Biobased Chemicals from d-Galactose: An Efficient Route to 5-Hydroxymethylfurfural Using a Water/MIBK System in Combination with an HCl/AlCl₃ Catalyst

5-Hydroxymethylfurfural (HMF) is an attractive building block for biobased chemicals. Typically, ketoses like d-fructose (FRC) are suitable starting materials and give good yields of HMF in a simple aqueous phase process with a Bro̷nsted acid catalyst. With aldoses, such as d-glucose (GLU), much lower yields were reported in the literature. Here, we report an experimental and modeling study on the use of d-galactose (GAL) for HMF synthesis, using a liquid-liquid system (water/MIBK) in combination with an HCl/AlCl₃ catalyst. Experiments were conducted in a batch system with temperatures between 112 and 153 °C, HCl and AlCl₃ concentrations ranging from 0.02 to 0.04 M, and initial GAL concentrations between 0.1 and 1.0 M. The highest HMF yield was 49 mol % obtained for a batch time of 90 min at 135 °C. This value is much higher than in experiments with GAL in a monophasic aqueous system with HCl as the catalyst (2 mol % HMF yield) under similar reaction conditions. Based on detailed product analyses, a reaction scheme is proposed in which the isomerization of GAL to tagatose (TAG), catalyzed by the Lewis acid AlCl_3, is the first and key step. TAG is then converted to HMF by Bro̷nsted acid HCl. The experimental data were modeled using a statistical approach as well as a kinetic approach. The kinetic model demonstrates a good agreement between the experimental and modeled data. Our findings reveal that temperature is the reaction variable with the most significant influence on the HMF yield. The use of a biphasic system appears to be a promising method for HMF production from GAL.