CN110306177A - Chemical technology for the primary Ioops system passivation during the pre- marginal test of nuclear power plant - Google Patents
Chemical technology for the primary Ioops system passivation during the pre- marginal test of nuclear power plant Download PDFInfo
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- CN110306177A CN110306177A CN201910422862.6A CN201910422862A CN110306177A CN 110306177 A CN110306177 A CN 110306177A CN 201910422862 A CN201910422862 A CN 201910422862A CN 110306177 A CN110306177 A CN 110306177A
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- chemical technology
- nuclear power
- marginal test
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- primary ioops
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/77—Controlling or regulating of the coating process
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention relates to a kind of chemical technologies of the primary Ioops system passivation during pre- marginal test for nuclear power plant, comprising: during the pre- marginal test carried out after initial load nuclear fuel in core reactor core, Zn is added into coolant2+, make Zn2+The metal surface in primary Ioops system is contacted during pre- marginal test to form initial film containing zinc oxide.The present invention is by adding zinc to coolant during the pre- marginal test of new nuclear power unit, zinc is set to contact the metal surface in primary Ioops system during pre- marginal test, and initial film containing zinc oxide is formed on the metal surface, the implementation of new nuclear power unit note zinc passivation improves the reliability of passivating film, ensure to run in the phase in longevity in nuclear power and provides good protection for primary Ioops metal parts, ensure the operation of nuclear power unit long time stability, it is significantly reduced the total amount that the corrosion product of activation can be deposited on fuel and become during normal power operation simultaneously, so as to improve fuel performance and reduce power plant's dosage rate to the greatest extent.
Description
Technical field
The present invention relates to the primary Ioops systems during technical field of nuclear power more particularly to a kind of pre- marginal test for nuclear power plant
The chemical technology of system passivation.
Background technique
Nuclear power plant's generally road system once, it includes reactor vessel, steam generator, reactor coolant pump, steady
Depressor and connecting pipe.Reactor coolant circuit includes that reactor coolant pump, steam generator are connected with by these components
To the pipeline of reactor vessel.Nuclear power plant can there are two, the circuits of three or four reactor coolants.Nuclear fuel is included in
In reactor core, it is accommodated in reactor vessel.One function of primary Ioops system is to be transferred to heat from nuclear fuel
Steam generator.
In order to make primary Ioops system execute its function, coolant is recycled by primary Ioops system.Coolant is contacted
System material and surface will be subjected to certain corrosion.The production for the protective oxide film being passivated on primary side metal surface
It is raw to be important for the corrosion of control material and component and for the release of control corrosion rate product during power plant's operation.With
Metal erosion will generate metal oxide.Part of the metal oxide forms adhesion layer, rest part quilt on a side surface
It is discharged into cooling water.As adhesiveness oxide skin(coating), it can become increasingly to be passivated, and slow down the corrosion with metal surface
Reaction, final corrosion reaction are reduced to low steady-state value.
Primary Ioops system in pressurized water reactor (PWR) is reactor coolant loop (RCP).In power plant's runtime
Between, when the structural material in RCP is exposed to the reactor coolant of high temperature, corrosion occurs and forms deposition.These corrosion products
It is then released into reactor coolant, and is deposited on the fuel in reactor core.Resistant material can be passed through in the past
Selection and Chemical Control additive and power plant's operative practice development, to reduce the formation of corrosion and heavy to the maximum extent
Product.During the operation of normal power plant, Chemical Control can be used for the passivating film on primary Ioops system material surface to control power plant
Corrosion rate during operation and corrosion rate of release, to reduce dirt deposits of the corrosion product on fuel and subsequent to the greatest extent
Activation.For reducing the risk of relevant to dirt fuel performance problem and power plant's dosage rate to the greatest extent, this is necessary.Presurized water reactor
The passivation of nuclear power unit primary Ioops is the temperature and chemical index by adjusting medium in primary Ioops system, holds the pressure of primary Ioops
The metal surface that device, main pipeline, in-pile component etc. are contacted with coolant generates passivating film.Nuclear power after passivating film loads nuclear fuel
The normal operation of unit is extremely important, can play the role of inhibiting, slow down metal erosion and reducing radioimpurity radioactive impurity generation.In core
The passivating film that motor group primary Ioops surface is formed is mainly FeFe2O4、NiFe2O4、FeCr2O4, Cr-O or in which a part it is mixed
It is combined into, primary Ioops corrosion of metal and radioactive substance after this layer of fine and close passivating film can prevent nuclear power unit from operating normally
Deposition, but as nuclear power runing time lengthens (longest can be postponed until 60 years operation phases in longevity), by being passivated this to be formed layer naturally
Passivating film weakens there may be protecting effect or insufficient risk.
