CN114280025B - Device and method for measuring uranium content in solution - Google Patents
Device and method for measuring uranium content in solution Download PDFInfo
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- CN114280025B CN114280025B CN202111628052.XA CN202111628052A CN114280025B CN 114280025 B CN114280025 B CN 114280025B CN 202111628052 A CN202111628052 A CN 202111628052A CN 114280025 B CN114280025 B CN 114280025B
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 155
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000006185 dispersion Substances 0.000 claims abstract description 47
- 238000000691 measurement method Methods 0.000 claims abstract description 39
- 238000001917 fluorescence detection Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims description 111
- 238000005259 measurement Methods 0.000 claims description 57
- 230000005284 excitation Effects 0.000 claims description 46
- 238000001514 detection method Methods 0.000 claims description 23
- 239000012086 standard solution Substances 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 11
- 238000004891 communication Methods 0.000 claims description 7
- 230000010354 integration Effects 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 description 9
- 239000012488 sample solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 239000012898 sample dilution Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to a device and a method for measuring uranium content in a solution, wherein a pulse light source generation module and a time-resolved fluorescence detection module are arranged, and the method for measuring the uranium content in a low-concentration uranium-containing solution to be measured by adopting a time-resolved fluorescence measurement method is adopted; the continuous light source generating module and the fluorescence wavelength dispersion detecting module are arranged, and the wavelength dispersion measuring method is adopted to measure the uranium content of high concentration.
Description
Technical Field
The invention relates to the technical field of laboratory analysis and test, in particular to a device and a method for measuring uranium content in a solution.
Background
Analysis and test of uranium are all related to analysis and test work of uranium from analysis and test of natural uranium ores to nuclear fuel post-treatment. Although the existing measuring method can basically cover the whole process flow, the content difference of different feed liquid matrix components and uranium is large, and various different methods are needed for measurement.
The fluorescent trace uranium determination method has the advantages of simple equipment, convenient operation, low detection lower limit and the like, and is used in uranium ore testing and post-treatment processes. But due to its relatively narrow linear range, only low concentrations of uranium content ranging from 0 to 100ppb can be measured directly.
Therefore, a device and a method for measuring uranium content in a solution are needed to improve the measurement range.
Disclosure of Invention
The invention aims to provide a device and a method for measuring the uranium content in a solution so as to improve the measuring range of the uranium content.
In order to achieve the above object, the present invention provides the following solutions:
a uranium content measurement device in solution, comprising:
The fluorescence cuvette is used for containing uranium-containing solution to be detected;
A pulse light source generation module; the ultraviolet pulse excitation light generated by the pulse light source generation module is incident into the fluorescent cuvette;
The time-resolved fluorescence detection module is used for collecting first fluorescence generated after the uranium-containing solution to be detected is excited by ultraviolet pulse excitation light, and detecting the intensity of the first fluorescence;
The first fluorescent light path received by the time-resolved fluorescence detection module is perpendicular to the ultraviolet pulse excitation light path;
a continuous light source generating module; the continuous excitation light generated by the continuous light source generation module is incident into the fluorescent cuvette;
the fluorescence wavelength dispersion detection module is used for collecting second fluorescence generated after the uranium-containing solution to be detected is excited by the continuous excitation light and detecting the intensity of the second fluorescence;
the second fluorescence light path received by the fluorescence wavelength dispersion detection module is perpendicular to the continuous excitation light path;
And the computer is respectively in communication connection with the time resolution fluorescence detection module and the fluorescence wavelength dispersion detection module, and is used for calculating the uranium content in a first concentration range according to the intensity of the first fluorescence, calculating the uranium content in a second concentration range according to the intensity of the second fluorescence, and the value of the first concentration range is smaller than the value of the second concentration range.
