烯烃和CO_(2)直接合成环状碳酸酯的催化剂研究进展  

Recent advances in catalysts for direct synthesis of cyclic carbonates from olefins and CO

作　　者：胡启鲁 赵国英[2] 于彩虹[1] Qilu HU;Guoying ZHAO;Caihong YU*(College of Chemistry and Environment Engineering,China University of Mining and Technology,Beijing 100083,China;Beijing Key Laboratory of Ionic Liquid Cleaning Process,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China)

机构地区：[1]中国矿业大学(北京)化学与环境工程学院,北京100083 [2]中国科学院过程工程研究所离子液体清洁过程北京市重点实验室,北京100190

出　　处：《过程工程学报》2021年第7期762-773,共12页The Chinese Journal of Process Engineering

基　　金：国家自然科学基金资助项目(编号:21878303,21676278);国家重点基础研究发展基金资助项目(编号:2016YFB0601303)。

摘　　要：利用丰富且价廉易得的烯烃和CO_(2)直接反应可提供一种经济安全环保的高附加值环状碳酸酯生产工艺,具有减少CO_(2)排放、缓解温室效应等优点。本工作以一步氧化羧化、顺序氧化羧化以及羟溴化羧化三种方法为主线,综述了近年来烯烃和CO_(2)直接制备环状碳酸酯相关催化剂的研究进展,包括用于氧化羧化反应的催化剂,主要是同时具有烯烃环氧化催化功能和CO_(2)羧化功能的多组分组合催化剂和多活性位点的单一催化剂,如金属氧化物、金属配合物、离子液体、改性分子筛、金属有机骨架化合物等;以及作用于羟溴化羧化反应的含Br-, I-阴离子的卤代试剂-无机/有机碱脱质子试剂组合催化剂。同时对未来烯烃和CO_(2)制备环状碳酸酯反应的催化剂的设计及工艺开发进行了展望。The valorization of CO_(2) into value-added chemical compounds via economically viable process could be one of effective strategies to reduce CO_(2) emission and therefore the climate change impact. The cyclic carbonates are industrially produced by cycloadditions between CO_(2) and epoxides. However, there are safety risks in this technology due to the need to handle the flammable and explosive epoxides. Direct synthesis of cyclic carbonates from olefins and CO_(2) could provide a safer, more economic and environment-friendly alternative technology. Herein,the latest research progress in catalysts for synthesis of cyclic carbonates via one-step oxidative carboxylation,sequential oxidative carboxylation and hydroxyl bromide carboxylation of olefins is summarized. The reported catalysts for oxidative carboxylation approach are mainly multi-component composite catalysts, of which include at least both catalytic components for epoxidation of olefins and carboxylation with CO_(2). Single component catalysts with catalytic active function or site for both epoxidation of olefins and carboxylation with CO_(2), have been rarely reported in the literature and are also described here. The catalysts for hydroxyl bromide carboxylation of olefins typically consist of a halogenating reagent and an inorganic/organic base deprotonating reagent. The effects of reaction approach, catalyst structure/components, catalytic mechanism and reaction conditions on the yields and selectivity of CC are also systematically summarized and explored. In the view of green chemistry, oxidation carboxylation of olefin is of higher atom-economy and environmental benefits while hydroxyl bromide carboxylation is always accompanied by the formation of a large number of side-products. An efficient heterogeneous single component catalyst with integrated cooperative catalytic active sites for epoxidation, carboxylation, CO_(2) adsorption concentration, etc., which simplity the separation and recovery of catalysts and products, will be the future research

关 键 词：烯烃 环氧化 羟溴化 二氧化碳 羧化 环状碳酸酯 

分 类 号：TQ426.6[化学工程]