CN112129689A - System and method for measuring corrosion behavior of reactor cladding material by in-situ spectrum - Google Patents
System and method for measuring corrosion behavior of reactor cladding material by in-situ spectrum Download PDFInfo
- Publication number
- CN112129689A CN112129689A CN202010939270.4A CN202010939270A CN112129689A CN 112129689 A CN112129689 A CN 112129689A CN 202010939270 A CN202010939270 A CN 202010939270A CN 112129689 A CN112129689 A CN 112129689A
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- cladding material
- pipeline
- corrosion behavior
- window
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000005253 cladding Methods 0.000 title claims abstract description 42
- 238000005260 corrosion Methods 0.000 title claims abstract description 30
- 230000007797 corrosion Effects 0.000 title claims abstract description 30
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000001228 spectrum Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- 238000010438 heat treatment Methods 0.000 claims abstract description 55
- 230000007246 mechanism Effects 0.000 claims abstract description 36
- 238000005070 sampling Methods 0.000 claims abstract description 35
- 230000002285 radioactive effect Effects 0.000 claims abstract description 30
- 238000004458 analytical method Methods 0.000 claims abstract description 21
- 238000007789 sealing Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000005259 measurement Methods 0.000 claims description 15
- 230000005855 radiation Effects 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000013307 optical fiber Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000003595 spectral effect Effects 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000003028 elevating effect Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 238000010884 ion-beam technique Methods 0.000 claims description 2
- 210000001503 joint Anatomy 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 7
- 238000004088 simulation Methods 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 6
- 238000004817 gas chromatography Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000004811 liquid chromatography Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 239000011257 shell material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 229910052805 deuterium Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000003608 radiolysis reaction Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- -1 hydroxyl free radical Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
Landscapes
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Pathology (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Ecology (AREA)
- Environmental Sciences (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses a system and a method for measuring corrosion behavior of reactor cladding material by in-situ spectrum, which comprises the steps of firstly placing the cladding material in a reaction kettle, then creating a high-temperature high-pressure environment in the reaction kettle, then safely placing the reaction kettle in an irradiation field created by a radioactive source, enabling detection light to pass through an irradiation window on a heating mechanism in the irradiation process, entering the reaction kettle, analyzing the change of the material in the reaction kettle on line by detection means such as a gas chromatography analyzer, a liquid chromatography analyzer and an infrared spectrometer after emission, and analyzing a gas product extracted from a gas sampling pipeline of the reaction kettle by an on-line analysis system, thereby knowing the corrosion behavior of the cladding material under the high-temperature high-pressure irradiation condition. And the stability of the simulation system is ensured through the pressure measuring pipeline, the pressure relief pipeline and the temperature sensor, and various dangers are avoided.
Description
Technical Field
The invention relates to the technical field of chemical analysis equipment, in particular to a system and a method capable of in-situ spectral measurement.
Background
The fukushima event again rings the alarm clock for human nuclear security. As the nuclear energy of future pillar energy of human beings is rapidly developed, the nuclear energy safety, particularly the nuclear power safety, becomes one of the cores of the national safety fields of China and even the whole world, and the traditional nuclear fuel cladding material leads the heat extraction system to be incapable of working normally under the condition of losing an off-site power supply due to the hydrothermal reaction, thereby leading to hydrogen explosion. Because of the urgent need of research on novel cladding materials and the extremely high cost of reactor irradiation research, the materials are generally required to be evaluated in complex coupling environments such as temperature, pressure, water environment, radiation field and the like in a simulated environment outside the reactor. However, because the requirements of environments such as an irradiation field, high temperature and high pressure and the like on detection equipment are severe, the change of the material before and after irradiation is evaluated mainly by a method of taking out the material after corrosion in a simulated environment for representation at present.
