Chemistry of Uranium in Aluminophosphate Glasses

The U(VI)-U(V)-U(IV) redox equilibria were monitored in two sodium aluminophosphate base compositions at a variety of melt temperatures, imposed oxygen fugacities, and uranium contents. The higher redox states of uranium were quite soluble in the phosphate glasses, whereas U(IV) would readily precipitate from the melts as UO₂. Comparisons of the uranium redox equilibria established in phosphate melts vs those in silicate melts indicated that the coordination sites of the individual uranium species are generally the same in both solvent systems although they differ in detail.     

Study of Uranium Removal from Groundwater by Supported Liquid Membranes

The separation of uranium from synthetic Hanford site groundwater by liquid-liquid extraction and by supported liquid membranes (SLM) was atudied. Bis(2,4,4-trimethylpentyl) phosphinic acid, H[DTMPeP], contained in the commercial extractant Cysnex 272, was selected for the membrane carrier because of its selectivity for uranium over calcium and magnesium. n-Dodecane was used as diluent and polypropylene membranea were used as the support. A water soluble complexing agent, 1-hydroxyethane-1,1-diphoaphonic acid, HEDPA, was used as atrlpping agent.

The permeability coefficient of U(V1) was evaluated from a detailed study of the permeation of U(VI) through flat-sheet SLMs as a function of the membrane carrier concentration. The diffusion coefficient of the uranium complex in the organic phase was also evaluated from permeation experiments performed under loading conditions. Experiments were also carried out with Cs(II) and Fe(III) to measure the membrane selectivity for U(VI) over these two cations. A very high selectivity of U(VI) over Cs(II) was obtained, due the very low distribution ratio of Cs(II) with the extractant H[DTMPeP] (thermodynamic selectivity). In the case of Fe(III), a good selectivity was also obtained, due to the slow reaction of Fe(III) species with H[DTMPeP] (kinetic selectivity).

The possibility of concentrating U(VI) in the strip solution by a factor of at least 10³ has been experimentally demonstrated by properly designed distribution experiments.     

Selective Separation of Uranium using Alizarin Red S (ARS)-Modified Anion-Exchange Resin or by Flotation of U-ARS Chelate

ABSTRACT

An alizarin red S (ARS)-modified anion-exchange resin was prepared by a simple reaction of ARS with the anion exchanger Doulite A101 and used for the efficient sorption of uranium from aqueous media. The effect of various parameters on the sorption of U(VI) (pH effect, sorption kinetics, resin capacity and breakthrough curves) was investigated. The modified resin sorbs U(VI) over a wide range of pH (2·8–5) with a maximum sorption capacity of 0·68 mmol.g^?1 at pH 3·2 to 4·0. Iron (III), Zr(IV), Ti(IV), Cu(II), and Th(IV) ions are also sorbed to different extents, but Be(II), Bi(III), Ca(II), Mg(II), Pb(II), Hg(II), Zn(II), Cd(II), AI(III), Mn(II), Co(II) and Ni(II) are not sorbed; thus, conditions for separating U(VI) from these metal ions have been identified. For eluting U(VI) from the resin, 0·2 mol.L^?1 HCl was used and the recovery recorded was as high as 99.9%. The use of ARS is extended to float uranium quantitatively and selectively from aqueous media at pH = 4 by using oleic acid as a surfactant. The different parameters affecting the flotation process have also been investigated. Uranium(VI) has been effectively separated from natural water samples and certified uranium ores using both procedures.     

Sorption of Uranium and other Metal Ions on Amine-Functionalized Silica Materials

Sorption of U(VI) and other metal ions on amine-functionalized silica was studied, including aminopropylsilica (APS), 3-(ethylenediamino)propyl silica (ENPS), and 3-[2-(2-aminoethylamino)ethylamino]propyl silica (DIENPS). DIENPS showed the strongest and fastest sorption for U(VI) that can be described by Langmuir isotherm, suggesting U(VI) was sorbed at well-defined and energetically identical sites independent from each other. The sorption efficiency of DIENPS follows the order: U(VI) > Fe(III) > Cu(II) > Pb(II) > Ni(II) > Mg(II) > Sr(II). Results demonstrate that the amine-functionalized silica materials could be used as efficient sorbents to remove uranium and hazardous metal ions in environmental remediation.     

