甲醇和氨基甲酸甲酯制碳酸二甲酯的热力学分析  

Thermodynamic Analysis of the Synthesis of Dimethyl Carbonate from Methyl Carbamate and Methanol

作　　者：郑卓群[1] 吴廷华[1] 茆福林[1] 张奇能[1] 陈飞[1] 

机构地区：[1]浙江师范大学物理化学研究所

出　　处：《石油与天然气化工》2005年第2期87-88,共2页Chemical engineering of oil & gas

基　　金：浙江省科技厅计划项目 2004C31053;浙江丰登化工股份有限公司资助。

摘　　要：用Benson基团贡献法计算了氨基甲酸甲酯(MC)和碳酸二甲酯的标准生成焓ΔfH0m、标准生成自由能ΔfG0m和热容Cp,m,并计算了不同温度下甲醇和MC催化合成碳酸二甲酯反应的焓变ΔrH0m、自由能变化ΔrG0m、平衡常数Kp及氨基甲酸甲酯的平衡转化率c。结果表明,此反应在热力学上是完全可行的。同时采用热力学计算方法讨论了温度及反应物配比对MC平衡转化率c的影响。The standard enthalpy of formation Δ_fH^0_m, free energy Δ_fG^0_m and heat capacity C_(p,m ) of methyl carbamate(MC)and dimethyl carbonate (DMC) were calculated by the method of group contribution discovered by Benson SW. The enthalpy change Δ_fH^0_m, free energy change Δ_fG^0_m, equilibrium constant K_p of the reaction under consideration and equilibrium conversion rate c of MC were evaluated and subsequently discussed according to the principles of chemical thermodynamics. Besides, the effect of temperature and molar ratio of methanol to MC (R) on the equilibrium conversion of MC was studied. The conclusion is that the synthesis of DMC by reacting MC with methanol is quite thermodynamically favorable, and temperature affects the equilibrium conversion of MC weakly. In addition, the equilibrium conversion of MC rises when R is increased. R=2 is considered to be the best choice allowing for other factors.

关 键 词：氨基甲酸甲酯 碳酸二甲酯 热力学分析 甲醇 标准生成自由能 平衡转化率 BENSON 标准生成焓 基团贡献法 反应物配比 催化合成 自由能变 平衡常数 计算方法 MC 温度 

分 类 号：TQ225.52[化学工程—有机化工] TS207.3[轻工技术与工程—食品科学]