In the commercialized running of nuclear power plant, there is experience to show to inject zinc in primary Ioops system at present, with zinc injection one
Circuit system, existing corrosive film oxide becomes more stable and more protectiveness on surface, can inhibit whole drawn game
The corrosion in portion.The PWR that the overwhelming majority executes zinc injection were mature power plant, at operation (such as 15 to 20 years enough for a long time
Start the process afterwards).They inject zinc during Power operation at normal working temperature.Therefore, in these mature electricity
In factory, since lasting power plant runs, existing oxidation film is own to be formed and establishes on the metal surface.In existing oxide
There are nickel and cobalt atom in film, reinject zinc for reconstructing existing oxidation film.Restructuring procedure can continue many a fuel
Circulation, until the existing oxidation film of reconstruct has the zinc and chromium of high concentration near metal oxide interface.Due to zinc atom
Existing oxidation film is included in for replacing or substituting other atoms, such as nickel and cobalt atom, injects zinc in the nuclear power plant of operation
The corrosion product of ion or dissolution can be caused additionally to be discharged into coolant.These additional corrosion products are discharged into coolant
Can be improved the release of the corrosion product recycled in primary Ioops system, increase the amount that can be deposited on fuel, thus potentially for
The performance issue of fuel increases risk.
Summary of the invention
The object of the present invention is to provide a kind of chemistry of the primary Ioops system passivation during pre- marginal test for nuclear power plant
Technique, the passivating film for solving to be formed according to existing natural passivating method in the prior art is within the phase in longevity that nuclear power unit is up to 60 years
There are problems that the rough sledding of protecting effect decrease and mature nuclear power unit note zinc band of passivation carry out potential fuel performance and cause to increase
Add the problem of risk etc..
The technical proposal for solving the technical problem of the invention is: one during a kind of pre- marginal test for nuclear power plant
The chemical technology of circuit system passivation, comprising: during the pre- marginal test carried out after initial load nuclear fuel in core reactor core, to
Zn is added in reactor coolant2+, make Zn2+The metal surface in primary Ioops system is contacted during pre- marginal test to be formed
Initial film containing zinc oxide.
Zn in chemical technology of the invention, in reactor coolant2+Concentration be 5-15ppb.
In chemical technology of the invention, Zn is added into reactor coolant2+Mode be to be added in a manner of zinc acetate
Add.
In chemical technology of the invention, start to add Zn into reactor coolant2+Temperature be the pre- marginal test phase
Between temperature >=260 DEG C when start add Zn2+。
In chemical technology of the invention, alkali is also added in reactor coolant.
In chemical technology of the invention, the alkali is lithium hydroxide or sodium hydroxide.
In chemical technology of the invention, the alkali is lithium hydroxide, Li+Concentration in reactor coolant maintains
3ppm-4ppm。
In chemical technology of the invention, alkali and Zn are added in reactor coolant2+Before further include: cold in reactor
But also add hydrazine in agent so that the dissolved oxygen in reactor coolant concentration≤100ppb.
In chemical technology of the invention, during the temperature that hydrazine is added in reactor coolant is pre- marginal test
Hydrazine is added when temperature≤120 DEG C.
