Hindawi Publishing Corporation

Journal of Engineering
Volume 2013, Article ID 101746, 7 pages
http://dx.doi.org/10.1155/2013/101746

Review Article
Latest Development on Membrane Fabrication for Natural Gas
�uri�cation� � Review

Dzeti Farhah Mohshim, Hilmi bin Mukhtar, Zakaria Man, and Rizwan Nasir
Chemical Engineering Department, Universiti Teknologi Petronas, Bandar Seri Iskandar, Perak Darul Ridzuan,
31750 Tronoh, Malaysia

Correspondence should be addressed to Dzeti Farhah Mohshim; [email protected]

Received 4 September 2012; Accepted 1 November 2012

Academic Editor: Hyun Seog Roh

Copyright © 2013 Dzeti Farhah Mohshim et al. is is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.

In the last few decades, membrane technology has been a great attention for gas separation technology especially for natural
gas sweetening. e intrinsic character of membranes makes them �t for process escalation, and this versatility could be the
signi�cant factor to induce membrane technology in most gas separation areas. Membranes were synthesized with various materials
which depended on the applications. e fabrication of polymeric membrane was one of the fastest growing �elds of membrane
technology. However, polymeric membranes could not meet the separation performances required especially in high operating
pressure due to de�ciencies problem. e chemistry and structure of support materials like inorganic membranes were also
one of the focus areas when inorganic membranes showed some positive results towards gas separation. However, the materials
are somewhat lacking to meet the separation performance requirement. Mixed matrix membrane (MMM) which is comprising
polymeric and inorganic membranes presents an interesting approach for enhancing the separation performance. Nevertheless,
MMM is yet to be commercialized as the material combinations are still in the research stage. is paper highlights the potential
promising areas of research in gas separation by taking into account the material selections and the addition of a third component
for conventional MMM.

1. Introduction Conventionally, natural gas treatment was predominated

with some methods such as absorption, adsorption, and cryo-
Natural gas can be considered as the largest fuel source
required aer the oil and coal [1]. Nowadays, the con- genic distillation. But these methods require high treatment
sumption of natural gas is not only limited to the industry, cost due to regeneration process, large equipments, and broad
but natural gas is also extensively consumed by the power area for the big equipments [6]. With the advantages of lower
generation and transportation sector [2]. ese phenomena capital cost, easy operation process, and high CO2 removal
supported the idea of going towards sustainability and green percentage, membrane technology offers the best treatment
technology as the natural gas is claimed to generate less-toxic for natural gas [6]. Natural gas is expected to contain less
gases like carbon dioxide (CO2 ) and nitrogen oxides (NO𝑥𝑥 ) than 2 vol% or less than 2 ppm of CO2 aer the natural
upon combustion as shown in Table 1 [3]. gas treatment in order to meet the pipeline and commercial
However, pure natural gas from the wellhead cannot speci�cation [7]. is speci�cation is made to secure the
directly be used as it contains undesirable impurities such as lifetime of the pipeline and to avoid an excessive budget for
carbon dioxide (CO2 ) and hydrogen sulphide (H2 S) [4]. All pipeline replacement.
of these unwanted substances must be removed as these toxic Membrane technology has received signi�cant attention
gases could corrode the pipeline since CO2 is highly acidic in from various sectors especially industries and academics
the presence of water. Furthermore, the existence of CO2 may in their research as it gives the most relevant impact in
waste the pipeline capacity and reduce the energy content reducing the environmental problem and costs. Membrane
of natural gas which eventually lowers the calori�c value of is de�ned as a thin layer, which separates two phases and
natural gas [5]. restricts transport of various chemicals in a selective manner
2 Journal of Engineering

