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ISSN : 1226-0088(Print)
ISSN : 2288-7253(Online)
Membrane Journal Vol.32 No.2 pp.91-99
DOI : https://doi.org/10.14579/MEMBRANE_JOURNAL.2022.32.2.91

Ion Exchange Membrane for Desalination by Electrodialysis Process: A Review

Sarsenbek Assel*, Rajkumar Patel**†
*Nano Science and Engineering (NSE), Integrated Science and Engineering Division (ISED), Underwood International College, Yonsei University, Incheon 21983, South Korea
**Energy and Environmental Science and Engineering (EESE), Integrated Science and Engineering Division (ISED), Underwood International College, Yonsei University, Incheon 21983, South Korea
†Corresponding author(e-mail: rajkumar@yonsei.ac.kr; http://orcid.org/0000-0002-3820-141X)
April 5, 2022 ; April 21, 2022 ; April 22, 2022

Abstract


It is a global challenge to fulfill the demand for clean water at an affordable cost to all the strata of the population. Desalination of seawater as well as brackish water by the membrane separation process is a well-established and cost-efficient method. However, there is still inherent problem of membrane fouling, disposal of the reject as well as a capital- intensive process. While electrodialysis (ED) is a membrane-based separation process in which a driving force is the potential difference. The advantages of ED process are excellent efficiency and low operation cost. Ion exchange membrane (IEM) used in the ED process needs to have higher chemical and thermal stability along with excellent mechanical strength for long-term use without losing its efficiency. The ion exchange capacity of the ED membrane is largely dependent on the conductivity of IEMs. In this review, the modification strategy of the pristine membrane to enhance the stability and ion conductivity of cation exchange membrane (CEM) and anion exchange membrane (AEM) is discussed.


ion exchange membrane , cation exchange membrane , anion exchange membrane , electrodialysis

전기투석법에 의한 담수화용 이온교환막: 총설

살센벡 아샐*, 라즈쿠마 파텔**†
*연세대학교 언더우드국제대학 융합과학공학부 나노과학공학
**연세대학교 언더우드학부 융합과학공학부 에너지환경융합전공

초록


모든 인구 계층에 저렴한 비용으로 깨끗한 물의 수요를 충족시키는 것은 해결해야 할 세계적인 문제이다. 막 분 리 공정을 통한 해수 및 기수의 탈염은 효율이 높고 확립된 방법이다. 그러나 막 분리 공정은 막 오염, 제거된 오염물의 처리, 그리고 자본집약적 공정이라는 본질적인 문제가 있다. 전기투석은 전위차가 구동력인 막 기반 분리 공정이다. 전기투석막의 장점은 뛰어난 효율과 저렴한 운영 비용이다. 전기투석공정에서 사용되는 이온교환막은 장기간 효율을 잃지 않기 위해 내화 학성과 내열성, 그리고 기계적 안정성이 필요하다. 이 때, 전기투석막의 이온교환용량은 이온교환막의 전도도에 따라 크게 달 라진다. 본 리뷰에서는 이온 전도도과 안정성을 향상시키기 위한 양이온 교환막과 음이온 교환막의 개조를 중점적으로 논의 하였다.


    1. Introduction

    Desalination of seawater is a very important process to generate clean water for application in various sectors. Ion exchange membrane (IEM) plays a key role in electro membrane process for energy production as well as desalination. Desalination through electro membrane process is basically divided into i) electrodialysis (ED) and ii) membrane capacitive deionization (MCDI) [1-4]. The Basic principle of this process is by application of potential difference to ionic solution, transportation of ion occurs through IEMs. It only allows the oppositely charged ion to pass through them.

    There are various reports of modification of IEM to improve the desalination performance. Surface modification of the membrane by incorporating different functional groups, blending with another polymer of interest or making nanocomposite membrane by incorporating nanoparticles with suitable functional group modification[5-8]. Crosslinking of the membrane improves the mechanical stability and durability of the membrane.

    Cation exchange membrane (CEM) can be prepared by mixing of pristine polymer with an inorganic filler such as graphene oxide modified with a cationic group like styrene sulfonic acid[9-12]. TiO2 as well as carbon nanofiber (CNF) are filler materials used in CEM. The incorporation of another component enhances the hydrophilicity, ionic conductivity, transport properties as well as selectivity of the IEMs. Advantages of CEM are selective separation of monovalent cation and higher recovery rate of water compared to reverse osmosis membrane, but neutral molecule cannot be removed.

