骨架镍催化1-环己烯乙腈选择加氢制备1-环己烯乙胺反应动力学研究

Kinetics of Hydrogenation of 1-Cyclohexenyl-Acetonitrile to Form 1-Cyclohex-1-en-1-Ethylamine Catalyzed by Skeletal Nickel

1-环己烯乙腈选择加氢是1-环己烯乙胺生产中的关键步骤之一。采用骨架镍催化剂在间歇高压釜中考察1-环己烯乙腈选择加氢制备1-环己烯乙胺的反应动力学。在消除内外扩散影响的条件下,通过测定催化加氢过程中1-环己烯乙腈浓度随时间的变化关系,获得了1-环己烯乙腈催化加氢动力学模型。动力学模型表明,1-环己烯乙腈选择加氢制备1-环己烯乙胺,对1-环己烯乙腈为零级反应而对氢压为一级反应。根据实验数据拟合出动力学参数,其中指前因子k0和活化能Ea分别为23.64和27.96 kJ mol 1。将动力学模型的方程、反应速率和反应物浓度的计算值和实验值进行比较,表明模型具有较高的拟合精度,能准确反映骨架镍催化1-环己烯乙腈选择加氢制备1-环己烯乙胺反应过程及其动力学特征。

Hydrogenation of l-cyclohexenyl-acetonitrile （CA） is the key step for producing l-cyclohex-l-en-l-ethylamine. Reaction kinetics of hydrogenation of 1-cyciohexenyi-acetonitrile to form l-eyclohex-l-en-l-ethylamine catalyzed by skeletal Nickel was studied in a batch reactor at elevated pressure under conditions with free from the influence of external, and internal diffusions, and the kinetics parameters were determined by fitting the changes of l-eyclohexenyl-acetonitrile concentrations with time. Based on the mechanisms of 1-cyclohexenyl-acetonitrile hydrogenation reaction, a kinetics model was proposed. The results indicate that the I-cyclohexenyl-acetonitrile hydrogenation to form 1-cyelohex-l-en-1-ethylamine is zero order with respect tol-cyclohexenyl-acetonitrile and first order with respect to hydrogen. The calculations show that the pre-exponential factor and the activation energy of the hydrogenation are 23.64 and 27.96 J-mol-1, respectively. The simulative data of the kinetic model was compared with those obtained by the experiment. The results indicate that the model exhibits high fitting precision for simulation.