EP0247933A1 - 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 PDFInfo
- Publication number
- EP0247933A1 EP0247933A1 EP87401159A EP87401159A EP0247933A1 EP 0247933 A1 EP0247933 A1 EP 0247933A1 EP 87401159 A EP87401159 A EP 87401159A EP 87401159 A EP87401159 A EP 87401159A EP 0247933 A1 EP0247933 A1 EP 0247933A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ruthenium
- alkali metal
- solution
- elements
- peroxydisulfate
- 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
Links
- 239000011343 solid material Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 27
- 230000002285 radioactive effect Effects 0.000 title claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title description 20
- 229910052707 ruthenium Inorganic materials 0.000 title description 19
- 230000008569 process Effects 0.000 title description 9
- -1 alkali metal peroxydisulphate Chemical class 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 5
- KJTLSVCANCCWHF-BKFZFHPZSA-N ruthenium-106 Chemical compound [106Ru] KJTLSVCANCCWHF-BKFZFHPZSA-N 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000003153 chemical reaction reagent Substances 0.000 claims description 29
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- 235000019394 potassium persulphate Nutrition 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910000929 Ru alloy Inorganic materials 0.000 claims 1
- 239000000356 contaminant Substances 0.000 claims 1
- 150000003304 ruthenium compounds Chemical class 0.000 claims 1
- 238000005202 decontamination Methods 0.000 abstract description 12
- 230000003588 decontaminative effect Effects 0.000 abstract description 12
- 239000000376 reactant Substances 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 238000004090 dissolution Methods 0.000 description 24
- 239000007800 oxidant agent Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 7
- 239000003637 basic solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000003758 nuclear fuel Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000004976 peroxydisulfates Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000005289 uranyl group Chemical group 0.000 description 1
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 the 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 from 10 to 25 g / l, but 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 6 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 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)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8607569 | 1986-05-27 | ||
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0247933A1 true EP0247933A1 (de) | 1987-12-02 |
| EP0247933B1 EP0247933B1 (de) | 1991-07-24 |
Family
ID=9335686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 (3)
| 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 |
| FR2820417A1 (fr) * | 2001-02-08 | 2002-08-09 | Commissariat Energie Atomique | Procede de dissolution et de decontamination |
| EP1624466A1 (de) | 2004-08-02 | 2006-02-08 | S.T.M.I. Société des Techniques en Milieu Ionisant | Verfahren zum Dekontaminieren von Bleigegenständen |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102073018B1 (ko) * | 2018-11-07 | 2020-02-04 | 한국원자력연구원 | 제염 폐액의 처리 방법 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2476823A (en) * | 1945-12-14 | 1949-07-19 | Firestone Tire & Rubber Co | Method of treating polonium plated metal |
| EP0164988A1 (de) * | 1984-06-05 | 1985-12-18 | Westinghouse Electric Corporation | Verfahren zur Dekontamination metallischer Oberflächen |
Family Cites Families (2)
| 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 |
| JPS5192736A (ja) * | 1975-02-12 | 1976-08-14 | Sankabutsusukeeruyokaijokyohoho |
-
1986
- 1986-05-27 FR FR8607569A patent/FR2599543B1/fr not_active Expired - Lifetime
-
1987
- 1987-05-22 EP EP19870401159 patent/EP0247933B1/de not_active Expired - Lifetime
- 1987-05-22 DE DE8787401159T patent/DE3771579D1/de not_active Expired - Lifetime
- 1987-05-26 JP JP12731487A patent/JPS62287199A/ja active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2476823A (en) * | 1945-12-14 | 1949-07-19 | Firestone Tire & Rubber Co | Method of treating polonium plated metal |
| EP0164988A1 (de) * | 1984-06-05 | 1985-12-18 | Westinghouse Electric Corporation | Verfahren zur Dekontamination metallischer Oberflächen |
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 85, 1976, page 264, résumé no. 50701e, Columbus, Ohio, US; & JP-A-75 25 895 (KURITA WATER INDUSTRIES LTD) 27-08-1975 * |
| CHEMICAL ABSTRACTS, vol. 85, no. 26, 27 décembre 1976, page 226, résumé no. 196340h, Columbus, Ohio, US; & JP-A-76 92 736 (KURITA WATER INDUSTRIES LTD) 14-08-1976 * |
Cited By (5)
| 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 |
| FR2820417A1 (fr) * | 2001-02-08 | 2002-08-09 | Commissariat Energie Atomique | Procede de dissolution et de decontamination |
| EP1231609A1 (de) * | 2001-02-08 | 2002-08-14 | Commissariat A L'energie Atomique | Verfahren zum Auflösen und Dekontaminieren |
| US6716402B2 (en) | 2001-02-08 | 2004-04-06 | Commissariat A L'energie Atomique | Dissolution and decontamination process |
| EP1624466A1 (de) | 2004-08-02 | 2006-02-08 | S.T.M.I. Société des Techniques en Milieu Ionisant | Verfahren zum Dekontaminieren von Bleigegenständen |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2599543B1 (fr) | 1992-01-17 |
| JPS62287199A (ja) | 1987-12-14 |
| EP0247933B1 (de) | 1991-07-24 |
| DE3771579D1 (de) | 1991-08-29 |
| FR2599543A1 (fr) | 1987-12-04 |
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