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Review Article

Recent advances in the development of supported

carbon membranes for gas separation

Janice B.S. Hamm*, Alan Ambrosi, Julia G. Griebeler, Nilson R. Marcilio,

Isabel Cristina Tessaro, Liliane D. Pollo
Department of Chemical Engineering, UFRGS e Universidade Federal Do Rio Grande Do Sul, Eng. Luiz Englert St., ZC
90040-040, Porto Alegre, RS, Brazil

article info abstract

Article history: Carbon membranes have emerged in the 70's and have been presenting promising results
Received 28 March 2017 for application in processes involving gas separation because of their sieving effects. The
Received in revised form carbon membranes are obtained by pyrolysis of a precursor polymer beyond its initial
3 August 2017 decomposition temperature under essentially inert conditions. Supported and unsup-
Accepted 9 August 2017 ported carbon membranes can be produced, but the former are distinguished for the in-
Available online xxx dustrial separation of gases due to the improved mechanical strength and high chemical
and thermal stability. In this context, different types of support, coating methods and
Keywords: pyrolysis conditions for supported carbon membranes have been reported in the literature,
Supported carbon membrane in order to improve the separation capability of gas mixtures in respect to permeability and
Coating methods selectivity. The aim of this review article is to report and discuss the evolution of supported
Gas separation carbon membrane in the last 10 years in respect to configuration, transport mechanisms,
Transport mechanism manufacturing processes and its main applications, highlighting the main challenges still
to be overcome for this technology to be applied industrially.
2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Carbon membranes: concept, characteristics, configurations, and applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Transport mechanisms of supported carbon membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Manufacturing methods of supported carbon membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Support modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Polymeric coating techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Pyrolysis techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

* Corresponding author.
E-mail address: jbs.nice@gmail.com (J.B.S. Hamm).
http://dx.doi.org/10.1016/j.ijhydene.2017.08.071
0360-3199/ 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

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2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6
Challenges and prospects for the future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Introduction
Since the beginning of the 60's, synthetic membranes have
been successfully used in a wide variety of industrial ap-
plications [1]. Among them, polymeric membranes stand
out, being developed for the separation of gas mixtures
with good efficiency. However, these membranes present
limitations in selectivity, are more likely to wear out in high
pressures and have low thermal and chemical resistance.
Accordingly, in order to increase the separation efficiency
in gas separation processes, chemical modifications of
existing polymers, physical modifications of membrane
shapes and the synthesis of new polymers have been per-
formed [2e4]. Carbon membranes (CM), usually obtained
from the thermal decomposition (pyrolysis) of polymeric
membranes used as precursors, stand out as a promising
alternative for gas separation, mainly due to their high
separation capability (sieving effect) compared to polymeric
membranes [5,6].
Carbon membranes for gas separation were initially pro-
duced in the early 70s, by Soffer and Koresh, from the pyrol-
ysis of thermosetting organic materials [7e9]. Since then,
efforts are being focused in the development of new carbon
membranes with uniform pore distribution, different struc-
tures, and characteristics able to overcome or achieve the
selectivity/permeability limit when compared to commer-
cially available polymeric membranes [10e15]. Furthermore,
the high chemical and thermal stability of carbon membranes
is an advantage for its utilization in processes that are per-
formed under high temperatures [15e17].
The CM separation performance is controlled by a wide
variety of parameters involved in the pyrolysis process. For
example, the heating protocol [18,19] and the atmospheric
composition [20,21] may lead to distinct microstructures of
carbon membrane layer. Furthermore, the gas permeation
properties of CM are also influenced by several polymer-
precursor-determined properties: (i) pendant groups [22,23],
(ii) glass transition temperature [24], and (iii) free volume
[23,25]. PIM-1 (Polymer of Intrinsic Microporosity) represents
an extreme case in all of these categories as it possesses
polar cyanide groups, undetectable glass transition temper-
ature and, at the same time, it is one of the most permeable
glassy polymers known to date due to its high free volume
[26].
Due to the fragile characteristic of the thin carbon selective
layer, the carbon membranes have to be manufactured along
a porous support, usually ceramic or metallic, for commercial
purpose. Thus, a membrane is formed with an improved
mechanical resistance and thermal stability, supporting high
temperatures and pressures, ideal characteristics for gas
separation in several applications [27,28]. These membranes
offer great potential for operations with low maintenance, low
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energy demand, ease in scaling up and reliability [29,30]. In
this context, the aim of this article is to present an overview of
the carbon membranes studied in the last decade, specifically
the supported membranes for gas separation, with emphasis
on the relationship between structure and properties of these
membranes, in addition to highlighting the challenges still to
be overcome.
Carbon membranes: concept, characteristics,
configurations, and applications
A carbon membrane is a porous inorganic membrane gener-
ally obtained from the pyrolysis of an organic precursor. The
interest on this membrane for gas separation has increased
because of their molecular sieving properties that provide
better selectivity, and their higher thermal and chemical sta-
bility than the polymeric membranes [31e33]. The sieving
effect on the separation of gases by carbon membranes is so
important that the membranes are also known as carbon
molecular sieve membranes (CMSM), though other mecha-
nisms are also present, as detailed in Section Transport
mechanisms of supported carbon membranes.
The manufacture of carbon membranes using polymeric
films as precursor involves the selection of a polymer, the
preparation of the polymeric film and pyrolysis, wherein the
polymeric precursor undergoes heat treatment above its
decomposition temperature [31,34,35]. Polymer precursor
should present the ability to support high temperatures with
little contraction (thermosetting effect) and have a high car-
bon yield upon controlled pyrolysis [34,36]. The most widely
used thermosetting polymers are: poly(vinylidene chloride)
(PVDC), poly(furfuryl alcohol) (PFA), cellulose acetate (CA),
polyacrylonitrile (PAN), polyetherimides (PEI), phenolic resins,
and polyimides (PI) [31,35,37e39].
Depending on the conditions of pyrolysis parameters, the
process removes the majority of the heteroatoms originally
present in the polymer macromolecules, thus achieving a
crosslinked matrix and a hard carbon structure with almost
pure carbon material [40]. Therefore, the carbon membranes
present an amorphous porous structure, usually turbostratic
with hexagonal rings (Fig. 1), created by the removal of atom
groups generated during the pyrolysis of the polymeric pre-
cursor, producing combustion gases [40e42].
Amorphous and nanocrystalline carbon films can exist in
different kinds of matrices. The most common chemical
bonds in amorphous and nanocrystalline carbon are sp3 and
sp2 hybridizations. In the sp3 configuration, a carbon atom
forms four sp3 orbitals making a strong s bond to the adjacent
atom. In these films, sp3 dominates to establish a diamond-
like base framework [43e45]. In the sp2 configuration, a car-
bon atom forms three sp2 orbitals forming three s bonds and
the remaining p orbital forms a p bond. The p orbital
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6 3

