Direct activation of CH4 to oxygenates and unsaturated hydrocarbons using N2O on Fe-modified zeolites

Abstract

Direct activation of CH4 to oxygenates and unsaturated light hydrocarbons was investigated using Fe-modified ZSM-5 and Ferrierite (FER) for a partial oxidation of CH4 with N2O oxidant. The amount of active α-oxygen sites and number of Bronsted acid sites on the Fe-modified zeolites were well correlated with CH4 conversion rate and product distributions. The amount of α-oxygen sites was largely changed according to preparation method such as wet impregnation or ion-exchange of iron precursor and types of zeolites. A large number of Bronsted acid sites and α-oxygen sites on the Fe-modified FER revealed a higher oxygenate formation such as methanol and dimethyl ether (DME) with COx, and a larger number of strong acid sites on Fe-modified ZSM-5 was also responsible for a higher selectivity to light hydrocarbons by a successive dehydration of oxygenates formed. The different catalytic performances were verified through proper measurements of the amount and type of acidic sites as well as the α-oxygen sites measured by N2O pulse chemisorption. The Fe-modified FER prepared by impregnation method possessed a larger amount of α-oxygen sites due to abundant Bronsted acid sites, which was responsible for a higher rate of CH4 conversion to oxygenates with the help of N2O decomposition on the α-oxygen sites originated from iron oxide nanoparticles.