EP2774155A1 - Method for treating a cladding containing sintered calcium hydride - Google Patents

Method for treating a cladding containing sintered calcium hydride

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Publication number
EP2774155A1
EP2774155A1 EP12794429.6A EP12794429A EP2774155A1 EP 2774155 A1 EP2774155 A1 EP 2774155A1 EP 12794429 A EP12794429 A EP 12794429A EP 2774155 A1 EP2774155 A1 EP 2774155A1
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EP
European Patent Office
Prior art keywords
sheath
sintered
treatment
calcium hydride
treatment according
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
Application number
EP12794429.6A
Other languages
German (de)
French (fr)
Other versions
EP2774155B1 (en
Inventor
Serge Sellier
Arnaud LECLERC
Janick Verdelli
Joël GODLEWSKI
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Publication of EP2774155A1 publication Critical patent/EP2774155A1/en
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Publication of EP2774155B1 publication Critical patent/EP2774155B1/en
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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
    • G21F9/28—Treating solids
    • 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

Definitions

  • the present invention is in the field of the treatment of nuclear waste.
  • It relates in particular to the treatment of a sheath containing sintered calcium hydride (Ca3 ⁇ 4).
  • This material is generally in the form of slabs which are stacked in a cylindrical sealed steel sheath.
  • the nuclear waste treatment sector must neutralize the chemical risk while reducing the volume of waste as much as possible and optimizing their subsequent conditioning. In order to meet this double constraint, it would therefore be desirable to have a treatment at the end of which, on the one hand, the waste resulting from the sheath, and on the other hand the waste resulting from the hydride wafers.
  • calcium irradiated are evacuated by ways adapted to the nature of each waste.
  • One of the aims of the invention is to provide a process for treating a sheath containing sintered calcium hydride and optionally a radioactive material, which exhibits all or some of the aforementioned advantages.
  • the present invention thus relates to a process for treating a sheath, in which there is a sintered material which consists wholly or partly of sintered calcium hydride which may optionally contain at least one radioactive material.
  • the method comprises a step in which the sintered material is contacted with a reaction mixture containing 0.5% to 5% by weight of water vapor, 5% to 25% carbon dioxide and 74.5% by molar percentage. % to 94.5% of a chemically inert gas, i.e. a gas preventing a reaction between oxygen (possibly present in the reaction atmosphere) and hydrogen (produced by the carbonation reaction described hereinafter).
  • a chemically inert gas i.e. a gas preventing a reaction between oxygen (possibly present in the reaction atmosphere) and hydrogen (produced by the carbonation reaction described hereinafter).
  • the contacting is carried out for a time to transform all the sintered calcium hydride into a calcium carbonate powder.
  • This transformation can be interrupted and resumed at the moment chosen by the operator, or its kinetics modulated depending on the amount of reaction mixture injected.
  • the particular treatment method of the invention is to convert the sintered calcium hydride into a calcium carbonate powder which is non-adherent to the sheath walls and chemically inert.
  • the non-adherent powder obtained at the end of the treatment process of the invention comprising calcium carbonate, is therefore naturally extracted from the sheath by simple gravity, with the radioactive material and / or any other material that may be present. 'it contains.
  • This property of non-adhesion avoids at best the dissemination of radioactive material possibly present in the calcium carbonate powder, as well as the contamination of the cladding by retention of material.
  • the calcium carbonate powder can be discharged to a conventional die or adapted to radioactive waste.
  • waste gas such as for example hydrogen (3 ⁇ 4), optionally tritiated (HT) and / or tritium ( 2 ).
  • This gaseous effluent can be extracted during or after the treatment process.
  • radioactive material possibly present is found at the end of the treatment in gaseous form (such as tritiated hydrogen or tritium), it is discharged as a radioactive gaseous effluent.
  • gaseous form such as tritiated hydrogen or tritium
  • radioactive material there is no longer any radioactive material in the calcium carbonate powder.
  • the possible initial presence of radioactive material nevertheless requires the evacuation of this powder to a simplified pathway adapted to radioactive waste, which is however less restrictive than that which would be imposed by the actual presence of a radioactive material in the waste to be discharged.
  • the sheath is not altered or destroyed during the treatment of the invention, because the calcium carbonate is a relatively chemically inert compound and its formation is accompanied by a limited expansion.
  • the sheath is not or only slightly contaminated with traces of calcium carbonate or any other radioactive material it contains.
  • the sheath can then be evacuated to a simplified stream adapted to radioactive waste to be scrapped or recycled in the nuclear industry.