The method for measuring the uranium content in the solution by using the uranium content measuring device comprises the following steps:
When the uranium content is measured by adopting a time-resolved fluorescence measurement method, taking the uranium content measured by the time-resolved fluorescence measurement method as a first preliminary measurement result;
calculating a first difference between the first preliminary measurement result and a maximum endpoint value of the first concentration range;
if the first difference value is larger than a threshold value, determining the preliminary measurement result as the final uranium content;
If the first difference value is smaller than the threshold value, carrying out uranium content measurement by adopting a wavelength dispersion measurement method to obtain a second uranium content measurement result;
taking the second uranium content measurement result as a final uranium content;
When the uranium content is measured by adopting the wavelength dispersion measuring method, taking the uranium content measured by the wavelength dispersion measuring method as a second preliminary measurement result;
calculating a second difference between the second preliminary measurement and a minimum endpoint value of the second concentration range;
if the second difference value is greater than a threshold value, determining the second preliminary measurement result as the final uranium content;
If the second difference value is smaller than the threshold value, carrying out uranium content measurement by adopting a time-resolved fluorescence measurement method to obtain a third uranium content measurement result;
And taking the third uranium content measurement result as the final uranium content.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
The invention provides a device and a method for measuring uranium content in a solution, wherein a pulse light source generation module and a time-resolved fluorescence detection module are arranged, and the method for measuring the uranium content in a low-concentration uranium-containing solution to be measured by adopting a time-resolved fluorescence measurement method is adopted; the continuous light source generating module and the fluorescence wavelength dispersion detecting module are arranged, and the wavelength dispersion measuring method is adopted to measure the uranium content of high concentration.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. The following drawings are not intended to be drawn to scale, emphasis instead being placed upon illustrating the principles of the invention.
Fig. 1 shows a schematic structural diagram of a uranium content measurement device in a solution according to the present invention;
fig. 2 shows a flow chart of a method for measuring uranium content in a solution according to the present invention.
Symbol description:
The device comprises a 1-fluorescence cuvette, a 2-pulse light source generation module, a 3-time resolution fluorescence detection module, a 4-continuous light source generation module, a 5-fluorescence wavelength dispersion detection module, a 6-computer, a 7-electronic circuit module, an 8-pulse excitation light source generator, a 9-excitation light filter, a 10-first focusing lens, a 11-pulse signal generator, a 12-second focusing lens, a 13-monochromatic grating, a 14-optical slit, a 15-first photoelectric detector, a 16-third focusing lens, a 17-emission light filter and a 18-second photoelectric detector.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As used in the specification and in the claims, the terms "a," "an," "the," and/or "the" are not specific to a singular, but may include a plurality, unless the context clearly dictates otherwise. In general, the terms "comprises" and "comprising" merely indicate that the steps and elements are explicitly identified, and they do not constitute an exclusive list, as other steps or elements may be included in a method or apparatus.
The invention aims to provide a device and a method for measuring the uranium content in a solution so as to improve the measuring range of the uranium content.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description.
Example 1:
Referring to fig. 1, this embodiment provides a device for measuring uranium content in a solution, including:
The fluorescence cuvette 1 is used for containing uranium-containing solution to be detected, and the optical path length of the fluorescence cuvette 1 is preferably 10-20 mm;
A pulse light source generation module 2; the ultraviolet pulse excitation light generated by the pulse light source generation module 2 is incident into the fluorescent cuvette 1;
The time-resolved fluorescence detection module 3 is used for collecting first fluorescence generated after the uranium-containing solution to be detected is excited by ultraviolet pulse excitation light, and detecting the intensity of the first fluorescence;
the first fluorescent light path received by the time-resolved fluorescence detection module 3 is perpendicular to the ultraviolet pulse excitation light path;
A continuous light source generating module 4; the continuous excitation light generated by the continuous light source generating module 4 is incident into the fluorescent cuvette 1, the continuous light source generating module 4 may be a lamp with a specific output wavelength, such as a semiconductor laser or a mercury lamp, as shown in fig. 1, and the pulse light source generating module 2 and the continuous light source generating module 4 may be respectively located at two sides of the fluorescent cuvette 1;
the fluorescence wavelength dispersion detection module 5 is used for collecting second fluorescence generated after the uranium-containing solution to be detected is excited by the continuous excitation light, and detecting the intensity of the second fluorescence;
the second fluorescence light path received by the fluorescence wavelength dispersion detection module 5 is perpendicular to the continuous excitation light path;
A computer 6, which is respectively connected with the time-resolved fluorescence detection module 3 and the fluorescence wavelength dispersion detection module 5 in a communication manner, and is configured to calculate the uranium content in a first concentration range according to the intensity of the first fluorescence, calculate the uranium content in a second concentration range according to the intensity of the second fluorescence, where the value of the first concentration range is smaller than the value of the second concentration range; the computer can also realize remote control of the equipment through software;
an electronic circuit module 7 connected to the time-resolved fluorescence detection module 3 and the fluorescence wavelength dispersion detection module 5 via signal lines, respectively, and connected to the computer 6 in communication;
The electronic circuit module 7 further comprises a power supply module, a signal acquisition module and a time sequence module; the signal acquisition module is in communication connection with the time sequence module and is respectively and electrically connected with the power supply module; the time sequence module is used for controlling the signal acquisition module to synchronize the acquisition signal of the first fluorescence with the emission signal of the ultraviolet pulse excitation light path.
