Lignin Extraction and Condensation as a Function of Temperature, Residence Time, and Solvent System in Flow-through Reactors

Brandner, David G.; Gracia Vitoria, Jaime; Kenny, Jacob K.; Bussard, Jeremy R.; Jang, Jun Hee; Woodworth, Sean P.; Vanbroekhoven, Karolien; Román-Leshkov, Yuriy; Beckham, Gregg T.

doi:10.1021/acssuschemeng.5c04198

Lignin Extraction and Condensation as a Function of Temperature, Residence Time, and Solvent System in Flow-through Reactors

Journal Article · Fri Aug 01 00:00:00 EDT 2025 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.5c04198· OSTI ID:2583635

^[1]; Gracia Vitoria, Jaime ^[2]; Kenny, Jacob K. ^[1]; ^[1]; ^[1]; ^[1]; Vanbroekhoven, Karolien ^[2]; ^[3]; ^[1]

National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Flemish Institute for Technological Research (Vito N.V.), Mol (Belgium)
Massachusetts Institute of Technology, Cambridge, MA (United States)

Solvolytic extraction of lignin from biomass is a critical step in lignin-first biorefining, including the reductive catalytic fractionation (RCF) process. Key to optimal RCF processing is the ability to rapidly extract lignin from biomass at high delignification extents and transfer the lignin molecules to a catalyst surface in a time frame that minimizes lignin condensation reactions. Here, we use a flow-through reactor to study the effects of temperature (175-250 °C), residence time (9 to 36 min), and solvent composition (methanol and methanol-water) on lignin extraction and condensation. We evaluated three metrics at each condition: total delignification, delignification rate, and extent of condensation, the latter measured by a decrease in monomer yield for batch hydrogenolysis reactions of solvolysis liquor compared to batch RCF reactions. We observe that delignification is predominantly determined by temperature, while residence time dictates the lignin condensation extent. Moreover, the extent of both extraction and condensation increased in the methanol-water solvent system compared to that in the methanol system. Lignin extracted in methanol is stable up to 18-min residence times at or below 225 °C, while a majority of the lignin extracted in methanol-water is condensed with a 9-min residence time at 200 °C. These results can inform reactor designs and solvent selection for lignin-first biorefining processes that aim to physically separate the biomass and catalyst.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 2583635

Report Number(s):: NREL/JA--2A00-94719

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 31 Vol. 13; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (56)

