Promotion of biomass pyrolytic saccharification and lignin depolymerization via nucleophilic reagents quenching of the carbonium ions

The condensation of lignin under acidic conditions inhibited the subsequent value-added utilization of lignin, and the condensed lignin covered the biomass surface. Here, a method of benzenesulfonic acid pretreatment combined with nucleophilic reagents promoted pyrolytic saccharification and lignin hydrogenation was reported. The anhydrosugar content in the pyrolysis bio-oil increased from 66.91% to 69.00%, 72.88%, and 72.16% via adding methanol, propionaldehyde, 3-hydroxylic-2-naphthoic acid, respectively. The characterization of the biomass surface structure and the calculation of bond lengths indicated that carbonium ions prefer to bind with the added nucleophilic reagent rather than the lignin fragment. Furthermore, the quenching of the carbonium ions preserved the β-O-4 bond, as demonstrated in 2D NMR. In the subsequent hydrogenation reaction, it was found that methanol facilitated the production of lignin monomer. The calculation also revealed that the quenching of the carbonium ions with methanol reduced the bond-breaking energy of the β-O-4 bond.