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Article history:
Received 23 February 2015
Revised 23 September 2015
Accepted 27 October 2015
Available online 16 November 2015
Keywords:
Ion exchange
Cobalt
Zeolite Y
Mixed matrix membrane
CO2 separation
a b s t r a c t
The nano-porous sodium zeolite Y (NaY) was ion exchanged with cobalt(II) cations. The Co2+ exchanged
NaY zeolite, Co(II)NaY, was incorporated (020 wt%) into the cellulose acetate (CA) membrane to form
new mixed matrix membranes (MMMs), the CA/Co(II)NaY. The particles and MMMs were characterized
by UVvis DRS, N2 adsorptiondesorption isotherm, XRD, SEM, and FTIR-ATR. The CO2 and N2 permeation
measurements (210 bar) were carried out to determine the potential of the MMMs for CO2 separation. Characterization results conrmed a suitable ion exchange treatment of the zeolite and as well the formation
of MMMs with favorable morphological/structural properties. The gas permeation results of CA/Co(II)NaY
membranes revealed considerable enhancement of CO2 /N2 ideal selectivities with respect to the neat CA
and CA/NaY membranes. The ideal selectivity (=29.9; with a permeability of 3.28 Barrer) of 15 wt% Co(II)
NaY loaded MMM at 4 bar was increased about 17.3% in comparison with the ideal selectivity of neat CA
membrane (=25.5; with a permeability of 2.28 Barrer) and also increased 44.4% in comparison with that of
15 wt% NaY loaded MMM (=20.7; with a permeability of 3.43 Barrer). Moreover, the CO2 permeability was
increased about 43.9% in comparison with the neat CA and approximately remained unchanged, compared
with the CA/NaY 15 wt%. In addition, the optimum zeolite loading decreased from 20 wt% for CA/NaY (with a
CO2 permeability of 4.87 Barrer and ideal selectivity of 25.0) to 15 wt% for CA/Co(II)NaY, which also causes
CA/Co(II)NaY to surpass the parents CA and CA/NaY membranes from the most prominent technical factor
of selectivity.
2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
1. Introduction
Facilitated transport membranes (FTMs) have been proposed as
an emerging area of membranes that attracted great attentions for
gas separation with respect to the high performances. A reactive
carrier agent which (1) covalently bonded to the polymeric backbone (solid/solidied or immobilized carrier FTMs) or (2) can move
freely across the membrane (liquid or mobilized carrier FTMs), serves
in mass transfer through the facilitated transport mechanisms [1,2].
The FTMs synthesized through the incorporation of noble transition
metal ions as Ag+ into the membrane matrix have shown superior
performances compared to other FTMs [3]. In this case, a reversible
Corresponding author at: Department of Chemical Engineering, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran, Iran. Tel.: + 98 21 64543197; fax: + 98
21 66405847.
E-mail address: kargari@aut.ac.ir, ali_kargari@yahoo.com (A. Kargari).
http://dx.doi.org/10.1016/j.jtice.2015.10.042
1876-1070/ 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
404
H. Sanaeepur et al. / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413
with faujasite (FAU) topology and Na+ as counter ion, was modied
with Co2+ through a cation exchange reaction to form Co(II)NaY.
The FAU-type zeolite was chosen because of its larger pore size compared to the other zeolites that facilitates the activated diffusion for
the penetrant gases [22]. It also serves a great adsorptive molecular
transport by differences in the adsorptivities of the penetrants [18].
The Si/Al ratio of Y-type zeolites (1.53.0) is larger than the X-type
ones (11.5). This means the lower Al content of Y-type zeolites or
their lower negative charge to be induced by each AlO4 5 tetrahedron
to maintain the electroneutrality. Thus, the number of cations, which
can be coordinated in the Y-types, is smaller than that in the X-types.
Therefore, the reduction in sizes of zeolite pores and micro-pore volumes through the ion exchange reaction in the Y-type zeolites would
be less than the X-types. It can be suitable for permeation of gases
through the Y-type zeolites. Moreover, a typically higher CO2 adsorption capacity of exchanged ions for CO2 compared to N2 is in favor
of CO2 /N2 separation [20]. Both NaY and Co(II)NaY zeolites were incorporated into cellulose acetate (CA) in different ller/polymer ratios (020 wt%) to prepare novel composite membranes for CO2 separation. CA, with a good mechanical strength, thermal stability and
chemical resistance [2326], is the earliest and the most common
membrane material for CO2 separation [27]. Gas permeation properties of CO2 and N2 were determined over a pressure range of 2
10 bar. Finally, a comparison was made between the obtained permeability/selectivity results for CA/Co(II)NaY and CA/NaY mixed matrix
membranes.
