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

Title: Ammonia-salt solvent promotes cellulosic biomass deconstruction under ambient pretreatment conditions to enable rapid soluble sugar production at ultra-low enzyme loadings

Abstract

In this paper, we report a novel ammonia : ammonium salt solvent based pretreatment process that can rapidly dissolve crystalline cellulose into solution and eventually produce highly amorphous cellulose under near-ambient conditions. Pre-activating the cellulose I allomorph to its ammonia–cellulose swollen complex (or cellulose III allomorph) at ambient temperatures facilitated rapid dissolution of the pre-activated cellulose in the ammonia-salt solvent (i.e., ammonium thiocyanate salt dissolved in liquid ammonia) at ambient pressures. For the first time in reported literature, we used time-resolved in situ neutron scattering methods to characterize the cellulose polymorphs structural modification and understand the mechanism of crystalline cellulose dissolution into a ‘molecular’ solution in real-time using ammonia-salt solvents. We also used molecular dynamics simulations to provide insight into solvent interactions that non-covalently disrupted the cellulose hydrogen-bonding network and understand how such solvents are able to rapidly and fully dissolve pre-activated cellulose III. Importantly, the regenerated amorphous cellulose recovered after pretreatment was shown to require nearly ~50-fold lesser cellulolytic enzyme usage compared to native crystalline cellulose I allomorph for achieving near-complete hydrolytic conversion into soluble sugars. Lastly, we provide proof-of-concept results to further showcase how such ammonia-salt solvents can pretreat and fractionate lignocellulosic biomass like corn stover under ambientmore » processing conditions, while selectively co-extracting ~80–85% of total lignin, to produce a highly digestible polysaccharide-enriched feedstock for biorefinery applications. Unlike conventional ammonia-based pretreatment processes (e.g., Ammonia Fiber Expansion or Extractive Ammonia pretreatments), the proposed ammonia-salt process can operate at near-ambient conditions to greatly reduce the pressure/temperature severity necessary for conducting effective ammonia-based pretreatments on lignocellulose.« less

