吡啶及其衍生物制备阴离子交换膜以及传质特性的研究
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摘要
离子交换膜是一种膜状的离子交换树脂。其用途非常广泛,其中比较重要的有海水淡化、苦咸水脱盐等。然而分离同电荷同价态的离子仍存在较大的困难。
离子交换膜的种类不同,相应的制备方法也不尽相同。其中均相阴离子交换膜的制备比较困难,原因之一是氯甲基化时需要使用剧毒物质—氯甲醚,因此探索不使用氯甲醚而制备阴离子交换膜的路线非常必要。同时随着工业生产对离子交换膜要求的提高,对具有高热稳定性、化学稳定性、机械稳定性以及较低膜电阻的高选择性膜的需求也日益增多。
用吡啶或其衍生物(4—乙烯基吡啶)对甲基溴化的聚2,6—二甲基—1,4—苯撑氧(BPPO)基膜进行胺化,可以得到系列阴离子交换膜。所制备的阴膜对各种具有不同水合自由能的一价阴离子有着较好的分离效果。
本论文共包括六章。第一章是绪论,对离子交换膜作简要介绍,包括离子交换膜的分类和制备以及应用与发展。最后提出本论文的设计思想和论文的主要工作。
第二章介绍了吡啶对BPPO基膜进行改性制备阴离子交换膜以及制备方法的优化。选择吡啶作为胺化试剂是由于吡啶的亲水亲油平衡值较三甲胺的小,所制备的阴膜也比由三甲胺制备的阴膜具有较强的憎水性。还讨论了所得阴离子交换膜的基本性质。
第三章介绍了4—乙烯基吡啶对BPPO基膜进行改性制备阴离子膜。选择4—乙烯基吡啶作为胺化试剂可以在引入吡啶基团的同时避免吡啶对BPPO基膜的腐蚀。该方法制备的阴膜具有较强的憎水性。讨论了所制备阴膜的基本性质,还比较了吡啶及4—乙烯基吡啶改性所制备膜的热稳定性和化学稳定性。
第四章通过实验进一步探讨了吡啶及其衍生物(4—乙烯基吡啶)所制备阴离子交换膜对单价阴离子的选择渗透性。并讨论了阴膜憎水性、阴离子的水合半径及其水合能对离子在膜内选择渗透性的影响。
第五章提出了一种通过测定电导率推测离子交换膜性质的简单方法。该方法基于离子交换膜的某些性能间的密切联系,以一组商业离子膜和一些本实验室制备的膜为例进行讨论。其正确性通过方程的线性,计算所得参数与所报道参数间的比较,以及所推测的结构参数的合理性进行验证。
第六章是对全文的总结。通过前面的实验和理论分析,得出一些对离子交换膜制备有意义的结论。
Ion exchange membrane is a type of ion exchange resin in the shape of membrane.They are used in many fields,such as desalination of seawater and saline water;however,there is still a great challenge in exploring high-permselectivity membranes so as to separate ions of a sigh and/or charge.
The preparing methods of ion exchange membranes vary with the species of membranes.Among these methods,the preparation of homogeneous anion exchange membranes is one of the most difficult since chloromethyl ether,a extremely toxic chemical,is often employed for chloromethylization.So it is necessary to find a route of preparing anion exchange membrane without using chloromethyl ether.Meanwhile,there are growing demands for the ion exchange membranes with high thermal,chemical,and mechanical stability,low membrane resistance,and high permselectivity.
When pyridine or its derivative(4-vinylpyridine)is used to aminate bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide)(BPPO),a series of anion exchange membranes can be obtained.The prepared anion exchange membranes can effectively separate some monovalent anions with different hydration free energy.
The dissertation comprises six chapters.ChapterⅠgives an overview on the research background-ion exchange membrane:classification,preparation, application,and development.Then the research ideas and outlines are purposed.
In chapterⅡ,a series of anion exchange membranes are successfully obtained by amination of pyridine on BPPO base membranes.Since pyridine is lower in hydrophilic-lipophilic balance(HLB)value than trimethylamine(TMA), the membranes prepared from pyridine will be higher in hydrophobicity than those prepared from TMA.The properties of the prepared anion exchange membranes are systematically investigated.
In chapterⅢ,a series of anion exchange membranes are successfully obtained by amination of 4-vinylpyridine on BPPO base membranes.The use of 4-vinylpyridine can introduce pyridinium groups into the base membrane and avoid the degradation of pyridine in the base membrane.The hydrophobicity of the obtained membrane is relatively high.The properties of the prepared anion exchange membranes are systematically studied.The thermal and chemical stability of the membranes prepared from pyridine and 4-vinylpyridine respectively are compared.
In chapterⅣ,the permselectivities of monovalent anions in the membranes prepared from pyridine or 4-vinylpyridine are further studied by experiments. And the factors impacting on membrane permselectivity to anions are fully discussed:the hydrophobicity of anion exchange membranes,and the Stokes radii and hydration free energies of the anions.
A simple evaluation of microstructure and transport parameters through membrane conductivity is presented in chapterⅤ.The method is based on the relation between these properties.The method is exemplified through a series of commercial membranes and some lab-made membranes.It is also validated on the basis of the linearity of equations,the comparison between calculated and reported parameters,and the reasonability of the predicted structural parameters.
ChapterⅥis a summary of the dissertation.Some important conclusions for preparation of the anion exchange membranes are underlined.
