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.

Developing Versatile Contactors for Direct Air Capture of CO2 through Amine Grafting onto Alumina Pellets and Alumina Wash-Coated Monoliths.

The optimization of the air-solid contactor is critical to improve the efficiency of the direct air capture (DAC) process. To enable comparison of contactors and therefore a step toward optimization, two contactors are prepared in the form of pellets and wash-coated honeycomb monoliths. The desired amine functionalities are successfully incorporated onto these industrially relevant pellets by means of a procedure developed for powders, providing materials with a CO2 uptake not influenced by the morphology and the structure of the materials according to the sorption measurements. Furthermore, the amine functionalities are incorporated onto alumina wash-coated monoliths that provide a similar CO2 uptake compared to the pellets. Using breakthrough measurements, dry CO2 uptakes of 0.44 and 0.4 mmol gsorbent-1 are measured for pellets and for a monolith, respectively. NMR and IR studies of CO2 uptake show that the CO2 adsorbs mainly in the form of ammonium carbamate. Both contactors are characterized by estimated Toth isotherm parameters and linear driving force (LDF) coefficients to enable an initial comparison and provide information for further studies of the two contactors. LDF coefficients of 1.5 × 10-4 and of 1.2 × 10-3 s-1 are estimated for the pellets and for a monolith, respectively. In comparison to the pellets, the monolith therefore exhibits particularly promising results in terms of adsorption kinetics due to its hierarchical pore structure. This is reflected in the productivity of the adsorption step of 6.48 mol m-3 h-1 for the pellets compared to 7.56 mol m-3 h-1 for the monolith at a pressure drop approximately 1 order of magnitude lower, making the monoliths prime candidates to enhance the efficiency of DAC processes.

Direct Measurement of Ion Redistribution and Resulting Modification of Chemical Equilibria in Polymer Thin Film Light-Emitting Electrochemical Cells.

The redistribution of ions in light-emitting electrochemical cells (LECs) plays a key role in their functionality. The direct quantitative mapping of ion density distributions in operating realistic sandwich-type devices, however, has not been experimentally achieved. Here we operate high-performing [Super Yellow/trimethylolpropane ethoxylate/lithium trifluoromethanesulfonate (Li+CF3SO3-)] LEC devices inside a time-of-flight secondary ion mass spectrometer and cool the devices after different operation times to liquid nitrogen temperatures before depth profiling is performed. The results reveal the dependence of the elemental and molecular distributions across the device layer on operation conditions. We find that the ion displacements lead to a substantial shift of the local chemical equilibria governing the free ion concentration.