4638 Ind. Eng. Chem. Res.

2009, 48, 4638–4663

Membrane Gas Separation: A Review/State of the Art

P. Bernardo,† E. Drioli,*,†,‡ and G. Golemme†,‡
National Research Council-Institute for Membrane Technology (ITM-CNR), Via Pietro Bucci, c/o UniVersity
of Calabria, cubo 17/C, 87030 Rende, Italy, and UniVersity of Calabria, Department of Chemical Engineering
and Materials and INSTM Consortium, cubo 45/A, Via Pietro Bucci, 87036 Rende, Italy

In the last years membrane processes for gas separation are gaining a larger acceptance in industry and in the
market are competing with consolidated operations such as pressure swing absorption and cryogenic distillation.
The key for new applications of membranes in challenging and harsh environments (e.g., petrochemistry) is
the development of new tough, high performance materials. The modular nature of membrane operations is
intrinsically fit for process intensification, and this versatility might be a decisive factor to impose membrane
processes in most gas separation fields, in a similar way as today membranes represent the main technology
for water treatment. This review highlights the most promising areas of research in gas separation, by
considering the materials for membranes, the industrial applications of membrane gas separations, and finally
the opportunities for the integration of membrane gas separation units in hybrid systems for the intensification
of processes.

1. Introduction scale of membrane GS technology in year 2020 to be five times

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 but also equipment size, energy utilization, and
waste generation.1 Membrane science and technology are
recognized today as powerful tools in solving some important
global problems, developing new industrial processes needed
for a sustainable industrial growth. In seawater desalination,
membrane operations or their combination in integrated systems
are already a successful approach for solving the situation of
freshwater demand in many regions of the world, at lower costs
and minimum environmental impact. Membranes are a factor
of 10 times more energetically efficient than thermal options
for water desalination.2
The major production cycles consume as much as 40-50%
of the energy used just for separations, often carried out by
inefficient thermally driven separation processes.
Membrane gas separation (GS) is a pressure-driven process
with different industrial applications that represent only a small
fraction of the potential applications in refineries and chemical
industries. Since 1980, when the serial production of commercial
polymeric membrane was implemented, membrane GS has
rapidly become a competitive separation technology. Differently
from conventional separation unit operations (e.g., cryogenic
distillation and adsorption processes), membrane GS does not
require a phase change. Moreover, the absence of moving parts
makes GS systems particularly suited for use in remote locations
where reliability is critical; in addition, the small footprint makes
them very attractive for remote applications such as offshore
gas-processing platforms.
The use of membranes in separation processes is growing at
a slow but steady rate.3 Baker in 2002 estimated the market
* To whom correspondence should be addressed. E-mail: e.drioli@
itm.cnr.it. Tel.: +39 0984 492029. Fax: +39 0984 402103.
†
National Research Council-Institute for Membrane Technology.
‡
University of Calabria.
10.1021/ie8019032 CCC: $40.75  2009 American Chemical Society
Published on Web 04/22/2009
of that of year 2000.3 It is expected that membrane GS will
play an increasingly important role in reducing the environ-
mental impact and costs of industrial processes,2 particularly
in the present scenario in which, although energy cost is volatile
(oil price is below $50 per barrel after a maximum of $147 last
summer), the global hydrocarbon reservoirs are destined to
reduce dramatically during this century.
There are many opportunities to extend markets for membrane
GS. In some cases, the membrane materials, membrane con-
figuration, and preparation routes are inadequate to fully exploit
these new fields. A broad range of materials was investigated
and different improvements were achieved by the time in this
field. Today, much of the research work is being addressed to
the investigation of new materials and to the development of
new membrane structures that exhibit both higher selectivity
and permeability to specific gases.
This review addresses current state-of-the art materials and
the major efforts in the development in the membrane GS field
at Research Institutions and major involved Companies.
2. Membrane GS Material Science Progress
The choice of a membrane material for GS applications is
based on specific physical and chemical properties, since these
materials should be tailored in an advanced way to separate
particular gas mixtures. Moreover, robust (i.e., long-term and
stable) materials are required to be applied in a membrane GS
process.
The GS properties of membranes depend upon:
• the material (permeability, separation factors),
• the membrane structure and thickness (permeance),
• the membrane configuration (e.g., flat, hollow fiber) and
• the module and system design.
Both membrane’s permeability and selectivity influence the
economics of a GS membrane process. Permeability is the rate
at which any compound permeates through a membrane; it

depends upon a thermodynamic factor (partitioning of species
between feed phase and membrane phase) and a kinetic factor
(e.g., diffusion in a dense membrane or surface diffusion in a
microporous membrane). The selectivity is the ability of a
membrane to accomplish a given separation (relative perme-
ability of the membrane for the feed species). Selectivity is a
key parameter to achieve high product purity at high recoveries.
Membrane GS has the potential to grow enormously if more
selective membranes will become available.
Process design aspects for membrane GS were discussed
recently in detail by Baker:4 different system configurations were
described from an industrial point of view, together with the
more suitable membrane system, depending on the selectivity
of the membrane and on the target performance of the process
considered. In multistage membrane systems there is a trade-
off between permeate composition and permeate pressure and
therefore, recompression costs.
GS commercial modules employ generally organic polymers
as asymmetric nonporous membranes based on solution-
diffusion transport mechanism. Both gas separation and vapor
permeation membrane processes are mostly based on the same
mechanism: sorption of the permeant into the membrane,
permeation by diffusion through the membrane, desorption at
the low pressure side of the membrane.
An important polymer feature for preparing GS membranes
is its processability into hollow fiber membranes (“spinnability”).
Hollow fiber modules (each module contains thousands of fibers)
are of interest for large-scale industrial applications, due to the
high membrane area to module volume ratio (>1000 m2/m3)
which results in high productivity per volume unit and cost-
efficient production.5 Examples of such membranes are PRISM
(Air Products) and MEDAL (Air Liquide).
Polymers cannot withstand high temperatures and aggressive
chemical environments; moreover, when applied in petrochemi-
cal plants, refineries, and natural gas treatment, heavy hydro-
carbons in feed gas streams can be a problem, particularly in
hollow fiber modules. Many polymers can be swollen or
plasticized when exposed to hydrocarbons or CO2 with high
partial pressure, even in low concentrations: their separation
capabilities can be dramatically reduced or the membranes
irreparably damaged. Therefore, pretreatment selection and
condensate handling are critical decision factors for a proper
operation of GS modules.
Typically, polymeric membranes show high selectivities and
low throughput when compared to porous materials, due to their
low free-volume. Polymeric membranes generally undergo a
trade-off limitation between permeability and selectivity:6 as
selectivity increases, permeability decreases, and vice versa.
Robeson,6 collecting a large number of permeation data for
different polymeric membranes, showed as for small gaseous
molecules (e.g., O2, N2, CO2, and CH4) a superior limit (upper
bound) exists in a selectivity/permeability diagram. The presence
of an upper bound can be theoretically rationalized on the basis
of the transition state theory.7 Chain stiffness and interchain
separation increases are recognized as ways to systematically
improve separation performance until the interchain separation
becomes large enough that the polymer segmental motion no
longer controls penetrant diffusion. Unless significant enhance-
ment in solubility selectivity could be achieved, the upper bound
would represent the asymptotic end point in the performance
of polymeric membranes whose separation properties are related
to solution-diffusion transport mechanisms. To achieve higher
selectivity/permeability combinations, materials that do not obey
these simple rules would be required.
Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009 4639
Table 1. Most Important Glassy and Rubbery Polymers Used in
Industrial Membrane GS
rubbery polymers glassy polymers
poly(dimethylsiloxane) cellulose acetate
ethylene oxide/propylene oxide - amide polyperfluorodioxoles
copolymers
polycarbonates
polyimides
poly(phenylene oxide)
polysulfone
The development of inorganic membranes (e.g., silica,
zeolites, etc.) and carbon -based molecular sieves is particularly
interesting because they can withstand aggressive chemicals as
well as high temperatures. Also these materials present draw-
backs: high cost, modest reproducibility, brittleness, low
membrane area to module volume ratio, low permeability in
the case of highly selective dense membranes (e.g., metal oxides
at temperatures below 400 °C) and difficult sealing at high
temperatures (greater than 600 °C).
The design of new polymers with enhanced selectivity offers
slow progress. Existing challenges of low selectivity and
permeability in polymer membranes are being addressed with
some degree of success with advanced materials. Two types of
nanoengineered materials have widely been studied also in terms
of their high performance in presence of aggressive agents:
cross-linked polymers and mixed-matrix materials.8
A better understanding of the transport mechanism of gases
in polymers on a molecular level is needed to develop also new
materials. There is an increasing interest in the predictive power
of the computational methods to calculate gas diffusion coef-
ficients and solubilities in polymeric membranes. Computer
simulation is widely used for the analysis of the molecular
structure of amorphous and semicrystalline polymers and the
diffusion of small gas molecules through these materials.9-11
First relatively simple flexible chain polymers (e.g., polydim-
ethylsiloxane and poly(isobutylene), poly(ethylene) and poly(pro-
pylene)) were studied to obtain qualitative information about
relations between transport mechanisms and structural proper-
ties, later the focus shifted also to stiff-chain and other complex
polymers (polyelectrolytes or catalytically active polymers) and
toward a more quantitative approach for the characterization of
structure property relations (e.g., relationships between free-
volume and gas transport properties). Molecular dynamics (MD)
simulations are successful only when detailed atomistic models
are used for both the polymer matrix and the gas molecules,
and if the thermal vibrations of the polymer matrix are taken
into consideration.12
2.1. Polymers. Despite the large number of polymeric
materials investigated and developed for GS applications, the
number of polymers used in commercial system is still limited.13
The main rubbery and glassy polymers employed for GS
membranes are listed in Table 1.
Within a polymer membrane, pores and channels have a wide
range of sizes and topologies. Polymer free-volume, the fraction
of the volume not occupied by the electronic clouds of the
polymer, plays an important role in the transport properties of
low molecular weight species and gases. Not only the overall
amount of free-volume, but also the distribution of the effective
micropore size if the free-volume elements are interconnected,
is likely to have a significant influence on polymer properties.
Some experimental techniques (probe methods such as e.g.,
Positron Annihilation Lifetime Spectroscopy, Inverse Gas
Chromatography, and 129Xe NMR) are available for determining
the average radius (1-10 Å) and the size distribution of the
4640 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009
free-volume elements.14 Atomistic modeling can only explain
the topology and structure of free-volume elements in polymers.
An amorphous polymer kept above its glass transition
temperature (Tg) is in a rubbery state. It presents a relatively
large amount of free-volume, owing to transient voids between
the highly mobile polymer chains. When the temperature is
lowered below its Tg, the polymer behaves as a rigid glass: the
fractional free-volume decreases, resulting in insufficient space
for large-scale co-operative movements of the polymer backbone.
Typically, rubbery polymers present high permeabilities and
their selectivity is mainly influenced by differences in the
condensability of the gas species. When applied to separate an
organic vapor from nitrogen, rubbery membranes preferentially
permeate the organic molecules. In this area, poly(organosilox-
anes) were studied in detail because of the vast utility of
polydimethylsiloxane (PDMS), which has high permeability
coefficients, owing to its large free-volume, and high selectivities
for condensable gases. Silicone rubber is extremely permeable
and has adequate vapor/inert gas selectivities for most applica-
tions; composite membranes of silicone rubber are used in
almost all of the installed vapor separation systems.15
Almost all industrial membrane GS processes utilize glassy
polymers because of high gas selectivity and good mechanical
properties. Usually in glassy polymers the more permeable
species are those with low molecular diameter and selectivity
is due to differences in molecular dimension. Usually, the glassy
state is characterized by a relatively small fraction of free-
volume. A larger amount of free-volume (up to 20%) can be
“frozen-in” by cooling or by a rapid removal of a solvent in
some polymers with stiff molecular structures. These voids are
not interconnected, and a low accessible surface area can be
measured by gas adsorption. Medium to high free-volume glassy
polymers (e.g., polyimides, polyphenyleneoxides, etc.) are used
to produce membranes since the voids aid the transport of gas
or liquid through the material.
Polyimides (PI) are rigid, high-melting point, high Tg and
thermally stable polymers obtained by polycondensation reac-
tions of dianhydrides with diamines.16 The polymer separation
properties can be tailored by using different type of dianhydrides
and diamines. The introduction of -C(CF3)2- groups is believed
to increase the chain stiffness which in turn reduces the
intrasegmental mobility, and reduces and limits the degree of
chain packing by increasing the free-volume, serving as mo-
lecular spacers and chain stiffeners in the polymer. As a
consequence, aromatic polyimides that contain -C(CF3)2-
groups tend to have higher CO2/CH4 selectivities. However,
fluorinated polyimides showed the tendency to plasticization
or physical aging.13 Postsynthesis modification by H+ ion beam
irradiation was reported for polyimide (Matrimid)-ceramic
composite membranes.17 Following irradiation at high ion
fluencessthe number of ions per unit membrane surface (H+/
cm2)sdue to an increase in permeability for different gases (e.g.,
He, CO2, O2, and N2), the Matrimid approached the 1991
Robeson’s upper-bound. The small molecules (e.g., He and O2)
exhibited larger increase, resulting in an overall increase in
selectivity for most gas pairs (e.g., He/N2, He/CH4, CO2/CH4,
and O2/N2). Cross-linking appeared to dominate the modification
of microstructure at the lowest irradiation ion fluence, while
the formation of small molecular size defects became increas-
ingly important at higher ion fluence. H+ ion beam irradiation
reduced the presence of polar carbonyl group of Matrimid,
which might result in the decrease in sorption of CO2 and in
smaller increase in CO2 permeability relative to other small
molecules.
Table 2. Fractional Free-Volume (FFV) and Permeation Properties
of “Very High Free-Volume” Polymers
O2/N2
O2 permeability selectivity
polymer FFV (%) (Barrer) (-) reference
PTMSP 32-34 6100 1.8 23
PMP 28 2700 2.0 24
Teflon AF 2400 33 1600 2.0 25
PIM-1 22-24a 370 4.0 26
PIM-7 190 4.5 26
a
FFV accessible to helium, from the PIM-1 density and the PIM-1
framework density.27
PEEK-WC is a phenolphthalein based poly(etheretherketone),
having a lactone group sticking out of the backbone. The good
thermal and mechanical properties of the semicrystalline PEEK
is preserved, the polymer is amorphous and therefore soluble
in chlorohydrocarbons, amides, and ethers. Therefore, it is well
suitable for the preparation of polymeric membranes by phase
separation techniques. CO2/N2 and O2/N2 selectivity of 33 and
6, respectively, comparable to typical commercial membranes,
but at a slightly lower permeance (2.3 × 10-11 m3 m-2 s-1 Pa-1
for CO2 and 4.3 × 10-12 m3 m-2 s-1 Pa-1 for O2) than typical
commercial membranes, like polyimide composites, were
measured for asymmetric PEEK-WC membranes prepared by
the dry-phase inversion method.18
Some interesting cases of the few “very high free-volume”
polymers are the polyalkynes poly(1-trimethylsilyl-1-propyne)
(PTMSP) and poly(4-methyl-2-pentyne) (PMP), and the per-
fluoropolymer Teflon AF 2400 (obtained by copolymerization
of tetrafluoroethylene and perfluoro-2,2-dimethyl-1,3-dioxole).19
These high Tg materials can be classified as microporous: they
show a high surface area in N2 adsorption experiments (BET),
their free-volume is interconnected20 and, therefore, they show
extremely high gas permeabilities, which can be 2-3 orders of
magnitude higher than those measured for conventional high
free-volume polymers (Table 2). As for nanoporous solids, it
is believed that these large free-volume elements (0.68 nm
radius, as determined by PALS in PTMSP21 and PMP22), about
twice the size of free-volume elements in conventional glassy
polymers, act as sorption sites that can be occupied by
condensable gases, hindering the passage for smaller molecules.
PTMSP was first described by Masuda28 and, owing to its
outstanding gas permeability and also vapor/gas selectivity, it
was the focus of considerable fundamental and applied research
for membrane GS.23 Merkel et al.29 reported a n-C4H10/CH4
mixed gas selectivity of 35 in PTMSP membranes, which is
the highest value reported for this gas pair. PTMSP and PMP
are even more permeable and more selective to condensable
vapors than silicone rubber, the industry benchmark polymer
for vapor/gas separation. However, the practical utility of
PTMSP is limited by a fast physical aging (gradual relaxation
of nonequilibrium excess free-volume in glassy polymers) and
also by its solubility in many organic compounds which results
in potential membrane dissolution in process streams of greatest
interest. Some studies were carried out to address the PTMSP
aging: Jia et al.30 cross-linked PTMSP with bis azides to stabilize
the large excess free-volume elements and observed an improved
physical stability, but reduced O2 and N2 permeability. Freeman
et al.31 observed a strong enhancement of PTMSP chemical
resistance by cross-linking (cross-linked PTMSP becomes
insoluble in common PTMSP solvents such as toluene and
cyclohexane). The initial permeability of the cross-linked
PTMSP membranes decreased when compared to un-cross-
linked PTMSP due to free-volume reduction; an increase in the