Extraction of Uranium(VI) and Plutonium(IV) with Tetra-Alkylcarbamides

ABSTRACT

The use of tetra-alkylcarbamides as novel extractants for the separation of uranium(VI) and plutonium(IV) by solvent extraction from spent nuclear fuels is investigated in this study. Batch extraction experiments show that tetra-alkylcarbamides strongly extract U(VI) with high distribution ratios. Plutonium(IV) can be co-extracted with U(VI) at high nitric acid concentration, while high U(VI)/Pu(IV) selectivities can be reached at lower acidity. Loading capacity experiments with high uranium concentrations show that alkyl chains longer than butyl are necessary to avoid third phase formation. Nevertheless, the viscosity of uranium-loaded solvents gets too high with alkyl chains longer than pentyl. Overall, this study shows that with TPU extractant (with four pentyl chains), an efficient co-extraction of uranium and plutonium can be reached (D_U,Pu > 1) for a concentration of nitric acid higher than 4 mol?L^?1, while the partition between uranium(VI) and plutonium(IV) could be operated even at 2 mol?L^?1 nitric acid without redox chemistry.     

Three-liquid-phase extraction and separation of V(V) and Cr(VI) from acidic leach solutions of high-chromium vanadium–titanium magnetite

A new method by liquid–liquid–liquid three phase system, consisting of acidified primary amine N1923(abbreviated as A-N1923), poly(ethylene glycol)(PEG) and (NH_4)_2SO_4 aqueous solution, was suggested for the separation and simultaneous extraction of V(V) and Cr(VI) from the acidic leach solutions of highchromium vanadium–titanium magnetite. Experimental results indicated that V(V) and Cr(VI) could be selectively enriched into the A-N1923 organic top phase and PEG-rich middle phase, respectively, while Al(III)and other co-existing impurity ions, such as Si(IV), Fe(III), Ti(IV), Mg(II) and Ca(II) in acidic leach solutions,could be enriched in the(NH_4)_2SO_4 bottom aqueous phase. During the process for extraction and separation of V(V) and Cr(VI), almost all of impurity ions could be removed. The separation factors between V(V) and Cr(VI) could reach 630 and 908, respectively in the organic top phase and PEG middle phase, and yields of recovered V(V) and Cr(VI) in the top phase and middle phase respectively were all above 90%.Various effects including aqueous p H, A-N1923 concentration, PEG added amount and(NH_4)_2SO_4 concentration on three-phase partitioning of V(V) and Cr(VI) were discussed. It was found that the partition of Cr(VI) into the PEG-rich middle phase was driven by hydrophobic interaction, while extraction of V(V) by A-N1923 resulted of anion exchange between NO_3~- and H_2V_(10)O_(28)~(-4). Stripping of V(V) and Cr(VI) from the top organic phase and the middle PEG-rich phase were achieved by mixing respectively with NaNO_3 aqueous solutions and Na OH-((NH_4)_2SO_4 solutions. The present work highlights a new approach for the extraction and purification of V and Cr from the complex multi-metal co-existing acidic leach solutions of high-chromium vanadium–titanium magnetite.     

X‐ray photoelectron spectroscopy investigation of the interaction of U(VI) and Fe(III) with natural humic acid in aqueous solutions

Complexes of U(VI) and Fe(III) with natural humic acid (NHA) were studied by X‐ray photoelectron spectroscopy (XPS). It follows from the analysis of the uranium and iron concentrations at the surface and in the bulk of the humates that the reaction in solution is heterogeneous. The NHA reacts as a particle. In solutions containing either U(VI) or Fe(III), NHA reacts similar with Fe(III) and U(VI). However, in a mixed solution of Fe(III) and U(VI), NHA reacts predominantly with iron. In comparison to Fe(III) complexes, the complexes with U(VI) are formed mostly in the inner of the NHA particle. Therefore, the concentration ratio U/Fe as measured by XPS increases by powdering of the particles. Salts of Fe(III) can be used to inhibit the uranium migration in form of its soluble humates.     

