Catalysis Today, Vol.33, No.1-3, 151-160, 1997
Catalytic Synergy via Spillover at Low-Temperature - The Dehydration and Dehydrogenation of SEC-Butanol in the Presence of Oxygen
This paper reports results concerning the dehydration-dehydrogenation of 2-butanol at low temperatures over mechanical mixtures of oxides : alpha-Sb2O4 + SnO2 and alpha-Sb2O4 + MoO3, where each pure oxide had been prepared separately. The temperatures of reaction were 240 degrees C and 190 degrees C, respectively, for the two mixtures. Both mixtures exhibited better performances than the pure oxides. The alpha-Sb2O4 + SnO2 mixture was not active in 2-butanol dehydration. The yields and the selectivities for butene and/or methyl-ethyl-ketone obtained in the other cases were higher than the theoretical values calculated from the activities of the pure oxides. SBET, XRD and XPS measurements before and after the catalytic reaction did not indicate any change of phase or a contamination during the preparation of the mixtures or during the reaction. The synergetic effects between the phases are therefore explained by the occurrence of a ’remote control mechanism’ acting via the migration of spillover oxygen species. These are the first instances of a remote control operating at temperatures of reaction below 250 degrees C. The actions of spillover are the same as at high temperature : creation of new acid sites on MoO3, regeneration (reoxidation) of the reduced deactivated redox sites on both SnO2 and MoO3 and inhibition of the coke formation during the reaction.
Keywords:SELECTIVE OXIDATION CATALYSTS;ETHYL FORMAMIDE DEHYDRATION;PHASE COOPERATION;ANTIMONY OXIDES;METHACROLEIN;ALPHA-SB2O4;ISOBUTENE;MIXTURES;MOO3;TIN