Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbons Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

Emily Catherine Nordvang; Elena Borodina; Javier Ruiz-Martínez; Rasmus Fehrmann; Bert M. Weckhuysen

doi:10.1002/chem.201503136

Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbons Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

Emily Catherine Nordvang, Elena Borodina, Javier Ruiz-Martínez, Rasmus Fehrmann, Bert M. Weckhuysen

Department of Chemistry

Utrecht University

Research output: Contribution to journal › Journal article › Research › peer-review

636 Downloads (Pure)

Abstract

The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ single crystal UV/Vis and confocal fluorescence micro-spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics at the periphery of the H-ZSM-5 crystals, which are transformed into more poly-aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H-ZSM-5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during catalytic testing with the single crystal in situ results.

Original language	English
Journal	Chemistry - A European Journal
Volume	21
Issue number	48
Pages (from-to)	17324-17335
Number of pages	12
ISSN	0947-6539
DOIs	https://doi.org/10.1002/chem.201503136
Publication status	Published - 2015

Bibliographical note

© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

Keywords

Methanol-to-olefins
Fluorescence microscopy
Heterogeneous catalysis
UV/Vis spectroscopy
Zeolites

Access to Document

10.1002/chem.201503136

Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H ZSM 5 Crystals during Alcohol to Hydrocarbons Reactions as Investigated by a Combination of Optical Spectroscopy and MicroscopyFinal published version, 4.77 MB

OpenUrl availability

Full text

Cite this

Nordvang, E. C., Borodina, E., Ruiz-Martínez, J., Fehrmann, R., & Weckhuysen, B. M. (2015). Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbons Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy. Chemistry - A European Journal, 21(48), 17324-17335. https://doi.org/10.1002/chem.201503136

@article{275bca624cf84fdf939b46b006ba9d8a,

title = "Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbons Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy",

abstract = "The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ single crystal UV/Vis and confocal fluorescence micro-spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics at the periphery of the H-ZSM-5 crystals, which are transformed into more poly-aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H-ZSM-5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during catalytic testing with the single crystal in situ results.",

keywords = "Methanol-to-olefins , Fluorescence microscopy, Heterogeneous catalysis , UV/Vis spectroscopy, Zeolites",

author = "Nordvang, {Emily Catherine} and Elena Borodina and Javier Ruiz-Mart{\'i}nez and Rasmus Fehrmann and Weckhuysen, {Bert M.}",

note = "{\textcopyright} 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.",

year = "2015",

doi = "10.1002/chem.201503136",

language = "English",

volume = "21",

pages = "17324--17335",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley",

number = "48",

}

Nordvang, EC, Borodina, E, Ruiz-Martínez, J, Fehrmann, R & Weckhuysen, BM 2015, 'Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbons Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy', Chemistry - A European Journal, vol. 21, no. 48, pp. 17324-17335. https://doi.org/10.1002/chem.201503136

Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbons Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy. / Nordvang, Emily Catherine; Borodina, Elena; Ruiz-Martínez, Javier et al.
In: Chemistry - A European Journal, Vol. 21, No. 48, 2015, p. 17324-17335.

Research output: Contribution to journal › Journal article › Research › peer-review

TY - JOUR

T1 - Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbons Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

AU - Nordvang, Emily Catherine

AU - Borodina, Elena

AU - Ruiz-Martínez, Javier

AU - Fehrmann, Rasmus

AU - Weckhuysen, Bert M.

N1 - © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

PY - 2015

Y1 - 2015

N2 - The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ single crystal UV/Vis and confocal fluorescence micro-spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics at the periphery of the H-ZSM-5 crystals, which are transformed into more poly-aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H-ZSM-5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during catalytic testing with the single crystal in situ results.

AB - The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ single crystal UV/Vis and confocal fluorescence micro-spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics at the periphery of the H-ZSM-5 crystals, which are transformed into more poly-aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H-ZSM-5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during catalytic testing with the single crystal in situ results.

KW - Methanol-to-olefins

KW - Fluorescence microscopy

KW - Heterogeneous catalysis

KW - UV/Vis spectroscopy

KW - Zeolites

U2 - 10.1002/chem.201503136

DO - 10.1002/chem.201503136

M3 - Journal article

C2 - 26463581

SN - 0947-6539

VL - 21

SP - 17324

EP - 17335

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 48

ER -

Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbons Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

Abstract

Bibliographical note

Keywords

Access to Document

OpenUrl availability

Fingerprint

Cite this