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The effect of CeO2 and CaO promoters on the ignition performance over Ni/MgO-Al2O3 catalyst for the partial oxidation of methane (POM) to synthesis gas was investigated. It was found that the POM reaction could not be ignited over 1wt%Ni/MgO-Al2O3 catalyst without the promoters in the temperature range from 773 K to 1073 K. CeO2 and CaO promoters enhanced the ignition performance and the POM reactivity of 1wt%Ni/MgO-Al2O3 catalyst remarkably. Moreover, the improving effect became greater with the increase of the promoter content under the investigated reactionconditions. The modification effects of CeO2 and CaO promoters were closely related to the concentration and reducibility of the surface and bulk oxygen species.