Microkinetic modelling and reaction pathway analysis of the steam reforming of ethanol over Ni/SiO2

Abstract Hydrogen production via the steam reforming of biomass-derived ethanol is a promising environmental alternative to the use of fossil fuels and a means of clean power generation. A microkinetic modelling study of ethanol steam reforming (ESR) on Nickel is presented for the first time and validated with minimal parameter fitting against experimental data collected over a Ni/SiO2 catalyst. The thermodynamically consistent model utilises Transition State Theory and the UBI-QEP method for the determination of kinetic parameters and is able to describe correctly experimental trends across a wide range of conditions. The kinetically controlling reaction steps are predicted to occur in the dehydrogenation pathway of ethanol, with the latter found to proceed primarily via the formation of 1-hydroxyethyl. C-C bond cleavage is predicted to take place at the ketene intermediate leading to the formation of CH2 and CO surface species. The latter intermediates proceed to react according to methane steam reforming and water-gas shift pathways that are enhanced by the presence of water derived OH species. The experimentally observed negative reaction order for water is explained by the model predictions via surface saturation effects of adsorbed water species. The model results highlight a possible distinction between ethanol decomposition pathways as predicted by DFT calculations on Ni close-packed surfaces and ethanol steam reforming pathways at the broad range of experimental conditions considered.