The development of efficient carbon dioxide sequestration and utilization technologies is an indispensable aspect of a wide range of measures directed at reducing the negative effects of anthropogenic emissions on the environment. One route is its capture via physical adsorption and further conversion to methane in the Sabatier reaction. The sorption process can be carried out, among others, in fixed-bed adsorptive reactors, in which the packing is made up of adsorbent and catalyst particles. Proper structuring of such a hybrid bed can contribute to increasing the efficiency of both stages of the process. Of importance in this regard is, first of all, the proper management of heat transfer. This study examines the sorption step of the operation of an adsorptive reactor for CO2 sequestration and methanation using a one-dimensional non-isothermal model of a layered fixed bed. Numerical calculations for different configurations and different volume adsorbent to catalyst ratios were carried out to determine how the hybrid structure of the bed and the atypical thermal waves it induces affect the sorption process. The results obtained prove that proper tailoring of the bed can be an excellent tool to control the temperature profiles and thus the performance of the apparatus and possibly its optimization.