Solvent Extraction Separation of Chromium(VI), Iron(III), Cobalt(II), and Nickel(II) with Di-n-pentyl Sulfoxide

Abstract

Di-n-pentyl sulfoxide (DPSO) was employed for the solvent extraction separation of some transition metals from hydrochloric acid medium. It was found that chromium(VI) gets extracted at low acid concentrations (3 to 4.5 M), and iron(III) and cobalt(II) only above 5 M HCl. Nickel was not extracted at any of the test conditions. These transition metals were separated from one another by suitable choice of the extraction conditions.     

EXTRACTION OF GALLIUM/III/ FROM HYDROCHLORIC ACID BY DIISOPROPYL ETHER AND MIXTURE DIISOPROPYL ETHER-PENTANOL

In systems containing gallium (III) and hydrochloric acid, extraction with pure IPE and a mixture of IPE - pentanol was studied. The influence of the initial concentration of acid and the solvent composition as well as the temperature on the extraction of the gallium and the equilibrated phase volumes was examined. The synergistic extraction of gallium (III)was found with a mixture of IPE - pentanol and a maximum value of ΔD in a 20 %vol. of alcohol mixture. The conditions of the third liquid phase formation were found and its effect on the extraction was discussed.     

Solvent extraction separation of titanium(IV), vanadium(V) and iron(III) from simulated waste chloride liquors of titanium minerals processing industry by the trialkylphosphine oxide Cyanex 923

The solvent extraction of magnesium(II), aluminium(III), titanium(IV), vanadium(V), chromium(III), manganese(II) and iron(III) from hydrochloric acid solutions has been investigated using the trialkylphosphine oxide Cyanex 923 (TRPO) in kerosene as extractant. The results demonstrate that titanium(IV), vanadium(V) and iron(III) are extracted into kerosene as TiOCl₂·2TRPO, VO₂Cl·TRPO and HFeCl₄·2TRPO, respectively. On the other hand magnesium(II), aluminium(III), chromium(III) and manganese(II) are not extracted with TRPO from hydrochloric acid solutions (1.0–4.0 mol dm^?3) under the experimental conditions. IR spectral studies of the extracted complexes were further used to clarify the nature of the extracted complexes. The effect of the diluent on the extraction of titanium(IV), vanadium(V) and iron(III) has been studied and correlated with the dielectric constant. The loading capacity of the TRPO system has been evaluated and the potential for the separation and recovery of titanium(IV), vanadium(V) and iron(III) from simulated waste chloride liquors of the titanium minerals processing industry has been assessed. Copyright © 2004 Society of Chemical Industry     

Analytical Separation of Gold(III) by Extraction with 4-Methyl-2-pentanol from Hydrochloric Acid Media

Abstract

A simple and rapid method is described for the analytical separation of gold(III) from iron, cobalt, nickel, ruthenium, rhodium, iridium, palladium, platinum, copper, lead, bismuth, and manganese by solvent extraction with 4-methyl-2-pentanol from hydrochloric acid media. Very few cations and anions interfere.     

Studies in Solvent Extraction of Ruthenium(III) From HCI Solutions by Sulfoxides

Abstract

Studies on the solvent extraction of Ru(III) by sulfoxides from hydrochloric acid solutions; are reported. A kinetic effect has been observed in the extraction process. The extraction efficiency varies with the nature of the sulfoxide, the diluent employed, and the molarity of the acid.     

SOLVENT EXTRACTION OF SCANDIUM(III), YTTRIUM(III), LANTHANIDES(III), ANDDIVALENT METAL IONS WITH SEC -NONYLPHENOXY ACETIC ACID

ABSTRACT

Such physicochemical properties of sec-nonylphenoxy acetic acid (CA-100) as the solubility in water, acid dissociation constant in water, dimerization constant in heptane, and distribution constant in organic solvent-water were measured by two-phase titration. The extraction behaviors of scandium (III), yttrium (III), lanthanides (III), and divalent metal ions from hydrochloric acid solutions with CA-100 in heptane have been investigated, and the possibilities of separating scandium (yttrium) from lanthanides and divalent metal ions have been carefully discussed. The stoichiometries of the extracted metal complexes were investigated by the slope-analysis technique. The effect of the nature of diluent on the extraction of yttrium (III) with CA-100 has been studied and correlated with the dielectric constant.     

