环戊醇液相脱氢本征动力学

Intrinsic Kinetics Study on Dehydrogention of Cyclopentanol

以Raney镍为催化剂,对环戊醇脱氢制环戊酮的本征动力学进行了研究。首先通过热力学分析消除了环戊酮加氢逆反应的可能性,并通过机理讨论,认为可以用指数形式来表达环戊醇脱氢速率。采用高斯-牛顿法,根据实验数据进行参数估算,得到了本征动力学模型参数,经统计检验表明,所得动力学模型是适当的。该反应的速率方程为-dcA/dt=kc2A,反应活化能为63 05kJ/mol,反应速率常数为3 1×104exp(-63050/RT)。在动力学研究的基础上,对脱氢微观机理进行了讨论。

Intrinsic kinetics of dehydrogenetion of cyclopentanol was investigated in the presence of Raney-Ni catalyst.Analysis on reaction thermodynamics denied occurrence of the hydrogenation of cyclopentanone,the reverse reaction.Based on reaction mechanism discussion it was reasonable to express the dehydrogenation rate equation of cyclopentanol in an exponential form.Parameters of the intrinsic kinetics model were solved by the Gauss-Newton method based on the experimental data.Through statistic test and residual error distribution the intrinsic kinetics model was proved to be adequate.Rate equation for the catalytic reaction was-dc/dt=kc^2_A,where E_a=63.05 kJ/mol;and k=3.1×10~4×exp(-63 050/RT).Micromechanism of dehydrogenation was also discussed.