EP1141445B1 - Method for decontaminating the surface of a component - Google Patents

Method for decontaminating the surface of a component Download PDF

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Publication number
EP1141445B1
EP1141445B1 EP99960849A EP99960849A EP1141445B1 EP 1141445 B1 EP1141445 B1 EP 1141445B1 EP 99960849 A EP99960849 A EP 99960849A EP 99960849 A EP99960849 A EP 99960849A EP 1141445 B1 EP1141445 B1 EP 1141445B1
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EP
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Prior art keywords
iron
ions
solution
divalent iron
oxalate
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Expired - Lifetime
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EP99960849A
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German (de)
French (fr)
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EP1141445A1 (en
Inventor
Horst-Otto Bertholdt
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Areva GmbH
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Framatome ANP GmbH
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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 decontamination of a Surface of a component low or mild steel according to claim 1.
  • the invention is therefore based on the object of a method for decontamination of a surface of a component Specify steel, especially if the component is made low or unalloyed steel, the base metal attack keeps very small.
  • the object is achieved according to the invention in that the Solution containing oxalic acid, with which the surface of the Component is brought into contact, including ions of the divalent Contains iron, and thereby on just exposed Protect parts of the base metal surface immediately builds up iron 3-oxalate by exposure to UV light is converted into iron 2-oxalate and carbon dioxide that after completing the detachment of the contaminated Layer the protective layer by reducing the content Ions of divalent iron are detached in the solution and that no longer needed ions of the divalent Iron and the substance that causes the contamination has to be bound to an ion exchange resin.
  • divalent iron is obtained from trivalent iron by irradiating the solution containing ions of the trivalent iron with UV light. UV radiation to reduce iron can be found in EP 0 753 196 B1.
  • the method disclosed there does not serve for the decontamination of component surfaces but for the disposal of a decontamination solution containing oxalic acid.
  • iron III oxalate is converted into divalent iron oxalate by UV radiation and then converted back into the starting complex. The oxalic acid is broken down into CO 2 and water.
  • the ions of divalent iron can be the Solution also added from the outside. This is particularly suitable an iron-2 salt.
  • the iron 2 ions can be obtained from the contaminated layer or detached from the base metal become. There is only an insignificant removal of Base metal, since only relatively little iron 2 ions are needed become.
  • the contaminated layer can both ions of divalent iron and ions of trivalent Iron can be extracted.
  • the advantage of the invention is in particular that with decontamination on little or unalloyed steel almost no base metal attack occurs and yet only a little Chemicals are needed and that very little waste is left remains that has to be disposed of.
  • oxides become divalent and trivalent Iron, which is part of the contamination-bearing Layer are, and from oxalic acid iron 2-oxalate and iron 3-oxalate educated. Then ions of the divalent are in solution and trivalent iron.
  • iron 3-oxalate (iron 3-ions) is irradiated with UV light in iron 2-oxalate (iron 2 ions) and carbon dioxide converted.
  • iron 2-oxalate iron 2 ions
  • the iron 2-oxalate forms, as well as due to the Decontamination of a pure, oxide-free base metal surface is there, a protective layer. Even while on elsewhere decontamination is still running, i.e. iron oxides detached from the acid is already attached to the cleaned areas on the protective layer.
  • iron 2-oxalate iron 2 ions
  • cation exchange resin ion exchange resin

Abstract

A method for decontaminating a surface includes the steps of bringing a surface of a component formed of an unalloyed steel or a low-alloy steel into contact with a solution containing an oxalic acid for dissolving a contaminated layer from the component. Ions of divalent iron in the solution instantly form a protective layer on exposed surfaces. Iron(III) oxalate is converted into iron(II) oxalate and carbon dioxide by irradiation with UV light in order to provide ions of divalent iron. Subsequent to dissolving the contaminated layer, the protective layer is dissolved by lowering the level of the ions of the divalent iron in the solution. The ions of the divalent iron and the substance having caused the contaminated layer are bound to an ion exchange resin.

Description

Die Erfindung betrifft ein Verfahren zur Dekontamination einer Oberfläche eines Bauteils aus niedrig oder unlegiertem Stahl gemäß Anspruch 1.The invention relates to a method for decontamination of a Surface of a component low or mild steel according to claim 1.

