Controlling coke deactivation and cracking selectivity of MFI zeolite by H3PO4 or KOH modification

Eva Epelde; José I. Santos; Pierre Florian; Andrés T. Aguayo; Ana G. Gayubo; Javier Bilbao; Pedro Castaño

doi:10.1016/j.apcata.2015.07.022

Controlling coke deactivation and cracking selectivity of MFI zeolite by H₃PO₄ or KOH modification

Eva Epelde, José I. Santos, Pierre Florian, Andrés T. Aguayo, Ana G. Gayubo, Javier Bilbao, Pedro Castaño^*

^*Corresponding author for this work

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

47 Scopus citations

Abstract

The effect of the basic (KOH) or acid (H₃PO₄) treatment of the MFI (HZSM-5) zeolite has been studied comparing the structural and acidic features with the catalytic performance and deactivation of a set of unmodified and modified zeolites (SiO₂/Al₂O₃ = 30-280, 0-3 wt% of K or P). The properties of the catalysts have been elucidated using XRD, ²⁷Al and ²⁹Si NMR, N₂ adsorption-desorption, and adsorption-TPD of tert-butylamine. The catalytic performance has been evaluated in the cracking of 1-butene by means of initial, 5 h on-stream activity and coke formation. Our results point to the fact that using zeolites with high SiO₂/Al₂O₃ ratio or neutralizing the strongest acid sites with KOH or H₃PO₄ increases propylene selectivity while decreases 1-butene conversion. The overall pathway of reaction involves propylene and other olefins as primary products that condensate in further steps to aromatics and ultimately to coke. This pathway can be controlled with less severe acidic features and by desilication with KOH or H₃PO₄ (particularly with the former).

Original language	English (US)
Pages (from-to)	105-115
Number of pages	11
Journal	Applied Catalysis A: General
Volume	505
DOIs	https://doi.org/10.1016/j.apcata.2015.07.022
State	Published - Aug 11 2015
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2015 Z. Published by Elsevier B.V.

Keywords

Acidity modification
Coke deactivation
Oligomerization-cracking
Propylene
ZSM-5 zeolite

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology

Access to Document

10.1016/j.apcata.2015.07.022

Cite this

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title = "Controlling coke deactivation and cracking selectivity of MFI zeolite by H3PO4 or KOH modification",

abstract = "The effect of the basic (KOH) or acid (H3PO4) treatment of the MFI (HZSM-5) zeolite has been studied comparing the structural and acidic features with the catalytic performance and deactivation of a set of unmodified and modified zeolites (SiO2/Al2O3 = 30-280, 0-3 wt% of K or P). The properties of the catalysts have been elucidated using XRD, 27Al and 29Si NMR, N2 adsorption-desorption, and adsorption-TPD of tert-butylamine. The catalytic performance has been evaluated in the cracking of 1-butene by means of initial, 5 h on-stream activity and coke formation. Our results point to the fact that using zeolites with high SiO2/Al2O3 ratio or neutralizing the strongest acid sites with KOH or H3PO4 increases propylene selectivity while decreases 1-butene conversion. The overall pathway of reaction involves propylene and other olefins as primary products that condensate in further steps to aromatics and ultimately to coke. This pathway can be controlled with less severe acidic features and by desilication with KOH or H3PO4 (particularly with the former).",

keywords = "Acidity modification, Coke deactivation, Oligomerization-cracking, Propylene, ZSM-5 zeolite",

author = "Eva Epelde and Santos, {Jos{\'e} I.} and Pierre Florian and Aguayo, {Andr{\'e}s T.} and Gayubo, {Ana G.} and Javier Bilbao and Pedro Casta{\~n}o",

note = "Publisher Copyright: {\textcopyright} 2015 Z. Published by Elsevier B.V.",

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doi = "10.1016/j.apcata.2015.07.022",

language = "English (US)",

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T1 - Controlling coke deactivation and cracking selectivity of MFI zeolite by H3PO4 or KOH modification

AU - Epelde, Eva

AU - Santos, José I.

AU - Florian, Pierre

AU - Aguayo, Andrés T.

AU - Gayubo, Ana G.

AU - Bilbao, Javier

AU - Castaño, Pedro

PY - 2015/8/11

Y1 - 2015/8/11

N2 - The effect of the basic (KOH) or acid (H3PO4) treatment of the MFI (HZSM-5) zeolite has been studied comparing the structural and acidic features with the catalytic performance and deactivation of a set of unmodified and modified zeolites (SiO2/Al2O3 = 30-280, 0-3 wt% of K or P). The properties of the catalysts have been elucidated using XRD, 27Al and 29Si NMR, N2 adsorption-desorption, and adsorption-TPD of tert-butylamine. The catalytic performance has been evaluated in the cracking of 1-butene by means of initial, 5 h on-stream activity and coke formation. Our results point to the fact that using zeolites with high SiO2/Al2O3 ratio or neutralizing the strongest acid sites with KOH or H3PO4 increases propylene selectivity while decreases 1-butene conversion. The overall pathway of reaction involves propylene and other olefins as primary products that condensate in further steps to aromatics and ultimately to coke. This pathway can be controlled with less severe acidic features and by desilication with KOH or H3PO4 (particularly with the former).

AB - The effect of the basic (KOH) or acid (H3PO4) treatment of the MFI (HZSM-5) zeolite has been studied comparing the structural and acidic features with the catalytic performance and deactivation of a set of unmodified and modified zeolites (SiO2/Al2O3 = 30-280, 0-3 wt% of K or P). The properties of the catalysts have been elucidated using XRD, 27Al and 29Si NMR, N2 adsorption-desorption, and adsorption-TPD of tert-butylamine. The catalytic performance has been evaluated in the cracking of 1-butene by means of initial, 5 h on-stream activity and coke formation. Our results point to the fact that using zeolites with high SiO2/Al2O3 ratio or neutralizing the strongest acid sites with KOH or H3PO4 increases propylene selectivity while decreases 1-butene conversion. The overall pathway of reaction involves propylene and other olefins as primary products that condensate in further steps to aromatics and ultimately to coke. This pathway can be controlled with less severe acidic features and by desilication with KOH or H3PO4 (particularly with the former).

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