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Lifetime improvement in methanol-to-olefins catalysis over chabazite materials by high-pressure H2 co-feeds

Nature Catalysis volume 1, pages 666–672 (2018)Cite this article

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Abstract

Mitigating catalyst deactivation in the industrially deployed process of methanol-to-olefins conversion over HSAPO-34 is a critical challenge. Here, we demonstrate that lifetime in methanol-to-olefins catalysis over HSAPO-34 at sub-complete methanol conversion, as determined by the cumulative turnover capacity per Brønsted acid site towards hydrocarbon products in the effluent before complete catalyst deactivation (~15% carbon final conversion), can be enhanced with increasing efficacy (~2.8× to >70×) by co-feeding H2 at increasing partial pressures (400–3,000 kPa) in the influent with methanol compared with co-feeding helium at equivalent pressures. The lifetime improvement in the presence of high-pressure H2 co-feeds is observed to be more prominent at complete methanol conversion than at sub-complete conversion. The improvements in catalyst lifetime by co-feeding H2 are rendered without any deleterious effects on C2–C4 olefins selectivity, which remains ~85% carbon irrespective of the inlet H2 pressure. These observations can be rationalized based on the participation of H2 in hydrogen transfer reactions, and in effect, the interception of pathways that promote the formation of deactivation-inducing polycyclic species.

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Fig. 1: Catalytic behaviour of HSAPO-34 with helium versus H2 co-feeds at sub-complete methanol conversion.
Fig. 2: Catalytic behaviour of HSAPO-34 with helium versus H2 co-feeds at complete methanol conversion.
Fig. 3: Catalytic behaviour of HZSM-5 with helium versus H2 co-feeds at sub-complete methanol conversion.
Fig. 4: Catalytic behaviour of HSAPO-34 with helium versus H2 co-feeds with methanol-formaldehyde feeds.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

We acknowledge: The Dow Chemical Company and National Science Foundation (CBET 1701534) for financial support; the Characterization Facility, University of Minnesota, which receives partial support from the National Science Foundation through the Materials Research Science and Engineering Centers programme, for providing the X-ray diffraction and X-ray photoelectron spectroscopy data; T. Whitmer, The Ohio State University, for providing the NMR data; The Dow Chemical Company, Analytical Science, Midland and Terneuzen for providing the quantitative elemental analysis, scanning electron microscopy and extracts analysis data; D. M. Millar, The Dow Chemical Company, for synthesis of the SSZ-13 sample; and J. F. DeWilde, The Dow Chemical Company, for helpful technical discussions.

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Authors and Affiliations

  1. Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN, USA

    Sukaran S. Arora & Aditya Bhan

  2. Dow Benelux B.V., Hoek, Netherlands

    Davy L. S. Nieskens

  3. The Dow Chemical Company, Midland, MI, USA

    Andrzej Malek

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  1. Sukaran S. Arora
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Contributions

D.L.S.N. and A.M conceptualized the research effort. The experimental outline was designed by all authors. A.M. synthesized the SAPO-34 sample. S.S.A. performed the experiments. S.S.A. and A.B. analysed the reaction data. All authors contributed towards data interpretation. S.S.A. drafted the initial manuscript. All authors reviewed and edited the manuscript and supplementary materials.

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Correspondence to Aditya Bhan.

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Supplementary Notes, Supplementary Figures 1–10; Supplementary Tables 1–6; Supplementary Methods; Supplementary References

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Arora, S.S., Nieskens, D.L.S., Malek, A. et al. Lifetime improvement in methanol-to-olefins catalysis over chabazite materials by high-pressure H2 co-feeds. Nat Catal 1, 666–672 (2018). https://doi.org/10.1038/s41929-018-0125-2

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