离子交换膜的种类不同,相应的制备方法也不尽相同。其中均相阴离子交换膜的制备比较困难,原因之一是氯甲基化时需要使用剧毒物质—氯甲醚,因此探索不使用氯甲醚而制备阴离子交换膜的路线非常必要。同时随着工业生产对离子交换膜要求的提高,对具有高热稳定性、化学稳定性、机械稳定性以及较低膜电阻的高选择性膜的需求也日益增多。
用吡啶或其衍生物(4—乙烯基吡啶)对甲基溴化的聚2,6—二甲基—1,4—苯撑氧(BPPO)基膜进行胺化,可以得到系列阴离子交换膜。所制备的阴膜对各种具有不同水合自由能的一价阴离子有着较好的分离效果。
本论文共包括六章。第一章是绪论,对离子交换膜作简要介绍,包括离子交换膜的分类和制备以及应用与发展。最后提出本论文的设计思想和论文的主要工作。
第二章介绍了吡啶对BPPO基膜进行改性制备阴离子交换膜以及制备方法的优化。选择吡啶作为胺化试剂是由于吡啶的亲水亲油平衡值较三甲胺的小,所制备的阴膜也比由三甲胺制备的阴膜具有较强的憎水性。还讨论了所得阴离子交换膜的基本性质。
第三章介绍了4—乙烯基吡啶对BPPO基膜进行改性制备阴离子膜。选择4—乙烯基吡啶作为胺化试剂可以在引入吡啶基团的同时避免吡啶对BPPO基膜的腐蚀。该方法制备的阴膜具有较强的憎水性。讨论了所制备阴膜的基本性质,还比较了吡啶及4—乙烯基吡啶改性所制备膜的热稳定性和化学稳定性。
第四章通过实验进一步探讨了吡啶及其衍生物(4—乙烯基吡啶)所制备阴离子交换膜对单价阴离子的选择渗透性。并讨论了阴膜憎水性、阴离子的水合半径及其水合能对离子在膜内选择渗透性的影响。
第五章提出了一种通过测定电导率推测离子交换膜性质的简单方法。该方法基于离子交换膜的某些性能间的密切联系,以一组商业离子膜和一些本实验室制备的膜为例进行讨论。其正确性通过方程的线性,计算所得参数与所报道参数间的比较,以及所推测的结构参数的合理性进行验证。
第六章是对全文的总结。通过前面的实验和理论分析,得出一些对离子交换膜制备有意义的结论。
Ion exchange membrane is a type of ion exchange resin in the shape of membrane.They are used in many fields,such as desalination of seawater and saline water;however,there is still a great challenge in exploring high-permselectivity membranes so as to separate ions of a sigh and/or charge.
The preparing methods of ion exchange membranes vary with the species of membranes.Among these methods,the preparation of homogeneous anion exchange membranes is one of the most difficult since chloromethyl ether,a extremely toxic chemical,is often employed for chloromethylization.So it is necessary to find a route of preparing anion exchange membrane without using chloromethyl ether.Meanwhile,there are growing demands for the ion exchange membranes with high thermal,chemical,and mechanical stability,low membrane resistance,and high permselectivity.
When pyridine or its derivative(4-vinylpyridine)is used to aminate bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide)(BPPO),a series of anion exchange membranes can be obtained.The prepared anion exchange membranes can effectively separate some monovalent anions with different hydration free energy.
The dissertation comprises six chapters.ChapterⅠgives an overview on the research background-ion exchange membrane:classification,preparation, application,and development.Then the research ideas and outlines are purposed.
In chapterⅡ,a series of anion exchange membranes are successfully obtained by amination of pyridine on BPPO base membranes.Since pyridine is lower in hydrophilic-lipophilic balance(HLB)value than trimethylamine(TMA), the membranes prepared from pyridine will be higher in hydrophobicity than those prepared from TMA.The properties of the prepared anion exchange membranes are systematically investigated.
In chapterⅢ,a series of anion exchange membranes are successfully obtained by amination of 4-vinylpyridine on BPPO base membranes.The use of 4-vinylpyridine can introduce pyridinium groups into the base membrane and avoid the degradation of pyridine in the base membrane.The hydrophobicity of the obtained membrane is relatively high.The properties of the prepared anion exchange membranes are systematically studied.The thermal and chemical stability of the membranes prepared from pyridine and 4-vinylpyridine respectively are compared.
In chapterⅣ,the permselectivities of monovalent anions in the membranes prepared from pyridine or 4-vinylpyridine are further studied by experiments. And the factors impacting on membrane permselectivity to anions are fully discussed:the hydrophobicity of anion exchange membranes,and the Stokes radii and hydration free energies of the anions.
A simple evaluation of microstructure and transport parameters through membrane conductivity is presented in chapterⅤ.The method is based on the relation between these properties.The method is exemplified through a series of commercial membranes and some lab-made membranes.It is also validated on the basis of the linearity of equations,the comparison between calculated and reported parameters,and the reasonability of the predicted structural parameters.
ChapterⅥis a summary of the dissertation.Some important conclusions for preparation of the anion exchange membranes are underlined.