Mild and Robust Redox-Neutral Pd/C-Catalyzed Lignol β-O-4′ Bond Cleavage Through a Low-Energy-Barrier Pathway Galkin, Maxim V.; Dahlstrand, Christian; Samec, Joseph S. M. ChemSusChem, Vol. 8, Issue 13 https://doi.org/10.1002/cssc.201500117	journal	April 2015
Lignin Valorization through Catalytic Lignocellulose Fractionation: A Fundamental Platform for the Future Biorefinery Galkin, Maxim V.; Samec, Joseph S. M. ChemSusChem, Vol. 9, Issue 13 https://doi.org/10.1002/cssc.201600237	journal	June 2016
Mesoscale Reaction–Diffusion Phenomena Governing Lignin‐First Biomass Fractionation Thornburg, Nicholas E.; Pecha, M. Brennan; Brandner, David G. ChemSusChem, Vol. 13, Issue 17 https://doi.org/10.1002/cssc.202000558	journal	May 2020
Downstream Processing Strategies for Lignin‐First Biorefinery Sun, Zhuohua; Cheng, Jinling; Wang, Dingsheng ChemSusChem, Vol. 13, Issue 19 https://doi.org/10.1002/cssc.202001085	journal	August 2020
β‐Zeolite‐Assisted Lignin‐First Fractionation in a Flow‐Through Reactor** Kramarenko, Alexei; Etit, Deniz; Laudadio, Gabriele ChemSusChem, Vol. 14, Issue 18 https://doi.org/10.1002/cssc.202101157	journal	August 2021
Lignin Stabilization and Carbohydrate Nature in H‐transfer Reductive Catalytic Fractionation: The Role of Solvent Fractionation of Lignin Oil in Structural Profiling** Rinken, Raul; Posthuma, Dean; Rinaldi, Roberto ChemSusChem, Vol. 16, Issue 3 https://doi.org/10.1002/cssc.202201875	journal	December 2022
2‐step lignin‐first catalytic fractionation with bifunctional Pd/ß‐zeolite catalyst in a flow‐through reactor Kramarenko, A.; Uslu, A.; Etit, D. ChemSusChem, Vol. 17, Issue 8 https://doi.org/10.1002/cssc.202301404	journal	January 2024
Reactivity of lignin in supercritical methanol studied with various lignin model compounds Tsujino, J.; Kawamoto, H.; Saka, S. Wood Science and Technology, Vol. 37, Issue 3-4 https://doi.org/10.1007/s00226-003-0187-3	journal	December 2003
Reductive catalytic fractionation: state of the art of the lignin-first biorefinery Renders, Tom; Van den Bossche, Gil; Vangeel, Thijs Current Opinion in Biotechnology, Vol. 56 https://doi.org/10.1016/j.copbio.2018.12.005	journal	April 2019
Lignin structure and its engineering Ralph, John; Lapierre, Catherine; Boerjan, Wout Current Opinion in Biotechnology, Vol. 56 https://doi.org/10.1016/j.copbio.2019.02.019	journal	April 2019
Flowthrough Reductive Catalytic Fractionation of Biomass Anderson, Eric M.; Stone, Michael L.; Katahira, Rui Joule, Vol. 1, Issue 3 https://doi.org/10.1016/j.joule.2017.10.004	journal	November 2017
Multi-pass flow-through reductive catalytic fractionation Jang, Jun Hee; Brandner, David G.; Dreiling, Reagan J. Joule, Vol. 6, Issue 8 https://doi.org/10.1016/j.joule.2022.06.016	journal	August 2022
Lignin condensation, an unsolved mystery Gong, Zhenggang; Shuai, Li Trends in Chemistry, Vol. 5, Issue 3 https://doi.org/10.1016/j.trechm.2022.12.005	journal	March 2023
Bright Side of Lignin Depolymerization: Toward New Platform Chemicals Sun, Zhuohua; Fridrich, Bálint; de Santi, Alessandra Chemical Reviews, Vol. 118, Issue 2 https://doi.org/10.1021/acs.chemrev.7b00588	journal	January 2018
Perspective on Overcoming Scale-Up Hurdles for the Reductive Catalytic Fractionation of Lignocellulose Biomass Cooreman, Elias; Vangeel, Thijs; Van Aelst, Korneel Industrial & Engineering Chemistry Research, Vol. 59, Issue 39 https://doi.org/10.1021/acs.iecr.0c02294	journal	July 2020
Hydrothermal Decomposition of a Lignin Dimer under Neutral and Basic Conditions: A Mechanism Study Nagel, Eric; Zhang, Cheng Industrial & Engineering Chemistry Research, Vol. 58, Issue 40 https://doi.org/10.1021/acs.iecr.9b00400	journal	September 2019
Ru-Catalyzed Hydrogenolysis of Lignin: Base-Dependent Tunability of Monomeric Phenols and Mechanistic Study Li, Helong; Song, Guoyong ACS Catalysis, Vol. 9, Issue 5 https://doi.org/10.1021/acscatal.9b00556	journal	March 2019
Two-Step Fractionation of a Model Technical Lignin by Combined Organic Solvent Extraction and Membrane Ultrafiltration Allegretti, Chiara; Fontanay, Simon; Rischka, Klaus ACS Omega, Vol. 4, Issue 3 https://doi.org/10.1021/acsomega.8b02851	journal	March 2019
Reducing Solvent Consumption in Reductive Catalytic Fractionation through Lignin Oil Recycling Jang, Jun Hee; Callejón Álvarez, Júlia; Neuendorf, Quinn S. ACS Sustainable Chemistry & Engineering, Vol. 12, Issue 34 https://doi.org/10.1021/acssuschemeng.4c04089	journal	August 2024
