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Title: Elucidating transfer hydrogenation mechanisms in non-catalytic lignin depolymerization

Abstract

Lignin undergoes catalytic depolymerization in the presence of a variety of transfer hydrogenation agents, however the mechanisms for non-catalytic depolymerization of lignin via transfer hydrogenation are not well understood; this makes process optimization difficult. Herein, for the first time a mechanism for this process is proposed. For the purposes of understanding the mechanisms involved in these non-catalytic lignin depolymerization processes, this study investigates the equilibrium system of formic acid, methyl formate and carbon monoxide, as agents for the depolymerization of lignin, in the presence of either water or methanol as solvents. In the methyl formate/water (at 300 °C) system, 73 wt%25 oil was produced which contained a significant amount of low molecular weight alkylphenols, with less than 1 wt%25 char produced. In aqueous media, the results showed that methyl formate maintains an equilibrium with formic acid which is itself in equilibrium with carbon monoxide. It was found that using either formic acid or methyl formate for non-catalytic transfer hydrogenation of lignin can produce high amounts of oil, and can be described as a two-stage mechanism. After 10 min of reaction at 300 °C, around a quarter of the formic acid is consumed via hydride transfer of the formate proton, preventingmore » the condensation of lignin fragments. At the same time, approximately three quarters of the formic acid decomposes to carbon dioxide and carbon monoxide. Once the formic acid is consumed, the carbon monoxide was identified as the precursor to a reactive reductive reagent and was able to activate the proton of the water molecule preventing further condensation of the lignin fragments. It has been previously thought that transfer hydrogenation in lignin using formic acid occurs via the production of molecular hydrogen. Here it is demonstrated that formic acid reacts directly with the lignin, without this hydrogen formation. Therefore the key parameters for efficient transfer hydrogenation of the lignin to maximize bio-oil yield appear to involve controlling the reactions between lignin and formic acid, methyl formate or carbon monoxide under aqueous conditions, thereby reducing the reagent cost and loading while maintaining efficient lignin conversion.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [2];  [4];  [5];  [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [3]
  1. Joint BioEnergy Institute; Lawrence Berkeley National Laboratory; Berkeley; USA
  2. Total Raffinage Chimie; 92400 Courbevoie; France
  3. Joint BioEnergy Institute; Lawrence Berkeley National Laboratory; Berkeley; USA; Biological and Engineering Sciences Center
  4. Hawaii Natural Energy Institute; University of Hawaii at Manoa; Honolulu; USA
  5. Total New Energies Inc.; Emeryville; USA
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1459223
Alternate Identifier(s):
OSTI ID: 1506292
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Published Article
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 20; 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; 59 BASIC BIOLOGICAL SCIENCES

Citation Formats

Bouxin, Florent P., Strub, Henri, Dutta, Tanmoy, Aguilhon, Julie, Morgan, Trevor J., Mingardon, Florence, Konda, Murthy, Singh, Seema, Simmons, Blake, and George, Anthe. Elucidating transfer hydrogenation mechanisms in non-catalytic lignin depolymerization. United States: N. p., 2018. Web. doi:10.1039/c7gc03239k.
Bouxin, Florent P., Strub, Henri, Dutta, Tanmoy, Aguilhon, Julie, Morgan, Trevor J., Mingardon, Florence, Konda, Murthy, Singh, Seema, Simmons, Blake, & George, Anthe. Elucidating transfer hydrogenation mechanisms in non-catalytic lignin depolymerization. United States. doi:10.1039/c7gc03239k.
Bouxin, Florent P., Strub, Henri, Dutta, Tanmoy, Aguilhon, Julie, Morgan, Trevor J., Mingardon, Florence, Konda, Murthy, Singh, Seema, Simmons, Blake, and George, Anthe. Fri . "Elucidating transfer hydrogenation mechanisms in non-catalytic lignin depolymerization". United States. doi:10.1039/c7gc03239k.
@article{osti_1459223,
title = {Elucidating transfer hydrogenation mechanisms in non-catalytic lignin depolymerization},
author = {Bouxin, Florent P. and Strub, Henri and Dutta, Tanmoy and Aguilhon, Julie and Morgan, Trevor J. and Mingardon, Florence and Konda, Murthy and Singh, Seema and Simmons, Blake and George, Anthe},
abstractNote = {Lignin undergoes catalytic depolymerization in the presence of a variety of transfer hydrogenation agents, however the mechanisms for non-catalytic depolymerization of lignin via transfer hydrogenation are not well understood; this makes process optimization difficult. Herein, for the first time a mechanism for this process is proposed. For the purposes of understanding the mechanisms involved in these non-catalytic lignin depolymerization processes, this study investigates the equilibrium system of formic acid, methyl formate and carbon monoxide, as agents for the depolymerization of lignin, in the presence of either water or methanol as solvents. In the methyl formate/water (at 300 °C) system, 73 wt%25 oil was produced which contained a significant amount of low molecular weight alkylphenols, with less than 1 wt%25 char produced. In aqueous media, the results showed that methyl formate maintains an equilibrium with formic acid which is itself in equilibrium with carbon monoxide. It was found that using either formic acid or methyl formate for non-catalytic transfer hydrogenation of lignin can produce high amounts of oil, and can be described as a two-stage mechanism. After 10 min of reaction at 300 °C, around a quarter of the formic acid is consumed via hydride transfer of the formate proton, preventing the condensation of lignin fragments. At the same time, approximately three quarters of the formic acid decomposes to carbon dioxide and carbon monoxide. Once the formic acid is consumed, the carbon monoxide was identified as the precursor to a reactive reductive reagent and was able to activate the proton of the water molecule preventing further condensation of the lignin fragments. It has been previously thought that transfer hydrogenation in lignin using formic acid occurs via the production of molecular hydrogen. Here it is demonstrated that formic acid reacts directly with the lignin, without this hydrogen formation. Therefore the key parameters for efficient transfer hydrogenation of the lignin to maximize bio-oil yield appear to involve controlling the reactions between lignin and formic acid, methyl formate or carbon monoxide under aqueous conditions, thereby reducing the reagent cost and loading while maintaining efficient lignin conversion.},
doi = {10.1039/c7gc03239k},
journal = {Green Chemistry},
issn = {1463-9262},
number = 15,
volume = 20,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/c7gc03239k

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Works referenced in this record:

Optimizing solvolysis conditions for integrated depolymerisation and hydrodeoxygenation of lignin to produce liquid biofuel
journal, May 2009

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The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
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Solution-state 2D NMR of Ball-milled Plant Cell Wall Gels in DMSO-d 6
journal, March 2008