EP1082728B1 - Verfahren zum abbau der radioaktivität eines metallteiles - Google Patents

Verfahren zum abbau der radioaktivität eines metallteiles Download PDF

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Publication number
EP1082728B1
EP1082728B1 EP99927700A EP99927700A EP1082728B1 EP 1082728 B1 EP1082728 B1 EP 1082728B1 EP 99927700 A EP99927700 A EP 99927700A EP 99927700 A EP99927700 A EP 99927700A EP 1082728 B1 EP1082728 B1 EP 1082728B1
Authority
EP
European Patent Office
Prior art keywords
agents
metal
decontamination solution
oxidizing
decontamination
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
EP99927700A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1082728A1 (de
Inventor
Horst-Otto Bertholdt
Rainer Gassen
Franz Strohmer
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.)
Areva GmbH
Original Assignee
Framatome ANP GmbH
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Filing date
Publication date
Application filed by Framatome ANP GmbH filed Critical Framatome ANP GmbH
Publication of EP1082728A1 publication Critical patent/EP1082728A1/de
Application granted granted Critical
Publication of EP1082728B1 publication Critical patent/EP1082728B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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 reducing radioactivity of a metal part, with a decontamination solution an oxide layer is removed from the metal part.
  • a process for the chemical decontamination of surfaces metallic components of nuclear reactor plants is for example known from EP 0 355 628 B1.
  • the goal of such The procedure is to remove the surface of metallic components from a rid radioactive contaminated oxide layer.
  • the z.3. Contains oxalic acid or another carboxylic acid.
  • radionuclides are mainly stored in the oxidic Protective layers that are metallic on the surfaces Components.
  • oxidic Protective layers that are metallic on the surfaces Components.
  • decontamination work during a normal revision of a nuclear power plant consequently removing the oxide layer.
  • suitable decontamination solution selected so that the Base metal of the components is not attacked.
  • the invention was based on the object of specifying a method with which it is possible to contaminate radioactive metal rid of radionuclides so far that it is considered inactive Scrap can be fed into the usual material cycle.
  • the redox potential in the decontamination solution becomes average lowered and there is also the corrosion potential of the base metal reduced. As a result, an attack on the base metal is made specifically. Doing some Micrometer of the base metal removed.
  • the advantage of the method according to the invention is achieved, that the targeted base metal attack the radionuclides be separated from the metal. It advantageously remains Metal scrap, which is, as usual, inactive scrap can be treated further. On the other hand, no more Base metal removed as necessary, so that little waste one Repository must be supplied.
  • Agents having an oxidizing action and which are removed from the decontamination solution are, for example, Fe 3+ and / or residual oxygen.
  • the oxidizing Fe 3+ comes from the oxide layer, which was detached from the metal surface in a previous decontamination step.
  • a reducing agent for example, is added to the decontamination solution.
  • the interfering Fe 3+ can be converted into non-interfering Fe 2+ .
  • This reducing agent can be ascorbic acid.
  • the decontamination solution can also be used with a Be gassed with inert gas. This will make the one that still exists Residual oxygen expelled.
  • a suitable inert gas is, for example Nitrogen.
  • the decontamination solution is irradiated with UV light in order to remove oxidizing agents.
  • the disruptive Fe 3+ and existing organic decontamination acid produce Fe 2+ and carbon dioxide when exposed to UV radiation.
  • the Fe 2+ formed in this way and the organic decontamination acid present then form Fe 3+ and carbon dioxide together with the disturbing residual oxygen when exposed to UV radiation. This reaction continues until there is no more oxygen.
  • the Fe 3+ formed is then converted into Fe 2+ and carbon dioxide after the first-mentioned reaction, so that only these two substances and no oxidizing agents are left.
  • Fe 2+ ions that are formed are removed with a cation exchanger.
  • a cation exchanger advantageously has a very large capacity. So you can get by with a small ion exchanger.
  • an anion exchanger would be required, since Fe 3+ forms organic complexes with organic decontamination acids, for example an oxalato complex, the capacity of which is significantly smaller than that of a cation exchanger.
  • the conversion of Fe 3+ into Fe 2+ also has the advantage that the remaining decontamination solution to be disposed of does not contain any chelates (complexes) which would have to be removed in a complex manner.
  • the decontamination solution can be used to improve the removal of base metal additionally nitric acid, e.g. in a concentration from 100 ppm to 10000 ppm can be added to the solution.
  • the removal process becomes oxidizing active agents not continued until no oxidizing agents Means more are available. This will be removing stopped, for example, by adding an oxidizing agent.
  • the oxidizing agent can e.g. Air, oxygen, iron (3) ions, Be hydrogen peroxide and / or ozone.
  • the base metal attack can be special advantageously only the exact amount of metal is removed, the radionuclides present in the near-surface area contains.
  • the treatment time and also the amount of waste to be disposed of, which is sent to a repository must be greatly minimized.
  • the basic metal removal can by alternating triggering and stopping in single Steps of up to a tenth of a micron can be controlled. Depending on requirements, up to several 100 micrometers can then be used or less.
  • the drawing shows the course of the corrosion potential of a metal part from triggering the removal oxidizing active agent from the decontamination solution until stopping of the process.
  • the lower curve shows the Base metal attack.
  • Period A During a normal decontamination process without attacking the base metal (Period A) is the corrosion potential about 200 mV. During this period A there is almost no base metal attack instead of what is a common decontamination process is also not desired.
  • Period B takes place a UV treatment, so that the corrosion potential drops to about -300 mV and the base metal attack rises slowly and then very quickly.
  • the desired base metal attack takes place in the following period C. instead, which contains at least some of the radionuclides Layer of the metal part is removed.
  • Period D becomes the base metal attack by adding Hydrogen peroxide stopped. The corrosion potential increases back to a value of almost 200 mV and the base metal attack goes back to a negligible value.
  • Period E can passivate the base metal respectively. But it can also be determined whether enough metal has been removed. The described procedure can join several times if necessary until the remaining one Metal is free of radionuclides and a common one Scrapping can be fed.

