基于结构导向集总的柴油加氢精制分子水平反应动力学模型 Ⅰ.模型的建立与验证

Molecular level reaction kinetic model of diesel hydrofining based on structure-oriented lumping Ⅰ. Establishment and verification of the model

为了从分子水平揭示柴油加氢精制反应过程的转化规律,基于结构导向集总方法,构建了表征柴油分子组成的包含846 个结构向量的分子组成矩阵。根据柴油加氢精制反应机理,编制了 34 条反应规则,建立了包含约 17 500 个反应的柴油加氢精制反应网络,并结合基于量子化学计算的反应动力学参数,建立了基于结构导向集总的分子尺度柴油加氢精制反应动力学模型。采用改进的 Runge-Kutta 法进行求解,并通过与工业装置数据对比验证了模型的可靠性。实验结果表明,加氢精制产物分布及典型分子含量的预测值与工业数据的最大误差在 1.0%以内,温升的预测误差不超过 2 ℃。

Based on the structure-oriented lumping method,a molecular matrix containing 846 structural vectors characterizing the molecular composition of diesel was constructed. According to the reaction mechanism of diesel hydrofining,34 reaction rules were compiled,and a diesel hydrofining reaction network containing about 17 500 reactions was constructed. Combined with the reaction kinetic parameters based on quantum chemical calculation,a molecular scale kinetic model of diesel hydrofining based on structure-oriented lumping was established. The improved Runge-Kutta method was used to solve the model,and the reliability of the model was verified by comparison with industrial equipment data. The results show that the maximum error between the predicted value and industrial data of hydrofining product distribution and typical molecular content is within 1.0%,and the prediction error of temperature rise is within 2 ℃.