Studies on the Separation and Recovery of Uranium from Phosphoric Acid Medium Using a Synergistic Mixture of (2-Ethylhexyl)phosphonic Acid Mono 2-Ethyl Hexyl Ester (PC-88A) and Tri-n-octylphosphine Oxide (TOPO)

This paper deals with studies on the extraction of uranium(VI) from phosphoric acid medium using (2-ethylhexyl)phosphonic acid mono 2-ethylhexyl ester and tri-n-octylphosphine oxide individually as well as from their synergistic mixture. Different extraction parameters were investigated. With an increase in phosphoric acid concentration in the aqueous phase, the distribution ratio (Du) was found to decrease in all the cases. Synergism was observed when a mixture of PC-88A and TOPO was used. The synergistic mixture in the mole ratio of 4:1 (1.80 M PC-88A: 0.45 M TOPO) in xylene was found to be most suitable for uranium extraction. Among the various strip liquors used, 5% (w/v) solution of (NH₄)₂CO₃ was found to be the most suitable. Using a mixture of 1.8 M PC-88A and 0.45 M TOPO as the extractant system and 0.5 M ammonium carbonate as the stripping agent, uranium recovery was found to be better than 97% ± 3% in multiple contacts, (n = 2) from actual Davies Gray Waste while in case of wet phosphoric acid more than 52% ± 3% (n = 3) only could be recovered where n is the number of contacts.     

Uranium Extraction from Phosphoric Acid Using Bifunctional Amido-Phosphonic Acid Ligands

Ligand systems containing amido-phosphonic acid moieties were synthesized for subsequent U(VI) extraction from phosphoric acid solutions. Studies have shown that the efficiency of extraction (distribution ratios and selectivity of U(VI) over Fe(III)) is influenced by the nature of the N-dialkyl substituents and the length and nature of the spacer. A structure-activity approach resulted in the identification of a specific ligand called DEHCBPA that exhibited larger D-values than the corresponding URPHOS reference system. The distribution ratios for U(VI) extraction increased considerably with a branched N-dialkyl chain when a steric hindrance was introduced into the methylene bridge of the amido-phosphonic acid ligands.     

Studies on the Recovery of Uranium from Phosphoric Acid Medium by D2EHPA/n-Dodecane Supported Liquid Membrane

Abstract

Present studies deal with the application of supported liquid membrane (SLM) technique for the separation of uranium (VI) from phosphoric acid medium using Di-2 ethyl hexyl phosphoric acid (D2EHPA)/n-dodecane as a carrier and ammonium carbonate as a receiving phase. The studies involve the investigation of process controlling parameters like feed acidity of phosphoric acid, carrier concentration, stripping agents, and the effect of thickness and the pore size of the membrane. The transport of uranium decreases with increase in the concentration of phosphoric acid in feed solution whereas it increases with increase in carrier concentration in supported liquid membrane. More than 90% uranium (VI) is recovered in 360 minutes using 0.5 M D2EHPA/dodecane as carrier and 0.5 M ammonium carbonate as stripping phase from the 0.001 M H₃PO₄ feed. Lower concentration of phosphoric acid and higher carrier concentration is found to be the most suitable condition for maximum transport of uranium (VI) from its lean sources like commercial phosphoric acid and analytical wastes generated from the analysis of uranium by Volumetric (Davis-Gray) method.     

Carrier Mediated Transport of Thorium from Nitric Acid Medium using 2-Ethyl Hexyl Hydrogen 2-Ethyl Hexyl Phosphonate (PC88A)/N-Dodecane as Carrier

The present study deals with the application of supported liquid membrane (SLM) technique for the separation of thorium from nitric acid medium using 2-ethyl hexyl hydrogen 2-ethyl hexyl phosphonate (PC88A) as a carrier and aqueous ammonium carbonate as a receiving phase. The effects of feed acidity, nature of strippant, and membrane pore size and membrane thickness on the transport of thorium have been studied in detail. Transport behavior of uranium (²³³U) and fission products from a radioanalytical laboratory waste is also studied. Stability of the membrane against the leaching of the extractant and stability of the membrane support have been investigated. An attempt has been made to model the physicochemical transport of thorium in SLM and establish the mechanism of thorium transport. Transport of thorium increased from 25% to about 96% using 0.75 M PC88A in n-dodecane as carrier and 2 M ammonium carbonate as stripping phase as the feed acidity decreased from 4 M HNO₃ to 0.5 M HNO₃. Optimum conditions obtained from this study were applied to recover thorium and ²³³U from analytical waste generated in the laboratory.     

