EP0180826B1 - Procédé pour décontaminer chimiquement les composants importants et les système métalliques des réacteurs nucléaires - Google Patents

Procédé pour décontaminer chimiquement les composants importants et les système métalliques des réacteurs nucléaires Download PDF

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Publication number
EP0180826B1
EP0180826B1 EP85113144A EP85113144A EP0180826B1 EP 0180826 B1 EP0180826 B1 EP 0180826B1 EP 85113144 A EP85113144 A EP 85113144A EP 85113144 A EP85113144 A EP 85113144A EP 0180826 B1 EP0180826 B1 EP 0180826B1
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EP
European Patent Office
Prior art keywords
ozone
process according
primary coolant
decontamination
systems
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.)
Expired - Lifetime
Application number
EP85113144A
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German (de)
English (en)
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EP0180826A1 (fr
Inventor
Horst-Otto Bertholdt
Bernhard Dipl.-Ing. Kress (Fh)
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.)
Siemens AG
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Siemens AG
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Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP0180826A1 publication Critical patent/EP0180826A1/fr
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/001—Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
    • G21F9/002—Decontamination of the surface of objects with chemical or electrochemical processes
    • G21F9/004—Decontamination of the surface of objects with chemical or electrochemical processes of metallic surfaces

Definitions

  • the invention relates to a method for the chemical decontamination of large components and systems made of metallic materials of nuclear reactors with a liquid primary coolant.
  • a decontamination process known from DE-OS-26 13 351 is a multi-stage process in which oxidative treatments and acid treatments are carried out alternately at temperatures above 90 ° C.
  • the ongoing change of chemicals requires a relatively large amount of time, chemicals and energy.
  • a multi-stage process is also known from the older European patent application 84304726.7 with the publication number 0134 664, a process step of the multi-stage process being described in more detail.
  • the oxidation step explained in more detail is preceded by a decontamination step with organic acids.
  • a cerium IV compound is used only in the second process step.
  • WO-A-84/03 170 describes a multi-stage process which provides at least two process steps. First, an oxidation step makes corrosion products acid-soluble. This is followed by the addition of an acidic decontamination solution in an acid treatment step. Among other things, permanganate and chromic acid and ozone are used to carry out the process.
  • Multi-stage decontamination processes require that all the chemicals required for this have to be removed from the container to be decontaminated after each stage or after each process step. Only then can the second process step be initiated. A rinsing step is often necessary as an intermediate step to remove chemical residues.
  • Multi-stage processes require a lot of time and leave a lot of secondary waste.
  • the invention was based on the object of proposing a method for chemical decontamination with which decontamination can be carried out quickly, the decontamination effect is increased compared to the known method and, at the same time, the amount of secondary waste is reduced.
  • the treatment temperature should be less than or equal to 50 ° C.
  • the object is achieved according to the invention by a process for the chemical decontamination of large components and systems made of metallic materials of nuclear reactors with a liquid primary coolant, the treatment being carried out as a one-step treatment without an acid treatment step using an aqueous solution of oxidizing chemicals which are contaminated by the large components and Systems is moved, with nitrates, chromates or cerium IV salts and additionally ozone being added to the primary coolant, which contains borate in particular, as oxidizing chemicals.
  • the decontamination is carried out as a one-step treatment using an aqueous solution of oxidizing chemicals with the additional addition of ozone.
  • the oxidizing chemicals for example nitrates, chromates, cerium salts are inexpensive and lead to ions that can be easily removed with ion exchange resins.
  • the pH value is lowered during the decontamination by withdrawing the cations using an ion exchanger.
  • the concentration range of the oxidizing chemicals is preferably 100-1000 mg kg- 1 , of ozone 10-40 mg kg- '.
  • the effectiveness of the solution is monitored by measuring the red-ox potential.
  • the ozone content is maintained according to the further invention by means of an external ozone enrichment path.
  • continuous degassing advantageously prevents gas cushions from forming in the system to be decontaminated.
  • the ozone fed in comes from an ozone generator 8, which is supplied with oxygen from the tank 9. This is partly converted into ozone by means of silent electrical discharge.
  • the gas containing ozone is sucked into the enrichment section 5 by the injector 6. The mass transfer between gas and liquid takes place in the injector 6 and in the subsequent liquid column.
  • Excess oxygen present in the decontamination circuit and the non-absorbed ozone from the enrichment section 5 are released from their upper end via an aerosol separator 10 and, after heating in a heating device 11, via a catalytic ozone destruction system 12.
  • the cations formed during the decontamination and the dissolved activity are withdrawn via ion exchangers 13 in a second bypass with a pump 14.
  • the ion exchangers 13 are then disposed of using known measures, for example dried and solidified with bitumen.