Extraction Chromatography of Actinides Using Cyanex‐923 as Stationary Phase

Abstract

Cyanex‐923 has been used as the stationary phase in the extraction chromatographic separation of actinide ions from simulated high‐level waste (SHLW). Chromosorb‐W was used as the solid inert support. The uptake behaviour of U(VI), Pu(IV), and Am(III) was studied by batch studies. Breakthrough capacity of the column for Am(III) in the presence of macro amount of Eu(III) has been determined in three successive cycles of loading and elution. The influence of interfering ions like Fe(III), Cr(VI), Al(III), and Ni(II), etc. has been investigated. Effect of column parameters like diameter and height on Am(III) elution profile has also been studied.     

黄腐酸和湖泊孔隙水对Fe(Ⅱ)还原Cr(Ⅵ)为Cr(Ⅲ)的影响

考查了缺氧条件下Fe(Ⅱ)-有机质(DOM)的络合物将Cr(Ⅵ)还原为Cr(Ⅲ)的还原能力。研究发现在没有或有萨旺尼河黄腐酸(SRFA)和波尼湖黄腐酸(PLFA)存在的情况下,Fe(Ⅱ)都能够将Cr(Ⅵ)快速地还原(几分钟)。Fe(Ⅱ)-DOM溶液不一定比仅含有Fe(Ⅱ)单一的体系具有更强的还原力。DOM的组成也影响了Cr(Ⅲ)的还原机制,湿地(俄亥俄州老妇人河河口区)沉积物进行缺氧萃取得到的沉积物孔隙水能够将Cr(Ⅵ)更快地还原。这些研究数据表明自然界中富含Fe(Ⅱ)和DOM的缺氧孔隙水对Cr(Ⅵ)的非生物还原反应速率远大于生物还原反应速率,并且这一非生物还原反应是自然环境中Cr(Ⅵ)被还原的主要途径。     

UPTAKE OF METAL IONS BY A NEW CHELATING ION-EXCHANGE RESIN. PART 4 : KINETICS

Abstract

The rate of uptake of several actinide ions [Am(III), U(VI), Th(IV), Np(IV) and Pu(IV)] and of some transition-metal ions [Co(II), Zn(II), Fe(III) and Cr(III)] at tracer concentration level, from solutions of various compositions, 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. It binds actinide and other ions through the formation of chelate complexes with the phosphoryl groups of the gem-diphosphonic acids. The experiments discussed in this work have allowed us to establish the paramount importance of the presence of the sulfonic groups in obtaining practically useful rates of metal ions uptake. Comparison of the kinetic behavior of Diphonix with that of commercial sulfonic-type resins has shown that Diphonix reacts with the investigated ions as rapidly as do the other resins. Conditions for efficient and rapid stripping of all the investigated cations, including Cr(III), have been found.     

Rapid Reduction of U(VI) on Activated Platinum Wire Gauze Electrode for the Primary Coulometric Determination of Uranium

A large enhancement in the active area of a hollow cylindrical platinum wire gauze electrode was achieved by repetitive multilayer growth of oxide followed by its reduction. Growth of oxide was obtained by a combination of chemical and electrochemical treatments. Enhancement in the active area of the electrode was checked by determining the time taken for the quantitative reduction of U(VI) to U(IV) at a controlled potential of –0.150 V vs SCE in 1 M H₂SO₄. A six-fold decrease in the reduction time was observed, indicating a corresponding six-fold increase in the active area of the electrode. The enhanced activity of the electrode was found to decay on ageing. Determination of uranium was carried out by a successive addition technique using the activated platinum wire gauze electrode and carrying out the reduction U(VI) to U(IV) at a controlled potential of –0.150 V vs SCE. Precision and accuracy of better than ±0.2% were obtained at 5 to 10 mg levels of uranium. This demonstrates the applicability of a platinum electrode, instead of the conventionally used Hg electrode, for determination of uranium by primary coulometry.     

