Transactions of the Indian Ceramic Society

ISSN: 0371-750X (Print) 2165-5456 (Online) Journal homepage: http://www.tandfonline.com/loi/tcer20

Ceramic Membranes for the Separation of Carbon

Dioxide—A Review

Biruh Shimekit, Hilimi Mukhtar, Farooq Ahmad & Saikat Maitra

To cite this article: Biruh Shimekit, Hilimi Mukhtar, Farooq Ahmad & Saikat Maitra (2009)
Ceramic Membranes for the Separation of Carbon Dioxide—A Review, Transactions of the
Indian Ceramic Society, 68:3, 115-138, DOI: 10.1080/0371750X.2009.11082166

To link to this article: http://dx.doi.org/10.1080/0371750X.2009.11082166

Published online: 19 Jan 2015.

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 Topical Reviews
Trans. Ind. Ceram. Soc., 68 (3) 115-138 (2009).
© 2009 The Indian Ceramic Society

Ceramic Membranes for the

Separation of Carbon Dioxide – A Review
Biruh Shimekit, Hilimi Mukhtar, Farooq Ahmad and Saikat Maitra*

Department of Chemical Engineering

Universiti Technologi PETRONAS
Tronoh – 31750, Malaysia
[MS received July 20, 2009; revised copy received September 14, 2009]

The separation and sequestration of CO2 produced from the combustion of fossil fuels is the need of the
day to encounter ‘Greenhouse Effect’ and ‘Global Warming’. Again, it is quite important also for improving
the calorific value of natural gas and for reutilization of flue gas. Membrane technology has the potential
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to play a crucial role in this regard. Compared to other traditional techniques for the separation and
sequestering of CO2, membrane technology, particularly ceramic membrane, is still in relatively developing
stage. But it has tremendous potential to emerge as a successful technology to meet the requirement in
future. This article reviews previous works and recent achievements by different researchers on various
CO 2 selective ceramic membranes with reference to other type of membranes, like polymeric, hybrid
and mixed matrix type. It also discusses various gas transport mechanism in membranes, different
features of ceramic membranes, parameters that affect the gas separation in ceramic membranes, new
generation ceramic and other types of membranes, industrial applications of membrane based gas
separation process and future direction in membrane research.
[Keywords : Ceramic membranes, Polymeric membranes, Hybrid membranes,
Carbon dioxide separation, M ixed matrix membranes]

Introduction surface and physical separation like membrane

The environmental concern due to the ‘much talked’
green house gases emitted from the combustion of fossil
fuels has prompted a worldwide interest in suitable
technologies for the economical separation and
sequestration of CO2. Much natural gas well processing
include liquefaction processes, which operate at a very
low temperature and pressure to freeze out CO 2 on
exchanger surface causing plugging of lines and
consequent reduction in plant efficiency. It shows that
CO2 needs to be removed before liquefaction process.
This is done not only to overcome the process difficulties
but also to meet the liquefied natural gas (LNG) product
specifications. CO2 reduces the energy content of the gas,
accelerates corrosion of process equipment due to its
acidic nature when present in water.
The preferable abatement options for the CO2 emissions
from fossil fuel utilization include increasing the efficiency
of fossil fuel combustion systems or substituting fossil
fuels with renewable energy sources. These alternatives
are found to be very attractive in controlling CO2 emissions
in the environment, but each has its own limitation.
Another option for managing CO2 emissions is carbon
sequestration, i.e. capturing and securely storing the CO2
emitted from large point sources such as fossil-fuel-fired
power plants. Carbon dioxide separation and capture may
be achieved by acid gas treating processes. 1 These
processes include absorption in different solvents,
adsorption on hybrid solution, adsorption process on solid
*Corresponding author; e-mail : drsaikat_maitra@petronas.com.my
separation, cryogenic separation, etc.2 Different types of
solvents have been used extensively in existing base load
LNG facilities.3 The details describing the integrated
processes are presented at the end of this article entitled
hybrid systems.
Membrane separation is the most modern and efficient
separation for different gases. There are several gas
transport mechanisms in membrane, e.g. molecular
diffusion, Knudsen diffusion, surface diffusion, etc. The
transport of a particular gas through a particular
membrane sometimes follows a specific mechanism and
sometimes a combination of different mechanisms.
Traditional polymeric membranes with high
permselectivities have significantly low fluxes. Moreover,
at high CO 2 pressure these membranes become
plasticized. Therefore, these types of membranes have
restricted uses for CO2 separation.
Ceramic membrane systems are an attractive option
and commercially proven technology for natural gas treating
application because they offer potential advantages for
operations at relatively higher temperatures encountered
in the power plants. Moreover, membranes are being used
more frequently in gas field operations in removing carbon
dioxide and water vapour to meet pipeline and LNG
specification. Lin et al.4 indicated that improved ceramic
membranes for the separation of CO2 from CH4 would reduce
the costs of natural gas purification. Membranes made from
microporous glasses, ceramics like Al2O3, Si3N4, SiC and
metal oxides can be used in severe operating conditions
requiring high abrasion, chemical and thermal resistance.

VOL. 68 (3) JULY – SEPTEMBER 2009 115

 Current efforts to develop CO2 selective membranes
focus on a number of approaches including development
of suitable polymeric membranes, hybrid membranes and
porous inorganic membranes which follows a permeation
mechanism. Stern5 provided a detailed review about
polymeric membrane for gas separation. Shekhawat
et al. 6 reviewed the performances of CO 2 selective
membrane. Koros et al.7 and Pandey and Chauhan8 also
reviewed the performance of membrane-based gas
separation. Hollow fiber ceramic membranes can be
fabricated by a number of ways, like dry spinning, wet
spinning, gas phase deposition, pyrolysis of polymers,
etc. Both microporous and dense ceramic membranes
can be fabricated and used as hollow fiber membrane.
Microporous inorganic membranes mostly comprise of
silica, carbon or zeolites. Alumina membranes are of
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limited use in the separation of gases. Due to presence
of cavities of molecular dimensions zeolites are very much
effective for a wide range of separation. Due to their high
chemical and thermal stabilities carbon molecular sieves
have strong potential for use in the separation of CO 2
from flue gases. Silica membranes also show high thermal,
chemical and structural stability in both oxidizing and
reducing atmosphere and can be used effectively for
CO2 separation. These articles highlighted the research
activities prior to the year 2003. The present article
reviews recent developments in the area of CO2 selective
ceramic membrane and also indicated further direction
of research in this area.
Gas Transport Mechanisms in Membranes
Gas separation in membranes takes place due to the
differences in permeabilities of the species flowing through
the membrane. With a few exceptions, membranes used
for gas separation can be broadly categorized into two
major categories: ceramic and polymeric.9
Gas transport through porous membranes takes
place through a number of mechanisms, like molecular
sieving, Knudsen diffusion, surface diffusion, capillary
condensation and micropore diffusion. A brief description
of these mechanisms as given by Javaid,9 is indicated
below :
Molecular Diffusion
In molecular diffusion, the mean free path of the gas
molecules is smaller than the pore size and diffusion
occurs primarily through molecule-molecule collisions
where the driving force is the composition gradient. If a
pressure gradient is applied in such pore regimes bulk
(laminar) flow occurs as following Poiseuille’s equation.
Such transport is often referred to as Poiseuille flow or
viscous flow.
Knudsen Diffusion
This mode of transport is important when the mean
free path of the gas molecules is greater than the pore
size. In such situations, the collisions of the molecules
with the pore wall are more frequent than the collisions
among molecules. Separation selectivities with this
116
mechanism are proportional to the ratio of the inverse
square root of the molecular weights. This mechanism
is often predominant in macroporous and mesoporous
membranes.
Surface Diffusion
Surface diffusion takes place when the permeating
species exhibit strong affinity for the membrane surface
and get adsorbed along the pore walls. In this mechanism,
separation occurs due to the differences in the amount
of adsorption of the permeating species. Surface diffusion
is predominantly low temperature and high pressure
process and it often occurs in parallel with other transport
mechanisms such as Knudsen diffusion.
Capillary Condensation
Capillary condensation is one form of surface flow
where one of the gases is a condensable gas. Typically
in mesopores and small macropores, at certain critical
relative pressures as determined by the Kelvin equation,
the pore gets completely filled by the condensed gas.
Due to the formation of menisci at both ends of the pore,
transport can take place through hydrodynamic flow
generated by capillary pressure difference between the
two ends. This mechanism of gas transport can be
considered as the limiting case adsorption process when
the pressure is increased. Theoretically, capillary
condensation can be used to achieve very high
selectivities as the formation of the liquid layer of the
condensable gas will block and prevent the flow of the
non-condensable gas.
Configurational or Micropore Diffusion
This type of diffusion may be considered as the
limiting value of surface diffusion where the pore size
becomes comparable to the molecular size. In this
mechanism, diffusion is perceived as an “activated”
process and separation is a strong function of molecular
shape, molecular size, pore size and interactions
between the pore wall and gas molecules. This type of
mechanism is dominant in microporous zeolite
membranes and carbon molecular sieves.
From the described mechanisms, it is worth reminding
that gas transport through porous membranes across
different pore size regimes can follow either of the stated
mechanisms individually or coupled with others depending
on pore size distribution, porosity, nature, concentration
of adsorbed species, differences in molecular mass of
the gas species and the affinity between permeating
species and the pore walls of the membrane material.
Polymeric Membranes
Glassy membranes and rubbery membranes are the
two types of polymeric membranes that are used widely
for gas separation applications.
Glassy membranes are rigid and glass-like, and
operate below their glass transition temperatures. On
the other hand, rubbery membranes are flexible and soft,
and operate above their glass transition temperatures.
TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
 Mostly, rubbery polymers show a high permeability but 120
a low selectivity whereas glassy polymers exhibit a low
permeability but a high selectivity. Glassy polymeric 100

CO2/N2 SELECTIVITY
membranes dominate industrial membrane separations
80
because of their high gas selectivity along with good
mechanical properties.
60
Gas transport in polymeric membranes is affected
by several polymer properties, such as morphology, 40
free volume content, intersegmental chain spacing,
orientation, cross-linking, polymer polarity, defects, 20
thermal processing history, glass transition temperature,
average molecular weight, molecular weight distribution, 0
composition, degree of crystallization, types of 1.00E-01 1.00E+00 1.00E+01 1.00E+02 1.00E+03 1.00E+04
crystallites, etc. The presence of crystalline domains in CO2 PERMEABILITY (BARRER)
a polymer adds a tortuosity factor to gas diffusion and,
thus, makes gas transport more complicated. In dense Fig. 1 – CO 2/N 2 selectiv ity versus CO 2 permeability for
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polymeric materials, solution-diffusion is widely accepted polymeric membranes 5, 9, 11

to be the main mechanism of transport. This mechanism
is generally considered to be a three-step process. 100
In the first step the gas molecules are absorbed by
the membrane surface on the upstream end. This is 80

followed by the diffusion of the gas molecules through
the polymer matrix. In the final step the gas molecules
evaporate on the downstream end. In glassy polymers,
the sorption of gases becomes a complex process, which
has been described by a combination of Henry’s law
and Langmuir expressions. This has been referred to as
“dual mode sorption theory”. Diffusion in glassy polymers
is usually an activated process and Arrhenius relations
may be used to express the permeability, diffusivity and
solubility coefficients.9, 10
Most polymer membranes with high permselectivity
have significantly low fluxes. This is illustrated in Figs. 1
and 2, which show an upper bound in the relationships
between CO2/N2 and CO2/CH 4 selectivities respectively,
and the permeability of CO 2 for various glassy and
rubbery polymers. It indicates that although the polymer
is efficient at separating molecules, diffusion through
the membrane is slow, resulting in little economic
benefit. For diffusivity-based separations, polymers
exhibit “inverse permeability / selectivity” behaviour.
In other words, membrane selectivity for different gas
pairs increases as the gas permeability through it
decreases.5 Robeson11 further investigated this inverse
relationship and suggested that there exists a hypo-
thetical “upper bound” in the relationship between
permeability and selectivity.
A significant part of the present research have
been focusing on pushing the polymer performance
above the upper bound as described in Figs. 1 and 2 and
into the economically attractive region currently enjoyed
by inorganic membranes.9 However, the problem with
polymeric membranes is that high CO2 pressure plasti-
cizes them and decreases their separation ability of
CO2/CH4. To overcome this, inorganic membranes have
been used to separate CO2 from CH4 because of their
superior thermal, chemical and mechanical stability at
high pressures of CO2.
CO2/CH4 SELECTIVITY
60
40
20
0
1.00E+03
1.00E-01 1.00E+00 1.00E+01 1.00E+02
CO2 PERMEABILITY (BARRER)
Fig. 2 – CO 2/CH 4 selectivity versus CO 2 permeability for
polymeric membranes 5, 9, 11
Ceramic Membranes
Porous ceramic membranes have intrinsic thermal
stability and potential for high permeance. There has been
a growing interest in the use of inorganic membrane for
several industrial and laboratory applications. This is
because they offer many advantages over their organic
counterparts in separation processes. These include
resistance to compaction under high pressure, chemical
stability at high temperature (including steam sterilization
procedures), insensitivity to bacterial action and a long
operational life.12
An important consideration in designing gas
separation membranes is the thickness of the membrane
itself, since the permeation rate is maximized when the
thickness is minimized. Additionally, during its
performance, the membrane must withstand the pressure
drop along with the impacts from aggressive reagents
and high temperatures.
Ceramic Hollow Fiber Membrane
A useful membrane process requires the development
of a membrane module containing large surface areas of
membrane. The earliest designs were based on simple

