COSMO-RS modeling on the extraction of stimulant drugs from urine sample by the double actions of supercritical carbon dioxide and ionic liquid

This work presents the first research linking chemical engineering and sport science as far as we know. The COSMO-RS (conductor-like screening model for real solvents) model was used to make a priori prediction for the extraction of stimulants from aqueous solution by the double action of supercritical carbon dioxide (SC CO₂) and ionic liquid. It was found that the suitable ionic liquids should have small molecular volume, unbranched group and no sterical shielding effect around anion charge center, and thus [C₂MIM]⁺[OAc]^- is the best among all the ionic liquids investigated. The calculated results from the COSMO-RS model were qualitatively consistent with those from experiments. On this basis, partition coefficients of amphetamine (C9N) and nikethamide (C10N) between aqueous phase and supercritical fluid (or MTBE) phase at different temperatures were calculated. It was shown that the separation efficiency of supercritical extraction with ionic liquid is generally higher than that of traditional liquid-liquid extraction. The modeling present can also be extended to the separation of trace amount of organic substances from aqueous solutions for other purposes.     

Numerical Simulation of Absorbing CO2 with Ionic Liquids

Although separating CO₂ from flue gas with ionic liquids has been regarded as a new and effective method, the mass transfer properties of CO₂ absorption in these solvents have not been researched. In this paper, a coupled computational fluid dynamic (CFD) model and population balance model (PBM) was applied to study the mass transfer properties for capturing CO₂ with ionic liquids solvents. The numerical simulation was performed using the Fluent code. Considering the unique properties of ionic liquids, the Eulerian‐Eulerian two‐flow model with a new drag coefficient correlation was employed for the gas‐liquid fluid dynamic simulation. The gas holdup, interfacial area, and bubble size distribution in the bubble column reactor were predicted. The mass transfer coefficients were estimated with Higbie's penetration model. Furthermore, the velocity field and pressure field in the reactor were also predicted in this paper.     

Measurement and correlation of supercritical CO2 and ionic liquid systems for design of advanced unit operations

Ionic liquids combined with supercritical fluid technology hold great promise as working solvents for developing compact processes. Ionic liquids, which are organic molten salts, typically have extremely low volatility and high functionality, but possess high viscosities, surface tensions and low diffusion coefficients, which can limit their applicability. CO₂, on the other hand, especially in its supercritical state, is a green solvent that can be used advantageously when combined with the ionic liquid to provide viscosity and surface tension reduction and to promote mass transfer. The solubility of CO₂ in the ionic liquid is key to estimating the important physical properties that include partition coefficients, viscosities, densities, interfacial tensions, thermal conductivities and heat capacities needed in contactor design. In this work, we examine a subset of available high pressure pure component ionic liquid PVT data and high pressure CO₂-ionic liquid solubility data and report new correlations for CO₂-ionic liquid systems with equations of state that have some industrial applications including: (1) general, (2) fuel desulfurization, (3) CO₂ capture, and (4) chiral separation. New measurements of solubility data for the CO₂ and 1-butyl-3-methylimidazolium octyl sulfate, [bmim][OcSO₄] system are reported and correlated. In the correlation of the CO₂ ionic liquid phase behavior, the Peng-Robinson and the Sanchez-Lacombe equations of state were considered and are compared. It is shown that excellent correlation of CO₂ solubility can be obtained with either equation and they share some common characteristics regarding interaction parameters. In the Sanchez-Lacombe equation, parameters that are derived from the supercritical region were found to be important for obtaining good correlation of the CO₂-ionic liquid solubility data.     

Thermodynamic analysis of absorption refrigeration cycles using ionic liquid + supercritical CO2 pairs

Absorption refrigerators are alternative systems to conventional compression cycles in which the energy necessary for the refrigeration is provided by heating instead of mechanical power. Commercial absorption refrigerators use two absorbent/refrigerant pairs: NH₃-H₂O and H₂O-LiBr. These systems have some limitations due to the difficulty of separating absorbent and refrigerant, the narrow refrigeration temperature range, or the possibility of corrosion and salt deposition. The application of ionic liquids as absorbents with supercritical carbon dioxide as refrigerant can solve some of these problems because separation of ionic liquid from CO₂ is easy due to the negligible vapor pressure of ionic liquids. In this work, suitable ionic liquids-CO₂ pairs have been selected considering their phase equilibrium properties, calculated with the Group-Contribution equation of state developed by Skjold-Jørgensen. The energetic efficiency of the process with ionic liquids has been estimated by calculation of the Coefficient of Performance (COP) of the process. It has been found that the process with ionic liquids has a lower COP than conventional NH₃-H₂O systems due to the necessity of operating with a higher solution flowrate. Nevertheless, near-optimum performance is obtained in a wide range of process conditions.     

Phase behavior of mixture of supercritical CO2 + ionic liquid: Thermodynamic consistency test of experimental data

Various models have been applied composed of the Peng‐Robinson equation of state (PR‐EoS) and the Soave‐Redlich‐Kwong equation of state (SRK‐EoS) associated with three mixing rules including the following: Wong‐Sandler (WS), van der Waals one (vdW1), and van der Waals two (vdW2) for phase behavior modeling of mixtures of supercritical CO₂ + different ionic liquids in vapor–liquid equilibrium (VLE) region. It has been found that the PR EoS implying the WS mixing rule can be used as a reliable thermodynamic model to perform a thermodynamic consistency test on the experimental data of phase behaviors of the supercritical CO₂ + ionic liquid systems (19 commonly‐used ionic liquids have been studied). The results show that 40% of the experimental data seem to be thermodynamically consistent, 55.5% seem to be thermodynamically inconsistent, and 4.5% seem to be not fully consistent. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3892–3913, 2013     

Lipase-catalyzed esterification of citronellol with lauric acid in supercritical carbon dioxide/co-solvent media

Direct esterification of citronellol and lauric acid catalyzed by immobilized lipase B from Candida antarctica was performed in supercritical carbon dioxide with different organic solvents and ionic liquids serving as co-solvents. The highest concentration of citronellol laurate after 1 h of reaction performance (3.95 mmol/g substrates) was obtained in SC CO₂ with ethyl methylketone serving as a co-solvent. The optimal temperature and pressure for citronellol laurate synthesis in SC CO₂/EMK medium was determined to be 60 °C and 10 MPa.     

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.     

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.     

Continuous Flow Enzymatic Kinetic Resolution and Enantiomer Separation using Ionic Liquid/Supercritical Carbon Dioxide Media

The combination of kinetic resolution in ionic liquids (IL) and selective extraction with supercritical carbon dioxide (scCO₂) provides a new approach for the separation of enantiomers as exemplified by the lipase‐catalyzed esterification of chiral secondary alcohols. Excellent enantioselectivities are achieved upon conversion of alcohols 1a–e to the corresponding acetates 4a–e or laureates 5a–e using various modifications of the lipase from Candida antarctica (CaL‐B) in imidazolium‐based ionic liquids. The anion of the ionic liquid has a significant influence on the performance of the bio‐catalyst with bis(trifluoromethanesulfonamide) [BTA] giving the best results. The acetates 4a–e can be extracted from the reaction mixture preferentially over the alcohols 1a–e with scCO₂ under certain conditions, but preparatively useful selectivities would require advanced multi‐step extraction procedures. In contrast, efficient separation is possible with relatively simple equipment if alcohols 1a–e are extracted preferentially from their corresponding laureates 5a–e . A “green” continuous process for the resolution of racemic alcohols without the use of organic solvents was devised on the basis of these findings.     

Ionic Liquids‐Based Membranes for Carbon Dioxide Separation

Ionic liquids (ILs) have gained wide‐spread focus owing to its negligible vapor pressure, low heat capacity, high thermal stability, and structural diversity. The solubility and selectivity toward carbon dioxide has made ILs a unique platform that possess the potential in gas separations. In particularly, combining functional ILs with membranes and porous supports is an efficient way to design task‐specific materials for CO₂ separations. This minireview summarizes the developments and advances of ionic liquids‐based membranes for CO₂ separations in recent three years, with an emphasis on the strategy of incorporating ionic liquids and CO₂ separation performance.     

