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Title: Toward biomass-derived renewable plastics: Production of 2,5-furandicarboxylic acid from fructose

Abstract

We report a process for converting fructose, at a high concentration (15 weight %), to 2,5-furandicarboxylic acid (FDCA), a monomer used in the production of polyethylene furanoate, a renewable plastic. In our process, fructose is dehydrated to hydroxymethylfurfural (HMF) at high yields (70%) using a γ-valerolactone (GVL)/H2O solvent system. HMF is subsequently oxidized to FDCA over a Pt/C catalyst with 93% yield. The advantage of our system is the higher solubility of FDCA in GVL/H2O, which allows oxidation at high concentrations using a heterogeneous catalyst that eliminates the need for a homogeneous base. In addition, FDCA can be separated from the GVL/H2O solvent system by crystallization to obtain >99% pure FDCA. Our process eliminates the use of corrosive acids, because FDCA is an effective catalyst for fructose dehydration, leading to improved economic and environmental impact of the process. Our techno-economic model indicates that the overall process is economically competitive with current terephthalic acid processes.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering. Great Lakes Bioenergy Research Center
  2. 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 Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1499959
Grant/Contract Number:  
FC02-07ER64494
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 1; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Motagamwala, Ali Hussain, Won, Wangyun, Sener, Canan, Alonso, David Martin, Maravelias, Christos T., and Dumesic, James A. Toward biomass-derived renewable plastics: Production of 2,5-furandicarboxylic acid from fructose. United States: N. p., 2018. Web. doi:10.1126/sciadv.aap9722.
Motagamwala, Ali Hussain, Won, Wangyun, Sener, Canan, Alonso, David Martin, Maravelias, Christos T., & Dumesic, James A. Toward biomass-derived renewable plastics: Production of 2,5-furandicarboxylic acid from fructose. United States. doi:10.1126/sciadv.aap9722.
Motagamwala, Ali Hussain, Won, Wangyun, Sener, Canan, Alonso, David Martin, Maravelias, Christos T., and Dumesic, James A. Fri . "Toward biomass-derived renewable plastics: Production of 2,5-furandicarboxylic acid from fructose". United States. doi:10.1126/sciadv.aap9722. https://www.osti.gov/servlets/purl/1499959.
@article{osti_1499959,
title = {Toward biomass-derived renewable plastics: Production of 2,5-furandicarboxylic acid from fructose},
author = {Motagamwala, Ali Hussain and Won, Wangyun and Sener, Canan and Alonso, David Martin and Maravelias, Christos T. and Dumesic, James A.},
abstractNote = {We report a process for converting fructose, at a high concentration (15 weight %), to 2,5-furandicarboxylic acid (FDCA), a monomer used in the production of polyethylene furanoate, a renewable plastic. In our process, fructose is dehydrated to hydroxymethylfurfural (HMF) at high yields (70%) using a γ-valerolactone (GVL)/H2O solvent system. HMF is subsequently oxidized to FDCA over a Pt/C catalyst with 93% yield. The advantage of our system is the higher solubility of FDCA in GVL/H2O, which allows oxidation at high concentrations using a heterogeneous catalyst that eliminates the need for a homogeneous base. In addition, FDCA can be separated from the GVL/H2O solvent system by crystallization to obtain >99% pure FDCA. Our process eliminates the use of corrosive acids, because FDCA is an effective catalyst for fructose dehydration, leading to improved economic and environmental impact of the process. Our techno-economic model indicates that the overall process is economically competitive with current terephthalic acid processes.},
doi = {10.1126/sciadv.aap9722},
journal = {Science Advances},
number = 1,
volume = 4,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
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Cited by: 61 works
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Figures / Tables:

Scheme 1. Scheme 1.: General reaction scheme for the production of FDCA from fructose.

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Works referenced in this record:

Water sorption in poly(ethylene furanoate) compared to poly(ethylene terephthalate). Part 1: Equilibrium sorption
journal, December 2014


A sulfuric acid management strategy for the production of liquid hydrocarbon fuels via catalytic conversion of biomass-derived levulinic acid
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A strategy for the simultaneous catalytic conversion of hemicellulose and cellulose from lignocellulosic biomass to liquid transportation fuels
journal, January 2014

  • Han, Jeehoon; Sen, S. Murat; Alonso, David Martin
  • Green Chem., Vol. 16, Issue 2
  • DOI: 10.1039/C3GC41511B

