Methane steam reforming over Ni/Ce–ZrO 2 catalyst: Influences of Ce–ZrO 2 support on reactivity, resistance toward carbon formation, and intrinsic reaction kinetics

Abstract

Ni/Ce–ZrO 2 showed good methane steam reforming performance in term of stability toward the deactivation by carbon deposition. It was first observed that the catalyst with Ce/Zr ratio of 3/1 showed the best activity among Ni/Ce–ZrO 2 samples with the Ce/Zr ratios of 1/0, 1/1, 1/3, and 3/1. Temperature-programmed oxidation (TPO) experiments indicated the excellent resistance toward carbon formation for this catalyst, compared to conventional Ni/Al 2O 3; the requirement of inlet H 2O/CH 4 to operate without the formation of carbon species is much lower. These benefits are related to the high oxygen storage capacity (OSC) of Ce–ZrO 2. During the steam reforming process, in addition to the reactions on Ni surface (*), the redox reactions between the gaseous components present in the system and the lattice oxygen (O x ) on Ce–ZrO 2 surface also take place. Among these reactions, the redox reactions between the high carbon formation potential compounds (CH 4, CH x -* n and CO) and the lattice oxygen (O x ) can prevent the formation of carbon species from the methane decomposition and Boudard reactions, even at low inlet H 2O/CH 4 ratio (1.0/1.0). Regarding the intrinsic kinetic studies in the present work, the reaction order in methane over Ni/Ce–ZrO 2 was observed to be approximately 1.0 in all conditions. The dependence of steam on the rate was non-monotonic, whereas addition of oxygen as an autothermal reforming promoted the rate but reduced CO and H 2 production selectivities. The addition of a small amount of hydrogen increased the conversion of methane, however, this positive effect became less pronounced and the methane conversion was eventually inhibited when high hydrogen concentration was added. Ni/Ce–ZrO 2 showed significantly stronger negative impact of hydrogen than Ni/Al 2O 3. The redox mechanism on ceria proposed by Otsuka et al. [K. Otsuka, T. Ushiyama, I. Yamanaka, Chem. Lett. (1993) 1517; K. Otsuka, M. Hatano, A. Morikawa, J. Catal. 79 (1983) 493; K. Otsuka, M. Hatano, A. Morikawa, Inorg. Chim. Acta 109 (1985) 193] can explain this high inhibition.