However, in material evaluation, it is very important to obtain the life and corrosion mechanism of a material in real time in a simulated environment. Researchers have adopted the method of water phase flow to react with the flowing water phase of the material, and detect the water flowing out of the system, and try to obtain the change situation of the water phase in the reaction process, but because of the inherent stability of the nuclear material, the influence on the water in the corrosion process is small, and in the case of the flowing water, the effect is more diluted, so the detection difficulty is very high. Secondly, in-situ monitoring is carried out on the research on the types of corrosion tracks, chemical bond fractures and particles absorbed by the material in real time, which are generated by the shell material in water radiolysis, on the microscopic scale, the method has practical guiding significance for the microscopic modification of the material, and the material deformation behavior data and the measurement standard on the microscopic scale are an urgent requirement for improving the performance of the material under the complex coupling condition, so that a sample in a simulated environment needs to be subjected to various spectroscopic analyses. In addition, for the safety of the reactor, the gas products generated by the materials under the working condition environment have a more fatal influence on the safety of the reactor, and therefore, the continuous sampling analysis of the gas under the coupling environment is not reported.
Researchers have reported an on-line high-temperature high-pressure radiation corrosion simulation system and a simulation method, and in order to realize the synergistic effect of multiple factors of a simulation material under the high-temperature high-pressure radiation condition, theoretical high-pressure pumps and preheaters are adopted for temperature increase and pressure increase. This kind of pressure boost mode efficiency is lower under the experimental condition, is not conform to the realistic condition of experiment, can't reach higher test pressure. More importantly, due to the inherent characteristics of the reaction container, the detection light cannot enter the reaction window, so that the experimental data related to the spectral measurement cannot be realized on line and in real time.
Disclosure of Invention
In order to solve the problems, the invention provides a system capable of measuring the corrosion behavior of a reactor cladding material by in-situ spectroscopy, and aims to introduce a series of in-situ spectroscopy and chromatographic analysis means to better combine in-situ monitoring with material modification so as to research the change rule of the reactor cladding material under complex coupling conditions of high temperature, high pressure, radiation and the like and guide the improvement of the traditional cladding material and the design of a novel cladding material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a system for in-situ spectrometric measurement of corrosion behavior of reactor cladding material, comprising:
the radioactive source provides irradiation for the system;
the reaction kettle comprises a kettle body, a window and a sealing cover, wherein the window and the sealing cover are arranged on the kettle body, and the top of the sealing cover is connected with a sample introduction pipeline and a sampling pipeline;
the heating mechanism comprises a heating sleeve and an irradiation window which is arranged on the heating sleeve and matched with the window;
the monitoring mechanism comprises a sample online analysis system, and the sample online analysis system is connected with the reaction kettle;
the lifting mechanism comprises a lifting platform, and the reaction kettle and the heating mechanism are arranged on the lifting platform and are parallel to the radioactive source;
and the control system comprises a heating control console arranged in the lifting control room, and the heating control console is in control connection with the heating sleeve through a labyrinth.
Further, the radiation source is one of gamma rays, X rays, electron beams, neutron beams, proton beams and heavy ion beams.
Furthermore, the window is arranged in a clamping groove extending outwards in the middle of the kettle body, a pressure measuring pipeline and a pressure relief pipeline are further arranged on the sealing cover, a detachable pressure sensor is mounted on the pressure measuring pipeline, and an adjustable safety valve is mounted on the pressure relief pipeline; the sampling pipeline is connected with a high-pressure gas generating device and a sampling valve, and the sampling pipeline is connected with a sampling valve.
Furthermore, the online sample analysis system comprises a gas chromatography analyzer, a liquid chromatography analyzer and an infrared optical fiber spectrometer, wherein the gas chromatography analyzer and the liquid chromatography analyzer are respectively connected with a sampling pipeline, and the infrared optical fiber spectrometer is in butt joint with the window.
Further, the sealing cover and the kettle body are sealed through a graphite gasket, and the kettle body is a stainless steel kettle body with a platinum lining.
Further, a magnetic stirrer is arranged at the bottom of the heating mechanism, and the magnetic stirrer is magnetically connected with magnetons arranged in the reaction kettle.
Furthermore, a temperature sensor is arranged in the heating mechanism and connected with a heating control console.
Further, elevating system is equipped with organism and elevator motor, inside elevator platform and elevator motor located the organism, just the pulley board car is installed to the bottom of organism, elevator platform is connected with elevator motor's output, elevator motor's shell adopts the interbedded stainless steel shell that contains the stereotype.
A method for in-situ spectral measurement of corrosion behavior of reactor cladding materials comprises the following steps:
1) adding a reactor cladding material and a solvent into a reaction kettle, introducing high-pressure gas, and then putting the reaction kettle and a heating mechanism into a radiation field formed by a radioactive source;
2) the heating mechanism is controlled by the heating control console to heat and stir the reaction kettle;
3) and carrying out chemical analysis on reactants in the reaction kettle through the window and the sampling pipeline in the reaction process.
