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1.
This paper describes ongoing research into the multi-physics model development of an electrorefining process for the treatment of spent nuclear fuel. A forced convection of molten eutectic (LiCl–KCl) electrolyte in an electrorefining cell is considered to establish an appropriate electro-fluid model within the 3-dimensional framework of a conventional computational fluid dynamic model. This computational platform includes the electrochemical reaction rate of charge transfer kinetics which is described by a Butler–Volmer equation, while mass transport is considered using an ionic transport equation. The coupling of the local overpotential distribution and uranium concentration gradient makes it possible to predict the local current density distribution at the electrode surfaces.  相似文献   

2.
The nitrate salt solution of the secondary amine Amberlite LA-1 in organic solvents extracts uranium(IV) from aqueous nitric acid solutions. The distribution ratio of uranium(IV) reaches a maximum at an equilibrium nitric acid concentration of 8.5M in the aqueous phase. Addition of n-octanol to the organic phase decreases, and the addition of nitrate to the aqueous phase increases the uranium(IV) distribution ratio. The extraction of uranium(IV) is fast and the equilibrium distribution is reached within less than one minute. At low uranium(IV) concentrations (<6·10−3 M) the distribution ratio is independent of the uranium(IV) concentration. At high uranium(IV) loadings of the organic phase an extrapolation gives a mole ratio of amine: uranium(IV)=2∶1. A double logarithmic plot of the dependence of the uranium(IV) distribution ratio vs. the LA-1 concentration in the organic phase gives a curve with a slope of two when polar diluents for LA-1 are used. This slope of two and the shapes of the absorption spectra of the organic phase from 400 to 700 nm make it very probable that uranium(IV) exists in the organic phase as a hexanitrato complex.   相似文献   

3.
A computational electrochemo-fluid dynamics model has been developed to describe the electrowinning behavior in an electrolyte stream through a planar electrode cell system. Electrode reaction of the uranium electrowinning process from a molten-salt electrolyte stream was modeled to illustrate the details of the flow-assisted mass transport of ions to the cathode. This modeling approach makes it possible to represent variations of the convective diffusion limited current density by taking into account the concentration profile at the electrode surface as a function of the flow characteristics and applied current density in a commercially available computational fluid dynamics platform. It was possible to predict the conventional current–voltage relation in addition to details of electrolyte fluid dynamics and electrochemical variables, such as the flow field, species concentrations, potential, and current distributions throughout the galvanostatic electrolysis cell.  相似文献   

4.
The polarographic behavior of uranium in hydroxylamine hydrochloride was investigated by differential oscillographic polarography. A procedure is presented for the determination of uranium in plutonium for concentrations of uranium greater than 10 p.p.m. Analyses of solutions containing 22 common impurities found in plutonium metal revealed that antimony, copper, and titanium cause significant interference. A reversible peak corresponding to a one-electron reduction was obtained with a peak potential of -0.167 V vs. Hg pool electrode. The diffusion coefficient is 0.51·10-5 cm2/sec and the diffusion current constant is 1.59 with an average relative standard deviation of 2.28%. The peak current of uranium can be affected by hydrochloric, nitric, perchloric, and sulfuric acids, depending on the acid concentration.  相似文献   

5.
The extraction behavior of uranium (VI) from chloride medium with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) in dodecane has been investigated under wide range of conditions. Attempts have been made to establish the extraction mechanism of uranium(VI) with PC-88A. Treatment of the distribution data by slope analysis technique showed the formation of a monomeric complex of the nature [UO2(A2H)2]. Formation of this species was also confirmed by non-linear least square regression of the distribution data to the mathematical expression correlating percentage extraction and acidity. In this investigation attempts have also been made to develop a mathematical model for the system (UO2Cl2-HCl-H2O-PC-88A-dodecane) using experimental data on the distribution of uranium against initial aqueous acidity at different initial metal concentration. The mathematical model D = 37.547±0.223/C i 1/2×[H i ]2 can be used to predict the concentration of uranium in organic as well as in aqueous phases at any initial concentration of uranium [C i ] and initial hydrogen ion concentration [H i ]. The extraction constant (K ex ) has been calculated.  相似文献   

