Kinetics of Levoglucosenone Isomerization
Abstract
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:
-
- Univ. of Wisconsin, Madison, WI (United States). Department of Chemical and Biological Engineering
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- Contributing Org.:
- University of Wisconsin-Madison Department of Chemistry
- OSTI Identifier:
- 1477849
- Grant/Contract Number:
- EE0006878
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- ChemSusChem
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1864-5631
- Publisher:
- ChemPubSoc Europe
- 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
Citation Formats
Krishna, Siddarth H., Walker, Theodore W., Dumesic, James A., and Huber, George W. Kinetics of Levoglucosenone Isomerization. United States: N. p., 2016.
Web. doi:10.1002/cssc.201601308.
Krishna, Siddarth H., Walker, Theodore W., Dumesic, James A., & Huber, George W. Kinetics of Levoglucosenone Isomerization. United States. https://doi.org/10.1002/cssc.201601308
Krishna, Siddarth H., Walker, Theodore W., Dumesic, James A., and Huber, George W. Thu .
"Kinetics of Levoglucosenone Isomerization". United States. https://doi.org/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},
url = {https://www.osti.gov/biblio/1477849},
journal = {ChemSusChem},
issn = {1864-5631},
number = 1,
volume = 10,
place = {United States},
year = {2016},
month = {12}
}
Web of Science
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