Catalytic activity and long-term stability of palladium oxide catalysts for natural gas combustion: Pd supported on LaMnO3-ZrO2

The catalytic activity and long-term stability of 2% Pd/LaMnO3-ZrO2 catalysts for natural gas combustion were deeply investigated. The catalyst, prepared via solution combustion synthesis, was completely characterized (XRD, BET, FESEM/EDS, TPC/TPD/TPR and FT-IR analysis) in the fresh status, and in the aged one, after prolonged treatment under hydro-thermal ageing and S-compounds poisoning (up to 3 weeks of hydro-thermal treatment at 800 °C under a flow of domestic boiler exhaust gases typical composition of 9% CO2, 18% H2O, 2% O2 in N2, including 200 ppmv of SO2). An increased catalytic activity towards NG combustion with ageing was detected: the T50, in fact, got lowered from 570 (fresh sample) to 465 °C (after 3 weeks ageing). Highly dispersed Pd centers were predominant on fresh catalyst. Upon ageing, oxygen covered Pd metal particles formed, at the expense of dispersed cationic and zerovalent Pd atoms. The increase in the catalytic activity was associated to the phase modification occurring in the bulk support, where Mn oxides, active towards CH4 combustion, segregated. Moreover, bands due to sulfate species were detected in aged samples: IR analysis showed that Pd atoms did not interact significantly with these species. The bands of sulfate species decreased in intensity after 3 weeks ageing, likely mostly due to sintering of the catalyst, with the corresponding decrease in the surface area.