Solvent extraction of U(VI) by trioctylphosphine oxide using a room-temperature ionic liquid

The unique physical and chemical properties of room-temperature ionic liquids(RTILs) have recently received increasing attention as solvent alternatives for possible application in the field of nuclear industry, particularly in liquid-liquid separations of radioactive nuclides. We investigated solvent extraction of U(VI) from aqueous solutions into a commonly used ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([C4mim][NTf2]) using trioctylphosphine oxide(TOPO) as an extractant. The effects of contact time, TOPO concentration, acidity, and nitrate ions on the U(VI) extraction are discussed in detail. The extraction mechanism was proposed based on slope analysis and UV-Vis measurement. The results clearly show that TOPO/[C4mim][NTf2] provides a highly efficient extraction of U(VI) from aqueous solution under near-neutral conditions. When the TOPO concentration was 10 mmol/L, the extraction of 1 mmol/L U(VI) was almost complete( 97%). Both the extraction efficiency and distribution coefficient were much larger than in conventional organic solvents such as dichloromethane. Slope analysis confirmed that three TOPO molecules in [C4mim][NTf2] bound with one U(VI) ion and one nitrate ion was also involved in the complexation and formed the final extracted species of [UO2(NO3)(TOPO)3]+. Such a complex suggests that extraction occurs by a cation-exchange mode, which was subsequently evidenced by the fact that the concentration of C4mim+ in the aqueous phase increased linearly with the extraction percent of U(VI) recorded by UV-Vis measurement.     

Fluorous ionic liquids as solvents for the liquid-liquid extraction of metal ions by macrocyclic polyethers

The predominant mode of strontium ion transfer from aqueous nitrate media into a series of 1-fluoroalkyl-3-methylimidazolium bis[(trifluoromethylsulfonyl)]imides containing dicyclohexano-18-crown-6 (DCH18C6) is shown to shift from cation exchange to strontium nitrato-crown ether complex partitioning as the length of the fluoroalkyl substituent is increased. Fluoroalkyl substituents are shown to be only slightly more effective than their non-fluorous analogs at inducing this shift. At the same time, the fluorinated ionic liquids (ILs) yield strontium distribution ratios as much as an order of magnitude lower than the corresponding 1-alkyl-3-methylimidazolium (C_nmim⁺) salts. Fluorous ILs thus appear to offer no compelling advantages over C_nmim⁺ ionic liquids as extraction solvents.     

Stir bar sorptive extraction for trace analysis

Stir bar sorptive extraction (SBSE) was introduced in 1999 as a solventless sample preparation method for the extraction and enrichment of organic compounds from aqueous matrices. The method is based on sorptive extraction, whereby the solutes are extracted into a polymer coating on a magnetic stirring rod. The extraction is controlled by the partitioning coefficient of the solutes between the polymer coating and the sample matrix and by the phase ratio between the polymer coating and the sample volume. For a polydimethylsiloxane coating and aqueous samples, this partitioning coefficient resembles the octanol-water partitioning coefficient. In comparison to solid phase micro-extraction, a larger amount of sorptive extraction phase is used and consequently extremely high sensitivities can be obtained as illustrated by several successful applications in trace analysis in environmental, food and biomedical fields. Initially SBSE was mostly used for the extraction of compounds from aqueous matrices. The technique has also been applied in headspace mode for liquid and solid samples and in passive air sampling mode. In this review article, the principles of stir bar sorptive extraction are described and an overview of SBSE applications is given.     