  • This separation of the dies reduces the volume of waste, since obtaining a powder makes it possible to obtain a compact package and the sheath can optionally be recycled.
  • the method of the invention makes it possible to treat with a minimum of manipulation a sheath containing a sintered material, which is particularly advantageous when this material contains at least one radioactive material.
  • the sintered material comprises sintered calcium hydride and optionally at least one radioactive material.
  • the radioactive material is for example a material containing the tritium element (T).
  • the treatment method of the invention comprises a step in which the sintered material is contacted with a reaction mixture containing 0.5 mol% of steam at 25% carbon dioxide and 74.5% at 25% carbon dioxide. 94.5% of an inert gas.
  • any gas that is chemically inert to calcium hydride may be suitable.
  • the inert gas is for example selected from nitrogen, argon, or mixtures thereof.
  • the nature and the proportion of the components of the reaction mixture allow a controlled and complete treatment of the sintered calcium hydride according to the following overall carbonation reaction:
  • the time of contacting the reaction mixture with the sintered calcium hydride depends on the amount of calcium hydride and the composition of the reaction mixture. Those skilled in the art can easily adapt this duration, in particular by prolonging it until the total treatment of the sheath is obtained, which results, for example, in the end of the evolution of a gas such as hydrogen.
  • the duration of contacting is for example at least
  • 1 day typically between 1 day and 15 days for amounts of sintered calcium hydride to be treated of the order of one hectogram.
  • the contacting is preferably carried out at a temperature of between 40 ° C. and 55 ° C. in order in particular to adjust the molar percentage of water vapor to prevent the water from condensing and reacting violently with the hydride. of calcium.
  • the treatment according to the invention is most often carried out in a confinement enclosure such as a glove box or a shielded cell.
  • the reaction mixture is then generally introduced into the confinement chamber at a rate allowing its continuous renewal at least once an hour.
  • the propagation mode of the reaction by successive transformations in powder form of the sintered material, makes it possible to treat a sheath in which this material is relatively inaccessible, for example a sheath of complex geometry or large size.
  • the sintered calcium hydride is converted into a calcium carbonate powder, but obtaining this powder does not limit the kinetics of the reaction, which makes it possible to treat the entire sintered calcium hydride present in the sheath.
  • the sintered material can be in contact with the reaction mixture. Moreover, this contacting allows the calcium hydride powder to be removed from the sheath. When the sheath is sealed, it is then necessary to make at least one opening, for example by drilling or cutting the sheath.
  • the sheath can be in an inclined or vertical position, in order to promote the extraction by gravity of the calcium carbonate powder (and if necessary of any material that it contains).
  • the sintered calcium hydride is converted into a calcium carbonate powder containing the radioactive material (s), if appropriate, and / or any other material present initially in the sintered material or resulting from its treatment.
  • This powder has no chemical reactivity with respect to water and air. In the absence of radioactive material, it can be evacuated as such to a conventional die.
  • radioactive material In the presence of radioactive material, it can be incorporated in glass or cement, or dissolved in the form of Ca (HC03) 2 in most of the acids used in the nuclear waste treatment sector.
  • the gases produced during the treatment process of the invention may be extracted as gaseous effluents and discharged into a specific stream in order to to be treated,
  • the sheath is most often intact or has not undergone any major alteration.
  • it may consist of metal (preferably a steel), plastic or ceramic.
  • FIGS. 1, 2, 3 and 4 show photographic photographs taken during treatment of a sheath according to the process of the invention, the sheath containing fried pellets of calcium hydride.
  • the following example deals with the treatment of a steel sheath. It is representative of a section of a sheath from a nuclear reactor type RNR that would be cut in the upper and lower part.
  • the treated sheath consists of an inner tube positioned along the axis of an outer tube. It contains four pancakes obtained after the sintering of calcium hydride.
  • the purity of the calcium hydride is 99% by mass. Trace impurities consist essentially of aluminum and magnesium.
  • the dimensions of the sheath and a slab are as follows:
  • the assembly is maintained by placing the lower part of the sheath on a removable grid disposed above a recovery tank.
  • calcium hydride slabs do not contain radioactive material.
  • the sheath is placed in a glove box with a volume of 550 liters serving as a reaction chamber.
  • the temperature is regulated at 43 ° C.
  • a reaction mixture is continuously introduced at a rate of 12 liters per minute.
  • This mixture consists, in percentage by volume, of 2.5% of water vapor, 10% of carbon dioxide, the remainder being nitrogen as an inert gas.
