Page 148 - 《精细化工》2021年第4期

第 38 卷第 4 期 精 细 化 工 Vol.38, No.4
202 1 年 4 月 FINE CHEMICALS Apr. 2021

催化与分离提纯技术
Mn/Ti-Zr 复合氧化物催化苯甲酸甲酯选择性加氢

2
2*
2
刘 森 1,2 ，黄 锐 2,3 ，孙培永 ，张胜红 ，姚志龙
（1. 安阳工学院 化学与环境工程学院，河南 安阳 455000；2. 北京石油化工学院 恩泽生物质精细化工
北京市重点实验室，北京 102617；3. 中国石化工程建设有限公司，北京 100101）

摘要：以五水合硝酸锆和钛酸四丁酯为原料，采用共沉淀法制备 Ti-Zr-O 氧化物载体，采用浸渍法制备了 Mn/Ti-Zr
催化剂；采用 XRD、N 2 物理吸-脱附、H 2 -TPR、NH 3 -TPD 和 TG 对 Mn/Ti-Zr 催化剂进行了表征，并考察了催化
剂组成、结构和反应条件对苯甲酸甲酯（MB）加氢性能的影响，以及催化剂的长周期稳定性、失活和再生行为。
结果表明，TiO 2 含量和 Mn 负载量分别为 12%和 8%（二者均以 Ti-Zr-O 的质量为基准，下同）时制备的 Mn/Ti-Zr
–1
催化剂性能最优，该催化剂在 390 ℃、1.0 MPa、n(H 2 )∶n(MB) = 9∶1 和重时空速（WHSV）= 0.5 h 的优化条
件下能够实现 98.0% 的苯甲酸甲酯转化率和 89.7%的苯甲醛和苯甲醇选择性；苯甲酸甲酯加氢反应的活性和选
择性分别与 Mn/Ti-Zr 表面 MnO x 物种的氧化还原性和催化剂的酸性密切相关。此外，Mn/Ti-Zr 催化剂具有良好
的结构稳定性，在反应 1000 h 后仅因积炭而丧失 11% 的活性，且轻微失活的催化剂可以通过焙烧恢复其初始活
性和选择性。
关键词：苯甲酸甲酯；催化；选择性加氢；苯甲醛；苯甲醇；催化技术
中图分类号：TQ032；O643.36 文献标识码：A 文章编号：1003-5214 (2021) 04-0782-08

Selective hydrogenation of methyl benzoate catalyzed by Mn/Ti-Zr mixed oxides

1,2
2,3
2
2*
2
LIU Sen , HUANG Rui , SUN Peiyong , ZHANG Shenghong , YAO Zhilong
（1. College of Chemistry and Environmental Engineering, Anyang Institute of Technology, Anyang 455000, Henan,
China; 2. Beijing Key Laboratory of Enze Biomass Fine Chemicals, Beijing Institute of Petrochemical Technology,
Beijing 102617, China; 3. Sinopec Engineering Incorporation, Beijing 100101, China）
Abstract: Ti-Zr-O oxide were prepared by coprecipitation with zirconium nitrate and tebutyl titanate and
then they were used as supports to prepare Mn/Ti-Zr catalysts by impregnation method. The catalysts were
characterized by XRD, N 2 physical adsorption-desorption, H 2-TPR, NH 3-TPD, and TG. The effects of the
composition and structure of catalysts, as well as reaction conditions on the performances in methyl
benzoate (MB) hydrogenation, as well as catalyst lifespan, deactivation, and regeneration of Mn/Ti-Zr
catalysts were investigated. The results indicated that when TiO 2 content and Mn loading in Ti-Zr-O support
were 12% and 8% (based on the mass of Ti-Zr-O oxide, the same below), the prepared catalyst had the best
properties. This catalyst produced a high MB conversion of 98.0% and an integrated selectivity of
benzaldehyde and benzyl alcohol at 89.7% under the optimized reaction conditions [390 ℃, 1.0 MPa,
–1
n(H 2)∶n(MB) = 9∶1 and weight hourly space velocity (WHSV) = 0.5 h ]. The activity and selectivity of
Mn/Ti-Zr catalysts in the hydrogenation of MB were are related to the redox behavior of MnO x species on
the surface of Mn/Ti-Zr and the acidity of the catalysts. Besides, the catalyst exhibited excellent structural
stability with about 11% loss in activity after reaction for 1000 h due to deposition of heavy molecules and
coke on its surface. The slightly deactivated catalyst could recover its initial activity and selectivity by
simple calcination.
Key words: methyl benzoate; catalysis; selective hydrogenation; benzaldehyde; benzyl alcohol; catalysis
technology

收稿日期：2020-09-02; 定用日期：2020-11-04; DOI: 10.13550/j.jxhg.20200825
基金项目：国家自然科学基金（21703012）；恩泽生物质精细化工北京市重点实验室开放课题（2019）
作者简介：刘 森（1981—），男，博士，E-mail：0105liusen@163.com。联系人：张胜红（1982—），男，副教授，E-mail：zshong@bipt.edu.cn。