Landscapes

  • Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
EP99927700A 1998-04-27 1999-04-21 Verfahren zum abbau der radioaktivität eines metallteiles Expired - Lifetime EP1082728B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19818772 1998-04-27
DE19818772A DE19818772C2 (de) 1998-04-27 1998-04-27 Verfahren zum Abbau der Radioaktivität eines Metallteiles
PCT/DE1999/001203 WO1999056286A2 (de) 1998-04-27 1999-04-21 Verfahren zum abbau der radioaktivität eines metallteiles

Publications (2)

Publication Number Publication Date
EP1082728A1 EP1082728A1 (de) 2001-03-14
EP1082728B1 true EP1082728B1 (de) 2002-08-07

Family

ID=7865927

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99927700A Expired - Lifetime EP1082728B1 (de) 1998-04-27 1999-04-21 Verfahren zum abbau der radioaktivität eines metallteiles

Country Status (12)

Country Link
US (1) US6613153B1 (ja)
EP (1) EP1082728B1 (ja)
JP (1) JP3881515B2 (ja)
KR (1) KR100446810B1 (ja)
AR (1) AR016220A1 (ja)
BR (1) BR9909968B1 (ja)
CA (1) CA2329814C (ja)
DE (2) DE19818772C2 (ja)
ES (1) ES2180306T3 (ja)
MX (1) MXPA00010614A (ja)
TW (1) TW418404B (ja)
WO (1) WO1999056286A2 (ja)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013041595A1 (de) 2011-09-20 2013-03-28 Nis Ingenieurgesellschaft Mbh Verfahren zum abbau einer oxidschicht
DE102012023938A1 (de) 2012-12-06 2014-06-12 Kathrein-Werke Kg Dualpolarisierte, omnidirektionale Antenne
DE102013102331B3 (de) * 2013-03-08 2014-07-03 Horst-Otto Bertholdt Verfahren zum Abbau einer Oxidschicht
WO2018149862A1 (de) 2017-02-14 2018-08-23 Siempelkamp NIS Ingenieurgesellschaft mbH Verfahren zum abbau einer radionuklidhaltigen oxidschicht

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100724710B1 (ko) * 2002-11-21 2007-06-04 가부시끼가이샤 도시바 방사화 부품의 화학적 오염제거 시스템 및 방법
JP4083607B2 (ja) * 2003-03-19 2008-04-30 株式会社東芝 放射能の化学除染方法および装置
JP2013064696A (ja) * 2011-09-20 2013-04-11 Toshiba Corp 放射能汚染物の化学除染方法
TWI457948B (zh) * 2011-09-29 2014-10-21 Atomic Energy Council 化學及電化學除污裝置及其方法
JP6005425B2 (ja) * 2012-07-13 2016-10-12 株式会社東芝 放射能汚染物の化学除染方法
JP6591225B2 (ja) * 2015-08-03 2019-10-16 株式会社東芝 除染方法
DE102016104846B3 (de) * 2016-03-16 2017-08-24 Areva Gmbh Verfahren zur Behandlung von Abwasser aus der Dekontamination einer Metalloberfläche, Abwasserbehandlungsvorrichtung und Verwendung der Abwasserbehandlungsvorrichtung
JP6408053B2 (ja) * 2017-03-21 2018-10-17 株式会社東芝 ニッケル基合金除染方法
DE102017115122B4 (de) * 2017-07-06 2019-03-07 Framatome Gmbh Verfahren zum Dekontaminieren einer Metalloberfläche in einem Kernkraftwerk

