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.

Key words： Ni/SiO₂-ZrO₂; synthesis gas; dry reforming; coking; steaming

Acknowledgements

Financial support of this work by the German government (Bundesministerium für Wirtschaft und Technologie, Fördernummer 0320327856D) is gratefully acknowledged. Thanks are also due to Katja König, Institut für Nichtklassische Chemie e.V. at Unviersität Leipzig, for the experiments with the magnetic suspension balance, and to Dr. Gerald Wagner, Institute for Mineralogy, Crystallography and Material Science, Universität Leipzig, for the electron microscopy images.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s11705-016-1568-0 and is accessible for authorized users.

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