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1.
The separation of Sc(III) from Y(III), La(III) and Yb(III) in [C8mim][PF6] containing Cyanex 925 has been investigated, and is reported in this paper. A cation exchange mechanism of Sc(III) in [C8mim][PF6] and Cyanex 925 is proposed by study of the influence of anionic and cationic species on the extraction. The coefficient of the equilibrium equation of Sc(III) was confirmed by slope analysis of log DSc vs log [Cyanex 925], and the loading capacity also confirmed the stoichiometry of Cyanex 925 to Sc(III) was close to 3:1. Infrared data for Cyanex 925 saturated with Sc(III) in [C8mim][PF6] indicated strong interaction between P?O of Cyanex 925 and Sc(III). In addition, the relationship between log DSc and temperature showed that temperature had little influence on the extraction process, and the resulting thermodynamic parameters indicated that an exothermic process was involved. Copyright © 2007 Society of Chemical Industry  相似文献   

2.
A reasonable project was presented for the extraction and separation of Pt(IV), Pd(II), Ru(III), and Rh(III) from the mixed imidazolium-based ionic liquids (ILs) [C6mim]Cl, [C6mim][NTf2], and [C6mim][DDTC]. Pt(IV) was first separated from other three platinum group metals with a mixture of [C6mim]Cl and [C6mim][NTf2]. Then, separation of Pd(II) and Ru(III) from Rh(III) was realized by changing the concentration of [C6mim][DDTC]. Back-extraction of Pt(IV), Pd(II), and Ru(III) from loaded hydrophobic phase and the recovery of Rh(III) in aqueous phase were also investigated. Mechanisms between Pd(II)/Ru(III) and [C6mim][DDTC] were further explored using ultraviolet spectrophotometry (UV-Vis), infrared spectrophotometry (FTIR), the method of continuous variations, ab initio quantum chemical studies, and X-ray crystallographic analysis. The results afford more directions for extracting and separating metals by introducing devisable functionalized group into ILs.  相似文献   

3.
《分离科学与技术》2012,47(8):2090-2102
Abstract

Liquid–liquid extraction with imidazolium based ionic liquids ([C4mim][PF6], [C6mim][PF6], and [C8mim][PF6]) is proposed for the separation of furfural or 5-methylfurfural from aqueous solution. Factors affecting the extraction of furfural or 5-methylfurfural have been studied. It was shown that the extraction equilibria can be achieved within 30 min and the process was less affected by the factors such as volume ratio and feed concentration. The partition coefficients of furfural and 5-methylfurfural decreased with increasing temperature. [C6mim][PF6] was found to have the best extraction ability among the three ionic liquids studied. Presence of small amount of NaCl or Na2SO4 in the aqueous phase results in the considerable increase in the partition coefficients of furfural because of the competitive hydration of the salts with furfural. A thermodynamic study revealed that the extraction process was driven mainly by hydrophobic interactions. Further experimental results indicated that furfural can be separated selectively from aqueous furfural/acetic acid mixtures.  相似文献   

4.
《分离科学与技术》2012,47(2):399-410
There is an increased interest in developing accurate tools to relate the physicochemical properties of ionic liquids (ILs) to their microscopic structure as this information is needed to speed up the design of new ionic liquids for chemical and industrial processes. Molecular models can be used for this purpose. We explore here the extended capabilities of a model previously developed in the context of soft-SAFT, by Andreu and Vega in 2007 to reproduce the thermodynamic behavior of imidazolium hexafluorophosphate-based ([Cnmim][PF6]) ionic liquids. The molecular parameters optimized in the previous work have been used here in a transferable manner; some new members of the [Cnmim][PF6] family have also been added, as new recent experimental data has been published. The interfacial tensions have been calculated using a Density Gradient Approach and the results have been compared with available experimental data. The solubility of carbon monoxide and hydrogen in those ILs has been studied in the range of temperatures and pressures of application for separation processes. Binary mixtures with other imidazolium ionic liquids with different anions have been calculated, in a predictive manner. Finally, calculations of mixtures of ionic liquids with water also show very good agreement with experimental data. This work highlights the importance of using a simple but robust thermodynamic model, including the right level of interactions, to accurately describe the properties of these highly non-ideal systems.  相似文献   

