CN114280025A - 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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- CN114280025A CN114280025A CN202111628052.XA CN202111628052A CN114280025A CN 114280025 A CN114280025 A CN 114280025A CN 202111628052 A CN202111628052 A CN 202111628052A CN 114280025 A CN114280025 A CN 114280025A
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 163
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 119
- 238000005259 measurement Methods 0.000 claims abstract description 55
- 239000006185 dispersion Substances 0.000 claims abstract description 49
- 238000000691 measurement method Methods 0.000 claims abstract description 46
- 238000001514 detection method Methods 0.000 claims abstract description 27
- 238000001917 fluorescence detection Methods 0.000 claims abstract description 23
- 230000005284 excitation Effects 0.000 claims description 36
- 239000012086 standard solution Substances 0.000 claims description 14
- 238000004891 communication Methods 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 7
- 230000010354 integration Effects 0.000 claims description 5
- 239000012898 sample dilution Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 description 9
- 239000012488 sample solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method 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
- 238000004458 analytical method Methods 0.000 description 3
- 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
- 230000008569 process Effects 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
- 230000035508 accumulation Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000010812 external standard method Methods 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
- 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
- 238000012805 post-processing Methods 0.000 description 1
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- 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, which are characterized in that a pulsed light source generation module and a time-resolved fluorescence detection module are arranged, and the uranium content in a low-concentration uranium-containing solution to be measured is measured by adopting a time-resolved fluorescence measurement method; the continuous light source generation module and the fluorescence wavelength dispersion detection module are arranged, the high-concentration uranium content is measured by adopting a wavelength dispersion measurement method, compared with the existing fluorescence uranium measuring instrument, the measurement device improves the measurement range of the uranium content, and compared with the method that the solution needs to be diluted when the relatively high-concentration uranium-containing solution needs to be measured in the prior art, the continuous light source generation module and the fluorescence wavelength dispersion detection module can directly measure the uranium content of the high-concentration uranium-containing solution, so that the inconvenience caused by sample dilution and repeated measurement is reduced.
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
The analysis and test work of uranium is related to the analysis and test work of natural uranium ores and the post-processing of nuclear fuels. Although the existing measurement 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 required for measurement.
The method for measuring the trace uranium by fluorescence has the advantages of simple equipment, convenience in operation, low detection lower limit and the like, and is used in uranium ore testing and post-treatment processes. But only low concentrations of uranium in the 0-100ppb range can be measured directly due to its relatively narrow linear range.
Therefore, there is a need for an apparatus and a method for measuring the content of uranium in a solution to improve the measurement range.
Disclosure of Invention
The invention aims to provide a device and a method for measuring the content of uranium in a solution, so as to improve the measurement range of the content of uranium.
In order to achieve the purpose, the invention provides the following scheme:
a device for measuring the uranium content in solution, comprising:
the fluorescence cuvette is used for containing a uranium-containing solution to be detected;
a pulse light source generating module; the ultraviolet pulse excitation light generated by the pulse light source generation module is incident into the fluorescence 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 light path between the pulse light source generation module and the time-resolved fluorescence detection module is vertical to the light path of the ultraviolet pulse excitation light;
a continuous light source generation module; continuous exciting light generated by the continuous light source generation module is incident into the fluorescence 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 continuous exciting light and detecting the intensity of the second fluorescence;
the light path between the continuous light source generation module and the fluorescence wavelength dispersion detection module is vertical to the light path of the continuous exciting light;
and the computer is in communication connection with the time-resolved fluorescence detection module and the fluorescence wavelength dispersion detection module respectively, and is used for calculating the uranium content in a first concentration range according to the intensity of the first fluorescence and calculating the uranium content in a second concentration range according to the intensity of the second fluorescence, wherein the value of the first concentration range is smaller than that of the second concentration range.
