Chemosphere 325 (2023) 138300

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

A critical review in recent progress of hollow fiber membrane contactors for

efficient CO2 separations
Aniqa Imtiaz a, b, Mohd Hafiz Dzarfan Othman a, b, *, Asim Jilani c, **, Imran Ullah Khan d,
Roziana Kamaludin a, b, Muhammad Ayub a, b, Ojo Samuel a, b, Tonni Agustiono Kurniawan e,
NurAwanis Hashim f, Mohd Hafiz Puteh g
a
Advanced Membrane Technology Research Centre, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia
b
Facultyof Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia
c
Centre of Nanotechnology, King Abdul-Aziz University, 21589, Jeddah, Saudi Arabia
d
Department of Chemical and Energy Engineering, Pak-Austria Fachhochshule, Institute of Applied Sciences &Technology, Khanpur Road, Mang, Haripur, 22650,
Pakistan
e
College of the Environment and Ecology, Xiamen University, Xiamen, Fujian, 361102, PR China
f
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
g
Faculty of Civil Engineering, Faculty of Engineering, Universiti Teknologi Malaysia, 81310, UTM Johor Bahru, Johor, Malaysia

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Comprehensive review of membrane

contactors for CO2 separation.
• Review for conventional membrane gas
separation technology and membrane
contactors.
• Latest innovations in membrane con­
tactor module designs.
• Challenges encountered by membrane
contactors for CO2 separation.

A R T I C L E I N F O A B S T R A C T

Handling Editor: Y Yeomin Yoon Among wide range of membrane-based operations, membrane contactors, as they reify comparatively modern
membrane-based mechanism are gaining quite an attention in both pilot and industrial scales. In recent litera­
Keywords: ture, carbon capture is one of the most researched applications of membrane contactors. Membrane contactors
Membrane contactor have the potential to minimize the energy consumption and capital cost of traditional CO2 absorptions columns.
Gas separation
In a membrane contactor, CO2 regeneration can take place below the solvent boiling point, resulting into lower
Carbon dioxide capture
consumption of energy. Various polymeric as well as ceramic membrane materials have been employed in gas
Hollow fiber
liquid membrane contactors along with several solvents including amino acids, ammonia, amines etc. This re­
view article provides detailed introduction of membrane contactors in terms of CO2 removal. It also discusses

Abbreviations: HF, Hollow fiber; MC, Membrane contactors; NOAA, National Ocean and Atmospheric Administration; MGS, Membrane gas separation; CC, Carbon
capture; NCCC, National Carbon Capture Center; TIPS RAS, Topchiev Institute of Petrochemical Synthesis Russian academy of Sciences; IL, Ionic liquids.
* Corresponding author. Advanced Membrane Technology Research Centre, UniversitiTeknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia.
** Co-corresponding author. Centre of Nanotechnology, King Abdul-Aziz University, 21589, Jeddah, Saudi Arabia.
E-mail addresses: hafiz@petroleum.utm.my (M.H.D. Othman), ajilani@kau.edu.sa (A. Jilani).

https://doi.org/10.1016/j.chemosphere.2023.138300
Received 3 January 2023; Received in revised form 21 February 2023; Accepted 2 March 2023
Available online 7 March 2023
0045-6535/© 2023 Elsevier Ltd. All rights reserved.
A. Imtiaz et al. Chemosphere 325 (2023) 138300

that the main challenge that is faced by membrane contactors is membrane pore wetting caused by solvent that
in turn can reduce the mass transfer coefficient. Other potential challenges such as selection of suitable solvent
and membrane pair as well as fouling are also discussed in this review and are followed by potential ways to
reduce them. Furthermore, both membrane gas separation and membrane contactor technologies are analysed
and compared in this study on the basis of their characteristics, CO2 separation performances and techno
economical transvaluation. Consequently, this review provides an opportunity to thoroughly understand the
working principle of membrane contactors along its comparison with membrane-based gas separation technol­
ogy. It also provides a clear understanding of latest innovations in membrane contactor module designs as well as
challenges encountered by membrane contactors along with possible solutions to overcome these challenges.
Finally, semi commercial and commercial implementation of membrane contactors has been highlighted.

1. Introduction
Because of the swift economic expansion since 20th century, the
environment and climate have been affected adversely. Manmade di­
sasters such as acid rain and greenhouse effect are related closely to
industrial output and usage of energy (Nieminen et al., 2020; Pan et al.,
2020; Zhang et al., 2020a). National Ocean and Atmospheric Adminis­
tration (NOAA) Earth System Research Laboratories analysed that car­
bon dioxide (CO2) emissions are rapidly increasing globally and also the
concentration of CO2 within the atmosphere has approached a new
higher record of 441 ppm (Zhang et al., 2020b). This increasing con­
centration of CO2 within the atmosphere arising from globally growing
CO2 emissions is directly linked to harmful outcomes of climatic change
(Mikkelsen et al., 2010). In order to capture and separate CO2 from point
sources of emission as well as from atmosphere, the establishment of
carbon capture technologies provides an interim solution to reduce CO2
emissions (Wilcox, 2012). CO2 and hydrogen sulfide (H2S) are main
impurities present in effluent gases arising from industries and are acidic
in nature, also their chemical and physical characteristics are quite
identical in many aspects and their existence in natural gas can cause
many difficulties during its process and usage. CO2 content because of its
acidic nature decrease natural gas heating value, also considered as
main cause of global warming and can cause corrosion in equipment.
Hence, to encourage economic development and to comply with envi­
ronmental protection, capturing CO2 and H2S from natural gas is
important.
The utilization of membrane contactors in order to control and
manage CO2 emissions is gaining quite an interest. Out of many tech­
nologies that are used for CO2 separations, such as solid adsorption,
physical and chemical absorption, cryogenic distillation, carbon mo­
lecular sieve (CMS) adsorption and membrane separation, the through
going involves absorption into alkanolamine solutions via employing
conventional contactor equipment such as tray or packed columns.
Unluckily, this technique is energy intensive and hard to operate
because of problems such as flooding, foaming and channelling (Meng
et al., 2020). So as a substitute, membrane contactor technology that
combines both chemical absorption and membrane separation tech­
nologies, is therefore deemed as one of the leading technologies for
controlling CO2 emissions (Yan et al., 2007). However, gas separation
through membrane has been studied systematically for well over a
century, but membrane development technology along with fabrication
of asymmetric membrane progressed significantly in 1970’s (Baker,
2012; Chen et al., 2019). After this, remarkable breakthrough in in­
dustrial applications of membrane based gas separation technology,
especially for CO2 separation applications is reported (Bernardo and
Clarizia, 2013). Although, several improvements and advancements are
still needed in order to attain high gas separation performance via uti­
lizing membranes like improving durability and selectivity of mem­
branes as well as producing higher CO2 rates.
Several efforts have been made in area of membrane development to
attain such improvements. Gas-Liquid membrane contactors, as
mentioned above is one of the choices of leading membrane-based
separation technology which amalgamates membrane with conven­
tional phase contacting operation like absorption, and as a consequence
the advantages of both of the technologies are taken and utilized. Within
the membrane contactor, in order to provide extra contact area between
liquid and gas phases and to prevent dispersion among them, porous
membrane is utilized. Hollow fiber (HF) membrane modules as they
provide greater specific surface area (almost 30 times greater than
conventional contactor) are mostly preferred (Li and Chen, 2005;
Mansourizadeh and Ismail, 2009b; Pabby and Sastre, 2013). Membrane
contactors amalgamates the intrinsic advantages of membrane based
separation technology with that of chemical absorption (Cui and
deMontigny, 2013); the membrane modules are normally designed as
hollow fibers as they are low cost and typically allows a higher inter­
facial area (up to 10,000 m2/m3) considerably higher than most of the
conventional absorber columns, which in turn results into higher overall
mass transfer rates (Li and Chen, 2005). This hybrid process besides
providing greater surface area, also provides other benefits such as low
cost, modularity and independent gas-liquid control of flow rates
without giving rise to flooding (Drioli et al., 2005). So, these appealing
characteristics of membrane contactors led the researcher’s interest to­
wards using this process for natural gas purification/CO2 removal. As
mentioned earlier that gas-liquid membrane contactor is a hybrid
technique which is combination of both membrane based separation and
solvent absorption. In it, the gas and liquid phase are separated by the
membrane at the interface, hence offering mass transfer contact area for
carbon dioxide absorption as well as desorption (Drioli et al., 2011).
Within CO2 gas-liquid contactor, ideally membrane solely permeates
molecules of CO2 and rejects solvent transport and also transport of
other molecules of gas like nitrogen in flue gas and methane in case of
natural gas. Though, all components of feed pass through membrane
pores but only CO2 diffuses into solvent because of it having greater CO2
selectivity. Membrane contactor, in comparison to conventional packed
amine absorption column process offers larger mass transfer area of
1500–3000 m2/m3 per unit volume in comparison to column contactor
which provides mass transfer area of 100–800 m2/m3(Kumar et al.,
2002b). It is considered beneficial for processes like brownfield carbon
capture process as well as for sweetening of natural gas where limited
space is available. Furthermore, by applying reduced pressure or sweep
gas within desorber unit, regeneration below solvent’s boiling point
becomes viable (Scholes et al., 2020). This low temperature desorption
minimizes demand of energy by reducing water and solvent vapor­
ization. It was depicted by Wang et al. that if regeneration pressure is
around 20 kPa, 28% of energy can be saved (Wang et al., 2014).
One of the drawbacks of membrane contactors is additional mass
transfer resistance and is normally caused by membranes. Polymeric
microporous materials such as polytetrafluoroethylene and poly­
propylene are most commonly used to reduce this resistance (Zhao et al.,
2016a). Also, one of the major hurdles in development and progress of
membrane absorption mechanism is membrane wetting and with in­
crease of operating time, membrane wetting is mostly unpreventable. To
combat wetting that is caused by aqueous absorbent, membrane should
be hydrophobic because mass transfer is strictly restricted if membrane
continues to operate in wetting mode (Mosadegh-Sedghi et al., 2014;
Zhang and Jiang, 2019). In order to prevent membrane wetting,
compatibility among absorbent and membrane material is important.
Even insignificant degree of membrane wetting can have severe effect on