Development of New Cationic Exchangers for the Recovery of Uranium (VI) from Concentrated Phosphoric Acid

The extraction of uranium (VI) from 5.3 mol.L^?1 phosphoric acid with a series of phosphoric, phosphinic, dithiophosphoric, or dithiophosphinic acid derivatives (0.5 mol.L^?1) in mixture with 0.125 mol.L^?1 TOPO in Isane IP 185 has been investigated. In the frame of the present work, eight acidic phosphorus and thiophosphorus compounds have been synthesized: bis(1,3-diisobutoxypropan-2-yl) phosphoric acid, bis(1,3-bis-(butylthio)propan-2-yl) phosphoric acid, bis(5,8,12,15-tetraoxanonadecan-10-yl) phosphoric acid, bis(1-butoxyheptan-2-yl) phosphoric acid, bis(undecan-6-yl) phosphoric acid, bis(2-(1,3-dibutoxypropan-2-yloxy)ethyl) phosphoric acid, bis(3-butoxy-2-(butoxymethyl)-2-methylpropyl) phosphinic acid, bis(1,3-dibutoxypropan-2-yl) dithiophosphoric acid. The properties of these molecules in mixtures with TOPO have been compared with those of other extractants such as bis(2-ethylhexyl) phosphoric acid, bis(2-ethylhexyl) dithiophosphoric acid, bis(2-ethylhexyl) phosphinic acid, Cyanex® 272, and Cyanex® 301. The replacement of phosphoric acid-type extractant by their phosphinic homologues dramatically decreases the affinity for uranium (VI) whereas the replacement of the phosphoric and phosphinic acid-type extractants by their dithio homologues affects positively the distribution coefficient of uranium (VI). It also appears that the steric hindrance effect is responsible for a significant decrease of the distribution coefficient of uranium (VI). Supplemental materials are available for this article. Go to the publisher's online edition of Separation Science and Technology to view the free supplemental file.     

Studies on the Separation and Recovery of Plutonium from Nitric Acid Medium using Di-nonyl Phenyl Phosphoric Acid (DNPPA) / n-Dodecane as Extractant System

This paper deals with the studies on the separation and recovery of plutonium from nitric acid medium using Di-nonyl phenyl phosphoric acid (DNPPA) in n-paraffin as an extractant system. The different extraction parameters were investigated. The percentage extraction of plutonium decreased with increase in nitric acid concentration. The optimum solvent concentration for quantitative separation of plutonium from aqueous feed solution was 0.15 M of DNPPA whereas n-paraffin/n-dodecane was the most suitable of diluents with an organic to aqueous phase ratio of 1:1. Among the various strippants used, 0.5 M solution of (NH₄)₂CO₃ was found to be the most suitable for back extraction of plutonium from the loaded organic phase. The developed method was used to separate and recover plutonium from actual wash solution of ion exchange column used for plutonium purification. More than 73% of plutonium was separated from 7 M HNO₃ wash solution using 0.15M of DNPPA in n-dodecane.     

Liquid–Liquid Extraction of Uranium from Phosphoric Acid by HDEHP–CYANEX-921 Mixture

The extraction of uranyl ions from different phosphoric acid media by CYANEX-921 (a commercial trioctyl phosphine oxide) mixed with di-2-ethylhexyl phosphoric acid diluted with odourless kerosene has been investigated. The effect of phosphoric acid, CYANEX-921 and HDEHP concentrations, as well as temperature on the extraction were studied. The extraction rate for UO₂²⁺ transfer from 5 M phosphoric acid to the organic phase containing a CYANEX-921–HDEHP mixture in a single drop column without external force was also studied. The mass transfer of uranium in the organic extractant single drop was investigated in terms of drop size, uranium concentration as well as other parameters. The extraction rate was found to be mainly dependent on uranium, HDEHP and phosphoric acid concentrations, and found to be mainly controlled by diffusion in the single drop. Further, it was found that CYANEX-921 can substitute TOPO to synergise the extraction of UO₂²⁺ by HDEHP. © 1997 SCI.     

Extraction Behavior of Am(III) and Eu(III) from Nitric Acid Medium in Tetraoctyldiglycolamide-Bis(2-Ethylhexyl)Phosphoric Acid Solution

The extraction behavior of Am(III) and Eu(III) in a solution of tetra-octyldiglycolamide (TODGA), bis(2-ethylhexyl)phosphoric acid (HDEHP), and n-dodecane (n-DD) was studied to understand the role of TODGA and HDEHP in the combined solvent system. The extraction behavior of these metal ions was compared with those observed in TODGA/n-DD and HDEHP/n-DD. The effect of various parameters such as concentrations of HNO₃, TODGA, and HDEHP on the distribution ratio of Am(III) and Eu(III) was studied. Synergistic extraction of both the metal ions observed at lower acidities (<2.0 M) was attributed to the involvement of TODGA and HDEHP for extraction. However, the extraction of Am(III) and Eu(III) in the combined solvent was comparable with that observed in TODGA at higher acidities. The slope analysis of the extraction data confirmed the involvement of both the extractants at all acidities investigated in the present study.     

