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.
All Science Journal Classification (ASJC) codes
- Chemical Engineering(all)
- Fuel Technology
- Energy Engineering and Power Technology