. The microreactor
indeed improved results in terms of yield gave a better yield of 14 % for phenol compared
(35.2 % vs. 25.1 %), conversion of hydrogen to 0.14 % in the conventional laboratory scale
peroxide to phenol (36.6 % vs. 25.9 %), and reaction. Reaction conditions such as reaction
productivity (0.97 g g(cat) 1 h 1 vs. 0.78 g g time, reaction pH, and applied potential were
(cat) 1 h 1) were obtained by using vanadium optimized. With optimized reaction conditions
(III) chloride compared to vanadium(IV) acetyl selectivity higher than 37 % and conversion of
acetonate. Higher phenol extraction/recovery in benzene higher than 88 % were obtained.
the organic phase (61.1 % vs. 46.3 %) and then The study of a new reactor design with sepa-
higher selectivity (97.5 % vs. 92.8 %) were rate membranes for distributed dosage of hydro-
obtained by increasing test duration from 270 to gen and oxygen, respectively, into
510 min. A weak membrane resistance was microstructured reaction channels for the direct
observed after 246 h of consecutive catalytic conversion of benzene to phenol in the gas phase
runs on the same membrane piece, showing deg- in a palladium membrane reactor has been inves-
radation of the membrane material tigated by Bortolotto and Dittmeyer (2010). The
(polypropylene) caused by the OH radical gener- highest phenol selectivity so far obtained on a
ated in the reacting mixture. palladium-coated PdCu foil at 423 K was 9.6 %
The one-step hydroxylation of benzene to phe- with carbon dioxide being the dominant product.
nol with oxygen and hydrogen was studied by
Shu et al. (2009). It is a promising process, but
there are severe challenges associated with the References
low phenol production. It was shown that the
reaction can be greatly promoted by the simulta- Basheer C (2013) Nanofiber-Membrane-Supported TiO2
as a catalyst for oxidation of benzene to phenol.
neous use of a dense palladium membrane as a
J Chem 2013, Article ID 562305, 7 pages
catalyst and as a hydrogen distributor. This reac- Bortolotto L, Dittmeyer R (2010) Direct hydroxylation of
tion concept with palladium membranes was benzene to phenol in a novel microstructured mem-
tested under different reaction conditions, but it brane reactor with distributed dosing of hydrogen and
oxygen. Sep Purif Technol 73:51–58
was found that the palladium membranes were Molinari R, Poerio T (2010) Remarks on studies for direct
almost inert for both the target reaction and the production of phenol in conventional and membrane
benzene combustion. The authors summarized reactors. Asia-Pac J Chem Eng 5:191–206
and compared their results with those reported Molinari R, Poerio T, Argurio P (2006) One-step produc-
tion of phenol by selective oxidation of benzene in a
in the literature investigating the effects of the
biphasic system. Catal Today 118:52–56
membrane preparation method and the combus- Molinari R, Argurio P, Poerio T (2012) Vanadium(III) and
tion of hydrogen and benzene. The hypotheses on vanadium(IV) catalysts in a membrane reactor for
the mechanism and feasibility of the membrane benzene hydroxylation to phenol and study of mem-
brane material resistance. Appl Catal Gen
concept are also given.
437:131–138
A simple, low-cost design of glass capillary Shu SL, Huang Y, Hu XJ, Fan YQ, Xu NP (2009) On the
microreactor for the catalytic oxidation of ben- membrane reactor concept for one-step hydroxylation
zene to phenol at ambient conditions was studied of benzene to phenol with oxygen and hydrogen.
J Phys Chem C 113:19618–19622
by Basheer (2013). Polyvinylchloride-nanofiber-
P
20–60 % of the overall mass-transfer resistance, steps of mass transfer were also identified in
and its value is comparable to the diffusion resis- both extraction and stripping modules. The
tance of both walls. major resistance in extraction and stripping was
Application of membrane techniques in the aqueous phase and in the membrane phase,
(pervaporation and membrane-based solvent respectively.
extraction) and adsorption to the removal of phe- The removal of phenols from wastewater has
nol from solutions modeling wastewater from been investigated under various operational con-
phenol production by cumene oxidation process ditions using hydrophobic hollow-fiber mem-
was investigated by Kujawski et al. (2004). The brane contactors (Shen et al. 2012).
transport and separation properties of composite Experimental overall mass-transfer coefficients
membranes PEBA, PERVAP 1060, and were obtained in both handmade and Liqui-
PERVAP 1070 in pervaporation of water-phenol Cel™ modules. Model predictions based on a
mixtures were determined. It was found that the resistance in series model with solvent-filled
best removal efficiency of phenol was obtained membrane pores matched well with experimental
using the PEBA membrane. MTBE, cumene, and values for tributyl phosphate/Shellsol extraction
the mixture of hydrocarbons were applied in the systems. However, the predictions were in poor
membrane-based phenol extraction. Extra-flow agreement with experimental data obtained when
contactor with Celgard X-30 polypropylene 50 % pentanol/xylene was used to treat industrial
hollow-fiber porous membranes was used in the wastewater in the handmade module. Further
experiments. MTBE was found the most efficient analysis showed that the operational pressure on
extractant. Adsorption of phenol on the different the aqueous side and the breakthrough pressure
Amberlite resins was also investigated. Among for the two solvents probably influenced the posi-
the Amberlite resins of various grades used, the tion of the interface within the membrane pores.
Amberlite XAD-4 had the best properties in the This change in wetting patterns resulted in sig-
phenol removal from the aqueous solutions. It nificant differences in mass transfer and solute
was shown that regeneration of the adsorbent recovery which can be accounted for by adjusting
bed could be effectively performed with sodium the position of the interface within the membrane
hydroxide solution. fiber.
The extraction and stripping of phenol using a
solution of tributyl phosphate in kerosene in a
hydrophobic polypropylene hollow-fiber mem- References
brane contactor was studied by Shen
et al. (2009). The effect of the aqueous and the Cichy W, Schlosser S, Szymanowski J (2001) Recovery of
phenol with CYANEX((R)) 923 in membrane
organic phase flow rates on the overall mass-
extraction-stripping systems. Solvent Extr Ion Exch
transfer coefficient for both extraction and strip- 19:905–923
ping steps was investigated. Experimental values Kujawski W, Warszawski A, Ratajczak W, Porebski T,
of the overall mass-transfer coefficient were Capala W, Ostrowska I (2004) Removal of phenol
from wastewater by different separation techniques.
determined and compared with predicted values
Desalination 163:287–296
from the resistance in series model. Results Shen SF, Smith KH, Cook S, Kentish SE, Perera JM,
showed that the overall mass-transfer coefficients Bowser T, Stevens GW (2009) Phenol recovery with
for extraction were about one order of magnitude tributyl phosphate in a hollow fiber membrane
contactor: experimental and model analysis. Sep
greater than those measured during the stripping Purif Technol. 69:48–56
process. The experimental values were in good Shen SF, Kentish SE, Stevens GW (2012) Effects of
agreement with the predicted values for the operational conditions on the removal of phenols
extraction module. However, the predicted from wastewater by a hollow-fiber membrane
contactor. Sep Purif Technol 95:80–88
values were slightly overestimated for the strip-
Schlosser S, Sabolova E (2002) Three-phase contactor
ping module. The individual mass-transfer resis- with distributed U-shaped bundles of hollow-fibers
tances were analyzed, and the rate-controlling for pertraction. J Membr Sci 210:331–347
P
experiments. MTBE was found the most efficient concentration of phenol from 0 to 7 wt.%. The
extractant. Adsorption of phenol on the different total flux also increased up to 930 gm 2h 1 with
Amberlite resins was also investigated. Among increasing phenol partial flux. In the sorption
the Amberlite resins of various grades used, the measurement at 60 C, the concentration of phe-
Amberlite XAD-4 had the best properties in the nol in the membrane was 68 wt.%, which was
phenol removal from the aqueous solutions. It higher than that of the permeate solution.
was shown that regeneration of the adsorbent The effect of the methylene group length in
bed could be effectively performed with sodium poly(alkylene glycols) on permselectivity and
hydroxide solution. solubility of phenol was studied by Hoshi
Application of pervaporation and adsorption et al. (2000) in dilute aqueous solution through
to the removal of phenol from solutions modeling polyurethane membranes by pervaporation. The
wastewater from phenol production with cumene poly(alkylene glycols) were obtained by poly-
oxidation process was investigated by Kujawski condensation of 1,6-hexanediol, 1,8-octanediol,
et al. (2004b). The transport and separation prop- and 1,10-decanediol with a sulfuric acid catalyst.
erties of composite membranes PEBA, PERVAP Polyethyleneglycol and polytetramethyle-
1060, and PERVAP 1070 in pervaporation of neglycol were commercially available. Progress
water-acetone, water-phenol, and water-phenol- of the polymerization in the poly(alkylene gly-
acetone mixtures were determined. It was found cols) was confirmed by FTIR, 1H-NMR analysis,
that all membranes were selective toward phenol. and size-exclusion chromatography (SEC) mea-
The PEBA membrane showed the best selectiv- surements. The polyurethanes were obtained by
ity. However, this membrane is not actually polyaddition reaction of
available on the commercial scale. Thus, in the 1,6-hexamethylenediisocyanate and the poly
practical applications, PERVAP-1060 and (alkylene glycol) and were confirmed by FTIR
PERVAP-1070 could be used. Adsorption of analysis and SEC measurements. The phenol
phenol on the different Amberlite resins was concentration in a permeate liquid increased
also investigated. Among the Amberlite resins from 25.1 to 36.2 wt.%, and the phenol partial
of various grades used, the Amberlite XAD-4 flux also increased from 49.3 to 68.9 gm 2h 1
had the best properties in decontamination of with increasing the methylene group length in the
aqueous phenol solutions. It was shown that poly(alkylene glycols), whereas the water partial
regeneration of the adsorbent bed could be effec- flux slightly decreased. As a result of sorption
tively performed with sodium hydroxide measurements, the change in the degree of swell-
solution. ing was small, and the phenol concentration in the
The separation of a phenol-water mixture membrane increased from 42.1 to 70.8 wt.%. The
using a polyurethane membrane by a increase in the methylene group length of the
pervaporation method was investigated by poly(alkylene glycols) should contribute to an
Hoshi et al. (1997). Polyurethane was selected increase in the hydrophobicity of the polyure-
as a membrane material because its affinity for thane so that the solubility of phenol to the mem-
phenol was considered to be high and was pre- brane should increase. The phenol concentration
pared by the polyaddition of in the permeate liquid and the phenol partial flux
1,6-diisocyanatohexane and polytetramethyle- increased with an increase in the methylene
neglycol. The polyurethane layer was group length of the poly(alkylene glycols) due
sandwiched with a porous polypropylene mem- to the increase in the phenol solubility for the
brane (Celgard ® 2500). Pervaporation measure- polyurethane membranes.
ments were carried out under vacuum on the
permeate side, and the permeate vapor was col-
lected with a liquid nitrogen trap. The phenol
concentration in the permeate solution increased
from 0 to 65 wt.% with increasing feed
Phenol Separation on PV Membrane Reactor 3
Flat Sheet Membrane Photocatalytic the initial 4NP concentration (40 mg/l) after a
Reactor transient period of 300 min.
In another method, the catalyst, TiO2 P25
Raffaele Molinari Degussa, was immobilized by physical deposi-
Dip.to di Ingegneria per l’Ambiente e il tion on a flat-sheet polymeric membrane, and
Territorio e Ingegneria Chimica (DIATIC), 4NP was used as a model molecule to evaluate
Università della Calabria, Rende, CS, Italy the reactor performance (Molinari et al. 2000).
A preliminary investigation of the stability, under
UV irradiation, of some eligible polymeric mem-
When membrane configuration is flat type and it branes was carried out by using scanning electron
is coupled to a photocatalytic reaction, the reactor microscopy (SEM), optical microscopy (OM),
can be named flat-sheet membrane photocatalytic determinations of water permeation flux (WPF),
reactor. and total organic carbon (TOC). These tests
A recirculation cell containing various types showed that commercial membranes made of
of flat-sheet membranes which were able to retain fluoride + PP (FS 50 PP-Dow), polysulfone +
the suspended catalyst and partially selective to PP (GR 51 PP-TechSep), and polyacrylonitrile
the pollutant was studied by Molinari (PAN-TechSep) seemed to be quite stable to
et al. (2001). The membranes were NTR7410 UV light over a 24 h period of irradiation. Immo-
and NTR7450 (Nitto Denko), N30F and bilization of TiO2 onto membranes by
NF-PES-010 (Hoechst), and MPCB0000R98 ultrafiltrating TiO2 suspensions showed an opti-
(SEPAREM). The measured permeate flux was mal layer density slightly >2.04 mg TiO2 per cm2
in the range 5–30 l/h m2 at 4 bar, and all mem- of membrane surface area. Results obtained from
branes showed both a rejection and a capacity to membrane reactor studies indicated that the
adsorb the pollutant with a transitory phase vary- observed initial rate constants for the degradation
ing from 80 to 400 min at 4 bar. This behavior of 4NP were almost independent on the amount
could be a benefit for the process because oscil- of TiO2 employed over the range
lations in the pollutant concentration were not 0.76–4.08 mg/cm2. A 50 % weight degradation
transmitted in the permeate. Three factors, rejec- of 4NP after 5 h of irradiation in the presence of
tion, photocatalytic degradation, and adsorption, air was obtained. An almost complete degrada-
were able to maintain the 4-nitrophenol (4NP) tion of 4NP, instead, was observed in the pres-
concentration in the permeate at very low values. ence of TiO2 suspended in the solution and pure
For the continuous system, the lowest 4NP con- oxygen. The permeate deriving from the mem-
centration in the permeate was 6–7 % (w/w) of brane photoreactor was clear, and 4NP
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_964-4
2 Flat Sheet Membrane Photocatalytic Reactor
concentration was approximately equal to that module was relatively higher than that of the edge
found in the retentate. The possibility of the con- regions when using a single orifice, but more
tinuous reuse of the photocatalyst and the contin- uniformity was achieved with two.
uous separation of products from the reaction Exploration of two major commercialized flat-
medium gave some advantages over traditional sheet and hollow-fiber membranes in a submerged
approaches. membrane fungi reactor fed with a synthetic tex-
A flat-sheet membrane photocatalytic reactor tile wastewater revealed striking differences in the
operates, generally, with suspended solids (the extent and mechanism of fouling between the two
catalyst) and air bubbling (oxygen feed), so, in types, indicating a case-specific scope of choice
the following, some cases of interest for operat- between them for industrial wastewater treatment
ing such reactors are reported. (Hai et al. 2005). The hollow-fiber membrane
Selection of a membrane configuration is a exhibited fouling with a cake layer composed of
crucial step in the design process and has a high fungi and starch, intensity being proportional to
impact on further plant operations. Despite the operating flux (0.05–0.3 m/d). Conversely, the
increasing experience with full-scale applica- flat-sheet membrane suffered from immediate
tions, practical knowledge concerning the impact internal pore blocking beyond a critical flux of
of different membrane configurations on process 0.2 m3 m 2 d 1. During the experiment with
performance and operational costs is still lacking. major constituents of the synthetic wastewater
Full-scale performance data of a membrane bio- separately, while media containing only starch
reactor (MBR) comparing the use of flat-sheet and only dye induced negligible fouling, flux-
and hollow-fiber membranes and analyses of the dependent pore blocking was evident for both the
consequences on operation, performance, and hollow-fiber (0.288 m3 m 2 d 1) and flat-sheet
treatment efficiency have been reported by membranes (1.3 m3 m 2 d 1) for the mixture of
Krzeminski et al. (2012). Hollow-fiber configu- starch and dye. Despite that a remarkable 99 %
rations, compared to the flat sheet, are designed color and 97 % TOC removal were achieved by
for higher fluxes, operated at lower concentra- both membranes, fouling with different modes and
tions, cleaned more often, and protected by intensity for the two types under similar conditions
stricter pretreatment. Filterability of activated and for the same type of membrane under different
sludge from municipal MBRs was better than exposure conditions warrants development of
from industrial MBRs and did not depend on suitable modules for such recalcitrant wastewater.
membrane configuration. The energy consump- The oxygen transfer across a microporous,
tion depends more on the influent type than on the flat-sheet membrane with and without a nitrifying
membrane configuration. membrane-aerated biofilm (MAB) was studied
An aerated flat-sheet module focusing on the by Shanahan and Semmens (2006). Clean mem-
effect of bubble distribution on the spatial varia- brane oxygen transfer was quantified via average
tion of surface mass transfer with intermittent mass transfer coefficients and local fluxes calcu-
slug bubbling was studied by Field et al. (2011). lated from profiles of dissolved oxygen
This mode of operation will delay the onset of the (DO) along the membrane length. Stoichiometric
transmembrane pressure jump if biomass calculations and DO profiles were used to
removal is more dependent upon maximum characterize oxygen transfer with a nitrifying
shear stress than mean shear stress. Two basic MAB. Comparison of the local fluxes with clean
setups were considered: an orifice in the middle and biofilm-coated membranes revealed that
of the aeration tube, at the base, and two symmet- oxygen transfer was decreased in upstream sec-
rically placed orifices in the aeration tube. With tions of the membrane during cultivation of an
relatively low air rates, a single orifice generates a MAB due to reduced advection and/or turbulence
higher average enhancement than two orifices, near the membrane surface. By contrast, oxygen
but the reverse was found at a relatively higher transfer was increased in downstream sections of
air rate. The enhancement in the center area of the the membrane via bacterial respiration. Oxygen
Flat Sheet Membrane Photocatalytic Reactor 3
fluxes generally decreased in the downstream Hai FI, Yamamoto K, Fukushi K (2005) Different fouling
direction with biofilm-coated membranes; how- modes of submerged hollow-fiber and flat-sheet mem-
branes induced by high strength wastewater with con-
ever, variability in biofilm structure and mem- current biofouling. Desalination 180:89–97
brane coverage altered this trend on several Krzeminski P, Gil JA, van Nieuwenhuijzen AF, van der
occasions. Furthermore, biofilm structures were Graaf JHJM, van Lier JB (2012) Flat sheet or hollow
observed to form via sloughing and settling of fibre – comparison of full-scale membrane bio-reactor
configurations. Desalination Water Treat 42:100–106
biomass at the membrane surface. Thus mem- Molinari R, Mungari M, Drioli E, Di Paola A, Loddo V,
brane configuration may have a significant influ- Palmisano L, Schiavello M (2000) Study on a
ence on oxygen transfer rates in membrane photocatalytic membrane reactor for water purifica-
reactors. tion. Catal Today 55:71–78
Molinari R, Grande C, Drioli E, Palmisano L, Schiavello
M (2001) Photocatalytic membrane reactors for deg-
radation of organic pollutants in water. Catal Today
References 67:273–279
Shanahan JW, Semmens MJ (2006) Influence of a nitrify-
Field RW, Zhang KS, Cui ZF, Hwang BK (2011) Flat ing biofilm on local oxygen fluxes across a micro-
sheet MBRs: analysis of TMP rise and surface mass porous flat sheet membrane. J Membr Sci 277:65–74
transfer coefficient. Desalination Water Treat
35:82–91
P
vanillin in water by TiO2 photocatalysis. Appl Catal Palmisano G, García-López E, Marcı̀ G, Loddo V,
Environ 111–112:555–561 Yurdakal S, Augugliaro V, Palmisano L (2010)
Camera Roda G, Augugliaro V, Loddo V, Palmisano L, Advances in selective conversions by heterogeneous
Palmisano G (2010) Production of aldehydes by oxi- photocatalysis. Chem Commun 46:7074–7089
dation in aqueous medium with selective recovery of Parrino F, Augugliaro V, Camera Roda G, Loddo V,
the product by means of pervaporation. Patent López-Muñoz MJ, Márquez-Álvarez C, Palmisano G,
RM10A000319 Palmisano L, Puma MA (2012) Visible light induced
Camera Roda G, Augugliaro V, Cardillo A, Loddo V, oxidation of trans-ferulic acid by TiO2 photocatalysis.
Palmisano G, Palmisano L (2013) A pervaporation J Catal 295:254–260
photocatalytic reactor for the green synthesis of vanil- Pillai UR, Sahle-Demessie E (2002) Selective oxidation of
lin. Chem Eng J 224:136–143. DOI: 10.1016/j. alcohols in gas phase using light-activated titanium
cej.2012.10.037 dioxide. J Catal 211:434–444
Fukuzumi S, Ohkubo K (2013) Selective photocatalytic Yurdakal S, Loddo V, Palmisano G, Augugliaro V,
reactions with organic photocatalysts. Chem Sci Berber H, Palmisano L (2010) Kinetics of 4-
4:561–574 methoxybenzyl alcohol oxidation in aqueous solution
Molinari R, Caruso A, Poerio T (2009) Direct benzene in a fixed bed photocatalytic reactor. Ind Eng Chem
conversion to phenol in a hybrid photocatalytic mem- Res 49:6699–6708
brane reactor. Catal Today 144:81–86
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activities of TiO2 particles immobilized on two The experimental results showed a satisfactory
kinds of support material, stainless steel mesh degradation efficiency of the photocatalytic
(SSM) and fiberglass cloth (FGC), were investi- membrane process. The influence of various
gated for photocatalytic oxidation of 2-propanol, parameters (e.g., feed concentration,
as a model volatile organic compound, dissolved recirculation rate) has been discussed to obtain
in aerated aqueous solution. The TiO2 particles high reaction rates, operating stability, and high
immobilized on both support materials exhibited membrane rejection, both for substrates and
photocatalytic activity to oxidize 2-propanol into by-products. Congo Red was photodegraded
acetone and carbon dioxide (CO2), and the activ- with higher rate under the same experimental
ity levels of the TiO2 particles immobilized on conditions probably due to its higher adsorption
the two kinds of support materials were compa- onto the catalyst surface. It was possible to treat
rable. Presumably due to the presence of a small successfully highly concentrated solutions
amount of metal species originating in SSM that (500 mg/L) of both dyes by means of a continu-
might work as reduction catalysts, molecular ous process obtaining good values of permeate
hydrogen H2 was also liberated on the TiO2- fluxes (30–70 L/m2h); this could be interesting
immobilized SSM. Results of analysis of weight for industrial applications. The reactor containing
loss after photoirradiation suggested that the sta- the suspended photocatalyst was significantly
bility of the TiO2-immobilized FGC was better more efficient than the reactor containing the
than that of the TiO2-immobilized SSM. On the catalyst entrapped into the membrane.
basis of these results, FGC was employed in An advanced oxidation process (AOP) with
construction of a photocatalytic reactor equipped reactor capacity of 150 L, using ultraviolet
with an O2-permeable Teflon membrane in order (UV) radiation and TiO2 photocatalyst, was eval-
to make oxygen pass from a gas space to a solu- uated for the destruction of toxic organic chemi-
tion space and to keep the surface of the cal, bisphenol A (BPA) by Thiruvenkatachari
immobilized TiO2 photocatalyst, facing an aque- et al. (2005). TiO2, in the form of powder, was
ous solution containing volatile organic com- suspended as slurry in the water avoiding the
pounds, saturated with dissolved O2. From the commonly adopted practice of immobilizing it
results of photocatalytic oxidative decomposition onto a carrier material such as glass, concrete,
of 2-propanol, it was clarified that the surfaces of or ceramics. Adsorption of BPA by TiO2 was
TiO2 particles could be sufficiently supplied with evaluated and was performed as a pretreatment
O2 from the gas space through the membrane to to AOP. The combined effect of ozone with the
accelerate the oxidation. AOP process was also studied. Coupling ozone
Dyes are organic compounds used in textile, with UV/TiO2 brought about a synergistic effect
food, and drug industries, and their abatement on BPA degradation and 10 ppm of BPA, and the
represents one of the main problems in the treat- intermediate organic compounds were
ment processes because generally they are very completely removed within 3 h. The highlight
stable toxic compounds. Two commercial of this study was the simultaneous degradation
azo-dyes, i.e., Congo Red (C32H22N6Na2O6S2) of BPA and separation of TiO2 particles from
and Patent Blue (C27H31N2NaO6S2), in aqueous water after the photocatalytic treatment, in order
solution were degraded in a photocatalytic mem- to obtain reusable quality water. Separation of
brane reactor (Molinari et al. 2004) by using TiO2 TiO2 particles was carried out by a unique
Degussa P25 as the catalyst. Different system two-stage coagulation and settling process
configurations and irradiating sources were stud- followed by submerged hollow fiber
ied, and the influence of some operational param- microfiltration membrane technique. With initial
eters such as the pressure in the membrane cell turbidity of 4,000 NTU, the turbidity of the final
and the initial concentration of the substrates permeate water was well below 0.1 NTU. Some
were determined. A comparison between of the main advantages of this hybrid treatment
suspended and entrapped TiO2 was also done. system include the possibility of large-scale
Photocatalytic Membrane Reactor: Degradation of Organic Compounds 3
treatment, complete and efficient BPA and its nanofiltration (NF) and ultrafiltration (UF), but
organic intermediates degradation, easy separa- these systems can lead to membrane fouling.
tion and reuse of TiO2 that resulted free from Only the combination of photocatalysis and
chemical coagulant contaminants, reusable qual- membrane distillation avoids this problem, but
ity water, and potentiality for continuous opera- it needs energy to reach pervaporation phenom-
tion with simple process modifications. ena. The MPR system worked at ambient temper-
A study of the photodegradation of different ature, with the membrane used as a barrier for
pharmaceuticals [furosemide, ranitidine particles and to extract the organic compounds
(hydrochloride), ofloxacine, phenazone, from the turbid water without transmembrane
naproxen, carbamazepine, and clofibric acid] in pressure. Thus it was possible to separate the
aqueous medium at various pHs by using a batch polluted turbid water from the photoreactor com-
photoreactor and a photocatalytic membrane partment and to separate TiO2 continuously from
reactor working in recirculation regime was car- the treated water. The photocatalytic reaction and
ried out by Molinari et al. (2006). Polycrystalline dialysis were studied separately before the MPR
TiO2 was used as the photocatalyst, and different process was developed. A model pollutant,
membranes (NTR 7410, PAN GKSS HV3/T, 2,4-dihydroxybenzoic acid (2,4-DHBA), was
N 30F, NF PES 10) were tested. A different mineralized from turbid waters by
adsorption of the substrates onto the catalyst sur- photocatalysis. By means of the membrane, the
face was observed owing to the hydrophilic/ TiO2 remained in the photoreactor compartment
hydrophobic character of the catalyst, depending without filtration and bentonite was kept away
on the pH. The photodegradation of the seven from the photoreactor.
molecules in the batch reactor was successfully The degradation of toxic organic compounds
carried out and the behavior was in accordance such as trichloroethylene (TCE) in water, using a
with pseudo-first-order kinetics. Furosemide and combined photocatalysis/microfiltration
ranitidine were selected to carry out the study of (MF) system, was focused by Choo
rejection and photodegradation in the hybrid et al. (2008). The performances of the hybrid
membrane system. The permeate flux of the system were investigated in terms of the removal
treated water was in the 31.5–60.0 L/(hm2) efficiency of TCE and membrane permeability, in
range for NTR 7410 membrane, whereas rejec- the presence or absence of humic acids and at
tion values in the range 10–60 % for furosemide different pHs. The fate of TCE during the
and 5–30 % for ranitidine in the dark (without photocatalytic reactions was checked in order to
photoreaction) were found. The degradation in evaluate the feasibility of the photocatalytic
the hybrid membrane photoreactor showed that membrane reactor (PMR). Greater TCE degrada-
the photocatalyst was retained by the membrane tion (>60 %) was achieved with an increase in
in the reaction ambient, while the membrane the TiO2 dosage (up to 1.5 g/L) in PMR, but a
rejection toward the pollutants was not very sat- substantially large TiO2 dosage brought about a
isfactory. A net decrease of the rejection down to decrease in TCE degradation efficiency. The
0 was observed in the contemporary presence of photocatalytic decomposition of TCE appeared
light, photocatalyst, and oxygen. to be more effective at acidic pH conditions than
The combination of a dialysis membrane and a at a neutral or alkaline pH. The alkalinity and the
photocatalytic reactor into an original membrane addition of humic acids into the feedwater did not
photoreactor (MPR) to mineralize organic com- produce a significant effect on TCE degradation,
pounds contained in artificial turbid waters which while humic acids (whose dose was 1 mg/L as
were obtained by using natural clay named ben- TOC) in the feedwater played a role in a decline
tonite was studied by Azrague et al. (2007). Var- of permeability by 60 %. Membrane permeability
ious systems have been described in the in the PMR was also affected by tangential veloc-
literature, combining photocatalysis with ities. An improvement of 60 % in flux was
pressure-driven membrane techniques, such as achieved when the tangential velocity increased
4 Photocatalytic Membrane Reactor: Degradation of Organic Compounds
from 0.19 to 1.45 m/s. This occurred because Molinari R, Pirillo F, Falco M, Loddo V, Palmisano
flow regimes can govern the deposition of TiO2 L (2004) Photocatalytic degradation of dyes by using
a membrane reactor. Chem Eng Process 43:1103–1114
particles on the membrane surface. Molinari R, Pirillo F, Loddo V, Palmisano L (2006) Het-
erogeneous photocatalytic degradation of pharmaceu-
ticals in water by using polycrystalline TiO2 and a
References nanofiltration membrane reactor. Catal Today
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Thiruvenkatachari R, Kwon TO, Moon IS (2005) A total
Azrague K, Aimar P, Benoit-Marquie F, Maurette MT solution for simultaneous organic degradation and par-
(2007) A new combination of a membrane and a ticle separation using photocatalytic oxidation and
photocatalytic reactor for the depollution of turbid submerged microfiltration membrane hybrid process.
water. Appl Catal Environ 72:197–204 Korean J Chem Eng 22:938–944
Choo KH, Chang DI, Park KW, Kim MH (2008) Use of an Villacres R, Ikeda S, Torimoto T, Ohtani B (2003) Devel-
integrated photocatalysis/hollow fiber microfiltration opment of a novel photocatalytic reaction system for
system for the removal of trichloroethylene in water. oxidative decomposition of volatile organic com-
J Hazard Mater 152:183–190 pounds in water with enhanced aeration. J Photochem
Lee SA, Choo KH, Lee CH, Lee HI, Hyeon T, Choi W, Photobiol A Chem 160:121–126
Kwon HH (2001) Use of ultrafiltration membranes for
the separation of TiO2 photocatalysts in drinking water
treatment. Ind Eng Chem Res 40:1712–1719
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experiments because permeability and rejection bisphenol A (BPA) as the model pollutant. Aera-
tests indicated that it was able to hold both cata- tion was applied in the submerged membrane
lyst and small molecules carrying the same mem- photoreactor (SMPR) to provide (i) mixing,
brane charge (negative), thanks to the Donnan (ii) dissolved oxygen, (iii) mechanical agitation
exclusion. Despite the fluxes ranged between (to prevent agglomeration of TiO2 particles), and
20 and 40 L h 1 m 2 in operating conditions at (iv) shear forces (to remove TiO2 particles from
6 bar and these values were interesting for appli- the membrane surface). It was found that inter-
cation purposes, the rejections of NTR-7410 mittent permeation enhanced the sustainability of
nanofiltration membrane, obtained during opera- the submerged membranes but showed no effect
tion of the membrane photoreactor in the degra- on the photoactivity of the system. An intermit-
dation of humic acids, patent blue dye, and 4- tence aeration frequency (IF) of 0.1 was sufficient
nitrophenol, were significantly lower than those to reduce the fouling rate of the membrane under
obtained in the absence of photodegradation, the experimental conditions. The SMPR appears
probably because of the small molecular size of to be very effective and can achieve removal of
the by-products and of the intermediate species low-concentration organics (such as BPA) in a
produced during the photodegradation process. compact, low-energy system. The combined
This means that in order to select a suitable mem- photocatalytic and membrane processes have
brane, rejection should be determined during been more recently addressed also toward the
operation of the photoreactor. selective production of high-value molecules in
A batch-recirculated photoreactor was com- mild experimental conditions by using suitable
bined with a hollow-fiber membrane ultrafiltra- photocatalysts, solvent, and starting substrates
tion (UF) unit for heterogeneous photocatalysis and membranes (Molinari et al. 2009a, b;
applications. The operation and modeling of the Augugliaro and Palmisano 2010).
UF process on the performance of the integrated
photoreactor-UF process was studied by
Sopajaree et al. (1999). Methylene blue and tita-
References
nium dioxide (Degussa P-25) were used as the
test pollutant and photocatalyst, respectively. The Augugliaro V, Palmisano L (2010) Green oxidation of
influence of cross-flow velocity, transmembrane alcohols to carbonyl compounds by heterogeneous
pressure, and TiO2 dose on the permeate flux photocatalysis. ChemSusChem 3:1135–1138
through the hollow-fiber membrane was Augugliaro V, Litter M, Palmisano L, Soria J (2006) The
combination of heterogeneous photocatalysis with
described. The data were modeled on the basis chemical and physical operations: a tool for improving
of concentration polarization and gel layer for- the photoprocess performance. J Photochem Photobiol
mation at the membrane surface/feed slurry C Photochem Rev 7:127–144
boundary. Chin SS, Lim TM, Chiang K, Fane AG (2007) Hybrid
low-pressure submerged membrane photoreactor for
The photocatalytic degradation of natural the removal of bisphenol A. Desalination 202:253–261
organic matter (NOM) is an attractive option in Choo KH, Tao R, Kim MJ (2008) Use of a photocatalytic
the treatment of drinking water (Choo membrane reactor for the removal of natural organic
et al. 2008). The performance of a submerged matter in water: effect of photoinduced desorption and
ferrihydrite adsorption. J Membr Sci 322:368–374
photocatalytic membrane reactor (PMR) was Molinari R, Borgese M, Drioli E, Palmisano L, Schiavello
investigated with regard to the removal of NOM M (2002) Hybrid processes coupling photocatalysis
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Molinari R, Caruso A, Palmisano L (2009a)
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module was investigated. Low-pressure sub- or degradation of organic compounds. In: Drioli E,
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Photocatalytic Processes by Membrane Operations 3
Molinari R, Caruso A, Poerio T (2009b) Direct benzene heterogeneous photocatalysis. Part II: experiments on
conversion to phenol in a hybrid photocatalytic mem- the ultrafiltration unit and combined operation. J Appl
brane reactor. Catal Today 144:81–86 Electrochem 29:1111–1118
Sopajaree K, Qasim SA, Basak S, Rajeshwar K (1999) An
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P
degradation and mineralization of dyes molecule (dyes or other color species). The
discharged into wastewater from textile and major advantage of these systems is that they
other industrial processes (Lam et al. 2012), are able to achieve the degradation of organic
although ZnO can give rise to anodic pollutants by using visible light from the sun as
photocorrosion in aqueous systems, depending energy and O2 in the air as the oxidant under
on the experimental conditions chosen. ambient conditions (Chen et al. 2010).
Removal of nitrogen-containing organic com-
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Photoelectrochemical cell and the factors that Lianos P (2011) Production of electricity and hydrogen by
photocatalytic degradation of organic wastes in a
affect efficient production of electricity and
photoelectrochemical cell. The concept of the
hydrogen by photocatalytic degradation of photofuelcell: a review of a re-emerging research
(principally) organic and (secondarily) inorganic field. J Hazard Mater 185:575–590
waste materials are reported by Lianos. Materials Molinari R, Pirillo F, Falco M, Loddo V, Palmisano
L (2003) Photocatalytic oxidation of dyes in a mem-
used for making a photoanode and the rest of the
brane reactor. J Catal Mater Environ 2:77–80
components of the cell as well as the models of Molinari R, Pirillo F, Loddo V, Palmisano L (2006) Het-
cell efficiency and photodegradation procedures erogeneous photocatalytic degradation of pharmaceu-
during cell operation have been also described ticals in water by using polycrystalline TiO2 and a
nanofiltration membrane reactor. Catal Today
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Efficient photochemical systems for environ- Yang CJ, Peng TY, Deng KJ, Zan L (2011) Solid-phase
mental remediation can be constituted by a semi- photocatalytic degradation of waste plastics. Prog
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stirred photoreactors, the presence of the irradiation rates at the reactor wall below
photocatalyst, usually a powdered micro- or 1 10 6 Einstein cm 2 s 1, and good mixing
nanocrystalline semiconductor, affects in a com- operation (Re >1700), mass transport limitations
plex way the depth of radiation penetration. in the bulk of the fluid can be considered virtually
Photoreactors and, thus, photocatalytic pro- nonexistent.
cesses are applicable in wastewater treatment, The photocatalyst with designed physico-
energy production, chemical synthesis, and chemical properties is the key in the process.
greenhouse gas mitigation. They have the poten- Recent research progress toward the design and
tial to address both the consumption of preparation of porous photocatalysts with struc-
nonrenewable fossil fuels and global warming, tural, compositional, and morphological proper-
two of the greatest problems facing humankind. ties suitable for use in a photocatalytic reactor for
The state-of-the-art in solar photoreactor design water treatment via advanced oxidation processes
to assess those systems which are most applicable have been reviewed by Pan et al. (2010). Various
for industrial-scale implementation has been synthetic strategies for fabricating porous
reviewed by Braham and Harris (2009). Designs photocatalysts with well-defined microscopic
for parabolic trough, compound parabolic, morphologies and nano/mesoscopic active
inclined plate, double-skin sheet, rotating disk, nanobuilding blocks and the synthesis-
water bell, fiber optic, and fixed/fluidized bed component-structure-property relationship work-
photoreactors are qualitatively discussed and ing in photocatalyst design are discussed.
compared. Compound parabolic photoreactors
are most suited to near-term applications at pilot
scale (>1000 L/day) due to their advantageous
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water treatment. But, nowadays, membrane Basile A, Gallucci F (eds) Simulation of membrane
reactors. Nova Science Publishers, New York,
photoreactors have shown to solve this drawback pp 401–443
(Molinari et al. 2002). Molinari R, Palmisano L, Drioli E, Schiavello M (2002)
The existence of mass transfer limitations in Studies on various reactor configurations for coupling
slurry photocatalytic reactors and experimental photocatalysis and membrane processes in water puri-
fication. J Membr Sci 206:399–415
validation was made in a flat reactor that was Pan JH, Dou HQ, Xiong ZG, Xu C, Ma JZ, Zhao XS
part of a recycling system by Ballari et al. (2010) Porous photocatalysts for advanced water puri-
(2010). When the photocatalytic reaction is not fications. J Mater Chem 20:4512–4528
fast, employing catalyst loadings below 1 g L 1,
H
Characterization of Porous and Dense Membranes, track etching, (d) a porous cellulose nitrate membrane
Fig. 1 Scanning electron micrographs of (a) a sintered prepared from a homogeneous polymer solution by
membrane prepared from a polymer powder, (b) a mem- water vapor precipitation, and (e) a porous polypropylene
brane prepared by stretching an extruded polytetrafluor- membrane precipitated by thermal gelation from a hot
oethylene film perpendicular to the direction of extrusion, polymer solution
(c) of a capillary pore polycarbonate membrane made by
the solution passing through the pores of the For the determination of the pure water flux, it
membrane, and Dp is the applied pressure. is very important to use a certain water quality.
Generally deionized or distilled water with a
Characterization of Porous and Dense Membranes 3
Characterization
of Porous and Dense
stress
Membranes,
Fig. 2 Stress versus strain
diagram of a membrane
sample indicating the
elastic and plastic
deformation and the
break point
breakpoint
elastic plastic
strain
deformation deformation
conductivity of <5 mS cm1, which is treated by fouling which is generally more pronounced for
microfiltration to remove suspended materials, is microfiltration than for ultrafiltration.
used as a test solution. The flux is determined at
different applied pressures and plotted as a func-
tion of the pressure. From the slope of the plot, Microscopic Techniques
the hydrodynamic permeability is obtained. Prior
to the flux measurements, the membranes should A variety of microscopic techniques are used to
be pressurized by filtration of pure water at a study membrane structures, such as scanning
hydrostatic pressure that is at the upper limit of electron microscopy, field emission electron
the recommended operating pressure for one to microscopy, transmission electron microscopy,
two hours to compress the membrane to a stable and atomic force microscopy. The advantage of
value that will not further deform when used at these techniques is that direct visual information
lower pressures. Possible preservatives, often of the membrane morphology is obtained. The
present in membranes, must be eliminated by a different microscopic techniques require differ-
washing procedure. ent preparation methods and have different reso-
Some inorganic membranes, like Al2O3-based lution. Scanning electron microscopy, e.g., has a
types, show an apparent internal pore clogging resolution of up to 5 nm and provides good infor-
when deionized water is used in the pure water mation on the structures of micro- and ultrafiltra-
flux measurements. In these cases an electrolyte tion membranes including pore sizes and pore
solution is used for determining the membrane shapes. To reach a high resolution, high electron
flux, e.g., a NaCl or KCl solution. Since there beam energy has to be applied, which can damage
exists no standard method for the determination the membrane samples. Another problem is that
of the pure water flux, companies use their own in electron microscopy, a conductive layer must
standards, which makes a reliable comparison of coat the samples. This is generally done in a high
pure water fluxes rather difficult. vacuum, which can lead to a change of the struc-
Typical pure water fluxes of microfiltration ture of membranes made from hydrophilic
membranes vary from 500 to 50,000 L m2 h1 polymers.
bar1, while pure water fluxes of ultrafiltration The pore sizes and pore shapes of ultrafiltra-
membranes vary from 50 to 800 L m2 h1 bar1. tion membranes can also be determined by trans-
In practical applications, fluxes are normally mission electron microscopy which has a
much lower, and a steep flux decline is observed resolution of 0.4–0.5 nm or by field emission
during the first period of operation. This flux electron microscopy which has a resolution of
decline is mainly determined by membrane 0.6–0.7 nm. The transmission electron
4 Characterization of Porous and Dense Membranes
the composition of the solution with which the membranes. The separation of various compo-
membrane is in contact. Especially the concen- nents is based on a sieving mechanism, i.e., this
tration of the solution has a significant effect on membrane retains particles or molecules that are
the water sorption of the membrane because of larger in size than the pores of a membrane.
osmotic effects that are directly related to the A relation as a function of the particle size and
chemical potential difference of the water in the the pore size for the membrane retention can be
membrane and in the solution. The state of the defined by a relation between the pore and the
water in the membrane can also be rather differ- particle radius (Ferry 1936). If the particles are
ent. Part of the water is so-called “free” water. spherical and have a radius rs and the membrane
Another part of the water is strongly bound within pores are cylindrical with a radius rp, the follow-
the hydration shell of the counterions and the ing relation can be applied to describe the mem-
fixed charges of the membrane, while again brane solute rejection:
another part is more loosely bound to the basic
polymer matrix. The different water structures in rs 2 2
ion-exchange membranes are studied by differ- R¼ 1 1 (3)
rp
ential scanning calorimetry, infrared spectros-
copy, and nuclear magnetic resonance For the radius of the molecule, either the radius of
(Komoroski and Mauritz 1982). Studies of the gyration or the hydrodynamic radius can be used.
water structure within the membrane and its The Ferry model is rather simplified, but gives a
interaction with the membrane polymer, fixed good approximation of the expected retention
charges, and counterions require more sophisti- when particle size and the membrane pore radius
cated spectroscopic measurements. The total are known.
water uptake of the membrane in equilibrium
with an electrolyte solution, however, can be
determined quite easily by measuring the weight
difference between a membrane in the wet and Retention and Molecular Weight Cutoff
dry state. To determine the water content of a
membrane, a sample is equilibrated in a test solu- To describe the retention of ultrafiltration mem-
tion. After removing the surface water from the branes, usually the molecular weight cutoff is
sample, the wet weight of the swollen membrane used. The molecular weight cutoff determination
is determined. The sample is then dried at ele- is very sensitive to the experimental conditions,
vated temperature over phosphorus pentoxide i.e., the solutes and their concentration used in the
under reduced pressure until a constant weight test, the applied pressure, and the temperature.
is obtained. The water content of a membrane is Therefore, a comparison of retention data given
obtained in weight percent by: by different manufacturers is generally
problematic. As test conditions for determining
W wet W dry the ultrafiltration membrane cutoff, a transmem-
wt% swelling ¼ 100 (2) brane pressure of 100 kPa, a feed solution con-
W wet
centration of 0.1 %, and a test temperature of
Here Wwet and Wdry are the weight of a mem- 25 C are recommended. Furthermore, a maxi-
brane sample in the wet and the dry state. mum of agitation of the feed solution at the mem-
brane surface is required to minimize
concentration polarization effects, and small
Membrane Separation Properties amounts of solution should be filtered to assure
Determined by Filtration Test a constant feed concentration.
The retention is generally expressed in % and
Both micro- and ultrafiltration are pressure- defined by:
driven membrane processes using porous
6 Characterization of Porous and Dense Membranes
Characterization force
of Porous and Dense
Membranes,
Fig. 3 Schematic drawing rp
that illustrates the capillary
effect of a membrane pore
wetting liquid
CP molecular weight of the retained components.
R¼ 1 100 (4) The sharpness of the cutoff of a membrane
Cf
depends mainly on the pore size distribution of
Here R is the retention or rejection of a membrane the membrane. For practical applications, the
and Cf and Cp are the feed and the permeate cutoff of a membrane should be as sharp as
concentration. possible.
The retention of molecules having identical
molecular weights may be rather different when
their shape is different. Globular proteins, e.g., The Bacterial Challenge Test
are rejected easier than branched polysaccharides
or flexible polymers (Porter 1979). Adsorption of Micro- and ultrafiltration membranes are often
the solute to the membrane surface, e.g., might used in the food and pharmaceutical industry for
result in high “apparent” retention values when the sterilization of solutions. In this application, it
the experiment is performed for a very short time is important that membranes retain undesired
period. Accumulation of solutes at the membrane microorganisms as completely as possible, i.e.,
surface due to concentration polarization effects the retention for microorganisms should be close
can also obscure the retention measurements and to 100 %. Therefore, these membranes are
must be considered when the true, i.e., intrinsic, exposed to a bacterial challenge test. In this test,
retention shall be determined. Using low pres- the membrane is challenged with a solution
sures, low feed concentrations, and a high degree containing a minimum concentration of organ-
of agitation can more or less eliminate these isms such as Pseudomonas diminuta per cm3 of
effects. solution (Cheryan 1998). The data obtained in
Manufactures of ultrafiltration membranes bacterial challenge tests are normally expressed
generally make use of marker molecules, e.g., in terms of the log reduction value, which is given
dextrans and proteins, for the determination of by the logarithms of the ratio of feed to filtrate
the molecular weight cutoff value of their mem- concentration. The bacterial challenge test is a
branes. In addition to the molecular weight cutoff destructive test and is therefore not suited as an
of a membrane, the sharpness of the cutoff is on-line quality control test. For this application,
important for the practical application. The the nondestructive diffusion test and the bubble
sharpness of the cutoff of a membrane is deter- point integrity test are generally applied.
mined by measuring the retention of the mem-
brane for components of different molecular
weights and plotting the retention versus the
Characterization of Porous and Dense Membranes 7
Characterization
of Porous and Dense minimum pore size
Membranes,
Fig. 4 Schematic drawing
illustrating the gas/liquid dry flow
gas flow
displacement measurement
to determine the pore size
and pore size distribution of
microfiltration membranes mean flow pore size
pressure
bubble point
(maximum pore size)
Membrane Properties Determined by the pore, h is the height of the liquid column, r is
Membrane Pore Size Measurement liquid density, and g the acceleration of gravity.
The term h r g in Eq. 5 can be replaced by the
In addition to filtration tests, micro- and ultrafil- pressure p. This results in the Laplace equation,
tration membranes are characterized by deter- which is given by:
mining their pore size and pore size distribution.
A number of techniques such as liquid/gas and 2s cos f
rp ¼ (6)
liquid/liquid displacement, mercury intrusion, p
permporosimetry, thermoporosimetry, etc. are
used for the determination of the membrane The bubble point method is a fairly simple tech-
pore size and pore size distribution. One of the nique where the pores of a membrane are filled
more simple methods is the so-called bubble with a liquid. From the bottom side of the mem-
point test. brane, nitrogen gas or air is introduced with
increasing pressure. At a certain pressure, the
gas will replace liquid in the largest pores perme-
The Bubble Point Test
ating the membrane, and a bubble rising from the
The bubble point test is a structure integrity test in
membrane surface can be observed.
which the largest pore or hole in a membrane is
Equation 6 referred to as Laplace equation
determined. The bubble point method is based on
gives a relation for the surface tension between
the capillary effect of small pores due to surface
the liquid and the gas and the required pressure to
tension forces. In equilibrium these forces are
open up pores of a certain size. In the bubble
balanced with gravity of the liquid in the pores.
point test, mostly water or isopropanol is used,
The principle is shown in Fig. 3.
since the surface tension of water/air is approxi-
This equilibrium between surface tension
mately 3.5 times higher than for isopropanol/air.
forces and gravity of the liquid in the pore can
Other techniques to determine the pore size
be expressed by the following equation:
and pore size distribution of a porous membrane
that are also based on the Laplace equation, but
2pr p s cos f ¼ r 2p phrg (5) cover different pore size ranges when the same
pressure range is applied, are mercury
Here rp is the pore radius, s is the surface tension porosimetry, gas-liquid displacement, and
of the liquid in contact with air, cosf is the liquid-liquid displacement.
contact angle between the liquid and the wall of
8 Characterization of Porous and Dense Membranes
damper
p recorder
HPLC
pump
liquid A
computer
membrane digital
containing liquid B balance
Characterization of Porous and Dense Membranes, Fig. 5 Schematic representation of a typical liquid-liquid
displacement setup (Capannelli et al. 1983)
Characterization of Porous and Dense Membranes, Table 1 Different porosimetry techniques and the influence
of the interfacial tension on the pressure required opening pores of 10 nm
Pressure
Technique System (mN/m) (Bar)
Mercury porosimetry (G-L) Air/mercury 480 749
Bubble point (G-L) Air/water 72.3 145
Coulter porometry (G-L) Air/Porofil ® 16 32
Gas-liquid displacement (G-L) Air/isobutanol 20.7 41
Liquid-liquid displacement (L-L) Water/isobutanol 1.85 3.7
Liquid-liquid displacement (L-L) Water/isobutanol/methanol 0.35 0.7
pair used is water/isobutanol. Both liquids are (Cuperus et al. 1992a, b) such as permporometry
first saturated with each other before one of the or thermoporometry, which is based on the
liquids is used to fill the pores and the other liquid microcalorimetric analysis of a solid-liquid tran-
is applied as replacement liquid. The experimen- sition using a sensitive differential scanning cal-
tal setup for the determination of pore sizes by orimetry. Permporometry is a technique based on
liquid-liquid displacement is shown in Fig. 5. gas adsorption/desorption measurements where
A slow increase the replacement liquid pressure pores are either filled by controlled condensation
pushes the liquid out of the largest pores first. of a vapor phase or where filled pores are emptied
With increasing in pressure, the liquid in the by controlled evaporation of the liquid inside the
smaller pores will also be replaced. The pore pores. The relation between the relative vapor
size distribution can be calculated from a plot of pressure and the pore radius is given by the Kel-
the flux versus the applied pressure (Capannelli vin equation. Thermoporometry is based on the
et al. 1983; Wienk et al. 1994). microcalorimetric analysis of a solid-liquid tran-
Whether isobutanol or water is used as sition using a sensitive differential scanning
displacing liquid depends very much on the calorimetry.
nature of the membrane material. Due to swelling Table 1 shows the pressures required to open
phenomena, different results might be obtained pores of 10 nm for different displacement sys-
depending on the liquid placed inside the pores. tems. A second advantage is that membranes are
The relation between the pore radius and the characterized in a wetted state, and therefore the
pressure required to open pores of a certain size is test conditions are closer to the real operating
again described by the Laplace equation, and the conditions.
pore size distribution can now be calculated when
the flux as a function of the pressure is measured.
Like in gas-liquid displacement, only active
Dense Membrane Characterization
pores contributing to transport are taken into
account. Pore diameters of approximately
Dense membranes are generally used for the sep-
5–100 nm can be analyzed using liquid-liquid
aration of low molecular mass materials such as
displacement. The advantage of liquid-liquid dis-
gases, salts, or solvents. The transport mechanism
placement over gas-liquid displacement is the
in these membranes is based on the solution and
lower interfacial tension between liquid pairs
diffusion of components within the membrane
compared to a gas/liquid pair. Therefore, pores
matrix. The intrinsic properties of the basic mem-
of the same size can be opened at much lower
brane material are often more relevant for char-
pressures in liquid-liquid displacement.
acterizing their transport behavior than is the
There are more methods that can be used to
macroscopic membrane structure. Characteriza-
determine pore sizes in porous membranes
tion methods used with microporous structures
10 Characterization of Porous and Dense Membranes
have therefore been supplemented with other pro- Capannelli G, Vigo F, Munary S (1983) UF characteriza-
cedures, such as sorption and diffusion measure- tion methods. J Membr Sci 15:289
Cheryan M (1998) Ultrafiltration and microfiltration hand-
ments or determination of the glass transition book. Lancaster Publishing Company, Lancaster
temperature and crystallinity of the basic mem- Cuperus FP, Bargeman D, Smolders CA (1992a)
brane material. For ion-exchange membranes, the Permporometry. The determination of active pores in
measurement of electrokinetic properties is ultrafiltration membranes. J Membr Sci 71:75
Cuperus FP, Bargeman D, Smolders CA (1992b) Critical
required. points in the analysis of membrane pore structure by
In addition to the determination of diffusion thermoporometry. J Membr Sci 66:45
and partition (solubility) coefficients, measure- Cussler EL (1971) Membranes which pump. AICHE
ments providing information on the physical J 17:1300–1303
Cussler EL (1984) Diffusion. Academic, Cambridge, MA
structure of the polymer, such as differential Fane AG, Fell CJD, Waters AG (1981) The relationship
scanning calorimetry, X-ray studies, or determi- between membrane pore characteristics and flux for
nation of the free volume in a polymer, are impor- ultrafiltration membranes. J Membr Sci 9:245
tant. These methods are described in Koros and Ferry JD (1936) Ultrafilter membranes and ultrafiltration.
Chem Rev 18:373
Chem (1987), Berens and Hopfenberg (1982), Fritsche A.K., Arevalo AR, Moore MD, O’Hara C (1992)
and Morel and Paul (1982). Permeability and Surface Structure and Morphology of Polyacrylonitrile
selectivity are the most interesting parameters; Membranes by Atomic Force Microscopy. J. Membr
they are determined in permeation tests and Sci. 46:167
Gierke TD, Munn GE, Wilson FC (1982) Morphology of
expressed in terms of rejection coefficients perfluorosulfonated membrane products – wide- angle
(in reverse osmosis) or separation coefficients and small-angle x-ray studies. ACS Symp Ser
(in gas separation and pervaporation). These 180:195–216
coefficients are usually not constant but a func- Hilal N, DJ Johnson (2010). The use of atomic force
microscopy in membrane characterisation. Compre-
tion of composition, temperature, and pressure. hensive Membrane Science and Engineering. E. Drioli
Furthermore, boundary layer effects at the mem- and L. Giorno. Oxford, Elsevier Science. 521–538
brane surface often obscure the determination of Kim KJ, Fane AG, Fell CJD, Suzuki T, Dickson MR
membrane fluxes and selectivities in practical (1990) Quantitative microscopic study of surface char-
acteristics of ultrafiltration membranes. J Membr Sci
measurements. 54:89
The methods used to determine the structural Komoroski RA, Mauritz KA (1982) Perfluorosulfonated
properties of ion-exchange membranes are simi- ionomer membranes. In: Eisenberg A, Yeager HL
lar to those used for characterizing other polymer (eds) ASC symposium series 180. American Chemical
Society, Washington, DC
membranes. Because ion-exchange membranes Koros WJ, Chern RT (1987) Separation of gaseous mix-
are used mainly in separation processes with tures using polymer membranes. In: Rousseau RW
electrical potential driving forces, their perme- (ed) Handbook of separation process technology.
ability and selectivity are determined under Wiley, New York
Morel G, Paul DR (1982) CO2 sorption and transport in
experimental conditions closely related to their miscible polyphenylene oxide/polystyrene blends.
practical use, and their properties are expressed in J Membr Sci 10:273
terms commonly used in electrochemistry (e.g., Porter MC (1979) Membrane filtration. In: Schweizer PA
electrical resistance, ion-transfer numbers, (ed) Handbook of separation techniques for chemical
engineers. Mac Graw-Hill, New York
charge densities) (Cussler 1971, 1984). Wienk IM, Folkers B, van den Boomgaard T, Schmolders
CA (1994) Critical factors in the determination of the
pore size distribution of UF membranes using a liquid
References displacement method. Sep Sci Technol 29:1433
for the overall performance of the membrane in a of their electrochemical properties such as the
given process. However, for the determination of fixed charge density, the electrical resistance,
pinholes in ion-exchange membranes will affect the ion permselectivity, and the transport of non-
the performance of a membrane severely in appli- ionic components such as water or of other neu-
cations with a hydrostatic pressure differences tral molecules under operating conditions.
across the membrane. Pinholes can be detected
quickly by placing a wet membrane sheet on a
sheet of white absorbent paper. Then, a 0.2 %
The Ion-Exchange Capacity of a
solution of methylene blue for an anion-exchange
Membrane
membrane or a 0.2 % solution of erythrosin B for
a cation-exchange membrane is spread over the
The ion-exchange capacity of membranes is a
entire surface of the membrane. If no spots of the
crucial parameter which affects almost all other
dye can be observed on the paper, the membrane
membrane properties. It is usually expressed in
is free of large pinholes. The hydraulic perme-
milliequivalent per gram of dry membrane. Exper-
ability of the membrane is determined at room
imentally, the ion-exchange capacity of strong
temperature using deionized water and a hydro-
acidic or strong basic ion-exchange membranes
static pressure driving force in a conventional
is readily determined by titration with NaOH or
filtration cell as used in reverse osmosis or ultra-
HCl, respectively. For these tests, cation- and
filtration experiments. The permeability can then
anion-exchange membranes are equilibrated in
be calculated from the volumetric flow rate.
1N HCl or 1N NaOH, respectively, and then
The economics of processes using
rinsed free from chloride or sodium ions with
ion-exchange membranes in different applications
deionized water. The ion-exchange capacity of
is determined to a large extent by the chemical
the samples is determined by back titration with
stability of the membranes under process condi-
1N NaOH or 1N HCl, respectively. Weak base
tions. Generally, the changes in membrane proper-
anion-exchange membranes are characterized by
ties are time and temperature dependent. Reliable
equilibration in 1N NaCl and titration with stan-
information about the long-term stability of the
dardized 0.1N AgNO3 solution. The samples are
membranes is of importance for a process design
then dried, and the ion-exchange capacity is cal-
and cost calculation. For a fast evaluation, mem-
culated based on the dry membrane. The accuracy
brane samples are exposed to oxidizing agents or
of the measurement depends on the complete
acids and bases and other chemical components in
exchange of ions in the membrane which can
much higher concentration and at higher tempera-
take some time. The concentration of the fixed
ture than expected in practical use. Structural
ion in commercial membranes is in the range
mechanical changes are determined by visual or
between 1 and 3 milliequivalent per gram. The
microscopic investigation and standard mechanical
experimentally measured ion-exchange capacity
and electrochemical tests comparing exposed with
of a membrane is an average value assuming that
unexposed membrane samples. Since the useful
the ions are homogeneously distributed over the
life of membranes under process conditions is gen-
entire polymer matrix. In many heterogeneous
erally in the range of a couple of years, membrane
membranes, such as most of the perfluorinated
stability tests are very time consuming. However,
cation-exchange membranes, the fixed ions are
in many cases long-term pilot plant tests are man-
clustered, and the local fixed ion concentration
datory to get a reliable estimation of the life of the
may be significantly higher than the average value.
membranes in practical applications.
The performance of ion-exchange membranes
in the various processes is determined to a very
large extent by their electrochemical properties.
