The Delplot kinetic method applied to systems with adsorbates: Hydrodeoxygenation of benzofuran on a bimetallic CoPd phosphide catalyst supported on KUSY

Movick, William J.; Yun, Gwang-Nam; Tyrone Ghampson, I.; Ted Oyama, S.

doi:10.1016/j.jcat.2021.08.051

Title: The Delplot kinetic method applied to systems with adsorbates: Hydrodeoxygenation of benzofuran on a bimetallic CoPd phosphide catalyst supported on KUSY

Journal Article · 07 September 2021 · Journal of Catalysis

DOI: https://doi.org/10.1016/j.jcat.2021.08.051 · OSTI ID:1977247

Movick, William J. ^[1];

^[2]; Tyrone Ghampson, I. ^[3]; Ted Oyama, S. ^[4]

Univ. of Tokyo (Japan); OSTI
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Korea Research Institute of Chemical Technology (KRICT), Daejeon (Korea, Republic of)
Univ. of Tokyo (Japan); Tokyo Metropolitan University (Japan)
Fuzhou Univ. (China); Univ. of Tokyo (Japan); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

The Delplot method provides a means of analyzing conversion and selectivity data to derive a reaction sequence and has been applied so far to gas-phase or liquid-phase species. This study analyses the applicability of the method for catalytic reactions and considers for the first time adsorbed intermediates. The method is applied to a contact time study of the hydrodeoxygenation (HDO) of benzofuran at 0.5 MPa and 350 °C over a catalyst consisting of bimetallic CoPd phosphide supported on a potassium ion-exchanged ultra-stable Y (KUSY) zeolite. Both simple and detailed reaction networks were derived. The simple networks considered only gas-phase species and were modeled by a first-order sequence of steps, whereas the detailed network took into account adsorbed intermediates and was simulated using a rake mechanism. The networks were compared using F-statistics, which accounted for the differences in the number of fitting parameters. The detailed network gave a better fit to the experimental data because it represented a more realistic description of the transformation. A suggested sequence from the Delplot method was consistent with the simple network but not with the detailed network. The lack of applicability of the Delplot analysis to the network with adsorbates was linked to overly large equilibrium constants, a determination supported by Delplot fitting for a model sequence. Further, this study indicated the inapplicability of the Delplot method in determining reaction sequences that involve adsorbed species with large equilibrium constants for formation.

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Research Organization:: Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: FG02-96ER14669

OSTI ID:: 1977247

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: C Vol. 404; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Benzofuran
Chemistry
CoPd phosphide
Delplot analysis
Engineering
Hydrodeoxygenation
Rake mechanism
Reaction network

Title: The Delplot kinetic method applied to systems with adsorbates: Hydrodeoxygenation of benzofuran on a bimetallic CoPd phosphide catalyst supported on KUSY

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