See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/322894697

Status and improvement of dual-layer hollow fiber membranes via co-

extrusion process for gas separation: A review

Article  in  Journal of Natural Gas Science and Engineering · February 2018

DOI: 10.1016/j.jngse.2018.01.043

CITATION READS

1 398

9 authors, including:

Imran Khan Ahmad Fauzi Ismail

Universiti Teknologi Malaysia Universiti Teknologi Malaysia
14 PUBLICATIONS   92 CITATIONS    1,042 PUBLICATIONS   19,905 CITATIONS   

SEE PROFILE SEE PROFILE

Takeshi Matsuura Haslenda Hashim

University of Ottawa Universiti Teknologi Malaysia
348 PUBLICATIONS   8,303 CITATIONS    193 PUBLICATIONS   2,605 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Electrolyte modification fo micro-tubular solid oxide fuel cell View project

Proton exchange membrane and Ultra filterartion membrane View project

All content following this page was uploaded by Imran Khan on 08 February 2018.

The user has requested enhancement of the downloaded file.

 Journal of Natural Gas Science and Engineering 52 (2018) 215–234

Contents lists available at ScienceDirect

Journal of Natural Gas Science and Engineering

journal homepage: www.elsevier.com/locate/jngse

Review Article

Status and improvement of dual-layer hollow fiber membranes via co- T

extrusion process for gas separation: A review
Imran Ullah Khana,b,d, Mohd Hafiz Dzarfan Othmana,∗, A.F. Ismaila, Takeshi Matsuurac,
Haslenda Hashimd, Nik Abdul Hadi Md Nordina,e, Mukhlis A. Rahmana, Juhana Jaafara,
Asim Jilania,f
a
Advanced Membrane Technology Research Centre (AMTEC), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, Skudai, Johor,
Malaysia
b
School of Chemical and Material Engineering (SCME), National University of Science and Technology (NUST), H-12, Islamabad, Pakistan
c
Department of Chemical and Biological Engineering, University of Ottawa, Ottawa, Ontario, K1N 6N5, Canada
d
Process System Engineering Centre (PROSPECT), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, Skudai, Johor, Malaysia
e
Department of Chemical Engineering, Universiti Teknologi Petronas, 32610, Seri Iskandar, Perak, Malaysia
f
Center of Nanotechnology, King Abdul-Aziz University, 21589, Jeddah, Saudi Arabia

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

Keywords: Carbon dioxide (CO2) is the main culprit of greenhouse gases produced mainly via the combustion of fossil fuel.
CO2 capture This paper reviewed the performance of emerging dual-layer hollow fiber membrane, its fabrication via co-
Dual-layer hollow fiber membrane extrusion process, improvement, challenges, spinning parameters, advantages and disadvantages in comparison
Co-extrusion to single-layer hollow fiber membrane for natural gas purification. Development of delamination-free dual-layer
Delamination
hollow fibers via co-extrusion and phase inversion technology is one of the potential solutions for the use of
Spinning parameters
expensive and brittle polymers for the outer selective layer and low cost polymers with high thermal and me-
chanical properties for the porous inner layer.

1. Introduction
Natural gas is a naturally occurring hydrocarbon gas mixture mainly
consisting of methane (CH4) and carbon dioxide (CO2) which are
formed due to decomposition of plants and animal matter by heat and
high pressure under the surface of the earth over millions of years. The
removal of CO2 is the most crucial and important step in natural gas
purification because its presence could cause pipeline corrosion, de-
crease the calorific value and consequently increase the maintenance
and operational cost (Choi and Nešić, 2011; Dashti et al., 2015). Fur-
thermore, environmental problems have become a big issue due to the
greenhouse gas (GHG) emission as the result of fossil fuel combustion
(Hosseini and Wahid, 2013; Zhang et al., 2013). Nowadays greenhouse
effect is a major environmental cause where CO2 from the power-plant
flue gas is the main source of generating CO2 emissions. Thus, the
technologies for CO2 separation have attracted the researcher's interest
throughout the world (Zhang, 2016). The technologies that are used
commercially for natural gas purification today are pressure swing
adsorption, high pressure water scrubbing, organic solvent scrubbing,
amine scrubbing, membrane separation and cryogenic separation
(Constantinou et al., 2014; Zhang, 2016; Zhang et al., 2017, 2014). The
selection of suitable technology by considering the efficiency and
economy of a specific application is important (Ullah Khan et al., 2017).
During the last four decades, the asymmetric single-layer hollow fiber
membrane (SLHF) has been considered to be a promising configuration
in the membrane-based gas separation systems due to their large sur-
face area per unit volume, self-mechanical support, high flexibility and
easy scale-up (Chung, 1996). However, the trade-off between perms-
electivity and permeability; where highly selective membrane possesses
poor permeability and vice versa hinders their potential. Also, they
provide relatively low removal efficiency of CO2 in comparison with
physical and chemical liquid solutions (Zhang et al., 2017). To further
develop membrane separation technology in industrial applications,
one must find ways to improve both gas permeance and selectivity.
Several polymeric materials such as thermally-rearrange (TR) polymer
and the polymer of intrinsic microporosity (PIM) were identified with
excellent performances. Nonetheless, they are bounded by their avail-
ability and cost of the materials. Therefore, improving existing polymer
materials via innovative hollow fiber (HF) fabrication technologies to
produce ultra-thin dense selective layer have been explored (Sharpe

∗
Corresponding author.
E-mail address: hafiz@petroleum.utm.my (M.H.D. Othman).

https://doi.org/10.1016/j.jngse.2018.01.043
Received 13 July 2017; Received in revised form 27 December 2017; Accepted 3 January 2018
Available online 02 February 2018
1875-5100/ © 2018 Elsevier B.V. All rights reserved.
I. Ullah Khan et al. Journal of Natural Gas Science and Engineering 52 (2018) 215–234

Abbreviations NMMO·H2O N-methyl morpholine-N-oxide monohydrate

NF Nanofiltration
ATBC Acetyl tributyl citrate NIPS Nonsolvent induced phase separation
CFD Computational fluid dynamics PVP Polyvinylpyrrolidone
DMAc N, N-dimethylacetamide PVDF Polyvinylidene difluoride
DMF Dimethylformamide PDMS Polydimethylsiloxane
DLHF Dual-layer hollow fiber PAPI Polymer-assisted phase inversion
DMSO Dimethyl sulfoxide PBI Polybenzimidazole
DCMD Direct contact membrane distillation PES Polyethersulfone
DER Dope extrusion rate PSf Polysulfone
DG Diethylene glycol PAI Polyamide-imide
DP Dispersed phase PEO Polyethylene oxide
GS Gas separation PU Polyurethane
GHG Greenhouse gas PEI Polyetherimide
HD Hemodialysis PEG Polyethylene glycol
HF Hollow fiber PI Polyimide
ISP Internally staged permeator RO Reverse osmosis
IPN Interpenetrating polymer network SLHF Single-layer hollow fiber
Lc Critical structure-transition thickness SPES Sulfonated polyethersulfone
LSCF La0.6Sr0.4Co0.8Fe0.2O3−δ SE Solvent evaporation
mPDA meta-Phenylenediamine TIPS Thermally induced phase separation
MCOC Mixed conducting oxide ceramic THF Tetrahydrofuran
MC Molten carbonate Tc Crystallization temperature
MF Microfiltration UF Ultrafiltration
MD Membrane distillation VIPS Vapours induced phase separation
NMP N-methyl-2-pyrrolidone

et al., 1999; Chung et al., 1997; Mahdavi et al., 2017). As the thin layer
is the responsible for the gas separation so a porous support layer,
however, is essential to maintain the desired mechanical strength of the
membrane. New investigations and advances in phase inversion and
membrane formation processes, therefore, are required to fabricate
membranes with a thin selective layer and fully porous support layer
that can minimize the problems faced by asymmetric SLHF membranes
such as plasticization at high feed pressure and low mechanical
strength. Hence, it is worthwhile to investigate further the fabrication
of multilayer membranes.
The conventional techniques to fabricate multilayer membranes
such as dip coating and in situ polymerization are multiple-step pro-
cesses that are costly, laborious and time consuming. Co-extrusion is a
breakthrough to prepare multilayer membranes in single a step (Dalane
et al., 2017). The double layer hollow fiber (DLHF) membranes pre-
pared via the co-extrusion process have all the advantages of SLHF
membranes such as: (1) they have high active surface area to volume
ratio, low resistance to gas flow, self-supporting structure and ability to
perform at high pressure (Li et al., 2004b and Suzuki et al., 1998), (2)
they can significantly reduce the cost of high-performance materials by
adjusting the ratio of the outer to inner layer thicknesses (Chung et al.,
1997), (3) brittle but highly selective and permeable polymers can be
employed as the selective thin outer layer, and (4) the second step of
depositing a selective layer upon HF membranes can be eliminated (Li
et al., 2004b). However, limited research has been done on the fabri-
cation of DLHF membranes for gas separation until now.
The advantages of DLHF over SLHF membranes have been high-
lighted by recent researchers (Aroon et al., 2010; Bonyadi and Chung,
2007; Chung et al., 2007; He et al., 2002; Hosseini et al., 2010; Li et al.,
2002, 2004a; Li et al., 2004b, 2008, 2006; Liu et al., 2003a,b; Peng
et al., 2010; Pereira and Nobrega, 2003; Suzuki et al., 1998; Teoh et al.,
2008; Tin et al., 2003; Li et al., 2011; Li and Koops, 1994; Li and Chung,
2010 and Widjojo et al., 2007a, 2007b, 2008; Wang et al., 2004; Jiang
et al., 2004, 2007, 2006, 2005). Li et al. (2004b) fabricated a DLHF
membrane for gas separation with a dense selective layer of 407 Å
thickness using the same polymer polyethersulfone (PES) in both layers.
The delamination-free structure was maintained by using the same
polymer but with different concentrations in two spinning dopes. The
separation performance of fabricated DLHF membrane was strongly
affected by the fabrication conditions. Pereira and Nobrega (2003) and
Li et al. (2004a) investigated the morphology of DLHF membranes for
gas separation by using Matrimid 5218 as the outer selective layer and
PES and polyetherimide (PEI) as the inner supporting layer. They
showed that interfacial delamination was caused due to the higher
shrinkage rate of the inner layer than the outer layer. They also iden-
tified that macrovoids formation in the outer layer was highly depen-
dent on the solution viscosity and the critical structure-transition
thickness. They tried to remove macrovoids in the inner layer using
additives and increasing the elongational draw ratio (Wang et al.,
2004). Li et al. (2006) and Jiang et al. (2005) fabricated DLHF mem-
branes with a mixed matrix dense selective layer for gas separation.
They extended their studies by using nano-sized zeolite beta particles to
further improve the gas separation performance. Suzuki et al. (1998)
reported that permeability could be improved by low polymer con-
centration in the inner spinning dope. Widjojo et al. (2008) enhanced
the permeance and selectivity of the HF membranes by incorporating
nanoparticles in the inner layer. Jiang et al. (2004) found that gas se-
paration performance of DLHF membranes could be affected by dope
flow rates, especially which of the outer layer dope.
The development of novel membranes is mainly based on the ex-
periments performed with focuses placed on the physicochemical and
morphological characteristics and performance of the newly designed
and synthesised materials (Alzahrani and Mohammad, 2014). Prior to
their commercialization, still insufficient attention has been devoted to
the complexity and interactions of the membrane materials availability
(Goh et al., 2016; Leather et al., 2013) However, the adoption of new
technologies strongly depends on the cost effectiveness. Therefore, it is
important to implement the technologies with minimal changes to the
existing infrastructure (Kumar et al., 2013). In this context, retrofitting
and upgrading of the current single layer membrane seems to be a more
promising approach (Drioli et al., 2015). Also, incorporating innovative
and sustainable materials and processes into currently existing facilities
can overcome the cost challenges. The implementation of membrane
technology in gas separation and other applications worldwide is still

