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International Journal of Greenhouse Gas Control 17 (2013) 4665

Contents lists available at ScienceDirect

International Journal of Greenhouse Gas Control


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

Review

Current challenges in membrane separation of CO2 from natural gas:


A review
J.K. Adewole a,b , A.L. Ahmad a, , S. Ismail a , C.P. Leo a
a
b

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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Corresponding author. Tel.: +60 45941012; fax: +60 45941013.


E-mail address: chlatif@eng.usm.my (A.L. Ahmad).
1750-5836/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijggc.2013.04.012

47
47
47
49
50
50
53
53
57
57
58
59
60
60
60
60
61
61
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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

Composition range (mol%)


0.01.8
0.2126.10
0.0642.66
0.03.3
29.9890.12
0.5514.22
0.2312.54
0.148.12
0.0373.0

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

PDMS means poly(dimethyl siloxane).

companies (Table 2). Two major processes in raw NG processing


are gas dehydration and gas sweetening (Mokhatab et al., 2006;
Scholes et al., 2010a,b). In gas sweetening, more research attention has been focused on the removal of CO2 due to its abundance
in the raw NG than H2 S (Table 1). CO2 removal will enhance the
energy content (caloric value) of NG, decrease the volume of gas
to be transported through pipeline and cylinders, prevent atmospheric pollution and reduces pipeline corrosion (Chew et al., 2010;
Mokhatab et al., 2006; Ren et al., 2002; Xiao et al., 2009). Thus
the removal of CO2 , which is the most prominent greenhouse gas
on earth (Mirfendereski et al., 2008) has both direct and indirect contribution to the control of atmospheric pollution. Removal
methods that are commonly used for CO2 include cryogenic distillation, adsorption, and membrane separation (Ahmad et al., 2008a,b,
2009; Chew et al., 2010; Kidnay et al., 2011; Meindersma and
Kuczynski, 1996). Among these methods, amine absorption is the
most developed commercial technology. However, high energy
consumption for solvent regeneration, equipment corrosion, and
ow problems caused by change in viscosity are some of the drawbacks that are militating against its continued usage (Ahmad et al.,
2008b; Chew et al., 2010; Merkel et al., 2001; Ohlrogge et al., 2002).
Therefore, there is need to seek alternative cost effective and energy
efcient technology such as membrane for CO2 removal. Today the
growth rate of membrane separation is higher than any of these
aforementioned methods (Baker, 2002). Ability to achieve higher
efciency of separation, be more capital efcient, yield faster separation coupled with the simplicity of operation in modern compact
modules and high space economy are some of the economic advantages of membrane gas separation which makes it attractive for
industrial application (Baker and Lokhandwala, 2008; Cao et al.,
2002; Ng et al., 2004; Reijerkerk et al., 2011a; Zhao et al., 2006). The
synergistic outcome of combining an energy efcient separation
technique for producing low carbon emission energy will go a long
way in addressing environmental issues relating to greenhouse gas
control.
1.2. Polymeric membrane gas separation
Membrane gas separation (MGS) technology involves the separation of individual gas component on the basis of the difference
in their rates of permeation through a thin membrane barrier
(Kohl and Nielsen, 1997). Several classication schemes have been
reported for placement of membrane materials into variety of
classes. Most common classes are organic (polymers) and inorganic

48

J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665

(ceramic, glass, metals, carbon molecular sieve and clay). Many of


the glassy polymers are known to have high selectivity but their
permeabilities are low and it may decline over time due to aging
(Hofmann and Tocci, 2009). On the other hand, most of rubbery
polymers exhibit high permeability but low selectivity and plasticization suppression properties. Inorganic membranes are capable
of given permselectivity that are ve to ten fold higher than that
of polymeric membrane at higher temperature, pressure and in
aggressive environment but they are very expensive for commercial applications (Koros and Mahajan, 2000). Generally, advantages
of using polymeric materials as membranes include: light weight,
processability into thin lms, porous beads, hollow bers and composites, and huge variations in structure and properties (Bernardo
et al., 2009; Toshima, 1992).
Grouping polymeric materials into a few categories about
which generalized statement can be made has made the study
of such complex topics as synthetic membrane an easy subject. Accordingly, polymeric membrane materials are further
subdivided into Rubbery (polymers above the glass-transition
temperature) and Glassy (polymer below the glass-transition temperature) (Rodriguez et al., 2003; Scholes et al., 2010a). In this
review, we have focused on polymeric membrane so as to keep
the subject under discussion to be more focused and manageable. However, interested readers are referred to recent review
and original articles on inorganic membranes (such as Zeolite,
Silica, Carbon Molecular Sieve and Ceramic) and mixed matrix
by Ahmad et al. (2008c,d, 2009), Ahn et al. (2010), Chew et al.
(2010, 2011), Chung et al. (2007), Cong et al. (2007), Ferrari
et al. (2010), Gavalas (2006), Golemme et al. (2010), Hibshman
et al. (2003), Hillock et al. (2008), Jana et al. (2012), Jiang
et al. (2006), Kita (2006), Koros and Lively (2012), Lee and Tsai
(2001), Li et al. (2007), Liu and Kulprathipanja (2010), Liu et al.
(2008), Meinema et al. (2005), Mirfendereski et al. (2008), Suzuki
et al. (2010), Way and Roberts (1992) and Zornoza et al. (2009,
2011).
Intensied efforts in research and technology innovations in the
1960s and 1970s led to large scale application membrane for gas
separation (Fried, 2003; Murphy et al., 2009). In 1989, a group of
six membrane experts were assigned the task of listing the research
priority topics in membrane technology, engineering and science.
Membrane materials for acid gas separation was ranked 12th out
of the 38 research topics constituting the research needs in the
membrane separation industry (Baker, 2010). Consequently, use of
membrane in CO2 removal from NG grew about tenfold since 1990
to become a $150 million/year business. However, amine absorption still has 90% of the NG processing market because todays
membranes are not good enough to displace the use of absorption
(Baker, 2010).

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

Selectivity CO2 /CH4

Reference

22.85
21.85
20.44
44
14
46.1
4.5

Askari et al. (2012a,b)


Askari et al. (2012a,b)
Askari et al. (2012a,b)
Kim et al. (2012)
Kim et al. (2012)
Han et al. (2010)
Yampolskii et al. (2010)

9.7
3.5
3.4

Staiger et al. (2008)


Nakagawa et al. (2002)
MedArray, Inc.

