Page 107 - 精细化工2020年第2期

第 37 卷第 2 期 精 细 化 工 Vol.37, No.2
202 0 年 2 月 FINE CHEMICALS Feb. 2020

催化与分离提纯技术
高分散镍硅催化剂对喹啉催化加氢的性能

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杨晓魏，夏张辉，王 涛，牛立博 ，胡泽楷，白国义
（河北大学 化学与环境科学学院，河北 保定 071002）

摘要：以硝酸镍和硅溶胶为原料，采用蒸氨水热法，制得了一系列负载量为 10%（以镍在催化剂中的质量分数
计，下同）的镍硅酸盐衍生的 Ni-PS-AEH-x（x 代表不同焙烧温度，下同）催化剂，并用于喹啉选择性加氢制取
1,2,3,4-四氢喹啉。通过考察不同镍基催化剂的加氢性能，发现 Ni-PS-AEH-400 催化性能最好。通过考察反应条
件的影响，确定最佳反应条件为：底物与金属镍投料比（物质的量之比，下同）为 30∶1、反应温度 100 ℃、
氢气压力 3 MPa、反应时间 120 min，此时喹啉转化率为 99.0%，1,2,3,4-四氢喹啉收率为 95.4%。采用 FTIR、
XRD、TEM、N 2 吸附-脱附、H 2 -TPR 和 XPS 对催化剂结构、组成、形貌进行了表征，结果表明：镍硅酸盐结构
使 Ni-PS-AEH-400 比表面积大、镍纳米粒子分散均匀，活性中心与载体间的相互作用力强，使其在喹啉加氢反
应中具有较浸渍法制备 Ni/SiO 2 -IMP 更优异的催化性能。
关键词：镍基催化剂；硅酸盐；催化加氢；喹啉；1,2,3,4-四氢喹啉
中图分类号：O643.38 文献标识码：A 文章编号：1003-5214 (2020) 02-0309-08

Catalytic performance of highly dispersed nickel-silica
catalysts in quinoline hydrogenation

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Yang Xiaowei, Xia Zhanghui, Wang Tao, Niu Libo , Hu Zekai, Bai Guoyi
（College of Chemistry and Environmental Science, Hebei University, Baoding 071002, Hebei, China）

Abstract: A series of Ni-PS-AEH-x (x means different calcination temperatures, the same below) catalysts
with a nickel loading around 10% (mass fraction of nickel in a catalyst, the same below) were prepared by
ammonia evaporation hydrothermal method using nickel nitrate and silica sol as raw materials. The
catalysts were used to synthesize 1,2,3,4-tetrahydroquinoline by selective hydrogenation of quinoline. The
results showed that Ni-PS-AEH-400 catalyst had the best catalytic performance by investigating the
hydrogenation performance of different nickel-based catalysts. The reaction conditions for hydrogenation of
quinoline were optimized. The optimal reaction conditions were as follows: molar ratio of quinoline to Ni
30∶1, reaction temperature 100 ℃, hydrogen pressure 3 MPa, reaction time 120 min. Under the above-
mentioned conditions, the conversion of quinoline rate was 99.0%, and the yield of 1,2,3,4-tetrahydroquinoline
was 95.4%. The structure, composition and morphology of the catalysts were characterized by XRD, TEM,
N 2 adsorption-desorption, H 2-TPR, and XPS. The results indicated that Ni-PS-AEH-400 exhibited better
catalytic performance than Ni/SiO 2-IMP prepared by impregnation method due to its larger specific surface
area, active particle with higher dispersion and stronger interaction between the active particles and the
support.
Key words: nickel-based catalyst; phyllosilicate; catalytic hydrogenation; quinoline; 1,2,3,4-tetrahydroquinoline

[1]
1,2,3,4-四氢喹啉及其衍生物是一类重要的精细 研究价值 。通过喹啉类化合物催化加氢法制备
化学品，在药物化学和染料合成研究中具有重要的 1,2,3,4-四氢喹啉是一种相对环保的生产途径 [2-3] 。其

收稿日期：2019-07-27; 定用日期：2019-09-03; DOI: 10.13550/j.jxhg.20190743
基金项目：国家自然科学基金（21676068）；河北省自然科学基金重点项目（B2019201341）
作者简介：杨晓魏（1994—），女，硕士生，E-mail：Yxwei1209@163.com。联系人：牛立博（1984—），男，副教授，硕士生导师，
E-mail：libo_niu@126.com；白国义（1975—），男，教授，博士生导师，E-mail：baiguoyi@hotmail.com。