脱硫废液电渗析法再生用膜的研究
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摘要
采用苯乙烯(ST)和二乙烯苯(DVB)为原料，以浓硫酸为磺化剂，AgSO_4为磺化催化剂，制备用于脱硫废液NaHSO_3溶液再生的阳离子交换膜，并对膜的性能进行了测量。膜的含水率约29％；交换容量约2.09mol·kg~(-1)：膜面电阻约20Ω；膜电位约14.5mV，并由此计算了离子迁移数和膜的选择透过性。用自制的阳离子交换膜和市售的双极性离子交换膜组成膜对进行脱硫废液NaHSO_3溶液的电渗析再生实验，发现制膜时增大阳膜的磺化时间可以提高电渗析的效率；但磺化时间大于8h后，电渗析效率增长很小，并且膜有损坏迹象。作为对比，用购买的商品膜重复了以上实验过程。发现自制膜的电性能接近和超过商品膜，在外加电压31V，NaHSO_3溶液1mmol／L条件下，约0.5h后采用自制膜的系统电渗析效率超过商品膜。
One type of cation exchange membranes was made for the purpuse of electrodialysis process ,which regenerate NaHSO3 waste water desulfurized by membrane process. The cation exchange membrane was prepared by sulfonation of a preformed polymer film. The film of polystyrene(PS) and divinybenzene(DVB) used oil of vitriol as sulfonate reagent,Ag2SO4 as catalyst. The average water content of the membrane was 29%.The cation exchange capacity was about 2.09 mol kg-1.The membrane conductance was around 20 cm2, equilibrated in 0.1molL-1 NaCl solution. The membrane potential reached up to 14.5mV,equilibrated in 0.1molL-1Vo.2molL-1 KCl solution. Then calculated the ion transport number and permselectivity of the membrane by it. Experiments were carried out to regenerate NaHSO3 waste water by electrodialysis using this home-made membrane Found that increase the sulfonation time can enhance the efficiency of the electrodialysis process; but if sulfonation time exceeded 8 hour, the enhancement was very minute, and the memb
rane began to destroyed. Use bought membranes repeated the experiments above to compare with, then found the electro-performance of the home-made membranes was close to, even exceed bought membranes. In the condition of 31 V voltage,1mmol L-1 NaHSO3 solution, after 0.5 hour electrodialysis, the efficiency of home-made memebranes began to exceed that of bought membrane.
One type of cation exchange membranes was made for the purpuse of electrodialysis process ,which regenerate NaHSO3 waste water desulfurized by membrane process. The cation exchange membrane was prepared by sulfonation of a preformed polymer film. The film of polystyrene(PS) and divinybenzene(DVB) used oil of vitriol as sulfonate reagent,Ag2SO4 as catalyst. The average water content of the membrane was 29%.The cation exchange capacity was about 2.09 mol kg-1.The membrane conductance was around 20 cm2, equilibrated in 0.1molL-1 NaCl solution. The membrane potential reached up to 14.5mV,equilibrated in 0.1molL-1Vo.2molL-1 KCl solution. Then calculated the ion transport number and permselectivity of the membrane by it. Experiments were carried out to regenerate NaHSO3 waste water by electrodialysis using this home-made membrane Found that increase the sulfonation time can enhance the efficiency of the electrodialysis process; but if sulfonation time exceeded 8 hour, the enhancement was very minute, and the memb
rane began to destroyed. Use bought membranes repeated the experiments above to compare with, then found the electro-performance of the home-made membranes was close to, even exceed bought membranes. In the condition of 31 V voltage,1mmol L-1 NaHSO3 solution, after 0.5 hour electrodialysis, the efficiency of home-made memebranes began to exceed that of bought membrane.
