膜法分离丙烯和氯化氢混合气
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摘要
气体膜渗透法和膜吸收法具有投资少、能耗低、高效、使用方便和操作简单等特点，此外膜吸收法还有传质面积大的优点和没有雾沫夹带、液泛、沟流、鼓泡等现象发生，因此本文采用气体膜渗透法和膜吸收法分离丙烯和氯化氢混合气。
本论文首先采用硅橡胶膜进行气体膜渗透实验的研究。在丙烯和氮气的纯气体系中考察了压差和温度对渗透系数和分离系数的影响，在丙烯和氮气的混合体系中考察了压差和切割率对渗透系数和分离系数的影响，比较纯气和混合体系的实验，得出混合体系中存在浓差极化现象，压差和切割率的增大都导致浓差极化程度加重。在氯化氢和氮气混合体系，考察了压差、浓度和切割率对渗透系数和分离系数的影响。在丙烯和氯化氢混合体系，考察了压差和切割率对渗透系数和分离系数的影响。实验结果表明硅橡胶膜在分离丙烯和氯化氢混合气的效果不太好。
本论文还用PP中空纤维膜进行了膜吸收实验的研究。在二氧化碳和氮气混合气体系中，考察了气体流率、气体浓度、吸收剂流率、吸收剂种类和浓度、流动方式对实验的影响。在丙烯和氯化氢混合气体系中，考察了气体流率和吸收剂流率对吸收效果的影响。并且还进行了从吸收剂中解吸氯化氢的实验，考察了解吸温度和解吸时间对解吸效果的影响。实验结果表明以乙二醇为吸收剂用膜吸收法分离丙烯和氯化氢的效果特别好，能达到完全分离，并且氯化氢相对容易从吸收剂中逸出。
Gas membrane permeation and membrane absorption have a lot of advantages, such as little investment, low energy use, convenient use and simple operation, in addition, membrane absorption also has some merits including surprisingly high interfacial area, absence of emulsions, no unloading at low flow rates, no flooding at high flow rates. So gas membrane permeation and membrane absorption are used for separation propylene / hydrogen chloride in this paper.
In the first, organophilic rubbery poly (dimethylsilicone) (PDMS) membrane is used for gas membrane permeation. In propylene/nitrogen pure gas system, the influence of pressure and temperature is researched on the permeability and separation factor, in propylene/nitrogen mixture gas system, the influence of pressure and cut-off ration is researched on the permeability and separation factor, the result shows that the concentration polarization has obvious adverse effect on the propylene/ nitrogen mixture system, the pressure and cut-off ration increase which lead to the increase of the concentration polarization. In the mixture gas of hydrogen chloride / nitrogen, the influence of pressure, concentration and cut-off ration are also researched on the permeability and separation factor. In the mixture gas of propylene / hydrogen chloride, the influence of pressure and cut-off ration are researched on the permeability and separation factor. The result shows that PDMS is unsuited for separation of propylene / hydrogen chloride.
Secondly, membrane absorption has been studied using polypropylene hollow fiber membrane. In the mixture gas of carbon dioxide/nitrogen, several influence factors are researched, including gas flow rate and concentration, absorbent flow rate and concentration, different absorbent, flow mode. In the mixture gas of propylene/hydrogen chloride, gas flow rate and absorbent flow rate are studied. Furthermore desorption of hydrogen chloride from glycol is researched, the influence factors include distillation temperature and time. The result shows that the effect of membrane absorption is very good in propylene/hydrogen chloride separation using glycol as absorbent, propylene can be separated entirely from the mixture gas, and hydrogen chloride can vaporized easily from glycol.
本论文首先采用硅橡胶膜进行气体膜渗透实验的研究。在丙烯和氮气的纯气体系中考察了压差和温度对渗透系数和分离系数的影响，在丙烯和氮气的混合体系中考察了压差和切割率对渗透系数和分离系数的影响，比较纯气和混合体系的实验，得出混合体系中存在浓差极化现象，压差和切割率的增大都导致浓差极化程度加重。在氯化氢和氮气混合体系，考察了压差、浓度和切割率对渗透系数和分离系数的影响。在丙烯和氯化氢混合体系，考察了压差和切割率对渗透系数和分离系数的影响。实验结果表明硅橡胶膜在分离丙烯和氯化氢混合气的效果不太好。
本论文还用PP中空纤维膜进行了膜吸收实验的研究。在二氧化碳和氮气混合气体系中，考察了气体流率、气体浓度、吸收剂流率、吸收剂种类和浓度、流动方式对实验的影响。在丙烯和氯化氢混合气体系中，考察了气体流率和吸收剂流率对吸收效果的影响。并且还进行了从吸收剂中解吸氯化氢的实验，考察了解吸温度和解吸时间对解吸效果的影响。实验结果表明以乙二醇为吸收剂用膜吸收法分离丙烯和氯化氢的效果特别好，能达到完全分离，并且氯化氢相对容易从吸收剂中逸出。
Gas membrane permeation and membrane absorption have a lot of advantages, such as little investment, low energy use, convenient use and simple operation, in addition, membrane absorption also has some merits including surprisingly high interfacial area, absence of emulsions, no unloading at low flow rates, no flooding at high flow rates. So gas membrane permeation and membrane absorption are used for separation propylene / hydrogen chloride in this paper.
