Pyrolysis of n-octane at very low concentration and low temperature
Identifieur interne : 000058 ( Main/Exploration ); précédent : 000057; suivant : 000059Pyrolysis of n-octane at very low concentration and low temperature
Auteurs : N. Razafinarivo ; R. Bounaceur [France] ; V. Burklé-Vitzthum ; F. Lannuzel [France] ; R. Michels [France] ; G. Scacchi [France] ; P. M. Marquaire [France]Source :
- Journal of Analytical and Applied Pyrolysis [ 0165-2370 ] ; 2015-11.
Abstract
tHydrocarbon pyrolysis concerns many different fields (petroleum geochemistry, refinery, fuel thermalstability, pyrocarbon deposition, etc.). It is therefore studied in a wide variety of temperature–pressureexperimental conditions, which strongly affect the chemistry of hydrocarbons cracking.An experimental study of the pyrolysis of n-octane has been performed at very low reactant concen-tration (1 mbar diluted in inert gas − total pressure 1500 mbar − molar fraction 0.07%) in a closed reactor,at temperatures ranging between 350◦C and 450◦C, and reaction time from 1 h to 70 h. The major prod-ucts of the reaction are 1-alkenes (C2H4to C7H14), methane and ethane; other alkanes (C3H8to C6H14)are minor products. At 450◦C and 4 h, the conversion is close to 9% and we observe, in terms of molarfractions:C2H4> C3H6≈ CH4> C4H8> C5H10> C6H12≈ C2H6> C7H14These experimental results are very different from those of the thermal decomposition of n-alkanesat the same low temperature but at high pressure. In particular, the cracking stoichiometric equations(for example: C8H18= C6H14+ C2H4) are not observed since alkanes (except methane and ethane) are invery low quantities. This can be explained by the very low concentration of reactant which limits thebimolecular reactions. In our conditions, the radicals decompose several times by beta-scissions of CCbonds when it is possible (unimolecular reaction), rather than react by H-transfers (metathesis) with thereactant (bimolecular reaction) which produce alkanes. A detailed free radical mechanism (184 reactions,16 molecules and 18 radicals— mechanism available as Supplementary material) allows modeling theexperimental results.
Url:
DOI: 10.1016/j.jaap.2015.11.004
Affiliations:
- France
- Grand Est, Lorraine (région)
- Metz, Nancy
- Institut national polytechnique de Lorraine, Université de Lorraine
Links toward previous steps (curation, corpus...)
- to stream Hal, to step Corpus: 000952
- to stream Hal, to step Curation: 000952
- to stream Hal, to step Checkpoint: 000043
- to stream Main, to step Merge: 000058
- to stream Main, to step Curation: 000058
Le document en format XML
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Razafinarivo</name></author><author><name sortKey="Bounaceur, R" sort="Bounaceur, R" uniqKey="Bounaceur R" first="R." last="Bounaceur">R. 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Scacchi</name><affiliation wicri:level="1"><hal:affiliation type="laboratory" xml:id="struct-211875" status="VALID"><idno type="IdRef">153068876</idno><idno type="RNSR">201320573K</idno><idno type="IdUnivLorraine">[UL]RQC--</idno><orgName>Laboratoire Réactions et Génie des Procédés</orgName><orgName type="acronym">LRGP</orgName><date type="start">2013-01-01</date><desc><address><addrLine>Université de Lorraine - ENSIC, 1 rue de Grandville BP 20451, 54001 Nancy Cedex</addrLine><country key="FR"></country></address><ref type="url">http://lrgp.univ-lorraine.fr/</ref></desc><listRelation><relation active="#struct-413289" type="direct"></relation><relation name="UMR7274" active="#struct-441569" type="direct"></relation></listRelation><tutelles><tutelle active="#struct-413289" type="direct"><org type="institution" xml:id="struct-413289" status="VALID"><idno type="IdRef">157040569</idno><idno type="IdUnivLorraine">[UL]100--</idno><orgName>Université de Lorraine</orgName><orgName type="acronym">UL</orgName><date type="start">2012-01-01</date><desc><address><addrLine>34 cours Léopold - CS 25233 - 54052 Nancy cedex</addrLine><country key="FR"></country></address><ref type="url">http://www.univ-lorraine.fr/</ref></desc></org></tutelle><tutelle name="UMR7274" active="#struct-441569" type="direct"><org type="institution" xml:id="struct-441569" status="VALID"><idno type="ISNI">0000000122597504</idno><idno type="IdRef">02636817X</idno><orgName>Centre National de la Recherche Scientifique</orgName><orgName type="acronym">CNRS</orgName><date type="start">1939-10-19</date><desc><address><country key="FR"></country></address><ref type="url">http://www.cnrs.fr/</ref></desc></org></tutelle></tutelles></hal:affiliation><country>France</country><placeName><settlement type="city">Nancy</settlement><settlement type="city">Metz</settlement><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Lorraine (région)</region></placeName><orgName type="university">Université de Lorraine</orgName></affiliation></author><author><name sortKey="Marquaire, P M" sort="Marquaire, P M" uniqKey="Marquaire P" first="P. M." last="Marquaire">P. M. Marquaire</name><affiliation wicri:level="1"><hal:affiliation type="laboratory" xml:id="struct-211875" status="VALID"><idno type="IdRef">153068876</idno><idno