Figure 1. Repeat units of glassy and amorphous perfluoropolymers used in the preparation of GS membranes. Teflon AF 2400: x ) 87, Tg ) 240 °C. Teflon
AF 1600: x ) 65, Tg ) 160 °C. Hyflon AD80X: x ) 80, Tg ) 134 °C. Hyflon AD60X: x ) 60, Tg ) 130 °C. Cytop, Tg ) 108 °C.
Table 3. Permeation Properties of Glassy and Amorphous
Perfluoropolymer Membranes
permeability selectivity
(barrer) (-)
polymer O2 N2 CH4 CO2 C2H6 C3H8 CO2/CH4 reference
Teflon AF 2400a 1600 780 600 3900 370 200 6.5
Teflon AF 1600 270 110 80 520 6.5
Hyflon AD 80 67 24 12 150 13
Hyflon AD 60 57 20 10 130 13
Cytop 16 5.0 2.0 35 18
a
Pure gases, P Feed ) 3.5 bar; thickness, 20 µm.
O2/N2 selectivity confirmed that the cross-linked membranes
were more size selective. Cross-linking was not successful in
maintaining the permeability and vapor/gas selectivity of
PTMSP over time, unless 10 wt % of polysiloxysilsesquioxane
was added to the polymer: N2, O2, CH4 permeabilities were
constant over 100 days. In a different study, it was shown that
n-butane permeability decreased for a cross-linked PTMSP
membrane, however its C4/CH4 selectivity was higher than for
a PTMSP membrane containing 30% nanosized fumed silica
(20-30 vs 13-18 at 35 °C).32 PMP, even with lower perme-
abilities than PTMSP, presents a much better chemical stability
which can be useful in hydrocarbon separation.13
Amorphous Teflon AF2400 possesses many advantages as a
membrane material, including good film forming properties,
extremely high chemical stability, low susceptibility to swelling,
and, differently from other high permeability polymers, no
detectable aging. In addition, it is insoluble in common organic
solvents but shows good solubility in perfluorinated solvents,
which are used in the preparation of composite membranes.33
Teflon AF2400 and Teflon AF1600 (DuPont) are the most
permeable among perfluoropolymers (Figure 1 and Table 3), a
family with excellent thermal and chemical resistance, melt
stability, good mechanical properties, usable in a broad tem-
perature range. These features originate from the high energy
of C-F (485 kJ/mol) and C-C (360 kJ/mol) bonds. Other
perfluoropolymers are the copolymers of tetrafluoroethylene
(TFE) and 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole (TTD),
known commercially as Hyflon AD, (produced by Ausimont,
now Solvay Solexis, Italy), and Cytop,34 produced by the Asahi
Glass Company (Japan). The FFV of Hyflon AD60X (23%)35
is lower than that of Teflons AF, but still much higher than
that of common polymers (e.g., polysulfone, poly(ether sulfone)
and polyimide). Hyflon AD60X is a compromise of a moder-
ately high selectivity and a still interesting permeability, in
comparison with the more permeable but less selective Teflon
AF. It is particularly suitable for use in dense GS membranes,
especially in the presence of organic vapors.
In perfluoropolymers the solubility selectivity substantially
changes, therefore they represent materials suited for challenging
separations (e.g., olefin/paraffin or natural gas treatment).
Experimental GS data obtained with membranes prepared
with TTD-TFE (Hyflon AD) copolymers and data from the
literature on Teflon AF membranes revealed an interesting linear
relationship between permeation and Tg.37 Perfluoropolymers
Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009 4641
present an unusually low hydrocarbon-vapor sorption, and a high
resistance toward swelling and plasticization.36 In the case of
Hyflon AD38 very high CO2 permeability (260-280 barrer) are
reported and CO2/CH4 selectivity around 9-11 in the case of
streams containing 20% of CO2 and up to 5.5 MPa. Membranes
prepared using Cytop and Hyflon AD present selectivity factors
25
36 CO2/CH4 of ca. 10-15 also in presence of important amounts
36 of C3+ hydrocarbons and/or CO2, and also at high feed pressure
36 values.36
36 A composite membrane made by a porous asymmetric hollow
fiber with a perfluoropolymer coating was patented by Praxair
Technology.39 Prior to coating, the substrate is impregnated with
a fluid immiscible with the perfluorinated solvent. Membranes
formed by depositing an ultrathin, dense separation layer of an
amorphous perfluoropolymer on top of a porous polyethersul-
fone substrate, and used for the volatile organic compounds
(VOCs) separation and recovery were described in a successive
patent to Praxair.40
Dense solution-cast membranes of Hyflon AD 60X present
an unusually high tendency to retain the solvent;41 this reduces
the thermo-mechanical stability and may cause foaming of the
polymer films upon strong heating under vacuum. Plasticization
of the polymer by the residual solvent decreases the Tg, reduces
the permselectivity of the membranes, and increases the gas
permeability and the diffusion coefficients of the larger gas
species. In comparison, melt-pressed films have a higher
selectivity, mostly due to a stronger size-sieving effect, penal-
izing the diffusion rate of the larger gas species (e.g., CO2, O2,
nitrogen, and methane). These differences may be related either
to the thermomechanical history of the samples but also to the
effect of the casting solvent. Complete removal of the residual
solvent from solution-cast films may require conditions (e.g.,
drying temperatures near or above the Tg) which are normally
prohibitive for the membrane integrity. The origin of the solvent
retention in Hyflon is not yet fully understood; it could be related
to the particularly high FFV, to the free-volume distribution of
Hyflon, and to specific polymer-solvent interactions.
Polymers of intrinsic microporosity (PIMs) were recently
synthesized by McKeown et al.26,27,42,43 These materials are
obtained by forming a backbone that has no conformational
freedom, but is sufficiently contorted to prevent an effective
packing. As conventional molecular sieves, they represent a new
class of microporous material (with interconnected pores less
than 2 nm in size), generated through polymer chemistry and
offering processability combined with control over surface
functionality and surface properties. Differently from conven-
tional nonsoluble microporous materials, they have good
solubility and easy processability. These materials swell revers-
ibly in the presence of a nonsolvent such as methanol. In PIM
polymers the permeability order is CO2 > H2 > He > O2 > Ar
> CH4 > N2 > Xe, while in many glassy polymers the typical
behavior is He > CO2. The permeation data reported for CO2
and CH4 in these membranes27 are located in between the 1991
and the 2008 Robeson’s upper bounds (e.g., CO2 permeability
of 2300 barrer and CO2/CH4 selectivity 18.4) (Figure 3).
4642 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009
Park et al.44 demonstrated that some dense glassy polyben-
zoxazoles and polybenzothiazoles permit outstanding molecular
and ionic transport and separation performance, beyond the
limits of conventional polymers. The peculiar free-volume
microstructure in these so-called “thermally rearranged poly-
mers” is created by the thermal decarboxylation of precursor
polyimides between 350 and 450 °C, which induces a change
in the chain conformations and spatial location of rigid moieties.
The size of free-volume elements can be rationally tailored by
controlling the degree of the rearrangement and the flexibility
of the original chain. CO2 and other small molecules go through
hourglass-shaped pores connected by size selective throats which
hinder the passage of larger molecules (e.g., CH4): CO2 moves
through them hundreds of times faster than in conventional
membranes. Thermally rearranged polymers work much better
than conventional membranes at separating out CO2 from
methane, since they are very permeable (1600 barrer for CO2)
and, differently from cellulose acetate and polyimides, maintain
CO2/CH4 selectivity high (in excess of 40) even with large CO2
partial pressures. If this material is used instead of conventional
cellulose acetate membranes to natural gas process plants, it
would require 500 times less space, and would lose less natural
gas in their waste products.45
2.2. Solubility-Controlled Membranes. Solubility controlled
membranes, sometimes referred to as “reverse-selective mem-
branes”, preferentially allow large gas or vapor molecules to
permeate in a gaseous mixture containing smaller molecules.
These membranes find application in the separation of CO2 from
lighter gases, in VOCs removal from permanent gas streams,
in monomer recovery from the exhaust of polymerization
reactors, and are studied for the removal of higher hydrocarbons
from methane.
An interesting application is represented by solubility con-
trolled H2 separation (e.g., CO2/H2 separation). Poly(ethylene
oxide) (PEO) is recognized as an interesting material for CO2
membrane separation46 owing to polar ether oxygens that
interact with quadrupolar CO2, molecules resulting in high
solubility selectivity. The affinity of the membrane material for
CO2 must not be too high such that its mobility is reduced,
otherwise the CO2 flux will suffer. Copolymers containing PEO
blocks, highly flexible, weak size-sieving and with high diffusion
coefficients, present high CO2 permeability and high CO2/H2
selectivity.47 PEO, however, shows very low CO2 permeability
(ca. 12 barrer at 35 °C and infinite dilution) due to high
crystallinity levels;48 the crystalline regions reduce the polymer
chain mobility in the amorphous phase and increase size-sieving
ability, thus decreasing CO2/H2 selectivity. To hinder crystal-
lization, Freeman et al.49 developed a series of cross-linked and
highly branched PEO, introducing short non-PEO segments into
the PEO backbone. These membranes were demonstrated to
have outstanding separation performance for H2 purification by
removing acid gases (CO2 and H2S) from feed streams of
practical interest, as well as SO2 and NH3 from nonpolar gases.
Differently from conventional membrane materials, the presence
of moisture and high-pressure CO2 in the feed improves
permeability and selectivity.
CO2/H2 separation is also exploited in a hydrocarbon synthesis
process (e.g., Fischer-Tropsch), from which both hydrocarbons
and high purity hydrogen are obtained. The use of a reverse-
selective membrane for the hydrogen-depleted stream will
provide a CO2-enriched permeate and, advantageously, a
hydrogen-containing retentate at elevated pressure.50,51
Solubility is the key factor that enables CO2 to preferentially
permeate over the less soluble components including H2.
Solubility controlled membranes based on polyether-polyamide
block copolymers (e.g., Pebax) and selectively permeable to
CO2 are available from MTR (U.S.A.). The permeation proper-
ties of these membranes are optimized for separating CO2 and
polar gases from nonpolar gases.
Poly(propylene glycol) and poly(ethylene oxide) copolymers
and blends with PEO, eventually containing nanofiller particles,
havebeenconsideredforsolubility-controlledCO2 separations.52-54
The ethylene oxide copolymers studied in the literature for this
purpose include polymers in which the rigid moieties are made
of polyimide, polyurethane,55 polystyrene,53 polyesters.56,57
Other polymeric materials that may be of interest for CO2/
H2 separation include polyphosphazenes.58,59 PDMS and PT-
MSP are more permeable to condensable gases such as CO2 or
H2S only at lower temperatures (25 °C); at higher temperatures
sorption selectivity decreases and the more mobile H2 becomes
more permeable.60
Very high free-volume polymersssuch as poly(4-methyl-2-
pentyne) (PMP) and PTMSPscontaining nanometric filler
particles, mainly fumed silica, have shown interesting n-butane/
CH4 reverse perm-selectivity; these hybrids membrane materials
will be discussed later in paragraph 2.4 with the other mixed-
matrix membranes.
2.3. Carbon-Based Membranes. Carbon-based membranes
can be classified into two classes: (1) carbon molecular sieve
membranes (CMSs) and (2) carbon nanotubes (CNTs) membranes.
2.3.1. Carbon Molecular Sieve (CMS) Membranes. Car-
bon molecular sieve membranes have a very long history. As
early as 1955 Barrer and Strachan produced a pioneering work
on the adsorption and the diffusion of six permanent gases in
microporous plugs made of compressed, high specific surface
carbon powder, evidencing the importance of surface flow for
the most polarizable species.61 In the next years Barrer and co-
workers produced an extensive, detailed, and sophisticated
analysis of gas and vapor sorption and diffusion through those
early compacted carbon membranes.62
CMSs show excellent intrinsic performance for GS applica-
tions. These micro- to nanosize materials are obtained today
through the pyrolysis (at high temperature in an inert atmo-
sphere) of polymeric precursors already processed in the form
of membranes, and may be considered as just a type of “very
high free-volume” materials.
Carbon membranes are believed to contain slit-shaped pores
among planar aromatic moieties. The mechanism of separation
in carbon membranes depends on the pore size, which deter-
mines the degree of interaction between molecules and pores.
Molecular sieving is dominant when the effective pore diameters
are on the molecular scale (3-5 Å). For larger pore sizes in
which both components in a mixture can be accommodated,
selective sorption is the key factor in determining the real
separation properties of the membrane (e.g., the surface selective
flow membranes described later in this paragraph).
Extensive studies were carried out on the preparation of CMS
membranes from both rubbery and glassy polymers.63-69
Polyimides are the most used precursors,70-74 but their use
results in high production costs. Therefore, efforts were made
to use less expensive starting materials (e.g., polyacrylonitrile75).
Other precursors investigated are poly(furfuryl alcohol)76 and
phenolic resin.77
Carbon membranes were prepared in both unsupported
(typically capillary tubes or hollow fibers and flat membranes)
and supported (typically flat or tubular) forms. Supported
membranes grafted onto macroporous materials were developed
to overcome the poor mechanical stability of unsupported carbon

