Extraction of uranium (VI) from hydrochloric acid solutions by long-chain aliphatic amines

The partition of uranium (vi) between hydrochloric acid solutions and organic solutions of long-chain aliphatic amines has been investigated at different concentrations of hydrochloric acid, solvent and aqueous uranium, and at different temperatures. The effects of amine structure and of organic solvent and the mechanism of uranium extraction are discussed on the basis of the results obtained. From infra-red spectral measurements it is postulated that a chloro complex of uranium (vi) is formed in the extraction of uranium (vi) from hydrochloric acid solution by tri-n-dodecylamine in benzene.     

RECOVERY OF URANIUM FROM ACID MEDIA BY MACROPOROUS BIFUNCTIONAL PHOSPHINIC ACID RESIN

ABSTRACT

The extraction of uranium from various acid media such as nitric acid, sulphuric acid, hydrochloric acid, phosphoric acid and perchloric acid by a macroporous bifunctional phosphinic acid resin (MPBPA) has been studied. The distribution coefficients for the extraction of uranium by the MPBPA resin are compared with the corresponding values reported in literature for the conventional sulphonic acid resin. The results clearly indicate the suitability of the MPBPA resin to recover uranium from different types of acid solutions of widely ranging acidities.     

High Molecular Weight Pyridine Amines as Solvents for Uranium(VI) and Its Separation from Thorium

Abstract

Three high-molecular-weight pyridine amines, 5-(4-pyridyl)nonane, 2-hexylpyridine, and diphenyl-2-pyridylmethane, have been studied as components of solvent extraction systems. Results are presented to show the dependence of the uranium extraction coefficient (D _a ^o = [U_org]/[U_aq]) on equilibrium concentrations of hydrochloric, nitric, and sulfuric acid solutions with and without thiocyanate ions. The optimal conditions for the extraction have been carefully selected from an extensive and critical investigation of the various factors involved; e.g., the effects of diluents, concentration of the mineral acids, thiocyanate ions, salting and complexing agents, and the concentration of the solvents. The extraction mechanism and composition of the extracted complexes of uranium have been studied from partition and slope-analysis data. The results obtained give an orderly picture of the mechanism of extraction of uranium thiocyanate complexes (partly in relation to the hydration and solvation of the compounds extracted). Anomalous extraction behavior was observed at solvent concentrations greater than 0.05 M. The results have been interpreted on the basis of the formation of micelles of the salt molecules of the solvents. It has been shown that these pyridines will extract the metal efficiently and reversibly from dilute acid chloride, nitrate, and sulfate solutions containing thiocyanate. Common salts have no depressing effect on extraction. Distribution coefficients and separation factors of several metal ions, with respect to uranium(VI), are reported for the three mineral acid systems, and a method for the separation of thorium-234 from uranium is also described.     

Extraction of cobalt (II) from hydrochloric acid solutions by long-chain aliphatic amines

The partition of cobalt (II) between hydrochloric acid solutions and organic solutions of long-chain aliphatic amines has been investigated under different conditions. The extracted species has been examined spectro-photometrically, and an infra-red study has also been made of the organic phases. The mechanism of extraction is discussed on the basis of the results obtained, and in addition a structure is proposed for the complex formed in this extraction system.     

DILUENT EFFECT ON THE EXTRACTION OF URANIUM(VI) FROM HYDROCHLORIC ACID SOLUTIONS BY TRIOCTYLMETHYLAMMONIUM CHLORIDE

ABSTRACT

The extraction of uranium(VI) from hydrochloric acid solutions by trioctylmethylammonium chloride (TOMAC) has been examined using various diluents such as benzene, chlorobenzene, o-dichlorobenzene, toluene, m-xylene, nitrobenzene, carbon tetrachloride, chloroform and 1,2-dichloroethane. It was found that by assuming a regular solution, the distribution coefficient and the enthalpy change associated with the metal extraction can be expressed in terms of the solubility parameter of TOMAC, diluent and the complex formed in the organic phase and their molar volumes. Additionally an empirical relation holds between distribution coefficient and the viscosity of diluent. Further results for the extraction of divalent manganese, cobalt, copper, zinc and cadmium from hydrochloric acid solutions by TOMAC are investigated in comparison with those of uranium(VI).     

