Capacities of sorbents prepared by impregnation of inorganic carriers with PEI using different methods
Authors: Staf Marek , Kyselová Veronika , Loos Adam 
Published: September 2024

The study presented here focused on the research of adsorbents for the separation of carbon dioxide from flue gas or other waste gases. Specifically, it focused on the possibility of eliminating the permanent problem with the insufficient resistance of inorganic adsorbents to unwanted – parasitic – adsorption of moisture from the processed gas. Based on the promising data published in recent papers regarding the wet impregnation of adsorbents with branched polyethyleneimine (PEI), four methods for the preparation of PEI-impregnated zeolite were tested. Penetration of the agent into the porous structure of the zeolite was achieved by: applying ultrasound, applying vacuum, combining vacuum and overpressure and boiling off the solvent without further operation.
The raw zeolite was characterized by X-ray fluorescence spectrometry and X-ray diffractometry and also subjected to textural analysis. The characterization of the impregnated products mainly included thermogravimetric analysis, textural analysis and organic elemental analysis. In addition to gravimetric screening, the adsorption capacities of raw zeolite and impregnated products were primarily determined using a pressure flow-through apparatus with a fixed bed adsorber. The experimental conditions were determined to be close to real industrial installations: temperature during adsorption 20 and 40 °C, pressure during adsorption 600 kPa and 15% volume fraction of CO2 in the gas. Desorption was carried out by a combination of thermal desorption at 80 °C and vacuum.
By reproducing the impregnation procedures from the literature, a PEI loading in the range of 4.1–23.7% was achieved, which is significantly lower than the literature sources state for the same preparation procedures. The measurement of textural properties verified that, depending on the value of PEI loading, there is a gradual reduction of the specific surface area, the total pore volume and the virtual disappearance of micropores and small mesopores. Specifically, at a PEI loading of 4%, the BET surface area decreased compared to the pristine zeolite from 29.4 to 2.9 m2 g–1 and at the same time the total pore volume decreased from 0.13 to 0.02 cm3 g–1, etc.
The measurement of capacities did not confirm almost any of the results published in the literature. Without exception, the adsorption capacity decreased with the amount of PEI introduced into the zeolite particles. E.g. if a gas with 80% relative humidity and a content of 15% CO2 was used at a pressure of 600 kPa and a temperature of 40 °C, the capacity (by mass) decreased due to impregnation from 2.4% (for raw zeolite) to 0.8% for the sample with PEI mass fraction of 19%. Tests using dry gas resulted in even more marked deterioration. Thus, one can only partially agree with the literature data in the sense that humidity slightly compensates the negative effect of PEI on capacity.
The effect, where the capacity increases with increasing temperature due to the replacement of physical CO2 adsorption by its chemisorption in the PEI layer, was also not confirmed. For example, for the above sample, humidity and pressure, the capacity was 0.9% at 20 °C.
The impregnation procedure based on boiling off the solvent turned out to be completely unusable and, despite repeated rigorous attempts to reproduce it, did not lead to a product with a measurable capacity. The results of the study can be summarized in the following sentence. The problem is not that the experiments did not lead to a positive result, but above all the fundamental discrepancy between the published data and the attempts to reproduce them.