As an alternative embodiment, the pulse light source generating module 2 includes a pulse excitation light source generator 8, an excitation light filter 9, and a first focusing lens 10;
the pulse excitation light source generator 8 is used for generating a pulse laser light source with adjustable light emitting frequency, and comprises a power supply and a pulse signal generator 11;
the excitation light filter 9 is used for obtaining an ultraviolet pulse excitation light source with a specific wavelength;
the first focusing lens 10 is used for shaping the ultraviolet pulse excitation light into approximately parallel light so as to improve the utilization rate of the ultraviolet pulse excitation light source.
The ultraviolet pulse excitation light generated by the pulse excitation light source generator 8 sequentially passes through the excitation light filter 9 and the first focusing lens 10, and then is incident into the fluorescence cuvette 1.
The time-resolved fluorescence detection module 3 comprises a second focusing lens 12, a monochromatic grating 13, an optical slit 14 and a first photoelectric detector 15;
the second focusing lens 12 is used for shaping the first fluorescence into approximately parallel light so as to improve the signal intensity of the fluorescence;
The monochromatic grating 13 is used for screening first fluorescence with specific wavelength;
the first fluorescent light is incident on the first photodetector 15 after passing through the second focusing lens 12, the monochromatic grating 13, and the optical slit 14 in this order.
The fluorescence wavelength dispersion detection module 5 comprises a third focusing lens 16, an emission optical filter 17 and a second photodetector 18;
the third focusing lens 16 is used for shaping the second fluorescence into approximately parallel light so as to improve the signal intensity of the fluorescence;
The emission optical filter 17 is used for filtering optical signals with other wavelengths and screening second fluorescence with specific wavelengths;
the second fluorescent light is incident on the second photodetector 18 after passing through the third focusing lens 16 and the emission filter 17 in order.
The wavelength of the first fluorescence screened by the monochromatic grating 13 is smaller than that of the second fluorescence screened by the emission light filter 17;
Preferably, the first photodetector 15 and the second photodetector 18 each include a photosensitive element for detecting fluorescence intensity, optionally a photomultiplier tube, a silicon photodiode, or the like, and an amplifying circuit for obtaining an optical signal of sufficient intensity.
The measuring device of the embodiment is simple and reliable, is easy to operate, and is suitable for on-site rapid measurement of uranium in the solution; the time-resolved fluorescence detection module is coupled with the pulse light source generation module in design, the fluorescence wavelength dispersion detection module is coupled with the continuous light source generation module, and the measurement of the uranium content with low concentration and high concentration can be respectively realized by respectively adopting different detection principles, so that the measurement range of the uranium content is widened; meanwhile, the two measuring channels are mutually independent and do not interfere with each other; in addition, the measuring device can directly measure the uranium content of the uranium-bearing solution with high concentration, and the inconvenience brought by sample dilution and repeated measurement is reduced.
