中空纤维膜溶剂吸收烟气脱硫研究
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摘要
采用自制的微孔聚丙烯中空纤维膜组件为膜吸收反应器，以Na_2SO_3溶液为吸收液，对中空纤维膜溶剂吸收烟气脱硫进行了实验研究。考察了吸收液性质、进气气速和膜组件结构参数等对分离过程和效率的影响，在理论和实验的基础上，研究了孔径、膜传质系数和脱硫效率之间的关系。实验结果表明，当吸收液pH值＞7时脱硫率最大，且保持稳定；吸收液浓度≥5％时，吸收液的液相阻力可以忽略；膜组件脱硫率随气速的增大而减小，而随膜组件有效长度、膜传质系数的增大而增大；膜孔径大易产生润湿现象。分别利用传质经验式和传质微分方程推导建立了非润湿性中空纤维膜组件脱硫效率传质模型，模拟结果与实验数据吻合较好。
An experimental research of FGD by hollow-fiber membrane-based absorption system was carried out, the hollow-fiber microporous membrane modules were used as membrane contactors and the aqueous solution of sodium sulfite was chosen as the absorbent. The effect of characteristics on desulfurization efficiency have been widely investigated, the relation of pore size, the membrane's coefficient and the desulfurization efficiency have been also examined both theoretically and experimentally. The results show that, when pH of absorbent is more than 7, the desulfurization efficiency is best and constant, concentration of absorbent is more than 5%, the mass-transfer resistance of the liquid is negligible, Increasing the effective length of module and the membrane's coefficient will help to increase the desulfurization efficiency of module but velocity of feed gas, and the larger pore size makes membrane leak easily. The mathematical model of desulfurization efficiency in hydrophobic hollow-fiber membrane was set up
respectively by using of the mass transfer empirical correlation and differential equation. The results from the model are in good agreement with the experimental data.
An experimental research of FGD by hollow-fiber membrane-based absorption system was carried out, the hollow-fiber microporous membrane modules were used as membrane contactors and the aqueous solution of sodium sulfite was chosen as the absorbent. The effect of characteristics on desulfurization efficiency have been widely investigated, the relation of pore size, the membrane's coefficient and the desulfurization efficiency have been also examined both theoretically and experimentally. The results show that, when pH of absorbent is more than 7, the desulfurization efficiency is best and constant, concentration of absorbent is more than 5%, the mass-transfer resistance of the liquid is negligible, Increasing the effective length of module and the membrane's coefficient will help to increase the desulfurization efficiency of module but velocity of feed gas, and the larger pore size makes membrane leak easily. The mathematical model of desulfurization efficiency in hydrophobic hollow-fiber membrane was set up
respectively by using of the mass transfer empirical correlation and differential equation. The results from the model are in good agreement with the experimental data.
引文
1 钟秦．燃煤烟气脱硫脱硝技术及工程实例．北京：化学工业出版社，2002：123～125
2 国家环境保护总局．2002年中国环境公报。
3 黄建彬．工业气体手册．北京：化学工业出版社，2002
4 汪大翚．化工环境工程概论．北京：化学工业出版社，2002
5 肖文德，吴志泉．二氧化硫脱除与利用．北京：化学工业出版社，2001
6 吴忠标．大气污染控制技术．北京：化学工业出版社，2002
7 郑领英，王学松．膜技术．北京：化学工业出版社，2000
8 陈翠仙，佘立新，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
9 Mulder M．膜技术基本原理．[李琳译]．第2版，北京：清华大学出版社，1999
10 钟秦，王娟，陈迁乔，曲虹霞．化工原理．北京：化学工业出版社，2002
