Himma2018-Review N2 - Membrane

Rev Chem Eng 2018; aop
Nurul F. Himma, Anita K. Wardani, Nicholaus Prasetya, Putu T.P. Aryanti and I Gede Wenten*
Recent progress and challenges in membrane-

based O2/N2 separation
https://doi.org/10.1515/revce-2017-0094
Received September 30, 2017; accepted April 18, 2018
1 Introduction
Abstract: Compared with current conventional technolo- Oxygen and nitrogen are the two most widely used and
gies, oxygen/nitrogen (O2/N2) separation using mem- important industrial gases after hydrogen. Due to this
brane offers numerous advantages, especially in terms relatively high demand, obtaining them in a high-purity
of energy consumption, footprint, and capital cost. How- condition is desirable. Therefore, technology for O2/N2
ever, low product purity still becomes the major challenge separation plays an important role and continues to be
for commercialization of membrane-based technologies. developed to achieve a highly efficient production process
Therefore, numerous studies on membrane development as well as low capital cost. Some conventional separation
have been conducted to improve both membrane proper- technologies such as solvent absorption, solid adsorp-
ties and separation performance. Various materials have tion, and cryogenic distillation are usually applied (Smith
been developed to obtain membranes with high O2 per- and Klosek 2001, Belaissaoui et al. 2014). Different from
meability and high O2/N2 selectivity, including polymer, the conventional technologies, membrane-based separa-
inorganic, and polymer-inorganic composite materials. tion offers numerous benefits including modular configu-
The results showed that most of the polymer membranes ration, relatively low energy and chemical consumption,
are suitable for production of low to moderate purity O2 and low capital cost (Drioli and Curcio 2007, Baker and
and for production of high-purity N2. Meanwhile, per- Lokhandwala 2008, Drioli et al. 2011, K hoiruddin et al.
ovskite membrane can be used to produce a high-purity 2014, Purwasasmita et al. 2015a, Purwasasmita et al.
oxygen. Furthermore, the developments of O2/N2 separa- 2015b, Ariono et al. 2016, Wardani et al. 2017, Wenten et al.
tion using membrane broaden the applications of oxygen 2017a,b). Its efficacy has also been proven to separate
enrichment for oxy-combustion, gasification, desulfuriza- various gas pairs (Ismail et al. 2002). It is then also prom-
tion, and intensification of air oxidation reactions, while ising to apply membrane technology for O2/N2 separation.
nitrogen enrichment is also important for manufacturing The gas transport through membrane has been sys-
pressure-sensitive adhesive and storing and handling tematically studied on more than a century ago (Baker
free-radical polymerization monomers. 2004). In general, membrane gas separations are based
on one of the following mechanisms: Knudsen-diffu-
Keywords: application; gas separation membrane; mem-
sion, molecular sieving, and solution-diffusion (Koros
brane preparation; oxygen and nitrogen separation.
and Fleming 1993). The two former mechanisms gener-
ally occur in the porous membrane. Based on Knudsen
flow, the ideal separation factor for the N2/O2 gas pair is
1.07 (Pandey and Chauhan 2001), which is very low. For
*Corresponding author: I Gede Wenten, Department of Chemical
Engineering, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung
molecular sieving, the membrane pore diameter must be
40132, Indonesia; and Research Center for Nanosciences and between the diameters of separated gas molecules, allow-
Nanotechnology, Institut Teknologi Bandung, Jl. Ganesha 10, ing only the smaller molecule to permeate and resulting
Bandung 40132, Indonesia, e-mail: igw@che.itb.ac.id. in a high separation. Meanwhile, the latter mechanism
http://orcid.org/0000-0002-5818-9286 describes the gas transport through the non-porous mem-
Nurul F. Himma: Department of Chemical Engineering, Universitas
brane; the main example is a dense polymer membrane
Brawijaya, Jl. Mayjen Haryono 167, Malang 65145, Indonesia
Anita K. Wardani: Department of Chemical Engineering, Institut (Ghosal and Freeman 1994, Murali et al. 2013).
Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia In membrane O2/N2 separation system, the permeate is
Nicholaus Prasetya: Department of Chemical Engineering, Institut an O2-enriched stream at low pressure, while the nitrogen-
Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia; rich stream is recovered in the high-pressure side (Figure 1).
and Barrer Centre, Department of Chemical Engineering, Imperial
From this, relatively pure nitrogen can be produced.
College London, Exhibition Road, London SW7 2AZ, UK
Putu T.P. Aryanti: Department of Chemical Engineering, Jenderal
However, O2-enriched air is usually produced in low purity
Achmad Yani University, Jl. Terusan Jendral Sudirman, Po Box 148, level (25–50% oxygen) (Smith and Klosek 2001), making
Cimahi, West Java, Indonesia the membrane process less economic and therefore less
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2 N.F. Himma et al.: Membrane-based O2/N2 separation
the membrane thickness is called permeability, P. The

common unit for P is barrer [1 barrer = 10−10 cm3 (STP) cm/
cm2 s cm Hg, or, in SI units, 3.348 × 10−16 mol m/(m2 s Pa)].
For ideal selectivity, αA/B, it can be defined as the ratio of
permeabilities of gases A and B. The permeance represents
the membrane productivity; meanwhile, the selectivity
represents the ability of the membrane to separate gases.
In order to improve the membrane performance, optimiza-
tion of the process parameters is also necessary.
Over the past 40 years, a total of 969 publications on
O2/N2 separation membranes were found, of which the
annual publications up to 2016 are shown in Figure 2. Since
1986, the number of published papers has increased line-
arly in every 5 years (shown in the insert), showing a great
progress in this field. Some related reviews can be found,
including those on the applications of membrane gas sep-
Figure 1: Schematic diagram of O2/N2 separating membrane.
aration (Koros and Fleming 1993, Baker 2002) and devel-
opment of the membranes for gas separation (Robeson
competitive for industrial oxygen applications that require 1999, Ismail and David 2001, Pandey and Chauhan 2001,
90% O2. As the kinetic diameters of oxygen and nitrogen Ismail et al. 2002, Ismail and Yean 2003, Dong et al. 2013).
molecules are very close, i.e. 3.46 Å for oxygen and 3.64 Å Focusing on O2/N2 separation or air separation, reviews
for nitrogen (Ghosal and Freeman 1994), numerous efforts can be found on air separation by polymer-based mem-
have been attempted to improve O2/N2 selectivity. Up to branes (Murali et al. 2013) and ceramic-based membranes
now, development of membrane materials for gas sepa- (Sunarso et al. 2008, Hashim et al. 2010). Concerning
ration still becomes an important topic to improve the the attractiveness of the membrane technology for O2/N2
membrane properties (thermal and chemical resistance) separation and the great advance in the development of
and separation performances (permeance or permeabil- membrane material and preparation, this review article
ity, and selectivity). Permeance is defined as permeate then focuses on membrane-based O2/N2 separation with
flux through a membrane under a particular pressure dif- more comprehensive discussion, including the membrane
ference. The common unit for permeance is GPU [1 GPU = materials and preparation, and the process parameters in
10−6 cm3 (STP)/cm2 s cm Hg, where STP is the Standard O2/N2 separation. The prospect application of membrane-
Temperature and Pressure (1 bar and 273 K); or, in SI units, based O2/N2 separation, as well as the challenges in practi-
3.348 × 10−10 mol/(m2 s Pa)]. The permeance multiplied by cal application, are finally discussed.
Figure 2: The number of published papers related to the search term of O2/N2 separation membrane. Indexed by Scopus [TITLE-ABS-KEY
(O2/N2 separation and membrane); June 2017].

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N.F. Himma et al.: Membrane-based O2/N2 separation 3
2 Membrane materials commonly used for O2/N2 separation membrane. Among

these polymers, PSf is the most promising polymer for O2/
and preparation N2 separation. The PSf membrane was first introduced
by Union Carbide in 1965 because of its permeability and
2.1 Polymer membranes selectivity as well as good mechanical strength (Wang
et al. 2002a). Besides PSf, PI is also widely used for O2/
Polymeric materials have been long developed for gas N2 separation membranes because of its good mechanical
separation membranes due to their light weight, ease of property coupled with high thermal and chemical stabil-
fabrication, and low cost (Baker and Low 2014, Wenten ity (Tul Muntha et al. 2016). Recently, PSf and PI-based
et al. 2017c). In polymer membranes, the separation of membranes showed good performance that is close to
gas molecules is commonly based on solution-diffusion or slightly above 2008 upper bound (Chong et al. 2016).
mechanism. The polymer membranes can be more per- Several works also used PU for preparing gas separation
meable to smaller penetrant molecules (based on diffu- membranes with different chemical characteristics and
sivity selectivity) or more permeable to larger penetrant microstructures (Chen et al. 2000). However, this mem-
molecules (based on solubility selectivity) (Freeman brane is limited by hard segments of urethane or urea that
and Pinnau 1999). For the former, the polymers are stiff influence the gas transport through the membrane. Due to
chain, glassy, and moderately high free-volume polymers. its low selectivity in gas separation, some modifications
Meanwhile, highly flexible, rubbery polymers or certain have then been conducted to improve the PU membrane
ultrahigh free-volume polymers are suitable for the latter performances (Sadeghi et al. 2011, Isfahani et al. 2016,
separation type. Typical rubbery polymers have O2/N2 dif- Mozaffari et al. 2017). Other polymers used as membrane
fusivity selectivity of 1.4–1.8, which is lower than those of materials are polyvinyl chloride (PVC) (Jones et al. 2011),
typical glassy polymers (i.e. 3.0–3.8) (Ghosal and Freeman poly(ether ether ketone) (PEEK) (Jansen et al. 2006), poly-
1994). Thus, the glassy polymers have gained great atten- mers of intrinsic microporosity (PIMs) (Yong et al. 2013),
tion in most of the membrane gas separation processes etc., which are then discussed in the following sections.
due to their superior gas selectivity as well as the excellent
thermal and mechanical properties (Madaeni and Moradi
2011). 2.1.1 Integrally skinned asymmetric membranes
Figure 3 shows membrane materials used in several
research studies from January 2000 to August 2017. Some For gas separation, asymmetric membranes are usually
polymeric materials such as polysulfone (PSf) (Konruang used. The integrally skinned asymmetric membrane
et al. 2015), polyamide (PA) (Hosseini et al. 2014), poly was first developed by Loeb and Sourirajan in the 1960s
urethane (PU) (Weibel et al. 2006), polydimethylsiloxane (Strathmann et al. 1975). The membrane consists of a
(Rao et al. 2007), polyimide (PI) (Fatyeyeva et al. 2014), dense skin layer with a thickness of 0.1–0.5 μm supported
and polyaniline (PANi) (Illing et al. 2005) have been by a porous sub-layer with a thickness of about 5 0–150 μm,
where both the skin and sub-layer are composed of the
same material (Mulder 1996). The actual separating
barrier is given by the skin layer, while the sublayer acts
only as a mechanical support. Thus, the skin layer forma-
tion is a crucial factor in determining the gas separation
performance. Since the permeability of the asymmet-
ric membrane is inversely proportional to the skin layer
thickness (Sharpe et al. 1999, Chauhan and Pandey 2004),
a very thin skin layer is necessary to achieve high permea-
bility. In this regard, the term ultrathin is used to describe
an asymmetric membrane having skin layer thickness less
than 1000 Å (Pinnau and Koros 1991a). In more recent
studies, the effective skin layer thickness of approximately
1000–5000 Å is commonly classified as ultrathin, whereas
Figure 3: Polymer-based membrane materials for O2/N2 separation
thickness much less than ultrathin skins is classified as
[according to the number of published papers (1998–2017) indexed hyperthin (Ismail and Lai 2003). Besides, the skin layer
by Scopus]. should be defect-free since gas separation membranes are

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far more sensitive to minor defects in the selective mem- In a continuous process of membrane preparation, the
brane layer than membranes used in other applications. evaporation time is proportional to the air gap length. The
Even a few tiny defects can easily allow an unseparated rheological factor refers to the shear rate determined by
gas flow equal to 1–2% of the total flux through the mem- casting rate (in flat sheet preparation) or extrusion rate
brane (Baker 2004). The defect-free selective layer can (in hollow fiber preparation). The schematic diagram of
avoid nonselective pore flow where gas transport occurs dry, wet, and dry-wet process with the important factors is
by viscous mechanism or Knudsen mechanism. shown in Figure 4.
The porous support layer has a very small effect on A high polymer concentration can give membranes
separation performance. However, its structure must also with high O2/N2 selectivities due to the enhanced chain
be optimized to minimize additional mass transfer resist- entanglement, reducing micro-defects (Chung et al. 1992).
ance (Rowe et al. 2011). Although the skin layer is defect- Thus, a high solid content dope is usually preferred.
free, the membrane selectivity can be low due to the Chung et al. (1997) have successfully prepared hollow
substantial substructure resistance. Therefore, the devel- fiber membranes with an ultrathin skin layer of 474 Å
opment of asymmetric gas separation membrane prepara- using polyethersulfone/N-methyl-pyrrolidone (PES/NMP)
tion to obtain defect-free and ultrathin skin layer should system, proving that adding non-solvents into spinning
also be directed to obtain highly permeable substructures dopes is not the prerequisite to fabricate hollow fiber
simultaneously (Pinnau and Koros 1991a). membranes with an ultrathin skin layer. With the criti-
Phase inversion is the most common method for fab- cal polymer concentration of 35 wt%, the prepared mem-
ricating an asymmetric membrane. In this method, the brane had an O2/N2 selectivity of 5.80 and O2 permeance of
membrane morphology is determined by the phase sepa- 9.3 GPU at room temperature. As shown by Ismail and Lai
ration and subsequent solidification of the cast polymer (2003), the solution viscosity increased with the increase
solution. The phase separation process can be accom- in polymer concentration, in which the critical concentra-
plished in dry phase, wet phase, or dry-wet phase (Pinnau tion was determined by the intersection of the two slopes,
and Koros 1991b). For this method, it has been identified a slope in a region with little change in viscosity and that
that polymer concentration, solvent ratio, evaporation in a region with a dramatic change in viscosity. Compared
time, and rheological factors are the dominating factors with polymer concentration below the critical concentra-
in controlling the membrane properties (Ismail and Yean tion, polymer concentration above the critical concen-
2003) that significantly affect its separation performance. tration resulted in membranes with a higher entangled
Figure 4: The sequence of processes and the important factors in dry-wet casting and spinning process.

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conformation, tighter intermolecular chain displacement, evaporation rate. The membranes with thick and dense
and less defective outer layers and therefore had higher skin layer were highly selective but low in flux. Jami’an et al.
selectivities. (2015) have used poly(lactic acid) (PLA), a b iodegradable
Incorporating non-solvent in the polymer solution can polymer. The results showed that the increase in evapora-
affect the membrane structure which then affects the gas tion time decreased the pore size and surface porosity but
separation properties. Wang et al. (2000) selected water as increased the skin layer thickness. The membranes pre-
the non-solvent in PES gas separation membrane prepara- pared using 60 s evaporation time showed O2 permeance
tion, considering the best miscibility with the coagulant of ~3.3 GPU and O2/N2 selectivity of about 1.03 at a pressure
(water). Water can also form a complex through multiple of 600 kPa. The gas pair selectivity was too low due to the
hydrogen bonding with NMP as the solvent, resulting in membrane surface defect; thus, a silicone coating may be
increased viscosity of NMP/H2O mixture. The resulting necessary as the secondary operation.
membranes exhibited higher permeance and selectivity Air gap can be used to introduce the dry process.
than the ones spun from NMP/alcohols and NMP/pro- Longer air gap length means longer solvent evaporation
pionic acid solvent systems. An investigation with other time in the drying process, and zero length of air gap means
non-solvents (Peng et al. 2009) showed that increase in that only a wet process exists. Unlike flat sheet membrane
the amount of both water and ethanol as non-solvent preparation, the dry phase separation in hollow fiber prep-
increased the shear viscosities of the high concentration aration may be intruded by the diffusion of internal bore
spinning dopes, which is due to the expanded polymer coagulant, damaging the skin layer formation. A study by
clusters that increase the resistance for shear-induced Wang et al. (1998) showed that there is an optimum range
deformation. The microstructure with big polymer clus- of air gap length that must be maintained to prevent the
ters may retard the nonsolvent intrusion and the mutual internal coagulant for reaching the outer skin layer before
diffusion of solvent-nonsolvent during phase inversion, the solidification of the outer skin layer in the wet process,
leading to the formation of macrovoid-free morphology. so a defect-free skin layer could be obtained. For their
Using water as the additive, the developed membrane had system (30 wt% of polyetherimide (PEI) in NMP/ethanol),
an ultrathin layer of 488 Å and showed O2/N2 selectivity the high selectivities were obtained from air gap lengths of
of 8.55. Yu et al. (2014) have prepared asymmetric mem- 0.1 and 0.15 m. The diffusion rate of the internal coagulant
branes based on trifluoromethylphenylated poly(ether can be accelerated by the strong interaction between the
ether ketone) (CF3-PEEK), in which the type and concen- internal coagulant and the polymer, as well as by the pres-
tration of internal solution were investigated. The results ence of nonsolvent in polymer dope. In a study by Wang
showed that the increasing nonsolvent concentration et al. (2002a), for a system of 30 wt% PSf in NMP/H2O, air
led to an increase in pore size and porosity due to the gap longer than 0.1 m resulted in membranes with poor
increased rate of liquid-liquid phase separation. At the selectivity. The internal coagulant (water) could quickly
same amount of nonsolvent, 1-butanol gave the smallest diffuse to the external walls due to the strong interaction
pore size and porosity, compared with iso-butanol, tert- between PSf and water. It has been also shown that the
butanol, and 2-propanol. The O2 and N2 permeabilities of presence of H2O in polymer dope accelerated the water
the asymmetric membrane were obviously higher (at least diffusion rate, requiring a shorter air gap to obtain a com-
24 times) than that of the CF3-PEEK dense membrane, parable selectivity. Compared with NMP/EtOH system, the
while the O2/N2 selectivity decreased slightly. NMP/H2O system gave better performance with O2 perme-
It has been recognized that the skin layer formation ance in the range 20–30 GPU and with an O2/N2 selectivity
is greatly determined by the solvent evaporation (dry of 5–16.5 at 298 K.
process) before solidification in the wet process. Yamasaki Madaeni and Moradi (2011) have prepared defect-free
et al. (1999) showed that increasing solvent evaporation skinned asymmetric PSf membrane using dual bath coagu-
time resulted in a decrease in O2 permeance and increase lation method. The first coagulation is for the formation of
in O2/N2 selectivity, which was due to the increase in skin ultrathin and dense skin layer through the delayed phase
layer thickness. Similar results were also shown by Ismail separation, while the second one is for formation of open
and Lai (2003). Longer evaporation time produced mem- substructure through the instantaneous phase separation.
branes with a thicker skin layer and lower surface porosity. It was found that the membrane prepared using single
Meanwhile, a reduction in the ratio of less volatile solvent coagulation bath has no distinctive skin layer in which
to more volatile solvent increased the skin layer thick- a long tear and finger-like pores extend to the bottom of
ness and decreased the membrane surface porosity due the membrane. The O2 permeance through the membrane
to the enlarged dry phase-separated region with the high was 1.26 × 10–7 m3/(m2 s Pa) at 50 kPa with no selectivity for

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O2/N2 separation, indicating that the skin layer of the developed (Fritzsche et al. 1989, Fritzsche et al. 1990b,
membrane was highly defective. Interestingly, all mem- Kesting et al. 1990). Kesting et al. (1990) have developed
branes prepared using dual coagulation bath (alcohol as graded skinned PSf membrane by using Lewis acid:base
first coagulation bath for 80 s and distilled water as second complexes (A:B) as transient templates to control free
coagulation bath for 24 h) had higher selectivity but lower volume and permeability. The membrane exhibited a
O2 permeance due to the thicker skin layer. The highest fourfold increase in O2 permeability at constant O2/N2
selectivity of 9.81 was given by iso-propanol, but it was the selectivity compared to the membrane obtained using
lowest in O2 permeance (1.36 × 10–10 m3/(m2 s Pa) at 150 kPa) a neat solvent. It has been reported that the structural
with the thickest skin layer of 8.3 μm. In hollow fiber mem- units forming the effective separating layer of the asym-
brane preparation, bore coagulant is used mainly to control metric membranes prepared from the Lewis acid:base
the lumen formation. Water is commonly used as bore complex were less tightly packed and distorted than
coagulant. Ismail et al. (1999) have fabricated asymmet- those in the bilayer membrane prepared from tradi-
ric PSf hollow fiber membrane using a dry/wet spinning tional solvent/nonsolvent mixture, resulting in higher
process. The uncoated membranes exhibited much lower free volume and microporosity (Fritzsche et al. 1990a).
selectivity than the silicone-coated membranes, indicat- However, membranes with such structure are rarely
ing the presence of surface pores or imperfections in the studied recently.
uncoated membrane. Two different bore coagulants were Hasbullah et al. (2012) have prepared integrally
used; one was pure water and another one was 20 wt% skinned hollow fiber membranes by dry-jet wet spinning
solution of potassium acetate in water, having water activi- from poly(o-anisidine), a more soluble PANi derivative.
ties of 1 and 0.9, respectively. A reduction in water activity The resulting membrane showed a high O2/N2 selectivity
increased the membrane selectivity but reduced the pres- of 13, which was 30% higher than that of PANi membrane.
sure-normalized flux. However, it had a lower O2 permeation rate of 0.37 GPU,
In asymmetric gas separation membrane preparation, although the permeation rates of other gases (H2 and CO2)
the investigation of rheological factors is rather new. Ismail significantly improved.
et al. (1999) showed that the pressure-normalized flux and In addition to the typical dry/wet phase inversion
selectivity increased with the increase in dope extrusion process, supercritical CO2 (SCCO2) was used to induce
rate (DER). It was expected that the increase in DER would asymmetry in PSf dense film (Torres-Trueba et al. 2008).
decrease the active layer thickness, contributing to high By contacting one face of the membrane with solvent
pressure-normalized flux. Besides, the increase in DER (chloroform)/SCCO2 for several minutes, the porous
improves the shear rate which promotes the polymer mole- structure layer was formed. The results showed that the
cule to be more aligned, resulting in an oriented and highly thickness of the porous layer increased, while the dense
ordered membrane active layer. This condition will in turn skin layer decreased as the chloroform/PSf mass ratio
improve the membrane selectivity. The highest selectivity was increased. The average pore size in the porous layer
of O2/N2 (7.32 for silicone-coated membrane) was obtained decreased at high SCCO2 densities and slightly decreased
using high DER of 4.17 × 10–8 m3/s and reduced water activ- when increasing the CO2 depressurization rates. As the
ity in the bore. As shown in a work of Ismail and Lai (2003), dense skin layer was reduced from 51.13 μm to 26.15 μm
it is interesting that the high-sheared casting increases (from an already dense film of ~101 μm), the gas perme-
both permeability and selectivity of the membrane due to ance improved from 0.0253 GPU to 0.0532 GPU, but the
the reduction of skin thickness as well as enhancement of O2/N2 selectivity remained constant, indicating that the
molecular orientation in the skin layer. In a further study dense skin layer is defect-free of any pinhole. Another
(Ismail and Lai 2004), the main effects and interaction method that may be used to prepare asymmetric mem-
effects of those variables were investigated. It was found brane is a melt-spinning and stretching method, but it is
that the optimized parameters were polymer concentration rarely reported in membrane development for gas separa-
of 22–26%, solvent ratio of 0.54–1.00 wt%/wt%, shear rate tion particularly for O2/N2 separation. Wang et al. (2006a)
of 254–381 s−1, and evaporation time of 15–18 s. Asymmet- have prepared poly(4-methyl-1-pentene) (PMP) asymmet-
ric PSf membranes having essentially defect-free skin layer ric hollow fiber membranes by melt-spun and cold-stretch
with effective thickness in the range of 6590–11,330 Å were method. The results revealed that the time of annealing
prepared. and stretching ratio were the key factors influencing the
Besides asymmetric bilayer composed of a uniform structure of the resulting membrane. Table 1 summarizes
density skin supported on a porous substructure, the integrally skinned asymmetric polymer membranes
asymmetric trilayer with graded density skin has been developed for O2/N2 separation.

