In this study, the preparation of hydrogen-rich gases from improved pyrolysis-catalytic reforming system by industrial solid waste calcium carbide slag was investigated in a fixed-bed reaction system. The differences in biomass pyrolysis gas compositions and yields over the bifunctional phase change catalyst NiO–Ca9Co12O28 with different Ni doping ratios, pyrolysis temperatures, and calcium carbide slag doping ratios have been investigated, and a model for the mechanism of the redox reaction over the NiO–Ca9Co12O28 catalyst is proposed at the same time. The results of the study indicated that the maximum hydrogen production is 447.23 mL/gbiomass at 600 °C when the mass ratio of bamboo to calcium carbide slag is 5:9, which is 549.29% higher than that of pyrolysis of bamboo alone. The hydrogen volume concentration increased from 17.93% to 63.78%. This study provides a green and efficient route for high-value conversion of biomass and adsorption-enhanced reforming of solid waste for hydrogen production.
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