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在大孔α-Al_2O3载体上采用二次水热生长法制备silicalite-1沸石膜。为了弥补沸石膜的缺陷并提高其疏水性，利用甲基三乙氧基硅烷(MTES)和正硅酸四乙酯(TEOS)水解共聚后的杂化有机硅Me-SiO2对沸石膜进行修饰改性。结果表明，形成的Me-SiO2溶胶平均粒径18 nm，经N2吸脱附等温线测试，表明其具有微介孔性质(孔径1.5和3.0 nm)；经凝胶化后形成疏水性的Me-SiO2/silicalite-1复合膜，其厚度分别为500 nm/10μm，表面静态接触角可达134°。在渗透汽化分离低质量分数乙醇/水时，经Me-SiO2修饰的silicalite-1膜渗透侧的水通量约为未修饰前的1/4，而在增加的膜层阻力下乙醇通量仍然得到保持甚至提高。这说明Me-SiO2修饰了膜的亲水缺陷，增强了乙醇的吸附和对水的排斥，从而提高了脱醇性能。通过优化溶胶质量分数，2.0%Me-SiO2溶胶修饰silicalite-1膜的分离性能达到最佳，在温度为60℃、质量分数为5%乙醇/水溶液中，渗透通量达到4.3 kg·m-2·h-1，分离因子为24.5。
Abstract：Silicalite-1 zeolite membranes were prepared by a secondary hydrothermal growth method on macroporous α-Al_2O3 support.In order to improve defects and hydrophobicity,the zeolite membranes were modified by Me-Si O2 sols prepared via hydrolysis and copolymerization of methyl triethoxy silane (MTES) and tetraethyl orthosilicate (TEOS).The results show that the average particle size of the Me-SiO2 sols is 18 nm,and it has micro-mesoporous structures (1.5 and 3.0 nm) analyzed by N2 adsorption-desorption isotherms.The hydrophobic Me-SiO2/silicalite-1 composite membranes were formed with a composite thickness of 500 nm/10μm and surface static contact angles up to 134°after gelation.In pervaporation of low-concentration ethanol/water,the water flux on the permeate side of the Me-SiO2 modified silicalite-1 membrane was 4 times lower than that of the unmodified one,while the ethanol flux was maintained or even increased with increased layer resistance.The results indicate that Me-SiO2 layer reduced hydrophilic defects,which enhances ethanol adsorption and water repulsion.2.0%Me-Si O2 modified silicalite-1 membranes showed optimized separation performance.In the pervaporation of 5%ethanol/water mixtures at 60℃,the permeation flux was 4.3 kg·m-2·h-1 with a separation factor of 24.5.
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基本信息:
中图分类号:TQ028.8;TQ223.122
引用信息:
[1]于欢,任秀秀,徐荣,等.疏水微介孔Me-SiO_2改性silicalite-1膜用于脱醇性能研究[J],2022,36(05):675-683.
基金信息:
中国石油化工股份有限公司科技项目(420037);; 武进区科技支撑(社会发展)项目(WS2018327);; 江苏省精细石油化工重点实验室开放课题(KF1904)