基于催化氨化反应由生物质基小分子合成腈类和吡啶碱

doi:10.16085/j.issn.1000-6613.2019-1722

摘要/Abstract

摘要：

基于催化氨化反应以生物质基小分子合成腈类、吡啶碱等含氮化学品，不但可减少生产此类产品对化石资源的依赖，还可促进生物质基小分子产业的可持续发展。本文结合本文作者课题组的研究成果总结了近年来在乙醇、甘油催化氨化合成腈类、吡啶碱的最新研究进展。其中，乙醇可高收率地生产乙腈，也可在脱氢、适宜酸性催化剂催化下生成吡啶碱。甘油在适宜催化剂上既可以通过一步法也可以通过两步法转化为腈类和吡啶碱，其中催化剂适宜的酸性、较强的加氢-脱氢性能以及较大的比表面是决定生成何种目标产物的关键。采用两步法比一步法由甘油合成腈类和吡啶碱的收率明显提高。发现催化剂在使用中逐渐失活，而催化剂失活主要是由于亚胺中间体在催化剂酸中心的不可逆吸附，从而生成积炭所致。失活催化剂经高温有氧煅烧去除积炭可恢复其大部分活性。

关键词: 催化氨化, 生物质基小分子, 乙醇, 甘油, 腈类, 吡啶碱

Abstract:

Synthesis of nitriles and pyridine base from bio-based small molecules by catalytic amination can not only reduce the dependency on fossil resources in the production of these kinds of chemicals, but also promote the sustainable development of bio-based small molecule industry. Herein, the latest development in the conversion of ethanol and glycerol to nitriles and pyridine bases via catalytic amination were reviewed including the research results of our group. Among which, acetonitrile can be produced from ethanol with high yield. Ethanol can also be converted to pyridine bases over a catalyst with dehydrogenation activity and suitable acidity. Glycerol can be converted to nitriles or pyridine bases via either one step or two-step process, in which perfect acidity, stronger dehydrogenation-hydrogenation activity and bigger surface areas of catalysts are key facts to enable the catalysts with good performances. Two-step process generally produced nitriles or pyridine bases with much higher yield than one-step process. Deactivation of the catalysts took place due to the coke formation by irreversible adsorption of imine intermediates on the acid sites. Most deactivated catalysts can be regenerated via calcination at high temperature and in the presence of oxygen.

Key words: catalytic amination, bio-based small molecules, ethanol, glycerin, nitriles, pyridine bases

中图分类号:

TQ426.94

朱赫, 张月成, 赵继全. 基于催化氨化反应由生物质基小分子合成腈类和吡啶碱[J]. 化工进展, 2020, 39(8): 3077-3085.

He ZHU, Yuecheng ZHANG, Jiquan ZHAO. Synthesis of nitriles and pyridine bases from bio-based small molecules by catalytic amination[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3077-3085.

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