Three-dimensional lattice Boltzmann (LB) simulations were carried out to investigate the mass transport and reaction inside and around catalytic porous particles used in fluidized beds for the synthesis of methane from biogas (H₂/CO mixtures). The 3D internal porous structure of a real particle with a size ∼200 μm was assessed with Synchrotron-based X-ray tomography (XTM). Pore-resolved simulations with a suitable LB model for catalytic reactions in microflows revealed that the preferential diffusion of H₂ and the resulting inability of CO to penetrate deep inside the pores led to segregated distributions of the two species, hindering reaction in the downstream parts of the particle and rendering CO the deficient reactant. The implications for practical fluidized beds are that, for specific bed zones with a high dense-phase (solid-phase) volume fraction and a predominant flow direction, CO starvation may occur and may thus limit the methane yields. Subsequent parametric studies of spherical particles with a diameter 2R=150 μm and an artificially generated porosity allowed comparisons of LB results with radially symmetric analytical continuum-model solutions. The LB simulations revealed appreciable angular variations in the CO concentration at the external surface (r=R) and the outer layers of particle, especially at the higher investigated Damköhler numbers, which were however diminished as the core of the particle (r→0) was approached. The large angular variations, in conjunction with the skewed CO distributions towards their lower values, led to LB-computed particle effectiveness factors ∼30% lower than the corresponding analytical solutions.