Page 83 - 《精细化工》2020年第5期

第 37 卷第 5 期 精 细 化 工 Vol.37, No.5
202 0 年 5 月 FINE CHEMICALS May 2020

功能材料
纳米尺度高配位活性钛 TS-1 的制备及性能评价

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李奕川 ，范 娟 ，范 清 ，朱国富 ，蔡 虹 ，柴永明 ，刘晨光
〔1. 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；2. 中国石油
大学（华东）石油工业训练中心，山东 青岛 266580〕
摘要：以低成本模板剂四丙基溴化铵和硅溶胶为原料，利用蒸汽辅助干胶晶化法，通过添加晶种的方式合成出
纳米级 TS-1 分子筛。再经二次水热晶化，采用乙胺和四丙基溴化铵的混合溶液对其进行处理，制备出了含有六
配位钛的高活性 TS-1 分子筛。采用 X 射线衍射、紫外漫反射可见光谱、紫外拉曼光谱、傅里叶变换红外光谱、
固体核磁共振、N 2 物理吸附-脱附测试对其物理化学性质进行了表征，并考察了其对丙烯环氧化反应的催化性能。
结果表明，纳米级 TS-1 分子筛后处理生成了活性更为优异的六配位钛物种，且其孔道结构得到了改善，比表面
积明显增大；其催化丙烯环氧化反应的活性明显提高，双氧水转化率由二次晶化处理前的 47.59%增至二次晶化
72 h 的 85.79%。
关键词：分子筛；后处理；高配位活性钛；催化氧化；功能材料
中图分类号：O641.4；O643.36；TB383.1 文献标识码：A 文章编号：1003-5214 (2020) 05-0933-08

Preparation of high coordination active titanium nano-scale TS-1
and its catalytic performance evaluation

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LI Yichuan , FAN Juan , FAN Qing , ZHU Guofu , CAI Hong ,
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CHAI Yongming , LIU Chenguang
〔1. College of Chemical Engineering, State Key Laboratory of Heavy Oil Processing, China University of Petroleum
(East China), Qingdao 266580, Shandong, China; 2. Petroleum Industry Training Center, China University of Petroleum
(East China), Qingdao 266580, Shandong, China〕
Abstract: Nano-scale TS-1 molecular sieves were synthesized using low-cost reagents (silicasol and
tetrapropylammonium bromide) by a steam-assisted crystallization method by adding the seeds. The
molecular sieves were post-modified using mixed solution of ethylamine and tetrapropylammonium
bromide by secondary hydrothermal crystallization to produce TS-1 molecular sieves with high catalytic
activity containing hexacoordinate titanium. The physicochemical properties of the obtained molecular
sieves were characterized by X-ray diffraction, UV diffuse reflectance visible spectroscopy, ultraviolet
Raman spectroscopy, Fourier transform infrared spectroscopy, solid state nuclear magnetic resonance, and
N 2 physical adsorption-desorption. The epoxidation of propylene was used as a probe reaction to evaluate
the catalytic performance of the samples. The results showed that the nano-scale TS-1 synthesized by
post-modification had hexacoordinate titanium species, with improved pore structure and obviously
increased specific surface area. The activity of catalyzing the epoxidation of propylene was obviously
improved. The conversion rate of hydrogen peroxide was significantly increased from before secondary
crystallization 47.59% to 85.79% for crystallization time 72 h.
Key words: zeolite; post-modification; hexacoordinate active titanium; catalytic oxidation; functional materials

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18 世纪中期，瑞典科学家 CRONSTEDT 在一次 始了对沸石分子筛的研究 。1983 年，意大利科学
[2]
鉴定工作中，偶然发现了沸石分子筛，从此人们开 家 TARAMASSO 等 采用传统水热合成方法，将金

收稿日期：2019-10-08; 定用日期：2020-01-15; DOI: 10.13550/j.jxhg.20190942
基金项目：国家自然科学青年基金项目（21706289）；青岛市应用基础研究项目（16-5-1-28-jch）
作者简介：李奕川（1984—），男，博士，讲师，E-mail：liyichuan@upc.edu.cn。