Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors
Abstract
We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; the aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.
- Authors:
-
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office
- OSTI Identifier:
- 1390574
- Alternate Identifier(s):
- OSTI ID: 1495817
- Report Number(s):
- PNNL-SA-127729
Journal ID: ISSN 0920-5861; PII: S0920586117304637
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysis Today
- Additional Journal Information:
- Journal Volume: 302; Journal ID: ISSN 0920-5861
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Levulinic acid; Gamma-valerolactone; Ketonization; Distillate fuels; Biomass
Citation Formats
Lilga, Michael A., Padmaperuma, Asanga B., Auberry, Deanna L., Job, Heather M., and Swita, Marie S. Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors. United States: N. p., 2017.
Web. doi:10.1016/j.cattod.2017.06.021.
Lilga, Michael A., Padmaperuma, Asanga B., Auberry, Deanna L., Job, Heather M., & Swita, Marie S. Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors. United States. https://doi.org/10.1016/j.cattod.2017.06.021
Lilga, Michael A., Padmaperuma, Asanga B., Auberry, Deanna L., Job, Heather M., and Swita, Marie S. Wed .
"Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors". United States. https://doi.org/10.1016/j.cattod.2017.06.021. https://www.osti.gov/servlets/purl/1390574.
@article{osti_1390574,
title = {Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors},
author = {Lilga, Michael A. and Padmaperuma, Asanga B. and Auberry, Deanna L. and Job, Heather M. and Swita, Marie S.},
abstractNote = {We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; the aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.},
doi = {10.1016/j.cattod.2017.06.021},
journal = {Catalysis Today},
number = ,
volume = 302,
place = {United States},
year = {Wed Jun 21 00:00:00 EDT 2017},
month = {Wed Jun 21 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
A review and perspective of recent bio-oil hydrotreating research
journal, January 2014
- Zacher, Alan H.; Olarte, Mariefel V.; Santosa, Daniel M.
- Green Chem., Vol. 16, Issue 2
Catalytic transformations of biomass-derived acids into advanced biofuels
journal, November 2012
- Serrano-Ruiz, Juan Carlos; Pineda, Antonio; Balu, Alina Mariana
- Catalysis Today, Vol. 195, Issue 1
Catalytic conversion of biomass to biofuels
journal, January 2010
- Alonso, David Martin; Bond, Jesse Q.; Dumesic, James A.
- Green Chemistry, Vol. 12, Issue 9, p. 1493-1513
Ketonization of Carboxylic Acids: Mechanisms, Catalysts, and Implications for Biomass Conversion
journal, October 2013
- Pham, Tu N.; Sooknoi, Tawan; Crossley, Steven P.
- ACS Catalysis, Vol. 3, Issue 11
Insights into the Ceria-Catalyzed Ketonization Reaction for Biofuels Applications
journal, February 2013
- Snell, Ryan W.; Shanks, Brent H.
- ACS Catalysis, Vol. 3, Issue 4
Reactions of Carboxylic Acids on Oxides
journal, June 1997
- Pestman, R.; Koster, R. M.; van Duijne, A.
- Journal of Catalysis, Vol. 168, Issue 2
Liquid hydrocarbonfuels from cellulosic feedstocks via thermal deoxygenation of levulinic acid and formic acid salt mixtures
journal, January 2012
- Case, Paige A.; van Heiningen, Adriaan R. P.; Wheeler, M. Clayton
- Green Chem., Vol. 14, Issue 1
Development of Heterogeneous Catalysts for the Conversion of Levulinic Acid to γ-Valerolactone
journal, August 2012
- Wright, William R. H.; Palkovits, Regina
- ChemSusChem, Vol. 5, Issue 9
Selective aldol condensation of biomass-derived levulinic acid and furfural in aqueous-phase over MgO and ZnO
journal, January 2016
- Liang, Guanfeng; Wang, Aiqin; Zhao, Xiaochen
- Green Chemistry, Vol. 18, Issue 11
Base-Catalyzed Condensation of Levulinic Acid: A New Biorefinery Upgrading Approach
journal, March 2016
- Faba, Laura; Díaz, Eva; Ordóñez, Salvador
- ChemCatChem, Vol. 8, Issue 8
Synthesis and utilisation of sugar compounds derived from lignocellulosic biomass
journal, January 2013
- Kobayashi, Hirokazu; Fukuoka, Atsushi
- Green Chemistry, Vol. 15, Issue 7
Molecular and industrial aspects of glucose isomerase.
journal, January 1996
- Bhosale, S. H.; Rao, M. B.; Deshpande, V. V.
