Production of Renewable p‑Xylene from 2,5-Dimethylfuran and Ethylene over MWW Zeolite Catalysts

The production of biobased p-xylene (PX) from 2,5-dimethylfuran (DMF) and ethylene has gained more and more attention from the aspects of both the environmentally friendly route and practical application. Despite the catalytic activity of the reported catalysts, the design and synthesis of new zeolite-based catalysts with strong durability are extremely desirable but still remain a significant challenge. Herein, we report MWW-type zeolite as highly efficient catalysts for PX production. The lamellar structure and external hemicavities endow MWW zeolite with a favorable mass transfer performance. Al-MWW synthesized with the H3BO3 additive exhibits a remarkably higher PX selectivity than conventional MCM-22 due to its lower Brønsted/Lewis ratio of 2.0 and a less strong Brønsted acid proportion of 53%. The incorporation of heteroatoms into the zeolite can further regulate the Brønsted/Lewis acidity, and Ga/Al-MWW zeolite with a B/L ratio of 1.0 and the least strong Brønsted acid proportion of 43% was found to be the most efficient catalyst (PX selectivity of 80.3%). This work pushes ahead the knowledge of MWW-type zeolite catalysts for PX production, which would also be constructive for the development of new zeolite catalysts.