Page 223 - 《精细化工》2021年第7期

第 38 卷第 7 期 精 细 化 工 Vol.38, No.7
202 1 年 7 月 FINE CHEMICALS July 2021

精细化工中间体
Ru/CN 催化对苯二甲酸二甲酯加氢制备

1,4-环己烷二甲酸二甲酯

苏佳娜 1,3 ，郭秀枝 1,3 ，王公应 1,3 ，邓志勇 1,2,3*

（1. 中国科学院成都有机化学研究所，四川 成都 610041；2. 成都信息工程大学 资源环境学院，中-塞
环境与能源“一带一路”联合实验室，四川 成都 610225；3. 中国科学院大学，北京 100049）

摘要：通过超声辅助 NaBH 4 还原法制备了 3% Ru/CN（3%为 Ru 的负载量，以 CN 的质量计，下同），其中，CN
为介孔结构的氮掺杂碳材料，该催化剂用于对苯二甲酸二甲酯（DMT）加氢制备 1,4-环己烷二甲酸二甲酯
（DMCD）。采用 Raman、SEM、TEM、N 2 吸附-脱附、XRD、XPS 对载体和催化剂的组成、表面性能进行了表
征。考察了催化剂用量、反应温度、H 2 压力、反应时间对催化剂加氢性能的影响。结果表明，氮元素成功掺入
碳骨架中且氮掺杂碳材料为介孔结构。在 DMT 1.00 g，催化剂 0.05 g、反应温度 140 ℃、反应压力 5.0 MPa、
反应时间 1.0 h 的最优反应条件下，DMT 转化率为 100%，DMCD 选择性为 99.3%。以 1000 ℃下炭化制备的
CN-1000 为载体，得到的 3% Ru/CN-1000 催化剂循环使用 4 次后，催化性能未见明显下降，DMT 转化率可达
98.8%，DMCD 选择性为 99.7%。
关键词：对苯二甲酸二甲酯；1,4-环己烷二甲酸二甲酯；催化加氢；Ru/CN 催化剂；精细化工中间体
中图分类号：TQ235；TQ426 文献标识码：A 文章编号：1003-5214 (2021) 07-1505-08

Catalytic hydrogenation of dimethyl terephthalate to dimethyl

1,4-cyclohexanedicarboxylate over Ru/CN catalyst

1,3
1,3
1,3
SU Jiana , GUO Xiuzhi , WANG Gongying , DENG Zhiyong 1,2,3*
（1. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, Sichuan, China; 2. China-Serbia
″the Belt and Road″ Joint Laboratory on Environment and Energy, College of Resources and Environment, Chengdu
University of Information Technology, Chengdu 610225, Sichuan, China; 3. University of Chinese Academy of Sciences,
Beijing 100049, China）

Abstract: 3% Ru/CN catalyst (3% being the loading amount of Ru, calculated by the mass of CN, the same
below) was prepared via a simple ultrasound-assisted NaBH 4 reduction method. In which, CN was a
nitrogen doped carbon material with mesoporous structure. Then the catalyst was used for the
hydrogenation of dimethyl terephthalate (DMT) to dimethyl 1,4-cyclohexanedicarboxylate (DMCD). The
composition and surface properties of the support and catalyst were characterized by Raman spectrum,
SEM, TEM, N 2 adsorption-desorption isotherms, XRD and XPS. The effects of catalyst dosage, reaction
temperature, H 2 pressure and reaction time on the hydrogenation properties were investigated. The results
showed that nitrogen was successfully incorporated into the carbon framework and the N-doped carbon
material had a mesoporous structure. Under optimal reaction conditions of DMT 1.00 g, catalyst 0.05 g,
reaction temperature 140 ℃, reaction pressure 5.0 MPa and reaction time 1.0 h, the conversion rate of
DMT was 100% and the selectivity of DMCD was 99.3%. After recycled for 4 times, the catalytic
performance of 3% Ru/CN-1000 catalyst (CN-1000 being the support which was prepared by carbonization
at 1000 ℃) did not decrease obviously, the conversion rate of DMT and the DMCD selectivity was 98.8%
and 99.7%, respectively.

收稿日期：2021-02-23; 定用日期：2021-03-05; DOI: 10.13550/j.jxhg.20210187
基金项目：四川省科技计划资助（2021YFG0225，2021ZHZY0006）
作者简介：苏佳娜（1991—），女，硕士生，E-mail: 1139068018@qq.com。联系人：邓志勇（1983—），男，研究员，E-mail: dengzhiyong@
cuit.edu.cn。