Catalytic Transformation of Lignocellulosic Biomass into Arenes, 5‐Hydroxymethylfurfural, and Furfural

Abstract The complete transformation of lignocellulosic biomass into valuable platform chemicals is of great significance. Herein, a catalytic process for the upgrading of lignocellulose to arenes, 5‐hydroxymethylfurfural (HMF), and furfural is reported. Firstly, the lignin fraction in lignocellulosic biomass is selectively converted into lignin oil (82.9 mol % yield of lignin monomers from birch wood) over a Pd/C catalyst and then further hydrodeoxygenated to arenes in catalytic hydrogen‐transfer reactions over a Ru/Nb 2 O 5 catalyst. High yields of C 7 –C 9 hydrocarbons (95.6 mol %) with 85.6 wt % selectivity to arenes based on lignin oil are achieved owing to the synergistic effect between Ru and Nb 2 O 5 , which enables direct hydrogenolysis of the C aromatic −OH bond in phenolics. Secondly, the cellulose and hemicellulose fractions in the Pd/C‐containing solid residue, as well as methylated C 5 sugars produced during the stripping of lignin, are converted into HMF and furfural with a total yield of up to 24.5 wt % (based on the amount of birch wood) in a THF/concentrated seawater (ca. 30 wt % salts) biphasic reaction system. Here, seawater played a key role in the conversion of cellulose and hemicellulose into HMF and furfural, respectively; more importantly, it made the separation and reuse of the Pd/C catalyst easier. With this catalytic process, the complete and efficient transformation of lignocellulose into highly value‐added products with recycling of each catalyst and solvent has been realized.