2
A. Imtiaz et al.
gas separation performance. Various techniques are employed by re­
searchers to prolong time needed for membrane wetting. Common
methods include modification of membrane material and improvement
of absorbent as well as of membrane structure.
This review article presents a detailed discussion about membrane
contactors employed for CO2 separation along with its comparison with
conventional membrane gas separation (MGS) technology. Previously,
many research studies have discussed the advancements in membrane
contactor technologies in terms of CO2 separations (Gugliuzza and
Basile, 2013; Li et al., 2020; Kim et al., 2021) but there are very limited
comprehensive research studies available that provides comparison
between membrane gas separation (MGS) and membrane contactors and
also highlights the challenges that are faced by membrane contactor
technologies along with possible ways to overcome them. This study is
novel as it provides a comparison between MGS and membrane con­
tactors employed for CO2 separation and also reviews the basic design
and operation principles of membrane contactors. It also provides brief
overview along with detailed discussion about the challenges encoun­
tered by MGS for CO2 separation and how membrane contactors can be
useful in overcoming these challenges as it is a combination of MGS and
chemical absorption technologies. It also covers the latest innovations in
membrane contactor module designs as well as the challenges encoun­
tered by membrane contactors and ways to overcome these challenges
during operation are also discussed. Later in this review, techno eco­
nomic analysis of membrane contactors in comparison to MGS is pre­
sented. Membrane contactors have been used both in industries and
academia for applications related to purification of biogas, natural gas
sweetening or cleaning of syngas. The studies on laboratory scale have
focussed on the fabrication of advanced membrane materials that have
the ability to overcome the challenges that are encountered by mem­
brane contactors during its operation and can provide greatest possible
advantages in terms of CO2 separation. In addition, several manufac­
tures have developed membrane modules as well as processes for pilot
scale trials and large scale operations and those are also highlighted in
this study.
2. Challenges encountered in membrane gas separation
In producing membrane for separation of CO2, achieving higher
permeability as well as selectivity is desired. Higher permeability is
preferred to minimize the membrane area required as well as the
operating pressure hence minimizing overall processing cost. While,
membrane with higher selectivity minimizes membrane area and it also
enhances the recovery of product. For CO2/CH4 separation, membrane
with higher selectivity is essential in order to minimize CH4 losses
throughout the process. In order to analyse the total processing cost, CH4
loses is considered as one of the essential parameters. Peter’s et al.
examined a membrane having CO2/CH4 selectivity of 35 for upgrading
natural gas (Peters et al., 2011). Simulation results displayed that CH4
loss of about 9.5% i.e. feed gas: 72.4 mol-% of CH4 and 9.5 mol-% of CO2
as well as of other gases such as propane, pentane, ethane, hexane,
butane were noticed in single stage membrane operation, however, in
two stage membrane operation just 0.47% of CH4 loses were observed.
Although two stage membrane process displayed lesser overall pro­
cessing cost, it could further be minimized if membrane’s selectivity is
enhanced.
The major disadvantage of employing polymeric membrane for gas
separation applications includes trade off phenomena among perme­
ability and selectivity as well as the occurrence of ageing and plastici­
zation. Second challenge that is encountered during development of
membrane for gas separation is the insufficient report on membrane
material’s selectivity in carbon dioxide-methane mixture measurements
(Baker and Low, 2014). Majority of notified performances of fabricated
membranes were based upon pure gas measurements. Few novel
membrane materials have displayed pure gas selectivity of 50; however
cellulose acetate having 10–15 mixed gas selectivity continues to remain
3
Chemosphere 325 (2023) 138300
as deployed material in natural gas purification plants. It has already
been made known that most of the membrane materials when being
tested with gas mixture at elevated natural gas processing pressures
might lose out their selectivity performances. Membrane’s permeability
is inversely related with selectivity, so the rise in membrane’s perme­
ability will in turn result in decreased selectivity and decrease in
permeability would result in increased selectivity. Robeson analysed this
characteristic, hence it is recognized as Robeson Upper bound (Robeson,
2008), yet only small number of membrane materials can cross afore­
mentioned upper bound. So, to attain remarkable improvement in per­
formance, it is necessary to develop and characterize membranes that
would cross upper bound i.e. higher permeability and selectivity. On the
subject of CO2/CH4 upper bound relation, thermally rearranged poly­
mers having benzothiazole-phenylene or benzoxazole-phenylene struc­
tures (Park et al., 2007) were classified by Robeson as the materials
having outstanding separation performance. Hence, this Robeson upper
bound plots for gas separations has now been extensively employed as a
standard for membrane’s fabrication and development because it dis­
plays the superiority of transport as well as separation characteristics of
developed membranes (Adewole et al., 2013a).
Membranes that are fabricated by employing glassy polymers have
high chemical resistance and permselectivity, also they possesses supe­
rior mechanical and thermal stability in comparison to rubbery poly­
mers hence, giving them superiority over other polymer materials
(Wang et al., 2009). But, glassy polymers endure plasticization at
elevated pressures and longer operational periods of CO2 removal, as the
membrane gets swollen and is susceptible to plasticization at higher
pressure when exposed to CO2 as well as other hydrocarbon compounds.
Plasticization is generally described as the increase in motion of poly­
meric chains because of the existence of single or several CO2 or heavy
hydrocarbon molecules. Consequently, each component’s permeability
increases while selectivity drops (Wang et al., 2007). In separation of
CO2/CH4 via membranes, sorption of CO2 in glassy polymers amelio­
rates local molecular organization hence, resulting in reduced permse­
lectivity. Occurrence of plasticization in polyimide membranes could
have three undesirable outcomes on gas separation. Firstly, many of the
membranes fabricated by employing glassy polymers exhibit a decline in
permeability by increasing pressure (Mikawa et al., 1999; Xiao et al.,
2007). But, rapid increase in permeability occurs if the feed pressure is
greater than plasticization pressure. Secondly, on increasing feed pres­
sure in case of CO2/CH4 separations, the separation factor declines
significantly (Hacarlioglu et al., 2003). Polymeric chains are stripped by
penetrant molecules hence resulting in swelling of polymeric matrix and
also leading towards increase in segmental mobility as well as free
volume of polymer matrix. Thirdly, the gas pair permeability is not
stable in case of plasticized glassy polymers and rises gradually with
time beyond plasticization pressure. The plasticization pressure gener­
ally works as an indicator for evaluation of polymeric material for
removal of CO2 and is defined as minimum pressure required that in­
duces surge in permeability (Dai et al., 2016a) (Fig. 1).
Membrane performance decreases at plasticization pressure which in
turn results in increased methane loss and hence can adversely affect the
economics (Wind et al., 2004). Dai et al. identified that plasticization
depends upon material’s thickness, CO2 exposure time and pressure,
aging time as well as its storage/preparation and thermal treatment (Dai
et al., 2016a). Several efforts have been made in order to reduce this
problem by modification of polymeric membranes which mostly in­
cludes polymer crosslinking and blending as well as thermal rear­
rangements (Zhang et al., 2013a, 2013b). These modification techniques
can reduce plasticization and enhance the membrane performance. The
improvement in membrane that was thermally modified was reported as
a result of arrangement of fraction free volume of membrane (Han et al.,
2010). Matrimid membrane’s thermal annealing has been developed in
order to overcome plasticization of this kind of polyimide (PI) mem­
brane (Dai et al., 2016a). Commercial PI Matrimid 5218 membranes
exhibited drastic decrease in CO2 plasticization after being annealed
A. Imtiaz et al.
Fig. 1. Schematic illustration of (a) permeability of CO2 vs. feed and plasticization pressure (b) aging time (Siagian et al., 2019).
thermally at 350 ◦ C for about 15–30 min for both mixed and pure gas
permeation tests (Bos et al., 1998). The use of thermal treatment for
commercial membrane fabrication process is considered difficult as they
require greater energy to produce. Hence, chemical cross linking
method to reduce plasticization is more efficient and uncomplicated
method with no use of heating (Zhou et al., 2003; Chen et al., 2012). The
cross-linking technique may bring about change in polymer’s chemical
structure and hence consequently changes the polymeric chain mobility.
Molecular free volume between polymeric chains increases on modi­
fying membranes by crosslinking technique (Zhang et al., 2013a). One of
the examples of cross-linking process to achieve high rigidity as well as
enhanced anti plasticization is cross linked PI. The process of cross
linking can be carried out via chemical, thermal and UV treatments. For
this purpose, diol crosslinking PIs containing carboxyl acid group have
been studied and explored extensively (Baker and Low, 2014).
In general, many impurities are present in natural gas stream that
could reduce membrane performance or cause damage to membrane.
The presence of moisture content could result in mechanical damage of
membrane, whereas heavy hydrocarbons could result in formation of
film on surface of membrane that in turn reduces membrane perme­
ability (George et al., 2016). Also, condensation must be avoided as it
could reduce membrane integrity. Uddin and Hagg (Washim Uddin and
Hägg, 2012) reported the effect of several impurities on the performance
of PVAm/PVA blend composite membrane. It was reported by them that
membrane performance as well as effect of impurities such as propane,
hydrogen sulphide and n-hexane are greatly affected by humidity. At
higher humidity, maximum loses of CO2 permeance as well as CO2/CH4
selectivity was about 18% and 16% respectively. Hence, it is necessary
that feed gas stream must undergo powerful pre-treatment in order to
avoid extreme damage to membrane performance (Baker and
Lokhandwala, 2008b).
Another major problem that is encountered in membrane based gas
separation is the physical aging phenomena associated with glassy
polymeric membranes application. Physical aging is linked with the
change of macrovoid or free volume within membrane matrix (Adewole
et al., 2013b). It is the outcome of polymer’s segmental motion that
steadily increases polymer density. Membrane’s permeability decreases
together with increase of membrane’s selectivity as the free volume
decreases as shown in Fig. 1 above. This occurrence could be detected by
decline of membrane flux with time. The process of rapid physical aging
which takes place within thin film membranes has not yet been clearly
understood. Although, many different key factors have been reported in
previous research studies that affects physical ageing response of thin
film membranes, they include membrane preparation as well as storage
history, thickness of membrane (thin membranes possibly have higher
rate of physical aging) and membrane’s operating temperature and
pressure (Dai et al., 2016a; Zhu et al., 2020). Strategies that are
employed in order to solve the problem of physical aging can be cate­
gorized into two different methods, (i) via freezing initial free volume
state in place such as polymer blending and hybrid material (ii) via
4
Chemosphere 325 (2023) 138300
employing cross linking agent in order to enhance structural rigidity
(Dai et al., 2016a). An attempt was reported by Lau et al. in order to
overcome the physical aging phenomena in glassy polymers employed
for gas separation applications (Amooghin et al., 2016). Three different
types of polymer membranes; poly (4-methyl-2-pentyne) (PMP), poly
(trime-thylsilylpropyne) (PTMSP) and PIM-1 were being modified by the
incorporation of porous aromatic framework (PAF), an ultra porous
additive. Extended performance test for up to 1 year specified that
modifications have the ability to successfully overcome physical aging of
above mentioned membranes while maintaining enhanced CO2 perme­
ability as well as higher CO2/N2 selectivity.
3. Membrane contactors as a promising technology for carbon
capture
Many patents were released during the past few decades with de­
velopments and inventions regarding removal of CO2 from gaseous
streams via membrane separations (Nogalska et al., 2017; Muthuku­
maraswamy Rangaraj et al., 2020) or by employing precipitation tech­
niques. Absorbent system employed to remove CO2 from flue gases via
precipitation generally comprises of absorbents like amine mixture and
amino acid salts (AAS), bicarbonates or metal oxides that are contacted
with gas stream containing CO2, hence resulting in precipitation of
solids. These salts are then drawn out from absorber and are then re­
generated within desorber via heat application. It is claimed by in­
ventors that capture efficiency of CO2 is greater than conventional
amine scrubbing unit with superior CO2 removal ability per cycle and
lesser loss of solvent vaporization. Even though, transport and separa­
tion of gases through membranes have been studied systematically for
over a century, but, membrane manufacturing technology together with
fabrication of asymmetric membranes made substantial progress in
1970s (Baker, 2012). Later, significant steps were taken in industrial
application of membrane based gas separation, especially for CO2
removal (Bernardo and Clarizia, 2013). Still, many advancements and
developments are still needed in order to attain higher gas separation
performance via employing membranes such as generating higher CO2
rates together with enhancing membrane’s durability and selectivity.
Many efforts have been made in area of membrane fabrication and
development aiming to achieve aforesaid membrane improvements. Gas
liquid membrane contactors is one of the novel options of membrane
based separation technologies and it amalgamates membranes with
conventional phase contacting operation and thus the advantages of
both technologies can be utilized fully. Since past few years there has
been an increase in publication trend based on membrane contactors for
gas separation applications as shown in Fig. 2 below. Besides CO2
removal, membrane contactors have also been employed for the gas and
water treatment. Various developed applications of membrane con­
tactors that have been made known in industries involve ammonia re­
covery from off gas stream, selective removal of heavy metal from
galvanic process bath and organic component recovery from process
A. Imtiaz et al.
Fig. 2. Publication trend of membrane contactors (Source: Googlescholars @
September 2022).
water in chemical industries (Klaassen et al., 2008b).
Membrane contactors as shown in Fig. 3 below are employed in
separation process because of many advantages such as they have
compact configuration and provide easy scale up, also they offer greater
gas-liquid contact area and hence helps in minimizing the contactor
weight and size. Furthermore, driving force is actually difference in
concentration gradients thus, there is no use to apply pressure and this in
turn eliminates flooding problem. It is important to select absorbent and
membrane that are compatible with each other for system efficiency. But
the most crucial factor is to control the wetting problem. High porosity
as well as open structure is beneficial for flux but regrettably they can
cause membrane wetting. Pores of membrane should remain dry and
open for gas in order to achieve efficient performance, as it helps in
keeping larger contact area. Hence, choosing a membrane having higher
hydrophobicity and absorbent solution having higher surface tension is
the perfect solution. Also, it is necessary that absorbent should display
higher affinity towards the gas consequently its gas absorption ability
should be higher along with the selectivity. Furthermore, absorbent
should also be compatible with the other components of system pos­
sessing such as, non corrosive characteristics. Though, membrane has to
provide higher gaseous permeability by having large open spaces in the
structure. Within membrane contactor, porous membrane is generally
utilized in order to provide extra contact area among gas and liquid
phases and in order to prevent dispersion among them. Hollow fiber
membrane modules as they provide higher specific surface area (Li and
Chen, 2005; Mansourizadeh and Ismail, 2009b; Pabby and Sastre, 2013)
which is almost up to 30 times greater than conventional contactor are
preferably used. Along with providing higher specific surface area, this
hybrid process provides further advantages such as low cost, modu­
larity, easy scale up and control as well as independent gas-liquid flow
rates without flooding (Drioli et al., 2005). These attractive attributes of
Fig. 3. Diagrammatic illustration of gas-liquid membrane contactors for
CO2 removal.
5
Chemosphere 325 (2023) 138300
membrane contactor have gained researcher’s interest to apply this
process for CO2 removal. Fig. 4 below shows the gas transport process
inside membrane contactor module.
3.1. Design of membrane contactor module
The configuration of membrane modules plays a vital role in order to
determine membrane contactor’s performance. Within gas-liquid
membrane contactors, it is essential that membrane module should
provide adequate gas liquid interface without the fluid’s convective flow
through membrane such as non dispersive gas-liquid contact. Both
tubular and flat sheet membrane module can be applied in gas liquid
membrane contactor. Tubular membrane module typically implies to­
wards hollow fiber (HF) membrane modules possessing inner diameter
that is less than 1 mm. HF MC’s have been studied widely for capturing
CO2 with extensive variety of absorbents. It must be recognized that in
some cases tubular membranes having internal diameter (>5 mm)
greater than that of HF membrane are employed in order to reduce the
pressure drop in post combustion carbon capture, in case of both inor­
ganic and polymeric membranes. A typical HF module is a bunch of fi­
bers that are aligned parallel in a shell, identical to shell and tube
configuration in heat exchanger. Most of the HF membranes have skin
layer on outer side, so liquid phase within HF membrane contactor is
mostly on shell side in order to reduce membrane wetting, while on the
contrary gas flows on lumen side, which is favourable for minimizing
pressure drop across membrane.
Flat sheet membrane modules can be organized in a plate and frame
configuration for MC’s applications. Within a flat sheet membrane
module, the membrane area is quite lower than in HF membrane mod­
ule, hence very few research studies are reported on utilization of flat
sheet MC’s, for applications related to CO2 separation (Dindore et al.,
2004a; Lin et al., 2009; Ahmad et al., 2010; Bougie et al., 2015). Though
various types of membrane module configurations have been progressed
but HF membrane modules with cross flow or longitudinal flow are
widely investigated for capturing CO2. Both cross flow and longitudinal
hollow fibers for gas-liquid contact were studied by Yang et al. and it
was inferred that cross flow MC’s exhibited enhanced absorption per­
formance (Yang and Cussler, 1986). However, most of the research
studies were carried out by employing longitudinal module design,
owing to the process simplicity (Yang and Cussler, 1986).
Fig. 4. Diagrammatic illustration of single HF membrane contactor and
membrane contactor module (Ramezani et al., 2022).
A. Imtiaz et al. Chemosphere 325 (2023) 138300