216
I. Ullah Khan et al.
considered insufficient, thus so future research in this area using DLHF
membranes is highly recommended. Currently, only polymeric and
mixed matrix membranes have been commercialized while others are
still in fundamental developmental stages (Jusoh et al., 2016). Other
factors such as process improvements which include a selection of
suitable spinning parameters, membrane materials need to be con-
sidered to lower the overall DLHF membrane costs. In future, DLHF
membrane technology will surely be used in various applications such
as wastewater treatment, gas separation, fuel cell, dairy industry, pet-
roleum industry and others which significantly reduce the global pol-
lution and cost (Karavalakis et al., 2012; Gao et al., 2018; Kuvarega
et al., 2018; Ghangrekar and Shinde, 2007). Many challenges need to be
addressed to optimize the design the DLHF for practical applications.
Most of the membranes suffer greatly from some inherent limitations
such as poor solubility and processability, which hinders their com-
mercialization for industrial applications. Hence, extra efforts should be
endeavored to resolve these issues.
To the best of our knowledge, only limited reports have been pub-
lished on the morphological study of DLHF membranes (Li et al., 2004a;
Widjojo et al., 2007a; Dzinun et al., 2015; Wang et al., 2004). Sur-
prisingly, review paper for the fabrication of DLHF membranes speci-
fically for CO2 removal from natural gas is yet to be critically discussed.
Therefore, the objectives of this paper are (1) to provide the compre-
hensive knowledge on the fabrication of DLHF membranes by the phase
inversion process for natural gas purification, (2) to illustrate the co-
extrusion process for DLHF membranes, (3) to present the basic prin-
ciples for the selection of materials, (4) to summarize the effects of
different spinning parameters for the fabrication of DLHF membranes,
(5) to provide different approaches to reduce the delamination by im-
proving the adhesion of two layers and lastly, and (6) to identify the
effects of post treatments such as solvent exchange, heat treatment,
cross-linking and coating.
To fulfill the above objectives, the present work consists of the
following sections.
Section 1: Introduction
Section 2: Discussions on the formation of the asymmetric HF
membranes. Most of the commercially available polymeric mem-
branes have an asymmetric structure formed by the phase inversion
process developed by Loeb and Sourirajan in the late 1950s (Loeb
and Sourirajan, 1962).
Section 3: Summary of different phase inversion processes.
Section 4: Review of the co-extrusion process and different appli-
cations of DLHF with focus on CO2 removal. Some polymers that
could not be used for SLHF can be used via co-extrusion method
(Wojciechowski, 2014). Polymeric materials of high separation
performance such as Matrimid®, Polyimide (PI) and Polyethylene
glycol (PEG) are expensive. DLHF enables to address the cost issue.
Section 5: Discussions on the effects of different spinning para-
meters. The dope composition is one of the factors that govern the
HF morphology (Ekiner and Vassilatos, 2001). The spinning condi-
tions also largely affect the HF performance. As well, the post
treatment can significantly improve the separation performance
(Husain, 2006).
Section 6: Discussions on the prevention of delamination between
the outer and inner layer of DLHF membranes. DLHF membranes
should be delamination-free to withstand high testing pressures for
industrial applications (Li et al., 2002).
Section 7: Conclusions.
2. Hollow fiber membrane
HF configuration has some advantages over the spiral wound, tub-
ular, and plate-and-frame membranes, such as (1) larger area per unit
volume; (2) self-mechanical support; and (3) higher flexibility in fab-
rication. The HF membrane performance is highly dependent on three
217
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
basic factors such as (1) pore size and its distribution generally control
the selectivity, (2) selective skin layer thickness controls the membrane
flux, and (3) membrane material properties govern the intrinsic per-
meability and permselectivity. Numerous works have been reported to
obtain HF with desired pore structures and thin selective layers (Sharpe
et al., 1999; Suzuki et al., 1998; Ekiner and Vassilatos, 2001). But until
now the discussions were rather qualitative than quantitative. It has
also been suggested that the formation of HF is primarily governed by
rheological properties of the spinning dope, the properties of the bore
fluid and external coagulant, the bore fluid flow rates, dope flow rate,
shear stress within an annular orifice of the spinneret, and temperature
(Shilton et al., 1994; Chung and Kafchinski, 1997). These controlling
parameters for HF fabrication are relatively different than those of flat
sheet membrane fabrication. Two coagulations (internal and external)
are often used in HF spinning, while only one coagulation surface is
required for the formation of asymmetric flat sheet membranes. Also in
the HF fabrication, the internal coagulation starts instantly after ex-
trusion from the spinneret and, while generally a waiting period is re-
quired for the flat sheet membrane before dipping into a coagulant bath
(Chung and Hu, 1997; Clausi and Koros, 2000; Qin, 2004). In addition,
the spinning dope for HF usually has higher viscosity and elasticity
compared to flat sheet membranes, thus the macrovoid development is
more complicated in the HF spinning process (Widjojo and Chung,
2006). HFs modules have the surface area to volume ratios 30 to 50
times more than spiral wound modules, that is, almost 10,000 m2/m3
(Kesting et al., 1990). The tubular structure of the HF can withstand
high pressure differences up to 1000 psi (Baker, 2002). The HF struc-
ture is workable in all of the polymer membrane separations such as
ultrafiltration (UF), hemodialysis (HD), reverse osmosis (RO), micro-
filtration (MF) and gas separation (GS) (Yang et al., 2006).
2.1. Formation of hollow fiber membranes
Membranes can be formed by phase inversion (asymmetric mem-
branes), stretching (porous membranes), melt-extrusion (dense mem-
branes), swelling a dense film (porous membranes), particles-sintering
(porous membrane), template-leaching (porous membranes), solution
coating, and nucleation-track-etching (membranes with cylindrical
pores) etc. Most of the commercially available polymeric membranes
are asymmetric membranes formed by the phase inversion (Strathmann
and Kock, 1977).
2.1.1. Asymmetric hollow fiber membranes
In the asymmetric HF membrane, the structure along the depth
direction (thickness direction) of the membrane is anisotropic (gradient
in pore size or apparent density). It consists of a thin integral skin
(dense or porous) and a relatively thick microporous substrate.
Separation is achieved mainly by the skin layer of the asymmetric
membrane and porous substrate provides the mechanical strength. The
gas separation process by asymmetric polymeric membranes has re-
ceived much attention during the last decades because of its higher
energy efficiency than other conventional separation processes
(Gallucci et al., 2013). Generally, six steps are required for the fabri-
cation of modern asymmetric HF membranes such as (1) dope pre-
paration, (2) degassing, (3) spinning, (4) evaporation (in the air gap
section), (5) coagulation, and (6) solvent exchange. Also, three forces
are involved such as (1) shear and elongational stresses within the
spinneret, (2) gravity induced by fiber's own weight, and (3) stresses
induced by the take-up drum and coagulation bath (Wang et al., 2004).
This modern asymmetric membrane fabrication technology is the ex-
tension of the Loeb-Sourirajan technique developed for reverse osmosis
(RO) applications about 40 years ago (Loeb and Sourirajan, 1962).
The asymmetric HF configuration is industrially preferred to im-
prove the performance and decrease the cost of gas separation. The
porous structure of HF underneath the outer skin layer has ideally
negligible transport resistance and increases the mechanical stability of
I. Ullah Khan et al.
membranes against high pressure feeds (Pereira and Nobrega, 2003).
The dense skin layer has a thickness as low as 10 nm and performs the
separation with high productivity. This decrease in skin thickness en-
hances the productivity of the membrane as the flux is inversely pro-
portional to the separating layer thickness while the selectivity remains
the same (Xiang et al., 2017; Malaeb and Ayoub, 2011). The skin for-
mation in asymmetric HF membrane takes place when solvent outflow
from membrane surpasses the non-solvent inflow causing a delayed
demixing (Aroon et al., 2010). It increases the concentration of the
polymer at the membrane-coagulant interface and forms the skin (Li
and Koops, 1994; Peng et al., 2012). An evaporative step can be in-
cluded (air gap) prior to the phase separation step to facilitate the skin
formation by the evaporation of the volatile solvent from the nascent
membrane. As the skin layer is responsible for the separation, the
highly selective dispersed phase (DP) need only be dispersed in the skin
layer. In DLHF membranes, DP is often incorporated only in the outer
selective layer that reduces the use of expensive DP.
3. Membrane fabrication methods
The selection of fabricating process depends on a choice of polymer
and desired structure of the membrane. Membranes can be fabricated
using various methods including phase inversion, melt extrusion, in-
terfacial polymerization, controlled stretching, electro-spinning, and
track etching (Kim et al., 2016b). Currently, the phase inversion
method is the most common type due to its flexibility and scalability
(Kim et al., 2016a). The phase inversion is a demixing process where
the polymer is transformed from liquid to solid phase. In the process, a
thermodynamically stable polymer solution spontaneously separates
into two phases (polymer rich and polymer lean phases) by the changes
in temperature and composition.
There are four main types of phase inversion methods: Thermally
induced phase separation (TIPS), Nonsolvent induced phase separation
(NIPS), vapor induced phase separation (VIPS), and solvent evaporation
(SE) or evaporation-induced phase separation. Among the phase in-
version methods, TIPS and NIPS are the most widely used methods.
VIPS and SE are not commonly used methods nowadays. Apart from the
phase inversion methods, the electrospinning method has been gaining
significant interests from researchers for membrane contactor applica-
tions.
3.1. Thermally induced phase separation (TIPS)
This method is used for the fabrication of microporous membranes
with a narrow pore size distribution, high porosity, and required mor-
phology (Kim et al., 2016a). Generally, a dope solution is prepared by
dissolving a polymer in a high-boiling point solvent at an elevated
temperature, usually above the crystallization temperature (Tc) of the
dope solution (Liu et al., 2017). The dope is then cast into a flat-sheet or
hollow fiber form, followed by a cooling step at a controlled rate to
induce phase inversion with subsequent solvent removal. TIPS method
offers many advantages such as process simplicity, high reproducibility
with a very low tendency to form defects, high porosity, and the ability
to form unique microstructures which is the most favourable require-
ments in most membrane applications (Ji et al., 2008). The membrane
is formed from a homogeneous dope solution by removing the thermal
energy to induce phase separation. Hence, TIPS method is a delicate
balance between the polymer-solvent interaction, cooling rate, cooling
media, and thermal gradient (Cui et al., 2013; Kim et al., 2016a; Nam
and Park, 1999).
One of the diverse advantages of the TIPS method is the ability to
prepare membranes from semi crystalline polymers that are commonly
not soluble in solvents at ambient temperatures (Ji et al., 2008; Jung
et al., 2016). TIPS method also offers a larger selection of potential
solvents because the higher solubility of the polymer could be attained
at higher temperatures. Selecting the appropriate solvent is one of the
218
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
key factors in this process (Kim et al., 2014). A suitable solvent should
have a high boiling temperature, low molecular weight, low toxicity,
low environmental impact, low cost, and reasonable compatibility with
the polymer over a wide temperature and concentration range. In ad-
dition, the thermal conductivity and the miscibility with the quenching
media are also very important factors influencing the final membrane
structure. A recently reported solvent is acetyl tributyl citrate (ATBC)
(Cui et al., 2013; Hassankiadeh et al., 2014) with minimum health
hazards as it is typically employed as a plasticizer for pharmaceutical
coatings and food packaging. More importantly, is not miscible with
water. Hence, this solvent meets all of the necessary requirements as a
TIPS solvent to fabricate microporous hollow fiber membranes.
3.2. Non-solvent induced phase separation (NIPS)
To prepare membranes by the most widely used NIPS method, a
dope solution is first prepared by dissolving a specific polymer in a
suitable solvent to form a homogeneous dope solution (Wang and Lai,
2013). The dope solution is then cast as a thin film and subsequently
immersed in a nonsolvent bath (e.g., water) to induce polymer pre-
cipitation (Kim et al., 2016b). In this process nonsolvent for polymer is
introduced to a homogeneous polymer solution to demix the solution
into two phases: a polymer-rich phase that turns into the matrix of
membranes after the precipitation of the solution, and a polymer-poor
phase that forms membrane pores after it is removed from the pre-
cipitated solution (Guillen et al., 2011). An advantage of NIPS is that it
can be easily modified to prepare hollow-fiber membranes, which have
high membrane surface area (Baker, 2012). As compared to the TIPS
system, NIPS is more complicated as it has three component system
comprised of a polymer, a solvent, and a nonsolvent. Also, it is widely
used not only to prepare polymer hollow fibers but also to fabricate
inorganic and organic-inorganic hybrid hollow-fiber membranes (Kuo
et al., 2008). NIPS can be further divided into three categories: dry
process phase inversion, wet process phase inversion and dry-wet phase
inversion process.
3.2.1. Dry process phase inversion
In dry phase inversion, a volatile solvent is evaporated leading to
phase separation in the polymer solution, which forms the asymmetric
fiber morphology. In most of the situations, the polymer solution for the
dry process consists of polymer, volatile solvent and pore formers. The
polymer solution is cast on a support template (e.g. glass plate) or on a
substrate (e. g. non-woven cloth) to form a nascent membrane. During
the membrane formation, the solvent is allowed to evaporate from the
nascent membrane surrounded by an inert gas. Final membrane
thickness is much thinner than as-cast thickness because of the solvent
loss. However, it is thicker than that of a dense membrane containing
the same quantity of polymer because of the existence of voids which
are formed due to the presence of the pore formers.
3.2.2. Wet process phase separation
Wet phase inversion involves extrusion of the nascent HF directly
into a coagulation bath of a strong non-solvent. A solvent having high
interaction with the non-solvent is chosen to accelerate phase separa-
tion. Different from the dry process, a non-solvent is introduced as a
coagulant in the wet process and the nascent membrane is immersed
into the coagulant immediately for solvent/non-solvent exchange. Most
of the commercially available asymmetric membranes are produced by
the non-solvent induced phase separation.
3.2.3. Dry-wet phase inversion process
The combination of the two processes, “dry-wet”, takes place when
the dope consisting of a polymer, volatile and non-volatile solvents is
spun through an air gap into a coagulation bath as shown in Fig. 1. The
evaporation of the volatile solvent in the air gap forms a stable skin
layer while the phase separation in the coagulation bath forms the
I. Ullah Khan et al.
Fig. 1. Schematic diagram for the formation of nascent HF membrane during phase in-
version (Peng et al., 2012).
underlying porous support layer of the membrane. Alternatively, the
skin can also be formed by a delayed demixing process.
3.3. Electrospinning method
Electrospinning method is used to prepare highly porous mem-
branes with high porosity and surface area with excellent pore inter-
connectivity (Kim et al., 2016b; Huang et al., 2003). This method is
used for various applications such as tissue engineering, sensor mate-
rials, piezoelectric nano-generators, lithium ion battery separators, and
membrane technology (Jia et al., 2007). Low scalability and pro-
ductivity are the main disadvantages of this method but it offers ex-
cellent advantages for membrane contactor applications such as high
surface porosity and hydrophobicity with low tortuosity (Ohgo et al.,
2002). A typical electrospinning apparatus consists of a high voltage
supply, a polymer solution feed system, and one or more collectors.
When an electric potential higher than the surface tension of the
polymer solution is applied, the polymer solution ejects from the nozzle
to the collector as a conically shaped nanofiber, as shown in Fig. 2.
During the travel from the nozzle to the collector, most of the solvent is
evaporated, leaving the dry nanofibers to mound and form an electro-
spun membrane. The morphology of the obtained membrane can be
tailored by varying processing conditions and the shapes of the needle
and collector.
An overall comparison between the various methods of fabrication,
performance and cost of polymer membranes are presented in Table 1.
We only attempt to give a general comparison, because it is quite
complicated to interpret and compare results of various fabrication
techniques. As the formation of membranes with different fabrication
methods depends on a large number of materials and specific process
parameters.
4. Co-extrusion process
Co-extrusion is a process of fabricating multilayer membranes in a
single step, where two or more polymeric solutions extruded through a
single die and join together at the orifices. The shape and structure of
the orifices are specifically designed to meet different requirements.
The co-extrusion can be employed to produce multilayer sheets, blown
films, cast films, tubing, wire coatings, profiles, DLHF membranes and
219
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
other products. Usually, the compositions of the polymer solutions
allow the formation of the selective dense structure in the outer layer
and porous structure in the inner layer that supports it (Wojciechowski,
2014). Some polymers with high selectivity and permeability are
challenging to be fabricated into SLHF membranes for some reasons,
such as low viscosity, brittle failure or long time precipitation. Some
polymers that could not be used in the conventional membrane fabri-
cation process can be employed in the co-extrusion method
(Wojciechowski, 2014). In the co-extrusion process, one dope is ex-
truded through the outer orifice of a triple orifice spinneret, while the
second one is simultaneously extruded through the inner orifice. The
internal coagulant must be introduced at the same time through the
central tube. The co-extrusion is more attractive as compared to con-
ventional spinning processes because of the following reasons such as
(i) Reducing the production cost and time because of the reduced
amount of expensive polymer for equal performance (Li et al., 2002),
(ii) Decreasing the risk of inducing defects (Ding et al., 2008), (iii)
Improved adhesion between layers (Droushiotis et al., 2009), (iv) Each
layer imparts a desired characteristic property, such as stiffness, heat
stability, permeability or resistance. It is impossible for any single
material to attain all of these properties, (v) It is possible to make
multilayer and multifunctional structures in a single process, and (vi) It
provides the possibility to handle polymers that are of excellent
permselectivity but cannot form an integrated asymmetric membrane
on their own. The co-extrusion is not a new technology. It has been used
since the early 1950s to improve product quality and process efficiency.
However, the application of the co-extrusion in the fabrication of
multilayer membranes for separation was just implemented in the
1970s. This process has progressively used in making multilayer ma-
terials and dual-layer structures in last two decades (Constantinou
et al., 2014). It is also important to know the major parameters of the
co-extrusion process where extruded layers are stable. Generally, for
the membrane system, this can be achieved by repeated, iterative and
experimental trial and error methods. Combining this technology with
the computational fluid dynamics (CFD) modeling approach could open
up new applications in extrusion. CFD modeling approach can be used
as a nondestructive and economical tool for process optimization.
Assempour and Razi (2003) give an idea of the simulation setup and
flow onset from the co-extrusion model of multiple plasticine billets.
Their work concentrates on studying the flow patterns within the de-
formation zone of the extrusion die. The effects of various material
properties e.g., shear rate, velocity, and viscosity, on polymer co-ex-
trusion process have been studied previously (Assempour and Razi,
2003; Bhowmick et al., 2013; Gupta, 2008). Until now, the literature
accumulated in this field is very limited and no systemic theory has
Fig. 2. Apparatus used for electrospinning method (Kim et al., 2016b).
I. Ullah Khan et al. Journal of Natural Gas Science and Engineering 52 (2018) 215–234

Table 1
Membrane fabrication techniques: fabrication parameters with their performances (Lalia et al., 2015, 2013).

Fabrication Technique Fabrication parameters Membrane performance Cost

Phase inversion High simplicity High flux Low

High reproducibility Medium retention
High flexibility Medium antifouling properties
High thermal resistance (up to 75 °C)
High mechanical and thermal strength
Wide pH tolerances (1–13)
Low operating pressure limits
Interfacial polymerization High simplicity Low flux Low
High reproducibility High retention
High antifouling properties
Better hydrophilicity
Stretching Medium simplicity High flux Medium
Medium reproducibility Low retention
Solvent free technique Low antifouling properties
Suitable for the highly crystalline polymers Highly porous hydrophobic membranes
Track etching Low simplicity Low flux High
High reproducibility Low retention
Control on the pore size distribution of the membrane Medium antifouling properties
Low porosity
Low surface roughness
Cylindrical shaped pores
Electrospinning Medium simplicity High flux Medium
Medium reproducibility Low retention
Low scalability and productivity Medium antifouling properties
Excellent mechanical properties
High surface porosity and hydrophobicity with low tortuosity

been presented.
4.1. Co-extrusion in dry-wet phase inversion process
A triple-orifice spinneret as shown in Fig. 3 is required in this ap-
proach, in which either the middle or outer channel in a spinneret can
be used to deliver the first coagulant (bore fluid). On the other hand,
the non-solvent in a main external coagulation bath is called the second
coagulant. All three solutions (outer layer, inner layer and bore fluid)
are simultaneously extruded from the respective channels and converge
at the orifice of the spinneret. The nascent HF is immediately brought
into contact with the first external coagulant (bore fluid). After passing
through an air gap, the fiber goes into the main external coagulation
bath (the second coagulant). The resultant membranes are DLHF. The
morphology of a membrane surface could be controlled by the com-
position and flow rate of the first coagulant (bore fluid).
The first one who applied the dry-wet phase inversion approach in
multilayer membrane fabrication is Yanagimoto in NOK Corp in 1988.

Fig. 3. Photographic images of triple orifice spinneret (a) from the side, (b) from the bottom, and (c) its dimensions (Othman et al., 2010).

