碳酸乙烯酯合成过程热力学分析与动力学模拟

石油炼制与化工 ›› 2024, Vol. 55 ›› Issue (3): 82-88.

碳酸乙烯酯合成过程热力学分析与动力学模拟

吕全明,刘银川,李娜,贺来宾

中石化（上海）石油化工研究院有限公司

收稿日期:2023-05-25 修回日期:2023-11-15 出版日期:2024-03-12 发布日期:2024-02-28
通讯作者: 贺来宾 E-mail:helb.sshy@sinopec.com

THERMODYNAMIC ANALYSIS AND KINETIC SIMULATING ON SYNTHESIS OF ETHYLENE CARBONATE

Received:2023-05-25 Revised:2023-11-15 Online:2024-03-12 Published:2024-02-28

摘要/Abstract

摘要： 由环氧乙烷（EO）和二氧化碳（CO₂）酯化加成生产碳酸乙烯酯（EC）是一条优选的“绿色化学”生产路线，可以为新能源汽车动力电池提供优良溶剂，更能开辟一条CO₂捕集利用与封存的绿色路线。为了研究此反应发生的可能性和反应程度，通过热力学公式对反应过程进行了热力学分析，同时建立了主反应宏观动力学模型，以指导工业反应器的设计。结果表明：除EC水解副反应为吸热反应外，主反应和其他副反应均为强放热反应；所有副反应均可以自发进行，而主反应受温度影响较大，当温度大于100 ℃时不能自发进行；通过对试验数据回归得到了该反应的动力学参数，并用工业数据进行了验证；通过动力学模型预测了反应器组合后的产物浓度，双釜串联反应器出口EC摩尔分数为98.91%，模型计算值与工业试验值误差小于0.12%。

关键词: 碳酸乙烯酯, 环氧乙烷, 热力学分析, 宏观动力学

Abstract: Ethylene carbonate (EC), produced from ethylene oxide (EO) and carbon dioxide (CO₂) via esterification addition reaction, can provide an excellent solvent for vehicle power batteries as a green new energy. The production route is a route in line with "green chemistry". More importantly, it can open up a green route of carbon capture, utilization and storage. In order to study the possibility and degree of the reaction, the thermodynamic analysis of the reaction process was carried out by the basic thermodynamic formula, and the macro-kinetic model of the main reaction was established to guide the design of industrial reactor. The results showed that the main reaction and other side reactions were all strong exothermic reactions except that the side reaction of EC hydrolysis was endothermic reaction, and all side reactions could proceed spontaneously, while the main reaction could not proceed spontaneously when the temperature was higher than 100 ℃. Then a macroscopic kinetic model including main reaction and side reactions was established to guide the design of industrial reactors. In this model, the kinetic parameters of all reactions were obtained by the regression of experimental data and verified by the industrial data. The product concentration at the outlet of the two CSTR in series was predicted by using the established kinetic model, and the EC molar fraction was 98.91%. The error between the calculated value of the kinetic model and the industrial test value was less than 0.12%.

Key words: ethylene carbonate, ethylene oxide, thermodynamic analysis, macroscopic kinetics

吕全明刘银川李娜贺来宾. 碳酸乙烯酯合成过程热力学分析与动力学模拟[J]. 石油炼制与化工, 2024, 55(3): 82-88.

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