VOL. 68 (3) JULY – SEPTEMBER 2009 117

 filtration technology and consisted of flat sheets of
membrane held in a type of filter press. These are called
plate and frame modules. Systems containing a number
of membrane tubes were developed at about the same
time. Both of these systems are still used, but because
of their relatively high cost they have been largely
displaced by two other designs, the spiral-wound and
hollow-fiber module.13
Inorganic membranes prepared from microporous
glasses, ceramic materials such as aluminium oxide
(Al2O3), silicon nitride (Si3N4), silicon carbide (SiC),14 metal
oxide or metal alloys have relatively high resistance to
abrasion and to chemical and thermal degradation, and
thus most appropriate for use in severe operating
conditions such as corrosive environments and high
temperatures. In contrast, various polymeric hollow fiber
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membranes have been prepared and been used widely
due to their high surface area per unit volume and high
permselectivity. However, the organic materials are only
limited to mild operating conditions because of their weak
thermal stability and ease of fouling. The inorganic
membranes are not only used directly as in micro-
filtration, ultrafiltration, and gas separation at high
temperatures, but also serve as porous supports for dense
membrane formation.15
Microporous Vycor glass, alumina, and some metals
are the well-known materials for inorganic membrane
production, and numerous studies have been reported
for fluid separation or separation/reaction using these
inorganic membranes.16–19 Studies on inorganic mem-
branes, especially inorganic hollow fiber membranes,
prepared from other materials are relatively scarce partly
because their production processes are complicated
and are too expensive.
There are many different methods used for preparing
inorganic hollow fibers including dry spinning a system
of inorganic material and binder,14 wet spinning a suitable
inorganic material containing solution and/or sols, 20
depositing fibers from the gas phase onto a substrate, or
pyrolyzing the polymers.21–23
Currently, ceramic membranes can only be developed
through multiple steps. A support layer is first prepared
to provide the membranes with mechanical strength,
followed by coating one or more intermediate layers on
the support layer before a final separation layer can be
fabricated. Each step involves a high temperature heat
treatment, making the ceramic membrane fabrication
extremely expensive. Clearly, combining the multiple
steps into a single step is desirable in cutting production
time and costs, and hence membrane price. In addition,
the membrane or membrane system price could be further
reduced if the membrane can be prepared in hollow fiber
geometry as it provides the largest membrane area per
unit volume ratio.24
Very little information is available regarding the
preparation of asymmetric / composite ceramic hollow
fiber membranes. Jong et al.25 attempted to use a triple
orifice spinneret to spin two particle suspensions containing
different sized Al2O3 particles at the same time, aiming at
118
achieving a single step production process of asymmetric
ceramic hollow fiber membranes. Li et al.26 believed that a
single step production of asymmetric ceramic hollow fiber
membranes could be simplified using a conventional tube-
in-orifice spinneret as long as particles dispersed in the
suspension showed distributed particle sizes. They
successfully demonstrated the production of a dense (non-
porous) ceramic hollow fiber membrane using an
immersion induced phase inversion technique equipped
with only a conventional tube-in-orifice spinneret.26
The fabrication of asymmetric ceramic hollow fiber
membranes in one step using an immersion induced
phase inversion technique was further elaborated by
Wei et al.27 The membranes prepared using this technique
showed either non-porous (dense) or porous (ultrafiltration
type) characteristics depending on the compositions of
starting suspensions, fiber spinning parameters and final
sintering conditions employed. Wei et al.27 selected yttria
stabilized zirconia (YSZ) as the membrane material as it
was relatively inexpensive and had superior mechanical
strength as well as oxygen ion conducting properties.
Therefore, their membranes prepared from YSZ were
robust with either a porous or non-porous structure. They
reported that the porous membranes could be used in
fluid separations in harshest of environments whereas
normal polymeric membranes were unsustainable.
Furthermore, it was reported that the non-porous membranes
could be used as a solid electrolyte in electrochemical
devices, for example, in solid oxide fuel cells, oxygen
pumps and chemical gas sensors.28–30
For high-temperature gas separation applications
two types of ceramic membranes are suitable: microporous
and dense membranes. The schematic diagrams of major
types of gas separation inorganic membranes based on
their structure are shown in Fig. 3.31
SYMMETRICAL MEMBRANES
ISOTROPIC NONPOROUS DENSE ELECTRICALLY CHARGED
MICROPOROUS MEMBRANE MEMBRANE
MEMBRANE
POLYMER
ANISOTROPIC MEMBRANES MATRIX
LIQUID
FILLED
PORES
LOEB-SOURIRAJAN THIN-FILM COMPOSITE
ANISOTROPIC ANISOTROPIC
MEMBRANE MEMBRANE SUPPORTED LIQUID
MEMBRANE
Fig. 3 – The schematic diagrams of gas separation inorganic
membranes based on their structure 31
TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
 Microporous Inorganic Membranes
These membranes, with pore sizes smaller than 2
nm, are composed either of amorphous silica, carbon or
zeolites. A microporous ceramic membrane system
generally consists of a macroporous ceramic support,
some ceramic intermediate layers and eventually a highly
selective top layer. The support provides mechanical
strength to the system. The intermediate layers bridge
the gap between the large pores of the support and the
small pores of the top layer. The top layer has the
separating capacities. Membrane properties such as
permeation and selectivity depend on the properties of
the membrane/support composites such as pore size
distribution, porosity and the affinity between permeating
species and the pore walls. Separation of a gas mixture
can take place based on the differences in molecular
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mass, size or shape, or on the differences in the affinity
of the gas molecules to the membrane material. An
increase in selectivity is generally achieved at the cost
of a decrease in membrane permeation. It happens due
to a decrease in not only the pore size but also in the
overall porosity of the membrane. The best answer to
permeation/selectivity optimization would be to
synthesize very thin layers of materials with high porosity
and with pore sizes in the range of 0.3-0.8 nm so as to
achieve molecular sieving effects.32 These membranes
are prepared as unsupported ones as well as thin films
on porous supports. They are made of polycrystalline
ceramic material, in particular, perovskites or metal
(palladium), which allow specific gas species to permeate
the dense material. Depending on the nature of the dense
membrane material, hydrogen selectively permeates in
atomic (Pd alloys), molecular (dense SiO 2) or protonic
(proton-conductive solid electrolytes) form. Both hydrogen
and oxygen can permeate selectively through various
types of dense membranes. Dense membranes are
impermeable to all gases except for a very limited number
of gases that can permeate the material (i.e. H2 through
Pd) or can be incorporated into the structure of the
membrane and transported through the material (i.e. O2
through perovskites).32
In this section, the state of the art and developments
in different microporous ceramic membranes (alumina,
zeolite, carbon, silica) for gas separation have been
discussed.
Alumina Membranes
Generally, mesoporous structure of alumina dictates
that transport within these membranes will take place
by a Knudsen diffusion mechanism.33 As selectivity in
this regime is limited, and the rate of diffusion is controlled
by molecular weight, alumina membranes are of limited
use in the separation of gases. With mixtures such as
CO 2 /N 2, where the gases have similar mass, and
CO2/H2, where selectivity towards the heavier component
is required, alumina is considered as less applicable
as a membrane material. However, alumina finds its
use in the separation of gases mainly as a support,
where its sound structural properties and chemical and
VOL. 68 (3) JULY – SEPTEMBER 2009
hydrothermal stabilities beyond 1000 oC make it very
desirable. A few attempts have been made to modify
alumina membranes to facilitate CO2 surface diffusion
with limited success. A typical SEM picture of alumina
membrane is shown in Fig. 4.34 In order to achieve high
separation factors in systems like CO 2 and N 2 an
interaction between one of the gases in the mixture and
the membrane surface can be introduced by chemical
modification of separation layers. Some of the important
works in this regard are given below.
Uhlhorn et al.35 reported the modification of -alumina
membrane systems by impregnating magnesia to induce
surface diffusion of CO2. The magnesia introduced into
-alumina creates stronger basic sites which result in
stronger bonding of CO2 to the modified surface and
results in the adsorption of CO 2 on the surface to be
partially irreversible. They concluded that more strongly
bonded CO2 was less mobile, resulting in lower CO 2
permeability across the membrane. Cho et al.36 reported
the separation of CO2 by modified -Al2O3 membranes at
high temperature by sol-gel coating with boehmite
(AlOOH) sol. CaO was impregnated on the -A1 2O 3
membrane to improve separation factor by introducing
interactions between CO2 gas molecules and the pore
wall. Silica-modified -alumina was also prepared to
increase the CO 2/N 2 separation factor. The authors
reported that the CO2/N2 separation factor was not different
from the Knudsen surface diffusion mechanism. The
CO2/N2 separation factor was 1.72 at 298 K and 1.5 at
673 K which were much higher than that of the Knudsen
diffusion mechanism (0.8) and decreased with increasing
temperature. They concluded that the main mechanism
of gas transport through -A12O3 membrane followed
Knudsen diffusion mechanism. Surface diffusion could
be applied as a separation mechanism when the pore
size is very small and the temperature is low. However,
high separation factors could not be obtained at high
temperatures. Kang et al. 37 reported modification of
-Al2O3 composite membranes with microporous silica
layers to improve the separation factor of CO 2 to N 2
by dip coating and pressurized coating, and CO 2/N 2
Fig. 4 – FESEM picture of a  -Al 2O 3 membrane surface
(G900 membrane) 34
119
 separation factors of 2.4 and 1.45 by dip coating and
pressurized coating respectively were achieved by the
workers with the following conditions,P = 0.3 MPa, stage
cut = 0.1 at 25oC for a CO2 feed gas mole fraction of 0.5.
Zeolite Membranes
Zeolites are crystalline aluminosilicates with a uniform
pore structure and a small channel diameter ranging from
0.3 to 1.0 nm. The presence of molecular sized cavities
and pores make the zeolites effective as shape-selective
materials for a wide range of separation applications. These
cavities are interconnected by pore openings through
which molecules can pass. The electrical charge or
polarity of the zeolites also attract or sort molecules. This
ability to selectively adsorb molecules by size and polarity
is the key to the unusual efficiency of synthetic zeolites
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as the basis for separation. By tailoring the chemistry
and structure of the materials used to prepare them,
synthetic zeolites can be modified to provide a wide range
of desired adsorption characteristics or selectivities and
can be used as a membrane for gas separation
applications. Zeolite membranes are usually prepared by
in situ hydrothermal synthesis on porous stainless steel,
-alumina or -alumina support tubes or disks for the
gas permeation studies. These supported zeolite
membranes have a thin and continuous zeolite separation
layer with the porous support to provide mechanical
strength to the membrane. Membranes of various zeolites,
such as ZSM-5,38 Y-type,39 silicalite,40 A-type,41 P-type,42
modernite43 and silicoaluminophosphate44 have been
synthesized on porous supports. Separation takes place
in zeolite membranes by both molecular sieving and
surface diffusion methods because the pore sizes of
zeolite membranes are of molecular dimensions. In zeolite
membranes, both molecular sizes relative to the zeolite
pore and the relative adsorption strengths determine the
faster permeating species in a binary mixture. A typical
SEM picture of zeolite membrane is shown in Fig. 5.45
Poshusta et al.44 identified three separation regimes
where both components are able to diffuse through the
zeolite pores. The first regime covers differences in
diffusivity, where there is a difference in the size of
molecules, but both molecules have similar adsorption
strengths. The higher membrane selectivity will be
observed for the smaller molecule in this regime. If the
sum of the diameters of both molecules is larger than
the pore size, then the molecules cannot pass each other
inside the molecular sieve. This will reduce the
permeation of the molecule with higher diffusivity, because
it is blocked by the molecule with lower diffusivity (or
slow moving molecule). The second regime is a
competitive adsorption, in which both molecules have
similar sizes, but differ in their adsorption strengths. The
molecules will be competing for the same adsorption site
within the zeolite pore. The strongly adsorbing molecule
will not spare many adsorption sites for the weakly
adsorbing molecule, and thus the higher membrane
selectivity will be observed for the strongly adsorbed
molecule in this regime. At higher temperatures the
120
Fig. 5 – SEM image of a zeolite membrane 45
adsorption capacity decreases. This results in reducing
the ability of the molecule to block adsorption sites for
weakly adsorbing molecules. Therefore, the separation
factor induced by competitive adsorption decreased with
temperature. The third regime is a combined difference
in diffusivity and competitive adsorption. The molecules
have significantly different sizes and adsorbing strengths.
In this regime, the effect of each mechanism may
combine to enhance the separation factor, or compete
to reduce the separation factor.
Typically, the heat of adsorption of gases on most
zeolites increases in this order: H2 < CH4 < N2 < CO2.
This order is consistent with the electrostatic properties
of each molecule. Carbon dioxide adsorbs the strongest
because it has the strongest electrostatic quadrupolar
moment of the four gases, which significantly contributes
to its attraction to polar surfaces, like those found in
zeolites containing cations. Carbon dioxide preferentially
permeates in CO 2 /N 2, CO 2/CH 4 and CO 2/H 2 binary
mixtures at low temperatures, because CO2 is adsorbed
more strongly on zeolites than the other gases. For the
CO2/N2 and CO2/CH 4 mixtures, CO2 is smaller in size
and thus permeates faster at elevated temperatures.
However, the permselectivities and separation factors are
the same for CO2/N2 and CO2/CH4 systems at elevated
temperatures due to the absence of competitive
adsorption. The CO2/N2 or CO2/CH4 mixture is separated
by the third regime at lower temperatures, where
differences in diffusivity and competitive adsorption
combine to enhance the separation factor. At higher
temperatures, the CO2/N2 or CO2/CH4 mixture is separated
by the first regime, due only to differences in diffusivity.
For the H 2/CO2 mixture, separation also occurs by the
third regime, where diffusivity difference and competitive
adsorption compete, because CO 2 is the larger and
more strongly adsorbing molecule. At higher temperatures,
the CO 2 /H 2 selectivity inversion occurs, where H 2
permeates faster than CO 2 by the first regime in the
absence of competitive adsorption.45 Niwa et al.46 reported
separation of a gaseous mixture of CO2 and CH4 using a
microporous, thin glass membrane coated on the surface
of porous ceramic tubing by repeating the procedure of
TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
 dipping the ceramic tubing into a metal alkoxide solution
containing B2O3, followed by drying, heating and leaching
in HCl solution. The thickness of the membrane was in
the range of 5-23 µm, depending upon the number of
dips. The maximum separation factor of 1.48 was
obtained with the composite membranes which were
coated over 15 times with a casting solution in which the
ratio of B2O3 : SiO2 was 0.25 : 1. Composite membranes
with less than 5 coatings showed no ability to separate.
While decreasing the content of B2O3, they observed that
carbon dioxide seemed to permeate through the
composite membrane by the surface diffusion mechanism
in the pores. Kusakabe et al.47 studied the development
of the ZSM-5 type zeolite film for a membrane by mixing
a fine silica powder in an aqueous solution of the template
and calcining it at 400o or 550oC. The template was the
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mixture of tetrapropylammonium hydroxide (TPAOH) and
tetrapropylammonium bromide (TPABr). Three zones
were observed in the film formed on the support tube: a
crystalline layer deposited on the support tube, -alumina
macropores partially filled with deposits, and an
intermediate layer that was a mixture of deposits and
-alumina particles. The permeance of zeolite membranes
increased with decreasing the thickness of the zeolite
top layer, while no correlation was reported between
membrane morphology and CO 2/N 2 permselectivity.
They also reported the synthesis of different zeolite
membranes by hydrothermal reaction on the surface of
a porous -alumina support tube. The tube has the
following characteristics: length 30-200 mm, outer
diameter 2.9 mm, internal diameter 1.9 mm, average pore
size ~150 nm, and void fraction ~0.45. They concluded
that the adsorption of CO2 on the surface became partially
irreversible. The more strongly bonded CO 2 was less
mobile, resulting in lower CO2 permeability across the
membrane. Bakker et al. 48 studied the temperature
dependence of gas permeation through a silicalite-1
membrane. Silicalite-1 layer with a thickness of 50-60
μm was grown on a porous stainless steel support where
silicalite was prepared from silica, tetrapropylammonium
hydroxide and water, and it was subsequently calcined
at 400oC. The maximum permselectivity, CO2/N2 of 2.25
was achieved through a silicalite-1 membrane at 30oC
with CO2 permeance of 3.1  10–7 mol.m–2.s–1.Pa–1. They
also compared a theoretical model to their experimental
results for silicalite-1 zeolite membranes.
Kusakabe et al.49 further reported the synthesis of a
Y-type zeolite membrane for the determination of the
permeation properties for single component, as well as
for the equimolar mixtures of gases. The CO2 permeance
was approximately the same for the single component
system and the mixed CO 2/N 2 or CO 2/CH 4 system.
However, the N 2 or CH 4 permeances significantly
decreased for an equimolar feed at lower temperatures.
Separation factors as high as 100 and 21 for CO2/N2 and
CO2/CH4 mixtures respectively were obtained at 30oC. A
decrease in separation factors and in permselectivities
with increasing permeation temperatures was observed.
CO 2 molecules in micropores of the Y-type zeolite
VOL. 68 (3) JULY – SEPTEMBER 2009
membrane got adsorbed on the mouth of the micropores
of the membrane, where it impeded the penetration of
non adsorptive molecules (N2 or CH4) from entering into
the pores. The CO2 and N2 permeances increased initially
due to water desorption from the membrane surface.
Afterwards it gradually decreased with time due to possible
adsorption of impurities.
Poshusta et al.50 reported silicoalumino phosphate
(SAPO-34) membranes that were prepared by in situ
synthesis from gels onto porous -alumina tubes. They
explained the temperature dependence of the gas
permeances with a zeolite diffusion model. According to