220
I. Ullah Khan et al.
He applied glycerol as a thickening agent (the first coagulant) at the
outer channel of a triple-orifice spinneret. A high-performance poly-
sulfone microfiltration (MF) HF membrane was prepared (Yanagimoto,
1988). Sasaki (1990) injected a solvent through the middle channel of
the spinneret and a non-solvent through the inner channel. The polymer
solution was extruded through the outer channel. A MF hollow fiber
with high flux was obtained. He et al. (2003) demonstrated that by
applying the dual-bath approach, asymmetric MF, ultrafiltration (UF)
as well as integrally skinned HF membranes with a defect-free top layer
could be prepared for gas separation and pervaporation.
4.2. Co-extrusion in fabrication of the dual-layer hollow fiber membranes
Development of DLHF via co-extrusion and phase inversion process
is an advanced direction in membrane technology. The study of
asymmetric DLHF fabrication via phase inverse process was initiated in
the late 1970s where Henne et al. (1979) patented the first asymmetric
DLHF composite membrane for hemodialysis. Since its inception, stu-
dies on DLHF has been broaden into other applications such as gas
separation (Chen et al., 2015), membrane distillation (Eykens et al.,
2017), nanofiltration (Thomas et al., 2017), ion exchange membrane
(Gohil and Ray, 2017) and pervaporation (Li et al., 2017). For example,
Ekiner et al. (1992) reported the fabrication of DLHF for gas separation
focusing on a potential solution to use costly polymers for membrane
applications. Li et al. (2002) also fabricated a delamination-free
asymmetric DLHF membrane for gas separation that has the perms-
electivity equal to the SLHF even at low material costs. The develop-
ment of DLHF membranes with required separation performance and
morphology is still not an easy task. An ideal DLHF membrane for gas
separation should have some major morphological aspects such as (1)
the outer layer should have a thin dense selective layer with porous
lumen side to decrease transport resistance (Li et al., 2004a), (2) no
delamination can be accepted between the layers of DLHF membrane
for reliable performance and long-term use, and (3) the ratio of DLHF
diameter and twice the wall thickness (D/2Δh) should be around 2 for
operating at high pressure (McKelvey et al., 1997). Therefore, the stu-
dies on selections of membrane materials, solvent systems and bore
fluids, as well as the optimization of spinning conditions, have to
scrutinize to achieve the desired DLHF membrane performance while
maintaining the adhesion of two layers.
Apart from the academic interest, there are also many challenging
engineering issues for the commercial applications of DLHF. For ex-
ample, interlayer instability and viscous encapsulation. The term “in-
terlayer instability” is used to describe the thickness change at the in-
terface between two layers that may become a serious issue when an
ultrathin layer is required. The viscous encapsulation is a phenomenon
in which the less viscous polymer tends to encapsulate the high viscous
polymer when they simultaneous flow through channels. In addition,
the shrinkage of a membrane, both in axial and radial directions,
usually takes place during the phase inversion due to the solvent ex-
change. The shrinkage rate has a minor effect on asymmetric SLHF but
serious effects on DLHF, since it may lead to delamination between
layers and increase mass transfer resistance, reduce mechanical
strength and easily decline the membrane separation performance (Li
et al., 2004a). Comparing the spinning process of the dual-layer with
that of the SLHF, the only difference for the DLHF process is probably
the structure of the spinneret. The spinneret is a key element in the
DLHF spinning. The structure must be well designed to meet rigorous
requirements. For gas separation, the outer diameter of HF is generally
between 100 and 300 μm and the diameter of the outer orifice of a
spinneret is roughly around 500–800 μm. It is a challenging task to fit
three individual concentric annular orifices in such a small space and
make the flow of the membrane solutions in the channels. Another
important feature to fabricate DLHF membrane is material selection
because compatibility between both layer's materials could eliminate
delamination. Low cost polymers with excellent mechanical and
221
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
thermal characteristics are the best option for the inner layer while
polymers with high permselectivity and permeability are very suitable
for the thin selective outer layer (Li et al., 2004b, 2006, 2008).
4.2.1. Advantages of dual-layer hollow fiber membrane
DLHF membranes retain all the advantages of SLHF membranes
such as the high active surface area to volume ratio, self-supporting
structure, fabrication facility, low resistance to gas flow and the ability
to operate at high pressure (He et al., 2002). In order to improve un-
derstanding of CO2 permeation through dual-layer membranes, Chung
et al. (2005) presented a simple permeation model based on Wagner
theory of permeation through metal-carbonate dual-phase membranes.
Wade et al. (2007) also developed a model to describe the flux of CO2
through a dual-layer membrane consisting of solid oxide and molten
carbonate phases. Their models deal with permeation of pure CO2
through the membranes. DLHF has the following advantages over SLHF.
1) DLHF can save largely the fabrication cost of SLHF since the novel
polymeric materials that have been found during the past twenty
years are mostly expensive (Sun et al., 2010, Duarte and Pereira,
2008 and Constantinou et al., 2014).
2) Unlike SLHF, DLHF enables to use brittle but high performance
material as the outer functional layer, while a reasonably in-
expensive material is usually adopted as the inner support layer
(Liu et al., 2007; Jiang et al., 2006).
3) The fabrication of DLHF has more spinning parameters, therefore,
the process is more flexible than SLHF (Jiang et al., 2005).
4) DLHF allows high separation performance by appropriate choice of
two different low cost polymers for the outer and inner layer.
5) DLHF can exhibit excellent pressure resistance compared to in-
tegrally skinned SLHF by adjusting the dope viscosity and the
porosity of the inner layer.
6) DLHF provides more opportunities to improve the separation per-
formance by decreasing the inner layer polymer concentration,
which leads to lower substrate resistance.
7) The dual-layer carbonate membranes represent a new direction for
developing inorganic membranes for high temperature CO2 se-
paration. As polymeric and inorganic microporous SLHF mem-
branes for CO2 separation are limited by either low selectivity or
permeability and tend to lose their selectivity at elevated tem-
peratures (> 300 °C) (Anderson and Lin, 2010; Rui et al., 2009)
8) Chung et al. (2005) fabricated dual-layer membranes consist of a
molten carbonate phase in a porous stainless-steel support which
give high selective permeation of CO2 and O2 at high temperatures.
Stainless steel was selected as the support because of its high
electronic conductivity. Results at high temperature showed that
the stainless steel based dual-layer membrane could separate CO2
efficiently between the temperature of 450 and 650 °C. However, at
temperature above 650 °C, the metal support can be oxidized
causing a reduction in CO2 permeance.
9) Rui et al. (2009) developed another theoretical model to describe
the high temperature CO2/O2 permeation characteristics of a dual-
layer membrane. Their membrane consists of a mixed conducting
oxide ceramic (MCOC) phase for the transport of O2 vacancies and
electron holes, and a molten carbonate (MC) phase for the trans-
port of carbonate ions. The modeling results show that CO2 per-
meation flux is much improved when compared with experimental
data.
10) To further improve the high temperature stability of the dual-layer
membrane and remove the O2 requirement in the feed stream,
Anderson and Lin (2010) proposed new ceramic based carbonate
dual-layer membrane for high temperature CO2 separation. They
used ceramic material, La0.6Sr0.4Co0.8Fe0.2O3−δ (LSCF) as the
supportive layer. This material has high electronic and ionic con-
ductivities (Xu et al., 2004). Furthermore, the nature of the ceramic
material provide greater chemical stability compared to stainless
I. Ullah Khan et al. Journal of Natural Gas Science and Engineering 52 (2018) 215–234

steel dual-layer membrane.
These models can provide useful information for the development of
dual-layer membrane for high temperature CO2 separation.
4.2.2. Application of dual-layer hollow fiber membrane
DLHF membranes have been applied to the fields of gas separation
(Li et al., 2002, Jiang et al., 2004), membrane distillation (Bonyadi and
Chung, 2007), pervaporation (Liu et al., 2007), ion exchange mem-
brane (He et al., 2002), forward osmosis (Wang et al., 2010), nanofil-
tration (Sun et al., 2010) and heavy metal removal from wastewater
(Zhu et al., 2014). Now the DLHF membrane technology has become an
emerging research area for gas separation due to its high applicability
and superior performance and saving on expensively functional

Table 2
Specifications of outer and inner layer of DLHF membranes fabricated by co-extrusion and their gas separation performance.

Materials for Outer layer Materials for inner Results Reference

layer

6FDA durene/mPDA/NMP/THF PES/NMP/Water • Delamination-free membrane (Li et al., 2002)

• Selectivity (O /N ) = 4.6
• Almost
2 2
90% of material costs
PU/NMP/THF PES/PVP/NMP • Production of membrane with dense skin and improved adhesion (Duarte and Pereira,
2008)
PAI/NMP/THF PES/NMP/DG • Defect-free DLHF membrane (Li et al., 2011)
• Ultrathin dense selective layer with thickness of 63 nm
• Selectivity (O /N ) = 7.73
• Selectivity
2 2
PSf/Zeolite/NMP Matrimid/NMP/ (O /N ) = 9.3 (Jiang et al., 2007)
• Selectivity
2 2
Ethanol (CO /CH ) = 150
• Mixed
2 4
gas selectivity (50/50 mol% CO /CH ) = 128
• High
2 4
Matrimid/NMP/Ethanol PEI/NMP/Ethanol draw ratio (Wang et al., 2004)
• No finger-like macrovoids structure
Matrimid/NMP/Ethanol PES/NMP • Delamination-free membrane (Li et al., 2004a)
/Ethanol • Outer layer thickness of 150 nm
• Macrovoid-free structure
Ultem/Al2O3/NMP/Ethanol P84/NMP/Ethanol • layer
Delamination can be reduced by addition of aluminium oxide (Al O ) in the inner 2 3 (Widjojo et al., 2007a)

• AlNo Opost-heat
decreases the shrinkage rate
• Mixed gas selectivity
2 3
treatment
PES/NMP/Ethanol PES/NMP/Ethanol • Pure gas selectivity (O(50/50 mol% of CO /CH ) = 50 (Li et al., 2008)
• Shear within the spinneret
2 4
/N ) = 6.96
• determines the nanoparticlesanddistribution
2 2
Matrimid/Zeolite/NMP Matrimid/NMP elongation drawing in the air gap region (Jiang et al., 2005)

• Post treatment required to eliminate defects of membrane

Matrimid/NMP/Methanol PES/NMP/Ethanol • Pure gas Selectivity (O /N ) = 6.26 (Jiang et al., 2004)
• Mixed
2 2
gas selectivity (40/60 mol% of CO /CH ) = 40
• Low
2 4
coagulant temperatures offer lower permeance and selectivity because of
high substructure resistance
PAI/LiCl/NMP PES/LiCl/NMP • Accumulated water in the interface caused the delamination between two layers (Setiawan et al., 2012)
6FDA-ODA-NDA/NMP/THF/ PSf/Al2O3/NMP • 90% of the intrinsic selectivity could be achieved (Widjojo et al., 2007b)
Ethanol • Low substructure resistance and high bulk and surface porosity due to Al O
nanoparticles
2 3

PES/NMP/Zeolite/Ethanol P84/NMP/Ethanol • AThedense selective layer of 0.55 μm (Li et al., 2006)

• neat selectivity's for O /N and CO /CH were improved 10-20% compared to
PES dense films
2 2 2 4

