Cben 201500020

A Review on Chitosan Utilization in Membrane Synthesis
Alireza Jafari Sanjari[1], Morteza Asghari[1],*
Abstract
Membrane separation technologies are very energy on the application of chitosan membranes. The ap-
efficient and the general interest has drastically in- plications include gas separation, direct methanol
creased over the last decade. Biopolymers as mem- fuel cells (DMFCs), pervaporation, water treatment
brane compounds have gained increased attention (heavy metal and dye removal, salt rejection), and
due to their renewability. Chitosan is a derivative of the biomedical field. The preparation of different
chitin, the second most abundant biopolymer and chitosan membranes is presented as well as its cap-
shows many advantages required for a membrane. abilities in the different fields of application.
This article provides an overview of recent progress
Keywords: Chitosan, Gas separation, Membrane Processes, Modification, Pervaporation
Received: August 24, 2015; revised: February 11, 2016; accepted: February 17, 2016
DOI: 10.1002/cben.201500020
1 Introduction byproducts of marine processing plants [13]. Chitosan (CS),

the deacetylated form of chitin, consists of linear b-1,4-linked
Membrane technology has become a favorite separation tech- D-glucosamine (GlcN) and N-acetyl glucosamine (GlcNAc)
nology over the last decades, owing to its low energy consump- units. Fig. 1 shows the structures of chitin and CS [14]. The
tion, operational easiness, ease of control, and scale-up [1, 2]. degree of deacetylation (%DD) generally indicates the biologi-
Membrane technology is highly energy efficient, since it pro- cal and physicochemical properties of CS. CS, as a natural bio-
vides a continuous process without the need for sorbent regen- polymer, possesses a number of inherent advantages such as
eration or desorption by temperature/pressure variation. More- biocompatibility, biodegradability, non-toxicity, low cost and
over, the membrane equipment is compact, without moving good sorption properties. Also, in particular, the free amino-
parts, easy to operate, control, and to scale up [3]. During the hydroxyl groups enable antibacterial features, heavy metal ion
last two decades, the focus on invention and development chelation capability, gel-forming properties, remarkable affinity
activity in the general field of membrane technology has been to proteins, water solubility, and ease of modification and proc-
drastically increasing. Thus, membrane technology has been essing [2].
applied in various fields such as water treatment [4, 5], gas Until now, numerous CS derivatives have been developed for
purification [6], environmental protection [7], pharmaceutical different applications. CS occupies positions in the biomedical
industry [8], food processing [9], and medical applications. field such as drug delivery, tissue engineering, wound dressing,
The membrane plays the most important role in the membrane bone substitution, suture material, etc. CS is a low cost and
separation technology, and it directly affects process efficiency effective adsorbent for the removal of dye, heavy metal ions
[10]. and other contaminants; therefore, it is used in water treatment
A favorable membrane has various structural and functional applications. Furthermore, CS also finds important application
features such as a combination of high permeation rate, high in other fields such as agriculture, cosmetics, food, etc. [2]. CS
species selectivity, long and reliable service life, low fouling rate, exists in various forms including gels, beads, microcapsules,
and sufficiently thermal, chemical, and mechanical resistances microspheres, fibers, and membranes that are fabricated for
under operating conditions [3]. Because of growing public various applications. Among them, CS membranes with the
health and environmental knowledge accompanied by an benefit of low energy cost and ease of operation, which allow
increasing number of stricter environmental regulations on dis- the selective transport of specific components, are widely used
charged wastes, attention has been focused on the use of bio-
polymers from renewable resources as alternatives to synthetic
polymers. Biopolymers are produced in nature by plants and
living organisms, take part in the natural biocycle, and are
—————
[1]
Alireza Jafari Sanjari, Dr. Morteza Asghari (corresponding author)
finally degraded and reabsorbed in nature [11]. Chitin, poly University of Kashan, Department of Engineering, Energy
(b-(1,4)-N-acetyl-D-glucosamine), is the second most abun- Research Institute, Separation Processes Research Group (SPRG),
dant biopolymer in nature [12]. The main source of chitin is Ghotb-e-Ravandi Ave., Kashan 8731751167, Iran.
the shells of crustaceans, from crabs and shrimps, as the E-Mail: asghari@kashanu.ac.ir
www.ChemBioEngRev.de ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ChemBioEng Rev 2016, 3, No. 3, 134–158 134
2 Chitosan Membranes in Gas
Separation
Gas separation through membranes has appeared
as a significant unit operation offering specific ben-
efits over conventional separation methods such as
adsorption and cryogenic distillation. Membrane
technology has contributed enormously to the de-
velopment of new research frontiers such as carbon
dioxide capture, which serves as an effective tool
for natural gas purification. Simplicity, ease of pro-
cess integration, process flexibility, low-energy
requirement, low capital and production costs
make the membrane processes for gas purification
highly competitive. Until now, a large range of
materials including zeolites, dense metals, poly-
mers, ceramics and biological polymers have been
used for fabricating membranes. But the polymers
are the most used materials. Selection of polymeric
materials for gas separation is based on sorption
Figure 1. Structure of chitin and CS [14]. capacity, good mechanical strength, and chemical
resistance. For an efficient separation, the polymer
should have good interaction with one of the com-
to provide solutions for chemical, biological, energy, and envi- ponents of the mixture [6, 15]. For a long time, chitosan mem-
ronmental issues [11]. CS membranes, owing to their hydro- branes have been studied in food packaging due to their good gas
philicity, biocompatibility, ease of modification, cationicity, and barrier properties in dry conditions. Furthermore, their excellent
remarkable affinity to dyes metals, etc., have been extensively antibacterial and fungicidal properties as well as biocompatibil-
applied. Many works have reported CS membrane applications, ity, non-toxicity, and ease of film forming make them attractive
including gas separation, DMFC, pervaporation, water treat- edible packaging materials [16]. Thereafter, researchers found
ment and other areas. Fig. 2 shows the number of literary that the sorption of water on chitosan at high humidity levels
works published by now. In this work, different types of CS damages its gas barrier properties and spoils it [17]. This case in-
membranes including derivative, cross-linked, blended, multi- spires the applications of CS for gas separation.
layered, inorganic filler-embedded and other modified CS
membranes have been reviewed. These membranes have been
utilized in the mentioned applications. The focus was on recent 2.1 Pure Chitosan Membranes
progresses in CS membranes synthesis and the influence of dif-
ferent types of CS membranes on their performance was inves- It is recognized that amines can serve as a carrier to facilitate
tigated. the transport of acidic gases through membranes [18]. CS is
expected to allow the selective permeation of CO2
due to the existence of amino groups in polymer
chain. In fully dry conditions, CS membranes are
dense and rigid and they show very low permeabil-
ity to gases [19]. Water acting as a plasticizer may
remarkably change the gas permeation properties
of CS. Until the relative partial vapor pressure in
the feed is under 70 %, for each monomer unit of
CS only one or two water molecules are absorbed.
Whenever the relative partial pressure of water
vapors increases, water molecules are more ad-
sorbed, leading to high swelling of the membrane
and, as a result, permeation flux increases. This is
more important in case of CO2 permeate, owing to
its high solubility in water. Furthermore, CO2 mol-
ecules can be transferred fast in the membrane with
the aid of protonated amino groups. Therefore, in
the selective separation of CO2 a swollen CS mem-
Figure 2. Number of literary works in application fields of CS membranes from brane is preferred. Since gas separation technology
1989 to 2015. using CS membranes is still at it infancy, a few
practical separation methods of gas mixtures have been report- the highest CO2 permeability of 2884 Barrer and a moderate
ed. A pure CS membrane was investigated by Ito et al. for the separation factor of 23.4 for CO2/CH4 and 65.3 for CO2/N2 at
separation of CO2/N2. For the swollen membranes, separation 85 C when the mass ratio of CS to PEBA was 1:1. CS mem-
factor and permeability was 70 and 2.5 · 10–8 Barrer, respective- branes for separation of CO2 from N2 may have the potential
ly. They reported several additional methods that increase the to compete with other membranes for the remedy of green-
separation performance of the original CS membrane. For house gas emission.
example, the addition of a trace amount of ammonia gas in the
feed can increase the CO2 separation factor of the wet CS
membrane. Furthermore, using the cast solution with a high 2.4 Chitosan Multi-Layer Membranes
concentration of acetic acid (83 %) can increase the permeation
rate [20]. In an additional work, Ito et al. [20] coated a thin layer of car-
boxymethylcellulose onto the surface of a CS membrane. They
observed an increase in separation factor and permeation flux
2.2 Chitosan-Modified and Cross-Linked simultaneously. As a result, they improved the separation per-
Membranes formance of the original CS membrane. In another work, a
poly (amidoamine) (PAMAM) dendrimer composite mem-
The effect of cross-linking was investigated on gas and water brane including a CS layer showed a promising result. A sepa-
transport behavior. According to the study of Xhiao et al. [19], ration factor of 400 for a CO2/N2 mixture and a CO2 perme-
they used trimesoyl chloride (TMC) as the cross-linking agent. ance of 1.6 · 10–7 m3(STP) m–2s–1kPa–1 were obtained. In this
The degree of cross-linking affected the pure gas permeations composite membrane, the CS layer just served as the gutter
of CO2 and N2 through swollen CS membranes. As a result, layer and adhesive medium without any selective function
they obtained a CO2 permeability of 163 Barrer and an ideal [24, 25].
separation factor of 42. Also, in another work, Liu et al. [21]
used cross-linking as an effective method to restrain the exces-
sive swelling although it may decrease the CO2 permeability 3 Chitosan Membranes in Direct
and water permeability. Amino-acid salt solutions provide an Methanol Fuel Cells
interesting alternative to amine-based solutions for CO2 cap-
ture. Therefore, El-Azzami et al. [22] studied CS membranes Owning to the growing concerns on the depletion of petro-
modified with amino acid salts (arginine-sodium) for separa- leum-based energy resources and climate change, fuel cell
tion of carbon dioxide from hydrogen and nitrogen. The num- technologies have received much attention in recent years
ber of amino groups for facilitated transport of CO2 increases because they have low emissions and high efficiencies. Fuel
with addition of arginine salts and, subsequently, the water cells as electrochemical devices are able to directly convert
levels in the arginine salt-CS membranes rise compared to chemical energy stored in fuels such as hydrogen to electrical
swollen CS membranes at the same humidification conditions. energy [26, 27]. Direct methanol fuel cells (DMFC) are nota-
El-Azzami et al. reported a CO2 permeability of 1500 Barrer. ble among the fuel cells. Owing to their promising qualities,
Also, the separation factor for CO2/H2 and CO2/N2 was 144 including propensity to be operated at low temperature, ex-
and 852, respectively. isting infrastructure, low pollution emission and high energy
efficiency, they have received much attention in recent years
[28, 29]. But several challenges hinder the commercialization
2.3 Chitosan-Blend Membranes of DMFCs. These challenges include high methanol crossover
of the proton exchange membrane (PEM) and low catalyst
For this class of membranes, Shen et al. [23] studied the facili- activity towards methanol oxidation at the anode [30]. This
tated transport of CO2 through carboxymethyl CS (CMCS)/ methanol permeability causes conversion losses in terms of
polyethylenimine (PEI) blend membranes. Water was utilized lost fuel and depolarization losses at the cathode, resulting in
as an activator for the reaction between CO2 and the carriers, overall poor fuel cell performance [31]. The crucial part in
which improved the permselectivity of the CMCS/PEI blend DMFCs is the PEM which controls the cost and durability of
membrane. Recently, Liu et al. [21] used hydrogel membranes DMFCs and also transfers newly formed protons from the
of CS/poly (ether-block-amide) (PEBA) blends for CO2 separa- anode to the cathode side of the cell [32, 33]. An ideal PEM
tion. Hydrogel membranes have been shown as attractive high should fulfill a number of requirements such as high proton
permeability materials for gas separation because hydrogel ma- conductivity, low methanol crossover, long-term chemical
terials are defined as cross-linked polymer networks with high and hydrolytic durability under heated and humidified con-
affinity towards water. They proposed that the gas permeation ditions [34]. Recently, as a PEM material, CS has attracted
through a hydrogel membrane has two ways: water passage- remarkable attention. Such an interest in CS has arisen from its
ways and polymer matrix channels. Thus, increasing the water unique features of facile chemical modification, high proton con-
content and constructing more polymer matrix channels will ductivity, excellent alcohol barrier property, good chemical and
both lead to further increase in the performance of the hydro- thermal resistance, high hydrophilicity, low costs, and conven-
gel membrane. As a result, hydrogel membranes with both bet- ient film forming properties [32, 35, 36]. In this study, four cate-
ter operation stability and high permeability are desired mate- gories of CS membranes are reported to be used as PEM material
rials for CO2 separation. At the end of this study, they reported in DMFCs.
3.1 Chitosan Cross-Linked Membranes terfaces, it can be utilized as a barrier layer in PEM. A signifi-
cantly reduced methanol crossover and remarkably higher
Due to their low methanol permeability properties compared membrane selectivity parameter was reported for fabricated
with Nafion, CS membranes are used in DMFCs and have multi-layer membranes compared to Nafion117. In another
shown a better performance among other polymer electrolyte similar work [40], they prepared a novel double layer PEM
membranes. But their low proton conductivity is a challenge composed of a layer of structurally modified CS, as a methanol
for researchers. Cross-linking is another way to overcome this barrier layer, coated on Nafion112. Methanol permeability and
problem. The amine (-NH2) groups in CS are reactive func- proton conductivity measurements showed improved transport
tional groups that allow for both physical and chemical modifi- properties of double layer membranes compared to Nafion117.
cations [28]. Researchers have proposed several cross-linking
agents such as glyoxal, glutaraldehyd (GA) and sulfuric acid
because the sulfate group allows for better proton conductivity. 3.4 Chitosan Hybrid Membranes
O. Osifo [28] and P. Mukoma [31] prepared CS cross-linked with Inorganic Fillers
membranes and used H2SO4 as cross-linking agent. Their
results demonstrated that methanol permeability of these In recent years, organic-inorganic hybrid membranes have
membranes was three times lower than the Nafion117 mem- been proposed as promising electrolytes for DMFC applica-
branes. Also, moderate proton conductivity was obtained. tions. As an organic material, and owing to its ion conductivity,
environmental benignity, excellent alcohol barrier property,
easy membrane-forming property and low cost, CS plays an
3.2 Chitosan-Blended Membranes important role in organic-inorganic hybrid membranes for
DMFCs [41]. Incorporating the inorganic additives (1) im-
Using blend membranes is another approach to overcome proves mechanical, thermal, and chemical stabilities by intrin-
problems of this application. For example, blending of CS with sic organic-inorganic interfacial interactions; (2) increases pro-
PVA improved mechanical stability, methanol permeability, ton conductivity by improving water retention property of the
and proton conductivity [37, 38]. In order to improve the sta- membranes and/or by constructing new proton transport path-
bility of these membranes, they were modified with GA and way; (3) reduces methanol crossover through suppressing
sulfonated graphene [37, 38]. Pore-filling membranes com- membrane swelling and/or blocking methanol transport path
prised of a porous substrate and a filling polymer electrolyte [42]. In other words, inorganic fillers within the membrane can
have demonstrated promising performances such as high pro- interfere with polymer chain packing and create a more tortu-
ton conductivity and low methanol crossover. Therefore, ous diffusion path. Thus, they play an important role in sup-
Zhang et al. [29] used PVA/CS blend membranes as the sub- pressing methanol crossover [43].
strate and Nafion ionomer as the filling polymer to obtain a Among all inorganic materials, solid superacids have triggered
pore-filling-like composite membrane. Nafion ionomer im- increasing attention due to their good hygroscopic and proton
proved the proton conductivity of the PVA/CS composite conductive properties and also mechanical property when incor-
membranes and the developed composite membranes also porated into polymers, which are useful for high performance
exhibit much lower methanol permeability compared with the PEM [42]. Metal oxide supported sulfate (MxOy–SO42–), heter-
widely used Nafion membrane. At last, Xiang et al. [39] devel- opoly acid (HPA), and zeolite solid superacid are the main solid
oped a series of cross-linked CS sulfate-blend membranes by superacids which have been utilized till now. A number of
grafting the CS monomers with sulfonic groups. They reported researchers have reported CS hybrid membranes with inor-
good proton conductivity and methanol permeability results. ganic fillers. For example, Zhiming Cui et al. [44] prepared
three types of composite membranes including CS/PMA,
CS/PWA, and CS/SiWA for DMFC. Since HPAs possess a
3.3 Chitosan Multi-Layer Membranes unique discrete ionic structure, it exhibits high proton mobility.
Thus, HPAs can be immobilized within the membranes
High methanol permeability of Nafion membranes is the most through electrostatic interaction, which overcomes the leakage
important challenge for DMFC. Therefore, coating them with problem from membranes. Among the three membranes,
methanol barrier layers or with layer-by-layer self-assembly CS/PMA exhibit low methanol permeability (2.7 · 10–7 cm2s–1)
thin polyelectrolyte films is another approach to reduce metha- and comparatively high proton conductivity (0.015 S cm–1 at
nol permeability and overcome their problems [32]. However, 25 C) and was identified as ideal for DMFC. Also cesium
CS-based PEMs are good options for reducing methanol per- phosphotungstate salt as a solid superacid with good perform-
meability and consequently increasing membrane selectivity, ance was utilized [36].
but their moderate proton conductivities are a challenge. So, Wang et al. [42] used another class of solid superacids as
multi-layer membranes can be used in this regard [40]. Hasa- inorganic filler for their study. They dispersed nano-sized
ni-Sadrabadi et al. [32] prepared a triple-layer membrane com- TiO2-SO42– (STiO2) into the CS matrix. The presence of the
posed of Nafion105 sandwiched between two thin structurally STiO2 particles within the CS matrix reduces the fractional free
modified CS barrier layers as a novel PEM for high-perfor- volume and creates a more tortuous diffusion pathway for
mance DMFC applications. Due to the presence of several ami- methanol molecules, which increased the methanol diffusion
no and hydroxyl groups on CS chains which can interact with resistance and remarkably reduced methanol crossover through
sulfonate groups in the Nafion structure and provide firm in- the matrix. Compared with TiO2 embedded membranes and
Nafion117 membranes, all the STiO2-filled hybrid membranes the suitability of a given membrane for DMFC applications
exhibit better performance. Besides, organophosphorylated [36, 41]. An overview of these reports is shown in Tab. 1.
titania submicrospheres (OPTi) [43] and SiO2 [45] incorpo-
rated into a CS matrix and displayed good results.
For the last class of solid superacids, Wu et al. [46] prepared 4 Chitosan Membranes
surface-modified Y zeolite-filled CS membranes using silane- in Pervaporation
coupling agents (APTEOS and MPTMS). By creating a transi-
tional phase between the polymer and the zeolite particle, an Pervaporation is one of the most well-known membrane sepa-
improved organic-inorganic interfacial morphology was ob- ration techniques [47]. In theory any liquid mixture can be sep-
tained leading to reduced methanol permeation. Compared arated by pervaporation, but in practice pervaporation tends to
with pure CS and Nafion117 membranes, the hybrid mem- be used to separate close boiling-point mixtures, azeotropic
branes exhibited a significant reduction in methanol perme- mixtures, and for the recovery of small quantities of impurities
ability and also the proton conductivity improved. In another [48, 49]. Membrane pervaporation has become a promising
work the effects of zeolite particles and pore size, content, and alternative to conventional processes such as distillation,
hydrophilic/hydrophobic nature on the membrane perform- extraction, and adsorption due to easy operation, high product
ance was investigated [35]. Based on the discovery that acid- quality, and low energy consumption [50, 51]. However, combi-
base pairs can construct efficient proton conduction channels, nations of pervaporation with one of these traditional separa-
Yin et al. [33] synthesized a kind of binary titania-silica sol tion techniques are also used in industry. Pervaporation can be
functionalized with carboxyl groups and amino groups (TiC- applied in three main fields categorized as follows: (1) dehydra-
SiN) by a facile chelation method. Then, they dispersed the re- tion of aqueous-organic mixtures, (2) separation of organic-
sultant TiC-SiN inorganic phase uniformly in CS matrix. The organic solvent mixtures, and (3) removal of trace volatile
hygroscopic inorganic silica, Titania and the hydrophilic -NH2, organic compounds from aqueous solutions. Generally, in per-
-COOH groups facilitate the proton transfer via vehicle mecha- vaporation a liquid feed is passed over the membrane surface,
nism. Moreover, the zwitterion-functionalized TiC-SiN dop- but one component can pass across the membrane preferential-
ants contribute to the proton migration via Grotthuss mecha- ly. The fraction of the feed that passes through the membrane
nism. Overall, the CS/TiC-SiN hybrid membranes possess is defined as permeate, and the fraction that fails to diffuse
higher selectivity than pure CS membranes. In the application through as the retentate [48, 49]. The principle of pervapora-
of DMFC, a similar parameter can be defined as b = s/P to tion process is presented in Fig. 3.
evaluate the selectivity of PEM for the proton and methanol, Mass flux and separation factor are two major parameters
where P and s describe the methanol permeability and proton that need to be considered for the selection of a membrane for
conductivity, respectively, and may be used as an indicator of a specific mixture. The key is to develop highly selective and
Table 1. CS membranes in DMFCs.
Membrane Proton Methanol Temperature Methanol b [· 104 S s cm–3] Description Ref.

