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

Title: Ammonia pretreatment of corn stover enables facile lignin extraction

Abstract

Thermochemical pretreatment of lignocellulose is often employed to render polysaccharides more digestible by carbohydrate-active enzymes to maximize sugar yields. The fate of lignin during pretreatment, however, is highly dependent on the chemistry employed and must be considered in cases where lignin valorization is targeted alongside sugar conversion—an important feature of future biorefinery development. Here, a two-step process is demonstrated in which anhydrous ammonia (AA) pretreatment is followed by mild NaOH extraction on corn stover to solubilize and fractionate lignin. As known, AA pretreatment simultaneously alters the structure of cellulose with enhanced digestibility while redistributing lignin. The AA-pretreated residue is then extracted with dilute NaOH at mild conditions to maximize lignin separation, resulting in a digestible carbohydrate-rich solid fraction and a solubilized lignin stream. Lignin removal of more than 65% with over 84% carbohydrate retention is achieved after mild NaOH extraction of AA-pretreated corn stover with 0.1 M NaOH at 25 °C. Two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy of the AA-pretreated residue shows that ammonolysis of ester bonds occurs to partially liberate hydroxycinnamic acids, and the AA-pretreated/NaOH-extracted residue exhibits a global reduction of all lignin moieties caused by reduced lignin content. A significant reduction (~70%) in the weight-average molecular weight (Mw)more » of extracted lignin is also achieved. Imaging of AA-pretreated/NaOH extracted residues show extensive delamination and disappearance of coalesced lignin globules from within the secondary cell walls. Glycome profiling analyses demonstrates ultrastructural level cell wall modifications induced by AA pretreatment and NaOH extraction, resulting in enhanced extractability of hemicellulosic glycans, indicating enhanced polysaccharide accessibility. The glucose and xylose yields from enzymatic hydrolysis of AA-pretreated/NaOH-extracted corn stover were higher by ~80% and ~60%, respectively, compared to untreated corn stover at 1% solids loadings. For digestions at 20% solids, a benefit of NaOH extraction is realized in achieving ~150 g/L of total monomeric sugars (glucose, xylose, and arabinose) in the enzymatic hydrolysates from AA-pretreated/NaOH-extracted corn stover. Altogether, this process enables facile lignin extraction in tandem with a leading thermochemical pretreatment approach, demonstrating excellent retention of highly digestible polysaccharides in the solid phase and a highly depolymerized, soluble lignin-rich stream.« less

Authors:
 [1];  [1];  [1];  [2];  [3];  [1];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Univ. of Georgia, Athens, GA (United States); Mascoma LLC (Lallemand Inc.), Lebanon, NH (United States)
  3. Univ. of Georgia, Athens, GA (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1346537
Report Number(s):
NREL/JA-2700-68056
Journal ID: ISSN 2168-0485
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 5; Journal Issue: 3; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ammonia; biofuels; fractionation; ligninocellulose; pretreatment