  • composition is analyzed upstream and downstream of the glove box by gas chromatography to determine the content of the following gases: N 2 , CO 2 , O 2 , H 2 .
  • the amount of water vapor introduced is measured with a Peltier-type mirror hygrometer.
  • the hydrogen content produced is also constantly monitored by an explosimeter.
  • the carbonation reaction can be stopped by stopping the introduction of the reaction mixture. and replacing it entirely with inert gas.
  • the carbonation reaction can be resumed according to its initial regime by reintroduction of steam and carbon dioxide in the glove box without this affecting the overall efficiency of the treatment process.
  • the method of the invention thus allows a controlled and secure treatment.
  • the reaction mixture is brought into contact with the sintered calcium hydride mainly at the outer face of the first and the last slab, but also, to a lesser extent, on the inner and outer perimeter of the slabs, which is spaced 0.5 mm from the facing surfaces of the sheath.
  • Figures 1, 2, 3 and 4 reproduce the photographs taken respectively at the following times: introduction in the glove box of the reaction mixture (time to), to + 2 days, to + 4 days, to + 14 days.
  • the vertical position of the sheath allows the spontaneous fall of the calcium carbonate powder and any other material it contains, such as the impurities initially present in the patties.
  • the monitoring of the hydrogen content evolved during the carbonation reaction makes it possible, from the stoichiometric coefficients of the carbonation reaction, to calculate the mass of sintered calcium hydride which is converted.
  • the residual mass of calcium hydride is in the recovery tank. It can be transformed in turn by extending the duration of treatment.
  • the metal sheath emptied of its contents, the calcium carbonate powder and the hydrogen are evacuated according to separate channels.
  • the treatment method of the invention makes it possible to completely treat a sheath, in which there is a sintered material which consists wholly or partly of sintered calcium hydride and which optionally contains at least one radioactive material, while limiting the volume of waste obtained, and by authorizing the evacuation see the valorization of this waste by adapted channels.

Abstract

The invention relates to a method for treating a cladding, which contains a sintered material made up entirely or partially of sintered calcium hydride, the method including a step during which the sintered material is placed in contact with a reaction mixture containing steam, carbon dioxide, and a chemically inert gas, said step being carried out for a time long enough to enable the sintered calcium hydride to be transformed into a calcium carbonate powder. The treatment method according to the invention makes it possible to produce chemically inert waste and to limit the amount of waste obtained while enabling said waste to be discharged or recycled by suitable systems.

Description

PROCEDE DE TRAITEMENT D'UNE GAINE CONTENANT DE  PROCESS FOR TREATING A SHEATH CONTAINING
L'HYDRURE DE CALCIUM FRITTE.  CALCIUM HYDRIDE FRITTE.
DESCRIPTION DESCRIPTION
DOMAINE TECHNIQUE TECHNICAL AREA
La présente invention se situe dans le domaine du traitement des déchets nucléaires. The present invention is in the field of the treatment of nuclear waste.
Elle concerne en particulier le traitement d'une gaine contenant de l'hydrure de calcium (Ca¾) fritté.  It relates in particular to the treatment of a sheath containing sintered calcium hydride (Ca¾).
ARRIERE-PLAN TECHNIQUE TECHNICAL BACKGROUND
Dans le cadre d'études d'irradiation réalisées en réacteur nucléaire à neutrons rapides (RNR) , on utilise de l'hydrure de calcium fritté qui agit en tant que modérateur de la réaction de fission nucléaire. In fast neutron nuclear reactor (NRR) irradiation studies, sintered calcium hydride is used as a moderator of the nuclear fission reaction.
Ce matériau se présente généralement sous forme de galettes qui sont empilées dans une gaine cylindrique étanche en acier.  This material is generally in the form of slabs which are stacked in a cylindrical sealed steel sheath.
Les études d'irradiation une fois réalisées, on obtient une gaine dans laquelle se trouvent des galettes qui présentent à la fois un risque radiologique (présence d'une matière radioactive telle qu'une matière contenant du tritium) , mais également un risque chimique, l'hydrure de calcium au contact de l'eau dégageant de l'hydrogène qui est un gaz extrêmement inflammable.  Once the irradiation studies have been carried out, a sheath is obtained in which pancakes are found which present both a radiological risk (presence of a radioactive material such as a material containing tritium), but also a chemical risk. calcium hydride in contact with water giving off hydrogen which is an extremely flammable gas.