Further, the reactor cladding material is one of SiC, FeCrAl and Zr-4 alloy, and the solvent is deionized water.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention discloses a system capable of measuring corrosion behavior of reactor cladding material by in-situ spectrum, which is characterized in that firstly, the cladding material is placed in a reaction kettle, then a high-temperature high-pressure environment is created in the reaction kettle, then the reaction kettle is safely placed in an irradiation field created by a radioactive source, irradiation enters the reaction kettle through an irradiation window on a heating mechanism to simulate the environment of the reactor, and then the reactor cladding material in the reaction kettle is chemically analyzed by an on-line analysis system, so that the corrosion behavior of the cladding material under the high-temperature high-pressure irradiation condition is known.
2. The simulation system provides an environment which is more consistent with the real condition of a reactor compared with the prior art for the cladding material by arranging the reaction kettle with the window, the heating mechanism and the high-pressure gas generating device, ensures the stability of the simulation system by the pressure measuring pipeline, the pressure relief pipeline and the temperature sensor, and avoids various dangers.
3. The reaction kettle and the heating mechanism are arranged on the lifting platform and are parallel to the radioactive source when the radioactive source rises, so that a sample in the reaction kettle can be continuously and stably irradiated, and the normal running state of the radioactive source is not influenced.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a schematic view of the structure of a reaction vessel in the present invention;
FIG. 3 is a view showing the structure of the reaction vessel, the heating jacket and the magnetic stirrer;
FIG. 4 is a schematic perspective view of the lifting mechanism of the present invention;
FIG. 5 is a side view of the lift mechanism of the present invention;
FIG. 6 is a graph showing changes in the infrared spectrum of SiC in example 1 of the present invention;
FIG. 7 shows Fe in example 2 of the present invention3+An ultraviolet absorption spectrum chart;
FIG. 8 is a schematic diagram of a hydrogen calibration curve in example 3 of the present invention;
FIG. 9 is a graph showing the hydrogen gas yield with time in example 3 of the present invention;
FIG. 10 is a graph showing the hydrogen gas yield with time in example 4 of the present invention;
in the figure: 1. a radioactive source; 2. a reaction kettle; 21. a kettle body; 22. a window; 23. a sealing cover; 24. a sample introduction line; 25. a sampling line; 26. a pressure measuring pipeline; 27. a pressure relief line; 3. heating a jacket; 4. an irradiation window; 5. a sample on-line analysis system; 6. a lifting mechanism; 7. a lifting platform; 8. a body; 9. a lifting motor; 10. a lift control room; 11. a heating console; 12. a high pressure gas generating device; 13. a trolley plate vehicle; 14. a detachable pressure sensor; 15. an adjustable safety valve; 16. a sample injection valve; 17. a sampling valve; 18. a magnetic stirrer.
Detailed Description
The following embodiments are provided to describe the embodiments of the present invention, and to further describe the detailed description of the embodiments of the present invention, such as the shapes, configurations, mutual positions and connection relationships of the components, the functions and operation principles of the components, the manufacturing processes and operation methods, etc., so as to help those skilled in the art to more fully, accurately and deeply understand the inventive concept and technical solutions of the present invention.
An in-situ spectral measurable reactor cladding material corrosion behavior high-temperature high-pressure reaction device, comprising:
a system for in-situ spectrometric measurement of corrosion behavior of reactor cladding material, comprising:
the radioactive source provides irradiation for the system;
the reaction kettle comprises a kettle body, a window and a sealing cover, wherein the window and the sealing cover are arranged on the kettle body, and the top of the sealing cover is connected with a sample introduction pipeline and a sampling pipeline;
the heating mechanism comprises a heating sleeve and an irradiation window which is arranged on the heating sleeve and matched with the window;
the monitoring mechanism comprises a sample online analysis system, and the sample online analysis system is connected with the reaction kettle;
the lifting mechanism comprises a lifting platform, and the reaction kettle and the heating mechanism are arranged on the lifting platform and are parallel to the radioactive source;
and the control system comprises a heating control console arranged in the lifting control room, and the heating control console is in control connection with the heating sleeve through a labyrinth.