引文
[1]李基森,许景文,徐元耀等.北京:科学出版社,1977
[2]王振坤编.离子交换膜-制备、性能及应用.北京:科学出版社,1985
[3]张维润等著.电渗析工程学.北京:科学出版社,1995
[4]徐铜文编.膜化学与技术教程.合肥:中国科学技术大学出版社,2003
[5]M.Y.Kariduraganavar,R.K.Nagarale,A.A.Kittur,S.S.Kulkarni,Desalination 197(2006)225-246
[6]R.K.Nagarale,G.S.Gohil,Vinod K.Shahi*,Advances in Colloid and Interface Science 119(2006)97-130
[7]K.Hideo,K.Tsuzura,H.Shimizu,Ion exchange membranes,in:K.Dorfner(Ed.),Ion Exchangers,Walter de Gruyter,Berlin,1991
[8]H.Strathmann,Electrodialysis and related processes,in:R.D
[9]W.Ostwald,Elektrische eigenschaften halbdurchl"assiger scheidewainde,Z.Phys.Chem.6(1890)71
[10]L.Michaelis,A.Fujita,The electric phenomen and ion permeability of membranes.Ⅱ.Permeability of apple peel,Biochem.Z.158(1925)28
[11]K.S"ollner,Uber mosaikmembranen,Biochem.Z.244(1932)390
[12]H..Wassenegger,K.Jaeger,Effecting cation-exchange in removing calcium from hard waters,U.S.Patent 2,204,539(1940)
[13]K.H.Meyer,H.Strauss,La perm'eabilit'e des membranes Ⅵ,sur le passage du courant 'electrique a travers des membranes s'elective,Helv.Chim.Acta 23(1940)795
[14]M.Juda,W.A.McRac,Coherent ion-exchange gels and membranes,J.Am.Chem.Soc.72(1950)1044
[15]W.G.Grot,Laminates of support material and fluorinated polymer containing pendant side chains containing sulfonyl groups.U.S.Patent 3,770,567(1973)
[16]F.P.Chlanda,L.T.C.Lee,K.J.Liu,Bipolar membranes and method of making same,U.S.Patent 4,116,889(1976)
[17]G.Pourcelly,C.Gavach,Electrodialysis water splitting-application of electrodialysis with bipolar membranes,in:A.J.B.Kemperman(Ed.),Handbook on Bipolar Membrane Technology,Twente University Press,Enschede,2000,pp.17-46
[18]T.W.Xu,Development of bipolar membrane-based process,Desalination 140(2001)247
[19]G.Daufin,J.P.Escudier,H.Carrere,S.Berot,L.Fillaudeau,M.Decloux,Recent emerging applications of membrane processes in the food and dairy industry,Food Bioproducts Process.79(2001)89
[20]T.Tarvainen,B.Svarfvar,S.Akerman,J.Savolaincn,M.Karhu,P.Paronen,K.Jarvinen,Drug release from a porous ion exchange membrane in vitro,Biomaterials 20(1999)2177
[21]Y.H.Kim,S.H.Moon,Lactic acid recovery from fermentation broth using one-stage electrodialysis,J.Chem.Technol.Biotechnol.76(2001)169
[22]G.Saracco,Ionic membrane technologies for the recovery of valuable chemicals from waste waters,Ann.Chim.Rome 93(2003)817
[23]L.Bazinet,F.Lamarche,D.Ippersiel,Bipolar membrane electrodialysis:applications of electrodialysis in the food industry,Trends Food Sci.Technol.9(1998)107
[24]T.W.Xu,Electrodialysis processes with bipolar membranes in environmental protection-a review,Resour.Conserv.Recycl.37(2002)1
[25]叶婴齐,李仲钦,水处理技术,1990,16(2):119-124
[26]江维达,李东.CN 87 104382.A.1981
[27]袁业明.水处理技术,1995,21:142-145
[28]谭春红,许志立,杨向民.膜科学与技术,1996,16:20-24
[29]何炳林,徐铜文,李向华.离子交换与吸附,1998,14(1):86-91
[30]Tongwen Xu,Ion exchange membranes:State of their development and perspective,Journal of Membrane Science 263(2005)1-29
[31]葛道才,膜科学与技术,1989,9:26-30
[32]T W Xu,W H Yang,Journal of Membrane Science,2001,183(2):193-200
[33]T W Xu,W H Yang,Journal of Membrane Science,2001,190:159-166
[34]T W Xu,W H Yang,Journal of Membrane Science,2002,199:203-210
[35]Lin M C,Takai N,Journal of Membrane Science,1994,88:77-83
[36]Sata T,Yamane Y,Matsusaki K,Journal of Polymer Science,1998,A36:49-58
[37]A M Mika,R F Childs,J M Dickson,B E McCarry and D R Gagnon,Journal of Membrane Science,1995,108:37-56
[38]D M Stachera,R F Childs,A M Mika and J M Dickson,Journal of Membrane Science,1998,148:119-127
[39]H Strathmann.Electrodialysis.In Membrane Seperations Technology-Principles and Applications,R D Noble and S A Stem(Eds.),Iland:Elseviver Press,1995
[40]R Yamane,T Izuo and Y Mizutani.Denkikagaku,1965,33(8):589-593
[41]W Gudernatsch,Ch Krumbholz and H Strathmann.In Proc.6th Intl.Symp.on Synthetic Membranes in Science and Technology,1989,Seot 4-8,Tubingen,Germany,pp223-226
[42]B Bauer,F J Gerner,H Strathmann.Desalination,1988,88:279-292
[43]D J Connolly,W F Gresham.1966,U.S.Patent 3,282,875
[44]Tongwen Xu,Keyan Hu,Separation and Purification Technology 40(2004)231-236
[1] G. Saracco, Ann. Chim. Rome 93 (2003) 817-826
[2] J.D. Way, R.D. Noble, D.L. Reed, G.M. Ginley, L.A. Jarr, AIChE J. 33 (1987) 480-487.
[3] D. Langevin, M. Pinoche, E. S'el'egny, M. M'etayer, R. Roux, J. Membr. Sci. 82 (1-2) (1993) 51-63.
[4] K. Adachi, W. Hu, H. Mastsumoto, K. Ito, A. Tanioka, Polymer 39 (11) (1998) 2315-2323.
[5] S. Srinivasan, E.A. Ticianelli, C.R. Derouin, A. Rendondo, J. Power Sources 22 (3-4) (1988) 359-375.
[6] H. Wang, G.A. Capuano, J. Electrochem. Soc. 145 (3) (1998) 780-784.
[7] A. Yasuda, N. Yamaga, K. Doi, T. Fujioka, S. Kusanagi, Solid State Ionics 40-1 (1990) 476-479.
[8] R. Rautenbach, W. Kopp, Desalination 65 (1987) 241.
[9] K. Kneifel, G. Luhrs, Desalination 68 (1988) 203.
