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纯硅MFI型分子筛膜的原位合成及其CO2/N2混合气体分离性能研究

作者：张宝泉，孙亮，郑孟瑶，杨军，刘秀凤

单位：（天津大学化工学院化学工程联合国家重点实验室，天津 300072）

关键词：分子筛膜；原位水热晶化；表面改性

DOI号：

分类号： O613.72；O611.4

出版年,卷(期):页码： 2017,37(2):26-31

摘要：

通过多孔?-Al2O3载体的处理或修饰改变其表面物化性质，并采用原位水热晶化法合成纯硅MFI分子筛（silicalite-1）膜。SEM、XRD和接触角的检测结果表明，未经处理、经过H2O2处理或带有氧化锆中间层的?-Al2O3载体为亲水性表面，其上不能形成连续的分子筛膜层；而经过3-氯丙基三甲氧基硅烷（3-CP-TMS）、十二烷基三甲氧基硅烷（DMS）修饰或带有壳聚糖中间层的?-Al2O3载体为疏水性表面，其上可以形成连续、致密的分子筛膜层，用DMS修饰或带有壳聚糖中间层的?-Al2O3载体上形成的分子筛膜有一定的择优取向。疏水性的载体表面是形成连续纯硅MFI分子筛膜层的先决条件，而合理的H2O/Si比是保证分子筛完全覆盖载体表面形成致密膜层的重要因素。将载体经DMS修饰后原位水热合成的纯硅MFI分子筛膜应用于CO2/N2混合气体分离过程表明，合成的膜对CO2具有分离选择性。

The porous ?-Al2O3 substrates were treated or modified to change the surface properties. The silica-MFI zeolite films were synthesized on treated or modified ?-Al2O3 substrates by in-situ crystallization. The experimental results by SEM, XRD and contact angle revealed that the untreated porous ?-Al2O3 substrate, and that treated by using H2O2 or with a zirconia intermediate layer were hydrophilic, on which the continuous zeolite film could not be formed. While the porous ?-Al2O3 substrate modified by using (3-chloropropyl)trimethoxysilane (3-CP-TMS) and dodecyltrimethoxysilane (DMS) or covered with a chitosan layer was hydrophobic, on which the continuous and dense zeolite membrane could be formed. The synthesized zeolite membrane on the porous ?-Al2O3 substrate modified with DMS or covered with a chitosan layer were preferentially oriented. The hydrophobic nature of the substrate surface should be the prerequisite for synthesizing continuous zeolite membranes, at the same time, a proper H2O/Si ratio would be a critical factor for the formation of a dense silica-MFI membrane. After being applied in separation of CO2/N2 gas mixture, the MFI membrane synthesized on DMS-modified ?-Al2O3 substrate had an increased selectivity for CO2.

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