EP0204634B1 - Process and device for treating non-organic solid tritiated wastes - Google Patents

Process and device for treating non-organic solid tritiated wastes Download PDF

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Publication number
EP0204634B1
EP0204634B1 EP19860401184 EP86401184A EP0204634B1 EP 0204634 B1 EP0204634 B1 EP 0204634B1 EP 19860401184 EP19860401184 EP 19860401184 EP 86401184 A EP86401184 A EP 86401184A EP 0204634 B1 EP0204634 B1 EP 0204634B1
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Prior art keywords
waste
gases
detritiation
hydrogen
bringing
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EP19860401184
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German (de)
French (fr)
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EP0204634A1 (en
Inventor
Pierre Giroux
Michel Maj
Gilbert Theis
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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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
    • G21F9/28—Treating solids
    • G21F9/30—Processing
    • G21F9/308—Processing by melting the waste
    • 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
    • G21F9/02—Treating gases

Definitions

  • the subject of the present invention is a method and a device for the treatment of non-organic solid waste having been in contact with tritium or having contained tritiated products.
  • document US Pat. No. 4,285,891 describes a method for removing fission gases such as tritium, krypton, xenon and iodine from an irradiated fuel.
  • an inert gas or mixture of inert gases containing hydrogen is passed in contact with the fuel in order to remove the tritium.
  • the inert gas or the mixture of inert gases alone, that is to say containing no hydrogen, is then passed through in order to remove the other products, the operation being carried out at a temperature above 1000 ° C. .
  • Document DE-A 2 434 876 also discloses a process for removing tritium and its compounds contained in a gas stream, in the. which the gas stream is passed through a reactor where it undergoes catalytic combustion to transform the tritium into tritiated water. The gas stream then passes over one or more dryers which retain water, including tritiated water.
  • the present invention specifically relates to a process for treating tritiated waste which is simple and easy to implement and which makes it possible to considerably reduce the tritium content of the treated parts. It also makes it possible to homogenize the residual content, which facilitates the measurement of this content.
  • hydroxogen used in the present description designates all the isotopes of this element, that is to say as well hydrogen as deuterium or tritium.
  • the oxidation of these elements therefore makes it possible to obtain either water, or heavy water, or tritiated water, or a mixture of the different molecular species.
  • the role of the molecular sieve is to retain the water molecules formed during contact with the oxidation catalyst, which makes it possible to trap, among other things, tritiated water. This is then subjected to further processing.
  • the airlock is in the form of a bell that can pivot relative to the tank.
  • the means for bringing the gases released during the melting to the detritiation unit comprise at least one pumping group connected to the tank of the furnace by a first pipe and to the detritiation unit. by a second pipe.
  • This pumping group can be a combination of primary pumps and / or secondary pumps. It must be particularly tight vis-à-vis the outside and contain the minimum of organic materials, in particular the minimum of lubricating oil or grease in the parts in contact with the fluid. This relates more particularly to gaseous tritium, tritiated water vapor and possibly tritiated hydrocarbons.
  • the availability sitive object of the invention first comprises an oven, bearing the general reference 2, placed inside a glove box 4.
  • This oven consists essentially of a tank 6 arranged horizontally and open at its upper part .
  • this tank is made of double-walled stainless steel and is cooled by a circulation of water.
  • a crucible 12 made of refractory material which contains the tritiated waste 14. These are heated by induction using a coil 16 when their nature allows. If it is aluminum waste, a graphite crucible can be used to achieve electromagnetic coupling. In this case, the temperature of the liquid mass is of the order of 900 ° C.
  • the liquid mass is at a temperature of the order of 1600 ° C.
  • graphite can be added to the waste in order to facilitate the realization of the electromagnetic coupling.
  • carbon can combine with iron to give a carbide with a lower melting point than stainless steel.
  • the tank 6 is closed by a vacuum valve 18, which is surmounted by an airlock 20 used for the introduction of the products to be treated.
  • the airlock 20 is in the form of a bell open downwards and which can pivot around an axis 22.
  • the airlock is thus movable between an open position 20a shown in lines mixed in the figure and a closed position 20b shown in solid lines.
  • a nacelle 13 containing the waste is introduced inside the airlock from below, when the latter is in the open position, thanks to a cable 24.
  • the mold is filled by pivoting the crucible 12.
  • a pipe 26 equipped with a valve 28 places the tank 6 of the oven in communication with a pumping assembly 30 which, in the example shown here, comprises a primary pump 32 and a secondary pump 34.
  • a pumping assembly 30 which, in the example shown here, comprises a primary pump 32 and a secondary pump 34.
  • These pumps allow on the one hand to create a vacuum inside the furnace and, on the other hand, to send the gases released during the melting of the waste 14 to the detritiation unit 36 which will be described later in the remainder of this text.
  • the primary pump 32 or the secondary pump 34 is used, depending on whether one wishes to obtain a more or less high vacuum. It is also possible to sweep the tank 6 with an appropriate gas, for example argon, hydrogen, dry air or helium.
  • a compressed gas bottle 17 placed outside of the glove box 4 and connected to the tank 6 by a pipe 19 while the pumping group 30 remains on the way in order to constantly extract the gases contained in the enclosure 6.
  • it can be maintained under a reduced pressure of the order of 300 millibars, or under a primary vacuum, the pressure being less than 1 millibar.
  • the pumping assembly 30 is connected to the detritiation assembly 36 by a pipe 38 fitted with a valve 40.
  • the pipe 38 opens into a container 42, which contains an oxidation catalyst 46 This may be, for example, a product from the Deoxo series marketed by the ENGELHARD Company.
  • a line 48 connects the container 42 to two containers 50 placed in parallel and each containing a molecular sieve 52.
  • the gases having passed through the detritiation assembly 36 and leaving at the bottom of the containers 50 are extracted through a line 54 connected to an extraction device.
  • a regeneration device 53 comprises a cold trap and a circulation pump. It allows a counter-current circulation of dry air in the molecular sieves. This is how the dry air goes from the regenerator 53 to the bottom of the containers 50, passes through the molecular sieves 52 from bottom to top and returns to the regenerator 53 by a pipe 57.
  • the line 48 is equipped with a heat exchanger 49 in order to cool the gases leaving the container 42 containing the oxidation catalyst 46.
  • the airlock is then emptied by means of the pumping group.
  • the vacuum valve is withdrawn and the airlock is in direct communication with the tank 6.
  • the basket 13 is then lowered inside the crucible 12.
  • the main advantage of the airlock is that it allows the successive introduction of several charges without. stop the heating means and without breaking the vacuum.
  • the waste to be treated when placed in bulk, occupies a significant volume since it is essentially containers, pipes, taps, valves, etc. When they are melted, the molten mass (and therefore the solid mass which will result from it after solidification) is much more compact and occupies only part of the volume of the crucible. This is why it is possible to carry out several loads during the same operation in order to completely fill the crucible 12.
  • the tank 6 of the oven is closed in a sealed manner by the vacuum valve. 18 and the vacuum still prevails inside the tank.
  • the nacelle itself melts with the waste and that it is therefore preferable to make it from a light and inexpensive material whose melting point is compatible with that of the waste to be treated.
  • the gases contained in the enclosure 6 are constantly released during the melting and are evacuated by the pumping group 30.
  • tritium is a gas and that l tritiated water vaporizes, this has the effect of removing most of the tritium or tritiated water absorbed in the waste.
  • the gases are sent, through the pipe 38, to the container 42. During their passage through this container, they are in contact with the oxidation catalyst 46, which has the effect of oxidizing the isotopes of hydrogen and in particular to transform tritium into tritiated water.
  • This tritiated water which is in the form of vapor, then passes along the pipe 48 and passes through the containers 50 which contain the molecular sieves 52. During the passage of the gases through these molecular sieves, these retain all the vapor of water, and therefore tritiated water which will then undergo a special treatment.
  • the method and the device which are the subject of the invention have particularly advantageous advantages, the main one of which is that they make it possible to obtain a metallic mass in which the level of tritium (and therefore the activity) has been considerably reduced. This is primarily due to the fact that most of the tritium was removed with the gases during the melting. On the other hand, the waste which initially occupied a large volume and had a large contact surface with air, is found, after fusion and solidification, in the form of a compact mass of small volume and having a contact surface. with little importance. As the degassing rate of the tritiated compounds is proportional to the surface, this rate is considerably reduced by the transformation of a mass of waste into a compact and homogeneous mass. In addition, while in the pipes, valves, containers from the dismantling of the factory, the contamination is extremely variable, the latter is homogeneous in the solid mass obtained after the fusion. We can therefore know the contamination rate by making a single measurement.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Processing Of Solid Wastes (AREA)
  • Catalysts (AREA)

