甲醇钠催化碳酸二甲酯和乙醇合成碳酸甲乙酯和碳酸二乙酯反应动力学  

Kinetics of Synthesis of Methyl Carbonate and Diethyl Carbonate From Dimethyl Carbonate and Ethanol by Sodium Methoxide

作　　者：岳昌海 黄益平 吴丹 黄晶晶 魏振浩 王雨晨 倪泽雨 YUE Chang-hai;HUANG Yi-ping;WU Dan;HUANG Jing-jing;WEI Zhen-hao;WANG Yu-chen;NI Ze-yu(China Construction Industrial&Energy Engineering Group Co.,Ltd.,Nanjing Jiangsu 210023,China)

机构地区：[1]中建安装集团有限公司,江苏南京210046

出　　处：《当代化工》2023年第11期2589-2592,2601,共5页Contemporary Chemical Industry

基　　金：江苏省产学研合作项目,超高纯度碳酸甲乙酯和碳酸二乙酯连续反应精馏绿色合成工艺开发(项目编号:BY2021060)。

摘　　要：以甲醇钠催化碳酸二甲酯和乙醇酯交换合成碳酸甲乙酯和碳酸二乙酯,研究了催化剂的用量、反应温度、醇酯摩尔比等因素对碳酸二甲酯转化率和碳酸二乙酯收率的影响,建立了酯交换反应动力学模型,并得到相关模型参数。结果表明:该反应为两步反应,第一步产物为碳酸甲乙酯,第二部产物为碳酸二乙酯,反应焓分别为ΔH10=-0.742 kJ·mol^(-1),ΔH20=5.659 kJ·mol^(-1);活化能分别为Ea1+=38.5 kJ·mol^(-1),Ea1-=39.2 kJ·mol^(-1),Ea2+=72.1 kJ·mol^(-1),Ea2-=66.4 kJ·mol^(-1);指前因子分别为k0,1+=1.78×10^(5) L·mol^(-1)·min^(-1),k0,1-=1.23×10^(5) L·mol^(-1)·min^(-1),k0,2+=3.41×10^(9) L·mol^(-1)·min^(-1),k0,2-=1.11×10^(9) L·mol^(-1)·min^(-1)。Methyl ethyl carbonate and diethyl carbonate were synthesized by transesterification of dimethyl carbonate and ethanol catalyzed by sodium methanol.The influences of the amount of catalyst,reaction temperature,the molar ratio of alcohol to ester and other factors on the conversion of dimethyl carbonate and the yield of diethyl carbonate were studied.The transesterification kinetics model was established and the relevant model parameters were obtained.The results show that the reaction is a two-step reaction,the first step product is ethyl carbonate,the second product is diethyl carbonate,the two step reaction enthalpiesare-0.742 kJ·mol^(-1) and 5.659 kJ·mol^(-1) respectively.The forward and reverse activation energies of the first reaction are 38.5 kJ⋅mol^(-1) and 39.2 kJ⋅mol^(-1),respectively,while those of the second reaction are 72.1 kJ⋅mol^(-1)and 66.4 kJ⋅mol^(-1).The forward and reverse pre-exponential factor are 1.78×10^(5)L·mol^(-1)·min^(-1),1.23×10^(5) L·mol^(-1)·min^(-1),3.41×10^(9) L·mol^(-1)·min^(-1) and 1.11×10^(9) L·mol^(-1)·min^(-1).

关 键 词：碳酸二甲酯 乙醇 甲醇钠 碳酸二乙酯 动力学 

分 类 号：TQ225.24[化学工程—有机化工]