A method for measuring the content of uranium in 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 and a maximum endpoint value of the first concentration range;
if the first difference 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, determining the uranium content 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 a wavelength dispersion measurement method, taking the uranium content measured by the wavelength dispersion measurement method as a second primary 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 is greater than the threshold, determining the second preliminary measurement result as a final uranium content;
if the second difference is smaller than the threshold value, determining the uranium content by adopting a time-resolved fluorescence measurement method to obtain a third uranium content measurement result;
taking the third uranium content measurement 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, which are characterized in that a pulsed light source generation module and a time-resolved fluorescence detection module are arranged, and the uranium content in a low-concentration uranium-containing solution to be measured is measured by adopting a time-resolved fluorescence measurement method; the continuous light source generation module and the fluorescence wavelength dispersion detection module are arranged, the high-concentration uranium content is measured by adopting a wavelength dispersion measurement method, compared with the existing fluorescence uranium measuring instrument, the measurement device improves the measurement range of the uranium content, and compared with the method that the solution needs to be diluted when the relatively high-concentration uranium-containing solution needs to be measured in the prior art, the continuous light source generation module and the fluorescence wavelength dispersion detection module can directly measure the uranium content of the high-concentration uranium-containing solution, so that the inconvenience caused by sample dilution and repeated measurement is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings 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 it is obvious for those skilled in the art to obtain other drawings without creative efforts. The following drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
Fig. 1 shows a schematic diagram of a device for measuring the uranium content in solution according to the invention;
fig. 2 shows a flow chart of a method for measuring the uranium content in a solution according to the invention.
Description of the symbols:
the system 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, an 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 technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
As used in this disclosure and in the claims, the terms "a," "an," "the," and/or "the" are not intended to be inclusive in the singular, but rather are inclusive in the plural, unless the context clearly dictates otherwise. In general, the terms "comprises" and "comprising" merely indicate that steps and elements are included which are explicitly identified, that the steps and elements do not form an exclusive list, and that a method or apparatus may include other steps or elements.
The invention aims to provide a device and a method for measuring the content of uranium in a solution, so as to improve the measurement range of the content of uranium.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Example 1:
referring to fig. 1, the present embodiment provides an apparatus for measuring uranium content in a solution, including:
the fluorescence cuvette 1 is used for containing a uranium-containing solution to be detected, and preferably the optical path of the fluorescence cuvette 1 is 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 fluorescence 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 light path between the pulse light source generation module 2 and the time-resolved fluorescence detection module 3 is vertical to the light path of the ultraviolet pulse excitation light;
a continuous light source generation module 4; the continuous excitation light generated by the continuous light source generation module 4 is incident into the fluorescence cuvette 1, the continuous light source generation 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, the pulsed light source generation module 2 and the continuous light source generation module 4 may be respectively located at two sides of the fluorescence 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 continuous exciting light and detecting the intensity of the second fluorescence;
the light path between the continuous light source generation module 4 and the fluorescence wavelength dispersion detection module 5 is vertical to the light path of the continuous exciting light;
the computer 6 is in communication connection with the time-resolved fluorescence detection module 3 and the fluorescence wavelength dispersion detection module 5, and is configured to calculate the uranium content in a first concentration range according to the intensity of the first fluorescence, and calculate the uranium content in a second concentration range according to the intensity of the second fluorescence, where a value of the first concentration range is smaller than a value of the second concentration range; the computer can also realize the remote control of the equipment through software;
the electronic circuit module 7 is respectively connected with the time-resolved fluorescence detection module 3 and the fluorescence wavelength dispersion detection module 5 through signal lines and is in communication connection with the computer 6;
the electronic circuit module 7 also 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 pulsed light source generation module 2 includes a pulsed 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 exciting light filter 9 is used for obtaining an ultraviolet pulse exciting 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.
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 enters 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 a specific wavelength;
the first fluorescence sequentially passes through the second focusing lens 12, the monochromatic grating 13 and the optical slit 14, and then enters the first photodetector 15.
The fluorescence wavelength dispersion detection module 5 comprises a third focusing lens 16, an emission light 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 light filter 17 is used for filtering light signals with other wavelengths and screening second fluorescence with a specific wavelength;
the second fluorescence sequentially passes through the third focusing lens 16 and the emission light filter 17, and then enters the second photodetector 18.
The wavelength of the first fluorescence screened by the monochromatic grating 13 is smaller than the wavelength 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 the fluorescence intensity, such as a photomultiplier tube, a silicon photodiode, etc., 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; in design, a time-resolved fluorescence detection module is coupled with a pulse light source generation module, a fluorescence wavelength dispersion detection module is coupled with a continuous light source generation module, and the measurement of the low-concentration uranium content and the high-concentration uranium content can be respectively realized by adopting different detection principles, so that the measurement range of the uranium content is widened; meanwhile, the two measurement channels are mutually independent and do not interfere with each other; in addition, the measuring device can directly measure the uranium content of the high-concentration uranium-containing solution, and inconvenience caused by sample dilution and repeated measurement is reduced.
