Ethanol steam reforming on Ni/Al2O3 catalysts: Effect of the addition of Zn and Pt

Abstract

Ni-based catalysts supported on Zn-modified alumina were investigated in the ethanol steam reforming reaction. A commercial γ-alumina was impregnated with different amounts of zinc nitrate (0, 2, 5, 10, 15, 20wt.% on Zn basis), calcined, and then impregnated with nickel nitrate aqueous solutions. The samples were characterized by a number of techniques: N2 adsorption at 77K, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray fluorescence (XRF), and temperature-programmed reduction (TPR). Their catalytic behavior in the ethanol steam reforming reaction was studied at 873K, with a H2O/ethanol ratio of 5:1. Two effects of the presence of Zn were detected. On the one hand, zinc modifies the surface structure and the surface chemistry of the catalysts by formation of zinc aluminates, and on the other hand, zinc oxide can be reduced to metallic zinc under reaction conditions, thus modifying the catalytic properties of the active phase. The presence of Zn increases the ethanol conversion to gaseous compounds as compared with the catalyst supported on the Zn-free commercial alumina. The addition of a small amount of Pt (1wt.%) causes a beneficial effect in the reaction. When Ni catalysts were used without a previous reduction treatment, ethylene was formed in high amounts; however, the Pt–Ni catalysts need no reduction pre-treatment to achieve high H2 yields (close to 70%) and showed a high stability versus time on stream because of the control of the production of ethylene, a coke precursor.