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Title: Kinetics of Levoglucosenone Isomerization

In this paper, we studied the acid-catalyzed isomerization of levoglucosenone (LGO) to 5-hydroxymethylfurfural (HMF) and developed a reaction kinetics model that describes the experimental data across a range of conditions (100–150 °C, 50–100 mm H 2SO 4, 50–150 mm LGO). LGO and its hydrated derivative exist in equilibrium under these reaction conditions. Thermal and catalytic degradation of HMF are the major sources of carbon loss. Within the range of conditions studied, higher temperatures and shorter reaction times favor the production of HMF. The yields of HMF and levulinic acid decrease monotonically as tetrahydrofuran is added to the aqueous solvent system, indicating that water plays a role in the LGO isomerization reaction. Initial-rate analyses show that HMF is produced solely from LGO rather than from the hydrated derivative of LGO. Finally, the results of this study are consistent with a mechanism for LGO isomerization that proceeds through hydration of the anhydro bridge, followed by ring rearrangement analogous to the isomerization of glucose to fructose.
Authors:
 [1] ;  [1] ;  [1] ; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Department of Chemical and Biological Engineering
Publication Date:
Grant/Contract Number:
EE0006878
Type:
Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Research Org:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Contributing Orgs:
University of Wisconsin-Madison Department of Chemistry
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 5-hydroxymethylfurfural; biomass; isomerization; kinetics; levoglucosenone
OSTI Identifier:
1477849

Krishna, Siddarth H., Walker, Theodore W., Dumesic, James A., and Huber, George W.. Kinetics of Levoglucosenone Isomerization. United States: N. p., Web. doi:10.1002/cssc.201601308.
Krishna, Siddarth H., Walker, Theodore W., Dumesic, James A., & Huber, George W.. Kinetics of Levoglucosenone Isomerization. United States. doi:10.1002/cssc.201601308.
Krishna, Siddarth H., Walker, Theodore W., Dumesic, James A., and Huber, George W.. 2016. "Kinetics of Levoglucosenone Isomerization". United States. doi:10.1002/cssc.201601308. https://www.osti.gov/servlets/purl/1477849.
@article{osti_1477849,
title = {Kinetics of Levoglucosenone Isomerization},
author = {Krishna, Siddarth H. and Walker, Theodore W. and Dumesic, James A. and Huber, George W.},
abstractNote = {In this paper, we studied the acid-catalyzed isomerization of levoglucosenone (LGO) to 5-hydroxymethylfurfural (HMF) and developed a reaction kinetics model that describes the experimental data across a range of conditions (100–150 °C, 50–100 mm H2SO4, 50–150 mm LGO). LGO and its hydrated derivative exist in equilibrium under these reaction conditions. Thermal and catalytic degradation of HMF are the major sources of carbon loss. Within the range of conditions studied, higher temperatures and shorter reaction times favor the production of HMF. The yields of HMF and levulinic acid decrease monotonically as tetrahydrofuran is added to the aqueous solvent system, indicating that water plays a role in the LGO isomerization reaction. Initial-rate analyses show that HMF is produced solely from LGO rather than from the hydrated derivative of LGO. Finally, the results of this study are consistent with a mechanism for LGO isomerization that proceeds through hydration of the anhydro bridge, followed by ring rearrangement analogous to the isomerization of glucose to fructose.},
doi = {10.1002/cssc.201601308},
journal = {ChemSusChem},
number = 1,
volume = 10,
place = {United States},
year = {2016},
month = {12}
}

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