Integrated Cascade Process for the Catalytic Conversion of 5‐Hydroxymethylfurfural to Furanic and TetrahydrofuranicDiethers as Potential Biofuels

The depletion of fossil resources is driving the research towards alternative renewable ones. Under this perspective, 5‐hydroxymethylfurfural (HMF) represents a key molecule deriving from biomass characterized by remarkable potential as platform chemical. In this work, for the first time, the hydrogenation of HMF in ethanol was selectively addressed towards 2,5‐bis(hydroxymethyl)furan (BHMF) or 2,5‐bis(hydroxymethyl)tetrahydrofuran (BHMTHF) by properly tuning the reaction conditions in the presence of the same commercial catalyst (Ru/C), reaching the highest yields of 80 and 93 mol%, respectively. These diols represent not only interesting monomers but strategic precursors for two scarcely investigated ethoxylated biofuels, 2,5‐bis(ethoxymethyl)furan (BEMF) and 2,5‐bis(ethoxymethyl)tetrahydrofuran (BEMTHF). Therefore, the etherification with ethanol of pure BHMF and BHMTHF and of crude BHMF, as obtained from hydrogenation step, substrates scarcely investigated in the literature, was performed with several commercial heterogeneous acid catalysts. Among them, the zeolite HZSM‐5 (Si/Al=25) was the most promising system, achieving the highest BEMF yield of 74 mol%. In particular, for the first time, the synthesis of the fully hydrogenated diether BEMTHF was thoroughly studied, and a novel cascade process for the tailored conversion of HMF to the diethyl ethers BEMF and BEMTHF was proposed.