    Anion exchange membranes are generally positively charge polyelectrolyte membranes[13-16]. The most commonly used polymer for AEMs are polybenzimidazole, polyether ether ketone, poly(arylene ether ketone), polysulfone etc. Block polymers used in AEMs enhance degree of microphase separation which enhance the efficiency of the IEMs. Monovalent anions can be separated by AEM but uncharged molecules are difficult to remove. This review is mainly classified into cation and anion exchange membranes. The classification of the review is presented in Fig. 1.

    2. Ion Exchange Membrane

    Mabrouk et al. studied about chloramine membrane which was formed by the reaction of sulfochlorated polyethersulfone, and aminated polyethersulfone which acts as crosslinking agent[17]. The main purpose of the membrane is to check the desalination performance of blackish water via electrodialysis. This was studied from different perspectives (contact angle, transport number, intrinsic conductivity, and water uptake) as well as electrodialysis. From that these data were confirmed: contact angle characterization showed hydrophilic properties; the membrane showed to be more stable at higher temperature; the water uptake was inversely proportional to rise in temperature. It was also reported that water uptake was also decreased after chemical crosslinking with fixed ion concentration. The membrane of chloramine was protected from dissolution due to cross linking, at 60°C in water. The ion exchange capacity (IEC) was 2.2 meq/g and transport number of cation is about unity. The demineralization properties were also increased which enabled ED results to elevate into 100% with the usage of new membrane. The membrane showed great performance in the elimination of NaCl from water in ED desalination applications. The membranes of chloramine can be successfully inserted not only in better water desalination processes via electrodialysis but also can be applied in various techniques for with various separation requirements.

    Roman et al. reported the transportation of salt ions through seawater to the wastewater by energy-efficient electrodialysis desalination processes[18]. Organic micropollutants (OMPs) migrate in the reverse direction and it is very sensitive to pH. Due to its large variation, environmentally correct simulations were created by pool of nineteen OMPs with different physicochemical properties. The analysis of adsorption and transport of OMPs influence mechanism, as pH function was determined by around 20 physicochemical properties. As well as how various current densities affected the transport of organisms was studied. During ED, the difference of pH variations impacted transport and adsorption of OMPs that were in a stream with low salinity simultaneously affecting the ionization of the particles. In low pH environment (unbuffered conditions), in IEMs, the OMPs adsorption was accelerating, that efficiently resists their transport into seawater. In comparison with neutral pH system, low pH adsorption had approximately same high result of OMPs, regardless of the charge. Nevertheless, the charge difference affected adsorption of OMPs. In buffered ED, it affected in the decrease of OMPs adsorption, also it was depending on the time between OMPs and IEMs. If the adsorption was lowered, if affected in OMPs transporting into seawater since its transportation dependent of the charge. Negatively charge OMPs determined to have the highest transportations results.

    Tian et al. reported wastewater treatment by electrodialysis through bipolar membrane[19]. Refinery wastewater with higher salinity is difficult to treat. Bipolar membrane with electrodialysis process (BMED) is alternative strategy for wastewater treatment. Simulated studied showed that wastewater with 8% sodium sulfate reduced to 0.37%. Fig. 2 represent the wastewater generation and Fig. 3 represent BMED process.

