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Title: Cellulose Hydrolysis in Acidified LiBr Molten Salt Hydrate Media

Abstract

In this work, we screened nine acidified molten salt hydrates (solutions with water to salt molar ratio equal or less than the coordination number of the cation) as reaction media for cellulose hydrolysis, and we found that cellulose can be efficiently hydrolyzed in LiBr acidified MSH under mild conditions (>90% yield to water-soluble products in 0.05 M H 2SO 4 at 85 °C for 30 min). The effect of various factors (temperature as well as acid and initial cellulose concentrations) on the kinetics of hydrolysis reaction was also investigated. At the lowest temperatures examined (70 and 85 °C) low amounts of degradation products have been observed, and glucose appears to be in equilibrium with its dimers and possibly other oligomers. Higher temperatures (100–115 °C) enhanced the formation of degradation products (organic acids and humins). Analysis of the kinetic data indicate that hydrolysis rates are first order in cellulose and in H 2SO 4 concentration, and the initial hydrolysis rates have an apparent activation energy ~123 kJ/mol. X-ray diffraction, SEM, and FTIR were also used to study cellulose’s structural/morphological changes upon treatment in the LiBr MSH media, in an attempt to understand the effects of the cellulose–salt interaction. Analysis of themore » data indicates that the enhancement of the hydrolysis rates can be attributed to the enhancement of the acidity of reaction media through synergistic effect of dilute acid and MSH, the breaking of crystalline structure through swelling, and the interaction of the salt with cellulose chains affecting the conformation and flexibility of the glycosidic bonds.« less

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Univ. of Delaware, Newark, DE (United States). Dept. of Chemical & Biomolecular Engineering, Catalysis Center for Energy Innovation (CCEI)
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
Energy Frontier Research Centers (EFRC) (United States)
OSTI Identifier:
1385934
Grant/Contract Number:  
SC0001004
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Industrial and Engineering Chemistry Research
Additional Journal Information:
Journal Volume: 54; Journal Issue: 19; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University; Journal ID: ISSN 0888-5885
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous); catalysis (heterogeneous); biofuels (including algae and biomass); bio-inspired; hydrogen and fuel cells; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing); vibrational spectroscopy; Raman; FTIR; biomass; green chemicals; biofuels

Citation Formats

Deng, Weihua, Kennedy, James R., Tsilomelekis, George, Zheng, Weiqing, and Nikolakis, Vladimiros. Cellulose Hydrolysis in Acidified LiBr Molten Salt Hydrate Media. United States: N. p., 2015. Web. doi:10.1021/acs.iecr.5b00757.
Deng, Weihua, Kennedy, James R., Tsilomelekis, George, Zheng, Weiqing, & Nikolakis, Vladimiros. Cellulose Hydrolysis in Acidified LiBr Molten Salt Hydrate Media. United States. doi:10.1021/acs.iecr.5b00757.
Deng, Weihua, Kennedy, James R., Tsilomelekis, George, Zheng, Weiqing, and Nikolakis, Vladimiros. Fri . "Cellulose Hydrolysis in Acidified LiBr Molten Salt Hydrate Media". United States. doi:10.1021/acs.iecr.5b00757. https://www.osti.gov/servlets/purl/1385934.
@article{osti_1385934,
title = {Cellulose Hydrolysis in Acidified LiBr Molten Salt Hydrate Media},
author = {Deng, Weihua and Kennedy, James R. and Tsilomelekis, George and Zheng, Weiqing and Nikolakis, Vladimiros},
abstractNote = {In this work, we screened nine acidified molten salt hydrates (solutions with water to salt molar ratio equal or less than the coordination number of the cation) as reaction media for cellulose hydrolysis, and we found that cellulose can be efficiently hydrolyzed in LiBr acidified MSH under mild conditions (>90% yield to water-soluble products in 0.05 M H2SO4 at 85 °C for 30 min). The effect of various factors (temperature as well as acid and initial cellulose concentrations) on the kinetics of hydrolysis reaction was also investigated. At the lowest temperatures examined (70 and 85 °C) low amounts of degradation products have been observed, and glucose appears to be in equilibrium with its dimers and possibly other oligomers. Higher temperatures (100–115 °C) enhanced the formation of degradation products (organic acids and humins). Analysis of the kinetic data indicate that hydrolysis rates are first order in cellulose and in H2SO4 concentration, and the initial hydrolysis rates have an apparent activation energy ~123 kJ/mol. X-ray diffraction, SEM, and FTIR were also used to study cellulose’s structural/morphological changes upon treatment in the LiBr MSH media, in an attempt to understand the effects of the cellulose–salt interaction. Analysis of the data indicates that the enhancement of the hydrolysis rates can be attributed to the enhancement of the acidity of reaction media through synergistic effect of dilute acid and MSH, the breaking of crystalline structure through swelling, and the interaction of the salt with cellulose chains affecting the conformation and flexibility of the glycosidic bonds.},
doi = {10.1021/acs.iecr.5b00757},
journal = {Industrial and Engineering Chemistry Research},
issn = {0888-5885},
number = 19,
volume = 54,
place = {United States},
year = {2015},
month = {4}
}

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