5.
BACKGROUND: Enzymes may exhibit enhanced activity, stability and selectivity in ionic liquids, depending on the properties of the liquid. The physical–chemical properties of ionic liquids, however, may be modified by altering the anion or cation in the ionic liquid. This feature is a key factor for realizing successful reactions. In this work, a new ionic liquid, 1‐isobutyl‐3‐methylimidazolium hexafluorophosphate (abbreviated as [i‐C4mim][PF6]), was synthesized and investigated as a novel medium for the transesterification reaction of 2‐phenylethanol with vinyl acetate catalyzed by pseudomonas capaci lipase. As contrasts, the reaction was also carried out in two reference solvents; the isomeric ionic liquid [i‐C4mim][PF6], 1‐butyl‐3‐methylimidazolium hexafluorophosphate (abbreviated as [C4mim][PF6]), and hexanes. RESULTS: As reaction medium, [i‐C4mim][PF6] was best among the three solvents. The initial reaction rate, the equilibrium conversion of 2‐phenylethanol and the half‐lifetime of the lipase in [i‐C4mim][PF6] medium were about 1.5, 1.2 and 3‐fold that obtained in [C4mim][PF6] medium, respectively. The lipase in [i‐C4mim][PF6] medium was recycled 10 times without substantial diminution in activity. CONCLUSION: The ionic liquid [i‐C4mim][PF6] has good biocompatibility, and can be used widely as green media in various biocatalysis reactions to improve the activity and stability of enzymes. Besides hydrophobicity and nucleophilicity, the spatial configuration of ionic liquids is also considered a key factor effecting the behaviour of the enzyme in ionic liquids. Copyright © 2008 Society of Chemical Industry  相似文献   

6.
Abstract

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y by N,N′‐dimethyl‐N,N′‐diphenyl‐3‐oxapentanediamide (DMDPhOPDA) in 1,2‐dichloroethane from aqueous media containing ClO4 ?, PF6 ?, (CF3SO2)2N? anions or by DMDPhOPDA in 1,2‐dichloroethane in the presence of 1‐butyl‐3‐methylimidazolium bis[(trifluoremethyl)sulfonyl]imide ([C4mim][Tf2N]) and 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([C4mim][PF6]) from HNO3 solutions has been studied. The effect of HNO3 concentration in the aqueous phase and that of the extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. The addition of HPF6 and (CF3SO2)2NH or their salts to the aqueous HNO3 or HCl solutions leads to an enchancement of lanthanides (III) extraction by DMDPhOPDA. A considerable synergistic effect was observed in the presence of ionic liquids (IL) in the organic phase containing DMDPhOPDA. This effect is connected with the hydrophobic nature of the IL anion. The distribution of ILs between the equilibrium organic and aqueous phases can govern the extractability of lanthanides (III) in DMDPhOPDA‐IL systems.  相似文献   

7.
BACKGROUND: The improved efficiency of steroid biotransformation using the biphasic system is generally attributed to the positive effect on the solubility of substrate in aqueous media. A promising alternative for the application of organic solvents in biphasic systems is the use of ionic liquids (ILs). This study aims to investigate the applicability of the biphasic ILs/water system for 11α hydroxylation of 16α, 17‐epoxyprogesterone (HEP) by Aspergillus ochraceus. RESULTS: Of the seven ILs tested, [C3mim][PF6] exhibited the best biocompatibility, with markedly improved biotransformation efficiency. In the [C3mim][PF6]‐based biphasic system, substrate conversion reached 90% under the condition in which buffer pH, volume ratio of buffer to ILs, cell concentration, and substrate concentration were 4.8, 10/1, 165 g L?1 and 20 g L?1, respectively. This is more efficient than that of the monophasic aqueous system. The effects of the cations and anions of these ILs on the 11α hydroxylation of 16α, 17‐epoxyprogesterone (HEP) by A. ochraceus is also discussed. CONCLUSION: The above results showed that IL/water biphasic system improved the efficiency of 11α hydroxylation of 16α, 17‐epoxyprogesterone (HEP) by A. ochraceus, thus suggesting the potential industrial application of ILs‐based biphasic systems for steroid biotransformation. © 2012 Society of Chemical Industry  相似文献   

