Renewable and Sustainable Energy Reviews 15 (2011) 1284–1293

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Oxygen separation from air using ceramic-based membrane technology

for sustainable fuel production and power generation
S.S. Hashim, A.R. Mohamed, S. Bhatia ∗
School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Penang, Malaysia

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

Article history: There has been tremendous progress in membrane technology for gas separation, in particular oxygen
Received 28 May 2010 separation from air in the last 20 years providing an alternative route to the existing conventional separa-
Accepted 13 October 2010 tion processes such as cryogenic distillation and pressure swing adsorption. This paper covers the review
of membrane separation process and recent developments of ceramic membranes for oxygen separation
Keywords: from air. This membrane based oxygen supply from air offers significant advantages for integration in
Ceramic membranes
power generation cycles with carbon dioxide (CO2 ) capture, coal gasification systems and gas-to-liquid
Oxygen separation from air
(GTL) plants. The critical issues in the implementation of membrane technology for power generation
Power generation
CO2 capture
and fuel production are also presented and discussed.
Coal gasification © 2010 Elsevier Ltd. All rights reserved.
GTL

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1285
1.1. The advances of air separation techniques for oxygen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1285
1.2. Cryogenic air separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1285
1.3. Swing adsorption-based systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1285
1.4. Mixed ionic–electronic conducting ceramic-based membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1286
1.5. Comparisons of process alternatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1286
2. Membranes for sustainable fuel production and power generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1286
2.1. Oxyfuel combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1286
2.2. Gasification systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1288
2.3. Coal gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1288
2.4. Gas-to-liquid (GTL) process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1289
3. Progress in high temperature membrane-based separation for oxygen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1289
3.1. Advanced zero emissions power plant (AZEP) project . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1289
3.2. Zero emission ion transport membrane oxygen power (ZEITMOP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1290
3.3. OXYCOAL-AC project at RWTH Aachen University . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1290
4. Critical issues in the implementation of membrane-based separation technology for oxygen production in the power generation and
fuel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1291
5. The way forward . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1291
6. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1292
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1292
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1292

∗ Corresponding author. Tel.: +60 4 5996409; fax: +60 4 5941013.

E-mail address: chbhatia@eng.usm.my (S. Bhatia).

