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Title: Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures

Abstract

In this paper, we demonstrate a process to produce levoglucosenone (LGO) and 5-hydroxymethylfurfural (HMF) from cellulose in up to 65% carbon yield using sulfuric acid as catalyst and a solvent consisting of a mixture of tetrahydrofuran (THF) with water. In pure THF, LGO is the major product of cellulose dehydration, passing through levoglucosan as an intermediate. Increasing the water content (up to 5 wt%) results in HMF as the major product. HMF is formed both by glucose dehydration and direct dehydration of LGA. The maximum combined yield of LGO and HMF (~65 carbon%) is achieved in the presence of 1–2.5 wt% H 2O, such that comparable amounts of these two co-products are formed. THF gave the highest total yields of LGO and HMF among the solvents investigated in this study (i.e., THF, diglyme, tetraglyme, gamma-valerolactone (GVL), cyclopentyl methyl ether (CPME), 1,4-dioxane, and dimethyl sulfoxide (DMSO)). Furthermore, the rate of LGO and HMF degradation in THF was lower than in the other solvents. LGO/HMF yields increased with increased strength of the acid catalyst (H 2SO 4 > H 3PO 4 > HCOOH), and HMF was produced more selectively than LGO in the presence of hydrochloric acid. Finally, techno-economic analysis for LGOmore » and HMF production from cellulose shows that the lowest LGO/HMF production costs are less than $3.00 per kg and occur at a cellulose loading and water content of 2–3% and 1.5–2.5% respectively.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1475401
Grant/Contract Number:  
EE0006878
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 19; Journal Issue: 15; 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

He, Jiayue, Liu, Mingjie, Huang, Kefeng, Walker, Theodore W., Maravelias, Christos T., Dumesic, James A., and Huber, George W. Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures. United States: N. p., 2017. Web. doi:10.1039/C7GC01688C.
He, Jiayue, Liu, Mingjie, Huang, Kefeng, Walker, Theodore W., Maravelias, Christos T., Dumesic, James A., & Huber, George W. Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures. United States. https://doi.org/10.1039/C7GC01688C
He, Jiayue, Liu, Mingjie, Huang, Kefeng, Walker, Theodore W., Maravelias, Christos T., Dumesic, James A., and Huber, George W. Thu . "Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures". United States. https://doi.org/10.1039/C7GC01688C. https://www.osti.gov/servlets/purl/1475401.
@article{osti_1475401,
title = {Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures},
author = {He, Jiayue and Liu, Mingjie and Huang, Kefeng and Walker, Theodore W. and Maravelias, Christos T. and Dumesic, James A. and Huber, George W.},
abstractNote = {In this paper, we demonstrate a process to produce levoglucosenone (LGO) and 5-hydroxymethylfurfural (HMF) from cellulose in up to 65% carbon yield using sulfuric acid as catalyst and a solvent consisting of a mixture of tetrahydrofuran (THF) with water. In pure THF, LGO is the major product of cellulose dehydration, passing through levoglucosan as an intermediate. Increasing the water content (up to 5 wt%) results in HMF as the major product. HMF is formed both by glucose dehydration and direct dehydration of LGA. The maximum combined yield of LGO and HMF (~65 carbon%) is achieved in the presence of 1–2.5 wt% H2O, such that comparable amounts of these two co-products are formed. THF gave the highest total yields of LGO and HMF among the solvents investigated in this study (i.e., THF, diglyme, tetraglyme, gamma-valerolactone (GVL), cyclopentyl methyl ether (CPME), 1,4-dioxane, and dimethyl sulfoxide (DMSO)). Furthermore, the rate of LGO and HMF degradation in THF was lower than in the other solvents. LGO/HMF yields increased with increased strength of the acid catalyst (H2SO4 > H3PO4 > HCOOH), and HMF was produced more selectively than LGO in the presence of hydrochloric acid. Finally, techno-economic analysis for LGO and HMF production from cellulose shows that the lowest LGO/HMF production costs are less than $3.00 per kg and occur at a cellulose loading and water content of 2–3% and 1.5–2.5% respectively.},
doi = {10.1039/C7GC01688C},
url = {https://www.osti.gov/biblio/1475401}, journal = {Green Chemistry},
issn = {1463-9262},
number = 15,
volume = 19,
place = {United States},
year = {2017},
month = {6}
}

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