催化学报

催化学报 ›› 2013, Vol. 34 ›› Issue (2): 391-396.DOI: 10.3724/SP.J.1088.2013.20959

• 研究论文 • 上一篇    

Ru-Fe/C催化剂上邻氯硝基苯原位液相加氢性能

许响生, 陈傲昂, 周莉, 李小青, 顾辉子, 严新焕?   

  1. 浙江工业大学绿色化学合成技术国家重点实验室培育基地, 浙江杭州 310014
  • 收稿日期:2012-11-09 修回日期:2012-12-01 出版日期:2013-02-05 发布日期:2013-02-05

Catalytic stability of othro-chloronitrobenzene hydrogenation on Ru-Fe/C catalyst

XU Xiangsheng, CHEN Ao’ang, ZHOU Li, LI Xiaoqing, GU Huizi, YAN Xinhuan*   

  1. State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
  • Received:2012-11-09 Revised:2012-12-01 Online:2013-02-05 Published:2013-02-05

PDF

832

被引次数

14

摘要： 采用浸渍法制备 Ru/C 催化剂, 并用于原位液相催化邻氯硝基苯 (o-CNB) 加氢合成邻氯苯胺 (o-CAN) 反应中. 考察了浸渍顺序、助剂、还原温度、载体和助剂含量等因素对催化剂稳定性的影响. 采用透射电子显微镜、X 射线光电子能谱、傅里叶红外光谱和 N2 吸附-脱附等手段表征催化剂. 结果表明, 以 15% Fe 为助剂, 活性炭为载体, 制备得到的 0.5% Ru-Fe/C 催化剂经过 523 K 氢气还原后 o-CNB 的转化率为 99.7%, o-CAN 的选择性达到 98.7%, 反应 140 h 未出现明显失活. 催化剂表面吸附 CO 导致中毒是失活的主要原因, 同时对催化剂再生方法进行了探究.

关键词: 钌, 四氧化三铁, 原位液相加氢, 邻氯硝基苯, 邻氯苯胺, 一氧化碳

Abstract: Ru-based crystalline catalysts were prepared by the impregnation method using different supports and promoters and were applied in the in-situ liquid phase catalytic hydrogenation of ortho-chloronitrobenzene (o-CNB) to ortho-chloroaniline (o-CAN). The effects of different preparation factors (including impregnation sequence, promoters, reduction temperature, supporters and promoter content) on the catalyst stability were investigated. The Ru-Fe/C catalyst was systematically characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and N2 adsorption-desorption with regard to physical-chemical properties such as particle size and distribution, electronic state, adsorption species, and surface parameters. The results indicated that the 0.5%Ru-15%Fe/C catalyst has higher hydrogenation activity with 99.7% o-CNB conversion and 98.7% o-CAN selectivity. The catalyst can be run for 140 h without obvious deactivation. Based on the results of characterization, the poisonous CO adsorption on catalyst surface was the main reason for deactivation, and the catalyst regeneration was studied.

Key words: ruthenium, iron oxide, in-situ liquid phase hydrogenation, ortho-chloronitrobenzene, ortho-chloroaniline, carbon monoxide