The invention discloses a system capable of measuring corrosion behavior of a reactor cladding material by in-situ spectroscopy, which is characterized in that the cladding material is firstly placed in a reaction kettle, then a high-temperature high-pressure environment is created in the reaction kettle, then the reaction kettle is safely placed in an irradiation field created by a radioactive source, irradiation enters the reaction kettle through an irradiation window on a heating mechanism to simulate the environment of the reactor, and then reactants in the reaction kettle are analyzed by an on-line analysis system, so that the corrosion behavior of the cladding material under the high-temperature high-pressure irradiation condition is known.
1-5, a system for in situ spectrometric measurement of corrosion behavior of reactor cladding materials, comprising: the device comprises a radioactive source 1, a reaction kettle 2, a heating jacket 3, an irradiation window 4, a sample online analysis system 5 and a lifting mechanism 6, wherein the radioactive source 1 provides irradiation for the system when raising the source; the reaction kettle 2 comprises a kettle body 21, a window 22 and a sealing cover 23, wherein the window 22 and the sealing cover 23 are arranged on the kettle body 21, and the top of the sealing cover 23 is connected with a sample introduction pipeline 24 and a sampling pipeline 25; the sample injection pipeline 24 is connected with the high-pressure gas generation device 12, and the sample injection pipeline 25 is respectively connected with a gas chromatography analyzer, a liquid chromatography analyzer and an infrared optical fiber spectrometer of the sample online analysis system 5. The heating jacket 3 is provided with an irradiation window 4 corresponding to the window 22; the heating jacket 3 is in control connection with a heating control console 11 arranged in a lifting control room 10 through a labyrinth. The reaction kettle 2 and the heating mechanism are arranged on the lifting platform 7 and are parallel to the radioactive source 1 when the radioactive source 1 rises, so that a sample in the reaction kettle 2 can be continuously and stably irradiated, and the normal running state of the radioactive source 1 is not influenced.
Preferably, the radiation source 1 emits gamma rays to the reaction vessel 2.
Preferably, in this embodiment, the window 22 is disposed in a clamping groove extending outward from the middle of the kettle 21, the sealing cover 23 is further provided with a pressure measuring pipeline 26 and a pressure relief pipeline 27, the pressure measuring pipeline 26 is provided with the detachable pressure sensor 14, and the pressure relief pipeline 27 is provided with the adjustable safety valve 15; the sample injection pipeline 24 is connected with the high-pressure gas generation device 12 and the sample injection valve 16, the sample injection pipeline 25 is connected with the sample injection valve 17, and the high-pressure gas generation device 12 inputs carbon dioxide gas into the reaction kettle 2.
Preferably, the online sample analysis system 5 includes a gas chromatograph, a liquid chromatograph, and an infrared fiber spectrometer, the gas chromatograph and the liquid chromatograph are respectively connected to the sampling pipeline, and the infrared fiber spectrometer is connected to the window 22.
In this embodiment, the sealing cover 23 and the kettle body 21 are preferably sealed by a graphite gasket, and the kettle body 21 is a stainless steel kettle body lined with platinum.
In this embodiment, a magnetic stirrer 18 is preferably disposed at the bottom of the heating mechanism, and the magnetic stirrer 18 is magnetically connected to the magnetons disposed in the reaction kettle 2.
In this embodiment, a temperature sensor is preferably provided in the heating mechanism, and the temperature sensor is connected to the heating console 11.
Preferably as this embodiment, elevating system 6 is equipped with organism 8 and elevator motor 9, inside elevator platform 7 and elevator motor 9 located organism 8, just pulley board car 13 is installed to the bottom of organism 8, elevator platform 7 is connected with elevator motor 9's output, elevator motor 9's shell adopts the stainless steel shell that contains the lead plate intermediate layer. The pulley plate trolley 13 is convenient to move to a shielding chamber where the radioactive source 1 is located after materials are added into the reaction kettle 2, and the stainless steel shell with the lead plate interlayer adopted by the shell of the lifting motor 9 effectively avoids the problem that the lifting motor 9 cannot work normally due to the influence of irradiation.