Recovery and Separation of Lanthanum(III), Aluminum(III), Cobalt(II), and Nickel(II) from Misch Metal by Solvent Extraction Using Bis(2-ethylhexyl) phosphinic Acid

Abstract

This paper describes use of bis(2-ethylhexyl) phosphinic acid as a reagent for extraction and mutual separation of lanthanum(III), aluminum(II), cobalt(II), and nickel(II) in 1.0 mol/L sodium nitrate. The extraction and stripping behavior of the four metal ions has been investigated using the extractant in Solvesso #150 as a diluent. The mutual separation and recovery of the metal ions from their mixtures has been tested by multistage extraction with a conventional separator funnel. A set of separation schemes has also been proposed for a continuous countercurrent multistage extraction which is comprised of ten extraction stages, four scrubbing stages, and seven stripping stages. Lanthanum(III) and aluminum(III) are coextracted but separated by selective stripping into different concentrations of hydrochloric acid. Cobalt(II) can be extracted with the nickel(II)-preloaded extractant solution, whereas nickel(II) remains in the aqueous phase. The successful separation of these metal ions from a misch metal-simulated sample is presented.     

EXTRACTION MECHANISM OF Sc(III) AND SEPARATION FROM ThUV).Fe(III) AND Lu(III) WITH BIS(2,4,4-TRIMETHYLPENTYL)PHOS- PHINIC ACID IN N-HEXANE FROM SULPHURIC ACID SOLUTIONS

ABSTRACT

The extraction equilibrium data of sulphuric acid and scandium(III) with bis(2,4,4-trimethylpenty)phosphinic acid (H[BTMPP]) from sulphuric acid solutions have been obtained. There are two extraction mechanisms of scandium(III) with H[BTMFP] at different ranges of aqueous acidity. The extraction of Sc(III) proceeds according to a cation exchange reaction at lower aqueous acidity and to a solvating reaction at higher acidity. The practicability of separating Sc(III) from Th(IV),Fe(III) and Lu(II) by controlling the aqueous acidity was discussed. The effect of temperature on extraction of Sc(III) was observed and thermodynamic, functions were caculated. IR and NMR spectra were made for organic extracts. The extraction characteristics of H[BTMPP] and di(2-ethylbexyl)phosphinic acid (H[DEHP]) were contrasted to obtain more information about extraction with H[BTMPP].     

Synthesis of Pre‐Organized Bisdiglycolamides (BisDGA) and Study of their Extraction Properties for Actinides(III) and Lanthanides(III)

Bisdiglycolamides 1–9 were synthesized and studied as extracting agents for An(III) and Ln(III) from nitric acid solutions. Compounds 1d‐3 with rigid spacers as m‐xylylene and 6b‐9 with more flexible alkyl chain linkers, show higher selectivity for Eu(III) extraction over Am(III) than diglycolamides (TBDGA, DMDODGA, TODGA) in (50:50)_%Vol HPT/1‐octanol mixture. Am(III) and Eu(III) extraction kinetics are very fast and back‐extraction with more than 99% efficiency of both cations is possible after four times of contact of the loaded solvent with fresh 0.01 mol/L nitric acid solutions.     

Selective Separation of Arsenic(III) and (V) Ions with Ferric Complex of Chelating Ion-Exchange Resin

Abstract

Trace levels of aqueous arsenic(III) and (V) ions were adsorbed selectively onto the ferric complex of a chelating resin, Uniselec UR-10. The adsorption was markedly dependent upon the pH of the aqueous phase. The distribution ratio and the specific adsorption capacity of arsenic(III) were 23,000 and 0.47 mmole/g, respectively, at the optimum pH for the adsorption, 9.2. The corresponding values of arsenic(V) were 22,000 and 0.53 mmole/g at the optimum pH 5.5. In the column operation the adsorption of the arsenic ions was also dependent upon the flow velocity and the size of the resin particle. A velocity of 60 cm/hr and 100 to 200 mesh size afforded satisfactory results. Adsorbed arsenic was recovered quantitatively by eluting the resin with 2 N hydrochloric acid, where the complexed iron was also eluted. A trace level of arsenic in wastewater from a geothermal power plant was successfully separated in the presence of a large excess of diverse cations and anions. Trace arsenic in natural seawater was also successfully preconcentrated 100 to 200 times over the original level by adsorption onto the ferric resin followed by elution with hydrochloric acid.     

