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Department of Chemical and Biomolecular Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260, Singapore
b UOP LLC, 50 East Algonquin Road, Des Plaines, IL 60017-5016, USA
Received 1 July 2005; received in revised form 28 August 2005; accepted 31 August 2005
Available online 30 September 2005
Abstract
A novel silane coupling agent, (3-aminopropyl)-diethoxymethyl silane (APDEMS) was used in this work to modify zeolite surface for mixed
matrix membranes (MMMs). Both elementary analysis and XPS spectra confirm the chemical modification, while BET measurements show no
changes in zeolite surface area and total pore volume after the modification. Polyethersulfone (PES)zeolite 3A, 4A and 5A MMMs were fabricated
at high processing temperatures using unmodified and chemical modified zeolite. SEM images of these MMMs indicate the interface between
polymer and zeolite phases becomes better if modified zeolite is used. The effects of chemical modification of zeolite surface and zeolite loadings
on the gas separation performance of these MMMs were investigated. Both permeability and selectivity of MMMs made from APDEMS modified
zeolite are higher than those of MMMs made from unmodified zeolite at 20 wt% zeolite loading because of a decrease in the degree of partial pore
blockage of zeolites. The permeability of all studied gases decreases with increasing zeolite content for PESzeolite 4A-NH2 MMMs, while for
PESzeolite 5A-NH2 MMMs, the gas permeability decreases and then increases with an increase in zeolite loadings. This unique phenomenon
implies that using large pore-size zeolite for MMMs would potentially offset the negative effects of partial pore blockage and polymer chain
rigidification on permeability. A modified Maxwell model with adjusted parameters was applied to study the PESzeolite 4A-NH2 MMM system.
The predicted permeability and selectivity show very good agreement with experimental data, indicating the modified Maxwell model is fully
capable of predicting the gas separation performance of MMMs made from both unmodified and modified zeolite.
2005 Elsevier B.V. All rights reserved.
Keywords: Mixed matrix membrane; Silane modification of zeolite surface; Polymer chain rigidification; Partial pore blockage; Maxwell model
1. Introduction
During the last 2 decades, polymer-based organicinorganic
composites have received world-wide attention in the field of
material science. This is due to the fact that the resultant materials may offer superior performance in terms of mechanical
toughness for engineering resins, permeability and selectivity
for gas/liquid separation, and photoconductivity for electronics
[13]. This new concept has also been applied to the membranebased gas/liquid separation by combining the easy processability
of organic polymers with the excellent separation properties
of inorganic materials [2,410]. However, it has been found
Corresponding author. Tel.: +65 6874 6645; fax: +65 6779 1936.
E-mail address: chencts@nus.edu.sg (T.-S. Chung).
0376-7388/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2005.08.015
that there is an obstacle to the successful introduction of inorganic molecular sieve materials into an organic polymer matrix
because of the poor compatibility between molecular sieve and
polymer matrix, especially for the case of rigid glassy polymer
materials [913].
Therefore, some methods have been proposed to improve
the interfacial strength in order to enhance the separation
performance [1318]. One of them is the chemical modification of the surface of molecular sieve with silane coupling agents, such as (-aminopropyl)-triethoxy silane, N-(aminoethyl)--aminopropyltrimethoxy silane, (-glycidyloxypropyl)-trimethoxy silane and (3-aminopropyl)-dimethylethoxy
silane [1417]. By means of FTIR and 29 Si MAS NMR, Matsumoto et al. have identified that there are three types of silanol
groups on the surface of zeolite [19], i.e., single ((SiO)3 SiOH);
hydrogen-bonded ((SiO)3 SiOH OHSi(SiO)3 ) and geminal
18
19
method with a pre-calibrated permeation cell described elsewhere [30]. Each pure gas was tested in the sequence of He, H2 ,
O2 , N2 , CH4 and CO2 , and measured three times for each membrane. The measurement of H2 gas for MMMs was performed
at 35 C and 3.546375 105 Pa (3.5 atm); the measurement
of other gases was conducted at 35 C and 10.1325 105 Pa
(10 atm).
Table 1
Comparison of elementary analysis data of zeolites before and after the chemical
modification
Sample name
N (%)
C (%)
H (%)
Zeolite 3 A
Zeolite 3A-NH2 a
0.0
2.47
0.16
7.42
2.16
2.44
Zeolite 4A
Zeolite 4A-NH2 a
0.0
2.42
0.16
7.30
2.12
2.30
Zeolite 5A
Zeolite 5A-NH2 a
0.0
2.43
0.15
7.28
2.10
2.28
20
Fig. 2. Comparison of XPS spectra of the zeolite before and after the chemical modification (A: zeolite 3A; B: zeolite 3A-NH2 ; C: zeolite 4A; D: zeolite 4A-NH2 ).
