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作 者:曹宏兵[1] 李峰波[2] 闫芳[2] 段晓宇[3] 袁国卿[2]
机构地区:[1]江苏索普集团有限公司,江苏镇江212006 [2]中国科学院化学研究所,北京100190 [3]中国人民大学数学系,北京100872
出 处:《化学通报》2008年第8期616-620,共5页Chemistry
摘 要:研究了Ni/聚合物衍生碳(Ni/PDC)催化甲醇气相羰基化过程的动力学行为。Langmuir-Hinshelwood反应机制用于建立动力学数学模型,在此模型基础上导出反应速率的表达式以及反应速率与碘甲烷、一氧化碳和甲醇等反应物分压之间的数学关系。这些关系得到了实验数据的证实。反应速率对反应温度的依赖性以Arrhenius曲线给出,升高反应温度会导致反应控制机制从动力学控制模式转化为扩散控制模式,同时反应的有效速率表达式和表观活化能都有相应的变化。Methanol carbonylation over nickel supported on polymer-derive carbon was studied kinetically. Langmuir- Hinshelwood mechanism was a better choice for this case. From the kinetic model a rate expression was derived where several assumptions were introduced and the dependence of rate on the concentrations of methyl iodide, carbon monoxide and methanol was validated by experimentally observed data. The dependence of rate on the temperature was given in form of Arrhenius plot. By increasing temperature, the transition from kinetic regime to the diffusion-controlled regime was observed and changes of the effective rate and the apparent activation energy were discussed.
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