Effect of Al Content on the Gas-Phase Dehydration of Glycerol over Silica-Alumina-Supported Silicotungstic Acid Catalysts

The gas-phase dehydration of glycerol to acrolein was carried out over silicotungstic acid ($H_4SiW_{12}O_{40}{\cdot}xH_2O$, HSiW) catalysts supported on $SiO_2$, ${\eta}-Al_2O_3$, and silica-aluminas with different Al contents. The HSiW catalysts supported on silica-aluminas showed higher glycerol conversions and acrolein yields during the initial 2 h at $315^{\circ}C$ than did $SiO_2$- and ${\eta}-Al_2O_3$-supported HSiW catalysts. Among the tested catalysts, HSiW/$Si_{0.9}Al_{0.1}O_x$ exhibited the highest space-time yield during the initial 2 h. The loaded HSiW species can change the acid types and suppress the formation of carbonaceous species on Al-rich silica-aluminas. The deactivated HSiW supported on silica-aluminas can be fully regenerated after calcination in air at $500^{\circ}C$. As long as the molar ratio between water and glycerol was in the range of 2-11, the acrolein selectivity increased significantly with increasing water content in the feed, while the surface carbon content decreased owing to the suppression of heavy compounds.