EXTRACTION AND SEPARATION OF HEAVY RARE EARTH(III) WITH EXTRACTION RESIN CONTAINING DI(2,4,4-TRIMETHYL PENTYL) PHOSPHINIC ACID (CYANEX 272)

ABSTRACT

Extraction resins, of the type of Levextrel, (which is a collective term for styrene/divinylbenzene based copolymers of predominantly macroporous structure that contain a selective extractant) are important for the recovery and separation of metal ions, as they combine features of solvent extraction and ion exchange resins. This paper presents the results of the adsorption of heavy rare earth ions (Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(II1)) from hydrochloric acid solutions at 0.2 mol/L ionic strength and 50°C by the extraction resin containing di (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272) and the chromatographic separation of (Er(III), Tm(III) and Yb(III)). Technological separation products, with purity and yield of Tm₂O3 >99.97%, >80%; Er₂O₃ >99.9%, >94% and Yb₂O₃ >99.8%, >80% respectively, have been obtained from a feed having the composition Tm₂O₃ 60%, Er₂O₃ 10%, and Yb₂O₃ 3%, the others 27%.

The distribution coefficients, extraction equilibrium constants and separation factors have been determined as a function of acidity, loading of the resin and rare earths, flow rates and column ratios. The resolutions and efficiencies of separation of Er/Tm/Yb each other have been calculated. The stoichiometry of the extraction of rare earth ions has been suggested as well.     

Extraction and Stripping Behavior of Iron (III) from Phosphoric Acid Medium by D2EHPA Alone and Its Mixtures with TBP/TOPO

In the present study an attempt has been made to understand the extraction and stripping behavior of iron (III) with D2EHPA alone and its mixture with TBP or TOPO in phosphoric acid medium. Effect of variables such as concentrations of iron (III), phosphoric acid, and phosphate in the aqueous phase, D2EHPA, TBP, and TOPO concentrations in the organic phase and temperature on the extraction process has been studied. The extraction of iron (III) decreased with increase in phosphoric acid concentration. The increase in D2EHPA concentration increased the extraction of iron (III). The presence of TOPO or TBP with D2EHPA showed antagonism. The increase in temperature decreased the extraction of iron (III) with D2EHPA alone and its mixture with either TOPO or TBP showing the exothermic nature of the extraction reaction. The stripping of iron (III) by various reagents followed the order: oxalic acid > phosphoric acid > hydrochloric acid > sulphuric acid > mixture of sulphuric and hydrofluoric acids > ascorbic acid > citric acid irrespective of extraction systems. Higher temperature favors the stripping. The effect of diluents on iron (III) extraction has also been studied. The mechanism of extraction has been explained in the light of the results obtained.     

Extraction separation of Ir(III) and Rh(III) with Cyanex 923 from chloride media: a possible recovery from spent autocatalysts

Liquid–liquid extraction of Ir(III) and Rh(III) with Cyanex 923 from aqueous hydrochloric acid media has been studied. Quantitative extraction of Ir(III) was observed in the range of 5.0–8.0 mol dm^?3 HCl with 0.1 mol dm^?3 Cyanex 923, while Rh(III) was extracted quantitatively in the range of 1.0–2.0 mol dm^?3 HCl with 0.05 mol dm^?3 Cyanex 923 in toluene along with 0.2 mol dm^?3 SnCl₂. The Ir(III) was back extracted with 4.0 mol dm^?3 HNO₃ quantitatively from the organic phase while Rh(III) was stripped with 3.0 mol dm^?3 HNO₃. The extraction of Rh(III) with Cyanex 923 was not quantitative without use of SnCl₂. However in the extraction of Ir(III) a negative trend was observed in the presence of SnCl₂. Varying the temperature of extraction showed that the extraction reactions of both the metal ions are exothermic in nature, and the stoichiometric ratio of Ir(III)/Rh(III) to Cyanex 923 in organic phase was found to be 1:3. The methods developed were applied to the recovery of these metal ions from a synthetic solution of similar composition to that from leaching of spent autocatalysts in 6.0 mol dm^?3 HCl. © 2002 Society of Chemical Industry     

Synergistic Solvent Extraction of Lanthanides (III) with Mixtures of Tetraphenylmethylenediphosphine Dioxide and Picrolonic Acid from HCl Solutions

The solvent extraction of lanthanides(III) from hydrochloric acid solutions into the organic phase containing neutral bidentate extractant tetraphenylmethylenediphosphine dioxide (L) and picrolonic acid (HP) has been studied. A considerable synergistic effect was observed in the presence of HP in the organic phase containing neutral bidentate organophosphorus ligand. The extraction equilibrium was investigated and the equilibrium constants were calculated. It was found that the lanthanide(III) ions are extracted from weak acidic solutions as LnP₃L and LnP₃L₂ complexes. The mixture L–HP offers higher extraction efficiency toward Ln(III) than mixtures of L with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 or picric acid.     