T 1: Fossil fuel emission levels (pounds per billion Btu of energy but, however, as the operating pressure increases, the per-
input). meability is decreasing due to experiencing lower diffusion
coefficients [34]. Polymeric membranes that are commer-
Fuel sources/pollutant Natural gas Oil Coal cially available for CO2 /CH4 separation include polysulfone
(pound/BTU)
(PSU), polyetehrsulfone (PES), polyamide (PI) and many
Carbon dioxide 117,000 164,000 208,000
more. Generally, as the permeability of the gas increases, the
Carbon monoxide 40 33 208 permselectivity was attended to decrease in most cases of
Nitrogen oxides 92 448 457 polymeric membranes [23].
Sulphur dioxide 1 1,122 2,591 Inorganic membrane like SAPO-34 could give higher
Particulates 7 84 2,744 separation performance compared to the polymeric mem-
Mercury 0.000 0.007 0.016 brane, but the separation performance is inversely propor-
tional to the pressure loaded. is observation may create
problem when we deal with high pressure natural gas well.
e performance of both organic and inorganic membrane is
[8]. Membrane restricts the penetration of some molecules
summarized in Robeson’s plot as in Figure 2 [35].
that have bigger kinetic diameter. e commercial value
of membrane is determined by the membrane’s transport
properties which are permeability and selectivity. Major gap 2.2. Conventional Mixed Matrix Membrane. A lot of
of the existing technologies is limited to low CO2 loading researches have been done to satisfy the needs of gas sep-
(<15 mol%). Ideally, we required high permeability and high aration requirement through both polymeric and inorganic
selectivity of membrane, but, however, most membranes membranes. e de�ciencies of these membranes have
exhibit high selectivity in low permeability and vice versa driven the researchers to develop an alternative material for
which make this is as a major tradeoff of membranes, membrane which is more mechanically stable and economic
and none of these technologies are yet to treat natural gas viable, and most important is having high separation
containing high CO2 (>80 mol%) [9]. performance. e combination of organic and inorganic
material which is known as mixed matrix membrane
(MMM) was then proposed in idea to get a better membrane
2. Membrane Technology Development gas separation performance at reasonable price [36]. e
fabrication of MMM was a promising technology as this
2.1. Early Membrane Development. Membrane technology
composite material has improved its mechanical and
has been started as early as in 1850 when Graham introduced
electrical properties [37], and it combines the exceptional
the Graham’s Law of Diffusion. en, gas separation uti-
separation ability and pleasant stability of molecular sieves
lization in membrane technology has been commercialized
with better processability of organic membrane [38]. e
in late 1900’s. Permea PRISM membrane was the �rst
MMM is characterized by dispersing the inorganic material
commercialized gas separation membrane produced in 1980
into the continuous phase of polymeric material which
[2]. Summary of early development of membranes is shown
can be almost any polymeric material such as polysulfone,
in Figure 1. is innovation has led to the further membrane
polyimide, and polyethersulfones [39, 40].
gas separation development. A lot of studies done by the
researchers for various gas separation mostly focus on the Various membrane materials can be selected based on
natural gas puri�cation. the process requirement. Selected materials can be “tailored-
Development of membrane for CO2 /CH4 separation has made� in order to meet the speci�c separation purpose in
been started since early 1990’s. Numbers of membranes were a wide range of application [39]. ere were many attempts
fabricated using different kind of materials in the early stage of developing polymer-inorganic membrane that started few
of this membrane gas separation. e desirable material decades back then.
selected must be well suited to the separation performance Based on Table 3, this was observed that the selection of
by which mean separation of gases works contrarily in dif- materials is important, and it depends on the system require-
ferent materials. Excellent gas membranes separation should ment. Higher intrinsic diffusion selectivity characteristic of
have the characteristic of high separation performance with glassy polymer makes this material better than rubbery
reasonable high permeability, high robustness, chemically, polymer [56]. Although MMM has proven an enhancement
thermally, and mechanically good and rational production of selectivity, it was noticed that most MMMs were endured
cost [10, 11]. Two types of materials are practically used in gas with poor adhesion between the organic matrix and inorganic
separation: polymeric membrane and inorganic membrane particles [55]. Even MMM fabrication does have its disadvan-
and the comparison of both polymeric and inorganic mem- tages, but the research of MMM with different materials is
branes is showed in Table 2. worth to work on since it has proven its ability to have high
Gas separation using polymeric membranes has taken its separation performance.
�rst commercial scale in late 1970’s a�er the demonstration
of rubbery membranes back in 1830’s [33]. Literally, the 2.3. Recent Development of Membrane Gas Separation
permeability of gas in a speci�c gas mixture varies inversely
with its separation factor. e tighter of molecular spacing it 2.3.1. Ionic Liquid-Supported Membrane (ILSM). In recent
has, the higher the separation characteristic of the polymer, years, many researches have been evaluated on the ionic
Journal of Engineering 3

