WO2012034989A1 - Procede de mesure de la concentration en uranium d'une solution aqueuse par spectrophotometrie - Google Patents
Procede de mesure de la concentration en uranium d'une solution aqueuse par spectrophotometrie Download PDFInfo
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- WO2012034989A1 WO2012034989A1 PCT/EP2011/065806 EP2011065806W WO2012034989A1 WO 2012034989 A1 WO2012034989 A1 WO 2012034989A1 EP 2011065806 W EP2011065806 W EP 2011065806W WO 2012034989 A1 WO2012034989 A1 WO 2012034989A1
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- WIPO (PCT)
- Prior art keywords
- uranium
- aqueous solution
- solution
- measuring
- absorbance
- Prior art date
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 92
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 42
- 238000002798 spectrophotometry method Methods 0.000 title description 14
- 239000000243 solution Substances 0.000 claims abstract description 74
- 238000002835 absorbance Methods 0.000 claims abstract description 37
- 238000005259 measurement Methods 0.000 claims abstract description 33
- 230000009467 reduction Effects 0.000 claims abstract description 33
- 230000003287 optical effect Effects 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000001514 detection method Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- HNVACBPOIKOMQP-UHFFFAOYSA-N uranium(4+) Chemical compound [U+4] HNVACBPOIKOMQP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000003758 nuclear fuel Substances 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 description 31
- 238000004458 analytical method Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 238000000691 measurement method Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 238000011481 absorbance measurement Methods 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- -1 iron cations Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C9/00—Electrostatic separation not provided for in any single one of the other main groups of this subclass
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/02—Details
- G01J3/0297—Constructional arrangements for removing other types of optical noise or for performing calibration
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N2021/3125—Measuring the absorption by excited molecules
Definitions
- the invention relates to a method for the determination of uranium present in an aqueous solution.
- This method is particularly applicable to the determination of uranium present in aqueous solutions for producing uranium-containing concentrates, in aqueous solutions for the treatment of irradiated nuclear fuel, in effluents containing uranium and from mining production sites.
- the "Bromo-Padap method" technique mentioned above is particularly sensitive to iron cations, which distort the absorbance measurements of the uranyl-bromo-padap complex since they are present in the solution in a concentration greater than or equal to 40 mg / L.
- the ions, and especially the iron cations are very often present in significant amounts (that is to say greater than 100 mg / L) in the solutions containing uranium, as the effluents resulting from the processes of treatment of uranium.
- the inventors have therefore set themselves the goal of designing a method for measuring the uranium concentration of an aqueous solution that does not have the drawbacks of the prior art, or for all the less, which would be less sensitive to the presence of ions in the solution and avoid the addition of additional chemical reagents.
- step b) measuring the absorbance of the solution obtained at the end of step a) at a wavelength chosen between 640 and 660 nm;
- step c) the determination of the uranium concentration of the aqueous solution by deducing the concentration of valence (IV) uranium present in the aqueous solution obtained at the end of step a) from the measurement of the absorbance obtained in step b).
- the pH of the aqueous solution is initially greater than or equal to 2
- the pH of the solution is lowered by adding a concentrated acid to a pH ⁇ 2, for example using sulfuric acid.
- the pH value of the aqueous solution as given in this description is a pH value measured under standard conditions of temperature and pressure, well known to those skilled in the art.
- the uranium concentration of the solution is deduced by determining the concentration of IV valence uranium present in the solution obtained at the end of step a ) by application of the Beer-Lambert Act. Indeed, according to the Beer-Lambert law, the absorbance is proportional to the concentration of analyte present in a solution and to the length of the optical path in this solution.
- the electrochemical reduction of the uranium present in the aqueous solution is carried out by performing the following successive steps:
- each compartment comprising an electrode intended to be in contact with the solution contained in this compartment and the first and the second compartment being separated the one of the other by means allowing only the passage of electrons from one compartment to another;
- the means allowing the passage of electrons does not allow the mixing of the solution fractions present in their respective compartments with each other.
- the means for the passage of electrons is a sintered material, for example sintered glass. It may for example be a sintered glass wall.
- step a) The absorbance of the solution obtained at the end of step a) is carried out by performing the following successive steps:
- step a) injection of all or part of the solution obtained at the end of step a) into at least one measuring cell whose interior forms an optical path greater than or equal to 5 centimeters between a first and a second end of said measuring cell;
- the solution obtained at the end of step a) is the fraction of solution which has undergone a reduction reaction, that is to say the fraction of solution present in the compartment in which the reaction took place. reduction.