Biocatalytic ester synthesis in ionic liquid media

Ionic liquids have shown potential as green reaction media compared with organic solvents, mainly due to their lack of vapour pressure. In non‐aqueous enzymology, ionic liquids are opening up new fields. The advantages of using ionic liquids over the use of organic solvents as reaction medium for biocatalysis include enhancement of enzyme activity, stability and selectivity. In this work, the enzymatic synthesis of esters in ionic liquids has been extensively reviewed. Numerous examples of the application of ionic liquids as reaction medium for the enzymatic production of esters have been included. The effect of the nature of the ionic liquid on activity, selectivity and stability of enzymes which catalyze esters synthesis has been carefully analysed. Innovative reaction methodologies for the biosynthesis of esters, including ionic liquid/supercritical carbon dioxide biphasic systems and the integrated reaction/separation processes using supported liquid membranes based on ionic liquids have been revised. Copyright © 2010 Society of Chemical Industry     

Composite blending of ionic liquid–poly(ether sulfone) polymeric membranes: Green materials with potential for carbon dioxide/methane separation

The incorporation of imidazolium‐based ionic liquids into a poly(ether sulfone) (PES) polymeric membrane resulted in a dense and void‐free polymeric membrane. As determined through the ideal gas permeation test, the carbon dioxide (CO₂) permeation increased about 22% compared to that of the pure PES polymeric membrane whereas the methane (CH₄) permeation decreased tremendously. This made the CO₂/CH₄ ideal separation increase substantially by more than 100%. This study highlighted the utilization of imidazolium‐based ionic liquids in the synthesis of ionic liquid polymeric membranes (ILPMs). Two different ionic liquids were used to compare the CO₂ separation performance through the membranes. The glass‐transition temperatures (T_gs) of ILPMs were found to be lower than the T_g of the pure PES polymeric membranes; this supported the high CO₂ permeation of the ILPMs due to the increase in PES flexibility caused by ionic liquid addition. The results also draw attention to new trends of ionic liquids as a potential green candidates for future membrane synthesis. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43999.     

State of the art of ionic liquid-modified adsorbents for CO2 capture and separation

The enormous emission of carbon dioxide (CO₂) from industries has triggered a series of environmental issues. In recent years, ionic liquids (ILs) as novel absorbents are widely used for CO₂ capture owing to their low vapor pressure and tunable structures. IL-modified adsorbents have the advantages of both ILs and porous supports, such as high CO₂ selectivity and high specific surface area, which are novel agents to capture CO₂ with broad application prospects. In this review, more than 140 IL-modified adsorbents for CO₂ capture in recent years were systematically summarized. The types of ILs including conventional ILs and functionalized ILs on CO₂ separation performance of different IL hybrid adsorbents, and their adsorption mechanisms were also discussed. Finally, future perspectives on IL-modified adsorbents for CO₂ separation were further posed.     

Progress in carbon dioxide capture and separation research for gasification-based power generation point sources

The purpose of the present work is to investigate novel approaches, materials, and molecules for the abatement of carbon dioxide (CO₂) at the pre-combustion stage of gasification-based power generation point sources. The capture/separation step for CO₂ from large point sources is a critical one with respect to the technical feasibility and cost of the overall carbon sequestration scenario. For large point sources, such as those found in power generation, the carbon dioxide capture techniques being investigated by the Office of Research and Development of the National Energy Technology Laboratory possess the potential for improved efficiency and reduced costs as compared to more conventional technologies. The investigated techniques can have wide applications, but the present research is focused on the capture/separation of carbon dioxide from fuel gas (pre-combustion gas) from processes such as the Integrated Gasification Combined Cycle (IGCC) process. For such applications, novel concepts are being developed in wet scrubbing with physical sorption, chemical sorption with solid sorbents, and separation by membranes. In one concept, a wet scrubbing technique is being investigated that uses a physical solvent process to remove CO₂ from fuel gas of an IGCC system at elevated temperature and pressure. The need to define an “ideal” solvent has led to the study of the solubility and mass transfer properties of various solvents. Pertaining to another separation technology, fabrication techniques and mechanistic studies for membranes separating CO₂ from the fuel gas produced by coal gasification are also being performed. Membranes that consist of CO₂-philic ionic liquids encapsulated into a polymeric substrate have been investigated for permeability and selectivity. Finally, processes based on dry, regenerable sorbents are additional techniques for CO₂ capture from fuel gas. An overview of these novel techniques is presented along with a research progress status of technologies related to membranes and physical solvents.     

Ionic liquids [EMIM][BF4], [EMIM][Otf] and [BMIM][Otf] as corrosion inhibitors for CO2 capture applications

We present the viability of using thermally stable, practically non-volatile ionic liquids as corrosion inhibitors in aqueous monoethanolamine systems. Carbon steel 1020, which is widely used as a construction material in CO₂ capture plants, has been taken as a test material. Corrosion inhibition capabilities of typical room-temperature ionic liquids constituting imidazolium cation in concentration range ≤3% in CO₂ capture applications were investigated. Electrochemical corrosion experiments using the potentiodynamic polarization technique for measuring corrosion current were carried out. Subsequent calculation of corrosion rate via Tafel fit was performed. The experimental findings suggest that the corrosion rate is significantly dependent on the process parameters, such as the CO₂ loading and the presence of oxygen. In addition, the value of the corrosion rate is sensitive to the type of ionic liquid added. Moreover, the results show that ionic liquids possess the ability of suppressing severe operational problems of corrosion in typical CO₂ capture plants to a reasonable extent (≥50%).     

High-pressure phase behavior of systems with ionic liquids: measurements and modeling of the binary system fluoroform+1-ethyl-3-methylimidazolium hexafluorophosphate

In order to gain insight into the phase behavior of ionic liquids+supercritical fluids, the phase boundaries of a binary mixture of an air- and water-stable ionic liquid and a supercritical fluid has been studied experimentally. For this purpose, fluoroform (CHF₃) was considered as the supercritical fluid and 1-ethyl-3-methylimidazolium hexafluorophosphate ([emim][PF₆]) was selected as the ionic liquid. A synthetic method was used to measure vapor–liquid and solid–liquid boundaries. Results are reported for CHF₃ concentrations ranging from 10.1 to 99.0 mol%, and within temperature and pressure ranges of 309.3–367.5 K and 1.6–51.6 MPa, respectively. The Peng–Robinson equation of state is used to model this binary system.     

Prediction of CO2/O2 absorption selectivity using supported ionic liquid membranes (SILMs) for gas–liquid membrane contactor

Given their unique and tunable properties as solvents, ionic liquids (ILs) have become a favorable solvent option in separation processes, particularly for capturing carbon dioxide (CO₂). In this work, a simple method that can be used to screen the suitable IL candidates was implemented in our modified gas–liquid membrane contactor system. Solubilities, selectivities of CO₂, nitrogen (N₂), and oxygen (O₂) gases in imidazolium-based ILs and its activity coefficients in water and monoethanolamine (MEA) were predicted using conductor-like screening model for real solvent (COSMO-RS) method over a wide range of temperature (298.15–348.15?K). Results from the analysis revealed that [emim] [NTf₂] IL is a good candidate for further absorption process attributed to its good hydrophobicity and CO₂/O₂ selectivity characteristics. While their miscibility with pure MEA was somehow higher, utilizing the aqueous phase of MEA would be beneficial in this stage. Data on absorption performances and selectivity of CO₂/O₂ are scarce especially in gas–liquid membrane contactor system. Therefore, considering [emim] [NTf₂] IL as a supporting material in supported ionic liquid membranes (SILMs), using aqueous phase of MEA as an absorbent would result in a great membrane-solvent combination system in furthering our gas–liquid membrane contactor process. In conclusion, COSMO-RS is a potentially great predictive utility to screen ILs for specified separation applications. In addition, this work provides useful results for the [emim] [NTf₂]-SILMs to be extensively applied in the field of CO₂ capture and selective O₂ removal.     

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.     

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