6.
Phaseolus vulgaris L. (bean) is a promising species for uranium rhizofiltration with high tolerance and accumulation ability. To further understand the mechanisms involved in uranium tolerance and detoxification, the present study investigated subcellular distribution and compartmentalization of uranium in bean. Subcellular fractionation of uranium containing tissues indicated that both in roots and shoots, the concentration of uranium in each subcellular fractions increased evidently with increasing solution uranium level, and the majority of uranium was located in cytosol and cell wall fraction, while a minor part of uranium associated with the organelle fraction. Meanwhile, with uranium concentration increasing from 100 to 1,000 μM, the proportion of uranium distribution in cytosol fraction was decreased but it was increased in cell wall fraction. However, the proportion of uranium distribution in organelle fraction is always less than 5 %. These results suggest that stored in the cytosol (such as uranium compartmentalization with organo-ligands in vacuole) and bound to the cell walls (may be integrated with polyose and protein) might play an important role in tolerance and detoxification of uranium in bean.  相似文献   

7.
《Analytical letters》2012,45(18):3085-3095
Abstract

A new method is presented for determination of uranium based on a cathodic adsorptive stripping of the complex of uranium with a 3-hydroxy-2-naphthoic hydrazide at a hanging mercury drop electrode (HMDE). The most suitable operating conditions and parameters, such as pH, deposition potential, deposition time, ligand concentration, and others, were selected and the determination of uranium from aqueous solutions using the standard addition method was possible. Under optimum conditions, the measured peak current is proportional to the concentration of uranium over the range of 1–500 nA with a detection limit of 0.75 nM.  相似文献   

8.
The polarographic behavior of the uranium-malonate complex was investigated over the pH range 1.1–6.5. A reversible, one-electron wave was obtained. Below pH 4.9, the rate of disproportionation is nearly instantaneous and gives rise to a pseudo uranium(VI)-uranium(IV) reduction. Above pH 4.8 the concentration of uranium(V) is stable with respect to disproportionation. The half-wave potential is pH-dependent below pH 4.9, but it is independent of the malonate concentration above O.1 M. The diffusion current constant is 2.78 for the conditions described. A procedure for the determination of uranium in plutonium was developed for uranium concentrations greater than 225 p.p.m. Of 21 common impurities found in plutonium metal, only Cu, Fe, Pb, Sb and Ti cause significant interference ; titanium can be removed by ion exchange, and the other interferences by mercury cathode electrolysis.  相似文献   

9.
Many advanced reprocessing schemes under development are aimed at co-processing and co-conversion of actinides, unlike current reprocessing plants that produce separate uranium and plutonium products. The most well developed option for the co-conversion stage is probably oxalate co-precipitation, followed by the thermal co-conversion to a mixed oxide product. It is thus envisaged that future processes will avoid separation of plutonium from uranium and instead allow part of the uranium to flow with the plutonium, resulting in co-precipitation as the oxalate, and finally co-conversion to a mixed uranium-plutonium oxide (MOX), which can be fabricated into recycled nuclear fuel for further energy generation.The co-crystallisation of uranium (IV) and plutonium (III) into a single oxalate structure ensures the homogenous distribution of the two actinides at the molecular scale. The joint conversion of uranium and plutonium to the oxide form makes it possible to remove the complicated step of blending and grinding the two distinct oxide powders, as currently employed for the purposes of MOX fuel fabrication. This concept can also be extended to other actinides, including minor actinides from partitioning processes such as SANEX (Selective Actinide Extraction) and GANEX (Grouped Actinide Extraction) processes or even a thorium containing product from recycle of thorium based fuels.A selection of UxTh1-x(C2O4)2 solids at varying concentrations of uranium and thorium were prepared by oxalate co-precipitation. Uranium (VI) was conditioned electrochemically at -0.7 V to uranium (IV), in the presence of hydrazine. The reduced uranium (IV) in nitric acid was mixed with thorium nitrate solutions at different concentration ratios with oxalic acid. The mixed tetravalent uranium-thorium oxalate solid products have been characterised by Raman and IR spectroscopies. The influence of thorium substituted into the uranium oxalate structure was evaluated. Several vibrational modes were found to be affected by the variation in ionic radius appearing to be metal sensitive and therefore, provide the initial indication in the evaluation of the chemical composition.  相似文献   

