Spectroscopic Investigation into Oxidative Degradation of Silica-Supported Amine Sorbents for CO2 Capture

• Published in: ChemSusChem Vol. 5; no. 8; pp. 1435 - 1442
• Main Authors: Srikanth, Chakravartula S., Chuang, Steven S. C.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.08.2012; WILEY‐VCH Verlag; ChemPubSoc Europe
• Subjects: adsorption; amines; Chemistry; imides; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; oxidation; polymers; Science & Technology - Other Topics
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.201100662

Oxidative degradation characteristics of silica‐supported amine sorbents with varying amounts of tetraethylenepentamine (TEPA) and polyethylene glycol (PEG; P200 or P600 represents PEG with molecular weights of 200 or 600) have been studied by IR and NMR spectroscopy. Thermal treatment of the sorbents and liquid TEPA at 100 °C for 12 h changed their color from white to yellow. The CO2 capture capacity of the TEPA/SiO2 sorbents (i.e., SiO2‐supported TEPA with a TEPA/SiO2 ratio of 25:75) decreased by more than 60 %. IR and NMR spectroscopy studies showed that the yellow color of the degraded sorbents resulted from the formation of imide species. The imide species, consisting of NH associated with two CO functional groups, were produced from the oxidation of methylene groups in TEPA. Imide species on the degraded sorbent are not capable of binding CO2 due to its weak basicity. The addition of P200 and P600 to the supported amine sorbents improved both their CO2 capture capacities and oxidative degradation resistance. IR spectroscopy results also showed that TEPA was immobilized on the SiO2 surface through hydrogen bonding between amine groups and the silanol groups of SiO2. The OH groups of PEG interact with NH2/NH of TEPA through hydrogen bonding. Hydrogen bonds disperse TEPA on SiO2 and block O2 from accessing TEPA for oxidation. Oxidative degradation resistance and CO2 capture capacity of the supported amine sorbents can be optimized through adjusting the ratio of hydroxyl to amine groups in the TEPA/PEG mixture. Supporting the mix: Oxidative degradation of tetraethylenepentamine (TEPA) occurs through oxidation of the methylene groups in TEPA to CO, forming imides/amides or amines, or to ONO, forming nitrite species (see picture). The presence of polyethylene glycol (PEG) slowed down the oxidative degradation of TEPA by hydrogen bonding.