In the first, organophilic rubbery poly (dimethylsilicone) (PDMS) membrane is used for gas membrane permeation. In propylene/nitrogen pure gas system, the influence of pressure and temperature is researched on the permeability and separation factor, in propylene/nitrogen mixture gas system, the influence of pressure and cut-off ration is researched on the permeability and separation factor, the result shows that the concentration polarization has obvious adverse effect on the propylene/ nitrogen mixture system, the pressure and cut-off ration increase which lead to the increase of the concentration polarization. In the mixture gas of hydrogen chloride / nitrogen, the influence of pressure, concentration and cut-off ration are also researched on the permeability and separation factor. In the mixture gas of propylene / hydrogen chloride, the influence of pressure and cut-off ration are researched on the permeability and separation factor. The result shows that PDMS is unsuited for separation of propylene / hydrogen chloride.
Secondly, membrane absorption has been studied using polypropylene hollow fiber membrane. In the mixture gas of carbon dioxide/nitrogen, several influence factors are researched, including gas flow rate and concentration, absorbent flow rate and concentration, different absorbent, flow mode. In the mixture gas of propylene/hydrogen chloride, gas flow rate and absorbent flow rate are studied. Furthermore desorption of hydrogen chloride from glycol is researched, the influence factors include distillation temperature and time. The result shows that the effect of membrane absorption is very good in propylene/hydrogen chloride separation using glycol as absorbent, propylene can be separated entirely from the mixture gas, and hydrogen chloride can vaporized easily from glycol.
引文
[1] 时钧，袁权，高从堦．膜技术手册．第一版．化学工业出版社，2001．1-766．
[2] Marcel Mulder．膜技术基本原理．第二版．清华大学出版社，1999．1-242．
[3] 董子丰．气体膜分离技术在石油工业中的应用．膜科学与技术，2000，20(3)：38-43．
[4] Baker R W, Simmons V L. Membrane systems for VOC recovery from air streams. Filtration&Separation, 1994 (5): 231-235.
[5] 苏毅，胡亮，刘谋盛．气体膜分离技术及应用．石油与天然气化工，2001，30(3)：113-116．
[6] 施得志，董声雄．气体膜分离技术的应用及发展前景．河南化工，2001，3：4-7．
[7] 华曼等．甲基硅橡胶膜的透过特性．膜科学与技术，1997，17(1)：58-62．
[8] Uhlborn R J, et al. Gas Separation with Inorganic Membranes. Membranes Synthesis Characteristics and Application. Ed.,by Bhave R R, New York: Van Nostrand Reinhold, 1991: 155-176.
[9] Bollinger W A, et al. Separation System for Oil Refining and Production. Chem. Eng. Prog., 1982, 78(10): 27-32.
[10] 吕仪军．化工生产中的膜技术．四川化工与腐蚀控制，1999，2(1)：44-46．
[11] Beaver E R，et al．Integration of Membrane with Other Air Separations Technologies. AICHE Symp.Ser., 1998,84(261);113-123.
[12] 张林，陈欢林，柴红．挥发性有机物废气的膜法处理工艺研究进展．化工环保，2002，22(2)：75-80．
[13] Murphy M K, et al. Post-Treatment of Asymmetric Membrane for Gas Application. AICHE Symp. Ser., 1989, 85(272): 34-40.
[14] 吴庸烈 等．压缩空气脱湿和乙醇气相脱水的集成膜过程研究．膜科学与技术，2000，20(2)：8-11．
[15] J.M. Watson, P.A. Payne, A study of organic compound pervaporation through silicone rubber, J. Membr. Sci. 49(1990)171-205.
[16] Anne Jonquieres, Robert Clement, Pierre Lochon, Jean Neel, Marlene Dresch, Bruno Chretien. Industrial state-of-the-art of pervaporation and vapour permeation in the western countries, J Membr Sci 206 (2002) 87-117.
[17] Technical Information about MTR available on line. Http://www. mtrinc.com/
[18] 邢丹敏，曹义鸣，李晖，刘富强，膜法有机蒸汽回收系统在工业中的应用，膜科学与技术，2000，20(4)：43-46．
[19] 邓麦村，曹义鸣，袁权，气体膜分离技术在我国的发展现状与展望，现代化工，1996，(10)：4-7．
[20] Cussler E L. Hollow fiber contactors. Membr-ane Processes in Separation and Purification, Net- herlands: Kluwer Academic Publishers, 1994,375-394.
[21] Gabelman Alan, Hwang Sun-Tak. Hollow fiber membrane contactors. J. Membr. Sci, 1999, 159:61-106.
[22] 高从堦，俞三传，蔡惠如．膜接触器及相关过程．水处理技术，1999，25(3)：311-316．
[23] 袁力，王志，王世昌．膜吸收技术及其在脱除酸性气体中的应用研究．膜科学与技术，2002，22(4)：55-59．
[24] 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．
[25] Chen H L, Sun L, Zhou Z J, et al. Study on CO_2 removal from air by hollow-fiber membrane contactors[A]. International Symposium on Membrane Technology and Environmental
Protection[C]. Beijng: China, 2000:146-151.
[26] Cooney D O, Jackson CC. Gas absorption in a hollow fiber device. Chem Eng Comm, 1989,179: 153-163.
[27] Wang K L, Cussler E L. Baffled membrane modules made with hollow fiber fabric. J Membr Sci, 1993, 85: 265-278.
[28] Xu Y, Wang J, Xu Z, et al. Separation and fixation of carbon dioxide by PP hollow fiber membrane contactors[A]. International Symposium on Membrane Technology and Environmental Protection[C]. Beijng: China, 2000:194-198.
[29] Nii S, Takeucbi H. Removal of CO_2 and/or SO_2 from gas streams by a membrane absorption method. Gas Separpurif, 1994, 18(2): 107-114.
[30] Wickramasinghe S R, Semmens M J, Cussler E L. Better hollow fiber contactors. J Membr Sci, 1991, 61: 371-388.
[31] Kreulen H, Smolers C A. Microporous hollow fiber membrane modules as gas-liquid contactors, Physical mass transfer processes. J Membr Sci, 1993, 78: 197-216.
[32] Iversen S B, Bbatia V K, Jahansen K D, et al. Charactericontactors. J Membr Sci, 1997, 130: 205-217.
[33] Li K, Teo W K. Gas absorption or stripping in hollow fiber membrane modules. Trends Chem Eng, 1998, 4: 115-132.
[34] Wang D, Li K, Teo W K. Removal of B_2S from air using asymmetric hollow fiber membrane contactors[A]. International Symposium on Membrane Technology and Environmental Protection[C]. Beijng:China, 2000:145.
[35] 李晖，刘富强，曹义鸣等．膜法分离有机蒸气／氮气混合气的过程研究．膜科学与技术，2000，20(2)：39-42．
[36] 胡伟，李晖，刘桂香等．有机蒸气／氮气膜分离的研究．膜科学与技术，1997，17(3)：25～29．
[37] 刘桂香，李晖，曾理，等．用于有机蒸气分离的PAN-SR膜的研究．膜科学与技术，1997，17(5)，21～27．
[38] Feng X S, Souriraian S,Tezel F B, et al, Separation of volatile organic compound/nitrogen mixtures by polymetric membranes. Ind Eng Chem Res, 1993, 32: 533-539.
[39] C K Yeom, S H Lee, H Y Song, et al. A characterization of concentration polarization in a boundary layer in the permeation of VOCs/N_2 mixtures through PDMS membrane. J Memb Sci, 2002, 205: 155~174.
[40] C. M. Bell. Solvent recovery from air. J Membr Sci, 1988, 36: 477.
[41] R. W. Baker, N. Yoshioka, J. Mohr, A. J. Khan. Separation of organic vapors from air. J Membr Sci, 1987, 31: 259.
[42] Woo-Ik Sohn, Dong-Hyun Ryu, Sae-Joong Oh, Ja-Kyung Koo. A study on the development of composite membranes for the separation of organic vapors. J Membr Sci, 2000,175:163-170.
[43] R. W. Baker, N. Yoshioka, J. Mohr, A. J. Khan. Separation of organic vapors from air. J Membr Sci, 1987,31: 259.
[44] D. I.M. Watson, G.S. Zhang and P.A. Payne. The diffusion mechanism in silicone rubber. J Membr Sci, 1992, 73 : 55-71.
