In this work, a heterogeneous catalytic system consisting of [HO₂CMMIm]Cl and ZrOCl₂ in isopropanol is demonstrated to be effective for 5-hydroxymethylfurfural (HMF) synthesis with glucose as the feedstock. Various reaction conditions for HMF synthesis by glucose dehydration were investigated systematically. Under optimized reaction conditions, as high as 43 mol% HMF yield could be achieved. Increasing the water content to a level below 3.17% led to the production of HMF with a higher yield, while a lower HMF yield was observed when the water content was increased above 3.17%. In addition, the data also showed that ZrOCl₂ could not only effectively convert glucose into intermediate species (which were not fructose, in contrast to the literature) but also catalyze the intermediate species’ in situ dehydration into HMF. [HO₂CMMIm]Cl was used to catalyze the intermediate species’ in situ conversion to HMF. The kinetics data showed that a temperature increase accelerated the intermediate species’ dehydration reaction rate. The reaction of glucose dehydration was a strong endothermal reaction.

TiO₂/SiO₂, Cr₂O₃-NiO/SiO₂, and TiO₂-Cr₂O₃/SiO₂ were prepared by the impregnation method for alkyl carbamate synthesis using urea as the carbonyl source. Up to 97.5% methyl carbamate yield, 97% ethyl carbamate yield, and 96% butyl carbamate yield could be achieved, respectively. The catalysts were characterized by ICP-AES, BET, XRD, XPS, NH₃-TPD, and EPMA. Catalytic activity investigation revealed that TiO₂/SiO₂, Cr₂O₃-NiO/SiO₂, and TiO₂-Cr₂O₃/SiO₂ were effective catalysts for methyl carbamate (MC), ethyl carbamate (EC), and butyl carbamate (BC), respectively. The recycling tests suggested that these silica gel supported catalyst system is active, stable, and reusable. A total of 96–97% alkyl carbamate (methyl, ethyl, and butyl) could be obtained in a 2 L autoclave, and these data suggested that our catalyst system is relatively easy to scale up.