- the measuring cell exists in different forms. For small useful volumes, there are circulating vessels or elongated optical paths of 1 to 10 cm and capillaries of 10 cm to 5 m. The choice is made according to the desired limit of quantification and the type of matrix to be analyzed.
- the measuring cells are two in number and have an optical path of different length in order to extend the dynamic range of measurement.
- the wavelength chosen is the wavelength for which the absorbance of uranium (IV) is maximum. Moreover, the chosen wavelength has the advantage of having less interference with the metal cations present in the solution. This wavelength is 652 nm.
- the method according to the invention further comprises a step of cleaning the first and second compartments of the electrochemical cell, this step being performed by injection of an acid diluted (for example a 1% diluted acid) in each of the compartments and application of a current between the electrodes, this current being applied in a direction opposite to the current applied to achieve the reduction of the uranium in step a) .
- the current is in fact applied so as to obtain an oxidation reaction in the compartment having previously been the seat of a reduction reaction.
- the method further comprises a step of cleaning said at least one measuring cell, this step being carried out after the step of detecting the light beam and being obtained by injection of an acid diluted to 1% in said at least one measuring cell. less a measuring cell.
- the aqueous solution is chosen from solutions for the production of uranium concentrates, the effluents produced during the treatment of a uranium ore or the effluents produced during the treatment of an irradiated nuclear fuel.
- the measurement method described above has the advantage of not requiring the use of reagents or additional chemical step.
- the process according to the invention does not use any reagent, that is to say no substance intended to react or interact with uranium.
- This measurement method also makes it possible to know the uranium concentration of a solution aqueous solution for a concentration of between 1 and 1500 mg / l.
- the method according to the invention also has the advantage of being able to be automated.
- the invention also relates to a method for on-line measurement of the uranium concentration of an aqueous solution, comprising the following successive steps:
- n an integer greater than or equal to 2.
- an online measurement method is an in situ and automated measurement method.
- the n measurements can be performed at regular time intervals or not. Measurements can also be made continuously.
- the two processes according to the invention can be used on the mining production sites, for the analysis of water from treatment processes and effluents.
- the on-line measurement process enables on-line monitoring of uranium fluxes at low concentrations, particularly for in situ leaching technique or ISR (for In Situ Recovery in English), the monitoring of the uranium concentration ...
- FIG. 1 shows a schematic sectional front view of an electrochemical cell with two compartments
- FIG. 2 groups different absorbance spectra as a function of the wavelength obtained according to the method of the invention by using a measurement cell having an optical path of 5 cm for different concentrations (calibration);
- FIG. 3 groups different absorbance spectra as a function of the wavelength obtained according to the method of the invention by using a measurement cell having an optical path of 10 cm for different concentrations (calibration);
- FIG. 4 represents a calibration curve obtained from the spectra of FIG. 2;
- FIG. 5 represents a calibration curve obtained from the spectra of FIG. 3;
- FIG. 6 is a schematic diagram of the online analysis according to the invention. It should be noted that the different elements in FIGS. 1 and 6 are not made on a scale.
- the measuring method according to the invention comprises a first electrochemical reduction step of the uranium contained in the aqueous solution to be analyzed, followed by a second step of spectrophotometric analysis of the solution obtained at the end of step a ) by measuring its absorbance.
- the process according to the invention is in fact based on the analysis of uranium at its valence IV (reduced form) at the wavelength for which the absorbance of uranium (IV) is maximum.
- An electrochemical reduction is thus carried out so that the uranium present in the aqueous solution passes from a state of valence VI to a state of valence IV.
- a spectrophotometric measurement is made at 652 nm, which corresponds to the maximum absorbance of the IV uranium.
- a further advantage of the process according to the invention is that few elements absorb at 652 nm: by performing a spectrophotometric analysis at 652 nm, the wavelength of the uranium is more sensitive and less interfered with, which allows, to a certain extent, to significantly reduce the impact of the interference due to metal cations on the measuring the absorbance.
- an electrochemical cell with two compartments, which is dimensioned to the volume that is useful for analysis;
- a working electrode glassy carbon electrode
- the electrochemical cell 1 used to carry out the reduction is a conventional bi-compartmented cell.
