Fuel Processing Technology 118 (2014) 125132

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Fuel Processing Technology

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

Carbon dioxide separation using asymmetric polysulfone mixed matrix

membranes incorporated with SAPO-34 zeolite
M.U.M. Junaidi a, C.P. Leo a,, A.L. Ahmad a, S.N.M. Kamal a, T.L. Chew b
a
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S., Pulau Pinang, Malaysia
b
Department of Petrochemical Engineering, Faculty of Engineering and Green Technology (FEGT), Perak Campus, Universiti Tunku Abdul Rahman, Jalan Universiti, Bandar Barat, 31900 Kampar,
Perak, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Tradeoff limitation on selectivity and permeability restricts the use of membranes for CO2 separation in natural
Received 25 April 2013 gas industry. Mixed matrix membranes (MMMs) with combined advantages of polymeric matrix and inorganic
Received in revised form 19 August 2013 llers have been long proposed to overcome this shortcoming, but thick dense symmetric layer structure with a
Accepted 19 August 2013
high mass resistance offers improvement in selectivity only. In this study, asymmetric polysulfone MMMs incor-
Available online xxxx
porated with small pore zeolite were proposed. SAPO-34 zeolite with a framework of 0.38 nm pore size and high
Keywords:
CO2 adsorption afnity was used as inorganic llers. The asymmetric mixed matrix membrane structure was pre-
Carbon dioxide separation pared using the phase inversion method. The effects of zeolite loading (530 wt.%) on the membrane character-
Mixed matrix membrane istics were studied using SEM with EDX, FT-IR, and TGA; while the gas transport properties were investigated
Polysulfone using pure gas permeation tests of N2, CO2 and CH4. Well dispersion of SAPO-34 particles in the polymer matrix
Zeolite was observed for zeolite loading less than 10 wt.%. The maximum CO2 permeance (314.02 GPU) was achieved by
incorporating 10 wt.% of SAPO-34 into asymmetric PSf membrane. Even without strong binding between PSf and
SAPO-34, CO2/N2 and CO2/CH4 selectivities up to 26.1 and 28.2 respectively were observed.
2013 Elsevier B.V. All rights reserved.

1. Introduction commercially applied [5]. However, these polymeric membranes showed

Natural gas reserves are typically contaminated with more than 40% of
carbon dioxide (CO2) and nitrogen (N2), which greatly reduce the caloric
value of the natural gas. For instance, Malaysia's natural gas reserves are
contaminated with about 2030% of CO2 [1]. The acidic nature of CO2
also causes serious corrosion in the gas pipeline. Hence, the CO2 content
in the natural gas transportation pipeline is specically limited to
4 vol.% [2].
Conventionally, natural gas is puried using gas absorption processes
which may involve physical absorption using solvents (polycarbonate,
tributylphosphate, etc.). However, the by-products from side reactions
of solvent with some natural gas components are difcult to be disposed
especially at offshore purication plants. Meanwhile, conventional chem-
ical absorption endures from several drawbacks such as ooding,
foaming, channeling, and high capital costs [3]. Besides the absorption
technology, various potential technologies such as adsorption [4] and
membrane separation [59] have been studied to separate CO2 from nat-
ural gas. In the adsorption technology, silica-alumina adsorbent combined
with pressure swing adsorption (PSA) has been adopted [5]. Whereas in
membrane technology, polymeric membranes such as cellulose acetate
(CA), polysulfone (PSf) and polyimide (PI) membranes have been
Corresponding author. Tel.: +60 4 5996425; fax: +60 4 5941013.
E-mail address: chcpleo@eng.usm.my (C.P. Leo).
less desirable separation performance due to the tradeoff between per-
meability and selectivity as propounded by Robeson [6]. Besides polymer-
ic membranes, inorganic membranes, especially zeolite membranes
(DDR, Silicalite-1, and SAPO-34) have been also explored in the high pres-
sure gas separation process. The zeolite membranes showed high selec-
tivity towards CO2 due to difference in diffusivity and competitive
adsorption [7]. Although inorganic membranes displayed excellent sepa-
ration selectivity, large-scale fabrication of these membranes is difcult as
it involves expensive raw materials, complex fabrication methods and
long preparation time. In order to overcome the limitations imposed by
both polymeric membranes and inorganic membranes, the idea to formu-
late composite membranes has emerged in the past few decades. Mixed
matrix membranes (MMMs) are composite polymeric membranes incor-
porated with inorganic adsorbent or molecular sieve material as llers [8].
Small pore zeolites especially SAPO-34 appealed as interesting llers
due to its high adsorption afnity to CO2. SAPO-34 zeolite is a chabazite
(CHA) structure zeolite that has a 0.38 nm framework pore size; which
is nearly similar to molecule sizes of the various gasses in a natural gas
mixture. A recent work by Hudiono et al. [9] described the uses of the
SAPO-34 zeolite to enhance separation performance of a neat solid po-
lymerized room-temperature ionic liquid (poly (RTIL)) membrane.
The poly (RTIL) material was used in their study because of its wetting
agent properties, which could improve adhesion between the polymer
and the zeolite particles. By adding 20 wt.% of SAPO-34 zeolite into the
poly (RTIL) polymer, the CO2/CH4 ideal selectivity factor increased to 39,

0378-3820/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2013.08.009
126 M.U.M. Junaidi et al. / Fuel Processing Technology 118 (2014) 125132
nearly 21.8% of enhancement compared to the neat membrane. A slight
increment in CO2 permeation was observed after blending SAPO-34
zeolite in poly (RTIL) membrane. On the other hand, Jha et al. [10]
used SAPO-34 zeolite particles as the llers to improve the separation
performance of polymer polyphophazene (PPZ) membrane for CO2
removal. For the neat PPZ membrane, the CO2/CH4 ideal selectivity of
15 was achieved at 22 C, whereas, the PPZ/SAPO-34 membrane
showed a slightly increased selectivity of 17.5. A more signicant incre-
ment in the CO2/CH4 selectivity could be observed at a lower tempera-
ture due to the increased relative adsorption of CO2 in the SAPO-34
pores and the decrease in relative diffusivity of CH4 [10]. The CO2 per-
meability for the PPZ/SAPO-34 membrane was lower than the neat
PPZ membrane due to PPZ polymer rigidication.
Karatay et al. [11] had conducted a similar work by fabricating
polyethersulfone (PES)/SAPO-34 membrane with an addition of a
low molecular weight additive, 2-hydroxy 5-methyl aniline (HMA).
PES/SAPO-34/HMA membrane showed a great increment in the
CO2/CH4 selectivity of 37.4 (about 50% increments) compared to
the pure PES membrane. The addition of SAPO-34 by 20 wt.% in the
PES polymer contributed into slight increment in the CO2 perme-
ation when the membrane solvent-evaporation fabrication method
was adopted in their works. This method tends to yield MMMs
with a thick dense symmetric layer structure with a high mass resis-
tance. Recent works on MMMs [1012] that utilized the homoge-
nous dense polymeric matrix conguration also showed little
improvement in the gas permeation when the inorganic phase was
implemented in the membrane fabrication. In order to reduce mass
transfer resistance, the dense selective layer must be engineered as
thin as possible. As the thin symmetric dense membrane suffered
from weak mechanical strength, asymmetric membrane with a thin
dense top layer supported by a porous sub-layer is proposed in this
work.
Asymmetric PSf membrane prepared via the simple phase inversion
route has been widely reported [3,13]. PSf is one of the most extensively
used materials in the production of industrial and commercial mem-
branes due to its high chemical stability, excellent mechanical strength,
compaction-resistance, and outstanding thermal resistance. PSf with
great resistance of plasticization is typically suitable to be applied for
CO2 removal in industries which require high operating pressure [14].
Incorporated with highly selective and porous SAPO-34 zeolite, asym-
metric PSf/SAPO-34 MMMs are expected to offer improvement not
only in selectivity but also in gas permeability. In this work, the effects
of the zeolite loading on the physical and separation characteristics of
asymmetric PSf membrane will be studied.
2. Materials and methods
2.1. Membrane preparation
The PSf pellets (MW: ~35,000) and methanol (MeOH) were pur-
chased from Aldrich, while the 1-methyl-2-pyrrolidinone (NMP) and
ethanol (EtOH) were supplied by Merck. Tetrahyrofuran (THF) was pur-
chased from Reidel-de Han. During the preparation of SAPO-34
particles, the solution with molar composition; Al2O3:P2O5:0.6SiO2:
1.07TEAOH:56H2O [15] was prepared by mixing ortho-phosphoric acid
(H3PO4, 85 wt.% aqueous solution, Merck), aluminium isopropoxide
(Al (i-C3H7O)3) from Aldrich and deionized water (DI) for 6 h to 12 h
at room temperature. Then, tetraethylammonium hydroxide template,
(TEAOH, 35 wt.% aqueous solution, Aldrich) was added and stirred for
30 min. After that, the colloidal silica sol (40 wt.% aqueous solution,
Ludox AS40) was inserted and mixed vigorously for 24 h. The solution
was then moved for hydrothermal synthesis in the autoclave for 24 h
at 200 C. Once the synthesis is done, the sediment containing zeolite
crystal was washed with DI water before drying in the oven at 100 C
for 24 h. The dried zeolite was then calcined in the furnace to eliminate
TEAOH template from zeolite framework at 500 C for 5 h.
Prior to membrane fabrication, the PSf pellets and calcined SAPO-34
were dried at 60 C and 125 C respectively overnight to remove excess
moisture. The other chemicals were used as received. In the preparation
of pure PSf membrane by phase inversion method, the polymer solution
which consisted of 25 wt.% of PSf, 47 wt.% NMP, 18 wt.% THF and
10 wt.% EtOH was prepared. The PSf pellets and EtOH were mixed in
the NMPTHF solution at ambient temperature for 5 h. Subsequently,
the solution was sonicated for 30 min before it was left for 1 day to
eliminate micro-bubbles trapped in the solution. The at sheet layer
membrane was prepared by pouring the polymer solution onto a
clean at glass plate and casting it by using a casting knife of 0.2 mm
gap at ambient temperature and left for force evaporation step in 30 s
to let the growth of thin dense layer [3]. After that, the at layered solu-
tion was immersed in the DI water bath and left overnight. Then, the
fabricated membrane was solvent-exchanged with MeOH for 2 h and
followed by drying at 110 C for 1 day.
The MMM solutions were prepared by stirring the required SAPO-34
zeolite crystal in EtOHNMPTHF solution for 2 h and then sonicating
for 10 min3 h, depending on the zeolite weight percentage loadings
in the solutions. The weight percentages of SAPO-34 loaded in each
membrane were varied as stipulated in Table 1. Subsequently, 10 wt.%
of the overall required PSf was mixed in the solution for 4 h. The solu-
tion was then sonicated for half an hour and followed by adding the
remaining PSf into the solution and stirred for 1 day. After that, the
solution was sonicated for 45 min to 2 h, depending on SAPO-34 load-
ing in the solution to ensure homogenous particle dispersion and elim-
inate trapped micro-bubbles as reported elsewhere [16,17,9]. The
remaining procedures that followed were done according to the steps
in pure PSf membrane fabrication.
2.2. SAPO-34 crystal characterization
Crystal characterization of the SAPO-34 zeolite was veried with
uncalcined SAPO-34 particles using high resolution X-ray diffraction,
XRD (Philips PAN analytical X-Pert PRO MRD PW3040, Spectris plc).
The surface area and pore volume of SAPO-34 particles were deter-
mined by running N2 adsorptiondesorption experiments using
Micromeritics ASAP 2020 on the calcined crystal particles. The particle
surface area was calculated using BrunauerEmmettTeller (BET)
method whereas the pore volume was calculated using t-Plot micropore
method. The crystal shapes and morphologies were observed by scan-
ning electron microscopy, SEM (Quanta FEG 450 Oxford Instruments,
Netherlands). The average particle size (average from 5 sets of data)
and particle size distribution condition of SAPO-34 were determined
by Zeta Sizer (Nano Sizer Malvern, United Kingdom).
2.3. Membrane characterization
The dried membrane samples were characterized using a Fourier
Transform Infrared (FT-IR) spectrometer (Nicolet iS10, Thermo Scientif-
ic, USA). All spectra were obtained from 32 scans at 4.00 cm1 resolu-
tion with wave numbers ranging from 400 to 4000 cm1. The
membrane sample morphologies and dense layer thickness were exam-
ined using a scanning electron microscope (SEM, Quanta FEG 450
Table 1
SAPO-34 concentration in membrane samples and average membrane thickness
estimated from SEM images.
Sample SAPO-34 conc. (%, w/w) Psf: SAPO-34 Thickness (m)
PSf-00 0 1:0 87
PSf-05 5 1:0.05 74
PSf-10 10 1:0.10 76
PSf-20 20 1:0.20 53
PSf-30 30 1:0.30 91
 M.U.M. Junaidi et al. / Fuel Processing Technology 118 (2014) 125132
Oxford Instrument, Netherlands). The membranes were fractured using
liquid nitrogen and coated with a thin layer of gold prior to scanning.
Energy dispersive X-ray (EDX, INCA, Oxford Instruments, Netherlands)
analysis was also conducted to conrm dispersion of the SAPO-34 parti-
cles in MMMs. Thermogravimetric (TGA) analysis of all fabricated mem-
branes was performed using a PerkinElmer Pyris-1 TGA. The analyses
were run in N2 from ambient temperature to 900 C at a heating rate
of 10 C/min.
2.4. Gas permeation performance test
The single gas permeation test was done for CO2, N2 and CH4 gasses
on membrane samples. Gasses with purities higher than 99% were pur-
chased from local companies. The test apparatus was set up as described
previously in detail elsewhere [3,9]. The test was carried out with a con-
stant pressure method at ambient temperature with feed pressure of
3.48 bar. Flat sheet disks with an effective diameter of 4 cm and effec-
tive membrane area of 12.6 cm2 were used. A soap bubble ow meter
was used to measure the volumetric ow rate of the permeate gas at at-
mospheric pressure. Each set of the volumetric ow rate data represents
an average of 3 replicates.
The unit for gas permeation measurement is Gas Permeation Unit
(GPU), where 1 GPU is equal to 106 cm3 (STP)/cm2 s cm Hg. The
permeance result data were calculated based on the equation below:
P Q
Permeance
l Ap
where P is permeability, l is membrane layer thickness, Q is volumetric
ow rate at standard temperature and pressure, A is effective mem-
brane area and p is the pressure difference across the membrane.
The ideal selectivity consisting of gas permeation i and j was determined
from the equation below:
Permeancei
i =
j Permeance j
3. Results and discussions
3.1. SAPO-34 crystal characterization
The XRD pattern of the SAPO-34 particles synthesized in this work is
shown in Fig. 1. The intensity of each peak at 9.7, 15.6 and 20.6
approximately, was in accordance with the literature [10,18]. This
Intensity (a.u.)
4 4 4 4
10 15 20 25
2
Fig. 1. X-ray diffraction pattern of SAPO-34 zeolite particle.
127
sample showed a high crystallinity degree of the CHA structure of the
SAPO-34 zeolite. Table 2 summarizes the particle characteristics of the
calcined SAPO-34. The SAPO-34 which was synthesized under hydro-
thermal heating at 200 C for 24 h exhibited BET surface area of
466 m2/g, showing a slightly lower surface area compared to those
reported by Chew et al. [18]. As shown in Fig. 4(a), the larger and ag-
glomerated particles tend to show lower surface area. Characterization
results in Table 2 indicated that the SAPO-34 zeolite sample in this
work has greater intensity of molecular sieve nano-pore formed within
the zeolite particle. As the SAPO-34 zeolite showed a higher micropore
surface volume than the literature value [18], the porosity of the
SAPO-34 crystals showed a tendency to increase as well [19]. According
to Carreon et al. [7], SAPO-34 crystal with a particle size smaller than
1 m and a narrow particle size distribution could produce pure zeolite
membranes with a superior separation performance, especially in CO2
separation. On the other hand, Rojey et al. [20] suggested that an aver-
age particle size of dispersed phase in the range of 2090 nm might
contribute into homogenous MMMs, resulting in excellent separation
performance. However, SAPO-34 in this work exhibited an average
size of 0.661 m (661 nm) as stated in Table 2. Hence, the large SAPO-
34 particles could disturb MMM separation performance as discussed
later. In addition, small nano-sized zeolite particles could affect the par-
ticle distribution in the polymer matrix leading to particle agglom-
eration. Hence, an increased period for particle dispersion using
ultrasonic equipment was recommended in the preparation of MMM
solution with elevated particle loading to ensure good dispersion of
the blended particles.
3.2. Membrane characterization
TGA curves for all of the fabricated membranes (PSf-00 to PSf-30)
were recorded from 29 C to 900 C as shown in Fig. 2. At 50 C to
100 C, PSf-20 membrane showed a 6% weight reduction while PSf-30
lost about 10% of the total weight. The material loss in this phase was
due to moisture release from the sample. It was veried that PSf-20
and PSf-30 samples have high moisture adsorption due to the increasing
load of the hydrophilic SAPO-34 framework [21]. Thermal stability can
be dened as the stability of a material at high temperature before it
starts to decompose. Higher thermal stability can be achieved when
a membrane maintains its stability at a higher temperature after
modication.
Between 500 C to 600 C, a rapid material loss was observed as PSf
material in all of the membranes decomposed. It was also observed that
the addition of 5 wt.% of SAPO-34 contributed to a decrement in ther-
mal stability as concurred by the lower degradation temperature com-
pared to the PSf-00 sample. Moreover, the degradation temperature
for samples with higher SAPO-34 loading (PSf-10, PSf-20 and PSf-30
samples) reduced continuously. The PSf-30 sample exhibited the lowest
thermal stability, corresponding to the lowest decomposition tempera-
ture. The TGA results of the MMM samples have a similar decrement
pattern with the work reported by Chen et al. [22]. The reduction in
thermal stability of the MMM samples in this work exposed the poor in-
terfacial interaction between the PSf polymer and SAPO-34 particles.
Above 600 C, the decomposition rate during temperature elevation
became constant for all of the membrane samples. PSf-00 showed the
highest material loss (above 70% weight reduction) as the analysis tem-
perature reached 900 C, while all of the other prepared MMM samples
Table 2
Comparison of SAPO-34 particles characteristic with literature.
4 4 Average particle size BET surface area t-Plot micropore volume Reference
30 35 (m) (m2/g) (cm3/g)
b1.0 535.00 0.24 [18]
0.661 466.25 0.32 This work
128 M.U.M. Junaidi et al. / Fuel Processing Technology 118 (2014) 125132

102 a
Weight Percentage (%)

100 (b)
(c)
98
(a)
96

94 (d)

92 (e)

30 40 50 60 70 80 90 100
Temperature (C)
120

100
Weight Percentage (%)

80 b
60
(d)
(e)
40 (c)
(b)
20 (a)

0
100 200 300 400 500 600 700 800 900
Temperature (C)

Fig. 2. TGA curves of (a) PSf-00, (b) PSf-05, (c) PSf-10, (d) PSf-20, and (e) PSf-30
membranes.

had a higher residue weight, depending on the amount of the SAPO-34

content in each of the MMMs.
Fig. 3 shows the typical FT-IR spectra of a pure PSf membrane, SAPO-
34 particles and all MMM samples fabricated in this work. Neat PSf-00
membrane exhibited bands at ~1290 cm1 and ~1325 cm1, signify-
c
PSf-00
ing the symmetric stretch vibration of O=S=O bonding. The bands oc-
curring at 2960 cm1 and 1380 cm1 signify the presence of PSf-05
asymmetric CH3, while the strong shoulder peak at ~1583 cm1 is
Arbitrary Transmittance (a.u.)

characteristic of C=C conjugation of the aromatic ring [23]. Meanwhile,

SAPO-34 particles showed great vibration in the range 8501200 cm1.
According to Lee et al. [24], this strong adsorption band represents the
PSf-10
internal tetrahedral asymmetric of SiO and AlO groups inside the ze-
olite crystal. As shown in Fig. 3(b), all the fabricated membranes dem-
onstrated analogous FT-IR patterns to the neat PSf-00 sample. PSf-20
However, MMM samples showing higher absorption band rose in the
range of 8001200 cm1, corresponding to the asymmetric vibration
of the SiO and AlO tetrahedral in the SAPO-34 structure, which is PSf-30
not observable in the neat PSf sample. Stronger vibrations of SiO and
AlO tetrahedral were observed with the increased of SAPO-34 loadings
in the membrane samples. Nevertheless, the interactions between zeo- 1200 1100 1000 900 800 700
lite ller and PSf phase in all MMM samples were poor, considering Wavenumbers (cm-1)
there were no detectable peaks for OH bond in the FT-IR spectra. As re-
ported by Dorosti et al. [25], the formation of OH bonding (vibration Fig. 3. FT-IR patterns of (a) PSf-00 with SAPO-34 particles, (b) produced membranes and
band at 3640 cm1 in FT-IR spectra) between the polymer phase and (c) produced membranes between 1200 to 600 cm1.

ller phase could indicate the existence of good adhesion between the
PSf and zeolite ller. Thus, poor adhesion of SAPO-34 zeolite in the PSf
matrix in this work can be concluded.
Surface and cross-sectional morphologies of the neat PSf membrane
and the MMMs were studied using SEM. The thickness of each mem-
brane sample is tabulated in Table 1. From the microscopic view in
Fig. 4(b), no void or defect was detected on the dense surface of the
pure PSf-00 membrane. Sponge-like membrane layer supporting an
ultrathin dense layer (thickness of about 2 m from SEM image) could
be observed from the cross-sectional view (Fig. 5(a)). Similar asymmet-
ric properties of the pure PSf membrane were also reported in the
literature [3,13]. The addition of THF into the polymer solution and
the evaporation step during membrane preparation facilitated a de-
layed liquidliquid demixing process to form a porous membrane
 M.U.M. Junaidi et al. / Fuel Processing Technology 118 (2014) 125132 129

a b

c d

Fig. 4. Surface view with SEM micrographs for (a) SAPO-34 crystals, (b) PSf-00, (c) PSf-10 and (d) PSf-30 membranes.

substructure supporting a thin dense top layer. THF reduced the interac-
tion between solvent and non-solvent as well, promoting the formation
of sponge-like sub-layer instead of nger-like macrovoid. The same
cross-sectional morphology (sponge-like structure and thin dense
layer) was noticed for all the fabricated MMMs in this work. On the
other hand, the addition of 10 wt.% of SAPO-34 zeolite into PSf-10 mem-
brane resulted in a homogenous dispersion of SAPO-34 on the surface
and within macropores with effective dense layer thickness about
1.8 m (Figs. 4(c) and 5(b)). However, agglomerated particles were vis-
ible from the cross-sectional view of PSf-20 and PSf-30 membranes
(Fig. 5 (c) and (d)). A few SAPO-34 aggregates with a more than 2 m
diameter can be distinguished across both membranes. The llers
were easily attracted to each other and formed larger aggregates at a
higher zeolite loading due to the lack of strong adhesion between the
SAPO-34 llers and the PSf matrix, as proven by the FT-IR analyses.
These large SAPO-34 aggregates caused large void formation on the sur-
face of the thin PSf dense layer, which induced a serious reduction in gas
selectivity performance as discussed later.
EDX scanning on the PSf-10 cross-sectional images shown in
Fig. 5(e) detected a high intensity of carbon (C) and sulphur (S) ele-
ments, representing the PSf polymer matrix. The presence of the
SAPO-34 particles was identied by low concentrations of aluminium
(Al) and phosphorus (P) elements. Fig. 5(f) showed the EDX scanning
on the PSf-30 membrane with the intensities of the Al and P elements
that were higher than the PSf-10 membrane. The scanning result
conrmed that the PSf-30 sample contained a high concentration of
SAPO-34 zeolite. Additionally, the intensity of oxygen (O) element
was also higher in the PSf-30 compared to the PSf-10, which could be
contributed by the presence of the O element in the SAPO-34 particle
structure (Al2O3 and PO4).
3.3. Gas performance analysis
In this study, single gas permeation measurements for N2, CH4 and
CO2 gasses were performed for all fabricated membranes. At least 2
samples from 2 different casting solutions for each of the membrane for-
mulation were used. The volumetric ow rate of each gas through the
membrane sample was measured in triplicate and the average value
was used for the permeation calculation. For all of the gas component
permeance results reported in this work, the percentage difference be-
tween the measured data was well below 1.5% and in the range of
4.55.6% for membranes from different casting solutions. The mem-
brane preparation and testing methods were conrmed to be reproduc-
ible in this work. Generally, the gas permeation tests for CO2 were
conducted at a pressure above 8 bar. Nevertheless, the pressure differ-
ence across the membrane in this work was maintained at 3.48 bar.
According to Ahn et al. [16], the solubility coefcient of CO2 was higher
at a lower operating pressure. The solubility coefcient is an important
character in gas transport mechanism through a polymeric dense layer
because a greater solubility of gas encourages a higher permeation rate.
130 M.U.M. Junaidi et al. / Fuel Processing Technology 118 (2014) 125132

a (b

1 m
1.8

c (d

1.5
m 00.9 m

e f

keV keV
V

Fig. 5. SEM micrographs for cross-section of (a) PSf-00, (b) PSf-05, (c) PSf-10 and (d) PSf-30 membranes and respective EDX results for (e) PSf-10 and (f) PSf-30 showing the concentration
of Al and P elements represent zeolite particles across a cross sectional line of the membrane.

Table 3
Thus, a low pressure is usually applied in pure gas permeation tests Gas permeance and ideal selectivities of MMMs at different SAPO-34 loadings at ambient
[16,19,26]. The pure gas permeation test was conducted according to temperature and 3.48 bar. Errors are 1 standard deviation from 3 samples.
the gas solubility, except for CO2 gas which must be the last gas to be
SAPO-34 Permeance (GPU)a Ideal selectivity
measured due to its encouragement of membrane plasticization [27].
loading
Separation performances of the fabricated membranes were summa- CO2 N2 CH4 (CO2/N2) (CO2/CH4)
(%, w/w)
rized and tabulated in Table 3.
0 22.01 3.42 1.33 0.59 1.26 0.44 16.5 17.3
For the pure PSf membrane, gas component permeation obtained is 5 205.92 7.26 9.63 0.56 9.12 0.65 21.4 22.5
higher than the values reported in the literature [13]. The difference 10 314.02 4.65 12.03 1.83 11.16 0.92 26.1 28.2
may be due to the shorter evaporation time in this work, leading to thin- 20 281.18 6.92 26.28 1.49 25.73 2.06 10.7 10.9
ner dense top layer formation. Accordingly, the prepared MMMs 30 232.35 3.21 78.10 3.42 77.36 5.28 2.9 3.0

showed gas permeance in the order of CO2 N CH4 N N2, similar to PSf- a
1 GPU = 106 cm3 (STP)/cm2 cm Hg s.
 M.U.M. Junaidi et al. / Fuel Processing Technology 118 (2014) 125132
00 membrane. The permeation ux of CO2, CH4 and N2 gasses via
MMMs was greatly amplied when an appropriate amount of the
SAPO-34 ller was added. The CO2 permeance of the PSf-05 membrane
increased drastically to 205.92 GPU with CO2/N2 and CO2/CH4 selectiv-
ities enhancement by 29.6% and 30.1% respectively, compared to the
PSf-00. The maximum increment of CO2 permeance was detected for
the PSf-10 (314.02 GPU), resulting in the highest CO2/N2 and CO2/CH4
selectivities up to 26.1 and 28.2 respectively.
On the other hand, the CO2/N2 selectivity decreased to 10.7 (35%
decrement) as the N2 permeance via the PSf-20 membrane raised to
26.28 GPU. A similar trend was observed in the permeation test of
CH4 gas through the PSf-20 membrane. The CH4 permeance was in-
creased to 25.73 GPU while the CO2/CH4 selectivity decreased by 37%.
As shown in the SEM images, the SAPO-34 aggregates formed in the
PSf-20 polymer matrix and disturbed the dense layer surface structure
by generating large interfacial voids [11]. The membrane resistance for
larger molecule gasses such as N2 and CH4 was greatly reduced. These
gas molecules could easily penetrate into the membrane via the large
interfacial voids generated due to the high amount of SAPO-34 incorpo-
ration. As shown in Table 3, the CO2 permeance through PSf-20 reduced
greatly compared to the PSf-10 samples. Besides the PSf dense layer, the
CO2 permeance through prepared membranes was greatly affected by
the good condition of SAPO-34 inside the membranes in terms of parti-
cle dispersion and its loading amount, and also interfacial void forma-
tion. The reduction of CO2 permeance could be related to the SAPO-34
agglomeration, which tends to reduce CO2 afnity effect on the sample.
A similar observation obtained from PSf-30 samples, the N2 and CH4
permeances increased drastically to 78.10 and 77.36 GPU with degrada-
tion in CO2 permeance. The CO2/N2 and CO2/CH4 selectivities also re-
duced to 82.4% and 82.6% respectively.
A comparison of the separation performance of the asymmetric
membranes fabricated in this work and the SAPO-34 MMMs reported
in the literature [9,10] could be easily conducted using the performance
graph plot for CO2/N2 gas pair as shown in Fig. 6. The PSf-10 membrane
achieved the highest MMM performance in terms of CO2 permeance.
Although both reported works have acquired higher CO2/N2 selectivity,
their CO2 permeances were much lower than the PSf-10 membrane.
Meanwhile, CO2/CH4 performance of the prepared membranes and
other reported MMMs incorporated with SAPO-34 [10,11] on the per-
formance graph plot was shown in Fig. 7. For this gas pair, PSf-10 mem-
brane from this work attained better performance than the other
104
PSf-00
PSf-05
PSf-10
PSf-20
103 PSf-30
Poly(RTIL)/SAPO-34
(80:20) [9]
CO2/N2
PPZ/ SAPO-34 [10]
100
10
1
1 10 100 103 104
PCO2 (GPU)
Fig. 6. Comparison of recent literatures [9,10] with all types of membranes prepared for
CO2/N2 gas pair.
131
104
PSf-00
PSf-05
PSf-10
103 PSf-20
PSf-30
PES/HMA/SAPO-34 [11]
CO2/CH4
PPZ/ SAPO-34 [10]
100
10
1
1 10 100 103 104
PCO2 (GPU)
Fig. 7. Comparison of recent literatures [10,11] with all types of membranes prepared for
CO2/CH4 gas pair.
reported works [10,11]. Compared to the dense matrix reported in the
literature [911], porous network of the asymmetric PSf membrane pre-
pared in this work could permit CO2 to easily reach microporous SAPO-
34 with great CO2 adsorption afnity. Thus, great improvements in both
CO2 selectivity and permeability were observed. The PSf-10 membrane
has great potential to be applied in Malaysia with natural gas production
rate of 6756 million standard cubic feet per day (MMSCFD) [28]. In
order to acquire this huge amount of high purity natural gas, about
1689 MMSCFD of CO2 needs to be removed by natural gas sweetening.
Based on a preliminary ideal estimation, the PSf-10 membrane (with ef-
fective membrane area 12.6 cm2) is expected to ideally permeate about
129 m3/h of CO2 gas equivalent to 0.11 MMSCFD. However, many
parameters such as other natural gas contents (ethane, propane, and
butane), undesirable impurity contents (CO2, N2, water, and hydrogen
sulde), membrane endurance towards harsh operating condition, plas-
ticization effect at high pressure situation, membrane fouling rate, gas
mixture separation performance etc. should be taken into consideration
before the membranes can be used in the gas industry.
4. Conclusions
The effects of SAPO-34 zeolite loading on the membrane characteris-
tic and gas transport properties for asymmetric PSf/SAPO-34 MMMs
had been successfully studied. All of the membrane samples were pre-
pared using phase inversion method. The surface and cross-section
SEM images of the MMMs provided evidence for good dispersion of
the particles in the polymer for zeolite loading less than 10 wt.%. The
PSf/SAPO-34 membrane with 10 wt.% SAPO-34 loading (PSf-10)
showed the highest separation performance enhancement on CO2/N2
and CO2/CH4 ideal gas pair properties compared to the pure PSf mem-
brane (PSf-00). For the higher zeolite loadings (20 wt.% and above),
the gas permeation properties of the MMMs were severely disturbed
by the massive formation of large interfacial voids across the membrane
surface due to the particle agglomeration. Moreover, TGA and FT-IR
results veried the poor interaction between PSf and the SAPO-34 par-
ticles which also resulted in great interfacial voids. In order to avoid the
formation of interfacial voids, better connection between ller and poly-
mer material is important, which can be done by polymer/ller modi-
cation. In conclusion, an optimum amount of SAPO-34 zeolite loading
(10 wt.% and below) for fabrication of the asymmetric PSf/SAPO-34
132 M.U.M. Junaidi et al. / Fuel Processing Technology 118 (2014) 125132
MMMs is essential to achieve a good dispersion of ller inside the poly-
mer phase and excellent CO2 removal performance that can be applied
specically in natural gas sweetening.
Acknowledgments
The authors would like to acknowledge MOSTI for providing Science
Fund (06-01-05-SF0579), Universiti Sains Malaysia for the nancial
support provided through Membrane Science and Technology Cluster
(1001/PSF/8610013), RUI Grant (1001/PJKMIA/811194), PRGS Grant,
and USM Fellowship. The authors would also like to thank Ms. Low Ee
Mee and Mrs. Norfarahiyah for their knowledge sharing and support.
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