DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Quenching of reactive intermediates during mechanochemical depolymerization of lignin

Abstract

Mechanochemical reactions are performed to depolymerize organosolv lignin with sodium hydroxide in a mixer ball mill. GPC analysis reveals that rapid depolymerization into small oligomers occurs within minutes of milling time, followed by a slower reduction in average relative molecular mass over the next 8 h of milling. Monomeric products are identified by GC–MS and quantified by GC-FID. The extent of depolymerization appears to be limited by repolymerization reactions that form bonds between products. Suppression of these repolymerization reactions can be achieved through the addition of methanol as a scavenger or adjustment of the moisture content of the feedstock. These modifications result in lower average relative molecular masses and higher yields of monomers. These results are an important step towards designing an efficient pathway for lignin valorization.

Authors:
 [1];  [1];  [1];  [1];  [2];  [2];  [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1364389
Alternate Identifier(s):
OSTI ID: 1550039
Report Number(s):
PNNL-SA-120623
Journal ID: ISSN 0920-5861; PII: S0920586117302997
Grant/Contract Number:  
AC05-76RL01830; AC06-76RLO-1830
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Today
Additional Journal Information:
Journal Volume: 302; Journal ID: ISSN 0920-5861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; mechanocatalysis; biomass; ball mill; Organosolv lignin; scavenger; hydrolysis

Citation Formats

Brittain, Alex D., Chrisandina, Natasha J., Cooper, Rachel E., Buchanan, Michael, Cort, John R., Olarte, Mariefel V., and Sievers, Carsten. Quenching of reactive intermediates during mechanochemical depolymerization of lignin. United States: N. p., 2017. Web. doi:10.1016/j.cattod.2017.04.066.
Brittain, Alex D., Chrisandina, Natasha J., Cooper, Rachel E., Buchanan, Michael, Cort, John R., Olarte, Mariefel V., & Sievers, Carsten. Quenching of reactive intermediates during mechanochemical depolymerization of lignin. United States. https://doi.org/10.1016/j.cattod.2017.04.066
Brittain, Alex D., Chrisandina, Natasha J., Cooper, Rachel E., Buchanan, Michael, Cort, John R., Olarte, Mariefel V., and Sievers, Carsten. Wed . "Quenching of reactive intermediates during mechanochemical depolymerization of lignin". United States. https://doi.org/10.1016/j.cattod.2017.04.066. https://www.osti.gov/servlets/purl/1364389.
@article{osti_1364389,
title = {Quenching of reactive intermediates during mechanochemical depolymerization of lignin},
author = {Brittain, Alex D. and Chrisandina, Natasha J. and Cooper, Rachel E. and Buchanan, Michael and Cort, John R. and Olarte, Mariefel V. and Sievers, Carsten},
abstractNote = {Mechanochemical reactions are performed to depolymerize organosolv lignin with sodium hydroxide in a mixer ball mill. GPC analysis reveals that rapid depolymerization into small oligomers occurs within minutes of milling time, followed by a slower reduction in average relative molecular mass over the next 8 h of milling. Monomeric products are identified by GC–MS and quantified by GC-FID. The extent of depolymerization appears to be limited by repolymerization reactions that form bonds between products. Suppression of these repolymerization reactions can be achieved through the addition of methanol as a scavenger or adjustment of the moisture content of the feedstock. These modifications result in lower average relative molecular masses and higher yields of monomers. These results are an important step towards designing an efficient pathway for lignin valorization.},
doi = {10.1016/j.cattod.2017.04.066},
journal = {Catalysis Today},
number = ,
volume = 302,
place = {United States},
year = {Wed May 10 00:00:00 EDT 2017},
month = {Wed May 10 00:00:00 EDT 2017}
}

Journal Article:

Citation Metrics:
Cited by: 33 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The Path Forward for Biofuels and Biomaterials
journal, January 2006

  • Ragauskas, Arthur J.; Williams, Charlotte K.; Davison, Brian H.
  • Science, Vol. 311, Issue 5760, p. 484-489
  • DOI: 10.1126/science.1114736

Current Challenges in Commercially Producing Biofuels from Lignocellulosic Biomass
journal, January 2014


Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis
journal, June 2016

  • Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T.
  • Angewandte Chemie International Edition, Vol. 55, Issue 29
  • DOI: 10.1002/anie.201510351

The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
journal, June 2010

  • Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L.
  • Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599
  • DOI: 10.1021/cr900354u

A sustainable approach for lignin valorization by heterogeneous photocatalysis
journal, January 2016

  • Li, Shao-Hai; Liu, Siqi; Colmenares, Juan Carlos
  • Green Chemistry, Vol. 18, Issue 3
  • DOI: 10.1039/C5GC02109J

Catalytic Transformation of Lignin for the Production of Chemicals and Fuels
journal, October 2015


Lignin Depolymerization and Conversion A Review of Thermochemical Methods
journal, November 2010

  • Pandey, M. P.; Kim, C. S.
  • Chemical Engineering & Technology, Vol. 34, Issue 1, p. 29-41
  • DOI: 10.1002/ceat.201000270

Lignin fate and characterization during ionic liquid biomass pretreatment for renewable chemicals and fuels production
journal, January 2014

  • Sathitsuksanoh, Noppadon; Holtman, Kevin M.; Yelle, Daniel J.
  • Green Chem., Vol. 16, Issue 3
  • DOI: 10.1039/C3GC42295J

Structural Modification of Lignin and Characterization of Pretreated Wheat Straw by Ozonation
journal, April 2013

  • Bule, Mahesh V.; Gao, Allan H.; Hiscox, Bill
  • Journal of Agricultural and Food Chemistry, Vol. 61, Issue 16
  • DOI: 10.1021/jf4001988

Lignin depolymerization/repolymerization and its critical role for delignification of aspen wood by steam explosion
journal, November 2007


Organosolv lignin depolymerization with different base catalysts
journal, April 2012

  • Toledano, Ana; Serrano, Luis; Labidi, Jalel
  • Journal of Chemical Technology & Biotechnology, Vol. 87, Issue 11
  • DOI: 10.1002/jctb.3799

Disassembly of lignin and chemical recovery—rapid depolymerization of lignin without char formation in water–phenol mixtures
journal, July 2004


Lignin depolymerisation in supercritical carbon dioxide/acetone/water fluid for the production of aromatic chemicals
journal, February 2012


Optimizing solvolysis conditions for integrated depolymerisation and hydrodeoxygenation of lignin to produce liquid biofuel
journal, May 2009

  • Kleinert, Mike; Gasson, James R.; Barth, Tanja
  • Journal of Analytical and Applied Pyrolysis, Vol. 85, Issue 1-2, p. 108-117
  • DOI: 10.1016/j.jaap.2008.09.019

Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization
journal, October 2016

  • Shuai, Li; Amiri, Masoud Talebi; Questell-Santiago, Ydna M.
  • Science, Vol. 354, Issue 6310
  • DOI: 10.1126/science.aaf7810

Mechanocatalytic Deconstruction of Cellulose: An Emerging Entry into Biorefinery
journal, October 2013


Deciphering ‘water-soluble lignocellulose’ obtained by mechanocatalysis: new insights into the chemical processes leading to deep depolymerization
journal, January 2014

  • Käldström, Mats; Meine, Niklas; Farès, Christophe
  • Green Chem., Vol. 16, Issue 7
  • DOI: 10.1039/C4GC00004H

Solvent-Free Catalytic Depolymerization of Cellulose to Water-Soluble Oligosaccharides
journal, April 2012


Mechanocatalytic depolymerization of cellulose combined with hydrogenolysis as a highly efficient pathway to sugar alcohols
journal, January 2013

  • Hilgert, Jakob; Meine, Niklas; Rinaldi, Roberto
  • Energy Environ. Sci., Vol. 6, Issue 1
  • DOI: 10.1039/C2EE23057G

Mechanocatalysis for biomass-derived chemicals and fuels
journal, January 2010

  • Hick, Sandra M.; Griebel, Carolin; Restrepo, David T.
  • Green Chemistry, Vol. 12, Issue 3
  • DOI: 10.1039/b923079c