Fig. 1 e Turbostratic graphite structure.

geometrically lies normal to the s bond plane and is the In addition to the bimodal pore structure, the carbon
weaker bond so that it is closer to the Fermi level, Ef. The three membranes have unique features when compared to poly-
s bonds and p bond usually constitute a ring plane in sp2 meric membranes: superior thermal resistance, chemical
clusters. A variety of larger clusters can be formed by fusing stability, high permeability/selectivity, and excellent struc-
double bonds and rings [46]. tural stability due to its material, carbon, which does not
Organized structures are still present in the subdomains of suffer with plastification and compaction [17,58]. Neverthe-
the CM, where the polymeric precursor structure is yet less, these membranes also have some limitations in respect
recognizable. This structural subdomain determines, in part, to fragility and production costs, which can reach three
the differences encountered in the performance of CM derived times the production costs of polymeric membranes
from various polymeric precursors [41,42,47]. The extent of [31,59,60]. In an effort to improve these characteristics,
the structure of this subdomain depends on the pyrolysis studies in material enhancement (polymeric precursor) and
conditions. The higher the temperature and the longer the development of new membrane configurations have been
pyrolysis period, the fewer similarities are found between the widely performed.
final carbon matrix and the initial structure of the polymeric Carbon membranes can be produced in similar configura-
membrane. For higher carbonization temperatures it was also tions as the polymeric membranes, such as hollow fiber, flat
observed that, in some cases, the final structure is composed sheet, tubular, etc, and they can be supported or non-
of graphite layers as well [41,42,47,48]. In carbon membranes, supported membranes [31,56,60e62], as summarized in
pores are created from imperfections between the micro- Fig. 3. Supported carbon membranes consist of a thin selective
crystalline regions of the polymeric material that are formed
during the pyrolysis, presenting a bimodal structure in the
form of grooves, which provides a single network combining
ultramicropores (Fp < 0.6 nm) and micropores (0.6 < Fp < 2 nm)
[49e51]. It is important to observe that although IUPAC clas-
sifies the pore sizes in micropores (Fp < 2 nm), mesopores
(2 < Fp < 50 nm) and macropores (Fp > 50 nm) [52], researchers
have also used the terminology ultramicropores due to the
sieving characteristic of carbon membranes [53]. Micropores
provide sorption sites, while ultramicropores enable molecu-
lar sieving, thereby making CM both highly permeable and
highly selective, with properties lying above the upper-bound
limit of polymers [54,55].
Carbon membranes with a bimodal pore distribution (mi-
cropores and ultramicropores) allow a high performance for the
separation of gas molecules under high temperature and pres-
sure and/or very similar sizes [25,36,56,57]. Fig. 2 presents the Fig. 2 e Pore size distribution devised for carbon
bimodal pore size distribution devised for carbon membranes. membranes. Adapted from Kiyono et al. [53].

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4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6

Fig. 3 e Configurations of non-supported and supported carbon membranes. Adapted from Ismail et al. [66].

film deposited on a support, which provides mechanical sta-
bility [63,64]. These membranes are distinguished from others
because they exhibit better mechanical properties and a very
thin separation layer, making them more suitable for use in
industrial applications [34,51,56]. They can also offer greater
flexibility, as the development of materials and/or technolo-
gies for different supports and selective layer can be opti-
mized [1,64]. In general, supported carbon membranes are
prepared by coating a ceramic or metallic support with an
adequate polymeric solution, and subsequent pyrolysis under
controlled conditions [12,34,56,65].
Ceramic supports, when compared to metallic ones, usu-
ally have a superior surface quality due to their greater surface
roughness, which facilitates the adhesion of the precursor to
the support, resulting in a thinner carbon membrane layer
[63,67]. Ceramic porous tubular supports are most often made
by the extrusion of a ceramic substrate [14,63,68].
A few factors directly influence the good performance of
supported carbon membranes, such as uniformity of the
support surface, penetration of the polymeric solution in the
pores of the support and adhesion of the polymeric layer to
the support [64,69]. In order to reduce flaws and improve
adhesion of the polymeric layer to the support, it is necessary
that the mean diameter of the support pores to be around one
order of magnitude smaller than the thickness of the poly-
meric layer deposited [1,58,70,71].
From the point of view of interfacial behavior, structure
and superficial roughness of the support also play an
important role in the pore size distribution of supported
carbon membranes and hence influence in their selectivity
[72]. The support structure, which is normally porous, may
influence the permeation of gases through CM, since the
major mechanism governing the transport of these gas
molecules is Pouiseille [34,72]. The support should offer a