3.1.1. Longitudinal flow module
One of the major classifications of membrane contactors modules is
longitudinal flow module, within which the liquid and gas flows are
parallel either in counter current or co current (Mansourizadeh and
Ismail, 2009b; Zhao et al., 2016b). Longitudinal flow module takes
advantage of easier manufacturing, well defined mass transfer calcula­
tions and fluid dynamics. Nevertheless, this module configuration could
endure channelling as well as fluid bypassing on shell side because of
non-uniform packing, and could also endure higher tube side pressure
drop, hence both of these issues could affect module performance.
Though, addition of baffles could reduce the bypassing effect on shell
side. As discussed above that main type of module that is investigated in
this category is HF membrane module in which tubular membrane are
packed together in shell in pattern similar to shell and tube heat
exchanger. Flat sheet membrane module is an alternative to HF mem­
brane module and consists of flat sheets of membranes that separate
liquid from gas phase. As mentioned above that this module type
because of their low membrane area as well as relative unfamiliarity is
not as extensively studied as HF modules but they do possesses some
advantages such as ease of assembly, fabrication and upscaling as well as
identical surface on both membrane sides along with high gas flux per
unit of surface (Bougie et al., 2015).
3.1.2. Cross flow and woven fiber membrane modules
Cross flow modules where the flow circulates perpendicularly have
been suggested as an alternative to longitudinal flow module (Man­
sourizadeh and Ismail, 2009b; Zhao et al., 2016b). Within it, tubes could
be placed vertically whereas flow on shell side circulates horizontally
and vice versa. The configuration of cross flow module takes advantage
of minimum pressure drop and shell side channelling, high mass transfer
coefficients and greater overall efficiency in comparison to longitudinal
flow. Woven fiber membrane modules were proposed by Wang et al.
(2018) and they are identical to HF modules but the fibers are helically
woven together, as the name implies. Their woven structure helps in
elimination of shell side channelling as well as bypassing problems
encountered within HF modules because of the meandering effect on
flow that leads towards decreased mass transfer resistance as well as
increased removal efficiency. Nevertheless, woven configuration causes
decreased surface areas because the fibers are in direct contact partially.

Table 1
Review of different module design.
Types of Arrangement Design of Specifications References
membrane module

Hollow fiber Standard Tubular membranes that are packed into shell.Most commonly used (deMontigny et al., 2006;
(HF) membrane type. On tube side, pumping of liquid is challenging, if it is Bougie et al., 2014)
viscous. Higher pressure drop at small tube diameter. Shell side could
be subjected to channelling.
Woven Consists of HF membranes that are woven helicoidally. Minimizes shell (Wang et al., 2018)
fiber side channelling as well as bypassing, however, low surface area.

Cross flow Two phases i.e. shell side and tube side circulates perpendicularly. (Mansourizadeh and
High mass transfer coefficient, low pressure drop and shell side Ismail, 2009b)
channelling as well as improved efficiency as compared with
conventional HF modules.

Tubular Tubular membranes positioned between hot and cold chamber. Higher (Li et al., 2019)
effective area, easy cleaning, lower tendency of fouling, but higher
operating costs as well as lower packing density.

Flat sheet Spiral Flat membranes as well as spacers enwrapped and rolled around a (Winter et al., 2017)
wound perforated collection tube and radial circulation of phases across
membrane. Moderate consumption of energy as well as fouling
potential, adequate packing density. Easier up scaling and module
radius increases by increasing membrane length.

Standard Phases are separated via flat membranes. Easy assembling, fabrication (Bougie et al., 2015)
as well as up scaling, equivalent surfaces on each side, however, low
overall membrane area. Ability to feature various stages within a single
module

