CN104593778B - 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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- CN104593778B CN104593778B CN201410730122.6A CN201410730122A CN104593778B CN 104593778 B CN104593778 B CN 104593778B CN 201410730122 A CN201410730122 A CN 201410730122A CN 104593778 B CN104593778 B CN 104593778B
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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 is and in particular to a kind of alleviate presurized water reactor primary Ioops structure
The method of material stress corrosion.
Background technology
The material that nuclear power plant reactor critical component adopts mainly includes nickel-base alloy, low-alloy steel, rustless steel and zirconium and closes
Gold etc..But the material selected also has different with heap-type difference, and in such as presurized water reactor, nickel-base alloy heat-transfer pipe accounts for primary Ioops
The 75% about of surface area, and boiling-water reactor key part structure material is mainly rustless steel and low-alloy steel.These materials are in height
Under the harshness running environment such as temperature, high pressure, high irradiation, the corrosion damage of various ways can be produced, including stress-corrosion cracking
(SCC), corrosion fatigue (CF), intercrystalline corrosion, spot corrosion, abrasion, flowing accelerated corrosion (FAC) etc., the ring wherein with SCC as representative
Border promotes cracking (EAC) and irradiation to promote stress-corrosion cracking (IASCC) the most prominent.
In order to alleviate and suppressing the stress corrosion of presurized water reactor structural material, in the world generally using in primary Ioops coolant
Hydrogenation and the method for zincification.But in primary Ioops coolant hydroprocessing than relatively hazardous, wayward hydrogen in heap point
Cloth, cost is also higher, is also easy to cause the suction hydrogen-type corrosion of cladding materials especially zircaloy；Add in primary Ioops coolant
Zinc, needs zinc is carried out dilution process, high cost and zinc is possible to cause corrosion product to deposit on the surface of zircaloy.Closely
Nian Lai, some research institutions development abroad adds noble metal to suppress structural wood under hot shutdown operating mode in boiling-water reactor primary Ioops
The research of the stress corrosion of material, because noble metal can cover one layer of noble metal nano particles protective layer on structural material surface,
This just can make structural material show the electrochemical properties of noble metal, reduces structural material electrochemical corrosion potential, thus suppressing
The stress corrosion cracking (SCC) germinating of structural material and cracking, but the addition species of not open noble metal, addition speed and position
The parameter such as put.There is presently no and add the open report especially adding noble metal online in presurized water reactor primary Ioops.Due to pressure
Temperature, pressure and pH regulator that water-water reactor runs are more complicated compared with boiling-water reactor, and the agent structure difference of presurized water reactor and boiling-water reactor
Larger, so urgent need development is a kind of adds the method to alleviate structural material stress corrosion for the noble metal to presurized water reactor primary Ioops.
Content of the invention
(1) goal of the invention
According to the problems of prior art, the invention provides one kind can alleviate presurized water reactor primary Ioops structural material table
The electrochemical corrosion potential in face, raising structural material stress corrosion resistant ability the method in extending structure materials'use life-span.
(2) technical scheme
For solving the problems of prior art, the present invention is achieved by the following technical solutions：
A kind of method alleviating presurized water reactor primary Ioops structural material stress corrosion, the method is：
Add precious metal salt solution into the coolant of presurized water reactor primary Ioops, wherein precious metal salt solution is in coolant
Concentration range is 10-1000 μ g/kg, and injection rate is 1～100 μ g/ days；Described precious metal salt solution is that the independent salt of Pt, Rh is molten
Liquid or the mixing salt solution of the two.
Preferably, precious metal salt solution is to add with step in such a way：
1) under hot shutdown operating mode, add precious metal salt solution in presurized water reactor primary Ioops coolant；Then normal in heap
Under operating condition, monitor the electrochemical corrosion potential of presurized water reactor primary Ioops using one or more electrochemical test system, work as prison
The arbitrary electrochemical corrosion potential surveyed is more than -300mV (standard hydrogen electrode current potential), is continuously added into precious metal salt solution again；Institute
State the independent saline solution that precious metal salt solution is Pt, Rh or the mixing salt solution of the two.
2) after presurized water reactor primary Ioops electrochemical corrosion potential to be monitored all drops to -400mV (standard hydrogen electrode current potential),
Stop injection precious metal salt solution；
3) when arbitrary electrochemical corrosion potential of monitoring raises 10mV (standard hydrogen electrode current potential), add precious metal salt molten
Liquid drops to below -400mV to electrochemical corrosion potential；
4) repeat step 2,3, make electrochemical corrosion potential drop to below -400mV (standard hydrogen electrode current potential).
Preferably, electrochemical test system be located at upper charging system, reactor core, at main pipeline and main steam generators sewage draining exit
Place.
