催化学报

催化学报 ›› 2006, Vol. 27 ›› Issue (10): 921-926.

• 研究论文 • 上一篇    下一篇

负载型纳米贵金属催化剂催化吡啶及其衍生物的加氢反应

薛芳1,林棋1,2,杨朝芬1,李贤均1,陈华1   

  1. 1 四川大学化学学院有机金属络合催化研究所绿色化学与技术教育部重点实验室, 四川成都 610064; 2 闽江学院化学与化学工程系, 福建福州 350008
  • 收稿日期:2006-10-25 出版日期:2006-10-25 发布日期:2010-11-28

Hydrogenation of Pyridine and Its Derivatives over Supported Nanometer Noble Metal Catalysts

XUE Fang1, LIN Qi1,2, YANG Chaofen1, LI Xianjun1, CHEN Hua1*   

  1. 1 Key Laboratory of Green Chemistry and Technology of Ministry of Education, Institute of Homogenous Catalysis, College of Chemistry, Sichuan University, Chengdu 610064, Sichuan, China; 2 Department of Chemistry and Chemical Engineering, Minjiang College, Fuzhou 350008, Fujian, China
  • Received:2006-10-25 Online:2006-10-25 Published:2010-11-28

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1116

被引次数

37

摘要： 制备了负载型高分散的纳米贵金属催化剂和含Ru的双金属催化剂,并考察了催化剂对吡啶及其衍生物加氢反应的催化性能. 结果表明, 5%Ru/C催化剂对吡啶加氢反应的催化活性高于5%Pd/C, 5%Pt/C和5%Ir/C. 在100 ℃, 3.0 MPa, 1 h和Ru/吡啶摩尔比=2.5/1000 的条件下, 5%Ru/C催化吡啶加氢的转化率大于99.9%, 生成哌啶的选择性为100%. 催化剂重复使用5次后,活性和选择性无明显下降. 在Ru催化剂中加入少量的Pd和Ir后催化剂活性没有明显的变化. 采用X射线衍射、高分辨透射电镜和X射线光电子能谱对还原后的5%Ru/C催化剂进行表征,结果表明Ru以高分散金属态存在,其平均粒径小于5 nm. 不同底物的加氢反应活性为: 吡啶≈2-甲基吡啶>2,6-二甲基吡啶>3-甲基吡啶>4-甲基吡啶>3,5-二甲基吡啶>2-甲氧基吡啶.

关键词: 钌, 活性炭, 负载型催化剂, 吡啶, 加氢, 哌啶, 甲基吡啶

Abstract: The highly dispersed supported noble metal catalysts were prepared and their catalytic performance for hydrogenation of pyridine was investigated. The results indicated that the 5%Ru/C catalyst exhibited the highest activity compared with Pd/C, Pt/C and Ir/C. The order of catalyst activity was Ru/C>Pd/C>Pt/C>Ir/C. Under the optimum reaction conditions of 100 ℃, p(H2)=3.0 MPa, and Ru/pyridine molar ratio=2.5/1?000, pyridine could be completely converted to piperidine with a 100% selectivity over 5%Ru/C. Furthermore, the activity and selectivity of 5%Ru/C did not decrease significantly after 5 cycle runs. The activity of bimetallic catalysts Ru-Pd/C and Ru-Ir/C was slightly lower than that of Ru/C, whereas the activity of Ru-Co/C was much lower than that of Ru/C. The reduced 5%Ru/C catalyst was characterized by high resolution transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results showed that ruthenium was reduced to zero valence and the average particle diameter of Ru crystallites was smaller than 5 nm. The hydrogenation reactivity of pyridine and its derivatives was in the order pyridine≈2-methylpyridine>2,6-dimethylpyridine>3-methylpyridine>4-methylpyridine>3,5-dimethylpyridine>2-methoxy-pyridine, indicating that the electron factor played an important role in the reaction process.

Key words: ruthenium, activated carbon, supported catalyst, pyridine, hydrogenation, piperidine, methylpyridine