The reaction mechanism of the partial oxidation of methane to synthesis gas: A transient kinetic study over rhodium and a comparison with platinum
- Eindhoven Univ. of Technology (Netherlands)
The partial oxidation of methane to synthesis gas over rhodium sponge has been investigated by admitting pulses of pure methane and pure oxygen as well as mixtures of methane and oxygen to rhodium sponge at temperatures from 873 to 1023 K. Moreover, pulses of oxygen followed by methane and vice versa as well as pulses of mixtures of methane and labeled oxygen were applied to study the role of chemisorbed oxygen and incorporated oxygen in the reaction mechanism. The decomposition of methane on reduced rhodium results in the formation of carbon and hydrogen adatoms. During the interaction of pure dioxygen with rhodium the catalyst is almost completely oxidized to Rh{sub 2}O{sub 3}. In addition to rhodium oxide, oxygen is also present in the form of chemisorbed oxygen species. During the simultaneous interaction of methane and dioxygen at a stoichiometric feed ratio and a temperature of 973 K only 0.4 wt% Rh{sub 2}O{sub 3} is present. The chemisorbed oxygen species are completely desorbed after 2 s. A Mars-Van Krevelen mechanism is postulated: methane reduces the rhodium oxide, which is reoxidized by dioxygen. Synthesis gas is produced as primary product. Hydrogen is formed via the associative desorption of two hydrogen adatoms from reduced rhodium and the reaction between carbon adatoms and oxygen present as rhodium oxide results in the formation of carbon monoxide. The consecutive oxidation of CO and H{sub 2} proceeds via both chemisorbed oxygen and oxygen present as rhodium oxide. Continuous flow experiments were performed to compare rhodium and platinum. When compared to platinum, rhodium shows a higher conversion to methane at a comparable temperature and also a higher selectivity to both CO and H{sub 2}, the difference for CO being most pronounced. 45 refs., 10 figs., 2 tabs.
- OSTI ID:
- 563499
- Journal Information:
- Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: 1 Vol. 167; ISSN 0021-9517; ISSN JCTLA5
- Country of Publication:
- United States
- Language:
- English
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