Gel-Liquid Extraction and Separation of U(VI), Th(IV), Ce(lll), and Co(ll)

Abstract

The gel-liquid extraction of U(VI), Th(IV), Ce(III), and Co(II) has been investigated in the 0.01 to 2 M HNO₃ range using a gel prepared by swelling styrene divinylbenzene with di-(2-ethylhexyl)phosphoric acid. Obtained results indicate that all of the tested cations can be extracted and that the extraction coefficients increase in the order Ce(III) < Co(II) < Th(IV) < U(VI) and generally decrease with acidity. Under suitable conditions, separation of Th(IV), Ce(III), or Co(II) from U(VI) or of Th(IV) from Ce(III) can be achieved. Kinetic studies indicate that the extraction process is controlled by a progressive shell sorption mechanism.     

Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery

The redox flow battery using uranium as the negative and the positive active materials in polar aprotic solvents was proposed. In order to establish the guiding principle for the uranium compounds as the active materials, the investigation of uranium β-diketonate complexes was conducted on (i) the solubility of active materials, (ii) the electrode reaction of U(VI) and U(IV) β-diketonate complexes and (iii) the estimation of the open circuit voltage of the battery. The solubilities of higher than 0.8 mol dm⁻³ of U(VI) complexes and higher than 0.4 mol dm⁻³ of a U(IV) complex were obtained in the solvents. The electrode reactions of U(pta)₄, UO₂(dpm)₂, UO₂(fod)₂ and UO₂(pta)₂ were first studied and the redox potentials of uranium β-diketonates were thermodynamically discussed. The open circuit voltage is estimated more than 1 V by using Hacac or Hdpm. The larger open circuit voltage is expected when a ligand with the larger basicity is used.     

Uranium stabilization in red mud by sintering: Mechanism and leachability

Uranium(VI)-bearing waste is inevitably produced in the process of aqueous U(VI) abatement by red mud (RM). Such U(VI)-bearing waste has been considered to be highly hazardous to the environment and human because of their easy mobility, high toxicity, and radioactive. The stabilization of uranium constitutes an urgent challenge that must be solved through an economic and feasible waste management strategy. Herein, a low thermal stabilization process was well-designed for stabilizing U(VI) in red mud into particular phase(s) such as geopolymer-like microstructures. Characterization and leaching experiments were further performed for U(VI)-bearing RM samples thermally stabilized at various temperatures, and the stabilization mechanism of uranium in the RM was explored. X-ray diffraction (XRD) results revealed that a geopolymer-like phase whose main components were Al, Si and O was formed when the U(VI)-bearing RM was treated at 600 °C; thus, uranium was successfully stabilized. When treated at higher temperature (i.e., 900 °C), the U(VI)-bearing RM formed feldspar minerals from the oxides of Si and Al, which originated from the broken geopolymers (a stable three-dimensional network), thus exposing uranium to the surface. The constant-pH leaching test evidenced that the sintering temperatures of 600–800 °C could facilitate the fixation of uranium by RM. The findings of this study offer us a promising strategy on the utilization of RM to eliminate and stabilize U(VI) from waste streams.     

Note: Effect of Temperature in the Extraction of Uranium and Plutonium by Triisoamyl Phosphate

Abstract

The extraction of uranium(VI) by triisoamyl phosphate (TiAP) has been studied to derive the thermodynamic parameters such as entropy change and the free-energy change. The extraction of U(VI) and Pu(IV) has also been studied with 1.1 M solutions of tri-n-butyl phosphate (TBP), tri-n-amyl phosphate (TAP), and TiAP as a function of temperature. While the enthalpy of U(VI) extraction was found to be exothermic, the enthalpy for the extraction of Pu(IV) was always found to be endothermic. The temperature at which the distribution ratios of U(VI) and Pu(IV) cross each other (the temperature of inversion) has been derived for TBP, TAP, and TiAP, and the results reveal the lowest temperature of inversion occurs for TiAP. The results indicate the advantage of TiAP as an extractant in avoiding plutonium reflux during the PUREX process involving high plutonium feed solutions, in addition to lower aqueous solubility, freedom from the third-phase formation problem, lower degradation, and better economics.     

