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Potassium-Doped Ni–MgO–ZrO2 Catalysts for Dry Reforming of Methane to Synthesis Gas

Abstract

Ni/K–MgO–ZrO2 catalysts for dry reforming of methane, with a range of Mg/Zr ratios and each containing about 10 wt% Ni, were prepared via Ni nitrate impregnation on MgO–ZrO2 supports synthesized by co-precipitation using K2CO3. It was found that a proportion of the potassium of the precipitant remained in the samples and improved the stability of the catalysts in the reaction. It was also shown that reduction of the catalysts at 1,023 K without calcination in air is necessary for stable and high activity; calcination in air at 1,073 K gives a deterioration of the catalytic properties, leading to rapid deactivation during the reaction. The order of the CH4 conversions of the reduced catalysts after 14 h on stream was as follows: Ni/K–Mg5Zr2 ~ Ni/K–Mg ≥ Ni/K–Mg2Zr5 ≫ Ni/K–Zr. A catalyst with 0.95 wt% K on MgO–ZrO2 with a Mg:Zr mole ratio of 5:2 showed the best resistance to deactivation. Experiments in a microbalance system showed that there was only negligible coke deposition on the surface of this sample. This behaviour was attributed to the presence of Ni nanoparticles with a diameter of less than 10 nm located on a MgO/NiO solid solution shell doped by K ions; this in turn covers a core of tetragonal ZrO2 and/or a MgO/ZrO2 solid solution. This conclusion was supported by EDS/TEM, XPS, XRD and H2 chemisorption measurements.

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Acknowledgments

We thank the Irish Research Council for Science, Engineering and Technology (IRCSET) financial for support in the framework of an ERA-chemistry project. The work on catalyst characterization was conducted under the framework of the INSPIRE programme by the Irish Government’s Programme for Research in Third Level Institutions, Cycle 4, National Development Plan 2007–2013. This publication has also emanated from research conducted with the financial support of Science Foundation Ireland under Grant Number 06/CP/E007. The authors thank Prof. A. Kiennemann, Dr. A.-C. Roger and Dr. A. Pietraszek (University of Strasbourg) for carrying out thermodynamic calculations at different temperatures and for valuable discussions of the results.

Author information

Correspondence to Julian R. H. Ross.

Additional information

The authors would like to dedicate this work to the memory of the late Professor Laszlo Guczi of the Institute of Isotopes in Budapest. This work was carried out in a joint project with him coordinated by Professor Alain Keinemann and funded under the ERA Chemistry programme. This project was completed shortly before his death in December 2012.

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Nagaraja, B.M., Bulushev, D.A., Beloshapkin, S. et al. Potassium-Doped Ni–MgO–ZrO2 Catalysts for Dry Reforming of Methane to Synthesis Gas. Top Catal 56, 1686–1694 (2013). https://doi.org/10.1007/s11244-013-0102-6

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Keywords

  • K-doped Ni–MgO–ZrO2
  • Synthesis gas
  • H2 production
  • Dry reforming of methane