- the two compartments 2, 3 are obtained by placing a separating wall 4 between two opposite walls of an enclosure.
- a separating wall 4 is placed between two opposite walls of an enclosure.
- at least a portion 5 of the separating wall 4 is porous.
- This porous part 5 is made of sintered material, for example sintered glass.
- the working electrode 6 In one of the compartments is positioned the working electrode 6 (this compartment being precisely called “working compartment”), while in the other compartment the auxiliary electrode 7 is positioned.
- the aqueous solution to be assayed is introduced into the electrochemical cell and distributed between the two compartments of this cell.
- the aqueous solution has a pH of less than 2 (this is a necessary condition for the successful proton reduction of uranium). Therefore, before initiating the oxidation-reduction reaction, it is ensured that the pH of the solution is well below 2 and if this is not the case, the solution is acidified, for example by pouring concentrated sulfuric acid.
- uranium (IV) concentration In order for the measurement of uranium (IV) concentration to accurately reflect the concentration of uranium in the aqueous solution to be analyzed, it is important that the reduction of uranium be complete. It is therefore important that the current between the electrodes be stopped only when the reduction of uranium is complete. It is therefore necessary to determine the minimum time necessary for the complete reduction of the VI uranium contained in the volume of the working compartment. For this purpose, tests are first carried out using the aqueous solution containing the highest uranium content among the solutions to be determined. As an indication, 20 minutes under a current of 1 Ampere are sufficient to reduce a volume of 3.5 mL of solution having a content of 1500 mg / L of uranium.
- the solution which has undergone the reduction is recovered and sent to the spectrophotometric analysis part.
- the solution that has undergone oxidation it is also removed from its compartment, but it is not used. It can for example be evacuated in a waste container.
- the delivery of the solution which has undergone the reduction can be obtained by using a suction capillary made of PTFE (Teflon ® ) placed at a sufficient height of the bottom so as not to suck any deposits, in the compartment containing the reduced uranium, which will bring the solution containing uranium (IV) to the measuring cell of the spectrophotometer, for example by means of a peristaltic pump.
- the compartments of the cell once emptied are preferably cleaned, for example by being filled with 1% diluted acid and applying a current to the electrodes in a direction opposite to the applied current to achieve the reduction, so that he is produce an oxidation reaction in the compartment having been the seat of a reduction reaction, and a reduction reaction in the other compartment.
- the oxidation will make it possible to iron the metallic deposit possibly present at the bottom of the compartment and possibly on the electrode, in solution in the form of cations.
- the cleaning solution is then removed from the compartments.
- the compartments of the electrochemical cell are operational again and can be reused to perform a reduction of a new sample of aqueous solution.
- the electrochemical cell may also comprise, in addition to the auxiliary electrode and the working electrode, a reference electrode, the role of which will be to control more precisely the reaction (potential monitoring), as represented in FIG. FIG. 1 by the protrusion disposed at the end of the electrode 7.
- the solution assay will be performed using a spectrophotometer.
- a spectrophotometer making it possible to perform an analysis at 652 nm;
- the light source of the spectrophotometer may for example be a halogen lamp;
- At least one measurement cell intended to receive a sample of solution to be measured, this measuring cell having an optical path adapted to the analytical needs;
- a switch useful when several measurement cells are used, to direct the light of the spectrophotometer towards one measuring cell rather than another; in this case, the solution sample is routed simultaneously in each of the measuring cells and the switch is used to pass the light into one of the measuring cells, then into another, and so on, in order to achieve independent acquisitions and extend the dynamic range of analysis.
- LWCC capillary-walled capillary measurement
- the absorbance of uranium (IV) is measured. But, in order for this measurement to be accurate, it is also important to know the absorbance of the spectral background of the solution containing uranium (IV). Subtracting this value from the absorbance of the spectral background at the value of the absorbance obtained at 652 nm gives the value of the net absorbance of uranium IV, which will be used to determine the uranium concentration of the uranium. solution to be analyzed using the Beer-Lambert law.
- the absorbance of the spectral background varies according to the study matrix of the solution. For example, for solutions from Ukraine, the absorbance of the spectral background is measured at 574 nm.
- 1% sulfuric medium is the acidic medium in which the samples to be analyzed are located (case of Ukraine).
