填充型醋酸纤维素膜渗透蒸发分离甲醇/MTBE混合物的研究
摘要
渗透蒸发作为新型的液体混合物分离技术,在有机物分离方面尤其是恒沸有机混合物分离方面具有突出的技术优势和良好的应用前景。渗透蒸发过程效率的高低主要取决于渗透蒸发膜性能的优劣,选择具有良好渗透蒸发分离特性的膜材料是渗透蒸发研究的核心内容之一。本文以甲醇/MTBE混合物为研究对象,从溶解度参数、化学结构、甲醇和甲基叔丁基醚(MTBE)分子的理化性质差异等角度出发,选用醋酸纤维素(CA)为基质膜材料,HZSM5沸石和4A沸石为填充剂,分别用丙酮(AC)和N,N-二甲基甲酰胺(DMF)为溶剂,制备了具有良好分离性能的渗透蒸发填充膜,探索制膜配方和渗透蒸发分离工艺。
采用红外光谱(FT-IR)、X-射线衍射(XRD)、扫描电镜(SEM)、热重分析(TGA)和机械性能测试等多种表征方法对膜的结构形态和物理化学性质进行了分析。
研究了CA-AC-HZSM5、CA-AC-4A和CA-DMF-HZSM5填充膜对甲醇和MTBE混合物的分离特性。考察了沸石填充量和甲醇浓度对膜渗透蒸发性能和溶胀吸附性能的影响。较为系统地考察了渗透蒸发过程操作条件(原料液浓度、温度、原料液流速)对膜分离性能的影响。实验结果表明,对于CA-AC-HZSM5填充膜,当HZSM5沸石含量为0.2wt%时,在原料液温度为30oC、流速为60L/h的操作条件下,分离甲醇浓度为20wt%的甲醇和MTBE混合物时的总渗透通量为226g/(m~2·h),分离因子为346。对于CA-AC-4A填充膜,当4A沸石含量为1wt%时,在原料液温度为30oC、流速为50L/h的操作条件下,分离甲醇浓度为20wt%的甲醇和MTBE混合物时的总渗透通量为202g/(m~2·h),分离因子为421。对于CA-DMF-HZSM5填充膜,当HZSM5沸石含量为1.5wt%时,在原料液温度为30oC、流速为50L/h的操作条件下,分离甲醇浓度为20wt%的甲醇和MTBE混合物时的总渗透通量为227g/(m~2·h),分离因子为806。
Pervaporation, as a novel liquid mixture separation technology, has outstanding technical advantages and favorable promising application prospects in the separation of organic- organic mixture especially azeotropic mixture. Separation performance of pervaporation process mainly depends on the property of the target membranes, therefore selecting the appropriative material with excellent separation performance constitutes an important issue in pervaporation research. In our work, methanol and MTBE mixture was the separation object, cellulose acetate(CA)was chosen out as the membrane material considering the solution parameters, chemical structures, properties difference of methanol and methyl-tertiary-butyl ether(MTBE). Cellulose acetate filled membranes were prepared with acetone(AC) and dimethylformamide (DMF) as solvents and HZSM5 zeolite and 4A zeolite as filler. The filled pervaporation membrane had better separation performance. The directions for prepare membranes and pervaporation separation technics were investigated.
The structure morphology, the physical and chemical properties of the membranes were characterized and analysed by FT-IR, XRD, SEM, TGA and universal testing machine.
The pervaporation performance of CA-AC-HZSM5, CA-AC-4A and CA-DMF-HZSM5 membranes for separation of methanol and MTBE mixture was investigated. The effects of zeolite content and methanol content in feed on the pervaporation performance and swelling behaviour were discussed. Moreover, effects of operating conditions (methanol concentration in feed, feed temperature, feed flow rate) on pervaporation performance were also studied. From the results, for the CA-AC-HZSM5 membrane, containing 0.2wt% HZSM5 exhibited the separation performance with a permeation flux of 226g/(m~2h) and a separation factor of 346 at 30oC for 20wt% in the feed, keeping feed flow rate 60L/h. for the CA-AC-4A membrane, containing 1wt% 4A exhibited the separation performance with a permeation flux of 202g/(m~2h) and a separation factor of 421 at 30oC for 20wt% in the feed, keeping feed flow rate 50L/h. for the CA-DMF-HZSM5 membrane, containing 1.5wt% HZSM5 exhibited the separation performance with a permeation flux of 227g/(m~2h) and a separation factor of 806 at 30oC for 20wt% in the feed, keeping feed flow rate 50L/h.
