Challenges of Green Production of 2,5‐Furandicarboxylic Acid from Bio‐Derived 5‐Hydroxymethylfurfural: Overcoming Deactivation by Concomitant Amino Acids

Abstract

The oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is highly attractive as FDCA is considered as substitute for the petrochemically derived terephthalic acid. There are only few reports on the direct use of unrefined HMF solutions from biomass resources and the influence of remaining constituents on the catalytic processes. In this work, the oxidation of HMF in a solution as obtained from hydrolysis and dehydration of saccharides in chicory roots was investigated without intermediate purification steps. The amount of base added to the solution was critical to increase the FDCA yield. Catalyst deactivation occurred and was attributed to poisoning by amino acids from the bio-source. A strong influence of amino acids on the catalytic activity was found for all supported Au, Pt, Pd, and Ru catalysts. A supported AuPd(2 : 1)/C alloy catalyst exhibited both superior catalytic activity and higher stability against deactivation by the critical amino acids.

Continuous flow oxidation of HMF using a supported AuPd-alloy

“…Nevertheless, the discrepancy was marginal for all the catalysts, and no significant differences in catalytic activity were anticipated due to these variations. 21…”

“…AuPd-alloyed particles with a targeted ratio of 52 : 48 (Au : Pd) were prepared according to a method previously published by our group. 21 In brief, PdCl 2 ( m = 0.0222 g) and HAuCl 4 ·3H 2 O ( m = 0.0533 mg) were dissolved in diluted HCl (3 mL conc. HCl in 77 mL H 2 O) for about 3 h. Subsequently, 620 mL H 2 O and poly(vinylalcohol) (PVA; m = 37.8 mg) were added.…”

“…In our study, we systematically explore the oxidation of HMF in a continuous flow reactor utilizing AuPd-based catalysts renowned for their efficacy in achieving high FDCA yields in batch reactors. 21,34,37,38,50 We implemented air as a sustainable and economical oxidant, water as a safe and green solvent, Na 2 CO 3 as a mild and non-toxic base, and heterogeneous catalysts in a fixed-bed reactor to avoid separation of the catalytic system from the reaction mixture. These measures collectively enable a more sustainable approach to the production of the important renewable monomer FDCA.…”

A Proposal for Evaluating the Economic Viability of Biorefineries against Petrochemical Benchmarks

“…Special attention has been paid to the oxidation of the hydroxymethyl and aldehyde groups, yielding 2,5-furandicarboxylic acid (FDCA), a promising monomer for plastics [17]. Bio-based plastics constitute an interesting and still growing market segment for HMF applications.…”

Toward effective electrocatalytic C–N coupling for the synthesis of organic nitrogenous compounds using CO2 and biomass as carbon sources

“…Biomass, a kind of carbon‐neutral energy source by absorbing CO 2 from the atmosphere through photosynthesis, is a vital renewable resource that is abundant on Earth and can be utilized to produce a diverse range of biomaterials and bioenergy, meeting the diverse development needs of modern society 14,158,159 . After processing, biomass raw materials could produce different biomass‐derived molecules such as 5‐hydroxymethylfurfural (HMF), 160 α‐hydroxy acids, and α‐keto acids 161,162 . These biomass‐derived molecules could be further transformed into fine chemicals that are conventionally produced from fossil fuel resources 163–166 .…”