2. Experimental
2.1. Materials
Cellulose acetate (CA) powder, with average Mn 30,000 by GPC,
acetyl content 39.8 wt% and a bulk density of 1.3 g/mL at 25 C, and
also sodium Y zeolite (NaY) powder with Si/Al ratio of 2.53 were purchased from Sigma-Aldrich (Saint Louis, MO, USA). The particle size
of the zeolite was determined by dynamic light scattering (DLS) analysis through a Scatteroscope-I advanced DLS type nano-micro particle size analyzer (Qudix Inc., Seoul, Korea) and found an average
particle diameter of 1.22 m. Moreover, 90% of the particles had diameters less than 1.95 m and also no particle was found with a
diameter beyond 4.81 m. Tetrahydrofuran (THF), with a normal
boiling point of 6566 C and a density of 0.89 g/mL at 20 C, and also,
cobalt(II) acetate tetrahydrate, ACS grade, molar mass 249.08 g/mol,
melting point 140 C (elimination of water of crystallization), density
1.70 g/cm3 (20 C), and bulk density 0.85 g/cm3 were acquired from
Merck Co. (Darmstadt, Germany) and used without further purication. High quality distilled water with the conductivity of 2 S/cm
was obtained by a laboratory double distillation apparatus, GFL 2104
(Burgwedel, Germany). All the gases with 99.999% purity were purchased from Technical Gases Ltd. supplied by Oxygen Yaran Company,
Mahshahr, Iran.
2.2. Ion exchange
NaY powder was dried overnight at 100 C in an oven that followed by further drying for two-days at 120 C in a vacuum oven before use. 100 ml distilled water was poured in a 250 ml round glass
bottle reactor equipped with a plastic stopper and 100 mM cobalt(II)
acetate tetrahydrate salt was added and stirred for 1 h at 400 rpm
to complete dissolution. Then, the white NaY powder was added in
a ratio of 10% (w/v) into the transparent pink Co2+ solution and was
stirred rigorously for 24 h at 700 rpm and 90 C. After completion of
the ion exchange reaction between the Co2+ and Na+ ions, a pale pink
suspension was obtained. Thereafter, the suspended solids were ltered and washed with hot distilled water repeatedly (5 20 ml) until a clear wash water was obtained. As stated by Hasegawa et al. [28],
H. Sanaeepur et al. / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413
405
P=
in the case of the NaY-type zeolite, if insucient washing after ion exchange is done, the micro-pores are partially blocked by the adsorbed
large cations or by the probable insoluble salt residues. This could affect the CO2 /N2 separation performance by the diculty in diffusion
of gases into the blocked pores and/or the strong CO2 adsorption by
the ions/salts. The ltrate solution was analyzed by a Perkin-Elmer
model AA300 (Perkin-Elmer Corp., Norwalk, CT) atomic absorption
spectrophotometer (AAS) to determine the degree of ion exchange. A
value of 67.4% was founded in this case for the degree of ion exchange.
Finally, the resulted solid was dried overnight at 100 C in an oven
that followed by further drying for two days at 120 C in a vacuum
oven. A very clear pink powder, Co(II)Na-Y, was acquired after drying.
273.15 1010V l
AT ( p0 76)
dp
dt
P=D S
(2)
Table 1
Adsorptiondesorption characteristics of NaY and Co(II)NaY zeolite powders.
Sample
Micro-pore
volume
(cm3 /g)a
Micro-pore
surface area
(m/g)a
Average
pore
diameter
(nm)b
Average
pore
diameter
(nm)c
Average
micro-pore
diameter
(nm)c
NaY
Co(II)NaY
0.285
0.272
596
572
1.92
2.01
2.33
2.44
1.58
1.60
a
b
c
(1)
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H. Sanaeepur et al. / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413
Fig. 2. UVvis DRS spectra of the pure NaY and Co(II)NaY zeolites.