Example 2:
the present embodiment provides a method for measuring the content of uranium in a solution by using the uranium content measuring apparatus according to embodiment 1, and with reference to fig. 2, the method includes:
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 and a maximum endpoint value of the first concentration range;
s3: if the first difference 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, determining the uranium content 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 a wavelength dispersion measurement method, taking the uranium content measured by the wavelength dispersion measurement method as a second primary 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 is greater than the threshold, determining the second preliminary measurement result as a final uranium content;
s9: if the second difference is smaller than the threshold value, determining the uranium content by adopting a time-resolved fluorescence measurement method to obtain a third uranium content measurement result;
s10: taking the third uranium content measurement as the final uranium content.
As an optional implementation, S1 specifically includes:
adding a fluorescence enhancement solution with a preset concentration and a 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 a uranium standard solution with a preset concentration and a quantitative volume into the first solution to obtain a second solution;
obtaining the fluorescence intensity of the second solution by adopting a time-resolved fluorescence measurement method;
adding a quantitative volume of the 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 obtaining of 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 a 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 the fluorescence intensities of the plurality of single pulses obtained within the preset time for acquiring the fluorescence intensity of the first solution to obtain the fluorescence intensity of the first solution.
As an optional implementation, S6 specifically includes:
adding a fluorescence enhancement solution with a preset concentration and a quantitative volume and a uranium standard solution with a preset concentration and a quantitative volume into a fluorescence cuvette to obtain a fourth solution;
obtaining the fluorescence intensity of the fourth solution by adopting a wavelength dispersion measurement method;
adding a uranium standard solution with preset concentration and a set multiple quantitative volume into the fourth solution to obtain a 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 wavelength dispersion measurement method for obtaining the fluorescence intensity of the fourth solution specifically includes:
calculating the average value of the fluorescence intensities of a plurality of fourth solutions obtained within the preset time for collecting the fluorescence intensity of the fourth solution;
the mean value is taken as the fluorescence intensity of the new fourth solution.
In order to make the above process more clear to those skilled in the art, the following is explained with specific examples.
Example 1:
the parameter configuration of the uranium content measuring device is 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 5 w;
the continuous light source generation module 4 selects a semiconductor laser, the power of the semiconductor laser is 5mw, and the wavelength is 405 nm;
wavelength range transmitted by the excitation light filter 9: 230-460 nm;
the emission light filter 17 transmits the wavelength range: 480-610 nm;
the first photodetector 15 is a photomultiplier tube;
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 mus;
time-resolved fluorescence detection module 3: the single pulse fluorescence signal acquisition time sequence is from 10 mu s to 1000 mu s 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 fluorescence intensity; the acquisition time was 10s, and the fluorescence intensity accumulations of 1000 single pulses were summed.
A semiconductor laser: 5mw continuously outputs for 10 s;
fluorescence wavelength dispersion detection module 5: sampling frequency is 100Hz, and the average value of signals in an interval of 1-10 s is taken.
a) And opening the time resolution fluorescence detection module 3 and closing the fluorescence wavelength dispersion detection module 5.
And setting the high voltage of a photomultiplier to 1000v, and collecting a fluorescence signal of uranium.
Calculating the content of uranium by adopting a standard addition method: to the direction ofAdding 4.5mL of 1% sodium pyrophosphate solution into a 5mL fluorescent pool, measuring the fluorescence intensity to be F0, then accurately adding 50 mu L of 100ppb uranium standard solution into the fluorescent pool, stirring uniformly, measuring the fluorescence intensity to be F1, then adding 50 mu L of sample solution into the fluorescent pool, stirring uniformly, measuring the fluorescence intensity to be F2, and obtaining C by calculating the uranium content in the solutionU＝(F2-F1)/(F1-F0)×100ppb。
Setting the first concentration range to be 0.02-500ppb, and if the difference value between the measured uranium content and 500ppb is smaller than a threshold value, performing uranium content measurement by using a wavelength dispersion measurement method, namely:
b) and closing the time resolution fluorescence detection module 3, opening the fluorescence wavelength dispersion detection module 5, and setting the high voltage of the photomultiplier to 1000 v.
