Professional Documents
Culture Documents
Review
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Seberang Prai Selatan, Pulau Pinang, Malaysia
Center for Petroleum & Minerals, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
a r t i c l e
i n f o
Article history:
Received 28 August 2012
Received in revised form 9 April 2013
Accepted 20 April 2013
Available online 21 May 2013
Keywords:
Membrane gas separation
CO2 removal
Penetrant-induced plasticization
Conditioning
Physical aging
Natural gas
Polymeric membrane
a b s t r a c t
In recent year, the need for more energy efcient and environmental friendly gas purication techniques
has lead to massive research efforts into membrane based gas separation technology. Today, this technology is widely used in removal of CO2 from raw natural gas components. Penetrant-induced plasticization,
physical aging, conditioning and poor balance between permeability and selectivity are some of the major
challenges facing the expansion of membrane market in industrial application. A comprehensive review
of research efforts in alleviating these problems is required to capture details of the progresses that have
already been achieved in developing membrane materials with better CO2 separation performance.
This paper presents details of recent research progresses that have been recorded in the context
of breakthrough and challenges in development of membrane materials. Descriptions of membrane
preparation methods that have been investigated to develop membranes with better gas separation
performance are discussed.
2013 Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1.
Natural gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2.
Polymeric membrane gas separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.
Fundamental of gas separation in polymer membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Achieving better balance of gas selectivity and permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Plasticization, conditioning and physical aging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Techniques for improving separation performance of polymeric membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Cross-linking and thermal treatment techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Grafting of polymer backbone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Template polymerization and use of porogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4.
Spinning processes and dual-layer hollow ber spinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5.
Thermal rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6.
Phase inversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.7.
Sulfonation of polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.8.
Copolymerization and blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.9.
Polymers of intrinsic microporosity (PIM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion and recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
47
47
47
49
50
50
53
53
57
57
58
59
60
60
60
60
61
61
61
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
Table 1
Typical natural gas compositions (Dung et al., 2008 and Kidnay and Parrish, 2006).
Component
Helium
Nitrogen
Carbon dioxide
Hydrogen sulde
Methane
Ethane
Propane
Butanes
Pentanes and heavier
1. Introduction
The world population was more than 6.8 billion in 2010 and it
is expected to increase to about 9.2 billion in 2050 (Armaroli and
Balzani, 2011). Logically, this expansion is expected to be accompanied by equivalent increase in overall energy consumption from
15 TW to more than 40 TW. Consequently, the world will be facing even more challenges of greenhouse gas emission and climate
change associated problems than it is presently facing. The fourth
assessment report of the United Nations Intergovernmental Panel
on Climate Change and other similar studies have revealed that
increased CO2 concentration in the atmosphere will lead to increase
in the greenhouse effect which in turn causes climate change (IPCC,
2007; Speight, 2007). CO2 gas accounts for about 60% of the effect
of greenhouse gases on global climate change (Shao et al., 2013).
Two of the most common components of national and international
policies for greenhouse gas mitigation are: use of cleaner energy,
and energy efcient products and services (Leggett et al., 2009).
1.1. Natural gas
Natural gas (NG) is the world cleanest, safest, and most efcient energy sources (Schoots et al., 2011; Speight, 2007; Xiao
et al., 2009). It has a CO2 emission factor of approximately 26% and
41% lower than that of oil and coal, respectively when combusted
(Armaroli and Balzani, 2011). It is found in oil elds, NG elds, condensate wells and coal beds (Speight, 2007). NG from crude oil wells
is termed associated gas while those from gas wells or condensate wells are called non-associated gas (Yergin, 2011). Raw NG
from methane deposits in the pores of coal seams is called coalbed
gas or coalbed methane (Mokhatab et al., 2006). NG consists primarily of methane (CH4 ) (Adewole et al., 2012a,b). It also contains
varying amount of heavier gaseous hydrocarbons, acid gases, water
vapour, mercury, radioactive gases and other gases such nitrogen
and helium (Yergin, 2011). Table 1 contains detailed composition
of a typical raw NG. Actually, NG composition varies from place
to place (Baker and Lokhandwala, 2008). The composition in this
table is the range obtained for Canada (Alberta), New Mexico (Rio
Arriba County), Nigeria (Eleme), Southwest Kansas, Texas (Cliffside
Field, Amarilla), Tunisia (Miskar), Vietnam (Bach Ho), and Western
Colorado. Indeed, NG is reported to be the fastest growing primary
source of energy in the present global economy (Kidnay et al., 2011;
Mokhatab et al., 2006; Nord et al., 2009; Speight, 2007). In 2004,
NG constitutes about 23.5% of the world primary sources of energy.
This is next to crude oil which constitutes 35.3%. The world market
for NG is estimated as US$22billion per annum (Ren et al., 2002).
With NG becoming more and more important, there is an increasing demand for information on the progress of NG processing and
purication using novel and energy efcient separation technique
such as membrane, however, less material is available on this subject.
Clearly, raw NG needs further purication to meet quality
standard specied by major pipeline transmission and distribution
47
Table 2
Natural gas specications for commercial applications (Kidnay and Parrish, 2006).
Major components
Minimum mol%
Maximum mol%
Methane
Ethane
Propane
Butanes
Pentanes and heavier hydrocarbons
Nitrogen and other inerts
Carbon dioxide
Total diluents gases
75
None
None
None
None
None
None
None
None
10
5
2
0.5
3
23
45
Table 3
Separation performance of CO2 /CH4 with rubbery and glassy polymers (Murphy
et al., 2009).
Membrane
Permselectivity
Diffusion
selectivity
Solubility
selectivity
Temperature
PDMSa
Polyisoprene
Polysulfone
3.1
4.5
22
2.9
3.6
3.7
1.1
1.2
5.9
35
25
35
48
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
Historically, application of membrane separation for gas mixtures has been limited due to low uxes and selectivities (Scott
and Hughes, 1996). Low ux membranes require large membrane area and high capital cost while low selectivity means high
operating cost which results from the energy intensive multistage processing required to compensate for low selectivity (Scott
and Hughes, 1996). Thus, the most important route for expanding the use of membrane technology in gas separation is the
development of materials with better balance of selectivity and
productivity (permeability), improved and stable long-term gas
separation performance by overcoming the problems of physical
aging, CO2 -induced plasticization, and conditioning (Askari et al.,
2012a; Chung and Teoh, 1999; Dorkenoo and Pfromm, 2000; Lin
and Chung, 2000; Liu et al., 2001; McCaig and Paul, 2000; Murphy
et al., 2009; Pfromm et al., 1993; Scholes et al., 2010a). Report
from literature showed that glassy polymers are the most widely
used in MGS processes due to their selectivity, excellent thin
lm forming, good mechanical properties, and higher permeability to low molecular weight species. In NG sweetening, most of
separation performances of glassy polymer outweighed that of rubbery polymers (Scholes et al., 2010a). The separation factors of two
rubbery polymers (silicone rubber, poly (dimethyl siloxane) and
natural rubber, polyisoprene) and a glassy polymer (polysulfone)
for CO2 /CH4 are shown in Table 3. Notwithstanding, there are also
some research efforts in search of rubbery membrane materials that
have exceptional selectivity for CO2 relative to other gases (Murphy
et al., 2009).
During our literature review, we found excellent research
works where membrane materials (both glassy and rubbery) with
extremely high CO2 permeability and CO2 /CH4 permselectivity
were synthesized (Table 4). Moreover, success stories of industrial membrane gas separation have been reported in literature.
For example, the rst industrial plants for CO2 removal using polymeric membrane (cellulose acetate) were installed in 1980s (Park
et al., 2010). Also, the SACROC gas plant represents a very large
breakthrough in the history of membrane in gas separation (Koros
et al., 2009). A membrane gas facility in KellySnyder oil eld is an
interesting example of membrane versatility in gas processing. An
eventual increase in the CO2 contents of the associated gas in the oil
eld necessitated an expansion of the CO2 handling facility of the
eld. In 2006, cellulose acetate hollow ber membrane units were
considered to be ideal for expanding the facilities from processing
70MMscfd to 600MMscfd with gas feed of 87 mol% CO2 . Table 5 contains other membrane gas separation plants that have come into
operations in recent years. However, achieving good gas selectivity without sacricing gas permeability, maintaining the long-term
gas separation performance by overcoming the problems of CO2 induced plasticization, physical aging, and conditioning remained
Table 4
Membrane with high permeability and selectivity.
Membrane
PPM--CD-425
PPM--CD-425
PPM--CD-425
Dense lm TR-PBO
TR-PBO Hollow bera
TR-PBI
Addition-type
poly(trimethylsilylnorbornene (PTMSN)
with Si(CH3 ) side groups
Spirobisindane polymers
Poly(dimethyl siloxane) (PDMS)
Silicone (polydimethyl siloxane, or PDMS)
a
Permeance is in GPU.
Permeation experiment
Mixed gas
Mixed gas
Mixed gas
Single gas
Single gas
Single
Pure gas
% CO2
50
50
50
Permeability (Barrer)
CO2
CH4
3976
2911
2392
3575
1938
1624
4480
174
133
117
80.8
137.1
35
990
3496
2850
3250
360
823
950
Reference
22.85
21.85
20.44
44
14
46.1
4.5
9.7
3.5
3.4
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
49
Table 5
Industrial membrane gas separation plants (Koros et al., 2009; Engelien, 2004).
