Stability of Ni/SiO₂-ZrO₂ catalysts towards steaming and coking in the dry reforming of methane with carbon dioxide

Abstract

Ni/SiO₂-ZrO₂ catalysts with Ni loadings of 1 to 13 wt-% were prepared, characterized by elemental analysis, X-ray diffraction, N₂ sorption, temperature programmed oxidation, temperature programmed reduction, and tested for their activity and stability in the dry reforming of methane with carbon dioxide at 850 °C, gas hourly space velocity of 6000 and 1800 h^–1 and atmospheric pressure. The SiO₂-ZrO₂ support as obtained through a simple and efficient sol-gel synthesis is highly porous (A_BET = 90 m²·g^–1, d_P = 4.4 nm) with a homogeneously distributed Si-content of 3 wt-%. No loss of Si or formation of monoclinic ZrO₂, even after steaming at 850 °C for 160 h, was detectable. The catalyst with 5 wt-% Ni loading in its fully reduced state is stable over 15 h on-stream in the dry reforming reaction. If the catalyst was not fully reduced, a reduction during the early stages of dry reforming is accompanied by the deposition of up to 44 mg·g^–1carbon as shown by experiments in a magnetic suspension balance. Rapid coking occurs for increased residence times and times-on-stream starting at 50 h. The Ni loading of 5 wt-% on SiO₂-ZrO₂ was shown to provide an optimal balance between activity and coking tendency.

Graphical abstract

Keywords

Ni/SiO₂-ZrO₂ / synthesis gas / dry reforming / coking / steaming

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