Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413

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Journal of the Taiwan Institute of Chemical Engineers

journal homepage: www.elsevier.com/locate/jtice

A novel Co2+ exchanged zeolite Y/cellulose acetate mixed matrix

membrane for CO2 /N2 separation
Hamidreza Sanaeepur a, Ali Kargari a,b,, Bahram Nasernejad b, Abtin Ebadi Amooghin c,
Mohammadreza Omidkhah d
a
Membrane Processes Research Laboratory (MPRL), Petrochemical Engineering Department, Amirkabir University of Technology (Tehran Polytechnic), Mahshahr
Campus, P.O. Box 415 Mahshahr, Iran
b
Department of Chemical Engineering, Amirkabir University of Technology, P.O. Box 15875-4413 Tehran, Iran
c
Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak 38156-8-8349, Iran
d
Faculty of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-143 Tehran, Iran

a r t i c l e

i n f o

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).

reaction occurs between the transition metal ions and O2 [4], CO

[5], CO2 [6], and unsaturated hydrocarbon molecules [3] to form complexation bonds. CO2 reacts at one reactive site of the carrier to
form a complex and then hops to another reactive carrier site where
a decomplexation reaction along with a recomplexation occurs. As a
result, CO2 is favorably transported via the hopping mechanism
a reactive diffusion downstream of the membrane in simultaneous
with the Fickian diffusion both for CO2 and other gas components [7].
The noble transition ions incorporated immobilized (xed) carrier FTMs, like the other FTMs, suffer from the durability (or stability) during the long-term operation. It is primarily due to the noble
metal ions are likely to be reduced to form metal nanoparticles and
further aggregate to each other [8]. To promote the stability of the
membranes, it can be aided from the concept of a mixed matrix membrane (MMM) to stabilize the ions. In this way, solid particles encompass the ions disperse into the membrane polymeric matrix. Better
thermo-mechanical membrane stability has also been achieved by a

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.

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H. Sanaeepur et al. / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 403413

MMM along with the durability of ions in species transport [9,10].