UPTAKE OF METAL IONS BY A NEW CHELATING ION-EXCHANGE RESIN. PART 5 : THE EFFECT OF SOLUTION MATRIX ON ACTINIDES

ABSTRACT

The influence of commonly occurring matrix constituents on the uptake of representative actinides in the tri-, tetra-, and hexavalent oxidation states by a new chelating ion exchange resin, called Diphonix?, has been investigated. The effect of increasing concentrations of HF at three fixed HC1 concentrations on the retention of U(VI), Np(IV), and Am(III) was measured. All three actinides showed strong retention in HF even up to a concentration of 1 M The effect of sulfuric, oxalic and phosphoric acids at three fixed HNO₃ concentrations on the retention of Th(IV), U(VI), and Am(III) was also measured. Only when the concentration of the complexing acids was above 0.1 M was the retention of the actinides decreased significantly at 0.1 M HNO₃ The effect was much less pronounced at higher HNO₃ concentrations.

Sodium, calcium, aluminum and iron were selected to study the influence of cationic matrix constituents on the uptake of actinide ions by Diphonix. In the case of tetra- and hexavalent actinides (represented by Th and U, respectively) only the very highest concentrations of Fe(III) and Al(III) caused a significant decrease in the retention of the two higher valent actinides. On the other hand, Am(III) retention was significantly lowered by Al and Fe(III) concentrations above 10^?2 M The influence of Al and Fe(III) on the uptake of Am(III) may be minimized by use of fluoride ion to complex Al and by reducing Fe(III) to Fe(II). Macroconcentrations of sodium and calcium had only minimal influence on the uptake of actinides in all three oxidation states.     

Change in the redox potential of a glass melt upon introducing a melting catalyst into the glass batch

The change in the direction of the redox equilibrium Fe(II)=Fe(III) and S(IV)=S(VI) in glass melting upon introducing sodium silicofluoride as a melting catalyst is considered. Translated from Steklo i Keramika, No. 3, pp. 5–7, March, 2000.     

Carbamoylalkylphosphonates for Dramatic Enhancement of Uranium Extraction from Phosphates Ores

We describe here the full synthesis of a novel family of bifunctional ligands and present a complete study of their extraction properties in regards to an aqueous phosphoric acid solution containing uranium. We developed a high yielding synthesis of amido phosphonate ligands and focused our investigation on the effect of steric hindrance on the methylene bridge between the two functions. These new bifunctional ligands were found to extract selectively hexavalent uranium U(VI) with high distribution coefficient (D) and selectivity towards iron Fe (III) in 5 M phosphoric acid solution. From a structure-activity approach a specific ligand called DEHCNPB has been put forward in regard to the outstanding results obtained for the selective extraction, and quantitative recovery of uranium compared to the URPHOS reference system.     

Actinide Valences in Borosilicate Glass

Optical and Mössbauer spectra show that actinide ions are incorporated in a borosilicate glass matrix as U(VI), Np(IV), P(IV), and Am(III). Uranium was reduced by graphite to U(V) and U(IV), but Pu(IV) remained unchanged. It is inferred from their valences that Np, Pu, and Am are part of the borosilicate network and U is probably a network-modifier.     

Electrochemical oxidation of divalent iron mixed oxides using carbon paste electrodes

The electrochemical behaviours of several iron(II) mixed oxides, Fe(II)M₂O₄ [where M = Fe(III), Al(III) and Cr(III)], and Fe(II) Ti(IV)O₃ were investigated using a carbon paste electrode with 1 M HCl binder. Solids containing Fe(III), Al(III) and Ti(IV) are not oxidized when the potential varies from +0.2 to + 1.1 V/sce whereas FeCr₂O₄ exhibits two oxidation peaks. The first one at about +0.4 V/sce, is due to iron(II) ions because the finest particles (< 100 nm) are immediately chemically solubilized. The second peak occurring at more positive potential is larger and corresponds to the oxidation of the biggest particles. This behaviour is similar to that of the reduction of Fe₂O₃ described elsewhere. So the oxidation phenomenon is the addition of two consecutive steps: a chemical solubilization followed by an oxidation and the shape of the second peak is influenced by the morphology of the oxide under study. Influences of the nature of the binder, of the synthesis procedure and of the grinding are reviewed.