Are Rh Catalysts a Suitable Choice for Bio-Oil Reforming? The Case of a Commercial Rh Catalyst in the Combined H2O and CO2 Reforming of Bio-Oil

Bio-oil combined steam/dry reforming (CSDR) with H2O and CO2 as reactants is an attractive route for the joint valorization of CO2 and biomass towards the sustainable production of syngas (H2 + CO). The technological development of the process requires the use of an active and stable catalyst, but also special attention should be paid to its regeneration capacity due to the unavoidable and quite rapid catalyst deactivation in the reforming of bio-oil. In this work, a commercial Rh/ZDC (zirconium-doped ceria) catalyst was tested for reaction–regeneration cycles in the bio-oil CSDR in a fluidized bed reactor, which is beneficial for attaining an isothermal operation and, moreover, minimizes catalyst deactivation by coke deposition compared to a fixed-bed reactor. The fresh, spent, and regenerated catalysts were characterized using either N2 physisorption, H2-TPR, TPO, SEM, TEM, or XRD. The Rh/ZDC catalyst is initially highly active for the syngas production (yield of 77% and H2/CO ratio of 1.2) and for valorizing CO2 (conversion of 22%) at 700 °C, with space time of 0.125 gcatalyst h (goxygenates)−1 and CO2/H2O/C ratio of 0.6/0.5/1. The catalyst activity evolves in different periods that evidence a selective deactivation of the catalyst for the reforming reactions of the different compounds, with the CH4 reforming reactions (with both steam and CO2) being more rapidly affected by catalyst deactivation than the reforming of hydrocarbons or oxygenates. After regeneration, the catalyst’s textural properties are not completely restored and there is a change in the Rh–support interaction that irreversibly deactivates the catalyst for the CH4 reforming reactions (both SR and DR). As a result, the coke formed over the regenerated catalyst is different from that over the fresh catalyst, being an amorphous mass (of probably turbostractic nature) that encapsulates the catalyst and causes rapid deactivation.