Plant
Initial capacity
CO2 (mol%)
Year commissioned
Kelly-Snyder Field
Cakerawala Production Platform
Qadirpur, Pakistan
Taiwan
Kadanwari, Pakistan
EOR facility, Mexico
Slalm & Tarek, Egypt
Texas, USA
70
265 at 59 bar
30 at 42 bar
210 at 90 bar
120
100 at 65 bar
30 at 42 bar
600
700
500
87
37
6.5
2006
1999
1999
70
30
Table 6
Mixed and multicompnent gas mixture permeability and selectivity of cross-linked copolyimides membrane (Wind et al., 2004).
Polymer membrane
Permeation test
Method
Temperature ( C)
Perm CO2
(Barrer)
Annealing
130
220
295
135
115
95
28
33
30
2025
>22.5
35
Cross-linked with
butylenes glycol monoester
220
40
26
>55
295
150
30
>30
CO2 /CH4
separation factor
Cross-linked with
benzenedimethanol
monoester
295
43
37
33
220
24
47
27
Multi-component
mixtures
Annealing
220
47
2328
>40
5055
2327
>10
(1)
PA
PB
(2a)
(yA /yB )
(xA /xB )
(2b)
50
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
where A is the permeated component and B is the rejected component. The values x and y are the mole fractions of the components
in the feed and the permeate, respectively. It is therefore essential
while reporting the selectivity to indicate the nature of the permeation experiment. From Eq. (1), it can be inferred that the selectivity
can also be expressed as:
AB =
DA
SA
DB
SB
(3)
PA
L
PA (denselm
(P/L)A (dual-layer
(5)
AB =
(P/L)A
(P/L)B
(6)
E
D
RT
(7a)
H
S
RT
(7b)
E
P
RT
(7c)
and
EP = ED + HS
S = kD +
CH b
1 + bp
(8a)
CH bDH
1 + bp2
(8b)
(4)
For dual-layer hollow ber, L is the dense-selective layer thickness and can be determined as follows (Li and Chung, 2010):
L=
(7d)
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
51
Fig. 1. Permeability and permselectivity for pure gases at feed pressure of 3.5 bar; membrane thickness of 20 m.
Bernardo et al. (2009).
Fig. 2. Robesons 1991 and 2008 upper bound curves representing a general trade-off for membrane gas separation performance for CO2 /CH4 [(a) Park and Lee, 2008; (b)
Xiao et al. (2009)].
52
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
10
Polysulfone (PSF)
20
16
14
12
10
8.5
8
8
Plasticization Pressure
7.5
Minimum Permeability
18
9.5
2
6
10
12
14
16
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
53
54
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
Table 7
Improved plasticization resistance of polyimide using thermal and chemical cross-linking (Staudt-Bickel and Koros, 1999; Kratochvil and Koros, 2008).
Treatment conditions
Cross-linking agents/method
Polymer
35 C
Non cross-linked
Ethylene glycol in DMAc
6FDA-mPD
6FDA-DABA
35 C
Non cross-linked
Ethylene glycol in DMAc
6FDA-mPD/DABA (9:1)
6FDA-mPD/DABA (9:1)
220 C, 23 h
220 C, 23 h + Quenching
6FDA-DAM:DABA (2:1)
6FDA-DAM:DABA (2:1)
Permeability was normalized with respect to the initial permeability measurement taken at 2 atm.
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
55
Table 8
Mixed gas (CO2 /CH4 :50/50) permeability, ideal selectivity and separation factor of cross-linked 6FDA-ODA and TemMPD membranes (Chen et al., 2012).
Membrane
Cross-linking approach
Permeability of CO2
(Barrer)
Permeability of CH4
(Barrer)
Ideal selectivity
Separation factor
6FDA-ODA
Original sample
Immersion in APTMDS methanol
Solution for time range of 124 h
Direct mixing of APTMDS (27%) in the
polyimide solution
18.6
12.116.6
0.35
0.140.25
53.1
66.289.8
48.9
38.962.0
12.313.7
0.150.19
71.282.0
54.864.3
Original sample
Immersion in APTMDS/methanol
Solution for time range of 224 h
Direct mixing of APTMDS (25.5%) in
the polyimide solution
56.8
17.754.2
3.66
0.433.67
15.4
14.841.2
14.2
14.240.0
24.233.1
1.012.10
19.424.0
14.723.5
Fig. 5. Separation performance of decarboxylation-induced thermal crosslinking of hollow ber 6FDA-DAM:DABA (3:2) membrane for 10%CO2 /90% CH4 gas.
Qiu et al. (2011).
56
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
Table 9
Plasticization properties of cross-linked 6FDA-ODA and 6FDA-ODA (50%)-TemMPD (50%) membranes (Chen et al., 2012).
Membrane
Original 6FDA-ODA
Cross-linked 6FDA-ODA by immersion in APTMDS methanol solution for
5h
Original 6FDA-ODA (50%)-TemMPD (50%)
Cross-linked 6FDA-ODA (50%)-TemMPD (50%) by direct mixing of APTMDS
(5.5%) in the polyimide solution
15
8
2024
>41
48
12
14
>41
Table 10
Pure gas permeation results for partially pyrolyzed polyimide with various porogens.
Porogens
Temperaturea ( C)
Sulfonic group
Carboxylic acid
Cyclodextrin
Saccharides
370450
425475
300450
200425
PCO2
CO2 /CH4
145380
39.194.8
568000
5331389
6047
3117
24.926.9
Reference
Islam et al. (2005)
Maya et al. (2010)
Xiao and Chung (2011)
Chua et al. (2012)
acid gas (CO2 and H2 S) from non polar gases (H2 , N2 , and CH4 )
(Freeman et al., 2006; Lin and Freeman, 2005a,b) due to its polarity and CO2 afnity (Charmette et al., 2004). PEO contains polar
ether oxygen that favourably interacts with CO2 molecules and thus
increases its selectivity towards the gas (Li et al., 2011). Major challenges in the use of PEO for CO2 separation is its crystallinity and
solubility in water. The highly crystalline nature reduces permeability of gases, hence the productivity is low. As earlier stated,
one of the strategies to enhance the gas separation properties of
PEO is to prepare an amorphous polymer containing PEO. Lin and
Freeman (2005a) prepared a family of cross-linked poly(ethylene
glycol diacrylate) (XLPEGDA) and investigated the effect of crosslinking on the crystalinity and on gas permeability. The results
revealed crosslinking to have successfully distrupt crystallinity but
with litle effect on gas permeability and diffussivity. However, the
polar units of PEO was found to exhibit favourable interactions with
CO2 and this lead to high solubility selectivity for CO2 /CH4 gas pair.
It must be noted that such interaction was reported to be stronger
at lower temperature and this contributes to higher selectivities
at lower temperature. Lin and Freeman (2006) reported the permeabilities of XLPEGDA to various penetrants including CO2 and
CH4 as a function of temperature and fugacity of the penetrants.
Permeability data of CO2 and CH4 as function of temperature and
pressure revealed that the permeability of CH4 is independent of
upstream fugacity whereas that of CO2 increased with increasing
fugacity or concentration of the gas. This is due to sorbing of a signicant amount of CO2 which lead to an increase in polymer chain
exibility and fractional free volume. Thus, it can be inferred that
cross-linking did not improve the CO2 induced plasticization of this
polymer. Copolymerization was used by Li et al. (2011) to synthesize a series of poly(urethane-urea)s using 4,4-metylenediphenyl
diisocyanate (MDI), various polyether diols and ethylene diamine
(EDA). Polyethers such as poly(ethylene glycol) (PEG) 2000,
poly(propylene glycol) (PPG) 2700, poly(tetramethylene ether glycol) (Terathane) 2000, Terathane 2900 and mixture of PEG 2000
and Terathane 2000 were employed for the study. Pure gas permeation measurements were performed using various gases including
CO2 and CH4 . Results of these measurements revealed an instantaneous increase in CO2 permeability with increasing feed pressure
for all the samples. This is typical of rubbery polymers which
often exhibit high tendency to sorption of CO2 and hence causes
plasticization. Mixed and pure gas membrane separation performance of highly permeable poly(ethylene) oxide based multi-block
copolymer (Reijerkerk et al., 2011a), cross-linked poly(ethylene)
oxide copolymer (Ribeiro et al., 2011), and blend of polyimideb-ethylene oxide)/polyethylene glycol (Yave et al., 2009) membranes showed no promising results especially with respect to
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
57
58
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
Table 11
Summary of CO2 -induced plasticization behaviour of 6FDA-Durene/DABA copolyimides grafted with , and -cyclodextrin (Askari et al., 2012a,b).
Plasticization
pressure (atm)
Polymer
Thermal treatment
temperature ( C)
Original PI
200
300
425
510
1015
1520
PI-g--CD
200
300
425
710
1015
25
PI-g--CD
200
300
425
710
10
>30
PI-g--CD
200
300
425
10
10
>30
the permeability of the CO2 and the selectivity of CO2 /CH4 for the
grafted membranes despite pressure rise from 10 to 20 atm. From
these results, it can be inferred that the plasticization resistance
property of the membrane in the presence of mixed CO2 and CH4
has been improved by decomposition of the porogens.