Synergetic Effects of Alcohol/Water Mixing on the Catalytic Reductive Fractionation of Poplar Wood Renders, Tom; Van den Bosch, Sander; Vangeel, Thijs ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 12 https://doi.org/10.1021/acssuschemeng.6b01844	journal	October 2016
Kinetic Studies of Lignin Solvolysis and Reduction by Reductive Catalytic Fractionation Decoupled in Flow-Through Reactors Anderson, Eric M.; Stone, Michael L.; Hülsey, Max J. ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 6 https://doi.org/10.1021/acssuschemeng.8b01256	journal	April 2018
Mild Organosolv Lignin Extraction with Alcohols: The Importance of Benzylic Alkoxylation Zijlstra, Douwe S.; Lahive, Ciaran W.; Analbers, Coen A. ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 13 https://doi.org/10.1021/acssuschemeng.9b07222	journal	March 2020
The Effect of Flow Rate of Compressed Hot Water on Xylan, Lignin, and Total Mass Removal from Corn Stover Liu, Chaogang; Wyman, Charles E. Industrial & Engineering Chemistry Research, Vol. 42, Issue 21, p. 5409-5416 https://doi.org/10.1021/ie030458k	journal	September 2003
Synergy of Single Atoms and Lewis Acid Sites for Efficient and Selective Lignin Disassembly into Monolignol Derivatives Meng, Ge; Lan, Wu; Zhang, Lilong Journal of the American Chemical Society, Vol. 145, Issue 23 https://doi.org/10.1021/jacs.3c04028	journal	May 2023
Aromatic Monomers by in Situ Conversion of Reactive Intermediates in the Acid-Catalyzed Depolymerization of Lignin Deuss, Peter J.; Scott, Martin; Tran, Fanny Journal of the American Chemical Society, Vol. 137, Issue 23 https://doi.org/10.1021/jacs.5b03693	journal	June 2015
A Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization in Acidic Environments Sturgeon, Matthew R.; Kim, Seonah; Lawrence, Kelsey ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 3, p. 472-485 https://doi.org/10.1021/sc400384w	journal	November 2013
Whole plant cell wall characterization using solution-state 2D NMR Mansfield, Shawn D.; Kim, Hoon; Lu, Fachuang Nature Protocols, Vol. 7, Issue 9 https://doi.org/10.1038/nprot.2012.064	journal	August 2012
Differences in S/G ratio in natural poplar variants do not predict catalytic depolymerization monomer yields Anderson, Eric M.; Stone, Michael L.; Katahira, Rui Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09986-1	journal	May 2019
Rational highly dispersed ruthenium for reductive catalytic fractionation of lignocellulose Liu, Zhenzhen; Li, Helong; Gao, Xueying Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-32451-5	journal	August 2022
Stabilization strategies in biomass depolymerization using chemical functionalization Questell-Santiago, Ydna M.; Galkin, Maxim V.; Barta, Katalin Nature Reviews Chemistry, Vol. 4, Issue 6 https://doi.org/10.1038/s41570-020-0187-y	journal	May 2020
Fractionation of ‘water-soluble lignocellulose’ into C ₅ /C ₆ sugars and sulfur-free lignins Käldström, Mats; Meine, Niklas; Farès, Christophe Green Chem., Vol. 16, Issue 5 https://doi.org/10.1039/C4GC00168K	journal	January 2014
Influence of bio-based solvents on the catalytic reductive fractionation of birch wood Schutyser, W.; Van den Bosch, S.; Renders, T. Green Chemistry, Vol. 17, Issue 11 https://doi.org/10.1039/C5GC01442E	journal	January 2015
Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading Schutyser, W.; Renders, T.; Van den Bosch, S. Chemical Society Reviews, Vol. 47, Issue 3 https://doi.org/10.1039/C7CS00566K	journal	January 2018
Lignin-first biomass fractionation: the advent of active stabilisation strategies Renders, T.; Van den Bosch, S.; Koelewijn, S. -F. Energy & Environmental Science, Vol. 10, Issue 7 https://doi.org/10.1039/C7EE01298E	journal	January 2017
Integrating lignin valorization and bio-ethanol production: on the role of Ni-Al ₂ O ₃ catalyst pellets during lignin-first fractionation Van den Bosch, S.; Renders, T.; Kennis, S. Green Chemistry, Vol. 19, Issue 14 https://doi.org/10.1039/C7GC01324H	journal	January 2017
Towards high-yield lignin monomer production Shuai, Li; Saha, Basudeb Green Chemistry, Vol. 19, Issue 16 https://doi.org/10.1039/C7GC01676J	journal	January 2017
Lignin depolymerization to monophenolic compounds in a flow-through system Kumaniaev, Ivan; Subbotina, Elena; Sävmarker, Jonas Green Chemistry, Vol. 19, Issue 24 https://doi.org/10.1039/C7GC02731A	journal	January 2017
Catalytic lignocellulose biorefining in n -butanol/water: a one-pot approach toward phenolics, polyols, and cellulose Renders, T.; Cooreman, E.; Van den Bosch, S. Green Chemistry, Vol. 20, Issue 20 https://doi.org/10.1039/C8GC01031E	journal	January 2018
