[go: up one dir, main page]

WO2019102768A1 - Procédé d'adhérence d'un métal noble à un élément en acier au carbone d'une centrale nucléaire et procédé de suppression de l'adhérence de radionucléides à un élément en acier au carbone d'une centrale nucléaire - Google Patents

Procédé d'adhérence d'un métal noble à un élément en acier au carbone d'une centrale nucléaire et procédé de suppression de l'adhérence de radionucléides à un élément en acier au carbone d'une centrale nucléaire Download PDF

Info

Publication number
WO2019102768A1
WO2019102768A1 PCT/JP2018/039314 JP2018039314W WO2019102768A1 WO 2019102768 A1 WO2019102768 A1 WO 2019102768A1 JP 2018039314 W JP2018039314 W JP 2018039314W WO 2019102768 A1 WO2019102768 A1 WO 2019102768A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon steel
steel member
nickel
pipe
film
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.)
Ceased
Application number
PCT/JP2018/039314
Other languages
English (en)
Japanese (ja)
Inventor
伊藤　剛
秀幸 細川
太田　信之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi GE Nuclear Energy Ltd
Original Assignee
Hitachi GE Nuclear Energy Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi GE Nuclear Energy Ltd filed Critical Hitachi GE Nuclear Energy Ltd
Publication of WO2019102768A1 publication Critical patent/WO2019102768A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21D—NUCLEAR POWER PLANT
    • G21D1/00—Details of nuclear power plant
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21D—NUCLEAR POWER PLANT
    • G21D3/00—Control of nuclear power plant
    • G21D3/08—Regulation of any parameters in the plant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin

Definitions

  • the present invention relates to a method of attaching noble metals to carbon steel members of a nuclear power plant (particularly a boiling water nuclear power plant) and a method of suppressing adhesion of radionuclides to carbon steel members of a nuclear power plant.
  • a nuclear power plant for example, a boiling water nuclear power plant (hereinafter referred to as a BWR plant) and a pressurized water nuclear power plant (hereinafter referred to as a PWR plant) are known.
  • a BWR plant steam generated in a reactor pressure vessel (referred to as a RPV) is directed to a turbine to rotate the turbine.
  • the steam discharged from the turbine is condensed by the condenser into water.
  • This water is supplied to the RPV through the water supply pipe as the water supply.
  • metal impurities contained in the feed water are removed by a filter demineralizer provided in the feed water pipe.
  • main components such as RPV use stainless steel, nickel base alloy or the like for the water contact portion in contact with water in order to suppress corrosion.
  • the components such as the reactor purification system, residual heat removal system, reactor isolation cooling system, core spray system and water supply system are derived from high-temperature water flowing through the water supply system, from the viewpoint of reducing the production cost of the plant.
  • carbon steel members are mainly used.
  • a part of the reactor water (cooling water present in the RPV) is purified by the reactor water purification device of the reactor purification system to actively remove metal impurities slightly present in the reactor water.
  • radionuclides attached to the outer surface of the fuel rod in the form of oxide elute as ions in the reactor water depending on the solubility of the incorporated oxide, and re-emit it into the reactor water as an insoluble solid called cladding. Be done.
  • Radionuclides in reactor water are removed by the reactor purification system.
  • radionuclide which has not been removed is accumulated on the surface of the component in contact with the reactor water while circulating with the reactor water and the like.
  • radiation is emitted from the surface of the component members, which causes radiation exposure of workers during the routine inspection operation.
  • the exposure dose of the employee is controlled so that each person does not exceed the specified value.
  • this specified value has been lowered, and it has become necessary to lower the radiation dose of each person as economically as possible.
  • Patent Document 1 As a technique which can reduce the adhesion amount of the radionuclide to the structural member of a nuclear power plant, there exists patent document 1, for example.
  • a reducing agent and a noble metal ion are respectively injected into the reactor water, and the reactor water containing the reducing agent and the noble metal ion is brought into contact with the surface of the structural member of the nuclear power plant
  • the generated noble metal is attached to the surface of the structural member
  • Ni ions are injected into the reactor water
  • the reactor water containing Ni ions is brought into contact with the surface of the structural member to which the noble metal is attached to generate Ni from Ni ions.
  • a method for suppressing the adhesion of radionuclides to structural members of a nuclear power plant is disclosed, which is characterized in that it is attached to a surface to which a noble metal is attached.
  • a first object of the present invention is to provide a method of depositing a noble metal on a carbon steel member of a nuclear power plant which can reduce the time required for depositing the noble metal on the carbon steel member.
  • the second object of the present invention is to provide a method of suppressing the adhesion of radionuclides to carbon steel members of a nuclear power plant which can maintain the effect of suppressing the adhesion of radionuclides to carbon steel members over a longer period of time. It is in.
  • a first invention for achieving the first object described above comprises the steps of: supplying a stabilizer capable of forming a complex with nickel ions on a surface of a carbon steel member of a nuclear power plant in contact with cooling water; Supplying a solution containing nickel to attach a complex formed by the nickel ion and the stabilizer to the surface; supplying a first reducing agent to the surface to reduce the nickel ion in the complex; A step of forming a nickel metal film on the surface, a step of supplying a solution containing a noble metal ion to the surface, and depositing the noble metal ion on the surface of the nickel metal film, and supplying a second reducing agent to the surface And attaching a noble metal to a carbon steel member of a nuclear power plant, comprising the steps of: reducing a noble metal ion to attach the noble metal to the surface of the nickel metal film.
  • the method of depositing a noble metal on a carbon steel member of a nuclear power plant according to the present invention is carried out, and nickel containing noble metal attached to water containing oxygen at 200 ° C. or higher.
  • the present invention provides a method for suppressing the adhesion of radionuclides to carbon steel members of a nuclear power plant characterized by converting a nickel metal film into a nickel ferrite film by contacting the metal film.
  • the time required for the deposition of the noble metal on the carbon steel member of the nuclear power plant can be shortened.
  • the effect of suppressing the adhesion of radionuclides to carbon steel members of a nuclear power plant can be sustained for a longer period of time.
  • Example 2 Block diagram of heating system of Example 2
  • the schematic diagram which shows the state of the inner surface of the carbon steel member (purification system piping) in step S17 implementation of Example 2.
  • the schematic diagram which shows the state of the inner surface of the carbon steel member (purification system piping) in step S17 implementation of Example 2.
  • the schematic diagram which shows the state of the inner surface of the carbon steel member (purification system piping) in step S17 implementation of Example 2.
  • Example 3 Flow chart showing the procedure of the method of attaching the noble metal to the carbon steel member of the nuclear power plant of Example 3 Flow chart showing the procedure of the method of attaching the noble metal to the carbon steel member of the nuclear power plant of Example 4 Block diagram of film forming apparatus used in Example 4 Graph showing the amounts of Ni metal films formed in Example 1 and Example 4
  • a noble metal for example, platinum
  • nickel is attached to the surface of the carbon steel member to which the noble metal is attached. It is described that the adhesion amount of the radionuclide to the surface of the carbon steel member is significantly reduced. Based on this finding, the present inventors have made it possible to shorten the time required for attaching a noble metal to a carbon steel member on the premise that the noble metal and nickel are attached to the surface of the carbon steel member and to reduce the time required for the adhesion of the noble metal to the carbon steel member. We have conducted intensive studies on the proposed measures that can further suppress the adhesion of radionuclides.
  • the inventor contains an iron (II) ion, an oxidant and a pH adjuster (for example, hydrazine).
  • a film forming solution in a low temperature range of 100 ° C. to 100 ° C. is brought into contact with the surface of a component of a nuclear power plant to form a magnetite film on the surface of the component and a noble metal is deposited on this magnetite film.
  • a phenomenon was found that the magnetite film elutes in reactor water due to the action of a noble metal during the operation of the plant.
  • the nickel ferrite film is The phenomenon of elution into reactor water was found by the action of precious metals. The elution of such a ferrite film from the surface of the carbon steel member eventually leads to the disappearance of the ferrite film on the carbon steel member, and after the ferrite film disappears, ie, at the end of the operation cycle, the radionuclide is carbon It adheres to the surface of the steel member.
  • radionuclide adhesion to the surface of carbon steel members is intended, but also radionuclides
  • Ni 0.7 Fe 2.3 O 4 is a form in the case where x is 0.3 in Ni 1-x Fe 2 + x O 4 .
  • Ni 0.7 Fe 2.3 O4 when the platinum is deposited, Ni 0.7 Fe 2.3 O 4 it is, by the action of the platinum It has been found that it elutes in reactor water during operation of a nuclear power plant.
  • Ni 0.7 Fe 2.3 O 4 film is formed in the above-mentioned low temperature range, small particles of Ni 0.7 Fe 2.3 O 4 are formed on the surface of the carbon steel member. Many are in the state of being attached. Also for this reason, a film of Ni 0.7 Fe 2.3 O 4 with platinum adhering to the upper surface is eluted.
  • Nickel metal which covers the surface of a carbon steel member is a substance which contributes to formation of a stable nickel ferrite film which controls adhesion of a radioactive nuclide to a carbon steel member, as mentioned later.
  • the formation of a nickel metal film on the surface of a carbon steel member is possible by bringing an aqueous solution containing nickel ions and a reducing agent into contact with the surface of the carbon steel member.
  • the nickel ion contained in the aqueous solution is substituted with Fe contained in the carbon steel member, and the substituted nickel ion becomes nickel metal by the action of the reducing agent, and a nickel metal film is formed on the surface of the carbon steel member.
  • adhesion of a noble metal to the surface of a nickel metal film formed on the surface of a carbon steel member is possible by bringing an aqueous solution containing noble metal ions (eg, platinum ions) and a reducing agent into contact with the formed nickel metal film. is there.
  • the examination result regarding the adhesion suppression over a long period of time of the radionuclide to the surface of a carbon steel member is demonstrated below.
  • the inventor does not form an unstable Ni 0.7 Fe 2.3 O 4 film on the surface of a carbon steel member in a low temperature range of 60 ° C. to 100 ° C., and does not dissolve even by the deposited noble metal. Aimed at the formation of various nickel ferrite films on the surface of carbon steel members. Then, the inventor forms a nickel metal film formed on the surface of the carbon steel member to effectively adhere the noble metal to the carbon steel member, forming the stable nickel ferrite film on the surface of the carbon steel member We examined variously whether it could not be used.
  • the nickel metal film is brought into contact by bringing high temperature (200 ° C. or more) water containing oxygen into contact with the surface of the nickel metal film formed on the surface of the carbon steel member to which the noble metal is attached. It could be converted into a stable nickel ferrite film (a nickel ferrite film in which x is 0 in Ni 1-x Fe 2 + x O 4 ) which covers the surface of the carbon steel member and which is not eluted even by the action of a noble metal.
  • test piece A made of carbon steel not having nickel and platinum attached and a test piece B made of carbon steel having a nickel metal film formed on the surface and platinum attached to the surface of the nickel metal film.
  • An experiment was conducted to confirm the adhesion of the nuclide Co-60.
  • test pieces A and B were placed in a closed loop circulation pipe, and simulated water simulating reactor water in the reactor was circulated and circulated in the circulation pipe.
  • the simulated water to be circulated contains Co-60, and the temperature of the simulated water is 280 ° C.
  • Each of the test pieces A and B installed in the circulation pipe was immersed in the simulated water flowing in the circulation pipe for 500 hours. After 500 hours had passed, each of the test pieces A and B was removed from the circulation pipe, and the amount of Co-60 deposited on each test piece was measured.
  • FIG. 1 is a graph showing the measurement results of the Co-60 adhesion amount of the test pieces A and B after the Co-60 adhesion experiment. As shown in FIG. 1, in the test piece B in which platinum was attached to the surface of the nickel metal film, the adhesion amount of Co-60 was significantly reduced as compared to the test piece A in which nickel and platinum were not attached.
  • FIG. 2 is a graph showing Raman spectra of test pieces A and B after the Co-60 adhesion test.
  • a film mainly composed of Fe 3 O 4 was formed on the surface of the test piece A, which is substantially carbon steel.
  • An oxide film containing nickel ferrite (NiFe 2 O 4 ) as a main component was formed on the surface of the test specimen B in which the amount of Co-60 attached was significantly reduced.
  • NiFe 2 O 4 is a form in which x is 0 in Ni 1 -xFe 2 + x O 4 .
  • FIG. 3 is a graph showing the Auger spectrum of the surface of the test piece B after the Co-60 adhesion experiment. From the results shown in FIG. 3, it was confirmed that NiFe 2 O 4 having a uniform composition was formed on the surface of the base material (carbon steel) of the test piece B. Due to the formation of NiFe 2 O 4 , the adhesion amount of Co-60 was remarkably suppressed in the test piece B.
  • a nickel metal film of a carbon steel member (test piece B) in which a nickel metal film is formed on the surface and a noble metal (for example, platinum) is attached to the surface of the nickel metal film is in contact with oxygen containing water at 200 ° C. or higher.
  • a nickel ferrite film a nickel ferrite film in which x is 0 in Ni 1 -x Fe 2 + x O 4 ) covering the surface of a carbon steel member will be described.
