Catalytic production of δ-valerolactone (DVL) from biobased 2-hydroxytetrahydropyran (HTHP) – Combined experimental and modeling study

Dastidar, Raka G.; Chavarrio, Javier E.; Jiang, Zhen; McClelland, Daniel J.; Mavrikakis, Manos; Huber, George W.

doi:10.1016/j.apcatb.2024.124519

Catalytic production of δ-valerolactone (DVL) from biobased 2-hydroxytetrahydropyran (HTHP) – Combined experimental and modeling study

Journal Article · Thu Aug 22 00:00:00 EDT 2024 · Applied Catalysis. B, Environmental

DOI:https://doi.org/10.1016/j.apcatb.2024.124519· OSTI ID:2439211

Dastidar, Raka G. ^[1]; Chavarrio, Javier E. ^[2]; Jiang, Zhen ^[2]; McClelland, Daniel J. ^[3]; ^[2]; Huber, George W. ^[2]

University of Wisconsin, Madison, WI (United States); Pyran, Inc., Madison, WI (United States); University of Wisconsin Madison
University of Wisconsin, Madison, WI (United States)
Pyran, Inc., Madison, WI (United States)

δ-Valerolactone (DVL) is a five-carbon (C5) cyclic ester that can undergo ring-opening polymerization to yield high-performance, biocompatible polyesters. But current market prices of C5 chemicals like DVL are very high due to poor availability of C5 feedstock in petroleum. Herein, we demonstrate a novel route to DVL synthesis via dehydrogenation of biomass-derived 2-hydroxytetrahydropyran (HTHP) over Cu/SiO₂ without the use of toxic reagents. Since HTHP exists in thermal equilibrium with 3,4-dihydropyran (DHP) via dehydration, and with 2,2’-oxybis(tetrahydropyran) and 5-(tetrahydropyran-2-yloxy)pentanal via acetalization, we have also determined the thermochemistry (ΔH_rxn and ΔG_rxn) of each competing reaction using density functional theory (DFT) calculations at the M06-2X/cc-pVTZ level. Finally, by developing a kinetic model of all 8 reactions involved, we have achieved 84% selectivity to DVL at 150°C in a packed bed reactor for over 72 hours of time on stream.

View Accepted Manuscript (DOE)

Research Organization:: University of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO)

Grant/Contract Number:: EE0009305

OSTI ID:: 2439211

Alternate ID(s):: OSTI ID: 2440117

Journal Information:: Applied Catalysis. B, Environmental, Journal Name: Applied Catalysis. B, Environmental Vol. 360; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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