引文
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2 钟秦．燃煤烟气脱硫脱硝工程实例．北京：化学工业出版社，2002
3 国家环境保护总局．2002中国环境公报
4 刑鹏．膜法烟气脱硫产物双极性膜电渗析再生的研究：[学位论文]，南京：南京理工大学，2004
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11 陈理．脱除烟气中SO_2和NO_x的新技术．化工环保，1997，17：336～341
12 曹连城．双极膜及其研究进展．化工科技市场，2002(8)：28～30
13 余立新，孟昭辉，林爱光等．双极性膜电渗析法在脱硫废液NaHSO_3再生过程中的应用研究．环境科学，1996，17(6)：40～42
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25 Graillon S, Persin F, Pourcelly G, et al. Development of electrodialysis with bipolar membrane for the treatment of concentrated nitrate effluents. Desalination, 1996, 107: 159～169
26 邵刚．膜法水处理技术．北京：冶金工业出版社，2000
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28 Juda W, McRea W A. Coherent ion-exchange gels and membrane. J Am Chem, 1950, 72: 1044～1054
29 方度，杨维驿．全氟离子交换膜—制法、性能和应用．北京：化学工业出版社．1993
30 刘建国，衣宝廉，王素力等．Nafion膜厚度对直接甲醇燃料电池性能的影响．电源技术，2002，26(1)：17～19
31 曾蓉，庞志成，朱鹤孙．Nafion膜表面改性—用等离子体聚合方法提高膜的阳离子选择性．高等学校化学学报，2001，22(4)：687～690
32 于春波，王玉江，华凯峰等．改性Nafionn膜在全固态二氧化硫气体传感器中的应用．分析化学，2002，30(4)：397～400
33 宋长军．旭硝子F-896与杜邦N-966-TX型离子交换膜运行实验情况．中国氯碱，2001(7)：19～20
34 赵国瑞．新型离子交换膜电解槽技术剖析—关于日本旭硝子公司的AZM-F2单极式离子交换．氯碱工业，1991(8)：10～12
35 王振堃．离子交换膜-制备、性能及应用．北京：化学工业出版社，1986
36 徐懋，赵春田，张贤等．聚丙烯微孔膜为基膜的离子交换膜及其制法．CN 1038562C，1998
37 Shahi V K., Thampy S K, Rangarajan R. Preparation and electrochemical characterization of
sulfonated interpolymer of polyethylene and styrene-divinylbenzenecopolymer membranes. Reactive & Functional Polymers, 2000, 46: 39～47
38 罗川南，杨勇．聚砜／聚醚砜相容性对合金膜结构和性能的影响．化学研究，2002，13(4)：30～33
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46 Wilhelm F G, Pünt I, Van der Vegt N F A, et al. Optimization strategies for the preparation of bipolar membranes with reduced salt ion leakage in acid-base eletrodialysis. Journal of Membrane Science, 2001, 182: 13～28
47 Lee, Lester T C, Dede, et al. High performance, quality controlled bipolar membrane. USP 4057481, 1977
48 Kedem, Ora, Warshawsky, et al. Supported, mechanically stable bipolar membrane for electrodialysis. USP 5288385, 1994
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2 钟秦．燃煤烟气脱硫脱硝工程实例．北京：化学工业出版社，2002
3 国家环境保护总局．2002中国环境公报
4 刑鹏．膜法烟气脱硫产物双极性膜电渗析再生的研究：[学位论文]，南京：南京理工大学，2004
5 Nagibin. Radiation-Chemical Method of Gas purification from SO_2 Radiate. Phys Chem 1992, 50 (4): 307～309.
6 Li G. The Experimental Facility & Results of Removal of SO_2 and NO_x in Flue Gases by the Electron Beam Process at SINR Academia SINICA. Radia Phys Chem. 1992, 40 (4): 295～300
7 郭东明．硫氮污染物防治工程技术及其应用．北京：化学工业出版社，2001
8 熊丹柳，邓修，戴干策．液膜法烟气脱硫试验．华东理工大学学报，1997，23(2)：156～161
9 熊丹柳，邓修，戴干策．中空纤维含浸液膜渗透器烟气脱硫．华东理工大学学报，1997，24(6)：623～626
10 金美芳，曹义铭，邢丹敏等．膜吸收法脱除二氧化硫．膜科学与技术，1999，19(3)：44～46
11 陈理．脱除烟气中SO_2和NO_x的新技术．化工环保，1997，17：336～341
12 曹连城．双极膜及其研究进展．化工科技市场，2002(8)：28～30
13 余立新，孟昭辉，林爱光等．双极性膜电渗析法在脱硫废液NaHSO_3再生过程中的应用研究．环境科学，1996，17(6)：40～42
14 保积庆，张启修．用膜电解法处理低浓度SO_2吸收液的三室电解槽材料的选择．湿法冶金，2002，21(4)：212～217
15 苏秦豫，刘丹，夏金法，戴琳，石宝珍．电渗析用于烟气脱硫吸收剂再生的研究．水处理技术，29(4)：230～232
16 Xu T, Yang W. Citric acid production by elecreodialysis with bipolar membranes. Chemical Engineering and Processing, 2002, 41: 519～524