this model, an increase in permeance with increasing
temperature is due to activated diffusion of a gas-like
phase in the zeolite pores. A decrease in permeance
with increasing temperature is due to a decrease in the
adsorbed concentration gradient. The heat of adsorption
and activation energy for diffusion of a particular gas-
zeolite pair determine the regime where the permeance
either increases or decreases with temperature. The
increase in CH4 permeance through SAPO-34 membrane
with temperature was attributed to a high activation
energy of diffusion because the kinetic diameter of CH4
(0.38 nm) is close to the zeolite pore diameter (0.45 nm).
The CO 2 permeance decreased with increasing
temperature because of a decrease in the adsorbed
concentration gradient. The CO 2/CH 4 mixture had the
highest separation factor of 30 at room temperature and
was separated by a combination of differences in diffusivity
and competitive adsorption because both favoured the
permeation of CO2 due to its smaller size and higher
adsorption strength compared to CH4.
Lovallo et al.51 studied synthesis of MFI membranes
on porous alumina disks and nonporous substrate using
secondary growth of precursor layers. They found that
the separation factor, CO2/CH4, decreased with increasing
permeation temperature, while the CO 2/N2 separation
factor increased first, and then decreased as temperature
increased. The permeation properties for the CO2/CH 4
mixture were independent of feed composition. The
separation factor, CO2/CH4 as high as 15 was observed
with CO2 permeance of 4  10–9 mol.m–2.s–1.Pa–1 at 120oC.
They further concluded that permeation properties
were attributed to both diffusion and adsorptive features
of the microstructure (thickness, grain size, degree of
orientation) of the molecular sieving layer of the MFI
membranes. The crystallographic orientation of the zeolite
MFI film also affected permeance ratios due to changes
in diffusivity with varying orientation of the crystals in the
film.52, 53 On the other hand, the CO2 permeance increased
and the N2 permeance decreased as the concentration
of CO2 in the feed composition was raised. The CO2/N2
separation factor reached values up to 20 (CO2 permeance
~1.8  10 –8 mol.m –2.s–1.Pa –1) at 180 oC for the feed
containing more than 60 per cent of CO2.
Kusakabe et al.53 also studied CO 2/N2 permeation
properties of Y-type zeolite membranes, ion exchanged
with Li+, Na+ and K+ cations, by a sorption-diffusion model.
They found that the high CO2/N2 separation factors for
121
 the binary mixed feed were caused by an increase in the
selective sorption of CO2. They concluded that the high
CO2/N2 separation factors for the binary mixed feed were
caused by an increase in the selective sorption of CO2.
They also confirmed the preferential transport of adsorptive
molecules through the Y-type zeolite membrane for the
CO2/H2 system, where CO2/H2 separation factor was 98
for an equimolar feed of CO2 and H2. Broeke et al.54 studied
pure gas permeation, as well as binary gas permeation
through a silicalite-1 zeolite membrane. They demon-
strated that the separation factor would be the same as
permselectivity if both components were weakly adsorbed
on silicalite-1 zeolite membrane. They further reported
that the permeation of the weakly adsorbed component
(N2 or CH4) would be reduced in a binary mixture in which
the other component (CO2) is moderately or strongly
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adsorbed. In such case, the separation factor and
permselectivity differ considerably.
Poshusta et al.55 also studied the synthesis of SAPO-34
that was conducted at 175oC for 24 h, whereas the synthesis
temperature was 185oC for 20 h in their previous study.
They found that the crystallization rate of SAPO-34
was reduced. They observed 2.5-40 times higher CO2
permeances than previous SAPO-34 membranes, but had
a similar CO2/CH4 separation factor. The highest CO2/CH4
selectivity achieved by them from SAPO-34 was 36 at
27oC. The mixture of CO2 and N2 also behaved similarly
to the CO2 and CH4 mixture through the SAPO-34 membrane.
A year after, Poshusta et al.45 reported the effects of
humidity on the gas permeation for SAPO-34 membranes.
The authors suggested that the membrane quality and
the fraction of transport through non-zeolite pores could
be determined by introducing humidity in the feed. It
was also noted that the effects of humidity on the gas
permeation are reversible, but long-term exposure can
permanently degrade SAPO-34 membranes.
Li et al.56 developed SAPO-34 membranes by in situ
crystallization onto tubular stainless steel supports where
the supports were placed directly on the synthesis gel.
A Maxwell-Stefan (MS) transport model with Lagmuir
adsorption was used to calculate the flux dependence
on pressure and drop, and these model results were
compared with the experimental results. The highest
CO2/CH 4 selectivity was reported to be 270 at 253 K
(pressure drop of 0.14 Mpa), and the CO2 permeance
was 2  10–7 mol.m–2.s–1.Pa–1. At 253 K and a pressure
drop of 3 Mpa, the CO2/CH 4 selectivity was 180 for a
50/50 feed mixture. The highest CO2 flux measured in a
mixture was 21 kg.m –2.h–1. They concluded that the
separation selectivity decreases as temperature
increases because separation is partially due to the
preferential adsorption of CO2. The overall effect is that
separation selectivities are higher than the ideal
selcetivities. Most of the observed pressure dependence
for CO2 flux in mixtures is predicted by Maxwell-Stefan
diffusion with an extended Lagmuir isotherm.
Cui et al.57 developed zeolite membranes of small pore
molecular sieves such as zeolite T (ERIOFF) (0.41 nm
pore size), DDR (0.36-0.44 nm) and SAPO-34 (0.38 nm)
122
that had pores of similar size as that of CH4 (0.38 nm)
but larger than that of CO2 (0.33 nm). It can be expected,
therefore, that these membranes showed high CO2/CH4
selectivities due to molecular sieving. For T-type (ERIOFF)
membranes they found a mixture separation factor,  =
400 with a CO2 permeance (P) of 4.6  10–8 mol.m–2.s–1.Pa–1
at 35oC for a transmembrane pressure drop of 0.1 MPa
and a vacuum at the permeate side. Li et al.58 obtained a
CO2/CH4 separation factor of 220 with a CO2 permeance
of 7  10–8 mol.m–2.s–1.Pa–1 at 28oC on a DDR membrane
for a pressure drop of 0.5 MPa.
In a recent study by Li et al.59 very powerful SAPO-34
membranes were synthesized by in situ crystallization
on a porous tubular stainless steel support. For a
SAPO-34 membrane with Si/Al gel ratio of 0.1, CO2/CH4
mixture selectivity of 170 with CO 2 permeance of
1.2  10 –7 mol.m –2.s–1.Pa –1 was found at 22oC. W ith
decreasing temperature the selectivity increases and at
–21oC a CO2/CH 4 separation factor of 560 was found.
SAPO-34 membranes prepared with the higher Si/Al ratio
of 0.15 had a slightly lower selectivity ( = 115) but a
higher CO2 permeance (P = 4  10–7 mol.m–2.s–1.Pa–1) at
35 o C. At 7 MPa, the SAPO-34 membrane showed
CO2/CH 4 selectivity of 100 for a 50% feed at room
temperature for a week. Li et al.58 found that SAPO-34
membranes can separate CO2 from CH4 effectively at low
temperatures with a selectivity of  = 270 at –20oC. The
SAPO-34 membranes effectively separate CO2 from CH4
for conditions at or near industrial requirements. However,
CO2 flux and selectivity decrease in the presence of
water since water has a strong affinity to the hydrophilic
SAPO-34 membrane. It has been shown in Fig. 6.59
Therefore, hydrophobic narrow pore zeolite mem-
branes are more appropriate to separate CO2 from humid
gases. Consequently DDR membranes show high CO2
flux and selectivity and an only negligible water influence
on the separation performance in the CO2 separation from
natural gas.60 Bergh et al.61 reported DDR membranes
that exhibited very high selectivities for CO 2 /CH 4
UPPER
100 BOUND
CO2/CH4 SELECTIVITY
10
POLYMERS
0
0.1 1 10 100 1000 10000
CO2 PERMEABILITY 10 2
 10 (cm (STP)/(s.cmHg))
Fig. 6 – Comparison of CO2/CH4 separation selectivity versus
CO 2 permeability (Robson plot) for polymeric membranes
and two SAPO-34 membranes at room temperature and feed
and permeate pressures of 222 and 84 kPa, respectively.
The two arrows indicate the experimental results on two
SAPO-34 membranes 59
TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
 separations with good permeances. At a total pressure of
101 kPa and at –50oC, the CO2 selectivity of an equimolar
mixture was found to be more than 3000. The CO 2
selectivity drops with increasing temperature and
pressure, but is still above 100 at 100oC and 10 bar total
feed pressure (Fig. 7). 61 The drop in selectivity with
increasing pressure is attributed to the dependence of
the diffusivity on the total loading. The high selectivity is
caused by the molecular sieving effect for CH 4 and to
some extent by the preferential adsorption of CO2. Hong
et al.62 reported the tuning of the CO2 permeation through
SAPO-34 by ion exchange. The SAPO-34 membranes
were synthesized inside the stainless steel tubes as
described by Poshusta et al.55 and Li et al.63 Ion exchange
of H+-SAPO-34 membranes with Li+, Na+, K+, NH4+, Cu2+
cations in non-aqueous solutions increased both the
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CO2/CH 4 mixture selectivities by about 60%. After ion
exchange, the mixture separation factors were found to
be of the order of 60-90.
The role of water was also addressed in the permeation
experiments using dry single component, binary and multi
component mixtures showing that the FAU membranes
are CO2 selective for dry feed gases over a wide range of
temperatures and compositions.
However, the presence of water vapour in the feed
enhances the CO2 flux significantly. The maximum CO2/H2
mixture separation factor () was 19.1 (60oC, P CO ,Feed2
= 30 kPa, CO 2 flux (J CO ) = 4 mmol.m –2 .s –1 ). The
2
membranes can separate also CO2/CH4 ( = 22.6, JCO
= 3.4 mmol.m –2.s –1) and CO 2/N 2 ( = 33.4, J CO =
4.6 mmol.m–2.s–1).64
Carreon et al.65 studied SAPO-34 membranes that
were prepared using different pivotal crystallization
templates and secondary structure directing agents on
porous -Al2O3 supports. They found that CO 2 /CH 4
separation performance depends on the sizes of the
zeolite crystals used as seeds for membrane growth.
They concluded that reproducible SAPO-34 membranes
(6-7.5 µm thick) could be synthesized by secondary
seeded growth on -A l 2O 3 porous supports. The
101
CO2 SELECTIVITY
500
1000
1000
TOTAL FEED PRESSURE (kPa)
100
200 300 400
TEMPERATURE (K)
Fig. 7 – The CO 2 selectivity of a DDR membrane for an
equimolar CO 2/CH 4 mixture as a function of permeation
temperature 61
VOL. 68 (3) JULY – SEPTEMBER 2009
membranes effectively separated CO2/CH 4 mixtures up
to 1.7 MPa, which was the highest pressure that could
be used for a zeolite layer on the inside of the ceramic
support. Crystals smaller than 1 μm yielded membranes
that displayed unprecedented CO2 permeances with high
CO 2/CH 4 selectivity. The membranes had CO 2/CH 4
separation selectivity higher than 170, with CO 2
permeances as high as ~2.0  10–6 mol.m –2.s–1.Pa–1 at
295 K and a feed pressure of 224 kPa.
Therefore, it has been observed that zeolite
membranes show the least variation in both selectivity
and permeability of any inorganic membrane type in
separations of CO2/H2, CO2/CH 4 and CO2/N2 mixtures.
These membranes have relatively high permeabilities
and relatively low selectivities (Figs. 8 and 9).51 The lack
of selectivity is less pronounced in CO 2/CH 4, probably
because of the considerable differences in shape and
size of the two molecules. This has enabled researchers
to take full advantage of the molecular sieving properties
of the zeolites. The lack of any internal trend in the zeolite
results (i.e. any approximate inverse relationship between
selectivity and permeability), however, is indicative of
the dual transport mechanism so well known in zeolite
membranes.
Carbon Membranes
Carbon membranes for gas separations are typically
produced by the pyrolysis of thermosetting polymers such
2
as polyimides, polyvinylidene chloride (PVDC),
2
polyfurfuryl alcohol (PFA), cellulose, cellulose triacetate,
polyacrylonitrile (PAN) and phenol formaldehyde.66 The
pyrolysis temperature, typically in the range of 500o to
1000oC, depends upon the type of precursor material
and dictates the separation performance of the carbon
membranes. At higher pyrolysis temperatures
graphitization takes place. The pore size of carbon
molecular sieve membranes (CMSM) depends upon the
pyrolysis chemistry (temperature, heating rate, heating
atmosphere, etc) as well as upon the morphology of the
organic precursor.49, 67 The porosity due to morphology is
12
10
CO2/N2 SELECTIVITY
8
6
2
0
1.00E+02 1.00E+03 1.00E+04 1.00E+05
CO2 PERMEABILITY (BARRER)
Fig. 8 – CO2/N2 selectivity versus CO2 permeability for zeolite
membr anes 5 1
123
 20
16
CO2/CH4 SELECTIVITY
12
8
4 the micropores rather than the total micropore volume.
0 by chemical vapour deposition (CVD) of carbon formed
1.00E+02 1.00E+03
CO2 PERMEABILITY (BARRER)
Fig. 9 – CO 2/CH 4 selectivity versus CO 2 permeability for
Downloaded by [University of California, San Diego] at 22:35 03 January 2016
z eolite membranes 51
coarse macroporosity, while microporosity depends
upon the pyrolysis chemistry. 67 Pyrolysis of polymeric
compounds leads to carbon material with a very narrow
micropore distribution below molecular dimensions
(<1 nm)68 which makes it possible to separate gases
with similar molecular sizes. Hence, the predominant
transport mechanism of most carbon membranes is
molecular sieving. In adsorption selective carbon
membranes (ASCM) the separation takes place because
of the selective surface diffusion mechanism.69 ASCMs
separate non-adsorbable or weakly adsorbable gases
(He, N2, O2, etc) from adsorbable gases, such as NH3,
CO2 and SO2. ASCMs possess slightly wider micropores
(5-7 Å) than those of CMSMs (3-5 Å).
Generally, carbon membranes can be categorized into
two types: supported membranes on a porous material
(tube or flat) and unsupported carbon membranes (flat,
hollow fiber, or capillary tube). Unsupported membranes
are very brittle and mechanically unstable, resulting in
handling problems. The permeance of carbon membranes
is quite low compared to other inorganic membranes due
to the large thickness of carbon membranes. The factors
that determine the performance of CMSMs include
the selection of the precursor polymer, the membrane
preparation method, and the carbonization process.70
The high cost of polyimides is a key factor that limits
their utilization in the preparation of carbon membranes.
The high thermal and chemical stability of CMSMs provide
tremendous possibility in gas separation applications,
such as separation of CO2 in flue gas emissions from
power plants. The mechanical stability of CMSMs can
be increased by supporting a thin carbon membrane on
a porous support material, such as -alumina, carbon,
etc. A review by Ismail et al.71 gives detailed information
on the latest developments associated with carbon
membranes for gas separation. Some of the other works
in this regard is given below.
Hayashi et al. 72 prepared carbon membranes by
coating a polyamic acid film formed from 3,3 / ,4,4 / -
biphenyltetracarboxylic dianhydride (BPDA) and
oxydianiline (ODA) on a porous -alumina support tube.
124
The polyamic acid film coated on the alumina tube was
imidized in N2 during a multi step heating procedure up
to 300oC. The resulting membrane was then carbonized
at 500o-900oC in air. They reported that the carbonization
above 600oC remarkably increased the permeances of
CO2 and other gases. Permeances decreased and the
permselectivity increased with increasing carbonization
temperatures beyond 600oC. It was concluded that the
CO2 permeance was controlled by the size distribution of
The carbonized membrane pores were further modified
1.00E+04 from the pyrolysis of propylene at 650oC. The CO2/N2
permselectivity of the membranes after 2 min CVD
treatment was increased from 47 to 73. Longer CVD
treatment decreased CO 2 permeance due to blocking
of pores with carbon deposits and hence, the perm-
selectivity also decreased. Fuertes et al.73 prepared flat,
asymmetric carbon membranes by casting a solution of
polyamic acid (BPDA-pPDA) in N-methylpyrrolidone
(NMP) upon a macroporous support and by subsequent
imidization at 380oC and carbonization at 550oC. They
emphasized that by using the phase inversion during the
preparation stage an almost defect-free carbon
membrane can be obtained in only one casting step. It
was observed that the CO2/N2 or CO2/CH4 permselectivity
decreased with increasing temperature, while the CO2
permeance remained unchanged. Their explanation for
this phenomenon was that the CO2 transport through
the membrane results from a combination of transport in
the gas phase (molecular sieving) and surface diffusion
of the adsorbed molecules across the micropores. The
decrease in CO2 adsorption with increasing temperature
was compensated by an increase in gas diffusivity, and
hence, CO2 permeance remained unchanged. Fuertes
et al.70 also prepared symmetric carbon molecular sieve
membranes in the same method from the same raw
materials by using the multicoating step. They reported
that the performance of these membranes was better
than those of the asymmetric carbon membranes
prepared in a single casting step.
In a different study, Fuertes et al.68 observed that only
the molecular sieving mechanism contributes in the
transport of CO 2 across the carbon molecular sieve
membranes, which were prepared by taking polyetherimide
as a precursor upon a porous carbon support. They chose
polyetherimide for its inexpensiveness and commercial
availability, compared to other materials used as
precursors for carbon membranes. Centeno et al. 74
prepared a carbon membrane by coating a phenolic resin
(Novolak type) on a macroporous carbon disk shaped
support and subsequent carbonization under vacuum
of the polymeric film. An almost defect-free carbon
membrane was obtained in a single casting step. The
separation factor of CO 2/N 2 or CO2/CH 4 from a feed
mixture (85% N2 + 15% CO2) or (10% CO2 + 90% CH4)
was higher than that calculated from the ratio of
permeances of pure gases. It was suggested that the
presence of CO2 in the mixture restricted N 2 diffusion
TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
 through the micropores of the membrane. The separation
factor for CO2/N2 or CO2/CH4 decreased with increasing
temperature, but remained unchanged with pressure.
They also studied phenolic resin based carbon
membranes supported on a porous alumina tube.75 They
showed that the gas permeability decreased significantly,
while the permselectivity did not change much with the
number of coats and, hence, claimed to obtain a defect-
free carbon membrane in a single casting step.
Kusuki et al. 76 prepared asymmetric carbon
membranes by pyrolyzing an asymmetric polyimide
hollow fiber membrane at temperatures ranging from 600o-
1000oC in N2. The polyimide hollow fiber membrane was
formed from BPDA and an aromatic diamine, such as
ODA. It was observed from scanning electron microscopy
(SEM) studies that the top thin layers of the carbon fibers
Downloaded by [University of California, San Diego] at 22:35 03 January 2016
pressure and were stable over time. The CO2 permeance
from the membrane was 3.4  10–8 mol.m–2.s–1.Pa–1 at 50oC
with CO2/CH4 permselectivity of about 30.
Ogawa and Nakano80 developed carbonized hollow fiber
membranes for CO2/CH4 separation by the phase inversion
of polyamic acid solution, imidization and carbonization.
They also studied the effect of gelation conditions (time,
temperature and pH of coagulation) on the permeation
properties of the resulting membrane. Polyamic acid
solution was prepared by dissolving 4,4/-diaminodiphenyl
ether in N,N-dimethylacetamide and then adding
pyromellitic dianhydride to the solution. They reported that
the micropore volume was independent of the gelation
time and, hence, gelation time was not a predominant
factor controlling the permeation properties of the hollow
fiber membrane. The CO2/CH4 and CO2/N2 permselectivities

