Development of a Predictive Model to Correlate the Chemical Structure of Amines with Their Oxidative Degradation Rate in a Post-Combustion Amine-Based CO₂ Capture Process Using Multiple Linear Regression and Machine Learning Regression Approaches

Abstract

In this study, the degradation behavior of 30 different amines was investigated, which were categorized into four distinct groups: alkanolamines, sterically hindered alkanolamines, multialkylamines, and cyclic amines. These experiments were conducted over a period of 14 days at a temperature of 60 °C, with a feed gas comprising 99.9% O 2 flowing at a rate of 200 mL/min. The primary objective was to establish a correlation between the chemical structures of these amines and their susceptibilities to degradation. To assess this, the concentration of the amines at various time points was measured to determine their degradation rates. Results showed that secondary amines exhibited degradation rates higher than those of primary and tertiary amines. Amines with cyclic structures demonstrated lower oxidative degradation rates. Longer alkyl chain lengths decreased degradation rates in all amine types because of their electronic and steric hindrance properties. A higher number of hydroxyl groups increased the degradation rate by destabilizing the free radical. An increase in hydroxyl groups in nonsterically hindered amines increased the degradation rate by decreasing free radical stability. In contrast, for sterically hindered amines, an increase in hydroxyl groups decreased the degradation rate because the steric hindrance effect is now more dominant than the electron-withdrawing effect. An increase in the number of amino groups led to higher degradation rates due to the presence of more reactive sites for free radical formation. Amines with tert-alkyl groups exhibited higher degradation rates than those with straight chains. Moreover, branched alkyl groups located between amino and hydroxyl groups significantly increased the degradation rates. Two degradation models, a semiempirical statistical model and a CatBoost machine learning regression model, were developed to predict amine degradation rates based on their chemical structure and relevant properties. To train these models, a data set of 27 different amines was used, while another set of 3 amines was reserved for testing the model's predictive performance. The average absolute deviations (AAD) achieved were, respectively, 22.2 and 0.3%.