Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Local phase separation of co-solvents enhances pretreatment of biomass for bioenergy applications

Abstract

Pretreatment facilitates more complete deconstruction of plant biomass to enable more economic production of lignocellulosic biofuels and byproducts. Various co-solvent pretreatments have demonstrated advantages relative to aqueous-only methods by enhancing lignin removal to allow unfettered access to cellulose. However, there is a limited mechanistic understanding of the interactions between the co-solvents and cellulose that impedes further improvement of such pretreatment methods. Recently, tetrahydrofuran (THF) has been identified as a highly effective co-solvent for the pretreatment and fractionation of biomass. Here, to elucidate the mechanism of the THF water interactions with cellulose, we pair simulation and experimental data demonstrating that enhanced solubilization of cellulose can be achieved by the THF water co-solvent system at equivolume mixtures and moderate temperatures (≤445 K). The simulations show that THF and water spontaneously phase separate on the local surface of a cellulose fiber, owing to hydrogen bonding of water molecules with the hydrophilic cellulose faces and stacking of THF molecules on the hydrophobic faces. Furthermore, a single fully solvated cellulose chain is shown to be preferentially bound by water molecules in the THF water mixture. In light of these findings, co-solvent reactions were performed on microcrystalline cellulose and maple wood to show that THF significantlymore » enhanced cellulose deconstruction and lignocellulose solubilization at simulation conditions, enabling a highly versatile and efficient biomass pretreatment and fractionation method.« less

Authors:
 [1];  [2];  [3];  [3];  [3];  [2];  [3]
+ Show Author Affiliations
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); The Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1326557
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 34; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS

Citation Formats

Mostofian, Barmak, Cai, Charles M., Smith, Micholas Dean, Petridis, Loukas, Cheng, Xiaolin, Wyman, Charles E., and Smith, Jeremy C. Local phase separation of co-solvents enhances pretreatment of biomass for bioenergy applications. United States: N. p., 2016. Web. doi:10.1021/jacs.6b03285.
Copy to clipboard
Mostofian, Barmak, Cai, Charles M., Smith, Micholas Dean, Petridis, Loukas, Cheng, Xiaolin, Wyman, Charles E., & Smith, Jeremy C. Local phase separation of co-solvents enhances pretreatment of biomass for bioenergy applications. United States. https://doi.org/10.1021/jacs.6b03285
Copy to clipboard
Mostofian, Barmak, Cai, Charles M., Smith, Micholas Dean, Petridis, Loukas, Cheng, Xiaolin, Wyman, Charles E., and Smith, Jeremy C. Tue . "Local phase separation of co-solvents enhances pretreatment of biomass for bioenergy applications". United States. https://doi.org/10.1021/jacs.6b03285. https://www.osti.gov/servlets/purl/1326557.
Copy to clipboard
@article{osti_1326557,
title = {Local phase separation of co-solvents enhances pretreatment of biomass for bioenergy applications},
author = {Mostofian, Barmak and Cai, Charles M. and Smith, Micholas Dean and Petridis, Loukas and Cheng, Xiaolin and Wyman, Charles E. and Smith, Jeremy C.},
abstractNote = {Pretreatment facilitates more complete deconstruction of plant biomass to enable more economic production of lignocellulosic biofuels and byproducts. Various co-solvent pretreatments have demonstrated advantages relative to aqueous-only methods by enhancing lignin removal to allow unfettered access to cellulose. However, there is a limited mechanistic understanding of the interactions between the co-solvents and cellulose that impedes further improvement of such pretreatment methods. Recently, tetrahydrofuran (THF) has been identified as a highly effective co-solvent for the pretreatment and fractionation of biomass. Here, to elucidate the mechanism of the THF water interactions with cellulose, we pair simulation and experimental data demonstrating that enhanced solubilization of cellulose can be achieved by the THF water co-solvent system at equivolume mixtures and moderate temperatures (≤445 K). The simulations show that THF and water spontaneously phase separate on the local surface of a cellulose fiber, owing to hydrogen bonding of water molecules with the hydrophilic cellulose faces and stacking of THF molecules on the hydrophobic faces. Furthermore, a single fully solvated cellulose chain is shown to be preferentially bound by water molecules in the THF water mixture. In light of these findings, co-solvent reactions were performed on microcrystalline cellulose and maple wood to show that THF significantly enhanced cellulose deconstruction and lignocellulose solubilization at simulation conditions, enabling a highly versatile and efficient biomass pretreatment and fractionation method.},
doi = {10.1021/jacs.6b03285},
journal = {Journal of the American Chemical Society},
number = 34,
volume = 138,
place = {United States},
year = {Tue Aug 02 00:00:00 EDT 2016},
month = {Tue Aug 02 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jacs.6b03285
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 65 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Isolation and characterization of cellulose from sugarcane bagasse
journal, May 2004