La filière du traitement des déchets nucléaires impose de neutraliser le risque chimique tout en diminuant autant que possible le volume des déchets et en optimisant leur conditionnement ultérieur. Afin de répondre à cette double contrainte, il serait dès lors souhaitable de disposer d'un traitement à l'issue duquel, d'une part les déchets issus de la gaine, et d'autre part les déchets issus des galettes d'hydrure de calcium irradiées, sont évacués par des voies adaptées à la nature de chaque déchet. The nuclear waste treatment sector must neutralize the chemical risk while reducing the volume of waste as much as possible and optimizing their subsequent conditioning. In order to meet this double constraint, it would therefore be desirable to have a treatment at the end of which, on the one hand, the waste resulting from the sheath, and on the other hand the waste resulting from the hydride wafers. calcium irradiated, are evacuated by ways adapted to the nature of each waste.
En pratique, ceci nécessite de limiter au mieux toute pollution, en particulier radioactive, d'un déchet par 1 ' autre .  In practice, this requires the best possible limitation of any pollution, particularly radioactive, of one waste by the other.
Si un tel résultat est atteint, cela permet avantageusement :  If such a result is achieved, this advantageously allows:
d'évacuer la gaine vers une filière dans laquelle la gestion des déchets est simplifiée grâce à l'absence de matière radioactive, voire de recycler cette gaine to evacuate the sheath to a sector in which the waste management is simplified thanks to the absence of radioactive material, or even to recycle this sheath
(transformation ou réutilisation) ; (transformation or reuse);
de gérer les déchets issus des galettes d'hydrure de calcium irradiées sous forme d'un déchet adapté aux filières d'évacuation de déchets radioactifs.  to manage the waste resulting from irradiated calcium hydride slabs in the form of a waste adapted to the radioactive waste disposal channels.
EXPOSE DE L' INVENTION SUMMARY OF THE INVENTION
Un des buts de l'invention est de fournir un procédé de traitement d'une gaine contenant de l'hydrure de calcium fritté et le cas échéant une matière radioactive, qui présente tout ou partie des avantages précités. One of the aims of the invention is to provide a process for treating a sheath containing sintered calcium hydride and optionally a radioactive material, which exhibits all or some of the aforementioned advantages.
La présente invention concerne ainsi un procédé de traitement d'une gaine, dans laquelle se trouve un matériau fritté qui est constitué en tout ou partie d'hydrure de calcium fritté qui peut éventuellement contenir au moins une matière radioactive. Le procédé comprend une étape au cours de laquelle le matériau fritté est mis en contact avec un mélange réactionnel contenant en pourcentage molaire 0,5 % à 5 % de vapeur d' eau, 5 % à 25 % de dioxyde de carbone et 74,5 % à 94,5 % d'un gaz inerte chimiquement, c'est-à-dire d' un gaz empêchant une réaction entre de l'oxygène (pouvant éventuellement être présent dans l'atmosphère réactionnelle) et de l'hydrogène (produit par la réaction de carbonatation décrite ci-après) . The present invention thus relates to a process for treating a sheath, in which there is a sintered material which consists wholly or partly of sintered calcium hydride which may optionally contain at least one radioactive material. The method comprises a step in which the sintered material is contacted with a reaction mixture containing 0.5% to 5% by weight of water vapor, 5% to 25% carbon dioxide and 74.5% by molar percentage. % to 94.5% of a chemically inert gas, i.e. a gas preventing a reaction between oxygen (possibly present in the reaction atmosphere) and hydrogen (produced by the carbonation reaction described hereinafter).
La mise en contact est effectuée pendant une durée permettant de transformer la totalité de l'hydrure de calcium fritté en une poudre de carbonate de calcium. Cette transformation peut donc être interrompue et reprise au moment choisi par l'opérateur, ou sa cinétique modulée en fonction de la quantité de mélange réactionnel injectée.  The contacting is carried out for a time to transform all the sintered calcium hydride into a calcium carbonate powder. This transformation can be interrupted and resumed at the moment chosen by the operator, or its kinetics modulated depending on the amount of reaction mixture injected.
Le procédé de traitement de 1 ' invention a pour particularité de transformer l'hydrure de calcium fritté en une poudre de carbonate de calcium qui est non adhérente aux parois de la gaine et inerte chimiquement.  The particular treatment method of the invention is to convert the sintered calcium hydride into a calcium carbonate powder which is non-adherent to the sheath walls and chemically inert.
Cette particularité est notamment due à la composition particulière du mélange réactionnel, ainsi qu'au fait que la transformation de l'hydrure de calcium fritté en une poudre de carbonate de calcium conduit à la destruction de la structure du matériau fritté.  This particularity is due in particular to the particular composition of the reaction mixture, as well as to the fact that the conversion of the sintered calcium hydride into a calcium carbonate powder leads to the destruction of the structure of the sintered material.
