Performance and pressure drop of CO2 absorption into task-specific and halide-free ionic liquids in a microchannel

The gas–liquid two-phase flow pattern, absorption rate and pressure drop of CO₂ absorbed into the aqueous solution of the task-specific ionic liquids (1-aminopropyl-3-methylimidazole tetrafluoroborate [Apmim][BF₄] and 1-hydroxyethyl-3-methylimidazole tetrafluoroborate [OHemim][BF₄]) and halide-free ionic liquid 1-butyl-3-methylimidazolium methylsulfate [Bmim][CH₃SO₄] were investigated in a microreactor. The absorption mechanism of the three ionic liquids was analyzed employing the ¹³C NMR spectroscopy. The [Apmim][BF₄] was found to have the best ability of CO₂ capture compared with the other two ionic liquids, as chemical absorption occurred between [Apmim][BF₄] and CO₂, while only physical absorption took place between [OHemim][BF₄]/[Bmim][CH₃SO₄] and CO₂. The sequence of CO₂ absorption rate in three ionic liquids aqueous solutions is: [Apmim][BF₄] > [Bmim][CH₃SO₄] > [OHemim][BF₄]. Furthermore, the effects of gas–liquid flow rate and ionic liquids concentration on CO₂ absorption rate and pressure drop were studied, the pressure drop models based on various flow patterns were proposed.     

Physical and electrochemical properties of 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium iodide,and 1-butyl-3-methylimidazolium tetrafluoroborate

The density, viscosity, refractive index, heat capacity, heat of dilution, ionic conductivity, and electrochemical stability of 1-butyl-3-methylimidazolium bromide ([bmim][Br]), 1-butyl-3-methylimidazolium iodide ([bmim][I]), and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) were measured at room temperature or over a temperature range of 293.2 to 323.2 K. The density and refractive index values of [bmim][I] appeared to be the highest among three ionic liquids (ILs). However, the experimental viscosity values of [bmim][Br] were higher than those of [bmim][BF₄], while the heat capacities and heats of dilution of [bmim][BF₄] were higher than those of [bmim][Br]. The cyclic voltammogram of [bmim][br] and [bmim][BF₄] indicated electrochemical windows in the stability range from 2.7 V of [bmim][[Br] to 4.7 V of [bmim][BF₄].     

Effect of small amount of water on the dynamics properties and microstructures of ionic liquids

A series of systems of 1‐butyl‐3‐methylimidazolium acetate ([Bmim][Ac]), 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim][BF₄]), and 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim][Tf₂N]) with a small amount of water were simulated. Viscosities of systems were obtained by nonequilibrium molecule dynamics simulation and the results show that the viscosities change in different ways: for [Bmim][BF₄] and [Bmim][Tf₂N], viscosities decrease rapidly in the first stage, and then decrease slowly with the increase of water content. But for [Bmim][Ac], the viscosities increase first and then decrease. The unique phenomenon of [Bmim][Ac] can be attributed to the formation of chain‐like structure of anion???water???anion???. Hydrogen bond (HB) interaction between ion pairs is weakened, but the number of HB between water and anions increases with increase of water content. Besides, the microstructures of water in ionic liquids‐water systems were compared and found that the distribution of water is more concentrated in [Bmim][Tf₂N]‐H₂O system, while it is isotropy in [Bmim][Ac]‐H₂O system. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2248–2256, 2017     

Solubility of CO2 in three cellulose-dissolving ionic liquids

The solubility of CO₂ in three cellulose-dissolving ionic liquids (1-ethyl-3-methylimidazolium diethylphosphate, [Emim][DEP], 1-allyl-3-methylimidazolium chloride, [Amim][Cl], and 1-butyl-3-methylimidazolium chloride, [Bmim][Cl]) at temperatures within 298 and 356 K and pressures up to 6.5 MPa was determined using a Van Ness-type apparatus (static isochoric). It was demonstrated that this device can work in isothermal and isoplethal modes, being the latter faster and more precise. Moreover, it was possible to determine CO₂ solubilities in metastable liquid [Bmim][Cl]. Experimental data were modeled using the Extended Henry's law correlation and the group contribution equation of state. New parameters for the binary interaction of CO₂ with ionic liquid groups were calculated.     

