膜科学与技术

继代晶种法合成NaA分子筛膜

作者：李贝贝，曾文豪，夏斌，金花，曹毅，陈晨，李砚硕

单位：宁波大学材料科学与化学工程学院，新型功能材料及其制备科学省部共建国家重点实验室培育基地，宁波 315211

关键词：分子筛膜；NaA；渗透汽化；二次生长；继代晶种法

出版年,卷(期):页码： 2020,40(1):110-116

摘要：

本实验开发继代晶种法合成低成本、易重复的NaA分子筛膜：采用前一代分子筛膜晶化后剩余的母液为晶种液，将其涂敷于载体表面，干燥后置于合成液中，并在微波加热条件下合成NaA分子筛膜。本文考察了初代母液合成时间对NaA分子筛膜的性能影响，渗透汽化性能测试结果显示：初代母液的合成时间和分子筛膜的晶化时间为12.5 min合成的NaA分子筛膜表现出最优的渗透汽化性能，其渗透通量和分离系数在70 °C时分别达到1.25 kg/m2·h和 > 10000。采用优化的合成条件，用继代晶种法连续合成出五代NaA分子筛膜，渗透汽化测试结果表明乙醇脱水性能基本相同，表明继代晶种法可以重复合成性能优良的NaA分子筛膜。

The low cost and highly reproducible NaA membrane is synthesized by a novel succeeding seeding method. The present generation of NaA membrane could be obtained by the secondary growth procedure of the prior generation of dried mother liquor over α-Al2O3 tube, which is named succeeding seeding method (SSM). Firstly, various original mother liquor are obtained by altering the crystallization time of the gel, and the effect of original mother liquor on the separation performance of NaA membrane is explored. The results reveal that the NaA membrane with the crystallization time of 12.5 min shows the best pervaporation performance with the separation factor larger than 10000 and the flux of 1.25kg/m2·h for the dehydration of 90 wt.% ethanol solution at 70°C. Then, five generations of NaA membranes are synthesized in sequence by SSM under the optimal conditions above. Five generations of NaA membranes show analogous crystallinity, surface morphology and thickness, so similar pervaporation performances with the separation factor larger than 10000 and the flux of ca. 1.25 kkg/m2·h are achieved . Therefore, highly reproducible NaA membrane with good separation performance can be obtained by SSM.

第一作者简介：李贝贝（1993-），男，安徽省宿州市，硕士研究生，硕士，研究方向：分子筛膜合成，E-mail：2587342429@qq.com 通讯作者，陈晨 E-mail：chenchen@nbu.edu.cn; 李砚硕E-mail：liyanshuo@nbu.edu.cn