type="RNSR">201320573K</idno><idno type="IdUnivLorraine">[UL]RQC--</idno><orgName>Laboratoire Réactions et Génie des Procédés</orgName><orgName type="acronym">LRGP</orgName><date type="start">2013-01-01</date><desc><address><addrLine>Université de Lorraine - ENSIC, 1 rue de Grandville BP 20451, 54001 Nancy Cedex</addrLine><country key="FR"></country></address><ref type="url">http://lrgp.univ-lorraine.fr/</ref></desc><listRelation><relation active="#struct-413289" type="direct"></relation><relation name="UMR7274" active="#struct-441569" type="direct"></relation></listRelation><tutelles><tutelle active="#struct-413289" type="direct"><org type="institution" xml:id="struct-413289" status="VALID"><idno type="IdRef">157040569</idno><idno type="IdUnivLorraine">[UL]100--</idno><orgName>Université de Lorraine</orgName><orgName type="acronym">UL</orgName><date type="start">2012-01-01</date><desc><address><addrLine>34 cours Léopold - CS 25233 - 54052 Nancy cedex</addrLine><country key="FR"></country></address><ref type="url">http://www.univ-lorraine.fr/</ref></desc></org></tutelle><tutelle name="UMR7274" active="#struct-441569" type="direct"><org type="institution" xml:id="struct-441569" status="VALID"><idno type="ISNI">0000000122597504</idno><idno type="IdRef">02636817X</idno><orgName>Centre National de la Recherche Scientifique</orgName><orgName type="acronym">CNRS</orgName><date type="start">1939-10-19</date><desc><address><country key="FR"></country></address><ref type="url">http://www.cnrs.fr/</ref></desc></org></tutelle></tutelles></hal:affiliation><country>France</country><placeName><settlement type="city">Nancy</settlement><settlement type="city">Metz</settlement><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Lorraine (région)</region></placeName><orgName type="university">Université de Lorraine</orgName></affiliation></author></analytic><idno type="DOI">10.1016/j.jaap.2015.11.004</idno><series><title level="j">Journal of Analytical and Applied Pyrolysis</title><idno type="ISSN">0165-2370</idno><imprint><date type="datePub">2015-11</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">tHydrocarbon pyrolysis concerns many different fields (petroleum geochemistry, refinery, fuel thermalstability, pyrocarbon deposition, etc.). It is therefore studied in a wide variety of temperature–pressureexperimental conditions, which strongly affect the chemistry of hydrocarbons cracking.An experimental study of the pyrolysis of n-octane has been performed at very low reactant concen-tration (1 mbar diluted in inert gas − total pressure 1500 mbar − molar fraction 0.07%) in a closed reactor,at temperatures ranging between 350◦C and 450◦C, and reaction time from 1 h to 70 h. The major prod-ucts of the reaction are 1-alkenes (C2H4to C7H14), methane and ethane; other alkanes (C3H8to C6H14)are minor products. At 450◦C and 4 h, the conversion is close to 9% and we observe, in terms of molarfractions:C2H4> C3H6≈ CH4> C4H8> C5H10> C6H12≈ C2H6> C7H14These experimental results are very different from those of the thermal decomposition of n-alkanesat the same low temperature but at high pressure. In particular, the cracking stoichiometric equations(for example: C8H18= C6H14+ C2H4) are not observed since alkanes (except methane and ethane) are invery low quantities. This can be explained by the very low concentration of reactant which limits thebimolecular reactions. In our conditions, the radicals decompose several times by beta-scissions of CCbonds when it is possible (unimolecular reaction), rather than react by H-transfers (metathesis) with thereactant (bimolecular reaction) which produce alkanes. A detailed free radical mechanism (184 reactions,16 molecules and 18 radicals— mechanism available as Supplementary material) allows modeling theexperimental results.</div></front></TEI><affiliations><list><country><li>France</li></country><region><li>Grand Est</li><li>Lorraine (région)</li></region><settlement><li>Metz</li><li>Nancy</li></settlement><orgName><li>Institut national polytechnique de Lorraine</li><li>Université de Lorraine</li></orgName></list><tree><noCountry><name sortKey="Burkle Vitzthum, V" sort="Burkle Vitzthum, V" uniqKey="Burkle Vitzthum V" first="V." last="Burklé-Vitzthum">V. Burklé-Vitzthum</name><name sortKey="Razafinarivo, N" sort="Razafinarivo, N" uniqKey="Razafinarivo N" first="N." last="Razafinarivo">N. Razafinarivo</name></noCountry><country name="France"><region name="Grand Est"><name sortKey="Bounaceur, R" sort="Bounaceur, R" uniqKey="Bounaceur R" first="R." last="Bounaceur">R. Bounaceur</name></region><name sortKey="Lannuzel, F" sort="Lannuzel, F" uniqKey="Lannuzel F" first="F." last="Lannuzel">F. Lannuzel</name><name sortKey="Marquaire, P M" sort="Marquaire, P M" uniqKey="Marquaire P" first="P. M." last="Marquaire">P. M. Marquaire</name><name sortKey="Michels, R" sort="Michels, R" uniqKey="Michels R" first="R." last="Michels">R. Michels</name><name sortKey="Scacchi, G" sort="Scacchi, G" uniqKey="Scacchi G" first="G." last="Scacchi">G. Scacchi</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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