skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Hydrogenation of levoglucosenone to renewable chemicals

Abstract

Here, we have studied the hydrogenation of levoglucosenone (LGO) to dihydrolevoglucosenone (Cyrene), levoglucosanol (Lgol), and tetrahydrofurandimethanol (THFDM) and elucidated the reaction network over supported palladium catalysts. At low temperature (40 °C) over a Pd/Al 2O 3 catalyst, LGO is selectively hydrogenated to Cyrene. At intermediate temperatures (100 °C) over a Pd/Al 2O 3 catalyst, Cyrene is selectively hydrogenated to Lgol, with an excess of the exo-Lgol isomer produced over the endo-Lgol isomer. At higher temperatures (150 °C) over a bifunctional Pd/SiO 2–Al 2O 3 catalyst, Lgol is converted to THFDM in 58% selectivity, with 78% overall selectivity to 1,6-hexanediol precursors. The ratio of cis-THFDM relative to trans-THFDM is approximately 2.5, and this ratio is independent of the Lgol feed stereoisomer ratio. Finally, tetrahydropyran-2-methanol-5-ketone (THP2M5one) and tetrahydropyran-2-methanol-5-hydroxyl (THP2M5H) are side-products of Lgol hydrogenolysis, but neither of these species are precursors to THFDM.

Authors:
 [1];  [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:
1477850
Grant/Contract Number:  
EE0006878
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 19; Journal Issue: 5; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Krishna, Siddarth H., McClelland, Daniel J., Rashke, Quinn A., Dumesic, James A., and Huber, George W. Hydrogenation of levoglucosenone to renewable chemicals. United States: N. p., 2016. Web. doi:10.1039/C6GC03028A.
Krishna, Siddarth H., McClelland, Daniel J., Rashke, Quinn A., Dumesic, James A., & Huber, George W. Hydrogenation of levoglucosenone to renewable chemicals. United States. https://doi.org/10.1039/C6GC03028A
Krishna, Siddarth H., McClelland, Daniel J., Rashke, Quinn A., Dumesic, James A., and Huber, George W. Mon . "Hydrogenation of levoglucosenone to renewable chemicals". United States. https://doi.org/10.1039/C6GC03028A. https://www.osti.gov/servlets/purl/1477850.
@article{osti_1477850,
title = {Hydrogenation of levoglucosenone to renewable chemicals},
author = {Krishna, Siddarth H. and McClelland, Daniel J. and Rashke, Quinn A. and Dumesic, James A. and Huber, George W.},
abstractNote = {Here, we have studied the hydrogenation of levoglucosenone (LGO) to dihydrolevoglucosenone (Cyrene), levoglucosanol (Lgol), and tetrahydrofurandimethanol (THFDM) and elucidated the reaction network over supported palladium catalysts. At low temperature (40 °C) over a Pd/Al2O3 catalyst, LGO is selectively hydrogenated to Cyrene. At intermediate temperatures (100 °C) over a Pd/Al2O3 catalyst, Cyrene is selectively hydrogenated to Lgol, with an excess of the exo-Lgol isomer produced over the endo-Lgol isomer. At higher temperatures (150 °C) over a bifunctional Pd/SiO2–Al2O3 catalyst, Lgol is converted to THFDM in 58% selectivity, with 78% overall selectivity to 1,6-hexanediol precursors. The ratio of cis-THFDM relative to trans-THFDM is approximately 2.5, and this ratio is independent of the Lgol feed stereoisomer ratio. Finally, tetrahydropyran-2-methanol-5-ketone (THP2M5one) and tetrahydropyran-2-methanol-5-hydroxyl (THP2M5H) are side-products of Lgol hydrogenolysis, but neither of these species are precursors to THFDM.},
doi = {10.1039/C6GC03028A},
url = {https://www.osti.gov/biblio/1477850}, journal = {Green Chemistry},
issn = {1463-9262},
number = 5,
volume = 19,
place = {United States},
year = {2016},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 26 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Selective heterogeneously catalyzed hydrogenations
journal, September 1997


Emerging catalytic processes for the production of adipic acid
journal, January 2013


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


Brønsted acidity of amorphous silica–alumina: The molecular rules of proton transfer
journal, December 2011


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


The selective hydrogenation of biomass-derived 5-hydroxymethylfurfural using heterogeneous catalysts
journal, January 2012


Effect of rhodium precursor and thermal treatment on the hydrogenation of 2-cyclohexenone on Rh/SiO 2 Catalysts
journal, December 1999


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


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


Dihydrolevoglucosenone (Cyrene) As a Green Alternative to N,N -Dimethylformamide (DMF) in MOF Synthesis
journal, October 2016


Some reactions of levoglucosenone
journal, June 1979


Formation of acid sites in amorphous silica-alumina
journal, January 2010


Selective Hydrogenolysis of Polyols and Cyclic Ethers over Bifunctional Surface Sites on Rhodium–Rhenium Catalysts
journal, August 2011


Chemoselective hydrogenation of carbonyl compounds over heterogeneous catalysts
journal, September 2005


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


On the selective acid-catalysed dehydration of 1,2,6-hexanetriol
journal, January 2014


Catalyst studies on the ring opening of tetrahydrofuran–dimethanol to 1,2,6-hexanetriol
journal, July 2013


Direct Synthesis of 1,6-Hexanediol from HMF over a Heterogeneous Pd/ZrP Catalyst using Formic Acid as Hydrogen Source
journal, November 2013


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


Recent Catalytic Advances in the Chemistry of Substituted Furans from Carbohydrates and in the Ensuing Polymers
journal, February 2004


    Works referencing / citing this record:

    Aerobic oxidation of C 4 –C 6 α,ω-diols to the diacids in base-free medium over zirconia-supported (bi)metallic catalysts
    journal, January 2019


    New catalytic strategies for α,ω-diols production from lignocellulosic biomass
    journal, January 2017


    Aerobic oxidation of C 4 –C 6 α,ω-diols to the diacids in base-free medium over zirconia-supported (bi)metallic catalysts
    journal, January 2019


    Homogeneous catalysed hydrogenation of HMF
    journal, January 2018


    Catalytic production of hexane-1,2,5,6-tetrol from bio-renewable levoglucosanol in water: effect of metal and acid sites on (stereo)-selectivity
    journal, January 2018


    Cyrene as a bio-based solvent for HATU mediated amide coupling
    journal, January 2018


    CNN pincer ruthenium complexes for efficient transfer hydrogenation of biomass-derived carbonyl compounds
    journal, January 2020


    Catalytic hydrogenation of dihydrolevoglucosenone to levoglucosanol with a hydrotalcite/mixed oxide copper catalyst
    journal, January 2019


    Tuning zirconia-supported metal catalysts for selective one-step hydrogenation of levoglucosenone
    journal, January 2019


    Development of bio-acrylic polymers from Cyrene™: transforming a green solvent to a green polymer
    journal, January 2019