The effect of protic ionic liquids incorporation on CO2 separation performance of Pebax-based membranes

The separation of carbon dioxide (CO₂) is of great importance for environment protection and gas resource purification. The ionic liquids (ILs)-based gas separation membrane provides a new chance for efficient CO₂ separation, while high permeability and selectivity of membranes is a great challenge. In this study, the influence of two protic ILs with different anion ([TMGH][Im] and [TMGH][PhO]) on the CO₂ separation performance of the prepared ILs/Pebax blended membranes were systematically investigated at different temperature. The results showed the CO₂ permeability exhibits the rising trend for ILs/Pebax blended membranes with the increment of IL content. Especially, the [TMGH][Im] with low viscosity and high CO₂ absorption capacity leads to the blended membranes showing better CO₂ permeability and ideal CO₂ selectivity than that of membranes with [TMGH][PhO] at high IL content. Besides, with operating temperature increasing, the gas permeability of 20% (mass) [TMGH][Im]/Pebax blended membrane increases due to the decreasing viscosity of IL and the rising chain mobility of polymer. Inversely, the gas selectivity shows decreasing trend because CO₂ absorption capacity obviously decreased at higher temperature.     

Ionic liquids for CO2 capture—Development and progress

Innovative off-the-shelf CO₂ capture approaches are burgeoning in the literature, among which, ionic liquids seem to have been omitted in the recent Intergovernmental Panel on Climate Change (IPCC) survey. Ionic liquids (ILs), because of their tunable properties, wide liquid range, reasonable thermal stability, and negligible vapor pressure, are emerging as promising candidates rivaling with conventional amine scrubbing. Due to substantial solubility, room-temperature ionic liquids (RTILs) are quite useful for CO₂ separation from flue gases. Their absorption capacity can be greatly enhanced by functionalization with an amine moiety but with concurrent increase in viscosity making process handling difficult. However this downside can be overcome by making use of supported ionic-liquid membranes (SILMs), especially where high pressures and temperatures are involved. Moreover, due to negligible loss of ionic liquids during recycling, these technologies will also decrease the CO₂ capture cost to a reasonable extent when employed on industrial scale. There is also need to look deeply into the noxious behavior of these unique species. Nevertheless, the flexibility in synthetic structure of ionic liquids may make them opportunistic in CO₂ capture scenarios.     

Synthesis of high molar mass poly(12-hydroxydodecanoic acid) in brønsted acid ionic liquids

An easy and fast direct polyesterification method using Brønsted acid ionic liquids (BAILs) as both reaction medium and catalyst was investigated. High molar mass polyesters of 12-hydroxydodecanoic acid (up to ) were obtained in good yields at atmospheric pressure and low temperature (90-130 °C) after 10-120 min reaction and without any added catalyst, reaction conditions that are much milder than conventional ones. Ionic liquids composed of an acidic cation bearing sulfonic acid groups and an acidic anion, such as 3-alkyl-1-(butyl-4-sulfonyl)imidazolium hydrogen sulfates, gave better results than ionic liquids containing only an acidic anion, such as 1-alkyl-3-methylimidazolium hydrogen sulfates. The 1/1 BAIL/12-hydroxydodecanoic acid molar ratio was found to yield polymers of the highest molar mass.     

High pressure solubility of CO2 in non-fluorinated phosphonium-based ionic liquids

High pressure solubility of carbon dioxide in three phosphonium-based ionic liquids has been measured experimentally. A synthetic method was used to measure vapor–liquid, vapor–liquid–liquid and liquid–liquid equilibria of carbon dioxide in the ionic liquids trihexyltetradecylphosphonium bromide [thtdp][Br], trihexyltetradecylphosphonium dicyanamide [thtdp][dca] and trihexyltetradecylphosphonium bis(2,4,4-trime-thylpentyl)phosphinate [thtdp][phos] for a temperature range of 271–363 K and up to 90 MPa. Furthermore, the densities and viscosities of these ILs have been measured in a temperature range of 293–363 K. The solubility of carbon dioxide in these ILs is (on mole fraction basis) significantly larger than most of the commonly used fluorinated imidazolium ionic liquids. The latter statement, however, does not hold for the [Br] and [dca] based IL if the solubility is compared on molality (mole/mass solvent) basis, where the solubility differences among physical ILs tends to vanish indicating a strong molecular weight effect. The solubility of carbon dioxide in [thtdp][phos], both on mole fraction and molality basis, is among the highest compared to all the other physical ILs reported so far in the literature. The Peng–Robinson equation of state in combination with Wong–Sandler mixing rules incorporating the NRTL Gibbs excess energy model was applied to represent the experimental data with acceptable accuracy.     

