Non-coking stable alkaline earth metal (M = Mg, Sr, and Ba) modified Ga-NaY catalysts were prepared by ionic-exchange and tested in oxidative dehydrogenation (ODH) of n-octane using air as the source of oxygen. The role of the alkaline earth metals in NaY was to poison the acid sites while enhancing the basic sites responsible for ODH. The exception was the calcium modified NaY, which was more acidic than the parent NaY, coking and unstable under the ODH conditions used in this study. The role of gallium was to enhance the dehydrogenation pathway and improve the stability of NaY. The sequence of increasing selectivity to octenes followed the order: CaGa-NaY < Ga-NaY< MgGa-NaY < SrGa-NaY < BaGa-NaY. The highest octene selectivity obtained was 37% at iso-conversion of 6 ± 1% when BaGa-NaY was used at a temperature of 450 °C. The activity of the catalysts was directly proportional to the reducibility of the catalysts, which is in agreement with expectations.

The effect of the thermal treatment of some zeolitic materials was studied on oxidative dehydrogenation (ODH) of n-octane. Gallium containing faujasite catalysts were synthesized using isomorphic substitution, specifically, a galosilicalite (Ga-BaY(Sil)) and an aluminosilicalite substituted with gallium (Ga-BaY(IS)), with constant Si/M ratio. The catalysts were thermally treated at different temperatures (250, 550, and 750 °C) before catalytic testing. The quantification of total and strength of acid sites by FT-IR (O-H region), pyridine-IR, and NH3-temperature-programmed desorption (TPD) confirmed a decrease in the number of Brønsted acid sites and an increase in the number of Lewis acid sites upon increasing the calcination temperature. Isothermal n-octane conversion also decreased with the catalysts’ calcination temperature, whereas octene selectivity showed the opposite trend (also at iso-conversion). The COx selectivity showed a decrease over the catalysts calcined from 250 to 550 °C and then an increase over the 750 °C calcined catalysts, which was due to the strong adsorption of products to strong Lewis acid sites on the catalysts leading to the deep oxidation of the products. Only olefinic-cracked products were observed over the 750 °C calcined catalysts. This suggested that the thermal treatment increases Lewis acid sites, which activate n-octane using a bimolecular mechanism, instead of a monomolecular mechanism.

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