Abstract

The validity of using kinetic scheme reduction procedures to compare various kinetic models as well as the values of kinetic parameters of individual steps present in the literature is analyzed. The peculiarities of the development of the gas-phase reaction block as a part of the heterogeneous-homogeneous model of the oxidative coupling of methane (OCM) are considered and approaches to the selection of kinetic parameters of elementary steps are analyzed. It has been demonstrated that kinetic models developed in accordance with the principle of “independence of kinetic parameters” can exhibit low predictive power due to existing uncertainties in the values of the parameters presented in well-known review papers and databases. In addition, the effects of the accounting of the heterogeneous reaction block and variation of the OCM reaction conditions on the results of the reduction of the detailed kinetic scheme are addressed. It has been shown that the use of reduction procedures to analyze the mechanism of complex processes is limited due to the high degree of conjugation between their individual stages and the strong dependence of kinetic constants on the parameters of state.

中文翻译：

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动力学方案还原法分析甲烷氧化偶联的均相-均相模型

摘要

分析了使用动力学方案简化程序比较各种动力学模型以及文献中存在的各个步骤的动力学参数值的有效性。作为甲烷氧化偶合（OCM）的异相-均相模型的一部分，气相反应嵌段的发展具有特殊性，并分析了选择基本步骤动力学参数的方法。已经证明，根据“动力学参数的独立性”原理开发的动力学模型由于众所周知的综述论文和数据库中给出的参数值存在不确定性而具有较低的预测能力。此外，解决了异质反应嵌段的计算和OCM反应条件的变化对详细动力学方案还原结果的影响。结果表明，由于还原过程在各个阶段之间的高度共轭以及动力学常数对状态参数的强烈依赖，因此使用还原过程来分析复杂过程的机制受到了限制。