  • Oxygen contained in the water is transferred into the nickel metal film, and Fe contained in the carbon steel member is converted into Fe 2+ and transferred into the nickel metal film.
  • Nickel in the nickel metal film reacts with oxygen and Fe 2+ transferred into the nickel metal film in a high temperature environment of 200 ° C. or higher to form nickel ferrite in which x is 0 in Ni 1-x Fe 2 + x O 4 Ru.
  • the nickel ferrite film covers the surface of the carbon steel member.
  • a nickel ferrite in which x is 0 in Ni 1-x Fe 2 + x O 4 generated as described above from a nickel metal contained in a nickel metal film covering the surface of a carbon steel member at a high temperature of 200 ° C. or higher The crystals are large growth, and even if precious metals are attached, they are stable as they do not elute in water like Ni 0.7 Fe 2.3 O 4 film, and they incorporate radionuclides such as Co-60. Absent.
  • the stable nickel ferrite in which x is 0 in Ni 1-x Fe 2 + x O 4 is because the corrosion potential of the carbon steel member and the nickel metal film is lowered by the action of a noble metal such as platinum attached to the nickel metal film.
  • the nickel ferrite film formed from nickel metal covering the surface of a carbon steel member can be formed by Ni 0.
  • the adhesion of radionuclides to carbon steel members can be suppressed for a longer time than the 7 Fe 2.3 O 4 coating.
  • the inventor examined the above-described efficient formation method of the nickel metal film.
  • a stabilizer capable of forming a complex with the nickel ion is provided on the surface of the carbon steel member. The reason is explained below.
  • the carbon steel member is chemically decontaminated to remove the oxide film containing the radionuclide formed on its surface.
  • Chemical decontamination is carried out by reductive decontamination using oxalic acid as a decontamination solution, and this oxalic acid and nickel ions supplied to the surface of the carbon steel member combine (form (Ni (COOH) 2 )) By doing so, the nickel ions supplied to the surface of the member may be reduced. Therefore, in the present invention, a nickel ion complex is formed by adding a stabilizer capable of forming a complex with the nickel ion before supplying the nickel ion to the surface of the carbon steel member, thereby forming a nickel ion complex with the nickel ion. Prevents the combination with oxalic acid. By doing so, it has been found that efficient supply to the surface of the carbon steel member can be realized.
  • a film forming aqueous solution containing a nickel ion, a stabilizer and a reducing agent is brought into contact with the surface of a carbon steel member to form a nickel metal film on the surface of the carbon steel member and a noble metal is attached to the surface of the nickel metal film
  • a film forming aqueous solution containing a nickel ion and a reducing agent is brought into contact with the surface of a carbon steel member, a nickel metal film is formed on the surface of the carbon steel member, a noble metal is deposited on the surface of the nickel metal film, and oxygen is absorbed.
  • Water containing at least 200 ° C is brought into contact with the nickel metal film on which the noble metal is attached, and based on the nickel metal contained in the nickel metal film, the nickel ferrite film is formed on the surface of the carbon steel member under high temperatures of 200 ° C or more Form.
  • (1) is an invention related to a method of attaching a noble metal to a carbon steel member of a nuclear power plant. According to the invention of (1), since the surface of the carbon steel member is covered with the nickel metal film, elution of Fe 2+ from the carbon steel member can be prevented, and the time required for adhesion of noble metal to the surface of the carbon steel member Can be shortened. Further, by forming a complex of a nickel ion and a stabilizer, which are raw materials of the nickel metal film, efficient formation of the nickel metal film can be realized.
  • (2) is an invention relating to a method for suppressing adhesion of radionuclides to carbon steel members of a nuclear power plant.
  • the nickel metal film formed on the surface of the carbon steel member to which the noble metal is attached is brought into contact with water containing oxygen and having a temperature of 200 ° C. or more, and nickel contained in the nickel metal film.
  • a nickel ferrite film is formed on the surface of the carbon steel member at a high temperature of 200 ° C. or higher.
  • the formed nickel ferrite film does not elute in water even if the noble metal adheres, and adheres to the radionuclide to the carbon steel member over a longer period of time (specifically, over multiple operation cycles) Can be suppressed.
  • FIG. 4 is a block diagram showing a state in which a radionuclide adhesion preventing film type apparatus is connected to a purification system pipe of a BWR plant
  • FIG. 5 is a block diagram showing details of the radionuclide adhesion preventing film forming apparatus in FIG.
  • the BWR plant 1 includes, as a rough configuration, a reactor 2, a turbine 9, a condenser 10, a recirculation system piping, a reactor purification system piping, a water supply system piping, and the like.
  • Reactor 2 has a reactor pressure vessel (hereinafter referred to as RPV) 3 incorporating core 4 and is formed between the outer surface of a core shroud (not shown) surrounding core 4 within RPV 3 and the inner surface of RPV 3
  • the jet pump 5 is installed in the annular down cover.
  • the core 4 is loaded with a number of fuel assemblies (not shown).
  • the fuel assembly includes a plurality of fuel rods filled with a plurality of fuel pellets made of nuclear fuel material.
  • the recirculation system has a stainless steel recirculation system pipe 6 and a recirculation pump 7 installed in the recirculation system pipe 6.
  • the water supply system includes a condensate pump 12, a condensate purification apparatus (for example, a condensate demineralizer) 13, a low pressure feed water heater 14, a feed water pump 15, and a high pressure feed water to a feed water pipe 11 connecting the condenser 10 and the RPV 3
  • the heater 16 is installed and arranged in this order from the condenser 10 toward the RPV 3.
  • the reactor purification system comprises a purification system pipe 18 connecting the recirculation system pipe 6 and the water supply pipe 11, with the purification system pump 19, the regenerative heat exchanger 20, the non-regeneration heat exchanger 21 and the reactor water purification device 22 in this order. It has been installed.
  • the purification system piping 18 is connected to the recirculation system piping 6 upstream of the recirculation pump 7.
  • the reactor 2 is installed in a reactor containment vessel 87 disposed in a reactor building (not shown).
  • the cooling water in the RPV 3 (hereinafter referred to as “furnace water”) is pressurized by the recirculation pump 7 and is jetted into the jet pump 5 through the recirculation system pipe 6.
  • Reactor water present in the downcomer around the nozzle of the jet pump 5 is also drawn into the jet pump 5 and supplied to the core 4.
  • the reactor water supplied to the core 4 is heated by the heat generated by the nuclear fission of the nuclear fuel material in the fuel rod. Some of the heated reactor water becomes steam.
  • the steam is led from the RPV 3 through the main steam piping 8 to the turbine 9 to rotate the turbine 9.
  • a generator (not shown) connected to the turbine 9 rotates to generate electric power.
  • the steam discharged from the turbine 9 is condensed by the condenser 10 into water.
  • This water is supplied to the RPV 3 through the water supply pipe 11 as water supply.
  • the feed water flowing through the feed water pipe 11 is pressurized by the condensate pump 12, impurities are removed by the condensate purification device 13, and the pressure is further boosted by the feed pump 15.
  • the feedwater is heated by the low pressure feedwater heater 14 and the high pressure feedwater heater 16 and introduced into the RPV 3.
  • Extracted steam extracted from the turbine 9 in the extraction pipe 17 is supplied to the low pressure feed water heater 14 and the high pressure feed water heater 16, respectively, and serves as a heating source of the feed water.
  • the purified reactor water is heated by the regenerative heat exchanger 20 and returned to the interior of the RPV 3 through the purification system piping 18 and the water supply piping 11.
  • a radionuclide adhesion preventing film type device (hereinafter simply referred to as "film forming device") 30 is used. As shown in FIG. 2, it is connected to the purification system piping 18 of the BWR plant.
  • the film forming apparatus 30 includes a surge tank 31, circulation pumps 32, 33, circulation piping 34, nickel ion injection apparatus 35, reducing agent injection apparatus 40, platinum ion injection apparatus 45, heater 51, cooler 52, cation exchange resin tower 53, a mixed bed resin tower 54, a decomposition device 55, an oxidant injection device 56, an ejector 61, and a stabilizer injection device 202.
  • An on-off valve 62, a circulation pump 33, valves 63, 66, 68 and 73, a surge tank 31, a circulation pump 32, a valve 76 and an on-off valve 77 are provided in the circulation pipe 34 in this order from the upstream.
  • a pipe 65 bypassing the valve 63 is connected to the circulation pipe 34, and the valve 64 and the filter 50 are installed in the pipe 65.
  • a cooler 52 and a valve 67 are installed in the pipe 100 which bypasses the valve 66 and is connected to the circulation pipe 34 at both ends.
  • the cation exchange resin tower 53 and the valve 69 are installed in the pipe 70 which is connected to the circulation pipe 34 at both ends and bypasses the valve 68.
  • the mixed bed resin tower 54 and the valve 71 are installed in the piping 72 whose both ends are connected to the piping 70 and which bypasses the cation exchange resin tower 53 and the valve 69.
  • the cation exchange resin column 53 is filled with a cation exchange resin
  • the mixed bed resin column 54 is filled with a cation exchange resin and an anion exchange resin.
  • the decomposition device 55 is filled with an activated carbon catalyst in which, for example, ruthenium is attached to the surface of activated carbon.
  • a surge tank 31 is installed in the circulation pipe 34 between the valve 73 and the circulation pump 32.
  • a heater 51 is disposed in the surge tank 31.
  • a pipe 79 provided with the valve 78 and the ejector 61 is connected to the circulation pipe 34 between the valve 76 and the circulation pump 32 and is further connected to the surge tank 31.
  • the ejector 61 is provided with a hopper (not shown) for supplying oxalic acid (reduction decontaminant) used for reducing and dissolving the contaminants on the inner surface of the recirculation system pipe 6 into the surge tank 31.
  • the nickel ion implantation apparatus 35 has a chemical solution tank 36, an injection pump 37 and an injection pipe 38.
  • the chemical solution tank 36 is connected to the circulation pipe 34 by an injection pipe 38 having an injection pump 37 and a valve 39.
  • An aqueous solution of nickel formate (an aqueous solution containing nickel ions) prepared by dissolving nickel formate (2Ni (HCOO) ⁇ 2H 2 O) in water is filled in the chemical solution tank 36.
  • the platinum ion implantation apparatus (precious metal ion implantation apparatus) 45 has a chemical solution tank 46, an injection pump 47 and an injection pipe 48.
  • the chemical solution tank 46 is connected to the circulation pipe 34 by an injection pipe 48 having an injection pump 47 and a valve 49.
  • An aqueous solution containing platinum ions prepared by dissolving a platinum complex (eg, sodium hexahydroxoplatinate hydrate (Na 2 [Pt (OH) 6 ] .nH 2 O) in water (eg, sodium hexahydroxoplatinate water) Hydrate solution (water solution) is filled in the drug solution tank 46.
  • the aqueous solution containing platinum ions is a kind of aqueous solution containing precious metal ions.
  • an aqueous solution containing noble metal ions an aqueous solution containing any of palladium, rhodium, ruthenium, osmium and iridium may be used in addition to an aqueous solution containing platinum ions.
  • the reducing agent injection device 40 has a chemical solution tank 41, an injection pump 42 and an injection pipe 43.
  • the chemical solution tank 41 is connected to the circulation pipe 34 by an injection pipe 43 having an injection pump 42 and a valve 44.
  • the chemical solution tank 41 is filled with a first reducing agent that reduces Ni ions and a second reducing agent that reduces precious metal ions.
  • the first reducing agent and the second reducing agent can be the same.
  • any of hydrazine derivatives such as hydrazine, form hydrazine, hydrazine carboxamide and carbohydrazide and hydroxylamine may be used.
  • the injection pipes 38, 48 and 43 are connected to the circulation pipe 34 between the valve 76 and the on-off valve 77 in order from the valve 76 to the on-off valve 77.
  • the oxidant injection device 56 includes a chemical solution tank 57, a supply pump 58 and a supply pipe 59.
  • the chemical solution tank 57 is connected to the pipe 75 upstream of the valve 74 by a supply pipe 59 having a supply pump 58 and a valve 60.
  • Hydrogen peroxide which is an oxidant, is filled in the chemical solution tank 57.
  • ozone or water in which oxygen is dissolved may be used.
  • the stabilizer injection device 202 includes an injection pump 203, a chemical solution tank 204, and an injection pipe 206.
  • the chemical solution tank 204 is connected to the circulation pipe 34 by an injection pipe 206 having an injection pump 203 and a valve 205.
  • the chemical tank 204 is filled with a stabilizer.
