Oxidative Dehydrogenation of 1-Butene to 1,3-Butadiene Over Metal Ferrite Catalysts

The oxidative dehydrogenation (ODH) of 1-butene to 1,3-butadiene was studied over a series of AFe2O4 catalysts, where A = Zn, Mn, Ni, Cu, Mg and Fe. The catalysts were characterised by XPS, EPR spectroscopy, BET surface area analysis, Raman spectroscopy and XRD. All the ferrites were active for ODH and gave an order of activity after 80 h on-stream of ZnFe2O4 > NiFe2O4 > MnFe2O4 > MgFe2O4 > CuFe2O4 > FeFe2O4. All catalysts lost significant surface area (up to ~ 80%) under reaction conditions of 0.75:1:15 oxygen:1-butene:steam with an overall GHSV of 10,050 h−1 at 693 K. Fe3O4 was unstable under reaction conditions and was converted to Fe2O3, which showed very low activity. Nickel ferrite was the only material that gave carbon dioxide as a significant product, all others were selective to 1,3-butadiene. Zinc ferrite gave a steady-state yield of 1,3-butadiene of ~ 80%. Inversion parameters were determined for the ferrites from XPS and a correlation was obtained between 1,3-butadiene yield and inversion parameter, indicating that Fe3+ in an octahedral hole is a key species in the mechanism of oxidative dehydrogenation. Butene isomerisation and ODH were shown to occur on different sites.