Preferably, when the mixed solution for Pt, Rh for the precious metal salt solution, the ratio of Pt and Rh is 1:1～1:10.
Preferably, concentration range in coolant for the precious metal salt solution is 200 μ g/kg, and injection rate is 20 μ g/ days.
Preferably, the saline solution of described Pt, Rh is respectively hexahydroxy platinic acid sodium solution and hexahydroxy rhodium acid sodium solution.
Preferably, described precious metal salt solution is to be added by upper charging system or independent injected system.
Preferably, described independent injected system includes precious metal salt solution storage tank, high accuracy micrometering pump, circulating pump.
Preferably, electrochemical test system mainly includes electrochemical workstation, working electrode, Cu/CuO reference electrode and Pt
Piece auxiliary electrode.
(3) beneficial effect
The method that the present invention provides be add in presurized water reactor primary Ioops coolant the independent saline solution of Pt, Rh or the two
The stress corrosion to alleviate structural material for the mixing salt solution, it is to avoid the drawbacks of traditional hydrogenation and zincification operation bring,
Solve the problems, such as to add precious metal salt solution online, can effectively reduce the electrochemical corrosion potential on structural material surface, carry
High structural material stress corrosion resistant ability, service life under High Temperature High Pressure water environment for the extending structure material, thus improve
The economy of high-temperature high pressure water system operation and safety.Specific explanations are：
(1) the method not only can add precious metal salt solution it is also possible to when heap normally runs under hot shutdown operating mode
Add precious metal salt solution.When heap normally runs, it is that foundation to judge primary Ioops agent structure material with electrochemical corrosion potential
The stress corrosion situation of material, thus further determine that the addition of suitable precious metal salt solution.
Because the electrochemical corrosion potential (ECP) of presurized water reactor structural material is in+100～+300mV (SHE, standard hydrogen electricity
Pole) it is easy to there is stress corrosion cracking；Work as ECP<During -230mV (SHE), then can effectively suppress structural material stress corrosion cracking
The germinating of stricture of vagina and extension.Method provided herein is proof stress corrosion potential (standard hydrogen electrode electricity below -400mV
Position), can effectively suppress germinating and the development of gentle solution structure material stress corrosion.
(2) control concentration range in coolant for this precious metal salt solution be 10-1000 μ g/kg, injection rate be 1～
100 μ g/ days, can significantly reduce the stress corrosion current potential of agent structure material.But the concentration of precious metal salt solution and addition speed
Spend nor excessive, because precious metal salt solution concentration is more than 1000 μ g/kg, coolant local water chemistry property can be led to uneven
One, cause the significantly variation of pH, accelerated corrosion, thus affecting the addition effect of noble metal；Speed is added to be more than 100 μ g/ days, meeting
Make skewness in coolant for the precious metal salt solution.
(3) coal addition position of precious metal salt solution can be upper charging system or the independent injected system note of presurized water reactor primary Ioops
Enter.Because the upper charging system that presurized water reactor particularly nuclear power station will pass through primary Ioops adds plurality of reagents, upper charging system is extremely complex
And stability is low.Add precious metal salt solution by designing independent injected system, this addition system is more stable, simple and goes out
It is easy to during existing accident investigate.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1
A kind of method alleviating presurized water reactor primary Ioops structural material stress corrosion, the method is：
(1) the upper charging system that micrometering pump passes through its primary Ioops is utilized to add hexahydroxy platinum under presurized water reactor hot shutdown operating mode
Sour sodium (Na2Pt(OH)6) solution, and respectively at upper charging system, reactor core, the cold lower limb of main pipeline and main steam generators sewage draining exit
Place's setting electrochemical monitoring system monitoring electrochemical corrosion potential；When heap normally runs, if arbitrary electrochemical corrosion of monitoring
Current potential is more than -300mV (standard hydrogen electrode current potential), is continuously added into precious metal salt solution again；Wherein electrochemical test system master
Electrochemical workstation to be included, working electrode, Cu/CuO reference electrode and Pt piece auxiliary electrode, working electrode is the master of monitoring
Body structural material itself.
2), after electrochemical corrosion potential to be monitored all drops to -400mV (standard hydrogen electrode current potential), injection six hydroxyls are stopped
Base sodium platinate (Na2Pt(OH)6) solution；
3) when arbitrary electrochemical corrosion potential of monitoring raises 10mV (standard hydrogen electrode current potential), it is intermittently added hexahydroxy platinum
Sour sodium drops to below -400mV to electrochemical corrosion potential；
4) repeat step 2,3, make electrochemical corrosion potential drop to below -400mV (standard hydrogen electrode current potential).
Making concentration range in coolant for the precious metal salt solution by above-mentioned steps is 10 μ g/kg, and injection rate is 1 μ
G/ days.