Bis(2-ethylhexyl)sulfoxide as an extractant for americium(III) from aqueous nitrate media

Solven extraction separation of americium(III) from dilute aqueous nitrate media into n-dodecane by bis(2-ethylhexyl)sulfoxide (BESO) has been investigated over a wide range of experimentgal conditioins. Very poor extractablity of Am(III), necessitated the use of calcium nitrate as the salting-out agent. Effects of certain variables such as acidity, extractant concentration, salting-out agent concentration, organic diluents on the metal extraction by BESO have been examined in detail. By increasing the concentration of BESO in organic phase or calcium nitrate in aqueous phase, nearly quantitative extraction of americium even from moderate acidity is accomplished. Slope analyses applied to Am(III) distribution experiments from acidic nitrate solutions indicate predominant formation of the risolvated organic phase complex, Am(NO₃)₃)·3BESO for which equilibrium constant is found to be, log K_x=1.99. Extraction behavior of Am(III) has also been evlauated in the presence of several water-miscible polar organic solvents to stuy their possible synergistic effects on its extraction. Extractability of americium increased 5 to 10-fold withi increasing conentration of some of these additives, with maximum enhancement being observed in the presence of acetone or acetonitrile. Recovery of BESO from loaded americium is easily obtained using dilute nitric acid as the strippant.     

Separation of AM(III) by extraction from nitrate solutions using some quaternary benzylammonium salts

Benzyldimethyldodecylammonium nitrate and benzyltrioctylammonium nitrate were used for the extraction of Am(III) from aqueous nitrate solutions. The dependence of the extraction performance for Am(III) on the concentration of nitric acid, the kind and concentration of salting-out agents in the aqueous phase, and the kind of solvent was investigated. Americium is extracted by the above quarternary salts as a R₄NAm(NO₃)₄ associate. The extraction of Am(III) is compared with the extraction of lanthanides. The high differences in the distribution coefficients for lanthanides and americium can be utilized for the separation of lanthanides and americium.     

Verteilung Von Uran(IV) Zwischen Wässriger Salpetersäure und Lösungen Des Nitratsalzes Des Primären Amins Primene JM-T

The distribution of uranium(IV) between aqueous nitric acid solutions and solutions of the nitrate salt of the primary amine Primene JM-T in various diluents is described. The influence of the concentration of the acid, nitrate and perchlorate in the aqueous phase is studied, taking into account the complex composition of uranium(IV) in the aqueous phase and the acid content of the organic phase. The uranium(IV) extraction may be explained by the competition between metal complex and nitric acid for the extracting agent. The absorption spectra of the organic phase and the results of maximum loading experiments indicate that the uranium(IV) species in the organic phase is the bis-alkylammonium-hexanitrato-uranium(IV) complex [(RNH₃)₂U(NO₃)₆].      

Selective extraction of iron(III) from aqueous nitrate solution in the presence of cobalt(II), copper(II) and nickel(II) ions using bis(delta2-2-imidazolinyl)-5,5'-dioxime.

The feasibility of using bis(delta2-2-imidazolinyl)-5,5'-dioxime (H2L) for the selective extraction of iron(III) from aqueous solutions was investigated by employing an solvent-extraction technique. The extraction of iron(III) from an aqueous nitrate solution in the presence of metal ions, such as cobalt(II), copper(II) and nickel(II), was carried out using H2L in binary and multicomponent mixtures. Iron(III) extraction has been studied as a function of the pH, equilibrium time and extractant concentration. From the extracted complex species in the organic phase, iron(III) was stripped with 2 M HNO3, and later determined using atomic-absorption spectrometry. The extraction was found to significantly depend on the aqueous solution pH. The extraction of iron(III) with H2L increases with the pH value, reaching a maximum in the zone of pH 2.0, remaining constant between 2 and 3.5 and subsequently decreasing. The quantitative extraction of iron(III) with 5 x 10(-30 M H2L in toluene is observed at pH 2.0. H2L was found to react with iron(III) to form ligand complex having a composition of 1:2 (Fe:H2L).     