1364-0321/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.rser.2010.10.002
 S.S. Hashim et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1284–1293
1. Introduction
1.1. The advances of air separation techniques for oxygen
production
Oxygen constitutes 21 vol.% of the air. It is among the most
widely used commodity chemicals in the world [1], with numer-
ous applications in almost every industrial sector. The separation of
oxygen from air is a big business, where nearly 100 million tons of
oxygen are produced every year [2]. This oxygen market is believed
to be expanding in the coming years because all large-scale clean
energy technologies will require oxygen as a feed [3]. More recently,
strong demand for tonnage quantities of oxygen is encouraged by
the steady growth in chemical process operations. For instance,
oxyfuel combustion process and oxygen-blown gasification to con-
vert coal and natural gas into an intermediate synthesis gas that can
be further processed to produce electricity, chemicals and trans-
portation fuels. There have been two fundamental approaches for
air separation, which are cryogenic and non-cryogenic distillation.
The cryogenic distillation is typically reserved for applications that
require tonnage quantity of oxygen at ultra-low-temperature. The
latter involves the separation of air at ambient temperatures using
either molecular sieve adsorbents via pressure swing adsorption
(PSA), or membrane separation process using the polymeric mem-
branes. Meanwhile, there is an air separation technique by chemical
processes that is based on the ability of certain materials, such as
molten salt to absorb and desorb oxygen at particular pressure and
temperature conditions [4]. Air Products and Chemicals operated
a small-scale pilot plant using this technique; however, this tech-
nique was not cost effective because of the corrosion of salt/oxygen
two-phase areas of the plant [4]. Recently, a third category of air
separation has emerged, which is based on specialized ceramic
membranes that separate oxygen from air at elevated tempera-
tures, in contrast to the super-cooled temperatures required by
conventional cryogenic distillation. Extensive demonstration-scale
testing suggests that this approach will lead to the development of
compact systems that produce tonnage oxygen supply with signif-
icant advantages, in terms of reductions in capital cost and energy
requirements. Advances in these three main techniques are dis-
cussed below.
1.2. Cryogenic air separation
Cryogenic air separation is the conventional technology for pro-
ducing large quantities of oxygen. This technology was pioneered
in the early 1900s and is still used today to produce high purity
oxygen [5]. While currently tonnage quantities of oxygen (oxygen
concentration ≥99%) are carried out by the cryogenic distillation
process, this technology is noted to be complex, expensive and
energy intensive. By cryogenic distillation, the inlet air must be
filtered, compressed and chilled to about −185 ◦ C. Thereafter,
the liquefied stream is distilled in large distillation towers to
separate air into its component phases (78 vol.% nitrogen, 21 vol.%
oxygen, 1 vol.% argon and other trace gases), according to their
boiling points. The use of cryogenic distillation for oxygen supply
(oxygen concentration ≥95%) in the field of oxyfuel power plant
and coal gasification has meanwhile reduced the power generation
efficiencies from current best practice of around 40–30% [3];
therefore, it is vital to optimize the energy efficiencies of cryogenic
air separation method for feasible energy delivery technologies.
Multi-tower processes, lowering the process air pressure and
more efficient compression are few strategies implemented that
practically resulting to the 20% energy savings. This particular
separation technology is almost reaching its maturity level. It
relies on the improved turbine, compressor and heat exchanger
efficiencies for better performances [6]. According to Allam [7],
1285
modern air compressors with high efficiency and advanced aero-
dynamic design will be available for the large single train oxygen
plants of up to 10,000 tons/day capacity, which is required for
power and hydrogen systems with CO2 capture. It has been noted
that there have been re-engineering efforts by some industrial gas
producers to reduce the energy consumption and both capital and
operating costs. For instance, the use of packed towers instead of
the traditional trayed towers have been implemented, while others
are working on improving heat exchangers, high efficiency com-
pressors and control systems that provide real time optimization
[7]. Some of these companies are also investigating on employing
higher operating pressures to reduce the overall distillation column
diameter. Coupled with fully utilization of the cryogenic distil-
lation process, current approaches towards reducing the energy
requirements of this conventional air separation technology for
large quantities of oxygen production are well in progress.
1.3. Swing adsorption-based systems
The utilization of swing adsorption (SA) in the production of
oxygen from air separation has been recognized and is mainly
dominated by large gas separation companies such as BOC, Prax-
air, Air Products & Chemicals, Air Liquide, and Linde. Swing
adsorption technology is suitable for small to medium-scale
plant (20–100 tons/day); hence, it is not applicable to large-scale
(100–300 tons/day and beyond) production of oxygen, which is
typically carried out by cryogenic distillation processes. Swing
adsorption process seems to be the best alternative because of
the matured technology, adsorbents availability as well as a low
cost energy, and highly efficient gas separation system [8,9]. Vac-
uum swing adsorption (VSA), pressure swing adsorption (PSA),
temperature swing adsorption (TSA) and hybrid vacuum-pressure
swing adsorption (VPSA) or temperature–pressure swing adsorp-
tion (TPSA) systems are the variation of this technology. Most of
these systems are relied entirely on zeolites to trap nitrogen in
order to produce oxygen with purities from 90% to 95%. It is noted
that the zeolites A and X are the most important component as
an adsorbent in the oxygen-pressure swing adsorption (O2 -PSA)
process [10]. Hitherto, the investigation on the processes with dif-
ferent adsorbents and operational conditions has been done by
few researchers. Recently, a new adsorbent, namely AgLiLsx was
described in a patent by Air Products & Chemicals [11] for use in
a vacuum pressure swing adsorption for the production of high
purity oxygen from air separation. In addition, Mendes and co-
workers [11] investigated on the use of silver exchanged zeolite
for oxygen separation from air while Zahra et al. [8] experimen-
tally and theoretically evaluated the four-bed PSA process using a
commercial 13X zeolite.
Ceramic authothermal recovery (CAR) technology is developed
by BOC Group for air separation and partial oxidation of hydrocar-
bons [12]. This concept was based on the adsorption and storage
of oxygen at high temperatures, typically 600–800 ◦ C. The process
employs fixed-bed vessel with multiple beds that are filled with
extruded pellets of ceramic perovskites, sandwiched between lay-
ers of alumina beads. This process operates more or less similar to a
PSA system, where multiple beds are cycled back and forth between
adsorption and desorption modes enabling continuous production
of an oxygen stream. The CAR process offers a significant advance-
ment in air separation technology because the oxygen production
cost is estimated to be 20–30% lower than the cryogenic air sepa-
ration technology [12]. However, it has been estimated that there
will be an increase of the electricity cost of about 26% for a CAR
integrated coal-fired power plant [12]. The main hurdles towards
the commercialization of CAR process are the cost of perovskite
and the impact of impurities on this particular material. As a final
remark, a good performance of adsorption processes relies on the
1286 S.S. Hashim et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1284–1293
800- 900oC
7- 20 bar
Pressurized 1 Oxygen
air feed 2 depleted air Non-permeate
MIEC ceramic O2- O2-
membrane
Electron Electron
Oxygen rich 1 Sweep gas Permeate
stream 2 matured cryogenic through developing ceramic membranes. As
Low pressure
Fig. 1. Schematic representation of the oxygen transport in dense MIEC ceramic
membrane.
pressure; however, increasing the pressure causes the increase in
cost. In brief, it is crucial to optimize this situation in order for
adsorption-based oxygen separation from air technology enters the
non-traditional industrial gas markets.
1.4. Mixed ionic–electronic conducting ceramic-based
membranes
Meanwhile, there is another promisingly potential technology
for oxygen separation from air, which is an alternative to the con-
ventional cryogenic air separation. This novel technique is based
on dense ceramic membranes, which carry out the separation of
oxygen from air at elevated temperatures, typically 800–900 ◦ C. In
the past decades, enormous efforts have been directed to ceramic
membranes with mixed ionic–electronic conducting (MIEC) char-
acteristics due to their potential application of producing high
purity oxygen. Interestingly, these membranes require neither
electrodes nor an external circuit to operate. As conceptualized
in Fig. 1, the electronic conductivity itself performs as an internal
short circuit that involves oxygen partial pressure gradient. The O2
permeates from the high oxygen partial pressure side to the low
oxygen partial pressure side, while the overall charge neutrality
is maintained by counterbalancing the flux of electrons [13]. Sev-
eral industrial gas companies are working on developing ceramic
membranes for oxygen separation from air at high temperatures.
Air Products and Chemicals has developed an ion transport mem-