17 Bailly M. Production of organic acids by bipolar electrodialysis: realizations and perspectives. Desalination, 2002, 144: 157～162
18 Lee E G, Moon S-H, Chang Y K, et al. Lactic acid recovery using two-stage electrodialysis and its modeling. Journal of Membrane Science, 1998, 145: 53～66
19 Grib H, Bonnal L, Sandeaux R, et al. Extraction of amphoteric amino acids by an electromembrane process-pH and electrical state control by electrodialysis with bipolar membranes. J Chem Technol Biotechnol, 1998, 73: 64～70
20 Novalic S, Kongbangkerd T, Kulbe K D. Recovery of organic acids with high molecular weight using a combined electrodialytic process. Journal of Membrane Science, 2000 (166): 99～104
21 Cauwenberg V, Peel J, Resbeut S, et al. Application of electrodialysis within fine chemistry. Separation and Purification Technology, 2001, 22: 115～121
22 林爱光，蒋维钧，余立新．双极性膜电渗析技术在维生素C生产中的应用研究．膜科学与技术，1998，18(5)：24～27
23 Bazinet L, Lamarche F, Ippersiel D. Bipolar-membrane electrodialysis: Applications of electrodialysis in the food industry. Trends in Food Science & Technology, 1998 (9): 107～113
24 余立新，郭庆丰，黄科等．极稀醋酸废水处理的双极性膜电渗析法．膜科学与技术，2000，20(2)：31～33
25 Graillon S, Persin F, Pourcelly G, et al. Development of electrodialysis with bipolar membrane for the treatment of concentrated nitrate effluents. Desalination, 1996, 107: 159～169
26 邵刚．膜法水处理技术．北京：冶金工业出版社，2000
27 徐铜文，杨伟华，张玉平等．双极膜在冶金工业中的应用．膜科学与技术，2002，22(5)：46～51
28 Juda W, McRea W A. Coherent ion-exchange gels and membrane. J Am Chem, 1950, 72: 1044～1054
29 方度，杨维驿．全氟离子交换膜—制法、性能和应用．北京：化学工业出版社．1993
30 刘建国，衣宝廉，王素力等．Nafion膜厚度对直接甲醇燃料电池性能的影响．电源技术，2002，26(1)：17～19
31 曾蓉，庞志成，朱鹤孙．Nafion膜表面改性—用等离子体聚合方法提高膜的阳离子选择性．高等学校化学学报，2001，22(4)：687～690
32 于春波，王玉江，华凯峰等．改性Nafionn膜在全固态二氧化硫气体传感器中的应用．分析化学，2002，30(4)：397～400
33 宋长军．旭硝子F-896与杜邦N-966-TX型离子交换膜运行实验情况．中国氯碱，2001(7)：19～20
34 赵国瑞．新型离子交换膜电解槽技术剖析—关于日本旭硝子公司的AZM-F2单极式离子交换．氯碱工业，1991(8)：10～12
35 王振堃．离子交换膜-制备、性能及应用．北京：化学工业出版社，1986
36 徐懋，赵春田，张贤等．聚丙烯微孔膜为基膜的离子交换膜及其制法．CN 1038562C，1998
37 Shahi V K., Thampy S K, Rangarajan R. Preparation and electrochemical characterization of
sulfonated interpolymer of polyethylene and styrene-divinylbenzenecopolymer membranes. Reactive & Functional Polymers, 2000, 46: 39～47
38 罗川南，杨勇．聚砜／聚醚砜相容性对合金膜结构和性能的影响．化学研究，2002，13(4)：30～33
39 叶震，刘丽，陈勇．聚砜／磺化聚砜共混及离子交换膜C_3H_6／C_3H_8渗透性能的研究．膜科学与技术，2002，22(5)：1～5
40 邢丹敏，刘富强，于景荣．磺化聚砜膜的燃料电池性能初步研究．膜科学与技术，2002，22(5)：12～16
41 张伟，戴干策．改性聚砜交联离子交换膜的合成．高分子学报，1998(5)：608～610
42 中科院有机化学研究所．聚苯醚阳离子交换膜研究报告，1974
43 全国电渗析技术交流会秘书组．电渗析技术资料选编．北京：中国建筑工业出版社，1976
44 陈翠仙，余立新，戴猷元．新膜及膜过程的研究现状及发展动向．水处理技术，1996，22(6)：307～313
45 廖尚志，莫剑雄．双极膜的制备．水处理技术，1997，23(3)：146～150
46 Wilhelm F G, Pünt I, Van der Vegt N F A, et al. Optimization strategies for the preparation of bipolar membranes with reduced salt ion leakage in acid-base eletrodialysis. Journal of Membrane Science, 2001, 182: 13～28
47 Lee, Lester T C, Dede, et al. High performance, quality controlled bipolar membrane. USP 4057481, 1977
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