Tri-reforming: A new biogas process for synthesis gas and hydrogen production

In this work biogas valorization – a renewable resource – for synthesis gas and hydrogen generation through dry reforming or tri-reforming (TR) is studied. Several Ni-based catalysts and a bimetallic Rh–Ni catalyst supported on magnesia or alumina modified with oxides like CeO₂ and ZrO₂ were used. For all the experiments, a synthetic biogas (molar composition: 60% CH₄ and 40% CO₂) was fed and the catalytic activities were measured in two different experimental facilities: a bench-scale fixed bed reactor system and a microreactor reaction system, at 1073 K and atmospheric pressure. Those catalysts which achieved high activity and stability in the fixed-bed reactor were impregnated in a microreactor to explore possible process intensification. For TR processes, different steam to carbon ratios, S/C, from 1.0 to 3.0, and O₂/CH₄ ratios of 0.25 and 0.50 were used. The high methane and carbon dioxide conversions reached in the fixed bed reactor were also achieved in the microreactor operating at much higher WHSV. In addition, process intensification improved catalysts stability. Physicochemical characterization of catalyst samples by ICP-OES, N₂ physisorption, H₂ chemisorption, TPR, SEM and XPS showed differences in chemical state, metal–support interactions, average crystallite sizes and redox properties of nickel and rhodium metal particles, indicating the importance of the morphological and surface properties of metal phases in driving the reforming activity.