In chemical technology of the invention, during the temperature that hydrazine is added in reactor coolant is pre- marginal test
Hydrazine is added when temperature is between 90 DEG C~110 DEG C.
Implement the chemical technology for the primary Ioops system passivation during the pre- marginal test of nuclear power plant of the invention, have with
Down the utility model has the advantages that the present invention makes zinc in pre- critical examination by adding zinc to coolant during the pre- marginal test of new nuclear power unit
Metal surface during testing in contact primary Ioops system, and initial film containing zinc oxide, new nuclear power are formed on the metal surface
The implementation of unit note zinc passivation improves the reliability of passivating film, it is ensured that mentions within the nuclear power operation phase in longevity for primary Ioops metal parts
For good protection, it is ensured that the operation of nuclear power unit long time stability, while being significantly reduced in the normal power runtime
Between can be deposited on fuel and become activation corrosion product total amount, so as to improve fuel performance and reduce power plant to the greatest extent
Dosage rate.
Specific embodiment
Below with reference to embodiment, to the change for the primary Ioops system passivation during the pre- marginal test of nuclear power plant of the invention
Technique is learned to be described further:
Abbreviation and Key Term definition:
Compacted clay liners: compacted clay liners are exactly a kind of reactor that nuclear fuel is cooled down using high pressure water,
Its working principle is that: the primary Ioops cooling water of 120~160 atmospheric pressure is sent into reactor core by reactor coolant pump, nuclear fuel
The thermal energy of releasing takes reactor core out of, then enters steam generator, imparts heat to secondary circuit water by heat-transfer pipe, makes its boiling simultaneously
Generate steam；The decline of primary Ioops cooling water temperature completes primary Ioops water circulation into reactor core；The high steam that secondary circuit generates
Pushing turbine power generation enters steam generator using condenser and preheater, completes secondary circuit water circulation；
Primary Ioops: also known as primary heat transport system or reactor coolant loop, are a closed circulatory system, major function
It is the nuclear fuel and coolant for containing nuclear power unit, mainly by pressure vessel, main pipeline, voltage-stablizer, steam generator and anti-
Reactor coolant pump is answered to constitute
Reactor coolant: for providing reactor cooling medium in primary Ioops, this medium is generally clear water, wherein
It is added to the chemical additives such as boric acid, lithium hydroxide.
Reactor coolant pump: for driving coolant in primary Ioops, circulation power is provided, it is ensured that coolant can press
It is recycled between force container and steam generator；
Pre- marginal test: refer to the general name for the starting test that nuclear power station carries out after loading nuclear fuel for the first time, mainly include
With the starting and correlation test for being related to primary Ioops and its auxiliary system, main purpose is done for the initial criticality of subsequent nuclear reactor
Prepare.Wherein, during pre- marginal test it is that the process of heap is piled up in reaction, and from normal temperature and pressure to the process of high temperature and pressure.
It is protected since the passivating film formed according to existing natural passivating method exists within the phase in longevity that nuclear power unit is up to 60 years
The rough sledding of decreased effectiveness is protected, and mature nuclear power unit note zinc band of passivation carrys out potential fuel performance problem and increases risk.This
Invention proposes to make zinc contact the metal in primary Ioops system to coolant addition zinc during the pre- marginal test of new nuclear power unit
Surface, and initial film containing zinc oxide is formed on the metal surface.The implementation of new nuclear power unit note zinc passivation improves passivation
The reliability of film, it is ensured that provide good protection within the nuclear power operation phase in longevity for primary Ioops metal parts, it is ensured that nuclear power unit
The operation of long time stability.Therefore this technology has apparent compared to nature passivating method and mature unit note zinc passivating method
Advantage.
