Abstract
Kinetic modelling of the catalytic hydrogenation of CO 2-expanded α-methylstyrene is reported. Langmuir–Hinshelwood rate equations are evaluated for the correlation of kinetic rate data obtained in an earlier study in which the reaction was carried out at 323 K and 7–13 MPa using a Pd/C catalyst. The Peng-Robinson equation of state is used for the estimation of concentration terms that appear in the rate equations. Overall, the phase equilibria and kinetic modelling provide evidence that the rate-enhancing effect of CO 2 is influenced by two competing factors: solvent strength and reactant concentration. The presence of CO 2 modifies the solvent strength of the liquid phase, leading to more favourable adsorption equilibrium constants for the surface reaction. However, CO 2 also acts as a diluent, an effect that leads to reduced reaction rates. The optimum level of CO 2 for rate enhancement depends on the operating pressure.
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