Cetirizine solubility in supercritical CO2 at different pressures and temperatures

A simple static technique was used to obtain the solubility of cetirizine in supercritical carbon dioxide. The solubility measurements were performed at temperatures and pressures ranging from 308.15 to 338.15 K and 160 to 400 bar, respectively; resulting in mole fractions in the 1.05 × 10⁻⁵ to 4.92 × 10⁻³ range. The Chrastil, Bartle, Kumar & Johnston and the Mendez-Santiago and Teja (MST) models were used to correlate the experimental data. The calculated solubilities showed good agreement with the experimental data in the temperature and pressure ranges studied.     

Supercritical CO2 and highly selective aromatase inhibitors: Experimental solubility and empirical data correlation

The solubility of highly selective and potent third-generation aromatase inhibitors includes the non-steroidal agents letrozole and anastrozole and the steroid exemestane in supercritical carbon dioxide (SC-CO₂) has been investigated. The experiments were carried out using the simple and static method at pressures in the range of 12.1–35.5 MPa and temperatures ranging from 308 to 348 K. The mole fraction solubilities ranged from 0.22 × 10⁻⁵ to 1.88 × 10⁻⁴. Solubility data were correlated using six empirical models (Chrastil model, dV–A model, K–J model, Bartle model, Yu model and Gordillo model). The results showed that these models can be applied to satisfactory solubility predictions at different pressures and temperatures. A comparison among the six models revealed that the K–J, and Gordillo models gave much better correlations of the solubility data with an average absolute relative deviation (AARD%) ranging from 0.2 to 2.3 and from 1.6 to 2.5%, respectively. Using the correlation results, the heat of drug–CO₂ solvation and that of drug vaporization was separately approximated in the range of −17.3 to −17.5 and 93.0–112.1 kJ mol⁻¹.     

Purification of ionic liquids by supercritical CO2 monitored by infrared spectroscopy

Transmission infrared and Attenuated Total Reflection (ATR) in situ infrared spectroscopies were combined for the time-resolved monitoring of both liquid and supercritical phases during extraction of water and other impurities from ionic liquids with supercritical carbon dioxide (scCO₂). Cleaning and drying by scCO₂ at 100 bar and 40 °C proved to be efficient for all ionic liquids tested, including 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), and 1-butyl-3-methylimidazolium trifluoromethansulfonate ([bmim][TfO] or [bmim] triflate). Despite the moderate solubility of water in scCO₂ compared to other classical solvents, the amount of water decreased continuously during the drying. The extraction could be followed by simple transmission IR spectroscopy of the supercritical phase. During the extraction, organic impurities and water were removed rapidly from the ionic liquid phase as scCO₂ improved the transport properties in the ionic liquids.     

Fixation and conversion of CO2 using ionic liquids

Ionic liquids (ILs), a kind of novel green media composed entirely of cations and anions, have recently attracted considerable attention due to their unique properties such as non-volatility, tunable polarity, high stability and so on. In this work, the latest progress on the fixation and conversion of carbon dioxide (CO₂) using ILs as absorbents, catalysts or promoters has been summarized. The absorption performance of conventional ILs and task-specific ILs was systematically investigated, the conversion of CO₂ with epoxides, propargyl alcohols and amines using ILs was critically evaluated, and the significant advantages in the fixation and conversion of CO₂ using the ILs were demonstrated compared to the conventional absorbents and the catalytic systems without ILs. This research progress may finally lead to building of an in situ fixation–conversion process of CO₂ with ILs. If so, we are near an epoch of the fixation and utilization of CO₂, although there is obviously a long way to go for us to achieve such a goal.     