Description

La présente invention a pour objet un procédé et un dispositif pour le traitement de déchets solides non organiques ayant été en contact avec du tritium ou ayant contenu des produits tritiés.The subject of the present invention is a method and a device for the treatment of non-organic solid waste having been in contact with tritium or having contained tritiated products.

Lors du démantèlement ou de la modification d'installations qui ont contenu du tritium ou ont été en contact avec des produits tritiés, il est nécessaire de faire subir à ces différentes pièces un traitement spécial afin de diminuer leur teneur en tritium et leur taux de dégazage. En effet, le tritium est fortement radioactif et il est difficile de stocker ou d'entreposer ces pièces en l'état. Or, les méthodes de décontamination de pièces tritiées connues à l'heure actuelle ne permettent pas de libérer le tritium contenu dans la masse du matériau.When dismantling or modifying installations which have contained tritium or have been in contact with tritiated products, it is necessary to subject these different parts to a special treatment in order to reduce their tritium content and their degassing rate . In fact, tritium is highly radioactive and it is difficult to store or store these parts as they are. However, the methods of decontamination of tritiated parts known at present do not make it possible to release the tritium contained in the mass of the material.

Ainsi, le document US-A 4 285 891 décrit une méthode pour éliminer les gaz de fission tels que le tritium, le krypton, le xénon et l'iode, d'un combustible irradié. Pour cela, on fait passer, au contact du combustible, un gaz inerte ou mélange de gaz inertes contenant de l'hydrogène afin d'éliminer le tritium. On fait ensuite passer le gaz inerte ou le mélange de gaz inertes seul, c'est-à-dire ne contenant pas d'hydrogène, afin d'éliminer les autres produits, l'opération étant effectuée à une température supérieure à 1000°C.Thus, document US Pat. No. 4,285,891 describes a method for removing fission gases such as tritium, krypton, xenon and iodine from an irradiated fuel. For this, an inert gas or mixture of inert gases containing hydrogen is passed in contact with the fuel in order to remove the tritium. The inert gas or the mixture of inert gases alone, that is to say containing no hydrogen, is then passed through in order to remove the other products, the operation being carried out at a temperature above 1000 ° C. .

