Quaternary ammonium-functionalized silica sorbents for the solid-phase extraction of aromatic amines under normal phase conditions

Quaternary ammonium-functionalized silica materials were synthesized and applied for solid-phase extraction (SPE) of aromatic amines, which are classified as priority pollutants by US Environmental Protection Agency. Hexamethylenetetramine used for silica surface modification for the first time was employed as SPE sorbent under normal phase conditions. Hexaminium-functionalized silica demonstrated excellent extraction efficiencies for o-toluidine, 4-ethylaniline and quinoline (recoveries 101–107%), while for N,N-dimethylaniline and N-isopropylaniline recoveries were from low to moderate (14–46%). In addition, the suitability of 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica as SPE sorbent was tested under normal phase conditions. The recoveries achieved for the five aromatic amines ranged from 89 to 99%. The stability of the sorbent was evaluated during and after 150 extractions. Coefficients of variation between 4.5 and 10.2% proved a high stability of the synthesized sorbent. Elution was carried out using acetonitrile in the case of hexaminium-functionalized silica and water for 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent. After the extraction the analytes were separated and detected by liquid chromatography ultraviolet detection (LC-UV). The retention mechanism of the materials was primarily based on polar hydrogen bonding and π–π interactions. Comparison made with activated silica proved the quaternary ammonium-functionalized materials to offer different selectivity and better extraction efficiencies for aromatic amines. Finally, 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent was successfully tested for the extraction of wastewater and soil samples.

Gas Storage Scale-up at Room Temperature on High Density Carbon Materials

In relation to the current interest on gas storage demand for environmental applications (e.g., gas transportation, and carbon dioxide capture) and for energy purposes (e.g., methane and hydrogen), high pressure adsorption (physisorption) on highly porous sorbents has become an attractive option. Considering that for high pressure adsorption, the sorbent requires both, high porosity and high density, the present paper investigates gas storage enhancement on selected carbon adsorbents, both on a gravimetric and on a volumetric basis. Results on carbon dioxide, methane, and hydrogen adsorption at room temperature (i.e., supercritical and subcritical gases) are reported. From the obtained results, the importance of both parameters (porosity and density) of the adsorbents is confirmed. Hence, the densest of the different carbon materials used is selected to study a scale-up gas storage system, with a 2.5 l cylinder tank containing 2.64 kg of adsorbent. The scale-up results are in agreement with the laboratory scale ones and highlight the importance of the adsorbent density for volumetric storage performances, reaching, at 20 bar and at RT, 376 g l-1, 104 g l-1, and 2.4 g l-1 for CO2, CH4,and H2, respectively.

Sorbent design for CO2 capture under different flue gas conditions

CO2 capture by solid sorbents is a physisorption process in which the gas molecules are adsorbed in a different porosity range, depending on the temperature and pressure of the capture conditions. Accordingly, CO2 capture capacities can be enhanced if the sorbent has a proper porosity development and a suitable pore size distribution. Thus, the main objective of this work is to maximize the CO2 capture capacity at ambient temperature, elucidating which is the most suitable porosity that the adsorbent has to have as a function of the emission source conditions. In order to do so, different activated carbons have been selected and their CO2 capture capacities have been measured. The obtained results show that for low CO2 pressures (e.g., conditions similar to post-combustion processes) the sorbent should have the maximum possible volume of micropores smaller than 0.7 nm. However, the sorbent requires the maximum possible total micropore volume when the capture is performed at high pressures (e.g., conditions similar to oxy-combustion or pre-combustion processes). Finally, this study also analyzes the important influence that the sorbent density has on the CO2 capture capacity, since the adsorbent will be confined in a bed with a restricted volume.

Post-combustion CO2 adsorption on activated carbons with different textural properties

Fixed bed CO2 adsorption tests were carried out in model flue-gas streams onto two commercial activated carbons, namely Filtrasorb 400 and Nuchar RGC30, at 303 K, 323 K and 353 K. Thermodynamic adsorption results highlighted that the presence of a narrower micropore size distribution with a prevailing contribution of very small pore diameters, observed for Filtrasorb 400, is a key factor in determining a higher CO2 capture capacity, mostly at low temperature. These experimental evidences were also corroborated by the higher value of the isosteric heat derived for Filtrasorb 400, testifying stronger interactions with CO2 molecules with respect to Nuchar RGC30. Dynamic adsorption results on the investigated sorbents highlighted the important role played by both a greater contribution of mesopores and the presence of wider micropores for Nuchar RGC30 in establishing faster capture kinetics with respect to Filtrasorb 400, in particular at 303 K. Furthermore, the modeling analysis of 15% CO2 breakthrough curves allowed identifying intraparticle diffusion as the rate-determining step of the process.

Applications for CO2-Activated Carbon Monoliths: I. Gas Storage

Carbon monoliths with high densities are studied as adsorbents for the storage of H2, CH4, and CO2 at ambient temperature and high pressures. The starting monolith A3 (produced by ATMI Co.) was activated under a CO2 flow at 1073 K, applying different activation times up to 48 h. Micropore volumes and apparent surface areas were deduced from N2 and CO2 adsorption isotherms at 77 K and 273 K, respectively. CO2 and CH4 isotherms were measured up to 3 MPa and H2 up to 20 MPa. The BET surface area of the starting monolith (941 m2/g) could be significantly increased up to 1586 m2/g, and the developed porosity is almost exclusively comprised of micropores <1 nm. Total storage amounts take into account the compressed gas in the void space of the material, in addition to the adsorbed gas. Remarkably, high total storage amounts are reached for CO2 (482 g/L), CH4 (123 g/L), and H2 (18 g/L). These values are much higher than for other sorbents with similar surface areas, due to the high density of the starting monolith and of the activated ones, for which the density decreases only slightly (from 1.0 g/cm3 to 0.8 g /cm3 upon CO2 activation). The findings reveal the suitability of high density activated carbon monoliths for gas storage application. Thus, the amounts of stored gas can be increased by more than a 70 % in the case of H2 at 20 MPa, almost 5.5 times in the case of CH4 at 3 MPa, and more than 7.5 times in the case of CO2 at 3 MPa when adsorbents are used for gas storage under the investigated conditions rather than simple compression. Furthermore, the obtained results have been recently confirmed by a scale-up study in which 2.64 kg of high density monolith adsorbent was filled a tank cylinder of 2.5 L (Carbon, 76, 2014, 123).