11 王保国，蒋维钧．中空纤维膜的研究现状与发展．化工进展，1999，4(2)：39～43
12 徐又一．聚烯烃中空纤维膜及分离新技术在环保工程中的开发应用．科技纵横，1996(10)：38～40
13 Hikita H, Asai S, Tsuji T. Absorption of sulfur dioxide into water. AIChE J, 1978, 24(1): 147～148
14 Hikita H, Asai S, Tsuji T. Absorption of sulfur dioxide into aqueous sodium hydroxide and sodium sulfite solutions. AIChE J, 1977, 23(4): 538～544
15 Roberts D L, Friedlander S K. Sulfur dioxide transport through aqueous solutions: Part Ⅰ-Theory. AIChE J, 1980, 26(4): 593～602
16 Roberts D L, Friedlander S K. Sulfur dioxide transport through aqueous solutions: Part Ⅱ-Experimental results and comparison with theory. AIChE J, 1980, 26(4): 602～610
17 Zhang Q, Cussler E L. Hollow fiber gas membranes. AIChE J, 1985, 31(9): 1548～1553
18 Zhang Q, Cussler E L. Micro porous hollow fiber for gas absorption Ⅰ-Mass transfer in the liquid. J Membr Sci, 1985, 23: 321～333
19 Zhang Q, Cussler E L. Microporous hollow fiber for gas absorption Ⅱ-Mass transfer across the membrane. J Membr Sci, 1985, 23:333～345
20 Kreulen H, Smolders C A, Versteeg G F, van Swaaij W P M. Mieroporous hollow fiber membrane modules as gas-liquid contactors. Part 1 Physical mass transfer processes. J Membr Sci, 1993, 78: 197～216
21 Kreulen H, Smolders C A, Versteeg G F, van Swaaij W P M. Microporous hollow fiber membrane modules as gas-liquid contaetors. Part 2 Mass transfer with chemical reaction. J Membr Sci, 1993, 78: 217～233
22 Li K, Kong J F, Wang D L, Teo W K. Tailor-made asymmetric PVDF hollow fibers for soluble gas
removal. AIChE J, 1999, 45(6): 1211～1219
23 Li K, Kong J F, Wang D L, Teo W K. Use of asymmetric hollow fiber modules for elimination of H_2S from gas streams via a membrane absorption method. Chem Eng Sci, 1998, 53(6): 1111～1119
24 Nii S, Takeuchi H. Removal of CO_2 and/or SO_2 form gas streams by a membrane absorption method. Gas Separ Purif, 1994, 18(2): 107～114
25 Sujatha K, Sirkar K K. Gas absorption studies in microporous hollow fiber membrane modules. Ind. Eng Chem Res, 1993, 32:674～684
26 GabelmanA, Hwang S T. Hollow fiber membrane contactors[J]. J Membrane Sci, 1999, 159: 61～106
27 Asim K G, Sudipto M, Sirkar K K. Gas separation modes in a hollow fiber contained liquid membrane permeator. Ind Eng Chem Res, 1992, 31: 593～604
28 Majumdar S, Sengupta A, Cha J S, Sirkar K K. Simultaneous SO_2/NO separation from flue gas in a contained liquid membrane permeator. Ind Eng Chem Res, 1994, 33:667～675
29 Majumdar S, Aism K G, Sirkar K K. A new liquid membrane technique for gas separation. AIChE J, 1988, 34(7): 1135～1145
30 Cooney D O, Jackson C C. Gas absorption in a hollow fiber device. Chem Eng Comm, 1989, 179: 153～163
31 Wang K L, Cussler E L. Baffled membrane modules made with hollow fiber fabric. J Membr Sci, 1993, 85: 265～278
32 Seiichi Mi, Andrew L Z. Theoretical analysis of pore size distribution effects on membrane transport. J Membr Sci, 1993, 82:211～227
33 Li K, Kong J F, Tan X Y. Design of hollow fiber membrane modules for soluble gas removal. Chem Eng Sci, 2000, 55:5579～5588
34 Paul H M, Flue gas treatment with membrane gas absorption. Membr.Tech, 1997, 102: 7～10