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

Expanded capacity (MMSCFD)

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)

6FDA-DAM: DABA 2:1

Mixed (50% CO2 )

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

Plasticization pressure (atm)

Mixed (50% CO2 )

Cross-linked with
benzenedimethanol
monoester

295

43

37

33

6FDA-6FpDA: DABA 1:2

Mixed (50% CO2 )

Cross-linked with ethylene


glycol monoester

220

24

47

27

6FDA-DAM: DABA 2:1

Multi-component
mixtures

Annealing

220

47

2328

>40

5055

2327

>10

painful problems in real time applications of membrane (Wind


et al., 2004).
Several approaches such as thermal treatment, polymer blending, reactively formed interpenetrating networks, cross-linking,
thermal rearrangement, mixed matrix and various novel spinning processes have been suggested and investigated for possible
enhancement in separation performance of polymeric membranes
for gas separation. Consequently, the need for information on the
progress and challenges resulting from such investigations cannot
be over emphasized.
The objective of this review is therefore to present the current
scientic and technological progresses that have been made in the
area of development of new material and improvement of existing ones. Comprehensive reviews of the results obtained from the
suggested methods for developing materials with better balanced
of productivity and selectivity, and improved resistance to plasticization, conditioning and physical aging are discussed. It also
highlights factors that are presently serving as bottleneck towards
achieving better material performance for NG processing and give
potential membrane materials for further research in this area.
While we do not claim to have presented an exhaustive review
of all the available literature results on new membrane materials
and fabrication technologies, we have ensured that some of the
most important representative membrane materials and emerging
methods of fabrication have been discussed in order to demonstrate the state-of-the-art research in material development for
membrane separation. This paper is believed to be a good reference work and sources of data for gas membrane system design
and future research for membrane material development.

membranes at the high pressure interface, then diffuse through


the membrane and later desorbed at the low pressure (Mulder,
2000; Park and Lee, 2008). According to this model, movement
of gas molecules through polymeric membranes is controlled by
diffusivity coefcient (D) and solubility coefcient (S). Diffusivity
coefcient is a kinetic parameter that measures the mobility of individual molecules through the polymer chains. The solubility is a
thermodynamic parameter that provides information on the sorption uptake in the membranes (Hagg, 2009). Thus, the permeability
(P), which represents the ability of the molecules to pass through
a membrane, is dened as the product of diffusivity coefcient and
solubility coefcient:
P = DS

(1)

Permeability is commonly measured in barrer and conversion


to other unit is 1 barrer = 1 1010 cm3 (STP)cm/(cm2 scmHg) =
7.5005 1018 m2 s1 Pa1 ) (Li and Chung, 2008). The ability of a
membrane to separate a mixture of two gas components (A and B)
is the ratio of their permeabilities. This ratio is often referred to as
the permselectivity or selectivity (AB ).
AB =

PA
PB

(2a)

Eq. (2a) is a representative model for calculating permselectivity


(ideal selectivity) of membrane based on pure (single) gas permeation experiment. For mixed gas permeation experiment, the mixed
gas selectivity (the separation factor) is often calculated using the
following expression (Chew et al., 2010; Hillock et al., 2008; Koros
et al., 2009; Zou and Ho, 2006):
Separation factor

1.3. Fundamental of gas separation in polymer membranes


Solution-diffusion mechanism is the most commonly used theory for describing gas permeation through non-porous dense
polymers. In this mechanism, gas molecules are rst sorped by the

(Composition of A downstream/Composition of B downstream)


(Composition of A upstream/Composition of B upstream)

(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)

The ratio DA /DB is called the mobility or diffusivity selectivity while


SA /SB is called the sorption or solubility selectivity (Liu et al., 2008;
Park and Lee, 2008).
It is noteworthy to mention that parameter that is used
for expressing membrane performance depends on the type of
membrane module. For hollow ber membranes, the separation
performance is commonly expressed in term of permeance. The
permeance of a hollow ber membrane to gas A is the permeability of the membrane (PA ) divided by the membrane thickness (L).
Mathematically,
Permeance =

PA
L

PA (denselm

(P/L)A (dual-layer

(5)

hollow ber membrane)

Accordingly, the selectivity is expressed as:

AB =

(P/L)A
(P/L)B

(6)

The unit commonly used for expressing permeance is GPU (1


GPU is equivalent to 1 106 cm3 (STP)/(cm2 scmHg) or 7.5005
1012 m s1 Pa1 ) (Li and Chung, 2010; Aroon et al., 2010). Eq. (4) is
also used to compare the permeabilities of asymmetric composite
membranes whose thickness are unknown (Tanaka and Okamoto,
2006).
The temperature dependence of diffusion coefcient of gas A in
polymer membrane is expressed using the activated relationship
similar to the Arrhenius equation (Adewole et al., 2012a; Park and
Lee, 2008):
DA = DA0 exp

 E 
D

RT

(7a)

where DA is the diffusion coefcient (cm2 /s), DA0 is pre-exponential


factor, ED is the activation energy of diffusion (kJ/mol), R is the
universal gas constant (8.31 J/mol), and T is the temperature in K.
Similarly, the solubility (SA ) can be expressed as a function of
temperature using the vant Hoff relationship:
SA = SA0 exp

 H 
S

RT

(7b)

SA0 is the pre-exponential factor, HS is the enthalpy of solution


of the gas. By substituting ((7a) and (7b)) into (1), a temperature
dependent model for permeability of a penetrant A can be written
as:
PA = PA0 exp

 E 
P

RT

(7c)

and
EP = ED + HS

S = kD +

CH  b
1 + bp

(8a)

where kD is Henrys law constant, CH  is the Langmuir capacity


constant, and b is the Langmuir afnity constant.
Using the extended form of this model, permeability of a gaseous
penetrant can be written as (Murphy et al., 2009):
P = kD DD +

CH  bDH
1 + bp2

(8b)

where DD and DH are diffusion coefcients for gas molecules


absorbed by Henry and Langmuir modes of sorption, respectively.

(4)

For dual-layer hollow ber, L is the dense-selective layer thickness and can be determined as follows (Li and Chung, 2010):
L=

permeabilitypressure relation is presented in subsequent section


of this review. For rubbery polymer, the simple solution-diffusion
model is sufcient to describe gas transport behaviour. Unlike rubbery polymers, gas transport behaviour in glassy polymers is more
complicated. Thus, changes in gas permeability as function of pressure is often explained using the dual-mode model and partial
immobilization models (Park and Lee, 2008). In this model, solubility is expressed as:

(7d)

where PA0 is the pre-exponential factor and EP is the activation


energy of permeation.
Transport of gases in polymer is also affected by variation
in feed pressure. Detailed description of the phenomenon of

2. Achieving better balance of gas selectivity and


permeability
The ability to achieve a higher permeability without compromising selectivity has been recognized as one of the routes
to expanding the market for gas membrane materials. Generally, structural modication to increase permeability unfortunately
leads to loss of permselectivity (Pixton and Paul, 1995) (Fig. 1). This
is a well known trade-off between membrane permeability and
permselectivity. In order to formulate a bench mark, an empirical upper-bound relationship between selectivity and permeability
was proposed by Robeson (1991) above which no materials was
once known to exist (Fig. 2a). Following a further study of the Robesons Upper Bound Curves by Freeman (1999), it was suggested that
to surpass the upper bound emphasis should be placed on increasing the selectivity by inter-chain spacing and chain stiffness. About
seventeen years later, the upper bound was again reviewed by
Robeson (2008) with more data from literature (Fig. 2b). Actually,
it took some time and skillful design of polymer molecular structure before material scientists were able to produce membrane
that exceeded the trade-off. Today, while many polymeric materials have surpassed the 1991 bound, the 2008 upper bound have
been surpassed by only very few polymers. Some of these polymers
include cross-linkable 6FDA-durene/DABA co-polyimides grafted
with , , and cyclodextrin (Askari et al., 2012a); polymers of
intrinsic microporosity (PIM) (Budd et al., 2008, 2010); thermally
rearranged aromatic polyimides (Park et al., 2010), polybenzoxazole (Kim et al., 2012); microporous polybenzimidazole (Han et al.,
2010), and poly(benzoxazole-co-pyrrolone) (Choi et al., 2010).
Nowadays, exceeding the Robeson bound is not always the utmost
target but it is always shown to supplement the supperiority of
the transport properties of a fabricated membranes. The prevailing
utmost concern of membrane material scientists in gas separation
are penetrant-induced plasticization, conditioning and physical
aging.
3. Plasticization, conditioning and physical aging
In polymer processing, low molecular weight compounds
(LMWC) are often introduced into glassy polymers in order to
improve their processability (Wadey, 2005). The LMWC that are
introduced to obtain a more exible polymer with increased rate
of segmental motion than the pure polymer are referred to as plasticizers. The phenomenon of increased chain exibility is called
plasticization (Lee et al., 2012b; Roussenova et al., 2010). On the