10.
11.
A multiphysics model for a production scale planar solid oxide fuel cell (SOFC) stack is important for the SOFC technology, but usually requires an unpractical amount of computing resource. The major cause for the huge computing resource requirement is identified as the need to solve the cathode O2 transport and the associated electrochemistry. To overcome the technical obstacle, an analytical model for solving the O2 transport and its coupling with the electrochemistry is derived. The analytical model is used to greatly reduce the numerical mesh complexity of a multiphysics model. Numerical test shows that the analytical approximation is highly accurate and stable. A multiphysics numerical modeling tool taking advantage of the analytical solution is then developed through Fluent®. The numerical efficiency and stability of this modeling tool are further demonstrated by simulating a 30-cell stack with a production scale cell size. Detailed information about the stack performance is revealed and brie y discussed. The multiphysics modeling tool can be used to guide the stack design and select the operating parameters.  相似文献   

12.
Adsorption studies of thorium and uranium radionuclides on 9 different pure clay minerals and 4 local Malaysian soil sediments were conducted. Solution containing dissolved thorium and uranium at pH 4.90 was prepared from concentrate sludges from a long term storage facility at a local mineral processing plant. The sludges are considered as low level radioactive wastes. The results indicated that the 9 clay minerals adsorbed more uranium than thorium at pH ranges from 3.74 to 5.74. Two local Malaysian soils were observed to adsorb relatively high concentration of both radionuclides at pH 3.79 to 3.91. The adsorption value 23.27 to 27.04 ppm for uranium and 33.1 to 50.18 ppm for thorium indicated that both soil sediments can be considered as potential enhanced barrier material for sites disposing conditioned wastes containing uranium and thorium.  相似文献   

13.
Simultaneous determination of uranium and thorium using arsenazo III as a chromogenic reagent at pH 1.70 by H‐point standard addition method (HPSAM) and partial least squares (PLS) calibration is described. Under optimum conditions, the simultaneous determinations of uranium and thorium by HPSAM were performed. The absorbencies at one pair of wavelengths, 649 and 669 nm, were monitored with the addition of standard solutions of uranium. The results of applying the HPSAM showed that uranium and thorium can be determined simultaneously with weight concentration ratios of uranium to thorium varying from 20:1 to 1:15 in the mixed sample. By multivariate calibration methods such as PLS, it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. In this study, the calibration model is based on absorption spectra in the 600–750 nm range for 25 different mixtures of uranium and thorium. Calibration matrices contained 0.10–21.00 and 0.25–18.5 μg mL?1 of uranium and thorium, respectively. The RMSEP for uranium and thorium were 0.7400 and 0.7276, respectively. Both proposed methods (HPSAM and PLS) were also successfully applied to the determination of uranium and thorium in several synthetic and real matrix samples.  相似文献   

14.
Chronic exposure to uranium compounds led to the development of a methodology in order to characterize those compounds. This methodology, based on the recommendation of the I.C.R.P,1 involves three main steps: the measurement of the uranium concentration and the particle size distribution at workstations; the characterization of the industrial compound, i.e. its physico-chemical properties; and the study of in-vitro solubility using chemical and cellular tests. Different methods for uranium analysis are presented. Results and comments on UF4, UO3, U3O8, UO2 and U+UO2 are given.  相似文献   

15.
The implementation of the new ICRP recommendations and the diversity of industrial exposure materials make it necessary to modify our approach of assessing internal dosimetry.This paper describes a methodology developed to assess different parameters such as (1) activity concentration and particle size distribution at the workplace; (2) physico-chemical characteristics of industrial dust handled, and (2) in vitro and in vivo, solubility in order to determine the absorption rate into blood. The determination of such specific parameters will lead to dose calculation in terms of committed effective Dose Per Unit of Intake (DPUI). Results obtained for an industrial uranium dioxide, UO2, at a French nuclear facility are presented.  相似文献   

