Catalytic dehydrogenation of propane by carbon dioxide: a medium-temperature thermochemical process for carbon dioxide utilisation

Abstract

The dehydrogenation of C₃H₈ in the presence of CO₂ is an attractive catalytic route for C₃H₆ production. In studying the various possibilities to utilise CO₂ to convert hydrocarbons using the sustainable energy source of solar thermal energy, thermodynamic calculations were carried out for the dehydrogenation of C₃H₈ using CO₂for the process operating in the temperature range of 300–500 °C. Importantly, the results highlight the enhanced potential of C₃H₈ as compared to its lighter and heavier homologues (C₂H₆ and C₄H₁₀, respectively). To be utilised in this CO₂ utilisation reaction the Gibbs free energy (Δ_rG^θ_m) of each reaction in the modelled, complete reacting system of the dehydrogenation of C₃H₈ in the presence of CO₂ also indicate that further cracking of C₃H₆ will affect the ultimate yield and selectivity of the final products. In a parallel experimental study, catalytic tests of the dehydrogenation of C₃H₈ in the presence of CO₂ over 5 wt%-Cr₂O₃/ZrO₂ catalysts operating at 500 °C, atmospheric pressure, and for various C₃H₈ partial pressures and various overall GHSV (Gas Hourly Space Velocity) values. The results showed that an increase in the C₃H₈ partial pressure produced an inhibition of C₃H₈ conversion but, importantly, a promising enhancement of C₃H₆ selectivity. This phenomenon can be attributed to competitive adsorption on the catalyst between the generated C₃H₆ and inactivated C₃H₈, which inhibits any further cracking effect on C₃H₆ to produce by-products. As a comparison, the increase of the overall GHSV can also decrease the C₃H₈ conversion to a similar extent, but the further cracking of C₃H₆ cannot be limited.