Thermodynamics of solvation in mixed solvents
journal, January 1993


Kinetics and mechanism of 5-hydroxymethylfurfural oxidation and their implications for catalyst development
journal, July 2014

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Biomass into Chemicals: Aerobic Oxidation of 5-Hydroxymethyl-2-furfural into 2,5-Furandicarboxylic Acid with Gold Nanoparticle Catalysts
journal, December 2009


Carbon Dioxide Sorption and Transport in Amorphous Poly(ethylene furanoate)
journal, March 2015


Production of Oxidized Derivatives of 5-Hydroxymethylfurfural (HMF)
journal, May 2010

  • Lilga, Michael A.; Hallen, Richard T.; Gray, Michel
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Chain Mobility, Thermal, and Mechanical Properties of Poly(ethylene furanoate) Compared to Poly(ethylene terephthalate)
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Dehydration reactions of fructose in non-aqueous media
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High molecular weight poly(ethylene-2,5-furanoate); critical aspects in synthesis and mechanical property determination
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Production and upgrading of 5-hydroxymethylfurfural using heterogeneous catalysts and biomass-derived solvents
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  • Gallo, Jean Marcel R.; Alonso, David Martin; Mellmer, Max A.
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Selective oxidation of 5-hydroxymethyl-2-furfural using supported gold–copper nanoparticles
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Effect of Support in Heterogeneous Ruthenium Catalysts Used for the Selective Aerobic Oxidation of HMF in Water
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Vapor–Liquid Equilibria, Excess Enthalpy, and Density of Aqueous γ-Valerolactone Solutions.
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    Works referencing / citing this record:

    Preparation and Single Crystal Structure Determination of the First Biobased Furan-Polydiacetylene Using Topochemical Polymerization
    journal, August 2019

    • Dory, Yves L.; Caron, Mia; Duguay, Vincent Olivier
    • Crystals, Vol. 9, Issue 9
    • DOI: 10.3390/cryst9090448

    Biomass into Chemicals: Aerobic Oxidation of 5-Hydroxymethyl-2-furfural into 2,5-Furandicarboxylic Acid with Gold Nanoparticle Catalysts
    journal, December 2009


    The Direct Conversion of Sugars into 2,5-Furandicarboxylic Acid in a Triphasic System
    journal, March 2015


    Dehydration reactions of fructose in non-aqueous media
    journal, January 1982

    • Brown, David W.; Floyd, Arthur J.; Kinsman, Richard G.
    • Journal of Chemical Technology and Biotechnology, Vol. 32, Issue 7-12
    • DOI: 10.1002/jctb.5030320730

    High molecular weight poly(ethylene-2,5-furanoate); critical aspects in synthesis and mechanical property determination
    journal, July 2013

    • Knoop, Rutger J. I.; Vogelzang, Willem; van Haveren, Jacco
    • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 51, Issue 19
    • DOI: 10.1002/pola.26833

    Production of Oxidized Derivatives of 5-Hydroxymethylfurfural (HMF)
    journal, May 2010

    • Lilga, Michael A.; Hallen, Richard T.; Gray, Michel
    • Topics in Catalysis, Vol. 53, Issue 15-18
    • DOI: 10.1007/s11244-010-9579-4

    Effect of Support in Heterogeneous Ruthenium Catalysts Used for the Selective Aerobic Oxidation of HMF in Water
    journal, September 2011

    • Gorbanev, Yury Y.; Kegnæs, Søren; Riisager, Anders
    • Topics in Catalysis, Vol. 54, Issue 16-18
    • DOI: 10.1007/s11244-011-9754-2

    Kinetics and mechanism of 5-hydroxymethylfurfural oxidation and their implications for catalyst development
    journal, July 2014

    • Davis, Sara E.; Benavidez, Angelica D.; Gosselink, Robert W.
    • Journal of Molecular Catalysis A: Chemical, Vol. 388-389
    • DOI: 10.1016/j.molcata.2013.09.013

    Oxygen sorption and transport in amorphous poly(ethylene furanoate)
    journal, September 2014


    Water sorption in poly(ethylene furanoate) compared to poly(ethylene terephthalate). Part 1: Equilibrium sorption
    journal, December 2014


    Vapor–Liquid Equilibria, Excess Enthalpy, and Density of Aqueous γ-Valerolactone Solutions.
    journal, January 2016

    • Zaitseva, Anna; Pokki, Juha-Pekka; Le, Huy Quang
    • Journal of Chemical & Engineering Data, Vol. 61, Issue 2
    • DOI: 10.1021/acs.jced.5b00724