Table 4. O2/N2 Selectivities Reported for Carbon Membranes
starting material
cellulosic or phenolic resins hollow fibers 800 and 950 °C (postpyrolysis steps required to open
the structure of the 950 °C membranes)
hexafluoroisopropylidene (6FDA)-based copolyimide 550 °C
hollow fibers with O2/N2 selectivities of 4
Kapton polyimide Flat homogeneous films 800 °C
Kapton hollow fibers up to 800 °C
up to 1000 °C
phenol formaldehyde resin Flat dense films 800-950 °C with a postpyrolysis activation
polyimide film coated on porous alumina tubes 700 °C
post pyrolysis carbon deposition step
poly(furfuryl alcohol) 450 °C, 120 min
membranes.78 The options for coating the supports with thin
polymeric films are ultrasonic deposition,79,80 dip coating,71
vapor deposition,81 spin coating,82 and spray coating.83 Detailed
descriptions of the steps involved in carbon-based membrane
fabrication (precursor selection, polymeric membrane prepara-
tion, pretreatment of the precursor, pyrolysis process, post-
treatment of pyrolyzed membranes, and module construction)
have been presented in the Ismail and David’s review.84 The
manipulation of the pretreatment variables, pyrolysis process
parameters, and post-treatment conditions was shown to provide
an opportunity to enhance the separation performance of carbon
membranes.82,85
Referring to the O2/N2 separation, interesting selectivities were
reported for carbon membranes, as summarized in Table 4.
One important example is that of the surface selective flow
(SSF) membranes developed by Air Products and Chemicals.89
The membrane consists of a thin layer (2-3 µm) of a
nanoporous carbon (6-7 Å pore diameter) supported on the
bore side of a macroporous alumina tube. This technology is
able to produce enriched hydrogen streams at high pressure.
Carbon hollow fibers were developed and commercially pro-
duced by Israel’s Carbon Membranes Ltd.90
Carbon membranes combine improved gas transport proper-
ties for light gases (gases of molecular sizes smaller than
4.0-4.5 Å) with thermal and chemical stability. However, they
are not suitable to separate some gas mixtures of interest to
industry, such as branched pentanes versus linear hydrocarbon
molecules or gas-vapor mixtures (e.g., H2/hydrocarbons).8 A
prepurifier is required for removing traces of strongly adsorbing
vapors, which can clog up the membrane pores. This pretreat-
ment is typical for many industrial adsorption separators and
may be avoided by operating at sufficiently high temperatures.91
One major disadvantage that hinders their commercialization
is their brittleness, making them require a careful handling.8,92-94
This may be prevented to a certain degree by optimizing
precursors and preparation methods.93 When compared to
polymeric membranes, the cost of carbon-based membranes is
1 to 3 orders of magnitude greater per unit area. Only when
they achieve a much better performance than polymeric
membranes might this high investment cost be justified.95
Despite the great experimental effort devoted to the develop-
ment of CMS membranes from the 1950s, aging, pore blocking
by higher organics, and brittleness are the reasons that induced
several companies to give up with their development programs.
To the best of our knowledge there is today no producer of
commercial CMS membrane modules.
2.3.2. Carbon Nanotubes as Membranes. The possibility
of using carbon nanotubes (CNTs) as membranes for GS was
initially proposed by MD simulations that predicted transport
of gases inside single-walled carbon nanotubes with diameter
of ca. 1 nm, orders of magnitude faster than in any other known
Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009 4643
pyrolysis conditions O2/N2 selectivity reference
7-8 86
11-14 70
4.2 72
11 87
23
11 88
9.7 71
14
30.4 80
materials with nanometer-scale pores (e.g., zeolites).96-99 CNTs
are different from other ceramic membranes with atomic-scale
pores, owing to the smoothness of the inner surface,100 the high
rigidity of the graphene plane and the nonpolar nature of the
sp2 carbon network.101 Some of the theoretical predictions were
verified experimentally with larger carbon nanotubes.102,103
Hinds et al.102,104 and then Holt et al.103 reported the synthesis
of free-standing and silicon-chip supported vertically aligned
carbon nanotubes membranes by complex multistep synthesis
procedures. They used chemical vapor deposition to grow
oriented carbon nanotube carpets. Hinds and co-workers102
developed polymer-nanotube composite membranes using mul-
tiwalled carbon nanotubes (MWNTs) with large diameters (6-7
nm) and verified that the transport of liquids (alkanes, water) is
orders of magnitude faster than can be accounted for by
conventional hydrodynamic flow.104 Holt et al.103 have devel-
oped nanotube-Si3N4 composite membranes. They produced
dense parallel arrangements of double-walled carbon nanotubes
(DWNTs) having a diameter of about 1.6 nm with both sides
open in a supported membrane structure. To develop this highly
perfect geometry they used advanced microfabrication facilities:
they surrounded the nanotubes with a matrix of silicon nitride,
before ion milling to remove excess silicon nitride, and reactive
ion etching to open up the ends of the nanotubes. Gas flow is
1-2 orders of magnitude faster than through a commercial
polycarbonate nanoporous membrane with 15 nm pore size. The
water flow through their membranes was more than 3 orders of
magnitude faster than expected from hydrodynamic flow
calculations. Moreover, these nanotube membranes exhibited
extraordinarily high size exclusion selectivity for 2 nm colloidal
gold particles.
The move to devices suitable for large-scale applications
requires to scale up the fabrication techniques to economically
produce membranes with large surface areas. Chemical vapor
deposition, while producing well-aligned carbon nanotubes, is
expensive, long, and is limited to fabricating samples with small
areas (e.g., subcm2). CNTs were aligned in the pores of a
hydrophilic polyamide filter105 although to date this approach
was successful only with multiwalled nanotubes (MWNTs). Lin
et al.106 developed vertically aligned MWCNT membranes using
CNTs grown above the surface of a porous R-Al2O3 disk; the
method can be scaled up for practical applications. These
membranes have lower areal tube density as compared to CNT
membranes on dense silicon and quartz support, and their gas
permeance is inversely proportional to the squared root of the
gas molecules. However, the diffusivity of gases is only about
four times larger than predicted by the Knudsen model.
Compared with other CNT membranes,103 the enhancement in
permeability or diffusivity in CNT membranes due to atomically
smooth CNT pore wall decreases with increasing CNT pore
size.
4644 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009
The use of single-walled carbon nanotubes (SWNT) with
smaller diameter as membranes is particularly interesting
because, in addition to fast transport rates, the 4-12 Å pore
openings might be size-selective for gas mixtures. However,
they have to be aligned vertically relative to the penetrant stream.
This is the most important challenge facing the fabrication of
SWNT membranes.
Marand et al. produced vertically aligned SWNT membranes
embedded in polysulfone.107 The authors believe that SWNTs
orient in the shear flow produced during filtration and propagate
the perpendicular alignment to the PTFE filter via long-range
repulsive forces between zwitterions attached to the carbon
nanotube surface. This filtration method facilitates the orientation
of carbon nanotubes on porous supports and can be adapted to
large-scale membrane formation. The gas transport properties
of the nanotube/polymer membranes are analogous to those of
CNT membranes grown by chemical vapor deposition. The
authors obtained the first data for transport of CO2/CH4 mixtures
through CNT membranes; the comparison with the predictions
of atomistic simulations of mixture diffusion seems to indicate
the presence of transport resistances for molecules entering and
leaving the nanotube ends.
Transport of gas and water through the nanotubes was much
higher than predicted by classical diffusion or hydrodynamics
models. The transport rates observed by Holt et al.103 for
different gases are one to 2 orders of magnitude larger than
would be predicted by assuming a Knudsen description, which
is in quantitative agreement with predictions from simulations.108
Alternative transport mechanisms were proposed that emphasize
transfer limitations at the tube entrance. The very efficient
transport in the tubes makes the kinetics of surface transfer
becomes more important.101 MD simulations for mixture
separation in SWNT membranes predict the preferential adsorp-
tion of CH4 relative to H2 and CH4/H2 selectivities as high as
10-20.109
Despite the exceptionally fast mass transport for both gas
and water, the enhancement of the selectivity of CNT mem-
branes is a big challenge. The DWNT membranes may not be
sufficiently cost-effective for large-scale applications but might
be developed for the separation of valuable molecular species
by size exclusion. The road to useful industrial applications of
CNT membranes may be a long and arduous one, due to the
selectivity and cost requirements, but the potential payoff is very
large. Atomistic simulations can provide some help and guid-
ance. These preliminary results should also motivate other
approaches to membrane fabrication that use CNTs in a
composite nanotube/polymer membrane which can result in the
mass production of very efficient devices.
2.4. Mixed-Matrix Membranes. Mixed-matrix membranes
(MMMs) are a well-known route to enhance the properties of
polymeric membranes.110 Their microstructure consists of an
inorganic material in the form of micro- or nanoparticles
(discrete phase) incorporated into a polymeric matrix (continu-
ous phase). The use of two materials with different flux and
selectivity provides the possibility to better design a GS
membrane, allowing the synergistic combination of polymers’
easy processability and the superior GS performance of inor-
ganic materials. In principle, the incorporation of the inorganic
component can be seen as a relatively easy modification of
existing methods for fabricating large-surface area polymeric
membranes; therefore, MMMs possess an economic advantage
over inorganic membranes. In addition, they may offer enhanced
physical, thermal, and mechanical properties for aggressive
environments and could be a way to stabilize the polymer
membrane against change in permselectivity with tempera-
ture.111 These membranes offer very interesting properties;
however, their cost, difficulties for commercial scale manufac-
ture, and brittleness remain important challenges. The successful
development of MMMs depends on several factors, such as the
proper selection of polymeric matrix and inorganic filler and
the elimination of interfacial defects between the two phases.
It is also important to control filler concentration, shape, and
dimensions in order to reach the expected performance. Koros
et al.112,113 proposed some criteria for material selection and
preparation protocols in order to match the necessary transport
characteristics of materials to prepare high GS performance
MMMs. A recent comprehensive review on this topic was
presented by Chung et al.114 The authors underline that the major
GS applications addressed by researchers working on MMMs
include air separation and natural gas separation, while the
investigations on high added value separations are limited.
Moreover, research on fabrication of MMMs hollow fibers is
still partial.115 For the formation of thin, defect-free mixed-
matrix structures as asymmetric membranes, several aspects are
relevant: the rheological properties of the dope solutions, the
spinning conditions, and the shape, size, and wettability of the
particles.
Several inorganic materials, porous and nonporous, were
considered for the preparation of MMMs. These inorganic
particles can improve the separation (e.g., by molecular sieving
mechanism) or increase the membrane free-volume.110
Molecular sieves were chosen to enhance selectivity for a
given gas mixture by increasing the sorption of the desired gas
component. In particular, zeolites were widely used in rubbery
and glassy polymers.116-120 Pioneer work was carried out by
Paul and Kemp118 and further expanded by Kulprathipanja et
al.121 using rubbery polymers. According to Paul and Kemp,118
the incorporation of zeolite 5A into silicone rubber did not
improve the separation properties of the polymer. Initial success
(significantly improved performance for separation of O2/N2 and
CO2/CH4) was then achieved incorporating zeolites in highly
flexible rubbers such as polydimethylsiloxane and ethylene-
propylene diene rubber (EPDM),116 and in glassy flexible
polymers, such as cellulose acetate121 and polyvinyl acetate
(PVAc).113 Jia et al.117 also found higher O2 permeabilities (from
571 to 655 barrer) and O2/N2 selectivities (from 2.14 to 2.92)
in silicalite-1 filled silicone rubber (PDMS) membranes than
unfilled membrane. Duval et al.116 showed that zeolites (sili-
calite-1, 13X and KY) improve, to a large extent, the separation
performances of poorly selective rubbery polymers for a CO2/
CH4 mixture, while the CMSs did not enhance the separation
performance. The flexibility of the rubbery polymers was
suggested as the primary cause of good polymer-zeolite
interaction and stress-free interfaces with the zeolite.113 An
adequate contact between the dispersed phase of the molecular
sieve and the polymeric phase was generally observed when
using rubbery polymers as membrane matrix. However, the high
gas fluxes of polymeric rubber matrices can lead to low
improvement in the MMM selectivity.
The improvements in separation performance found by adding
zeolites to rubber polymers stimulated other research to the use
of rigid glassy polymers. This theme has faced some difficulties,
particularly in controlling the adhesion between the polymer
phase and the external surface of the particles.122-124 Initial
efforts at fabricating MMMs using glassy polymers and zeolites
resulted in the formation of voids at the interface between the
polymer and the filler due to the weak polymer-filler interac-
tion125 that reduced the separation performance of the composite

