Bipolar막에서 전류/전압곡선에 미치는 중간계면 성분의 영향

정세일; 유철휘; 황용구; 강안수; Se Il Jung; Cheol Hwi Ryu; Yong Koo Hwang; An Soo Kang

HWAHAK KONGHAK, Vol.40, No.4, 474-481, August, 2002

Export Citation

Bipolar막에서 전류/전압곡선에 미치는 중간계면 성분의 영향

Effect of Intermediate Component on Current-Voltage Curves of a Bipolar Membrane

정세일, 유철휘, 황용구, 강안수 ^†

명지대학교 화학공학과, 용인 449-728

Se Il Jung, Cheol Hwi Ryu, Yong Koo Hwang, and An Soo Kang^†

Department of Chemical Engineering, Myongji University, Yongin 449-728, Korea

E-mail:

초록

Bipolar막을 이용한 전기투석공정은 에너지 효율이 높고, 매우 경제적이며 다양한 용도를 갖고 있다. 이 공정은 성능이 좋은 bipolar막의 제조 및 공정의 개선으로 폐수처리, 고가의 순수한 유기 및 무기산의 제조 등에 그 적용 범위가 확대되고 있는 추세이다. 그러나, bipolar막을 이용한 전기투석 공정은 bipolar막이 매우 고가로 경제성과 bipolar막을 이용한 공정을 최적화하기에는 현재 water-splitting 메커니즘에 대한 이해가 부족하다는 문제점이 있으며, 이에 대한 연구와 막의 개발이 시급한 형편이다. 본 연구에서는 polysulfone을 poly(phenylene sulfide sulfone)와 공중합시켜 block copolymer를 제조하였고 sulfonation과 amination을 통하여 각각 양/음이온교환막을 제조하였다. 양/음이온 교환막 제조 시 전기화학적 특성과 물리적 특성을 고려하여 최적 제막조건을 확립하였고, 이를 적층하여 bipolar막을 제조하였다. Bipolar막의 최적조건을 찾기 위해 중간계면 성분의 변화에 따른 전류/전압 곡선을 측정하였고, 전기투석의 응용으로서 pH 변화를 측정하여 우수한 bipolar막을 제조하였다. 중간계면에 변화를 주어 bipolar막 제조 시 아민기가 도입된 bipolar막의 성능이 좋았고, 특히 3차 아민기가 도입된 bipolar막이 가장 우수한 water-splitting 특성을 보였으며, 100 mA/cm(2)의 전류밀도에서 2.4 V의 막전위를 보였다.

Electrodialysis process with bipolar membrane is economically very attractive and has a multitude of interesting potential applications. Although the process expand applications such as waste water treatment, and recovery of pure organic and inorganic acids with the efficient bipolar membrane, the large scale utilization of bipolar membrane is still limited by unsatisfactory membrane properties and by a lack of application knowhow. In this study, the block copolymer(BPSf) was prepared by copolymerization of polysulfone(PSf) and poly(phenylene sulfide sulfone)(PPSS). The cation exchange membranes were prepared by the sulfonation of BPSf with chlorosulfonic acid and the anion exchange membranes were prepared by the chloromethylation by chloromethyl ether and the amination by triethyl amine. The bipolar membranes were fabricated by stacking anion exchange membrane over cation one with the conditions of good electrochemical characteristics and physical properties. The influence of intermediate layer components on the bipolar membrane properties such as current-voltage curve and pH was investigated, and the components were varied by pasting non-woven cloth, various polymers, and amine groups. Among the various bipolar membranes, the membranes prepared by tertiary amine group exhibited the best water-splitting effect and 2.4 V of membrane potential at 100 mA/cm(2) of current density.

Keywords:Bipolar Membrane;Polysulfone;Electrodialysis;Current-Voltage Curve;Intermediate Component

[References]

