EP0568408B1 - Enceinte de séparation et de confinement de produits radioactifs contenus dans des effluents liquides et installation et procédé pour le traitement de ces effluents - Google Patents

Enceinte de séparation et de confinement de produits radioactifs contenus dans des effluents liquides et installation et procédé pour le traitement de ces effluents Download PDF

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Publication number
EP0568408B1
EP0568408B1 EP19930400989 EP93400989A EP0568408B1 EP 0568408 B1 EP0568408 B1 EP 0568408B1 EP 19930400989 EP19930400989 EP 19930400989 EP 93400989 A EP93400989 A EP 93400989A EP 0568408 B1 EP0568408 B1 EP 0568408B1
Authority
EP
European Patent Office
Prior art keywords
effluents
vessel
electrolysis
tank
radioactive
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
EP19930400989
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German (de)
English (en)
French (fr)
Other versions
EP0568408A1 (fr
Inventor
Christian Brun
Pierre Guillermier
Pierre Saurin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Areva NP SAS
Original Assignee
Framatome SA
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Filing date
Publication date
Application filed by Framatome SA filed Critical Framatome SA
Publication of EP0568408A1 publication Critical patent/EP0568408A1/fr
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    • 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 an enclosure for separation and confinement of radioactive products contained in liquid effluents, and to an installation and a method for the treatment of these effluents.
  • the steam generators of a pressurized water nuclear reactor constitute, by their configuration, their position in the secondary circuit, and the thermohydraulic phenomena linked to their operation, a preferential zone for the accumulation of sludge constituted by particles and oxides. metal from the secondary circuit. It is known to clean this secondary circuit with chemical solutions.
  • Liquid effluents from chemical cleaning of the secondary circuit or decontamination of the primary part of the nuclear reactor are radioactive and must be treated, in particular with a view to their storage. These effluents essentially contain metal cations and organic molecules. Metal cations contain most of the radioactivity in the effluents.
  • the object of the invention is to separate the radioactive products contained in liquid effluents and to store them separately from liquid effluents, this with simple and safe means.
  • the subject of the invention is an enclosure for the separation and confinement of radioactive products contained in liquid effluents, characterized in that it comprises walls made of material absorbing the radiations liable to be emitted by radioactive products, electrodes comprising at least one anode and a cathode, fixed inside the enclosure, means for connecting the electrodes to an electrical supply circuit and means for connecting the enclosure to supply and supply means evacuation of liquid effluents.
  • the invention also relates to an installation for the treatment of liquid effluents containing radioactive products, characterized in that it comprises an enclosure for separation and confinement of radioactive products, the enclosure comprising walls made of radiation absorbing material likely to be emitted by radioactive products, an electrical circuit connected to an anode and a cathode fixed inside the enclosure, means for supplying and discharging liquid effluents connected to the enclosure and means for measuring the radiation dose rate emitted by the contents of the enclosure outside of it.
  • FIG. 1 shows an installation 10 according to a first embodiment of the invention, for the treatment of a predetermined volume of a radioactive solution.
  • the radioactive solution consists of liquid effluents from cleaning or decontamination operations on elements of a nuclear reactor. These effluents include metal ions and organic molecules, in particular carboxylic acids.
  • the installation 10 comprises, from left to right considering FIG. 1, an electro-electrodialysis cell 12, an electrolytic cell 14, and means 16 for ozonating the solution after electrolysis.
  • the electro-electrodialysis cell 12 is of known type and will not be described.
  • the electrolytic cell 14 includes an enclosure 18 for separation and confinement of radioactive products of low and medium activity.
  • the enclosure 18 comprises a body 20 provided with a cover 22 and sealing means of known type, not shown in the figures.
  • the walls of the body 20 and of the cover 22 of the enclosure 18 consist of an internal metallic envelope 24 and an external envelope 26 of concrete, these envelopes being adapted to absorb the radiations emitted by the products stored in the enclosure. 18.
  • the enclosure 18 is adapted to receive the radioactive solution for treatment by electrolysis.
  • the solution is treated in volumes of approximately 200 l.
  • a cathode 28 is fixed to the body 20 of the enclosure 18 and covers its internal wall.
  • An anode 30 is fixed to the cover 22 of the enclosure 18 and extends inside the latter.
  • the cathode 28 is of a known type called "volume". This type of cathode has a large area of contact per unit volume of electrolyte and allows ion transfers from the electrolyte (liquid effluents) to the cathode at high speeds.
  • This type of cathode consists for example of a metallic foam or a metallic expanded.
