低碳化学与化工2025，Vol.50Issue(2)：38-44,7.DOI:10.12434/j.issn.2097-2547.20240316
乙烯羰基化催化反应工艺研究
Research on catalytic reaction process of ethylene carbonylation
摘要
Abstract
As the key step in the two-step synthesis of methyl methacrylate(MMA)from ethylene,ethylene carbonylation to produce methyl propionate usually uses a homogeneous catalytic system composed of precious metals,phosphine ligands and acidic additives.Sulfonic acid,as the generally used acidic additive,is beneficial for improving catalyst activity and stability,but also has process problems such as equipment corrosion and sulfonic acid accumulation.By optimizing the catalytic system,the appropriate amount of sulfonic acid required to maintain the performance of ethylene carbonylation reaction was determined,and a second additive to replace sulfonic acid was further introduced.An impact evaluation was conducted on the core elements of process development,including reaction atmosphere and solution compositions,trace impurities and reactor volumes.The potential application of this catalytic system in ethylene and high carbon alcohol carbonylation was also explored.The results show that under the conditions of reaction temperature of 100℃and operating pressure of 1.2 MPa,when the amount of sulfonic acid added(mass fraction,the same below)is 0.0145%,the turnover frequency(TOF)reaches 44400 h-1.The TOF significantly decreases to 34868 h-1,when the amount of sulfonic acid added in the reaction solution decreases to 0.0070%.Maintaining the amount of sulfonic acid added at approximately 0.0070%and introducing a second additive with an addition amount of 0.0304%to 0.0596%does not contribute to the recovery of ethylene carbonylation reaction performance.When no sulfonic acid added and the amount of the second additive added is 0.0595%,the TOF decreases to 11941 h-1,but when the amount of the second additive added increases to 2.0125%,the TOF increases to 38758 h-1.After the reaction,there is no obvious precipitation in the solution,and the catalyst stability is good(TOF is the average value of reaction for 3 h).Within a certain range,the higher the CO volume fraction and methanol content,the faster the rate of ethylene carbonylation reaction.Adding 0.1%(mass fraction)ethanol to the reaction solution and 0.442%(volume fraction)H2 to the reaction gas does not significantly affect the ethylene carbonylation reaction rate,thus reducing the purification requirements for the methanol,ethylene and CO in raw materials.After enlarging the reactor volume from 250 mL to 1000 mL,the reaction indicators such as TOF and turnover number(TON)are basically consistent,with a TON about 130000 and a selectivity of over 99%for methyl propionate after reaction for 3 h.This study can provide reference for the development of ethylene carbonylation reaction processes.关键词
羰基化/乙烯/催化剂/均相反应Key words
carbonylation/ethylene/catalyst/homogeneous reaction分类
化学化工引用本文复制引用
王光永,李荣,姚佩,丁明月,王莉,李克兵,陈鹏..乙烯羰基化催化反应工艺研究[J].低碳化学与化工,2025,50(2):38-44,7.基金项目
四川省科技计划(2019YJ0267). （2019YJ0267）