Example 2:
The embodiment provides a method for measuring uranium content in a solution by using the uranium content measuring device of embodiment 1, referring to fig. 2, including:
S1: when the uranium content is measured by adopting a time-resolved fluorescence measurement method, taking the uranium content measured by the time-resolved fluorescence measurement method as a first preliminary measurement result;
S2: calculating a first difference between the first preliminary measurement result and a maximum endpoint value of the first concentration range;
s3: if the first difference value is larger than a threshold value, determining the preliminary measurement result as the final uranium content;
S4: if the first difference value is smaller than the threshold value, carrying out uranium content measurement by adopting a wavelength dispersion measurement method to obtain a second uranium content measurement result;
S5: taking the second uranium content measurement result as a final uranium content;
S6: when the uranium content is measured by adopting the wavelength dispersion measuring method, taking the uranium content measured by the wavelength dispersion measuring method as a second preliminary measurement result;
S7: calculating a second difference between the second preliminary measurement and a minimum endpoint value of the second concentration range;
S8: if the second difference value is greater than a threshold value, determining the second preliminary measurement result as the final uranium content;
S9: if the second difference value is smaller than the threshold value, carrying out uranium content measurement by adopting a time-resolved fluorescence measurement method to obtain a third uranium content measurement result;
s10: and taking the third uranium content measurement result as the final uranium content.
As an alternative embodiment, S1 specifically includes:
adding a fluorescence enhancement solution with preset concentration and quantitative volume into a fluorescence cuvette to obtain a first solution;
Obtaining the fluorescence intensity of the first solution by adopting a time-resolved fluorescence measurement method;
adding uranium standard solution with preset concentration and quantitative volume into the first solution to obtain second solution;
obtaining the fluorescence intensity of the second solution by adopting a time-resolved fluorescence measurement method;
adding a quantitative volume of uranium-containing solution to be detected into the second solution to obtain a third solution;
obtaining the fluorescence intensity of the third solution by adopting a time-resolved fluorescence measurement method;
and calculating to obtain the first preliminary measurement result according to the fluorescence intensity of the first solution, the fluorescence intensity of the second solution, the fluorescence intensity of the third solution and the preset concentration of the uranium standard solution.
The method for obtaining the fluorescence intensity of the first solution by adopting the time-resolved fluorescence measurement method specifically comprises the following steps:
performing area integration on the single ultraviolet pulse excitation light path trigger attenuation time and the fluorescence attenuation intensity to obtain single pulse fluorescence intensity, wherein the fluorescence attenuation intensity is the first solution fluorescence intensity corresponding to the single ultraviolet pulse excitation light path trigger attenuation time;
And summing a plurality of single pulse fluorescence intensities obtained in the time of presetting and collecting the fluorescence intensity of the first solution to obtain the fluorescence intensity of the first solution.
As an alternative embodiment, S6 specifically includes:
adding a fluorescence enhancement solution with preset concentration and quantitative volume and a uranium standard solution with preset concentration and quantitative volume into the fluorescence cuvette to obtain a fourth solution;
obtaining the fluorescence intensity of the fourth solution by adopting a wavelength dispersion measurement method;
adding uranium standard solution with preset concentration and set multiple quantitative volume into the fourth solution to obtain fifth solution;
Obtaining the fluorescence intensity of the fifth solution by adopting a wavelength dispersion measurement method;
Adding a quantitative volume of uranium-containing solution to be detected into the fourth solution to obtain a sixth solution;
obtaining the fluorescence intensity of the sixth solution by adopting a wavelength dispersion measurement method;
And calculating to obtain the second preliminary measurement result according to the fluorescence intensity of the fourth solution, the fluorescence intensity of the fifth solution, the fluorescence intensity of the sixth solution and the quantitative volume of the uranium-containing solution to be measured.
The method for measuring wavelength dispersion obtains the fluorescence intensity of the fourth solution, specifically including:
Calculating an average value of the fluorescence intensities of a plurality of fourth solutions obtained in a preset time for collecting the fluorescence intensities of the fourth solutions;
the average value was taken as the new fluorescence intensity of the fourth solution.
