The Synthesis of Different Series of Cobalt BEA Zeolite Catalysts by Post-Synthesis Methods and Their Characterization

Three series of zeolite catalysts Co all-silica and Co Al-containing zeolites beta were prepared for use in the selective oxidative dehydrogenation of propane to propylene. Two series of zeolite catalysts Co all-silica were prepared by a two-step postsynthesis method at pH = 2.5 and pH = 3.0–9.0, respectively, which allows the incorporation of cobalt into SiBEA zeolite in the form of isolated framework pseudo-tetrahedral Co(II) species. The incorporation of Co ions into vacant T-atom sites and their reaction with silanol groups were demonstrated by NMR and FTIR methods. The generation of Lewis acid sites without the formation of Brønsted sites was proved by FTIR using pyridine and CO as probe molecules. The state of cobalt in three series of prepared and calcined zeolite catalysts was characterized by DR UV-vis. This technique allowed to show that for low Co content (<2 wt.%) cobalt is present in the form of framework pseudo-tetrahedral Co(II) species. For higher Co content (>2 wt.%), both framework pseudo-tetrahedral and extra-framework octahedral Co(II) species are present. The Co Al-containing zeolite beta series prepared on non-dealuminated support shows the presence of extra-framework octahedral Co(II) only.