EP0483053B1 - Dekontaminationsmittel und Verfahren zur Lösung von radioaktiv kontaminierten Oberflächen von Komponenten aus Metall - Google Patents

Dekontaminationsmittel und Verfahren zur Lösung von radioaktiv kontaminierten Oberflächen von Komponenten aus Metall Download PDF

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Publication number
EP0483053B1
EP0483053B1 EP91810731A EP91810731A EP0483053B1 EP 0483053 B1 EP0483053 B1 EP 0483053B1 EP 91810731 A EP91810731 A EP 91810731A EP 91810731 A EP91810731 A EP 91810731A EP 0483053 B1 EP0483053 B1 EP 0483053B1
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EP
European Patent Office
Prior art keywords
process according
contaminated
oxidant
lead
mixture
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
EP91810731A
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German (de)
English (en)
French (fr)
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EP0483053A1 (de
Inventor
Jozef Hanulik
Jean-Francois Equey
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Recytec SA
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Recytec SA
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Publication date
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Publication of EP0483053A1 publication Critical patent/EP0483053A1/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23G1/10—Other heavy metals
    • 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 present invention relates to a method and a decontamination agent for dissolving oxidized or non-oxidized, radioactively contaminated surfaces of objects made of metal, according to the preamble of claim 1 or claim 22.
  • shielding stones are formed from lead or lead alloys, which are used to create entire walls around highly radioactive components. Heavily radioactive tubes are also covered with lead mats. Of course, these shielding stones, lead mats or lead plates can also be radioactively contaminated. They therefore have to be decontaminated from time to time. So far, this has been unsatisfactory.
  • the lead or lead-containing elements were scraped off on the surface or brushed manually, the contaminated scraped material was radioactively disposed of and the remaining, still slightly contaminated components were melted down.
  • a second variant was to provide the lead shielding stones or plates with a plastic covering that is renewed from time to time. The contaminated plastic cover was always disposed of by nuclear waste. Both variants led to a relatively large amount of nuclear waste to be disposed of.
  • the radioactive contaminated metallic components are placed in a fluoroboric acid bath and this is electrochemically regenerated and the metals are recovered while the regenerated fluoroboric acid is fed back into the process.
  • this method has proven to be too time-consuming that it can also only be used at elevated temperature and concentration.
  • the solubility of lead and other metals such as Ni, Cu, Hg, Ag or steel is also an extremely slow process in HBF4 acid at room temperature, which also takes place with the development of hydrogen H2.
  • This information relates to a reagent of 5% HBF4 with 0.5% H2O2 at a temperature of 25 ° C.
  • a first step (1) as shown in Figure 3, the contaminated components must be degreased. Then they are placed in a solution bath (2). This contains the reagent already described, consisting of a 5% HBF4 acid and 0.5% hydrogen peroxide.
  • the now decontaminated lead plates are removed from the solution bath (2).
  • the solution, which is now contaminated, is led (4) to an electrolysis bath by performing the electrolysis (5).
  • the contaminated lead or lead dioxide is now deposited on the anode or cathode.
  • the concentrated radioactive contaminated material (6) is now in a highly concentrated form and can now be disposed of in a nuclear manner in a known manner.
  • the remaining HBF4 acid is removed from the electrolysis cell (7). Now the return (9) of the HBF4 acid can take place in the solution bath (2). This is done with addition (8) of H2O2 until the desired concentration is reached again.
  • the process can be terminated by neutralizing the acid after the electrolysis has been carried out by adding calcium hydroxide or regenerating it on a cationic ion exchanger to the pure, uncontaminated acid. As is known, this produces a precipitate that can be filtered out or sedimented. The remaining, contaminated filter cake can solidify and be disposed of by nuclear waste. The remaining filtrate is free of activity and also no longer contains lead. It can therefore be disposed of without additional precautionary measures, for example by disposing of it in the waste water disposal system.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Food Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Electrochemistry (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
EP91810731A 1990-10-26 1991-09-16 Dekontaminationsmittel und Verfahren zur Lösung von radioaktiv kontaminierten Oberflächen von Komponenten aus Metall Expired - Lifetime EP0483053B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH3429/90 1990-10-26
CH3429/90A CH682023A5 (enrdf_load_stackoverflow) 1990-10-26 1990-10-26

Publications (2)

Publication Number Publication Date
EP0483053A1 EP0483053A1 (de) 1992-04-29
EP0483053B1 true EP0483053B1 (de) 1995-03-01

Family

ID=4255784

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91810731A Expired - Lifetime EP0483053B1 (de) 1990-10-26 1991-09-16 Dekontaminationsmittel und Verfahren zur Lösung von radioaktiv kontaminierten Oberflächen von Komponenten aus Metall

Country Status (12)

