Modeling and experimental analysis of CO₂ methanation reaction using Ni/CeO₂ monolithic catalyst

In this study, the effect of the cell density of monolithic catalysts was investigated and further mathematically modeled on cordierite supports used in CO₂ methanation. Commercial cordierite monoliths with 200, 400, and 500 cpsi cell densities were coated by immersion into an ethanolic suspension of Ni/CeO₂ active phase. SEM-EDS analysis confirmed that, owing to the low porosity of cordierite (surface area < 1 m² g^-1), the Ni/CeO₂ diffusion into the walls was limited, especially in the case of low and intermediate cell density monoliths; thus, active phase was predominantly loaded onto the channels' external surface. Nevertheless, despite the larger exposed surface area in the monolith with high cell density, which would allow for better distribution and accessibility of Ni/CeO₂, its higher macro-pore volume resulted in some introduction of the active phase into the walls. As a result, the catalytic evaluation showed that it was more influenced by increments in volumetric flow rates. The low cell density monolith displayed diffusional control at flow rates below 500 mL min^-1. In contrast, intermediate and high cell density monoliths presented this behavior up to 300 mL min^-1. These findings suggest that the interaction reactants-catalyst is considerably more affected by a forced non-uniform flow when increasing the injection rate. This condition reduced the transport of reactants and products within the catalyst channels and, in turn, increased the minimum temperature required for the reaction. Moreover, a slight diminution of selectivity to CH₄ was observed and ascribed to the possible formation of hot spots that activate the reverse water-gas shift reaction. Finally, a mathematical model based on fundamental momentum and mass transfer equations coupled with the kinetics of CO₂ methanation was successfully derived and solved to analyze the fluid dynamics of the monolithic support. The results showed a radial profile with maximum fluid velocity located at the center of the channel. A reactive zone close to the inlet was obtained, and maximum methane production (4.5 mol m^-3) throughout the monolith was attained at 350 °C. Then, linear streamlines of the chemical species were developed along the channel.