AB =
PA
PB
(3)
where PA and PB are the permeability of pure A and B gases, respectively. According to Eq. (2), the ideal selectivity can be written as the
product of the mobility (or diffusivity) and solubility selectivity factors [32]:
AB =
DA
SA
D
S
= AB
AB
DB
SB
(4)
2.5. Characterizations
The ultravioletvisible diffuse reectance spectroscopy (UVvis
DRS) of the powder samples were recorded on an Avantes AvaSpec2048-TEC spectrometer (Avantes Inc., Apeldoorn, The Netherlands)
H. Sanaeepur et al. / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413
407
Na+ (=1.02 A)
The decrease in micro-pore volume and surface area of Co(II)NaY
is probably due to the complex formation with the water molecules
present in the host lattice [42].
Fig. 4. SEM images of the cross sections of (a) CA/NaY and (b) CA/Co(II)NaY mixed
matrix membranes with 15 wt% ller contents.
3.1.3. DRS
Fig. 2 shows the diffuse reectance spectra of the pure NaY and
Co(II)NaY zeolite samples. As it is observed, NaY zeolite shows a
large minimum absorption at 261 nm in the UV region. This also appeared for the Co(II)NaY sample while its intensity reduced. This is
attributed to the formation of CoO bonds between the Co2+ cations
with framework oxygen atoms of the zeolite structure [43]. The difference in the absorptivity of CoO and that of NaO bonds of pure
NaY results in the observed intensity reduction. In addition, Co(II)
NaY shows an additional broad absorption band centered at 524 nm
in the visible region. This absorption peak could be related to an
octahedral [Co(H2 O)6 ]2+ complex (the hydrated pink zeolite sample) which is formed through the octahedral coordination of the exchanged cobalt ion located in the super-cages of Y-type zeolite with
water molecules [44]. In fact, the complex deposition does not take
place after complete washing the ion-exchanged zeolite samples in
the preparation procedure but mainly in the step of drying (100
120 C), which follows the washing. It leads to the complex precipitation on the micro-pore surfaces [45,46]. As already mentioned above
(SEM observations), the complex is also responsible for the acidic attack which results in hydrolysis and dissolution of zeolites, i.e. a local
lattice destruction.
3.1.4. XRD
XRD patterns of NaY and Co(II)NaY are presented in Fig. 3. All
the characteristic peaks of NaY zeolite are demonstrated at diffraction
angles 2 , in accordance with the literature [4749]. The peak intensities of I1 , I2 and I3 are assigned for positions 2 = 11.81, 13.85 and
18.24 and have been considered as the locations of cations in the NaY
zeolite. The peak intensities are in the order of I3 >> I1 > I2 , while it
rearranged for the Co(II)NaY zeolite in the order of I3 >> I2 > I1 . This
could be assigned to the rearrangement which occurred in the zeolite
structure through the ion exchange reaction [50].
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Fig. 5. FTIR-ATR spectra of the neat CA membrane, CA/NaY and CA/Co(II)NaY mixed matrix membranes with 15 wt% ller contents.
Fig. 6. XRD spectra of the neat CA membrane, CA/NaY and CA/Co(II)NaY mixed matrix membranes with 15 wt% ller contents.
Generally, all the peaks present in the XRD spectra of NaY were repeated for the Co(II)NaY sample too, however, a slight decrease was
observed in the peak intensities for Co(II)NaY which is attributed
to the less crystalline structure of the Co2+ ion exchanged sample.
The percentage of crystallinity was calculated for both samples based
on the intensities for the sample and the background according to
Eq. (5). The XRD pattern of the background sample holder in the XRD
experiments was used as the reference,
Crystallinity (% ) =
sum of peak intensities of sample
100.
sum of peak intensities of sample + sum of peak intensities of background
(5)
The calculated results demonstrated that the crystallinity of 88.4%
for NaY was decreased to 75.0% for Co(II)NaY which shows more
than a 15% decrease in the crystallinity of NaY through the Co2+ ion
exchange reaction. This is in good agreement with the SEM observations and the adsorptiondesorption results of the particle samples.
3.2. Membrane characterization
3.2.1. SEM
Cross sectional SEM images of the two MMMs (CA/NaY and
CA/Co(II)NaY) are presented in Fig. 4. As it is observed, both the
pure and ion exchanged zeolites were dispersed in the CA matrices, but more particle agglomerates with larger sizes could be seen
for CA/NaY. A relatively better dispersion of Co(II)NaY compared
to pure NaY particles in the CA matrix could be the result of better ller/polymer compatibility due to the cobaltous zeolite/CA functional groups weak acid-base interactions. This leads to better adhesion between the two phases and reducing the non-selective voids at
the zeolite/polymer interface.
