Steam Reforming Of Methane To Syngas Over Nial2o4 Spinel Catalysts

摘要

A series of several mixed oxides close to NiAl2O4 (NiAl2O4, 5 wt% NiO/NiAl2O4,10 wt% NiO/ NiAl2O4 and 15 wt% NiO/NiAl2O4) were prepared by a pseudo sol gel method using pro-pionic acid then calcinated at 900 °C during 4 h. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), surface areas (BET) and temperature-programmed reduction (TPR). The nature of the crystalline structure, the surface area and the reduction temperature depend on the Ni/ Al ratio. For the stoichiometric ratio Ni/Al exactly equal to 0.5, homogeneous crystalline spinel phase was formed after temperature of calcination was equal or higher than 725 °C. The spinel structure being a non-tolerant structure for an excess of Ni, when Ni/Al is higher than 0.5, free NiO in strong interaction with the spinel was present and favoured the reduction of the nickel of the structure at lower temperature compared to the spinel. Till 700 °C, the spinel structure was well conserved even if it was partially reduced. For a temperature higher than 700 °C, the structure leads to Ni species formation on y-Al2O3. Comparative steam reforming of methane was conducted to control the formation of Ni and its sintering. The stoichiometric spinel showed relevant catalytic performances: high CH4 conversion, high selectivities of CO and H2 and low carbon formation. The presence of nickel inside the spinel structure of NiAl2O4 catalyst confers a high stability and strong dispersion for the metallic particles. The low formation of carbon was due to the high dispersion and the limited growing of the Ni particles on y-Al2O3. Over 5 wt% of NiO excess, a rough decrease of the CH4 conversion, CO and H2 selectivities were observed. The x wt% NiO/NiAl2O4 systems give an important carbon formation due to a large Ni particle formation after rapid sintering.