Downstream processing of lignin derived feedstock into end products Wong, Sie Shing; Shu, Riyang; Zhang, Jiaguang Chemical Society Reviews, Vol. 49, Issue 15 https://doi.org/10.1039/D0CS00134A	journal	January 2020
Guidelines for performing lignin-first biorefining Abu-Omar, Mahdi M.; Barta, Katalin; Beckham, Gregg T. Energy & Environmental Science, Vol. 14, Issue 1 https://doi.org/10.1039/D0EE02870C	journal	January 2021
Reductive catalytic fractionation of lignocellulose: when should the catalyst meet depolymerized lignin fragments? Qiu, Shi; Wang, Meng; Fang, Yunming Sustainable Energy & Fuels, Vol. 4, Issue 11 https://doi.org/10.1039/D0SE01118E	journal	January 2020
Techno-economic analysis and life cycle assessment of a biorefinery utilizing reductive catalytic fractionation Bartling, Andrew; Stone, Michael L.; Hanes, Rebecca J. Energy & Environmental Science https://doi.org/10.1039/D1EE01642C	journal	January 2021
Flow-through solvolysis enables production of native-like lignin from biomass Brandner, David G.; Kruger, Jacob S.; Thornburg, Nicholas E. Green Chemistry, Vol. 23, Issue 15 https://doi.org/10.1039/D1GC01591E	journal	January 2021
Feedstock-agnostic reductive catalytic fractionation in alcohol and alcohol–water mixtures Jang, Jun Hee; Morais, Ana Rita C.; Browning, Megan Green Chemistry, Vol. 25, Issue 9 https://doi.org/10.1039/D2GC04464A	journal	January 2023
Catalyst choice impacts aromatic monomer yields and selectivity in hydrogen-free reductive catalytic fractionation Kenny, Jacob K.; Brandner, David G.; Neefe, Sasha R. Reaction Chemistry & Engineering, Vol. 7, Issue 12 https://doi.org/10.1039/D2RE00275B	journal	January 2022
Stepping away from purified solvents in reductive catalytic fractionation: a step forward towards a disruptive wood biorefinery process Arts, W.; Van Aelst, K.; Cooreman, E. Energy & Environmental Science, Vol. 16, Issue 6 https://doi.org/10.1039/D3EE00965C	journal	January 2023
Kinetic and mechanistic insights into hydrogenolysis of lignin to monomers in a continuous flow reactor Li, Yanding; Demir, Benginur; Vázquez Ramos, Leida M. Green Chemistry, Vol. 21, Issue 13 https://doi.org/10.1039/c9gc00986h	journal	January 2019
Condensation Reactions of Softwood and Hardwood Lignin Model Compounds Under Organic Acid Cooking Conditions Shimada, K.; Hosoya, S.; Ikeda, T. Journal of Wood Chemistry and Technology, Vol. 17, Issue 1-2 https://doi.org/10.1080/02773819708003118	journal	February 1997
An “ideal lignin” facilitates full biomass utilization Li, Yanding; Shuai, Li; Kim, Hoon Science Advances, Vol. 4, Issue 9 https://doi.org/10.1126/sciadv.aau2968	journal	September 2018
Lignin Valorization: Improving Lignin Processing in the Biorefinery Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J. Science, Vol. 344, Issue 6185, p. 1246843-1246843 https://doi.org/10.1126/science.1246843	journal	May 2014
Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization Shuai, Li; Amiri, Masoud Talebi; Questell-Santiago, Ydna M. Science, Vol. 354, Issue 6310 https://doi.org/10.1126/science.aaf7810	journal	October 2016
Chemical Structures of Sulfuric Acid Lignin - Pt.X.Reaction of Syringylglycerol-ß-syringyl Ether and Condensation of Syringyl Nucleus with Guaiacyl Lignin Model Compounds in Sulfuric Acid Yasuda, Seiichi; Ota, Katsuhito Holzforschung, Vol. 41, Issue 1 https://doi.org/10.1515/hfsg.1987.41.1.59	journal	January 1987
Highly Efficient Semi-Continuous Extraction and In-Line Purification of High β-O-4 Butanosolv Lignin Zijlstra, Douwe Sjirk; de Korte, Joren; de Vries, Ernst P. C. Frontiers in Chemistry, Vol. 9 https://doi.org/10.3389/fchem.2021.655983	journal	May 2021
Recent Efforts to Prevent Undesirable Reactions From Fractionation to Depolymerization of Lignin: Toward Maximizing the Value From Lignin Kim, Kwang Ho; Kim, Chang Soo Frontiers in Energy Research, Vol. 6 https://doi.org/10.3389/fenrg.2018.00092	journal	September 2018
Efficient Mild Organosolv Lignin Extraction in a Flow-Through Setup Yielding Lignin with High β-O-4 Content Zijlstra, Douwe S.; Analbers, Coen A.; de Korte, Joren Polymers, Vol. 11, Issue 12 https://doi.org/10.3390/polym11121913	journal	November 2019
Acid Degradation of Lignin. III. Formation of Formaldehyde. Lundquist, Knut; Ericsson, Lennart; Karlsson, Sune Acta Chemica Scandinavica, Vol. 24 https://doi.org/10.3891/acta.chem.scand.24-3681	journal	January 1970

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