원자이동 라디칼 그래프트 중합법을 이용한 양이온 교환 멤브레인의 제조 및 바나듐 레독스 흐름 전지 격막으로의 응용

서미영(Mi-Young Seo),최성호(Seong-Ho Choi) 융복합지식학회 2022 융복합지식학회논문지 Vol.10 No.2

바나듐 레독스 흐름전지 격막으로 사용하기 위하여, 양이온 교환멤브레인을 원자이동 라디칼 그래프트 중합법으로 합성하였다. 구체적으로 양이온 교환 멤브레인의 주쇄사슬로써 범용플라스틱인 poly(vinyl chloride)를 사용하였다. 여기에 술폰산기(-SO₃Na)를 갖은 4-styrene sulfonate를 원자이동 라디칼 그래프트 중합시킴으로서 poly(vinyl chloride)-g-poly(styrene sulfonate), 약칭 PVC-g-PSS, 합성한 후, 핸디 캐스팅하여 양이온 교환 멤브레인을 제작하였다. 제조된 양이온 교환 멤브레인에 대하여 물 흡착률과 팽창률, 이온 전도도, 이온 교환 용량, 바나듐 투과도, 인장강도를 측정 평가되었다. 또한, 제조된 양이온 교환 멤브레인의 직접 바나듐 레독스 흐름 전지에 적용하여 1,000회 충전 및 방전시킴으로써 이온-교환 막으로써의 안정성이 평가하였다. 이 결과 제조된 PVC-g-PSS 양이온 교환 멤브레인의 경우 바나듐 레독스 흐름전지에 사용할 수 있다. In order to use vanadium redox flow battery separator, we synthesized a cation exchange membrane by atom transfer radical graft polymerization. Poly(vinyl chloride) which is known as a general plastic materials, was used as the main chain polymer of the cation exchange membrane. The poly(vinyl chloride) is grafted by atom transfer radical graft polymerization of 4-styrene sulfonate with sulfonate group (-SO₃Na) to give poly(vinyl chloride)-g-poly(styrene sulfonate), PVC-g-PSS. The cation exchange membrane was fabricated by hand casting of the solution after dissolving N-methyl-2-pyrrolidone of PVC-g-PSS. The obtained cation exchange membranes were characterized by water adsorption ratio, expansion ratio, ion conductivity, ion exchange capacity, vanadium permeability, and tensile strength for using separator of vanadium redox flow battery. The vanadium redox flow battery system with PVC-g-PSS separator during charging and discharging with 1,000 cycles had very higher stability. From these results, the synthesized cation exchange membrane could be used as separator in vanadium redox flow battery system.

Ion Exchange Membrane for Desalination by Electrodialysis Process: A Review

라즈쿠마파텔,살센벡 아샐 한국막학회 2022 멤브레인 Vol.32 No.2

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 capi- tal-intensive process. While electrodialysis (ED) is a membrane-based separation process in which a driving force is the po- tential 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 depend- ent 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.

A Review Based on Ion Separation by Ion Exchange Membrane

라즈쿠마파텔,살센벡 아샐 한국막학회 2022 멤브레인 Vol.32 No.4

Ion exchange membrane (IEM) is an important class of membrane applied in batteries, fuel cells, chloride-alkali processes, etc to separate various mono and multivalent ions. The membrane process is based on the electrically driven force, green separation method, which is an emerging area in desalination of seawater and water treatment. Electrodialysis (ED) is a technique in which cations and anions move selectively along the IEM. Anion exchange membrane (AEM) is one of the important components of the ED process which is critical to enhancing the process efficiency. The introduction of cross-linking in the IEM improves the ion-selective separation performance due to the reduction of free volume. During the desalination of seawater by reverse osmosis (RO) process, there is a lot of dissolved salt present in the concentrate of RO. So, the ED process consisting of a monovalent cation-selective membrane reduces fouling and improves membrane flux. This review is divided into three sections such as electrodialysis (ED), anion exchange membrane (AEM), and cation exchange membrane (CEM).

