High pressure phase behaviour of mixtures of hydrogen and the ionic liquid family [cnmim][Tf2N]

The high-pressure solubility of hydrogen gas in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulphonyl)amide ([emim][Tf₂N]) was measured experimentally in an equipment based on the synthetic technique. Measurements were carried out within a temperature range of 310–450 K and pressures up to 15 MPa. Hydrogen solubility was shown to be low in this ionic liquid, reaching a maximum concentration of about 6 mole percent at the highest temperatures and pressures investigated. Hydrogen solubility showed an “inverse” temperature effect, indicating increased solubility at higher temperatures in contrast to other commonly investigated gas solubilities in ionic liquids, such as carbon dioxide. Within the temperature and pressure range investigated, solubility isotherms on a pressure–concentration diagram approximated linear behaviour. It was also shown that the solubility of hydrogen increases as the alkyl side chain of the cation increases in size within the homologous family.     

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.     

Planar thin film supercapacitor based on cluster-assembled nanostructured carbon and ionic liquid electrolyte

The fabrication of a planar supercapacitor based on cluster-assembled nanostructured carbon (ns-C) thin films deposited by supersonic cluster beam deposition and ionic liquid as electrolyte has been demonstrated. Cluster-assembled carbon has a density of about 0.5 g/cm³ and a highly disordered structure with predominant sp² hybridization, high surface roughness and granular nanoscale morphology. The electric double layer capacity of ns-C films (thickness variable in the range of 140–500 nm) was investigated by electrochemical impedance spectroscopy and cyclic voltammetry employing four different hydrophobic room-temperature ionic liquids featuring the same anion and with different cations as electrolyte. Evidence of good impregnation of the ns-C nanoporous matrix by the different ionic liquids was found. The highest EDL capacity, 75 F/g, was obtained by using [Bmim][NTf2], the ionic liquid with the shortest alkyl chain. Using [Bmim][NTf2] a supercapacitor with single electrode area of 0.2 cm² and specific capacity of ∼80 μF/cm² was obtained.     

含离子液体乙腈-正丙醇体系的等压汽液平衡

常压(101.3 kPa)下, 测定了如下体系的汽液平衡数据:乙腈-正丙醇-氯化1-苄基-3-甲基咪唑([BzMIM][Cl])、乙腈-正丙醇-溴化1-苄基-3-甲基咪唑([BzMIM][Br])、乙腈-正丙醇-溴化1-己基-3-甲基咪唑([HMIM][Br]), 考察了3种离子液体对乙腈-正丙醇体系相平衡行为的影响。实验结果表明, 3种离子液体都能够提高乙腈对正丙醇的相对挥发度, 3种离子液体提高相对挥发度的顺序为 [BzMIM][Cl] > [BzMIM][Br] > [HMIM][Br]。用NRTL模型对测得的汽液平衡数据进行了关联, 关联结果与实验结果具有良好的一致性。     

萃取精馏分离甲醇-丁酮萃取剂的选择

为了解决工业生产中甲醇-丁酮共沸体系难分离的问题,本研究采用一步法合成了N-乙基吡啶溴盐([EPy][Br])、N-丁基吡啶溴盐([BPy][Br])和N-己基吡啶溴盐([HPy][Br])3种离子液体(IL),测定了101.3 kPa下这3种离子液体对甲醇-丁酮共沸物系的溶剂选择性,并考察了溶剂比对其选择性的影响,同时将离子液体的分离性能与有机溶剂进行了比较。实验结果表明:合成的3种离子液体都可提高甲醇对丁酮的相对挥发度,它们的选择性大小顺序为[EPy][Br]> [BPy][Br]> [HPy][Br],同时,它们的选择性随溶剂比的增加而增大,与常规有机溶剂相比,离子液体作为萃取剂具有显著优势。因此,可以选用[EPy][Br]作为分离甲醇-丁酮共沸物系的萃取剂。     

Ionic liquid effects on the reaction of β-enaminones and tert-butylhydrazine and applications for the synthesis of pyrazoles

In order to evaluate the effect of a series of 10 different ionic liquids ([BMIM][BF₄], [BMIM][Br], [OMIM][BF₄], [BMIM][PF₆], [DBMIM][Br], [DBMIM][BF₄], [BMIM][OH], [BMIM][SCN], [HMIM][HSO₄] and [HMIM][CF₃CO₂]) the cyclocondensation reaction between 4-dimethylamino-1-phenyl-3-alken-2-ones (RC(O)CHCHNMe₂, where R = Ph, 4-Me-Ph, 4-F-Ph, 4-Cl-Ph, 4-Br-Ph, 4-NO₂-Ph, thien-2-yl, fur-2-yl, pyrrol-2-yl, pyrid-2-yl, hexyl, dimethoxymethyl) and tert-butylhydrazine was performed. The effects of each ionic liquid are discussed and the best yields for the cyclocondensation reaction studied were obtained using [BMIM][BF₄].     