Surface tension and viscosity of 1-butyl-3-methylimidazolium iodide and 1-butyl-3-methylimidazolium tetrafluoroborate, and solubility of lithium bromide+1-butyl-3-methylimidazolium bromide in water

The surface tension and viscosity of 1-butyl-3-methylimidazolium iodide ([bmim][I]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) were measured over a temperature range of 298. 15 to 323.15 K. It was found that both the viscosity and surface tension decrease with increasing temperature and that the surface tension and viscosity values of [bmim][I] were higher than those of [bmim][BF₄]. Additionally, the solubility of lithium bromide (2)+1-butyl-3-methylimidazolium bromide ([bmim][Br]) (3) in water (1) was measured at three different mass ratios (w₂/w₃=4 and 7, w₃=0) by using a visual polythermal method. The solubility of the suggested systems was better than that of lithium bromide in water.     

Phase equilibria and structural properties of thiophene/[Bmim][BF4]: A molecular insight from monte carlo simulations

The phase equilibria of thiophene in 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim][BF₄]) is calculated by Monte Carlo simulation in Gibbs ensemble using a united atom force field. The liquid density of studied ionic liquid and the vapor pressure of thiophene in [Bmim][BF₄] were compared with corresponding experimental data reported in the literature, and a good agreement was obtained. In order to describe the solubility of thiophene in this ionic liquid, we have calculated the radial distribution functions and spatial distribution functions of thiophene/IL mixtures to study the interaction of thiophene with cations and anions of [Bmim][BF₄] in the liquid phase. The local composition concept in fluid was also examined to give further insight into the liquid structure. The results show that thiophene is well organized around the terminal carbon atom of the butyl or methyl chain attached to the imidazolium ring of cations and tends to adopt a symmetrically distribution on the anions. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3916–3924, 2014     

Efficient recovery of ionic liquid by electrodialysis in the acid hydrolysis process

Electrodialysis (ED) has been recently known as a highly effective technique to remove and recover ionic liquids from aqueous solution. When a conventional electrolyte solution for the ED process containing Na₂SO₄ was used, a recovery ratio of an acidic IL, 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim][HSO₄]), was 90%. On the other hand, the value clearly increased to 96% when we employed [Bmim][HSO₄] as the electrolyte solution. In an acid hydrolysis of bagasse using the IL under microwave irradiation, the recovery ratio maintains 96%, irrespective of reaction time. This demonstrates the applicability of the proposed ED system in biomass processing.     

Reverse atom transfer radical polymerization of methyl methacrylate in imidazolium ionic liquids

Reverse atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) employing 2,2-azobisisobutyronitrile (AIBN)/CuCl₂/bipyridine(bipy) as the initiating system was approached at 80 °C in two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate ([C₄mim][BF₄]) and 1-dodecyl-3-methylimidazolium tetrafluoroborate ([C₁₂mim][BF₄]), respectively. The polymerization in [C₁₂mim][BF₄] proceeded in a well-controlled manner as evidenced by kinetic studies, end group analysis, chain extension, and block copolymerization results, but not in [C₄mim][BF₄] presumably due to poor solubility of PMMA in it. The kinetic study of reverse ATRP of MMA in recycled [C₁₂mim][BF₄] suggested that this ionic liquid could be re-used as reaction solvent after simple purification, without affecting the living nature of polymerization.     

Improving Physical Adsorption of CO2 by Ionic Liquids‐Loaded Mesoporous Silica

CO₂ sorption capacities of the neat and silica‐supported 1‐butyl‐3‐methylimidazolium‐based ionic liquids (ILs) were measured under atmospheric pressure. The silica‐supported ILs were synthesized by the impregnation‐vaporization method and charactrized by N₂ adsorption/desorption and thermogravimeteric analysis (TGA). Evaluation of the effects of influential factors on sorption capacity demonstrated that by increase of the temperature, flow rate, and the weight percentage of ILs in sorbents, the sorption capacity decreases. Among the sorbents, [Bmim][TfO] and SiO₂‐[Bmim][BF₄](50) had the highest capacity. By increasing the IL portion in SiO₂‐[Bmim][BF₄], the selectivity for CO₂ to CH₄ could be improved. The CO₂‐rich sorbents could be easily recycled.     

