Production and purification of crystallized levoglucosan from pyrolysis of lignocellulosic biomass
Abstract
Levoglucosan has significant potential in commercial applications for the synthesis of polymers, solvents and pharmaceuticals. It is currently overlooked for commercial applications due to its high cost of synthesis and purification. We have developed a system to produce pure crystals of levoglucosan based on the fast pyrolysis of lignocellulosic biomass. A novel bio-oil recovery system concentrated levoglucosan along with other anhydrosugars, sugars and phenolic compounds in a non-aqueous “heavy ends” fraction. Liquid–liquid water extraction separated sugar-rich solubilized carbohydrates from non-soluble phenolic compounds. The solubilized carbohydrate fraction, contaminated with partially soluble phenolic monomers, was filtered through Sepabeads SP207 adsorption resin to produce clarified juice. The composition of the clarified juice on a dry basis after resin filtration and rotary evaporation was 81.2% sugars, 4.45–4.60% volatile non-sugar, 1.71% carboxylic acids and 12.5–12.6% unidentified compounds, which was sufficiently pure to crystallize the sugars by evaporation. A cold solvent rinse of the crystal mass separated and purified levoglucosan from other sugars. Levoglucosan purity was 102.5% ± 3.109% at the 99% confidence level. Techno-economic analysis of a plant pyrolyzing 250 tonne per day of pretreated biomass to produce cellulosic sugars indicated a minimum selling price (MSP) for pure levoglucosan crystals of $1333 per MT, whichmore »
- Authors:
-
- Bioeconomy Institute, Iowa State University, Ames, USA
- Department of Mechanical Engineering, Iowa State University, Ames, USA
- Bioeconomy Institute, Iowa State University, Ames, USA, Department of Mechanical Engineering
- Publication Date:
- Research Org.:
- RAPID Manufacturing Institute, New York, NY (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Manufacturing Office
- OSTI Identifier:
- 1572133
- Alternate Identifier(s):
- OSTI ID: 1642392
- Grant/Contract Number:
- EE0007888
- Resource Type:
- Published Article
- Journal Name:
- Green Chemistry
- Additional Journal Information:
- Journal Name: Green Chemistry Journal Volume: 21 Journal Issue: 21; Journal ID: ISSN 1463-9262
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Rover, Marjorie R., Aui, Alvina, Wright, Mark Mba, Smith, Ryan G., and Brown, Robert C. Production and purification of crystallized levoglucosan from pyrolysis of lignocellulosic biomass. United Kingdom: N. p., 2019.
Web. doi:10.1039/C9GC02461A.
Rover, Marjorie R., Aui, Alvina, Wright, Mark Mba, Smith, Ryan G., & Brown, Robert C. Production and purification of crystallized levoglucosan from pyrolysis of lignocellulosic biomass. United Kingdom. https://doi.org/10.1039/C9GC02461A
Rover, Marjorie R., Aui, Alvina, Wright, Mark Mba, Smith, Ryan G., and Brown, Robert C. Mon .
"Production and purification of crystallized levoglucosan from pyrolysis of lignocellulosic biomass". United Kingdom. https://doi.org/10.1039/C9GC02461A.
