ABO3 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'xCoO3, La(1-x)A'xMnO3 and La(1-x)A'xFeO3, 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 LaFeO3, from both the points of view of activity and of resistance to sulphur * Corresponding author: fax +39-02-50314300, e-mail ilenia.rossetti@unimi.it 2 poisoning. La0,9Sr0,1MnO3 showed, the best results, exhibiting very high activity and good resistance even after the addition of up to 8.4 mg of THT per 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.Keywords: Methane, catalytic combustion; Sulphur poisoning; Perovskite-like catalysts. -INTRODUCTIONThe catalytic flameless combustion (CFC) of methane outperforms conventional flame combustion because of lower emission of pollutants (HC, CO and NOx) and high thermal efficiency. The catalysts traditionally used for CFC are mainly based on supported noble metals, such as Pd and Pt, which ensure high activity, however accompanied by some drawbacks, due to high cost and poor thermal and chemical stability. La-based catalysts with ABO3 perovskite-like structure [1][2][3][4] have been proposed as a valid alternative for the present application. Indeed, perovskite catalysts combine low cost, thermo-chemical stability at high operating temperature and satisfactory catalytic activity [5][6][7][8]. In spite of this, there are still some open questions, especially regarding their resistance to sulphur poisoning when used for the CFC of methane. Indeed, the poisoning mechanism of perovskite-like catalysts has not been completely understood a...

Ag represents an interesting dopant for the highly active LaCoO3 perovskites used for the catalytic flameless combustion (CFC) of methane, due to its ability to adsorb and activate oxygen and to the possibility of incorporation into the framework Higher activity was observed, in general, with fresh catalysts synthesised by FP. The SG samples demonstrated a slightly better resistance to sulphur poisoning when considering the conversion decrease between the fresh and the poisoned samples, due to lower surface exposure. However, interesting data have been

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LaMnO(3), either pure or doped with 10 mol % Sr, has been prepared by flame pyrolysis in nanostructured form. Such catalysts have been tested for the catalytic flameless combustion of methane, achieving very high catalytic activity. The resistance toward poisoning by some model N-containing impurities has been checked in order to assess the possibility of operating the flameless catalytic combustion with biogas, possibly contaminated by S- or N-based compounds. This would be a significant improvement from the environmental point of view because the application of catalytic combustion to gas turbines would couple improved energy conversion efficiency and negligible noxious emissions, while the use of biogas would open the way to energy production from a renewable source by means of very efficient technologies. A different behavior has been observed for the two catalysts; namely, the undoped sample was more or less heavily poisoned, whereas the Sr-doped sample showed slightly increasing activity upon dosage of N-containing compounds. A possible reaction mechanism has been suggested, based on the initial oxidation of the organic backbone, with the formation of NO. The latter may adsorb more or less strongly depending on the availability of surface oxygen vacancies (i.e., depending on doping). Decomposition of NO may leave additional activated oxygen species on the surface, available for low-temperature methane oxidation and so improving the catalytic performance.

QUESTIONNAIREThe catalytic flameless combustion (CFC) of methane outperforms conventional flame combustion because of lower emission of pollutants (HC, CO and NO x ) and high thermal efficiency. The catalysts traditionally used for CFC are mainly based on supported noble metals, such as Pd and Pt, which ensure high activity, however accompanied by some drawbacks, due to high cost and poor thermal and chemical stability. La-based catalysts with ABO 3 perovskite-like structure have been proposed as a valid alternative for the present application. Indeed, perovskite catalysts combine low cost, thermochemical stability at high operating temperature and satisfactory catalytic activity. In spite of this, there are still some open questions, especially regarding their resistance to sulphur poisoning when used for the CFC of methane. Indeed, the poisoning mechanism of perovskite-like catalysts has not been completely understood and only a few papers deal with this very important topic.In general, the partial substitution of the perovskitic lattice metal ions is one of the important means to modulate catalytic activity. In LaBO 3 perovskites, the influence of dopants such as A' 2+ and A' 4+ has been widely investigated in the literature.* Corresponding author: fax +39-02-50314300; e-mail ilenia.rossetti@unimi.it 2In the recent past, attention has been devoted to catalyst nanostructuring, aiming at obtaining high surface area and defectivity, which should enhance oxygen mobility through the lattice and ensure good catalytic activity. To this purpose, we set up and optimised a flame-pyrolysis (FP) apparatus for the onestep synthesis of perovskitic mixed oxides. It is based on a specially designed burner fed with oxygen and an organic solution of the precursors, the solvent acting as fuel for the flame. FP-synthesized perovskites, showed good phase purity, along with nanometer-size particles and hence very high surface area (sometimes in excess of 100 m 2 /g). In addition, the high temperature of the flame in principle should also ensure thermal stability.In the present work we prepared a set of samples by FP, namely La 1-x A x MeO 3 , with A' = Ce, Sr, Ag Me=Mn, Co, x=0, 0.1, 0.2, either pure or doped with noble metals (Pt, Pd or Ag). In addition silver containing samples were synthesized by a traditional sol-gel (SG) method. The catalysts were tested for the CFC of methane, monitoring the activity by online mass spectrometry. Also the resistance to sulphur poisoning was investigated, using tetrahydrothiophene as poisoning agent.