  • the stabilizer is not particularly limited as long as it can form a complex with the nickel ion and does not promote stress corrosion cracking of carbon steel. Ammonia (NH 3 ) is preferred as such.
  • a pH meter 88 is attached to the circulation pipe 34 between the connection point of the injection pipe 43 and the circulation pipe 34 and the on-off valve 77.
  • the BWR plant 1 is stopped after the operation in one operation cycle is finished. After the shutdown, a part of the fuel assemblies loaded in the core 4 is taken out as a spent fuel assembly, and a new fuel assembly with a burnup of 0 GWd / t is loaded in the core 4. After such refueling is completed, the BWR plant 1 is restarted for operation in the next operation cycle. Maintenance inspection of the BWR plant is performed using a period during which the BWR plant 1 is stopped for refueling.
  • a carbon steel piping system communicated with the RPV 3 which is one of the carbon steel members in the BWR plant 1, for example, the purification system piping 18
  • the method of depositing the noble metal on the carbon steel member of the nuclear power plant of the present embodiment is performed.
  • adhesion treatment of nickel metal to the inner surface of the purification system pipe 18 in contact with the furnace water and adhesion treatment of noble metal such as platinum to the attached nickel metal are performed.
  • FIG. 6 is a flow chart showing the procedure of the method of depositing the noble metal on the carbon steel member of the nuclear power plant of the first embodiment.
  • the film forming apparatus 30 is connected to a carbon steel piping system to be subjected to film formation (step S1).
  • step S1 the film forming apparatus 30 is connected to a carbon steel piping system to be subjected to film formation.
  • the bonnet of the valve 23 installed in the purification system piping 18 connected to the recirculation system piping 6 is opened to close the recirculation system piping 6 side.
  • One end of the circulation piping 34 of the film forming apparatus 30 on the side of the on-off valve 77 is connected to the flange of the valve 23, and one end of the circulation piping 34 is connected to the purification system piping 18 upstream of the purification system pump 19.
  • the bonnet of the valve 25 installed in the purification system pipe 18 is opened between the regenerative heat exchanger 20 and the non-regenerating heat exchanger 21 to close the non-regenerating heat exchanger 21 side.
  • the other end of the circulation pipe 34 on the side of the on-off valve 62 is connected to the flange of the valve 25, and the other end of the circulation pipe 34 is connected to the purification system pipe 18 downstream of the regenerative heat exchanger 20. Both ends of the circulation pipe 34 are connected to the purification system pipe 18, and a closed loop including the purification system pipe 18 and the circulation pipe 34 is formed.
  • the film forming apparatus 30 is connected to the purification system pipe 18 of the reactor purification system, but in addition to the purification system pipe 18, a residual heat removal system which is a carbon steel member and communicated with the RPV 3
  • the film forming apparatus 30 is connected to a carbon steel pipe of either the reactor isolation cooling system or the core spray system, and the carbon steel pipe is connected to the noble metal to the carbon steel member of the nuclear power plant of the present embodiment.
  • a deposition method may be applied.
  • step S2 chemical decontamination is performed on a carbon steel piping system to be subjected to film formation.
  • an oxide film containing a radionuclide is formed on the inner surface of the purification system pipe 18 in contact with the reactor water flowing from the RPV 3.
  • the dose rate of the purification system pipe 18 is lowered in advance, and the film to be formed and the purification system pipe 18
  • chemical decontamination in particular, reduction decontamination using a reduction decontamination solution containing oxalic acid which is a reduction decontamination agent, is performed on the inner surface of the purification system pipe 18.
  • the chemical decontamination applied to the inner surface of the purification system pipe 18 in step S2 is, for example, a known reductive decontamination described in JP-A-2000-105295. This reduction decontamination will be described.
  • the circulation pumps 32 and 33 are driven with the on-off valve 62, the valves 63, 66, 68, 73 and 76 and the on-off valve 77 opened and the other valves closed.
  • the water heated by the heater 51 in the surge tank 31 in the purification system piping 18 circulates in the closed loop formed by the circulation piping 34 and the purification system piping 18.
  • the circulating water is adjusted to 90 ° C. by the heater 51.
  • the valve 78 When the temperature of the water reaches 90 ° C., the valve 78 is opened to guide a portion of the water flowing in the circulation pipe 34 into the pipe 79. A predetermined amount of oxalic acid supplied from the hopper and ejector 61 into the pipe 79 is introduced into the surge tank 31 by the water flowing through the pipe 79. The oxalic acid is dissolved in water in the surge tank 31, and an oxalic acid aqueous solution (reduction decontamination solution) is generated in the surge tank 31.
  • the oxalic acid aqueous solution is discharged from the surge tank 31 to the circulation pipe 34 by driving the circulation pump 32.
  • the hydrazine solution in the chemical solution tank 41 of the reducing agent injection device 40 is injected into the oxalic acid aqueous solution in the circulation pipe 34 through the injection pipe 43 by opening the valve 44 and driving the injection pump 42.
  • Purification system by controlling the injection pump 42 (or the opening degree of the valve 44) based on the pH value of the aqueous solution of oxalic acid measured by the pH meter 88 to adjust the injection amount of the hydrazine aqueous solution into the circulation pipe 34
  • the pH of the aqueous solution of oxalic acid supplied to the pipe 18 is adjusted to 2.5.
  • nickel metal when nickel metal is attached to the inner surface of the purification system pipe 18 and a noble metal such as platinum is attached on the nickel metal film, hydrazine which is a reducing agent used for reduction decontamination is used. In the process, it is used as a pH adjuster to adjust the pH of an aqueous solution of oxalic acid.
  • An aqueous solution of oxalic acid having a pH of 2.5 and a temperature of 90 ° C. is supplied from the circulation pipe 34 to the purification system pipe 18 and contacts an oxide film containing a radionuclide formed on the inner surface of the purification system pipe 18. This oxide film is dissolved by oxalic acid.
  • the oxalic acid aqueous solution flows in the purification system pipe 18 while dissolving the oxide film, passes through the purification system pump 19 and the regenerative heat exchanger 20, and is returned to the circulation pipe 34.
  • the aqueous solution of oxalic acid returned to the circulation pipe 34 is pressurized by the circulation pump 33 through the on-off valve 62, passes through the valves 63, 66, 68 and 73, and reaches the surge tank 31.
  • the aqueous solution of oxalic acid circulates in the closed loop including the circulation pipe 34 and the purification system pipe 18 to carry out reduction decontamination of the inner surface of the purification system pipe 18 to dissolve the oxide film formed on the inner surface. .
  • the radionuclide concentration and Fe concentration of the aqueous solution of oxalic acid increase with the dissolution of the oxide film.
  • the cation exchange resin tower 53 is operated to suppress the increase in the concentration of each of the radionuclide and Fe contained in the aqueous solution of oxalic acid. That is, by adjusting the opening degree of the valve 69 by opening the valve 69, a part of the oxalic acid aqueous solution returned from the purification system pipe 18 to the circulation pipe 34 is conducted to the cation exchange resin tower 53 through the pipe 70. It is eaten.
  • the radionuclide contained in the oxalic acid aqueous solution and the metal cation such as Fe are adsorbed to the cation exchange resin in the cation exchange resin tower 53 and removed.
  • the oxalic acid aqueous solution discharged from the cation exchange resin column 53 and the oxalic acid aqueous solution passed through the valve 68 are again supplied from the circulation piping 34 to the purification system piping 18 and used for reduction decontamination of the purification system piping 18.
  • the valve 60 is opened to start the supply pump 58, and the hydrogen peroxide in the chemical solution tank 57 flows through the supply pipe 59 and the pipe 75 through the circulation pipe 34. Supply to aqueous acid solution. At this time, the valve 74 is closed.
  • An aqueous solution of oxalic acid containing hydrogen peroxide is led from the circulation pipe 34 into the purification system pipe 18 and Fe (II) contained in iron oxalate (II) formed on the inner surface of the purification system pipe 18 is an oxalic acid aqueous solution Is oxidized to Fe (III) by the action of hydrogen peroxide contained therein, and the iron (II) oxalate is dissolved in an aqueous solution of oxalic acid as an iron (III) oxalate complex (the following formula (1)).
  • iron oxalate (II) and hydrogen peroxide and oxalic acid contained in an aqueous solution of oxalic acid form an iron (III) oxalate complex, water and hydrogen ions by the reaction shown in formula (1).
  • the valve 69 is opened.
  • the opening degree of the valve 68 is adjusted, and a part of the aqueous solution of oxalic acid flowing in the circulation pipe 34 and passing through the valve 66 is supplied to the cation exchange resin tower 53 through the pipe 70.
  • Metal cations such as radionuclide contained in the aqueous solution of oxalic acid are adsorbed to the cation exchange resin in the cation exchange resin tower 53 and removed.
  • the disappearance of hydrogen peroxide in the oxalic acid aqueous solution can be confirmed by attaching a test paper reacting with hydrogen peroxide to the oxalic acid aqueous solution sampled from the circulation pipe 34 and observing the color appearing on the test paper.
  • the decomposition of oxalic acid and hydrazine is carried out as follows.
  • the valve 74 is opened to partially reduce the opening degree of the valve 73, and the oxalic acid aqueous solution containing hydrazine which has flowed through the circulation pipe 34 and passed through the valve 68 is supplied to the disassembling apparatus 55 through the valve 74 through the pipe 74. Be done.
  • the hydrogen peroxide in the chemical solution tank 57 is supplied to the pipe 75 through the supply pipe 59 and flows into the decomposition device 55.
  • the oxalic acid and hydrazine contained in the aqueous oxalic acid solution are decomposed in the decomposition unit 55 by the action of the activated carbon catalyst and the supplied hydrogen peroxide (the following formulas (2) and (3)).
  • the decomposition of oxalic acid and hydrazine in the decomposition apparatus 55 is performed while circulating the oxalic acid aqueous solution in a closed loop including the circulation pipe 34 and the purification system pipe 18.
  • the supply amount of hydrogen peroxide from the chemical solution tank 57 to the decomposition device 55 is set so that the supplied hydrogen peroxide is not completely consumed by the decomposition device 55 for decomposition of oxalic acid and hydrazine and does not flow out of the decomposition device 55.
  • the rotational speed of the feed pump 58 is controlled and adjusted.
  • the aqueous solution of oxalic acid containing hydrogen peroxide discharged from the decomposition device 55 is led from the circulation pipe 34 to the purification system pipe 18.
  • the iron (II) oxalate formed on the inner surface of the purification system pipe 18 which is a carbon steel member becomes an iron (III) oxalate complex by the action of hydrogen peroxide and is dissolved in an aqueous oxalic acid solution Do.
  • Injection of formic acid is carried out, for example, by supplying the formic acid from the hopper and ejector 61 described above to the oxalic acid aqueous solution and guiding it to the surge tank 31 while the valve 78 is opened and the oxalic acid aqueous solution is flowing in the pipe 79. It will be.
  • the supplied formic acid is mixed with the aqueous oxalic acid solution.
  • the aqueous solution of oxalic acid containing formic acid supplied contains hydrogen peroxide discharged from the decomposition apparatus 55 in addition to the lowered concentrations of oxalic acid and hydrazine.
  • the oxalic acid aqueous solution containing this formic acid and hydrogen peroxide is supplied to the purification system pipe 18.
  • the hydrogen peroxide contained in the oxalic acid aqueous solution dissolves iron (II) oxalate deposited on the inner surface of the purification system pipe 18, and the formic acid dissolves Fe (OH) 3. Since the oxalic acid aqueous solution circulates in a closed loop including the circulation pipe 34 and the purification system pipe 18, the decomposition of oxalic acid and hydrazine is also continued in the decomposition device 55.
  • the hydrogen peroxide concentration of the oxalic acid aqueous solution flowing in the circulation pipe 34 is reduced, and the oxalic acid aqueous solution is supplied to the cation exchange resin tower 53.
  • the valve 60 is closed and the valve 78 is closed to stop the injection of formic acid.
  • the valve 69 is opened to reduce the opening degree of the valve 68, and the oxalic acid aqueous solution is supplied to the cation exchange resin tower 53.
  • the metal cation contained in the oxalic acid aqueous solution is removed by the cation exchange resin in the cation exchange resin tower 53, and the metal cation concentration of the oxalic acid aqueous solution decreases.
