Liquid-liquid extraction separation of iron (III) with 2-ethyl hexyl phosphonic acid mono 2-ethyl hexyl ester

Liquid-liquid extraction separation of iron(III) with 2-ethyl hexyl phosphonic acid mono 2-ethyl hexyl ester (PC-88A) in toluene has been studied. Quantitative extraction of iron(III) with 5 x 10(-3) M PC-88A in toluene is observed in the pH range 0.75-2.5. From the extracted complex species in the organic phase iron(III) was stripped with 1-4 M HNO(3), 1.5-4 M H(2)SO(4) and 1.5-4 M HCl, and later determined spectrophotometrically by thiocyanate method. Separation of iron(III) was carried out with some of the first transition metals in binary and multicomponent mixtures. This method was extended for the determination of iron in real samples.     

Extraction of Uranium with 2-Ethylhexyl Phosphonic Acid Mono-2-Ethylhexyl Ester (PC-88A)

The extraction behavior of uranium (VI) from chloride medium with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) in dodecane has been investigated under wide range of conditions. Attempts have been made to establish the extraction mechanism of uranium(VI) with PC-88A. Treatment of the distribution data by slope analysis technique showed the formation of a monomeric complex of the nature [UO₂(A₂H)₂]. Formation of this species was also confirmed by non-linear least square regression of the distribution data to the mathematical expression correlating percentage extraction and acidity. In this investigation attempts have also been made to develop a mathematical model for the system (UO₂Cl₂-HCl-H₂O-PC-88A-dodecane) using experimental data on the distribution of uranium against initial aqueous acidity at different initial metal concentration. The mathematical model D = 37.547±0.223/C _i ^1/2×[H _i ]² can be used to predict the concentration of uranium in organic as well as in aqueous phases at any initial concentration of uranium [C _i ] and initial hydrogen ion concentration [H _i ]. The extraction constant (K _ex ) has been calculated.     

Studies on extraction of beryllium by di-(2-ethyl hexyl)-phosphoric acid from hydrochloric acid solutions

The distribution of Be between aqueous HCl solutions and organic phases of di-(2-ethyl hexyl)-phosphoric acid, has been described. The dependence of extraction on aqueous acidity, metal and extractant concentration as also on the diluent type, was thoroughly examined. The possible mechanism of extraction has been discussed in the light of results obtained.     

Synergic extraction of some lanthanide and actinide elements by a mixture of bis/2-ethyl hexyl/phosphoric acid and dinonylnaphthalene-sulfonic acid in aromatic diluents

Extraction of lanthanides and actinides were found to be synergically enhanced by a mixture of bis/2-ethyl hexyl/phosphoric acid /HA/ and dinonylnaphthalene sulfonic acid /HD/ in aromatic diluents covering a wide range of dielectric constant. The main extracted species is found to be in the form MA₂H_m–1D_m. Experimental results indicate that the extraction mechanism is governed by the extraction of HD in the organic phase.     

The extraction of beryllium(II) by di-(2-ethyl hexyl)-phosphoric acid from sulphate media

The distribution of Be(II) between aqueous sulphuric acid solutions and organic phases of di-(2-ethyl hexyl)-phosphoric acid (HDEHP) has been described. The dependence of extraction on contact time, acidity, metal and extractant concentration, diluent type and temperature was thoroughly investigated. The possible mechanism of the extraction is discussed on the basis of results obtained.     

Solvent extraction studies of plutonium(IV) and americium(III) in room temperature ionic liquid (RTIL) by di-2-ethyl hexyl phosphoric acid (HDEHP) as extractant

Solvent extraction of Pu(IV) and Am(III) from aqueous nitric acid into room temperature ionic liquid (RTIL) by an acidic extractant HDEHP (di-2-ethyl hexyl phosphoric acid) was carried out. The D values indicated substantial extraction for Pu(IV) and poor extraction for Am(III) at 1M aqueous nitric acid concentration. However at lower aqueous nitric acid concentrations (pH 3), the Am(III) extraction was found to be quantitative. The least squares analysis of the extraction data for both the actinides ascertained the stoichiometry of the extracted species in the RTIL phase for Pu(IV) and Am(III) as [PuH(DEHP)₂]³⁺, AmH(DEHP)²⁺. From the D values at two temperatures, the thermodynamic parameters of the extraction reaction for Pu(IV) was calculated.     