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Table 1: Permeation performances of integrally skinned asymmetric polymer membranes.
Membrane material O2 permeance (GPU) or O2/N2 Skin layer Reference

permeability (barrer) selectivity thicknessa (Å)
PC 36.0 GPU 5.3 – Pinnau and Koros (1991a)

PI (6FDA-IPDA) 65.0 GPU 6.3 – Pinnau and Koros (1991a)
PSf 1.1 barrer 6.2 270 Pinnau and Koros (1991b)
PES 9.3 GPU 5.8 474 Chung et al. (1997)
PSf 7.8–21.6 GPU 5.4–6.7 490–1351 Pesek and Koros (1993)
PSf 6.9 GPU 7.3 – Ismail et al. (1999)
PES (Victrex 4800P) 15.7 GPU 5.8 – Wang et al. (1996)
PES (Radel A-300) 12.0 GPU 6.2 – Wang et al. (1996)
PI (Matrimid) 18.1 GPU 6.6 730 Clausi and Koros (2000)
PI (6FDA-6FAP) 794 GPU 5.3 100 Niwa et al. (2000)
PI (6FDA-6FAP) 19.5 GPU 5.4 4700 Niwa et al. (2000)
PI (6FDA-6FAP) 66.0 GPU 5.1 1200 Niwa et al. (2001)
PES 14.3 GPU 6.8 600 Wang et al. (2000)
PSf 1.1 GPU 6.0 130,000b Lee et al. (2000)
PSf 20.0–30.0 GPU 5–6.5 370–500 Wang et al. (2002a)
PSf 3.4 GPU 4.5 – Ismail and Nasri (2002)
PSf 1.4 barrer 5.6 – Chen et al. (2014)
PSf 0.84 barrer 5.1 – Kim et al. (2007)
PLA 0.3 GPU 1.0 – Mohamed et al. (2015)
PC, polycarbonate; PES, polyethersulfone; PI, polyimide; PLA, poly(lactic acid); PSf, polysulfone; 6FDA-IPDA, poly(hexafluorodianhydride
isopropylidinedianiline); 6FDA, 2,2′-Bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 6FAP, 2,2′-Bis(4-aminophenyl)
hexafluoropropane.
a
Apparent skin layer thickness calculated from the O2 permeance and the intrinsic permeability.
b
Skin layer thickness approximately measured from SEM photographs.
2.1.2 C
opolymer and polymer blends significant increase in selectivity without losing perme-
ability compared with commercial PSf membrane.
Copolymer and polymer blends intend to combine the Polymer blending is a simple method to modify the
properties of monomers or polymers in the resulting polymer properties (Aryanti et al. 2015, Aryanti et al.
membrane. Block copolymers have gained a great inter- 2016). In this method, a certain polymer solution is gener-
est in gas separation. The structure and the properties of ally mixed with another polymer in different proportions
these materials can be tuned by using block copolymers and the resulting solution is used for the preparation of
with different structures (Buonomenna et al. 2012). Lokaj the membrane. An important aspect that needs to be con-
et al. (2002) have synthesized tri-block copolymers from sidered is miscibility, i.e. the ability of the polymers to
poly(styrene-co-acrylonitrile) and polystyrene blocks. The form a homogenous mixture. Regarding this, the ratio of
resulting films showed high O2/N2 selectivity (PO2/PN2 > 6). polymers becomes an aspect that is often investigated. Li
Camacho-Zuñiga et al. (2009) have synthesized new PSf et al. (2001) have prepared blend membrane from poly(4-
copolymers containing naphthalene moieties and bulky vinyl-pyridine) (PVP) and ethylcellulose (EC) by solution
bisphenols: tetramethyl (TM), hexafluoro (HF), and tetra- casting technique. The selectivity of O2/N2, as well as CO2/
methyl-hexafluoro (TMHF), showing high glass transition CH4 and H2/N2 increased continuously with increasing
temperatures (498–513 K), high thermal decomposition PVP content from zero to 100 wt%, but the O2 permeabil-
temperatures (669–745 K), and large free volume sites ity decreased with it. A significant increase in selectivity
(112–135 Å3). Regarding O2/N2 separation, the copolymers was in the PVP content range 50–60 wt%; thus, it might
showed O2 permeability values in the following order: be that the inversion from EC to PVP as the coherent
TM-NPSF < HF-NPSF < TMHF-NPSF, the inverted order fol- phase in the blend membrane occurred at 50 wt% of PVP.
lowed by their O2/N2 selectivity. However, the interesting Komatsuka et al. (2008) prepared PLA blend membranes.
finding is the TMHF-NPSF membrane showed simultane- PLA blend membrane from L96D4:L88D12 with ratio of 8:2
ously higher permeability and selectivity than naphtha- exhibited a higher O2/N2 selectivity (6.67) but lower O2 per-
lene polysulfone (NPSF) membrane, and even showed a meability 0.33 barrer than one from L96D4 homopolymer

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(selectivity: 6.22; permeability: 0.34 barrer). As the higher (–CF3) and phenylsulfone (–SO2C6H5) side groups. The
permeability was exhibited by PLA blend membrane with introduction of the side groups on the polymer chains
higher crystallinity (L96D4 homopolymer), this suggests made TFMPSPIM1–4 exhibit high O2/N2 selectivity (3.4–4.7)
that the size and distribution of free volume in the crys- while maintaining high O2 permeability (156–737 barrer),
talline PLA blend membrane are different from those in exceeding the Robeson upper bound. The O2/N2 selectiv-
other crystalline polymer membranes. Performances of ity of TFMPSPIM was also significantly higher than that
polymer blend membranes in O2/N2 separation are shown of PIM-1. PI with intrinsic microporosity (PIM-PI) prepared
in Table 2. by Ghanem et al. (2008) also exhibited high selectivity and
permeability above or near to Robeson’s 1991 upper bound.
Performances of PIMs for O2/N2 separation are summarized
2.1.3 Microporous polymers in Table 3.
Besides PIMs, another type of microporous polymer
In order to improve the O2/N2 separation performance, is thermally rearranged (TR) polymers. Their microporous
research is also directed to find a new polymeric material properties are due to the presence of microcavities formed
with improved properties. A polymer of intrinsic micr- during thermal rearrangement of the precursor polymer.
oporosity (PIM), a rather new type of polymer, has been The thermal rearrangement is a thermal conversion of a
developed for gas separation membrane material. For precursor polymer to a more rigid structure in the solid
this polymer, all rotational freedom is removed from the state (Kim and Lee 2015). With a more rigid structure, the
polymer backbone, but it has a randomly contorted mole- microporosity is enhanced with sufficient free volume
cular structure (Budd et al. 2005). The rigid and contorted sizes; thus, the separation performances are improved.
molecular structures of PIMs reduce packing efficiency However, thermal treatment in high temperature makes
and offer high free volume and high surface areas, making TR polymer brittle, which has been a concern in the
them intrinsically microporous materials (Du et al. 2008). development of TR polymer membrane. Li et al. (2013a)
Budd et al. (2005) reported that PIM-1 (prepared from mon- reported that spirobisindane-containing TR benzoxazole
omers of 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′- (spiroTR-PBO) membrane showed better mechanical prop-
spirobisindane and tetrafluoroterephthalonitrile) and PIM-7 erties (in terms of elongation and tensile strength) than
(prepared from monomers of 5,5′,6,6′-tetrahydroxy-3,3,3′,3′- PIM-1 which might be due to the entanglement degree of
tetramethyl-1,1′-spirobisindane and 7,7′,8,8′-tetrachloro- molecular chains by the kink at the spiro center reducing
phenazyl-3,3,3′,3′-tetramethyl-1,1′-spirobisindane) showed the elongational stress.
high O2/N2 separation performance surpassing Robeson’s
1991 upper bound, making them promising candidates
for generation of oxygen-enriched air for enhanced com- 2.1.4 Polymer membrane surface modification
bustion. The O2 permeability and O2/N2 selectivity were
370 barrer and 4.0 for PIM-1 and 190 barrer and 4.5 for PIM-7, Surface modification has been of interest in membrane
respectively. Du et al. (2008) have prepared PIM ladder development for various separation processes (Rana
polymers (TFMPSPIM1–4) containing trifluoromethyl and Matsuura 2010, Nady et al. 2011, Himma et al. 2016,
Table 2: Performances of polymer blend membranes for O2/N2 separation.
Sample O2 permeability O2/N2 Reference

(barrer) selectivity
SBR 602 5.8 George et al. (2001)

SBR/NR (50/50) 1457 2.9 George et al. (2001)
PLA (L96D4/L88D12: 10/0) 0.34 6.2 Komatsuka et al. (2008)
PLA (L96D4/L88D12: 8/2) 0.33 6.7 Komatsuka et al. (2008)
PVP/EC (50/50) 3.10 5.9 Gibson et al. (2001)
PU/PVAc/Pluronic (85/15/4) 0.58 5.3 Semsarzadeh and Ghalei (2012)
6FDA-TAB 15.2 5.9 Zimmerman and Koros (1999)
6FDA/PMDA (10/90)-TAB 0.453 12.5 Zimmerman and Koros (1999)
SBR, styrene-butadiene rubber; NR, natural rubber; PVP, poly(4-vinyl-pyridine); EC, ethylcellulose; PU, polyurethane; PVAc, polyvinyl
acetate; PLA, poly(lactic acid).

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Table 3: Performances of PIM and TR polymer membranes for O2/N2 separation.
Sample O2 permeability O2/N2 Reference

PIM-1 370 4.0 Budd et al. (2005)

PIM-7 190 4.5 Budd et al. (2005)
PIM-1 1610 3.3 Budd et al. (2008)
PIM-1 786 3.3 Staiger et al. (2008)
PIM-1 1133 3.2 Du et al. (2008)
TFMPSPIM1 156 4.7 Du et al. (2008)
PIM-PI-1 150 3.2 Ghanem et al. (2008)
spiroTR-PBO-6F 120 3.9 Li et al. (2013a)
spiroTR-PBO-PM 48 4.4 Li et al. (2013a)
spiroTR-PBO-BP 20 3.9 Li et al. (2013a)
spiroTR-PBO-BPA 2.1 4.7 Li et al. (2013a)
TR-DAP350 4.2 7.0 Comesaña-Gándara et al. (2015)
TR-DAR350 5.1 5.7 Comesaña-Gándara et al. (2015)
PIM-1 from 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindane (monomer 1) and tetrafluoroterephthalonitrile (monomer 2);

PIM-7 from monomer 1 and 7,7′,8,8′-tetrachloro-phenazyl-3,3,3′,3′-tetramethyl-1,1′-spirobisindane (monomer 5).
A series of TFMPSPIM ladder polymers 1–4 from polycondensation of TTSBI, HFTPS (heptafluoro-p-tolylphenylsulfone), and TFTPN (with the
molar ratio 1:1:0; 3:2:1; 2:1:1; 3:1:2).
PIM-PI-1, PIM-PI-3, and PIM-PI-8 from 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4′-(hexafluoroisopropylidene)dianiline,
and 3,3′-dimethylnaphthidine, respectively, reacted with bis(carboxylic anhydride).
Wenten et al. 2016, Wenten and Khoiruddin 2016, Ariono the reduction in the mobility of the intrasegment and the
et al. 2017, Aryanti et al. 2017, Himma et al. 2017b, Himma openness of the polymer matrix as a result of the cross-
et al. 2017a, Khoiruddin et al. 2017). This enables improve- linking of the polymer matrix (Liu et al. 1999). Long UV
ment of surface characteristic of a polymer membrane treatment may result in a decrease in both p ermeability
without changing the bulk properties of the membrane. In and selectivity. Konruang et al. (2015) modified PSf mem-
general, surface modification methods for gas separation brane with UV rays. Using a wavelength of 312 nm and a
membrane can be classified into two different ways: cross- power of 3.6 W/m2, the water contact angle of the modi-
linking modification and dense layer coating. fied membrane was reduced to 10–12°, the O2 permeation
decreased to 5.56 × 10–10 – 6.39 × 10–9 m3/(m2 s Pa), and the
O2/N2 selectivity decreased to 0.6–1.5. To enhance the selec-
2.1.4.1 Crosslinking modification tivity, the reactive oxygen can be used in a combination
Cross-linking modification has been widely used to with the UV irradiation, named UV-ozone treatment (Fu
improve the membrane selectivity. The enhanced selec- et al. 2010).
tivity is due to the restriction of mobility and increase in Ion beam irradiation of polymer membrane can induce
packing density of polymer chains. Cross-linking can be cross-linking in the polymer matrix but also can enhance
induced by UV irradiation, ion beam irradiation, plasma the chain scission (Lee 1999, Jain and Agarwal 2011). Irradi-
treatment, thermal treatment, and chemical compounds. ation of PI-ceramic composite membranes with 180 keV H+
Hsu et al. (1993) used UV irradiation to modify poly at ion fluence of 2.5 × 1019 H+/m2 has successfully improved
trimethylsilylpropyne (PTMSP) membrane. The O2/N2 both O2 permeance and O2/N2 selectivity from 12.64 to 18.79
selectivity of the modified membrane increased from the GPU and from 3.34 to 6.61, respectively (Xu and Coleman
intrinsic value of 1.4 to approximately 4. However, the per- 1999). The simultaneous improvement of O2 permeance
meance significantly decreased about 7 times. UV irradia- and O2/N2 selectivity was attributed to the increase in free
tion of PI membrane conducted by Meier et al. (1994) also volume due to the polymer degradation and the increased
significantly increased O2/N2 selectivity and decreased O2 rigidity of the polymer structure due to crosslinking of the
permeability. The decrease in permeability can be due to polymer chains. However, high dose of irradiation may

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lead to a non-selective resistance layer formation, result- 1,3-propane diamine (PDA); 1,4-butane diamine (BuDA);
ing in a decrease in both gas permeance and selectivity 1,3-cyclohexanebis(methylamine) (CHBA) to modify
(Ilconich et al. 2003). Matrimid and 6FDA-durene membrane. The chemical
Plasma treatment is probably the most used method crosslinking modification increased the O2/N2 selectiv-
to modify polymer membrane for O2/N2 separation. The ity but decreased the gas permeability. For 6FDA-durene
use of various gas types have been studied, including membrane, the highest O2/N2 selectivity of 5.36 was
fluorine- (Lin et al. 1993, Le Roux et al. 1994a,b, Hopkins achieved by cross-linking with 1.65 m PDA for 1 min,
and Badyal 1996, Kim et al. 2009, Fatyeyeva et al. 2014), whereas for Matrimid membrane, the highest O2/N2 selec-
chlorine- (Lin et al. 1995, Chen et al. 1997), and nitrogen- tivity of 7.91 was achieved by cross-linking with 1.65 m
containing gases (Iwa et al. 2004, Teramae and Kumazawa BuDA for 10 h. Liu et al. (2001) modified 6FDA-durene PI
2007), as well as inert gas such as argon (Ar) (Houston membrane by using p-xylenediamine methanol. The use
et al. 2002). Borisov et al. (1997) used SF6 for plasma treat- of p-xylenediamine solution was also reported by Tin et al.
ment of PTMSP and polyvinyltrimethylsilane films. The (2003) for chemical crosslinking modification of Matrimid
fluorination resulted in a decrease in permeability but an membranes. The highest selectivity of 7.4 was achieved
increase in selectivity, which might be associated with a when the immersion time was 21 days.
decrease in segmental mobility of the polymer molecule Heat treatment is another method that is often used
due to the crosslinking formation. Other studies reported as post-treatment in gas separation membrane prepara-
that treatment of polypropylene membrane (Teramae and tion. This treatment causes the polymer membrane to
Kumazawa 2007) and polyethylene membrane (Nakata shrink leading to a higher packing density of polymer
and Kumazawa 2006) with NH3 plasma and N2 plasma chains. Once the skin layer of the membrane becomes
could increase both O2 permeability and O2/N2 selectiv- more compact, it becomes less permeable to the larger
ity. Plasma chlorination of polybutadiene (PB)/polycar- molecule (N2); thus, the O2/N2 selectivity of PES membrane
bonate (PC) composite membrane surface using CHCl3 (Li et al. 2004) and Matrimid/PSf membrane (Ding et al.
significantly increased O2/N2 selectivity but decreased O2 2008) increased after heat treatment. However, heat treat-
permeance (Chen et al. 1997). The selectivity improvement at a higher temperature may increase substructure
ment was mostly attributed to the alteration of the physi- resistance, resulting in a decrease in both permeance and
cal structure on the membrane surface (i.e. morphology selectivity.
alternation) rather than the chemical effect introduced
by chlorine. Surface modification of the PB/PC compos-
ite membrane with ethylenediamine (EDA) plasma also 2.1.4.2 Coating
resulted in enhanced O2/N2 selectivity and decreased O2 Coating is a common method to prepare composite mem-
permeability (Ruaan et al. 1998). But the increase in selec- branes. Generally, a thin dense top layer is coated on the
tivity was attributed to the affinity of EDA toward oxygen, porous sublayer; thus, each layer can be optimized inde-
while the decrease in permeability was attributed to the pendently. Coating method is usually performed by solu-
surface cross-linking. The important factors in plasma tion coating and plasma polymerization.
treatment are plasma power and treatment time. Plasma Chung et al. (1994) have developed a defect-free 6FDA-
treatment using high discharge power may lead to microc- durene asymmetric hollow fiber having a dense layer of
racking in the surface layer, resulting in decrease in selec- around 250 nm by dip-coating of the 6FDA-durene asym-
tivity (Lin et al. 1993). Meanwhile, plasma treatment in metric hollow fibers in 4-PVP/MeOH mixtures. Membrane
longer time may result in almost constant selectivity. This with impressive properties was obtained when 4-PVP con-
is because further fluorination only increases the thick- centration of 0.15% was used. The PVP/6FDA-durene com-
ness of surface fluorinated layer. posite fiber showed an O2 permeance of 14.5 GPU and O2/
Chemical crosslinking modification may significantly N2 selectivity of 6.9. Another polymer that is ideal to use
change the membrane structure, while the material deg- because of its dense skin layer material is PANi, which is
radation can be avoided. This method is often used to highlighted for its very high O2 selectivity (Lee et al. 1999).
modify PI membrane. A typical procedure is immers- The high selectivity is attributed to the electrical conduc-
ing the PI membrane in a reagent solution (diamines) tivity of PANi (especially in the case of the emeraldine
at ambient temperature for a certain period of time. In base form of PANi) once exposed to either an oxidizing or
this method, the immersion time is one of the impor- a reducing agent (Pellegrino et al. 1996). However, pure
tant factors determining the degree of crosslinking. Shao PANi films have poor mechanical properties and such
et al. (2008) used different diamines, including EDA; PANi membranes have low permeability. Thus, composite

