EP1141445A1 - Procede de decontamination d'une surface d'un element - Google Patents

Procede de decontamination d'une surface d'un element

Info

Publication number
EP1141445A1
EP1141445A1 EP99960849A EP99960849A EP1141445A1 EP 1141445 A1 EP1141445 A1 EP 1141445A1 EP 99960849 A EP99960849 A EP 99960849A EP 99960849 A EP99960849 A EP 99960849A EP 1141445 A1 EP1141445 A1 EP 1141445A1
Authority
EP
European Patent Office
Prior art keywords
ions
iron
divalent iron
solution
base metal
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.)
Granted
Application number
EP99960849A
Other languages
German (de)
English (en)
Other versions
EP1141445B1 (fr
Inventor
Horst-Otto Bertholdt
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
Siemens AG
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 Siemens AG filed Critical Siemens AG
Publication of EP1141445A1 publication Critical patent/EP1141445A1/fr
Application granted granted Critical
Publication of EP1141445B1 publication Critical patent/EP1141445B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids
    • 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
    • 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
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange

Definitions

  • the invention relates to a method for the decontamination of a surface of a component made of steel, in particular of low or unalloyed steel, the surface being brought into contact with a solution which contains an organic acid and detaches a contaminated layer from the base metal of the component.
  • the invention is therefore based on the object of a method for decontaminating a surface of a component Specify steel that keeps the base metal attack very small, especially if the component consists of low or unalloyed steel.
  • the solution with which the surface of the component is brought into contact also contains ions of divalent iron, and thus immediately builds up a protective layer on parts of the base metal surface that have just been exposed, that after the closure the detachment of the contaminated layer, the protective layer is detached again by reducing the content of divalent iron ions in the solution, and that ions of the divalent iron that are no longer required and the substance that caused the contamination are bound to an ion exchange resin.
  • the advantage of the method according to the invention is that a protective layer is formed which, on the one hand, protects the base metal from attack during decontamination and, on the other hand, can be easily removed again at the end of the actual decontamination. Expensive inhibitors are advantageously not required, so that the amount of decontamination waste to be disposed of is minimized for this reason alone, but also because the base metal attack is largely avoided.
  • a suitable organic acid is, for example, oxalic acid, which is inexpensive.
  • the ions of divalent iron are added to the solution from the outside, for example.
  • An iron-2 salt is particularly suitable for this.
  • the iron 2 ions can be removed from the contaminated layer or from the base metal. There is only an insignificant removal of Base metal, since only relatively little iron 2 ions are needed.
  • a protective layer is immediately formed from the iron ions and the organic acid on already exposed decontaminated steel. If the acid is oxalic acid, this protective layer consists of iron 2-oxalate.
  • both ions of divalent iron and ions of trivalent iron can be extracted from the contaminated layer.
  • Ions of divalent iron that are no longer needed are bound to ion exchange resin during the decontamination process. Iron 2 ions still present in the solution at the end of decontamination can also be disposed of using ion exchange resin.
  • any oxalic acid that is no longer required can be broken down to carbon dioxide using UV light and hydrogen peroxide.
  • a method known from EP 0 527 416 B1 can be used for this.
  • only oxalic acid is required for the decontamination process, since the required iron ions can be obtained directly from the oxide layer carrying the contamination or from the base metal.
  • the advantage is achieved in particular that with decontamination of little or unalloyed steel almost no base metal attack occurs and nevertheless only a few chemicals are required, and that very little waste remains which has to be disposed of.
  • oxides of divalent and trivalent iron, which are part of the layer carrying the contamination, and oxalic acid form iron 2-oxalate and iron 3-oxalate.
  • ions of divalent and trivalent iron are present in solution.
  • the iron-3-oxalate (iron-3-ions) is converted into iron-2-oxalate (iron-2-ions) and carbon dioxide by irradiation with UV light.
  • the iron-2-oxalate (iron-2-ions) forms, as well as a pure, oxide-free base metal surface due to the decontamination, forms a protective layer there. Even while decontamination is still taking place elsewhere, that is, iron oxides are being detached from the acid, the protective layer is deposited on the areas that have already been cleaned.
  • iron 2-oxalate iron 2-ions
  • cation exchange resin ion exchange resin

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Apparatuses For Bulk Treatment Of Fruits And Vegetables And Apparatuses For Preparing Feeds (AREA)
EP99960849A 1998-11-10 1999-11-02 Procede de decontamination d'une surface d'un element Expired - Lifetime EP1141445B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19851852 1998-11-10
DE19851852A DE19851852A1 (de) 1998-11-10 1998-11-10 Verfahren zur Dekontamination einer Oberfläche eines Bauteiles
PCT/DE1999/003489 WO2000028112A1 (fr) 1998-11-10 1999-11-02 Procede de decontamination d'une surface d'un element

Publications (2)

Publication Number Publication Date
EP1141445A1 true EP1141445A1 (fr) 2001-10-10
EP1141445B1 EP1141445B1 (fr) 2003-03-12

