乙烯羰基化催化反应工艺研究  

Research on catalytic reaction process of ethylene carbonylation

作　　者：王光永 李荣 姚佩 丁明月 王莉 李克兵 陈鹏 WANG Guangyong;LI Rong;YAO Pei;DING Mingyue;WANG Li;LI Kebing;CHEN Peng(State Key Laboratory of Industrial Vent Gas Reuse,National Center of C1 Chemical Engineering Research,Southwest Institute of Chemical Co.,Ltd.,Chengdu 610225,Sichuan,China)

机构地区：[1]西南化工研究设计院有限公司工业排放气综合利用国家重点实验室,国家碳一化学工程技术研究中心,四川成都610225

出　　处：《低碳化学与化工》2025年第2期38-44,共7页Low-Carbon Chemistry and Chemical Engineering

基　　金：四川省科技计划(2019YJ0267)。

摘　　要：作为乙烯两步法制甲基丙烯酸甲酯(MMA)的重要步骤,乙烯羰基化制丙酸甲酯通常采用贵金属、膦配体与酸性助剂构成的均相催化体系,常用的酸性助剂磺酸有利于提升催化剂活性与稳定性,但同时也具有设备腐蚀与磺酸累积等工艺问题。通过优化催化体系,确定了维持乙烯羰基化反应性能所需的适宜磺酸添加量,并进一步引入了第二助剂替代磺酸。针对反应气氛与反应液组成、原料微量杂质以及反应釜体积等工艺开发的核心要素进行了影响评价,并探讨了该催化体系在乙烯高碳醇羰基化方面的应用潜力。结果表明,在反应温度100℃、操作压力1.2 MPa条件下,磺酸添加量(质量分数,下同)为0.0145%时,转化频率(TOF)达44400 h^(-1);反应液中磺酸添加量降低至0.0070%时,TOF显著降低至34868 h^(-1)。维持磺酸添加量为约0.0070%,并引入添加量为0.0304%~0.0596%的第二助剂无助于乙烯羰基化反应性能的恢复。反应液中无磺酸添加、第二助剂添加量为0.0595%时,TOF降低至11941 h^(-1),但当第二助剂添加量提高到2.0125%时,TOF升至38758 h^(-1),反应后釜液无明显沉淀,催化剂稳定性良好(TOF均为反应3 h的平均值)。在一定范围内,CO体积分数和甲醇含量越高,乙烯羰基化反应速率越快。反应液中添加质量分数为0.1%的乙醇、反应气氛中添加体积分数为0.442%的H_(2),未对乙烯羰基化反应速率造成明显影响,可降低对原料中甲醇、乙烯和CO的纯化要求。反应釜体积由250 mL放大至1000 mL,反应3 h后,TOF与总转化数(TON)等反应指标基本一致,TON均约为130000,丙酸甲酯选择性均为99%以上。该研究可为乙烯羰基化反应工艺的开发提供借鉴。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 ethyl

关 键 词：羰基化 乙烯 催化剂 均相反应 

分 类 号：TQ225.24[化学工程—有机化工] TQ426