- Microbiological reviews, Vol. 60, Issue 2
Salt-Promoted Glucose Aqueous Isomerization Catalyzed by Heterogeneous Organic Base
journal, August 2016
- Yang, Qiang; Lan, Wu; Runge, Troy
- ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 9
Selective preparation of furfural from xylose over microporous solid acid catalysts
journal, January 1998
- Moreau, Claude; Durand, Robert; Peyron, Delphine
- Industrial Crops and Products, Vol. 7, Issue 2-3
Experimental and theoretical studies of the acid-catalyzed conversion of furfuryl alcohol to levulinic acid in aqueous solution
journal, January 2012
- González Maldonado, Gretchen M.; Assary, Rajeev S.; Dumesic, James
- Energy & Environmental Science, Vol. 5, Issue 5
High Yield Conversion of Residual Pentoses into Furfural via Zeolite Catalysis and Catalytic Hydrogenation of Furfural to 2-Methylfuran
journal, June 2010
- Lessard, Jean; Morin, Jean-François; Wehrung, Jean-François
- Topics in Catalysis, Vol. 53, Issue 15-18
Solvent Effects on Fructose Dehydration to 5-Hydroxymethylfurfural in Biphasic Systems Saturated with Inorganic Salts
journal, January 2009
- Román-Leshkov, Yuriy; Dumesic, James A.
- Topics in Catalysis, Vol. 52, Issue 3, p. 297-303
Integrated Catalytic Conversion of γ-Valerolactone to Liquid Alkenes for Transportation Fuels
journal, February 2010
- Bond, J. Q.; Alonso, D. M.; Wang, D.
- Science, Vol. 327, Issue 5969, p. 1110-1114
Characterization and Combustion of Crude Thermal Deoxygenation Oils Derived From Hydrolyzed Woody Biomass
journal, August 2013
- Eaton, Scott J.; Beis, Sedat H.; Bunting, Bruce G.
- Energy & Fuels, Vol. 27, Issue 9
Hydroprocessing of Biorenewable Thermal Deoxygenation Oils
journal, April 2015
- Eaton, Scott J.; Beis, Sedat H.; Karunarathne, Sampath A.
- Energy & Fuels, Vol. 29, Issue 5
Ketonization and deoxygenation of alkanoic acids and conversion of levulinic acid to hydrocarbons using a Red Mud bauxite mining waste as the catalyst
journal, August 2012
- Karimi, Elham; Teixeira, Ivo Freitas; Ribeiro, Leandro Passos
- Catalysis Today, Vol. 190, Issue 1, p. 73-88
The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms
journal, January 1951
- Barrett, Elliott P.; Joyner, Leslie G.; Halenda, Paul P.
- Journal of the American Chemical Society, Vol. 73, Issue 1
A Mild and Efficient Flow Procedure for the Transfer Hydrogenation of Ketones and Aldehydes using Hydrous Zirconia
journal, April 2013
- Battilocchio, Claudio; Hawkins, Joel M.; Ley, Steven V.
- Organic Letters, Vol. 15, Issue 9
Liquid-phase catalytic transfer hydrogenation and cyclization of levulinic acid and its esters to γ-valerolactone over metal oxide catalysts
journal, January 2011
- Chia, Mei; Dumesic, James A.
- Chemical Communications, Vol. 47, Issue 44
ZrO 2 /SBA-15 as an efficient catalyst for the production of γ-valerolactone from biomass-derived levulinic acid in the vapour phase at atmospheric pressure
journal, January 2016
- Enumula, Siva Sankar; Gurram, Venkata Ramesh Babu; Kondeboina, Murali
- RSC Advances, Vol. 6, Issue 24
Reduction of Benzaldehyde on Metal Oxides
journal, November 1997
- Haffad, D.; Kameswari, U.; Bettahar, M. M.
- Journal of Catalysis, Vol. 172, Issue 1
Interconversion between γ-valerolactone and pentenoic acid combined with decarboxylation to form butene over silica/alumina
journal, July 2011
- Bond, Jesse Q.; Wang, Dong; Alonso, David Martin
- Journal of Catalysis, Vol. 281, Issue 2
Works referencing / citing this record:
Cascade Strategy for the Tunable Catalytic Valorization of Levulinic Acid and γ-Valerolactone to 2-Methyltetrahydrofuran and Alcohols
journal, July 2018
- Licursi, Domenico; Antonetti, Claudia; Fulignati, Sara
- Catalysts, Vol. 8, Issue 7