8.
The solvent extraction of Li+ by Cyanex 923 was investigated upon the addition of different imidazolium-based ionic liquids (ILs). The results showed 1-hydroxylethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([HOEmim][NTf2]) can improve the extraction of Li+ most effectively. The fundamental mechanism is that [HOEmim][NTf2] can remarkably enhance the coordination ability of Cyanex 923 to Li+ to form more stable and hydrophobic ion-pair species [Li(Cyanex 923)n][NTf2] (nmax = 3) resulting from the electrostatic interaction and typical hydrogen bonding of IL, and thus facilitating the transfer of Li+ into organic phase. This work has revealed the transfer mechanism of Li+ in a solvent extraction system comprising of IL and neural ligand. The knowledge of the coordination environment of Li+ in the presence of IL also gives us a new insight into the separation of 6Li/7Li. The disadvantage of this process is the loss of IL. However, this study provides guidance for the design of better IL-based systems for the separation of metal ions.  相似文献   

9.
The extraction behavior of U(VI), Pu(IV), and Np(IV) from nitric acid medium has been studied using branched chain di(2-ethylhexyl)isobutyramide (D2EHiBA) dissolved in different room temperature ionic liquids (RTILs) [Cnmim][NTf2] (where n = 4, 6, or 8). Uranium extraction (DU) increased gradually with aqueous phase acidity for the three RTILs used in this study suggesting solvation mechanism. There was a reversal in the extraction behavior of Pu(IV) and Np(IV) from nitric acid medium using D2EHiBA dissolved in RTILs as solvents as compared to the behavior reported in the molecular diluent, n-dodecane, which shows negligible extraction of these metal ions. The extraction of Pu(IV) increased with aqueous phase acidity in different RTILs in the order: [C8mim][NTf2] > [C6mim][NTf2] > [C4mim][NTf2]. The distribution ratio values of these metal ions followed the order: DPu(IV) ≥ DNp(IV) > DU(VI) using D2EHiBA as extractant suggesting that RTILs can modify the extraction behavior of extractants.  相似文献   

10.
《分离科学与技术》2012,47(12):1895-1902
Extraction of uranium (UO22+) and thorium (Th4+) from a nitric acid solution into an imidazolium-type ionic liquids (ILs) of 1-alkyl-3-methylimidazolium hexafluorophosphate ([Cnmim][PF6], n = 6 or 8) was carried out using N,N,N′,N′-tetraoctyl-3-oxapentanediamide (TODGA) as an extractant. It was found that the extraction efficiencies of UO22+ and Th4+ ions are higher in comparison with that done in n-dodecane. The extraction mechanism was deduced by the slope analysis and extraction experiment. Transfer of both ions is assumed to proceed predominantly through the neutral solvation mechanism from nitric acid solution into ILs. The UO22+ ion forms a 1:2 complex with TODGA in ILs at lower acidity, and a 1:1 complex in ILs and in n-dodecane at higher acidity. The Th4+ ion forms a 1:2 complex with TODGA in C6mimPF6 IL or a 1:1 complex in C8mimPF6 IL at lower acidity and a 1:1 complex in both ILs, and n-dodecane at higher acidity. Stripping studies were conducted using sodium salt of EDTA as a stripping ligand. The thermodynamics of extracting UO22+ ions and Th4+ ions from a 3 M HNO3 solution was also studied. The results indicated that the extraction reactions are spontaneous and go through an exothermic process.  相似文献   