Nanostructure of cellulose microfibrils in spruce wood
journal, November 2011

  • Fernandes, A. N.; Thomas, L. H.; Altaner, C. M.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 47
  • DOI: 10.1073/pnas.1108942108

Fuel Ethanol from Cellulosic Biomass
journal, March 1991

Biocommodity Engineering
journal, October 1999

  • Lynd, L. R.; Wyman, C. E.; Gerngross, T. U.
  • Biotechnology Progress, Vol. 15, Issue 5
  • DOI: 10.1021/bp990109e

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

Cost of Abating Greenhouse Gas Emissions with Cellulosic Ethanol
journal, February 2015

  • Dwivedi, Puneet; Wang, Weiwei; Hudiburg, Tara
  • Environmental Science & Technology, Vol. 49, Issue 4
  • DOI: 10.1021/es5052588

Can biofuels finally take center stage?
journal, July 2006

Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production
journal, February 2007

  • Himmel, M. E.; Ding, S.-Y.; Johnson, D. K.
  • Science, Vol. 315, Issue 5813, p. 804-807
  • DOI: 10.1126/science.1137016

Biomass recalcitrance: a multi-scale, multi-factor, and conversion-specific property: Fig. 1.
journal, June 2015

  • McCann, Maureen C.; Carpita, Nicholas C.
  • Journal of Experimental Botany, Vol. 66, Issue 14
  • DOI: 10.1093/jxb/erv267

Pretreatment of lignocellulosic biomass for enhanced biogas production
journal, June 2014

Biomass Size Reduction Machines for Enhancing Biogas Production
journal, February 2011

The chemistry involved in the steam treatment of lignocellulosic materials
journal, January 2003

Biomass pretreatment: Fundamentals toward application
journal, November 2011

Dissolution of Cellose with Ionic Liquids
journal, May 2002

  • Swatloski, Richard P.; Spear, Scott K.; Holbrey, John D.
  • Journal of the American Chemical Society, Vol. 124, Issue 18, p. 4974-4975
  • DOI: 10.1021/ja025790m

Biological conversion of lignocellulosic biomass to ethanol
journal, July 1997

Importance of chemical pretreatment for bioconversion of lignocellulosic biomass
journal, August 2014

  • Behera, Shuvashish; Arora, Richa; Nandhagopal, N.
  • Renewable and Sustainable Energy Reviews, Vol. 36
  • DOI: 10.1016/j.rser.2014.04.047

Effects of Two-Stage Dilute Acid Pretreatment on the Structure and Composition of Lignin and Cellulose in Loblolly Pine
journal, September 2008

  • Sannigrahi, Poulomi; Ragauskas, Arthur J.; Miller, Stephen J.
  • BioEnergy Research, Vol. 1, Issue 3-4, p. 205-214
  • DOI: 10.1007/s12155-008-9021-y

The use of high-solids loadings in biomass pretreatment-a review
journal, February 2012