Table 1 e Support configurations of carbon membranes manufactured over the last decade.
Author Year Support/geometry Pore size (nm) Reference
Centeno et al. 2004 Ceramic tube ~20 [74]
Ho Bum Park et al. 2004 Alumina tube ~150 [75]
Wang et al. 2005 Alumina disk ~20 [76]
Wang e Hong 2005 Alumina disk ~20 [62]
Lee et al. 2006 Ceramic tube ~100 [77]
Rajagopalan et al. 2006 Stainless steel disk ~2850 [78]
Wei et al. 2007 Novolac phenolic resin substrate with additives 100e300 [34]
Song et al. 2007 Coal-based carbon tube ~110 [61]
Zhang et al. 2007 Methyl-cellulose tube 100e560 [15]
Kong et al. 2007 a-alumina tube ~500 [79]
Song et al. 2008 Coal-based carbon tube ~110 [61]
Elyassi et al. 2008 a-alumina tube ~130 [80]
Weng et al. 2010 Alumina disk 140e400 [81]
Song et al. 2010 Carbon tube ~110 [82]
Tseng e Itta 2011 Alumina disk ~140 [57]
Itta et al. 2011 Alumina disk ~140 [83]
Song et al. 2011 Carbon tube ~100 [84]
Briceno ~ et al. 2012 Ceramic substrate with TiO2 structure 4500e5500 [85]
Bricen~ o et al. 2012 Ceramic tube ~1000 [67]
Tseng et al. 2012 Alumina disk ~1400 [72]
Wey et al. 2013 Alumina disk ~6.5e17 [86]
Hirota et al. 2013 a-alumina tube ~100 [87]
Cheng et al. 2014 Flat ceramic substrate ~10 [88]
Teixeira et al. 2014 a-alumina substrate e [89]
Rodrigues et al. 2014 Ceramic substrate with alumina nanoparticles ~200 [35]

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 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6 5

minor or negligible resistance to the passage of gas. In

contrast, when the surface roughness of the ceramic support
is high compared to the viscosity of the polymer solution to
be used, it eventually penetrates the support considerably
and in this way, influence on the increase of the pore size,
since the defects of the support are transferred to the se-
lective layer, leading to a decrease in selectivity and
increasing permeability [34,73]. Table 1 presents the main
support configurations for carbon membranes reported in
the literature over the last decade, with their respective
materials and pore size.
Along with the search for new materials and the
improvement of their properties, carbon membranes have
been increasingly used along unit operations, in integrated
systems. The applications that are gaining space and are
object of study of many research groups include propane/
propene separation [37], oxygen/nitrogen [13], hydrogen/
carbon monoxide [27], H2 recovery [85,90], methane separa-
tion from other biogas components [12], CO2 removal from
natural gas [88,91,92], among others [31,91,93]. As stated
above, the advantages include chemical and thermal stabil-
ity, especially in processes that occur at high temperatures
[15,16].
Transport mechanisms of supported carbon
membranes
The gas separation by membranes is based on the differ-
ences existent in the interaction between the components of
a gas mixture and the membrane, the critical membrane
pore size and the pore size distribution, and the mean free
path length of gas molecules [94,95]. In this sense, different
models have been proposed to explain the transport of gases
through carbon membranes. Since the membrane support is
not supposed to affect the gas permeation, and the carbon
membrane is an inorganic porous layer, the molecular sieve
(activated diffusion), the surface diffusion (selective
adsorption), the Knudsen diffusion, and the viscous flow
(Poiseuille flow) are the most accepted mechanisms [96,97].
The contribution of each mechanism to the gas transport is
dependent on the properties of membrane material, the
permeated gases and the operating conditions of the
permeation system, such as temperature and pressure used
[98]. Fig. 4 presents a schematic drawing of the main mech-
anisms and the pore size range in which they are considered
prominent.

Fig. 4 e Schematic drawing of the main mechanisms used to explain gas transport through carbon membranes. Pore size
cutoffs depends on the literature consulted, and contribution of each mechanism may vary depending on operating
conditions. Black and white spheres correspond to representative gas molecules.