6
A. Imtiaz et al.
3.1.3. Spiral wound and tubular modules
The concept of spiral wound and tubular modules was also put for­
ward (Alkhudhiri et al., 2012). Within the spiral wound module, spacers
and membrane that are spiral in shape are encased and rolled around
perforated collection tube, also the feed flows radially into the module
moving towards collection tube in middle. Spiral wound module is
represented because of its moderate consumption of energy and fouling
potential as well as good packing density. Tubular module comprises of
tubular membrane that is inserted into two chambers, a hot chamber
and cold chamber (Alkhudhiri et al., 2012). This module is appealing as
it provides advantages such as easy cleaning, lower tendency towards
fouling as well as higher effective area, but lower packing density as well
as higher operating costs counterbalances it. Different module designs
that are described above are presented in Table 1 below.
3.1.4. Temperature swing membrane absorption process
Membrane contactor module was developed by Mulukutla et al.
(2015) for gas separation integrating absorption as well as stripping in
single HF module which could allow minimizing requirements in
equipment. This process itself is termed as temperature swing mem­
brane absorption process (TSMAP). It comprises of a cylindrical shell
having Y fitting on each side as well as two sets of polymeric HF
membranes that are positioned evenly together within the shell (Fig. 5).
Gas that is to be treated flows into the porous membrane, having shell
side filled up with the absorbent solution that remains static in course of
absorption or desorption. Once the liquid phase is saturated with CO2 as
the result of absorption cycle, the circulating flue gas is stopped.
Desorption can then be started via circulation of hot water within the set
of non-porous tubes that induces CO2 diffusion back into porous mem­
branes, that can afterwards be retrieved at higher concentration. After
desorption cycle, in order to cool down the absorbent, cold water is then
circulated into non-porous membranes, which afterwards is ready for
next absorption cycle. By utilizing a blend of 80 wt% of polyamidoamine
and 20 wt% ionic liquid as an absorbent, 2.92 × 10− 4 mol/m2/s of ab­
sorption flux was attained with an absorption temperature and gas flow
rate of 25 ◦ C and 24.1 cm3/min respectively (Mulukutla et al., 2015).
A functionally identical module was designed by Cai et al. (2016)for
physical absorption with propylene carbonate and water, but rather
operated in cross flow manner with absorption and desorption steps
operating at same time. Polypropylene membranes were employed for
gas phase while silicon rubber membranes were employed for process of
desorption. When CO2 is absorbed by the absorbent from Polypropylene
membranes, at the same time CO2 is desorbed from liquid by rubber
membranes owing to their higher CO2 permeability, which is afterwards
recovered by vacuum or stripping gas. Simultaneous CO2 absorption as
well as stripping indicated 78% improvement in permeation flux in
comparison to conventional modules. By employing water as a solvent,
2.66 × 10− 5 mol/m2/s of optimal absorption flux was achieved at the
Fig. 5. Temperature swing absorption-desorption module design (Mulukutla
et al., 2015).
7
Chemosphere 325 (2023) 138300
time when 45% of total membrane area consisted of porous membranes
(Cai et al., 2016).
3.2. Working process of membrane contactors
Separation of CO2 via membrane contactors comprises of two pro­
cesses i.e. absorption and desorption. In absorption, CO2 from the feed
gas is absorbed selectively within lean solvent phase. While in desorp­
tion, also termed as stripping, CO2 within a rich solvent is then released
as a purified stream for sequestration as illustrated in Fig. 6. The flow
diagrams of column and membrane contactors are quite similar, as in
case of membrane contactors, the column contactors are essentially
replaced with membrane modules. Gas and the solvent flows on the
opposite side of membrane that can be flat sheet or hollow fiber. Exis­
tence of pores within the membrane behaves as an independent and
fixed interface among solvent and gas stream. As described earlier that
unlike most of the membrane processes including gas separation or
microfiltration, driving force that is required for mass transfer is con­
centration gradient instead of pressure gradient, having selectivity
deriving from solvent properties. Membrane contactor’s advantages
over column contactors normally includes lower operational costs,
flexibility in operation as well as conveniently predictable design
(Ansaloni et al., 2019). The modular design of membrane contactor’s
permits operations over broad range of capacities, which means that
turndown and scale up is easier and straightforward. Significant mem­
brane configuration aids independent handling of flow of both liquid
and gas phases. Interfacial area do not varies along with operating
conditions which signifies that loading and overall performance is more
certain and predictable, hence leading towards lesser operational com­
plications (Criscuoli, 2009). One of the disadvantages involves arising of
additional mass transfer resistance because of the existence of mem­
brane. Also, gas phase impurities or solvent degradation could cause
fouling that may cause blockage of membrane pores, reduces mass
transfer as well as can shorten membrane’s lifespan.
The main target of a membrane contactor is to bring about mass
transfer among two phases without dispersion of one phase into another
(Gabelman and Hwang, 1999). Depending upon the particular
Fig. 6. (a) Flow diagram of packed column (b) Flow diagram of membrane
contactors for removal of CO2 from flue gas (Kim et al., 2021).
A. Imtiaz et al.
application, liquid phase could be organic or aqueous, while membrane
could be hydrophilic or hydrophobic (Kosaraju and Sirkar, 2007). The
separation factor in liquid/liquid extraction or gas adsorption is nor­
mally determined by component’s distribution coefficient in two phases,
though the transport efficiency is dependent upon the difference in the
chemical or physical properties among permeating compounds and
membrane. Whereas in membrane contactor’s, the idea of membrane is
quite different, it behaves as a physical support permitting the formation
of reliable interface among two phases at each single pore’s entrance.
Dependent upon the established equilibrium conditions, at that inter­
face, the component can either be removed or can be dissolved into one
of the two contacting phases. Major assumption should be made with
reference to membrane’s chemistry and structure. Some of the
physico-chemical and morphological elements such as controlled pore
size (0.02–0.2 μm), higher porosity, narrow distribution as well as
non-wetting should be well considered intending to meet the membrane
contactor’s key requirements which include: (1) higher volumetric mass
transfer rate (2) higher interfacial area per unit volume and (3) mem­
brane liquid controlled mutual interactions.
In order to produce the optimal surface exchange, higher pore fre­
quencies as well as uniform pore distribution throughout each surface
area are two important parameters. Also, limited transport resistance is
important for higher productive processing. Lower porosity along with
encroachment of viscous liquid inside pores of membranes can, conse­
quently, represents a major problem. For example, within gas-liquid
system, diffusion can only be allowed if pore are completely filled
with gas and wetting phenomena is avoided (Fig. 7). This goal is nor­
mally achieved with an adjustment among pore size and restrained
wettability.
While processing a membrane that is hydrophobic and have small
pores, lower membrane affinity towards water will restrict aqueous
phase to pass through pores except for if the pressure that is greater than
breakthrough pressure is applied. Breakthrough pressure is defined as
the pressure surpassing aqueous phase pressure in the course of opera­
tion and is represented by Young-Laplace equation (i), which is precisely
valid for cylindrical pores.
− 2γ cos θ
Pb = (i)
r
Fig. 7. CO2- Liquid membrane contactors (a)with no top layer (b) presence of
top layer (Gugliuzza and Basile, 2013).
8
Chemosphere 325 (2023) 138300
Where.
Pb= Breakthrough pressure
γ = Surface free tension among two phases
θ = Contact angle between membrane and two phases
r = Maximum pore radius
Generally, in case of hydrophobic membranes, aqueous phase pres­
sure is slightly greater than organic/gas phase pressure, yet is lesser than
breakthrough pressure. Gugliuzza and Drioli (2007, 2009a) proposed a
strategy in order to improve water repellence in case of hydrophobic
membrane contactors while taking care of higher breakthrough pressure
(Gugliuzza and Drioli, 2007, 2009). Roughness driven wettability was
suggested by them for microporous PVDF (poly (vinylidene fluoride)
membranes, indicating that in what way spherulitic morphologies can
improve surface roughness factor and reduces the line of adhesion be­
tween aqueous phase and membrane as illustrated in Fig. 8.
PVDF membranes that are greatly non wetted (ѳ ~ 150⁰) and having
breakthrough pressure that is greater than 2.5 bar and porosity equal to
80% have been modified via large spherical crystallites to create
membranes. Therefore, this indicates that how liquid-membrane mutual
interactions can be conveniently controlled by membrane topography.
During the course of operation, in order to avoid pore filling, porous
hydrophobic membrane could be coated with highly permeable and
dense layers. This technique is more beneficial as it permits membrane
processing with broad range of pressures (Fig. 6b). In certain case, the
component diffusion can be further enhanced by existence of immensely
specific carrier; hence, bringing forth improved selective processing.
That carrier could be dissolved into aqueous or organic phase that is
contained within the pores. The carrier’s higher specificity/selectivity
ratio could overcome the possibility of additional resistance to mass
transfer that is resulted from filling of the pores. Though, it should be
acknowledged that system’s stability is dependent upon several factors
which include miscibility, viscosity binding and volatility. Table 2 below
Fig. 8. (a) SEM illustration displaying PVDF membrane’s particulate like
morphology (b)membrane wettability dependence on pore size. (c)spherulitic
polymer particles effect on surface roughness of membrane (Gugliuzza and
Basile, 2013).
A. Imtiaz et al.
Table 2
General advantages and disadvantages of membrane contactors.
Advantages Disadvantages
Constant and high specific interfacial Additional mass transfer resistance caused
area (Gugliuzza and Basile, 2013) by membranes (Ramezani et al., 2022)
Absence of corrosion with no moving Low membrane lifetime along with higher
parts or usage of plastic equipment ( replacement costs (Mansourizadeh and
Drioli et al., 2005) Ismail, 2009a)
High compatibility and modularity, Risk of membrane fouling and wetting (
easy scale up and control (Simons Mosadegh-Sedghi et al., 2014)
et al., 2009)
illustrates the general advantages and disadvantages of membrane
contactors.
4. Development of membrane contactor technology for removal
of CO2
Significant research on the applications of membrane contactors for
removal of CO2 from several gas streams have been carried out, although
just a few of them had been tested in large or pilot scale. In relation to
that, the two main applications of membrane contactors for removal of
CO2 include CO2 removal from natural gas and post combustion carbon
capture (CC) (Zhao et al., 2016b; Sreedhar et al., 2017). The section
below reviews the experimental research carried out in progression of
membrane contactor technology for CO2 removal.
Quite a lot of research studies on membrane contactors were carried
out that were associated with realistic conditions of separation of CO2
from natural gas. Poly fluoroalkoxy (PFA) hollow fiber membrane con­
tactor’s long term operating stability has been summarized by Al Mar­
zouqi et al. in simultaneous removal of H2S and CO2 from gaseous
stream whose composition was quite identical to that of natural gas at an
elevated pressure of 50 bar and employing hot absorbent at 100◦ Cof
temperature (Al-Marzouqi et al., 2017). High-pressure membrane con­
tactors were also notified in other works (Marzouk et al., 2010, 2012;
Kang et al., 2017). In case of natural gas sweetening, simulation and
modelling of membrane contactors have also been carried out (Reza­
kazemi et al., 2011; Quek et al., 2018), hence providing meaningful
insight for operation and design characteristics.
A unique approach was suggested by Vericella et al. termed as
encapsulated solvent in order to combine the application of solvent
absorption and membrane to trap CO2 from flue gases. Solvent is
encapsulated within a thin membrane capsule having thickness and
diameter of 10 μm and 100–600 μm respectively. This idea amalgamates
the advantages of both technologies where, selectivity of solvent reacts
with CO2 and not with N2 in a contactor having high surface area that is
provided by silicone based membrane capsule (Vericella et al., 2015). In
comparison to conventional absorber, this results into smaller contactor
dimensions. It is advantageous as the solvent selectivity and microcap­
sule (membrane capsule) permeability can be modified independently
and, this is different to traditional membrane based gas separation
where selectivity and permeability are competitive parameters (trade off
phenomena) (Powell and Qiao, 2006). This aforementioned design has
