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Title: Speciation and kinetic study of iron promoted sugar conversion to 5-hydroxymethylfurfural (HMF) and levulinic acid (LA)

Journal Article · · Organic Chemistry Frontiers (Online)
DOI:https://doi.org/10.1039/C5QO00194C· OSTI ID:1386965
 [1];  [1];  [1];  [2];  [2];  [3];  [2];  [1];  [1]
  1. Purdue Univ., West Lafayette, IN (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio)
  2. Purdue Univ., West Lafayette, IN (United States)
  3. Energy Frontier Research Centers (EFRC) (United States). Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio); Purdue Univ., West Lafayette, IN (United States)
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Cellulose, a major component of renewable biomass, is a polymer of glucose. Abundant and cheap iron salts promote the conversion of glucose to 5-hydroxymethylfurfural (HMF) and levulinic acid (LA). In this study, glucose transformations catalyzed by iron(III) chloride (FeCl3) in aqueous and in biphasic media (water and 2-methyltetrahydrofuran (MeTHF)) were investigated. Speciation via mass spectrometry (MS), UV-Vis, and X-ray absorption spectroscopy (XAS) show that FeIII is reduced to FeII (over 95%) readily in the early stage of carbohydrate conversion. The reaction time profiles of reactants (glucose and fructose) as well as products (HMF and LA) were modeled using MATLAB to obtain reaction rate constants. The contributions of iron and the intrinsic Brønsted acidity of iron salts in the sugar conversion are discussed. The kinetic study of sugar conversion indicated that the water–MeTHF biphasic system hinders the conversion of sugars to humins and unknown byproducts and increases the yields of HMF and LA. By adjusting concentrations of FeII and Brønsted acidity, yields of 88% LA (FeCl3, pH = 1) or 56% HMF (FeSO4, pH = 2) from glucose in a water–MeTHF biphasic system are achieved. In this work, the optimized reaction conditions proved effective in the conversion of milled poplar biomass to LA (53% yield based on glucose content) and furfural (64% yield based on xylan content) using iron salt, outperforming aluminum and chromium salts.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0000997
OSTI ID:
1386965
Journal Information:
Organic Chemistry Frontiers (Online), Vol. 2, Issue 10; Related Information: C3Bio partners with Purdue University (lead); Argonne National Laboratory; National Renewable Energy Laboratory; Northeastern University; University of Tennessee; ISSN 2052-4129
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 38 works
Citation information provided by
Web of Science

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Cited By (7)

Biosynthesized Quantum Dot Size Cu Nanocatalyst: Peroxidase Mimetic and Aqueous Phase Conversion of Fructose journal November 2018
Selective Colorimetric Detection of Fe (III) Using Metallochromic Tannin‐Impregnated Silica Strips journal November 2018
Optimization of Biomass Conversion to Levulinic Acid in Acidic Ionic Liquid and Upgrading of Levulinic Acid to Ethyl Levulinate journal July 2016
Kinetic study on the impact of acidity and acid concentration on the formation of 5-hydroxymethylfurfural (HMF), humins, and levulinic acid in the hydrothermal conversion of fructose journal September 2019
NIR emission and luminescent sensing of a lanthanide–organic framework with Lewis basic imidazole and pyridyl sites journal January 2017
Renewable thermoset polymers based on lignin and carbohydrate derived monomers journal January 2018
The effect of different Brønsted acids on the hydrothermal conversion of fructose to HMF journal January 2018

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synthesis (self-assembly)
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