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

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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.

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Authors and Affiliations

  1. Institute of Chemical Technology, Universität Leipzig, Linnéstr. 3, 04103, Leipzig, Germany

    Bettina Stolze, Juliane Titus & Roger Gläser

  2. hte GmbH, Kurpfalzring 104, 69123, Heidelberg, Germany

    Stephan A. Schunk

  3. BASF SE, Carl-Bosch-Straße 38, 67056, Ludwigshafen, Germany

    Andrian Milanov & Ekkehard Schwab

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  1. Bettina Stolze
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  2. Juliane Titus
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  3. Stephan A. Schunk
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  4. Andrian Milanov
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  5. Ekkehard Schwab
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  6. Roger Gläser
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Correspondence to Roger Gläser.

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Stolze, B., Titus, J., Schunk, S.A. et al. Stability of Ni/SiO2-ZrO2 catalysts towards steaming and coking in the dry reforming of methane with carbon dioxide. Front. Chem. Sci. Eng. 10, 281–293 (2016). https://doi.org/10.1007/s11705-016-1568-0

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