三组元反应网络动力学模型及算法改进研究

石油炼制与化工 ›› 2023, Vol. 54 ›› Issue (7): 26-33.

三组元反应网络动力学模型及算法改进研究

袁胜华¹,张艳萍²,魏春金³,方维平²,伊晓东²,赖伟坤²

1. 中石化(大连)石油化工研究院有限公司
2. 厦门大学化学化工学院醇醚酯化工清洁生产国家工程实验室
3. 集美大学理学院

收稿日期:2022-12-13 修回日期:2023-03-13 出版日期:2023-07-12 发布日期:2023-06-21
通讯作者: 赖伟坤 E-mail:laiweikun@xmu.edu.cn
基金资助:
国家自然科学基金;国家自然科学基金;国家自然科学基金;国家自然科学基金;广西省科技项目

IMPROVED KINETIC MODELING AND ALGORITHM OF THREE-COMPONENT REACTION NETWORK

Received:2022-12-13 Revised:2023-03-13 Online:2023-07-12 Published:2023-06-21

摘要/Abstract

摘要： 针对特征方向法无法处理复杂反应网络、等时间改进法计算反应速率常数易出现负数和虚数的问题，对原有反应网络动力学模型进行了改进，一是对组元浓度进行了线性无关处理以保证相关逆矩阵的存在，二是将真实浓度恰当变换成虚拟浓度以简化浓度-时间关系表达式；进而，基于改进模型，采用等时间概念对模型算法进行了改进。结果表明：改进模型中，组元平衡浓度只由速率常数确定，与初始浓度无关；随着速率常数分布熵减小，组元浓度-时间曲线中段向上迁移，而初始点和终点值不变，改进算法使速率常数的计算顺利进行；通过调节矩阵分解方程中△t取值，可使计算结果更合理；当△t=0.5时，组元浓度计算值与试验值的平均偏差最小。这表明新建模型弥补了等时间法的缺点，该模型改进算法有效可行。

关键词: 反应网络, 反应动力学, 速率常数, 特征方向法, 等时间法

Abstract: In order to solve the problem that the eigenvector method cannot deal with complex reaction networks and that the equal time method is easy to appear negative and imaginary numbers, the reaction network kinetic model was improved. Firstly, the concentration of components was linearly independent solutions of component concentration to ensure the existence of the inverse matrix. Secondly, the real concentration was appropriately transformed into a virtual concentration to simplify the expression of concentration-time equation. Finally, the model algorithm was improved by using the concept of equal time. The results showed that in the improved model, the equilibrium concentration of components was determined only by the rate coefficient, which was independent of the initial concentration. With the decrease of the distribution entropy of rate coefficient, the middle of concentration-time curve of the components moved up, but the initial and terminal values did not change, and the improved algorithm made the calculation of the rate constant go on smoothly. The calculation results could be more reasonable by adjusting the value of △t in the matrix decomposition equation. When △t = 0.5, the mean deviation between the calculated concentration and the experimental value was the smallest, which showed that the new model made up for the shortcomings of the equal time method and the improved algorithm was effective and feasible.

Key words: reaction network, reaction kinetics, rate coefficient, eigenvector method, equal time method

袁胜华张艳萍魏春金方维平伊晓东赖伟坤. 三组元反应网络动力学模型及算法改进研究[J]. 石油炼制与化工, 2023, 54(7): 26-33.

参考文献

[1]朱炳辰.催化反应工程 [M]. 中国石化出版社, 2001. [2]朱开宏, 陈敏恒, 袁渭康.多元可逆反应网络的一个工程模型[J].化工学报, 1983, 34(1):1-12 [3]黄云清，舒适，陈艳萍, 等.数值计算方法 [M]. 北京：科学出版社, 2009. [4]粟智.微分-积分法确定反应速率常数[J].新疆师范大学学报：自然科学版, 2004, 23(4):62-66 [5]Kuo J, Wei J.Lumping analysis in monomolecular reaction systems[J].Industrial & Engineering Chemistry Fundamentals, 1969, 8(1):124-133 [6]Christoffel E G.Cheminform abstract: laboratory reactors and heterogenous catalytic processes[J].Chemischer Informationsdienst, 1982, 13(2):159-232 [7]祝敬民, 黄国雄, 李承烈, 等.催化反应中的等时间数据在复杂一级反应网络动力学研究中的应用[J].石油学报(石油加工), 1985, 1:21-28 [8]祝敬民, 黄国雄, 李承烈, 等.正戊烷在Pd/氢型丝光沸石催化剂上临氢异构化的动力学[J].催化学报, 2985, 1:46-51 [9]祝敬民, 黄国雄, 李承烈, 等.己烷在M-1型催化剂上临氢异构化反应的动力学[J].燃料化学学报, 1986, 3:38-44 [10]祝敬民, 邢士峰, 黄国雄, 等.己烷在M23型催化剂上异构化反应动力学的脉冲法研究[J].催化学报, 1985, 4:332-338 [11]Messner J, Schulz P S, Taccardi N, et al.Isomerisation of 1,4-dichlorobenzene using highly acidic alkali chloroaluminate melts[J].Chemical Communications, 2014, 50(79):11705-11708 [12]佘卫民, 许小亮, 吴春江, 等.邻二氯苯异构化生产间二氯苯工艺[J].氯碱工业, 2017, 53(7):24-25 [13]Simic-Milosevic V, Meyer J, Morgenstern K.Electron-induced isomerisation of dichlorobenzene on Cu(111) and Ag(111)[J].Physical Chemistry Chemical Physics, 2008, 10(14):1916-1920 [14]李心园.渣油加氢反应动力学模型的研究 [D]; 厦门大学, 2019. [15]师宝仁, 李柏春, 韩俏飞.邻二氯苯异构反应动力学研究[J].化学工程, 2019, 47(06):69-73 [16]Wei J, Prater C D.The structure and analysis of complex reaction systems[J].Advances in Catalysis, 1962, 13:203-392 [17]程开敏, 陈相兵.线性代数 [M]. 重庆大学出版社, 2017. [18]郭汉贤.应用化工动力学 [M]. 化学工业出版社, 2003. [19]胡英.物理化学参考 [M]. 高等教育出版社, 2003.