4.4. Spinning processes and dual-layer hollow ber spinning
Some of the previous spinning processes and conditions of fabricating hollow ber membrane are not environmentally benign
and usually pose challenges in application for commercial production. Avrillon (1997) disclosed a hollow ber membrane spun
from 6FDA-2,6-DAT/1,4-dioxane/NMP. Pure gas permeation test
conducted on this membrane at 118 psi revealed a permeance of
162 GPU (where 1 GPU = 1 106 cm3 (STP)/cm2 scmHg) for CO2
and selectivity of 74 for CO2 /CH4 . The mixed gas test conducted
at higher pressure of 368 psi showed a CO2 permeance of 155 GPU
and CO2 /CH4 selectivity of 59. Major challenges with this method
include total dissolution and stability of 6FDA-2,6-DAT in the mixture of 1,4-dioxane and NMP, the use of mixture of acetic acid, water
and 1,4-dioxane as bore uid, and the use of 53 wt% aqueuos solution of acetic acid as coagulant. The corrosive nature of acetic acid
and the toxicity of 1,4-dioxane contitute an environmental concern
for the use of this process. In addition, this process condition make
scale up unrealistic. In order to simplify hollow ber fabrication
processes, Cao et al. (2002) developed a new one-polymer and onesolvent system (6FDA-2,6-DAT/N-methyl-pyrrolidone (NMP)) for
fabrication of hollow ber 6FDA-2,6-DAT membrane for CO2 /CH4
separation. The authors employed 6FDA-2,6-DAT/NMP, NMP/water
mixture and water as the spinning dope, internal and external coagulants, respectively. The separation performance of the membrane,
including CO2 -induced plasticization resistance was evaluated
using both pure and mixed gas permeation experiments. In addition, the time-dependent drifts in permeability and selectivity were
monitored to conrm long-term applicability of the membrane.
Results of these tests indicate that the membrane exhibit tendency
to be plasticized and prone to physical agin. However, the membrane still posses an impressive stable performamnce under mixed
gas tests better than the available membrane operating at low
pressure. A further investigation on improvement of CO2 /CH4 separation performance of 6FDA-2,6-DAT was done by Chung et al.,
2003 and Ren et al. (2002). The authors observed that spinning at
different shear rates and take-up rates did not effectively produce
membrane with better plasticization suppression properties however, thermally treated 6FDA-2,6-DAT hollow ber membranes
exhibit a signicant resistance to CO2 -induced plasticization. Thus,
samples were thermally treated at various temperatures and physical aging, and then subjected to pure gas permeation tests. Results
obtained showed increase in plasticization pressure due to heat
treatment. In addition, XRD tests were performed to evaluate the
plasticization suppression charateristics of the membrane. Unlike
other studies where enhancement in the plastization suppression
properties was attributed to cross-linking, here the main causes
was said to have arisen from better chain packing, module interaction and more compact selective skin induced at elevated heat
treatment temperatures. The treated hollow ber membrane was
found to dissolved easily in NMP solvent within 10 min.
Table 12
Permeability coefcients and ideal gas selectivities of CO2 and CH4 in various types of thermally rearranged polymers.
Polymers
Poly(benzimidazole)
Polyhydroxyamide
Poly(benzoxazole)
HAB-6FDA TR polymers
Cardo-copoly(hydroxyimide)
Refences
Han et al. (2010)
Wang and Chung (2011)
Wang et al. (2011)
Sanders et al. (2012)
Yeong et al. (2012)
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
For more than 40 years, the symmetric single layer hollow ber
conguration remained a favourable conguration used for membrane gas separation (Li et al., 2008). The need to further expand
industrial application of membrane in gas separation required an
enhancement in both the gas productivity and selectivity. The complexity of spinning process and conditions make it difcult to
produce ultra-thin dense selective and defect free layer of membrane with higher selectivity. The thinner the membrane, the more
the tendency of surface defects formation in membrane. One of the
methods to solve this problem is the combination of heat treatment
with effective sealing of membrane by coating with highly permeable polymer such as silicone rubber (Li et al., 2008; Murphy et al.,
2009). With advancement in the polymer fabrication technology,
development of ultrathin dense selective layer is no longer a challenge (Li et al., 2004). Moreover, another trend that has emerged
due to a further advancement in membrane fabrication technology is co-extrusion technique for fabricating dual-layer hollow
ber membranes (Peng et al., 2010). Dual-layer hollow ber consists of an asymmetric separating outer layer and a microporous
supporting inner layer (Li et al., 2004, 2008). The outer layer is usually made of high selectivity and permeability materials in order
to provide good permselectivity. The inner layer is made mainly
from low-cost materials and it provides the necessary mechanical
support for the outer layer (Li et al., 2004). Obviously, the evolution of co-extrusion technology for dual-layer fabrication provided
an opportunity to exploit the use of high-performance but expensive materials for membrane application (Hosseini et al., 2010; Li
et al., 2008; Peng et al., 2010). Ideally, it is very important to ensure
that dual-layer hollow bers are delamination-free at the interface in order to withstand high-pressure feed streams (Li et al.,
2004). Problem of delamination could be minimized by choosing
compatible materials or use of spinnerets with modied designs
(Hosseini et al., 2010). Also, the interface between the two layers
and between the bulk structures of the inner layers must be porous
enough to prevent gas transport resistances which could result in
signicant decrease in both the permeance and permselectivity of
the membranes (Li et al., 2004).
Fabrication of novel high performance gas separation membranes through an integration of polymer blending technology
and dual-layer hollow ber spinning process was exploited by
Hosseini et al. (2010). The authors used a polymer blend constructed from an interpenetrated networks of poly (benzimidazole)
(PBI) and Matrimid, and then investigated the effect of air gap
distance, chemical cross-linking modications and elongation
drawings on the separation performance of the membranes. The
results obtained showed that the method is efcient for fabricating
membrane with very good resistance to CO2 -induced plasticization. The improved separation performance was attributed to
improved microstructutral properties of the dense skin layer and
the role of PBI molecules in providing an integrated interpenetration networks through strong hydrogen bonding interactions with
Matrimid chains. Samples were evaluated based on the spinning
parameters and conditions (such as outer dope ow rates, inner
dope ow rates, bore uid ow, air gap, take-up speed and ber collection state) that were used in preparation of the dual-layer hollow
ber membranes. Details of the conditions are provided in the original work of the authors. Also, a systematical study of fabrication
parameters on dual-layer hollow ber Matrimid/polyethersulfone
membranes was performed by Jiang et al. (2004). The authors
investiagted the effects of spinning conditions such as spinneret
temperature, coagulant temperature, and dope ow rate on the
membrane morphology and gas separation performance. Results
obtained showed that the spinneret and coagulant temperatures
are very important in dual layer membrane performance. Moreover, it was observed that both the outer layer and the inner layer
dope ow rates have different levels of inuence on gas separation
59
performance of the membranes. The developed dual-layer membranes have impressive CO2 /CH4 selectivity of 40 in mixed gas
test.
4.5. Thermal rearrangement
Global rise in the use of membrane for gas separation required
the development membrane that will be suitable for high temperature application such as 300 C and above. Polyimide and
polybenzimidazole are few of the polymers that are available for
this purpose (Park et al., 2010). In addition to excellent thermal
properties, aromatic polymers interconnected with heterocyclic
rings such as polybenzoxazoles (PBO) and polybenzothiazoles (PBT)
show very promising high selectivities. However, due to the lack of
solubility of these polymers in common solvents, practical fabrication of these polymers membrane using conventional solution
casting method remained a fabrication challenge. Park et al. (2007)
reported a breakthrough in overcoming the fabrication challenge
by adopting a post-fabrication polymer modifying reactions (Braz
et al., 1966; Lucero and Likhatchev, 2002; Tullos et al., 1999) to
obtain dense PBO and PBT membranes. The authors employed
thermal rearrangement of soluble aromatic polymers containing
ortho-positioned functional group such as OH and SH (Tullos et al.,
1999). Resulting membrane from these methods was subjected to
a mixed-gas permeation test to investigate its plasticization property using high CO2 concentration of about 80 mol% and a CO2
fugacity of about 15 atm. The membrane was found to exhibit high
resistance to plasticization and a signicant reduction in selectivity with increasing CO2 fugacity. Gas permeation performance
of the membrane was further investigated by varying template
molecules and heat treatment protocols. Results of this investigation are presented in Park et al. (2007). Following a successful
development of thermal rearrangement procedure for synthesis of
at-sheet and dense TR-PBO membrane, other studies have been
conducted in order to further investigate the behaviour of thermally rearranged polymers. For example, studies on the evolution
of structural changes, physicochemical and transport properties
of thermally rearranged polyhydroxyamide (PHA) was done by
Wang and Chung (2011), and Wang et al. (2011). Stepwise thermal cyclization was used to transform poly(hydroxyamide amic
acid) to poly(benzoxazole). Also, a series of new cardo-copolyimide
with different compositions of ortho-functional cardo-diamine,
9,9-bis(3-amino-4-hydroxyphenyl) uorene were synthesized and
then thermally rearranged to cardo-copolybenzaxole membranes
by Yeong et al. (2012). A two step polycondensation method
with chemical imidization was employed by Sanders et al.
