三组元反应网络动力学模型及算法改进研究  

IMPROVED KINETIC MODEL AND ALGORITHM OF THREE-COMPONENT REACTION NETWORK

作　　者：袁胜华 张燕萍 魏春金[3] 方维平[2] 伊晓东[2] 赖伟坤 Yuan Shenghua;Zhang Yanping;Wei Chunjin;Fang Weiping;Yi Xiaodong;Lai Weikun(SINOPEC(Dalian)Research Institute of Petroleum and Petrochemicals Co.,Ltd.,Dalian,Liaoning 116041;National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters,College of Chemistry and Chemical Engineering,Xiamen University;School of Science,Jimei University)

机构地区：[1]中石化(大连)石油化工研究院有限公司,辽宁大连116041 [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

出　　处：《石油炼制与化工》2023年第7期26-33,共8页Petroleum Processing and Petrochemicals

基　　金：国家自然科学基金资助项目(22172122,22072057,22172126,21773194);广西省科技厅资助项目(AD17195067)。

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Δt取值,可使计算结果更合理;当Δt=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。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 ofΔt in the matrix decomposition equation.WhenΔt=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.

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 

分 类 号：O643.1[理学—物理化学]