3.2.2. FTIR-ATR
FTIR-ATR spectra of the neat CA, CA/NaY, and CA/Co(II)NaY membranes are depicted in Fig. 5. CA presents a broad band at 3484 cm1
that corresponds to OH stretching vibrations of the hydroxyl group
in the CA structure. In addition, a band at 1637 cm1 is attributed
to the interlayer stretching and bending vibration modes of molecular water. The characteristic absorption bands of CA occur at 1738
(C=O stretching), 1368 (CH3 symmetric deformation), 1220 (acetate
CCO stretching), and 1035 (CO stretching) cm1 which are generally in accordance with Yang [51] and Benosmane et al. [52]. Furthermore, absorptions at 2942 and 1432 cm1 are respectively attributed to CH3 asymmetric stretching and CH3 asymmetric deformation. The characteristic bands of the saccharide structure of
CA are observed at 1161 (stretching of the CO bridge), 1122
and 1035 (skeletal vibration involving the CO stretching) cm1 .
H. Sanaeepur et al. / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413
Fig. 7. The effect of Co(II)NaY particle loadings on (a) CO2 permeability, (b) N2 permeability, and (c) CO2 /N2 selectivity; solid lines are used only for connecting the data.
409
410
H. Sanaeepur et al. / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413
Scheme 1. Schematic representation of Co2+ ions distribution on the extra-framework sites in the Co(II)NaY zeolites.
H. Sanaeepur et al. / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413
411
Fig. 9. Comparing the performance of NaY and Co(II)NaY zeolites in the MMMs at
4 bar.
advantages from the issue by a high increase in the slope of N2 permeability lines from 15 to 20 wt% which results in the obvious decline in the CO2 /N2 ideal selectivity in this region.
Fig. 8. The effect of feed pressure on (a) CO2 permeability and (b) CO2 /N2 selectivity;
solid lines are used only for connecting the data.
pass through [16, 20]. On the other hand, as stated by Li et al. [8] for
the A-type zeolites dispersed in a glassy polymer matrix, CO2 permeability is decreased by an increase in the amounts of both pure (NaA)
and the silver ion exchanged (AgA) zeolites. As previously mentioned,
it was attributed to the effect of partial pore blockage of zeolites and
polymer chain rigidication. It is less likely here to have an important
pore blockage of Y-type zeolites by Co2+ ions since the Co2+ ionic radius is 0.75 A [41], considerably smaller than the Ag+ and Na+ having
respectively. The CO2 /N2 ideal selectivthe radius of 1.15 and 1.02 A,
ity (Fig. 7c) was increased for the zeolite loadings up to 15 wt% due
to the greater contribution of CO2 facilitated transport by increasing
the amounts of Co2+ cations. Afterwards, the ideal selectivity was declined considerably at 20 wt% Co(II)NaY. The decline in the ideal selectivity values at high particle loadings was frequently observed for
the MMMs containing zeolite particles. This is related to the formation of a low density layer of the polymer around the zeolite particles.
The coalescence of these coated particles results in the formation of
interconnected non-selective voids having high permeability and less
selectivity [63,64]. Comparing Fig. 7a and b for particle loading from
15 to 20 wt% shows that the non-interacting N2 molecules take more
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H. Sanaeepur et al. / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413
CA/Co(II)NaY MMMs as well as the neat CA decreases with increasing the feed pressure (Fig. 8b). A sharp decline in the ideal selectivity
of CA/Co(II)NaY 20 wt% samples with an increase in feed pressure
can be due to the percolation effect of the solid particles.
3.3.3. Performance comparison
Fig. 9 shows a comparison between the performances of NaY and
Co(II)NaY loaded MMMs. The highest CO2 permeability of 4.87 Barrer was obtained by a 20 wt% NaY loaded CA membrane [9,11] while
the highest CO2 /N2 ideal selectivity of 29.2 was obtained by a 15 wt%
Co(II)NaY loaded CA membrane. These phenomena may be arisen
from a better compatibility of Co(II)NaY than NaY particles with CA
matrix (see the SEM images) to form a better polymer/ller interface.
