Role of operating conditions in the catalyst deactivation in the in-line steam reforming of volatiles from biomass fast pyrolysis

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The effect of reforming conditions (temperature, space time and steam/biomass ratio (S/B)) has been studied in the continuous biomass pyrolysis and in-line catalytic steam reforming process in order to establish suitable conditions for attenuating the deactivation of a commercial Ni catalyst by coke deposition. The experiments have been performed in a conical spouted bed and a fluidized bed reactor for the pyrolysis and reforming steps, respectively. Biomass fast pyrolysis was performed at 500 °C and the reforming operating conditions studied are as follows: 550–700 °C; space time, 10–30 gcat min gvolatiles−1, and; S/B ratio, 2–5. The coke deposited on the catalyst has been analyzed by temperature programmed oxidation (TPO), and two types of coke have been identified, i.e., the coke deposited on the Ni active sites and the one separated from these sites, without filamentous coke being observed by transmission electron microscopy (TEM). Coke deposition has been related to the decomposition of the oxygenates derived from biomass pyrolysis and the re-polymerization of phenolic oxygenates. Suitable conditions to achieve almost full conversion with a H2 yield of up to 95% and stability for 160 min on stream, are as follows: 600 °C, space time of 30 gcat min gvolatiles−1 and S/B ratio of 3.