Extraction of U(VI), Th(IV), Pu(IV), and Am(III) from nitric acid solutions with polyfunctional organophosphorus acids

Extraction of microamounts of U(VI), Th(IV), Pu(IV), and Am(III) nitrates from aqueous HNO₃ solutions with solutions of (diphenylphosphinylmethyl)phenylphosphinic, (di-p-tolylphosphinylmethyl)phenylphosphinic, and (dioctylphosphinylmethyl)phosphinic acids and of butyl hydrogen (diphenylphosphinylmethyl)phosphonate in organic diluents was studied. The metal: extractant stoichiometric ratio in the extractable complexes was determined, and the diluent effect on the extraction efficiency was examined. The possibility of using a macroporous polymeric sorbent impregnated with (dioctylphosphinylmethyl)phenylphosphinic acid for concentrating metal ions from HNO₃ solutions was demonstrated.     

Extraction and sorption preconcentration of U(VI), Am(III), and Pu(IV) from nitric acid solutions with alkylenediphosphine dioxides

The extraction of U(VI), Am(III), and Pu(VI) from nitric acid solutions in the form of complexes with alkylenebis(diphenylphosphine) dioxides and their sorption with POLIORGS F-6 sorbent prepared by noncovalent immobilization of methylenebis(diphenylphosphine) dioxide (MDPPD) on a KhAD-7M? polymeric matrix were studied. The preconcentration conditions and distribution coefficients of U(VI), Am(III), and Pu(IV) in their sorption from 3 M HNO₃ were determined. The possibility of concentrating actinides from multicomponent solutions was demonstrated. The composition and nature of complexes of U(VI) with MDPPD were determined from the ³¹P NMR data.     

Preconcentration of U(VI), Th(IV), and REE(III) from nitric acid solutions using carbon nanotubes modified with bis(dioctylphosphinylmethyl)phosphinic acid

The extraction of microamounts of U(VI) and Th(IV) from HNO₃ solutions in the form of complexes with bis(dioctylphosphinylmethyl)phenylphosphinic acid was studied. The stoichiometry of the extractable complexes was studied, and the influence of the extractant structure on the efficiency and selectivity of the U(VI) and Th(IV) extraction was examined. U(VI), Th(IV), and REE(III) can be preconcentrated from nitric acid solutions with a complexing sorbent prepared by noncovalent immobilization of bis(dioctylphosphinylmethyl) phosphinic acid on the surface of carbon nanotubes.     

Extraction of U(VI), Th(IV), Pu(IV), Am(III), and rare-earth elements from nitric acid solutions with diphenyl(dialkylcarbamoylmethyl)phosphine oxides substituted in the methylene bridge

The extractive power and selectivity of diphenyl(dialkylcarbamoylmethyl)phosphine oxides in extraction of U(VI), Th(IV), Pu(IV), Am(III), and rare-earth elements from nitric acid solutions was studied, as influenced by substitution of one or two hydrogen atoms in the methylene bridge with alkyl, cycloalkyl, CH₂P(O)Ph₂, and CH₂C(O)NBu₂ groups.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 427–432.Original Russian Text Copyright © 2004 by Turanov, Karandashev, Yarkevich, Safronova, Kharitonov, Radygina, Fedoseev.     

Extraction of REEs(III), U(VI), and Th(IV) with acidic phosphoryl-containing podands from nitric acid solutions

The extraction of microamounts of REEs(III), U(VI), and Th(IV) from HNO₃ solutions with solutions of acidic phosphoryl-containing podands in 1,2-dichloroethane was studied. The stoichiometry of the extractable complexes was determined. The influence of the extractant structure and aqueous phase composition on the efficiency and selectivity of the recovery of REEs(III), U(VI), and Th(IV) into the organic phase was considered.     

