Asphaltene Reaction Pathways. 4. Pyrolysis of Tridecylcyclohexane and 2-Ethyltetralin

Phillip E. Savage, Michael T. Klein, Phillip E. Savage

Research output: Contribution to journalArticle

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Abstract

The thermal reactions of the alkylnaphthenic and alkylhydroaromatic moieties likely present in petroleum asphaltenes were investigated Via pyrolysis of the model compounds tridecylcyclohexane (TDC) and 2-ethyltetralin (2ET), respectively. TDC pyrolyzed to the major product pairs cyclohexane plus 1-tridecene and methylenecyclohexane plus n-dodecane, both in initial selectivities of about 0.08. Cyclohexene, methylcyclohexane, and n-tridecane also formed but in lower selectivities of about 0.0388, 0.035, and 0.030, respectively. Arrhenius parameters of [log A (s-1), E* (kcal/mol)] = [14.9, 59.4] were determined over the temperature range 400-450 °C. 2ET pyrolyzed to 2-ethylnaphthalene, 2-ethyldialins, naphthalene, dialin, and tetralin as major products in yields of 1.73%, 1.19%, 1.13%, 1.09%, and 0.17%, respectively, at low (≈5%) conversions and 3.79%, 0, 30.2%, 2.19%, and 6.49%, respectively, at high (≈65%) conversions. The temporal variation of these products permitted deduction of the reaction network. It includes pathways for primary reaction of 2ET to dialin and the 2-ethyldialins and secondary reactions accounting for the formation of the other major products. The Arrhenius parameters for the disappearance of 2ET were [log A (s-l),E* (kcal/mol)] = [12.7, 53.5]. The pyrolyses of both compounds were consistent with free-radical reaction mechanisms. The implications of the results of this model compound study to the reactions of the analogous moieties in asphaltenes are suggested.

Original languageEnglish (US)
Pages (from-to)1348-1356
Number of pages9
JournalIndustrial and Engineering Chemistry Research
Volume27
Issue number8
DOIs
StatePublished - Aug 1 1988

Fingerprint

Asphaltenes
Pyrolysis
Free radical reactions
Petroleum
Naphthalene
Cyclohexane
Crude oil
Temperature
asphaltene
Hot Temperature
1-tridecene
n-dodecane
tetralin
cyclohexene
methylcyclohexane
tridecane
naphthalene

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Industrial and Manufacturing Engineering

Cite this

@article{158a5de66c9341e0b6d032423ea6811b,
title = "Asphaltene Reaction Pathways. 4. Pyrolysis of Tridecylcyclohexane and 2-Ethyltetralin",
abstract = "The thermal reactions of the alkylnaphthenic and alkylhydroaromatic moieties likely present in petroleum asphaltenes were investigated Via pyrolysis of the model compounds tridecylcyclohexane (TDC) and 2-ethyltetralin (2ET), respectively. TDC pyrolyzed to the major product pairs cyclohexane plus 1-tridecene and methylenecyclohexane plus n-dodecane, both in initial selectivities of about 0.08. Cyclohexene, methylcyclohexane, and n-tridecane also formed but in lower selectivities of about 0.0388, 0.035, and 0.030, respectively. Arrhenius parameters of [log A (s-1), E* (kcal/mol)] = [14.9, 59.4] were determined over the temperature range 400-450 °C. 2ET pyrolyzed to 2-ethylnaphthalene, 2-ethyldialins, naphthalene, dialin, and tetralin as major products in yields of 1.73{\%}, 1.19{\%}, 1.13{\%}, 1.09{\%}, and 0.17{\%}, respectively, at low (≈5{\%}) conversions and 3.79{\%}, 0, 30.2{\%}, 2.19{\%}, and 6.49{\%}, respectively, at high (≈65{\%}) conversions. The temporal variation of these products permitted deduction of the reaction network. It includes pathways for primary reaction of 2ET to dialin and the 2-ethyldialins and secondary reactions accounting for the formation of the other major products. The Arrhenius parameters for the disappearance of 2ET were [log A (s-l),E* (kcal/mol)] = [12.7, 53.5]. The pyrolyses of both compounds were consistent with free-radical reaction mechanisms. The implications of the results of this model compound study to the reactions of the analogous moieties in asphaltenes are suggested.",
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Asphaltene Reaction Pathways. 4. Pyrolysis of Tridecylcyclohexane and 2-Ethyltetralin. / Savage, Phillip E.; Klein, Michael T.; Savage, Phillip E.

In: Industrial and Engineering Chemistry Research, Vol. 27, No. 8, 01.08.1988, p. 1348-1356.

Research output: Contribution to journalArticle

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AB - The thermal reactions of the alkylnaphthenic and alkylhydroaromatic moieties likely present in petroleum asphaltenes were investigated Via pyrolysis of the model compounds tridecylcyclohexane (TDC) and 2-ethyltetralin (2ET), respectively. TDC pyrolyzed to the major product pairs cyclohexane plus 1-tridecene and methylenecyclohexane plus n-dodecane, both in initial selectivities of about 0.08. Cyclohexene, methylcyclohexane, and n-tridecane also formed but in lower selectivities of about 0.0388, 0.035, and 0.030, respectively. Arrhenius parameters of [log A (s-1), E* (kcal/mol)] = [14.9, 59.4] were determined over the temperature range 400-450 °C. 2ET pyrolyzed to 2-ethylnaphthalene, 2-ethyldialins, naphthalene, dialin, and tetralin as major products in yields of 1.73%, 1.19%, 1.13%, 1.09%, and 0.17%, respectively, at low (≈5%) conversions and 3.79%, 0, 30.2%, 2.19%, and 6.49%, respectively, at high (≈65%) conversions. The temporal variation of these products permitted deduction of the reaction network. It includes pathways for primary reaction of 2ET to dialin and the 2-ethyldialins and secondary reactions accounting for the formation of the other major products. The Arrhenius parameters for the disappearance of 2ET were [log A (s-l),E* (kcal/mol)] = [12.7, 53.5]. The pyrolyses of both compounds were consistent with free-radical reaction mechanisms. The implications of the results of this model compound study to the reactions of the analogous moieties in asphaltenes are suggested.

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