  • the decomposition of oxalic acid, hydrazine and formic acid is continued in the decomposition unit 55.
  • oxalic acid hydrazine and formic acid
  • hydrazine is decomposed first, then oxalic acid is decomposed, and formic acid remains last. In this state, the oxalic acid decomposition process is completed.
  • FIG. 7 is a schematic view showing the state of the inner surface of the carbon steel member (purification system piping) after completion of step S2 of the first embodiment.
  • the purification system piping 18 when chemical decontamination is completed, the purification system piping 18 is in a state where the oxide film containing radionuclide is removed from the inner surface of the purification system piping 18, and the inner surface of the purification system piping 18 is It is in contact with an aqueous solution containing the above-mentioned remaining formic acid.
  • step S3 the temperature of the film forming solution is adjusted (step S3). Open valves 68 and 73 and close valves 69 and 74. Since the circulation pumps 32 and 33 are driven, the remaining aqueous solution containing formic acid circulates in the closed loop including the circulation pipe 34 and the purification system pipe 18.
  • the aqueous solution containing the formic acid is heated to 90 ° C. by the heater 51.
  • the temperature of the formic acid aqueous solution (a film-forming aqueous solution described later) is preferably in the range of 60 ° C. to 100 ° C. (60 ° C. or more and 100 ° C. or less). Further, the valve 64 is opened and the valve 63 is closed.
  • the aqueous solution of formic acid flowing in the circulation pipe 34 is supplied to the filter 50, and the fine solid content remaining in the aqueous solution of formic acid is removed by the filter 50.
  • fine solid content is not removed by the filter 50, when a nickel formic acid aqueous solution is injected into the circulation pipe 34 when forming a nickel metal film on the inner surface of the purification system pipe 18, nickel is also formed on the surface of the solid. A metal film is formed, and the implanted nickel ions are wasted. Supply of the formic acid aqueous solution to the filter 50 is to prevent such wasteful use of nickel ions.
  • a stabilizer is injected (S4), and a nickel ion solution is injected (step S5).
  • the Ni ion as the raw material of the Ni metal film is reacted with the stabilizer to form a Ni complex, thereby preventing the compound of the oxalic acid and the Ni ion existing on the surface of the member, and the surface of the member It is possible to supply Ni ions efficiently.
  • the valve 205 of the stabilizer injection device 202 is opened to drive the injection pump 203, and the stabilizer (in the present embodiment, ammonia) in the chemical solution tank 204 is injected into the circulation piping 34 through the injection piping 206.
  • the valve 39 of the nickel ion implantation apparatus 35 is opened to drive the injection pump 37, and Ni ions in the chemical solution tank 36 are injected into the circulation pipe 34 through the injection pipe 38.
  • the stabilizer forms a complex (Ni (NH3) 2) with the Ni ion, so that the Ni ion can be efficiently supplied to the surface of the member without the Ni ion and the oxalic acid being combined.
  • the nickel ion concentration of the aqueous solution of nickel formate to be injected is, for example, 200 ppm.
  • a reducing agent is injected (step S6).
  • the valve 44 of the reducing agent injection device 40 is opened and the injection pump 42 is driven to flow the aqueous solution of hydrazine which is the reducing agent in the chemical solution tank 41 through the injection pipe 43 in the circulation pipe 34. It is injected into a 90 ° C. aqueous solution containing formic acid.
  • the hydrazine concentration of the aqueous hydrazine solution to be injected is, for example, 200 ppm.
  • the aqueous hydrazine solution contains a complex of ammonia and nickel ions and a formic acid, so that the pH of the aqueous solution at 90 ° C. is in the range of 4.0 to 11.0 (4.0 to 11.0), for example, 4.0
  • the amount injected into the aqueous solution is adjusted to
  • FIG. 8 is a schematic view showing the state of the inner surface of the carbon steel member (purification system piping) after step S6 in the first embodiment.
  • An aqueous solution containing a complex of nickel ion and ammonia, formic acid and hydrazine and having a pH of 4.0 at 90 ° C., ie, a film forming aqueous solution (film forming solution) 83 is purified from the circulation pipe 34 by driving the circulation pump 32.
  • the pipe 18 is supplied.
  • a nickel metal film 80 is formed on the inner surface of the purification system pipe 18 as shown in FIG. 8.
  • the formation of the nickel metal film 80 is performed as follows.
  • the nickel ion in the complex of the stabilizer and the nickel ion contained in the aqueous solution 83 for film formation and the Fe (II) in the aqueous solution for purification system 18 by the contact of the inner surface of the purification system piping 18 with the film formation aqueous solution 83 of pH 4.0.
  • the substitution reaction with ions is accelerated, the amount of nickel ions taken into the inner surface of the purification system pipe 18 increases, and the elution of iron (II) ions into the film forming aqueous solution 83 increases.
  • the nickel ions taken into the inner surface of the purification system pipe 18 become nickel metal by the action of the hydrazine contained in the film forming aqueous solution 83, and thus the nickel metal film 80 is formed on the inner surface of the purification system pipe 18.
  • the substitution reaction between nickel ions and iron (II) ions is most active when the pH of the film-forming aqueous solution 83 in contact with the inner surface of the purification system pipe 18 is 4.0, and is taken into the inner surface of the purification system pipe 18 The amount of nickel ions is the highest.
  • the pH of the aqueous solution for film formation 83 is increased (the pH is about 7) by the injection of the reducing agent, the amount of the incorporated nickel ion becoming a nickel metal increases.
  • the film forming aqueous solution 83 discharged from the purification system pipe 18 to the circulation pipe 34 is pressurized by the circulation pumps 33 and 32, and ammonia from the stabilizer injection device 202, nickel formate aqueous solution from the nickel ion injection device 35, and reducing agent
  • the aqueous hydrazine solution from the injection device 40 is injected, and injected again into the purification system pipe 18.
  • the nickel metal film eventually becomes in contact with the film-forming aqueous solution 83 of the purification system pipe 18. Cover the entire surface uniformly.
  • the amount of nickel metal present on the inner surface of the purification system pipe 18 is 50 ⁇ g (50 ⁇ g / cm 2 ) per square centimeter.
  • step S7 it is determined whether the formation of the nickel metal film is completed.
  • the steps S4 to S6 are repeated.
  • the injection pump 203 is stopped to close the valve 205 and stop the injection of the stabilizer into the circulation pipe 34.
  • the reducing agent is decomposed (step S8).
  • the valve 74 is opened to reduce the opening degree of the valve 73 and closed, and a portion of the film forming aqueous solution 83 containing nickel ions and hydrazine pressurized by the circulation pump 33 is led to the disassembling apparatus 55 through the pipe 75.
  • the hydrogen peroxide in the chemical solution tank 57 is supplied to the decomposition device 55 through the supply pipe 59 and the pipe 75.
  • the reducing agent hydrazine contained in the film-forming aqueous solution 83 is decomposed into nitrogen and water in the decomposition device 55 by the action of the activated carbon catalyst and hydrogen peroxide.
  • the film-forming aqueous solution in which the reducing agent is decomposed is purified (step S9).
  • the valve 73 is opened and the valve 74 is closed to stop the supply of the aqueous film forming aqueous solution 83 not containing hydrazine to the decomposition apparatus 55
  • the valve 67 is opened and the valve 66 is closed
  • the valve 71 is opened to reduce the opening degree of the valve 68.
  • the valve 69 is closed.
  • the circulation pumps 33 and 32 are driven.
  • the film forming aqueous solution 83 not containing hydrazine returned from the purification system pipe 18 to the circulation pipe 34 is cooled to 60 ° C. by the cooler 52.
  • the aqueous solution for film formation at 60 ° C. not containing hydrazine is led to the mixed bed resin tower 54, and nickel ions, other cations and anions remaining in the aqueous solution for film formation 83 are contained in the mixed bed resin tower 54.
  • the cation exchange resin and the anion exchange resin are adsorbed and removed (first purification step).
  • the aqueous solution for film formation at 60 ° C. not containing hydrazine is circulated through the circulation pipe 34 and the purification system pipe 18 until the above-described ions are substantially eliminated.
  • the film-forming aqueous solution substantially free of each ion is substantially 60 ° C. water.
  • a platinum ion aqueous solution is injected (step S10).
  • the valve 68 is opened and the valve 71 is closed, and the valve 49 is opened to drive the infusion pump 47.
  • the water flowing in the circulation pipe 34 is kept at 60 ° C. by heating by the heater 51.
  • An aqueous solution eg, sodium hexahydroxoplatinate hydrate (Na 2 [Pt (OH) 6 ] .nH 2 ) containing platinum ions in the chemical solution tank 46 through the injection piping 48 in water at 60 ° C. flowing in the circulation piping 34
  • An aqueous solution of O is injected.
  • the concentration of platinum ions in this aqueous solution to be injected is, for example, 1 ppm.
  • platinum is in an aqueous solution of sodium hexahydroxoplatinate hydrate, platinum is in an ionic state.
  • An aqueous solution containing platinum ions at 60 ° C. is supplied from the circulation pipe 34 to the purification system pipe 18 by driving the circulation pumps 32 and 33, and is returned from the purification system pipe 18 to the circulation pipe 34.
  • the aqueous solution containing platinum ions circulates in a closed loop including the circulation pipe 34 and the purification system pipe 18.
  • the amount of the aqueous solution of Na 2 [Pt (OH) 6 ] .nH 2 O to be filled in the chemical solution tank 46 is calculated, and the calculated amount of the aqueous solution of Na 2 [Pt (OH) 6 ] .nH 2 O Fill in 46
  • the rotational speed of the injection pump 47 is controlled in accordance with the calculated injection rate of the aqueous solution of Na 2 [Pt (OH) 6 ] ⁇ nH 2 O into the circulation pipe 34, and the Na 2 [Pt (OH 6 )
  • the nH 2 O aqueous solution is injected into the circulation pipe 34.
  • a reducing agent is injected (step S11).
  • the valve 44 of the reducing agent injection device 40 is opened to drive the injection pump 42, and an aqueous solution of hydrazine, which is the second reducing agent in the chemical solution tank 41, flows through the injection pipe 43 and in the circulation pipe 34. Pour into an aqueous solution at 60 ° C.
  • the hydrazine concentration of the aqueous hydrazine solution to be injected is, for example, 100 ppm.
  • the aqueous hydrazine solution is injected into the circulation pipe 34 after the aqueous solution of Na 2 [Pt (OH) 6 ] ⁇ nH 2 O at 60 ° C. reaches the connection point of the injection pipe 43 and the circulation pipe 34 which are injection points of the hydrazine aqueous solution. Be done.
  • a 60 ° C. aqueous solution containing platinum ions and hydrazine is supplied from the circulation pipe 34 to the purification system pipe 18.
  • the hydrazine aqueous solution is circulated It is desirable to inject into 34.
  • the aqueous solution 84 (see FIG. 9 described later) is supplied from the circulation pipe 34 to the purification system pipe 18.
  • FIG. 9 is a schematic view showing the state of the inner surface of the carbon steel member (purification system piping) after completion of step S11.
  • a 60 ° C. aqueous solution 84 containing platinum ions and hydrazine is injected, a reduction reaction to make platinum ions into platinum with hydrazine first occurs in an aqueous solution containing hydrazine and platinum ions flowing in circulation pipe 34. .
  • the concentration of hydrazine at the connection point of the aqueous hydrazine solution injected from the chemical solution tank 41 through the connection point of the circulation pipe 34 and the injection pipe 43 becomes 100 ppm, for example.
  • the rate of injection of the hydrazine solution into the circulation pipe 34 is calculated.
  • the platinum ion adsorbed on the surface of the nickel metal film 80 formed on the inner surface of the purification system pipe 18 is converted to platinum 81 by setting the hydrazine in the aqueous solution containing platinum ions at 60.degree.
  • the amount of the aqueous hydrazine solution to be charged into the chemical solution tank 41 necessary for reduction is calculated, and the calculated amount of the aqueous hydrazine solution is charged into the chemical solution tank 41.
  • the rotational speed of the injection pump 42 is controlled according to the calculated injection rate of the hydrazine aqueous solution into the circulation pipe 34, and the hydrazine aqueous solution in the chemical solution tank 41 is injected into the circulation pipe 34.
  • the platinum ion adsorbed on the surface of the nickel metal film 80 is reduced by the injected hydrazine to become platinum 81, and therefore, the platinum 81 adheres to the surface of the nickel metal film 80 formed on the inner surface of the purification system pipe 18 (see FIG. 9) ).