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).

other hand, the addition of LMWC at relatively low concentration


can lead to loss in free volume and subsequently retard segmental
mobility of polymer chains. In this case, LMWC are referred to as
antiplasticizers (Larocca and Pessan, 2003). Since this phenomenon
is opposite of what is expected for plasticization, it is often called
antiplasticization (Larocca and Pessan, 2003; Lee et al., 2012b; RuizTrevino and Paul, 1998). In membrane gas separation processes,
plasticization is dened as pressure dependent phenomena caused
by the dissolution of certain penetrants within the polymer matrix
which disrupts the chain packing and enhance inter-segmental
mobility of polymer chains (Xiao et al., 2009). Antiplasticization is
usually used to refer to the mechanism of membrane performance
degradation in the presence of aggressive feed streams (Lee et al.,
2010a). Detailed investigation on impact of both plasticization and
antiplasticization phenomena on observed loss in membrane transport properties and performance on exposure to highly sorbing feed
gas stream was performed by Larocca and Pessan (2003), Lee et al.
(2010a,b), Maeda and Paul (1987a,b,c,d).
The effect of the presence of plasticizer on gas permeability
in polymer membranes was demonstrated by Flaconnche and
Klopffer (2001) by incorporating a platicizing agent in the form
of n-butyl-benzene sulfonamide. Also, a carefully dened experiment was used by Horn and Paul (2011a,b) to explore the inuences
of lm thickness on CO2 -plasticization and conditioning in glassy
polymers. Results from the studies carried out by Cui et al. (2011)
and Xia et al. (2012) on aging and CO2 -plasticization indicated
that the plasticization and physical aging phenomena are function of lm thickness, aging time, exposure time, pressure and
prior history. At this juncture, it is worthy of note to mention

that plasticization and antiplasticization are two important terms


of practical use in membrane separation. Both terms are used to
describe changes in thermal, mechanical and gas permeation properties of membrane materials (Immergut and Mark, 1965; Koros,
1991; Roussenova et al., 2010). In this review, attention is focused
on progress in plasticization suppression in membrane gas separation operations. In gas separation, plasticization behaviour can
be induced by condensable gases which include CO2 , hydrocarbon
and other organic vapours. CO2 -induced plasticization remains a
painful problem commonly encountered in gas separation involving aggressive feed streams, such as in NG stream (Qiu et al.,
2011; Wind et al., 2004). At low pressure, the permeability of polymers usually decreases with increase in pressure due to volume
relaxation and gradual saturation of microvoids in the membrane
(Murphy et al., 2009; Reijerkerk et al., 2011b; Xiao et al., 2009).
Plasticization occurs at high partial pressure (concentration) of CO2 .
When this phenomenon sets in, CO2 increases the mobility of polymer chain segments, thereby increasing the diffusion coefcients
of all penetrants in the membrane (Murphy et al., 2009). Plasticization causes an increase in permeability and a decrease in selectivity
as the partial pressure of plasticizing penetrant rises beyond a critical level. The pressure at which the permeability starts to increase
with increasing pressure is referred to as the plasticization pressure
(Fig. 3). Correspondingly, it is also the pressure at which gas permeability exhibits a minimum value (Scholes et al., 2010a; Xiao et al.,
2009). At this pressure, membrane performance begins to decline
and this negatively impacts process economics due to increased
methane loss and decline in process reliability (Wind et al., 2004).
In addition to plasticization, glassy polymers are also affected by

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

Polyethylene oxide (PEO)

Permeability in PSF (Barrer)

16
14

12
10

8.5

8
8

Plasticization Pressure

7.5
Minimum Permeability

Permeability in PEO (Barrer)

18
9.5

2
6

10

12

14

16

Feed Pressure (atm)


Fig. 3. Permeability of CO2 as a function of feed pressure in Glassy PSF and rubbery
PEO.
Data used for this plot were obtained from Scholes et al. (2010a); and Lin and
Freeman (2004) and copied from Adewole and Ahmad (2012).

conditioning. Membrane conditioning involves sorbing sizeable


quantities of penetrant into glassy polymer which alters its state of
the glass in such a way that after removal of the penetrant the membrane does not return to its original state (Murphy et al., 2009). The
phenomenon permanently changes the morphology and transport
properties of membrane due to irreversible volume dilation (Xiao
et al., 2009).
Polymers below their glass transition temperature are known
to be in their state of nonequilibrium (Chung and Kafchinski, 1996;
Murphy et al., 2009). A gradual molecular rearrangement process
of polymers toward attaining a state of equilibrium is termed physical aging (Xiao et al., 2009). During this rearrangement properties
such as density, refractive index, free volume and gas permeability are affected. Usually, variances are observed in reported glassy
polymer properties. On a macroscopic level, these variances are
so small that they can be neglected (Murphy et al., 2009). However, recent studies showed that the aging phenomenon can be
signicantly pronounced in thin lms due to their more rapid evolution toward the equilibrium state. Physical aging of thin lms
are most often observed in terms of volume relaxation or densication (Murphy et al., 2009). Polymer properties such as free
volume and permeabilities are affected by densication. Resulting
changes in these properties can be very signicant on time scale
of weeks to years. For example, the apparent activation energy of
permeation of CO2 increases due to increase in both the activation
energies of diffusion (ED ) and heats of solution (HS ). Increase in
ED is due to decrease in molar volume as a result of densication
during aging. Also, the observed increase in solubility coefcient is
attributed to decrease in the available number of sites for sorption
which results from decrease in microvoids and interstitial chain
space (Lin and Chung, 2001). Thus, it is expected that productivity
of commercial polymer membrane modules will decline signicantly over their life time of several years due to physical aging.
This in turn affects the reliability of the membrane performance and
hinders commercialization of membrane for industrial separation
(Xiao et al., 2009).
Denitely, it is beyond the scope of this review to go into
detailed explanation of the physics involved in the mechanism
of aging which has already been presented elsewhere (Murphy
et al., 2009; Pfromm, 2006; Xiao et al., 2009). Rather, our focus
is directed towards reviewing the advancements that have so far
been achieved in understanding the mechanism of aging and providing ways of alleviating the problem. Several methods have been
investigated for tracking physical aging in polymer membrane.