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membranes comprising thin and selective PANi layer (0.8– used hexafluoroethane/hydrogen mixtures for plasma
10.5 μm) supported on porous polyvinylidene difluoride polymerization of composite membranes. The increase
were prepared (Illing et al. 2005). Gupta et al. (2006) then in hexafluoethane content in the feed gas improved the
prepared a composite membrane with selective PANi layer fluorine content of the polymers. This would lead to the
thickness as thin as 0.6 μm, and the ideal separation increase in solubility selectivity, resulting in improved
factors for O2/N2 was 5.8. Besides, carboxylated styrene oxygen permeability and O2/N2 selectivity.
butadiene rubber (XSBR) coating on PVC-PEG membrane A rather new technology is co-extrusion, which
had significantly increased O2/N2 selectivity up to 15 due enables the composite membrane preparation in one-step.
to the difference of polar and non-polar gas adsorption Ding et al. (2008) have prepared Matrimid/PSf dual-layer
within the XSBR skin layer (Lamlong and Taweepreda hollow fiber membranes using co-extrusion and dry-jet
2016). wet-spinning phase-inversion techniques. The resulting
Plasma polymerization enables the deposition of hollow fiber membranes had an O2/N2 selectivity of 7.55
ultrathin pinhole-free layers. In this method, a highly exceeding the intrinsic value of Matrimid (typically 7.2).
crosslinked plasma polymer is formed through repeated Both outer layer (Matrimid) and inner layer (PSf) had an
fragmentation of organic gas molecules into radicals asymmetric structure. The outer layer consisted of a dense
under a glow discharge exposure, generation of larger selective layer and a fully porous layer, while the inner
molecules, and combination of the molecules (Huber layer had porous outer skin with a pore size of 3.8 μm and
et al. 1997). The discharge power and monomer flow rate more porous inner skin with a smaller pore size of 2.5 μm.
are important factors controlling the deposition rate and The porous sublayer was obtained without a non-solvent
the coating layer characteristics. Nomura et al. (1984) in the inner spinning dope.
used the relationship between the conversion factor
DR/FM, which consists of the deposition rate of plasma
polymer DR, monomer flow rate F, and molecular weight 2.1.5 Progress of permeability-selectivity trade-off
M, and W/FM, where W is the discharge power, to deter-
mine which conditions result in an effective coating. The It has been recognized that there is a trade-off relation
maximum enrichment factor was obtained from plasma between permeability and selectivity in polymer gas sepa-
polymerization in the region between the power-deficient ration membrane. Polymers that have higher permeabil-
and monomer-deficient regions. However, it seems rarely ity generally give lower selectivity and vice versa. In 1991,
used in studies investigating plasma polymerization. Robeson (1991) analyzed the correlation of separation
Numerous gases and gas mixtures have been employed factor versus permeability for various binary gas mixtures
as feed in the plasma reactor, as summarized in Table 4. from the literature data and for the first time revealed an
Regarding O2/N2 separation membrane preparation, fluo- empirical upper bound relationship, which is then known
rocompounds are often used as the primary monomer as Robeson’s upper bound. Numerous studies of polymer
since the sorption coefficient of oxygen increases with membrane preparation have been conducted to achieve
the fluorine content of the solvent. Huber et al. (1997) and exceed the upper bound. New upper bound for O2/N2
Table 4: Permeation performances of thin plasma polymer layers.
Substrate Monomer gas mixtures (ratio) O2 permeability O2/N2 Reference

MF Milipore VSWP 04700 HFP/CH4 (3:1 mol ratio) 95 2.8 Inagaki and Ohkubo (1986)
Aluminium oxide and sinter glass C2F6/H2 (5.5: vol ratio) 21 3.4 Huber et al. (1997)
NR 4-Vpy 136 5.8 Kawakami et al. (1984)
NR 2-VPy/Ar (0.32: 1 vol ratio) 96 4.8 Kawakami et al. (1984)
NR PFTBA 153 4.1 Kawakami et al. (1984)
SR 4-Vpy 1150 4.9 Kawakami et al. (1984)
2-Vpy 1790 4.3 Kawakami et al. (1984)
PSf – 4.6 5.0 Kawakami et al. (1984)
PSf 4-Vpy 1.3 4.7 Kawakami et al. (1984)
NR, natural rubber; SR, poly(dimethylsiloxane); PSf, polysulfone; HFP, hexafluoropropene; CH4, methane; C2F6, hexafluoroethane;
H2, hydrogen; Ar, argon; 4-Vpy, 4-vinylpyridine; 2-Vpy, 2-vinylpiridine; PFTBA, perfluoro-tri-n-butylamine.

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separation has been published in 2008 (Robeson 2008) as polymer-based membranes beyond the upper bound line
the emergence of data of selectivity versus permeability (Liu et al. 2013, Jiang et al. 2017). However, O2/N2 separa-
above the 1991 upper bound. In order to observe the pro- tion performance tests of such membranes have not been
gress of the trade-off relation between permeability and reported.
selectivity in polymer membranes for O2/N2 separation,
Figure 5 is presented. It can be seen that most PIMs have
permeability and selectivity above the 1991 upper bound 2.2 Inorganic membranes
and a few lie on the 2008 upper bound. Some surface
modifications such as UV irradiation, plasma treatment, Inorganic membranes have attracted attention in gas
and plasma polymerization can push the separation separation field because of their ability to withstand high
performance beyond the 2008 upper bound. The shift operating temperature and pressure. In air separation
of trade-off relation due to surface modification of the process, the inorganic membrane is commonly used for
polymer membrane has been shown in our previous paper oxygen separation from air at elevated temperature (typi-
(Himma and Wenten 2016). The shift line with a positive cally 1073–1173 K). The common inorganic materials used
gradient to the right was not successfully achieved by for O2/N2 separation membrane are perovskites (Athayde
all works. In general, improvement of O2/N2 selectivity is et al. 2016), carbon, graphene, and zeolite (Figure 6).
accompanied with reduced O2 permeability, shown by the Other inorganic membranes are based on silica, zirconia,
shift line with a negative gradient to the left. An analysis and metal. In general, the inorganic membranes are clas-
by Freeman (1999) suggests that simultaneous chain stiff- sified into two basic types, dense (nonporous) and porous
ness and interchain separation increases (i.e. fractional membranes. Zeolite, silica, and zirconia are examples of
free volume) should be used to systematically improve the microporous membranes. In these membranes, O2/N2
separation performance until the interchain separation separation can be achieved by molecular diffusion mech-
becomes large enough that the polymer segmental motion anism. Meanwhile, the main group of dense inorganic
no longer governs penetrant diffusion. membranes is perovskite oxide membrane, wherein the
In general, gas permeability increases as the crystal- oxygen is permeated via ionic diffusion mechanism.
linity of the polymer membrane decreases. As reported by
Lin and Freeman (2004), amorphous poly(ethylene oxide)
(PEO) exhibited O2 and N2 permeability of 8.1 and 3.0 barrer, 2.2.1 Perovskite membranes
respectively. While in the semi-crystalline PEO, the O2 and
N2 permeability were much lower, i.e. 0.68 and 0.25 barrer, Several reviews of the ceramic-based membrane for oxygen
respectively. Reducing the crystallinity of PEO membrane separation from the air have been published (Sunarso
using crosslinking, copolymerization or blending strate- et al. 2008, Hashim et al. 2010, Zhang et al. 2011, Geffroy
gies could be used to push the separation performance of et al. 2013, Zhang et al. 2017). The ceramic-based mem-
branes are categorized based on conduction mechanism,
Figure 6: Inorganic-based membrane materials for O2/N2 separation

Figure 5: Trade-off relation between O2/N2 selectivity and O2 [according to the number of published papers (2000–2017) indexed
permeability of polymer membranes. by Scopus].

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namely, solid oxygen ionic conducting membranes (solid into the permeate stream. Therefore, high selectivity of
electrolyte) and mixed ionic-electronic conducting mem- oxygen (in theory 100% oxygen purity) can be achieved
branes (MIEC). In pure oxygen conducting membranes, as other gas molecular transports are blocked in case of
electrodes are provided as the electron pathway from the gas-tight membranes with perfect sealing.
anode to cathode; meanwhile, oxygen ions are transported The highest oxygen flux is generally observed for
by ionic diffusion through the solid or dense membrane dense ceramic membranes with a perovskite oxide struc-
(Figure 7A). The number of oxygen ions diffusing through ture. This oxygen semi-permeability is generally attributed
a dense membrane can be controlled by setting the gener- to the partial substitution of both A site (mainly composed
ated electric current during the separation process. of alkaline earth ions) and B cations (mainly composed of
As in the solid electrolyte membranes, MIEC has a transition metal ions) in the perovskite lattice structure
unique separation mechanism, i.e. oxygen or hydrogen (ABO3), as shown in Figure 8A (Teraoka et al. 1985, Zhang
is transported through the membranes in a dissociated et al. 2011, Athayde et al. 2016, de Larramendi et al. 2016).
or ionized form rather than the conventional molecular The ideal ABO3 structure consists of a cubic array of corners
diffusion (Figure 7B). Both oxygen ions and electrons are sharing BO6 octahedra. In the perovskites structure, the
transported through the ceramic membrane by the oxygen substitution of divalent alkaline-earth ions on the A site
partial pressure gradient applied across the membrane. At at elevated temperature enhances the oxygen vacancies
the permeate side (the low-pressure side), recombination concentration (Zhang et al. 2011). Therefore, the formula
occurs to form oxygen molecules which are then released of perovskite is written as ABO3−δ due to the deficiency of
Figure 7: Ceramic-based membranes for oxygen separation from air: (A) solid electrolyte cell and (B) mixed ionic electronic conductor (MIEC).
Figure 8: Schematic of perovskite structure (A) and oxygen transport mechanism through the perovskite membrane (B).

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anion oxygen. The presence of oxygen vacancies in per- demonstrates better oxygen permeation flux (Gao et al.
ovskite lattice structure induces the adsorption of oxygen 2011, Leo et al. 2011).
gas and acts as an oxygen carrier to migrate the oxygen Tan et al. (2011) have investigated the influence of the
ions to another side of the membrane surface (Figure 8B). membrane morphology on the performance of perovskite
Thus, the oxygen ion has a high mobility through the hollow fiber membrane, La0.6Sr0.4Co0.2Fe0.8O3–α (LSCF6428).
membrane, and a very high selectivity to oxygen is then The membrane morphology or microstructure was con-
obtained (Readman et al. 2005, Kharton et al. 2008, Tan trolled by using different bore fluids, i.e. H2O-NMP and
et al. 2010). The rate of oxygen ions transport in perovs- etanol-NMP mixtures. When a high NMP concentration
kite structure depends on the distribution state of oxygen in ethanol was used, a highly asymmetric hollow fiber
vacancies (Zhang et al. 2011). Simultaneously, the multi- membrane with one dense layer and highly porous struc-
valent ions on the B site experience reduction or oxida- ture showed the highest oxygen fluxes, which could be
tion, allowing neutralization of the overall charge by due to the decreased membrane effective thickness and
counterbalancing the flux of electrons. increased membrane area leading to reduced bulk diffu-
Commercial interest has been given to the transi- sion resistance. Ba0.5Sr0.5Co0.8Fe0.2O3–α (BSCF5582) hollow
tion metal perovskite type with Ba, La, and Sr at the A fiber membrane having a morphology of one dense layer
site with the B site occupied by transition elements Fe, integrated on the porous structure has also been obtained
Cr, and Co (Nagendra and Bandopadhyay 2003). Exam- when etanol-NMP mixture was used as the bore fluid (Han
ples of these perovskite-type membranes are BSCF et al. 2013). Perovskite membrane with such morphology
(barium-based, BaxSr1−xCoyFe1−yO3−δ), LSCF (lanthanum- has successfully provided very high oxygen permeation
based, La1−xSrxCo1−yFeyO3−δ), and STF (strontium-based, flux up to 1.92 × 10–3 m3/(m2 s). The oxygen flux can be
SrTi1−xFexO3−δ). The first study of oxygen separation based further enhanced by applying catalytic surface modifica-
on MIEC perovskite membrane was conducted by Teraoka tion on the membrane surface. As reported by Leo et al.
et al. (1985) using lanthanum-based material. Among the (2011), coating the BSCF hollow fibers with Pd nano-
perovskite-type membranes, BSCF has received particular particles improved the oxygen flux to 2.42 × 10–3 m3/(m2 s).
attention because of a more densified structure, which The oxygen permeation flux of the perovskite membranes
Table 5: Performances of perovskite-type membrane for oxygen separation.
Plannar perovskite-type Thickness Operating temperature O2 flux (10 − 4 Reference

(10 − 3 m) (K) m3 m − 2 s − 1)
Barium-based BaCo0.7Fe0.2In0.1O3−δ (BCFI) 1 1173 2.47 (Yang et al. 2015)

BaCo0.7Fe0.22Y0.08O3−δ (BCFY) 1 1173 2.88 (Zhao et al. 2010)
Ba0.8La0.2Co0.68Fe0.2Nb0.12O3−δ (BLCFN) 1 1173 1.60 (Tang et al. 2016)
BaCo0.7Fe0.24Zr0.06O3−δ (BCFZ) 1 1198 4.50 (Yao et al. 2016)
BaCo0.9Nb0.1O3−δ (BCN) 1173 4.35 (Wu et al. 2015)
Lanthanum-based La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) – 1343 5.17 (Tan et al. 2010)
La0.5Sr0.5Bi0.2Co0.35Fe0.45O3−δ 2 1173 0.38 (Islam et al. 2016)
Strontium-based SrCo0.8Fe0.2O3−δ (SCF) – 1123 4.00 (Teraoka et al. 1985)
SrCo0.8Fe0.1Ga0.1O3−δ (SCFG) – 1223 5.83 (Yang et al. 2013)
SrFe0.8Nb0.2O3−δ 1 1173 0.42 (Yi et al. 2013)
Hollow fiber Polymer solution Operating Swept gas (flow rate) O2 flux (10−4 m3 Reference
perovskite-type temperature m−2 s−1)
(K)
BaCoxFeyZrzO3−δ (BCFZ) – 1148 – 12.50 (Wang et al. 2005)

BaZrxCoyFezO3−δ (BCFZ) PSf in NMP 1173 – 12.67 (Schiestel et al. 2005)
BaNb0.05Fe0.95O3−δ (BNF) 1173 – 2.25 (Xu et al. 2014)
La0.6Sr0.4Co0.2Fe0.8O3−δ PES in NMP 1223 He (1.67 × 10−6 kg/s) 0.57 (Wang et al. 2015)
(LSCF) Steam (5 × 10−5 kg/s) 0.73
La0.6Sr0.4CoO3−δ (LSC) PSf in NMP 1273 He (1 × 10−6 m3/s) 3.82 (Wang et al. 2016)
Ba0.5Sr0.5Co0.8Fe0.2O3−δ PEI in NMPa 1223 Ar (2.5 × 10−2 m3 m−2 s−1) 24.17 (Leo et al. 2011)
(BSCF) PEI in NMP 1223 16.67
a
With catalyst surface modification on the hollow fiber.
PSf, polysulfone; PES, polyethersulfone; PEI, polyetherimide.

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with plannar or hollow fiber configuration is summarized cations (Tanasescu et al. 2013). Meanwhile, higher Ba
in Table 5. content resulted in lower oxygen dissolution because of
Brisotto et al. (2016) investigated the stability of the higher concentration of lattice defects that is attrib-
BSCF5582 and LSCF6428 during long-term annealing of uted by partial ordering of oxygen vacancies. Recently,
membrane at high temperature (1053–1093 K). They found cobalt-free perovskite-type membrane has also been
that a thin layer of carbon atoms was formed as a second- developed to reduce the membrane preparation cost and
ary phase on the BSCF-based membrane while LSCF mem- improve the membrane stability. It has been reported that
brane remained stable. The decomposition of BSCF during the presence of cobalt could negatively impact the mem-
operation at 1073 K is attributed to reversible rearrange- brane structure which then reduced oxgen permeation
ment of the AO3 layer from cubic into non-cubic (hexago- performance (Efimov et al. 2010, Luo et al. 2012). Cobalt
nal) structure, which is driven by the change of spin-state ions are easily reduced by reducing atmosphere at high
configuration of cobalt ions (Li et al. 2013b, Lumeij et al. temperature, which led to the decomposition of Co-based
2014). The formation of non-cubic phases might limit the perovskite membrane.
performance of the oxygen ion conductor, by increasing Besides the high cost of membrane preparation
the lattice stress and decreasing the oxygen vacancies and degradation of oxygen transport through the mem-
mobility (Lumeij et al. 2014). In BSCF perovskite structure, brane, another challenge in perovskite ceramic mem-
the loss of oxygen is mainly attributed to a reduction of brane is CO2 attack. A compact BaCO3 surface layer was
cobalt site compared to the iron site (Arnold et al. 2009). found on perovskite-type BaCo0.4Fe0.4Nb0.2O3−δ membranes
A number of studies have been conducted to improve during exposure to CO2-containing atmosphere (Yi et al.
the oxygen permeation and stability of perovskite-oxide- 2010).
based membranes by modifying the A site or B site Recently, a dual-phase composite ceramic mem-
(Kharton et al. 2001, Teraoka et al. 2006). For instance, brane containing perovskite has also been developed to
BSCF perovskite-type membranes can be modified by improve the chemical stability of the membrane, such
varying Ba:Sr and Co:Fe ratios, which strongly influ- as higher CO2 tolerance and better reduction tolerance.
ences the perovskite-type membrane phase structure and This membrane is commonly prepared by mixing two
ionic conductivity. Tanasescu et al. (2013) studied ther- ceramic material phases, in which one material pro-
modynamic stability of perovskite oxide in BSCF system vides large ionic conductivity and another offers large
(BaxSr1−xCo0.8Fe0.2O3−δ) by varying Ba:Sr ratios (x = 0.25–4) electronic conductivity. Fang et al. (2015b) mixed 80wt%
at constant Fe:Co ratio. They found that Ba-rich BSCF fluorite oxide (Ce0.8Gd0.15Cu0.05O2−δ) and 20wt% perovskite
perovskite-type membrane was more thermodynamically oxide (SrFeO3−δ). The CGCO-SFO composite membrane
stable than Sr-rich membrane. A mixture of phases with showed high and stable oxygen permeation fluxes over
cubic, hexagonal, and rhombohedral symmetries was 1.4 × 10 –4 m3/(m2 s) during long-term operation at 1173 K.
found in Ba-rich perovskite membrane at the investigated Other oxygen flux performance results of different com-
temperature (800–1273 K). Doping high concentration posite membranes are presented in Table 6.
of Ba increases the ability of lattice oxygen exchange, in
which less symmetrical non-cubic phases are expected
to have highly ordered oxygen vacancies. High concen- 2.2.2 Carbon-based membranes
tration of oxygen vacancies was formed in 50–60 mol%
Ba, which resulted in higher oxygen ionic conductivity Porous carbon membranes have also been considered as
and also stabilized the lower oxidation states of B-site promising candidates for low-cost gas separation instead
Table 6: Dual-phase oxygen transport ceramic membranes.
Material composition of membrane Membrane Operating Oxygen flux Reference

thickness temperature
Ionic oxygen conductor Electronic conductor
(10 − 3 m) (K)
Ce0.8Gd0.15Cu0.05O2−δ (80 wt%) SrFeO3−δ (20 wt%) 0.5 1173 2.83 × 10−4 m3/(m2 s) (Fang et al. 2015b)
Ce0.8Sm0.2O2−δ (63 wt%) La0.8Sr0.2CrO3−δ (37 wt%) 0.33 1223 8.6 × 10−5 mol/(m2 s) (Wang et al. 2006b)
Ce0.9Pr0.1O2−δ (60 wt%) Pr0.6Sr0.4FeO3−δ (40 wt%) 0.6 1223 3 × 10−5 m3/(m2 s) (Luo et al. 2012)
CeGd0.1Cu0.05O2−δ (75 wt%) La0.6Ca0.4FeO3−δ (25 wt%) 0.5 1223 1.17 × 10−4 m3/(m2 s) (Fang et al. 2015a)
Zr0.84Y0.16O1.92−δ (60 wt%) La0.8Sr0.2Cr0.5Fe0.5O3−δ (40 wt%) 1 1223 1.18 × 10−3 mol/(m2 s) (air/CO) (He et al. 2015)

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of the polymer membrane. The offered advantages to be the most critical factors affecting the properties of
include better molecular sieving properties, high hydro- the resulting carbon membrane. Numerous studies of
phobicity, heat resistance, and high corrosion resistance carbon membrane preparations have been performed
(Tanihara et al. 1999, Salleh and Ismail 2015). Based on by using synthetic polymer precursors, such as poly-
the separation mechanism, they can be categorized into acrylonitrile (PAN) (Sánchez-Soto et al. 2001, David and
two types: molecular sieve carbon membrane (MSCM) Ismail 2003), PEI (Fuertes and Centeno 1998, Sedigh et al.
and adsorption-selective carbon membrane (ASCM). 1999, Barbosa-Coutinho et al. 2003), PI (Vu et al. 2003),
MSCMs have average pore size less than 4.5 Å and poly(vinylidenechloride) (Centeno and Fuertes 2000),
are effective to separate gas molecules that have smaller and polyfurfuryl alcohol (Acharya 1999), or blending two
molecular size than the membrane pore size, such as O2, different kinds of polymers (Hosseini et al. 2014). It has
N2, CO2, and CH4 (Fuertes 2000). The separation mecha- been found that a strong trade-off relationship between
nism is based on the molecular size of gases, where the selectivity and permeability occurred in pure carbon-
smaller molecules are permeated through the membrane based membrane prepared from a synthetic polymer.
pores, while the larger ones are blocked. The permeation Some strategies have been proposed to minimize the
of gases can be enhanced by changing the operating tem- challenge; one of them is synthesizing a composite mem-
perature. Meanwhile, the separation mechanism of gas brane by incorporating zeolite (Liu et al. 2006b, Yin et al.
molecules in ASCM depends on their adsorption proper- 2010).
ties and interaction with the membrane material. The Liu et al. (2006a) embedded zeolite (ZSM-5) nano-
ASCMs have a larger pore size compared to MSCM, in the particles in carbon matrix made of PA precursor, which
range of 5–7 Å. This membrane is suitable for separating showed excellent separation performance for O2/N2 sepa-
non-adsorbable or weakly adsorbable gases (i.e. He, H2, ration. The oxygen permeability increased from 2.21 to 431
air, O2, N2, CH4, etc.) from adsorbable gases, such as hydro- barrer when 9.1 wt% of ZSM-5 was mixed into the polymer
carbons (C2+), NH3, SO2, H2S, and CFCs (Fuertes 2000). The precursor. The high gas permeability and selectivity of
schematic of separation mechanism in MSCM and ASCM the composite membranes were affected by the zeolite
is shown in Figure 9. Up to now, most of the studies on particle sizes (Liu et al. 2009). Kong et al. (2007) pre-
carbon membranes for gas separation are mainly focused pared composite carbon/zeolite membrane on a porous
on the preparation of MSCMs. alumina support by using vacuum slip casting method.
Carbon membranes are generally prepared by The selectivity of the composite membrane for pure O2/
pyrolysis (carbonization) of suitable polymer precur- N2 separation was 5.13. When it is used for air separation,
sors or carbon-containing materials such as thermoset- the composite membrane selectivity decreased to 3.69 due
ting resin, graphite, coal, pitch, and plants, under inert to the presence of competition adsorption of another pen-
atmosphere or vacuum (Saufi and Ismail 2004). The pre- etrant. Higher O2/N2 selectivity was found by dispersing
cursor type and operating parameters (such as temper- zeolite LTA (Linde Type A) or NaA (A-type zeolite of ca.
ature and time) in the pyrolysis process are considered 0.4 nm pore size) in carbon matrix (Zeng et al. 2008) or
Figure 9: The separation mechanism of gas mixture in (A) molecular sieve carbon membranes (MSCMs) and (B) adsorption-selective carbon
membranes (ASCMs).

