摘要
采用基团贡献法对碳酸乙烯酯和氯气的反应进行热力学分析,计算了反应体系中各物质的熵变、焓变、吉普斯自由能、反应平衡常数,与文献中热力学数据的误差进行对比,并探讨了反应温度对氯化自由基反应的影响。热力学数据分析表明,在50~100℃之间,氯化自由基反应的主副反应均为放热反应、自发反应;两者的反应平衡常数随温度升高而升高,且反应的平衡常数很大,主反应的平衡常数低于副反应,升温不利于产物的选择性,需要适宜控制反应温度。该理论研究对碳酸乙烯酯氯化反应条件的优化及应用具有指导意义。
The thermodynamic analysis of the reaction between vinyl carbonate and chlorine gas was carried out by group contribution method.The entropy change,enthalpy change,Gipps free energy and equilibrium constant of each substance in the reaction system were calculated.The error of thermodynamic data was compared with those in literature.Thermodynamic data analysis showed that the main and secondary reactions of chlorination free radical reactions are exothermic and spontaneous reactions at 50~100℃.The equilibrium constant of the reaction increases with the increase of temperature,and the equilibrium constant of the reaction is very large,and the equilibrium constant of the main reaction is lower than that of the side reaction.The temperature rise is not conducive to the selectivity of the product,and it is suitable to control the reaction tem-perature.The theoretical research has guiding significance for the optimization and application of chlorination conditions of vinyl carbonate.
作者
朱荣振
魏玉玉
刘辉
耿德敏
凌奇
刘建路
ZHU Rongzhen;WEI Yuyu;LIU Hui;GENG Demin;LING Qi;LIU Jianlu(Shandong Haihua Group Co.,Ltd.,Weifang 262737,China;Petrochemical Branch of Shandong Haihua Group Co.,Ltd.,Weifang 262737,China)
出处
《盐科学与化工》
CAS
2024年第7期27-31,共5页
Journal of Salt Science and Chemical Industry
基金
山东省企业技术创新资助项目(202360700605)
山东海化集团有限公司科技项目(sdhh-kjxm20237JSYFZX)。