  • the anode 30 is of known type, for example graphite.
  • the cathode 28 is electrically insulated from the internal metal casing 24 by an intermediate insulating layer 31 of paint or varnish.
  • the anode 30 is also electrically isolated from the metal casing 24 of the cover 22 by known means not shown in the figures.
  • the cathode 28 and the anode 30 comprise means 32,34 for connection to a circuit 36 of electrical supply provided with a current generator 38.
  • the connection means 32,34 are of known type and are accessible from the outside the enclosure 18.
  • a remote detector 40 for measuring the dose rate of the radiation emitted by the products contained in the enclosure 18 outside of the latter is disposed on the external surface of the enclosure 18.
  • the electrolytic cell 14 is connected to a closed circuit 42 for circulating the electrolyte, on the one hand by a conduit 44 for supplying liquid effluents, and on the other hand by a conduit 46 for discharging liquid effluents .
  • the conduit 44 for supplying liquid effluents comprises a first section 44A internal to the enclosure 18 and a second section 44B external to the enclosure 18.
  • the two sections 44A, 44B are interconnected by connection means 48 of the type known, accessible from outside the enclosure 18.
  • the conduit 46 for discharging liquid effluents comprises an internal section 46A and a section 46B external interconnected by connection means 50 accessible from outside the enclosure 18.
  • the closed circuit 42 includes a circulation pump 52, the suction of which is connected by a conduit 54 to the discharge conduit 46, and the discharge conduit 56 of which is connected to the supply conduit 44.
  • the discharge conduit 56 includes means 58 for measuring the activity of the gamma radiation of the solution forming the electrolyte.
  • the electrolytic cell 14 can be isolated from the closed circuit 42 by means of a first valve 60 arranged on the suction duct 54 and a second valve 62 disposed on the discharge duct 56.
  • the electrolytic cell 14 is connected to the electro-electrodialysis cell 12 by means for transferring the volume of radioactive solution comprising a conduit 64 connecting the electro-electrodialysis cell 12 to the supply conduit 44 of the electrolytic cell 14.
  • the solution transfer conduit 64 is provided with a valve 66 making it possible to isolate the electro-electrodialysis cell 12 from the electrolysis cell 14.
  • These means 16 comprise means for transferring the volume of solution after electrolysis comprising a conduit 68 connecting the evacuation conduit 46 of the electrolytic cell 14 to the suction of a self-priming pump 70.
  • This conduit 68 comprises a valve 72 making it possible to isolate the self-priming pump 70 from the electrolytic cell 14.
  • the discharge of the self-priming pump 70 is connected by a conduit 74 to a tank 76 for circulation of the solution.
  • the circulation tank 76 is connected to a closed ozone injection circuit 78 comprising a pump 80, the suction of which is connected by a conduit 82 to the tank 76 for circulation and the outlet of which is connected by a conduit 84 to the upstream end of an ozone injection tube 86.
  • the downstream end of the tube 86 is connected by a conduit 88 to the circulation tank 76.
  • the ozone injection tube 86 is connected to an ozonator 92 by known means comprising a conduit 90.
  • the circulation tank 76 is also connected to means 94 for taking samples of solution during ozonation.
  • These means 94 comprise a conduit 96 fitted with a valve 98, connecting the circulation tank 76 to a container 100 for taking samples.
  • This container 100 is associated with means 102 for measuring the Total Organic Carbon of a solution sample.
  • the circulation tank 76 is connected to means 104 for draining the solution after ozonation.
  • These means 104 comprise a conduit 106, fitted with a valve 108, connecting the circulation tank 76 to evacuation means not shown in the figures.
  • These evacuation means are for example connected to an effluent collector of a nuclear power plant or to the sewer of this power plant.
  • a predetermined volume of radioactive solution undergoes successively an electro-electrodialysis in the cell 12, an electrolysis in the cell 14 and an ozonation thanks to the ozonization means 16.
  • the entire volume of solution is electroelectrodialysis radioactive so as to increase the concentration of radioactive products in the solution.
  • This step is optional and can be eliminated or substituted by adding an electrolyte-support in the solution, as we will describe later in a second embodiment of the invention.
  • valve 66 is closed so as to isolate the electro-electrodialysis cell 12 from the electrolytic cell 14.
  • the entire volume of radioactive solution is transferred to the electrolytic cell 11 to undergo electrolysis there.
  • valve 66 placed between the electro-electrodialysis cell 12 and the electrolytic cell 14 as well as the valve 72 placed between this cell 14 and the ozonization means 16 are closed.
  • the valves 60, 62 at the suction and discharge of the circulation pump 52 are open in order to circulate the solution in the circuit 42.
  • the radioactive cations are deposited on the volume cathode 28. In this way, the solution becomes depleted in radioactive cations and the activity of gamma radiation decreases.
  • the evolution of the gamma radiation activity is monitored using the measurement means 58. When the gamma radiation activity is less than a predetermined threshold, this threshold depending in particular on national standards, the electrolysis is stopped.
  • the entire volume of solution is then transferred to the ozonization tank 76 by the transfer pump 70, after opening of the valve 72.
  • the enclosure 18 As long as the radiation dose rate emitted by the contents of the enclosure 18 outside of it is below a predetermined threshold, successive electrolyses of volumes of radioactive solution are carried out according to the previous steps. When this dose rate exceeds the predetermined threshold, the enclosure 18 is removed from the installation 10 and replaced by a new enclosure. The enclosure 18 containing the radioactive products is then placed in a storage unit, leaving inside the internal sections 44A, 46A of the supply and solution discharge conduits, the cathode 28 on which is located. the radioactive cations and the anode 30 are deposited.
  • the concrete is introduced through the external opening end of an internal section 44A, 46A of the supply duct 44 or the discharge duct 46, after having separated this internal section 44A, 46A from the corresponding external section 44B, 46B.
  • the solution contains a negligible quantity of radioactive elements and ozonation makes it possible to destroy the organic products contained in the solution, in particular the carboxylic acids.
  • the solution is ozonated by circulating this solution in the ozonization circuit 78.
  • Ozone destroys organic molecules by oxidizing them.
  • the ozone consumed by the solution is continuously renewed by means of the ozone injection tube 86.
  • samples are taken using the sampling means 94 so as to measure the Total Organic Carbon of the solution.
  • the value of the Total Organic Carbon is less than a threshold value, corresponding to the destruction of most of the organic molecules, the entire solution is emptied by means 104.
  • the solution is rejected after ozonization in a sewer or in a plant effluent collector.
  • Electro-electrodialysis, electrolysis and ozonation operations are carried out independently. Thus, as soon as one of these operations is finished, it can be started again with a new solution.
  • FIG. 2 shows an installation 10 comprising an electrolytic cell 14 for the treatment of a radioactive solution comprising metal ions and organic molecules. Unlike the first embodiment of the invention, the installation 10 does not include an electro-electrodialysis cell or ozonation means.
  • the installation 10 includes means 110 for injecting a support electrolyte into the volume of radioactive solution before electrolysis.
  • the support electrolyte comprises, for example, iron, cobalt or nickel salts.
  • the addition of a support electrolyte makes it possible to increase the conductivity of the solution and thus improves the efficiency of the electrolysis.
  • the support electrolyte injection means comprise a three-way valve 110 making it possible to add the support electrolyte when the solution is transferred to the electrolytic cell 14.
  • the organic molecules contained in the radioactive solution are destroyed in an incineration unit 112 of known type.
  • This incineration unit 112 destroys organic molecules by transforming them into molecules of water and carbon dioxide.
  • the method for treating the radioactive solution using the installation 10 according to the second embodiment of the invention successively comprises the addition of electrolyte-support in a predetermined volume of radioactive solution, the electrolysis of the radioactive solution and incineration of the solution after electrolysis.
  • the invention is not limited to the two embodiments described. In particular, it is possible to carry out no operation prior to the electrolysis of the radioactive solution. You can choose to add a supporting electrolyte or electroelectrodialysis before electrolysis of the solution. Likewise, ozonation or incineration can be carried out as desired after electrolysis of the solution.
  • liquid effluent treatment process could also be carried out continuously, just as the separation and containment enclosure could be used in the case of a continuous process.
  • the invention makes it possible to treat the liquid effluents produced during decontamination or cleaning operations of elements of a nuclear reactor. It makes it possible to store and very easily isolate the radioactive metallic cations from these effluents. It makes it easy to destroy organic molecules that cannot be stored with radioactive waste or released into the environment.
  • volume cathode integrated in a containment enclosure for radioactive waste makes it possible to collect the radioactive cations directly in an enclosure suitable for their storage.
  • volume cathode makes it possible to obtain a relatively high rate of transfer of the cations from the radioactive solution to the volume cathode.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
EP19930400989 1992-04-21 1993-04-15 Enceinte de séparation et de confinement de produits radioactifs contenus dans des effluents liquides et installation et procédé pour le traitement de ces effluents Expired - Lifetime EP0568408B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9204864 1992-04-21
FR9204864A FR2690270A1 (fr) 1992-04-21 1992-04-21 Enceinte de séparation et de confinement de produits radioactifs contenus dans des effluents liquides et installation et procédé pour le traitement de ces effluents.

Publications (2)

Publication Number Publication Date
EP0568408A1 EP0568408A1 (fr) 1993-11-03
EP0568408B1 true EP0568408B1 (fr) 1996-11-06

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EP19930400989 Expired - Lifetime EP0568408B1 (fr) 1992-04-21 1993-04-15 Enceinte de séparation et de confinement de produits radioactifs contenus dans des effluents liquides et installation et procédé pour le traitement de ces effluents

Country Status (4)

Country Link
EP (1) EP0568408B1 (enrdf_load_stackoverflow)
DE (1) DE69305780T2 (enrdf_load_stackoverflow)
ES (1) ES2093375T3 (enrdf_load_stackoverflow)
FR (1) FR2690270A1 (enrdf_load_stackoverflow)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2736631B1 (fr) * 1995-07-11 1997-10-10 Framatome Sa Procede de traitement par electrolyse d'un effluent liquide contenant des metaux dissous et application au traitement d'effluents contenant du cerium
FR2772510B1 (fr) * 1997-12-15 2000-02-18 Electricite De France Procede de decontamination d'effluents radioactifs
WO2004005586A1 (en) * 2002-07-09 2004-01-15 Gagik Martoyan Electrolytic method of the extraction of metals
DE102008016020A1 (de) * 2008-03-28 2009-10-01 Areva Np Gmbh Verfahren zum Konditionieren einer bei der nasschemischen Reinigung eines nuklearen Dampferzeugers anfallenden Reinigungslösung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2517663B1 (fr) * 1981-12-09 1985-08-09 Commissariat Energie Atomique Procede et dispositif de traitement d'effluents aqueux contenant de l'eau tritiee, electrode utilisable dans un tel dispositif et son procede de preparation
GB2222602A (en) * 1988-08-22 1990-03-14 British Nuclear Fuels Plc Electric cell having removeable electrode assembly
FR2642746A1 (en) * 1989-01-17 1990-08-10 Commissariat Energie Atomique Process and device for the removal of organophosphorus products by electrochemical mineralisation of a nitric solution, capable of being employed in a process for extracting an actinide

Also Published As

Publication number Publication date
EP0568408A1 (fr) 1993-11-03
FR2690270A1 (fr) 1993-10-22
ES2093375T3 (es) 1996-12-16
FR2690270B1 (enrdf_load_stackoverflow) 1994-07-13
DE69305780D1 (de) 1996-12-12
DE69305780T2 (de) 1997-04-03

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