These include; change in permeability, activation energies and


heat of solutions (Pfromm, 2006), change in density and change
in free volume distribution (Lin and Chung, 2000; Pfromm, 2006)
and change in optical properties (Huang and Paul, 2006). Due
to the high sorbing nature of CO2 and to distinguish the phenomenon of plasticization and conditioning from aging using gas
permeability tracking, O2 , CH4 and N2 are always used to investigate the phenomenon of aging in polymer membranes (Cui et al.,
2011; Horn and Paul, 2011a,b; Huang and Paul, 2004a; Staiger
et al., 2008). Almost all the research works on aging are focused
on study the mechanism and their effects on separation performance. For example, mechanism of polymer aging in PTMSP and
its effect on gas permeability was investigated by Starannikova
et al. (2004). The authors investigated various types of aging including chemical aging (by oxidation), physical and absorption aging
using PTMSP samples obtained from various catalysts such as
TaCl5 /BuLi, TaCl5 /i-Bu3 Al and NbCl5 . The samples were stored at
ambient temperatures for 28 years. It was observed that the
absorption aging was the main contributor to the decrease in gas
permeability of the aged polymer. Accordingly, the authors suggested that re-precipitation followed by a subsequent recasting
can be used to eliminate the effect of absorption aging. Huang
and Paul (2004a) developed experimental methodologies for studying the physical aging of free-standing polymer thin lms. This
method was used to study the physical aging of polysulfone samples fabricated by both solution casting and spin coating methods.
Also, Huang and Paul (2004b) used the developed methodologies to study the physical aging of polysulfone, polyimide and
poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) by tracking the permeabilities of O2 , N2 and CH4 gases in the three glassy polymers
for 200 days. The pronounced decrease in the gas permeability over time was reported to have been due to physical aging.
The author also investigated the effect of crystalinity of PPO on
physical aging and results obtained showed that it has little or
no effect. The work of Staiger et al. (2008) was focused on the
measurement of pore size distribution and physical aging of Spirobisindane polymers and comparison of the results obtained with
that of traditional high free volume polymers such as PTMSP,
Teon and PMP. Aging experiment was performed using O2 permeability. Murphy et al. (2011) investigated the physical aging of
polymers in conned environment by tracking the change in permeability of O2 and N2 in polymer lms with alternating glassy
polysulfone and rubbery polyolen layers. Their results showed
that the physical aging of free standing polysulfone lm is rapid
and thickness dependent while that of multilayered lms was
independent of layer thickness. The effect of catalyst type (TaCl5
and NbCl5 ) on physical aging of PTMSP lms was investigated by
Nagai et al. (2000) using permeability of CH4 in the polymer. The
authors also demonstrated the restoration of gas permeability of
aged polymer by soaking it in methanol. Apart from permeability, solubility and diffusivity have also been employed to evaluate
the relationship between transport property of polymer membranes and physical aging. For example, a study by Punsalan and
Koros (2005) was focused on direct observation of gas sorption
isotherm in thick and thin samples. The authors observed significant differences in gas solubility due to the lm thickness and
aging time. In fact, Horn and Paul (2012) did a comprehensive
study on CO2 permeability, sorption and diffusivity as function of
CO2 pressure and exposure time using optical methods. In their
study, a spectroscopic Ellipsometry was used to simultaneously
measure the polymer lm thickness and CO2 sorption capacities
of thin lms of Matrimid 5218, polysulfone made from bisphenol A, Poly(2,6-dimethyl-1,4-phenylene oxide), and commercial
polystyrene (Styron 685d). Generally, Ellipsometry and positron
annihilation lifetime spectroscopy (PALS) are commonly used for
evaluating the physical aging of glassy polymer. This is done by

J.K. Adewole et al. / International Journal of Greenhouse Gas Control 17 (2013) 4665

taking an accurate measurement of lm thickness and refractive


index (Murphy et al., 2009).
4. Techniques for improving separation performance of
polymeric membranes
In principle, the availability of large number of monomers
is expected give to rise to the production of endless number
of polymers through polymerization. However, development of
new polymeric membranes with specic properties via polymer
modication is reported to be less costly and can be achieved
more readily than through synthesis of new polymers (Ebewele,
2000). Several polymer modication techniques have been suggested and investigated for improving the separation performance
of polymeric membranes. These include: crosslinking and thermal treatment (Kanehashi et al., 2010; Qiu et al., 2011) such
as decarboxylation-induced thermal cross-linking (Kratochvil and
Koros, 2008), cross-linking by diamino compounds at ambient
temperature (Chen et al., 2012), monoesterication and transesterication reaction of carboxylic acid, imide ring opening
reactions, and diols-alder type cyclization reactions; copolymerization (Nakagawa et al., 2002; Xiao et al., 2009); polymer sulfonation
(Khan et al., 2011); template polymerization and use of porogens
(Askari et al., 2012a); thermal rearrangement (Choi et al., 2010;
Kim et al., 2012; Park et al., 2007, 2010; Tullos et al., 1999); polymer blending (Hosseini et al., 2010; Xiao et al., 2009); mixed-matrix
(Adewole et al., 2012a; Chung et al., 2007; Koros et al., 2009); grafting of polymer backbone (Bhattacharya and Misra, 2004; Pixton
and Paul, 1995; Scholes et al., 2010a); and dual-layer hollow ber
spinning process (Hosseini et al., 2010). This section is devoted to
progresses that have so far been achieved on improved gas separation performance for polymer membranes.
4.1. Cross-linking and thermal treatment techniques
Crosslink was dened by IUPAC as a small region in a macromolecule from which at least four chains emanate, and formed by
reactions involving sites or groups on existing macromolecules or
by interactions between existing macromolecules (Jenkins et al.,
1996). It is a formation of intermolecular connections through
chemical bonds. The necessity for the development of membrane
materials that can withstand the swelling and plasticization caused
by the presence of CO2 at high concentration made researchers
to investigate the use of cross-linking in order to curb this problem. Generally, cross-linking methods that are widely applied
for improving the membrane properties include chemical crosslinking, thermal treatment, and photochemical cross-linking by
ultraviolet and ion beam irradiations (Askari et al., 2012a; Scholes
et al., 2010a,b; Tin et al., 2003; Xiao et al., 2009). These methods
have been adopted in various ways to achieve better separation performance for membranes. For example ester crosslinking,
decarboxylation-induced thermal cross-linking, cross-linking by
diamino compounds at ambient temperature, monoesterication,
transesterication reaction of carboxylic acid, imide ring opening reactions, grafting with epoxy reactions, and diols-alder type
cyclization reactions were adopted to enhance the plasticization
suppression properties of membrane materials (Kanehashi et al.,
2010; Qiu et al., 2011). Cross-linking process leads to a reduction
in chain mobility accompanied by a consequent increase in Tg .
Today, crosslinking have been successfully employed to produce
membranes with tunable transport properties that offer significantly higher performance with better plasticization and aging
resistance than that for the commercial polymers Matrimid and
cellulose acetate for removing CO2 from NG mixtures (Wind et al.,
2004). Crosslinking a polymer membrane is expected to increase

