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Al-MFI Nanosheets as Highly Active and Stable Catalysts for the Conversion of Propanal to Hydrocarbons

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Abstract

The conversion of propanal to hydrocarbons is investigated over mesoporous aluminosilicate MFI nanosheets (Al-MFI-ns) of single-unit-cell thickness and conventional aluminum MFI zeolite (Al-MFI) at 673 K and atmospheric pressure. Al-MFI-ns exhibits a fivefold increase in stability attributed to the shorter diffusion path lengths and open architecture of the nanosheets, which minimizes pore blocking from fouling. The overall ratio of olefin to aromatic products is similar for Al-MFI-ns and Al-MFI at all conversion levels. However, the product distribution within each group shows that the Al-MFI-ns generate a fivefold increase in selectivity to C6–8 olefins and a twofold increase in selectivity to C9–10 aromatics compared to Al-MFI. The very high selectivity to C9– aromatic trimethylbenzene supports an aromatization mechanism involving sequential aldol condensation and dehydration sequences. The very short diffusion paths in the single-unit-cell thick nanosheets allows for the C9 aromatics to diffuse out of the pores before they can be converted to lighter aromatics or olefins. Al-MFI-ns shows no indication of irreversible deactivation, fully recovering its original activity after regeneration by calcination, and retaining similar deactivation rates and product selectivities as the fresh catalyst. Al-FMI-ns improves the production of aromatics from light oxygenates at mild conditions, a key feature for bio-oil upgrading.

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Acknowledgments

This research was supported with funds from the Small Business Innovation Research (SBIR) program at the Department of Energy under contract 97329S11-11.

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Authors and Affiliations

  1. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA

    Helen Luo, Teerawit Prasomsri & Yuriy Román-Leshkov

Authors
  1. Helen Luo
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  2. Teerawit Prasomsri
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  3. Yuriy Román-Leshkov
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Correspondence to Yuriy Román-Leshkov.

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Dedication

This article is dedicated to Prof. Mark E. Davis, a great mentor and friend, who recently received the prestigious Somorjai award honouring his important contributions to the field of molecular sieves. Undoubtedly, his work has shaped our understanding of solid acid chemistry and catalysis with porous materials. While his work has profoundly impacted many research areas in both industrial and academic settings, an equally important aspect of his contributions have stemmed from mentoring and inspiring those around him to take risks and undertake new, challenging research directions. During my postdoctoral stay in his group from 2008–2010, we explored the use of solid Lewis acids, such as Sn-Beta, for the activation carbohydrates [1–3]. In turn, this work strongly influenced the research direction undertaken in my independent academic career, including, for example, the use of hafnium-based materials to activate oxygenates [4, 5]. In this contribution, we show how controlling the morphology of zeolite crystals through amphiphilic structure directing agents that produce nanosheets results in materials with drastically higher stability and lifetime for the conversion of short oxygenates to aromatics.

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Luo, H., Prasomsri, T. & Román-Leshkov, Y. Al-MFI Nanosheets as Highly Active and Stable Catalysts for the Conversion of Propanal to Hydrocarbons. Top Catal 58, 529–536 (2015). https://doi.org/10.1007/s11244-015-0394-9

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