Biogas reforming for hydrogen production over nickel and cobalt bimetallic catalysts

Ni/Co bimetallic catalysts supported by commercial γ-Al₂O₃ modified with La₂O₃ for biogas reforming were prepared by conventional incipient wetness impregnation. The catalysts were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), BET surface area and porosity analysis (BET), H₂ temperature-programmed reduction (H₂-TPR), transmission electron microscopy (TEM) and thermogravimetry coupled to differential scanning calorimetry (TG–DSC). XRD and XPS analysis revealed that a Ni/Co alloy was formed in the bimetallic catalysts. The Ni/Co ratio could be adjusted to improve pore textural properties, which enhanced the metal particle dispersion and resulted in smaller metal particle size, and thus increased the catalytic activity and resistance to carbon deposition. The activity and stability of the catalysts for biogas reforming was tested at 800 °C, ambient pressure, GHSV of 6000 ml g_cat⁻¹ h⁻¹ and a CH₄/CO₂ molar ratio of 1 without dilute gas. Experimental results showed that the catalytic activity could be closely related to the Ni/Co ratio. The bimetallic catalyst 7Ni3Co/LaAl exhibited better catalytic and anti-coking performance due to smaller metal particles, higher metal dispersion, uniform pore distribution, surface enrichment of Co, as well as the synergetic effect between Ni and Co. During a 290 h stability test over the catalyst 7Ni3Co/LaAl, the average conversion of CH₄ and CO₂, selectivity to H₂ and CO, and ratio of H₂/CO were 93.7%, 94.0%, 94.9%, 97.8%, and 0.97, respectively. The average coking rate was 0.0946 mg g_cat⁻¹ h⁻¹.