  • step S12 It is determined whether the deposition of platinum is completed (step S12). When the elapsed time from the injection of the platinum ion aqueous solution and the reducing agent aqueous solution reaches a predetermined time, it is determined that the adhesion of a predetermined amount of platinum to the surface of the nickel metal film 80 formed on the inner surface of the purification system pipe 18 is completed. . When the elapsed time does not reach the predetermined time, each process of steps S10 to S12 is repeated.
  • the aqueous solution remaining in the purification system pipe 18 and the circulation pipe 34 is purified (step S13).
  • the valve 71 is opened to make the valve 68 smaller and the pressure is increased by the circulation pump 33 Further, a 60 ° C. aqueous solution containing platinum ions and hydrazine is supplied to the mixed bed resin column 54.
  • Platinum ions, other metal cations (for example, sodium ions), hydrazine and OH groups contained in the aqueous solution are adsorbed to the ion exchange resin in the mixed bed resin column 54 and removed from the aqueous solution (second purification) Process).
  • the waste liquid is treated (step S14).
  • the circulation pipe 34 and the waste liquid treatment apparatus (not shown) are connected by a high pressure hose (not shown) having a pump (not shown).
  • the aqueous solution as radioactive waste liquid remaining in the purification system pipe 18 and the circulation pipe 34 is driven by the pump from the circulation pipe 34 through the high pressure hose to the waste liquid treatment apparatus (not shown) It is discharged and treated by the waste liquid treatment device.
  • wash water is supplied into the purification system pipe 18 and the circulation pipe 34, and the circulation pumps 32 and 33 are driven to wash the inside of these pipes.
  • the cleaning water in the purification system piping 18 and the circulation piping 34 is discharged to the above-described waste liquid treatment apparatus.
  • the method of attaching the noble metal to the carbon steel member of the nuclear power plant of the present embodiment is completed. Then, the film forming device 30 connected to the purification system piping 18 is removed from the purification system piping 18, and the purification system piping 18 is restored.
  • a film forming aqueous solution containing nickel ions, a stabilizer and a reducing agent for example, hydrazine
  • a reducing agent for example, hydrazine
  • a nickel metal film 80 covering the inner surface can be formed.
  • a complex is formed between the nickel ion and the stabilizer, so that the nickel ion is prevented from combining with the oxalic acid present on the inner surface of the purification system pipe 18.
  • Nickel ions can be efficiently supplied to the inner surface in contact with the reactor water.
  • FIG. 10 is a graph showing the formation amounts of the Ni metal film of Example 1 in which a Ni metal film was formed using a stabilizer and Reference Example 1 in which a Ni metal film was formed without using a stabilizer.
  • the formation of the Ni metal film was performed under the same conditions (the amount of injected nickel ion solution) except for the presence or absence of the stabilizer. As shown in FIG. 10, it was confirmed that the formation amount of the Ni metal film of Example 1 increased to five times the formation amount of the Ni metal film of Reference Example 1.
  • the nickel metal film 80 can prevent the elution of Fe 2+ from the purification system pipe 18 to the aqueous solution for film formation, and the adhesion of noble metal (eg, platinum) to the inner surface of the purification system pipe 18 is inhibited by the elution of Fe 2+ Therefore, the time required for the adhesion of the noble metal to the inner surface (specifically, the adhesion of the noble metal to the surface of the nickel metal film 80 formed on the inner surface of the purification system pipe 18) can be shortened. Further, the adhesion of the noble metal to the inner surface can be efficiently performed, and the adhesion amount of the noble metal to the inner surface of the purification system pipe 18 is increased.
  • noble metal eg, platinum
  • 50 ⁇ g / cm 2 of nickel metal is present in the nickel metal film 80 formed on the inner surface of the purification system pipe 18.
  • the nickel metal film 80 covers the entire inner surface of the purification system pipe 18 in contact with the film forming solution, and during operation of the BWR plant The contact of the reactor water flowing in the purification system piping 18 with the base material of the purification system piping 18 is blocked by the nickel metal film 80. For this reason, uptake of the radionuclide contained in the reactor water into the base material of the purification system pipe 18 does not occur.
  • the nickel metal film 80 formed on the inner surface of the purification system piping 18 not only shortens the time required for adhesion of platinum to the purification system piping 18 but also adheres as described in Example 2 and Example 3 described later. Together with the action of the platinum 81, it contributes to the formation of a stable nickel ferrite film which does not elute into the reactor water even by the platinum attached to the inner surface of the purification system pipe 18.
  • nickel metal film 80 In the formation of the nickel metal film 80 on the inner surface of the purification system pipe 18, nickel ions contained in the aqueous solution for film formation are replaced with iron ions contained in the purification system pipe 18 and taken into the inner surface of the purification system pipe 18.
  • the nickel ion incorporated on the inner surface is reduced to a nickel metal by hydrazine (reducing agent) contained in the aqueous solution.
  • reducing agent reducing agent
  • the nickel metal film 80 is formed on the inner surface of the purification system pipe 18, so oxidation formed with the radionuclide is formed on the inner surface of the purification system pipe 18.
  • a nickel metal film is not formed on the film, radiation emitted from the purification system piping 18 is reduced, and the surface dose rate of the purification system piping 18 is significantly reduced.
  • an oxidizing agent eg, hydrogen peroxide
  • a method of suppressing adhesion of radionuclides to carbon steel members of a nuclear power plant of a second embodiment which is another preferred embodiment of the present invention will be described below with reference to FIG. 11 and FIG.
  • the method of suppressing adhesion of radionuclides to the carbon steel member of the present embodiment is applied to the purification system piping of a BWR plant.
  • FIG. 11 is a flow chart showing the procedure of the method of depositing the noble metal on the carbon steel member of the nuclear power plant of the second embodiment.
  • each step of steps S1 to S14 in the method for adhering noble metals to carbon steel members of the nuclear power plant of embodiment 1 and new steps S15 to S18 Each step is performed.
  • the film forming apparatus 30 used in the first embodiment is used in each of the steps S1 to S14, and a new heating system 90 is used.
  • FIG. 12 is a block diagram of a heating system of a second embodiment.
  • the heating system 90 is a pressure-resistant structure, and includes a circulation pipe 91, a circulation pump 92, a heater 93, and a valve 94 which is a pressure booster.
  • a circulation pump 92 is provided in the circulation pipe 91, and a heater 93 is provided in the circulation pipe 91 upstream of the circulation pump 92.
  • the heater 93 may be disposed downstream of the circulation pump 92.
  • the pipe 95 bypasses the circulation pump 92, one end of the pipe 95 is connected to the circulation pipe 91 upstream of the circulation pump 92, and the other end of the pipe 95 is downstream of the circulation pump 92 to the circulation pipe 91.
  • a valve 94 is provided in the pipe 95.
  • An on-off valve 96 is provided at the upstream end of the circulation pipe 91, and an on-off valve 97 is provided at the downstream end of the circulation pipe.
  • the film forming apparatus 30 is removed from the piping system (step S15).
  • the film forming apparatus 30 connected to the purification system pipe 18 is performed after each step of steps S1 to S14 described in the first embodiment is performed. It is removed from the purification system piping 18.
  • One end of the circulation pipe 34 of the film forming apparatus 30 is removed from the flange of the valve 23, and the other end of the circulation pipe 34 is removed from the flange of the valve 25.
  • the heating system 90 is connected to the piping system (step S16).
  • One end of the circulation piping 91 of the heating system 90 on the side of the on-off valve 97 is connected to the flange of the valve 23, and one end of the circulation piping 91 is connected to the purification system piping 18 upstream of the purification system pump 19.
  • the other end of the circulation pipe 91 on the open / close valve 96 side is connected to the flange of the valve 25, and the other end of the circulation pipe 91 is connected to the purification system pipe 18 downstream of the regenerative heat exchanger 20.
  • Both ends of the circulation pipe 91 are connected to the purification system pipe 18 to form a closed loop including the purification system pipe 18 and the circulation pipe 91.
  • Water containing oxygen at 200 ° C. or more is brought into contact with the platinum-deposited nickel metal film (step S17).
  • Water containing oxygen is filled in a closed loop including the circulation pipe 91 and the purification system pipe 18.
  • the circulation pump 92 is driven to circulate oxygen-containing water in the closed loop.
  • the rotational speed of the circulation pump 92 is increased to a certain rotational speed, and then the opening degree is decreased while the valve 94 is gradually closed to increase the pressure of the oxygen-containing water discharged from the circulation pump 92.
  • the heater 93 heats the oxygen-containing water circulating in the closed loop to raise the temperature of the water.
  • the pressure of the water discharged from the circulation pump 92 is increased, the temperature of the water is raised.
  • the rotational speed of the circulation pump 92 is further increased.
  • the pressure of water circulating in the closed loop is increased to, for example, 1.6 MPa, and the temperature of water is increased to about 201 ° C.
  • the pressure and the temperature of the water circulating in the closed loop are kept at the respective values mentioned above.
  • the temperature of the water can be raised to about 276 ° C. by raising the pressure of the water circulating in the closed loop to 6 MPa.
  • FIG. 13 to 15 are schematic views showing the state of the inner surface of the carbon steel member (purification system piping) during step S17 of the second embodiment.
  • Water 85 at approximately 201 ° C. containing oxygen is supplied from the circulation pipe 91 to the purification system pipe 18 and contacts the nickel metal film 80 formed on the inner surface of the purification system pipe 18 to which platinum 81 adheres (see FIG. 13) ).
  • the purification system piping 18 is surrounded by a heat insulating material (not shown) except for the vicinity of the valves 23 and 25 to which both ends of the circulation piping 91 are connected.
  • each of the water 85 containing oxygen, the purification system pipe 18 and the nickel metal film 80 reaches about 201 ° C. of 200 ° C. or more, oxygen (O 2 ) contained in the water 85 is transferred into the nickel metal film 80
  • the Fe contained in the purification system pipe 18 becomes Fe 2+ and migrates into the nickel metal film 80 (see FIG. 14).
  • the action of the platinum 81 attached to the nickel metal film 80 lowers the corrosion potential of the purification system pipe 18 and the nickel metal film 80. Due to the reduction of the corrosion potential of the nickel metal film 80 and the formation of a high temperature environment of about 201 ° C., the nickel in the nickel metal film 80 reacts with the oxygen and Fe 2+ transferred into the nickel metal film 80 to obtain Ni 1 -x Fe 2 + x.
  • nickel ferrite in O 4 x is 0 (NiFe 2 O 4) is generated. Therefore, the nickel metal film 80 formed on the inner surface of the purification system pipe 18 is converted into the film 82 of nickel ferrite, and the nickel ferrite film 82 covers the inner surface of the purification system pipe 18 (see FIG. 15). The nickel ferrite film 82 covers the entire inner surface of the purification system pipe 18 covered by the nickel metal film 80. Platinum 81 adheres on the nickel ferrite film 82.
  • Nickel ferrite having x of 0 in the formed Ni 1-x Fe 2 + x O 4 is formed under a high temperature environment of about 201 ° C., so that the crystal is larger than Ni 0.7 Fe 2.3 O 4 ing.
  • the heating system is removed from the piping system (step S18).
  • a film 82 of nickel ferrite in which x is 0 in Ni 1-x Fe 2 + x O 4 is formed to cover the inner surface of the purification system pipe 18, the heating system 90 connected to the purification system pipe 18 is a purification system pipe Removed from 18
  • One end of the circulation pipe 91 of the heating system 90 is removed from the flange of the valve 23, and the other end of the circulation pipe 91 is removed from the flange of the valve 25. Thereafter, the purification system piping 18 is restored.
  • a purification system piping 18 in which a nickel ferrite film 82 to which platinum 81 is attached is formed on the inner surface to enter the operation in the next operation cycle.
  • the BWR plant 1 is activated.
  • the reactor water flowing in the purification system pipe 18 is not in direct contact with the base material of the purification system pipe 18 because the nickel ferrite film 82 is formed.
  • the present embodiment can obtain the effects produced in the first embodiment.