    2.1. Cation exchange membrane

    Alabi et al. reported the cation exchange membrane nanocomposite which was fabricated by in-house developed mold-casting technique[20]. Where graphene- based nanomaterials were incorporated in poly (vinylidene fluoride) (PVDF) matrix without any charge. The usage of poly (sodium 4-styrenesulfonate)/ 3,4-dihydroxy-L-phenylalanine (PSS/L- DOPA) (altered graphene oxide nanosheets (SGO) or altered reduced graphene oxide SrGO), which is group-bearing agent established from sulfonic acid, was held into transformation of ion exchange group carriers from graphene oxide (GO) or reduced graphene oxide (rGO) nanosheets. These changes of nanocomposite CEMs were based on exchange properties of ions in SrGO as well as SGO fused into polyvinylidene fluoride (PVDF), as SrGO/PVDF and SGO/PVDF, respectively. The composites CEMs with 45 wt% observed to be without cracks in contrast to materials above that value, CEMs composites went through cracking and deformation. The SGO/PVDF_45 or SrGO/PVDF_45 CEM did not aggregate. The fillers of pores affected in lower linear swelling ratios and high membrane stiffness in CEMs nanocomposites therefore they experienced good membrane stability. In contrast, the SGO/PVDF_45 CEM’s perm selectivity as well as ion exchange capacity (IEC) were higher than the numbers of SrGO/ PVDF_45 CEM (because of the grown resistance of area in the CEM due to SrGO). In contrast, the latter had higher efficiency of current because of developed rGO conductivity properties. In terms of characterizations, the scanning electron microscopy (SEM) was used to initially coated membrane to receive an image where both SGO and SrGO samples had excellent orientation and structure of stacking sheets. In addition, through Fourier-transform infrared (FTIR) technique, the functional groups were identified between rGO and GO, also compared to one another. Finally, the electrodialysis process can be improved through the functional groups of graphene oxide nanosheets that are inserted into matrix of polymer to achieve better results.

    Jashini et al. reported electrodialysis process in cation exchange membrane for application in desalination process[21]. The new cation exchange membrane mixed matrix (MM) was created from carbon nanofibers (CNFs) incorporation in matrix of membrane. The nanofibers enabled membrane to increase its potential, perm selectivity, transport number, ionic conductivity, hydrophilicity, and simultaneously decrease the uptake of water. Due to CNFs surface uniformity (better transportation) as well as sodium flux also showed positive results. The latter ratios changed from 0 to 0.5 wt% and 2 to 8 wt% whereas for 0.5 to 2 wt% CNF, it dropped. The flux ratio of potassium ion to sodium ion (K+/Na+) is about 2.14 through electrodialysis. The results reviled that K+ ions transported more across a membrane than Na+ ions. Their migration was characterized by potential of hydration, hydration entropy, ionic and hydrated radius, the Jones-Dole coefficient, as well as free energy of hydration. To see the structural integrity of the sample, SEM was measured. It showed that the surface was uniform and heterogeneous. As well as the scanning optical microscopy (SOM) was used with various percentage of CNF on the matrix, which also confirmed previous observation. Due to that the membrane matrix had uniform distribution. of elements which enabled better transportation of particles. Consequently, 0.5 wt% ratio of CNFs containing samples reveled excellent results with selectivity greater than 88%, maximum number of transport (> 93), and flux, whilst maintaining the minimum of MER (< 5.6 Ω cm2).

    Ma et al. reported cation-exchange membrane, for desalination and anti-organic fouling for treatment of water, from polyethyleneimine (PEI), graphene oxide (GO) and titanium dioxide (TiO2) nanoparticles[22]. Foulants such as humic acid (HA) and bovine serum albumin (BSA), were used to test the unmodified and modified membranes’ fouling property. The former membrane surface results in dramatical surface deposition as well as in polyethyleneimine-titanium dioxide (PEI-TiO2) and modified PEI membrane. In comparison, on PEI-GO membranes the fouling of HA was observed. The fouling of BSA, on the contrary, was small for all modified as compared to unmodified membranes. The electrodialysis with the membrane, which is unmodified, did not experienced improvements in synthetical water treatment in terms of HA fouling while most of the modified membranes did due to great bond between PEI and HA’s amino groups. They also increased desalination in BSA containing synthetic water treatment, which showed maintaining results in desalination for all membranes. In practical comparison between unaltered and altered PEI membranes in term of removing salts, the former separated 20-40% while latter did 80%, respectively. The antifouling properties of nanocomposite membranes (specifically membrane of PEI-GO) were exquisite during operation for 100 h, in comparison with the fouling unmodified membranes after 50 h treating wastewater. The alteration on the surface of cation-exchange membranes can provide advanced, environmentally friendly organic-inorganic membranes. Those membranes have better performance, savage of energy as well as efficiency of desalination that are essential in applications in water treatment.