Ein derartiges Verfahren ist in EP 278 256 beschreiben. Bei einem aus DE 41 17 625 C2 bekannten Verfahren besteht das zu dekontaminierende Bauteil beispielsweise aus C-Stahl und die Dekontaminationslösung enthält zumindest eine organische Säure. In der genannten Patentschrift ist auch ausgeführt, dass eine Dekontamination mit Oxalsäure möglich ist. Es wird aber darauf hingewiesen, dass Oxalsäure ungeeignet sei, da sie mit zweiwertigem Eisen schwer lösliche Niederschläge bilden soll.Such a method is described in EP 278 256. at a method known from DE 41 17 625 C2 exists decontaminating component made of carbon steel and the Decontamination solution contains at least one organic one Acid. In the mentioned patent specification is also stated that decontamination with oxalic acid is possible. It will but pointed out that oxalic acid is unsuitable because precipitation difficult to dissolve with divalent iron should form.

Inzwischen hat sich herausgestellt, dass bei einer Dekontamination von niedrig oder unlegiertem Stahl das Grundmetall angegriffen werden kann. Ein solcher Grundmetallangriff führt einerseits zu einer nicht unerheblichen Wandstärkenminderung des Bauteiles und andererseits zu einer Vergrößerung der zu entsorgenden radioaktiven Abfallmenge.It has now been found that decontamination the base metal attacked by low or unalloyed steel can be. Such a base metal attack leads on the one hand to a not inconsiderable reduction in wall thickness of the component and on the other hand to an increase in radioactive waste disposal.

Eine Verminderung des Grundmetallangriffes durch Inhibierung ist bisher nicht möglich gewesen, da einerseits zur Verfügung stehende Inhibitoren wegen der notwendigen hohen Prozesstemperaturen versagen würden und andererseits die Verwendung möglicher schwefelhaltiger Inhibitoren in kerntechnischen Anlagen nicht erlaubt sind. A reduction in the base metal attack by inhibition has not been possible so far because it is available on the one hand standing inhibitors because of the necessary high process temperatures would fail and on the other hand the use possible sulfur-containing inhibitors in nuclear facilities are not allowed.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren zur Dekontamination einer Oberfläche eines Bauteiles aus Stahl anzugeben, das insbesondere dann, wenn das Bauteil aus niedrig oder unlegiertem Stahl besteht, den Grundmetallangriff sehr klein hält.The invention is therefore based on the object of a method for decontamination of a surface of a component Specify steel, especially if the component is made low or unalloyed steel, the base metal attack keeps very small.

Die Aufgabe wird gemäß der Erfindung dadurch gelöst, dass die Oxalsäure enthaltende Lösung, mit der die Oberfläche des Bauteiles in Kontakt gebracht wird, auch Ionen des zweiwertigen Eisens enthält, und dadurch auf gerade freigelegten Teilen der Grundmetalloberfläche sofort eine Schutzschicht aufbaut, dass Eisen-3-Oxalat durch Bestrahlung mit UV-Licht in Eisen-2-Oxalat und Kohlenstoffdioxid umgewandelt wird , dass nach dem Abschluss des Ablösens der kontaminierten Schicht die Schutzschicht durch Verringerung des Gehalts an Ionen des zweiwertigen Eisens in der Lösung wieder abgelöst wird, und dass nicht mehr benötigte Ionen des zweiwertigen Eisens und die Substanz, die die Kontamination verursacht hat, auf ein Ionenaustauscherharz gebunden werden.The object is achieved according to the invention in that the Solution containing oxalic acid, with which the surface of the Component is brought into contact, including ions of the divalent Contains iron, and thereby on just exposed Protect parts of the base metal surface immediately builds up iron 3-oxalate by exposure to UV light is converted into iron 2-oxalate and carbon dioxide that after completing the detachment of the contaminated Layer the protective layer by reducing the content Ions of divalent iron are detached in the solution and that no longer needed ions of the divalent Iron and the substance that causes the contamination has to be bound to an ion exchange resin.