By in coolant add hexahydroxy platinic acid sodium solution make each electrochemical corrosion potential of primary Ioops be less than-
230mV, illustrates that this method has remarkable result to alleviating stress corrosion.
Embodiment 2
As different from Example 1, precious metal salt solution is added by independent injected system, and precious metal salt solution is six
Hydroxyl rhodium acid sodium solution (Na2Rh(OH)6).Concentration range in coolant for the precious metal salt solution is 200 μ g/kg, and injection rate is
20 μ g/ days.
Described independent injected system include precious metal salt solution storage tank, micrometering pump, circulating pump and corresponding pipeline and
Valve.
Embodiment 3
As different from Example 1, the precious metal salt solution of addition is 1 for ratio:1 hexahydroxy rhodium acid sodium solution and six
The mixed solution of hydroxyl platinic acid sodium solution.Concentration range in coolant for the precious metal salt solution 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 of addition is 1 for ratio:5 hexahydroxy rhodium acid sodium solution and six
The mixed solution of hydroxyl platinic acid sodium solution.Concentration range in coolant for the precious metal salt solution 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 of addition is 1 for ratio:10 hexahydroxy rhodium acid sodium solution and
The mixed solution of hexahydroxy platinic acid sodium solution.
Claims (8)
1. a kind of method alleviating presurized water reactor primary Ioops structural material stress corrosion is it is characterised in that the method is to presurized water reactor
Precious metal salt solution is added, wherein concentration range in coolant for the precious metal salt solution is 10- in the coolant of primary Ioops
1000 μ g/kg, injection rate is 1～100 μ g/ days；Described precious metal salt solution is independent saline solution or the mixing of the two of Pt, Rh
Saline solution；
Described precious metal salt solution is to add with step in such a way：
1) under hot shutdown operating mode, add precious metal salt solution in presurized water reactor primary Ioops coolant；Then normally run in heap
Under operating mode, monitor the electrochemical corrosion potential of presurized water reactor primary Ioops using one or more electrochemical test system, when monitoring
Arbitrary electrochemical corrosion potential is more than -300mV, is continuously added into precious metal salt solution again；Described precious metal salt solution is Pt, Rh
Independent saline solution or the mixing salt solution of the two；
2), after presurized water reactor primary Ioops electrochemical corrosion potential to be monitored all drops to -400mV, stop injection precious metal salt molten
Liquid；
3) when arbitrary electrochemical corrosion potential of monitoring raises 10mV, add precious metal salt solution to electrochemical corrosion potential
It is down to below -400mV；
4) repeat step 2), 3), make electrochemical corrosion potential drop to below -400mV；
Described electrochemical corrosion potential refers to the current potential with respect to standard hydrogen electrode current potential.
2. a kind of method alleviating presurized water reactor primary Ioops structural material stress corrosion according to claim 1, its feature exists
In the electrochemical test system described in step (1) at upper charging system, reactor core, main pipeline and arrange by main steam generators
At dirty mouth.
3. a kind of method alleviating presurized water reactor primary Ioops structural material stress corrosion according to claim 1, its feature exists
In when the mixed solution for Pt, Rh for the precious metal salt solution, the ratio of Pt and Rh is 1:1～1:10.
4. a kind of method alleviating presurized water reactor primary Ioops structural material stress corrosion according to claim 1, its feature exists
In concentration in coolant for the precious metal salt solution is 200 μ g/kg, and injection rate is 20 μ g/ days.
5. a kind of method alleviating presurized water reactor primary Ioops structural material stress corrosion according to claim 1, its feature exists
In the saline solution of described Pt, Rh is respectively hexahydroxy platinic acid sodium solution and hexahydroxy rhodium acid sodium solution.
6. a kind of method alleviating presurized water reactor primary Ioops structural material stress corrosion according to claim 1, its feature exists
In precious metal salt solution described in step (1) is to be added by upper charging system or independent injected system.
7. a kind of method alleviating presurized water reactor primary Ioops structural material stress corrosion according to claim 6, its feature exists
In described independent injected system includes precious metal salt solution storage tank, high accuracy micrometering pump, circulating pump.
8. a kind of method alleviating presurized water reactor primary Ioops structural material stress corrosion according to claim 1, its feature exists
In described electrochemical test system mainly includes electrochemical workstation, working electrode, Cu/CuO reference electrode and Pt piece auxiliary
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 |
-
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 |
|---|
| 压水堆一回路添加Pt技术研究;海正银等;《中国原子能科学研究院年报》;20140630;第150-151页 * |
| 模拟压水堆一回路条件添加Pt技术研究;海正银等;《中国腐蚀与防护学报》;20140630;第34卷(第3期);第253-256页 * |
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