On the effect of mesoporosity of FAU Y zeolites in the liquid-phase catalysis

The porosity and acidity of three commercial FAU Y zeolites (including the original HY-2.6 and dealuminated HY-15/-30 zeolites) were studied comprehensively using nitrogen (N-2) physisorption, and mercury (Hg) porosimetry, ammonia temperature-programmed desorption (NH3-TPD) and pyridine Fourier transform infrared (pyridine-IR) analyses. The combined N-2 physisorption and Hg porosimetry is a useful tool to evaluate the hierarchical mesoporosity in the dealuminated samples, revealing that HY-15 and HY-30 possess > 50% open mesoporosity in the mesopores range of 5-10 nm. The acidity of the dealuminated Y zeolites has been reduced significantly in comparison to that of the original HY-2.6, e.g. Bronsted acidity decreased by ca. 69 folds by dealuminating HY-2.6 to HY-30. Catalytic results of Fischer esterification of methanol with carboxylic acids and aldol condensation of benzaldehyde with 1-heptanal have evidenced that the critical role of mesoporosity of the dealuminated Y zeolites in liquid-phase reactions. For example, in the esterification of lauric acid with methanol, HY-15 and HY-30 with hierarchical mesopores showed better catalytic activity (Le. conversion of lauric acid: 7.9% and 24.5%, respectively) than HY-2.6 (4.0%). The analysis of the catalytic results along with the acidic property suggests that the acidity is less influential than the porosity of zeolite catalysts. Results from this study allow us to explain the origin of the high activity of zeolites with mesoporosity in the liquid-phase catalysis.