Solvent extraction of lanthanum(III) and cerium(III) with dialkyldithiophosphoric acids. Separation from thorium(IV)

The extraction of lanthanum(III) and cerium(III) with dialkyldithiophosphoric acids, Hdtp, into different polar and nonpolar solvents (cyclohexane, benzene, carbon tetrachloride, chloroform, diethyl ether, dibutyl ether, n-butanol and cyclohexanone) from aqueous solutions containing perchlorate, nitrate and chloride anions has been investigated. The effect of various factors, such as nature of the solvent, pH, metal concentration and foreign anions present in the aqueous phase was investigated in order to establish the mechanism of extraction process. The data obtained suggest an ion-exchange mechanism. The anions present in the aqueous phase do not participate in the extraction process and do not influence significantly the magnitude of the extraction ratios either. The extracted species in the organic phase is a 12 complex of lanthanide with Hdtp. The extraction efficiency (E%) is calculated and the possibility of Th-rare earths separation is discussed.     

Separation of Uranium(VI) by Extraction with Dibutylditiophosphoric Acid

The extraction of uranium(VI) from aqueous solutions with dibutylditiophosphoric acid in organic solvents was studied. The influence of different factors as pH of the aqueous phase, extractant concentration and nature of solvent was investigated in order to find the optimum conditions for separation of metal from aqueous nitrate solutions. The effect of neutral donor extractants was also searched and the efficiency of the extraction was calculated.     

Complexation of uranium(VI) with acetohydroxamic acid

The advanced separation extraction process based on tri-n-butyl phosphate organic phase called UREX is being developed to separate uranium from fission products and other actinides, and the acetohydroxamic acid (AHA) is employed to reduce and complex plutonium and neptunium in order to decrease their distribution to the TBP-organic phase. In this study, the extraction of uranium was performed from various aqueous matrices with different concentrations of HNO₃, LiNO₃, and AHA. Extraction of uranium increases with increasing both initial HNO₃ and total nitrate concentration. UV-VIS spectrophotometry confirmed that AHA is involved in the complex of uranium with TBP.     

Extraction of uranyl nitrate from aqueous nitrate solutions by open cell polyurethane foam sponge (OCPUFS)

The extraction of uranyl nitrate into open cell polyurethane foam sponge (OCPUFS) from aqueous solution, in the presence of salting agents, has been examined. The extraction efficiency was observed to depend on the concentration of uranyl and nitrate ions. The charge of the cation was also found to influence the distribution ratio. The effect of the change in temperature and pH was also studied. The results are interpreted in terms of OCPUFS acting as a viscous organic ether of moderate dielectric constant.     

Determination of low level nitrite and nitrate in biological, food and environmental samples by gas chromatography-mass spectrometry and liquid chromatography with fluorescence detection

Gas chromatography-mass spectrometry (GC-MS) and liquid chromatography with fluorescence detection (LC-FL) methods have been proposed for the determination of low level nitrite and nitrate in biological, food and environmental samples. The methods include derivatization of aqueous nitrite with 2,3-diaminonaphthalene (DAN), enzymatic reduction of nitrate to nitrite, extraction with toluene and chromatographic analyses of highly fluorescent 2,3-naphthotriazole (NAT) derivative of nitrite by using GC-MS in selected-ion-monitoring (SIM) mode and LC-FL. Nitrite and nitrate ions in solid samples were extracted with 0.5 M aqueous NaOH by sonication. The recoveries of nitrite and nitrate ions based on GC-MS and LC-FL results were 98.40% and 98.10% and the precision of these methods, as indicated by the relative standard deviations (RSDs) were 1.00% for nitrite and 1.20% for nitrate, respectively. The limits of detection of the GC-MS in SIM mode and LC-FL methods based on S/N = 3 were 0.02 and 0.29 pg/ml for nitrite and 0.03 and 0.30 pg/ml for nitrate, respectively.     

Die Verteilung von Uran(IV) zwischen wässriger Salpetersäure und organischen Lösungen des Nitratsalzes des sekundären Amins Amberlite LA-1

