The upgradation of methane in biogas by hydrogenation of CO2has been currently recognized as a promising route for efficient full utilization of renewable biogas with potential benefits for storage of renewable hydrogen energy and abatement of greenhouse gas emission. As a main constituent of biogas, CO2can act as a backbone for the formation of additional CH4by hydrogenation, then producing higher amounts of biomethane. In this work, the upgradation process was investigated in a prototype reactor of double pass operation with vertical alignment using an optimized Ni-Ce/Al-MCM-41 catalyst. The experimental results show that the double pass operation that removes water vapor during the run can significantly increase CO2conversion, resulting in higher CH4production yield. As a result, the purity of biomethane increased by 15% higher than a single pass operation. In addition, search for optimum condition of the process was carried out within an investigated range of conditions including flowrate (77–1108 ml min−1), pressure (1 atm–20 bar), and temperature (200–500 °C). The durability test for 458 h was performed using the obtained optimum condition, and it shows that the optimized catalyst can perform excellent stability with negligible influence by the observed change in catalyst properties. The comprehensive characterization on physicochemical properties of fresh and spent catalysts was performed, and the results were discussed.