  • Modenbach, Alicia A.; Nokes, Sue E.
  • Biotechnology and Bioengineering, Vol. 109, Issue 6
  • DOI: 10.1002/bit.24464

Woody biomass pretreatment for cellulosic ethanol production: Technology and energy consumption evaluation☆
journal, July 2010

A mild biomass pretreatment using γ-valerolactone for concentrated sugar production
journal, January 2016

  • Shuai, Li; Questell-Santiago, Ydna M.; Luterbacher, Jeremy S.
  • Green Chemistry, Vol. 18, Issue 4
  • DOI: 10.1039/C5GC02489G

Ethanol organosolv pretreatment of softwood (Picea abies) and sugarcane bagasse for biofuel and biorefinery applications
journal, May 2015

  • Agnihotri, Swarnima; Johnsen, Ingvild A.; Bøe, Maren S.
  • Wood Science and Technology, Vol. 49, Issue 5
  • DOI: 10.1007/s00226-015-0738-4

Impact of high biomass loading on ionic liquid pretreatment
journal, January 2013

  • Cruz, Alejandro G.; Scullin, Chessa; Mu, Chen
  • Biotechnology for Biofuels, Vol. 6, Issue 1
  • DOI: 10.1186/1754-6834-6-52

Co-solvent Pretreatment Reduces Costly Enzyme Requirements for High Sugar and Ethanol Yields from Lignocellulosic Biomass
journal, February 2015

CELF pretreatment of corn stover boosts ethanol titers and yields from high solids SSF with low enzyme loadings
journal, January 2016

  • Nguyen, Thanh Yen; Cai, Charles M.; Osman, Omar
  • Green Chemistry, Vol. 18, Issue 6
  • DOI: 10.1039/C5GC01977J

On the Molecular Origins of Biomass Recalcitrance: The Interaction Network and Solvation Structures of Cellulose Microfibrils
journal, October 2010

  • Gross, Adam S.; Chu, Jhih-Wei
  • The Journal of Physical Chemistry B, Vol. 114, Issue 42
  • DOI: 10.1021/jp106452m

Insights into Hydrogen Bonding and Stacking Interactions in Cellulose
journal, December 2011

  • Parthasarathi, R.; Bellesia, G.; Chundawat, S. P. S.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 49
  • DOI: 10.1021/jp203620x

Hydration Control of the Mechanical and Dynamical Properties of Cellulose
journal, October 2014

  • Petridis, Loukas; O’Neill, Hugh M.; Johnsen, Mariah
  • Biomacromolecules, Vol. 15, Issue 11
  • DOI: 10.1021/bm5011849

Probing the Early Events Associated with Liquid Ammonia Pretreatment of Native Crystalline Cellulose
journal, August 2011

  • Bellesia, Giovanni; Chundawat, Shishir P. S.; Langan, Paul
  • The Journal of Physical Chemistry B, Vol. 115, Issue 32
  • DOI: 10.1021/jp2048844

The solvation structures of cellulose microfibrils in ionic liquids
journal, December 2011

  • Mostofian, Barmak; Smith, Jeremy C.; Cheng, Xiaolin
  • Interdisciplinary Sciences: Computational Life Sciences, Vol. 3, Issue 4
  • DOI: 10.1007/s12539-011-0111-8

Observed Mechanism for the Breakup of Small Bundles of Cellulose Iα and Iβ in Ionic Liquids from Molecular Dynamics Simulations
journal, March 2013

  • Rabideau, Brooks D.; Agarwal, Animesh; Ismail, Ahmed E.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 13
  • DOI: 10.1021/jp310225t

Cosolvent pretreatment in cellulosic biofuel production: effect of tetrahydrofuran-water on lignin structure and dynamics
journal, January 2016

  • Smith, Micholas Dean; Mostofian, Barmak; Cheng, Xiaolin
  • Green Chemistry, Vol. 18, Issue 5
  • DOI: 10.1039/C5GC01952D