conductivity permeability [C] concentration
[· 10–2 S cm–1] [· 10–7 cm2s–1] [mol]
CS/Beta (10 %) 1.4 3.1 – 2 4.5 For Nafion 117: [41]

b » 1.69 · 104
CS/Beta-GPTMS 1.31 2.2 – 2 5.9 (H) For Nafion 117: [41]

(10 %) b » 1.69 · 104
CS/OPTi (5–15 %) 1.14 2.8 – 12 4 For Nafion 117: [43]

P » 39 · 10–7
CS/Cs2-PTA-%5 0.6 5.6 25 – 1.1 (H) For Nafion 212: [36]

P » 84 · 10–7
CS/1TiC-2SiN-%5 3.8 7.83 25 2 4.85 For chitosan: [33]

b = 1.67 · 104
CS/PMA 1.5 2.7 25 – 5.5 for Nafion 117: [44]

b = 3.5 · 104
CS/STiO2-%10 1.55 6.48 – – 2.4 For chitosan: [42]

b = 1.6 · 104
CS/HO3SY-%10 2.58 6 – 12 4.28 For Nafion 117: [46]

b = 1.8 · 104
For chitosan:
b = 2.35 · 104
been developed. Fig. 4 presents some details of the structures of
these membranes. Tab. 2 generalizes their performances in vari-
ous applications.
4.1 Chitosan Derivatives and Cross-Linked