Therefore, a major task in characterizing
ion-exchange membranes is the determination
Ion-Exchange Membrane Characterization 3
volt meter
calomel electrode
electrode electrode
solution A A C solution
gas gas
(O2) (H2)
anode cathode
+ porous plug -
- - - +
Ion-Exchange Membrane Characterization, Fig. 1 Schematic drawing of a test cell for determining the resistance
of ion-exchange membranes with direct current
without the membrane is subtracted from the the thickness of the membrane and the distance
resistance of the cell with the membrane. between the electrodes.
The area resistance is given by: The specific resistance r is:
U Am
r mþs ¼ RAm ¼ (1) r¼R (4)
i d
The membrane resistance is: Here Am is the cross-sectional area of the cell as
indicated in Fig. 2 and R is the resistance mea-
r m ¼ r mþs r s (2) sured between the electrodes.
For an accurate determination of the mem-
Here R is the resistance, Am is the area of the brane resistance, it is important that the differ-
membrane, U is the voltage drop measured ence between the measurement of the cell
between the Haber-Luggin capillaries and I is resistance with and without a membrane is as
the current density, rm+s and rs are the area resis- large as possible. Since the specific resistances
tances of the cell with and without the membrane of the membrane and the electrolyte solution are
between the Haber-Luggin capillaries, and rm is in the same order of magnitude and the mem-
the area resistance of the membrane. brane thickness dm is small, the distance d has to
The determination of the membrane resistance be as small as possible.
by direct current measurements is quite accurate Comparing the direct and alternating current
as long as the position of the Haber-Luggin cap- membrane characterization processes often sig-
illaries is as close as possible to the membrane nificant differences in the measured resistances of
and kept identical in the test with and without the more than 50 % is often observed. The alternating
membrane. To avoid boundary layer effects, the current measurements give a much lower mem-
bulk solution must be well mixed. But even if the brane resistance than the direct current measure-
boundary layer effects are well controlled, the ments. This is a general finding. However, the
direct current measurements are always magnitude of the difference in the results depends
connected with a transport of ions resulting in a on the membrane structure. In very heteroge-
concentration change in the electrolyte solution neous membranes, the difference is larger than
at the membrane surface which affects the accu- in more homogeneous membrane structures. The
racy of the measurement. reason for the different results is that in direct
Concentration changes at the membrane sur- current measurements, the ions are physically
face are avoided in resistance measurements with transported through the membrane matrix,
alternating current. A typical test cell used for whereas in alternating current measurements,
resistance measurements with alternating current the ions are only oscillating around their loca-
is shown in Fig. 3. The membrane resistance is tions. Assuming the structure of an
determined from resistance measurements in a ion-exchange membrane consists of a micro-
cell with and without membrane. The resistance scopic scale of a solid neutral polymer phase
of the membrane can be calculated from the fol- and electrolyte-filled pores, then the mobility of
lowing relation: the ions in the pore liquid is high. But their
The area resistance rm is related to the specific transport through the membrane is hindered by
resistance by: the solid polymer structure which acts as a bot-
tleneck between pores. This type of structure is
r m ¼ rmþs ðd m þ dÞ rs d (3) typical for fluorocarbon membranes. In alternat-
ing current measurements, the transport of the
Here rm are the area resistances of the membrane, ions on a very small scale, i.e., in a pore, is
rm+s and rs are the specific resistances of the cell measured. In direct current measurements, the
with and without the membrane, and dm and d are transport of the ions is measured on a
Ion-Exchange Membrane Characterization 5
Ion-Exchange A U
Membrane
Characterization,
Fig. 2 Schematic drawing
of a test cell used for
membrane resistance
measurements using
alternating current
membrane
dm
electrolyte solution
# # Crown 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_998-1
M
# Crown 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1000-1
2 Membrane Topography
Membrane Topography, a
Fig. 1 The three-
dimensional images of 20.0 nm
membranes by AFM. (a)
0.0 nm
A6DT and (b) PA6DT-C
(Cheng et al. 2011)
0.8 µm
0.8 µm
0.6
0.6
0.4
0.4
0.2 0.2
b
20.0 nm
0.0 nm
0.8 µm
0.8 µm
0.6
0.6
0.4 0.4
0.2 0.2
# Crown 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1002-1
M
Membrane Charge (Zeta Potential) (the pH at which point where there is no effective
Effect charge) of a membrane can be determined from
the minimum rejection value obtained when fil-
Paul Melvyn Williams tering a charged species (like sodium chloride
College of Engineering, Swansea University, (NaCl)), by varying the pH value at a fixed elec-
Swansea, UK trolyte concentration and constant applied pres-
sure (Cheng et al. 2011).
For ultrafiltration membranes, the charge on
Membrane surface charge (zeta potential) the membrane surface will affect the interactions
effect: The membrane surface charge or zeta between the membrane and the particles in the
potential is most often characterized using the feed solution. If the charge on both the membrane
streaming potential method (Hunter 1981) (see surface and the particles is of the same sign,
“▶ Membrane Charge Characterization”). The repulsion will occur, and there will be less fouling
charge of a membrane is significant to membrane and concentration polarization at the membrane
performance because charge affects the electro- surface. However, if the charge on the membrane
static repulsion between the ions or charged mol- surface is of the opposite sign to the particles,
ecules and the membrane surface. attractive forces will dominate and the membrane
Due to the materials used in the fabrication of will foul easily, thus reducing performance. The
membranes, most membrane surfaces show a membrane charge can have a significant effect on
negative charge at neutral pH values (i.e., pH 7). the flux obtained (Bacchin et al. 2006).
However, due to the amphoteric nature of the The determination of the membrane surface
chemical groups on the surface of a membrane, zeta potential can also be used as an indicator
the charge may be altered by adjusting the solu- for membrane fouling (Lawrence et al. 2006;
tion conditions (i.e., pH and electrolyte concen- Al-Amoudi et al. 2007). The effect of foulants
tration) (Cheng et al. 2011). Surface can be investigated, and based on the measure-
modifications may also be made to membranes ment results, the membrane surface can be spe-
in order to change the charge from negative to cifically treated to decrease membrane fouling
positive (Cheng et al. 2011; Kobayashi and extend the membrane lifetime (Lawrence
et al. 1996). et al. 2006; Al-Amoudi et al. 2007).
Membrane surface charge has a big influence
on the rejection of charged species (i.e., salt,
charged dyes, amino acids, etc.) for nanofiltration
membranes. The isoelectric point (Hunter 1981)
# Crown 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1003-1
2 Membrane Charge (Zeta Potential) Effect
# Crown 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1005-1
E
showed the separation factor of 1.1–2.7 toward discrimination during diffusion. On the other
amino acids (Higuchi et al. 2010). hand, in a sorption-selective membrane, chiral
selectors are embedded in a polymer matrix. To
reach permeation selectivity in sorption-selective
Molecular Imprinting Membranes membranes, the selectively adsorbed population
(MIMs) has to be mobile. An electrical potential is some-
times used for the purpose.
Molecular imprinting membranes are fabricated
by incorporating the template molecules into the
membranes and then removing the template mol-
References
ecules. The formed cavities in the membranes
show the specific affinity with the template mol- Higuchi A, Tamai M, Ko Y, Tagawa Y, Wu Y, Freeman B,
ecules and their analogue (Yoshikawa Bing J, Chang Y, Ling Q (2010) Polymeric membranes
et al. 1995). Although MIMs currently show for chiral separation of pharmaceuticals and
low enantioselectivity, this method has the poten- chemicals. Polym Rev 50:113–143
van der Ent EM, van’t Riet K, Keurentjes JTF, van der
tial of higher enantioselectivity (Xie et al. 2008). Padt A (2001) Design criteria for dense permeation-
Solid enantioselective membranes can be selective membranes for enantiomer separations.
divided into two classes: diffusion-selective J Membr Sci 185:207–221
membranes and sorption-selective membranes Xie R, Chu L, Deng J (2008) Membranes and membrane
processes for chiral resolution. Chem Soc Rev
(van der Ent et al. 2001; Xie et al. 2008). A - 37:1243–1263
diffusion-selective membrane is defined as a Yoshikawa M, Izumi J, Kitano T (1995) Molecularly
membrane with no specific chiral selectors for imprinted polymeric membranes for optical resolution.
the chiral interaction but consists of a chiral poly- J Membr Sci 108:171–175
mer. Diffusion selectivity is caused by the chiral
S
Supported Liquid Membrane over the other methods, such as low energy
for Enantioselective Separation demand, continuous operation, and easy scale-
up. Both liquid membrane and solid membrane
Keiji Sakaki have been applied to enantiomeric separation.
National Institute of Advanced Industrial Science The important factor of membrane-based
and Technology (AIST), Research Institute for enantioselective separation is the way how to
Sustainable Chemistry, Tsukuba, Ibaraki, Japan give the function of chirality recognition to mem-
branes. In the process using solid membranes,
chirality recognition exists in main polymer
An enantiomer is one of two stereoisomers that chain, chiral polymer branch, and doped chiral
are mirror images of each other and selector or cavity formed by molecular imprint-
nonsuperposable. This feature of an enantiomer ing (Higuchi et al. 2010). On the other hand, in
is called “chirality.” Many chiral molecules not the separation with liquid membranes,
only appear in nature but also can be synthesized enantioselective carriers are usually doped in
artificially. Amino acids and sugars are the rep- the liquid membranes. In a supported liquid
resentative chiral molecules found in nature, and membrane (SLM), a liquid containing
they exist in the form of one isomer. Enantio- enantioselective carriers is impregnated into a
meric pairs frequently show different biological porous support membrane. The separation con-
activity from each other. So the technology to cept in SLM process is shown in Fig. 1. On the
separate enantiomers has been an important sub- membrane surface in the feed phase, a doped
ject in the industries dealing with pharmaceuti- carrier combines with one isomer more preferen-
cals, foods, agrochemicals, and so on. However, tially than the other, and the carrier-isomer com-
enantioselective separation has been a challeng- plex diffuses in the liquid membrane toward the
ing subject because each enantiomer has the same strip phase. On the membrane surface of strip
physical and chemical properties. phase, the carrier releases the isomer. In the
Some methods have been reported for enan- SLM process, the driving force is the concentra-
tiomeric separation, for example, preferential tion gradient of co- or counterions (indicated as
crystallization, chromatographic separation, X in Fig. 1) between feed and strip phases. Typ-
enzyme-mediated resolution, and membrane- ical carriers used in SLM processes are crown
based separation (Xie et al. 2008). Among them, ethers. Figure 2 shows the structure of one of
membrane-based method has some advantages crown ethers that shows high enantioselectivity
Palladium-Based H2
Membrane (Palladium a) External diffusion
Alloy Membrane),
Fig. 1 Solution-diffusion b) Dissociation
H H H H
mechanism of hydrogen
permeation through a H H H H c) Dissolution
palladium-based
membrane (Yun and d) Internal diffusion
Oyama 2011)
H H H H
e) Association
H H2 H2 H
f) Desorption
g) External diffusion
H2
(Tc) for formation of the b-phase is around room cost of the whole membrane will be sharply
temperature (Paglieri and Way 2002). Besides, increased by increasing the membrane thickness.
Pd-Cu alloys do not show embrittlement even at Thus, there is a threshold between membrane
low temperatures (Kulpatripanja et al. 2005). mechanical stability and membrane thickness
Pd-Cu, Pd-Au, Pd-Pt, Pd-Rh, and Pd-Ru (and thus flux and costs). For this reason it is
alloys have been used for increasing the tolerance foreseen that the first industrially available mem-
to sulfur (Paglieri and Way 2002; Morreale branes will be supported membranes. Supported
et al. 2004; Way et al. 2008). According to membranes consist of a thin selective film depos-
McKinley, a Pd60Au40 (mass%) is superior to a ited onto a support that provides mechanical sta-
Pd60Cu40 (mass%) concerning poisoning by sul- bility. Thus, the hydrogen permeance of the
fur (McKinley and Nitro 1967). According to membrane will be higher so that less membrane
Morreale et al., face-centered cubic (fcc) Pd-Cu area is required and the whole membrane cost
showed a decline of 0–10 % permeability when will be lower than that for unsupported mem-
exposed to 1,000 ppm of sulfur, and body- branes. However, in the total membrane cost,
centered cubic (bcc) Pd-Cu showed a decline of the cost of the support also becomes important.
99 % at the same sulfur content stream (Morreale Especially when very thin film membranes are
et al. 2004). Thus, the final structure of the palla- selected, the support pore size should be much
dium alloy is an important issue. In general, the lower and the surface much smoother, so that its
sulfides of Pt, Ir, Rh, and Ru are much less stable cost will increase. There are mainly two types of
than those of the Pd, and thus these elements porous support materials: metallic and
show better tolerance to poisoning by sulfur. ceramic. Ceramic supports typically have better
Currently, novel Pd-based ternary alloy mem- surface quality providing membranes with thin-
branes are being studied (Peters et al. 2011, ner selective layers. However, they are more
2013). fragile. Metallic supports are more robust than
ceramic, but the commercial ones, mainly tubu-
lar, have lower surface qualities. Some research
Unsupported and Supported groups are developing hollow fiber supports
Membranes (both ceramic and metallic) in order to increase
the surface area to volume ratio and also improve
Unsupported Pd-based membranes need to be the surface quality (Luiten-Olieman et al. 2012).
thick self-standing films (>50 mm thick) in In the case of the Pd-based membrane, support is
order to have a minimum mechanical stability. metallic and is used at temperatures above the
The main drawback of these membranes is their Tamman temperature of one of the metallic parts,
low hydrogen permeance. Moreover, in the case common situation for high-temperature
of using an expensive membrane material, the reforming reactions; it is necessary to position
Palladium-Based Membrane (Palladium Alloy Membrane) 3
Edlund DJ, Pledger WA (1994) Catalytic platinum-based Morreale BD, Ciocco MV, Howard BH, Killmeyer RP,
membrane reactor for removal of H2S from gas natural Cugini AV, Enick RM (2004) Effect of hydrogen-
streams. J Membr Sci 84:111–119 sulfide on the hydrogen permeance of palladium-
Gallucci F, Fernandez E, Corengia P, Van Sint Annaland copper alloys at elevated temperatures. J Membr Sci
M (2013) Recent advances on membrane and mem- 241:219–224
brane reactors for hydrogen production. Chem Eng Sci Pacheco Tanaka DA, Llosa Tanco MA, Nagase T,
92:40–66 Okazaki J, Wakui Y, Mizukami F, Suzuki TM
Grashoff GJ, Pilkington CE, Corti CW (1983) The purifi- (2006) Fabrication of hydrogen permeable composite
cation of hydrogen: a review of the technology empha- membranes packed with palladium nanoparticles. Adv
sizing the current status of palladium membrane Mater 18:630–632
diffusion. Report 27(4):157–169 Paglieri SN, Way JD (2002) Innovations in palladium
Holleck GL (1970) Diffusion and solubility of hydrogen in membrane research. Sep Purif Rev 31:1–169
palladium and palladium-silver alloys. J Phys Chem Palo E, Iaquaniello G, Cucchiella B, Salladini A (2012)
74(3):503 Membrane module design: a general introduction in Pd
Hsieh HP (1989) Inorganic membrane reactors – a review. membrane technology scale-up workshop
AIChE Symp Ser 85:53–67 Peters TA, Kaleta T, Stange M, Bredesen R (2011) Devel-
Iniotakis N, Von Der Decken CB, Fedders H, opment of thin binary and ternary Pd-based alloy
Froehling W, Semetz F (1987) Hydrogen permeation membranes for use in hydrogen production. J Membr
membrane. US Patent 4699637 Sci 383:124–134
Klette H (2005) Thin Pd-Ag foil prepared by PVD, Peters TA, Kaleta T, Stange M, Bredesen R (2013) Devel-
supported on porous SS. Membr Technol 5:7 opment of ternary Pd-Ag-TM alloy membranes with
Knapton AG (1977) Palladium alloys for hydrogen diffu- improved sulphur tolerance. J Membr Sci
sion membranes. Platin Met Rev 21(2):44–50 429:448–458
Kulpatripanja A, Alptekin GO, Falconer JL, Way JD Qiao A, Zhang K, Tian Y, Xie L, Luo H, Lin YS, Li
(2005) Pd and Pd–Cu membranes: inhibition of H2 Y (2010) Hydrogen separation through palladium-
permeation by H2S. J Membr Sci 254:49–62 copper membranes on porous stainless steel with
Li A, Ling W, Hughes R (2000) The effect of carbon sol-gel derived ceria as diffusion barrier. Fuel
monoxide and steam on the hydrogen permeability of 89:1274–1279
a Pd/stainless steel membrane. J Membr Sci Sanz R, Calles JA, Alique D, Furones L, Ordoñez S,
165:135–141 Marín P, Corengia P, Fernandez E (2011) Preparation,
Li X, Liu TM, Fan YQ, Xu NP (2008) Preparation of testing and modelling of hydrogen selective Pd/YSZ/
composite palladium-silver alloy membranes by SS composite membrane. Int J Hydrogen Energy
photocatalytic deposition. Thin Solid Films 36:15783–15793
516:7282–7285 Tarditi A, Gerboni C, Cornaglia L (2013) PdAu mem-
Luiten-Olieman MW, Raaijmakers MJT, Winnubst L, Bor brane supported on top of vacuum-assisted ZrO2-
TC, Wessling M, Nijmeijer A, Benes NE modified porous stainless steel substrates. J Membr
(2012) Towards a generic method for inorganic porous Sci 428:1–10
hollow fibers preparation with shrinkage-controlled Uemiya S, Endo T, Yoshiie R, Katoh W, Kojima T (2007)
small radial dimensions, applied to Al2O3 Ni, SiC, Fabrication of thin palladium-silver alloy film by using
stainless steel, and YSZ. J Membr Sci electroplating technique. Mater Trans 48:1119–1123
407–408:155–163 Way JD, Lusk M, Thoen P (2008) Sulfur-resistant com-
Mallory O, Hajdu JB (1990) Electroless plating: funda- posite metal membranes. US Patent 2008/0038567
mentals and applications. American Electroplaters and Yun S, Oyama ST (2011) Correlations in palladium mem-
Surface Finishers Society, Orlando. ISBN branes for hydrogen separation: a review. J Membr Sci
9780815512776 375:28–45
McKinley DL, Nitro WV (1967) Metal alloy for hydrogen
separation and purification. US Patent 3350845
P
Palladium-Based
Membrane Reactor,
Fig. 1 Two approaches in
membrane reactors: (a)
extractor and (b) distributor
(Julbe et al. 2001)
Palladium-Based a
Membrane Reactor,
Fig. 2 Packed-bed tubular
membrane reactor
configurations: (a) catalyst FEED RETENTATE
in tube and (b) catalyst in
shell (Gallucci et al. 2013)
b FEED
Hydrogen
Membrane
Catalyst
RETENTATE
Palladium-Based Exhaust
Membrane Reactor,
Fig. 3 Schematic Hydrogen
representation of a
fluidized-bed membrane
reactor for selective
removal of hydrogen is
presented (Adris
et al. 1994)
Membrane
tubes
Heat
exchangers
Reactants
4 Palladium-Based Membrane Reactor
Palladium-Based
Feed Retentate
Membrane Reactor,
Fig. 4 Schematic Feed
representation of the Channel housing
microchannel reactor
configuration used by
Bredesen for Pd-based Membrane
membrane tests (Mejdell Retentate
et al. 2009) Perforated plate
Copper gasket
Apertures
Permeate housing
Sweep Permeate
bed-to-wall mass transfer limitations but also Gallucci F, Basile A, Tosti S, Iulianelli A, Drioli E (2007)
allows operating the reactor at a virtually isother- Methanol and ethanol steam reforming in membrane
reactors: an experimental study. Int J Hydrogen Eng
mal condition (due to the movement of catalyst). 32:1201–1210
The MMR configuration is interesting due to: Gallucci F, Tosti S, Basile A (2008) Pd-Ag tubular mem-
(i) improved mass and heat transfer owing to the brane reactors for methane dry reforming: a reactive
reduction of the scale length in the method for CO2 consumption and H2 production.
J Membr Sci 317:96–105
microchannels; (ii) removal of mass transfer lim- Gallucci F, Basile A, Hai FI (2011) Introduction – a review
itations (concentration polarization); and (iii) of membrane reactors. In: Basile A, Gallucci F (eds)
high degree of process intensification by integrat- Membranes for membrane reactors: preparation, opti-
ing different process steps in a small-scale mization and selection. Wiley, West Sussex, pp 1–61
Gallucci F, Fernandez E, Corengia P, Van Sint Annaland
device. (Gallucci et al. 2013). The microchannel M (2013) Recent advances on membrane and mem-
reactor configuration proposed by Bredesen and brane reactors for hydrogen production. Chem Eng Sci
coworkers is presented in Fig. 4. 92:40–66
Galuszka J, Giddings T, Iaquaniello G (2012) Membrane
assisted WGSR – experimental study and reactor
modelling. Chem Eng J 213:363–370
References Gryaznov VM, Polyakova VP, Savitskii EM, Frades L,
Khrapova EV, Khuares E, Shkola GV (1970) Influence
Adris AM, Grace JR, Lim CJ, Elnashaie SS (1994) Fluid- of the nature and amount of the second component of
ized bed reaction system for steam/hydrocarbon gas binary-palladium alloys on their catalytic activity with
reforming to produce hydrogen. US Patent 5,326,550 respect to the dehydrogenation of cyclohexane. Bull
Basile A, Paturzo L (2001) An experimental study of Acad Sci USSR Div Chem Sci 19(11):2368–2371
multilayered composite palladium membrane reactors Julbe A, Farrusseng D, Guizard C (2001) Porous ceramic
for partial oxidation of methane to syngas. Catal Today membranes for catalytic reactors – overview and new
67:55–64 ideas. J Membr Sci 181:3–20
Chen Y, Wang Y, Xu H, Xiong G (2008) Efficient pro- Mejdell AL, Jøndahl M, Peters TA, Bredesen R, Venvik
duction of hydrogen from natural gas steam reforming HJ (2009) Experimental investigation of a
in palladium membrane reactor. Appl catal B Environ microchannel membrane configuration with a 1.4 mm
80:283–294 Pd/Ag 23 wt% membrane – effects of flow and pres-
Cheng YS, Peña MA, Yeung KL (2009) Hydrogen pro- sure. J Membr Sci 327(1–2):6–10
duction from partial oxidation of methane in a mem- Rohde MP, Unruh D, Schaub G (2005) Membrane appli-
brane reactor. J Taiwan Inst Chem Eng 40:281–288 cation in fischer-tropsch synthesis reactors – overview
De Falco M, Marrelli L, Iaquaniello G (2011) Membrane of concepts. Catal Today 106:143–148
reactors for hydrogen production processes. Springer, Zaman J, Chakma A (1994) Inorganic membrane reactors.
London J Membr Sci 1994:1–28
I
Isotherm Palladium Phase Diagram b-phase is formed at high H/Pd atomic ratios
and coexists with the a-phase at low temperature
Ekain Fernandez (Fig. 1). The hydrogen vapor pressure is constant
Energy and Environment, TECNALIA, in the region of phase coexistence and is bounded
Donostia-San Sebastian, Gipuzkoa, Spain by an envelope defining amax and bmin, the com-
positions of maximum and minimum H/Pd ratio
for pure palladium (Yun and Oyama 2011). The
Isotherm palladium phase diagram represents change in volume accompanying the phase trans-
the palladium–hydrogen system as a function of formation can give rise to strain and, conse-
pressure, temperature, and H/Pd concentration as quently, after a few cycles to a metal lattice
shown in Fig. 1. distortion (Shu et al. 1991), and micro-failures
The isotherm palladium diagram is used to inside the metallic bulk are induced.
show the nature of one of the biggest problems The alloying of palladium with other metals,
of pure palladium membranes: hydrogen embrit- lowering the coexistence temperature of the two
tlement. As shown in Fig. 1, the absorption of crystalline phases, reduces the internal strength
hydrogen below its critical point of 571 K generated and avoids micro-failure formation
(298 C) and 2 MPa produces two different inside the alloy bulk. Silver is the most used
phases (a and b), both of which retain the pure metal for avoiding hydrogen embrittlement phe-
palladium face-centered cubic (fcc) lattice but nomenon in Pd–alloy membranes. The critical
with the crystal unit cell lattice parameter temperature for the formation of b-phase of
increasing from 0.3890 nm for hydrogen-free Pd–Ag alloy with a composition of 77 and
palladium to 0.3895 nm for the a-phase and up 23 (%wt) is around room temperature (Paglieri
to 0.410 nm for the b-phase at room temperature and Way 2002).
(Lewis 1967; Ohira et al. 1996). The a-phase is
obtained at low H/Pd atomic ratios and becomes
the dominant phase at high temperature. The
Isotherm Palladium
Phase Diagram,
Fig. 1 Pressure–
concentration–temperature
phase diagram of the
palladium–hydrogen
system (Lewis 1967)
phase. It was postulated that Keggin’s anions of DTA curves. It corresponds to exothermic trans-
WPA-0 phase are stabilized by protons – “free formation which is followed by the mass loss
protons.” At higher temperatures, about 400 C (TGA) corresponding to about 0.5–0.3 water
(the broad peak) was defined as Tg anomaly on molecules.
(1)
175-230°C 230-580°C 580-604°C 604-1000°C
It was evident that these water molecules are tungsten bronzes (PWB) happen (Mioč
formed from protons and few oxygen atoms et al. 1994, 2005). All WPA phases were indexed
from host lattice in endothermic process, which and corresponding unit cell dimension calcu-
is simultaneous with water dehydration. Nowa- lated. Some of them for the first time: WPA-14
days, this water is called protonated (Janik as triclinic. All phases from WPA-6 up to struc-
et al. 2004). Metastable (D-phase–denuded tural phase transformation are cubic. Phosphate
phase) is stable up to 604 C, for WPA, when tungsten bronzes (PWB) have also been obtained
structural phase transformation to phosphate and defined for the first time using HPAs as
precursor (Mioč et al. 1994). Fournier noted
also the same large peak for WPA and identified
it as a new Q phase. He claims that a new Q phase
a is formed after the loss of “constitutional” water
14-29 H2O
(Fournier et al. 1992).
These investigations have been followed by
IR and Raman spectroscopic study in situ, in
temperature range from temperature of liquid
nitrogen 195 to 220 C, and with 18O-labeled
a H5O2+ 6 H2O
compounds. On the basis of the obtained spectra,
few proton species were identified (H5O2+, H3O+,
H2O, and OH groups): terminal OH groups of
Keggin’s anions at about 3,550; OH groups
from water molecules, due to the most frequent
a H+
interaction H2O. . .H2O at about 3,490; and OH
0.2 H2O
bands belonging to H3O+. . .H2O, the strongest
interaction at about 3,292 and 3,225 and
3,140 cm 1; bands in the region 2,250–2,050
were assigned to n3 and/or n4 of H3O+ and water
libration modes. Dioxonium ion was identified
a 0 H2O
also, thanks to the band n4 at 1,720 and n2 at
about 1,220 cm 1. Special attention in the pro-
cess of calcination/dehydration was paid to the
Heteropolyacids, Fig. 1 Schematic survey of different intensity changes of bands n4(H3O+) at 1,720 and
steps of hydration of HPAs
Heteropolyacids 3
Heteropolyacids, a 100 12
Fig. 2 DTA and TGA
curves of WPA-29 in 10
98
Endo.← DT →Exo.
different temperature 8
regions. Scanning rates 96
(wt %)
6
were 1, 5, and 10 C/min
(mV )
94 4
2
92
0
90 –2
10 20 30 40 50 60 70 80 90 100
t (°C)
b 99.5 4
3
Endo.← DT →Exo.
98.5 2
1
97.5
(wt %)
(mV )
–1
96.5 –2
–3
95.5 –4
–5
94.5 –6
c 100 25
98 20
Endo.← DT →Exo.
96
15
(wt %)
94
(mV )
10
92
5
90
0
88
86 –5
0 200 400 600 800 1000
t (°C)
DTA and TGA curves of 29-WPA
at temperatures up to 1000 C
n2(H2O) at 1,610 cm 1 (Mioč et al. 1990, 1994, temperature, frequency, and so on) as character-
2005). istics of these compounds.
Protonic entities and their dynamic equilib-
rium influence the host structure too. Identifica-
tion of proton species and following of its
References
dynamic equilibrium is also very important for
understanding catalytic (formation of Brønsted Fournier M, Feumi-Jantou C, Rabia C, Herve G, Launay
acid centers) and conductive processes (defining S (1992) Polyoxometalates catalyst materials: X-ray
charge carriers, conductivity dependence of thermal stability study of phosphorus-containing
heteropolyacids H3+xPM12 xVxO40 13-14H2O
(M = Mo,W; x = 0–1). J Mater Chem 2:971–978
4 Heteropolyacids
Janik MJ, Davis RJ, Neurock M (2004) A first principles Mioč UB, Todorović MR, Davidović M, Colomban P,
analysis of the location and affinity of protons in the Holclajtner-Antunović I (2005) Heteropoly
secondary structure of phosphotungstic acid. J Phys compounds-from proton conductors to biomedical
Chem B 108:12292–12300 agents. Solid State Ion 176:3005–3017
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Raman study of some heteropolyacid hydrates. J Mol Insoluble heteropoly compounds as highly active cat-
Struct 218:123–128 alysts for liquid-phase reaction. J Mol Catal
Mioč UB, Dimitrijević RŽ, Davidović M, Nedić ZP, 74:247–256
Mitrović MM, Colomban P (1994) Thermally induced Pope MT, M€ uller A (eds) (1994) Polyoxometalate: from
phase transformations of 12-tungstophosphoric acid platonic solids to anti-retroviral activity. Kluwer,
29-hydrate: synthesis and characterization of Dordrecht
PW8O26-type bronzes. J Mater Sci 29:3705–3718
M
The heteropolyanions undergo several rapid PMo12 O40 3 þ 2e þ 2Hþ ¼ H2 PMo12 O40 3
one- and two-electron reversible reductions to
produce the so-called “heteropoly blue” and fur- H 2 PMo12 O40 3 þ 2e þ 2H þ
ther irreversible multielectron reductions with
concomitant decomposition. The electrons are ¼ H 4 PMo12 O40 3 pH ¼ 1
accepted by the addenda ions of the heteropo-
lyanions. If the addenda ions are all identical, H 4 PMo12 O40 3 þ 2e þ 2Hþ
the electrons are delocalized on the addenda ion ¼ H 6 PMo12 O40 3
oxide framework at room temperature by rapid
electron hopping (intramolecular electron trans-
Dawson-type heteropolyanions undergo several
fer). The reduction increases the negative charge
reversible one-electron reductions in organic
density at the heteropolyanions and thus their
and aqueous solvents if no protonation accom-
basicity. As a consequence, the reduction can be
panies the reductions.
accompanied by protonation depending on the
pKa of the produced oxometalates (Sadakane
P2 W 18 O62 6 þ e ¼ P2 W 18 O62 7
and Steckhan 1998).
Keggin-type heteropolyanions can accept a
limited number of electrons without decomposi- P2 W 18 O62 7 þ e ¼ P2 W 18 O62 8 0 < pH < 3
tion, and in some cases the reduced compounds
have been isolated. P2 W 18 O62 8 þ 2e þ 2Hþ ¼ H2 P2 W 18 O62 8
PW 12 O40 5 þ 2e þ H þ ¼ HPW 12 O40 6 P2 W 18 O62 9 þ e ¼ P2 W 18 O62 10 0 < pH < 8:2
With increasing pH, the third reversible P2 W 18 O62 10 þ 2e þ 2Hþ ¼ H2 P2 W 18 O62 10
two-electron wave moves to a more negative
potential and splits into two reversible P2 W 18 O62 10 þ e ¼ P2 W 18 O62 11
one-electron reduction waves at pH 4:
P2 W 18 O62 11 þ e ¼ P2 W 18 O62 12 8:2 < pH
PW 12 O40 5
þ e ¼ PW 12 O40 6
The stability of tungstophosphoric acid in aque-
ous solutions is considerable dependent on pH
PW 12 O40 6
þ e ¼ PW 12 O40 7
with regard to the dominant species present in
For phosphopolyoxomolybdate, it is difficult to the solution (Holclajtner-Antunović et al. 2008).
obtain well-defined redox waves in cyclic Many factors influence the equilibrium, primarily
voltammetry in aqueous electrolytes due to the pH and HPA concentration, while the perfor-
easy hydrolysis of PMo12O403. However, it is mance of different analytical techniques used
stabilized by addition of comparatively large for speciation should be taken in account as
amounts of organic solvents. The reduction well. Tungstophosphoric acid decomposes first
potentials depend on pH as a result of protonation to components of the Dawson series, while the
(Sadakane and Steckhan 1998; Gómez-Romero total decomposition of the Keggin anion to phos-
and Casañ-Pastor 1996). phate and tungstate occurs at pH >7.5.
It should be noted that, besides the ability to
perform multielectron redox transformations,
Multielectron Redox Catalysts 3
HPAs also have a very strong Brönsted acidity Gómez-Romero P, Casañ -Pastor N (1996) Photoredox
approaching superacid region. Their acid-base chemistry in oxide clusters. Photochromic and redox
properties of polyoxometalates in connection with
and redox properties can be varied over a wide analog solid state colloidal systems. J Phys Chem
range by changing the chemical composition 100:12448–12454
(Damjanović et al. 2005). HPAs catalyze a wide Holclajtner-Antunović I, Bajuk-Bogdanović D,
variety of reactions in homogeneous liquid phase. Todorović MR, Mioč UB, Zakarevska J, Uskokovi-
ć-Marković S (2008) Spectroscopic study of stability
Being stronger acids, HPAs will have signifi- and molecular species of 12-tungstophosphoric acid in
cantly higher catalytic activity than mineral aqueous solution. Can J Chem 86:996–1004
acids. HPA catalysis lacks side reactions such as Huynh MHV, Meyer TJ (2007) Proton-coupled electron
sulfonation, chlorination, nitration, etc., which transfer. Chem Rev 107:5004–5064
Kozhevnikov IV (1998) Catalysis by heteropoly acids and
occur with mineral acids (Kozhevnikov 1998). multicomponent polyoxometalates in liquid-phase
reactions. Chem Rev 98:171–198
Sadakane M, Steckhan E (1998) Electrochemical proper-
References ties of polyoxometalates as electrocatalysts. Chem
Rev 98:219–237
Takashima T, Yamaguchi A, Hashimoto K, Nakamura
Bard AJ, Inzelt G, Scholz F (eds) (2008) Electrochemical R (2012) Multielectron-transfer reactions at single Cu
dictionary, 2nd edn. Springer, Berlin (II) centers embedded in polyoxotungstates driven by
Damjanović L, Rakić V, Mioč UB, Auroux A (2005) photo-induced metal-to-metal charge transfer from
Influence of cations on active sites of the alkaline anchored Ce(III) to framework W(VI). Chem
earth salts of 12-tungstophosphoric acid:microcalori- Commun 48:2964–2966
metric study. Thermochim Acta 434:81–87 Wang T, Brudvig GW, Batista VS (2010) Study of proton
Fendler J, Bolton J (1986) Panel discussion on sensitiza- coupled electron transfer in a biomimetic dimanganese
tion and immobilization of catalysts on various sup- water oxidation catalyst with terminal water ligands.
ports. Homog Heterog Photocatal NATO ASI Ser J Chem Theory Comput 6:2395–2401
174:699–701
O
0 0
0 10 20 30 40
Temperature of membrane surroundings (˚C)
membrane by permeation with a temperature differ- Uragami T, Yamada H (2003) Dehydration from alcohols
ence. J Membr Sci 74:183 by polyion complex cross-linked chitosan composite
Uragami T, Yamada H (1999) Removal of volatile organic membranes during evapomeation. Biomacro-
compounds from dilute aqueous solutions by molecules 4:137
pervaporation. Netw Polym 20:203
P
Pervaporation for Chloroform DMS content of more than about 40 and 70 mol%,
Separation respectively. It is noticeable that the benzene and
chloroform permselectivity and the normalized
Tadashi Uragami permeation rates for the graft copolymer mem-
Organization for Research and Development of branes changed remarkably at the same DMS
Innovative Science and Technology (ORDIST), content. These results suggest that the PMMA-
Kansai University, Suita, Osaka, Japan g-PDMS and PEMA-g-PDMS membrane struc-
ture changed at the corresponding DMS content.
On the other hand, the PBMA-g-PDMS mem-
Chloroform/water-selective membranes are brane showed a gradual increase in chloroform
effective for the removal of chloroform in permselectivity and normalized permeation rate
water. These membranes can be contributed to with increasing DMS content. From the above
the environmental problem. results, it was found that the structural change in
Removal of chloroform in an aqueous chloro- the PBMA-g-PDMS membrane with variations in
form solution through the poly DMS content was quite different from that of the
(methylmethacrylate)-poly(dimethylsiloxane) PMMA-g-PDMS and PEMA-g-PDMS mem-
(PMMA-g-PDMS), poly(ethylmethacrylate)- branes (Uragami et al. 2001).
PDMS (PEMA-g-PDMS), and poly(n- The permeation and separation characteristics
butylmethacrylate)-PDMS (PBMA-g-PDMS) of chloroform from water by PV through cross-
graft copolymer membranes was investigated by linked PDMS membranes prepared from
pervaporation (PV). PDMSDMMA and divinyl compounds, such as
Figure 1 shows the results of PV for an aque- EGDM, DVB, DVS, and DVF, were studied
ous solution of 0.02 wt.% chloroform through the (Ohshima et al. 2005). Those membranes showed
graft copolymer membranes. The chloroform high chloroform selectivity and permeability.
permselectivity of PMMA-g-PDMS and PEMA- Both chloroform/water selectivity and perme-
g-PDMS membranes increased dramatically at a ability were affected significantly by the divinyl
Pervaporation for Chloroform Separation, Table 1 Permeation separation characteristics for chloroform/water
mixture during PV (Khayet and Matsuura 2004)
Membrane Permeation rate for water Permeation rate for chloroform Separation factor
thickness (mm) (10 4kgm 2s 1) (10 5kgm 2s 1) aCH3Cl/H2O
38.81 1.69 2.47 146.02
49.77 1.28 1.81 141.69
59.70 1.17 1.91 163.15
83.15 0.87 1.40 160.47
110.77 0.66 1.14 173.32
Initial chloroform concentration 1 kg/m3, feed temperature 25 C, reduced pressure 1,666.5 Pa
Pervaporation for Chloroform Separation 3
Removal of Dissolved VOCs from The permeation rate and VOC/water selectivity
Aqueous Solutions (Pervaporation of the PBMA-g-PDMS membranes, however,
Application) increased gradually with increasing DMS con-
tent, unlike those of PMMA-g-PDMS and
Tadashi Uragami PEMA-g-PDMS membranes. Furthermore,
Organization for Research and Development of TEM observations revealed that the PMMA-
Innovative Science and Technology (ORDIST), g-PDMS and PEMA-g-PDMS membranes had
Kansai University, Suita, Osaka, Japan microphase-separated structures, consisting of a
PDMS phase and a poly(alkyl methacrylate)
phase. On the other hand, the PBMA-g-PDMS
Organic liquid/water selective membranes are membrane was homogeneous. It was found that
effective for the removal of organics in water the permeability and selectivity of these graft
and recovery of organic solvents from water. copolymer membranes for treatment of aqueous
These membranes can contribute to the environ- VOC solutions by PV were significantly related
mental problem and effective use of organic to a PDMS continuous layer in the phase-
solvents. separated structure (Uragami et al. 1999, 2001a).
The removal of volatile organic compounds Hydrophobically surface-modified mem-
(VOCs) such as benzene and chloroform from branes were prepared by adding a fluorine-
aqueous benzene and chloroform solutions containing graft copolymer to a microphase-
using poly(methyl methacrylate)-poly separated membrane consisting of PDMS and
(dimethylsiloxane) (PMMA-g-PDMS), poly PMMA to improve organic component selectiv-
(ethyl methacrylate)-PDMS (PEMA-g-PDMS), ity. Contact angle measurements and X-ray pho-
and poly(n-butyl methacrylate)-PDMS (PBMA- toelectron spectroscopy (XPS) revealed that the
g-PDMS) graft copolymer membranes was inves- addition of a fluorine-containing copolymer pro-
tigated by pervaporation (PV). When aqueous duced a hydrophobic surface at the air side of the
solutions of dilute VOCs were permeated through membrane due to surface localization of the fluo-
the PMMA-g-PDMS and PEMA-g-PDMS mem- rinated copolymer. It was apparent from TEM
branes, these membranes were Bz/H2O- and that adding a fluorine-containing copolymer of
CHCl3/H2O selective. The permeation and sep- less than small amount did not affect the mor-
aration characteristics of the PMMA-g-PDMS phology of the microphase-separated membrane.
and PEMA-g-PDMS membranes changed drasti- However, adding a fluorine-containing copoly-
cally at a DMS content of about 40 mol% and mer over a certain amount resulted in a morpho-
70 mol%, respectively, as shown in Fig. 1. logical change, from a continuous PDMS phase
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1038-3
2 Removal of Dissolved VOCs from Aqueous Solutions (Pervaporation Application)
4 100
Normalized pemeation rate
80
60
2
40
1
20
0 0
0 20 40 60 80 100 0 20 40 60 80 100
DMS content (mol%) DMS content (mol%)
Removal of Dissolved VOCs from Aqueous Solutions 0.05 wt.% benzene through PMMA-g-PDMS (○), PEMA-
(Pervaporation Application), Fig. 1 Effects of the g-PDMS (●), and PBMA-g-PDMS (□) membranes
DMS content on the benzene concentration in the perme- during PV
ate and normalized permeate for an aqueous solution of
Removal of Dissolved VOCs from Aqueous Solutions (Pervaporation Application), Table 1 Performance for
Bz/H2O of various membranes containing PDMS component
asep. asorp. adiff.
Bz/ Bz/ Bz/
Various PDMS membranesa H2O H2O H2O NPRb PSIc Refs
PMMA 53 422 0.13 0.29 16 Uragami et al. (2001a)
PMMA-g-PDMSd 620 739 0.86 0.13 226 Uragami et al. (2006)
CA/PMMA-g-PDMSe 1,772 1,267 1.40 0.71 1,240 Uragami et al. (2006)
PFA-g-PDMS/PMMA- 4,492 0.64 2,879 Miyata et al. (2001)
g-PDMSf
PDMSDMMA-DVBg 3,171 1,436 2.21 1.46 4,629 Uragami and Ohshima
(2003)
PDMSDMMA-DVSh 2,886 1,270 2.46 1.96 5,656 Uragami and Ohshima
(2003)
PDMSDMMA-DVFi 4,316 1,804 2.49 1.72 7,423 Ohshima et al. (2005)
CA/PDMSDMMA-DVBj 4,021 1,689 2.18 1.75 7,037 Ohshima et al. (2005)
CA/PDMSDMMA-DVSk 3,866 1,620 2.39 1.97 7,616 Ohshima et al. (2005)
CA/PDMSDMMA-DVFl 5,027 1,998 2.52 1.86 9,350 Ohshima et al. (2005)
a
PV experimental conditions: feed solution, an aqueous solution of 0.05 wt.% benzene; permeation temperature, 40 C;
pressure of permeation side, 1.33 Pa
b
Normalized permeation rate [10 5 mkg(m2h) 1]
c
PV separation index (NPR asep. Bz/H2O)
d
PDMS content 74 mol%
e
PDMS content 74 mol%; CA content 40 mol%
f
PDMS content 74 mol%; PFA-g-PDMS content 1.2 wt.%
g
DVB content 80 mol%
h
DVS content 90 mol%
i
DVF content 90 mol%
j
DVB content 80 mol%; CA content 0.5 wt.%
k
DVS content 90 mol%; CA content 0.5 wt.%
l
DVF content; CA content
Table 1, both the normalized permeation rate and difference between air and liquid phase/fiber
the Bz/H2O selectivity of each of the CA/ matrix (Juang et al. 2005).
PDMSDMMA-DVB, CA/PDMSDMMA-DVS,
and CA/PDMSDMMA-DVF membranes were
improved as compared to each of the References
PDMSDMMA-DVB, PDMSDMMA-DVS, and
PDMSDMMA-DVF membranes. Although the Huang RYM, Rhim JW (1991) Separation characteristics
of pervaporation membrane separation processes. In:
separation factors of the CA/PDMSDMMA-
Huang RYM (ed) Pervaporation membrane separation
DVB and CA/PDMSDMMA-DVS membranes processes, Membrane science technology series 1.
were lower than that of the PFA-g-PDMS/ Elsevier, Amsterdam, pp 111–180, Chapter 3
PMMA-g-PDMS membranes, the PSI of the for- Juang RS, Lin SH, Yang MC (2005) Mass transfer analy-
sis on air stripping of VOCs from water in microporous
mer membranes was much greater than that of the
hollow fibers. J Memb Sci 255:79
latter one. In Table 1, it was found that the addi- Miyata T, Yamada H, Uragami T (2001) Surface modifi-
tion of CA into the cross-linked PDMSDMMA cation of microphase-separated membranes by
membranes cross-linked with a suitable cross- fluorine-containing polymer additive and removal of
dilute benzene in water through these membranes.
linker is significantly effective to obtain higher
Macromolecules 34:8026
permeation and separation characteristics. A CA/ Ohshima T, Miyata T, Uragami T (2005a) Cross-linked
PDMSDMMA-DVF membrane with DVF of smart polydimethylsiloxane membranes for removal
90 mol% and CA of 0.4 wt.% showed the best of volatile organic compounds from water. J Mol
Struct 739:47
membrane performance, i.e., the normalized per-
Ohshima T, Miyata T, Uragami T (2005b) Selective
meation rate, separation factor for Bz/H2O selec- removal of dilute benzene from water by various
tivity, and PSI were 1.86 10 5mkg(m2h) 1, cross-linked poly(dimethylsiloxane) membranes
5,027, and 9,350, respectively. containing tertbutylcalix [4] arene. Macromol Chem
Phys 206:2521
The air stripping removal of VOCs such as
Uragami T, Ohshima T (2003) Removal of benzene from
toluene and phenol from water by microporous an aqueous solution of dilute benzene by various cross-
polypropylene (PP) hollow fibers was studied. linked poly(dimethylsiloxane) membranes during
The VOC stream passed through the lumen pervaporation. Macromolecules 36:9430
Uragami T, Yamada H, Miyata T (1999) Removal of
side of the module, while air (stripping gas) flowed
volatile organic compounds from dilute aqueous solu-
across the shell side. Experiments were performed tions by pervaporation. Trans Mater Res Soc Jpn
at different liquid flow rates (8–16 cm3min 1), gas 24:165
flow rates (60–180 cm3min 1), feed VOC concen- Uragami T, Yamada H, Miyata T (2001a) Removal of
dilute volatile organic compounds (VOCs) in water
trations (100–1,000 ppm), and temperatures
through graft copolymer membranes consisting of
(24–35 C). The removal was more effective poly(alkylmethacrylate) and poly(dimethylsiloxane)
when feed VOC level and liquid or gas flow rate by pervaporation and their membrane morphology.
increased. The applicability of a mass transfer J Memb Sci 187:255
Uragami T, Meotoiwa T, Miyata T (2001b) Effects of the
model that considers diffusion in the liquid layer,
addition of calixarene to microphase-separated mem-
membrane, and gas layer under steady state was branes for the removal of volatile organic compounds
checked. Unlike phenol with a very small dimen- from dilute aqueous solutions. Macromolecules
sionless Henry’s law constant (equilibrium gas 34:6806
Uragami T, Meotoiwa T, Miyata T (2003) Effects of
concentration divided by liquid concentration)
morphology of multicomponent polymer membranes
and a relatively low amount of sorption on PP containing calixarene on permselective removal of
fibers, the measured overall mass transfer coeffi- benzene from a dilute aqueous solution of benzene.
cients for toluene reasonably agreed with those Macromolecules 36:2041
Uragami T, Yamada H, Miyata T (2006) Effects of
predicted from the model. The large deviation
fluorine-containing graft- and block-copolymer addi-
observed for phenol indicated unsteady state tives on removal characteristics of dilute benzene in
nature, likely due to its small concentration water by microphase-separated membranes modified
with these additives. Macromolecules 39:1890
D
Dissolved Oxygen (DO) in Water by one phase into another. The DO removal from
Membrane Operations, Removal of water on a membrane contactor requires genera-
tion of a driving force for oxygen transmembrane
V. V. Volkov transfer, and this process demands reduction in
A.V.Topchiev Institute of Petrochemical oxygen concentration in a gas phase. This goal
Synthesis Russian Academy of Sciences (TIPS can be accomplished in one of three ways: (1) by
RAS), Moscow, Russian Federation applying vacuum to the water, (2) by supplying
an appropriate sweep gas to the gas side, and
(3) by a combination of the first two where a
Dissolved oxygen (DO) is one of the principal small flow of sweep gas is used to improve sep-
components which should be removed for the aration driving force but the gas side is still
production of ultrapure water. Even though con- maintained under vacuum (Sengupta
centration of DO in water is very low et al. 1998). In industrial (commercial) Liqui-
(approximately 8 ppm under ambient condi- Cel ® gas-liquid membrane contactors, polypro-
tions), DO leads to oxidation of dissolved com- pylene porous hollow fiber membranes are used.
ponents and materials, for example, boiler piping These membrane contactors offer a serious alter-
in (nuclear) power plants. In such systems, the native to the traditional two-stage vacuum
desired DO concentration in the boiler feed water degassing towers in the high-purity water treat-
is 7–10 ppb. Therefore, DO removal from water ment systems in the semiconductor industry.
presents a challenging problem for various indus- DO removal from water can be performed on a
tries such as production of semiconductors, membrane-UV reactor because DO can react
power plants, pharmaceuticals, and biotechnol- with hydrogen to yield water under the action of
ogy. In the production of semiconductors, stan- UV irradiation with a wavelength of 185 nm. This
dard DO level in ultrapure water is the most reaction requires dissolution of hydrogen in
stringent (below 1 ppb). Removal of DO from water, and this process is provided by gas-liquid
water by membrane technology can be accom- membrane contactors based on hollow fiber
plished by using gas-liquid membrane contactors membranes which are permeable for hydrogen
and membrane reactors. and UV irradiation (Li and Tan 2001).
Gas-liquid membrane contactors generally Most efficient existing methods for deep
incorporate a porous hollow fiber membrane for removal of DO from water are based on the
direct contacting of two immiscible phases, principle of oxygen reduction by hydrogen on a
namely, a gas and a liquid, for the purpose of palladium catalyst which yields water. The
absorption or stripping without dispersion of existing catalytic processes for water
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1039-4
2 Dissolved Oxygen (DO) in Water by Membrane Operations, Removal of
metal surface and this hydrogen concentration is case of Pd–Ag alloys, hydrogen solubility
proportional to the square root of the hydrogen increases with increasing Ag content up to
pressure. When mass transport to or from the 20–40 wt.%; hydrogen diffusivity decreases
surface (a, g) or dissociative adsorption (b) or with increasing Ag content. Concomitant
associative desorption (e) becomes rate- changes in solubility and diffusivity lead to
controlling steps, the expected value of n is higher hydrogen permeability (1.7 times higher)
1 because these processes depend linearly on the as compared with that of pure Pd at 23 wt.% of Ag
concentration of molecular hydrogen. In the case and at 623K (Ma et al. 2003).
of the Pd-based composite membranes with thick
(>5 mm) Pd layers, the n values are higher than
0.5, and this fact can be explained by defects or
References
pinholes through which substantial amounts of
hydrogen can permeate. This process proceeds Ma YH, Mardilovich IP, Engwal EE (2003) Thin compos-
via the Knudsen or Poiseuille flow mechanisms, ite palladium and palladium/alloy membranes for
and the corresponding exponents are higher than hydrogen separation. Ann N Y Acad Sci 984:346–360
0.5. Paglieri SN, Way JD (2002) Innovations in palladium
membrane research. Sep Purif Rev 31:1–169
In the case of binary palladium alloys, hydro- Yun S, Oyama ST (2011) Correlations in palladium mem-
gen permeation is generally proportional to the branes for hydrogen separation: a review. J Membr Sci
average bond distance of the alloys. Permeability 375:28–45
is the product of diffusivity and solubility. In the
H
steam reforming yields a gaseous mixture Palladium-alloy diffusers present a key compo-
containing hydrogen and also carbon dioxide nent for the recovery of hydrogen radioisotopes
and carbon monoxide. Solubility-controlled which are used and produced by the nuclear fis-
membranes (e.g., carbon-based membranes) are sion in the fusion reactors. Hydrogen recovery
preferentially permeable for big-sized gas mole- from waste gases or purge streams (e.g.,
cules (e.g., CO2) in relation to hydrogen. This hydrotreater off-gas) presents a potentially large
peculiarity offers evident economic advantages application of the palladium-based membrane
that maintaining/collecting hydrogen in the technology. Coal gasification or natural gas
retentate at nearly bulk feed pressure mitigates reforming coupled to a palladium membrane
the demands for costly hydrogen recompression reactor can offer an alternative huge source of
steps, even though a CO2 compression step is hydrogen. Production of pure hydrogen for its
required (Ockwig and Nenoff 2007). use in fuel cells also seems to be another impor-
Hydrogen-separating membranes made of pal- tant mission of the palladium-based membrane
ladium alloys have been developed over the past reactor (Paglieri and Way 2002).
50 years into a technology that in some instances
is used in practice. In an early work in the United
States and in the former Soviet Union, relatively
References
thick-walled tubes were used. This design has
been advanced for ultra-purification of hydrogen Bernardo P, Drioli E, Golemme G (2009) Membrane gas
and for its application in the semiconductor separation: a review/state of the art. Ind Eng Chem Res
manufacturing processes and in the hydrogen 48:4638–4663
Ockwig NW, Nenoff TM (2007) Membranes for hydrogen
generators for remote or small-scale usage. Cur-
separation. Chem Rev 107:4078–4110
rent research topics in this area are concerned Paglieri SN, Way JD (2002) Innovations in palladium
with membrane reactors for hydrogen gas supply membrane research. Sep Purif Rev 31:1–169
for fuel cells or for the chemical process industry.
H
alloys (typically Group IV and Group V metals); removing hydrogen from gas mixtures. Examples
and (v) coated metals such as Pd on Ta, V, etc. of membrane materials for commercial polymer
(Adhikari and Fernando 2006). Dense ceramic membranes include polyimide and polysulfone
membranes (e.g., perovskite, bismuth oxide, and (asymmetric hollow fiber membranes) or polyvi-
solid electrolyte) have been developed and com- nyl trimethylsilane and cellulose acetate
mercialized. Dense inorganic membranes are (asymmetric flat membranes). Such polymer
generally designed as a thin film on a porous membranes operate according to the solution-
inorganic support. diffusion mechanism.
To overcome the relatively low permeance In general, hydrogen selectivity is low, mod-
and high cost of dense metallic membranes, erate, and very high for polymeric, microporous
researchers are exploring the utility of high- inorganic, and metallic membranes, respectively.
permeance, less costly, and less selective micro- Polymeric membranes primarily operate at tem-
porous inorganic (silica or carbon or zeolite) peratures below 373 K, whereas carbon, silica,
membranes. The structure of these membranes and dense ceramic membranes can function at
presents a network of interconnected micropores higher temperatures (773–1,173 K). Metallic
with a diameter of ~0.5 nm. In general, micropo- membranes can be used at ~573–873 K.
rous silicas show the highest hydrogen selectiv-
ities, and they exhibit the best H2/N2 selectivity
which exceeds 10,000 for the membranes pre- References
pared by chemical vapor deposition (Ritter and
Ebner 2007). Adhikari S, Fernando S (2006) Hydrogen membrane sep-
aration techniques. Ind Eng Chem Res 45:875–888
Since the 1970s, gas separation polymer mem-
Ockwig NW, Nenoff TM (2007) Membranes for hydrogen
branes have been used industrially for hydrogen separation. Chem Rev 107:4078–4110
separation from gaseous mixtures in the United Ritter JA, Ebner AD (2007) State-of-the-art adsorption
States (Ockwig and Nenoff 2007) and in the and membrane separation processes for hydrogen pro-
duction in the chemical and petrochemical industries.
former Soviet Union (Yampolskii and Volkov
Sep Sci Technol 42:1123–1193
1991). Membranes made of glassy polymers Yampolskii YP, Volkov VV (1991) Studies in gas perme-
(i.e., polymers with glass transition temperatures ability and membrane gas separation in the Soviet
above the operating temperature) are used for Union. J Membr Sci 64:191–228
H
ΔH < 0
Substrate
Palladium q
‹H› ~ 50 – 100 μm
alloy
Gas R (opt.)
H2 or R-H2
ΔH > 0
Hydrogenation Contactors and Reactors, and this process is endothermic; both reactions are accom-
Fig. 1 Principle of a dense and self-supporting palladium panied by hydrogen transfer. Due to excellent thermal
alloy membrane (a thin-walled tube or a foil) for liquid conductivity of the membrane, the heat released by hydro-
phase hydrogenation. Hydrogen or hydrogen-containing genation can be utilized to facilitate endothermic dehy-
source R–H2 is supplied to the gas side; a to-be- drogenation (autothermic operation) (Dittmeyer
hydrogenated substrate is supplied to the liquid side. et al. 2004)
Dehydrogenation of R–H2 occurs on the gas-side surface
References
H2O
van der Vaart R, Hafkamp B, Koele PJ, Querreveld M,
Jansen AE, Volkov VV, Lebedeva VI, Gryaznov VM
(2001) Oxygen removal from water by two innovative
membrane techniques. Ultrapure Water 18:27–32
Volkov VV, Lebedeva VI, Petrova IV, Bobyl AV,
H2 Konnikov SG, Roldughin VI, van Erkel J,
Tereshchenko GF (2011) Adlayers of palladium parti-
cles and their aggregates on porous polypropylene
hollow fiber membranes as hydrogenization contrac-
tors/reactors. Adv Colloid Interface 164:144–155
2
sulfonic groups to membrane is an efficient way charge. Membranes with fixed charges are
to improve the hydrophilicity of PES membrane, predicted to exclude solutes or colloids bearing
which can be carried out through the introduction the same sign of charge and to decrease mem-
of sulfonic groups directly into PES or by blend- brane fouling. SPS/PES asymmetric blend
ing with another sulfonated material, such as nanofiltration membranes with functional group,
sulfonated polysulfones (SPSs). Sulfonated sulfonic group, can gain negative charges and
polysulfone (repeating unit shown in Fig. 2) give them great selectivity with respect to ions
with hydrophilic group, sulfonic group, has ade- or charged molecules.
quate hydrophilicity. The high hydrophilicity can SPS/PES asymmetric blend nanofiltration
improve the water flux and pollution resistibility. membranes are primarily characterized by pure
But sulfonated polysulfones possess weak water flux, rejection, and hydrophilicity.
strength, which will cause bad stability for oper- An SPS/PES asymmetric blend nanofiltration
ation. The miscibility of PES with SPS is better membrane is a combination of good hydrophilic-
enough. Sulfonated polysulfone can be induced ity and mechanical strength, which can improve
to increase hydrophilicity of the PES the water flux, antipollution ability, and stability
nanofiltration membrane. of blend membrane. The negative charge due to
Besides increasing hydrophilicity, sulfonated sulfonic group leads to a high selectivity over
polysulfone offers another advantage, negative ions or molecules with positive charges.
The SPS/PES asymmetric blend nanofiltration
membrane has the asymmetric morphology, as
O shown in Fig. 3. Blending of PES with SPS in
O S the casting dope leads to interesting asymmetric
structure. There are fingerlike macropores and
O n
spongelike pores in SPS/PES membranes.
A dense layer supported on a porous layer, as
SPS/PES Asymmetric Blend Nanofiltration Mem-
brane, Fig. 1 Polyethersulfone repeating unit shown in Fig. 4.
SPS/PES Asymmetric Blend Nanofiltration Membrane, Fig. 3 Typical cross section morphology of SPS/PES
asymmetric blend nanofiltration membrane
SPS/PES Asymmetric Blend Nanofiltration Membrane 3
References
Microscale Modeling
and Membranes,
Fig. 2 FAU structure with
equilibrated Na+ cations
(Accelrys Material Studio)
Mesoscopic Transport
Simulation,
Fig. 1 Representative
element of porous medium
the heat conduction equation, the Stokes or physicochemical phenomena can be treated.
