Suppression of the Aromatic Cycle in Methanol-to-Olefins Reaction over ZSM-5 by Post-Synthetic Modification Using Calcium

Irina Yarulina; Simon Bailleul; Alexey Pustovarenko; Javier Ruiz Martinez; Kristof De Wispelaere; Julianna Hajek; Bert M. Weckhuysen; Klaartje Houben; Marc Baldus; Veronique Van Speybroeck; Freek Kapteijn; Jorge Gascon

doi:10.1002/cctc.201600650

Suppression of the Aromatic Cycle in Methanol-to-Olefins Reaction over ZSM-5 by Post-Synthetic Modification Using Calcium

Irina Yarulina, Simon Bailleul, Alexey Pustovarenko, Javier Ruiz Martinez, Kristof De Wispelaere, Julianna Hajek, Bert M. Weckhuysen, Klaartje Houben, Marc Baldus, Veronique Van Speybroeck, Freek Kapteijn, Jorge Gascon^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

61 Scopus citations

Abstract

Incorporation of Ca in ZSM-5 results in a twofold increase of propylene selectivity (53 %), a total light-olefin selectivity of 90 %, and a nine times longer catalyst lifetime (throughput 792 g_MeOH g_catalyst ⁻¹) in the methanol-to-olefins (MTO) reaction. Analysis of the product distribution and theoretical calculations reveal that post-synthetic modification with Ca²⁺ leads to the formation of CaOCaOH⁺ that strongly weaken the acid strength of the zeolite. As a result, the rate of hydride transfer and oligomerization reactions on these sites is greatly reduced, resulting in the suppression of the aromatic cycle. Our results further highlight the importance of acid strength on product selectivity and zeolite lifetime in MTO chemistry.

Original language	English (US)
Pages (from-to)	3057-3063
Number of pages	7
Journal	ChemCatChem
Volume	8
Issue number	19
DOIs	https://doi.org/10.1002/cctc.201600650
State	Published - Oct 6 2016
Externally published	Yes

Keywords

acidity
alkenes
calcium
density functional calculations
zeolites

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1002/cctc.201600650

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Yarulina, I., Bailleul, S., Pustovarenko, A., Martinez, J. R., Wispelaere, K. D., Hajek, J., Weckhuysen, B. M., Houben, K., Baldus, M., Van Speybroeck, V., Kapteijn, F., & Gascon, J. (2016). Suppression of the Aromatic Cycle in Methanol-to-Olefins Reaction over ZSM-5 by Post-Synthetic Modification Using Calcium. ChemCatChem, 8(19), 3057-3063. https://doi.org/10.1002/cctc.201600650

@article{8b667f04b7f0440ab1a76f7deb6940cc,

title = "Suppression of the Aromatic Cycle in Methanol-to-Olefins Reaction over ZSM-5 by Post-Synthetic Modification Using Calcium",

abstract = "Incorporation of Ca in ZSM-5 results in a twofold increase of propylene selectivity (53 %), a total light-olefin selectivity of 90 %, and a nine times longer catalyst lifetime (throughput 792 gMeOH gcatalyst −1) in the methanol-to-olefins (MTO) reaction. Analysis of the product distribution and theoretical calculations reveal that post-synthetic modification with Ca2+ leads to the formation of CaOCaOH+ that strongly weaken the acid strength of the zeolite. As a result, the rate of hydride transfer and oligomerization reactions on these sites is greatly reduced, resulting in the suppression of the aromatic cycle. Our results further highlight the importance of acid strength on product selectivity and zeolite lifetime in MTO chemistry.",

keywords = "acidity, alkenes, calcium, density functional calculations, zeolites",

author = "Irina Yarulina and Simon Bailleul and Alexey Pustovarenko and Martinez, {Javier Ruiz} and Wispelaere, {Kristof De} and Julianna Hajek and Weckhuysen, {Bert M.} and Klaartje Houben and Marc Baldus and {Van Speybroeck}, Veronique and Freek Kapteijn and Jorge Gascon",

note = "Publisher Copyright: {\textcopyright} 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2016",

month = oct,

day = "6",

doi = "10.1002/cctc.201600650",

language = "English (US)",

volume = "8",

pages = "3057--3063",

journal = "ChemCatChem",

issn = "1867-3880",

publisher = "Wiley",

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Yarulina, I, Bailleul, S, Pustovarenko, A, Martinez, JR, Wispelaere, KD, Hajek, J, Weckhuysen, BM, Houben, K, Baldus, M, Van Speybroeck, V, Kapteijn, F & Gascon, J 2016, 'Suppression of the Aromatic Cycle in Methanol-to-Olefins Reaction over ZSM-5 by Post-Synthetic Modification Using Calcium', ChemCatChem, vol. 8, no. 19, pp. 3057-3063. https://doi.org/10.1002/cctc.201600650

TY - JOUR

T1 - Suppression of the Aromatic Cycle in Methanol-to-Olefins Reaction over ZSM-5 by Post-Synthetic Modification Using Calcium

AU - Yarulina, Irina

AU - Bailleul, Simon

AU - Pustovarenko, Alexey

AU - Martinez, Javier Ruiz

AU - Wispelaere, Kristof De

AU - Hajek, Julianna

AU - Weckhuysen, Bert M.

AU - Houben, Klaartje

AU - Baldus, Marc

AU - Van Speybroeck, Veronique

AU - Kapteijn, Freek

AU - Gascon, Jorge

PY - 2016/10/6

Y1 - 2016/10/6

N2 - Incorporation of Ca in ZSM-5 results in a twofold increase of propylene selectivity (53 %), a total light-olefin selectivity of 90 %, and a nine times longer catalyst lifetime (throughput 792 gMeOH gcatalyst −1) in the methanol-to-olefins (MTO) reaction. Analysis of the product distribution and theoretical calculations reveal that post-synthetic modification with Ca2+ leads to the formation of CaOCaOH+ that strongly weaken the acid strength of the zeolite. As a result, the rate of hydride transfer and oligomerization reactions on these sites is greatly reduced, resulting in the suppression of the aromatic cycle. Our results further highlight the importance of acid strength on product selectivity and zeolite lifetime in MTO chemistry.

AB - Incorporation of Ca in ZSM-5 results in a twofold increase of propylene selectivity (53 %), a total light-olefin selectivity of 90 %, and a nine times longer catalyst lifetime (throughput 792 gMeOH gcatalyst −1) in the methanol-to-olefins (MTO) reaction. Analysis of the product distribution and theoretical calculations reveal that post-synthetic modification with Ca2+ leads to the formation of CaOCaOH+ that strongly weaken the acid strength of the zeolite. As a result, the rate of hydride transfer and oligomerization reactions on these sites is greatly reduced, resulting in the suppression of the aromatic cycle. Our results further highlight the importance of acid strength on product selectivity and zeolite lifetime in MTO chemistry.

KW - acidity

KW - alkenes

KW - calcium

KW - density functional calculations

KW - zeolites

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DO - 10.1002/cctc.201600650

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ER -

Suppression of the Aromatic Cycle in Methanol-to-Olefins Reaction over ZSM-5 by Post-Synthetic Modification Using Calcium

Abstract

Keywords

ASJC Scopus subject areas

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