A method for in-situ spectral measurement of corrosion behavior of reactor cladding materials comprises the following steps:
1) adding a reactor cladding material and a solvent into a reaction kettle 2, introducing high-pressure gas, and then putting the reaction kettle 2 and a heating mechanism into a radiation field formed by a radioactive source 1;
2) the heating mechanism is controlled by the heating control console 11 to heat and stir the reaction kettle 2;
3) during the reaction, the reactants in the reaction kettle are chemically analyzed through the window 22 and the sampling pipeline.
Preferably, in this embodiment, the reactor cladding material is SiC, and the solvent is deionized water.
Example 1
Measuring the infrared spectrum change of the SiC under the high-temperature radiation condition;
0.6767 g of SiC powder with different particle sizes and 35 ml of deionized water are prepared into turbid liquid to be put into a reaction kettle, and a wrench is used for sealing and fastening a sealing cover after stainless steel magnetons are put into the reaction kettle. Closing the sampling valve, connecting the carbon dioxide gas bottle pipe with a reaction kettle sample injection pipeline to enable the pressure in the reaction kettle to reach 1 Mpa, closing the sample injection valve, placing the reaction kettle on a lifting table, enabling an irradiation window to be vertical to the direction of a radioactive source, enabling the irradiation aperture to be the minimum, enabling the radioactive source to ascend, and starting heating after the height of the radioactive source is stable; the target temperature is 573.15K, the heating power supply is closed after the temperature is raised and the stirring is carried out for 1h, the pressure reaches 25 Mpa, the irradiation is carried out for 13h, and the irradiation dose is 480 Gy/h. In the irradiation process, a deuterium lamp is used as a light source to enter from one side of an irradiation window, the deuterium lamp penetrates through a reactant and is detected by an infrared optical fiber spectrometer, and the absorption spectrum of the reactant is measured after one hour.
SiO can be generated in the hydrothermal reaction of the reactant SiC2The generated hydroxyl free radical with high reaction activity can be generated after the water is subjected to the radiolysis, and the SiO can be further promoted2Dissolving in high-temperature and high-pressure water to generate Si (OH)4If the Si — OH chemical bond (having an infrared absorption peak) is detected in the product as shown in fig. 6, it is confirmed that SiC is corroded.
Example 2:
ultraviolet spectrum of charge transfer at the interface of the reaction kettle;
0.06g FeCrAl alloy powder with the particle size of 50 nm and 35 mL deionized water are prepared into turbid liquid and put into a reaction kettle, and a wrench is used for sealing and fastening a sealing cover after stainless steel magnetons are put into the reaction kettle. Closing the sampling valve, connecting the carbon dioxide gas bottle tube with a reaction kettle sampling pipeline to ensure that the pressure in the reaction kettle reaches 2 Mpa, closing the sampling valve, connecting the gas chromatographic analyzer with the reaction kettle sampling pipeline, then placing the reaction kettle on a lifting table, ensuring that the irradiation window is vertical to the direction of a radioactive source, ensuring that the irradiation aperture is the minimum, the radioactive source rises the source, stirring for 1h simultaneously and ensuring that the irradiation dose is 480 Gy/h. In the irradiation process, a deuterium lamp is used as a light source to emit from an irradiation window, the deuterium lamp penetrates through a reactant and is detected by an ocean optics USB2000+ optical fiber spectrometer, and the absorption spectrum of the reactant is measured after irradiation for one hour.
The FeCrAl alloy powder generates high-valence iron ions through hydrothermal reaction, and if the Fe ions are detected in the product as shown in FIG. 73+(having an ultraviolet absorption peak), the FeCrAl alloy powder is proved to be corroded.
Example 3:
measurement of H under Zr-4 alloy high-temperature radiation condition2The yield of the reactor can be indirectly proved to be corroded by measuring the yield of the hydrogen through a gas chromatographic analyzer because the zirconium water can generate the hydrogen after reacting;
0.06g of Zr-4 alloy powder with the particle size of 50 nm and 35 mL of deionized water are prepared into turbid liquid to be put into a reaction kettle, and a wrench is used for sealing and fastening a sealing cover after stainless steel magnetons are put into the reaction kettle. Closing the sampling valve, connecting the carbon dioxide gas bottle tube with a reaction kettle sampling pipeline to ensure that the pressure in the reaction kettle reaches 2 Mpa, closing the sampling valve, connecting the gas chromatographic analyzer with the reaction kettle sampling pipeline, then placing the reaction kettle on a lifting table, ensuring that the irradiation window is vertical to the direction of the radioactive source, ensuring that the irradiation aperture is the minimum, the radioactive source raises the source, and simultaneously stirring the mixture for the time length shown in the figure 8, wherein the irradiation dose is 480 Gy/h. In the reaction process, gas in the reaction kettle is extracted at regular time through a sampling pipeline, and the yield of hydrogen in the kettle is analyzed by a gas chromatographic analyzer.
