本文采用二次生长法，在ɑ-Al2O3陶瓷管上制备亲水性NaA、T型、ZSM-5沸石膜，采用SEM对其进行表征。比较三种亲水性膜在异丙醇/水体系的渗透汽化性能，考察其在不同的料液温度下对异丙醇的分离效果。通过优化膜合成液中Si/Al和F-/Si的摩尔比、合成时间等条件，提高ZSM-5沸石膜的渗透汽化性能。分析考察膜的耐酸性能，结果显示ZSM-5沸石膜具有良好的耐酸性；将ZSM-5沸石膜在pH为5.8的酸性溶液浸泡10 d后，用于97 wt.%的乙酸乙酯/水体系中渗透汽化脱水，渗透液水含量可达99.59 wt.%，渗透通量可达0.12 kg·m-2·h-1，分离因数高达7894。

In this paper, hydrophilic NaA, T-type and ZSM-5 zeolite membranes on α-Al2O3 tubular supports were prepared by the secondary growth method and characterized by means of SEM. The pervaporation performance of membranes was compared using isopropanol/water mixture at different feed temperatures. The pervaporation performance of ZSM-5 membranes was improved by optimizing the synthesis conditions, such as the molar ratio of Si/Al and F-/Si in the synthesis solution, the crystallization time. The acid resistance of the membranes was investigated and the results indicate that ZSM-5 zeolite membranes have good acid resistance. The ZSM-5 zeolite membrane was characterized using an 97 wt.% ethyl acetate/water system after soaking in acidic solution of pH=5.8 for 10 days; the permeate water content is 99.59 wt.%, permeate flux could reach 0.12 kg·m-2·h-1 and the separation factor could reach to 7894.

[1]  Aiouach F, Goto S. Reactive distillation-pervaporation hybrid column for tert-amyl alcohol etherification with ethanol [J]. Chem Eng Sci, 2003, 58(12): 2465-2477.
[2]  Li G, Kikuchi E, Matsukata M. A study on the pervaporation of water–acetic acid mixtures through ZSM-5 zeolite membranes [J]. J Membrane Sci, 2003, 218(1-2): 185-194.
[3]  Li G, Kikuchi E, Matsukata M. Separation of water-acetic acid mixtures by pervaporation using a thin mordenite membrane [J]. Sep Purif Technol, 2003, 32(1-3): 199-206.
[4]  王献武,王金渠,杨建华,等. Sn-ZSM-5沸石膜的合成及其在废水脱除乙酸中的应用[J].膜科学与技术,2009,29(3):56-60.
[5]  梅金凤,周志辉,刘红,等. NaA沸石膜的制备及在一氯甲烷脱水中的应用[J]. 硅酸盐学报,2012,40(9):1363-1368.
[6]  罗钢元,周志辉,刘红,等. NaA沸石膜渗透蒸发脱除二氯甲烷中的痕量水[J]. 石油化工,2011,40(12):1297-1301.
[7]  展侠,李继定,操建华等. 高通量ZSM-5填充硅橡胶复合膜渗透汽化性能研究[J]. 膜科学与技术,2009,29(4):25-28.
[8]  周志辉,丁武龙,王涛等. NaA分子筛膜渗透蒸发制备高纯糠醛[J]. 石油化工,2013,42(3):292-297.
[9]  王龙,郑均林,孔德金,等. 二次生长法合成ZSM-5分子筛膜的影响因素[J]. 化学通报,2009,72(9):790-797.
[10] 成岳,王连军,李健生,等. 二次生长法中ZSM-5型沸石分子筛膜合成规律的研究[J].膜科学与技术,2006,26(4):39-43.
[11] Snyder M A, Tsapatsis M. Hierarchical Nanomanufacturing: from shaped zeolite nanoparticles to high-performance separation membranes [J]. Angew Chem Int Ed, 2007, 46(40):7560-7573.
[12] 苏小辉,厉刚,余林,易国斌,等. 沸石分子筛膜渗透汽化分离机理及其影响因素研究进展[J]. 化学试剂,2012,34(4):337-341.
[13] Ma Y H, Zhou Y J, Poladi R, et al. The synthesis and characterization of zeolite A membranes [J]. Sep Purif Technol, 2001, 25: 235-240.
[14] Yu C L, Liu Y M, Chen G L, et al. Pretreatment of isopropanol solution from pharmaceutical industry and pervaporation dehydration by NaA zeolite membranes [J]. Chin J Chem Eng, 2011, 19(6): 904-910.
[15] 张雄福,王金渠,刘长厚,等. ZSM-5型沸石膜的合成及应用于乙苯脱氢反应研究进展[J]. 膜科学与技术,2001,21(2):55-61
[16] Kondo M, Kita H. Permeation mechanism through zeolite NaA and T-type membranes for practical dehydration of organic solvents [J]. J Membrane Sci, 2010, 361(1-2): 223-231.
[17] Hasegawa Y, Abe C, Nishioka M, et al. Formation of high flux CHA-type zeolite membranes and their application to the dehydration of alcohol solutions [J]. J Membrane Sci, 2010, 364(1-2): 318-324
[18] 王金渠,杨建华,陈赞,等. 沸石分子筛膜苛刻环境有机物脱水的研究进展[J]. 膜科学与技术,2011,31(3):118-126.
[19] 任秀秀,杨建华,陈赞,等. 含氟体系下高性能丝光沸石分子筛膜的制备及其性能[J]. 催化学报,2012,33(9):1558-1564.
[20] Tanaka K, Yoshikawa R, Ying C, et al. Application of zeolite membranes to esterification reactions [J]. Catal Today, 2001, 67(1-3):121-125.