The
concept of eutectic solvents as a platform technology for a
variety of applications including gas separation has become a popular
approach. To date, the number of known deep eutectic solvents (DESs)
is limited mainly to halide salts easily interacting with a hydrogen-bond
donor (HBD) and resulting in the formation of a liquid phase. Actually,
the DESs properties may be tuned by selecting the appropriate HBD,
while the structure of the anion is not a decisive factor. However,
the presence of other anions may be favorable for certain applications;
therefore, expanding the range of deep eutectic solvents seems a relevant
issue of chemistry and material science. In this study, we report
the high absorption properties of the DES based on 1-butyl-3-methyl
imidazolium methanesulfonate–urea toward ammonia. The structure
features investigations have revealed the major contribution of C(2)-H
to hydrogen bonding. To assess the possibility of selective separation,
the solubility of ammonia and two acidic gases (H2S and
CO2) in the absorbent has been measured. A superior gas
sorption capacity was observed for ammonia, for which the Henry’s
law constant was equal to 1.52 bar. The obtained results exceeded
the solubility data reported in the literature for various ILs containing
hydrogen-donating groups. The DESs demonstrated lower yet acceptable
solubility toward hydrogen sulfide, whereas the solubility of CO2 was relatively poor. The thermostimulated desorption has
demonstrated that the ability of gases to bind with DES molecules
can be ranked as follows: NH3 > H2S >
CO2. The physical sorption mechanism of ammonia, hydrogen
sulfide,
and carbon dioxide in the DES was proven by FTIR and thermal desorption
analysis. The absorption was totally reversible, and the solubility
of gases remains almost unchanged after three cycles.
Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N2, NH3, H2S, and CO2 gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF6] and [emim][Tf2N]. The modification of SILMs by nanosize silica particles leads to an increase of NH3 separation relatively to CO2 or H2S.
Herein, we studied the absorption of H 2 S and CO 2 by alkanolamine−protic ionic liquids binary mixtures based on 2-hydroxyethylammonium (MEA) or triethanolammonium cations and residues of 2hydroxy-5-sulfobenzoic acid or pyridine-3-carboxylic acid at various temperatures and partial gases pressures. It was found that absorbents based on the 2-hydroxyethylammonium cation, performed high absorption properties toward the H 2 S. The solubility of hydrogen sulfide, characterized by the Henry's Law constant, in MEA-based binary mixtures had the values comparable to the commercially available ionic liquids. The results of thermal desorption analysis demonstrated that the capture of acid gases in MEAbased absorbents occurred at two stages: through the dissolution in MEA component and in protic ionic liquid.
Nowadays, the imidazolium-based ionic liquids containing acetate counter-ions are attracting much attention as both highly selective absorbents of the acidic gases and CO2 carriers in the supported ionic liquid membranes. In this regard, the investigation of the gas transport properties of such membranes may be appropriate for better understanding of various factors affecting the separation performance and the selection of the optimal operating conditions. In this work, we have tested CH4, CO2 and H2S permeability across the supported ionic liquid membranes impregnated by 1-butyl-3-methylimidazolium acetate (bmim[OAc]) with the following determination of the ideal selectivity in order to compare the facilitated transport membrane performance with the supported ionic liquid membrane (SILM) that provides solution-diffusion mechanism, namely, containing 1-butyl-3-methylimidazolium tetrafluoroborate (bmim[BF4]). Both SILMs have showed modest individual gases permeability and ideal selectivity of CO2/CH4 and H2S/CH4 separation that achieves values up to 15 and 32, respectively. The effect of the feed gas mixture composition on the permeability of acidic gases and permeselectivity of the gas pair was investigated. It turned out that the permeation behavior for the bmim[OAc]-based SILM toward the binary CO2/CH4, H2S/CH4 and ternary CO2/H2S/CH4 mixtures was featured with high acidic gases selectivity due to the relatively low methane penetration through the liquid phase saturated by acidic gases.
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