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The molecular sieving or activated transport is the pre-
dominant transport mechanism present in carbon mem-
branes, in which the gas separation is based on the gas
molecule size; membrane pores contain large and narrow
apertures with constrictions that have similar molecular di-
mensions to the diffusive gas. In those constrictions, the
interaction energy between the molecule and the carbon
structure is composed by dispersive and repulsive forces
[99e101]. When the aperture becomes sufficiently small rela-
tive to the diffusive molecule size, the repulsive forces domi-
nate the molecule and it requires activation energy [11,12] to
pass through these constrictions. In this region of activated
diffusion, molecules with small size differences, such as He,
Xe, CH4, CO2, O2, N2, and SF6 can be efficiently separated by
molecular sieves, obtaining ideal separation factors ranging
from 4 to more than 170 [31,102].
The surface diffusion transport mechanism occurs when
permeate gases show a strong affinity for the membrane
surface and are adsorbed along the pore wall. In this mecha-
nism, separation occurs due to the difference in adsorption
quantities of the permeate species [103]. High permeability
and selectivity of the species can be observed due to the pore
filling effect by the adsorbable gases in the membrane struc-
ture, which reduces the open porosity and limits the diffusion
of less adsorbent gases in the micropores [15,104]. Surface
diffusion often takes place in parallel with other transport
mechanisms, such as Knudsen diffusion and/or molecular
sieve [67], and temperature determines this transition. Low
temperatures contribute to the adsorption of gases, then, the
transition depends on the species considered. Zito et al. found
selective adsorption to be greater than Knudsen diffusion for
temperatures lower than 330, 350, 400 and 500 K for N2, CO,
CH4 and CO2, respectively [105]. In this sense, non or low-
adsorbable gases such as He, H2, O2, N2, CH4 are effectively
separated from more adsorbable gases such as hydrocarbons
(C2), NH3, SO2, H2S, CFCs, etc. [38]. More details of this
mechanism can be found in the work by Rao & Sirkar [103],
which details the transport of gases and the requirements
needed for a practical surface diffusion membrane.
Knudsen diffusion is a mechanism that takes place along
pores with a narrow diameter, wherein the collision of the
molecules to the pore wall is prevalent. This mechanism oc-
curs when the mean free path of gas molecules is larger than
the pore size. In these situations, the collision of molecules to
the pore walls are more frequent than the collision between
molecules and the separation selectivity is proportional to the
inverse ratio of the square root of the molecular weights
[67,106]. The separation factor achievable by this mechanism
is generally low (for example, equal to 0.8, 0.6 and 4.7 for the
selectivities of CO2 with respect to N2, CH4 and H2, respec-
tively) and not practical, except in special cases (high tem-
peratures) [103].
In the gas separation by carbon membranes, the Viscous
(Poiseuille) flow mechanism has practical applicability for
explaining the high permeability and low selectivity pre-
sented by membranes with cracks or pinholes in the selective
layer. These defects, usually generated during the fabrication
steps, are not easily observable in the membrane structure but
can be detected by the continuous increase of gas perme-
ability with the upstream pressure and the lack of selectivity,
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evidence of the viscous transport through meso/macropores
(Fp > 20 nm) [107].
Manufacturing methods of supported carbon
membranes
Several manufacturing methods of supported carbon mem-
branes for gas separation have been reported in the literature
[65,108]. The process often requires a multi-step procedure,
such as the modification of support material, several stages of
polymeric coating, multiple carbonization cycles and post
treatments that are discussed as follows.
Support modifications
The porous supports play a fundamental role in the formation
of a uniform, thin and defect-free carbon selective layer.
Among the characteristics to be evaluated in these materials
are the pore structure and the roughness [33,69]. Large pore
diameter (LPD) supports, with pores usually larger than
2000  A, have rough surface. The use of these substrates
commonly lead to lower quality CM due to the occurrence of
interfacial defects during the formation of the selective layer
[34,77,109]. Small pore diameter (SPD) supports, with pores
generally smaller than 2000  A, have smoother surface and
should be preferably used. However, they are more difficult to
produce and, consequently, have a higher manufacturing
cost. The solution of these problems still is one of the major
challenges for the commercial application of supported car-
bon membranes [56]. Therefore, many studies related to the
modification of the supports, or even to the modification of
the operating conditions used for the support fabrication,
have been developed.
Liu et al. [58] studied the modification of Al2O3 supports
structure by immersing them into boehmite (g-AlOOH) solu-
tion, pursuing a more homogeneous coating of the polymeric
precursor polyamide-imide (PAI). The authors observed that
after several immersions, the support surface presented a g-
Al2O3 film with smaller pore sizes (4 nm) than the commercial
support (0.8e1 mm pore size), contributing to the attainment of
a homogeneous carbon structure, without fissures or other
imperfections. Rajagopalan et al. [78] studied the incorpora-
tion of silica nanoparticles in porous stainless steel supports
to verify the influence on the formation of carbon membranes.
The researchers noted a reduction of the pore mean size and
that the metallic support presented a flatter surface. In addi-
tion, they observed a significant improvement in oxygen
permeation by almost two orders of magnitude when
compared to membranes manufactured in unmodified
support.
Wey et al. [110] proposed the modification of the physical
properties of a a-Al2O3 substrate through a sintering technique
in the fabrication of carbon membranes with polymeric pre-
cursor polyetherimide. The authors observed that the specific
surface area of the a-Al2O3 substrate decreased and the mean
pore size improved with the increase of sintering temperature
from 1373 to 1673 K. Thus, the surface became rougher, hin-
dering coating of the polymeric layer homogeneously in the
surface of the ceramic support. Texeira et al. [89] studied the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6
fabrication of carbon membranes derived from a phenolic
resin-based polymeric precursor, using a non-porous ceramic
tube as support, the same being modified by the addition of