On connaît aussi par le document DE-A 2 434 876, un procédé pour éliminer le tritium et ses composés contenus dans un courant gazeux, dans le- . quel on fait passer le courant gazeux dans un réacteur où il subit une combustion catalytique pour transformer le tritium en eau tritiée. Le courant gazeux passe ensuite sur un ou plusieurs dessica- teurs qui retiennent l'eau, y compris l'eau tritiée.Document DE-A 2 434 876 also discloses a process for removing tritium and its compounds contained in a gas stream, in the. which the gas stream is passed through a reactor where it undergoes catalytic combustion to transform the tritium into tritiated water. The gas stream then passes over one or more dryers which retain water, including tritiated water.

La présente invention a précisément pour objet un procédé de traitement de déchets tritiés simple et facile à mettre en oeuvre et qui permet de diminuer considérablement la teneur en tritium des pièces traitées. Elle permet également d'homogénéiser la teneur résiduelle, ce qui facilite la mesure de cette teneur.The present invention specifically relates to a process for treating tritiated waste which is simple and easy to implement and which makes it possible to considerably reduce the tritium content of the treated parts. It also makes it possible to homogenize the residual content, which facilitates the measurement of this content.

Selon la principale caractéristique du procédé objet de l'invention, celui-ci comprend les étapes suivantes consistant à:

  • - faire fondre les déchets à l'intérieur d'une enceinte, un courant d'hydrogène étant envoyé à l'intérieur de la masse de déchets en fusion, réalisant ainsi un barbotage d'hydrogène dans la masse de déchets en fusion, et l'hydrogène et les gaz absorbés dans la masse de déchets étant extraits constamment de l'enceinte; et
  • - soumettre les gaz extraits à un traitement de détritiation consistant à amener le courant gazeux au contact d'un catalyseur d'oxydation afin de transformer l'hydrogène en vapeur d'eau, et à piéger cette vapeur d'eau sur un tamis moléculaire.
According to the main characteristic of the process which is the subject of the invention, it comprises the following steps consisting in:
  • melt the waste inside an enclosure, a stream of hydrogen being sent inside the mass of molten waste, thus effecting a bubbling of hydrogen into the mass of molten waste, and l hydrogen and the gases absorbed in the mass of waste being constantly extracted from the enclosure; and
  • - subjecting the extracted gases to a detritiation treatment consisting in bringing the gas stream into contact with an oxidation catalyst in order to transform the hydrogen into water vapor, and in trapping this water vapor on a molecular sieve.

Le mot "hydrogène" utilisé dans la présente description désigne tous les isotopes de cet élément, c'est-à-dire aussi bien l'hydrogène que le deutérium ou le tritium. L'oxydation de ces éléments permet donc d'obtenir soit de l'eau, soit de l'eau lourde, soit de l'eau tritiée, soit un mélange des différentes espèces moléculaires. Le rôle du tamis moléculaire est de retenir les molécules d'eau formées lors du contact avec le catalyseur d'oxydation, ce qui permet de piéger, entre autres, l'eau tritiée. Celle-ci est ensuite soumise à un traitement ultérieur.The word "hydrogen" used in the present description designates all the isotopes of this element, that is to say as well hydrogen as deuterium or tritium. The oxidation of these elements therefore makes it possible to obtain either water, or heavy water, or tritiated water, or a mixture of the different molecular species. The role of the molecular sieve is to retain the water molecules formed during contact with the oxidation catalyst, which makes it possible to trap, among other things, tritiated water. This is then subjected to further processing.

L'invention a également pour objet un dispositif pour la mise en oeuvre de ce procédé. Selon la principale caractéristique de ce dispositif, celui-ci comprend:

  • - un ensemble de détritiation des gaz libérés au cours de la fusion, et
  • - des moyens pour amener les gaz libérés au cours de la fusion à l'ensemble de détritiation.
The invention also relates to a device for implementing this method. According to the main characteristic of this device, it includes:
  • - a set of detritiation of the gases released during the fusion, and
  • - Means for bringing the gases released during the fusion to the detritiation assembly.

Selon un mode préféré de réalisation de ce dispositif, le four comprend:

  • 1 °) un four pour la fusion des déchets comprenant
    • - une cuve apte à recevoir un creuset contenant les déchets,
    • - des moyens de chauffage,
    • - une vanne à vide fermant ladite cuve, et
    • - un sas d'introduction des déchets, ce sas étant mobile entre une position d'ouverture et une position de fermeture et étant séparé de la cuve par la vanne à vide lorsqu'il est en position de fermeture;
  • 2°) des moyens pour réaliser un barbotage d'hydrogène dans la masse de déchets en fusion;
  • 3°) un ensemble de détritiation des gaz libérés au cours de la fusion, comprenant
    • - au moins un récipient contenant un catalyseur d'oxydation, et
    • - au moins un récipient contenant un tamis moléculaire; et
  • 4°) des moyens pour amener les gaz libérés au cours de la fusion à l'ensemble de détritiation.
According to a preferred embodiment of this device, the oven comprises:
  • 1) a melting furnace waste comprising
    • - a tank capable of receiving a crucible containing the waste,
    • - heating means,
    • a vacuum valve closing said tank, and
    • - an airlock for introducing waste, this airlock being movable between an open position and a closed position and being separated from the tank by the vacuum valve when it is in the closed position;
  • 2) means for carrying out a hydrogen bubbling into the molten waste mass;
  • 3) a set of Tritium gases released during melting, comprising
    • - at least one container containing an oxidation catalyst, and
    • - at least one container containing a molecular sieve; and
  • 4 °) means for bringing the gases released during melting to the entire Tritium.