brane (ITM) system, which is based on patented, high temperature
ceramic membranes for the production of oxygen from air sep-
aration. Praxair is also working on oxygen-conducting ceramic
membrane systems that are specially designed to separate oxygen
from air at elevated temperature environment.
1.5. Comparisons of process alternatives
The ongoing improvements of the adsorption and polymeric
membrane processes in both energy and cost efficient are expected
through continuous research and development of adsorbents and
membrane materials. Both adsorption and polymeric membrane
systems yield nitrogen containing a significant amount of oxygen
as a byproduct; on the contrary, these processes are less compli-
cated and more passive than the cryogenic process. Meanwhile,
chemical processes show the potential for continuous operation
and economies of scale through large production output from single
trains; on the other hand, the material corrosion is one of the major
Table 1
The comparisons of process alternatives for oxygen production from air separation [4].
Process Status
Cryogenic Mature
Adsorption Semi-mature
Polymeric membrane Semi-mature
Chemical Developing
Ceramic membrane Developing
problems. More recently, ceramic membranes are foreseen as the
best candidate to replace cryogenic technology for high purity, ton-
nage supply of oxygen from air separation at high temperatures.
Similar to the other non-cryogenic processes, this technology is
engaged with the production of pure byproducts and liquids for
Oxygen vacancies
in lattice
storage and backup. Table 1 compares various oxygen produc-
tion technologies, where the status of the technologies is from
for the economy-feasibility technology comparison, less-efficient
but simple adsorption and polymeric membrane systems are pre-
ferred at lower production rates. The cryogenic process is excellent
in producing relatively pure nitrogen or argon streams. All tech-
nologies, except polymeric membrane systems are able to produce
oxygen at maximum purity. Adsorption and polymeric membrane
systems require less time to restart the process and reach purity
after a shutdown. Apart from the fact that integrating ceramic
membranes can reduce oxygen energy costs by more than 35% as
in comparison to the conventional separation technology [14,15],
the potential of these membranes for oxygen separation from air
at high temperatures in industrial scale is not fully developed. This
is due to the non-availability of general design methodologies and
comprehensive process know-how. Therefore, it is wise to develop
the modeling of membrane processes integrating with the process
simulator to model membrane separation process, predictive mem-
brane and module performance models. This paper will focus on the
recent advances of ceramic membranes suitably for oxygen sepa-
ration from air and their integration in power generation cycles
with carbon dioxide (CO2 ) capture, coal gasification systems and
gas-to-liquid (GTL) plants. The issues and problems regarding the
implementation of this new technology for power generation and
energy conversion processes will be further discussed, as well as the
future directions of ceramic-based membrane for the production of
tonnage supply of oxygen from air separation.
2. Membranes for sustainable fuel production and power
generation
2.1. Oxyfuel combustion
Oxyfuel combustion, also called oxyfired, oxycombustion or
oxycoal combustion technology uses oxygen instead of air for fuel
combustion, which produces flue gas that contains mostly of H2 O
and CO2 that are readily captured [16]. By oxyfuel combustion pro-
cess, coal is burned in a high-oxygen environment rather than in
an air-based environment. The exhaust combustion flue gas stream
turns out to be more highly concentrated in CO2 by keeping out the
nitrogen from the system. Pure CO2 is easily captured, compressed
and liquefied that can be sold or sequestered using particular meth-
ods as reported elsewhere [17,18]. CO2 concentrations above 90%
are obtainable. It is noticeable that the penalty for purification and
compression of the CO2 by oxyfuel combustion can be reduced
to around 110–170 kWh/tCO2 [19,20]. However, the production of
oxygen in oxyfuel power plants has been resulting to the rise of an
extra energy demand.
It is worthwhile to be noted that there are two different tech-
niques for the production of oxygen in the oxyfuel power plants.
Economic range (sTPD) Byproduct capability Purity limit (vol.%) Start-up time
>20 Excellent 99+ Hours
<150 Poor 95 Minutes
<20 Poor ∼40 Minutes
Undetermined Poor 99+ Hours
Undetermined Poor 99+ Hours
 S.S. Hashim et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1284–1293
Fig. 2. Schematic of an oxyfuel power plant incorporating MIEC membrane module [3].
Allam [7] has presented an overview on the development stage of
oxygen production techniques in his paper, while Ekstrom et al. [21]
have successfully evaluated these techniques in terms of economic
perspectives. Cryogenic air separation is a well-established method
for large-scale oxygen production, but the operation of the cryo-
genic separation unit consumes about 15% of the electrical output of
the power station [3]. The current work requirement is reported to
be 220 kWh/tO2 by Foster Wheeler [22] and 245 kWh/tO2 from Hong
et al. [23] for the large-scale production of several thousand tons
of oxygen needed by oxyfuel process. For a standalone system, the
energy demand for the production of oxygen is about 240 kWh/tO2 ,
which causes the overall plant efficiency to decrease to about 8–10%
points [24]. The improvement of heat recovery from the cryogenic
unit separation process as well as the optimization of the separation
process could reduce the energy demand to 160 kWh/tO2 [19].
The second method for the production of oxygen from air
separation is by using novel ceramic membranes with MIEC char-
acteristics. Fig. 2 illustrates the schematic of an oxyfuel combustion
power plant incorporating MIEC membrane. As shown in Fig. 2, air
compressor functions to pressurize the air up to 10 bar. In order
to obtain the separation of air, both membrane and air have to be
exposed to temperatures above 800 ◦ C and an oxygen partial pres-
sure ratio across the membrane has to be applied as well. The heat to
bring this high temperature can be extracted from the combination
of compression of the air, flue gas recycle and also heat exchange
from the boiler. Interestingly, the ceramic membrane module can
be integrated at the front end of the oxyfuel combustion plant. One
of the technical features of such integration is the use of recycled
CO2 from the combustion process could lead to a high oxygen driv-
ing force resulting from the constant oxygen partial pressure drop
across the membrane. The oxygen permeates selectively through
a membrane, from the compressed air side into the recycled CO2
stream, enriching it to about 20% (v/v) [3]. Thereafter, the oxy-
gen enriched CO2 stream can be burnt directly in the boiler that
will yield the superheated steam to drive the steam turbines and
subsequently, produce electricity.
There are two different concepts for incorporating MIEC mem-
brane into the oxyfuel combustion process, as illustrated in Fig. 3.
As shown in Fig. 3(a), the concept of allowing the flow of recircu-
1287
lated flue gas over the membrane surface is employed; thus, the
oxygen can be assimilated directly. This so-called four-end con-
cept [25–27] is designated for IGCC processes; however, membrane
materials with high permeation rate like Ba0.5 Sr0.5 CO0.8 Fe0.2 O3−ı
(BSCF) are not CO2 -resistant. As a result, the BSCF membranes can
only be applied when there is no direct contact between the mem-
brane material and flue gas. On the contrary, the three-end concept
[28,29] illustrated in Fig. 3(b) seems to be an attractive option, in
which direct contact between the membrane and flue gas can be
avoided. In this particular case, the oxygen is extracted from the
membrane module by a vacuum pump. It is worthwhile to be noted
that although higher thermal efficiency of the oxyfuel combustion
process is obtainable if the first concept is employed, the three-end
concept is likely to be more feasible because there are no mem-
brane materials are available that can withstand the direct contact
with the flue gas; therefore, the development of membrane materi-
als is very crucial [30,31]. Kneer et al. [25] successfully presented in
their paper on membrane-based air separation modules and their
design for oxycoal conditions, the specifications of coal combustion
in a CO2 /O2 atmosphere including related burner design as well as
the cleaning of hot flue gas from oxycoal combustion.
It is worth being noted that there are issues related to the imple-
mentation of this novel method for the oxygen supply from air
separation. First, the membrane separation system has to be oper-
ated at temperatures above 900 ◦ C in order to deliver high oxygen
permeation flux. As a result, there will be large energy penalties
in this process because the heated air contains about 80% (v/v)
of nitrogen, as a waste gas. The energy losses can be reduced
through proper implementation of the heat recovery, although the
process efficiency losses can never be completely recovered. Sec-
ondly, although high CO2 partial pressure is practically attractive
to membranes due to the high oxygen driving force, the aggressive
conditions would cause these membrane materials to destabilize;
thus, their performance in producing oxygen for the oxyfuel com-
bustion process will be limited. It is expected that the large demand
for oxygen supply for oxyfuel combustion process in the near future
will result to the implementation of oxygen membrane separation
technology; however, ongoing research and development is crucial
to overcoming the major hurdles. In brief, a significant cost reduc-
1288 S.S. Hashim et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1284–1293

