膦基复合催化剂高效催化二氧化碳合成环状碳酸酯  

Efficient catalytic synthesis of cyclic carbonates from carbon dioxide by phosphine-based composite catalysts

作　　者：张贺明 孟婵 董丽[2] 苏倩[2] 成卫国 Heming ZHANG;Chan MENG;Li DONG;Qian SU;Weiguo CHENG(Henan Institute of Advanced Technology,Zhengzhou University,Zhengzhou,Henan 450001,China;Beijing Key Laboratory of Ionic Liquids Cleaning Process,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China)

机构地区：[1]郑州大学河南先进技术研究院,河南郑州450001 [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》2023年第7期987-994,共8页The Chinese Journal of Process Engineering

摘　　要：二氧化碳(CO_(2))既是造成温室效应的主要气体,也是一种重要的C1资源,CO_(2)资源化利用是全球战略目标和研究热点,以CO_(2)与环氧化合物为原料合成环状碳酸酯是其高效高值化利用的主要途径。为解决以往催化剂体系存在的催化剂稳定性差、催化活性低、催化剂制备复杂等问题,本研究以高稳定性的氧膦化合物与过渡金属盐进行复配,通过调控过渡金属盐和氧膦化合物的比例,形成不同配比的二元复合催化体系,优选了最佳过渡金属盐和最佳比例(三丁基氧膦与溴化锌摩尔比为2:1,即[2Bu3PO-ZnBr2]),考察了催化剂用量、CO_(2)压力、反应时间、反应温度的影响,在最佳反应条件下(130℃,3 h,3 MPa),环氧丙烷(PO)的转化率可达92%。通过相关表征揭示了膦基复合催化体系与反应物之间的相互作用,提出了可能的催化机理。[2Bu3PO-ZnBr2]催化体系在循环使用5次后,依然能够保持高催化活性。本研究提出的膦基二元复合催化体系可为催化剂设计和CO_(2)利用提供思路。Carbon dioxide(CO_(2))is both a major contributor to the greenhouse effect and an important C1 resource.The synthesis of cyclic carbonates from CO_(2)and epoxides is an important way of high efficiency and high value utilization.The development of high efficiency catalyst is the focus of research for this reaction.In the past,there were some problems such as poor stability,low catalytic activity and complex preparation of catalyst.Therefore,the aim of this study was to develop phosphine-based catalysts with high catalytic activity,low price and good stability.In this study,a binary composite catalytic system was formed between phosphine oxide compound and metal salt with high stability.By regulating different proportions of metal salts and phosphine oxide compounds,the binary composite catalytic system with different proportions was formed,and the optimal transition metal salts and the optimal ratio were selected(Bu3PO:ZnBr2=2:1,namely[2Bu3PO-ZnBr2]).The influence of catalyst dosage,CO_(2)pressure,reaction time,and reaction temperature on propylene oxide(PO)conversion and the selectivity of propylene carbonate(PC)was investigated.The results showed that under optimum reaction conditions(130℃,3 h,3 MPa),the PO conversion was 92%,the PC selectivity was 99%and the catalyst maintained high catalytic activity after five cycles.Finally,the interactions between the phosphine-based binary composite catalytic system and the reactants were revealed through relevant characterization,and the Lewis acid cocatalytic mechanism was proposed.The phosphine-based binary composite catalytic system proposed in this study provides a new idea for efficient and inexpensive catalyst utilization.

关 键 词：二氧化碳 环加成反应 环状碳酸酯 

分 类 号：X701[环境科学与工程—环境工程] TQ225.52[化学工程—有机化工] TQ426