[10] V.K. Indusekhar, G.S. Trivedi, B. Shah, Desalination 84 (1-3) (1991) 213-221.
[11] R.B. Meller, J. Ronnenberg, W.H. Campbell, S. Diekmann, Nature 355 (1992) 717-719.
[12] S. Jankovic, Manual de chimie de l'environnement, O.M.S. Geneve, 1974, p. 251.
[13] M. Hichour, F. Persin, J. Sandeaux, C. Gavach, Sep. Purif. Technol. 18 (2000) 1-11.
[14] A. Eyal, O. Kedem, J. Membr. Sci. 38 (1998) 101-111.
[15] T. Sata, J. Membr. Sci. 167 (2000) 1-31.
[16] T. Sata, T. Yamaguchi, K. Matsusaki, J. Phys. Chem. 99 (1995) 12875-12882.
[17] T. Sata, Y. Yamane, K. Matsusaki, J. Polym. Sci.: Part A Polym. Chem. 36 (1998) 49-58.
[18] T. Sata, S. Nojima, K. Katsusaki, Polymer 40 (1999) 7243-7249.
[19] T. Sata, S. Nojima, J. Polym. Sci.: Part B Polym. Phys. 37 (1999) 1773-1785.
[20] A. Blair, N. Kazerouni, Cancer Causes Control 8 (1997) 473-490.
[21] International Agency for Research on Cancer, Some Aromatic Amines, Hydrazine and Related Substances, Nnitroso Compounds and Miscellaneous Alkylating Agents, vol. 4, IARC, IARC Monogr Eval Carcinog Risks Humans, Lyon, France, 1974, pp. 231-245.
[22] T.W. Xu, W.H. Yang, J. Membr. Sci. 190 (2001) 159-166.
[23] T.W. Xu, F.F. Zha, J. Membr. Sci. 199 (2002) 203-210.
[24] T.W. Xu, Z.M. Liu, W.H. Yang, J. Membr. Sci 249 (2005) 183-191.
[25]T.W.Xu,W.H.Yang,J.Hazard.Mater.B 109(2004)157-164.
[26]J.X.Mo,S.M.Liu,Technol.Water Treat.8(1982)5(in Chinese).
[27]Q.Xue,Spectroscopy Methodology in Polymer Structure,Press of Senior Education of China,Beijing,1995,pp.6-60.
[28]T.W.Xu,W.H.Yang,B.L.He,Chem.Eng.Sci.56/18(2001)5343-5350.
[29]B.J.Robbins,R.W.Field,S.T.Kolaczkowski,A.D.Lockett,J.Membr.Sci.118(1996)101-110.
[1]Y.Li,T.W.Xu,M.Gong,J.Membr.Sci.279(1-2)(2006)200-208
[2]T.W.Xu and K.Y.Hu,Sep.Purif.Tech.40(2004)231-236.
[3]T.W.Xu,Z.M.Liu,W.H.Yang,J.Membr.Sci 249(2005)183-191.
[4]T.W.Xu,W.H.Yang,J.Membr.Sci.190(2001)159-166.
[5]M.S.Kang,Y.J.Choi,and S.H.Moon,AIChE J.49(2003)3213-3220.
[6]T.Sata,S.Nojima,K.Katsusaki,Polymer 40(1999)7243-7249.
[7]D.Wu,R..Q.Fu,T.W.Xu,L.Wu,W.H.Yang,J.Membr.Sci.DOI:10.1016/j.memsci.2007.11.042
[8]J.Fang,P.K.Shen,J.Membr.Sci.285(2006)317-322
[9]T.Sata,T.Yamaguchi,K.Matsusaki,J.Phys.Chem.99(1995)12875-12882.
[10]T.Sata,Y.Yamane,K.Matsusaki,J.Polym.Sci.:Part A Polym.Chem.36(1998)49-58.
[11]J.X.Mo,S.M.Liu,Technol.Water Treat.8(1982)5(in Chinese).
[12]T.W.Xu,W.H.Yang,and B.L.He,Chem.Eng.Sci.56/18(2001)5343-5350.
[1] R.K. Nagarale, G.S. Gohil, V.K. Shahi, Adv. Colloid 348 Interface Sci. 119 (2006) 97-130.
[2] T.W. Xu, K.Y. Hu, Sep. Purif. Technol. 40 (2004) 231-236.
[3] Y. Li, T.W. Xu, M. Gong, J. Membr. 371 Sci. 279 (1-2) (2006) 200-208.
[4] T.B. Qian (Ed.), Applications of Ion Exchange Agents, Press of Science 377 and Technology of Tianjin, Tianjin, 1984, pp. 50-51.
[5] T. Sata, J. Membr. Sci. 167 (2000) 1-31.
[6] T. Sata, T. Yamaguchi, K. Kawamura, K. Matsusaki, J. Chem. Soc, Faraday Trans. 93 (1997) 381 457-462.
[7] T.W. Xu, Z.M. Liu, W.H. Yang, J. Membr. Sci 249 (2005) 385 183-191.
[8] D.N. Amang, S. Alexandrova, P. Schaetzel, Chem. Eng. J. 99 388 (2004) 69-76.
[9] Z. Palaty, A. Zakova, Desalination 160 (2004) 51-66.
[10] Y. Marcus, Ion Solvation, John Wiley and Sons, New York, 1985, pp. 398 107-109.
[11] T. Sata, T. Yamaguchi, K. Matsusaki, J. Phys. Chem. 99 (1995) 12875-12882.
[12] T. Sata, Y. Yamane, K. Matsusaki, J. Polym. Sci.: Part A Polym. Chem. 36 (1998) 49- 357 58.
[13] S. Koizumi, T. Imato, N. Ishibashi, J. Membr. Sci. 132 (1997) 149-158.