(2012) to prepare thermally rearranged polymers. Polyimide
synthesized from 3,3 -dihydroxy-4,4 -diamino-biphenyl (HAB)
and 2,2 -bis(3,4-dicarboxyphenyl) hexauoropropane dianhydride
(6FDA) was used as precursors. A new synthesis route for preparing
a thermally rearranged microporous polybenzimidazole TR-PBI)
membranes with exceptionally high gas separation characteristics
were reported by Han et al. (2010). Highly permeable TR-PBI membranes were prepared by the alkaline hydrolysis of carbonyl group
of polypyrrolone followed by simple thermal treatment. A summary of the CO2 /CH4 separation performance of all these polymers
is presented in Table 12.
Thermal rearrangement technique was employed, for the rst
time, by Kim et al. (2012), to fabricate a hollow ber membranes.
The hollow ber was fabricated by spinning its soluble precursor polymer, hydroxyl poly(amic acid) (HPAAc), via non-solvent
induced phase separation process of TR-polymers. Highly permeable TR-PBO hollow ber membranes can then be obtained
by thermal imidization followed by thermal rearrangement of
hydroxyl ployimide (HPI) (Kim et al., 2012). The gas permeance
of TR-PBO was investigated as a function of thermal treatment
60
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
Table 13
Permeance of 6FDA-6FAP as a function of thickness and molecular weights (Mikawa et al., 2002).
Samples thickness (nm)
Molecular weight
65
64
75
1.2 105
2.0 105
4.3 105
575
540
450
3
8
>10.53
Degree of sulfonation
S-PEEK 1
S-PEEK 2
S-PEEK 3
0.44
0.76
1.10
8
10.5
14.5
11
32
>40
et al. (2002), three copolyimides were prepared by the condensation polymerization of alicyclic 2,3,5-tricarboxy cyclopentyl
acetic dianhydride (TCDA) with diamino diphenyl ether (DADE)
and bis(aminopropyl) polydimethylsiloxane (BAS) of different
chain length. The effect of CO2 pressure on the permeability of
the polyimides containing soft segment of PDMS was studied
(Table 15). Results obtained revealed that membranes produced
by copolyrization of PDMS and polyimides have lower permeability properties thant the PDMS and are affected by plasticization at
low pressure. However, the silicone modied membrane where silicone atoms are contained in the backbone chains of the polyimides
are observed to be promising materials and need to be further
investigated especially for CO2 induced plasticization. Moreover,
mixed and pure gas membrane separation performance of highly
permeable poly(ethylene) oxide based multi-block copolymer
(Reijerkerk et al., 2011a), cross-linked poly(ethylene) oxide copolymer (Ribeiro et al., 2011), and blend of polyimide-b-ethylene
oxide)/polyethylene glycol (Yave et al., 2009) membranes showed
no promising results especially with respect to plasticization phenomenon. Molecular engineering of PIM-1/Matrimid blend was
carried out by Yong et al. (2012) to produce gas separation membranes. Mixed and pure gas permeation tests were performed on
these membranes for CH4 and CO2 . Results obtained were in the
range of 123355 barrer for CO2 permeability and 1436 ideal
selectivity. Further investigation into the techniques of blending
and the blending ratio is very crucial in this method.
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
61
Table 15
Plasticization pressure and permeability at plasticization pressure of silicon-modied polyimide and polyimides containing PDMS at 35 C for pure and mixed (50% CO2 )
(Stern and Vaidyanathan, 1990; Nakagawa et al., 2002).
Polymer sample
TCDA-DADE
SPI-9
Copolyimide Aa
Copolyimide Ba
Copolyimide Ca
SiDA-4,4 -ODAa
SiDA-p-PDAa
a
0.00
12.60
21
19
18
Mixed
Pure
Mixed
2.65
9.5
288.26
134.69
60.51
2.92
2.79
2.3
8.5
10
5
7.5
1.5
1.5
1.5
>7
5
5
Permeability at plasticization pressure were estimated from the relation provided by the author.
Table 16
Pure gas transport properties of various PIMs (30 C, 200300 mbar).
Membrane
Experimental conditions
Feed pressure
PIM-1a
PIM-7a
Polybenzodioxane-PIM-1
Thioamide-PIM
CarboxylatedPIMs
Decarboxylation-induced cross-linked PIMs
PIMs containing Triuoromethyl and Phenylsulfone groups
200 mbar
200 mbar
1 atm
1 bar
50 psig
3.4 atm
50 psig
Permeability (Barrer)
Temperature ( C)
CO2
CH4
30
30
25
25
25
30
25
23000
1100
4390
1120
6206715
12912345
7313616
125
62
310
56
52.6192
Reference
a
PIM-1 was prepared by reacting 5,5,6,6-tetrahydroxy-3,3,3,3 tetramethyl-1,1-spirobisindane and tetrauoroterephthalonitrile while PIM-7 was prepared by reacting
5,5,6,6-tetrahydroxy-3,3,3,3 tetramethyl-1,1-spirobisindane with 7,7,8,8-tetrachloro-phenazyl-3,3,3,3-tetramethyl-1,1-spirobisindane.
62
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
nanoparticles in a polymer of intrinsic microporosity (PIM-1). Journal of Membrane Science 346, 280287.
Armaroli, N., Balzani, V., 2011. Energy for a Sustainable World From the Oil Age to
a Sun-Powered Future. WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Aroon, M.A., Ismail, A.F., Montazer-Rahmati, M.M., Matsuura, T., 2010. Morphology
and permeation properties of polysulfone membranes for gas separation: effects
of non-solvent additives and co-solvent. Separation and Purication Technology
72, 194202.
Askari, M., Xiao, Y., Li, P., Chung, T.-S., 2012a.
Natural gas purication
and olen/parafn separation using cross-linkable 6FDA-Durene/DABA copolyimides grafted with , , and -cyclodextrin. Journal of Membrane Science
390391, 141151.
Askari, M., Yang, T., Chung, T.-S., 2012b. Natural gas purication and olen/parafn
separation using cross-linkable dual-layer hollow ber membranes comprising
b-cyclodextrin. Journal of Membrane Science 423424, 392403.
Avrillon, R., 1997. Highly selective asymmetric membranes for gas separation. US
Patent Number 5, 674, 629, France.
Baker, R.W., 2002. Future directions of membrane gas separation technology. Industrial and Engineering Chemistry Research 41, 13931411.
Baker, R.W., Lokhandwala, K., 2008. Natural gas processing with membranes. An
overview. Industrial and Engineering Chemistry Research 47, 21092121.
Baker, W.B., 2010. Research needs in the membrane separation industry: looking
back, looking forward. Journal of Membrane Science 362, 134136.
Bernardo, P., Drioli, E., Golemme, G., 2009. Membrane gas separation: a
review/state of the art. Industrial and Engineering Chemistry Research 48,
46384663.
Bhattacharya, A., Misra, B., 2004. Grafting: a versatile means to modify polymers
techniques, factors and applications. Progress in Polymer Science 29, 767814.
Braz, Kardash, G.I., Yakubovich, I.Y., Myasnikova, V., Ardashnikov, G., Oleinik, A.,
Pravednikov, A.F., Yakubovich, A.N., Ya, A., 1966. Polybenzoxazoles, their synthesis and thermal degradation. Polymer Science USSR 8, 295301.
Budd, P.M., McKeown, N.B., Fritsch, D., Yampolskii, Y., 2010. Gas permeation
parameters and other physicochemical properties of a polymer of intrinsic
microporosity (PIM-1). In: Yampolskii, Y., Freeman, B. (Eds.), Membrane Gas
Separation. John Wiley & Sons Ltd., West Sussex, pp. 2942.
Budd, P.M., McKeown, N.B., Fritschc, D., 2005a. Free volume and intrinsic microporosity in polymers. Journal of Materials Chemistry 15, 19771986.
Budd, P.M., McKeownb, N.B., Ghanemb, B.S., Msayibb, K.J., Fritschc, D., Starannikovad, L., Belovd, N., Sanrovad, O., Yampolskii, Y., Shantaroviche, V., 2008. Gas
permeation parameters and other physicochemical properties of a polymer of
intrinsic microporosity: Polybenzodioxane PIM-1. Journal of Membrane Science
325, 851860.
Budd, P.M., Msayib, K.J., Tattershall, C.E., Ghanema, B.S., Reynolds, K.J., McKeownb,
N.B., Fritsch, D., 2005b. Gas separation membranes from polymers of intrinsic
microporosity. Journal of Membrane Science 251, 263269.
Budd, P., Ghanem, B.S., Makhseed, S., McKeown, N., Msayib, K.J., Tattershall,
C.E., 2004. Polymers of intrinsic microporosity (PIMs): robust, solutionprocessable, organic nanoporous materials. Chemical Communications (2),
230231.
Cao, C., Wang, R., Chung, T.S., Liu, Y., 2002. Formation of high-performance 6FDA-2,6DAT asymmetric composite hollow ber membranes for CO2 /CH4 separation.
Journal of Membrane Science 209, 309319.
Charmette, C., Sanchez, J., Gramain, P., Rudatsikira, A., 2004. Gas transport properties
of poly(ethylene oxide-coepichlorohydrin) membranes. Journal of Membrane
Science 230, 161169.
Chen, X.Y., Rodrigue, D., Kaliaguine, S., 2012. Diamino-organosilicone APTMDS: a
new cross-linking agent for polyimides membranes. Separation and Purication
Technology 86, 221233.