been examined both at pilot and laboratory scale; 1MWe of coal testing
facility at DOE National Carbon Capture Center (NCCC) (Hornbostel
et al., 2019). By employing their presumed capsule properties and 30 wt
% of sodium carbonate Na2CO3 solution as working solvent, the required
height of absorber and also the energy penalty are about 10% and 18%
lesser than traditional MEA absorber system. Intending to be economi­
cally competitive in comparison to traditional absorber, it was described
that the thickness of capsule should be reduced by order of magnitude
without affecting capsule’s integrity and stability (Raksajati et al.,
2018).
Membrane contactors have also been broadly designed in order to
separate CO2 from renewable resources like biogas. Different re­
searchers from TIPS RAS (Topchiev Institute of Petrochemical Synthesis
9
Chemosphere 325 (2023) 138300
Russian academy of Sciences) in an association with NPK BIOTEST
constructed and tested a pilot scale membrane contactor based upon
PVTMS non porous membrane for conditioning of biogas (Shalygin
et al., 2011). The results proposed that flow of the controlling absorbent
is quite important in order to deal with varying flow and compositions of
biogas. Significant efforts in development of membrane contactors were
proclaimed by Park et al. for upgradation of biogas suggesting mem­
brane contactor with pressure cascading stripping configuration (Park
et al., 2017), and also pilot and bench scale tests of membrane contactors
were conducted by Schiavon Maia et al. for removal of CO2 and H2S from
biogas by employing regenerable Fe-EDTA solution (Schiavon Maia
et al., 2017). Separation of CO2 from biogas was carried out by Lee et al.
(2020)via employing hollow fiber membrane contactors and the effect
of temperature on performance of membrane contactors was examined.
According to them, the temperature of solvent had no major effect on
removal efficiency of CO2, although gas temperature rendered a signif­
icant effect on CO2 removal efficiency. On increasing the gas tempera­
ture from 20 to 35 ◦ C at 0.75Nm3/hof gas flow rate, the CO2 removal
efficiency was increased and reached a maximal value of 71%. On
further increasing the gas temperature to 50 ◦ C, the removal efficiency
was decreased (Lee et al., 2020).
5. Challenges encountered in membrane contactors
5.1. Selection of suitable solvent membrane pair
In case of membrane contactors, it is essential to select the solvent
wisely and carefully, aiming to attain higher separation performance.
Normally, the solvent is supposed to be compatible with the membrane
type that is utilized in membrane contactors and must have higher CO2
absorption capacity. It is essential to examine compatibility between
solvent and membrane as the solvent could react with polymeric
membrane, which in turn could cause membrane degradation (Luis
et al., 2012). In order to prevent membrane damage both chemically and
physically, it is important to select solvent membrane pair carefully. The
change in the properties of membrane when it is exposed to sorbent has
already been explored by various studies. The changes in the surface
morphology of polypropylene (PP) membrane amid its initial contact
with water have been investigated by Barbe and co-workers (Barbe
et al., 2000b). They noticed that after 72 h of contact, membrane surface
morphology, e.g. pore (length, diameter and area), porosity and also
pore spread factor were changed because of non wetting intrusion of
water into some of the pores that enlarged pore entrance (Barbe et al.,
2000b). In a study carried out by deMontigny et al., two different types
of hydrophobic HF membranes including PTFE and PP, were utilized in
capturing carbon from flue gas by employing membrane contactors, and
aqueous solutions of MEA (monoethanol amine) and AMP (2-ami­
no-2-methyl-1-propanol) were employed as solvents (deMontigny et al.,
2006). It appeared that PP membrane experienced deterioration in
performance with time, while PTFE membrane managed maintaining its
initial performance (deMontigny et al., 2006). Kamo et al. investigated
the effect of several solvents on polyethylene microporous membrane’s
properties (Kamo et al., 1992). Solvents utilized for their research study
included ethyl alcohol, Monochlorobenzene, n-hexane, p-Xylene, DMSO
and DMF. On treating with those solvents, the membrane’s permeability
increased, pore size enlarged and the membrane appeared shrinking. It
was concluded by them that it happened because of the deformation of
microfibrils of HF membrane, that could be caused by solvent’s surface
tension (Kamo et al., 1992). This micro fibril’s deformation was fol­
lowed by adhesion of adjacent microfibrils.
The compatibility between membrane and solvent for applications
involving CO2 removal by employing membrane contactors were also
explored by Dindore et al. (2004b). Five different types of membrane
materials such as PVDF, PS, PTFE, PES and PP along with eight different
types of solvents such as selexol, water, dimethyl formamide, propylene
carbonate, N methyl pyrrolidone, tributyl phosphate,
A. Imtiaz et al.
n-formylmorpholine and glycerol triacetate were employed in the study
(Dindore et al., 2004b). The study revealed that only PP and PTFE were
appropriate and compatible with organic solvents while other materials
were quite incompatible in terms of shrinkage, colour changes,
morphological damage, swelling and dissolution. It was found out by
authors that PP and PTFE membrane materials when employed in
combination with propylene carbonate solvent came out to be a
favourable membrane solvent pair for CO2 absorption. Also, in terms of
membrane’s fabrication cost, combination of PP and propylene car­
bonate was reviewed as the best candidate (Dindore et al., 2004b).
5.2. Fouling
One of the main problems that are encountered during membrane
operations is membrane fouling (Kang and Cao, 2012; Khoiruddin et al.,
2017; Zhang and Jiang, 2019). This phenomenon of membrane fouling
results in reducing membrane flux which in turn restricts membrane
process applications (Rana and Matsuura, 2010; Aryanti et al., 2017;
Zhang et al., 2021). Hence, fouling of membrane is another major
challenge encountered in membrane contactor applications, although
it’s harmful impact on membrane contactor’s performance is lesser as
compared to the impact of membrane wetting phenomena. In membrane
contactor, fouling is recorded to be less severe than membrane filtration.
Yet, membrane fouling grows into a major concern in industrial appli­
cations where stream of flue gases contains contaminants such as sus­
pended particles or dust. It was reported by Zhang et al. that the
presence of fine particles in flue gas coming from desulphurized coal
fired power plant reduces CO2 removal efficiency because of the
adsorption and deposition of fine particles on the pores and surface of
microporous membrane (Zhang et al., 2015). To prevent membrane
fouling, it is essential that contaminants must be eliminated in flue gas
pre-treatment facility. Also, the utilization of membranes possessing
antifouling and self-cleaning properties could reduce the problems
related to membrane fouling without requirement of pre-treatment fa­
cility (Zhang et al., 2015). It was reported by Xue et al. and Bhushan
et al. that super hydrophobic membranes possesses self-cleaning prop­
erty (Bhushan et al., 2009; Xue et al., 2010). This self-cleaning ability of
super hydrophobic membranes enables foulants to be released easily
from surface of membrane (Zhao et al., 2013; Himma et al., 2019).
Hence, it is reported that employing super hydrophobic membrane
could alleviate the problem of membrane fouling within membrane
contactors. Yu et al. reported that utilization of super hydrophobic
ceramic membrane exhibited superior anti fouling property in com­
parison to PP membranes without super hydrophobicity. The surface of
the ceramic membrane was not covered up with dust particles even after
it is operated for treatment of flue gas for 30 day long operation (Yu
et al., 2015). It was suggested by Huang et al. that an ideal membrane
should be fabricated possessing anti fouling and anti-wetting properties,
appropriate mechanical strength and enhanced chemical stability
(Huang et al., 2021). Simply put, specific membranes must be fabricated
that can withstand the challenges related to membrane wetting and
fouling encountered during membrane contactor operation. Fabrication
of appropriate membrane according to desired situation will also help in
enhancing membrane’s lifespan and reducing membrane wastage.
5.3. Membrane wetting
Wetting of membrane is generally considered as a major problem in
membrane contactor’s utilization as membrane wetting can increase
membrane’s mass transfer resistance and decrease mass transfer effi­
ciency of system. Membrane wetting takes place when liquid absorbent
enters the pores of membrane over an extended time of operation,
hence, leading towards gradual membrane wetting. Membrane wetting
is generally categorized into three distinct modes of operation;
completely wetted, partially wetted and non wetted mode. In case of
completely or partially wetted mode, the pores of the membrane are
10
Chemosphere 325 (2023) 138300
completely or partially filled with liquid absorbent with time. While in
non-wetted mode, the pores of the membrane are completely filled with
gas phase over time. Mavroudi et al. proposed that if membrane pores
are 13% liquid filled, the membrane’s mass transfer resistance could
increase up to 98% (Mavroudi et al., 2006). In a simulation study carried
out by Wang et al. it was evaluated that if 5% of pores are wetted, overall
mass transfer coefficient could be reduced by about 20% (Wang et al.,
2005). Also, it was asserted that rate of absorption within wetted mode
was almost 6 times lesser than in nonwetted mode. Hence, it was sug­
gested that in order to maintain best membrane performance in CO2
absorption as well as stripping, the maximum percentage of membrane
wetting that is acceptable is 40% (Khaisri et al., 2009).
The phenomena of membrane wetting could occur in many ways and
it varies according to mutual interactions of membrane materials and
liquid absorbent. It is easier to deal with physical absorbent in com­
parison to chemical absorbent as wetting problem is less significant in
physical absorbent. But, physical absorbent’s CO2 absorption capacity is
lower than chemical absorbent. For that reason, experimental work is
focusing more on wetting of chemical absorbent on membrane material.
Celgard X50-215 and Celgard X40-200 (PP membrane) were tested by
Wang et al. in diethanolamine aqueous solution for 3, 10 and 30 days
(Wang et al., 2004). It was found out that both of the fibers were wetted
by diethanolamine solution and can be noticed by morphological
changes through SEM analysis. X-ray photoelectron spectroscopy and
atomic force microscopy analysis exhibited that membrane’s surface
roughness as well as pore structure was also significantly changed
(Wang et al., 2004). It may be possible that chemical reactions among
diethanolamine aqueous solution and membrane have reduced surface
hydrophobicity that lead towards membrane matrix deterioration.
Also, a quite similar research on Celgard membrane for absorption of
CO2 in diethanolamine solution experienced the same problem of wet­
ting and was indicated by changes in membrane’s morphology, reduc­
tion of absorption flux as well as overall mass transfer coefficient (Wang
et al., 2005). Lv et al. (2010) also experimented PP HF membranes on
extended contact in several liquid absorbents like deionized water,
MDEA and MEA for about 90 days and having 3 M chemical absorbent
concentration. The results identified the diffusion of absorbent mole­
cules onto membrane pores and this resulted into reduction in mem­
brane’s hydrophobic properties along with alteration in surface
properties. This in turn increased the extend of wetting of membrane
pores, hence significantly reducing the contact angle (Lv et al., 2010).
Therefore, it was proposed that productive methods that could control
and overcome membrane’s wetting problem includes improvement of
membrane’s surface hydrophobicity as absorbent’s high surface tension
favours smaller changes within membranes surface morphology. Khaisri
et al. (2011) studied the result of membrane porosity in two distinct
modules having porosity of 23% and 40% for desorption. Though the
results indicated that module having higher porosity of 40% produced
higher rate of desorption but, the module performance decreased when
it was carried out for longer operating hours because of wetting problem
(Khaisri et al., 2011). The PTFE membrane that was utilized in their
research study is considered as the most chemical resistant polymers
that are commercially available.
Though, it was speculated that the outcome of increasing tempera­
ture and probable reaction with MEA aqueous solution could contribute
towards continuous reduction of desorption flux. Lu et al. also supported
this research trend where membrane having higher porosity aids pore
wetting as compared to one having low porosity (Lu et al., 2008).
Though, selections of liquid absorbents that are utilized are normally
compatible with membrane material but harsh operating conditions
might affect the performance as well as physical appearance of mem­
brane. Commercial membranes also experienced this, where they could
react with absorbent such as amine solution and sodium hydroxide when
contacted for longer operating hours and prone to higher temperature
conditions (Hashim et al., 2011). As discussed above, Wang et al. re­
ported that on exposing PP (polypropylene) membranes to aqueous
A. Imtiaz et al. Chemosphere 325 (2023) 138300

