Regularities of the formation of cool-flame oxidation products of rich propane-oxygen mixtures in a two-section reactor

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The effect of the ratio of the reagents on a stabilized cool flame of rich propane-oxygen mixtures is investigated. It was found that with an increase in the initial concentration of propane in the mixture, its consumption, as well as the concentration of propylene, has a maximum a ratio of C3H8 : O2 = 1 : 1. In this case, the selectivity of propylene formation reaches a maximum a ratio of C3H8 : O2 = 4 : 1. It is shown that an increase in the initial propane concentration in the mixture increases the yield of methane, but reduces the yield of propylene, ethylene, hydrogen, CO, CO2, methanol, formaldehyde and acetaldehyde. At a ratio of C3H8 : O2 = 6 : 1, ethane was also found in the reaction products. The possibility of ethanol formation in the reactions of ethoxyl and hydroxyethyl radicals with acetaldehyde has been analyzed using the CBS-QB3 quantum-chemical method.

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Sobre autores

N. Poghosyan

Nalbandyan Institute of Chemical Physics, National Academy of Sciences of Republic of Armenia

Email: strekova@bk.ru
Armênia, Yerevan

M. Poghosyan

Nalbandyan Institute of Chemical Physics, National Academy of Sciences of Republic of Armenia

Email: strekova@bk.ru
Armênia, Yerevan

A. Davtyan

Nalbandyan Institute of Chemical Physics, National Academy of Sciences of Republic of Armenia

Email: strekova@bk.ru
Armênia, Yerevan

S. Arsentev

Nalbandyan Institute of Chemical Physics, National Academy of Sciences of Republic of Armenia

Email: strekova@bk.ru
Armênia, Yerevan

L. Strekova

Semenov Federal Research Center for Chemical Physics of Russian Academy of Sciences

Autor responsável pela correspondência
Email: strekova@bk.ru
Rússia, Moscow

V. Arutyunov

Semenov Federal Research Center for Chemical Physics of Russian Academy of Sciences

Email: strekova@bk.ru
Rússia, Moscow

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2. Fig. 1. Effect of the propane/oxygen ratio in the initial mixture on the selectivity S for the formation of methane (1), ethylene (2) and hydrogen (3) during propane oxidation in the stabilized cold flame mode; T = 350 °C, P = 340 Torr, τ = 18.2 s.

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3. Fig. 2. Dependence of the partial pressure P of oxygen-containing products of propane oxidation at the reactor outlet in the stabilized cold flame mode on the propane/oxygen ratio in the initial mixture: 1 – CO, 2 – CH3OH, 3 – CH2O, 4 – CO2, 5 – CH3CHO; T = 350 °C, P = 340 Torr, τ = 18.2 s.

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4. Fig. 3. Dependence of propane consumption ∆[C3H8] (1), partial pressure of propylene (2) and selectivity of its formation (3) on the propane/oxygen ratio in the initial mixture; T = 350 °C, P = 340 Torr, τ = 18.2 s.

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5. Fig. 4. Dependences of the selectivity of formation of methanol (1), formaldehyde (2) and acetaldehyde (3) on the propane/oxygen ratio in the initial mixture; T = 350 °C, P = 340 Torr, τ = 18.2 s.

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6. Fig. 5. Structures of the ethoxyl radical (a), the transition state (b) of the reaction C2H5O● ↔ ●C2H4OH and the hydroxyethyl radical (c), calculated by the CBS-QB3 quantum chemical method.

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7. Fig. 6. Total energy diagram (∆E) for the system describing the interaction of ethoxyl and hydroxyethyl radicals with acetaldehyde. The reaction system was calculated by the CBS-QB3 method. The energies are shown relative to C2H5OH + CH3CO●, CR1–[C2H5O–CH3CHO], CP1–[C2H5OH–CH3CO]_1, CR2–[C2H4OH-CH3CHO], CP2–[C2H5OH–CH3CO]_2, CP3–[CH3CHOH–CH3CHO] – pre- and postreaction complex states corresponding to the reactants and products of reactions (3), (3a), and (3b).

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