Extraction of Am(III), U(VI), and Pu(IV) from HCl Solutions with Diphenyl(dibutylcarbamoylmethyl)phosphine Oxide

Extraction of Am(III), U(VI), and Pu(IV) from HCl solutions with solutions of diphenyl(dibutylcarbamoylmethyl)phosphine oxide in dichloroethane and m-nitrobenzotrifluoride was studied. The curves of the Am(III) and U(VI) extraction as a function of the acid concentration pass through a minimum at [HCl] = 1 M, followed by a steep ascent at the acid concentration increased further. The logarithmic dependences of the distribution factors on the extractant concentration are nonlinear, with the slope of the upper portions close to 2 for Am(III) and 1 for U(VI). Pu(IV) is extracted noticeably worse than U(VI). A significant anomalous aryl strengthening effect is observed in HCl solutions.     

Sorption of U(VI) from aqueous solutions with carbon sorbents

The sorption characteristics of ordinary and oxidized sorts of synthetic (SKN) and kernel (KAU) carbons and also carbon fabric oxidized with HNO₃ (AUTo) with respect to U(VI) were studied. The influence of solution pH on the sorption capacity of carbon materials with respect to uranium was elucidated. The influence of chlorine and sulfate anions on the sorption rate and sorption capacity was studied. Based on kinetic curves and sorption isotherms of uranyl ions and their derivatives, possible mechanisms of uranium adsorption with carbon sorbents were considered. It was shown that carbon sorbents can be used for treatment of aqueous media, among them drinking water, to remove U(VI) compounds.     

Extraction and sorption preconcentration of U(VI), Th(IV), and REE(III) from nitric acid solutions using amine-substituted tetraarylethylenediphosphine dioxides

Extraction of U(VI), Th(IV), and REE(III) from HNO₃ solutions in the form of complexes with amine-substituted tetraarylethylenediphosphine dioxides was studied. The effect of substituents at the P atoms in the extractant molecule on its extraction ability was examined. The stoichiometry of the extractable complexes was determined. The possibility of preconcentration of U(VI), Th(IV), and REE(III) with the complexing sorbent prepared by noncovalent immobilization of the examined extractants on a polymer matrix was demonstrated.     

Extraction of U(VI), Th(IV), and rare-earth elements from nitric acid solutions with phosphoryl-and carbonyl-containing podands

The distribution of HNO₃ and microamounts of nitrates of U(VI), Th(IV), La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y between aqueous solutions of HNO₃ and solutions of N,N′-dimethyl-N,N′-diphenyl-3-oxapentanediamide (I) and 1,3-bis(diphenylphosphinoyl)-2-oxapropane (II) in organic diluents was studied. The stoichiometry of the extractable complexes was determined, and the effect exerted by the extractant structure and by the organic diluent on the efficiency of recovery of rare-earth elements (REE) into the organic phase was examined. In nitric acid solutions, carbonyl-containing podand I surpasses in the extraction ability phosphoryl-containing podand II. The possibility of using a macroporous polymeric sorbent impregnated with compound I for recovering REE from nitric acid solutions was demonstrated. Original Russian Text A.N. Turanov, V.K. Karandashev, V.E. Baulin, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 3, pp. 226–232.     

Solid-phase extractants based on taunit carbon nanotubes for actinide and REE preconcentration from nitric acid solutions

The sorption properties of solid-phase extractants (SPEs) prepared by impregnation of Taunit carbon nanotubes with adducts of diphenyl(dibutylcarbamoylmethyl)phosphine oxide (CMPO) and tri-n-octylphosphine oxide (TOPO) in HNO₃ solutions were studied. The SPEs exhibit high ability to sorb U(VI), Pu(IV), Np(V), Am(III), and Eu(III) from nitric acid solutions, with good kinetic properties. The impregnation conditions and distribution coefficients of the radionuclides in their recovery from 3 M HNO₃ were determined. The possibility of preparing SPEs by Taunit impregnation in HNO₃ solutions with adducts of tributyl phosphate (TBP) and N,N′-dimethyl-N,N′-dioctylhexylethoxymalonamide (DMDOHEMA) and with Cyphos IL-101 phosphonium ionic liquid was demonstrated.     

