半再生重整分子水平反应动力学模型

Molecular Level Kinetic Model for Semi-Regenerative Reforming

根据实验数据建立了半再生重整分子水平反应动力学模型。模型包括305个C1-C12分子组分及864个化学反应,其中包括数十种烯烃及C6-C9所有芳烃异构体的生成与转化。以Langmuir-Hinshelwood-Hougen-Watson（LHHW）方程模拟反应速率,采用线性自由能关联方法（LFER）获取动力学参数,利用实验数据对模型进行了校正及检验。结果表明,芳烃脱烷基速率较低,应区分于加氢裂化反应;芳烃甲基迁移速率不容忽视,对C8＋芳烃产物分布有影响;模型对贫、富芳烃2种原料在10组不同反应条件下的C5＋液收、正构烷烃和环烷烃产率的预测较为准确,对C6-C9芳烃组分产率（质量分数）的预测偏差平均值小于3%。

Based on experiment results, a kinetic model was built in molecular level for semi-regenerative reforming involving 305 of Ci -C12 molecular species and 864 of chemical reactions. Formation and conversion of dozens of olefin and all C6 - C9 aromatic species were considered in the model. The reaction rate laws were expressed with Langmuir-Hinshelwood-Hougen-Watson （LHHW） formalism, and kinetic parameters were obtained by Linear free energy relationship （LFER）. With the analysis data of feeds and products, the model was tuned and the prediction precision of the model was tested. The results indicated that dealkylation of aromatics was slow enough to differ from hydrocracking. The rates of aromatic methyl shift reactions were not negligible and their contribution should lie in the distributions of C8＋ aromatics. With 2 feeds of different potential aromatic abundance processed under 10 different reaction conditions, the yields of C5＋ liquid products,normal paraffins and naphthenes were accurately predicted by the model,and the average yield（mass fraction） prediction errors of all C6 - C9 aromatic species were under 3%.