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Title: Direct Conversion of Biomass Carbohydrates to Platform Chemicals: 5-Hydroxymethylfurfural (HMF) and Furfural

Abstract

5-hydroxymethylfurfural (HMF) and furfural are promising platform molecules which can be converted to fuel intermediates and hydrocarbon fuels. Herein, one-step, direct conversion of the carbohydrates in never treated biomass to HMF and furfural in a microwave reactor was investigated. The influence of reaction temperature, time, feedstock, addition of Lewis and Bronsted acids, solvent and solvent to aqueous ratio were studied to find the optimum process conditions to maximize the yields of furfurals. The reaction conditions of 200 degrees C for 5 min with 33 mM HCl and 8 mM AlCl3 using a dioxane/water (4:1) miscible solvent system were found to be the most conducive for direct dehydration of the glucan and hemicelluloses present in untreated poplar wood to furfural and HMF in yields of 91 and 69%, respectively. Furfural could be easily produced in yields greater than 80%, and once formed, it was found to be stable under the various process conditions explored. In contrast, HMF yields varied with both reaction time and temperature, as it readily underwent rehydration to levulinic acid in yields approaching 25-30% at increased reaction severity. The additions of both Bronsted (HCl) and Lewis (AlCl3) acids in catalytic amounts, i.e., 33 and 8 mM, respectively, weremore » required to maximize the yield of furfurals. Reactions were also performed on other feedstocks (corn stover, switchgrass, loblolly pine, and pure cellulose) to investigate the effect of feedstock type on furfurals yields. Results showed that HMF and furfural yields were primarily dependent on hexosan and pentosan loading regardless of the type of feedstock. In addition, biomass physical features, such as crystallinity or the presence of other biomass constituents, such as lignin, had little influence on furfurals yields.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1602687
Report Number(s):
NREL/JA-2700-74720
Journal ID: ISSN 0887-0624; MainId:15206;UUID:4685d627-13c9-e911-9c26-ac162d87dfe5;MainAdminID:3684
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Energy and Fuels
Additional Journal Information:
Journal Volume: 34; Journal Issue: 3; Journal ID: ISSN 0887-0624
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; biomass; carbohydrate; dehydration; 5-hydroxymethylfurfural; HMF; furfural; crystallinity

Citation Formats

Mittal, Ashutosh, Pilath, Heidi M., and Johnson, David K. Direct Conversion of Biomass Carbohydrates to Platform Chemicals: 5-Hydroxymethylfurfural (HMF) and Furfural. United States: N. p., 2020. Web. doi:10.1021/acs.energyfuels.9b04047.
Mittal, Ashutosh, Pilath, Heidi M., & Johnson, David K. Direct Conversion of Biomass Carbohydrates to Platform Chemicals: 5-Hydroxymethylfurfural (HMF) and Furfural. United States. https://doi.org/10.1021/acs.energyfuels.9b04047
Mittal, Ashutosh, Pilath, Heidi M., and Johnson, David K. Sun . "Direct Conversion of Biomass Carbohydrates to Platform Chemicals: 5-Hydroxymethylfurfural (HMF) and Furfural". United States. https://doi.org/10.1021/acs.energyfuels.9b04047. https://www.osti.gov/servlets/purl/1602687.
@article{osti_1602687,
title = {Direct Conversion of Biomass Carbohydrates to Platform Chemicals: 5-Hydroxymethylfurfural (HMF) and Furfural},
author = {Mittal, Ashutosh and Pilath, Heidi M. and Johnson, David K},
abstractNote = {5-hydroxymethylfurfural (HMF) and furfural are promising platform molecules which can be converted to fuel intermediates and hydrocarbon fuels. Herein, one-step, direct conversion of the carbohydrates in never treated biomass to HMF and furfural in a microwave reactor was investigated. The influence of reaction temperature, time, feedstock, addition of Lewis and Bronsted acids, solvent and solvent to aqueous ratio were studied to find the optimum process conditions to maximize the yields of furfurals. The reaction conditions of 200 degrees C for 5 min with 33 mM HCl and 8 mM AlCl3 using a dioxane/water (4:1) miscible solvent system were found to be the most conducive for direct dehydration of the glucan and hemicelluloses present in untreated poplar wood to furfural and HMF in yields of 91 and 69%, respectively. Furfural could be easily produced in yields greater than 80%, and once formed, it was found to be stable under the various process conditions explored. In contrast, HMF yields varied with both reaction time and temperature, as it readily underwent rehydration to levulinic acid in yields approaching 25-30% at increased reaction severity. The additions of both Bronsted (HCl) and Lewis (AlCl3) acids in catalytic amounts, i.e., 33 and 8 mM, respectively, were required to maximize the yield of furfurals. Reactions were also performed on other feedstocks (corn stover, switchgrass, loblolly pine, and pure cellulose) to investigate the effect of feedstock type on furfurals yields. Results showed that HMF and furfural yields were primarily dependent on hexosan and pentosan loading regardless of the type of feedstock. In addition, biomass physical features, such as crystallinity or the presence of other biomass constituents, such as lignin, had little influence on furfurals yields.},
doi = {10.1021/acs.energyfuels.9b04047},
journal = {Energy and Fuels},
number = 3,
volume = 34,
place = {United States},
year = {Sun Feb 16 00:00:00 EST 2020},
month = {Sun Feb 16 00:00:00 EST 2020}
}

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