Navier–Stokes equations for flow problems, the Single- and two-phase flow phenomena with or
convection–diffusion equation, etc. Another cat- without phase transition can be studied in the
egory involves the simulation of the motion of a context of membrane separations, including gas
number of molecule deputies that carry, in an separation, filtration, membrane distillation,
efficient manner, the properties of the actual membrane emulsification, etc. (Fig. 1).
fluid molecules that are obviously too many to
follow individually. Such methods include the
direct simulation Monte Carlo (Bird 1963, 1976,
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Bird GA (1994) Molecular gas dynamics and the direct
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from the classical statistical physics and is based Chen S, Wang Z, Shan X, Doolen G (1992) Lattice
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using well-defined features of propagation–- Hoogerbrugge PJ, Koelman JMVA (1992) Simulating
collision dynamics. Thanks to the explicit rela- microscopic hydrodynamic phenomena with dissipa-
tive particle dynamics. Europhys Lett 19:155–160
tion with details of the geometry and physics of Moeendarbary E, Ng T, Zangeneh M (2009) Dissipative
the problem, complex boundaries and various particle dynamics: introduction, methodology and
Mesoscopic Transport Simulation 3
complex fluid applications – a review. Int J Appl Mech Wolfram S (1986) Theory and applications of cellular
1:737–763 automata. World Scientific, Singapore
Rothman D, Keller JM (1988) Immiscible cellular-
automaton fluids. J Stat Phys 52:1119–1127
D
Digitized Structure
Model, Fig. 1 Stochastic
reconstruction of porous
material using the
fractional Brownian motion
method, showing
individual volume elements
(Kirkpatrick et al. 1983) that, theoretically, is pores, scattering techniques can be used that
capable of reproducing three-dimensional offer in an implicit manner the autocorrelation
descriptions of materials from an arbitrary num- function, thus sidestepping the stage of micros-
ber of moments of the correlation function at the copy and the subsequent phase of image analysis
expense, of course, of heavy requirements in for the extraction of two-dimensional features.
computational time. A simpler procedure that
has proven efficient for several types of porous
membranes including asymmetric ones is the
References
so-called fractional Brownian motion technique
that respects the first two moments of the corre- Adler PM (1992) Porous media- geometry and transports.
lation function and, in addition, offers an inter- Butterworth-Heinemann, Stoneham
weaving option that allows three-dimensional Gelb LD (2009) Modeling amorphous porous materials
and confined fluids. MRS Bull 34:592–601
reconstruction (Fig. 1) at much greater scale
Kikkinides ES, Burganos VN (2000) Permeation proper-
than the correlation length of the structure ties of three-dimensional self-affine reconstructions of
(Kikkinides and Burganos 2000). For materials porous materials. Phys Rev E 62:6906–6915
that have evolved from powders through some Kirkpatrick S, Gelatt CD, Vecchi MP (1983) Optimization
by simulated annealing. Science 220:671–680
agglomeration or sintering process, ballistic or
Quiblier JA (1984) A new 3-dimensional modeling tech-
random placement methods can be used that nique for studying porous-media. J Colloid Interface
allow mass transfer between coalescing particles Sci 98:84–102
at a controlled fashion so as to reproduce the Torquato S (2002) Random heterogeneous
materials – microstructure and macroscopic proper-
actual grain-size distribution and porosity or
ties. Springer-Verlag, New York
solid fraction. Reconstruction of fiber-type mate- Torquato S (2010) Optimal design of heterogeneous mate-
rials can proceed in a similar manner. In the case rials. Annu Rev Mater Res 40:101–129
of porous membranes that contain nanoscale
P
Fiber Models and the elastic properties of the fibers that deter-
mine the macroscopic mechanical properties of
Vasilis Burganos the material. Carbon cloth, electrospun polyacry-
Institute of Chemical Engineering Sciences, lonitrile, and polyester are common examples of
Foundation for Research and Technology, fibrous materials that can be represented by fiber
Hellas, Patras, Hellas models. To convert to a pore model, various
attempts have been made to infer some effective
pore sizes from the fiber model, usually with the
A fiber model is a model that uses straight or help of inscribed spheres among neighboring
curved fibers, either finite in length or infinitely fiber segments. Skeletonization of a fiber model
long, to represent the solid phase in a porous is often part of the analysis routine to facilitate the
material or a reinforcement component in a com- comprehension of the fiber cluster articulation
posite material. Fiber models are the appropriate and the eventual determination of the topology
choice for modeling fibrous media, woven or of the system. Useful concepts from straight-line
nonwoven, typically synthetic but occasionally path statistics or randomness of secant distribu-
also natural ones. Typical examples include the tion through convex bodies (Coleman 1969) are
representation of membranes and porous media incorporated in this type of models. The fibers
for fuel cells (Mathias et al. 2003), filters for the can be hollow or solid, randomly oriented or
separation or sieving of particulate matter, or ordered to arbitrary degree, and either charged
filters for the exclusion of bubbles in diverse or neutral depending on the application. Fiber
applications of microfluidics. There is a recent models of membrane materials and, more gener-
rapid growth of interest in the utilization of fiber ally, fibrous media lend themselves to the numer-
models for the description of the structure of gas ical simulation of transport phenomena through
diffusion layers in fuel cells but also of modern their structure, usually diffusion, single or,
textiles and fabrics for specialized applications two-phase flow, dispersion, particle attraction
(Thiedmann et al. 2009; Gaiselmann et al. 2012). and deposition, combined phase transition and
The typical features that characterize a fiber flow, heat conduction, electrical conduction, and
model include the diameter and length of the light transmission (Torquato 2002; Tomadakis
fiber, the number or length density per unit vol- and Sotirchos 1993).
ume, the solid fraction, the shape of the fibers,
Grain Models,
Fig. 1 Ballistic
reconstruction followed by
partial sintering
is closely related to molecular dynamics, the inter-filler distances, and degree of agglomera-
method is generally differentiated by its inclusion tion (Fig. 1).
of rotational degrees of freedom, as well as
compacted and other complex granular geome-
tries. Grain models have also been used for the References
description of micro- or nanoparticle additives,
also called nanofillers (at least one of the parti- Conway JH, Sloane NJA (1993) Sphere packings, lattices,
and groups, 2nd edn. Springer, New York
cles’ dimensions is in the nanometer range), into Finney JL (1970) Random packings and the structure of
a polymer membrane to form a polymeric com- simple liquids. I. The geometry of random close pack-
posite membrane or a hybrid, mixed matrix mem- ing, Proc R Soc Lond A-Math Phys Sci 319:479–493
brane (Sanchez et al. 2005). This is a promising Jaeger HM, Nagel SR (1992) Physics of granular states.
Science 255(5051):1523–1531
idea to improve the separation properties of the
Preparata FP, Shamos MI (1985) Computational geome-
neat polymer and produce the so-called try: an introduction. Springer, New York
nanobarriers with numerous applications in gas Rogers CA (1964) Packing and covering. Cambridge Uni-
separation, fuel cells, preservation of sensitive versity Press, Cambridge
Sanchez C, Julian B, Belleville P, Popall M (2005) Appli-
products, etc. The enhancement of barrier prop-
cations of hybrid organic-inorganic nanocomposites.
erties through the addition of inorganic J Mater Chem 15:3559–3592
nanoparticles in polymer matrices can be studied Zhu HP, Zhou ZY, Yang RY, Yu AB (2007) Discrete
with the help of grain models and elucidate their particle simulation of particulate systems: theoretical
developments. Chem Eng Sci 62:3378–3392
complex dependence on interfacial interactions, Zhu HP, Zhou ZY, Yang RY, Yu AB (2008) Discrete
filler shape and orientation with respect to the particle simulation of particulate systems: a review of
transport direction, filler size, distribution of major applications and findings. Chem Eng Sci
63(23):5728–5770
A
deformation
Amorphous Polymers and the Amorphous Region, Fig. 1 Thermomechanical curve of an amorphous polymer
Amorphous Polymers
and the Amorphous
Region,
Fig. 2 Temperature specific
dependence of the specific volume
volume of an amorphous
polymer
glass transition
temperature
temperature
ones. Chains of such polymers may be organized semicrystalline polymers varies from that of the
in spherulites having a well-ordered lamellar amorphous polymer. These regions are affected
structure (i.e., a folded chain) with an incorpo- by the presence of crystalline phase, and this
rated disordered amorphous fraction (Fig. 3). phenomenon influences also transport character-
Amorphous polymers are usually transparent; istics of the penetrating media. Traditionally, the
semicrystalline ones are opaque. A segmental “more dense” crystalline phase decreases a chain
mobility of the amorphous regions in mobility and prolongs a transport trajectory of
Amorphous Polymers and the Amorphous Region 3
Amorphous Polymers
and the Amorphous
Region, Fig. 3 Schematic
amorphous region
arrangement of the
spherulite
lamellar structure
Density Functional Theory Modeling EDFT ½rðrÞ ¼ Ts ½rðrÞ þ J½rðrÞ þ Exc ½rðrÞ
ð
of Membrane Systems
þ vðrÞrðrÞdr
Giorgio De Luca
Institute on Membrane Technology ITM-CNR, where Ts[r(r)] is the kinetic energy of an isoelec-
University of Calabria, Rende (CS), Italy tronic noninteracting system, while J[r(r)]
describes the Coulomb electrostatic energy. The
Exc[r(r)] is the exchange and correlation func-
Density functional theory is a new methodology tional, which takes into account the difference
in the frame of quantum mechanics (ab initio). between the kinetic energies of the isoelectronic
The assessment of material features depending on interacting and noninteracting systems in addi-
the electron interactions or electron density tion to the difference between the quantum
polarization necessarily needs the use of quantum electron-electron and Coulomb electrostatic
mechanics. Large molecular systems cannot be energy. r(r) can be evaluated by the nonlinear
described with accurate quantum mechanical Kohn-Sham equations, defined by means of an
approaches, such as correlated Hartree-Fock effective potential. The electron density allows to
(Szabo and Ostlund 1994), due to the huge com- calculate all the properties of the quantum system
putational time required by these. Instead, the in addition to the total energy. Computational
density functional theory (Parr and Yang 1989) approaches, based on density functional theory,
allows to get results with similar precision in are applied in the study of catalysts used in mem-
relatively shorter computational time. Thus, branes and in the study of noncovalent interac-
density functional theory is a powerful tool to tions, such as hydrogen-bonding and London
investigate large chemical systems like the dispersion interactions (De Luca et al. 2009). In
nanostructures involved in the membrane prepa- fact, hydrogen-bonding, electrostatic interactions
ration. In density functional theory, the total and London force are important for membranes at
energy of an electronic system is evaluated the basis of fundamental properties such as
through a total functional which depends on the molecular adsorption and sorption, recognition,
electron density of the quantum system, r(r), and and self-assembly. Also size, shape, and electro-
external potential v(r). It is defined as follows: static features of supramolecular architectures
can be studied using density functional theory.
All these properties control the selectivity of the
materials, used in membranes, the permission as
well as the antifouling or anti-embrittlement
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1062-1
2 Density Functional Theory Modeling of Membrane Systems
features. Density functional theory studies of the and products through the membrane derived by
catalysis in membrane reactors require the defi- the adsorption/absorption of different molecules.
nition of structural models of the catalysts. For
the most part, they are modeled by infinite sur-
faces, slabs, or different types of adsorbed or
References
absorbed atomic clusters. These studies could be
treated independently from the aforementioned De Luca G, Gugliuzza A, Drioli E (2009) Competitive
analysis. However, it is important to emphasize hydrogen-bonding interactions in modified polymer
that the merging of the results obtained by the membranes: a density functional theory investigation.
different investigations would be advisable. For J Phys Chem B 113:5473–5477
Parr RG, Yang W (1989) Density functional theory of
example, the kinetic constants characterizing a atoms and molecules. Oxford University Press, New
reaction path, related to a particular catalyst, York
evaluated by the density functional theory, Szabo A, Ostlund NS (1994) Modern quantum chemistry.
should be compared with the diffusion coeffi- Macmillan Publishing CO, New York
cients characterizing the permeability of reagents
E
Ethanol-Water Mixtures: Separation like alcohols, ketones, ethers, etc. (EP 765682A1
by Pervaporation 1997); separation of mixtures from narrow boiling
temperatures to constant (azeotrope) boiling tem-
Kew-Ho Lee peratures (EP 811420A1 1997); removal of
Department of Chemical and Biomolecular organic pollutants from water and air streams
Engineering, National Research Laboratory for (EP 749351A1 1996); separation of fermentation
Environmental Catalysis, Korea Research products; and separation of organic-organic liquid
Institute of Chemical Technology (KRICT), mixtures (Kujawski 2000). Pervaporation is also
Yuseong-gu, Daejeon, South Korea considered as so-called clean technologies, espe-
cially well suited for the treatment and recycling
of volatile organic compounds and pollution pre-
Pervaporation is an important membrane process vention (Anne et al. 2002).
in chemical industries in which valuables are iso- Transport mechanism of PV through poly-
lated from the liquid mixture. Liquid and vapor meric membranes was studied by many research
separation by thermal processes has always been groups, and it was explained by the solution-
highly energy intensive, and new separation pro- diffusion model (Binning et al. 1961; Paul and
cesses taking advantage of mass transfer through Paciotti 1975; Lee 1975; Mulder and Smolders
dense membranes have already shown they enable 1984; Kataoka et al. 1991a, b). According to the
very significant energy savings as compared to solution-diffusion model, each component of the
more classic technologies (Anne et al. 2002). permeation molecules dissolves into the mem-
Membranes can be used for the selective removal brane and diffuses through the membrane due to
of water from aqueous organic mixtures. the concentration gradient (Mikihiro et al. 1998)
Pervaporation (PV) is a separation process that (Fig. 1).
involves separation of liquid mixtures, in contact Transport through the membrane is driven by
with a membrane. With feed solution on one side, the vapor pressure difference between the feed
permeate is removed as a vapor from the other solution and the permeate vapor. The vapor pres-
side (Brian et al. 2011); pervaporation (PV) is a sure difference can be maintained by applying a
very well-known membrane process for the sepa- vacuum on the permeate side or by cooling the
ration of liquid and vapor mixtures due to its permeate vapor so that it condenses, thus creating
energetic aspects (EP 909209A1 1999; EP a partial vacuum. Commercial systems for the
944575A1 1999; EP 880400A1 1998). dehydration of concentrated alcohol and other
Pervaporation mostly allows a variety of possible solutions have been developed since the 1980s,
application areas: dewatering of organic fluids much of the push coming from interest in the
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1063-1
2 Ethanol-Water Mixtures: Separation by Pervaporation
Ethanol-Water Mixtures:
Separation by
Pervaporation, 1. Sorption
Fig. 1 Solution-diffusion
mechanism (Graham 1866) Micrivoids
Polymer
2. Diffusion
Microchannels
3. Desorption
production of pure ethanol as an alternative liquid membranes are exceptions in that they are hydro-
fuel, where PV can be used to dehydrate (Brian philic but exhibit low fluxes (Brian et al. 2011)
et al. 2011). (Table 1).
The emphasis is on selectivity, postulated to be
determined by selective sorption and selective
Pervaporation Membranes diffusion. Selective sorption is governed by the
presence in the membrane of active centers such
Polymeric Membranes as charged sites which are capable of specific
For dehydration, where the small molar volume interaction with water, while selective diffusion
favors the preferential sorption of water, materials is governed by the rigidity and regularity of the
have to be selected with a higher affinity for water polymer structure and the nature of the polymer
than for the other component. The polymeric interspace, exemplified by the degree of swelling
materials can be broadly classified into three cat- and the frequency of the cross-links. The results
egories: glassy polymers, rubbery or elastomeric for a series of membranes made by grafting neu-
polymers, and ionic polymers. In general, the tral or charged polymers onto supporting mem-
glassy and ionic polymers are more suited for branes are reported in (Table 2).
making water-selective membranes for Polysalts, formed from anionic and cationic
dehydration. polyelectrolytes, would be appropriate for
For water-selective membranes, the most obtaining both highly permeable and highly selec-
important factor responsible for the separation is tive membranes (Semenova et al. 1997) (Table 3).
the specific interaction between water and the The best performers in terms of flux, which at a
polymer. To obtain high selectivities, it is neces- maximum of 5 kg/m2h never achieve high values,
sary to use polymers, which contain specific are charged polymers of one type or another,
groups/active centers, capable of strong interac- including polysalts. Anionic and polysalt mem-
tions with water. branes are superior. For anionic polymers, the
The highest fluxes are those for the hydrophilic proton form has a significantly higher flux than
membranes based on cellulose and Nafion and the metal or quaternary ammonium salt versions,
grafts of hydrophilic poly(vinylpyrrolidone) on owing to the greater free space within the polymer
Teflon and polyacrylonitrile. The PVA/TEOS network (Table 4).
Ethanol-Water Mixtures: Separation by Pervaporation 3
Ethanol-Water Mixtures: Separation by Pervaporation, Table 3 PV dehydration of aqueous ethanol with mem-
brane based on various polysalts (Brian et al. 2011)
Feed (wt% Temp. Separation Flux
Polyanion Polycation water) ( C) factor (g/m2h)
Poly(acrylonitrile-co- Poly(acrylonitrile-co-vinyl pyridine) 10 – 5000 400
acrylic acid)
Cellulose-SO3-Na+ Polyethyleneimine 16 50 295 1900
Cellulose-SO3-Na+ PolyDADMAC, linear 16 50 140 3200
Cellulose-SO3-Na+ Same, but branched 16 50 123 4900
Cellulose-SO3-Na+ Poly-N, N-dimethyl-3, 5- 16 50 123 2700
dimethylenepiperidine chloride
Aromatic polyamide Polyethyleneimine 20 60 15 300
sulphonate
Poly(acrylic acid) Chitosan
On polysulphone supporting membrane 5 30 1008 132
No supporting membrane 5 30 2216 33
Na+ polystyrene Polyallylamine HC1 6.2 70 70 230
sulphonate
Na+ CMC Chitosan 10 70 1062 1140
Na+ CMC N-Ethyl-4-vinyl-pyridinium bromide 10 70 782 1320
Anionic PVA Cationic PVA
DS 2.3 % DS 2.9 % 4.6 75 2250 378
DS 5.0 % DS 5.2 % 4.6 75 1910 284
Ethanol-Water Mixtures: Separation by Pervaporation, Table 4 Highest fluxes for PV dehydration of aqueous
ethanol (Brian et al. 2011)
Separation
Membrane polymer Mem. type Feed (wt% water) Temp. ( C) Flux (g/m2h) factor
Nafion-H+ Anionic 4 70 5000 2.5
Cellulose-SO3-Na+ and Polysalt 16 50 4900 125
polyDADMAC, branched
K+ acrylate graft on poly(vinyl Anionic 20 70 4700 156
fluoride)
PEI/PAA on RO membrane Polysalt 10+ 70 4050 1075
Cellulose-SO3-Na+ and Polysalt 16 50 3200 140
polyDADMAC, linear
K+ acrylate graft on PAN Anionic 20 70 3000 500
separation factor of water/ethanol system was The silicalite membrane showed high ethanol
over 10,000 at 348 K. For ethanol permselective permselectivity, and a separation factor of 58 was
membranes, Sano et al. (1994) prepared polycrys- realized at 333 K by PV. Silicalite membranes
talline silicalite membrane by the hydrothermal seem to have great potential for the ethanol recov-
synthesis. ery by PV (Table 5).
Ethanol-Water Mixtures: Separation by Pervaporation 5
Pd–Cu Alloys for Hydrogen Separations, McKinley DL (1969) Method for hydrogen separation and
Table 1 Permeabilities of Pd–Cu alloys with different purification, USA
wt.% of Cu at 350 C, 300 psig Miller JB, Morreale BD, Gellman AJ (2008) The effect of
adsorbed sulfur on surface segregation in a polycrys-
wt.% Permeability (Cm3/cm2.s)
talline Pd70Cu30 alloy. Surf Sci 602:1819–1825
90Pd–10Cu 0.69 Morreale BD, Ciocco MV, Howard BH, Killmeyer RP,
70Pd–30Cu 0.12 Cugini AV, Enick RM (2004) Effect of hydrogen-
60Pd–40Cu 1.52 sulfide on the hydrogen permeance of palladium-
550Pd–45Cu 0.25 copper alloys at elevated temperatures. J Membr Sci
241:219–224
45Pd–55Cu 0.01
O’Brien CP, Howard BH, Miller JB, Morreale BD,
90Pd–10Cu 0.69 Gellman AJ (2010) Inhibition of hydrogen transport
through Pd and Pd47Cu53 membranes by H2S at
350 C. J Membr Sci 349:380–384
Pomerantz N, Ma YH (2009) Effect of H2S on the perfor-
mance and long-term stability of Pd/Cu membranes.
warping and cracking; and avoids a to b phase Ind Eng Chem Res 48:4030–4039
transition in pure Pd (Gabitto and Tsouris 2009). Roa F, Block MJ, Way JD (2002) The influence of alloy
composition on the H2 flux of composite Pd–Cu mem-
branes. Desalination 147:411–416
Sonwane CG, Wilcox J, Ma YH (2006) Solubility of
References hydrogen in PdAg and PdAu binary alloys using den-
sity functional theory. J Phys Chem
Gabitto JF, Tsouris C (2009) Sulfur poisoning of metal B 110:24549–24558
membranes for hydrogen separation. Int J Chem Eng Yang JY, Nishimura C, Komaki M (2007) Effect of H2S
1:394–411 on hydrogen permeation of Pd60Cu40/V–15Ni com-
Karpova RA, Tverdovskii IP (1959) Sorption of hydrogen posite membrane. J Alloys Compd 446–447
by disperse Pd-Cu alloys. Zhur Fiz Khim 33:1393 Yuan L, Goldbach A, Xu H (2007) Segregation and H2
Kulprathipanja A, Alptekin GO, Falconer JL, Way JD transport rate control in body centered cubic PdCu
(2005) Pd and Pd–Cu membranes: inhibition of H2 membranes. J Phys Chem B 111:10952–10958
permeation by H2S. J Membr Sci 254:49–62
McKinley DL (1969) US. Patent 3,439,474
E
SEDIMENTATION PHASE
INVERSION
If the droplet size exhibits a wide statistical processes may occur on storage depending on
distribution, the emulsion is described as polydis- particle size distribution and density difference
perse, in contrast to monodisperse systems with a between the droplets and the medium (Fig. 1).
uniform droplet size. The ideal particle size In sedimentation, the uniform dispersion of
depends on the available methods of preparation the droplets is disturbed by aggregation, which
and industrial application in each case. Another leads to settling or creaming of the internal phase.
important emulsion property is the ratio of the This process results from external forces usually
volume of the dispersed phase (Vi) to the volume gravitational or centrifugal. When such forces
of the continuous phase or (Ve) is called the phase exceed the thermal motion of the droplets
volume ratio (F). If F < 0.43 (Vi = 30 % of (Brownian motion), a concentration gradient
total volume), the flow properties of the emulsion builds up in the system with the larger droplets
are determined primarily by the continuous moving faster to the top (if their density is lower
phase. If F > 0.43, the viscosity of the emulsion than that of the medium) or to the bottom (if their
generally increases. As F increases, either phase density is larger than that of the medium) of the
reversal or cream formation occurs. container. To keep an emulsion stable, such
Emulsion stability should match its applica- aggregation must be prevented since droplet
tion. Thus, for a number of applications, the aggregates sediment faster than individual small
emulsion should be stable under very specific droplets. Sedimentation is not always necessarily
conditions, but it should break after its purpose accompanied by coalescence. Although the dis-
has been achieved according to a specific condi- tribution has been altered, the original dispersion
tion (such as temperature, pH, or salts, or the can be restored by shaking or stirring. Floccula-
like). An emulsion is stable if fusion of the drop- tion refers to aggregation of the droplets (without
lets is prevented by a sufficiently high energy any change in primary droplet size) into larger
barrier (Tadros 2013). In general, the energy bar- units. It is the result of the van der Waals attrac-
rier is built up by the film of emulsifier that forms tion that is universal with all disperse systems.
at the surface of the droplets. Several breakdown Flocculation occurs when there is no sufficient
Emulsion 3
repulsion to keep the droplets apart to distances until two continuous phases are finally formed.
where the van der Waals attraction is weak. Floc- The driving force for coalescence is the surface or
culation may be “strong” or “weak,” depending film fluctuations which results in close approach
on the magnitude of the attractive energy of the droplets whereby the van der Waals forces
involved. One way to overcome the van der is strong thus preventing their separation. Two
Waals attraction is by electrostatic stabilization droplets can only coalesce if the intervening layer
using ionic surfactants, which results in the for- of liquid is pierced when they approach each
mation of electrical double layers that introduce a other. Therefore, coalescence is opposed in two
repulsive energy that overcomes the attractive ways by the emulsifier film surrounding the drop-
energy. The second and most effective method lets. First, as in the case of aggregation, the like
of overcoming flocculation is by “steric stabili- charges of the electrical double layer prevent
zation” using nonionic surfactants or polymers. them from approaching each other. Second, the
Ostwald ripening (disproportionation) results buildup of an elastic surface film causes the emul-
from the finite solubility of the liquid phases. sion droplets to bounce off each other when they
Liquids that are referred to as being immiscible collide. Coalescence is always followed by accel-
often have mutual solubilities that are not negli- erated settling or creaming, which destroys the
gible. With emulsions, which are usually poly- emulsion completely. The emulsion is then bro-
disperse, the smaller droplets will have larger ken and cannot be reconstituted by shaking or
solubility when compared with the larger ones stirring. The driving force for prevention of coa-
(due to curvature effects). With time, the smaller lescence is to produce a stable film that can be
droplets disappear and their molecules diffuse to achieved by two mechanisms and their combina-
the bulk and become deposited on the larger tion: (i) increased repulsion both electrostatic and
droplets. With time, the droplet size distribution steric and (ii) dampening of the fluctuation. In
shifts to larger values. Several methods may be general, smaller droplets are less susceptible to
applied to reduce Ostwald ripening: (i) Addition surface fluctuations and hence coalescence is
of a second dispersed phase component that is reduced. This explains the high stability of
insoluble in the continuous medium. In this case, nanoemulsions. The phase inversion refers to
partitioning between different droplet sizes the process whereby there will be an exchange
occurs, with the component having low solubility between the disperse phase and the medium. For
expected to be concentrated in the smaller drop- example, an O/W emulsion may with time or
lets. During Ostwald ripening in a change of conditions invert to a W/O emulsion.
two-component system, equilibrium is In many cases, phase inversion passes through a
established when the difference in chemical transition state whereby multiple emulsions are
potential between different size droplets (which produced. Phase inversion of emulsions can be
results from curvature effects) is balanced by the one of two types: transitional inversion induced
difference in chemical potential resulting from by changing the facers that affect the HLB of the
partitioning of the two components. This effect system, for example, temperature and/or electro-
reduces further growth of droplets. lyte concentration, and catastrophic inversion,
(ii) Modification of the interfacial film at emul- which is induced by increasing the volume frac-
sion interface. By using surfactants that are tion of the disperse phase.
strongly adsorbed at the emulsion interface (i.e., Emulsions have application in several indus-
polymeric surfactants) and that do not desorb trial systems such as food emulsion, for example,
during ripening (by choosing a molecule that is mayonnaise, salad creams, deserts, and bever-
insoluble in the continuous phase), the rate could ages; personal care and cosmetics, for example,
be significantly reduced. In coalescence, the indi- hand creams, lotions, hair sprays, and sunscreens;
vidual droplets fuse together. First, the smaller and pharmaceuticals, paints, and bitumen
droplets are absorbed by the larger droplets, and emulsions.
then increasingly larger drops merge together
4 Emulsion
Bimetallic Electrocatalyst for Fuel typical operating conditions. In the case of spe-
Cells cific application of PEM fuel cells, when hydro-
gen is produced from a reformate, an additional
Dmitri Bessarabov requirement such as tolerance of the anode
Faculty of Engineering, DST HySA electrocatalyst toward the traces of CO in the
Infrastructure Center of Competence, North- feed fuel stream must also be met. In order to
West University, Potchefstroom, South Africa reduce costs of the fuel cells, an increased mass
activity of the cathode electrocatalyst is required
that would allow a decrease in the amount of the
General Requirements for Fuel Cells electrocatalyst in a fuel cell device.
was also shown to be lower than that in trend is to make use of unique nanoscale struc-
Pt. However, it is also well recognized that tural effects that can be observed in structurally
these bimetallic electrocatalysts are subject to modified alloys (e.g., de-alloyed Pt-based cata-
significant degradation rates (sintering/dissolu- lysts) and intermetallic systems to enhance
tion) as well as carbon-support corrosion under greatly ORR. These include novel structures
specific voltage cycling conditions that are com- observed in thin film extended surfaces
mon for automotive drive cycles during fuel cell (Stamenkovic et al. 2007; Debe 2012) as well as
startup and shutdown. a multilayer Pt-skin surface (Wang et al. 2011,
A lot of efforts have also been made during the 2012).
last two decades to improve anode electrocatalyst
in fuel cells that are designed to use hydrogen
obtained by means of reforming other fuels. In References
that case an anode electrocatalyst is required for
hydrogen oxidation reaction to take place in the Debe MK (2012) Electrocatalyst approaches and chal-
lenges for automotive fuel cells. Nature 486:43–51
presence of CO, as well as to improve perfor-
Stamenkovic VR, Mun BS, Arenz M, Mayrhofer KJJ,
mance of the methanol fuel cells. The focus has Lucas CA, Wang G, Ross PN, Markovic NM
been on the development of bimetallic platinum- (2007) Trends in electrocatalysis on extended and
based electrocatalysts to reduce the amount of nanoscale Pt-bimetallic alloy surfaces. Nat Mater
6:241–247
adsorbed CO and/or to improve performance of
Vielstich W, Lamm A, Gasteiger HA (eds) (2003a)
electrooxidation of CO. Many metals have been Handbook of fuel cells, vol 1, Fundamentals and sur-
considered for modifying the activity of the plat- vey of systems. Wiley, New York
inum catalyst, but only a few of them (Ru, Ir, Sn, Vielstich W, Lamm A, Gasteiger HA (eds) (2003b)
Handbook of fuel cells, vol 2, Electrocatalysis.
Mo, etc.) lead to improved performances. The
Wiley, New York
most studied bimetallic electrocatalyst is the fam- Wang C, Chi M, Li D, Strmcnik D, van der Vliet D,
ily of Pt/Ru alloys, which enhance greatly the Wang G, Komanicky V, Chang K-C, Paulikas AP,
rate of oxidation of many alcohols (methanol, Tripkovic D, Pearson J, More KL, Markovic NM,
Stamenkovic VR (2011) Design and synthesis of
ethanol, etc.).
bimetallic electrocatalyst with multilayered Pt-skin
surfaces. J Am Chem Soc 133:14396–14403
Wang C, Markovic N, Stamenkovic VR (2012) Advanced
Current Trends platinum alloy electrocatalysts for the oxygen reduc-
tion reaction. ACS: Catalysis 2:891–898
Zhang J (ed) (2008) PEM fuel cell electrocatalysts and
Research and development in the area of bime- catalyst layers. Springer, London
tallic and ternary electrocatalysts is ongoing. The
F
Fuel Cell Components other components are gas diffusion layer, electric
connections, current collectors, separator plates,
Rajnish Kaur Calay and seals. In PEM fuel cell bipolar plates made up
Energy Technology Research Group, Narvik of metal or conductive polymer (or carbon com-
University College, Navrik, Norway posites) have more than one function. Bipolar
plates allow the transfer of electrons from the
anode side of one cell to the cathode side of the
All fuel cells essentially consist of two adjacent cell, provide structural rigidity of the
electrodes – an anode (negative side) and a cath- stack, distribute reactant gas to each cell within
ode (positive side) – and an electrolyte to allow a stack, and distribute reactant gas within the cell
charges to move between the two sides of the fuel in the stack through proprietary flow field topol-
cell. Electrons are drawn from the anode to the ogy (shape designs). In some cases, heat manage-
cathode through an external circuit, producing ment can be integrated in BPP design which
direct current electricity. On both sides of the typically involves a thermally conductive
electrolyte and two electrodes (cathode, anode) medium being supplied through the stack to
are the catalyst layers. A catalyst lowers the acti- remove heat from the stack. Thermally conduc-
vation energy to undergo a reaction and helps the tive mediums typically can be air, de-ionized
reaction to take place at a faster rate. The fuel cell water, or a coolant with high specific heat capac-
type is defined based on the nature of the electro- ity. Liquid electrolyte fuel cells will have elec-
lyte. The six types are alkaline fuel cell (AFC), trodes immersed in the liquid electrolyte and
molten carbonate fuel cell (MCFC), phosphoric often benefit from simplified design and also
acid fuel cell (PAFC), proton exchange mem- less expensive catalyst materials. As a result,
brane or polymer electrolyte membrane (PEM) liquid fuel cells, such as PAFC and MCFC, are
fuel cell, and solid oxide fuel cell (SOFC). The well-established technologies and have been
PEM and SOFC have solid electrolyte, while widely used for medium-scale (<250 kW) sta-
other three fuel cell types have liquid electrolyte. tionary applications. Table 1 shown below gives
In a solid electrolyte fuel cell, for example, a an overview of each type of fuel cell, its electro-
PEMFC, the catalyst layer is spread either on lyte, and the primary catalyst used.
the electrolyte (as in PEM or SOFC) or on the
electrode. In addition to these basic components,
depends strongly on such variables as the O2 current density, jd is hydrodynamic diffusion lim-
adsorption energy, the dissociation energy of the iting current density, and jf is film diffusion lim-
O–O bond, and the binding energy of OH on the iting current density. RDE experiments should be
catalyst surface. The electronic structure of the Pt designed to maximize jf. In that case, 1j ¼ j1 þ j1
k d
catalyst (Pt d-band vacancy) and the Pt–Pt and after rearrangement jk ¼ j jd =ðjd jÞ.
interatomic distance (geometric effect) can For ORR the value of jd is normally taken at
strongly affect these variables. Theoretical calcu- 0.4 V during RDE experiments.
lations on O2 and OH binding energy on several Once jk is known, activity is often reported in
metals have predicted that Pt should have the practical values as mass activity (A/mg Pt) by
highest electrocatalytic activity among other normalization to the value of Pt loading of the
metals with the ORR activity of Pt > Pd > Ir > sample on the disk electrode.
Rh, which is in agreement with experimental Another practically important way of
results. Calculations have also predicted that reporting the electrocatalyst activity is to use
Pt–M (M = Fe, Co, Ni, etc.) bimetallic alloys area-specific activity. The area-specific activity,
should have higher catalytic activity than pure expressed in the following units, uA/cm2 Pt, is
Pt, which has again been proven by experiments reported by normalization of jk to the electro-
(Nørskov et al. 2004). chemical surface area (ECSA) of the catalyst.
pasteurization
pulp
Fresh juice
permeate
(10-11 °Brix)
UF RO
preconcentrated concentrated
juice diluted stripping
stripping solution
(25-26 °Brix) solution
OD
PV concentrated
aromatic compounds juice
(64-65 °Brix)
Fruit Juice Processing by Integrated Membrane Operations, Fig. 1 Integrated membrane process for the
production of concentrated fruit juice
Recovery of Polyphenols from Olive phenolic compounds from OMWs including sol-
Mill Wastewaters by Membrane vent extraction, supercritical fluid extraction, and
Operations chromatographic separation.
Membrane operations such as
Alfredo Cassano microfiltration (MF), ultrafiltration (UF),
Institute on Membrane Technology, ITM-CNR, nanofiltration (NF), and reverse osmosis (RO),
Rende (CS), Italy mostly in sequential form, represent useful tech-
nologies for the recovery, purification, and con-
centration of polyphenols with regard to their
Olives contain an appreciable amount of bioac- molecular weight cutoff values. They offer sig-
tive compounds such as polyphenols with nificant advantages over conventional methodol-
remarkable health benefits. They are potent anti- ogies in terms of low energy consumption, no
oxidants and exhibit various other physiological additive requirements, and no phase change.
activities including antiinflammatory, antimicro- Integrated membrane processes based on the
bial, antiallergic, anticarcinogenic, and antihy- use of these operations permit to obtain purified
pertensive activities (Obied et al. 2005). water which can be discharged in aquatic systems
The biophenolic fraction of olive oil com- according to national regulations or to be used for
prises only 1–2 % of the total phenolic content irrigation. NF is typically employed for the sep-
of the fruits; the remaining 53 % and 45 % are lost aration of most part of phenolic compounds
in olive mill wastewaters (OMWs) and the olive (Paraskeva et al. 2007).
cake, respectively. Typical biophenols occurring
in OMWs are benzoic acid derivatives
(4-hydroxybenzoic, protocatechuic, vanillic
References
acids), hydroxycinnamic acid derivatives
(ferulic, caffeic acids), tyrosol, homovanillyl Obied HK, Allen MS, Bedgood DR, Prenzler PD,
alcohol, hydroxytyrosol, and oleuropein. These Robards K, Stockmann R (2005) Bioactivity and anal-
compounds represent a precious resource of ysis of biophenols recovered from olive mill waste.
potentially useful chemical substances (after J Agric Food Chem 53:823–837
Paraskeva CA, Papadakis VG, Kanellopoulou DG,
their direct recovery or chemical transformation) Koutsoukos PG, Angelopoulos KC (2007) Membrane
for cosmetic and pharmaceutical industries and in filtration of olive mill wastewater (OMW) and OMW
food processing and food product conservation. fractions exploitation. Water Environ Res 79:421–429
Several techniques have been proposed indi-
vidually or in integrated forms to recover
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1089-1
R
food additives,
cosmeceuticals,
nutraceuticals
Olive Mill Wastewater Treatment by (RO) have been proposed and combined in inte-
Membrane Operations grated processes to obtain effluent streams from
OMWs of acceptable quality for safe disposal
Alfredo Cassano into the environment (surface water or soil) for
Institute on Membrane Technology, ITM-CNR, irrigation or even for recycling and use in the
Rende (CS), Italy olive mill. Basically, MF and UF processes are
used for primary treatment purpose, while NF
and RO are used for final treatment (Cassano
The extraction of olive oil generates huge quan- et al. 2013; Paraskeva et al. 2007).
tities of wastes having a great impact on land and Integrated systems based on the use of these
water environments because of their high phyto- processes permit to obtain a COD reduction of
toxicity. Pressure and three-phase centrifugation about 99 %, the recovery of high percentage of
systems produce a liquid effluent called olive mill purified water (60–70 %) (permeate of RO mem-
wastewater (OMW). branes), a production of an organic fraction
Several waste management approaches, (retentate of MF and UF membranes) which can
including physicochemical treatments (natural be submitted to anaerobic digestion for the pro-
evaporation, treatment with lime and clay, oxida- duction of biogas, the recovery of a phenolic
tion), agronomic methods (land spreading), ani- fraction (retentate of NF and RO membranes) of
mal breeding, and biological treatments (both potential interest for food, phytotherapic, or cos-
aerobic and anaerobic) have been proposed to metic applications (Fig. 1).
reduce the polluting load and, consequently, the
final waste disposal. The efficiency of the pro-
cess, the complexity, and the costs involved may References
vary remarkably. In addition, different legisla-
tions existing in olive-oil producing countries Cassano A, Conidi C, Giorno L, Drioli E (2013) Fraction-
ation of olive mill wastewaters by membrane separa-
play an important role in the selection of appro-
tion techniques. J Hazard Mater 248–249:185–193
priated technologies. Paraskeva CA, Papadakis VG, Tsarouchi E,
Pressure-driven membrane operations, includ- Kanellopoulou DG, Koutsoukos PG (2007) Membrane
ing microfiltration (MF), ultrafiltration (UF), processing for olive mill wastewater fractionation.
Desalination 213:218–229
nanofiltration (NF), and reverse osmosis
pretreatment
MF UF NF RO
purified water
Olive Mill Wastewater Treatment by Membrane Operations, Fig. 1 Integrated membrane process for the
treatment of OMWs
O
Biological UF
treatment
discharge in
superficial water
Dynamic Mechanical
Analysis, Fig. 1 Dynamic
mechanical analysis
(DMA) curve of
perfluorosulfonic acid
(PFSA) ionomer. tan d is
the ratio between the loss
modulus E00 and the storage
modulus E0 (Xie 2010)
(Reprinted with permission
from Macmillan Publishers
Ltd: Nature 464:267–270,
copyright (2010))
effect of PFSA (Xie 2010). Mano focused on the follows: Budd et al. studied the mechanical sta-
advantage of DMA that the test conditions can be bility of polymer of intrinsic microporosity
more closely set to the physiological environ- (PIM-1) by DMA in the temperature range from
ments which the biomaterials will be applied to 30 C to 450 C for pervaporation application
(Mano 2008). Using chitosan membranes, their (Budd et al. 2004); Nagarale et al. synthesized
mechanical properties were measured under poly(vinyl alcohol)-SiO2 hybrid membrane by
low/moderate hydration conditions at different sol-gel method for a cation-exchange membrane,
relative humidity (RH) levels and in completely and its mechanical stability was measured by
wet (immersed) condition. Weng DMA (Nagarale et al. 2004); Gholap
et al. synthesized intrinsically dopable polyimide et al. synthesized hydrophobically modified
(DPI) membranes containing an amine-capped PVA-g-polyNTBA membranes, where DMA
aniline trimer (ACAT) having high gas separa- was used to detect the crystallinity of the mem-
tion properties, where DMA results reported branes as a function of annealing (Gholap
higher mechanical and thermal stabilities of the et al. 2004); using DMA, Arjun and Ramesh
membranes than those of polyaniline (PANI) and studied the mechanical stability of the oxida-
conventional nondopable polyimide (NDPI) tively stable polycarbonate urethane (PCU)
(Weng et al. 2011). Other examples are as membranes fabricated by electrospinning method
Dynamic Mechanical Analysis 3
Fig. 2 (continued)
4 Dynamic Mechanical Analysis
Dynamic Mechanical Analysis, Fig. 2 (a) General sample holding method) (www.ngb.netzsch.com)
schematic diagram of dynamic mechanical analysis (Reprinted with permission from NETZSCH-Gerätebau
(DMA) apparatus and (b) modes of deformation (i.e., GmbH)
Dynamic Mechanical Analysis 5
for biomedical application (Arjun and Ramesh Ghassemi H, Schiraldi DA, Zawodzinski TA, Hamrock
2012); Ghassemi et al. synthesized poly(arylene S (2011) Poly(arylene ether)s with pendant
perfluoroalkyl sulfonic acid groups as proton-
ether)s with pendant perfluoroalkyl sulfonic acid exchange membrane materials. Macromol Chem
groups for fuel cell application, where their Phys 212(7):673–678
a-relaxation temperature was reported around Gholap SG, Jog JP, Badiger MV (2004) Synthesis and
196 C (Ghassemi et al. 2011); Love investigated characterization of hydrophobically modified poly
(vinyl alcohol) hydrogel membrane. Polymer
thermal and mechanical transitions for commer- 45(17):5863–5873
cially available polymer Li-ion battery separators Love CT (2011) Thermomechanical analysis and durabil-
(Love 2011). ity of commercial micro-porous polymer Li-ion bat-
tery separators. J Power Sources 196(5):2905–2912
Mano JF (2008) Viscoelastic properties of chitosan with
different hydration degrees as studied by dynamic
References mechanical analysis. Macromol Biosci 8(1):69–76
Nagarale RK, Gohil GS, Shahi VK, Rangarajan R (2004)
Arjun GN, Ramesh P (2012) Structural characterization, Organic–inorganic hybrid membrane: thermally stable
mechanical properties, and in vitro cytocompatibility cation-exchange membrane prepared by the Sol–gel
evaluation of fibrous polycarbonate urethane mem- method. Macromolecules 37(26):10023–10030
branes for biomedical applications. J Biomed Mater Page KA, Cable KM, Moore RB (2005) Molecular origins
Res A Article first published online. doi:10.1002/jbm. of the thermal transitions and dynamic mechanical
a.34255 relaxations in perfluorosulfonate ionomers. Macro-
Budd PM, Elabas ES, Ghanem BS, Makhseed S, molecules 38(15):6472–6484
McKeown NB, Msayib KJ, Tattershall CE, Wang Weng C-J, Jhuo Y-S, Huang K-Y, Feng C-F, Yeh J-M,
D (2004) Solution-processed, organophilic membrane Wei Y, Tsai M-H (2011) Mechanically and thermally
derived from a polymer of intrinsic microporosity. enhanced intrinsically dopable polyimide membrane
Adv Mater 16(5):456–459 with advanced gas separation capabilities. Macromol-
Dynamic Mechanical Analyzer DMA 242 C. Online ecules 44(15):6067–6076
accessible poster. NETZSCH-Gerätebau GmbH. Xie T (2010) Tunable polymer multi-shape memory
http://www.netzsch-thermal-analysis.com/download/ effect. Nature 464:267–270
Poster_DMA_242C_65.pdf. Accessed 25 Aug 2012
W
Wide-Angle X-ray Diffraction Pattern material is a PET with a high degree of crystal-
linity. The thin solid line at the bottom shows a
Doriano Lamba compressed image of the corresponding scatter-
Institute of Crystallography, National Research ing curve from a completely amorphous sample.
Council, Trieste, Italy Compared to the semicrystalline material it only
shows two very broad peaks – the so-called first
and second order of the amorphous halo.
According to the Wide-Angle X-ray Diffraction It is obvious that the semicrystalline material
(WAXD) method, the sample is scanned in a contains this amorphous feature as well, under-
wide-angle X-ray goniometer, and the scattering neath the reflections. In the semicrystalline mate-
intensity is plotted as a function of the 2y angle. rial, the halo is shifted to higher scattering angle.
When X-rays are directed in solids, they will In fact, the dash-dotted curve is simply an image
scatter in predictable patterns based upon the of the scattering curve of the amorphous material
internal structure of the solid. A crystalline solid stretched in the vertical as well as in the horizon-
consists of regularly spaced atoms (electrons) tal direction.
that can be described by imaginary planes. The The dash-dot-dotted curve shows the instru-
distance between these planes is called the mental background of the goniometer. Identifica-
d-spacing. The intensity of the d-space pattern is tion of the observed peaks can be accomplished
directly proportional to the number of electrons by means of data listed in the Polymer Handbook
(atoms) that are found in the imaginary planes (Brandrup et al. 2005).
(Warren 1990). A simple method can be used to describe
Every crystalline solid will have a unique pat- changing crystallinity from WAXD data of iso-
tern of d-spacings, which represents a fingerprint tropic materials. It is based on the computation of
for that solid. In fact, solids with the same chem- areas in Fig. 1. At first, the border between first-
ical composition but different phases can be iden- order and second-order amorphous halo is iden-
tified by their pattern of d-spacings. tified. For PET, this is at 2y 37 (vertical line
For semicrystalline isotropic materials, a qual- in the plot). Then the area, Aam, between the
itative measure of crystallinity is directly amorphous halo and the machine background is
obtained from the respective WAXD curve. integrated. Finally the area, Acr, between the crys-
Figure 1 shows the phenomenon for poly(eth- talline reflections and the amorphous halo is inte-
ylene terephthalate) (PET) membrane (Stribeck grated and the crystallinity index Xc,
2007). The curve in bold solid line shows a Xc = Acr/(Aam + Acr), is computed.
WAXD curve with many reflections. The
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1099-1
2 Wide-Angle X-ray Diffraction Pattern
Wide-Angle X-ray
Diffraction Pattern,
Fig. 1 WAXD curves
from semicrystalline and
amorphous poly(ethylene
terephthalate) (PET).
Separation of the observed
intensity into crystalline,
amorphous, and machine
background (laboratory
goniometer Philips PW
1078, symmetrical-
reflection geometry) (This
figure has been taken from
Stribeck (2007) (Fig. 8.2,
p. 102))
Wide-Angle X-Ray Scattering (WAXS), Fig. 1 Wide- crystalline polyethylene, showing sharp ‘powder’ rings
angle X-ray scattering from (a) polystyrene, showing a (This figure has been taken from Bower (2002), Fig. 3.9,
diffuse halo from an amorphous sample; and (b) highly p. 81)
Amorphous structures yield scattering halos the scattering intensity is plotted as a function of
(broad peaks) whereas crystalline structures are the 2y angle.
characterized by Bragg peaks (Fig. 1). WAXS is
therefore a good monitor of crystallinity in the
sample. References
This technique is a time-honored but a some-
what out-of-favor technique for the determina- Bower DI (2002) An introduction to polymer physics.
Cambridge University Press, Cambridge/New York/
tion of degree of crystallinity of inorganic
Melbourne/Madrid/Cape Town/Singapore/São Paulo
and/or organic membrane polymeric samples. Guinier A (1963) X-ray diffraction in crystals, imperfect
The diffraction pattern generated allows to deter- crystals and amorphous bodies. W. H. Freeman and
mine the chemical composition or phase compo- Company, San Francisco
Nozue Y, Shinohara Y, Amemiya Y (2007) Application of
sition of the membrane film, the texture of the
microbeam small- and wide-angle x-ray scattering to
membrane film (preferred alignment of crystal- polymeric material characterization. Polym
lites), the crystallite size, and presence of film J 39:1221–1237
stress. Stribeck N (2007) X-ray scattering of soft matter. Springer
laboratory manuals in polymer science. Springer, Ber-
According to this method, the sample is
lin/Heidelberg
scanned in a wide-angle x-ray goniometer and
X
X-Ray Diffraction (XRD), a 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Fig. 1 (a) 2D powder
2000 2000
diffraction pattern of a
copolymer based on
alternate benzothiadiazole 1800 1800
and dioctylfluorene
moieties and (b) its 1600 1600
integrated pattern
(Courtesy of Drs W. Porzio 1400 1400
and L. Barba)
1200 1200
Rows
1000 1000
800 800
600 600
400 400
200 200
0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Columns
b 50000
40000
Intensity (arb. units)
30000
20000
10000
0
0 3 6 9 12 15 18 21
2q (∞)
also for the analysis of physical processes occur- diffraction pattern geometry and intensities.
ring at membrane interfaces. A more quantitative study, normally carried out
X-ray diffraction has been the main technique on polycrystalline samples (powder diffraction,
for the determination of crystalline polymers Fig. 1), may lead to the structural determination
structure. From the diffraction pattern of well- of the unit cell content, thus giving a molecular
aligned polymer crystallites, it is possible to model of the crystalline polymer. Besides, poly-
obtain the unit cell parameters, by inspecting the mer crystal diffraction patterns generally do not
X-Ray Diffraction (XRD) 3
contain the full information needed for a com- analysis of the membrane diffraction pattern
plete crystal structure determination, and a may give important insights into the material
modeling procedure is employed by exploiting modification upon membrane preparation.
crystal packing hypothesis based on polymer
physics knowledge. The final accepted model is
the one which best reproduces the experimental
References
diffraction pattern.
X-ray diffraction is also used in polymer Bower DI (2002) An introduction to polymer physics.
chemistry to estimate the crystallinity index, by Cambridge University Press, Cambridge, UK
evaluating the different contributions to the total Roe RJ (2000) Methods of x-ray and neutron scattering in
diffracted intensity of the amorphous and crystal- polymer science. Oxford University Press, Oxford
Warren BE (1990) X-ray diffraction. Dover, New York
line components of the sample.
Finally, if one or more of the components of
the membrane are in the crystalline state, the
X
electrons
electrons
relativistic speed
radiation
non-relativistic speed
radiation
X-Ray Synchrotron, Fig. 1 Simplified representation of the angular distribution of emitted radiation from electrons
moving at relativistic and nonrelativistic speed and traveling in a circular path
X-Ray Synchrotron, Fig. 2 Sketch of a modern (wigglers, undulators); (D) quadrupole magnets; (E)
SR-dedicated storage ring. (A) Emitted synchrotron radi- radio-frequency cavity; (F) injection magnet. Electron
ation; (B) bending magnets; (C) insertion devices path is represented in magenta
domain inhomogeneities in both size and orien- microbeam approach was also applied to SAXS
tations (Riekel and Davies 2004). The same and WAXS techniques.
X-Ray Synchrotron 3
Highly intense and extremely collimated SR from the use of X-ray synchrotron radiation.
beams have also been largely used in SAXS Chemical analysis with photoelectron spectros-
experiments, to provide structural information copy requires tunable and brilliant SR beams in
on the nm size of polymeric and biological mem- order to chemically and electronically character-
branes (like lipid bilayers). Soft matter, like bio- ize surfaces like metal-based membranes.
logical membranes, is well known as low X-ray
scattering material, and the intense SR beam is a
unique tool for SAXS studies. Moreover, the
References
strong collimation of the beam allows a resolu-
tion impossible to be reached with conventional Chu B, Hsou B (2001) Small-angle x-ray scattering of
sources. Wavelength tunability is another charac- polymers. Chem Rev 101:1727–1761
teristic of SR largely exploited in SAXS, where Duke P (2008) Synchrotron radiation. Oxford University
time structure of SR has been used in time- Press, New York
Margaritondo G (2002) Elements of synchrotron light.
resolved experiments (Chu and Hsou 2001). Oxford University Press, New York
X-ray-based imaging techniques applied to Riekel C, Davies RJ (2004) Applications of synchrotron
hard and soft matter gained a great benefit from radiation micro-focus techniques to the study of poly-
the use of intense and small X-ray beam as for mer and biopolymer fibers. Curr Opin Colloid Inter-
face Sci 9:396–403
tomographic methods. X-ray photoelectron spec-
troscopy methods also received a great impulse
X
Monochromator
X-ray beam Detector
Sample
Synchrotron
Slits
Goniometer
3D reconstruction
sliced maps
Image
Processing
of images can be collected in a relatively small membrane porosity. Exploiting the different
amount of time. Image processing is computed absorption coefficient between the polymer and
offline by using appropriate algorithms such as water is possible to investigate the porosity of the
the “filtered back projection” or “direct Fourier membrane in a quantitative way. Different poros-
inversion” methods which are found in dedicated ity across the membrane is easily spotted from 3D
image reconstruction software packages (Fig. 1). sample reconstruction, and an estimation of the
SR-mCT is a valuable tool in membrane struc- shape and dimensions of the pores is also possible
ture analysis as provided by a nondestructive due the high resolution attainable with SR-mCT
method for the investigation, at the micrometric (Remigny et al. 2007).
size, of both the bulk and the interface structure
of the membrane. Tomographic methods do not
require specific sample preparation, finally giv-
References
ing a high-resolution 3D representation of the
“native” sample under study. Bonse U, Busch F (1996) X-ray computed
SR-mCT has been widely used in order to gain microtomography (mCT) using synchrotron radiation
insights into the water distribution in polymer (SR). Prog Biophys Mol Biol 65:133–169
Manke I, Markötter H, Tötzke C, Kardjilov N,
electrolyte membrane fuel cells (PEMFC) in
Grothausmann R, Dawson M, Hartnig C, Haas S,
response to various operation conditions. By Thomas D, Hoell A, Genzel C, Banhart J (2011) Inves-
using SR-mCT the correlation between the wet- tigation of energy-relevant materials with synchrotron
ness of the polymer electrolyte membrane, its x-rays and neutrons. Adv Eng Mat 13:712–729
Remigny JC, Meireles M, Thibault X (2007) Morpholog-
structure, and its proton conductivity has been
ical characterization of a polymeric microfiltration
established (Manke et al. 2011). membrane by synchrotron radiation computed
A typical application of SR-mCT to membrane microtomography. J Membr Sci 305:27–35
science is the structural investigation of the
G
Mon (gas) + e
1
R (gas) + e
the membranes are prepared feeding the plasma
with an acid precursor and a fluorocarbon mono-
2 mer. The challenge in this kind of process is to
Substrate + I+ Substrate*
retain in the deposited films the acid functional-
3 ity, which can be easily cleaved in plasma. This is
R (gas) + Substrate* a- (film)
usually obtained by lowering the energy of the
5 plasma by properly adjusting process parameters.
4
n R (gas) R n(gas) Powders Proton conductivities in the range of
6 6 10 3–2 mS/cm have been reported; however,
values as high as 180 mS/cm have been recently
a- (film)
achieved (Brault et al. 2006; Thery et al. 2010).
Plasma-Enhanced Chemical Vapor Deposition, Polyethersulfone (PES) membranes have been
Fig. 1 Sketch of the activated growth model coated with plasma-polymerized acrylic acid for
the subsequent immobilization of galactonic acid
this second route generally leads to polymers less through a hydrophilic spacer arm molecule. This
compact and with poor adhesion to the substrate. strategy allowed the setup of a bioreactor for
Based on this mechanism it appears quite biomimicking the cellular microenvironment
straightforward that the chemical composition accomplishing long-term maintenance and dif-
and structure of PECVD films can be finely ferentiation of human hepatocytes (Memoli
tuned by properly adjusting process parameters et al. 2007; De Bartolo et al. 2005).
such as input power, pressure, feed composition,
substrate temperature, and self-bias (see ▶ Cold
Plasma in this encyclopedia). References
In the field of membrane processing, PECVD
can be used both to modify the surface of com- Brault P, Roualdes S, Caillard A, Thomann A-L,
Mathias J, Durand J, Coutanceau C, Leger J-M,
mercially available membranes and to prepare Charles C, Boswell R (2006) Solid polymer fuel cell
freestanding ones. These membranes mainly synthesis by low pressure plasmas: a short review. Eur
find applications in the field of gas and liquid Phys J Appl Phys 34:151–156
separation, fuel cells, sensors, and biomaterials Coclite AM, Milella A, d’Agostino R, Palumbo F (2010)
On the relationship between the structure and the bar-
(Roualdes et al. 2010; Memoli et al. 2007; De rier performance of plasma deposited silicon dioxide-
Bartolo et al. 2005). like film. Surf Coat Technol 204:4012–4017
The gas and liquid permeability of membranes Creatore M, Palumbo F, d’Agostino R, Fayet P (2001) RF
can be tuned with the aid of suitable PECVD plasma deposition of SiO2-like films: plasma phase
diagnostics and gas barrier film properties optimiza-
coatings, through the control of the surface wet- tion. Surf Coat Technol 163:142–144
tability or inducing specific chemical interactions d’Agostino R (1990) Plasma deposition, treatments and
between the permeant molecules and the film. etching of polymers. Academic, San Diego
Silicon oxide-like coatings have been widely d’Agostino R, Palumbo F (2012) Comment on “Ion-
assisted processes of polymerization in low-pressure
exploited as barrier to control gas and vapors plasmas”. Plasma Process Polym 9:844–849
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functionalized coatings can be deposited on con- Gristina R, d’Agostino R, Drioli E (2005) Biotransfor-
mation and liver-specific functions of human hepato-
ventional membranes to enhance their liquid or cytes in culture on RGD-immobilized plasma-
vapor separation performances (Weibel processed membranes. Biomaterials 26:4432–4441
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PECVD ion exchange membranes can mainly approaches in the design of ceramic and hybrid mem-
branes. J Membr Sci 316:176–185
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ton exchange membrane fuel cells. Commonly, Procino A, Barbieri G, Curcio E, Giorno L, Esposito P,
Cozzolino M, Brancaccio D, Andreucci V,
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Milella A, Palumbo F, Favia P, Cicala G, d’Agostino carboxylic membranes deposited by plasma enhanced
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Pure Appl Chem 77:399–414 Weibel DE, Vilani C, Habert AC, Achete CA (2007) Sur-
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cycle must balance to zero and a self-bias that is
negative with respect to the plasma potential
develops. If the surface is electrically isolated, References
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Chen FF (1974) Introduction to plasma physics. Plenum
immersed in a plasma will be bombarded by ions. Press, New York
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can be also ignited at atmospheric pressure, and etching of polymers. Academic, San Diego
Favia P, Sardella E, Lopez LC, Laera S, Milella A,
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Pistillo B, Intranuovo F, Nardulli M, Gristina R,
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dielectric barrier discharge, corona, and atmo- cation processes for biomedical materials and devices.
spheric jet) to material processing (Kogelschatz In: G€uçeri S, Fridman A (eds) Plasma assisted decon-
tamination of biological and chemical agents.
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Springer, Dordrecht, pp 203–226
Cold plasmas can modify the surface of mate- Fontananova E, Donato L, Drioli E, Lopez LC, Favia P,
rial by depositing thin films (plasma-enhanced d’Agostino R (2006) Heterogenization of
chemical vapor deposition), by grafting specific polyoxometalates on the surface of plasma-modified
polymeric membranes. Chem Mater 18:1561–1568
chemical functionalities (plasma treatment), or
Grill A (1994) Cold plasma in materials fabrication-from
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Membranes can be processed by means of Kogelschatz U (2003) Dielectric-barrier discharges: their
cold plasmas to activate the surface by introduc- history, discharge physics, and industrial applications.
Plasma Chem Plasma Proc 3:1–46
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C
Crystal Nucleation,
Fig. 1 Effect of the
nucleus radius (r) on the
free energy of germination
DGg (in black color).
Interfacial free energy and
free energy of aggregation
are reported in red and
green color, respectively
nucleation is welcome, the presence of dust or causes an increase of the local level of supersat-
small foreign particles, such as mica or silica able uration (Curcio et al. 2006), inducing the forma-
to promote heterogeneous nucleation, can repre- tion of crystal nuclei also in the presence of lower
sent an advantage (Falini et al. 2002; Saridakis amount of initial substance. For this reason,
and Chayen 2009). These particles, also called membrane crystallizers are particularly attractive
crystallization seeds, act as nucleant and usually for crystallization processes where the solute is
increase the chances of crystallization by facili- expensive, such as in the case of proteins. In
tating the proper molecular orientation during the addition, a fine regulation of the nucleation rate
formation of the crystal nuclei (Bolanos-Garcia can be achieved by managing the transmembrane
and Chayen 2009). The result is the reduction of flux of the solvent from the crystallizing solution
the activation energy and, consequently, the toward the stripping solution located on the other
decrease of the supersaturation level required to side of the membrane. Nucleation mechanism on
induce the formation of crystal nuclei with the membrane (Fig. 2) consists of a first phase
respect to that required in the homogeneous where solute molecules are adsorbed on the sur-
nucleation. In these conditions, nucleation could face by means of attractive interactions able to
even occur in the metastable zone where crystals properly orient the molecule and that usually
grow larger and better ordered than those grown drive the growth of the crystal toward a specific
at higher supersaturation level. The direct contact crystal structure (Di Profio et al. 2009). The effec-
between crystallizing solution and an irregular tive control of the nucleation process by means of
surface can induce heterogeneous nucleation, as an appropriate choice of the porosity and hydro-
occurs in membrane crystallizers (Di Profio phobicity of the membrane and by managing the
et al. 2003, 2005). The local entrapping of the transmembrane flux makes membrane
solute molecules in the pores of the membrane
Crystal Nucleation 3
References
a b
Pressure
Free energy
Monoclinic form 153°C
1420 atm
95°C Liquid
1 atm
A form
Rhombic 445°C
form
115°C
10-5 atm Gas
115°C
B form 10-5 atm
c
Free energy
A form
B form
Crystal Polymorphism, Fig. 1 Enantiotropic and diagram for the enantiotropic system rhombic sulfur-
monotropic systems. (a) Variation of free energy with monoclinic sulfur. (c) Variation of free energy with tem-
temperature for enantiotropic substances. The tempera- perature for enantiotropic substances. No crossing of free
ture Tx, which marks the boundary between stability energy curves belonging to the A and B forms can be
zones for A and B forms, is below the melting tempera- observed below of their melting temperatures (TmA and
tures of the two substances (TmA and TmB). (b) Phase TmB)
in several crystal forms, as a consequence of the properties (Di Profio et al. 2007, 2009, 2013).
different conformations assumed by peptide So crystallization assisted by membrane can
chain in a given condition. A classic example of occur both under thermodynamic and kinetic
polymorphism for crystal of proteins is the lyso- control: low evaporation rates through the mem-
zyme that crystallizes in six different crystalline brane allow the growth of the more stable nuclei
forms. Another important example is the at the expense of the less stable forms
ubiquitin, whose crystal form depends on the (thermodynamic control), while the induction of
nature and the amount of the metal ion used a more rapid nucleation increases in the presence
during the crystallization (Arnesano et al. 2011; of higher evaporation rates and increases the con-
Falini et al. 2009). The technology of membrane version rate from the stable to the metastable
crystallizers gives the opportunity to drive the form (kinetic control). The relative amount of
crystallization toward a specific polymorph. the two forms depends on the ratio between the
This is possible by regulating the degree and the conversion and crystallization rate. Similarly, the
rate to which of supersaturation is reached production of a specific polymorph can be
through the managing of the transmembrane obtained by using antisolvent membrane crystal-
flux and an accurate choose of the membrane lization processes (Di Profio et al. 2010).
Crystal Polymorphism 3
from more rapid precipitations, where the inser- (Ye et al. 2013). In addition, membrane devices
tion of the impurities results facilitate. In addi- are also used to produce high-purity cocrystal, a
tion, high supersaturation often leads to challenge particularly interesting for pharmaceu-
contaminant inclusions that reduce the crystal tical industry.
purity. At the present, membrane technology rep-
resents one of more promising tools to produce
high-purity crystal. By controlling the transmem-
References
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maximum level of supersaturation and reduce the Burton JA, Prim RC, Slichter WP (1953) The distribution
growth rate to reach the critical threshold, beyond of solute in crystals grown from the melt. Part
which inclusion of impurities occurs (Weckesser I. Theoretical. J Chem Phys 21:1987–1991
Davis KJ, Dove PM, Wasylenki LE, Deyoreo JJ
and Konig 2008; Mullin 1993). Today, the
(2004) Morphological consequences of differential
advances made in the development of Mg2+ incorporation at structurally distinct steps on
membrane-assisted crystallization allow produc- calcite. Am Mineral 89:714–720
ing crystalline materials having the purities Mullin JW (1993) Crystallization, 3rd edn. Butterworth-
Heinemann, Oxford
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van Enckevort WJP, van der Berg (1998) Impurity
product. One of the most important examples is blocking of crystal growth: a Monte Carlo study.
represented by the production of sodium carbon- J Cryst Growth 183:441–455
ate crystals having purity grade that reaches Weckesser D, Konig A (2008) Particle shape and purity in
membrane based crystallization. Chem Eng Technol
ca. 99.5 % also starting from crystallizing solu-
31:157–162
tions containing concentrations ranging from 0.2 Ye W, Lin L, Shen J, Luis P, Van der Bruggen B (2013)
to 0.6 M of impurities, such as sodium nitrate, Cryst Growth Des 13:2362–2372
sodium sulfate, and sodium chloride
C
Crystal Seeding, Table 1 Seeding procedures for zeo- Caro J, Noack M, Kolsch P, Schafer R (2000) Zeolite
lite membrane preparation membranes-state of their development and perspec-
tive. Micropor Mesopor Mater 38:3–24
Seeding procedure References
Hasegawa Y, Sotowa KI, Kusakabe K, Morooka S (2002)
Secondary growth Lovallo and Tsapatsis (1996) The influence of feed composition on CO oxidation
Dip coating (Lovallo et al. 1998; Bernal using zeolite membranes loaded with metal catalysts.
et al. 2001) Micropor Mesopor Mater 53:37–43
Spin coating Mintova and Bein (2001) Hasegawa Y, Ikeda T, Nagase T, Kiyozumi Y, Hanaoka T,
Rubbing (Kusakabe et al. 1998; Mizukami F (2006) Preparation and characterization
Hasegawa et al. 2002) of silicalite-1 membranes prepared by secondary
growth of seeds with different crystal sizes. J Membr
Cationic polymer use (Hedlund et al. 1999; Weh
Sci 280:397–405
et al. 2002)
Hedlund J, Noack M, Kolsch P, Creaser D, Caro J, Sterte
Cross-flow filtration Pera-Titus et al. (2005) J (1999) ZSM-5 membranes synthesized without
Dead-end filtration Huang et al. (2004) organic templates using a seeding technique.
(vacuum seeding) J Membr Sci 159:263–273
Hermes M, Vermolen ECM, Leunissen ME, Vossen DLJ,
van Oostrum PDJ, Dijkstra M, van Blaaderen A (2011)
Nucleation of colloidal crystals on configurable seed
structures. Soft Matter 7:4623–4628
strong control of the seeding in order to obtain Huang A, Lin YS, Yang W (2004) Synthesis and proper-
high-quality membranes having determined fea- ties of A-type zeolite membranes by secondary growth
tures, such as a specific crystalline orientation method with vacuum seeding. J Membr Sci 245:41–51
Kusakabe K, Kuroda T, Morooka S (1998) Separation of
(Caro et al. 2000). Several seeding techniques carbon dioxide from nitrogen using ion-exchanged
have been developed to produce a membrane of faujasite-type zeolite membranes formed on porous
zeolite crystal (Table 1), and the secondary support tubes. J Membr Sci 148:13–23
growth together with dip coating is considered Li G, Lin RS, Kikuchi E, Matsukata M (2005) Growth
mechanism of a preferentially oriented mordenite
among those most promising: secondary growth membrane. J Zhejiang Univ Sci B 6:369–372
exploits a hydrothermal treatment of the mem- Liu YX, Wang XJ, Lu J, Ching CB (2007) Influence of the
brane support that has been previously covered roughness, topography, and physicochemical proper-
with layers of seeds (Lovallo and Tsapatsis ties of chemically modified surfaces on the heteroge-
neous nucleation of protein crystals. J Phys Chem
1996), while dip coating takes advantage from B 111:13971–13978
the capillary force to aid the deposition of crystal Lovallo MC, Tsapatsis M (1996) Preferentially oriented
seeds (Lovallo et al. 1998; Bernal et al. 2001). In submicron silicalite membranes. AIChE
addition, filtration procedures, such as cross-flow J 42:3020–3029
Lovallo MC, Gouzinis A, Tsapatsis M (1998) Synthesis
filtration and dead-end filtration (Pera-Titus and characterization of oriented MFI membranes pre-
et al. 2005; Huang et al. 2004), based on the pared by secondary growth. AIChE J 44:1903–1913
seed deposition on the membrane support under Mintova S, Bein T (2001) Microporous films prepared by
the action of a difference of pressure applied, spin-coating stable colloidal suspensions of zeolites.
Adv Mater 13:1880–1883
have been also developed. Pera-Titus M, Llorens J, Cunill F, Mallada R, Santamarıa
J (2005) Preparation of zeolite NaA membranes on the
inner side of tubular supports by means of a controlled
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References Saridakis E, Chayen NE (2009) Towards a ‘universal’
nucleant for protein crystallization. Trends Biotechnol
Bergfors T (2003) Seeds to crystals. J Struct Biol 27:99–106
142:66–76 Weh K, Noack M, Sieber I, Caro J (2002) Permeation of
Bernal MP, Xomeritakis G, Tsapatsis M (2001) Tubular single gases and gas mixtures through faujasite-type
MFI zeolite membranes made by secondary (seeded) molecular sieve membranes. Micropor Mesopor Mater
growth. Catal Today 67:101–107 54:27–36
C
Crystallizing Solution, Fig. 1 Vapor phase transfer in of antisolvent membrane crystallizers, the solubility of the
membrane crystallizers. (a) On the crystallizing solution solute decreases due to the increase of the antisolvent
side, the solute concentration increases due to the solvent concentration inside the crystallizing solution usually gen-
removal triggered by the gradient of vapor pressure erated by a temperature difference between the two sides
between the two sides of the membrane. (b) In the case of the membranes
change when the supersaturation level is reached produce crystal of L-asparagine with narrow size
in the time by using vapor or liquid diffusion distribution (Zarkadas and Sirkar 2006).
techniques. Techniques that exploit membranes
to put in contact a crystallizing solution
containing the molecule to crystallize and a strip- Cross-References
ping hypertonic solution or an antisolvent on the
other side of the membrane (distillate side) ▶ Antisolvent
belong to the latter category. Due to its hydro- ▶ Antisolvent Membrane Devices
phobicity, membrane is not wet by the two liquids ▶ Crystallization
on the two sides and the flux of solvent molecules ▶ Hydrophobicity
through the membrane can occur by vapor diffu- ▶ Multivariate Analyses
sion (Fig. 1a). Accordingly, it is possible to ▶ Solubility
achieve a fine regulation to the rate to which
solute increases its concentration in the crystal-
lizing solution by managing the transmembrane References
flux. Similarly, in the case of antisolvent mem-
brane devices, vapor diffusion triggers the Di Profio G, Stabile C, Caridi A, Curcio E, Drioli E (2009)
Antisolvent membrane crystallization of pharmaceuti-
increase of the antisolvent concentration inside cal compounds. J Pharm Sci 98:4902–4913
the crystallizing solution (Fig. 1b), resulting in a Segelke BW (2001) Efficiency analysis of sampling pro-
decrease of the solute solubility (Di Profio tocols used in protein crystallization screening. J Cryst
et al. 2009). By using hydrophilic membranes, it Growth 232:553–562
Wilson WW (2003) Light scattering as a diagnostic for
is possible to exploit liquid-phase transfer: in this
protein crystal growth-a practical approach. J Struct
case, crystallizing solution is directly pressed Biol 142:56–65
through a porous membrane in an antisolvent Zarkadas DM, Sirkar KK (2006) Antisolvent crystalliza-
(or vice versa). This technique has been used to tion in porous hollow fiber devices. Chem Eng Sci
61:5030–5048
C
Crystallization,
Fig. 1 Crystallization
phase diagram. Crystal
nucleation takes place in
metastable zone (in yellow)
and crystals growth in
labile zone (in pink), both
belonging to the
supersaturation zone. The
condition of
supersaturation is reached
when solute concentration
is slightly higher than the
solubility (gray line);
differently, a much higher
solute concentration leads
to amorphous precipitation
(light cyan area)
Nanofiltration for Reuse of Sharpless solvent, using an aqueous system that includes a
Catalytic Systems surfactant, such as sodium dodecyl sulfate and
sodium cholate, or an ionic liquid such as
Frederico Castelo Ferreira hexadecyltrimethylammonium bromide (Branco
Department of Bioengineering, Instituto Superior and Afonso 2002; Branco et al. 2008). Moreover,
Técnico, Institute for Bioengineering and the use of aqueous/surfactant or ionic liquid sys-
Biosciences, Universidade de Lisboa, Lisbon, tems avoids the continuous gradual slow addi-
Portugal tion, required to obtain high enantiomer
excesses in the aqueous/organic system. Wide-
spread industrial application of the Sharpless sys-
Nanofiltration for reuse of Sharpless catalytic tem has been restricted by the high cost of the
systems combines reaction and separation in a catalyst and toxicity of the osmium species.
single vessel, allowing successive reaction and Aqueous and ▶ organic solvent nanofiltration
filtration steps, to recycle the catalytic system in had been assayed to isolate chiral product and
successive batches with isolation of the chiral recycle the osmium salt and chiral ligand
product on the permeated solution. The Sharpless hydroquinidine 1,4-phthalazinediyl diether
catalysis is a robust strategy for production of (molecular weights, MW, of 368 Da and
chiral 1,2-diols from olefins at high yields and 779 Da, respectively) (Branco et al. 2008;
enantiomer excesses, using a catalytic system Ferreira et al. 2007) into successive reactions.
based on OsO4 or K2OsO2(OH)4 salt and a chiral NMO with a molecular weight of 135 Da was
dimeric ligand (Bolm et al. 2000; Kolb used as co-oxidant for both aqueous/organic and
et al. 1994). Chiral ligands used are based on a aqueous/surfactant systems. Starmem120, a
cinchona alkaloid (dihydroquinidine or polyimide membrane with nominal ▶ molecular
dihydroquinine) with phathalazina, pyrimidine, weight cutoff (MWCO) of 200 Da, was used for
or indoline groups. The reaction requires a the aqueous/organic system, composed of a
co-oxidant, which can be organic or inorganic, water/acetone (25 v% acetone) mixture, with a
such as N-methylmorpholine-N-oxide (NMO) or lower water content than in the conventional
K3Fe(CN)6, respectively. The reaction media is Sharpless system, to improve solvent mixture
conventionally an aqueous/organic (50 v/v% sol- flux through the membrane (Ferreira
vent) mixture with tert-butanol, methyl tert-butyl et al. 2007). On the other hand, a ▶ polyamide
ether, or acetone. The feasibility of Sharpless membrane, Desal DK, with a MWCO of about
reaction was also attained for a range of seven 250 Da, was used in the aqueous/surfactant sys-
different olefins on the absence of organic tem to retain both catalytic system and sodium
# Springer-Verlag Berlin Heidelberg 2012
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1149-1
2 Nanofiltration for Reuse of Sharpless Catalytic Systems
but this relationship can be disrupted by the Jean YC, Mallon PE, Schrader DM (2003) Principles and
chemical nature of the sample (Pethrick 1997; applications of positron and positronium chemistry.
World Scientific, London
Xie et al. 2011; Kobayashi et al. 2009). This Ju H, Sagle AC, Freeman BD, Mardel JI, Hill AJ
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because free volume in these materials is related Sci 358:131–141
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material (Ju et al. 2010; Xie et al. 2011; Hill fuel cells. J Phys Chem B 113:5698–5701
et al. 1996, 2005; Rowe et al. 2009; Zhang Liao K-S, Chen H, Awad S, Yuan J-P, Hung W-S, Lee
et al. 2012; Freeman and Yampolskii 2010; K-R, Lai J-Y, Hu C-C, Jean YC (2011) Determination
of free-volume properties in polymers without
Chen et al. 2012; Yampol’skii et al. 2006; orthopositronium components in positron annihilation
Cohen and Turnbull 1959; Matteucci et al. 2006). lifetime spectroscopy. Macromolecules 44:6818–6826
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Freeman B, Yampolskii Y (2010) Membrane gas separa- disulfonated poly(arylene ether sulfone) random
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DR (2009) A variable energy positron annihilation
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T
Pd-Based Membrane: Exposure with the source of the feedstock and the gasifica-
to Coal Gas tion technology applied. Even though some field
tests applying Pd-based membranes in actual
Thijs Peters coal-derived syngas have been performed, the
SINTEF Materials and Chemistry, Oslo, Norway reactivity of the majority of these compounds
with Pd and its alloys is not known.
With current understanding, production of
Pd-based membranes have frequently been stud- hydrogen from coal and other sulfur-containing
ied in membrane reactors for steam reforming sources is challenging for Pd-based membranes
(SR-MR) and water-gas shift (WGS-MR) reac- particularly due to their limited stability toward
tions to simultaneously achieve a high methane sulfur. Even a few ppm of sulfur in the gas
conversion and production of pure H2. A key reduces the flux drastically due to strong surface
feature of this process intensification is that such adsorption leading to reduced permeability,
a membrane reactor would produce both a high- while higher concentrations (typically above
pressure CO2 stream and high-purity H2. Synthe- 100 ppm depending on operating temperature)
sis gas may also be produced by gasification of even lead to a complete deterioration of the mem-
coal or biomass, enabling production of hydrogen brane caused by formation of bulk Pd4S. This has
from these important sources. Downstream led to the development of a number of new alloys
processing of gasification effluents, i.e., separa- with higher sulfur tolerance (see entry “▶ Ter-
tion or further reaction, is however more chal- nary Pd-Alloy Membranes”). Still, however, flux
lenging than in the case of natural gas because of targets remain a challenge for these alloys in
the wide range of possible impurities and large-scale applications in the presence of sulfur
by-products associated with the coal or biomass. impurities. For application of Pd-alloy mem-
Coal-derived synthesis gas can contain up to branes in coal-derived synthesis gas, sulfur
15,000 ppm H2S as well as COS (<0.1 %), needs thus to be removed by processes such as
NH3 + HCN (<0.3 %), C2 hydrocarbons, ZnO beds and hydrodesulfurization. This
polyaromatic hydrocarbons (PAHs), halides desulfurized synthesis gas may still contain
(such as CH3F, CH3Cl at around 2 ppmv), trace levels of H2S, and it is therefore important
heavy metals (such as Hg, Cd, Pb), tellurides to assess the stability of Pd-alloy membranes
(arsenides, selenium, antimony), alkali metals under long-term exposure to trace levels of H2S
(Na, K, Ca), phosphorous, tars, and other and to determine the upper acceptable H2S level.
unknown compounds, in concentrations varying
The hollow fibers can be spun at room temper- gas is used to evaporate the solvent(s) so that the
ature (20–22 C) or at a temperature higher than fiber solidifies and collected on a take-up wheel.
the ambient temperature. During spinning the Spinning is followed by stretching of the as-spun
take-up speed is normally maintained nearly the fibers to orient the polymer chains along the gas
same as the dope extrusion speed so that no gap (i.e., fiber axis). The as-spun fibers do not
external elongational stresses, except gravity, come into contact with a precipitating liquid. In
can be applied to the nascent hollow fiber. dry spinning and melt spinning, the dimensions
A very large air gap distance may lead to flow of the spinneret are not so crucial because the
instability of the fiber resulting in nonuniform fiber dimensions are mainly determined by the
fiber dimensions. Examples of typical applied ratio of the extrusion rate and “tearing rate”
spinning parameters of different poly(vinylidene (Mulder 1992). The gas flow used for solvent
fluoride), PVDF, dope solutions are bore liquid evaporation and solidification of the fibers influ-
flow rate (0.5–3 ml/min), air gap distance ences to a significant extent the quality of the
(0–3 cm), take-up speed (free fall, 5 m/min), produced fibers.
dope solution flow rate (2–4 ml/min), applied In melt spinning, the polymer is first com-
pressure over the dope solution (138–207 kPa), pressed, heated, and melted by an extrusion
and temperature of the coagulants (15.5–25 C) screw, then forced through the annular space of
(Wu et al. 2005, 2006, 2007; Wang et al. 2008). the spinneret. The polymer solidifies by cooling
In dry spinning, air or an inert gas is used after being extruded from the spinneret and then
instead of the bore liquid so that solidification is collected by means of take-up wheels. The spin-
achieved through evaporation of the solvent. As ning rate in melt spinning (thousands of meter per
the dope solution exit the spinneret, air or an inert minute) is much higher than that used in the
Hollow Fiber Spinning 3
dry/wet spinning technique (meters per minute) (vinyl chloride) hollow fiber membranes prepared at
(Mulder 1992). different air gap lengths. J Membr Sci 330:30–39
Mulder M (1992) Basic principles of membrane technol-
The spinneret geometry, the dope solution, ogy. Kluwer, Dordrecht
and the spinning conditions (bore fluid type and Wang KY, Chung TS, Gryta M (2008) Hydrophobic
its flow rate, dope solution extrusion rate, take-up PVDF hollow fiber membranes with narrow pore size
speed, air gap distance, external coagulant, spin distribution and ultra-skin for the fresh water produc-
tion through membrane distillation. Chem Eng Sci
draw ratio, spinning temperature, cold stretching, 63:2587–2594
etc.) affect the hollow fiber geometrical parame- Wu B, Tan X, Teo WK, Li K (2005) Removal of benzene/
ters (inner and outer diameters, thickness), its toluene from water by vacuum membrane distillation
internal structure, as well as the structural mor- in a PVDF hollow fiber membrane module. Sep Sci
Technol 40:2679–2695
phology of the inner and outer surfaces. Wu B, Tan X, Li K, Teo WK (2006) Removal of 1,1,1-
trichloroethane from water using a poly(vinylidene
fluoride) hollow fiber membrane module: vacuum
References membrane distillation operation. Sep Purif Technol
52:301–309
Wu B, Li K, Teo WK (2007) Preparation and characteri-
Khayet M, Matsuura T (2011) Membrane distillation: zation of poly(vinylidene fluoride) hollow fiber mem-
principles and applications. Elsevier, Amsterdam branes for vacuum membrane distillation. J Appl
Khayet M, Garcı́a-Payo MC, Qusay FA, Zubaidy MA Polym Sci 106:1482–1495
(2009) Structural and performance studies of poly
H
Hollow Fiber, Fig. 2 Scanning electron microscopy (a) and inner (b) microstructure (Reprinted from
(SEM) images of polyethersulfone/polyimide (PES/PI) (Nijdam et al. 2005). Copyright 2005, with kind permis-
blend hollow fiber membranes with a corrugated outer sion from Elsevier)
The first hollow fiber membranes were pat- spinning or wet spinning techniques requires
ented by Mahon in late the 1960s (Mahon both internal (bore liquid) and external coagu-
1966a, b). Various types of hollow fiber mem- lants and involves more controlling parameters
branes, hydrophobic or hydrophilic, dense or than the flat sheet membrane. Shape and dimen-
porous, single or double layered, have been pro- sion of the spinneret, viscosity of the spinning
posed for different membrane separation pro- dope (whether hollow fibers can be spun from
cesses leading to a fast growth of synthetic the dope), temperature of the spinning dope,
membrane technology. Since then significant properties of the internal and external coagulants,
efforts have been made to develop new hollow flow rate of the bore liquid, dope extrusion rate,
fibers with desirable structures and morphol- length and humidity of the air gap, wind-up
ogies. However, until now, various scientists speed, and fiber take-up speed are some of those
admit that understanding the mechanisms of hol- examples. As a consequence, the major parts of
low fiber formation is rather qualitative than hollow fibers that appeared in the literature with
quantitative. It is not easy to control the charac- different structures and morphologies are based
teristics of hollow fibers because various impor- mostly on trial-and-error experiments.
tant spinning parameters are involved Hollow fibers are mechanically self-
simultaneously. For example, the preparation of supporting, have good flexibility, and are easy
the hollow fiber membrane by the dry/wet to assemble in module and to handle for different
Hollow Fiber 3
Hollow Fiber, Fig. 3 Cross-sectional structure of PVDF 40 wt.% NMP aqueous solution as internal coagulant
hollow fiber membranes prepared with wet spinning tech- (Reprinted from (Bonyadi et al. 2007). Copyright 2007,
nique and dry/wet spinning technique using 20 wt.% with kind permission from Elsevier)
PVDF in the solvent N-methylpyrrolidone (NMP) and
applications. The feed is supplied to either the The use of corrugated membrane surfaces is to
inside or outside of the fiber, and the permeate enhance the heat and mass transfer by increasing
passes through the fiber wall to the other side of the membrane surface area and the turbulence
the fiber. The fiber wall may have an asymmetric near the membrane surface. Corrugations act as
structure being the active skin layer placed to the turbulence promoters but also may lead to an
feed side. A bundle of hollow fibers are often increase of pressure drop in the flow channel. It
mounted in a shell and tube module, which is was observed that the size of the corrugations on
featured by a very large packing density (i.e., the fiber was very sensitive to the air gap length
high surface area per unit module volume), and and even disappeared from the external surface
therefore the size of the hollow fiber module is for high air gap lengths. When used in gas sepa-
smaller than other modules for a given perfor- ration, the selectivity (oxygen/nitrogen) and
mance capacity. The packing capacity of a hol- permeance of polyethersulfone/polyimide
low fiber module may reach 500–9,000 m2/m3 (PES/PI) blend corrugated hollow fiber mem-
resulting in a high productivity per unit volume. brane were found to be similar to those of smooth
Spinning corrugated hollow fibers is similar to cylindrical fibers (i.e., circular-shaped fibers) pre-
spinning smooth cylindrical fibers; the only dif- pared under the same operating conditions. How-
ference is the use of a modified spinneret (Cao ever, the gas permeate flow was increased by
et al. 2004; Çulfaz et al. 2010; Nijdam et al. 2005; 19 %, which is the increase of membrane surface
Wang et al. 2004). For example, to prepare a area due to corrugations (Nijdam et al. 2005). It is
hollow fiber with a corrugated inner microstruc- worth quoting that an increase of membrane sur-
ture instead of a cylindrical needle, the spinneret face area of 89 % can be obtained with a corru-
is fabricated with a structured needle. To spin a gated hollow fiber membrane (Çulfaz et al. 2010).
hollow fiber with a corrugated outer surface, a Furthermore, PES/PVP blend hollow fiber mem-
microstructured orifice is incorporated to the branes were used in UF, and it was found that the
spinneret. Figure 2 shows SEM images of corru- water permeability, molecular weight cutoff, and
gated hollow fiber membranes. pore size distribution of both the corrugated and
4 Hollow Fiber
circular-shaped fibers were similar (Çulfaz hollow fibers during the non-solvent induced phase-
et al. 2010). This indicates a higher permeate separation process. J Membr Sci 299:200–210
Cao C, Chung TS, Chen SB, Dong ZJ (2004) The study of
flow of the corrugated hollow fiber compared to elongation and shear rates in spinning process and its
the circular-shaped fiber and a similar UF sepa- effect on gas separation performance of poly(ether
ration factor. sulfone) (PES) hollow fiber membranes. Chem Eng
Instabilities and irregularities may occur dur- Sci 59:1053–1062
Çulfaz PZ, Rolevink E, van Rijn C, Lammertink RGH,
ing hollow fiber spinning inducing corrugations Wessling M (2010) Microstructured hollow fibers for
at their external or internal contours. These cor- ultrafiltration. J Membr Sci 347:32–41
rugations can be eliminated increasing the air gap Khayet M, Matsuura T (2011) Membrane distillation:
distance (Fig. 3). The number of corrugations in principles and applications. Elsevier, Amsterdam
Mahon HI (1966a) Permeability separatory apparatus and
the internal surface of the hollow fiber mem- membrane element, method of making the same and
branes is reduced approaching a final circular process utilizing the same. US Patent 3,228,876
shape. The hydrodynamic instability, which Mahon HI (1966b) Permeability separatory apparatus and
leads to nonuniform cross-section and wavy process using hollow fibers. US Patent 3,228,877
Mulder M (1992) Basic principles of membrane technol-
geometry, might be due to the pressure induced ogy. Kluwer, Dordrecht
in the nascent fiber (as a result of diffusion/con- Nijdam W, de Jong J, van Rijn CJM, Visser T, Versteeg L,
vection, precipitation, densification, and shrink- Kapantaidakis G, Koops GH, Wessling M (2005) High
age), which will buckle the rigid elastic shell performance micro-engineered hollow fiber mem-
branes by smart spinneret design. J Membr Sci
formed at the interface between the bore fluid 256:209–215
and the spinning dope solution (Bonyadi Wang KY, Matsuura T, Chung TS, Guo WF (2004) The
et al. 2007). effects of flow angle and shear rate within the spinneret
on the separation performance of poly(ethersulfone)
(PES) ultrafiltration hollow fiber membranes. J Membr
Sci 240:67–79
References Wu B, Li K, Teo WK (2007) Preparation and characteri-
zation of poly(vinylidene fluoride) hollow fiber mem-
Bonyadi S, Chung TS, Krantz WB (2007) Investigation of branes for vacuum membrane distillation. J Appl
corrugation phenomenon in the inner contour of Polym Sci 106:1482–1495
M
1.58 mm
0.83 mm
N2
polymer
solution
bore liquid
0.6 mm
spinneret
air gap
take-up winder
Melt Spinning, Fig. 1 Schematic diagram of a hollow fiber preparation system via thermally induced phase separation
(TIPS) technique (Reprinted from (Matsuyama et al. 2003). Copyright 2003, with kind permission from Elsevier)
temperature must be less than the boiling iv. The diluent(s) that is trapped in the polymer
point of the diluent and is typically matrix during phase separation and solidifi-
25–100 C greater than the melting tempera- cation is removed by solvent extraction
ture or glass transition temperature of the procedure.
polymer. The polymer must be stable at this v. The extractant is removed by evaporation to
initial temperature. To avoid confusion, the yield microporous structures if required.
term diluent will be used instead of solvent, vi. Posttreatment processing might be applied to
hereafter. The diluent acts as a solvent only improve the desired separation characteris-
when it can dissolve all polymers. When the tics of the TIPS membrane. Stretching might
solvent power decreases sufficiently so that be included in this step.
liquid-liquid demixing takes place, the term
solvent is not appropriate anymore. TIPS can be applied to a wide range of poly-
ii. The hot solution is extruded or spun in the mers, including those that cannot be otherwise
desired shape including a hollow fiber. formed into membranes because of poor solubil-
iii. The solution is cooled at controlled rate or ity in solvent.
quenched to induce phase separation and The type of phase separation (liquid-liquid
solidification. phase separation, solid-liquid phase separation,
combined liquid-liquid and solid-liquid phase
Melt Spinning 3
separation) that is likely to occur for a given Laxminarayan A, McGuire KS, Kim SS, Lloyd DR
system (composition and temperature) is indi- (1994) Effect of initial composition, phase separation
temperature and polymer crystallization on the forma-
cated by the phase diagram (Khayet and tion of microcellular structures via thermally induced
Matsuura 2011; Laxminarayan et al. 1994). This phase separation. Polymer 35:3060–3068
is a useful tool explaining the morphology and Lloyd DR (1990) Microporous membrane formation via
bulk structure of TIPS membranes. Polymers thermally-induced phase separation. I Solid-liquid
phase separation. J Membr Sci 52:239–261
such as polyethylene (PE), polypropylene (PP), Matsuyama H, Okafuji H, Maki T, Teramoto M, Kubota
and poly(2,6-dimethyl-1,4-phenylene ether) N (2003) Preparation of polyethylene hollow fiber
(PPE) were used in melt spinning (Khayet and membrane via thermally induced phase separation.
Matsuura 2011). J Membr Sci 223:119–126
Mulder M (1992) Basic principles of membrane technol-
ogy. Kluwer, Dordrecht
References
Spinneret Spinneret
after exiting from the spinneret will play impor- elongation stress along the spin line is small as
tant roles on final hollow fiber structure. Further- spinning dope solution is a viscoelastic fluid or
more, the induced elongation stresses outside the might be enhanced if the spin line stress is high.
spinneret from gravity through the air gap com- In other words, the elongation stress caused by
plicate the kinetics and dynamics of the phase gravity along the spinning line becomes more
inversion process. In addition, non-Newtonian pronounced with increasing the distance between
polymer solutions may exhibit die swell and the spinneret or jets and the take-up wheel.
relaxation after exiting from spinneret.
Molecular chains tend to align themselves
much better, and this enhanced orientation causes References
the polymer molecules to pack closer to each
other leading to a tighter skin fiber structure. Khayet M, Matsuura T (2011) Membrane distillation:
principles and applications. Elsevier, Amsterdam
The molecular orientation induced by shear stress
Mulder M (1992) Basic principles of membrane technol-
within the spinneret might relax in the air gap ogy. Kluwer, Dordrecht
region, before reaching the take-up wheel, if the
E
External Coagulant in Fiber the hollow fiber strongly depend on the chemistry
Preparation and the composition of the coagulant. The molec-
ular sizes and solubility parameters of the used
Khayet Mohamed solvent and the internal and the external coagu-
Department of Applied Physics I, Universidad lant play important roles on hollow fiber mor-
Complutense de Madrid, Madrid, Spain phology. Solvent of a large size may have
difficulties to leach out during the coagulation
step. The difference in solubility parameters
External coagulant is a non-solvent liquid or a between the spinning dope solution and the bore
mixture of solvent/non-solvent in a collecting liquid (internal coagulant) or the external coagu-
bath (coagulation bath) used for fabrication of lant affects the coagulation rate and subsequently
fibers by the dry-/wet-spinning technique or the the porosity of the spun hollow fiber membrane.
wet-spinning technique. Coagulation of the The interactions between solvent and external
external surface of the nascent fiber can start coagulant and between solvent and polymer play
immediately after its extrusion from the spinneret important roles affecting the rate of polymer pre-
(wet spinning) or after the as-spun fiber crosses cipitation. The temperature of the external coag-
an air gap (i.e., distance between the spinneret ulant affects also the polymer precipitation rate.
and the coagulation bath) through which the The maximum amount of solvent that can be
external surface experiences coalescence and ori- added to the non-solvent in the coagulation bath
entation of polymer aggregates (wet/dry spin- can be roughly determined by the position of the
ning). In general, the nascent fiber is partially binodal (liquid-liquid boundary separating the
coagulated by the internal coagulant (bore liquid) miscible region from the immiscible one) in the
and/or through the air gap by solvent evaporation, ternary phase diagram presenting the composi-
and finally the coagulation is completed in the tion of the polymer, solvent, and non-solvent.
coagulation bath by an external coagulant. When the binodal shifts toward the polymer/sol-
The type of the external coagulant affects con- vent axis, more solvent can be added in the exter-
siderably the structural morphology of the nal coagulant. It is also possible to change from
resulted fiber. Usually, water is the preferred porous to nonporous external fiber surface by
external coagulant because of its low cost and adding solvent to the coagulation bath (Mulder
environmental friendliness. The proper choice 1992). For example, when a strong coagulant
of the coagulant is very important because such as water for poly(vinylidene fluoride),
the rate of demixing (i.e., phase separation) and PVDF, polymer is used for hollow fiber fabrica-
the resultant inner and outer surface structures of tion, a dense and smooth surface with no obvious
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1179-2
2 External Coagulant in Fiber Preparation
External Coagulant in Fiber Preparation, internal coagulant water and external coagulant 50 %
Fig. 1 Cross-sectional scanning electron microscopy ethanol in water (Reprinted from (Khayet et al. 2002).
(SEM) structure of PVDF hollow fiber membranes pre- Copyright 2002, with kind permission from Elsevier)
pared with different coagulants: (a) water coagulant; (b)
pores is formed. However, when a weaker coag- the mutual diffusivity of solvent/non-solvent
ulant is employed such as methanol, which may exchange and solubility parameters of the mate-
be mixed with water, the roughness of the formed rials involved in hollow fiber spinning. The addi-
hollow fiber surface may increase considerably tion of ethanol in water reduces the diffusion of
due partially to the formation of pores. These are non-solvent into the nascent hollow fiber mem-
the reasons for using the coagulants: 80 wt.% brane and consequently decreases the rate of pre-
N-methylpyrrolidone (NMP) aqueous solution cipitation. Khayet et al. (2002) observed an
by Wang et al. (2008) for preparation of PVDF increase of the external surface roughness of
hollow fiber membranes and 80 wt.% methanol PVDF hollow fibers when ethanol was added to
aqueous solution by Bonyadi and Chung (2007) the external coagulant and attributed the result to
for fabrication of dual hydrophilic/hydrophobic the increase of the pore size at the outer surface as
hollow fiber membranes for direct contact mem- ethanol was added in the coagulation bath.
brane distillation (DCMD) process. Figure 1
shows the effects of the external coagulant on
the cross-sectional structure of porous hydropho- References
bic hollow fiber membranes (Khayet et al. 2002).
Water and 50 % (by volume) ethanol in water Bonyadi S, Chung TS (2007) Flux enhancement in mem-
brane distillation by fabrication of dual layer
were used as internal and external coagulants. In
hydrophilic-hydrophobic hollow fiber membranes.
Fig. 1a prepared with water as internal and exter- J Membr Sci 306:134–146
nal coagulants, long finger-like voids are formed Khayet M, Feng CY, Khulbe KC, Matsuura T (2002)
near the inner surface, while smaller cavities are Preparation and characterization of polyvinylidene
fluoride hollow fiber membranes for ultrafiltration.
formed near the outer surface. Between the inner
Polymer 43:3879–3890
and outer layers, sponge-like structure appears. In Mulder M (1992) Basic principles of membrane technol-
Fig. 1b the outer layer is eliminated when ethanol ogy. Kluwer Academic Publishers, Dordrecht
is added to the external coagulant. The addition of Wang KY, Chung TS, Gryta M (2008) Hydrophobic
PVDF hollow fiber membranes with narrow pore size
ethanol delays the external coagulation process
distribution and ultra-skin for the fresh water produc-
and the finger-like structure changes to a sponge- tion through membrane distillation. Chem Eng Sci
like structure. The slow coagulation of the hollow 63:2587–2594
fiber membranes can be explained on the basis of
B
Bore Liquid: Solvent and Non-solvent, Fig. 2 Cross- coagulant, (b) internal coagulant 50 % ethanol in water
sectional scanning electron microscopy (SEM) structure and external coagulant water, (c) 50 % ethanol in water
of PVDF hollow fiber membranes prepared by wet/dry coagulant (Reprinted from Khayet et al. (2002), Copyright
spinning technique with different coagulants: (a) water 2002, with kind permission from Elsevier)
R1 R2
R3
liquid vapour
phase phase
R1 R2 R1 R2
R3 R3
Membrane (Definition, Function, Structure), separates a liquid and a vapor phase and allows passage of
Fig. 1 Schematic drawing illustrating (a) a membrane vapor molecules but is not selective for the transport of
which is selective for the transport of different compo- different components
nents such as two enantiomers and (b) a membrane which
from more than 1,000,000 Ω cm2 to less than 1 Ω membrane which is highly selective and capable
cm2. of separating, e.g., two enantiomers, and (b) a
The term “membrane,” therefore, includes a membrane that acts as a barrier between two
great variety of materials and structures, and a phases and avoids the mixing of the phases but
membrane can often be better described by its has no selective properties related to the transport
function rather than by its structure. Some mate- of different components from one phase to the
rials, such as protective coatings or packaging other.
materials, show typical membrane properties A porous structure represents a very simple
and are in fact membranes. Most materials func- form of a membrane, which closely resembles
tioning as membranes have the characteristic the conventional filter as far as the mode of sep-
property in common of restricting the passage of aration is concerned. These membranes consist of
different components in a very specific manner. a solid matrix with defined holes or pores which
In some cases, they may restrict the passage of the have diameters ranging from less than 1 nm to
same component, depending on the state: a more than 10 mm. The macromolecular size of the
hydrophobic polymeric membrane may allow species to be separated plays an important role in
the passage of water as vapor phase but not as determining the pore size of the membrane to be
liquid phase, as, for example, in membrane dis- utilized and the related membrane process.
tillation. In other cases, e.g., membrane Porous membranes with average pore diameters
contactors, the porous structure of the membrane larger than 50 nm are classified as macroporous,
material functions as a barrier that keeps in con- and those with average pore diameters in the
tact two adjacent phases between which a mass intermediate range between 2 and 50 nm are
transfer occurs and separates them at the same classified as mesoporous. Membranes with
time. In this case the membrane has no direct average pore diameters between 0.1 and 2 nm
effect on the transport of various components are classified as microporous. Dense membranes
and is nonselective toward the passing species. have no individual permanent pores, but the
The concept of a selective and nonselective mem- separation occurs through fluctuating free
brane is illustrated in Fig. 1 which shows (a) a volumes, by solution-diffusion mechanism
Membrane (Definition, Function, Structure) 3
Membrane (Definition, Function, Structure), Fig. 2 Schematic classification of membranes, related processes, and
separated components
Membrane (Definition, Function, Structure), Fig. 3 Porous symmetric (a) and asymmetric membrane (b)
(Strathmann et al. 2010). The schematic repre- over the membrane cross section, or they can be
sentation of such classification is illustrated in asymmetric (Fig. 3b), i.e., the pore diameters
Fig. 2. increase from one side of the membrane to the
In pressure-driven membrane processes, the other typically by a factor of 10–1,000.
separation of the various components is achieved The mechanism by which certain components
by a sieving mechanism with the pore diameters are transported through a membrane can also be
and the particle sizes being the determining very different. In some membranes, for example,
parameters. In thermally driven membrane pro- the transport is based on viscous flow of a mixture
cesses, the separation is based on the principle of through individual pores of the membrane caused
phase equilibrium, and the non-wettability of by a hydrostatic pressure difference between the
membrane pores is the determining parameter. two phases separated by the membrane. This type
Membrane structure may be symmetric of transport is referred to as viscous flow. The
(Fig. 3a), i.e., the pore diameters do not vary components that permeate through the membrane
4 Membrane (Definition, Function, Structure)
a b
Membrane (Definition, Function, Structure), Fig. 4 Schematic diagram illustrating (a) the sieving mechanism of a
porous membrane and (b) the solution-diffusion mechanism in a nonporous membrane
Material Configuration
polymer flat-sheet
ceramic Membrane spiral wound
glass classification tubular
metal capillary
liquid hollow fiber
composite structures:
homogeneous skin layer
Structure
symmetric symmetric asymmetric
asymmetric
integral asymmetric
homogeneous films cylindrical pores sponge-type structures porous skin layer homogeneous skin layer
are transported by convective flow through diffusivity of components into the membrane
macropores under a pressure gradient as driving material as indicated in (Fig. 4b).
force and the separation occurs because of size Fick’s law describes this type of transport. The
exclusion as indicated in (Fig. 4a). Darcy’s Law diffusion of molecules through homogeneous
describes this type of transport. It is the dominant dense membranes occurs through the free volume
form of mass transport in micro- and ultrafiltra- elements, or empty spaces between polymer
tion but also occurs in other membrane processes. chains caused by thermal motion of the polymer
If the transport through a membrane is based molecules, which fluctuate in position and vol-
on the solution and diffusion of individual mole- ume on the same time scale as the molecule
cules in the nonporous membrane matrix due to a permeates. The transition between fluctuating
concentration or chemical potential gradient, the free volumes and individual permanent pores is
transport is referred to as diffusion. The separa- controversial. In general it is considered in the
tion occurs because of different solubility and range of 5–10 Å in diameter.
Membrane (Definition, Function, Structure) 5
progenitor cells, and stem cells. These devices improve the mass transfer (Gerlach et al. 1994).
have been used in replacement therapy for acute Spirally wound bioreactor has been proposed for
and chronic organ failure and in the management the culture of hepatocytes and other mammalian
of immunological disease as well as in tissue cells. This bioreactor consists of spiral-wound
engineering for the realization of tissue- membranes, and some devices include also a
engineered constructs and defined models layer of polypropylene hollow fiber membranes
supporting investigations on cell function, tissue for cell oxygenation (Flendrig et al. 1997). Bio-
development, and drug testing. Different config- reactors using multibore capillaries have been
urations of membrane bioreactor have been developed in the last years for the culture of
explored for the culture and growth of mamma- human hepatocytes (De Bartolo et al. 2007a).
lian cells. Primary cells, immortalized cells, and This device is composed of multibore membranes
stem cells can be cultured (a) on flat-sheet mem- of modified poly(ethersulfone) constituted of
branes, (b) in the lumen or shell of hollow fiber seven compartments represented by seven capil-
membranes in suspension or attached to the mem- laries arranged in one single fiber. The seven
brane surface, (c) in a network of hollow fiber compartments communicate through a porous
membranes, (d) in a spirally wound membrane foamy support structure that is located in between
device, (e) in multibore fibers, and (f) in the capillaries. In this bioreactor human hepato-
gas-permeable membrane bioreactor. Flat mem- cytes have been cultured inside the lumen of the
brane bioreactor is a simple device that has been multibore fibers and lumen in the shell compart-
developed for the small-scale culture of cells ment. In the last years membrane bioreactors
(e.g., neurons, hepatocytes) as tool for drug have been developed for the expansion and
screening and toxicological studies (De Bartolo transdifferentiation of stem cells to be used in
et al. 2006a). In this device a microporous flat- cell therapy and tissue engineering applications
sheet membrane separates the medium compart- (Salerno et al. 2013).
ment from the cells that are adhered on the mem-
brane. Advanced bioreactors use additionally
gas-permeable membranes (e.g., fluorocarbon
References
membranes), which are permeable to oxygen,
carbon dioxide, and water vapor, in order to De Bartolo L, Salerno S, Giorno L, Morelli S, Barbieri G,
improve the oxygenation of cells. In this device Curcio E, Rende M, Drioli E (2006a) Membrane bio-
cells receive oxygen directly from the bottom reactor using pig hepatocytes for in vitro evaluation of
membrane sheet where they are seeded and indi- anti-inflammatory drugs. Catal Today 118:172–180
De Bartolo L, Salerno S, Morelli S, Giorno L, Rende M,
rectly from the microporous membrane in contact Memoli B, Procino A, Andreucci VE, Bader A, Drioli
with the medium overlaying the cells (De Bartolo E (2006b) Long-term maintenance of human hepato-
et al. 2006b). Hollow fiber membrane bioreactors cyte in oxygen permeable membrane bioreactor. Bio-
are the most used bioreactors for high cell density materials 27(27):4794–4803
De Bartolo L, Morelli S, Rende M, Campana C, Salerno S,
culture. In these devices cells usually are cultured Quintiero N, Drioli E (2007a) Human hepatocyte mor-
in the shell of a bundle of hollow fiber mem- phology and functions in a multibore fiber bioreactor.
branes parallel-assembled, and the medium Macromol Biosci 7:671–680
flows in the lumen (De Bartolo et al. 2007b). De Bartolo L, Piscioneri A, Cotroneo G, Salerno S,
Tasselli F, Campana C, Morelli S, Rende M, Caroleo
Alternatively cells can be cultured inside the MC, Bossio M, Drioli E (2007b) Human lymphocyte
lumen of hollow fiber and the medium flows in PEEK-WC hollow fiber membrane bioreactor.
the shell (Demetriou et al. 1986). In both cases J Biotechnol 132:65–75
the medium and cell compartments communicate Demetriou AA, Whiting JF, Levenson AM et al (1986)
New method of hepatocyte transplantation and extra-
through the pores of the fiber wall. Advanced corporeal liver support. Ann Surg 204(3):259–270
designs of bioreactors using a network of hollow Flendrig LM, La Soe JW, Joerning GGA et al (1997) In
fiber membranes with different properties have vitro evaluation of a novel bioreactor based on an
been developed for the culture of cells in order to integral oxygenator and a spirally wound nonwoven
Membrane Bioreactors for Cell Growth 3
polyester matrix for hepatocyte culture as small aggre- biotechnology, 2nd edn, vol 2. Elsevier, Amsterdam/
gates. J Hepatol 26:1379–1392 Oxford/Walthaman pp 263–288.
Gerlach JC, Schnoy N, Smith MD, Neuhaus P (1994) Salerno S, Piscioneri A, Morelli S, Al-Fageeh MB,
Hepatocyte culture between woven capillary net- Drioli E, De Bartolo L (2013) Membrane bioreactor
works: a microscopy study. Artif Organs 18:226–230 for expansion and differentiation of embryonic liver
Giorno L, De Bartolo L, Drioli E (2011) Membrane bio- cells. Ind Eng Chem Res 52(31):10387–10395
reactors. In: Moo-Young M (ed) Comprehensive
H
Hollow Fiber Membrane Bioreactor As bioreactors, they are extensively used for
for Cell Growth production of biochemicals and for the develop-
ment of bioartificial organs. Recently they found
Loredana De Bartolo applications in tissue engineering applications for
Institute on Membrane Technology, ITM-CNR, the development of tissue constructs, cell ther-
National Research Council of Italy, Rende (CS), apy, and the expansion and transdifferentiation of
Italy stem cells. Hollow fiber bioreactor offers several
advantages for the culture and growth of adherent
and suspension cells including: (i) an in vivo-like
Hollow fiber membrane bioreactor consists of microenvironment regarding nutrient supply and
hollow fiber membranes parallel-assembled in metabolic waste removal as each fiber replicates
an external shell, which is usually in the shape a blood capillary, (ii) high surface area to volume
of a cylinder. The fibers are potted in the shell, ratio, (iii) cells can be grown to high density,
thus creating a medium and a cell compartment (iv) cells are protected from shear stress, and
which are separated by the membranes. Hollow (v) support of three-dimensional growth of cells
fiber membranes of suitable MWCO separate for the development of tissue-engineered con-
cells from the medium compartment allowing structs. Different types of polymers
the communication between the compartments (polyethersulfone, polysulfone, polyacryloni-
through the pores of fiber wall. Depending on trile, modified polyetheretherketone, polyamide,
the pore sizes, the passage of nutrients, metabo- cellulose acetate, etc.), generally hydrophilic
lites, and catabolites occurs and cells are retained. polymers or with moderate wettability, are used
The principle of a hollow fiber bioreactor based for the development of hollow fiber bioreactors in
on hemodialyzer modules was first described by order to favor the adhesion of cells or the
Knazek (Knazek et al. 1972). Usually cells are exchange of medium. Hydrophobic hollow fibers
cultured in suspension or attached to the outer (e.g., polypropylene) are included in some
surface of the membranes in the extracapillary devices for a separate oxygenation of cells
space. Culture medium containing nutrients (Flendrig et al. 1997). A major drawback of the
flows in the lumen of the fibers and diffuses out hollow fiber bioreactors is represented by the
through the pores of the fiber wall to the cells. mass transfer resistance due to the membrane
The metabolic species together with waste mole- because while it separates cells from the medium
cules produced by cells permeates back into the compartment, it does reduce diffusion of nutri-
fibers and is removed from cell compartment ents and oxygen to the cells. In addition, fouling
(Fig. 1). due to the adsorption of plasma proteins or the
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1191-1
2 Hollow Fiber Membrane Bioreactor for Cell Growth
a b
Culture
cells medium flow Hollow fiber
membranes cells
Hollow Fiber Membrane Bioreactor for Cell Growth, cultured in the extracapillary space, and the medium flows
Fig. 1 Schematic diagram of hollow fiber membrane in the lumen of fibers; (b) cells are cultured in the lumen of
bioreactor used for cell culture and growth: (a) cells are fiber, and the medium flows in the extracapillary space
development of biofilms further increases the hepatocytes, pancreatic islets, neurons, osteo-
resistance to mass transport. In the membrane blasts, fibroblasts), cell lines, progenitor cells,
bioreactors, mass transfer is determined by the and stem cells (De Bartolo and Bader 2013).
MWCO or pore diameter of membrane and Usually cells are cultured in adhesion or suspen-
occurs by diffusion and/or convection in response sion outside the fibers, and the medium flows in
to existing transmembrane concentration or pres- the lumen of fibers (De Bartolo et al. 2007a). In
sure gradients. Most of the bioreactors use mem- other bioreactors cells are cultured inside the
branes with MWCO ranging from 70 to 100 kDa lumen of fibers, and the medium flows in the
that allow the transport of small molecules that shell of fiber (Fig. 1) (Nyberg et al. 1994). More
are fed or produced by cells but exclude proteins complex devices have been explored for the cul-
with high MW such as immunoglobulins and ture of hepatocytes, stem cells, and progenitor
cells. These membranes provide cells that include the use of different fibers.
immunoprotection, which is important when the A bioreactor with four interwoven independent
devices are used in the organ replacement therapy capillary membrane systems that serve different
in order to avoid the passage of immunocompe- functions has been developed by Gerlach
tent species present in the patient’s blood. Other et al. (1994). The cells are cultured on the outer
bioreactors use microporous membranes with a surface and among the capillaries. Each fiber type
large pore diameter (0.2 mm) that permit the free exhibits a different function: silastic membranes
passage of proteins, toxins, and clotting factors, for oxygen supply and removal of carbon diox-
but they exclude the passage of cells. The advan- ide, polyamide fiber for the plasma inflow,
tage of using a membrane with large pore diam- polyethersulfone fiber for the plasma outflow,
eter is that it increases the fluid convection and hydrophilic polypropylene membranes for
improving the mass transfer conditions. Several the sinusoidal endothelial coculture. A crossed
hollow fiber membrane bioreactors have been hollow fiber membrane bioreactor was developed
developed for the culture of cells that grow in as an in vitro liver tissue model to study disease,
adhesion and/or in suspension. Different config- drugs, and therapeutic molecules alternative to
urations have been investigated for the culture animal experimentation (De Bartolo
and growth of primary cells (e.g., lymphocytes, et al. 2009). The bioreactor consists of two
Hollow Fiber Membrane Bioreactor for Cell Growth 3
types of fibers with different MWCO and physi- monitor key culture parameters (pH, temperature,
cochemical properties cross-assembled in alter- oxygen, etc.), and to guide the transdiffer-
nating manner: modified polyetheretherketone entiation of cells by engineering membranes
and polyethersulfone used for the medium inflow with targeted properties.
and outflow, respectively. The combination of
these two fiber sets produces an extracapillary
network for the adhesion of cells and a high References
mass exchange through the crossflow of culture
medium. This bioreactor has been developed for De Bartolo L, Bader A (2013) Biomaterials for stem cell
therapy: state of art and vision for the future. CRC
the culture of human hepatocytes and expansion
Press, Boca Raton
and differentiation of liver progenitor cells. De Bartolo L, Piscioneri A, Cotroneo G, Salerno S,
Multibore fiber membrane bioreactor consisting Tasselli F, Campana C, Morelli S, Rende M, Caroleo
of modified polyethersulfone fiber has been MC, Bossio M, Drioli E (2007a) Human lymphocyte
PEEK-WC hollow fiber membrane bioreactor.
developed for the long-term maintenance of
J Biotechnol 132:65–75
human hepatocytes. Each fiber is composed of De Bartolo L, Morelli S, Rende M, Campana C, Salerno S,
seven compartments that communicate through Quintiero N, Drioli E (2007b) Human hepatocyte mor-
a porous foamy support structure that is located in phology and functions in a multibore fiber bioreactor.
