Page 19 - 《精细化工》2021年第1期

第 38 卷第 1 期 精 细 化 工 Vol.38, No.1
202 1 年 1 月 FINE CHEMICALS Jan. 2021

综论
钛硅分子筛 TS-1 催化烯烃环氧化反应的研究进展

刘 亚 1,2,3 ，张月成 1,2,3 ，赵继全 1,2,3*

（1. 河北工业大学 化工学院，天津 300131；2. 河北省绿色化工与高效节能重点实验室，天津 300131；
3. 天津市本质安全化工技术重点实验室，天津 300131）

摘要：TS-1 催化的烯烃环氧化反应具有条件温和、环境友好、符合绿色化学理念、应用前景广阔等优点。该文
首先介绍了不同介质中 TS-1 催化过氧化氢（H 2 O 2 ）氧化脂肪烯烃反应的进展，结果表明，在甲醇等质子溶剂中，
溶剂可以和 Ti—OOH（钛氧活性中心）通过氢键作用形成活性中间体，实现烯烃的环氧化；同时，TS-1 的酸中
心易引发环氧化物开环、聚合等副反应，适量的碱性添加剂可减少酸性位点，抑制副产物生成，提高环氧化产
物的选择性。其次，采用酸改性、碱改性、硅烷化改性或金属盐改性等方法可改善 TS-1 的催化性能。积炭是
TS-1 失活的主要原因，高温焙烧、原位 H 2 O 2 氧化或热溶剂洗涤可基本恢复 TS-1 的活性。最后指出：探索 TS-1
新的合成与改性方法以及再生方法与 TS-1 活性的关系是该领域未来的发展方向。
关键词：钛硅分子筛 TS-1；烯烃；催化；环氧化反应；改性；再生
中图分类号：TQ426.94 文献标识码：A 文章编号：1003-5214 (2021) 01-0009-09

Progress on epoxidation of alkene catalyzed by titanium silicalite-1

LIU Ya 1,2,3 , ZHANG Yuecheng 1,2,3 , ZHAO Jiquan 1,2,3*
（1. School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300131, China; 2. Hebei
Provincial Key Laboratory of Green Chemical Technology and High Efficient Energy Saving, Tianjin 300131, China;
3. Tianjin Key Laboratory of Chemical Process Safety, Tianjin 300131, China）

Abstract: The epoxidation of alkene catalyzed by titanium silicalite-1(TS-1) has the advantages of mild
conditions, environmental friendliness, conforming to the concept of green chemistry, and wide application
prospects. Firstly, the research progress of epoxidation of aliphatic alkenes catalyzed by TS-1 with
hydrogen peroxide (H 2O 2) as oxidant in different media is introduced. It is found that in protonic solvents
such as methanol, an reactive intermediate can be formed between Ti—OOH (titanium oxide active center)
and solvent through hydrogen bonding, which realizes the epoxidation of alkenes to epoxide. Meanwhile,
the acid center of TS-1 can promote side reactions such as ring-opening and polymerization of epoxides.
Treatment of TS-1 with appropriate amount of alkaline additives can reduce the amounts of acid sites and
inhibit the formation of by-products, so improve the selectivity of epoxidation products. Secondly, the
catalytic performances of TS-1 can be improved by modification with acid, alkali, silanization or metal salt.
In addition, carbon deposition is the main cause of deactivation of TS-1. The activity of the catalyst can be
recovered by calcination at high temperature, oxidation by hydrogen peroxide in situ or washing with hot
solvent. Novel synthetic and modifying methods of TS-1, as well as the relationship between the
regeneration protocol and the activity of TS-1 are the future development trends in this field.
Key words: titanium silicalite-1; alkene; catalysis; epoxidation; modification; regeneration

环氧化物是重要的有机合成中间体，广泛应用 的环氧化合物产品有环氧乙烷、环氧丙烷等。由烯
[1]
[3]
[2]
于塑料 、医药 及食品 等生产领域。目前，主要 烃合成环氧化合物的方法有过酸法、卤醇法和间接

收稿日期：2020-06-30; 定用日期：2020-08-18; DOI: 10.13550/j.jxhg.20200575
基金项目：国家自然科学基金（21776056）
作者简介：刘 亚（1996—），女，硕士生，E-mail：15230861157@163.com。联系人：赵继全（1963—），男，教授，E-mail：zhaojq@
hebut.edu.cn。