Polyethylenimine (PEI) has been grafted on a 2D hexagonal mesostructured porous silica of MCM-41 type (LUS silica) using 3-glycidoxypropyltrimethoxysilane (GTMS) as a grafting agent to develop sorbents for CO2 capture. The advantage of this tether is to create ethanolamine units upon reaction of the epoxy group with the amine functions of PEI. Two synthetic routes have been explored: (1) reaction of GTMS and PEI and then grafting on a calcined MCM-41 silica (M-1), and (2) grafting of GTMS on the silica and then reaction with PEI (M-2). In both cases, the grafted solids are well structured according to the XRD patterns. The amounts of glycidoxypropylsilane (GS) and PEI are 14 and 9 wt%, and 21 and 16 wt%, respectively, for samples M-1 and M-2. The CO2 adsorption capacity of both materials has been tested at 303 K and 101 kPa and compared to a bare LUS silica sample impregnated with 25 wt% PEI (M-3-25). Samples M-1 and M-2 containing ethanolamine groups show higher CO2 adsorption capacities, with loading of about 150 and 134 mgCO2 / gPEI (36 and 43 mgCO2 / g-sorbent), respectively, while the CO2 adsorption capacity was about 55 mgCO2 / gPEI (14 mgCO2 / g-sorbent) for the impregnated solid M-3-25.
In this study, we present the results of a preliminary investigation on the influence of operating variables (temperature, sweep gas flow rate, and total feed vapor pressure) on xylene vapor mixture separation using tubular nanocomposite MFI-alumina zeolite membrane prepared by the pore-plugging synthesis technique. Within the detection limit of our analytical system, neither m- nor o-xylene was detected in the permeate stream, the membranes displaying therefore “infinite” p-xylene selectivity. The mixture's p-xylene flux displayed a maximum value of ca. 3.5 µmol·m−2·s−1, corresponding to a mixture permeance of 11 nmol·m−2·s−1·Pa−1, at 473 K and for a feed composition 0.63 kPa p-xylene/0.27 kPa m-xylene/0.32 kPa o-xylene, being almost unchanged for sweep gas flow rates (N2) higher than 20 mL(STP)/min and increasing with the total xylene vapor pressure at 1 : 1 : 1–3 p/m/o-xylene composition. The experimental p-xylene fluxes can be well predicted by a Maxwell-Stefan model, as expected for a mass transfer process driven by competitive adsorption / surface diffusion. Unlike film-like MFI membranes, the membranes presented here preserved their selectivity to p-xylene for total xylene pressures as high as 150 kPa. This behavior is attributed to the intimate contact between the alumina confining pores and MFI nanoparticles, reducing long-term stresses and thus preventing distortion of the MFI framework during p-xylene adsorption. These results open up potential applications of nanocomposite MFI-alumina for selective p-xylene separations at high loadings, for instance in pervaporation, where the use of film-like MFI membranes is discouraged.