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Title: Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

Abstract

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. We demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents.

Authors:
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Publication Date:
DOE Contract Number:  
AC05-00OR22725
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
Subject:
biorefining; catalytic; fractionation; lignin; lignocellulose; reductive; valorization
OSTI Identifier:
3012881
DOI:
https://doi.org/10.25983/CBI/3012881

Citation Formats

Webber, Matthew S., Myers, Allen Puente-UrbinaLogan C., Woodworth, Sean P., Pellerin, Emma J., Jang, Jun Hee, Bussard, Jeremy R., Metzger, Arlo, Donohoe, Bryon S., Stone, Michael L., Brandner, David G., Beckham, Gregg T., and Román-Leshkov, Yuriy. Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation. United States: N. p., 2026. Web. doi:10.25983/CBI/3012881.
Webber, Matthew S., Myers, Allen Puente-UrbinaLogan C., Woodworth, Sean P., Pellerin, Emma J., Jang, Jun Hee, Bussard, Jeremy R., Metzger, Arlo, Donohoe, Bryon S., Stone, Michael L., Brandner, David G., Beckham, Gregg T., & Román-Leshkov, Yuriy. Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation. United States. doi:https://doi.org/10.25983/CBI/3012881
Webber, Matthew S., Myers, Allen Puente-UrbinaLogan C., Woodworth, Sean P., Pellerin, Emma J., Jang, Jun Hee, Bussard, Jeremy R., Metzger, Arlo, Donohoe, Bryon S., Stone, Michael L., Brandner, David G., Beckham, Gregg T., and Román-Leshkov, Yuriy. 2026. "Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation". United States. doi:https://doi.org/10.25983/CBI/3012881. https://www.osti.gov/servlets/purl/3012881. Pub date:Tue Jan 13 00:00:00 UTC 2026
@article{osti_3012881,
title = {Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation},
author = {Webber, Matthew S. and Myers, Allen Puente-UrbinaLogan C. and Woodworth, Sean P. and Pellerin, Emma J. and Jang, Jun Hee and Bussard, Jeremy R. and Metzger, Arlo and Donohoe, Bryon S. and Stone, Michael L. and Brandner, David G. and Beckham, Gregg T. and Román-Leshkov, Yuriy},
abstractNote = {Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. We demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents.},
doi = {10.25983/CBI/3012881},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Jan 13 00:00:00 UTC 2026},
month = {Tue Jan 13 00:00:00 UTC 2026}
}