Impact of thickness on CO2 concentration profiles within polymer films swollen near the critical pressure

The isothermal swelling of polymer thin films by a supercritical fluid does not increase monotonically with increasing chemical potential (pressure), but rather a maximum in swelling is generally observed near the critical pressure. A reactive templating approach utilizing the condensation of silica within hydrophilic domains of a swollen amphiphilic polymer film enables visualization of the qualitative concentration profile of CO₂ by the changes in the size of hydrophobic domains (pores) with cross sectional TEM microscopy; specifically, isothermal swelling of poly(ethylene oxide-propylene oxide-ethylene oxide) films by CO₂ at 60 °C is examined. Films that contain thickness gradients are used to avoid any uncertainties in the impact of thickness due to variations in the temperature or pressure during the silica modification. A uniform pore size (local swelling) is observed for all film thicknesses when the pressure is outside of the anomalous maximum in the film swelling, except for a small increase at the buried interface due to preferential adsorption of CO₂ to the native silicon oxide surface of the substrate. However at this swelling maximum, a gradient in the pore size is observed at both interfaces. These swelling gradients at interfaces appear to be responsible for the anomalous maximum in thin films. As the film thickness increases beyond 350 nm, there is a decrease in the maximum swelling at the free interface.     

Artificial Neural Network modeling of solubility of supercritical carbon dioxide in 24 commonly used ionic liquids

Application of supercritical CO₂ for separation of ionic liquids from their organic solvents or extraction of various solutes from ionic liquid solvents have found great interest during recent years. Knowledge of phase behaviors of the mixtures of supercritical CO₂+ionic liquids is therefore drastic in order to efficiently design such separation processes. In this communication, Artificial Neural Network procedure has been applied to represent the solubility of supercritical CO₂ in 24 mostly used ionic liquids. An optimized Three-Layer Feed Forward Neural Network using critical properties of ionic liquids and operational temperature and pressure has been developed. Application of this model for 1128 data points of 24 ionic liquids show squared correlation coefficients of 0.993 and average absolute deviation of 3.6% from experimental values for calculated/estimated solubilities. The aforementioned deviations show the prediction capability of the presented model.     

Low-pressure CO2 sorption in ammonium-based poly(ionic liquid)s

Ammonium-based ionic liquid monomers and their corresponding polymers [poly(ionic liquid)s] are synthesized and characterized for CO₂ sorption. The polymers have much higher CO₂ sorption capacities than the room-temperature ionic liquids and imidazolium-based poly(ionic liquid)s. For example, P[VBTMA][PF₆] with polystyrene backbone has a CO₂ sorption capacity of 10.67 mol%. The CO₂ sorption is selective over N₂ and O₂. The effects of cation, backbone, substituent, anion and crosslinking on CO₂ sorption are discussed. The sorption mechanism study indicates that CO₂ sorption by the poly(ionic liquid)s is a bulk and surface phenomenon.     

Effect of menthol as solid cosolvent on the solubility enhancement of clozapine and lamorigine in supercritical CO2

The solubilities of mixed clozapine and menthol also lamotrigine and menthol in supercritical carbon dioxide were determined at 313 and 323 K and over pressure ranging from 123 to 337 bar. The solubility of both solutes with solid cosolvent system is observed to increase relative to the value of the corresponding without solid cosolvent system. As compared with their respective binary system (without solid cosolvent), the mixed clozapine (with solid cosolvent) solubility enhancement greatly by around 56 times and the lamotrigine one does by approximately eight times. In presence of menthol these chemicals have solubilities with values ranging from 1.88 × 10⁻⁴ to 4.48 × 10⁻⁴ (clozapine) and 0.09 × 10⁻⁴ to 0.36 × 10⁻⁴ (lamotrigine) mole fraction. The solubility data were correlated using five semi-empirical density-based models (Chrastil, Bartle, K-J, M-T and Thakur models). Correlated results for clozapine with the Chrastil, M-T, K-J, and Bartle models and for lamotrigine with the Chrastil, M-T and Bartel models are in excellent agreement with the experimental data.     