were composed of dense aggregation of nodules having
diameter of about 50 nm. The asymmetric carbon
membranes, pyrolyzed at 850oC, showed lower permeability
than the membrane pyrolyzed at 700oC, but had higher
permselectivities for the CO2/CH4 system (Table I).
Wang et al. 77 used a different technique, vapour
deposition polymerization (VDP), to prepare supported
carbon membranes using a PFA thin layer. The VDP
technique can provide better control of film depositions
inside the pores of supports. In another study Wang and
Gavalas78 used two different support tubes, -Al2O3/-Al2O3
and glass/-Al2O3, prepared in their laboratory. Membranes
were prepared by two cycles of VDP, and two carbonization
cycles at 600oC. The CO2/CH4 separation factor was lower
than the CO2/CH4 permselectivity by a factor of 3 (Table II).
It was concluded that the low CO2 permeance of the VDP
membranes was due to deeper penetration of gaseous
furfuryl alcohol into the support during VDP, or due to a
different pore structure of the carbon. Tanihara et al.79
prepared asymmetric carbon hollow fiber membranes by
pyrolysis of asymmetric polyimide hollow fiber membranes
at 700oC. It was observed that the permeation properties
of the carbon membranes did not depend on the feed
were the highest when the polyamic acid solution was
gelated for 1 h (Table III). The CO 2/CH 4 and CO2/N 2
permselectivities were maintained at approximately
60 and 30, respectively, in further gelation. The micropore
volume increased as gelation temperature increased
and as pH decreased. High permeance of CO2 and high
CO2/N2 and CO2/CH4 permselectivities through the carbon
membrane were achieved at the following gelation
conditions: time 6 h, temperature 2oC and pH 9.4. It was
found that the CO 2 transport was enhanced by an
adsorption effect, while transport of CH 4 and N2 was
restricted by a molecular sieving effect in the carbonized
membrane.
In another study, Ogawa and Nakano81 investigated
the separation of CO2/CH 4 mixtures and the effect of
membrane micropore diameter on the permeation properties.
Three different pore sizes of membrane for the CO2/CH4
separation were studied: membrane A (> 0.50 nm),
membrane B (0.43-0.50 nm) and membrane C (< 0.43 nm).
The permeances of CO2 and CH4 through membranes A
and C were independent of the composition of the feed
gas (Table IV). For membrane B, the CH 4 permeance
decreased with the increase in CO2 content in the feed

Table I : Summary of results from asymmetric carbon membranes

prepared from polyimide hollow fiber membrane 76

Carbonization Permeation CO2 permeance Permselectivity

temperature (oC) temperature (oC) (mol.m–2.s –1.Pa–1) CO2/N2 CO2/CH4

270 50 2.6  10–9 36 27

–9
75 3.3  10 20 17
–9
120 4.0  10 10 10

700 50 4.0  10–8 17 30

75 6.7  10–8 17 25

120 1.0  10–7 14 21

850 50 1.8  10–9 18 37

–9
75 3.0  10 15 45
–9
120 5.0  10 13 48

VOL. 68 (3) JULY – SEPTEMBER 2009 125

 Table II : Summary of results from supported carbon membranes prepared from PFA by VDP 77

Permeation Support CO2 permeance Selectivity

temperature (oC) (mol.m–2.s –1.Pa–1) CO2/N2 CO2/CH4
–9
25 -Al2O 3/-Al2O 3 5.8  10 79 92

150 -Al2O 3/-Al2O 3 3.3  10–8 9 15

25 Glass/-Al2O 3 2.7  10–9 40 82

150 Glass/-Al2O 3 3.0  10–9 11 17

a –9
25 -Al2O 3/-Al2O 3 2.3  10 – 27b

25a Glass/-Al2O 3 1.1  10–9 – 25b

a
Feed : 85% CO 2 and 15% CH4; bSeparation factor

Table III : Effects of gelation conditions on permeation of carbon hollow fiber membranes 80
Downloaded by [University of California, San Diego] at 22:35 03 January 2016

Gelation condition Permeation CO2 permeance Permselectivity

Time (h) pH Temperature (oC) temperature (oC) (mol.m–2.s –1.Pa–1) CO2/N2 CO2/CH4

1 6.5 2 25 9  10–9 45 100

–9
6 6.5 2 25 5  10 25 50
–8
10 6.5 2 25 1  10 33 66

6 6.5 25 25 7  10–8 18 12

6 6.5 39 25 1.6  10–8 12 17

6 3 2 25 2  10–8 28 13
–9
6 9.4 2 25 7  10 230 23
–11
6 11 2 25 7  10 5 2

gas that resulted in increase in the CO2/CH4 separation
factor. It was concluded that the CO2/CH4 separation factor
for membrane B increased due to the restriction of CH4
permeation by CO 2 molecules adsorbed inside the
micropores of the membrane.
It is obvious from the above discussion that carbon
membranes have a great potential to perform gas
separations efficiently, particularly when the gas
molecules to be separated are of similar sizes. Carbon
membranes, illustrated in Figs. 10 and 11,80, 81 show the
greatest variation in selectivity and permeability of any
of the types of inorganic membrane for the separation
of CO 2 from H 2, N 2 and CH 4. The expected inverse
relationship of selectivity to permeability is present
across the range of literature, resulting primarily from
the abundance of work on CMSMs. These membranes
have the highest demonstrated selectivities in most
separations, but the permeability limitations associated
with them are unlikely to be overcome. Also, high
production costs of carbon membranes along with
expensive modules have prevented their intended
commercial scale use. A significant amount of research
is required in order to find more economical precursors
for carbon membrane production, while improving their
permeation properties at elevated temperatures and
pressures in the presence of complex feeds.

Table IV : Separation of CO2/CH4 through carbonized membrane prepared by gel modification 81

Membrane Pure gas permeation Mixed gas permeation

CO2 permeance Permselectivity Feed gas CO2 permeance Separation factor
(mol.m–2.s –1.Pa–1) (CO2/CH4) CO2 : CH4 (mol.m–2.s –1.Pa–1) (CO2/CH4)

A 3.16  10–8 42 15 : 85 3.13  10–8 51

B 1.3  10–9 181 15 : 85 1.36  10–8 265

–8
65 : 35 1.01  10 310

C 4.84  10–11 5 15 : 85 4.05  10–11 4

o o
Permeation temperature 25 C; Gelation conditions: time 6 h, temp 2 C, and pH 9.4.