Mit dem Verfahren nach der Erfindung wird der Vorteil erzielt, dass die Bildung einer Schutzschicht gegeben ist, die einerseits das Grundmetall während der Dekontamination vor einem Angriff schützt, und andererseits am Ende der eigentlichen Dekontamination wieder leicht entfernt werden kann. Man benötigt vorteilhafterweise keine aufwendigen Inhibitoren, so dass schon deshalb, aber auch wegen der weitgehenden Vermeidung eines Grundmetallangriffes die Menge des zu entsorgenden Dekontaminationsabfalls minimiert wird. Erfindungsgemäß wird Zweiwertiges Eisen aus dreiwertigem Eisen gewonnen, indem die Lösung, die Ionen des dreiwertigen Eisens enthält, mit UV-Licht bestrahlt wird. Eine UV-Bestrahlung zur Reduzierung von Eisen ist der EP 0 753 196 B1 zu entnehmen. Das dort offenbarte Verfahren dient jedoch nicht zur Dekontamination von Bauteiloberflächen sondern zur Entsorgung einer Oxalsäure enthaltenden Dekontaminationslösung. Dazu wird in einem Kreisprozess Eisen-III-Oxalat durch UV-Bestrahlung in zweiwertiges Eisenoxalat und anschließend wieder in den Ausgangskomplex umgewandelt wird. Dabei wird die Oxalsäure zu CO2 und Wasser abgebaut.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. According to the invention, divalent iron is obtained from trivalent iron by irradiating the solution containing ions of the trivalent iron with UV light. UV radiation to reduce iron can be found in EP 0 753 196 B1. However, the method disclosed there does not serve for the decontamination of component surfaces but for the disposal of a decontamination solution containing oxalic acid. For this purpose, iron III oxalate is converted into divalent iron oxalate by UV radiation and then converted back into the starting complex. The oxalic acid is broken down into CO 2 and water.

Die Ionen des zweiwertigen Eisens (Eisen-2-Ionen) können der Lösung auch von außen zugegeben. Dazu eignet sich besonders ein Eisen-2-Salz.The ions of divalent iron (iron 2 ions) can be the Solution also added from the outside. This is particularly suitable an iron-2 salt.

Die Eisen-2-Ionen können nach einem anderen Beispiel aus der kontaminierten Schicht oder aus dem Grundmetall herausgelöst werden. Dabei kommt es nur zu einem unbedeutenden Abtrag von Grundmetall, da nur relativ wenig Eisen-2-Ionen gebraucht werden.According to another example, the iron 2 ions can be obtained from the contaminated layer or detached from the base metal become. There is only an insignificant removal of Base metal, since only relatively little iron 2 ions are needed become.

Das Zugeben und das Herauslösen von Eisen-2-Ionen sind auch kombinierbar.The addition and removal of iron 2 ions are also combined.

Sowohl nach dem Einspeisen von Eisen-2-Ionen in die Lösung als auch nach dem Herauslösen von Eisen-2-Ionen aus vorhandenem Material (Grundmetall, Schicht) bildet sich sofort aus den Eisenionen und der organischen Säure eine Schutzschicht auf bereits freigelegtem dekontaminiertem Stahl. Falls die Säure Oxalsäure ist, besteht diese Schutzschicht aus Eisen-2-Oxalat.Both after feeding iron 2 ions into the solution as well as after the release of iron 2 ions from existing Material (base metal, layer) forms immediately a protective layer against iron ions and organic acid on already exposed decontaminated steel. if the Acid is oxalic acid, this protective layer consists of iron 2-oxalate.

Je nach Kraftwerkstyp können aus der kontaminierten Schicht sowohl Ionen des zweiwertigen Eisens als auch Ionen des dreiwertigen Eisens herausgelöst werden.Depending on the type of power plant, the contaminated layer can both ions of divalent iron and ions of trivalent Iron can be extracted.

Nicht mehr benötigte Ionen des zweiwertigen Eisens werden während des Dekontaminationsverfahrens auf Ionenaustauscherharz gebunden. Auch am Ende der Dekontamination in der Lösung noch vorhandene Eisen-2-Ionen können durch Ionenaustauscherharz entsorgt werden. Ions of divalent iron that are no longer required during the decontamination process on ion exchange resin bound. Even at the end of decontamination in the solution Iron 2 ions still present can be replaced by ion exchange resin to be disposed of.