In order to make the above-described procedure more clearly known to those skilled in the art, the following description is given by way of specific examples.
Example 1:
Parameters of the uranium content measuring device are configured as follows:
The pulse excitation light source generator 8 selects a pulse xenon lamp light source, and the power of the pulse xenon lamp is 5w;
The continuous light source generation module 4 selects a semiconductor laser, the power of the semiconductor laser is 5mw, and the wavelength is 405nm;
wavelength range through which the excitation light filter 9 transmits: 230-460nm;
the emission filter 17 transmits the wavelength range: 480-610nm;
the first photodetector 15 is a photomultiplier;
The second photodetector 18 is a photomultiplier tube.
Setting working parameters:
Operating frequency of the pulsed excitation light source generator 8: 100Hz, pulse width 2 μs;
Time-resolved fluorescence detection module 3: the acquisition time sequence of the single pulse fluorescent signal is that 10 mu s starts to 1000 mu s ends after the pulse laser light source is triggered, and area integration is carried out according to the attenuation time and the fluorescence attenuation intensity to obtain the single pulse fluorescent intensity; the acquisition time is 10s, and the fluorescent intensity of 1000 single pulses is cumulatively summed.
A semiconductor laser: 5mw continuously output for 10s;
Fluorescent wavelength dispersion detection module 5: sampling frequency is 100Hz, and signal average value in 1-10 s interval is taken.
A) The time-resolved fluorescence detection module 3 is turned on and the fluorescence wavelength dispersion detection module 5 is turned off.
Setting the high voltage of a photomultiplier to 1000v, and collecting fluorescence signals of uranium.
The content of uranium is calculated by adopting a standard addition method: adding 4.5mL of 1% sodium pyrophosphate solution into a 5mL fluorescence tank, measuring the fluorescence intensity to be F0, accurately adding 50 mu L of 100ppb uranium standard solution into the fluorescence tank, uniformly stirring, measuring the fluorescence intensity to be F1, adding 50 mu L of sample solution into the fluorescence tank, uniformly stirring, measuring the fluorescence intensity to be F2, and calculating the uranium content in the solution to obtain C U = (F2-F1)/(F1-F0) x100 ppb.
Setting the first concentration range to be 0.02-500ppb, and if the difference between the measured uranium content and 500ppb is smaller than a threshold value, adopting a wavelength dispersion measurement method to measure the uranium content, namely:
b) The time-resolved fluorescence detection module 3 is closed, the fluorescence wavelength dispersion detection module 5 is opened, and the high voltage of the photomultiplier is set to 1000v.
Calculating the uranium content in the solution by adopting an external standard method: 4.5mL of 1% sodium pyrophosphate solution is added into a 5mL fluorescence pool, 10 mu L of 10ppm uranium standard solution is accurately added, the measured fluorescence intensity is recorded as F1, the steps are repeated, the fluorescence intensities F2, F3, F4 and F5 corresponding to 20 mu L,30 mu L,40 mu L and 50 mu L uranium standard solution are sequentially measured, a content-intensity curve is manufactured according to the content of uranium in the fluorescence pool and the corresponding fluorescence intensity, y=ax+b, wherein y is the fluorescence intensity, x is the content of uranium, a is the slope of the curve, and b is the intercept of the curve. To a 5mL fluorescence cell, 4.5mL of 1% sodium pyrophosphate solution was added, 10. Mu.L of the sample solution was precisely added, the fluorescence intensity was measured and recorded as Fs, and the uranium content in the sample solution was calculated to give C U = (Fs-b)/a/10. Mu.L.
The second concentration range is set to 10-500ppm, i.e., 10 4-5*105 ppb.
Example 2:
Parameters of the uranium content measuring device are configured as follows:
The pulse excitation light source generator 8 selects a pulse xenon lamp light source, and the power of the pulse xenon lamp is 15w;
the continuous light source generation module 4 selects a semiconductor laser, the power of the semiconductor laser is 100mW, and the wavelength is 405nm;
the angle of the monochromatic grating 13 is adjusted so that the wavelength range transmitted through the optical slit 14: 300-350 nm;
semiconductor laser power: 100mW;
Semiconductor laser wavelength: 405nm;
the first photodetector 15 is a photomultiplier;
The second photodetector 18 is a silicon photodiode.
