A scalable carboxylation route to furan-2,5-dicarboxylic acid

doi:10.1039/C7GC01059A

Paper

A scalable carboxylation route to furan-2,5-dicarboxylic acid

Published Jul 3, 2017 · Graham R. Dick, Amy D. Frankhouser, Aanindeeta Banerjee

Green Chemistry

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Abstract

Furan-2,5-dicarboxylic acid (FDCA) is a biomass-derived diacid that can be used to make polymers including polyethylene furandicarboxylate (PEF), a highly attractive substitute for petroleum-derived polyethylene terephthalate (PET). Current FDCA syntheses require edible fructose as the feedstock, entail a difficult oxidation step that generates undesirable aldehyde impurities, and have moderate yields. As an alternative, carbonate-promoted C–H carboxylation enables the synthesis of FDCA from 2-furoic acid and CO2. This route is potentially advantageous because 2-furoic acid is made from furfural, a feedstock produced commercially from inedible lignocellulosic biomass, and it obviates late-stage oxidation. In the carboxylation reaction, salt mixtures composed of alkali furan-2-carboxylate (furoate) and alkali carbonate (M2CO3) are heated under CO2 in the absence of solvent or catalysts to form furan-2,5-dicarboxylate (FDCA2−), which is subsequently protonated to produce FDCA. Previously, high yields were achieved on small-scale reactions using caesium furoate and Cs2CO3. In this work, we investigate the carboxylation reaction using alkali furoate/M2CO3 salts containing cation blends and describe reaction conditions that provide high yields on a preparative scale. We show that the carboxylation proceeds efficiently with K+/Cs+ blends that have a high K+ content (up to 4 : 1 K+ : Cs+). Removing H2O, which is a by-product of the reaction, is important for suppressing decomposition pathways. The accumulation of the FDCA2− product inhibits the reaction. Integrating these lessons, we demonstrate the carboxylation of furoate on a 1 mol scale using a fixed-bed flow reactor with 89% isolated yield of pure FDCA upon protonation.

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Study Snapshot

This study demonstrates a scalable carboxylation route to furan-2,5-dicarboxylic acid using alkali furoate/M2CO3 salts, achieving 89% isolated yield of pure FDCA upon protonation, using inedible lignocellulosic biomass

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

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A scalable carboxylation route to furan-2,5-dicarboxylic acid

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References

Catalytic Aerial Oxidation of Biomass‐Derived Furans to Furan Carboxylic Acids in Water over Bimetallic Nickel–Palladium Alloy Nanoparticles

Bimetallic Ni0.90Pd0.10 nanoparticle catalysts effectively catalyze aerial oxidation of biomass-derived furans to produce furan carboxylic acids, with high yields and excellent stability.

Renewable building blocks for sustainable polyesters: new biotechnological routes for greener plastics

Renewable building blocks and biotechnological production can significantly reduce carbon footprint in the production of advanced polyesters for applications in clothing, food packaging, car manufacturing, and biomedical devices.

Carbon dioxide utilization via carbonate-promoted C–H carboxylation

Carbonate-promoted C-H carboxylation enables efficient carbon-carbon bond formation, potentially transforming inedible biomass and CO2 into valuable feedstock chemicals for renewable synthetic fuels.

New unsaturated copolyesters based on 2,5-furandicarboxylic acid and their crosslinked derivatives

New unsaturated polyesters based on 2,5-furandicarboxylic acid show promising potential as renewable-based materials with similar thermal and mechanical properties to petrochemical ones.

Advances in catalytic production of bio-based polyester monomer 2,5-furandicarboxylic acid derived from lignocellulosic biomass.

Catalytic production of 2,5-furandicarboxylic acid (FDCA) from lignocellulosic biomass offers a promising pathway for producing bio-based polyester to replace petroleum-based polyester.

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