Bulk Ni-based catalysts derived from hydrotalcite-type (HT) compounds show enhanced stability in the hydrogenation of CO2 into CH4, in comparison to their supported counterparts. The composition of the parent hydrotalcite determines the Ni loading and particle size, as well as the basicity of the catalysts. In this work, a comparison between the effect of Fe and La on the performance of NiMgAl HT compounds (Ni/Mg/Al = 25/50/25 atomic ratio) calcined at 600 °C is investigated. After a reduction pretreatment at 750 °C, both promoters enhance the activity in the low-temperature range; however, the La-containing catalyst reaches a better CH4 productivity rate at high oven temperature (i.e., 200 L gNi –1 h–1 at 325 °C). Although the formation of the NiFe alloy improves the activity, lanthanum keeps smaller Ni0 particles and provides a higher basicity to the mixed oxide than Fe. The activity of the NiMgLaAl catalyst can be further tailored by increasing the Ni loading from 25.6 wt % (Ni25Mg50La5Al20) to 44.6 wt % (Ni50Mg25La5Al20). Lastly, the feasibility of HT-derived catalysts in the direct methanation of clean biogas is proved.

Clean biogas, produced by anaerobic digestion of biomasses or organic wastes, is one of the most promising substitutes for natural gas. After its purification, it can be valorized through different reforming processes that convert CH4 and CO2 into synthesis gas (a mixture of CO and H2). However, these processes have many issues related to the harsh conditions of reaction used, the high carbon formation rate and the remarkable endothermicity of the reforming reactions. In this context, the use of the appropriate catalyst is of paramount importance to avoid deactivation, to deal with heat issues and mild reaction conditions and to attain an exploitable syngas composition. The development of a catalyst with high activity and stability can be achieved using different active phases, catalytic supports, promoters, preparation methods and catalyst configurations. In this paper, a review of the recent findings in biogas reforming is presented. The different elements that compose the catalytic system are systematically reviewed with particular attention on the new findings that allow to obtain catalysts with high activity, stability, and resistance towards carbon formation.