    Carbon Dioxide Sorption and Transport in Amorphous Poly(ethylene furanoate)
    journal, March 2015


    Recent Advances in the Catalytic Synthesis of 2,5-Furandicarboxylic Acid and Its Derivatives
    journal, October 2015


    Chain Mobility, Thermal, and Mechanical Properties of Poly(ethylene furanoate) Compared to Poly(ethylene terephthalate)
    journal, February 2014

    • Burgess, Steven K.; Leisen, Johannes E.; Kraftschik, Brian E.
    • Macromolecules, Vol. 47, Issue 4
    • DOI: 10.1021/ma5000199

    Catalytic Conversion of Fructose and 5-Hydroxymethylfurfural into 2,5-Furandicarboxylic Acid over a Recyclable Fe 3 O 4 –CoO x Magnetite Nanocatalyst
    journal, February 2015

    • Wang, Shuguo; Zhang, Zehui; Liu, Bing
    • ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 3
    • DOI: 10.1021/sc500702q

    Selective oxidation of 5-hydroxymethyl-2-furfural using supported gold–copper nanoparticles
    journal, January 2011

    • Pasini, Thomas; Piccinini, Marco; Blosi, Magda
    • Green Chemistry, Vol. 13, Issue 8
    • DOI: 10.1039/c1gc15355b

    On the mechanism of selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over supported Pt and Au catalysts
    journal, January 2012

    • Davis, Sara E.; Zope, Bhushan N.; Davis, Robert J.
    • Green Chemistry, Vol. 14, Issue 1, p. 143-147
    • DOI: 10.1039/c1gc16074e

    A sulfuric acid management strategy for the production of liquid hydrocarbon fuels via catalytic conversion of biomass-derived levulinic acid
    journal, January 2012

    • Sen, S. Murat; Alonso, David Martin; Wettstein, Stephanie G.
    • Energy & Environmental Science, Vol. 5, Issue 12
    • DOI: 10.1039/c2ee22526c

    Production and upgrading of 5-hydroxymethylfurfural using heterogeneous catalysts and biomass-derived solvents
    journal, January 2013

    • Gallo, Jean Marcel R.; Alonso, David Martin; Mellmer, Max A.
    • Green Chem., Vol. 15, Issue 1
    • DOI: 10.1039/c2gc36536g

    A strategy for the simultaneous catalytic conversion of hemicellulose and cellulose from lignocellulosic biomass to liquid transportation fuels
    journal, January 2014

    • Han, Jeehoon; Sen, S. Murat; Alonso, David Martin
    • Green Chem., Vol. 16, Issue 2
    • DOI: 10.1039/c3gc41511b

    Thermodynamics of solvation in mixed solvents
    journal, January 1993


    Preparation and Single Crystal Structure Determination of the First Biobased Furan-Polydiacetylene Using Topochemical Polymerization
    journal, August 2019

    • Dory, Yves L.; Caron, Mia; Duguay, Vincent Olivier
    • Crystals, Vol. 9, Issue 9
    • DOI: 10.3390/cryst9090448

    Recent Advances in the Catalytic Production of Platform Chemicals from Holocellulosic Biomass
    journal, March 2019

    • Gómez Millán, Gerardo; Hellsten, Sanna; Llorca, Jordi
    • ChemCatChem, Vol. 11, Issue 8
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    Catalytic Transformation of Biomass Derivatives to Value‐Added Chemicals and Fuels in Continuous Flow Microreactors
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    journal, June 2018


    Polymers Based on Cyclic Carbonates as Trait d'Union Between Polymer Chemistry and Sustainable CO 2 Utilization
    journal, February 2019


    When Will 5‐Hydroxymethylfurfural, the “Sleeping Giant” of Sustainable Chemistry, Awaken?
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    Continuous‐Flow Oxidation of HMF to FDCA by Resin‐Supported Platinum Catalysts in Neat Water
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    Aerobic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid over Holey 2 D Mn 2 O 3 Nanoflakes from a Mn‐based MOF
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    Valorisation of Biomass Derived Furfural and Levulinic Acid by Highly Efficient Pd@ND Catalyst
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    Solvent system for effective near-term production of hydroxymethylfurfural (HMF) with potential for long-term process improvement
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    • Energy & Environmental Science, Vol. 12, Issue 7
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    • Zhou, Hua; Xu, Huanghui; Wang, Xueke
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    Synthesis of biomass-derived feedstocks for the polymers and fuels industries from 5-(hydroxymethyl)furfural (HMF) and acetone
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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.