Effects of Co-fed O 2 and CO 2 on the deactivation of Mo/HZSM-5 for methane aromatization

Abstract

The aromatization of methane in the presence of H 2, CO and CO 2 over a 2 wt.% Mo/HZSM-5 catalyst was studied. The results were compared with those for the aromatization reaction in pure methane and with added O 2. The addition of O 2 up to 5.3% or CO 2 up to 12.8% reduces deactivation so that, at the reaction temperature of 770 °C, an aromatic yield of ca. 4% can be maintained for 6 h; in the absence of the gaseous additive, however, the catalyst would have been completely deactivated for aromatic formation within 4 h. XPS analysis revealed that, in the presence of O 2 or CO 2, the molybdenum oxide supported on the HZSM-5 located at the reactor inlet was not converted to molybdenum carbide, whereas in the zone away from the reactor inlet, Mo 2C was found. Investigation by temperature-programmed surface reaction showed that the production of aromatic compounds was always preceded by the reaction of molybdenum oxide with methane to form Mo 2C and CO. The beneficial effect of adding CO 2 and O 2 in low concentration was mainly attributed to the formation of CO and H 2 by oxidation and the reforming of methane in the zone closed to the reactor inlet. H 2 enhances the stability of the catalyst by suppressing the excessive dehydrogenation of the reaction intermediates into inactive entities. When the concentration of CO 2 and O 2 was too high, the entire catalyst bed remained oxidized and the methane aromatization reaction could not occur.