• Heat treatment was used to reduce the voids to the range that could be treated by
silicon rubber coating
Cellulose/NMMO.H2O PSf/DMAc • Pure gas Selectivity of CO /CH = 38, CO /N = 53 and CO /H = 17 (Mao et al., 2011)
• that
2 4 2 2 2 2
The resulted DLHF membrane exhibited CO permeance five times greater than 2
of SLHF of the same composition
PES/NMP/Ethanol PES/NMP/DG • Pure gas selectivity of O /N = 9.5 and CO /CH = 118 (Li and Chung, 2010)
• Mixed
2 2 2 4
gas selectivity (CO /CH ) = 87.9
• Ultrathin
2 4
dense selective layer of 1092 Å.
• The DLHF membrane modified by silver ions
• High suppression capability for the CO -induced plasticization
• Pure
2
Matrimid/PBI PSf/NMP gas selectivity of H /CO and CO /CH was 14.49 and 46.84, respectively (Hosseini et al., 2010)
• Large
2 2 2 4
/DMAc air gap distance
• Use of elongational drawing
• High resistance toward CO -induced plasticization.
• High
2
outer dope flow rate increase the separation performance
PES/NMP/Ethanol PES/NMP/Ethanol • DLHF membrane with an ultrathin dense selective layer of 407 Å (Li et al., 2004b)
• Heat treatment at 75 °C increased the gas permeance and selectivity of O /N
• Heat
2 2
treatment at 150 °C significantly decreased permeance and selectivity
because of the increased substructure resistance
Matrimid/NMP/THF PSf/NMP • Pure gas selectivity (O /N ) = 7.55 (Ding et al., 2008)
• Selectivity
2 2
increased while permeance decreased with time
PEI/NMP/Water PEI/NMP/Ethanol • The ultrathin dense layer thickness of about 876 Å (Peng et al., 2010)
• Pure gas selectivity (O /N ) = 6.15
• High
2 2
PES/Zeolite/NMP/Ethanol PES/Al2O3/NMP/ permeance and selectivity (Widjojo et al., 2008)
Ethanol • Higher elongation draw ratio
• Heat treatment at 240 °C
• Two step coating
222
I. Ullah Khan et al.
materials compared to SLHF membranes. The recent development of
DLHF membranes of fluoropolyimide/polyethersulfone (PES) (Li et al.,
2002, Liu et al., 2003a,b), Matrimid/PES (Jiang et al., 2004), poly-
sulfone (PSf)-zeolite/polyimide (Jiang et al., 2006), PES-zeolite/P84
copolyimide (Li et al., 2006) and polyetherimide (PEI)-HSSZ 13 zeolite/
polyetherimide (PEI) (Husain and Koros, 2007) for various gas se-
paration are vivid examples. The advantages of the implementation of
hydrophobic-hydrophilic DLHF membranes for membrane distillation
(MD) have been proven to be advantageous compared to SLHF mem-
branes (Bonyadi and Chung, 2007; Edwie et al., 2012; Teoh et al., 2011;
Wang et al., 2011). For the first time, Bonyadi and Chung (2007) fab-
ricated hydrophilic–hydrophobic DLHF membrane for the direct con-
tact membrane distillation (DCMD) process. They investigated the ef-
fect of non-solvents on the morphology of the PVDF membranes and
found that weak coagulants such as water/methanol (20/80, w/w) can
induce a three-dimensional porous structure on PVDF membranes with
high surface and bulk porosities, big pore size, sharp pore size dis-
tribution, high surface contact angle and high permeability but rather
weak mechanical properties. Later clay particles were incorporated into
the outer and inner layer dope solutions, in order to enhance me-
chanical properties and modify the surface tension properties in the
membrane inner and outer layers. The fabricated hollow fibers were
tested for the DCMD process and flux as high as 55 kg/(m2 h) at 90 °C
was achieved in the test. This performance is much higher than most of
the previous reports for SLHF indicating that the application of dual
layer hydrophilic–hydrophobic hollow fibers may be a promising ap-
proach for MD. According to our literature research, most of the pre-
vious nanofiltration (NF) studies on lead, cadmium and chromate re-
moval used flat sheet or tubular membranes (Qian et al., 2017; Sajid
et al., 2018; Zhang et al., 2018). But fabrication of NF hollow fiber
membranes for heavy metal removal is still lacking. Therefore, Zhu
et al. (2014) develop DLHF membranes for effective removal of various
heavy metal ions (Cd+2, Cr2O3−2, Pb+2) from wastewater. They fab-
ricated DLHF membranes by the simultaneous co-extrusion of poly-
benzimidazole (PBI) and polyethersulfone (PES)/polyvinylpyrrolidone
(PVP) dopes through a triple-orifice spinneret using a dry-jet wet phase
inversion process. This newly developed DLHF membrane has superior
rejections performance compared to SLHF membranes for various salts.
The rejections of the membrane to Mg+2 and Cd+2 achieve 98% and
95%, respectively. Also by changing the pH of the solution, the rejec-
tions to Cr2O3−2 and Pb+2 can reach more than 98% and 93%, corre-
spondingly. He et al. (2002) produced NF membranes by employing the
dual-layer hollow fiber spinning technique. By increasing the outer
dope concentration, they obtained DLHF membranes with good adhe-
sion between the two layers. However, the NF performance of the
membrane was lower compared to SLHF. This was possibly due to the
lack of comprehensive knowledge that available to bridge the fabrica-
tion conditions and their influence on the NF performance of the re-
sultant DLHF membranes. Therefore, it is our major contribution to
present a systematic review on the molecular engineering and design of
DLHF membranes in terms of their high performance with improved
spinning conditions. Such a study may be useful in developing non
defective and delaminated free membranes for various industrial ap-
plications.
Materials for outer and inners layers, selectivity's and results of
different works using co-extrusion approach for gas separation are
summarized in Table 2. It is identified that delamination-free and de-
fects free DLHF membrane with improved CO2/CH4 selectivity can be
fabricated by testing different materials, solvents and various post
treatment procedures.
5. Effect of different fabrication parameters on DLHF morphology
and performance
Defect-free fabrication of DLHF membrane is highly dependent on
different parameters that affect its morphology, structure and
223
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
separation performance. In this section, major factors in fabricating
defect-free DLHF membrane is identified i.e. effects of dope prepara-
tion, spinning parameters and post treatment, are thoroughly discussed
in this section.
5.1. Polymer solution composition
Polymer solution composition and its preparation play a significant
role in the morphology and gas separation performance of DLHF
membranes. The thermodynamic interaction of polymer solution (or
nascent fiber) with air or quench medium significantly affects the for-
mation of the skin layer and porous sublayer. The polymer is the fra-
mework of the HF and therefore, the polymer concentration in the dope
solution must have sufficient mechanical strength and decent separa-
tion performance. Whereas, excessive polymer concentration would
increase the solution viscosity due to severe polymer chain entangle-
ment and hardly spinnability to form the fiber. A good choice for the
polymer concentration is often in the range between 25 and 35%. The
dope with significant chain entanglement during fiber fabrication is one
of the important requirement to produce HF with least defects. Below
critical concentration, HF formed with defective pores that cannot be
repaired by silicone rubber coating. However, the concentration far
above the critical value results in a thick dense selective layer with less
permeance. According to the rule of thumb, minimum polymer con-
centration for HF should be 1-2 wt% above the critical concentration for
enhanced gas separation (Liu et al., 2005).
The solvent dissolves the polymer to form a homogeneous single
phase solution. The choice of the solvent depends on the properties of
the polymer, but higher boiling point solvents, such as N-methyl-2-
pyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide
(DMSO) and dimethylacetamide (DMAc) are often used due to their
strong dissolving power of polymer and miscibility with water or
ethanol. Especially, DMAc is preferred as it has low volatility and high
boiling point (∼165 °C). As a common practice in the asymmetric
membrane for gas separation, volatile solvent (i.e. tetrahydrofuran
(THF) and chloroform (CHCl3) is necessary to promote the skin layer
formation during phase separation. Its volatility can produce a polymer
rich phase in the outer layer of nascent fibers while traveling in the air
gap, and accelerate the formation of skin layer (Carruthers, 2003).
5.1.1. Polymer for inner and outer layer
Polymer selection for both layers is a step of primary importance as
it may affect the separation performance by material compatibility.
Ideally, DLHF membrane consists of high performance polymer in the
outer layer and abundant polymer as an inner layer. However, the
properties differences between both layers are often reported as a major
culprit in delamination phenomena. The major properties affecting
DLHF membrane formation is the difference in their glass transition
temperature (Tg). Thus, the polymer of the inner support layer should
have higher Tg than the polymer of the thin selective outer layer. It
would allow the subsequent heat treatment to remove the voids in the
outer selective layer without increasing the substructure resistance of
the inner support layer (Tin et al., 2003; Widjojo et al., 2007b). For this
reason, Jiang et al., 2004, 2005; Li et al. (2004a) and Li et al. (2006)
used PSf and PES of low Tg for the outer selective mixed-matrix layer,
while Matrimid and P84 of high Tg were used for the inner layer. This
practice has solved the issues of interfacial delamination efficiently. But
generally, it is not practical to use Matrimid and P84 for the inner
supportive layer because they are very expensive (e.g. approximately
∼USD 600/kg Matrimid). This raises a question of whether the ex-
pensive materials can be substituted with a cheaper alternative.
5.1.2. Viscosity of the dope solutions
The increase in the viscosity of the dope solution played an im-
portant and critical role in the morphology of the fabricated membrane.
It was observed that a high polymer solution viscosity lead to minimize
I. Ullah Khan et al.
the die-swell effect, mutual diffusion and mass transfer between solvent
and nonsolvent (water) in coagulation bath (Kong and Li, 2001;
Mansourizadeh and Ismail, 2011a,b). Subsequently, the delayed pre-
cipitation takes place, which provides enough time for accommodating
the tensions due to viscoelastic expansion. In addition, the higher shear
stress in the spinneret due to the increase of viscosity resulted in the
thicker skin layer (Mansourizadeh and Ismail, 2011a,b). Indeed, mo-
lecular chains of the polymer tend to align themselves much better at
higher shear. This better molecular orientation results in closer packing
of the polymer molecules and denser outer skin layer (Bakeri et al.,
2012; Mansourizadeh and Ismail, 2010a). So, a lower surface porosity is
expected for the resultant membranes with denser outer skin layer
which consequently impact the performance of the membrane. A
minimum dope viscosity is required to avoid capillary instability in the
air gap. This minimum viscosity depends on the cohesive strength of the
polymer solution under elongation that takes place after the fiber exits
the spinneret. Based on the air gap and the draw ratio, this minimum
viscosity must be defined for each polymer-solvent-nonsolvent system
(Atchariyawut et al., 2006; Ren et al., 2006).
Despite using the same spinning conditions for fabricating the
membranes, there were some differences in the membrane structures,
which can be attributed to the viscosity difference. As the membrane
structure depends on the thermodynamic and kinetic effects of the
additives in the spinning dopes during the phase inversion process
(Feng et al., 2013; Mansourizadeh and Ismail, 2010b). The additives
can increase spinning dope viscosity by increasing the polymer con-
centration in the dope. Generally, low molecular weight additives
which can be used to fabricate porous membranes include: polymeric
additives such as polyvinyl pyrrolidone (C6H9NO)n and polyethylene
glycol (C2nH4n+2On+1), organic and inorganic acids such as phosphoric
acid (H3PO4), acetic acid (CH3COOH) and propionic acid (C3H6O2),
weak non-solvents such as glycerol (C3H8O3), ethylene glycol (C2H6O2)
and diethylene glycol (C4H10O3), weak co-solvents such as methanol
(CH3OH), ethanol (C2H5OH), acetone (C3H6O), and inorganic salts such
as lithium chloride (LiCl), lithium nitrate (LiNO3) and lithium per
chlorate (LiClO4) (Mansourizadeh and Ismail, 2010a). It results in de-
crease of mutual diffusion between solvent in spinning dope and non-
solvent in coagulation bath. Among the additives, glycerol showed the
highest precipitation rate (Pesek and Koros, 1994; Rahbari-sisakht
et al., 2012). Therefore, rapid phase inversion caused to form the small
and narrow finger likes from outer layer of the membrane. The viscosity
Fig. 4. Schematic diagram of DLHF spinning via triple-orifice spinneret (a) outer and inner dope solutions, (b) bore fluid, (c) filter, (d) spinneret, (e) coagulation bath, and (f) take-up
drum (Hosseini et al., 2010).
224
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
of spinning dope with glycerol was obviously higher than the other
dopes, which resulted in higher resistance of mass transfer during the
phase inversion process and delay demixing (Atchariyawut et al., 2006;
Mansourizadeh and Ismail, 2010a; Ren et al., 2006). Therefore, the
kinetic hindrance due to viscosity overcame the thermodynamic factor
and thus resulted in the formation of a thick sponge-like layer. More-
over, formation of some drop shape cavities in the inner layer was also
associated to the slow solidification process during phase inversion.
However, for the polymer dope without glycerol with lower viscosity,
the finger likes were approximately two times larger than the polymer
dope with glycerol. Moreover, glycerol suppressed the cavities forma-
tion, which can be related to the enhanced solution viscosity
(Mansourizadeh and Ismail, 2010a). An essential difference in the dope
formulation of flat sheet and hollow fiber membranes is their dope
viscosity required to cast or spin. Generally, a flat-sheet membrane can
be cast from a polymer dope with its viscosity as low as a few hundred
centipoises, while a minimum dope viscosity required to spin hollow
fibers is of the order of a few thousand centipoise (Ismail &
Mansourizadeh, 2010).
5.2. Spinning parameters
To spin HF with desired separation performance successfully, the
following parameters must be considered: spinneret type, extrusion
rate, draw ratio, air gap, bore fluid composition, bore fluid flow rate
spinning and coagulant temperature (Fig. 4). Good adhesion between
outer and inner polymer dopes can be achieved by optimizing these
spinning conditions. The spinning parameters strongly influence the
phase separation kinetics and thus largely determine the final mor-
phology of the membrane. As discussed below, the spinning parameters
control the rate of phase separation and can thus be used to fine tune
the final membrane morphology.
5.2.1. Spinneret design
Spinnerets have different dimensions depending upon the require-
ment of the specific fiber formation goals. Generally, a spinneret with a
smaller dimension produces smaller fibers, which can withstand high
feed pressure. For instance, 200 μm outer diameter fibers can withstand
high pressure up to 1000 psia in the gas permeation in some cases
(Baker and Lokhandwala, 2008). The spinneret dimension also sig-
nificantly affects the separation performance. The delamination could
I. Ullah Khan et al.
be eliminated by the modification of the spinneret structure (Li et al.,
2004a). The spinneret dimensions directly influence the HF mor-
phology. Spinnerets with smaller spinneret dimension will facilitate the
formation of macrovoid-free morphology. Peng and Chung (2008) have
identified the following effects of the spinneret dimension. (1) As the
spinneret dimension increases, a higher elongation draw ratio is es-
sential to produce defect-free HF membranes; (2) The bigger the spin-
neret, the higher the selectivity; (3) The bigger the spinneret, the
thinner the dense selective layer.
5.2.2. Internal coagulant (Bore fluid)
Similar to the fabrication of asymmetric SLHF membrane, the bore
fluid composition, temperature, and its flow rate controls the internal
skin morphology of DLHF membrane by affecting the rate of phase
separation. (Liu and Koops, 1994). The bore fluid serves to prevent the
collapse of nascent fibers. Yu et al. (2006) identified that low tem-
perature of bore fluid is the main reason for increased tensile strength.
Lower coagulant temperature causes slower demixing rate between the
polymer and solvent thus promoting macrovoids formation, which fa-
vors higher mechanical properties compared to macrovoids formed at
higher bore fluid temperature. In regards to bore fluid composition,
Feng et al. (2011) investigated polyvinylidene difluoride (PVDF) HF
membrane using various aqueous NMP solutions as the internal coa-
gulant. It is reported that at high NMP concentration, the resulted HF
membrane gradually shifted from a double-skin to a single-skin struc-
ture with increased permeability and low mass transfer resistance. This
is because the dense inner skin gradually developed into a porous inner
surface as the NMP concentration increased. Rahbari-sisakht et al.
(2012) investigated the effect of bore fluid composition on membrane
morphology and gas separation performance. It is also identified that
porosity of HF membrane increases at high NMP concentration. Qin
(2004) and Chung et al. (1997) reported that the chemistry of bore fluid
is one of the key parameters to fabricate HF membrane with ultrathin
skin layer for gas separation. Choi et al. (2010) also highlighted the
effect of bore fluid composition on the structure of PVDF hollow fiber