Setting working parameters:
Operating frequency of the pulsed excitation light source generator 8: 10Hz, pulse width 5 μs;
Operating frequency of the pulsed excitation light source generator 8: 100Hz, pulse width 2 μs;
Time-resolved fluorescence detection module 3: the acquisition time sequence of the single pulse fluorescent signal is that 10 mu s starts to 100 mu s ends after the pulse light source is triggered, and area integration is carried out according to the attenuation time and the fluorescence attenuation intensity to obtain the single pulse fluorescent intensity; the acquisition time was 20s and the 200 single pulse fluorescence intensities were cumulatively summed.
A semiconductor laser: 5mw continuously output for 10s;
Fluorescent wavelength dispersion detection module 5: sampling frequency is 10Hz, and signal average value in 1-10 s interval is taken.
A) The time-resolved fluorescence detection module 3 is turned off and the fluorescence wavelength dispersion detection module 5 is turned on.
Calculating the uranium content in the solution by adopting an external standard method: adding 4.5mL of 1% sodium dihydrogen phosphate solution into a 5mL fluorescence pool, accurately adding 10ppm uranium standard solution 10 mu L, recording the measured fluorescence intensity as F1, repeating the steps, sequentially measuring fluorescence intensities F2, F3, F4 and F5 corresponding to 20 mu L,30 mu L,40 mu L and 50 mu L uranium standard solution, and manufacturing a content-intensity curve according to the content of uranium in the fluorescence pool and the corresponding fluorescence intensity, wherein y=ax+b, y is the fluorescence intensity, x is the content of uranium, a is the slope of the curve, and b is the intercept of the curve. To a 5mL fluorescence cell, 4.5mL of 1% sodium dihydrogen phosphate solution was added, and 50. Mu.L of a sample solution was precisely added, the fluorescence intensity was measured and recorded as Fs, and the uranium content in the sample solution was calculated to give C U = (Fs-b)/a/50. Mu.L.
When the second concentration range is set to be 10-500ppm, if the difference value between the measured uranium content and 10ppm is smaller than a threshold value, the uranium content is measured by adopting a time-resolved fluorescence measurement method, namely:
b) The time-resolved fluorescence detection module 3 is turned on and the fluorescence wavelength dispersion detection module 5 is turned off.
And setting high voltage of a photomultiplier to 500v, and collecting fluorescence signals of uranium.
Adding 4.5mL of 1% sodium dihydrogen phosphate solution into a 5mL fluorescence pool, measuring a fluorescence background value to be F0, accurately adding 50 mu L of 300ppb uranium standard solution into the fluorescence pool, uniformly stirring, measuring a fluorescence value to be F1, adding 50 mu L of sample solution into the fluorescence pool, uniformly stirring, measuring a fluorescence value to be F2, and calculating the uranium content in the solution to obtain C U = (F2-F1)/(F1-F0) x 300ppb.
The first concentration range is set to 0.02 to 500ppb.
According to the measuring method, the time-resolved fluorescence measuring method is adopted to measure the uranium content in the low-concentration uranium-containing solution to be measured, the wavelength dispersion measuring method is adopted to measure the high-concentration uranium content, the measuring range of the uranium content is improved, the high-concentration uranium-containing solution is not required to be diluted, the wavelength dispersion measuring method can be directly used for measuring the uranium content of the high-concentration uranium-containing solution, and inconvenience caused by sample dilution and repeated measurement is reduced.
In addition, the measuring method of the embodiment adopts a software control mode, realizes functions such as integration of uranium fluorescence and the like through a software algorithm, reduces functions which can be realized by circuits in the past, reduces redundant circuits and improves the portability of equipment.