Stripping dispersion hollow fiber liquid membrane containing carrier PC-88A and HNO3 for the extraction of Sm3+

Stripping dispersion hollow fiber liquid membrane system（SDHFLM） containing feed phase adding acetate buffer solution and dispersion solution with HNO₃ solution as the stripping solution and membrane solution of 2-ethyl hexyl phosphoric acid-mono-2-ethylhexyl ester（PC-88A） dissolved in kerosene,has been studied for the extraction of Sm³⁺.Many factors including pH value, volume ratio of membrane solution to stripping solution（OAV） and carrier concentration on Sm³⁺ extraction were investigated. Experimental results indicate that the optimum extraction conditions of Sm³⁺ were obtained as that PC-88A concentration was 0.120 mol/L,and OAV was 1.00 in the dispersion phase,and pH value was 4.80 in the feed phase.When initial Sm³⁺ concentration was 1.20×10^-4 mol/L,the extraction percentage of Sm³⁺ was up to 92.8%in 160 min.     

Extraction of U(VI) by cyanex-272

Extraction of U(VI) from HNO₃, HCl and HClO₄ media using cyanex-272 (bis[2,4,4 trimethyl pentyl] phosphinic acid)/n-dodecane has been carried out. In the case of HNO₃ and HClO₄ media, the distribution ratio (D) value first decreases and then increases, whereas from HCl medium it first decreases and then remains constant with increase in H⁺ ion concentration. At lower acidities, U(VI) was extracted as UO₂(HA₂)₂ by an ion exchange mechanism, whereas at higher acidities as UO₂(NO₃)₂ ^.2(H₂A₂) following a solvation mechanism. The D for U(VI) by cyanex-272, PC-88A and DEHPA at low acidities follows the order cyanex-272 > PC-88A > DEHPA. Also, cyanex-272 was found to extract U(VI) more efficiently than TBP at 2M HNO₃. The effect of diluents on the extraction of U(VI) by cyanex-272 followed the order cyclohexane > n-dodecane > CCl₄ > benzene. The loading of U(VI) into cyanex-272/n-dodecane from 2M HNO₃ has shown that at saturation point, cyanex-272 was 78% loaded. No third phase was observed at the saturation level. The stripping of U(VI) from the loaded organic phase was not possible with water, it was poor with acetic acid and sodium acetate but quantitative with oxalic acid, ammonium carbonate and sodium carbonate.     

Mathematical modeling of solvent extraction of uranium from sulphate media employing 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and its mixture with trioctylphosphine oxide (TOPO) as extractants

The extraction of U(VI) from sulphate medium with 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A, H₂A₂ in dimeric form) in n-dodecane has been investigated under varying concentrations of sulphuric acid and uranium. Slope analysis of uranium (VI) distribution data as a function of PC88A concentration suggests the formation of monomeric species, viz. UO₂(HA₂)₂. This observation was further supported by the mathematical expression obtained during non-linear least square regression analysis of U(VI) distribution data correlating the percentage extraction (%E) and the acidity (H _i). A mathematical model correlating the experimental distribution ratio values of U(VI) (D _U) with initial acidity (H _i) and initial uranium concentrations (C _i) was developed: D_\textU = 12.98( ±0.90)/{ C_\texti ^{- 0.75( ±0.05)} ×[ H_\texti ]² } D_{\text{U}} = 12.98( \pm 0.90)/\left\{ {C_{\text{i}}^{ - 0.75( \pm 0.05)} \times \left[ {H_{\text{i}} } \right]^{2} } \right\} . This expression can be used to predict the concentration of uranium in organic as well as in aqueous phase at any C _i and H _i. The extraction data were used to calculate the conditional extraction constant (K _ex) values at different acidities (2–7 M H⁺), uranium (0.02–0.1 M) and PC88A (0.2–0.6 M) concentrations. These studies were also extended for the extraction of U(VI) using synergistic mixtures of PC88A and TOPO from sulphate medium.     