- 1% diluted acid is introduced into the optical path of the measuring cell and an spectrophotometer acquisition of the spectrophotometer is started by blocking the light from the source of the spectrophotometer in order to determine the noise of the spectrophotometer. background of the source (also called black current).
- the spectrophotometer is placed in absorbance mode: the apparatus is then ready to acquire absorbance spectra.
- measurements are made in a measurement cell having an optical path of 5 cm on standard samples respectively comprising the following concentrations of uranium in sulfuric medium: 1000 mg / L (curve 1), 750 mg / L (curve 2), 500 mg / L (curve 3), 250 mg / L (curve 4), 100 mg / L (curve 5), 75 mg / L ( curve 6), 50 mg / L (curve 7).
- the solution is reduced as described in the "reduction step" paragraph. It is specified that, given the concentrations of the samples and for a volume of 3.5 mL to be reduced, the oxidation-reduction reaction is conducted for a period of 20 minutes by imposing a current of 1 Ampere between the electrodes.
- the aliquot containing the reduced uranium is introduced into the optical path of the measuring cell and the acquisition of the spectrum is realized.
- the net absorbance value at 652 nm is calculated.
- the calibration line of the absorbance as a function of the concentration is calculated and plotted using a suitable software, for example an Excel® type software.
- the correlation coefficient must be close to 1 and the intercept must be close to 0.
- Figures 4 and 5 show the results of a 1% sulfuric calibration for an optical path length of 5 cm and 10 cm, respectively.
- the lower limit of detection of the process according to the invention is 50 mg / L using a measurement cell having a path optical 5 cm ( Figure 4), but this limit increases to 20 mg / L using a measuring cell having an optical path of 10 cm ( Figure 5).
- This detection limit can therefore be lowered by choosing a measuring cell having a longer optical path and can thus go down to 1 mg / L for an optical path of 200 cm.
- the net intensity of absorbance at 652 nm is calculated and this value is entered on the calibration line to determine the uranium concentration of this sample.
- the pH of the solution to be analyzed is less than 2 and, if not, to acidify it with a concentrated acid, preferably using the same acid as that used to perform the calibration, that is to say, in our example embodiment, sulfuric acid.
- Samples 1 to 13 are samples taken from the site. The results obtained are shown in the table below:
- the measuring method according to the invention is reliable: the difference between the measured concentration and the theoretical concentration is less than 20%, except for the samples having a uranium content close to the detection limit of 20 mg / L.
- the steps of the measurement method according to the invention are automatable and it is therefore possible to perform online analyzes of the uranium concentration.
- a sampler is used to convey an aliquot of solution to the electrochemical cell and the spectrophotometer.
- FIG. 6 shows a possible example of integration of the steps of the method according to the invention.
- the solution to be assayed for example a solution from a mining production well, (not shown) is withdrawn and supplied by a pump (not shown) into the two compartments 2, 3 of the electrochemical cell 1 whose electrodes 7, 6 are connected to a potentiostat 8.
- the solution contained in the compartment having been the seat of an oxidation reaction is discharged to a collection container 9 by the opening of a valve; the solution contained in the compartment having been the seat of a reduction reaction is in turn sucked by the pump 15 and conveyed simultaneously into two measuring cells 10 and 11 each having an optical path of different length, for example 10 cm and 200 cm.
- a switch (not shown) makes it possible to pass the light coming from the lamp 12 in one of the optical paths and then in the other. Thus, it is possible to assay the samples of low uranium concentration with the measuring cell having a long optical path and the determination of high concentrations with the other measuring cell.
- Software and a computer 14 allow data storage and signal processing.
- Rinsing for example with sulfuric acid diluted to 1%) and oxidation of the compartments of the electrochemical cell 1 is carried out during the performance of the spectrophotometric measurement (measurement performed by the spectrophotometer 13).
- Rinsing with acid eg 1% sulfuric acid
- a correction of the background noise of the white lamp is made before each analysis.
