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MODELING OXIDATION AND HYDROLYSIS REACTIONS IN SUPERCRITICAL WATER—FREE RADICAL ELEMENTARY REACTION NETWORKS AND THEIR APPLICATIONS

机译:超临界水-无自由基基反应网络中氧化和水解反应的模拟及其应用

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From the beginning of supercritical water oxidation (SCWO) research in the early 1980s, mathematical models have been used to correlate, predict, and explain experimental reaction kinetic data. Initially, these were simple global rate laws, involving only a single overall reaction or a few reactions, each with its own arbitrary rate law. As computational power increased and the library of elementary reactions from the combustion literature grew, it became feasible to construct elementary reaction rate models, which are a more accurate means of representing the SCWO process. Early efforts to construct elementary reaction rate models resulted in very poor agreement with experimental data unless model parameters were adjusted to optimize the fit. However, today with considerably more computing power and a more robust collection of elementary rate parameters from the combustion literature, rate predictions in the relatively low-temperature, high-pressure SCWO environment are more effective and accurate. These enhancements make it possible to build models that hold the predictive capacity to help guide experimental design and gain a greater mechanistic understanding. This paper details current best practices for the construction of these elementary reaction rate models, including selection of a base model from the combustion literature, identification of possible intermediate compounds, and estimation of unknown rate constants by ab initio calculations or analogy to known chemistry. A set of model compounds was selected to illustrate rate modeling approaches for both oxidation and hydrolysis pathways.
机译:从1980年代初期开始进行超临界水氧化(SCWO)研究以来,数学模型已用于关联,预测和解释实验反应动力学数据。最初,这些是简单的全局费率定律,只涉及一个整体反应或几个反应,每个反应都有其自己的任意费率定律。随着计算能力的提高和来自燃烧文献的基本反应库的增加,构建基本反应速率模型变得可行,该模型是表示SCWO过程的更准确方法。除非构建模型参数以优化拟合,否则早期构建基本反应速率模型的努力与实验数据的一致性很差。但是,如今,由于具有更多的计算能力和来自燃烧文献的更基本的速率参数集合,在相对低温,高压SCWO环境中的速率预测更加有效和准确。这些增强功能使构建具有预测能力的模型成为可能,以帮助指导实验设计并获得更深入的机械理解。本文详细介绍了构建这些基本反应速率模型的当前最佳实践,包括从燃烧文献中选择基本模型,鉴定可能的中间化合物以及通过从头算或与已知化学类似的方法估算未知的速率常数。选择了一组模型化合物来说明氧化和水解途径的速率建模方法。

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