Studies on extraction behaviour of molybdenum (VI) from acidic radioactive waste using 2(ethylhexyl) phosphonic acids,mono 2(ethylhexyl) ester (PC-88A)/<Emphasis Type="Italic">n</Emphasis>-dodecane

This paper describes the studies on the extraction of molybdenum (VI) from aqueous nitric acid medium by (2-ethylhexyl) phosphonic acid, mono (2-ethylhexyl) ester (PC-88A). The extraction affecting parameters such as concentration of HNO₃ in aqueous feed, effect of concentration of extractants, effect of diluents, and molybdenum concentration in the aqueous phase are investigated to optimize the extraction conditions for the quantitative separation of molybdenum from nitric acid medium. With increase of HNO₃ concentration in aqueous phase, percentage extraction was found to be decreased in all the cases. Percentage extraction of molybdenum increases with increase in PC-88A concentration till the 0.15 M of PC88A, and after that it becomes constant. Kerosene and n-dodecane was found to be most suitable diluents. Among the various strippants used 0.2 M (w/v) solution of Na₂CO₃ and 0.2 M (w/v) solution (NH₄)₂CO₃ are found to be the equally suitable for stripping of molybdenum from the loaded organic phase. The stripping of molybdenum from loaded organic layer by various reagents followed the order: (NH₄)₂CO₃ >Na₂CO₃ >0.1 M sodium salt of EDTA >2 M NaOH >8 M HNO₃. The optimized process conditions are employed to extract molybdenum (VI) from actual Davies–Gray waste as well as from diluted high level waste generated in the purex stream. More than 94% Mo(VI) was extracted from radioanalytical as well as from high level waste of purex process and quantitative recovery was achieved in both the cases when 0.2 M sodium carbonate was used as stripping agent.     

Synergistic extraction of uranium with mixtures of PC88A and neutral oxodonors

The extraction of uranium(VI) from nitric acid medium is investigated using 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A in dimeric form, H₂A₂) as extractant either alone or in combination with neutral extractants such as tri-n-butyl phosphate (TBP), trioctyl phosphine oxide (TOPO), and dioctyl sulfoxide (DOSO). The effects of different experimental parameters such as aqueous phase acidity (up to 10 M HNO₃), nature of diluent [xylene, carbon tetrachloride (CCl₄), n-dodecane and methyl iso-butyl ketone (MIBK)] and of temperature (303–333 K) on the extraction behavior of uranium were investigated. Synergistic extraction of uranium was observed between 0.5 and 6 M HNO₃. Use of MIBK as diluent was also studied. Temperature variation studies using PC88A as extractant showed exothermic nature of extraction process. Studies were carried out to optimize the conditions for the recovery of uranium from the raffinate generated during the purification of uranium from nitric acid medium. Inductively Couple Plasma Atomic Emission Spectroscopy (ICP-AES) and Energy Dispersive X-Ray Fluorescence (EDXRF) techniques were employed for analysis of uranium in equilibrated samples.     

Extraction and separation studies of tellurium(IV) with tris-(2-ethyl hexyl) phosphate

A method is proposed for the extraction of microgram levels of tellurium(IV) from halide media with tris-(2-ethyl hexyl) phosphate dissolved in toluene as extractant. The optimum conditions have been evaluated from a critical study of acid concentration, extractant concentration, period of equilibration and effect of solvent. Tellurium ion from the organic phase is stripped with water and determined spectrophotometrically with stannous chloride. The method affords binary separation of tellurium from copper, bismuth, gold and selenium and is applicable to the analysis of alloy samples and synthetic mixtures. The method is fast, accurate and precise.     

