Effect of Support on Stability and Coke Resistance of Ni-Based Catalyst in Combined Steam and CO₂ Reforming of CH₄

Abstract

Ni-based catalysts dispersed on different supports (MgO-α-Al 2 O 3 , CeO 2 , SBA-15, and MgO-SBA-15) were prepared by the impregnation method. Characteristics of the catalysts, including specific surface areas (N 2 physisorption), crystalline phase compositions (powder X-ray diffraction, Raman spectroscopy), reducibility (hydrogen temperature-programmed reduction, H 2 -TPR), and morphology (scanning electron microscopy (SEM) and transmission electron microscopy, TEM)) were investigated. The activity and stability of the catalysts were tested for the combined steam and CO 2 reforming of methane at 700 °C in a microflow system. The results show that the catalysts exhibit high activity in the BRM reaction. At 700 °C, the conversion of CH 4 and CO 2 reached 86–99% and 67–80%, respectively, in which the Ni/Mg–SBA catalyst is the best with conversions of CH 4 and CO 2 reaching 99% and 80%. Coke accumulation on the surface of the catalysts for 100 h time on stream (TOS) was evaluated by the temperature-programmed oxidation (TPO) technique. The major cause of the catalytic deactivation was elucidated by combining the determination of the amount and type of deposited coke with the changes in the physicochemical properties of the catalysts after the long-term reaction. Almost complete loss of activity was observed on Ni/Mg–Al catalyst after 100 h TOS, while the activity drop was slow on the Ni/Mg–SBA sample, about 15–20% of the total value. Otherwise, the Ni/CeO 2 and Ni/SBA catalysts firmly retained their stable activity for 100 h TOS due to the minimal carbon deposition and stability of these catalysts’ structure. The highly considerable formation of inert C γ carbon and sintering over Ni catalyst supported on MgO-α-Al 2 O 3 were responsible for the lower stability of this catalyst compared to those supported on CeO 2 and SBA-15.