Macromol Biosci 7:671–680
between the capillaries. Cells have been cultured
De Bartolo L, Salerno S, Curcio E, Piscioneri A, Rende M,
inside the lumen of the multibore fibers and Morelli S, Tasselli F, Bader A, Drioli E (2009) Human
lumen in the shell compartment (De Bartolo hepatocyte functions in a crossed hollow fiber mem-
et al. 2007b). brane bioreactor. Biomaterials 30:2531–2543
Flendrig LM, La Soe JW, Joerning GGA et al (1997) In
Hollow fiber membrane bioreactors have a
vitro evaluation of a novel bioreactor based on an
great potential for the expansion and differentia- integral oxygenator and a spirally wound nonwoven
tion of embryonic and adult stem cells, which polyestermatrix for hepatocyte culture as small aggre-
have ability to either self-renew or differentiate gates. J Hepatol 26:1379–1392
Gerlach JC, Schnoy N, Smith MD, Neuhaus P (1994)
into multiple cell lineages. These properties make
Hepatocyte culture between woven capillary net-
stem cells attractive as a cell source for cell works: a microscopy study. Artif Organs 18:226–230
therapies, tissue engineering, and model systems Knazek RA, Gullino PM, Kohler PO, Dedrick RL
for drug screening. Depending on the application, (1972) Cell culture on artificial capillaries: an
approach to tissue growth in vitro. Science 178:65–66
hollow fiber membrane bioreactors can be used
Nyberg SL, Remmel RP, Mann HJ et al (1994) Primary
for the production of expanded stem cells with outperform hep G2 cells as source of biotransforma-
uniform properties and/or for a controlled and tion functions in a bioartificial liver. Ann Surg
reproducible differentiation into selected mature 220:59–67
Salerno S, Piscioneri A, Morelli S, Al-Fageeh MB,
cell types (Salerno et al. 2013). They are partic-
Drioli E, De Bartolo L (2013) Membrane bioreactor
ularly advantageous with respect to the other for expansion and differentiation of embryonic liver
culture systems because of their capacity to cells. Ind Eng Chem Res 52(31):10387–10395
ensure a more homogeneous environment, to
A
(PES), polyacrylonitrile (PAN), polyamide (PA), significant advantage of being able to be broken
polyimide (PI), polyethylene (PE), polypropyl- down and removed after they have served their
ene (PP), polytetrafluoroethylene (PTFE), function (De Bartolo and Bader 2013).
polyvinylidene fluoride (PVDF), polyarylether- Responsive membranes are used in the area of
sulfones (PAES), polyvinyl chloride (PVC), eth- cell sheet engineering for the in vitro tissue
ylene vinyl alcohol (EVAL), polyethyleneimine reconstruction. These membranes allow the
(PEI), and polymethyl methacrylate (PMMA) adhesion and proliferation of cells at a tempera-
(Baker 2004). These membranes are used extra- ture above the lower critical solution temperature
corporeally connected to the patient’s body of the grafted polymer (a state where in the sur-
through blood circulation as, for example, in face is hydrophobic) and the detachment of cells
hemodialysis, hemodiafiltration, blood oxygena- when the temperature is lowered below the lower
tion, and bioartificial organs. critical solution, because of spontaneous hydra-
In tissue engineering or in implants are used tion of the grafted polymer chains.
mainly biodegradable membranes that undergo
hydrolytic or enzymatic degradation. These
membranes are mainly made of polyglycolide or References
poly(glycolic acid) (PGA), polylactide (PLA),
poly(lactic-co-glycolic acid) (PLGA), Baker RW (2004) Membrane technology and applica-
tions. Wiley, Chichester
polycaprolactone (PCL), polycarbonate (PC),
De Bartolo L, Bader A (2013) Biomaterials for stem cell
polyurethanes (PU), polyphosphazenes therapy. CRC Press, Boca Raton
(PPHOS), polyamide (PA), chitosan (CHT), De Bartolo L, Drioli E (1998) Membranes in artificial
hyaluronic acid (HA), collagen, and poly organs. In: Haris PI, Chapman D (eds) Biomedical
and health research, vol 16, New biomedical
(p-dioxanone) (PDO). Biodegradable membrane
materials – basic and applied studies. Ios Press,
biomaterials can be implanted in situ into the Amsterdam
body. An example is the commercial collagen Ratner BD, Hoffman AS, Schoen FJ, Lemons JE
resorbable membrane from highly purified type (2012) Biomaterials science: an introduction to mate-
rials in medicine, 3rd edn. Elsevier, Amsterdam
I collagen that is used for repairing tears and
Williams DF (2009) On the nature of biomaterials. Bio-
wound healing. Specifically, membrane biomate- materials 30:5897–5909
rials that are biodegradable provide the
B
Biomaterial and they have binding sites for cells and adhesion
molecules so that they usually avoid immunolog-
Loredana De Bartolo ical reactions and toxicity. Their principal disad-
Institute on Membrane Technology, CNR-ITM, vantage lies in the development of reproducible
National Research Council of Italy, Rende (CS), production methods, because their structural
Italy complexity often makes modification and purifi-
cation difficult. Additionally, significant batch-
to-batch variations occur because of their “bio
A biomaterial is any material in contact with a preparation” in living organism (plants, crusta-
biological system. The first nonbiological mate- ceans) while their mechanical properties are also
rial entered in contact with the human body seem limited. Chemical modification and cross-linking
to date back to the prehistory 9000 years old with are common methods for altering mechanical
the “Kennewick Man,” who had a spearpoint properties such as elasticity and tensile strength
embedded in his hip. This spearpoint was the of natural materials which are often not appropri-
first foreign material implant, which was “toler- ate for dynamic physiologic environments. The
ated” by the body (Ratner et al. 2012). Although most frequently used natural biomaterials are the
the use of biomaterials dates back to the ancient collagen derived from connective tissues of ani-
time, the study of biomaterials is about mals, fibrinogen obtained from plasma, and other
60 years old. proteins of ECM. Among natural biomaterials,
Biomaterials can be classified on the basis of polysaccharides are also frequently used. These
its (i) source in natural or synthetic materials if natural polymers include agarose, hyaluronan,
they are from nature or synthesized in laboratory, chitosan, and alginate. They are derived from
respectively; (ii) chemical nature in organic, inor- plant (seaweed) or animal origin and are used as
ganic, and composites; and (iii) degradation hydrogels to support wound healing and also cell
properties in biodegradable and nonbiode- growth and differentiation (Mano et al. 2007).
gradable. They can be used in biomedical devices Synthetic biomaterials different from natural
for the replacement of an organ function or materials can be synthesized to give various prop-
implanted into the body for the replacement of erties and have high reproducibility, availability,
tissue, organ, or body parts. Biomaterials are also lot-to-lot uniformity, and constant quality. They
used every day in dental applications, surgery, have a well-known structure and properties so
and drug delivery (Williams 2009). that mechanical properties, degradation rate,
Natural-based polymers offer the advantage of shape, and composition can be adjusted to the
being similar to extracellular matrix components, specific application. However, the
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1198-1
2 Biomaterial
biocompatibility and immune reactions are the are shaped with heat-forming porous, brittle
big concern because they often lack sites for cell materials. Hydroxyapatite and tricalcium phos-
adhesion therefore their interactions with cells phate owing to their structural similarity to the
could be questionable. Synthetic biomaterials mineral phase of bone are used alone or in com-
include biodegradable polymers as poly(lactic- bination with organic polymers like PLA, PLGA,
co-glycolic acid) (PLGA), poly-lactic acid collagen, or chitosan in the bone replacement or
(PLA), poly-caprolactone (PCL), poly(ethylene regeneration (De Bartolo and Bader 2013;
glycol) (PEG), etc. and synthetic polymers (e.g., Morelli et al. 2015). Metals like alumina and
polyurethane, polyetheretherketone, polyethyl- titanium alloys that are bioinert materials are
ene, polyvinylidene fluoride, polyvinyl alcohol, used as implant materials where implants are
polymethyl methacrylate, polydioxanone, etc.). subjected to extreme mechanical load, like artic-
For example, PLGA is one of the most frequently ular prostheses, dental implants, or heart valves.
used biomaterials applied in neural, bone, and
cartilage tissue engineering for its degradation
rate that can be modulated. PLA is fast References
reabsorbed and widely used in tissue engineering
applications alone or blended with other poly- De Bartolo L, Bader A (2013) Biomaterials for stem cell
therapy. CRC Press, Boca Raton/New York/Oxon
mers. PCL is a very good elastic biodegradable
Mano JF, Silva GA, Azevedo HS, Malafaya PB, Sousa
polymer that finds several applications in tissue RA, Silva SS, Boesel LF, Oliveira JM, Santos TC,
engineering. PEG that is used in pharmaceutical Marques AP, Neves NM, Reis RL (2007) Natural ori-
technology to modulate the degradation and gin biodegradable systems in tissue engineering and
regenerative medicine: present status and some mov-
absorption of bioactive proteins is also frequently
ing trends. J R Soc Interface 4:999–1030
used in bone, cartilage, nerve, liver, and vascular Morelli S, Salerno S, Holopainen J, Ritala M, De Bartolo
tissue engineering. Peptide-based biomaterials L (2015) Osteogenic and osteoclastogenic differentia-
(e.g., the tripeptide Arg-Gly-Asp, RGD) tion in polylactic acid-nanohydroxyapatite fiber scaf-
folds. J Biotechnol 204: 53–62
consisting of short amino acid sequences exhibit
Ratner BD, Hoffman AS, Schoen FJ, Lemons JE
cell-binding sequences found in the extracellular (2012) Biomaterials science: an introduction to mate-
matrix natural proteins. Ceramic-based biomate- rials in medicine, 3rd edn. Elsevier, Amsterdam
rials that are totally or partly inorganic are Williams DF (2009) On the nature of biomaterials. Bio-
materials 30:5897–5909
applied in bone tissue engineering. Mostly they
C
1640, Iscove’s DMEM, Leibovitz’s L-15), and culture of anchorage-independent cells, as the
serum-free media (HAM F10, HAM F12), this blood or lymphatic cells that survive floating in
specific isotonic solution is constituted by ele- suspension and assuming a spherical shape
mentary substances and nutrients, as glucose, defined lymphoblast-like (Alberts et al. 2002;
salts, amino acids, growth factors, carbohydrates, Karp 2010).
vitamins, lipids, and proteins, and a supplement Isolation of cells. In order to set up a culture,
of antibiotics is also requested for the inhibition the early stage is to acquire an already established
of the bacterial growth (penicillin 10,000 ug/ml; cell line or strain or to isolate the desired cells
streptomycin 10,000 U/ml). A vitally important from a tissue fragment. When cells are immedi-
supplement of the medium is also the animal ately placed in a suitable culture environment
serum (FBS, NCS, HF). The serum, used in con- after mechanical removal from a tissue, the
centration of 5–20 %, is the main source of so-called primary cultures are defined. To
growth and adhesion factors (PDGF, EGF, IGF), degrade the extracellular matrix responsible of
hormones, lipids, and energetic sources. More- the cell layer unity and to obtain a cell suspen-
over, it regulates cell membrane permeability and sion, the tissue is enzymatically treated
protects the cells from mechanical and chemical (collagenase, trypsin, protease), and the highly
stresses, and its buffer power balances the pH heterogeneous cell population is cultured in spe-
value at 7–7.7. All the cell types need proper cific media able to separate single cell types
culture medium and supplements that must be interacting with the cytoplasmatic molecules
refreshed regularly in aseptic condition to guar- expressed onto the plasmatic membranes
antee their survival (Alberts et al. 2002; Karp (antigens). Despite having a finite life span due
2010). to the phenomenon of senescence, these cells
Culture conditions. In artificial systems, the proliferate until they occupy all the substrate
cell is traditionally cultured in plastic or glass available, reaching the confluence. At this stage,
vessels purposely made with different shapes in order to avoid the degeneration and their death,
and properties (flasks, Petri dishes, bottles). the cells are enzymatically removed (e.g., tryp-
They are put in incubators where a temperature sin, papain, collagenase in combination with
of 37 C and a controlled atmosphere (95 % EDTA) and transferred into a fresh growth
air – 5 % CO2) are set in order to mimic the native medium in a new vessel (Hayflick 1998; Karp
environment. In the field of tissue engineering 2010). This procedure is called subculturing
and bioartificial organs, isolated cells are cultured (passaging or splitting) and transforms primary
on several types of biomaterials including poly- cultures in “cell lines” or subclones, where the
meric and composite membranes, extracellular cells with the highest growth capacity predomi-
matrix components, and batch and dynamic sys- nate resulting in a degree of genotypic and phe-
tems. Depending on the cell types, there are two notypic uniformity in the population. Moreover,
basic systems for growing cells in culture: the when a subpopulation is further selected, this cell
adherent culture system and the suspension sys- line becomes “cell strains” able to acquire addi-
tem. The adherent culture system has been spe- tional genetic changes. The survival ability of
cifically developed for the growth of anchorage- normal cell cultures lasts only for a limited num-
dependent cells that derive from solid tissues and ber of passages; however, some cells can become
require to adhere to a substrate in order to survive immortal due to a spontaneous or a viral-/
and proliferate. On the basis of their morphology chemical-induced modification. Acquiring the
(shape and appearance) or on their functional ability to proliferate indefinitely like the tumor
characteristics, these cells are divided into two cells, the characteristics of these transformed
different typologies: the epithelial-like cells that “continuous cell lines” are (i) the fast growth,
appear flattened and polygonal in shape and the (ii) the ability to grow up to higher cell density,
fibroblast-like cells, elongated and bipolar. The (iii) reduced serum and anchorage dependence
suspension culture, on the contrary, refers to the that allow the culture in suspension more than in
Cell Culture 3
adherent vessels, (iv) different in phenotypes and organs, either in 2D or 3D systems. Nowa-
from native tissue, and (v) stop expressing days, the cell cultures are the “model system” and
tissue-specific genes (Hayflick 1998; Alberts the perfect instrument for many applications:
et al. 2002; Karp 2010). In order to preserve cell (i) production of pharmacological substances
characteristic from further transformation or con- (antibodies, vaccines, growth factors, etc.),
taminations and to ensure the reproducibility of (ii) toxicity testing of drug effects, (iii) study of
experimentation in time, a surplus of cells, basic cell physiology, (iv) cancer research,
derived from subculturing, can be treated with a (v) genetic engineering, (vi) tissue engineering
cryoprotective agent (DMSO or glycerol) and and regenerative medicine, and (vii) gene
stored at a temperature below 130 C in liquid therapy.
nitrogen directly in the laboratories. Working
stocks of cell lines are reposted in many cryo-
preservation banks including the American Type
References
Culture Collection (ATCC) and the European
Collection of Cell Cultures (ECACC) (Alberts Alberts B, Johnson A, Lewis J, et al (2002) Table 8-3:
et al. 2002). some landmarks in the development of tissue and cell
The cell culture technology opens up new culture. In: Molecular biology of the cell, 4th edn.
perspectives in many fields, as the manufacturing Garland Science, New York
Hayflick L (1998) A brief history of the mortality and
of vaccines and other products of biotechnology, immortality of cultured cells. Keio J Med
and above all they became the turning point for 47(3):174–182
the development of the tissue engineering, sci- Karp GC (2010) Cell and molecular biology: concepts and
ence entrusted of the study and production of experiments, 6th edn. Wiley, New York
artificial tissues and the regeneration of tissue
U
flush through the modules. System cleaning more than four times as a result of surface charge.
involves thoroughly flushing out remaining prod- Ratings are not standardized among vendors and
uct and recirculating a cleaning solution at the depend on the marker solute selected (e.g., pro-
desired time, temperature, and concentration. tein, dextran in a particular buffer) and the level
Multiple fouling agents may require cleaning of retention selected for the marker solute (e.g.,
steps with multiple cleaning agents (e.g., NaOH 90 %). Retention is also affected by fouling due to
for proteins, acid for precipitated salts). Cleaning adsorbed components and polarized solutes on
effectiveness is measured by the restoration of the membrane surface. A rule of thumb for
water permeability. Sanitization involves selecting membrane NMWL is to take 0.2–0.3
recirculating a sanitizing solution at the desired of the MW of the solute that is to be retained by
time, temperature, and concentration. This is fre- the membrane. This should be taken as a rough
quently done as a separate additional step even if guide to select membranes for testing.
the chemical is the same as for cleaning. The Selected membrane module manufacturers in
rationale is to ensure that no protective biofilm 2012 include: EMD Millipore (Billerica, MA,
is present that would prevent sanitization from USA), Pall (Port Washington, NY, USA), Sarto-
being effective. At the end of a production cam- rius (Germany), Asahi Kasei (Japan), GE Energy
paign, modules can be stored in a liquid storage (Raytown, MO, USA), Siemens (Warrendale,
solution. Modules at the end of their life are PA, USA), TriSep (Goleta, CA, USA), Aquatech
discarded. Lifetimes can be set by number of (Canonsburg, PA, USA), Degremont Technolo-
uses, age, or process performance such as perme- gies (Richmond, VA, USA), Spintek (Los
ability, retention, integrity, and feed channel Alamitos, CA, USA), Koch Membrane Systems
pressure drop. (Wilmington, MA, USA), Berghof (M€uhlhausen,
Key UF membrane properties include reten- Germany), Daicel (Tokyo, Japan), DSS
tion capability, solvent permeability, chemical (Silkeborg, Denmark), Matrix (Oceanside, CA,
compatibility, mechanical strength for module USA), and Nitto Denko Hydranautics
fabrication and repeated use, consistency, and (Oceanside, CA, USA).
cost. UF membranes come with a nominal molec-
ular weight limit (NMWL) rating of
1.0–5,000.0 KDa. The smaller rating means a
References
tighter filter able to retain a smaller solute with
a lower molecular weight. While these ratings are Ho WS, Sirkar K (1992) Membrane Handbook, Van
convenient for testing and rough selection, solute Nostrand Reinhold, NY
retention is based on effective solute dimensions Lutz H (2008) Membrane Separation Procsses in Perry’s
and not on molecular weight. Nonspherical sol- Chemical Engineer’s Handbook, 8th ed., McGraw-
Hill, NY
utes will orient themselves under shear so that Lutz H (2015) Ultrafiltration for Bioprocessing,
their major axis is parallel to the pores. Linear Woodhead Publishing, Cambridge UK
chain dextrans and DNA show a higher passage Zeman LJ, Zydney AL (1996) Microfiltration and Ultra-
than globular proteins of the same molecular filtration, Marcel Dekker, NY
weight. The effective solute radius can increase
U
concentrate and change buffers (for final formu- Wastewater treatment and water purification
lation into a storage buffer). For drug products applications employ UF in a TFF or NFF mode to
with potential viral contaminants (sourced from produce permeate product with reduced colloids,
mammalian cells or human and animal blood pyrogens, and viruses. Oil droplets in wastewater
plasma), virus removal filters employed in either are retained by UF for recycle or disposal at
a TFF or NFF mode retain the viruses, while the significantly reduced volumes (Table 1).
drug product is recovered in the permeate. UF has
displaced size exclusion chromatography (SEC)
for buffer exchange due to its lower cost and
References
ability to run higher protein concentrations.
These applications require high yields, Ho WS, Sirkar K (1992) Membrane Handbook, Van
maintaining high purity, consistent operation, Nostrand Reinhold, NY
and scale-up of the valuable product. Lutz H (2015) Ultrafiltration for Bioprocessing,
UF is used to clarify various fruit juices (apple, Woodhead, Cambridge, UK
Lutz H (2008) Membrane Sepataion Processes in Perry’s
grape, pear, pineapple, cranberry, orange, and Chemical Engineering Handbook, 8th ed, McGraw-
lemon) which are recovered as the permeate. UF Hill, NY
has also been used to remove pigments and Zeman LJ, Zydney AL (1996) Microfiltration and Ultra-
reduce browning in wine production. Low-cost filtration, Marcel Dekker, NY
operation is required.
U
UF Modeling, Fig. 1 UF
Modeling Diafiltrate D
Retentate R
Feed F
Permeate P
Single-pass Batch
Recycle Tank
Fed-Batch Continuous
Batch operation involves recycling the volumes in a single skid. For a fed-batch opera-
retentate to the feed tank to create a multipass tion, the retentate is returned to a smaller recycle
flow of the feed through the module. The compo- tank, not the large feed tank. Feed is added to the
sitions in batch systems change over time. High recycle tank as permeate is withdrawn to main-
flow rates generate better fluxes but recycling is tain a constant recycle tank volume. The recycle
necessary to generate either the desired permeate tank can allow a smaller working volume without
flow or a concentrated retentate. Multipass oper- entrainment. Reducing the size of the recycle
ation increases residence times and pump passes tank results in just a section of the pipe or bypass
that may degrade retentate components. For sys- line that returns the retentate directly into the
tems requiring high pressures to generate perme- pump feed. Fluid from the feed tank is added
ate flow, it is useful to run the entire system at slowly into this recirculation loop. This allows a
high pressure to save energy. As before, holdup volume consisting of just the recirculation
unsteady-state solvent and component mass bal- loop. This configuration can be problematic to
ances can be written for batch operation and flush, vent, and drain leading to cleaning and
combined and integrated to yield concentration product recovery issues. Fed-batch retentate con-
behavior. TFF systems have a maximum volume centrations exceed the batch concentrations until
reduction capability, typically about 40x. This the curves intersect and any further concentration
arises because tanks must be large enough to would proceed in batch mode. The benefits
hold the batch volume while allowing operation sought from higher concentrations can lead to
at a minimum working volume. The minimum other problems such as reduced fluxes, larger
working volume may be limited by air entrain- area and pumps, possible denaturation, and
ment into the feed pump, mixing in the feed tank, extra lines that may have issues with cleaning
or level measurement capabilities. and product recovery. This has not only caused
Fed-batch operation extends the volume significant commissioning and validation delays
reduction capability to 100x and provides some but also led to the scrapping of a process skid as
flexibility in processing a variety of batch unworkable. The number of pump passes will
UF Modeling
also be higher, leading to more potential solute diavolumes. It is common to add an extra 1–2
degradation. Fed batch and bypass should be used diavolumes as a safety factor to ensure complete
only when necessary. buffer exchange. For final formulation pharma-
Diafiltration mode involves adding a new ceutical applications, 8–10 diavolumes are
buffer to the system while withdrawing permeate standard.
at the same rate so the tank level remains con- Diafiltration usually takes much more time
stant. Over time, the retained solute sees a buffer than concentration. When a fully retained solute
change. This is characterized by the controls the flux by the gel model, the batch
diavolumes N, the ratio of buffer volume added diafiltration time is given by
0 1
to tank volume for batch systems, and the ratio of
buffer flow to feed flow for continuous systems. V B N=X C
0 B C, where C and X are related
t¼ A @
Table 1 shows how solute concentrations change Cg A
kln
with N. A fully retained solute (Si = 0) maintains C
its retentate concentration constant at the initial as in Table 1. This equation shows that more
value. For fully passing solutes, >4.5 diavolumes initial volume reduction and higher concentration
are needed to achieve a specification of <1 % of lead to reduced batch volume and lower
the original buffer components. Incomplete diafiltration fluxes. A minimum time solution
mixing (due to dead legs and liquid droplets on exists when C = Cg/e.
tank walls) becomes significant at high
U
ity, m is the fluid viscosity, and l is the membrane mass transfer coefficient and Cg is a constant “gel
thickness. Any retained solute will accumulate on point” wall concentration. An actual gel is not
the upstream membrane surface causing an formed. The osmotic model describes the flux
osmotic pressure P. Membrane fouling reduces across the linear and polarized regions. These
the membrane permeability to Lf. Process flow is models strictly apply to a uniform upstream,
described by the osmotic model while in membrane modules, properties change
J ¼ Lf ðTMP s0 DPÞ where s0 is the osmotic along the upstream channel. The models can be
or Staverman reflection coefficient. For a totally integrated along the feed channel but are com-
retained solute, s0 = 1, and for a totally passing monly used with an average TMP across the feed
solute, s0 = 0. When TMP<DP, reverse flow is channel and feed velocities and concentrations.
observed.
A hydrodynamic analysis of steady-state solute and Kd 1 1:004l þ 0:418l3 þ 0:21l4 0:619l5 :
flux by diffusion and convection along a pore yields The “actual” solute sieving coefficient becomes
a net solute flux of N ¼ ½fKc J=e ½Cwall expðPem Þ Sa ¼ Cpermeate =Cwall ¼ S1 expðPem Þ=½S1 þ expðPem Þ
Cpermeate =½expðPem Þ 1. The membrane Peclet 1 where S1 ¼ fKc ¼ 1 s0 is the asymptotic
number is Pem ¼ ½Jl=D1 ½fKc =efKd for solute- sieving coefficient for large Pem where convection
free solution binary diffusivity D1, partitioning dominates. The presence of surface charges reduces
coefficient f, convective hindrance coefficient Kc, both membrane permeability and solute sieving
and diffusive hindrance coefficient Kd. Pore shapes coefficients. Average sieving across a membrane
fall in-between cylindrical and slit geometries in thickness from the wall to the permeate requires
terms of solute and pore wall interactions. For a integration across the pore size distribution. Mea-
spherical solute in a cylindrical pore, Cpore =Cwall sured sieving coefficients from the bulk feed to the
¼ f ¼ ð1 lÞ2 where l ¼ rsolute =rpore , while permeate requires accounting for polarization. Sol-
h i
utes are diluted within pores, but multicomponent
asymptotic analysis yields Kc 2 ð1 lÞ2
interaction is required within the polarization layer
exp 0:7146l2 and Kd ð1 lÞ13=2 . For a where large solute polarization reduces the sieving
spherical solute in a slit pore, steric considerations of smaller solutes. Sieving along devices requires
imply an equilibrium partitioning Cpore =Cwall ¼ integration along the feed channel.
f ¼ ð1 lÞ where l ¼ rsolute =rpore, while asymp-
totic analysis yields Kc ð3 fÞ2 1=2 l2 =6
U
UF Membranes, Fig. 1 Regenerated cellulose ultrafiltration membrane side view SEM. (a) Conventional UF,
(b) Composite UF (Courtesy of Millipore Corporation)
Foam or nodular structures form depending on Inorganic UF membranes (alumina, glass, and
the formation path. Asymmetry or skin structures zirconia) are formed by sintering. Layers of
can form depending on the kinetics of diffusive spherical particles are deposited on a substrate
transport and nucleation. The key control and heated to fuse them together. Pores are
parameters are the composition of the lacquer, formed in the gaps between the spherical parti-
composition of the immersion bath, coating or cles. Successive layers of smaller and smaller
extrusion thickness, casting speed, bath tempera- particles can be deposited to make tighter
ture, and bath flow velocity. membranes. These membranes find use in corro-
Residual solvent and anti-solvent are washed sive applications where their high cost can be
out of the polymeric membrane structure in justified (Table 1, Fig. 1).
separate extraction baths. Hydrophobic polymers
are surface modified to render them hydrophilic
and thereby reduce fouling, reduce product References
losses, and increase flux.
Zeman LJ, Zydney AL (1996) Microfiltration and Ultra-
filtration, Marcel Dekker, NY
A
Alkane Oxidative
Dehydrogenation by
Membrane Reactor,
Fig. 1 Scheme of a
membrane reactor for the
selective oxidation of
hydrocarbons with a
distributed feed of oxygen
Maleic Anhydride Production by approach implies the use of large feed and prod-
Membrane Reactor uct flows, increasing the operating and capital
costs. The use of a membrane reactor allows the
Miguel Menendez operation with a large butane concentration (up to
Department of Chemical and Environmental 10 % butane) but avoiding the coexistence in a
Engineering, University of Zaragoza, Zaragoza, given point of large butane and oxygen concen-
Spain trations (Mallada et al. 2000), in a similar way as
when membrane reactors are used for oxidative
dehydrogenation. A critical point in this kind of
Maleic anhydride is a valuable intermediate reactor is to avoid too low oxygen concentrations,
product in the manufacture of polyester fiber, since a reducing atmosphere changes the oxida-
succinic acid, tetrahydrofuran, tartaric acid, and tion degree of vanadium, with a catastrophic
several other chemicals. Most of the maleic anhy- decrease in selectivity.
dride is produced by the oxidation of butane with A way to decrease the risk of vanadium reduc-
VPO catalyst. This reaction is unique because no tion is using CO2 as inert gas. In fact, there are
other commercial process achieves the insertion experimental proofs that under reaction condi-
of three oxygen atoms in one paraffin molecule in tions, CO2 is not fully “inert” but can contribute
a single step using molecular oxygen. The cata- to achieve a more oxidized catalyst (Mallada
lyst is a complex mixture of vanadium and phos- et al. 2002; Xue et al. 2001).
phorous oxides, which is often close to the Another factor that may contribute to improve
chemical composition of vanadyl pyrophosphate, the maleic anhydride yield in a membrane reactor
but in fact the oxidation degree of vanadium is the catalyst bed configuration. If the catalyst
varies between +4 and +5 depending on the oper- bed is located around the membrane, instead of
ating conditions. inside, the achievable yield increases.
Industrial operation is limited by need to avoid A mathematical model of both reactors explains
explosive atmospheres, which requires low this result by the differences in radial partial
butane or low oxygen concentration. In conven- pressure profiles (Pedernera et al. 2000).
tional reactors a low oxygen concentration would Finally, in order to apply a membrane reactor
imply a too low butane conversion, which would industrially, the temperature control is critical.
be economically unsuitable. Therefore the indus- While fixed bed reactors use a bath of fused
trially employed approach, both for fixed and salts to keep the catalyst bed temperature under
fluidized bed reactors, is to feed a low butane control, this approach would not be feasible in
concentration (typically below 2 %) in air. This membrane reactors. A method proposed to
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1212-1
2 Maleic Anhydride Production by Membrane Reactor
control the temperature in a membrane reactor is Mallada R, Menéndez M, Santamarı́a J (2000) Use of
to surround the reactor with a fluidized bed. The membrane reactors for the oxidation of butane to
maleic anhydride under high butane concentrations.
high isothermicity and excellent heat exchange Catal Today 56:191–197
are well-known characteristics of fluidized beds, Mallada R, Menéndez M, Santamarı́a J (2002) On the
and the same oxygen containing stream that is favourable effect of CO2 addition in the oxidation of
permeated through the membrane can be used to butane to maleic anhydride using membrane reactors.
Appl Catal A Gen 231:109–116
keep the bed fluidized. This configuration has Pedernera M, Mallada R, Menéndez M, Santamaria
been employed in a pilot plant (Alonso J (2000) Simulation of an inert membrane reactor for
et al. 2001). the synthesis of maleic anhydride. AIChE
J 46:2489–2498
Xue E, Ross JR, Mallada R, Menendez M, Santamaria J,
Perregard J, Nielsen PEH (2001) Catalytic oxidation of
References butane to maleic anhydride enhanced yields in the
presence of CO2 in the reactor feed. Appl Catal
Alonso M, Lorences MJ, Pina MP, Patience GS A Gen 210:271–274
(2001) Butane partial oxidation in an externally fluid-
ized bed-membrane reactor. Catal Today 67:151–157
N
Introduction
Modifications in the Reactor
Configuration
Butene, isobutene, and butadiene are mainly
obtained from steam crackers, but the increased
This approach has been employed by several
use of natural gas as feedstock has decreased the
researchers with a variety of modification in the
availability of C4 olefins. Therefore, these olefins
configuration:
are increasingly produced by the dehydrogena-
tion of the corresponding alkane. Since that is an
– Pure butane in the feed to the bed entry and
equilibrium-limited reaction, oxidative dehydro-
homogeneous oxygen distribution along the
genation has been proposed as an alternative that
bed using a membrane.
has raised much interest (Mamedov and Cortés-
– Butane diluted with inert gas and/or oxygen
Corberán 1995; Madeira and Portela 2002). As it
diluted with inert gas. In comparison with the
happens in many selective oxidations, the
previous approach, safety is increased and
undesired formation of carbon oxides (CO and
often the achieved selectivity is better, but
CO2) is a serious problem. As in other selective
the industrial application would require the
oxidations, membrane reactors have been also
separation of inert gases from the reaction
proposed for this reaction. Significant improve-
products, increasing the process operation
ment of yield has been observed when the oxygen
costs.
is distributed to a fixed bed of catalyst enclosed in
– Nonhomogeneous distribution of oxygen feed.
a porous membrane (Téllez et al. 1997).
In order to obtain a greater reaction rate at the
A progressive distribution has been found to be
reactor entry, a larger permeation of oxygen
advantageous (Ge et al. 2001). An interesting
near the propane entry may be useful.
alternative is the use of CO2 instead of O2 as
# Springer-Verlag Berlin Heidelberg 2015
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1213-2
2 N-Butane Oxidative Dehydrogenation by Membrane Reactor
Propane Oxidative the reaction zone. For many catalysts, a low par-
Dehydrogenation by Membrane tial pressure of oxygen implies a better selectivity
Reactor to propene (Ziaka et al. 1993; Pantazidis et al.
1995; Tonkovich et al. 1996). The use of porous
Miguel Menendez membranes has been reviewed by Coronas and
Department of Chemical and Environmental Santamarı́a (1999) and Julbe et al. (2001).
Engineering, University of Zaragoza, Zaragoza,
Spain
Modifications in the Reactor
Configuration
Propene is industrially obtained in naphtha crack-
ers, in FCC units, and in a growing proportion, by
This approach has been employed by several
dehydrogenation of propane. Propane dehydro-
researchers with a variety of modification in the
genation is an endothermic reaction, and the
configuration:
maximum achievable conversion is limited by
thermodynamic equilibrium. An alternative to
– Pure propane and homogenous oxygen distri-
propane dehydrogenation is the oxidative dehy-
bution along the bed.
drogenation of propane. In such case, the reaction
– Propane diluted with inert gas and/or oxygen
is irreversible, but the inconvenience is the
diluted with inert gas. In comparison with the
appearance of nonselective oxidation reactions
previous approach, safety is increased and
of propane and propene to carbon oxides
often the selectivity achieved is better, but the
(CO and CO2). The success of propane oxidative
industrial application would require the separa-
dehydrogenation will be linked to the achieve-
tion of inert gases from the reaction products,
ment of high selectivity to propene and high
increasing the process operation costs.
enough conversion (Cavani et al. 2007). A large
– Nonhomogenous distribution of oxygen feed.
amount of research has been devoted to the opti-
In order to obtain a greater reaction rate at the
mization of the catalyst, and this is obviously a
reactor entry, a larger permeation of oxygen
key factor, but the selection of a suitable reactor
near the propane entry may be useful.
may be another factor contributing to achieve a
– Combination of a conventional fixed bed reac-
successful result. A packed bed membrane reac-
tor with a membrane reactor. In such case, the
tor in which propane is fed at the catalyst bed
feed to the fixed bed reactor contains a small
entry and oxygen is permeated along the mem-
amount of oxygen.
brane provides a low partial pressure of oxygen in
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1215-2
2 Propane Oxidative Dehydrogenation by Membrane Reactor
– The use of a catalytic membrane. In this case, tested in propane dehydrogenation, the most
part of the membrane is loaded with catalyst, employed are the simplest ones: vanadium oxide
preferentially in the side where propane is fed. supported on alumina or on magnesium oxide.
The operation principle is the same as when a
packed bed of catalyst is employed: the lower
oxygen partial pressure in the reaction zone
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(Alfonso et al. 1999; Julbe et al. 2000). Alfonso MJ, Julbe A, Farrusseng D, Menendez M,
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The membrane employed for this reaction does not drogenation of ethane and propane: how far from com-
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membrane may be employed. In such case, the Coronas J, Santamarı́a J (1999) Catalytic reactors based on
porous ceramic membranes. Catal Today 51:377–389
back permeation of hydrocarbon to the shell side Czuprat O, Werth S, Caro J, Schiestel T (2010) Oxidative
must be avoided. This usually requires a significant dehydrogenation of propane in a perovskite membrane
pressure drop of oxygen. Examples of membranes reactor with multi-step oxygen insertion. AIChE
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Julbe A, Farrusseng D, Jalibert JC, Mirodatos C, Guizard
membranes with the pores filled with silica, C (2000) Characteristics and performance in the oxi-
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trips to reduce the permeation or zeolite mem- zeolite membranes. Catal Today 56:199–209
branes. In an alternative configuration, the mem- Julbe A, Farrusseng D, Guizard C (2001) Porous ceramic
membranes for catalytic reactors-overview and new
brane has catalytic activity (Alfonso et al. 1999). ideas. J Membr Sci 181:3–20
Alternatively dense ceramic membranes, i.e., Pantazidis A, Dalmon JA, Mirodatos C (1995) Oxidative
oxygen selective, can be employed (Wang dehydrogenation of propane on catalytic membrane
et al. 2003; Czuprat et al. 2010). In such case, in reactors. Catal Today 25:403–408
Tonkovich ALY, Zilka JL, Jimenez DM, Roberts GL, Cox
addition to the improvement in propene selectivity JL (1996) Experimental investigations of inorganic
provided by the oxygen distribution and the avoid- membrane reactors: a distributed feed approach for
ance of back permeation problems, the previous partial oxidation reactions. Chem Eng Sci 51:789–806
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dehydrogenation of propane in a dense tubular mem-
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the following. Plasma treatment can induce radi- plasma-induced graft polymerization (Inagaki
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PECVD makes it possible to work out very by conventional ways: chemical inertia, good
thin films with thicknesses of a few nanome- thermal stability, anticorrosive character, and
ters to a few microns, which is impossible with barrier properties with respect to oxygen and
liquid-route synthesis methods. The deposi- water vapor in particular.
tion rate can be high (several mm min 1) – PECVD makes it possible to adjust the chem-
(Storgaard-Larsen and Leistiko 1997) making ical composition and the microstructure of
the process ideal for industrial applications. deposited materials and thus to modify the
– One of the major interests of this technique is physical and chemical properties of these
the possibility of depositing materials at ambi- materials by the simple variation of the param-
ent temperature on substrates sensitive to heat eters of the process, and this in a field much
such as conventional organic polymers (which broader than the other deposition techniques.
is not possible with conventional chemical If, from a technological point of view, this
vapor deposition (CVD): chemical plating in requires a rigorous control of the parameters
pyrolytic phase vapor). The polymeric sup- of the process, the complexity and variety of
ports constitute, with glasses, semiconductors, active species and reaction steps directly
ceramics, and metal surfaces, the large variety related to the plasma parameters offer a high
of substrates on which the plasma deposits degree of flexibility in prepared materials
have a good adherence. properties.
– The materials deposited by PECVD are gen-
erally dense, amorphous, strongly cross-
linked, and present a low density of defects
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plasma-polymerized thin layer on porous mate- Roualdes S, Rouessac V, Durand J (2010) Plasma mem-
branes. In: Drioli E, Giorno L (eds) Comprehensive
rials such as filter paper or polyester textile membrane science and engineering, vol 1. Academic,
(Bankovic et al. 2004). The development of Oxford, pp 159–197
plasma membranes has been more recently Teramae T, Kumazawa H (2007) Gas permeability and
applied to fields using ion-conducting mem- permselectivity of plasma-treated polypropylene
membranes. J Appl Polym Sci 104:3236–3239
branes such as electromembrane processes Upadhyay DJ, Bhat NV (2004) Pervaporation studies of
(electrodialysis in particular), electrochemical gaseous plasma treated PVA membrane. J Membr Sci
sensors, or, more broadly, the energy production 239:255–263
devices (fuel cells, Li-ion batteries, etc.) Vilani C, Weibel DE, Zamora RRM, Habert AC, Achete
CA (2007) Study of the influence of the acrylic acid
(Roualdes et al. 2010). plasma parameters on silicon and polyurethane sub-
strates using XPS and AFM. Appl Surf Sci
254:131–134
References Weibel DE, Vilani C, Habert AC, Achete CA (2007) Sur-
face modification of polyurethane membranes using
acrylic acid vapor plasma and its effects on the
Bankovic P, Demarquette NR, da Silva MLP pervaporation processes. J Membr Sci 293:124–132
(2004) Obtention of selective membranes for water
P
deposition, on the other hand by liquid-route syn- light species due to strong fragmentation in
thesis methods (see article entitled “PECVD”). highly energetic plasmas.
The microstructural properties of plasma Although considered as dense materials,
polymers depend mostly on the parameters of plasma polymers are characterized by a free vol-
plasma polymerization and more particularly on ume comparable to ultramicroporosity (spaces
the W/FM parameter. In the monomer-sufficient between chains lower than 0.7 nm). Changing
region (low W/FM values), monomer molecules the plasma parameters in the preparation of
are subjected to less fragmentation to be plasma films can enable to tune this free volume as well
polymerized, and plasma polymers with less as the chains flexibility. The approaches that may
arrangement and small loss of some groups such achieve enhanced free volume and chain flexibil-
as hydrogen, methyl, hydroxyl, and carbonyl ity can be summarized as follows: (1) minimiza-
groups are formed. Under such soft synthesis tion of the W/FM parameter, (2) pulsing of the RF
conditions, plasma polymerization retains more field to reduce the plasma-on time, (3) use of a
the molecular structure of the monomer; plasma Faraday cage around the substrate, (4) positioning
polymers are more organic and less highly cross- the sample downstream from the plasma zone
linked and thus resemble more conventional (post-discharge configuration), (5) use of mono-
polymers; they are said to be polymer-like mate- mers containing polymerizable double bonds,
rials. In the monomer-deficient region (high and (6) use of a cold substrate. It is possible to
W/FM values), monomer molecules are further increase the free volume and change it
subjected to heavier fragmentation, and plasma into micro- (pores diameter between 0.7 and
polymers with much more rearrangements and a 2 nm) or meso- (pores diameter of some nanome-
larger loss of some groups (especially carbon- ters) porosity by adding a porogen in the plasma
based ones) are formed. Under such drastic syn- reactor as comonomer and then eliminating it
thesis conditions, plasma polymers are harder, from the prepared film by thermal or UV
more inorganic, and more highly cross-linked; posttreatment (Favennec et al. 2004; Rouessac
they are said to be ceramic-like. For intermediate et al. 2006). The porogen approach is mainly
values of W/FM, a wide range of hybrid materials applied to polymer-like plasma films. Indeed,
can be manufactured. Let us consider the case of ceramic-like plasma materials are usually
hexamethyldisiloxane (HMDSO), widely used as required for their highly dense structure; never-
monomer in plasma polymerization (Ayral theless, they sometimes naturally contain some
et al. 2008). In soft plasma conditions, the plasma microporosity because of chain breakings due to
film synthesized from HMDSO has a structure very high cross-linking degrees (Roualdes
close to those of the HMDSO monomer and et al. 2002).
also the polydimethylsiloxane (PDMS), which is For membrane applications, plasma polymer-
the closest conventional polymer, as shown by ization is usually performed on a highly porous
Fourier transform infrared (FTIR) spectroscopy; substrate whose only role is to mechanically sup-
this plasma film is thus called PDMS-like plasma port the thin plasma polymer, called plasma-
polymer; its density is quite low, equal to 1.1. In polymerized membrane in this case. Neverthe-
hard plasma conditions, the obtained plasma film less, plasma polymerization can also be applied
is similar to amorphous hydrogenated silica with on a dense or poorly porous substrate being
a density of 2.2; it is noted a-SiO2:H (“a” for already an active membrane; in this case, it
amorphous, “:H” for hydrogenated); the dilution could achieve the same effect as plasma etching
with an oxidative gas as O2 or N2O in the plasma or plasma functionalization (i.e., modification of
reactor can enable to achieve this silica structure surface characteristics of the membrane sub-
at lower W/F values. Mass spectrometry (MS) is strate) with additional advantageous characteris-
a very useful technique to reveal the low frag- tic features of the nanometer film of plasma
mentation of the monomer in soft plasma condi- polymer. Moreover, a special kind of plasma
tions and, on the contrary, the formation of many polymerization that has received increased
Plasma Polymerization 3
in essence, polymer-like plasma materials are such materials by plasma polymerization is par-
generally not as permeable as conventional mem- ticularly challenging and requires a delicate
branes. In order to enhance their permeability, the research task in the choice of the precursor
easiest solution consists in reducing their thick- (s) and the adjustment of plasma parameters.
ness, to the detriment of their mechanical stabil-
ity. Another solution is to increase their free
volume and/or chain flexibility to make them
References
resemble more conventional polymers. For gas
retention (packaging application essentially), Inagaki N, Tsutsumi D (1986) Plasma-polymerization of
membranes providing low fluxes of penetrants F-propene/acetylene and F-propene/ethylene mixtures
are required. Ceramic-like plasma films are and their gas permeability. Polym Bull 16:131–136
more suitable in this case; their transport proper- Inagaki N, Tasaka S, Park MS (1990) Gas separation
membrane made by plasma polymerization of
ties are rather controlled by the molecular sieve 1,3-ditrifluoromethylbenzene/CF4 mixture. J Appl
mechanism as for classical crystallized ceramics. Polym Sci 40:143–153
The development of polymer-like plasma Julbe A, Rouessac V, Durand J, Ayral A (2008) New
films has been more recently applied to fields approaches in the design of ceramic and hybrid mem-
branes. J Membr Sci 316:176–185
using ion-conducting membranes such as Roualdes S, Sanchez J, Durand J (2002) Gas diffusion and
electromembrane processes (electrodialysis in sorption properties of polysiloxane membranes pre-
particular), electrochemical sensors, or, more pared by PECVD. J Membr Sci 198(2):299–310
broadly, the energy production devices (fuel Roualdes S, Rouessac V, Durand J (2010) Plasma mem-
branes. In: Drioli E, Giorno L (eds) Comprehensive
cells, Li-ion batteries, etc.) (Roualdes membrane science and engineering, vol 1. Academic,
et al. 2010). Such applications require the use of Oxford, pp 159–197
materials having a good swelling in water and Yasuda H (1984) Plasma polymerization for protective
containing specific functions, often charged, dis- coatings and composite membranes. J Membr Sci
18:273–284
tributed in an ordered manner in order to form
effective channels of ionic conduction. Obtaining
V
Vapor Plasma Membrane Treatment (up to 50 eV) to induce the ionization of gas
molecules. Such ionized species (acquiring ener-
Stephanie Roualdes gies typically in the range of 0–2 eV) initiate a
IEM/UM II – CC 047, Place Eugene Bataillon, high number of complex reactions (ionization,
Montpellier, France excitation, neutralization, recombination,
deexcitation, etc.) constituting what is called a
glow discharge. A glow discharge implies a
Plasma processes (Yasuda 1985; d’Agostino high variety of species: electrons, negative and
1990; Biederman and Osada 1992; Inagaki positive ions, radicals, neutral atoms and mole-
1996) were initially developed for microelectron- cules, and also photons (emitted by radiative
ics in the 1950s. They represent a clean deexcitation) whose mixture constitutes the
(producing few or not effluents) and also plasma state. A plasma is essentially character-
extremely flexible technology whose basic equip- ized by its energy and its electronic density.
ment, well adapted to automation, makes it pos- Depending on the values of both microscopic
sible to achieve goals as various as singular in parameters, different kinds of natural or artificial
terms of specific properties of use; their costs of plasmas can be distinguished, being classified in
operation are moreover relatively weak. Based on two categories: hot plasmas and cold plasmas.
these advantages, they are used today in many Artificial plasmas, generated by a low frequency
fields of the materials chemistry (in particular the (25–450 kHz), radio frequency (1–500 MHz), or
membranes field) even if their industrialization microwave (500 MHz–some GHz) continue or
still remains not very developed, because of the alternative discharge at rather low pressure
high cost of the equipment necessary to their (10–2–10 Torr), are cold plasmas. Cold plasmas
implementation and of a certain conservatism of are characterized by energy and electronic den-
the industrialists reticent to introduce this new sity equal to 1–10 eV and 1,010 cm 3, respec-
technology, however so promising. tively. Their ionization degree is lower than 10 3
Defined by Crookes in 1879 as the fourth state so that the gas phase is mainly made up of neutral
of the matter, a plasma is a partially ionized and species in an excited state (radicals).
overall neutral medium generated by the applica- A characteristic of these plasmas is the absence
tion of an electric field to a gas phase at low of thermodynamic balance between the elec-
pressure (<10 Torr). The energy of the applied tronic temperature (several thousands of degrees)
electric field is transferred to free electrons which and that of gas (near to the ambient).
collide with the gas molecules. Such inelastic The interaction between a cold plasma and a
impacts make electrons achieve enough energy material placed within it (substrate) results in
# Springer-Verlag Berlin Heidelberg 2012
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1230-3
2 Vapor Plasma Membrane Treatment
Drioli E, De Bartolo L (2010) Influence of micro- Didymin on H2O2-Induced Injury in Neuronal Mem-
patterned PLLA membranes on outgrowth and orien- brane System. Cells Tissues Organs 199:184–200
tation of hippocampal neurites. Biomaterials Piscioneri A, Morelli S, Mele M, Canonaco M, Bilotta E,
31:7000–7011 Pantano P, Drioli E, De Bartolo L (2015)
Morelli S, Piscioneri A, Salerno S, Rende M, Campana C, Neuroprotective effect of human mesenchymal stem
Tasselli F, Di Vito A, Giusi G, Canonaco M, Drioli E, cells in a compartmentalized neuronal membrane sys-
De Bartolo L (2012) Flat and tubular membrane sys- tem. Acta Biomaterialia 24:297–308.
tems for the reconstruction of hippocampal neuronal Wolfrum B, Mourzina Y, Sommerhage F, Offenhausser
network. J Tissue Eng Regen Med 6:299–313 A (2006) Suspended nanoporous membranes as inter-
Morelli S, Piscioneri A, Messina A, Salerno S, Al-Fageeh faces for neuronal biohybrid systems. Nano Lett
MB, Drioli E, De Bartolo L (2015) Neuronal growth 6:453–457
and differentiation on biodegradable membranes. Zhang N, Yan H, Wen X (2005) Tissue-engineering
J Tissue Eng Regen Med. 9:106–117 approaches for axonal guidance. Brain Res Rev
Morelli S, Piscioneri A, Salerno S, Al-Fageeh M, Drioli E, 49:48–64
De Bartolo L (2014) Neuroprotective Effect of
A
improved biocompatibility and reduce comple- renal failure. A potential solution to ease the
ment activation; however, they may enhance pro- demand for donor kidneys may be the use of
tein adsorption to the membrane in the absence of tissue engineering techniques that could be used
further modification. Despite the improved com- to develop functional kidneys. A primary chal-
patibility of synthetic membranes, the most lenge in renal tissue engineering, however, is the
recent large review does not demonstrate benefits production of tissues with the functional com-
conveyed by biocompatibility. The ultrastructure plexity required for kidney transplantation. The
of membranes is predominantly the capillary first step in achieving this aim could be to pro-
design, or hollow fiber structure, in which blood duce acellular kidney matrices for use as biolog-
flows through a series of small tubes held together ical scaffolds that support cell growth and
in a bundle. This allows for a low-resistance, high facilitate new tissue formation by potentiating
surface area membrane. Membrane properties cell–cell interaction. Several groups have used
such as charge, wall thickness, and pore size different perfusion-based decellularization proto-
affect function. The radius of the pore is related cols to produce naturally derived kidney scaf-
to the ultrafiltrate flow through the membrane, folds (Arenas-Herrera et al. 2013).
but overall fluid transfer is a function of the In the last decade, several studies have been
mean pore size. The number or density of pores performed on the development of the implantable
and the radius of the pore affect solute transfer in artificial kidneys, but these studies reported only
diffusive clearances. Membrane characteristics developmental concepts, in vitro or in vivo stud-
such as flux and permeability to water are deter- ies using small animals. It is difficult to control
minants of pore characteristics and wall thickness certain research aspects of an implantable artifi-
(Vigano et al. 2008). cial kidney to a preclinical level, and these
As dialysis membrane technology has aspects include long-term maintenance of the
improved, high-flux membranes with larger pore antithrombogenic properties of the systems and
sizes have been developed to allow greater clear- each of its components, and the function of an
ances of larger retention molecules with reduced implanted, miniaturized system, whose function
induction of inflammatory mediators. While must be maintained for a year’s duration. Further
observational studies suggest that high-flux progress in nanotechnology and biotechnology is
hemodialysis is associated with lower and required to realize a treatment with an implant-
dialysis-related amyloidosis, individual random- able kidney (Saito et al. 2011).
ized controlled trials have not confirmed that New directions in dialysis research include
high-flux hemodialysis improves clinical out- cheaper treatments, home-based therapies, and
comes. High-flux dialysis membranes have larger simpler methods of blood purification. These
pore sizes that may increase transportation of objectives may be probably obtained with inno-
dialysate impurities or contaminants from the vations in the field of artificial kidney through the
dialysate to the bloodstream even when the dial- utilization of new disciplines such as miniaturi-
ysate quality complies with acceptable standards, zation, microfluidics, and nanotechnology. This
although some evidence suggests that high-flux research may lead to a new era of dialysis in
membranes may actively absorb endotoxins and which the new challenges are transportability,
impede their back transfer from dialysate into the wearability, and why not the possibility to
bloodstream (Palmer and Strippoli 2013). develop implantable devices (Ronco et al. 2011).
Although dialysis is currently an available
treatment for chronic renal disease, it replaces
only the filtration function of the kidneys, and
References
thus, it is associated with a number of complica-
tions and is not a permanent solution. Kidney Arenas-Herrera JE, Ko IK, Atala A, Yoo JJ
transplantation performed in a heterotopic loca- (2013) Decellularization for whole organ
tion is the only definitive solution for end-stage
Artificial Kidney 3
bioengineering. Biomed Mater 8:014106. Saito A, Sawada K, Fujimura S (2011) Present status and
doi:10.1088/1748-6041/8/1/014106 future perspectives on the development of bioartificial
Fleming GM (2011) Renal replacement therapy review. kidneys for the treatment of acute and chronic renal
Past, present and future. Organogenesis 7:2–12 failure patients. Hemodial Int 15:183–192
Palmer SC, Strippoli G (2013) High-flux versus low-flux Vigano SM, Di Filippo S, Manzoni C, Locatelli F (2008)
haemodialysis membranes for end-stage kidney dis- Membrane characteristics. In: Ronco C, Cruz DN (eds)
ease. Nephrology 18:313–314 Hemodialysis-from basic research to clinical trials,
Ronco C, Davenport A, Gura V (2011) The future of the vol 161, Contribution of nephrology. Karger, Basel,
artificial kidney: moving towards wearable and mini- pp 162–167
aturized devices. Nefrologia 31:9–16
E
Emulsification by Membrane Operations, Table 1 Different membrane operations used for the production
emulsion droplets
Advantages Disadvantages
Dynamic membrane emulsification
Stirred ME Suitable for low volumes of continuous Emulsion production at batch scale
phase
Useful to study the effect of different The shear stress at the membrane surface is
experimental conditions on the emulsion nonuniform and depends on the cell geometry
preparation
Cross-flow ME Constant shear stress at the membrane Emulsion droplet breakup as a consequence
surface of the recirculation
Suitable for large-scale production and High dispersed phase concentration is
continuous or semicontinuous operation obtained after a long time of operation
Cross-flow ME with Constant shear stress at the membrane High dispersed phase concentration is
static promoter surface obtained after a long time of operation
Suitable for large-scale production and
continuous or semicontinuous operation
Suitable to prevent droplet breakup
Rotating ME Suitable for large-scale production and Complicated and more expensive design
continuous or semicontinuous operation Higher power consumption
Able to prevent droplet breakup
High dispersed phase concentrations
obtained in a single pass
Vibrating ME Suitable for large-scale production and Complicated and more expensive design
continuous or semicontinuous operation
Able to prevent droplet breakup Higher power consumption
Nonuniform temporal distribution of shear
stress on the membrane surface
(continued)
Emulsification by Membrane Operations 3
Comparing to the conventional emulsification emulsification with pulsed (oscillatory) flow. Ind Eng
processes, emulsification by membrane operation Chem Res 52:507–515
Koris A, Piacentini E, Vatai G, Bekassy-Molnar E,
permits to obtain a better control of droplet size Drioli E, Giorno L (2011) Investigation on the effects
and droplet size distribution, low energy and of a mechanical shear-stress modification method dur-
material consumption, and modular and easy ing cross-flow membrane emulsification. J Membr Sci
scale-up. Nevertheless, productivity (m3/day) is 371:28–36
Kukizaki M (2009) Shirasu porous glass (SPG) membrane
much lower, and therefore the challenge in the emulsification in the absence of shear flow at the
future is the development of new membranes and membrane surface: influence of surfactant type and
innovative membrane operations to keep the concentration, viscosities of dispersed and continuous
known advantages and maximize the phases, and transmembrane pressure. J Membr Sci
327:234–243
productivity. Stillwell MT, Holdich RG, Kosvintsev SR, Gasparini G,
Cumming IW (2007) Stirred cell membrane emulsifi-
cation and factors influencing dispersion drop size and
uniformity. Ind Eng Chem Res 6:965–972
References Vladisavljević GT, Williams RA (2006) Manufacture of
large uniform droplets using rotating membrane emul-
Holdich RG, Dragosavac MM, Vladisavljevic GT, sification. J Colloid Interface Sci 299:396–402
Kosvintsev SR (2010) Membrane emulsification with Williams RA, Peng SJ, Wheeler DA, Morley NC,
oscillating and stationary membranes. Ind Eng Chem Taylor D, Whalley M, Houldsworth DW (1998) Con-
Res 49:3810–3817 trolled production of emulsions using a crossflow
Holdich RG, Dragosavac MM, Vladisavljevic GT, membrane, part II: industrial scale manufacture.
Piacentini E (2013) Continuous membrane Chem Eng Res Des 76:902–910
C
Controlled Drug Release particular site and contain drug in liquid or pow-
der form in a reservoir surrounded by a semiper-
Sacide Alsoy Altinkaya meable membrane to allow slow release of the
Department of Chemical Engineering, Izmir drug. The membrane can be made from a degrad-
Institute of Technology, Urla, Izmir, Turkey able or nondegradable polymer, and the release is
controlled by rate of diffusion and degradation.
Patches are typical membrane-controlled reser-
Controlled drug release is defined as delivery of a voir systems and frequently used for controlled
drug to a specific site, in specific time and release drug delivery. In ocular patches, a drug is
pattern. Controlled drug release eliminates over- enclosed by two release-controlling polymer
or underdosing, maintains drug levels in desired membranes, and through diffusion, drug is deliv-
range, needs less dosing, prevents side effects, ered to the target area. Transdermal patches are
and increases patient compliance. Most of the used to deliver drugs with low solubility since the
commercially available systems for controlled skin has a large surface area. The simplest patch
release of drugs rely on membranes where drug consists of a drug-containing reservoir placed
release is generally controlled by (1) osmotic between an impermeable backing layer and a
pumping or (2) solution–diffusion mechanism. membrane. The total resistance to drug perme-
Pills, implants, and patches are commonly used ation is controlled by sum of the resistances in the
dosage forms to deliver drugs where drug release membrane and the skin. In the case of passive
is controlled by diffusion through a rate-limiting drug transport where the drug concentration dif-
membrane. Pills are prepared by pressing the ference between the patch and the skin is main
drug into a tablet and then coating with a water- driving force, the release rate of the drug may
insoluble or water-soluble polymeric membrane, vary significantly from patient to patient due to
such as hydroxylpropyl methylcellulose, strong variations in skin permeability. In order to
ethylcellulose, povidone, or polyethylene glycol. provide an effective rate control and to ensure
Tablets are also coated with a membrane to pro- that drug delivery does not depend on patient or
tect drugs against decomposition in the acid envi- patch position, the permeability of membrane
ronment of the stomach. Commonly used should be less than that of the skin, i.e., the
polymers for this purpose are cellulose acetate release rate should be controlled by the mem-
trimellitate (CAT), hydroxypropylmethyl- brane. To expand the spectrum of transdermally
cellulose phthalate (HPMCP), polyvinyl acetate deliverable drugs, chemical permeation
phthalate (PVAP), and cellulose acetate phthalate enhancers, microneedles, ultrasound, heat, or
(CAP). Implants are used to deliver drug at a short- or high-voltage bursts of electricity are
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1234-2
2 Controlled Drug Release
temporarily applied to the skin to disrupt its bar- stimuli-responsive polymers are also used as
rier function. Alternatively, drugs can be deliv- membrane material for controlling the release
ered by iontophoresis, in which small amounts of rate of drugs through the membrane. For exam-
electrical current are applied through the skin to ple, hydrogel membranes manufactured from
allow delivery of charged drug molecules into the glucose-containing copolymers could respond to
body. The device consists of two patches: one of the dynamic changes in external glucose concen-
them contains a drug reservoir, while the other tration, and this response can be used to control
patch contains reference electrolyte or gel. The the release of insulin through the hydrogel mem-
drug placed in the patch electrode which has the brane (Obaidat and Park 1997).
same charge as the drug is delivered into the skin
by electrostatic repulsion when electric current is
applied. The rate of transport of a charged drug
Reference
during iontophoresis is controlled by passive dif-
fusion, migration due to electric current applied, Obaidat AA, Park K (1997) Characterization of protein
and electroosmosis due to bulk fluid flow in the release through glucose-sensitive hydrogel mem-
same direction as the flow of the counter ions. In branes. Biomaterials 18:801
addition to classical polymers, intelligent,
C
another commercial implant used for treatment of less cleared than free drugs and they may also
advanced prostate cancer. have favorable distribution properties into target
Drug-eluting stents were developed to prevent tissues. Targeting ligands can be incorporated
restenosis or reclosing of coronary arteries. In into the nanoparticles, and they permit particles
these systems, the implantable metal stents are to bind specific cells and promote the cell uptake
coated with small amounts of anti-inflammatory and release of drug into the cells. Drug-loaded
and antiproliferative drugs that are released nanoparticles can easily reach to target tumor
directly into the arterial tissue by dissolution, tissues since tumors have leaky capillaries that
partitioning, and diffusion. The release rate is permit the passage of nanoparticulates.
influenced by the thickness of the coating, type Microemulsions, liposomes, dendrimers, block
of the coating material, and diffusivity and solu- polymer micelles, and solid lipid and polymer
bility of drug in the coating material. nanoparticles are typical examples of
Nanocarriers are alternative systems for nanocarriers.
targeted controlled drug delivery since they are
C
Controlled-release systems that are not depen- system releases the agent in a way typical of
dent on diffusion have also been developed. For diffusion-controlled matrix systems upon expo-
example, in the case of bioerodible systems, the sure to aqueous media. On other hand, when the
release rate is controlled by either polymer dis- system is exposed to an oscillating external mag-
solution or a chemical reaction at the polymer netic field, the release rate becomes much higher.
surface; therefore, geometric shape of the release Various types of polymers have been used in
system is important. In pendant chain systems, the design of controlled-release systems. The
the active agent is bound to a polymer backbone choice of polymer can affect diffusion and parti-
chain chemically and is released by hydrolytic or tion coefficients in diffusion-controlled systems,
enzymatic cleavage. The agent can be attached the rate of erosion or hydrolysis in chemically-
directly or via a spacer group. The spacer group controlled systems, permeation rates of solvents
can be used to affect the release rate and hydro- in swelling-controlled systems, and mechanical
philicity of the system. In a magnetically forces in magnetically controlled systems.
controlled-release system, the active agent is uni-
formly dispersed within a polymer matrix. The
C
kinetics is observed and the release rate is and Csa is the solubility of the active agent in the
predicted by Eq. 4 (Baker and Londsdale 1974): membrane.