The present invention relates to the passivation of the primary Ioops system surfaces in nuclear power plant.During the pre- marginal test of new nuclear power unit
Develop passivating film in primary Ioops system surfaces.Passivating film helps to control in primary Ioops system surfaces during nuclear power plant runs
Corrosion and corrosion release, the preprocessing process can be carried out under the conditions of specified chemical time and temperature.
For ease of description, using the nuclear power with compacted clay liners and reactor coolant loop as primary Ioops system
Embodiments of the present invention are described for factory.It is austenite stainless in known compacted clay liners primary Ioops system main material
Steel, 690 alloys etc..Pre- critical duration, duration in each stage especially during pre- marginal test can be with
Change, and usually required for the various system tests to be executed time quantum determines.In addition, starting or terminating each stage
Temperature is exemplary, and the design based on specific power plant and operation can change.
Before pre- marginal test, reactor coolant loop is filled with the reactor coolant of boronic acid containing.Boric acid can be with
Neutron is absorbed, prevents neutron from excessively causing to fission.At this time or normal temperature and pressure state.
With the process of pre- marginal test, temperature can be gradually risen, and be added at≤120 DEG C to reactor coolant loop
Hydrazine oxygen scavenger, with the dissolved oxygen concentration in cleaning reaction reactor coolant.Hydrazine additive amount can change, and usually make in cooling
Dissolved oxygen concentration≤100ppb in agent.Wherein, ppb refers to part per billion, and ppb is equivalent to quality in the present invention
Volume ratio, unit are μ g/L, i.e., so that dissolved oxygen concentration≤100 μ g/L in coolant.Specifically, cooling to reactor
During agent system adds hydrazine oxygen scavenger, timing sampling carries out detection until dissolved oxygen concentration≤100 μ g/L, are added with determination
Add the dosage of hydrazine.
Hydrazine is added when preferably, between 90 DEG C~110 DEG C, adds the efficiency highest that hydrazine carries out deoxygenation at this time, i.e.,
It reacts most active, can save the reaction time, save cost.
After addition hydrazine and starting heating, at reactor coolant temperature >=260 DEG C, chemistry can be started and added
Add.This stage includes Zn2+Addition, wherein Zn2+Addition manner be to be added in a manner of zinc acetate, in other embodiments
It is also possible to by other to add in the form of containing zinc ion compound.Zn in reactor coolant2+Concentration be maintained at 5-
15ppb.Wherein, ppb refers to part per billion, and ppb is equivalent to mass volume ratio in the present invention, and unit is μ g/L,
Zn i.e. in reactor coolant2+Concentration be maintained at 5-15 μ g/L.
Furthermore it is possible to alkali is added into reactor coolant, such as lithium hydroxide, sodium hydroxide etc., to maintain alkaline pH,
For control corrosion rate and corrosion product rate of release.It is preferred that using lithium hydroxide, wherein Li+Concentration in reactor coolant
3ppm-4ppm is maintained, preferably about 3.5ppm or so.Wherein, ppm refers to part per million, in the present invention ppm
It is equivalent to mass volume ratio, unit is mg/L, i.e. Li+Concentration in reactor coolant maintains 3mg/L-4mg/L, preferably
It is about 3.5mg/L or so.
Since new power plant is with the new metal surface (maturation with the existing oxidation film with formation on the metal surface
It is opposite to run power plant), the zinc of significant quantity will be included in the oxidation film newly formed, then be formed in oxide lattice with less
The highly stable and protective oxide of defect.Less defect for reduce oxidation film electronics and ionic conductivity be
Effectively, which limit reaction is further corroded in metal oxide interface and at the oxide-solution interface, corrosion is produced
Object rate of release is lower, while reducing the surface that radioactive cobalt enters primary Ioops metal component.Technical application of the invention is arrived
The country can significantly improve the formation of nuclear power unit primary Ioops passivating film at present in the debugging stage for the pressurized-water reactor nuclear power plant built
Quality, it is ensured that the safe and stable operation of subsequent nuclear power unit has apparent economy and safe value.