Kemperman AJB, "Handbook on Bipolar Membrane Technology," Twente Univ. Press, Enschede (2000)
Mafe S, Manzanares TA, Phys. Rev., A, 42, 6245 (1990)
Ramirez P, Aguilella VM, Manzanares JA, Mafe S, J. Membr. Sci., 73, 191 (1992)
Tanioka A, Shimizu K, Miyasaka K, Zimmer HJ, Minoura N, Polymer, 37(10), 1883 (1996)
Hinke E, Staude E, J. Appl. Polym. Sci., 42, 2951 (1991)
Cherif AT, Molenat J, Elmidaoui A, J. Appl. Electrochem., 27(9), 1069 (1997)
Mani KN, Chlanda FP, Byszewski CH, Desalination, 68, 149 (1988)
Elmoussaoui R, Pourcelly G, Maeck M, Hurwitz HD, Gavach C, J. Membr. Sci., 90(3), 283 (1994)
Shimizu K, Tanioka A, Polymer, 38(21), 5441 (1997)
Simons R, Electrochim. Acta, 30, 275 (1985)
Simons R, Electrochim. Acta, 31, 1175 (1986)
Simons R, J. Membr. Sci., 78, 13 (1993)
Simons R, J. Membr. Sci., 82, 65 (1993)
Sridhar S, J. Membr. Sci., 113(1), 73 (1996)
Strathmann H, Rapp HJ, Bauer B, Bell CM, Desalination, 90, 303 (1993)
Strathmann H, Krol JJ, Rapp HJ, Eigenberger G, J. Membr. Sci., 125(1), 123 (1997)
Strathmann H, Membr. J., 11, 97 (2001)
Chou TJ, Tanioka A, J. Colloid Interface Sci., 212(2), 576 (1999)
Hao JH, Chen CX, Li L, Yu LX, Jiang WJ, J. Appl. Polym. Sci., 80(10), 1658 (2001)
Aritom TD, Boomgaard TVD, Strathmann H, Desalination, 104, 13 (1996)
Chou TJ, Tanioka A, J. Phys. Chem. B, 102(40), 7866 (1998)
Mulder M, "Basic Principles of Membrane Technology," Kluwer Academ. Publishers, Boston (1996)
Pouchert CJ, "The Aldrich Library of FT-IR Spectra," 1st ed., Aldrich Chem. Co., Wisconsin (1998)
Lim HC, Kang AS, Membr. J., 10, 66 (2000)
Roncail J, J. Am. Chem. Soc., 97, 173 (1997)

[Related Articles]

[1] Kemperman AJB, "Handbook on Bipolar Membrane Technology," Twente Univ. Press, Enschede (2000)

[2] Mafe S, Manzanares TA, Phys. Rev., A, 42, 6245 (1990)

[3] Ramirez P, Aguilella VM, Manzanares JA, Mafe S, J. Membr. Sci., 73, 191 (1992)

[4] Tanioka A, Shimizu K, Miyasaka K, Zimmer HJ, Minoura N, Polymer, 37(10), 1883 (1996)

[5] Hinke E, Staude E, J. Appl. Polym. Sci., 42, 2951 (1991)

[6] Cherif AT, Molenat J, Elmidaoui A, J. Appl. Electrochem., 27(9), 1069 (1997)

[7] Mani KN, Chlanda FP, Byszewski CH, Desalination, 68, 149 (1988)

[8] Elmoussaoui R, Pourcelly G, Maeck M, Hurwitz HD, Gavach C, J. Membr. Sci., 90(3), 283 (1994)

[9] Shimizu K, Tanioka A, Polymer, 38(21), 5441 (1997)

[10] Simons R, Electrochim. Acta, 30, 275 (1985)

[11] Simons R, Electrochim. Acta, 31, 1175 (1986)

[12] Simons R, J. Membr. Sci., 78, 13 (1993)

[13] Simons R, J. Membr. Sci., 82, 65 (1993)

[14] Sridhar S, J. Membr. Sci., 113(1), 73 (1996)

[15] Strathmann H, Rapp HJ, Bauer B, Bell CM, Desalination, 90, 303 (1993)

[16] Strathmann H, Krol JJ, Rapp HJ, Eigenberger G, J. Membr. Sci., 125(1), 123 (1997)

[17] Strathmann H, Membr. J., 11, 97 (2001)

[18] Chou TJ, Tanioka A, J. Colloid Interface Sci., 212(2), 576 (1999)

[19] Hao JH, Chen CX, Li L, Yu LX, Jiang WJ, J. Appl. Polym. Sci., 80(10), 1658 (2001)

[20] Aritom TD, Boomgaard TVD, Strathmann H, Desalination, 104, 13 (1996)

[21] Chou TJ, Tanioka A, J. Phys. Chem. B, 102(40), 7866 (1998)

[22] Mulder M, "Basic Principles of Membrane Technology," Kluwer Academ. Publishers, Boston (1996)

[23] Pouchert CJ, "The Aldrich Library of FT-IR Spectra," 1st ed., Aldrich Chem. Co., Wisconsin (1998)

[24] Lim HC, Kang AS, Membr. J., 10, 66 (2000)

[25] Roncail J, J. Am. Chem. Soc., 97, 173 (1997)