In swelling-controlled release systems, the
dMt A DCms ð2C1 Cms Þ 1=2 release rate depends on the degree of swelling
¼ (4) of the matrix which is influenced both by the
dt 2 t
diffusion of solvent into the polymer and relaxa-
where Cms is the saturation concentration of the tion of the polymer chains. When diffusion is the
active ingredient in the polymer and C1 is the rate-controlling step, t1/2 kinetics is observed
concentration of active ingredient initially loaded and the release controlled by relaxation follows
into polymer matrix. zero-order release kinetics (Alfrey et al. 1966).
Osmotic-controlled release which is usually
reservoir-type systems follow zero-order release
kinetics as long as the osmotic pressure gradient References
through the membrane is constant. The release
rate of the active agent from these types of sys- Alfrey T, Gurnee EF, Lloyd WG (1966) Diffusion in
tems is defined with the following equation glassy polymers. J Polym Sci C 12:249
Baker RW, Londsdale HK (1974) Controlled release:
(Theeuwes et al. 1983):
mechanisms and rates. In: Tanquary AC, Lacey RE
(eds) Controlled release of biologically active agents.
dMt APw DpCsa Plenum Press, New York, pp 15–72
¼ (5) Theeuwes F, Swanson D, Wong P (1983) Elementary
dt L
osmotic pump for ındomethacin. J Pharm Sci 72:253
where Pw is the permeability of water through the
membrane, Dp is the osmotic pressure difference,
C
@C
Controlled Release by Membrane J ¼ DK (2)
@x
Sacide Alsoy Altinkaya
where C is the concentration of drug in the sur-
Department of Chemical Engineering, Izmir
rounding medium. Under steady-state conditions,
Institute of Technology, Urla, Izmir, Turkey
flux through the membrane is obtained by inte-
grating Eq. 2.
Many controlled-release systems commercially
DC
available now are based on membrane technol- J ¼ DK (3)
L
ogy. These systems consist of a core containing
the drug surrounded by a thin polymer membrane Controlled-release systems based on membranes
and transport of drug through membrane occurs usually provide constant release rate as long as
by a solution-diffusion mechanism. Drug mole- the concentration of drug within core is at satu-
cules first dissolve in the membrane and then ration concentration. Deviations from constant
diffuse from interior part of the membrane to its release kinetics occur depending on the storage
surface. The diffusive flux through the membrane history of the release device. Time lag is observed
is described by Fick’s first law of diffusion. when the system is used shortly after being
manufactured while migration of the agent from
@Cm the core into the membrane due to long-term
J ¼ D (1)
@x storage causes initial burst effect. Equation 3
clearly shows that the release rate of drug is
where D is the diffusivity of drug in the mem-
controlled by diffusivity and solubility of drug
brane, J is the flux of the drug, and Cm is the
in the membrane as well as the thickness of the
concentration of drug in the membrane. At the
membrane. Diffusivity of drug in the membrane
membrane surface, drug molecules choose to
is influenced by the size and shape of the drug
partition into either membrane or surrounding
molecules, flexibility, packing density, or crys-
medium. The partition coefficient gives a mea-
tallinity of polymer chains. Flexibility of polymer
sure of the preference of drug molecules between
chains depends on glass transition temperature
two phases. Defining the partition coefficient, K,
and degree of crosslinking of the polymer. Diffu-
as the ratio of the concentration in the membrane
sivities are higher in rubbery polymers than those
to the concentration in the solution, flux in Eq. 1
in glassy polymers and decrease as crosslinking
is rewritten as follows:
density in the polymer increases. Diffusion takes
place in the amorphous phase of the polymers; applications. These devices contain the drug
therefore, diffusivities are lower in more- either in a reservoir surrounded by a membrane
crystalline polymers than in less-crystalline or dispersed in a polymeric matrix and deliver
ones. Solubility of drugs in the membrane drugs directly through the skin and into the blood-
depends on the interaction between the polymer stream. The flux of the drug through the skin is
and drug. Simply, solubility of drug is higher in enhanced by using penetration enhancers or elec-
polymers containing similar functional groups tric current. Osmotic controlled-release systems
with those of drug, in addition, solubility also depend on diffusion of water across a semi-
decreases with an increase in crystallinity of the permeable membrane. These systems for oral
polymer. Design of membrane-based controlled- delivery of drugs are prepared by compressing
release system for a particular drug requires to an osmotically active agent into a tablet, coating
choose an appropriate polymer as a membrane the tablet with a semipermeable membrane, and
material and appropriate thickness to adjust the drilling a small hole through the coating. As
release rate at a desired level. water permeates through the membrane into the
Diffusion-controlled release systems are com- tablet, a solution of the agent is pumped out of the
monly used in commercial products and the most hole. Such a device provides a constant rate of
successful example is in transdermal release as drug traverses the gastrointestinal tract.
C
dosage form should deliver the drug within 24 h Drug is released rapidly if the molecular weight
which corresponds to the total gastrointestinal of the polymer is low. If a high molecular weight,
tract (GI) transit time in humans. To protect water-soluble polymer is used for coating, ini-
drug from hydrolysis in acidic environment of tially it swells into a gel through which drug
the stomach, dosage forms are prepared with diffuses. Following ingestion, the rate of swelling
membranes made from pH-sensitive polymers and diffusion through the membrane affect the
that are insoluble in acid but dissolve in the neu- time for passage of the dosage form through the
tral or slightly alkaline environment of the gut. stomach to the small intestine.
R
When highly swellable polymers are used as since this condition promotes repulsion between
packaging material, in addition to diffusion of them. Thus, the choice of the polymer matrix for
the antimicrobial agent, diffusion of water into the charged antimicrobial agent should be done
the matrix and the rate of swelling of the matrix based on the pH of the target food.
are also important factors that control the release
rate of the antimicrobial agent. In cases where the
characteristic diffusion time is lower than the References
relaxation time of the polymer, relaxation
becomes the limiting phenomena controlling the Buonocore GG, Sinigaglia M, Corbo MR, Bevilacqua A,
La Notte E, Del Nobile MA (2004) Controlled release
solvent uptake, consequently the release of the
of antimicrobial compounds from highly swellable
antimicrobial agent. Food packaging materials polymers. J Food Prod 67:1190
based on proteins or polysaccharides are usually Gemili S, Yemenicioglu A, Altınkaya SA (2009) Devel-
charged at the pH of the release medium. When opment of cellulose acetate based antimicrobial
food packaging materials for controlled release of
both the antimicrobial agent and the food pack-
lysozyme. J Food Eng 90:453
aging material are charged, then the release rate Han JH, Floros JD (1998) Simulating diffusion model and
depends on the pH of the release medium. In this determining diffusivity of potassium sorbate through
case, the release of the agent occurs only if both plastic to develop antimicrobial packaging films.
J Food Proc Preserv 22:107
the agent and the polymer are similarly charged
U
of the membrane were generated by different which clearly indicates the beneficial effect of a
surface modification techniques and by cross- polyelectrolyte environment. Immobilization of
linking with multifunctional, low molecular urease in between two polyelectrolyte layers
reagents. In recent years, the layer-by-layer decreased the activity compared to the previous
assembly technique was shown to be an efficient case most probable due to the diffusion-limited
method for enzyme immobilization (Smuleac accessibility of the catalytic site. Adsorption of
et al. 2006). The method involves layer-by-layer negatively charged urease directly onto nega-
deposition of oppositely charged polyelectrolytes tively charged support resulted in a loss of
by consecutive, alternating immersion of a enzyme activity in a short period of time. On
charged substrate into aqueous solutions of an the other hand, immobilization of urease between
anionic and a cationic polyelectrolyte. Since two polyelectrolyte layers appeared to bring bet-
enzymes are multiply charged molecules, the ter environment to ensure long-term enzyme
layer-by-layer (LBL) assembly offers a simple stability.
method to perform the immobilization. In some
cases, electrostatic interactions in the assembly
help stabilize the enzymes to maintain their activ-
References
ity. The LBL method was used to immobilize
urease on polystyrene particles, silicon Guedidi S, Yurekli Y, Deratani A, Dejardin P, Innocent C,
microchannels, or NH3 electrode (Krajewska Altinkaya SA, Roudesli S, Yemenicioglu A (2010)
2009). Guedidi et al. (2010) immobilized urease Effect of enzyme location on activity and stability of
on polyacrylonitrile-based membranes using trypsin and urease immobilized on porous membranes
by using layer-by-layer self-assembly of polyelectro-
LBL assembly. The optimum pH for both native lyte. J Membr Sci 365:59
and immobilized urease was found to be at about Krajewska B (2009) Properties and their customizing by
seven. Immobilized form of urease retained enzyme immobilizations: a review. J Mol Catal
higher activity at lower pH than the soluble coun- B Enzym 59:22
Smuleac V, Butterfield DA, Bhattacharyya D (2006)
terpart. Immobilization onto a polyelectrolyte Layer-by-layer-assembled microfiltration membranes
layer (urease forms the last layer of the assembly) for biomolecule immobilization and enzymatic catal-
resulted in a higher catalytic activity than that of ysis. Langmuir 22:10118
enzyme directly immobilized on the membrane
H
Hemodialysis (HD) and Hemodiafiltration (HDF) with high water removal, partially replaced by
sterile dialysate. In addition, polymeric mem-
HD HDF branes are often more biocompatible than cellu-
losic ones. They are also superior for patient
Post dilution quality of life, reducing b2-M amyloidosis, infec-
tions, and loss of residual kidney function. High-
flux membranes with larger pores increase
removal of middle molecules such as b2-
microglobulin, cytokines, resistin, immunoglob-
ulins, parathyroid hormones, and dinucleoside
polyphosphates. Their removal protects the
patient against cardiovascular problems and
other side effects of uremic syndrome
(Vanholder et al. 2011).
References Chuang FR, Lee CH, Chuang HW, Lee CN, Chen TC
(2008) A quality and cost benefit analysis of dialysers.
Bouré T, Vanholder R (2004) Which dialyser membrane Ren Fail 30:521–526
to choose? Nephrol Dial Transplant 19:293–296 Vanholder R, Glorieux G, Van Biesen W (2011) Advan-
tages of new hemodialysis membranes and equipment.
Nephron Clin Pract 114:c165–c170
H
Hollow Fibre Enzymatic Reactor, the axial space coordinate, m. The momentum
Modeling of equations are as
Endre Nagy @u @u @p
r u þu ¼
Research Institute of Chemical and Process @r @z @z
Engineering, University of Pannonia, Veszprèm,
@ 1 @ ðruÞ @2u
Hungary þm þ 2
@r r @r @z
(2)
Modeling of hollow fiber enzymatic reactor.
@u @u @p
The complete description of the transport of r u þu ¼
fluid in hollow fiber capillary membrane requires @r @z @z
that the local transport equations that describe the @ 1 @ ðruÞ @2u
þm þ 2
flow and transport conditions should be solved. @r r @r @z
The starting Navier-Stokes flow models (Bird (3)
et al. 1960) are very complex; significant simpli-
fication is needed to obtain applicable model for and for solute concentration in case of constant
engineering points of view. In a capillary mem- density
brane with permeable wall, three regions of flow
should be considered: flow in lumen, within @c @c @ @c 1 @ ðDcÞ
membrane matrix, and in the extracapillary u þu ¼ D þ
@z @r @r @r r @r
space (Nagy 2011, p. 179). Let us consider a
@ @c
steady-state, laminar, incompressible, isother- þ D (4)
mal, fully developed flow in vertically oriented @z @z
tube; thus the Navier-Stokes equations (Bird
et al. 1960) will be as the continuity equation: where r is the density, p is the pressure, m is
dynamic viscosity, and g is gravitational
1 @ @u acceleration.
ðrur Þ þ ¼0 (1) Equations 2 and 3 may be reduced by consider-
r @r @z
ing the fact that for a small wall Reynolds number,
where u is the axial convective velocity, m/s; ur is the inertial terms can be negligible. In most viscous
the transverse convective velocity, m/s; and z is flows, normal stress effects,@ 2 u=@z2, are negligible
when the ratio, ro/L (L is length of capillary, ro is
lumen radius), is less than 102, a condition that is Replacing Eq. 10 into Eq. 5, one can get for the
satisfied in almost all hollow fiber membrane radial convective velocity in the lumen side (for
devices. Depending on the transmembrane convec- distinction for the membrane’s velocity, f sub-
tive velocity, the axial velocity often can be much script denotes the fluid phase here in the lumen
larger than that of the permeation rate. Due to its side)
large values, the axial diffusion term can be
( )
neglected. The radial convective velocity is rather r3o r 1 r 3 d2 pt
low; accordingly, momentum equation of the trans- ut ¼ (11)
m8 ro 2 ro dz2
verse velocity can be neglected. Accordingly,
Eqs. 2 to 4 can be simplified as
From Eq. 11 the wall velocity, uw, can be given as
@p 1 @ @u
0¼ þm r (5) r3o @ 2 pt
@z r @r @r uw ¼ (12)
16m @z2
The component balance will be as:
The radial convective velocity through the mem-
brane can also be expressed by the next equation
@ci @ @c
u ¼D r (6) ▶ Biocatalytic membrane reactor: mass transport
@z @r ℑ r
as
When Eq. 6 is integrated twice with respect to r,
k r o pt ð z Þ pe ð z Þ
one can get as uM ðr, zÞ ¼ (13)
em r lnð1 þ d=ro Þ
dp r2
u¼ þ Alnr þ B (7) From equality of Eqs. 12 and 13, a second-order
dz 4 differential equation can be obtained neglecting
For the hydrodynamic analysis in the lumen and the radial pressure gradient (Nagy 2011, p. 187).
in the shell, the continuity Eq. 1 and the momen- Solving this equation the p(z) and uw(z) functions
tum Eq. 5 have to be solved with suitable bound- can be obtained (Nagy 2011). This convection
ary conditions. In the lumen (t) these are velocity can then be replaced in the mass balance
equation for the membrane (see “▶ Biocatalytic
@u Membrane Reactor: Mass Transport).
at r ¼ 0 then ¼ 0, u ¼ 0; (8)
@z
Spacer Arm Length the base support and one to serve as the chro-
matographic ligand (Zou et al. 2001).
Jiahui Shao For charge-modified membranes with differ-
School of Environmental Science and ent spacer arm lengths, recent researchers dem-
Engineering, Shanghai Jiao Tong University, onstrated that the spacer arm length can have a
Shanghai, People’s Republic of China strong effect on the performance characteristics
of electrically charged membranes by electro-
static exclusion effects. Even though the hydrau-
The spacer arm length refers to the length of lic permeabilities of these membranes were
hydrocarbon chain between the solid support essentially identical, membranes with larger
and the functional ligand. spacer arm length have greater retention of a
For ion exchange and affinity chromatogra- like-charged molecule. The greater retention
phy/membrane, studies have demonstrated that with larger spacer arm length is directly related
the spacer arm length can affect the overall sys- to the effective surface charge or apparent zeta
tem performance. In general, when the potential (Rohani and Zydney 2010; Shao et al.
immobilized ligand is a small molecule, such as 2013). The permeability-selectivity trade-off plot
a receptor substrate or a chemical antigen, steric for the charge-modified membranes with differ-
hindrance occurs between the immobilization ent spacer arm length demonstrated that the
support and the substance to be isolated. This electro-static interactions led to much better
phenomenon may cause a reduction or complete ultrafiltration performance of enhanced selectiv-
lack of specific binding (Zou et al. 2001). To ity and permeability than could be obtained with
overcome this problem, it is often necessary conventional (neutral) membranes. Figure 1
either to select a different support (i.e., one with shows a plot of the selectivity (or separation
a spacer arm already attached) or to bind a spacer factor) as a function of the permeability for cyto-
molecule to the support prior to attaching the chrome c for unmodified and positively charged
ligand. An optimal spacer arm ensures that the versions of composite regenerated cellulose
functional groups are placed a suitable distance ultrafiltration membranes. The format for plot-
from the surface of the solid support and are ting the data is analogous to the classical Robeson
easily accessible to the macromolecules. An plot used to analyze the behavior of gas separa-
ideal spacer arm should have (1) proper length tion membranes. High-performance membranes
(at least three atoms), (2) no active center that would lie in the upper right hand corner of the
could cause nonspecific adsorption, and (3) at plot, having both large selectivity and large per-
least two functional groups, one to react with meability. Unmodified and po. For example, at a
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1244-2
2 Spacer Arm Length
Selectivity, 1/Sa
membranes. The solid and
dashed curves represent
model calculations for an 100
uncharged membrane and a
positively charged
membrane consisting of a
parallel array of cylindrical
10
pores with a log-normal
pore size distribution
(Rohani and Zydney 2010)
1
0 5 10 15 20 25 30
Permeability, ¥ 10–10 (m/s/Pa)
hydraulic permeability of about 6.0 10 10 m/s/ diaminodecane in combination with the greater
Pa (15 L/m2/h/psi), the selectivity for the posi- displacement of the charge functionality into the
tively charged membrane is more than three interior of the membrane pore for the larger
orders of magnitude larger than that of the ligand. Later, Shao et al. (2013) generate a series
unmodified membrane. The charge-modified of negatively charged ultrafiltration membranes
membranes with different spacer arm lengths that differed in spacer arm length by covalent
can be well exploited to enhance the performance attachment of negatively charged group to a com-
of ultrafiltration processes for real applications. mercially available regenerated cellulose mem-
Mehta and Zydney (2008) generated a series of brane. Results indicated that the membrane with
positively-charged membranes with different larger spacer arm length has better rejection of
spacer arm length by activation of base cellulose humic acid and less membrane fouling compared
membrane with epichlorohydrin followed by to that with smaller spacer arm length, which is
reaction with diamines having different numbers also consistent with the larger charge of the mem-
of alkyl groups between the two amines. Experi- brane having larger spacer arm length.
mental data showed that at low ionic strength
(5 mM), the observed sieving coefficient for cyto-
chrome c through the 30 kDa membrane made
References
with 1,10-diaminodecane (n = 10) was more than
an order of magnitude smaller than that for a Mehta A, Zydney AL (2008) Effect of spacer arm length
similar membrane made using 1,2-diaminoethane on the performance of charge-modified ultrafiltration
(n = 2) even though these membranes had very membranes. J Membr Sci 313:304–314
similar hydraulic permeabilities and pore size Rohani MM, Zydney AL (2010) Role of electrostatic
interactions during protein ultrafiltration. Adv Colloid
distributions, where n is the number of alkyl Interf Sci 160:40–48
groups between the amine functionalities. This Shao J, Zhao L, Chen X, He Y (2013) Humic acid rejec-
large reduction in the protein sieving coefficient tion and flux decline with negatively charged mem-
was found to be consistent with the observed branes of different spacer arm lengths and charge
groups. J Membr Sci 435:38–45
increase in the membrane zeta potential, which Zou H, Luo Q, Zhou D (2001) Affinity membrane chro-
was most likely due to the increase in net charge matography for the analysis and purification of pro-
associated with the reduction in electrical inter- teins. J Biochem Biophys Methods 49:199–240
actions between the two amine groups in the
U
generally classified into two main configura- membrane with photocatalyst (such as TiO2)
tions: (a) reactors with photocatalyst particles on the surface or entrapped in, the fouling can
suspended in feed solution and (b) reactors be effectively controlled because the pollut-
with photocatalyst immobilized on/in the ants can be effectively degraded by the
membrane. The major disadvantage of the photocatalyst with UV irradiation during fil-
configuration with photocatalyst in suspension tration process. The fouled membranes after
is deterioration of the permeate flux and mem- membrane filtration can also be cleaned with
brane fouling. PMRs with photocatalyst on/in only UV irradiation, which provides the
membrane are one solution for this problem. photocatalyst-doped membrane self-cleaning
In this configuration, oxidation by hydroxyl property (Song 2012).
radicals occurs on the external surface and
within the pores of the membrane, while reac-
tants are permeating in a one-pass flow. How- References
ever, fixation of the photocatalyst often results
in a loss of photoactivity and might cause He D, Susanto H, Ulbricht M (2009) Photo-irradiation for
preparation, modification and stimulation of polymeric
destruction to the membrane structure
membranes. Prog Polym Sci 34:62–98
(Mozia 2010). Mozia S (2010) Photocatalytic membrane reactors
3. UV irradiation for membrane fouling/biofoul- (PMRs) in water and wastewater treatment.
ing control and membrane clean. UV irradia- A review. Sep Purif Technol 73:71–91
Song H, Shao J, He Y, Liu B, Zhong X (2012) Natural
tion integrated in membrane system is able to
organic matter removal and flux decline with PEG-
mitigate membrane biofouling, which is TiO2-doped PVDF membranes by integration of ultra-
caused by deposition or growth of microor- filtration with photocatalysis. J Membr Sci 405: 48–56
ganisms on membrane causes. For the
P
Pore Forming Agent agents may eventually leach out from the
resulting membrane due to their relative small
Jiahui Shao sizes and their high affinity to the water (Liu
School of Environmental Science and et al. 2011).
Engineering, Shanghai Jiao Tong University, Pore-forming agents are mainly divided into
Shanghai, People’s Republic of China three categories: (1) low molecular weight inor-
ganic salts; (2) high molecular weight additives,
known as polymeric additives; and (3) other types
High porosity, suitable pore size, and pore size of additives. Sometimes, mixture of more than
distribution are essential for the usefulness of the one agent is used to provide the membrane with
membranes. In order to improve the membrane appropriate permeation properties:
permeation properties, a commonly adopted
approach is adding pore-forming agents 1. Low molecular weight inorganic salts: These
(additives) in casting solution through adjusting inorganic salts include lithium chloride (LiCl),
the membrane structure. Based on the fundamen- zinc chloride (ZnCl2), magnesium chloride
tal concept that the sublayer of asymmetric poly- (MgCl2), calcium chloride (CaCl2), lithium
meric membrane is strongly influenced by the perchlorate (LiClO4), magnesium perchlorate
additives and that of their aggregates which are (Mg(ClO4)2), calcium perchlorate (Ca
in the casting solution, there is always an ongoing (ClO4)2), and others. Currently, lithium chlo-
research in exploring new suitable additives for ride (LiCl) is commonly used. It is generally
membrane making (Mohanty and Purkait 2011). believed that ion-dipole interactions between
It is generally believed that pore-forming agents metal ions and membrane polymers enhance
increase the polymer dope viscosity, create a the demixing process and form more and
spongy membrane structure by prevention of larger pores (Mohanty and Purkait 2011).
macrovoid formation, enhance the pore intercon- With these inorganic salts added, the mem-
nectivity when added in appropriate amounts, or brane porosity increases while the mean pore
speed up the displacement of solvent with size is almost constant, which causes the water
non-solvent in the coagulation bath, that is, flux to significantly increase without causing
enhance the liquid-liquid demixing process dur- an obvious drop in solution rejection.
ing precipitation of the dope solution, and there- 2. Polymeric additives: Polymeric additives are
fore the formation of larger pores is favored. normally hydrophilic in nature. These addi-
However, the mechanical strength of these mem- tives not only enhance the permeation proper-
branes normally decreases, and pore-forming ties of the membrane but also increase its
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1253-2
2 Pore Forming Agent
hydrophilicity. Polyvinylpyrrolidone (PVP) decreases but normally does not have signifi-
and poly(ethylene glycol) (PEG) are com- cant reduction.
monly used and studied. The addition of poly- 3. Other types of additives: Other frequently
meric membranes promotes non-solvent flux used pore-forming agents include glycerol,
upon immersion in the coagulation bath, thus water, alcohol, formamide, and polyethylene
favoring the formation of large finger-like oxide (PEO) or the mixture of them.
macrovoids. The membrane permeation prop-
erties change with the concentration and
molecular weight of the polymer added. Gen-
References
erally, as the concentration of adding polymer
increases, the membrane porosity and perme- Liu F, Hashim NA, Liu Y, Abed MRM, Li K (2011)
ation flux increase. The membrane porosity Progress in the production and modification of PVDF
and permeation flux normally also increase membranes. J Membr Sci 375:1–27
with increasing molecular weight of the poly- Mohanty K, Purkait MK (2011) Membrane technologies
and applications. CRC Press, New York
mer (Mohanty and Purkait 2011); Liu
et al. 2011). However, the solute rejection
S
where:
The ▶ solubility parameter d is a thermodynamic
quantity introduced by Hildebrand and Scatchard xi v~i
Fi ¼ (4)
(HS) to describe the behavior of the so-called x1 v~1 þ x2 v~2
regular solutions. Such solutions have a negligi-
ble mixing volume and excess entropy of mixing, And for the activity coefficient of species i:
so that the excess Gibbs free energy coincides 2
with the mixing enthalpy. The HS model uses RTlngi ¼ v~i F2j di dj (5)
the idea of cohesive energy density (CED), that
is, the difference between the internal energy of The model is predictive for the solubility as far as
the system and that of the corresponding system the d values of the two species are known and the
in the ideal gas state, per volume of liquid sub- theory can depict correctly the physical behavior
stance, estimated as follows: (Sandler 2006) of the mixture; indeed the equilibrium composi-
tion or solubility can be found applying the phase
~ VAP
DU equilibrium condition for the solute species.
CED ¼ L!IG
Although the HS theory is not always appro-
v~L
priate, especially for solutions containing poly-
~ VAP
DH RT
¼ L!IG
(1) mers, as it does not account for mixing volume
v~L and excess entropy of mixing, and it uses the
geometric mean rule assumption for the binary
And the solubility parameter d is defined as: interactions between unlike molecules, the d
pffiffiffiffiffiffiffiffiffiffi value is widely used to estimate a priori the
d CED (2) mutual solubility of two species. Two species
with similar d values show little excess free
The solubility parameter is related to the molar energy and are mutually soluble in the entire
~ EX , and to the mixing
excess Gibbs free energy, G
composition range. Two components with dis- but it accounts also for the polar groups interac-
similar solubility parameters have high values tions and for the hydrogen bonds:
of the excess free energy and can show a
miscibility gap. CED ¼ CEDD þ CEDP þ CEDH (6)
In gas sorption in membrane systems the
values of solubility is higher if the gas and poly- And correspondingly:
mer solubility parameters are similar, and lower
if they are dissimilar, at fixed condensability of d2 ¼ d2D þ d2P þ d2H (7)
the gaseous penetrant.
In some cases, it is evident that the solubility Some values of the solubility parameters for
of different fluids in a membrane is strongly cor- polymers of interest in membrane separations,
related to the solubility parameter difference. as measured from mixture data and as estimated
Normally d values are tabulated at 25 C and by the group contribution method of Hoftyzer and
their value is almost constant with temperature. Van Krevelen are reported in Table 1 (Van
For fluids, the values are easily retrievable. For Krevelen 1990).
polymers, the vaporization quantities cannot be
measured, and the d values can be estimated from
experimental mixing data or with group contri- References
bution methods like the ones by Hoftyzer and
Van Krevelen and by Hoy (Van Krevelen 1990). Sandler SI (2006) Chemical, biochemical and engineering
In both methods the same assumption is made thermodynamics, 4th edn. Wiley, New York
van Krevelen DW (1990) Properties of polymers: their
that the cohesive energy is not only represented correlation with chemical structure; their numerical
by the dispersion interaction forces between mol- estimation and prediction from additive group contri-
ecules, as originally assumed by the HS theory, butions, 3rd edn. Amsterdam, Elsevier
L
LTA Zeolite Membranes in Pervaporation, Table 1 Typical PV/VP performances of LTA zeolite membrane for
dewatering organics
Feed solution (10 wt.% of water) Temperature [ C] Water flux (kg/m2h) Separation factor
Water/methanol 65 (PV) 0.6 116
Water/ethanol 65 (PV) 1.0 10,000
Water/ethanol 120 (VP) 3.1 10,000
Water/n-propanol 110 (VP) 2.5 10,000
Water/i-propanol 65 (PV) 1.8 10,000
Water/ethyl acetate 65 (PV) 1.2 10,000
Water/acetone 50 (PV) 0.9 10,000
Water/i-propylamine 105 (VP) 3.2 10,000
L
LTA Zeolite Membranes, Fig. 1 (a) Framework structure of LTA zeolite, (b) typical SEM image of a NaA zeolite
single crystal, (c, d) typical SEM image of a LTA zeolite membrane
Bioinspired Membranes,
Fig. 1 Concept of
nanotube-based
hierarchically structured
membrane with durable
high permeability and
selectivity
membrane may turn to improving the fundamen- membranes show great promise in membrane
tal mechanism and extending the application science and technology (Tokarev and Minko
fields. Of course, new bioinspired platform tech- 2010). For instance, self-healing membrane,
niques will be continuously explored. self-cleaning membrane, and many sorts of
Selective transport properties and the stimuli-responsive membranes have been
corresponding membrane structures are another reported (Chen et al. 2011; Wang et al. 2011b;
major concern in bioinspired membrane realm. In Capadona et al. 2008; Tokarev and Minko 2010).
biology, the most effective membrane-mediated Such smart behaviors can endow the membrane
separation/transport processes often involve with ultra-high stability, switchable permeation
complex, nonplanar articulations of structure flux, alternative driving force, etc. Other proper-
that are highly optimized to support the multiple ties, such as mechanical strength, interface adhe-
functions. Inspired by the hierarchical structures sion, water retention, etc., have been successfully
in biology, rational design and synthesis hierar- reinforced by learning from nature (Zeng
chical structures within membranes may offer et al. 2010; Ma et al. 2010; Wang et al. 2011a).
immense opportunities for efficient molecular/ Breakthroughs in understanding how a living
ion sieving processes. For example, nanotubes system works and exploring new inspiration
have been utilized to mimic biological channels source will ensure the sustainable development
for rapid and selective molecule transport. With of bioinspired membrane.
the aid of nanotubes, an ideal concept of verti-
cally aligned biomimetic channels within a mem-
brane matrix have been proposed and shown in
References
Fig. 1, where membrane permeability, selectiv-
ity, and durability are individually manipulated Capadona JR, Shanmuganathan K, Tyler DJ, Rowan SJ,
by the highly permeable nanopores, the entrance Weder C (2008) Stimuli-responsive polymer
chemistry of the nanotube, and the robust nanocomposites inspired by the sea cucumber dermis.
nonporous filling matrix. Here, the aligned Science 319:1370–1374
Chen WJ, Su YL, Peng JM, Dong YA, Zhao XT, Jiang ZY
nanotubes are extremely like the channel proteins (2011) Engineering a robust, versatile amphiphilic
inserted through cell membranes. This concept membrane surface through forced surface segregation
has partially come true recently (Xu et al. 2011), for ultralow flux-decline. Adv Funct Mater
and it requires much more efforts to fulfill all the 21:191–198
Li B, Liu WP, Jiang ZY, Dong X, Wang BY, Zhong YR
potentials of this concept. Also, many block (2009) Ultrathin and stable active layer of dense com-
copolymers have been designed to mimic the posite membrane enabled by poly(dopamine). Lang-
hydrophilic-hydrophobic mosaic structure of muir 25:7368–7374
biomembrane for antifouling (Chen et al. 2011). Ma J, Zhang MH, Jiang ZY, Nie MC, Liu GX (2010) Fac-
ile fabrication of structurally stable hyaluronic acid-
Moreover, many efforts have been dedicated to based composite membranes inspired by bioadhesion.
mimicking the proton pump and ion channel so as J Membr Sci 364:290–297
to accelerate proton transport (Wang et al. 2012; Matsusaki M, Ajiro H, Kida T, Serizaw T, Mitsuru
Sharma et al. 2010). In addition to selective trans- A (2012) Layer-by-layer assembly through weak inter-
actions and their biomedical applications. Adv Mater
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Pan FS, Cheng QL, Jia HP, Jiang ZY (2010) Facile Wang M, Janout V, Regen SL (2011b) Hyper-thin organic
approach to polymer-inorganic nanocomposite mem- membranes with exceptional H2/CO2 permeation
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J Membr Sci 357:171–177 healing. Chem Commun 47:2387–2389
Rawlings AE, Bramble JP, Staniland SS (2012) Innovation Wang JT, Yue XJ, Zhang ZZ, Yang Z, Li YF, Zhang H,
through imitation: biomimetic, bioinspired and Yang XL, Wu H, Jiang ZY (2012) Enhancement of
biokleptic research. Soft Matter 8:2675–2679 proton conduction at low humidity by incorporating
Sharma M, Yi MG, Dong H, Qin HJ, Peterson E, Busath imidazole microcapsules into polymer electrolyte
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B
of BLM for its higher stability, controllability, (2) deepen the insight into the structure-function
and ability to prevent the direct contact of embed- relationship of membrane proteins.
ded proteins to solid substrate, which otherwise
will inactivate the proteins (Duong et al. 2012;
Nielsen 2009). The supported BLM or BPM can References
be prepared by several methods, of which vesicle
collapse technique is commonly used (Eeman Duong PHH, Chung TS, Jeyaseelan K, Armugam A,
and Deleu 2010). In addition to act as model of Chen Z, Yang J, Hong M (2012) Planar biomimetic
aquaporin-incorporated triblock copolymer mem-
biological membrane for investigating protein-
branes on porous alumina supports for nanofiltration.
lipid interaction, this type of biomimetic mem- J Membr Sci 409–410:34–43
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various fields by incorporating different func- biomimetic model membranes. Biotechnol Agron Soc
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Kim YR, Jung S, Ryu H, Yoo YE, Kim SM, Jeon TJ
converter, energy-production devices), (2) signal (2012) Synthetic biomimetic membranes and their
transduction (biosensor and bioanalysis), and sensor applications. Sensors 12:9530–9550
(3) substance transport and conversion (drug Li X, Wang R, Tang C, Vararattanavech A, Zhao Y,
Torres J, Fane T (2012) Preparation of supported
delivery, immobilized enzyme catalysis, and
lipid membranes for aquaporin Z incorporation. Col-
membrane-based separation). To further exploit loids Surf B 94:333–340
the application efficiency and area of biomimetic Nielsen CH (2009) Biomimetic membranes for sensor and
membrane, more efforts may be devoted to the separation applications. Anal Bioanal Chem
395:697–718
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Zhu B, Li J, Xu D (2011) Porous biomimetic membranes:
teins directly for the preparation of biomimetic fabrication, properties and future applications. Phys
membrane while acquiring the good control over Chem Chem Phys 13:10584–10592
the channel density and the protein activity and
F
membrane fouling release mechanism during separation (NIPS) process through forced surface
membrane filtration. The lower surface energy segregation showed enhanced oil, protein, and
and larger chemical heterogeneity correspond to bacteria release ability (Chen et al. 2011). The
a lower driving force for the adsorption of the low surface energy microdomains on the mem-
foulants, thereby resulting in effective fouling brane surface minimize the intermolecular forces
release ability. Surfaces which fulfill these of interactions (polar or and hydrogen-bonding
requirements are often derived from interactions) between the foulants and the mem-
polysiloxane- and fluorine-based polymers. In brane surface, remarkably reducing the flux
situ forced surface segregation of amphiphilic decline and reducing energy consumption during
copolymers and grafting low surface energy mol- the dynamic filtration process.
ecules or monomers to already formed mem- In the application of antifouling membranes
branes are popular methods to fabricated fouling for water treatment and biomedical application,
release membrane. Membranes with low surface fouling release membranes offer an interesting
energy chains (such as PDMS, poly(ethylene alternative to environmentally friendly strategies
glycol)-fluoropolymers, perfluoroalkyl polymers, to facilitate foulants removal, such as hydrocar-
perfluoropolyether polymers, and fluorine- bon substances, biomolecules, and
containing block)showed a high release rate. microorganisms.
The release rates of PDMS and perfluoroalkane
polymer-functionalized membranes are about
five times higher than those of hydrophilic sur- References
face as a result of the low interaction between the
low surface energy surfaces and protein (Thérien- Brady RF, Singer IL (2000) Mechanical factors favoring
Aubin et al. 2011). There is a growing body of release from fouling release coatings. Biofouling
15:73–81
evidence that amphiphilic or chemically hetero-
Chen WJ, Su YL, Peng JM, Dong Y, Zhao XT, Jiang ZY
geneity membrane surfaces can present both low (2011) Engineering a robust, versatile amphiphilic
surface energy and high hydration energy membrane surface through forced surface segregation
microdomains and show promising performance for ultralow flux-decline. Adv Funct Mater
21:191–198
against a wide range of foulants. Membrane pre-
Thérien-Aubin H, Chen L, Ober CK (2011) Fouling-
pared from amphiphilic copolymers with hydro- resistant polymer brush coatings. Polymer
philic segments and fluorine-containing 52:5419–5425
segments via nonsolvent-induced phase
F
agitating agitating
agitating
Fouling Release Membranes, Fig. 1 Tentative illustration of the flux decline resistant mechanism of membranes
(Chen et al. 2011b)
surface energy microdomains prevent the coales- Chen WJ, Su YL, Peng JM, Zhao XT, Jiang ZY, Dong YN,
cence, migration, and spreading of the hydropho- Zhang Y, Liang YP, Liu JZ (2011b) Efficient waste-
water treatment by membranes through constructing
bic oil droplets or limit the accumulation/ tunable antifouling membrane surfaces. Environ Sci
coalescence of polar biofoulants, thus endowing Technol 45:6545–6552
the membrane surface with outstanding fouling Thérien-Aubin H, Chen L, Ober C (2011) Fouling-
release potential without inducing a flux decline. resistant polymer brush coatings. Polymer
52:5419–5425
Worz A, Berchtold B, Moosmann K, Prucker O, Ruhe
J (2012) Protein-resistant polymer surfaces. J Mater
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Zhao XT, Su YL, Chen WJ, Peng JM, Jiang ZY
Chen WJ, Su YL, Peng JM, Dong YN, Zhao XT, Jiang ZY (2012) Grafting perfluoroalkyl groups onto polyacry-
(2011a) Engineering a robust, versatile amphiphilic lonitrile membrane surface for improved fouling
membrane surface through forced surface segregation release property. J Membr Sci 415–416:824–834
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M
Zhongyi Jiang1, Xiaoli Wang1, Hong Wu1 and Microcapsule membrane can be categorized into
Jiafu Shi2 inorganic, organic, and inorganic–organic hybrid
1
School of Chemical Engineering and membranes based on the material composition.
Technology, Tianjin University, Tianjin, China Inorganic microcapsule membrane usually pos-
2
School of Environment Science and sesses porous structure and high mechanical sta-
Engineering, Tianjin University, Tianjin, China bility, which is often synthesized under relatively
harsh conditions (e.g., hydrothermal treatment,
calcinations, or organic solvent treatment). In
Definition comparison, the synthesis of organic microcap-
sule membrane (mainly self-assembly of amphi-
Microcapsule is defined as a hollow microsphere pathic polymer, layer-by-layer self-assembly, or
comprising large interior void and semiperme- surface polymerization) is often conducted under
able shells. The interior void serves as storage rather mild conditions; however, the mechanical
space or reaction chamber, while the shell pro- stability of organic microcapsule membrane is
tects the bioactive materials/nanoparticles in the usually much lower than that of inorganic micro-
interior void from the attack of surrounding envi- capsule membrane as a result of lack of stiff
ronment or controls the transfer of substance blocks. Recently, incorporating inorganic com-
in/out the microcapsule. Till now, microcapsule ponents/moieties into organic microcapsule
with single shell, double shells, and multiple membrane has been demonstrated as a facile,
shells as well as yolk-in-shell structure has been generic to enhance the mechanical stability.
designed and prepared. Since the shell of the Moreover, considering the advantage that hybrid-
microcapsule often possesses nanometer/ ization could offer new opportunities to create
micrometer thickness and distinct semipermeable multifunctional materials with unique properties
property, it fits the typical features of membrane. by combining the merits of inorganic and organic
Therefore, microcapsule shell can be also called building blocks, hybrid microcapsule membrane
microcapsule membrane, which was first intro- may win more promising applications in the
duced by Chang in 1960s (Chang 1964). future.
Microcapsule membrane has single-, double-,
or multiple-layered structure. Single-layered
microcapsule membrane is usually composed of
homogeneous polymers or inorganics, while
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1284-9
2 Microcapsule Membranes
double-layered microcapsule membrane is often to remove an organic pollutant (azo dye Congo
composed of two separate layers with different red) in wastewater, which was ascribed to the
kinds of materials. Multiple-layered microcap- excellent dye adsorption capability of porous
sule membrane mainly refers to the microcapsule microcapsule membrane (Fei et al. 2008). Yu
membrane which is composed of multilayers et al. prepared polymeric microcapsule mem-
through the alternative deposition/self-assembly brane and encapsulated rhodamine 6G. The cap-
of two kinds of oppositely charged polymers, sules rapidly released rhodamine 6G in ethanol
polymer/inorganic hybrids. but cannot release in aqueous solution. This was
Microcapsule has been applied in diverse because the charge density of microcapsule mem-
areas, including biocatalysis, drug delivery, pol- brane in ethanol was markedly decreased due to
lutants removal, biosensing, etc., where micro- its low dielectric constant as compared to that in
capsule membrane plays the crucial role in aqueous solution (Yu et al. 2009).
governing the overall performance of the micro-
capsule. For instance, Jiang et al. prepared
protamine–titania hybrid microcapsule mem- References
brane and encapsulated the biocatalyst enzyme
in the capsule lumen. The enhanced recycling Chang TMS (1964) Semipermeable microcapsules. Sci-
stability of enzyme was due to the high mechan- ence 146:524–525
Fei JB, Cui Y, Yan XH, Qi W, Yang Y, Wang KW, He Q,
ical stability of microcapsule membrane (Jiang
Li JB (2008) Controlled preparation of MnO2 hierar-
et al. 2009). Caruso et al. developed a redox- chical hollow nanostructures and their application in
responsive microcapsule membrane and encap- water treatment. Adv Mater 20:452–456
sulated hydrophobic cargo in the capsule lumen. Jiang YJ, Yang D, Zhang L, Sun QY, Sun XH, Li J, Jiang
ZY (2009) Preparation of protamine-titania microcap-
The cargo could be released in simulated intra-
sules through synergy between layer-by-layer assem-
cellular conditions, which were ascribed to bly and biomimetic mineralization. Adv Funct Mater
reversible disulfide linkages of membrane mate- 19:150–156
rials (Yan et al. 2011). Kreft et al. designed a Kreft O, Skirtach AG, Sukhorukov GB, Möhwald
H (2007) Remote control of bioreactions in multicom-
light-responsive microcapsule membrane and
partment capsules. Adv Mater 19:3142–3145
encapsulated dextran in the capsules. The dextran Yan Y, Wang YJ, Heath JK, Nice EC, Caruso F (2011)
is released when near-infrared laser light illumi- Cellular association and cargo release of redox-
nated the capsules, which was ascribed to the responsive polymer capsules mediated by exofacial
thiols. Adv Mater 23:3916–3921
incorporation of light-absorbing gold
Yu B, Wang D, Ye Q, Zhou F, Liu W (2009) Robust
nanoparticles into the microcapsule membrane polydopamine nano/microcapsules and their loading
(Kreft et al. 2007). Li et al. reported that the and release behavior. Chem Commun 6789–6791
porous MnO2 microcapsules showed good ability
B
1f References
Deff ¼ D
af
1þ Di Felice R, Cazzola D, Cobror S, Oriani L (2008) Oxygen
2
permeation in PET bottles with passive and active
walls. Packag Technol Sci 21:405–415
where a is the dispersed material aspect ratio. Maxwell JC (1873) A treatise on electricity and magne-
Nielsen relationship has been shown to do a sat- tism, vol 1. Clarendon Press, Oxford
isfactory job against experimental evidence Nielsen LE (1967) Models for the permeability of filled
(Di Felice et al. 2008). polymer systems. J Macromol Sci A1(5):929–942
E
sffiffiffiffiffiffiffiffi
Effectiveness Factor f¼L
k
Deff
Renzo Di Felice
University of Genova, Genova, Italy with L the pore length, k the chemical reaction
kinetic factor, and Deff the reacting species effec-
tive diffusivity.
The concept of effectiveness factor is utilized As expected the effectiveness factor
when the effect of diffusion on the overall rate approaches 1 when Thieles module is very
of a reacting process wants to be taken into small, i.e., for very short pores or very slow
account. Let’s consider a catalytic solid particle reaction or very high diffusion coefficients. On
where a reaction takes place. For a species to the other hand, for very high value of Thiele
react, it must, at the same time, diffuse inside modules, effectiveness factor approaches the
the catalytic particle and react. It is intuitive that inverse of the Thiele module.
the diffusion step slows the overall process rate, The above result can be easily generalized for
and an effectiveness factor is defined as the case of flat plate by putting L equal to half the
plate width, for the case of long cylindrical pellets
¼ by putting L equal to half the pellet radius, and to
actual rate of process
the case of spherical pellets by putting L equal to
rate of process if diffusion were infinitively fast
one third the sphere radius. Extension to kinetic
This definition is equivalent to consider reactant different from the first order has been presented in
concentration on any point in the catalytic parti- literature, and a summary can be found, for exam-
cle equal to that at the external surface. ple, in Satterfield (1991).
A rather straightforward mass balance allows
the determination of the effectiveness factor for a
single cylindrical pore where a first-order reac- References
tion is taking place on the wall:
Satterfield CN (1991) Heterogeneous catalysis in indus-
tanhf trial practice. McGraw-Hill, New York
¼
f
Liquid Entry Pressure (LEP or LEPW) Given the practical difficulty of obtaining the
exact value of the above physical parameters, it is
Renzo Di Felice not uncommon to estimate LEP experimentally,
University of Genova, Genova, Italy and Smolders and Franken (1989) described a
detailed procedure which should be followed in
this case. Basically pressure difference is gradu-
In membrane distillation it is of paramount ally applied on both side of the membrane until
importance that liquid does not fill the membrane the first drop of the liquid appears on the perme-
pores, in order to keep membrane efficiency to ate side (more specific description is given in the
the highest possible value. To this end hydropho- suggested reference). Typical values of LEP
bic membranes are normally used. The hydro- range from tenth to tens of bars (0.1–20 bar): for
phobicity can be quantified through the example, with liquid water at ambient condition,
so-called liquid entry pressure (LEP) parameter, a PTFE membrane with 95 % porosity, 25 mm
defined as the pressure difference at which liquid thickness, and 3 mm nominal pore size has an LEP
penetrates into the membranes pores. of 0.13 bar, whereas a PTFE supported mem-
The pressure required to force water through brane with 75 % porosity, 120 mm thickness,
the structure is inversely proportional to the open- and 0.2 nominal pore size has an LEP of 4.0 bar
ing size and dependent on the polymeric proper- (Kim and Harriot 1987).
ties of the membrane. A theoretical expression,
based on Young-Laplace equation, enables the
estimation of LEP (see, e.g., El Bourawi References
et al. 2006):
El Bourawi S, Ding Z, Ma R, Khayet M (2006)
A framework for better understanding membrane dis-
2gcosy
DP ¼ tillation separation processes. J Membr Sci 285:4–29
r Kim B-S, Harriot P (1987) Critical entry pressure for
liquids in hydrophobic membranes. J Colloid Interface
where g is the liquid surface tension, y the contact Sci 115:1–8
angle between liquid and membrane, and r is the Smolders K, Franken ACM (1989) Terminology for mem-
brane distillation. Desalination 72:249–262
pore radius.
or the flow outside and perpendicular to a capil- driving force, a parameter which is given by the
lary bed “homogenized” difference between pA and CA
obtained by substituting the concentration in
Nu ¼ 0:80 Re0:47 Sc0:33 one phase with the corresponding equilibrium
value in the other phase. In other word
The concept of mass transfer coefficient can also
be utilized when transfer between different pA
Driving force ¼ pA HCA ¼ CA
phases is considered, such as mass transfer H
between a gas and a liquid phase or mass transfer
where H is the parameter expressing the partition
between fluids separated by a dense membrane.
equilibrium of the component A between the gas
The definition given in Eq. 1 is still applicable
and the liquid phase (which assumes a constant
although care must be taken when the driving
value if a Henry law type equilibrium applies).
force is to be quantified. As a descriptive exam-
ple, let’s consider the case of mass transfer of a
component A taking place between the bulk of
gas phase, with pA the component partial pressure References
and the bulk of a liquid phase, with CA the com-
ponent concentration. The overall mass transfer Cussler EL (1997) Diffusion. Mass transfer in fluid sys-
tems, vol 2. University Press, Cambridge
coefficient can be defined in this case as the ratio
between component A mass flux and overall
B
ABA triblock
Block Copolymer Membrane, Fig. 1 Linear and nonlinear architecture of block copolymers
of different comonomers into a living copolymer- the precursors because most of the reactive end
ization system or, alternatively, by the coupling groups are segregated inside the polymer chains
of difunctional homopolymeric precursors. coiled in good solvent. Moreover, for long poly-
In the first case, anionic polymerization or, mer chains, the concentration of the reactive end
more recently, living radical polymerization groups is too low to have an effective coupling or
methods can be in principle used. In real cases linking reaction because the overall polymer con-
(Ekizoglou and Hadjichristidis 2002; Buzdugan centration cannot be too high. Therefore, the
et al. 2000; Reuter et al. 1991), each addition of a essential problem is how to expose and concen-
new monomer will inevitably make some living trate the reactive end groups of long polymer
chains dead because of impurities, leading to the chains, while the overall polymer concentration
resultant block copolymer with lower block num- will not be increased.
bers and broad molecular weight distribution.
Therefore, the sequential addition method can
only be used to make copolymers with a few
Block Copolymers in Membranes
blocks, such as triblock copolymers. Another
limitation of the sequential addition of different
Copolymers, and in particular block copolymers
comonomers is their reaction compatibility: each
(BCPs), in recent years have aroused great inter-
added monomer must be sufficiently reactive so
est in the field of specialty polymer applications,
that the chain can propagate. Often, a living
including nanotechnologies (Park et al. 2003;
A block can initiate comonomer B, but a living
Krausch and Magerle 2002; Hamley 2003;
B block cannot initiate comonomer A.
Lazzari and Lopez-Quintela 2003; Lu and Sastry
In the second approach, multiblock copoly-
2007; Hawker and Russell 2005; Li et al. 2005;
mers could be in principle prepared by coupling
Segalman 2005; Cheng et al. 2006; Stoykovich
(Yagci and Tasdelen 2006) different polymer
and Nealey 2006; Krishnamoorthy et al. 2006; Li
chain di-ends terminated with suitable reactive
and Ober 2006; Fasolka and Mayes 2001; Darling
groups or by linking (Yagci and Tasdelen 2006;
2007; Kim and Hinsberg 2008; Bates and
Rahman et al. 2007) di-end-functionalized poly-
Fredrickson 1999; Abetz and Simon 2005; van
mer chains using so-called difunctional linking
Zoelen and ten Brinke 2009), given their ability
agents in solution. However, both coupling and
to self-organize into structures with periodicity
linking reactions are extremely ineffective when
down to the nanometer scale.
long polymer chains (Mw >5 103) are used as
Block Copolymer Membrane 3
Block Copolymer
Membrane,
Fig. 2 Schematic of “self- A
assembly” in BCPs due to
phase separation
block copolymer
phase-separated
block copolymer
If the different polymer blocks are chemically that of the analogous homopolymers (Guan and
incompatible, phase separation occurs with spon- De Simone 1994).
taneous segregation of different macromolecules The polyethylene oxide [PEO] is, for example,
in different microdomains (Fig. 2). one of the most interesting materials for the sep-
Microdomains formed are not arranged in a ran- aration of CO2, especially when cross-linked with
dom but show a regular arrangement which other polymers or incorporated into block copol-
involves the formation of periodic structures. ymers (Lin et al. 2006; Pethe et al. 2008).
This phenomenon, called “self-assembly,” Because of its amorphous character and of its
determines the spontaneous formation of flexibility, it suitably directs the permselectivity
nanostructures. It is associated with the competi- of CO2 through the polymer matrices, especially
tion between the tendency to separation of phase, when the length of the segment, the weight, and
due to the incompatibility of the blocks, and the molecular ratio with the other blocks of the
chemical connectivity that prevents it; periodic copolymer complexes are changed.
structures are formed in which the contact area Bondar et al. (2000) observed that the perme-
between the incompatible microdomains is min- ability of CO2 increases with the amount of
imized. The minimization of the interfacial area polyether [PEO or PTMEO] when segmented
between the domains involves a reduction in block copolymers are incorporated into the
interfacial energy for which even if from an polyether-b-polyamide, where they form the seg-
entropic point of view the individual polymer regated phase of nylon-6 [PA6] or nylon-12
chains prefer a conformation random coil, in the [PA12]. In particular, they have observed that
case of block copolymers, macromolecules tend the copolymers 57PEO/PA6 and 55PEO/PA12
to assume more extended conformations at the exhibit a better selectivity to pure gas CO2/N2
interface between the two blocks so as to allow 56 (PCO2 66 barrer) and CO2/H2 9.8 (PCO2
similar blocks to organize into microstructures 20 barrer), respectively, compared to more con-
that minimize the ratio (surface exposed/ ventional polymers rubbery and glassy.
volume). Higher performance was observed when more
The frequency and size of these domains than one unit polar (PEO and PA6) were included
depend on the lengths of the regular blocks and, in the polymer chain, suggesting the critical role
therefore, from the molecular masses. of interesting polar intermolecular interactions
Block copolymers find many interesting appli- between the polymer chain and the penetrating
cations in membrane technology. molecules. Membranes PEO/PBT have been ad
Block copolymers have found application in a hoc designed in order to obtain block copolymers
class of rubbery membranes, having the unique with high performance for the separation of CO2
ability to separate CO2 from gas streams, with a (Zhao et al. 2008). Separation factors for the pairs
consequent increase in performance compared to of gases, such as CO2/H2, CO2/N2, and CO2/CH4,
4 Block Copolymer Membrane
were obtained in different ratios of the polymer Krishnamoorthy S, Hinderling C, Hcinzelmann H (2006)
chain. When mixed with the polyether glycol Nanoscale patterning with block copolymers. Mater
Today 9:40
[PEG], a significant improvement of the perme- Lazzari M, Lopez-Quintela MA (2003) Block copolymers
ability and selectivity for various block copoly- as a tool for nanomaterial fabrication. Adv Mater
mers was observed. 15:1583
Li MQ, Ober CK (2006) Block copolymer patterns and
templates. Mater Today 9:30
Li MQ, Coenjarts CA, Ober CK (2005) Patternable Block
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P
The US Department of Energy has established a polymer showed very desirable stability under
goal of 0.1 S/cm for the proton conductivity of the fuel cell operations, even at high-temperature
PEM, with target operating conditions at 120 C (>150 C) conditions. However, acid leakage
and 50 % RH (Hickner et al. 2004). through such membranes during long-term fuel
Cost-effective and thermally stable alternative cell operations remains to be a concern. Signifi-
membranes, including sulfonated polyimide cant research efforts are continuing in both aca-
(SPI), sulfonated poly(arylene ether sulfone) demia and industry for the further improvement/
(SPAES), sulfonated poly(aryl ether ketone) development of perfluorinated, alternative hydro-
(SPAEK), and polybenzimidazole (PBI)-based carbon polymer-based and polymer/inorganic
membranes, etc., have drawn interests in the hybrid PEMs.
past decade. SPI, SPAES, and SPAEK copoly-
mers are synthesized by copolymerization of
sulfonated monomers (Hickner et al. 2004).
References
These sulfonated copolymer-based membranes
are still highly dependent on water content, and Bai H, Ho WSW (2011) Recent developments on fuel
a hydrophilic component has been incorporated processing and proton-exchange membranes for fuel
into the membrane for water retention (Bai and cells. Polym Int 60:26–41
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a successful approach for the application of PBI temperature proton exchange membranes based on
polybenzimidazoles for fuel cells. Prog Polym Sci
as high-temperature and low humidity PEMs 34:449–477
(Li et al. 2009; Bai and Ho 2011). In this case, Song C (2002) Fuel processing for low-temperature and
fuel humidification is not necessary in fuel cell high-temperature fuel cells: challenges and opportuni-
operations due to the unique proton conduction ties for sustainable development in the 21st century.
Catal Today 77:17–49
mechanism by self-ionization and self-
dehydration of H3PO4. In addition, the PBI
B
Biobutanol Recovery from Biomass ABE from the dilute fermentation broth by dis-
Fermentation Broth tillation. Therefore, several in situ product-
removal technologies, such as adsorption, gas
Wanqin Jin stripping, liquid-liquid extraction, perstraction,
State Key Laboratory of Materials-Oriented pervaporation, and reverse osmosis, have been
Chemical Engineering, Nanjing Tech University, developed. These technologies could be coupled
Nanjing, China with ABE fermentation process to reduce the
effect of product inhibition and improve the
sugar utilization and solvent productivity
Biobutanol recovery from biomass acetone- (Garcı́a et al. 2011).
butanol-ethanol (ABE) fermentation broth by Pervaporation (PV) is a membrane process for
pervaporation is a process that couples ABE fer- liquid separation, in which a polymeric or inor-
mentation with in situ pervaporation recovery ganic membrane usually serves the separating
acetone, butanol, and ethanol from fermentation barrier. The application of PV for butanol recov-
broth. ery from fermentation broth is based on the selec-
During the past decade, there has been an tive permeation of organic compounds through
increasing interest for the production of biofuels the membrane when the nature of the membrane
from renewable resources because of growing is hydrophobic. PV is especially effective for the
concerns about global warming and increasing system in which the concentration of the targeted
consumption of crude oil. Butanol, as compared species is low; for instance, the butanol content in
to ethanol, is less volatile and explosive, contains the fermentation broth is very low. Furthermore,
more energy, and can easily mix with gasoline in the pervaporation process is energy efficient and
any proportion. In addition, butanol can be used it is harmless to the fermentation broth.
directly or blended with gasoline or diesel with- PV membranes can be made from either poly-
out any vehicle retrofit, since the air to fuel ratio meric or inorganic materials, even both of them
and the energy content of butanol are close to (Qureshi and Blaschek 1999). The polymeric
gasoline (Qureshi and Ezeji 2008). Biobutanol pervaporation membranes for extracting butanol
is produced from renewable resources (biomass) from fermentation broth include polydimethyl-
by acetone butanol ethanol (ABE) fermentation siloxane (PDMS) membranes, poly
process. However, usually the maximum concen- [1-(trimethylsilyl)-1-propyne] (PTMSP) mem-
tration of total solvents (ABE) do not exceed branes, poly(ether block amide) (PEBA) mem-
20 g/L due to the end-product inhibition on branes, liquid membranes, other modified
microbes, resulting in high energy cost to recover polymer membranes, as well as porous
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1317-1
2 Biobutanol Recovery from Biomass Fermentation Broth
polypropylene (PP) membranes and polytetra- alternatively installed before the pervaporation
fluoroethylene (PTFE) membranes. Among module, in order to retain microbes and avoid
them, the commonly used PDMS membranes the biofouling of pervaporation membranes.
with good selectivity and stability are regarded
as the most potential PV membranes for butanol
recovery application. The typical inorganic mem-
References
brane for PV is hydrophobic zeolite membrane,
such as ZSM-5 and silicalite-1 membrane. The Garcı́a V, Päkkilä J, Ojamo H, Muurinen E, Keiski
process of biobutanol recovery from biomass R (2011) Challenges in biobutanol production: how
ABE fermentation broth by pervaporation is to improve the efficiency. Renew Sustain Energy Rev
15:964–980
also called ABE fermentation-pervaporation-
Liu G, Wei W, Wu H, Dong X, Jiang M, Jin W (2011)
coupled process; its conventional flow chart is Pervaporation performance of PDMS/ceramic com-
shown in Fig. 1 (Liu et al. 2011). A pervaporation posite membrane in acetone butanol ethanol (ABE)
membrane module is connected to the fermentor, fermentation-PV coupled process. J Membr Sci
373:121–129
and the ABE solvent can be selectively and con-
Qureshi N, Blaschek H (1999) Butanol recovery from
tinuously removed from the fermentation broth model solution/fermentation broth by pervaporation:
and then concentrated in the membrane down- evaluation of membrane performance. Biomass
stream side. As result, the ABE concentration in Bioenergy 17:175–184
Qureshi N, Ezeji T (2008) Butanol “a superior biofuel”
the broth is kept at low level to facilitate the
production from agricultural residues (renewable bio-
continuous fermentation process as well as mass): recent progress in technology. Biofuels
enhance the solvent productivity. In addition, a Bioprod Biorefin 2:319–330
microfiltration/ultrafiltration unit can be
C
Ceramic Membrane
for Pervaporation,
Fig. 1 Atomic stick
representations for the
frameworks of CHA (a),
MFI (b), and MOR (c)
zeolite structures. The
nodes represent tetrahedral
framework atoms and the
sticks represent oxygen
bridges (Reproduced from
Bowen et al. 2004)
Ceramic Membrane for Pervaporation, Table 1 Characteristics of the zeolite applied in membrane and an example
of its application in pervaporation (Reproduced from Baerlocher et al. 2002)
Zeolite
A Y ZSM-5 Mordenite
Structure type LTA FAU MFI MOR
Si/Al ratio 1 2.3 81 4
Cations Na Na, Ca Na Na
Pore size 0.41 nm 0.74 nm 0.74 nm 0.51 nm 0.55 nm 0.65 nm 0.70 nm
0.41 nm 0.53 nm 0.56 nm 0.34 nm 0.48 nm
0.26 nm 0.57 nm
Channel network Three Three dimensional Three dimensional One dimensional
dimensional
Application Dehydration of Separation of Separation of Separation of benzene/
organic mixture methanol/MTBE xylene isomers p-xylene mixture
mixture
benzene mixtures), and acid separations (e.g., zeolite membranes have been commercialized by
acetic acid/water mixtures). In 2000, the first the Busan Nano-Research Institute Inc. (BNRI, a
industrial-scale separation plant, based on NaA subsidiary of Mitsui), SMART Chemical company
zeolite membrane for pervaporation dehydration (UK), Inocermic GmbH (Germany), and Nanjing
of organic-water mixtures, was developed by Jiusi Hi-Tech Co. (China) (Gascon et al. 2012).
