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Recent trends and fundamental insights in the methanol-to-hydrocarbons process

Nature Catalysis volume 1, pages 398–411 (2018)Cite this article

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Abstract

The production of high-demand chemical commodities such as ethylene and propylene (methanol-to-olefins), hydrocarbons (methanol-to-hydrocarbons), gasoline (methanol-to-gasoline) and aromatics (methanol-to-aromatics) from methanol—obtainable from alternative feedstocks, such as carbon dioxide, biomass, waste or natural gas through the intermediate formation of synthesis gas—has been central to research in both academia and industry. Although discovered in the late 1970s, this catalytic technology has only been industrially implemented over the past decade, with a number of large commercial plants already operating in Asia. However, as is the case for other technologies, industrial maturity is not synonymous with full understanding. For this reason, research is still intense and a number of important discoveries have been reported over the last few years. In this review, we summarize the most recent advances in mechanistic understanding—including direct C–C bond formation during the induction period and the promotional effect of zeolite topology and acidity on the alkene cycle—and correlate these insights to practical aspects in terms of catalyst design and engineering.

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Fig. 1: Milestones and mechanism development of the MTH process.
Fig. 2: Several proposed direct mechanistic routes during the early stages of the zeolite-catalysed MTH process.

panel a adapted from ref. 18, American Chemical Society; panels b and c adapted from refs 11,13, Wiley, respectively; panels d and e reproduced from refs 29,33, Royal Society of Chemistry; panels f–i reproduced from ref. 14, Wiley; panel j adapted from ref. 13, Wiley; panel k adapted from ref. 17, American Chemical Society.

Fig. 3: The spectroscopic signatures of crucial intermediates during the zeolite catalysed methanol-to-hydrocarbon (MTH) process.

panels a–c from refs 13,14 and 13, Wiley, respectively; panel d reproduced from ref. 46, American Chemical Society; panel e reproduced from ref. 13, Wiley; panel f reproduced from ref. 53, Wiley

Fig. 4: Steady-state mechanism development of the MTH process.
Fig. 5: Impact of topology on cycles propagation.
Fig. 6: Impact of acidity on cycles propagation.
Fig. 7: Resolving the location of the first coke species formed during the MTH process using APT.

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Author notes

  1. These authors contributed equally: Irina Yarulina, Abhishek Dutta Chowdhury.

Authors and Affiliations

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

    Irina Yarulina & Jorge Gascon

  2. Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, The Netherlands

    Abhishek Dutta Chowdhury, Florian Meirer & Bert M. Weckhuysen

Authors
  1. Irina Yarulina
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  2. Abhishek Dutta Chowdhury
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  3. Florian Meirer
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  4. Bert M. Weckhuysen
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  5. Jorge Gascon
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Correspondence to Bert M. Weckhuysen or Jorge Gascon.

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Yarulina, I., Chowdhury, A.D., Meirer, F. et al. Recent trends and fundamental insights in the methanol-to-hydrocarbons process. Nat Catal 1, 398–411 (2018). https://doi.org/10.1038/s41929-018-0078-5

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