another porous ceramic tube with different alumina concen-
trations. According to the authors, the addition of a porous
support with a higher alumina concentration led to an increase
in the C/Al2O3 ratio, producing CM with greater volume of mi-
cropores and mean length. Hence, membranes with a higher
ratio of C/Al2O3 showed higher permeability for the gases used
and inferior permeability/selectivity.
Based on the studies presented, it is clear that promoting
modifications of the support is considered a promising alter-
native for certain applications. These modifications allow the
improvement of support characteristics, besides making
possible the use of supports with more accessible costs, such
as supports with larger pores or rougher surfaces. In addition,
another advantage is the possibility of using such modifica-
tions for simultaneous production/separation of the synthesis
gas. One example may be the manufacture of catalytic
membranes, where the insertion of catalysts may occur dur-
ing the manufacture of the ceramic support.
Polymeric coating techniques
To perform the polymeric coating on supports in the shape of
thin films, various options are available. The following tech-
niques stand out: dip coating [61,89,104,106], spin coating
[13,38,56,57,67,78,111,112], spray coating [61,102,113], ultra-
sonic deposition [114] and chemical vapor deposition (CVD)
[62,76,115].
Obtaining a supported polymeric membrane through the
dip coating technique involves dipping the support into a
polymeric solution, followed by solvent evaporation. This
technique is sometimes accompanied by vacuum utilization
to assist the solution adherence to the support [14,89,104].
Several authors utilized the dip coating technique
[14,15,61,80,89,104,116] for the fabrication of supported poly-
meric membranes. Teixeira et al. [89] coated a porous alumina
ceramic tube, supported in a non-porous ceramic tube, with a
solution of 10% (wt.) of phenolic resin in N-methyl-2-
pyrrolidone (NMP) with vacuum assist. These researchers
observed the formation of a homogeneous polymeric mem-
brane, well adhered to the surface and without flaws. Tanaka
et al. [104] made two coatings of a a-alumina ceramic tube in a
solution with resorcinol, formaldehyde, ethanol and sodium
hydroxide, and observed a smooth and homogeneous surface,
without flaws or defects. Sazali et al. [117] used a ceramic
tubular support and carried out two coatings with a polymeric
solution containing polyimide BTDA-TDI/MDI (P-84), nano-
crystalline cellulose and N-methyl-2-pyrrolidone. They
observed that the selective carbon layer formed presented no
and, that the presence of nanoparticles resulted in a decrease
of the thermal stability of the polymer blends.
The spin coating technique consists on depositing a pre-
determined quantity of polymeric precursor on the substrate
inside a chuck under vacuum in constant rotational speed for
a determined period of time [118]. In this technique, solvent
evaporation is accelerated by the induced air flux from the
high rotational speed. Thus, application, coating and drying
of a supported membrane can be carried out simultaneously
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separation, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.08.071
7
in a short time (<1 min) [118]. In recent years, many re-
searchers have used the spin coating technique to obtain
supported membranes, mainly because the coating efficiency
and production time [38,56,57,67,74,112]. Li et al. [56] applied
this method for coating carbon disks with a phenolic resin/
polyamic acid (PAA) polymeric solution and obtained homo-
geneous and crack-free films. Briceno ~ et al. [67] used the
same technique to coat ceramic tubes with polymeric solu-
tions of polyimide in NMP, at different ratios of polymer/
solvent (m/m). The authors reported flawless polymeric
membranes with only one coat by centrifugation. According
to them, the good result obtained is related to the high mo-
lecular weight of the applied polymer, which makes it
appropriate as a precursor for the fabrication of supported
carbon membranes. The molecular weight of a polymer and
its interaction with the solvent determine the hydrodynamic
volume of solvated polymer molecules. When the solvated
polymer molecules have a small diameter or the polymer has
a broad molecular weight distribution, the capillary forces
tend to draw the fine polymeric solution into the interior of
support pores, interrupting thereby the coating layer [119].
Thus, polyimide, a high molecular weight polymer, when
dissolved in solvents results in polymeric solutions of high
viscosity, even at low polymer concentrations. The viscosity
of the polymeric solution is directly related to the changes in
the entanglement of polymer chains during the polymer
coating on the ceramic support and its penetration into the
porous structure. Briceno ~ et al. [67] reported that using
polymeric solutions (polymer/solvent) with low polymer
concentrations (3e10%), the formation of a regular polymeric
film was not possible. By using a concentration of 13% (wt.)
(polymer/solvent), they observed the formation of a film with
regular and smooth thickness. Increasing the polymer con-
centration from 16 to 20% (wt.) in solvent, polymeric films
with uneven surface were produced.
The ultrasonic deposition technique (UD) consists in
inserting the solution in a sonifying syringe and pump it
through a nozzle, where the atomization happens generating
a thin mist, with micronized droplets that are deposited on
the support. UD provides a highly precise precursor deposi-
tion, producing extremely thin and reproducible films, strictly
distributed droplet size, and between 10 and 102 mm thick
[114,120]. However, in this last decade, no studies were found
about coating of supported carbon membranes using UD. It is
believed that the non-utilization of the technique is due to its
higher cost and greater sensitivity than other techniques used
for this purpose, with similar results.
The fabrication of supported membranes from the spray
coating technique involves the application of the polymeric
solution by spraying it on the support surface. Polymeric so-
lutions used in this coating technique usually have a very low
viscosity, which ensures the formation of fine droplets and
therefore obtaining an uniform membrane, making the tech-
nique ideal for the formation of carbon membranes [121,122].
However, there are no published studies with the application
of this technique for the fabrication of supported carbon
membranes in the last decade. Among the applications that
employ this technique, it is worth mentioning the manufac-
ture of polymeric solar cells [121], besides the fabrication of
supported membranes for gas separation [15].
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6
The chemical vapor deposition technique (CVD) in a sup-
