CN104593778A - Method for alleviating stress corrosion of pressurized-water-reactor primary-loop structure material - Google Patents
Method for alleviating stress corrosion of pressurized-water-reactor primary-loop structure material Download PDFInfo
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- CN104593778A CN104593778A CN201410730122.6A CN201410730122A CN104593778A CN 104593778 A CN104593778 A CN 104593778A CN 201410730122 A CN201410730122 A CN 201410730122A CN 104593778 A CN104593778 A CN 104593778A
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Abstract
The invention belongs to the technical field of reactor engineering stress corrosion, and discloses a method for alleviating stress corrosion of a pressurized-water-reactor primary-loop structure material. The method comprises adding a noble metal salt solution into a coolant of a pressurized-water-reactor primary loop, wherein the concentration scope of the noble metal salt solution in the coolant is 10-1000 mu g/Kg, the injection amount is 1-100 mu g/day, and the noble metal salt solution is a salt solution of one or a mixture of Pt and Rh. The method possesses the advantages of being capable of alleviating the electrochemical corrosion potential at the surface of the pressurized-water-reactor primary-loop structure material, improving the stress corrosion resistance of the structure material and prolonging the service life of the structure material.
Description
Technical field
The invention belongs to reactor engineering stress corrosion technical field, be specifically related to a kind of method alleviating the stress corrosion of pressurized-water reactor primary Ioops structured material.
Background technology
The material that nuclear power plant reactor key part adopts mainly comprises nickel-base alloy, low alloy steel, stainless steel and zirconium alloy etc.But the material selected also has different with heap-type difference, in such as pressurized-water reactor, nickel-base alloy heat-transfer pipe accounts for about 75% of primary Ioops surface-area, and boiling-water reactor key part structure material is mainly stainless steel and low alloy steel.These materials are under the harsh running environment such as high temperature, high pressure, high irradiation, the corrosion damage of various ways can be produced, comprising stress corrosion cracking (SCC), corrosion fatigue (CF), intergranular corrosion, spot corrosion, abrasion, flowing accelerated corrosion (FAC) etc., is wherein that the environment of representative promotes that cracking (EAC) and irradiation promote that stress corrosion cracking (IASCC) is the most outstanding with SCC.
In order to alleviate and suppress the stress corrosion of pressurized-water reactor structured material, usually adopt the method to hydrogenation in primary Ioops refrigerant and zincification in the world.But the distribution of more dangerous, the wayward hydrogen of hydroprocessing in heap in primary Ioops refrigerant, cost is also higher, also easily causes the suction hydrogen-type corrosion of can material especially zirconium alloy; Zincification in primary Ioops refrigerant, needs to carry out dilution process to zinc, and cost is high and zinc likely can cause corrosion product at the surface deposition of zirconium alloy.In recent years; some research institution external carries out and in boiling-water reactor primary Ioops, add precious metal to suppress the research of the stress corrosion of structured material under hot shut down operating mode; because precious metal can at structured material surface coverage one deck noble metal nano particles protective layer; this just can make structured material show the electrochemical properties of precious metal; reduce structured material electrochemical corrosion potential; thus suppress stress corrosion cracking germinating and the cracking of structured material, but not openly the adding kind, add the parameter such as speed and position of precious metal.Also in pressurized-water reactor primary Ioops, do not add the open report adding precious metal especially online at present.Due to the temperature of water pressuring stacking operation, pressure and pH regulator, comparatively boiling-water reactor is more complicated, and the agent structure of pressurized-water reactor and boiling-water reactor differs greatly, so be badly in need of that development is a kind of adds precious metal to alleviate the method for structured material stress corrosion to pressurized-water reactor primary Ioops.
Summary of the invention
(1) goal of the invention
Problem existing for prior art, the invention provides a kind of alleviate pressurized-water reactor primary Ioops structured material surface electrochemical corrosion potential, improve structured material stress corrosion resistant ability and the method in extending structure materials'use life-span.