Citation Formats

Mittal, Ashutosh, Katahira, Rui, Donohoe, Bryon S., Pattathil, Sivakumar, Kandemkavil, Sindhu, Reed, Michelle L., Biddy, Mary J., and Beckham, Gregg T. Ammonia pretreatment of corn stover enables facile lignin extraction. United States: N. p., 2017. Web. doi:10.1021/acssuschemeng.6b02892.
Copy to clipboard
Mittal, Ashutosh, Katahira, Rui, Donohoe, Bryon S., Pattathil, Sivakumar, Kandemkavil, Sindhu, Reed, Michelle L., Biddy, Mary J., & Beckham, Gregg T. Ammonia pretreatment of corn stover enables facile lignin extraction. United States. https://doi.org/10.1021/acssuschemeng.6b02892
Copy to clipboard
Mittal, Ashutosh, Katahira, Rui, Donohoe, Bryon S., Pattathil, Sivakumar, Kandemkavil, Sindhu, Reed, Michelle L., Biddy, Mary J., and Beckham, Gregg T. Thu . "Ammonia pretreatment of corn stover enables facile lignin extraction". United States. https://doi.org/10.1021/acssuschemeng.6b02892. https://www.osti.gov/servlets/purl/1346537.
Copy to clipboard
@article{osti_1346537,
title = {Ammonia pretreatment of corn stover enables facile lignin extraction},
author = {Mittal, Ashutosh and Katahira, Rui and Donohoe, Bryon S. and Pattathil, Sivakumar and Kandemkavil, Sindhu and Reed, Michelle L. and Biddy, Mary J. and Beckham, Gregg T.},
abstractNote = {Thermochemical pretreatment of lignocellulose is often employed to render polysaccharides more digestible by carbohydrate-active enzymes to maximize sugar yields. The fate of lignin during pretreatment, however, is highly dependent on the chemistry employed and must be considered in cases where lignin valorization is targeted alongside sugar conversion—an important feature of future biorefinery development. Here, a two-step process is demonstrated in which anhydrous ammonia (AA) pretreatment is followed by mild NaOH extraction on corn stover to solubilize and fractionate lignin. As known, AA pretreatment simultaneously alters the structure of cellulose with enhanced digestibility while redistributing lignin. The AA-pretreated residue is then extracted with dilute NaOH at mild conditions to maximize lignin separation, resulting in a digestible carbohydrate-rich solid fraction and a solubilized lignin stream. Lignin removal of more than 65% with over 84% carbohydrate retention is achieved after mild NaOH extraction of AA-pretreated corn stover with 0.1 M NaOH at 25 °C. Two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy of the AA-pretreated residue shows that ammonolysis of ester bonds occurs to partially liberate hydroxycinnamic acids, and the AA-pretreated/NaOH-extracted residue exhibits a global reduction of all lignin moieties caused by reduced lignin content. A significant reduction (~70%) in the weight-average molecular weight (Mw) of extracted lignin is also achieved. Imaging of AA-pretreated/NaOH extracted residues show extensive delamination and disappearance of coalesced lignin globules from within the secondary cell walls. Glycome profiling analyses demonstrates ultrastructural level cell wall modifications induced by AA pretreatment and NaOH extraction, resulting in enhanced extractability of hemicellulosic glycans, indicating enhanced polysaccharide accessibility. The glucose and xylose yields from enzymatic hydrolysis of AA-pretreated/NaOH-extracted corn stover were higher by ~80% and ~60%, respectively, compared to untreated corn stover at 1% solids loadings. For digestions at 20% solids, a benefit of NaOH extraction is realized in achieving ~150 g/L of total monomeric sugars (glucose, xylose, and arabinose) in the enzymatic hydrolysates from AA-pretreated/NaOH-extracted corn stover. Altogether, this process enables facile lignin extraction in tandem with a leading thermochemical pretreatment approach, demonstrating excellent retention of highly digestible polysaccharides in the solid phase and a highly depolymerized, soluble lignin-rich stream.},
doi = {10.1021/acssuschemeng.6b02892},
journal = {ACS Sustainable Chemistry & Engineering},
number = 3,
volume = 5,
place = {United States},
year = {2017},
month = {2}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acssuschemeng.6b02892
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 6 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:

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

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

Effects of Cellulose Crystallinity, Hemicellulose, and Lignin on the Enzymatic Hydrolysis of Miscanthus sinensis to Monosaccharides
journal, March 2008

  • Yoshida, Makoto; Liu, Yuan; Uchida, Satoshi
  • Bioscience, Biotechnology, and Biochemistry, Vol. 72, Issue 3
  • DOI: 10.1271/bbb.70689

Cellulose crystallinity - a key predictor of the enzymatic hydrolysis rate: Cellulose crystallinity
journal, February 2010

Coordinated development of leading biomass pretreatment technologies
journal, December 2005

Lignin Valorization: Improving Lignin Processing in the Biorefinery
journal, May 2014

  • Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.
  • Science, Vol. 344, Issue 6185, p. 1246843-1246843
  • DOI: 10.1126/science.1246843

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

Adipic acid production from lignin
journal, January 2015

  • Vardon, Derek R.; Franden, Mary Ann; Johnson, Christopher W.
  • Energy & Environmental Science, Vol. 8, Issue 2
  • DOI: 10.1039/C4EE03230F

Enhancing muconic acid production from glucose and lignin-derived aromatic compounds via increased protocatechuate decarboxylase activity
journal, December 2016

  • Johnson, Christopher W.; Salvachúa, Davinia; Khanna, Payal
  • Metabolic Engineering Communications, Vol. 3
  • DOI: 10.1016/j.meteno.2016.04.002

cis,cis-Muconic acid: separation and catalysis to bio-adipic acid for nylon-6,6 polymerization
journal, January 2016

  • Vardon, Derek R.; Rorrer, Nicholas A.; Salvachúa, Davinia
  • Green Chemistry, Vol. 18, Issue 11
  • DOI: 10.1039/C5GC02844B

A Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization in Acidic Environments
journal, November 2013

  • Sturgeon, Matthew R.; Kim, Seonah; Lawrence, Kelsey
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 3, p. 472-485
  • DOI: 10.1021/sc400384w

