AbstractThe formation of sulphates in an industrial Ni‐W Hydroprocessing (HP) catalyst was investigated by X‐ray Photoelectron Spectroscopy (XPS). A small fluidized bed test unit with on‐line sampling device was constructed to simulate industrial sulfidation and oxyregeneration processes of HP catalysts. The results obtained show that the sulfates observed on the surface of sulfided catalysts are not formed during the sulfidation process. Two oxidation processes seem to be responsible for the formation of sulfates. One of the processes happens when the catalyst is exposed to air before it is properly cooled. The other is a slow conversion at ambient temperature. The two different processes might be associated to different sulfidic species formed during the sulfidation processes, with the sulfides in the bulk of catalyst particles being more easily oxidized than the ones on the external surface of the catalyst particles. The sulfate formed during the air oxidation of sulfided catalysts, as well as that after oxyregeneration is not aluminum sulfate but nickel sulfate in both cases. XPS results also indicate that oxygenates in the feedstock are not directly involved in the sulfate form