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Catalyst design for natural-gas upgrading through oxybromination chemistry

Nature Chemistry volume 8, pages 803–809 (2016)Cite this article

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Abstract

Natural gas contains large volumes of light alkanes, and its abundant reserves make it an appealing feedstock for value-added chemicals and fuels. However, selectively activating the C–H bonds in these useful hydrocarbons is one of the greatest challenges in catalysis. Here we report an attractive oxybromination method for the one-step functionalization of methane under mild conditions that integrates gas-phase alkane bromination with heterogeneously catalysed HBr oxidation, a step that is usually executed separately. Catalyst-design strategies to provide optimal synergy between these two processes are discussed. Among many investigated material families, vanadium phosphate (VPO) is identified as the best oxybromination catalyst, as it provides selectivity for CH3Br up to 95% and stable operation for over 100 hours on stream. The outstanding performance of VPO is rationalized by its high activity in HBr oxidation and low propensity for methane and bromomethane oxidation. Data on the oxybromination of ethane and propane over VPO suggest that the reaction network for higher alkanes is more complex.

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Figure 1: Closed loop bromine-mediated light-alkane conversion scheme to produce value-added chemicals and fuels.
Figure 2: Catalytic performance expressed as single-pass carbon yields (Y) of products for selected catalysts in the oxybromination of methane at 753 K.
Figure 3: Evolution of VPO in the oxybromination of methane at 753 K.
Figure 4: Performance descriptors for the design of selective methane oxybromination catalysts.
Figure 5: Heterogeneous gas-phase reaction pathways and improvement of the CH3Br productivity by optimizing reaction conditions.
Figure 6: The performance of VPO in the oxybromination of methane, ethane and propane.

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Acknowledgements

The authors acknowledge financial support from the Swiss National Science Foundation (project no. 200021-156107). The Scientific Center for Optical and Electron Microscopy (ScopeM) at ETH Zurich is thanked for providing access to the facility. Z. Guo is acknowledged for assistance with catalyst preparation. The authors are grateful to F. Krumeich for HRTEM analyses and R. Verel for 31P MAS NMR analyses.

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  1. Department of Chemistry and Applied Biosciences, Institute for Chemical and Bioengineering, ETH Zurich, Vladimir-Prelog-Weg 1, Zurich, CH-8093, Switzerland

    Vladimir Paunović, Guido Zichittella, Maximilian Moser, Amol P. Amrute & Javier Pérez-Ramírez

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  1. Vladimir Paunović
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  2. Guido Zichittella
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  5. Javier Pérez-Ramírez
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Contributions

J.P.-R. conceived and coordinated all the stages of this research. V.P. prepared the catalyst samples, performed the catalytic tests and characterized materials by XRD and H2-TPR, and G.Z. and M.M. conducted part of the catalytic tests. A.P.A. assisted in the HRTEM and solid-state NMR characterization. V.P., M.M., A.P.A. and J.P.-R. wrote the paper.

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Correspondence to Javier Pérez-Ramírez.

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Paunović, V., Zichittella, G., Moser, M. et al. Catalyst design for natural-gas upgrading through oxybromination chemistry. Nature Chem 8, 803–809 (2016). https://doi.org/10.1038/nchem.2522

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