Influence of Temperature on Extraction

Abstract

The literature data related to the influence of temperature on extraction are very often controversial. It appeared advisable to undertake an investigation of such an influence in systems containing diisopropyl ether (IPE), because of their ability to form three coexisting liquid phases.

In the extraction system H₂O-HC1-FeC13-IPE, the volume changes and the metal distribution depending on temperature (ranging from 13 to 40° C) and the initial concentration of hydrochloric acid (5 to 11 M) were examined. The formation of the third phase (heavy organic phase) is of special interest in the separation processes because a very high concentration of metal can be expected. The complexity of such a multi-component and multiphase system makes a phenomenological approach more appropriate than a thermodynamic one.

In the three-phase system an increase in temperature increases the distribution ratio of iron(III) whereas in the two-phase system, the distribution ratio decreases. The extraction factors based on phase volume and distribution ratio were calculated. Phase transformations occur in a narrow temperature range. A decrease of the initial acid concentration and an increase in temperature contribute to an increase in the number of equilibrated phases. Choice of the appropriate temperature in similar systems offers new possibilities in the application of extraction in separation procedures.     

Kinetics of Americium(III) Extraction and Back Extraction with BTP

Abstract

2,6‐Di(5,6‐dipropyl‐1,2,4‐triazin‐3‐yl)pyridine (BTP) extracts trivalent actinides from nitric acid with high separation factors over the lanthanides. The kinetics of americium(III) extraction and back extraction of this extraction system was studied in a constant‐interface stirred cell. The americium(III) extraction rate was found to be independent of the stirring speed. This means that the rate of mass transfer is limited by a slow chemical complexation reaction (“chemical regime”). The americium(III) extraction rate was found to increase linearly with BTP concentration. Nitric acid concentration had a strong influence on the rate of the americium(III) extraction, due to its influence on the free extractant concentration. The addition of ammonium nitrate did not affect the rate of americium(III) extraction. By investigating the influence of the interfacial area on the americium(III) extraction rate, the interface was identified as the site of the chemical reaction. The americium(III) back extraction rate increased linearly with the stirring speed, indicating that the back extraction is limited by diffusion. The extraction and the back extraction rates could be calculated by a simple model based on equilibrium data for the co‐extraction of americium(III) and nitric acid.     

Complexation Behavior of Iron(III) with Aloxime 800, D2EHPA,CYANEX 272, CYANEX 302, and CYANEX 301

Abstract

The extraction of iron(III) has been studied from chloride solutions with di(2‐ethylhexyl)phosphoric acid (D₂EHPA), bis(2,4,4‐trimethylpentyl)phosphinic acid (CYANEX 272) and its sulfur‐substituted analogs, called CYANEX 302, and CYANEX 301, and 5‐dodecylsalicylaldoxime (Aloxime 800).

Job's method was applied for the characterization of the iron(III) complexes dissolved in hexane. In the case of D₂EHPA and CYANEX 272, a 1:1 ligand‐to‐metal ratio was observed, thus inferring the coordination of additional compounds. No chloride transport occurred during extraction, therefore suggesting the formation of [Fe(OH)₂L] complexes. With CYANEX 302, a ratio of 2:1 was obtained, whereas for CYANEX 301, the results of Job's method indicated the presence of four extractant molecules around the metal ion. Less hydrolysis or the possible oxidation of the sulfur‐substituted organophosphinic acids and the corresponding reduction of Fe(III) towards Fe(II) may explain this behavior. In the case of Aloxime 800, the formation of the [FeL₃] species is suggested.

A comparative study was carried out to identify the ligand‐to‐metal ratio of the iron(III) complexes in anhydrous circumstances. These studies showed that 1:1 ligand‐metal complexes are easily formed in the case of the organophosphoric‐ and organophosphinic‐acid extractants. A higher ligand‐metal ratio may be possible, but is not always a necessary condition for iron(III) extraction. Even the coexistence of [FeCl₂L], [FeClL₂] and to a smaller extent [FeL₃] is quite presumable in anhydrous media. Finally, FT‐IR spectra as well as UV‐VIS spectra of the hexane phases make it possible to gain a better insight into the complexation characteristics of iron(III).     

