Kinetic and Equilibrium Reactions of a New Heterocyclic Aqueous 4-Aminomethyltetrahydropyran (4-AMTHP) Absorbent for Post Combustion Carbon Dioxide (CO2) Capture Processes

Abstract

<p>Aqueous amine absorbent processes remain at the forefront of existing technologies for the removal of CO₂ from industrial and large-scale power generation flue gas streams. It is essential that improvements in amine-based absorbent technologies are made in order to reduce both capital and operational costs. Intimate understanding of the fundamental chemical behavior of new amine absorbent systems is an intelligent pathway toward higher efficiency amine-based CO₂ capture processes. Herein, we investigate and report for the first time the complete temperature-dependent kinetic and equilibrium behavior of a new heterocyclic amine 4-aminomethyltetrahydropyran (4-AMTHP), with CO₂, in aqueous solutions. Stopped-flow spectrophotometry, ¹H NMR spectroscopy, and potentiometric titration measurements performed over the temperature range 25.0–45.0 °C and the corresponding rate constants for the reversible formation of the carbamic acid, together with equilibrium constants describing the stability of the carbamate, and the protonation of the amine are reported here. Thermodynamic analysis of the resulting constants using the Eyring, Arrhenius, and van’t Hoff relationships has revealed the activation energies, enthalpies, and entropies for the reactions, allowing a comparison to the industrial standard monoethanolamine (MEA). From the kinetic data, the performance of 4-AMTHP was found to be superior to MEA and in line with the established Brønsted relationship between the second-order rate constant and the protonation constant or basicity of the amine. The largely negative protonation enthalpy (−47 kJ/mol), among the key chemical drivers for CO₂ regeneration, is again superior to MEA (−41 kJ/mol). Together, a combination of kinetic and equilibrium properties of 4-AMTHP strongly position 4-AMTHP as a promising candidate for more intensive evaluations as a CO₂ capture absorbent.</p>