53

the pressure at which plasticization occurs, thus stabilizing the


membrane at higher partial pressure of CO2 (Kratochvil and Koros,
2008). Thermal annealing has been used to obtain higher packing
density, smaller free volumes, slightly higher Tg and suppression of
CO2 -induced plasticization.
Polyamides and other specialty polymers are one of the
most widely investigated polymers for gas membrane separation.
Research efforts to produce a synthetic material with similar characteristics as naturally occurring proteins were dated back to 1890s
(Rodriguez et al., 2003). Nylon 66 was commercialized before 1940
and since then polyamide has continued to grow in its importance. Today, polyimides constitute one of the most widely studied
polymer family for membrane gas separation. Polyimides and polybenzimidazole are two related polymer families that combine chain
stiffness with thermal stability which makes them suitable for wide
range of engineering applications. For more than two decades,
polyimides have become increasingly popular polymer membrane
materials for research in gas and vapour separation. It is used in
aggressive feed separations such as NG separations with a high CO2
content (Kratochvil and Koros, 2008). This is due to its excellent
thermal, chemical, mechanical and high membrane gas separation
properties (Tanaka and Okamoto, 2006). Moreover, researchers
have also taken the advantage of polyimides excellent lm forming properties as well as the relative ease in preparing polyimides
with variety of different chemical structures (Tanaka and Okamoto,
2006). It is worthy of mentioning that the rst commercial application of polyimide for membrane gas separation was done by
Du Pont in 1967 for Helium separation from NG and the application was subsequently extended to CO2 removal from various
gas mixtures (Xiao et al., 2009). Detailed information on molecular architectures, design and the effect of chemical structure on the
permeation properties of various polyimides can be found in Xiao
et al. (2009) and Tanaka and Okamoto (2006).
Judging by the high number of publications on cross-linked
polyimide (PI), it is evident that these polymers have attracted
the attention of researchers due to its excellent separation properties (Kanehashi et al., 2010). Moreover, PIs are excellent membrane
materials owing to their rigid chemical structure which allows for
the production of larger fractional free volume (Kanehashi et al.,
2010). One of the early works to determine if swelling and plasticization can be reduced by cross-linking was done by Staudt-Bickel
and Koros (1999). The authors focused on the study of simultaneuos inhibition of chain mobility and intrasegmental packing
by changes in the backbone structure. Polyimides with strong
polar associating functional groups as well as chemical cross-linked
polyimides and copolyimides were synthesized and permselectivity and permeability properties of CO2 /CH4 separation were
investigated. Permselectivity of CO2 /CH4 was enhanced by 6FDAbased polyimides which contains C(CF3 ) linkages.The author also
investigated the effects of the strong polar carboxylic groups on
separation properties of CO2 /CH4 . The inuence of the degree of
crosslinking on CO2 induced swelling and plasticization was studied up to 41atm pure CO2 pressure using both the conventional
crosslinking with Ethylene glycol in DMAc as cross-linking agents
and cross-linking by post treatment. It was concluded that incorporation of polar associating functional groups such as COOH
in polyimide structures leads to strongly reduced permeability.
However, the CO2 induced plasticization can be reduced due to
crosslinking of the polyimides.
NG permeation in 6FDA-DAM:DABA and 6FpDA:DABA copolymers membranes was studied by Wind et al. (2004). Cross-linked
polyimides copolymers were used to separate 50/50 CO2 /CH4
mixtures and multicomponents NG mixtures at 35 C and a feed
pressure up to 55 atm. The cross-linking was done at various
temperature ranging from 220 C to 295 C with 1,4-butylene glycol and 1,4-cyclohexanedimethanol as cross-linking agents while

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

Decarboxylation at high Temperature


Rapid Quenching from above Tg

6FDA-DAM:DABA (2:1)
6FDA-DAM:DABA (2:1)

Perm CO2 (Barrer)


9
7.5
7
11
0.65a
0.64a

Plasticization pressure (atm)


57
24
15
36
2532
>49

Permeability was normalized with respect to the initial permeability measurement taken at 2 atm.

annealing was done at temperatures between 130 and 295 C.


The effect of thermal treatment and covalent cross-linking were
decoupled with respect to their effects on separation performance
of the membrane. The multicomponent gas mixtures consist of the
following (in mol%): CO2 (30.0130.02), CH4 (61.062.95), C2 H6
(3.994.0), C3 H8 (2.993.0), C4 H10 (2.01) and Toluene (0.0299)
while the mixed gas is 50 mol% each of CO2 and CH4 . Membranes
obtained from these studies exhibit higher transport properties and
better plasticization resistance than commercial polymers such as
Matrimid and cellulose acetate. Table 6 shows the summary of the
results of its plasticization resistance properties. Results from this
table showed that both the covalent cross-linking and the thermal
annealing are effective for suppressing CO2 -induced plasticization.
In a similar study (Omole et al., 2010), performance of propane-diol
monoesteried cross-linkable polyimide (PDMC) was investigated
in form of asymetric hollow ber membranes. Separation performance of PDMC was studied under aggressive high CO2 content
mixed gas feeds. It was observed that the cross-linked membranes
showed a good performance in NG purication. Plasticizisation was
effectively suppressed. However, this was accompanied with a drop
in membrane productivity. The reduction in productivity was said
to be due to densication in the selective skin layer during annealing of the membrane.
An extremely simple room temperature chemical cross-linking
technology for the modication polyimide was developed by Liu
et al. (2001). This technology was tested on 6FDA-durene using
a p-xylenediamine methanol solution as cross-linking agent. Gas
permeation properties of the modied polyimides to He, O2 , N2
and CO2 were investigated at 35 C and 10 atm. However, transport
property of CH4 and CO2 -induced plasticization were not investigated. Tin et al. (2003) applied this technology to chemically
modify a commercially available polyimide (Matrimid 5218). Pure
and mixed gas permeation tests were performed for CH4 and CO2
gases. In addition, the effect of cross-linking on CO2 -induced plasticization phenomenon was evaluated. The results showed that
plasticization pressure increased by more than 100% (from 15
to 32 atm) after polymer cross-linking for 7 days. However, this
increase was accompanied by 45% decrease in permeability and
a practically constant ideal selectivity. The use of rapid quenching to solve the problem of reduced permeability as a result of
cross-linking has been investigated. Rapid quenching does not only
solve the reduced permeability problems but also improve the
plasticization resistance. For example, decarboxylation-induced
cross-linking was employed by Kratochvil and Koros (2008) to
enhance CO2 plasticization resistance of 6FDA-DAM:DABA (2:1)
copolyimides. One of the resulting polymer lms was annealed
and the other one was rapidly quenched from above Tg . Both
samples were then tested for gas permeability and solvent dissolution. The rapidly quenched sample was found to exhibit enhanced
CO2 plasticization resistance from 28 atm to more than 49 atm
(Table 7). The normalized CO2 permeability was stable up to 49 atm.
Moreover, the samples did not redissolve in solvents such as cyclohexanone, THF, and NMP which were known solvents for dissolving
polyimides. In fact, the quenched lm remained undissolved after

boiling in NMP for 18 h. Both responses were concluded to be due


to cross-linking which occurred in the polymer.
Literature report has revealed that the use of chemical crosslinking has its challenges. For instance, diol cross-linking agents
formed ester linkages through a carboxylic acid pendant group.
The ester linkages formed may be hydrolyzed in aggressive acid
gas feed streams which would reverse the effects of cross-linking,
greatly reduce the separation efciency of the membrane and
make it susceptible to plasticization (Kratochvil and Koros, 2008).
This problem was solved using a new cross-linking approach that
prevents the formation of the vulnerable ester linkages. The mechanism of the new approach involves the decarboxylation of the
acid pendant of the polymer at high temperature and creation of
free radical sites capable of cross-linking without diol cross-linking
agent.
Again, one of the major disadvantages of decarboxylation at high
temperature is that it may result in collapse of substructure and
transition layers in asymmetric structures of a hollow ber membrane fabricated from these materials. To overcome this problem,
Qiu et al. (2011) developed a thermal cross-linking technique in
which polymer can be cross-linked at temperatures much below
its glass transition. The sub-Tg cross-linking is a step towards a
large scale production of asymetric membranes. Polyimide 6FDADAM:DABA (3:2) was synthesized through polycondensation of
dianhydride with diamine. Resulting membrane lms was characterized with solubility testing, thermal analysis and permeation
tests with aggressive gas feed streams at higher pressure using
both pure and mixed gases of CO2 /CH4 . Reuslts obtained showed
an improvement in the plasticization pressure of the membranes
(Figs. 46). Some of the membanes were found to be insoluble in
hot NMP at high temperature of 100 C for 1 week. Variation in the
condition of thermal treatment was used to reveal the tempearture above which cross-linking was observed (Qiu et al., 2011).
The results obtained showed that there was no cross-linking at
temperature below 300 C.
Actually, samples with plasticization pressure of 48 bar did not
show any sign of plasticization up to the highest feed pressure

Fig. 4. Separation performance of decarboxylation-induced thermal cross-linking


of hollow ber 6FDA-DAM:DABA (3:2) membrane for pure CO2 gas.
Qiu et al. (2011).

