Tungstoborate heteropolyacid-catalyzed lignin liquefaction: Product yield and component distribution

Tungstoborate heteropolyacid catalysts have good catalytic degradation performance, especially for selective cleavage of C–C bonds in biomass. In this paper, the product yield and component distribution of tungstoborate heteropolyacid (BW12)-catalyzed lignin liquefaction were investigated at different parameters, including temperatures (120, 140, 160, 180, and 200 °C), catalyst amount (0, 2.5, 5, 10, and 20 wt. %), and reaction time (0, 30, 60, 90, and 120 min). It was found that a higher conversion (72.16 wt. %) and bio-oil yield (68.41 wt. %) could be obtained under suitable reaction conditions (180 °C, 60 min, 5 wt. %). Bio-oil analysis showed that the BW12 catalyst had a significant effect on the distribution of bio-oil fractions, in which mono-aromatic components increased from 32.96% to 47.56% compared to those without the catalyst. In particular, carbonyl substances in the mono-aromatic components increased from 18.66% to 26.97%. Spectroscopic analysis (FT-IR) found that the absorption peaks of C–O and C–C bonds in the liquefied residue catalyzed by BW12 decreased compared to the raw lignin. Moreover, the mechanism of BW12-catalyzed lignin depolymerization was investigated by DFT simulations. The simulation results demonstrated that the shortening of Cα–O bond, the breaking of Cβ–Cγ and Cα–Cβ bonds in lignin promoted the formation of vanillin and benzaldehyde, 3-hydroxy-4-methoxy. Finally, based on the experimental data and simulation results, a possible reaction pathway for the BW12-catalyzed liquefaction of lignin into mono-aromatic substances was proposed.