Poly (phenylene oxide, PPO) 고분자 전해질을 이용한 불균질 바이폴라막 제조 및 물분해 특성

김인식 ( In Sik Kim ),황성연 ( Seong Yeon Hwang ),강병관 ( Byung Gwan Kang ),황택성 ( Taek Sung Hwang ) 한국화학공학회 2019 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.57 No.1

본 연구에서는 PPO 이온선택성 용액과 이온교환수지의 혼합비율을 달리하여 캐스팅법으로 불균질 이온교환막을 제조하였고 이를 이용하여 불균질 바이폴라막을 제조하였다. 불균질 양이온교환막 및 음이온교환막의 함수율은 각각 60~80% 이었고 이온교환용량은 2.81~3.26 meq/g, 2.31~2.74 meq/g 이었으며 전기저항은 1.65~1.45Ω·㎠, 1.55~1.05 Ω·㎠ 이었다. 또한 불균질 이온교환막의 최대 수지함량은 60 wt% 이었다. 불균질 바이폴라막의 인장강도는 관능화 전 PPO 수지의 인장강도(700 Kgf/㎠) 보다 모두 낮았고, 촉매층이 형성된 불균질 바이폴라막의 인장강도는 무촉매 불균질 바이폴라막보다 인장강도가 낮았다. 또한 촉매층이 형성된 불균질 바이폴라막의 물분해 전압은 최소 1.7~1.8 V, 최대 3.9~4.0 V로 낮고 매우 안정적이었고, 무촉매 불균질 바이폴라막의 물분해 전압은 3.8~4.0 V로 일정하였다. In this study, heterogeneous ion exchange membranes were prepared by casting method with various mixing ratios of PPO ion-selective solution and ion exchange resin. Then heterogeneous bipolar membranes were prepared by using this. The water content of heterogeneous cation and anion exchange membranes were 60~80% respectively, the ion exchange capacity was 2.81~3.26 meq/g, 2.31~2.74 meq/g and electrical resistances were 1.65~1.45 Ω·㎠ and 1.55 ~1.05 Ω·㎠. The tensile strength of heterogeneous bipolar membrane was lower than that of PPO resin before functionalization (700 Kgf/㎠). The tensile strength of heterogeneous bipolar membrane with catalyst layer was lower than that of non-catalytic heterogeneous bipolar membrane. The water splitting voltage of the heterogeneous bipolar membrane with catalyst layer was low and stable at a minimum of 1.7~1.8 V, maximum 3.9~4.0 V, and the water splitting voltage of the non-catalytic heterogeneous bipolar membrane was constant at 3.8~4.0 V.

Preparation of Highly Tough Ethylene Vinyl Acetate (EVA) Heterogeneous Cation Exchange Membranes and Their Properties of Desalination

( In Sik Kim ),( Dae Young Ko ),( Ali Canlier ),( Taek Sung Hwang ) 한국화학공학회 2018 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.56 No.3

A manufacturing method has been devised to prepare novel heterogeneous cation exchange membranes by mixing ethylene vinyl acetate (EVA) copolymers with a commercial cation exchange resin. Optimum material characteristics, mixture ratios and manufacturing conditions have been worked out for achieving favorable membrane performance. Ion exchange capacity, electrical resistance, water uptake, swelling ratio and tensile strength properties were measured. SEM analysis was used to monitor morphology. Effects of vinyl acetate (VA) content, melt index (MI) and ion exchange resin content on properties of heterogeneous cation exchange membranes have been discussed. An application test was carried out by mounting a selected membrane in a membrane capacitive deionization (MCDI) system to investigate its desalination capability. 0.92 meq/g of ion exchange capacity, 8.7 Ω.㎠ of electrical resistance, 40 kgf/ ㎠ of tensile strength, 19% of swelling ratio, 42% of water uptake, and 56.4% salt removal rate were achieved at best. VA content plays a leading role on the extent of physical properties and performance; however, MI is important for having uniform distribution of resin grains and achieving better ionic conductivity. Overall, manufacturing cost has been suppressed to 5-10% of that of homogeneous ion exchange membranes.