126 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

 140
120
CO2/N2 SELECTIVITY
100
80
60
40
20
0 0
1.00E+00 1.00E+01 1.00E+02 1.00E+03
CO2 PERMEABILITY (BARRER)
Fig. 10 – CO 2/N 2 selectiv ity versus CO 2 permeability for
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carbon membranes 80
Silica Membrane
Silica is considered to be a viable starting material in
the fabrication of CO2 selective membranes, primarily
because of its innate stability. Unlike alumina, this tends
to undergo phase transition at relatively low temperatures,
or carbon, which can exhibit substantial changes in pore
size in oxidizing environments, silica shows exceptional
thermal, chemical and structural stability in both oxidizing
and reducing environments. 48, 81 Different fabrication
procedures, including those not as advanced as those for
carbon and alumina membranes, are capable of producing
defect-free silica membranes with molecular sieving pores.
Though surface diffusion has been named as an important
mechanism in a number of studies on silica membranes
for the selective separation of CO2, most researches have
only considered silica as a complement to the molecular
sieving mechanism. Research then, has focused primarily
on separation of CO2 from N2 and CH4, the surface diffusion
mechanism not being considered strong enough for the
more difficult separation from H 2. Notable exceptions
include the works of Hayashi et al.82 and Uhlhorn et al.83
Both studies conclude that surface diffusional control
in membranes fabricated by the sol-gel method is the
most common type of preparation procedure for silica
membranes.
Silica is a very versatile material for gas separation
membranes because its structure can be tailored by
changing the preparation method and conditions.
Generally, microporous silica membranes are prepared
by deposition of a silica layer onto a porous support by
either the sol-gel method, or chemical vapour deposition
(CVD) technique, or phase separation method. The porous
support provides mechanical strength to the selective top
layer of silica. Kusakabe et al.84 formed silica membranes
on a -alumina coated -alumina tube using sols prepared
from the co-polymerization of tetraethoxysilane (TEOS)
and octyltriethoxysilane (C8TES), C12TES, or C18TES.
The alkyltriethoxysilanes were used as the template to
control the pore size of the silica membranes. The authors
obtained defect-free silica membranes from C8TES and
C12TES. Silica membranes prepared from C18TES
VOL. 68 (3) JULY – SEPTEMBER 2009
300
250
CO2/CH4 SELECTIVITY
200
150
100
50
1.00E+04 1.00E+00 1.00E+01 1.00E+02 1.00E+03 1.00E+04
CO2 PERMEABILITY (BARRER)
Fig. 11 – CO 2/CH 4 selectivity versus CO 2 permeability for
carbon membranes 81
contained defects and mesopores, and hence, the
transport across these membranes was controlled by the
Knudsen diffusion mechanism. It was concluded that the
silica structure, which was formed from C18TES, might
not be strong enough to withstand shrinkage during
calcination. The effect of the molar ratio of water to total
alkoxides, x, in the sols was also studied. High
permeances and low selectivities were found for the
membrane formed with x = 4. The size of micropores,
before calcination, of silica membranes prepared from
alkyltriethoxysilanes was found to be very close to the
minimum dimension of the alkyl groups and increased
slightly with increase in the size of the alkyl group. The
micropores in the range of 0.3-0.4 nm for the silica
membranes were formed after calcination at 600oC. The
permselectivities for the CO2/N2 and CO2/CH 4 systems
increased with increasing calcination temperature of silica
membranes (Table V).
In the sol-gel technique (Hayashi et al.82, Munoz-
Aguado et al.85) polymeric silica sols are deposited on
top of a support system consisting of about a micron
thick -alumina over a macroporous -alumina of desired
thickness. The silica layer is then calcined at 400o-800oC
to develop a separating top layer with thickness of
50-100 nm. The silica sols are obtained from the hydrolysis
condensation reaction of alkoxysilanes, such as
tetramethoxysilane (TMOS), TEOS or chlorosilane. It is
technically challenging to get uniform thickness and
pinhole-free silica membranes from the method described
above. In the CVD technique, organic precursors in vapour
phase are introduced to porous support. A uniform and
almost pinhole-free top membrane layer is obtained from
the CVD technique. This technique is also used to narrow
down or to plug the mesopores of silica membranes.86
A typical SEM photograph of silica membrane is shown
in Fig. 12.87
In the phase separation method of Burggraaf et al.33
and Wang et al. 78 the homogeneous glass, sodium
borosilicate, separates into two phases under certain time
and temperature conditions: an acid soluble boric acid
rich phase and an insoluble silica rich phase. Leaching of
127
 Table V : Summary of results from different silica membranes 53, 113

Precursor a Temperature CO2 permeance Permselectivity

(oC) (mol.m–2.s –1.Pa–1) CO2/N2 CO2/CH4 H2/CO2
c b –8
TEOS + C8TES 100 7  10 3.5 2.5 0.9

(200) c 100 1  10–7 3 2 1.3

c –7
(600) 100 2.2  10 7 7 2
d –9
(600) 100 8  10 8 4.5 12
–10
TEOS (600) 30 3.6  10 0.7 0.7 12
–10
200 3.3  10 0.7 0.7 67
–10
400 3.3  10 0.7 0.7 150
–9
PTES (500) 30 8  10 5 6 1.2
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–8
200 1  10 6 6 6
e –8
DPDES (500) 30 8.1  10 9 11 6
–8
200 3.3  10 4 6 16
–8
400 1.8  10 2 2 25
f –8
DPDES (500) 30 2.1  10 1 – –
200 1.9  10–8 0.9 – –

DPDES (500)e, g 30 1.4  10–8 1.4h – –

–8
200 1.5  10 1.2h – –
f, g –8 h
DPDES (500) 30 2.3  10 1.1 – –
–8
200 2.1  10 1.0 – –
a b c d
Calcination temperature in parenthesis; No calcination; Gel formation temperature 80°C; Gel formation temperature 60°C;
e
Sweep gas: argon; f Sweep gas: helium; gFeed: 10% CO2 and 90% N2; hSeparation factor

the boric acid phase in a mineral acid solution removes
the acid soluble boric acid phase, leaving behind a porous
insoluble silica phase. The silica pore size can be
controlled by changing glass composition, annealing time
and temperature. Mesoporous silica membranes obtained
from the phase separation method is not suitable for gas
separations, so they find applications mostly as a support
for microporous or nonporous membranes. Some of the
important works on silica membrane are given below.
Fig. 12 – SEM image of a Si(400) membrane cross-section
showing a part of the -Al2O3 layer and the silica layer at high
magnification 87
Uhlhorn et al. 83 formed a ~30 nm thin layer of
microporous silica on top of a -alumina membrane using
the sol-gel technique. The permeability to CO2 strongly
increased with the mean pressure of the system, while
the permeability to N2 and CH4 remained unchanged. The
transport across the silica-modified membrane is due to
the surface diffusion mechanism, as indicated by the
observed pressure dependence and very small pores of
the silica. Permselectivities for CO2/N2 and CO2/CH4 were
as high as 15 and 10 respectively, with CO2 permeances
of about 3  10–6 mol.m–2.s–1.Pa–1.
De Vos et al.88 prepared almost defect-free silica
membranes by applying two sol-gel derived silica
(thickness 30 nm and pore size ~5 Å) layers on top of a
-alumina layer, supported by an -alumina structure. A
silica sol was prepared by acid-catalyzed hydrolysis and
condensation of TEOS in ethanol. They reported that
the silica membranes showed a slight increase in the
permeances of gases with increasing temperature and a
slight decrease for CO2 permeance (Table VI). The CO2/CH4
permselectivities in the silica membrane calcined at
400oC (Si400) were very large and the H 2/CO2 perm-
selectivities were very large in Si600 because the
membranes were so dense that CH4 could not permeate
in Si400 and CO2 in Si600.
Raman et al. 89 tried to deposit a hybrid organic-
inorganic sol, prepared by co-polymerization of TEOS and
methyltriethoxysilane (MTES) on a porous alumina

128 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

 Table VI : Summary of results from different silica membranes 88, 89. 114

Precursor a Permeation CO2 permeance Permselectivity

temperature (oC) (mol.m–2.s –1.Pa–1) CO2/N2 CO2/CH4 H2/CO2

TEOS (400) 25 2.3  10–7 23 325 2.6

100 2.9  10–7 15 190 4

–7
200 2.3  10 8 75 7.5
b
200 – – – 7d

200c – – 45d –

TEOS (600) 100 9.4  10–9 – – 26

200 6.1  10–9 – – 66

300 4.6  10–9 – – 139

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TEOS, methylated 100 5.1  10–7 1.8 1.9 4.5

(400) –7
200 4.1  10 1.6 1.5 5
–7
300 3.0  10 1.3 1.1 6.4

Hollow fiber 25 2  10–8 20 156 3

150 2  10–6 9 21 5
c d
25 – – 180 –
c d
150 – – 20 –

TEOS + MTES 25 8.6  10–7 1 – 12

(550) e –7
25 7  10 0.9 – 72
a b c d e
Calcination temperature in parenthesis; Equimolar feed of CO2 and H2; Equimolar feed of CO2 and CH4; Separation factor; After surface
derivatization with 1:12 TEOS monomer.

support. The calcined silica membrane was further
modified by derivatization of the pore surfaces with
monomeric TEOS to allow monolayer by monolayer
“fine tuning” of pore size. Subsequent derivatization of
the pore surfaces significantly increased the CO 2/CH 4
separation factor with only a slight decrease in CO 2
permeance (Table V). The CO2/CH4 permselectivity of the
fine-tuned membranes was 72 with the CO2 permeance of
about 7  10–7 mol.m–2.s–1.Pa–1.
Tsai et al. 90 formed dual layer microporous silica
membranes using a sol-gel dip-coating process. They
deposited a surfactant-templated silica (STS) intermediate
layer on the top of the -alumina support to improve its
surface finish and to prevent the subsequently deposited
sol from penetrating into the support. The resulting
membranes were dip-coated under clean room conditions
to avoid dust contamination, and vacuum-calcined at 300oC
for 6 h to promote further pore shrinkage and to enhance
surface hydrophobicity. The source of the silica sol was
TEOS, and surfactants used in the STS layer were C6-
surfactant (triethylhexylammonium bromide) and C16-
surfactant (cetyltrimethylammonium bromide). The dual
layer asymmetric membranes possess a gradual change
of pore size from 50 (-alumina support layer) to 10-12 Å
(STS intermediate layer), and then to 3-4 Å (300 Å thick
microporous top layer). They achieved a high CO 2
permeance (1.1  10–7 mol.m–2.s–1.Pa–1) along with a high
CO2/CH4 separation factor of over 300 at 26oC from the
dual layer silica membrane for a separation of an equimolar
CO2/CH4 gas mixture. They reported shrinkage of larger
pores upon further calcination at 450oC in air for 1 h. The
resulting membrane provided 92 mol% H2 purity with 50
times reduction of CO from a simulated reformat mixture
(33.98% N2, 15.00% CO2, 0.997% CO and 50.023% H2)
for application in fuel cells. The same membrane also
gave CO2/CH4 and CO2/N2 permselectivities of 240 and
60 respectively, along with CO 2 permeance of around
2  10–8 mol.m–2.s–1.Pa–1 at 80oC.
McCarley et al. 91 fabricated gas separation
membranes by modifying mesoporous -alumina with
octadecyltrichlorosilane (ODS). Based on ellipsometry
measurements and XPS analysis the authors concluded
that the composite membrane contained a very thin
selective polymer film of ODS molecules (~10.1 nm)
interconnected with the porous alumina surface. Selectivity
of CO2/N2 increased by 10%, while the CO2/CH4 selectivity
almost doubled for the mixed gas separations, compared
to the pure gas permeances (Table VII). The increase in
selectivity for the mixed gases was attributed to the
competitive adsorption. They also found that the pure gas

VOL. 68 (3) JULY – SEPTEMBER 2009 129

 Table VII : Permeation properties of surface (Figs. 13 and 14).90, 92 The exceptions, as discussed above,
flow membrane 91 are the works of Asaeda et al.92 and Tsai et al.,90 which
showed the greatest promise for development of practical,
Membrane Permeation CO2 permeance Permselectivity
CO2 selective silica membranes.
temp (oC) (mol.m–2.s –1.Pa–1) CO2/N2 CO2/CH4

ODS/ 20 2  10–8 5.14 2.1 Mass Transfer in Gas Separation Membranes

-alumina
20a 4  10–8
20 b
1.4  10 –8
a b
Feed: 51.3% CO2 and 48.7% N2; Feed: CO2 and CH4 equimolar
mixture; cSeparation factor
permeances followed an exponential relationship with the
critical temperature, which showed that the transport was
controlled by preferential adsorption since solubility of
gases is an exponential function of critical temperature.
Asaeda et al.92 applied sol-gel techniques to fabricate
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Mass transfer in porous media for gas separation by
5.84c 4.31c membrane has been frequently studied by many
– – researchers.93, 94 Although several mechanisms have been
presented based on pore size and mean free path of gas
molecules, in many cases, these mechanisms cannot
be used alone due to the existence of a large range of
pore sizes. Nearly all cases of combination of basic
models have been utilized in different studies. Detailed
discussion of transport mechanism models, such as
viscous flow model, Knudsen diffusion model, surface
diffusion model, dusty gas model (DGM) and confi-

thin layer silica membranes on porous silica and silica- gurational diffusion model applied in porous ceramic
membranes can be referred from Pakizeh et al.95 Miranda
zirconia supports coated on -alumina porous cylindrical
and Campos96 reported that in the mass boundary layer
tubes. The pore size of the silica membrane was around
over the membrane, mass transfer rate quantification is
0.35 nm. The CO2 permeance increased through the silica
essential to design membrane separation processes and
membrane as the temperature decreased, while N2 and
they further reported that mass transfer coefficient data
CH4 permeances increased very slightly, because CO2 is
for impermeable systems can be shown in the design of
more adsorptive on the silica surface than N2 or CH4 (Table
membrane separation processes.
VIII). They reported that the porous silica membranes were
Li et al.97 showed that for a membrane with a smaller
quite stable when used in dry conditions, while a silica
average pore size and a higher standard deviation in pore
membrane on a silica-zirconia sub-layer was even stable
in humid conditions. Shelekhin et al. 87 used the 30
microporous silica hollow fibers (PPG Industries, Inc) as
membranes for gas separations. The fiber had a 22 μm 25
inner diameter, 32 μm outer diameter and a length of 0.135
CO2/N2 SELECTIVITY

m. The membranes from the fibers were resistant to high 20

temperature as well as chemically resistant with very
competitive transport properties. However, the fiber was 15
very brittle to fabricate the membrane module. Selectivity
in the hollow fiber membrane was found to be a function 10
of differences in the gas kinetic diameters and decreased
with increasing temperature (Table IX). 5
From these works it is apparent that silica membranes
0
have a variety of permeabilities, but lack in good selectivity 1.00E-02 1.00E+00 1.00E+02 1.00E+04
CO2 PERMEABILITY (BARRER)
Table VIII : Gas permeances for porous silica membranes 92
Fig. 13 – CO2/N2 selectivity versus CO2 permeability for silica
Membrane Permeation CO2 permeance Permselectivity membranes 90, 92
temp (oC) (mol.m–2.s –1.Pa–1) CO2/N2 CO2/CH4
350
Silica/silica/ 35 7  10–7 17 80
-alumina 300
300 2  10–7 6 25
CO2/CH4 SELECTIVITY

Silica/silica- 35 9  10–7 25 100 250

zirconia/- –7
300 3.5  10 8 16 200
alumina

150
Table IX : Permeation of gases in microporous
glass membranes 87 100

Permeation CO2 permeance Permselectivity 50

temp (oC) (mol.m–2.s –1.Pa–1) CO2/N2 CO2/CH4
0
30 1.8  10–9 34 1675 1.00E-02 1.00E+00 1.00E+02 1.00E+04