(2) technical scheme
For solving the problem existing for prior art, the present invention is achieved by the following technical solutions:
Alleviate a method for pressurized-water reactor primary Ioops structured material stress corrosion, the method is:
In the refrigerant of pressurized-water reactor primary Ioops, add precious metal salt solution, wherein the concentration range of precious metal salt solution in refrigerant is 10-1000 μ g/kg, and injection rate is 1 ~ 100 μ g/ days; Described precious metal salt solution is independent salts solution or the mixing salt solution of the two of Pt, Rh.
Preferably, precious metal salt solution adds with step in such a way:
1) under hot shut down operating mode, in pressurized-water reactor primary Ioops refrigerant, precious metal salt solution is added; Then under heap accidental conditions, one or more electrochemical test system is used to monitor the electrochemical corrosion potential of pressurized-water reactor primary Ioops, when arbitrary electrochemical corrosion potential of monitoring is greater than-300mV (standard hydrogen electrode current potential), again continue to add precious metal salt solution; Described precious metal salt solution is independent salts solution or the mixing salt solution of the two of Pt, Rh.
2), after pressurized-water reactor primary Ioops electrochemical corrosion potential to be monitored all drops to-400mV (standard hydrogen electrode current potential), stop injecting precious metal salt solution;
3) when arbitrary electrochemical corrosion potential of monitoring raises 10mV (standard hydrogen electrode current potential), add precious metal salt solution and drop to below-400mV to electrochemical corrosion potential;
4) repeating step 2,3, makes electrochemical corrosion potential drop to below-400mV (standard hydrogen electrode current potential).
Preferably, electrochemical test system is positioned at charging system, reactor core, main pipeline place and main steam generators sewage draining exit place.
Preferably, when precious metal salt solution is the mixing solutions of Pt, Rh, the ratio of Pt and Rh is 1:1 ~ 1:10.
Preferably, the concentration range of precious metal salt solution in refrigerant is 200 μ g/kg, and injection rate is 20 μ g/ days.
Preferably, the salts solution of described Pt, Rh is respectively hexahydroxy-sodium platinate solution and hexahydroxy-rhodium acid sodium solution.
Preferably, described precious metal salt solution is added by upper charging system or independent injected system.
Preferably, described independent injected system comprises precious metal salt solution storage tank, high precision micrometering pump, recycle pump.
Preferably, electrochemical test system mainly comprises electrochemical workstation, working electrode, Cu/CuO reference electrode and Pt sheet supporting electrode.
(3) beneficial effect
Method provided by the invention in pressurized-water reactor primary Ioops refrigerant, adds the independent salts solution of Pt, Rh or the mixing salt solution of the two to alleviate the stress corrosion of structured material, avoid traditional hydrogenation and zincification operates the drawback brought, also the problem adding precious metal salt solution is online solved, effectively can reduce the electrochemical corrosion potential on structured material surface, improve structured material stress corrosion resistant ability, the work-ing life of extending structure material under High Temperature High Pressure water surrounding, thus improve economy and the security of high-temperature high pressure water system cloud gray model.Specific explanations is:
(1) the method not only can add precious metal salt solution under hot shut down operating mode, also can add precious metal salt solution when piling normal operation.When heap normally runs, take electrochemical corrosion potential as the stress corrosion situation according to judging primary Ioops agent structure material, thus determine the add-on of suitable precious metal salt solution further.
Because the electrochemical corrosion potential of pressurized-water reactor structured material (ECP) is in+100 ~+300mV (SHE, standard hydrogen electrode), be easy to stress corrosion crack occurs; As ECP<-230mV (SHE), then effectively can suppress the initiation and propogation of structured material stress corrosion cracking.The method provided in the application is proof stress corrosion potential (standard hydrogen electrode current potential) below-400mV, effectively can suppress germinating and the development of gentle solution structure material stress corrosion.
(2) controlling the concentration range of this precious metal salt solution in refrigerant is 10-1000 μ g/kg, and injection rate is 1 ~ 100 μ g/ days, significantly can reduce the stress corrosion current potential of agent structure material.But the concentration of precious metal salt solution and add speed can not be excessive, because precious metal salt solution concentration is greater than 1000 μ g/kg, refrigerant partial water chemical property heterogeneity can be caused, cause the significantly variation of pH, accelerated corrosion, thus affect precious metal add effect; Add speed and be greater than 100 μ g/ days, the skewness of precious metal salt solution in refrigerant can be made.