1st commercialized Development of membrane

Early membrane
development gas separation for CO2 /CH4
membrane was separation
introduced
Medal polyimide hollow-fiber
membrane for CO2 /CH4
separation installed 1994

1850 1950 1960 1970 1980 1990 2000

Advanced membrane materials
for O2 /N2 , H 2 /N2
Van amerongen Permea PRISM and H2 /CH4
Graham’s law barrer made first membrane separations, Ube medal, generon,
of diffusion systematic was introduced 1980 1987
permeability
measurement Dried CA membrane
for CO2 /CH4
natural gas separation,
separex, cynara, GMS

F 1: Membrane development timeline.

T 2: Comparison between polymeric and inorganic membranes.

Polymeric membranes Inorganic membranes

Materials Present in either rubbery or glassy type which depends Made from inorganic-based material like glass,
on the operating temperature [12]. aluminium, and metal [13].
(i) Polymer is more rigid and hard in glassy state while (i) Able to withstand with solvent and other chemicals
in rubbery state it is more so� and �exible and also susceptible to microbial attack.
Characteristics (ii) Glassy polymeric membranes exhibit higher glass (ii) Comprise signi�cantly higher permeability and
transition temperature compared to rubbery selectivity, but they are also more resistant towards
membranes, and glassy types tend to have higher higher pressure and temperature, aggressive feeds, and
CO2 /CH4 selectivity [14]. fouling effects [15].
(i) May have plasticization problem when handling
high CO2 .
(ii) Presence of CO2 may result in membrane
performance reduction at certain elevated pressure. (i) Inherent brittleness characteristic.
(iii) As the membranes expose to CO2 , polymer (ii) Performed well under low pressure which does not
Disadvantages network in the membrane will swell, and segmental suit the natural gas well which required high pressure
mobility will also increase which consequently cause a for the exploration.
rise in permeability for all gas components [16]. (iii) High production cost which seems not practical for
(iv) e components with low permeability large industrial applications [20].
characteristic will experience more permeability
increment; thus, the selectivity of the membrane will
de�nitely decrease [17–19].
Polyethylene (PE), poly(dimethylsiloxane) (PDMS),
polysulfone (PSU), polyethersulfone (PES), polyimide Aminoslicate membrane [29], carbon-silicalite
Examples (PI) [21], polycarbonate [22], polyimide [23], composite membrane [30], MFI membranes [31], and
polyethers [24], polypyrrolones [25, 26], polysulfones microporous silica membranes [32].
[27], and polyethersulfones [28].

liquid supported membrane (ILSM) for gas separation mem- which make them also known as “green” solvents [58–
brane since ionic liquids are known materials that could 60]. Extensive researches have been carried out to develop
dissolve CO2 and stable at high temperature ranges [57]. To room temperature ionic liquid (RTIL)-based solvents for
be speci�c, ionic liquids are molten salt that are liquid at room CO2 separation with various types of ionic liquids such as
temperature [58]. Furthermore, ionic liquids are of particular pyridinium and imidazolium based. Among RTILs tested,
interest for membrane gas separation application as they imidazolium-based RTIL was chosen as the most feasible
are in�ammable, negligible vapour pressure, and nonvolatile solvent for CO2 separation as they are commercially viable
4 Journal of Engineering

T 3: Few researches of mixed matrix membranes.

