Kinetic modeling of pore mouth catalysis in the hydroconversion of n-octane on Pt-H-ZSM-22

Narasimhan, C.S. Laxmi; Thybaut, Joris W.; Marin, Guy; Jacobs, Pierre; Martens, Johan A.; Denayer, Joeri; Baron, Gino V.

doi:10.1016/s0021-9517(03)00281-1

Cited by 90 publications

(79 citation statements)

References 35 publications

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“…A fundamental Single-Event MicroKinetic (SEMK) methodology has been developed to describe the complex reaction mechanism in gas-phase hydroconversion of n-alkanes over large-pore USY zeolites [20][21][22][23], and has later been extended to deal with extreme shape selectivity [24] and also bulk-phase non-idealities encountered during liquid hydrocracking [25,26]. For other well-known large-pore zeolites, such as mordenite and beta, a fundamental microkinetic model has not yet been constructed.…”

Section: Introductionmentioning

confidence: 99%

n-Hexadecane hydrocracking Single-Event MicroKinetics on Pt/H-beta

Vandegehuchte

Thybaut

Martı́nez

et al. 2012

Applied Catalysis A: General

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The Single-Event MicroKinetic (SEMK) model constructed for gas-phase hydroconversion of light n-alkanes on large-pore USY zeolites was applied, for the first time, to the hydrocracking of n-hexadecane on a Pt/H-Beta catalyst. Despite the 12-ringed pore channels, shape selectivity was observed in the formation of ethyl side chains.Additionally, heavy feed molecules such as n-hexadecane lead to physisorption saturation of the catalyst pores by strong Van der Waals interactions of the long alkyl chains with the zeolite framework. Intermolecular interactions and packing efficiencies in the pores induce deviations from typical Henry-regime physisorption characteristics as the physisorption selectivity, which is expected to increase with increasing carbon number, appeared to be independent of the latter. Micropore saturation effects were described by the 'size entropy' which quantifies the difference in standard entropy loss between physisorption in the Henry regime and hindered physisorption on a saturated surface. The size entropy is proportional to the catalyst loading with physisorbed species and the adsorbate carbon number. The addition of a size entropy term in the SEMK model, amounting to 102 J mol -1 K -1 for a hexadecane molecule at full saturation, allowed accurately reproducing the contribution of secondary isomerization and cracking reactions, as quantified by means of a contribution analysis.2

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Section: Introductionmentioning

confidence: 99%

n-Hexadecane hydrocracking Single-Event MicroKinetics on Pt/H-beta

Vandegehuchte

Thybaut

Martı́nez

et al. 2012

Applied Catalysis A: General

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“…Many automated network generation algorithms have been developed and described in the literature for different applications: hydrocarbon pyrolysis (Clymans and Froment, 1984;Hillewaert et al, 1988;Chinnick et al, 1988;Froment, 1991;Dente et al, 1992;DiMaio and Lignola,Dewachtere et al, 1999;Christensen et al, 1999;Moustafa and Froment, 2003;Froment, 2005;Quintana-Solórzano et al, 2007a, b), hydrocracking (Baltanas and Froment, 1985;Baltanas et al, 1989;Vynckier and Froment, 1991;Quann andJaffe, 1992, 1996;Quann, 1998;Martens and Froment, 1999;Mizan and Klein, 1999;Martens et al, 2000Martens et al, , 2001Thybaut and Marin, 2003;Laxmi Narasimhan et al, 2003, 2004Chavarría-Hernández et al, 2004Jaffe et al, 2005;Klein et al, 2006;Kumar and Froment, 2007a, b), hydrotreating (Hou and Klein, 1999;Klein et al, 2006), methanol-to-olefins Froment, 2001, 2004;Al Wahabi and Froment, 2004;Froment, 2005), FischerTropsch synthesis (Klinke and Broadbelt, 1999;Temkin et al, 2002;Lozano et al, 2006Lozano et al, , 2008, coke formation (Moustafa and Froment, 2003;Quintana-Solórzano et al, 2005), silicon hydride clustering …”

Section: Introductionmentioning

confidence: 99%

Reduction of Single Event Kinetic Models by Rigorous Relumping: Application to Catalytic Reforming

Cochegrue

Gauthier

Verstraete

et al. 2011

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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Résumé -Réduction de modèles cinétiques basée sur les événements constitutifs à l'aide d'un regroupement rigoureux : application au reformage catalytique -La modélisation des procédés de raffinage utilisant des catalyseurs bifonctionnels métal-acide fait intervenir un nombre exponentiellement croissant d'espèces et de réactions qui peut rapidement dépasser plusieurs milliers pour des charges industrielles complexes. Lors de la réalisation d'un modèle de procédé, l'utilisation de modèles cinétiques de regroupement a priori par familles chimiques ne satisfait plus les besoins actuels de simulation détail-lée, de prédictivité et d'extrapolabilité. À cause du grand nombre d'étapes élémentaires impliquées dans la catalyse bifonctionnelle, il est déraisonnable de vouloir construire à la main un réseau cinétique détaillé d'une telle ampleur. La génération informatique du réseau réactionnel à partir de règles simples propose une solution élégante dans un tel cas. Malgré cela, l'établissement des équations cinétiques et leur résolu-tion reste difficile, essentiellement à cause du manque de détail analytique demandé par un modèle détaillé. Néanmoins, pour plusieurs procédés de raffinage, des hypothèses raisonnables concernant les équilibres entre espèces permettent d'effectuer un regroupement a posteriori des espèces, réduisant de cette manière la taille du réseau réactionnel tout en maintenant un réseau cinétique entre familles chimiques qui est strictement équivalent au réseau détaillé. Nous présentons ici les outils de génération de réseau et la méthode de regroupement a posteriori associés à la méthode de modélisation cinétique par événements constitutifs. Cette approche de regroupement a posteriori est illustrée et appliquée à la modélisation cinétique des réactions de reformage catalytique. Abstract

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“…Branched C5-C9 alkanes penetrate inside ZSM-22 crystals only when applied in liquid phase but not in vapor phase relevant to the hydroisomerization experiments run in the laboratory [16]. A fundamental kinetic model based on pore-mouth and key-lock catalysis has been developed and successfully implemented for the description of the shape-selective hydroconversion on Pt/H-ZSM-22 [17].…”

Section: Introductionmentioning

confidence: 99%

Skeletal isomerization of octadecane on bifunctional ZSM-23 zeolite catalyst

et al. 2005

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Octadecane was isomerized over three different Pt/H-ZSM-23 samples. The distributions of methylheptadecane and dimethylheptadecane skeletal isomers obtained on the Pt/ZSM-23 samples were very similar. Positional isomer distributions are fingerprints of the zeolite framework structure. The independence of skeletal isomer distributions from Al-gradients and particle size constitutes a strong argument in favor of pore-mouth catalysis.

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Kinetic modeling of pore mouth catalysis in the hydroconversion of n-octane on Pt-H-ZSM-22

Cited by 90 publications

References 35 publications

n-Hexadecane hydrocracking Single-Event MicroKinetics on Pt/H-beta

n-Hexadecane hydrocracking Single-Event MicroKinetics on Pt/H-beta

Reduction of Single Event Kinetic Models by Rigorous Relumping: Application to Catalytic Reforming

Skeletal isomerization of octadecane on bifunctional ZSM-23 zeolite catalyst

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