Chew, T.L., Ahmad, A.L., Bhatia, S., 2011. Ba-SAPO-34 membrane synthesized from
microwave heating and its performance for CO2 /CH4 gas separation. Chemical
Engineering Journal 171, 10531059.
Chew, T.-L., Ahmad, A.L., Bhatia, S., 2010. Ordered mesoporous silica (OMS) as an
adsorbent and membrane for separation of carbon dioxide (CO2). Advances in
Colloid and Interface Science 153, 4357.
Choi, J.I., Jung, C.H., Han, S.H., Park, H.B., Lee, Y.M., 2010. Thermally rearranged (TR)
poly(benzoxazole-co-pyrrolone) membranes tuned for high gas permeability
and selectivity. Journal of Membrane Science 349, 358368.
Chua, M.L., Xiao, Y.C., Chung, T.-S., 2012. Effects of thermally labile saccharide units
on the gas separation performance of highly permeable polyimide membranes.
Journal of Membrane Science 415416, 375382.
Chung, T.S., Ren, J., Wang, R., Li, D., Li, Y., Pramoda, K.P., Cao, C., Loh, W.W., 2003.
Development of asymmetric 6FDA-2,6DAT hollow ber membranes for CO2 /CH4
separation Part 2, suppression of plasticization. Journal of Membrane Science
214, 5769.
Chung, T.S., Teoh, S.K., 1999. The aging phenomenon of polyethersulphone hollow bre membranes for gas separation and their characteristics. Journal of
Membrane Science 152, 175.
Chung, T., Kafchinski, E., 1996.
Aging phenomenon of 6FDApolyimide/polyacrylonitrile composite hollow bers. Journal of Applied
Polymer Science 59, 77.
Chung, T.-S., Jiang, L.Y., Lia, Y., Kulprathipanja, S., 2007. Mixed matrix membranes
(MMMs) comprising organic polymers with dispersed inorganic llers for gas
separation. Progress in Polymer Science 32, 483507.
Cong, H., Radosz, M., Towler, B.F., Shen, Y., 2007. Polymerinorganic nanocomposite membranes for gas separation. Separation and Purication Technology 55,
281291.
Cruden, B., Chu, K., Gleason, K., Sawin, H., 1999. Thermal decomposition of low
dielectric constant pulsed plasma uorocarbon lms II. Effect of postdeposition
annealing and ambients. Journal of Electrochemical Society 146, 45974604.
Cui, L., Qiu, W., Paul, D., Koros, W., 2011. Responses of 6FDA-based polyimide thin
membranes to CO2 exposure. Polymer 52, 55285537.
Dorkenoo, K.D., Pfromm, P., 2000.
Accelerated physical aging of thin
poly[1(trimethylsilyl)-1-propyne] lms. Macromolecules 33, 37473751.
Du, N., Dal-Cin, M.M., Robertson, G.P., Guiver, M.D., 2012. Decarboxylation-induced
cross-linking of polymers of intrinsic microporosity (pims) for membrane gas
separation. Macromolecules 45, 51345139.
Du, N., Robertson, G.P., Song, J., Pinnau, I., Guiver, M.D., 2009. High-performance carboxylated polymers of intrinsic microporosity (PIMS) with tunable gas transport
properties. Macromolecules 42, 60386043.
Du, N., Robertson, G.P., Song, J., Pinnau, I., Thomas, S., Guiver, M.D., 2008. Polymers
of intrinsic microporosity containing triuoromethyl and phenylsulfone groups
as materials for membrane gas separation. Macromolecules 41, 96569662.
Dung, E.J., Bombom, L.S., Agusomu, T.D., 2008. The effects of gas aring on crops in
the Niger Delta Nigeria. Geological Journal 73, 297305.
Ebewele, R.O., 2000. Polymer Science and Technology. CRC Press, New York.
Engelien, H.K., 2004. Process Integrated Membrane Separationwith Application
to the Removal of CO2 from Natural Gas. Presentation. NTNU, Department of
Chemical Engineering.
Ferrari, M.C., Galizia, M., De Angelis, M.G., Sarti, G.C., 2010. Vapor sorption and
diffusion in mixed matrices based on Teon AF 2400. In: Yampolskii, Y., Freeman,
B. (Eds.), Membrane Gas Separation. John Wiley & Sons, Ltd., West Sussex, pp.
125142.
Flaconnche, B.J.M., Klopffer, M.H., 2001. Permeability, diffusion and solubility of
gases in polyethylene, polyamide 11 and poly(vinylidene uoride). Oil & Gas
Science and Technology 56, 261278.
Freeman, B.D., 1999. Basis of permeability/selectivity tradeoff relations in polymeric
gas separation membranes. Macromolecules 32, 375380.
Freeman, B.D., Sanders, D., Ribeiro JR, C.P., Smith, Z., Guo, R., 2012. Patent No. US
2012/0329958 A1. USA.
Freeman, B.D., Toy, L., Lin, H., Van Wagner, E., Toy, L., Gupta, R., 2006. Plasticization enhanced hydrogen purication using polymeric membranes. Science 311,
639642.
Fried, J.R., 2003. Polymer Science and Technology, second ed. Prentice Hall, New
Jersey.
Furukawa, M., Yamada, Y., Tsujita, Y., Takizawa, A., 1990. Gas separation properties
of silicone modied polyimides. In: 3rd SPSJ International Polymer Conference
on Membrane and Interfacial Phenomenon and Polymer, Nagoya, Japan.
Gavalas, G.R., 2006. Zeolite membranes for gas and liquid separations. In:
Yampolskii, Y., Pinnau, I., Freeman, B. (Eds.), Materials Science of Membranes for Gas and Vapor Separation. John Wiley & Sons Ltd., West Sussex,
pp. 307336.
Golemme, G., Jansen, J.C., Muoio, D., Bruno, A., Manes, R., Buonomenna, M.G., Choi,
J., Tsapatsis, M., 2010. Glassy Peruorolymerzeolite hybrid membranes for gas
separations. In: Yampolskii, Y., Freeman, B. (Eds.), Membrane Gas Separation.
John Wiley & Sons, Ltd., West Sussex, pp. 113124.
Hagg, M.-B., 2009. Membrane for gas separation. In: Pabby, A.K., Rivzi, S.S., Sastre,
A.M. (Eds.), Handbook of Membrane Separations: Chemical, Pharmaceautical,
Food, and Biotechnological Applications. CRC Press, Boca Raton, pp. 65105.
Han, L., Lin, Y., Tsui, T.Y., Vlassak, J.J., 2009. The effect of porogen loading on the stiffness and fracture energy of brittle organosilicates. Journal of Materials Research
24, 107116.
Han, S.H., Lee, J.E., Lee, K.-J., Park, H.B., Lee, Y.M., 2010. Highly gas permeable and
microporous polybenzimidazole membrane by thermal rearrangement. Journal
of Membrane Science 357, 143151.
Hibshman, C., Cornelius, C., Marand, E., 2003. The gas separation effects of annealing
polyimideorganosilicate hybrid membranes. Journal of Membrane Science 211,
2540.
Hillock, A.M., Miller, S.J., Koros, W.J., 2008. Cross-linked mixed matrix membranes
for the purication of natural gas: effects of sieve surface modication. Journal
of Membrane Science 314, 193199.
Hofmann, D., Tocci, E., 2009. Molecular modeling, a tool for the knowledge-based
design of polymer-based membrane materials. In: Drioli, E., Giomo, L. (Eds.),
Membrane Operations Innovative Separations and Transformations. Wiley- VCH
Verlag GmbH & Co. KGaA, Weinhelm, pp. 317.
Horn, N.R., Paul, D.R., 2011a. Carbon dioxide plasticization and conditioning effects
in thick vs thin glassy. Polymer 52, 16191627.
Horn, N.R., Paul, D.R., 2011b. Carbon dioxide plasticization of thin glassy polymer
lms. Polymer 52, 55875594.
Horn, N.R., Paul, D.R., 2012. Carbon dioxide sorption and plasticization of
thin glassy polymer lms tracked by optical methods. Macromolecules 45,
28202834.
Hosseini, S.S., Peng, N., Chung, T.S., 2010. Gas separation membranes developed
through integration of polymer blending and dual-layer hollow ber spinning
process for hydrogen and natural gas enrichments. Journal of Membrane Science
349, 156166. http://en.wikipedia.org/wiki/Polyethylene oxide
Huang, Y., Paul, D.R., 2006. Physical aging of thin glassy polymer lms monitored
by optical properties. Macromolecules 39, 15541559.
Huang, Y., Paul, D.R., 2004a. Experimental methods for tracking physical aging of
thin glassy polymer lms by gas permeation. Journal of Membrane Science 244,
167178.
Huang, Y., Paul, D.R., 2004b. Physical aging of thin glassy polymer lms monitored
by gas permeability. Polymer 45, 83778393.
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
Immergut, E.H., Mark, H.F., 1965. Principles of plasticization. In: Platzer, N.A. (Ed.),
Plasticization and Plasticizer Processes, vol. 48. American Chemical Society,
Washington, DC, pp. 126.
IPCC, 2007. Intergovernmental Panel on: Climate Change 2007: ThePhysicalScience
Bases Contribution of Working Group 1 to the Fourth Assessment Report of the
Intergovernmental Panel on Climate Change Series. Cambridge University Press,
Cambridge, United Kingdom and NewYork, USA.