This may lead to rigidifying the polymer chains around the Co(II)
NaY particles, which restricts their mobility, and thus, reduces the
penetrant transport in this region. N2 is more inuenced by the issue
because of its diffusive dominant transport. As a result, CO2 /N2 ideal
selectivity is increased by the facilitated transport of CO2 through the
Co(II)NaY particles.
Finally, it can be said that the enhanced ideal selectivity of 29.2 for
the CA/Co(II)NaY (15 wt%) membrane in comparison with the ideal
selectivities of 25.5 and 25.0 for the CA and CA/NaY (20 wt%) membranes respectively, can introduce it as a potential for investigation of
commercial gas separation membranes.
4. Conclusions
The NaY zeolite was ion exchanged with cobalt(II) cations in order to investigate the effect of the ion exchanged zeolite (Co(II)NaY
zeolites) incorporated in the cellulose acetate (CA) dense membrane
for gas separation. The results of particle characterizations by SEM,
N2 adsorptiondesorption isotherm, UVvis DRS, and XRD showed
a proper ion exchange reaction. Moreover, characterization of the
membranes by SEM, XRD, and FTIR-ATR showed a better compatibility of Co(II)NaY particles than NaY ones with the CA matrix, lower
crystallinity of the CA/zeolite mixed matrix membranes (MMMs)
compared to the neat CA membrane, and also no chemical interaction between the zeolites and CA structure in the MMMs.
An optimum ideal permselectivity was obtained for the prepared
MMMs at 15 wt% Co(II)NaY loading into the CA matrix whereas at
a pressure of 4 bar, CO2 permeability was increased from 2.28 to
3.28 Barrer (up to 43.9%) as compared to the neat CA membrane.
This almost coincided with a slight decrease in the CO2 permeability
of CA/Co(II)NaY as compared to the CA/NaY membrane. Generally,
the CA/Co(II)NaY MMMs showed a better CO2 /N2 ideal selectivity
(=29.2, at 4 bar) than both the CA (=25.5) and CA/NaY(=25.0) membranes. These make the cobalt(II) substituted NaY zeolite an attractive
candidate for modication of CO2 separation membranes.
References
[1] Huang J, Zou J, Winston Ho WS. Carbon dioxide capture using a CO2 -selective
facilitated transport membrane. Ind Eng Chem Res 2008;47:12617.
[2] Shen J-N, Yu C-C, Zeng G-N, van der Bruggen B. Preparation of a facilitated transport membrane composed of carboxymethyl chitosan and polyethylenimine for
CO2 /N2 separation. Int J Mol Sci 2013;14:362138.
[3] Takht Ravanchi M, Kaghazchi T, Kargari A. Application of membrane separation
processes in petrochemical industry: a review. Desalination 2009;235:199244.
[4] Barsema JN, van der Vegt NFA, Koops GN, Wessling M. Ag-functionalized carbon
molecular-sieve membranes based on polyelectrolyte/polyimide blend precursors. Adv Funct Mater 2005;15:6975.
[5] Takahashi A, Yang RT, Munson CL, Chinn D. Cu(I)Y-zeolite as a superior adsorbent for diene/olen separation. Langmuir 2001;17:840513.
[6] Hosseinkhani O, Kargari A, Sanaeepur H. Facilitated transport of CO2 through
Co(II)-S-EPDM ionomer membrane. J Membr Sci 2014;469:15161.
[7] Hgg M-B, Quinn R. Polymeric facilitated transport membranes for hydrogen purication. MRS Bull 2006;31:7505.
[8] Li Y, Chung T-S, Kulprathipanja S. Novel Ag+ -zeolite/polymer mixed matrix membranes with a high CO2 /CH4 selectivity. AIChE J 2007;53:61016.
[9] Sanaeepur H, Nasernejad B, Kargari A. Cellulose acetate/nano-porous zeolite mixed matrix membrane for CO2 separation. Greenh Gases: Sci Technol
2015;5:291304.
[10] Rezakazemi M, Ebadi Amooghin A, Montazer-Rahmati MM, Ismail AF, Matsuura T.
State-of-the-art membrane based CO2 separation using mixed matrix membranes (MMMs): an overview on current status and future directions. Prog Polym
Sci 2014;39:81761.
[11] Sanaeepur H, Kargari A, Nasernejad B. Aminosilane-functionalization of a
nanoporous Y-type zeolite for application in a cellulose acetate based mixed matrix membrane for CO2 separation. RSC Adv 2014;4:6396676.