Silver Extraction from Hydrochloric Acid Solutions with the Disulfide of Bis(2,4,4-trimethylpentyl)Dithiophosphinic Acid

Silver extraction from hydrochloric acid solutions with the disulfide of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (L) in toluene is described in this work. Based on the analysis of the extraction data, it was concluded that silver extraction is due to the formation of the compound AgCl?2L in the organic phase. An increase in the concentration of hydrochloric acid in the aqueous phase leads to a decrease in AgCl extraction because of the formation of non-extractable anionic complexes of silver. Solvent extraction efficiency decreases in the series octanol > decane > chloroform > toluene, which is due to the preferential solvation of the extracted complex by the solvent. A significant increase in the extraction of silver chloride with disulfide in the presence of octanol is caused by the strong interaction of the extracted compound and the alcohol, due to the chloride ion solvation by octanol. The possibility of using the disulfide for silver extraction from hydrochloric acid solutions containing metal impurities (Ni, Cu, Co, Zn, Fe (III), and Na) has been demonstrated. The degree of silver recovery in one stage was 98.62%, while the extractant showed high selectivity toward silver: the separation factors of silver over metal (β_Ag/_Me) ranged from 9000 to 30,000. Almost complete silver stripping from the organic phase was achieved when using a mixture of thiourea and sulfuric acid solutions. The extraction characteristics of the disulfide are much better as compared to that of the well-known commercially available extractant triisobutylphosphine sulfide. The disulfide of bis(2,4,4-trimethylpentyl)dithiophosphinic acid can be used for efficient extraction of silver from industrial hydrochloric acid solutions of different origin.     

Combined Ion Exchange—Solvent Extraction (CIESE): A Novel Separation Technique for Inorganic Ions

Abstract

In the present paper a novel separation technique for inorganic ions is described. This has been termed combined ion exchange—solvent extraction (CIESE), because it is assumed that both ion exchange and solvent extraction are operative simultaneously to effect the separations. This concept is illustrated with two examples: the separation of iron(III), Co(II), and Ni(II) on the ion-exchange resins Dowex 50 and Dowex 1 using acetone or tetrahydrofuran—hydrochloric acid mixtures, and the separation of uranium from numerous metal ions on Dowex 50, employing as eluent a medium consisting of tetrahydrofuran—nitric acid. Because this separation principle is superior to methods employing the conventional separation techniques of ion exchange in pure aqueous solutions and of common liquid-liquid extraction, it is expected that it will also find application for the solution of other problems encountered in inorganic analytical chemistry.     

The extraction of uranium (VI) and thorium (IV) from nitric acid solutions by tri-n-octyl phosphine oxide

The distribution of uranium(vi) and thorium(iv) between nitric acid solutions and solutions of tri-n-octyl phosphine oxide (TOPO) in kerosene has been investigated. The organic phases have been studied by infrared and nuclear magnetic resonance spectroscopy. Further the absorption spectra of both the aqueous and organic phases have been examined in the extraction of uranium(vi).     

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.     

SEPARATION OF URANIUM ON POLYURETHANE FOAM IMPREGNATED WITH TRIOCTYLPHOSPHINE OXIDE

ABSTRACT

A method is described for the quantitative separation of uranium from practically all other elements in 1M hydrochloric acid solution containing ascorbic acid. From such a solution uranium is retained selectively by a column containing open-cell polyurethane foam Impregnated with tri-n-octylphosphine oxide (TOPO). The uranium together with TOPO is eluted with ethanol and then 1t is adsorbed on a column of Dowex 1 anion exchange resin from a HC1-organic solvent system. Uranium is eluted with 1M hydrochloric acid.     

Preparation conditions effect on the properties of uranium tetrafluoride

Uranium tetrafluoride precipitation from hydrochloric acid solutions of uranium(IV) and from uranium dioxide pulp is reported. The physicochemical properties of the precipitated uranium tetrafluoride crystalline hydrates and those of their dehydration products are demonstrated to depend on various processing parameters.     

