In this study, the dynamic behavior of CO2 desorption in an aqueous blend of 2‐amino‐2‐methyl‐1‐propanol (AMP) and piperazine (PZ) was investigated. Solvent desorption, an important method used to capture CO2 by absorption into amines, was carried out in a laboratory column with a film promoter and monitored online by infrared spectroscopy. A PLS model was used to quantify the free amines, carbonated species, and total absorbed CO2 in all its chemical forms present in the liquid phase. The desorption was performed at atmospheric pressure and temperatures of 323, 333, and 343 K with blend solutions of 30/0, 25/5, 20/10, and 0/15 wt.% AMP/PZ. The liquid mass transfer coefficient (kL) decreased with higher CO2 loadings and was not significantly affected by temperature. AMP enhanced the liquid mass transfer coefficient of the PZ solvents, and the highest kL occurred at the higher PZ blend concentrations. © 2021 Society of Chemical Industry and John Wiley & Sons, Ltd.