Selective Skeletal Butene Isomerization Through a Bimolecular Mechanism

n-Butene transformation was carried out at 350°C over medium pore size zeolites (H-FER, H-TON, H-EU-1 and H-MFI) and at 500°C over alumina. With fresh catalysts, not only isobutene but also propene and pentenes are primary products, which indicates that at least some of the butene isomerization occurs through oligomerization-isomerization-cracking steps (bimolecular mechanism). The large differences in selectivity are due to many factors, including whether or not trimer intermediates participate in the mechanism and limited product desorption. All the catalysts exhibit increasing isobutene selectivity with increasing time on-stream. This increase in selectivity can be explained by the selective isomerization of n-butene through a reaction process whose first step is the formation of trimethylpentene intermediates from isobutene product and n-butene reactant. This autocatalytic reaction can render the bimolecular transformation of n-butenes very selective to isobutene