ABSTRACT
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.
ABSTRACT
The reaction of [Pt15(CO)30](2-) with increasing amounts of SnCl2 affords [Pt8(CO)10(SnCl2)4](2-) (2), [Pt10(CO)14{Cl2Sn(OH)SnCl2}2](2-) (5), [Pt6(CO)6(SnCl2)2(SnCl3)4](4-) (3), [Pt9(CO)8(SnCl2)3(SnCl3)2(Cl2SnOCOSnCl2)](4-) (4) and [Pt5(CO)5{Cl2Sn(OR)SnCl2}3](3-) (R = H, Me, Et, and (i)Pr) (1-R). 1-R and 2 have been previously described, whereas 3-5 are herein reported for the first time. The species 1-3 are the main products of the reaction under different experimental conditions, whereas 4 and 5 are by-products of the synthesis of 3 and 2, respectively. From a structural point of view, the clusters 1-5 all show a perfect segregation of the two metals, which are composed of a low valent Pt core decorated on the surface by Sn(II) fragments such as SnCl2, [SnCl3](-), [Cl2Sn(OH)SnCl2](-) and [Cl2SnOCOSnCl2](2-). These fragments behave as two electron donor ligands via each Sn-atom (and also the C-atom in the case of [Cl2SnOCOSnCl2](2-)). The [Cl2SnOCOSnCl2](2-) ligand is rather unique and may be viewed as a bis-stannyl-carboxylate, a carbon dioxide µ3:k(3)-C,O,O'-CO2 or a carbonite ion [CO2](2-) stabilized by coordination to metal atoms. Compounds 1-5 have been fully characterised via IR spectroscopy, X-ray crystallography and DFT calculations.
