钛硅分子筛催化环己酮氨肟化反应过程——本征动力学

INTRINSIC KINETICS OF AMMOXIMATION OF CYCLOHEXANONE TO CYCLOHEXANONE OXIME OVER HTS ZEOLITE

对钛硅分子筛(HTS)催化环己酮氨肟化反应本征动力学进行了研究。利用经验方程拟合了试验数据,并采用Marquardt算法对经验方程的参数进行确定,获得了不同试验条件下的反应初速率,然后再用高斯-牛顿法对本征动力学模型进行了参数估计,得出了氨肟化反应以及该反应体系中H_2O_2分解的本征动力学。并对该模型进行了残差分析和F检验,对氨肟化反应和H_2O_2分解的动力学模型的计算值与试验值进行了比较,获得相对误差绝对值的平均值分别为5.21％和6.25％。表明该模型能真实反映HTS催化环己酮氨肟化的反应特性,是合理可靠的,能为进一步的过程开发与工程设计提供一些理论上的指导和设计上的依据;而H_2O_2分解副反应动力学模型仅适用于该反应体系。

The intrinsic kinetics of cyclohexanone ammoximation over HTS zeolite was inves-tigated. Experimental data were fit using an empirical equation and the values of the empirical parameters were determined by Marquardt technique, thus the initial reaction rates of the cyclohexanone am-moximation and the decomposition of hydrogen peroxide at different reaction conditions were obtained. The parameters were estimated for the rate models by Gauss-Newtonian algorithm and the kinetic equa-tions were established. The models were tested by mathematics statistic method and residual distribu-tion. Comparing the predicted values based on models with experimental values showed that the average values of relative error absolute values were 5. 21% and 6. 25% respectively. The models were reasona-ble and reliable which could reflect the reaction characteristics of cyclohexane ammoximation over HTS zeolite. The models could also provide theoretical instruction and design basis for process development and engineering design. However, the modei of hydrogen peroxide decomposition could only used in the said reaction system.