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

6FDA-ODA (50%)-TemMPD (50%)

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).

of 48 bar employed in the study. The continuous decrease in CO2


permeability with increasing upstream pressure is a characteristic
evident of non plasticization behaviour. It is most likely expected
that the sample would maintain its plasticization resistance properties at higher feed pressure. Furthermore, in this study, mixed
gas permeation properties was also conducted at 69 bar upstream
pressure with 10.3% and 50.0% CO2 contents to investigate the
effect of cross-linking. This is important because, once plasticization pressure is reached, the pure gas permeation test is no longer
a good representative of the membrane performance. Again, it
should be noted that 69 bar was the maximum pressure employed
by the authors, thus it is most likely the plasticization pressure
is more than 69 bar and this is another area that needs further

Fig. 6. Separation performance of decarboxylation-induced thermal cross-linking


of hollow ber 6FDA-DAM:DABA (3:2) membrane for 50%CO2 /50% CH4 gas.
Qiu et al. (2011).

investigation. In both cases, the separation factor decreased with


increasing feed pressure. The results also showed that the crosslinked membrane showed higher CO2 permeability than the
uncross-linked membrane. Clearly, the outcome of this research
showed that such membrane will be benecial for CO2 /CH4 separation applications.
A new cross-linking agent, diamino-organosilicone (bis(3aminopropyl)-tetramethyldisiloxane)) (APTMDS), was proposed
by Chen et al. (2012) for producing cross-linked polyimides membrane for CO2 /CH4 separation. Two approaches were employed by
the authors to produce homopolyimides and copolyimides (6FDAODA and 6FDA-ODA (50%)-TemMPD (50%)) membrane which
include direct mixing of the crosslinking agent in the polyimide
solution and immersing the PI in an APTMDS/methanol solution.
One of the uniqueness of this method is its implementation at ambient temperature. As usual, the cross-linking method was shown to
effectively decrease permeability of the polymer while the ideal
selectivity and the separation factor of the membrane for CO2 /CH4
separation was found to increase. Tables 8 and 9 showed the
summary of the results obtained. Overall, both methods investigated were observed to yield enhanced membrane properties. The
immersion was however recommended for industrial scale application due its ease of implementation. Samples of both types of
membrane were shown to possess selectivity higher than the Robeson upper bound curve.
Apart from PI, other polymers have also been investigated for
use in fabricating the platicization resistant membrane materials for gas separation application. Example of such polymer is
Poly[1-(trimethylsilyl)-1-propyne] (PTMS) which is a stiff chain
glassy polymer with exceptionally high free volume of about

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

Permeability of CO2 (Barrer)

Plasticization pressure (atm)

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)

Temperature at which partial pyrolysis takes place.

0.29. It belongs to the family of polyacetylenes. Kelman et al.,


2008 investigated the effect of cross-linking (PTMS) on its solvent
resistance and physical aging by using a commercially available 3,3 -diazidodiphenylsulfone as the cross-linking agent. It was
observed that the cross-linked polymer was insoluble in toluene,
cyclohexane and tetrahydrofuran (THF) which are known solvent
for dissolving uncross-linked PTMS. The polymer lm was soaked
in toluene for two (2) years and it remained insoluble after the long
exposure period. Pure gas permeation of CO2 and CH4 in PTMS was
performed at 35 C and 4.4 atm upstream pressure. In contrast to
improvement in solvent resistance, the results obtained from the
studies of gas permeability as a funtion of membrane age revealed a
decrease in permeability to the tune of up to 80% of the initial value
for both cross-linked and uncross-linked polymers. However, a critical look at the results showed that both the initial permeability
and aging-induced permeability were reduced by cross-linking. For
example, the initial permeabilities of CH4 were about 16,000 and
13,500 barrer for uncross-linked and cross-linked PTMS, respectively. The rate of decrease in the aging-induced permeabilities
with time, for the same gas, is slighly higher in cross-linked PTMS
than uncross-linked. For example, the aging-induced permeability
decrease with time in uncross-linked PTMS is 38.94 while in crosslinked PTMS it is 82% of the initial value. The results reported in
this studies were in contrast to other similar studies where crosslinking was found to reduce aging.
For CO2 separation, research focus has been dominated by the
search for materials with exceptional CO2 selectivity relative to
other gases. Interestingly, majority of the most promising materials
are in the rubbery state (Murphy et al., 2009). Polymers containing PEO segments have attractive solubility selectivities because
of their interaction with CO2 quadrapole. However, to achieve
practically useful gas separation membranes from such materials, it necessary to suppress PEO crystallization so as to achieve
high uxes and to retard swelling. This could be achieved by
using cross-linking, blending or block-copolymerization (Murphy
et al., 2009). Polyethylene glycol (PEG) is a polyether compound with many industrial applications. It has also been known
as polyethylene oxide (PEO) or polyoxyethylene (POE), depending on its molecular weight. PEG, PEO, or POE refers to an
oligomer or polymer of ethylene oxide. Although, the three names
are chemically synonymous, however, historically PEG is usually refer to as oligomers and polymers with a molecular mass
below 20,000 g/mol, PEO to polymers with a molecular mass
above 20,000 g/mol, while POE to a polymer of any molecular
mass (http://en.wikipedia.org/wiki/Polyethylene oxide). Among
the polyether family, PEO has been identied as an excellent membrane material particular for separation of polar, quadrupolar or