An additional mechanism of surface-activated diffusion of species in
porous particles can be also accompanied with the two abovementioned mechanisms for the FTMs [11,12]. It happens in the porous
particles by which some of the CO2 molecules adsorb (physically) to
the porous solids and are able to jump from a sorption site to adjacent sorption site in a manner similar to solid-state diffusion. Zeolites, with suitable physio-chemical properties can be introduced as a
proper candidate in the eld.
Zeolites are aluminosilicate inorganic materials whose framework
5
contains AlO4 and SiO4
4 tetrahedral linked to each other by the
sharing of oxygen atoms in each corner and one Al or Si atom at
the center of the tetrahedron [13]. Al is located in the neighboring
of Si in period 3 on the periodic table, respectively in groups III and IV
of the main-group elements, with approximately similar atomic radii
for both the elements. Isomorphic substitution of an Al atom with a
Si atom in the zeolite framework causes a negative charge to be in5
duced by each AlO4 tetrahedron. To maintain the electroneutrality
of the zeolite, it requires the presence of organic or inorganic cations
[14]. Typically these accompanying cations are alkali or alkali-earth
metal ions (such as sodium, potassium, magnesium and calcium) or
quaternary ammonium ions. However, it is possible to exchange them
by other mono- or di-positive ions without producing any alteration
of the crystalline network [15]. Kusakabe and coworkers [16] have
synthesized a Y-type zeolite membrane on a porous -alumina support specialized for potential application in CO2 /N2 separation and
observed a CO2 permeance in the order of 107 mol/(m2 s Pa) and
a selectivity of 20100 at 30 C and 1 atm. In addition, they have
investigated the CO2 /N2 separation properties of NaY zeolite membranes ion-exchanged with alkali (K, Rb, Cs) and alkali-earth (Mg, Ca,
Ba) cations for the rst time and observed higher selectivities than
NaY-type zeolite membrane almost in all cases [1720]. This coincided with almost no considerable changes in the CO2 permeances.
In case of ion-exchanged zeolites incorporated into polymeric matrix to form MMMs a few works have been reported. Li et al. [8]
have prepared Ag+ ion-exchanged zeolites from A-type zeolite particles via ion exchange by Ag+ ions. They have embedded both the
NaA and AgA zeolites (050 wt%) into polyethersulfone (PES) to prepare PES/zeolite mixed matrix membranes (MMMs). They observed
a decrease in CO2 permeability and an increase in CO2 /CH4 selectivity with the increment in zeolite loadings. This was described by
the effects of partial pore blockage of the zeolites (since the pore
size of NaA is 3.8 A and that of AgA should be smaller because the
this is
Ag+ ionic radius is 1.15 A and the Na+ ionic radius is 1.02 A;
and also the polymer
while the kinetic diameter of CO2 is 3.30 A)
chain rigidication. Moreover, the CO2 permeability and CO2 /CH4 selectivity of AgA-lled membranes were higher than those lled with
NaA which was attributed to a reversible reaction between the Ag+
ion and CO2 molecule. Qi et al. [21] prepared Ag+ ion-exchanged Ytype zeolite and incorporated it into a polydimethylsiloxane (PDMS)
matrix to prepare a MMM for desulfurization of gasoline. They observed the AgY zeolite in comparison with the pristine NaY zeolite
led to a greater increase in total ux with approximately no decrease
in the selectivity. This was attributed to the continuous complexation
and decomplexation reaction between Ag+ ions and organo-sulfurs
and consequently changing the local concentration. This would accelerate sorption onto and desorption from the zeolite particles, and
hence, facilitate transport of the molecules.
The present work is aimed at combining the facilitated transport
mechanism of a transition metal ion with the surface-activated diffusion mechanism of a zeolite through a new cobalt ion-exchanged
zeolite. Then the treated zeolites are applied to improve the CO2 /N2
separation performance of the MMMs. In this case, the cobalt a transition metal but not a noble one ion with a same electronegativity
of silver was chosen to minimize the reduction of ions to the analogous metallic nanoparticles. A hydrophilic sodium zeolite-Y (NaY),

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],

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405

2.3. Membrane preparation

THF was selected as the solvent due to its sucient vapor pressure to form a uniform polymer lm within an appropriate time. In
order to remove the adsorbed water vapors, the polymer was dried
one day at 80 C in an oven. A certain amount of Co(II)NaY and CA
were well mixed in THF solvent during the following process. First,
a certain amount (e.g., 0.150 g for CA/Co(II)NaY 5 wt%) of Co(II)
NaY powder was added to 8.5 g THF in a 100 ml round glass bottle with a plastic stopper and stirred for 24 h at room temperature.
Next, about 10% of the total polymer (e.g., 0.135 g of 1.350 CA for
CA/Co(II)NaY 5 wt%) was added to the Co(II)NaY/THF suspension
and stirred for an additional 4 h to form a thin coating layer of CA
around the solid Co(II)NaY zeolites. After ltration, the remaining
part of CA was added to the mixture and mixed for 6 h. This has
the advantage of more organicorganic compatibility with the previously formed CA layer. Afterwards, the nal solution was degassed
for about an hour at room temperature and was cast onto a clean
glass plate using a doctors blade with a 300 m gap. After sucient
solvent evaporation through 24 h, the membrane was separated from
the plate surface and placed in a vacuum oven for 48 h at 150 C,
with special attention to slow initial heating and nal cooling rates.
The prepared membrane thicknesses were measured by a digital micrometer (Mitutoyo , Seisakusho, Tokyo, Japan) with an accuracy of
1 m and found an average of about 30 1 m.
2.4. Gas permeation experiments
The pure gas permeability was measured by the known time-lag
method. All the membrane samples were tested at room temperature (25 C) and the test pressure in the range of 210 bar. The rate
of pressure increase (dp/dt) at the permeate side at a steady state was
measured by a precise absolute pressure transmitter (Type 691, Huba
Control, Wrenlos, Switzerland) and used to calculate the permeability through the following equation:

P=

Fig. 1. SEM images of (a) NaY and (b) Co(II)NaY zeolites.

