EP0247933B1 - Verfahren zur Dekontamination von mit kontaminierenden Elementen kontaminierten festen Materialien, insbesondere durch radioaktive Elemente wie Ruthenium - Google Patents

Verfahren zur Dekontamination von mit kontaminierenden Elementen kontaminierten festen Materialien, insbesondere durch radioaktive Elemente wie Ruthenium Download PDF

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Publication number
EP0247933B1
EP0247933B1 EP19870401159 EP87401159A EP0247933B1 EP 0247933 B1 EP0247933 B1 EP 0247933B1 EP 19870401159 EP19870401159 EP 19870401159 EP 87401159 A EP87401159 A EP 87401159A EP 0247933 B1 EP0247933 B1 EP 0247933B1
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EP
European Patent Office
Prior art keywords
ruthenium
process according
solution
alkali metal
contaminating
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
EP19870401159
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English (en)
French (fr)
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EP0247933A1 (de
Inventor
René Chazot
Lucien Dolle
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Commissariat à l'Énergie Atomique et Aux Énergies Alternatives
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Commissariat a lEnergie Atomique CEA
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Classifications

    • 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 for decontaminating contaminated solid materials.
  • Radioactive decontamination of metallic parts carrying deposits of radioactive colloidal particles constituted for example by nodules of precious metals or of alloys of precious metals insoluble in nitric solution.
  • Metal parts contaminated by such deposits are found in particular in facilities for reprocessing irradiated nuclear fuels.
  • the present invention specifically relates to a process for decontaminating contaminated solid materials, which precisely avoids this drawback.
  • the process according to the invention for decontaminating solid materials contaminated with one or more radioactive elements contaminating the platinum mine is characterized in that it consists in applying to said material a reagent consisting of a metal hydroxide solution alkali metal and alkali metal peroxydisulfate, so as to selectively dissolve said contaminating element (s) without appreciably attacking the solid material to be decontaminated.
  • a basic solution containing an oxidizing agent is thus used to directly dissolve the contaminating elements of the platinum mine.
  • these contaminating elements are formed by platinum group metals, by alloys of a platinum group metal or by compounds of platinum group metals.
  • the platinum group metals are, for example, ruthenium, rhodium, palladium, osmium, irridium and platinum, in particular ruthenium 106.
  • European patent EP-A 0 164 988 and Japanese patent JP-A- 76/92 736 disclose methods for removing sparingly soluble deposits, in which an oxidizing agent such as hypohalogenite is first used or an ammonium persulfate in order to oxidize the element to be dissolved in order to then dissolve it in a second reagent consisting of an acid solution.
  • an oxidizing agent such as hypohalogenite is first used or an ammonium persulfate in order to oxidize the element to be dissolved in order to then dissolve it in a second reagent consisting of an acid solution.
  • the mechanisms used in these latter processes are therefore different from those of the invention since, in this case, direct contamination of the contaminating elements in the basic solution of the oxidizing agent is not obtained.
  • the oxidizing agents used in the invention are peroxydisulfates of alkali metals such as potassium peroxydisulfate.
  • the solution is preferably a strongly basic solution and it can be constituted by a sodium hydroxide solution.
  • the peroxydisulfate concentrations of the solution are chosen so as to obtain a good rate of dissolution of the noble metal using relatively short application times.
  • concentration of alkali metal peroxydisulfate is 10 to 25 g / l, but amounts less than 10 g / l can be used.
  • concentrations higher than 25 g / l would involve excessive consumption of reagent.
  • a strongly basic solution for example an alkali metal hydroxide solution, the concentration of which is preferably 6 to 8 N.
  • the reagent consists of an 8N sodium hydroxide solution containing 25 g / l of potassium peroxydisulfate.
  • the reagent for dissolving contaminating elements is prepared only at the time of use since the potassium peroxydisulfate exhibits moderate stability in the aqueous sodium hydroxide solution. Also, to maintain sufficient activity of the reagent, it is preferable to prepare it at the last moment.
