Catalyst Deactivation Due to Glaze Formation from Oil-Derived Phosphorus and Zinc

The deactivation of automotive catalysts by engine oil-derived components of phosphorus and zinc can occur by the formation of an amorphous zinc pyrophosphate (Zn₂P₂O₇) that is impervious to gas diffusion. The catalyst poison, derived from antiwear oil additive zinc dialkyl dithiophosphate (ZDP) in low-temperature exhaust environments, appears as glassy, amorphous deposits on catalysts as shown by scanning electron microscopy (SEM).

Laboratory studies were performed to understand the effects of exhaust stoichiometry, temperature, rate of oil burn, and chemical form of P and Zn compounds on glaze formation. The formation of the amorphous deposits using a laboratory pulsator apparatus showed that noncombusted ZDP causes the glaze formation. Electron microprobe studies indicated the association of P with Zn on precious metal films exposed to ZDP combustion products. Secondary ion mass spectrometry (SIMS) confirmed a similar P to Zn correspondence on the vehicle-aged catalysts. Once formed, the amorphous zinc pyrophosphate glaze could only be removed under high-temperature, reducing conditions which sintered the catalyst with no significant improvement in activity. Guidelines are presented for exhaust temperatures necessary for catalyst operation and prevention of catalyst deactivation by the formation of Zn pyrophosphate glaze.