UPTAKE OF METAL IONS BY A NEW CHELATING ION-EXCHANGE RESIN. PART 1: ACID DEPENDENCIES OF ACTINIDE IONS*

ABSTRACT

The uptake of several actinide ions [U(VI), Pu(IV), Np(IV), Th(IV] and Am(DI)) from nitric and hydrochloric acid solutions, and of U(VI) from near-neutral solutions by the new chelating ion-exchange resin, Diphonix^TM, has been investigated. Diphonix is a polyfunctional resin containing sulfonic and gem-diphosphonic acid groups chemically bonded in a styrene-divinylbenzene polymeric network. Comparison of the acid dependencies of the actinide ions uptake measured with Diphonix with those obtained using a commercial sulfonic -type resin and a resin containing both sulfonic and monophosphonic aCid groups, hat Shown that Diphonix binds the actinides via a different kind of chemical interaction, involving the.formation of chelate complexes through the phosphoryl groups of the gem-diphosphonic acids. As a consequence, Diphonix is superior to other resins in extracting actinide ions from very acidic solutions. A better performance of Diphonix is also observed with the uptake of uranium from neutral solutions. Conditions for efficient stripping of actinide species from the resin have been found.     

PALLADIUM WITH TRIOCTYLMETHYLAMMONIUM CHLORIDE SOLVENT EXTRACTION OF PALLADIUM(II) WITH TRIOCTYLMETHYLAMMONIUM CHLORIDE

Equilibrium distribution of palladium(II) was investigated in the solvent extraction with tri-octylmethylammonium chloride (QC1) in toluene from hydrochloric acid solutions at 303 K. The title extracting reagent extracted hydrochloric acid as the species of the types, QC1(HC1) (_n(n= 1,2), according to the similar extraction reactions as observed in the extraction of organic acids such as acetic acid and phenol with high-molecular-weight amines in the previous works. From the concentration dependencies of the reactant species on the distribution ratio and from the result of loading test, it was elucidated that palladium(II) is extracted as a mononuclear ion pair complex of the type, Q⁺;[PdCl]₃ (HCl)] in the very high concentration region of hydrochloric acid. The equilibrium constant of the extraction reaction was evaluated.     

Studies on the Development of a Flow-Sheet for AHWR Spent Fuel Reprocessing Using TBP

The present paper describes the results of solvent extraction studies carried out in batch mode to collect data on distribution of uranium, plutonium, and thorium using 5% TBP in n-dodecane. Extraction studies are carried out from feed solutions having bulk thorium containing aluminum and fluoride ions in ～3.00–4.00 M nitric acid at concentration levels anticipated in feed solutions during Advanced Heavy Water Reactor (AHWR) spent fuel reprocessing. Studies are carried out under varied experimental conditions. Parameters such as organic to aqueous phase ratio during extraction, concentration of nitric acid for scrubbing co-extracted thorium from loaded organic phase etc., are studied in detail. Hydroxylamine nitrate is selected for reductive stripping of plutonium in preliminary studies. Reagent mixture containing 0.30 M HAN + 0.60 M HNO₃ and 0.20 M N₂H₄ is found to be optimum for plutonium partitioning. This paper also describes the extraction and stripping of uranium and plutonium in co-current mode. The extraction behavior of relevant fission products is studied from a simulated feed solution. A preliminary study on a few commercially available reducing agents is also included. These data are useful in developing a flow-scheme for the recovery of uranium and plutonium from spent fuel originating from AHWR.     

黑曲霉产有机酸浸出铀矿石的影响因素

为了解培养基种类、培养温度和pH值等因素对黑曲霉产生的混合有机酸浸出铀矿石的影响,从铀矿山水样中分离、纯化得到了一株真菌--黑曲霉,应用马铃薯-蔗糖培养基（potato sucrose agar,PSA）和葡萄糖-玉米浆培养基(dextrose corn syrup,PCS)进行黑曲霉培养,获得了不同培养温度下产生的pH值不同的黑曲霉产混合有机酸,并将之作为浸出剂用于浸铀实验研究。研究表明,黑曲霉产生的有机酸的主要组分为草酸和柠檬酸等有机酸,培养基种类的不同会影响黑曲霉所产有机酸的浸铀效果,采用PSA培养基培养的黑曲霉产生的有机酸浸铀效果更好（p<0.05）。培养温度和混合有机酸的pH值也会对黑曲霉代谢产物的铀浸出率有显著性影响（p<0.05）,且二者具有交互效应,pH值对铀浸出率的影响相对较大。应用PSA培养基时,最佳培养温度为25℃,最佳代谢产物pH值为2.3;应用PCS培养基时,最佳培养温度为30℃,最佳混合有机酸pH值为2.0。培养基种类、温度和pH值主要通过改变黑曲霉产生的有机酸的成分和含量对铀浸出率产生影响。     