  • the solid material After applying the reagent to the part to selectively dissolve the contaminating element (s), the solid material is preferably subjected to washing.
  • the purpose of this washing is in particular to promote the total removal of the reagent containing the contaminating elements in solution, which could remain on the part after the first application.
  • potassium peroxydisulfate which has a reduced stability in basic solutions
  • the solution used for washing must be able to dissolve this decomposition residue.
  • sulfuric acid is advantageously used diluted, for example 1N sulfuric acid.
  • the reagent can be applied to the part by the conventional techniques usually used.
  • the reagent can be applied to the surface of the part with a brush, but when it is a question of decontaminating small parts, they can be soaked in the reagent.
  • This decontamination can also be carried out by spraying the reagent on the parts by appropriate means to promote sufficient contact time and these operations can be repeated several times.
  • the washing of the part can be carried out by the same techniques.
  • the washing solution consists of dilute sulfuric acid
  • it can also be applied as a mixture with a pasty matrix such as silica gel, which makes it possible to limit the volume of acid while increasing the concentration of this several times the amount contained in a normal solution.
  • the duration of application of the reagent to the part is chosen according to the nature of the parts to be treated and their contamination. Generally, contact times of one hour are sufficient at room temperature. It is also possible to operate at temperatures above ambient temperature to accelerate the process of dissolution of the contaminating elements.
  • the parts capable of being decontaminated by the process of the invention can be made of different materials and the surface to be decontaminated can be made of this material or possibly be formed by a coating deposited on the part.
  • these may be parts made of stainless steel which is a material widely used in installations for the reprocessing of irradiated nuclear fuels.
  • Examples 1 to 7 describe the results obtained with various reagents for dissolving ruthenium. Among these examples, only examples 1, 5, 6 and 7 use the reagent of the invention.
  • Example 1 a reagent according to the invention is used to carry out this dissolution, which consists of 8N sodium hydroxide containing 25 g / l of potassium peroxydisulfate mixed only at the time of use.
  • aqueous colloidal suspension of Ru (OH) introduit are introduced into 200 cm3 of the reagent, and the operation is carried out at 30 ° C. After one hour, the quantity of aqueous colloidal suspension of Ru (OH) 3 which has been dissolved in the solution is determined. The results obtained are given in table I appended.
  • Example 2 an aqueous solution of potassium peroxydisulfate at 25 g / l is used as dissolution reagent and the dissolution is carried out under the same conditions.
  • the results obtained are also given in Table I.
  • Example 3 a fluonitric mixture of 6N hydrofluoric acid and 6N nitric acid is used and the dissolution is carried out under the same conditions. The results obtained are given in Table I.
  • Example 4 8N sodium hydroxide is used and the dissolution is carried out under the same conditions. The results are also given in Table I.
  • Example 5 a solution of 0.1% potassium permanganate in 0.01N sodium hydroxide and the dissolution is carried out under the same conditions.
  • the procedure of example 6 is repeated, but the ruthenium comes from a suspension of Ru (OH) 3 in the same uranyl nitrate solution which was brought to 102 ° C. for 40 h and then cooled. . Under these conditions, the fraction of dissolved ruthenium is 97.3%.
  • Example 2 the procedure of Example 1 is repeated, but using 8.9 mg of powdered ruthenium metal. Under these conditions, the fraction of dissolved ruthenium is 99.92%.
  • the method of the invention is used to decontaminate contaminated 316L stainless steel sheets. with ruthenium using for the dissolution of ruthenium a 25 g / l solution of potassium peroxydisulfate in 8N sodium hydroxide and by carrying out two successive applications of this reagent on the sheets for a period of 1 hour. At the end of the treatment, rinsing is carried out with 1N sulfuric acid.
  • the sheets are rough rolled 316L steel sheets, while in Example 10, they are pickled and passivated 316L steel sheets.
  • the decontamination factor F D in ruthenium is determined which corresponds to the ratio of the surface activities of the radioactive ruthenium before and after the decontamination treatment as well as the loss of thickness of the sheets in micrometers. The results obtained are given in Table II.

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)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (9)

  1. Verfahren zur Dekontamination eines festen Materials, das durch ein oder mehrere in Salpetersäure unlösliche radioaktive Elemente aus der Gruppe der Metalle der Platin-Gruppe, der Legierungen, die ein Metall der Platin-Gruppe enthalten, und der Verbindungen der Metalle der Platin-Gruppe kontaminiert ist, dadurch gekennzeichnet, daß es darin besteht, daß man auf dieses Material ein Reagens, bestehend aus einer Lösung eines Alkalimetallhydroxids und eines Alkalimetallperoxydisulfats in der Weise aufbringt, daß das oder die kontaminierenden Elemente aufgelöst werden, ohne daß das zu dekontaminierende feste Material merklich angegriffen wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem Alkalimetallhydroxid um Natriumhydroxid handelt.
  3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß es sich bei dem Alkalimetallperoxydisulfat um Kaliumperoxydisulfat handelt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Konzentration der Lösung an Alkalimetallperoxydisulfat 10 bis 25 g/l beträgt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Konzentration der Lösung an Alkalimetallhydroxid 6 bis 8 N beträgt.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man das feste Material anschließend mit einer Waschlösung, welche die Rückstände der Zersetzung des Alkalimetallperoxydisulfats auflösen kann, wäscht.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß es sich bei der Waschlösung um verdünnte Schwefelsäure handelt.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das kontaminierende Element umfaßt Ruthenium-106, eine Legierung von Ruthenium-106 oder eine Verbindung von Ruthenium-106.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es sich bei dem festen Material um einen nichtoxidierbaren Stahl handelt.
EP19870401159 1986-05-27 1987-05-22 Verfahren zur Dekontamination von mit kontaminierenden Elementen kontaminierten festen Materialien, insbesondere durch radioaktive Elemente wie Ruthenium Expired - Lifetime EP0247933B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8607569A FR2599543B1 (fr) 1986-05-27 1986-05-27 Procede de decontamination de materiaux solides contamines par des elements contaminants, en particulier par des elements radioactifs tels que le ruthenium
FR8607569 1986-05-27

Publications (2)

Publication Number Publication Date
EP0247933A1 EP0247933A1 (de) 1987-12-02
EP0247933B1 true EP0247933B1 (de) 1991-07-24

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EP19870401159 Expired - Lifetime EP0247933B1 (de) 1986-05-27 1987-05-22 Verfahren zur Dekontamination von mit kontaminierenden Elementen kontaminierten festen Materialien, insbesondere durch radioaktive Elemente wie Ruthenium

Country Status (4)

Country Link
EP (1) EP0247933B1 (de)
JP (1) JPS62287199A (de)
DE (1) DE3771579D1 (de)
FR (1) FR2599543B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200143952A1 (en) * 2018-11-07 2020-05-07 Korea Atomic Energy Research Institute Method for Treating Radioactive Liquid Waste

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2119688C1 (ru) * 1997-03-04 1998-09-27 Государственное предприятие Ленинградская атомная электростанция им.В.И.Ленина Способ дезактивации кремния
FR2820417B1 (fr) * 2001-02-08 2003-05-30 Commissariat Energie Atomique Procede de dissolution et de decontamination
FR2873848B1 (fr) 2004-08-02 2006-11-17 Tech En Milieu Ionisant Stmi S Procede de decontamination d'objets en plomb

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1484690A (en) * 1919-02-27 1924-02-26 Percy H Walker Material for and method of cleaning metal surfaces
US2476823A (en) * 1945-12-14 1949-07-19 Firestone Tire & Rubber Co Method of treating polonium plated metal
JPS5192736A (ja) * 1975-02-12 1976-08-14 Sankabutsusukeeruyokaijokyohoho
US4654170A (en) * 1984-06-05 1987-03-31 Westinghouse Electric Corp. Hypohalite oxidation in decontaminating nuclear reactors

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200143952A1 (en) * 2018-11-07 2020-05-07 Korea Atomic Energy Research Institute Method for Treating Radioactive Liquid Waste

Also Published As

Publication number Publication date
JPS62287199A (ja) 1987-12-14
FR2599543B1 (fr) 1992-01-17
FR2599543A1 (fr) 1987-12-04
EP0247933A1 (de) 1987-12-02
DE3771579D1 (de) 1991-08-29

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