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Title: 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 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.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
  1. 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:
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. doi:10.1002/cssc.201601308.
Krishna, Siddarth H., Walker, Theodore W., Dumesic, James A., and Huber, George W. Thu . "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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Works referenced in this record:

Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates
journal, June 2007

  • Román-Leshkov, Yuriy; Barrett, Christopher J.; Liu, Zhen Y.
  • Nature, Vol. 447, Issue 7147, p. 982-985
  • DOI: 10.1038/nature05923

Kinetics of Non-catalyzed Decomposition of Glucose in High-temperature Liquid Water
journal, December 2008


Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals
journal, September 2007

  • Chheda, Juben N.; Huber, George W.; Dumesic, James A.
  • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7164-7183
  • DOI: 10.1002/anie.200604274

Dehydration of cellulose to levoglucosenone using polar aprotic solvents
journal, January 2015

  • Cao, Fei; Schwartz, Thomas J.; McClelland, Daniel J.
  • Energy & Environmental Science, Vol. 8, Issue 6
  • DOI: 10.1039/C5EE00353A

Hydrochloric acid-catalyzed levulinic acid formation from cellulose: data and kinetic model to maximize yields
journal, March 2011

  • Shen, Jiacheng; Wyman, Charles E.
  • AIChE Journal, Vol. 58, Issue 1, p. 236-246
  • DOI: 10.1002/aic.12556

Insights into the Interplay of Lewis and Brønsted Acid Catalysts in Glucose and Fructose Conversion to 5-(Hydroxymethyl)furfural and Levulinic Acid in Aqueous Media
journal, March 2013

  • Choudhary, Vinit; Mushrif, Samir H.; Ho, Christopher
  • Journal of the American Chemical Society, Vol. 135, Issue 10
  • DOI: 10.1021/ja3122763

Caprolactam from Renewable Resources: Catalytic Conversion of 5-Hydroxymethylfurfural into Caprolactone
journal, June 2011

  • Buntara, Teddy; Noel, Sebastien; Phua, Pim Huat
  • Angewandte Chemie, Vol. 123, Issue 31
  • DOI: 10.1002/ange.201102156

Caprolactam from Renewable Resources: Catalytic Conversion of 5-Hydroxymethylfurfural into Caprolactone
journal, June 2011

  • Buntara, Teddy; Noel, Sebastien; Phua, Pim Huat
  • Angewandte Chemie International Edition, Vol. 50, Issue 31
  • DOI: 10.1002/anie.201102156

Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
journal, September 2006

  • Huber, George W.; Iborra, Sara; Corma, Avelino
  • Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098
  • DOI: 10.1021/cr068360d

A kinetic study on the decomposition of 5-hydroxymethylfurfural into levulinic acid
journal, January 2006

  • Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J.
  • Green Chemistry, Vol. 8, Issue 8
  • DOI: 10.1039/b518176c

Some reactions of levoglucosenone
journal, June 1979

  • Shafizadeh, Fred; Furneaux, Richard H.; Stevenson, Thomas T.
  • Carbohydrate Research, Vol. 71, Issue 1, p. 169-191
  • DOI: 10.1016/S0008-6215(00)86069-3

Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water
journal, October 2010

  • Román-Leshkov, Yuriy; Moliner, Manuel; Labinger, Jay A.
  • Angewandte Chemie, Vol. 122, Issue 47
  • DOI: 10.1002/ange.201004689

Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites
journal, June 2012

  • Bermejo-Deval, R.; Assary, R. S.; Nikolla, E.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 25
  • DOI: 10.1073/pnas.1206708109

Production of liquid hydrocarbon fuels by catalytic conversion of biomass-derived levulinic acid
journal, January 2011

  • Braden, Drew J.; Henao, Carlos A.; Heltzel, Jacob
  • Green Chemistry, Vol. 13, Issue 7
  • DOI: 10.1039/c1gc15047b

Catalytic Isomerization of Biomass-Derived Aldoses: A Review
journal, March 2016


Kinetics and Reaction Engineering of Levulinic Acid Production from Aqueous Glucose Solutions
journal, June 2012


Dihydrolevoglucosenone (Cyrene) as a bio-based alternative for dipolar aprotic solvents
journal, January 2014

  • Sherwood, James; De bruyn, Mario; Constantinou, Andri
  • Chem. Commun., Vol. 50, Issue 68
  • DOI: 10.1039/C4CC04133J

Synthesis of 1,6-hexanediol from HMF over double-layered catalysts of Pd/SiO 2 + Ir–ReO x /SiO 2 in a fixed-bed reactor
journal, January 2016

  • Xiao, Bin; Zheng, Mingyuan; Li, Xinsheng
  • Green Chemistry, Vol. 18, Issue 7
  • DOI: 10.1039/C5GC02228B

Total Synthesis of (+)-Chloriolide
journal, April 2014

  • Ostermeier, Michael; Schobert, Rainer
  • The Journal of Organic Chemistry, Vol. 79, Issue 9
  • DOI: 10.1021/jo500527g

Kinetic Study on the Acid-Catalyzed Hydrolysis of Cellulose to Levulinic Acid
journal, March 2007

  • Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J.
  • Industrial & Engineering Chemistry Research, Vol. 46, Issue 6
  • DOI: 10.1021/ie061186z

Catalytic pyrolysis of cellulose in sulfolane with some acidic catalysts
journal, April 2007


A two-step approach for the catalytic conversion of glucose to 2,5-dimethylfuran in ionic liquids
journal, January 2010

  • Chidambaram, Mandan; Bell, Alexis T.
  • Green Chemistry, Vol. 12, Issue 7
  • DOI: 10.1039/c004343e

Katalytische Flüssigphasenumwandlung oxygenierter Kohlenwasserstoffe aus Biomasse zu Treibstoffen und Rohstoffen für die Chemiewirtschaft
journal, September 2007

  • Chheda, Juben N.; Huber, George W.; Dumesic, James A.
  • Angewandte Chemie, Vol. 119, Issue 38
  • DOI: 10.1002/ange.200604274

3-Deoxy-glucosone is an Intermediate in the Formation of Furfurals from D-Glucose.
journal, June 2011

  • Jadhav, Harishchandra; Pedersen, Christian Marcus; Sølling, Theis
  • ChemSusChem, Vol. 4, Issue 8
  • DOI: 10.1002/cssc.201100249

Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water
journal, October 2010

  • Román-Leshkov, Yuriy; Moliner, Manuel; Labinger, Jay A.
  • Angewandte Chemie International Edition, Vol. 49, Issue 47, p. 8954-8957
  • DOI: 10.1002/anie.201004689