Membranes
Figure 3. Principle of pervaporation.
CS derivatives membranes were prepared from hydroxypropy-
stable membranes capable of dealing with high flux input. lation [57], phosphporylation [58, 59], N-alkalylation [60] and
Moreover, sorption capacity, chemical resistance and mechani- benzoylation [61]. New functional groups can change the
cal strength of membrane are other main parameters in the mobility and arrangement of polymer chains and as a result
selection [52]. Hence, suitable selection of membrane materials affect the separation performance. The most popular modifica-
is essential in pervaporation because the materials critically tion for CS membranes is cross-linking. Decreased polymer
affect the performance of the process [53]. Recently, employing crystallinity and shrinkage of the crystal size will obtained by
biodegradable polymers in pervaporation membranes has cross-linking [62–65]. Cross-linking will improve selectivity,
increased. CS has become one of the most studied biodegrad- but is often accompanied by a reduction of permeation flux
able pervaporation membranes owing to its significant hydro- [66]. Researchers explored eight various cross-linking agents
philicity, excellent chemical resistance and good film-forming including metal salts [57, 67, 68], organic chemicals [19, 56, 62,
properties [53]. However, excessive swelling of pure CS mem- 63, 65, 69–74], and inorganic acids [64, 75–78]. The effect of
branes in aqueous solutions decreases selectivity of these mem- cross-linking on the separation performance varies enormously
branes [53–55]. with the cross-linking degree, the interaction with CS, the
Moreover, other factors such as temperature can affect per- structure of cross-linking agents, and process conditions, etc.
meation flux and separation factor. Generally, the permeation
flux increases with the increase in temperature, but the separa-
tion factors vary depending on the relationship between the 4.2 Chitosan Composite Membranes
solubility and diffusion selectivity with temperature. An
increase in temperature often decreases the diffusion selectivity 4.2.1 Chitosan-Blended Membranes
because of the enhanced swelling of membranes. Moreover, the
reduction of diffusion selectivity can be compensated with the Over the years, polymer blending has become an approach for
increase in solution selectivity at the same time, so the overall the development of pervaporation membranes. Polymer blend-
selectivity can be maintained or enhanced [56]. To overcome ing proves to be an efficient way to compose membranes with a
the swelling issue, chemical or physical modification is neces- number of desired properties. Successful blending by altering
sary. In addition to CS derivatives, blended, cross-linked, multi- polymer chain mobility through intermolecular interaction
layered, or inorganic fillers embedded CS membranes have between polymers can improve membrane performance [79].
Figure 4. Overview of CS membranes used in pervaporation.
Table 2. CS membranes for pervaporation.
Type of membranes Solution mixture Separation Flux Thickness Temperature Ref.

factor [g m–2h–1] [mm] [C]
CS DMSO(50 wt %)/water 120 20 20 40 [54]
CS DMC/methanol/water – – 28.4 – [55]
Phosphorylated CS Ethanol(90 wt %)/water 600 200 ~20 70 [58]
Benzoyl CS Benzene(10 wt %)/water ~65 – 30 40 [61]
Phosphorylated CS Ethanol(95.58 wt %)/water 213 580 – – [76]

2+
CS with Cu Ethanol(80 wt %)/water 1996 450 ~20 50 [68]
GA cross-linked CS Dimethylhydrazine(50 wt %)/water 10.6 167 40 - [65]

2+
GA cross-linked CS treated with Cu Propanol(85 wt %)/water 220 500 20 60 [57]
Isopropanol(85 wt %)/water 240 500 20 60 [57]
Maleic anhydride surface modified GA Ethanol(90wt %)/water 634 300 – 60 [73]

cross-linked CS
SSA cross-linked CS Ethanol(80 wt %)/water 9000 450 – 60 [69]
H2SO4 cross-linked CS DMC/methanol/water – – – – [78]
H2SO4 cross-linked CS EG(96.437 wt %)/water 234 378 50 30 [64]
TDI cross-linked CS Isopropanol(87.5 wt %)/water 472 390 10 30 [63]
Blocked diisocyanate cross-linked CS Isopropanol(95 wt %)/water 5918 22 – 30 [62]
TMC cross-linked CS Isopropanol(90 wt %)/water ~350 – 140 60 [19]
Chitosan composite membranes:
(a) Blended membranes
CS/SA Ethanol(95.4 wt %)/Water 436 22 10 30 [82]
Carboxymethylated CS(CMCS)/alginate Alcohol/water ¥ 8 – – [84]
CS/PAA Ethanol(95 wt %)/water >19 000 22 45–50 80 [81]
CS/PAA Isopropanol(87.5 wt %)/water 1736 140 10 30 [80]
CS/PAA EG(80 wt %)/water 105 216 ~30 70 [85]
CS/PVA Isopropanol(90 wt %)/water >899 991 644 18–25 60 [88]
CS/PVA Isopropanol(90 wt %)/water 17991 113 35–40 30 [87]
THF(95 wt %)/water 4203 98 35–40 30 [87]
CS/PVA 1,4-Dioxane(82 wt %)/water 117 366 50 30 [86]
CS/PVA EG(90 wt %)/water 986 460 34 70 [79]
CS/PVA Benzene(50 %)/cyclohexane 49.9 51.41 – 50 [89]
CS/PVP THF(94.31 wt %)/water 1025 99.5 40 35 [96]
CS/HEC Ethanol(90 wt %)/water 10 491 112 30–35 25 [91]
Isopropanol(90 wt %)/water 26 091 175 30–35 25 [91]
CS/HEC 2-Butanol(77 wt %)/water 554 2100 50 30 [90]
CS/CMCNa Ethanol(90 wt %)/water 1062 1140 – 70 [97]
CS/Nylon 66 1,4-Dioxane(82 wt %)/water 865 89 50 30 [94]
CS/N-methylol Nylon Ethanol(95 wt %)/water 560 350 10 60 [93]
Table 2. Continued.

CS/KGM CPL(70 wt %)/water >3000 – – Every temp. [92]
CS/PEO Ethanol(92 wt %)/water 4.4 900 20 20 [95]
CS/HPC Isopropanol(90 wt %)/water 11 241 132 50+1 30 [98]
(b) Chitosan membranes with porous substrate
CS/PES Ethanol(90 wt %)/water – – 10 80 [101]
CS/PES Glycol(80 wt %)/water >796 1130 10 80 [102]
CS/PES modified by surfactants Methanol(20 wt %)/water 50 100 – 25 [102]
CS/PSf EG(90 wt %)/water >103.5 300 – 30 [99]
CS/PSf Isopropanol(90 wt %)/water 348 ~350 – 30 [100]
CS/PSf Isopropanol(90 wt %)/water 5912 446 10 50 [103]
CS/PAA/PSf Ethanol(95 wt %)/water 1008 132 20–40 30 [83]
CS/SA/PSf Methanol(25 wt %)/water ¥ 250 – 40 [107]
CS/PSf hollow fiber Ethanol(90 wt %)/water 2440 60 – 25 [109]
CMCS/PSf hollow fiber Isopropanol(87.5 wt %)/water 3238.5 38.6 24–100 45 [108]
CS/PAN Ethanol(90 wt %)/water > 8000 260 - 60 [113]

6
Isopropanol(80 wt %)/water > 10 981
6
Propanol(80 wt %)/water > 10 800
CS/PAN Ethanol(90 wt %)/water 1410 330 - 70 [112]
Isopropanol(90 wt %)/water 5000 430 70
Methanol(90 wt %)/water 123 170 60
GCCS/PAN Ethanol/water 256 1247 – 80 [114]
CS/PVA/PAN Ethanol(95 wt %)/water 93.7 320 18–25 30 [115]
CS/HEC/CA Ethanol(95 wt %)/water 16 606 220 4 60 [118]
CS/CA hollow fiber Isopropanol(90 wt %)/water 809 169.5 – 25 [116]
CS/SA Ethanol(95 wt %)/water 1110 70 <10 60 [110]
CS/SA/PVDF Isopropanol(90 wt %)/water 2010 554 5 50 [111]
CS/BC Ethanol(95 wt %)/water 9.2 42 800 – 24 [119]
Chitin/PEI Ethanol(10 wt %)/toluene 126 282 – 35 [120]
Methanol(10 wt %)/toluene 607 484
CS/PSS/Zeolite A Alcohol/water – – – – [121]
(c) Inorganic particle-filled membranes
CS/NaY zeolite (40 %) Isopropanol(90 wt %)/water 11 241 113.7 40 + 2 30 [124]
CS/NaY zeolite (40 %) Isopropanol(95 wt %)/water 2620 115 40 + 2 30 [128]
CS/NaY zeolite (0.4 %) Isopropanol(90 wt %)/water 47.83 60 20–30 – [126]
CS/HY zeolite (20 %) Ethanol(90 wt %)/water 102 353 – – [127]
CS/Silicalite zeolite (10 %) Toluene(10–40 wt %)/methanol 19–264 31–19 – 30 [133]
CS/PAA/modernite zeolite (4 %) EG(80 wt %)/water 258 165 25 + 2 70 [132]
Table 2. Continued.

CS/ZSM-5 zeolite (5 %) DMC(90 wt %)/methanol 29.4 56 35 + 2 25 [129]
CS/H-ZSM-5 zeolite (8 %) Ethanol(90 wt %)/water 152.82 230.96 25 80 [130]
CS/MPTMS-modified H-ZSM-5 zeolite Ethanol(90 wt %)/water 274.46 278.54 25 80 [131]

(8 %)
CS/ZIF zeolite (5 %) Ethanol/water 2812 322 18 25 [50]
CS/PVA/CNT (1 %) Benzene(50 wt %)/cyclohexane 53.4 65.9 ~80 50 [134]
CS/Ag+-MWCNT (1.5 %) Benzene(50 wt %)/cyclohexane 7.89 357.96 2.3 20 [135]
CS/PHB functionalized-MWCNT 1,4-Dioxane(95 wt %)/water 623.11 17 – – [53]
CS/modified-TNT(6 %)/PAN Isopropanol(90 wt %)/water 6237 1498 50–90 80 [136]
CS/TEOS Ethanol(96.5 wt %)/water ¥ 8 – 40 [143]
CS/TEOS Ethanol(90 wt %)/water 460 284 45 + 5 80 [141]
CS/PVA/TEOS Isopropanol(90 wt %)/water 2991 23.9 40 + 5 30 [138]
CS/APTEOS Methanol(70 wt %)/water 30.1 1265 20 + 0.5 50 [137]
CS/APTEOS Ethanol(85 wt %)/water 597 887 18 + 0. 5 50 [56]
CS/ST-GPE-S Ethanol(90 wt %)/water 919 410 32 70 [139]
CS/GPTMS Isopropanol(70 wt %)/water 694 1730 12 + 1.2 70 [140]
CS/GPTMS/PAN Isopropanol(90 wt %)/water 2991 145 – 25 [145]
CS/GPTMS/PTFE-g-PSSA Isopropanol(70 wt %)/water 775 1730 – 70 [144]
NSBCS/SBAPTS Ethanol(90 wt %)/water 5282 590 100 30 [142]

