CO_(2)合成醇酯类化学品和高分子材料研究进展  

Research progress on CO_(2) to alcohols and ester chemicals and polymer materials

作　　者：白煜 梁杰[1] 王利国[2,3,4] 曹妍 贺鹏[2,3] 李会泉 BAI Yu;LIANG Jie;WANG Liguo;CAO Yan;HE Peng;LI Huiquan(School of Chemical and Environmental Engineering,China University of Mining and Technology-Beijing,Beijing 100083,China;CAS Key Laboratory of Green Process and Engineering,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China;School of Chemical Engineering,University of Chinese Academy of Sciences,Beijing,100049,China;Dalian National Laboratory for Clean Energy,Dalian 116023,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绿色过程与工程中科院重点实验室,北京100190 [3]中国科学院大学化工学院,北京100049 [4]大连洁净能源创新研究院,辽宁大连116023

出　　处：《洁净煤技术》2021年第2期117-131,共15页Clean Coal Technology

基　　金：中国科学院洁净能源先导科技专项资助项目(XDA 21030600);STS中科院区域重点项目(KFJ-STS-QYZD-138)。

摘　　要：我国作为煤炭大国,燃烧化石燃料产生大量CO_(2)。通过化学作用将CO_(2)转化为能源燃料、基础化学品或高分子材料,有利于实现碳氧资源综合利用。从CO_(2)直接利用和间接利用的角度出发,分别综述了CO_(2)资源化利用研究进展。直接利用方面,重点阐述了CO_(2)直接加氢合成甲醇和乙醇;同时CO_(2)可作为羰化剂合成有机碳酸酯和高分子材料,包括碳酸二乙酯、聚碳酸酯和CO_(2)基可降解聚合物。在间接利用方面,重点综述了CO_(2)经碳酸乙烯酯的酯交换反应合成碳酸二甲酯,以及碳酸乙烯酯加氢制备甲醇联产乙二醇的研究进展。CO_(2)加氢直接合成甲醇催化剂主要包括铜基催化剂、贵金属催化剂,由于贵金属的成本高,廉价的Cu基催化剂研究较为广泛。CO_(2)加氢直接合成乙醇研究较广泛的催化剂为贵金属(Rh、Pd、Ru)基催化剂体系,还需进一步研究廉价、高活性和高稳定性的催化剂。CO_(2)与乙醇直接合成碳酸二乙酯(DEC)研究较多的催化剂为铈基多相催化剂,但由于生成物中水分的影响,限制了DEC的收率。环氧化物和CO_(2)耦合反应生成DEC过程中不产生水,可以有效克服热力学的限制,因此高能化合物与CO_(2)的耦合路线是高效制备DEC的有效途径。CO_(2)与环氧化物共聚制备聚碳酸酯材料多采用稀土三元催化剂体系,环氧化物的转化率和聚碳酸酯选择性较高,目前已经实现工业应用。CO_(2)通过碳酸乙烯酯与甲醇酯交换合成DMC,多使用碱性较强的催化剂和含碱性基团的离子交换树脂。CO_(2)经碳酸乙烯酯加氢制备甲醇和乙二醇的反应中,铜基催化剂展现出优异的催化性能。CO_(2)化学转化利用是CO_(2)碳氧资源综合利用的重要途径,将有效支撑我国未来碳中和目标实现。As a country rich in coal,a lot of CO_(2) is produced by burning fossil fuels.CO_(2) can be transformed into energy products,chemi⁃cals or polymer materials through chemical utilization,which is favorable for realizing its resource utilization.From the perspective of direct and indirect utilization of CO_(2),the research progress of CO_(2) resource utilization was reviewed..In terms of direct utilization,the direct hy⁃drogenation of CO_(2) to methanol and ethanol was emphasized.l Meanwhile,the syntheses of organic carbonates,such as diethyl carbonate,as well as polymerization of CO_(2) with epoxide to synthesize degradable polycarbonate were emphasized.In addition,in the aspect of indirect utilization,the research progress of synthesis of dimethyl carbonate from CO_(2) via transesterification of ethylene carbonate and hydrogenation of ethylene carbonate to methanol and ethylene glycol was reviewed.Catalysts for direct methanol synthesis from CO_(2) hydrogenation mainly include copper-based catalysts and noble metal catalysts.Because of the high cost of noble metals,inexpensive Cu-based catalysts have been studied extensively.The noble metal(Rh,Pd,Ru)-based catalyst system is widely used in the direct synthesis of ethanol from CO_(2) hydrogenation,while,inexpensive,active and stable catalysts are needed to be further studied.Cerium-based heterogeneous catalyst is the most widely studied catalyst for the direct synthesis of diethyl carbonate from CO_(2) and ethanol,but the yield of DEC is low due to the water produced in the product.No water is produced in the process of coupling reaction between epoxides and CO_(2),which can effectively overcome the limitation of thermodynamics.Therefore,the coupling reaction of epoxide and CO_(2) is an effective way to prepare DEC.Rare earth ternary catalyst system is mostly used in the copolymerization of CO_(2) and epoxides to prepare polycarbonate materials.The conversion of epoxides and the selectivity of polycarbonate are relatively high,and the industrial applications h

关 键 词：CO_(2) 催化 醇 有机酯 高分子材料 

分 类 号：O623[理学—有机化学] X51[理学—化学]