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

Title: Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures

Abstract

In this paper, we demonstrate a process to produce levoglucosenone (LGO) and 5-hydroxymethylfurfural (HMF) from cellulose in up to 65% carbon yield using sulfuric acid as catalyst and a solvent consisting of a mixture of tetrahydrofuran (THF) with water. In pure THF, LGO is the major product of cellulose dehydration, passing through levoglucosan as an intermediate. Increasing the water content (up to 5 wt%) results in HMF as the major product. HMF is formed both by glucose dehydration and direct dehydration of LGA. The maximum combined yield of LGO and HMF (~65 carbon%) is achieved in the presence of 1–2.5 wt% H 2O, such that comparable amounts of these two co-products are formed. THF gave the highest total yields of LGO and HMF among the solvents investigated in this study (i.e., THF, diglyme, tetraglyme, gamma-valerolactone (GVL), cyclopentyl methyl ether (CPME), 1,4-dioxane, and dimethyl sulfoxide (DMSO)). Furthermore, the rate of LGO and HMF degradation in THF was lower than in the other solvents. LGO/HMF yields increased with increased strength of the acid catalyst (H 2SO 4 > H 3PO 4 > HCOOH), and HMF was produced more selectively than LGO in the presence of hydrochloric acid. Finally, techno-economic analysis for LGOmore » and HMF production from cellulose shows that the lowest LGO/HMF production costs are less than $3.00 per kg and occur at a cellulose loading and water content of 2–3% and 1.5–2.5% respectively.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. 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), Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1475401
Grant/Contract Number:  
EE0006878
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 19; Journal Issue: 15; 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

He, Jiayue, Liu, Mingjie, Huang, Kefeng, Walker, Theodore W., Maravelias, Christos T., Dumesic, James A., and Huber, George W. Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures. United States: N. p., 2017. Web. doi:10.1039/C7GC01688C.
He, Jiayue, Liu, Mingjie, Huang, Kefeng, Walker, Theodore W., Maravelias, Christos T., Dumesic, James A., & Huber, George W. Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures. United States. doi:10.1039/C7GC01688C.
He, Jiayue, Liu, Mingjie, Huang, Kefeng, Walker, Theodore W., Maravelias, Christos T., Dumesic, James A., and Huber, George W. Thu . "Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures". United States. doi:10.1039/C7GC01688C. https://www.osti.gov/servlets/purl/1475401.
@article{osti_1475401,
title = {Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures},
author = {He, Jiayue and Liu, Mingjie and Huang, Kefeng and Walker, Theodore W. and Maravelias, Christos T. and Dumesic, James A. and Huber, George W.},
abstractNote = {In this paper, we demonstrate a process to produce levoglucosenone (LGO) and 5-hydroxymethylfurfural (HMF) from cellulose in up to 65% carbon yield using sulfuric acid as catalyst and a solvent consisting of a mixture of tetrahydrofuran (THF) with water. In pure THF, LGO is the major product of cellulose dehydration, passing through levoglucosan as an intermediate. Increasing the water content (up to 5 wt%) results in HMF as the major product. HMF is formed both by glucose dehydration and direct dehydration of LGA. The maximum combined yield of LGO and HMF (~65 carbon%) is achieved in the presence of 1–2.5 wt% H2O, such that comparable amounts of these two co-products are formed. THF gave the highest total yields of LGO and HMF among the solvents investigated in this study (i.e., THF, diglyme, tetraglyme, gamma-valerolactone (GVL), cyclopentyl methyl ether (CPME), 1,4-dioxane, and dimethyl sulfoxide (DMSO)). Furthermore, the rate of LGO and HMF degradation in THF was lower than in the other solvents. LGO/HMF yields increased with increased strength of the acid catalyst (H2SO4 > H3PO4 > HCOOH), and HMF was produced more selectively than LGO in the presence of hydrochloric acid. Finally, techno-economic analysis for LGO and HMF production from cellulose shows that the lowest LGO/HMF production costs are less than $3.00 per kg and occur at a cellulose loading and water content of 2–3% and 1.5–2.5% respectively.},
doi = {10.1039/C7GC01688C},
journal = {Green Chemistry},
issn = {1463-9262},
number = 15,
volume = 19,
place = {United States},
year = {2017},
month = {6}
}

