Kinetic modeling of paraffins hydrocracking based upon elementary steps and the single event concept

Martens, Gert; Froment, Gilbert F.

doi:10.1016/s0167-2991(99)80164-5

Cited by 29 publications

(24 citation statements)

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“…Transition states in hydroisomerization and in the hydrocracking mechanism of the isomers that hydrocrack most easily. 476,[478][479][480][481] Hydroisomerization of a linear n-alkane into a branched alkane (top, R 1 , R 2 a H(CH 2 ) x -moiety with x g 0) involves a protonated dialkylcycloalkane intermediate. RRγ-trimethylalkane hydrocracking involves only the most stable, tertiary carbocation transition states and therefore exhibits the highest hydrocracking rate.…”

Section: Basic Mechanismmentioning

confidence: 99%

Molecular Simulations of Zeolites: Adsorption, Diffusion, and Shape Selectivity

2008

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Section: Basic Mechanismmentioning

confidence: 99%

Molecular Simulations of Zeolites: Adsorption, Diffusion, and Shape Selectivity

2008

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“…As earlier work (Svoboda et al, 1995;Martens and Froment, 1999; showed that the total concentration of carbenium ions could be neglected compared to the total concentration of acid sites, the forward reaction rate for the gas-phase reaction is therefore reduced to:…”

Section: A Posteriori Relumping Of Large Networkmentioning

confidence: 99%

“…An other explanation of the overprediction of the reactivity of squalane may be linked to the chemisorption of the carbenium ions, as the proposed kinetic model does not contain an inhibition term due to chemisorption on acid sites. Indeed, previous literature studies (Svoboda et al, 1995;Martens and Froment, 1999;) have shown that the total concentration of carbenium ions could be neglected compared to the total concentration of acid sites. However, these observations were based on hydrocracking experiments on n-C 8 to n-C 12 paraffins and on mixtures of n-C 8 with 10 mole% of branched C 8 paraffins.…”

Section: Parameter Identificationmentioning

confidence: 99%

“…The single event methodology has already been extensively described in the literature. This acid-catalyzed modelling approach has been applied to isomerization (Guillaume et al, 2003a;Surla et al, 2004Surla et al, , 2011, alkylation (Martinis and Froment, 2006), olefin oligomerization (Guillaume, 2006;Shahrouzi et al, 2008), methanol-to-olefins Froment, 2001a, b, 2004;Al Wahabi and Froment, 2004;Froment, 2005), catalytic reforming (Sotelo-Boyás and Froment, 2009;Cochegrue et al, 2011), catalytic cracking (Feng et al, 1993;Dewachtere et al, 1999;Beirnaert et al, 2001;Moustafa and Froment, 2003;Froment, 2005;Quintana-Solórzano et al, 2005, b, 2010 and hydrocracking (Baltanas and Froment, 1985;Baltanas et al, 1989;Vynckier and Froment, 1991;Svoboda et al, 1995;Schweitzer et al, 1999;Martens and Froment, 1999;Martens et al, 2000Thybaut et al, 2001Thybaut et al, , 2009Thybaut and Marin, 2003;Laxmi Narasimhan et al, 2003a, b, 2004, 2006Chavarría-Hernández et al, 2004Kumar and Froment, 2007a, b;Chavarría-Hernández and Ramírez, 2009;Mitsios et al, 2009;Choudhury et al, 2010).…”

Section: Introductionmentioning

confidence: 99%

“…Concerning the modelling of the hydrocracking process, good results have been obtained for the modelling of hydrocracking at lab scale (Baltanas et al, 1989;Vynckier and Froment, 1991;Svoboda et al, 1995;Martens and Froment, 1999;Thybaut and Marin, 2003;Kumar and Froment, 2007a, b;Chavarría-Hernández et al, 2008;Chavarría-Hernández and Ramírez, 2009;Thybaut et al, 2009) and at pilot plant scale (Schweitzer et al, 1999;Mitsios et al, 2009). The direct approach of the methodology, as described by Baltanas and Froment (1985) and Vynckier and Froment (1991), becomes unpractical when it is applied to heavy feeds with high carbon numbers, as the size of the generated network, both in terms of species and reactions, increases extremely rapidly with carbon number, resulting in colossal computing times and intractable networks.…”

Section: Introductionmentioning

confidence: 99%

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Single Event Kinetic Modelling without Explicit Generation of Large Networks: Application to Hydrocracking of Long Paraffins