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Table 7: Carbon membrane types for O2/N2 separation.
Precursor types Synthesis conditions Modifiers O2/N2 selectivity Reference
Polyimide 500°C, 2 h – 8.5–11.5 Jones and Koros (1994)

Poly(benzimidazole)/polyimide 800°C, 2 h – 12.85 Hosseini et al. (2014)
6FDA/DETDA:DABA (3:2) 800°C, with precrosslinking – 8.0 Fu et al. (2016)
Resorcinol-formaldehyde (RF) 600°C, 6 h – 3.3 Zhang et al. (2014)
resin – Pluronic F127
Polyimide 600°C, 6 h Zeolite (ZSM-5) 9.1 wt% in 14.4 Liu et al. (2006b)
precursor solution
Phenolic resin 600°C, 1 h Nano-sized NaA zeolite 14.6 Zeng et al. (2008)
(2 wt% in precursor solution)
synthesizing the zeolite membrane on a carbon support kinetic diameters as their selectivities are in the range of
(Domínguez-Domínguez et al. 2008). Performances of Knudsen values (Li and Qi 2015).
other carbon-based membranes for O2/N2 separation are
shown in Table 7.
2.3 Polymer-inorganic composite
membranes
2.2.3 O
ther inorganic membranes
2.3.1 Mixed matrix membranes
Besides perovskite and carbon membranes, a few other
inorganic membranes have also been investigated and In order to address the trade-off in polymer membranes,
considered as an alternative for O2/N2 separation. Zeolite a mixed matrix membrane (MMM) is developed. MMM
is one of the promising materials for gas separation is a heterogeneous membrane composed of inorganic
membrane due to its uniform and well-defined pore size filler and polymer matrix (Aroon et al. 2010, Khoiruddin
as well as high porosity (Huang et al. 2012). The zeolite and Wenten 2016, Sianipar et al. 2017). Except for addi-
membrane is commonly coated on a porous support with tion of filler particles into dope solution, the prepara-
a defect-free crystalline structure. Nishiyama et al. (2007) tion of MMM is substantially the same with membrane
used NaA zeolite to separate several gas mixtures. The preparation from unfilled dope solution. Compatibility
NaA membrane showed excellent separation factors of between inorganic filler and polymer matrix becomes a
>1200 (H2/CH4), >1600 (H2/N2), and >660 (H2/CO) at 298 K. significant criterion in MMM preparation, especially when
However, when it is used to separate O2/N2, low selec- glassy polymer matrix is used. Poor adhesion between
tivity was achieved, i.e. about 2–11 (Wang et al. 2002b, the polymer phase and the external surface of the particle
Domínguez-Domínguez et al. 2008). Nanoporous gra- leads to voids formation around the inorganic filler. This
phene membrane is another candidate for gas separation, can result in higher permeability but loss in selectivity.
where the separation mechanisms are commonly based To improve the adhesion, various attempts have been
on molecular sieving (Koenig et al. 2012). Fatemi et al. made. Functionalization or surface modification with
(2016) studied the graphene-based membrane perfor- coupling agents is usually used (Hu et al. 2006, Kim et al.
mance to separate a gas mixture containing Kr-85, O2, and 2007). The coupling agents could then interact simultane-
N2. It has been observed that nitrogen was more strongly ously with inorganic filler and polymer. It has been shown
adsorbed onto the graphene membrane than oxygen. Due that functionalization of filler particles with long-chain
to its low selectivity to O2/N2, further research is needed alky amines made them well dispersed in polymer matrix,
to improve the selectivity of the inorganic membrane and which provided high permeability while maintaining high
use as an alternative for household oxygen enrichment. selectivity (Kim et al. 2007). Another way is modification
Silica-based microporous membranes are also molecular in preparation technique. This includes annealing (Chen
sieving materials that can be used for separation of small et al. 2014) and priming (Vu et al. 2003). Another tech-
gaseous molecules such as O2 and N2. However, very few nique that can be used is to do a “priming” of inorganic
studies on it can be found (Hassan et al. 1995, Lin 2001). filler during the dope solution preparation. During the
Other ceramic materials such as titania and zirconia are “priming”, the inorganic filler is dispersed in a solution
not suitable for separation of gases with relatively small containing a polymer fraction. The function of “priming”

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is to envelope the fillers with the polymer before the rest microporous structures (Adams et al. 2010). Some advan-
of the polymer is added to the solution. “Priming” has tages of incorporating MOF in MMM are the high surface
been found to be able to improve filler-polymer interac- area, controllable porosity, and high affinity for certain
tion resulting in defect-free MMM. gases. More importantly, in comparison with other inor-
Numerous fillers can be used, including zeolite, ganic filler, MOF has higher compatibility with polymer
carbon molecular sieve (CMS), silica and metal oxide chains because of its organic linkers (Goh et al. 2011).
nanoparticles, carbon nanotubes, layered silicate, metal- Several studies have been conducted to test MOF per-
organic framework (MOF), and graphene (Goh et al. 2011). formance in MMM for O2/N2 separation. Zornoza and co-
Zeolite and CMS attracts great attention in MMM prepara- workers have studied HKUST-1 and ZIF-8 in a PSf matrix.
tion due to their size- and shape-selective nature allowing An increase in oxygen permeability and O2/N2 selectivity
molecular sieving discrimination. Zeolite 4A has a pore could be obtained compared with bare PSf membrane
size of 3.8 Å; thus, it is more favorable for separation of (Zornoza et al. 2011). The best result was obtained in a
O2/N2 than other zeolites, providing an accurate discrimi- PSf-ZIF8 MMM. They argue that, although both HKUST-1
nation between the size and shape difference of O2 and and ZIF-8 contribute in increasing oxygen permeability by
N2 molecules. Hu et al. (2006) have prepared MMM com- increasing membrane free volume, smaller pore aperture
posed of poly(methyl methacrylate) as polymer matrix of ZIF-8 than HKUST-1 brings more efficiency in the mole-
and zeolite as the inorganic filler. Using 3-(trimethox- cular separation of O2/N2 resulting in improved membrane
ysilyl) propylmethacrylate as compatibilizer, the MMM performance.
exhibited improved O2 permeability with maintained A rather different result was obtained when ZIF-8
selectivity. Incorporation of CMS in MMM was proven to and Matrimid were used as the filler and polymer matrix,
enhance O2/N2 selectivity by as much as 8% and 20% for respectively (Ordonez et al. 2010, Song et al. 2012). Com-
Ultem®-CMS and Matrimid®-CMS MMMs, respectively (Vu pared with the nascent Matrimid membrane, there was no
et al. 2003). The CMS particles seemed to have better affin- significant increase in O2/N2 ideal selectivity. This phenom-
ity to glassy polymers than zeolites; thus, good adhesion enon was observed even until 50 wt% loading of ZIF-8 in
and polymer-sieve contact can be achieved with minimal MMM (Ordonez et al. 2010). When the loading was further
modifications in casting. It was reported that incorpora- increased to 60 wt%, a decrease in selectivity was even
tion of octadecylammonium-functionalized single-walled observed. They argue that this phenomenon is caused
carbon nanotubes (SWNTs) in PSf matrix provided high by an increase in membrane free volume without render-
permeability while maintaining high selectivity (Kim ing any positive effect to membrane selectivity. Loading
et al. 2007). The unchanged O2/N2 selectivity was due to ZIF-8 particle in MMM only then contributes to increasing
unselectivity of SWNT for either O2 or N2. Performances of permeability (only up to 40 wt%) and also gives adverse
MMMs for O2/N2 separation from available literature are effect such as defective area in MMM.
summarized in Table 8. ZIF-8 has also been used in a PIM-1 for MMM fab-
Fernández-Barquín et al. (2016) have also system- rication (Bushell et al. 2013). ZIF-8 could be loaded
atically investigated the effect of three different zeolites into PIM-1 up to 43 vol%. Together with permeability
topologies (LTA, CHA, and Rho) for air separation. Using increase, ZIF-8-PIM1 MMM also exhibited an increase
PTMSP as the polymer, they found that selectivity of the in O2/N2 selectivity as the concentration of ZIF-8 in the
zeolite-PTMSP MMM could be significantly increased MMM was increased. Furthermore, the resulting MMM
compared with the pristine PTMSP, although a decrease was reported to be able to surpass the 2008 Robeson
in permeability in MMM was observed. The best performer plot for O2/N2 separation.
was 5 wt% LTA5/PTMSP with O2 permeability around 2727 Cu3(BTC)2 is also another MOF that has been investi-
barrer and 3.43 in selectivity. In addition to that, the per- gated to be used as filler for MMM. This particular MOF
meability of all MMM did not diminish as the temperature has been studied in a flat sheet configuration using
was raised up as observed in the pristine PTMSP. Good 4,4′-oxydiphthalicanhydride (ODPA)–2,4,6-trimethyl-1,3-
interaction between polymer and zeolites, enhance- phenylenediamine (TMPDA) polymer matrix (Duan et al.
ment of adsorption and surface diffusion, and molecular 2014). Although O2/N2 selectivity could not be significantly
sieving effect imparted from the zeolite are considered as improved, O2 permeation through the MMM could still
the positive aspects brought by the zeolites. increase. The maximum loading of the MOF was found
MOF is a relatively new class of microporous materi- to be 40 wt% since further increase would lead to defec-
als. It comprises metals or metal clusters connected by an tive membrane resulting in a significant drop in O2/N2
organic linker to create one-, two-, and three-dimensional selectivity.

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Table 8: Performances of MMMs for O2/N2 separation.
MMM composition Inorganic P(O2) O2/N2 Reference

filler loadinga (barrer) selectivity
Polymer Filler
Zeolite-MMM
PSf Zeolite 4A 60 wt% 23.30 4.0 Chen et al. (2014)
PMMA Zeolite 4A 20 wt% 2.04 5.1 Hu et al. (2006)
PSf Silicalite-1 16 wt% 2 4.3 Zornoza et al. (2011)
PSf SWNTs 10 wt% 1.23 5.4 Kim et al. (2007)
PSf Silica 0.1 wt% 15.83 GPU 6.4 Wahab et al. (2012)
PI (Matrimid) CMS 36 vol% 3.00 7.9 Vu et al. (2003)
PEI (Ultem) CMS 35 vol% 1.09 8.0 Vu et al. (2003)
PSf MCM 41 20 wt% 2.2 5.5 Reid et al. (2001)
PSf Xerogel 5 wt% 15.3 GPU 7.0 Magueijo et al. (2013)
PTMSP CHA 5 wt% 885 3.03 Fernández-Barquín et al. (2016)
LTA5 5 wt% 2727 3.43
Rho 5 wt% 1368 1.43
MOF-MMM
PVAc CuTPA 15 wt% 0.624 6.79 Adams et al. (2010)
Matrimid Cu-BPY-HFS 10 wt% 1.44 6.04 Zhang et al. (2008)
20 wt% 1.77 5.76
30 wt% 1.98 6.33
40 wt% 3.06 6.27
PSf MIL-101 (Cr) 8 wt% 2.7 4.5 Jeazet et al. (2012)
16 wt% 4.5 4.6
24 wt% 5.7 5.1
PSf ZIF-8 16 wt% 2.6 8.3 Zornoza et al. (2011)
HKUST-1 2.2 5.3
Matrimid ZIF-8 20 wt% 2.13 7.16 Ordonez et al. (2010)
30 wt% 3.39 5.76
40 wt% 5.88 5.56
50 wt% 1.13 6.67
60 wt% 1.99 4.55
5 wt% 3.15 6.6 Song et al. (2012)
10 wt% 4.64 7.3
20 wt% 5.63 6.4
30 wt% 10.18 6.1
ODPA-TMDPA Cu3(BTC)2 10 wt% 9 5 Duan et al. (2014)
20 wt% 28 5
30 wt% 36 5.1
40 wt% 44 5.2
Ultem MIL-53 2 wt% 6.3 GPU 6.9 Zhu et al. (2016)
5 wt% 8.1 7
8 wt% 9.5 GPU 6.7
PI, polyimide; PEI, polyetherimide; PVAc, poly(vinyl acetate); PSf, polysulfone; PMMA, poly(methyl methacrylate); PTMSP, polytri-
methylsilylpropyne; ODPA, 4,4′-oxydiphthalicanhydride; TMPDA, 2,4,6-trimethyl-1,3-phenylenediamine; SWNTs, single-walled carbon
nanotubes; CMS, carbon molecular sieve; MCM-41, mobil composition of matter-41); CuTPA, copper and terephthalic acid; Cu-BPY-HFS,
Cu-4,4′-bipyridine-hexafluorosilicate.
a
Based on polymer.
A water-stable MIL-101 (Cr) MOF has also been inves- at 24 wt% MOF loading, no selectivity enhancement could
tigated for O2/N2 separation in a MMM (Jeazet et al. 2012). be obtained. The authors suggest that gain in perme-
During the study, PSf was used as the polymer matrix. ability is due to the increase in membrane free volume.
Although an increase in permeability for both O2 and N2 However, the presence of MOF also contributes to increas-
gas could be observed, O2/N2 selectivity could not be sig- ing intersegmental spacing between polymer chains. This
nificantly improved compared with the pristine PSf. Even then results in enhancement of polymer mobility and

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facilitates gas diffusion without giving a negative effect 2.3.2 Polymer magnetic membranes
on the membrane selectivity.
Hollow fiber MOF-MMM configuration has also been A new concept of the magnetic membrane was proposed
tested for this purpose (Hu et al. 2010). Cu3(BTC)2 and PI recently as a promising way to effectively separate oxygen
were used as the MOF and polymer, respectively, to fabri- and nitrogen. This is based on the magnetic properties
cate MOF-MMM. The authors tested the 3 and 6 wt% MMM difference of O2(paramagnetic) and N2(diamagnetic). As a
for oxygen and nitrogen permeability. Upon increasing result, they behave differently in response to the magnetic
of MOF loading, both oxygen and nitrogen permeability field (Strzelewicz and Grzywna 2007).
decreased. The 3 wt% MMM gave oxygen and nitrogen For this purpose, magnets are dispersed in a mem-
permeability around 40 and 8 GPU, respectively. When brane, “magnetic membrane”, and/or placed on both
the MOF loading was increased to 6 wt%, the oxygen and sides of the permeation cell, “magnetic cell”. Magnetic
nitrogen permeability decreased to around 30 and 7 GPU, hybrid membranes based on EC, LPI (linear PI), HBPI
respectively. This then also indicates the decrease in O2/N2 (hyperbranched PI), and poly(2,6-dimethyl-1,4-phenylene
selectivity. They argue that this phenomenon is due to the oxide) with various magnetic praseodymium and neo-
MOF pore blockage by the polymer and rigidification of PI. dymium powder microparticles as fillers have been pre-
Another hollow fiber configuration has also been pared for O2/N2 separation (Rybak et al. 2009, Krasowska
studied using MIL-53 as the inorganic phase (Zhu et al. et al. 2012, Rybak et al. 2013, Rybak and Kaszuwara 2015).
2016). At the beginning, the attempt was not too success- Rybak et al. (2009) have prepared magnetic mem-
ful since defects on the membrane could still be observed. branes by dispersing magnetic neodynum powder in EC
They argue that the unsuccessful attempt is caused by solution and magnetizing the membrane in an external
MIL-53 that changes the phase-inversion behavior and magnetic field (magnetic induction up to 0.04 T during the
non-solvent ratio in the dope solution during membrane membrane casting and about 2 T for final magnetization).
fabrication process. This was then corrected by taking into The oxygen content in permeate strongly depended on the
account the pseudo-effect brought by MIL-53 during spin- magnetic field induction. Almost 56% of oxygen enrich-
ning process resulting in improved performance of the ment was achieved by using a magnetic induction of
hollow fiber MMM. 2.25 mT. As shown in Figure 10, the oxygen enrichment of
The results for MMM then indeed vary. Some studies magnetic membrane increases with the increase in mag-
showed the improvement for both permeability and O2/N2 netic field induction, with linear or almost linear relation-
selectivity, while some of them showed the opposite trend. ship. Regardless of the effect of the other parameters such
It is then important to carefully choose the inorganic as the loading of magnetic materials, magnetic membrane
fillers and polymer matrix to obtain MMMs with promis- from HBPI exhibited a higher oxygen enrichment for the
ing performance. magnetic field induction below about 2 mT than that from
Polyhedral oligomeric silsesquioxanes (POSS) is an LPI and EC.
emerging nanoporous filler, the structure of which is cage- Ferroferric oxide nanoparticles have also been used
like comprising 6–12 silicon atoms together with oxygen as the magnetic material. Madaeni et al. (2011) have pre-
atoms. A few studies have investigated the use of POSS pared magnetic membrane by coating fluidMAG-PAD
in MMM preparation for O2/N2 separation. Li et al. (2010)
reported that POSS-Matrimid MMM exhibited a decrease
in O2 and N2 permeability and a similar selectivity to the
neat Matrimid membrane. A work done by Iyer et al. (2010)
also showed that incorporation of POSS into PI matrix
decreased O2 permeability but increased O2/N2 selectivity.
The decrease in gas permeability can be due to the decrease
in free volume in MMM with the POSS loading, increase in
polymer chain rigidity, and pore blockage of POSS parti-
cles. The permeability might be improved by diminishing
the pore blockage so that the POSS cage is accessible by
the gas penetrants. One way is by increasing the separa-
tion test temperature (Li et al. 2017). However, this way can
result in lower selectivity. Thus, designing MMM with both Figure 10: Oxygen content in permeate as a function of magnetic
enhanced permeability and selectivity is still a challenge. field induction for different polymer matrices.

