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Phosphoric Acid Modification of Hβ Zeolite for Guaiacol Hydrodeoxygenation

Regulating the acid property of zeolite is an effective strategy to improve dehydration of intermediate alcohol, which is the rate-determining step in hydrodeoxygenation of lignin-based phenolic compounds. Herein, a commercial Hβ (SiO2/Al2O3 = 25) was modified by phosphoric acid, and evaluated in the catalytic performance of guaiacol to cyclohexane, combined with Ni/SiO2 prepared by the ammonia evaporation hydrothermal (AEH) method. Incorporating a small amount of phosphorus had little impact on the morphology, texture properties of Hβ, but led to dramatic variations in acid property, including the amount of acid sites and the ratio of Brønsted acid sites to Lewis acid sites, as confirmed by NH3-TPD, Py-IR, FT-IR and 27Al MAS NMR. Phosphorus modification on Hβ could effectively balance competitive adsorption of guaiacol on Lewis acid sites and intermediate alcohol dehydration on Brønsted acid sites, and then enhanced the catalytic performance of guaiacol hydrodeoxygenation to cyclohexane. By comparison, Hβ containing 2 wt.% phosphorus reached the highest activity and cyclohexane selectivity.