RESUMEN
The current investigation is focused on the development of composite membranes based on polymeric ionic liquids (PILs) containing imidazolium and pyridinium polycations with various counterions, including hexafluorophosphate, tetrafluoroborate, and bis(trifluoromethylsulfonyl)imide. A combination of spectroscopic methods was used to identify the synthesized PILs and characterize their interaction with carbon dioxide. The density and surface free energy of polymers were performed by wettability measurements, and the results are in good agreement with the permeability and selectivity obtained within the gas transport tests. It was shown that the membranes with a selective layer based on PILs exhibit relatively high permeability with CO2 and high ideal selectivity CO2/CH4 and CO2/N2. Additionally, it was found that the type of an anion significantly affects the performance of the obtained membranes, with the most pronounced effect from bis-triflimide-based polymers, showing the highest permeability coefficient. These results provide valuable insights into the design and optimization of PIL-based membranes for natural and flue gas treatment.
RESUMEN
Herein, we report for the first time a study dedicated to acidic gases' solubility in ionic liquids with sterically hindered bulky anion, namely bis(2-ethylhexyl) sulfosuccinate ([doc]), experimentally evaluated at low pressures. The effect of cation change (imidazolium, pyridinium, and pyrrolidinium) on the thermophysical properties and sorption capacities was also discussed. The densities and the activation energies of the tested ILs exhibited minor differences. Furthermore, the COSMO-RS model was used to predict the free volumes of ILs aiming to investigate its influence on gas solubilities. The conducted calculations have revealed an antibate correlation between the fractional free volume (FFV) and Henry's law constant. In particular, the lowest FFV in 1-methylimidazolium [doc] corresponded to the minimal sorption and vice versa. In addition, it was shown that the presence of protic cation results in a significant reduction in CO2 and H2S solubilities. In general, the solubility measurement results of the synthesized ILs have shown their superiority compared to fluorinated ILs based on the physical absorption mechanism.
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A mesoporous silica support was synthesized using the sol-gel method from trichlorosilane. There is a tendency for the specific surface area and the proportion of silica particles mesopores to increase during all stages of sol-gel synthesis. It has been shown that the insertion of hexane and toluene, as additional solvents, into the structure-forming polyethylene glycol, makes it possible to regulate the pore size and specific surface area of silica. Silica functionalization was carried out using SILP technology. The activities of the catalytic systems based on polymer and inorganic supports immobilized by imidazole-based ionic liquids during the trichlorosilane disproportionation reaction were compared. There is a tendency for the monosilane yield for catalytic systems based on an inorganic support to increase. We identified the most promising catalyst in terms of monosilane yield and proposed a bifunctional catalyst that exhibited activity in two parallel reactions: trichlorosilane disproportionation and silicon tetrachloride hydrogenation.
Asunto(s)
Líquidos Iónicos , Silanos , Dióxido de SilicioRESUMEN
The present study continues the development and enhancement of a highly efficient unique hybrid technique-membrane-assisted gas absorption in designing the separation unit, which provides the improvement in mass-transfer of a target component during the ammonia capture process from a process loop of the Haber-Bosch technological route. In order to minimize the absorbent volume to membrane area ratio, the special separation cell was designed based on a combination of two types of hollow fiber membranes, dense gas separation membrane and porous pervaporation membrane. The separation performance tests were implemented under two sets of conditions, sweeping the bore (permeate) side of a cell with helium and hydrogen-nitrogen mix. For both cases, the membrane-assisted gas absorption cell demonstrated high separation efficiency, and the ammonia concentration in the permeate was never lower than 81 mol%; meanwhile, under the hydrogen-nitrogen bore sweep conditions, the ammonia concentration in the permeate reached 97.5 mol% in a single-step process. Nevertheless, there is a product purity-recovery rate trade-off, which is a typical issue for separation processes.
RESUMEN
The contribution of surface roughness of nonporous polymeric membranes to their gas separation and mechanical properties was studied in terms of surface free energy. The membranes samples were prepared based on glassy polymers with different chain rigidity, namely polysulfone (PSU), cellulose triacetate (CTA), and poly(vinyl alcohol) (PVA). The results were obtained by atomic force and scanning electron microscopy (AFM and SEM) with individual gas permeation, wettability, and mechanical testing. The specific surface free energy (as well as its polar and dispersive components) for the polymers was calculated by the Owens-Wendt method. It was proven that the surface roughness of the polymer membranes affects both energy components; however, the degree of this influence depends on the chemical nature of the corresponding polymer. Moreover, it was assumed that the dispersive energy component is inversely correlated with any gases' total permeability. In contrast, the polar one is inversely correlated with the permeability by gases with the ability for site-specific interactions. The gas separation results confirmed this assumption. It was also shown that the mechanical properties of the polymer membranes are also influenced by the surface energy, namely, its dispersive component.
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Pervaporation has been applied for tetrahydrofuran (THF) dehydration with novel composite membranes advanced by a thin selective layer composed of chitosan (CS) modified by copolymerization with vinyl monomers, acrylonitrile (AN) and styrene, in order to improve the chemical and mechanical stability of CS-based membranes. Composite membranes were developed by depositing a thin selective layer composed of CS copolymers onto a commercially-available porous support based on aromatic polysulfonamide (UPM-20®). The topography and morphology of the obtained materials were studied by atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). Thermal properties and stability were determined by coupled evolved gas analysis (EGA-MS). Transport properties were estimated in pervaporation dehydration of THF. The effect of operating parameters for the pervaporation dehydration of THF such as feed compositions and temperatures (295, 308 and 323 K) was evaluated. It was shown that CS modification with different vinyl monomers led to a difference in physical and transport properties. The composite membrane with the thin selective layer based on CS-PAN copolymer demonstrated optimal transport properties and exhibited the highest water content in the permeate with a reasonably high permeation flux.
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CO2 separation was found to be facilitated by transport membranes based on novel chitosan (CS)-poly(styrene) (PS) and chitosan (CS)-poly(acrylonitrile) (PAN) copolymer matrices doped with methylimidazolium based ionic liquids: [bmim][BF4], [bmim][PF6], and [bmim][Tf2N] (IL). CS plays the role of biodegradable film former and selectivity promoter. Copolymers were prepared implementing the latest achievements in radical copolymerization with chosen monomers, which enabled the achievement of outstanding mechanical strength values for the CS-based membranes (75-104 MPa for CS-PAN and 69-75 MPa for CS-PS). Ionic liquid (IL) doping affected the surface and mechanical properties of the membranes as well as the gas separation properties. The highest CO2 permeability 400 Barrers belongs to CS-b-PS/[bmim][BF4]. The highest selectivity α (CO2/N2) = 15.5 was achieved for CS-b-PAN/[bmim][BF4]. The operational temperature of the membranes is under 220 °C.
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A novel method for rapid, quantitative determination of trace permanent gases and carbon dioxide in ultra-high purity ammonia by dual-channel two-dimensional GC-PDHID is presented. An improved matrix back-flush-to-vent approach combining back-flush column switching technique with auxiliary NaHSO4 ammonia trap is described. The NaHSO4 trap prevents traces of ammonia from entering the analytical column and is shown not to affect the impurity content of the sample. The approach allows shortening the analysis time and increasing the amount of measurements without extensive maintenance of the GC-system. The performance of the configuration has been evaluated utilizing ammonia- and helium-based calibration standards. The method has been applied for the analysis of 99.9999+% ammonia purified by high-pressure distillation at the production site.
