Kinetic conjugation effects in oxidation of C1-C2 hydrocarbons: Experiment and modeling Научная публикация
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XXIII International Conference on Chemical Reactors 04-11 нояб. 2018 , Ghent |
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| Журнал |
Chemical Engineering Journal
ISSN: 1385-8947 |
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| Вых. Данные | Год: 2019, Том: 370, Страницы: 1210-1217 Страниц : 8 DOI: 10.1016/j.cej.2019.04.006 | ||
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| Организации |
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Реферат:
Oxidation of individual C1-C2 alkanes and their mixture (CH4:C2H6 = 8:1) was studied in an empty flow reactor and in the presence of two model catalysts used for oxidative coupling of methane (OCM) and oxidative transformations of C2+ alkanes, namely NaWMn/SiO2 and Ca-La/Al2O3. Ethane is much more reactive in homogeneous oxidation due to a high rate of free radical chain branching. Methane inhibits both homogeneous and catalytic oxidation of ethane, while ethane accelerates the conversion of methane. Methane reactivity is higher over the Ca-La/Al2O3 catalyst. In the presence of NaWMn/SiO2 ethane reacts faster, and the ‘conversion vs. contact time’ kinetic curves preserve an S-shape character typical for homogeneous branching chain processes. The observed features were rationalized using the numerical simulations in the framework of heterogeneous-homogeneous kinetic scheme that accounted both free-radical gas phase processes and reactions of molecular and radical species with catalytic active sites. It was shown that typical OCM catalysts play a dual role: they activate hydrocarbons by capturing H-atoms from C–H bonds and also efficiently terminate chain reactions by trapping free radicals. Consequently, over the catalyst that is more active in methane oxidation (Ca-La/Al2O3) ethane reacts slower due to the elimination of free radical chain branching and development. During the oxidation of ethane, methane – as an efficient radical scavenger – improves the selectivity to ethylene due to the inhibition of its secondary transformations (mainly to CO via HCOradical dot radicals).
Библиографическая ссылка:
Lomonosov V.
, Gordienko Y.
, Ponomareva E.
, Sinev M.
Kinetic conjugation effects in oxidation of C1-C2 hydrocarbons: Experiment and modeling
Chemical Engineering Journal. 2019. V.370. P.1210-1217. DOI: 10.1016/j.cej.2019.04.006 WOS Scopus OpenAlex
Kinetic conjugation effects in oxidation of C1-C2 hydrocarbons: Experiment and modeling
Chemical Engineering Journal. 2019. V.370. P.1210-1217. DOI: 10.1016/j.cej.2019.04.006 WOS Scopus OpenAlex
Даты:
| Опубликована online: | 2 апр. 2019 г. |
Идентификаторы БД:
| Web of science: | WOS:000467387200103 |
| Scopus: | 2-s2.0-85063738206 |
| OpenAlex: | W2931732920 |