n-Dodecane reforming over nickel-based monolith catalysts: Deactivation and carbon deposition Original Research Article

The carbon deposition behavior of Ni-based monolith reforming catalysts was studied during n-dodecane autothermal reforming, partial oxidation, and steam reforming. One catalyst formulation was nickel deposited on cerium zirconium oxide (CZO) coated monolith, while the second formulation was nickel directly deposited on bare monolith. In both formulations, a series of catalysts with a range of nickel loadings (0–16 wt.%) were prepared to examine the influence of nickel loading on carbon deposition and to elucidate the benefits of the reducible oxide support CZO on carbon deposition. Carbon deposition was generally more pronounced at higher nickel loadings and on catalysts lacking CZO. Nickel supported on bare monolith suffered from excessive carbon deposition and carbon-induced monolith disintegration. The morphologies of carbon were determined by scanning electron microscopy (SEM). Temperature programmed oxidation (TPO) indicated the presence of two types of carbon. The low-temperature TPO peak can be attributed to coating carbon, while the high-temperature peak corresponds to filamentous carbon structures, including large whiskers and smaller filaments. Accumulation of whisker carbon had a deleterious effect on the monolith substrate resulting in the physical destruction of some samples. X-ray diffraction (XRD) gave no evidence for the presence of graphite or carbide species in carbon-deposited catalysts. The experimental results of this study are used to diagnose the causes for nickel catalyst deactivation during autothermal reforming and for proposing strategies to mitigate the deactivation.