The use of metal nitrate-modified amorphous nano silica for synthesizing solid amine CO2 adsorbents with resistance to urea linkage formation

Abstract

The formation of urea linkages is a limitation to the application of solid amine CO2 adsorbents. Therefore, the development of solid amine adsorbents with resistance to urea linkage formation has attracted much interest over the last 5 years. In this study, we developed a facile method for synthesizing solid amine adsorbents with effective resistance to urea linkage formation. For the first time, metal nitrates were used to modify amorphous nano SiO2 to support polyethyleneimine (PEI). Three metal nitrates were investigated: aluminum, magnesium, and zinc nitrates. A series of adsorbents were prepared by controlling the mass ratios of metal nitrates and nano SiO2. After 50 cycles of adsorption–desorption tests, adsorbing at 75 °C under 15 % CO2 balanced with N2 and desorbing at 130 °C under pure CO2, Al-20%@SiO2-PEI, Al-15%@SiO2-PEI, Al-10%@SiO2-PEI, Zn-10%@SiO2-PEI, and Mg-10%@SiO2-PEI lost only 2.6 %, 4.0 %, 5.2 %, 15.9 %, and 28.8 % of their original CO2 adsorption capacities, respectively. However, SiO2-PEI, calcined SiO2-PEI, and Al-5%@SiO2-PEI lost 42.9 %, 48.6 %, and 49.6 %, respectively. By combining the infrared spectra of all the adsorbents through cyclic adsorption–desorption tests, inhibitory effects on urea linkage formation were proven for Al-20%@SiO2-PEI, Al-15%@SiO2-PEI, Zn-10%@SiO2-PEI, and Mg-10%@SiO2-PEI, and especially for Al-10%@SiO2-PEI. Through a relatively comprehensive analysis, we found that a desirable amount of metal nitrates could modify nano SiO2 samples and their corresponding adsorbents possessed a stronger H2O binding ability at 130 °C. The retained H2O could act as an inhibiting agent for the inhibition of urea linkage formation.