membrane for gas separation processes. They showed that increasing
the concentration of solvent DMAc in the bore fluid changed the inner
skin of membrane from finger-like macrovoids structure to sponge-like
structure.
5.2.3. Air gap
Similar to SLHF membrane the air gap primarily determines the
time that the nascent fibers are exposed to the air during DLHF spinning
(Clausi and Koros, 2000). A larger air gap means a longer residence
time of nascent fibers in the air and may promote the formation of a
thicker skin layer. However, the air gap distance is limited by many
Fig. 5. Influence of coagulation temperature on the formation of macrovoids (Matrimid/PEI) (Li et al., 2004a).
225
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
factors, such as the elasticity of dope and draw ratio. Moreover, a larger
air gap may also generate defects due to gravity and elongational
stresses. Recently, Chung and coworkers have found that air gap dis-
tance plays important roles on the mass-transfer in HF formation
(Chung and Hu, 1997). An increase in air gap distance may reduce
fingerlike voids, permeance, and Tg. At a larger air gap distance, the
moisture-induced and gravity-induced partial phase separation occur
simultaneously. The former may form an ultrathin skin layer with a
high viscosity that is a barrier for nonsolvent intrusion (Tsai et al.,
2006), while the later encourages a radial outer flow that hinders
nonsolvent intrusion (Wang et al., 2004).
The gravity has a major role to determine the membrane mor-
phology while the nascent HF is traveling in the air gap. The nascent
fibers will be stretched and become thinner in the flow direction due to
axial elongation and subsequently, the bulk polymer solution moves
inward leading to gravity-induced radial outflow phenomena (Widjojo
and Chung, 2006). The spinning line can be broken easily along a long
air gap as the gravity and elongational stress overcome the strength of
the nascent fibers. At a constant air gap, a higher draw ratio produces a
stronger tension stress in the fiber, which tends to break the fibers.
Therefore, the air gap must be adjusted carefully so that a stable and the
smooth spinning line can be established. The air gap can also promote
skin formation. In the presence of a volatile solvent within the dope,
evaporation of the solvent within the air gap can increase the con-
centration of the polymer in the outer circumference of the fiber. A
minimum critical air gap is essential to ensure interaction between the
inner and outer layer before phase separation in the water coagulation
bath takes place. Usually, a large air gap distance initiates the unstable
dope line leading to fiber curling and disruption due to gravity and
elongational stresses. The inner and outer layers were found to well
adhere to 3–15 cm air gap distance. Also, the residence time of 0.1–3 s
was calculated for the nascent fiber in the air gap distance (Bhandari
et al., 2013).
5.2.4. Coagulation bath
Outer layer morphology can be controlled by the external coagulant
chemistry and temperature. As for the coagulant chemistry, water is
often used as an external coagulant as it is cheap and environmentally
friendly. If the water has a higher diffusion rate in the outer layer
compared to the diffusion of bore fluid into the inner layer, large
macrovoids are formed on the outer layer surface and hold extra water
at the interface, hindering the adhesion of the two layers and giving rise
to delamination. Therefore, a low penetration rate of the water through
the outer layer leads to a delamination-free structure of membrane
(Setiawan et al., 2012). Furthermore, the mass transfer between the
polymer, solvent, and non-solvent, and subsequently the membrane
I. Ullah Khan et al.
morphology, are highly dependent on the external coagulation bath
temperature (Jiang et al., 2004). When water is selected as the internal
and external coagulants, the coagulation process starts immediately in
the lumen side after extrusion of the dope solutions from the spinneret.
However, only partial phase separation occurs at the external surface of
the outer layer in the air gap by moisture-induced phase separation
(Feng et al., 2011). The complete phase separation of the external layer
is achieved by fully immersing the fibers in the coagulant bath.
Therefore, the outer layer surface acts as a moving boundary surface in
the air gap region while the inner surface skin is supposed to be a fixed
boundary surface.
As mentioned above, water is commonly used as the coagulant
medium (nonsolvent medium) since most polymers are hydrophobic.
Nevertheless, other solvents can be added to the water depending on
the requirement of membrane formation. For example, water/alcohol
mixtures provide more flexibility for the coagulant composition than
water alone. Ethanol is often preferred as the non-solvent due to its high
volatility, which affects the skin layer formation (Carruthers, 2003),
and low toxicity. Regarding the effect of coagulant temperature, Fig. 5
shows the morphology of DLHF fabricated at different coagulation
temperatures. It implies that only fibers spun at 10 °C gives the small
number of macrovoids, and their length and diameter are comparable
for three cases. High inner layer dope viscosity at low temperature is
the main cause for less number of macrovoids. Also, macrovoids are
opened to the lumen of the HF.
The coagulant bath depth is also critical in the formation of HF, as it
determines the residence time of fibers in the coagulant medium. A
deeper coagulant bath may help the formation of the skin layer and
porous structure of HF as the nascent fibers have a longer residence
time in the coagulant bath. The coagulant bath medium, the height, and
the temperature must be adjusted carefully to allow complete phase
separation so that the nascent fibers are not squeezed by the guide roll
to form oval structures. Use of poor nonsolvent results in denser, low
porosity membranes with large skin thicknesses. The addition of sol-
vents and salts to the generally strong non-solvent in the coagulant bath
has also been attempted to lower non-solvent activity, thus also leading
to denser membranes (Boom and Wienk, 1992).
5.2.5. Spinneret temperature
The spinneret temperature has several effects on determining the HF
morphology. 1) Kinetic effect; the increase in spinneret temperature
increases the interlayer diffusion (Li et al., 2004a) leading to low dope
viscosities and high molecular diffusion rate. The increase in spinneret
temperature also increases the evaporation of solvent from the external
Fig. 6. Influence of spinneret temperature on the cross-sectional morphology of DLHF (Matrimid/PEI) membrane structure (Li et al., 2004a).
226
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
surface while the nascent HF is traveling through the air gap. 2)
Rheological effect; the “pulsing” problem of fibers can be resolved by
lowering the spinneret temperature because the viscosity of dope is
increased at a lower temperature and this often dumps such instabilities
(Cao et al., 2004). On the other hand, a high spinneret temperature can
reduce the viscosity of dope and improve the spinnability of viscous
dope. Usually, an appropriate spinneret temperature is between room
temperature and 80 °C. The spinneret temperature has been found to be
not as crucial as coagulation temperature since no clear and noticeable
change was observed in the cross-sectional morphology (Fig. 6). But,
spinning temperature becomes very vital and key parameter during
thermally induced phase separation process (TIPS).
5.2.6. Extrusion flow rate
The DLHF spinning is more complex compared to SLHF because it
involves two different polymer dopes being co-extruded and pre-
cipitated simultaneously. The dope flow rates determine the layer
thicknesses after precipitation and subsequently play a significant role
in membrane separation performance. The outer selective layer should
be as thin as possible to reduce the cost of materials. But, it is a great
challenge for membrane researchers to achieve it. A low dope flow rate
can produce a defective dense selective outer layer while a high flow
rate may make it thicker or defective. The inner layer dope flow rate
also affects the performance and morphology of the inner porous layer
(Jiang et al., 2004). East et al. (1986) have studied the effect of polymer
extrusion rate on dry-jet wet-spun PSf hollow fiber membrane and
found that increasing dope extrusion rate (DER) would reduce the gas
permeation rate and increase the selectivity. In addition, to produce a
thin selective layer of mixed matrix membrane, the adjustment of the
ratio of the outer and inner dope flow rate is very important (Li et al.,
2006). A faster extrusion rate tends to produce larger outer diameter
fibers. At a given extrusion rate, the draw ratio is increased with the
take-up rate and eventually the radial dimension of fibers is reduced
with faster extrusion rate (Bhandari et al., 2013).
5.2.7. Elongational draw ratio
The ratio of take-up rate to extrusion rate defines the practical draw
ratio which significantly controls the diameter and separation perfor-
mance of fibers. It has to be noted that a high draw ratio may introduce
elongational forces at the outer layer of nascent fibers. This stress may
orientate the segmental chains in polymer and cause a higher perms-
electivity; however if excessive, defects and even fiber breaks can occur
(Ismail et al., 1997). The elongational draw ratio for the DLHF is de-
fined as follows:
I. Ullah Khan et al.
2
[(DOuterorifice 2
− DInner 2 2
tube OD ) − (DOuter tube OD − DInner tube ID )]Spinneret
ϕ= 2 sired morphology and high separation performance. In essence, both
[(DOD − D 2ID]Fiber
Elongation draw ratio also affects the morphology. Generally, its
high value is advantageous as it increases productivity and reduces the
diameter of HF (increases the surface to volume ratio). It was found that
macrovoids were completely eliminated at a draw ratio of 145 (Fig. 7).
Furthermore, increase in draw ratio has the following effects. (1) as
already mentioned, high elongational stress can change the segmental
orientation of the polymer (Wolf, 1984) and it can suppress the mac-
rovoid formation (Ren et al., 2002), (2) the high elongational rates may
induce chain packing (Cao et al., 2004), that may retard the penetration
of external coagulant. When HFs are spun with nanoparticles in the
outer layer, it has been observed elongation-induced radial outflow can
push nanoparticles towards outer surface during the fabrication of
DLHF membranes and modify the nanoparticle dispersion across the HF
membrane (Jiang et al., 2005).
5.2.8. Drying process
Solvent and non-solvent must be removed from HF without col-
lapsing the fiber structure. The fibers that come out of the coagulation
bath contain water and must be dried before being potted into modules.
However, the wet fibers must not be dried immediately because the
pores of the HF are collapsed and the fibers destroyed by the capillary
force when water is removed from the pores. Thus, the solvent ex-
change is the final spinning step. In the solvent exchange procedure
water in the HF is replaced progressively by methanol and a volatile
hydrocarbon (e.g. hexane or heptane) (Pellegrino and Kang, 1995;
Story and Koros, 1992). When the hydrocarbon evaporates, the pore
does not collapse because there is practically no capillary force due to
the low surface tension of the hydrocarbon. Deprived of appropriate
solvent exchange, it has been testified that the apparent dense selective
layer thickness may increase from 730 Å (after water, methanol, and
hexane treatments) to 4400 Å and 18,800 Å (only after water treat-
ment) (Clausi and Koros, 2000).
5.3. The optimization of hollow fiber spinning process parameters for high
performance
The fine tuning of the above stated fabrication process parameters
to achieve defect free DLHF membrane is a quite challenging and
complex method. All the spinning parameters should be optimized and
Fig. 7. Effect of draw ratio and take-up speed for macrovoids formation (Matrimid/PEI) membrane structure (Li et al., 2004a).
227
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
systematically controlled to obtain hollow fiber membranes with de-
permeability and selectivity are the most important parameters as they
play a major key role in determining the process economics and spin-
ning parameters (Dzinun et al., 2015). The performance of DLHF
membranes strongly relies on the spinning parameters such as the
spinneret dimensions and design (Zulhairun et al., 2014b), dope ex-
trusion rate (DER) (Zulhairun et al., 2014a), bore fluid compositions
and its flow rate (Zulhairun and Ismail, 2014), air gap distance
(Bhowmick et al., 2013), force convective gas flow rate and take-up
speed (Rezaei DashtArzhandi et al., 2015). The temperature of spin-
neret, dope solution, and coagulation bath are the secondary para-
meters that also plays additional role in affecting the membrane mor-
phology and hence the performance of the hollow fibers (Sun et al.,
2010). Although the effects of various spinning parameters have been
extensively discussed throughout literature, unfortunately there is no
established guide to select the appropriate spinning conditions for
specific spinning systems. Consequently, spinning may involve intricate
trial-and-error experiments in order to obtain desired gas separation
performance (Wallace et al., 2006). The present study, hence seeks for
the optimum spinning conditions in which defect free DLHF membrane
may exhibit superior performance so as to surpass the intrinsic se-
paration performance of its pristine counterpart.
5.4. Post heat treatment and additional coating
After the solvent exchange, the HFs are ready to be potted into
modules. DLHF defects are sealed by different post treatment methods.
But two post treatment methods are often used for HF modification. The
first one is to coat a thin layer of the high molecular weight poly-
dimethylsiloxane (PDMS) solution in heptane. The solution is heated so
that the crosslinking of PDMS chains can caulk the defects in the fibers.
The other post treatment method is called reactive post treatment. Two
solutions are applied on the defective fibers: diethyl toluene diamine in
iso-octane and trimesoyl chloride/PDMS mixture in iso-octane. The si-
licone rubber coating is the well-known procedure to seal HF defects
and improve separation properties, and this method is widely practiced
in industries (Henis and Tripodi, 1981). The objective of post treatment
is to caulk the fiber outer surface with a highly permeable polymer
layer, thereby repair the pinholes defects in the fibers. The main chal-
lenge is to reduce the voids between nanoparticles and the polymer
matrix in mixed matrix membrane of DLHF due to their mutual
I. Ullah Khan et al.
incompatibility. Silicone rubber coating is not enough to seal these
voids that are in the range of ten of nanometers and allow the Knudsen
diffusion of gas molecules, lowering the selectivity (Quan et al., 2017;
Liu et al., 2005). Jiang et al. (2006) have proved that heat treatment is
the only way to narrow these voids that cannot be treated by silicon
rubber coating.
The heat treatment induces the relaxation of the stresses imposed on
the HFs while they were spun, leading to the higher packing density of
polymer chain, reduces the outer surface defects, controls and reduces
pores size and removes membrane surface defects. It is observed that
the heat treatment not only eradicates the delamination of the layers
but also reduces voids between the polymer and inorganic phases.
However, for mixed matrix membrane, the heat treatment will sig-
nificantly reduce the gas separation performance and increase the se-
lective layer thickness due to densification of the mixed matrix outer
layer (Jiang et al., 2006). Other than the heat treatment, extensive
works including tailoring the chemical structures and performing cross-
linking modifications by different methods such as thermal and che-
mical treatment and UV irradiation have been carried out with the aim
of obtaining membranes with better gas separation properties. Among
all of the efforts, the cross-linking modification seems one of the most
promising approaches to improve chemical resistance and resistance to
plasticization of polymeric membranes (Liu et al., 2003a,b). The che-
mical alteration of membrane materials improves the gas separation
performance and the “upper-bound” limit of the permeability-se-
lectivity relationship can often be exceeded. Main modification tech-
niques are bromination (Chern et al., 1987), carboxylation (Story and
Koros, 1992), acylation (Percec, 1987), sulfonation (Pellegrino and
Kang, 1995) and amine modification (Nordin et al., 2015).
Fig. 8. The effect of shrinkage percentage on DLHF membrane structure (Li et al., 2004a).
228
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
6. Delamination phenomena
To fabricate DLHF membranes via co-extrusion process, the dela-
mination is crucial and cannot be ignored as it will affect the reliability
of HF. To be delamination-free is very important and a key factor for
the performance of DLHF membranes. A seamless interface may be
achieved if both dope solutions are thermodynamically miscible and
mutually diffused with each other. However, other factors cannot be
ignored. It is well-known that the miscibility of the two polymer layers
plays an important role in their adhesion (Li et al., 2004b). Well mis-
cible polymer pairs often lead to good adhesion, immiscible polymer
pairs often result in delaminated structures. The controlling parameters
to the adhesion/delamination are of great importance since polymers
with different separation characteristics are often chemically different
and not miscible. He et al. (2002) and Li et al. (2002) eliminated the