Extraction of U(VI), Th(IV), and REE(III) from nitric acid solutions with (N,N-dialkylcarbamoylmethyl)- and (N-alkylcarbamoylmethyl)phenylphosphinic acids

Extraction of microamounts of U(VI), Th(IV), and REE(III) from HNO₃ solutions with solutions of (N,N-dialkylcarbamoylmethyl)- and (N-alkylcarbamoylmethyl)phenylphosphinic acids in dichloroethane was studied. The stoichiometry of the extractable complexes was determined, and the influence exerted on the efficiency of the U(VI), Th(IV), and REE(III) recovery into the organic phase by the extractant structure, organic diluent, and aqueous phase composition was examined. The possibility of selective recovery and concentration of U(VI), Th(IV), and REE(III) from nitric acid solutions with a complexing sorbent prepared by noncovalent immobilization of the examined polyfunctional organophosphorus acids on a macroporous polymeric matrix was demonstrated.     

Extraction of REEs(III), U(VI), and Th(IV) from nitric acid solutions with carbamoylmethylphosphine oxides in the presence of an ionic liquid

The extraction of REEs(III), U(VI), and Th(IV) from nitric acid solutions with solutions of diphenyl(dialkylcarbamoylmethyl)phosphine oxides is considerably enhanced in the presence of an ionic liquid, 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide. The extraction efficiency varies in a wide range depending on substituents at the P and N atoms and on the structure of the fragment linking the coordinating groups in the extractant molecule.     

Complexation of An(VI) (An = U, Np, Pu, Am) with 2,6-pyridinedicarboxylic acid in aqueous solutions. Synthesis and structures of new crystalline compounds of U(VI), Np(VI), and Pu(VI)

Complexation of An(VI) (An = U, Np, Pu, Am) with 2,6-pyridinedicarboxylic (dipicolinic) acid in aqueous solutions was studied. All these actinides form with dipicolinic acid anion, PDC^2? 1: 1 and 1: 2 complexes. The PDC^2? ion coordinates to actinide(VI) ions in solutions in tridentate fashion. In 1: 2 complexes, the f-f transition bands in the electronic absorption spectra are very weak, which is associated with approximate central symmetry of the coordination polyhedron (CP) of the An atom. The apparent stability constants of Pu(VI) complexes were measured in a wide pH range, and the concentration stability constants of An(VI) (An = U, Np, Pu, Am) were determined. The crystalline complexes [Li₂AnO₂(PDC)₂]·2H₂O (An = U, Np, Pu) and [AnO₂(PDC)] _n (An = Np, Pu) were synthesized, and their structures were determined by single crystal X-ray diffraction. The X-ray data confirmed the conclusion that CP of An atoms in the complex ions AnO₂·(PDC) ₂ ^2? is centrosymmetrical. In the isostructural series of [Li₂AnO₂(PDC)₂]·2H₂O, the actinide contraction is manifested in shortening of the An-O distances in the “yl” groups in going from U to Pu.     

Selectivity of extraction of U(VI), Th(IV), and REE(III) from perchloric acid solutions with bidentate phosphoryl-substituted butyl phenylphosphinates

Extraction of microamounts of U(VI), Th(IV), and REE(III) from HClO₄ solutions with solutions of bidentate phosphoryl-substituted butyl phenylphosphinates R₂P(O)CH₂P(O)Ph(OBu) [R = phenyl (I), octyl (II)] in dichloroethane was studied. The effect of substituents at the phosphorus atom in the phosphine oxide moiety of these compounds on their extraction ability and selectivity was examined, and the stoichiometry of the extractable complexes was determined. In going from nitric to perchloric acid solutions, the efficiency of the extraction of U(VI) and REE(III) considerably increases, the U/REE separation factors increase, but the Th/U separation factors decrease.     