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4226640A (en) * 1978-10-26 1980-10-07 Kraftwerk Union Aktiengesellschaft Method for the chemical decontamination of nuclear reactor components
DE3161291D1 (en) * 1980-01-08 1983-12-08 Central Electr Generat Board Descaling process
GB2085215A (en) * 1980-08-11 1982-04-21 Central Electr Generat Board An application technique for the decontamination of nuclear reactors
EP0071336B1 (en) * 1981-06-17 1986-03-26 Central Electricity Generating Board Process for the chemical dissolution of oxide deposits
JPS58213300A (ja) * 1982-06-04 1983-12-12 株式会社日立製作所 放射性廃棄物の処理方法
US4537666A (en) * 1984-03-01 1985-08-27 Westinghouse Electric Corp. Decontamination using electrolysis
SE451915B (sv) * 1984-03-09 1987-11-02 Studsvik Energiteknik Ab Forfarande for dekontaminering av tryckvattenreaktorer
DE3413868A1 (de) * 1984-04-12 1985-10-17 Kraftwerk Union AG, 4330 Mülheim Verfahren zur chemischen dekontamination von metallischen bauteilen von kernreaktoranlagen
DE3578635D1 (de) * 1984-10-31 1990-08-16 Kraftwerk Union Ag Verfahren zur chemischen dekontamination von grosskomponenten und systemen aus metallischen werkstoffen von kernreaktoren.
EP0355628B1 (de) * 1988-08-24 1993-11-10 Siemens Aktiengesellschaft Verfahren zur chemischen Dekontamination der Oberfläche eines metallischen Bauteils einer Kernreaktoranlage
FR2644618B1 (fr) * 1989-03-14 1994-03-25 Commissariat A Energie Atomique Procede de decontamination de surfaces metalliques, notamment de parties constitutives d'un reacteur nucleaire a eau sous pression, et solutions de decontamination utilisees dans ce procede
FR2648946B1 (fr) * 1989-06-27 1994-02-04 Electricite De France Procede de dissolution d'oxyde depose sur un substrat metallique et son application a la decontamination
JPH0695155B2 (ja) * 1990-03-15 1994-11-24 動力炉・核燃料開発事業団 高放射性廃棄物の処理方法
US5078894A (en) * 1990-04-30 1992-01-07 Arch Development Corporation Formulations for iron oxides dissolution
US5135709A (en) * 1991-05-13 1992-08-04 General Electric Company Method for reducing corrosion of components exposed to high-temperature water
DE4117625C2 (de) * 1991-05-29 1997-09-04 Siemens Ag Reinigungsverfahren
FR2699936B1 (fr) * 1992-12-24 1995-01-27 Electricite De France Procédé de dissolution d'oxydes déposés sur un substrat métallique.
US5958247A (en) * 1994-03-28 1999-09-28 Siemens Aktiengesellschaft Method for disposing of a solution containing an organic acid
DE4423398A1 (de) * 1994-07-04 1996-01-11 Siemens Ag Verfahren und Einrichtung zum Entsorgen eines Kationenaustauschers
GB9422539D0 (en) * 1994-11-04 1995-01-04 British Nuclear Fuels Plc Decontamination processes
GB9610647D0 (en) * 1996-05-21 1996-07-31 British Nuclear Fuels Plc Decontamination of metal
US6147274A (en) * 1996-11-05 2000-11-14 Electric Power Research Insitute Method for decontamination of nuclear plant components

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013041595A1 (de) 2011-09-20 2013-03-28 Nis Ingenieurgesellschaft Mbh Verfahren zum abbau einer oxidschicht
DE102012023938A1 (de) 2012-12-06 2014-06-12 Kathrein-Werke Kg Dualpolarisierte, omnidirektionale Antenne
DE102013102331B3 (de) * 2013-03-08 2014-07-03 Horst-Otto Bertholdt Verfahren zum Abbau einer Oxidschicht
US9502146B2 (en) 2013-03-08 2016-11-22 Horst-Otto Bertholdt Process for dissolving an oxide layer
WO2018149862A1 (de) 2017-02-14 2018-08-23 Siempelkamp NIS Ingenieurgesellschaft mbH Verfahren zum abbau einer radionuklidhaltigen oxidschicht

Also Published As

Publication number Publication date
CA2329814A1 (en) 1999-11-04
DE19818772A1 (de) 1999-11-04
JP3881515B2 (ja) 2007-02-14
DE19818772C2 (de) 2000-05-31
DE59902279D1 (de) 2002-09-12
WO1999056286A2 (de) 1999-11-04
US6613153B1 (en) 2003-09-02
WO1999056286A3 (de) 1999-12-23
ES2180306T3 (es) 2003-02-01
BR9909968B1 (pt) 2011-04-19
JP2002513163A (ja) 2002-05-08
KR20010071186A (ko) 2001-07-28
EP1082728A1 (de) 2001-03-14
BR9909968A (pt) 2000-12-26
KR100446810B1 (ko) 2004-09-01
AR016220A1 (es) 2001-06-20
TW418404B (en) 2001-01-11
CA2329814C (en) 2007-01-09
MXPA00010614A (es) 2002-06-04

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