Poly (phenylene oxide, PPO) 고분자 전해질을 이용한 불균질 바이폴라막 제조 및 물분해 특성

김인식,황성연,강병관,황택성 한국화학공학회 2019 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.57 No.7

In this study, heterogeneous ion exchange membranes were prepared by casting method with various mixing ratios of PPO ion-selective solution and ion exchange resin. Then heterogeneous bipolar membranes were prepared by using this. The water content of heterogeneous cation and anion exchange membranes were 60~80% respectively, the ion exchange capacity was 2.81~3.26 meq/g, 2.31~2.74 meq/g and electrical resistances were 1.65~1.45 Ω·cm2 and 1.55 ~1.05 Ω·cm2. The tensile strength of heterogeneous bipolar membrane was lower than that of PPO resin before functionalization (700 Kgf/cm2). The tensile strength of heterogeneous bipolar membrane with catalyst layer was lower than that of non-catalytic heterogeneous bipolar membrane. The water splitting voltage of the heterogeneous bipolar membrane with catalyst layer was low and stable at a minimum of 1.7~1.8 V, maximum 3.9~4.0 V, and the water splitting voltage of the non-catalytic heterogeneous bipolar membrane was constant at 3.8~4.0 V. 본 연구에서는 PPO 이온선택성 용액과 이온교환수지의 혼합비율을 달리하여 캐스팅법으로 불균질 이온교환막을 제조하였고 이를 이용하여 불균질 바이폴라막을 제조하였다. 불균질 양이온교환막 및 음이온교환막의 함수율은 각각60~80% 이었고 이온교환용량은 2.81~3.26 meq/g, 2.31~2.74 meq/g 이었으며 전기저항은 1.65~1.45Ω·cm2, 1.55~1.05 Ω·cm2 이었다. 또한 불균질 이온교환막의 최대 수지함량은 60 wt% 이었다. 불균질 바이폴라막의 인장강도는 관능화 전 PPO 수지의 인장강도(700 Kgf/cm2) 보다 모두 낮았고, 촉매층이 형성된 불균질 바이폴라막의 인장강도는 무촉매 불균질 바이폴라막보다 인장강도가 낮았다. 또한 촉매층이 형성된 불균질 바이폴라막의 물분해 전압은 최소 1.7~1.8 V, 최대3.9~4.0 V로 낮고 매우 안정적이었고, 무촉매 불균질 바이폴라막의 물분해 전압은 3.8~4.0 V로 일정하였다.

Preparation and Characterization of cation exchange membranes based on Polyphenylene oxide/Acrylate monomer Semi-Interpenetrating Network for reverse electrodialysis(RED)

이영주,차민석,신상훈,한승희,김형중,홍영택,이장용 한국공업화학회 2019 한국공업화학회 연구논문 초록집 Vol.2019 No.1

As blue energy the oceans have been investigated to obtain various forms of renewable energy. One of the ocean energy sources is salinity gradient energy, which is available from the change in Gibbs energy during mixing of seawater and river water. The main components of a reverse electrodialysis system are ion-selective membranes such as cation exchange membrane, anion exchange membrane. Cation exchange membranes require low electric resistance, high permselectivity. Semi-interpenetrating network have high mechanical property and good chemical stability. In this study, cation exchange membranes based on semi-IPNs were prepared for RED application. Membrane properties, such as chemical structure(FT-IR), ion exchange capacity, water uptake, morphology, permselectivity, area resistance were measured. In conclusion, sIC2 showed excellent power density relatively greater than commercial CMV membrane under the same condition.

