Research ArticleAPPLIED SCIENCES AND ENGINEERING

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

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Science Advances  19 Jan 2018:
Vol. 4, no. 1, eaap9722
DOI: 10.1126/sciadv.aap9722
  • Scheme 1 General reaction scheme for the production of FDCA from fructose.

  • Fig. 1 HMF oxidation, FDCA solubility, and fructose dehydration.

    (A) HMF oxidation over 5 wt % Pt/C. 0.5 wt % HMF in GVL/H2O (80:20) solution; temperature, 373 K; pressure, 40 bar; 5 wt % Pt/C, 2.0 g; solvent flow rate, 0.05 ml/min; O2 flow rate, 20 ml/min. Black squares represents FDCA yield. Red circles represents FFCA yield. (B) HMF oxidation over 5 wt % Pt/C. 1.0 wt % HMF in GVL/H2O (50:50) solution, temperature, 373 K; pressure, 40 bar; 5 wt % Pt/C, 2.0 g; solvent flow rate, 0.02 ml/min; O2 flow rate, 25 ml/min. Black squares represent FDCA yield. Red circles represent FFCA yield. (C) FDCA solubility as a function of GVL concentration. Red circles represent solubility of FDCA at 303 K. Red triangles represent solubility of FDCA at 373 K. Black squares represent heat of mixing of GVL and H2O. (D) FDCA solubility as a function of temperature. Red circles represent GVL/H2O (50:50). Black squares represent H2O. (E and F) Fructose conversion and HMF yield for fructose dehydration at 453 K. Black squares represent fructose dehydration using 3 mM HCl. Blue triangles represent fructose dehydration using 0.53 wt % FDCA. Red diamonds represent FDCA stability under dehydration reaction. Solid lines are visual guides.

  • Fig. 2 Process and economics for the production of FDCA from fructose.

    (A) Pictorial representation of FDCA production from fructose. (i) 15 wt % fructose in GVL/H2O (50:50) containing 0.53 wt % FDCA. (ii) Solution after dehydration at 453 K containing 7.5% HMF and humins. (iii) Humin removal by adsorption over activated carbon (a red colored solution instead of a black solution is obtained). (iv) Solution obtained after oxidation over a Pt/C catalyst. (B) Sankey diagram for FDCA production process and (C) costs and revenues. LA, levulinic acid; AC, activated carbon; ROI, return on investment.

  • Table 1 Results for HMF oxidation reactions.

    Reaction was carried over the 5% Pt/C catalyst (under 40-bar O2 pressure and 383 K). DFF, furan-2,5-dicarbaldehyde.

    #HMF concentrationSolvent
    (GVL/H2O)
    HMF/Pt*Time (hours)HMF conversion
    (%)
    DFF yield
    (%)
    FFCA yield
    (%)
    FDCA yield
    (%)
    10.5 wt %80:2015:1209795
    25 wt %80:2020:12010093111
    37.5 wt %50:5030:12010094
    47.5 wt % F-D HMF50:5030:1161000
    57.5 wt % F-D HMF using
    HCl + ion exchange +
    humin adsorption
    50:5030:11610093
    67.5 wt % F-D HMF using
    FDCA + humin adsorption
    50:5030:11610091

    *Molar ratio of HMF to platinum.

    Supplementary Materials

    • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/4/1/eaap9722/DC1

      Supplementary Materials and Methods

      fig. S1. Chromatogram of product solution obtained by the dehydration of fructose.

      fig. S2. CO chemisorption isotherms for the 5% Pt/C catalyst.

      fig. S3. Image showing the separation of catalyst, solvent, and crystallized FDCA.

      fig. S4. PDA chromatogram of freeze-dried FDCA.

      fig. S5. Gas chromtography–mass spectrometry analysis of freeze-dried FDCA.

      fig. S6. Nuclear magnetic resonance spectroscopy analysis of freeze-dried FDCA.

      fig. S7. Differential scanning calorimetry curve of freeze-dried FDCA.

      fig. S8. Process block flow diagram for the integrated FDCA production strategy.

      fig. S9. Safety in the oxidation reactor.

      table S1. Product composition after fructose dehydration using FDCA as a dehydration catalyst.

      table S2. Product concentration before and after removal of humins by adsorption.

      table S3. Characterization of the Pt/C catalyst.

      table S4. Results for HMF oxidation reactions over the 5% Pt/C catalyst (under 40-bar O2 pressure and 383 K).

      table S5. Mass and energy balances (basis: 500 metric tons of fructose per day).

      table S6. Energy requirements (basis: 500 metric tons of fructose per day).

      table S7. Capital and operating costs (basis: 500 metric tons of fructose per day).

      table S8. List of economic parameters and assumptions.

      table S9. Effect of transport resistance and O2 pressure on HMF oxidation over a Pt/C catalyst.

      References (2934)

    • Supplementary Materials

      This PDF file includes:

      • Supplementary Materials and Methods
      • fig. S1. Chromatogram of product solution obtained by the dehydration of fructose.
      • fig. S2. CO chemisorption isotherms for the 5% Pt/C catalyst.
      • fig. S3. Image showing the separation of catalyst, solvent, and crystallized FDCA.
      • fig. S4. PDA chromatogram of freeze-dried FDCA.
      • fig. S5. Gas chromtography–mass spectrometry analysis of freeze-dried FDCA.
      • fig. S6. Nuclear magnetic resonance spectroscopy analysis of freeze-dried FDCA.
      • fig. S7. Differential scanning calorimetry curve of freeze-dried FDCA.
      • fig. S8. Process block flow diagram for the integrated FDCA production strategy.
      • fig. S9. Safety in the oxidation reactor.
      • table S1. Product composition after fructose dehydration using FDCA as a dehydration catalyst.
      • table S2. Product concentration before and after removal of humins by adsorption.
      • table S3. Characterization of the Pt/C catalyst.
      • table S4. Results for HMF oxidation reactions over the 5% Pt/C catalyst (under 40-bar O2 pressure and 383 K).
      • table S5. Mass and energy balances (basis: 500 metric tons of fructose per day).
      • table S6. Energy requirements (basis: 500 tons of fructose per day).
      • table S7. Capital and operating costs (basis: 500 metric tons of fructose per day).
      • table S8. List of economic parameters and assumptions.
      • table S9. Effect of transport resistance and O2 pressure on HMF oxidation over a Pt/C catalyst.
      • References (29–34)

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