Table 2
Comparison of total pore volume and multipoint BET surface area of zeolites before and after the chemical modification
Sample name
Zeolite 3 A
Zeolite 4A
Zeolite 5A
Before modifying
After modifying
Before modifying
After modifying
0.197
0.200
0.198
0.196
0.198
0.196
557.6
567.0
561.1
553.5
561.6
556.7
After modifying
215 1
216
217
218
219
1
1
1
1
216
217
218
219
1
1
1
1
218
219
220
221
1
1
l
1
217
218
220
221
1
1
l
1
21
Fig. 3. Comparison of gas permeability of PESzeolite A MMMs before and after the chemical modification of zeolite surface (A: He permeability; B: H2 permeability;
C: O2 permeability; D: CO2 permeability).
Fig. 4. Comparison of gas pair selectivity of PESzeolite A MMMs before and after the chemical modification of zeolite surface (A: He/N2 selectivity; B: H2 /N2
selectivity; C: O2 /N2 selectivity; D: CO2 /CH4 selectivity).
22
Fig. 5. Comparison of cross-section SEM images of MMMs before and after the chemical modification of zeolite surface (AC: PESzeolite 3A, 4A and 5A MMMs,
respectively; DF: PESzeolite 3A-NH2 , 4A-NH2 and 5A-NH2 MMMs, respectively).
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Fig. 6. Effect of zeolite loadings on gas permeability of PESzeolite 4A-NH2 and PESzeolite 5A-NH2 MMMs (A: He and H2 permeability; B: CO2 permeability;
C: O2 permeability; D: N2 and CH4 permeability).
24
Fig. 7. Effect of zeolite loadings on gas pair selectivity of PESzeolite 4A-NH2 and PESzeolite 5A-NH2 MMMs (A: He/N2 selectivity; B: H2 /N2 selectivity; C:
O2 /N2 selectivity; D: CO2 /CH4 selectivity).
25
Thirdly, the permeability of the second phase can be determined with the aid of Maxwell equation a second time by
regarding the rigidified polymer region as the continuous phase
and the third phase as the dispersed phase
P3rd + 2Prig 2v2 (Prig P3rd )
P2nd = Prig
(3)
P3rd + 2Prig + v2 (Prig P3rd )
where P2nd is the composite permeability of the second phase,
Prig the permeability of the rigidified polymer region and v2 is
the volume fraction of the third phase in the second phase and
can be estimated by the following equation:
v2 =
vD + vblo
vD + vblo + vrig
(4)
26
Table 4
Change of O2 and N2 permeability in different regions of the PESzeolite 4A-NH2 MMM
Permeability in the
PES matrix (Pc )a
O2
0.479
0.160
0.00308
0.770
N2
0.0825
0.0206
0.00208
0.0208
a
b
c
d
Gas permeability data in the PES matrix come from experiment results of neat PES dense film.
is 3 for O2 gas, while is 4 for N2 gas.
is 250 for O2 gas, while is 10 for N2 gas.
Gas permeability data in the bulk of zeolite 4A come from reference [36].
Table 5
Calculated volume fraction data of dispersed phase in different phases of PESzeolite 4A-NH2 MMMs in the modified Maxwell model which simultaneously
considers both polymer chain rigidification and partial pore blockage of zeolites
Calculated volume fraction of the bulk of zeolite 4A (considered as the
dispersed phase) in the third phase (v3 ) (defined in Fig. 8)
Calculated volume fraction of the third phase (considered as the dispersed
phase) in the second phase (v2 ) (defined in Fig. 8)
Calculated volume fraction of the second phase (considered as the
dispersed phase) in the whole mixed matrix membrane (defined in Fig. 8)
0.972
0.641
20 wt% Zeolite loading (18.6 vol% zeolite loading)
30 wt% Zeolite loading (28.1 vol% zeolite loading)
40 wt% Zeolite loading (37.8 vol% zeolite loading)
50 wt% Zeolite loading (47.7 vol% zeolite loading)
0.290
0.439
0.590
0.745
Figs. 9 and 10 illustrate the ultimate prediction of O2 permeability and O2 /N2 selectivity of PESzeolite 4A-NH2 MMMs,
respectively. It can be found that the prediction from the modified Maxwell model is in very good agreement with experimental
data. Therefore, this demonstrates our revised Maxwell model
can be utilized for MMMs made from both unmodified and modified zeolite.
4. Conclusions
The following conclusions can be drawn from this work:
(1) Results from elementary analysis and XPS demonstrate that
the silane coupling agent (APDEMS) has been successfully
grafted onto the external surface of zeolite after the chemical
modification. BET results show that the surface area and
total pore volume of zeolites before and after modification
are almost the same, indicating the micropore of zeolites is
almost not influenced by the addition of APDEMS. These
characterizations assure the zeolite modified by APDEMS
as a good candidate which can be applied in the fabrication
of MMMs.
(2) Both gas permeability and gas pair selectivity of
PESzeolite A-NH2 MMMs are higher than those of
PESzeolite A MMMs at 20 wt% zeolite loading. This may
be mainly due to the fact that the presence of APDEMS
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