Mixed matrix membrane (MMM)
Year Ref.
Organic Inorganic Observations
Poor adhesion of organic and inorganic selected leads
to poor separation performance.
1973 is poor interaction of both materials may result in [44]
Silicon rubber Molecular sieves
nonselective voids present at the interface which
consequently causes insufficient membrane
performance [41–43].
Zeolite like silicalite-1, 13X, and KY have enhanced the
Polydimethylsiloxane separation performance of poorly selective rubbery
1992 (PDMS) Silicalite-1, 13X, KY, and membrane for the carbon dioxide (CO2 ) and methane
zeolite-5A (CH4 ) mixture. [45]
Zeolite-5A showed no change in gas selectivity with
Propylene diene rubber
decrease permeability due to impermeable
(EPDM)
characteristic towards CO2 .
2000 Silicalite did in fact reverse the selectivity of CA [46]
Cellulose acetate (CA) Silicalite, NaX, and AgX
membrane from H2 to CO2 for CO2 /H2 separation.
Formation of chemical bonds gave good adhesion, but
2000 Polyvinyl acetate 4A there is still nonselective “leakage” from the existence of [47]
nanometric region.
Selectivity of CO2 /CH4 mixture has increased up to
45%.
Zeolites loading also affects both gas permeability and
2003 Matrimid Carbon molecular sieves gas mixture selectivity. ere were also a number of [50]
records where permeability increased with selectivity
decreased as the zeolites loading was increased [48, 49]
and vice versa [42].
2006 Polyethersulfone (PES) Zeolite 4A Due to low mobility of the polymer chain in glassy [53]
2001 polymer such as to prevent them to completely cover [54]
Polyimide (PI) Zeolite 13X
the zeolites surface which resulted in void interface
2008 Polycarbonate Zeolite 4A [51, 52]. [55]

Low P ILSMs have been proven that they offered an increase

Upper bound in permeability that outperforms many neat polymer mem-
100
High P branes. ILSMs synthesized from poly(vinylidene �uoride)
(P�DF) and 1-butyl-3-methylimidazolium tetra�uororate
(BMImBF4 ) showed high permeation performance of CO2
CO2 /CH4 selectivity

Zeolite membranes and mechanically stable while operating at high pressure

(SAPO-34) condition [63]. e consumption of RTILs showed an
10 increment especially for 1-R-3-methylimidazolium (R-mim)-
based RTILs as this type is preferable due to its properties of
less viscous compared to other RTILs. In addition, gases like
CO2 , nitrogen (N2 ), and other hydrocarbons demonstrated
Polymers
high solubility in Rmim-based RTILs [64, 65]. Besides,
1 the use of Rmim-based RTILs could calculate the latent
0.1 1 10 100 1000 10000 permeability and selectivity of the mixture of given gases
CO2 permeability ×10−10 cm2 (STP)/(s·cmHg) by using the molar volume of these RTILs [60]. RTIL can
be functionalized and set up in according to the system
Rubbery requirement and application, and these researches could
Glassy be good benchmark for designing the functionalized RTIL
efficiently as showed in Table 4.
F 2: Zeolite (SAPO-34) membrane performance in Robeson’s
plot.
2.3.2. Polymerized Room Temperature Ionic Liquid Membrane
(Poly(RTIL)). Comparatively, RTIL especially imidazolium
based can be also polymerized into a solid, dense, and thin
and easily tunable by tailoring the cation and anion to meet �lm membrane due to their modular nature [66–68]. It
the system requirements [60]. was a successful breakthrough when the researcher found
Journal of Engineering 5

