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Title: Natural deep eutectic solvent mediated extrusion for continuous high-solid pretreatment of lignocellulosic biomass

Abstract

Several deep eutectic solvents (DESs) have been demonstrated to be highly effective for lignocellulosic biomass pretreatment, combining the advantages of simple synthesis, relatively low chemical cost and better biocompatibility. However, low biomass loading that is usually involved with DES pretreatment hinders its practical use. Here, a twin-screw extruder was used for pretreating biomass sorghum bagasse at solid loadings up to 50%, mediated by a neutral-pH DES, choline chloride : glycerol (ChCl : Gly). This continuous extrusion process led to high glucose and xylose yields of >85% from enzymatic saccharification of the pretreated sorghum. A combination of microscopic, spectroscopic, and X-ray diffraction analyses demonstrate a high degree of defibration and disruption of the biomass cell wall structures; however, little or no change in chemical compositions. Further results from gel permeation chromatographic (GPC) and nuclear magnetic resonance (NMR) spectroscopic analyses indicate that ChCl : Gly-mediated extrusion preserved the basic lignin structural characteristics with no significant differences between extruded biomass at a solid loading of 30% and 50%. This study demonstrates the potential of DES-mediated extrusion as a highly effective continuous high-solid biomass pretreatment technology for industrially relevant applications.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [4];  [5];  [5];  [2]; ORCiD logo [6]; ORCiD logo [2]
  1. Chinese Academy of Tropical Agricultural Sciences, Haikou (China). Haikou Experimental Station; Univ. of Kentucky, Lexington, KY (United States). Biosystems and Agricultural Engineering
  2. Univ. of Kentucky, Lexington, KY (United States). Biosystems and Agricultural Engineering
  3. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Forestry, Wildlife, and Fisheries, Center for Renewable Carbon
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Institute for Biological Sciences (JICS), Center for BioEnergy Innovation, Biosciences Division
  5. Chinese Academy of Tropical Agricultural Sciences, Haikou (China). Haikou Experimental Station
  6. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Forestry, Wildlife, and Fisheries, Center for Renewable Carbon and Dept. of Chemical and Biomolecular Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Institute for Biological Sciences (JICS), Center for BioEnergy Innovation, Biosciences Division
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDA; National Natural Science Foundation of China (NSFC); Chinese Scholarship Council; Central Public-interest Scientific Institution Basal Research Fund for Chinese Academy of Tropical Agricultural Sciences
OSTI Identifier:
1651282
Alternate Identifier(s):
OSTI ID: 1642252
Grant/Contract Number:  
AC05-00OR22725; 1015068; 1018315; 51708548; 201803260012; 17CXTD-05
Resource Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 22; Journal Issue: 16; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ai, Binling, Li, Wenqi, Woomer, Joseph, Li, Mi, Pu, Yunqiao, Sheng, Zhanwu, Zheng, Lili, Adedeji, Akinbode, Ragauskas, Arthur J., and Shi, Jian. Natural deep eutectic solvent mediated extrusion for continuous high-solid pretreatment of lignocellulosic biomass. United States: N. p., 2020. Web. doi:10.1039/d0gc01560a.
Ai, Binling, Li, Wenqi, Woomer, Joseph, Li, Mi, Pu, Yunqiao, Sheng, Zhanwu, Zheng, Lili, Adedeji, Akinbode, Ragauskas, Arthur J., & Shi, Jian. Natural deep eutectic solvent mediated extrusion for continuous high-solid pretreatment of lignocellulosic biomass. United States. https://doi.org/10.1039/d0gc01560a
Ai, Binling, Li, Wenqi, Woomer, Joseph, Li, Mi, Pu, Yunqiao, Sheng, Zhanwu, Zheng, Lili, Adedeji, Akinbode, Ragauskas, Arthur J., and Shi, Jian. Tue . "Natural deep eutectic solvent mediated extrusion for continuous high-solid pretreatment of lignocellulosic biomass". United States. https://doi.org/10.1039/d0gc01560a. https://www.osti.gov/servlets/purl/1651282.
@article{osti_1651282,
title = {Natural deep eutectic solvent mediated extrusion for continuous high-solid pretreatment of lignocellulosic biomass},
author = {Ai, Binling and Li, Wenqi and Woomer, Joseph and Li, Mi and Pu, Yunqiao and Sheng, Zhanwu and Zheng, Lili and Adedeji, Akinbode and Ragauskas, Arthur J. and Shi, Jian},
abstractNote = {Several deep eutectic solvents (DESs) have been demonstrated to be highly effective for lignocellulosic biomass pretreatment, combining the advantages of simple synthesis, relatively low chemical cost and better biocompatibility. However, low biomass loading that is usually involved with DES pretreatment hinders its practical use. Here, a twin-screw extruder was used for pretreating biomass sorghum bagasse at solid loadings up to 50%, mediated by a neutral-pH DES, choline chloride : glycerol (ChCl : Gly). This continuous extrusion process led to high glucose and xylose yields of >85% from enzymatic saccharification of the pretreated sorghum. A combination of microscopic, spectroscopic, and X-ray diffraction analyses demonstrate a high degree of defibration and disruption of the biomass cell wall structures; however, little or no change in chemical compositions. Further results from gel permeation chromatographic (GPC) and nuclear magnetic resonance (NMR) spectroscopic analyses indicate that ChCl : Gly-mediated extrusion preserved the basic lignin structural characteristics with no significant differences between extruded biomass at a solid loading of 30% and 50%. This study demonstrates the potential of DES-mediated extrusion as a highly effective continuous high-solid biomass pretreatment technology for industrially relevant applications.},
doi = {10.1039/d0gc01560a},
journal = {Green Chemistry},
number = 16,
volume = 22,
place = {United States},
year = {Tue Jul 07 00:00:00 EDT 2020},
month = {Tue Jul 07 00:00:00 EDT 2020}
}

