TY - JOUR
T1 - Model-Based Design of Experiments for Temporal Analysis of Products (TAP)
T2 - A Simulated Case Study in Oxidative Propane Dehydrogenation
AU - Yonge, Adam
AU - Gusmão, Gabriel S.
AU - Fushimi, Rebecca
AU - Medford, Andrew J.
N1 - Funding Information:
Support for this work was provided by the U.S. Department of Energy (USDOE), Office of Energy Efficiency and Renewable Energy (EERE), Advanced Manufacturing Office Next Generation R&D Projects under Contract No. DE-AC07-05ID14517 and acknowledgment is made to the donors of the American Chemical Society Petroleum Research Fund for partial support of this research (61165-DNI5). This research made use of Idaho National Laboratory computing resources that are supported by the Office of Nuclear Energy of the U.S. Department of Energy and the Nuclear Science User Facilities under Contract No. DE-AC07-05ID14517.
Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
PY - 2024/3/20
Y1 - 2024/3/20
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85187576917&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/98496a0f-0536-3b54-94be-bd161521ef2b/
U2 - 10.1021/acs.iecr.3c03418
DO - 10.1021/acs.iecr.3c03418
M3 - Article
AN - SCOPUS:85187576917
SN - 0888-5885
VL - 63
SP - 4756
EP - 4770
JO - Industrial and Engineering Chemistry Research
JF - Industrial and Engineering Chemistry Research
IS - 11
ER -