A general binary isotherm model for amines interacting with CO2 and H2O

Abstract

CO₂ capture by primary or secondary amines has been a topic of great research interests for a century because of its industrial importance. Interest has grown even more, because of the need to eliminate CO₂ emissions that lead to global warming. Experimental evidence shows that CO₂ sorption by primary or secondary amines is accompanied by co-absorption of H₂O. A quantitative analysis of such CO₂–H₂O co-absorption behavior is important for practical process design and theoretical understanding. Even though there is almost an experimental consensus that water enhances CO₂ uptake capacity, an analytical model to explain this phenomenon is not well established. Instead, some empirical models such as the Toth model are used to describe the isotherm without accounting for the presence of water. Recently, we have demonstrated that the isotherm equation of CO₂ sorption into strong-base anion exchange materials with quaternary ammonium can be derived from that of strong-base aqueous alkaline solutions by correcting for the drastic change in the water activity and by including an appropriate parameterization of the water activity terms. In this paper, we generalize this model from quaternary ammonium to primary, secondary and tertiary amines either in solutions or as functional groups in polymer resins. For primary, secondary and tertiary amines, the isotherm equation can be derived by extending that of a weak-base aqueous alkaline solution such as aqueous ammonia. The model has been validated using experimental data on CO₂ sorption for aqueous ammonia from the literature. This general model even includes quaternary ammonium as a special limit. Hence, this general model offers a platform that can treat the isotherms of solid amines, aqueous amines and aqueous alkaline solutions in a unified manner.