Mitsui Engineering and Shipbuilding Co. Ltd. in Unfortunately, NaA zeolite membranes are very
Japan (Morigami et al. 2001). Until Now, NaA sensitive to even the slightest acidity.
Ceramic Membrane for Pervaporation 3
Thermopervaporation
(Thermo-PV), F T11 x20 R T10 x10
Fig. 1 Concept of
thermopervaporation (Eva
et al. 2010) T11 x11 T10 x10
membrane
Saturated vapor
Liquid feed
Liquid permeate
Saturated vapor
Condensing
sheet
P T21 x21
Thermopervaporation (Thermo-PV), Table 1 Features of thermopervaporation in contrast with pervaporation (Nitta et al. 1986)
Thermopervaporation Pervaporation
Principle Model
Th > Tc
Thermopervaporation (Thermo-PV)
Evacuation
Feed
Cooling
Feed Water
Permeate
Permeate
Mechanism Evaporation to permeation Permeation to evaporation
Driving force Temperature (steam pressure) difference Pressure difference
Membrane Material Hydrophobic Hydrophilic
Structure Porous Nonporous
Operation pressure Normal pressure Evacuation
Operation temperature Less than boiling point Room temperature
3
4 Thermopervaporation (Thermo-PV)
a small and suboptimally configured module; Franken ACM, Mulder MHV, Smolders CA
results showed that this concept has great poten- (1990) Pervaporation process using a thermal gradient
as the driving force. J Membr Sci 53:127–141
tial for commercial applications (Eva et al. 2010). Nitta K, Ashida A, Mitani K, Ebara K, Yamada A (1986)
Water recycling system using thermopervaporation
method, In: International Symposium on Space
Technology and Science, 15 th, Tokyo, Japan, 1986,
References pp. 1355–1359
Volkov VV, Bortisov IL (2012) Thermopervaporation
Eva SF, Peter G, Earl L, Goetheer V (2010) Thermo membrane bioreactor as a new concept for the
pervap: the next step in energy efficient pervaporation. low-cost production of biobutanol. In: Euromembrane
Desalination 250:1053–1055 conference, London, 23–27 Sept 2012
S
has been showed that the membrane modification leads to a higher total flux but a lower sulfur
methods lead to achieve high selectivity or high enrichment factor. By increasing the feed tem-
flux (Lin et al. 2009). For example, cross-linking perature, the total flux increased while sulfur
modification for PEG increased sulfur enrich- enrichment factor decreased. It was appropriate
ment factor from 3.31 to 7.31 for model com- that low permeate pressure and high feed flow
pounds feed and from 1 to 3.05 for FCC gasoline. rate were beneficial to improve total flux and
AgY zeolite incorporation in PDMS membranes sulfur enrichment factor (Xu et al. 2010).
led to a significant increase in total flux. At the
same time, higher sulfur enrichment factor and
permeation flux were obtained from References
PEG/polyurethane (PU) blend membranes for
gasoline desulphurization. It should not be Lin L, Kong Y, Wang G (2006) Selection and crosslinking
modification of membrane material for FCC gasoline
ignored that the performance for various mem-
desulphurization. J Membr Sci 285:144–151
branes mainly depends on the properties of the Lin L, Zhang YZ, Kong Y (2009) Recent advances in
membrane materials while the types of mem- sulfur removal from gasoline by pervaporation. Fuel
brane structure also have a significant influence 88:1799–1809
Saxton RJ, Minhas BS (2004) Ionic membranes for
on the membrane performance. Ceramic-
organic sulfur separation from liquid hydrocarbon
supported PDMS membrane exhibits a higher solutions. US Patent 6,702,945
permeation flux and an acceptable sulfur enrich- Qi R, Wang Y, Li J (2006) Pervaporation separation of
ment factor in comparison with those composite alkane/thiophene mixtures with PDMS membrane.
J Membr Sci 280:545–552
membranes using polymeric supports
White LS, Wormsbecher RF, Lesemann M (2004) Mem-
(Xu et al. 2010). The operating parameters of brane separation for sulfur reduction. Patent US
PV, including feed temperature, feed concentra- 0211706 A1
tion, feed flow rate, permeate pressure, etc., have Xu R, Liu GP, Dong XL, Jin WQ (2010) Pervaporation
separation of n-octane/thiophene mixtures using
significant impacts on membrane performance.
polydimethylsiloxane/ceramic composite membranes.
Take ceramic-supported PDMS membrane as an Desalination 258:106–111
example; the increase of sulfur content in feed
A
low-fat product such as double emulsions and Christov NC, Ganchev DN, Vassileva ND, Denkov ND,
spread. Foamed food product where air is present Danov KD, Kralchevsky PA (2002) Capillary mecha-
nisms in membrane emulsification: oil-in-water emul-
as a component of several food products present sions stabilized by Tween 20 and milk proteins.
(dispersed phase of bubbles or pores) was pro- Colloids Surf A 209:83–104
duced by membrane foaming. The method is Gudipati V, Sandra S, McClements DJ, Decker EA
based on pressing the dispersed phase as a form (2010) Oxidative stability and in vitro digestibility of
fish oil-in-water emulsions containing multilayered
of gas through the membrane pores into the con- membranes. J Agric Food Chem 58:8093–8099
tinuous phase while the continuous phase, Joscelyne SM, Trägårdh G (1999) Food emulsions using
containing whey proteins as surface-active sub- membrane emulsification: conditions for producing
stances, flowed along the membrane surface small droplets. J Food Eng 39:59–64
Kukizaki M (2009) Preparation of solid lipid microcap-
(Bals and Kulozik 2003a, b). Rotating membrane sules via solid-in-oil-in-water dispersions by premix
emulsification was also used in the preparation of membrane emulsification. Chem Eng J 151:387–396
gas dispersion to improve the foam microstruc- Kukizaki M, Goto M (2007) Preparation and evaluation of
ture in terms of size and size distributions uniformly sized solid lipid microcapsules using mem-
brane emulsification. Colloids Surf A 293:87–94
(M€uller-Fischeret al. 2007). The Morinaga Milk M€uller-Fischer N, Bleuler H, Windhab EJ (2007) Dynam-
Industry (Japan) developed and commercialized ically enhanced membrane foaming. Chem Eng Sci
a low-fat spread using membrane technology 62:4409–4419
(Okonogi et al. 1992). The volume fraction of Okonogi S, Kumazawa R, Toyama K, Kato M, Asano Y,
Takahashi IK, Fujimoto M (1992) Production of dou-
dispersion water-phase reaches up to 75 % and ble emulsified spread and its production. JP4258251
the product is reported to be very stable, with Piacentini E, Giorno L, Dragosavac MM, Vladisavljević
suitable texture, and tasty. The potential for the GT, Holdich RG (2013) Microencapsulation of oil
easy scale-up is another attractive quality of droplets using cold water fish gelatine/gum Arabic
complex coacervation by membrane emulsification.
membrane emulsification technology. Microen- Food Res Int 53:362–372
capsulation of vegetable oil droplets using cold Ramakrishnan S, Ferrando M, Aceña-Muñoz LS, Lamo-
water fish gelatine/gum arabic complex coacer- Castellví D, G€ uell C (2013) Fish oil microcapsules
vation has been obtained at batch and large scale from O/W emulsions produced by premix membrane
emulsification. Food Bioprocess Technol
production using the stirred and the pulsed flow 6:3088–3101
membrane emulsification (Piacentini et al. 2013). Ribeiro HS, Rico LG, Badolato GG, Schubert H (2005)
Production of o/w emulsions containing astaxanthin
by repeated premix membrane emulsification. J Food
Sci 70:117–123
References Scherze I, Marzilger K, Muschiolik G (1999) Emulsifica-
tion using micro porous glass (MPG): surface behav-
Bals A, Kulozik U (2003a) The influence of pore size, the iour of milk proteins. Colloids Surf B 12:213–221
foaming temperature and the viscosity of the continu- Song SH, Cho YH, Park J (2003) Microencapsulation of
ous phase on the properties of foams produced by Lactobacillus casei YIT 9018 using a microporous
membrane foaming. J Membr Sci 220:5–11 glass membrane emulsification system. J Food Sci
Bals A, Kulozik U (2003b) Effect of pre-heating on the 68:195–200
foaming properties of whey protein isolate using a
membrane foaming apparatus. Int Dairy J 13:903–908
H
Hollow Fiber Carbon Molecular Sieve application as reported by He et al. (He and
Membranes Hägg 2011a). Different techniques such as scan-
ning electron microscopy (SEM), Fourier trans-
Xuezhong He form infrared spectroscopy (FTIR), and X-ray
Department of Chemical Engineering, diffraction (XRD) have been used to characterize
Norwegian University of Science and the membrane’s structure and morphology.
Technology, Trondheim, Sør-Trøndelag, Figure 1 shows the cross section and inside sur-
Norway face of the precursors and HFCMs, respectively
(He et al. 2011). The outer diameter and wall
thickness of the HFCMs were approximately
Carbon molecular sieve (CMS) membranes have 250 mm and 30 mm, respectively, indicating a
been studied in more than twenty years as prom- significant radical shrinkage comparing to the
ising and energy-efficient membranes for gas precursor membranes with 400 mm and 50 mm.
separation. Due to their high permeability, selec- The pore size and pore-size distribution (PSD)
tivity, and also thermal and chemical stability can be estimated by gas gravimetric adsorption
under adverse and harsh conditions, the CMS measurements equipped with a Rubotherm mag-
membranes are becoming increasingly important netic suspension balance (MSB) (Belmabkhout
for separating gas mixtures with quite similar et al. 2009). The structural parameters of a
molecular kinetic diameter. Carbon molecular cellulosic-based carbon membrane have been
sieve membranes can be prepared by controlling estimated from CO2 sorption measurements, and
the carbonization procedure during carbonization a narrow pore-size distribution was found by He
of different polymeric materials such as et al. (He and Hägg 2012), and the results were
polyimide, polyacrylonitrile (PAN), phenolic shown in Table 1, which will be helpful to under-
resin, poly(phthalazinone ether sulfone ketone), stand the transport mechanism through carbon
poly(phenylene oxide), cellophane paper, cellu- membranes.
lose, and deacetylated cellulose acetate. The car- The operating parameters such as feed pres-
bonization parameters (e.g., purge gas, purge gas sure, temperature, and flow rate of retentate will
flow rate, final temperature, heating rate, and final greatly affect the CMS membrane separation per-
soak time) will affect the resulting carbon mem- formances and need to be optimized for a specific
brane performance, and the optimal condition application as reported by He et al. (He and Hägg
was obtained on the basis of experimental design 2011b). Considering the aging problem for most
and statistical analysis to prepare the high- carbon membranes, different regeneration tech-
performance carbon membranes for a specific niques can be used to recover the performances
# Springer-Verlag Berlin Heidelberg 2014
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1332-9
2 Hollow Fiber Carbon Molecular Sieve Membranes
Hollow Fiber Carbon Molecular Sieve Membranes, Fig. 1 SEM images of cross section of precursor and HFCM-2.
(a, c) are the cross section of the precursor; (b, d) are the cross section of the prepared carbon membrane (He et al. 2011)
Hollow Fiber Carbon Molecular Sieve Membranes, Table 1 Structural parameters of the cellulosic-based carbon
membranes (He and Hägg 2012)
W0 Average
Carbon True density, rs Bulk density, rb (cm3 E0 micropore width
membranes (g cm 3)a (g cm 3) g 1) (kJ mol 1) (Å) Reference
HFCM-1 1.53 1.24 0.15 32.2 5.2 This work
HFCM-2 1.38 1.12 0.17 30.8 5.6 This work
CMSM1 1.6 1.1 0.28 31.6 5.5 (Lagorsse
et al. 2004)
CM-V823 0.16 22.75 (Lua and Su
2006)
a
Density of carbons is 1.3–1.8 g/cm3 as compared to 2.2 g/cm3 for graphite (Koresh and Soffer 1983)
online or off-line (Lie 2005; Hagg and He 2011). constructed. Figure 2 shows a schematic and
In order to ensure the efficiency of the carbon lab-scale hollow fiber carbon membrane module
membrane separation process, a hollow fiber (He and Hägg 2011b), while Fig. 3 shows a small
membrane module should be designed and pilot-scale module (designed by one of
Hollow Fiber Carbon Molecular Sieve Membranes 3
Retentate Feed
Hollow fibre
carbon membranes
Epoxy Epoxy
Feed
Retentate
Permeate
Hollow Fiber Carbon Molecular Sieve Membranes, Fig. 2 A schematic and lab-scale carbon membrane module
(He and Hägg 2011b)
NanoGloWa project partner, HyGear B.V.) (Hägg and Lie 2006), H2-CH4 separation wher-
(He 2011). Single-gas permeability tests at dif- ever relevant (Grainger and Hägg 2008), and CO2
ferent temperatures and pressures were mostly capture from flue gases (He and Hägg 2011b; He
conducted by using the lab-scale module, while et al. 2009). Moreover, carbon molecular sieve
the small pilot-scale module was employed to test membranes also show a great potential in air
the gas mixture at a higher permeate flux in order separation, petrochemical, and high-temperature
to determine the gas composition more precisely. membrane reactor applications.
Based on the experimental investigations and
process simulations, the carbon membranes show
high potential for selected industrial applications
such as CO2-CH4 separation for biogas upgrading
4 Hollow Fiber Carbon Molecular Sieve Membranes
Membranes for CO2 Capture from (e.g., Selexol, Rectisol), physical adsorption
Flue Gas (e.g., molecular sieves, metal-organic frame-
works), cryogenics, and membrane separation
Xuezhong He could be used for CO2 capture. Chemical absorp-
Department of Chemical Engineering, tion has been widely used in natural gas for over
Norwegian University of Science and 60 years and separates out relatively high purity
Technology, Trondheim, Sør-Trøndelag, CO2 stream. However, conventional amine
Norway absorption technologies are energy intensive
and costly, which would result in large incremen-
tal costs. National Energy Technology Labora-
The control of anthropogenic emissions of green- tory (NETL) estimates that amine unit will
house gases (GHG) is one of the most challenging increase the cost of electricity production by
environmental issues owing to the implications of 70 % (Elwell and Grant). Membranes are already
GHG for global climate change. Among these an alternative and competitive technology for the
GHG, CO2 is the largest contributor in regard of selected gas separation processes such as air sep-
its amount present in the atmosphere contributing aration, natural gas sweetening, biogas
to 60 % of global warming effects, although upgrading, and hydrogen production during the
methane and chlorofluorocarbons have much last two or three decades. Membrane technology
higher greenhouse effect as per mass of gases will become steadily more attractive due to its
(Yamasaki 2003). A lot of efforts have been put high energy efficiency and low economical costs.
on the reduction of CO2 emission from large CO2 Although polymeric membranes are still domi-
point sources such as fossil fuel power plants and nating, the current industrial uses for gas separa-
other industries (e.g., cement, steel and iron pro- tion, the trade-off of permeability/selectivity, and
duction, natural gas sweetening, and biogas the limitation of operating temperature and
upgrading processes). Such plants emit large adverse conditions such as the presence of acid
quantities of CO2; for example, the fossil fuel gases SO2 and NOx could probably direct the
power plants are responsible for roughly 40 % development of polymer membranes into the
of total CO2 emissions and coal-fired plants being other types of membranes such as microporous
the main contributor. Clearly, coal-fired plants organic polymers (MOPs), fixed-site-carrier
need to be addressed first, especially by (FSC) membranes, mixed matrix membranes,
retrofitting existing plants. carbon molecular sieve membranes, as well as
Different techniques such as chemical absorp- inorganic (ceramic, metallic, zeolites)
tion (e.g., MEA, MDEA), physical absorption membranes.
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1333-12
2 Membranes for CO2 Capture from Flue Gas
CO2,
ADJ-2 retentate1 vent
3.3%
E19 E17
mix1 K-108
E-100 feed1 E11 CO2,
retentate2
MIX-100 sweep1 RCY-1 0 92%
Carbon E15 E-105
membrane E14 to
module E-107 feed2 pipeline
E-106
cooling 3 sweep permeate2
membrane
cooling
permeate1 cooling1
8
CO2, Mix2 cooling 2
15%
Flue
gas
E1 E13 E16 E12
K-100 K-106 K-107 ADJ-1 K-105
Membranes for CO2 Capture from Flue Gas, Fig. 1 A schematic flow sheet of two-stage membrane units for CO2
capture from flue gases (He and Hägg 2013)
Gas separation membrane system offers a results showed that membrane process using a
potentially lower cost, more energy-efficient high-performance FSC membrane was feasible
CO2 capture option. However, there are some for CO2 capture, even with a low CO2 concentra-
challenges related to the limited application of tion (~10 %) in flue gas, compared to amine
membrane system for CO2 capture from flue gas absorption in terms of energy requirement, and
in post-combustion process; examples are as fol- it was possible to achieve >90 % CO2 recovery
lows: large quantities of gas need to be treated and a purity above 95 % CO2 in permeate stream.
due to a low CO2 concentration, high compres- Recently, this type of membrane performance has
sion energy consumption required to achieve a been significantly improved as reported by Kim
high driving force for membrane operation, and et al. (2013). Thus, this environmentally friendly
challenges of acid gases such as SO2 and NOx and technique could promote membrane gas separa-
high content of water. According to these chal- tion system as a promising candidate for CO2
lenges, highly CO2-permeable and CO2-selective capture from flue gas in post-combustion process
membranes with a low cost are required for mem- if the abovementioned challenges can be well
brane system to compete with traditional chemi- addressed.
cal absorption method for CO2 capture. He
et al. investigated the application of hollow fiber
carbon membranes for CO2 capture from flue
References
gases (He and Hägg 2013). They reported that a
capital cost of 100 $/tonne CO2 avoided for a Elwell LC, Grant WS (nd) Technology options for
two-stage carbon membrane system (illustrated capturing CO2. [Cited 25 Sept 2010]; Available from:
in Fig. 1), which is still higher than a traditional http://www.powermag.com/coal/Technology-options-
chemical method of MEA (59 $/tonne CO2 for-capturing-CO2_582.html
Grainger D (2007) Development of carbon membranes for
avoided reported by Rao and Rubin (Stoeckli hydrogen recovery. Norwegian University of Science
et al. 2002)), but the referred carbon membranes and technology. PhD thesis
had a clear potential of further optimization. He X, Hägg M-B (2013) Hollow fiber carbon membranes:
Hussain et al. conducted a feasibility analysis by from material to application. Chem Eng
J 215–216:440–448
HYSYS integrated with an in-house membrane Hussain A, Hägg M-B (2010) A feasibility study of CO2
program (ChemBrane, developed by Grainger capture from flue gas by a facilitated transport mem-
(2007)) to investigate the influence of process brane. J Membr Sci 359(1–2):140–148
parameters on energy demand and flue gas Kim T-J, Vrålstad H, Sandru M, Hägg M-B (2013) Sepa-
ration performance of PVAm composite membrane for
processing cost using a novel CO2-selective CO2 capture at various pH levels. J Membr Sci
FSC membrane (Hussain and Hägg 2010). The 428(0):218–224
Membranes for CO2 Capture from Flue Gas 3
Stoeckli F, Slasli A, Hugi-Cleary D, Guillot A (2002) The Yamasaki A (2003) An overview of CO2 mitigation
characterization of microporosity in carbons with options for global warming – emphasizing CO2
molecular sieve effects. Microporous Mesoporous sequestration options. J Chem Eng Jpn 36(4):361–375
Mater 51(3):197–202
M
Membranes for Natural Gas sweetening are still using cellulose acetate/triac-
Sweetening etate and polyimide, the novel, high-performance
fixed-site-carrier (FSC) membranes showed a
Xuezhong He great interest for CO2/CH4 separation (Deng
Department of Chemical Engineering, et al. 2009a).
Norwegian University of Science and High-pressure operation is the main challenge
Technology, Sør-Trøndelag, Trondheim, for natural gas processing with membrane sys-
Norway tem. Membrane plasticization is found to be a
well-known phenomenon in most polymer mem-
branes which absorb a high content of CO2 at
Natural gas sweetening (CO2 removal from nat- high pressure (Donohue et al. 1989; Wind
ural gas) is mandatory to meet the specifications et al. 2004), resulting to a significant decrease of
of natural gas grid. Decision on which technology CO2 permeance as well as selectivity of CO2/
to use for CO2 removal from natural gas is mainly CH4. The possible strategies to overcome mem-
dependent on process conditions and the crude brane plasticization are cross-linking of mem-
natural gas composition. Conventional chemical brane material (Wind et al. 2002) and
absorption is well known and has been commer- fabrication of mechanical strength-enhanced
cially used for CO2 removal in various processes membranes, e.g., mixed matrix membrane, by
and considered as a state-of-the-art technology. adding inorganic fillers into polymer matrix.
However, membrane system shows a great poten- Adams et al. prepared a 50 % (vol.) zeolite
tial for natural gas sweetening since it possesses 4A/poly(vinyl acetate) (PVAc) MMM for CO2
many advantages such as small footprint, low separation from natural gas (Adams et al. 2011).
capital and operating costs, and environmental They found that the prepared MMMs can
friendly and exhibits process flexibility even approach Robeson CO2/CH4 upper bound, and
though it has only 5 % of the market today. CO2 permeability remained effectively
Membrane unit cost and CH4 loss are two crucial unchanged with a 63 % increase in selectivity
parameters used for evaluation of membrane pro- compared to pure PVAc. Their membranes
cess efficiency, which are mainly dependent on showed a promising application in high-pressure
the membrane performance and process design. natural gas sweetening. Deng et al. reported that
Some representative suppliers of membrane sys- carbon nanotubes (CNTs) reinforced PVAm/
tems using different materials for CO2 separation PVA blend FSC membrane and presented a
from natural gas are shown in Table 1. Although good CO2/CH4 separation performance (Deng
common polymer membranes for natural gas et al. 2009b; He et al. 2014). It shows a much
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1334-6
2 Membranes for Natural Gas Sweetening
Membranes for Natural Gas Sweetening, Table 1 Representative commercial membrane systems for CO2 removal
from natural gas
Membrane Material Company Module
SeparexTM Cellulose acetate UOP Spiral wound
Cynara ® Cellulose acetate NATCO Hollow fiber
Prism ® Polysulfone Air Products Hollow fiber
Cytop Perfluoropolymers MTR –
Medal Polyimide Air Liquide Hollow fiber
strong mechanical strength which could have Moreover, how to predict the long-term perfor-
possibility to maintain a good separation perfor- mance in commercial application based on the
mance even at high pressure. short-term lab-scale tests could be a continuing
Process design for CO2 removal by membrane challenge of membrane system for high-pressure
system from natural gas depends on the mem- natural gas sweetening.
brane permeability and selectivity, CO2 concen-
tration in feed stream, specific separation
requirement, as well as the location of the plant.
References
Peters et al. conducted process design, simula-
tion, and optimization for CO2 removal from Adams RT et al (2011) CO2–CH4 permeation in high
natural gas using HYSYS integrated with an zeolite 4A loading mixed matrix membranes.
in-house membrane program (ChemBrane) J Membr Sci 367(1–2):197–203
(Peters et al. 2011). They reported that a Deng L et al (2009a) PVA/PVAm blend FSC membrane
for natural gas sweetening. In: Hassan EA
two-stage membrane system with a CO2 (ed) Proceedings of the 1st annual gas processing
permeance 0.3 m3 (STP)/(m2 h bar) and a CO2/ symposium. Elsevier, Amsterdam, pp 247–255
CH4 selectivity 40 is comparable to that of amine Deng L, Zhao T, Hägg M-B (2009b) CNTs reinforced
process. Although the purity of sweet gas is a nanocomposite FSC membrane for CO2 separation.
In: The 8th China international nanoscience and tech-
little low, it can still achieve the sales gas stan- nology symposium, Xiangtan
dards (<2 % CO2 in natural gas). A combination Donohue MD, Minhas BS, Lee SY (1989) Permeation
of hybrid processes comprising a membrane sys- behavior of carbon dioxide-methane mixtures in cel-
tem for bulk removal of CO2 from crude natural lulose acetate membranes. J Membr Sci
42(3):197–214
gas feed with an amine unit for final purification He X, Kim T-J, Hägg M-B (2014) Hybrid fixed-site-
to reach the pipeline specification (<2 % CO2) carrier membranes for CO2 removal from high pres-
could be the optimal process for natural gas sure natural gas: Membrane optimization and process
sweetening. Future direction of natural gas condition investigation. J Membr Sci 470:266–274
Peters L et al (2011) CO2 removal from natural gas by
sweetening using membrane systems will focus employing amine absorption and membrane
on the development of high-performance mem- technology – a technical and economical analysis.
branes with an active layer on the order of 0.1 mm Chem Eng J 172(2–3):952–960
to compete with the other separation methods. In Wind JD et al (2002) The effects of crosslinking chemistry
on CO2 plasticization of polyimide gas separation
addition, membranes should also have to be resis- membranes. Ind Eng Chem Res 41(24):6139–6148
tant to warm and high-pressure operating condi- Wind JD, Paul DR, Koros WJ (2004) Natural gas perme-
tions and mechanically strong. Membrane ation in polyimide membranes. J Membr Sci
plasticization and long-term compaction at high 228(2):227–236
pressure should be further investigated.
B
Biogas Upgrading, Table 1 Typical gas composition from different sources (Rasi et al. 2007)
Composition (vol, %)
Process CO2 CH4 N2 O2 H2O H2S/SO2 (ppm)
Farm biogas plant 37–38 55–58 <2 <1 4–7 32–169
Sewage digester 38.6 57.8 3.7 0 4–7 62.9
Landfill 37–41 47–57 <1 <1 4–7 36–115
CH4 65%
CO2 35%
H2S 200-300ppm
FeCl2 Water saturated
Drier
Filter
Raw biogas
Compressor Cooler
Biomass
Bioreactor Filter
10-30 bar
Propane/ odour
Compressor
Waste solids
Upgraded biogas,
CH4>96% Cooler 2nd membrane 1st membrane
CO2-rich permeate
Biogas Upgrading, Fig. 1 A schematic diagram for biogas upgrading process by membrane systems
(~200 bar). The main challenge of a membrane Makaruk et al. pointed out that membrane system
system is the pretreatment of biogas to protect the provides enough flexibility for heat integration
membrane materials, especially for the biogas within biogas plants (Makaruk et al. 2010), and
produced from the sewage treatment plants and the expected energy requirement for a single-
landfill sites where it usually have a lot of mali- produced cubic meter of natural gas substitute is
cious gas components. Polyvinyl amine (PVAm)/ estimated to be around 0.3 kWh, which is close to
polyvinyl alcohol (PVA) blend fixed-site-carrier the values reported in an industrial scale demon-
(FSC) membranes for biogas upgrading have strator for membrane biogas upgrading plant at
been investigated by Deng et al. (Deng and Bruck an der Leitha in Austria (Miltner
Hägg 2010). Their results indicated that a mem- et al. 2008). Moreover, a new carbon membrane
brane process with a CH4 recovery of 99 % at a company MemfoACT (http://www.memforact.
low operation cost could be designed to achieve no) was launched in 2008 in Norway, which
the specification of natural gas network distribu- mainly focuses on the biogas upgrading using
tion, which makes this environmentally friendly their patented hollow fiber carbon molecular
technology more competitive compared to the sieve membranes. Their contributions could
other conventional technologies currently used.
Biogas Upgrading 3
promote to bring this technology into the com- Makaruk A, Miltner M, Harasek M (2010) Membrane
mercial application in the near future. biogas upgrading processes for the production of nat-
ural gas substitute. Sep Purif Technol 74:83–92
Miltner M, Makaruk A, Harasek M (2008) Application of
gas permeation for biogas upgrade – operational expe-
riences of feeding biomethane into the Austrian gas
References grid. 16th European Biomass Conference & Exhibition
from Research to Industry and Markets, Valencia
Deng L, Hägg M-B (2010) Techno-economic evaluation Rasi S, Veijanen A, Rintala J (2007) Trace compounds of
of biogas upgrading process using CO2 facilitated biogas from different biogas production plants. Energy
transport membrane. IJGGC 4:638–646 32:1375–1380
C
a b
cells plasma/blood
nutrients
IgG
oxygen
metabolites
barrier cells
Cell Encapsulation, Fig. 1 Principle of biohybrid constructs. (a) Description of the mass transfer expected between
cell compartment and host. (b) Application to microencapsulation
damage during cryopreservation and allows thus used and/or combined in biomaterials to form
an easy storage before use, leading to readily biohybrid constructs (Fig. 1).
available encapsulated cells when needed.
The choice of cells depends on the targeted
application as organ supply. For clinical applica- References
tion of tissue engineering, only primary cells
(from animal or human origin) and cell lines Chang TM (1964) Semipermeable microcapsules. Science
146(3643):524–525
have been employed. To reconstitute the func-
Orive G et al (2006) Biocompatibility of alginate-poly-
tions of a failing organ or tissue, multiple L-lysine microcapsules for cell therapy. Biomaterials
pre-differentiated stem cell populations could be 27(20):3691–3700
B
Biocatalytic Membrane Reactors with Chemically Bound Enzyme, Table 1 Protein functional groups involved in
covalent bond with membranes in mild conditions
Protein chemical group Structure
Epsilon amino groups of lysine
O
H2N
OH
NH2
Epsilon amino groups of arginine
NH O
H2N N OH
H NH2
Beta and gamma carboxyl groups of aspartic and glutamic acids
O
HO OH
O NH2
OH
NH2
HO
HS OH
NH2
Hydroxyl groups of serine and threonine
O OH O
OH OH
HO
NH2 NH2
Imidazole group of histidine
O
H
N OH
N NH2
OH
N NH2
H
Biocatalytic Membrane Reactors with Chemically Bound Enzyme 3
Biocatalytic Membrane Reactors with Chemically Bound Enzyme, Table 2 Bi/multifunctional reagents com-
monly used in enzymatic covalent immobilization
Reactive chemical
Cross-linker Structure group
Glutaraldehyde (GA) Aldehydic groups
O O
(3-aminopropyl) triethoxysilane (APTES) Ethoxyl and amino
O groups
Si NH2
O O
O O
Cl Cl
1-ethyl-3-(3-dimethylaminopropyl) carbodiimide Carbodiimide group
hydrochloride (EDC) + Cl–
Spacer Arm 0.0 Å N NH
C
N
Dicyclohexylcarbodiimide (DCC) Carbodiimide group
Spacer Arm 0.0 Å
N
C
N
covalent binding of the enzyme can be achieved Poly(vinylidene fluoride) (PVDF) membrane
by direct reaction with the aldehyde-active has been used either for scientific research or
groups on the membrane surface (Xiao-Jun industrial application in particular micro- and
et al. 2011) or via different spacers. The introduc- ultrafiltration process. The great interest to
tion of an appropriate spacer between the enzyme PVDF membrane is due to its extraordinary ther-
and the membrane often improves the perfor- mal, mechanical, and chemical resistance in addi-
mance of immobilized enzyme, such as enzyme tion to membrane-forming properties. Its
stability and retained activity. Spacers of differ- structure consisting of repeated – (CH2-
ent lengths are generally introduced by using CF2)n – units confers to PVDF these good prop-
bifunctional agents such as diamines (esp. erties, but makes impossible enzyme immobili-
ethylenediamine, pentaethylenehexamine, etc.) zation on native PVDF in a covalent manner. This
that are coupled or activated with glutaraldehyde disadvantage can be overcome performing PVDF
before enzyme immobilization (Peng-Cheng functionalization, in order to introduce on the
et al. 2011). The reaction mechanism involves polymeric membrane structure, reactive groups
the amino groups of the enzyme and the aldehyde that can covalently couple with enzyme func-
groups of glutaraldehyde on the membrane sur- tional groups. Surface modification of existing
face. The schematic representation of an enzyme PVDF membrane can be performed by coating
covalently attached onto cellulose-activated or grafting. Coating modification is preferred when
membrane is reported in Fig. 1. only an improved hydrophilicity of the membrane
4 Biocatalytic Membrane Reactors with Chemically Bound Enzyme
H OH H OH H OH
H O periodate H O
O H2N-(CH2)n-NH2 H O
HO oxidation O O
H O O O
OH H O diamine spacer OH
H H H
H H N H
Cellulose H (CH2)n NH2
dialdehyde
H OH H OH
OHC (CH2)3 CHO H O H2N
H O
O
O OH O
glutaraldehyde enzyme coupling O OH
activation H H
N H
H (CH2)n (CH2)3 O N H
N H (CH2)n N
C (CH2)3 N
H C C
H C
H H
Biocatalytic Membrane Reactors with Chemically activated with periodate oxidation and a generic diamine
Bound Enzyme, Fig. 1 Schematic representation of an spacer, n represent the number of CH2 groups
enzyme covalently immobilized onto cellulose membrane
–
–H2O – –F
[n
—[ CF2– CH– CF2– CH2 — [n
—[ CF2– CH– CF – CH2 — [n
—[ CF2– CH= CF – CH2 —
H F
–
OH
H F
–
–
[n
—[ CF2– CH= CF – CH2 — –HF
[n
—[ CF2– C – C – CH2 — [n
—[ CF2– CH= C – CH2 —
– +
+
¨ H2N HN
H2N
NH2 NH2
NH2
Biocatalytic Membrane Reactors with Chemically Bound Enzyme, Fig. 2 Possible mechanism of alkaline-
induced DAMP grafting on PVDF
H O O
Na2CO3
+ H2N NH2 NH2 + O H N H N N
pH11 50°C Enzyme
DAMP GA
Biocatalytic Membrane Reactors with Chemically Bound Enzyme, Fig. 3 Illustration of various steps for PVDF
functionalization with amino groups and subsequent enzyme attachment via cross-linking with glutaraldehyde
surface is required, but it is not useful as anchor acting on degree of grafting and type of func-
point for enzyme immobilization because of the tional chain introduced, it is possible to affect or
instability of the coated layer which interacts with not affect membrane bulk properties as, for
the membrane merely by physical adsorption. example, hydrophobicity.
More interesting for enzyme immobilization is Surface grafting can be performed by high-
grafting modification which can introduce on energy radiation techniques like plasma treat-
the PVDF backbone functional chains that can ment, ozonation, and UV or by wet chemistry in
be used for enzyme immobilization; in addition harsh basic environment. For example, grafting
Biocatalytic Membrane Reactors with Chemically Bound Enzyme
Biocatalytic Membrane Reactors with Chemically Bound Enzyme, Fig. 4 Schematic representation of stages involved in an example of enzymatic covalent immobili-
zation onto inorganic membranes
5
6 Biocatalytic Membrane Reactors with Chemically Bound Enzyme
of amino groups on PVDF membrane surface can (APTES). APTES exhibits terminal amino
be achieved by treatment at high pH and high groups available for the attachment of cross-
temperature with diamine reagent. The high pH linking reagents such as glutaraldehyde. Termi-
promotes fluorine elimination from the PVDF nal aldehydic group of glutaraldehyde reacts with
chains and the grafting of diamino reagent the exposed amino groups of the organosilane by
(Vitola et al. 2015) (Fig. 2). forming a Schiff base. Final covalent binding
Subsequently the pendant amino groups can occurs through formation of a new Schiff base
be activated for enzyme immobilization in mild between aldehydic terminal group of glutaralde-
conditions using condensing reagent like glutar- hyde and amino groups exposed from the enzy-
aldehyde (Fig. 3). matic amino acid residues of lysine (S. Tanvir
Polymeric membrane based on et al. 2009). Schematic reaction of an example of
polyethersulfone (PES) is widely used mem- enzymatic covalent immobilization onto inor-
branes in ultrafiltration processes due to their ganic supports is illustrated in Fig. 4.
high performance and low-cost profile. PES Applications of covalently immobilized mem-
membranes have been used also in more sophis- brane systems are membrane electrodes for ana-
ticated application such as carrier for immobili- lytical purposes, reactions of substrates whose
zation of bioactive molecules in membrane molecular weight is low as compared to mem-
bioreactors. For this aim effort has been done to brane molecular weight cut-off, and enzymatic
introduce reactive groups for biomolecule immo- conversion of macromolecules to lower molecu-
bilization without affecting the overall bulk prop- lar weight species able to permeate the
erties. Photochemical surface modification of supporting membrane.
existing PES membrane is the most popular tech-
nique for introduction of reactive groups on PES
membrane. In fact PES has an intrinsic References
photoreactivity making possible to perform the
modification in mild reaction condition. Mono- Chen P-C, Huang X-J, Huang F, Ou Y, Chen M-R, Xu Z-K
(2011) Immobilization of lipase onto cellulose
mer like acrylic acid has been grafted in this way
ultrafine fiber membrane for oil hydrolysis in high
on PES membrane and then activated for enzyme performance bioreactor. Cellulose 18:1563–1571
immobilization using 1-ethyl-3-(3-dimethylami- Huang X-J, Chen P-C, Huang F, Ou Y, Chen M-R, Xu Z-K
nopropyl) carbodiimide hydrochloride (EDC). (2011) Immobilization of Candida rugosa lipase on
electrospun cellulose nanofiber membrane. J Mol
Inorganic membranes, such alumina, titania,
Catal B Enzym 70:95–100
silica, etc., can be also used for enzymatic immo- Tanvir S, Pantigny J, Boulnois P, Pulvin S (2009) Cova-
bilization via covalent binding if functionalized lent immobilization of recombinant human cyto-
in a suitable way. Hydroxyl groups present onto chrome CYP2E1 and glucose-6-phosphate
dehydrogenase in alumina membrane for drug screen-
inorganic membrane surface are not able to
ing applications. J Membr Sci 329:85–90
directly coupling enzymes. Activation of Vitola G, Mazzei R, Fontananova E, Giorno L (2015)
hydroxyl groups can be performed by silanization PVDF membrane biofunctionalization by chemical
reagents, such as (3-aminopropyl)triethoxysilane grafting. J Membr Sci 476:483–489
S
(i) (ii)
Solubility
Solubility
a
Supercritical
behavior
b
c
Supercritical
behavior
Solubility of Gases in Membranes, Fig. 1 Different membranes (e.g., CO2 in PDMS), (iii) sigmoidal sorption
shapes of solubility isotherms in polymeric membranes. of polar vapors in hydrocarbon glassy membranes (e.g.,
(i) (a) Sorption of gases and vapors in glassy membranes, alcohols in PTMSP) (Nakanishi et al. 1987), and (iv) CO2
(b) sorption of light gases in glassy and rubbery mem- sorption in an initially glassy membrane (e.g., PMMA)
branes, and (c) sorption of gases and vapors in rubbery (Carlà et al. 2005)
membranes. (ii) Supercritical sorption in rubbery
can show a sigmoidal shape of the solubility (sorption-induced glass transition), which occurs
isotherm (Fig. 1iii). as a change of concavity of the solubility iso-
If the glassy membrane is close to its glass therm (Fig. 1iv). The solubility in glassy mem-
transition temperature and/or if the penetrant branes can be modeled by the dual mode
has high solubility in the membrane and is able empirical model (Barrer et al. 1958) or the
to significantly swell and plasticize the mem- nonequilibrium approaches proposed by
brane, a glass transition can be observed at con- Doghieri and coworkers (Doghieri and Sarti
stant temperature by increasing the gas pressure 1996, De Angelis and Sarti 2011).
Solubility of Gases in Membranes 3
UF
pickling
L
proteic flour
desulfidation
desalination
drying
water,
Ca(OH)2, concentrated
Na2S proteic fractions
skins
exhausted
bath
UF
Permeate
(low M.W. species, sulfide)
treated skins,
exhausted liquor
References
CH3OCH2Cl
R R CH2Cl
SnCl4
R + R CH2Cl R CH2 R
Chloromethylation and Amination of Polymers (for AEM), Fig. 1 Chloromethylation and methylene bridge
crosslinking of polymers
Chloromethylation R R
and Amination
of Polymers (for AEM),
Fig. 2 Amination reaction R1
of chloromethylated
N H
polymers
NH3 R2 R1
Cl− N+H3 R
N+H Cl−
R2
R1 R1
R N H N R3 R
H R2
CH2Cl
R1 R1
Cl− N+H2 N+ Cl−
R2
R3
Polyelectrolyte Membrane for OSN, Table 1 NF performance of PEM membranes in aqueous applications
Retention (%)
Membrane Permeance (l.m 2.bar 1.h 1) Cl SO42
(PAA pH 4.5/PDADMAC pH 4.5)4.5 12.15 4.34 4.4 4.3 24 14
(PSS/PDADMAC)4.5 20.83 0.86 15.5 1.4 92.3 0.9
(PDADMAC/SPEEK)5 15.6 1.04 15.9 4 93.9 1
Polyelectrolyte Membrane for OSN, Table 2 OSN performance of PEM membranes in solvent applications (RB in
IPA)
Membrane Permeance (l.m 2.bar 1.h 1) RB retention (%)
(PAA pH 4/PDADMAC pH 7)5 0.03 97.0 2.1
(PDADMAC/SPEEK)5 0.08 98.2
Polyelectrolyte Membrane for OSN, Table 3 Comparison of performance between PEM membranes and other OSN
membranes
RB/IPA RB/DMF
Membrane Permeance (l/m2.h.bar) Retention (%) Permeance (l/m2.h.bar) Retention (%)
Multilayered PEC 0.12–1.57 >99 0.06–0.2 94–98
Polypyrrole 1.42 98 0.03 90
PDMS 0.086 91 n.m. n.m.
Poly(sulfone) 0.14 77.5 n.m. n.m.
Poly(sulfone)/SPEEK 0.47 95.6 n.m. n.m.
Starmem™ 120 0.49 100 – –
Starmem™ 228 0.087 99.6 – –
Starmem™ 240 0.29 97.9 – –
MPF-50 0.72 96 – –
n.m. not measured
– unstable in the solvent
cationic and anionic polyelectrolytes. Langmuir Schönhoff M (2003) Layered polyelectrolyte complexes:
16(2):287–290 physics of formation and molecular properties. J Phys
Li X, De Feyter S, Chen D, Aldea S, Vandezande P, Du Condens Matter 15(49):R1781–R1808
Prez F, Vankelecom IFJ (2008) Solvent-resistant Vandezande P, Gevers LEM, Vankelecom IFJ (2008) Sol-
nanofiltration membranes based on multilayered poly- vent resistant nanofiltration: separating on a molecular
electrolyte complexes. Chem Mater level. Chem Soc Rev 37:365–405
20(12):3876–3883
H
Nuclear Science and Technology, enrichment of uranium in its less abundant 235U
Membrane in isotope for military purposes during the Second
World War. The method is still applied in several
Grażyna Zakrzewska-Kołtuniewicz installations producing the enriched uranium for
Institute of Nuclear Chemistry and Technology nuclear fuel for power reactors. The studies on
(Instytut Chemii i Techniki Ja˛drowej), separation of isotopes of other elements like
Warszawa, Poland hydrogen, oxygen, nitrogen, carbon, lithium,
chlorine, and lanthanides, by using different
membrane processes are carried out in many
Recent achievements in the area of membrane laboratories.
processes are being applied for solving the prob-
lems in nuclear science and technology. The most
important application of membrane processes is Radioactive Waste Treatment
the treatment of liquid radioactive waste, often
combined with the recovery of valuable materials The application of membrane processes for radio-
such as water, boric acid, metals, or radioactive active waste treatment (Membranes in nuclear
isotope of hydrogen – tritium. Separation of stable waste treatment) is a common industrial practice.
isotopes and enrichment of uranium in the 235U Nuclear waste processing by pressure-driven
isotope for production of nuclear fuel, as well as membrane processes (nuclear waste processing
cleaning the exhaust gas from nuclear power by pressure-driven membrane processes) is a
plants, are possible with membrane processes. standard method applied in nuclear power plants
Reverse osmosis may be applied in nuclear desali- and nuclear centers; thermal membrane process
nation; other membrane processes, like membrane (nuclear waste processing by thermal processes),
distillation, are also considered as an alternative to namely, membrane distillation, was proposed for
energy-intensive distillation methods. liquid low and intermediate waste concentration.
Advanced researches are carried out to employ
liquid membranes for processing radioactive
Separation of Isotopes waste, especially the waste from the back-end of
nuclear fuel cycle. Membrane contactors pose
The issue of membrane in isotope separation new field of applications including such tech-
(▶ membrane for the isotope separation) is niques like supported liquid membranes (nuclear
discussed in the scientific literature from the waste processing by supported liquid membranes)
first application of molecular diffusion for and membrane liquid–liquid extraction.
# Springer-Verlag Berlin Heidelberg 2014
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1372-3
2 Nuclear Science and Technology, Membrane in
Khayet M, Mengual JI, Zakrzewska-Trznadel G (2006) Nörenberg H, Burlakov VM, Kosmella HJ, Smith GDW,
Direct contact membrane distillation for nuclear desa- Briggs GAD, Miyamoto T, Tsukahara Y (2001)
lination, part II- experiments with radioactive solu- Pressure-dependent permeation of noble gases (He,
tions. J Nucl Desalin 2:56–73 Ne, Ar, Kr, Xe) through thin membranes of oriented
Kim SH, Kim GT, Yim SK, Choi KH, Yoon CH, Choo polypropylene (OPP) studied by mass spectrometry.
KH, Choi SJ (2002) Application of energy efficient Polymer 42:10021–10026
reverse osmosis system for seawater desalination. Sasaki S, Tega E, Shimada A, Akahori S, Suzuki T,
Desalination 144:361–365 Okuno K, Kondo K (2003) Basic characteristics of
Le Digabel M, Truan PA, Duret D, Laquerbe C, Perriat P, hollow-filament polyimide membrane in gas separa-
Niepce JC, Pelletier T (2003) Application of gas sep- tion and application to tritium monitors. J Radioanal
aration membranes to detritiation systems. Desalina- Nucl Chem 255:91–95
tion 148:297–302 Zakrzewska-Trznadel G (2006) Tritium removal from
water solutions. Desalination 1–3:737–738
I
rffiffiffiffiffiffiffi
Isotope Separation, Membrane for yð1 xÞ M2
a¼ ¼
xð1 y Þ M1
Grażyna Zakrzewska-Kołtuniewicz
Institute of Nuclear Chemistry and Technology where x and y are mole fractions of two separated
(Instytut Chemii i Techniki Ja˛drowej), isotopes and M1 and M2 are molecular weights of
Warszawa, Poland these components of the isotopic mixture.
In 1895 Rayleigh and Ramsey have separated
argon and nitrogen using this method, and in
The use of membranes for the separation of iso- 1920 Aston employed molecular effusion for
topes is one of the first practical applications for enrichment of neon-22 isotope. Large improve-
membrane processes. The first application was ment of the technology was achieved by Gustav
based on the effects that were described in 1846 Ludwig Hertz who developed the separating cas-
by Thomas Graham, as a phenomenon of molec- cade, which was composed of several diffusion
ular effusion, i.e., differentiated flow rate of gases stages. They also used of the 24-stage cascade in
through small holes. When a mixture of two gases 1932, which almost completely separated iso-
in a closed vessel is allowed to permeate through topes of neon, and by applying of the 48-stage
the porous barrier, assuming an equal concentra- cascade, they have separated isotopes of hydro-
tion of the two gases, the molecules of the lighter gen. In 1936 Wooldridge, Jenkins, and Smythe
component strike the barrier more frequently than have enriched isotopes of neon, hydrogen, and
the molecules of the heavier gas. If the holes of carbon in methane with 34-stage cascade. The
the barrier are sufficiently small to avoid convec- most spectacular application of molecular effu-
tion flow (flow by volume) of gas and large sion was enrichment of uranium-235 in natural
enough to allow passage of the individual mole- uranium for military purposes within the frames
cules, then the lighter molecules escape more of Manhattan Project during the Second World
readily through the pores and the permeate is War. The all of the mentioned processes of sep-
enriched in the light component. The efficiency aration of isotopes were carried out in the gas
of partitioning is described by separation factor a phase. In case of uranium isotope separation, the
expressed as the ratio of mole fractions of sepa- gas applied in the process was uranium
rated components after and before passing hexafluoride, UF6. The membrane material had
through the porous barrier or as the square root to be chemically resistant in this case, since the
of the inverse ratio of the corresponding molecu- uranium hexafluoride used to produce enriched
lar weights: uranium-235 is highly corrosive (easily
converted into hydrofluoric acid and harmful
oxyfluorides as UO2F2). The important parame- membranes made of polymers, such as polyeth-
ters of the molecular effusion barrier are the pore ylene terephthalate (PET), polyethylene (PE),
diameter and the permeation rate since according polytetrafluoroethylene (PTFE), cellulose acetate
to the theory of molecular effusion, the diffusion (CA), and plasticized polyvinyl chloride (PVC),
transport through the membrane is selective when were taken by Marcea (1983). Although the
the pore size is commensurate with the mean free selectivity of polymers is lower than metallic
path of the molecules under the given conditions. membranes, it is worthy to point out, since the
Also the large plants employing the molecular numerous benefits of their use, such as the
effusion (which is also called molecular diffusion low-cost of membranes, the possibility of forma-
or gaseous diffusion) were built in the United tion of capillaries resulting in large areas for
States with the most famous K-25 plant in Oak permeation, and no need of high pressures and
Ridge, Tennessee. The other systems were temperatures.
constructed in 1950s at Oak Ridge, Paducah, The studies on separation of hydrogen and
Kentucky, and Portsmouth, Ohio, in the United oxygen in the liquid phase (water) were carried
States, Capenhurst in England, and at Pierrelatte out in Pacific Northwest Laboratory, USA
and Tricastin in France. There are also some (Nelson et al. 1996). Polymeric membranes
reports on gaseous diffusion plants in the former were used in Institute of Nuclear Chemistry and
USSR, Great Britain, Argentina, and in the Peo- Technology, (Poland). They were made of
ple’s Republic of China (Kirk-Othmer 1997). regenerated cellulose, cellulose acetate
Today, the gaseous diffusion is an important (Chmielewski et al. 1991), and polytetrafluor-
method for uranium-235 enrichment, despite the oethylene (Zakrzewska-Trznadel et al. 1996).
competitiveness of the centrifugal methods. This The economic assessment showed that mem-
is used in the United States and France, including brane permeation is competitive with other
Eurodif, led by France, Italy, Spain, and Belgium, methods of hydrogen and oxygen isotopes sepa-
which holds the plants in Tricastin and Pierrelatte ration. The demand for heavy oxygen water, due
(France). to the development of PET diagnostic method,
For preparation of membranes, different has intensified the interest in new processes of
methods are applied: etching with strong acids separating isotopes of oxygen, among
(alloys of gold and silver), sintering and extrusion others – membrane method (Kim et al. 2004).
of fine metal powders and oxides of metals The following isotopes of chlorine (Campbell
(nickel, aluminum oxides), and the anodic oxida- 1985), carbon (Fritz et al. 1987), lithium
tion (aluminum oxides). Typical gas diffusion (Whitworth et al. 1994) in aqueous solutions,
membrane has a pore size of 0.006–0.04 mm and uranium (Okamoto et al. 1980) in ammonia
and operates at temperature of 60–200 C and at were separated by means of various membrane
pressure of 0.4–3.3 bar. Support layer of the techniques and by using of different membranes.
membrane is a porous material with a pore size Gadolinium and neodymium isotopes were sepa-
of 2–10 mm. Ceramic and metallic microporous rated by means of a hybrid complexation/
membranes were applied for separation of iso- nanofiltration (Chitry et al. 2001) processes. The
topes, including other than uranium, such as iso- new complexing agents and ligands, which were
topes of argon, neon, and hydrogen. Although used in the hybrid process, were developed based
information about the materials used for on DTPA (see also Chitry et al. 2001).
manufacturing gaseous diffusion membranes are
very scarce, it is known that French technology
used sintered anode and aluminum, alloys of gold
References
and silver, nickel, Teflon, porcelain (Burggraaf
and Cot 1996), and zirconium (Hsieh 1996). Burggraaf AJ, Cot L (1996) Membrane science and tech-
Attempts of using the polymeric membranes nology series, vol 4, Fundamentals of inorganic
for the separation of isotopes of hydrogen with
Isotope Separation, Membrane for 3
membrane science and technology. Elsevier, Amster- Kirk-Othmer A (1997) Diffusion separation methods. In:
dam/Lausanne/New York/Oxford/Shannon/Tokyo Ruthven DM (ed) Encyclopedia of separation technol-
Campbell DJ (1985) Fractionation of stable chlorine iso- ogy, vol 1. Wiley, New York/Chichester/Weinheim/
topes during transport through semi-permeable mem- Brisbane/Singapore/Toronto
branes. M.Sc. thesis, University of Arizona Marcea P (1983) Permeation of H2 and D2 through poly-
Chitry F, Pellet-Rostaing S, Vigneau O, Lemaire M (2001) mers. Isotopenpraxis 19(5):153–156
Nanofiltration-complexation: a new method for isoto- Nelson DA, Duncan JB, Jensen GA, Burton SD
pic separation of heavy metals. Chem Lett (1996) Isotopomeric water separations with supported
30(8):770–771 polyphosphazene membranes. J Membr Sci
Chmielewski AG, Zakrzewska-Trznadel G, Miljević N, 112:105–113
Van Hook WA (1991) 16O/18O and H/D separation Okamoto M, Oi T, Fujii Y, Kakihana H (1980) Dependen-
factors for liquid/vapour permeation of water through cies of pH and current density on the isotope effect
an hydrophobic membrane. J Membr Sci 60:319–329 occured by the electromigration of uranyl ions in a
Fritz SJ, Hinz DL, Grossman EL (1987) Hyperfiltration- cation exchange membrane. Isotopenpraxis
induced fractionation of carbon isotopes. Geochim 16(2):58–61
Cosmochim Acta 51:1121–1134 Whitworth TM, Mariñas BJ, Fritz SJ (1994) Isotopic frac-
Hsieh HP (1996) Membrane science and technology tionation and overall permeation of lithium by a thin-
series, vol 3, Inorganic membranes for separation and film composite polyamide reverse osmosis membrane.
reaction. Elsevier, Amsterdam/Lausanne/New York/ J Membr Sci 88:231–241
Oxford/Shannon/Tokyo Zakrzewska-Trznadel G, Chmielewski AG, Miljević N
Kim J, Park SE, Kim TS, Jeong DY, Ko KH (2004) Isoto- (1996) Separation of protium/deuterium and oxygen-
pic water separation using AGMD and VEMD. 16/oxygen-18 by membrane distillation process.
Nuklonika 49(4):137–142 J Membr Sci 113:337–342
M
Vo
Membranes in Nuclear Waste VRC ¼
Treatment VR
Nuclear Waste Processing: Supported Liquid Membranes, Table 1 Supported liquid membranes for treatment of
radioactive waste
Separated Stripping
radionuclides Application Extracting agent (LM) solution Support Reference
Pu(IV) Separation of Tri-n-butyl phosphate 0.1 M Hollow fiber Rathore
plutonium from (TBP) NH2OHHCl polypropylene et al. 2001
radioactive in 3 M HNO3 (Enka) membrane
waste
Pu(IV) Separation of 2-ethylhexyl 2- 0.05 M Polypropylene Kedari
plutonium from ethylhexyl phosphonic HNO3 and Enka 2E HF-PP et al. 1999
radioactive acid in n-dodecane 0.3 oxalic membrane
waste acid solution
U(VI) Recovery of Alamine 336 in toluene Distilled PTFE flat sheet Lakshmi
233
U, uranium from water membrane et al. 2004
6 M HCl at the
back-end of fuel
cycle
232
Th U/Th separation N,N-di(2-ethylhexyl) 0.01 M PTFE flat sheet Shailesh
in 4 M HNO3 in isobutyramide HNO3 membranes, et al. 2006
the presence (D2EHIBA) in 0.45 mm, 72 %
of137 Cs,85,89 Sr, n-dodecane porosity
and59 Fe (Sartorius)
U(VI) Actinides N,N,N0 ,N0 -tetra-2- 0.01 M PTFE flat sheet Panja
partitioning ethylhexyl-3-pentane- HNO3 membranes, et al. 2011
diamide (T2EHDGA) in 0.45 mm, 64 %
n-dodecane, 30 % porosity
iso-decanol as the
modifier
U(VI) Recovery of Tetraoctyldiglycolamide 0.1 M HNO3 PTFE flat sheet Panja
actinides at the (TODGA) in n-dodecane membranes et al. 2009
back-end of fuel
cycle from acidic
feeds
U(VI) Recovery of N,N,N0 ,N0 -tetra-2- 0.01 M PTFE flat sheet Panja
actinides at the ethylhexyl-3-pentane- HNO3 membranes et al. 2012
back-end of fuel diamide (T2EHDGA) in
cycle from acidic n-dodecane, 30 %
feeds iso-decanol as the
modifier
U(VI) Extracting of Aliquat 336 (N-methyl- Distilled PTFE flat sheet Mohapatra
uranyl ions from N,N-dioctyloctan-1- water membranes et al. 2006
6 M HCl ammonium chloride) (Sartorius)
environment
U(VI) Recovery of TBP in kerosene NaOH Hollow fiber Ramkul
uranium from membrane et al. 2007
nitrate media contactor
U(VI) Separation of Tri-n-octylphosphine Ammonium PTFE flat sheet Singh
uranium from oxide (TOPO) in carbonate membranes, et al. 2007
phosphoric acid n-dodecane 0.45 mm, 84 %
porosity
Am(III) Extraction Am TEHDGA in dodecane 0.1 M HNO3 PTFE flat sheet Panja
(III) from 1–6 M membranes et al. 2008
HNO3 (Sartorius)
0.20–5 mm
(continued)
Nuclear Waste Processing: Supported Liquid Membranes 3
hollow fiber-supported liquid membrane and perme- liquid membrane containing N, N-di(2-ethylhexyl)
ability analysis. J Chin Inst Chem Eng 38:489–494 isobutyramide (D2EHIBA) as the carrier. J Membr
Ramanujam A, Achuthan PV, Dhami PS, Kannan R, Sci 272:143–151
Gopalakrishnan V, Kansra VP, Iyer RH, Balu Singh SK, Misra SK, Sudersanan M, Dakshinamoorthy A,
K (2001) Separation of carrier-free 90Y from high Munshi SK, Dey PK (2007) Carrier-mediated transport
level waste by supported liquid membrane using of uranium from phosphoric acid medium across
KSM-17. J Radioanal Nucl Chem 247:185–191 TOPO/n-dodecane-supported liquid membrane.