Islam, M.N., Zhou, W., Honda, T., Tanaka, K., Kita, H., Okamoto, K., 2005. Preparation and gas separation performance of exible pyrolytic membranes by
low-temperature pyrolysis of sulfonated polyimides. Journal of Membrane Science 261, 1726.
Ismail, A.F., 2010. Preparation of carbon membranes for gas separation. In: Drioli,
E.G. (Ed.), Comprehensive Membrane Science and Engineering, vol. 1, 1st ed.
Elsevier, Kidlington, pp. 275290.
Jana, S., Purkait, M.K., Mohanty, K., 2012. Preparation and applications of zeolite
membranes: a review. In: Mohanty, K., Purkait, M.K. (Eds.), Membrane Technologies and Applications. CRC Press Taylor and Francis Group, New York, pp.
5776.
Jenkins, A.D., Kratochvil, P., Stepto, R.F., Suter, U.W., 1996. Glossary of basic terms in
polymer science (IUPAC recommendations 1996). Pure and Applied Chemistry
68, 15911595.
Jiang, L.Y., Chung, T.S., Kulprathipanja, S., 2006. Fabrication of mixed matrix hollow
bers with intimate polymerzeolite interface for gas separation. AIChE Journal
52 (8), 28982908.
Jiang, L., Chung, T.-S., Li, D.F., Cao, C., Kulprathipanja, S., 2004. Fabrication of
matrimid/polyethersulfone dual-layer hollow ber membranes for gas separation. Journal of Membrane Science 240, 91103.
Kanehashi, S., Sato, S., Nagai, K., 2010. Synthesis and gas permeability of hyperbranched and cross-linked polyimide membranes. In: Yampolskii, Y., Freeman,
B. (Eds.), Membrane Gas Separation. John Wiley & Sons, Ltd., West Sussex, pp.
327.
Kelman, S.D., Rowe, B.W., Bielawski, C.W., Pas, S.J., Hill, A.J., Paul, D.R., Freeman, B.D.,
2008. Crosslinking poly[1-(trimethysilyl)-1-propyne] and its effect on physical
stability. Journal of Membrane Science 320, 123134.
Khan, A.L., Li, X., Vankelecom, I.F.J., 2011. Mixed-gas CO2 /CH4 and CO2 /N2 separation
with sulfonated PEEK membranes. Journal of Membrane Science 372, 8796.
Kidnay, A.J., Parrish, W.R., 2006. Fundamentals of Natural Gas Processing. Taylor &
Francis Group, Boca Raton.
Kidnay, A.J., Parrish, W.R., McCartney, D.G., 2011. Fundamentals of Natural Gas
Processing. Taylor & Francis Group, Boca Raton.
Kim, S., Han, S.H., Lee, Y.M., 2012. Thermally rearranged (TR) polybenzoxazole hollow ber membranes for CO2 capture. Journal of Membrane Science 403404,
169178.
Kita, H., 2006. Gas and vapor separation membranes based on carbon membranes.
In: Yampolkii, Y., Pinnau, I., Freeman, B.D. (Eds.), Materials Science of Membranes
for Gas and Vapor Separation. John Wiley & Sons Ltd., West Sussex, pp. 337354.
Kohl, A.L., Nielsen, R., 1997. Gas Purication, fth ed. Gulf Professional Publishing,
Texas.
Koros, W.J., 1991. Gas separation. In: Baker, R., Cussler, E., Eykamp, W., Koros, W.,
Riley, R., Strathmann, H. (Eds.), Membrane Separation SystemsRecent Developments and Future Directions, vol. II. William Andrew Publishing/Noyes, New
Jersey, pp. 189241.
Koros, W.J., Lively, R.P., 2012. Water and beyond: expanding the spectrum of largescale energy efcient separation processes. AIChE Journal 58 (9).
Koros, W.J., Mahajan, R., 2000. Pushing the limits on possibilities for large scale gas
separation: which strategies? Journal of Membrane Science 175, 181196.
Koros, W.K., Krotochvil, A., Shu, S., Husain, S., 2009. Energy and environmental
issues and impacts of membranes in industry. In: Drioli, E., Giorno, L. (Eds.),
Membrane Operations Innovative Separations and Transformations. Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim, pp. 139165.
Kratochvil, A.M., Koros, W.J., 2008. Decarboxylation-induced cross-linking of a
polyimide for enhanced CO2 plasticization resistance. Macromolecules 41,
79207927.
Larocca, N.M., Pessan, L.A., 2003. Effect of antiplasticisation on the volumetric,
gas sorption and transport properties of polyetherimide. Journal of Membrane
Science 218, 6992.
Lee, B., Oh, W., Hwang, Y., Park, Y.-H., Yoon, J., Jin, Jin K.S., Heo, K., Kim, J., Kim,
K.-W., Ree, M., 2005a. Imprinting well-controlled nanopores in organosilicate
dielectric lms: triethoxysilyl-modied six armed poly (-caprolactone) and its
chemical hybridization with an organosilicate precursor. Chemistry of Materials
17, 18451852.
Lee, B., Park, Y.-E., Hwang, Y.-T., Oh, W., Yoon, J., Ree, M., 2005b. Ultralow-k
nanoporous organosilicate dielectric lms imprinted with dendritic spheres.
Nature Materials 4, 147151.
Lee, J.S., Leisen, J., Choudhury, R.P., Kriegel, R.M., Beckham, H.W., Koros, W.J., 2012a.
Antiplasticization-based enhancement of poly(ethylene terephthalate) barrier
properties. Polymer 53, 213222.
Lee, J.S., Madden, W., Koros, W.J., 2010a. Antiplasticization and plasticization of
Matrimid asymmetric hollow ber membranesPart A. Experimental. Journal
of Membrane Science 350, 232241.
Lee, J.S., Madden, W., Koros, W.J., 2010b. Antiplasticization and plasticization of
Matrimid asymmetric hollow ber membranesPart B. Modeling. Journal of
Membrane Science 350, 242251.
Lee, L.-L., Tsai, D.-S., 2001. Synthesis and permeation properties of silicon-carbonbased inorganic membrane for gas separation. Industrial and Engineering
Chemistry Research 40, 612616.
63
Lee, Y. M., Kim, K.-Y., Jung, C.-H., Park, H.-B., Kwon, J., Han, S. H., 2012. Patent No. US
2012/0042777 A1. Korea.
Leggett, J. A., Lattanzio, R. K., Ek, C., Parker, L.,;1; 2009. An Overview of Greenhouse
Gas (GHG) Control Policies in Various Countries. Congressional Research Service.
CRS Report for Congress.
Gas permeation properties of
Li, H., Freeman, B.D., Ekiner, O.M., 2011.
poly(urethane-urea)s containing different polyethers. Journal of Membrane Science 369, 4958.
Li, Y., Cao, C., Chung, T., Pramoda, K., 2004. Fabrication of dual-laye r polyethersulfone (PES) hollow ber membranes with an ultrathin dense selective layer for
ga sseparation. Journal of Membrane Science 245, 5360.
Li, Y., Chung, T.-S., 2008. Highly selective sulfonated polyethersulfone (SPES)-based
membranes with transition metal counterions for hydrogen recovery and natural gas separation. Journal of Membrane Science 308, 128135.
Li, Y., Chung, T.S., 2010. Silver ionic modication in dual-layer hollow ber membranes with signicant enhancement in CO2/CH4 and O-2/N-2 separation.
Journal of Membrane Science 350, 226231.
Li, Y., Chung, T.-S., Kulprathipanja, S., 2007. Novel Ag+-Zeolite/Polymer Mixed Matrix
Membranes with a High CO2/CH4 Selectivity. (610-616, Ed.) AIChE J., 53 (3).
Li, Y., Chung, T.-S., Xiao, Y., 2008. Superior gas separation performance of duallayer hollow ber membranes with an ultrathin dense-selective layer. Journal
of Membrane Science 325, 2327.
Lin, H., Freeman, B.D., 2005a. Gas and vapor solubility in cross-linked poly(ethylene
glycol diacrylate). Macromolecules 38, 83948407.
Lin, H., Freeman, B.D., 2005b. Materials selection guidelines for membranes that
remove CO2 from gas mixtures. Journal of Molecular Structure 739, 5774.
Lin, H., Freeman, B., 2004. Gas solubility, diffusivity and permeability in
poly(ethylene oxide). Journal of Membrane Science 239, 105117.
Lin, H., Freeman, D.B., 2006. Gas permeation and diffusion in cross-linked
poly(ethylene glycol diacrylate). Macromolecules 39, 35683580.
Lin, W.H., Chung, T., 2000. Aging phenomenon of 6FDA-durene polyimide hollow
bers. Journal of Polymer Science, Polymer Physics 38, 765.
Lin, W.-H., Chung, T.-S., 2001. Gas permeability, diffusivity, solubility, and aging
characteristics of 6FDA-durene polyimide membranes. Journal of Membrane
Science 186, 183193.
Liu, C., Kulprathipanja, S., 2010. Mixed-matrix membranes. In: Zeolites in Industrial
Separation and Catalysis. WILEY-VCH Verlag GmbH & Co KGaA, Weinheim, pp.
329353.
Liu, C., Kulprathipanja, S., Hillock, A.M., Husain, S., Koros, W.J., 2008. Recent progress
in mixed-matrix membranes. In: Li, N.N., Fane, A.G., Ho, W.S., Matsuura, T. (Eds.),
Advanced Membrane Technology and Applications. John Wiley & Sons, Inc., New
Jersey, pp. 789820.