Country Link
US (1) US5340505A (enrdf_load_stackoverflow)
EP (1) EP0483053B1 (enrdf_load_stackoverflow)
JP (1) JPH04285898A (enrdf_load_stackoverflow)
BG (1) BG95366A (enrdf_load_stackoverflow)
CA (2) CA2054234A1 (enrdf_load_stackoverflow)
CH (1) CH682023A5 (enrdf_load_stackoverflow)
CS (1) CS325391A3 (enrdf_load_stackoverflow)
DE (1) DE59104768D1 (enrdf_load_stackoverflow)
ES (1) ES2071278T3 (enrdf_load_stackoverflow)
FI (1) FI914870A7 (enrdf_load_stackoverflow)
HU (1) HU212234B (enrdf_load_stackoverflow)
RU (1) RU2029400C1 (enrdf_load_stackoverflow)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9422539D0 (en) * 1994-11-04 1995-01-04 British Nuclear Fuels Plc Decontamination processes
US5458745A (en) * 1995-01-23 1995-10-17 Covofinish Co., Inc. Method for removal of technetium from radio-contaminated metal
US5724668A (en) * 1995-11-07 1998-03-03 Electronic Power Research Institute Method for decontamination of nuclear plant components
US6147274A (en) * 1996-11-05 2000-11-14 Electric Power Research Insitute Method for decontamination of nuclear plant components
US5805654A (en) * 1997-04-08 1998-09-08 Wood; Christopher J. Regenerative LOMI decontamination process
US5901368A (en) * 1997-06-04 1999-05-04 Electric Power Research Institute Radiolysis-assisted decontamination process
US6320675B1 (en) 1997-07-15 2001-11-20 Canon Kabushiki Kaisha Image processing apparatus and method and storage medium
US7384529B1 (en) 2000-09-29 2008-06-10 The United States Of America As Represented By The United States Department Of Energy Method for electrochemical decontamination of radioactive metal
RU2195728C2 (ru) * 2000-11-22 2002-12-27 Государственное предприятие "Курская атомная станция" Способ малореагентной дезактивации
FR2873848B1 (fr) 2004-08-02 2006-11-17 Tech En Milieu Ionisant Stmi S Procede de decontamination d'objets en plomb
US20100010285A1 (en) * 2008-06-26 2010-01-14 Lumimove, Inc., D/B/A Crosslink Decontamination system
RU2397558C1 (ru) * 2009-07-27 2010-08-20 Федеральное государственное унитарное предприятие "Научно-исследовательский технологический институт имени А.П. Александрова" Способ очистки и дезактивации оборудования атомных электрических станций (варианты)
JP6220114B2 (ja) * 2011-11-30 2017-10-25 荏原工業洗浄株式会社 放射性セシウム固体状被汚染物の除染方法及び装置
RU2502567C1 (ru) * 2012-07-27 2013-12-27 Федеральное государственное унитарное предприятие "Российский Федеральный ядерный центр - Всероссийский научно-исследовательский институт экспериментальной физики" - ФГУП "РФЯЦ-ВНИИЭФ" Способ удаления металлических покрытий с поверхности деталей из радиоактивного химически активного металла
JP6403517B2 (ja) * 2014-09-25 2018-10-10 三菱重工業株式会社 放射性廃棄物除染方法
RU2646535C1 (ru) * 2017-04-12 2018-03-06 Федеральное государственное унитарное предприятие "Научно-исследовательский институт Научно-производственное объединение "ЛУЧ" (ФГУП "НИИ НПО "ЛУЧ") Способ переработки отходов ядерного производства
CN112176393B (zh) * 2020-09-28 2021-09-21 中核四川环保工程有限责任公司 一种电化学去污电解液及其制备方法和应用