Fig. 3. Schematic of membrane for oxygen separation in oxyfuel processes using (a) four-end concept and (b) three-end concept [31].

tion in the oxygen production causes the oxyfuel power plant as an
attractive option when the carbon capture becomes a requirement
in the future. Hence, it is believed that ceramic membranes are an
effective high temperature air separation technique that may offer
a considerable cost reduction in the production of oxygen for this
particular application.
2.2. Gasification systems
Gasification is an energy extraction method that converts rela-
tively low cost feedstocks such as coal, natural gas petroleum coke
in isolated or geographically unfavorable sites, biomass or organic
waste. The reaction of these feedstocks with a controlled amount
of oxygen and/or steam at high temperatures produces synthesis
gas (syngas), which consists of carbon monoxide (CO) and hydro-
gen (H2 ). Subsequently, the produced syngas stream is fired in
a combined-cycle power plant. The combined-cycle power plant
uses one or more gas turbines and steam turbines in series to gen-
erate electricity. Electricity generation using gasification is called
integrated gasification combined cycle (IGCC). The syngas can also
be further refined to yield a variety of petrochemical products in
a coal-to-liquid (CTL) plant, or by catalytically reacting the syn-
gas using Fisher–Tropsch synthesis in a gas-to-liquid (GTL) plant
to produce liquid transportation fuels, such as naphtha, jet fuel
and low-sulfur diesel. The heart of any gasification-based facility
is the partial oxidation reactor where the reaction of the feedstock
with a high-pressure oxygen stream to produce the syngas occurs.
Hence, the gasification technique is fundamentally relied on the
use of pure oxygen. Large-scale commercial gasification facilities
require an enormous amount of oxygen, which lead to the technol-
ogy requirements to meet the large oxygen demand.
carriers as alternative methods to produce oxygen has also been
studied, which includes the close cycle looping of CaSO4 [35,36]
and other oxygen carriers such as manganese [37], nickel [38] and
iron [39,40] oxides. Nevertheless, there are problems of employing
this particular method such as slow reaction rates, solid handling
and large solid oxygen carrier inventory [39,40]. The introduction
of novel method based on ceramic membranes for oxygen produc-
tion from air separation is believed to increase the efficiency of IGCC
power plant because these membrane modules involve no moving
parts; thus, it is easy to operate and maintain. Fig. 4 illustrates the
incorporation of the ceramic membrane and coal gasification in
an IGCC plant. It should be noted that the syngas produced by the
gasifier is used as fuel in the gas turbine and the heat generated by
the combustion is used to generate steam to drive the steam tur-
bine. Meanwhile, the turbine that functions to run the generator
can be used to supply compressed air to the membrane unit while
the steam from the steam turbine can be sent directly to the mem-
brane unit. Unlike the membrane operated in oxyfuel plant that
must be resistant to the reducing effects of CO2 in the permeate