[14] T. Sata, S. Nojima, J. Polym. Sci.: Part B Polym. Phys. 37 (1999) 1773-1785.
[15] T. Sata, Y. Kakuyama, K. Matsusaki, Y. Kagiyama, F. Kishimoto, Bull. Soc. Sea Water Sci. Jpn. 50(1996)449-455.
[16] D.N. Amang, S. Alexandrova, P. Schaetzel, Desalination 159 (2003) 393 267-271.
[17] Y. Li, T.W. Xu, Sep. Purif. Tech. DOI: 10.1016/j.seppur.2007.12.009
[1]H.Strathmarm,Ion-Exchange Membrane Separation Processes,Elsevier,Amsterdam,2004.
[2]T.W.Xu,J.Membr.Sci.263(2005)1-29.
[3]C.H.Huang,T.W.Xu,Environ.Sci.Technol.40(17)(2006)5233-5243.
[4]S.Koter,A.Warszawski,Pol.J.Environ.Stud.9(2000)45-56.
[5]R.K.Nagarale,G.S.Gohil,V.K.Shahi,Adv.Colloid Inter.Sci.119(2006)97-130.
[6]S.Sridhar,J.Membr.Sci.113(1996)73-79.
[7]C.H.Huang,T.W.Xu,Y.P.Zhang,Y.H.Xue,G.W.Chen,J.Membr.Sci.288(2007)1-12.
[8]M.S.Kang,S.H.Cho,S.H.Kim,Y.J.Choi,S.H.Moon,J.Membr.Sci.222(2003)149-161.
[9]I.N.Widiasa,P.D.Sutrisna,I.G.Wenten,Sep.Purif.Technol.39(2004)89-97.
[10]F.N.Xu,C.Innocent,G.Pourcelly,Sep.Purif.Technol.43(2005)17-24.
[11]C.Fargues,B.Broyart,M.Benmami,M.L.Lameloise,Sep.Sci.Technol.41(2006)359-377.
[12]A.Oehmen,R.Viegas,S.Velizarov,M.A.M.Reis,J.G.Crespo,Desalination 199(1-3)(2006)405-407.
[13]A.A.Khan,Inamuddin,Sens.Actuators B:Chem.120(1)(2006)10-18.
[14]B.Auclair,V.Nikonenko,C.Larchet,M.M'etayer,L.Dammak,J.Membr.Sci.195(2002)89-102.
[15]L.Michaeli,O.Kedem,Trans.Faraday Soc.57(1961)1185.
[16]O.Kedem,A.Katchalsky,Trans.Faraday Soc.59(1963)1918.
[17]R.Paterson,C.Gardner,J.Chem.Soc.A 13(1971)2254.
[18]O.Kedem,M.Perry,J.Membr.Sci.14(1983)249-262.
[19]A.Narebska,S.Koter,W.Kujawski,Desalination 51(1984)3-17.
[20]O.Kedem,J.Membr.Sci.206(2002)333-340.
[21]N.P.Gnusin,N.P.Berezina,O.A.Demina,N.A.Kononenko,Russ.J.Electrochem.32(1996)154-163.
[22]V.I.Zabolotsky,V.V.Nikonenko,J.Membr.Sci.79(1993)181-198.
[23]N.Berezina,N.Gnusin,O.Dyomina,S.Timofeyev,J.Membr.Sci.86(1994)207-229.
[24]N.P.Berezina,S.V.Timofeyev,O.A.Dyomina,A.N.Ozerin,A.V.Rebrov,Elektrokhimiya(Russ.J.Electrochem.)28(1992)1050.
[25]N.P.Gnusin,N.P.Berezina,N.A.Kononenko,O.A.Dyomina,J.Membr.Sci.243(2004)301-310.
[26] C. Larchet, L. Dammak, B. Auclair, S. Parchikov, V. Nikonenko, New J. Chem. 28(2004)1260-1267.
[27] J.H. Choi, S.H. Kim, S.H. Moon, J. Colloid Interf. Sci. 241 (2001) 120-126.
[28] V. Punita, P. Vyas, R. Ray, S.K. Rangarajan, Adhikary, J. Phys. Chem. B 106 (2002) 11910-11915.
[29] N.P. Gnusin, V.I. Zabolotsky, V.V. Nikonenko, M.R. Urtenow, Russ. J. Electrochem. 22 (1986) 273-277.
[30] T.W. Xu, W.H. Yang, B.L. He, Chem. Eng. Sci. 56 (2001) 5343-5350.
[31] S. Koter, Sep. Purif. Technol. 22/23 (2001) 643-654.
[32] A.G. Guzm'an-Garcia, P.N. Pintauro, M.W. Verbrugge, R.F. Hill, AIChE J. 36 (1990) 1061.
[33] S. Koter, J. Membr. Sci. 206 (2002) 201-215.
[34] J.H. Choi, S.H. Moon, J. Membr. Sci. 191 (2001) 225-236.
[35] M.S. Kang, Y.J. Choi, I.J. Choi, T.H. Yoon, S.H. Moon, J. Membr. Sci. 216 (2003) 39-53.
[36] T.W. Xu,W.H.Yang, J. Membr. Sci. 190 (2) (2001) 159-166.
[37] L.Wu, T.W. Xu,W.H. Yang, J. Membr. Sci. 286 (2006) 185-192.
