Maximizing the production of aromatic hydrocarbons from lignin conversion by coupling methane activation.

Maximizing the production of aromatic hydrocarbons from lignin conversion by coupling methane activation without solvent was investigated over Zn-Ga modified zeolite catalyst. The co-loading of Zn and Ga greatly improves lignin conversion, arene yield along with BTEX (i.e., benzene, toluene, ethylbenzene, and xylene) selectivity, which gives 37.4 wt% yield of aromatic hydrocarbons with 62.2 wt% selectivity towards BTEX at 400 °C and 3.0 MPa. Methane presence has a negligible impact on lignin conversion, but improves arene yield and BTEX selectivity. Liquid 13C, 1H and 2H NMR investigations confirm the incorporation of methane into the final arene products. The NMR results reveal that methane might be incorporated into both the methyl group and aromatic ring, possibly via methylation of aryl moieties and co-aromatization of alkyl moieties. Pyridine and ammonia as probes for surface acidity analysis of the developed catalysts demonstrate that HZSM5 modification with Zn and Ga species could redistribute BAS (Brønsted acid sites) and LAS (Lewis acid sites) and significantly increase the fraction of weak acidic sites on the catalyst, rendering better catalytic performance on the depolymerization of lignin to arene products with higher BTEX selectivity. The results reported in this work may open a novel route to a promising technique for lignin valorization into aromatics and cost-efficient utilizations of biomass and natural gas resources.