Pathways, kinetics, and mechanisms for 2-dodecyl-9,10-dihydrophenanthrene pyrolysis
- Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemical Engineering
The authors pyrolyzed 2-dodecyl-9,10-dihydrophenanthrene (DDPh) in batch microreactors. The reaction conditions included neat pyrolyses between 375--450C for times of 15--240 min and also pyrolyses in benzene at 400 C and 90 min but at different initial DDPh concentrations ranging from 0.0095 to 0.238 mol/L. The disappearance of DDPh followed first-order kinetics, and the global first-order rate constant had Arrhenius parameters of log{sub 10} A (s{sup {minus}1}) = 13.6 {+-} 2.8 and E (kcal/mol) = 54.5 {+-} 9.1, where the uncertainties are the 95% confidence intervals. The decomposition of DDPh can be described by a reaction network that possesses four parallel primary pathways. The major primary path, which involves dehydrogenation, leads to 2-dodecylphenanthrene. The other three primary paths involve C{single_bond}C bond cleavage, and they lead to 2-methyl-9,10-dihydrophenanthrene plus undecene, to 2-vinyl-9,10-dihydrophenanthrene plus decane, and to numerous minor products. Important secondary and tertiary reactions include the rapid reduction of 2-vinyl-9,10-dihydrophenanthrene to 2-ethyl-9,10-dihydrophenanthrene and the facile dehydrogenation of 2-methyl- and 2-ethyl-9,10-dihydrophenanthrene to form 2-methyl- and 2-ethylphenanthrene, respectively. The identities and relative abundances of the major products are consistent with a free-radical chain reaction mechanism for DDPh pyrolysis. Application is to the processing of hydrocarbon resources such as coals and heavy crude oils.
- OSTI ID:
- 253750
- Journal Information:
- Industrial and Engineering Chemistry Research, Journal Name: Industrial and Engineering Chemistry Research Journal Issue: 5 Vol. 35; ISSN IECRED; ISSN 0888-5885
- Country of Publication:
- United States
- Language:
- English
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