Catalytic partial oxidation of n-octane and iso-octane: Experimental and modeling results

The Catalytic Partial Oxidation (CPO) of two octane isomers, 2,2,4-trimethyl pentane (iso-octane) and n-octane, chosen as representative of gasoline is investigated by means of adiabatic tests and mathematical modeling. CPO experiments were carried out in a lab scale auto-thermal reformer with honeycomb monolith catalysts (2% Rh/α-Al2O3), equipped with probes for spatially resolved measurements of temperature and concentration. Tests were performed with about 50% N2dilution to prevent risks of deactivation due to catalyst over temperature. The CPO of the two isomers follows similar reaction pathways, which mainly consist of the exothermic combustion reaction and the endothermic steam reforming. This results in a close similarity of the concentration profiles of the main species and of the temperature profiles obtained with the two isomers. On the other hand, gas phase reactions proceed to a different extent and bring about a different distribution of thermal cracking products, iso-octane being more reactive and selective to iso-butylene and propene, while n-octane being selective to ethylene. Coke formation was observed upon adiabatic tests which was responsible for partial deactivation of the reforming zone of the catalyst. Post mortem TPO tests show that n-octane exhibits a higher tendency to coke deposition than iso-octane in the adopted CPO conditions. Thermodynamic and modeling calculations show that the risk of coking can be reduced by using exhaust gas recycling instead of N2to dilute the reactants.