Understanding cage effects in the n-alkane conversion on zeolites

Theo L.M. Maesen; Edith Beerdsen; Sofia Calero; David Dubbeldam; Berend Smit

doi:10.1016/j.jcat.2005.11.007

Understanding cage effects in the n-alkane conversion on zeolites

Theo L.M. Maesen, Edith Beerdsen, Sofia Calero, David Dubbeldam, Berend Smit

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

62 Citations (Scopus)

Abstract

Molecular simulations are used to provide insight into published catalytic reactivity data for zeolites that exhibit a cage effect, the selective and preferential conversion of short-chain rather than long-chain n-alkanes. This paper demonstrates that understanding cage effects for ERI-, AFX-, and FER-type zeolites requires consideration of four components: (1) adsorption thermodynamics, (2) adsorption kinetics, (3) conversion at the exterior surface of the catalysts, and (4) coke-induced modifications to the pore texture. By breaking down the Gibbs free energy of adsorption into its enthalpic and entropic contributions, we can further elucidate the influence of the zeolite topology on the adsorption of n-alkanes with different hydrocarbon chain lengths. This analysis indicates that zeolite topologies with cages accessible through windows <0.47nm wide are particularly prone to exhibiting a cage effect, because they impose a high thermodynamic penalty on the adsorption of molecules that are too long to fit comfortably in a single cage. This improved understanding of the cage effect could facilitate its renewed use in commercial practice.

Original language	English
Pages (from-to)	278-290
Number of pages	13
Journal	Journal of Catalysis
Volume	237
Issue number	2
DOIs	https://doi.org/10.1016/j.jcat.2005.11.007
Publication status	Published - 25 Jan 2006
Externally published	Yes

Funding

These investigations were supported in part by the Netherlands Research Council for Chemical Sciences (CW) with financial aid from the Netherlands Technology Foundation, by the Netherlands Organization for Scientific Research (NWO) through PIONIER, by Chevron and by the Stichting Nationale Computer Faciliteiten (National Computing Facilities Foundation) through the use of their supercomputer facilities. The authors thank the European Commission for an ERG (to S.C.) and also thank C. Wilson, C.H. Roemkens, R. Krishna, A. Kuperman, S.I. Zones, and A.W. Burton for their comments on an earlier version of the manuscript.

Keywords

Cage effects
Enthalpy-entropy compensation
ERI-, AFX-, FER-type zeolites
n-Alkane conversion
n-Pentacosane
Shape selectivity

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10.1016/j.jcat.2005.11.007

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abstract = "Molecular simulations are used to provide insight into published catalytic reactivity data for zeolites that exhibit a cage effect, the selective and preferential conversion of short-chain rather than long-chain n-alkanes. This paper demonstrates that understanding cage effects for ERI-, AFX-, and FER-type zeolites requires consideration of four components: (1) adsorption thermodynamics, (2) adsorption kinetics, (3) conversion at the exterior surface of the catalysts, and (4) coke-induced modifications to the pore texture. By breaking down the Gibbs free energy of adsorption into its enthalpic and entropic contributions, we can further elucidate the influence of the zeolite topology on the adsorption of n-alkanes with different hydrocarbon chain lengths. This analysis indicates that zeolite topologies with cages accessible through windows <0.47nm wide are particularly prone to exhibiting a cage effect, because they impose a high thermodynamic penalty on the adsorption of molecules that are too long to fit comfortably in a single cage. This improved understanding of the cage effect could facilitate its renewed use in commercial practice.",

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AU - Calero, Sofia

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AU - Smit, Berend

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AB - Molecular simulations are used to provide insight into published catalytic reactivity data for zeolites that exhibit a cage effect, the selective and preferential conversion of short-chain rather than long-chain n-alkanes. This paper demonstrates that understanding cage effects for ERI-, AFX-, and FER-type zeolites requires consideration of four components: (1) adsorption thermodynamics, (2) adsorption kinetics, (3) conversion at the exterior surface of the catalysts, and (4) coke-induced modifications to the pore texture. By breaking down the Gibbs free energy of adsorption into its enthalpic and entropic contributions, we can further elucidate the influence of the zeolite topology on the adsorption of n-alkanes with different hydrocarbon chain lengths. This analysis indicates that zeolite topologies with cages accessible through windows <0.47nm wide are particularly prone to exhibiting a cage effect, because they impose a high thermodynamic penalty on the adsorption of molecules that are too long to fit comfortably in a single cage. This improved understanding of the cage effect could facilitate its renewed use in commercial practice.

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Understanding cage effects in the n-alkane conversion on zeolites

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