The nitrate salt solution of the secondary amine Amberlite LA-1 in organic solvents extracts uranium(IV) from aqueous nitric acid solutions. The distribution ratio of uranium(IV) reaches a maximum at an equilibrium nitric acid concentration of 8.5M in the aqueous phase. Addition of n-octanol to the organic phase decreases, and the addition of nitrate to the aqueous phase increases the uranium(IV) distribution ratio. The extraction of uranium(IV) is fast and the equilibrium distribution is reached within less than one minute. At low uranium(IV) concentrations (<6·10⁻³ M) the distribution ratio is independent of the uranium(IV) concentration. At high uranium(IV) loadings of the organic phase an extrapolation gives a mole ratio of amine: uranium(IV)=2∶1. A double logarithmic plot of the dependence of the uranium(IV) distribution ratio vs. the LA-1 concentration in the organic phase gives a curve with a slope of two when polar diluents for LA-1 are used. This slope of two and the shapes of the absorption spectra of the organic phase from 400 to 700 nm make it very probable that uranium(IV) exists in the organic phase as a hexanitrato complex.      

Method of separating uranium from iron and thorium

Acid leaching of uranium deposits is not a selective process. Sulfuric acid solubilizes iron(III) and half or more of the thorium depending on the mineralog of this element. In uranium recovery by solvent extraction process, uranium is separated from iron by an organic phase consisting of 10 vol% tributylphosphate(TBP) in kerosine diluent. Provided that the aqueous phase is saturated with ammonium nitrate or made 4–5 M in nitric acid prior to extraction. Nitric acid or ammonium nitrate is added to the leach solution in order to obtain a uranyl nitrate product. Leach solutions containing thorium(IV) besides iron are treated in an analogous fashion. Uranium can be extracted away from thorium using 10 vol% TBP in kerosine diluent. The aqueous phase should be saturated with ammonium nitrate and the pH of the solution lowered to 0.5 with sufficient amount of sulfuric acid. In other words, the separation of uranium and thorium depends on the way the relative distributions of the two materials between aqueous solutions and TBP vary with sulfuric acid concentration. Thorium is later recovered from the waste leach liquor, after removal of sulfate ions. Uranium can be stripped from the organic phase by distilled water, and precipitated as ammonium diuranate.     

In situ electro-oxidation and liquid-liquid extraction of cerium(IV) from nitric acid medium using tributyl phosphate and 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate

The process of in situ electro-oxidation of Ce(III) to Ce(IV) followed by its extraction into the organic phase has been investigated for its applicability in the separation of Ce from nitrate medium. Solvent extraction of cerium from nitric acid after its electro-oxidation to fourth valency state was carried out using tributyl phosphate (TBP) and 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate (KSM-17, equivalent to PC-88A). The efficiency of the extractants at different aqueous phase nitric acid concentrations and different electrode potentials were determined. Various reducing agents such as hydroxylamine hydrochloride, sodium nitrite, ferrous sulphate as well as complexing agents like EDTA, oxalic acid etc, were studied as strippants for the back extraction of cerium from the loaded organic phase. The method developed for the extraction of cerium was further extended to the partitioning of cerium from Ce-Am mixture obtained during the KSM-17 based extraction chromatographic elemental fractionation of PUREX High Activity Waste (HAW) solutions. Recovery of Ce obtained in the extraction experiments by batch as well as by continuous flow organic phase was >95% with good radiochemical purity.     

On the influence of some inorganic salts on the partitioning of citric acid between water and organic solutions of tri-n-octylamine: Part I: Methyl isobutyl ketone as organic solvent

Reactive extraction is a commonly applied process to recover carboxylic acids from aqueous solutions. Such processes are nowadays designed using process simulation software. However, the essential prerequisite for such a simulation is the availability of a reliable thermodynamic model for the encountered phase equilibrium. Industrial experience revealed that even very small amounts of a strong electrolyte (e.g., sodium chloride) can considerably reduce the amount of carboxylic acid extracted from the aqueous into the organic phase. This contribution presents new experimental results for the influence of sodium nitrate, sodium chloride, sodium sulfate, sodium citrate and hydrochloric acid on the partitioning of citric acid to the coexisting aqueous/organic liquid phases of the system water + methyl isobutyl ketone (organic solvent) + tri-n-octylamine (chemical extractant) at 25 °C. A detailed discussion of the experimental results reveals that the dramatic decrease of the partition coefficient of carboxylic acid is caused by the chemical loading of the extractant by the inorganic acid, i.e. both acids (the weak carboxylic acid as well as the strong inorganic acid) compete for the sodium ions (in the aqueous phase) and for the amine (in the organic phase). In phase equilibrium the amine is predominantly loaded with the inorganic acid while the sodium salt of the carboxylic acid remains in the aqueous phase. That behavior is described by a thermodynamic framework that is able to predict the complex liquid–liquid equilibrium from information determined exclusively from investigations on subsystems.     

