Global Vision of the Reaction and Deactivation Routes in the Ethanol Steam Reforming on a Catalyst Derived from a Ni–Al Spinel

Ethanol steam reforming (ESR) over a Ni/Al2O3 catalyst prepared by reduction of a NiAl2O4 spinel is a promising alternative route to produce H2 from biomass. This work deepens into the effect of reaction conditions (450–650 °C, a steam/ethanol (S/E) ratio of 3–9, and a weight space time up to 1.3 h) and evaluates the time on stream evolution of the yields of H2, gaseous byproducts (CO, CO2, CH4, C2H4, C2H4O), and formed carbon/coke. The results are explained taking into consideration the thermodynamics, the extent of each individual reaction, and the catalyst deactivation. Up to 600 °C, the predominant intermediate in the H2 formation is C2H4 (formed by ethanol dehydration) with the preferential formation of nanostructured carbon (nanotubes/filaments) by C2H4 decomposition. The deposition of this type of carbon partially deactivates the catalyst, mainly affecting the extent of the C2H4 decomposition causing a sharp decrease in the H2 and carbon yields. Nevertheless, the catalyst reaches a pseudosteady state with an apparent constant activity for other reactions in the kinetic scheme. At 650 °C, C2H4O (formed by the ethanol dehydrogenation) is the main intermediate in the H2 formation, which is the precursor of an amorphous/turbostratic carbon (coke) formation that initially causes a rapid deactivation of the catalyst, affecting the ethanol dehydration and, to a lower extent, the reforming and water gas shift reactions. The increase in the S/E ratio favors the H2 formation, attenuates the catalyst deactivation due to the suppression of the ethanol dehydration to C2H4, and promotes the reforming, water gas shift, and carbon/coke gasification reactions. A H2 yield of 85% stable for 48 h on stream is achieved at 600 °C, with a space time of 0.1 h and an S/E ratio of 9.