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1899734A (en) * 1930-01-18 1933-02-28 American Sheet & Tin Plate Removal of oxids from ferrous metal
US2154451A (en) * 1934-12-17 1939-04-18 Du Pont Bright dip
GB891760A (en) * 1957-07-08 1962-03-21 Derek Richard Stuckey Improvements in or relating to sleeved garments
GB891670A (en) * 1957-09-04 1962-03-14 English Electric Co Ltd Improvements in and relating to the removing of scale from silicon iron and other metals
US3080323A (en) * 1959-04-07 1963-03-05 Purex Corp Ltd Composition for radioactive decontamination and descaling of cobalt alloys
BE670521A (enrdf_load_stackoverflow) * 1964-10-05 1900-01-01
US3341304A (en) * 1966-04-08 1967-09-12 Billie J Newby Separation of uranium from uranium dioxide-zirconium dioxide mixtures
US3409413A (en) * 1967-08-11 1968-11-05 Atomic Energy Commission Usa Method of dissolving aluminum-clad thoria target elements
US3668131A (en) * 1968-08-09 1972-06-06 Allied Chem Dissolution of metal with acidified hydrogen peroxide solutions
US3565707A (en) * 1969-03-03 1971-02-23 Fmc Corp Metal dissolution
SU398702A1 (ru) * 1970-04-29 1973-09-27 Раствор для стравливания гальванических покрытий сплавами олово—свинец
DE2058766A1 (de) * 1970-11-30 1972-05-31 Siemens Ag Verfahren zur Reinigung von metallischen Oberflaechen,insbesondere radioaktiv verseuchten Oberflaechen
US3891741A (en) * 1972-11-24 1975-06-24 Ppg Industries Inc Recovery of fission products from acidic waste solutions thereof
US3986970A (en) * 1973-05-02 1976-10-19 The Furukawa Electric Co., Ltd. Solution for chemical dissolution treatment of tin or alloys thereof
US3873362A (en) * 1973-05-29 1975-03-25 Halliburton Co Process for cleaning radioactively contaminated metal surfaces
US3965237A (en) * 1975-04-11 1976-06-22 The United States Of America As Repesented By The United States Energy Research And Development Administration Dissolution process for ZrO2 -UO2 -CaO fuels
DE2553569C2 (de) * 1975-11-28 1985-09-12 Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe Verfahren zur Verfestigung von radioaktiven wäßrigen Abfallstoffen durch Sprühkalzinierung und anschließende Einbettung in eine Matrix aus Glas oder Glaskeramik
BE838533A (fr) * 1976-02-13 1976-05-28 Procede de sechage des solutions contenant de l'acide borique
CH619807A5 (enrdf_load_stackoverflow) * 1976-04-07 1980-10-15 Foerderung Forschung Gmbh
DE2910677C2 (de) * 1979-03-19 1983-12-22 Kraftwerk Union AG, 4330 Mülheim Verfahren zur Behandlung von borhaltigen radioaktiven Konzentraten aus Abwässern von Druckwasserreaktoren
US4217192A (en) * 1979-06-11 1980-08-12 The United States Of America As Represented By The United States Department Of Energy Decontamination of metals using chemical etching
US4443269A (en) * 1979-10-01 1984-04-17 Health Physics Systems, Inc. Tool decontamination method
JPS57164984A (en) * 1981-04-06 1982-10-09 Metsuku Kk Exfoliating solution for tin or tin alloy
CH653466A5 (de) * 1981-09-01 1985-12-31 Industrieorientierte Forsch Verfahren zur dekontamination von stahloberflaechen und entsorgung der radioaktiven stoffe.
US4686019A (en) * 1982-03-11 1987-08-11 Exxon Research And Engineering Company Dissolution of PuO2 or NpO2 using electrolytically regenerated reagents
US4530723A (en) * 1983-03-07 1985-07-23 Westinghouse Electric Corp. Encapsulation of ion exchange resins
US4620947A (en) * 1983-10-17 1986-11-04 Chem-Nuclear Systems, Inc. Solidification of aqueous radioactive waste using insoluble compounds of magnesium oxide
US4537666A (en) * 1984-03-01 1985-08-27 Westinghouse Electric Corp. Decontamination using electrolysis
US4701246A (en) * 1985-03-07 1987-10-20 Kabushiki Kaisha Toshiba Method for production of decontaminating liquid
WO1986007184A1 (en) * 1985-05-28 1986-12-04 Jozef Hanulik Agent for decontaminating contaminated metal materials or cement-containing materials, production method and utilization
JPS6267500A (ja) * 1985-09-20 1987-03-27 日立プラント建設株式会社 放射能汚染物の化学的除染方法及び装置
CH679158A5 (enrdf_load_stackoverflow) * 1989-07-20 1991-12-31 Recytec S A C O Orfigest S A
JPH0375386A (ja) * 1989-08-18 1991-03-29 Metsuku Kk 錫又は錫‐鉛合金の剥離方法
US5084253A (en) * 1989-11-13 1992-01-28 Nuclear Metals, Inc. Method of removing niobium from uranium-niobium alloy

Also Published As

Publication number Publication date
CH682023A5 (enrdf_load_stackoverflow) 1993-06-30
FI914870A7 (fi) 1992-04-27
BG95366A (bg) 1993-12-24
EP0483053A1 (de) 1992-04-29
HU913363D0 (en) 1992-01-28
JPH04285898A (ja) 1992-10-09
HUT69460A (en) 1995-09-28
US5340505A (en) 1994-08-23
RU2029400C1 (ru) 1995-02-20
DE59104768D1 (de) 1995-04-06
FI914870A0 (fi) 1991-10-16
HU212234B (en) 1996-04-29
ES2071278T3 (es) 1995-06-16
CS325391A3 (en) 1992-06-17
CA2054236A1 (en) 1992-04-27
CA2054234A1 (en) 1992-04-27

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