Dans un mode de réalisation préféré, le sas se présente sous la forme d'une cloche pouvant pivoter par rapport à la cuve.In a preferred embodiment, the airlock is in the form of a bell that can pivot relative to the tank.

Selon une autre caractéristique de ce dispositif, les moyens pour amener les gaz libérés au cours de la fusion à l'ensemble de détritiation comprennent au moins un groupe de pompage relié à la cuve du four par une première canalisation et à l'ensemble de détritiation par une deuxième canalisation. Ce groupe de pompage peut être une combinaison de pompes primaires et/ou de pompes secondaires. Il doit être particulièrement étanche vis-à-vis de l'extérieur et comporter le minimum de matériaux à caractère organique, notamment le minimum d'huile ou de graisse de lubrification dans les parties en contact avec le fluide. Ceci concerne plus particulièrement le tritium gazeux, la vapeur d'eau tritiée et éventuellement les hydrocarbures tritiés.According to another characteristic of this device, the means for bringing the gases released during the melting to the detritiation unit comprise at least one pumping group connected to the tank of the furnace by a first pipe and to the detritiation unit. by a second pipe. This pumping group can be a combination of primary pumps and / or secondary pumps. It must be particularly tight vis-à-vis the outside and contain the minimum of organic materials, in particular the minimum of lubricating oil or grease in the parts in contact with the fluid. This relates more particularly to gaseous tritium, tritiated water vapor and possibly tritiated hydrocarbons.

L'invention apparaîtra mieux à la lecture de la description qui va suivre, donnée à titre d'exemple purement illustratif et nullement limitatif, en référence au dessin annexé, lequel comporte une figure unique représentant de manière schématique l'ensemble du dispositif objet de l'invention.The invention will appear better on reading the description which follows, given by way of purely illustrative and in no way limitative example, with reference to the appended drawing, which comprises a single figure schematically representing the whole of the device object of the invention. 'invention.

Si l'on se reporte au dessin, on voit que le dispositif objet de l'invention comporte d'abord un four, portant la référence générale 2, placé à l'intérieur d'une boîte à gants 4. Ce four est essentiellement constitué d'une cuve 6 disposée horizontalement et ouverte à sa partie supérieure. Dans le mode de réalisation préféré, cette cuve est réalisée en acier inoxydable à double paroi et elle est refroidie par une circulation d'eau. A l'intérieur de cette cuve peut être placé un creuset 12 en matériau réfractaire qui contient les déchets tritiés 14. Ceux-ci sont chauffés par induction grâce à une bobine 16 lorsque leur nature le permet. S'il s'agit de déchets en aluminium, on peut utiliser un creuset en graphite afin de réaliser un couplage électromagnétique. Dans ce cas, la température de la masse liquide est de l'ordre de 900°C. On peut encore ajouter un fondant pour faciliter la fusion ou ajouter un autre métal afin de réaliser un eutectique et abaisser ainsi la température de fusion. S'il s'agit de déchets en acier inoxydable, la masse liquide est à une température de l'ordre de 1600°C. Dans ce cas, on peut ajouter du graphite aux déchets afin de faciliter la réalisation du couplage électromagnétique. Even- tuellement, le carbone peut se combiner avec le fer pour donner un carbure dont le point de fusion est inférieur à celui de l'acier inoxydable. A sa partie supérieure, la cuve 6 est fermée par une vanne à vide 18, laquelle est surmontée d'un sas 20 servant à l'introduction des produits à traiter. Dans le mode de réalisation préferé illustré ici, le sas 20 se présente sous la forme d'une cloche ouverte vers le bas et pouvant pivoter autour d'un axe 22. Le sas est ainsi mobile entre une position d'ouverture 20a représentée en traits mixtes sur la figure et une position de fermeture 20b représentée en traits pleins. Une nacelle 13 contenant les déchets est introduite à l'intérieur du sas par le bas, lorsque celui-ci est en position d'ouverture, grâce à un câble 24. On voit encore, à l'intérieur de la cuve 6, une lingotière 15 dans laquelle on coule le liquide contenu dans le creuset 12 une fois que celui-ci est rempli. Ceci facilite le démoulage du lingot une fois solidifié. Dans le cas particulier décrit ici, le remplissage de la lingotière se fait par pivotement du creuset 12.If we refer to the drawing, we see that the availability sitive object of the invention first comprises an oven, bearing the general reference 2, placed inside a glove box 4. This oven consists essentially of a tank 6 arranged horizontally and open at its upper part . In the preferred embodiment, this tank is made of double-walled stainless steel and is cooled by a circulation of water. Inside this tank can be placed a crucible 12 made of refractory material which contains the tritiated waste 14. These are heated by induction using a coil 16 when their nature allows. If it is aluminum waste, a graphite crucible can be used to achieve electromagnetic coupling. In this case, the temperature of the liquid mass is of the order of 900 ° C. It is also possible to add a flux to facilitate melting or to add another metal in order to produce a eutectic and thus lower the melting temperature. If it is stainless steel waste, the liquid mass is at a temperature of the order of 1600 ° C. In this case, graphite can be added to the waste in order to facilitate the realization of the electromagnetic coupling. Optionally, carbon can combine with iron to give a carbide with a lower melting point than stainless steel. At its upper part, the tank 6 is closed by a vacuum valve 18, which is surmounted by an airlock 20 used for the introduction of the products to be treated. In the preferred embodiment illustrated here, the airlock 20 is in the form of a bell open downwards and which can pivot around an axis 22. The airlock is thus movable between an open position 20a shown in lines mixed in the figure and a closed position 20b shown in solid lines. A nacelle 13 containing the waste is introduced inside the airlock from below, when the latter is in the open position, thanks to a cable 24. We can still see, inside the tank 6, an ingot mold 15 into which the liquid contained in the crucible 12 is poured once the latter is filled. This facilitates the release of the ingot once solidified. In the particular case described here, the mold is filled by pivoting the crucible 12.

