Molecular structure and sour gas surface chemistry of supported K 2 O/WO 3 /Al 2 O 3 catalysts
Molecular structures of the unprompted and K 2 O-promoted supported WO 3 /Al 2 O 3 catalysts were studied with in situ Raman and UV-vis spectroscopy. In situ Raman spectra revealed that supported 20% WO 3 /Al 2 O 3 corresponds to near monolayer coverage of isolated and oligomeric surface WOx species on Al 2 O 3 . Above monolayer surface WO x coverage (21% WO 3 /Al 2 O 3 ), crystalline WO 3 nanoparticles are also present. The addition of K 2 O to the supported WO 3 /Al 2 O 3 catalyst increased the concentration of isolated surface WO x species and did not form K 2 WO 4 nanoparticles. The reducibility of the tungsten oxide structures depends on their structures (2D or 3D) and the K 2 O promoter. Their interaction with acidic CO 2 and SO 2 gases was also investigated. Adsorption of CO 2 creates several surface carbonate species of varying acidity that were detected using a combination of in situ IR and mass spectroscopy. Adsorbed bicarbonate form on weakly basic surface sites on tungsten oxide monolayer WO 3 /Al 2 O 3 catalyst as well as in the presence of low 2.5% K 2 O loading. At high 5% K 2 O loading, the presence of the strong surface basic sites yields adsorbed carbonates. In conclusion, after SO 2 pretreatment, however, new strongly adsorbed sulfate appears on the surface that inhibit CO 2 adsorption.