钛硅分子筛催化环己酮氨肟化本征动力学

对钛硅分子筛(TS-1)催化环己酮氨肟化反应进行了研究。根据该反应体系中环己酮可能部分吸附在TS-1分子筛活性中心上与氨发生亚胺机理,未被吸附的环己酮和羟胺中间体发生羟胺机理(双机理),建立了氨肟化反应以及该反应体系中过氧化氢分解的动力学方程,结合实验数据,对参数进行了估算及统计检验,对氨肟化反应和过氧化氢分解的动力学模型的计算值与实验值进行了比较,结果表明该模型能真实反映TS-1分子筛催化环己酮氨肟化的反应规律。同时,对双机理模型中各机理也进行了模拟计算,结果表明,双机理模型中的亚胺和羟胺机理在反应体系中发生的几率跟反应温度有很大关系。另外,过氧化氢分解动力学模型只适用于该反应体系。

Intrinsic Kinetics of Cyclohexanone Ammoximation Catalized by Titanium Silicalite Zeolite

Cyclohexanone ammoximation over TS-1 zeolite was investigated,and intrinsic kinetics was built on base of two-mechanism model which was speculated.Adsorbed cyclohexanone reacted with ammonia and cyclohexanone which was not absorbed on TS-1 reacted with hydrocylamine intermediate in cyclohexanone ammoximation.Experimental data were fitted and the values of the empirical parameters were estimated.The models were tested by mathematics statistic method and residual distribution.The model of hydrogen peroxide decomposition and two-mechanism model could reflect the reaction characteristics of cyclohexanone ammoximation over TS-1 zeolite.Model calculating based on two-mechanism model showed that reaction temperature could affect happenning ratio of hydrocylamine mechanism and imine mechanism.Otherwise,the model of hydrogen peroxide decomposition could only be used in the said reaction system.