Im günstigsten Fall wird nur Oxalsäure für das Verfahren zur Dekontamination benötigt, da die erforderlichen Eisenionen direkt aus der die Kontamination tragenden Oxidschicht oder aus dem Grundmetall gewonnen werden können.In the best case, only oxalic acid is used for the process Decontamination is required because of the required iron ions directly from the oxide layer carrying the contamination or can be obtained from the base metal.

Zur Beseitigung des Abfalls ist neben einem Ionenaustauscherharz nur noch Wasserstoffperoxid erforderlich. Am Ende der Dekontamination und dem damit verbundenen Abbau der Schutzschicht verbleibt dann neben dem beladenen Ionenaustauscherharz nur noch Kohlenstoffdioxid.To remove the waste is next to an ion exchange resin only hydrogen peroxide required. At the end of Decontamination and the associated degradation of the protective layer then remains next to the loaded ion exchange resin only carbon dioxide.

Mit der Erfindung wird insbesondere der Vorteil erzielt, dass bei einer Dekontamination an wenig oder unlegiertem Stahl fast kein Grundmetallangriff auftritt und trotzdem nur wenig Chemikalien benötigt werden, und dass sehr wenig Abfall übrig bleibt, der entsorgt werden muss.The advantage of the invention is in particular that with decontamination on little or unalloyed steel almost no base metal attack occurs and yet only a little Chemicals are needed and that very little waste is left remains that has to be disposed of.

Es wird auch der Vorteil erzielt, dass keine Schwefelverbindungen und auch keine anderen aufwendigen Inhibitoren benötigt werden, und dass trotzdem der Grundmetallangriff sehr klein ist. Es besteht keine Gefahr einer selektiven Korrosion (Lochfraß).The advantage is also achieved that no sulfur compounds and also no other complex inhibitors are required be, and that nevertheless the base metal attack very is small. There is no risk of selective corrosion (Pitting).

Im folgenden werden die einzelnen chemischen Reaktionen, die während des Verfahrens nach der Erfindung ablaufen, anhand eines Beispiels aufgelistet:The following are the individual chemical reactions that expire during the method according to the invention, based on an example:

Zunächst werden aus Oxiden des zweiwertigen und des dreiwertigen Eisens, die Bestandteil der die Kontamination tragenden Schicht sind, und aus Oxalsäure Eisen-2-Oxalat und Eisen-3-Oxalat gebildet. In Lösung sind dann Ionen des zweiwertigen und des dreiwertigen Eisens vorhanden.First of all, oxides become divalent and trivalent Iron, which is part of the contamination-bearing Layer are, and from oxalic acid iron 2-oxalate and iron 3-oxalate educated. Then ions of the divalent are in solution and trivalent iron.

Das Eisen-3-Oxalat (Eisen-3-Ionen) wird durch Bestrahlung mit UV-Licht in Eisen-2-Oxalat (Eisen-2-Ionen) und Kohlenstoffdioxid umgewandelt. The iron 3-oxalate (iron 3-ions) is irradiated with UV light in iron 2-oxalate (iron 2 ions) and carbon dioxide converted.

Das Eisen-2-Oxalat (Eisen-2-Ionen) bildet, sowie aufgrund der Dekontamination eine reine, oxidfreie Grundmetalloberfläche vorhanden ist, dort eine Schutzschicht aus. Auch während an anderer Stelle noch die Dekontamination läuft, also Eisenoxide von der Säure abgelöst werden, lagert sich an den bereits gereinigten Stellen die Schutzschicht an.The iron 2-oxalate (iron 2 ions) forms, as well as due to the Decontamination of a pure, oxide-free base metal surface is there, a protective layer. Even while on elsewhere decontamination is still running, i.e. iron oxides detached from the acid is already attached to the cleaned areas on the protective layer.

Ein möglicher Überschuss von Eisen-2-Oxalat (Eisen-2-Ionen) wird auf einem Ionenaustauscherharz (Kationenaustauscherharz) gebunden, wobei wieder Oxalsäure freigesetzt wird.A possible excess of iron 2-oxalate (iron 2 ions) is on an ion exchange resin (cation exchange resin) bound, releasing oxalic acid again.

Sowie die Dekontamination beendet ist, d.h. wenn alle Eisenoxide von der Oberfläche abgelöst worden sind, entsteht kein neues Eisenoxalat mehr. Dann wird vorteilhafterweise die nicht mehr benötigte Schutzschicht aus Eisen-2-Oxalat in die Lösung abgebaut, d.h. das Eisen-2-Oxalat der Schutzschicht wird abgelöst und anschließend, wie schon zuvor ein möglicher Oxalatüberschuss, in einem Ionenaustauscherharz bei Abgabe von Oxalsäure gebunden. Danach verbleibt außer dem beladenen Ionenaustauscherharz noch Oxalsäure. Diese Oxalsäure wird durch Zugabe von Wasserstoffperoxid in Verbindung mit UV-Licht zur Kohlenstoffdioxid abgebaut.As soon as the decontamination has ended, i.e. if all iron oxides have been detached from the surface, no new iron oxalate more. Then advantageously protective layer of iron 2-oxalate no longer required in the Solution dismantled, i.e. the iron 2-oxalate of the protective layer is replaced and then, as before, a possible one Excess oxalate, in an ion exchange resin upon delivery bound by oxalic acid. After that, besides the loaded one remains Ion exchange resin still oxalic acid. This is oxalic acid by adding hydrogen peroxide in combination with UV light degraded to carbon dioxide.

Es verbleibt neben Ionenaustauscherharz nur Kohlenstoffdixoid.In addition to ion exchange resin, only carbon dioxide remains.

Claims (4)

  1. Process for the decontamination of a surface of a component made from low-alloy or unalloyed steel, the surface being brought into contact with a solution which contains an oxalic acid and dissolves a contaminated layer from the base metal of the component, characterized in that the solution also contains ions of divalent iron and as a result immediately forms a protective layer on parts of the base-metal surface which have just been exposed, in that iron(III) oxalate is converted into iron(II) oxalate and carbon dioxide by irradiation with UV light, in that after the dissolving of the contaminated layer has finished the protective layer is removed again by lowering the level of ions of divalent iron in the solution, and in that ions of divalent iron which are no longer required and the substance which caused the contamination are bound to an ion exchange resin.
  2. Process according to Claim 1, characterized in that ions of divalent iron are added to the solution.
  3. Process according to Claim 1 or 2, characterized in that ions of divalent iron are dissolved out of the contaminated layer or out of the base metal.
  4. Process according to one of Claims 1 to 3,
    characterized in that oxalic acid which is no longer required is broken down into carbon dioxide by means of UV light and hydrogen peroxide.
EP99960849A 1998-11-10 1999-11-02 Method for decontaminating the surface of a component Expired - Lifetime EP1141445B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19851852A DE19851852A1 (en) 1998-11-10 1998-11-10 Process for the decontamination of a surface of a component
DE19851852 1998-11-10
PCT/DE1999/003489 WO2000028112A1 (en) 1998-11-10 1999-11-02 Method for decontaminating the surface of a component

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EP1141445A1 EP1141445A1 (en) 2001-10-10
EP1141445B1 true EP1141445B1 (en) 2003-03-12

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

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KR100637950B1 (en) 2006-10-23
US20010031320A1 (en) 2001-10-18
CA2350214A1 (en) 2000-05-18
JP2002529719A (en) 2002-09-10
MXPA01004773A (en) 2002-05-06
US6444276B2 (en) 2002-09-03
KR20010080408A (en) 2001-08-22
JP4421114B2 (en) 2010-02-24
ATE234374T1 (en) 2003-03-15
TW436815B (en) 2001-05-28
EP1141445A1 (en) 2001-10-10
ES2192407T3 (en) 2003-10-01
DE59904578D1 (en) 2003-04-17
WO2000028112A1 (en) 2000-05-18
CA2350214C (en) 2007-05-01
DE19851852A1 (en) 2000-05-11

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