参考文献：

[1] Koros, W.J. Evolving beyond the thermal age of separation processes: Membranes can lead the way[J]. AIChE Journal, 2004. 50(10):2326-2334.
[2] Van Hoof, V., L. Van den Abeele, A. Buekenhoudt, et al. Economic comparison between azeotropic distillation and different hybrid systems combining distillation with pervaporation for the dehydration of isopropanol[J]. Separation and Purification Technology, 2004. 37(1):33-49.
[3] Smitha, B. Separation of organic-organic mixtures by pervaporation-a review[J]. Journal of Membrane Science, 2004. 241(1):1-21.
[4] Sato, K., K. Aoki, K. Sugimoto, et al. Dehydrating performance of commercial LTA zeolite membranes and application to fuel grade bio-ethanol production by hybrid distillation/vapor permeation process[J]. Microporous and Mesoporous Materials, 2008. 115(1-2):184-188.
[5] Sato, K., K. Sugimoto, N. Shimotsuma, et al. Development of practically available up-scaled high-silica CHA-type zeolite membranes for industrial purpose in dehydration of N-methyl pyrrolidone solution[J]. Journal of Membrane Science, 2012. 409-410:82-95.
[6] Zeng, W., B. Li, H. Li, et al. Mass produced NaA zeolite membranes for pervaporative recycling of spent N-Methyl-2-Pyrrolidone in the manufacturing process for lithium-ion battery[J]. Separation and Purification Technology, 2019. 228.
[7] Gui, T., F. Zhang, Y. Li, et al. Scale-up of NaA zeolite membranes using reusable stainless steel tubes for dehydration in an industrial plant[J]. Journal of Membrane Science, 2019. 583:180-189.
[8] Bowen, T.C., R.D. Noble, and J.L. Falconer Fundamentals and applications of pervaporation through zeolite membranes[J]. Journal of Membrane Science, 2004. 245(1-2):1-33.
[9] Wee, S.-L., C.-T. Tye, and S. Bhatia Membrane separation process—Pervaporation through zeolite membrane[J]. Separation and Purification Technology, 2008. 63(3):500-516.
[10] Huang, A.S. and J. Caro Cationic Polymer Used to Capture Zeolite Precursor Particles for the Facile Synthesis of Oriented Zeolite LTA Molecular Sieve Membrane[J]. Chemistry of Materials, 2010. 22(15):4353-4355.
[11] Yu, C., C. Zhong, Y. Liu, et al. Pervaporation dehydration of ethylene glycol by NaA zeolite membranes[J]. Chemical Engineering Research and Design, 2012. 90(9):1372-1380.
[12] Morigami, Y., M. Kondo, J. Abe, et al. The first large-scale pervaporation plant using tubular-type module with zeolite NaA membrane[J]. Separation and Purification Technology, 2001. 25(1-3):251-260.
[13] Li, H., J. Wang, J. Xu, et al. Synthesis of zeolite NaA membranes with high performance and high reproducibility on coarse macroporous supports[J]. Journal of Membrane Science, 2013. 444:513-522.
[14] Caro, J., M. Noack, and P. Kolsch Zeolite membranes: From the laboratory scale to technical applications[J]. Adsorption-Journal of the International Adsorption Society, 2005. 11(3-4):215-227.
[15] Zah, J., H.M. Krieg, and J.C. Breytenbach Layer development and growth history of polycrystalline zeolite A membranes synthesised from a clear solution[J]. Microporous and Mesoporous Materials, 2006. 93(1-3):141-150.
[16] Li, Y., H. Chen, J. Liu, et al. Microwave synthesis of LTA zeolite membranes without seeding[J]. Journal of Membrane Science, 2006. 277(1-2):230-239.
[17] Wang, Z.B., Q.Q. Ge, J. Shao, et al. High Performance Zeolite LTA Pervaporation Membranes on Ceramic Hollow Fibers by Dipcoating-Wiping Seed Deposition[J]. Journal of the American Chemical Society, 2009. 131(20):6910-6911.
[18] Pera-Titus, M., J. Llorens, F. Cunill, et al. Preparation of zeolite NaA membranes on the inner side of tubular supports by means of a controlled seeding technique[J]. Catalysis Today, 2005. 104(2-4):281-287.
[19] Huang, A.S., Y.S. Lin, and W.S. Yang Synthesis and properties of A-type zeolite membranes by secondary growth method with vacuum seeding[J]. Journal of Membrane Science, 2004. 245(1-2):41-51.
[20] Cheng, Z.-L., Z.-S. Chao, and H.-L. Wan Preparation of NaA Zeolite Membrane with High Permeability by Using a Modified VPT Method[J]. Chemistry Letters, 2006. 35(9):1056-1057.
[21] 胡子益, 李洪波, 谭宇鑫, 等. 微波合成的NaA型分子筛膜在乙醇脱水中试及3万吨/年工业示范装置的蒸汽渗透性能研究[J]. 化工进展, 2016. 35(S2):438-442.
[22] Zah, J., H.M. Krieg, and J.C. Breytenbach Pervaporation and related properties of time-dependent growth layers of zeolite NaA on structured ceramic supports[J]. Journal of Membrane Science, 2006. 284(1-2):276-290.

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