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.; Beckham, Gregg T.; Román-Leshkov, Yuriy

doi:10.1021/acssuschemeng.8b01256

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 »« less

Authors:

Anderson, Eric M. ^[1]; Stone, Michael L. ^[1];

^[1];

^[2];

^[1]

Chemical Engineering, Massachusetts Institute of Technology, 25 Ames Street, Cambridge, Massachusetts 02139, United States
National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States

Publication Date:: 2018-04-24

Research Org.:: National Renewable Energy Laboratory (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), Sustainable 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.  doi:10.1021/acssuschemeng.8b01256.

Copy to clipboard


                    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

Copy to clipboard


                    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.

Copy to clipboard


                    
@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}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1021/acssuschemeng.8b01256

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 76 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

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

Wang, Min; Wang, Feng
Advanced Materials, Vol. 31, Issue 50
DOI: 10.1002/adma.201901866

Catalytic Scissoring of Lignin into Aryl Monomers
journal, July 2019

Wang, Min; Wang, Feng
Advanced Materials, Vol. 31, Issue 50
DOI: 10.1002/adma.201901866

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

Qiu, Shi; Guo, Xuan; Huang, Yong
ChemSusChem, Vol. 12, Issue 4
DOI: 10.1002/cssc.201802130

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

Sultan, Zafar; Graça, Inês; Li, Yueqin
ChemSusChem, Vol. 12, Issue 6
DOI: 10.1002/cssc.201802747

Rapid Nondestructive Fractionation of Biomass (≤15 min) by using Flow‐Through Recyclable Formic Acid toward Whole Valorization of Carbohydrate and Lignin
journal, February 2019

Zhou, Hao; Tan, Liping; Fu, Yingjuan
ChemSusChem, Vol. 12, Issue 6
DOI: 10.1002/cssc.201802803

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

Anderson, Eric M.; Stone, Michael L.; Katahira, Rui
Nature Communications, Vol. 10, Issue 1
DOI: 10.1038/s41467-019-09986-1

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

Rapid flow-through fractionation of biomass to preserve labile aryl ether bonds in native lignin
journal, January 2019

Zhou, Hao; Xu, Jia Yun; Fu, Yingjuan
Green Chemistry, Vol. 21, Issue 17
DOI: 10.1039/c9gc02315a

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

Enhanced Selective Production of Arenes and Regenerating Rate in Aryl Ether Hydrogenolysis over Mesoporous Nickel in Plug-Flow Reactors
journal, October 2019

Zheng, Chunming; Wang, Dongxue; Hu, Xudong
Catalysts, Vol. 9, Issue 11
DOI: 10.3390/catal9110904

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

Similar Records in DOE PAGES and OSTI.GOV collections:

Reductive Catalytic Fractionation of Corn Stover Lignin

Journal Article Anderson, Eric M. ; Katahira, Rui ; Reed, Michelle ; ... - ACS Sustainable Chemistry & Engineering

Reductive catalytic fractionation (RCF) has emerged as an effective biomass pretreatment strategy to depolymerize lignin into tractable fragments in high yields. We investigate the RCF of corn stover, a highly abundant herbaceous feedstock, using carbon-supported Ru and Ni catalysts at 200 and 250 °C in methanol and, in the presence or absence of an acid cocatalyst (H₃PO₄ or an acidified carbon support). Three key performance variables were studied: (1) the effectiveness of lignin extraction as measured by the yield of lignin oil, (2) the yield of monomers in the lignin oil, and (3) the carbohydrate retention in the residual solidsmore »« less
Cited by 177
https://doi.org/10.1021/acssuschemeng.6b01858
Flowthrough Reductive Catalytic Fractionation of Biomass

Journal Article Anderson, Eric M. ; Stone, Michael L. ; Katahira, Rui ; ... - Joule