采用红外光谱(FT-IR)、X-射线衍射(XRD)、扫描电镜(SEM)、热重分析(TGA)和机械性能测试等多种表征方法对膜的结构形态和物理化学性质进行了分析。
研究了CA-AC-HZSM5、CA-AC-4A和CA-DMF-HZSM5填充膜对甲醇和MTBE混合物的分离特性。考察了沸石填充量和甲醇浓度对膜渗透蒸发性能和溶胀吸附性能的影响。较为系统地考察了渗透蒸发过程操作条件(原料液浓度、温度、原料液流速)对膜分离性能的影响。实验结果表明,对于CA-AC-HZSM5填充膜,当HZSM5沸石含量为0.2wt%时,在原料液温度为30oC、流速为60L/h的操作条件下,分离甲醇浓度为20wt%的甲醇和MTBE混合物时的总渗透通量为226g/(m~2·h),分离因子为346。对于CA-AC-4A填充膜,当4A沸石含量为1wt%时,在原料液温度为30oC、流速为50L/h的操作条件下,分离甲醇浓度为20wt%的甲醇和MTBE混合物时的总渗透通量为202g/(m~2·h),分离因子为421。对于CA-DMF-HZSM5填充膜,当HZSM5沸石含量为1.5wt%时,在原料液温度为30oC、流速为50L/h的操作条件下,分离甲醇浓度为20wt%的甲醇和MTBE混合物时的总渗透通量为227g/(m~2·h),分离因子为806。
Pervaporation, as a novel liquid mixture separation technology, has outstanding technical advantages and favorable promising application prospects in the separation of organic- organic mixture especially azeotropic mixture. Separation performance of pervaporation process mainly depends on the property of the target membranes, therefore selecting the appropriative material with excellent separation performance constitutes an important issue in pervaporation research. In our work, methanol and MTBE mixture was the separation object, cellulose acetate(CA)was chosen out as the membrane material considering the solution parameters, chemical structures, properties difference of methanol and methyl-tertiary-butyl ether(MTBE). Cellulose acetate filled membranes were prepared with acetone(AC) and dimethylformamide (DMF) as solvents and HZSM5 zeolite and 4A zeolite as filler. The filled pervaporation membrane had better separation performance. The directions for prepare membranes and pervaporation separation technics were investigated.
The structure morphology, the physical and chemical properties of the membranes were characterized and analysed by FT-IR, XRD, SEM, TGA and universal testing machine.
The pervaporation performance of CA-AC-HZSM5, CA-AC-4A and CA-DMF-HZSM5 membranes for separation of methanol and MTBE mixture was investigated. The effects of zeolite content and methanol content in feed on the pervaporation performance and swelling behaviour were discussed. Moreover, effects of operating conditions (methanol concentration in feed, feed temperature, feed flow rate) on pervaporation performance were also studied. From the results, for the CA-AC-HZSM5 membrane, containing 0.2wt% HZSM5 exhibited the separation performance with a permeation flux of 226g/(m~2h) and a separation factor of 346 at 30oC for 20wt% in the feed, keeping feed flow rate 60L/h. for the CA-AC-4A membrane, containing 1wt% 4A exhibited the separation performance with a permeation flux of 202g/(m~2h) and a separation factor of 421 at 30oC for 20wt% in the feed, keeping feed flow rate 50L/h. for the CA-DMF-HZSM5 membrane, containing 1.5wt% HZSM5 exhibited the separation performance with a permeation flux of 227g/(m~2h) and a separation factor of 806 at 30oC for 20wt% in the feed, keeping feed flow rate 50L/h.
引文
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[2]吴千里,甲基叔丁基醚(MTBE)对汽油性能的改善,江苏化工,1995,23(1):29～32,35
[3]谭文革,甲基叔丁基醚生产及其应用,环境工程,2000,(76):48～49
[4]徐怡珊,甲基叔丁基醚的研究进展,化工环保,2004,24(6):416～420
[5]邹劲松,MTBE供需现状及其前景展望,当代石油石化,2003,11(7):23～27
[6]申文杰,胡津仙,甲基叔丁基醚(MTBE)的合成,合成化学,1997,5(4):331～337
[7]陈翠仙,蒋维钧,渗透汽化研究进展,现代化工,1991,4:14～17
[8]陈翠仙,余立新,祁喜旺等,渗透汽化膜分离技术的进展及在石油化工中的应用,膜科学与技术,1997,17(3):14～18
[9]祁喜旺,陈洪钫,渗透蒸发膜及其传质的研究进展,膜科学与技术,1995,15(3):1～9
[10]史宝利,吴庸烈,甲基叔丁基醚/甲醇膜法分离的研究进展,膜科学与技术,2004,24(1):70～75
[11] J.P.G. Villaluenga, M. Khayet, P. Godino, etal.Analysis of the membrane thickness effect on the pervaporation separation of methanol/methyl tertiary butyl ether mixtures, Mengual Separation and Purification Technology,2005, 47: 80～87
[12] R.Y.M. Huang, G.Y. Moon, R. Pal, Chitosan/anionic surfactant complex membranes for the pervaporation separation of methanol/MTBE and characterization of the polymer/surfactant system, Journal of Membrane Science, 2001, 184: 1～15
[13] S. G. Kim, Y. I. Kim, J. G. Jegal, Characterization and Preparation of Polyion Complex Composite Membranes for the Separation of Methyl tert-Butyl Ether/Methanol Mixtures, Journal of Applied Polymer Science, 2002, 85: 714～725
[14]昊庸烈,刘静芝,孔庆怡,聚酰亚胺、聚砜、聚醚砜及其共混改性中空纤维膜用于醇/醚气相分离的研究,功能高分子学报, 1999, 12(4): 453～456
[15] Yin Lu, Lin Zhang, Huan-Lin Chen, etal, Hybrid process of distillation side-connected with pervaporation for separation of methanol/MTBE/C4 mixture, Desalination, 2002,149:81～87
[16] Hans-Hartmut Schwarz, R.Apostel, D. Paul, Membranes based on polyelectrolyte–surfactant complexes for methanol separation, Journal of Membrane Science, 2001,194: 91～102
[17] Shuguang Cao, Yanqiao Shi, Guanwen Chen, Permeation behaviour in cellulose triacetate dense membrane during pervaporation separation of methanol/methyl tert-butyl ether mixture, Polymer International, 2000,49: 209～215
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