+
CS/Na -MMT clay (10 %) Isopropanol(90 wt %)/water 14 992 142.3 40 + 2 30 [146]
CS/TiCl4(14 %)/PAN Ethanol(90 wt %)/water 730 1403 77 [147]
CS/TiO2 (6 %) Ethanol(90 wt %)/water 196 340 80 [122]
CS/Fe3O4 (15 %) Ethanol/water 3.27 – – – [47]
(d) Chitosan grafted membrane
CS-g-PANI Isopropanol(90 wt %)/water 2092 11.9 40 30 [148]
CS can be blended with either hydrophobic or hydrophilic linking is necessary because of the weak interaction between
polymers such as nylon, PVA, poly(acrylic acid) (PAA), etc., to CS and HEC. The GA [90] and urea-formaldehyde-sulfuric
improve the pervaporation performance. Polyion membranes acid mixture [91] cross-linked blendings were used to dehy-
have been prepared by using anionic polymers with cationic drate 2-butanol and ethanol, respectively. Cross-linking im-
CS. Their dehydration performance has been studied for aque- proves selectivity towards 2-butanol and also a good mechani-
ous organic mixtures such as isopropanol [80, 81], ethanol cal resistance were obtained. Furthermore, it was found that
[81–84], and ethylene glycol (EG) [85]. These blendings make the ratio of HEC to CS is very important in the separation per-
membranes water selective, mechanically and thermally stable. formance. The uncommon material Konjac glucomannan
Blending CS with non-charged polymers can avoid some (KGM) was blended with CS for pervaporation separation [92].
defects such as precipitation which emerges in polyion mem- Intermolecular interaction between KGM and CS formed
branes. PVA has been blended with CS to dehydrate 1,4-dioxane hydrogen bonding. Their CS/KGM blending membrane dis-
[86], isopropanol [87, 88], tetrahydrofuran (THF) [87], EG played good pervaporation performance and a superior separa-
[79], and to separate benzene-cyclohexane mixtures [89]. The tion factor of 3000 at every temperature.
ratio of CS to PVA plays an important role in obtaining the In addition, other polymers including nylon [93, 94],
separation factor higher than the pure PVA membranes poly(ethylene oxide) (PEO) [95], poly(vinylpyrrolidone) (PVP)
[87–89]. [96, 97], hydroxypropyl cellulose (HPC) [98], and sodium car-
Another highly soluble and non-ionic polymer used to blend boxymethyl cellulose [97], etc., had been blended with CS for
with CS is hydroxyethylcellulose (HEC). In this case, cross- dehydration of alcohols or separation of organic liquid mix-
tures. Generally, improvement of separation efficiency, 4.2.3 Chitosan Composite Membranes with Inorganic
mechanical resistance and thermal/chemical stability can be Fillers
obtained by blending CS with those polymers. Researchers
have found that blending CS with hydrophilic polymers gives In recent years, there has been remarkable interest in organic/
better permeability and separation factors than hydrophobic inorganic hybrid membranes composed of a polymer matrix
polymers for dehydration processes. and inorganic nanoparticles which can be applied in pervapo-
ration processes. In these composite membranes, the advan-
tages of the polymer moieties such as processability and flexi-
4.2.2 Chitosan Membranes with Porous Substrate bility are combined with the advantages of inorganic moieties
such as selectivity and thermal stability. So, it was found that
An effective reduction in transport resistance without compro- the inorganic moiety plays an important role in the improve-
mising the mechanical strength can be obtained by multilayer ment of the membrane performance [122]. Various inorganic
membranes. These membranes comprise a thin selective layer fillers such as zeolite, carbon nanotube, graphite, and silicate
and a porous substrate. These membranes are chemically and particles have been used in many applications. The fillers are
mechanically stable and display low mass transport resistance. A classified into (1) class 1 materials, in which weak interactions
few ultrafiltration (UF) membranes have been chosen as sub- such as van der waals, weak hydrogen bonding and electro-
strate including polysulfone (PSf) and polyethersulfone (PES) static forces exist between organic and inorganic phases and (2)
UF membranes and a good permeation flux was obtained with a class 2 materials, in which organic and inorganic phases can be
very thin selective layer [99–102]. Also, cross-linking [100–103] linked together through strong ionic-covalent bonding [123].
or modification with surfactants [102] can compensate the Incorporation of inorganic fillers decreases the crystallinity of
reduction in the separation factor. Composite membranes com- CS because intermolecular hydrogen bonding in original CS
prised of CS-sodium alginate (SA) polyion and a PSf support crystallites is disrupted and CS chains interact with these fillers.
have been prepared. Their separation performances were studied Zeolites are unique molecular sieving and adsorbents because
towards water-alcohol [104] and methyl tert-butyl ether of their structure [124]. The Al/Si ratio determines the hydro-
(MTBE)-methanol mixtures [105–107]. Characteristics of per- philic-hydrophobic nature while the pore size of the channel
meate molecules affect the selectivity and permeability. Increas- depends on the number of oxygen atoms in the aperture ring
ing the CS content enhances the ionic interaction and conse- [125]. Hydrophilic zeolites have been used to fabricate CS-zeo-
quently improves the separation factor; however, it decreases lite composite membranes [124, 126–131]. The performance of
permeation flux [106, 107]. Also, PSf hollow fiber membranes these membranes varies with zeolite type and loading ratio.
have been used as the microporous support for CS [108, 109]. A NaY zeolite is the best choice among zeolites due to its
low improvement in the pervaporation performance was investi- unique properties such as uniform pore size distribution, high
gated by a two-ply CS-SA membrane [110]. However, mechani- void volume, high surface area, and presence of sodalite and
cal resistance was enhanced. In another work, porous poly(vinyl- super cages in the framework. A membrane containing 40 wt %
idene fluoride) (PVDF)-blended hydrophilic poly(methyl of NaY zeolite showed a separation factor of 11 241 and a flux
metharylate) (PMMA) hollow fibers were used as the support of 11.37 · 10–2 Kg m–2h–1 for 10 wt % water in the feed for the
[111]. Another material used as the substrate is polyacrylonitrile dehydration of an isopropanol solution. The low content of
(PAN). Interaction of -CN in PAN with -NH2 in CS will form NaY (0.4 wt %) [126] and NH4Y (0.2 wt %) was found inferior
the intermolecular cross-linking layer which improves the se- to the 40 % NaY-CS membrane. Furthermore, HY [127] and
lectivity and durability of the membranes [112, 113]. H-ZSM-5 [130]-filled CS membranes were prepared for dehy-
In similar work, a composite membrane comprised of CS as dration of ethanol solutions. In a similar work, the silane cou-
an active layer, PAN as support layer and carbopol (CP) as an pling agent 3-mercaptopropyltrimethoxysilane (MPTMS) was
intermediate layer was prepared [114]. Introduction of mussel- employed to modify the external surface of H-ZSM-5. Modify-
adhesive-mimetic carbopol molecules significantly increased ing H-ZSM-5 by MPTMS introduced the ion-ion interaction
the interfacial adhesion strength of CS/PAN membrane and the between organic and inorganic phase which eliminated the
separation factor. Dehydration of ethanol aqueous solutions nonselective voids of the filled membranes. Consequently, the
was performed by CS-PVA-blended membranes with the PAN modified H-ZSM-5 filled membrane exhibited much higher
substrate. The separation factor was enhanced with increase in selectivity than the H-ZSM-5-filled membrane [131]. Morden-
the PVA weight ratio [115]. Until now, other membranes such ite-filled CS-PAA blending membranes were appropriate for
as CS-coated cellulose acetate (CA) hollow fiber membranes dehydration of EG [132]. ZSM-5-filled CS membrane for sepa-
[116], CS-HEC membranes with CA substrate [117, 118] and ration of dimethyl carbonate (DMC)-methanol increased the
CS-impregnated bacterial cellulose (BC) membranes [119] have permeation flux but decreased the separation factor [129]. The
been studied for the dehydration of alcohols. The chitin mem- addition of silicalite zeolite particles into CS improved mem-
branes with polyetherimide (PEI) porous substrate have been brane performance for two mixtures of toluene-methanol and
used to separate alcohol-toluene mixtures. The introduction of toluene-ethanol [133].
acetyl groups along with intermolecular interaction enhances Zeolitic imidazolate frameworks (ZIFs) are a sub-family of
the permselectivity and the mechanical and chemical stability metal-organic frameworks (MOF). ZIF-7/CS mixed-matrix
were improved because of the rigid structure of chitin [120]. membranes were prepared and it was found that the separation
Inorganic porous substrates are also frequently used to fabri- efficiency of 5 wt % ZIF-7/CS membrane was 19 times higher
cate composite CS membranes [121]. than that of the pristine CS membrane [50]. Graphite may
enhance the selectivity of benzene because of the structural Nano-clays are other inorganic fillers have also been used in
similarity. A graphite-filled CS-PVA hybrid membrane was organic-inorganic hybrid membranes for dehydration of iso-
prepared for the pervaporation of a benzene-cyclohexane mix- propanol. Novel composite membranes were prepared by
ture and the resultd showed that the solubility selectivity played incorporating sodium montmorillonite (Na+-MMT) clay into
a more important role than the diffusion selectivity [133]. Also, quaternized CS [146]. The opposite charges on the CS and clay
a nanocomposite membrane comprised of CS wrapped nano- establish the strong electrostatic interaction between them and
tube fillers with PVA matrix improved the separation factor of also aid the better dispersion of the clay within the CS matrix.
the benzene-cyclohexane mixture [134]. MWNTs have a pi-pi The incorporation of inorganic moieties into the polymer bulk
stacking interaction between carbon nanotube and aromatic can be categorized by physical blending and in situ sol-gel reac-
compounds, which has a potential for strong interaction tion. Compared to physical blending, the in situ sol-gel reac-
between benzene and hydrophilic polymeric materials (such as tion can form covalent bonds between the polymeric phase and
CS). In addition, silver ions (Ag (I)) can improve the perform- inorganic phase. The in situ formation of inorganic particles
ance of membranes for benzene/cyclohexane mixtures due to inhibits the aggregation of particles and the formation of non-
benzene-monovalent metal (I) coordinate complex formation. selective voids. For example, robust, ultrathin CS-titania hybrid
Therefore, a MWNTs-Ag+/CS hybrid membrane showed very membranes were prepared in a facile way by introducing
good results owing to inherent properties of all components for 3-(3,4-dihydroxyphenyl)propionic acid (DHPPA) as a bio-
separation of benzene/cyclohexane mixtures [135]. inspired multifunctional modifier to mediate the in situ sol-gel
Carbon nanotubes can render desirable transport channels reaction of TiCl4 within the CS matrix [147]. As a result, the
for water molecules owing to their large surface area, open end, hybrid membranes showed higher swelling resistance, long-
tubular and layered-wall structure. But their hydrophobicity is term operation stability and separation performance. In anoth-
an important problem [136]. In another work, a CS-wrapped er study, composite CS membranes filled with iron ferroferric
multi-walled carbon nanotubes (CS-wrapped MWCNTs)- oxides (Fe3O4) were prepared for dehydration of ethanol [47].
incorporated SA membrane was prepared for isopropanol Fe3O4 nanoparticles are useful materials for separation applica-
dehydration [51]. CS wrapped the MWCNTs with a prime aim tions due to their specific properties such as superparamag-
to improve hydrophilicity. Therefore, the developed membrane netic, nontoxic, great surface/area ratio and small size. The
was highly selective toward water. Poly(3-hydroxybutyrate)- influence of iron oxide powder content on the transport prop-
functionalized MWCNTs/CS green nanocomposite membranes erties was discussed and it was revealed that with an increasing
showed a relatively high permeation flux and selectivity toward content of iron oxide nanoparticles permeation of water gradu-
water for 1,4-dioxane dehydration [53]. It should be noted that ally increases due to the rising of diffusivity.
the presence of the poly(3-hydroxybutyrate) (PHB) functional
moieties helped to improve the dispersion and compatibility of
the MWCNTs in the CS matrix. Unlike carbon nanotubes, tita- 4.2.4 Chitosan-Grafted Membranes
nate nanotubes (TNTs) possess high hydrophilicity. In another
work for dehydration of isopropanol, CS-MTNTs/PAN compo- Sometimes membranes developed only with highly hydrophilic
site membranes were used [136]. The presence of MTNTs polymers lack mechanical strength and chemical resistance in
reduces the crystallinity of CS, enlarges the fractional free- aqueous solution mainly due to excessive swelling. Chemical
volume and improves the hydrophilicity of CS membranes. modification of hydrophilic polymers through grafting is
And as a result, a high isopropanol dehydration performance anticipated to be a promising method providing a wide variety
was obtained. One of the typical class 2 CS composite mem- of molecular design. Moreover, the properties of polymer can
branes is the CS-silica hybrid prepared using organofunction- be properly tuned depending on the nature and concentration
ized silanes, such as s-(glycidyloxypropyl)trimethoxysilane of grafting. So, grafting is an important approach to enhance
(GPTMS), tetraethoxysilane (TEOS), 3-aminopropyl-triethoxy- the separation performance of the membrane. For example,
silane (APTEOS), and sodium 2-formylbenzenesulfonatepoly- CS-g-polyaniline membranes were prepared and the resulting
siloxane (SBAPTS) [56, 137–143], or functionalized silica membranes were employed for pervaporation separation of
nanoparticles, e.g., silica nanoparticles with sulfonic acid water- isopropanol mixtures and exhibited better pervapora-
groups (ST-GPE-S) [139] as the cross-linking agents. Silica tion performances than that of pure CS membranes [148]. On
nanoparticle-derived membranes exhibit high permeability and the other hand, most of membranes suffer relatively low per-
permselectivity for small molecules such as water, while rela- meation fluxes due to their dense and hydrophobic features.
tively low permeability for larger molecules such as ethanol. Surface modification of these membranes through grafting is
The loading ratio and the characteristics affect the degree of an effective way to increase the solubility of the selective mole-
improvement. An over-loading of silica cross-linking agents cules. One example is incorporation of CS chains into poly-
may cause a heterogeneous structure and leads to a sharp benzoimidazole (PBI) and as a result the performance of PBI-
decrease of selectivity [143]. Moreover, the reduction of diffu- based membrane for pervaporation dehydration of isopropanol
sion selectivity can be compensated by the increase in solution has been remarkably enhanced [149]. The surface hydrophilici-
selectivity at same time. Thus, the overall selectivity can be ty and the dissolution rate of water into the membrane en-
maintained or enhanced [56]. Permeation flux and the long hanced the separation performance.
term durability can be improved with coating the CS-silica
hybrid membrane onto the porous substrate [144, 145].
5 Water Treatment for the removal of heavy metal ions and Tab. 3 generalizes their
performances in this regard.
Fig. 5 shows an overview of the water treatment structure, the
CS membranes used in it, and other information.
5.1.1 Chitosan Adsorptive Membranes
5.1 Heavy Metal Removal Several studies focus on adsorptive membranes to remove
heavy metal ions from aqueous solutions. Reactive functional
Heavy metals are one of the main categories of water pollutants groups, including -COOH, -SO3H and -NH2 groups, on the
which cause severe problems to public health and the environ- surface of adsorptive membranes could bond with heavy metal
ment. The heavy metals are not biodegradable and tend to ions by ion exchange mechanisms or form surface complexa-
assemble in living organisms. Many heavy metal ions are tions [155]. Fast separation rate, high efficiency, low energy
known as toxic and carcinogenic contaminants. Heavy metal requirement, good selectivity and large permeate flux are the
ions exist in aqueous waste streams of various industries unique advantages of adsorptive membranes [156]. Many pub-
including mining operations, battery manufacturing, metal lications have reported the performance of CS adsorptive
plating, etc. Heavy metal removal from wastewater streams is membranes and the porosity, thickness, metal-complexing
important for the protection of the environment and public ligand density, temperature, pore size and etc., can dramatically
health. Various efficient methods such as chemical precipita- affect their performances.
tion, adsorption, ion-exchange, electrochemical treatment and Several methods have been used to modify natural CS, but as
membrane filtration have been investigated for heavy metal we know, the most common modification for CS is cross-link-
elimination from aqueous solutions [150]. Membrane separa- ing. Cross-linking of CS improves pore size distribution,
tion is a promising technology due to its energy-saving poten- mechanical resistance, chemical stability and adsorption/de-
tial for the selective separation of heavy metal ions, and is sorption properties. The most popular cross-linking agents that
known to be more appropriate for this application than other have been proposed and used are epichlorohydrin (ECH) and
methods [151, 152]. CS has been reported to be a suitable bio- GA [153, 157–160]. Baroni et al. [157] prepared cross-linked
polymer for the removal of metal ions from wastewater [153]. CS membranes to remove chromium ions from aqueous solu-
The high adsorption potential of CS for heavy metals can be tions and used ECH and GA as cross-linking agents. They
ascribed to great hydrophilicity due to the large number of reported that the maximum adsorption capacity occurred in
hydroxyl groups of the glucose units, the presence of large ECH-cross-linked CS at pH 6.0. Their results indicate that the
functional groups, great chemical reactivity of these functional adsorption process occurs mainly in CS amino groups. On the
groups and the flexible structure of the polymer chain [154]. In other hand, Vieira et al. [160] prepared same ECH and GA
the following, we present various types of CS membranes used cross-linked membranes for the removal of mercury (Hg (II))
Figure 5. Overview of CS membranes used in water treatment.
Table 3. CS membranes for removal of heavy metal ions.
Type of Membrane Adsorbate Adsorption pH Temperatuere Kinetic Model Isotherm Ref.

