多级孔道纳米尺度TS-1的制备及性能评价

doi:10.16085/j.issn.1000-6613.2017-2447

化工进展 ›› 2018, Vol. 37 ›› Issue (10): 3911-3918.DOI: 10.16085/j.issn.1000-6613.2017-2447

多级孔道纳米尺度TS-1的制备及性能评价

李奕川, 李亚仙, 范清, 柴永明, 刘晨光

中国石油大学(华东)化学工程学院, 重质油国家重点实验室, 山东青岛 266580

收稿日期:2017-11-27 修回日期:2018-04-17 出版日期:2018-10-05 发布日期:2018-10-05
通讯作者: 刘晨光,教授,博士生导师,主要从事油品加氢精制和工业催化研究。
作者简介:李奕川(1984-),男,讲师,主要从事绿色催化研究。E-mail:liyichuan@upc.edu.cn。
基金资助:
国家青年自然科学基金（21706289）、中央高校基础研究项目（15CX02021A）及青岛市应用基础研究项目（16-5-1-28-jch）。

Preparation of hierarchical nanosized TS-1 and its catalytic performance

LI Yichuan, LI Yaxian, FAN Qing, CHAI Yongming, LIU Chenguang

State Key Laboratory of Heavy Oil Processing, School of Chemical Engineering, China University of Petroleum(East China), Qingdao 266580, Shandong, China

Received:2017-11-27 Revised:2018-04-17 Online:2018-10-05 Published:2018-10-05

摘要/Abstract

摘要： 以四丙基溴化铵（TPABr）为模板剂、正丁胺（NBA）为碱源、可溶性淀粉作为硬模板空间填充剂，利用添加晶种且蒸汽辅助晶化的方式，制备出富含四配位Ti物种且具有多级孔道的纳米尺度TS-1，采用X射线衍射、紫外漫反射可见光谱、傅里叶变换红外光谱、电感耦合等离子光谱、N₂物理吸附-脱附及固体核磁共振等手段对所制备的样品进行一系列表征，并考察其对氯丙烯（ALC）环氧化反应的催化性能。结果表明，采用晶种辅助的方式晶粒尺寸可减小至280nm×170nm×500nm，淀粉的加入可制备出多级孔道结构且有效抑制非骨架Ti的产生；对于ALC的环氧化反应，当淀粉的添加量与SiO₂的质量比为0.4时，所制备的多级孔道TS-1催化活性最高，H₂O₂的转化率达到99.15%，环氧氯丙烷（ECH）的选择性为97.23%，并且此时ECH的收率及H₂O₂的有效利用率均较高。

关键词: 晶种辅助, 分子筛, 纳米粒子, 多级孔道, 淀粉, 氧化

Abstract: Hierarchical nanosized TS-1 with abundant tetrahedrally coordinated Ti species was synthesized by steam-assisted method under seeding. Tetrapropylammonium bromide was used as template, butylamine as alkali source, and soluble starch as a hard template. The obtained samples were characterized by powder X-ray diffraction, ultraviolet visible diffuse reflectance spectra, Fourier transform infrared spectroscopy, inductively coupled plasma spectroscopy, N₂ physical adsorption/desorption and NMR. The epoxidation of allyl chloride was used as a probe reaction to evaluate the catalytic performance of the samples. The particle size of TS-1 could reduce to 280nm×170nm×500nm using the seed-assisted method, and the addition of starch could create hierarchical structure and inhibit the formation of the extra-framework Ti effectively. For the allyl chloride epoxidation, the hierarchical TS-1 prepared with the starch/SiO₂ (mass ratio) of 0.4 exhibits an outstanding activity, with a conversion 99.15% for H₂O₂ and the selectivity of epichlorohydrin of 97.23%, respectively. Meanwhile, the yield of epichlorohydrin and the utilization efficiency of H₂O₂ are also increased.

Key words: seed-assisted, zeolite, nanoparticles, hierarchical, starch, oxidation

中图分类号:

O643

李奕川, 李亚仙, 范清, 柴永明, 刘晨光. 多级孔道纳米尺度TS-1的制备及性能评价[J]. 化工进展, 2018, 37(10): 3911-3918.

LI Yichuan, LI Yaxian, FAN Qing, CHAI Yongming, LIU Chenguang. Preparation of hierarchical nanosized TS-1 and its catalytic performance[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 3911-3918.

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多级孔道纳米尺度TS-1的制备及性能评价

Preparation of hierarchical nanosized TS-1 and its catalytic performance

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