Extraction of protactinium from acid media using Aliquat 336

Solvent extraction studies on protactinium were carried out from hydrofluoric acid, hydrochloric acid, and a mixture of hydrochloric and hydrofluoric acids using Aliquat 336 and ²³¹Pa. The extraction of protactinium from hydrofluoric acid (0.025–10 M) decreased with increasing acid concentration and was less than 10% above 5 M. The extraction from hydrochloric acid (0.5–8 M) started only above 4 M and increased with increasing acid concentration. The extraction of protactinium from a mixture containing hydrochloric acid (0.5–8 M) and 0.03 M hydrofluoric acid decreased with increasing acid concentration reached to a minimum at about 2 M and then increased with increasing acid concentration. At low acidity, extraction of protactinium from hydrofluoric acid was higher compared to hydrochloric acid and the mixture of hydrochloric and hydrofluoric acids. Nitric acid (10 M) and hydrofluoric acid (10 M) were suitable for quantitative recovery of protactinium from organic phase. The extraction of ²³¹Pa from real thorium lean raffinate of thorium–uranium extraction process was studied using optimized extraction conditions.     

The recovery of uranium from zircaloy-uranium alloy

A process has been studied in which Zircaloy-uranium alloy is dissolved in a mixture of hydrofluoric acid and potassium fluoride. The uranium can be precipitated with an efficiency of 99.9%, as a complex potassium uranium fluoride, together with some of the zirconium in analogous complexes. These precipitates, when dissolved in a mixture of aluminium nitrate and nitric acid, give stable solutions from which uranium may be recovered by solvent extraction with an overall efficiency of 99.7%.     

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.     

Chloride-free biodegradable organic acid hydrolyzed zinc silicate coating

Partially hydrolyzed ethyl silicate has widely been used as a binder to formulate inorganic zinc silicate paint for anticorrosive coating applications. Hydrochloric acid is used most popularly to catalyze the hydrolysis of ethyl silicate. Although different acids have been tried as catalysts for ethyl silicate hydrolysis, no attempt has been made to make stable paints out of those hydrolyzed silicate binders. In this study, environment benign biodegradable organic acids such as oxalic acid, citric acid, lactic acid and acetic acid were used for the hydrolysis of ethyl silicate and compared with the hydrolysis using conventional hydrochloric acid. The hydrolyzed silicate sols were pigmented further with silica powder and evaluated for their stability. Of the various organic acids catalyst used, only oxalic acid catalyzed sol acted as a stable binder system. The pigmented binder was then mixed with metallic zinc to formulate anticorrosive inorganic zinc silicate paint. The resultant coatings were characterized for various physical, surface, mechanical and chemical resistance properties such as drying, hardness, adhesion (cross hatch) and solvent resistance. Corrosion resistance properties were analyzed by means of salt spray, open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS). The results revealed that the physical, mechanical, chemical and anticorrosive properties of the coating hydrolyzed with hydrochloric acid and oxalic acid are comparable. Thus, a chloride free biodegradable organic acid hydrolyzed inorganic zinc silicate primer is reported and due to its long term stability same also can be scaled up commercially.     

Distribution of hydrochloric acid between tri-n-butyl phosphate and water

The distribution of hydrochloric acid between water and 40 vol.-% solutions of tri-n-butyl phosphate (TBP) in six diluents and also between water and 20. 40 and 60 vol.-% solutions of TBP in odourless kerosene and pure TBP at 20°, 30° and 50° has been studied to find the effects of temperature, diluent and TBP concentration on the extractability of hydrochloric acid and on third-phase formation.