Optimization of [Bmim][HSO4]-Catalyzed Transesterification of Camelina Oil

1-Butyl-3-methylimidazolium hydrogen sulfate ([Bmim][HSO₄]) is utilized to catalyze transesterification of camelina oil with methanol. The major compositions of camelina biodiesel are saturated fatty acid esters (C16:0, C18:0), monounsaturated, and polyunsaturated fatty acid esters (C18:2, C18:3). The effects of reaction temperature, reaction time, M_methanol:M_{Camelina oil}, and M_[Bmim][HSO4]:M_{Camelina oil} on biodiesel production are investigated in detail, and a general mathematical model is developed to well predict the biodiesel yield. Also, [Bmim][HSO₄] is thermally stable to recycle for four times with a high biodiesel yield. The fuel properties of camelina biodiesel are all comparable to the American Society for Testing Materials (ASTM) standards.     

Critical properties and acentric factors of ionic liquids

Since most ionic liquids (ILs) decompose before reaching their critical state, the experimental measurement of their critical properties are not possible. In this study, the critical temperatures, critical pressures and acentric factors of ten commonly investigated ILs were determined by making an optimum fit of the calculated vapor-liquid equilibrium data of binary mixtures of CO₂+IL to the experimental values found in literature. For this purpose, the Peng-Robinson equation of state (PR EoS) and the differential evolution optimization method were used. The ILs considered were 1-ethyl-3-methylimidazolium hexafluorophosphate ([emim][PF₆]), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([emim][Tf₂N]), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([bmim][Tf₂N]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([hmim][BF₄]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([hmim][PF₆]), 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([hmim][Tf₂N]), 1-octyl-3-methylimidazolium tetrafluoroborate ([omim][BF₄]) and 1-octyl-3-methylimidazolium hexafluorophosphate ([omim][PF₆]). To evaluate the ability of the determined parameters in predicting the phase behavior of systems other than the systems that were used for parameter optimization, both sets of parameters obtained in this work and that of Valderrama et al. were used to predict bubble-point pressures of CHF₃+[bmim][PF₆] (by using the PR EoS and the Soave-Redlich-Kwong equation of state. The bubble-point pressures of CO₂+IL systems optimized in this study by the PR EoS were also determined using the Soave-Redlich-Kwong equation of state (SRK EoS). In addition, liquid densities of pure ILs were predicted using a generalized correlation proposed by Valderrama and Abu-Shark. In all cases, the various predicted properties of these ten ILs, were in better agreement with the experimental data, using the critical properties and acentric factor obtained in this study, compared to the values suggested by Valderrama et al.     

Gold-ionic liquid nanofluids with preferably tribological properties and thermal conductivity

Gold/1-butyl-3-methylimidazolium hexafluorophosphate (Au/[Bmim][PF₆]) nanofluids containing different stabilizing agents were fabricated by a facile one-step chemical reduction method, of which the nanofluids stabilized by cetyltrimethylammonium bromide (CTABr) exhibited ultrahighly thermodynamic stability. The transmission electron microscopy, UV-visible absorption, Fourier transform infrared, and X-ray photoelectron characterizations were conducted to reveal the stable mechanism. Then, the tribological properties of these ionic liquid (IL)-based gold nanofluids were first investigated in more detail. In comparison with pure [Bmim][PF₆] and the nanofluids possessing poor stability, the nanofluids with high stability exhibited much better friction-reduction and anti-wear properties. For instance, the friction coefficient and wear volume lubricated by the nanofluid with rather low volumetric concentration (1.02 × 10^-3%) stabilized by CTABr under 800 N are 13.8 and 45.4% lower than that of pure [Bmim][PF₆], confirming that soft Au nanoparticles (Au NPs) also can be excellent additives for high performance lubricants especially under high loads. Moreover, the thermal conductivity (TC) of the stable nanofluids with three volumetric fraction (2.55 × 10^-4, 5.1 × 10^-4, and 1.02 × 10^-3%) was also measured by a transient hot wire method as a function of temperature (33 to 81°C). The results indicate that the TC of the nanofluid (1.02 × 10^-3%) is 13.1% higher than that of [Bmim][PF₆] at 81°C but no obvious variation at 33°C. The conspicuously temperature-dependent and greatly enhanced TC of Au/[Bmim][PF₆] nanofluids stabilized by CTABr could be attributed to micro-convection caused by the Brownian motion of Au NPs. Our results should open new avenues to utilize Au NPs and ILs in tribology and the high-temperature heat transfer field.     

Retention mechanism of some solutes using ionic liquids as mobile phase modifier in RP-high-performance liquid chromatography (HPLC)

Two kinds of ionic liquid, 1-Hexyl-3-methylimidazolium tetrafluoroborate ([Hmim][BF₄]) and 1-Methyl-3-octylimidazolium tetrafluoroborate ([Omim][BF₄]), were used as additives in the linear solvation energy relationships (LSERs) model to investigate the fundamental chemical interactions governing the retention of nine aromatic compounds in acetonitrile/water mobile phases on a C₁₈ column. The effects of the [Hmim][BF₄] and [Omim][BF₄] were compared and the ability of the LSERs to account for the chemical interactions underlying solute retention was shown. A comparison of predicted and experimental retention factors suggests that LSER formalism is able to reproduce adequately the experimental retention factors of the solutes studied in the different experimental conditions investigated.     

Physical and electrochemical properties of lithium-doped 1-butyl-3-methylimidazolium salts

Two well known room temperature ionic liquids (RTILs), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF₄]) and 1-butyl-3-methylimidazolium iodide ([BMIm][I]), were synthesized. Their physical properties such as reflective indices, densities, viscosities, heat capacities, and heats of dilution were measured. The overall properties of [BMIm][BF₄] obtained after two-step reactions were superior to those of the IL with a halide anion. The incorporation of lithium ions using lithium tetrafluoroborate (LiBF₄) in each IL was carried out and ionic conductivities as a function of temperature and Li ion concentration were investigated. The isothermal conductivity graph showed a parabolic curve shape suggesting that the maximum values exist at a specific concentration condition while they continuously increased as the temperature increased. The conductivities reached as high as 10⁻³ S·cm⁻¹.     

离子液体催化聚乳酸丁醇醇解反应

以离子液体[Bmim][OAc]为反应介质和催化剂, 对聚乳酸 (PLA)丁醇醇解反应进行了研究。考察了反应温度、反应时间、离子液体用量、丁醇(n-butanol)用量对反应结果的影响。得到较佳工艺条件为:反应温度为150℃、反应时间为3 h、m([Bmim][OAc]):m(PLA)=0.2:1、n(n-butanol):n(PLA)=5:1。在上述条件下, PLA醇解反应转化率≥81%, 乳酸正丁酯收率≥70%。采用FT-IR技术对产品的结构进行了表征。 离子液体的回用性能结果表明:[Bmim][OAc]重复利用6次后, PLA转化率和乳酸正丁酯收率无明显变化。     

Fabrication of silver nanoparticles via self-regulated reduction by 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate

Silver nanoparticles exhibiting antimicrobial properties via self-regulated reduction were successfully prepared by using hydroxylated ionic liquids in an aqueous phase without additives. A new water-phase synthesis of silver nanoparticles using 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate ([HEMIm][BF₄]) and 1-(2′-hydroxyethyl)-2-methyl-3-dodecylimidazolium chloride ([C₁₂HEMIm][Cl]) was described. 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate serves as both a reductant and a stabilizer in this fabrication. Furthermore, we presented the antimicrobial properties of the resulting silver nanoparticles through the minimal inhibitory concentrations (MIC) test.     

Novel homogeneous gel fibers and capillaries from blend of titanium tetrabutoxide and siloxane functionalized ionic liquid

The preparation of ionogels by sol–gel processing has attracted much attention, because the final ceramic materials combine properties of both inorganic matrix (thermal and mechanical stability) and the ionic liquid (ionic conductivity). The aim of this study was to combine different imidazolium based ionic liquids (1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF₄], 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM][BF₄], 1-decyl-3-methylimidazolium tetrafluoroborate [DMIM][BF₄] and 1-methyl-3-[3′-(triethoxysilyl)propyl]imidazolium chloride MTICl) with titanium(IV) butoxide to prepare homogenous hybrid fibers through aqueous sol–gel reaction. The study showed that ionic liquid miscibility with metal alkoxide plays an important role in the preparation of homogenous fibers. Unlike simple imidazolium salts functionalized ionic liquid was dispersed homogenously in fibers, but the main advantage is derived from its chemical structure. New stable ionic liquid can be involved in sol–gel processes through ethoxy groups and as a result it associates with titanium alkoxide network by covalent bonding providing non-leaking ceramic hybrid material. Indirect and direct characterization studies of the product were carried out by energy-dispersive X-ray spectroscopy (EDX), silicon-29 nuclear magnetic resonance spectroscopy (²⁹Si NMR), scanning electron microscopy (SEM) and optical microscopies; also infrared spectra (IR) were recorded. Thermal analyses were performed by differential scanning calorimetry (DSC).     

Measurement of activity coefficients at infinite dilution for hydrocarbons in imidazolium-based ionic liquids and QSPR model

The separations of olefin/paraffin, aromatic/aliphatic hydrocarbons or olefin isomers using ionic liquids instead of volatile solvents have interested many researchers. Activity coefficients γ ^∞ at infinite dilution of a solute in ionic liquid are generally used in the selection of solvents for extraction or extractive distillation. In fact, the measurement of γ ⁻⁸ by gas-liquid chromatography is a speedy and cost-saving method. Activity coefficients at infinite dilution of hydrocarbon solutes, such as alkanes, hexenes, alkylbenzenes, styrene, in 1-allyl-3-methylimidazolium tetrafluoroborate ([AMIM][BF₄]) and 1-butyl-3-methyl imidazolium hexafluorophosphate ([BMIM][PF₆]), 1-isobutenyl-3-methylimidazolium tetrafluoroborate ([MPMIM][BF₄]) and [MPMIM][BF₄]-AgBF₄ have been determined by gas-liquid chromatography using ionic liquids as stationary phase. The measurements were carried out at different temperatures from 298 to 318 K. The separating effects of these ionic liquids for alkanes/hexane, aliphatic hydrocarbons/benzene and hexene isomers have been discussed. The hydrophobic parameter, dipole element, frontier molecular orbital energy gap and hydration energy of these hydrocarbons were calculated with the PM3 semi-empirical quantum chemistry method. The quantitative relations among the computed structure parameters and activity coefficients at infinite dilution were also developed. The experimental activity coefficient data are consistent with the correlated and predicted results using QSPR models.     

Disposable screen-printed antimony film electrode modified with carbon nanotubes/ionic liquid for electrochemical stripping measurement

In this paper, two disposable screen-printed antimony film electrodes (SPSbFEs) modified with multi-walled carbon nanotubes (MWCNTs) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄), respectively for electrochemical stripping measurement are introduced. The modified screen-printed electrode substrate was prepared by homogeneously doping the attractive material into the graphite-based printing ink, and then an antimony film was in situ formed by simultaneously electrodepositing the antimony precursor with interesting analytes on the modified substrate. The electroanalytical performance of the modified SPSbFE for heavy metals based on the anodic stripping protocol was intensively evaluated. It was found that stripping voltammetric measurements of mercury (II) and lead (II) at the modified SPSbFEs resulted in good peaks with very low background contribution. In comparison with the bare SPSbFE, the modifications of both MWCNTs and [Bmim]BF₄ were demonstrated providing more sensitive responses. The results indicated that the SPSbFE modified with 4 wt% [Bmim]BF₄ exhibited well linear behavior in the mercury (II) concentration range from 20 to 140 μg/L (R² = 0.998) with a detection limit of 0.36 μg/L (S/N = 3) under a 120 s accumulation, and good repeatability with a relative standard deviation (RSD) of 4.16% (40 μg/L, n = 12). The proposed electrodes, as new styles of “mercury-free” electrodes, also exhibit encouraging properties for measurements of practical samples.     

Controllable growth of TiO2-B nanosheet arrays on carbon nanotubes as a high-rate anode material for lithium-ion batteries

To meet the increasing demands of electrode materials with high capacity and fast charge–discharge capability for next-generation lithium-ion batteries (LIBs), well-designed nanostructures of carbon-supported metal oxides have been extensively investigated. Here we design and fabricate a novel hybrid nanoarchitecture of carbon nanotubes (CNTs) coated with TiO₂-B nanosheets (CNTs@TiO₂-B NSs) by using an imidazolium-based ionic liquid of [Bmim][BF₄] as a guiding agent. The ionic liquid of [Bmim][BF₄] interacts with CNTs via cation-π interactions and further guides the in situ growth of TiO₂-B nanosheet arrays onto CNTs. The resultant hybrid nanoarchitecture possesses a large specific surface area, porous nature, and abundant electron/lithium pathways. These features combined with the fast pseudocapacitive behavior and the reduced ion-diffusion length of TiO₂-B nanosheet arrays, contribute to a high reversible capacity and superior rate capability for LIB applications.