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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]
+ Show Author Affiliations
  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.
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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.
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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.
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@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}
}
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DOI: 10.1039/c9gc03524a
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