Synergic Extraction of Folic Acid with Di(2-ethylhexyl) Phosphoric Acid and Amberlite LA-2

The influences of extractants concentrations and solvent polarity on the efficiency of folic acid separation by synergic extraction with Amberlite LA-2 and di(2-ethylhexyl) phosphoric acid (D2EHPA) mixture have been analyzed. The results indicated the formation of an interfacial compound which includes one molecule of folic acid and one of D2EHPA, the hydrophobicity of this compound being increased by solvation with Amberlite LA-2 molecules. The number of aminic molecules participating in the interfacial complex formation is controlled by solvent polarity and D2EHPA concentration, decreasing from 3 to 1 with the increase of these two parameters. The results indicated that the most important synergic effect corresponds to the extractants mixture dissolved n-heptane, at low D2EHPA concentration in the organic phase (5 g/l).     

Extraction of Lanthanides(III) by a Mixture of a Malonamide and a Dialkyl Phosphoric Acid

Several hydrometallurgical processes studied in France for lanthanide/minor actinide separation use a combination of DMDOHEMA and HDEHP as extractants. Although these processes have proved to be reliable, the modeling of their extraction properties remains a difficult task due to a lack of knowledge about the behavior of the mixed DMDOHEMA-HDEHP organic phase. In the present work, it was found that the solvent extraction of Ln(III) ions by a mixture of these extractants exhibits a complex behavior involving a synergistic effect at either 1 M HNO₃ or high metal concentration, and an antagonistic effect on extraction of metal traces at higher pH (> 2). To understand these effects, Ln(III) complexes formed after extraction by DMDOHEMA and/or HDEHP were characterized by several spectroscopic techniques (FT-IR, UV-Vis, ESI-MS, TRLIFS). Results suggested formation of DMDOHEMA-HDEHP adducts and ternary mixed complexes involving both extractants and possibly a nitrate ion.     

Sorption Behavior of Y(III) from Chloride Medium with Polymer Composites Containing Di-2-ethyl Hexyl Phosphoric Acid and Multiwall Carbon Nanotube

Extractant impregnated polyethersulfone beads have been prepared by phase inversion method and investigated for yttrium recovery from aqueous medium. The effect of experimental parameters on yttrium sorption has been studied. Quantitative sorption of yttrium (> 90%) was attained after 8 hours of equilibration time in the case of D2EHPA impregnated composite beads. Analysis of sorption data by different kinetic and diffusion models suggested that the sorption of Y(III) followed the pseudo-second order model. Stability tests with polymeric composite beads by multiple cycles of sorption and desorption of Y(III) have established the feasibility of reusing the beads for sorption of metal ions.     

乳状液膜法去除湿法磷酸中Mg(Ⅱ)的研究

采用乳化液膜技术对湿法磷酸进行脱镁净化是一种净化湿法磷酸的新途径。以-(2-乙基己基)磷酸酯为流动载体乳状液膜体系,系统研究了油水体积比(Roi)、膜试剂、增稠剂(石蜡量)、外水相pH值等因素对Mg(Ⅱ)的迁移行为。得出了乳化液膜法去除湿法磷酸中镁离子的最佳工艺条件：表面活性剂：L113A,膜试剂：环己烷;反萃取剂：HCl3mol／L,增稠剂：石蜡量0．5mL。     

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.     

Studies on the Separation and Recovery of Thorium from Nitric Acid Medium using (2-ethyl hexyl) Phosphonic Acid,Mono (2-ethyl hexyl) Ester (PC88A)/N-Dodecane as Extractant System

This paper deals with the studies on the separation and recovery of thorium and 233-uranium from nitric acid medium using (2-ethyl hexyl) phosphonic acid, mono (2-ethyl hexyl) ester/n-dodecane as an extractant system. The different extraction parameters were investigated. The distribution ratio of thorium decreased with increase in nitric acid concentration. The optimum solvent concentration for quantitative separation of thorium from aqueous feed solution was 0.75 M of PC88A whereas dodecane was the most suitable of diluents with an organic to aqueous phase ratio of 1:1. Among the various strippants used, 2 M solution of (NH₄)₂CO₃ was found to be the most suitable for back extraction of thorium. The developed method was used to recover thorium and ²³³U from radioanalytical waste generated during thorium analysis by ethylene diamine tetraacetic acid (EDTA) titremtric method and recoveries for both Th and U were more than 85%.