Abstract The viability of thermochemical energy storage for a given application is often determined by the reaction kinetics under process conditions. For high exergetic efficiency the process needs to operate in close proximity to the reaction equilibrium. Thus, accurate kinetic models that include the effect of the reaction equilibrium are required. In the present work, different parametrization methods for the equilibrium term in the General Kinetic Equation are evaluated by modeling the kinetics of two reaction systems relevant for thermochemical energy storage ( CaC 2 O 4 and CuO ) from experimental data. A non-parametric modeling method based on tensor decompositions is used that allows for a purely data driven assessment of different parametrization methods. Our analysis shows that including a suitable equilibrium term is crucial. Omitting the equilibrium term when modeling formation reactions can lead to seemingly negative activation energies. Our tests also show that for formation reactions, the reaction rate decreases much faster towards the equilibrium than theory predicts. We present an empirical modeling approach that can predict the reaction rate of gas-solid reactions, regardless of the shortcomings of theory. In this way, non-parametric modeling offers a powerful tool for applied research and may contribute to the advancement of the thermochemical energy storage technology.

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反应平衡对气固反应动力学的影响——非参数建模研究

摘要 对于给定应用，热化学储能的可行性通常由工艺条件下的反应动力学决定。为了获得高火用效率，该过程需要在非常接近反应平衡的情况下运行。因此，需要包含反应平衡效应的准确动力学模型。在目前的工作中，通过对来自实验数据的与热化学储能相关的两个反应系统（CaC 2 O 4 和 CuO ）的动力学进行建模，评估了一般动力学方程中平衡项的不同参数化方法。使用基于张量分解的非参数建模方法，允许对不同参数化方法进行纯数据驱动的评估。我们的分析表明，包括一个合适的平衡项是至关重要的。在模拟形成反应时省略平衡项会导致看似负的活化能。我们的测试还表明，对于地层反应，反应速率向平衡下降的速度比理论预测的要快得多。我们提出了一种经验建模方法，可以预测气固反应的反应速率，而不管理论的缺陷。通过这种方式，非参数建模为应用研究提供了强大的工具，并可能有助于热化学储能技术的进步。我们提出了一种经验建模方法，可以预测气固反应的反应速率，而不管理论的缺陷。通过这种方式，非参数建模为应用研究提供了强大的工具，并可能有助于热化学储能技术的进步。我们提出了一种经验建模方法，可以预测气固反应的反应速率，而不管理论的缺陷。通过这种方式，非参数建模为应用研究提供了强大的工具，并可能有助于热化学储能技术的进步。