2.3. Coal gasification

The technical advantages of coal gasification for power genera-

tion include its high efficiency and low emissions of SOx , NOx and
particulate matter. It is to be noted that an IGCC coal-fired power
plant comprises of two technologies, which are coal gasification and
combined cycle that leads to the most efficient method for elec-
tricity generation [32,33]. Traditionally, the oxygen feed for coal
gasification is carried out by cryogenic distillation method; how-
ever, it has been reported that there are several inefficiencies by Fig. 4. Incorporation of coal gasification and MIEC membrane module in an IGCC
using this conventional technology [34]. The use of solid oxygen power plant [3].
 S.S. Hashim et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1284–1293
Natural Gas
Methane
Gas Processing
CO
Syngas Fisher
Production Tropsch
H2
Air Separation
Oxygen Synthetic Crude
Air LPG Product
Naphtha Refining
Diesel
Fig. 5. Main steps in the commercial GTL process [42].
side, the membrane used in coal gasification plant must be resis-
tant to steam; so that, the heat from the steam does not affect the
membrane applications [41]. In a nutshell, the use of MIEC mem-
branes in coal gasification systems has a promisingly potential for
the production of tonnage supply of oxygen from air separation if
further research is directed to overcome the design and engineer-
ing problems related to these membrane materials and gas tight
sealing of the membranes in the modules.
2.4. Gas-to-liquid (GTL) process
Gas-to-liquid (GTL) technology converts natural gas to clean and
useful liquid hydrocarbons, suitably to overcome problems such as
remote gas utilization, crude oil price and environmental pollution
[42]. Fig. 5 shows the main steps in the commercial GTL process,
which are: (1) air separation, (2) gas processing, (3) syngas pro-
duction, (4) Fisher–Tropsch (FT) synthesis, (5) hydrocracking and
(6) product separation. Autothermal reforming (ATR) is a conven-
tional syngas technology for FT process that requires high purity
oxygen, which is traditionally produced by the cryogenic distilla-
tion process. However, the large cryogenic distillation consumes
10–15% of the total capital costs. An enormous power demand
to carry out compression and chilling is required. The introduc-
tion of ceramic membranes to replace the conventional cryogenic
distillation method is considered as an attractive option for the pro-
duction of oxygen from air separation at high temperatures. This
novel technology significantly reduces the capital costs as well as
offers high efficiency method to produce syngas from the natural
gas. Fig. 6 illustrates the schematic of syngas production process.
As shown in Fig. 6, the membrane structure incorporates the dense
ceramic membrane undergoing reduction containing reforming
catalyst. The ceramic membranes are attractive because oxygen
permeates from low pressure side to high pressure fuel stream
without the need of mechanical compression. Because of the oxy-
Fig. 6. The synthesis gas production incorporates the dense ceramic membrane and
reduction and reforming catalyst [14].
1289
gen partial pressure on the fuel side of the membrane is on the
order of 10−12 –10−16 units regardless of the fuel side total pres-
sure, a substantial driving force is established across the membrane
[43]. Additionally, by membrane-based separation, the need for air
compression is minimized; sufficiently enough to overcome the
pressure drop through the membrane separation unit and air heat
exchangers. A considerable attention has to be focused on the mem-
brane stability to withstand the extreme temperatures and stresses
of an ATR environment, as well as their resistance to the creep,
corrosion and poisoning [43]; also, the long term compatibility
with the reduction and reforming catalysts. Besides, the oxidation
process on the fuel side is very rapid and exhibits the so-called
autocatalytic effect that reduces the oxygen partial pressure and
increases the temperature, which leads to the increase in the oxy-
gen permeation flux. Therefore, it is necessary to control the partial
oxidation exotherm by providing a stable thermal operating mode
and control mechanisms to avoid thermal runways and formation
of hot spots. It is to be noted that MIEC ceramic membranes could
replace the conventional cryogenic distillation by offering cheaper
and higher efficiency technology for the production of syngas from
natural gas for ultra-clean fuel applications if problems related to
membrane incompatibility are solved.
3. Progress in high temperature membrane-based
separation for oxygen production
3.1. Advanced zero emissions power plant (AZEP) project
Prior to the Griffin et al. [44] work, the most efficient and
cost-effective utilization of the MIEC membrane reactor is by inte-
grating it into a conventional gas turbine system to initiate an
advanced zero emissions plant, namely an AZEP concept. The aim
of this project is to replace a gas turbine-based power genera-
tion process to reduce CO2 emissions by an oxyfuel system using
MIEC membrane with natural gas fuel [45]. The core element in
AZEP is an integrated MIEC membrane reactor [46], which involves
three steps: (1) the separation of oxygen from air using MIEC
membrane, (2) the combustion of natural gas in a nitrogen-free
environment and (3) the heat of combustion is transferred to air
by heat exchange. The required heat to operate MIEC membrane is
supplied by the heat generated from this combustion; thereafter,
the oxygen depleted air that leaves the reactor is heated from this
combustion. The design of the MIEC membrane reactor is a combi-
nation of square section multichannel extruded ceramic monolith
heat exchange and ion transport membrane (ITM). The membrane
material used is a mixed metallic oxide that could withstand the
combustion temperature of 1300 ◦ C [7]. Fig. 7 demonstrates the
simplified sketch of the AZEP concept. The process exhaust com-
prises of two separate flows, which are oxygen-depleted air flow
and CO2 and H2 O flow, in which the CO2 can be sending off for
end disposal by condensing the water. The combustion products on
the permeate side, which are mostly of CO2 and H2 O are partially
recirculated into the reactor and partially expanded in the “sweep
turbine” for additional power generation. Moller et al. [47] did a
thermo-economic analysis on the AZEP gas turbine combined cycle
power plants. These researchers concluded that uncertainties in the
MIEC membrane reactor cost and useful life of ceramic membrane
materials do not have an immense influence on the electricity cost.
Hence, towards the reduction of CO2 avoided cost, the AZEP con-
cept is believed to be more fuel efficient than the baseline system
[7]. It is noticeable that there is a problem of using ceramic mem-
branes to supply oxygen; the ceramic membranes cannot be heated
to too high temperature because it may cause these membranes to
destabilize; however, in order for the gas turbine to achieve high
efficiency, the combustion process should occur at the highest pos-
1290 S.S. Hashim et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1284–1293

Fig. 7. A schematic of an AZEP concept [48].