Reductive catalytic fractionation (RCF) has emerged as a leading biomass fractionation and lignin valorization strategy. Here, flowthrough reactors were used to investigate RCF of poplar. Most RCF studies to date have been conducted in batch, but a flow-based process enables the acquisition of intrinsic kinetic and mechanistic data essential to accelerate the design, optimization, and scale-up of RCF processes. Time-resolved product distributions and yields obtained from experiments with different catalyst loadings were used to identify and deconvolute events during solvolysis and hydrogenolysis. Multi-bed RCF experiments provided unique insights into catalyst deactivation, showing that leaching, sintering, and surface poisoning are causesmore »« less
https://doi.org/10.1016/j.joule.2017.10.004
Activity and selectivity of palladium catalysts during the liquid-phase hydrogenation of phenol. Influence of temperature and pressure

Journal Article Gonzalez-Velasco, J R ; Gonzalez-Marcos, M P ; Arnaiz, S ; ... - Industrial and Engineering Chemistry Research

Two series of highly dispersed palladium catalysts supported on alumina have been prepared by adsorption from solution, with palladium contents varying from 0.25 to 2.0 wt %. The first series was calcined at 773 K for 4 h in air, whereas the second series was just heated at 423 K for 1 h in nitrogen, before reduction. Complete dispersion of the metal has been found for the calcined catalysts, and metal dispersion was favored with low palladium contents for the noncalcined catalysts. The kinetic behavior of the catalysts has been analyzed for the liquid-phase hydrogenation of phenol in a stirredmore »« less
https://doi.org/10.1021/ie00043a004
2.2.3.106 - Lignin-First Biorefinery Development

Conference Beckham, Gregg T.

The Lignin-First Biorefinery Development (LigFirst) project aims to develop a cost-effective, and scalable biomass fractionation strategy based on reductive catalytic fractionation (RCF). The RCF process uses a protic solvent, hydrogen gas or a hydrogen donor, and a metal catalyst in the presence of intact biomass to produce a stable, depolymerized lignin oil and a polysaccharide pulp, which can both be converted to value-added products in parallel processes. RCF is a promising strategy to enable the use of woody feedstocks in biochemical conversion processes and is also promising as a means to valorize lignin with equal emphasis to biomass carbohydrates. Guidedmore »« less
Full Text Available
DEVELOPMENT OF HIGH ACTIVITY, COAL-DERIVED, PROMOTED CATALYTIC SYSTEMS FOR NOx REDUCTION AT LOW TEMPERATURES

Technical Report Calo, Joseph M

This project is directed at an investigation of catalytic NO{sub x} reduction mechanisms on coal-derived, activated carbon supports at low temperatures. Promoted carbon systems offer some potentially significant advantages for heterogeneous NO{sub x} reduction. These include: low cost; high activity at low temperatures, which minimizes carbon loss; oxygen resistance; and a support material which can be engineered with respect to porosity, transport and catalyst dispersion characteristics. During the reporting period, the following has been accomplished: (1) A packed bed reactor/gas flow system has been tested and applied to performing NO-carbon reactivity studies. This system employs a Kin-Tek gas calibration/mixing systemmore »« less
https://doi.org/10.2172/783589

Full Text Available

Similar Records

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

Abstract

Citation Formats

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

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

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

Rapid Nondestructive Fractionation of Biomass (≤15 min) by using Flow‐Through Recyclable Formic Acid toward Whole Valorization of Carbohydrate and Lignin 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

Catalytic Strategies Towards Lignin-Derived Chemicals journal, August 2018

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

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

Rapid flow-through fractionation of biomass to preserve labile aryl ether bonds in native lignin journal, January 2019

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

Enhanced Selective Production of Arenes and Regenerating Rate in Aryl Ether Hydrogenolysis over Mesoporous Nickel in Plug-Flow Reactors journal, October 2019

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

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

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

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

Rapid Nondestructive Fractionation of Biomass (≤15 min) by using Flow‐Through Recyclable Formic Acid toward Whole Valorization of Carbohydrate and Lignin
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

Catalytic Strategies Towards Lignin-Derived Chemicals
journal, August 2018

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

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

Rapid flow-through fractionation of biomass to preserve labile aryl ether bonds in native lignin
journal, January 2019

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

Enhanced Selective Production of Arenes and Regenerating Rate in Aryl Ether Hydrogenolysis over Mesoporous Nickel in Plug-Flow Reactors
journal, October 2019

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