环己酮肟液相重排反应机理及动力学研究  

Study of the Mechanism and Kinetics of Oxime Liquid Rearrangement Reaction

作　　者：吴素芳[1] 刘建青 徐有田 王樟茂[1] 

机构地区：[1]浙江大学化学工程与生物工程学系,浙江杭州310027 [2]浙江巨化集团公司锦纶厂,浙江衢州324004

出　　处：《高校化学工程学报》2003年第3期284-288,共5页Journal of Chemical Engineering of Chinese Universities

摘　　要：研究了环己酮肟重排反应生成己内酰胺的机理及反应动力学方程.在建立用分光光度法测定环己酮肟浓度方法的基础上,实验研究了反应温度为20～45℃范围内的液相重排反应动力学.提出了此反应的化学反应动力学速率方程式: (r肟= k0exp (-E/RT)Ca肟Cb硫酸,其中环己酮肟反应级数a为2,硫酸反应级数b为1,活化能为(E/R = (19.86 kJ·mol-1, 频率因子k0为1.35×1027.通过实验研究证实了作为催化剂的硫酸参与重排反应的机理,认为重排反应过程中游离SO3不参与反应,仅作为水的吸收剂,此结论对环己酮肟液相重排反应的生产技术改造提供了有力依据,并在生产中得到了应用.The kinetics of the oxime liquid rearrangement reaction and its mechanisum were studied. At first, the analysis method of the concentration of oxime in reaction liquid was established. In the condition of temperature 20-45°C, oxime concentration 0.0426-0.3697 mol&middotL-1 and sulfuric acid concentration 8.53-9.03 mol&middotL-1, the reaction kinetics equation is -roxime= k0exp(-E/RT) CoximeaCsulfuric acidb, in which the reaction order of oxime a is 2 and the reaction order of sulfuric acid b is 1, and the activation energy of the reaction E/R is 19.8 kJ&middotmol-1, frequency factor k0 is 1.35×1027. By experiments, the reaction mechanism has been confirmed that the sulfuric acid attends the rearrangement reaction while the free SO3 does not. SO3 is only a water absorption agent. This conclusion provides a basis for developing the technology of oxime rearrangement reaction and it has also been applied successfully in the industry.

关 键 词：重排反应 环己酮肟 动力学 己内酰胺 

分 类 号：O621.259.4[理学—有机化学] O623.542[理学—化学]