CO2 methanation and reverse water gas shift reaction. Kinetic study based on in situ spatially-resolved measurements

The reaction kinetics for the CO2 methanation and reverse water gas shift reaction over an ordered-mesoporous Ni/Al2O3 catalyst were determined. For the parameter estimation and model discrimination, the kinetic data were obtained by means of spatially-resolved measurement in a catalytic plate reactor. In detail, ~21,000 high-resolution gas composition data were gathered along the reactor axis using a movable sampling capillary connected to a mass spectrometer. Additionally, the catalyst surface temperature was determined via infrared thermography. The influence of reaction temperature (320–420 °C), total pressure (1.2–7.3 barabs), and GHSV, as well as possible inhibition of products such as CH4 and H2O, were investigated. A one-dimensional model of the reactor was developed describing the conservation of mass in the bulk gas and catalyst phase. The Bayesian approach was used to estimate the kinetic parameters of 20 proposed Langmuir-Hinshelwood rate expressions for the CO2 methanation that were derived based on three different mechanisms (i.e., direct dissociation, hydrogen assisted dissociation, and hybrid mechanism). Two kinetic models reflected the measured data very well. The most probable models suggest that the rate determining step includes the reaction of an oxygenated complex (COH* or HCOO*) with an active site (*) or an adsorbed hydrogen (H*). Furthermore, water was assumed to be adsorbed as a hydroxyl species (OH*), while methane did not influence the reaction. Temperature- and time-resolved Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) measurements confirmed the presence of both adsorbed surface intermediates.