Investigations of novel nitrile-based ionic liquids as pre-treatment solvent for extraction of lignin from bamboo biomass

In this work, nitrile-based ionic liquids (ILs) i.e., 1-propyronitrile-3-butylimidazolium chloride [C2CNBim]Cl, 1-propyronitrile-3-allylimidazolium chloride [C2CNAim]Cl, 1-propyronitrile-3-(2-hydroxyethyl)imidazolium chloride [C2CN HEim]Cl and 1-propyronitrile-3-benzyllimidazolium chloride [C2CN Bzim]Cl were used as pre-treatment solvent for the extraction of lignin from bamboo biomass. The pre-treatment process was investigated with respect to several factors such as the types of ionic liquid cation used, the effect of pretreatment temperature and time, sample loading and particle size, the effect of recycling the ionic liquid on lignin extraction and the effect of multi-extraction to enhance the recovery of lignin which were collectively found to have an impact on the lignin extraction as a whole. The crystallinity of the cellulose-rich material obtained from the extraction was analyzed using XRD while the extracted lignin was characterized using FTIR, NMR, TGA and elemental analysis. From the XRD analysis, the crystallinity of the cellulose-rich material obtained after treatment with the synthesized nitrile-based ILs was found to remain the same. Among the nitrile-based ILs used, [C2CN Bzim]Cl demonstrate the best performance for the extraction process in a predetermined condition (T = 120 °C, t = 24 h) where 53% of the lignin from the bamboo was successfully extracted. This was confirmed from the FTIR and NMR analysis showing the characteristic peaks indicating the presence of lignin in the spectra of the respective samples tested.     

Experimental measurement and correlation for solubility of piroxicam (a non-steroidal anti-inflammatory drugs (NSAIDs)) in supercritical carbon dioxide

Since the knowledge of pharmaceutical solubilities in the supercritical carbon dioxide is one of the first essential necessities for designing the supercritical carbon dioxide-based processes, solubility of piroxicam a non-steroidal anti-inflammatory drug was experimentally measured. In this regard, a static method coupled with gravimetric method was used to measure the solubility of piroxicam in the supercritical carbon dioxide in temperature and pressure range of 308.15–338.15 K and 16–40 MPa, respectively. The obtained solubility data were in the range of 1.17 × 10⁻⁵ and 5.12 × 10⁻⁴ based on the mole fraction (mole piroxicam/(mole piroxicam + mole CO₂)) then modeled using four different density based correlations namely Bartle et al., Mendez-Santiago-Teja, Chrastil and Kumar and Johnston models. The results of error analysis revealed that the used correlations were potential to correlate the solubility of piroxicam with minimum and maximum average absolute relative deviation percents (AARD%) of 14.4% and 15.2%, respectively.     

Modified COSMO-UNIFAC model for ionic liquid–CO2 systems and molecular dynamic simulation

A new predictive molecular thermodynamic model (i.e., modified COSMO-SAC-UNIFAC) was first proposed and extended to predict the solubility of CO₂ in pure and mixed ionic liquids (ILs) at the temperatures down to 263.2 K. It is interesting to discover that with equimolar amounts, the solubility of CO₂ in such 1:1 IL pairs, that is, [A₁][B₁] + [A₂][B₂] and [A₁][B₂] + [A₂][B₁], was consistent at the same temperature and pressure in the case of exchanging their respective cations and anions. The molecular dynamic (MD) simulation for CO₂ + mixed ILs was performed to deeply analyze and explain this intriguing phenomenon. Not only the CO₂ gas drying experiment with the ILs ([C2mim][OAc], [C2mim][dca], and [C2mim][OAc] + [C2mim][dca]) as absorbents but also the corresponding process simulation and optimization were made to stress the effectiveness and applicability of the new thermodynamic model. Thus, this work ranges from molecular level to systematic scale.     

Phase behavior of catalytic deactivated compounds and water with 1-ethyl-3-methylimidazolium acetate [EMIM][OAc] ionic liquid at T = 298.15–323.15 K and p = 1 bar

Density, surface tension and refractive index of the binary mixture of catalytic deactivated compounds with 1-ethyl-3-methylimidazolium acetate {[EMIM][OAc]} ionic liquid were measured at temperature of 298.15–323.15 K from which the derived thermodynamic properties including excess molar volume and deviation of surface tension and refractive index were calculated. The derived thermodynamic properties could be explained well by the interaction between similar and dissimilar aromatic structure of the molecules over the entire mole fraction of ILs. It was observed that all the catalytic deactivated compounds and water molecules have significant structural interaction with [EMIM][OAc] via CH?π bond interaction, π?π stacking and n?π interaction over the entire mole fraction of IL at T = 298.15 K. Further the composition of ionic liquid have significant influence on the interaction between dissimilar aromatic structure of molecules like pyridine, indoline and quinoline in liquid phase as compared to temperature. The surface tension increases in the order of: hiophene > pyridine > quinoline > pyrrole > indoline > water; while the refractive index increases in the order: pyridine < water < pyrrole < thiophene < indoline < quinoline. The deviation of surface tension was found to be inversely proportional to the deviation of refractive index at T = 298.15 K. From these results it was concluded that the structure of the ionic liquids is very important for extraction processes on catalytic deactivated compounds, especially for pyridine, indoline and quinoline as compared to water molecules.     

High-pressure phase equilibria for the synthesis of ionic liquids in compressed CO2 for 1-hexyl-3-methylimidazolium bromide with 1-bromohexane and 1-methylimidazole

The use of carbon dioxide in the synthesis of ionic liquids (ILs) has many advantages over conventional solvents. Here, the high-pressure phase equilibria (including CO₂ solubility, volume expansion, and mixture critical points) are measured and modeled for the system involved in the synthesis of a model imidazolium ionic liquid 1-hexyl-3-methylimidazolium bromide ([HMIm][Br]) from 1-bromohexane and 1-methylimidazole. The global phase behavior of 1-methylimidazole was investigated and found to be a Type V system (or potentially IV) from the classification of Scott and van Konynenburg with regions of vapor–liquid equilibrium, vapor–liquid–liquid equilibrium, liquid–liquid equilibrium, an upper and lower critical endpoint and mixture critical points. The solubility and volume expansion of CO₂ in 1-methylimidazole, 1-bromohexane, a 1:1 mixture of 1-methylimidazole and 1-bromohexane and [HMIm][Br] was determined at 313.15 K and 333.15 K for pressures ranging from 10 to 160 bar. The solubility of CO₂ and the volume expansion increases in the order of [HMIm][Br]  1-methylimidazole < 1:1 mixture of reactants < 1-bromohexane. The Peng–Robinson equation of state with van der Waals 2-parameter mixing rules was used with estimated critical properties to well correlate the vapor–liquid equilibrium. The results have important ramifications on the kinetics and process constraints of an actual IL synthesis with CO₂.     

Coconut shell activated carbon tethered ionic liquids for continuous cycloaddition of CO2 to epichlorohydrin in packed bed reactor

Various ionic liquids (ILs) were in situ prepared on coconut shell activated carbon (CSAC) granules. Cycloaddition of CO₂ to epichlorohydrin (ECH) was continuously carried out in a packed-bed reactor without using solvent or cocatalyst. The conversion rates of ECH over the CSAC tethered Bmim/Br, Bmim/BF₄, Bmim-OH/Br and Bmim-COOH/Br were 63.4%, 74.5%, 83.4% and 85.9% at 140 °C and 1.4 MPa, respectively. The selectivities to epichlorohydrin carbonate (ECHC) were over 98% for the four catalysts. The ECH conversion stabilized at 82% for the CSAC tethered Bmim-COOH/Br after 50 h of continuous performance in the packed bed reactor.     

Liquid‐liquid phase split in ionic liquid + toluene mixtures induced by CO2

High pressure carbon dioxide was dissolved in ionic liquid + toluene mixtures to obtain the conditions of pressure and composition where a liquid‐liquid phase split occurs at constant temperature. Ionic liquids (ILs) with four different cations paired with the bis(trifluoromethylsulfonyl)imide ([Tf₂N]^?) anion were selected: 1‐hexyl‐3‐methylimidazolium ([hmim]⁺), 1‐hexyl‐3‐methylpyridinium ([hmpy]⁺), triethyloctylphosphonium ([P₂₂₂₈]⁺), and tetradecyltrihexylphosphonium ([P₆₆₆₁₄]⁺). The solubility of CO₂ was measured in the liquid mixtures at temperatures between 298 and 333 K and at pressures up to 8 MPa, or until the second liquid phase appeared, for initial liquid phase compositions of 0.30, 0.50, and 0.70 mole fraction of IL. Ternary isotherms were compared with the binary solubility of CO₂ in each IL and pure toluene. The lowest pressure for separating toluene in a second liquid phase was achieved by decreasing the temperature of the system, increasing the amount of toluene in the initial liquid mixture and using [hmim][Tf₂N]. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2968–2976, 2015     

Solubility and thermodynamics of lamotrigine in ternary mixtures of ionic liquids ([OMIm][Br]+[HMIm][Br]+water) at different temperatures

Experimental mole fraction solubility of lamotrigine (LTG) in ternary aqueous mixtures of two ionic liquids (ILs), 1-hexyl and 1-octyl-3-methylimidazolium bromide,[HMIm][Br] and [OMIm][Br] were reported at several temperatures T=(293.15 to 313.15) K. The van't Hoff and (Jouyban-Acree-van't Hoff, E-Jouyban-Acree-van't Hoff, e-NRTL, UNIQUAC and Wilson) models were used to correlate the solubility data. The comparison of the models with temperature and solvent composition dependencies shows that the Wilson model has the minimum ARD which are relatively close to those obtained from Jouyban-Acree-van't Hoff and E-Jouyban-Acree-van't Hoff models and maximum ARD belonged to the UNIQUAC model. The order of ARDs for these models is:Wilson < Jouyban-Acree-van't Hoff, E-Jouyban-Acree-van't Hoff < e-NRTL < UNIQUAC. Moreover, the apparent thermodynamic functions, Gibbs free energy, enthalpy and entropy of dissolution and mixing were calculated based on the van't Hoff and Gibbs free energy equations. The strong LTG-ILs interactions and enthalpic contribution of the dissolution process resulted from the calculated thermodynamic functions.     

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.     

Phase equilibrium of two CO2+ biodegradable oil systems up to 72 MPa

A setup based on a static visual synthetic method for determining phase equilibria up to 100 MPa is presented. Solubilities of carbon dioxide (CO₂) in a high-oleic sunflower oil (HOSO) and in an additivated vegetable lubricant (BIO-2T-05) were determined from 298 K to 363 K up to CO₂ mass compositions of 0.42. The experimental device was verified comparing the solubilities of CO₂ in HOSO with values from other laboratory. For both systems, the values of CO₂ solubility show cross-over pressures among the different isotherms. A new equation was used to correlate the solubility data, with deviations in CO₂ mole fraction in the oil-rich phase lower than 1.6%. The prediction ability of Carvalho and Coutinho equation was tested with experimental data. Vapor–liquid–liquid equilibria were also investigated for CO₂ + BIO-2T-05 in the range 288–305 K. Furthermore, densities and viscosities at 0.1 MPa for BIO-2T-05 were measured from 278 K to 373 K.     

Anhydrous proton-conducting glass membranes doped with ionic liquid for intermediate-temperature fuel cells

Proton-conducting glass membranes based on SiO₂ monoliths and a protic ionic liquid (diethylmethylammonium trifluoromethanesulfonate, [dema][TfO]) as the anhydrous proton conductor were studied. The [dema][TfO]/SiO₂ hybrid glass membranes were prepared via a sol–gel process. The stability and ionic conductivity of the glass membrane were investigated. The [dema][TfO]/SiO₂ hybrid glass monoliths exhibit very high anhydrous ionic conductivities that exceed 10^?2 S cm^?1 at 120–220 °C.     

Simple three parameter equations for correlating liquid phase compositions in subcritical and supercritical systems

Two Chrastil type expressions have been developed to model the solubility of supercritical fluids/gases in liquids. The three parameter expressions proposed correlates the solubility as a function of temperature, pressure and density. The equation can also be used to check the self-consistency of the experimental data of liquid phase compositions for supercritical fluid–liquid equilibria. Fifty three different binary systems (carbon-dioxide + liquid) with around 2700 data points encompassing a wide range of compounds like esters, alcohols, carboxylic acids and ionic liquids were successfully modeled for a wide range of temperatures and pressures. Besides the test for self-consistency, based on the data at one temperature, the model can be used to predict the solubility of supercritical fluids in liquids at different temperatures.     

Catalytic performance of zinc containing ionic liquids immobilized on silica for the synthesis of cyclic carbonates

Cycloaddition of carbon dioxide and epoxides was investigated using zinc halide based Lewis acidic ionic liquids (ILs) as catalysts. ILs such as 1-butyl-3-methylimidazolium bromide (BMImBr), 1-butylpyridinium bromide (BPyBr), tetra-n-butylammonium bromide (TBABr) were mixed with zinc halide and supported on silica gel to produce heterogeneous catalysts. Catalytic reaction tests demonstrated that the incorporation of zinc ions can significantly enhance the catalytic activity of the silica-supported ILs for the cycloaddition of CO₂ to epoxides in solvent-free conditions. BPyBr-ZnCl₂/SiO₂ showed the highest propylene carbonate yield of 98% when the reaction was carried out with 0.5 g of catalyst at 120 °C at 1.89 MPa of CO₂ pressure for 4 h. The immobilized zinc containing IL catalyst could be reused for at least four cycles without any considerable loss of its activity.