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

plasticization phenomenon. From these results, one can infer


that poly(ether compound) polymers are not good candidates for
CO2 /CH4 separation where highly sorbing gas are involved especially at higher partial pressure of the highly sorbing penetrant.
More research efforts are needed on how the plasticization pressure
of these polymers can be improved.
4.2. Grafting of polymer backbone
The incorporation of highly rigid segments, such as aromatic
and the substitution of small groups onto the rotating unit are
some of the ways of improving gas separation properties of membrane. This simple method have been applied by Pixton and Paul
(1995) to study the gas transport properties of adamantane based
polysulfone (2,2-(4-hydroxy-phenyl)adamantane polysulfone and
1,3-(4-hydroxyphenyl)adamantane polysulfone. Results obtained
from the pressure dependent permeability analysis on the lms
(5075 m in thickness) of the two polymers revealed both polymers to be CO2 plasticization resistant up to a pressure of 20 atm.
This is the maximum pressure of the experiment. Thus it is possible for the plasticization pressure to be more than 20 atm. This
improvement in the plasticization suppression properties is however dependent on the lm thickness of the polymer. This is evident
from the studies that were later carried on ultra-thin lm polysulfone membranes where the plasticization pressure was lower
(Scholes et al., 2010a). Details of grafting techniques that can be
used to modify polymers for applications in gas separation can be
found in Bhattacharya and Misra (2004).
4.3. Template polymerization and use of porogens
The concept of template polymerization was derived from natural polymerization processes such as replication of DNA and
biosynthesis of proteins (Polowinski, 2003). Today, this process is
widely used for synthetic polymers because it mimics the impressive polymerization techniques found in nature. Also, research
advances in templation using synthetic polymers have attracted
much attention because templation allows for a high degree of
control and tuning of polymer properties during polymerization
(South and Weck, 2007). In addition, the method can be employed
in the synthesis of ultrathin lm polymers. It can proceed as template polycondensation, polyaddition, ring opening polymerization
and ionic or radical polymerization (Polowinski, 2003; South and
Weck, 2007). The production of materials in which the daughter
polymer and the template together form a nal product has been
identied as a promising application of template polymerization.
This is due to problem usually encountered during the separation of daughter polymer from the template. Interestingly, recent
research ndings have also revealed methods in which daughter
polymers can easily be separated from the support based template (South and Weck, 2007). The process is a convenient way of
producing polycomplexes, polycomplex composites, and polymer
blends. Polycomplexes obtained by template polymerization have
been used for spinning bers. In polymer membrane synthesis,
template polymerization has been employed in conjunction with
other emerging polymeric membrane synthesis techniques to fabricate gas separation membrane with balanced permeability and
selectivity as well as excellent plasticization resistance properties.
The word porogen is an acronym meaning Pore Generator (Han
et al., 2009). The mechanisms of pore formation induced by the use
of porogens have been investigated by many authors (Okay, 2000;
Rolls et al., 1990). Schematically, the mechanism was depicted by
Marti et al. (2005) as shown in Fig. 7. Traditionally, it is widely used
for manufacturing porous materials used for dielectric applications.
For example, templated polymerization of polysilsesquioxane precursor in the presence of labile organic porogens was used to create

Fig. 7. Schematic representation of the formation of macroporous materials by the


use of porogens. (a) starting suspension droplet containing monomer, cross-linker
and porogen (b) precipitation of a polymer-rich phase into microspheres (c) growth
and aggregation of microspheres (d) polymerization of the residual monomer in the
monomer-rich phase acting to glue the microspheres.
Figures were copied from Marti et al. (2005).

pores in the resulting dielectric materials (Lee et al., 2005a,b). The


process was carried out through a sacricial thermal decomposition
of the porogens in the range of 350 and 400 C (Cruden et al., 1999;
Lee et al., 2005a,b). Detailed description of another new approach
on the use of porogens can be found in Marti et al. (2005). Recently,
it has been found to be very useful in improving the permeability and plasticization suppression properties of polymers for gas
separation.
Application of template polymerization and use of porogens in
preparing polymeric membrane materials can be traced back to the
role of polyimides in preparation of carbon molecular sieve (CMS).
Detailed description of the preparation of CMS is beyond the scope
of this review and can be found in Ismail (2010); Kita (2006) and
Williams and Koros (2008). In previous research ndings, aromatic
polyimides were used as polymer precursors for preparation of CMS
membranes due their excellent balance of permeabilityselectivity
(Maya et al., 2010). The process of fabricating CMS membranes
from polyimides involves heating the polyimides up to very high
temperature in the range of 700900 C. Heating at high temperature often results into degradation of polyimides chain (Maya
et al., 2010). Relatively low temperature pyrolysis was therefore
adopted to modify polymer properties for gas separation. Polyimides containing labile groups that can be removed by the low
temperature pyrolysis have been proposed as good candidate for
this technique. Sulfonated polyimides were pyrolyzed at 370 and
450 C to produce dense and exible pyrolytic at membranes with
large amount of microvoids (Islam et al., 2005; Zhou et al., 2002).
The microvoids were said to have been caused by template-like
effect of SO3 H groups. Carbon-dioxide (CO2 ) gas permeability of
the pyrolytic membranes increased by 378 barrer in comparison
with the polymer precursor. This method was also employed by
Maya et al. (2010) to prepare a partially pyrolyzed membranes.
The effect of nal pyrolysis temperature (425, 450 and 475 C)
on gas separation performance of copolyimides that contain carboxylic acid labile groups was investigated. CO2 permeability of
the pyrolyzed membranes increased by about 18 times while the
ideal selectivity of CO2 /CH4 dropped by about 1.8 times when
compared with homogenous copolyimide without carboxylic acid
groups. In another similar approach (Xiao and Chung, 2011), betacyclodextrin (a thermal labile molecule with large dimensions) was
rst grafted on a rigid but cross-linkable polyimide containing carboxylic acid pendant groups. Grafting was done by esterication
process. The resulting cyclodextrin grafted polyimide membranes
were subjected to thermal treatment from 300 to 450 C to decompose the grafted cyclodextrin and at the same time preserve the
polyimide backbone. Thus, the thermal treatment caused large
amount of micro-pores which in turn resulted into enhanced
CO2 /CH4 gas separation performance and physico-chemical stability of the membranes. Reuslts obtained also revealed that the
membrane cured at 425 C does not exhibit plasticization up to
25 atm. Effect of thermal labile saccharide units on gas separation
performance of polyimide was also studied by Chua et al. (2012).

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

Gas separation performance including permeability, selectivity and


resistance to plasticization was also studied. Generally, cyclodextrin was observed to be the best candidate for membranes with
thermally generated micro pores (especially based on improvement in permeability of CO2 ). This conclusion is illustrated in
Table 10 which contains gas separation performance and the porogens that were employed.
A thorough investigation of plasticization behaviour of polyimide comprising cyclodextrin (CD) porogens was done by Askari
et al. (2012a,b) using a cross-linkable co-polyimide (6FDADurene/DABA (9/1)). A new high performance gas separation
membrane (made into both at sheet and hollow ber) with
enhanced membrane permeability and resistance to plasticization were developed. Thermal decomposition of CD converted the
spaces originally occupied by CD to micro-pores which consequently increase fractional free volume and gas permeability. The
newly developed membranes are reported to be highly exible and
posses good mechanical properties. The single and mixed gas permeability of the resulting membranes was determined using six
different gases including CO2 and CH4 at 35 C. Results of single
gas permeation experiments revealed a maximum CO2 and CH4
permeabilities of 4211.12 and 187.66 barrer at 35 C and 10 atm,
respectively. In addition, the highest selectivity obtained was
reported to be 22.44. A unique part of the work is the involvement of
permeability testing for the higher hydrocarbon components (C3 H6
and C3 H8 ) of NG. This has made the membrane a potential candidate for NG treatment. Analysis of the CO2 -plasticization behaviour
of the membrane is summarized in Table 11. Clearly, thermal treatment temperature contributes very signicantly to the permeation
properties of these membranes. The higher the temperature of
thermal treatment, the better the plasticization resistance of the
membrane. Thus the best of the membrane samples is the one heat
treated at 425 C. It is well established that pure gas permeation
test is not a good representation of membrane especially at the
plasticization pressure. Based on this, the authors have conducted
a mixed gas permeation tests at higher pressure of 20 atm for the
best of the samples tested with pure gas permeation tests. Results
from the mixed gas permeation tests showed a slight decrease in