Thermodynamic studies of partitioning behavior of cytochrome c in ionic liquid-based aqueous two-phase system

The ionic liquid/aqueous two-phase extraction systems (ATPSs) based on imidazolium ionic liquids were used to extract cytochrome c. Effects of the alkyl chain length of the ionic liquid cations, concentration of potassium citrate, temperature and pH on the extraction efficiency have been investigated. The thermodynamic parameters (ΔG(T)°, ΔH(T)° and ΔS(T)°) associated with Cyt-c partitioning in aqueous two phase systems were determined. Thermodynamic studies indicated that the partitioning of Cyt-c was driven by both hydrophobic and electrostatic interactions in the extraction process. Under the optimum conditions, experiment results showed that 94% of the cytochrome c could be extracted into the ionic liquid-rich phase in a one-step extraction. The structural characterization of Cyt-c in the IL ATPS was investigated by UV-vis and circular dichroism (CD) spectra. The results demonstrated that no direct bonding interaction observed between ionic liquid and cytochrome c, while the native properties of the cytochrome c were not altered. Compared with traditional liquid-liquid extractions based on toxic organic solvents, ionic liquid/aqueous two phase extraction offers clear advantages due to no use of volatile organic solvent and low consumption of imidazolium ionic liquids.     

Reverse Micellar Extraction of β-Galactosidase from Barley (Hordeum vulgare)

The reverse micellar system of sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/isooctane was used for the extraction and primary purification of beta-galactosidase (EC 3.2.1.23) from the aqueous extract of barley (Hordeum vulgare) for the first time. The process parameters such as the concentration of the surfactant, the volume of the sample injected, and its protein concentration, pH, and ionic strength of the initial aqueous phase for forward extraction, buffer pH, and salt concentration for back extraction are varied to optimize the extraction efficiency. Studies carried out with both phase transfer and injection mode of reverse micellar extraction confirmed the injection mode to be more suitable for beta-galactosidase extraction. The extent of reverse micellar solubilization of proteins increased with an increase in protein concentration of the feed sample. However, back extraction efficiency remained almost constant (13-14.4%), which indicates the selectivity of AOT reverse micelles for a particular protein under given experimental conditions. beta-Galactosidase was extracted with an activity recovery of 98.74% and a degree of purification of 7.2-fold.     

Solvent extraction of uranium(VI) with DI-2-ethylhexyldithiophosphoric acid from aqueous nitrate,chloride, sulfate and phosphate media

The extraction of uranium(VI) with di-2-ethylhexyldithiophosphoric acid (HEhdtp) in benzene from aqueous solutions containing nitrate, chloride, sulfate and phosphate anions was investigated. The data obtained show hat the mechanism of extraction is similar to that established for perchlorate media. The inorganic anions present in the aqueous phase do not participate in the extraction process but affect the magnitude of the distribution ratio by the complexation phenomena which occur in the aqueous phase. In benzene the extracted species is a 12 complex of uranium(VI) with HEhdtp.     

Some parameters affecting the extraction chromatographic performance of TBP impregnated macroporous XAD-4 columns for Am(III)−Eu(III) separations

TBP impregnated macroporous styrene-divinylbenzene XAD-4 polymer was employed as the stationary phase in extraction chromatography of Eu(III) and Am(III). Parameters affecting the performance (HETP) of the chromatographic column were investigated. These include the effect of flow rate, TBP loading, aqueous nitrate concentration, and particle size. One striking result obtained is that the column performance improves as the TBP loading increases.