[12] Ebadi Amooghin A, Omidkhah M, Kargari A. The effects of aminosilane grafting on
NaY zeoliteMatrimid 5218 mixed matrix membranes for CO2 /CH4 separation. J
Membr Sci 2015;490:36479.
[13] Flanigen EM, Broach RW, Wilson ST. Introduction. In: Kulprathipanja S, editor. Zeolites in industrial separation and catalysis. Weinheim: WILEY-VCH Verlag GmbH
& Co. KGaA; 2010. editor p. 126.
[14] Corma A, Garcia H. Supramolecular host-guest systems in zeolites prepared by
ship-in-a-bottle synthesis. Eur J Inorg Chem 2004;6:114364.
[15] Corma A, Garcia H. Carbocations and organic radical cations inside zeolite matrices: generation, characterization, stability and properties. Top Catal 1998;6:127
40.
[16] Kusakabe K, Kuroda T, Murata A, Morooka S. Formation of a Y-type zeolite
membrane on a porous -alumina tube for gas separation. Ind Eng Chem Res
1997;36:64955.
[17] Kusakabe K, Kuroda T, Morooka S. Separation of carbon dioxide from nitrogen using ion-exchanged faujasite-type zeolite membranes formed on porous support
tubes. J Membr Sci 1998;148:1323.
[18] Kusakabe K, Kuroda T, Uchino K, Hasegawa Y, Morooka S. Gas permeation
properties of ion-exchanged faujasite-type zeolite membranes. AIChE J
1999;45:12206.
[19] Hasegawa Y, Watanabe K, Kusakabe K, Morooka S. The separation of CO2 using Ytype zeolite membranes ion-exchanged with alkali metal cations. Sep Purif Technol 2001;22-23:31925.
[20] Hasegawa Y, Tanaka T, Watanabe K, Jeong B-H, Kusakabe K, Morooka S. Separation
of CO2 CH4 and CO2 N2 systems using ion-exchanged zeolite membranes with
different Si/Al ratios. Korean J Chem Eng 2002;19:30913.
[21] Qi R, Wang Y, Chen J, Li J, Zhu S. Removing thiophenes fromn-octane using PDMS
AgY zeolite mixed matrix membranes. J Membr Sci 2007;295:11420.
[22] Dong G, Li H, Chen V. Challenges and opportunities for mixed-matrix membranes
for gas separation. J Mater Chem A 2013;1:461030.
[23] Mischnick P, Momcilovic D. Chemical structure analysis of starch and cellulose
derivatives. Adv Carbohyd Chem Bi 2010;64:117210.
[24] Greish YE, Meetani MA, Al Matroushi EA, Al Shamsi B. Effects of thermal and
chemical treatments on the structural stability of cellulose acetate nanobers.
Carbohydr Polym 2010;82:56977.
[25] Perez S, Samain D. Structure and engineering of celluloses. Adv Carbohydr Chem
Bi 2010;64:25116.
[26] Wu J, Yuan Q. Gas permeability of a novel cellulose membrane. J Membr Sci
2002;204:18594.
[27] Rufford TE, Smart S, Watson GCY, Graham BF, Boxall J, Diniz da Costa JC, et al. The
removal of CO2 and N2 from natural gas: a review of conventional and emerging
process technologies. J Petrol Sci Eng 2012;94-95:12354.
[28] Hasegawa Y, Watanabe K, Kusakabe K, Morooka S. Inuence of alkali cations on
permeation properties of Y-type zeolite membranes. J Membr Sci 2002;208:415
18.
[29] Ebadi Amooghin A, Sanaeepur H, Kargari A, Moghadassi A. Direct determination
of concentration-dependent diffusion coecient in polymeric membranes based
on the Frisch method. Sep Purif Technol 2011;82:10213.
[30] Sanaeepur H, Ebadi Amooghin A, Moghadassi A, Kargari A, Moradi S,
Ghanbari D. A novel acrylonitrilebutadienestyrene/poly(ethylene glycol) membrane: preparation, characterization, and gas permeation study. Polym Adv Technol 2012;23:120718.
[31] Sanaeepur H, Ebadi Amooghin A, Moghadassi A, Kargari A. Preparation and characterization of acrylonitrilebutadienestyrene/poly(vinyl acetate) membrane
for CO2 removal. Sep Purif Technol 2011;80:499508.