Une canalisation 26 équipée d'une vanne 28 met la cuve 6 du four en communication avec un ensemble de pompage 30 qui, dans l'exemple représenté ici, comporte une pompe primaire 32 et une pompe secondaire 34. Ces pompes permettent d'une part de faire le vide à l'intérieur du four et, d'autre part, d'envoyer les gaz libérés au cours de la fusion des déchets 14 à l'ensemble de détritiation 36 qui sera décrit plus loin dans la suite du présent texte. Suivant les cas, on utilise soit la pompe primaire 32, soit la pompe secondaire 34, suivant que l'on désire obtenir un vide plus ou moins poussé. On peut aussi réaliser un balayage de la cuve 6 par un gaz approprié, par exemple l'argon, l'hydrogène, l'air sec ou l'hélium. Pour cela, on utilise par exemple une bouteille de gaz comprimé 17 placée à l'extérieur de la boîte à gants 4 et reliée à la cuve 6 par une canalisation 19 tandis que le groupe de pompage 30 reste en route afin d'extraire constamment les gaz contenus dans l'enceinte 6. Suivant les cas, on peut maintenir celle-ci sous une pression réduite de l'ordre de 300 millibars, ou sous un vide primaire, la pression étant inférieure à 1 millibar. On peut également, tout. en réalisant un tel balayage, insuffler de l'hydrogène dans la masse de déchets en fusion 14, par exemple grâce à une bouteille d'hydrogène 21 placée à l'extérieur de la boîte à gants 4 et reliée au creuset 12 par une canalisation 23. On réalise ainsi une dilution isotopique : la teneur des déchets en isotopes de l'hydrogéne restant constante, si on introduit de l'hydrogène par barbotage, on augmente la teneur en hydrogène et on diminue la teneur en tritium. Cette méthode a donc pour effet d'accélérer la détritiation, d'autant plus que l'hydrogène en excès entraîne le tritium qui s'est ainsi dégagé.A pipe 26 equipped with a valve 28 places the tank 6 of the oven in communication with a pumping assembly 30 which, in the example shown here, comprises a primary pump 32 and a secondary pump 34. These pumps allow on the one hand to create a vacuum inside the furnace and, on the other hand, to send the gases released during the melting of the waste 14 to the detritiation unit 36 which will be described later in the remainder of this text. Depending on the case, either the primary pump 32 or the secondary pump 34 is used, depending on whether one wishes to obtain a more or less high vacuum. It is also possible to sweep the tank 6 with an appropriate gas, for example argon, hydrogen, dry air or helium. For this, use is made, for example, of a compressed gas bottle 17 placed outside of the glove box 4 and connected to the tank 6 by a pipe 19 while the pumping group 30 remains on the way in order to constantly extract the gases contained in the enclosure 6. Depending on the case, it can be maintained under a reduced pressure of the order of 300 millibars, or under a primary vacuum, the pressure being less than 1 millibar. We can also, everything. by carrying out such a sweep, inject hydrogen into the mass of molten waste 14, for example using a hydrogen bottle 21 placed outside the glove box 4 and connected to the crucible 12 by a pipe 23 Isotopic dilution is thus carried out: the content of isotopes of hydrogen isotopes remaining constant, if hydrogen is introduced by bubbling, the hydrogen content is increased and the tritium content is reduced. This method therefore has the effect of accelerating detritiation, especially since the excess hydrogen entrains the tritium which is thus released.