양이온 교환막에 의한 암모니아 흡착 특성

김민,최혁준,양갑석,허광범,김병식 한국막학회 2007 멤브레인 Vol.17 No.1

본 연구에서는 복막 투석 시스템에 있어서, 요소를 가수분해 후 발생하는 암모니아를 제거하기 위하여, 방사선 그라프트 중합법에 의해 다공성 중공사막에 술폰산기(SO3H)를 도입시킨 양이온 교환막(이때 얻어진 막을 SS막이라 함)을 합성하였다. 여기에 금속이온(Cu, Ni, Zn)을 이용하여 그라프트 체인을 가교시킨 이온가교형 양이온 교환막(이때 얻어진 막을 SS-M막이라 함)을 합성하여, SS막과 SS-M막의 투과 유속과 암모니아의 흡착에 대하여 고찰하였다. 술폰산기 밀도에 따라 순수투과 유속은 술폰산기 밀도가 높아짐에 따라 투과 유속이 급격히 감소하였으나, 금속 이온이 도입됨에 따라, 투과 유속이 빨라진다는 것을 알 수 있었다. SS막의 경우 암모니아 흡착은 이온교환기 용량에 따라 1 : 1로 흡착되었고, SS-M막 보다 높은 흡착량을 나타났다. 또한, SS막, SS-M막 모두 pH 9에서 가장 높은 흡착량을 나타냈다. In this research, the cation-exchange membrane (SS membrane) containing sulfonic acid group was prepared by radiation induced grafted polymerization onto a porous hollow fiber membrane to effectively remove ammonia which was produced by urea decomposition for peritoneum dialysis system. And the metal ionic cross-linking cation-exchange membrane (SS-M membrane) was prepared by the adsorption of metallic ions (Cu, Ni, Zn) to the SS membranes. The pure water flux and adsorption capacities of ammonia to SS and SS-M membranes were examined. The pure water flux of SS membrane decreased rapidly with the density of SO3H group increasing. As the metallic ions were adsorbed to the SS membrane, the pure water flux was increased. The adsorption capacities of ammonia at the SS membrane increased with increasing of density of SO3H group. The ion-exchange capacity of ammonia of the SS membrane was approximately proportional 1 : 1 to the density of SO3H group. The SS membrane had higher adsorption capacities than the SS-M membrane. The highest adsorption capacities of SS and SS-M membrane appeared the highest pH 9.

Surface modification of heterogeneous cation exchange membrane through simultaneous using polymerization of PAA and multi walled carbon nano tubes

A.R. Moghadassi,P. Koranian,S.M. Hosseini,M. Askari,S.S. Madaeni 한국공업화학회 2014 Journal of Industrial and Engineering Chemistry Vol.20 No.5

Polyvinylchloride based heterogeneous cation exchange membrane was modified by using in situ polymerization of polyacrylic acid and multi walled carbon nano tubes simultaneously. Spectra analysis confirmed graft polymerization decisively. SEM images illustrated that grafted-PAA/MWCNTs filled the cracks in membrane by simple gel network entanglement. Ion exchange capacity was improved by PAA/MWCNTs grafting in modified membranes. Membrane water content was decreased by PAA grafting and then showed increasing trend by using MWCNTs in modifier solution up to 0.1%wt. Water content was decreased again by more MWCNTs loading ratio. Grafted-PAA membranes showed lower membrane potential, transport number, selectivity and flux compared to pristine membrane in sodium chloride ionic solution. These parameters were decreased more by using MWCNTs up to 0.1%wt in modifier solution and then showed increasing trend by more MWCNTs concentration from 0.1 to 0.3%wt. All mentioned parameters were declined again by more increase in MWCNTs content from 0.3 to 1.0%wt. Results exhibited lower membrane selectivity for the modified membranes compared to pristine ones in bivalent ionic solution. The grafted-PAA/MWCNTs modified membranes also showed lower electrical resistance compared to unmodified ones. Obtained results showed different behavior for permeability in bivalent ionic solution compared to monovalent type.

Synthesis of Polyketone-g-Sodium Styrene Sulfonate Cation Exchange Membrane via Irradiation and Its Desalination Properties

김인식,황치원,김영중,Ali Canlier,정경석,황택성 한국고분자학회 2017 Macromolecular Research Vol.25 No.11

Using the radiation grafting technique, polyketone membranes were graft copolymerized with sodium styrene sulfonate (SSS) in the presence of additives such as Mohr’s salt and H2SO4. Fourier-transform infrared (FT-IR) spectroscopy was used to characterize the grafted membranes. Water uptake (WU), ion exchange capacity (IEC) and electrical resistance (ER) of the prepared membranes were measured in order to evaluate their physical properties The prepared membranes were applied to the membrane capacitive deionization (MCDI) process, in which their salt removal rates were evaluated and compared to those of CDI (capacitive deionization) process. The degree of grafting rose from 14.4% to 81.4% as the irradiation dose and the monomer concentration were increased. The water uptake ranged from 7.9% to 34.2%. The ionexchange capacity was observed between 0.43meq/g and 1.1meq/g, and the electrical resistance had values ranging from 12.2Ω·cm2 to 2.1Ω·cm2. The electrical resistance decreased as the ion-exchange capacity was extended. When the prepared cation exchange membrane was used in the MCDI process, the salt removal rate reached 87.6%, which was much higher than 28.8% of CDI process.