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Title: Relationship between lignocellulosic biomass dissolution and physicochemical properties of ionic liquids composed of 3-methylimidazolium cations and carboxylate anions

Abstract

The ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([EMIM]Acetate) has been widely used for biomass processing, i.e., to pretreat, activate, or fractionate lignocellulosic biomass to produce soluble sugars and lignin. However, this IL does not achieve high biomass solubility, therefore minimizing the efficiency of biomass processing. In this paper, [EMIM]Acetate and three other ILs composed of different 3-methylimidazolium cations and carboxylate anions ([EMIM]Formate, 1-allyl-3-methylimidazolium ([AMIM]) formate, and [AMIM]Acetate) were analyzed to relate their physicochemical properties to their biomass solubility performance. While all four ILs are able to dissolve hybrid poplar under fairly mild process conditions (80 °C and 100 RPM stirring), [AMIM]Formate and [AMIM]Acetate have particularly increased biomass solubility of 40 and 32%, respectively, relative to [EMIM]Acetate. Molecular dynamics simulations suggest that strong interactions between IL and specific plant biopolymers may contribute to this enhanced solubilization, as the calculated second virial coefficients between ILs and hemicellullose are most favorable for [AMIM]Formate, matching the trend of the experimental solubility measurements. The simulations also reveal that the interactions between the ILs and hemicellulose are an important factor in determining the overall biomass solubility, whereas lignin–IL interactions were not found to vary significantly, consistent with literature. Finally, the combined experimental and simulation studies identify [AMIM]Formatemore » as an efficient biomass solvent and explain its efficacy, suggesting a new approach to rationally select ionic liquid solvents for lignocellulosic deconstruction.« less

Authors:
 [1];  [2];  [1];  [3];  [2];  [2];  [3]
+ Show Author Affiliations
  1. Univ. of Tennessee, Knoxville, TN (United States). Center for Renewable Carbon. Dept. of Biosystems Engineering and Soil Science
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Molecular Biophysics; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Biochemistry and Cellular and Molecular Biology
  3. Univ. of Tennessee, Knoxville, TN (United States). Center for Renewable Carbon
Publication Date:
Research Org.:
Oak Ridge National Laboratory, Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Science Foundation (NSF)
OSTI Identifier:
1423012
Grant/Contract Number:  
AC05-00OR22725; 151181
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 20; Journal Issue: 4; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Moyer, Preenaa, Smith, Micholas Dean, Abdoulmoumine, Nourredine, Chmely, Stephen C., Smith, Jeremy C., Petridis, Loukas, and Labbé, Nicole. Relationship between lignocellulosic biomass dissolution and physicochemical properties of ionic liquids composed of 3-methylimidazolium cations and carboxylate anions. United States: N. p., 2018. Web. doi:10.1039/C7CP07195G.
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Moyer, Preenaa, Smith, Micholas Dean, Abdoulmoumine, Nourredine, Chmely, Stephen C., Smith, Jeremy C., Petridis, Loukas, & Labbé, Nicole. Relationship between lignocellulosic biomass dissolution and physicochemical properties of ionic liquids composed of 3-methylimidazolium cations and carboxylate anions. United States. doi:10.1039/C7CP07195G.
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Moyer, Preenaa, Smith, Micholas Dean, Abdoulmoumine, Nourredine, Chmely, Stephen C., Smith, Jeremy C., Petridis, Loukas, and Labbé, Nicole. Tue . "Relationship between lignocellulosic biomass dissolution and physicochemical properties of ionic liquids composed of 3-methylimidazolium cations and carboxylate anions". United States. doi:10.1039/C7CP07195G. https://www.osti.gov/servlets/purl/1423012.
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@article{osti_1423012,
title = {Relationship between lignocellulosic biomass dissolution and physicochemical properties of ionic liquids composed of 3-methylimidazolium cations and carboxylate anions},
author = {Moyer, Preenaa and Smith, Micholas Dean and Abdoulmoumine, Nourredine and Chmely, Stephen C. and Smith, Jeremy C. and Petridis, Loukas and Labbé, Nicole},
abstractNote = {The ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([EMIM]Acetate) has been widely used for biomass processing, i.e., to pretreat, activate, or fractionate lignocellulosic biomass to produce soluble sugars and lignin. However, this IL does not achieve high biomass solubility, therefore minimizing the efficiency of biomass processing. In this paper, [EMIM]Acetate and three other ILs composed of different 3-methylimidazolium cations and carboxylate anions ([EMIM]Formate, 1-allyl-3-methylimidazolium ([AMIM]) formate, and [AMIM]Acetate) were analyzed to relate their physicochemical properties to their biomass solubility performance. While all four ILs are able to dissolve hybrid poplar under fairly mild process conditions (80 °C and 100 RPM stirring), [AMIM]Formate and [AMIM]Acetate have particularly increased biomass solubility of 40 and 32%, respectively, relative to [EMIM]Acetate. Molecular dynamics simulations suggest that strong interactions between IL and specific plant biopolymers may contribute to this enhanced solubilization, as the calculated second virial coefficients between ILs and hemicellullose are most favorable for [AMIM]Formate, matching the trend of the experimental solubility measurements. The simulations also reveal that the interactions between the ILs and hemicellulose are an important factor in determining the overall biomass solubility, whereas lignin–IL interactions were not found to vary significantly, consistent with literature. Finally, the combined experimental and simulation studies identify [AMIM]Formate as an efficient biomass solvent and explain its efficacy, suggesting a new approach to rationally select ionic liquid solvents for lignocellulosic deconstruction.},
doi = {10.1039/C7CP07195G},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 4,
volume = 20,
place = {United States},
year = {2018},
month = {1}
}
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Journal Article:
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DOI:  10.1039/C7CP07195G
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Table 1. Table 1.: Chemical composition of hybrid poplar.
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