delamination by using different methods. The former developed co-
extruded HF membrane using sulfonated polyethersulfone (SPES) as the
outer selective layer and PSf as the inner supportive layer for nano-
filtration. It was identified that for good adhesion, SPES concentration
should be high. In addition, adhesion could be improved by premixing
dope solutions before exiting the spinneret. The latter group introduced
the concept of “inter-diffusion” (an assumption that polymer chains can
diffuse freely as long as no water reaches the interface). It also im-
proved the adhesion between layers.
Li et al. (2002) fabricated the fluoro polyimide/polyethersulfone
DLHF for gas separation and found that the difference in the shrinkage
rates was the major cause of delamination. Li et al. (2004a) further
reported that reducing the shrinkage difference between the two layers
resulted in the delamination-free interface. They also concluded that
increased inner layer PES concentration gave good adhesion between
layers due to less shrinkage. Delamination arises when the inter-
I. Ullah Khan et al.
diffusion of the polymer chains in the outer and inner dope solutions is
interrupted by the penetration of the nonsolvent from the coagulation
bath (He et al., 2002). Similarly, Sun et al. (2010) showed that dela-
mination occurs due to the accumulation of H2O at the interface. Fur-
thermore, the additive from the inner dope solution may move across
the outer dope solution due to a concentration difference, which causes
phase separation in the interfacial region and subsequent delamination
between two layers (Pereira and Nobrega, 2003). The adhesion can be
enhanced if the solutions have enough time to interpenetrate with each
other. But, large shrinkage difference and immediate precipitation lead
to delamination (Pereira and Nobrega, 2003).
6.1. Consolidation of asymmetric dual-layer hollow fiber membrane
Consolidation is immensely important for the DLHF membrane
fabrication. Both layers must have a uniform thickness and suitable
concentricity. The structural integrity and delamination between layers
are crucial in DLHF membrane fabrication (Dzinun et al., 2015). The
development of DLHF membranes now faces the challenge of interface
integrity. One aspect of the problems which have been intensively in-
vestigated is the interface delamination and the microstructure dis-
continuity (Wang et al., 2004; Jiang et al., 2005). Also, it significantly
affects the long-term stability of the fibers during applications. It is
observed that delamination can be minimized by selecting compatible
materials with improved spinnerets designs (Widjojo et al., 2007a).
Interfacial resistance is critical for DLHF membranes fabricated by
co-extrusion and dry-jet wet spinning. The demands of high separation
performance have motivated researchers to develop membranes with
minimum flow resistance. As DLHF membrane has the distinction of
synergizing the physicochemical strengths of various materials in
composite membrane by a significantly simplified production process.
For the first time, the importance of interface structural resistance in
overall membrane transport property was revealed by Jiang and Song
(2011) using PSf as outer layer and Matrimid as inner layer of DLHF
membrane as a demonstration system. They observed that dope for-
mulation of the two layers is the main factor to control interfacial re-
sistance between layers. But evolution of interface structure still re-
quires further exploration for fully understanding and utilizing the
composite membrane by co-extrusion and phase inversion approach.
Since DLHF membranes involves the co-precipitation of two individual
dope solutions which possibly are made from different materials and
have different solvent compositions, the membrane forming process is
much more complicated than that of single-layer ones. Till present, only
very limited literature are available on the fundamentals of DLHF
Fig. 9. Effect of dope flow rates on delamination of DLHF (Matrimid/PEI) membrane structure (ratio of outer to inner dope flow rates: (a) 0.83, (b) 0.285, and (c) 0.125 (Li et al., 2004a).
229
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
formation. The membrane with high mass transfer resistance may not
withstand high pressures, especially for gas separation (Li et al., 2008).
When the feed pressure is high, the outer layer may collapse and de-
taches from the inner support layer. Therefore, the objectives of this
work are to fundamentally investigate the effects of different spinning
parameters to improve the membrane morphology and its performance.
6.2. Layers' shrinkage percentages versus delamination
Membrane structure is highly affected by different shrinkage per-
centages (Fig. 8). Delamination-free membrane structure is possible
with same shrinkage percentages of both layers (Fig. 8A). Higher
shrinkage rate of inner layer gives a gap between both layers (Fig. 8B).
Three following different cases are discussed for higher outer layer
shrinkage rate. (1) If the mechanical outer layer material is brittle and
its mechanical strength is weaker than the inner layer, the weak outer
layer may rupture due to the internal stresses (Fig. 8C), (2) For
stretchable outer layer, it is possible to get delamination-free structure
as the inner layer may get tightened by the outer layer (Fig. 8D), and (3)
when the outer layer is stronger than the inner one, it produces a fully
collapsed inner layer (Fig. 8E).
The adjustment of the ratio between layers ‘dope flow rates is the
key parameter to control the delamination. It remarkably decreased
with a decrease in the ratio and was totally removed at a ratio of 0.125
(0.1/0.8) (Jiang et al., 2005) (Fig. 9C). They also identified that high
shrinkage rate of the inner layer is causing the interfacial delamination.
6.3. The effect of dope chemistry influence on interfacial structure
The choice of solvents in the dope solution of the two layers is very
important since it affects the diffusion rate and compatibility of two
layers. Li et al. (2004a) and Dzinun et al. (2015) reported that using the
same solvents in both layers could create less resistance for gas trans-
port at the interface. Different solvents have different solubility with
polymers and offer different interfacial morphologies adding more re-
sistance to gas transport.
6.4. Delamination influence on interfacial structure
The interfacial structure is greatly disturbed by delamination.
Fig. 10 illustrates the inner surface morphology of the delamination-
free outer layer and a delaminated DLHF membrane. A uniform and
completely porous structure can be seen for delamination-free DLHF
(Fig. 10A), while irregular porous and dense inner surface structure was
I. Ullah Khan et al.
Fig. 10. Delamination effect on the outer layer's inner surface morphology of DLHF (Matrimid/PEI) membrane (Li et al., 2004a).
observed for the delaminated membrane (Fig. 10B). This is possibly
because of the fact that the delamination forms a gap between layers
during the coagulation process.
6.5. The formation of macrovoid-free structure
Macrovoids can be reduced in membrane structure by greater dope
viscosity and low fluidity while contacting non-solvents (Cabasso et al.,
1977; Strathmann et al., 1975; Strathmann and Kock, 1977). Kesting
et al. (1990) testified that macrovoid free membranes could be made by
high solid content (30 wt %), high viscosity and low non-solvent tol-
erance. In addition, the membrane thickness has a significant effect on
the formation of the macrovoid-free structure. Vogrin et al. (2002)
could prepare macrovoid-free membrane when the membrane was
ultra-thin. Li et al. (2004b) also testified a critical structure-transition
thickness for membrane morphology from a sponge-like to a finger-like
structure. Widjojo and Chung (2006) showed that membrane mor-
phology could also be transformed from a sponge-like to a finger-like
structure with an increase in membrane thickness. There is the critical
structure-transition thickness (Lc), therefore, below which membranes
have fully sponge-like structure, while above Lc membranes show a
mainly finger-like macrovoid structure. The Lc value is governed by
materials characteristics, dope formulation, and membrane fabrication
230
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
parameters.
Macrovoids are the fragile mechanical points that result in mem-
brane poor performance at high pressures. There are many methods to
reduce or eliminate macrovoids in the membrane structure such as (1)
by means of high polymer concentration solutions (Kesting et al.,
1990), (2) addition of high viscosity components (Liu et al., 2003a,b),
(3) spinning at high shear rates (Ren et al., 2002), (4) introducing de-
layed demixing (Kim et al., 2001), (5) introducing gelation (Lin et al.,
2002), (6) addition of surfactants (Tsai, 2000), (7) small air gap and
flow channel thickness in the spinneret (Widjojo and Chung, 2006), (8)
with a high elongational draw ratio (Wang et al., 2004), (9) introduc-
tion of moisture (Chung et al., 1997), (10) higher coagulation bath
temperature (Chung and Kafchinski, 1997), and (11) the excellent
nonsolvent with low coagulation rate or high coagulation value (Yao
et al., 1988). Some researchers believe that macrovoids are initiated by
an immediate liquid-liquid demixing (Kim et al., 2001; Lin et al., 2002),
while others said that it arises from a local surface instability, skin
rupture and solvent intrusion (Nordin et al., 2015; Tsai, 2000). There
are mainly four types of macrovoids such as (1) inward-pointed, (2)
outward-pointed, (3) elliptical, and (4) teardrop shapes. The residual
traces of nonsolvent intrusion is the major cause for the inward-pointed
and outward-pointed macrovoids (Widjojo and Chung, 2006). Elliptical
and teardrop shape macrovoids originate from solution capillary
I. Ullah Khan et al.
convection (Pekny et al., 2003). But mainly all macrovoids result from
surface instability, rapid coagulation during phase inversion and skin
rupture (Strathmann et al., 1975).
7. Research opportunities
Natural gas can be considered as the largest fuel source required
after the oil and coal. Nowadays, the consumption of natural gas is not
only limited to the industry but also extensively consumed by the power
generation and transportation sector. These phenomena supported the
idea of going towards sustainability and green technology as the natural
gas is claimed to generate less-toxic gases. Latest research area using
DLHF membranes fabricated via a dry-wet phase inversion using co-
extrusion technique offer a number of advantages, such as self-sup-
porting structure, high active surface area, a single-step fabrication
process and ability to withstand high operating pressure for gas se-
paration, low capital cost with improving performance, chemical,
thermal, and mechanical strength. But the material selection and
method of preparation are the most important part in the fabrication of
DLHF membrane. So the next research must be much optimized in
determining the materials for gas separation and new methods of fab-
rication. As DLHF membranes are fabricated by extruding two different
dope solutions simultaneously, the morphology and properties of both
inner and outer layers are highly dependent on the spinning conditions.
Also, producing high performance DLFH membranes via the co-extru-
sion process could be very challenging because it involves a sophisti-
cated spinning mechanism where two different phase inversion path-
ways occur simultaneously. The main problem in DLHF membrane
fabrication is its structural integrity and delamination between layers.
Good adhesion between inner and outer polymer dopes can be achieved
by optimizing the spinning parameters such as dope extrusion rates,
bore fluid composition and flow rate, spinneret and coagulation tem-
perature, air gap and collection speed. Also, development and com-
mercialization, process stability, and challenges in terms of energy
consumption and economic assessment for the DLHF membranes are
still exist. Also, fabrication of DLHF highly depends on its optimization
design with low operational cost (González et al., 2017). Other tech-
nologies like SLHF membrane, water scrubbing, amine scrubbing, and
PSA have been developed for many years, a lot of research has already
been conducted to improve their efficiency. DLHF membrane tech-
nology may have a breakthrough within a short period if the opera-
tional and economic problems are properly fixed.
8. Concluding remarks
A significant development has been made to fabricate DLHF mem-
brane via phase inversion in a single step co-extrusion process since
DLHF has all the benefits of SLHF and great potentials to overcome all
challenges with inexpensive alternatives. It has been attempted to solve
engineering issues and provide a great flexibility for modifying the
membrane morphology. In particular, polymer material selection, dope
flow rates, air gap, bore fluid, coagulant type, and temperature, as well
as post treatment processes, have been found to play critical roles for
the production of high performance DLHF membranes for gas separa-
tion. Delamination, which is a serious issue of DLHF, can be controlled
by using the same polymers in both layers and optimizing spinning
conditions. This paper also reviews the co-extrusion process and spin-
ning parameters for the fabrication of a novel class of high performance
DLHF membrane for gas separation. Recently DLHF membrane fabri-
cation has gained much attention due to improving performance and
economic issues. However, more efforts are required to investigate its
fabrication parameters for required morphology and gas separation
performance. Although high separation can be achieved by commercial
single layer membranes, DLHF membrane with specific functionalities,
better defined pores or functionalized transport channels and delami-
nation free structure could provide breakthroughs in the industry.
231
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
However, non-ideal morphologies that undesirably affect membrane
properties remain a big problem to be overcome prior to its practical
application. Also, the use of computational fluid dynamics (CFD)
modeling approach in the co-extrusion process could enhance the se-
paration performance by optimizing the spinning parameters.
Therefore, it can be concluded that DLHF will remain key in research
areas to fully exploit its potentials for gas separation and other appli-
cations. Based on the discussion, it still requires many improvements
before it can be routinely applied in industrial applications.
Acknowledgement
The authors gratefully acknowledge financial support from the
Universiti Teknologi Malaysia under the Research University Grant Tier
1 (Project number: Q. J130000.2546.12H25) and Nippon Sheet Glass
Foundation for Materials Science and Engineering under Overseas
Research Grant Scheme (Project number: R. J130000.7346.4B218). The
authors would also like to thank Research Management Centre,
Universiti Teknologi Malaysia for the technical support. Lastly, the first
author would also like to thank National University of Science and
Technology, Pakistan for their scholarship under Faculty Development
Programme (FDP).
References
Alzahrani, S., Mohammad, A.W., 2014. Challenges and trends in membrane technology
implementation for produced water treatment: a review. J. Water Process Eng.
http://dx.doi.org/10.1016/j.jwpe.2014.09.007.
Anderson, M., Lin, Y.S., 2010. Carbonate-ceramic dual-phase membrane for carbon di-
oxide separation. J. Membr. Sci. 357, 122–129. http://dx.doi.org/10.1016/j.memsci.
2010.04.009.
Aroon, M.A., Ismail, A.F., Matsuura, T., Montazer-Rahmati, M.M., 2010. Performance
studies of mixed matrix membranes for gas separation: a review. Sep. Purif. Technol.
75, 229–242. http://dx.doi.org/10.1016/j.seppur.2010.08.023.
Assempour, A., Razi, S., 2003. Physical modeling of extrusion process. J. Mech. Eng. 4 (1),
61–69.
Atchariyawut, S., Feng, C., Wang, R., Jiraratananon, R., Liang, D.T., 2006. Effect of
membrane structure on mass-transfer in the membrane gas-liquid contacting process
using microporous PVDF hollow fibers. J. Membr. Sci. 285, 272–281. http://dx.doi.
org/10.1016/j.memsci.2006.08.029.
Baker, R., 2002. Future directions of membrane gas separation technology. Ind. Eng.
Chem. Res. 41 (6), 1393–1411.
Baker, R., Lokhandwala, K., 2008. Natural gas processing with membranes: an overview.
Ind. Eng. Chem. Res. 47 (7), 2109–2121.
Baker, R.W., 2012. Membrane Technology and Applications. http://dx.doi.org/10.1016/
S0958-2118(96)90133-0. Membrane Technology.
Bakeri, G., Ismail, A.F., Rahimnejad, M., Matsuura, T., Rana, D., 2012. The effect of bore
fluid type on the structure and performance of polyetherimide hollow fiber mem-
brane in gas-liquid contacting processes. Sep. Purif. Technol. 98, 262–269. http://dx.
doi.org/10.1016/j.seppur.2012.07.024.
Bhandari, D., Olanrewaju, K.O., Bessho, N., Breedveld, V., Koros, W.J., 2013. Dual layer
hollow fiber sorbents: concept, fabrication and characterization. Sep. Purif. Technol.
104, 68–80. http://dx.doi.org/10.1016/j.seppur.2012.11.003.
Bhowmick, K., Morvan, H.P., Furniss, D., Seddon, A.B., Benson, T.M., 2013. Co-extrusion
of multilayer glass fiber-optic preforms: prediction of layer dimensions in the ex-
trudate. J. Am. Ceram. Soc. 96, 118–124. http://dx.doi.org/10.1111/jace.12003.
Bonyadi, S., Chung, T.S., 2007. Flux enhancement in membrane distillation by fabrication
of dual layer hydrophilic-hydrophobic hollow fiber membranes. J. Membr. Sci. 306,
134–146. http://dx.doi.org/10.1016/j.memsci.2007.08.034.
Boom, R., Wienk, I., 1992. Microstructures in phase inversion membranes. Part 2. The
role of a polymeric additive. J. Membr. Sci. 73 (2), 277–292.
Cabasso, I., Klein, E., Smith, J.K., 1977. Polysulfone hollow fibers. II. morphology. J.
Appl. Polym. Sci. 21, 165–180. http://dx.doi.org/10.1002/app.1977.070210115.
Cao, C., Chung, T.-S., Chen, S.B., Dong, Z., 2004. The study of elongation and shear rates
in spinning process and its effect on gas separation performance of Poly(ether sul-
fone) (PES) hollow fiber membranes. Chem. Eng. Sci. 59, 1053–1062. http://dx.doi.
org/10.1016/j.ces.2003.10.023.
Carruthers, S., 2003. Morphology of integral-skin layers in hollow-fiber gas-separation
membranes. J. Appl. Polym. Sci. 90 (2), 399–411.
Chen, X., Vinh-Thang, H., Ramirez, A.A., Rodrigue, D., Kaliaguine, S., 2015. Membrane
gas separation technologies for biogas upgrading. RSC Adv. 5 (31), 24399–24448.
http://dx.doi.org/10.1039/C5RA00666J.
Chern, R.T., Sheu, F.R., Jia, L., Stannett, V.T., Hopfenberg, H.B., 1987. Transport of gases
in unmodified and arylbrominated 2,6-dimethyl- 1,4-poly (phenylene oxide). J.
Membr. Sci. 35, 103–115. http://dx.doi.org/10.1016/S0376-7388(00)80925-4.
Choi, S., Tasselli, F., Jansen, J., Barbieri, G., 2010. Effect of the preparation conditions on
the formation of asymmetric poly (vinylidene fluoride) hollow fibre membranes with
a dense skin. Eur. Polym. 46 (8), 1713–1725.
I. Ullah Khan et al.
Choi, Y.-S., Nešić, S., 2011. Determining the corrosive potential of CO2 transport pipeline
in high pCO2-water environments. Int. J. Greenh. Gas Contr. 5, 788–797. http://dx.
doi.org/10.1016/j.ijggc.2010.11.008.
Chung, S.J., Park, J.H., Li, D., Ida, J.-I., Kumakiri, I., Lin, J.Y.S., 2005. Dual-phase
Metal−Carbonate membrane for high-temperature carbon dioxide separation. Ind.
Eng. Chem. Res. 44, 7999–8006. http://dx.doi.org/10.1021/ie0503141.
Chung, T., 1996. A review of microporous composite polymeric membrane technology for
air-separation. Polym. Polym. Compos. 4, 269–283.
Chung, T., Hu, X., 1997. Effect of air-gap distance on the morphology and thermal
properties of polyethersulfone hollow fibers. J. Appl. Polym. Sci. 66 (6), 1067–1077.
Chung, T., Jiang, L., Li, Y., Kulprathipanja, S., 2007. Mixed matrix membranes (MMMs)
comprising organic polymers with dispersed inorganic fillers for gas separation. Prog.
Polym. Sci. 32 (4), 483–507.
Chung, T., Kafchinski, E., 1997. The effects of spinning conditions on asymmetric 6FDA/
6FDAM polyimide hollow fibers for air separation. J. Appl. Polym. Sci. 65 (8),
1555–1569.
Chung, T., Teoh, S., Hu, X., 1997. Formation of ultrathin high-performance poly-
ethersulfone hollow-fiber membranes. J. Membr. Sci. 133 (2), 161–175.
Clausi, D., Koros, W., 2000. Formation of defect-free polyimide hollow fiber membranes
for gas separations. J. Membr. Sci. 167 (1), 79–89.
Constantinou, A., Barrass, S., Gavriilidis, A., 2014. CO2 absorption in polytetra-
fluoroethylene membrane microstructured contactor using aqueous solutions of
amines. Ind. Eng. Chem. Res. 53, 9236–9242. http://dx.doi.org/10.1021/ie403444t.
Cui, Z., Hassankiadeh, N.T., Lee, S.Y., Lee, J.M., Woo, K.T., Sanguineti, A., Arcella, V.,
Lee, Y.M., Drioli, E., 2013. Poly(vinylidene fluoride) membrane preparation with an
environmental diluent via thermally induced phase separation. J. Membr. Sci. 444,
223–236. http://dx.doi.org/10.1016/j.memsci.2013.05.031.
Dalane, K., Dai, Z., Mogseth, G., Hillestad, M., Deng, L., 2017. Potential applications of
membrane separation for subsea natural gas processing: a review. J. Nat. Gas Sci.
Eng. http://dx.doi.org/10.1016/j.jngse.2017.01.023.
Dashti, H., Zhehao Yew, L., Lou, X., 2015. Recent advances in gas hydrate-based CO2
capture. J. Nat. Gas Sci. Eng. http://dx.doi.org/10.1016/j.jngse.2015.01.033.
Ding, X., Cao, Y., Zhao, H., Wang, L., Yuan, Q., 2008. Fabrication of high performance
Matrimid/polysulfone dual-layer hollow fiber membranes for O2/N2 separation. J.
Membr. Sci. 323, 352–361. http://dx.doi.org/10.1016/j.memsci.2008.06.042.
Drioli, E., Ali, A., Macedonio, F., 2015. Membrane distillation: recent developments and
perspectives. Desalination. http://dx.doi.org/10.1016/j.desal.2014.10.028.
Droushiotis, N., Othman, M.H.D., Doraswami, U., Wu, Z., Kelsall, G., Li, K., 2009. Novel
co-extruded electrolyte–anode hollow fibres for solid oxide fuel cells. Electrochem.
Commun. 11, 1799–1802. http://dx.doi.org/10.1016/j.elecom.2009.07.022.
Duarte, L., Pereira, C., 2008. Polyurethane/polyethersulphone composite hollow fibers
produced by simultaneous spinning of two polymer solutions. J. Membr. Sci. 311,
12–22.
Dzinun, H., Othman, M., Ismail, A., 2015. Morphological study of co-extruded dual-layer
hollow fiber membranes incorporated with different TiO 2 loadings. J. Membr. Sci.
479, 123–131.
East, G., McIntyre, J., Rogers, V., Senn, S., 1986. Production of porous hollow polysulfone
fibers for gas separation. In: Proc. 4th BOC Priestly Conf. R. Soc. Chem. London, pp.
130–135.
Edwie, F., Teoh, M.M., Chung, T.-S., 2012. Effects of additives on dual-layer hydro-
phobic–hydrophilic PVDF hollow fiber membranes for membrane distillation and
continuous performance. Chem. Eng. Sci. 68, 567–578. http://dx.doi.org/10.1016/j.
ces.2011.10.024.
Ekiner, O., Hayes, R., Manos, P., 1992. Porous Polymeric Substrate and Polyamide
Separating Layer. US Pat. 5,085,676.
Ekiner, O., Vassilatos, G., 2001. Polyaramide hollow fibers for H 2/CH 4 separation: II.
Spinning and properties. J. Membr. Sci. 186 (1), 71–84.
Eykens, L., De Sitter, K., Dotremont, C., Pinoy, L., Van der Bruggen, B., 2017. Membrane
synthesis for membrane distillation: a review. Sep. Purif. Technol. http://dx.doi.org/
10.1016/j.seppur.2017.03.035.
Feng, C., Wang, R., Zhang, H., Shi, L., 2011. Diverse morphologies of PVDF hollow fiber
membranes and their performance analysis as gas/liquid contactors. J. Appl. Polym.
Sci. 119 (3), 1259–1267.
Feng, C.Y., Khulbe, K.C., Matsuura, T., Ismail, A.F., 2013. Recent progresses in polymeric
hollow fiber membrane preparation, characterization and applications. Sep. Purif.
Technol. 111, 43–71. http://dx.doi.org/10.1016/j.seppur.2013.03.017.
Gallucci, F., Fernandez, E., Corengia, P., van Sint Annaland, M., 2013. Recent advances on
membranes and membrane reactors for hydrogen production. Chem. Eng. Sci. 92,
40–66. http://dx.doi.org/10.1016/j.ces.2013.01.008.
Gao, Y., Li, Z., Cheng, B., Su, K., 2018. Superhydrophilic poly(p-phenylene sulfide)
membrane preparation with acid/alkali solution resistance and its usage in oil/water
separation. Sep. Purif. Technol. 192, 262–270. http://dx.doi.org/10.1016/j.seppur.
2017.09.065.
Ghangrekar, M.M., Shinde, V.B., 2007. Performance of membrane-less microbial fuel cell
treating wastewater and effect of electrode distance and area on electricity produc-
tion. Bioresour. Technol. 98, 2879–2885. http://dx.doi.org/10.1016/j.biortech.2006.
09.050.
Goh, P.S., Matsuura, T., Ismail, A.F., Hilal, N., 2016. Recent trends in membranes and
membrane processes for desalination. Desalination 391, 43–60. http://dx.doi.org/10.
1016/j.desal.2015.12.016.
Gohil, J.M., Ray, P., 2017. A review on semi-aromatic polyamide TFC membranes pre-
pared by interfacial polymerization: potential for water treatment and desalination.
Sep. Purif. Technol. http://dx.doi.org/10.1016/j.seppur.2017.03.020.
González, M.O.A., Gonçalves, J.S., Vasconcelos, R.M., 2017. Sustainable development:
case study in the implementation of renewable energy in Brazil. J. Clean. Prod. 142,
461–475. http://dx.doi.org/10.1016/j.jclepro.2016.10.052.
232
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
Guillen, G.R., Pan, Y., Li, M., Hoek, E.M.V., 2011. Preparation and characterization of
membranes formed by nonsolvent induced phase separation: a review. Ind. Eng.
Chem. Res. 50, 3798–3817. http://dx.doi.org/10.1021/ie101928r.
Gupta, M., 2008. Mesh partitioning technique for three-dimensional simulation of coex-
trusion new algorithm for coextrusion simulation. SPE ANTEC Tech. Pap. 54,
217–222.
Hassankiadeh, N.T., Cui, Z., Kim, J.H., Shin, D.W., Sanguineti, A., Arcella, V., Lee, Y.M.,
Drioli, E., 2014. PVDF hollow fiber membranes prepared from green diluent via
thermally induced phase separation: effect of PVDF molecular weight. J. Membr. Sci.
471, 237–246. http://dx.doi.org/10.1016/j.memsci.2014.07.060.
He, T., Mulder, M., Wessling, M., 2003. Preparation of porous hollow fiber membranes
with a triple-orifice spinneret. J. Appl. Polym. Sci. 87 (13), 2151–2157.
He, T., Mulder, M.H., Strathmann, H., Wessling, M., 2002. Preparation of composite
hollow fiber membranes: co-extrusion of hydrophilic coatings onto porous hydro-
phobic support structures. J. Membr. Sci. 207, 143–156. http://dx.doi.org/10.1016/
S0376-7388(02)00118-7.
Henis, J., Tripodi, M., 1981. Composite hollow fiber membranes for gas separation: the
resistance model approach. J. Membr. Sci. 8 (3), 233–246.
Henne, W., Dunweg, G., Schmitz, W., 1979. Layers of Regenerated Cellulose. US Pat.
4,164,437.
Hosseini, S., Wahid, M., 2013. Feasibility study of biogas production and utilization as a
source of renewable energy in Malaysia. Renew. Sustain. Energy Rev. 19, 454–462.
Hosseini, S.S., Peng, N., Chung, T.S., 2010. Gas separation membranes developed through
integration of polymer blending and dual-layer hollow fiber spinning process for
hydrogen and natural gas enrichments. J. Membr. Sci. 349, 156–166. http://dx.doi.
org/10.1016/j.memsci.2009.11.043.
Huang, Z.M., Zhang, Y.Z., Kotaki, M., Ramakrishna, S., 2003. A review on polymer na-
nofibers by electrospinning and their applications in nanocomposites. Compos. Sci.
Technol. 63, 2223–2253. http://dx.doi.org/10.1016/S0266-3538(03)00178-7.
Husain, S., 2006. Mixed matrix dual layer hollow fiber membranes for natural gas se-
paration in chemical engineering. Georg. Inst. Technol. Atlanta, Georg. 11, 214–220.
Husain, S., Koros, W.J., 2007. Mixed matrix hollow fiber membranes made with modified
HSSZ-13 zeolite in polyetherimide polymer matrix for gas separation. J. Membr. Sci.
288, 195–207. http://dx.doi.org/10.1016/j.memsci.2006.11.016.
Ismail, A.F., Mansourizadeh, A., 2010. A comparative study on the structure and per-
formance of porous polyvinylidene fluoride and polysulfone hollow fiber membranes
for CO2 absorption. J. Membr. Sci. 365, 319–328. http://dx.doi.org/10.1016/j.
memsci.2010.09.021.
Ismail, A., Shilton, S., Dunkin, I., Gallivan, S., 1997. Direct measurement of rheologically
induced molecular orientation in gas separation hollow fibre membranes and effects
on selectivity. J. Membr. Sci. 126 (1), 133–137.
Ji, G.L., Zhu, L.P., Zhu, B.K., Zhang, C.F., Xu, Y.Y., 2008. Structure formation and char-
acterization of PVDF hollow fiber membrane prepared via TIPS with diluent mixture.
J. Membr. Sci. 319, 264–270. http://dx.doi.org/10.1016/j.memsci.2008.03.043.
Jia, Y.T., Gong, J., Gu, X.H., Kim, H.Y., Dong, J., Shen, X.Y., 2007. Fabrication and
characterization of poly (vinyl alcohol)/chitosan blend nanofibers produced by
electrospinning method. Carbohydr. Polym. 67, 403–409. http://dx.doi.org/10.
1016/j.carbpol.2006.06.010.
Jiang, L., Chung, T.-S., Li, D.F., Cao, C., Kulprathipanja, S., 2004. Fabrication of
Matrimid/polyethersulfone dual-layer hollow fiber membranes for gas separation. J.
Membr. Sci. 240 (1), 91–103. http://dx.doi.org/10.1016/j.memsci.2004.04.015.
Jiang, L.Y., Chung, T.S., Cao, C., Huang, Z., Kulprathipanja, S., 2005. Fundamental un-
derstanding of nano-sized zeolite distribution in the formation of the mixed matrix
single- and dual-layer asymmetric hollow fiber membranes. J. Membr. Sci. 252 (1),
89–100. http://dx.doi.org/10.1016/j.memsci.2004.12.004.
Jiang, L.Y., Chung, T.S., Kulprathipanja, S., 2006. An investigation to revitalize the se-
paration performance of hollow fibers with a thin mixed matrix composite skin for
gas separation. J. Membr. Sci. 276, 113–125. http://dx.doi.org/10.1016/j.memsci.
2005.09.041.
Jiang, L.Y., Chung, T.S., Rajagopalan, R., 2007. Dual-layer hollow carbon fiber mem-
branes for gas separation consisting of carbon and mixed matrix layers. Carbon N. Y.
45, 166–172. http://dx.doi.org/10.1016/j.carbon.2006.07.008.
Jiang, L.Y., Song, Z.W., 2011. Interfacial resistance of dual-layer asymmetric hollow fiber
pervaporation membranes formed by co-extrusion. J. Polym. Res. 18, 2505–2514.
http://dx.doi.org/10.1007/s10965-011-9659-6.
Jung, J.T., Kim, J.F., Wang, H.H., di Nicolo, E., Drioli, E., Lee, Y.M., 2016. Understanding
the non-solvent induced phase separation (NIPS) effect during the fabrication of
microporous PVDF membranes via thermally induced phase separation (TIPS). J.
Membr. Sci. 514, 250–263. http://dx.doi.org/10.1016/j.memsci.2016.04.069.
Jusoh, N., Fong Yeong, Y., Leng Chew, T., Keong Lau, K., Mohd Shariff, A., 2016. Current
development and challenges of mixed matrix membranes for CO 2/CH 4 separation
current development and challenges of mixed matrix membranes for CO 2/CH 4
separation. Sep. Purif. Rev. 454, 321–344. http://dx.doi.org/10.1080/15422119.
2016.1146149.
Karavalakis, G., Durbin, T.D., Villela, M., Miller, J.W., 2012. Air pollutant emissions of
light-duty vehicles operating on various natural gas compositions. J. Nat. Gas Sci.
Eng. 4, 8–16. http://dx.doi.org/10.1016/j.jngse.2011.08.005.
Kesting, R.E., Fritzsche, A.K., Murphy, M.K., Cruse, C.A., Handermann, A.C., Malon, R.F.,
Moore, M.D., 1990. Second-generation polysulfone gas-separation membrane. I. The
use of Lewis acid. Base complexes as transient templates to increase free volume. J.
Appl. Polym. Sci. 40, 1557–1574.
Kim, J.F., Jung, J.T., Wang, H.H., Lee, S.Y., Moore, T., Sanguineti, A., Drioli, E., Lee, Y.M.,
2016a. Microporous PVDF membranes via thermally induced phase separation (TIPS)
and stretching methods. J. Membr. Sci. 509, 94–104. http://dx.doi.org/10.1016/j.
memsci.2016.02.050.
Kim, J.F., Kim, J.H., Lee, Y.M., Drioli, E., 2016b. Thermally induced phase separation and
I. Ullah Khan et al.
electrospinning methods for emerging membrane applications: a review. AIChE J. 62,
461–490. http://dx.doi.org/10.1002/aic.15076.
Kim, J.F., Szekely, G., Schaepertoens, M., Valtcheva, I.B., Jimenez-Solomon, M.F.,
Livingston, A.G., 2014. In Situ solvent recovery by organic solvent nanofiltration.
ACS Sustain. Chem. Eng. 2, 2371–2379. http://dx.doi.org/10.1021/sc5004083.
Kim, J.H., Min, B.R., Won, J., Park, H.C., Kang, Y.S., 2001. Phase behavior and me-
chanism of membrane formation for polyimide/DMSO/water system. J. Membr. Sci.
187, 47–55. http://dx.doi.org/10.1016/S0376-7388(00)00648-7.
Kong, J., Li, K., 2001. Preparation of PVDF hollow-fiber membranes via immersion pre-
cipitation. J. Appl. Polym. Sci. 81, 1643–1653. http://dx.doi.org/10.1002/app.1595.
Kumar, P., Sharma, N., Ranjan, R., Kumar, S., Bhat, Z.F., Jeong, D.K., 2013. Perspective of
membrane technology in dairy industry: a review. Asian-Australasian J. Anim. Sci.
26, 1347–1358. http://dx.doi.org/10.5713/ajas.2013.13082.
Kuo, C.Y., Lin, H.N., Tsai, H.A., Wang, D.M., Lai, J.Y., 2008. Fabrication of a high hy-
drophobic PVDF membrane via nonsolvent induced phase separation. Desalination
233, 40–47. http://dx.doi.org/10.1016/j.desal.2007.09.025.
Kuvarega, A.T., Khumalo, N., Dlamini, D., Mamba, B.B., 2018. Polysulfone/N,Pd co-
doped TiO 2 composite membranes for photocatalytic dye degradation. Sep. Purif.
Technol. 191, 122–133. http://dx.doi.org/10.1016/j.seppur.2017.07.064.
Lalia, B.S., Kochkodan, V., Hashaikeh, R., Hilal, N., 2015. A review on electrospinning for
membrane fabrication: challenges and applications. Desalination. http://dx.doi.org/
10.1016/j.desal.2013.06.016.
Lalia, B.S., Kochkodan, V., Hashaikeh, R., Hilal, N., 2013. A review on membrane fab-
rication: structure, properties and performance relationship. Desalination 326,
77–95. http://dx.doi.org/10.1016/j.desal.2013.06.016.
Leather, D.T.B., Bahadori, A., Nwaoha, C., Wood, D.A., 2013. A review of Australia's
natural gas resources and their exploitation. J. Nat. Gas Sci. Eng. 10, 68–88. http://
dx.doi.org/10.1016/j.jngse.2012.09.003.
Li, D., Chung, T.S., Wang, R., 2004a. Morphological aspects and structure control of dual-
layer asymmetric hollow fiber membranes formed by a simultaneous co-extrusion
approach. J. Membr. Sci. 243 (1), 155–175. http://dx.doi.org/10.1016/j.memsci.
2004.06.014.
Li, D.F., Chung, T.S., Wang, R., Liu, Y., 2002. Fabrication of fluoropolyimide/poly-
ethersulfone (PES) dual-layer asymmetric hollow fiber membranes for gas separation.
J. Membr. Sci. 198, 211–223. http://dx.doi.org/10.1016/S0376-7388(01)00658-5.
Li, F., Li, Y., Chung, T., Chen, H., 2011. Development and positron annihilation spec-
troscopy (PAS) characterization of polyamide imide (PAI)–polyethersulfone (PES)
based defect-free dual-layer. J. Membr. Sci. 378, 541–550.
Li, J., Si, X., Li, X., Wang, N., An, Q., Ji, S., 2017. Preparation of acid-resistant perva-
poration membranes for the dehydration of ethanol at low pH. Sep. Purif. Technol.
192, 205–212. http://dx.doi.org/10.1016/j.seppur.2017.09.038.
Li, S., Koops, G., 1994. Wet spinning of integrally skinned hollow fiber membranes by a
modified dual-bath coagulation method using a triple orifice spinneret. J. Membr.
Sci. 94 (1), 329–340.
Li, Y., Cao, C., Chung, T.S., Pramoda, K.P., 2004b. Fabrication of dual-layer poly-
ethersulfone (PES) hollow fiber membranes with an ultrathin dense-selective layer
for gas separation. J. Membr. Sci. 245, 53–60. http://dx.doi.org/10.1016/j.memsci.
2004.08.002.
Li, Y., Chung, T., 2010. Silver ionic modification in dual-layer hollow fiber membranes
with significant enhancement in CO 2/CH 4 and O 2/N 2 separation. J. Membr. Sci.
350, 226–231.
Li, Y., Chung, T.S., Huang, Z., Kulprathipanja, S., 2006. Dual-layer polyethersulfone
(PES)/BTDA-TDI/MDI co-polyimide (P84) hollow fiber membranes with a submicron
PES-zeolite beta mixed matrix dense-selective layer for gas separation. J. Membr. Sci.
277 (1), 28–37. http://dx.doi.org/10.1016/j.memsci.2005.10.008.
Li, Y., Chung, T.S., Xiao, Y., 2008. Superior gas separation performance of dual-layer
hollow fiber membranes with an ultrathin dense-selective layer. J. Membr. Sci. 325,
23–27. http://dx.doi.org/10.1016/j.memsci.2008.08.018.
Lin, K.-Y., Wang, D.-M., Lai, J.-Y., 2002. Nonsolvent-induced gelation and its effect on
membrane morphology. Macromolecules 35, 6697–6706. http://dx.doi.org/10.
1021/ma020073y.
Liu, R., Qiao, X., Chung, T., 2007. Dual-layer P84/polyethersulfone hollow fibers for
pervaporation dehydration of isopropanol. J. Membr. Sci. 294 (1), 103–114.
Liu, R., Qiao, X., Chung, T., 2005. The development of high performance P84 co-poly-
imide hollow fibers for pervaporation dehydration of isopropanol. Chem. Eng. Sci. 60
(23), 6674–6686.
Liu, Y., Chung, T., Wang, R., Li, D.F., Chng, M.L., 2003a. Chemical cross-linking mod-
ification of polyimide/poly ( ether sulfone ) dual-layer hollow fiber membranes for
gas separation. Society 1, 1190–1195. http://dx.doi.org/10.1021/ie020750c.
Liu, Y., Koops, G., Strathmann, H., 2003b. Characterization of morphology controlled
polyethersulfone hollow fiber membranes by the addition of polyethylene glycol to
the dope and bore liquid solution. J. Membr. Sci. 223, 187–199. http://dx.doi.org/
10.1016/S0376-7388(03)00322-3.
Liu, Z., Cui, Z., Zhang, Y., Qin, S., Yan, F., Li, J., 2017. Fabrication of polysulfone
membrane via thermally induced phase separation process. Mater. Lett. 195,
190–193. http://dx.doi.org/10.1016/j.matlet.2017.02.070.
Loeb, S., Sourirajan, S., 1962. Sea water demineralization by means of a semipermeable
membrane. Adv. Chem. Ser. 1, 117–132.
Mahdavi, H.R., Azizi, N., Arzani, M., Mohammadi, T., 2017. Improved CO2/CH4 se-
paration using a nanocomposite ionic liquid gel membrane. J. Nat. Gas Sci. Eng. 46,
275–288. http://dx.doi.org/10.1016/j.jngse.2017.07.024.
Malaeb, L., Ayoub, G.M., 2011. Reverse osmosis technology for water treatment: state of
the art review. Desalination. http://dx.doi.org/10.1016/j.desal.2010.09.001.
Mansourizadeh, A., Ismail, A.F., 2011a. Preparation and characterization of porous PVDF
hollow fiber membranes for CO2 absorption: effect of different non-solvent additives
in the polymer dope. Int. J. Greenh. Gas Contr. 5, 640–648. http://dx.doi.org/10.
233
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
1016/j.ijggc.2011.03.009.
Mansourizadeh, A., Ismail, A.F., 2011b. A developed asymmetric PVDF hollow fiber
membrane structure for CO2 absorption. Int. J. Greenh. Gas Contr. 5, 374–380.
http://dx.doi.org/10.1016/j.ijggc.2010.09.007.
Mansourizadeh, A., Ismail, A.F., 2010a. Effect of additives on the structure and perfor-
mance of polysulfone hollow fiber membranes for CO2 absorption. J. Membr. Sci.
348, 260–267. http://dx.doi.org/10.1016/j.memsci.2009.11.010.
Mansourizadeh, A., Ismail, A.F., 2010b. Effect of LiCl concentration in the polymer dope
on the structure and performance of hydrophobic PVDF hollow fiber membranes for
CO2 absorption. Chem. Eng. J. 165, 980–988. http://dx.doi.org/10.1016/j.cej.2010.
10.034.
Mao, Z., Jie, X., Cao, Y., Wang, L., Li, M., Yuan, Q., 2011. Preparation of dual-layer
cellulose/polysulfone hollow fiber membrane and its performance for isopropanol
dehydration and CO2 separation. Separ. Purif. Technol. 77, 179–184. https://doi.org/
10.1016/j.seppur.2010.11.031.
McKelvey, S., Clausi, D., Koros, W., 1997. A guide to establishing hollow fiber macro-
scopic properties for membrane applications. J. Membr. Sci. 124, 223–232.
Nam, Y.S., Park, T.G., 1999. Porous biodegradable polymeric scaffolds prepared by
thermally induced phase separation. J. Biomed. Mater. Res. 47, 8–17. http://dx.doi.
org/10.1002/(SICI)1097-4636(199910)47. 1 < 8::AID-JBM2 > 3.0.CO;2-L.
Nordin, N., Racha, S., Matsuura, T., 2015. Facile modification of ZIF-8 mixed matrix
membrane for CO 2/CH 4 separation: synthesis and preparation. RSC Adv. 5 (54),
43110–43120.
Ohgo, K., Zhao, C., Kobayashi, M., Asakura, T., 2002. Preparation of non-woven nano-
fibers of Bombyx mori silk, Samia cynthia ricini silk and recombinant hybrid silk with
electrospinning method. Polymer (Guildf) 44, 841–846. http://dx.doi.org/10.1016/
S0032-3861(02)00819-4.
Othman, M., Wu, Z., Droushiotis, N., 2010. Single-step fabrication and characterisations
of electrolyte/anode dual-layer hollow fibres for micro-tubular solid oxide fuel cells.
J. Membr. 351 (1–2), 196–204.
Pekny, M., Zartman, J., Krantz, W., 2003. Flow-visualization during macrovoid pore
formation in dry-cast cellulose acetate membranes. J. Membr. Sci. 211 (1), 71–90.
Pellegrino, J., Kang, Y.S., 1995. CO2CH4 transport in polyperfluorosulfonate ionomers:
effects of polar solvents on permeation and solubility. J. Membr. Sci. 99, 163–174.
http://dx.doi.org/10.1016/0376-7388(94)00211-G.
Peng, N., Chung, T.S., 2008. The effects of spinneret dimension and hollow fiber di-
mension on gas separation performance of ultra-thin defect-free Torlon® hollow fiber
membranes. J. Membr. Sci. 310, 455–465. http://dx.doi.org/10.1016/j.memsci.
2007.11.018.
Peng, N., Chung, T.S., Chng, M.L., Aw, W., 2010. Evolution of ultra-thin dense-selective
layer from single-layer to dual-layer hollow fibers using novel Extem® polyetherimide
for gas separation. J. Membr. Sci. 360, 48–57. http://dx.doi.org/10.1016/j.memsci.
2010.04.046.
Peng, N., Widjojo, N., Sukitpaneenit, P., Teoh, M., 2012. Evolution of polymeric hollow
fibers as sustainable technologies: past, present, and future. Prog. Polym. Sci. 37 (10),
1401–1424.
Percec, S., 1987. Chemical modification of poly (2,6-demethyl-1,4-phenylene oxide by
friedel-crafts reactions. J. Appl. Polym. Sci. 33, 191–203.
Pereira, C., Nobrega, R., 2003. Hollow fiber membranes obtained by simultaneous spin-
ning of two polymer solutions: a morphological study. J. Membr. Sci. 226, 35–50.
Pesek, S.C., Koros, W.J., 1994. Aqueous quenched asymmetric polysulfone hollow fibers
prepared by dry/wet phase separation. J. Membr. Sci. 88, 1–19. http://dx.doi.org/
10.1016/0376-7388(93)E0150-I.
Qian, Y., Huang, L., Pan, Y., Quan, X., Lian, H., Yang, J., 2017. Dependency of migration
and reduction of mixed Cr 2 O 7 2-, Cu 2+ and Cd 2+ on electric field, ion exchange
membrane and metal concentration in microbial fuel cells. Sep. Purif. Technol. 192,
78–87. http://dx.doi.org/10.1016/j.seppur.2017.09.049.
Qin, J., 2004. Effects of orientation relaxation and bore fluid chemistry on morphology
and performance of polyethersulfone hollow fibers for gas separation. J. Membr. Sci.
229, 1–9. http://dx.doi.org/10.1016/j.memsci.2003.10.014.
Quan, S., Li, S.W., Xiao, Y.C., Shao, L., 2017. CO2-selective mixed matrix membranes
(MMMs) containing graphene oxide (GO) for enhancing sustainable CO2 capture. Int.
J. Greenh. Gas Contr. 56, 22–29. http://dx.doi.org/10.1016/j.ijggc.2016.11.010.
Rahbari-sisakht, M., Ismail, A.F., Matsuura, T., 2012. Effect of bore fluid composition on
structure and performance of asymmetric polysulfone hollow fiber membrane con-
tactor for CO2 absorption. Sep. Purif. Technol. 88, 99–106. http://dx.doi.org/10.
1016/j.seppur.2011.12.012.
Ren, J., Chung, T., Li, D., Wang, R., Liu, Y., 2002. Development of asymmetric 6FDA-2, 6
DAT hollow fiber membranes for CO 2/CH 4 separation: 1. The influence of dope
composition and rheology on membrane morphology and separation performance. J.
Membr. Sci. 207 (2), 227–240.
Ren, J., Wang, R., Zhang, H.Y., Li, Z., Liang, D.T., Tay, J.H., 2006. Effect of PVDF dope
rheology on the structure of hollow fiber membranes used for CO2 capture. J. Membr.
Sci. 281, 334–344. http://dx.doi.org/10.1016/j.memsci.2006.04.003.
Rezaei DashtArzhandi, M., Ismail, A.F., Matsuura, T., Ng, B.C., Abdullah, M.S., 2015.
Fabrication and characterization of porous polyetherimide/montmorillonite hollow
fiber mixed matrix membranes for CO2 absorption via membrane contactor. Chem.
Eng. J. 269, 51–59. http://dx.doi.org/10.1016/j.cej.2015.01.095.
Rui, Z., Anderson, M., Lin, Y.S., Li, Y., 2009. Modeling and analysis of carbon dioxide
permeation through ceramic-carbonate dual-phase membranes. J. Membr. Sci. 345,
110–118. http://dx.doi.org/10.1016/j.memsci.2009.08.034.
Sajid, M., Nazal, M.K., Ihsanullah, Baig, N., Osman, A.M., 2018. Removal of heavy metals
and organic pollutants from water using dendritic polymers based adsorbents: a
critical review. Sep. Purif. Technol. http://dx.doi.org/10.1016/j.seppur.2017.09.
011.
Sasaki, J., 1990. Production of Porous Hollow Yarn Membrane. Japanese Pat.
I. Ullah Khan et al.
02,102,720.
Setiawan, L., Shi, L., Krantz, W., Wang, R., 2012. Explorations of delamination and ir-
regular structure in poly (amide-imide)-polyethersulfone dual layer hollow fiber
membranes. J. Membr. Sci. 423, 73–84.
Sharpe, I., Ismail, A., Shilton, S., 1999. A study of extrusion shear and forced convection
residence time in the spinning of polysulfone hollow fiber membranes for gas se-
paration. Sep. Purif. Technol. 17 (2), 101–109.
Shilton, S., Bell, G., Ferguson, J., 1994. The rheology of fibre spinning and the properties
of hollow-fibre membranes for gas separation. Polymer (Guildf) 35 (24), 5327–5335.
Story, B.J., Koros, W.J., 1992. Sorption and transport of CO2 and CH4 in chemically
modified poly(phenylene oxide). J. Membr. Sci. 67, 191–210. http://dx.doi.org/10.
1016/0376-7388(92)80025-F.
Strathmann, H., Kock, K., 1977. The formation mechanism of phase inversion mem-
branes. Desalination 21, 241–255. http://dx.doi.org/10.1016/S0011-9164(00)
88244-2.
Strathmann, H., Kock, K., Amar, P., Baker, R.W., 1975. The formation mechanism of
asymmetric membranes. Desalination 16, 179–203. http://dx.doi.org/10.1016/
S0011-9164(00)82092-5.
Sun, S.P., Wang, K.Y., Peng, N., Hatton, T.A., Chung, T.-S., 2010. Novel polyamide-imide/
cellulose acetate dual-layer hollow fiber membranes for nanofiltration. J. Membr. Sci.
363, 232–242. http://dx.doi.org/10.1016/j.memsci.2010.07.038.
Suzuki, H., Tanaka, K., Kita, H., Okamoto, K., 1998. Preparation of composite hollow fiber
membranes of poly (ethylene oxide)-containing polyimide and their CO 2/N 2 se-
paration properties. J. Membr. Sci. 146 (1), 31–37.
Teoh, M.M., Bonyadi, S., Chung, T.S., 2008. Investigation of different hollow fiber module
designs for flux enhancement in the membrane distillation process. J. Membr. Sci.
311, 371–379. http://dx.doi.org/10.1016/j.memsci.2007.12.054.
Teoh, M.M., Chung, T.S., Yeo, Y.S., 2011. Dual-layer PVDF/PTFE composite hollow fibers
with a thin macrovoid-free selective layer for water production via membrane dis-
tillation. Chem. Eng. J. 171, 684–691. http://dx.doi.org/10.1016/j.cej.2011.05.020.
Thomas, N., Mavukkandy, M.O., Loutatidou, S., Arafat, H.A., 2017. Membrane distillation
research & implementation: lessons from the past five decades. Sep. Purif. Technol.
http://dx.doi.org/10.1016/j.seppur.2017.07.069.
Tin, P.S., Chung, T.S., Liu, Y., Wang, R., Liu, S.L., Pramoda, K.P., 2003. Effects of cross-
linking modification on gas separation performance of Matrimid membranes. J.
Membr. Sci. 225, 77–90. http://dx.doi.org/10.1016/j.memsci.2003.08.005.
Tsai, H., 2000. Effect of surfactant addition on the morphology and pervaporation per-
formance of asymmetric polysulfone membranes. J. Membr. Sci. 176, 97–103. http://
dx.doi.org/10.1016/S0376-7388(00)00435-X.
Tsai, H., Kuo, C., Lin, J., Wang, D., 2006. Morphology control of polysulfone hollow fiber
membranes via water vapor induced phase separation. J. Membr. Sci. 278 (1),
390–400.
Ullah Khan, I., Hafiz Dzarfan Othman, M., Hashim, H., Matsuura, T., Ismail, A.F., Rezaei-
DashtArzhandi, M., Wan Azelee, I., 2017. Biogas as a renewable energy fuel – a re-
view of biogas upgrading, utilisation and storage. Energy Convers. Manag. http://dx.
doi.org/10.1016/j.enconman.2017.08.035.
Vogrin, N., Stropnik, Č., Musil, V., Brumen, M., 2002. The wet phase separation: the effect
of cast solution thickness on the appearance of macrovoids in the membrane forming
ternary cellulose acetate/acetone/water system. J. Membr. Sci. 207, 139–141. http://
dx.doi.org/10.1016/S0376-7388(02)00119-9.
Wade, J.L., Lackner, K.S., West, A.C., 2007. Transport model for a high temperature,
mixed conducting CO2 separation membrane. Solid State Ionics 178, 1530–1540.
http://dx.doi.org/10.1016/j.ssi.2007.09.007.
Wallace, D.W., Staudt-Bickel, C., Koros, W.J., 2006. Efficient development of effective
hollow fiber membranes for gas separations from novel polymers. J. Membr. Sci. 278,
92–104. http://dx.doi.org/10.1016/j.memsci.2005.11.001.
Wang, D.M., Lai, J.Y., 2013. Recent advances in preparation and morphology control of
polymeric membranes formed by nonsolvent induced phase separation. Curr. Opin.
Chem. Eng. 2, 229–237. http://dx.doi.org/10.1016/j.coche.2013.04.003.
Wang, K.Y., Fei Li, D., Chung, T.-S., Bor Chen, S., 2004. The observation of elongation
dependent macrovoid evolution in single- and dual-layer asymmetric hollow fiber
membranes. Chem. Eng. Sci. 59, 4657–4660. http://dx.doi.org/10.1016/j.ces.2004.
06.035.
Wang, P., Teoh, M.M., Chung, T.S., 2011. Morphological architecture of dual-layer hollow
fiber for membrane distillation with higher desalination performance. Water Res. 45,
5489–5500. http://dx.doi.org/10.1016/j.watres.2011.08.012.
Wang, R., Shi, L., Tang, C.Y., Chou, S., Qiu, C., Fane, A.G., 2010. Characterization of novel
forward osmosis hollow fiber membranes. J. Membr. Sci. 355, 158–167. http://dx.
doi.org/10.1016/j.memsci.2010.03.017.
234
View publication stats
Journal of Natural Gas Science and Engineering 52 (2018) 215–234
Widjojo, N., Chung, T., 2006. Thickness and air gap dependence of macrovoid evolution
in phase-inversion asymmetric hollow fiber membranes. Ind. Eng. Chem. Res. 45
(22), 7618–7626.
Widjojo, N., Chung, T.S., Krantz, W.B., 2007a. A morphological and structural study of
Ultem/P84 copolyimide dual-layer hollow fiber membranes with delamination-free
morphology. J. Membr. Sci. 294, 132–146. http://dx.doi.org/10.1016/j.memsci.
2007.02.026.
Widjojo, N., Chung, T.S., Kulprathipanja, S., 2008. The fabrication of hollow fiber
membranes with double-layer mixed-matrix materials for gas separation. J. Membr.
Sci. 325 (1), 326–335. http://dx.doi.org/10.1016/j.memsci.2008.07.046.
Widjojo, N., Zhang, S.D., Chung, T.S., Liu, Y., 2007b. Enhanced gas separation perfor-
mance of dual-layer hollow fiber membranes via substructure resistance reduction
using mixed matrix materials. J. Membr. Sci. 306, 147–158. http://dx.doi.org/10.
1016/j.memsci.2007.08.038.
Wojciechowski, C., 2014. Fabrication and characterization of polysulfone/cellulose
acetate dual-layer capillary membranes. Monogr. Environ. Eng. Comm. 118,
253–264.
Wolf, B., 1984. Thermodynamic theory of flowing polymer solutions and its application to
phase separation. Macromolecules 17 (4), 615–618.
Xiang, L., Pan, Y., Jiang, J., Chen, Y., Chen, J., Zhang, L., Wang, C., 2017. Thin poly
(ether-block-amide)/attapulgite composite membranes with improved CO2 per-
meance and selectivity for CO2/N2 and CO2/CH4. Chem. Eng. Sci. 160, 236–244.
https://doi.org/10.1016/j.ces.2016.11.037.
Xu, Q., Huang, D., Chen, W., Lee, J., Kim, B., Wang, H., Yuan, R., 2004. Influence of
sintering temperature on microstructure and mixed electronic–ionic conduction
properties of perovskite-type La0.6Sr0.4Co0.8Fe0.2O3 ceramics. Ceram. Int. 30,
429–433. http://dx.doi.org/10.1016/S0272-8842(03)00127-5.
Yanagimoto, T., 1988. Method for Manufacture of Hollow Fiber Porous Membranes.
Japanese Pat. 63,092,712.
Yang, C.-C., Hsu, S.-M.S.-P., Wu, M.-S., Chien, C.-T., 2006. Effects of vitamin C infusion
and vitamin E-coated membrane on hemodialysis-induced oxidative stress. Kidney
Int. 69, 706–714. http://dx.doi.org/10.1038/sj.ki.5000109.
Yao, C., Burford, R., Fane, A., Fell, C., 1988. Effect of coagulation conditions on structure
and properties of membranes from aliphatic polyamides. J. Membr. Sci. 38 (2),
113–125.
Yu, D., Chou, W., Yang, M., 2006. Effect of bore liquid temperature and dope con-
centration on mechanical properties and permeation performance of polyacrylonitrile
hollow fibers. Sep. Purif. Technol. 51 (1), 1–9.
Zhang, Y., Liu, R., Lang, Q., Tan, M., Zhang, Y., 2018. Composite anion exchange
membrane made by layer-by-layer method for selective ion separation and water
migration control. Sep. Purif. Technol. 192, 278–286. http://dx.doi.org/10.1016/j.
seppur.2017.10.022.
Zhang, Y., Sunarso, J., Liu, S., Wang, R., 2013. Current status and development of
membranes for CO 2/CH 4 separation: a review. Int. J. Greenh. Gas Contr. 12,
84–107.
Zhang, Z., 2016. Comparisons of various absorbent effects on carbon dioxide capture in
membrane gas absorption (MGA) process. J. Nat. Gas Sci. Eng. 31, 589–595. http://
dx.doi.org/10.1016/j.jngse.2016.03.052.
Zhang, Z., Cai, J., Chen, F., Li, H., Zhang, W., Qi, W., 2017. Progress in enhancement of
CO 2 absorption by nanofluids: a mini review of mechanisms and current status.
Renew. Energy 118, 527–535. http://dx.doi.org/10.1016/j.renene.2017.11.031.
Zhang, Z., Yan, Y., Zhang, L., Chen, Y., Ran, J., Pu, G., Qin, C., 2014. Theoretical study on
CO2absorption from biogas by membrane contactors: effect of operating parameters.
Ind. Eng. Chem. Res. 53, 14075–14083. http://dx.doi.org/10.1021/ie502830k.
Zhu, W.P., Sun, S.P., Gao, J., Fu, F.J., Chung, T.S., 2014. Dual-layer polybenzimidazole/
polyethersulfone (PBI/PES) nanofiltration (NF) hollow fiber membranes for heavy
metals removal from wastewater. J. Membr. Sci. 456, 117–127. http://dx.doi.org/10.
1016/j.memsci.2014.01.001.
Zulhairun, A.K., Ismail, A.F., 2014. The role of layered silicate loadings and their dis-
persion states on the gas separation performance of mixed matrix membrane. J.
Membr. Sci. 468, 20–30. http://dx.doi.org/10.1016/j.memsci.2014.05.038.
Zulhairun, A.K., Ismail, A.F., Matsuura, T., Abdullah, M.S., Mustafa, A., 2014a.
Asymmetric mixed matrix membrane incorporating organically modified clay par-
ticle for gas separation. Chem. Eng. J. 241, 495–503. http://dx.doi.org/10.1016/j.
cej.2013.10.042.
Zulhairun, A.K., Ng, B.C., Ismail, A.F., Surya Murali, R., Abdullah, M.S., 2014b.
Production of mixed matrix hollow fiber membrane for CO2/CH4 separation. Sep.
Purif. Technol. 137, 1–12. http://dx.doi.org/10.1016/j.seppur.2014.09.014.