solution of diethanolamine for 3 and 10 days not only altered the
membrane’s pore structure but also increased the surface roughness of
membrane (Wang et al., 2004). It is a general agreement with a research
study that was conducted by Rangwala (Rangwala, 1996), where it was
presumed that PP membrane’s partial wetting could occur when
aqueous solution of amine was utilized. PP membranes were examined
by Rangwala having different module sizes with aqueous DEA and
NaOH liquid absorbents. The membrane’s mass transfer measurement
exhibited that PP fiber was partially wetted by both of aqueous solutions
even though the membrane have to be non-wetted by any solution
(Rangwala, 1996). PP membrane’s (Accurel and Celgard 2500) surface
morphology was also studied by Barbe et al. (2000a) and they identified
that both of the membranes underwent changes in porosity, pore length
and pore size when exposed to water for about 72 h. This was because of
the higher lateral forces that were exerted by water on surrounding fi­
brils within the larger pores that contributed towards pore enlargement.
Aiming to eliminate or minimize the problem of membrane wetting,
research workers have focused recently on screening of membrane
materials and liquid absorbents such as amalgamating different types of
absorbents (Ma’mum et al., 2005; Zhang et al., 2022), surface modifi­
cation of membranes through grafting (Wongchitphimon et al., 2011)
and/or by incorporating inorganic filler (Zhang and Wang, 2013) or
pore former onto membrane surface (Naim et al., 2012). Polymer pos­
sessing higher surface energy is susceptible to wetting. In order to pre­
vent this, polymer should possess lowest possible maximum pore size
and lower surface energy. Wetting pressure has an inverse relation with
membrane’s pore size, at which high pressure is required for low pore
size i.e. 0.1 μm and low pressure is required for high pore size i.e. 10 μm.
Table 3 below exemplifies polymer’s surface energy along with their
contact angle with water.
For liquid absorbents, several types of aqueous solutions have been
utilized such as aqueous solution of KOH, NaOH, amine and amino acid
salts and also pure water. Every absorbent possesses its own speciality
which in turn specifies a suitable selective process application. A study
was carried out by Li and Chen for the selection of appropriate liquid
absorbent for membrane contactor and it highlighted the selection
criteria of suitable chemical solvent to be used in membrane contactor
which included; liquids possessing lower surface tension, higher reac­
tivity with CO2, adequate compatibility with membrane material, good
thermal stability, regenerability and lower vapour pressure (Li and
Chen, 2005). The solvents employed should possess high surface tension
than the value of critical surface tension of polymer as any liquid pos­
sessing surface tension that is lower than polymer’s critical surface
tension could spontaneously wet the membrane. Lower value of critical
surface tension implies that surface has lower energy per unit area. A
comprehensive research study was done by Dindore et al. (2004a) on
combination of membrane-solvent for removal of CO2 in gas liquid
membrane contactors. It was highlighted by them that the likelihood of
membrane wetting is mainly governed by mutual interaction of mem­
brane material and liquid absorbent, pore size of membrane and liquid’s
surface tension. Their research study concluded that combination of PP
membrane along with propylene carbonate as an absorbent is preferable
option for future research. Though, their research study was limited only
to PTFE membrane and there was no comparison made with other
membrane types (Dindore et al., 2004a).
6. Comparison of conventional membranes and membrane
contactors
In applications involving removal of CO2, membrane gas separation
(MGS) and membrane contactors have some specific advantages and
disadvantages. Concerning commercialization status, MGS has been
working on large scale commercially especially for natural gas sweet­
ening and is competing with traditional amine based absorption process.
Baker and Lokhandwala (2008b) illustrated the effect of CO2 concen­
tration along with gas flow rate on the selection of CO2 removal tech­
niques from natural gas (Fig. 9).
So, in accordance with the plot, when gas stream has higher con­
centration of CO2 (up to 40 mol %) and lower gas flow rate (lower than
10 MMscfd), then MGS is considered as a favourable option. While,
when gas stream has lower CO2 concentration (∼ 2–25 mol %) and
higher gas flow rate (up to 500MMscfd), then amine based absorption
process is mostly preferred. Whereas, in case of gas stream having higher
concentration of CO2 and higher flow rate, combination of amine based
absorption process and MGS is preferred (Baker and Lokhandwala,
2008a). A dominant feature of MGS is that it does not require a solvent,
hence solvent makeup, chemical regeneration and other associated
controlling is not required. The separation in MSG is not dependant onto
chemical sorbent; hence its utilization for separation of high concen­
tration is more cost effective than amine absorption process. Also, when
CO2 concentration is high, driving force that is required for separation
will increase which is favourable for MGS. But, it bears mentioning that
as the concentration of CO2 increases, the membrane will more be prone
to plasticization (Bos et al., 1999). If MGS process is utilized for treat­
ment of feed gas having lower concentration of CO2, the driving force is
decreased and as a result substantial amount of product gas or CH4 in
case of CH4/CO2 separation is lost. Hence, the MGS performance is
decreased which in turn results into increment in processing cost. MGS
usually requires relatively higher energy consumption than membrane
contactors, and is mostly linked with utilization of dense membranes
and higher operating pressure.

Table 3
Polymeric material’s surface energy.
Polymer Water contact Critical surface References
angle tension

Polyethylene – 33.2 Starkweather Jr.

(1965)
Polytetrafluoroethylene 109.2 19.4 Wang et al. (2016)
Polydimethylsiloxane 107.2 20.1 Kim et al. (2019)
Polyvinylidenefluoride 89 31.6 Duca et al. (1998) Fig. 9. Schematic illustration of the effect of CO2 concentration along with gas
Polypropylene 102.1 30.5 Schreier et al.
flow rate on the selection of CO2 removal techniques (Baker and Lokhand­
(2014)
wala, 2008a).

11
A. Imtiaz et al. Chemosphere 325 (2023) 138300

Membrane contactors can be utilized to efficiently treat feed gas
stream having low CO2 concentration and can provide higher selectivity
(Klaassen et al., 2008a). In contrast to MGS, membrane contactors
possess higher selectivity so it could potentially be applied in various
concentrations and gas flow rates without the loss of any product gas.
Higher selectivity is usually provided by physical or chemical interac­
tion between gas and absorbent. The operating cost of membrane con­
tactors is normally lower than MGS as it is typically operated under
lower operating pressure. In spite of many advantages, membrane
contactors also has several disadvantages such as fouling, wetting of
membrane etc and they have been discussed in detail in section 5. Some
of the other drawbacks of membrane contactors that should be taken
into consideration include: (1) membrane that is utilized in membrane
contactors develop into additional transport resistance as it can decrease
overall mass transfer and reduces selectivity. The resistance will become
more considerable if membrane gets wetted. (2) Within the membrane
module, the non-uniform distribution of hollow fibers could lead to­
wards bypassing and channelling which in turn reduces mass transfer
efficiency. Hence, module geometry and flow configuration must be
taken into consideration. (3) The performance of membrane contactors
is seriously affected by operating conditions, hence pressure, tempera­
ture as well as flow rates, both solvent and gas or liquid streams must be
controlled in order to prevent the formation of gas bubbles which could
lead towards loss of gas and also membrane wetting by solvent should be
prevented. Membrane contactors usually require organic solvents such
as amine solution for applications related to CO2 removal. In spite of the
fact that organic solvents provide higher selectivity, the utilization of
this sort of solvents also have several disadvantages. Amine solution
possesses high vapour pressure as well as higher energy for regeneration
and is also corrosive (Babamohammadi et al., 2015). In the recent past, a
new category of absorbents named as ionic liquids (IL) has gained re­
searchers interest in terms of utilizing it in membrane contactors for
carbon capturing. IL is actually a salt having melting point lower than
100 ◦ C and consists of organic cation and inorganic or organic anion
(Dai et al., 2016b). Their attractive features includes high selectivity,
high CO2 solubility, higher thermal stability and low vapour pressure
(Karadas et al., 2010). Because of these attractive qualities, the mem­
brane contactor’s performance for removal of CO2 can be further
enhanced specifically when it is operated at high temperatures, for
example for the treatment of flue gas. Yet, considerable efforts are still to
be made for ionic liquids in order to make them favourable for use at
commercial scale for forthcoming applications (Dai et al., 2016a).
7. Techno-economic evaluation of MGS and membrane
contactors for carbon capturing
In comparison to MGS, the economical evaluation of membrane
contactors for the purpose of carbon capture is rarely found in literature.
Yan et al. (2008) conducted the comparison between membrane con­
tactors and traditional amine based system for capturing carbon from
flue gas stream, within which the performances along with the eco­
nomics of both the processes were examined (Yan et al., 2008). The
results indicated that the performance as well as the cost of gas pro­
cessing of membrane contactors is affected significantly by wetting
phenomena. Membrane contactor displayed 2.9 times greater overall
mass transfer coefficient than traditional amine-based system on uti­
lizing a fresh membrane. Consequently, the membrane contactor’s gas
processing cost was lesser than MGS as listed in Table 4. Though, the
favourable and superior performance of membrane contactor could not
be continued when half of the pores of membrane contactors were
wetted. Hence, in order to maintain the superior performance of mem­
brane contactor, wetted phenomena should be avoided. It was inferred
from economic analysis that the cost of CO2 capture as well as the capital
investment of membrane contactor was greatly influenced by lifetime
and price of the membrane as well as by the concentration of SO2 in feed
stream. If the membrane’s lifetime was lesser than critical value, the CO2
capture cost of membrane contactor should be higher than amine based
system.
In a study carried out by Yang et al. it was indicated that carbon
capturing from the flue gas stream by employing membrane contactors
experienced low CO2 capturing cost than MGS narrated by various
studies (Yan et al., 2008). This could be connected with higher selec­
tivity, lower membrane cost and operating pressure of membrane con­
tactor and higher mass transfer of porous membrane. However as
described in Section 1-4, membrane contactor also possesses several
drawbacks that must be addressed before its use in commercial

Table 4
Economic analysis of MGS and membrane contactors for capturing CO2 from flue gas.
Technique Flowrates Inlet feed gas CO2 in Operating CO2 capturing Membrane: cost ($/m2) Assertion References
(P; T) feed conditions cost
($/tonne)a

MGS 1652.4 (k N 95 kPa; 110 ◦ C 13% 1.5 MPa; 82 Polyphenyleneoxide; 50 α(CO2/N4): 20; Ho et al.
m3/hr) 30 ◦ C PCO2: 72 Barrer; (2008)
AƮ = 2 × 105
MGS 500 m3/s 0.1 MPa; 93 ◦ C 14%- 2 MPa; 30 ◦ C 50 PPO; 80 α(CO2/N4): 20; Ho and
mole PCO2: 100 barrer; Wiley (2004)
two stages
MGS 578.7 Atmospheric; 14% 2 MPa; 30 ◦ C 55 Hollow α(CO2/N4): 20; Ho et al.
(tonne/h) 95 ◦ C fiberPolyphenyleneoxidemembrane; PCO2: 72 Barrer; (2006)
150
MGS 500 (m3/s) – 11.6% 0.2 MPa 39 Polaris™; 50 α(CO2/N4): 500; Merkel et al.
PCO2: 1000 GPU; (2010)
AƮ = 3 × 106; two
stages
MGS 535 (m3/s) 0.1 MPa 12%- 0.4 MPa; 46.8 50; α(CO2/N4): 50; Zhai and
mole 30 ◦ C; PCO2: 1000 GPU; AƮ Rubin
= 2521b; two stages; (2013)
Membrane 894 kg/s – 13.31%- 11.3 kPa; 39.3 Polypropylene; 7.4; Absorbent: MEA Yan et al.
contactor vol 40 ◦ C; (30%) (2011)
MGS 18,260 0.1 MPa; 12.9% 0.25 MPa; 47.87 FSC; 35 α(CO2/N4): 135; He et al.
kmol/h 21.5 ◦ C 35 ◦ C PCO2: 740 GPU; two (2015)
stages;
MGS 635 kg/s 0.1 MPa; 13.5%- 0.2 MPa; 120.9 50 α(CO2/N4): 500; Tuinier et al.
150 ◦ C; vol 30 ◦ C PCO2: 1000 GPU; (2011)
Membrane 40,000 m3/ 2 kPa; 150 ◦ C; 15%-wt 5–10 kPa; 2.9–4.4 Polypropylene; 4.8; Absorbent: MEA Yan et al.
contactor h 25 ◦ C (20%; 40 ◦ C) (2008)

12
A. Imtiaz et al.
applications. While the major challenge that is faced by MGS for treat­
ment of flue gas is scaling up of the process, which is generally linked
with considerably large volume of gas stream as well as lower concen­
tration of CO2(Luis et al., 2012). This will specifically affect MGS sep­
aration performance i.e. selectivity and mass transfer as well as the
membrane area required. Yet, many different strategies can be utilized
to enhance the driving force of MGS like increasing the feed pressure,
decreasing permeates pressure, recirculating CO2 enriched stream and
also by reducing the concentration of CO2 in permeate pressure by
sweep gas but all this will require additional cost and extra energy
consumption (Luis et al., 2012).
Favre (Favre, 2007) indicated various aspects that must be consid­
ered if MGS is to be employed for capturing carbon from flue gas stream
(Favre, 2007). These aspects pointed out that: (1) high energy con­
sumption is required by MGS than absorption in case of feed gas stream
having 10% of CO2 even if the membrane’s selectivity is more than 120;
(2) the MGS energy consumption would be competitive in order to treat
feed gas stream having greater than 20% of CO2; (3) the membrane’s
selectivity have to be proximately 60 or above so as to be competitive in
last mentioned case; (4) the consumption of energy can significantly be
reduced on applying vacuum condition within permeate side; (5) as
mass transfer in case of MGS is quite lower than membrane contactors
(around 4–6 times), hence improvement in permeability is required; and
also (6) it is necessary to identify perfect type of operation in order to fit
in with the residual water concentration target as it is analysed very
rarely.
Improvement in performance of membrane in order to achieve CO2/
N2 selectivity greater than 40 and CO2 permeance of 3 m3(STP)/m2h bar
is required in membrane material’s development (He, 2018). Also,
additional improvements are necessary in order to reduce CO2 capture
cost to $20/tonne of CO2 in order to improve and make MGS process
economically beneficial for commercial applications. One more
intriguing case for selecting membrane-based carbon capture is that
when it is to be employed for natural gas sweetening having higher
concentration of CO2, such as, for reserves of natural gas in East Natuna
gas field in Indonesia. East Natuna gas field is one of the largest gas fields
in Asia Pacific and hence the use of natural gas in East Natuna gas field is
impugned by higher CO2 concentration i.e. up to 71% (Batubara et al.,
2014). It generates a higher processing cost and barely a very small CH4
portion is remained in sales gas. There is a strong need to develop a
reliable process as this gas field is meant to accomplish the persistent
natural gas demand. Higher CO2 concentration would be favourable for
membrane based gas separation as it would bring about higher driving
force as well as transfer rate. But, the membrane will be prone to plas­
ticization because of higher CO2 concentration. Also, the CH4 losses are
inevitable during the process. Hence, in this situation, membrane con­
tactors have the potential to be used as a favourable alternative.
Normally, the feed gas from gas field has higher pressure and permits
the utilization of physical absorption for removal of CO2. The CO2 ab­
sorption can be carried out in membrane contactor via employing water,
for instance from seawater as an absorbent or solvent. Utilization of
water from seawater as an absorbent can perhaps reduce the CO2 cap­
ture cost because of its large and inexpensive resource, even in case
when a higher gas flow rate is to be handled and considerable absorbent
volume is required because of higher CO2 concentration. A German
company named Ingenieurbüro Buse developed a biogas upgrading unit
by employing commercial membrane contactor with water as an
absorbent (Vogler et al., 2013). With a closed loop operation system
including absorption and degassing steps, methane having 98% of op­
timum purity was obtained (Vogler et al., 2013). Also, the utilization of
water rather than employing alkanolamaine solutions could potentially
reduce the likelihood of membrane wetting (in case of super­
hydrophobic and hydrophobic membranes) as it possesses higher sur­
face tension. As the absorbent has higher concentration of CO2 and still
possesses higher pressure, perhaps it could directly be introduced into
nearby oil well for the sake of pressure maintenance as it is favourable
13
Chemosphere 325 (2023) 138300
for increasing oil production. One more good point of this scenario is
carbon credits that are acquired from carbon storage. Hence, as an
overall outcome, the cost that is involved in generation of high pressure
water during absorption process would in turn be adjusted and accom­
modated by benefits of carbon storage. Hence, by employing suggested
strategy, the gas stream processing having higher concentration of CO2
might sound logical and reasonable economically.
8. Semi-commercial and pilot scale tests of membrane
contactors
Up to the present time, several semi-commercial and pilot tests have
successfully been carried off by employing membrane contactors based
upon porous membranes (Herzog and Falk-Pedersen, 2000; Yeon et al.,
2005; Vogt et al., 2011; Scholes et al., 2012, 2014; Bazhenov and Lyu­
bimova, 2016). Kvaerner Process Systems Company carried out revo­
lutionary work towards this direction, while major work on the
development and design was initiated in 1992 that in turn resulted in
establishment of various large scale pilot plants for capturing CO2
(Bazhenov and Lyubimova, 2016). In order to clean the flue gas, the very
first pilot plant was installed in Karsto, Norway at statoil Gas company
terminal. The plant was tested for about 7000 h from 1998 to 2001 and
flue gas of 2610 kg/h was treated having CO2 capturing rate of 85% and
in it 30% solution of MEA was utilized as an absorbent. The second pilot
plant unit at gas terminal in Scotland was tested for purification process
of natural gas within which activated MDEA was utilized as an absor­
bent. Eight membrane contactors having different configurations were
being tested between 1998 and 1999 and it was exhibited that modules
could perhaps be operated for about 5000 h without jeopardizing its
performance. Moreover, Kvaerner Process Systems Company introduced
the utilization of physical solvent i.e. Morphysorb® for capturing CO2
from natural gas in Texas USA at Shell/Tejas Gas Fandango gas pro­
cessing plant. Extended tests for about 20 weeks exhibited reliable
performances of utilized membrane contactors. It was concluded from
semi commercial prosecution that utilizing membrane contactors can
reduce the capital costs by 35–40%, the size and weight characteristics
of equipment by 65–75% as well as operational costs by 38–42% (Baz­
henov and Lyubimova, 2016). A technology was developed by
Netherlands Organization for Applied Scientific Research (TNO) for
capturing CO2 from flue gas streams of thermal power plants (TPPs).
Commercially available and cheap porous HF polypropylene (PP)
membranes along with combination of CORAL absorption liquid that
was patented by TNO was employed in the process. Absorption liquid
that was employed in the process is actually aqueous solution of salts of
amino acids having higher absorption characteristics quite similar to
aqueous solution of alkanoamines, however, it has superior desorptive
properties and also do not wets PP membranes (Kumar et al., 2002a).
System was then tested in pilot scale having following specifications:
flow rate of flue gas, 25 m3/h, flow rate of liquid, 20–100 L/h; flow rate
of captured CO2, 150 kg/h; concentration of CO2 in flue gas, 3.5% (Feron
and Jansen, 2002).
Membrane contactors were investigated by Colin et al. for the pur­
pose of capturing CO2 from syngas of a precombustion CO2 capturing
pilot plant located in Mulgrave, Victoria, Australia (Scholes et al., 2012)
and also in process of lignite TPP flue gas cleaning in Victoria, Australia
(Scholes et al., 2014). In first situation, 30% K2CO3 and 30% MEA were
employed as absorbents, while in second situation, amino acid salt so­
lution (PuraTreat™ patented liquid) was employed. The research of this
group is noteworthy because they provided an analysis based on com­
parison between the porous membrane performance made up of PTFE
and PP in real industrial environment. It was concluded in accordance
with the results of both of the studies that employing PTFE membranes is
more favourable; but, they did underwent pore wetting under pilot scale
conditions, which decreases the system performance. Authors have
emphasized on the significance of controlling transmembrane pressure
to avoid this occurrence (Scholes et al., 2012, 2014). Yeon et al.
A. Imtiaz et al.
employed asymmetric porous PVDF HF membrane for capturing CO2
from CO2/N2 simulating flue gas mixtures in pilot scale testing of
membrane contactors (Yeon et al., 2005). Mixed absorbent was used in
this process which consisted of aqueous solution of 5 wt% of TEA and 5
wt% of MEA. Stable operational performance for more than 80 h and
90% CO2 capture efficiency was displayed by membrane contactors as
long as the transmembrane pressure control is provided within the range
of 0.1–0.3 atm (Yeon et al., 2005).
Integrating more than one membrane contactor modules in series
provides a better way to enhance the efficiency of membrane contactors.
For instance, it was indicated that combining two or more membrane
contactor modules in series could notably enhance the CO2 absorption
rate as well as efficiency (deMontigny et al., 2006; Ghobadi et al., 2018).
Moreover, the increase in number of modules also leads towards
increasing the rate of gas feed that is required to attain 90% CO2 re­
covery and is attributed to increment in absorption capacity because of
greater surface area and also due to reduction of gas-liquid trans­
membrane pressure (Boributh et al., 2012). Integrating of multiple
membrane contactor modules in parallel is also subjected to improve
absorption performance (Ghobadi et al., 2018). In general terms,
although multistage module has displayed the potential to improve
absorption performance, the result of liquid splitting and recycling
seems to be marginal and not always appropriate (Tantikhajorngosol
et al., 2018). A setup for multistage membrane contactors at pilot scale
was developed by Choi et al. in order to separate CO2 from flue gas of
boiler that is powered by LNG (liquefied natural gas) at a rate of
1000Nm3/day. For this purpose, up till four stages were employed and
each stage consisted of a HF module, a vacuum pump, a heat exchanger
and a compressor. With this, 95–99 vol% of outlet CO2 concentration
could be attained, together with 70–95% of recovery rate. An optimal
permeate pressure of 19.6 KPa was in turn determined for minimum CO2
outlet concentrations as well as minimal area requirements (Choi et al.,
2013). Recently, it was concluded by He et al. (2018) that conventional
HF membrane contactors were not suitable for gas separation applica­
tions at large scale owing to their complex production as well as their
prohibitive maintenance. Creating a large module by framing and
combining various laboratory scale contactor modules in parallel was
proposed by He et al. as a substitute to up scaling individual membrane
contactor modules (He et al., 2018). This configuration is beneficial
because of its simpler production, easier maintenance and scalability as
well as improved general performance as compared to conventional HF
modules. A major factor that affects the performance involves poor flow
distribution and is dependent upon each of the contactor’s packing
density, shell geometry as well as inlet flow velocity. Hence, the appli­
cation of membrane contactors at pilot scale was susceptible to many
obstacles, particularly the non-uniform and poor flow distribution,
higher influence of temperature and water evaporation, all of them
tends to be relatively insignificant at lab scale. Therefore, the fabrication
of improved models bearing in mind the imperfections of pilot stage
module operations is essential in order to make precise predictions on
their overall performances. On the other hand, the fabrication of pilot
scale module by framing and assembling different laboratory scale
membrane contactor units in parallel was suggested to ease production,
maintenance and upscaling. Although, non-uniform and poor flow dis­
tribution still remains an issue.
9. Commercialization of membrane contactors for gas
separation
After pilot scale testing, the next step involves its implementation on
industrial scale along with its commercialization. For profitable
commercialization along with effective cost reduction, much informa­
tion was obtained from Kvaerner membrane contactor’s trials couple of
years ago which includes: (a) Developing project incentive, (b) attempt
to maintain interest of consumers, (c) identifying a solution to the
problem, (d) must have flexibility as well as focussed objective
14
Chemosphere 325 (2023) 138300
regarding methodology and (e) attempting to work with already existing
material and equipment instead of making an attempt to recreate
something (Herzog and Falk-Pedersen, 2000). Anyhow, with increased
research being done on membrane contactors, it became apparent that
novel ideas and innovative concepts must be put forward like appro­
priate choice of absorbents and membrane materials along with
appropriate module design, that are important for efficient and persis­
tent performance of membrane contactors. Recently, a comprehensive
techno economic research study was carried out for the purpose of
upscaling of CO2 capturing process for 800 MW electrical coal power
plant by employing polytetrafluoroethylene (PTFE) based membrane
contactors and 30 wt% aqueous MEA absorbent, that was compared
with traditional packed column (Kimball et al., 2014). On the basis of
experimental data from pilot and lab scale trials, a two-dimensional
convection diffusion model was constructed. It was stated that upscal­
ing that is based on small scale models is subjected to many uncertainties
and is risky too. Hence, mass transfer coefficient of local membrane (km)
for ‘ideal case’ was calculated on the assumption that gas and liquid flow
rates are uniform, together with lower ‘worst case’ coefficient trying to
resolve the non-uniformities in gas and liquid flow as noticed during
experimental testing. Ideal case coefficient was almost five times greater
than the worst case. In order to maintain the needs of power station,
almost altogether 100 modules were needed with each of them pos­
sessing over 10 million fibers in order to obtain a quite similar packing
density as that of pilot scale module, for module diameter of about 4 m
each. The length that was required in order to obtain almost 90% re­
covery in ideal case scenario was comparatively lower i.e. 1.23 m,
whereas almost 4 m was required for worst case scenario, hence speci­
fying the powerful influence of discrepancies in mass transfer coefficient
on requirements and performance of modules. A decline in mass transfer
coefficients by factor of 5 results in increasing membrane area as well as
module volume by about 325%. Moreover, module requirements in case
of ideal scenario are somehow comparable to structured packed column
requirements; it means that worst case scenario approximately triples
them on comparison. For the purpose of economic analysis, different
values were fixed based upon the latest designs of time. Whilst taking
into consideration the annuity factor as well as the operating and capital
costs, the annual costs that were acquired by authors for worst case
membrane contactors, ideal case membrane contactors as well as for
structured packing was 52.81 M€, 45.62 M€ and 43.24 M€ respectively
with total cost/ton of CO2 avoided to be 60.75€, 53.65€ and 51.62€
respectively. So, for each of the case, the structured packing cost remains
to be the lowest, specifically when it is compared with the worst case.
Hence, in order to make membrane contactors competitive with packed
columns, the specific cost of module must be reduced by 86% and 56%
for worst case and ideal case respectively, means reducing them to
2.75€/m2 and 8.85€/m2respectively. It must be noted that while
considering the lifetime of membrane to be 5years and replacement
costs to be 50%, this will eventually leads towards a significant increase
in annual cost, hence it is necessary to reduce the cost of module to
1.23€/m2 and 3.95€/m2, that could be done by choosing a low cost
alternative to PTFE membrane like PVDF and PP membranes. Many
important parameters such as membrane lifetime as well as mass
transfer coefficient should be determined carefully in order to ensure
precise assessment of economical feasibility. There is a need of im­
provements which must be carried out not only in material of membrane
as well as in module construction and assuring uniform distribution of
liquid and gas flows. Significant reduction in costs is needed, particu­
larly in module casings and membranes, for sake of HF membrane
module contactors to compete with structured packed absorption
column.
On contrary, the cost of employing polyether ether ketone (PEEK) HF
membrane contactor for absorption of CO2 was compared with con­
ventional absorber from United States Department of Energy (DOE) by
Li et al. (2013), where membrane contactors came out to be more cost
effective (Li et al., 2013). Total costs for running the process for 626.2
A. Imtiaz et al.
Mt/h of CO2 removal rate and 90% of the recovery rate from coal power
plant of 50MWe were estimated, for treating gaseous mixture consisting
of 3.5% oxygen, nitrogen with 145ppmv of SO2 and 14.96% CO2⋅ In
order to calculate total capital expenditure that includes the costs of
reboiler, module unit, stripper as well as other associated equipment, a
cost of 377 M$ and 345 M$ was attained for membrane contactor
employing activated MEA and potassium carbonate as an absorbent. On
comparison, a total capital expenditure of 436 M$ was attained for
conventional absorber. For coal power plant, the levelized cost of energy
(LCOE) that usually includes operating and capital costs, cost of coal as
well as CO2 storage, monitoring and transport cost was also evaluated in
ten cents per kilowatt hour (mills/kWh). LCOE of 118.36, 107.57 and
100.11 mills/KWh was attained for absorber, K2CO3 and MEA based
membrane contactor, in comparison with 64 mills/KWh without
capturing carbon. Thus, implementing membrane contactor escalates
energy cost by 55–86%, and this is much lower than 85% increase from
the conventional absorber reviewed.
A model was developed by Rezakazemi et al. (2017) in order to es­
timate the operating cost for H2S and CO2 removal from natural gas. The
key factors that influence cost of separation were analysed. The CO2
fraction that is to be removed, inlet concentration of CO2 as well as
methane cost contribute towards increasing the costs, whereas CO2/CH4
membrane selectivity as well as feed flow rate when increased can lower
the costs. The existence of H2S almost doubled the separation costs,
bringing attention towards the influence of the existence of impurities
on overall costs. In another study done by Usman et al. (2018), the costs
for precombustion CO2 capture from synthesis gas arising from inte­
grated gasification combined cycle plant (IGCC) was evaluated. Ionic
liquid [BMIM][TCM] having 90% of target capture efficiency was
employed as an absorbent. Total project cost was estimated to be 47.4 M
$ and almost half to the total capital cost was ascribed to the compressor,
around 40% was associated to membrane contactor and lesser than 5%
of the total cost was attributed to heat exchanger, flash separator and
pump. The total operating expenses of 9.04 M$/yr were estimated
having specific costs of 87$/ton of CO2. The usefulness of pilot scale
biogas upgrading with membrane contactors was evaluated by Park
et al. (2017). The process of absorption was integrated with pressure
cascaded stripping for the purpose of optimizing CO2/CH4 selectivity
through stripping CH4 that was absorbed with CO2within the liquid
phase due to thermodynamic non idealities of system. Over 97% of CH4
purity could be attained. Costs for polypropylene (PP) membranes was
fixed at 20$/m2 having replacement after every 5 years and cost of
methane was fixed at 0.13$/m3. Annual expenses for maintenance and
operation were estimated to be 3.4% with 10% of annual capital
depreciation. Breakeven point was calculated as a function of plant ca­
pacity that was shown to be at two years or lesser and drops below a year
for capacities that are above 750 Nm3/h. On comparison with tradi­
tional membrane contactor setup, the pressure cascaded process was
competitive in general, mostly at high capacities. One of the notable
advantages of pressure cascaded process included major reduction of
greenhouse warming potential (GWP) because of high yield of CH4 and
lesser release, that was almost about two third of the level of traditional
one (Park et al., 2017).
10. Conclusions and future development prospects
At present, various membrane systems have been installed for
offshore platforms as well as for small scale applications. Specifically,
over last few years several membrane based systems have been practi­
cally applied to large scale offshore natural gas upgrading projects
where footprint is the major constrained. For gas permeation through
the membranes, it is important to investigate new membrane materials
that are more selective and have better plasticization resistance in order
to minimize costs and to reduce the footprint of pre-treatment systems
that are almost about 15–50% of footprint of entire membrane systems.
Membrane contactors can be employed as an alternative to
15
Chemosphere 325 (2023) 138300
conventional absorption process and together with membrane gas
permeation it serves as an efficient solution for gas purification with
reduced consumption of energy, overall plant size as well as reduced
operational and investment cost. Regardless of the promising applica­
tions of membrane based carbon capture technologies, i.e. membrane
gas separation and membrane contactors, they possess some limitations
that should be addressed before employing them for industrial appli­
cations. In case of membrane based gas separation, it is important to
develop new generation of membranes having higher mechanical sta­
bility against high pressure and temperature, and must possess anti
plasticization characteristics in order to ensure membrane’s durability
along with higher permeability and selectivity. On the other side,
membrane contactors have gained significant attention for CO2 capture
as it amalgamates the advantages of both membrane separation
(compactness and modularity) and liquid absorption (higher selec­
tivity). Till now, most of the research on capturing CO2 by employing
membrane contactors is still carried out at laboratory scale because of
some critical challenges that are faced by them during their operation.
Out of all challenges, membrane wetting is most crucial. A better com­
bination of membrane and liquid absorbent is important in order to
establish effective mass transfer hence leading towards higher removal
of CO2. In order to minimize the influence of membrane wetting as well
as to lower the cost of membrane contactor system, new and cheap
polymeric membranes having anti wetting and fouling properties are
supposed to be fabricated and studied in future. Also, surface modifi­
cation of polymeric membranes in order to improve its chemical prop­
erties is considered as a promising technique for enhancing the
membrane’s performance during membrane contactor operation.
Observing the characteristics of membranes before and after the process
of stripping must be carried out in order to closely inspect the effect of
longer contact of membrane with liquid absorbent. This can be carried
out by executing the morphological analysis of membrane via FESEM or
SEM, by measuring tensile strength as well as contact angle before and
after the process of stripping. It will help in defining and highlighting the
correlation of membrane properties employed in membrane contactor
before and after stripping.
Regarding the design of module, several substitutes of traditional flat
sheet and hollow fiber modules have been proposed. Not merely new
module designs were put forward in order to increase mass transfer
performance, like woven fiber, cross flow, tubular and spiral wound
modules, but also hybrid modules were proposed where the absorption
and desorption of gas could be achieved in same module thus reducing
the equipment requirements for wide scale applications. One of the
interesting approaches that are to be considered for the up scaling of
practical and efficient membrane contactor modules normally consists
of assembling and forging several lab scale membrane contactor units
and facilitating the production along with maintenance and upscaling.
On the other hand, the model accuracy in case of pilot scale membrane
contactor is jeopardized by non uniform flow distribution as well as by
higher influence of temperature. Apart from improving and upgrading
the model in order to deal with these non idealities, production of
modules by amalgamating several lab scale units as well as incorpo­
rating the absorption and desorption phases into one module is
considered to be a favourable pathway for applications of membrane
contactors on large scale.
Finally, this review also focussed on the semicommercial and com­
mercial implementations of membrane contactors. Some examples of
semi commercial and pilot scale implementation of membrane con­
tactors for absorption and desorption of carbondioxide are highlighted.
The results of pilot and semi commercial implementation exhibited that
employing membrane contactors can reduce the capital cost by 35–40%,
the size and weight characteristics of equipment by 65–75% and oper­
ating costs by 38–42%. However, commercialization of membrane
contactors at industrial level is most important challenge to deal with.
Considerable success was achieved by them particularly for applications
in gas separation sector. But, recent techno economical analyses of
A. Imtiaz et al.
membrane contactor’s applications at commercial level have exhibited
mixed results, and it may or may not be competitive with conventional
technologies like packed columns. Hence, further research and investi­
gation on economical feasibility of membrane contactors for gas sepa­
ration applications is required to be done.
Credit author statements
Mohd Hafiz Dzarfan Othman, Asim Jilani: Conceptualization, Su­
pervision, Methodology Aniqa Imtiaz.: Data curation, Methodology,
Writing – original draft.: Ojo Samuel, Tonni Agustiono Kurniawan, Nur
Awanis Hashim, Mohd Hafiz Puteh:Writing- Reviewing and Editing,
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
The authors would like to acknowledge the financial supports from
Ministry of Higher Education Malaysia under the Higher Institution
Center of Excellent (HICoE) (Project number: R.J090301.7809.4J430),
and Universiti Teknologi Malaysia under the Matching Grant, (Project
number: R.J130000.7309.4B676/Q.J130000.3009.03M23) and UTM
Fundamental Research (UTMFR) (Project number: Q.
J130000.3809.22H07). The author also would like to acknowledge
UMW Holdings for the research contract (Project number: R.
J130000.7609.4C471).
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