100 2.9  10–9

23 780 CO2 PERMEABILITY (BARRER)

–9 Fig. 14 – CO2/CH4 selectivity versus CO2 permeability for silica

250 3.1  10 7 62
membranes 90, 92

130 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

 size distribution, significant error in membrane’s coefficient
can be caused by the pore size distribution. This is
because, as the average pore size decreases, the
membrane’s coefficient is progressively dominated by the
Knudsen diffusion coefficient. Under this regime, the pore
size distribution has a great effect on the membrane’s
coefficient. LuÈdtke et al.98 in their study reported the
overall mass transfer coefficient for n-butane kC4 as a
function of the Reynolds number for four different feed
pressures (PH) on PDMS layer. The measurements were
made with 2.2 vol% n-butane in nitrogen at 295 K and a
permeate pressure of 0.3 bar. In the legend, the nitrogen
permeability (LN2) and n-butane permeability (LC4) are
given for the investigated conditions calculated with the
extended free volume model from single gas
measurements (Fig. 15).98
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With increasing Reynolds number, the overall mass
transfer coefficient increases in gas transport. This is
related to better mass transfer through the boundary layer
on the feed side of the membrane (concentration
polarization effects) with higher flow rates over the
membrane. For a constant Reynolds number, the overall
mass transfer coefficient decreases with increasing feed
pressure. This behaviour is related to the fact that mass
transfer through the boundary layer is mainly based on a
diffusion mechanism. Since the diffusion coefficient is
inversely proportional to the pressure, with increasing feed
pressure the diffusion coefficient decreases and the
resistance in the boundary layer increases. Thus, with
an increase in the part due to boundary layer resistance,
the separation properties of the membrane decrease. This
was further noticed in Fig. 16,98 where the selectivity for
n-butane/nitrogen versus Reynolds number for the
measurements from Fig. 15 is shown. In the legend, the
same information was given as in Fig. 15. The selectivity
showed the same behaviour as the total mass transfer
coefficient of n-butane in Fig. 15. LuÈdtke et al. also
12
COEFFICIENT FOR n-BUTANE kC4
OVERALL M ASS TRANSFER
10
8
[m3(ST P)/(m2 h bar)]
6
4
2 6/16.65; 0.387
0
0 500 1000
REYNOLDS NUMBER
Fig. 15 – Overall mass transfer coefficient for n-butane kC 4 as a function of the Reynolds number for four different feed
pressures, P H . The measurements were made with 2.2 vol% n-butane in nitrogen at 295 K and a permeate pressure of 0.3
bar. In the legend, the nitrogen LN2 and n-butane permeability LC 4 are given for the investigated conditions calculated with
the extended free volume model from single gas measurements 98
VOL. 68 (3) JULY – SEPTEMBER 2009
compared the measured overall mass transfer coefficient
and the permeability of n-butane and found that for the
thicker membrane the resistance in the separation layer
was dominant.
In Fig. 17, 98 the measured overall mass transfer
coefficient of n-butane and the n-butane/nitrogen
selectivity for two different PDMS layer thicknesses are
shown as a function of the Reynolds number. It may be
seen that there exists a small difference between the
n-butane permeability, LC4 (6.9) for the pure resistance
in the separation layer and the n-butane overall mass
transfer coefficient, kC4 (5:5) (Re = 2200) calculated from
the measurement data. In the ideal case of only one
resistance in the separation layer the n-butane
permeability and the measured n-butane overall mass
transfer coefficient would be equal. For the thinner
membrane, the boundary layer resistance dominates,
resulting in a small overall mass transfer coefficient (kC4)
of approximately 14 (Re = 1500) compared to the
predicted n-butane permeability (LC 4) of 41:4 m 3 /
(m2.h.bar). For the thicker membrane the boundary layer
resistance was approximately 20% of the total resistance
and for the thinner membrane the boundary layer
resistance was approximately 75%. This increase in the
boundary layer resistance is related to the higher fluxes
through the thinner membrane. It may be seen by
comparing the measured selectivity of n-butane/nitrogen.
The selectivity is defined as the ratio of the n-butane
overall mass transfer coefficient, kC4, over the nitrogen
overall mass transfer coefficient, kN 2. For the thicker
membrane the selectivity has a value around 32 and for
the thinner membrane around 12. This difference is based
on the fact that the boundary layer resistance degrades
the separation properties of the membrane. For the thinner
membrane the part due to the boundary layer resistance
is much larger than that for the thicker membrane. In the
ideal case of resistance only in the PDMS layer, a
PH / LC4; LN2
2.5/15.19; 0.365
3.5/15.6; 0.371
4.5/16.1; 0.377
1500 2000 2500
131
 35

30
kC4/kN2 SELECTIVITY

25

20
PH / LC4; LN2
15
2.5/15.19; 0.365

10 3.5/15.6; 0.371
4.5/16; 0.377
5
6/16.65; 0.387
0
0 500 1000 1500 2000 2500

REYNOLDS NUMBER
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Fig. 16 – n-butane/nitrogen selectivity as function of the Reynolds number for four different feed pressures, P H. The selectivities
were calculated from the data shown in Fig. 15. In the legend, the nitrogen LN2 and n-butane permeability LC 4 are given for
the investigated conditions calculated with the extended free volume model from single gas measureme nts98
OVERALL MASS TRANSFER COEFFICIENT

16 45 technology is attractive for CO2 and H2S removal because

OF n-BUTANE kC4 [m3(STP)/(m2 h bar)]

OPEN SYMBOLS: MASS TRANSFER COEFFICIENT many membrane materials are permeable to these
species (enabling a high recovery of the acid gases
12 35
without significant loss of pressure in the methane
kC4/kN4 SELECTIVITY

pipeline product gases) and treatment can be

8
4 15
BLACK SYMBOLS: SELECTIVITY
0
0 500 1000
REYNOLDS NUMBER
Fig. 17 – Overall mass transfer coefficient for n-butane kC 4
and n-butane/nitrogen selectivity in dependence of the
Reynolds number for two different membrane thicknesses.
The measurements were made with 2.2 vol% n-butane in
nitrogen at 295 K and a permeate pressure of 0.3 bar. In the
legend the membrane thickness and the nitrogen LN 2 and
n-butane permeability LC 4 are given for the investigated
conditions calculated with the extended free volume model
from single gas measurements 98
selectivity of approximately 43 for the measurement
conditions would be expected for both the membranes.98
Therefore, it is worth noting that the mass transfer
coefficient is an important parameter for designing the
membrane separation modules.
Industrial Applications of Membrane for CO2
Separation
Carbon dioxide removal from natural gas (natural gas
sweetening) is mandatory to meet pipeline specifications
(e.g. down to 2 vol% in USA) since CO 2 reduces the
heating value of natural gas, is corrosive and freezes at a
relatively high temperature forming blocks of dry ice that
can clog equipment lines and damage pumps. Membrane
thickness / LC4; LN2 accomplished using the high wellhead gas pressure as
0.8/41.4; 0.977 25
4.4/6.9; 0.164 the driving force for separation. A high natural gas recovery
(~95%) can be achieved in multistage systems.
Membrane systems are typically installed for small size
applications (less than 6000 Nm 3.h –1 ) and remote
locations, since amine processes are too complicated
for small productions. Membrane and amine systems
1500 2000 2500
5 become competitive for a size of 6000-50000 Nm3.h–1,
while bigger plants are installed for offshore platforms or
for enhanced oil recovery. GS (gas separation) membrane
presents significant advantages for the offshore industry;
moreover, it is an environmental friendly alternative to
traditional amine absorption.99
Cynara-NATCO produces hollow fiber modules in
cellulose triacetate 100 and has recently provided a
membrane system (16 inch modules) for the natural gas
sweetening in an offshore platform in the Thailand
gulf (830000 Nm3.h–1), which is the biggest membrane
system for CO2 removal.101 The plant reduces the CO2
concentration from 36 to 16% (in southeast Asia a CO2
concentration of 23% can be acceptable for using the
gas in power stations).
In the field of natural gas treatment, commercially
proven membranes (NitroSep process, MTR) 102 are
beginning to be used to separate hydrocarbons from
nitrogen. These systems, using composite membranes,
allow production from high nitrogen gas reserves.
The injection of gases miscible with oil, like CO 2
and/or N2, increases the recovery rates of oil and/or gas
from a petroleum reservoir (enhanced oil recovery).
Membranes are useful for recovering CO2 from natural gas
in enhanced oil recovery applications because of the high
CO2 concentrations (typically ~50%) and high pressure
(up to 140 bar) involved in these processes.

132 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

 The other important field where membranes can
contribute is CO2 capture. The aim is to reduce CO 2
emissions into the atmosphere due to combustion of fossil
fuels, contributing to global warming. The key issue for
CO2 capture is minimizing the energy required in the overall
process (capture and sequestration). CO 2 captures in
power generation processes, that involve fossil fuels, are
divided into pre-combustion, post combustion and oxy-
fuel combustion strategies, whose detailed description
has been provided by Bernardo et al.99
Established methods for CO2 capture are absorption,
adsorption and membrane processes. Amine absorption
is at present the best available technology for post
combustion capture, with an energetic cost in the range
of 4-6 GJ.ton–1 CO2 recovered (mainly due to significant
energy consumption in the regeneration step). This option
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requires large scale equipment for the CO2 removal and
chemicals handling. It also consumes heat and results in
additional exhaust gas pressure losses, producing a
reduced thermal efficiency. In post combustion capture
CO2 must be separated from waste gases (where N2 is
the main component). Due to the low CO2 concentration
and pressure in this gas, the commercial membranes
used to separate CO2 from natural gas at high pressures
are not suited. Their use will result in a large membrane
area and in high compression costs.
Membranes based on alumina, zeolites, silica and
carbon have received considerable attention in both
amorphous and crystalline forms for separating CO2 at
high temperature.103 Materials which conduct CO32– ions
(e.g. molten Li2CO3 formed from the reaction of Li2ZrO3
with CO2) have also been studied for CO2/CH4 separation
up to 600oC.103, 104 These membranes may provide an
economically efficient, stable and robust separation
membrane in applications where excess heat / energy
are readily available to melt the carbonate.
Inorganic membranes can find application in high
temperature membrane reactors for integration in power
generation cycles with CO2 capture. Integrated H2, O2 or
CO 2 membrane separation is analysed, and it is
concluded that development of power plant concepts
including membrane technology is not yet fully explored.
Significant design optimization would be required in order
to identify efficient, feasible and environmentally sound
technical solutions. In addition, further development and
validation of performance of membranes in real
applications are needed.
Future Directions
A number of the microporous inorganic membranes
discussed in this paper show good permeation properties
for CO2 over N2 and CH4 at low temperatures, but loses
CO2 selectivity at elevated temperatures due to surface
diffusion based transport mechanism through the
membrane. These membranes also suffer from stability
problems at the desired operating conditions, and/or
economic feasibility issues. While development of current
techniques continues to move these membranes closer
to commercial application, it is also worth considering
VOL. 68 (3) JULY – SEPTEMBER 2009
innovative materials that could lead to new generation
of membranes for CO 2 separation. Some of the new
approaches in this regard are described below.
Hybrid Membranes
Modified inorganic membranes retain the rigidity and
pore morphology of the ceramic material, while the organic
component alters the ceramic membrane functionality.
It is a well-known fact that CO2 permeation increases when
there is a chemical affinity with some molecular groups
in the membrane. This has been observed for the
fluorogroup, phenyl group and carbonyl group in esters
and ketones.5, 105
The exceptional CO 2 permselectivities of fluorine
containing polyimides, as well as their stability at higher
temperatures and in harsh environments, make them
highly attractive for gas separation membranes. However,
their high cost has prevented their widespread uses in
gas separation processes. A composite membrane
comprising of a thin polyimide film coated on a strong
and stable porous support would be an ideal membrane
for economical and favourable gas separations.
In the production of membranes using sol-gel
techniques as designed to leave a particular organic group
in the membrane structure, low coverage or over-
coordination of the organic group results in a lower than
desired surface affinity. W hen previously fabricated
inorganic membranes is modified by organic reagents,
such as silanes, mass transfer into the pore and the
reactivity of those reagents results in very thin “polymer-
like” membranes covering the surface to varying
thicknesses, depending upon the silane used. These
techniques hold considerable potential, but research will
be required to further develop the fabrication techniques
required to produce membranes with monolayer coverage
of a particular organic group inside the pores.
Mixed Matrix Membranes
Many inorganic membranes are stable at high
temperatures, but the competitive adsorption process
does not work well at high temperatures. Molecular sieving
membranes have a greater potential than competitive
adsorption at high temperatures, but tailored micropores
are required to separate light gases with smaller size
differences.
Zeolites, carbon molecular sieves (CMS), and many
polymeric materials offer attractive transport properties,
but are difficult and expensive to process. Mixed matrix
composite (MMC) materials, comprised of molecular
sieving materials embedded in a polymer matrix, have
potential to provide economical and high performance
gas separation membranes if defects at the molecular
sieve/polymer interface can be eliminated. The molecular
sieving material could be zeolite or CMS. Additionally,
careful matching of the intrinsic permeability and
selectivity of the support matrix and the molecular sieve
domains is necessary. Composite organic-inorganic
membranes have become an expanding field of research
as the introduction of organic molecules in the suitable
inorganic system.106
133
 Facilitated Transport Membranes
Facilitated transport membranes (FTM) have received
a lot of attention in gas separations because they offer
higher selectivities and larger fluxes. Higher selectivity in
FTM is achieved by incorporating a carrier agent into a
membrane, which reacts reversibly with the penetrating
species. In addition to the solution-diffusion mechanism
of the polymeric membranes, FTMs also involve a
reversible complex reaction. In FTM, the permeating
species dissolves in the upstream portion of the membrane
and reacts with the carrier agent to form a complex. The
formed complex diffuses across the membrane, and then
releases the permeants on the downstream side of the
membrane, while the carrier agent is simultaneously
recovered and diffuses back to the feed side.107, 108
FTMs can be divided into three general categories:
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fixed carrier or chained carrier membranes, solvent-swollen
polymer membrane, and mobile carrier membranes or
immobilized liquid membranes (ILMs). Fixed carrier
membranes are solid polymer films into which reactive
functional groups, or complexing agents, are incorporated.
Transport in the fixed carrier membranes is limited by the
absence of mobility of the complexing agents. An ILM is
usually prepared by impregnating the liquid carrier into
the pores of a microporous support. The liquid (carrier
agent) in ILM is held in the support pores by capillary
forces. The chemical instability of the carrier agent in ILMs
limits its application for gas separations. Membrane
degradation might also occur by evaporation or drying
out of the liquid carrier agent in the gas separation
applications. Fixed carrier membranes are generally
considered more stable than ILMs because there is less
chance of carrier loss. There have been several efforts
made to overcome this membrane leaching problem, such
as the use of molten salts with very low vapour pressure,
or the use of hollow fiber contained liquid membranes.
Solvent-swollen membranes are intermediate in structure
and stability between ILMs and fixed carrier membranes.
They can be made by swelling a polymer film in a solvent
and introducing the carrier species by diffusion or by ion
exchange in the case of ionomer membranes.108
Palladium-based Membranes
Dense palladium membranes have been prepared by
depositing palladium or other metals ranging in thickness
from a submicron to a few microns on a porous support.
These Pd or metallic membranes are 100 per cent
selective to H2 from a H2 containing feed mixture because
other gases do not diffuse through the metal. The
permeation of H2 through metal membranes involves the
dissociative chemisorption of H2 on the membrane surface
followed by dissolution of the atomic hydrogen from the
surface into the bulk of the metal.106 This is followed by
atomic diffusion of dissolved hydrogen in the membrane
and desorption of hydrogen atoms as molecules. The rate
limiting step for H2 permeation is the hydrogen diffusion
through the bulk of the metal membrane. Hence, the H2
flux through the membrane is directly proportional to the
difference in the square roots of H2 pressures between
134
the feed and permeation sides of the membrane according
to Sievert’s law. The H 2 permeability of the supported
membrane is significantly higher than a single layered
Pd membrane. The supported membrane also has the
advantage of having high mechanical strength imparted
by the support. Besides Pd and its alloys, other metals,
such as tantalum, niobium and vanadium also have high
selectivities and, hence, are also candidates for the H2
selective dense membranes. The high cost of these
precious metals, lower permeabilities, brittleness and high
susceptibility to poisoning compounds are some of the
disadvantages of the precious metal membranes and have
limited their intended use. However, researchers have
overcome most of these disadvantages by depositing a
very thin layer of metal alloy on a porous support. Three
methods have generally been used to deposit thin metal
films on porous supports: electrodeless plating, chemical
vapour deposition and physical sputtering.109
Hydrotalcite Membranes
Mesoporous ceramic materials are still very attractive
for CO2 selective membranes at elevated temperatures
although these materials have low CO 2 selectivity at
higher temperatures. Nevertheless, these types of
membranes enjoy some advantages, like, these are
thermally stable materials and have the potential for
commercial availability. Additionally, the flux is higher with
mesoporous membranes, compared to microporous or
dense membranes. As mentioned earlier, transport across
mesoporous membranes is governed by the Knudsen
diffusion mechanism, and the separation efficiency
(CO2/N2 = 0.8; CO2/CH4 = 0.6) according to that mechanism
would be unacceptable for all practical purposes. In order
to improve the separation efficiency of mesoporous
membranes, the transport through the membrane should
be facilitated by the surface diffusion mechanism.
Therefore, hydrotalcites (HTs) are quite promising as
membrane materials in this regard. Structurally HTs
consist of layers containing octahedrally coordinated
bivalent cations (e.g. Mg2+, Ni2+, Co2+, Zn2+, Cu2+) and
trivalent cations (e.g. Al3+, Fe3+, Cr3+), as well as interlayer
anions (e.g. CO32–, SO42–, NO3–, Cl–, OH–, [Fe(CN)6]4–).
Some of the important works with hydrotalcite
membranes are stated to be important for future
application. Kim et al.110 utilized electrophoretic deposition
(EPD) as a new method for the preparation of hydrotalcite
(HT) thin film. The films were deposited on mesoporous
alumina substrates and on alumina substrate that has
been previously coated by conventional dip coating
technique using slurries of HT colloidal particles. The films
were shown to be permselective towards CO2. In another
work111 a vacuum suction method was used for the synthesis
of HT films and their properties were characterized using
both single and mixed gas permeation tubes as well as
by nitrogen adsorption and by SEM and XRD. The HT
films were microporous as indicated by the adsorption
data as well as by the fact that the ideal selectivities of
pair of inert gases (e.g. He, N 2 and Ar) through the
mesopore were higher than the Knudsen values. However,
TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
 the as prepared materials contained a substantial fraction
of voids and pin holes. Plugging these voids and pinholes
using a silicone coating resulted in CO2 permselective film,
which exhibited CO2/N2 and CO2/He ideal separation factor
of 34.4 and 12.4 respectively.