  • the nickel ferrite film 82 formed of the nickel metal film 80 and having x of 0 in Ni 1-x Fe 2 + x O 4 has the effect of the deposited platinum 81 even during the operation of the BWR plant 1. Is a stable nickel ferrite film which does not elute into reactor water.
  • a stable nickel ferrite film 82 which does not elute into reactor water due to the action of platinum 81 even during operation of the BWR plant 1 can be formed on the inner surface of the purification system pipe 18.
  • the stable nickel ferrite film 82 which does not elute into the reactor water due to the action of the deposited platinum 81 lasts longer than the Ni 0.7 Fe 2.3 O 4 film formed at a low temperature range of 60 ° C. to 100 ° C.
  • the adhesion of the radionuclide to the purification system pipe 18 can be suppressed.
  • the stable nickel ferrite film 82 formed on the inner surface of the purification system pipe 18 can suppress the adhesion of radionuclides to the purification system pipe 18 over a plurality of operation cycles. For this reason, the number of times of chemical decontamination performed on the purification system pipe 18 can be reduced.
  • the adhesion between the nickel metal film 80 and the base material of the purification system pipe 18 is strong, the adhesion between the nickel ferrite film 82 generated in this embodiment and the base material of the purification system pipe 18 is also strong. Become. The nickel ferrite film 82 also does not peel off from the purification system pipe 18.
  • the formation of the nickel metal film 80 on the inner surface of the purification system pipe 18 and the adhesion of the platinum 81 to the nickel metal film 80 are performed after the shutdown of the BWR plant 1 and before restart of the BWR plant 1. Since the conversion to the nickel ferrite film 82 of the nickel metal film 80 is performed during the shutdown, and also the conversion of the nickel metal film 80 to the nickel ferrite film 82 is performed during shutdown of the BWR plant 1, the reactor power is 100 It is possible to suppress the adhesion of radionuclides to the purification system piping 18 at the time of startup of the BRW plant 1 which is% output.
  • a stable nickel ferrite film 82 which is not eluted even by the action of platinum covers the inner surface of the purification system pipe 18 and platinum 81 adheres to the surface of the nickel ferrite film 82.
  • the corrosion potential of the purification system pipe 18 and the nickel ferrite film 82 is lowered by the action of platinum 81 adhered to the nickel ferrite film 82, and the radiation to the purification system pipe 18 and the nickel ferrite film 82 is There is no uptake of nuclides.
  • hydrogen is injected into the reactor water during the operation of the BWR plant 1
  • the corrosion potential of the purification system pipe 18 and the nickel ferrite film 82 is lowered, and the uptake of radionuclides into these does not occur.
  • FIG. 16 is a flow chart showing the procedure of the method of depositing the noble metal on the carbon steel member of the nuclear power plant of the third embodiment.
  • the method of suppressing adhesion of radionuclides to the carbon steel member of the present embodiment is applied to the purification system piping of a BWR plant.
  • each step of steps S1 to S14 in the method for adhering a noble metal to a carbon steel member of a nuclear power plant of the first embodiment and new steps S15, S19 and Each step of S20 is performed.
  • the film forming apparatus 30 used in the first embodiment is used in each of steps S1 to S14.
  • each step of steps S15 to S18 in the method for suppressing adhesion of radionuclides to the carbon steel member of Example 2 is S15, S19 and S20. It is the method replaced with the process.
  • step S15 the film forming apparatus is removed from the piping system (step S15).
  • step S14 the film forming device 30 connected to the purification system piping 18 is removed from the purification system piping 18 as in the second embodiment. Then, the purification system piping 18 is restored.
  • the nuclear plant is started (step S19). After the end of refueling and maintenance inspection of the BWR plant 1, the BWR plant 1 having the purification system pipe 18 having the nickel metal film 80 formed on the inner surface is started to enter the operation in the next operation cycle. Be done.
  • the reactor water of 200 ° C. or more is brought into contact with the platinum-deposited nickel metal film (step S20).
  • the reactor water in the RPV 3 is pressurized by the recirculation pump 7 and is jetted into the jet pump 5 through the recirculation system pipe 6.
  • Reactor water present in the downcomer around the nozzle of the jet pump 5 is also drawn into the jet pump 5 and supplied to the core 4.
  • Reactor water discharged from the core is returned to the downcomer.
  • Control rods (not shown) are withdrawn from the core 4 to bring the core 4 from a subcritical state to a critical state, and the reactor water in the core 4 is heated by the heat generated by the nuclear fission of the nuclear fuel material in the fuel rods.
  • the rated operation of the BWR plant 1 maintaining the rated output is continued until the end of the operating cycle.
  • the reactor power rises, for example, to 10% power the steam generated in the core 4 is supplied to the turbine 9 through the main steam piping 8 to start power generation.
  • the reactor water 86 contains oxygen and hydrogen peroxide. Oxygen and hydrogen peroxide are generated by radiolysis of the reactor water 86 in the RPV 3.
  • the reactor water 86 in the RPV 3 is led from the recirculation system pipe 6 into the purification system pipe 18 and contacts the nickel metal film 80 to which platinum 81 adheres formed on the inner surface of the purification system pipe 18 (FIG. 13) reference).
  • the temperature of the reactor water 86 in contact with the nickel metal film 80 is raised by heating the reactor water due to the heat generated by the above-mentioned nuclear fission, and eventually becomes 200 ° C. or higher, 280 It rises to ° C.
  • the temperature of the reactor water 86 becomes 200 ° C.
  • the temperature of each of the purification system piping 18 surrounded by the nickel metal film 80 and the heat insulating material also becomes 200 ° C. or more.
  • oxygen contained in the reactor water 86 is transferred into the nickel metal film 80, and Fe contained in the purification system pipe 18 is converted into Fe 2+ to be transferred into the nickel metal film 80 (see FIG. 14).
  • the corrosion potential of the cleaning system pipe 18 and the nickel metal film 80 is reduced by the action of platinum 81 attached to the nickel metal film 80.
  • the nickel in the nickel metal film 80 reacts with migrated oxygen and Fe 2 + to obtain Ni 1 nickel ferrite in the -x Fe 2 + x O 4 x is 0 (NiFe 2 O 4) is generated.
  • the nickel metal film 80 formed on the inner surface of the purification system pipe 18 is converted into the film 82 of nickel ferrite, and the nickel ferrite film 82 covers the inner surface of the purification system pipe 18 (see FIG. 15).
  • the nickel ferrite film 82 covers the entire inner surface of the purification system pipe 18 covered by the nickel metal film 80.
  • Platinum 81 adheres on the nickel ferrite film 82.
  • the present embodiment can obtain each effect produced in the second embodiment. Furthermore, in the present embodiment, as in the second embodiment, the work of connecting the heating system 90 to the purification system piping 18 after removing the film forming apparatus 30 from the purification system piping 18, and the nickel ferrite film 82 is a purification system piping. It is not necessary to remove the heating system 90 from the purification system pipe 18 after it has been formed on the inner surface of the P.18. After removing the film forming apparatus 30 from the purification system pipe 18, just by starting the BWR plant 1, the platinum 81 is adhered to the nickel metal film 80 formed on the inner surface of the purification system pipe 18 and to which platinum 81 is adhered. It can be changed to a nickel ferrite film 82.
  • the time required for the formation of a stable nickel ferrite film 82 which does not elute in the reactor water 86 even by the adhered platinum on the inner surface of the purification system piping 18 is controlled by connecting the heating system 90 to the purification system piping 18 and heating
  • the system 90 can be shortened as compared with the second embodiment as it does not carry out each operation of removing it from the purification system piping 18.
  • the formation of the nickel metal film 80 on the inner surface of the purification system pipe 18 and the adhesion of the platinum 81 to the nickel metal film 80 are performed during shutdown of the BWR plant 1 as in the second embodiment.
  • the conversion of the nickel metal film 80 into the nickel ferrite film 82 is performed at the start of the BWR plant 1. Therefore, when the temperature of the reactor water is less than 200 ° C., the nickel metal film 80 is not changed to the nickel ferrite film 82, and the inner surface of the purification system pipe 18 is covered with the nickel metal film 80 to which platinum 81 adheres. (See FIG. 13).
  • the reactor water 86 when the reactor water 86 is in contact with the nickel metal film 80, nickel contained in the nickel metal film 80, which is a very small amount, is eluted in the reactor water 86.
  • the period of time in which the reactor water 86 contacts the nickel metal film 80 is extended, for example, the nickel metal film 80 may disappear over the period of one operation cycle.
  • the temperature of the reactor water 86 reaches 200 ° C. or more in the temperature rising and pressurizing step at the start of the BWR plant 1, the platinum 81 adheres and contacts the reactor water 86 as described above.
  • the nickel metal film 80 Since the nickel metal film 80 is changed to the nickel ferrite film 82, a stable nickel ferrite film 82 which is not eluted even by the action of the platinum 81 covers the inner surface of the purification system pipe 18 during most of the operation cycle.
  • the adhesion of the radionuclide to the purification system pipe 18 is suppressed by the nickel ferrite film 82 to which the platinum 81 adheres.
  • the period in which the temperature of the reactor water 86 is less than 200 ° C., in which the nickel metal film 80 covers the inner surface of the purification system pipe 18, is an extremely short period in the period of one operation cycle. Therefore, the amount of nickel eluted from the nickel metal coating 80 into the reactor water 86 is very small, and the thickness of the nickel metal coating 80 hardly changes.
  • Each of the embodiments 1 to 3 can be applied to carbon steel members in contact with reactor water of pressurized water nuclear plants and Canadian heavy water cooled pressure tube nuclear plants.
  • FIG. 17 is a flow chart showing the procedure of the method of depositing a noble metal on a carbon steel member of a nuclear power plant of a fourth embodiment.
  • the method of suppressing adhesion of radionuclides to the carbon steel member of the present embodiment is applied to the purification system piping of a BWR plant.
  • step S24 of injecting the oxidizing agent is added before step S4 of injecting the stabilizer in the first embodiment.
  • FIG. 18 is a block diagram of a film forming apparatus used in Example 4.
  • a film forming apparatus 30 'shown in FIG. 18 is used in each of steps S1 to S14.
  • the film forming apparatus 30 of the present embodiment differs from the film forming apparatus 30 ′ of FIG. 5 in that the oxidant injection device 56 is connected to the circulation pipe 34 by the pipe 101. With this configuration, the oxidant injection device 56 can inject the oxidant into the circulation pipe 34 before injecting the stabilizer into the circulation pipe 34.
  • step S24 the iron oxalate formed on the surface of the carbon steel after completion of step S23 is reformed into iron hydroxide by bringing an oxidant (hydrogen peroxide) into contact with the iron oxalate. Since iron hydroxide is more easily substituted by Ni ions than iron oxalate, formation of a Ni metal film is promoted.
  • FIG. 19 is a graph showing the amounts of Ni metal films formed in Example 1 and Example 4. As shown in FIG. 19, it can be seen that the formation amount of Ni metal is increased to 5 times that of Example 1 by the method of Example 4.
  • the other construction procedures and the Co-60 adhesion suppression mechanism are the same as in the other examples.
  • the present invention it is possible to provide a method of depositing a noble metal on a carbon steel member of a nuclear power plant, which can reduce the time required for depositing the noble metal on the carbon steel member of a nuclear power plant. It has been demonstrated that it is possible to provide a method for suppressing the adhesion of radionuclides to carbon steel members of nuclear power plants, which can sustain the effect of suppressing the adhesion of radionuclides to carbon steel members of nuclear power plants over a longer period of time.
  • the present invention is not limited to the embodiments described above, but includes various modifications.
  • the embodiments described above are described in detail in order to explain the present invention in an easy-to-understand manner, and are not necessarily limited to those having all the configurations described.
  • part of the configuration of one embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of one embodiment.
  • Injection pump 40: reducing agent injection device, 45: platinum ion injection device, 51, 93: heater, 52: cooler, 53: cation exchange resin tower, 54: mixed bed resin tower, 55: decomposition device, 56: Oxidizer injection device 58: supply pump 80: nickel metal film 81: platinum 82: nickel ferrite film 90: heating system 202: stabilizer injection device.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Chemically Coating (AREA)