Extraction of Am(III) from different acid media by di-2-ethyl hexyl phosphoric acid containing phosphorous pentoxide

The extraction of Am(III) from nitric, hydrochloric, oxalic, phosphoric and hydrofluoric acids was studied using 0.4F di-2-ethyl hexyl phosphoric acid (HDEHP) containing 0.1M phosphorous pentoxide (P₂O₅) in dodecane/xylene. The extraction with pure 0.4F HDEHP was found to be negligible from all the media studied. However, the presence of a small amount of P₂O₅ in it increased the extraction substantially. The distribution ratios of Am(III) obtained for HDEHP - P₂O₅ mixture 3M nitric acid containing different concentrations of oxalic acid/phosphoric acid/hydrofluoric acid are in the order of 200-250. The same for 3M hydrochloric acid is very high (800). These distribution ratios are sufficiently high for the quantitative extraction of Am(III) from all the acid media studied. Different reagents such as ammonium oxalate, sodium oxalate, oxalic acid, hydrofluoric acid, sodium carbonate and potassium sulphate were explored for the back extraction of Am(III) from 0.4F HDEHP + 0.1M P₂O₅ in dodecane/xylene. Of these, 0.35M ammonium oxalate and 1M sodium carbonate were found to be most suitable. The back extraction of Am(III) was also attempted with water and 1M H₂SO₄, HNO₃, HClO₄ and HCl solutions after allowing the extracted organics to degrade on its own. It was found that more than 90% of Am could be back extracted with these acids. Using this method more than 90% of Am(III) was recovered from nitric acid solutions containing calcium and fluoride ions.     

Solvent extraction of uranium from lean grade acidic sulfate leach liquor with alamine 336 reagent

This paper describes the solvent extraction studies carried out on an acidic low assay uranium bearing leach liquor generated during sulfuric acid leaching of a refractory uranium ore using alamine 336?Cisodecenol?Ckerosene reagent combine. The leach liquor has a U₃O₈ content of about 270?mg/L, free acidity 2.4?N H₂SO₄ and total dissolved solids concentration of 260?g/L. Process parameteric variation studies indicated strong influence of free acidity of the leach liquor, alamine 336 concentration and aqueous to organic phase ratio on the extraction efficiency of uranium. An extraction efficiency of about 95% was achieved when the free acidity of leach liquor was 1?N H₂SO₄ or lower, using 2% (v/v) alamine 336 at ambient temperature with an aqueous to organic phase ratio of 1:1. The loading capacity under these conditions was 1.2?g/L of U₃O₈. About 98% of the uranium values could be stripped from the loaded organic using 1?N NaCl in 0.2?N H₂SO₄. The solvent extraction studies aided in developing a suitable process flowsheet for treating refractory uranium ores which need high acidity during leaching and relatively lower acidity for purification by solvent extraction.     

Extraction of uranium and plutonium from oxalate bearing solutions using phosphonic acid: Solvent extraction, extraction chromatography and infrared studies

Solvent extraction and extraction chromatography studies of uranium and plutonium from oxalate supernatant solutions were carried out using 2-ethyl hexyl-2-ethyl hexyl phosphonic acid (PC88A). Based on the distribution data, it was inferred that both the uranium and plutonium could be recovered satisfactorily from such a solution. These studies were found to be useful in optimising the appropriate concentration of PC88A, HNO₃, oxalic acid and temperature to recover more than 90% of plutonium from the large volumes of oxalate bearing waste solutions. Spectral characteristics of the extractant and its complexing behavior with U(VI) was also studied using IR & FTIR.     