SYNERGISTIC EXTRACTION OF Eu(III) AND Am(III) BY THENOYLTRIFLUOROACETONE AND NEUTRAL DONOR EXTRACTANTS: (CARBAMOYLMETHYL)PHOSPHINE OXIDE AND 2,6-BIS((DIPHENYLPHOSPHINO)METHYL)PYRIDINE N,P, P-TRIOXIDE

ABSTRACT

Solvent extraction of Eu(III) and Am(III) from weakly acidic solutions with octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and 2,6-bis((diphenylphosphino)methyl)pyridine N, P, P-trioxide (NOPOPO) in 1,2-dichloroethane was studied on a comparative basis. NOPOPO was found to exhibit unusually high extractability for Eu(III) and Am(III), probably due to its trifunctional nature, sufficient steric flexibility and basicity of the functional groups. Both CMPO and NOPOPO demonstrated synergistic effects in extraction of Eu(III) and Am(III) when used in combination with thenoyltrifluoroacetone (HTTA). However, the stoichiometry of the extracted species with CMPO/HTTA and NOPOPO/HTTA was different under similar experimental conditions. The extractant dependencies of the synergistic extractions suggest that the extracted species are the adduct complexes, M(ClO₄)(TTA)₂(CMPO)₂ and M(ClO₄)₂(TTA)(NOPOPO)₂, respectively. It was also observed that CMPO and CMPO/HTTA in dichloroethane extracted Eu(III) and Am(III) equally well, with very similar extraction constants. However, NOPOPO and NOPOPO/HTTA in dichloroethane demonstrated a slight preference for Eu(III) over Am(III), with the extraction constants for Eu(III) more than one order of magnitude higher than that for Am(III).     

Extraction behavior of Am(III) and Eu(III) by tri-n-octylmethylammonium diglycolamate ionic liquid impregnated XAD-7

Aliquat-336-based strongly hydrophobic ionic liquid, tri-n-octylmethylammonium diglycolamate ([A336]⁺[DGA]^?), was prepared and impregnated in Amberlite XAD-7 (abbreviated as [A336]⁺[DGA]^?/XAD-7) for studying the extraction behavior of Am(III) and Eu(III) from nitric acid medium. The distribution ratio of Am(III) and Eu(III) in [A336]⁺[DGA]^?/XAD-7 decreased with an increase in the concentration of nitric acid and the mechanism of trivalent metal ion extraction in the resin phase was elucidated. The uptake of Am(III) and Eu(III) in [A336]⁺[DGA]^?/XAD-7 followed a second order and from the Langmuir adsorption model the apparent europium extraction capacity was determined. The conditions needed for efficient separation of Am(III) from Eu(III) was optimized.     

Solvent-Extraction Behavior of Cobalt(II), Nickel(II), Copper(II), and Palladium(II) with Tri-n-butylphosphate

Abstract

A systematic study of the extraction behavior of cobalt(II), nickel(II), copper(II), and palladium(II) with TBP from thiocyanate system in various ranges of acid concentrations has been performed. The thiocyanate medium leads to enhanced extractions in all these cases compared to those in the previously used chloride medium. For palladium, the chloride and nitrate systems have been critically examined. Sixty-two per cent extraction occurs from 4 M hydrochloric acid using 100% TBP in a single run and the extraction becomes quantitative (>99%) after four successive equilibrations. A simpler method has been proposed for rapid extraction of palladium(II) as the thiocyanate complex. Quantitative extraction occurs in the presence of 1.2% thiocyanate solution from 0.5 to 2 M hydrochloric acid (initial) up to pH 8.0. The extractable species of cobalt(II), nickel(II), copper(II), and palladium(II) from thiocyanate medium are probably similar and of the type [M(CNS)₄]^2? [K·TBP·3H₂O]₂ ⁺ (buffer solution) and [M(CNS)₄]^2? [H·TBP·3H₂O]⁺ ₂ (acid solution). A simple extraction scheme has been worked out for the separation of palladium(II) from iron(III), cobalt(II), nickel, manganese(II), copper(II), and platinum.