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [3];  [1];  [4];  [1]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [3]; ORCiD logo [3]
  1. Department of Chemical & Biochemical Engineering;Rutgers The State University of New Jersey;Piscataway;USA
  2. Department of Chemical Engineering & Materials Science;Michigan State University;East Lansing;USA
  3. Center for Structural Molecular Biology and Neutron Scattering Division;Oak Ridge National Laboratory;Oak Ridge;USA
  4. Department of Mechanical & Aerospace Engineering;Rutgers The State University of New Jersey;Piscataway;USA
  5. UT/ORNL Center for Molecular Biophysics;Oak Ridge National Laboratory;Oak Ridge;USA
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1577381
Alternate Identifier(s):
OSTI ID: 1649428
Grant/Contract Number:  
AC05-00OR22725; FC02-07ER64494; ERKP291; ERKP752; 1604421; 1846797
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Name: Green Chemistry Journal Volume: 22 Journal Issue: 1; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chundawat, Shishir S., Sousa, Leonardo Costa, Roy, Shyamal, Yang, Zhi, Gupta, Shashwat, Pal, Ramendra, Zhao, Chao, Liu, Shih-Hsien, Petridis, Loukas, O'Neill, Hugh, and Pingali, Sai Venkatesh. Ammonia-salt solvent promotes cellulosic biomass deconstruction under ambient pretreatment conditions to enable rapid soluble sugar production at ultra-low enzyme loadings. United Kingdom: N. p., 2020. Web. doi:10.1039/c9gc03524a.
Chundawat, Shishir S., Sousa, Leonardo Costa, Roy, Shyamal, Yang, Zhi, Gupta, Shashwat, Pal, Ramendra, Zhao, Chao, Liu, Shih-Hsien, Petridis, Loukas, O'Neill, Hugh, & Pingali, Sai Venkatesh. Ammonia-salt solvent promotes cellulosic biomass deconstruction under ambient pretreatment conditions to enable rapid soluble sugar production at ultra-low enzyme loadings. United Kingdom. doi:10.1039/c9gc03524a.
Chundawat, Shishir S., Sousa, Leonardo Costa, Roy, Shyamal, Yang, Zhi, Gupta, Shashwat, Pal, Ramendra, Zhao, Chao, Liu, Shih-Hsien, Petridis, Loukas, O'Neill, Hugh, and Pingali, Sai Venkatesh. Wed . "Ammonia-salt solvent promotes cellulosic biomass deconstruction under ambient pretreatment conditions to enable rapid soluble sugar production at ultra-low enzyme loadings". United Kingdom. doi:10.1039/c9gc03524a.
@article{osti_1577381,
title = {Ammonia-salt solvent promotes cellulosic biomass deconstruction under ambient pretreatment conditions to enable rapid soluble sugar production at ultra-low enzyme loadings},
author = {Chundawat, Shishir S. and Sousa, Leonardo Costa and Roy, Shyamal and Yang, Zhi and Gupta, Shashwat and Pal, Ramendra and Zhao, Chao and Liu, Shih-Hsien and Petridis, Loukas and O'Neill, Hugh and Pingali, Sai Venkatesh},
abstractNote = {In this paper, we report a novel ammonia : ammonium salt solvent based pretreatment process that can rapidly dissolve crystalline cellulose into solution and eventually produce highly amorphous cellulose under near-ambient conditions. Pre-activating the cellulose I allomorph to its ammonia–cellulose swollen complex (or cellulose III allomorph) at ambient temperatures facilitated rapid dissolution of the pre-activated cellulose in the ammonia-salt solvent (i.e., ammonium thiocyanate salt dissolved in liquid ammonia) at ambient pressures. For the first time in reported literature, we used time-resolved in situ neutron scattering methods to characterize the cellulose polymorphs structural modification and understand the mechanism of crystalline cellulose dissolution into a ‘molecular’ solution in real-time using ammonia-salt solvents. We also used molecular dynamics simulations to provide insight into solvent interactions that non-covalently disrupted the cellulose hydrogen-bonding network and understand how such solvents are able to rapidly and fully dissolve pre-activated cellulose III. Importantly, the regenerated amorphous cellulose recovered after pretreatment was shown to require nearly ~50-fold lesser cellulolytic enzyme usage compared to native crystalline cellulose I allomorph for achieving near-complete hydrolytic conversion into soluble sugars. Lastly, we provide proof-of-concept results to further showcase how such ammonia-salt solvents can pretreat and fractionate lignocellulosic biomass like corn stover under ambient processing conditions, while selectively co-extracting ~80–85% of total lignin, to produce a highly digestible polysaccharide-enriched feedstock for biorefinery applications. Unlike conventional ammonia-based pretreatment processes (e.g., Ammonia Fiber Expansion or Extractive Ammonia pretreatments), the proposed ammonia-salt process can operate at near-ambient conditions to greatly reduce the pressure/temperature severity necessary for conducting effective ammonia-based pretreatments on lignocellulose.},
doi = {10.1039/c9gc03524a},
journal = {Green Chemistry},
number = 1,
volume = 22,
place = {United Kingdom},
year = {2020},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/c9gc03524a

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

True molecular solutions of natural cellulose in the binary ionic liquid-containing solvent mixtures
journal, November 2014


Cellulose Dissolution in Ionic Liquid: Ion Binding Revealed by Neutron Scattering
journal, September 2018


Reflections on the Solubility of Cellulose
journal, November 2010

  • Pinkert, André; Marsh, Kenneth N.; Pang, Shusheng
  • Industrial & Engineering Chemistry Research, Vol. 49, Issue 22
  • DOI: 10.1021/ie1006596

A study on the mechanism of dissolution of the cellulose/NH3/NH4SCN system. I
journal, January 1994

  • Cuculo, J. A.; Smith, C. B.; Sangwatanaroj, U.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 32, Issue 2
  • DOI: 10.1002/pola.1994.080320203

Nonenzymatic Sugar Production from Biomass Using Biomass-Derived  -Valerolactone
journal, January 2014


Next-generation ammonia pretreatment enhances cellulosic biofuel production
journal, January 2016

  • da Costa Sousa, Leonardo; Jin, Mingjie; Chundawat, Shishir P. S.
  • Energy & Environmental Science, Vol. 9, Issue 4
  • DOI: 10.1039/C5EE03051J

The solubility of cellulose in liquid ammonia/salt solutions
journal, December 1980

  • Hudson, Samuel M.; Cuculo, J. A.
  • Journal of Polymer Science: Polymer Chemistry Edition, Vol. 18, Issue 12
  • DOI: 10.1002/pol.1980.170181214

