Department of Chemical Engineering, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China.
J Phys Chem A. 2010 Mar 25;114(11):3811-7. doi: 10.1021/jp9060363.
To investigate the kinetics behaviors of dicyclopentadiene hydrogenation, a series of experiments were performed at different temperatures (323-353 K) under varying hydrogen pressure (0.5-1.5 MPa) with a range of Pd/C catalyst loading (0.25-1.00 wt %) using ethanol as solvent in a batch reactor. The time dependent concentration variations for each component were traced under the conditions of removing both the internal and external diffusion effects. The Langmuir-Hinshelwood mechanism was proposed with the consideration of the noncompetitive adsorption between the organic species with hydrogen, and the surface reaction was the rate-determining step. The kinetic equations for the sequence reaction were derived on the basis of the analysis of mechanisms, and the model parameters were determined by fitting the experimental data in differential temperature using the method of Runge-Kutta. The reaction activation energies for the first and second steps are 3.19 and 31.69 kJ x mol(-1), respectively, and the reliability of the model was verified by these experimental results to change hydrogen pressure, reactant concentration and catalyst loading. The simulation results agreed well with the experimental data.
为了研究双环戊二烯加氢的动力学行为,在间歇式反应器中使用乙醇作为溶剂,在不同温度(323-353 K)和不同氢压(0.5-1.5 MPa)下,用一系列 Pd/C 催化剂负载量(0.25-1.00 wt %)进行了一系列实验,以消除内扩散和外扩散的影响。在这些条件下,跟踪了每个组分随时间的浓度变化。考虑到有机物种与氢之间的非竞争性吸附,提出了 Langmuir-Hinshelwood 机理,并且表面反应是速率决定步骤。基于对机理的分析,推导出了顺序反应的动力学方程,并通过在微分温度下使用龙格-库塔法拟合实验数据来确定模型参数。第一和第二步的反应活化能分别为 3.19 和 31.69 kJ x mol(-1),通过改变氢压、反应物浓度和催化剂负载量对模型的可靠性进行了验证,模拟结果与实验数据吻合较好。