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 »
- Authors:
-
- Joint BioEnergy Institute, Lawrence Berkeley National Laboratory, Berkeley, USA
- Total Raffinage Chimie, 92400 Courbevoie, France
- Joint BioEnergy Institute, Lawrence Berkeley National Laboratory, Berkeley, USA, Biological and Engineering Sciences Center
- Hawaii Natural Energy Institute, University of Hawaii at Manoa, Honolulu, USA
- Total New Energies Inc., Emeryville, USA
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1459223
- Alternate Identifier(s):
- OSTI ID: 1506292
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Green Chemistry
- Additional Journal Information:
- Journal Name: Green Chemistry Journal Volume: 20 Journal Issue: 15; 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; 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 Kingdom: 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 Kingdom. https://doi.org/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. Mon .
"Elucidating transfer hydrogenation mechanisms in non-catalytic lignin depolymerization". United Kingdom. https://doi.org/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},
number = 15,
volume = 20,
place = {United Kingdom},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}
https://doi.org/10.1039/C7GC03239K
Web of Science
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