Pyrolysis of alkylcyclohexanes in or near the supercritical phase. Product distribution and reaction pathways

Wei Chuan Lai, Chunshan Song

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

Cyclohexane and seven n-alkylcyclohexanes (alkyl side-chain CmH2m + 1, m = 1, 2, 3, 4, 6, 8, 10) were pyrolyzed in or near the supercritical phase in a batch reactor at 450°C under relatively high (≥ 2 MPa) and continuously increasing pressure for 6-480 min. The thermal stability of alkylcyclohexanes decreases with increasing side-chain length. The major reaction pathways of alkylcyclohexanes are strongly dependent on the side-chain length. For cyclohexane and methyl-cyclohexane, the dominant reaction is isomerization to form alkylcyclopentanes via ring contraction. The tendency to isomerization decreases with increasing side-chain length. For alkylcyclohexanes with m ≥ 3, the major reaction at early decomposition stages is β-scission, leading to C-C bond cleavage in the side-chain at or near the ring followed by H-abstraction. The decomposition resulted in three pairs of most abundant products: cyclohexane plus 1-CmH2m, methylenecyclohexane plus n-C(m - 1)H2(m - 1)+ 2, and cyclohexene plus n-CmH2m + 2. Under the conditions used, alkylcyclohexanes do not undergo ring-opening cracking to any significant extent. An empirical equation was developed to correlate the rate constant with the molecular structure of alkylcyclohexanes using a group contribution method.

Original languageEnglish (US)
Pages (from-to)1-27
Number of pages27
JournalFuel processing technology
Volume48
Issue number1
DOIs
StatePublished - Jan 1 1996

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Cyclohexane
Pyrolysis
Chain length
Isomerization
Decomposition
Batch reactors
Molecular structure
Rate constants
Thermodynamic stability

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology

Cite this

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title = "Pyrolysis of alkylcyclohexanes in or near the supercritical phase. Product distribution and reaction pathways",
abstract = "Cyclohexane and seven n-alkylcyclohexanes (alkyl side-chain CmH2m + 1, m = 1, 2, 3, 4, 6, 8, 10) were pyrolyzed in or near the supercritical phase in a batch reactor at 450°C under relatively high (≥ 2 MPa) and continuously increasing pressure for 6-480 min. The thermal stability of alkylcyclohexanes decreases with increasing side-chain length. The major reaction pathways of alkylcyclohexanes are strongly dependent on the side-chain length. For cyclohexane and methyl-cyclohexane, the dominant reaction is isomerization to form alkylcyclopentanes via ring contraction. The tendency to isomerization decreases with increasing side-chain length. For alkylcyclohexanes with m ≥ 3, the major reaction at early decomposition stages is β-scission, leading to C-C bond cleavage in the side-chain at or near the ring followed by H-abstraction. The decomposition resulted in three pairs of most abundant products: cyclohexane plus 1-CmH2m, methylenecyclohexane plus n-C(m - 1)H2(m - 1)+ 2, and cyclohexene plus n-CmH2m + 2. Under the conditions used, alkylcyclohexanes do not undergo ring-opening cracking to any significant extent. An empirical equation was developed to correlate the rate constant with the molecular structure of alkylcyclohexanes using a group contribution method.",
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Pyrolysis of alkylcyclohexanes in or near the supercritical phase. Product distribution and reaction pathways. / Lai, Wei Chuan; Song, Chunshan.

In: Fuel processing technology, Vol. 48, No. 1, 01.01.1996, p. 1-27.

Research output: Contribution to journalArticle

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N2 - Cyclohexane and seven n-alkylcyclohexanes (alkyl side-chain CmH2m + 1, m = 1, 2, 3, 4, 6, 8, 10) were pyrolyzed in or near the supercritical phase in a batch reactor at 450°C under relatively high (≥ 2 MPa) and continuously increasing pressure for 6-480 min. The thermal stability of alkylcyclohexanes decreases with increasing side-chain length. The major reaction pathways of alkylcyclohexanes are strongly dependent on the side-chain length. For cyclohexane and methyl-cyclohexane, the dominant reaction is isomerization to form alkylcyclopentanes via ring contraction. The tendency to isomerization decreases with increasing side-chain length. For alkylcyclohexanes with m ≥ 3, the major reaction at early decomposition stages is β-scission, leading to C-C bond cleavage in the side-chain at or near the ring followed by H-abstraction. The decomposition resulted in three pairs of most abundant products: cyclohexane plus 1-CmH2m, methylenecyclohexane plus n-C(m - 1)H2(m - 1)+ 2, and cyclohexene plus n-CmH2m + 2. Under the conditions used, alkylcyclohexanes do not undergo ring-opening cracking to any significant extent. An empirical equation was developed to correlate the rate constant with the molecular structure of alkylcyclohexanes using a group contribution method.

AB - Cyclohexane and seven n-alkylcyclohexanes (alkyl side-chain CmH2m + 1, m = 1, 2, 3, 4, 6, 8, 10) were pyrolyzed in or near the supercritical phase in a batch reactor at 450°C under relatively high (≥ 2 MPa) and continuously increasing pressure for 6-480 min. The thermal stability of alkylcyclohexanes decreases with increasing side-chain length. The major reaction pathways of alkylcyclohexanes are strongly dependent on the side-chain length. For cyclohexane and methyl-cyclohexane, the dominant reaction is isomerization to form alkylcyclopentanes via ring contraction. The tendency to isomerization decreases with increasing side-chain length. For alkylcyclohexanes with m ≥ 3, the major reaction at early decomposition stages is β-scission, leading to C-C bond cleavage in the side-chain at or near the ring followed by H-abstraction. The decomposition resulted in three pairs of most abundant products: cyclohexane plus 1-CmH2m, methylenecyclohexane plus n-C(m - 1)H2(m - 1)+ 2, and cyclohexene plus n-CmH2m + 2. Under the conditions used, alkylcyclohexanes do not undergo ring-opening cracking to any significant extent. An empirical equation was developed to correlate the rate constant with the molecular structure of alkylcyclohexanes using a group contribution method.

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