Conversion of raw lignocellulosic biomass into branched long‐chain alkanes through three tandem steps

Abstract Synthesis of branched long‐chain alkanes from renewable biomass has attracted intensive interest in recent years, but the feedstock for this synthesis is restricted to platform chemicals. Here, we develop an effective and energy‐efficient process to convert raw lignocellulosic biomass (e.g., corncob) into branched diesel‐range alkanes through three tandem steps for the first time. Furfural and isopropyl levulinate (LA ester) were prepared from hemicellulose and cellulose fractions of corncob in toluene/water biphasic system with added isopropanol, which was followed by double aldol condensation of furfural with LA ester into C 15 oxygenates and the final hydrodeoxygenation of C 15 oxygenates into branched long‐chain alkanes. The core point of this tandem process is the addition of isopropanol in the first step, which enables the spontaneous transfer of levulinic acid (LA) into the toluene phase in the form of LA ester through esterification, resulting in LA ester co‐existing with furfural in the same phase, which is the basis for double aldol condensation in the toluene phase. Moreover, the acidic aqueous phase and toluene can be reused and the residues, including lignin and humins in aqueous phase, can be separated and carbonized to porous carbon materials.