Synthesis gas produced through biomass gasification can be converted into H2‐rich gas by catalytic methane decomposition or reforming reactions. In this study, we investigate the promotion of hydrogen production by the catalytic reforming of a model biomass‐gasification‐derived syngas over Ni/MAl2O4 (M=Mg, Ni, and Ca) catalysts. Three mesoporous spinel supports were synthesized by solution combustion. Ni/NiAl2O4 and Ni/CaAl2O4 exhibited better catalytic activities and stabilities for syngas reforming than the other catalysts. These results are ascribable to interactions between the metallic catalyst and spinel supports, and stronger interactions lead to smaller catalyst particles. The formation of coke deposits is associated with CH4 decomposition during the syngas reforming reaction. Clearly, H2 production is lower at 900 °C because of increased competition from the reverse water–gas shift reaction that shifts the reaction between CO2 and H2 toward the generation of CO and H2O.
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