The invention uses specific words to describe embodiments of the invention. Reference to "a first/second embodiment," "an embodiment," and/or "some embodiments" means that a particular feature, structure, or characteristic is associated with at least one embodiment of the invention. Thus, it should be emphasized and should be appreciated that two or more references to "an embodiment" or "one embodiment" or "an alternative embodiment" in various positions in this specification are not necessarily referring to the same embodiment. Furthermore, certain features, structures, or characteristics of one or more embodiments of the invention may be combined as suitable.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The foregoing is illustrative of the present invention and is not to be construed as limiting thereof. Although a few exemplary embodiments of this invention have been described, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the following claims. It is to be understood that the foregoing is illustrative of the present invention and is not to be construed as limited to the specific embodiments disclosed, and that modifications to the disclosed embodiments, as well as other embodiments, are intended to be included within the scope of the appended claims. The invention is defined by the claims and their equivalents.
Claims (10)
1. A uranium content measuring device in solution, characterized by comprising:
The fluorescence cuvette is used for containing uranium-containing solution to be detected;
A pulse light source generation module; the ultraviolet pulse excitation light generated by the pulse light source generation module is incident into the fluorescent cuvette;
The time-resolved fluorescence detection module is used for collecting first fluorescence generated after the uranium-containing solution to be detected is excited by ultraviolet pulse excitation light, and detecting the intensity of the first fluorescence;
The first fluorescent light path received by the time-resolved fluorescence detection module is perpendicular to the ultraviolet pulse excitation light path;
a continuous light source generating module; the continuous excitation light generated by the continuous light source generation module is incident into the fluorescent cuvette;
the fluorescence wavelength dispersion detection module is used for collecting second fluorescence generated after the uranium-containing solution to be detected is excited by the continuous excitation light and detecting the intensity of the second fluorescence;
the second fluorescence light path received by the fluorescence wavelength dispersion detection module is perpendicular to the continuous excitation light path;
And the computer is respectively in communication connection with the time resolution fluorescence detection module and the fluorescence wavelength dispersion detection module, and is used for calculating the uranium content in a first concentration range according to the intensity of the first fluorescence, calculating the uranium content in a second concentration range according to the intensity of the second fluorescence, and the value of the first concentration range is smaller than the value of the second concentration range.
2. The uranium content measurement device of claim 1, wherein the pulsed light source generation module includes a pulsed excitation light source generator, an excitation light filter, and a first focusing lens;
Ultraviolet pulse excitation light generated by the pulse excitation light source generator sequentially passes through the excitation light filter and the first focusing lens and then enters the fluorescent cuvette.
3. The uranium content measurement device of claim 1, wherein the time-resolved fluorescence detection module includes a second focusing lens, a monochromatic grating, an optical slit, a first photodetector;
the first fluorescence is incident to the first photodetector after passing through the second focusing lens, the monochromatic grating and the optical slit in sequence.
4. The uranium content measurement device of claim 1, wherein the fluorescence wavelength dispersion detection module includes a third focusing lens, an emission optical filter, and a second photodetector;
And the second fluorescence sequentially passes through the third focusing lens and the light emitting filter and then enters the second photoelectric detector.
5. The uranium content measurement device of claim 1, further comprising: the electronic circuit module is respectively connected with the time resolution fluorescence detection module and the fluorescence wavelength dispersion detection module through signal wires and is in communication connection with the computer;
The electronic circuit module further comprises a power supply module, a signal acquisition module and a time sequence module; the signal acquisition module is in communication connection with the time sequence module and is respectively and electrically connected with the power supply module; the time sequence module is used for controlling the signal acquisition module to synchronize the acquisition signal of the first fluorescence with the emission signal of the ultraviolet pulse excitation light path.