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Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2011303944A AU2011303944B2 (en) | 2010-09-16 | 2011-09-13 | Method of measuring the uranium concentration of an aqueous solution by spectrophotometry |
RU2013117129/28A RU2573445C2 (ru) | 2010-09-16 | 2011-09-13 | Способ измерения концентрации урана в водном растворе методом спектрофотометрии |
US13/824,339 US20130206599A1 (en) | 2010-09-16 | 2011-09-13 | Method for measuring the uranium concentration of an aqueous solution by spectrophotometry |
CA2811304A CA2811304A1 (fr) | 2010-09-16 | 2011-09-13 | Procede de mesure de la concentration en uranium d'une solution aqueuse par spectrophotometrie |
SE1350295A SE1350295A1 (sv) | 2010-09-16 | 2011-09-13 | Förfarande för mätning av urankoncentrationen i en vattenlösning genom spektrofotometri |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1057407 | 2010-09-16 | ||
FR1057407A FR2965056B1 (fr) | 2010-09-16 | 2010-09-16 | Procede de mesure de la concentration en uranium d'une solution aqueuse par spectrophotometrie |
Publications (1)
Publication Number | Publication Date |
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WO2012034989A1 true WO2012034989A1 (fr) | 2012-03-22 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2011/065806 WO2012034989A1 (fr) | 2010-09-16 | 2011-09-13 | Procede de mesure de la concentration en uranium d'une solution aqueuse par spectrophotometrie |
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US (1) | US20130206599A1 (fr) |
AU (1) | AU2011303944B2 (fr) |
CA (1) | CA2811304A1 (fr) |
FR (1) | FR2965056B1 (fr) |
RU (1) | RU2573445C2 (fr) |
SE (1) | SE1350295A1 (fr) |
WO (1) | WO2012034989A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103207153A (zh) * | 2013-03-11 | 2013-07-17 | 中国原子能科学研究院 | 一种小量铀的精密测定方法 |
Families Citing this family (7)
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KR101281105B1 (ko) * | 2011-01-06 | 2013-07-02 | 한국수력원자력 주식회사 | 수용액 내 존재하는 우라늄 농도의 정량방법 |
KR101390738B1 (ko) * | 2012-09-20 | 2014-04-30 | 한국원자력연구원 | 산화제를 이용한 우라늄 발광검출법 및 산화제의 조성 |
CN106569250B (zh) * | 2016-10-21 | 2019-03-22 | 核工业北京化工冶金研究院 | 一种在线铀矿山浸出矿浆铀浓度测量装置及使用方法 |
CN111024624B (zh) * | 2019-12-20 | 2022-04-26 | 东南大学 | 基于暗场散射成像的parp-1单粒子检测方法 |
CN112630177A (zh) * | 2020-12-31 | 2021-04-09 | 中国原子能科学研究院 | 有机相中铀、钚、硝酸含量的分析方法 |
CN113324929B (zh) * | 2021-05-14 | 2023-03-07 | 中国原子能科学研究院 | 铀浓度分析方法、分析系统、分析模型和构建方法 |
CN115099363B (zh) * | 2022-07-22 | 2023-04-07 | 核工业北京地质研究院 | 识别砂岩铀矿成矿流体作用类型的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58135439A (ja) * | 1982-02-05 | 1983-08-12 | Asahi Chem Ind Co Ltd | ウラン還元反応終点検出方法 |
FR2691542A1 (fr) * | 1992-05-20 | 1993-11-26 | Cogema | Procédé de dosage de l'uranium par chromatographie en phase liquide. |
US6107098A (en) * | 1998-02-27 | 2000-08-22 | The United States Of America As Represented By The Secretary Of The Army | Uranium-containing/metal binding complex, process of making and method of use for the determination of natural, and depleted uranium in biological samples |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB832494A (en) * | 1945-03-24 | 1960-04-13 | Atomic Energy Authority Uk | Electrodeposition of uranium compounds |
DE2146262C3 (de) * | 1971-09-16 | 1981-05-21 | Deutsche Gesellschaft für Wiederaufarbeitung von Kernbrennstoffen mbH, 3000 Hannover | Vorrichtung zur Reduktion von Salzlösungen von Verbindungen kernphysikalisch spaltbarer Elemente |
US4219395A (en) * | 1972-02-28 | 1980-08-26 | Smith Maryanne | Electrochemical fractionation process |
US3923611A (en) * | 1974-12-23 | 1975-12-02 | Ferro Corp | Direct-on ceramic coating of carbon-rich iron |
SU581798A1 (ru) * | 1975-11-10 | 1981-10-23 | Предприятие П/Я Р-6575 | Способ определени урана |