sible temperature. As a summary, it is important to develop both
membranes and high temperature heat exchanger for a successful
AZEP concept.
3.2. Zero emission ion transport membrane oxygen power
(ZEITMOP)
Yantovski et al. [49] proposed Zero Emission Ion Transport
Membrane Oxygen Power (ZEITMOP), using MIEC membrane to
extract the oxygen required for combustion from air. The ZEITMOP
cycle requires a membrane unit that operates at 920 ◦ C and a sepa-
rate combustion chamber that operates at 1400 ◦ C. Physically, the
air separation unit could be smaller if oxygen is consumed by a
chemical reaction on the permeate side if the membrane whence
the large oxygen flux is obtainable. Besides, no additional heating
is required if this reaction is exothermic where the air separa-
tion unit is heated by the reaction itself. Interestingly, these two
requirements are fulfilled by combustion; hence, combustion in
the membrane module would permit a smaller air separation unit,
which would also act as a combustion chamber. However, most
membranes are easy to get damaged as the combustion cham-
ber operates at 1400 ◦ C. Since the worldwide expectations towards
oxygen separation membranes are extremely high, an extensive
research is continually engaged in developing new materials;
therefore, it may be possible to have an oxygen membrane chamber
operating at 1400 ◦ C. Additionally, the combustion chamber may be
cooled, so that it could operate at more realistic temperatures for
current available membrane materials. A comprehensive analysis
of the effects of combining air separation with combustion in a ZEIT-
MOP was presented by Foy and McGovern [50]. These researchers
concluded that the use of a combined ion transport membrane oxy-
gen combustion chamber and air separation unit in the ZEITMOP
cycle did not perform well, unless the unit can be operated at high
temperatures. In addition, the use of a high temperature combined
ion transport oxygen combustion chamber and air separation unit
appears brought only minor effect on the thermodynamic efficiency
of the ZEITMOP. Furthermore, further investigation of the effect
of combining the two units must be done by simulating the heat
exchange between the combustion and air streams in the combined
unit. The optimization of the ZEITMOP cycle could help to increase
its efficiency since this particular cycle is not commercially avail-
able yet. Since all types of fossil fuels are suitable for this cycle [51],
it is believed to be one of the attractive options for the development
of zero CO2 -emission fossil fuel-based power plants.
3.3. OXYCOAL-AC project at RWTH Aachen University
Six research institutes at Rheinisch-Westfälische Technische
Hochschule Aachen (RWTH Aachen University) and five industry
partners worked cooperatively since September 2004 to develop a
free CO2 -emission oxycoal combustion power plant incorporating
MIEC membrane for electricity generation [52]. This OXYCOAL-AC
project is based on pulverized coal combustion in a CO2 /H2 O/O2
atmosphere and targeted high CO2 concentrations in the flue gas
for subsequent CO2 capture and storage [52]. Fig. 8 shows the
key component of this concept is ion transport membrane for
oxygen production where oxygen molecules are transferred from
the pressurized air side across a mixed conducting membrane to
the recirculated low pressure flue gas stream [52]. The scope of
this project includes screening and testing of available membrane
materials, especially perovskites; advanced manufacturing pro-
cesses for tubes and discs as well as searching for relevant material
properties for their applicability to oxycoal conditions. Accordingly,
MEM-OXYCOAL was initiated in 2006 focusing on the development
of membrane materials for the OXYCOAL-AC process [52]; there-
after, a comprehensive analysis on varying thermal, mechanical and
chemical conditions can be possibly done; and, module geometry
can also be properly designed, which are still under development.
The detailed information on the design of the membrane reactor
for the OXYCOAL-AC cycle is well-discussed by Renz et al. [53]. It
is noted that the commercialization of this particular process is
possible through the ongoing developments of oxygen separation
Fig. 8. Schematic of an OXYCOAL-AC power plant process [25].
 S.S. Hashim et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1284–1293
membranes as well as proper design concepts for scaling up the
membrane modules and their integration into pilot or power plant
scale facilities.
4. Critical issues in the implementation of
membrane-based separation technology for oxygen
production in the power generation and fuel production
The energy demand for oxygen production is one of the major
reasons for the efficiency losses in implementing carbon capture
and storage (CCS) based on oxyfuel combustion system as well
as gasification systems. Hence, the membrane separation technol-
ogy based on ceramic membrane material is adopted to replace
the conventional cryogenic separation technology. However, there
are several issues that need to be addressed. One of the issues in
implementing high temperature MIEC membrane air separation is
the large penalty associated with heating the air up to 900 ◦ C for the
membrane to operate. Another issue is the current instability of the
membrane material with reducing and extreme environments [3].
The energy demand for the production of oxygen by ceramic-
based membrane air separation is determined by the required high
temperature heat [54]. It is crucial to note that there will be a large
energy penalty associated with high air volume heating, as the max-
imum theoretical recovery rate is the concentration of oxygen (21%)
in an air; thus, to operate the high temperature ceramic membrane-
based air separation unit, these membranes have to be heated
well, typically at 700–1100 ◦ C. Although some of the energy can be
recovered from the waste gases, the process efficiencies could be
improved with the recovery of energy. As for coal-fired power plant,
the heat required is supplied by the flue gases. In Oxycoal-AC pro-
cess, the flue gas provides the required high temperature heat and
also enhances the oxygen permeation flux by sweeping the mem-
brane. To supply high temperature heat up to 700 ◦ C, about 70% of
the flue gas is fed to the membrane separation unit; thereafter, it
is recycled to the combustion chamber at the temperature around
500–700 ◦ C after oxygen enrichment. One of the major problems is
that the membrane material may be destabilized or incompatible
to high temperature gas cleaning unit for removal of dust and flue
gas components; moreover, the recirculation fan should operate in
the high temperature, ranging from 500 to 700 ◦ C. Therefore, the
effect of the hot end flue gas recirculation fan on the overall power
plant efficiency should be accounted. Furthermore, although the
high temperature of the gases is useful to provide a better gas tur-
bine power output in the process, more energy is definitely required
for the permeate recompression due to the higher quantity of this
stream. Pfaff and Zwick [55] analyzed that the oxyfuel process with
high temperature membrane air separation unit shows the depen-
dency on the heat recovery of the off-gas leaving the expansion
turbine. These researchers claimed that it is irrelevant to minimize
the thermal and electrical energy demand to run this particular air
separation unit for overall process optimization purposes. Accord-
ing to these researchers, it is also inevitable for a minimal degree
of the integration of ceramic membrane with regards to the heat
recovery to compete with the net efficiency of the oxyfuel process
with the conventional cryogenic separation (oxygen purity 99.5%,
v/v) without any integration. The application of high temperature
MIEC ceramic membrane-based air separation is dependent on the
process [3]. It is questionable, at a different pressure operating con-
dition, which process incorporating MIEC membrane for oxygen
production results to less energy demand. The integration of the
MIEC membrane unit requires the oxyfuel combustion system to
be operated at ambient pressure operating conditions, while IGCC
process at elevated pressures. Obviously, the IGCC incorporating
MIEC membrane is an energy intensive process due to the com-
pression of oxygen until the gasifier pressure level is achieved.
1291
Therefore, it can be said that the integration of the MIEC mem-
brane air separation unit in the oxyfuel process is technically more
advantageous in comparison to the IGCC process with respect to the
pressure operating conditions. It is also crucial to consider the issue
of membrane materials for the production of oxygen from air sep-
aration for power generations and fuel production. The challenges
that are needed to be overcome are to ensure that these membranes
have high permeability, specific selectivity and long-term stability
up to 100,000 h [56]. It is noticeable that the availability of mem-
branes for used gas separation in other fields such as in chemical
industry is not yet reached its level of suitability for large-scale
industrial applications as required in power generation and fuel
production. Therefore, it is important to come out with remark-
able strategies for these ceramic MIEC membranes with regards to
materials science and technology into the research and technology
development. Conclusively, membrane operating conditions and
membrane materials are related to each other. Membrane materi-
als used must be compatible to the process conditions; hence, the
implementation of ceramic membranes for oxygen production in
power generation and fuel production can be fully utilized in the
power generation and fuel production applications.
5. The way forward
Presently, membrane separation is a new technology in compar-
