Progress of ionic liquids and supported palladium catalysts in the hydrogenation reactions

doi:10.16085/j.issn.1000-6613.2017.02.021

Abstract

Abstract: Ionic liquids can be used as solvents,catalytic active sites,stabilizers,dispersants et al owing to their unique solvent performances,catalytic performances and designable structures. Supported palladium catalysts have many advantages such as high specific surface area,metal dispersion and good thermal stability,as well as problems of low selectivity of target selectivity,high cost and unclear reaction mechanism. Taking selective hydrogenation of phenol as the probe reaction,this paper summarizes the requirements for the catalysts and the advantages of palladium. Hydrogenation catalysts of phenol are divided into inorganic supported Pd catalysts,polymer supported Pd catalysts and ionic liquid-polymer supported Pd catalysts. The influences of carriers,ionic liquids,palladium salts,additives on the catalytic performance are analyzed. The results show that non-porous,polyfunctional alkaline carriers with certain microstructures,and certain elements such as P,N have better catalytic performance. And carriers with more basic sites are more likely to have higher activity and selectivity. Additives such as Na、K、Al、Ni、Ca、Cs et al can improve the catalytic performance while reducing costs. The hydrogenation performance of Pd(OAc)₂ is better than that of the other three. The application of ILs makes it easier to separate the catalysts from the reaction system,relieves the reaction requirements,and improves the activity and selectivity of catalysts. So the in-depth studies of ionic liquids in the catalytic hydrogenation process,catalytic hydrogenation mechanisms and catalyst stability are the primary directions in the future.

Key words: ionic liquid, palladium-based catalyst, support, hydrogenation, selectivity

摘要： 离子液体因其独特的溶剂性能、催化性能及结构可设计性，在催化体系中可作溶剂、催化活性中心、稳定剂、分散剂等。负载型钯催化剂具有比表面积大、金属分散性和热稳定性好等优点，但存在着催化剂对目标产物选择性差、成本高、反应机理尚不明确等问题。本文以苯酚选择性加氢为探针反应，综述了该反应对催化剂的要求及贵金属钯的优势。将苯酚加氢催化剂分为无机负载钯催化剂、聚合物负载钯催化剂和离子液体-聚合物负载钯催化剂三类，并分析了载体性质、助剂、离子液体、钯盐等对催化性能的影响。分析表明：具有一定规则微观形貌、含P、N等元素的非多孔性多官能团碱性载体催化效果较好，且载体中含有较多碱性中心，有利于催化剂活性和选择性的提高；助剂Na、K、Al、Ni、Ca、Cs等的加入可在降低成本的同时提高催化性能；钯盐Pd（OAc）₂加氢性能优于Pd（acac）₂、PdCl₂、Pd（NO₃）₂；离子液体的引入不仅使反应体系易分离、反应条件降低，而且提高了催化剂活性和选择性。今后的主要发展方向是深入研究离子液体在催化加氢过程中的作用、催化加氢机理、催化剂稳定性等。

关键词: 离子液体, 钯基催化剂, 载体, 加氢, 选择性

CLC Number:

TQ032.4

ZHANG Wenlin, ZHANG Jiali, JIN Fei, GAO Zhanyan, CHEN Yao, LI Chunli. Progress of ionic liquids and supported palladium catalysts in the hydrogenation reactions[J]. Chemical Industry and Engineering Progree, 2017, 36(02): 548-554.

张文林, 张佳莉, 靳斐, 高展艳, 陈瑶, 李春利. 离子液体及负载型钯催化剂在加氢反应中的研究进展[J]. 化工进展, 2017, 36(02): 548-554.

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