EP0018923A1 - Process for ruthenium decontamination of liquid radioactive wastes - Google Patents
Process for ruthenium decontamination of liquid radioactive wastes Download PDFInfo
- Publication number
- EP0018923A1 EP0018923A1 EP80400616A EP80400616A EP0018923A1 EP 0018923 A1 EP0018923 A1 EP 0018923A1 EP 80400616 A EP80400616 A EP 80400616A EP 80400616 A EP80400616 A EP 80400616A EP 0018923 A1 EP0018923 A1 EP 0018923A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- effluent
- ruthenium
- iron
- contact
- cupric ions
- 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
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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
- G21F9/04—Treating liquids
- G21F9/06—Processing
Definitions
- the present invention relates to a ruthenium decontamination process for radioactive effluents usable for raw effluents or for effluents subjected beforehand to chemical decontamination treatments of conventional type.
- radioactive effluents such as solutions originating from the treatment of irradiated fuels can be subjected to various chemical decontamination treatments making it possible in particular to remove ruthenium.
- Most of these treatments consist of forming precipitates capable of fixing ruthenium within the effluent to be treated, for example by adding ferrous ions and cupric ions to this effluent and then alkalizing the medium to precipitate the corresponding compounds. of iron and copper.
- the present invention specifically relates to a ruthenium decontamination process for liquid radioactive effluents which in particular makes it possible to improve the ruthenium decontamination rate of effluents treated beforehand by chemical methods of conventional type.
- the process of the invention advantageously takes advantage of the fact that by bringing an effluent containing Cu 2+ ions with iron, according to the following reaction scheme: j a copper deposit which entails most of the ruthenium, this copper deposit being accompanied by partial dissolution of the iron in the effluent in the state of ferrous iron.
- the decontamination rate of the ruthenium effluent can be further improved by then adjusting the pH of the effluent to a value greater than 8 to precipitate the iron that has gone into solution, which makes it possible to fix- on the precipitate of iron hydroxide an additional quantity of ruthenium.
- the quantity of cupric ions added to said effluent is from 50 to 100 mg of Cu 2+ ions per liter of effluent
- said effluent containing the cupric ions is brought into contact with a molar quantity of iron greater than the molar quantity of cupric ions added to said effluent.
- the quantity of iron used corresponds to approximately 500 mg of iron per liter of effluent.
- the process of the invention has the particular advantage of leading to a satisfactory decontamination rate and moreover of avoiding the formation of large volumes of precipitates and sludge which must then be stored.
- a radioactive effluent from a reprocessing plant for irradiated nuclear fuels is treated according to the method of the invention, this effluent having been treated beforehand by chemical means.
- cupric sulphate is added to the effluent so as to introduce approximately 100 mg of cupric ions per liter of effluent.
- pH of the effluent was adjusted to a value of 3 by addition of nitric acid in order to avoid precipitation of the cupric ions in the form of cupric hydroxide.
- the effluent After stabilization of the pH, the effluent is brought into contact with iron powder, the amount of iron used being 500 mg per liter of effluent, by subjecting the whole to stirring for a few minutes in a contactor of conventional type. , which makes it possible to obtain according to the following reaction scheme: a copper deposit and the partial solution of iron in the ferrous state.
- a quantity of sodium hydroxide sufficient to bring the pH to a value substantially equal to 8.5 is then added to the effluent, which leads to the precipitation of the iron passed into solution, and provides additional decontamination in ruthenium because the ruthenium binds on the iron precipitate thus formed.
- the liquid effluent is separated from the sludge formed, for example by decantation.
- the volume of sludge formed represents 1.5% of the volume of the treated effluent.
- the FD decontamination rate of the ruthenium effluent which corresponds to the ratio between the ruthenium activities of the effluent before and after decontamination treatment is of the order of 8.
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
L'invention a pour objet un procédé de décontamination en ruthénium d'effluents radioactifs liquides. Ce procédé consiste: a) à ajuster le pH dudit effluent à une valeur inférieure à 5 et à lui ajouter des ions cuivriques; b) à mettre en contact avec du fer l'effluent ainsi traité pour former un précipité de cuivre qui entraîne le ruthénium; c) à séparer l'effluent liquide des boues formées. Application au traitement d'effluents radioactifs provenant d'une installation de traitement de combustibles irradiés.The invention relates to a ruthenium decontamination process for liquid radioactive effluents. This process consists of: a) adjusting the pH of said effluent to a value less than 5 and adding cupric ions thereto; b) bringing the effluent thus treated into contact with iron to form a precipitate of copper which entrains the ruthenium; c) separating the liquid effluent from the sludge formed. Application to the treatment of radioactive effluents from an irradiated fuel treatment installation.