Calculating the content of uranium in the solution by adopting an external standard method: adding 4.5mL of 1% sodium pyrophosphate solution into a 5mL fluorescence pool, accurately adding 10 mu L of 10ppm uranium standard solution, measuring fluorescence intensity and marking 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 solutions, and preparing a content-intensity curve according to the content of uranium in the fluorescence pool and the corresponding fluorescence intensity, 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. Adding 4.5mL of 1% sodium pyrophosphate solution into a 5mL fluorescence pool, accurately adding 10 mu L of sample solution, recording the measured fluorescence intensity as Fs, and obtaining C by calculating the content of uranium in the sample solutionU＝(Fs-b)/a/10μL。
Setting the second concentration range to 10-500ppm, i.e. 104-5*105ppb。
Example 2:
the parameter configuration of the uranium content measuring device is 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 15 w;
the continuous light source generation module 4 selects a semiconductor laser, the power of the semiconductor laser is 100mW, and the wavelength is 405 nm;
the angle of the monochromatic grating 13 is adjusted so that the wavelength range transmitted through the optical slit 14 is: 300-350 nm;
power of the semiconductor laser: 100 mW;
wavelength of semiconductor laser: 405 nm;
the first photodetector 15 is a photomultiplier tube;
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 mus;
operating frequency of the pulsed excitation light source generator 8: 100Hz, pulse width 2 mus;
time-resolved fluorescence detection module 3: the single pulse fluorescence signal acquisition time sequence is from 10 mu s to 100 mu s 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 fluorescence intensity; the acquisition time was 20s, and the fluorescence intensity accumulations of 200 single pulses were summed.
A semiconductor laser: 5mw continuously outputs for 10 s;
fluorescence wavelength dispersion detection module 5: sampling frequency is 10Hz, and the average value of signals in an interval of 1-10 s is taken.
a) And closing the time resolution fluorescence detection module 3 and opening the fluorescence wavelength dispersion detection module 5.
Calculating the content of uranium 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 10 mu L of 10ppm uranium standard solution, measuring the fluorescence intensity and marking the fluorescence intensity as F1, repeating the steps, sequentially measuring the fluorescence intensities corresponding to 20 mu L, 30 mu L, 40 mu L and 50 mu L uranium standard solutions, namely F2, F3, F4 and F5, preparing a content-intensity curve according to the content of uranium in the fluorescence pool and the corresponding fluorescence intensity, wherein y is 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. Adding 4.5mL of 1% sodium dihydrogen phosphate solution into a 5mL fluorescence pool, accurately adding 50 mu L of sample solution, measuring the fluorescence intensity, recording as Fs, and obtaining C by calculating the content of uranium in the sample solutionU＝(Fs-b)/a/50μL。
And 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, determining the uranium content by adopting a time-resolved fluorescence measurement method, namely:
b) and opening the time resolution fluorescence detection module 3 and closing the fluorescence wavelength dispersion detection module 5.
And setting the high voltage of a photomultiplier tube to be 500v, and collecting a fluorescence signal of uranium.
Adding 4.5mL of 1% sodium dihydrogen phosphate solution into a 5mL fluorescent pool, measuring the fluorescence background value as F0, accurately adding 50 mu L of 300ppb uranium standard solution into the fluorescent pool, stirring uniformly, measuring the fluorescence value as F1, adding 50 mu L of sample solution into the fluorescent pool, stirring uniformly, measuring the fluorescence value as F2, and calculating the uranium content in the solution to obtain CU＝(F2-F1)/(F1-F0)×300ppb。
The first concentration range is set to 0.02 to 500 ppb.
According to the measuring method, the uranium content in the low-concentration uranium-containing solution to be measured is measured by adopting a time-resolved fluorescence measuring method, the high-concentration uranium content is measured by adopting a wavelength dispersion measuring method, the measuring range of the uranium content is improved, the high-concentration uranium-containing solution does not need to be diluted, the uranium content in the high-concentration uranium-containing solution can be directly measured by utilizing the wavelength dispersion measuring method, and inconvenience brought by sample dilution and repeated measurement is reduced.
