CO₂ Capture and Release in Amine Solutions: To What Extent Can Molecular Simulations Help Understand the Trends?

Absorption in amine solutions is a well-established advanced technology for CO₂ capture. However, the fundamental aspects of the chemical reactions occurring in solution still appear to be unclear. Our previous investigation of aqueous monoethanolamine (MEA) and 2-amino-2-methyl-1,3-propanediol (AMPD), based on ab initio molecular dynamics simulations aided with metadynamics, provided new insights into the reaction mechanisms leading to CO₂ capture and release with carbamate formation and dissociation. In particular, the role of water-strongly underestimated in previous computational studies-was established as essential in determining the development of all relevant reactions. In this article, we apply the same simulation protocol to other relevant primary amines, namely, a sterically hindered amine (2-amino-2-methyl-1-propanol (AMP)) and an aromatic amine (benzylamine (BZA)). We also discuss the case of CO₂ capture with the formation of bicarbonate. New information is thus obtained that extends our understanding. However, quantitative predictions obtained using molecular simulations suffer from several methodological problems, and comparison among different chemical species is especially demanding. We clarify these problems further with a discussion of previous attempts to explain the different behaviors of AMP and MEA using other types of models and computations.