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

where P is the gas permeability in Barrer (1 Barrer = 1010 cm3 (STP)

cm/(cm2 cmHg s)), V is the dead-volume of the downstream chamber
(cm3 ), l is the membrane thickness (cm), p0 is the feed pressure (atm),
dp/dt is the steady rate of pressure increment in the downstream side
(atm/s), A is the effective membrane area (cm2 ), and T is the absolute temperature (K). It should be noted that to ensure the accuracy
of the data acquisitions, each measurement is replicated on at least
three different membrane samples with the same composition and
the reported value is the arithmetic mean of the samples.
In the case of gas transport through dense membranes, the
solution-diffusion mechanism can also be used to express the permeability (P) as the product of a kinetic (diffusion) and a thermodynamic
factor (sorption) [29,30]:

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)

Calculated by the t-plot method.

Desorption average pore width (4Vp /SBET by BET).
Calculated by the HK-based SF model.

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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.

Figu. 3. XRD spectra of the pure NaY and Co(II)NaY zeolites.

where D and S are the average diffusivity and solubility coecients,

respectively.
In addition, the ideal selectivity of the two pure components was
calculated by dividing the respected permeabilities in the same conditions [31]:

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)

D and S are the diffusivity and solubility selectivities, rewhere AB

AB
spectively.

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)

in the wave-length range of 200900 nm. Reectance values

were measured relative to pure barium sulfate, BaSO4 , as a standard reference material because in the above wavelength range
its absorption coecient is so low that it can be considered
negligible.
The X-ray diffraction (XRD) patterns of the particles and membranes were analyzed on an XPert MPD wide-angle X-ray diffractometer (Philips, Eindhoven, Netherlands). The measurements were
carried out at room temperature using monochoromatic radiation of
accelerating volt -rays emitted by cobalt at a wave-length of 1.79 A,
age of 40 kV, and tube current of 40 mA. To identify the crystal structure, the scan range the angle (2 ) of diffraction was varied from
3 to 70 with a step increment of 0.02s1 .
The textural properties of particles were determined by N2
adsorptiondesorption isotherms at 76 K (liquid nitrogen) using a
TriStar II 3020 V1.03 analyzer (Micromeritics Instrument Co., Norcross, GA, USA) after degassing the zeolite samples at 150 C for at
least 4 h under vacuum (<103 Pa). The t-plot method was applied
to calculate the surface area and volume of micro-pores of the particles. The average pore diameter dp = 4Vp /SBET (assuming a cylindrical shape of pores) were calculated from the desorption data, where
SBET and Vp are respectively the specic surface area and volume of

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407

3. Results and discussion

3.1. Particle characterization
3.1.1. SEM
Fig. 1 shows the SEM spectra of NaY and Co(II)NaY zeolite samples. NaY zeolites showed polygonal layered-like crystals with the
sharp edges. Co(II)NaY samples were also polygonal in shape but
with more or less rounded edges. This structural change after cation
exchange reaction could be resulted from an acidic attack; the hydrated Co2+ is an acidic ion which reacts with H2 O molecules in the
exchange solution to form hydronium ions, H3 O+ and CoOH+ . All the
three cations can exchange with Na+ ions of the zeolite. Through an
acidic attack the hydronium ion can dissolve the Al+3 ion of the zeolite and cause damage to the unit cell structure [40].
3.1.2. Adsorptiondesorption characteristics
Table 1 presents adsorptiondesorption characteristics of NaY and
Co(II)NaY zeolite samples. As it is observed, both the micro-pore
volume and surface area were reduced for Co(II)NaY samples as
compared to pure NaY zeolites. However, the average pore/micropore diameters were increased. A higher pore diameter of Co(II)NaY,
calculated by both the BET and SF models, in comparison with NaY
can be due to a considerable smaller effective ionic radius of Co2+
compared to that of Na+ , which has been measured by Shannon [41]:

> Co2+ (=0.75 A)

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.

micro-pores calculated according to the standard BrunauerEmmet

Teller (BET) method. The total desorption pore volume Vp estimated
at p/p0 = 0.98, where p and p0 denote the equilibrium and saturation pressures of nitrogen, respectively. Additionally, the Horvath and
Kawazoe (HK)-based Saito and Foley (SF) model for cylindrical pores
[33], which can be a useful mean for the transformation of nitrogen
adsorption/desorption data on a zeolite into a micropore size distribution, was also considered here and the obtained results were compared with the BET ones. The SF model calculates the radius of micropore cylinder, rp , from the N2 desorption data up to p/p0 = 0.98
in NaY and Co(II)NaY zeolites, as described in the standard DIN
66135-4 [34]. In this case, the values of parameters adopted from
[3539].
Fourier transform infrared-attenuated total reectance (FTIRATR) investigations were conducted on the membranes using a Perkin-Elmer Spectrum, Frontier model, Version 10.03.06
(Perkin-Elmer Instruments, Norwalk, CT, USA) in the range of
6004000 cm1 .
The membrane morphologies were evaluated by scanning electron microscopy (SEM). After fracturing the membrane samples in
liquid nitrogen and sputter-coating with gold by a BAL-TEC SCD 005
sputter coater (BAL-TEC AG, Balzers, Liechtenstein), the samples were
tested by a SEM (KYKY-EM3200, KYKY Technology Development Ltd.,
Beijing, China).

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

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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.

The absorption band at 901 cm1 is attributed to the -linked glucan

structure [53]. In addition, a small absorption band at 2119 cm1
is attributed to a high temperature dried CA. This is assigned to a
heat-dissociated or weakly bound CC which is a characteristic absorption band of the acetylene. This band can be observed as
enough thermal energy required for disassociation of intra-and/or
inter-molecular hydrogen bonding adsorbed which leads to formation of a methylenic proton (OCH2 CC). This could be explained
by considering a rearrangement reaction that results in a new fragment [54].
In the FTIR-ATR spectra of NaY and Co(II)NaY lled membranes,
the band intensities of CA are generally decreased by incorporating
both the pure and Co2+ exchanged zeolites into the polymer matrix. This reduction in the band intensities for the Co(II)NaY contained sample is more than that for NaY contained membranes. However, the intensities of multiple characteristic bands of neat CA in
the range of 12001000 cm1 , which correspond to CO stretching vibrations, show less reduction upon introducing the zeolites in
the membrane. This is caused by overlapping the SiOSi stretching
(11001000 cm1 ) of the zeolites, which appears approximately at
the same frequency of CO stretching [55,56]. This is repeated almost in the range of 800600 cm1 which may be corresponded
to AlO stretching vibrations [53]. Other characteristic bands corresponding to SiOH stretching (36503200 cm1 ) and bending
(900850 cm1 ) vibrations of zeolites are also overlapped respectively with the OH stretching vibrations of the hydroxyl group in
the CA and the interlayer stretching and bending vibration modes of
molecular water. Indeed, these two latter bands are not observed in
the FTIR-ATR spectra of the MMMs due to a considerable reduction in
their overall band intensities as compared to the neat CA membrane.
3.2.3. XRD
Fig. 6 presents the XRD patterns of the neat CA, CA/NaY, and
CA/Co(II)NaY membranes. CA showed two broad crystalline peaks
at 12 and 22, in accordance with Achoundong et al. [57] and Ma et
al. [56]. After incorporating the NaY or Co(II)NaY zeolites into the
CA matrix, the resulted patterns showed the characteristic peaks of
both the zeolites (see also the Fig. 3) and CA. However, a slight decrease in the intensity of CA peaks suggests that the crystallinity of
CA is reduced in the presence of the zeolites.

