Propene metathesis over silica-supported tungsten oxide catalyst—Catalyst induction mechanism

Abstract

The propene metathesis reaction was studied from the point of view of elucidating the mechanism of catalyst induction and establishing conditions for maximum activity. Instrumental techniques such as ESR, IR, and TPD were used to study the various aspects. During catalyst induction, trace quantities of acetone and acetaldehyde were detected in the product stream, indicating that lattice oxygen from tungsten oxide might be responsible for these products. Induction appeared to proceed via two steps since pretreatment of the catalyst with nitrogen and hydrogen yielded a decreased amount of acetone in the latter case whereas acetaldehyde remained unaffected. ESR studies indicated some interaction between tungsten oxide and silica at the catalyst preparatory stage as well as stabilisation of reduced tungsta species on the catalyst after its use and regeneration. Catalyst activity appeared to depend on conditions of pretreatment. Change in nitrogen pretreatment temperature from 500 to 600°C resulted in transition from strong to negligible external mass transfer behaviour of the catalyst. TPD studies in this context showed possible loss of lattice oxygen from tungsten oxide under the above-mentioned conditions of catalyst pretreatment. ESR studies indicated the reduction of W03 to a nonstoichiometric oxidation state. Hence catalytic activity appears to be related to the nonstoichiometric state of tungsten oxide, which may be WO 2.9 (as deduced from the blue-violet colour of the used catalyst).