Enhanced sampling simulation analysis of the structure of lignin in the THF–water miscibility gap
journal, January 2016

  • Smith, Micholas Dean; Petridis, Loukas; Cheng, Xiaolin
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 9
  • DOI: 10.1039/C5CP07088K

Simulation Analysis of the Temperature Dependence of Lignin Structure and Dynamics
journal, December 2011

  • Petridis, Loukas; Schulz, Roland; Smith, Jeremy C.
  • Journal of the American Chemical Society, Vol. 133, Issue 50
  • DOI: 10.1021/ja206839u

Common processes drive the thermochemical pretreatment of lignocellulosic biomass
journal, January 2014

  • Langan, Paul; Petridis, Loukas; O'Neill, Hugh M.
  • Green Chem., Vol. 16, Issue 1
  • DOI: 10.1039/C3GC41962B

CHARMM Additive All-Atom Force Field for Glycosidic Linkages between Hexopyranoses
journal, August 2009

  • Guvench, Olgun; Hatcher, Elizabeth; Venable, Richard M.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 9
  • DOI: 10.1021/ct900242e

CHARMM Additive All-Atom Force Field for Carbohydrate Derivatives and Its Utility in Polysaccharide and Carbohydrate–Protein Modeling
journal, August 2011

  • Guvench, Olgun; Mallajosyula, Sairam S.; Raman, E. Prabhu
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 10
  • DOI: 10.1021/ct200328p

Additive and Classical Drude Polarizable Force Fields for Linear and Cyclic Ethers
journal, March 2007

  • Vorobyov, Igor; Anisimov, Victor M.; Greene, Shannon
  • Journal of Chemical Theory and Computation, Vol. 3, Issue 3
  • DOI: 10.1021/ct600350s

Comparison of simple potential functions for simulating liquid water
journal, July 1983

  • Jorgensen, William L.; Chandrasekhar, Jayaraman; Madura, Jeffry D.
  • The Journal of Chemical Physics, Vol. 79, Issue 2
  • DOI: 10.1063/1.445869

GROMACS 4.5: a high-throughput and highly parallel open source molecular simulation toolkit
journal, February 2013

Particle mesh Ewald: An N ⋅log( N ) method for Ewald sums in large systems
journal, June 1993

  • Darden, Tom; York, Darrin; Pedersen, Lee
  • The Journal of Chemical Physics, Vol. 98, Issue 12
  • DOI: 10.1063/1.464397

A smooth particle mesh Ewald method
journal, November 1995

  • Essmann, Ulrich; Perera, Lalith; Berkowitz, Max L.
  • The Journal of Chemical Physics, Vol. 103, Issue 19
  • DOI: 10.1063/1.470117

Canonical sampling through velocity rescaling
journal, January 2007

  • Bussi, Giovanni; Donadio, Davide; Parrinello, Michele
  • The Journal of Chemical Physics, Vol. 126, Issue 1
  • DOI: 10.1063/1.2408420

Molecular dynamics with coupling to an external bath
journal, October 1984

  • Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.
  • The Journal of Chemical Physics, Vol. 81, Issue 8
  • DOI: 10.1063/1.448118

LINCS: A linear constraint solver for molecular simulations
journal, September 1997

Characterizing the Catalyzed Hydrolysis of β-1,4 Glycosidic Bonds Using Density Functional Theory
journal, December 2013

  • Fleming, Kelly L.; Pfaendtner, Jim
  • The Journal of Physical Chemistry A, Vol. 117, Issue 51
  • DOI: 10.1021/jp4081178

Definition of the hydrogen bond (IUPAC Recommendations 2011)
journal, July 2011

  • Arunan, Elangannan; Desiraju, Gautam R.; Klein, Roger A.
  • Pure and Applied Chemistry, Vol. 83, Issue 8
  • DOI: 10.1351/PAC-REC-10-01-02