35 K Li, Xiaoyao Tan. Mass Transfer and Chemical Reaction in Hollow-Fiber Membrane Reactors. AICHE Journal Feb, 2001, 47(2): 427～436
36 Malek A, K Li, Teo W K. Modeling of micro porous hollow fiber membrane modules operated under partially wetted conditions, Ind Eng Chem Res, 1997, 36:784～793
37 reulen H, Smolders C A, Versteeg G F. Determination of mass transfer rates in wetted and non-wetted micro porous membranes. Chem Eng Sci, 1993, 48(11): 2093～2102
38 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，1998，24(6)：623～626
39 熊丹柳，邓修，戴干策．液膜法烟气脱硫实验Ⅰ-含浸液膜渗透器特性．华东理工大学学报，1997，23(2)：156～161
40 熊丹柳，邓修，戴干策．液膜法烟气脱硫实验Ⅱ-促进传质机理与数学模型．华东理工大学学报，1998，24(1)：1～6
41 金美芳，曹义鸣，邢丹敏，李晖，孙晓珊，杨丹．膜吸收法脱除二氧化硫．膜科学与技术，1999，19(3)：44～46
42 秦向东，温铁军，金美芳．脱除与浓缩二氧化碳的膜分离技术．膜科学与技术，1998，18(6)：7～13
43 刘涛，史季芬，徐静年，吴祥芝．中空纤维膜气体溶剂的吸收分离过程．化工冶金，1999，20(1)：11～16
44 郭占虎，史季芬，徐静年，魏素英，吴祥芝．中空纤维膜组件分离酸性气体．化工冶金，2000，21(3)：268～273
45 朱宝库，陈炜，王建黎，徐又一，徐志康．膜接触器分离混合气中二氧化碳的研究．环境科学，2003，24(5)：34～38
46 张慧峰，张卫东，张泽廷，史季芬．中空纤维膜吸收法脱除SO_2的实验研究．环境科学与技术，2003，26(5)：8～10
47 王志，龚彦文，袁立，王世昌．中空纤维膜吸收器中CO_2吸收过程模拟．化工学报，2003，54(11)：1563～1568
48 Andrew L Z, Pierre A, Martine M, Joseph M P. Use of the lognormal probability density function to analyze membrane pore size distributions: Functional forms and discrepancies. J Membr Sci, 1994, 91: 293～298
49 Gerhard M. Gas separation with polymer membranes. Chem Int Ed, 1998, 37: 2960～2974
50 Bryan P, Wudneh A. Effect of chemical impurities on gas permeation and diffusion in polymeric membranes. Separation Science and Technology, 2001, 36(14): 3121～3140
51 Sudipto M, Sirrkar K K. A larger-scale study of gas separation by hollow fiber contained liquid membrane permeator. J Membr Sci, 1991, 62: 293～307
52 Wickramasinghe S R, Michael J S, Cussler E L. Better hollow fiber contactors. J Membr Sci, 1991, 62: 371～388
53 Li K, Mona S L T, Teo W K. Design ofa CO_2 scrubber for self-contained breathing systems using a microporous membrane. J Membr Sci, 1994, 86:119～125
54 Zhang Q, Cussler E L. Hollow fiber gas membranes. AIChE J, 1985, 31(9): 1548～1553
55 Sengupta A, Raghuraman B, Sirkar K K. Liquid membranes for flue gas desulfurization. J Membr Sci, 1990, 5: 105～126
56 Hassan M, Ashwani K, Roberto M N, Takeshi M. A study of mass transfer in the membrane air-stripping process using micro porous polyproplylene hollow fibers. J Membr Sci, 2000, 179: 29～41
57 薛为岚，曾作祥，邓修．天然气净化膜及膜内气体传质机理研究．高校化学工程学报，1999，13(5)：408～414
58 陈理．脱除烟气中SO_2和NO_x的新技术．化工环保，1997，17(6)：336～341
59 徐振良．膜法水处理技术．北京：化学工业出版社，2001
60 Matson S L, Lopez J, Quinn J A. Separation of gases with synthetic membranes. Chem Eng Sci, 1983, 38(4): 503～524
61 王学松．膜分离技术及其应用．北京：科学出版社，1994
62 Iversen S B, Bhatia V K, Johansen D, Jonsson G. Characterization of microporous membrane contractors. J Membr Sci, 1997, 130:205～217
63 Costello M J, Fane A G, Hogan P A, Schofield R W. The effect of shell side hydrodynamics on the performance of axial flow hollow fibre modules. J Membr Sci, 1993, 80: 1～11
64 柯斯乐．扩散流体系统中的传质．北京：化学工业出版社，2002
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2 国家环境保护总局．2002年中国环境公报。
3 黄建彬．工业气体手册．北京：化学工业出版社，2002