@article{osti_1572133,
title = {Production and purification of crystallized levoglucosan from pyrolysis of lignocellulosic biomass},
author = {Rover, Marjorie R. and Aui, Alvina and Wright, Mark Mba and Smith, Ryan G. and Brown, Robert C.},
abstractNote = {Levoglucosan has significant potential in commercial applications for the synthesis of polymers, solvents and pharmaceuticals. It is currently overlooked for commercial applications due to its high cost of synthesis and purification. We have developed a system to produce pure crystals of levoglucosan based on the fast pyrolysis of lignocellulosic biomass. A novel bio-oil recovery system concentrated levoglucosan along with other anhydrosugars, sugars and phenolic compounds in a non-aqueous “heavy ends” fraction. Liquid–liquid water extraction separated sugar-rich solubilized carbohydrates from non-soluble phenolic compounds. The solubilized carbohydrate fraction, contaminated with partially soluble phenolic monomers, was filtered through Sepabeads SP207 adsorption resin to produce clarified juice. The composition of the clarified juice on a dry basis after resin filtration and rotary evaporation was 81.2% sugars, 4.45–4.60% volatile non-sugar, 1.71% carboxylic acids and 12.5–12.6% unidentified compounds, which was sufficiently pure to crystallize the sugars by evaporation. A cold solvent rinse of the crystal mass separated and purified levoglucosan from other sugars. Levoglucosan purity was 102.5% ± 3.109% at the 99% confidence level. Techno-economic analysis of a plant pyrolyzing 250 tonne per day of pretreated biomass to produce cellulosic sugars indicated a minimum selling price (MSP) for pure levoglucosan crystals of $1333 per MT, which is less than one-tenth its current average market price. Operating hours of the plant, fermentable syrup yield and fixed capital are the most significant parameters affecting MSP.},
doi = {10.1039/C9GC02461A},
journal = {Green Chemistry},
number = 21,
volume = 21,
place = {United Kingdom},
year = {2019},
month = {10}
}
https://doi.org/10.1039/C9GC02461A
Web of Science
Figures / Tables:

Works referenced in this record:
New Derivatives of Levoglucosan by Tandem Epoxide Allyl Alcohol Rearrangement-Cuprate Cross-Coupling
journal, July 2005
- Krohn, Karsten; Gehle, Dietmar; Flörke, Ulrich
- European Journal of Organic Chemistry, Vol. 2005, Issue 13
Continuous production of sugars from pyrolysis of acid-infused lignocellulosic biomass
journal, January 2014
- Dalluge, Dustin L.; Daugaard, Tannon; Johnston, Patrick
- Green Chem., Vol. 16, Issue 9
Process intensification of biomass fast pyrolysis through autothermal operation of a fluidized bed reactor
journal, September 2019
- Polin, Joseph P.; Peterson, Chad A.; Whitmer, Lysle E.
- Applied Energy, Vol. 249
The effect of pyrolysis temperature on recovery of bio-oil as distinctive stage fractions
journal, January 2014
- Rover, Marjorie R.; Johnston, Patrick A.; Whitmer, Lysle E.
- Journal of Analytical and Applied Pyrolysis, Vol. 105
Characterization of bio-oil recovered as stage fractions with unique chemical and physical properties
journal, January 2012
- Pollard, A. S.; Rover, M. R.; Brown, R. C.
- Journal of Analytical and Applied Pyrolysis, Vol. 93
Comparative Techno-economic, Uncertainty and Life Cycle Analysis of Lignocellulosic Biomass Solvent Liquefaction and Sugar Fermentation to Ethanol
journal, October 2018
- Li, Wenqin; Ghosh, Arpa; Bbosa, Denis
- ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 12
Erratum to “Detailed characterization of red oak-derived pyrolysis oil: Integrated use of GC, HPLC, IC, GPC and Karl–Fischer” [J. Anal. Appl. Pyrol. 110 (2014) 147-154]
journal, March 2015
- Choi, Fischer Yong S.; Johnston, Patrick A.; Brown, Robert C.
- Journal of Analytical and Applied Pyrolysis, Vol. 112
The impacts of biomass properties on pyrolysis yields, economic and environmental performance of the pyrolysis-bioenergy-biochar platform to carbon negative energy
journal, October 2017
- Li, Wenqin; Dang, Qi; Brown, Robert C.
- Bioresource Technology, Vol. 241
Synthesis of protected glucose derivatives from levoglucosan by development of common carbohydrate protecting group reactions under continuous flow conditions
journal, October 2018
- Marion, Keevan C.; Wooke, Zachary; Pohl, Nicola L. B.
- Carbohydrate Research, Vol. 468
Production of Clean Pyrolytic Sugars for Fermentation
journal, April 2014
- Rover, Marjorie R.; Johnston, Patrick A.; Jin, Tao
- ChemSusChem, Vol. 7, Issue 6, p. 1662-1668
Techno-economic analyses of solid-state anaerobic digestion and composting of yard trimmings
journal, February 2019
- Lin, Long; Shah, Ajay; Keener, Harold
- Waste Management, Vol. 85
Characterization of cane sugar crystallization using image fractal analysis
journal, September 2010
- Velazquez-Camilo, Oscar; Bolaños-Reynoso, Eusebio; Rodriguez, Eduardo
- Journal of Food Engineering, Vol. 100, Issue 1
Lignocellulosic Biomass to Ethanol Process Design and Economics Utilizing Co-Current Dilute Acid Prehydrolysis and Enzymatic Hydrolysis for Corn Stover
report, June 2002
- Aden, A.; Ruth, M.; Ibsen, K.