Perovskite Oxide Type Membranes

A perovskite is any material with the same type of
crystal structure as calcium titanium oxide (CaTiO 3).
Perovskites are of the form ABO3, where A is a lanthanide
element, B is a transition metal, and O is oxygen. The
A component and/or the B component may be doped
with other materials to enhance the stability and
performance of perovskite oxide type materials. These
ion-conductive perovskite oxide membranes have been
extensively studied for O 2 separations at elevated Fig. 18 – SEM morphology of a perovskite sample 112
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temperatures. The stability of perovskite type materials

at very high temperatures makes them a perfect
candidate towards CO2 selective membranes at elevated
temperatures. A typical SEM picture of perovskite
membrane is shown in Fig. 18.112 Some of the works
with perovskite membrane is given below.
Kusakabe et al.47 applied a porous -alumina support
for separation of CO2 with BaTiO3 membrane prepared
by the sol-gel method where BaTiO3 was synthesized
by hydrolysis of Ba(iso-OC3H7)2 and Ti(iso-OC3H7)4 and
calcination at 873 K in a N2 atmosphere. A clear BaTiO3
sol, synthesized with peptization, was coated onto a
porous -alumina support by repeating a dipping-drying-
firing procedure. They found that under a CO2 partial
pressure of 10 kPa, it adsorbed 4-6 µmol.m–2 of CO2 at
298 K and 2-3 μmol.m–2 at 773 K. The separation factor
of CO2 to N2 through the membrane was 1.12-1.2, which
was higher than the value of the Knudsen diffusion
mechanism, 0.8. These low values of separation factors
through BaTiO3 impregnated membranes were caused by
the presence of pinholes in the membrane layer. The
dynamic adsorption by gas chromatography suggested
that the CO2 molecules adsorbed on the BaTiO3 powder
were mobile at 773 K.
Their stability at elevated temperatures, low
susceptibility to poisoning by sulfur and other compounds,
and their higher CO 2 adsorption capacity at higher
temperatures make the perovskite type oxides as
attractive membrane materials for CO2 separation.113
Comparison of Different Ceramic Membranes
A comparison of different ceramic membranes is
given in Table X.
Hybrid Systems for Process Synergies
Modern membrane engineering is an important way
to implement the process intensification (PI) strategy by
innovative design and process development methods
aimed at decreasing production costs with optimum
equipment size, energy utilization and waste generation.
As has been highlighted earlier, hybrid membrane
processes are integrated processes in which the
membrane system operates in combination with another

Table X : Comparison of different ceramic membrane materials

Parameters Alumina membrane Zeolite membrane Carbon membrane Silica membrane

Gas separation Mostly as membrane Mostly as membrane Mostly as membrane Mostly as membrane
application support material material material

Selectivity and Limited selectivity and Show the least variation in both Low permeance, but high High permeances and low
permeability permeation selectivity and permeability of selectivity selectivities
any inorganic membrane type
in separations of CO2/H2, CO2/
CH4 and CO2/N2 mixtures

Thermal and Sound structural proper- High thermal and chemical High thermal and chemical Shows exceptional thermal,
chemical stability ties and chemical and stability stability chemical and sructural
hydrothermal stabilities stability in both oxidizing
and reducing environments

Mechanism of Mostly Knudsen diffusion Molecular sieving, surface Molecular sieving and some- Mostly surface diffusion
separation mechanism diffusion and combined times by a combination of
differences transport in the gas phase
(molecular sieving) and
surface diffusion of the
adsorbed molecules