ison to the well-matured cryogenic air separation in the production
of oxygen from air separation for power generation and fuel
production purposes; namely, oxyfuel combustion process, coal
gasification systems as well as syngas production. Importantly, the
heart of the membrane-based separation at high temperatures is
the membrane materials that are exclusively stable, strong, and
creep resistant and with high oxygen flux. Therefore, it is expected
that there will be improvements in the performance of membrane
in oxidizing and reducing environments. Moreover, there will be a
focus on long term membrane materials testing programs, which
will emphasize on the pressure and temperature cycling to exploit
these membranes useful life. The mentioned vision will only be
realized through extensive research and development (R&D). Even-
tually, there is a need to develop reasonable demonstration-scale
projects under practical operating conditions to obtain the remark-
able oxygen production required by the industry. The so-called
MEM-BRAIN project’s primary objective is to pool the expertise of
scientists and engineers that includes improving the membrane
performance, to analyze the technical requirements for optimal
use during operation and also to define targets for the develop-
ment of the membrane system [56]. Consequently, it is believed
that the continuous cooperative research and development work
would lead to the clear identification of the optimal membrane
development approaches for the long-term applications in reduced
time operation.
The size of the membrane module unit for an oxyfuel power or
coal gasification plant should be as small as feasible for the techni-
cally and economically purposes [3]. A considerable attention has
to be directed to the required membrane surface area because the
membrane surface area increases with lowered differential oxy-
gen partial pressure, which is equivalent to the increase of oxygen
recovery rate and decrease of compressor outlet pressure. There are
several conceptual options available and these include monolithic
tubes [55], hollow fiber membranes [57], honeycomb structures
[58], and planar arrangements [59]. Schiestel et al. [57] suggested
hollow fiber membrane modules for their high packing density
and high flux features; at the same time, the engineering parame-
ters must be accounted for scaling up technology purpose because
they are relatively fragile and difficult to seal. The design of scale
up modules for oxygen separation where tubes were favored over
1292 S.S. Hashim et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1284–1293
the hollow fibers or flat plate multi-channel monoliths has been
demonstrated by Vente et al. [60]. The ion transport membrane
using a flat membrane with wafer configuration module operat-
ing at 800–900 ◦ C is well-developed by Air Products and Chemicals
[61]. Norsk Hydro is developing composite multi-channel heat
exchanger plus membrane modules in extruded ceramics oper-
ating at temperatures up to 1300 ◦ C while Praxair uses tubes at
800–900 ◦ C [7]. It is worth being noted that it is also difficult to
seal multi-channel monoliths, in particular when small channels
are employed to maximize the membrane surface area, while it is
less difficult for sealing single tube configurations. The use of glass
ceramic seals that consist of boro-silicate glass has been adopted
[62]; however, the seals must be well-designed for each application
and prone to be extremely brittle [3]. A comprehensive review on
the material choice, membrane and module design, seal develop-
ment and fabrication issues has been presented by den Exter et al.
[63] in their paper.
For the integration of high MIEC membrane into the oxyfuel
coal-fired combustion system, the improvement of the individual
efficiencies is emphasized towards improving the overall system
efficiency [31]. Stadler et al. [31] claimed that the increase of pres-
surized air temperature offers significant improvements of the
efficiency of the system. They reported that by heating the pres-
surized air to the conventional gas turbine inlet temperatures in
the order of 1500 K would increase the energy. The gas turbine
is already integrated in the oxyfuel system with MIEC membrane
module; therefore, the increase of temperature level seems to be
a wise option towards improving the overall system. The increase
of nitrogen turbine temperature can be made possible by heating
the nitrogen in the furnace or by employing an additional combus-
tion chamber. For the heating up of nitrogen in a furnace, a good
heat exchanger must be designed to minimize heat loss and lower
operating costs [3]. The investigations of operating heat exchang-
ers within a furnace are currently underway [64,65]; therefore, this
particular path is not applicable yet in the industry. Interestingly,
Stadler et al. [31] estimated that an overall oxycoal combustion
plant efficiency of 42.8% maybe achieved with the availability of
these heat exchangers. It is quite common to heat up the nitro-
gen in a separate combustion chamber in oxyfuel power cycles
incorporated with MIEC membrane air separation unit [48,66–68].
The minimum amount of oxygen, which is by decreasing the oxy-
gen separation degree in the membrane, has to be contained. In
addition to the increased mass flow through the membrane, the
compressor has to supply the cooling air flow for the turbine. The
downside of this second option is that the increase of the nitrogen
content of the combustion air would produce high NOx emissions;
furthermore, the exhaust gas of the turbine exhaust gas is no longer
CO2 free. Meanwhile, the research on heat exchangers capable of
heating pressurized air up to 1000 ◦ C is still underway, pursuing
application in externally fired combustion cycles [64].
6. Concluding remarks
Membrane technology offers significant advantages for the
production of oxygen from high temperature air separation by
reducing energy demands, capital and operating costs, plant foot-
prints and also improving plant efficiency; however, there is a large
gap to be filled for energy-related applications by MIEC ceramic-
based membranes. It can be concluded that full implementation
of ceramic membrane technology for the oxygen production from
air separation in power generation and fuel production cannot be
expected in the short term. There are still numbers of issues regard-
ing membrane materials and technology that need to be addressed
although some efforts have been taken to overcome the challenges
of implementing this novel oxygen production method. Further
research should be directed to the chemical and thermal stabil-
ity of the membrane, membrane geometries as well as sealing
technology. Moreover, there is a need from the pools of scien-
tific and engineering community to investigate the impact of high
temperature membrane operation to the overall efficiency and the
energy requirement for the technology could be employed for the
tonnage production of oxygen from air separation, replacing the
energy-intensive; conventional air separation technologies. There-
fore, it is expected that the oxygen separation from air by using
ceramic-based membrane technology will be implemented in the
near future for its promisingly potential for sustainable energy
delivery, fuel production and a cleaner environment.
Acknowledgements
The authors gratefully acknowledge financial support by the
Ministry of Science, Technology and Innovation, Malaysia (E-
Science grant) as well as by the Universiti Sains Malaysia (Research
University grant).
References
[1] Burggraaf HJM, Bouwmeester AJ. In: Buggraaf HJM, Cot L, editors. Fundamentals
of inorganic membrane science and technology. Chapter 10. Elseiver; 1996.
[2] Ermsley J. Oxygen. In: Nature’s building blocks: an A–Z guide to the elements.
Oxford, England (UK): Oxford University Press; 2001.
[3] Leo A, Liu SM, Diniz da Costa JC. Development of mixed conducting membranes
for clean coal energy delivery. International Journal of Greenhouse Gas Control
2009;3:357–67.
[4] Smith AR, Klosek J. A review of air separation technologies and their
integration with energy conversion processes. Fuel Processing Technology
2001;70:115–34.
[5] Cengel Y, Boles M. Thermodynamics: an engineering approach. 5th ed. New
York: McGraw-Hill; 2006.
[6] Burdyny T, Struchtrup H. Hybrid membrane/crogenic separation of oxygen
from air for use in the oxy-fuel process. Energy 2010;35:1884–97.
[7] Allam RJ. Improved oxygen production technologies. Energy Procedia
2009;1:461–70.
[8] Zahra M, Jafar T, Masoud M. Study of a four-bed pressure swing adsorption
for oxygen separation from air. World Academy of Science, Engineering and
Technology 2008;47:99–103.
[9] Masoud M, Mojtaba S, Jafar T. Four-bed vacuum pressure swing adsorption
process for propylene/propane separation. Industrial & Engineering Chemistry
Research 2005;44:1557–64.
[10] Yoshida S, Ogawa N, Kamioka K, Hirano S, Mori T. Study of zeolite molecular
sieves for production of oxygen by using pressure swing adsorption, vol. 5.
Kluwer Academic Publisher; 1999. p. 57–61.
[11] Santos JC, Cruz P, Regala T, Magalhaes FD, Mendes A. High-purity oxygen pro-
duction by pressure swing adsorption. Industrial & Engineering Chemistry
Research 2007;46:591–9.
[12] Acharya D, Krishnamurthy KR, Leison M, MacAdam S, Sethi VK, Anheden M,
Jordal K, Yan J. Development of a high temperature oxygen generation pro-
cess and its application to oxycombustion power plants with carbon dioxide
capture. In: Proceedings of the 22nd annual international Pittsburgh coal con-
ference. 2005.
[13] Liu S, Gavalas GR. Oxygen selective ceramic hollow fiber membranes. Journal
of Membrane Science 2005;246:103–8.
[14] Kakaras E, Doukelis A, Giannakopoulus D, Koumanakos A. Economic implica-
tions of oxyfuel application in a lignite-fired power plant. Fuel 2007;86:2151–8.