- NREL/TP-510-32438
Separation of bio-oil by molecular distillation
journal, May 2009
- Wang, Shurong; Gu, Yueling; Liu, Qian
- Fuel Processing Technology, Vol. 90, Issue 5
Production of Levoglucosan by Pyrolysis of Carbohydrates
journal, September 1969
- Lakshmanan, C. M.; Gal-or, Benjamin; Hoelscher, H. E.
- Industrial & Engineering Chemistry Product Research and Development, Vol. 8, Issue 3
Pyrolytic Sugars from Cellulosic Biomass
journal, September 2012
- Kuzhiyil, Najeeb; Dalluge, Dustin; Bai, Xianglan
- ChemSusChem, Vol. 5, Issue 11
Total water-soluble sugars quantification in bio-oil using the phenol–sulfuric acid assay
journal, November 2013
- Rover, Marjorie R.; Johnston, Patrick A.; Lamsal, Buddhi P.
- Journal of Analytical and Applied Pyrolysis, Vol. 104
Separation of sugars and phenolics from the heavy fraction of bio-oil using polymeric resin adsorbents
journal, April 2018
- Stanford, John P.; Hall, Patrick H.; Rover, Marjorie R.
- Separation and Purification Technology, Vol. 194
Direct synthesis of 1,6-anhydro sugars from unprotected glycopyranoses by using 2-chloro-1,3-dimethylimidazolinium chloride
journal, May 2009
- Tanaka, Tomonari; Huang, Wei Chun; Noguchi, Masato
- Tetrahedron Letters, Vol. 50, Issue 18
Techno-economic and uncertainty analysis of in situ and ex situ fast pyrolysis for biofuel production
journal, November 2015
- Li, Boyan; Ou, Longwen; Dang, Qi
- Bioresource Technology, Vol. 196
1,6-Anhydroglucose in organic synthesis; preparation of fragments suitable for natural product synthesis
journal, January 1985
- Hodges, Paul J.; Procter, Garry
- Tetrahedron Letters, Vol. 26, Issue 34
Ring-locking enables selective anhydrosugar synthesis from carbohydrate pyrolysis
journal, January 2016
- Chen, Li; Zhao, Jinmo; Pradhan, Sivaram
- Green Chemistry, Vol. 18, Issue 20
Product distribution from fast pyrolysis of glucose-based carbohydrates
journal, November 2009
- Patwardhan, Pushkaraj R.; Satrio, Justinus A.; Brown, Robert C.
- Journal of Analytical and Applied Pyrolysis, Vol. 86, Issue 2
Economic optimization of heat pump-assisted distillation columns in methanol-water separation
journal, February 2015
- Shahandeh, Hossein; Jafari, Mina; Kasiri, Norollah
- Energy, Vol. 80
An Economic Analysis of Three Operational Co-digestion Biogas Plants in Germany
journal, October 2011
- Balussou, David; Kleyböcker, Anne; McKenna, Russell
- Waste and Biomass Valorization, Vol. 3, Issue 1
Stabilization of bio-oils using low temperature, low pressure hydrogenation
journal, August 2015
- Rover, Marjorie R.; Hall, Patrick H.; Johnston, Patrick A.
- Fuel, Vol. 153
Techno-Economic Analysis of the Stabilization of Bio-Oil Fractions for Insertion into Petroleum Refineries
journal, December 2016
- Li, Wenqin; Dang, Qi; Smith, Ryan
- ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 2
Influence of inorganic salts on the primary pyrolysis products of cellulose
journal, June 2010
- Patwardhan, Pushkaraj R.; Satrio, Justinus A.; Brown, Robert C.
- Bioresource Technology, Vol. 101, Issue 12
Techno-economic analysis of electricity and heat generation from farm-scale biogas plant: Çiçekdağı case study
journal, August 2012
- Akbulut, Abdullah
- Energy, Vol. 44, Issue 1
Synthesis of polynitrogenated analogues of glucopyranoses from levoglucosan
journal, January 2004
- Bailliez, Vincent; Olesker, Alain; Cleophax, Jeannine
- Tetrahedron, Vol. 60, Issue 5