6. A method for measuring uranium content in a solution using the uranium content measurement device of any one of claims 1 to 5, comprising:
When the uranium content is measured by adopting a time-resolved fluorescence measurement method, taking the uranium content measured by the time-resolved fluorescence measurement method as a first preliminary measurement result;
calculating a first difference between the first preliminary measurement result and a maximum endpoint value of the first concentration range;
if the first difference value is larger than a threshold value, determining the preliminary measurement result as the final uranium content;
If the first difference value is smaller than the threshold value, carrying out uranium content measurement by adopting a wavelength dispersion measurement method to obtain a second uranium content measurement result;
taking the second uranium content measurement result as a final uranium content;
When the uranium content is measured by adopting the wavelength dispersion measuring method, taking the uranium content measured by the wavelength dispersion measuring method as a second preliminary measurement result;
calculating a second difference between the second preliminary measurement and a minimum endpoint value of the second concentration range;
if the second difference value is greater than a threshold value, determining the second preliminary measurement result as the final uranium content;
If the second difference value is smaller than the threshold value, carrying out uranium content measurement by adopting a time-resolved fluorescence measurement method to obtain a third uranium content measurement result;
And taking the third uranium content measurement result as the final uranium content.
7. The uranium content measurement method according to claim 6, wherein the uranium content measurement is performed by using a time-resolved fluorescence measurement method, and the uranium content measured by using the time-resolved fluorescence measurement method is used as a first preliminary measurement result, and specifically includes:
adding a fluorescence enhancement solution with preset concentration and quantitative volume into a fluorescence cuvette to obtain a first solution;
Obtaining the fluorescence intensity of the first solution by adopting a time-resolved fluorescence measurement method;
adding uranium standard solution with preset concentration and quantitative volume into the first solution to obtain second solution;
obtaining the fluorescence intensity of the second solution by adopting a time-resolved fluorescence measurement method;
adding a quantitative volume of uranium-containing solution to be detected into the second solution to obtain a third solution;
obtaining the fluorescence intensity of the third solution by adopting a time-resolved fluorescence measurement method;
and calculating to obtain the first preliminary measurement result according to the fluorescence intensity of the first solution, the fluorescence intensity of the second solution, the fluorescence intensity of the third solution and the preset concentration of the uranium standard solution.
8. The uranium content measurement method according to claim 7, wherein the obtaining the fluorescence intensity of the first solution by using a time-resolved fluorescence measurement method specifically includes:
performing area integration on the single ultraviolet pulse excitation light path trigger attenuation time and the fluorescence attenuation intensity to obtain single pulse fluorescence intensity, wherein the fluorescence attenuation intensity is the first solution fluorescence intensity corresponding to the single ultraviolet pulse excitation light path trigger attenuation time;
And summing a plurality of single pulse fluorescence intensities obtained in the time of presetting and collecting the fluorescence intensity of the first solution to obtain the fluorescence intensity of the first solution.
9. The uranium content measurement method according to claim 6, wherein when the uranium content is measured by using a wavelength dispersion measurement method, the uranium content measured by the wavelength dispersion measurement method is used as a second preliminary measurement result, and specifically includes:
adding a fluorescence enhancement solution with preset concentration and quantitative volume and a uranium standard solution with preset concentration and quantitative volume into the fluorescence cuvette to obtain a fourth solution;
obtaining the fluorescence intensity of the fourth solution by adopting a wavelength dispersion measurement method;
adding uranium standard solution with preset concentration and set multiple quantitative volume into the fourth solution to obtain fifth solution;
Obtaining the fluorescence intensity of the fifth solution by adopting a wavelength dispersion measurement method;
Adding a quantitative volume of uranium-containing solution to be detected into the fourth solution to obtain a sixth solution;
obtaining the fluorescence intensity of the sixth solution by adopting a wavelength dispersion measurement method;
And calculating to obtain the second preliminary measurement result according to the fluorescence intensity of the fourth solution, the fluorescence intensity of the fifth solution, the fluorescence intensity of the sixth solution and the quantitative volume of the uranium-containing solution to be measured.
10. The uranium content measurement method according to claim 9, wherein the obtaining the fluorescence intensity of the fourth solution by using a wavelength dispersion measurement method specifically includes:
Calculating an average value of the fluorescence intensities of a plurality of fourth solutions obtained in a preset time for collecting the fluorescence intensities of the fourth solutions;
the average value was taken as the new fluorescence intensity of the fourth solution.
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