Family

ID=7887331

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99960849A Expired - Lifetime EP1141445B1 (fr) 1998-11-10 1999-11-02 Procede de decontamination d'une surface d'un element

Country Status (11)

Country Link
US (1) US6444276B2 (fr)
EP (1) EP1141445B1 (fr)
JP (1) JP4421114B2 (fr)
KR (1) KR100637950B1 (fr)
AT (1) ATE234374T1 (fr)
CA (1) CA2350214C (fr)
DE (2) DE19851852A1 (fr)
ES (1) ES2192407T3 (fr)
MX (1) MXPA01004773A (fr)
TW (1) TW436815B (fr)
WO (1) WO2000028112A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090003507A1 (en) * 2007-06-27 2009-01-01 Makoto Nagase Method and apparatus for suppressing corrosion of carbon steel, method for suppressing deposit of radionuclide onto carbon steel members composing a nuclear power plant, and film formation apparatus
US8115045B2 (en) * 2007-11-02 2012-02-14 Areva Np Inc. Nuclear waste removal system and method using wet oxidation
DE102009002681A1 (de) 2009-02-18 2010-09-09 Areva Np Gmbh Verfahren zur Dekontamination radioaktiv kontaminierter Oberflächen
US8591663B2 (en) * 2009-11-25 2013-11-26 Areva Np Inc Corrosion product chemical dissolution process
KR101219526B1 (ko) 2010-09-20 2013-01-11 대한민국 다공질 문화재 표면의 금속오염물 제거용 습포제 및 이를 이용한 다공질 문화재 표면의 금속오염물 제거 방법
KR102055752B1 (ko) 2019-06-24 2019-12-17 대한민국 토벽화 보존처리용 고착제 제거용 습포팩, 이의 제조방법, 및 이를 이용한 제거방법
JP7411502B2 (ja) * 2020-05-20 2024-01-11 日立Ｇｅニュークリア・エナジー株式会社 原子力プラントの炭素鋼部材の化学除染方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2613351C3 (de) * 1976-03-29 1982-03-25 Kraftwerk Union AG, 4330 Mülheim Verfahren zur chemischen Dekontamination von metallischen Bauteilen von Kernreaktoranlagen
CH653466A5 (de) * 1981-09-01 1985-12-31 Industrieorientierte Forsch Verfahren zur dekontamination von stahloberflaechen und entsorgung der radioaktiven stoffe.
DE3413868A1 (de) * 1984-04-12 1985-10-17 Kraftwerk Union AG, 4330 Mülheim Verfahren zur chemischen dekontamination von metallischen bauteilen von kernreaktoranlagen
JPH0765204B2 (ja) * 1985-12-24 1995-07-12 住友化学工業株式会社 鉄酸化物の溶解除去法
EP0278256A1 (fr) * 1987-01-28 1988-08-17 Siemens Aktiengesellschaft Procédé et dispositif pour éliminer les couches d'oxydes
US4828743A (en) * 1987-11-20 1989-05-09 Boyle-Midway Household Products, Inc. Composition for rust removal and method of use thereof
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
US5024805A (en) * 1989-08-09 1991-06-18 Westinghouse Electric Corp. Method for decontaminating a pressurized water nuclear reactor system
DE4117625C2 (de) * 1991-05-29 1997-09-04 Siemens Ag Reinigungsverfahren
DE4126971A1 (de) * 1991-08-14 1993-02-18 Siemens Ag Verfahren und einrichtung zur entsorgung einer organischen substanz
JP3287074B2 (ja) * 1993-09-03 2002-05-27 栗田工業株式会社 酸化鉄スケールの溶解除去方法
US5958247A (en) * 1994-03-28 1999-09-28 Siemens Aktiengesellschaft Method for disposing of a solution containing an organic acid
DE4410747A1 (de) * 1994-03-28 1995-10-05 Siemens Ag Verfahren und Einrichtung zum Entsorgen einer Lösung, die eine organische Säure enthält
GB9422539D0 (en) * 1994-11-04 1995-01-04 British Nuclear Fuels Plc Decontamination processes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0028112A1 *

Also Published As

Publication number Publication date
WO2000028112A1 (fr) 2000-05-18
CA2350214C (fr) 2007-05-01
ATE234374T1 (de) 2003-03-15
TW436815B (en) 2001-05-28
CA2350214A1 (fr) 2000-05-18
ES2192407T3 (es) 2003-10-01
DE19851852A1 (de) 2000-05-11
US20010031320A1 (en) 2001-10-18
US6444276B2 (en) 2002-09-03
KR20010080408A (ko) 2001-08-22
EP1141445B1 (fr) 2003-03-12
JP4421114B2 (ja) 2010-02-24
JP2002529719A (ja) 2002-09-10
MXPA01004773A (es) 2002-05-06
DE59904578D1 (de) 2003-04-17
KR100637950B1 (ko) 2006-10-23

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