The volume of a quantitative tube connected with the sampling valve is 50 ml, and a gas sample in the quantitative tube enters a gas chromatographic analyzer to detect the hydrogen yield, and the specific method comprises the following steps: 50 ml of sample gas enters a quantitative ring (1 ml) of a gas chromatograph, a complete measurement process from gas inlet to gas outlet takes 10 minutes, and a chromatographic interface shows a peak area of hydrogen after the measurement is finished, and the peak area is converted by a standard curve made by using standard gas before, namely, hydrogen molar quantity = (peak area +16891.38)/(1.18 × POWER (10, 12)) × 50; FIG. 9 is a graph of a standard curve and hydrogen production for un-reacted DI water versus added reactant DI water as a function of irradiation dose.
Example 4:
0.06g of Zr-4 alloy powder with the particle size of 500nm and 35 mL of deionized water are prepared into suspension, the suspension is placed into a reaction kettle, and a wrench is used for sealing and fastening a sealing cover after stainless steel magnetons are placed into the reaction kettle. Close the sample valve, with carbon dioxide gas cylinder and reation kettle sampling pipeline connection, make reation kettle internal pressure reach 2 Mpa, close the injection valve, gas chromatography appearance and reation kettle sampling pipeline connection, then place reation kettle on the elevating platform, the irradiation window is perpendicular with the radiation source direction, the irradiation aperture is minimum, the radiation source rises the source, stir the time as shown in figure 10 simultaneously, the irradiation dose is 480 Gy/h, the buret volume of connecting on the sample valve is 50 ml, gas sample through in the buret gets into gas chromatography appearance with this detection hydrogen yield, concrete method is: 50 ml of sample gas enters a quantitative ring (1 ml) of a gas chromatograph, a complete measurement process from gas inlet to gas outlet of the chromatograph takes 10 minutes, and after the measurement is completed, a chromatographic interface shows a peak area of hydrogen, which is converted by a standard curve previously made by using standard gas, namely, hydrogen molar quantity = (peak area +16891.38)/(1.18 × POWER (10, 12)) × 50, and a change curve of hydrogen yield with time is shown in fig. 10.
In the invention, the system provides an environment which is more consistent with the real condition of a reactor compared with the prior art for the cladding material by arranging the reaction kettle 2 with the window 22, the heating mechanism and the high-pressure gas generating device 12, ensures the stability of the simulation system by the pressure measuring pipeline 26, the pressure relief pipeline 27 and the temperature sensor, and avoids various dangers, and in addition, the system can carry out real-time observation and detection on various secondary products generated by the sample in the reaction kettle 2 under the action of radiolysis water by the sample on-line analysis system 5.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A system for in-situ spectrometric measurement of corrosion behavior of reactor cladding material, comprising:
the radioactive source provides irradiation for the system;
the reaction kettle comprises a kettle body, a window and a sealing cover, wherein the window and the sealing cover are arranged on the kettle body, and the top of the sealing cover is connected with a sample introduction pipeline and a sampling pipeline;
the heating mechanism comprises a heating sleeve and an irradiation window which is arranged on the heating sleeve and matched with the window;
the monitoring mechanism comprises a sample online analysis system, and the sample online analysis system is connected with the reaction kettle;
the lifting mechanism comprises a lifting platform, and the reaction kettle and the heating mechanism are arranged on the lifting platform and are parallel to the radioactive source;
and the control system comprises a heating control console arranged in the lifting control room, and the heating control console is in control connection with the heating sleeve through a labyrinth.
2. The system for in situ spectrally measurable reactor cladding material corrosion behavior according to claim 1, characterized by: the radioactive source is one of gamma rays, X rays, electron beams, neutron beams, proton beams and heavy ion beams.