Extraction and sorption preconcentration of U(VI), Th(IV), and REE(III) from nitric acid solutions using bis[2-(diphenylphosphinyl)phenoxymethyl]phosphinic acid

Extraction of microamounts of U(VI) and Th(IV) from HNO₃ solutions in the form of complexes with polyfunctional organophosphorus acids was studied. The influence of the extractant structure on the efficiency and selectivity of the extraction of U(VI) and Th(IV) was examined, and the stoichiometry of the extractable complexes was determined. The possibility of preconcentration of U(VI), Th(IV), and REE(III) from nitric acid solutions with a complexing sorbent prepared by noncovalent immobilization of bis[2-(diphenylphosphinyl) phenoxymethyl]phosphinic acid on a macroporous polymeric matrix was demonstrated.     

1,3-Bis[(diphenylphosphorylacetamido)methyl]benzene as reagent for extraction and sorption preconcentration of REE(III), U(VI), and Th(IV) from nitric acid solutions

The extraction of microamounts of REE(III), U(VI), and Th(IV) from HNO₃ solutions in the form of complexes with a polyfunctional neutral organophosphorus compound, 1,3-bis[(diphenylphosphorylacetamido)-methyl]benzene, was studied. The influence exerted by the structure of the bridge binding two carbamoylmethyl-phosphine oxide fragments on the efficiency of the extraction of REE(III), U(VI), and Th(IV) and on the stoichiometry of the extractable complexes was analyzed. The possibility of recovering and concentrating REE(III), U(VI), and Th(IV) from nitric acid solutions with a complexing sorbent prepared by noncovalent immobilization of 1,3-bis[(diphenylphosphorylacetamido)methyl]benzene on the surface of carbon nanotubes was examined.     

Reduction of Pu(IV) and Np(VI) with carbohydrazide in nitric acid solution

The reduction of Pu(IV) and Np(VI) with carbohydrazide (NH₂NH)₂CO in 1–6 M HNO₃ solutions was studied. The Pu(IV) reduction is described by a first-order rate equation with respect to Pu(IV). At [HNO₃] ≥ 3 M, the reaction becomes reversible. The rate constants of the forward and reverse reactions were determined, and their activation energies were estimated. Neptunium(VI) is reduced to Np(V) at a high rate, whereas the subsequent reduction of Np(V) to Np(IV) is considerably slower and is catalyzed by Fe and Tc ions. The possibility of using carbohydrazide for stabilizing desired combinations of Pu and Np valence states was examined.     

Synthesis and Structure of U(VI), Np(VI), and Pu(VI) Phenylacetates

Radiochemistry - Phenylacetates [AnO2(C6H5CH2COO)2], where An = U (I), Np (II), or Pu (III), were synthesized and studied by single crystal X-ray diffraction. Compounds I–III are...     

Sorption of U(VI) from sulfate solutions with spherically granulated chitosans

Sorption of U(VI) from sulfate solutions with spherically granulated chitosans was examined. It was shown that the best sorption and kinetic characteristics are exhibited by freshly formed and cross-linked chitosan granules. The total static exchange capacity for the freshly formed granules was 0.7 mmol of U(VI) per gram of dry sorbent. The diffusion coefficients and similarity criteria describing the diffusion process parameters were calculated. It was found that, irrespective of the method by which the granules were prepared (freshly formed, cross-linked, air-dried), the dominating process is U(VI) sorption on the surface, mainly controlled by external diffusion. Physicomechanical tests of the films of the irradiated chitosan and cellophane (absorbed dose 100–250 kGy) revealed higher strength characteristics of the irradiated chitosan.     

Coprecipitation of tellurium(IV), tungsten(VI), and lanthanum(III) hydroxides from aqueous solutions

We have investigated the coprecipitation of tellurium(IV), tungsten(VI), and lanthanum(III) hydroxides through the addition of aqueous ammonia to a mixture of tellurium dioxide, lanthanum oxide, and tungstic acid solutions in hydrochloric acid. The effects of initial solution composition and precipitation pH on the composition of the precipitate have been assessed. It has been shown that the composition of the precipitate is essentially identical to that of the starting solution if the relative contents of lanthanum and tungsten in the mixture are within 20 mol % and precipitation is ceased at pH 7.