In addition, the measurement 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 present invention has been described using specific terms to describe embodiments of the invention. Such as "first/second embodiment," "an embodiment," and/or "some embodiments" means a feature, structure, or characteristic described in connection with at least one embodiment of the invention. Therefore, it is emphasized and should be appreciated that two or more references to "an embodiment" or "one embodiment" or "an alternative embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, some of the features, structures, or characteristics of one or more embodiments of the present 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 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 a uranium-containing solution to be detected;
a pulse light source generating module; the ultraviolet pulse excitation light generated by the pulse light source generation module is incident into the fluorescence 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 light path between the pulse light source generation module and the time-resolved fluorescence detection module is vertical to the light path of the ultraviolet pulse excitation light;
a continuous light source generation module; continuous exciting light generated by the continuous light source generation module is incident into the fluorescence 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 continuous exciting light and detecting the intensity of the second fluorescence;
the light path between the continuous light source generation module and the fluorescence wavelength dispersion detection module is vertical to the light path of the continuous exciting light;
and the computer is in communication connection with the time-resolved fluorescence detection module and the fluorescence wavelength dispersion detection module respectively, and is used for calculating the uranium content in a first concentration range according to the intensity of the first fluorescence and calculating the uranium content in a second concentration range according to the intensity of the second fluorescence, wherein the value of the first concentration range is smaller than that of the second concentration range.
2. A uranium content measuring device according to claim 1, wherein the pulsed light source generation module comprises 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 is incident into the fluorescence cuvette.
3. A uranium content measurement device according to claim 1, wherein the time-resolved fluorescence detection module comprises a second focusing lens, a monochromatic grating, an optical slit, a first photodetector;
and the first fluorescence sequentially passes through the second focusing lens, the monochromatic grating and the optical slit and then enters the first photoelectric detector.
4. A uranium content measuring device according to claim 1, wherein the fluorescence wavelength dispersion detection module comprises a third focusing lens, an emission light filter and a second photodetector;
and the second fluorescence sequentially passes through the third focusing lens and the emission light filter and then enters the second photoelectric detector.
5. A uranium content measurement device according to 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 also 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 of measuring the content of uranium in a solution using the uranium content measuring device according to 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 and a maximum endpoint value of the first concentration range;
if the first difference 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, determining the uranium content 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 a wavelength dispersion measurement method, taking the uranium content measured by the wavelength dispersion measurement method as a second primary 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 is greater than the threshold, determining the second preliminary measurement result as a final uranium content;
if the second difference is smaller than the threshold value, determining the uranium content by adopting a time-resolved fluorescence measurement method to obtain a third uranium content measurement result;
taking the third uranium content measurement as the final uranium content.
7. The method according to claim 6, wherein the uranium content is measured by a time-resolved fluorescence measurement method, and the uranium content measured by the time-resolved fluorescence measurement method is used as a first preliminary measurement result, and the method specifically comprises:
adding a fluorescence enhancement solution with a preset concentration and a 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 a uranium standard solution with a preset concentration and a quantitative volume into the first solution to obtain a second solution;
obtaining the fluorescence intensity of the second solution by adopting a time-resolved fluorescence measurement method;
adding a quantitative volume of the 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 method for measuring the uranium content according to claim 7, wherein the obtaining of the fluorescence intensity of the first solution by using a time-resolved fluorescence measurement method specifically comprises:
performing area integration on the single ultraviolet pulse excitation light path trigger attenuation time and the fluorescence attenuation intensity to obtain a 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 the fluorescence intensities of the plurality of single pulses obtained within the preset time for acquiring the fluorescence intensity of the first solution to obtain the fluorescence intensity of the first solution.
9. The method according to claim 6, wherein when the uranium content is measured by using the wavelength dispersion measurement method, taking the uranium content measured by using the wavelength dispersion measurement method as a second preliminary measurement result specifically comprises:
adding a fluorescence enhancement solution with a preset concentration and a quantitative volume and a uranium standard solution with a preset concentration and a quantitative volume into a fluorescence cuvette to obtain a fourth solution;
obtaining the fluorescence intensity of the fourth solution by adopting a wavelength dispersion measurement method;
adding a uranium standard solution with preset concentration and a set multiple quantitative volume into the fourth solution to obtain a 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. A method according to claim 9 for measuring the uranium content, wherein the obtaining of the fluorescence intensity of the fourth solution by a wavelength dispersion measurement method specifically comprises:
calculating the average value of the fluorescence intensities of a plurality of fourth solutions obtained within the preset time for collecting the fluorescence intensity of the fourth solution;
the mean value is taken as the fluorescence intensity of the new fourth solution.
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Effective date of registration: 20240926 Address after: 100029 Beijing, Chaoyang District Anwai Kanto small courtyard 10 Patentee after: BEIJING Research Institute OF URANIUM GEOLOGY Country or region after: China Patentee after: CNNC Geological Technology Co.,Ltd. Address before: 100029 courtyard 10, xiaoguandongli, Chaoyang District, Beijing Patentee before: BEIJING Research Institute OF URANIUM GEOLOGY Country or region before: China |