[15] Kakaras E, Koumanakos A, Doukelis A, Giannakopoulos D, Vorrias I. Oxyfuel
boiler design in a lignite-fired power plant. Fuel 2007;86:2144–50.
[16] IPCC. Special report on carbon dioxide capture and storage. Chapter 3. New
York: Cambridge University Press; 2005.
[17] Flett M, Gurton R, Weir G. Hetereogeneous saline formations for carbon dioxide
disposal: impact of varying heterogeity on containment and trapping. Journal
of Petroleum Science and Engineering 2007;57(1-2):106–18.
[18] Bhacu S. Sequestration of CO2 in geological media: criteria and approach for site
selection in response to climate change. Energy Conversion and Management
2000;41:9.
[19] Darde A, Prabhakar R, Tranier JP, Perrin N. Air separation and flue gas compres-
sion and purification units for oxy-coal combuation systems. Energy Procedia
2009;1:527–34.
[20] Pipitone G, Bolland O. Power generation with CO2 capture: technology for CO2
purification. International Journal of Greenhouse Gas Control 2009;3:528–34.
[21] Ekstrom C, Schwendig F, Biede O, Franci F, Haupt G, de Koeijer G, Papapavlou C,
Rokke PE. Techno-economic evaluation and benchmarking of precombustion
CO2 capture and oxyfuel processes developed in the European ENCAP project
2009. Energy Procedia 2009;1:4223–40.
 S.S. Hashim et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1284–1293
[22] Seltzer A, Fan Z, Hack H. Oxyfuel coal combustion power plant system opti-
mization. Foster Wheeler North America Corporation R&D; 2007. p. 1–17.
[23] Hong J, Chaudry G, Brisson JG, Field R, Gazzino M, Ghoniem AF. Analysis of oxy-
fuel combustion power cycle utilizing a pressurized coal combustor. Energy
2009;34:1332–40.
[24] Davidson J. Performance and costs of power plants with capture and storage of
CO2 . Energy 2007;32:1163–76.
[25] Kneer R, Toporov D, Fcorster M, Christ D, Broeckmann C, Pfaff E, Zwick M,
Engels S, Modigell M. OXYCOAL-AC: towards an integrated coal-fired power
plant process with ion transport membrane-based oxygen supply. Energy and
Environmental Science 2010;3:198–207.
[26] Sundkvist SG, Julsrud S, Vigeland B, Naas T, Budd M, Leistner H, Winkler D.
Development and testing of AZEP reactor components. International Journal of
Greenhouse Gas Control 2007;1:180–7.
[27] Wilson J, Christie M, Degenstein N, Shah M, Li J, Venkateswaran V, Eddings E,
Adams J. OTM based oxycombustion for CO2 capture from coal power plants.
In: Proceedings of the 34th international technical conference on clean coal &
fuel systems. 2009.
[28] Air Products and Chemical Inc. Ion transport membrane module and vessel
system with directed internal gas flow. Patent EP1676811A2; 2006.
[29] den Exter MJ, Haije WG, Vente JF. Viability of ITM technology for oxygen pro-
duction and oxidation processes: material, system, and process aspects. In:
Inorganic membranes for energy and environmental applications. Chapter 2.
Springer; 2009. p. 27–51.
[30] Beggel F, Engels S, Modigell M, Nauels N. Oxyfuel combustion by means of
high temperature membranes for air separation. In: Proceedings of the fourth
international conference on clean coal technologies CCT2009 held in Dresden,
Germany. 2009.
[31] Stadler H, et al. Oxyfuel coal combustion by efficient integration of oxygen
transport membranes. International Journal of Greenhouse Gas Control 2010,
doi:10.1016/j.ijggc.2010.03.004.
[32] Christou C, Hadjipaschalis I, Poullikkas A. Assesment of integrated gasifica-
tion combined cycle technology competitiveness. Renewable and Sustainable
Energy Reviews 2007;12:2459–71.
[33] Ordorica-Garcia G, Douglas P, Croiset E, Zheng L. Techno-economic evaluation
of IGCC power plants with CO2 capture. Greenhouse Gas Control Technologies
2005;7:1193–8.
[34] Bohm MC, Herzog HJ, Parsons JE, Sekar RC. Capture-ready coal plants-options,
technologies and economics. International Journal of Greenhouse Gas Control
2007;3:113–20.
[35] Wang J, Anthony EJ. Clean combustion of solid fuels. Applied Energy 2008;85(2-
3):73–9.
[36] Zheng Y, Wang B, Song K, Zheng C. Performance research on a new oxygen-
carrier CaSO4 used in chemical-looping. Journal of Engineering Thermophysics
2006;27(531):3.
[37] Abad A, Mattison T, Lyngfelt A, Ryde’n M. Chemical-looping combustion in
a 300 MW continuously-operating reactor system using a manganese-based
oxygen carrier. Fuel 2006;85(85):1174.
[38] Mattison T, Johansson M, Lyngfelt A. The use of NiO as an oxygen carrier in
chemical-looping combustion. Fuel 2006;85(47):736.
[39] Abad A, Ada’nez J, Garci’a-Labiano F, Diego LFD, Gaya’n P, Celaya J. Mapping of
the range of operational conditions for Cu-, Fe-, and Ni-based oxygen carrier
in a chemical-looping combustion. Chemical Engineering Science 2007;62(1-
2):533–49.
[40] Abad A, Mattison T, Lyngfelt A, Johansson M. The use of iron oxide as the oxygen
carrier in a chemical-looping reactor. Fuel 2007;86(35):1021.
[41] Weil KS, Hardy JS, Rice JP, Kim JY. Brazing as means of sealing ceramic mem-
branes for use in advanced coal gasification processes. In: Proceedings of the
2st annual international Pittburgh coal conference held in Pittsburgh, PA, USA,
85(2). 2006. p. 156–62.
[42] Keshav TR, Basu S. Gas-to-liquid technologies: India’s perspective. Fuel Pro-
cessing Technology 2007;88:493–500.
[43] Robinson ET. Oxygen transport membrane for ultra-clean fuel production. Fuel
Chemistry Division Reprints 2003;48(1):347–9.
[44] Griffin T, Sundkvist SG, Asen KI, Bruun T. Advanced zero emissions gas turbine
power plant. In: Proceedings of ASME TurboExpo held in Atlanta, GA, USA. 2003.
[45] Sundkvist SG, et al. AZEP gas turbine combined cycle power plants-thermal
optimization and LCA analysis. GHGT-7 Elsevier; 2004.
1293
[46] Griffin T, Bill A, Marion JL, Nsakala NY.Proceedings of GHGT-6 held in Kyoto,
Japan, vol. 1. 2003. p. 81–6.
[47] Moller BF, Torisson T, Assadi M, Sundkvist SG, Sjodin M, Klang A, Asen KI, Wil-
helmsen K. AZEP gas turbine combined cycle power plants-thermo-economic
analysis. International Journal of Thermodynamics 2006;9(1):2–28.
[48] Bredesen R, Jordal K, Bolland O. High-temperature membranes in power
generation with CO2 capture. Chemical Engineering and Processing
2004;43:1129–58.
[49] Yantovski E, Gorski J, Smyth B, ten Elshof JE. ZEITMOP cycle (Zero Emission Ion
Transport Membrane Power). In: Proceedings of the Int. Conf. ECOS 200 held
in Berlin, vol. 2. 2002. p. 1153–60.
[50] Foy K, McGovern J. Analysis of the effects of combining air separation with
combustion in a zero emissions (ZEITMOP) cycle. Energy Conversion and Man-
agement 2007;48:3046–52.
[51] Gorski J, Yantovski E. ZEITMOP conceot—a polygeneration system for municipal
energy demands. Indoor and Built Environment 2009;18:454–60.
[52] Eckl et al. Public summary report of ENCAP deliverable D5.3.11: developments
of the high temperature oxygen generation technology outside ENCAP in EU
and USA [online]. Available from Internet: www.encapco2.org.
[53] Renz U, Kneer R, Abel D, Niehuis R, Maier H, Modigell M, Peters N. Entwicklung
eines CO2 -emissionsfreien Kohleverbrennungsprocesses zur Stromerzeugung.
In: CCS-Tagung Juelich held in RWTH, Aachen. 2005.
[54] Smart S, Lin CXC, Ding L, Thambimuthu K, da Costa JCD. Ceramic mem-
branes for gas processing in coal gasification. Energy & Environmental Science
2010;3:268–78.
[55] Pfaff EM, Zwick M. Oxyfuel combustion using perovskite membranes. In:
Mechanical properties and performance of engineering ceramics and compos-
ites III. Ceramic engineering and science proceedings, 28(2). 2007. p. 23–31.
[56] Czyperek M, Zapp P, Bouwmeester HJM, Modigell M, Ebert K, Voigt I,
Meulenberg WA, Singheiser L, St’over D. Gas separation membranes for zero-
emission fossil power plants: MEM-BRAIN. Journal of Membrane Science 2008,
doi:10.1016/j.memsci.2010.04.012.
[57] Schiestel T, Kilgus M, Peter S, Caspary KJ, Wang H, Caro J. Hollow fibre
perovskite membranes for oxygen separation. Journal of Membrane Science
2005;258:1–4.
[58] Bruun T, Werswick B. Method and equipment for distribution of two fluids into
and out of the channels in a multi-channel monolithic structire and use thereof.
EP 1 627 198 B1 February 21; 2007.
[59] Armstrong P, Underwood R, Stein V, Foster T. ITM oxygen for the real world:
pilot scale testing and beyond. In: International Pittsburgh coal conference held
in Pittsburgh, PA, USA. 2008.
[60] Vente JF, Haije WG, IJpelaan R, Rusting FT. On the full-scale module design
of an air separation unit using mixed ionic electronic conducting membranes.
Journal of Membrane Science 2006;278(1–2):66–71.
[61] Stiegel GJ, Bose A, Armstrong P. Development of ion transport membrane (ITM)
oxygen technology for integration in IGCC and other advanced power genera-
tion systems. Project Facts U D o Energy 2006.
[62] Thursfield A, Metcalfe IS. Air separation using a catalytically modified mixed
conducting ceramic hollow fiber membrane module. Journal of Membrane Sci-
ence 2007;288(1-2):175–87.
[63] den Exter M, Vente JF, Jansen D, Haije WG. Viability of mixed conducting mem-
branes for oxygen production and oxyfuel processes in power production.
Energy Procedia 2009;1:455–9.
[64] Aquaro D, Pieve M. High temperature heat exchangers for power plants:
performance of advanced metallic recuperators. Applied Thermodynamic Engi-
neering 2007;27:389–400.
[65] Kumada M, Hanamura K. Research and development on the high perfor-
mance ceramic heat exchangers. International Journal of Heat Exchange
2003;4:201–18.
[66] Vratsanos LA, Armstrong PA, Underwood RP, Stein VE, Foster E. ITM oxygen for
the real world: pilot scale testing and beyond. In: International Pittsburgh coal
conference held in Pittsburgh, PA, USA. 2008.
[67] Griffin T, Sundkvist SG, Asen K, Bruun T. Advanced zero emissions gas
turbine power plant. Journal of Engineering for Gas Turbines and Power
2005;127:81–5.
[68] Dyer PN, Richards RE, Russek SL, Taylor DM. Ion transport membrane tech-
nology for oxygen separation and syngas production. Solid State Ionics
2000;134:21–33.