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(super-paramagnetic polymer containing magnetic Fe2O3

and Fe3O4 nanoparticles) on PES membrane. Oxygen per-
meability and O2/N2 selectivity increased with the increase
in external magnetic field because of O2 attraction by the
magnetized Fe2O3 and Fe3O4 nanoparticles. Besides the
external magnetic field, magnetic nanoparticles loading
also significantly affect the separation properties.
As reviewed above, magnetic particles can be intro-
duced by dispersing them in the polymer solution (as filler
in MMM) or by coating magnetic particles onto the exist-
ing membrane (surface modification). It has been shown
that the preparation method has an influence on the mem-
brane morphology which then affected the O2 separation
performance (Velianti et al. 2014). Compared with super-
paramagnetic MMM, superparamagnetic particle coated
membrane showed better O2 separation performance with
Figure 11: Effect of feed pressure on O2 permeance and O2/N2
the increase in O2 permeance and O2 mass transfer coef- selectivity.
ficient by about 580% and 11%, respectively. The gas per-
meation was improved with the increase in pore size and
porosity of the membranes. However, the selectivity was permeate as the base case. They were able to produce up to
too low; hence, controlling the morphological structure 95% of nitrogen by increasing the feed pressure by 345 kPa
needs to be further investigated. from the base case condition. Other studies (Ye et al. 2014,
2015) showed that maximum O2/N2 separation factors
decreased significantly as the feed pressure was increased.
3 P
rocess parameters in O2/N2 However, Hosseini et al. (2015) and Ettouney et al. (1998)
observed that elevating feed pressure increased the
separation oxygen content in the permeate up to a certain point, but
further increase brought a negative impact on the perme-
Besides the membrane characteristics, operating condi- ate stream. A rather conflicting result was also reported
tions are also a determining factor in the O2/N2 separation by Ruaan and co-workers. (1997). They found that both
process. These include operating pressure, tempera- oxygen and nitrogen permeability were independent of
ture, feed flow rate, and feed composition. Optimization the operating pressure while the oxygen/nitrogen selec-
of these parameters is then necessary to obtain good tivity remained constant. As the pressure was increased,
performance. oxygen and nitrogen showed different solubility behavior.
The former experienced a decrease in solubility, while the
latter remained constant.
3.1 Pressure At low pressure, the separation process is dominated
by competitive sorption of components thus resulting in
For gas separation application, membrane driving force permeance reduction. An increase in feed pressure will
is usually generated by applying (a) high pressure at increase the driving force that is needed for mass transfer
feed side and atmospheric pressure for permeate; (b) because of the augmented pressure difference across the
atmospheric pressure at feed side and vacuum condition membrane (Hosseini et al. 2015). However, when the feed
at permeate, or combination of both (a) and (b) models pressure is increased, nitrogen is preferentially adsorbed
(Bernardo and Clarizia 2013). Furthermore, the increase in resulting in its transport enhancement and lower O2/N2
feed pressure and the decrease in the permeate pressure selectivity (Ye et al. 2014).
give a great influence to the product recovery and produc-
tivity, while the required membrane area is reduced for a
given separation task (Feng et al. 1999). 3.2 Temperature
Some studies have observed the influence of feed pres-
sure on O2/N2 separation (Figure 11). Feng et al. (1999) used It has been shown that gas transport through the mem-
a feed pressure of 690 kPa and atmospheric pressure of brane with various structures is dependent on the

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temperature (Ismail et al. 2015). In solution-diffusion fiber lumen. This concentration polarization still becomes
model for a nonporous membrane, the permeability, P, is a big concern for the development of air separation mem-
controlled by diffusivity coefficient and solubility coeffi- brane processes (Feng et al. 1999).
cient. The diffusivity and solubility are a function of tem- Besides the flow configuration, feed flow rate also has a
perature, and the diffusivities of small gas molecules such big impact on the O2/N2 separation. Dong et al. (2015) found
as N2 and O2 is more sensitive to temperature than their that increasing the feed flow rate reduced the retentate N2
solubilities (Ghosal and Freeman 1994). Thus, the operat- concentration and increased the permeate O2 concentra-
ing temperature in O2/N2 separation has an influence on tion. Therefore, the increase in feed flow rate is important
the separation performance, prominently the permeabil- for O2 production where a feed flow rate in the range of
ity. The O2 and N2 permeability typically increased with 15–100 Nm3/h results in O2 concentration between 25% and
the increase in temperature (Ruaan et al. 1997, Feng et al. 40%. Meanwhile, for N2 enrichment, it is more appropriate
1999, Villaluenga et al. 2007, Ye et al. 2014). The increase to use feed flow rate lower than 18 Nm3/h to produce 95% of
in permeability was attributed to the increase in diffusiv- N2. Furthermore, Ettouney et al. (1998) observed that higher
ity with the increase in temperature. However, elevating gas flow rate leads to lower gas residence time and then
the operating temperature could decrease the O2 and N2 increases the permeation resistance. The optimum oxygen
solubilities and the solubility ratio, resulting in decreased enrichment was obtained at the lowest pressures and the
selectivity (Ruaan et al. 1997). This has been shown for highest flow rate where the permeation resistance was high
instance in PTMSP since it has a high free volume and is and resulted in higher O2 permeation rate.
more prone to solubility fluctuation rather than diffusiv-
ity (Fernández-Barquín et al. 2016). Apart from this, it has
3.4 Feed composition
also been reported that the decreased selectivity with the
increase in temperature in homogeneous and heterogene-
Feed composition is one of the important factors determin-
ous membranes could also be due to the decreased diffu-
ing membrane performance. Feed composition directly
sivity selectivity (Villaluenga et al. 2007). Based on those
affects the solubility and sorption-diffusion phenomena
studies, it is suggested that a small or negligible decrease
at the gas-membrane interface. In multi-component feeds,
in selectivity can be obtained when the decrease in solu-
coupling effects between two or more species may occur
bility ratio is balanced with the increase in diffusivity
and could influence the selectivity. In addition, the pres-
ratio or diffusivity selectivity. The selectivity determines
ence of condensable species could plasticize the mem-
the product purity and recovery; thus, changes in temper-
brane and deteriorate its long-term performance (Dong
ature can also effect the purity of product. A simulation
et al. 2013). Hosseini et al. (2015) found that increase in
by Hosseini et al. (2015) for non-ideal model showed that
concentration of the more permeable component (i.e. O2)
the purity of O2 in permeate and the purity of N2 in reten-
in the feed stream increases the concentration of O2 in per-
tate decreased with the increase in temperature, but the
meate. It is due to the increase in the driving force for O2
decrease in the purity of N2 was less pronounced.
permeation, while the driving force for N2 permeation is
reduced. Therefore, the feed with higher oxygen content
results in permeate streams with high-purity oxygen.
3.3 F eed flow rate and flow configuration
However, for both O2 and N2 enrichment, higher product
purity leads to the reduction of product recovery, thus
The commercial membrane systems for O2/N2 separations
affecting the energy consumption and operating cost.
are mainly based on asymmetric hollow fiber membranes.
Therefore, optimization of feed composition and operat-
The feed is usually passed from the bore side since it gives
ing conditions is needed in order to maximize the separa-
a better separation than the shell-side feed. The separa-
tion potential of the membrane (Feng et al. 1999).
tion performance difference of bore-side feed and shell-
side feed becomes more prominent with the increase in
pressure since it will affect the fiber diameter. Bore-side
feed mode will expand the fiber and increase permeance,
4 Applications
while shell-side feed will compress the fiber and decrease
permeance (Rautenbach et al. 1998). However, in the bore- 4.1 Oxygen enrichment
side feed, concentration polarization is more likely to
occur because of the stagnant gas zones in the porous sub- Many industries use oxygen for a variety of reasons, such
strate of the hollow fibers as the feed gas passes down the as in the glass, gasification, and gas-to-liquid industries

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(Rao and Muller 2007). The use of high concentration pass membrane produced 95% nitrogen, and 99.5% purity
of oxygen can reduce heating time, while CO concentra- was obtainable with a further stage.
tion increased almost linearly with the oxygen concen-
tration (Wu et al. 2010). Oxygen-enriched air can also
be used to optimize hydrogen production by filtration 4.1.1 Oxy-combustion
combustion of methane. The increase in oxygen concen-
tration makes combustion temperature drop, while the Oxy-combustion has become one of the most attractive
absolute flame propagation rate increases (Bingue et al. combustion technologies in the last decade for a more
2004). economical way to produce oxygen (Alsayed 2008). Oxy-
Recently, some studies have reported oxygen produc- combustion is recognized as an alternative process for
tion by membrane processes. Smith and Klosek (2001) coal-fired power plants to continue operation in a carbon-
used inorganic oxide ceramic materials to produce high constrained world. In 1982 oxy-coal combustion was origi-
concentration oxygen. The inorganic oxide ceramic mem- nally proposed to produce CO2 for enhanced oil recovery
brane is able to produce nearly 99% oxygen. The system (Abraham et al. 1982, Scheffknecht et al. 2011, Shaddix
was operated at high temperatures, over 866 K. First, and Molina 2011, Lockwood 2014). But lately, interest has
the oxygen molecules were converted to oxygen ions at been paid to oxy-coal combustion to reduce pollutant
the surface of the membrane. The oxygen ions were then emission and create a CO2 gas stream that can easily be
transported through the membrane by applying electri- removed.
cal voltage or oxygen partial pressure difference. After In oxy-combustion, a high-purity oxidant stream
passing through the membrane, the oxygen ions turned is used for the combustion process. The aim of this
back into oxygen molecules. concept is to obtain a CO2-rich stream that can be recov-
Murali et al. (2013) also used membrane-based sepa- ered by sequestration, after removing water vapor and
ration for O2 production. Production of pure O2 is difficult other impurities (Favre et al. 2009, Murali et al. 2013).
since a little quantity of N2 always permeates through the Replacing combustion air with a mixture of oxygen and
membranes; thus, it is commonly named oxygen-enriched recycled flue gases gives several advantages, such as
air (OEA) rather than pure O2 production. However, as increased efficiency, lower emissions, improved temper-
pure O2 is being desired by most users, the addition of a ature stability and heat transfer, increased productivity,
second separation stage appears more promising. Clark improved ignition characteristics, and low risk (Ochs
and Rowan (1996) studied an efficient method for oxygen et al. 2004, U.S. Department of Energy 2005, Alsayed
enrichment from the air stream by passing the incoming 2008).
air through a series of membranes. The results showed that Schematic diagram of the oxy-combustion process
there is a preferential diffusion rate for oxygen through is presented in Figure 12. The fuel and recycled flue gas
the membrane over the other gases in the air. Thirty-five are combusted with OEA to produce a gas mixture that
percent of oxygen was successfully achieved by a single mainly contains CO2 and water vapor. The net flue gas
pass through the membrane, while second stage mem- contains about 80–98% CO2 depending on the fuel used
brane was needed to improve the oxygen concentration and the particular oxy-fuel combustion process. Due to
up to 50%. Similarly, for nitrogen enrichment, a single its high concentrations, CO2 can be recovered with the
Figure 12: Schematic diagram of oxy-combustion process.

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flue gas compression train (Shaddix and Molina 2011). to produce electricity or steam. Gasification is able to
Meanwhile, the water in the flue gas is condensed, and use low-BTU fuels for energy production, while carbon
the small amounts of impurities (i.e. SOx, NOx, O2, noble dioxide can be easily captured compared to traditional
gases, metals, and particulates) are removed (Buhre et al. sequestration methods. Besides, this process can also be
2005, Tan et al. 2006, Skeen et al. 2009). Captured CO2 is used to produce hydrogen gas. In gasification, the fuel is
then transported to an injection site and sequestered for ground up into slurry and then pyrolyzed in an oxygen-
long-term storage in any of a variety of suitable geologic starved environment to turn the majority of the carbon
formations. into a gas. After that, oxygen or air (“direct gasification”)
The oxy-combustion process has numerous environ- or steam (“indirect gasification”) is added at high temper-
mental benefits as well as improved energy efficiency atures to form carbon monoxide and hydrogen (Rao and
and productivity. This energy saving comes from the Muller 2007).
nitrogen-free combustion process. As a result, energy An appropriate concentration of oxygen is required to
lost from heating nitrogen can be avoided (Ming et al. initiate the exothermic reactions that provide energy for
2003). Moreover, as the oxygen concentration increased, the endothermic reactions to produce more hydrogen. In
more energy is available and less fuel is required. gasification process, the hydrogen content is affected by
By increasing O2 in combustion air from the ambient the increase in oxygen concentration. However, the effects
21%–30%, fuel savings of ~20% were possible, with may vary depending on the oxidation reactions that pos-
the furnace temperature held constant. Meanwhile, the sibly convert H2 to H2O. Similar to H2, CO content in syngas
energy saving of up to 60% can be achieved by increas- also increased when oxygen percentage changed from 21
ing oxygen concentration from 21% to 35%, as shown in to 40 vol%, although the increase in CO is much less than
Figure 13. Besides energy savings, another advantage of H2. It is because three moles of H2 are produced, while
oxy-combustion is the CO2 capture efficiency of nearly only one mole of CO is produced in a steam reforming
100%. Using OEA as the feed to the power plant ensures reaction. The higher concentration of oxygen introduced
that the flue gas contains nearly pure CO2, which elimi- into the reactor, the higher carbon conversion efficiency
nates the expensive CO2/N2 separation necessary for can be achieved since the presence of extra oxygen may
capture and sequestration. enhance the oxidation reactions, thus releasing more
heat to accelerate the gasification process (Van Huynh
and Kong 2013).
4.1.2 Gasification
Gasification is a process to transform coal or another 4.1.3 Desulfurization

carbon-based fuel into a synthesis gas (“syngas”). This
syngas is made up mostly of CO and H2 that can be used Nowadays, oxygen enrichment becomes a cost-effective
solution to increase a plant’s sulfur handling capac-
ity. It also addresses the problems associated with con-
taminants, including ammonia and hydrocarbons.
Higher concentration of oxygen significantly increases
sulfur handling capacity and thus increases productiv-
ity without changing the pressure drop. The use of OEA
is also effective for ammonia-containing feeds. Further-
more, oxygen enrichment can be used to improve Claus
plant and increase the capacity up to 150% (Ahamparam
and Harrison 2012). The oxygen can be injected via a
diffuser into the process air to the sulfur recovery unit.
The maximum oxygen concentration that can be accom-
modated via this method is 28% and provides a capacity
increase in approximately 30%. When greater capacity
is needed, increase in oxygen beyond 28% is required.
Figure 13: Effect of oxygen concentration and temperature on
However, it is necessary to introduce oxygen into the
energy saving (data from U.S. Department of Energy 2005, Ming reaction furnace separately from the air supply to main-
et al. 2003). tain the piping and burners.

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4.1.4 I ntensification of air oxidation reactions (now part of MG) produced the first air separation system
based on PMP membranes with an O2/N2 selectivity of
Oxygen enrichment is a simple way of increasing the effi- about 4 (Baker 2002). Then, the milestones in the indus-
ciency of air oxidation processes, from refinery operations trial application of membrane O2/N2 separation systems
to downstream chemical processes. OEA can replace part are as follows (Bernardo and Clarizia 2013): PSf hollow
of the process air feed or it can be added to the existing fiber membranes for O2/N2 (Dow Chemicals – 1984), com-
supply, depending on the process requirements. OEA can posite hollow fiber membranes for O2/N2 (IMS – 1987),
bring similar benefits to production processes that use and polyphenylene oxide membranes for air separation
catalytic air oxidation in the gas or gas-liquid phase (Rein- (Delair – 1991). Recently, Air Products – supported in part
hardt et al. 2015). There are some advantages of oxidation by the U.S. Department of Energy – has developed ion
reactions with oxygen enrichment, such as increase in transport membrane for air separation. They have suc-
capacity (often by 10–20%) and oxidation temperature, cessfully operated the 5 TPD sub-scale engineering proto-
higher yield, improvement in operation flexibility, lower type (Air Products 2008). This will be then further scaled
off-gas volume, and reduction of CO2 emission (The Linde up for large-scale future energy applications (1000 TPD O2,
Group 2012). power) and industrial applications (100 TPD O2, <100 MW)
by the end of this decade (Air Products 2013). Concur-
rently with the development in the large scale, intensive
4.2 Nitrogen enrichment research in the laboratory scale also continues to grow
since there are still many challenges to be addressed to
Since air contains approximately 80% nitrogen and it obtain highly efficient membrane-based O2/N2 separation.
remains on the residue side of the membrane, production Various materials have been developed to obtain
of pure nitrogen is comparatively easier than pure oxygen. membranes with high O2 permeability and high O2/N2
Generally, membrane technology can produce up to 95% selectivity, including polymer, polymer-inorganic com-
nitrogen with a recovery of 50%. posite, and inorganic materials. Polymer membranes
Nitrogen is important as an inert gas or liquid for have long been developed. Numerous approaches have
cooling and freezing. It supports a multitude of commer- been made to overcome the trade-off relation between
cial and technical applications, since nitrogen’s unique permeability and selectivity, including improvement of
properties can be used to improve yields, optimize per- phase inversion process to obtain ultrathin and defect-
formance, protect product quality, and make operations free skinned asymmetric membrane, polymer blending,
safer (Ivanova and Lewis 2012). Some applications of developing microporous polymer, and membrane surface
nitrogen enrichment air are manufacturing pressure- modification using UV irradiation, ion beam irradiation,
sensitive adhesives (Czech 2004, Czech and Wesolowska plasma treatment, plasma polymerization, chemical
2007), storing and handling free-radical polymerization cross-linking, coating, and heat treatment. From the trade-
monomers (Kottke and Stalke 1993), and handling vinyl off relation between O2/N2 selectivity and O2 permeability
chloride monomer (VCM) (Crider et al. 1979, Ivanova and of polymer membranes, most PIMs have permeability and
Lewis 2012). Nitrogen-enriched air (NEA) produced by selectivity above the 1991 upper bound, and a few lie on
membrane process can also be used for inerting aircraft the 2008 upper bound. Meanwhile, some surface modi-
fuel tanks. This process involves replacing the vapor head- fications such as UV irradiation, plasma treatment, and
space containing 21% O2 by the liquid fuel with NEA con- plasma polymerization can give high permeability and
taining 1–5% O2. The compressed air is passed through selectivity above the 2008 upper bound.
the membrane module and then NEA is forced into vapor In large-scale production, the use of membranes can
headspace to displace the initial air. be classified as the following (Prasad et al. 1994): (1) mem-
branes with selectivities of 3–4 combined with high perme-
abilities (~600 barrers) for O2 production with low purity,
5P
rogress in large scale, challenges, i.e. <50%; (2) membranes with selectivity of 8–10 and per-
meability of 10 barrers for N2 production with high purity;
and future outlook and (3) membranes with very high selectivity (>30) and
very high permeabilities (>50 barrers) for O2 production
The advance in membrane fabrication technology for O2/ with high purity, i.e. over 90%. Thus, from the available
N2 separation began with the development of asymmetric data of permeability and selectivity of polymer membranes,
membrane in the 1970s (Baker 2004). In 1982, Generon it can be concluded that most of the polymer membranes

Authenticated
are suitable for the production of low to moderate purity separation membrane with a superhydrophobicity may
O2 and for production of high-purity N2. Although it is not be a solution, preventing membrane wetting by the liquid
impossible, high-purity O2 production using a polymer water. However, the use of membranes for air separation
membrane is still a huge challenge to be addressed. process in the presence of heavy organics and liquid water
Aside from polymeric materials, inorganic materi- is still limited and rarely investigated.
als also play a significant role in membrane-based O2/N2 All these developments then broaden the application
separation. Ceramic membranes can give high selectiv- of membrane for O2/N2 separation. Oxygen enrichment
ity towards oxygen up to 100%. For dense ceramic mem- for oxy-combustion, gasification, desulfurization, and
branes with a perovskite oxide structure, a high oxygen intensification of air oxidation reactions; and nitrogen
flux of about 3 × 10–4–24 × 10–4 m3/(m2 s) can be achieved. enrichment for manufacturing pressure-sensitive adhe-
In addition, inorganic membranes are superior over sive, storing and handling free-radical polymerization
polymer membranes in terms of durability at high temper- monomers, and handling VCM are among the promising
ature and pressure. Thus, the ceramic membrane is very areas where such a membrane can play a major role. For
suitable for the production of high-purity O2. However, air separation application, a portable membrane-based
high-cost membrane preparation, degradation of oxygen air purifier is also a promising development because of its
transport through the membrane, and CO2 attack are the compactness and its ability to produce fresh air for house-
major challenges. Porous carbon membranes have also hold application.
been considered as promising candidates for low-cost gas In conclusion, this review has extensively discussed
separation instead of the polymer membrane, which has membrane-based O2/N2 separation. Membrane perfor-
shown its better molecular sieving properties. However, mance in this area is greatly affected by membrane mate-
their selectivities are still in the range of 8–14. rials and its fabrication process and also by membrane
MMM combines the advantages of both polymeric operating conditions. Although challenging, once these
and inorganic materials. Zeolite attracts great attention parameters have been efficiently tuned, various prom-
as an inorganic filler due to their size and shape selec- ising applications that require oxygen separation from
tive nature. Besides, a relatively new class of microporous nitrogen, for instance, air separation and gas enrichment,
materials, MOF, can also be incorporated in MMM, giving can then be well handled by membrane process.
the advantages of high surface area, controllable porosity,
high affinity for certain gases, and, more importantly, high
compatibility with polymer chains. Zeolite-MMMs perme-
ability is in the range of 1.09–23 barrers and selectivity References
of 4–8.0, and MOF-MMMs give permeability of 0.624–23
Abraham B, Asbury J, Lynch E, Teotia A. Coal-oxygen process provides
barrers and selectivity of 4.5–8.0. A new concept in the
CO2/for enhanced recovery. Oil Gas J 1982; 80: 11.
polymer-inorganic composite membrane is by incorporat- Acharya M. Engineering design and theoretical analysis of
ing magnetic microparticles as fillers, namely, magnetic nanoporous carbon membranes for gas separation. PhD Thesis,
membrane. It could be a promising way of the effective Univ. of Delaware, Newark, 1999.
O2/N2 separation due to the substantial differences of O2 Adams R, Carson C, Ward J, Tannenbaum R, Koros W. Metal organic
framework mixed matrix membranes for gas separations.
and N2 in response to the magnetic field (oxygen is par-
Microporous Mesoporous Mater 2010; 131: 13–20.
amagnetic, whereas nitrogen is diamagnetic). Oxygen Ahamparam S, Harrison S. Oxygen enrichment in desulphurisation.
enrichment up to 70% could be achieved by using a high Pet Technol Q 2012; 17: 51–53.
magnetic induction of about 2 mT. Air Products. Air separation technology – ion transport membrane
Regardless of the membrane materials, when under (ITM). Allentown, PA: Air Products and Chemicals, Inc., 2008.
operation, the presence of contaminants is regarded as the Air Products. Advanced oxygen for energy intensive markets: ion
transport membrane (ITM) oxyge. Allentown, PA: Air Products
most crucial aspect that affects membrane performance. It
and Chemicals, Inc., 2013.
has been recognized that many air separation membranes Alsayed MFM. Oxygen enriched combustion of high emission fuels.
suffer significant degradation in performance when ME thesis, An-Najah National University, 2008.
exposed to very low concentrations of heavy organics Ariono D, Purwasasmita M, Wenten IG. Brine effluents:
(primarily oil vapors from the compressed air) in the feed characteristics, environmental impacts, and their handling.
J Eng Technol Sci 2016; 48: 367–387.
stream. In addition, the membranes may be susceptible to
Ariono D, Khoiruddin K, Subagjo S, Wenten IG. Heterogeneous
degradation from liquid water, especially in combination structure and its effect on properties and electrochemical
with other feed stream contaminants that can produce behavior of ion-exchange membrane. Mater Res Express 2017;
acids (Prasad et al. 1994). For this reason, rendering gas 4: 024006.