port is used to produce supported carbon membranes with
high quality. In this method, the substrate is exposed to one or
more volatile precursors, which react and/or decompose over
the substrate surface to obtain the desired deposit. The heat-
ing process of the traditional CVD treatment occurs through
two steps: reduction of the catalyzed precursor and carbon
deposition. One disadvantage of this technique as compared
to traditional techniques, such as dip coating or spin coating, is
that these two steps have a relatively low productivity and
high cost [68,76,115]. Wang and Hong [62] used the CVD tech-
nique to coat carbon-based porous aluminium oxide disks
(substrate) in a vacuum chamber. The authors report obtain-
ing of smooth porous carbon films free of imperfections.
However, these membranes did not show molecular sieve
transport due to the pore size being greater than 0.7 nm.
Pyrolysis techniques
Pyrolysis is a slow process in which a precursor (polymer, coal,
resin, among others), adhered to a support, is heated to tem-
peratures between 673 K and 1673 K in a controlled atmo-
sphere (vacuum or inert) with a determined heating rate that
depends on the particular nature of the precursor [102]. In
pyrolysis, the diffusion of volatile components from the
membrane to the atmosphere is a critical step and it must
happen slowly to avoid interruption or fracture of carbon
networks. Pyrolysis time may vary considerably, depending
on film thickness, precursor type, final product composition,
among other factors [40,102].
During pyrolysis, split and reorganization of the main
polymer chains occur, and small gas molecules are released
and free radicals formed. The free radicals then become
crosslinked, giving rise to the graphene structure. Graphene is
a carbon allotrope, which bidimensional structure is a single
flat sheet of bonded carbon atoms, with hybridization sp2.
Carbon atoms are highly packed, and when the allotrope
presents itself in the shape of superposed sheets, there is a
graphite structure [12,77].
With the increase of pyrolysis temperature, occurs the
removal of the majority of heteroatoms originally present in
the precursor macromolecules, resulting in a matrix
composed mainly of amorphous, rigid, crosslinked and
porous carbon. This new structure is then obtained by the
removal of the gases and also by a reorganization of the
molecular structure of the polymeric precursor, where
consequently a great loss of mass occurs [55,102]. The ob-
tained amorphous carbon material presents specific pore
size distribution. This distribution consists of micropores
that connect the ultramicropores and are responsible for the
properties of molecular sieve separation, allowing a high
efficiency of gas separation [123]. A factor of great impor-
tance in pyrolysis is the temperature, since it has a direct
influence on the carbon membrane properties in terms of
structure, separation performance (permeability/selectivity)
and the transport mechanism for gas separation [124].
Several authors emphasize that an increase in pyrolysis
temperature reduces the permeability and increases the
selectivity, because it generates a more turbostratic struc-
ture, with higher crystallinity and density, decreasing the
Please cite this article in press as: Hamm JBS, et al., Recent advances in the development of supported carbon membranes for gas
separation, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.08.071
average interplanar spacing between carbon layers of
graphite [66,123,125,126]. At the same time, high heating
rates may lead to the formation of small holes, cracking,
microscopic bubbles and distortions that in extreme cases,
may restrict the membrane use.
Based on the exposed, the obtaining of supported carbon
membranes with different heating ramps during pyrolysis
was studied by several authors, with the aim of permeating
different gas pairs [13,36,61,71,78,79,83,113,127,128]. Song
et al. [84] produced supported carbon membranes from the
precursor poly(furfuryl alcohol). The pyrolysis procedure was
conducted using a segmented temperature ramp up to 1173 K
in an argon atmosphere. The authors obtained a uniform
composite membrane, with a fine top layer free of defects. The
selectivity results on the separation of gas pairs H2/N2, CO2/N2,
O2/N2 and CO2/CH4 were 465, 58.8, 13.2 e 160.5, respectively. In
addition, the researches further highlighted that selectivity
increases as the pyrolysis temperature increases, probably
due to the reduction of pore size. Teixeira et al. [89] performed
the pyrolysis in a straight ramp with heating until 1173 K
under nitrogen atmosphere; they manufactured supported
carbon membranes on ceramic tubes from phenolic resin
solutions with boehmite nanoparticles. The researchers noted
that the supported carbon membrane performance was su-
perior to the Robeson upper bound for the C3H6/C3H8 pair,
which indicates a membrane with good separation properties
and high efficiency. The C3H6 permeability was 420 Barrer, and
the selectivity in relation to the C3H8 was 18.1. Ma et al. [128]
used straight and segmented ramps with a maximum tem-
perature of 1073 K for the straight ramp and 903 K on the
segmented, under nitrogen atmosphere. The utilized precur-
sor was polyamide supported on a stainless steel ring. Ac-
cording to the authors, after pyrolysis at 903 K, the obtained
membrane was made of graphitic carbon and exhibited
excellent separation properties for the pair CO2/CH4, with
selectivity of 38 and CO2 permeability of 5040 Barrer. The same
researchers also noted that above 873 K a higher quantity of
micropores (<0.7 nm) was formed.
Based on the foregoing and emphasizing the polymeric
precursors that are mainly used in researches related to the
supported carbon membrane fabrication, Table 2 presents a
summary of the main studies reported in the literature over
the past decade, with the respective precursor polymers,
coating method, pyrolysis conditions and main permeability/
selectivity results.
Challenges and prospects for the future
Various aspects related to carbon membranes with emphasis
on supported membranes were reviewed in this paper.
Although a broad literature related to this theme is available,
it is poor in terms of presentation and comparison of mem-
brane features, configurations, transport mechanisms and
fabrication steps. Supported carbon membranes (CM) are a
derived from polymeric membranes, but they have greater
selectivity, permeability and resistance to heat and corrosion,
proving their importance in gas separation processes. The
increased research for supported carbon membranes in-
dicates that they have become a promising alternative to
separation, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.08.071
Please cite this article in press as: Hamm JBS, et al., Recent advances in the development of supported carbon membranes for gas

Table 2 e Main studies reported in the literature over the last decade for the manufacture of supported carbon membranes, with the respective polymer types, coating
methodology, pyrolysis conditions and main results of permeability/selectivity tests. This table is separated by the type of support, for better comparison.
Year Polymer Support material Coating method Pyrolysis conditions Permeability Ideal selectivity Perm/Select Ref
(pure gas) [Barrer]
2002 PFA Steel disk Ultrasonic Straight ramp Ar 79.8 Ar/N2 1.3 e [129]
1 coating Tmax: 723 K CO2 6.01 He/N2 15.4
5  C/min O2 2.6 O2/N2 4.3
Atm N2 60.4 CO2/N2 10
N2 He 9.27
2014 Phenolic Resin/PAA Coal disk Spin coating Segmented ramp H2 545.5 H2/N2 76.3 [56]

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6
e
2 coatings Tmax: 1073, 973 K CO2 88 CO2/N2 12.3
1 and 2  C/min O2 74.5 O2/N2 10.4
Atm Ar N2 7.15
Gas flow: 200 ml/min
2008 PEI/PVP Ceramic disk Spin coating Segmented ramp CO2 1463 CO2/N2 48.8 e [130]
1 coating Tmax: 773 K O2 723.7 O2/N2 24.2
0.5 and 1  C/min Vacuum N2 30
2011 PMDS Ceramic disk Spin coating Segmented ramp H2 1121 H2/N2 163 e [83]
Multiple Tmax: 1073 K N2 6.8 H2/CH4 160
5  C/min CH4 6.9
Vacuum
2011 PEI Ceramic disk Slide coating Segmented ramp H2 667.5 e H2/CO2 11.5 [131]
1 coating Tmax: 873 K CO2 222.5 CO2/CH4 75
1  C/min O2 57.8 O2/N2 75
Vacuum N2 8.9
CH4 8.9
2012 PPO/PI and PPO/PEI Ceramic disk Spin coating Segmented ramp H2 1448.3 H2/N2 171.9 [57]
1 coating Tmax: 873 K CO2 1318.2 H2/CH4 172.4
5  C/min O2 57.8 CO2/N2 156.4
Vacuum N2 8.4 CO2/CH4 156.9
CH4 8.4
2014 PEI Ceramic disk Spin coating Segmented ramp e H2/CH4 174.6 H2/CH4 174.2 [110]
1 coating Tmax: 873 K O2/N2 8.05 CO2/CH4 56.4
5  C/min CO2/CH4 56.4
Vacuum
2013 Phenolic resin Graphite Dip coating Straight ramp e e e [10]
1 coating Tmax: 973 K
1  C/min
Atm N2
2008 PFA Carbon Dip coating Straight ramp H2 9.33; e H2/N2 465 [61]
tube 1 coating Tmax: 1173 K CO2 1.18 CO2/N2 58.8
1  C/min O2 0.26 O2/N2 13.2
Atm Ar N2 0.020 CO2/CH4 160.5
CH4 0.007
(continued on next page)

