Production of 5-Hydroxymethylfurfural (HMF) from Sucrose in Aqueous Phase Using S, N-Doped Hydrochars

5-Hydroxymethylfurfural (HMF) is a versatile platform molecule with the potential to replace many fossil fuel derivatives. It can be obtained through the dehydration of carbohydrates. In this study, we present a simple and cost-effective microwave-assisted method for producing HMF. This method involves the use of readily available sucrose as a substrate and glucose-derived bifunctional hydrochars as carbocatalysts. These catalysts were produced via hydrothermal carbonisation using thiourea and urea as nitrogen and sulphur sources, respectively, to introduce Brønsted acidic and basic sites into the materials. Using a microwave reactor, we found that the S, N-doped hydrochars were active in sucrose dehydration in water. Catalytic results showed that HMF yield depended on the balance between acidic and basic sites as well as the types of S and N species present on the surfaces of these hydrochars. The best-performing catalyst achieved an encouraging HMF yield of 37%. The potential of N, S-co-doped biochar as a green solid catalyst for various biorefinery processes was demonstrated. A simple kinetic model was developed to elucidate the kinetics of the main reaction pathways of this cascade process, showing a very good fit with the experimental results. The calculated rate constants revealed that reactions with a 5% sucrose loading exhibited significantly higher fructose dehydration rates and produced fewer side products than reactions using a more diluted substrate. No isomerisation of glucose into fructose was observed in an air atmosphere. On the contrary, a limited rate of isomerisation of glucose into fructose was recorded in an oxygen atmosphere. Therefore, efforts should focus on achieving a high glucose-to-fructose isomerisation rate (an intermediate reaction step) to improve HMF selectivity by reducing humin formation.