The Chemical Control of pre- critical PCT present invention reactor coolant is needed to be improved in the art as preprocessing process,
With the normal power of nuclear power plant operation before be passivated the surface RCP, so as to control corrosion rate and optimization nuclear power plant system performance and
Long-term integrity.This will also can be deposited on fuel and become the corrosion product of activation during being substantially reducing at normal power operation
Total amount, so as to improve fuel performance and reduce power plant's dosage rate to the greatest extent.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description,
Within all these improvement or transformation should all belong to the protection domain of appended claims of the present invention.
Claims (10)
1. the chemical technology that the primary Ioops system during a kind of pre- marginal test for nuclear power plant is passivated characterized by comprising
During the pre- marginal test carried out after initial load nuclear fuel in core reactor core, Zn is added into reactor coolant2+, make Zn2+
The metal surface in primary Ioops system is contacted during pre- marginal test to form initial film containing zinc oxide.
2. chemical technology according to claim 1, which is characterized in that the Zn in reactor coolant2+Concentration be 5-
15ppb。
3. chemical technology according to claim 1, which is characterized in that add Zn into reactor coolant2+Mode be
It is added in a manner of zinc acetate.
4. chemical technology according to claim 1, which is characterized in that start to add Zn into reactor coolant2+Temperature
Degree be pre- marginal test during temperature >=260 DEG C when start add Zn2+。
5. chemical technology according to claim 1, which is characterized in that be also added with alkali in reactor coolant.
6. chemical technology according to claim 5, which is characterized in that the alkali is lithium hydroxide or sodium hydroxide.
7. chemical technology according to claim 6, which is characterized in that the alkali is lithium hydroxide, Li+It is cooling in reactor
Concentration in agent maintains 3ppm-4ppm.
8. chemical technology according to claim 5, which is characterized in that add alkali and Zn in reactor coolant2+Before
Further include: in reactor coolant also add hydrazine so that the dissolved oxygen in reactor coolant concentration≤100ppb.
9. chemical technology according to claim 8, which is characterized in that the temperature of addition hydrazine is in reactor coolant
Hydrazine is added when temperature≤120 DEG C during pre- marginal test.
10. chemical technology according to claim 9, which is characterized in that add the temperature of hydrazine in reactor coolant
Hydrazine is added when temperature during being pre- marginal test is between 90 DEG C~110 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112853339A (en) * | 2020-12-10 | 2021-05-28 | 中国辐射防护研究院 | Preparation method of corrosion oxide generated under AP1000 water chemistry working condition |
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| CN106574378A (en) * | 2014-07-30 | 2017-04-19 | 西屋电气有限责任公司 | Chemical process for primary system material passivation during hot functional testing of nuclear power plants |
| CN108137362A (en) * | 2015-11-12 | 2018-06-08 | 艺康美国股份有限公司 | Non phosphorous passivation agent and its purposes |
| EP3385405A1 (en) * | 2015-11-30 | 2018-10-10 | Baoshan Iron & Steel Co., Ltd. | Chromium-free surface-treated tinplate, production method and surface treating agent therefor |
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2019
- 2019-05-21 CN CN201910422862.6A patent/CN110306177A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106574378A (en) * | 2014-07-30 | 2017-04-19 | 西屋电气有限责任公司 | Chemical process for primary system material passivation during hot functional testing of nuclear power plants |
| CN108137362A (en) * | 2015-11-12 | 2018-06-08 | 艺康美国股份有限公司 | Non phosphorous passivation agent and its purposes |
| EP3385405A1 (en) * | 2015-11-30 | 2018-10-10 | Baoshan Iron & Steel Co., Ltd. | Chromium-free surface-treated tinplate, production method and surface treating agent therefor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112853339A (en) * | 2020-12-10 | 2021-05-28 | 中国辐射防护研究院 | Preparation method of corrosion oxide generated under AP1000 water chemistry working condition |
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Application publication date: 20191008 |