3. The system for in situ spectrally measurable reactor cladding material corrosion behavior according to claim 1, characterized by: the window is arranged in a clamping groove extending outwards in the middle of the kettle body, the sealing cover is further provided with a pressure measuring pipeline and a pressure relief pipeline, the pressure measuring pipeline is provided with a detachable pressure sensor, and the pressure relief pipeline is provided with an adjustable safety valve; the sampling pipeline is connected with a high-pressure gas generating device and a sampling valve, and the sampling pipeline is connected with a sampling valve.
4. The system for in situ spectrally measurable reactor cladding material corrosion behavior according to claim 1, characterized by: the online sample analysis system comprises a gas chromatographic analyzer, a liquid chromatographic analyzer and an infrared optical fiber spectrometer, wherein the gas chromatographic analyzer and the liquid chromatographic analyzer are respectively connected with a sampling pipeline, and the infrared optical fiber spectrometer is in butt joint with a window.
5. The system for in situ spectrally measurable reactor cladding material corrosion behavior according to claim 1, characterized by: the sealing cover and the kettle body are sealed through a graphite gasket, and the kettle body is a stainless steel kettle body with a platinum lining.
6. The system for in situ spectrally measurable reactor cladding material corrosion behavior according to claim 1, characterized by: and a magnetic stirrer is arranged at the bottom of the heating mechanism and is magnetically connected with magnetons arranged in the reaction kettle.
7. The system for in situ spectrally measurable reactor cladding material corrosion behavior according to claim 6, characterized by: and a temperature sensor is arranged in the heating mechanism and is connected with a heating console.
8. The system for in situ spectrally measurable reactor cladding material corrosion behavior according to claim 1, characterized by: elevating system is equipped with organism and elevator motor, inside elevator platform and elevator motor located the organism, just the pulley board car is installed to the bottom of organism, elevator platform is connected with elevator motor's output, elevator motor's shell adopts the stainless steel shell that contains the stereotype intermediate layer.
9. A method for in-situ spectral measurement of corrosion behavior of reactor cladding materials is characterized by comprising the following steps:
1) adding a reactor cladding material and a solvent into a reaction kettle, introducing high-pressure gas, and then putting the reaction kettle and a heating mechanism into a radiation field formed by a radioactive source;
2) the heating mechanism is controlled by the heating control console to heat and stir the reaction kettle;
3) and carrying out chemical analysis on reactants in the reaction kettle through the window and the sampling pipeline in the reaction process.
10. The method for in situ spectrally measurable reactor cladding material corrosion behavior according to claim 9, characterized by: the reactor cladding material is one of SiC, FeCrAl and Zr-4 alloy, and the solvent is deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010939270.4A CN112129689A (en) | 2020-09-09 | 2020-09-09 | System and method for measuring corrosion behavior of reactor cladding material by in-situ spectrum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010939270.4A CN112129689A (en) | 2020-09-09 | 2020-09-09 | System and method for measuring corrosion behavior of reactor cladding material by in-situ spectrum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112129689A true CN112129689A (en) | 2020-12-25 |
Family
ID=73845269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010939270.4A Pending CN112129689A (en) | 2020-09-09 | 2020-09-09 | System and method for measuring corrosion behavior of reactor cladding material by in-situ spectrum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112129689A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012181199A (en) * | 2012-04-11 | 2012-09-20 | Toshiba Corp | Adhesion amount monitoring method of titanium oxide |
| CN102928255A (en) * | 2012-11-14 | 2013-02-13 | 天津市先权工贸发展有限公司 | Liquid in-situ chromatographic sampling device inside high-temperature high-pressure reaction kettle and method of liquid in-situ chromatographic sampling device |