9
 10
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Please cite this article in press as: Hamm JBS, et al., Recent advances in the development of supported carbon membranes for gas

Table 2 e (continued )
Year Polymer Support material Coating method Pyrolysis conditions Permeability Ideal selectivity Perm/Select Ref
(pure gas) [Barrer]
2009 PFA Carbon tube Dip coating Straight ramp H2 12.48 e H2/N2 196.47 [84]
1 coating Tmax: 973 K CO2 1.33 CO2/N2 20.95
1  C/min O2 0.76 O2/N2 11.89
Atm Ar N2 0.06 CO2/CH4 79.6
CH4 0.02

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6
2005 PIS Ceramic tube Dip coating Segmented ramp He 1107 He/N2 1845 e [75]
1 coating Tmax: 1073 K CO2 26 CO2/N2 43.3
3 and 5  C/min O2 19.3 O2/N2 32.1
Atm Ar N2 0.6
Gas flow:150 cc/min
2006 Phenolic Ceramic Dip coating Straight ramp H2 10 He/N2 2.3 e [132]
Resin 2 coatings Tmax: 873 K CO2 22 CO2/N2 5.1
1  C/min O2 4.5 O2/N2 1.0
Atm N2 N2 4.3 CO2/H2 2.2
2007 Phenolic Resin/PAA Ceramic tube VSC Segmented ramp O2 158 O2/N2 5.13 e [79]
Tmax: 893 K N2 30.8
2  C/min
Atm N2
Gas flow:
120 ml/min
2010 Phenolic Resin Ceramic tube Spin coating Straight ramp e e H2/CH4 15 [36]
Multiple Tmax: 1073 K H2/CF4 > 5910
5  C/min H2/i-C4H10>5910
Atm N2
2011 PP Ceramic tube Spin coating Straight ramp H2 8.7 e H2/CO2 2.02 [133]
2 coatings Tmax: 773 K CO2 4.3 CO2/CH4 0.75
1  C/min O2 5.2 H2/N2 1.98
Atm Ar N2 4.4 H2/CH4 1.53
CH4 5.7 O2/N2 1.18
2014 Phenolic Resin Ceramic tube Dip coating Segmented ramp H2 5.04 He/N2 > 544 H2/N2 445.6 [35]
1 coating Tmax: 823 K O2 9.85 H2/N2 > 586 He/N2 413.8
1  C/min He 4.68 O2/N2 > 11.5 O2/N2 8.7
Atm N2 CO2/N2 > 23.3
Gas flow: 170 ml/min
2014 Phenolic Resin Ceramic tube Dip coating Straight ramp H2 2047 H2/N2 65.6 e [89]
1 coating Tmax: 823 K CO2 1148 CO2/N2 35.1
273  C/min O2 153; O2/N2 4.7
Atm N2 N2 32.7 H2/CO2 1.8
Gas flow:100 ml/min He 971 He/N2 29.7
C3H8 1.96 H2/O2 13.4
C3H6 36.2 C3H6/C3H8 18.5
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6 11

commercial polymeric membranes for industrial gas separa-

[106]

[34]

[12]
tion. In this context, the application of supported carbon
membranes appears as a robust alternative to the substitution
or even to work in conjunction with traditional systems. The
use of the correct porous support improves the mechanical

N2/CH4 7.69
stability and reduces the fragility of the carbon membranes. It
CO2/N2 11
O2/N2 5.3
H2/N2 24

was observed that promoting the modification of less

expensive supports can be interesting to reduce
manufacturing costs of the CM. Dip coating and spin coating
e

have shown to be the most appropriate techniques to the

moment to promote the deposition of the polymer precursor
because they lead to better adherence on the support and a
CO2/CH4 0.69

H2/CH4 3.13
O2/Nz 0.97

shorter fabrication time than that found in other methods.

H2/N2 4.0

Other key step in carbon membrane manufacturing is the

pyrolysis procedure, in which the best selectivity/perme-
ability results obtained in the reported studies were from
e

segmented temperature ramps and slow heating rates.

In addition, the gas separation process through supported
carbon membranes still needs research for its better under-
standing and applicability. Hence, for carbon membranes to
CH4 75.96
CO2 52.67

N2 59.41
H2 237.7

O2 57.86

N2 6.78
CO2 20

become competitive with polymeric membranes there is a

N2 1.8
O2 9.6
H2 44

need to develop appropriate configurations for industry,

increasing packing density and, at the same time, maintaining
a permeability/selectivity with a high separation factor,
especially when it comes to the separation of gases with very
similar kinetic diameters. Accordingly, several strategies and
techniques have been discussed and studied with the goal of
Gas flow:500 ml/min

overcoming these drawbacks and developing a method for

Segmented ramp

carbon membrane fabrication that is possible to be applied at

Straight ramp

an industrial scale. Among the factors limiting its application

Tmax: 1173 K

Tmax: 1123 K
0.5  C/min

are the low mechanical resistance and the lack of a better

1  C/min
Atm Ar

Atm Ar

understanding of the phenomena that govern the separation

of gases/liquids through the membrane structure, heavily
e

dependent on the manufacturing conditions.

The use of computer simulation, present in several areas of
knowledge, has great importance for analysis and prediction
of the physical properties the materials can present, their
Dip coating

Dip coating
1 coating

1 coating

relation to their structure, and provide lower cost (time and

resources) when compared to experimental tests. In develop-
ment of new materials, for example, there is the possibility of
e

analyzing properties of materials that have not yet been syn-

thesized. Thanks to the simulations at the atomic level it is
possible to predict information at the microscopic scale, such
as reaction mechanisms and structural transformations that
Ceramic tube

Resin tube

would be very difficult and expensive to obtain experimen-

tally. Considering this, the computational tools can help to
cm (STP) cm/cm s cmHg.

predict the possible nanostructures formed in the carbon

e

membranes, corroborating the experimental data obtained. As

2

example, we can cite the recent work by Hamm et al. [134], who
performed a study on supported carbon membranes derived
from poly(ether imide). Furthermore, the computer simula-
tions can be used to evaluate the performance of separation
Phenolic Resin

modules at industrial units under different process conditions.

Considering the advances observed in this review and the
10

challenges to overcome, it is possible to visualize that the

1barrer 1  10
PFA

improvement of the technology of gas separation through

PI

carbon membranes would allow the upgrade of several areas

of industry. Among them, we can cite the nitrogen or oxygen
2014

2007

2014

enrichment from air for medical and industry purposes, the

separation of hydrogen from synthesis gas, the natural gas

Please cite this article in press as: Hamm JBS, et al., Recent advances in the development of supported carbon membranes for gas
separation, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.08.071
12 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6
purification, and the recovery of hydrogen from hydrocarbon
streams for energy, and the separation of alkenes/alkanes for
the petrochemical industry.
Acknowledgments
The authors thank the financial support from the Conselho
 gico (CNPq)
Nacional de Desenvolvimento Cientfico e Tecnolo
from Brazil.
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Please cite this article in press as: Hamm JBS, et al., Recent advances in the development of supported carbon membranes for gas
separation, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.08.071