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

Citation Metrics:
Cited by: 32 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Direct Production of 5-Hydroxymethylfurfural via Catalytic Conversion of Simple and Complex Sugars over Phosphated TiO 2
journal, August 2015

  • Atanda, Luqman; Shrotri, Abhijit; Mukundan, Swathi
  • ChemSusChem, Vol. 8, Issue 17
  • DOI: 10.1002/cssc.201500395

Review: Sustainable production of hydroxymethylfurfural and levulinic acid: Challenges and opportunities
journal, January 2015


Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources
journal, February 2013

  • van Putten, Robert-Jan; van der Waal, Jan C.; de Jong, Ed
  • Chemical Reviews, Vol. 113, Issue 3
  • DOI: 10.1021/cr300182k

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

THF co-solvent enhances hydrocarbon fuel precursor yields from lignocellulosic biomass
journal, January 2013

  • Cai, Charles M.; Zhang, Taiying; Kumar, Rajeev
  • Green Chemistry, Vol. 15, Issue 11
  • DOI: 10.1039/c3gc41214h

Understanding solvent effects in the selective conversion of fructose to 5-hydroxymethyl-furfural: a molecular dynamics investigation
journal, January 2012

  • Mushrif, Samir H.; Caratzoulas, Stavros; Vlachos, Dionisios G.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 8
  • DOI: 10.1039/c2cp22694d

Catalytic fast pyrolysis of cellulose and biomass to produce levoglucosenone using magnetic SO42−/TiO2–Fe3O4
journal, November 2014


1,2,6-Hexanetriol in Alkyd Resins
journal, March 1957

  • Tess, Roy W.; Harline, Richard D.; Mika, Thomas F.
  • Industrial & Engineering Chemistry, Vol. 49, Issue 3
  • DOI: 10.1021/ie51392a028

Second dissociation constant of sulfuric acid in acetonitrile and in dimethyl sulfoxide
journal, October 1968

  • Kolthoff, I. M.; Chantooni, M. K.
  • Journal of the American Chemical Society, Vol. 90, Issue 22
  • DOI: 10.1021/ja01024a003

Simple Chemical Transformation of Lignocellulosic Biomass into Furans for Fuels and Chemicals
journal, February 2009

  • Binder, Joseph B.; Raines, Ronald T.
  • Journal of the American Chemical Society, Vol. 131, Issue 5, p. 1979-1985
  • DOI: 10.1021/ja808537j

Chloride ions enhance furfural formation from d-xylose in dilute aqueous acidic solutions
journal, January 2010

  • Marcotullio, Gianluca; De Jong, Wiebren
  • Green Chemistry, Vol. 12, Issue 10
  • DOI: 10.1039/b927424c

Conversion of Hemicellulose into Furfural Using Solid Acid Catalysts in γ-Valerolactone
journal, December 2012

  • Gürbüz, Elif I.; Gallo, Jean Marcel R.; Alonso, David Martin
  • Angewandte Chemie International Edition, Vol. 52, Issue 4, p. 1270-1274
  • DOI: 10.1002/anie.201207334

Dehydration of fructose to 5-hydroxymethylfurfural in sub- and supercritical acetone
journal, February 2003

  • Bicker, M.; Hirth, J.; Vogel, H.
  • Green Chemistry, Vol. 5, Issue 2
  • DOI: 10.1039/b211468b

Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides
journal, January 2007

  • Chheda, Juben N.; Román-Leshkov, Yuriy; Dumesic, James A.
  • Green Chem., Vol. 9, Issue 4, p. 342-350
  • DOI: 10.1039/B611568C

Techno-economic analysis of dimethylfuran (DMF) and hydroxymethylfurfural (HMF) production from pure fructose in catalytic processes
journal, May 2011

  • Kazi, Feroz Kabir; Patel, Akshay D.; Serrano-Ruiz, Juan Carlos
  • Chemical Engineering Journal, Vol. 169, Issue 1-3
  • DOI: 10.1016/j.cej.2011.03.018

Single-step conversion of cellulose to 5-hydroxymethylfurfural (HMF), a versatile platform chemical
journal, June 2009


Mediating acid-catalyzed conversion of levoglucosan into platform chemicals with various solvents
journal, January 2012

  • Hu, Xun; Wu, Liping; Wang, Yi
  • Green Chemistry, Vol. 14, Issue 11, p. 3087-3098
  • DOI: 10.1039/c2gc35961h

An ionic liquid reaction and separation process for production of hydroxymethylfurfural from sugars
journal, November 2013

  • Liu, Wei; Richard Zheng, Feng; Li, Joanne
  • AIChE Journal, Vol. 60, Issue 1
  • DOI: 10.1002/aic.14289

Dissociation constants of uncharged and monovalent cation acids in dimethyl sulfoxide
journal, January 1968

  • Kolthoff, Izaak M.; Chantooni, Miran K.; Bhowmik, Sadhana.
  • Journal of the American Chemical Society, Vol. 90, Issue 1
  • DOI: 10.1021/ja01003a005

Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass
journal, January 2013

  • Alonso, David Martin; Wettstein, Stephanie G.; Dumesic, James A.
  • Green Chemistry, Vol. 15, Issue 3
  • DOI: 10.1039/c3gc37065h

Sulfonate Ionic Liquid as a Stable and Active Catalyst for Levoglucosenone Production from Saccharides via Catalytic Pyrolysis
journal, September 2013


High yield conversion of cellulosic biomass into 5-hydroxymethylfurfural and a study of the reaction kinetics of cellulose to HMF conversion in a biphasic system
journal, January 2016

  • Atanda, Luqman; Konarova, Muxina; Ma, Qing
  • Catalysis Science & Technology, Vol. 6, Issue 16
  • DOI: 10.1039/C6CY00820H

Synthesis of C-glycosyl compounds and other natural products from levoglucosenone
journal, January 1994


Recent Applications of Levoglucosenone as Chiral Synthon
journal, July 2012

  • M. Sarotti, Ariel; M. Zanardi, Maria; A. Spanevello, Rolando
  • Current Organic Synthesis, Vol. 9, Issue 4
  • DOI: 10.2174/157017912802651401

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


Simulation Analysis and Nondestructive Testing of Flexural Performance of wood Single lap Glued Joints
journal, August 2012


An efficient microwave-assisted green transformation of cellulose into levoglucosenone. Advantages of the use of an experimental design approach
journal, January 2007

  • Sarotti, Ariel M.; Spanevello, Rolando A.; Suárez, Alejandra G.
  • Green Chemistry, Vol. 9, Issue 10
  • DOI: 10.1039/b703690f

Production of 5-Hydroxymethylfurfural from Glucose Using a Combination of Lewis and Brønsted Acid Catalysts in Water in a Biphasic Reactor with an Alkylphenol Solvent
journal, April 2012

  • Pagán-Torres, Yomaira J.; Wang, Tianfu; Gallo, Jean Marcel R.
  • ACS Catalysis, Vol. 2, Issue 6, p. 930-934
  • DOI: 10.1021/cs300192z

High yield synthesis of 5-hydroxymethylfurfural from cellulose using FePO 4 as the catalyst
journal, November 2016


Cellulose dehydration and depolymerization reactions during pyrolysis in the presence of phosphoric acid
journal, February 1999


The Role of Metal Halides in Enhancing the Dehydration of Xylose to Furfural
journal, January 2015


5-Hydroxymethylfurfural production from sugars and cellulose in acid- and base-catalyzed conditions under hot compressed water
journal, November 2012

  • Daorattanachai, Pornlada; Namuangruk, Supawadee; Viriya-empikul, Nawin
  • Journal of Industrial and Engineering Chemistry, Vol. 18, Issue 6, p. 1893-1901
  • DOI: 10.1016/j.jiec.2012.04.019

Continuous production of 5-hydroxymethylfurfural from fructose: a design case study
journal, January 2010

  • Torres, Ana I.; Daoutidis, Prodromos; Tsapatsis, Michael
  • Energy & Environmental Science, Vol. 3, Issue 10
  • DOI: 10.1039/c0ee00082e

Catalytic and catalytic free process for cellulose conversion: fast pyrolysis and microwave induced pyrolysis studies
journal, November 2014

  • Nieva, María Luz; Volpe, María Alicia; Moyano, Elizabeth Laura
  • Cellulose, Vol. 22, Issue 1
  • DOI: 10.1007/s10570-014-0484-z

Hydrothermal Conversion of Cellulose to 5-Hydroxymethyl Furfural
journal, March 2011


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

Cellulose recycling as a source of raw chirality
journal, July 2013

  • Corne, Valeria; Botta, María Celeste; Giordano, Enrique D. V.
  • Pure and Applied Chemistry, Vol. 85, Issue 8
  • DOI: 10.1351/PAC-CON-12-11-10

A mechanistic model of fast pyrolysis of glucose-based carbohydrates to predict bio-oil composition
journal, January 2012

  • Vinu, R.; Broadbelt, Linda J.
  • Energy & Environmental Science, Vol. 5, Issue 12
  • DOI: 10.1039/c2ee22784c

A kinetic model for production of glucose by hydrolysis of levoglucosan and cellobiosan from pyrolysis oil
journal, November 2007


Selective Conversion of Cellulose to Hydroxymethylfurfural in Polar Aprotic Solvents
journal, July 2014

  • Weingarten, Ronen; Rodriguez-Beuerman, Alexandra; Cao, Fei
  • ChemCatChem, Vol. 6, Issue 8
  • DOI: 10.1002/cctc.201402299

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

Depolymerization of Cellulose Using Solid Catalysts in Ionic Liquids
journal, October 2008

  • Rinaldi, Roberto; Palkovits, Regina; Schüth, Ferdi
  • Angewandte Chemie International Edition, Vol. 47, Issue 42, p. 8047-8050
  • DOI: 10.1002/anie.200802879

Formation of Furfural in Catalytic Transformation of Levoglucosan over Mesoporous Materials
journal, April 2010


5-Hydroxymethylfurfural (HMF). A Review Focussing on its Manufacture
journal, January 1990


Influence of pyrolysis temperature and time on the cellulose fast pyrolysis products: Analytical Py-GC/MS study
journal, November 2011

  • Lu, Qiang; Yang, Xiao-chu; Dong, Chang-qing
  • Journal of Analytical and Applied Pyrolysis, Vol. 92, Issue 2, p. 430-438
  • DOI: 10.1016/j.jaap.2011.08.006

Conversion of carbohydrates into 5-hydroxymethylfurfural catalyzed by ZnCl2 in water
journal, January 2012

  • Deng, Tiansheng; Cui, Xiaojing; Qi, Yongqin
  • Chemical Communications, Vol. 48, Issue 44, p. 5494-5496
  • DOI: 10.1039/c2cc00122e

Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural
journal, June 2007


Biomass to chemicals: Design of an extractive-reaction process for the production of 5-hydroxymethylfurfural
journal, July 2012


Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose
journal, June 2006

  • Roman-Leshkov, Yuriy; Chheda, Juben N.; Dumesic, James A.
  • Science, Vol. 312, Issue 5782, p. 1933-1937
  • DOI: 10.1126/science.1126337

Efficient levoglucosenone production by catalytic pyrolysis of cellulose mixed with ionic liquid
journal, January 2011

  • Kudo, Shinji; Zhou, Zhenwei; Norinaga, Koyo
  • Green Chemistry, Vol. 13, Issue 11
  • DOI: 10.1039/c1gc15975e

Kinetics of Levoglucosenone Isomerization
journal, December 2016

  • Krishna, Siddarth H.; Walker, Theodore W.; Dumesic, James A.
  • ChemSusChem, Vol. 10, Issue 1
  • DOI: 10.1002/cssc.201601308

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


Catalytic Dehydration of Carbohydrates Suspended in Organic Solvents Promoted by AlCl 3 /SiO 2 Coated with Choline Chloride
journal, November 2014

  • Yang, Jie; De Oliveira Vigier, Karine; Gu, Yanlong
  • ChemSusChem, Vol. 8, Issue 2
  • DOI: 10.1002/cssc.201402761

Hydrogenation of levoglucosenone to renewable chemicals
journal, January 2017

  • Krishna, Siddarth H.; McClelland, Daniel J.; Rashke, Quinn A.
  • Green Chemistry, Vol. 19, Issue 5
  • DOI: 10.1039/C6GC03028A

Ionic Liquid-Mediated Formation of 5-Hydroxymethylfurfural—A Promising Biomass-Derived Building Block
journal, February 2011

  • Zakrzewska, Małgorzata E.; Bogel-Łukasik, Ewa; Bogel-Łukasik, Rafał
  • Chemical Reviews, Vol. 111, Issue 2, p. 397-417
  • DOI: 10.1021/cr100171a

Preparation of levoglucosenone through sulfuric acid promoted pyrolysis of bagasse at low temperature
journal, January 2012


Pitting corrosion mechanism of Type 304 stainless steel under a droplet of chloride solutions
journal, March 2007


    Works referencing / citing this record:

    Catalytic dehydration of levoglucosan to levoglucosenone using Brønsted solid acid catalysts in tetrahydrofuran
    journal, January 2019

    • Oyola-Rivera, Oscar; He, Jiayue; Huber, George W.
    • Green Chemistry, Vol. 21, Issue 18
    • DOI: 10.1039/c9gc01526d

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

    • He, Jiayue; Huang, Kefeng; Barnett, Kevin J.
    • Faraday Discussions, Vol. 202
    • DOI: 10.1039/c7fd00036g

    Catalytic dehydration of levoglucosan to levoglucosenone using Brønsted solid acid catalysts in tetrahydrofuran
    journal, January 2019

    • Oyola-Rivera, Oscar; He, Jiayue; Huber, George W.
    • Green Chemistry, Vol. 21, Issue 18
    • DOI: 10.1039/c9gc01526d

    Leather‐Promoted Transformation of Glucose into 5‐Hydroxymethylfurfural and Levoglucosenone
    journal, April 2019

    • Bobbink, Felix D.; Huang, Zhangjun; Menoud, Florent
    • ChemSusChem, Vol. 12, Issue 7
    • DOI: 10.1002/cssc.201802830

    Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents
    journal, March 2019

    • Mellmer, Max A.; Sanpitakseree, Chotitath; Demir, Benginur
    • Nature Communications, Vol. 10, Issue 1
    • DOI: 10.1038/s41467-019-09090-4

    Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates
    journal, January 2018

    • Walker, Theodore W.; Chew, Alex K.; Li, Huixiang
    • Energy & Environmental Science, Vol. 11, Issue 3
    • DOI: 10.1039/c7ee03432f

    Direct catalytic conversion of glucose and cellulose
    journal, January 2018

    • Li, Zhenhuan; Su, Kunmei; Ren, Jun
    • Green Chemistry, Vol. 20, Issue 4
    • DOI: 10.1039/c7gc03318d

    Propylene carbonate and γ-valerolactone as green solvents enhance Sn( iv )-catalysed hydroxymethylfurfural (HMF) production from bread waste
    journal, January 2018

    • Yu, Iris K. M.; Tsang, Daniel C. W.; Yip, Alex C. K.
    • Green Chemistry, Vol. 20, Issue 9
    • DOI: 10.1039/c8gc00358k

    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

    • Krishna, Siddarth H.; De bruyn, Mario; Schmidt, Zachary R.
    • Green Chemistry, Vol. 20, Issue 19
    • DOI: 10.1039/c8gc02455c

    Combining steam distillation with microwave-assisted pyrolysis to maximise direct production of levoglucosenone from agricultural wastes
    journal, January 2019

    • Bouxin, Florent P.; Clark, James H.; Fan, Jiajun
    • Green Chemistry, Vol. 21, Issue 6
    • DOI: 10.1039/c8gc02994f

    From waste biomass to chemicals and energy via microwave-assisted processes
    journal, January 2019

    • Calcio Gaudino, Emanuela; Cravotto, Giancarlo; Manzoli, Maela
    • Green Chemistry, Vol. 21, Issue 6
    • DOI: 10.1039/c8gc03908a

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

    • De bruyn, Mario; Sener, Canan; Petrolini, Davi D.
    • Green Chemistry, Vol. 21, Issue 18
    • DOI: 10.1039/c9gc00564a

    Making natural products from renewable feedstocks: back to the roots?
    journal, January 2020

    • Kühlborn, Jonas; Groß, Jonathan; Opatz, Till
    • Natural Product Reports, Vol. 37, Issue 3
    • DOI: 10.1039/c9np00040b