Authenticated
Arnold M, Xu Q, Tichelaar FD, Feldhoff A. Local charge disproportion Buonomenna MG, Yave W, Golemme G. Some approaches for high
in a high-performance perovskite. Chem Mater 2009; 21: performance polymer based membranes for gas separation:
635–640. block copolymers, carbon molecular sieves and mixed matrix
Aroon MA, Ismail AF, Matsuura T, Montazer-Rahmati MM. membranes. RSC Advances 2012; 2: 10745–10773.
Performance studies of mixed matrix membranes for gas Bushell AF, Attfield MP, Mason CR, Budd PM, Yampolskii Y,
separation: a review. Sep Purif Technol 2010; 75: 229–242. Starannikova L, Rebrov A, Bazzarelli F, Bernardo P, Jansen JC.
Aryanti P, Yustiana R, Purnama R, Wenten IG. Performance and Gas permeation parameters of mixed matrix membranes based
characterization of PEG400 modified PVC ultrafiltration on the polymer of intrinsic microporosity PIM-1 and the zeolitic
membrane. Membr Water Treat 2015; 6: 379–392. imidazolate framework ZIF-8. J Membr Sci 2013; 427: 48–62.
Aryanti P, Joscarita SR, Wardani AK, Subagjo S, Ariono D, Wenten Camacho-Zuñiga C, Ruiz-Treviño FA, Hernández-López S, Zolotukhin
IG. The influence of PEG400 and acetone on polysulfone MG, Maurer FHJ, González-Montiel A. Aromatic polysulfone
membrane morphology and fouling behaviour. J Eng Technol copolymers for gas separation membrane applications.
Sci 2016; 48: 135–149. J Membr Sci 2009; 340: 221–226.
Aryanti P, Sianipar M, Zunita M, Wenten IG. Modified membrane with Centeno TA, Fuertes AB. Carbon molecular sieve gas separation
antibacterial properties. Membr Water Treat 2017; 8: 463–481. membranes based on poly (vinylidene chloride-co-vinyl
Athayde DD, Souza DF, Silva AM, Vasconcelos D, Nunes EH, da Costa chloride). Carbon 2000; 38: 1067–1073.
JCD, Vasconcelos WL. Review of perovskite ceramic synthesis Chauhan R, Pandey P. Preparation of gas separation membranes and
and membrane preparation methods. Ceram Int 2016; 42: their evaluation. Def Sci J 2004; 54: 335.
6555–6571. Chen S-H, Chuang W-H, Wang AA, Ruaan R-C, Lai J-Y. Oxygen/
Baker RW. Future directions of membrane gas separation nitrogen separation by plasma chlorinated polybutadiene/
technology. Ind Eng Chem Res 2002; 41: 1393–1411. polycarbonate composite membrane. J Membr Sci 1997; 124:
Baker RW. Membrane technology and applications, West Sussex, 273–281.
England: John Wiley & Sons Ltd, 2004. Chen S-H, Yu K-C, Houng S-L, Lai J-Y. Gas transport properties of
Baker RW, Lokhandwala K. Natural gas processing with membranes: HTPB based polyurethane/cosalen membrane. J Membr Sci
an overview. Ind Eng Chem Res 2008; 47: 2109–2121. 2000; 173: 99–106.
Baker RW, Low BT. Gas separation membrane materials: a Chen J-T, Shih C-C, Fu Y-J, Huang S-H, Hu C-C, Lee K-R, Lai J-Y.
perspective. Macromolecules 2014; 47: 6999–7013. Zeolite-filled porous mixed matrix membranes for air
Barbosa-Coutinho E, Salim VM, Borges CP. Preparation of carbon separation. Ind Eng Chem Res 2014; 53: 2781–2789.
hollow fiber membranes by pyrolysis of polyetherimide. Carbon Chong K, Lai S, Thiam H, Teoh H, Heng S. Recent progress of oxygen/
2003; 41: 1707–1714. nitrogen separation using membrane technology. J Eng Sci
Belaissaoui B, Le Moullec Y, Hagi H, Favre E. Energy efficiency of Technol 2016; 11: 1016–1030.
oxygen enriched air production technologies: cryogeny vs Chung T-S, Kafchinski ER, Foley P. Development of asymmetric
membranes. Sep Purif Technol 2014; 125: 142–150. hollow fibers from polyimides for air separation. J Membr Sci
Bernardo P, Clarizia G. 30 years of membrane technology for gas 1992; 75: 181–195.
separation. Chem Eng Trans 2013; 32: 1999–2004. Chung T-S, Kafchinski ER, Vora R. Development of a defect-free
Bingue JP, Saveliev AV, Kennedy LA. Optimization of hydrogen 6FDA-durene asymmetric hollow fiber and its composite hollow
production by filtration combustion of methane by oxygen fibers. J Membr Sci 1994; 88: 21–36.
enrichment and depletion. Int J Hydrogen Energy 2004; 29: Chung TS, Teoh SK, Hu X. Formation of ultrathin high-performance
1365–1370. polyethersulfone hollow-fiber membranes. J Membr Sci 1997;
Borisov S, Khotimsky VS, Rebrov AI, Rykov SV, Slovetsky DI, Pashunin 133: 161–175.
YM. Plasma fluorination of organosilicon polymeric films for gas Clark GA, Rowan M. A feasibility study of using oxygen enrichment
separation applications. J Membr Sci 1997; 125: 319–329. for fuel cell air independent propulsion. Melbourne: DSTO
Brisotto M, Cernuschi F, Drago F, Lenardi C, Rosa P, Meneghini C, Aeronautical and Maritime Research Laboratory, 1996.
Merlini M, Rinaldi C. High temperature stability of Clausi DT, Koros WJ. Formation of defect-free polyimide hollow fiber
Ba0.5Sr0.5Co0.8Fe0.2O3–δ and La0.6Sr0.4Co1−yFeyO3–δ oxygen membranes for gas separations. J Membr Sci 2000; 167: 79–89.
separation perovskite membranes. J Eur Ceram Soc 2016; Comesaña-Gándara B, Hernández A, de la Campa JG, de Abajo J,
36: 1679–1690. Lozano AE, Lee YM. Thermally rearranged polybenzoxazoles
Budd PM, Msayib KJ, Tattershall CE, Ghanem BS, Reynolds KJ, and poly(benzoxazole-co-imide)s from ortho-hydroxyamine
McKeown NB, Fritsch D. Gas separation membranes from monomers for high performance gas separation membranes.
polymers of intrinsic microporosity. J Membr Sci 2005; 251: J Membr Sci 2015; 493: 329–339.
263–269. Crider LB, O’Mara MM, Bowles RL. A model for the diffusion of
Budd PM, McKeown NB, Ghanem BS, Msayib KJ, Fritsch D, vinyl chloride monomer from PVC under various conditions of
Starannikova L, Belov N, Sanfirova O, Yampolskii Y, storage. J Vinyl Technol 1979; 1: 168–171.
Shantarovich V. Gas permeation parameters and other Czech Z. Development of solvent-free pressure-sensitive adhesive
physicochemical properties of a polymer of intrinsic acrylics. Int J Adhes Adhes 2004; 24: 119–125.
microporosity: polybenzodioxane PIM-1. J Membr Sci 2008; Czech Z, Wesolowska M. Development of solvent-free acrylic
325: 851–860. pressure-sensitive adhesives. Eur Polym J 2007; 43:
Buhre BJP, Elliott LK, Sheng CD, Gupta RP, Wall TF. Oxy-fuel 3604–3612.
combustion technology for coal-fired power generation. Prog David L, Ismail A. Influence of the thermastabilization process and
Energy Combust Sci 2005; 31: 283–307. soak time during pyrolysis process on the polyacrylonitrile

Authenticated
carbon membranes for O2/N2 separation. J Membr Sci 2003; Fernández-Barquín A, Casado-Coterillo C, Valencia S, Irabien A.
213: 285–291. Mixed matrix membranes for O2/N2 separation: the influence of
de Larramendi IR, Ortiz-Vitoriano N, Dzul-Bautista IB, Rojo T. temperature. Membranes 2016; 6: 28.
Designing perovskite oxides for solid oxide fuel cells. In: Pan Freeman BD. Basis of permeability/selectivity tradeoff relations in
L, editor. Perovskite materials-synthesis, characterisation, polymeric gas separation membranes. Macromolecules 1999;
properties, and applications. Rijeka: InTech, 2016: 589–617. 32: 375–380.
Ding X, Cao Y, Zhao H, Wang L, Yuan Q. Fabrication of high Freeman BD, Pinnau I. Polymeric materials for gas separations. In:
performance Matrimid/polysulfone dual-layer hollow fiber Freeman BD, Pinnau I, editors. Polymer membranes for gas
membranes for O2/N2 separation. J Membr Sci 2008; 323: and vapor separation. Washington, DC: American Chemical
352–361. Society, 1999: 1–27.
Domínguez-Domínguez S, Berenguer-Murcia A, Morallón E, Fritzsche AK, Murphy MK, Cruse CA, Malon RF, Kesting RE.
Linares-Solano A, Cazorla-Amorós D. Zeolite LTA/carbon Characterization of asymmetric hollow fibre membranes with
membranes for air separation. Microporous Mesoporous Mater graded-density skins. Gas Sep Purif 1989; 3: 106–116.
2008; 115: 51–60. Fritzsche AK, Armbruster BL, Fraundorf PB, Pellegrin CJ. The
Dong G, Li H, Chen V. Challenges and opportunities for mixed-matrix structure of the effective separating layer of asymmetric hollow
membranes for gas separation. J Mater Chem A 2013; 1: fiber membranes with graded density skins. J Appl Polym Sci
4610–4630. 1990a; 39: 1915–1932.
Dong G, Woo KT, Kim J, Kim JS, Lee YM. Simulation and feasibility Fritzsche AK, Cruse CA, Murphy MK, Kesting RE. Polyethersulfone
study of using thermally rearranged polymeric hollow fiber and polyphenylsulfone hollow fiber trilayer membranes spun
membranes for various industrial gas separation applications. from Lewis acid:base complexes – structure determination by
J Membr Sci 2015; 496: 229–241. SEM, DSC, and oxygen plasma ablation. J Membr Sci 1990b; 54:
Drioli E, Curcio E. Membrane engineering for process intensification: 29–50.
a perspective. J Chem Technol Biotechnol 2007; 82: 223–227. Fu Y-J, Qui H-z, Liao K-S, Lue SJ, Hu C-C, Lee K-R, Lai J-Y. Effect of
Drioli E, Stankiewicz AI, Macedonio F. Membrane engineering in UV-ozone treatment on poly(dimethylsiloxane) membranes:
process intensification – an overview. J Membr Sci 2011; 380: surface characterization and gas separation performance.
1–8. Langmuir 2010; 26: 4392–4399.
Du N, Robertson GP, Song J, Pinnau I, Thomas S, Guiver MD. Fu S, Wenz GB, Sanders ES, Kulkarni SS, Qiu W, Ma C, Koros WJ.
Polymers of intrinsic microporosity containing trifluoromethyl Effects of pyrolysis conditions on gas separation properties
and phenylsulfone groups as materials for membrane gas of 6FDA/DETDA:DABA(3:2) derived carbon molecular sieve
separation. Macromolecules 2008; 41: 9656–9662. membranes. J Membr Sci 2016; 520: 699–711.
Duan C, Jie X, Liu D, Cao Y, Yuan Q. Post-treatment effect on gas Fuertes AB. Adsorption-selective carbon membrane for gas
separation property of mixed matrix membranes containing separation. J Membr Sci 2000; 177: 9–16.
metal organic frameworks. J Membr Sci 2014; 466: 92–102. Fuertes A, Centeno T. Carbon molecular sieve membranes from
Efimov K, Halfer T, Kuhn A, Heitjans P, Caro J, Feldhoff A. Novel polyetherimide. Microporous Mesoporous Mater 1998; 26:
cobalt-free oxygen-permeable perovskite-type membrane. 23–26.
Chem Mater 2010; 22: 1540–1544. Gao D, Zhao J, Zhou W, Ran R, Shao Z. Influence of high-energy ball
Ettouney HM, El-Dessouky HT, Abou Waar W. Separation milling of the starting powder on the sintering; microstructure
characteristics of air by polysulfone hollow fiber membranes in and oxygen permeability of Ba0.5Sr0.5Co0.5Fe0.5O3−δ membranes.
series. J Membr Sci 1998; 148: 105–117. J Membr Sci 2011; 366: 203–211.
Fang W, Liang F, Cao Z, Steinbach F, Feldhoff A. A mixed ionic and Geffroy PM, Fouletier J, Richet N, Chartier T. Rational selection of
electronic conducting dual-phase membrane with high oxygen MIEC materials in energy production processes. Chem Eng Sci
permeability. Angew Chem Int Ed 2015a; 54: 4847–4850. 2013; 87: 408–433.
Fang W, Steinbach F, Chen C, Feldhoff A. An approach to enhance George SC, Ninan KN, Thomas S. Permeation of nitrogen and oxygen
the CO2 tolerance of fluorite-perovskite dual-phase oxygen- gases through styrene-butadiene rubber, natural rubber and
transporting membrane. Chem Mater 2015b; 27: 7820–7826. styrene-butadiene rubber/natural rubber blend membranes.
Fatemi SM, Sepehrian H, Arabieh M. Simulation studies of the Eur Polym J 2001; 37: 183–191.
separation of Kr-85 radionuclide gas from nitrogen and Ghanem BS, McKeown NB, Budd PM, Selbie JD, Fritsch D.
oxygen across nanoporous graphene membranes in different High-performance membranes from polyimides with intrinsic
pore configurations. The European Physical Journal Plus 2016; microporosity. Adv Mater 2008; 20: 2766–2771.
131: 131. Ghosal K, Freeman BD. Gas separation using polymer membranes:
Fatyeyeva K, Dahi A, Chappey C, Langevin D, Valleton J-M, Poncin- an overview. Polym Adv Technol 1994; 5: 673–697.
Epaillard F, Marais S. Effect of cold plasma treatment on surface Gibson P, Schreuder-Gibson H, Rivin D. Transport properties of
properties and gas permeability of polyimide films. RSC porous membranes based on electrospun nanofibers. Colloids
Advances 2014; 4: 31036–31046. Surf Physicochem Eng Aspects 2001; 187–188: 469–481.
Favre E, Bounaceur R, Roizard D. A hybrid process combining Goh PS, Ismail AF, Sanip SM, Ng BC, Aziz M. Recent advances of
oxygen enriched air combustion and membrane separation for inorganic fillers in mixed matrix membrane for gas separation.
post-combustion carbon dioxide capture. Sep Purif Technol Sep Purif Technol 2011; 81: 243–264.
2009; 68: 30–36. Gupta Y, Hellgardt K, Wakeman RJ. Enhanced permeability of
Feng X, Ivory J, Rajan VSV. Air separation by integrally asymmetric polyaniline based nano-membranes for gas separation.
hollow-fiber membranes. AICHE J 1999; 45: 2142–2152. J Membr Sci 2006; 282: 60–70.

Authenticated
Han D, Tan X, Yan Z, Li Q, Liu S. New morphological Huber F, Springer J, Muhler M. Plasma polymer membranes from
Ba0.5Sr0.5Co0.8Fe0.2O3−α hollow fibre membranes with high oxygen hexafluoroethane/hydrogen mixtures for separation of oxygen
permeation fluxes. Ceram Int 2013; 39: 431–437. and nitrogen. J Appl Polym Sci 1997; 63: 1517–1526.
Hasbullah H, Kumbharkar S, Ismail AF, Li K. Asymmetric hollow Ilconich JB, Xu X, Coleman M, Simpson PJ. Impact of ion beam
fibre membranes based on ring-substituted polyaniline and irradiation on microstructure and gas permeance of polysulfone
investigation towards its gas transport properties. J Membr Sci asymmetric membranes. J Membr Sci 2003; 214: 143–156.
2012; 397–398: 38–50. Illing G, Hellgardt K, Schonert M, Wakeman RJ, Jungbauer A. Towards
Hashim SM, Mohamed AR, Bhatia S. Current status of ceramic-based ultrathin polyaniline films for gas separation. J Membr Sci
membranes for oxygen separation from air. Adv Colloid 2005; 253: 199–208.
Interface Sci 2010; 160: 88–100. Inagaki N, Ohkubo J. Plasma polymerization of hexafluoropropene/
Hassan MH, Douglas Way J, Thoen PM, Dillon AC. Single component methane mixtures and composite membranes for gas
and mixed gas transport in a silica hollow fiber membrane. separations. J Membr Sci 1986; 27: 63–75.
J Membr Sci 1995; 104: 27–42. Isfahani AP, Sadeghi M, Dehaghani AHS, Aravand MA. Enhancement
He W, Liu J-j, Chen C-S, Ni M. Oxygen permeation modeling for of the gas separation properties of polyurethane membrane by
Zr0.84Y0.16O1.92–La0.8Sr0.2Cr0.5Fe0.5O3−δ asymmetric membrane epoxy nanoparticles. J Ind Eng Chem 2016; 44: 67–72.
made by phase-inversion. J Membr Sci 2015; 491: 90–98. Islam Q, Raja M, Basu R. LaxSr1−xCo0.35Bi0.2Fe0.45O3−δ (x = 0.5 to 0.8):
Himma NF, Wenten IG. Surface engineering of polymer membrane a new series of oxygen separation membrane. Int J Hydrogen
for air separation. AIP Conf Proc, AIP Publishing, 2016; 1840: Energy 2016; 41: 4682–4689.
090005. Ismail AF, David LIB. A review on the latest development of carbon
Himma NF, Anisah S, Prasetya N, Wenten IG. Advances in membranes for gas separation. J Membr Sci 2001; 193: 1–18.
preparation, modification, and application of polypropylene Ismail AF, Lai PY. Effects of phase inversion and rheological factors
membrane. J Polym Eng 2016; 36: 329–362. on formation of defect-free and ultrathin-skinned asymmetric
Himma NF, Wardani AK, Wenten IG. The effects of non-solvent polysulfone membranes for gas separation. Sep Purif Technol
on surface morphology and hydrophobicity of dip-coated 2003; 33: 127–143.
polypropylene membrane. Mater Res Express 2017a; 4: Ismail AF, Lai PY. Development of defect-free asymmetric
054001. polysulfone membranes for gas separation using response
Himma NF, Wardani AK, Wenten IG. Preparation of superhydrophobic surface methodology. Sep Purif Technol 2004; 40: 191–207.
polypropylene membrane using dip-coating method: the Ismail AF, Nasri NS. Effects of dope extrusion rate on the
effects of solution and process parameters. Polym Plast morphology and gas separation performance of asymmetric
Technol Eng 2017b; 56: 184–194. polysulfone hollow fiber membranes for 024 separation.
Hopkins J, Badyal JPS. CF4 plasma treatment of asymmetric Songklanakarin J Sci Technol 2002; 24: 833–842.
polysulfone membranes. Langmuir 1996; 12: 3666–3670. Ismail AF, Yean LP. Review on the development of defect-free and
Hosseini SS, Omidkhah MR, Zarringhalam Moghaddam A, Pirouzfar ultrathin-skinned asymmetric membranes for gas separation
V, Krantz WB, Tan NR. Enhancing the properties and gas through manipulation of phase inversion and rheological
separation performance of PBI-polyimides blend carbon factors. J Appl Polym Sci 2003; 88: 442–451.
molecular sieve membranes via optimization of the pyrolysis Ismail AF, Dunkin IR, Gallivan SL, Shilton SJ. Production of super
process. Sep Purif Technol 2014; 122: 278–289. selective polysulfone hollow fiber membranes for gas
Hosseini SS, Najari S, Kundu PK, Tan NR, Roodashti SM. Simulation separation. Polymer 1999; 40: 6499–6506.
and sensitivity analysis of transport in asymmetric hollow fiber Ismail AF, Ridzuan N, Rahman SA. Latest development on the
membrane permeators for air separation. RSC Advances 2015; membrane formation for gas separation. Songklanakarin J Sci
5: 86359–86370. Technol 2002; 24: 1025–1043.
Houston KS, Weinkauf DH, Stewart FF. Gas transport characteristics Ismail AF, Khulbe KC, Matsuura T. Gas separation membrane
of plasma treated poly(dimethylsiloxane) and polyphosphazene materials and structures. In: Gas separation membranes.
membrane materials. J Membr Sci 2002; 205: 103–112. Switzerland: Springer, Cham, 2015: 37–192.
Hsu KK, Nataraj S, Thorogood RM, Puri PS. O2/N2 Selectivity Ivanova S, Lewis R. Producing nitrogen via pressure swing
improvement for polytrimethylsilypropyne membranes by adsorption. Chem Eng Prog 2012; 108: 38–42.
UV-irradiation and further enhancement by subambient Iwa T, Kumazawa H, Bae SY. Gas permeabilities of NH3-plasma-
temperature operation. J Membr Sci 1993; 79: 1–10. treated polyethersulfone membranes. J Appl Polym Sci 2004;
Hu C-C, Liu T-C, Lee K-R, Ruaan R-C, Lai J-Y. International Congress 94: 758–762.
on Membranes and Membrane Processes. Zeolite-filled PMMA Iyer P, Iyer G, Coleman M. Gas transport properties of
composite membranes: influence of coupling agent addition on polyimide-POSS nanocomposites. J Membr Sci 2010; 358:
gas separation properties. Desalination 2006; 193: 14–24. 26–32.
Hu J, Cai H, Ren H, Wei Y, Xu Z, Liu H, Hu Y. Mixed-matrix membrane Jain IP, Agarwal G. Ion beam induced surface and interface
hollow fibers of Cu3 (BTC)2 MOF and polyimide for gas engineering. Surf Sci Rep 2011; 66: 77–172.
separation and adsorption. Ind Eng Chem Res 2010; 49: Jami’an WNR, Hasbullah H, Mohamed F, Wan Salleh WN, Ibrahim N,
12605–12612. Ali RR. Biodegradable gas separation membrane preparation
Huang A, Wang N, Caro J. Synthesis of multi-layer zeolite LTA by manipulation of casting parameters. Chem Eng Tran 2015;
membranes with enhanced gas separation performance by 43: 1105–1110.
using 3-aminopropyltriethoxysilane as interlayer. Microporous Jansen J, Buonomenna M, Figoli A, Drioli E. Ultra-thin asymmetric
Mesoporous Mater 2012; 164: 294–301. gas separation membranes of modified PEEK prepared by the