Rathore NS, Sonawane JV, Kumar A, Venugopalan AK, Hydrometallurgy 87:190–196
Singh RK, Bajpai DD, Shukla JP (2001) Hollow fiber Teramoto M, Sheng Fu S, Takatani K, Ohnishi N, Fukui T,
supported liquid membrane: a novel technique for sep- Arai K (2000) Treatment of simulated lo level radioac-
aration and recovery of plutonium from aqueous acidic tive wastewater by supported liquid membranes: uphill
wastes. J Membr Sci 189:119–128 transport of Ce(III)using CMPO carrier. Sep Purif
Raut DR, Mohapatra PK, Manchanda VK (2012) A highly Technol 18:57–69
efficient supported liquid membrane system for selec- Ura P, Prakom R, Weerawat P, Milan HJ (2005) Purely
tive strontium separation leading to radioactive waste extraction and separation of mixture of cerium(IV) and
remediation. J Membr Sci 390–391:76–83 lanthanum(III) via hollow fiber supported liquid mem-
Rawat N, Mohapatra PK, Lakshmi DS, Bhattacharyya A, brane. J Ind Eng Chem 11:926–931
Manchanda VK (2006) Evaluation of supported liquid Yassine T (2000) Separation of 99mTc from 99Mo by using
membrane containing a macrocyclic ionophore for TOPO – kerosene supported liquid membrane.
selective removal of strontium from nuclear waste solu- J Radoanal Nucl Chem 246:665–669
tion. J Membr Sci 275:82–88 Youn IJ, Lee Y, Lee WH (1995) Analysis of permeation
Shailesh S, Pathak PN, Mohapatra PK, Manchanda VK rate of cobalt ions across a supported liquid membrane
(2006) Transport studies of uranium across a supported containing HEH(EHP). J Membr Sci 100:69–75
N
Nuclear Waste Processing: Pressure- It is used for removal of radionuclides from var-
Driven Membrane Processes ious streams in nuclear power plants: reactor
coolant, floor drains, reactor outage waste, spent
Grażyna Zakrzewska-Kołtuniewicz resin sluice water, the waste from steam genera-
Institute of Nuclear Chemistry and Technology tor chemical cleaning, and fuel cooling pond
(Instytut Chemii i Techniki Ja˛drowej), water. It can be applied for the liquid waste
Warszawa, Poland from research activities and medical applications
(Fig. 2), as well as for cleaning the defense and
reprocessing effluents (IAEA Technical Reports
The pressure-driven membrane processes such as Series 2004). Since RO rejects all dissolved mat-
reverse osmosis (RO), nanofiltration (NF), ultra- ters from water solution, the product from RO
filtration (UF), and microfiltration (MF) are the modules – high-purity water – may be recycled
most commonly used membrane methods of within the nuclear power plant. Big variety of RO
radioactive waste processing. The reasons for a systems is available in the market and various
wide use of membrane methods are numerous: polymeric materials are used for membrane
they are mature technologies with long design manufacturing.
and operation experience, well proven in nuclear Nanofiltration is able to separate monovalent
industry, with broad spectrum of membranes and ions from multivalent ions or organic compounds
membrane modules developed. The variety of from monovalent ions. The best known applica-
pressure-driven membrane processes covers tion of NF is boric acid recovery from reactor
wide spectrum of media: from ionic species to cooling water (Zakrzewska-Trznadel 2008). NF
large particles (Fig. 1). Therefore, they are suit- can be applied for removal of dissolved uranium
able for large number of applications, being flex- ions from wash solutions discharged from fuel
ible in process configurations and system fabrication plants. Integrated with macromolecu-
optimization. They can be easily integrated with lar ligands, NF was applied for separation of
other conventional methods to form efficient lanthanides and actinides (Chitry et al. 2001a)
treatment systems. Pressure-driven membrane and separation of neodymium and gadolinium
processes are especially convenient for the con- isotopes (Chitry et al. 2001b).
centration of large volumes of low and interme- Ultrafiltration is a good pretreatment method
diate level radioactive waste with low salinity before reverse osmosis. It is used for removal of
and low radioactive species content. colloid matters and particles to avoid the fouling
Reverse osmosis, well-developed technology, of RO membranes, as well as alpha-emitting sub-
has found many applications in nuclear industry. stances, namely, actinides, which are often in
# Springer-Verlag Berlin Heidelberg 2013
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1376-2
2 Nuclear Waste Processing: Pressure-Driven Membrane Processes
Nuclear Waste
Processing: Pressure-
Driven Membrane
Processes, Fig. 2 Three-
stage RO plant for the
treatment of institutional
radioactive waste at
Radioactive Waste
Management Plant at
Swierk, Poland
colloidal form. Combined with chelating com- effluents from fuel fabrication plants. The decon-
pounds or dispersed sorbents that bind small tamination factors reported in the literature are in
ions, UF can be applied for removal of dissolved the range of 1000 for a emitters and 100 for b and
radioactive metal ions from diluted aqueous solu- g species, and the overall volume reduction of the
tions. UF membranes reject complexed or sorbed order of 104 is achieved with UF systems. Inor-
ions allowing uncomplexed ions to pass through ganic, ceramic membranes in the region of UF
as permeate. Ultrafiltration may be employed for pore size are offered in the market, which
the treatment of water from fuel storage ponds, enhance the potential of the process.
cleaning the laundry wastes, solvent wash Microfiltration is applied as a pretreatment
liquors, and plutonium evaporator overheads stage before RO or UF; it can be also used sepa-
from reprocessing lines or purification of rately for the concentration of radioactive
Nuclear Waste Processing: Pressure-Driven Membrane Processes 3
suspensions and dewatering of concentrated method for isotopic separation of heavy metals.
sludge. It may be applied with conjunction of Chem Lett 30(8):770–771
IAEA Technical Reports Series No 431 (2004) Applica-
precipitation process to remove various kinds of tion of membrane technologies for liquid radioactive
radionuclides. Both polymeric and inorganic waste processing. International Atomic Energy
membranes are employed for MF process. Agency, Vienna
In spite of intensive studies in the field of Zakrzewska-Kołtuniewicz G (2015) Advancement in
membrane methods for liquid radioactive waste
membrane technologies and continuous develop- processing: current opportunities, challenges, and the
ment of novel processes, the pressure-driven global scenario. In: Pabby AK, Rizvi SSH, Sastre AM
membrane processes remain the leading mem- (eds) Handbook of membrane separations: Handbook
brane methods in nuclear industry Zakrzewska- of membrane separations: chemical, pharmaceutical,
and biotechnological applications. CRC Press/Taylor &
Kołtuniewicz (2015). Francis Group, Boca Raton/London/New York, pp
665–708
Zakrzewska-Trznadel G (2008) Radioactive waste
References processing: advancement in pressure driven processes
and current world scenario. In: Pabby AK, Rizvi SSH,
Sastre AM (eds) Handbook of membrane separations:
Chitry F, Pellet-Rostaing S, Gozzi C, Lemaire M (2001a) chemical, pharmaceutical, and biotechnological appli-
Separation of lanthanides(III) by nanofiltration- cations. CRC Press/Taylor & Francis Group, Boca
complexation in aqueous medium. Sep Sci Technol Raton/London/New York, pp 843–882
36(4):605–618
Chitry F, Pellet-Rostaing S, Vigneau O, Lemaire
M (2001b) Nanofiltration-complexation: a new
N
10
0 4 8 12 16 20
time (h)
Nuclear Waste Processing: Thermal Processes 3
(Bq/dm3)
radioactive waste
10
distillate
1
0 4 8 12 16 20
time (h)
References
Liquid
qw
Substate
Wenzel Model, Fig. 1 Liquid droplet on a rough surface. The contact angle can be predicted by Wenzel model (Hsu
2010)
C
The Wenzel regime is usually recognized as From Eq. 2, it can be found that droplets will have
homogeneous wetting, since the liquid a higher apparent contact angle if less area is in
completely penetrates into the grooves. While contact with the solid substrate. The CB equation
under some circumstances, especially the simply indicates the contact angle can be
increase of the surface roughness, vapor pockets increased even when the intrinsic contact angle
may be trapped underneath the liquid yielding a of a liquid on the original smooth surface is less
composite interface. This heterogeneous wetting than 90 .
is usually described by the Cassie-Baxter New developments in the field show that there
(CB) model, from which the apparent contact may need to be taken other considerations for
angle (yCB) is given by equation: (Cassie and contact angles and contact angle hysteresis. It is
Baxter 1944) suggested that the contact line model is a better
approach to predict the superhydrophobicity of
cos yCB ¼ f s cos yc þ f v cos yv (1) surfaces (Gao and McCarthy 2007, 2009)
(Fig. 1).
Liquid
q cs
Substate
Cassie-Baxter Model, Fig. 1 Vapor pockets are trapped Cassie-Baxter model (Hsu et al. 2011, reproduced with
between the grooves and the liquid droplet. This state is permission from Elsevier Ltd.)
essential for superhydrophobicity and is described by
Hairy Superhydrophobic Surface, Fig. 1 SEM images water repellency. (a) The hair on strider’s abdomen is
of the hair layer of the water strider’s body. The hair tips tilted at around 30–45 relative to the body surface. (b)
are bent inward toward the body to enhance the degree of The hair on strider’s leg (Hsu 2010)
Hairy Superhydrophobic
Surface, Fig. 2 A water
droplet forms a spherical
bead on Lady’s Mantle leaf
on underwater respiration can be found in the Herminghaus 2004). Water droplets are pinned
section of plastron effect. by the hydrophilic trichomes causing high con-
Hairy leaves with a feature similar to lotus tact angle but roll-off angle.
effect are also common. These plants, i.e.,
Lady’s Mantle (Alchemilla vulgaris), exhibit a
plurality of flexible hairs, termed trichomes, on
Cross-References
their leaves and stems (Fig. 2). Water droplets on
the fuzzy leaves can be suspended by the tri-
▶ Lotus Effect
chomes, which effectively prevent the droplets
▶ Plastron Effect
from wetting the leaf. Although the leaf itself
▶ Young’s Model
shows an excellent hydrophobicity, those tri-
chomes are found to be hydrophilic (Otten and
Hairy Superhydrophobic Surface 3
Cross-References
Hydrophobicity is the term frequently used in
surface chemistry describing the tendency of ▶ Super-hydrophobicity
moving away from water or aqueous environ-
ment. The name, the combination of hydro- and
Lotus Effect, Fig. 1 SEM micrographs of lotus leaf showing its relatively rough surface covered by small micron-sized
protrusions (a) and submicron-sized wax crystals (b) (Hsu 2010)
References
Porous Silicon,
Fig. 1 Schematic of the
etching cell used for the
anodic etching of silicon
Porous Silicon, Fig. 2 SEM images of (a) top-down view of porous silicon showing the irregularly shaped pores
produced and (b) side-on view of porous silicon still supported on bulk silicon (at bottom)
Porous Silicon,
Fig. 3 Photographs of pSi
membranes (a) attached to
the silicon wafer and (b)
lifted off the silicon wafer
Porous Silicon 3
bottom of the film to liberate it from the bulk fabry-perot films for loading and release of a steroid.
Si. Electropolishing is achieved by increasing Langmuir 20(25):11264–11269
Canham L (1997) Properties of porous silicon. The insti-
the current density and/or decreasing the HF con- tution of electrical engineers. United Kingdom,
centration. The brittle nature of pSi membranes London
makes them unsuitable for commercial mem- Cruz S, Honig-dOrville A, Muller J (2005) Fabrication
brane applications. However, the small pores and optimization of porous silicon substrates for dif-
fusion membrane applications. J Electrochem Soc
make interesting systems for fundamental trans- 152(6):C418–C424
port investigations such as gas (Solanki Jane A, Dronov R, Hodges A, Voelcker NH (2009) Porous
et al. 2004; Cruz et al. 2005) and fluid silicon biosensors on the advance. Trends Biotechnol
(Velleman et al. 2010, Fig. 3). 27(4):230–239
Lehmann V (2002) Electrochemistry of silicon: instru-
mentation, science, materials and applications.
Weinheim, Germany
Cross-References Schmeltzer JM, Buriak JM (2005) Recent developments
in the chemistry and chemical applications of porous
silicon. In: Rao CN, M€ uller A, Cheetham AK (eds)
▶ Biodegradable The chemistry of nanomaterials: synthesis, properties
▶ Biointerface and applications. Wiley, Weinheim, pp 518–550
▶ Porous Alumina Searson PC (1991) Porous silicon membranes. Appl Phys
▶ Silicon Lett 59(7):832–833
Solanki CS, Bilyalov RR, Poortmans J et al (2004) Self-
standing porous silicon films by one-step anodizing.
J Electrochem Soc 151(5):C307
References Velleman L, Shearer CJ, Ellis AV et al (2010) Fabrication
of self-supporting porous silicon membranes and
Anglin EJ, Schwartz MP, Ng VP et al (2004) Engineering tuning transport properties by surface functiona-
the chemistry and nanostructure of porous silicon lization. Nanoscale 2(9):1756–1761
A
Aligned Carbon Nanotube, Fig. 1 SEM image CNTs produced via CVD showing (a) randomly entangled, (b)
horizontally aligned, and (c) vertically aligned
nanotubes chemically attached to silicon. Nanoscale Yamamoto T, Watanabe K, Hernández E (2008) Mechan-
Res Lett 7(1):432 ical properties, thermal stability and heat transport in
Wu J, Paudel KS, Strasinger C et al (2010) Programmable carbon nanotubes. In: Jorio A, Dresselhaus G,
transdermal drug delivery of nicotine using carbon Dresselhaus MS (eds) Carbon nanotubes. Springer,
nanotube membranes. Proc Natl Acad Sci Berlin, pp 165–194
107(26):11698–11702
B
Biosensor-Based Membrane, Fig. 1 Schematic of basic mechanism of a membrane-based biosensor based upon the
change in conductance upon interaction between an antibody tethered to the ion channel and target analyte (antigen)
Polyacrylonitrile (PAN),
T >200°C
Fig. 2 Radical mechanism
of polyacrylonitrile · ·
N N N N· N N N N· N
cyclization
good chemical stability and low water adsorption support for fabrication of thin film composite
and can be operated at low and high temperatures. membranes for gas and vapor separations,
ABS can be processed with standard methods pervaporation and organic solvent nanofiltration.
(Rosato et al. 2000). Several companies have manufactured thin film
PAN has been widely used as a membrane composite membranes based on PAN porous sup-
material. Regarding transport properties, PAN ports over the years.
belongs to the group of extra low permeable
(barrier) polymers (e.g., P(CO2)~10 Barrer).
Due to high chemical stability, PAN is used for References
fabrication of micro- and ultrafiltration mem-
branes both for aqueous and nonaqueous applica- Gupta AK, Paliwal DK, Bajaj P (1991) Acrylic precursors
for carbon fibers. J Macromol Sci C 31:1–89
tions. These flat membranes are fabricated on a
Mark JE (2009) Polymer data handbook, 2nd edn. Oxford
nonwoven by a phase inversion process. It is University Press, New York
worth to mention, that PAN ultrafiltration mem- Rosato DV, Rosato MG, Rosato DV (2000) Concise ency-
branes are attractive for use as an efficient porous clopedia of plastics. Kluwer
P
Membrane Collapsing, Fig. 1 Collapsing of membrane porous structure: initial membrane (left), collapsed mem-
brane after TMP of 20 bar (right)
Membrane Compaction, 40
Fig. 1 Effect of reversible
membrane compaction on
the ethanol permeability
through dense membrane of
10
0
0 50 100 150 200
Pressure, bar
Pressure Decay Method the gas J through the membrane surface A over
the time period Dt can be described as a function
Alexey Volkov of pressure drop in the following equation with
A.V. Topchiev Institute of Petrochemical approximation of ideal gas law:
Synthesis, Russian Federation, Russian Academy
of Sciences (TIPS RAS), Moscow, Russia V upstream Dp
J mole=m2 h ¼
R T A Dt
Pressure decay method is one of the standard where R is universal gas constant and T is tem-
experimental techniques for characterization of perature. The method accuracy can be improved
membranes and membrane materials in terms of by avoiding any temperature fluctuations (e.g., in
sorption, diffusivity, or permeance; this method case of gas expansion) during single measure-
has a rather high sensitivity (Ferrari et al. 2010; ment and proper selection of highly sensitive
Mulder 1996). The principle of this method is and accurate pressure indicator(s) for required
based on estimation of amount of molecules pressure range.
sorbed or permeated through the membrane by The drawback of this method is that the driv-
monitoring of pressure decay in a chamber with a ing force across the membrane is continuously
constant known volume, where the membrane is changing during the single test since the upstream
placed. The amount of gas or vapor sorbed by side is isolated from the gas supply. However, it
membrane material at a given pressure is deter- is possible to consider a constant transmembrane
mined by the difference between initial and pressure difference if the pressure drop for single
actual pressures; for sorption experiments, the test is negligible in comparison with absolute
actual pressure is equilibrium one. Mass flow pressure in upstream side. On the other hand,
through the membrane is determined by monitor- such a pressure drop value should be sufficiently
ing of pressure decay in a chamber above the high enough to eliminate the undesired effect of
membrane with a constant volume (upstream temperature fluctuation and instrumental noise.
side) in time. This technique is more commonly From this end, the upstream side typically
used for measurement of gas transport due to includes two or more vessels with different cali-
higher values of compression coefficients, and brated volumes (see Fig. 1), so the overall volume
the schematic view of this experimental setup is can be adjusted by connecting one of the vessels
shown in Fig. 1. or its combination to the main line in order to
If the volume of upstream side Vupstream is measure the membranes with different
already calibrated and known, the mole flow of
# Springer-Verlag Berlin Heidelberg 2013
E. Droli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1405-1
2 Pressure Decay Method
Downstream
References
Pressure Decay Method, Fig. 1 Schematic view of
experimental setup to measure gas flow with pressure AWWA Staff (2005) Microfiltration and ultrafiltration
decay method: PI pressure indicator, V1 calibrated volume membranes for drinking water, 1st edn. American
of pipelines and fittings, V2 calibrated vessel volume, V3 Water Works Association
calibrated vessel volume Ferrari MC, Galizia M, De Angelis MG, Sarti GC
(2010) Vapor sorption and diffusion in mixed matrices
permeance at the same experimental setup within based on Teflon AF 2400. In: Freeman B, Yampolskii
Y (eds) Membrane gas separation. Wiley, New York,
desired experimental error. pp 125–142
Pressure decay method is also used as a rapid Grekhov A, Belogorlov A, Yushkin A, Volkov A (2012)
test for evaluation of the integrity of micro- and New express dynamic technique for liquid permeation
ultrafiltration membranes as well as membrane measurements in a wide range of trans-membrane
pressures. J Membr Sci 390–391:160–163
modules (AWWA Staff 2005). The upper side of
Mulder M (1996) Basic principles of membrane technol-
wetted membrane is pressurized with a gas, ogy. Kluwer, Dordecht/Boston/London
which is below its bubble point pressure. Broken
S
Better models have been proposed to study the hydrogen bonding as well as the interactions
non-Fickian diffusion. The following relation has with counterions in specific chemical environ-
been, for example, proposed for systems wherein ments can decide the expansion or the collapse
Mt/M1 ratio is 0.60 (Crank and Park 1951): of the polymer network, making smart gels/mem-
branes whereby a transport phenomenon can
Mt reversibly be controlled (Chaterji et al. 2007;
¼ 1 Aek2 t (2)
M1 Diaconu et al. 2012).
(Pearce 2007). Larger modules can also reduce In electrodialysis (ED) an external electric
operating and capital costs (Ng et al. 2008), with field is used to separate dissolved ions in the
16- and 18-in. modules now being offered on the saline feed, riving them to oppositely charged
market. ions through ion selective membranes. ED sys-
RO membranes require extensive tems consist of a series of cation and anion
pretreatment steps to remove solids, organic exchange membranes separated by spacers
foulants, and, in some cases, chlorine. RO mem- through which the concentrate streams and the
branes operate at pressures varying from 40 to demineralized water separately flow out of the
70 bar to overcome the osmotic pressure of the membrane module. Fouling, which occurs at the
saline feed and resistance due to concentration electrodes due to the accumulation of ions, can be
polarization buildup over time. Due to the high removed by periodical reversal of the electrodes’
pressures applied, RO membranes suffer from polarity.
compaction as well as significant fouling buildup The charge-based separation mechanism is
over time. These factors all contribute to the high effective at removing not just salt ions but also
energy cost of operating RO plants, despite sig- nitrates and other charged species (Voutchkov
nificant innovation in the last 50 years which has 2013). On the other hand, removal of charge
brought RO operations close to the thermody- neutral contaminants, such as nutrients or organic
namic limit (Elimelech and Phillip 2011). substances, is less effective than RO systems. ED
Forward osmosis as a desalination method was is economically competitive compared to RO
first proposed in the 1970s, but the first industrial when TDS of the water source is less than
FO plant has opened only in 2012 in Oman. FO 3,000 mg/L, so far mainly limiting its use to
uses a draw solution that has a higher osmotic brackish water desalination.
pressure than seawater to extract water from the ED membranes tend to be thicker than RO
saline feed into the draw solution through a semi- ones and prepared mixing an ion exchange resin
permeable membrane. Intense research and with a polymer binder. Requirements for the
development is now being focused on novel selection of the resin and binders are low electri-
membranes and draw solutions. Membranes for cal resistance, resistance to osmotic swelling, and
FO differ from those for RO mainly due to effects long life expectancy (Murray 1995). The latter
of concentration polarization and the need to aspect is crucial as most commercial ED mem-
prevent reverse draw solute permeation. Cellu- branes are sold as sealed filter cartridges.
lose acetate membranes, originally developed for Recent developments and future directions:
RO, have made a comeback for FO uses, partic- Alongside continuous optimization of polymeric
ularly due to their hydrophilic surface and good membranes, there is intense research in novel
chemical stability (Alsvik and Hägg 2013). membrane materials or membrane designs.
A combination of the two techniques has been A promising area of research is the incorporation
recently proposed (Klaysom et al. 2013), though of carbon nanotubes in thin-film composite mem-
its economic viability and social acceptance are branes to enhance permeability with no compro-
uncertain (Elimelech and Phillip 2011). In this mise on salt rejection (Mattia et al. 2014). In fact,
FO-RO hybrid system, wastewater is used as feed in these RO CNT-TFC membranes, the selectiv-
in a first FO unit with seawater used as draw ity is still determined by the selective layer of the
solution. The latter is, therefore, diluted before TFC, whereas the CNTs, embedded in it, provide
entering the RO stage. The RO concentrate is a high flux conduit for permeated water mole-
then fed to a second FO unit as draw solution cules. Other nanotube materials, such as boron
and, as a consequence, diluted before discharge. nitride and silicon carbide, have shown promise
To close the cycle, the wastewater feed from the in molecular dynamic simulations.
first FO unit is concentrated, thereby reducing its Another emerging class of materials for
discharge volume as well. RO-based desalination is represented by
graphene at its derivative, graphene oxide. Initial
Membranes for Seawater Desalination 3
reports on desalination using graphene oxide Alsvik I, Hägg M-B (2013) Pressure retarded osmosis and
membranes show high permeability and salt forward osmosis membranes: materials and methods.
Polymers 5(1):303–327
rejection (Nair et al. 2012), while molecular Cohen-Tanugi D, Grossman JC (2012) Water desalination
dynamic simulations have investigated the possi- across nanoporous graphene. Nano Lett
bility of high flux/high rejection through nano- 12(7):3602–3608
meter scale defects in a graphene layer (Cohen- Cotruvo J, Voutchkov N, Fawell J, Payment P, Cunliffe D,
Lattemann S (2010) Desalination technology: health
Tanugi and Grossman 2012). and environmental impacts. CRC Press, Boca Raton
In either case it should be noted that the Elimelech M, Phillip WA (2011) The future of seawater
increase in permeability promised by these desalination: energy, technology, and the environ-
novel membranes does not automatically trans- ment. Science 333(6043):712–717
Fritzmann C, Löwenberg J, Wintgens T, Melin T (2007)
late in a decrease in the energy cost of RO desa- State-of-the-art of reverse osmosis desalination. Desa-
lination. The latter, in fact, is related to the lination 216(1–3):1–76
pressure gradient across the membrane that, as IDA Desalination Yearbook (2012–2013) International
discussed, is already close to the thermodynamic desalination association and global water intelligence
Klaysom C, Cath TY, Depuydt T, Vankelecom IFJ
limit. Higher permeability membranes, though, (2013) Forward and pressure retarded osmosis: poten-
could reduce the footprint of RO plants and tial solutions for global challenges in energy and water
decrease the amount of chemicals for membrane supply. Chem Soc Rev 42(16):6959–6989
cleaning accordingly (Elimelech and Phillip Lee KP, Arnot TC, Mattia D (2011) A review of reverse
osmosis membrane materials for
2011). desalination – development to date and future poten-
Other potential RO membrane materials, at an tial. J Membr Sci 370(1–2):1–22
earlier developmental stage, include aquaporins Mattia D, Lee KP, Calabrò F (2014) Water permeation in
and polymer dendritic structures (Lee carbon nanotube membranes. Curr Opin Chem Eng
4:32–37
et al. 2011). Murray P (1995) Electrodialysis and electrodialysis
reversal – manual of water supply practices, M38.
American Water Works Association, Denver
Cross-References Nair RR, Wu HA, Jayaram PN, Grigorieva IV, Geim AK
(2012) Unimpeded permeation of water through
helium-leak – tight graphene-based membranes. Sci-
▶ Concentration Polarization ence 335(6067):442–444
▶ Draw Solution Ng HY, Tay KG, Chua SC, Seah H (2008) Novel 16-inch
▶ Fouling spiral-wound RO systems for water reclamation – a
quantum leap in water reclamation technology. Desa-
▶ Nanotube Membranes lination 225(1–3):274–287
▶ Thin Film Composite Membranes Pearce G (2007) Water and wastewater filtration: mem-
brane module format. Filtr Sep 44(4):31–33
Voutchkov N (2013) Desalination engineering – planning
and design. McGraw-Hill, New York
References
Blue Energy, a b c
Fig. 1 Osmotic processes ΔP ΔP
using semipermeable
membranes: (a) RO; (b)
PRO; (c) FO (arrow
indicates the direction of
water flow)
P F F DS F DS
Blue Energy,
Fresh water Fresh water @ low pressure
Fig. 2 Schematic of PRO
process for power
generation membrane
Water flow
Brine
P Diluted
Brine @ high pressure brine
Pump Turbine
generator
et al. 2009), resulting in the recovery of the harnessed directly when an external load is
chemical potential energy from the difference in connected to the circuit through the electrical
osmotic pressures of the two water streams, as current (movement of electrons) and the potential
shown schematically in Fig. 2. difference over the electrodes. Although the
applied electrical potential difference will reduce
RED Working Principles the driving force of the ions when the external
Unlike PRO, RED primarily depends on ion load is connected to the circuit, ions will continue
transport through the membranes when waters to be transported toward the cathode and anode as
of different salinities are placed on opposite long as the electrochemical potential difference is
sides of either cation or anion exchange mem- greater than the electrical potential difference.
branes. These membranes are stacked in an alter-
nating pattern between a cathode (reduction Challenges and Potential Large-Scale
electrode) and an anode (oxidation electrode) Applications
(Post et al. 2007). Another distinctive difference The PRO process requires a robust membrane
is that the RED system is not pressurized like that can withstand high-operating pressures and
PRO to obtain the osmotic energy mechanically. achieve a reasonable high water flux (Chou
Instead, direct electrical energy can be harvested et al. 2012), while RED requires not only a mem-
from the movement of the electrons required to brane of minimal electrical resistance but also the
maintain electroneutrality of the overall solution whole stack design with a low electrical resis-
as the ions from the saline solution are tance. Normally, seawater and freshwater are
transported toward either the anode or cathode used as a pair for both PRO (Lewis et al. 2011;
electrodes, as shown schematically in Fig. 3. Thorsen et al. 2009; Ramon et al. 2011) and RED
Specifically, electroneutrality is maintained (Ramon et al. 2011; Długołecki et al. 2010) pro-
via reduction at the cathode and oxidation at the cesses to harvest salinity gradient energy. Other
anode via an external electric circuit that results salinity gradient pairs such as concentrated brine
in electrons being transferred from the anode to from seawater desalination (Enomoto et al. 2010)
the cathode. Electrical energy can then be or hypersaline lakes such as the Dead Sea (Loeb
Blue Energy 3
e−
Cathode Electrode
Less Saline Solution
(River water)
C
External Na+ Cl− Na+ Cl− Saline Solution
Load (Sea water)
A
Less Saline Solution
(River water)
Anode Electrode
e−
Blue Energy, Fig. 3 A simple RED process showing the transport of ions where A is an anion exchange membrane and
C is a cation exchange membrane
1976, 2001; Lacey 1980) are also possible Chou S, Wang R, Shi L, She Q, Tang CY, Fane AG
resources for utilization. It is expected that (2012) Thin-film composite hollow fiber membranes
for pressure retarded osmosis (PRO) process with high
large-scale applications for PRO and RED power density, J Membr Sci 389:25–33
would be near river estuaries, hypersaline lakes, Długołecki P, Da˛browska J, Nijmeijer K, Wessling
or seawater desalination plants. In particular, the M (2010) Ion conductive spacers for increased power
co-location of PRO/RED with seawater desalina- generation in reverse electrodialysis, J Membr Sci
347:101–107
tion plants would allow the recovered energy Enomoto H, Fujitsuka M, Hasegawa T, Kuwada M,
from the RO brines to be used to desalinate the Tanioka A, Minagawa M (2010) A feasibility study
water. of pressure-retarded osmosis power generation system
In the oil and gas and mining industries, large based on measuring permeation volume using reverse
osmosis membrane, Electr Eng Jpn 173:1129–1138
amounts of water streams with high total Lacey RE (1980) Energy by reverse electrodialysis, Ocean
dissolved salts (TDS) are produced from the Eng 7:1–47
hydraulic methods used in the harvesting of gas Lewis A, Estefen S, Huckerby J, Musial W, Pontes T,
from coal beds (McBeth et al. 2003), oil from Torres-Martinez J (2011) In: Edenhofer O, Pichs-
Madruga R, Sokona Y, Seyboth K, Matschoss P,
subsurface formation (Ahmadun et al. 2009), or Kadner S, Zwickel T, Eickemeier P, Hansen G,
from mining activities (Balaba and Smart 2012). Schlomer S, Stechow CV (eds) IPCC special report on
Thus, the recovery of osmotic energy from such renewable energy sources and climate change mitiga-
produced water streams is also possible for large- tion. Cambridge University Press, Cambridge/New York
Loeb S (1976) Production of energy from concentrated
scale applications. brines by pressure-retarded osmosis: I. Preliminary
technical and economic correlations, J Membr Sci
1:49–63
Loeb S (2001) One hundred and thirty benign and renew-
References able megawatts from Great Salt Lake? The possibili-
ties of hydroelectric power by pressure-retarded
Ahmadun F-R, Pendashteh A, Abdullah LC, Biak DRA, osmosis, Desalination 141:85–91
Madaeni SS, Abidin ZZ (2009) Review of technolo- McBeth IH, Reddy KJ, Skinner QD (2003) Chemistry of
gies for oil and gas produced water treatment, J Hazard trace elements in coalbed methane product water,
Mater 170:530–551 Water Res 37:884–890
Balaba RS, Smart RB (2012) Total arsenic and selenium Post JW, Veerman J, Hamelers HVM, Euverink GJW,
analysis in Marcellus shale, high-salinity water, and Metz SJ, Nymeijer K, Buisman CJN (2007) Salinity-
hydrofracture flowback wastewater, Chemosphere gradient power: Evaluation of pressure-retarded osmo-
89:1437–1442 sis and reverse electrodialysis, J Membr Sci
288:218–230
4 Blue Energy
Ramon GZ, Feinberg BJ, Hoek EMV (2011) Membrane- Thorsen T, Holt T (2009) The potential for power
based production of salinity-gradient power, Energy production from salinity gradients by pressure retarded
Environ Sci 4:4423–4434 osmosis, J Membr Sci 335:103–110
F
FO membrane
module
Diluted draw
solution
Air
Sludge
Retentate
Purified water
Wastewater
in
Draw
solution
Feed Draw solution
Air
regeneration process
Bioreactor FO membrane
polymeric substances (EPS), and soluble macro-/ leading to flux decline and toxic effects on the
microorganics and inorganics. FOMBR, on the microbial community. In addition, the draw solu-
other hand, has an additional potential scaling tion must be able to be regenerated easily and
issue caused by inorganic salts due to solute accu- economically for reuse (Cornelissen et al. 2008).
mulation (Zhang et al. 2012).
Secondly, the bioprocess must be optimized to
handle accumulated recalcitrant organics, nutri- References
ents, and elevated salt concentrations, as the FO
membrane possesses a dense-selective layer with Achilli A, Cath TY, Marchand EA, Childress AE
(2009) The forward osmosis membrane bioreactor: a
high retentions to the organic species and salts.
low fouling alternative to MBR processes. Desalina-
The accumulation of organic matters improves tion 239:10–21
the biological degradation which may enhance Cath TY, Childress AE, Elimelech M (2006) Forward
the removal of micropollutants. The salt accumu- osmosis: principles, applications, and recent develop-
ments. J Membr Sci 281:70–87
lation, however, (i) could have adverse effects on
Cornelissen ER, Harmsen D, de Korte KF, Ruiken CJ, Qin
biological treatment and cause microbial inhibi- J-J, Oo H, Wessels LP (2008) Membrane fouling and
tion (Zhang et al. 2012; Nawaz et al. 2013); process performance of forward osmosis membranes
(ii) reduces the osmotic driving force available, on activated sludge. J Membr Sci 319:158–168
Nawaz MS, Gadelha G, Khan SJ, Hankins N (2013)
resulting in the reduction of water flux; and (iii)
Microbial toxicity effects of reverse transported draw
increases the concentration of sparingly soluble solute in the forward osmosis membrane bioreactor
salts, and spontaneous chemical precipitation (FO-MBR). J Membr Sci 429:323–329
may occur when the saturation limits are Wang R, Shi L, Tang CY, Chou S, Qiu C, Fane AG
(2010) Characterization of novel forward osmosis hol-
exceeded, leading to scaling on the FO
low fiber membranes. J Membr Sci 355:158–167
membranes. Yap WJ, Zhang J, Lay WCL, Cao B, Fane AG, Liu
The third challenge relates to draw solute Y (2012) State of the art of osmotic membrane bio-
selection and regeneration. A proper draw solu- reactors for water reclamation. Bioresour Technol
122:217–222
tion is necessary to provide high osmotic pressure
Zhang J, Loong WLC, Chou S, Tang C, Wang R, Fane AG
and low salt back diffusion (Cath et al. 2006). (2012) Membrane biofouling and scaling in forward
When the salts from the draw solution diffuse to osmosis membrane bioreactor. J Membr Sci
the feed tank, the driving force will be reduced, 403–404:8–14
H
High-Rejection Seawater
Reverse Osmosis
Membrane,
Fig. 1 Structure of
composite RO membrane Active skin layer
(Uemura et al. 2012)
Support layer
Substrate
Fane AG, Chong TH, Le-Clech P (2009) Fouling in mem- Matsuura T, Fane AG (2013) Editorial: new directions in
brane processes. In: Drioli E, Giorno L (eds) Mem- desalination. Desalination 308:1
brane operations: innovative separations and Misdan N, Lau WJ, Ismail AF (2012) Seawater reverse
transformations. Wiley-VCH, Weinheim, pp 121–138 osmosis (SWRO) desalination by thin film composite
Jonsson G, Macedonio F (2010) Fundamentals in reverse membrane – current development, challenges and
osmosis. In: Drioli E, Giorno L (eds) Comprehensive future prospects. Desalination 287:228–237
membrane science and engineering, vol 2. Elsevier, Uemura T, Kotera K, Henmi M, Tomioka H (2012) Mem-
Oxford, pp 1–22 brane technology in seawater desalination: history,
Kurihara M, Tomioka H (2010) Preparation of industrial recent developments and future prospects. Desalin
RO, NF membranes, and their membrane modules and Water Treat 33(1–3):283–288
applications. In: Drioli E, Giorno L (eds) Comprehen- Wijmans JG, Baker RW (1995) The solution-diffusion
sive membrane science and engineering, model: a review. J Membr Sci 107:1–21
vol 2. Elsevier, Oxford, pp 23–34
A
References
Anion-Exchange Resin like a weak base. The weak base resin does not
have a hydroxide ion form as does the strong base
Tongwen Xu resin. Consequently, its regeneration needs only
Collaborative Innovation Centre of Chemistry to neutralize the absorbed acid and does not need
for Energy Materials, School of Chemistry and to provide hydroxide ions. Less expensive
Material Science, University of Science and weakly basic reagents such as ammonia (NH3)
Technology of China, Hefei, P.R. China or sodium carbonate can be employed.
The selectivity of a resin for a given ion is
measured by the selectivity coefficient (K), as for
Anion-exchange resin contains positively the reaction
charged groups, such as –NH3+, NRH2+,
NR2H+, NR3+, PR3+, SR2+, etc., which R A þ B ¼ R B þ A
are fixed to the membrane backbone and allow
the exchange of anions but repulse cations. As The K can be expressed as K = (concentration of
shown in Fig. 1, the active groups existed in the B in resin/concentration of A in resin)
body of resin determine its chemical behavior. It (concentration of A in solution/concentration
has a highly developed structure of pores on the of B in solution).
surface, which could easily trap and release ions. In general, introducing ionic groups could
There are two main types of anion-exchange start with a monomer containing a moiety, a
resins differing in their active groups: strongly polymer film, or start with polymers or polymer
basic and weakly basic. (1) Strongly basic resins blends (Helfferich 1962; Strathmann 2004). As
are highly ionized, and their chemical behavior is summarized in our recent book chapter, the spe-
similar to that of a strong base which can be used cific implementation methods include
over the entire pH range. They can react with (1) amidoalkylation of cross-linking polystyrene,
anions in solution and convert an acid solution (2) copolymerization of (chloromethyl) styrene,
to pure water. The exhausted resin can be (3) chloroacetylation of polymers, (4) acetylation
regenerated with concentrated sodium hydroxide of cross-linked polystyrene, and (5) grafting
(NaOH) and converted to the hydroxide form. vinylbenzyl ammonium chloride onto inert poly-
(2) The degree of ionization of weakly basic mers (Xu 2009).
resin is strongly influenced by pH because it is
Anion-Exchange Resin,
Fig. 1 Diagram of anion-
backbone
exchange resin
–
– + +
+ + active group
– –
–
+ active group (fixed group)
–
+ –
free ion
+
Regeneration of the Ion-Exchange regeneration, where the fluids are flowing from
Resin the top to the bottom of the column both during
the service run and during regeneration (Fig. 1),
Tongwen Xu and (2) reverse flow regeneration, where the
Collaborative Innovation Center of Chemistry for fluids are flowing alternatively upward and
Energy Materials, School of Chemistry and downward during service and regeneration
Material Science, University of Science and (Fig. 2). Traditional regenerants are salts (such
Technology of China, Hefei, P.R. China as NaCl, KCl, NH4Cl), acids (HCl, H2SO4,
HNO3, acetic acid, citric acid), and alkali
(NaOH, KOH, NH3, Na2CO3). For instance,
Regeneration of the ion-exchange resin is the NaCl is normally used to regenerate SAC resins
procedure for recovering the ion-exchange capa- in the softening process. SAC resins need to be
bilities of exhausted ion-exchange resins. Most regenerated with a strong acid for the purpose of
ion-exchange resins are used in columns. decationization, and SBA resins are always
Ion-exchange operation is basically discontinu- regenerated with NaOH in the demineralization
ous: a loading phase, called service run, is process. The disadvantages of the use of tradi-
followed by regeneration of the exhausted resins tional regenerants are the low regeneration effi-
(Calmon 1986). Regeneration ratio is calculated ciency and the discharge of large amount of
as the total amount of regenerant (in equivalents) wastewater, leading to serious environmental
divided by the total ionic load (also in equiva- pollution and resource waste. Improvement
lents) during one cycle. It is also equal to the methods include (1) the recovery of the
number of eq./L regenerant per eq./L of resin discharged wastewater; nanofiltration can be uti-
operating capacity. A (theoretical) regenerant lized for recovery of the wastewater, or the waste
ratio of 1.00 (i.e., 100 %) would correspond to can be used to produce composite flocculant;
the stoichiometric quantity. Nevertheless, all (2) the modification of the regenerants; alcohol,
resins need a certain excess of regenerant above ketone, and surfactant are added, or new
the stoichiometric quantity. The regeneration regenerants are developed; and (3) the strength-
ratio is influenced by the technological process, ening of the regeneration process. Ultrasonic,
the type and amount of regenerant, etc. There are microwave, electrodialysis, or thermal treatment
two main methods for the regeneration process is applied for the strengthening.
(Dardel and Arden 2008): (1) co-flow
Exhaustion Regeneration
lon leakage
Regenerated resin Exhausted resin
Regeneration of the Ion-Exchange Resin, Fig. 1 Illustration of co-flow regeneration (CFR) (Dardel and Arden
2008)
a Exhaustion Regeneration
b Exhaustion Regeneration
Clean zone: almost no leakage
Regeneration of the Ion-Exchange Resin, Fig. 2 Illustration of reverse flow regeneration (RFR), including (a)
upflow loading and downflow regeneration and (b) downflow loading and upflow regeneration (Dardel and Arden 2008)
Regeneration of the Ion-Exchange Resin 3
References
Titania Membranes, Fig. 1 Molecular weight cutoff Benfer S, Popp U, Richter H, Siewert C, Tomandl G
curves for TiO2 porous membranes (solutes: sugars, (2001) Development and characterization of ceramic
500 ppm) (Wildman et al. 1993) nanofiltration membranes. Sep Purif Technol
22–23:231
Puhlf€
urß P, Voigt A, Weber R, Morbé M (2000) Micro-
Atomique (CEA). Colloidal sols with a diameter porous TiO2 membranes with a cut off <500 Da. J
of 15 nm, which showed an anatase phase and Membr Sci 174:123
which were stable up to 600 C, were coated on Sarrade SJ, Rios GM, Carlès M (1996) Nanofiltration
porous alumina supports and fired at 500 C. Voigt membrane behavior in a supercritical medium. J
Membr Sci 114:81
et al. (Puhlf€
urß et al. 2000) prepared polymeric Soria R, Cominottim S (1996) In: Proceedings of fourth
sols from a solution of Ti-isopropoxide in isopro- international conference on inorganic membranes,
pyl alcohol by the addition of a small amount of p 194
water. NF membranes, which were prepared by Tsuru T, Hironaka D, Yoshioka T, Asaeda M. (2001)
Titania membranes for liquid phase separation: effect
coating the polymeric sols on a TiO2 intermediate of surface charge on flux. Sep Purif Technol 25: 307
layer (pore size 5 nm, prepared by colloidal TiO2 Wildman DL, Peterson RA, Anderson MA, Hill CG
sols), followed by firing at 450 C, had an (1993) In: Proceedings of third international confer-
MWCO of 480 and a pure water flux of 20 l/ ence on inorganic membranes, p 111
Xu Q, Anderson M (1994) Sol–Gel Route to Synthesis of
(m2 h bar) and were applied to the separation of Microporous Ceramic Membranes: Preparation and
electrolytes. Benfer et al. (2001) also developed Characterization of Microporous TiO2 and ZrO2
TiO2 NF membranes by the polymeric sol route. Xerogel. J Am Ceram Soc 77: 1939
A
Reactants retentate
Reactants retentate
COx-free H2
Silica membrane
Intermediate layer
Ru catalyst
γ-Al2O3
Bimodal catalytic support layer
α-Al2O3
¬
NH3 ¬ 1.5H2ˇ 0.5N2
NH3 N2
Ammonia Decomposition in Catalytic Membrane Reactors, Fig. 2 Schematic diagram of the proposed bimodal
catalytic membrane reactor for COx-free H2 production via NH3 decomposition (Li et al. 2013)
Ammonia
Decomposition
in Catalytic Membrane
Reactors, Fig. 3 Bimodal
catalytic membrane reactor
performance for NH3
decomposition at 450 C
(Li et al. 2013)
Chemical Vapor Deposition take place at the location where the reactants
contact each other. Therefore, the deposition
Hiroki Nagasawa and Toshinori Tsuru occurs inside the pores and the pore size will be
Department of Chemical Engineering, Hiroshima decreased. The deposition continues until the
University, Higashi-Hiroshima, Japan pore size becomes small enough to reduce diffu-
sion of the reactants. As a result, uniform pore
size can be obtained by using the counter-
Chemical vapor deposition (CVD) is a method diffusion CVD.
for depositing thin films of various materials The hydrogen-selective silica membranes
(Smith 1995). CVD process involves a series of reported by Gavalas et al. were prepared by
gas phase and surface reactions of volatile precur- depositing a dense silica layer on the top of
sors, which are induced by, for example, heat, light, Vycor glass membranes by the oxidation of SH4
and/or plasma-discharge. CVD has been used at 450 C (Gavalas et al. 1989). The obtained
extensively in a number of industries such as semi- membranes were reported to have high H2/N2
conductor, electronics, and optics industries. selectivities as high as 3,000 but low H2
CVD techniques have also been utilized in the permeances of 2.1 10 8 mol/(m2 s Pa) at
fabrication of inorganic molecular sieve mem- 450 C. Until then, a great deal of progress has
branes. Among the types of CVD technique, ther- been made by several research groups. For exam-
mal CVD has been most extensively studied since ple, Gu and Oyama prepared a silica membrane
Gavalas and coworkers first reported successful on the substrate with a graded g-alumina inter-
synthesis of the hydrogen-selective silica mem- mediate layer by the thermal decomposition of
branes in 1989 (Gavalas et al. 1989). There are tetraethoxysilane (TEOS) at 600 C and reported
two types of reaction geometries available for H2 permeance of 5.0 10 7 mol/(m2 s Pa) at
thermal CVD, as shown in Fig. 1: one-sided 600 C, with H2/CH4 selectivity of 5,900
CVD and counter-diffusion CVD (Nomura (Gu and Oyama 2007). Ohta et al. prepared silica
et al. 1997; Nakao et al. 2000). For the case of membranes on the g-alumina intermediate layer
the one-sided CVD, all of the reactants are fed to by using oxidation of tetramethoxysilane
the same side of the porous substrate, and then, (TMOS), phenyltrimethoxysilane (PTMS), or
the film-forming reactions occur at the surface of dimethoxydiphenylsilane (DMDPS) at 600 C
the substrate. On the other hand, for the case of and reported that larger pores were formed
the counter-diffusion CVD, the reactants are fed when the number of phenyl groups on the precur-
to the opposite side of the substrate. The reactants sor was increased (Ohta et al. 2008). The
diffuse into the porous substrate and the reactions DMDPS-derived membrane showed a high H2
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_1425-1
2 Chemical Vapor Deposition
Chemical Vapor
Deposition,
Fig. 1 Schematic diagram
of (a) one-sided and (b)
counter-diffusion CVD
processes
permeance of the order of 10 6 mol/(m2 s Pa) at the membrane prepared via 2-step PECVD
300 C, with H2/SF6 selectivity of 6,800. showed a good thermal stability, although the
Plasma-enhanced CVD (PECVD) is another membrane was fabricated at room temperature.
type of CVD technique utilized for the membrane The 2-step PECVD-derived membrane showed
fabrication. PECVD offers a low processing tem- high He and H2 permeances of 5.2 10 7 and
perature compared with thermal CVD due to the 2.4 10 7 mol/(m2 s Pa) at 400 C, respec-
high reactivity of plasma. Several research tively, with He/N2 and H2/N2 permeance ratios
groups reported the PECVD-derived membranes of 4,200 and 1,900, respectively (Tsuru
prepared at room temperature by using several et al. 2011; Nagasawa et al. 2013).
kinds of precursors such as hexamethyldisiloxane
(HMDSO) (Roualdes et al. 2002; Tsuru
et al. 2011; Nagasawa et al. 2013), hexamethyl-
References
disilazane (HMDS) (Kafrouni et al. 2009), or bis
(dimethylamino)dimethylsilane (BDMADMS) Gavalas GR, Megiris CE, Nam CW (1989) Chem Eng Sci
(Kafrouni et al. 2010). Typical PECVD-derived 44:1829–1835
membranes showed moderate selectivity (e.g., Gu Y, Oyama ST (2007) High molecular permeance in a
He/N2 selectivity of <10 at 25 C and ~30 at poreless ceramic membrane. Adv Mater
19:1636–1640
150 C) with He permeance of the order of Kafrouni W, Rouessac V, Julbe A, Durand J (2009) Syn-
10 8–10 7 mol/(m2 s Pa), probably because the thesis of PECVD a-SiCxNy:H membranes as molecu-
PECVD-derived layer remains to have high con- lar sieves for small gas separation. J Membr Sci
tent of organofunctional groups which make the 329:130–137
Kafrouni W, Rouessac V, Julbe A, Durand J (2010) Syn-
structure more loose (Roualdes et al. 2002; Tsuru thesis and characterization of silicon carbonitride films
et al. 2011; Nagasawa et al. 2013; Kafrouni by plasma enhanced chemical vapor deposition
et al. 2009, 2010). Selectivity of PECVD-derived (PECVD) using bis(dimethylamino)dimethylsilane
membranes can be improved by 2-step PECVD (BDMADMS), as membrane for a small molecule
gas separation. Appl Surf Sci 257:1196–1203
sequence, which involves HMDSO/Ar-PECVD Nagasawa H, Shigemoto H, Kanezashi M, Yoshioka T,
followed by HMDSO/O2-PECVD (Tsuru Tsuru T (2013) Characterization and gas permeation
et al. 2011; Nagasawa et al. 2013). Moreover, properties of amorphous silica membranes prepared
Chemical Vapor Deposition 3
via plasma enhanced chemical vapor deposition. silica membranes for gas separation by chemical vapor
J Membr Sci 441:45–53 deposition. J Membr Sci 315:93–99
Nakao S, Suzuki T, Sugawara T, Tsuru T, Kimura Roualdes S, Sanchez J, Durand J (2002) Gas diffusion and
S (2000) Preparation of microporous membranes by sorption properties of polysiloxane membranes pre-
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Microporous Mesoporous Mater 37:145–152 Smith DL (1995) Thin-Film Deposition: Principles and
Nomura M, Yamaguchi T, Nakao S (1997) Silicalite Practice, McGraw-Hill, Inc.,
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Nakao S (2008) Development of pore size-controlled performance. Chem Commun 47:8070–8072
H
(S)-isomer (acid)
Aqueous Phase (lumen side)
a biphasic membrane reactor using enzyme libraries of potential selectors are generated, and
immobilized on the membrane surface. The the systems with desirable properties are
immobilized enzyme on a membrane hydrolyzes extracted from the libraries.
preferentially one isomer ester in the organic feed
phase, and the produced acid is extracted into the
aqueous phase. In this system, reaction and sep-
References
aration occur simultaneously in/on membranes.
Membrane technology has a potential to Li B, Haynie DT (2007) Chiral drug separation. In: Ency-
improve the application of enzymatic reactions clopedia of chemical processing. Taylor & Francis
to the industrial scale production of chiral drugs. Online, pp 449–458
The recent progress of enzymatic membrane Lopez JL, Matson JL (1997) A multiphase/extractive
enzyme membrane reactor for production of diltiazem
reactors was reviewed elsewhere (Rios chiral intermediate. J Membr Sci 125:189–211
et al. 2004). Maier NM, Franco P, Lindner W (2001) Separation of
The most important factor for successful opti- enantiomers: needs, challenges, perspectives.
cal resolution of enantiomers in a racemate is the J Chromatogr A 906:3–33
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design of a chiral selector fitting for the separa- Progress in enzymatic membrane reactors – a review.
tion, because many drugs have complicated steric J Membr Sci 242:189–196
structures. One of the measures devised to deal Sekhon BS (2010) Enantioseparation of chiral drugs – an
with this problem is the implementation of com- overview. Int J PharmTech Res 2:1584–1594
binatorial strategies (Maier et al. 2001). Large
M
Magnetically Responsive Membranes, Fig. 1 Types Xianghong Qian, S Ranil Wickramasinghe, Responsive
of stimuli (Reprinted from Current Opinion in Chemical membranes for advanced separations, 98–104, 2015, with
Engineering, vol number: 8, Siavash Darvishmanesh, permission from Elsevier)
polymer conformational and/or property changes weak base and acid groups respond to a specific
(Darvishmanesh et al. 2015). Figure 1 chemical cue, H+ ions in solution.
(Darvishmanesh et al. 2015) gives a schematic Solution ionic strength is another example of a
representation of the three types of stimuli: direct, direct stimulus and can affect the degree of poly-
indirect, and field induced. Direct stimulation is mer swelling in a number of ways. The presence
specific. The responsive groups on the membrane of salt ion and its type and concentration affect
respond to a specific chemical or biological cue. charge interactions in the membrane/solution
For example, pH-responsive groups respond to system. It affects the degree of swelling for
changes in pH (H+ ion concentration) (Himstedt pH-responsive membranes. Salt ions can cause
et al. 2013a; Gugliuzza 2013; Wee et al. 2013). charge screening thus limiting the amount of
A carboxylic group (e.g., acrylic acid) at pH swelling. Strong acid and base groups such as
below its pKa is protonated leading to its quaternary amines are insensitive to solution pH
decreased hydration and de-swelling effect. The but respond to changes in ionic strength (Husson
polymer network swells when the pH exceeds its 2012). In addition poly (zwitterion)-based multi-
pKa as the carboxylic groups become layer membranes have also been shown to
deprotonated and repel each other. Thus mem- respond to solution ionic strength (de Grooth
brane permeability can be adjusted. In the case of et al. 2014). However unlike weak polyelectro-
pH-responsive groups, a number of different lytes such as weak acids and weak bases, increas-
ing ionic strength leads to an increase in swelling.
Magnetically Responsive Membranes 3
Biologically inspired responsive groups date most responses to ultrasound waves lead to
include (i) antigen-responsive membranes irreversible cleavage of weak bonds in the poly-
(Zhang et al. 2007; Lu et al. 2003), (ii) redox/ mer structure. Consequently, unlike the other
thiol-responsive groups (Wong et al. 2008; responsive mechanisms described here,
Cerritelli et al. 2007; Ghosh et al. 2009), (iii) ultrasound-responsive membranes tend to
enzyme-responsive membranes (Ulijn 2006), undergo irreversible transformations
and (iv) glucose-responsive membranes (Chu (Li et al. 2010; Zhang et al. 2009). Development
et al. 2004). In these cases a chemical or biolog- of reversible ultrasound-responsive polymers that
ical cue directly interacts with a specific chemical undergo reversible transformations could be an
groups on the membrane surface. Thus they are area of future development.
much more specific than the pH and ionic Field-induced responsive behavior is funda-
strength-responsive group describe above. mentally different to the direct and indirect
Indirect stimulation, like direct stimulation, responses as no mass transfer is required. Three
involves mass transfer to the responsive groups. types of external field, electric, magnetic, and
However unlike direct stimulation, changes in electromagnetic waves, have been considered in
polymer conformation/property occur due to the past. Electric field-responsive membranes
changes in the thermodynamic environment and shrink, swell, or twist in response to an external
not to a specific interaction with a chemical or electric field due to the interaction of charged
biological cue. Most temperature-responsive species with the external field. These changes in
polymers display a lower critical solution tem- polymer confirmation can be used to control sol-
perature (LCST). A common example is poly ute permeation through the membranes. In addi-
(N-isopropylacrylamide) (PNIPAM). PNIPAM tion development of fouling-resistant membranes
is a hydrogel that is water soluble when the tem- based on desorption of adsorbed solutes due to
perature is below its LCST. Above its LCST, the changes in polymer conformation induced by
polymer becomes hydrophobic and will phase changes in an external electric field has been
separate. When PNIPAM chains are attached to described (Wandera et al. 2010).
a membrane surface, the grafted polymer layers Magnetic field-responsive groups such as
swell and de-swell when the local temperature magnetic nanoparticles are usually physically
fluctuates below or above the LCST. Previous entrapped within the membrane structure or
studies have shown that conformational immobilized onto the membrane surface.
switching can lead to the release of adsorbed Changes in an external magnetic field can cause
foulants (Wandera et al. 2011, 2012; Tomer movement and/or heating of these magnetically
et al. 2009). The LCST of thermo-responsive responsive groups. Recent studies indicate that
polymers is strongly affected by the salt ion, its movement of magnetically responsive polymer
type, and concentration. An increase in concen- chains attached to the membrane surface can
tration will lead to a decrease in LCST. The suppress concentration polarization during
actual decrease in ionic strength depends on the nanofiltration (Himstedt et al. 2011; Yang
specific ion present in solution. Recent studies et al. 2013). In addition magnetically responsive
suggest that modulation of LCST by solution polymer chains attached to the inside pore sur-
ionic strength could be used to develop high- face of microfiltration membranes can be used to
performance ligands for applications such as modulate membrane permeability by applying an
membrane-based hydrophobic interaction chro- external magnetic field (Himstedt et al. 2012).
matography (Wu et al. 2014; Himstedt Electromagnetic radiation such as UV, IR,
et al. 2013b). etc. has been used to trigger structural transfor-
Ultrasound represents another method of indi- mations of functional species such as azo groups
rect stimulation. Ultrasound-responsive mem- (Ishihara et al. 1984; Ishihara and Shinohara
branes have been reported for biomedical 1984; Kinoshita et al. 1986). For example,
applications such as controlled drug release. To photo-responsive polyethersulfone (PES)
4 Magnetically Responsive Membranes
membranes were prepared from blending PES Ghosh S, Yesilyurt V, Savariar EN, Irvin K,
with azobenzene(Azo) and b-cyclodextrin Thayumanavan S (2009) Redox, ionic strength, and
pH sensitive supramolecular polymer assemblies.
(b-CD). The water permeability of the mem- J Polym Sci A Polym Chem 47:1052–1060
branes was tested under light irradiation at Gugliuzza A (2013) Intelligent membranes: dream or
450 and 365 nm, respectively. At 450 nm, the reality? Membranes 3:151–154
membrane pores close and water flux decreases Himstedt HH, Yang Q, Dasi LP, Qian X, Wickramasinghe
SR, Ulbricht M (2011) Magnetically activated
due to the complex formation between Azo and micromixers for separation membranes. Langmuir
b-CD. By changing irradiation wavelength to 27:5574–5581
365 nm, the membrane pores open due to com- Himstedt HH, Yang Q, Qian X, Wickramasinghe SR,
plex dissociation between Azo and b-CD, and the Ulbricht M (2012) Toward remote-controlled valve
functions via magnetically responsive capillary pore
membranes show higher permeability. membranes. J Membr Sci 423:257–266
Himstedt HH, Du H, Marshall KM, Wickramasinghe SR,
Qian X (2013a) pH responsive nanofiltration mem-
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Himstedt HH, Qian X, Weaver JR, Wickramasinghe SR
(2013b) Responsive membranes for hydrophobic
Though very much in its infancy, development of
interaction chromatography. J Membr Sci
responsive membranes offers numerous opportu- 447:335–344
nities for designing high-performance mem- Husson SM (2012) Synthesis aspects in the design of
branes for future separations needs. It is likely responsive membranes. In: Responsive membranes
and materials, Wiley, Chichester, West Sussex, UK.
that more complicated responsive mechanisms
pp 73–96
that involve a cascade of stimuli-response inter- Ishihara K, Shinohara I (1984) Photoinduced permeation
actions will be developed analogous to biological control of proteins using amphiphilic azoaromatic
membranes. It is also likely that computational polymer membrane. J Polym Sci: Polym Chem
22:515–518
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Ishihara K, Hamada N, Kato S, Shinohara I (1984) Photo-
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Magnetically Responsive Membranes 5