Landscapes

  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Claims (13)

1. Procédé de décontamination chimique d'éléments de grandes dimensions et de systèmes en matériaux métalliques de réacteurs nucléaires à agent de refroidissement primaire liquide, le traitement étant effectué sous la forme d'un traitement à un seul stade, sans phases de traitement acide, au moyen d'une solution aqueuse de produits chimiques oxydants, qui est mise en mouvement dans les éléments de grandes dimensions et les systèmes à décontaminer, en chargeant comme produits chimiques oxydants des nitrates, des chromates, ou des sels de Cer-IV et, en outre, de l'ozone, dans l'argent de refroidissement primaire contenant notamment un borate.
2. Procédé suivant la revendication 1, caractérisé en ce qu'il consiste à utiliser de l'ozone dans une plage de concentration de 10 à 40 mg kg-'.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce qu'il consiste à alimenter l'agent de refroidissement primaire en ozone, d'une manière continue, par une zone d'enrichissement en ozone.
4. Procédé suivant la revendication 3, caractérisé en ce que l'enrichissement en ozone a lieu par un injecteur, par une colonne à bulles, ou par un réacteur en aval à colonne à bulles.
5. Procédé suivant la revendication 4, caractérisé en ce qu'il consiste à effectuer, en amont, dans le sens de l'écoulement, de l'endroit de l'enrichissement en ozone, un dégazage continu d'élimination de l'oxygène et de l'ozone avec destruction ultérieure de l'ozone.
6. Procédé suivant la revendication 5, caractérisé en ce qu'il consiste à effectuer la destruction de l'ozone par voie catalytique.
7. Procédé suivant l'une des revendications 1 à 6, caractérisé en ce qu'il consiste à contrôler l'efficacité de la solution de décontamination par détection du potentiel rédox.
8. Procédé suivant l'une des revendications 1 à 7, caractérisé en ce qu'il consiste à surveiller analytiquement et en continu la concentration de l'ozone dissoute.
9. Procédé suivant la revendication 8, caractérisé en ce qu'il consiste à effectuer la surveillance continue par voie photométrique sur un courant partiel séparé par entraînement par de l'air.
10. Procédé suivant l'une des revendications 1 à 9, caractérisé en ce qu'il consiste à enlever l'activité dissoute de l'agent de refroidissement primaire en continu, au moyen d'un échange d'ion.
11. Procédé suivant la revendication 10, caractérisé en ce qu'il consiste à enlever aux produits chimiques oxydants leurs cations, pendant la décontamination.
12. Procédé suivant l'une des revendications 1 à 11, caractérisé en ce qu'il consiste à utiliser les produits chimiques oxydants en une plage de concentration de 100 à 1000 mg kg-'.
13. Procédé suivant l'une des revendications 1 à 12, caractérisé en ce qu'il consiste à maintenir l'agent de refroidissement primaire, lors du traitement, à des températures de 20 à 60°C.
EP85113144A 1984-10-31 1985-10-16 Procédé pour décontaminer chimiquement les composants importants et les système métalliques des réacteurs nucléaires Expired - Lifetime EP0180826B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3439857 1984-10-31
DE3439857 1984-10-31

Publications (2)

Publication Number Publication Date
EP0180826A1 EP0180826A1 (fr) 1986-05-14
EP0180826B1 true EP0180826B1 (fr) 1990-07-11

Family

ID=6249196

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85113144A Expired - Lifetime EP0180826B1 (fr) 1984-10-31 1985-10-16 Procédé pour décontaminer chimiquement les composants importants et les système métalliques des réacteurs nucléaires

Country Status (5)