Abstract

L'invention concerne un procédé qui permet de faire adhérer un métal noble à un élément en acier au carbone d'une centrale nucléaire, ce qui permet de réduire le temps nécessaire à l'adhérence de métal noble sur l'élément en acier au carbone. Ce procédé qui permet de faire adhérer un métal noble à un élément en acier au carbone d'une centrale nucléaire comprend les étapes suivantes : (S4) l'utilisation d'un stabilisant pouvant former un complexe ayant des ions nickel sur une surface qui est sur un élément en acier au carbone d'une centrale nucléaire et qui doit entrer en contact avec de l'eau de refroidissement, (S5) l'utilisation d'une solution comprenant des ions nickel à la surface et l'adhérence d'un complexe formé à partir des ions nickel et du stabilisant à la surface, (S6) l'utilisation d'un premier agent réducteur à la surface et la formation d'un film métallique de nickel sur la surface par la réduction des ions nickel dans le complexe, (S10) l'utilisation d'une solution comprenant des ions de métal noble à la surface et l'adhérence des ions de métal noble à la surface du film métallique de nickel, et (S11) l'utilisation d'un second agent réducteur à la surface et l'adhérence d'un métal noble à la surface du film métallique de nickel par réduction des ions de métal noble.
PCT/JP2018/039314 2017-11-22 2018-10-23 Procédé d'adhérence d'un métal noble à un élément en acier au carbone d'une centrale nucléaire et procédé de suppression de l'adhérence de radionucléides à un élément en acier au carbone d'une centrale nucléaire Ceased WO2019102768A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-224592 2017-11-22
JP2017224592A JP2019095283A (ja) 2017-11-22 2017-11-22 原子力プラントの炭素鋼部材への貴金属の付着方法及び原子力プラントの炭素鋼部材への放射性核種の付着抑制方法

Publications (1)

Publication Number Publication Date
WO2019102768A1 true WO2019102768A1 (fr) 2019-05-31

Family

ID=66631575

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/039314 Ceased WO2019102768A1 (fr) 2017-11-22 2018-10-23 Procédé d'adhérence d'un métal noble à un élément en acier au carbone d'une centrale nucléaire et procédé de suppression de l'adhérence de radionucléides à un élément en acier au carbone d'une centrale nucléaire

Country Status (2)

Country Link
JP (1) JP2019095283A (fr)
WO (1) WO2019102768A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10339793A (ja) * 1997-06-06 1998-12-22 Toshiba Corp 水質制御システムおよび水質制御方法
US20020101953A1 (en) * 1998-10-13 2002-08-01 General Electric Company Application of noble metals to internal surfaces of operating boiling water reactors in the presence of zinc in reactor water
JP2003535311A (ja) * 1999-12-30 2003-11-25 ゼネラル・エレクトリック・カンパニイ 水冷型原子炉用の貴金属付着操作に関して適正な貴金属付加量を維持するための方法及びシステム
JP2011032551A (ja) * 2009-08-04 2011-02-17 Hitachi-Ge Nuclear Energy Ltd 炭素鋼部材の防食方法
JP2014182020A (ja) * 2013-03-19 2014-09-29 Toshiba Corp 放射性物質付着抑制方法
JP2016161466A (ja) * 2015-03-04 2016-09-05 日立Ｇｅニュークリア・エナジー株式会社 原子力プラントの構造部材への放射性核種付着抑制方法
JP2016201364A (ja) * 2016-06-09 2016-12-01 日本化学工業株式会社 導電性粒子及びそれを含む導電性材料
JP2017020786A (ja) * 2015-07-07 2017-01-26 日立Ｇｅニュークリア・エナジー株式会社 原子力プラントの構造部材への貴金属付着方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10339793A (ja) * 1997-06-06 1998-12-22 Toshiba Corp 水質制御システムおよび水質制御方法
US20020101953A1 (en) * 1998-10-13 2002-08-01 General Electric Company Application of noble metals to internal surfaces of operating boiling water reactors in the presence of zinc in reactor water
JP2003535311A (ja) * 1999-12-30 2003-11-25 ゼネラル・エレクトリック・カンパニイ 水冷型原子炉用の貴金属付着操作に関して適正な貴金属付加量を維持するための方法及びシステム
JP2011032551A (ja) * 2009-08-04 2011-02-17 Hitachi-Ge Nuclear Energy Ltd 炭素鋼部材の防食方法
JP2014182020A (ja) * 2013-03-19 2014-09-29 Toshiba Corp 放射性物質付着抑制方法
JP2016161466A (ja) * 2015-03-04 2016-09-05 日立Ｇｅニュークリア・エナジー株式会社 原子力プラントの構造部材への放射性核種付着抑制方法
JP2017020786A (ja) * 2015-07-07 2017-01-26 日立Ｇｅニュークリア・エナジー株式会社 原子力プラントの構造部材への貴金属付着方法
JP2016201364A (ja) * 2016-06-09 2016-12-01 日本化学工業株式会社 導電性粒子及びそれを含む導電性材料

Also Published As

Publication number Publication date
JP2019095283A (ja) 2019-06-20

Similar Documents

Publication Publication Date Title
JP6620081B2 (ja) 原子力プラントの炭素鋼部材への貴金属の付着方法及び原子力プラントの炭素鋼部材への放射性核種の付着抑制方法
JP2012247322A (ja) プラント構成部材への白金皮膜形成方法
JP6619717B2 (ja) 原子力プラントの炭素鋼部材への貴金属の付着方法及び原子力プラントの炭素鋼部材への放射性核種の付着抑制方法
JP2016102727A (ja) 原子力プラントの炭素鋼部材への放射性核種付着抑制方法及び皮膜形成装置
JP6931622B2 (ja) 原子力プラントの炭素鋼部材への貴金属の付着方法及び原子力プラントの炭素鋼部材への放射性核種の付着抑制方法
JP5500958B2 (ja) 原子力部材へのフェライト皮膜形成方法、応力腐食割れの進展抑制方法及びフェライト成膜装置
JP6751044B2 (ja) 原子力プラントの炭素鋼部材への貴金属の付着方法、及び原子力プラントの炭素鋼部材への放射性核種の付着抑制方法
JP7344132B2 (ja) 原子力プラントの炭素鋼部材への貴金属付着方法及び原子力プラントの炭素鋼部材への放射性核種の付着抑制方法
JP2009210307A (ja) 原子力プラント構成部材への放射性核種の付着抑制方法及びフェライト皮膜形成装置
JP6868545B2 (ja) プラントの炭素鋼部材の腐食抑制方法
JP7104616B2 (ja) 原子力プラントの炭素鋼部材への放射性核種の付着抑制方法
JP6059106B2 (ja) 原子力プラントの炭素鋼部材の化学除染方法
JP7142587B2 (ja) 原子力プラントの炭素鋼部材への貴金属付着方法及び原子力プラントの炭素鋼部材への放射性核種の付着抑制方法
WO2019102768A1 (fr) Procédé d'adhérence d'un métal noble à un élément en acier au carbone d'une centrale nucléaire et procédé de suppression de l'adhérence de radionucléides à un élément en acier au carbone d'une centrale nucléaire
JP2017122593A (ja) 放射性核種の付着抑制方法、及び炭素鋼配管への皮膜形成装置
JP6894862B2 (ja) 原子力プラントの炭素鋼部材への放射性核種付着抑制方法
JP6751010B2 (ja) 放射性物質付着抑制皮膜の形成方法
JP2016099159A (ja) 炭素鋼部材への放射性核種の付着抑制方法及びその装置
JP7001534B2 (ja) 原子力プラントの構造部材への放射性核種の付着抑制方法
JP2016003940A (ja) 原子力プラントの炭素鋼部材への放射性核種付着抑制方法
JP7475171B2 (ja) 化学除染方法および化学除染装置
JP2020160030A (ja) 原子力プラント構成部材の線量抑制方法
JP2019157215A (ja) プラントの炭素鋼部材の腐食抑制方法
JP2019164059A (ja) 原子力プラントの炭素鋼部材への放射性核種の付着抑制方法
JP5645759B2 (ja) 原子力プラント構成部材の線量低減方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18882024

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18882024

Country of ref document: EP

Kind code of ref document: A1