11.
The extraction of lanthanides(III) from aqueous nitric acid solutions with N,N,N’,N’-tetra(n-octyl)diglycolamide (TODGA) and with mixtures of TODGA and the hydrophobic ionic liquid (IL) [C4mim][Tf2N] into 1,2-dichloroethane (DCE) has been investigated. The extraction efficiency of Ln(III) ions was greatly enhanced by the addition of a small amount of IL to an organic phase containing TODGA. The synergistic effect comes from the higher hydrophobicity of Ln(III) extracted species formed by TODGA and the weakly coordinating Tf2N? anions compared with those formed by TODGA and NO3? ions as the counter-anions. The partition of Tf2N? anions between the organic and aqueous phases is the dominant factor governing the extractability of lanthanides(III) with mixtures of TODGA and [C4mim][Tf2N]. The extraction of Ln(III) from aqueous nitric acid solutions by TODGA alone and its mixtures with [C4mim][Tf2N] into DCE can be described on the basis of the solvation extraction mechanism. However, in the extraction system with added [C4mim][Tf2N], the partition of Tf2N? between two immiscible phases and the interaction between HTf2N and TODGA in the organic phase should be taken into account. Possible reasons of the antagonistic effect in the TODGA–[C4mim][Tf2N] extraction system are discussed.  相似文献   

12.
《分离科学与技术》2012,47(5):663-669
Both hydrophibic [C8mim][PF6] and [C4mim]Cl/(K2CO3, K2HPO4 or K3PO4) aqueous biphasic system (ABS) were employed for the enrichment of aromatic compounds including nitrobenzene, 4-nitrophenol, phenol and aniline from aqueous solutions. In [C8mim][PF6] enrichment system, the distribution ratio (D) of nitrobenzene and aniline increase with the increasing of pH values of aqueous phase from 2 to 8, but there is no obvious change for 4-nitrophenol and phenol. And the D values of the aromatic compounds decrease with the phase ratio change from 1/5 to 1/30 (IL phase volume/aqueous phase volume). In [C4mim]Cl/(K2CO3, K2HPO4 or K3PO4), the distribution ratio increase with the increasing of the salts concentrations. The distribution ratio order in [C8mim][PF6] and [C4mim]Cl/kosmotropic salt ABS is nitrobenzene > phenol > aniline > 4-nitrophenol. It is expected that these results are promising for the removal of the aromatic compounds from water, especially for sample enrichment in analytical science.  相似文献   

13.
Novel functionalized ionic liquid (IL) combining an imidazolium‐based cation with branched alkyl chain bearing silyl group, 1‐methyl‐3‐(2‐methyl‐3‐(trimethylsilyl)propyl)imidazolium ([Si?C1?C3‐mim]+), and bis(trifluoromethylsulfonyl)imide ([NTf2]?) anion was synthesized and its thermophysical properties (density, viscosity, surface tension, surface entropy and enthalpy, thermal stability) were studied in a wide temperature range and compared with those of ILs having linear alkyl ([Cn‐mim][NTf2]) and siloxane ([(SiOSi)C1mim][NTf2]) side chains. It was found that at 25 °C [Si?C1?C3‐mim][NTf2] is a liquid with dynamic viscosity of 224 cP (224 mPa s) and density of 1.32 g cm?3. The presence of side branched alkyl chain with trimethylsilyl end‐group prevents crystallization of IL and leads to higher viscosities and lower densities in comparison with commonly known [Cn‐mim][NTf2] (n=2–4). As surface excess enthalpy was found to be in the lower end of the usual range of values for ILs, the interactions between silyl‐functionalized cation and [NTf2] anion can be considered as relatively weak. Finally, [Si?C1?C3‐mim][NTf2] was used for the preparation of polymer supported ionic liquid membranes (SILMs) and their CO2 and N2 permeation properties at 20 °C and 100 kPa were determined: permeability PCO2=311, PN2=12 Barrer, diffusivity DCO2=115×1012, DN2=227×1012 m2 s?1 and CO2/N2 permselectivity αCO2/N2=25.3.  相似文献   

14.
The extractive removal of sulfur compounds (S-compounds) from Dongying and Liaohe diesel fuels with [BF4]^--based ionic liquids were systematically investigated. The results show that the absorption capacity of an ionic liquid for the S-compounds in diesel fuels relies on its structure and its size. In the case of the two examined diesel fuels, both elongating the cation tail length and increasing the mass ratio of ionic liquid/diesel fuel promote the desulfurization ability of the examined ionic liquids. The results also show that imidazolium-based ionic liquids display higher extraction efficiencies than pyridinium-based ionic liquids, presumably owing to the fact that the rings of the S-compounds are similar to the imidazolium head ring. With the 1 : 1 mass ratio of ionic liquid/diesel fuel, the rates of the first desulfurization of Dongying and Liaohe diesel fuels using [C8mim][BF4] amount to 29.96% and 39.76%, suggesting that [C8mim][BF4] is a promising extractant for desulfurization of these diesel fuels.  相似文献   

15.
《分离科学与技术》2012,47(8):1166-1174
The inability of traditional hydrodesulfurization (HDS) to effectively remove aromatic sulfur compounds such as thiophene (TS) and dibenzothiophene (DBT) has called for alternative methods to be studied, among which extractive desulfurization using ionic liquids (ILs) has attracted increasing interest. In this work, we prepared a new IL, 1-butyl-3-methylimidazolium dicyano(nitroso)methanide ([C4mim][dcnm]), and investigated its extractive desulfurization for both model oils and real FCC gasoline, where model diesel fuel was composed of n-hexane and droplets of DBT and model gasoline was composed of n-hexane, toluene and droplets of TS. Other three [dcnm]-based ILs, 1-ethyl-3-methylimidazolium dicyano(nitroso)methanide ([C2min][dcnm]), N-ethyl-N-methylpyrrolidinium dicyano(nitroso)methanide ([C2mpyr][dcnm]), and N-butyl-N-methylpyrrolidinium dicyano(nitroso)methanide ([C4mpyr][dcnm]), were also comparatively investigated. These [dcnm]-based ILs have low viscosity which favors the mass transfer and reduces the extractive equilibrium time, also are fluorine-free which avoids the corrosion by hydrogen fluoride from anion decomposition that occurs generally in fluorine-containing ILs. The desulfurization ability follows the order [C4min][dcnm] > [C4mpyr][dcnm] > [C2min][dcnm] > [C2mpyr][dcnm]. Typically, [C4min][dcnm] is capable of removing 66% DBT and 53% TS from their respective model oils after one cycle (initial 500 ppm S, 25°C, 15 min, mass ratio of IL:oil 1:1), and < 10 ppm S-content can be obtained after 4 cycles. It was observed interestingly that the S-content in real FCC gasoline can be reduced from initial 250 ppm to < 30 ppm after 6 cycles using [C4min][dcnm] as extractive reagent, which is better than some previous results for real feedstocks. Mutual solubility, extractive temperature, IL:oil mass ratio, multiple extraction, initial S-content, and regeneration were also studied. These dcnm-based ILs are competitive extractive reagents compared with some other ILs to remove those aromatic S-compounds from fuel oils.  相似文献   

16.
The acylation of ethane-1,2-diol catalyzed by lipase (Novozym 435) with ethyl acetate in 1-butyl-3-methyl imidazolium hexaflorophosphate [BMIM][PF6] and 1-butyl-3-methyl imidazolium tetrafloroborate [BMIM][BF4] was studied. It was demonstrated that the activity of the enzyme in [BMIM][BF4] was very low for this reaction, while it was very active in [BMIM][PF6]. Both the equilibrium conversion and the selectivity to ethane-1,2-diol monoacetate (EDMA) in [BMIM][PF6] could be considerably higher than that at solvent-free condition. The IL and enzyme have synergetic effect to prevent thermal deactivation of the enzyme. Addition of small amount of water in [BMIM][PF6] could enhance the conversion and selectivity to EDMA.  相似文献   

17.
In this study, an ionic liquid (IL), 1-butyl-2,3-dimmmethylimidazolium hexafluorophosphate ([Bmmim][PF6]), was used in combination with a composite solvent of methyl acetate and n-heptane to enhance the oil extraction from oily sludge. The oil recovery increased by approximately 15% compared with that of solvent extraction without [Bmmim][PF6] at the optimal ratios of IL to sludge and solvents to sludge, which were at 2:5 (M/M) and 4:1 (V/M), respectively. The saturate, aromatic, resin and asphaltene (SARA) analysis revealed that the recovery of resins and asphaltenes was increased by 14% and 38%, respectively, in the solvent extraction with the addition of [Bmmim][PF6]. [Bmmim][PF6] maintained a good performance after its reuse four times. The addition of [Bmmim][PF6] changed the adhesion forces between oil and soil. The IL-assisted solvent extraction procedure followed the pseudo second-order kinetic model, while the unassisted solvent extraction procedure followed the pseudo first-order kinetic model. The results also demonstrated that [Bmmim][PF6] decreased the solvent consumption by approximately 60% each time. Additionally, [Bmmim][PF6] can be easily separated. The results suggested that enhancing the solvent extraction with this IL is a promising way to recover oil from oily sludge with a higher oil recovery rate and lower organic solvent consumption than those with the unassisted solvent extraction method.  相似文献   

18.
The activity and stability of lipase from Candida antarctica were investigated in the kinetic resolution of (R,S)-1-phenylethanol with vinyl acetate using ionic liquids (ILs) as reaction media. Among ILs tested, the highest activity of lipase was observed in [Edmim][Tf2N]. In hydrophobic ILs such as [Edmim][Tf2N], [Emim][Tf2N] and [Pmim] [PF6], lipase could retain its activity after 5 times reuse, while the activity of lipase in hydrophilic ILs and organic solvents was drastically decreased. The activities of lipase in [Edmim][Tf2N], [Emim][Tf2N] and [Pmim][PF6] were also well maintained after 1 day incubation at 80 °C. The lipase suspended in [Edmim][Tf2N] could be successfully reused 6 times without loss of activity.  相似文献   

19.
《分离科学与技术》2012,47(8):1208-1214
The FeCl3-containing Lewis-acidic ionic liquids (ILs) [C6mim]Cl/FeCl3(1:1.5), [C6mim]Cl/FeCl3(1:2), [C8mim]Cl/FeCl3(1:1.5), and [C8mim]Cl/FeCl3(1:2) were used as extractants for desulfurization of model fuel and gasoline fuel, respectively. The results demonstrate that these ILs are effective for the removal of sulfur compounds from model fuel under different mass ratio of IL to model fuel (1:1, 1:3, 1:5, 1:10) at 25°C. The extractive performance of ILs increased as the molar ratio of FeCl3 to [Cnmim]Cl(n = 6, 8) varied from 1:1 to 1:2. The selectivity of sulfur compounds by extraction process followed the order of dibenzothiophene (DBT)>benzothiophene (BT) > 4,6-dimethyldibenzothiophene (4,6-DMDBT). The sulfur removal of gasoline fuel containing sulfur content of 440.3 ppmw could be up to 85.8%; that is to say that the sulfur content of gasoline fuel varied from 440.3 ppmw to 62.4 ppmw after one extraction stage. Moreover, the [C6mim]Cl/FeCl3(1:2) can be recycled for at least 4 times with a little decrease in the desulfurization activity.  相似文献   

20.
Liquid-liquid extraction of U(VI) from nitric acid medium was carried out using three different class of CHON based molecular extractants namely monoamide, malonamide, and diglycolamide present in 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide ([C4mpip][NTf2]) ionic liquid. The extractants investigated were di-n-hexyloctanamide (DHOA), N,N-dimethyl-N,N-di-octyl-2-(2-hexyloxylethyl)malonamide (DMDOHEMA) and N,N,N’,N’-tetra(ethylhexyl)diglycolamides (T2EHDGA). The extraction behavior of uranium(VI) in ionic liquid medium was investigated as a function of various parameters, such as the duration and temperature of equilibration, aqueous phase concentrations of feed acid, extractant, NaNO3, and ionic liquid cation, etc. The extraction of U(VI) observed in these systems were compared with each other and the distribution ratios of U(VI) decreased in the order T2EHDGA > DMDOHEMA > DHOA. The slope analysis of the extraction data was carried out to understand the mechanistic aspects of extraction. The extraction of U(VI) observed in [C4mpip][NTf2] ionic liquid was also compared with pyrrolidinium ([C4mpyr][NTf2]) and imidazolium ([C4mim][NTf2]) based ionic liquids under identical experimental condition.  相似文献   

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