Phase equilibria in the system tetrahydrofuran(1)-water(2)
journal, January 1972

  • Matouš, J.; Novák, J. P.; Šobr, J.
  • Collection of Czechoslovak Chemical Communications, Vol. 37, Issue 8
  • DOI: 10.1135/cccc19722653

Molecular Driving Forces behind the Tetrahydrofuran–Water Miscibility Gap
journal, January 2016

  • Smith, Micholas Dean; Mostofian, Barmak; Petridis, Loukas
  • The Journal of Physical Chemistry B, Vol. 120, Issue 4
  • DOI: 10.1021/acs.jpcb.5b09770

Solvent-Driven Preferential Association of Lignin with Regions of Crystalline Cellulose in Molecular Dynamics Simulation
journal, September 2013

  • Lindner, Benjamin; Petridis, Loukas; Schulz, Roland
  • Biomacromolecules, Vol. 14, Issue 10
  • DOI: 10.1021/bm400442n

Mechanism of lignin inhibition of enzymatic biomass deconstruction
journal, December 2015

  • Vermaas, Josh V.; Petridis, Loukas; Qi, Xianghong
  • Biotechnology for Biofuels, Vol. 8, Issue 1
  • DOI: 10.1186/s13068-015-0379-8

Hydrogen-bond kinetics in liquid water
journal, January 1996

  • Luzar, Alenka; Chandler, David
  • Nature, Vol. 379, Issue 6560
  • DOI: 10.1038/379055a0
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Geminal Coordinatively Unsaturated Sites on MOF‐808 for the Selective Uptake of Phenolics from a Real Bio‐Oil Mixture
    journal, February 2019

    • Jia, Chunmei; Cirujano, Francisco G.; Bueken, Bart
    • ChemSusChem, Vol. 12, Issue 6
    • DOI: 10.1002/cssc.201802692

    Molecular-level driving forces in lignocellulosic biomass deconstruction for bioenergy
    journal, October 2018

    Cellulose–hemicellulose interactions at elevated temperatures increase cellulose recalcitrance to biological conversion
    journal, January 2018

    • Kumar, Rajeev; Bhagia, Samarthya; Smith, Micholas Dean
    • Green Chemistry, Vol. 20, Issue 4
    • DOI: 10.1039/c7gc03518g

    Performances of Several Solvents on the Cleavage of Inter- and Intramolecular Linkages of Lignin in Corncob Residue
    journal, April 2018

    Reaction engineering implications of cellulose crystallinity and water-promoted recrystallization
    journal, January 2019

    • Tyufekchiev, Maksim; Kolodziejczak, Alex; Duan, Pu
    • Green Chemistry, Vol. 21, Issue 20
    • DOI: 10.1039/c9gc02466b

    Use of bacteria for improving the lignocellulose biorefinery process: importance of pre-erosion
    journal, May 2018

    Structural changes in lignocellulosic biomass during activation with ionic liquids comprising 3-methylimidazolium cations and carboxylate anions
    journal, September 2018

    • Moyer, Preenaa; Kim, Keonhee; Abdoulmoumine, Nourredine
    • Biotechnology for Biofuels, Vol. 11, Issue 1
    • DOI: 10.1186/s13068-018-1263-0

    Organosolv-Water Cosolvent Phase Separation on Cellulose and its Influence on the Physical Deconstruction of Cellulose: A Molecular Dynamics Analysis
    journal, November 2017

    Use of bacteria for improving the lignocellulose biorefinery process: importance of pre-erosion
    journal, May 2018

    Structural changes in lignocellulosic biomass during activation with ionic liquids comprising 3-methylimidazolium cations and carboxylate anions
    journal, September 2018

    • Moyer, Preenaa; Kim, Keonhee; Abdoulmoumine, Nourredine
    • Biotechnology for Biofuels, Vol. 11, Issue 1
    • DOI: 10.1186/s13068-018-1263-0
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: