Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock
Abstract
Abstract Supercritical methanol (SCM) solvolysis and catalysis has recently emerged as a promising pathway to produce gasoline‐range light alcohols from woody biomass through staged depolymerization and hydro‐deoxygenation (DHDO). Here, structure–property relationships of Cu“M”AlO x catalysts (M = Mg, Zr, and Ce) are examined for upgrading delignified hybrid poplar via SCM‐DHDO. CuCeAlO x displays the highest activity, increasing the C 2 C 7 alcohol production rate and selectivity by twofold in batch reactions, and > 50% in semicontinuous reactions relative to the current state‐of‐the‐art CuMgAlO x . The performance of CuCeAlO x is correlated with its high reducibility and acidity. Cu sintering and biogenic impurity poisoning are identified as possible deactivation mechanisms over 60 h of continuous testing. The gasoline‐range SCM‐DHDO products are comprised of primarily aliphatic alcohols that result in improved energy density and favorably reduced vapor pressure, relative to ethanol, with the tradeoff of nonsynergistic octane blending with conventional gasoline and lower oxidation stability. Overall, this work highlights the potential to produce suitable light oxygenates by SCM‐DHDO processing for gasoline bioblendstock applications.
- Authors:
-
[1];
[1];
[1];
[1];
[1];
[1];
[2];
[1];
[1];
[3];
[4]
- National Renewable Energy Lab. (NREL), Golden, CO (United States). Catalytic Carbon Transformation and Scale-Up Center
- National Renewable Energy Lab. (NREL), Golden, CO (United States). Center for Integrated Mobility Sciences
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- National Renewable Energy Lab. (NREL), Golden, CO (United States). Catalytic Carbon Transformation and Scale-Up Center; Alder Fuels, Washington, DC (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1845685
- Alternate Identifier(s):
- OSTI ID: 1842392
- Report Number(s):
- NREL/JA-5100-80793
Journal ID: ISSN 2366-7486; MainId:78571;UUID:0cd5f484-4773-449e-b0e4-a167d3464e3c;MainAdminID:63852
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Sustainable Systems
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 4; Journal ID: ISSN 2366-7486
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; bioblendstock; catalysis; gasoline; light-duty; solvolysis; woody biomass
Citation Formats
Nguyen, Hannah, Huq, Nabila A., Stuck, Daniela, Tifft, Stephen M., Conklin, Davis R., Koehler, Andrew J., McNeary, William Wilson, Fioroni, Gina M., Hays, Cameron, Christensen, Earl D., McNamara, Ian, Bartling, Andrew, Davis, Ryan, Unocic, Kinga A., and Vardon, Derek R. Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock. United States: N. p., 2022.
Web. doi:10.1002/adsu.202100310.
Nguyen, Hannah, Huq, Nabila A., Stuck, Daniela, Tifft, Stephen M., Conklin, Davis R., Koehler, Andrew J., McNeary, William Wilson, Fioroni, Gina M., Hays, Cameron, Christensen, Earl D., McNamara, Ian, Bartling, Andrew, Davis, Ryan, Unocic, Kinga A., & Vardon, Derek R. Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock. United States. https://doi.org/10.1002/adsu.202100310
Nguyen, Hannah, Huq, Nabila A., Stuck, Daniela, Tifft, Stephen M., Conklin, Davis R., Koehler, Andrew J., McNeary, William Wilson, Fioroni, Gina M., Hays, Cameron, Christensen, Earl D., McNamara, Ian, Bartling, Andrew, Davis, Ryan, Unocic, Kinga A., and Vardon, Derek R. Thu .
"Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock". United States. https://doi.org/10.1002/adsu.202100310. https://www.osti.gov/servlets/purl/1845685.
@article{osti_1845685,
title = {Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock},
author = {Nguyen, Hannah and Huq, Nabila A. and Stuck, Daniela and Tifft, Stephen M. and Conklin, Davis R. and Koehler, Andrew J. and McNeary, William Wilson and Fioroni, Gina M. and Hays, Cameron and Christensen, Earl D. and McNamara, Ian and Bartling, Andrew and Davis, Ryan and Unocic, Kinga A. and Vardon, Derek R.},
abstractNote = {Abstract Supercritical methanol (SCM) solvolysis and catalysis has recently emerged as a promising pathway to produce gasoline‐range light alcohols from woody biomass through staged depolymerization and hydro‐deoxygenation (DHDO). Here, structure–property relationships of Cu“M”AlO x catalysts (M = Mg, Zr, and Ce) are examined for upgrading delignified hybrid poplar via SCM‐DHDO. CuCeAlO x displays the highest activity, increasing the C 2 C 7 alcohol production rate and selectivity by twofold in batch reactions, and > 50% in semicontinuous reactions relative to the current state‐of‐the‐art CuMgAlO x . The performance of CuCeAlO x is correlated with its high reducibility and acidity. Cu sintering and biogenic impurity poisoning are identified as possible deactivation mechanisms over 60 h of continuous testing. The gasoline‐range SCM‐DHDO products are comprised of primarily aliphatic alcohols that result in improved energy density and favorably reduced vapor pressure, relative to ethanol, with the tradeoff of nonsynergistic octane blending with conventional gasoline and lower oxidation stability. Overall, this work highlights the potential to produce suitable light oxygenates by SCM‐DHDO processing for gasoline bioblendstock applications.},
doi = {10.1002/adsu.202100310},
journal = {Advanced Sustainable Systems},
number = 4,
volume = 6,
place = {United States},
year = {Thu Jan 27 00:00:00 EST 2022},
month = {Thu Jan 27 00:00:00 EST 2022}
}
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Works referenced in this record:
Scaling reducibility of metal oxides
journal, August 2017
- Helali, Z.; Jedidi, A.; Syzgantseva, O. A.