VOL. 68 (3) JULY – SEPTEMBER 2009 135

 unit operation, or processes in which the basic functioning
of the membrane is joined with another physical or
chemical process in a single unit operation. A properly
designed hybrid process will balance the drawbacks of
the specific process and favourably combine their
advantages. The result will be a better separation,
contributing to a sustainable process improvement by
allowing the reduction of investment and operational costs.
Typically, membranes provide a moderately pure product
at low cost (bulk separation) that may be economically
upgraded by a subsequent process. The integration of
membranes with other separation processes, well-
established in the chemical and petrochemical industries,
such as pressure swing adsorption (PSA), was considered
in different works.114, 115 Membrane permeation can be an
effective aid in the pressurization and high pressure
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adsorption steps of a typical PSA process; the pressure
difference available from the PSA can be used for operating
the membrane incorporated into the blow down step of
the PSA cycle. Usually, the combination membranes
integrated with PSA are considered in H2 separation, while
hybrid membranes integrated with amine absorption are
applied to the CO2 separation.116
A comparison of the separation cost for the membrane
process with that for the diethanolamine (DEA) absorption
showed that the membrane process is more economical
for CO2 concentrations in the feed range of 5-40 mol%.117
When the feed contains H2S, the cost for reducing CO2
and H2S concentrations to pipeline specifications increases
with increasing H2S concentration (1000-10000 ppm). As
the membrane processes are not economically
competitive because of the high H2S concentration in the
feed, the separation cost could be significantly lowered
by using hybrid membrane processes. In such processes,
the bulk of CO2 and H2S is separated from sour natural
gas with membranes and the final purification is performed
by means of suitable gas absorption processes.118 A hybrid
system (Cynara membranes integrated with amine
absorption) has been operating since 1994 in Mallet
(Texas, USA) to perform the bulk removal of CO2 from
associated gas (90% CO2 and heavy hydrocarbons) before
downstream treament. The membrane system offered a
30% reduction in operating cost when compared with a
methyl diethanolamine (MDEA) system and significantly
reduced the size of the subsequent operations.119
In the process industry the final choice of a separation
process is the result of a balance between the economics,
the desired purity and recovery of the product and other
conditions and restrictions, such as the desired capacity
and the composition of the feed and the possibility of
integration with other processes.
Technology Forecast
A great deal of research is still to be carried out on
improved membrane materials of ceramics, polymers and
a combination thereof, membrane configuration and
preparation routes for gas separation, The essential focus
for research and development is on developing robust
membranes in order to meet the key criteria of reliability
136
and durability for industrial applications. Ceramic
membranes, when industrially available, can find
application at high temperature, or in new applications
involving hydrocarbon vapours, contributing to the success
of membrane technology. Technological advancement
towards modelling of membrane processes (integrated
process simulator to model complete hybrid process,
predictive membrane and module performance models)
can be very useful to fulfil the lack of general design
methodologies and detailed process know-how. With
the development of new technologies and process
concepts, new membrane applications will emerge.
Therefore, it has been shown that ceramic membranes
have tremendous potential to emerge as a successful
technology to meet the requirement in future.
Summary
This review summarizes previous studies conducted
and recent accomplishment by different researchers on
various CO2 selective ceramic membranes available in
literature with respect to their stability, effect of operational
parameters on their performance, relationship of their
structure to their permeation properties, and their
observed transport mechanisms. Different membrane
materials were also described showing high CO 2
absorbing capacity and stability at elevated temperatures,
coupled with their reasonable cost. So advanced research
should continue to stimulate the scientists to explore
them as promising membrane materials for CO 2
separation at higher temperatures. Several other issues,
still need to be addressed, include: further improvements
in the membrane flux by reducing the thickness of the
membrane without sacrificing gas separation, automating
the fabrication process to increase coating uniformity and
to reduce the cost of manufacturing, and increasing the
membrane area by fabricating larger supported
nanoporous carbon membranes (SNPCMs) in bundles
with multiple tubes.
Furthermore, the review describes the future direction
for research and development for CO 2 selective
membranes. That is, hybrid organic-inorganic membranes
have become an expanding field of research as the
introduction of organic molecules can improve the
characteristics of a matrix. Hydrotalcite type materials,
perovskite type oxides and certain lithium compounds
are also suggested as suitable candidate materials for
high temperature CO2 selective membranes.
To the end of this review, the applications of process
synergies or integration of the membrane together with
other separation techniques in hybrid processes have
been described. Nevertheless, the potential of hybrid
separation processes in industrial scale was not fully
exploited because of the lack of general design metho-
dologies and detailed process know-how. In this regard,
modelling of membrane processes (integrated process
simulator to model complete hybrid process, predictive
membrane and module performance models) can be
recommended for further study. Moreover, a great deal of
investigation is needed to improve membrane materials
TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
 for gas separation, as materials science and analyses
are critical issues.
Better engineering (design of super molecular
membrane morphologies and economical modules)
together with molecular dynamics studies, leading to better
insights into the separation processes are equally critical
to the development of molecularly engineered chemical
structures with high fluxes at high selectivity.
Acknowledgement : The authors acknowledge the Universiti
Teknologi PETRONAS, Malaysia for this work.
References
1. C. M. White, B. R. Strazisar, E. J. Granite, J. S. Hoffman and
H. W. Pennline. J. Air Waste Manage. Assoc., 53, 645-715
(2003).
2. A. L. Kohl and R. B. Nielsen, Gas Purification, 5th edition,
Downloaded by [University of California, San Diego] at 22:35 03 January 2016
Gulf Publishing Company, Texas, USA (1997).
3. C. David, B. Kellogg and S. Pankaj, Soc. Petr. Eng. Conf.,
SPE Paper 84252, p. 3 (2003).
4. H. Lin, E. Van Wagner, R. Raharjo, B. D. Freeman and I.
Roman, Adv. Mater., 18, 39-44 (2006).
5. S. A. Stern, J. Membr. Sci., 94, 1-65 (1994).
6. D. Shekhawat, R. D. Luebke and W. H. Pennline, A Review of
Carbon Dioxide Selective Membranes, National Energy
Technology Laboratory, Morgantown, USA (2003).
7. W. J. Koros and G. K. Fleming, J. Membr. Sci., 83, 1-80
(1993).
8. P. Pandey and R. S. Chauhan. Prog. Polym. Sci., 26, 853-93
(2001).
9. A. Javaid, Chem. Eng. J., 112, 219-26 (2005).
10. R. E. Kesting and A. K. Fritzsche, Polymeric Gas Separation
Membranes, John Wiley and Sons, New York, USA (1993).
11. L. M. Robeson, J. Membr. Sci., 62, 165-85 (1991).
12. J. Caro, M. Noack, P. Kolsch and R. Schafer, Micropor.
Mesopor. Mater., 38, 3-24 (2000).
13. R. W. Baker, Membrane Separation Systems, Recent
Developments and Future Direc tions, Noyes Data
Corporation, Park Ridge, New Jersey, USA (1991).
14. R. A. Terpstra, J. P. G. M. Van Eijk and F. K. Feenstra, US
Patent No. 5,707,584 (1998).
15. J. J. Hammel, US Patent No. 4,853,001 (1989).
16. J. D. Way and D. L. Roberts, Sep. Sci. Technol., 27, 29-41
(1992).
17. M. Bhandarkar, A. B. Shelekhin, A. G. Dixon and Y. H. Ma, J.
Membr. Sci., 75, 221-31 (1992).
18. V. Shindo, T. Hakuta, H. Yoeshitome and H. Inouei, J. Chem.
Eng. Jpn., 16, 120-26 (1983).
19. H. P. Hsieh, Catal. Rev. Sci. Eng., 33, 1-2 (1991).
20. K. H. Lee and Y. M. Kim, Key Eng. Mater., 17, 61-62 (1991).
21. J. E. Koresh and A. Sofer, Sep. Sci. Technol., 18, 723-34
(1983).
22. J. E. Koresh and A. Soffer, J. Chem. Soc., Faraday Trans.,
82, 2057-64 (1986).
23. V. M. Linkov, R. D. Sanderson and E. P. Jacobs, Proc. 34th
IUPAC Symp. Macromol., 7, 56 (1992).
24. M. Mulder, Basic Principles of Membrane Technology, Kluwer
Academic, Dordrecht, Netherlands (1996).
25. J. de Jong, N. E. Benes, G. H. Koops and M. Wessling, J.
Membr. Sci., 239, 265-69 (2004).
26. K. Li, X. Tan and Y. Liu, J. Membr. Sci., 272, 1-5 (2006).
27. C. C. Wei, O. Y. Chen, Y. Liu and K. Li, J. Membr. Sci., 320,
191-97 (2008).
VOL. 68 (3) JULY – SEPTEMBER 2009
28. Q. M. Nguyen and T. Takahashi, Science and Technology of
Ceramic Fuel Cells, Elsevier, Amsterdam, Netherlands
(1995).
29. W. Gopel, T. A. Jones, M. Kleitz, I. Lundstrom and T. Seiyama,
Sensors: A Comprehensive Survey, Chemical and Biochemical
Sensors, New York, USA (1991).
30. H. L. Tuller, J. Schoonman and H. Riess, Oxygen Ion and
Mixed Conductors and Their Technological Applications,
Kluwer Academic, Dordrecht, Netherlands (2000).
31. R. W. Baker, Membrane Technology and Applications, 2nd
edition, Membrane Technology and Research, California, USA
(2004).
32. H. A. Meinema, R. W. J. Dirrix, H. W. Brinkman, R. A. Terpstra,
J. Jekerle and P. H. Kösters, High Perform. Ceram., 54, 86-
90 (2005).
33. A. J. Burggraaf and K. Keizer, “Synthesis of Inorganic
Membranes”, pp. 10-63 in: Inorganic Membranes: Synthesis,
Characteristics and Applications, Ed. R. R. Bhave, Van
Nostrand Reinhold, New York, USA (1991).
34. J. Schaep, C. Vandecasteele, B. Peeters, J. Luyten, C.
Dotremont and D. Roels, J. Membr. Sci., 163, 229-37 (1999).
35. R. J. R. Uhlhorn, K. Keizer and A. J. Burggraaf, J. Membr.
Sci., 46, 2225-41 (1989).
36. Y. K. Cho, K. Han and K. H. Lee, J. Membr. Sci., 104, 219-30
(1995).
37. B. S. Kang and S. H. Hyun, J. Mater. Sci., 34, 1391-98 (1999).
38. K. Kusakabe, S. Yoneshige, A. Murata and S. Morooka, J.
Membr. Sci., 116, 39-46 (1996).
39. Y. Hasegawa, K. Watanabe, K. Kusakabe and S. Morooka,
Sep. Purif. Technol., 22, 319-25 (2001).
40. L. J. P. van den Broeke, W. J. W. Bakker, F. Kapteijn and J. A.
Moulijn, Chem. Eng. Sci., 54, 245-58 (1999).
41. K. Aoki, K. Kusakabe and S. Morooka, Ind. Eng. Chem., 39,
2245-51 (2000).
42. J. Dong and Y. S. Lin, Ind. Eng. Chem., 37, 2404-2409 (1998).
43. M. P. Bernal, E. Piera, J. Coronas, M. Menendez and J.
Santamaria, Catal. Today, 56, 221-27 (2000).
44. J. C. Poshusta, R. D. Noble and J. L. Falconer, J. Membr.
Sci., 186, 25-40 (2001).
45. S. Alfaro and M. A. Valenzuela, AZojomo, J. Mater. Online,
Vol. 2, DOI: 10.2240/azojomo0187, March (2006).
46. M. Niwa, H. Ohya, Y. Tanaka, N. Yoshikawa, K. Matsumoto
and Y. Negishi, J. Membr. Sci., 39, 301-14 (1988).
47. K. Kusakabe, Z. Y. Li, H. Maeda and S. Morooka, J. Membr.
Sci., 103, 175-80 (1995).
48. W. J. W. Bakker, L. J. P. van den Broeke, F. Kapteijn and J. A.
Moulijn, AIChE J., 43, 2203-14 (1997).
49. K. Kusakabe, M. Yamamoto and S. Morooka, J. Membr. Sci.,
149, 59-67 (1998).
50. J. C. Poshusta, V. A. Tuan, J. L. Falconer and R. D. Noble,
Ind. Eng. Chem. Res., 37, 3924-29 (1998).
51. M. C. Lovallo, A. Gouzinis and M. Tsapatsis, AIChE J., 44,
1903-13 (1998).
52. F. Jareman and J. Hedlund, Micropor. Mesopor. Mater., 82,
201-207 (2005).
53. K. Kusakabe, T. Kuroda, K. Uchino, Y. Hasegawa and S.
Morooka, AIChE J., 45, 1220-26 (1999).
54. L. J. P. Van den Broeke, W. J. W. Bakker, F. Kapteijn and J. A.
Moulijn, Chem. Eng. Sci., 54, 245-58 (1999).
55. J. C. Poshusta, V. A. Tuan, E. A. Pape, R. D. Noble and J. L.
Falconer, AIChE J., 46, 779-89 (2000).
56. S. Li, J. G. Martinek, J. L. Falconer R. D. Noble and T. Q.
Gardner, Ind. Eng. Chem. Res., 44, 3220-28 (2005).
57. Y. Cui, H. Kita and K. I. Okamoto, J. Mater. Chem., 14, 924-32
(2004).
137
 58. S. Li, J. G. Martinek, J. L. Falconer, R. D. Noble and T. Q.
Gardner, Ind. Eng. Chem. Res., 44, 3220-28 (2005).
59. S. Li, J. L. Falconer and R. D. Noble, Adv. Mater., 18, 2601-
2603 (2006).
60. T. Tomita, K. Nakayama and H. Sakai, Micropor. Mesopor.
Mater., 68, 71-75 (2004).
61. J. van den Bergh, W. Zhu, J. C. Groen, F. Kapteijn, J. A.
Moulijn, K. Yajima, K. Nakayama, T. Tomita and S. Yoshida,
Stud. Surf. Sci. Catal., 170, 1021-27 (2007).
62. M. Hong, S. Li, H. F. Funke, J. L. Falconer and R. D. Noble,
Micropor. Mesopor. Mater., 106, 140-46 (2007).
63. S. Li, J. L. Falconer and R. D. Noble, J. Membr. Sci., 241,
121-35 (2004).
64. I. G. Giannakopoulos, D. Kouzoudis, C. A. Grimes and V.
Nikolakis. Adv. Funct. Mater., 15, 1165-70 (2005).
65. M. A. Carreon, S. Li, J. L. Falconer and R. D. Noble, J. Am.
Chem. Soc., 130, 5412-13 (2008).
Downloaded by [University of California, San Diego] at 22:35 03 January 2016
66. J. E. Koresh and A. Soffer, J. Chem. Soc., 76, 2457-71
(1980).
67. J. E. Koresh and A. Sofer, Sep. Sci. Tech., 18, 723-34 (1983).
68. A. B. Fuertes and T. A. Centeno, Micropor. Mesopor. Mater.,
26, 23-26 (1998).
69. A. B. Fuertes, J. Membr. Sci., 177, 9-16 (2000).
70. A. B. Fuertes, D. M. Nevskaia and T. A. Centeno, Micropor.
Mesopor. Mater., 33, 115-25 (1999).
71. A. F. Ismail and L. I. B. David, J. Membr. Sci., 193, 1-18
(2001).
72. J. I. Hayashi, H. Mizuta, M. Yamamoto, K. Kusakabe and S.
Morooka, J. Membr. Sci., 124, 243-51 (1997).
73. A. B. Fuertes and T. A. Centeno, J. Membr. Sci., 144, 105-11
(1998).
74. T. A. Centeno and A. B. Fuertes, J. Membr. Sci., 160, 201-11
(1999).
75. T. A. Centeno and A. B. Fuertes, Sep. Purif. Tech., 25, 379-
84 (2001).
76. Y. Kusuki, H. Shimazaki, N. Tanihara, S. Nakanishi and T.
Yoshinaga, J. Membr. Sci., 134, 245-53 (1997).
77. H. Wang, L. Zhang and G. R. Gavalas, J. Membr. Sci., 177,
25-31 (2000).
78. H. Wang and G. R. Gavalas, J. Membr. Sci., 176, 75-85
(2000).
79. N. Tanihara, H. Shimazaki, Y. Hirayama, S. Nakanishi, T.
Yoshinaga and Y. Kusuki, J. Membr. Sci., 160, 179-86
(1999).
80. M. Ogawa and Y. Nakano, J. Membr. Sci., 162, 189-98
(1999).
81. M. Ogawa and Y. Nakano, J. Membr. Sci., 173, 123-32
(2000).
82. J. I. Hayashi, M. Yamamoto, K. Kusakabe and S. Morooka,
Ind. Eng. Chem. Res., 36, 2134-40 (1997).
83. R. J. R. Uhlhorn, M. H. B. J. Huis In’t Veld, K. Keizer and A. J.
Burggraaf, J. Mater. Sci. Lett., 8, 1135-38 (1989).
84. K. Kusakabe, S. Sakamoto, T. Saie and S. Morooka, Sep.
Purif. Tech., 16, 139-46 (1999).
85. M. J. Munoz-Aguado and M. Gregorkiewitz, J. Membr. Sci.,
111, 7-18 (1996).
86. C. A. Cooper and Y. S. Lin, J. Membr. Sci., 195, 35-50 (2002).
87. A. B. Shelekhin, A. G. Dixon and Y. H. Ma, J. Membr. Sci., 75,
233-44 (1992).
88. R. M. De Vos and H. Verweij, J. Membr. Sci., 143, 37-51
(1998).
138
89. N. K. Raman and C. J. Brinker, J. Membr. Sci., 105, 273-79
(1995).
90. C. Y. Tsai, S. Y. Tam, Y. Lu and C. J. Brinker, J. Membr. Sci.,
169, 255-68 (2000).
91. K. C. McCarley and J. D. Way, Sep. Purif. Tech., 25, 195-210
(2001).
92. M. Asaeda and S. Yamasaki, Sep. Purif. Tech., 25, 151-59
(2001).
93. J. Karger and D. M. Ruthven, Diffusion in Zeolites and Other
Microporous Solids, Wiley, New York, USA (1992).
94. E. A. Mason and A. P. Malinauskas, Gas Transport in Porous
Media: The Dusty Gas Model, Elsevier, Amsterdam,
Netherlands (1983).
95. M. Pakizeh, M. R. Omidkhah and A. Zarringhalam. Int. J.
Hydrog. Eng., 32, 2032-42 (2007).
96. J. M. Miranda and J. B. L. M. Campos, J. Membr. Sci., 188,
49-59 (2001).
97. K. Li, J. Kong and X. Tan, Chem. Eng. Sci., 55, 5579-88
(2000).
98. O. LuÈdtke, R. D. Behling and K. Ohlrogge, J. Membr. Sci.,
146, 145-57 (1998).
99. P. Bernardo, E. Drioli and G. Golemme, Ind. Eng. Chem. Res.,
DOI: 10.1021/ie8019032.
100. R. Kelly and M. Cynara, US Patent No. 4,659,343 (1987).
101. A. Callison and G. Davidson, Oil Gas J., 105, 56-65 (2007).
102. P. Hale and K. Lokhandwala, Advances in Membrane
Materials Provide New Solutions in the Gas Business ,
www.mtrinc.com/publications.
103. Y. S. Lin, Sep. Purif. Technol., 25, 39-55 (2001).
104. H. Kawamura, T. Yamaguchi, B. N. Nair, K. Nakagawa and S.
Nakao, J. Chem. Eng. Jpn., 38, 322-28 (2005).
105. M. Smaihi, T. Jermoumi, J. Marignan and R. D. Noble, J. Membr.
Sci., 116, 211-20 (1996).
106. C. M. Zimmerman, A. Singh and W. J. Koros, J. Membr. Sci.,
137, 145-54 (1997).
107. J. D. Way and R. D. Noble, pp. 833-66 in: Facilitated Transport
in Membrane, Handbook, Van Nostrand Reinhold, New York,
USA (1992).
108. H. P. Hsieh, pp. 1-13 in: Membrane and Membrane Processes
in Inorganic Membranes for Separation and Reaction,
Elsevier, Amsterdam, Netherlands (1996).
109. Y. S. Lin, Sep. Purif. Tech., 25, 34-55 (2001).
110. T. W. Kim, M. Sahimi and T. T. Tsotis, Ind. Eng. Chem. Res.,
47, 9127-32 (2008).
111. T. W. Kim, M. Sahimi and T. T. Tsotis, Ind. Eng. Chem. Res.,
48, 5794-5801 (2009).
112. U. Balachandran and B. Ma, J. Solid State Electrochem., 10,
617-24 (2006).
113. J. M. D. Tascon and L. G. Tejuca, J. Chem. Soc. Faraday
Trans. I, 77, 591-602 (1981).
114. M. H. Hassan, J. D. Way, P. M. Thoen and A. C. Dillon, J.
Membr. Sci., 104, 27-42 (1995).
115. B. K. Sea, K. Kusakabe and S. Morooka, J. Membr. Sci.,
130, 41-52 (1997).
116. K. J. Doshi and W. B. Dolan, US Patent No. 5,411,721 (1995).
117. I. A. A. C. Esteves and J. P. B. Mota, Ind. Eng. Chem. Res.,
46, 5723-33 (2007).
118. B. D. Bhide, A. Voskericyan and A. Stem, J. Membr. Sci.,
140, 27-49 (1998).
119. G. Blizzard, G. Parro and K. Hornback, Oil Gas J., 103, 48-
53 (2005).
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