T 4: Effects of ionic liquid functionalization. that the RTIL used which is emim[Tf2 N] was not selective
towards CO2 /CH4 separation [71]. Nonetheless, the result
Functionalization Effects proved that the addition of RTIL could increase the polymer-
(i) Gas solubility and separation zeolite adhesion in MMM as RTIL also acts as the wetting
performance have been tailored. agent for the zeolite.
(ii) Functionalized RTIL solvents displayed a Hudiono again repeated the same experiment fabricating
Nitrile and alkyne decreasing in CO2 , N2 , and CH4 solubility,
group a three-component mixed matrix membrane but by varying
but, however, the selectivity of CO2 /N2 and
CO2 /CH4 increased when compared to the
the composition of RTIL and zeolite added in order to
nonfunctionalized RTIL [61]. determine the optimum condition for the membrane. e
CO2 permeability seems to rise with the increasing amount of
(i) As the temperature increases, the CO2 RTIL. e CO2 /CH4 selectivity of the MMM also improved
solubility is decreasing while the CH4 with the presence of SAPO-34 compared to neat poly(RTIL)-
solubility remains unchanged. RTIL membrane as long as there is sufficient amount of
Temperature (ii) e ideal solubility selectivity of mix RTIL as the wetting agent. Besides, the team also conducted
gases for CO2 /N2 , CO2 /CH4 , and
an investigation of the separation performance by using the
CO2 /H2 increased as the temperature
decreased [62]. vinyl-based poly(RTIL). e addition of RTIL is not essential
as they are structurally similar [73].
In contrast, a ternary MMM has been fabricated by Oral
and his coworkers by using different materials. e project
that polymer from ionic liquid monomer had higher CO2 study on the effect of different RTIL loadings which are
absorption capacity with faster absorption and desorption emim[Tf2 N] and emim[CF3 SO3 ] towards MMM composed
rate compared to the neat RTIL [69]. Moreover, poly(RTIL) of polyimide-zeolite (SAPO-34). e addition of emim[Tf2 N]
is also attributed with higher mechanical strength [66]. has performed as expected when the permeability of CO2
ese characters have proven that polymerized ionic liquid increased while the incorporation of emim[CF3 SO3 ] has
(poly(RTIL)) is also a promising material for membrane gas increased the CO2 /CH4 selectivity since emim[CF3 SO3 ] is
separation. Polymerization of RTIL monomer by varying the selective towards CO2 /CH4 [74].
n-alkyl length also showed a pleasant result when increase
of permeability of given gases like CO2 , N2 , and methane
(CH4 ) was observed as the n-alkyl group was lengthened
3. Conclusion
[68]. Additionally, poly(RTIL) is also up to extend when it e escalating research in the membrane fabrication for gas
practically absorb about twice as much CO2 as their liquid separation applications signi�es that membranes technology
analogue which makes it much better than molten RTIL is currently growing and becoming the major focus for
[68]. Apparently, performance of poly(RTIL) also depends industrial gas separation processes. Latest research area using
on the substituent attached to it. In a research done on the mixed matrix membranes combines the �exibility and low
inclusion of a polar oligo(ethylene glycol) on the cation side capital cost with improving selectivity, permeability, chem-
of imidazolium-based RTIL, the separation selectivity has ical, thermal, and mechanical strength. Material selection
seemed to increase [70]. and method of preparation are the most important part
As discussed earlier, mixed matrix membrane is a known in fabricating a membrane. So the next research must be
membrane that composed of a compatible organic-inorganic very careful in determining the materials for gas separation
pair which demonstrated having good separation properties and methods applied in the fabrication stage. Even the
subject to no interfacial adhesion problem. e improvement synthesized MMMs were only tested in a small scale, the
of separation performance is expected in an MMM compris- research of MMMs is worth to be further explored since
ing poly(RTIL) (polymer matrix) and zeolite (inorganic). In MMMs have shown better separation performance compared
a very recent work, the bene�t of MMM has become an idea to polymeric and inorganic membranes.
to the researcher in ionic liquid membrane �eld. Hudiono
and his coworkers have introduced a three-component mixed
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