Denis

Valéry

Verstraete

et al. 2011

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

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Résumé -Modélisation cinétique par événements constitutifs sans génération explicite de grands réseaux : application à l'hydrocraquage des paraffines longues -Le concept de modélisation par événements constitutifs permet de développer des modèles cinétiques pour la simulation des procédés de raffinage. Pour des réseaux réactionnels de centaines de milliers d'espèces, comme cela est le cas pour le reformage catalytique, le regroupement rigoureux par nombre d'atomes de carbone et degré de ramification a été utilisé efficacement en faisant l'hypothèse de l'équilibre chimique dans chaque groupe. Cette technique de regroupement conduit à un modèle regroupé compact sans perte d'information, mais nécessite tous les détails d'un réseau réactionnel complet, généré de manière explicite. Les techniques classiques de génération de réseaux deviennent inutilisables quand les hydrocarbures contiennent au delà d'environ 20 atomes de carbone à cause de la croissance extrêmement rapide du réseau réactionnel. Ainsi, des techniques implicites de regroupement ont été développées afin de calculer les coefficients de regroupement sans avoir à générer le réseau réactionnel détaillé. Deux approches alternatives et équivalentes sont présentées, basées soit sur une décomposition en classes structurales, soit une décomposition en chaînes latérales. Ces deux méthodes sont comparées et la méthode de décomposition en chaînes latérales est appliquée à la modélisation cinétique de l'hydrocraquage des paraffines longues. La méthode de décomposition en chaînes latérales est strictement équivalente à la méthode originelle basée sur la génération explicite du réseau réactionnel détaillé, pour autant que la méthode de contribution de groupe de Benson soit utilisée pour calculer les propriétés thermodynamiques dans chacune des approches. Abstract -Single Event Kinetic Modelling without Explicit Generation of Large Networks:Application to Hydrocracking of Long Paraffins -The single event modelling concept allows developing kinetic models for the simulation of refinery processes. For reaction networks with several hundreds of thousands of species, as is the case for catalytic reforming, rigorous relumping by carbon atom number and branching degree were efficiently employed by assuming chemical equilibrium in each lump. This relumping technique yields a compact lumped model without any loss of information, but requires the full detail of an explicitly generated reaction network. Classic network generation techniques become impractical when the hydrocarbon species contain more than approximately 20 carbon atoms, because of the extremely rapid growth of reaction network. Hence, Oil & Gas Science and Technology -Rev. IFP Energies nouvelles, Vol. 66 (2011), No. 3, pp. 399-422 Copyright © 2011, IFP Energies nouvelles DOI: 10.2516/ogst/2011118 Chemical Reaction Modelling of Refining Processes Modélisation cinétique des procédés de raffinage D o s s i e rOil & Gas Science and Technology -Rev. IFP Energies nouvelles, Vol. 66 (2011), No. 3 400 implicit relump...

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Shape Selectivity in Hydrocarbon Conversion

et al. 2001

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Molecular sieves with three-dimensional framework structures find many applications in catalysis. [1, 2] A comprehensive and fundamental understanding of the product selectivity associated with these catalytic processes remains a formidable challenge of considerable practical significance. [3] Herein we focus on conversion reactions of alkanes. We demonstrate that molecular sieves favor the formation of reaction intermediates that have a shape commensurate with their pore shape. Bis(bidentate) catecholamide ligands (Scheme 2) were synthesized according to previously published procedures. [26] Libraries were obtained following a simple procedure: H 4 -L 2 (33.1 mg, 0.077 mmol), H 4 -L 3 (39.0 mg, 0.077 mmol), Et 4 NCl, (4.3 mg, 0.026 mmol), and [Ga(acac) 3 ] (acac acetylacetonate) (37.1 mg, 0.102 mmol) were suspended in methanol (20 mL). A 0.5 n NaOH solution (620 mL) in H 2 O was added slowly, and a clear solution was obtained. After the mixture had been stirred for 2 h, the solvent was reduced to 4 mL, and excess acetone was added to precipitate the product, which was collected by ultracentrifugation, washed with acetone and dried (quantitative yields). The same library was obtained by mixing solutions of [Ga 4 L 2 6 ' (Et 4 N)] 11À and [Ga 4 L 3 6 ' (Et 4 N)] 11À at pD 7.5 after heating for several hours at 60 8C.

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Kinetic modeling of paraffins hydrocracking based upon elementary steps and the single event concept

Cited by 29 publications

References 3 publications

Molecular Simulations of Zeolites: Adsorption, Diffusion, and Shape Selectivity

Molecular Simulations of Zeolites: Adsorption, Diffusion, and Shape Selectivity

Single Event Kinetic Modelling without Explicit Generation of Large Networks: Application to Hydrocracking of Long Paraffins

Shape Selectivity in Hydrocarbon Conversion

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