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Structure–performance descriptors and the role of Lewis acidity in the methanol-to-propylene process

Nature Chemistry volume 10, pages 804–812 (2018)Cite this article

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A Publisher Correction to this article was published on 10 July 2018

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Abstract

The combination of well-defined acid sites, shape-selective properties and outstanding stability places zeolites among the most practically relevant heterogeneous catalysts. The development of structure–performance descriptors for processes that they catalyse has been a matter of intense debate, both in industry and academia, and the direct conversion of methanol to olefins is a prototypical system in which various catalytic functions contribute to the overall performance. Propylene selectivity and resistance to coking are the two most important parameters in developing new methanol-to-olefin catalysts. Here, we present a systematic investigation on the effect of acidity on the performance of the zeolite ‘ZSM-5’ for the production of propylene. Our results demonstrate that the isolation of Brønsted acid sites is key to the selective formation of propylene. Also, the introduction of Lewis acid sites prevents the formation of coke, hence drastically increasing catalyst lifetime.

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Fig. 1: Schematic illustrations of the HP concept for the MTO reaction and the synthesis of pre- and post-synthetically modified zeolites.
Fig. 2: Evaluation of Brønsted and Lewis acid site interactions.
Fig. 3: Catalytic behaviour of pre- and post-synthetically modified catalysts.
Fig. 4: Modified zeolites decrease the stability and growth rate of aromatic MTO intermediates.
Fig. 5: DFT-based enthalpy calculations at 500 °C reveal the most stable structure of binuclear Ca species in ZSM-5.
Fig. 6: Visualization of the trapped hydrocarbon species in Z- and AE-series.

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Change history

  • 10 July 2018

    In the version of this Article originally published, on the right side of Fig. 4b, the ‘Aromatic cycle’ label was erroneously shifted outside of the central circular arrow into a position on part of the reaction cycle. This has been corrected in the online versions of the Article.

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Acknowledgements

This research received funding from the Netherlands Organization for Scientific Research (NWO) in the framework of the TASC Technology Area ‘Syngas, a Switch to Flexible New Feedstock for the Chemical Industry (TA-Syngas). S.B., K.D.W. and V.V.S. acknowledge the Fund for Scientific Research: Flanders (FWO), the Belgian American Educational Foundation, the Research Board of Ghent University (BOF), BELSPO in the frame of IAP/7/05 and funding from the European Union’s Horizon 2020 research and innovation programme (consolidator ERC grant agreement no. 647755—DYNPOR (2015–2020)). The computational resources and services used were provided by Ghent University (Stevin Supercomputer Infrastructure) and the VSC (Flemish Supercomputer Center), funded by the Research Foundation: Flanders (FWO).

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Authors and Affiliations

  1. Catalysis Engineering, Chemical Engineering Department, Delft University of Technology, Delft, the Netherlands

    Irina Yarulina, Mike Radersma, Ina Vollmer, Freek Kapteijn & Jorge Gascon

  2. King Abdullah University of Science and Technology, KAUST Catalysis Center, Advanced Catalytic Materials, Thuwal, Saudi Arabia

    Irina Yarulina & Jorge Gascon

  3. Center for Molecular Modeling, Ghent University, Zwijnaarde, Belgium

    Kristof De Wispelaere, Simon Bailleul & Veronique Van Speybroeck

  4. Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, the Netherlands

    Joris Goetze & Bert M. Weckhuysen

  5. King Abdullah University of Science and Technology (KAUST), Core Labs, Thuwal, Saudi Arabia

    Edy Abou-Hamad

  6. Schuit Institute of Catalysis, Laboratory of Inorganic Materials Chemistry, Eindhoven University of Technology, Eindhoven, the Netherlands

    Maarten Goesten, Brahim Mezari & Emiel J. M. Hensen

  7. Centre for Materials Science and Nanotechnology, Department of Chemistry, University of Oslo, Oslo, Norway

    Juan S. Martínez-Espín, Magnus Morten & Unni Olsbye

  8. Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Zurich, Switzerland

    Sharon Mitchell & Javier Perez-Ramirez

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  1. Irina Yarulina
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Contributions

I.Y. and J.Ga. conceived, coordinated the research and designed the experiments in close collaboration with V.V.S. I.Y. synthesized and characterized most catalysts and performed all catalytic tests with support from M.R. and I.V.S.M. and J.P.R. provided several demetallated zeolite catalysts and J.S.M.E. and M.M. provided the ZSM-5 nanosheets and performed the methylation reactions. S.B., K.D.W. and V.V.S. performed the DFT and ab initio MD calculations. B.M. and E.A.H. performed NMR characterization and J.Go. performed the in situ UV–vis analysis. All authors contributed to analysis and discussion of the data. The manuscript was primarily written by I.Y., K.D.W., V.V.S. and J.Ga. with input from all authors.

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Correspondence to Jorge Gascon.

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Supplementary information

Supplementary Information

Supplementary Experimental Data, including detailed catalyst preparation and co-feeding experiments, Supplementary Computational Details, Supplementary Figures 1–41, Supplementary Tables 1–9

Supplementary Data 1

Calculated XYZ coordinates. Calculated XYZ coordinates of all considered structures including structural analysis, protonation energy and propene methylation

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Yarulina, I., De Wispelaere, K., Bailleul, S. et al. Structure–performance descriptors and the role of Lewis acidity in the methanol-to-propylene process. Nature Chem 10, 804–812 (2018). https://doi.org/10.1038/s41557-018-0081-0

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