Description
La présente invention a pour objet un procédé de décontamination en ruthénium d'effluents radioactifs utilisable pour des effluents bruts ou pour des effluents soumis préalablement à des traitements de décontamination chimique de type classique.The present invention relates to a ruthenium decontamination process for radioactive effluents usable for raw effluents or for effluents subjected beforehand to chemical decontamination treatments of conventional type.
On sait que des effluents radioactifs tels que des solutions provenant du traitement de combustibles irradiés peuvent être soumis à différents traitements chimiques de décontamination permettant en particulier d'éliminer le ruthénium. Ces traitements consistent pour la plupart à former au sein de l'effluent à traiter des précipités aptes à fixer le ruthénium, par exemple en ajoutant à cet effluent des ions ferreux et des ions cuivriques et en alcalinisant en suite le milieu pour précipiter les composés correspondants de fer et de cuivre.It is known that radioactive effluents such as solutions originating from the treatment of irradiated fuels can be subjected to various chemical decontamination treatments making it possible in particular to remove ruthenium. Most of these treatments consist of forming precipitates capable of fixing ruthenium within the effluent to be treated, for example by adding ferrous ions and cupric ions to this effluent and then alkalizing the medium to precipitate the corresponding compounds. of iron and copper.
Cependant, les effluents ainsi traités présentent encore une teneur en ruthénium trop importante, ce qui nécessite un traitement complémentaire pour amener leur activité résiduelle en ruthénium à des valeurs acceptables.However, the effluents thus treated still have too high a ruthenium content, which requires additional treatment to bring their residual ruthenium activity to acceptable values.
La présente invention a précisément pour objet un procédé de décontamination en ruthénium d'effluents radioactifs liquides qui permet en particulier d'améliorer le taux de décontamination en ruthénium d'effluents traités préalablement par des procédés chimiques de type classique.The present invention specifically relates to a ruthenium decontamination process for liquid radioactive effluents which in particular makes it possible to improve the ruthenium decontamination rate of effluents treated beforehand by chemical methods of conventional type.
Le procédé selon l'invention de décontamination en ruthénium d'un effluent liquide radioactif se caractérise en ce qu'il consiste :
- a) - à ajuster le pH dudit effluent à une valeur inférieure à 5 et à lui ajouter des ions cuivriques ;
- b) - à mettre en contact avec du fer ledit effluent ainsi traité pour former un précipité de cuivre qui entraîne le ruthénium, et
- c) - à séparer l'effluent liquide des boues formées.
- a) - adjusting the pH of said effluent to a value less than 5 and adding cupric ions thereto;
- b) - bringing said effluent thus treated into contact with iron to form a copper precipitate which entrains ruthenium, and
- c) - to separate the liquid effluent from the sludge formed.
Le procédé de l'invention tire avantageusement profit du fait qu'en mettant en contact un effluent contenant des ions Cu2+ avec du fer, on obtient selon le schéma réactionnel suivant : j
Par ailleurs, selon l'invention on peut encore améliorer le taux de décontamination de l'effluent en ruthénium en ajustant ensuite à une valeur supérieure à 8 le pH de l'effluent pour précipiter le fer passé en solution, ce qui permet de fixer-sur le précipité d'hydroxyde de fer une quantité complémentaire de ruthénium.Furthermore, according to the invention, the decontamination rate of the ruthenium effluent can be further improved by then adjusting the pH of the effluent to a value greater than 8 to precipitate the iron that has gone into solution, which makes it possible to fix- on the precipitate of iron hydroxide an additional quantity of ruthenium.
Selon une caractétistique avantageuse du procédé de l'invention, la quantité d'ions cuivriques ajoutés audit effluent est de 50 à 100 mg d'ions Cu2+ par litre d'effluerAccording to an advantageous characteristic of the process of the invention, the quantity of cupric ions added to said effluent is from 50 to 100 mg of Cu 2+ ions per liter of effluent
Selon une autre caractéristique du procédé de l'invention; on met en contact ledit effluent contenant les ions cuivriques avec une quantité molaire de fer supérieure à la quantité molaire d'ions cuivriques ajoutée audit effluent.According to another characteristic of the method of the invention; said effluent containing the cupric ions is brought into contact with a molar quantity of iron greater than the molar quantity of cupric ions added to said effluent.