(3) coal addition position of precious metal salt solution can be upper charging system or the injection of independent injected system of pressurized-water reactor primary Ioops.Because pressurized-water reactor particularly Nuclear power plants will add plurality of reagents by the upper charging system of primary Ioops, upper charging system is very complicated and stability is low.Add precious metal salt solution by designing independently injected system, this add system more stable, simple and there is accident time be easy to investigation.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1
Alleviate a method for pressurized-water reactor primary Ioops structured material stress corrosion, the method is:
(1) under pressurized-water reactor hot shut down operating mode, micrometering pump is utilized to add hexahydroxy-sodium platinate (Na by the upper charging system of its primary Ioops
2pt (OH)
6) solution, and respectively electrochemical monitoring system monitoring electrochemical corrosion potential is set at upper charging system, reactor core, the cold leg place of main pipeline and main steam generators sewage draining exit place; When heap normally runs, if arbitrary electrochemical corrosion potential of monitoring is greater than-300mV (standard hydrogen electrode current potential), again continue to add precious metal salt solution; Wherein electrochemical test system mainly comprises electrochemical workstation, working electrode, Cu/CuO reference electrode and Pt sheet supporting electrode, and working electrode is the agent structure material of monitoring itself.
2), after electrochemical corrosion potential to be monitored all drops to-400mV (standard hydrogen electrode current potential), stop injecting hexahydroxy-sodium platinate (Na
2pt (OH)
6) solution;
3) when arbitrary electrochemical corrosion potential of monitoring raises 10mV (standard hydrogen electrode current potential), interval adds hexahydroxy-sodium platinate and drops to below-400mV to electrochemical corrosion potential;
4) repeating step 2,3, makes electrochemical corrosion potential drop to below-400mV (standard hydrogen electrode current potential).
Make the concentration range of precious metal salt solution in refrigerant be 10 μ g/kg by above-mentioned steps, injection rate is 1 μ g/ days.
Making each electrochemical corrosion potential of primary Ioops be less than-230mV by adding hexahydroxy-sodium platinate solution in refrigerant, illustrating that this method has unusual effect to relieve stresses corrosion.
Embodiment 2
As different from Example 1, add precious metal salt solution by independent injected system, and precious metal salt solution is hexahydroxy-rhodium acid sodium solution (Na
2rh (OH)
6).The concentration range of precious metal salt solution in refrigerant is 200 μ g/kg, and injection rate is 20 μ g/ days.
Described independent injected system comprises precious metal salt solution storage tank, micrometering pump, recycle pump and corresponding pipeline and valve.
Embodiment 3
As different from Example 1, the precious metal salt solution added is ratio is the hexahydroxy-rhodium acid sodium solution of 1:1 and the mixing solutions of hexahydroxy-sodium platinate solution.The concentration range of precious metal salt solution in refrigerant is 500 μ g/kg, and injection rate is 50 μ g/ days.
Embodiment 4
As different from Example 1, the precious metal salt solution added is ratio is the hexahydroxy-rhodium acid sodium solution of 1:5 and the mixing solutions of hexahydroxy-sodium platinate solution.The concentration range of precious metal salt solution in refrigerant is 1000 μ g/kg, and injection rate is 100 μ g/ days.
Embodiment 5
As different from Example 1, the precious metal salt solution added is ratio is the hexahydroxy-rhodium acid sodium solution of 1:10 and the mixing solutions of hexahydroxy-sodium platinate solution.
Claims (9)
1. alleviate the method for pressurized-water reactor primary Ioops structured material stress corrosion for one kind, it is characterized in that, the method adds precious metal salt solution in the refrigerant of pressurized-water reactor primary Ioops, and wherein the concentration range of precious metal salt solution in refrigerant is 10-1000 μ g/kg, and injection rate is 1 ~ 100 μ g/ days; Described precious metal salt solution is independent salts solution or the mixing salt solution of the two of Pt, Rh.
