Comparative Study on Ni/MgO-Al₂O₃ Catalysts for Dry and Combined Steam–CO₂ Reforming of Methane

The dry reforming of methane (DRM) and the combined steam–CO₂ reforming of methane (CSCRM) are promising routes for syngas production while simultaneously utilizing two major greenhouse gases—CO₂ and CH₄. In this study, a series of Ni/MgO-Al₂O₃ catalysts with varying Mg/Al molar ratios (Ni/MgAl(x), x = 0.5–0.9), along with Ni/MgO and Ni/Al₂O₃, were synthesized, characterized, and evaluated in both the DRM and CSCRM. Ni/MgO and Ni/Al₂O₃ exhibited a lower activity due to fewer active sites and a poor CH₄/CO₂ activation balance. In contrast, Ni/MgAl(0.6), Ni/MgAl(0.7), and Ni/MgAl(0.8) showed an enhanced activity, attributed to more abundant active sites and a more balanced activation of CH₄ and CO₂. Ni/MgAl(0.7) delivered the best DRM performance, whereas Ni/MgAl(0.8) was optimal for the CSCRM, likely due to its greater number of strong basic sites promoting CO₂ and H₂O adsorption. At 750 °C and 0.1 MPa over 100 h, Ni/MgAl(0.7) maintained a stable DRM performance (77% CH₄ and 86% CO₂ conversion; H₂/CO = 0.9) at 120 L/(g_cat·h), while Ni/MgAl(0.8) achieved a stable CSCRM performance (80% CH₄ and 62% CO₂ conversion; H₂/CO = 2.1) at 132 L/(g_cat·h). This study provides valuable insights into designing efficient Ni/MgO-Al₂O₃ catalysts for targeted syngas production.