Country Link
US (1) US4942594A (fr)
EP (1) EP0180826B1 (fr)
JP (1) JPS61110100A (fr)
DE (1) DE3578635D1 (fr)
ES (1) ES8700486A1 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0278256A1 (fr) * 1987-01-28 1988-08-17 Siemens Aktiengesellschaft Procédé et dispositif pour éliminer les couches d'oxydes
EP0355628B1 (fr) * 1988-08-24 1993-11-10 Siemens Aktiengesellschaft Procédé pour décontaminer chimiquement la surface d'un élément de construction métallique d'une installation de réacteur nucléaire
DE3919885C2 (de) * 1989-06-19 1994-06-30 Wedeco Umwelttechnologien Wass Verfahren und Anlage zur Behandlung von mit schwer abbaubaren Schadstoffen belasteten wässrigen Flüssigkeiten
US5205999A (en) * 1991-09-18 1993-04-27 British Nuclear Fuels Plc Actinide dissolution
US5244000A (en) * 1991-11-13 1993-09-14 Hughes Aircraft Company Method and system for removing contaminants
FR2689298B1 (fr) * 1992-03-24 1994-10-21 Framatome Sa Procédé d'élimination de dépôts de corrosion dans la partie secondaire d'un générateur de vapeur d'un réacteur nucléaire refroidi par de l'eau sous pression.
FR2701155B1 (fr) * 1993-02-02 1995-04-21 Framatome Sa Procédé et installation de décontamination de couvercles usagés de cuves de réacteurs nucléaires à eau légère.
BE1011754A3 (fr) * 1998-02-20 1999-12-07 En Nucleaire Etabilissement D Procede et installation de decontamination de surfaces metalliques.
DE19818772C2 (de) * 1998-04-27 2000-05-31 Siemens Ag Verfahren zum Abbau der Radioaktivität eines Metallteiles
US6635232B1 (en) * 1999-05-13 2003-10-21 Kabushiki Kaisha Toshiba Method of chemically decontaminating components of radioactive material handling facility and system for carrying out the same
JP3977963B2 (ja) * 1999-09-09 2007-09-19 株式会社日立製作所 化学除染方法
US6466636B1 (en) * 2000-07-26 2002-10-15 Westinghouse Electric Company Llc Decontamination method
TW529041B (en) * 2000-12-21 2003-04-21 Toshiba Corp Chemical decontamination method and treatment method and apparatus of chemical decontamination solution
JP3849925B2 (ja) * 2000-12-21 2006-11-22 株式会社東芝 化学除染方法
KR100724710B1 (ko) * 2002-11-21 2007-06-04 가부시끼가이샤 도시바 방사화 부품의 화학적 오염제거 시스템 및 방법
JP2004191259A (ja) * 2002-12-12 2004-07-08 Toshiba Corp 化学除染方法
JP3945780B2 (ja) * 2004-07-22 2007-07-18 株式会社日立製作所 原子力プラント構成部材の放射性核種の付着抑制方法および成膜装置
JP6901947B2 (ja) * 2017-09-29 2021-07-14 三菱重工業株式会社 化学除染方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1517664C3 (de) * 1965-02-27 1978-08-24 Gesellschaft Fuer Kernforschung Mbh, 7500 Karlsruhe Verfahren zum Dekontaminieren radioaktiver Wasser in Anwesenheit von Störsubstanzen
DE2613351C3 (de) * 1976-03-29 1982-03-25 Kraftwerk Union AG, 4330 Mülheim Verfahren zur chemischen Dekontamination von metallischen Bauteilen von Kernreaktoranlagen
CH619807A5 (fr) * 1976-04-07 1980-10-15 Foerderung Forschung Gmbh
US4226640A (en) * 1978-10-26 1980-10-07 Kraftwerk Union Aktiengesellschaft Method for the chemical decontamination of nuclear reactor components
US4287002A (en) * 1979-04-09 1981-09-01 Atomic Energy Of Canada Ltd. Nuclear reactor decontamination
US4284428A (en) * 1980-10-29 1981-08-18 Western Electric Co., Inc. Separation of contaminant material from copper wire and cable
SE435329B (sv) * 1983-02-09 1984-09-17 Studsvik Energiteknik Ab Dekontaminering av tryckvattenreaktorer
CA1229480A (fr) * 1983-07-12 1987-11-24 Alexander P. Murray Reduction a l'ozone des depots dans les circuits de refroidissement de reacteurs nucleaires
US4685971A (en) * 1983-07-12 1987-08-11 Westinghouse Electric Corp. Ozone oxidation of deposits in cooling systems of nuclear reactors
US4481090A (en) * 1984-01-23 1984-11-06 The United States Of America As Represented By The United States Department Of Energy Decontaminating metal surfaces

Also Published As

Publication number Publication date
EP0180826A1 (fr) 1986-05-14
ES548371A0 (es) 1986-10-16
ES8700486A1 (es) 1986-10-16
US4942594A (en) 1990-07-17
DE3578635D1 (de) 1990-08-16
JPS61110100A (ja) 1986-05-28

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