3.3. Membrane performance

3.3.1. The effect of particle loadings
Fig. 7ac depicts the effect of Co(II)NaY loadings on the (a) CO2
permeability, (b) N2 permeability, and (c) CO2 /N2 ideal selectivity of
the prepared membranes. CO2 permeability of all membrane samples in Fig. 7a shows a continuous increase by a moderate change in
the slope of lines between two adjacent situations with the increment in Co(II)NaY content from 0 to 20 wt%. This is a predictable behavior due to the effect of CO2 facilitated transport via the Co2+ ions
distributed on the extra-framework sites in the Co(II)NaY zeolites
(Scheme 1); it is worthy to state that Co2+ ions are preferably found
in site (a) (the hexagonal prism) of Co2+ exchanged faujasite if the
sample is [completely] dehydrated. In this case, half of the Co2+ ions
occupied the site (a) avoid electrostatic repulsion with Na+ ions. Another half of these Co2+ ions each coordinate additionally to an OH
ion [58]. Therefore, they are inactivated for an effective interaction
with CO2 and N2 molecules. Their only possible effect on molecule
transport is a small change in the anity of the Co(II)NaY framework
for CO2 and N2 , as well as a very small expansion of the micro-pore
diameter (see the adsorptiondesorption results). On the other hand,
Co2+ ions are mainly located in sites (b) (the sodalite or cages) and
(c) (the large cavities, super or cages) if the sample is at least partially hydrated [59]. As the DRS spectra indicated, the molecular water, as an octahedral [Co(H2 O)6 ]2+ complex, can still exist after dehydration under vacuum at 120 C. This is in accordance with Bae and
Seff [58] results for the Co2+ exchanged samples from aqueous solution at 80 C (a temperature close to what was done herein at 90 C).
Moreover, Hutta and Lunsford [60] obtained the same results by dehydration of samples under 200 C. In general, the important cation
site for interaction with adsorbed gas molecules is site (c) which is
accessible by a three-dimensional 12-ring. On the other hand, site (b)
which is only accessible through the deactivated 6-ring cages is disabled for interaction with penetrant molecules [61].
In addition to the above-mentioned, the large pores of the Y-type
zeolite facilitate the activated diffusion, not only for the less adsorptive lighter N2 molecules (Fig. 7b) but also for the adsorptive heavier CO2 molecules [18, 62]. The average pore size of the Y-type zeolite is 0.74 nm which is suciently large in comparison with the
kinetic diameter of CO2 and N2 (respectively, 0.33 and 0.37 nm) to

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

3.3.2. The effect of feed pressure

Fig. 8a and b shows the effect of feed pressure, 210 bar, on the
CO2 permeability and CO2 /N2 ideal selectivity of the neat CA and
CA/Co(II)NaY membranes. It is worthy to note that all the applied
pressure is lower than the CA plasticization pressure (=11 bar, at 27 C
[65]). This is a common behavior of glassy polymers and their MMMs
below the plasticization pressure for which their CO2 permeability
decreases as the feed pressure is increased [6668]. An increase in
feed pressure forces the polymer chains to form a closer packing density and thus decreases the gas permeability (Fig. 8a). It was demonstrated by Kusakabe et al. [18] for Y-type zeolites that the effect of
cation exchange on the CO2 diffusivities is considerably more than
that for N2 because of the dependence of CO2 diffusivities on the
adsorption properties, which vary with the cation species. Their results also revealed that the diffusivity selectivities of both pure NaY
and ion-exchanged Y-type zeolites are < 1, some order of magnitude lower than the corresponding results of sorption selectivities.
In addition, Snider and Verweij [69] investigated CO2 and N2 sorption
isotherms for NaY zeolite powders (with a typical grain size of 0.2 m
and Si/Al ratio of 1.59) at wide pressure and temperature ranges (1
50 bar, 30150 C). They showed a reduction in CO2 /N2 sorption selectivity with increasing the feed pressure, especially at lower temperatures. Therefore, it can be concluded that the overall selectivity of

412

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.
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