[32] Ebadi Amooghin A, Sanaeepur H, Moghadassi A, Kargari A, Ghanbari D, Sheikhi
Mehrabadi Z. Modication of ABS membrane by PEG for capturing carbon dioxide
from CO2 /N2 streams. Sep Sci Technol 2010;45:138594.
[33] Saito A, Foley HC. Curvature and parametric sensitivity in models for adsorption
in micropores. AIChE J 1991;37:42936.
[34] German Draft Standard DIN 66135-4. Micropore analysis by gas adsorption. Part
4: determination of pore distribution according to HorvathKawazoe and Saito
Foley. September 2004.
[35] Cheng LS, Yang RT. Predicting isotherms in micropores for different molecules
and temperatures from a known isotherm by improved HorvathKawazoe equations. Adsorption 1995;1:18796.
[36] Taniguchi K, Takaishi T. Polarizability of zeolite crystals determined by XPS techniques. In: Proceedings of the 7th international zeolite conference, No 4A-10;
1986. p. 1556.
[37] Derouane EG. The energetics of sorption by molecular sieves: surface curvature
effects. Chem Phys Lett 1987;142:2004.
[38] Breck DW. Zeolite molecular sieves: structure, chemistry and use. New York: John
Wiley & Sons, Ltd; 1974.
[39] Venero AE, Chiou JN. Characterization of zeolites by gas adsorption at low pressures. MRS Syrup Proc 1988;111:23540.
H. Sanaeepur et al. / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413
[40] Shukla P, Wang S, Singh K, Ang HM, Tad MO. Cobalt exchanged zeolites for heterogeneous catalytic oxidation of phenol in the presence of peroxymonosulphate.
Appl Catal B: Environ 2010;99:1639.
[41] Shannon RD. Revised effective ionic radii and systematic studies of interatomic
distances in halides and chalcogenides. Acta Cryst 1976;A32:75167.
[42] Kumar KS, TS, Natarajan P. Photoprocess of molecules encapsulated in porous
solids X: photosensitization of zeolite-Y encapsulated tris(2,2 -bipyridinenickel(II)ion by phenosafranine adsorbed onto the external surface of the nanoporous
host. J Chem Sci 2014;126:94554.
[43] Nezamzadeh-Ejhieh A, Moazzeni N. Sunlight photodecolorization of a mixture
of methyl orange and bromocresol green by CuS incorporated in a clinoptilolite
zeolite as a heterogeneous catalyst. J Ind Eng Chem 2013;19:143342.
[44] Sebastian J, Jinka KM, Jasra RV. Effect of alkali and alkaline earth metal ions
on the catalytic epoxidation of styrene with molecular oxygen using cobalt(II)exchanged zeolite X. J Catal 2006;244:20818.
[45] Verberckmoes AA, Weckhuysen BM, Schoonheydt RA. Spectroscopy and coordination chemistry of cobalt in molecular sieves. Microporous Mesoporous Mater
1998;22:16578.
[46] Vakros J, Bourikas K, Perlepes S, Kordulis C, Lycourghiotis A. Adsorption of cobalt
ions on the electrolytic solution/ -alumina interface studied by diffuse reectance spectroscopy (DRS). Langmuir 2004;20:1054250.
[47] Noiroj K, Intarapong P, Luengnaruemitchai A, Jai-In S. A comparative study of
KOH/Al2 O3 and KOH/NaY catalysts for biodiesel production via transesterication
from palm oil. Renew Energy 2009;34:114550.
[48] Kariduraganavar MY, Kittur AA, Kulkarni SS, Ramesh K. Development of novel
pervaporation membranes for the separation of waterisopropanol mixtures using sodium alginate and NaY zeolite. J Membr Sci 2004;238:16575.
[49] Madadi M, Rahimi R. Zeolite-immobilized Mn(III), Fe(III) and Co(III) complexes
with 5,10,15,20-tetra(4-methoxyphenyl)porphyrin as heterogeneous catalysts for
the epoxidation of (R)-(+)-limonene: synthesis, characterization and catalytic activity. Reac Kinet Mech Cat 2012;107:21529.