La poudre non adhérente obtenue à l'issue du procédé de traitement de l'invention, comprenant du carbonate de calcium, est dès lors naturellement extraite de la gaine par simple gravité, avec le cas échéant la matière radioactive et/ou toute autre matière qu'elle contient.  The non-adherent powder obtained at the end of the treatment process of the invention, comprising calcium carbonate, is therefore naturally extracted from the sheath by simple gravity, with the radioactive material and / or any other material that may be present. 'it contains.
Cette propriété de non-adhérence évite au mieux la dissémination de matière radioactive éventuellement présente dans la poudre de carbonate de calcium, ainsi que la contamination de la gaine par rétention de matière.  This property of non-adhesion avoids at best the dissemination of radioactive material possibly present in the calcium carbonate powder, as well as the contamination of the cladding by retention of material.
Cela permet également de traiter la totalité du matériau fritté malgré son caractère massif et son confinement dans la gaine. En effet, même si l'hydrure de calcium fritté réagit en surface, sa désagrégation sous forme d'une poudre non adhérente permet de régénérer en permanence une nouvelle surface réactive d'hydrure de calcium fritté. Puisque la poudre de carbonate de calcium est extraite de la gaine par simple gravité, le traitement peut se poursuivre naturellement, sans intervention humaine, et être mené jusqu'à la transformation totale du matériau fritté massif. This also makes it possible to treat all the sintered material despite its massive nature and its confinement in the sheath. Indeed, even if the sintered calcium hydride reacts on the surface, its disintegration in the form of a non-adherent powder makes it possible to regenerate permanently a new reactive surface of hydride of sintered calcium. Since the calcium carbonate powder is extracted from the sheath by simple gravity, the treatment can proceed naturally, without human intervention, and be conducted until the total conversion of the solid sintered material.
Le risque chimique dû à l'hydrure de calcium ayant été supprimé, la poudre de carbonate de calcium peut être évacuée vers une filière classique ou adaptée aux déchets radioactifs .  Since the chemical risk due to calcium hydride has been eliminated, the calcium carbonate powder can be discharged to a conventional die or adapted to radioactive waste.
Parmi les autres déchets obtenus au cours du traitement de l'invention, figure également un déchet gazeux tel que par exemple l'hydrogène (¾) , éventuellement tritié (HT) et/ou le tritium ( 2) . On peut extraire cet effluent gazeux au cours ou à l'issue du procédé de traitement. Among the other wastes obtained during the treatment of the invention, there is also a waste gas such as for example hydrogen (¾), optionally tritiated (HT) and / or tritium ( 2 ). This gaseous effluent can be extracted during or after the treatment process.
En particulier, lorsque la matière radioactive éventuellement présente se retrouve à l'issue du traitement sous forme gazeuse (telle que l'hydrogène tritié ou le tritium), elle est évacuée en tant qu ' effluent gazeux radioactif .  In particular, when the radioactive material possibly present is found at the end of the treatment in gaseous form (such as tritiated hydrogen or tritium), it is discharged as a radioactive gaseous effluent.
II ne subsiste alors plus de matière radioactive dans la poudre de carbonate de calcium. L'éventuelle présence initiale de matière radioactive impose néanmoins l'évacuation de cette poudre vers une filière simplifiée adaptée aux déchets radioactifs, qui est toutefois moins contraignante que celle qui serait imposée par la présence effective d'une matière radioactive dans le déchet à évacuer .  There is no longer any radioactive material in the calcium carbonate powder. The possible initial presence of radioactive material nevertheless requires the evacuation of this powder to a simplified pathway adapted to radioactive waste, which is however less restrictive than that which would be imposed by the actual presence of a radioactive material in the waste to be discharged.
La gaine n'est quant à elle pas altérée ou détruite au cours du traitement de l'invention, car le carbonate de calcium est un composé relativement inerte chimiquement et sa formation s'accompagne d'une expansion limitée.  The sheath is not altered or destroyed during the treatment of the invention, because the calcium carbonate is a relatively chemically inert compound and its formation is accompanied by a limited expansion.
De plus, la poudre de carbonate de calcium n'étant pas adhérente, la gaine n'est pas ou peu contaminée par des traces de carbonate de calcium ou de toute autre matière éventuellement radioactive qu'il contient. In addition, since the calcium carbonate powder is not adherent, the sheath is not or only slightly contaminated with traces of calcium carbonate or any other radioactive material it contains.
