Quantitative Kinetic Model of CO₂ Absorption in Aqueous Tertiary Amine Solvents

Aqueous tertiary amine solutions are increasingly used in industrial CO₂ capture operations because they are more energy-efficient than primary or secondary amines and demonstrate higher CO₂ absorption capacity. Yet, tertiary amine solutions have a significant drawback in that they tend to have lower CO₂ absorption rates. To identify tertiary amines that absorb CO₂ faster, it would be efficacious to have a quantitative and predictive model of the rate-controlling processes. Despite numerous attempts to date, this goal has been elusive. The present computational approach achieves this goal by focusing on the reaction of CO₂ with OH^- forming HCO₃^-. The performance of the resulting model is demonstrated for a consistent experimental data set of the absorption rates of CO₂ for 24 different aqueous tertiary amine solvents. The key to the new model's success is the manner in which the free energy barrier for the reaction of CO₂ with OH^- is evaluated from the differences among the solvation free energies of CO₂, OH^-, and HCO₃^-, while the pK_a of the amines controls the concentration of OH^-. These solvation energies are obtained from molecular dynamics simulations. The experimental value of the free energy of reaction of CO₂ with pure water is combined with information about measured rates of absorption of CO₂ in an aqueous amine solvent in order to calibrate the absorption rate model. This model achieves a relative accuracy better than 0.1 kJ mol^-1 for the free energies of activation for CO₂ absorption in aqueous amine solutions and 0.07 g L^-1 min^-1 for the absorption rate of CO₂. Such high accuracies are necessary to predict the correct experimental ranking of CO₂ absorption rates, thus providing a quantitative approach of practical interest.