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)

Permeability CO2 (Barrer)


11234
44.7532
5.06456
35.3410
9351539

Permeability CH4 (Barrer)


0.38.0
1.5628.9
0.1017.4
0.7718.2
41.765.0

Selectivity CO2 /CH4


1493.1
18.428.6
26.249.4
22.446
20.525.9

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

Permeance of CO2 (GPU)

Plasticization pressure (atm)

65
64
75

1.2 105
2.0 105
4.3 105

575
540
450

3
8
>10.53

1 GPU = 1 106 cm3 (STP)/cm2 scmHg.


Table 14
Permeability (barrer) of S-PEEK with sodium ions (Khan et al., 2011).
Polymer sample

Degree of sulfonation

Permeability of CO2 (barrer)

Plasticization pressure (bar)

S-PEEK 1
S-PEEK 2
S-PEEK 3

0.44
0.76
1.10

8
10.5
14.5

11
32
>40

conditions by varying the time (from 10 to 60 min) as well as the


temperature (from 450 to 500 C). Membrane annealed at 500 C for
10 min has the highest CO2 /CH4 selectivity of 22 with CO2 and CH4
permeance of 2326 and 105 GPU, respectively. Detailed descriptions on methods for preparing thermally rearranged polymers
(such as polybenzoxazoles and polyimide) for gas separation applications are available in patents (Freeman et al., 2012; Lee et al.,
2012a).
4.6. Phase inversion
It was demonstrated by Mikawa et al. (2002) that ultra thin
defect free skin layer membranes can be produced by varying the
weight of non-solvent in the casting solutions and the free standing time. Using 6FDA-6FAP polyimides with molecular weights of
1.2 105 , 2.0 105 , and 4.3 105 , asymmetric polyimide membranes with controlled thickness varying from 0.05 to 0.35 m were
fabricated. Membranes produced were subjected to CO2 gas permeation test at varying pressure up to 800 cmHg. Results obtained
were summarized in Table 13.
4.7. Sulfonation of polymers
Modication of gas transport properties of polymers by sulfonation is one the new methods of fabricating membrane with
enhanced separation performance. Previously, selected polymers
are modied by post-sulfonation. This method degrades the thermal and mechanical stabilities of the polymers and makes it
very difcult to achieve high degrees of sulfonation. To overcome
this problem, Khan et al. (2011) prepared sulfonated aromatic
poly (ether ether ketone) (S-PEEK) membranes using sulfonated
monomers. The stability and possible industrial applications of the
S-PEEK membranes for CO2 separation from gas mixtures were
investigated. The effects of increasing degree of sulfonation and the
presence of various types of ions (H, Na, Li, Mg, Ba and Al) on the
permeability and selectivity were also investigated. Table 14 contains the results obtained for the plasticization pressure and CO2
permeability.
4.8. Copolymerization and blending
The gas permeability and selectivity of copolyimides have
been investigated by many authors. However, the gas transport
properties in glassy copolyimides containing rubbery dimethylsiloxane structure have been investigated only by few researchers
(Furukawa et al., 1990; Nakagawa et al., 2002; Stern and
Vaidyanathan, 1990). Two methods were employed by Stern and
Vaidyanathan (1990) namely: copolymerization of PDMS and
polyimides; and copolymerization of two polyimides containing
silicon atoms in their backbone chains. In the work of Nakagawa

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.

4.9. Polymers of intrinsic microporosity (PIM)


Report of a breakthrough in the successful synthesis of a new
class of amorphous nanoporous polymers was published by Budd
et al. (2004). These polymers were developed from microporous
networks of planar functional units such as phthalocyanine, porphyrin and hexaazatrinaphthylene (Budd et al., 2004). This material
is often referred to as polymers of intrinsic microporosity (PIMs)
because their micropores are a consequence of their molecular structure (Budd et al., 2010). They are robust, nanoporous
(0.40.8 nm), soluble, processable by solvent based techniques,
thermally stable (initial decomposition at around 460 C) and
posses very high surface areas (800 m2 /g) and free volume (Budd
et al., 2004; Du et al., 2012). Detailed concept of PIMs is presented
by Budd et al. (2005a, 2010). Since the pioneering paper on the
successful synthesis, PIMs have been investigated for various applications such as gas absorption, gas permeation and inverse gas
chromatography (Budd et al., 2008, 2010). In gas separation, the
high permeability is also accompanied by high selectivity above
Robesons upper bound for a number of gas pairs. Research ndings
on gas (CO2 and CH4 ) transport properties of PIMs are summarized
in Table 16.

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

PDMS content (wt%)

0.00
12.60
21
19
18

Plasticization pressure* (atm)

Permeability of CO2 (barrer)


Pure

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

Budd et al. (2005b)


Budd et al. (2005b)
Budd et al. (2008)
Mason et al. (2011)
Du et al. (2009)
Du et al. (2012)
Du et al. (2008)

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.

5. Conclusion and recommendations


Current challenges in the use of polymeric membranes for
separation of CO2 from natural gas were reviewed. CO2 induced
plasticization remains a painful problem dominating the commercial use of polymeric membranes in natural gas processing. It
was observed that plasticization property is evolving into a conventional trade-off pattern where a membrane exhibiting a high
plasticization suppression property has relatively low permeability
and sometimes low selectivity. A mathematical model is required
to generate a three dimensional (x, y, z) upper-bound curve of CO2
permeability (barrer), CO2 /CH4 Selectivity and polymer plasticization pressure (atm) that will represent a general trade-off which
can be used for optimization of performance of plasticization resistant polymeric membranes for CO2 removal from natural gas. This
curve is expected to provide quick information on the status of plasticization resistance properties of the newly developed membrane
materials. Accordingly, this is the focus of our ongoing research.
Polyimides were observed to be the most widely investigated
polymer membranes for plasticization resistance property. Other
polymers that have also been investigated include SPEEK, PEO,
PIMs and polysulfone. Almost all the investigations were performed using at sheet and hollow ber membranes. Polymers
such as 6FDA-DAM:DABA, adamantane based polysulfone, 6FDADurene/DABA copolyimides grafted with , , and cyclodextrin
and SPEEK did not show any sign of plasticization up to the highest
feed pressures of 69, 20, 30 and 40 atm, respectively. Thus, the maximum plasticization pressure for the current polymer membranes
is 69 atm. This is below the 90atm at which one of the commercial separation plants is presently being operated. It was revealed
that the investigation of plasticization resistance of these polymers
have been limited due to the upstream pressure capacity of the permeation test set up that were employed for their investigations.
It is therefore recommended that these polymers are tested with
permeation apparatus with capacity for higher upstream pressures.
Thermal rearrangement, cross-linking, thermal treatment, template polymerization, use of porogens, polymer blending, and
dual-layer hollow ber spinning are observed to be promising

methods for the fabrication of polymer membranes with better


plasticization suppression properties. These methods should be
employed to improve the plasticization suppression properties of
more polymers. Reviews of other interesting topics such as the
theories of polymer plasticization, aging and conditioning, and current research status on thin lm technology are recommended. It is
hoped that with continued efforts, more achievements can be made
to produce membranes with excellent gas separation performance.
Acknowledgements
The authors gratefully acknowledge the supports of the Membrane Cluster Research Group, Universiti Sains Malaysia, and Center
for Petroleum & Minerals, King Fahd University of Petroleum &
Minerals, Saudi Arabia.
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