CNT and H2 Production during CH4 Decomposition over Ni/CeZrO2. II. Catalyst Performance and Its Regeneration in a Fluidized Bed

In this work, a ceria-zirconia supported nickel catalyst (Ni/CeZrO2) was for the first time used in a fluidized bed reactor in order to obtain carbon nanotubes (CNTs) and H-2 in the reaction of the decomposition of CH4. The same catalyst was afterward regenerated with H2O, which was accompanied with the production of H-2. The impact of catalyst granulation, temperature, and gas hourly space velocity (GHSV) on the amount and type of carbon deposits was determined using thermogravimetric analysis (TGA) and scanning and transmission electron microscopy (SEM and TEM). The presence of randomly oriented and curved CNTs with an outer diameter of up to 64 nm was proved. The Ni/CeZrO2 particles were loosely covered with CNTs, freely dispersed over CNTs, and strongly attached to the external CNT walls. TEM proved the presence of a Ni/CeZrO2@CNT hybrid material that can be further used as catalyst, e.g., in WGS or DRM reactions. The impact of GHSV on hydrogen production during catalyst regeneration was determined. The catalyst was subjected to cyclic tests of CH4 decomposition and regeneration. According to the obtained results, Ni/CeZrO2 can be used in CH4 conversion to CNTs and H-2 (instead of CH4 combustion), e.g., in the vicinity of installations that require methane utilization.