[50] Salavati-Niasari M, Salimi Z, Bazarganipour M, Davar F. Synthesis, characterization and catalytic oxidation of cyclohexane using a novel host (zeolite-Y)/guest
(binuclear transition metal complexes) nanocomposite materials. Inorg Chem
Acta 2009;362:371524.
[51] Yang Y. Cellulose acetate. In: Mark JE, editor. Polymer data handbook. New York:
Oxford University Press; 1999. editor p. 4956.
[52] Benosmane N, Guedioura B, Hamdi SM, Hamdi M, Boutemeur B. Preparation,
characterization and thermal studies of polymer inclusion cellulose acetate membrane with calix[4]resorcinarenes as carriers. Mater Sci Eng C 2010;30:8607.
[53] Dogan H, Hilmioglu ND. Zeolite-lled regenerated cellulose membranes for pervaporative dehydration of glycerol. Vacuum 2010;84:112332.
[54] Badarau C, Wang ZY. Synthesis and optical properties of thermally and photochemically cross-linkable diacetylene-containing polymers. Macromolecules
2004;37:14753.
413
[55] Kittur AA, Kulkarni SS, Aralaguppi MI, Kariduraganavar MY. Preparation and
characterization of novel pervaporation membranes for the separation of waterisopropanol mixtures using chitosan and NaY zeolite. J Membr Sci 2005;247:75
86.
[56] Ma X, Hu C, Guo R, Fang X, Wu H, Jiang Z. HZSM5-lled cellulose acetate membranes for pervaporation separation of methanol/MTBE mixtures. Sep Purif Technol 2008;59:3442.
[57] Achoundong CSK, Bhuwania N, Burgess SK, Karvan O, Johnson JR, Koros WJ. Silane
modication of cellulose acetate dense lms as materials for acid gas removal.
Macromolecules 2013;46(14):558494.
[58] Bae D, Seff K. Structures of cobalt(II)-exchanged zeolite X. Microporous Mesoporous Mater 1999;33:26580.
[59] Frising T, Leaive P. Extraframework cation distributions in X and Y faujasite zeolites: a review. Microporous Mesoporous Mater 2008;114:2763.
[60] Hutta PJ, Lunsford JH. Spectroscopic evidence for the location of Co2+ ions in zeolite Y upon dehydration. J Chem Phys 1977;66:471617.
[61] Broach RW. Zeolite types and structures. In: Kulprathipanja S, editor. Zeolites in
industrial separation and catalysis. Weinheim: WILEY-VCH Verlag GmbH & Co.
KGaA; 2010. editor p. 2759.
[62] Bastani D, Esmaeili N, Asadollahi M. Polymeric mixed matrix membranes containing zeolites as a ller for gas separation applications: a review. J Ind Eng Chem
2013;19:37593.
[63] Golemme G, Jansen JC, Muoio D, Bruno A, Manes R, Buonomenna MG, et al. Glassy
peruorolymerzeolite hybrid membranes for gas separations. In: Yampolskii Y,
Freeman BD, editors Membrane gas separation. West Sussex, United Kingdom:
John Wiley & Sons Ltd; 2010. editors p. 11324.
[64] Baker RW. Membrane technology and applications. 3rd ed. West Sussex, United
Kingdom: John Wiley & Sons Ltd; 2012.
[65] Bos A, Pnt IGM, Wessling M, Strathmann H. CO2 -induced plasticization phenomena in glassy polymers. J Membr Sci 1999;155:6778.
[66] Sanders DF, Smith ZP, Guo R, Robeson LM, McGrath JE, Paul DR, et al. Energyecient polymeric gas separation membranes for a sustainable future: a review.
Polymer 2013;54:472961.
[67] Sanaeepur H, Ebadi amooghin A, Moghadassi A, Kargari A, Ghanbari D, Sheikhi
Mehrabadi Z, et al. CO2 /CH4 separation via polymeric blend membrane. Iran J
Polym Sci Technol 2010;23:1728 (in Persian).
[68] Ebadi amooghin A, Zamani Pedram M, Omidkhah M, Yegani R. A novel
CO2 -selective synthesized amine-impregnated cross-linked polyvinylalcohol/glutaraldehyde membrane: fabrication, characterization, and gas permeation
study. Greenh Gases: Sci Technol 2013;3:37891.
[69] Snider MT, Verweij H. Gas sorption studies on zeolite Y membrane materials
for post-combustion CO2 capture in coal-red plants. Microporous Mesoporous
Mater 2014;192:37.