Catalytic steam gasification of waste rigid polyurethane foam, in the fixed-bed reactor, was performed to produce hydrogen-rich gas. The influence of nine kinds of additives on the yield of products (gaseous, solid and liquid product) and the volume fraction of hydrogen was investigated. Among the additives, calcium carbonate, as the catalyst, could effectively enhance the gas yield and the volume fraction of hydrogen. A three-factor three-level completely randomised factorial (3 × 3 × 3) design, with calcium carbonate as the catalyst, was applied to investigate the influence of experimental conditions (temperature, steam flowrate and catalyst dosage) on the volume fraction of gaseous product components. The data were processed with SPSS statistical software. The result showed that the main effects of one variable, the interactive effects between two factors and the interactive effects among three factors all have statistical high significance. The best catalysed process is realised when calcium carbonate is the catalyst, gasification temperature is 1100°C, steam flowrate is 0.7 kg h−1, catalyst dosage is 10 wt% of waste rigid polyurethane foam. Under this condition, the volume fraction of hydrogen reaches up to 79.85%.