Di(2-ethyl hexyl) butyramide and di(2-ethyl hexyl)isobutyramide as extractants for uranium(VI) and plutonium(IV)

The extraction of uranium(VI) and plutonium(IV) from nitric acid into n-dodecane was studied using two isomeric branched alkyl amides, di(2-ethyl hexyl) butyramide (DEHBA) and di(2-ethyl hexyl) isobutyramide (DEHIBA). The extraction ratios of Pu(IV) at relatively high acidities were higher than the corresponding values for U(VI) in the case of DEHBA. However, with DEHIBA the values for Pu(IV) were negligibly small. Pu(IV) was found to be extracted as trisolvate by DEHBA and as disolvate by DEHIBA. U(VI) was extracted by both the amides. From the study of the extraction reactions at different temperatures, it was shown that all the reactions in the present investigation were enthalpy favoured and entropy disfavoured. Separation of Pu(IV) from bulk of U(VI) was feasible. However, the purity of the separated plutonium was not satisfactory in batch extraction studies.     

Binary mixture of PC88A and TOPO as extractant for thorium(IV) from aqueous HNO3 and H2SO4 media

Synergism is observed in the extraction of thorium(IV) by the binary mixture of PC88A and TOPO in the range 0.1–2.5M HNO₃ solution. The increase in acidity decreases the synergistic effect. Antagonism is observed when the extraction is carried out in H₂SO₄ medium.     

Solvent extraction of zinc by 2-hexylpyridine in benzene from aqueous mineral acid — Thiocyanate media

Solvent extraction of Zn(II) by 2-hexylpyridine (HPy) in benzene has been studied from aqueous mineral acid—thiocyanate media. The extraction, though dependent on the acidity of the aqueous phase, is poor from mineral acids (HCl, HNO₃ or H₂SO₄). Addition of 0.02M KSCN to the aqueous phase enhances the distribution ratio by a factor of almost one thousand. The stoichiometry of the extracted complex established by the usual slope analysis method indicates that an ionic type complex, e.g. Zn(SCN)₄·(HPyH)₂, is responsible for extraction. Complexing anions like acetate, oxalate or citrate at 1 M concentration mask the extraction of Zn(II) almost completely. Separation factors determined at optimal conditions (0.1M HPy in benzene −0.05M H₂SO₄+0.2M SCN⁻) indicate that Zn(II), along with Hg(II), can be separated in a single extraction from a number of metals, e.g. Cs(I), Sr(II), Ln(III), Y(III), Cr(III) and (VI). Other metals of interest like Cu(II), Co(II), Fe(III), Mo(VI), U(VI) and Tc(VII) are coextracted but the separation factors are large enough to allow separation in a multistage extraction process.     

High preconcentration of ultra-trace metal ions by liquid–liquid extraction using water/oil/water emulsions as liquid surfactant membranes

A high preconcentration method by liquid–liquid extraction using liquid surfactant membranes was developed. The water-in-oil (w/o) emulsion containing dilute hydrochloric acid, 2-ethylhexyl hydrogen 2-ethylhexylphosphonate (PC-88A), liquid paraffin, and kerosene was used for the extraction. In a resulting volume of 1000 cm³ of an aqueous sample solution (pH 5.0) containing less than 1 mg of each metal ion, 2 cm³ of w/o emulsion droplets coated with sorbitan monooleate were dispersed. The analyte metal ions in the outer bulk aqueous phase were extracted into the organic phase to form a complex with PC-88A and successively back-extracted into the inner aqueous phase. The analytes in the resulting inner aqueous phase were determined subsequently by graphite furnace atomic absorption spectrometry applied as a detector. By this procedure, concentration factors of 570, 820, 750, 970, 860, and 880 were achieved for chromium(III), manganese(II), cobalt(II), nickel(II), copper(II), and cadmium(II), respectively, and also the respective detection limits (3σ) of 0.4, 20, 1.2, 18, 18, and 0.7 pg cm⁻³ were obtained.     

PVT properties of di-(2-ethyl hexyl) phosphoric acid

Di-(2-ethyl hexyl) phosphoric acid (hereafter referred as D2EHPA) is an important solvent for solvent extraction industry. It is also used in nuclear solvent extraction as a solvent for TALSPEAK and REVERSED TALSPEAK processes for actinide (III)–lanthanide (III) separation. Its PVT properties are not available in literature. In this work, group-contribution approach was used to predict its PVT properties as well as selected physical properties like normal boiling point.