new improvements in modeling kinetic schemes for hydrocarbons pyrolysis reactors

Dente, Mario; Pierucci, Sauro; Ranzi, E.; Bussani, G.

doi:10.1016/0009-2509(92)87104-x

Cited by 63 publications

(43 citation statements)

References 3 publications

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“…Assuming that the rate of abstraction 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 largely depends on the nature of the H-atom to be abstracted, it is clear how intrinsic bond dissociation energies directly affect the rate values, and, more importantly, the relative selectivities of the available abstraction sites. Figure 2 shows the H-abstraction rates of primary, secondary, and tertiary H-atoms by H, OH and CH 3 radicals on a per H-atom basis, according to the generic rate rules [19]. Considering Habstractions on n-butane by OH at 1000 K, the four available secondary H-atoms contribute to ~60% of the total rate constant, while ~40% undergoes a H-abstraction on the terminal methyl groups.…”

Section: Selectivities Of H-abstraction Reactionsmentioning

confidence: 99%

Relative Reactivity of Oxygenated Fuels: Alcohols, Aldehydes, Ketones, and Methyl Esters

et al. 2016

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This work aims at comparing and highlighting the main reaction pathways characterizing the combustion behavior of oxygenated fuels. Ethanol and heavier alcohols are already viable biofuels, despite some concern about their aldehydes and ketones emissions. Recently, the potential of 2-butanone (methyl ethyl ketone, MEK) as anti-knocking fuel was investigated at engine-relevant conditions. Moving from methyl butanoate (MB), long-chain fatty acid methyl esters are largely considered and used as biodiesels, mainly in Europe. Starting from a consistent assessment of C-H and C-C bond dissociation energies (BDEs) in n-butane, n-butanol, n-butanal, MEK, and MB, their impact on the selectivity of the different H-abstraction reactions and their relative reactivity are analyzed. Low-temperature oxidation mechanisms of 1-butanol and 2-butanone are also presented and discussed. Based on the upgraded Politecnico di Milano (POLIMI) kinetic mechanism, the relative reactivity of n-butane and the different oxygenated fuels is discussed here in depth. Stoichiometric fuel/air mixtures at 10 and 30 atm and 600-1450 K are analyzed. At low temperatures (T < 675 K), n-butanol and 2-butanone show the lowest reactivity, whereas the other fuels tend to converge to a very similar behavior. n-Butanal is the fastest to ignite in the whole T range, because it has the weakest C-H BDEs. No negative temperature coefficient (NTC) behavior is observed for n-butanal and n-butanol under the investigated conditions. A weak NTC is predicted for MB, similar to that of propane. MB and 2-butanone are the slowest to ignite between 750 and 850 K. A limited number of fuel-specific reactions characterizing each fuel and deserving more accurate investigation are highlighted, together with the lack of experimental targets below 850 K for MB and 2-butanone

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Section: Selectivities Of H-abstraction Reactionsmentioning

confidence: 99%

Relative Reactivity of Oxygenated Fuels: Alcohols, Aldehydes, Ketones, and Methyl Esters

et al. 2016

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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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“…MAMOX++, developed by Ranzi et al, produces a sequence of lumped mechanisms numerically derived from automatically generated mechanisms. This software represents an extension of the MAMA program in the SPYRO system that was originally developed to generate pyrolysis mechanisms of naphthas and heavy gasoils. The application of this software was extended to combustion processes by including the interactions of oxygen with alkyl radicals with the aim of identifying a few classes of primary propagation reactions responsible for the low‐temperature phenomena during hydrocarbon oxidation …”

Section: Network Generators: a Reviewmentioning

confidence: 99%

Discerning complex reaction networks using automated generators

Vernuccio

Broadbelt

2019

AIChE Journal

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new improvements in modeling kinetic schemes for hydrocarbons pyrolysis reactors

Cited by 63 publications

References 3 publications

Relative Reactivity of Oxygenated Fuels: Alcohols, Aldehydes, Ketones, and Methyl Esters

Relative Reactivity of Oxygenated Fuels: Alcohols, Aldehydes, Ketones, and Methyl Esters

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

Discerning complex reaction networks using automated generators

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