Self-sustained oscillations in oxidation of methane over palladium: Experimental study and mathematical modeling.

An experimental study of the catalytic oxidation of methane over Pd foil in a flow reactor revealed that regular temporal oscillations in the reaction rate can arise at atmospheric pressure under methane-rich conditions. CO, CO2, H2, and H2O were detected as products. The oscillations of partial pressures of products and reactants in the gas phase were accompanied by oscillations of the catalyst temperature. According to an operando x-ray diffraction and mass-spectrometry study, the oscillations originate due to spontaneous oxidation and reduction of palladium; the high active catalyst surface is represented by metallic palladium, and the transition to the low-active state is accompanied by the formation of the PdO phase. In addition, it was detected that carbon dissolves in near-surface layers of palladium to form the PdCx phase. To describe the oscillations in the oxidation of methane, a 17-step reaction mechanism and a corresponding kinetic model were developed. The mechanism considers direct dissociative adsorption of methane and oxygen, pyrolytic activation of methane, oxidation and reduction of palladium, and direct formation and desorption of CO, CO2, H2, and H2O. Numerical solutions from the mathematical model of the continuously stirred-tank reactor qualitatively reproduce experimentally observed oscillatory dynamics. We have also developed a model, which considers the reversible diffusion of adsorbed oxygen and carbon atoms into the Pd bulk that allows us to explain the long induction period preceding the appearance of the oscillations. Mathematical modeling shows that the concentrations of dissolved oxygen and carbon atoms also oscillate under reaction conditions.

Experimental Study and Mathematical Modeling of Self-Sustained Kinetic Oscillations in Catalytic Oxidation of Methane over Nickel.

The self-sustained kinetic oscillations in the oxidation of CH4 over Ni foil have been studied at atmospheric pressure using an X-ray diffraction technique and mass spectrometry. It has been shown that the regular oscillations appear under oxygen-deficient conditions; CO, CO2, H2, and H2O are detected as the products. According to in situ X-ray diffraction measurements, nickel periodically oxidizes to NiO initiating the reaction-rate oscillations. To describe the oscillations, we have proposed a five-stage mechanism of the partial oxidation of methane over Ni and a corresponding three-variable kinetic model. The mechanism considers catalytic methane decomposition, dissociative adsorption of oxygen, transformation of chemisorbed oxygen to surface nickel oxide, and reaction of adsorbed carbon and oxygen species to form CO. Analysis of the kinetic model indicates that the competition of two processes, i.e., the oxidation and the carbonization of the catalyst surface, is the driving force of the self-sustained oscillations in the oxidation of methane. We have compared this mechanism with the detailed 18-stage mechanism described previously by Lashina et al. (Kinetics and Catalysis 2012, 53, 374-383). It has been shown that both kinetic mechanisms coupled with a continuous stirred-tank reactor model describe well the oscillatory behavior in the oxidation of methane under non-isothermal conditions.