Mechanocatalytic Depolymerization of Dry (Ligno)cellulose As an Entry Process for High-Yield Production of Furfurals
journal, April 2013

  • Carrasquillo-Flores, Ronald; Käldström, Mats; Schüth, Ferdi
  • ACS Catalysis, Vol. 3, Issue 5
  • DOI: 10.1021/cs4001333

Lignin Depolymerization into Aromatic Monomers over Solid Acid Catalysts
journal, November 2014

  • Deepa, Ayillath K.; Dhepe, Paresh L.
  • ACS Catalysis, Vol. 5, Issue 1
  • DOI: 10.1021/cs501371q

Mechanochemical degradation of lignin and wood by solvent-free grinding in a reactive medium
journal, January 2013

  • Kleine, Tillmann; Buendia, Julien; Bolm, Carsten
  • Green Chem., Vol. 15, Issue 1
  • DOI: 10.1039/C2GC36456E

Mechanochemistry: opportunities for new and cleaner synthesis
journal, January 2012

  • James, Stuart L.; Adams, Christopher J.; Bolm, Carsten
  • Chem. Soc. Rev., Vol. 41, Issue 1
  • DOI: 10.1039/C1CS15171A

Mechanically initiated chemical reactions in solids
journal, February 1975


Mechanocatalytic depolymerization of cellulose and raw biomass and downstream processing of the products
journal, October 2014


Kinetic model for the hydrolysis of lignocellulosic biomass in the ionic liquid, 1-ethyl-3-methyl-imidazolium chloride
journal, January 2009

  • Vanoye, Laurent; Fanselow, Markus; Holbrey, John D.
  • Green Chemistry, Vol. 11, Issue 3
  • DOI: 10.1039/b817882h

Mechanical depolymerisation of acidulated cellulose: understanding the solubility of high molecular weight oligomers
journal, January 2013

  • Shrotri, Abhijit; Lambert, Lynette Kay; Tanksale, Akshat
  • Green Chemistry, Vol. 15, Issue 10
  • DOI: 10.1039/c3gc40945g

Quantitative carbon detector (QCD) for calibration-free, high-resolution characterization of complex mixtures
journal, January 2015

  • Maduskar, Saurabh; Teixeira, Andrew R.; Paulsen, Alex D.
  • Lab on a Chip, Vol. 15, Issue 2
  • DOI: 10.1039/C4LC01180E

Characterization of lignin derived from water-only and dilute acid flowthrough pretreatment of poplar wood at elevated temperatures
journal, December 2015


Standardization of chemical analytical techniques for pyrolysis bio-oil: history, challenges, and current status of methods: Bio-oil Analytical Standardization
journal, July 2016

  • Ferrell, Jack R.; Olarte, Mariefel V.; Christensen, Earl D.
  • Biofuels, Bioproducts and Biorefining, Vol. 10, Issue 5
  • DOI: 10.1002/bbb.1661

A Comprehensive Approach for Quantitative Lignin Characterization by NMR Spectroscopy
journal, April 2004

  • Capanema, Ewellyn A.; Balakshin, Mikhail Y.; Kadla, John F.
  • Journal of Agricultural and Food Chemistry, Vol. 52, Issue 7
  • DOI: 10.1021/jf035282b

Structural Characterization and Comparison of Switchgrass Ball-milled Lignin Before and After Dilute Acid Pretreatment
journal, August 2009

  • Samuel, Reichel; Pu, Yunqiao; Raman, Babu
  • Applied Biochemistry and Biotechnology, Vol. 162, Issue 1
  • DOI: 10.1007/s12010-009-8749-y

Characterization of Lignin Structures and Lignin–Carbohydrate Complex (LCC) Linkages by Quantitative 13 C and 2D HSQC NMR Spectroscopy
journal, October 2011

  • Yuan, Tong-Qi; Sun, Shao-Ni; Xu, Feng
  • Journal of Agricultural and Food Chemistry, Vol. 59, Issue 19
  • DOI: 10.1021/jf2031549

The Chromatographic Separation of Hardwood Extractive Components Giving Color Reactions with Phloroglucinol
journal, November 1953