- Theoretical Chemistry Accounts, Vol. 136, Issue 9
Selective hydrogenolysis of glycerol to propylene glycol by using Cu:Zn:Cr:Zr mixed metal oxides catalyst
journal, May 2014
- Sharma, Rajesh V.; Kumar, Pardeep; Dalai, Ajay K.
- Applied Catalysis A: General, Vol. 477
Guidelines for performing lignin-first biorefining
journal, January 2021
- Abu-Omar, Mahdi M.; Barta, Katalin; Beckham, Gregg T.
- Energy & Environmental Science, Vol. 14, Issue 1
The octane numbers of ethanol blended with gasoline and its surrogates
journal, January 2014
- Foong, Tien Mun; Morganti, Kai J.; Brear, Michael J.
- Fuel, Vol. 115
Vapor Pressures of Alcohol−Gasoline Blends
journal, June 2010
- Andersen, V. F.; Anderson, J. E.; Wallington, T. J.
- Energy & Fuels, Vol. 24, Issue 6
Production of Alcohols from Cellulose by Supercritical Methanol Depolymerization and Hydrodeoxygenation
journal, February 2018
- Galebach, Peter H.; McClelland, Daniel J.; Eagan, Nathaniel M.
- ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 3
Hydrogen Transfer from Supercritical Methanol over a Solid Base Catalyst A Model for Lignin Depolymerization
journal, March 2009
- Macala, Gerald S.; Matson, Theodore D.; Johnson, Charles L.
- ChemSusChem, Vol. 2, Issue 3, p. 215-217
Production of renewable alcohols from maple wood using supercritical methanol hydrodeoxygenation in a semi-continuous flowthrough reactor
journal, January 2020
- Galebach, Peter H.; Soeherman, Jimmy K.; Gilcher, Elise
- Green Chemistry, Vol. 22, Issue 23
The role of Copper–Ceria interactions in catalysis science: Recent theoretical and experimental advances
journal, December 2016
- Konsolakis, Michalis
- Applied Catalysis B: Environmental, Vol. 198
Study on Solid Acid Catalyzed Hydrolysis of Maltose and Related Polysaccharides
journal, January 1998
- Abbadi, Abdelilah; Gotlieb, Kees F.; van Bekkum, Herman
- Starch - Stärke, Vol. 50, Issue 1
Kinetic and mechanistic insights into hydrogenolysis of lignin to monomers in a continuous flow reactor
journal, January 2019
- Li, Yanding; Demir, Benginur; Vázquez Ramos, Leida M.
- Green Chemistry, Vol. 21, Issue 13
Impact of Higher Alcohols Blended in Gasoline on Light-Duty Vehicle Exhaust Emissions
journal, November 2013
- Ratcliff, Matthew A.; Luecke, Jon; Williams, Aaron
- Environmental Science & Technology, Vol. 47, Issue 23
Determining the Ce2O2S–CeOx phase boundary for conditions relevant to adsorption and catalysis
journal, July 2003
- Ferrizz, R. M.; Gorte, R. J.; Vohs, J. M.
- Applied Catalysis B: Environmental, Vol. 43, Issue 3
Oxidation Mechanism of Aliphatic Ethers: Theoretical Insights on the Main Reaction Channels
journal, August 2012
- Di Tommaso, Stefania; Rotureau, Patricia; Adamo, Carlo
- The Journal of Physical Chemistry A, Vol. 116, Issue 36
Reductive catalytic fractionation: state of the art of the lignin-first biorefinery
journal, April 2019
- Renders, Tom; Van den Bossche, Gil; Vangeel, Thijs
- Current Opinion in Biotechnology, Vol. 56
Heat of Vaporization Measurements for Ethanol Blends Up To 50 Volume Percent in Several Hydrocarbon Blendstocks and Implications for Knock in SI Engines
journal, April 2015
- Chupka, Gina M.; Christensen, Earl; Fouts, Lisa
- SAE International Journal of Fuels and Lubricants, Vol. 8, Issue 2
Measurement of Heat of Vaporization for Research Gasolines and Ethanol Blends by DSC/TGA
journal, November 2018
- Fioroni, Gina M.; Fouts, Lisa; Christensen, Earl
- Energy & Fuels, Vol. 32, Issue 12
Selection Criteria and Screening of Potential Biomass-Derived Streams as Fuel Blendstocks for Advanced Spark-Ignition Engines
journal, March 2017
- McCormick, Robert L.; Fioroni, Gina; Fouts, Lisa
- SAE International Journal of Fuels and Lubricants, Vol. 10, Issue 2
Characteristics of Isohexene as a Novel Promising High-Octane Gasoline Booster
journal, June 2020
- Ershov, Mikhail A.; Abdellatief, Tamer M. M.; Potanin, Dmitriy A.
- Energy & Fuels, Vol. 34, Issue 7
Catalytic Conversion of Nonfood Woody Biomass Solids to Organic Liquids
journal, April 2014
- Barta, Katalin; Ford, Peter C.
- Accounts of Chemical Research, Vol. 47, Issue 5, p. 1503-1512
Rapid prediction of fuel research octane number and octane sensitivity using the AFIDA constant-volume combustion chamber
journal, October 2021
- Luecke, Jon; Zigler, Bradley T.
- Fuel, Vol. 301
Activity and structure-sensitivity of the water-gas shift reaction over CuZnAl mixed oxide catalysts
journal, October 1995
- Ginés, M. J. L.; Amadeo, N.; Laborde, M.
- Applied Catalysis A: General, Vol. 131, Issue 2
Kinetic Studies of Lignin Solvolysis and Reduction by Reductive Catalytic Fractionation Decoupled in Flow-Through Reactors
journal, April 2018
- Anderson, Eric M.; Stone, Michael L.; Hülsey, Max J.
- ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 6
Unraveling the Dynamic Nature of a CuO/CeO 2 Catalyst for CO Oxidation in Operando : A Combined Study of XANES (Fluorescence) and DRIFTS
journal, April 2014
- Yao, Siyu; Mudiyanselage, Kumudu; Xu, Wenqian
- ACS Catalysis, Vol. 4, Issue 6
Aqueous-phase hydrodeoxygenation of sorbitol with Pt/SiO2–Al2O3: Identification of reaction intermediates
journal, March 2010
- Li, Ning; Huber, George W.
- Journal of Catalysis, Vol. 270, Issue 1
One-Pot Catalytic Conversion of Cellulose and of Woody Biomass Solids to Liquid Fuels
journal, September 2011
- Matson, Theodore D.; Barta, Katalin; Iretskii, Alexei V.
- Journal of the American Chemical Society, Vol. 133, Issue 35, p. 14090-14097
Supercritical methanol depolymerization and hydrodeoxygenation of lignin and biomass over reduced copper porous metal oxides
journal, January 2019
- McClelland, Daniel J.; Galebach, Peter H.; Motagamwala, Ali Hussain
- Green Chemistry, Vol. 21, Issue 11
Oxidative Methanol Reforming Reactions on CuZnAl Catalysts Derived from Hydrotalcite-like Precursors
journal, March 2001
- Murcia-Mascarós, S.; Navarro, R. M.; Gómez-Sainero, L.
- Journal of Catalysis, Vol. 198, Issue 2
Catalytic Conversion of Pyrolysis Oil to Alcohols and Alkanes in Supercritical Methanol over the CuMgAlO x Catalyst
journal, January 2021
- Galebach, Peter H.; Beussman, Micaela; Johnson, Jillian
- ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 5
Deactivation of supported copper metal catalysts for hydrogenation reactions
journal, April 2001
- Twigg, Martyn V.; Spencer, Michael S.
- Applied Catalysis A: General, Vol. 212, Issue 1-2, p. 161-174
New Synthesis Method of Ethanol from Dimethyl Ether with a Synergic Effect between the Zeolite Catalyst and Metallic Catalyst
journal, May 2009
- San, Xiaoguang; Zhang, Yi; Shen, Wenjie
- Energy & Fuels, Vol. 23, Issue 5
Complete lignocellulose conversion with integrated catalyst recycling yielding valuable aromatics and fuels
journal, January 2018
- Sun, Zhuohua; Bottari, Giovanni; Afanasenko, Anastasiia
- Nature Catalysis, Vol. 1, Issue 1
Supercritical Methanol Depolymerization and Hydrodeoxygenation of Maple Wood and Biomass-Derived Oxygenates into Renewable Alcohols in a Continuous Flow Reactor
journal, August 2019
- Galebach, Peter H.; Soeherman, Jimmy K.; Wittrig, Ashley M.
- ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 18
Comparative study of biodiesel oxidation stability using Rancimat, PetroOXY, and low P-DSC
journal, March 2014
- Murta Valle, M. L.; Leonardo, R. S.; Dweck, J.
- Journal of Thermal Analysis and Calorimetry, Vol. 116, Issue 1
Hydrogenolysis of cellulose to C4–C7 alcohols over bi-functional CuO–MO/Al2O3 (M=Ce, Mg, Mn, Ni, Zn) catalysts coupled with methanol reforming reaction
journal, June 2013
- Wu, Yanhua; Gu, Fangna; Xu, Guangwen
- Bioresource Technology, Vol. 137