CO直接酯化技术研究进展  

Research Progress of CO Direct Esterification Technology

作　　者：张孜群 徐玉平 刘耀虎 孙径[1] 徐忠宁[1] 郭国聪[1] Zhang Ziqun;Xu Yuping;Liu Yaohu;Sun Jing;Xu Zhongning;Guo Guocong(State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy ofSciences,Fujian,350002;Bureau of Frontier Science and Education,Chinese Academy of Sciences,Beijing,100864)

机构地区：[1]结构化学国家重点实验室,中国科学院福建物质结构研究所,福建350002 [2]中国科学院前沿科学与教育局,北京100864

出　　处：《当代化工研究》2022年第4期156-161,共6页Modern Chemical Research

基　　金：国家重点研发计划项目“重要反应过程贵金属催化材料的等效减量研究”(项目编号:2021YFB3801600);国家重点研发计划项目“高附加值精细化工产品的多相纳米催化材料与工程化”(项目编号:2017YFA0206800);国家重点研发计划项目“甲烷和二氧化碳催化转化及外场耦合化学键精准重构”(项目编号:2017YFA0700100);国家自然科学基金面上项目“CO酯化催化剂的载体结构对Pd电子结构的精细调控研究”(项目编号:22172171)。

摘　　要：CO直接酯化是以CO为起始原料,酯类化学品为目标产品的反应过程,其目标产品包括但不限于草酸二甲酯、碳酸二甲酯、甲酸甲酯等高附加值酯类化学品。催化剂是CO直接酯化过程的关键核心技术。如何突破催化剂构建与工程化的技术瓶颈,研发出高性能、长寿命的催化剂并进行催化剂规模化制备是CO酯化领域的关键科学与技术问题。本文综述了近几年CO直接酯化制草酸二甲酯、碳酸二甲酯、甲酸甲酯催化剂的研究进展,阐述了“CO直接酯化”共性关键技术的内涵:(1)揭示并证实了活性组分Pd裸露的(111)晶面是CO酯化制草酸二甲酯反应高活性的择优晶面;(2)揭示了活性组分Pd的聚集状态是CO酯化产物选择性控制的关键结构基元:原子级分散的孤立态Pd活性中心有利于生成碳酸二甲酯,而聚集态Pd活性中心则有利于生成草酸二甲酯;(3)揭示了载体的Lewis酸碱性对CO酯化产物选择性控制的影响:Lewis酸性载体有利于生成碳酸二甲酯,而Lewis碱性载体有利于生成草酸二甲酯;(4)通过载体晶格调控或引入缺陷,可形成金属-金属键,增强金属与载体之间的电子转移,有效提升催化剂稳定性。本综述将为CO直接酯化制酯类化学品研究提供有益指导。CO direct esterification is a reaction process in which CO is the starting material and ester chemicals are the target products,including but not limited to high value-added ester chemicals such as dimethyl oxalate,dimethyl carbonate and methyl formate.Catalysts are the key technology of CO direct esterification.How to break through the technical bottleneck of catalyst construction and engineering,develop high performance,long life catalyst and carry out large-scale preparation of catalysts are the key scientific and technical issues in the field of CO direct esterification.This article reviews the research progress of catalysts for the production of dimethyl oxalate,dimethyl carbonate,and methyl formate by CO direct esterification in recent years,and reveals the nature of the common key technology of“CO direct esterification”:1)The exposed(111)crystal face of active component Pd has been confirmed to be the preferred crystal face with high activity for the esterification of CO to dimethyl oxalate;2)It was revealed that the aggregation state of active component Pd was the key structural element for the selective control of CO esterification products:the atomically dispersed isolated active center of Pd was conducive to the formation of dimethyl carbonate,while the aggregated active center of Pd was conducive to the formation of dimethyl oxalate;3)The effect of the Lewis acidity and basicity of the support on the selective control of CO esterification products is revealed:the Lewis acidic support is conducive to the production of dimethyl carbonate,while the Lewis basic support is conducive to the production of dimethyl oxalate;4)By adjusting or introducing defects in the support lattice,a metal-metal bond can be formed,which enhances the electron transfer between the metal and the support,and effectively improves the stability of the catalyst.This review will provide useful guidance for the study of ester chemicals produced by the CO direct esterification.

关 键 词：CO直接酯化 催化剂 草酸二甲酯 碳酸二甲酯 甲酸甲酯 

分 类 号：O6[理学—化学]