[45] Gaohong HE, Yongli MI, Polock YUE, et al. Theoretical study on concentration
polarization in gas separation membrane processes. J Memb Sci, 1999, 153(2): 243~258.
[46] 郭占虎，史季芬，徐静年，等．中空纤维膜组件分离酸性气体．化工冶金，2000，21(3)：268-273．
[47] 金美芳，曹义鸣，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．
[48] Paul H M Feron, Albert E Jansen. CO_2 separation with polyolefin membrane contactors and dedicated absorption liquids:performances and prospects. Separation and Purification Technology, 2002, 27: 231-242.
[49] Kumar P S, Hogendoorn J A, Feron P H M, Versteeg G F. New absorption liquids for the removal of CO_2 from dilute gas streams using membrane contactors. Chemical Engineering Science, 2002, 57:1639-1651.
[50] Li K, Teo W K. Use of permeation and absorption methods for CO_2 removal in hollow fibre membrane modules. Separation and Purification Technology, 1998,13:79-88.
[51] Young-Seok Kim, Seung-Man Yang. Absorption of carbon dioxide through hollow fiber membranes using various aqueous absorbents. Separation and Purification Technology, 2000, 21:101-109.
[52] Yongtaek Lee, Richard D. Noble, Bong-Yeol Yeom, and so on. Analysis of CO_2 by hollow fibre membrane contactors..J Membr Sci, 2001, 194:57-67.
[53] K. Li, W. K. Teo. Use of permeation and absorption methods for CO_2 removal in hollow fibre membrane modules. J Membr Sci, 1998,13:79-88.
[54] 朱广宇，罗保林，辛玲玲．反应-膜分离耦合过程的传质特性．化工冶金，1999，20(2)：118-124．
[55] 宋文煜，王风云，吕英姿，王静．水-乙二醇体系中氯化氢的电池热力学[J]．南京师大学报．1995，18(4)：55-59．
[56] 王琴萍，吕殿祯，张莉等．乙二醇和水混合溶剂多组分电解质热力学．物理化学学报，2003，19：115-119
[2] Marcel Mulder．膜技术基本原理．第二版．清华大学出版社，1999．1-242．
[3] 董子丰．气体膜分离技术在石油工业中的应用．膜科学与技术，2000，20(3)：38-43．
[4] Baker R W, Simmons V L. Membrane systems for VOC recovery from air streams. Filtration&Separation, 1994 (5): 231-235.
[5] 苏毅，胡亮，刘谋盛．气体膜分离技术及应用．石油与天然气化工，2001，30(3)：113-116．
[6] 施得志，董声雄．气体膜分离技术的应用及发展前景．河南化工，2001，3：4-7．
[7] 华曼等．甲基硅橡胶膜的透过特性．膜科学与技术，1997，17(1)：58-62．
[8] Uhlborn R J, et al. Gas Separation with Inorganic Membranes. Membranes Synthesis Characteristics and Application. Ed.,by Bhave R R, New York: Van Nostrand Reinhold, 1991: 155-176.
[9] Bollinger W A, et al. Separation System for Oil Refining and Production. Chem. Eng. Prog., 1982, 78(10): 27-32.
[10] 吕仪军．化工生产中的膜技术．四川化工与腐蚀控制，1999，2(1)：44-46．
[11] Beaver E R，et al．Integration of Membrane with Other Air Separations Technologies. AICHE Symp.Ser., 1998,84(261);113-123.
[12] 张林，陈欢林，柴红．挥发性有机物废气的膜法处理工艺研究进展．化工环保，2002，22(2)：75-80．
[13] Murphy M K, et al. Post-Treatment of Asymmetric Membrane for Gas Application. AICHE Symp. Ser., 1989, 85(272): 34-40.
[14] 吴庸烈 等．压缩空气脱湿和乙醇气相脱水的集成膜过程研究．膜科学与技术，2000，20(2)：8-11．
[15] J.M. Watson, P.A. Payne, A study of organic compound pervaporation through silicone rubber, J. Membr. Sci. 49(1990)171-205.
[16] Anne Jonquieres, Robert Clement, Pierre Lochon, Jean Neel, Marlene Dresch, Bruno Chretien. Industrial state-of-the-art of pervaporation and vapour permeation in the western countries, J Membr Sci 206 (2002) 87-117.