| CN103712931A (en) * | 2013-12-31 | 2014-04-09 | 陕西师范大学 | High-pressure ultraviolet visible near-infrared spectroscopy device for online monitoring of supercritical system |
| CN109994231A (en) * | 2019-04-28 | 2019-07-09 | 东华理工大学 | A kind of radiation corrosion test device and test method |
| CN110553974A (en) * | 2019-08-16 | 2019-12-10 | 西安交通大学 | System and method for testing ultrahigh-temperature corrosion of structural material under severe accident of nuclear reactor |
-
2020
- 2020-09-09 CN CN202010939270.4A patent/CN112129689A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012181199A (en) * | 2012-04-11 | 2012-09-20 | Toshiba Corp | Adhesion amount monitoring method of titanium oxide |
| CN102928255A (en) * | 2012-11-14 | 2013-02-13 | 天津市先权工贸发展有限公司 | Liquid in-situ chromatographic sampling device inside high-temperature high-pressure reaction kettle and method of liquid in-situ chromatographic sampling device |
| CN103712931A (en) * | 2013-12-31 | 2014-04-09 | 陕西师范大学 | High-pressure ultraviolet visible near-infrared spectroscopy device for online monitoring of supercritical system |
| CN109994231A (en) * | 2019-04-28 | 2019-07-09 | 东华理工大学 | A kind of radiation corrosion test device and test method |
| CN110553974A (en) * | 2019-08-16 | 2019-12-10 | 西安交通大学 | System and method for testing ultrahigh-temperature corrosion of structural material under severe accident of nuclear reactor |
Non-Patent Citations (2)
| Title |
|---|
| （美）哈密德•荷马提编: "《近地激光通信》", 31 May 2017 * |
| 边秀房等编著: "《金属熔体结构》", 30 June 2003, 上海交通大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guzonas et al. | Water chemistry in a supercritical water-cooled pressure tube reactor | |
| CN103837558A (en) | Device and method for detecting multiple elements and content thereof in water solution based on PGNAA (Prompt Gamma-Ray Neutron Activation Analysis) technology | |
| CN109712724A (en) | A kind of double reactor core zero-power facilities | |
| CN105758830A (en) | Method for measuring content of total arsenic by digesting marine product in steps through microwave humidifying method | |
| CN106706588B (en) | A kind of accurate multiphase photocatalysis resonance fluorescence method for detecting determination of trace uranium in environmental water sample | |
| CN112129689A (en) | System and method for measuring corrosion behavior of reactor cladding material by in-situ spectrum | |
| Palazhchenko | Pourbaix Diagrams at Elevated Temperatures A Study of Zinc and Tin | |
| CN218848014U (en) | Test system for high-burnup fuel rod bulging blasting | |
| Mihalczo et al. | 252 Cf-source-driven neutron noise analysis method | |
| CN107907493A (en) | The high sensitivity spectrophotometry of rhenium or technetium in a kind of measure solution and water environment | |
| Camaioni et al. | Organic tanks safety program FY96 waste aging studies | |
| CN110208075A (en) | A kind of radioactivity organic matter pre-treating method | |
| Youker et al. | Peroxide Formation, Destruction, and Precipitation in Uranyl Sulfate Solutions: Simple Addition and Radiolytically Induced Formation | |
| Gallmeier | A New MCNP Option: KCORR—The use of the correlated sampling method to study reactivity effects due to changes of a reactor arrangement | |
| Guerin | Radiation Chemistry in Pressurized Water Nuclear Reactors: H2 Generation by 10B (n, α) 7Li, and the Reaction of Borate With• OH | |
| RU2527489C2 (en) | Neutron-activation method of monitoring burning of spent fuel assemblies of thermal neutron reactors and apparatus therefor | |
| Kysela et al. | Loop capabilities in Rez for water chemistry and corrosion control of cladding and in-core components | |
| CN114689617A (en) | Method for measuring gamma energy emissivity of fission product in neptunium dioxide sample | |
| Daughtry et al. | FFTF reactor characterization program | |
| Orlova et al. | Formation and investigation of nitride fuel compatible protective coatings on ferrite–martensite steel | |
| Smith | Speciation and spectroscopy of the uranyl and tetravalent plutonium nitrate systems: Fundamental studies and applications to used fuel reprocessing | |
| Ošmera et al. | The Activity of the Czechoslovak Working Group on Reactor Dosimetry in the Period from 1980 to 1983 | |
| Paranjpe | Review of fast reactor activities in India | |
| Sreenivasulu | Studies related to spent fuel reprocessing using tri iso amyl phosphate as an alternate extractant to tri n butyl phosphate | |
| CN109655439A (en) | A method of uranium is surveyed containing europium (III) complex surface fluorescence sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |