On Comparing Packed Beds and Monoliths for CO₂ Capture from Air Through Experiments, Theory, and Modeling

This study compares the performance of amine-functionalized γ-alumina sorbents in the form of 3 mm γ-alumina pellets and of a γ-alumina wash-coated monolith for CO₂ capture for direct air capture (DAC). Breakthrough experiments were conducted on the two contactors to analyze the adsorption kinetics and performance for different gas feeds. A constant pattern analysis revealed dominant mass transfer resistances in the gas film and in the pores, with axial dispersion also observed, particularly at higher concentrations. A 1D, physical model was used to fit the experiments and thus to estimate mass transfer and axial dispersion coefficients, which appear to be consistent with the hypotheses derived from constant pattern analysis. A dual kinetic model to describe mass transfer was found to better describe the tail behavior in the monolith, whereas a pseudo-first-order model was sufficient to describe breakthroughs on packed beds. A substantial two-order magnitude decrease in mass transfer coefficients was noted when reducing the feed concentration from 5.6% to 400 ppm CO₂, thus underscoring the significant mass transfer limitations observed in DAC. Comparison between the contactors revealed notably higher mass transfer coefficients in the monolith compared to the packed beds, which are attributed to shorter diffusion lengths and lower equilibrium capacity. While the faster mass transfer coefficients observed in the monolith experiments led to reduced specific energy consumption and increased adsorption productivity compared to the packed bed at 400 ppm, no significant improvement was observed for the same process at the higher concentration of 5.6% CO₂ in the feed. This finding highlights the need to tailor the contactor design to the specific gas separation requirements. This research contributes to the understanding and quantification of mass transfer kinetics at DAC concentrations in both packed bed and monolith contactors. It demonstrates the crucial role of the contactor in DAC systems and the importance of optimizing the adsorption step to enhance productivity and DAC performance.