US4080273A (en) * | 1976-09-07 | 1978-03-21 | The United States Of America As Represented By The United States Department Of Energy | Method for photochemical reduction of uranyl nitrate by tri-N-butyl phosphate and application of this method to nuclear fuel reprocessing |
FR2433587A1 (fr) * | 1978-08-17 | 1980-03-14 | Rhone Poulenc Ind | Procede de recuperation de l'uranium contenu dans une phase organique |
US4534940A (en) * | 1982-03-26 | 1985-08-13 | Utah State University Foundation | Atomic absorption spectrophotometric measurement of mercury |
US4939119A (en) * | 1987-04-22 | 1990-07-03 | Sumitomo Electric Industries, Inc. | Process for producing a superconducting article |
JPH03158485A (ja) * | 1989-11-16 | 1991-07-08 | Tanaka Kikinzoku Kogyo Kk | ウラニル塩の還元方法 |
US6107908A (en) * | 1998-08-17 | 2000-08-22 | Santa Cruz; Cathy D. | Blown fuse commutator strip and method of use |
EP1889034A1 (fr) * | 2005-05-24 | 2008-02-20 | Agilent Technologies, Inc. | Correction de cuve de circulation multivoies |
FR2917227A1 (fr) * | 2007-06-07 | 2008-12-12 | Commissariat Energie Atomique | Utilisation de l'oxime de butyraldehyde en tant qu'agent anti-nitreux dans le retraitement de combustibles nucleaires uses. |
RU2370760C1 (ru) * | 2008-03-24 | 2009-10-20 | Институт прикладной механики УрО РАН | Способ определения урана (vi) в растворах |
US20100072059A1 (en) * | 2008-09-25 | 2010-03-25 | Peters Michael J | Electrolytic System and Method for Enhanced Radiological, Nuclear, and Industrial Decontamination |
-
2010
- 2010-09-16 FR FR1057407A patent/FR2965056B1/fr not_active Expired - Fee Related
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2011
- 2011-09-13 RU RU2013117129/28A patent/RU2573445C2/ru not_active IP Right Cessation
- 2011-09-13 AU AU2011303944A patent/AU2011303944B2/en not_active Ceased
- 2011-09-13 SE SE1350295A patent/SE1350295A1/sv not_active Application Discontinuation
- 2011-09-13 US US13/824,339 patent/US20130206599A1/en not_active Abandoned
- 2011-09-13 CA CA2811304A patent/CA2811304A1/fr not_active Abandoned
- 2011-09-13 WO PCT/EP2011/065806 patent/WO2012034989A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58135439A (ja) * | 1982-02-05 | 1983-08-12 | Asahi Chem Ind Co Ltd | ウラン還元反応終点検出方法 |
FR2691542A1 (fr) * | 1992-05-20 | 1993-11-26 | Cogema | Procédé de dosage de l'uranium par chromatographie en phase liquide. |
US6107098A (en) * | 1998-02-27 | 2000-08-22 | The United States Of America As Represented By The Secretary Of The Army | Uranium-containing/metal binding complex, process of making and method of use for the determination of natural, and depleted uranium in biological samples |
Non-Patent Citations (2)
Title |
---|
KHAN M H ET AL: "Spectrophotometric determination of uranium with arsenazo-III in perchloric acid", CHEMOSPHERE, PERGAMON PRESS, OXFORD, GB, vol. 63, no. 7, 1 May 2006 (2006-05-01), pages 1165 - 1169, XP025041768, ISSN: 0045-6535, [retrieved on 20060501], DOI: DOI:10.1016/J.CHEMOSPHERE.2005.09.060 * |
SHIBATA M AND FURUYA N: "New methods of uranium (IV) production using a Pt-loaded gas-diffusion electrode", JOURNAL OF APPLIED ELECTROCHEMISTRY, vol. 21, 1991, pages 226 - 230, XP002635279 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103207153A (zh) * | 2013-03-11 | 2013-07-17 | 中国原子能科学研究院 | 一种小量铀的精密测定方法 |
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US20130206599A1 (en) | 2013-08-15 |
AU2011303944B2 (en) | 2015-05-07 |
FR2965056A1 (fr) | 2012-03-23 |
AU2011303944A1 (en) | 2013-05-02 |
FR2965056B1 (fr) | 2013-05-10 |
RU2013117129A (ru) | 2014-10-27 |
CA2811304A1 (fr) | 2012-03-22 |
RU2573445C2 (ru) | 2016-01-20 |
SE1350295A1 (sv) | 2013-04-11 |
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