High-throughput microplate technique for enzymatic hydrolysis of lignocellulosic biomass
journal, January 2008

  • Chundawat, Shishir P. S.; Balan, Venkatesh; Dale, Bruce E.
  • Biotechnology and Bioengineering, Vol. 99, Issue 6
  • DOI: 10.1002/bit.21805

Transforming biomass conversion with ionic liquids: process intensification and the development of a high-gravity, one-pot process for the production of cellulosic ethanol
journal, January 2016

  • Xu, Feng; Sun, Jian; Konda, N. V. S. N. Murthy
  • Energy & Environmental Science, Vol. 9, Issue 3
  • DOI: 10.1039/C5EE02940F

Solubility of Cellulose in Ammonia salt Solutions
journal, November 1931

  • Scherer, Philip C.
  • Journal of the American Chemical Society, Vol. 53, Issue 11
  • DOI: 10.1021/ja01362a012

SANS study of cellulose extracted from switchgrass
journal, October 2010

  • Pingali, Sai Venkatesh; Urban, Volker S.; Heller, William T.
  • Acta Crystallographica Section D Biological Crystallography, Vol. 66, Issue 11
  • DOI: 10.1107/S0907444910020408

The initial structure of cellulose during ammonia pretreatment
journal, March 2014


Techno-economic analysis of a lignocellulosic ethanol biorefinery with ionic liquid pre-treatment
journal, June 2011

  • Klein-Marcuschamer, Daniel; Simmons, Blake A.; Blanch, Harvey W.
  • Biofuels, Bioproducts and Biorefining, Vol. 5, Issue 5
  • DOI: 10.1002/bbb.303

Multi-scale visualization and characterization of lignocellulosic plant cell wall deconstruction during thermochemical pretreatment
journal, January 2011

  • Chundawat, Shishir P. S.; Donohoe, Bryon S.; da Costa Sousa, Leonardo
  • Energy & Environmental Science, Vol. 4, Issue 3, 973
  • DOI: 10.1039/c0ee00574f

Liquid Ammonia as a Solvent. III. The Solubility of Inorganic Salts at 25°
journal, September 1933

  • Hunt, Herschel; Boncyk, L.
  • Journal of the American Chemical Society, Vol. 55, Issue 9
  • DOI: 10.1021/ja01336a005

Theory, practice and prospects of X-ray and neutron scattering for lignocellulosic biomass characterization: towards understanding biomass pretreatment
journal, January 2015

  • Cheng, Gang; Zhang, Xin; Simmons, Blake
  • Energy & Environmental Science, Vol. 8, Issue 2
  • DOI: 10.1039/C4EE03147D

CHEM21 selection guide of classical- and less classical-solvents
journal, January 2016

  • Prat, Denis; Wells, Andy; Hayler, John
  • Green Chemistry, Vol. 18, Issue 1
  • DOI: 10.1039/C5GC01008J

Molecular-Level Origins of Biomass Recalcitrance: Decrystallization Free Energies for Four Common Cellulose Polymorphs
journal, April 2011

  • Beckham, Gregg T.; Matthews, James F.; Peters, Baron
  • The Journal of Physical Chemistry B, Vol. 115, Issue 14
  • DOI: 10.1021/jp1106394

X-Ray Studies of Reactions of Cellulose in Non-Aqueous Systems. II. Interaction of Cellulose and Primary Amines 1
journal, July 1943

  • Davis, W. E.; Barry, A. J.; Peterson, F. C.
  • Journal of the American Chemical Society, Vol. 65, Issue 7
  • DOI: 10.1021/ja01247a012

Design of low-cost ionic liquids for lignocellulosic biomass pretreatment
journal, January 2015

  • George, Anthe; Brandt, Agnieszka; Tran, Kim
  • Green Chemistry, Vol. 17, Issue 3
  • DOI: 10.1039/C4GC01208A

Dry-grind processing using amylase corn and superior yeast to reduce the exogenous enzyme requirements in bioethanol production
journal, October 2016


A study on the mechanism of dissolution of the cellulose/NH3/NH4SCN system. II.
journal, January 1994

  • Cuculo, J. A.; Smith, C. B.; Sangwatanaroj, U.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 32, Issue 2
  • DOI: 10.1002/pola.1994.080320204

Efficient biomass pretreatment using ionic liquids derived from lignin and hemicellulose
journal, August 2014

  • Socha, A. M.; Parthasarathi, R.; Shi, J.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 35
  • DOI: 10.1073/pnas.1405685111

Coarse-Grained Model for the Interconversion between Native and Liquid Ammonia-Treated Crystalline Cellulose
journal, July 2012

  • Bellesia, Giovanni; Chundawat, Shishir P. S.; Langan, Paul
  • The Journal of Physical Chemistry B, Vol. 116, Issue 28
  • DOI: 10.1021/jp300354q

Recent process improvements for the ammonia fiber expansion (AFEX) process and resulting reductions in minimum ethanol selling price
journal, November 2008


Deactivation of Cellulase at the Air-Liquid Interface Is the Main Cause of Incomplete Cellulose Conversion at Low Enzyme Loadings
journal, January 2018


The solubility of cellulose in liquid ammonia/ammonium thiocyanate solution: The effect of composition and temperature on dissolution and solution properties
journal, March 1983

  • Hudson, S. M.; Cuculo, J. A.; Wadsworth, L. C.
  • Journal of Polymer Science: Polymer Chemistry Edition, Vol. 21, Issue 3
  • DOI: 10.1002/pol.1983.170210302

Irena : tool suite for modeling and analysis of small-angle scattering
journal, February 2009


Deconstruction of Lignocellulosic Biomass to Fuels and Chemicals
journal, July 2011


Liquid ammonia solutions. XII. Raman study of nitrates and thiocyanates
journal, March 1974

  • Lemley, A. T.; Lagowski, J. J.
  • The Journal of Physical Chemistry, Vol. 78, Issue 7
  • DOI: 10.1021/j100600a013

Differential Fermentation of Cellulose Allomorphs by Ruminal Cellulolytic Bacteria
journal, January 1991


Impact of Ammonia Pretreatment Conditions on the Cellulose III Allomorph Ultrastructure and Its Enzymatic Digestibility
journal, August 2019

  • Sousa, Leonardo da Costa; Humpula, James; Balan, Venkatesh
  • ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 17
  • DOI: 10.1021/acssuschemeng.9b00606

Effects of alkaline or liquid-ammonia treatment on crystalline cellulose: changes in crystalline structure and effects on enzymatic digestibility
journal, January 2011

  • Mittal, Ashutosh; Katahira, Rui; Himmel, Michael E.
  • Biotechnology for Biofuels, Vol. 4, Issue 1
  • DOI: 10.1186/1754-6834-4-41

Mixture optimization of six core glycosyl hydrolases for maximizing saccharification of ammonia fiber expansion (AFEX) pretreated corn stover
journal, April 2010

  • Gao, Dahai; Chundawat, Shishir P. S.; Krishnan, Chandraraj
  • Bioresource Technology, Vol. 101, Issue 8, p. 2770-2781
  • DOI: 10.1016/j.biortech.2009.10.056

Breakdown of Cell Wall Nanostructure in Dilute Acid Pretreated Biomass
journal, September 2010

  • Pingali, Sai Venkatesh; Urban, Volker S.; Heller, William T.
  • Biomacromolecules, Vol. 11, Issue 9
  • DOI: 10.1021/bm100455h

Restructuring the Crystalline Cellulose Hydrogen Bond Network Enhances Its Depolymerization Rate
journal, July 2011

  • Chundawat, Shishir P. S.; Bellesia, Giovanni; Uppugundla, Nirmal
  • Journal of the American Chemical Society, Vol. 133, Issue 29
  • DOI: 10.1021/ja2011115

The effect of liquid anhydrous ammonia in the structure and morphology of cotton cellulose
journal, January 1971

  • Lewin, Menachem; Roldan, Luis G.
  • Journal of Polymer Science Part C: Polymer Symposia, Vol. 36, Issue 1
  • DOI: 10.1002/polc.5070360115

Small-Angle Scattering from Polymeric Mass Fractals of Arbitrary Mass-Fractal Dimension
journal, April 1996


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

Isolation and characterization of new lignin streams derived from extractive-ammonia (EA) pretreatment
journal, January 2016

  • da Costa Sousa, Leonardo; Foston, Marcus; Bokade, Vijay
  • Green Chemistry, Vol. 18, Issue 15
  • DOI: 10.1039/C6GC00298F

An X-ray Diffraction Study of the Action of Liquid Ammonia on Cellulose and Its Derivatives
journal, June 1937

  • Clark, G. L.; Parker, E. A.
  • The Journal of Physical Chemistry, Vol. 41, Issue 6
  • DOI: 10.1021/j150384a001

x-Ray Studies of Reactions of Cellulose in Non-Aqueous Systems. I. Interaction of Cellulose and Liquid Ammonia 1
journal, February 1936

  • Barry, A. J.; Peterson, F. C.; King, A. J.
  • Journal of the American Chemical Society, Vol. 58, Issue 2
  • DOI: 10.1021/ja01293a043

Inexpensive ionic liquids: [HSO 4 ] -based solvent production at bulk scale
journal, January 2014

  • Chen, Long; Sharifzadeh, Mahdi; Mac Dowell, Niall
  • Green Chem., Vol. 16, Issue 6
  • DOI: 10.1039/C4GC00016A

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

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


Proteomics-based Compositional Analysis of Complex Cellulase–Hemicellulase Mixtures
journal, October 2011

  • Chundawat, Shishir P. S.; Lipton, Mary S.; Purvine, Samuel O.
  • Journal of Proteome Research, Vol. 10, Issue 10
  • DOI: 10.1021/pr101234z

Approximations Leading to a Unified Exponential/Power-Law Approach to Small-Angle Scattering
journal, December 1995


EQUILIBRIUM IN THE SYSTEM AMMONIA-AMMONIUM THIOCYANATE. 1
journal, January 1920

  • Foote, H. W.; Hunter, M. A.
  • Journal of the American Chemical Society, Vol. 42, Issue 1
  • DOI: 10.1021/ja01446a010

Fractionating recalcitrant lignocellulose at modest reaction conditions
journal, January 2007

  • Zhang, Yi-Heng Percival; Ding, Shi-You; Mielenz, Jonathan R.
  • Biotechnology and Bioengineering, Vol. 97, Issue 2
  • DOI: 10.1002/bit.21386

Integrated enzyme production lowers the cost of cellulosic ethanol: INTEGRATED ENZYME PRODUCTION LOWERS THE COST OF CELLULOSIC ETHANOL
journal, February 2016

  • Johnson, Eric
  • Biofuels, Bioproducts and Biorefining, Vol. 10, Issue 2
  • DOI: 10.1002/bbb.1634

Process and technoeconomic analysis of leading pretreatment technologies for lignocellulosic ethanol production using switchgrass
journal, December 2011


Multifaceted characterization of cell wall decomposition products formed during ammonia fiber expansion (AFEX) and dilute acid based pretreatments
journal, November 2010


Cellulase-Inspired Solid Acids for Cellulose Hydrolysis: Structural Explanations for High Catalytic Activity
journal, January 2018


Bio-SANS—A dedicated facility for neutron structural biology at Oak Ridge National Laboratory
journal, November 2006


Cellulose solvent-based biomass pretreatment breaks highly ordered hydrogen bonds in cellulose fibers of switchgrass
journal, November 2010

  • Sathitsuksanoh, Noppadon; Zhu, Zhiguang; Wi, Sungsool
  • Biotechnology and Bioengineering, Vol. 108, Issue 3
  • DOI: 10.1002/bit.22964

Light-scattering studies on solutions of cellulose in the ammonia/ammonium thiocyanate solvent system. I. Classical light-scattering
journal, April 1991

  • De Groot, A. W.; Guinnup, D. E.; Theil, M. H.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 29, Issue 5
  • DOI: 10.1002/polb.1991.090290504

Light-scattering studies on solutions of cellulose in the ammonia / ammonium thiocyanate solvent system. II. Quasielastic light-scattering and liquid crystal study
journal, April 1991

  • De Groot, A. W.; Guinnup, D. E.; Thiel, M. H.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 29, Issue 5
  • DOI: 10.1002/polb.1991.090290505

A 13C-NMR spectral study of cellulose and glucopyranose dissolved in the NH3/NH4SCN solvent system
journal, April 1986

  • Degroot, A. W.; Carroll, F. I.; Cuculo, J. A.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 24, Issue 4
  • DOI: 10.1002/pola.1986.080240410

    Works referencing / citing this record:

    In operando monitoring of wood transformation during pretreatment with ionic liquids
    journal, April 2020