  • Black, R. A.; Rosen, A. A.; Adams, S. L.
  • Journal of the American Chemical Society, Vol. 75, Issue 21
  • DOI: 10.1021/ja01117a058

In-depth investigation on quantitative characterization of pyrolysis oil by 31 P NMR
journal, January 2016


Influence of alkali carbonates on benzyl phenyl ether cleavage pathways in superheated water
journal, March 2010

  • Roberts, Virginia; Fendt, Sebastian; Lemonidou, Angeliki A.
  • Applied Catalysis B: Environmental, Vol. 95, Issue 1-2, p. 71-77
  • DOI: 10.1016/j.apcatb.2009.12.010

Insights into Oxidative Conversion of Lignin to High-Added-Value Phenolic Aldehydes
journal, January 2011

  • Rodrigues Pinto, Paula C.; Borges da Silva, Eduardo A.; Rodrigues, Alírio Egídio
  • Industrial & Engineering Chemistry Research, Vol. 50, Issue 2
  • DOI: 10.1021/ie102132a

Hydrolytic degradation of alkaline lignin in hot-compressed water and ethanol
journal, December 2010


Batch microreactor studies of lignin and lignin model compound depolymerization by bases in alcohol solvents
journal, September 1999


Examination of water phase transitions in Loblolly pine and cell wall components by differential scanning calorimetry
journal, April 2012


Review of current and future softwood kraft lignin process chemistry
journal, September 2004


Effects of short-time vibratory ball milling on the shape of FT-IR spectra of wood and cellulose
journal, October 2004


Acid-Assisted Ball Milling of Cellulose as an Efficient Pretreatment Process for the Production of Butyl Glycosides
journal, September 2015

  • Boissou, Florent; Sayoud, Nassim; De Oliveira Vigier, Karine
  • ChemSusChem, Vol. 8, Issue 19
  • DOI: 10.1002/cssc.201500700

Direct acid-catalysed mechanical depolymerisation of fibre sludge to reducing sugars using planetary milling
journal, March 2016


Efficient mechano-catalytic depolymerization of crystalline cellulose by formation of branched glucan chains
journal, January 2015

  • Dornath, Paul; Cho, Hong Je; Paulsen, Alex
  • Green Chemistry, Vol. 17, Issue 2
  • DOI: 10.1039/C4GC02187H

The Kinetics of Simultaneous Hydrolysis and Alcoholysis of Esters in Aqueous Alcohol Solutions 1
journal, April 1959

  • Bender, Myron L.; Glasson, William A.
  • Journal of the American Chemical Society, Vol. 81, Issue 7
  • DOI: 10.1021/ja01516a020

Effects of sodium hydroxide on cereal straws in relation to the enhanced degradation of structural polysaccharides by rumen microorganisms
journal, August 1981


The Effect of Water Plasticization on the Molecular Mobility and Crystallization Tendency of Amorphous Disaccharides
journal, December 2011

  • Heljo, Ville Petteri; Nordberg, Antti; Tenho, Mikko
  • Pharmaceutical Research, Vol. 29, Issue 10
  • DOI: 10.1007/s11095-011-0658-4

Works referencing / citing this record:

Kinematic Modeling of Mechanocatalytic Depolymerization of α-Cellulose and Beechwood
journal, January 2018

  • Kessler, Martin; Woodward, Robert T.; Wong, Narumi
  • ChemSusChem, Vol. 11, Issue 3
  • DOI: 10.1002/cssc.201702060

Analysis of gas chromatography/mass spectrometry data for catalytic lignin depolymerization using positive matrix factorization
journal, January 2018

  • Gao, Yu; Walker, Michael J.; Barrett, Jacob A.
  • Green Chemistry, Vol. 20, Issue 18
  • DOI: 10.1039/c8gc01474d

From Synthesis of Amino Acids and Peptides to Enzymatic Catalysis: A Bottom-Up Approach in Mechanochemistry
journal, March 2018


Kinematic Modeling of Mechanocatalytic Depolymerization of α‐Cellulose and Beechwood
journal, February 2018

  • Kessler, Martin; Woodward, Robert T.; Wong, Narumi
  • ChemSusChem, Vol. 11, Issue 3
  • DOI: 10.1002/cssc.201800163