[2]王振坤编.离子交换膜-制备、性能及应用.北京:科学出版社,1985
[3]张维润等著.电渗析工程学.北京:科学出版社,1995
[4]徐铜文编.膜化学与技术教程.合肥:中国科学技术大学出版社,2003
[5]M.Y.Kariduraganavar,R.K.Nagarale,A.A.Kittur,S.S.Kulkarni,Desalination 197(2006)225-246
[6]R.K.Nagarale,G.S.Gohil,Vinod K.Shahi*,Advances in Colloid and Interface Science 119(2006)97-130
[7]K.Hideo,K.Tsuzura,H.Shimizu,Ion exchange membranes,in:K.Dorfner(Ed.),Ion Exchangers,Walter de Gruyter,Berlin,1991
[8]H.Strathmann,Electrodialysis and related processes,in:R.D
[9]W.Ostwald,Elektrische eigenschaften halbdurchl"assiger scheidewainde,Z.Phys.Chem.6(1890)71
[10]L.Michaelis,A.Fujita,The electric phenomen and ion permeability of membranes.Ⅱ.Permeability of apple peel,Biochem.Z.158(1925)28
[11]K.S"ollner,Uber mosaikmembranen,Biochem.Z.244(1932)390
[12]H..Wassenegger,K.Jaeger,Effecting cation-exchange in removing calcium from hard waters,U.S.Patent 2,204,539(1940)
[13]K.H.Meyer,H.Strauss,La perm'eabilit'e des membranes Ⅵ,sur le passage du courant 'electrique a travers des membranes s'elective,Helv.Chim.Acta 23(1940)795
[14]M.Juda,W.A.McRac,Coherent ion-exchange gels and membranes,J.Am.Chem.Soc.72(1950)1044
[15]W.G.Grot,Laminates of support material and fluorinated polymer containing pendant side chains containing sulfonyl groups.U.S.Patent 3,770,567(1973)
[16]F.P.Chlanda,L.T.C.Lee,K.J.Liu,Bipolar membranes and method of making same,U.S.Patent 4,116,889(1976)
[17]G.Pourcelly,C.Gavach,Electrodialysis water splitting-application of electrodialysis with bipolar membranes,in:A.J.B.Kemperman(Ed.),Handbook on Bipolar Membrane Technology,Twente University Press,Enschede,2000,pp.17-46
[18]T.W.Xu,Development of bipolar membrane-based process,Desalination 140(2001)247
[19]G.Daufin,J.P.Escudier,H.Carrere,S.Berot,L.Fillaudeau,M.Decloux,Recent emerging applications of membrane processes in the food and dairy industry,Food Bioproducts Process.79(2001)89
[20]T.Tarvainen,B.Svarfvar,S.Akerman,J.Savolaincn,M.Karhu,P.Paronen,K.Jarvinen,Drug release from a porous ion exchange membrane in vitro,Biomaterials 20(1999)2177
[21]Y.H.Kim,S.H.Moon,Lactic acid recovery from fermentation broth using one-stage electrodialysis,J.Chem.Technol.Biotechnol.76(2001)169
[22]G.Saracco,Ionic membrane technologies for the recovery of valuable chemicals from waste waters,Ann.Chim.Rome 93(2003)817
[23]L.Bazinet,F.Lamarche,D.Ippersiel,Bipolar membrane electrodialysis:applications of electrodialysis in the food industry,Trends Food Sci.Technol.9(1998)107
[24]T.W.Xu,Electrodialysis processes with bipolar membranes in environmental protection-a review,Resour.Conserv.Recycl.37(2002)1
[25]叶婴齐,李仲钦,水处理技术,1990,16(2):119-124
[26]江维达,李东.CN 87 104382.A.1981
[27]袁业明.水处理技术,1995,21:142-145
[28]谭春红,许志立,杨向民.膜科学与技术,1996,16:20-24
[29]何炳林,徐铜文,李向华.离子交换与吸附,1998,14(1):86-91
[30]Tongwen Xu,Ion exchange membranes:State of their development and perspective,Journal of Membrane Science 263(2005)1-29
[31]葛道才,膜科学与技术,1989,9:26-30
[32]T W Xu,W H Yang,Journal of Membrane Science,2001,183(2):193-200
[33]T W Xu,W H Yang,Journal of Membrane Science,2001,190:159-166
[34]T W Xu,W H Yang,Journal of Membrane Science,2002,199:203-210
[35]Lin M C,Takai N,Journal of Membrane Science,1994,88:77-83
[36]Sata T,Yamane Y,Matsusaki K,Journal of Polymer Science,1998,A36:49-58
[37]A M Mika,R F Childs,J M Dickson,B E McCarry and D R Gagnon,Journal of Membrane Science,1995,108:37-56
[38]D M Stachera,R F Childs,A M Mika and J M Dickson,Journal of Membrane Science,1998,148:119-127
[39]H Strathmann.Electrodialysis.In Membrane Seperations Technology-Principles and Applications,R D Noble and S A Stem(Eds.),Iland:Elseviver Press,1995
[40]R Yamane,T Izuo and Y Mizutani.Denkikagaku,1965,33(8):589-593
[41]W Gudernatsch,Ch Krumbholz and H Strathmann.In Proc.6th Intl.Symp.on Synthetic Membranes in Science and Technology,1989,Seot 4-8,Tubingen,Germany,pp223-226
[42]B Bauer,F J Gerner,H Strathmann.Desalination,1988,88:279-292
[43]D J Connolly,W F Gresham.1966,U.S.Patent 3,282,875
[44]Tongwen Xu,Keyan Hu,Separation and Purification Technology 40(2004)231-236
[1] G. Saracco, Ann. Chim. Rome 93 (2003) 817-826
[2] J.D. Way, R.D. Noble, D.L. Reed, G.M. Ginley, L.A. Jarr, AIChE J. 33 (1987) 480-487.
[3] D. Langevin, M. Pinoche, E. S'el'egny, M. M'etayer, R. Roux, J. Membr. Sci. 82 (1-2) (1993) 51-63.
[4] K. Adachi, W. Hu, H. Mastsumoto, K. Ito, A. Tanioka, Polymer 39 (11) (1998) 2315-2323.
[5] S. Srinivasan, E.A. Ticianelli, C.R. Derouin, A. Rendondo, J. Power Sources 22 (3-4) (1988) 359-375.