113,113
membrane with respect to the unfilled polymer. To
eliminate the unselective gaps between the polymer and zeolite,
different strategies were proposed:120,125-128 (i) surface modi-
fication of the zeolite external surface, (ii) use of a silane
coupling agent to introduce favorable interactions between
polymer and zeolite, (iii) addition of a plasticizer to increase
the flexibility of the polymer or chemically linking the two
components together, and (iv) high temperature casting and
removal of the dense films from the casting surface at solution
T g.
Vankelecom et al.,129 investigating the incorporation of
zeolites in polyimide matrices, observed a weak adhesion
between the two phases. The same authors then proposed the
silylation of the zeolite outer surface to improve their incorpora-
tion in PI films,130 with nonappreciable improvement of the
polymer-filler contact. However, the use of modification
techniques has resulted in progress in this field:131,132 some
efforts seemed to eliminate the presence of voids between the
polymer and the zeolite, but the resulting permeability of the
MMM was often sacrificed.
Marand et al.133 used a block copolymer containing both
flexible and rigid segments. The polydimethyl siloxane (PDMS)
segments provide flexibility and good contact with the zeolite
surface, removing the need of coupling agents, plasticizers, or
chemical reactions. The addition of PDMS moieties to the rigid
polyimide backbone (with higher selectivity than the PDMS)
resulted in increased permeability and decreased selectivity.
However, the further addition of zeolite L (0-20%) to the
copolymer systems resulted in a loss of both permeability and
selectivity. These effects were attributed to the blocking of the
zeolite pores by the flexible PDMS segments.
An increase of n-butane/i-butane selectivity was observed
instead after the addition of silicalite-1 (MFI) crystals to a
PTMSP matrix.134
Interesting results for MMMs from polyethersulfone and
hydrophilic zeolites (13X and 4A) were reported by Süer et
al.135 For both zeolites, gas permeabilities (N2, O2, Ar, CO2,
H2) and selectivities increase with the zeolite loading. However,
a high amount of zeolite induces formation of microporous
cavities and channelling, demonstrating the weak interactions
and incompatibility of these materials. To reduce the voids
between polymer and filler, 2,4,6-triaminopyrimidine (TAP) was
used by Yong et al.126 and different zeolites of LTA and FAU
topology (4A, 5A, 13X, Na-Y) were dispersed in a Matrimid
polyimide matrix, resulting in very high CO2/CH4 separation
factors (617 in the case of PI/4A/TAP).
In the past few years it has been demonstrated experimentally
that in some cases mixed-matrix membranes containing well-
dispersed “flakes” obtained by exfoliation of molecular
sieves136-138 show improved separation performances and
sieving capabilities. If the platelets are selective for only one
species in a mixture, and their larger surface is parallel to the
membrane skin, that is, normal to the direction of the flux, then
theoretical results indicate that minor amounts of well-dispersed
sieving “flakes” (3-5%) can enhance dramatically the separation
performance.139,140 Very thin (2-3 nm), porous, exfoliated
zeolite sheets have been obtained already for incorporation in
polymeric matrices.141 These developments are particularly
interesting since in real industrial GS membranes the separating
layer is only 100-200 nm thick.
The industrial interest in MMMs can be also appreciated from
four recent patents, two to UOP, one each to Air Liquide and
Chevron. The first UOP patent142 presents high flux MMMs
that are prepared by incorporating porous inorganic fillers (e.g.,
Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009 4645
Table 5. CO2 and CH4 Pure Gas Permeation for AlPO-18-PIM1
MMMsa 142
Pe CO2 ∆Pe Pe CH4 CO2/CH4 ∆CO2/CH4
membrane dense film (Barrer) CO2 (%) (Barrer) (-) (%)
PIM1 4792 590 8.13
30% AlPO-18-PIM1 8202 71 630 13.0 60
a
Tests at 50°C and 690 kPa.
Table 6. Propylene and Propane Pure Gas Permeation for
AlPO-14-PIM1 MMMsa 142
Pe C3) ∆Pe Pe C3 C3)/C3 ∆C3)/C3
membrane dense film (Barrer) C3 (%) (Barrer) (-) (%)
PIM1 2046 657 3.12
30% AlPO-14-PIM1 3111 52.1 759 4.10 31
a
C3), propylene; C3, propane. Tests at 50°C and 207 kPa.
microporous and mesoporous molecular sieves, carbon molec-
ular sieves, porous metal-organic frameworks) into the high
flux PIMs. Some permeation data for these membranes are
presented in Tables 5-6, showing improved separation perfor-
mance in the CO2/CH4 and propylene/propane separation.
MMMs of polyimide and SSZ-13, a zeolite of CHA topology
with narrow pore size, were patented by Air Liquide143 for the
production of O2-enriched air or N2-enriched-air, for the sepa-
ration of CO2 from hydrocarbons or nitrogen, and the separation
of helium or hydrogen from various streams. The MMMs
provide improved performance compared to pure polymer
membranes, particularly when used to form asymmetric film
membranes or hollow fiber membranes and do not interact with
organic solvents present in the process streams. Chevron144
patented MMMs by using silica molecular sieves washed in
water at 95 °C for 18 h prior to calcination, a process called
“super water washing”. It is claimed that “super washing” the
sieves removes foreign amorphous materials adhering to the
outer surface and most alkali metals from the sieves, and
therefore enhances, compared to conventional preparation
techniques, the ability of the molecular sieves to bond with an
organic polymer to form a highly selective and permeable
MMM.
PDMC, a fluorinated polyimide containing dangling carboxy-
lic acid groups, can be cross-linked with 1,3-propane diol. When
SSZ-13 is treated with aminopropyldimethylethoxysilane and
dispersed in cross-linked PDMC, an increase is observed in both
mixed gas CO2/CH4 selectivity (up to 47) and CO2 permeability
(up to 89 barrer) compared to the pure cross-linked PDMC,
surpassing the 1991 Robeson’s upper bound,145 even though
these membranes did not display the selectivity enhancements
forecast by the Maxwell model.146 In addition, these membranes
proved resistant to CO2 plasticization up to 30 bar.
Among the works involving the addition of CMS to polymeric
matrices, Vu et al.147 prepared MMMs by using two commercial
glassy polymers: Ultem 1000 (polyetherimide) and Matrimid
5218 (polyimide). These MMMs exhibited excellent polymer-
filler contact and a remarkable higher performance compared
with those of the pure polymer. For example, Ultem-CMS and
Matrimid-CMS MMM, showed enhancements by up to 40-45%,
respectively, in CO2/CH4 selectivity (pure gas) with respect to
the pure polymers. Marchese et al.148 developed MMMs for
CO2/CH4 separation using an acrylonitrile-butadiene-styrene
copolymer and two micro-mesoporous activated carbons. The
composite membranes did not exceed the 1991 Robeson’s upper
bound, but they displayed improved performances within the
attractive region. The best GS performance at 20 °C (PeCO2 )
4646 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009
11-21 barrer; CO2/CH4 selectivity ) 35-51) were achieved
without compromising their mechanical stability.
Metal oxides nanoparticles were also considered for preparing
MMMs for GS applications. Moaddeb and Koros149 introduced
SiO2 particles into six high performance polymers and found
improved GS performance of the selective layer, particularly
for O2 and N2. This was mainly attributed to the enhanced
rigidity of polymer matrix due to the adsorption of polymer
chains to the surface of silica. Hu et al.111 developed MMMs
based on fluorinated poly(amide-imide) and TiO2 via sol-gel
technique. Their composite membranes showed higher perm-
selectivities for selected gas pairs when compared to the pure
polymer. These results were attributed to the denser and more
rigid structure of the composite membranes which was detected
by the increase in apparent activation energy of permeation.
Lin et al.150 introduced the use of MgO nanoparticles as fillers
into a cross-linked poly(ethylene glycol) diacrylate matrix for
CO2/H2 separation. In the optimum condition, they achieved
significantly improved CO2 permeability while maintaining
selectivity by loading ca. 32 wt % of MgO. The enhanced CO2
permeability was ascribed to the effect of nanoparticles on gas
diffusivity. Hosseini et al.151 introduced MgO nanoparticles into
a Matrimid matrix followed by treatment with silver ions. The
best performance (CO2/CH4 and H2/N2 selectivity increased by
50% and 35%, respectively, compared to the pure Matrimid
membrane) was observed for nanocomposite membranes with
20 wt % MgO and after a 10-day silver ion treatment.
In principle, the gas permeation properties of nonporous
inorganic filled MMMs can be predicted by the Maxwell
equation146 as a decreasing permeability with increasing filler
content, provided that the filler particles do not interact with
each other (diluted phase), and the bulk properties in one phase
are not influenced by the other phase. Extended Maxwell
equations can be devised in order to take into account relatively
high volume fractions of fillers, both porous and nonporous.152
An enhancement of the gas permeability with nanosized particles
was reported by different groups, and explained as a result of
an increase in free-volume because of the inefficient chain
packing as well as the presence of extra void volume at the
interface between polymer and filler. This behavior was
observed for polysulfone/silica nanoparticles MMMs.153 More-
over, the permeability of large gases is preferentially enhanced
by the addition of silica resulting from the increase in free-
volume, which strongly increases the diffusion coefficient and
permeability, and results in a reduction in pure-gas selectivity.
Nanoscale, nonporous fumed silica (FS) particles were reported
to systematically increase penetrant permeability also in Teflon
AF2400, similar to the behavior observed in vapor-selective
polyacetylenes, but contrary to results in traditional filled
polymer systems.154 This is the result of increased diffusion
coefficients, as already observed for filled PMP and PTMSP.
PALS revealed that FS addition increases the size of free-volume
elements, resulting in augmented penetrant permeability and
diffusion coefficients, similar to the behavior of FS-filled
polyacetylenes. Permeability of large penetrants increases more
than those of small molecules in filled Teflon AF2400, thereby
decreasing the size selectivity of this polymer. As a result,
AF2400 exhibits a selectivity reversal for the vapor-gas pair
n-C4H10/CH4, becoming n-butane selective above 18 wt % FS.
Moreover, while AF2400 is readily plasticized by n-butane,
AF2400 containing 40 wt % FS exhibits an antiplasticization
behavior. The addition of nanoscale FS particles to Teflon
AF2400 has no detectable effect on the polymer’s Tg, indicating
that the filler has little impact on polymer chain stiffness or
mobility. FS-induced permeability enhancement decreases with
increasing base polymer permeability. The incorporation of FS
nanoparticles to cross-linked PTMSP increased the initial
permeabilities;32 however, these composite membranes did not
show stable permeability over time. The addition of hydrophobic
silica (up to 50 wt %) to PTMSP was reported to increase
permeability and decrease the propane/H2 selectivity.155 Besides
an increase in large free-volume size (determined by PALS)
with increasing filler content, interstitial mesopores (located
among the particles of a silica agglomerate) were observed. The
size of these interstitial cavities was increasing with filler
concentration. The presence of mesopores in the MMMs
explains also the reduced selectivity compared with unfilled
PTMSP membranes. Thermal analysis showed that FS has a
retarding effect on polymer decomposition.
Few discussions are present in the open literature on the
spinning of asymmetric hollow fiber MMMs for GS. Jiang et
al.156 described the formation of zeolite-polymer hollow fiber
MMMs which were defective. Successful mixed-matrix hollow
fibers for GS were presented by Husain and Koros.157 The
authors increased the hydrophobicity of the zeolite surface by
capping surface hydroxyls with hydrophobic organic chains via
a Grignard-type reaction. The fibers incorporating the treated
zeolites showed a selectivity enhancement of 10% for O2/N2,
29% for He/N2, and 17% for CO2/CH4 pure gas pairs,
respectively, and 25% for CO2/CH4 mixed gas. The success of
the “Grignard treated” zeolites in the polymer matrix also
highlights that coupling of the polymer to the sieve surface is
not a prerequisite for successful MMM formation.
2.5. Zeolite Membranes. In the last two decades, zeolite
membranes were extensively studied, considering preparation
techniques and separation features because of their higher
thermal and chemical resistance compared with those of polymer
membranes. Zeolite membranes in principle might separate
continuous mixtures on the basis of differences in the molecular
size and shape,158 but also on the basis of different adsorption
properties.159 The separation ability of a microporous membrane
can be described by the interplay of the mixture adsorption
equilibrium and the mixture diffusion in a way similar to the
solubility-diffusion model established for describing the per-
meation behavior of dense organic polymer membranes.
Different methods for the controlled preparation of supported
zeolite membranes have been established.160 Basically, they can
be distinguished into one-step methods and in secondary growth
(seeding techniques) methods. The latter, decoupling zeolite
nucleation from crystal growth, allows optimizing the conditions
of each step independently, reducing or suppressing any
secondary nucleation.161 Seeding, the first step, consists in the
deposition of the crystal seeds on the surface of a support,
followed by a crystal growth by means of a hydrothermal
treatment. The advantage of the membranes made by secondary
growth is the high flux and the possibility to orient the seed
crystals;162 the drawback is the ease of formation of defects or
non-zeolitic pores, which form intercrystalline pathways, larger
than the zeolite pores and therefore not selective. In an
interesting one-step method (pore-plugging synthesis) zeolite
crystals are grown within the pores of a macroporous support,
yielding very robust, defect-free MFI membranes,163 whose
permeance however is not very high.
Researchers from Colorado164 have recently demonstrated that
MFI zeolite membranes swell when exposed to normal alkanes
(C3-C6) and SF6, but not to CO2 or benzene. The experimental
evidence indicates that MFI membranes with significant flow
through defects can be highly selective if the defects are small

enough and one of the molecules in the mixture swells the
crystals, thereby shrinking the defect size.
Usually, the transport of a gas through a zeolite membrane
as a function of temperature goes through a maximum, then
decreases, and rises again at higher temperatures.165 For
several years the transport of gases in zeolite membranes has
been interpreted by the superposition of the Stefan Maxwell
approach at low temperatures, which takes into account only
adsorption,166,167 and of the so-called activated Knudsen
diffusion at higher temperatures.168,169 Interestingly, the
transport of gases through MFI membranes prepared by
plugging the pores of the ceramic support, rather than
growing them on top, do not show any increase of permeance
after the lower temperature maximum and can be perfectly
fitted by the Maxwell-Stefan model alone.170 The authors
believe that the increase in the gas permeance observed at
higher temperatures through film-like membranes on top of
a support is due to the reversible opening of defects, probably
because of the mismatch of the thermal expansion coefficients
of zeolite and support.
Many types of zeolite membrane have been studied (e.g.,
MFI, LTA, MOR, FAU). The first commercial application is
that of LTA zeolite membranes for solvent dehydration by
pervaporation.171 Some other plants were installed since 2001,
but no industrial applications are reported for zeolite membranes
in the GS field.160,172 The reasons for this limited application
in industry might be due to economical feasibility (development
of higher flux membranes should reduce both costs of mem-
branes and modules) and poor reproducibility.
Little progress is seen in the development of small-pore
zeolite membranes for H2 separation.160 A H2/N2 separation
factor of 24 was reported for the small-pore zeolite A.173 No
higher values were reported, owing to the presence of inter-
crystalline spaces in the zeolite layer. Interesting methods to
improve the separation performance of zeolite membranes,
particularly for small gas molecules, are related to postsynthesis
modification by silylation to decrease the pore size and to
increase the hydrophobicity.174,175 A MFI membrane with a H2/
N2 separation factor of 1.4-4.5 reached values of 90-140 after
silane catalytic cracking.174
Y-type zeolite membranes were demonstrated as potential
candidates for CO2/N2 separation.176 The separation of light
hydrocarbon (C3H6 and C3H8)/N2 mixtures was investigated
using FAU membranes,177 considering a ternary mixture having
a composition of a typical polypropylene vent stream (12.5%
C3H6, 12.5% C3H8, 75% N2). Only C3H6 can be recovered from
such a mixture. This result is very important because C3H6 is
the valuable monomer and if recovered with suitable purity it
can be recycled back to the polymerization reactor.
With the development of capillaries, fibers, and multi-
channel modules the membrane area to module volume ratio
could be improved. Current estimated costs per zeolite
membrane GS module are of ca. $4,000/m2, comparing
favorably with that of metal membranes and modules (ca.
$16,000/m2). It can be expected that, once in mass use and
production, those costs will reduce significantly to less than
$1,000/m2, allowing zeolite membranes to compete both in
economics and on performance.95 Challenging separations
as paraffin/olefin, CO2/other gases, and aromatics/aliphatics
might be solved using zeolite membranes.160
2.6. Facilitated Transport Membranes. Facilitated transport
membranes (FTMs) have also shown promising results for GS.
These membranes comprise a carrier (typically metal ions) with
Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009 4647
a special affinity toward a target gas molecule and this
interaction controls the rate of transport.
FTMs can be categorized into four major types:178 (1)
immobilized liquid membranes, (2) ion-exchange membranes,
(3) polymer/metal ion dispersions, and (4) modified polymer
membranes. Selection of suitable carrier with high affinity
toward the desired molecules, in conjunction with the adoption
of appropriate strategy for design and fabrication of membranes,
are the principal criteria to use the advantages of facilitated
transport for GS.
The primary drawback to supported liquid membranes is that
over time the aqueous carrier solution evaporates or is pushed
out of the membrane pores, resulting in a nonselective transport.4
Thick membranes will present improved stability and reasonable
lifetimes but a lower gas flux. Even though other means of
improving the stability of supported liquid FTMs have been
explored, including adding dense sealing layers, or less volatile
carrier solvents, their inherent instability limits their commercial
exploitation.
Room temperature ionic liquids (RTILs), with negligible
vapor pressure, overcome the problem of volatility. Suitable
polymerizable surfactant RTILs form a variety of lyotropic
liquid crystalline phases when mixed with water or simple
RTILs. The polymerization of RTILs may yield polymeric
materials with ordered nanopores, which are of great interest
for CO2 separations from N2 and CH4.179,180
Kovvali and Sirkar reported an excellent CO2/N2 selectivity
at atmospheric pressure for the viscous and nonvolatile liquid
poly(amidoamine) (PAMAM) dendrimer, as an immobilized
liquid membrane.181,182 The PAMAM dendrimers kept the good
CO2 selectivity also in the presence of water vapor. This is very
interesting for the application in CO2 separation from combus-
tion flue gases, since exhausted gases usually contain saturated
water vapor. However, this immobilized liquid membrane has
insufficient tolerance to handle the large trans-membrane
pressure differences often required for obtaining sufficiently
large gas fluxes. To overcome this problem, PAMAM dendrimer
composite membranes comprising a gas selective layer on a
porous substrate were developed.183 The composite membrane
showed a CO2 permeance of 4.6 × 10-10 m3 (STP) m-2 s-1
Pa-1 (61 GPU) and a CO2/N2 selectivity of 230 at a pressure
difference of 97 kPa at 40 °C, meeting the conditions for
practical application. The PAMAM dendrimer composite mem-
brane also showed CO2/CH4 selectivity similar to that of CO2/
N2. Improvements to the mechanical properties and CO2
separation capabilities of the PAMAM dendrimer composite
membrane are required.
Limitations of immobilized liquid membranes in real operat-
ing conditions184,185 led to the development of ion-exchange
membranes. Way et al. prepared ion-exchange membranes
containing organic amine counterions which showed enhanced
performance for CO2 removal from methane streams.186
A FTM for CO2 separation was patented by Hägg et al.187
The membrane has a support coated with cross-linked polyvi-
nylamine; a fixed carrier in the membrane helps so that the CO2
molecules in combination with moisture form HCO3- ions,
which are then quickly and selectively transported through the
membrane.188 The technology is effective and eco-friendly, and
can be used for CO2 removal in coal-powered plants. Its
effectiveness increases proportionally to the CO2 feed concen-
tration. Within a 5 year period, these membranes will be tested
in four large power plants in Europe. These membranes are
4648 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009
under further development within the European project Nano-
GloWa (Nanostructured Membranes against Global Warm-
ing).189
Silver ions were widely investigated as carriers for the
production of FTMs: they facilitate the transport of olefins,
forming reversible π-complexation with molecules containing
double-bonds, leading to a subsequent solubility enhancement.
This mechanism was successfully exploited for the laboratory
scale olefin/paraffin separation.190,191 Long-term instability were
recognized for polyether-polyamide block copolymer (Pebax
2533) membranes containing high loadings (>30%) of AgBF4.192
This study highlights as olefin permeation rates and olefin/
paraffin selectivities in silver salt membranes are time dependent,
both decreasing over time. This behavior is mainly related to
the reduction of the available silver carrier ions (e.g., owing to
hydrogen, hydrogen sulfide, and acetylene) and to olefin-induced
structural changes that occur in the membranes over time.
Almost all aged and some poisoned Pebax +AgBF4 membranes
(except those exposed to H2S) can be regenerated by a periodic
contact with an oxidizing vapor or liquid treatment, similarly
to back-flushing treatments for ultra- or microfiltration mem-
branes to manage fouling. Today sulfur poisoning is the major
problem that makes Ag+ containing membranes unfit for
industrial use.
An interesting recent paper on new materials for natural gas
separation presented the development of polyethersulfone (PES)-
NaA zeolite and PES-AgA zeolite MMMs fabricated at high
temperatures.193 The CO2 permeability of PES-AgA zeolite
MMMs is higher than that of PES-zeolite NaA, whereas their
CH4 permeability is lower. This trend might be the result of a
reversible complexation reaction between the silver ion and the
CO2 molecule. CO2 and CH4 permeability of PES-zeolite AgA
MMMs decreases with increasing zeolite content owing to the
partial pore blockage of the zeolite and to the polymer chain
rigidification, whereas their CO2/CH4 selectivity increases with
zeolite loadings: the highest value reaches 59.6 at 50 wt %
zeolite loading, probably because of a combined effect of the
facilitated transport mechanism of the silver ion and the
molecular sieving mechanism of the zeolite. Both CO2-induced
plasticization test and CO2/CH4 mixed gas measurement through
this PES-zeolite AgA MMMs proved suitable for the separation
of natural gas.
3. Summary of Literature Data
For comparison purposes of different materials suited for a
particular separation, a selectivity vs permeability diagram can
be employed. Membrane permeance provides a figure of merit
for membrane performance for practical applications, but
permeability data are often reported and for research purposes
can be more interesting. In the following, some literature data
are presented in selectivity vs permeability representation for
the main gas separation applications. An upper bound for
polymeric materials is also represented.
Figure 2 reports some experimental results reported for
different polymers, PIM materials, MMMs, and carbon mem-
branes in the case of O2/N2 separation, together with the 1991
and the 2008 Robeson’s upper bound.6,194
An improvement in selectivity was observed for Hyflon
membranes,195 together with a reduced permeability when the
membranes are heated up to 200 °C for the removal of any
residual solvent. PIMs data are close to the “present” upper
bound; some MMMs and carbon MMMs overcome this limit.
Figure 3 reports some data for the separation CO2/CH4,
together with the upper bound presented in the Robeson’s papers
in 19916 and 2008.194 When the performances of MMMs and
the one of the pure polymer are compared (Figure 2) the latter
is always worse.
The data available for PIMs are close to the last reported
upper bound, while the points over the upper bounds are related
to MMMs prepared with PIMs, other types of MMMs, and the
XLPEO operated at -20 °C.
The performance of commercial membranes used to separate
carbon dioxide from high-pressure natural gas, reported by
Baker,208 is enclosed in the shaded area below the 1991 upper
bound.
In Figure 4 are collected different data for the case of CO2/
N2 separation. No upper bound was reported by Robeson for
this separation in 1991; the limits in Figure 4 are taken from
three different literature papers206,221,222 together with the 2008
upper bound.194
Also in this case the materials showing better transport
properties are carbon membranes and MMMs.
4. Industrial Applications of Membrane GS
The main industrial applications developed for membrane GS
are summarized in Table 7. In the following paragraphs some
of the industrial processes will be discussed.
4.1. Hydrogen Recovery. Hydrogen recovery was among
the first large-scale commercial applications of membrane GS
technology. A comprehensive review on this topic was recently
presented by Ockwig and Nenoff.95
The commercial success in the mid-1970s of the Permea
hollow-fiber prism system for in-process recycling of hydrogen
from ammonia purge gases was the starting point of the
penetration of membrane technology in large-scale manufactur-
ing. (Formerly a Monsanto Company, Permea, Inc. is now
owned by Air Products and Chemicals, Inc.) A two-step
membrane design (as that in Figure 5a) was chosen for this
ideal application for membrane technology. In fact, the ammonia
reactor operates at high pressures (ca. 130 bar), thus providing
the necessary driving force for separation; the H2/N2 membrane
selectivity is high and the feed gas is free of contaminants (e.g.,
heavier hydrocarbons). This technology has been extended to
other situations for recovery of hydrogen from gas mixtures
(H2/CO or H2/CH4 ratios adjustment for syngas production) and
has been successfully competing with cryogenic distillation and
pressure swing adsorption (PSA) processes. H2 recovery from
refinery streams is an emerging field for membrane GS in the
petrochemical industry; it is a key approach to meet the
increased demand of hydrogen (for hydrotreating, hydrocrack-
ing, or hydrodesulfurization processes) owing to new environ-
mental regulations. An example is the H2 recovery from high
pressure purge gas of a hydrotreater (Figure 5b). A lower
investment cost than PSA or cryogenic separation was
estimated by Spillman for the H2 recovery from refinery off-
gas by polymeric membranes (polyimide membranes,
Ube).230 This comparison is from 1989; since then membrane
capital prices have dropped and the separation performances
have improved.
China’s first hydrogen recovery unit by membrane technology
from refinery’s hydrocracking dry gas and PSA resolving gas
ran a successful trial production in Sinopec Zhenhai Refining
Plant.231
The membrane in the Prism system is a polysulfone hollow
fiber with a thin silicone film on it. Polyimide membranes are
currently successfully applied for H2-recovery in refineries, due
to their stability and interesting separation factors (H2/N2 of ca.
100-200).233,234

Figure 2. Robeson’s diagram for the O2/N2 separation.
Commercial polymeric membrane modules (e.g., MEDAL)235
can operate at high pressure (120 bar), with flow rates up to
330 000 Nm3/h; hydrogen recovery can reach 98% in volume,
with hydrogen purity as high as 99.9%.
Hydrogen is largely produced by natural gas steam reforming
which results in a gaseous mixture containing mainly hydrogen
Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009 4649
and also carbon dioxide and carbon monoxide. Conventional
membranes, which allow H2 to pass through while retaining
other gases, would decrease hydrogen pressure. Solubility
controlled membranes that permit larger gas molecules like CO2
and polar molecules pass through, allow the bulk gas to be
retained at feed pressure, thereby minimizing or avoiding
4650 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009

Figure 3. Robeson’s diagram for the CO2/CH4 separation.

 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009 4651

Figure 4. Robeson’s diagram for the CO2/N2 separation.

4652 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009

Table 7. Main Industrial Applications of Membrane GS Table 8. Progresses of the Membranes for the O2/N2 Separation
(25°C)236-240
separation process
O2/N2
H2/N2 ammonia purge gas O2 permeability selectivity
H2/CO syngas ratio adjustment year polymer (Barrer) (-)
H2/hydrocarbons hydrogen recovery in refineries
O2/N2 nitrogen generation, oxygen-enriched 1970s poly(vinyltrimethylsilane) 47 4.3
air production 1982 poly(4-methyl-1-pentene) 24 3.6
CO2/hydrocarbons (CH4) natural gas sweetening, landfill gas 1985 ethyl cellulose 15 3.4
upgrading 1986 polysulfone 1.2 6.0
H2O/hydrocarbons (CH4) natural gas dehydration 1989 poly(phenylene oxide) 16 4.0
H2S/hydrocarbons sour gas treating 1989 halogenated polycarbonates (35 °C) 2.3-1.4 6.4-7.4
He/hydrocarbons helium separation 1996 polyimides 4-0.1 6-9
He/N2 helium recovery 2005 polyimides 18-0.079 9-19.8
hydrocarbons/air hydrocarbons recovery, pollution control
H2O/air air dehumidification
membrane performance for separation of air components has
volatile organic species polyolefin purge gas purification
(e.g., ethylene or propylene)/ advanced during the past 15 years, as shown in Table 8 that
light gases (e.g., nitrogen) evidences the trade-off between permeability and selectivity with
polymeric membranes.
H2recompression, even if it potentially adds a CO2 compression As pointed out by Baker,3 improvements in membrane O2/
step. Hydrogen membrane rejection and contaminate permeation N2 selectivity are beginning to reach a point of diminishing
is currently explored for H2 purification, primarily using carbon- returns. Increasing the O2/N2 membrane selectivity from the
based membranes.95 actual value of 8 to 12 (at the same permeation rate), will reduce
4.2. Air Separation. The small difference between kinetic compressor size by about 20%, resulting in a 10-15% reduced
diameters of nitrogen (3.64 Å) and oxygen (3.46 Å) molecules nitrogen production costs.3 In today’s highly competitive world,
makes air separation very difficult by a simple size effect. The such an improvement is unlikely to greatly expand the total
market.
Nitrogen production by membrane systems was a great
success and today is the largest GS process in use. Nitrogen
gas is used in many applications related to safety (e.g., to prevent
fires and explosions in tanks and piping systems and to prevent
equipment degradation, during shutdown periods, in compres-
sors, pipelines, and reactors). Membranes are dominating for
applications of less than 50 tons/day and relatively low purity
(0.5-5% O2). As pretreatment, particulates, water, and oil in
compressed air are removed by coalescing/particle filters. Single-
stage membrane operation is preferred. Air is pressurized and
fed into the membrane separators; faster gases (O2, CO2, water
vapor) permeate through the polymeric fiber walls and are
collected and vented to the atmosphere while the slower,
nonpermeate N2 gas is available at the other end of the separator.
Oxygen production by membrane systems is still underde-
veloped, since most of the industrial O2 applications require
purity higher than 90%, which is easily achieved by adsorption
or cryogenic technologies but not by single-stage membranes.
However, membrane are applied to the production of oxygen-
enriched air (OEA), to be used in chemical and related
industries, in the medical field, food packaging, etc. In industrial
furnaces and burners, OEA (25-35% O2) injection results in
higher flame temperatures and reduces the volume of parasite
nitrogen to be heated; this means lower energy consumption.
Belyaev et al.241 proposed to use OEA produced by membrane
systems in low quality coal gasification. Membranes are
economically convenient when the final O2 concentration is in
the range 25-50%;242 in this case, a single stage is the most
economic configuration.243 The separation is carried out with
the permeate under vacuum (with a flow rate lower than the
feed stream side).
Thousands of compact on-site membrane systems generating
nitrogen gas are installed in offshore and petrochemical industry.
Air Products Norway has delivered more than 670 PRISM
Figure 5. Photographs showing H2 membrane separation plants (from systems producing N2 for different ship applications, and more
PRISM brochure232). Top photograph: two-stage ammonia installation than 160 PRISM systems for offshore installations.244 In October
operated since 1979, that recycles 90% pure H2 to the reactor. Bottom 2008, Air Products announced to expand its manufacturing
photograph: refining installation operated since 1980 for upgrading a portion
of a naphtha hydrotreater off-gas to produce make-up H2 (>97%) for a
capacity (40000 membrane modules per year) by over 50% with
hydrocracker. Reprinted with permission from ref 232. Copyright Air a new facility near its PRISM production plant in Missouri
Products and Chemicals, Inc. (U.S.A.).245 In addition to generating N2, Air Products’ modules

are also used in enriching oxygen for passengers on the world’s
longest and highest highland railway (Qinghai-Tibet). Air
Liquide is installing in Dalian (China) a new air separation unit
with a capacity of 550 ton/day of oxygen to supply gaseous
O2, nitrogen, and argon by pipeline to the steelworks (Dongbei
Special Steel Group).246
In Japan, Ube Industries, originally focused on membranes
for hydrogen recovery in the petroleum refining and chemical
industries, has scheduled to double its module production,
passing from 20000 to 40000 units by October 2007.247 The
company is increasing its production of polyimide hollow fibers
to meet the demand for nitrogen separation membranes and
alcohol dehydration membranes. Membranes produced by this
technology are being introduced at a number of ethanol refining
plants, mainly in the USA and Europe, driven by the rapid
increase in the demand for bioethanol as an additive for petrol.
Dense inorganic membranes (ion transport membranes, ITM),
able to be permeated only by oxygen (or hydrogen), are being
developed to operate at high temperature, typically greater than
700 °C.248,249 High-temperature air separation process has better
synergy with power generation systems. Commercial-scale ITM
oxygen modules have been fabricated by Air Products (0.5 ton/
day of oxygen); this technology requires 35% less capital (much
simpler flow sheet) and 35-60% less energy (less compression
energy associated with oxygen separation) than cryogenic air
separation.250
4.3. CO2 Separation. Depending on the specific use of the
CO2 membrane in the production of power or hydrogen, the
necessary membrane properties may be significantly different.
Polymeric membranes are today more developed and com-
mercially available for CO2 separation. Rubbery polymers have
attracted greater interest for the separation of CO2 from H2 due
to higher flux rates and high selectivity (solubility controlled
or reverse selective H2 separation membranes). A limited
number of reports is related to this topic; polyacetylenes24 and
organosilane modified porous glass251 were studied for CO2/
H2 separation at low temperatures (25-40 °C). Glassy polymers
(mainly cellulose acetate and polyimides) dominate industrial
CO2 separation applications such as in the separation of CO2
from CH4, CO, N2 or other hydrocarbons.24
Carbon dioxide removal from natural gas (natural gas
sweetening) is mandatory to meet pipeline specifications (e.g.,
down to 2% vol. in U.S.A.), since CO2 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 technology is attractive
for CO2 and H2S removal, because many membrane materials
are very permeable to these species (enabling a high recovery
of the acid gases without significant loss of pressure in the
methane pipeline product gases), and because treatment can be
accomplished using the high wellhead gas pressure as the driving
force for the 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
Nm3/h) and remote locations, since amine processes are too
complicated for small productions. Membrane and amine
systems become competitive for a size of 6000-50000 Nm3/h,
while bigger plants are installed for offshore platforms or for
enhanced oil recovery. Membrane GS presents significant
advantages for the offshore industry; moreover, it is an
environmentally friendly alternative to traditional amine
absorption.
Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009 4653
Table 9. Permeation Data for Cellulose Acetate Commercial
Membranes
permeability (Barrer) separation factor (i/CH4) (-)
CO2 H2O CO2 H2S N2 C2H6 reference
8.9 500 20-25 50 1 0.42 230
8.9 500 21 19 1 0.42 253
Table 10. Cynara Hollow Fiber Modules
diameter (in) 5 12 16 30
length (in) 40 40 72 72
Cellulose acetate, initially developed for membrane reverse
osmosis, is the most widely used and tested material for natural
gas sweetening (Table 9), as in UOP’s membrane systems.252
Cynara-NATCO produces hollow fiber modules in cellulose
triacetate254 and has recently provided a membrane system (16
in. modules) for the natural gas sweetening in an offshore
platform in the Thailand gulf (830000 Nm3/h), which is the
biggest membrane system for CO2 removal.255 The plant reduces
the CO2 concentration from 36 down to 16% (in southeast Asia
a CO2 concentration of 23% can be acceptable for using the
gas in power stations). The geometric characteristics of the
Cynara modules are reported in Table 10. The 16 in. module
has a 17.5 times higher feed capacity than the flow-rate allowed
by a 5 in. module, while the 30 in. module (the last development)
allows a feed capacity 62.5 times higher than the smallest one,
reducing weight and footprint of more than 90%. This is
extremely important on offshore platforms and other space-
constrained facilities.
PRISM (Air Products) are other commercial membranes for
CO2 separation. Figure 6 represents a plant installed in July 2004
with a capacity of 9,500 Nm3/h of natural gas and reducing the
CO2 concentration from 4.5% down to ca. 2%.256
In the field of the natural gas treatment, commercially proven
membranes (NitroSep process, MTR)257 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 CO2 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. Polymeric membranes (e.g., MEDAL)258 are applied
to separate these streams into natural gas and a CO2 enriched
Figure 6. Natural gas treatment membrane plant. Reprinted with permission
from ref 256. Copyright Air Products and Chemicals, Inc.
4654 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009
Figure 7. (a) Natural gas treatment (one stage); (b) natural gas treatment (two stage); (c) CO2 enrichment [from ref 263].
stream, which is recompressed and injected in the wells. Cynara,
in 1983, installed the first membrane plant of this type in Texas
(U.S.A.). The plant, initially designed to reduce CO2 from 45%
to 28%, treating 60000 Nm3/h in 160 modules (5 in × 12 in),
is still working and today has a capacity of more 120000 Nm3/
h, decreasing the CO2 content from 80% to less than 10%.259
The high solubility of CO2 and H2S in cellulose acetate
induces plasticization, causing the polymer to swell with
disruption of the polymer matrix, with an increase in the mobility
of the polymer chains, thereby adversely changing the membrane
permeation characteristics. To overcome plasticization problems,
polyimides, in particular, have attracted considerable attention
due to their relatively high thermal, chemical, and mechanical
stability combined with high selectivity and permeability for
CO2.260 Polyimide membranes were initially used for hydrogen
recovery, but were then modified for CO2 removal. Cross-linking
was investigated as a method for reducing the incidence of
swelling and plasticization resulting from the exposure of
polyimides to CO2. This approach has led to significant
improvement without reducing CO2 permeability.261,262 Ube
industries commercialize aromatic polyimide modules, suggest-
ing 100 °C as the maximum operating temperature and a
pressure of 150 bar. Some examples of the use of these
membranes in CO2 separation applications263 are reported in
Figure 7.
The other important field where membranes can contribute
is CO2 capture. The aim is to reduce CO2 emissions into the
atmosphere, due to combustion of fossil fuels and contributing
to global warming. The key issue for CO2 capture is minimizing
the energy required in the overall process (capture + sequestra-
tion). CO2 capture in power generation processes that involve
fossil fuels can be divided into three strategies:
Precombustion fuel decarbonization involves the initial
conversion of a fossil fuel into H2 and CO2 (through, e.g., partial
oxidation, methane-steam reforming, or autothermal reforming,
followed by water-gas shift). Therefore, carbon of the fuel is
removed prior to combustion, whereby the fuel heating value
is transferred to hydrogen. In these cases, the CO2 separation

will happen at very high pressures (up to 7 MPa ∆P) and high
temperatures (300-700 °C).
Postcombustion capture involves the separation of CO2 from
the flue gas coming from the combustion of fossil fuels (from
a standard gas turbine combined cycle, or a coal-fired steam
power plant). This technology involves CO2 separation at a
relatively low temperature, from a gaseous stream at atmospheric
pressure and with low CO2 concentration (ca. 5-15% if air is
used during combustion). SO2, NO2 and O2 may also be present
in small amounts.
Oxy-fuel combustion is the process of firing a fossil-fueled
power plant with an oxygen-enriched gas mixture (95% oxygen)
instead of air. Usually, oxygen comes from a cryogenic air
separation unit, since this is a technology that is applicable for
large-scale plants. To keep combustion temperatures at a
permissible level, the mixture is diluted with recycled flue gas
(CO2). Oxy-fuel combustion produces approximately 75% less
flue gas than air-fueled combustion and produces exhaust
consisting primarily of CO2 and H2O and, therefore, ready for
sequestration. However, because of the energy and economic
costs of producing oxygen, an oxy-fuel power plant is less
efficient than a traditional air-fired plant.
Established methods for CO2 capture are absorption, adsorp-
tion, and membrane processes. Amine absorption is today’s best
available technology for postcombustion capture, with an
energetic cost in the range 4-6 GJ/ton CO2 recovered (mainly
due to significant energy consumption in the regeneration step).
This option 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 postcombustion 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. Favre et al.264
presented a simulation study on the separation performances
and energy cost of a single-stage membrane module for
postcombustion applications, considering coal-fired power plants
(10% CO2 in the flue gas) and binary dry CO2/N2 feed mixtures.
The authors found that the membranes currently available (CO2/
N2 selectivities less than 50) are not adequately selective to
produce the recovery ratios and permeate compositions called
for by government regulations, but membranes with a selectivity
above 100 are required. However, for flue streams containing
20% or more CO2, reasonable recoveries and permeate com-
positions (that do not exceed 80%) can be attained with currently
available materials and the related cost will be only about 0.5-1
GJ/ton CO2 recovered, which is lower than amine absorption
(steel or cement production).
Quite recently researchers from MTR have presented a two-
stage membrane process design for the postcombustion separa-
tion of CO2 from the flue gas of a 500 MWe coal fired power
plant.265 The design is based on bench scale test results of MTR
Polaris membranes with CO2 permeance of 1000 GPU and CO2/
N2 selectivity of 50. The flue gas is emitted at low pressure;
therefore, in order to reduce the compression costs, a blower is
used, and the driving force for the first membrane stage is a
downstream low vacuum (0.11 bar), whereas in the second stage
it is a sweep of air which then is sent to the combustion. In
turn, the CO2 entrained in the air stream and recycled increases
the driving force (19% CO2) for the separation in the first stage.
A 90% recovery of CO2 requires 18% of the energy produced
by the power plant, which compares well with the 30% of power
Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009 4655
required by an amine absorption process. The membrane surface
required for one single power plant, producing 500 m3/s of flue
gas and 460 ton/h of CO2, is about 5-10 × 105 m2: this huge
surface needs to be packed in spiral wound modules of very
large diameter, which require only 135 skids. The modest
pressures involved will not demand steel pressure vessels,
thereby reducing the investment costs. According to the
researchers of MTR, in real operations one of the main problems
that can be forecast is the effective removal of ashes with a
reasonably low pressure drop, and, in general, the removal of
CO2 from combustion flue gases remains an economical
challenge.
Amine absorption is the best option when a high purity is
desired, as for natural gas treatment, where methane losses must
be minimized. High purities systematically induce higher energy
consumption. Since N2 entrainment during capture has a
negligible impact on CO2 sequestration and only moderately
increases energy consumption due to compression, a less
selective process such as membrane permeation could be of
interest in order to minimize the overall energy penalty (capture
+ sequestration).264 These observations support the need for
materials development, but also show that membranes are
already promising for CO2 capture in certain industries.
When it comes to the reuse of CO2 separated from combustion
flue gases, one option is the dry reforming of methane, that is
the use of carbon dioxide instead of substantial parts of steam
for the production of synthesis gas. Since reforming is carried
at 600-800 °C, the economy of the process dictates that CO2
must be separated hot.266 Therefore, for the power generation
process the membranes are required to be stable at higher
temperatures, in excess of 300 °C. When coal is gasified, CO
in the syngas can be converted CO2 by means of the water gas
shift reaction (CO + H2O / H2 + CO2) at 350∼600 °C, whose
conversion is severely limited by thermodynamics. The mem-
brane removal of CO2 from the mixture during the reaction
would improve the yields, and at the same time would reduce
the costs of postcombustion CO2 separation. Even in this case
a CO2 selective membrane able to withstand high temperatures
is required. Yet an other case in which CO2 (and O2) selective
membranes resistant at high temperatures are needed is the
treatment of combustion flue gases, containing residual oxygen,
in order to obtain the oxidant of the oxyfuel combustion
process.267
Membranes based on alumina, zeolites, silica, and carbon
have received considerable attention in both amorphous and
crystalline forms for separating CO2 at high temperature.268
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 600 °C.268,269 These
membranes may provide an economically efficient, stable, and
robust separation membrane in applications where excess heat/
energy is 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.270 Integrated H2, O2, or CO2 membrane
separation is analyzed, 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 environ-
mentally sound technical solutions. In addition, further develop-
ment and validation of performance of membranes in real
applications are needed.
4656 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009
Table 11. Main Industrial Applications of Vapour/Gas Membrane
Separation
process recovery (%)
system
cost ($)
polyolefin plant resin 91 (hydrocarbon) 50 (N2) - ambient temperature); they are recovered as a liquid after
degassing
gasoline vapor recovery 95-99 (hydrocarbons) - brane also preferentially permeates water vapor, the residue gas
systems at large terminals
polyvinyl chloride 99 (VCM) -
manufacturing vent gas
ethylene recovery in 75 (ethylene) 550,000
ethylene oxide
manufacturing plants
ethylene recovery in vinyl 70 (ethylene) 700,000
acetate manufacturing
plants
natural gas processing/fuel 80 (C3+ hydrocarbons) - already large free-volume determines an increasingly larger
gas conditioning
4.4. Separation and Recovery of Organics from Gas
Streams. The separation and recovery of organic solvents from
gas streams is also rapidly growing at the industrial level. This
is an interesting field, which created a new market for
membranes, coupling economic and environmental benefits. This
area concerns the recovery of high-value organic vapors and
off-gas treatment. The main industrial applications of vapor/
gas membrane separation are listed in Table 11.15
The introduction of more stringent emission standard in
Germany at the end of the 1980s and in the United States at
the beginning of 1990s271 was an important driving force for
this advance.
The first small membrane units for separating organic vapors
from air were installed in the late 1980s. By the mid-1990s,
MTR (U.S.A.) was selling million-dollar systems (spiral-wound
modules) to petrochemical plants to recover olefins from
polyolefin production plants. In the same period, in Europe
GKSS and its licensees began installing large systems (plate-
and-frame modules) to capture gasoline vapors from tank farms
and fuel terminals. Baker15 in 2006 reported the following data:
the market for vapor separation systems was at least $20-30
million per year; more than 100 large systems, with a cost of
$1-5 million each, were installed; there were at least 500 small
systems, with a cost of $10,000-$100,000 each, operating to
capture vapor emissions from retail gasoline stations, industrial
refrigerator units, and petrochemical process vents.
For economic reasons, membranes for this application should
be organic vapor selective materials such as polymeric rubbery
membranes that selectively permeate VOCs (due to their high
solubility) from air or nitrogen. PDMS is used. Such systems
typically achieve greater than 99% removal of VOC from the
feed gas and reduce the VOC content of the stream to 100 ppm
or less. Membrane systems are competitive with carbon adsorp-
tion or condensation for streams containing more than 5000
ppm, particularly if high VOC recovery is required.
MTR and OPW Fueling Components have developed a
membrane vapor recovery system for the fuel storage tanks of
retail gasoline stations. The OPW Vaporsaver system, fitted with
MTR’s membranes, reduces hydrocarbon emissions by
95-99%272 and pays for itself with the value of the recovered
gasoline.
Recovery of natural gas liquids (NGL) is also attractive
because these hydrocarbons (C3+) have a better value as a
chemical feedstock than as a fuel and their removal is mandatory
in order to meet pipeline specifications for dew point and heating
value. Typically, NGL recovery is done in refrigeration and
turbo-expander plants, complicated to operate, with moving parts
and with high capital and operating costs. Membrane systems
(e.g., VaporSep, MTR272) are simple and low-cost solutions for
this application. Membranes are competitive with propane
refrigeration for flows up to 0.6-0.8 million Nm3/day.3 Heavy
hydrocarbons permeate faster than CH4 in these membranes (at
recompression and condensation. In addition, since the mem-
will also be dehydrated, reducing or eliminating the need for a
conventional dehydration system.
Glassy PTMSP and PMP are the most permeable and
selective polymers for the separation of n-butane from CH4.
Fumed silica as a filler proved effective in enhancing both the
permeability and the selectivity of PMP due to an increase of
free-volume.22,110,273 In PTMSP, instead, an increase of the
contribution of a methane selective Knudsen type gas transport,
which lowers the n-butane/CH4 selectivity.
4.5. Air and Natural Gas Dehydration. Finally, the air and
natural gas dehydration are placed among the most interesting
applications of membrane separation processes. In these opera-
tions the heavier species are present in dilute concentrations
and preferential permeation of the heavier species results in
lower surface area requirements; furthermore, the “cleaned”
lighter component is kept on the high-pressure side, which may
be advantageous.
An efficient membrane system for air dehumidification has
been commercialized by Permea (Cactus Membrane Air
Dryer).274,275 The membrane removes water, in the form of
water vapor, from compressed air, while nitrogen, argon, and
most of the oxygen continue through the hollow core of the
fibers to the end of the separator. Liquids should be removed
by coalescing filters upstream of the membrane. A small amount
of the slower gases passes through the fiber, and this is used to
sweep the water vapor through the separator. Cactus membranes
work on the principle of dew point depression. If inlet conditions
change, for example, compressed air with a lower inlet dew
point is supplied, the separator will provide dry air at an even
lower dew point. A refrigerated dryer dehydrates air by cooling
it down to condense the water, and with an electricity consump-
tion. Membrane dryers have a wide range of drying capability,
while desiccant dryers dehydrate air by adsorbing water on a
solid granular desiccant. Because the desiccant must be regener-
ated, two desiccant towers are used, and the air to be dried is
periodically switched between the two towers. Maintenance is
required on the switching valves, and there is the issue of
desiccant carryover into the dried air as well as desiccant life.
5. Hybrid Systems
Hybrid membrane processes are integrated processes in which
the membrane system operates in combination with another 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 favorably
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. An example is the pilot BP distillation/
membrane hybrid process for propane/propylene separation,276
where a part of the vapor mixture from the cryogenic distillation
column is sent in the membrane system which extracts the

propylene using an aqueous solution of silver nitrate (which
forms a reversible complex with propylene).
The integration of membranes with other separation processes
well-established in the chemical and petrochemical industries,
such as PSA, was considered in different works.277-281 Mem-
brane permeation can be an effective aid in the pressurization
and high-pressure adsorption steps of a typical PSA process;
the pressure difference available from the PSA can be used for
operating the membrane incorporated into the blowdown step
of the PSA cycle.282 Usually, the combination membranes +
PSA is considered in H2 separation, while hybrid membranes
+ amine absorption are applied to the CO2 separation. A
comparison of the separation cost for the membrane process
with diethanolamine (DEA) absorption showed that the mem-
brane process is more economical for CO2 concentrations in
the feed in the range 5-40 mol %.283 When the feed also
contains H2S, the cost for reducing the CO2 and H2S concentra-
tions to pipeline specifications increases with increasing H2S
concentration (1000-10000 ppm). If membrane processes are
not economically competitive because of the high H2S concen-
tration 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.283 A hybrid system (Cynara
membranes + amine absorption) is operating since 1994 in
Mallet (Texas, U.S.A.) to perform the bulk removal of CO2 from
associated gas (90% CO2 and heavy hydrocarbons), before
downstream treating. 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.284
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.
In this logic, the integration of commercial membrane separation
units (i.e., GS for hydrogen recovery, microfiltration for coke
removal, membrane contactors for water purification) within an
existing ethylene production cycle by steam cracking was
proposed.285 GS membranes for H2/CH4 separation reduce
significantly the energy required in the cryogenic distillation
section, allowing less severe operating conditions with respect
to the typical cycle. Other membrane units could be introduced
in the future, such as membrane systems for olefin/paraffin
separation which are very likely to be developed at a commercial
stage in the next few years.3 In a subsequent analysis, ethylene
production by a catalytic process (ethane oxidative dehydroge-
nation) was considered. The introduction of a membrane reactor
with an oxygen conducting membrane for the separate feeding
of oxygen was proposed.286 Moreover, the integration of a GS
membrane system, producing an O2-enriched stream, with the
traditional reactor was proposed. The membrane reactor process,
compared to the traditional one, achieves essential targets as
improved safety, the reduction of plant size and complexity,
energy and exergy savings, increased flexibility. These are
important aspects to be taken into account (e.g., by new
metrics287) in the evaluation of the overall performance in the
PI logic. In the PI strategy, the process quality evaluation should
take into account not only economical aspects, but also safety,
environmental and technical aspects, such as fire and explosion
risk, noise, emissions/waste, energy efficiency, flexibility and
controllability, reliability, and maintainability.
Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009 4657
6. Conclusions
In the chemical process industry, membrane-based gas and
vapor separations are today well consolidated and compete with
cryogenic distillation, absorption, and pressure swing adsorption.
Membranes compete with other separation processes on the basis
of overall economics, safety, and environmental and technical
aspects.
Originally, these systems were developed for hydrogen
recovery. Presently, there are several industrial applications
(production of nitrogen and oxygen enriched gases, H2 recovery
from refinery streams and CO2 separation from natural gas).
Membrane units are smaller than the conventional plants of
corresponding capacity, therefore they are suited for off-shore
natural gas treatment. The recovery of CO2 from flue gas streams
for environmental reasons is also under development. Emerging
fields are vapor/gas separation or N2/methane separation. There
are already developed applications of membrane units in the
petrochemical field; others might come with the availability of
new membrane materials able to withstand more demanding
process conditions of temperature, pressure, and aggressive
media. The permanent challenge in membrane GS technology
is to improve the current processes, extending the range of
application of this technology. Research in polymeric membrane
technology in recent years has resulted in the development of
systems which offer the potential for generation or separation
of gases for use in a range of applications at attractive costs.
The significant positive results reached in GS membrane systems
are, however, still far away to realize the potentialities of this
technology. Problems related to the pretreatment of the streams,
to the membrane lifetime, to their selectivity and permeability
slow down the growth of large scale industrial applications.
A great deal of research was carried out on improved
membrane materials for GS, since materials science is a critical
issue. The essential focus for R&D is on developing robust
membranes, in order to meet the key criteria of reliability and
durability for industrial applications.
Promising materials, such as carbon hollow fibers and hybrids
containing carbon nanotubes, still require other work. Inorganic
membranes, when industrially available, can find application
at high temperature, or in new applications involving hydro-
carbon vapors, contributing to the success of this technology.
However, a better engineering (design of supermolecular
membrane morphologies and economical modules) are equally
critical to the full field development. Besides the experimental
search for better membrane materials, molecular dynamics
studies, leading to better insights into the separation processes,
might help to develop molecularly engineered chemical struc-
tures with high fluxes at high selectivity.
The application of the membrane processes together with
other separation techniques in hybrid processes may be advanta-
geous. Despite all advantages, however, the potential of hybrid
separation processes in industrial scale is not fully exploited
because of the lack of general design methodologies and detailed
process know-how. In this respect, modeling of membrane
processes (integrated process simulator to model complete
hybrid process, predictive membrane and module performance
models) can be very useful. With the development of new
process concepts, new membrane applications will emerge.
Proper demonstration projects, such as some in progress, will
help this development.
Acknowledgment
The Italian Ministry of Education, University and Research
(Progetto “FIRB-CAMERE RBNE03JCR5sNuove membrane
4658 Ind. Eng. Chem. Res., Vol. 48, No. 10, 2009

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ReceiVed for reView December 10, 2008
ReVised manuscript receiVed March 6, 2009
Accepted March 9, 2009
IE8019032