Alkaline Pretreatment of Corn Stover: Bench-Scale Fractionation and Stream Characterization
journal, May 2014

  • Karp, Eric M.; Donohoe, Bryon S.; O’Brien, Marykate H.
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 6, p. 1481-1491
  • DOI: 10.1021/sc500126u

Alkaline Pretreatment of Switchgrass
journal, May 2015

  • Karp, Eric M.; Resch, Michael G.; Donohoe, Bryon S.
  • ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 7
  • DOI: 10.1021/acssuschemeng.5b00201

Optimization of the ammonia fiber explosion (AFEX) treatment parameters for enzymatic hydrolysis of corn stover
journal, December 2005

  • Teymouri, Farzaneh; Laureano-Perez, Lizbeth; Alizadeh, Hasan
  • Bioresource Technology, Vol. 96, Issue 18, p. 2014-2018
  • DOI: 10.1016/j.biortech.2005.01.016

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

Process optimization to convert forage and sweet sorghum bagasse to ethanol based on ammonia fiber expansion (AFEX) pretreatment
journal, February 2010

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

Pretreatment of Switchgrass by Ammonia Fiber Explosion (AFEX)
journal, January 2005

  • Alizadeh, Hasan; Teymouri, Farzaneh; Gilbert, Thomas I.
  • Applied Biochemistry and Biotechnology, Vol. 124, Issue 1-3, p. 1133-1142
  • DOI: 10.1385/ABAB:124:1-3:1133

An integrated paradigm for cellulosic biorefineries: utilization of lignocellulosic biomass as self-sufficient feedstocks for fuel, food precursors and saccharolytic enzyme production
journal, January 2012

  • Lau, Ming W.; Bals, Bryan D.; Chundawat, Shishir P. S.
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee03596k

Cellulosic ethanol production from AFEX-treated corn stover using Saccharomyces cerevisiae 424A(LNH-ST)
journal, January 2009

  • Lau, M. W.; Dale, B. E.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 5, p. 1368-1373
  • DOI: 10.1073/pnas.0812364106

Evaluation of ammonia fibre expansion (AFEX) pretreatment for enzymatic hydrolysis of switchgrass harvested in different seasons and locations
journal, January 2010

  • Bals, Bryan; Rogers, Chad; Jin, Mingjie
  • Biotechnology for Biofuels, Vol. 3, Issue 1
  • DOI: 10.1186/1754-6834-3-1

Enzymatic hydrolysis of pelletized AFEX™-treated corn stover at high solid loadings: Hydrolysis of Pelletized AFEX Corn Stover
journal, September 2013

  • Bals, Bryan D.; Gunawan, Christa; Moore, Janette
  • Biotechnology and Bioengineering, Vol. 111, Issue 2
  • DOI: 10.1002/bit.25022

Lignin solubilisation and gentle fractionation in liquid ammonia
journal, January 2015

  • Strassberger, Zea; Prinsen, Pepijn; Klis, Frits van der
  • Green Chemistry, Vol. 17, Issue 1
  • DOI: 10.1039/C4GC01143K

Attempted Delignifications with Sodium Bicarbonate - Carbon Dioxide, and with Anhydrous Liquid Ammonia, Under Pressure
journal, November 1956

  • Yan, M. M.; Purves, C. B.
  • Canadian Journal of Chemistry, Vol. 34, Issue 11
  • DOI: 10.1139/v56-207

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

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. 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

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

Liquid-Ammonia and Caustic Mercerization of Cotton Fibers: Changes in Fine Structure and Mechanical Properties
journal, April 1976

  • Rousselle, M. A.; Nelson, M. L.; Hassenboehler, C. B.
  • Textile Research Journal, Vol. 46, Issue 4
  • DOI: 10.1177/004051757604600412

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

Plasticizing wood with Liquid Ammonia
journal, October 1963

  • Schuerch, Conrad
  • Industrial & Engineering Chemistry, Vol. 55, Issue 10
  • DOI: 10.1021/ie50646a004

Cellulose III I Crystal Structure and Hydrogen Bonding by Synchrotron X-ray and Neutron Fiber Diffraction
journal, November 2004

  • Wada, Masahisa; Chanzy, Henri; Nishiyama, Yoshiharu
  • Macromolecules, Vol. 37, Issue 23
  • DOI: 10.1021/ma0485585

Conversion of Cellulose I to Stable Cellulose III
journal, July 1986

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

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

Enzymatic digestibility and pretreatment degradation products of AFEX-treated hardwoods ( Populus nigra )
journal, March 2009

  • Balan, Venkatesh; Sousa, Leonardo da Costa; Chundawat, Shishir P. S.
  • Biotechnology Progress, Vol. 25, Issue 2
  • DOI: 10.1002/btpr.160

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

Extraction of a Lignin Fraction from Maple wood by Liquid Ammonia
journal, December 1956

  • Yan, M. M.; Purves, C. B.
  • Canadian Journal of Chemistry, Vol. 34, Issue 12
  • DOI: 10.1139/v56-227

Reactive extraction of lignin from wood using supercritical ammonia-water mixtures
journal, December 1993

Whole plant cell wall characterization using solution-state 2D NMR
journal, August 2012

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

Insights into plant cell wall structure, architecture, and integrity using glycome profiling of native and AFEX TM -pre-treated biomass
journal, April 2015

  • Pattathil, Sivakumar; Hahn, Michael G.; Dale, Bruce E.
  • Journal of Experimental Botany, Vol. 66, Issue 14
  • DOI: 10.1093/jxb/erv107

Access of cellulase to cellulose and lignin for poplar solids produced by leading pretreatment technologies
journal, May 2009

  • Kumar, Rajeev; Wyman, Charles E.
  • Biotechnology Progress, Vol. 25, Issue 3
  • DOI: 10.1002/btpr.153

Simultaneous saccharification and fermentation of pretreated hardwoods: Effect of Native Lignin Content
journal, January 1997

  • Vinzant, Todd B.; Ehrman, Christine I.; Adney, William S.
  • Applied Biochemistry and Biotechnology, Vol. 62, Issue 1
  • DOI: 10.1007/BF02787987

New perspective on glycoside hydrolase binding to lignin from pretreated corn stover
journal, December 2015

  • Yarbrough, John M.; Mittal, Ashutosh; Mansfield, Elisabeth
  • Biotechnology for Biofuels, Vol. 8, Issue 1
  • DOI: 10.1186/s13068-015-0397-6

The Techno-Economic Basis for Coproduct Manufacturing To Enable Hydrocarbon Fuel Production from Lignocellulosic Biomass
journal, May 2016

Lignin valorization through integrated biological funneling and chemical catalysis
journal, August 2014

  • Linger, J. G.; Vardon, D. R.; Guarnieri, M. T.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 33, p. 12013-12018
  • DOI: 10.1073/pnas.1410657111

Towards lignin consolidated bioprocessing: simultaneous lignin depolymerization and product generation by bacteria
journal, January 2015

  • Salvachúa, Davinia; Karp, Eric M.; Nimlos, Claire T.
  • Green Chemistry, Vol. 17, Issue 11
  • DOI: 10.1039/C5GC01165E

An Empirical Method for Estimating the Degree of Crystallinity of Native Cellulose Using the X-Ray Diffractometer
journal, October 1959

Solution-state 2D NMR of Ball-milled Plant Cell Wall Gels in DMSO-d 6
journal, March 2008

Visualizing lignin coalescence and migration through maize cell walls following thermochemical pretreatment
journal, December 2008

  • Donohoe, Bryon S.; Decker, Stephen R.; Tucker, Melvin P.
  • Biotechnology and Bioengineering, Vol. 101, Issue 5
  • DOI: 10.1002/bit.21959

Immunological Approaches to Plant Cell Wall and Biomass Characterization: Glycome Profiling
book, January 2012

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Perspective on Lignin Oxidation: Advances, Challenges, and Future Directions
    journal, July 2018

    • Vangeel, Thijs; Schutyser, Wouter; Renders, Tom
    • Topics in Current Chemistry, Vol. 376, Issue 4
    • DOI: 10.1007/s41061-018-0207-2

    Revisiting alkaline aerobic lignin oxidation
    journal, January 2018

    • Schutyser, Wouter; Kruger, Jacob S.; Robinson, Allison M.
    • Green Chemistry, Vol. 20, Issue 16
    • DOI: 10.1039/c8gc00502h

    Structural Characterization of Lignin and Its Degradation Products with Spectroscopic Methods
    journal, January 2017

    Effects of Corn Stover Pretreated with NaOH and CaO on Anaerobic Co-Digestion of Swine Manure and Corn Stover
    journal, December 2018

    • You, Zhaoyang; Zhang, Shujuan; Kim, Hyunook
    • Applied Sciences, Vol. 9, Issue 1
    • DOI: 10.3390/app9010123

    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

    Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading
    journal, January 2018

    • Schutyser, W.; Renders, T.; Van den Bosch, S.
    • Chemical Society Reviews, Vol. 47, Issue 3
    • DOI: 10.1039/c7cs00566k

    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
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: