在等温固定床反应器中考察了HZSM~5分子筛催化剂催化甲醇制丙烯(MTP)反应产物分布随空时(0.5~12min)和反应温度(400500℃)的变化规律.根据实验结果,提出新的产物集总方法.将反应产物集总为甲烷、乙烯、乙烷、丙烯、丙烷、C4、C5+等物质;结合HZSM-5催化剂上MTP反应的特点,在平行反应网络的基础上加入了高碳烃类与低碳烯烃间的转化步骤,以Runge—Kutta法求解动力学方程,用非线性最小二乘曲线拟合得到模型参数,建立考虑产物间相互转化的HZSM-5催化甲醇制丙烯反应动力学模型,通过统计检验验证了所建模型以及估值结果的可靠性.模拟值与实验结果的对比表明:该模型能够准确地反映MTP反应主要产物分布随温度和空时的变化规律,并能体现产物间的相互转化.
The transformation of methanol to propene (MTP) on HZSM-5 zeolite catalyst was carried out in a fixed-bed isothermal reactor. The product distribution of the MTP reaction was investigated at space time range 0.5-12 min and temperature range 400-500 ~C. According to the experimental results, a new product lumping method was proposed. The reaction products were lumped into seven groups including methane, ethene, ethane, propene, propane, C4, C5+. A kinetic model was proposed on the basis of par- allel reaction network. The conversion between high carbon hydrocarbons and light olefins was added to the parallel reaction network. The parameters of the kinetic model were obtained by the Runge-Kutta method and the nonlinear least squares curve fitting. The reliability of the model and the results of the pa- rameter estimation were verified by statistical test. The comparison between the experimental data and the model prediction results shows that the model reflects the MTP product distribution and the conversion between the products accurately under the experimental conditions.