Purposes High-pressure dry reforming of methane(DRM), as a key technology for direct production of high-pressure syngas, improves overall energy efficiency by more than 40% compared with that of atmospheric systems. However, carbon deposition under high-pressure conditions severely restricts its industrial application. Methods In this study, CeO2 modification strategies via co-precipitation (CP) and impregnation (I) methods were comparatively investigated, revealing the crucial role of CeO2 crystallite size in anti-coking performance of a hydrotalcite-derived Ni-based catalyst (Ni/MgAl2O4-MgO). Results Comprehensive characterization techniques including BET, O2-TPO, XRD, and CO2-TPD demonstrate that the co-precipitation derived NiCe/MgAl2O4-MgO(C) catalyst exhibits larger CeO2 crystallites (10.98 nm) and formation of CeAlO3 (XRD 2θ=33.1°) caused by the combination of Ce³⁺ with Al in MgAl2O4, which disrupts the original support structure and leads to severe Ni sintering. In contrast, the impregnation-derived NiCe/MgAl2O4-MgO(I) catalyst restricts the CeO2 crystallite size to 5.13 nm, resulting in small-sized, low-crystallinity CeO2 particles while maintaining a high specific surface area (153.864 m2/g). This superior structure enhances the CO2 adsorption capacity by 4.5 times (CO2-TPD) and reduces the proportion of graphitic carbon from 86.1% to 24.7% (O2-TPO-MS). A 72 h high-pressure stability test confirmes that the deactivation rate of the impregnated catalyst is only 12.93%, significantly lower than that of the co-precipitation catalyst (25.97%) and the unmodified system (27.54%). Conclusions This study elucidates that CeO2 crystallite size is one of the core factors governing the differential catalytic performance, providing a new paradigm for the design of high-pressure DRM catalysts.
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