La gaine peut dès lors être évacuée vers une filière simplifiée adaptée aux déchets radioactifs pour être mise au rebut ou recyclée dans la filière nucléaire.  The sheath can then be evacuated to a simplified stream adapted to radioactive waste to be scrapped or recycled in the nuclear industry.
Cette séparation des filières réduit le volume des déchets, puisque l'obtention d'une poudre permet d'obtenir un conditionnement compact et la gaine peut éventuellement être recyclée.  This separation of the dies reduces the volume of waste, since obtaining a powder makes it possible to obtain a compact package and the sheath can optionally be recycled.
II résulte donc de l'obtention d'une poudre non adhérente que le procédé de l'invention permet de traiter complètement la gaine et son contenu, de limiter le volume des déchets obtenus, tout en autorisant l'évacuation voir la valorisation de ces déchets par des filières adaptées.  It therefore follows from obtaining a non-adherent powder that the process of the invention makes it possible to completely treat the sheath and its contents, to limit the volume of waste obtained, while allowing the evacuation see the recovery of this waste by adapted channels.
EXPOSE DETAILLE DE L' INVENTION DETAILED DESCRIPTION OF THE INVENTION
De par sa simplicité de mise en œuvre, le procédé de 1 ' invention permet de traiter avec un minimum de manipulation une gaine contenant un matériau fritté, ce qui s'avère particulièrement avantageux lorsque ce matériau contient au moins une matière radioactive. Because of its simplicity of implementation, the method of the invention makes it possible to treat with a minimum of manipulation a sheath containing a sintered material, which is particularly advantageous when this material contains at least one radioactive material.
Le matériau fritté comprend de l'hydrure de calcium fritté et éventuellement au moins une matière radioactive.  The sintered material comprises sintered calcium hydride and optionally at least one radioactive material.
La matière radioactive est par exemple une matière contenant l'élément tritium (T) .  The radioactive material is for example a material containing the tritium element (T).
Le procédé de traitement de l'invention comprend une étape au cours de laquelle le matériau fritté est mis en contact avec un mélange réactionnel contenant en pourcentage molaire 0,5 de vapeur d' à 25 % de dioxyde de carbone et 74,5 % à 94,5 % d'un gaz inerte.  The treatment method of the invention comprises a step in which the sintered material is contacted with a reaction mixture containing 0.5 mol% of steam at 25% carbon dioxide and 74.5% at 25% carbon dioxide. 94.5% of an inert gas.
Tout gaz qui est inerte chimiquement vis-à-vis de l'hydrure de calcium peut convenir. Le gaz inerte est par exemple choisi parmi l'azote, l'argon, ou leurs mélanges. La nature et la proportion des composants du mélange réactionnel permettent un traitement maîtrisé et complet de l'hydrure de calcium fritté selon la réaction de carbonatation globale suivante : Any gas that is chemically inert to calcium hydride may be suitable. The inert gas is for example selected from nitrogen, argon, or mixtures thereof. The nature and the proportion of the components of the reaction mixture allow a controlled and complete treatment of the sintered calcium hydride according to the following overall carbonation reaction:
CaH2(s) + 2H20( i ) -> Ca(OH)2(s) + 2H2(g) CaH 2 (s) + 2H 2 O (i) -> Ca (OH) 2 (s) + 2H 2 (g)
Le dioxyde de carbone réagit ensuite avec l'hydroxyde de calcium : Carbon dioxide then reacts with calcium hydroxide:
Ca(OH)2(s) + C02(g) -> CaCO3,H20(s) Ca (OH) 2 (s) + C0 2 (g) -> CaCO 3 , H 2 O (s)
La durée de mise en contact du mélange réactionnel avec l'hydrure de calcium fritté dépend de la quantité d'hydrure de calcium et de la composition du mélange réactionnel. L'homme du métier peut aisément adapter cette durée, notamment en la prolongeant jusqu'à l'obtention du traitement total de la gaine qui se traduit par exemple par la fin du dégagement d'un gaz tel que l'hydrogène. The time of contacting the reaction mixture with the sintered calcium hydride depends on the amount of calcium hydride and the composition of the reaction mixture. Those skilled in the art can easily adapt this duration, in particular by prolonging it until the total treatment of the sheath is obtained, which results, for example, in the end of the evolution of a gas such as hydrogen.
La durée de mise en contact est par exemple d'au moins The duration of contacting is for example at least
1 jour, typiquement comprise entre 1 jour et 15 jours pour des quantités d'hydrure de calcium fritté à traiter de l'ordre de l'hectogramme. 1 day, typically between 1 day and 15 days for amounts of sintered calcium hydride to be treated of the order of one hectogram.