Capacity [C]
[mg g–1]
CS Cu(II) 25.64 – – Pseudo-First Order, Freundlich, Langmuir, [163]

Pseudo-Second Order Redlich-Peterson
Ni(II) 10.3
CS/CA Cu(II) 35.3 5 – Pseudo-Second Order – [166]
CS/CA Cu(II) 31 5 – – – [156]
CS/PVA/PEG (5 %) Cu(II) 30 5.5 20 Pseudo-First Order, – [176]

Pseudo-Second Order
CS/PVA/MWCNTs-NH2 19
CS/PVA/PEG/MWNTs-NH2 35
CS/PEG Fe(II) 38 5 27 – Freundlich, Langmuir [154]
Mn(II) 18 5.9
CS/PVA/MWNTs-NH2 (2 %) Cu(II) 20.1 – 40 Pseudo-First Order, Freundlich, Langmuir [175]

Pseudo-Second Order
CS (ENM) Cu(II) 485.44 – – – Langmuir [184]
Pb(II) 263.15
CS/PEG (ENM) As(V) 30.8 - - Pseudo-Second Order Langmuir [188]
CS/HAp (ENM) Pb(II) 296.7 – 45 Pseudo-Second Order Freundlich, Langmuir [187]
Co(II) 213.8
Ni(II) 180.2
ECH-Cross-linked-CS Cr(II) 1400 6 – – Freundlich, Langmuir [157]
CS Hg(II) 25.3 6 – – Langmuir [160]
ECH-Cross-linked-CS 30.3
GA-Cross-linked-CS 75.5
CS/Silica Particles Cu(II) 4.8 5 20 Pseudo-First Order, Freundlich, Langmuir [152]

Pseudo-Second Order
Vanillin-Modified-CS Cu(II) 18.2 6 25 Lagergren Pseudo-Second – [164]

Order, Avrami
Histidine-Modified-CS Cu(II) 25.1 4.6 25 – – [161]
ions. They reported that the maximum adsorption capacity Notably, porogens such as NaCl or silica gel can be added to
occurred in GA-cross-linked CS at pH 6.0. Their results indi- the casting solution to increase the porosity of CS membranes.
cate that adsorption does not occur only on amino groups, but Also, the effect of pore size was investigated by Chao et al.
that other groups added by cross-linking agents are also impor- [162]. The effect of CS membrane morphology on copper ion
tant. Dense membranes have low porosity, which limits diffu- adsorption was studied by Ghaee et al. [152]. By increasing
sion and flux in a continuous process. polymer concentration, more amine groups are available for
Porosity is a factor that affects adsorptive membrane per- chelation and, accordingly, copper adsorption increases. More-
formance [161, 162]. Immobilization of histidine on porous CS over, increasing silica (as a porogen) content leads to higher
membranes showed synergistic effects with the porosity in the porosity and roughness. Thus, macro porous membranes have
ability to complex with Cu (II) ions [161]. Depending on the a higher flux and surface area than dense membranes
initial membrane porosity, this synergy may be positive or neg- [152, 163]. In other studies, the influence of temperature on
ative. A positive synergy on the adsorption capacity of Cu (II) adsorption of metals was investigated [164, 165]. The results
can be observed when highly porous membranes incorporate showed that a rise of temperature accelerated the mass transfer
histidine. As a result, it was found that membranes with higher of Cu(II) to the vanilline-modified thin CS membrane surfaces
porosity showed increased capacity of Cu (II) adsorption. [164]. In these works, the exprimental datas were fitted to
adsorption kinetic equations to abtain the characteristic para- the spinning process, etc., on structures and morphologies of
meters of each model. the membranes were investigate and the objective is to obtain
highly porous, macrovoids-free adsorptive hollow fiber mem-
branes with different pore sizes [166, 179].
5.1.2 Chitosan Adsorptive Blend Membranes
Pure CS membranes suffer from poor mechanical strength and 5.1.3 Chitosan Composite UF Membranes
chemical stability. Hence, blending CS with other polymers has
been found to be an effective way to overcome the shortcom- Membrane filtration technologies with different types of mem-
ings of CS, because it can provide CS with the desired mechani- branes show great promise for heavy metal removal due to
cal strength and chemical stability [166–172]. Blended CS their easy operation, space saving and great efficiency. UF is a
membranes not only show great mechanical properties, but membrane process used to remove metals from wastewater and
they also benefit from the intrinsic advantages of each polymer working at low transmembrane pressures for the elimination of
involved in the blend [166, 173]. Two widely used polymers colloidal and dissolved material. Generally, the UF membranes
that, blended with CS, have resulted in high performance have larger pore sizes than dissolved metal ions in the form of
adsorptive membranes, are CA and PVA [156, 166, 174–176]. hydrated ions or as low molecular weight complexes would
PVA, a highly hydrophilic and biocompatible polymer, is pass simply through. Complexation-UF proves to be a new
employed to enhance mechanical, thermal, and chemical stabil- promising technology for separation of heavy metals from
ity of CS [154, 155, 174, 176]. Blending CS with PVA resulted in effluents. The use of water-soluble metal-binding polymers in
homogeneously dense membranes because of strong affinity combination with UF is known as polymer-enhanced ultrafil-
between the polymeric chains. tration (PEUF) process. It is a hybrid approach for the removal
In two works, NH2-MWCNT was prepared and applied for of heavy metals. Kumar et al. prepared PSf/CS, PSf/NSCS, and
the modification of CS/PVA adsorptive membranes [175, 176]. PSf/NPPCS membranes and studied the rejection of these
NH2-MWCNT can increase the quantity of NH2 functional membranes towards the copper, cadmium and nickel ions dur-
groups which act as adsorption sites throughout the mem- ing UF by the PEUF processes [180]. The PEUF process
branes. In these studies, the adsorptive characteristics and resulted in cosiderable improvement in metal ion rejection. In
mechanical stability of CS/PVA membranes were improved. In another work, CS-based ceramic UF membranes were fabri-
one of them, poly(ethylene glycol) (PEG) was also employed as cated using dip coating methods. The UF range membrane
a porogen agent and had a superior effect on copper ion with a pore size of 13 nm was successfully used for the removal
adsorption than NH2-MWCNT [176]. Moreover, CNTs were of mercury and arsenic from aqueous medium by PEUF using
mixed with blends of CS/PVA and cross-linked with silane and polyvinyl alcohol as the chelating agent. The heavy metal con-
these membranes were utilized for the removal of polyaromatic centration in the permeate increased with the increase in its
hydrocarbons (PAHs) from water [174]. Novel modified CS initial concentration and decreased with the increase in initial
transparent thin membranes (MCTTM) were prepared by PVA concentration [181]. Another technique to make UF
blending CS with PVA. These membranes are able to eliminate membranes applicable for heavy metal removal is modification.
copper ions of lower concentrations by adsorption and can The presence of -NH2, -COOH and -POOH functionalities on
indicate heavy metal ions by color changes [177]. Also, the the membrane surfaces can improve the adsorption perfor-
influence of membrane thickness on adsorption performance mance. New blend membranes were prepared by using poly-
has been investigated. For the MCTTM, thickness clearly mer blend (CS and acrylonitrile-butadiene-styrene (ABS)) on a
affects the adsorption capacity of copper ions from solutions. PES UF substrate membrane. In this work, the effects of
Furthermore, the adsorption kinetics of copper ions onto the applied pressure and feed concentration on permeate flux and
MCTTM was investigated and the results indicated that the rejection of mercury were investigated [182].
pseudo-second order model described the adsorption process.
[155]. In these works, PVA played both roles of blending and
cross-linking agents. Furthermore, PEG-CS blends have good 5.1.4 Chitosan-Based Electrospun Nanofiber Membranes
physico-chemical properties comparable to CS alone. An
adsorptive cross-linked CSB membrane with micro porous Electrospun nanofiber membranes have been used for removal
structure was directly prepared from extraction of PEG from a of heavy metal ions due to their unique properties such as high
CS/PEG blend membrane and was highly adsorptive for iron specific surface area and high porosity with fine pores. They
and manganese ions [154]. The blend hollow fiber membranes combine the advantages of nanomaterials (high specific surface
were found to achieve relatively good adsorption performance. area) and bulk material (easy separation from water). CS, due
These membranes have highly porous structures and mechani- to the presence of hydroxyl and amine groups, is widely used
cal strength compared to commercial membranes that are for the elimination of heavy metal ions from aqueous solutions
desirable for adsorptive membranes. CS/CA blend hollow fiber [183, 184]. But the electrospinning of CS is extremely difficult
membranes have been reported as another adsorptive mem- due to the low chain flexibility, poor solubility, high viscosity,
branes [156, 166, 178, 179]. In these blend hollow fiber mem- and low mechanical properties. Therefore, CS has been blended
branes, CA acts as matrix support and CS provides the func- to polymers such as poly(ethylene oxide)(PEO), PVA, cellulose,
tional groups for metal ion adsorption [166]. In these studies, zein, poly(lactic acid), poly(caprolactone), and nylon-6 to
the effects of the CS/CA ratio and type of coagulants used in improve the mechanical properties of CS nanofibers [185]. A
PEO/CS nanofiber membrane was prepared by the electrospin- capability for removal of textile dyes. The effects of time, con-
ning method and its application for the removal of copper, centration, pH and temperature on adsorption kinetics of
lead, cadmium and nickel ions from aqueous solution was in- Bezactiv Orange V-3R were investigated. The increase of mass
vestigated [186]. But these polymers have not remarkable effect amount of MMT and dye concentration in solution increased
in improving adsorption process efficiency. the adsorption capacity. The results of adsorption kinetics and
Hence, a CS/hydroxyapatite (HAp) composite nanofiber isotherms showed that the adsorption process can be fitted by
membrane was prepared by the electrospinning process for the the pseudo-second order equation and Freundlich equation,
removal of lead, cobalt, and nickel ions from aqueous solution. respectively. Novel thin film composite (TFC) membranes were
HAp, as a binding material, can improve the mechanical prop- prepared by organoclay/CS nanocomposite coated on the
erties of CS nanofibers and also increase metal ions sorption PVDF microfiltration membrane. Two differently modified
efficiency [187]. In another work, a pure CS electrospun nano- nanoclays (Cloisite15A and 30B) were introduced into CS
fiber membrane was prepared in an environmentally friendly aqueous solution. The Cloisite15A showed higher water flux
way for the adsorptive removal of arsenate from water. They than the Cloisite 30B series. Moreover, the Cloisite 15A and
first fabricated electrospun CS/PEO blended nanofiber mem- Cloisite 30B were appropriate for methylene blue removal and
branes and then removed PEO from the blended nanofiber acidic dye (acid orange 7), respectively. The prepared TFC
membrane via immerging and thoroughly washing with water membranes eliminated the dyes dominantly because of their
[188]. The effects of different process parameters such as solu- adsorption potential along with other effective mechanisms
tion pH, initial ion concentration, and contact time were inves- such as inertia effects, sieving and concentration polarization
tigated to obtain the optimum conditions for the maximum which might cooperate in the separation process [197]. Zhu et
adsorption capacity of metal ions. al. [198] prepared the nanocomposite PES membranes by
directly incorporating CS-MMT nanosheets into a polymeric
matrix via phase inversion methods. The hydrophilicity and
5.2 Dye Removal water flux of hybrid membranes were greatly improved after
adding CS-MMT nanosheets. Unlike the conventional nanofil-
Dyes are known as one of the main sources of severe water pol- tration (NF) membranes, these ‘‘loose’’ NF membranes demon-
lution because of the rapid development of the textile industries strated higher rejection for Reactive Black 5 and Reactive Red
and other dyeing industries such as paper, printing, leather, 49 and lower rejection for bivalent salts.
food and plastic [189]. Dyes in textile wastewater are an envi- In another work, PES NF membranes were synthesized
ronmental problem because of their high visibility, resistance, through blending of O-carboxymethyl CS/Fe3O4 nanoparticles
and toxic impact [190]. The release of the colorant effluent has (CC-Fe3O4 NPs) via the phase inversion method. Owing to its
triggered a concern on the human health and marine lives. well adsorptive features, Fe3O4 was used as a support for prepa-
Because of the low concentration of dye molecules in waste- ration of carboxylated CS to induce its hydrophilic properties
water and their inert properties, the removal of dyes from to the membrane surface. These modified membranes showed
wastewaters is difficult. Thus, it is necessary to choose a suit- higher water flux and permeation due to their better hydro-
able way for the removal of dye from wastewater and to philicity compared to the unfilled PES membrane. NF per-
improve the quality of treated wastewater discharged into the formance of the membranes demonstrated that addition of
environment. In view of the fact that adsorption is rapid, con- O-carboxymethyl CS-coated Fe3O4 nanoparticles induced the
venient, and inscrutable to toxic contaminants, it is preferred negative charge on the membrane surface and enhanced rejec-
over other conventional methods of removing dyes [189]. High tion of the Direct Red 16 dye [199]. Karim et al. [200] reported
adsorption capacity and large surface area, easy accessibility, the preparation of fully biobased composite membranes for
cost effectiveness, suitable pore size and volume, mechanical water purification. These membranes were fabricated with cel-
stability, compatibility, ease of regeneration, environmentally lulose nanocrystals (CNCs) as functional entities in the CS
friendly, and high selectivity to remove a wide range of dyes are matrix via freeze-drying. Freeze-drying resulted in well individ-
the properties of an ideal adsorbent for dye removal [191]. As ualized CNCs and consequently led to high efficiency of these
an adsorbent material, CS has received a lot of focus due to its membranes in term of adsorption. In this study, CNCs are used
unique properties [192]. Many researchers have reported the as functional entity for the fabrication of composite membrane
application of unmodified and modified CS in adsorption of because they require functional groups (SO3– and/or COO–)
different types of dye .They have employed different forms of for the removal of targeted dyes by electrostatic interaction.
CS including powder, flakes, gel (beads, film, membranes, Finally, after a contact time of 24 h, the membranes successfully
etc.) [189, 193, 194]. Converting CS flakes into membrane removed 98 %, 84 %, and 70 % of positively charged dyes like
and film is a method to prepare adsorbents from CS present- Victoria Blue 2B, Methyl Violet 2B, and Rhodamine 6G, respec-
ing fibrous structure, higher surface areas and good mechani- tively.
cal properties [195]. CS membranes have been reported by a
few researchers as an adsorbent for dye removal from aque-
ous solutions. 5.3 Salt Rejection
In addition to CS, clays are the other attractive adsorbents
due to their abundance and low cost. Thus, combining CS with For this case several membranes have been employed as
clays may produce a very good sorbent. Nesic et al. [196] pre- follows. Tab. 4 generalizes the application of these mem-
pared CS/MMT membranes and investigated their adsorption branes.
Table 4. CS membranes for salt rejection.
Type of membrane Cross-linking Salt rejection rate R Permeate flux Water flux Conditions Ref.
agent [%] [kg m–2h–1] [kg m–2h–1MPa–1]
Modified-CS/PSf GA R(NaCl) = 66.3 2543.6 L m–2h–1 1000 mg L–1 NaCl; [203]

p = 0.4 MPa
SCS/PSf ECH R(Na2SO4) = 90.8 22.9 1000 mg L–1; [201]

p = 0.4 MPa;
R(NaCl) = 32.5 58.4 T = ambient
NOCC/PSf ECH R(Na2SO4) = 90.4 7.9 1000 mg L–1; [205]

p = 0.4 MPa;
R(NaCl) = 27.4 10.8 T = 20 C
SCS/PAN GA R(K2SO4) = 92.8 11.3 1000 mg L–1; [204]

p = 0.4 MPa;
R(Na2SO4) = 92.1 7.1 T = 25 C
R(NaCl) = 50.3 10.4
O-CMC/PAN ECH R(Na2SO4) = 94.36 16.78 L m–2h–1 1000 mg L–1; [202]

p = 0.5 MPa;
T = 25 C
HACC/PAN TDI R(MgCl2) = 87.2 11.5 8.96 p = 1.0 MPa; [206]

T = 20 C;
R(MgSO4) = 58.3 12.5 cycling flow = 30 L h–1
R(Na2SO4) = 27.3 10.8
R(NaCl) = 62.5 13.6
GCTACC/PAN TDI R(MgCl2) = 91.7 8.48 14.1 p = 1.2 MPa; [208]

T = 20 C;
R(MgSO4) = 61.9 11.3 cycling flow = 30 L h–1
R(Na2SO4) = 20.1 8.57
R(K2SO4) = 14.5 9.49
R(KCl) = 41.9 8.57
R(NaCl) = 57.0 8.57
HACC/PAN Anhydride R(MgCl2) = 94.8 7.44 L m–2h–1 1000 mg L–1; [207]

mixture –2 –1 p = 1.0 MPa;
R(NaCl) = 60.6 13.5 L m h T = 25 C
CS/PAN GA R(NaCl) = 54.1 52.8 L m–2h–1 1000 mg L–1; [211]

p = 0.9 MPa
CS/PDMCHEA GA R(ZnCl2) = 97.5 20.6 L m–2h–1 CS: PDMCHEA = [209]

50 %:50 %;
R(NaCl) = 57.1 1000 mg L–1;
p = 0.6 MPa;
T = 25 C
N-phthaloyl-CS/SPSf R(MgSO4) = 93 SPSf:CS = 60:40 [212]
R(Na2SO4) = 89
R(NaCl) = 69
CS/PPEES TPP R(MgSO4) = 55 pH = 5 [210]
R(NaCl) = 21
5.3.1 Chitosan Composite NF Membranes of Na2SO4, NaCl, MgSO4, and MgCl2 [188]. Zhou et al. [189]
reported novel composite NF membranes comprised of
NF membranes, a novel kind of separation membrane between O-carboxymethyl CS (O-CMC) as active layer, PAN UF mem-
reverse osmosis (RO) membrane and UF membrane, have been brane as supporting layer and ECH as cross-linking agent.
actively expanded in the recent years. NF membranes give O-CMC acts as a zwitterionic polymer. O-CMC composed of
higher permeate flux than RO membranes, even under low CS and monochloroacetic acid was synthesized through an or-
operating pressure and high salinity [201]. NF membranes can ganic phase grafting modified method. The permeation flux
be categorized into negatively charged, positively charged, and and the salt rejection of the optimal NF membrane were
neutral NF membranes. Positively charged membranes are usu- 16.78 L m–2h–1 and 94.36 % for 1000 mg L–1 Na2SO4 solution,
ally prepared with materials containing amino groups or their respectively. The rejection of the optimal NF membrane to the
derivatives and materials of negatively charged membranes electrolyte solutions decreased in the order of Na2SO4, NaCl,
contain sulfo or carboxyl groups [202]. The ability of these MgSO4, and MgCl2. In another similar work, amphoteric com-
membranes to separate substances depends on both of the size posite NF membranes were prepared through a method of
sieving effect and the electrostatic repulsive effect. Typically, coating and cross-linking. In this study, N,O-carboxymethyl CS
NF involves separation of monovalent and divalent salts, or (NOCC), PSf UF membranes and ECH were used as the active
organic solutes with a molecular weight in the range of 200 to layer material, the base membranes, and the cross-linking
1000 g mol–1 [188]. Most of the commercial NF membranes are agent, respectively. The rejections of the obtained membrane to
composite membranes, which consist of an active layer and a Na2SO4 and NaCl solutions (1000 mg L–1) were 90.4 % and
permeable supporting layer [189]. This membrane morphology 27.4 %, respectively. Moreover, the permeation fluxes were 7.9,
allows the production of materials featured by high water flux and 10.8 kg m–2h–1, respectively. The rejection of this kind of
due to the thin top layer and strength owing to the mechanical NF membrane to inorganic electrolyte solutions was similar to
performances of the support [195]. Various CS derivatives, previous work [205].
such as quaternized CS, N,O-carboxymethyl CS and sulfated Huang et al. [206] employed quaternation to modify CS in
CS (SCS), have been used in the preparation of NF membranes. order to improve its hydrophilicity and introduce positively
Novel composite NF membranes were prepared by coating the charged groups into this polymer. Quaternized CS here means
mixture of CS and mesogenic compounds modified CS onto a 2-hydroxypropyltrimethyl ammonium chloride CS (HACC).
PSf UF membrane. The rejection of the membrane was 66.3 % They prepared a positively charged composite NF membrane
with flux as high as 2543.3 L m–2h–1 with the 1000 mg L–1 of from HACC by coating and cross-linking sequentially. PAN
NaCl at 0.4 MPa. The flux was about three orders of magnitude UF membrane and toluene diisocyanate (TDI) were used as
greater than other conventional CS NF membranes and the support layer and cross-linking reagent, respectively. The rejec-
rejection was inconsiderably greater than the reported value of tion to different salt solutions increased in the order of Na2SO4,
a NF membrane based on CS. This excellent high flux was the MgSO4, NaCl, and MgCl2, suggesting the positively charged
outcome of the membrane structure and function modification characteristic of this membrane. Compared to the previous
through the introduction of mesogenic compounds [203]. By study, they changed only the cross-linking agent and used an
coating the aqueous solution of SCS onto a PAN UF mem- anhydride mixture instead of TDI. With an increase in anhy-
brane, subsequently cross-linked with GA, an amphoteric com- dride mixture concentration, the pure water permeability
posite NF membrane was prepared. Changing the composition decreased whereas the rejection increased. Besides, the rejec-
of the casting solution of the active layer, the preparation tech- tion declined with the increasing feed concentration [207]. In
nique and the concentration of cross-linking agent can adjust another similar work, quaternation is applied to modify CS in
the rejection properties of the SCS/PAN composite membranes. order to introduce positively charge groups. A quaternized CS,
The rejection of this type of membrane to the electrolyte solu- being a graft copolymer of trimethylallyl ammonium chloride
tions decreased in the order of K2SO4, Na2SO4, KC1, NaC1, onto CS (GCTACC), was obtained. In this study, a positively
MgSO4, and MgCl2 [204]. charged composite NF membrane was prepared using
Miao et al. [201] prepared a novel kind of amphoteric GCTACC, PAN UF membrane, and TDI as the selective layer,
TFC NF membrane for the separation of mono/divalent inor- the support layer, and cross-linking agent, respectively. The
ganic electrolytes through the way of coating and cross-link- rejection to different salt solutions was similar to the previous
ing. They used SCS, PSf UF membrane, and ECH as the study [208].
active layer substance, the base membrane, and the cross- In a different work, Ji et al. [209] prepared the CS/
linking agent, respectively. At ambient temperature and PDMCHEA blend positively charged NF membranes via
0.40 MPa, the resultant membrane had a rejection of 90.8 % chemical cross-linking. PDMCHEA was made from 2-meth-
and 32.5 % for Na2SO4 and NaCl solutions (1000 mg L–1), acryloyloxy ethyl trimethylammonium chloride (DMC) and
while the permeate fluxes were 22.9 and 58.4 kg m–2h–1, 2-hydroxyethyl acrylate (HEA). The copolymer PDMCHEA
respectively. Furthermore, the effects of preparation and possesses lots of quaternary ammonium groups, which have
operation variables, including SCS concentration, ECH con- strong electrostatic repulsive force toward cationic ions. The
centration, cross-linking time, and pressure on the rejection presence of hydroxyl groups on PDMCHEA increases the
performance of these membranes were investigated. Both the hydrophilicity of CS/PDMCHEA and consequently improves
rejection and permeate flux increased with the increase of the water flux. A high water permeability of 20.6 L m–2h–1 and
the operating pressure. The rejection of this type of mem- salt rejection of 97.5 % and 57.1 % were obtained for this mem-
brane of inorganic electrolyte solutions reduced in the order brane containing 50 % PDMCHEA.
5.3.2 Other Chitosan Membranes Asymmetric membranes have shown to be promising wound
dressings for the treatment of skin wounds. They contain a
A TFC membrane was prepared using CS as active layer, a dense surface skin layer and the sponge-like sublayer. The top
poly(1,4-phenylene ether ether sulfone) (PPEES) membrane as layer is designed to prevent bacterial invasion and also act as
support layer, and sodium tripolyphosphate (TPP) as cross- rate controller for water vapor permeation while the sublayer is
linking agent. Unlike other cross-linking agents, TPP is physi- designed to attach to wound tissue and to drain wound exu-
cally cross-linking agent that can interact with cationic CS by dates [217, 218]. In this regard, Morgado et al. [219] prepared
electrostatic forces. These membranes displayed rejection up to CS/PVA asymmetric membranes and these membranes pre-
55 % and 21 % towards MgSO4 and NaCl, respectively, at sented the most required characteristics of an ideal wound
pH = 5 [210]. Xu et al. [211] prepared polyamide nanofilm dressing. These membranes were highly biocompatible and
composite membranes (NCMs) with unique PA-TFC mem- could protect the wound from physical damage. Moreover, they
brane morphologies of ridge-and-valley structure by interfacial provided adequate moisture. Based on these results, it can be
polymerization on the CS coated electrospun PAN nanofibrous concluded that CS/PVA asymmetric membranes are promising
membranes. The factors influencing the CS coating layers, such dressing systems to be used on skin regeneration.
as GA and CS concentrations, definitely affect the structures In another similar work, Han et al. [220] prepared an algi-
and desalination properties of the obtained NCMs. At 0.9 MPa nate/CS based bi-layer composite membrane as novel wound
with the initial NaCl concentration of 1000 mg L–1, these mem- dressing. CS and Alginate were employed as dense surface skin
branes exhibited a permeation of as high as 52.8 L m–2h–1 with layer and sublayer, respectively. This membrane could avoid
a NaCl rejection of 54.1 %. A cation-exchange membrane providing substrate for microbial breeding, reduce the risk of
(CEM) was prepared by blending sulfonated PSf (sPSf) and wound infection and could work as a drug reservoir. Results
N-phthloyl CS in different ratios. Hydrophilicity and mem- demonstrate that the membranes could inhibit the growth of
brane charge are greatly affected by sulfonation of PSf and tend microorganisms for longer than 7 days. Moreover, in order to
to increase with the sPSf concentration. Membrane sPSf:CS improve the CS properties, it was also blended with some natu-
60:40 showed 93 %, 89 % and 69 % rejection of MgSO4, Na2SO4 ral polymers for wound dressing applications [221]. CS/silk
and NaCl, respectively [212]. In another work, CS-MWCNTs fibroin (CS/SF) blending membranes cross-linked with alginate
blended membranes were prepared using PES UF membranes dialdehyde (ADA) were prepared as wound dressings. The
as the substrate and GA as the cross-linking agent. The resulted resulted membranes could meet the property needs of a wound
membranes were used for the removal of sodium and magnesi- dressing such as water vapor transmission rate, water absorp-
um salts from aqueous solutions. The solute rejection increased tion, and cell proliferation.
with MWCNT content. The salt rejection of this type of mem- Addition of ADA into CS/SF membranes improved the cell
brane from aqueous solutions decreased in the order of proliferation and enhanced the stability of the membranes
Na2SO4, MgSO4, and NaCl [213]. [216]. Silva et al. [222] prepared CS-aloe vera-based mem-
branes for wound dressing. Totally, the effect of CS/aloe Vera-
based membranes on bacterial growth, the relatively good cel-
6 Other Applications for Chitosan lular response, and their suitable mechanical and physical
Membranes properties suggest that these blended membranes can be useful
as wound dressings. In addition, electrospun collagen/CS nano-
Apart from the applications mentioned above, CS membranes fibrous membranes were prepared for wound dressing applica-
have also been used in some other areas. CS has been used in a tions [223]. These membranes were found to promote wound
large variety of biomedical areas such as drug delivery carriers, healing and induce cell migration and proliferation.
bone healing materials, and especially wound dressings [214].
6.2 Drugs Transportation

6.1 Wound dressing
Another application of CS membranes in the biomedical field
Wound dressings play a very important role in treatment of is the transport of drugs. A CS macroporous membrane with
burns. An ideal wound dressing should be required to provide asymmetric morphology was prepared by using silica particles
a favorable environment for the wound healing process such as as an inorganic porogen agent [224]. These membranes showed
maintaining a high humidity at the wound-dressing interface, good drug permeability with two model drugs (sodium
absorbing exudates and toxic components, providing thermal sulfamerazine and sulfametoxipyridazine). In another work, a
insulation, protecting the wound from bacterial penetration, novel CS nanopore membrane was prepared by using PEG as
allowing gaseous exchange, being simple to utilize and be the porogen agent [225]. The prepared CS nanopore mem-
removed without causing new trauma [215]. CS could achieve brane could well control the diffusion of model drugs (vitamin
hemostasis and accelerate tensile strength of wounds by speed- B1 and sodium sulfamerazine), implying that the CS nanopore
ing the fibroblastic synthesis of collagen in the first few days of membranes can be used to transport drugs in a controlled dif-
wound healing. For these reasons, it has been used as one of fusion manner.
the significant biomaterials for wound dressing in recent years.
Hence, several CS composite membranes have been reported
for wound dressing applications [216].
6.3 Tissue Engineering 6.5 Antibacterial Application
Tissue engineering is another application of CS membranes in CS membranes have also been used in antibacterial applica-
biomedical fields. Tissue engineering is the technology of tions. Sun et al. [233] prepared novel curdlan/CS blending
remodeling living organisms in vitro and involves architecture membranes for antibacterial applications. They chose 4 bacte-
of artificial cellular scaffolds, which mimic extracellular matrix. ria strains as target bacteria using the optical density method to
Ideal membranes for tissue engineering should have good prove the antibacterial activity of the membranes. These mem-
mechanical properties, swelling behavior, biocompatibility, bio- branes displayed outstanding antibacterial activity. In another
activity, and so on. Madhumathi et al. [226] prepared CS work, Liu et al. [234] employed novel starch/CS blending mem-
hydrogel-HAp composite membranes for tissue engineering branes for antibacterial applications. In this study, Escherichia
applications. Great biocompatibility results indicate that these coli were chosen as the target bacteria using the optical density
membranes can have potential applications in the tissue-engi- method to prove the antibacterial activity of the membranes.
neering field. Nano-HAp (n-HAp)/CS cross-linking composite The resulting membranes exhibited an outstanding antibacteri-
membranes were prepared by Li et al. [227]. They suggested al activity against E. coli. Protein adsorption and separation is
that the developed membranes, due to their good cytocompati- another application of CS membranes but few CS membranes,
bility, water adsorption, and suitable tensile strength, can serve have been utilized in recent years. Liu et al. [235] developed a
as the vehicle for bone tissue engineering applications. In CS-based membrane chromatography using natural CS/
another study, carboxymethyl CS-graft-d-glucuronic acid carboxymethylchitosan (CS/CMCS) in the form of a blend
membranes were prepared and the bioactivity behavior of these membrane as the matrix. In this work, Lysozyme was selected
membranes showed that they are very useful for tissue engi- as the model protein and the effect of the flow rate, pore size of
neering applications [228]. Moreover, their results indicated the membrane and the initial concentration of feed solution
that these membranes are effective for drug delivery. was investigated on dynamic adsorption properties of the
CS/CMCS membrane chromatography.
And finally, other applications of CS membranes are in pro-
6.4 GTR and GBR ton batteries [236], microbial growth [237], etc.
Another application of CS membranes in the biomedical field

is guided tissue regeneration (GTR) and guided bone regenera- 7 Conclusion
tion (GBR) for treatment of periodontal diseases. In GTR and
GBR techniques, a barrier membrane is used to prevent the CS membranes show great capability and versatility for the sep-
appearance of epithelial migration and connective tissue. The aration of gaseous mixtures, azeotropic mixtures, heavy metal
GBR technique also aims to promote bone regeneration [229]. ions, dyes, salts, and in DMFC applications. CS cross-linked
Ho et al. [230] prepared an asymmetric CS membrane for the membranes and CS hybrid membranes with inorganic fillers
GTR. This membrane possessed good biocompatibility, tissue are the two major CS modified membranes that have been used
integration, cell occlusivity and osteoconduction. The results in these applications. Cross-linking can improve the plasticiza-
indicated that these asymmetric CS GTR membranes are tion resistance and stability of membranes to stand harsh con-
promising for the treatment of periodontal diseases. CS/bio- ditions. Furthermore, cross-linking limits the chain mobility
active glass nanoparticle (BG-NPs) composite membranes were and as a result a more compact structure is achieved. In the
studied for possible application as GTR membranes and for separation of gaseous mixtures, CS membranes are still in their
GBR [231]. The addition of BG-NPs to CS membranes im- infancy, but the humidity-controlled separation is noteworthy
proved the bioactivity, but on the other hand decreased the of further investigation. CS membranes have a selective perme-
mechanical potential of these membranes. The results ation of CO2 due to the existence of amino groups in the poly-
showed that these composite membranes can be used as a mer chain. Moreover, in the selective separation of CO2 a swol-
temporary GTR membrane in periodontal regeneration. len CS membrane is preferred because the CO2 molecules can
Xianmiao et al. [229] prepared nano-hydroxyapatite (n-HA)/ dissolve in water.
CS composite membranes for the function of GBR. These In this regard, other types of membranes are utilized to
membranes possess good biocompatibility and have no nega- improve the separation performances. Blending CS with other
tive effect on the cell morphology, viability and proliferation. polymers, coating a polymeric layer on the surface of CS mem-
Thus, the CS/n-HA composite membranes show good poten- branes or cross-linking CS membranes with cross-linking
tial for future GBR membrane applications. A novel asym- agents improved separation factor or permeation flux or both
metric CS GBR membrane was prepared. This membrane of them in each case. CS membranes are used in DMFCs appli-
contains a loose layer which can modify cell adhesion and cations. As a PEM material in DMFCs, CS has attracted con-
stabilize blood clots and a dense layer isolating the bone siderable attention due to its high proton conductivity and
defect from the invasion of surrounding connective fibrous excellent alcohol barrier property. CS hybrid membranes with
tissue [232]. Animal experiments show that this membrane inorganic fillers have been employed more than other CS mem-
can fulfill the requirements of GBR due to its biodegradation, branes (CS multilayer, cross-linked and blended membranes)
tensile strength and biocompatibility. Accordingly, the asym- in DMFCs. These membranes improved the selectivity factor
metric CS membrane is a promising GBR membrane for (as an indicator of the suitability of a given membrane for
bone regeneration. DMFC applications) by enhancing the proton conductivity or
decreasing the methanol permeability values. Among all
inorganic materials, solid superacids have triggered significant Alireza Jafari Sanjari received
attention due to their good conductive properties. Many his M.Sc. degree in Chemical
articles have been published about pervaporation applications Engineering from the Univer-
and CS membranes. Hybrid and modified CS membranes sity of Kashan. He is currently
showed good potential in this regard. Inorganic fillers used in a Superior Researcher Scholar
hybrid CS membranes are very promising materials in perva- at the University of Kashan
poration applications. They may offer the solution for separat- and interested in the synthesis
ing such azeotropic mixtures as benzene-cyclohexane and of mixed matrix membranes
MTBE-methanol, etc. Also, in pervaporation it has been found for gas separation and per-
that blending CS with hydrophilic polymers gives better pervaporation.
meability and separation factor than hydrophobic polymers for
dehydration processes.
In water treatment applications including removal of heavy
metal ions and dyes and salts, many CS membranes have been
employed till now and different efforts have been applied to
improve their performances in these fields. For instance, vari- Morteza Asghari, currently a
ous CS adsorptive membranes have been utilized for removal candidate for Associated Pro-
of heavy metal ions from aqueous solutions, but these mem- fessor, received his Ph.D. in
branes suffer from lack of reactive sites in their structures and Chemical Engineering from
sufficient stability in adsorption systems. Hence, blending, the Islamic University of
coating, cross-linking, etc., are good approaches to overcome Science and Technology, Teh-
these problems. The most popular cross-linking agents that ran, Iran. Currently, he is
have been proposed and used for removal of heavy metal ions Superior Researcher & Superi-
are ECH and GA. Also, two widely used polymers that blended or Master of Education at the
with CS have resulted in high performance adsorptive mem- University of Kashan, Iran. He
branes are CA and PVA. In the field of salt rejection, most of is interested in membrane syn-
the used NF membranes are composite membranes, which thesis and modification, mem-
consist of an active layer and a permeable supporting layer. brane gas separation, MD, PV
This membrane morphology allows the production of materials and synthesis of related nano-
featured by high water flux due to the thin top layer and structured materials. As head of Separation Processes
strength owing to the mechanical performances of the support. Research Group (SPRG), he also attempts to apply novel
Other applications of CS membranes are wound dressing, methods to enhance membrane specifications to fit environ-
drugs transportation, tissue engineering, GTR, GBR and anti- mental purposes (green technologies).
bacterial application. CS membranes are mostly utilized for
wound dressing. CS asymmetric membranes are promising
wound dressings for the treatment of skin wounds. They con-
tain a dense surface skin layer and the sponge-like sublayer. Symbols used
The top layer is designed for the prevention of bacterial inva-
sion and also acts as rate controller for water vapor permeation Barrer [m3(STP) m–2s–1kPa–1] permeability unit
while the sublayer is designed for attachment to wound tissue b [S s cm–3] selectivity
and the drainage of wound exudates. R [%] salt rejection rate
T [C] temperature
The authors have declared no conflict of interest p [MPa] pressure
P [cm2s–1] permeability
Abbreviations
ABS acrylonitrile butadiene styrene
ADA alginate dialdehyde
APTEOS 3-aminopropyl-triethoxysilane
CA cellulose acetate
CEM cation-exchange membrane
CMCS carboxymethyl chitosan
CNC cellulose nanocrystal
CP carbopol
CS chitosan
DMC dimethyl carbonate
DMFC direct methanol fuel cell
ECH epichlorohydrin References
EG ethylene glycol
GA glutaraldehyd [1] R. W. Baker, Ind. Eng. Chem. Res. 2002, 41 (6), 1393–1411.
GBR guided bone regeneration DOI: 10.1021/ie0108088
GCTACC graft copolymer of trimethylallyl ammonium [2] D. Xu, S. Hein, K. Wang, Mater. Sci. Technol. 2008, 24 (9),
chloride onto chitosan 1076–1087. DOI: 10.1179/174328408X341762
GTR guided tissue regeneration [3] Z. Y. Yeo et al., J. Nat. Gas Chem. 2012, 21 (3), 282–298.
Hap hydroxyapatite DOI: 10.1016/S1003-9953(11)60366-6
HACC 2-hydroxypropyltrimethyl ammonium chloride [4] M. Elimelech, W. A. Phillip, Science 2011, 333 (6043),
chitosan 712–717. DOI: 10.1126/science.1200488
HEC hydroxyethylcellulose [5] M. M. Pendergast, E. M. Hoek, Energy Environ. Sci. 2011,
HPA heteropoly acid 4 (6), 1946–1971. DOI: 10.1039/c0ee00541j
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A Review on Chitosan Utilization in Membrane Synthesis

Alireza Jafari Sanjari[1], Morteza Asghari[1],*

1 Introduction byproducts of marine processing plants [13]. Chitosan (CS),

Table 1. CS membranes in DMFCs.

Membrane Proton Methanol Temperature Methanol b [· 104 S s cm–3] Description Ref.

CS/Beta (10 %) 1.4 3.1 – 2 4.5 For Nafion 117: [41]

CS/Beta-GPTMS 1.31 2.2 – 2 5.9 (H) For Nafion 117: [41]

CS/OPTi (5–15 %) 1.14 2.8 – 12 4 For Nafion 117: [43]

CS/Cs2-PTA-%5 0.6 5.6 25 – 1.1 (H) For Nafion 212: [36]

CS/1TiC-2SiN-%5 3.8 7.83 25 2 4.85 For chitosan: [33]

CS/PMA 1.5 2.7 25 – 5.5 for Nafion 117: [44]

CS/STiO2-%10 1.55 6.48 – – 2.4 For chitosan: [42]

CS/HO3SY-%10 2.58 6 – 12 4.28 For Nafion 117: [46]

4.1 Chitosan Derivatives and Cross-Linked

Figure 4. Overview of CS membranes used in pervaporation.

Type of membranes Solution mixture Separation Flux Thickness Temperature Ref.

CS DMSO(50 wt %)/water 120 20 20 40 [54]

CS DMC/methanol/water – – 28.4 – [55]

Phosphorylated CS Ethanol(90 wt %)/water 600 200 ~20 70 [58]

Benzoyl CS Benzene(10 wt %)/water ~65 – 30 40 [61]

Phosphorylated CS Ethanol(95.58 wt %)/water 213 580 – – [76]

GA cross-linked CS Dimethylhydrazine(50 wt %)/water 10.6 167 40 - [65]

Isopropanol(85 wt %)/water 240 500 20 60 [57]

Maleic anhydride surface modified GA Ethanol(90wt %)/water 634 300 – 60 [73]

SSA cross-linked CS Ethanol(80 wt %)/water 9000 450 – 60 [69]

H2SO4 cross-linked CS DMC/methanol/water – – – – [78]

H2SO4 cross-linked CS EG(96.437 wt %)/water 234 378 50 30 [64]

TDI cross-linked CS Isopropanol(87.5 wt %)/water 472 390 10 30 [63]

Blocked diisocyanate cross-linked CS Isopropanol(95 wt %)/water 5918 22 – 30 [62]

TMC cross-linked CS Isopropanol(90 wt %)/water ~350 – 140 60 [19]

Chitosan composite membranes:

(a) Blended membranes

CS/SA Ethanol(95.4 wt %)/Water 436 22 10 30 [82]

Carboxymethylated CS(CMCS)/alginate Alcohol/water ¥ 8 – – [84]

CS/PAA Ethanol(95 wt %)/water >19 000 22 45–50 80 [81]

CS/PAA Isopropanol(87.5 wt %)/water 1736 140 10 30 [80]

CS/PAA EG(80 wt %)/water 105 216 ~30 70 [85]

CS/PVA Isopropanol(90 wt %)/water >899 991 644 18–25 60 [88]

CS/PVA Isopropanol(90 wt %)/water 17991 113 35–40 30 [87]

THF(95 wt %)/water 4203 98 35–40 30 [87]

CS/PVA 1,4-Dioxane(82 wt %)/water 117 366 50 30 [86]

CS/PVA EG(90 wt %)/water 986 460 34 70 [79]

CS/PVA Benzene(50 %)/cyclohexane 49.9 51.41 – 50 [89]

CS/PVP THF(94.31 wt %)/water 1025 99.5 40 35 [96]

CS/HEC Ethanol(90 wt %)/water 10 491 112 30–35 25 [91]

Isopropanol(90 wt %)/water 26 091 175 30–35 25 [91]

CS/HEC 2-Butanol(77 wt %)/water 554 2100 50 30 [90]

CS/CMCNa Ethanol(90 wt %)/water 1062 1140 – 70 [97]

CS/Nylon 66 1,4-Dioxane(82 wt %)/water 865 89 50 30 [94]

CS/N-methylol Nylon Ethanol(95 wt %)/water 560 350 10 60 [93]

Type of membranes Solution mixture Separation Flux Thickness Temperature Ref.

CS/KGM CPL(70 wt %)/water >3000 – – Every temp. [92]

CS/PEO Ethanol(92 wt %)/water 4.4 900 20 20 [95]

CS/HPC Isopropanol(90 wt %)/water 11 241 132 50+1 30 [98]

(b) Chitosan membranes with porous substrate

CS/PES Ethanol(90 wt %)/water – – 10 80 [101]

CS/PES Glycol(80 wt %)/water >796 1130 10 80 [102]

CS/PES modified by surfactants Methanol(20 wt %)/water 50 100 – 25 [102]