Authenticated
dry-wet phase inversion technique. Desalination 2006; 193: Konruang S, Sirijarukul S, Wanichapichart P, Yu L, Chittrakarn T.
58–65. Ultraviolet-ray treatment of polysulfone membranes on the O2/
Jeazet H, Staudt C, Janiak C. A method for increasing permeability N2 and CO2/CH4 separation performance. J Appl Polym Sci 2015;
in O2/N2 separation with mixed-matrix membranes made of 132: 42074.
water-stable MIL-101 and polysulfone. Chem Commun (Camb) Koros WJ, Fleming GK. Membrane-based gas separation. J Membr
2012; 48: 2140–2142. Sci 1993; 83: 1–80.
Jiang X, Li S, Shao L. Pushing CO2-philic membrane performance to Kottke T, Stalke D. Crystal handling at low temperatures. J Appl
the limit by designing semi-interpenetrating networks (SIPN) Crystallogr 1993; 26: 615–619.
for sustainable CO2 separations. Energy Environ Sci 2017; 10: Krasowska M, Rybak A, Dudek G, Strzelewicz A, Pawełek K, Grzywna
1339–1344. ZJ. Structure morphology problems in the air separation by
Jones CW, Koros WJ. Carbon molecular sieve gas separation polymer membranes with magnetic particles. J Membr Sci
membranes-I. Preparation and characterization based on 2012; 415–416: 864–870.
polyimide precursors. Carbon 1994; 32: 1419–1425. Lamlong C, Taweepreda W. Coating of porous PVC-PEG memebrane
Jones C, Gordeyev S, Shilton S. Poly (vinyl chloride)(PVC) hollow with crosslinkable XSBR for O2/N2 and CO2/N2 separation.
fibre membranes for gas separation. Polymer 2011; 52: Polymer 2016; 96: 205–212.
901–903. Le Roux JD, Paul DR, Arendt M, Yuan Y, Cabasso I. Modification
Kawakami M, Yamashita Y, Iwamoto M, Kagawa S. Modification of of asymmetric polysulfone membranes by mild surface
gas permeabilities of polymer membranes by plasma coating. J fluorination Part II. Characterization of the fluorinated surface.
Membr Sci 1984; 19: 249–258. J Membr Sci 1994a; 94: 143–162.
Kesting RE, Fritzsche AK, Murphy MK, Cruse CA, Handermann AC, Le Roux JD, Paul DR, Kampa J, Lagow RJ. Modification of asymmetric
Malon RF, Moore MD. The second-generation polysulfone polysulfone membranes by mild surface fluorination Part I.
gas-separation membrane. I. The use of Lewis acid:base Transport properties. J Membr Sci 1994b; 94: 121–141.
complexes as transient templates to increase free volume. J Lee EH. Ion-beam modification of polymeric materials – fundamental
Appl Polym Sci 1990; 40: 1557–1574. principles and applications. Nucl Instrum Methods Phys Res,
Kharton V, Kovalevsky A, Viskup A, Jurado J, Figueiredo F, Naumovich Sect B 1999; 151: 29–41.
E, Frade J. Transport properties and thermal expansion of Lee YM, Ha SY, Lee YK, Suh DH, Hong SY. Gas separation through
Sr0.97Ti1−xFexO3−δ (x = 0.2–0.8). J Solid State Chem 2001; 156: conductive polymer membranes. 2. Polyaniline membranes with
437–444. high oxygen selectivity. Ind Eng Chem Res 1999; 38: 1917–1924.
Kharton VV, Tsipis EV, Naumovich EN, Thursfield A, Patrakeev MV, Lee W-J, Kim D-S, Kim J-H. Preparation and gas separation properties
Kolotygin VA, Waerenborgh JC, Metcalfe IS. Mixed conductivity, of asymmetric polysulfone membranes by a dual bath method.
oxygen permeability and redox behavior of K2NiF4-type Korean J Chem Eng 2000; 17: 143–148.
La2Ni0.9Fe0.1O4+δ. J Solid State Chem 2008; 181: 1425–1433. Leo A, Smart S, Liu S, Diniz da Costa JC. High performance
Khoiruddin K, Wenten IG. Investigation of electrochemical perovskite hollow fibres for oxygen separation. J Membr Sci
and morphological properties of mixed matrix polysulfone- 2011; 368: 64–68.
silica anion exchange membrane. J Eng Technol Sci 2016; 48: Li L, Qi H. Gas separation using sol-gel derived microporous zirconia
1–11. membranes with high hydrothermal stability. Chin J Chem Eng
Khoiruddin K, Widiasa IN, Wenten IG. Removal of inorganic 2015; 23: 1300–1306.
contaminants in sugar refining process using Li X-G, Kresse I, Springer J, Nissen J, Yang Y-L. Morphology and gas
electrodeionization. J Food Eng 2014; 133: 40–45. permselectivity of blend membranes of polyvinylpyridine with
Khoiruddin K, Ariono D, Subagjo, Wenten IG. Surface modification ethylcellulose. Polymer 2001; 42: 6859–6869.
of ion-exchange membranes: methods, characteristics, and Li Y, Cao C, Chung T-S, Pramoda KP. Fabrication of dual-layer
performance. J Appl Polym Sci 2017; 134: 45540. polyethersulfone (PES) hollow fiber membranes with an
Kim S, Lee YM. Rigid and microporous polymers for gas separation ultrathin dense-selective layer for gas separation. J Membr Sci
membranes. Prog Polym Sci 2015; 43: 1–32. 2004; 245: 53–60.
Kim S, Chen L, Johnson JK, Marand E. Polysulfone and functionalized Li F, Li Y, Chung T-S, Kawi S. Facilitated transport by hybrid POSS®-
carbon nanotube mixed matrix membranes for gas separation: Matrimid®-Zn2+ nanocomposite membranes for the separation
theory and experiment. J Membr Sci 2007; 294: 147–158. of natural gas. J Membr Sci 2010; 356: 14–21.
Kim D-H, Im H-S, Kim M-S, Lee B-S, Lee B-S, Yoon S-W, Kim B-S, Li S, Jo HJ, Han SH, Park CH, Kim S, Budd PM, Lee YM. Mechanically
Park Y-I, Cheong S-I, Rhim J-W. Study on the gas permeation robust thermally rearranged (TR) polymer membranes with
behaviors of surface fluorinated polysulfone membranes. spirobisindane for gas separation. J Membr Sci 2013a; 434:
Polymer Korea 2009; 33: 537–543. 137–147.
Koenig SP, Wang L, Pellegrino J, Bunch JS. Selective molecular sieving Li X, Kerstiens T, Markus T. Oxygen permeability and phase
through porous graphene. Nat Nanotechnol 2012; 7: 728–732. stability of Ba0.5Sr0.5Co0.8Fe0.2O3−δ perovskite at intermediate
Komatsuka T, Kusakabe A, Nagai K. Characterization and gas temperatures. J Membr Sci 2013b; 438: 83–89.
transport properties of poly(lactic acid) blend membranes. Li S, Jiang X, Yang Q, Shao L. Effects of amino functionalized
Desalination 2008; 234: 212–220. polyhedral oligomeric silsesquioxanes on cross-linked
Kong C, Wang J, Yang J, Lu J, Wang A, Zhao Q. Thin carbon-zeolite poly(ethylene oxide) membranes for highly-efficient CO2
composite membrane prepared on ceramic tube filter by separation. Chem Eng Res Des 2017; 122: 280–288.
vacuum slip casting for oxygen/nitrogen separation. Carbon Lin YS. Microporous and dense inorganic membranes: current status
2007; 45: 2848–2850. and prospective. Sep Purif Technol 2001; 25: 39–55.

Authenticated
Lin H, Freeman BD. Gas solubility, diffusivity and permeability in Mohamed F, Hasbullah H, Jamian WNR, Rani ARA, Saman MFK,
poly(ethylene oxide). J Membr Sci 2004; 239: 105–117. Salleh WNH, Ali RR. Gas permeation performance of poly(lactic
Lin X, Xiao J, Yu Y, Chen J, Zheng G, Xu J. Gas permeabilities of acid) asymmetric membrane for O2/N2 separation. In: Hashim
poly(trimethylsilylpropyne) membranes surface modified with AM, editor. ICGSCE 2014: Proceedings of the International
CF4 plasma. J Appl Polym Sci 1993; 48: 231–236. Conference on Global Sustainability and Chemical Engineering.
Lin X, Qiu X, Zheng G, Xu J. Gas permeabilities of Singapore: Springer Singapore, 2015: 149–156.
poly(trimethylsilylpropyne) membranes surface modified with Mozaffari V, Sadeghi M, Fakhar A, Khanbabaei G, Ismail
CCI4 plasma. J Appl Polym Sci 1995; 58: 2137–2139. A. Gas separation properties of polyurethane/poly
Liu Y, Pan C, Ding M, Xu J. Gas permeability and permselectivity of (ether-block-amide)(PU/PEBA) blend membranes. Sep Purif
photochemically crosslinked copolyimides. J Appl Polym Sci Technol 2017; 185: 202–214.
1999; 73: 521–526. Mulder M. Basic principles of membrane technology, Netherlands:
Liu Y, Wang R, Chung T-S. Chemical cross-linking modification of Kluwer Academic Publisher, 1996.
polyimide membranes for gas separation. J Membr Sci 2001; Murali RS, Sankarshana T, Sridhar S. Air separation by polymer-based
189: 231–239. membrane technology. Sep Purif Rev 2013; 42: 130–186.
Liu Q, Wang T, Liang C, Zhang B, Liu S, Cao Y, Qiu J. Zeolite married to Nady N, Franssen MCR, Zuilhof H, Eldin MSM, Boom R, Schroën
carbon: a new family of membrane materials with excellent gas K. Modification methods for poly(arylsulfone) membranes: a
separation performance. Chem Mater 2006a; 18: 6283–6288. mini-review focusing on surface modification. Desalination
Liu Q, Wang T, Qiu J, Cao Y. A novel carbon/ZSM-5 nanocomposite 2011; 275: 1–9.
membrane with high performance for oxygen/nitrogen Nagendra N, Bandopadhyay S. Room and elevated temperature
separation. Chem Commun 2006b: 1230–1232. strength of perovskite membrane tubes. J Eur Ceram Soc 2003;
Liu Q, Wang T, Guo H, Liang C, Liu S, Zhang Z, Cao Y, Su DS, 23: 1361–1368.
Qiu J. Controlled synthesis of high performance carbon/ Nakata M, Kumazawa H. Gas permeability and permselectivity of
zeolite T composite membrane materials for gas separation. plasma-treated polyethylene membranes. J Appl Polym Sci
Microporous Mesoporous Mater 2009; 120: 460–466. 2006; 101: 383–387.
Liu SL, Shao L, Chua ML, Lau CH, Wang H, Quan S. Recent progress Nishiyama N, Yamaguchi M, Katayama T, Hirota Y, Miyamoto M,
in the design of advanced PEO-containing membranes for CO2 Egashira Y, Ueyama K, Nakanishi K, Ohta T, Mizusawa A, Satoh
removal. Prog Polym Sci 2013; 38: 1089–1120. T. Hydrogen-permeable membranes composed of zeolite
Lockwood T. Developments in oxyfuel combustion of coal. London, nano-blocks. J Membr Sci 2007; 306: 349–354.
UK: IEA Clean Coal Centre, Report No CCC/240, August 2014. Niwa M, Kawakami H, Nagaoka S, Kanamori T, Shinbo T. Fabrication
Lokaj J, Brožová L, Holler P, Pientka Z. Synthesis and gas of an asymmetric polyimide hollow fiber with a defect-free
permeability of block copolymers composed of poly(styrene- surface skin layer. J Membr Sci 2000; 171: 253–261.
co-acrylonitrile) and polystyrene blocks +. Collect Czech Chem Niwa M, Kawakami H, Kanamori T, Shinbo T, Kaito A, Nagaoka S.
Commun 2002; 67: 267–278. Gas separation of asymmetric 6FDA polyimide membrane
Lumeij M, Gilleßen M, Bouwmeester H, Markus T, Barthel J, Roitsch S, with oriented surface skin layer. Macromolecules 2001; 34:
Mayer J, Dronskowski R. Influence of the Ba2+/Sr2+ content and 9039–9044.
oxygen vacancies on the stability of cubic BaxSr1−xCo0.75Fe0.25O3−δ. Nomura H, Kramer PW, Yasuda H. Preparation of gas separation
Phys Chem Chem Phys 2014; 16: 1333–1338. membranes by plasma polymerization with fluoro compounds.
Luo H, Jiang H, Klande T, Cao Z, Liang F, Wang H, Caro Jr. Novel Thin Solid Films 1984; 118: 187–195.
cobalt-free, noble metal-free oxygen-permeable Ochs TL, Summers CA, Oryshchyn DB, Gross D, Patrick B, Gross A,
40Pr0. 6Sr0.4FeO3−δ−60Ce0. 9Pr0.1O2−δ dual-phase membrane. Chem Dogan C, Simmons W, Schoenfeld M. Oxy-fuel combustion
Mater 2012; 24: 2148–2154. systems for pollution free coal fired power generation. The
Madaeni SS, Moradi P. Preparation and characterization of 29th International Technical Conference on Coal Utilization
asymmetric polysulfone membrane for separation of oxygen and Fuel Systems, Clearwater, Florida, 2004.
and nitrogen gases. J Appl Polym Sci 2011; 121: 2157–2167. Ordonez MJC, Balkus KJ, Ferraris JP, Musselman IH. Molecular
Madaeni SS, Enayati E, Vatanpour V. Separation of nitrogen sieving realized with ZIF-8/Matrimid® mixed-matrix
and oxygen gases by polymeric membrane embedded membranes. J Membr Sci 2010; 361: 28–37.
with magnetic nano-particle. Polym Adv Technol 2011; 22: Pandey P, Chauhan RS. Membranes for gas separation. Prog Polym
2556–2563. Sci 2001; 26: 853–893.
Magueijo VM, Anderson LG, Fletcher AJ, Shilton SJ. Polysulfone Pellegrino J, Radebaugh R, Mattes BR. Gas sorption in polyaniline. 1.
mixed matrix gas separation hollow fibre membranes filled Emeraldine base. Macromolecules 1996; 29: 4985–4991.
with polymer and carbon xerogels. Chem Eng Sci 2013; 92: Peng N, Chung TS, Li KY. The role of additives on dope rheology and
13–20. membrane formation of defect-free Torlon® hollow fibers for
Meier IK, Langsam M, Klotz HC. Selectivity enhancement via gas separation. J Membr Sci 2009; 343: 62–72.
photooxidative surface modification of polyimide air Pesek SC, Koros WJ. Aqueous quenched asymmetric polysulfone
separation membranes. J Membr Sci 1994; 94: 195–212. membranes prepared by dry/wet phase separation. J Membr
Ming X, Borgnakke DS, Campos MA, Olszewski P, Atreya A, Sci 1993; 81: 71–88.
Borgnakke C. Possibility of combustion furnace operation Pinnau I, Koros WJ. Relationship between substructure resistance
with oxygen-enriched gas from nitrogen generator. University and gas separation properties of defect-free integrally
of Michigan, ACEEE Summer Study on Energy Efficiency in skinned asymmetric membranes. Ind Eng Chem Res 1991a; 30:
Industry 2003. 1837–1840.

Authenticated
Pinnau I, Koros WJ. Structures and gas separation properties Sadeghi M, Semsarzadeh MA, Barikani M, Chenar MP. Gas
of asymmetric polysulfone membranes made by dry, wet, separation properties of polyether-based polyurethane-silica
and dry/wet phase inversion. J Appl Polym Sci 1991b; 43: nanocomposite membranes. J Membr Sci 2011; 376: 188–195.
1491–1502. Salleh W, Ismail AF. Carbon membranes for gas separation
Prasad R, Notaro F, Thompson DR. Evolution of membranes in processes: recent progress and future perspective. Journal of
commercial air separation. J Membr Sci 1994; 94: 225–248. Membrane Science and Research 2015; 1: 2–15.
Purwasasmita M, Kurnia D, Mandias FC, Khoiruddin K, Wenten IG. Sánchez-Soto PJ, Avilés M, del Rıo J, Ginés J, Pascual J, Pérez-
Beer dealcoholization using non-porous membrane distillation. Rodrıguez J. Thermal study of the effect of several solvents on
Food Bioprod Process 2015a; 94: 180–186. polymerization of acrylonitrile and their subsequent pyrolysis. J
Purwasasmita M, Nabu EBP, Khoiruddin K, Wenten IG. Non Anal Appl Pyrolysis 2001; 58: 155–172.
dispersive chemical deacidification of crude palm oil in Saufi SM, Ismail AF. Fabrication of carbon membranes for gas
hollow fiber membrane contactor. J Eng Technol Sci 2015b; 47: separation – a review. Carbon 2004; 42: 241–259.
426–446. Scheffknecht G, Al-Makhadmeh L, Schnell U, Maier J. Oxy-fuel coal
Rana D, Matsuura T. Surface modifications for antifouling combustion – a review of the current state-of-the-art. Int J
membranes. Chem Rev 2010; 110: 2448–2471. Greenhouse Gas Control 2011; 5, Supplement 1: S16–S35.
Rao P, Muller M. Industrial oxygen: its generation and use. ACEEE Schiestel T, Kilgus M, Peter S, Caspary K, Wang H, Caro J. Hollow
Summer Study on Energy Efficiency in Industry, 2007. fibre perovskite membranes for oxygen separation. J Membr Sci
Rao H-X, Liu F-N, Zhang Z-Y. Preparation and oxygen/nitrogen 2005; 258: 1–4.
permeability of PDMS crosslinked membrane and PDMS/ Sedigh MG, Xu L, Tsotsis TT, Sahimi M. Transport and morphological
tetraethoxysilicone hybrid membrane. J Membr Sci 2007; 303: characteristics of polyetherimide-based carbon molecular sieve
132–139. membranes. Ind Eng Chem Res 1999; 38: 3367–3380.
Rautenbach R, Struck A, Melin T, Roks MFM. Impact of operating Semsarzadeh MA, Ghalei B. Characterization and gas permeability
pressure on the permeance of hollow fiber gas separation of polyurethane and polyvinyl acetate blend membranes with
membranes. J Membr Sci 1998; 146: 217–223. polyethylene oxide-polypropylene oxide block copolymer. J
Readman JE, Olafsen A, Larring Y, Blom R. La0.8Sr0.2Co0.2Fe0.8O3−δ as a Membr Sci 2012; 401–402: 97–108.
potential oxygen carrier in a chemical looping type reactor, an Shaddix C, Molina A. Ignition, flame stability, and char combustion
in-situ powder X-ray diffraction study. J Mater Chem 2005; 15: in oxy-fuel combustion. In: Zheng L, editor. Oxy-fuel combustion
1931–1937. for power generation and carbon dioxide (CO2) capture.
Reid BD, Ruiz-Trevino FA, Musselman IH, Balkus KJ, Ferraris JP. Gas Cambridge, UK: Woodhead Publishing, 2011: 101–124.
permeability properties of polysulfone membranes containing Shao L, Liu L, Cheng S-X, Huang Y-D, Ma J. Comparison of diamino
the mesoporous molecular sieve MCM-41. Chem Mater 2001; cross-linking in different polyimide solutions and membranes
13: 2366–2373. by precipitation observation and gas transport. J Membr Sci
Reinhardt H-J, Obermeyer H-D, Schreiner B, Wolf S. Oxygen 2008; 312: 174–185.
enrichment for intensification of air oxidation reactions. Sharpe ID, Ismail AF, Shilton SJ. A study of extrusion shear and
Pullach, Germany: The Linde Group, 2015. forced convection residence time in the spinning of polysulfone
Robeson LM. Correlation of separation factor versus permeability for hollow fiber membranes for gas separation. Sep Purif Technol
polymeric membranes. J Membr Sci 1991; 62: 165–185. 1999; 17: 101–109.
Robeson LM. Polymer membranes for gas separation. Curr Opin Sianipar M, Kim SH, Khoiruddin K, Iskandar F, Wenten IG.
Solid State Mater Sci 1999; 4: 549–552. Functionalized carbon nanotube (CNT) membrane: progress
Robeson LM. The upper bound revisited. J Membr Sci 2008; 320: and challenges. RSC Advances 2017; 7: 51175–51198.
390–400. Skeen SA, Yablonsky G, Axelbaum RL. Characteristics of
Rowe B, Freeman B, Paul D. Physical aging of membranes for non-premixed oxygen-enhanced combustion: I. The presence
gas separations. In: Drioli E, Barbieri G, editor. Membrane of appreciable oxygen at the location of maximum temperature.
engineering for the treatment of gases volume 1: Combust Flame 2009; 156: 2145–2152.
gas-separation problems with membranes. Cambridge, UK: Smith AR, Klosek J. A review of air separation technologies and their
Royal Society of Chemistry, 2011: 58–83. integration with energy conversion processes. Fuel Process
Ruaan RC, Chen SH, Lai JY. Oxygen/nitrogen separation by Technol 2001; 70: 115–134.
polycarbonate/Co(SalPr) complex membranes. J Membr Sci Song Q, Nataraj S, Roussenova MV, Tan JC, Hughes DJ, Li W,
1997; 135: 9–18. Bourgoin P, Alam MA, Cheetham AK, Al-Muhtaseb SA. Zeolitic
Ruaan R-C, Wu T-H, Chen S-H, Lai J-Y. Oxygen/nitrogen separation by imidazolate framework (ZIF-8) based polymer nanocomposite
polybutadiene/polycarbonate composite membranes modified membranes for gas separation. Energy Environ Sci 2012; 5:
by ethylenediamine plasma. J Membr Sci 1998; 138: 213–220. 8359–8369.
Rybak A, Kaszuwara W. Magnetic properties of the magnetic hybrid Staiger CL, Pas SJ, Hill AJ, Cornelius CJ. Gas separation, free
membranes based on various polymer matrices and inorganic volume distribution, and physical aging of a highly
fillers. J Alloys Compd 2015; 648: 205–214. microporous spirobisindane polymer. Chem Mater 2008; 20:
Rybak A, Grzywna ZJ, Kaszuwara W. On the air enrichment by 2606–2608.
polymer magnetic membranes. J Membr Sci 2009; 336: 79–85. Strathmann H, Kock K, Amar P, Baker RW. The formation mechanism
Rybak A, Grzywna ZJ, Sysel P. Mixed matrix membranes composed of asymmetric membranes. Desalination 1975; 16: 179–203.
of various polymer matrices and magnetic powder for air Strzelewicz A, Grzywna ZJ. Studies on the air membrane separation in
separation. Sep Purif Technol 2013; 118: 424–431. the presence of a magnetic field. J Membr Sci 2007; 294: 60–67.

Authenticated
Sunarso J, Baumann S, Serra JM, Meulenberg WA, Liu S, Lin YS, Vu DQ, Koros WJ, Miller SJ. Mixed matrix membranes using carbon
Diniz da Costa JC. Mixed ionic-electronic conducting (MIEC) molecular sieves: I. Preparation and experimental results. J
ceramic-based membranes for oxygen separation. J Membr Sci Membr Sci 2003; 211: 311–334.
2008; 320: 13–41. Wahab MFA, Ismail AF, Shilton SJ. Studies on gas permeation
Tan Y, Croiset E, Douglas MA, Thambimuthu KV. Combustion performance of asymmetric polysulfone hollow fiber mixed
characteristics of coal in a mixture of oxygen and recycled flue matrix membranes using nanosized fumed silica as fillers. Sep
gas. Fuel 2006; 85: 507–512. Purif Technol 2012; 86: 41–48.
Tan X, Wang Z, Meng B, Meng X, Li K. Pilot-scale production of Wang D, Li K, Teo WK. Polyethersulfone hollow fiber gas separation
oxygen from air using perovskite hollow fibre membranes. J membranes prepared from NMP/alcohol solvent systems. J
Membr Sci 2010; 352: 189–196. Membr Sci 1996; 115: 85–108.
Tan X, Liu N, Meng B, Liu S. Morphology control of the perovskite Wang D, Li K, Teo WK. Preparation and characterization of
hollow fibre membranes for oxygen separation using different polyetherimide asymmetric hollow fiber membranes for gas
bore fluids. J Membr Sci 2011; 378: 308–318. separation. J Membr Sci 1998; 138: 193–201.
Tanasescu S, Yáng Z, Martynczuk J, Varazashvili V, Maxim F, Wang D, Li K, Teo WK. Highly permeable polyethersulfone
Teodorescu F, Botea A, Totir N, Gauckler LJ. Effects of hollow fiber gas separation membranes prepared using
A-site composition and oxygen nonstoichiometry on the water as non-solvent additive. J Membr Sci 2000; 176:
thermodynamic stability of compounds in the Ba-Sr-Co-Fe-O 147–158.
system. J Solid State Chem 2013; 200: 354–362. Wang H, Huang L, Holmberg BA, Yan Y. Nanostructured zeolite 4A
Tang X, Zhang X, Luo W, Wu C, Zhang Y, Ding W, Sun C. Iron-doping molecular sieving air separation membranes. Chem Commun
effects on the CO2 tolerance of a perovskite oxygen permeable 2002a: 1708–1709.
membrane. J Mater Sci 2016; 51: 3971–3978. Wang D, Teo WK, Li K. Preparation and characterization of high-flux
Tanihara N, Shimazaki H, Hirayama Y, Nakanishi S, Yoshinaga T, polysulfone hollow fibre gas separation membranes. J Membr
Kusuki Y. Gas permeation properties of asymmetric carbon Sci 2002b; 204: 247–256.
hollow fiber membranes prepared from asymmetric polyimide Wang H, Werth S, Schiestel T, Caro J. Perovskite hollow-fiber
hollow fiber. J Membr Sci 1999; 160: 179–186. membranes for the production of oxygen-enriched air. Angew
Teramae T, Kumazawa H. Gas permeability and permselectivity of Chem Int Ed 2005; 44: 6906–6909.
plasma-treated polypropylene membranes. J Appl Polym Sci Wang J, Xu Z, Xu Y. Preparation of poly(4-methyl-1-pentene)
2007; 104: 3236–3239. asymmetric or microporous hollow-fiber membranes by
Teraoka Y, Zhang H-M, Furukawa S, Yamazoe N. Oxygen permeation melt-spun and cold-stretch method. J Appl Polym Sci 2006a;
through perovskite-type oxides. Chem Lett 1985; 14: 1743–1746. 100: 2131–2141.
Teraoka Y, Shimokawa H, Kang CY, Kusaba H, Sasaki K. Fe-based Wang B, Yi J, Winnubst L, Chen C. Stability and oxygen permeation
perovskite-type oxides as excellent oxygen-permeable and behavior of Ce0.8Sm0.2O2−δ–La0.8Sr0.2CrO3−δ composite membrane
reduction-tolerant materials. Solid State Ionics 2006; 177: under large oxygen partial pressure gradients. J Membr Sci
2245–2248. 2006b; 286: 22–25.
The Linde Group. Oxygen for the chemical industry: process Wang R, Meng B, Meng X, Tan X, Sunarso J, Liu L, Liu S. Highly stable
intensification of air oxidations by O2 enrichment. Murray Hill: La0.6Sr0.4Co0.2Fe0.8O3−δ hollow fibre membrane for air separation
Linde North America, Inc., 2012. swept by steam or steam mixture. J Membr Sci 2015; 479:
Tin PS, Chung TS, Liu Y, Wang R, Liu SL, Pramoda KP. Effects of 232–239.
cross-linking modification on gas separation performance of Wang B, Song J, Tan X, Meng B, Liu J, Liu S. Reinforced perovskite
Matrimid membranes. J Membr Sci 2003; 225: 77–90. hollow fiber membranes with stainless steel as the reactive
Torres-Trueba A, Ruiz-Treviño FA, Luna-Bárcenas G, Ortiz-Estrada CH. sintering aid for oxygen separation. J Membr Sci 2016; 502:
Formation of integrally skinned asymmetric polysulfone gas 151–157.
separation membranes by supercritical CO2. J Membr Sci 2008; Wardani AK, Hakim AN, Wenten IG. Combined ultrafiltration-
320: 431–435. electrodeionization technique for production of high purity
Tul Muntha S, Kausar A, Siddiq M. Progress in applications of water. Water Sci Technol 2017; 75: 2891–2899.
polymer-based membranes in gas separation technology. Weibel D, Vilani C, Habert A, Achete C. Surface modification of
Polym Plast Technol Eng 2016; 55: 1282–1298. polyurethane membranes using RF-plasma treatment with
U.S. Department of Energy. Oxygen-Enriched Combustion. polymerizable and non-polymerizable gases. Surf Coat Technol
Wahington DC: Energy Efficiency and Renewable Energy, U.S. 2006; 201: 4190–4194.
Department of Energy, 2005. Wenten IG, Khoiruddin K. Recent developments in heterogeneous
Van Huynh C, Kong S-C. Performance characteristics of a pilot-scale ion-exchange membrane: preparation, modification,
biomass gasifier using oxygen-enriched air and steam. Fuel characterization and performance evaluation. J Eng Sci Technol
2013; 103: 987–996. 2016; 11: 916–934.
Velianti, Park SB, Heo PW. The enhancement of oxygen separation Wenten IG, Dharmawijaya P, Aryanti P, Mukti R. LTA zeolite
from the air and water using poly(vinylidene fluoride) membranes: current progress and challenges in pervaporation.
membrane modified with superparamagnetic particles. J RSC Adv 2017a; 7: 29520–29539.
Membr Sci 2014; 466: 274–280. Wenten IG, Khoiruddin K, Hakim A, Himma N. The bubble gas transport
Villaluenga JPG, Seoane B, Hradil J, Sysel P. Gas permeation charac- method. In: Hilal N, Ismail AF, Matsuura T, Oatley-Radcliffe D,
teristics of heterogeneous ODPA-BIS P polyimide membranes editors. Membrane Characterization. Amsterdam, Netherlands:
at different temperatures. J Membr Sci 2007; 305: 160–168. Elsevier, 2017b: 199–218.

Authenticated
Wenten IG, Khoiruddin K, Himma NF. Membrane-based carbon poly(ether ether ketone) for gas separation. High Perform
capture technology: challenges and opportunities in Indonesia. Polym 2014; 27: 10–18.
Adv Sci Lett 2017c; 23: 5768–5771. Zeng C, Zhang L, Cheng X, Wang H, Xu N. Preparation and
Wenten IG, Aryanti PTP, Khoiruddin K, Hakim AN, Himma NF. gas permeation of nano-sized zeolite NaA-filled carbon
Advances in polysulfone-based membranes for hemodialysis. J membranes. Sep Purif Technol 2008; 63: 628–633.
Memb Sci Res 2016; 2: 78–89. Zhang Y, Musselman IH, Ferraris JP, Balkus KJ. Gas permeability
Wu K-K, Chang Y-C, Chen C-H, Chen Y-D. High-efficiency combustion properties of Matrimid® membranes containing the metal-organic
of natural gas with 21–30% oxygen-enriched air. Fuel 2010; 89: framework Cu-BPY-HFS. J Membr Sci 2008; 313: 170–181.
2455–2462. Zhang K, Sunarso J, Shao Z, Zhou W, Sun C, Wang S, Liu S. Research
Wu C, Gai Y, Zhou J, Tang X, Zhang Y, Ding W, Sun C. Structural progress and materials selection guidelines on mixed
stability and oxygen permeability of BaCo1−xNbxO3−δ ceramic conducting perovskite-type ceramic membranes for oxygen
membranes for air separation. J Alloys Compd 2015; 638: production. RSC advances 2011; 1: 1661–1676.
38–43. Zhang B, Shi Y, Wu Y, Wang T, Qiu J. Preparation and characterization
Xu X, Coleman MR. Preliminary investigation of gas transport of supported ordered nanoporous carbon membranes for gas
mechanism in a H+ irradiated polyimide-ceramic composite separation. J Appl Polym Sci 2014; 131: 39925.
membrane. Nucl Instrum Methods Phys Res, Sect B 1999; 152: Zhang C, Sunarso J, Liu S. Designing CO2-resistant oxygen-selective
325–334. mixed ionic-electronic conducting membranes: guidelines,
Xu D, Dong F, Chen Y, Zhao B, Liu S, Tade MO, Shao Z. Cobalt-free recent advances, and forward directions. Chem Soc Rev 2017;
niobium-doped barium ferrite as potential materials of dense 46: 2941–3005.
ceramic membranes for oxygen separation. J Membr Sci 2014; Zhao H, Xu N, Cheng Y, Wei W, Chen N, Ding W, Lu X, Li F.
455: 75–82. Investigation of mixed conductor BaCo0.7Fe0.3−xYxO3−δ with
Yamasaki A, Tyagi RK, Fouda AE, Matsuura T, Jonasson K. Effect of high oxygen permeability. J Phys Chem C 2010; 114:
solvent evaporation conditions on gas separation performance 17975–17981.
for asymmetric polysulfone membranes. J Appl Polym Sci 1999; Zhu H, Jie X, Wang L, Kang G, Liu D, Cao Y. Effect of MIL-53 on phase
71: 1367–1374. inversion and gas separation performance of mixed matrix
Yang N-T, Kathiraser Y, Kawi S. New asymmetric SrCo0.8Fe0.1Ga0.1O₃−δ hollow fiber membranes. RSC Advances 2016; 6: 69124–69134.
perovskite hollow fiber membrane for stable oxygen Zimmerman CM, Koros WJ. Polypyrrolones for membrane gas
permeability under reducing condition. J Membr Sci 2013; separations. I. Structural comparison of gas transport and
428: 78–85. sorption properties. J Polym Sci, Part B: Polym Phys 1999; 37:
Yang F, Zhao H, Yang J, Fang M, Lu Y, Du Z, Świerczek K, Zheng 1235–1249.
K. Structure and oxygen permeability of BaCo0.7Fe0.3−xInxO3−δ Zornoza B, Seoane B, Zamaro JM, Téllez C, Coronas J. Combination
ceramic membranes. J Membr Sci 2015; 492: 559–567. of MOFs and zeolites for mixed-matrix membranes.
Yao W, Cheng H, Zhao H, Lu X, Zou X, Li S, Li C. Synthesis, oxygen ChemPhysChem 2011; 12: 2781–2785.
permeability, and structural stability of BaCo0.7Fe0.3−xZrxO3−δ
ceramic membranes. J Membr Sci 2016; 504: 251–262.
Ye P, Sjöberg E, Hedlund J. Air separation at cryogenic temperature
using MFI membranes. Microporous Mesoporous Mater 2014; Bionotes
192: 14–17.
Ye P, Korelskiy D, Grahn M, Hedlund J. Cryogenic air separation at Nurul F. Himma
low pressure using MFI membranes. J Membr Sci 2015; 487: Chemical Engineering Department,
135–140. Universitas Brawijaya, Jl. Mayjen Haryono
Yi J, Schroeder M, Martin M. CO2-tolerant and cobalt-free 167, Malang 65145, Indonesia
SrFe0.8Nb0.2O3−δ perovskite membrane for oxygen separation.
Chem Mater 2013; 25: 815–817.
Yi J, Schroeder M, Weirich T, Mayer J. Behavior of Ba(Co, Fe, Nb)O3−δ
perovskite in CO2-containing atmospheres: degradation
mechanism and materials design. Chem Mater 2010; 22:
6246–6253.
Yin X, Wang J, Chu N, Yang J, Lu J, Zhang Y, Yin D. Zeolite L/carbon Nurul F. Himma received her bachelor’s degree in chemical engi-
nanocomposite membranes on the porous alumina tubes neering from Institut Teknologi Sepuluh Nopember, Indonesia, in
and their gas separation properties. J Membr Sci 2010; 348: 2013. In 2015, she completed her master’s degree from Institut
181–189. Teknologi Bandung, Indonesia, under the supervision of Professor
Yong WF, Li FY, Xiao YC, Chung TS, Tong YW. High performance Wenten, and then worked as a research asisstant in Prof. Wenten’s
PIM-1/Matrimid hollow fiber membranes for CO2/CH4, O2/N2 laboratory. She is currently a lecturer in the Department of Chemical
and CO2/N2 separation. J Membr Sci 2013; 443: 156–169. Engineering, Universitas Brawijaya, Indonesia. Her research inter-
Yu Y, Liu S, Wang Y, Zhang H, Li X, Jiang Z, Liu B. Asymmetric ests include wastewater treatment and membrane development for
membranes prepared with trifluoromethylphenylated environmental protection.

Authenticated
Anita K. Wardani Putu T.P. Aryanti: Chemical Engineering

Chemical Engineering Department, Institut Department, Jenderal Achmad Yani
Teknologi Bandung, Jl. Ganesha 10, Bandung University, Jl. Terusan Jendral Sudirman, Po
40132, Indonesia Box 148, Cimahi, West Java, Indonesia
Anita K. Wardani graduated with bachelor’s and master’s degrees

Putu T.P. Aryanti received her PhD in chemical engineering from
in chemical engineering from Institut Teknologi Bandung in 2013
Institut Teknologi Bandung (Indonesia) in 2016 under the supervi-
and 2016, respectively. She is currently a PhD student in chemical
sion of Prof. Wenten. Her master’s degree was received in 2002
engineering, Institut Teknologi Bandung, under supervision of Prof.
from Institut Teknologi Sepuluh Nopember (ITS), Indonesia, and
I Gede Wenten. Her research interests focus on modification of poly-
her bachelor’s degree from Institut Teknologi Nasional Malang (ITN
propylene for air separation, water treatment, and other filtration
Malang), Indonesia, in 1997. She joined the Chemical Engineering
processes.
Department at Universitas Jenderal Achmad Yani (UNJANI), Indone-
sia, in 2016, and her current research interests include membrane
Nicholaus Prasetya
preparation and modification.
Chemical Engineering Department, Institut
Teknologi Bandung, Jl. Ganesha 10, Bandung
I Gede Wenten
40132, Indonesia; and Barrer Centre,
Chemical Engineering Department,
Chemical Engineering Department, Imperial
Institut Teknologi Bandung, Jl. Ganesha
College London, Exhibition Road, London
10, Bandung 40132, Indonesia; and
SW7 2AZ, UK
Research Center for Nanosciences and
Nanotechnology, Institut Teknologi Bandung,
Jl. Ganesha 10, Bandung 40132, Indonesia.
Nicholaus Prasetya completed his bachelor’s degree in chemical http://orcid.org/0000-0002-5818-9286,
engineering at Institut Teknologi Bandung (ITB). After working as a igw@che.itb.ac.id
research assistant (at Research Center for Nanosciences and Nano-
technology, ITB) under Prof. Wenten’s supervision, he continued his I Gede Wenten received his bachelor in chemical engineering
master’s degree at Imperial College London as an awardee of Indo- from Institut Teknologi Bandung (ITB), Indonesia, and MSc and
nesia Endowment Fund for Education. He is currently a PhD student PhD degrees from DTU Denmark. He is a professor of chemical
under the supervision of Dr. Bradley Ladewig at Imperial College engineering and a member of Research Center for Nanosciences
London. His research is focused on development of light-responsive and Nanotechnology, ITB. I G. Wenten has long time experience in
metal-organic framework (MOF) and membrane for gas separation. membrane technology at both industrial and academic fields with
a career spanning more than 20 years. He received several awards
such as Suttle Award (1994), Toray Science and Technology Award
(1996), ASEAN Outstanding Engineering Award (2010), and other
national awards from academic and professional foundations. He
is a founder of GDP Filter Indonesia – a membrane manufacturing
company and also a founder of ASEAN Association on Membrane
(Membrane Science and Technology conference).

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Rev Chem Eng 2018; aop

Recent progress and challenges in membrane-

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the membrane thickness is called permeability, P. The

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2 Membrane materials commonly used for O2/N2 separation membrane. Among

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Table 1: Permeation performances of integrally skinned asymmetric polymer membranes.

Membrane material O2 permeance (GPU) or O2/N2 Skin layer Reference

PC 36.0 GPU 5.3 – Pinnau and Koros (1991a)

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Table 2: Performances of polymer blend membranes for O2/N2 separation.

Sample O2 permeability O2/N2 Reference

SBR 602 5.8 George et al. (2001)

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Table 3: Performances of PIM and TR polymer membranes for O2/N2 separation.

Sample O2 permeability O2/N2 Reference

PIM-1 370 4.0 Budd et al. (2005)

PIM-1 from 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindane (monomer 1) and tetrafluoroterephthalonitrile (monomer 2);

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Table 4: Permeation performances of thin plasma polymer layers.

Substrate Monomer gas mixtures (ratio) O2 permeability O2/N2 Reference

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Figure 6: Inorganic-based membrane materials for O2/N2 separation

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Table 5: Performances of perovskite-type membrane for oxygen separation.

Plannar perovskite-type Thickness Operating temperature O2 flux (10 − 4 Reference

Barium-based BaCo0.7Fe0.2In0.1O3−δ (BCFI) 1 1173 2.47 (Yang et al. 2015)

BaCoxFeyZrzO3−δ (BCFZ) – 1148 – 12.50 (Wang et al. 2005)

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Table 6: Dual-phase oxygen transport ceramic membranes.

Material composition of membrane Membrane Operating Oxygen flux Reference

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Table 7: Carbon membrane types for O2/N2 separation.

Precursor types Synthesis conditions Modifiers O2/N2 selectivity Reference

Polyimide 500°C, 2 h – 8.5–11.5 Jones and Koros (1994)

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Table 8: Performances of MMMs for O2/N2 separation.

MMM composition Inorganic P(O2) O2/N2 Reference

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(super-paramagnetic polymer containing magnetic Fe2O3

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Figure 12: Schematic diagram of oxy-combustion process.

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Gasification is a process to transform coal or another 4.1.3 Desulfurization

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2 Membrane materials commonly used for O2/N2 separation membrane. Among

Gasification is a process to transform coal or another 4.1.3 Desulfurization