液相氧化羰化合成碳酸二乙酯及动力学研究  

Kinetics of the Oxidative Carbonylation of Ethanol to Diethyl Carbonate in CuCl/1,10-phen/NMI Catalytic System

作　　者：莫婉玲[1] 黄荣生[1] 梅付名[1] 李光兴[1] 

机构地区：[1]华中科技大学化学系,武汉430074

出　　处：《天然气化工—C1化学与化工》2003年第4期1-6,共6页Natural Gas Chemical Industry

基　　金：华中科技大学理学院基金资助项目

摘　　要：研究了不同含氮有机物配合CuCl对乙醇液相氧化羰化合成碳酸二乙酯反应的影响,筛选出活性高、溶解性好、腐蚀性小的多功能催化体系。推导出该催化体系的动力学方程,得到相关动力学参数。研究结果表明,CuCl/phenathroline(phen)/N methylimidazole(NMI)络合催化体系的催化活性最高,当CuCl的浓度为0 2mol/L,c(N donor)/c(CuCl)=5/2,c(phen)/c(NMI)=1/1,反应温度为120℃,反应压力为2 4MPa,CO与O2的进气比为2/1时,乙醇转化率为14 2%,碳酸二乙酯的选择性大于98%。该催化体系的动力学方程为-dpCOCO,活化能为53 36kJ/mol。对氧化羰化反应机理也进行了讨论。dt=0 246p1The influence of different Ndonor organic ligands coordinated with CuCl on the reaction of the oxidative carbonylation of ethanol to diethyl carbonate in homogeneous catalytic system has been investigated The multifunctional catalyst system which has better performance on catalytic activity, solubility and inhibition of corrosion is found The kinetic equation and relative parameters of different complex catalyst systems of CuCl and Ndonor organic ligands are obtained after the experiment data are fitted Experimental results show that in the case of concentration of catalyst CuCl 02mol/L,CNdonor /CCuCl=5/2, Cphen/CNMI=1/1,120℃,240MPa,pCO/ pO2 =2/1, the complex catalyst system of CuCl /phen/NMI has the best catalytic activity among the CuCl /Ndonor organic ligands catalytic system The conversion of ethanol is about 142% and the selectivity to diethyl carbonate is over 98% The kinetic equation could be expressed as and active energy is about 5336kJ/mol The mechanism of oxidative carbonylation of ethanol to diethyl carbonate by this CuCl /phen/NMI catalytic system has also been discussed in datail

关 键 词：碳酸二乙酯 氧化羰化 均相催化 动力学方程 

分 类 号：O631[理学—高分子化学]