Works referenced in this record:

Deep eutectic solvent pretreatment enabling full utilization of switchgrass
journal, September 2018


Facile pretreatment of lignocellulosic biomass using deep eutectic solvents
journal, November 2016


Continuous pretreatment of sugarcane biomass using a twin-screw extruder
journal, March 2017

  • Kuster Moro, Mariana; Sposina Sobral Teixeira, Ricardo; Sant’Ana da Silva, Ayla
  • Industrial Crops and Products, Vol. 97
  • DOI: 10.1016/j.indcrop.2016.12.051

Biocompatible Deep Eutectic Solvents Based on Choline Chloride: Characterization and Application to the Extraction of Rutin from Sophora japonica
journal, October 2015


Xylooligomers are strong inhibitors of cellulose hydrolysis by enzymes
journal, December 2010


Pretreatment of lignocellulose: Formation of inhibitory by-products and strategies for minimizing their effects
journal, January 2016


Multiple hydrogen bond coordination in three-constituent deep eutectic solvents enhances lignin fractionation from biomass
journal, January 2018

  • Xia, Qinqin; Liu, Yongzhuang; Meng, Juan
  • Green Chemistry, Vol. 20, Issue 12
  • DOI: 10.1039/C8GC00900G

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

Assessing the Facile Pretreatments of Bagasse for Efficient Enzymatic Conversion and Their Impacts on Structural and Chemical Properties
journal, November 2018


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

Isolation of Cellulolytic Enzyme Lignin from Wood Preswollen/Dissolved in Dimethyl Sulfoxide/ N -Methylimidazole
journal, March 2010

  • Zhang, Aiping; Lu, Fachuang; Sun, Run-Cang
  • Journal of Agricultural and Food Chemistry, Vol. 58, Issue 6
  • DOI: 10.1021/jf903998d

Evaluation of toxicity and biodegradability of choline chloride based deep eutectic solvents
journal, February 2015

  • Radošević, Kristina; Cvjetko Bubalo, Marina; Gaurina Srček, Višnje
  • Ecotoxicology and Environmental Safety, Vol. 112
  • DOI: 10.1016/j.ecoenv.2014.09.034

Biocompatible Choline-Based Deep Eutectic Solvents Enable One-Pot Production of Cellulosic Ethanol
journal, May 2018


Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies
journal, September 2009


Influence of furfural on anaerobic glycolytic kinetics ofSaccharomyces cerevisiae in batch culture
journal, February 1999


Pretreatment of wheat straw leads to structural changes and improved enzymatic hydrolysis
journal, January 2018


Application of cellulase and hemicellulase to pure xylan, pure cellulose, and switchgrass solids from leading pretreatments
journal, December 2011


Techno‐economic evaluation of a natural deep eutectic solvent‐based biorefinery: Exploring different design scenarios
journal, May 2020

  • Kumar, Adepu K.; Sharma, Shaishav; Dixit, Gaurav
  • Biofuels, Bioproducts and Biorefining, Vol. 14, Issue 4
  • DOI: 10.1002/bbb.2110

Dry jet-wet spinning of strong cellulose filaments from ionic liquid solution
journal, September 2014


Economic impact of total solids loading on enzymatic hydrolysis of dilute acid pretreated corn stover
journal, April 2010

  • Humbird, David; Mohagheghi, Ali; Dowe, Nancy
  • Biotechnology Progress, Vol. 26, Issue 5
  • DOI: 10.1002/btpr.441

Deep eutectic solvents’ ability to solubilize lignin, cellulose, and hemicellulose; thermal stability; and density
journal, August 2017


Soluble inhibitors/deactivators of cellulase enzymes from lignocellulosic biomass
journal, April 2011


Effect of constituents molar ratios of deep eutectic solvents on rice straw fractionation efficiency and the micro-mechanism investigation
journal, September 2018


New insights into the structure and composition of technical lignins: a comparative characterisation study
journal, January 2016

  • Constant, Sandra; Wienk, Hans L. J.; Frissen, Augustinus E.
  • Green Chemistry, Vol. 18, Issue 9
  • DOI: 10.1039/C5GC03043A

The path forward for lignocellulose biorefineries: Bottlenecks, solutions, and perspective on commercialization
journal, September 2018


Characterization and Catalytic Transfer Hydrogenolysis of Deep Eutectic Solvent Extracted Sorghum Lignin to Phenolic Compounds
journal, June 2018


Waste glycerol from biodiesel synthesis as a component in deep eutectic solvents
journal, October 2015


IONCELL-P&F: Pulp Fractionation and Fiber Spinning with Ionic Liquids
journal, July 2016

  • Stepan, Agnes M.; Michud, Anne; Hellstén, Sanna
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 29
  • DOI: 10.1021/acs.iecr.6b00071

Fractionation and characterization of lignin streams from unique high-lignin content endocarp feedstocks
journal, November 2018


Continuous pretreatment of sugarcane bagasse at high loading in an ionic liquid using a twin-screw extruder
journal, January 2013

  • da Silva, Ayla Sant'Ana; Teixeira, Ricardo Sposina Sobral; Endo, Takashi
  • Green Chemistry, Vol. 15, Issue 7
  • DOI: 10.1039/c3gc40352a

pK a -Values of Guaiacyl and Syringyl Phenols Related to Lignin
journal, August 2000

  • Ragnar, Martin; Lindgren, Christofer T.; Nilvebrant, Nils-Olof
  • Journal of Wood Chemistry and Technology, Vol. 20, Issue 3
  • DOI: 10.1080/02773810009349637

An economically viable ionic liquid for the fractionation of lignocellulosic biomass
journal, January 2017

  • Brandt-Talbot, Agnieszka; Gschwend, Florence J. V.; Fennell, Paul S.
  • Green Chemistry, Vol. 19, Issue 13
  • DOI: 10.1039/C7GC00705A

Linking lignin source with structural and electrochemical properties of lignin-derived carbon materials
journal, January 2018

  • Li, Wenqi; Zhang, Yan; Das, Lalitendu
  • RSC Advances, Vol. 8, Issue 68
  • DOI: 10.1039/C8RA08539K

Sugar production from wheat straw biomass by alkaline extrusion and enzymatic hydrolysis
journal, February 2016


Recent advances in understanding the role of cellulose accessibility in enzymatic hydrolysis of lignocellulosic substrates
journal, June 2014


Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance
journal, January 2010

  • Park, Sunkyu; Baker, John O.; Himmel, Michael E.
  • Biotechnology for Biofuels, Vol. 3, Issue 1
  • DOI: 10.1186/1754-6834-3-10

Advances in lignin valorization towards bio-based chemicals and fuels: Lignin biorefinery
journal, November 2019


Extrusion as a pretreatment for lignocellulosic biomass: Fundamentals and applications
journal, December 2017


Natural Deep Eutectic Solvents: Properties, Applications, and Perspectives
journal, November 2017


Optimization of integrated alkaline–extrusion pretreatment of barley straw for sugar production by enzymatic hydrolysis
journal, May 2013


Understanding Factors that Limit Enzymatic Hydrolysis of Biomass: Characterization of Pretreated Corn Stover
journal, January 2005

  • Laureano-Perez, Lizbeth; Teymouri, Farzaneh; Alizadeh, Hasan
  • Applied Biochemistry and Biotechnology, Vol. 124, Issue 1-3
  • DOI: 10.1385/ABAB:124:1-3:1081

Effect of crystallinity and degree of polymerization of cellulose on enzymatic saccharification
journal, October 1984


Enzymatic saccharification of woody biomass micro/nanofibrillated by continuous extrusion process I – Effect of additives with cellulose affinity
journal, January 2009


Natural Deep Eutectic Solvents – Solvents for the 21st Century
journal, March 2014

  • Paiva, Alexandre; Craveiro, Rita; Aroso, Ivo
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 5
  • DOI: 10.1021/sc500096j

New natural and renewable low transition temperature mixtures (LTTMs): screening as solvents for lignocellulosic biomass processing
journal, January 2012

  • Francisco, María; van den Bruinhorst, Adriaan; Kroon, Maaike C.
  • Green Chemistry, Vol. 14, Issue 8
  • DOI: 10.1039/c2gc35660k

Contribution of Deep Eutectic Solvents for Biomass Processing: Opportunities, Challenges, and Limitations
journal, March 2015

  • Vigier, Karine De Oliveira; Chatel, Gregory; Jérôme, François
  • ChemCatChem, Vol. 7, Issue 8
  • DOI: 10.1002/cctc.201500134

One-pot ionic liquid pretreatment and saccharification of switchgrass
journal, January 2013

  • Shi, Jian; Gladden, John M.; Sathitsuksanoh, Noppadon
  • Green Chemistry, Vol. 15, Issue 9
  • DOI: 10.1039/c3gc40545a

Glycerol from biodiesel production: Technological paths for sustainability
journal, May 2018

  • Monteiro, Marcos Roberto; Kugelmeier, Cristie Luis; Pinheiro, Rafael Sanaiotte
  • Renewable and Sustainable Energy Reviews, Vol. 88
  • DOI: 10.1016/j.rser.2018.02.019