Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock

Hannah Nguyen; Nabila A. Huq; Daniela Stück; Stephen M. Tifft; Davis R. Conklin; Andrew J. Koehler; William Wilson McNeary; Gina M. Fioroni; Cameron Hays; Earl D. Christensen; Ian McNamara; Andrew Bartling; Ryan Davis; Kinga A. Unocic; Derek R. Vardon

doi:10.1002/adsu.202100310

Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock

Hannah Nguyen, Nabila A. Huq, Daniela Stück, Stephen M. Tifft, Davis R. Conklin, Andrew J. Koehler, William Wilson McNeary, Gina M. Fioroni, Cameron Hays, Earl D. Christensen, Ian McNamara, Andrew Bartling, Ryan Davis, Kinga A. Unocic, Derek R. Vardon

Materials MicroAnalysis

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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 C₂-C₇ 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.

Original language	English
Article number	2100310
Journal	Advanced Sustainable Systems
Volume	6
Issue number	4
DOIs	https://doi.org/10.1002/adsu.202100310
State	Published - Apr 2022

Funding

A portion of this research was conducted as part of the Chemical Catalysis for Bioenergy Consortium sponsored by BETO through Contract No. DE‐AC36‐08GO28308 at NREL, as well the Co‐Optimization of Fuels & Engines (Co‐Optima) project sponsored by the U.S. Department of Energy—Office of Energy Efficiency and Renewable Energy, BETO, and Vehicle Technologies Offices at NREL through Contract No. DE347AC36‐99GO10337. Microscopy was performed in collaboration with the Chemical Catalysis for Bioenergy Consortium under Contract No. DE‐AC05‐00OR22725 with Oak Ridge National Laboratory (ORNL) and through a user project supported by ORNL's Center for Nanophase Materials Sciences (CNMS), which is sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Part of the microscopy research was also supported by the Office of Nuclear Energy, Fuel Cycle R&D Program, and the Nuclear Science User Facilities. The views expressed in the article do not necessarily represent the views of the U.S. Department of Energy or the U.S. Government. The U.S. Government retains, and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid‐up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. A portion of this research was conducted as part of the Chemical Catalysis for Bioenergy Consortium sponsored by BETO through Contract No. DE-AC36-08GO28308 at NREL, as well the Co-Optimization of Fuels & Engines (Co-Optima) project sponsored by the U.S. Department of Energy?Office of Energy Efficiency and Renewable Energy, BETO, and Vehicle Technologies Offices at NREL through Contract No. DE347AC36-99GO10337. Microscopy was performed in collaboration with the Chemical Catalysis for Bioenergy Consortium under Contract No. DE-AC05-00OR22725 with Oak Ridge National Laboratory (ORNL) and through a user project supported by ORNL's Center for Nanophase Materials Sciences (CNMS), which is sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Part of the microscopy research was also supported by the Office of Nuclear Energy, Fuel Cycle R&D Program, and the Nuclear Science User Facilities. The views expressed in the article do not necessarily represent the views of the U.S. Department of Energy or the U.S. Government. The U.S. Government retains, and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes.

Keywords

bioblendstocks
catalysis
gasoline
light duty
solvolysis
woody biomass

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Nguyen, H., Huq, N. A., Stück, D., Tifft, S. M., Conklin, D. R., Koehler, A. J., McNeary, W. W., Fioroni, G. M., Hays, C., Christensen, E. D., McNamara, I., Bartling, A., Davis, R., Unocic, K. A., & Vardon, D. R. (2022). Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock. Advanced Sustainable Systems, 6(4), Article 2100310. https://doi.org/10.1002/adsu.202100310

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title = "Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock",

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”AlOx catalysts (M = Mg, Zr, and Ce) are examined for upgrading delignified hybrid poplar via SCM-DHDO. CuCeAlOx displays the highest activity, increasing the C2-C7 alcohol production rate and selectivity by twofold in batch reactions, and >50% in semicontinuous reactions relative to the current state-of-the-art CuMgAlOx. The performance of CuCeAlOx 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.",

keywords = "bioblendstocks, catalysis, gasoline, light duty, solvolysis, woody biomass",

author = "Hannah Nguyen and Huq, {Nabila A.} and Daniela St{\"u}ck and Tifft, {Stephen M.} and Conklin, {Davis R.} and Koehler, {Andrew J.} and McNeary, {William Wilson} and Fioroni, {Gina M.} and Cameron Hays and Christensen, {Earl D.} and Ian McNamara and Andrew Bartling and Ryan Davis and Unocic, {Kinga A.} and Vardon, {Derek R.}",

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year = "2022",

month = apr,

doi = "10.1002/adsu.202100310",

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Nguyen, H, Huq, NA, Stück, D, Tifft, SM, Conklin, DR, Koehler, AJ, McNeary, WW, Fioroni, GM, Hays, C, Christensen, ED, McNamara, I, Bartling, A, Davis, R, Unocic, KA & Vardon, DR 2022, 'Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock', Advanced Sustainable Systems, vol. 6, no. 4, 2100310. https://doi.org/10.1002/adsu.202100310

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T1 - Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock

AU - Nguyen, Hannah

AU - Huq, Nabila A.

AU - Stück, Daniela

AU - Tifft, Stephen M.

AU - Conklin, Davis R.

AU - Koehler, Andrew J.

AU - McNeary, William Wilson

AU - Fioroni, Gina M.

AU - Hays, Cameron

AU - Christensen, Earl D.

AU - McNamara, Ian

AU - Bartling, Andrew

AU - Davis, Ryan

AU - Unocic, Kinga A.

AU - Vardon, Derek R.

PY - 2022/4

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N2 - 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”AlOx catalysts (M = Mg, Zr, and Ce) are examined for upgrading delignified hybrid poplar via SCM-DHDO. CuCeAlOx displays the highest activity, increasing the C2-C7 alcohol production rate and selectivity by twofold in batch reactions, and >50% in semicontinuous reactions relative to the current state-of-the-art CuMgAlOx. The performance of CuCeAlOx 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.

AB - 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”AlOx catalysts (M = Mg, Zr, and Ce) are examined for upgrading delignified hybrid poplar via SCM-DHDO. CuCeAlOx displays the highest activity, increasing the C2-C7 alcohol production rate and selectivity by twofold in batch reactions, and >50% in semicontinuous reactions relative to the current state-of-the-art CuMgAlOx. The performance of CuCeAlOx 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.

KW - bioblendstocks

KW - catalysis

KW - gasoline

KW - light duty

KW - solvolysis

KW - woody biomass

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VL - 6

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ER -

Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock

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