Modelling carbon dioxide solubility in ionic liquids

Solubility information for CO₂ in different ionic liquids, ILs, in part can potentially be used to select a specific IL for the separation of CO₂ from hydrocarbon fluids. Unfortunately, not all CO₂–IL systems have been experimentally described at similar temperatures and pressures; therefore, a direct comparison of performance by process simulation is not always possible. In the extreme cases, the design of a CO₂ separation process may require predicting the CO₂–IL equilibria for which there are no available solubility data. To address the need for this information, a semi‐empirical correlation was developed to estimate the dissolution of CO₂ in CO₂–IL solvent systems. The theoretical COSMO–RS calculation method was used to calculate the chemical potential of CO₂ in a wide variety of ILs and the Soave–Redlich–Kwong equation was used to calculate the fugacity coefficient of the CO₂ vapour phase. The model was correlated with available literature data, yielding an average error of AAR = 23% and small bias. © 2012 Canadian Society for Chemical Engineering     

Synthesis of cyclic carbonate from vinyl cyclohexene oxide and CO2 using ionic liquids as catalysts

Synthesis of cyclic carbonate from 4-vinyl-1-cyclohexene-1,2-epoxide (VCHO) and carbon dioxide was investigated without using any solvent in the presence of ionic liquid as a catalyst. Ionic liquids based on 1-alkylmethylimidazolium salts of different alkyl groups (ethyl, butyl, hexyl, octyl) and different anions (Cl⁻, BF₄⁻, PF₆⁻) were used as catalysts. The conversion of VCHO was affected by the structure of the imidazolium salt ionic liquids; the ones with the cations of bulkier alkyl chain length and with more nucleophilic anion showed better reactivity. Reaction temperature, carbon dioxide pressure, and zinc halide cocatalyst enhanced the addition of CO₂ to VCHO. Semi-batch operation with continuous supply of carbon dioxide showed higher VCHO conversion than batch operation did.     

High-pressure solubility of carbon dioxide in imidazolium-based ionic liquids with anions [PF6] and [BF4]

The solubility of carbon dioxide in three ionic liquids (ILs) under supercritical fluid condition was measured at pressures up to 32 MPa and at temperatures of 313.15, 323.15, and 333.15 K in a high-pressure view cell. The imidazolium-derivative ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), and 1-octyl-3-methylimidazolium tetrafluoroborate ([omim][BF₄]) were employed in this research. The effects of pressure, temperature, nature of anion and cation as well as the water content on the solubility of CO₂ in the ILs were investigated experimentally. The solubility of CO₂ in the IL was higher for the ILs with longer cationic alkyl group and for the ILs with lower anion polarity. The lower the water content or the lower the temperature as well as the higher the pressure, the higher was the solubility of CO₂.     

High pressure density and solubility for the CO2 + 1-ethyl-3-methylimidazolium ethylsulfate system

The solubility and density of the CO₂ + 1-ethyl-3-methylimidazolium ethylsulfate system were investigated. The carbon dioxide solubility in the IL was measured in the temperature range 273–413 K, for pressure up to 5 MPa and CO₂ mole fractions ranging from 0.02 to 0.5 using the isochoric method, while the system density was carried out at temperatures ranging from 278.15 K to 398.15 K, pressures from 10 MPa to 120 MPa and 0.2, 0.4, 0.7 and 0.8 CO₂ mole fractions. Similar to what was previously observed for phosphonate-based ILs, the ionic liquid high polarity leads to positive deviations from ideality resulting from unfavorable interactions with the CO₂.The results from the density and solubility derived properties show that the system presents important negative excess molar volumes, over the whole range of compositions and temperatures, and a negative entropy of solvation that suggests an increase in ordering of the solvent molecules surrounding the solute. The observed negative excess molar volumes result from the large difference between the molecular volumes of the species involved, with the small carbon dioxide molecules occupying the empty spaces between the larger IL ions, supporting the notion that the carbon dioxide, upon dissolution, occupies essentially the bulk free volume since the IL does not significantly expand upon gas absorption. These results portray ionic liquids as a porous media, like a soft sponge, with a huge free volume in which large amounts of carbon dioxide are able to accommodate during the dissolution process.     

