Kinetic Modeling of Homogenous Catalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid

2,5-Furandicarboxylic acid (FDCA) is a valuable biomass-based monomer with broad market prospects that can replace terephthalic acid (TPA) in all kinds of polymer applications. In this work, the homogeneous catalytic oxidation of 5-hydroxymethylfurfural (HMF) to FDCA was investigated over a Co/Mn/Br catalyst with acetic acid/water as a solvent. On the basis of free radical oxidation reaction mechanisms, one simplified main reaction kinetic model for the oxidation of HMF with six parameters was proposed, which considered the formation of FDCA and the most important intermediates. The effects of catalyst, temperature, and water content on the liquid-phase oxidation kinetics of HMF were investigated. The model fitted the experimental data well, in which only the chain initiation rate constant was found to be dependent on experimental conditions, while other rate constants can be kept constant in the investigated range. Hopefully, the kinetic model in this work can provide valuable insights for the design and optimization of the industrial process of HMF oxidation to FDCA.