skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Kinetic Studies of Lignin Solvolysis and Reduction by Reductive Catalytic Fractionation Decoupled in Flow-Through Reactors

Abstract

Reductive catalytic fractionation (RCF) is an effective active-stabilization strategy to selectively extract and depolymerize lignin into aromatic monomers. Here, the kinetics of RCF were investigated by using flow-through reactors to decouple the two limiting mechanistic steps, namely lignin solvolysis and reduction. When operating in a solvolysis-limited regime, apparent energy barriers of 63 ± 1 and 64 ± 2 kJ mol–1 were measured for the solvent mediated lignin extraction of poplar using particle diameters of 0.5 < d < 1 mm and 0.075 < d < 0.25 mm, respectively. In contrast, when using mechanically stirred batch reactors, apparent barriers of 32 ± 1 and 39 ± 3 kJ mol–1 were measured for particle diameters of 0.5 < d < 1 mm and 0.075 < d < 0.25 mm, respectively. The difference of activation barriers between flow and batch reactors indicated that lignin extraction under typical RCF conditions in a 100 mL batch reactor stirred at 700 rpm was mass-transfer limited. In the reduction-limited regime, cleavage of the β-O-4 bond in a model compound exhibited an apparent activation barrier of 168 ± 14 kJ mol–1. This study demonstrates RCF occurs by two limiting processes that can be independently controlled. Furthermore, both controllingmore » which process limits RCF and verifying if transport limitations exist, are critical steps to develop a mechanistic understanding of RCF and to design improved catalysts.« less

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Chemical Engineering, Massachusetts Institute of Technology, 25 Ames Street, Cambridge, Massachusetts 02139, United States
  2. National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office; National Science Foundation (NSF)
OSTI Identifier:
1436364
Alternate Identifier(s):
OSTI ID: 1462319; OSTI ID: 1508813
Report Number(s):
NREL/JA-2A00-72048
Journal ID: ISSN 2168-0485
Grant/Contract Number:  
AC36?08GO28308; AC36-08GO28308; 1454299
Resource Type:
Published Article
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Name: ACS Sustainable Chemistry & Engineering Journal Volume: 6 Journal Issue: 6; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; biomass pretreatment; flow-through extraction; lignin conversion; lignin first; lignin kinetics; reductive catalysis; semicontinuous processing

Citation Formats

Anderson, Eric M., Stone, Michael L., Hülsey, Max J., Beckham, Gregg T., and Román-Leshkov, Yuriy. Kinetic Studies of Lignin Solvolysis and Reduction by Reductive Catalytic Fractionation Decoupled in Flow-Through Reactors. United States: N. p., 2018. Web. https://doi.org/10.1021/acssuschemeng.8b01256.
Anderson, Eric M., Stone, Michael L., Hülsey, Max J., Beckham, Gregg T., & Román-Leshkov, Yuriy. Kinetic Studies of Lignin Solvolysis and Reduction by Reductive Catalytic Fractionation Decoupled in Flow-Through Reactors. United States. https://doi.org/10.1021/acssuschemeng.8b01256
Anderson, Eric M., Stone, Michael L., Hülsey, Max J., Beckham, Gregg T., and Román-Leshkov, Yuriy. Tue . "Kinetic Studies of Lignin Solvolysis and Reduction by Reductive Catalytic Fractionation Decoupled in Flow-Through Reactors". United States. https://doi.org/10.1021/acssuschemeng.8b01256.
@article{osti_1436364,
title = {Kinetic Studies of Lignin Solvolysis and Reduction by Reductive Catalytic Fractionation Decoupled in Flow-Through Reactors},
author = {Anderson, Eric M. and Stone, Michael L. and Hülsey, Max J. and Beckham, Gregg T. and Román-Leshkov, Yuriy},
abstractNote = {Reductive catalytic fractionation (RCF) is an effective active-stabilization strategy to selectively extract and depolymerize lignin into aromatic monomers. Here, the kinetics of RCF were investigated by using flow-through reactors to decouple the two limiting mechanistic steps, namely lignin solvolysis and reduction. When operating in a solvolysis-limited regime, apparent energy barriers of 63 ± 1 and 64 ± 2 kJ mol–1 were measured for the solvent mediated lignin extraction of poplar using particle diameters of 0.5 < d < 1 mm and 0.075 < d < 0.25 mm, respectively. In contrast, when using mechanically stirred batch reactors, apparent barriers of 32 ± 1 and 39 ± 3 kJ mol–1 were measured for particle diameters of 0.5 < d < 1 mm and 0.075 < d < 0.25 mm, respectively. The difference of activation barriers between flow and batch reactors indicated that lignin extraction under typical RCF conditions in a 100 mL batch reactor stirred at 700 rpm was mass-transfer limited. In the reduction-limited regime, cleavage of the β-O-4 bond in a model compound exhibited an apparent activation barrier of 168 ± 14 kJ mol–1. This study demonstrates RCF occurs by two limiting processes that can be independently controlled. Furthermore, both controlling which process limits RCF and verifying if transport limitations exist, are critical steps to develop a mechanistic understanding of RCF and to design improved catalysts.},
doi = {10.1021/acssuschemeng.8b01256},
journal = {ACS Sustainable Chemistry & Engineering},
number = 6,
volume = 6,
place = {United States},
year = {2018},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acssuschemeng.8b01256

Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Kinetic and mechanistic insights into hydrogenolysis of lignin to monomers in a continuous flow reactor
journal, January 2019

  • Li, Yanding; Demir, Benginur; Vázquez Ramos, Leida M.
  • Green Chemistry, Vol. 21, Issue 13
  • DOI: 10.1039/c9gc00986h

Catalytic Scissoring of Lignin into Aryl Monomers
journal, July 2019


Catalytic Scissoring of Lignin into Aryl Monomers
journal, July 2019


Kinetic and mechanistic insights into hydrogenolysis of lignin to monomers in a continuous flow reactor
journal, January 2019

  • Li, Yanding; Demir, Benginur; Vázquez Ramos, Leida M.
  • Green Chemistry, Vol. 21, Issue 13
  • DOI: 10.1039/c9gc00986h

Task-Specific Catalyst Development for Lignin-First Biorefinery toward Hemicellulose Retention or Feedstock Extension
journal, January 2019


Membrane Fractionation of Liquors from Lignin‐First Biorefining
journal, February 2019


Cooperative Co 0 /Co II Sites Stabilized by a Perovskite Matrix Enable Selective C−O and C−C bond Hydrogenolysis of Oxygenated Arenes
journal, April 2019

  • Shetty, Manish; Zanchet, Daniela; Green, William H.
  • ChemSusChem, Vol. 12, Issue 10
  • DOI: 10.1002/cssc.201900664

Catalytic Strategies Towards Lignin-Derived Chemicals
journal, August 2018

  • Van den Bosch, S.; Koelewijn, S. -F.; Renders, T.
  • Topics in Current Chemistry, Vol. 376, Issue 5
  • DOI: 10.1007/s41061-018-0214-3

Differences in S/G ratio in natural poplar variants do not predict catalytic depolymerization monomer yields
journal, May 2019


Catalytic lignocellulose biorefining in n -butanol/water: a one-pot approach toward phenolics, polyols, and cellulose
journal, January 2018

  • Renders, T.; Cooreman, E.; Van den Bosch, S.
  • Green Chemistry, Vol. 20, Issue 20
  • DOI: 10.1039/c8gc01031e

Supercritical methanol depolymerization and hydrodeoxygenation of lignin and biomass over reduced copper porous metal oxides
journal, January 2019

  • McClelland, Daniel J.; Galebach, Peter H.; Motagamwala, Ali Hussain
  • Green Chemistry, Vol. 21, Issue 11
  • DOI: 10.1039/c9gc00589g

Microwave-assisted depolymerization of various types of waste lignins over two-dimensional CuO/BCN catalysts
journal, January 2020

  • Cao, Yang; Chen, Season S.; Tsang, Daniel C. W.
  • Green Chemistry, Vol. 22, Issue 3
  • DOI: 10.1039/c9gc03553b

Efficient Mild Organosolv Lignin Extraction in a Flow-Through Setup Yielding Lignin with High β-O-4 Content
journal, November 2019

  • Zijlstra, Douwe S.; Analbers, Coen A.; de Korte, Joren
  • Polymers, Vol. 11, Issue 12
  • DOI: 10.3390/polym11121913