4 汪大翚．化工环境工程概论．北京：化学工业出版社，2002
5 肖文德，吴志泉．二氧化硫脱除与利用．北京：化学工业出版社，2001
6 吴忠标．大气污染控制技术．北京：化学工业出版社，2002
7 郑领英，王学松．膜技术．北京：化学工业出版社，2000
8 陈翠仙，佘立新，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
9 Mulder M．膜技术基本原理．[李琳译]．第2版，北京：清华大学出版社，1999
10 钟秦，王娟，陈迁乔，曲虹霞．化工原理．北京：化学工业出版社，2002
11 王保国，蒋维钧．中空纤维膜的研究现状与发展．化工进展，1999，4(2)：39～43
12 徐又一．聚烯烃中空纤维膜及分离新技术在环保工程中的开发应用．科技纵横，1996(10)：38～40
13 Hikita H, Asai S, Tsuji T. Absorption of sulfur dioxide into water. AIChE J, 1978, 24(1): 147～148
14 Hikita H, Asai S, Tsuji T. Absorption of sulfur dioxide into aqueous sodium hydroxide and sodium sulfite solutions. AIChE J, 1977, 23(4): 538～544
15 Roberts D L, Friedlander S K. Sulfur dioxide transport through aqueous solutions: Part Ⅰ-Theory. AIChE J, 1980, 26(4): 593～602
16 Roberts D L, Friedlander S K. Sulfur dioxide transport through aqueous solutions: Part Ⅱ-Experimental results and comparison with theory. AIChE J, 1980, 26(4): 602～610
17 Zhang Q, Cussler E L. Hollow fiber gas membranes. AIChE J, 1985, 31(9): 1548～1553
18 Zhang Q, Cussler E L. Micro porous hollow fiber for gas absorption Ⅰ-Mass transfer in the liquid. J Membr Sci, 1985, 23: 321～333
19 Zhang Q, Cussler E L. Microporous hollow fiber for gas absorption Ⅱ-Mass transfer across the membrane. J Membr Sci, 1985, 23:333～345
20 Kreulen H, Smolders C A, Versteeg G F, van Swaaij W P M. Mieroporous hollow fiber membrane modules as gas-liquid contactors. Part 1 Physical mass transfer processes. J Membr Sci, 1993, 78: 197～216
21 Kreulen H, Smolders C A, Versteeg G F, van Swaaij W P M. Microporous hollow fiber membrane modules as gas-liquid contaetors. Part 2 Mass transfer with chemical reaction. J Membr Sci, 1993, 78: 217～233
22 Li K, Kong J F, Wang D L, Teo W K. Tailor-made asymmetric PVDF hollow fibers for soluble gas
removal. AIChE J, 1999, 45(6): 1211～1219
23 Li K, Kong J F, Wang D L, Teo W K. Use of asymmetric hollow fiber modules for elimination of H_2S from gas streams via a membrane absorption method. Chem Eng Sci, 1998, 53(6): 1111～1119
24 Nii S, Takeuchi H. Removal of CO_2 and/or SO_2 form gas streams by a membrane absorption method. Gas Separ Purif, 1994, 18(2): 107～114
25 Sujatha K, Sirkar K K. Gas absorption studies in microporous hollow fiber membrane modules. Ind. Eng Chem Res, 1993, 32:674～684
26 GabelmanA, Hwang S T. Hollow fiber membrane contactors[J]. J Membrane Sci, 1999, 159: 61～106
27 Asim K G, Sudipto M, Sirkar K K. Gas separation modes in a hollow fiber contained liquid membrane permeator. Ind Eng Chem Res, 1992, 31: 593～604
28 Majumdar S, Sengupta A, Cha J S, Sirkar K K. Simultaneous SO_2/NO separation from flue gas in a contained liquid membrane permeator. Ind Eng Chem Res, 1994, 33:667～675
29 Majumdar S, Aism K G, Sirkar K K. A new liquid membrane technique for gas separation. AIChE J, 1988, 34(7): 1135～1145
30 Cooney D O, Jackson C C. Gas absorption in a hollow fiber device. Chem Eng Comm, 1989, 179: 153～163
31 Wang K L, Cussler E L. Baffled membrane modules made with hollow fiber fabric. J Membr Sci, 1993, 85: 265～278
32 Seiichi Mi, Andrew L Z. Theoretical analysis of pore size distribution effects on membrane transport. J Membr Sci, 1993, 82:211～227
