The direct conversion of glucose to 5-ethoxymethylfurfural (EMF) is a promising biomass transformation due to the potential application of the product as a biofuel. Here, the conversion of glucose to EMF was examined over several solid acid catalysts in ethanol between 96 and 125 °C. Among the catalysts employed, dealuminated beta zeolites [DeAl-H-beta-12.5 (700)] gave a moderate yield of EMF (37%) in a single step catalytic process. A combined catalytic system consisting of H-form zeolite and Amberlyst-15 was found to be more efficient for the transformation of glucose to EMF (46%) via a one-pot, two-step reaction protocol. Alternative biomass-based mono-, di- and polysaccharides also gave moderate to good yields of EMF with the catalytic systems, including fructose which yielded 67% of EMF and 4% of ethyl levulinate (ELevu) along with 10% 5-hydroxymethyl furfural (HMF) in the combined reaction protocol. A significant amount of ELevu (1–16%), a rehydrated product of EMF and a promising fuel additive, was observed in this study. Recyclability studies suggested that it was possible to reuse the DeAl-H-beta-12.5 (700) catalyst in consecutive reactions without significant changes in product yields due to its easy recovery and thermal stability during regeneration.

Catalytic valorisation of biomass with solid functional materials has been recognised as a promising approach to produce value-added biochemicals and biofuels. Furanic compounds such as 5-hydroxymethylfurfural (HMF), 5-ethoxymethylfurfural, 2,5-dimethylfuran, 2,5-diformylfuran and 2,5-furandicarboxylic acid can be obtained from hexoses and pentoses via selective dehydration and subsequent etherification, hydrogenation, oxidation reactions, which show great potential for industrial applications to replace petroleum-based chemicals and fuels. Zeolite and zeotype micro- and mesoporous materials with tuneable acidity, good thermal stability and shape-selectivity have recently emerged as promising solid catalysts, exhibiting superior catalytic performance to other heterogeneous catalysts. This review focuses on the synthesis of biomass-derived furanic compounds catalysed by zeolitic materials, firstly introducing zeolite-catalysed hydrolysis of di-, oligo- and polysaccharides and isomerization reactions of monomeric sugars. Subsequently, the catalytic dehydration reactions of hexoses and pentoses to obtain HMF and furfural are reported. Particularly, a variety of reaction pathways towards upgrading of the resulting platform furanic molecules to valuable bioproducts over zeolitic materials are discussed.