The fractionation of lignocellulose utilizing green solvents is essential for the effective operation of biorefineries. In this study, a deep eutectic solvent (DES) system composed of benzoic acid (BA, hydrogen bond donor) and choline chloride (ChCl, hydrogen bond acceptor) was fabricated and successfully applied to the lignocellulose fractionation. The DES has low toxicity and little pollution. In this system, 67.8 % of lignin and 91.2 % of hemicellulose in poplar were removed, leaving 95.8 % of cellulose intact as solid residue. Due to the removal of the amorphous components, crystallinity of cellulose-rich water-insoluble solid (CIS) substantially increased from 55.6 % to 68.6 %, and CIS was used as feedstock for nanocrystalline cellulose preparation with excellent properties. The results showed that the obtained lignin had similar properties to CEL by GPC, FT-IR, 2D-NMR and TGA. A high-purity lignin rich in G units was recovered with a well-preserved structure, which has β-O-4 linkage content up to 53.01 %, low molecular weight, low polydispersity (1.99). Finally, the hydrolyzate can be used for fermentation. This study demonstrated that BA is suitable for DES design with excellent properties on lignin extraction, and this promising DES enable efficient pretreatment for economically feasible biomass conversion. This ChCl-BA DES facilitates environmentally friendly production of functional materials derived from cellulose and lignin under mild conditions.
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