Liu, Y., Wang, R., Chung, T.-S., 2001. Chemically cross-linking modication of
polyimide membranes for gas separation. Journal of Membrane Science 189,
231.
Lucero, D.G., Likhatchev, D., 2002. Imide-to-benzoxazole rearrangement in ortho
substituted poly(4,4-diphenylene pyromellitimides)s. Polymer Bulletin 48,
261269.
Maeda, Y., Paul, D.R., 1987a. Effect of antiplasticization on gas sorption and transport.
I Polysulfone. Journal of Polymer Science Part B: Polymer Physics Edition 25,
957980.
Maeda, Y., Paul, D.R., 1987b. Effect of antiplasticization on gas sorption and transport. II Poly(phenylene oxide). Journal of Polymer Science Part B: Polymer
Physics Edition 25, 9811003.
Maeda, Y., Paul, D.R., 1987c. Effect of antiplasticization on gas sorption and transport. III Free volume interpretation. Journal of Polymer Science Part B: Polymer
Physics Edition 25, 10051016.
Maeda, Y., Paul, D.R., 1987d. Effect of antiplasticization on selectivity and productivity of gas separation membranes. Journal of Membrane Science 30 (1),
19.
Marti, N., Quattrini, F., Butte, A., Morbidelli, M., 2005. Production of polymeric
materials with controlled pore structure: the reactive gelation process. Macromolecular Materials and Engineering 290, 221229.
Mason, C.R., Maynard-Atem, L., Al-Harbi, N.M., Budd, P.M., Bernardo, P., Bazzarelli,
F., Clarizia, G., Jansen, J.C., 2011. Polymer of intrinsic microporosity incorporating thioamide functionality: preparation and gas transport properties.
Macromolecules 44, 64716479.
Maya, E., Tena, A., de Abajo, J., de la Campa, J., Lozano, A., 2010. Partially pyrolyzed
membranes (PPMs) derived from copolyimides having carboxylic acid groups.
Preparation and gas transport properties. Journal of Membrane Science 349,
385392.
McCaig, M., Paul, D., 2000. Effect of lm thickness on the changes in gas permeability
of a glassy polyarylate due to physical aging. Part I. Experimental observations.
Polymer 41, 629.
Meindersma, G., Kuczynski, M., 1996. Implementing membrane technology in the
process industry: problems and opportunities. Journal of Membrane Science
113, 285292.
Meinema, H.A., Dirrix, R.W., Brinkman, H.W., Terpstra, R.A., Jekerle, J., Kosters, P.H.,
2005. Ceramic membranes for gas separationrecent developments and state
of the art. Interceram: International Ceramic Review 54, 8691.
Merkel, T.C., Gupta, R., Turk, B.F., 2001. Mixed-gas permeation of syngas components
in poly(dimethylsiloxane) and poly(1-trimethylsilyl-1-propyne) at elevated
temperatures. Journal of Membrane Science 191, 8594.
Mikawa, M., Nagaoka, S., Kawakami, H., 2002. Gas permeation stability of asymmetric polyimide membrane with thin skin layer: effect of molecular weight of
polyimide. Journal of Membrane Science 208, 405414.
64
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
Mirfendereski, M., Sadrzadeh, M., Mohammadi, T., 2008. Effect of synthesis parameters on single gas permeation through T-type zeolite membranes. International
Journal of Greenhouse Gas Control 2, 531538.
Mokhatab, S., Poe, W.A., Speight, J.G., 2006. Handbook of Natural Gas Transmission
and Processing. Gulf Professional Publishing, Oxford.
Mulder, M., 2000. Basic Principles of Membrane Technology. Kluwer Academic
Publishers, Dordrecht.
Murphy, T.M., Langhe, D., Ponting, M., Baer, E., Freeman, B., Paul, D.R., 2011. Physical
aging of layered glassy polymer lms via gas permeability tracking. Polymer 52,
61176125.
Murphy, T.M., Offord, G.T., Paul, D.R., 2009. Fundamentals of membrane gas
separation. In: Drioli, E., Giorno, L. (Eds.), Membrane Operations: Innovative Separations and Transformations. WILEY-VCH Verlag GmbH & Co KGaA, Weinheim,
pp. 6382.
Nagai, K., Freeman, B.D., Hill, A.J., 2000. Effect of physical aging of poly(1trimethylsilyl-1-propyne) lms synthesized with TaCl5 and NbCl5 on gas
permeability, fractional free volume, and positron annihilation lifetime spectroscopy parameters. Journal of Polymer Science Part B: Polymer Physics 38,
12221239.
Nakagawa, T., Nishimura, T., Higuchi, A., 2002. Morphology and gas permeability
in copolyimides containing polydimethylsiloxane block. Journal of Membrane
Science 206, 149163.
Ng, B.C., Ismail, A.F., Abdul Rahman, W.A., Hasbullah, H., Abdullah, M.S., Hassan,
A.R., 2004. Formation of asymmetric polysulfone at sheet membrane for gas
separation: rheological assessment. Jurnal of Teknolologi 41, 7388.
Nord, L.O., Anantharaman, R., Bolland, O., 2009. Design and off-design analyses of
a pre- combustion CO2 capture process in a natural gas combined cycle power
plant. International Journal of Greenhouse Gas Control 3, 385392.
Ohlrogge, K., Wind, J., Brinkmann, T., 2002. Membrane Technology for Natural Gas
Processing. SPE Gas Technology Symposium, Calgary.
Okay, O., 2000. Macroporous copolymer networks. Progress in Polymer Science 25,
711779.
Omole, I.C., Adams, R.T., Miller, S.J., Koros, W.J., 2010. Effects of CO2 on a high performance hollow-ber membrane for natural gas purication. Industrial and
Engineering Chemistry Research 49, 48874896.
Park, H.B., Han, S.H., Jung, C.H., Lee, Y.M., Hill, A.J., 2010. Thermally rearranged
(TR) polymer membranes for CO2 separation. Journal of Membrane Science 359,
1124.
Park, H.B., Jung, C.H., Lee, Y.M., Hill, A.J., Pas, S.J., Mudie, S.T., Van Wagner, E., Freeman,
B.D., Cookson, D.J., 2007. Polymers with cavities tuned for fast selective transport
of small molecules and ions. Science 318, 254258.
Park, H., Lee, Y., 2008. Polymeric membrane materials and potential use in gas
separation. In: Li, N., Fane, A., Winston Ho, W., Matsuura, T. (Eds.), Advanced
Membrane Technology and Applications. John Wiley & Sons, Hoboken, pp.
633664.
Peng, N., Chung, T.-S., Chng, M.L., Aw, W., 2010. Evolution of ultra-thin denseselective layer from single-layer to dual-layer hollow bers using novel
Extem polyetherimide for gas separation. Journal of Membrane Science 360,
4857.
Pfromm, P.H., 2006. The impact of physical aging of amorphous glassy polymers
on gas separation membranes. In: Yampolskii, Y., Freeman, B., Pinnau, I. (Eds.),
Material Science of Membranes for Gas and Vapor Separation. John Wiley & Sons,
New York, pp. 293306.
Pfromm, P.H., Pinnau, I., Koros, W.J., 1993. Aging of thin polyimide ceramic and polycarbonate ceramic composite membranes. Journal of Applied Polymer Science
48, 21612171.
Pixton, M.R., Paul, D.R., 1995. Gas transport properties of adamantane-based polysulfones. Polymer 36, 31653172.
Polowinski, S., 2003. Template polymerization. In: Mark, H.F. (Ed.), Encyclopedia of
Polymer Science and Technology, vol. 12. Wiley-Interscience, New Jersey, pp.
130142.
Punsalan, D., Koros, W.J., 2005. Thickness-dependent sorption and effects of physical aging in a polyimide sample. Journal of Applied Polymer Science 96,
11151121.
Qiu, W., Chen, C.-C., Xu, L., Cui, L., Paul, D.R., Koros, W., 2011. Sub-Tg cross-linking
of a polyimide membrane for enhanced CO2 plasticization resistance for natural
gas separation. Macromolecules 44, 60466056.
Reijerkerk, S.R., Jordana, R., Nijmeijer, K., Wessling, M., 2011b. Highly hydrophilic,
rubbery membranes for CO2 capture and dehydration of ue gas. International
Journal of Greenhouse Gas Control 5, 2636.
Reijerkerk, S.R., Nijmeijer, K.R., Freeman, B.D., Wessling, M., 2011a. On the effects
of plasticization in CO2 /light gas separation using polymeric solubility selective
membranes. Journal of Membrane Science 367, 3344.
Ren, J., Chung, T.S., Li, D., Wang, R., Liu, Y., 2002. Development of asymmetric
6FDA- 2,6DAT hollow ber membranes for CO2 /CH4 separation 1. The inuence
of dope composition and rheology on membrane morphology and separation
performance. Journal of Membrane Science 207, 227240.
Ribeiro Jr., C.P., Freemana, B.D., Paulb, D.R., 2011. Pure- and mixed-gas carbon dioxide/ethane permeability and diffusivity in a cross-linked poly(ethylene oxide)
copolymer. Journal of Membrane Science 377, 110123.
Robeson, L.M., 1991. Correlation of separation factor versus permeability for polymeric membranes. Journal of Membrane Science 62, 165185.