[6] H. Wang, G.A. Capuano, J. Electrochem. Soc. 145 (3) (1998) 780-784.
[7] A. Yasuda, N. Yamaga, K. Doi, T. Fujioka, S. Kusanagi, Solid State Ionics 40-1 (1990) 476-479.
[8] R. Rautenbach, W. Kopp, Desalination 65 (1987) 241.
[9] K. Kneifel, G. Luhrs, Desalination 68 (1988) 203.
[10] V.K. Indusekhar, G.S. Trivedi, B. Shah, Desalination 84 (1-3) (1991) 213-221.
[11] R.B. Meller, J. Ronnenberg, W.H. Campbell, S. Diekmann, Nature 355 (1992) 717-719.
[12] S. Jankovic, Manual de chimie de l'environnement, O.M.S. Geneve, 1974, p. 251.
[13] M. Hichour, F. Persin, J. Sandeaux, C. Gavach, Sep. Purif. Technol. 18 (2000) 1-11.
[14] A. Eyal, O. Kedem, J. Membr. Sci. 38 (1998) 101-111.
[15] T. Sata, J. Membr. Sci. 167 (2000) 1-31.
[16] T. Sata, T. Yamaguchi, K. Matsusaki, J. Phys. Chem. 99 (1995) 12875-12882.
[17] T. Sata, Y. Yamane, K. Matsusaki, J. Polym. Sci.: Part A Polym. Chem. 36 (1998) 49-58.
[18] T. Sata, S. Nojima, K. Katsusaki, Polymer 40 (1999) 7243-7249.
[19] T. Sata, S. Nojima, J. Polym. Sci.: Part B Polym. Phys. 37 (1999) 1773-1785.
[20] A. Blair, N. Kazerouni, Cancer Causes Control 8 (1997) 473-490.
[21] International Agency for Research on Cancer, Some Aromatic Amines, Hydrazine and Related Substances, Nnitroso Compounds and Miscellaneous Alkylating Agents, vol. 4, IARC, IARC Monogr Eval Carcinog Risks Humans, Lyon, France, 1974, pp. 231-245.
[22] T.W. Xu, W.H. Yang, J. Membr. Sci. 190 (2001) 159-166.
[23] T.W. Xu, F.F. Zha, J. Membr. Sci. 199 (2002) 203-210.
[24] T.W. Xu, Z.M. Liu, W.H. Yang, J. Membr. Sci 249 (2005) 183-191.
[25]T.W.Xu,W.H.Yang,J.Hazard.Mater.B 109(2004)157-164.
[26]J.X.Mo,S.M.Liu,Technol.Water Treat.8(1982)5(in Chinese).
[27]Q.Xue,Spectroscopy Methodology in Polymer Structure,Press of Senior Education of China,Beijing,1995,pp.6-60.
[28]T.W.Xu,W.H.Yang,B.L.He,Chem.Eng.Sci.56/18(2001)5343-5350.
[29]B.J.Robbins,R.W.Field,S.T.Kolaczkowski,A.D.Lockett,J.Membr.Sci.118(1996)101-110.
[1]Y.Li,T.W.Xu,M.Gong,J.Membr.Sci.279(1-2)(2006)200-208
[2]T.W.Xu and K.Y.Hu,Sep.Purif.Tech.40(2004)231-236.
[3]T.W.Xu,Z.M.Liu,W.H.Yang,J.Membr.Sci 249(2005)183-191.
[4]T.W.Xu,W.H.Yang,J.Membr.Sci.190(2001)159-166.
[5]M.S.Kang,Y.J.Choi,and S.H.Moon,AIChE J.49(2003)3213-3220.
[6]T.Sata,S.Nojima,K.Katsusaki,Polymer 40(1999)7243-7249.
[7]D.Wu,R..Q.Fu,T.W.Xu,L.Wu,W.H.Yang,J.Membr.Sci.DOI:10.1016/j.memsci.2007.11.042
[8]J.Fang,P.K.Shen,J.Membr.Sci.285(2006)317-322
[9]T.Sata,T.Yamaguchi,K.Matsusaki,J.Phys.Chem.99(1995)12875-12882.
[10]T.Sata,Y.Yamane,K.Matsusaki,J.Polym.Sci.:Part A Polym.Chem.36(1998)49-58.
[11]J.X.Mo,S.M.Liu,Technol.Water Treat.8(1982)5(in Chinese).
[12]T.W.Xu,W.H.Yang,and B.L.He,Chem.Eng.Sci.56/18(2001)5343-5350.
[1] R.K. Nagarale, G.S. Gohil, V.K. Shahi, Adv. Colloid 348 Interface Sci. 119 (2006) 97-130.
[2] T.W. Xu, K.Y. Hu, Sep. Purif. Technol. 40 (2004) 231-236.
[3] Y. Li, T.W. Xu, M. Gong, J. Membr. 371 Sci. 279 (1-2) (2006) 200-208.
[4] T.B. Qian (Ed.), Applications of Ion Exchange Agents, Press of Science 377 and Technology of Tianjin, Tianjin, 1984, pp. 50-51.
[5] T. Sata, J. Membr. Sci. 167 (2000) 1-31.
[6] T. Sata, T. Yamaguchi, K. Kawamura, K. Matsusaki, J. Chem. Soc, Faraday Trans. 93 (1997) 381 457-462.
[7] T.W. Xu, Z.M. Liu, W.H. Yang, J. Membr. Sci 249 (2005) 385 183-191.
[8] D.N. Amang, S. Alexandrova, P. Schaetzel, Chem. Eng. J. 99 388 (2004) 69-76.
[9] Z. Palaty, A. Zakova, Desalination 160 (2004) 51-66.
