Absorption Of Ionic Liquids Research Articles

Anion Effects on Kinetics and Thermodynamics of CO2 Absorption in Ionic Liquids

A thermogravimetric technique based on a magnetic suspension balance operating in dynamic mode was used to study the thermodynamics (in terms of solubility and Henry's law constants) and kinetics (i.e., diffusion coefficients) of CO2 in the ionic liquids [bmim][PF6], [bmim][NTf2], and [bmim][FAP] at temperatures of 298.15, 308.15, and 323.15 K and pressures up to 20 bar. The experimental technique employed was shown to be a fast, accurate, and low-solvent-consuming method to evaluate the suitability of the ionic liquids (ILs) to be used as CO2 absorbents. Thermodynamic results confirmed that the solubility of CO2 in the ILs followed the order [bmim][FAP] > [bmim][NTf2] > [bmim][PF6], increasing with decreasing temperatures and increasing pressures. Kinetic data showed that the diffusion coefficients of CO2 in the ILs followed a different order, [bmim][NTf2] > [bmim][FAP] > [bmim][PF6], increasing with increasing temperatures and pressures. These results evidenced the different influence of the IL structure and operating conditions on the solubility and absorption rate of CO2, illustrating the importance of considering both thermodynamic and kinetic aspects to select adequate ILs for CO2 absorption. On the other hand, the empirical Wilke-Chang correlation was successfully applied to estimate the diffusion coefficients of the systems, with results indicating the suitability of this approach to foresee the kinetic performance of ILs to absorb CO2. The research methodology proposed herein might be helpful in the selection of efficient absorption solvents based on ILs for postcombustion CO2 capture.

Styrene and ethylbenzene absorption in ionic liquids: comparing DFT affinity calculations with experimental data

Styrene is a widely used bulk chemical produced by dehydrogenation of ethylbenzene (EB). Purification of styrene to contain < 100 ppm EB is not cost-effective by conventional separation methods. One separation method is extractive distillation with an ionic liquid (IL) as a binding agent for one of the components, thereby lowering the vapour pressure of this component. In this study, using quantum density functional theory (DFT), we have simulated 22 IL anion–cation pairs, styrene and EB affinities to them, and ion-pair dimer affinities of the ILs. These are compared with experimental liquid–liquid equilibrium studies of M.T.G. Jongmans, B. Schuur, and A.B. de Haan, Ind. Eng. Chem. Res. 50 (2011), pp. 10800–10810. It is shown that experimental selectivity and distribution coefficients of styrene and EB in the ILs are related to computed gas phase anion–cation stabilisation energies and ion-pair–ion-pair dimer affinities. The inverse of molar volume is found to strongly correlate with the selectivity. The computational results also qualitatively correlate with molar volume, and consequently, it is possible to use DFT calculations as a qualitative prediction tool in screening of ILs for this separation process. This tool does not account for effects caused by long alkyl chains, as the length does not seem to affect dimer stabilisation energy beyond ethyl group.

Experimental and modelling study of CO2 absorption in ionic liquids containing Zn (II) ions

This paper studies an ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide ([EMIM][TFSI]) containing Zn2+ ions as a novel functional group for CO2 absorption. Their physical properties including the density, decomposition temperature, phase transition temperature, heat capacity and viscosity have been characterised. The CO2 solubility measurements have been carried out under constant pressures of 0.1, 0.3, 0.5, 0.7 and 1.0 bar at 40 °C. The result shows an appealing solubility of 8.2 wt% CO2 at 1.0 bar. The real-time absorption kinetics was studied using a comprehensive diffusion model for a reacting system. Based on this model, the corresponding diffusion coefficients and the reaction rate constant have been obtained. The diffusion and reaction behavior of CO2 in the physical/chemical absorption has also been discussed.

Vapor Pressure of Water in Mixtures with Hydrophilic Ionic Liquids – A Contribution to the Design of Processes for Drying of Gases by Absorption in Ionic Liquids

AbstractThe low water vapor pressures of mixtures of water with the ionic liquids (ILs), [EMIM][EtSO4] and [BEIM][EtSO4], indicate that a process of gas dehydration by absorption in ILs might be an alternative to the classical absorption process with triethylene glycol (TEG). The activity coefficient for an infinite dilution of water in the IL (xIL → 1), which should be low for efficient dehydration, is only about 0.2 for [EMIM][EtSO4] compared to 0.6 for triethylene glycol. In contrast to TEG, losses by evaporation are excluded with ILs as solvents, because they have a negligible vapor pressure. The number of separation stages needed for the absorption in the IL and for the subsequent regeneration of the water‐loaded IL is small, about six and eight, respectively. IL regeneration can be achieved by distillation of water out of the IL (e.g., at 120 °C) and stripping with ambient air, which is not possible in the case of TEG (chemical attack by O2).

Examination of the Potential of Ionic Liquids for Gas Separations

:Ionic liquids have received increasing interest in recent years for “green” synthesis and separations because they have essentially no vapor pressure. We have begun an investigation of the potential of ionic liquids for gas separations, including the removal of carbon dioxide from stack gas generated in coal-fired power plants. In this paper, we report results from measurements of the permeance of nitrogen and carbon dioxide in supported ionic liquid membranes. Preliminary results for a porous alumina membrane saturated with l-butyl-3-methyl imidazolium bis[trinuoromethylsulfonyl] amide yielded a CO2 : N2 selectivity of 127. Using previously reported measurements of CO2 solubility in ionic liquids (1) and the measured membrane transport characteristics, a preliminary economic analysis of a separation process based on supported ionic liquid membranes has been performed. A comparison of cost estimates for this membrane-based separation to cost estimates reported for carbon dioxide removal using a conventional amine scrubbing operation shows that, with continued technology development, an ionic liquid membrane process may potentially be economically competitive with amine scrubbing. A preliminary cost estimate for an ionic liquid scrubber indicates that an ionic liquid absorption process shows less favorable economics than a supported ionic liquid membrane or an amine scrubber. However, results indicate that a more comprehensive technical and economic assessment is warranted.