Robeson, L.M., 2008. The upper bound revisited. Journal of Membrane Science 320,
390400.
Rodriguez, F., Cohen, C., Ober, C.K., Archer, L.A., 2003. Principles of Polymer Systems,
fth ed. Taylor & Francis, London.
Rolls, W., Svecand, F., Frechet, J.M., 1990. Design and synthesis of macroporous polymeric separation media based on substituted phenols. Polymer 31, 165174.
Roussenova, M., Murith, M., Alam, A., Ubbink, J., 2010. Plasticization, antiplasticization, and molecular packing in amorphous carbohydrate-glycerol matrices.
Biomacromolecules 11, 32373247.
Ruiz-Trevino, F.A., Paul, D.R., 1998. Gas permselectivity properties of high free volume polymers modied by a low molecular weight additive. Journal of Applied
Polymer Science 68, 403415.
Sanders, D.F., Smith, Z.P., Ribeiro Jr., C.P., Guo, R., McGrath, J.E., Paul, D.R., Freeman, B.D., 2012. Gas permeability, diffusivity, and free volume of thermally
rearranged polymers based on 3,3-dihydroxy-4,4-diamino-biphenyl (HAB) and
2,2-bis-(3,4-dicarboxyphenyl) hexauoropropane dianhydride (6FDA). Journal
of Membrane Science 409-410, 232241.
Scholes, C.A., Chen, G.Q., Stevens, G., Kentish, S.E., 2010a. Plasticization of ultra-thin
polysulfone membranes by carbon dioxide. Journal of Membrane Science 346,
208214.
Scholes, C.A., Smith, K.H., Kentish, S.E., 2010b. CO2 capture from pre-combustion
processesstrategies for membrane gas separation. International Journal of
Greenhouse Gas Control 4, 739755.
Schoots, K., Rivera-Tinocoa, R., Verbongb, G., van der Zwaan, B., 2011. Historical variation in the capital costs of natural gas, carbon dioxide and hydrogen pipelines
and implications for future infrastructure. International Journal of Greenhouse
Gas Control 5, 16141623.
Scott, K., Hughes, R., 1996. Introduction to industrial membrane processes. In: Scott,
K., Hughes, R. (Eds.), Industrial Membrane Separation Technology. Blackie Academic and Professional, London, pp. 17.
Shao, P., Dal-Cin, M.M., Guiver, M.D., Kumar, A., 2013. Simulation of membranebased CO2 capture in a coal-red powerplant. Journal of Membrane Science 427,
451459.
South, C.R., Weck, M., 2007. Template-enhanced ring-opening metathesis polymerization. Macromolecules 40, 13861394.
Speight, J.G., 2007. Natural Gas: A Basic Handbook. Gulf Publishing Company, Houston.
Staiger, C.L., Pas, S.J., Hill, A.J., Cornelius, C.J., 2008. Gas separation, free volume
distribution, and physical aging of a highly microporous spirobisindane polymer.
Chemistry of Materials 20, 26062608.
Starannikova, L., Khodzhaeva, V., Yampolskii, Y., 2004. Mechanism of aging of
poly[1-(trimethylsilyl)-1-propyne] and its effect on gas permeability. Journal
of Membrane Science 244, 183191.
Staudt-Bickel, C., Koros, W.J., 1999. Improvement of CO2 /CH4 separation characteristics of polyimides by chemical crosslinking. Journal of Membrane Science 155,
145154.
Stern, S.A., Vaidyanathan, R., 1990. Structure/permeability relationships of siliconcontaining polyimides. Journal of Membrane Science 49, 114.
Suzuki, T., Yamada, Y., Sakai, J., Itahashi, K., 2010. Physical and gas transport properties of hyperbranched polyimidesilica hybrid membranes. In: Yampolskii, Y.,
Freeman, B. (Eds.), Membrane Gas Separation. John Wiley & Sons, Ltd., West
Sussex, pp. 143158.
Tanaka, K., Okamoto, K., 2006. Structure and transport properties of polyimides
as materials for gas and vapor membranes separation. In: Yampolskii, Y., Pinnau, I., Freeman, B.D. (Eds.), Material Science of Membranes for Gas and Vapor
Separation. John Wiley & Sons, Ltd., West Susssex, pp. 271291.
Tin, P.S., Chung, T.-S., Liu, Y., Wang, R., Liu, S.L., Pramoda, K.P., 2003. Effects of crosslinking modication on gas separation performance of Matrimid membranes.
Journal of Membrane Science 225, 7790.
Toshima, N., 1992. Introduction to gas separation by polymers. In: Toshima, N. (Ed.),
Polymers for Gas Separation. VCH Publishers, Inc., New York, pp. 312.
Tullos, G., Powers, J., Jeskey, S., Mathias, L., 1999. Thermal conversion of hydroxycontaining imides to benzoxazoles: polymer and model compound study.
Macromolecules 32, 35983612.
Wadey, B.L., 2005. Plasticizers. In: Mark, H.F. (Ed.), Encyclopedia of Polymer Science
and Technology, vol. 3. Wiley-Interscience, New Jersey, pp. 498524.
Wang, H., Chung, T.-S., 2011. The evolution of physicochemical and gas transport properties of thermally rearranged polyhydroxyamide (PHA). Journal of
Membrane Science 385386, 8695.
Wang, H., Liu, S., Chung, T.-S., Chen, H., Jean, Y.-C., Pramoda, K.P., 2011. The
evolution of poly(hydroxyamide amic acid) to poly(benzoxazole) via stepwise
thermal cyclization: Structural changes and gas transport properties. Polymer
52, 51275138.
Way, J.D., Roberts, D.L., 1992. Hollow ber inorganic membranes for gas separations.
Separation Science and Technology 27, 2941.
Williams, P.J., Koros, W.J., 2008. Gas separation by carbon membranes. In: Li, N.N.,
Fane, A.G., Winston Ho, W.S., Matsuura, T. (Eds.), Advanced Membrane Technology and Applications. John Wiley & Sons Inc., New Jersey, pp. 599631.
Wind, J.D., Paul, D.R., Koros, W.J., 2004. Natural gas permeation in polyimide membranes. Journal of Membrane Science 228, 227236.
Xia, J., Chung, T.-S., Li, P., Horn, R.N., Paul, D.R., 2012. Aging and carbon dioxide
plasticization of thin polyetherimide lms. Polymer 52, 20992108.
Xiao, Y., Chung, T.-S., 2011. Grafting thermally labile molecules on cross-linkable
polyimide to design membrane materials for natural gas purication and CO2
capture. Energy and Environmental Science 4, 201208.
Xiao, Y., Low, B.T., Hosseini, S.S., Chung, T.S., Paul, D.R., 2009. The strategies of molecular architecture and modication of polyimide-based membranes for CO2
removal from natural gasa review. Progress in Polymer Science 34, 561580.
Yampolskii, Y., Starannikova, L., Belov, N., Gringolts, M., Finkelshtein, E., Shantarovich, V., 2010. Addition-type polynorbornene with Si(CH3)3 side groups:
J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665
detailed study of gas permeation, free volume and thermodynamic properties.
In: Yampolskii, Y., Freeman, B. (Eds.), Membrane Gas Separation. John Wiley &
Sons, Ltd., West Sussex, pp. 4357.
Yave, W., Car, A., Peinemann, K.-V., Shaikh, M.Q., Rtzke, K., Faupel, F., 2009. Gas
permeability and free volume in poly(amide-b-ethylene oxide)/polyethylene
glycol blend membranes. Journal of Membrane Science 339, 177183.
Yeong, Y.F., Wang, H., Pramoda, K.P., Chung, T.-S., 2012. Thermal induced structural rearrangement of cardo-copolybenzoxazole membranes for enhanced gas
transport properties. Journal of Membrane Science, 5165, 397398.
Yergin, D., 2011. Natural Gas. In: Armaroli, N., Balzani, V. (Eds.), Energy for a Sustainable World: From the Oil Age to a Sun-Powered Future. Wiley-VCH Verlag
GmbH & Co KGaA, Weinheim, pp. 6984.
Yong, W., Li, F., Xiao, Y., Li, P., Pramoda, K., Tong, Y.W., Chung, T.S., 2012. Molecular
engineering of PIM-1/Matrimid blend membranes for gas separation. Journal of
Membrane Science 407408, 4757.
65
Zhao, J., Wang, Z., Wang, J., Wang, S., 2006. Inuence of heat-treatment on
CO2 separation performance of novel xed carrier composite membranes
prepared by interfacial polymerization. Journal of Membrane Science 283,
346356.
Zhou, W., Watari, T., Kita, H., Okamoto, K., 2002. Gas permeation properties of
exible pyrolytic membranes from sulfonated polyimides. Chemistry Letters 5,
534535.
Zornoza, B., Irusta, S., Tellez, C., Coronas, J., 2009. Mesoporous silica spherepolysulfone mixed matrix membranes for gas separation. Langmuir 25 (10),
59035909.
Zornoza, B., Tllez, C., Coronas, J., 2011. Mixed matrix membranes comprising glassy
polymers and dispersed mesoporous silica spheres for gas separation. Journal
of Membrane Science 368, 100109.
Zou, J., Ho, W.W., 2006. CO2 -selective polymeric membranes containing amines in
cross-linked poly(vinyl alcohol). Journal of Membrane Science 286, 310321.