2. a kind of method alleviating the stress corrosion of pressurized-water reactor primary Ioops structured material according to claim 1, it is characterized in that, precious metal salt solution adds with step in such a way:
1) under hot shut down operating mode, in pressurized-water reactor primary Ioops refrigerant, precious metal salt solution is added; Then under heap accidental conditions, one or more electrochemical test system is used to monitor the electrochemical corrosion potential of pressurized-water reactor primary Ioops, when arbitrary electrochemical corrosion potential of monitoring is greater than-300mV (standard hydrogen electrode current potential), again continue to add precious metal salt solution; Described precious metal salt solution is independent salts solution or the mixing salt solution of the two of Pt, Rh;
2), after pressurized-water reactor primary Ioops electrochemical corrosion potential to be monitored all drops to-400mV (standard hydrogen electrode current potential), stop injecting precious metal salt solution;
3) when arbitrary electrochemical corrosion potential of monitoring raises 10mV (standard hydrogen electrode current potential), add precious metal salt solution and drop to below-400mV to electrochemical corrosion potential;
4) repeating step 2,3, makes electrochemical corrosion potential drop to below-400mV (standard hydrogen electrode current potential).
3. a kind of method alleviating the stress corrosion of pressurized-water reactor primary Ioops structured material according to claim 2, it is characterized in that, the electrochemical test system described in step (1) is positioned at charging system, reactor core, main pipeline place and main steam generators sewage draining exit place.
4. a kind of method alleviating the stress corrosion of pressurized-water reactor primary Ioops structured material according to claim 1 and 2, is characterized in that, when precious metal salt solution is the mixing solutions of Pt, Rh, the ratio of Pt and Rh is 1:1 ~ 1:10.
5. a kind of method alleviating the stress corrosion of pressurized-water reactor primary Ioops structured material according to claim 1, is characterized in that, the concentration of precious metal salt solution in refrigerant is 200 μ g/kg, and injection rate is 20 μ g/ days.
6. a kind of method alleviating the stress corrosion of pressurized-water reactor primary Ioops structured material according to claim 1 and 2, is characterized in that, the salts solution of described Pt, Rh is respectively hexahydroxy-sodium platinate solution and hexahydroxy-rhodium acid sodium solution.
7. a kind of method alleviating the stress corrosion of pressurized-water reactor primary Ioops structured material according to claim 2, it is characterized in that, described in step (1), precious metal salt solution is added by upper charging system or independent injected system.
8. a kind of method alleviating the stress corrosion of pressurized-water reactor primary Ioops structured material according to claim 7, it is characterized in that, described independent injected system comprises precious metal salt solution storage tank, high precision micrometering pump, recycle pump.
9. a kind of method alleviating the stress corrosion of pressurized-water reactor primary Ioops structured material according to claim 2, is characterized in that, described electrochemical test system mainly comprises electrochemical workstation, working electrode, Cu/CuO reference electrode and Pt sheet supporting electrode.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0671486A1 (en) * | 1994-03-10 | 1995-09-13 | General Electric Company | Noble metal doping or coating of crack interior for stress corrosion cracking protection of metals |
| KR20080077505A (en) * | 2007-02-20 | 2008-08-25 | 한국원자력연구원 | Method for surface treatment of pwr piping materials by platinum powder doping |
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2014
- 2014-12-04 CN CN201410730122.6A patent/CN104593778B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0671486A1 (en) * | 1994-03-10 | 1995-09-13 | General Electric Company | Noble metal doping or coating of crack interior for stress corrosion cracking protection of metals |
| KR20080077505A (en) * | 2007-02-20 | 2008-08-25 | 한국원자력연구원 | Method for surface treatment of pwr piping materials by platinum powder doping |
Non-Patent Citations (2)
| Title |
|---|
| 海正银等: "压水堆一回路添加Pt技术研究", 《中国原子能科学研究院年报》 * |
| 海正银等: "模拟压水堆一回路条件添加Pt技术研究", 《中国腐蚀与防护学报》 * |
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