    2.2. Anion exchange membrane

    The Poly(vinyl chloride) (PVC) based anion exchange membrane with excellent antifouling property for electrodialysis application was reported by Liu et al.[23]. The Quaternized crosslinked PVC film was prepared by treatment with triethylenetetramine. It has excellent antifouling property with 90.2% sodium chloride ratio of removal, efficiency of current is 65.8% and consumption of energy is 1.99 kW.h/kg NaCl. This anion exchange performance outperforms the commercially available AEM. Fig. 4 represent the digital image of the membrane and Fig. 5 shows the mechanism of antifouling property.

    Liu et al. reported eco-friendly method of chloromethylated polysulfone (CMPSF) preparation in which degree of chlorination can be controlled and without the use of chloromethyl ether to prepare AEMs[24]. Different compositions of AEMs were formulated with CMPSF by different concentration type of CMPSF with various degree of chloromethylation. The results were compared between one another and AEM-1.95 elucidated to own better performance than other samples due to highest degree of chloromethylation. In AEM-1.95 rate of desalination was possible to increase to 94.5% whilst consumption of energy was merely 7.5 kWh/kg. It outstood with both physical and chemical as well as electrical properties. The possible application of AEM is realizable in construction of high-quality polymers.

    Bipyridine modified with hexyl group and 1,4-diazabicyclo[ 2.2.2] octane (DABCO) di-cations functionalized anion exchange membranes (QPPO-DP and QPPODABCO respectively) were prepared by reacting with brominated poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and synthesized quaternizing molecules[25]. The exchange capacity (IEC), swelling ratio (SR), area resistance (Rm) water uptake (WU), ion mechanical and thermal stabilities, transport number (t-), morphology and limiting current density properties were used to describe QPPO-DP and QPPO- DABCO.

    Thermo-gravimetric analysis was performed to check the weight loss of QPPO-DP and QPPO-DABCO. Because of distinction in di-cation mass, the IECs of QPPO-DP and QPPO-DABCO were 2.27 and 2.63 mmol g-1 respectively. Due to bipyridine di-cations’ aromatic bicyclic structure, the QPPO-DP has higher WU than QPPO-DABCO. In contrast, QPPO-DABCO performed better in ED with salt flux of 81.39%, efficiency of current of 89.58%, and consumption of energy of 1.76 kWh/kg. Those results in potential application of QPPO- DABCO in electrodialysis because it has excellent stability during desalination.

    Peng et al. developed AEMs with both efficient ionic transportation as well as mechanical and dimensional stabilities[26]. The membrane was prepared by cross linking between 2-chloroacetamide (CAA) linked poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and N, N,N′,N′-tetramethyl-1,4-diaminobutane (TMDAB). In comparison with AEM without crosslinkers, the prepared AEMs showed higher values in IEC (1.38–1.84 mmol g-1) and lower values of water uptake (13.14– 22.45%). Membrane with cross-linked three dimensional structure outperformed in terms of thermal and mechanical stabilities by comparing with membranes without cross-linkage. Through atomic force microscopy (AFM) the degree of phase separation was measured that increase with enhancement in degree of crosslinking. The crosslinked AEM, additionally, has more significant efficiency of current (78.6%) and less consumption of energy (2.01 kWh kg-1 NaCl) in electrodialysis. These results state that better desalination for electrodialysis can be achieved with more transportation of ions simultaneously less consumption of energy.

    Singh et al. prepared 1,4-bis(4-vinylbenzyl)-1,4-diazabicyclo[ 2,2,2] octane-1,4-diium) (BVDOD) a crosslinking agent and cross-linked dehydro-halogenated poly (vinylidene fluoride-co-hexafluoro propylene) (PVDF-co-HFP)[27]. Multiple side chain with cationic group and main chain of polymer with fluorine substitution are important criteria of AEMs. AEMs properties were determined by the crosslinking in the matrix which dictated chemical and physical properties of membranes. FTIR spectra of PVDF-co-HFP dehydrofluorination indicates the crosslinkage of polymer fluorinated carbon. Best cross-linked AEM (Cr-AEM) displayed IEC of 1.02 × 10-3 equiv /g and ionic conductivity of 5.7 × 10-2 S /cm and 23.5% of water content. Perm selectivity of the membrane 0.94-0.96 and limiting current density was 2.36 mA/cm2, which are relatively high.

    Yadav et al. prepared AEMs based on poly (vinylidene fluoride-co-hexafluoropropylene) for electrodialysis applications in water treatment[28]. For suitability tests different kinds of membranes were examined through general stability as well as ion transport behavior. TEM and AFM characterizations showed phases the separation between hydrophobicity and hydrophilicity, lighter and darker regions, ionic domains, and their morphology. Different membranes with different IEC were prepared by the usage of backbone with dehydrohalogenated poly (vinylidene fluoride-co-hexafluoropropylene). AEM-1.0 was the most efficient because of excellent electro-chemical properties with 44.3% of uptake of water, IEC of 1.56 meq g-1 and 21.1 mS cm-1 of ionic conductivity. Faster electro dialytic desalination properties are enabled through significantly higher transport number of 0.94 and limiting current density of 43.7 Am-2. Moreover, AEM-1.0 possessed low energy consumption of 1.05 kWh kg-1 and very good energy efficiency of 87.33% which is very effective for desalination purpose of blackish water by electrodialysis process.

    Yu et al. prepared PSU based crosslinked quatermized AEM by exposure to ultraviolet (UV) light[29]. The method is simple and avoid the uneven reactions as well as unintended aggregation of trimethylamine by heterogeneous quaternization. In comparison with the traditional method, the ultraviolet cross-linkage made the reactions easier and convenient. By crosslinking, AEMs water uptake declined approximately by about 30% (62.6% to 36.9%) whereas the linearly expansion ratios decreased from 26.3% to 13.4% without significant effect of the resistance of surface area. The method creates stronger AEMs with high tensile strength that enhanced from 4.32 to 11.89 MPa for cross-linked AEMs as well as elongation at break improve from 13.8~30.9%. The crosslinking also increased the dimensional and mechanical stabilities by decreasing the water absorption. AFM of membrane was analyzed to see the roughness at the surface which smothered out with rise of acrylate groups. During electrodialysis (ED), AEMs with cross-linking performed better with NaCl removal was 75.0%, consumption of energy was 6.06 kWh Kg-1, current efficiency was 92.7% as compared to uncross linked membrane.

    3. Conclusions

    Ion exchange membrane is the key component for membrane separation process by electrodialysis. IEC of the ion exchange membrane is dependent on the ionic conductivity of the membrane. Commercially available cation exchange membrane such as Nafion showed excellent stability and conductivity but its disadvantage is cost. There are various strategies such as blending, nanocomposite, crosslinking and semi-interpenetrating network to improve mechanical strength as well as swelling properties. Polymer with aromatic backbone like polyethersulfone, polysulfone and polyether ether ketone are excellent class of polymer for modification with various ionic group. In this review different type of ion exchange polymers are classified into cationic and anionic exchange polymers for application in electrodialysis process for seawater or brackish water desalination.

    Figures

    MEMBRANE_JOURNAL-32-2-91_F1.gif

    Schematic presentation of the classification of the review.

    MEMBRANE_JOURNAL-32-2-91_F2.gif

    Flow diagram of the wastewater generation process (Reproduced with permission from Tian et al., 19, Copyright 2019, American Chemical Society).

    MEMBRANE_JOURNAL-32-2-91_F3.gif

    Experimental schematic diagram of BMED treatment of sodium sulfate wastewater (Reproduced with permission from Tian et al., 19, Copyright 2019, American Chemical Society).

    MEMBRANE_JOURNAL-32-2-91_F4.gif

    (a) Digital photographs of c-QPVC-3N and the possible chemical structure. (b) FTIR spectra of PVC (1), c-QPVC-1N (2), c-QPVC-2N (3), and c-QPVC-3N (4). (c) The appearance of PVC and c-QPVC-3N films (~75 μm in thickness) in DMAc with time at room temperature (Reproduced with permission from Liu et al., 23, Copyright 2021, American Chemical Society).

    MEMBRANE_JOURNAL-32-2-91_F5.gif

    (a) Potential across c-QPVC-1N, c-QPVC-2N, c-QPVC-3N, and JAM-II-5 AEMs with time using the SDBS foulant model. (b) FTIR spectra of the pristine and fouled AEMs. (c) Schematic diagram of the antifouling mechanism of c-QPVC-3N AEM (Reproduced with permission from Liu et al., 23, Copyright 2021, American Chemical Society).

    Tables

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