16.
Studying the growth and stability of anisotropic or isotropic disordered surfaces in electrodeposition is of importance in catalytic electrochemistry. In some cases, the metallic nature of the electrode defines the topography and roughness, which are also controlled by the experimental time and applied external potential. Because of the experimental restrictions in conventional electrochemical techniques and ex situ electron microscopies, a theoretical model of the surface geometry could aid in understanding the electrodeposition process and current distributions. In spite of applying a complex theory such as dynamic scaling method or perturbation theories, the resolution of mixed mass‐/charge‐transfer equations (tertiary distribution) for the electrodeposition process would give reliable information. One of the main problems with this type of distribution is the mathematics when solving the spatial n‐dimensional differential equations. Use of a primary current distribution is proposed here to simplify the differential equations; however it limits wide application of the first assumption. Distributions of concentration profile, current density, and electrode potential are presented here as a function of the distance normal to the surface for the cases of smooth and rough platinum growth. In the particular case of columnar surfaces, cycloid curves are used to model the electrode, from which the concentration profile is presented in a parameterized form after solving a first‐type curvilinear integral. The concentration contour results in a combination of a trigonometric inverse function and a linear distribution leading to a negative concavity curve. The calculation of the current density and electrode potential contours also show trigonometric shapes exhibiting forbidden imaginary values only at the minimal values of the trochoid curve.  相似文献   

17.
The paper describes the radiochemical and chemical analyses of industrial graphite scraps showing high radioactivity levels. The uranium concentration in some graphite scraps was very high (up to l kBq/g, 7.7%w/w) and its distribution greatly heterogeneus. Some uranium solubility tests carried out on the graphite scraps showed that 60–70% of the element could be dissolved with a buffer solution at pH 4 and that complete dissolution could be obtained by leaching with conc. HNO3 . By taking into account these results it can be concluded that the radioactive contaminant consists of uranium chemically purified and isotopically treated.  相似文献   

18.
《Electroanalysis》2005,17(8):719-723
A very sensitive and selective adsorptive cathodic stripping procedure for trace measurement of uranium is presented. The method is based on adsorptive accumulation of the uranium‐pyromellitic acid (benzene‐1,2,4,5‐tetracarboxylic acid) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species by voltammetric scan using differential pulse modulation. Influences of effective parameters such as pH, concentration of pyromellitic acid, accumulation potential and accumulation time on the sensitivity were studied. The peak current was proportional to the concentration of U(IV) up to 40 ng mL?1 with a limit of detection of 0.136 ng mL?1 with an accumulation time of 120 s. The range of linearity enhanced to 71.4 ng mL?1and the detection limit improved to 0.058 ng mL?1with accumulation times of 60 s and 300 s respectively. The relative standard deviation for 10 replicate determination of 4.76 ng mL?1 U(IV) was equal to 2.7%. The possible interference by major cations and anions are investigated. The method was applied to the determination of uranium in some analytical grade salts, seawater and in synthetic samples corresponding to some uranium alloys with satisfactory results.  相似文献   

19.
The uranium(VI) accumulation was studied in detail by using the biomass of mangrove endophytic fungus Fusarium sp.#ZZF51 from the South China Sea. The uranium(VI) biosorption process onto the tested fungus powders was optimized at pH 4.0, adsorption time 60 min, and uranium(VI) initial concentration 50 mg L−1 with 61.89% of removal efficiency. According to Fourier transform infrared spectra for the tested fungus before and after loaded with uranium(VI), the results showed that both of hydroxyl and carboxyl groups acted as the important roles in the adsorption process. In addition, the experimental data were analyzed by using parameter and kinetic models, and it was obtained that the Langmuir isotherm model and the pseudo-second-order kinetic model provided better correlation with the experimental data for adsorption of uranium(VI).  相似文献   

20.
Mumbai Harbour Bay (MHB) is a recipient of low level treated effluents from BARC, Trombay. In addition, the Bay is also a recipient of domestic and industrial wastes from the city of Mumbai and adjoining areas. The average value of uranium concentration reported for Indian Bay water at Tarapur and Mumbai is ~3.0 ppb which is comparable with the reported value for Arabian sea. As such the global average is reported to be ~3.3 ppb by Oceanologists. The present study deals with the distribution of uranium in seawater of MHB. The uranium activity in MHB by alpha spectrometry was found to be between 1.0 and 4.4 ppb with an average concentration of 2.5 ppb which is comparable with the earlier reported average activity of 2.6 ppb in the MHB as well as those reported globally. To compare the results obtained by alpha spectrometry, uranium estimation was also carried out using Laser fluorimeter and the levels of uranium concentration have ranged between 0.8 and 4.9 ppb with an average concentration of 2.7 ppb.  相似文献   

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