CO2 absorption properties of Brønsted acid-base ionic liquid composed of N,N-dimethylformamide and bis(trifluoromethanesulfonyl)amide

The solubilities of CO₂ and the liquid densities in a Brønsted acid-base ionic liquid, [DMFH][Tf₂N], composed of N,N-dimethylformamide (DMF) and bis(trifluoromethanesulfonyl)amide (HTf₂N) have been investigated at high pressures and at different temperatures. The results were compared with those in DMF and a typical 1-butyl-3-methylimidazolium analogue with the same anion, [BMIM][Tf₂N]. The mole fraction scaled solubilities of CO₂ in the three liquids showed a slight increase in the following order, DMF < [DMFH][Tf₂N] < [BMIM][Tf₂N], whereas more remarkable difference was observed in the volume scaled concentrations of CO₂, [BMIM][Tf₂N] < [DMFH][Tf₂N] « DMF, mainly due to the bulkiness of liquid entities.     

CO2 reforming of CH4 over stabilized mesoporous Ni-CaO-ZrO2 composites

Mesoporous Ni-CaO-ZrO₂ nanocomposites with high thermal stability were designed and employed in the CO₂/CH₄ reforming. The nanocomposites with appropriate Ni/Ca/Zr molar ratios exhibited excellent activity and prominent coking resistivity. The Ni crystallites were effectively controlled under the critical size for coke formation in such nanocomposites. It was found that low Ni content resulted in high metal dispersion and good catalytic performance. Moreover, the basicity of the matrices improved the chemisorption of CO₂ and promoted the gasification of deposited coke on the catalyst.     

Thermodynamic modeling of CO2 solubility in aqueous solutions of NaCl and Na2SO4

A thermodynamic model based on the electrolyte NRTL activity coefficient equation and PC-SAFT equation-of-state is developed for CO₂ solubility in aqueous solutions of NaCl and Na₂SO₄ with temperature up to 473.15 K, pressure up to 150 MPa, and salt concentrations up to saturation. The Henry's constant parameters of CO₂ in H₂O and the characteristic volume parameters for CO₂ required for pressure correction of Henry's constant are identified from fitting the experimental gas solubility of CO₂ in pure water with temperature up to 473.15 K and pressure up to 150 MPa. The NRTL binary parameters for the CO₂-(Na⁺, Cl⁻) pair and the CO₂-(Na⁺, SO₄²⁻) pair are regressed against the experimental VLE data for the CO₂-NaCl-H₂O ternary system up to 373.15 K and 20 MPa and the CO₂-Na₂SO₄-H₂O ternary system up to 433.15 K and 13 MPa, respectively. Model calculations on solubility and heat of solution of CO₂ in pure water and aqueous solutions of NaCl and Na₂SO₄ are compared to the available experimental data of the CO₂-H₂O binary, CO₂-NaCl-H₂O ternary and CO₂-Na₂SO₄-H₂O ternary systems with excellent results.     

Exceptionally effective H2S absorption and conversion into thiols in novel superbase protic ionic liquids

We demonstrate an effective strategy for capture and conversion of H₂S in novel superbase protic ionic liquids (SPILs). It is found that the synthesized SPILs with the multiple active sites exhibit the unprecedented H₂S uptake via chemical absorption (up to 1.81 mol mol⁻¹ at 298.2 K and 1 bar). More importantly, H₂S molecule is activated by these SPILs during the absorption process, so that the activated H₂S can be converted further into high value-added thiols in situ with excellent yields under mild conditions (303.2 K and 1 bar) without any solvents and metallic catalysts. Since H₂S-saturated SPILs can be regenerated by chemical conversion of absorbed H₂S into thiols, thereby eliminating the higher input of energy consumption during the process of H₂S stripping. This SPIL-mediated scheme provides an alternative approach for the capture and chemical conversion of H₂S.