Catalytic Oxidation of Methane by Nitrous Oxide on H[Al]ZSM-5 Zeolite, Silicalite, and Amorphous SiO2 Modified by Iron, Silver, and Gadolinium Ions

Abstract

Methane oxidation by an excess of N2O on the catalytic sites formed in HZSM-5 zeolite, silicalite, and SiO2 after modification with iron, silver, and gadolinium cations in different combinations is studied. Introduction of iron and silver ions into H[Al]ZSM-5 zeolite is shown to result in the formation of the sites that are active in methane oxidation, while the systems obtained on the basis of crystalline silicalite or amorphous SiO2 demonstrate poor or no catalytic activity, respectively. Complete oxidation of methane with 100% conversion is observed on the Fe/HZSM-5 and Ag/HZSM-5 catalysts at temperatures higher than 350 and 450°C, respectively. A decrease in the reaction temperature and in the methane conversion is accompanied by coking of the catalysts and, in the case of Fe/HZSM-5, by the appearance of trace amounts of methanol and formic acid in the gas phase. The temperature dependence of the activity and selectivity for the Ag/HZSM-5 and (Ag + Gd)/HZSM-5 catalysts exhibits a pronounced hysteresis at 330–480°C, and the formation of coke proceeds much faster than in the case of iron-containing samples. Catalytic properties of (Fe + Ag)/HZSM-5 are similar to those of Fe/HZSM-5. The introduction of Gd does not influence significantly the activity and selectivity of the catalysts. ESR and TG–DTA were used to determine the state and distribution of Fe, Ag, and Gd in the samples and to examine the processes of coke formation.