Gallium-loaded zeolites for light paraffin aromatization: evidence for exchanged gallium cation active centers

It is shown that certain metal-loaded zeolites (e.g., Ga-MFI) initially prepared as separate metal-containing and zeolite phases are reducible, resulting in solid-state transfer of the metal to the zeolite. The final material is similar to those initially prepared as ‘unsegregated’ by methods such as aqueous impregnation. Reduction occurs either through appropriate pretreatment or onstream in certain hydrocarbon reactions. First, preparation methods leading to one or the other type of material are examined. Then it is shown that reduced catalysts give far higher ratios of dehydrogenation to cracking rates (for alkanes) than either segregated or unsegregated but unreduced systems. The product distributions of the propane reaction at low partial pressure and low conversion are also reviewed, and new data presented for unsegregated, reduced catalysts. There are great differences in the distribution obtained using reduced 1/1 metal/A1 catalysts from corresponding distributions for the H-form zeolites or for segregated systems. The differences suggest a mechanism which may be entirely independent of catalysis by protons.