A kinetic study on CH4 combustion over a PdO/ZrO2 (10%, w/w) catalyst has been performed in a temperature range between 400 and 550degreesC by means of an annular catalytic microreactor.The role of mass transfer phenomena including diffusion in the catalyst pore, gas-solid diffusion and axial diffusion in the gas phase, has been preliminary addressed by means of mathematical modeling. Simulation results have pointed out the key role of internal diffusion showing that thicknesses of the active catalyst layer as thin as 10-15 mum are required to minimize the impact of mass transfer limitations. The thermal behavior of the reactor has been also addressed by means of catalytic combustion tests with CH4 and CO-H-2 mixtures as fuels. The results have demonstrated the possibility to obtain nearly isothermal temperature profiles under severe conditions (up to 3% of CH4) thanks to effective dissipation of reaction heat by radiation from the catalyst outer skin.Finally the effect of reactants (CH4 and O-2) and products (H2O and CO2) on CH4 combustion rate has been addressed. The results have shown that both H2O and CO2 markedly inhibit the reaction up to 550degreesC. The data have been fitted by the following simple power law expression r = k(r) PCH4PH2Op-0.32 P-CO2(-0.25) with an apparent activation energy of 108 kJ/mol.Evidences have been found and discussed indicating a key role of the support on the extent of such inhibition effects. (C) 2003 Elsevier B.V. All rights reserved.