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:: Tue Apr 24 00:00:00 EDT 2018

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.

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                    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

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                    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.

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@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         = {Tue Apr 24 00:00:00 EDT 2018},

  month        = {Tue Apr 24 00:00:00 EDT 2018}

}

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

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