Yonge Adam, Gusmão Gabriel S, Fushimi Rebecca, Medford Andrew J
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States.
Catalysis and Transient Kinetics Group, Idaho National Laboratory, Idaho Falls, Idaho 83415, United States.
Ind Eng Chem Res. 2024 Mar 11;63(11):4756-4770. doi: 10.1021/acs.iecr.3c03418. eCollection 2024 Mar 20.
Temporal analysis of products (TAP) reactors enable experiments that probe numerous kinetic processes within a single set of experimental data through variations in pulse intensity, delay, or temperature. Selecting additional TAP experiments often involves an arbitrary selection of reaction conditions or the use of chemical intuition. To make experiment selection in TAP more robust, we explore the efficacy of model-based design of experiments (MBDoE) for precision in TAP reactor kinetic modeling. We successfully applied this approach to a case study of synthetic oxidative propane dehydrogenation (OPDH) that involves pulses of propane and oxygen. We found that experiments identified as optimal through the MBDoE for precision generally reduce parameter uncertainties to a higher degree than alternative experiments. The performance of MBDoE for model divergence was also explored for OPDH, with the relevant active sites (catalyst structure) being unknown. An experiment that maximized the divergence between the three proposed mechanisms was identified and provided evidence that improved the mechanism discrimination. However, reoptimization of kinetic parameters eliminated the ability to discriminate between models. The findings yield insight into the prospects and limitations of MBDoE for TAP and transient kinetic experiments.
产物的时间分析（TAP）反应器能够通过改变脉冲强度、延迟或温度，在单一组实验数据中探究众多动力学过程的实验。选择额外的TAP实验通常涉及对反应条件的任意选择或化学直觉的运用。为了使TAP中的实验选择更可靠，我们探索了基于模型的实验设计（MBDoE）在TAP反应器动力学建模精度方面的有效性。我们成功地将这种方法应用于一个涉及丙烷和氧气脉冲的合成氧化丙烷脱氢（OPDH）案例研究。我们发现，通过MBDoE确定为精度最优的实验，通常比其他实验能更大程度地降低参数不确定性。还针对OPDH研究了MBDoE在模型分歧方面的性能，其中相关的活性位点（催化剂结构）未知。确定了一个能使三种提出的机理之间分歧最大化的实验，并提供了有助于机理辨别的证据。然而，动力学参数的重新优化消除了区分模型的能力。这些发现为MBDoE在TAP和瞬态动力学实验中的前景和局限性提供了见解。
