Towards an intensified process of biomass-derived monomers: The influence of HMF by-products on gold-catalyzed synthesis of 2,5-furandicarboxylic acid

The utilization of biomass and development of intensified processes are essential to establish a sustainable production of chemicals in the future. Herein, we report on a strategy that allows one to directly convert the biomass-derived platform molecule 5-(hydroxymethyl)furfural (HMF) over Au/ZrO2 in aqueous medium to 2,5-furandicarboxylic acid (FDCA), a renewable building block for biobased polymers like polyethylene furanoate. The focus lies on identifying the influence of 5-(hydroxymethyl)furfural synthesis byproducts, like unconverted sugars, levulinic acid, and formic acid as well as the remaining inorganics, on the synthesis of 2,5-furandicarboxylic acid to save the intermediate step of HMF purification. These components were added to the reaction mixture individually and in combination to study their effect. Although most of these substances lowered the FDCA yield, the reaction conditions could be optimized to produce FDCA quantitatively. Only the addition of levulinic acid led to a severe deterioration of the production of FDCA, which was attributed to poisoning of the catalyst. In a realistic technical scenario, the direct oxidation of impure HMF from unconcentrated sugar syrup in high FDCA yield (74%) was demonstrated. Catalyst stability was investigated in the presence of sugars. On the basis of these studies, highly needed recommendations for the HMF synthesis were developed to establish a more sustainable, technically feasible, and intensified process for direct FDCA production from sugars at industrial scales