Effect of sulphur poisoning on perovskite catalysts prepared by flame-pyrolysis

ABO(3) perovskite-like catalysts are known to be sensitive to sulphur-containing compounds. Possible solutions to increase resistance to sulphur are represented by either catalyst bed protection with basic guards or catalyst doping with different transition or noble metals. In the present work La((1-x))A(x)'CoO(3), La((1-x))A(x)'MnO(3) and La((1-x))A(x)'FeO(3), with A' = Ce, Sr and x = 0, 0.1, 0.2, either pure or doped with noble metals (0.5 wt% Pt or Pd), were prepared in nano-powder form by flame-pyrolysis. All the catalysts were tested for the catalytic flameless combustion of methane, monitoring the activity by on-line mass spectrometry. The catalysts were then progressively deactivated in operando with a new procedure, consisting of repeated injection of some doses of tetrahydrothiophene (THT), usually employed as odorant in the natural gas grid, with continuous analysis of the transient response of the catalyst. The activity tests were then repeated on the poisoned catalyst. Different regenerative treatments were also tried, either in oxidising or reducing atmosphere. Among the unsubstituted samples, higher activity and better resistance to poisoning have been observed in general with manganites with respect to the corresponding formulations containing Co or Fe at the B-site. The worst catalyst showed LaFeO(3), from both the points of view of activity and of resistance to sulphur poisoning. La(0.9)Sr(0.1)MnO(3) showed, the best results, exhibiting very high activity and good resistance even after the addition of up to 8.4 mg of THT/g of catalyst. Interesting results were attained also by adding Sr to Co-based perovskites. Sr showed a first action by forcing Mn or Co in their highest oxidation state, but, in addition, it could also act as a sulphur guard, likely forming stable sulphates due to its basicity. Among noble metals, Pt doping proved beneficial in improving the activity of both the fresh and the poisoned catalyst.