33 Li K, Kong J F, Tan X Y. Design of hollow fiber membrane modules for soluble gas removal. Chem Eng Sci, 2000, 55:5579～5588
34 Paul H M, Flue gas treatment with membrane gas absorption. Membr.Tech, 1997, 102: 7～10
35 K Li, Xiaoyao Tan. Mass Transfer and Chemical Reaction in Hollow-Fiber Membrane Reactors. AICHE Journal Feb, 2001, 47(2): 427～436
36 Malek A, K Li, Teo W K. Modeling of micro porous hollow fiber membrane modules operated under partially wetted conditions, Ind Eng Chem Res, 1997, 36:784～793
37 reulen H, Smolders C A, Versteeg G F. Determination of mass transfer rates in wetted and non-wetted micro porous membranes. Chem Eng Sci, 1993, 48(11): 2093～2102
38 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，1998，24(6)：623～626
39 熊丹柳，邓修，戴干策．液膜法烟气脱硫实验Ⅰ-含浸液膜渗透器特性．华东理工大学学报，1997，23(2)：156～161
40 熊丹柳，邓修，戴干策．液膜法烟气脱硫实验Ⅱ-促进传质机理与数学模型．华东理工大学学报，1998，24(1)：1～6
41 金美芳，曹义鸣，邢丹敏，李晖，孙晓珊，杨丹．膜吸收法脱除二氧化硫．膜科学与技术，1999，19(3)：44～46
42 秦向东，温铁军，金美芳．脱除与浓缩二氧化碳的膜分离技术．膜科学与技术，1998，18(6)：7～13
43 刘涛，史季芬，徐静年，吴祥芝．中空纤维膜气体溶剂的吸收分离过程．化工冶金，1999，20(1)：11～16
44 郭占虎，史季芬，徐静年，魏素英，吴祥芝．中空纤维膜组件分离酸性气体．化工冶金，2000，21(3)：268～273
45 朱宝库，陈炜，王建黎，徐又一，徐志康．膜接触器分离混合气中二氧化碳的研究．环境科学，2003，24(5)：34～38
46 张慧峰，张卫东，张泽廷，史季芬．中空纤维膜吸收法脱除SO_2的实验研究．环境科学与技术，2003，26(5)：8～10
47 王志，龚彦文，袁立，王世昌．中空纤维膜吸收器中CO_2吸收过程模拟．化工学报，2003，54(11)：1563～1568
48 Andrew L Z, Pierre A, Martine M, Joseph M P. Use of the lognormal probability density function to analyze membrane pore size distributions: Functional forms and discrepancies. J Membr Sci, 1994, 91: 293～298
49 Gerhard M. Gas separation with polymer membranes. Chem Int Ed, 1998, 37: 2960～2974
50 Bryan P, Wudneh A. Effect of chemical impurities on gas permeation and diffusion in polymeric membranes. Separation Science and Technology, 2001, 36(14): 3121～3140
51 Sudipto M, Sirrkar K K. A larger-scale study of gas separation by hollow fiber contained liquid membrane permeator. J Membr Sci, 1991, 62: 293～307
52 Wickramasinghe S R, Michael J S, Cussler E L. Better hollow fiber contactors. J Membr Sci, 1991, 62: 371～388
53 Li K, Mona S L T, Teo W K. Design ofa CO_2 scrubber for self-contained breathing systems using a microporous membrane. J Membr Sci, 1994, 86:119～125
54 Zhang Q, Cussler E L. Hollow fiber gas membranes. AIChE J, 1985, 31(9): 1548～1553
55 Sengupta A, Raghuraman B, Sirkar K K. Liquid membranes for flue gas desulfurization. J Membr Sci, 1990, 5: 105～126
56 Hassan M, Ashwani K, Roberto M N, Takeshi M. A study of mass transfer in the membrane air-stripping process using micro porous polyproplylene hollow fibers. J Membr Sci, 2000, 179: 29～41
57 薛为岚，曾作祥，邓修．天然气净化膜及膜内气体传质机理研究．高校化学工程学报，1999，13(5)：408～414
58 陈理．脱除烟气中SO_2和NO_x的新技术．化工环保，1997，17(6)：336～341
59 徐振良．膜法水处理技术．北京：化学工业出版社，2001
60 Matson S L, Lopez J, Quinn J A. Separation of gases with synthetic membranes. Chem Eng Sci, 1983, 38(4): 503～524
61 王学松．膜分离技术及其应用．北京：科学出版社，1994
62 Iversen S B, Bhatia V K, Johansen D, Jonsson G. Characterization of microporous membrane contractors. J Membr Sci, 1997, 130:205～217
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