Applicability of the Delplot method for the determination of catalytic reaction sequences: Hydrodeoxygenation of $\gamma$-valerolactone on Ni2P/MCM-41

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

doi:10.1016/j.ces.2020.115697

Title: Applicability of the Delplot method for the determination of catalytic reaction sequences: Hydrodeoxygenation of $$\gamma$$-valerolactone on Ni₂P/MCM-41

Journal Article · Fri Apr 17 00:00:00 EDT 2020 · Chemical Engineering Science

DOI:https://doi.org/10.1016/j.ces.2020.115697· OSTI ID:1800849

Yun, Gwang-Nam ^[1]; Tyrone Ghampson, I. ^[2]; Movick, William J. ^[2]; Vargheese, Vibin ^[2]; Kobayashi, Yasukazu ^[3];

^[4]

University of Tokyo (Japan); Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States); Korea Research Institute of Chemical Technology (KRICT), Daejeon (Korea, Republic of)
University of Tokyo (Japan)
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
Fuzhou University (China); University of Tokyo (Japan); Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States)

Contact-time measurements based on sites are used to investigate the reaction sequence of the hydrodeoxygenation of γ-valerolactone (GVL) on Ni₂P/MCM-41. Here the study is carried out at 300 °C and 0.5 MPa with site times of 0.29–6.1 s. A reaction network is proposed in which pentanoic acid and 2-methyltetrahydrofuran (2-MTHF) are formed in parallel initially and pentanal, butane and pentane are formed subsequently. A first-rank Delplot analysis (selectivity) gives a good fit, but higher-rank Delplots do not. The lack of applicability is explained by the magnitude of the rate constants, in which the rate constant for one of the later steps (the consumption of pentanal) is substantially larger than those for the preceding steps. For this reason, pentanal demonstrated the characteristics of a primary product and consequently affected the discrimination of higher rank products. A simulation of a model sequence with assumed rate constants confirms the reason why the Delplot method does not work for this reaction. Since the rate constants cannot be determined a priori to be of close magnitude, the Delplot method cannot be generally used to ascertain reaction sequences.

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Research Organization:: Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: FG02-96ER14669

OSTI ID:: 1800849

Alternate ID(s):: OSTI ID: 1616620

Journal Information:: Chemical Engineering Science, Vol. 223, Issue C; ISSN 0009-2509

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Applicability of the Delplot method for the determination of catalytic reaction sequences: Hydrodeoxygenation of $$\gamma$$-valerolactone on Ni2P/MCM-41

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Title: Applicability of the Delplot method for the determination of catalytic reaction sequences: Hydrodeoxygenation of $$\gamma$$-valerolactone on Ni₂P/MCM-41