On voit encore sur la figure que l'ensemble de pompage 30 est relié à l'ensemble de détritiation 36 par une canalisation 38 équipée d'une vanne 40. La canalisation 38 débouche dans un récipient 42, qui contient un catalyseur d'oxydation 46. Celui-ci peut être, par exemple, un produit de la série Déoxo commercialisé par la Société ENGELHARD. Une canalisation 48 relie le récipient 42 à deux récipients 50 placés en parallèle et contenant chacun un tamis moléculaire 52. Les gaz ayant traversé l'ensemble de détritiation 36 et sortant à la partie inférieure des récipients 50 sont extraits à travers une canalisation 54 reliée à un dispositif d'extraction. Dans le cas particulier décrit ici, il y a deux tamis moléculaires placés en parallèle, mais un seul est utilisé à la fois. En effet, lorsque l'un de ces tamis est saturé, on envoie le gaz à traiter sur l'autre et le premier est désorbé au moyen d'un dispositif de régénération 53. Ce dispositif comprend un piège froid et une pompe de circulation. Il permet de réaliser une circulation d'air sec à contre-courant dans les tamis moléculaires. C'est ainsi que l'air sec va du régénérateur 53 à la partie inférieure des récipients 50, traverse les tamis moléculaires 52 de bas en haut et retourne au régénérateur 53 par une canalisation 57. Enfin, on voit encore sur la figure que la canalisation 48 est équipée d'un échangeur de chaleur 49 afin de refroidir les gaz qui sortent du récipient 42 contenant le catalyseur d'oxydation 46.It can also be seen in the figure that the pumping assembly 30 is connected to the detritiation assembly 36 by a pipe 38 fitted with a valve 40. The pipe 38 opens into a container 42, which contains an oxidation catalyst 46 This may be, for example, a product from the Deoxo series marketed by the ENGELHARD Company. A line 48 connects the container 42 to two containers 50 placed in parallel and each containing a molecular sieve 52. The gases having passed through the detritiation assembly 36 and leaving at the bottom of the containers 50 are extracted through a line 54 connected to an extraction device. In the particular case described here, there are two molecular sieves placed in parallel, but only one is used at a time. Indeed, when one of these sieves is saturated, the gas to be treated is sent to the other and the first is desorbed by means of a regeneration device 53. This device comprises a cold trap and a circulation pump. It allows a counter-current circulation of dry air in the molecular sieves. This is how the dry air goes from the regenerator 53 to the bottom of the containers 50, passes through the molecular sieves 52 from bottom to top and returns to the regenerator 53 by a pipe 57. Finally, we can still see in the figure that the line 48 is equipped with a heat exchanger 49 in order to cool the gases leaving the container 42 containing the oxidation catalyst 46.

Une opération de détritiation se déroule de la manière suivante :

  • On place une première nacelle de déchets dans le creuset. On ferme la cuve du four. On met alors en route les moyens de chauffage 16 afin d'obtenir la fusion des déchets 14. Le sas 20 est alors pivoté afin de l'amener en position d'ouverture 20a, puis une nacelle 13 contenant une masse de déchets métalliques est introduite à l'intérieur du sas au moyen du câble 24. On fait ensuite pivoter le sas afin de l'amener en position de fermeture.
A detritiation operation takes place as follows:
  • A first basket of waste is placed in the crucible. We close the oven bowl. The heating means 16 are then started in order to obtain the melting of the waste 14. The airlock 20 is then pivoted in order to bring it into the open position 20a, then a nacelle 13 containing a mass of metallic waste is introduced inside the airlock by means of the cable 24. The airlock is then pivoted in order to bring it into the closed position.

On vide alors le sas au moyen du groupe de pompage. On retire la vanne à vide et le sas est en communication directe avec la cuve 6. On descend alors la nacelle 13 à l'intérieur du creuset 12.The airlock is then emptied by means of the pumping group. The vacuum valve is withdrawn and the airlock is in direct communication with the tank 6. The basket 13 is then lowered inside the crucible 12.

Le principal avantage du sas est qu'il permet d'introduire successivement plusieurs charges sans . arrêter les moyens de chauffage et sans casser le vide. En effet, les déchets à traiter, lorsqu'ils sont placés en vrac, occupent un volume important puisqu'il s'agit essentiellement de récipients, tuyaux, robinets, vannes, etc... Lorsqu'ils sont fondus, la masse en fusion (et donc la masse solide qui en résultera après solidification) est beaucoup plus compacte et n'occupe qu'une partie du volume du creuset. C'est pourquoi on peut procéder à plusieurs chargements au cours d'une même opération afin de remplir complètement le creuset 12. Lorsque le sas est en position d'ouverture, la cuve 6 du four est fermée de manière étanche par la vanne à vide 18 et le vide règne toujours à l'intérieur de la cuve. Il est à remarquer que la nacelle elle-même fond avec les déchets et qu'il est donc préférable de la réaliser en un matériau léger et peu coûteux et dont le point de fusion soit compatible avec celui des déchets à traiter.The main advantage of the airlock is that it allows the successive introduction of several charges without. stop the heating means and without breaking the vacuum. Indeed, the waste to be treated, when placed in bulk, occupies a significant volume since it is essentially containers, pipes, taps, valves, etc. When they are melted, the molten mass (and therefore the solid mass which will result from it after solidification) is much more compact and occupies only part of the volume of the crucible. This is why it is possible to carry out several loads during the same operation in order to completely fill the crucible 12. When the airlock is in the open position, the tank 6 of the oven is closed in a sealed manner by the vacuum valve. 18 and the vacuum still prevails inside the tank. It should be noted that the nacelle itself melts with the waste and that it is therefore preferable to make it from a light and inexpensive material whose melting point is compatible with that of the waste to be treated.

Comme les gaz contenus dans l'enceinte 6 sont ' extraits en permanence, les gaz contenus dans les produits 14 se dégagent en permanence au cours de la fusion et sont évacués grâce au groupe de pompage 30. Comme le tritium est un gaz et que l'eau tritiée se vaporise, ceci a pour effet d'éliminer la plus grande partie du tritium ou de l'eau tritiée absorbé dans les déchets. Les gaz sont envoyés, à travers la canalisation 38, jusqu'au récipient 42. Au cours de leur passage à travers ce récipient, ils sont en contact avec le catalyseur d'oxydation 46, ce qui a pour effet d'oxyder les isotopes de l'hydrogène et en particulier de transformer le tritium en eau tritiée. Cette eau tritiée, qui est sous forme de vapeur, passe ensuite le long de la canalisation 48 et traverse les récipients 50 qui contiennent les tamis moléculaires 52. Lors du passage des gaz à travers ces tamis moléculaires, ceux-ci retiennent toute la vapeur d'eau, et donc l'eau tritiée qui subira ensuite un traitement particulier.As the gases contained in the enclosure 6 are 'permanently extracted, the gases contained in the products 14 are constantly released during the melting and are evacuated by the pumping group 30. As tritium is a gas and that l tritiated water vaporizes, this has the effect of removing most of the tritium or tritiated water absorbed in the waste. The gases are sent, through the pipe 38, to the container 42. During their passage through this container, they are in contact with the oxidation catalyst 46, which has the effect of oxidizing the isotopes of hydrogen and in particular to transform tritium into tritiated water. This tritiated water, which is in the form of vapor, then passes along the pipe 48 and passes through the containers 50 which contain the molecular sieves 52. During the passage of the gases through these molecular sieves, these retain all the vapor of water, and therefore tritiated water which will then undergo a special treatment.

Le procédé et le dispositif objets de l'invention présentent des avantages particulièrement intéressants dont le principal est qu'ils permettent d'obtenir une masse métallique dans laquelle le taux de tritium (et donc l'activité) a été considérablement diminué. Ceci est d'abord dû au fait que la plus grande partie du tritium a été évacuée avec les gaz pendant la fusion. D'autre part, les déchets qui initialement occupaient un grand volume et présentaient une surface de contact importante avec l'air, se retrouvent, après fusion et solidification, sous la forme d'une masse compacte de faible volume et présentant une surface de contact avec l'air peu importante. Comme le taux de dégazage des composés tritiés est proportionnel à la surface, ce taux est considérablement diminué par la transformation d'une masse de déchets en une masse compacte et homogène. De plus, alors que dans les tuyaux, vannes, récipients provenant du démantèlement de l'usine, la contamination est extrêmement variable, cette dernière est homogène dans la masse solide obtenue après la fusion. On peut donc connaître le taux de contamination en faisant une seule mesure.The method and the device which are the subject of the invention have particularly advantageous advantages, the main one of which is that they make it possible to obtain a metallic mass in which the level of tritium (and therefore the activity) has been considerably reduced. This is primarily due to the fact that most of the tritium was removed with the gases during the melting. On the other hand, the waste which initially occupied a large volume and had a large contact surface with air, is found, after fusion and solidification, in the form of a compact mass of small volume and having a contact surface. with little importance. As the degassing rate of the tritiated compounds is proportional to the surface, this rate is considerably reduced by the transformation of a mass of waste into a compact and homogeneous mass. In addition, while in the pipes, valves, containers from the dismantling of the factory, the contamination is extremely variable, the latter is homogeneous in the solid mass obtained after the fusion. We can therefore know the contamination rate by making a single measurement.

A titre d'essai, on a réalisé une installation capable de traiter 60 kg de déchets au cours d'un cycle, c'est-à-dire en plusieurs chargements du creuset jusqu'à remplissage de celui-ci. Certains essais ont permis de ramener l'activité des déchets de 0,57 millicurie par kilogramme à 2.10 -3 millicurie par kilogramme, c'est-à-dire de diminuer la concentration en tritium d'un facteur de 250. D'autres essais ont permis d'obtenir des lingots manipulables sans protection particulière contre le dégazage.As a test, an installation was made capable of treating 60 kg of waste during a cycle, that is to say in several loads of the crucible until it is filled. Some tests have made it possible to reduce the waste activity from 0.57 millicurie per kilogram to 2.10 -3 millicurie per kilogram, that is to say to reduce the tritium concentration by a factor of 250. Other tests have made it possible to obtain ingots which can be handled without special protection against degassing.

Enfin, il est bien entendu que l'invention ne se limite pas au seul mode de réalisation qui vient d'être décrit ici, mais qu'on peut envisager des variantes sans sortir pour autant du cadre de l'invention. C'est ainsi que l'homme de l'art pourra utiliser d'autres types de fours ou choisir le type de pompe qui convient le mieux pour l'installation de pompage, ou modifier le nombre et la disposition des récipients de l'ensemble de détritiation, et les placer en parallèle ou en série.Finally, it is understood that the invention is not limited to the single embodiment which has just been described here, but that variants can be envisaged without departing from the scope of the invention. Thus, a person skilled in the art can use other types of ovens or choose the type of pump which is most suitable for the pumping installation, or modify the number and arrangement of the containers of the assembly. detritiation, and place them in parallel or in series.

Claims (7)

1. Process for the treatment of solid and meltable tritiated waste, characterized in that it comprises the following stages of melting the waste (14) within an enclosure (6), a hydrogen flow being passed into the molten waste mass (14), thus bringing about a hydrogen bubbling into the molten waste mass, and the hydrogen and gases absorbed in the waste mass are constantly extracted from the enclosure and subjecting the extracted gases to a detritiation treatment consisting of bringing these gases into contact with an oxidation catalyst in order to transform the hydrogen into water vapour and trap said water vapour on a molecular sieve.
2. Process according to claim 1, characterized in that the enclosure (6) is scavenged by a gaseous flow.
3. Apparatus for the treatment of solid and meltable tritiated waste, characterized in that it comprises:
1) a furnace (2) for melting the waste (14) incorporating a vessel (6) able to receive a crucible (12) containing the waste (14), heating means (16), a vacuum valve (18) sealing said vessel (6) and a lock (20) for introducing the waste, said lock (20) being mobile between an open position (20a) and a closed position (20b) and being separated from the vessel (6) by the vacuum valve (18) when it is in the closed position;
2) means for carrying out a hydrogen bubbling into the molten waste mass;
3) an assembly (36) for detritiating gases released during melting incorporating at least one container (42) containing an oxidation catalyst (46) and at least one container (50) containing a molecular sieve (52); and
4) means (32, 34) for bringing the gases released during melting to the detritiation assembly (36).
4. Apparatus according to claim 3, characterized in that the lock (20) is in the form of a bell able to pivot with respect to the vessel (6).
5. Apparatus according to either the claims 3 and 4, characterized in that the means for bringing the gases released during melting to the detritiation assembly (36) include at least one pump (32) connected to the vessel (6) of furnace (2) by a first pipe (26) and to the detritiation assembly (36) by a second pipe (38).
6. Apparatus according to claim 5, characterized in that said pump is a primary pump (32).
7.. Apparatus according to claim 6, characterized in that the means for bringing the gases released during melting to the detritiation assembly (36) also include a secondary pump (34) associated with the primary pump (32).
EP19860401184 1985-06-07 1986-06-03 Process and device for treating non-organic solid tritiated wastes Expired - Lifetime EP0204634B1 (en)

Applications Claiming Priority (2)

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FR8508666 1985-06-07
FR8508666A FR2583208B1 (en) 1985-06-07 1985-06-07 PROCESS AND DEVICE FOR THE TREATMENT OF NON-ORGANIC SOLID TRITY WASTE

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EP0204634A1 EP0204634A1 (en) 1986-12-10
EP0204634B1 true EP0204634B1 (en) 1990-05-23

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JP (1) JPS61284697A (en)
DE (1) DE3671563D1 (en)
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FR2620262B1 (en) * 1987-09-09 1989-11-17 Commissariat Energie Atomique PROCESS AND PLANT FOR THE TREATMENT OF SOLID ORGANIC WASTE CONTAMINATED WITH TRITIUM
DE3930420C1 (en) * 1989-09-12 1990-11-22 Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Der Verteidigung, Dieser Vertreten Durch Den Praesidenten Des Bundesamtes Fuer Wehrtechnik Und Beschaffung, 5400 Koblenz, De Radioactive waste tritium sepn. - by flushing in gas flow with oxygen, heating and passing tritium through water
DE4029222C1 (en) * 1990-09-14 1991-08-22 Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Der Verteidigung, Dieser Vertreten Durch Den Praesidenten Des Bundesamtes Fuer Wehrtechnik Und Beschaffung, 5400 Koblenz, De Economical and efficient tritium sepn. - involves passing gas to molten electrodes to ionise molecules, wash tower for absorption and condensate prodn.
LU87907A1 (en) * 1991-03-13 1992-11-16 Euratom METHOD FOR REPROCESSING ABSORBER BARS FROM WATER-COOLED CORE REACTORS
IT1400531B1 (en) * 2010-06-22 2013-06-11 Commissariat Energie Atomique PROCESS FOR THE DETRIFICATION OF SOFT HOUSEKEEPING WASTE AND RELATIVE PLANT
FR2974444B1 (en) * 2011-04-21 2015-11-27 Commissariat Energie Atomique DEVICE AND METHOD FOR DETERIATION
FR3101558B1 (en) 2019-10-03 2021-10-22 Onet Tech Cn Process for decontaminating a metal part containing a gas by laser irradiation in a liquid medium

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GB1096072A (en) * 1964-02-27 1967-12-20 Atomic Energy Authority Uk Improvements in or relating to incinerators
US4178350A (en) * 1973-08-27 1979-12-11 Engelhard Minerals & Chemicals Corp. Removal of tritium and tritium-containing compounds from a gaseous stream
US4285891A (en) * 1979-12-31 1981-08-25 Exxon Nuclear, Inc. Method of removing fission gases from irradiated fuel
DE3011602A1 (en) * 1980-03-26 1981-10-08 Kernforschungsanlage Jülich GmbH, 5170 Jülich METHOD AND DEVICE FOR THE FINAL STORAGE OF TRITIUM, ESPECIALLY TRITIUM WASTE FROM NUCLEAR POWER PLANTS, WITH THE POSSIBILITY OF TRITIUM RECOVERY

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EP0204634A1 (en) 1986-12-10
ES555832A0 (en) 1987-12-16
DE3671563D1 (en) 1990-06-28
FR2583208A1 (en) 1986-12-12
FR2583208B1 (en) 1992-04-24
JPS61284697A (en) 1986-12-15
ES8801473A1 (en) 1987-12-16

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