Avantageusement, la quantité de fer utilisée correspond à environ 500 mg de fer par litre d'effluent.Advantageously, the quantity of iron used corresponds to approximately 500 mg of iron per liter of effluent.
Selon l'invention, on peut réaliser l'étape de mise en contact avec du fer de l'effluent contenant des ions cuivriques des deux manières suivantes :
- - soit en faisant percoler cet effluent sur une colonne contenant du fer, par exemple sous la forme de copeaux, de laine ou de grenaille de fer ;
- - soit en agitant l'effluent avec du fer en poudre dans un contacteur de type classique.
- - Either by percolating this effluent on a column containing iron, for example in the form of shavings, wool or iron shot;
- - or by stirring the effluent with powdered iron in a conventional type contactor.
Le procédé de l'invention présente notamment l'avantage de conduire à un taux de décontamination satisfaisant et d'éviter par ailleurs la formation de volumes importants de précipités et de boues qui doivent être ensuite stockés.The process of the invention has the particular advantage of leading to a satisfactory decontamination rate and moreover of avoiding the formation of large volumes of precipitates and sludge which must then be stored.
L'invention sera mieux comprise à la lecture de l'exemple suivant donné bien entendu à titre illustratif et non limitatif.The invention will be better understood on reading the following example given of course by way of illustration and not limitation.
Dans cet exemple, on traite selon le procédé de l'invention un effluent radioactif provenant d'une usine de retraitement de combustibles nucléaires irradiés, cet effluent ayant été traité au préalable par voie chimique.In this example, a radioactive effluent from a reprocessing plant for irradiated nuclear fuels is treated according to the method of the invention, this effluent having been treated beforehand by chemical means.
Lors de ce traitement chimique préalable, on a ajouté à l'effluent qui présentait initialement une activité radiochimique en ruthénium 106 de 45 000 microcuries par m3, des ions cuivriqués et des ions ferreux sous la forme d'une solution aqueuse des sulfates correspondants, puis de la soude pour amener le pH de l'effluent à une valeur d'environ 8,5, ce qui a permis de former dans cet effluent des précipités entraînant le ruthénium. Après coagulation et filtration des précipités, l'effluent présentait une activité en ruthénium 106 de 3 180 microcuries par m3 et avait les caractéristiques suivantes :During this preliminary chemical treatment, copper effluents and ferrous ions were added to the effluent which initially exhibited a radiochemical activity in ruthenium 106 of 45,000 microcuries per m 3 , in the form of an aqueous solution of the corresponding sulfates, then soda to bring the pH of the effluent to a value of about 8.5, which made it possible to form in this effluent precipitates entraining ruthenium. After coagulation and filtration of the precipitates, the effluent exhibited a ruthenium 106 activity of 3,180 microcuries per m 3 and had the following characteristics:
Radiochimiques en 1.10-6 Ci/m3:
Après ce traitement préalable, on ajoute à l'effluent une solution de sulfate cuivrique de façon à introduire environ 100 mg d'ions cuivriques par litre d'effluent. Au préalable, on a ajusté le pH de l'effluent à une valeur de 3 par addition d'acide nitrique afin d'éviter la précipitation des ions cuivriques sous la forme d'hydroxyde cuivrique.After this preliminary treatment, a solution of cupric sulphate is added to the effluent so as to introduce approximately 100 mg of cupric ions per liter of effluent. Beforehand, the pH of the effluent was adjusted to a value of 3 by addition of nitric acid in order to avoid precipitation of the cupric ions in the form of cupric hydroxide.
Après stabilisation du pH, on met en contact l'effluent avec du fer en poudre, la quantité de fer utilisée étant de 500 mg par litre d'effluent, en soumettant l'ensemble à une agitation pendant quelques minutes dans un contacteur de type classique, ce qui permet d'obtenir selon le schéma réactionnel suivant :
On ajoute ensuite à l'effluent une quantité de soude suffisante pour amener le pH à une valeur sensiblement égale à 8,5, ce qui conduit à la précipitation du fer passé en solution, et assure une décontamination complémentaire en ruthénium car le ruthénium se fixe sur le précipité de fer ainsi formé. On sépare enfin, par exemple par décantation, l'effluent liquide des boues formées.A quantity of sodium hydroxide sufficient to bring the pH to a value substantially equal to 8.5 is then added to the effluent, which leads to the precipitation of the iron passed into solution, and provides additional decontamination in ruthenium because the ruthenium binds on the iron precipitate thus formed. Finally, the liquid effluent is separated from the sludge formed, for example by decantation.
A la fin de ce traitement, le volume des boues formées représente 1,5 % du volume de l'effluent traité. Le taux de décontamination FD de l'effluent en ruthénium, qui correspond au rapport entre les activités en ruthénium de l'effluent avant et après traitement de décontamination est de l'ordre de 8.At the end of this treatment, the volume of sludge formed represents 1.5% of the volume of the treated effluent. The FD decontamination rate of the ruthenium effluent, which corresponds to the ratio between the ruthenium activities of the effluent before and after decontamination treatment is of the order of 8.
Des expériences similaires conduites sur des effluents analogues en faisant varier le pH initial de l'effluent entre 2 et 3 et la quantité d'ions cuivriques ajoutée entre 50 et 100 mg par litre d'effluent ont montré que l'on obtenait un FD en ruthénium compris entre 3 et 10. Le volume des boues formées représentait entre 1 et 2 % du volume de l'effluent traité.Similar experiments carried out on similar effluents by varying the initial pH of the effluent between 2 and 3 and the amount of cupric ions added between 50 and 100 mg per liter of effluent have shown that an FD is obtained by ruthenium between 3 and 10. The volume of sludge formed represented between 1 and 2% of the volume of the treated effluent.
On constate ainsi que la mise en oeuvre de l'invention permet d'améliorer de façon importante le taux de décontamination en ruthénium d'un effluent prétraité par voie chimique.It is thus noted that the implementation of the invention makes it possible to significantly improve the ruthenium decontamination rate of an effluent pretreated by chemical means.
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR7911470A FR2456372A1 (en) | 1979-05-07 | 1979-05-07 | PROCESS FOR RUTHENIUM DECONTAMINATION OF LIQUID RADIOACTIVE EFFLUENTS |
FR7911470 | 1979-05-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0018923A1 true EP0018923A1 (en) | 1980-11-12 |
EP0018923B1 EP0018923B1 (en) | 1983-09-21 |
Family
ID=9225134
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80400616A Expired EP0018923B1 (en) | 1979-05-07 | 1980-05-06 | Process for ruthenium decontamination of liquid radioactive wastes |
Country Status (5)
Country | Link |
---|---|
US (1) | US4331551A (en) |
EP (1) | EP0018923B1 (en) |
JP (1) | JPS5619499A (en) |
DE (1) | DE3064890D1 (en) |
FR (1) | FR2456372A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60161598A (en) * | 1983-12-15 | 1985-08-23 | 日本原子力研究所 | Method of treating radioactive waste liquor containing radioactive ruthenium |
JPS60196700A (en) * | 1984-03-21 | 1985-10-05 | 株式会社日立製作所 | Method of removing radioactivity in radioactive waste liquor |
JPH06300042A (en) * | 1993-04-13 | 1994-10-25 | Nippon Seiko Kk | Static pressure gas bearing |
EP1157076A1 (en) * | 1998-11-18 | 2001-11-28 | Radiovascular Systems, L.L.C. | Radioactive coating solutions, methods, and substrates |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2124126A1 (en) * | 1971-02-08 | 1972-09-22 | Commissariat Energie Atomique |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2792412A (en) * | 1954-03-04 | 1957-05-14 | Harold R Schmidt | Recovery of ruthenium from aqueous solutions |
-
1979
- 1979-05-07 FR FR7911470A patent/FR2456372A1/en active Granted
-
1980
- 1980-04-29 US US06/144,911 patent/US4331551A/en not_active Expired - Lifetime
- 1980-05-06 DE DE8080400616T patent/DE3064890D1/en not_active Expired
- 1980-05-06 EP EP80400616A patent/EP0018923B1/en not_active Expired
- 1980-05-07 JP JP6046280A patent/JPS5619499A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2124126A1 (en) * | 1971-02-08 | 1972-09-22 | Commissariat Energie Atomique |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, Vol. 84, No. 12, 22 Mars 1976 ref. 79402y, page 369 Colombus Ohio, US & JP-A-50 140799 (EBARA MFG CO LTD)(12-11-1975). * |
Also Published As
Publication number | Publication date |
---|---|
DE3064890D1 (en) | 1983-10-27 |
JPS5619499A (en) | 1981-02-24 |
FR2456372A1 (en) | 1980-12-05 |
US4331551A (en) | 1982-05-25 |
EP0018923B1 (en) | 1983-09-21 |
FR2456372B1 (en) | 1981-08-14 |
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