[10] Y. Marcus, Ion Solvation, John Wiley and Sons, New York, 1985, pp. 398 107-109.
[11] T. Sata, T. Yamaguchi, K. Matsusaki, J. Phys. Chem. 99 (1995) 12875-12882.
[12] T. Sata, Y. Yamane, K. Matsusaki, J. Polym. Sci.: Part A Polym. Chem. 36 (1998) 49- 357 58.
[13] S. Koizumi, T. Imato, N. Ishibashi, J. Membr. Sci. 132 (1997) 149-158.
[14] T. Sata, S. Nojima, J. Polym. Sci.: Part B Polym. Phys. 37 (1999) 1773-1785.
[15] T. Sata, Y. Kakuyama, K. Matsusaki, Y. Kagiyama, F. Kishimoto, Bull. Soc. Sea Water Sci. Jpn. 50(1996)449-455.
[16] D.N. Amang, S. Alexandrova, P. Schaetzel, Desalination 159 (2003) 393 267-271.
[17] Y. Li, T.W. Xu, Sep. Purif. Tech. DOI: 10.1016/j.seppur.2007.12.009
[1]H.Strathmarm,Ion-Exchange Membrane Separation Processes,Elsevier,Amsterdam,2004.
[2]T.W.Xu,J.Membr.Sci.263(2005)1-29.
[3]C.H.Huang,T.W.Xu,Environ.Sci.Technol.40(17)(2006)5233-5243.
[4]S.Koter,A.Warszawski,Pol.J.Environ.Stud.9(2000)45-56.
[5]R.K.Nagarale,G.S.Gohil,V.K.Shahi,Adv.Colloid Inter.Sci.119(2006)97-130.
[6]S.Sridhar,J.Membr.Sci.113(1996)73-79.
[7]C.H.Huang,T.W.Xu,Y.P.Zhang,Y.H.Xue,G.W.Chen,J.Membr.Sci.288(2007)1-12.
[8]M.S.Kang,S.H.Cho,S.H.Kim,Y.J.Choi,S.H.Moon,J.Membr.Sci.222(2003)149-161.
[9]I.N.Widiasa,P.D.Sutrisna,I.G.Wenten,Sep.Purif.Technol.39(2004)89-97.
[10]F.N.Xu,C.Innocent,G.Pourcelly,Sep.Purif.Technol.43(2005)17-24.
[11]C.Fargues,B.Broyart,M.Benmami,M.L.Lameloise,Sep.Sci.Technol.41(2006)359-377.
[12]A.Oehmen,R.Viegas,S.Velizarov,M.A.M.Reis,J.G.Crespo,Desalination 199(1-3)(2006)405-407.
[13]A.A.Khan,Inamuddin,Sens.Actuators B:Chem.120(1)(2006)10-18.
[14]B.Auclair,V.Nikonenko,C.Larchet,M.M'etayer,L.Dammak,J.Membr.Sci.195(2002)89-102.
[15]L.Michaeli,O.Kedem,Trans.Faraday Soc.57(1961)1185.
[16]O.Kedem,A.Katchalsky,Trans.Faraday Soc.59(1963)1918.
[17]R.Paterson,C.Gardner,J.Chem.Soc.A 13(1971)2254.
[18]O.Kedem,M.Perry,J.Membr.Sci.14(1983)249-262.
[19]A.Narebska,S.Koter,W.Kujawski,Desalination 51(1984)3-17.
[20]O.Kedem,J.Membr.Sci.206(2002)333-340.
[21]N.P.Gnusin,N.P.Berezina,O.A.Demina,N.A.Kononenko,Russ.J.Electrochem.32(1996)154-163.
[22]V.I.Zabolotsky,V.V.Nikonenko,J.Membr.Sci.79(1993)181-198.
[23]N.Berezina,N.Gnusin,O.Dyomina,S.Timofeyev,J.Membr.Sci.86(1994)207-229.
[24]N.P.Berezina,S.V.Timofeyev,O.A.Dyomina,A.N.Ozerin,A.V.Rebrov,Elektrokhimiya(Russ.J.Electrochem.)28(1992)1050.
[25]N.P.Gnusin,N.P.Berezina,N.A.Kononenko,O.A.Dyomina,J.Membr.Sci.243(2004)301-310.
[26] C. Larchet, L. Dammak, B. Auclair, S. Parchikov, V. Nikonenko, New J. Chem. 28(2004)1260-1267.
[27] J.H. Choi, S.H. Kim, S.H. Moon, J. Colloid Interf. Sci. 241 (2001) 120-126.
[28] V. Punita, P. Vyas, R. Ray, S.K. Rangarajan, Adhikary, J. Phys. Chem. B 106 (2002) 11910-11915.
[29] N.P. Gnusin, V.I. Zabolotsky, V.V. Nikonenko, M.R. Urtenow, Russ. J. Electrochem. 22 (1986) 273-277.
[30] T.W. Xu, W.H. Yang, B.L. He, Chem. Eng. Sci. 56 (2001) 5343-5350.
[31] S. Koter, Sep. Purif. Technol. 22/23 (2001) 643-654.
[32] A.G. Guzm'an-Garcia, P.N. Pintauro, M.W. Verbrugge, R.F. Hill, AIChE J. 36 (1990) 1061.
[33] S. Koter, J. Membr. Sci. 206 (2002) 201-215.
[34] J.H. Choi, S.H. Moon, J. Membr. Sci. 191 (2001) 225-236.
[35] M.S. Kang, Y.J. Choi, I.J. Choi, T.H. Yoon, S.H. Moon, J. Membr. Sci. 216 (2003) 39-53.
[36] T.W. Xu,W.H.Yang, J. Membr. Sci. 190 (2) (2001) 159-166.
[37] L.Wu, T.W. Xu,W.H. Yang, J. Membr. Sci. 286 (2006) 185-192.