[17] Technical Information about MTR available on line. Http://www. mtrinc.com/
[18] 邢丹敏，曹义鸣，李晖，刘富强，膜法有机蒸汽回收系统在工业中的应用，膜科学与技术，2000，20(4)：43-46．
[19] 邓麦村，曹义鸣，袁权，气体膜分离技术在我国的发展现状与展望，现代化工，1996，(10)：4-7．
[20] Cussler E L. Hollow fiber contactors. Membr-ane Processes in Separation and Purification, Net- herlands: Kluwer Academic Publishers, 1994,375-394.
[21] Gabelman Alan, Hwang Sun-Tak. Hollow fiber membrane contactors. J. Membr. Sci, 1999, 159:61-106.
[22] 高从堦，俞三传，蔡惠如．膜接触器及相关过程．水处理技术，1999，25(3)：311-316．
[23] 袁力，王志，王世昌．膜吸收技术及其在脱除酸性气体中的应用研究．膜科学与技术，2002，22(4)：55-59．
[24] 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．
[25] Chen H L, Sun L, Zhou Z J, et al. Study on CO_2 removal from air by hollow-fiber membrane contactors[A]. International Symposium on Membrane Technology and Environmental
Protection[C]. Beijng: China, 2000:146-151.
[26] Cooney D O, Jackson CC. Gas absorption in a hollow fiber device. Chem Eng Comm, 1989,179: 153-163.
[27] Wang K L, Cussler E L. Baffled membrane modules made with hollow fiber fabric. J Membr Sci, 1993, 85: 265-278.
[28] Xu Y, Wang J, Xu Z, et al. Separation and fixation of carbon dioxide by PP hollow fiber membrane contactors[A]. International Symposium on Membrane Technology and Environmental Protection[C]. Beijng: China, 2000:194-198.
[29] Nii S, Takeucbi H. Removal of CO_2 and/or SO_2 from gas streams by a membrane absorption method. Gas Separpurif, 1994, 18(2): 107-114.
[30] Wickramasinghe S R, Semmens M J, Cussler E L. Better hollow fiber contactors. J Membr Sci, 1991, 61: 371-388.
[31] Kreulen H, Smolers C A. Microporous hollow fiber membrane modules as gas-liquid contactors, Physical mass transfer processes. J Membr Sci, 1993, 78: 197-216.
[32] Iversen S B, Bbatia V K, Jahansen K D, et al. Charactericontactors. J Membr Sci, 1997, 130: 205-217.
[33] Li K, Teo W K. Gas absorption or stripping in hollow fiber membrane modules. Trends Chem Eng, 1998, 4: 115-132.
[34] Wang D, Li K, Teo W K. Removal of B_2S from air using asymmetric hollow fiber membrane contactors[A]. International Symposium on Membrane Technology and Environmental Protection[C]. Beijng:China, 2000:145.
[35] 李晖，刘富强，曹义鸣等．膜法分离有机蒸气／氮气混合气的过程研究．膜科学与技术，2000，20(2)：39-42．
[36] 胡伟，李晖，刘桂香等．有机蒸气／氮气膜分离的研究．膜科学与技术，1997，17(3)：25～29．
[37] 刘桂香，李晖，曾理，等．用于有机蒸气分离的PAN-SR膜的研究．膜科学与技术，1997，17(5)，21～27．
[38] Feng X S, Souriraian S,Tezel F B, et al, Separation of volatile organic compound/nitrogen mixtures by polymetric membranes. Ind Eng Chem Res, 1993, 32: 533-539.
[39] C K Yeom, S H Lee, H Y Song, et al. A characterization of concentration polarization in a boundary layer in the permeation of VOCs/N_2 mixtures through PDMS membrane. J Memb Sci, 2002, 205: 155~174.
[40] C. M. Bell. Solvent recovery from air. J Membr Sci, 1988, 36: 477.
[41] R. W. Baker, N. Yoshioka, J. Mohr, A. J. Khan. Separation of organic vapors from air. J Membr Sci, 1987, 31: 259.
[42] Woo-Ik Sohn, Dong-Hyun Ryu, Sae-Joong Oh, Ja-Kyung Koo. A study on the development of composite membranes for the separation of organic vapors. J Membr Sci, 2000,175:163-170.
[43] R. W. Baker, N. Yoshioka, J. Mohr, A. J. Khan. Separation of organic vapors from air. J Membr Sci, 1987,31: 259.
[44] D. I.M. Watson, G.S. Zhang and P.A. Payne. The diffusion mechanism in silicone rubber. J Membr Sci, 1992, 73 : 55-71.
[45] Gaohong HE, Yongli MI, Polock YUE, et al. Theoretical study on concentration
polarization in gas separation membrane processes. J Memb Sci, 1999, 153(2): 243~258.
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