La mise en contact est préférentiellement effectuée à une température comprise entre 40 °C et 55 °C afin notamment d'ajuster le pourcentage molaire de vapeur d'eau pour éviter que l'eau ne condense et ne réagisse de façon violente avec l'hydrure de calcium.  The contacting is preferably carried out at a temperature of between 40 ° C. and 55 ° C. in order in particular to adjust the molar percentage of water vapor to prevent the water from condensing and reacting violently with the hydride. of calcium.
Lorsque le matériau fritté contient au moins une matière radioactive, le traitement selon l'invention est le plus souvent réalisé dans une enceinte de confinement telle qu'une boîte à gants ou une cellule blindée.  When the sintered material contains at least one radioactive material, the treatment according to the invention is most often carried out in a confinement enclosure such as a glove box or a shielded cell.
Le mélange réactionnel est alors généralement introduit dans l'enceinte de confinement selon un débit permettant son renouvellement en continu au moins une fois par heure . The reaction mixture is then generally introduced into the confinement chamber at a rate allowing its continuous renewal at least once an hour.
Le mode de propagation de la réaction, par transformations successives sous forme pulvérulente du matériau fritté, permet de traiter une gaine dans lequel ce matériau est relativement inaccessible, par exemple une gaine de géométrie complexe ou de dimension importante.  The propagation mode of the reaction, by successive transformations in powder form of the sintered material, makes it possible to treat a sheath in which this material is relatively inaccessible, for example a sheath of complex geometry or large size.
En effet, durant la réaction de carbonatation, l'hydrure de calcium fritté se transforme en une poudre de carbonate de calcium, mais l'obtention de cette poudre ne limite pas la cinétique de la réaction, ce qui permet de traiter la totalité de l'hydrure de calcium fritté présent dans la gaine.  Indeed, during the carbonation reaction, the sintered calcium hydride is converted into a calcium carbonate powder, but obtaining this powder does not limit the kinetics of the reaction, which makes it possible to treat the entire sintered calcium hydride present in the sheath.
Il convient néanmoins de veiller à ce que le matériau fritté puisse être en contact avec le mélange réactionnel. Qui plus est, cette mise en contact permet à la poudre d'hydrure de calcium de s'extraire de la gaine. Lorsque la gaine est étanche, il est alors nécessaire d'y réaliser au moins une ouverture, par exemple par perçage ou découpe de la gaine.  However, care should be taken that the sintered material can be in contact with the reaction mixture. Moreover, this contacting allows the calcium hydride powder to be removed from the sheath. When the sheath is sealed, it is then necessary to make at least one opening, for example by drilling or cutting the sheath.
La gaine peut être en position inclinée ou verticale, afin de favoriser l'extraction par gravité de la poudre de carbonate de calcium (et le cas échéant de toute matière qu'elle contient).  The sheath can be in an inclined or vertical position, in order to promote the extraction by gravity of the calcium carbonate powder (and if necessary of any material that it contains).
A l'issue du procédé de traitement de l'invention, divers déchets sont obtenus :  At the end of the treatment process of the invention, various wastes are obtained:
- l'hydrure de calcium fritté est transformé en une poudre de carbonate de calcium contenant la ou les matières radioactives le cas échéant et/ou toute autre matière présente initialement dans le matériau fritté ou résultant de son traitement. Cette poudre ne présente aucune réactivité chimique vis-à-vis de l'eau et de l'air. En absence de matière radioactive, elle peut être évacuée telle quelle vers une filière classique. the sintered calcium hydride is converted into a calcium carbonate powder containing the radioactive material (s), if appropriate, and / or any other material present initially in the sintered material or resulting from its treatment. This powder has no chemical reactivity with respect to water and air. In the absence of radioactive material, it can be evacuated as such to a conventional die.
En présence de matière radioactive, elle peut être incorporée à du verre ou du ciment, ou dissoute sous forme de Ca(HC03)2 dans la majorité des acides utilisés dans la filière de traitement des déchets nucléaires. - le cas échéant, les gaz produits au cours du procédé de traitement de l'invention (par exemple de l'hydrogène éventuellement tritié et/ou du tritium) peuvent être extraits en tant qu'effluents gazeux et évacués dans une filière spécifique afin d'être traités,  In the presence of radioactive material, it can be incorporated in glass or cement, or dissolved in the form of Ca (HC03) 2 in most of the acids used in the nuclear waste treatment sector. if necessary, the gases produced during the treatment process of the invention (for example optionally tritiated hydrogen and / or tritium) may be extracted as gaseous effluents and discharged into a specific stream in order to to be treated,
la gaine est le plus souvent intacte ou n'a subi aucune altération majeure. A ce titre, afin de limiter l'impact du mélange réactionnel sur la gaine, celle-ci peut être constituée de métal (de préférence un acier) , de matière plastique ou de céramique.  the sheath is most often intact or has not undergone any major alteration. As such, in order to limit the impact of the reaction mixture on the sheath, it may consist of metal (preferably a steel), plastic or ceramic.
D'autres objets, caractéristiques et avantages de l'invention vont maintenant être précisés dans la description qui suit d'un mode de réalisation particulier du procédé de l'invention, donné à titre illustratif et non limitatif, en référence aux Figures 1 à 4 annexées. Other objects, features and advantages of the invention will now be specified in the following description of a particular embodiment of the method of the invention, given by way of nonlimiting illustration, with reference to FIGS. 1 to 4. attached.
BREVE DESCRIPTION DES FIGURES Les Figures 1, 2, 3 et 4 représentent des clichés photographiques pris au cours du traitement d'une gaine selon le procédé de l'invention, la gaine contenant des pastilles fritées d'hydrure de calcium. BRIEF DESCRIPTION OF THE FIGURES FIGS. 1, 2, 3 and 4 show photographic photographs taken during treatment of a sheath according to the process of the invention, the sheath containing fried pellets of calcium hydride.
EXPOSE D ' UN MODE DE REALISATION PARTICULIER DESCRIPTION OF A PARTICULAR EMBODIMENT
L'exemple qui suit porte sur le traitement d'une gaine en acier. Elle est représentative d'un tronçon d'une gaine issue d'un réacteur nucléaire de type RNR qui serait découpée en partie haute et basse. The following example deals with the treatment of a steel sheath. It is representative of a section of a sheath from a nuclear reactor type RNR that would be cut in the upper and lower part.
La gaine traitée est constituée d'un tube interne positionné le long de l'axe d'un tube externe. Elle contient quatre galettes obtenues après le frittage d'hydrure de calcium .  The treated sheath consists of an inner tube positioned along the axis of an outer tube. It contains four pancakes obtained after the sintering of calcium hydride.
La pureté de l' hydrure de calcium est de 99 % massique. Les impuretés à l'état de trace sont essentiellement constituées d'aluminium et de magnésium.  The purity of the calcium hydride is 99% by mass. Trace impurities consist essentially of aluminum and magnesium.
Les dimensions de la gaine et d'une galette sont les suivantes :  The dimensions of the sheath and a slab are as follows:
- tube externe : hauteur = 85 mm, diamètre externe = 116 mm, diamètre interne = 113 mm ;  outer tube: height = 85 mm, external diameter = 116 mm, internal diameter = 113 mm;
- tube interne : hauteur = 85 mm, diamètre externe = 49 mm, diamètre interne = 46 mm ;  - inner tube: height = 85 mm, outer diameter = 49 mm, internal diameter = 46 mm;
- galette d'hydrure de calcium : épaisseur = 20 mm, diamètre externe = 112,5 mm, diamètre interne = 49,5 mm .  calcium hydride slab: thickness = 20 mm, outer diameter = 112.5 mm, internal diameter = 49.5 mm.
L'ensemble est maintenu en plaçant la partie basse de la gaine sur une grille amovible disposée au-dessus d'un bac de récupération.  The assembly is maintained by placing the lower part of the sheath on a removable grid disposed above a recovery tank.
Dans cet exemple, les galettes d'hydrure de calcium ne contiennent pas de matière radioactive.  In this example, calcium hydride slabs do not contain radioactive material.
La gaine est disposée dans une boîte à gants d'un volume de 550 litres servant d'enceinte réactionnelle . La température est régulée à 43 °C.  The sheath is placed in a glove box with a volume of 550 liters serving as a reaction chamber. The temperature is regulated at 43 ° C.
On y introduit de façon continue un mélange réactionnel selon un débit de 12 litres par minute.  A reaction mixture is continuously introduced at a rate of 12 liters per minute.
Ce mélange est constitué, en pourcentage volumique, de 2,5 % de vapeur d'eau, 10 % de dioxyde de carbone, le reste étant de l'azote en tant que gaz inerte.  This mixture consists, in percentage by volume, of 2.5% of water vapor, 10% of carbon dioxide, the remainder being nitrogen as an inert gas.
Sa composition est analysée en amont et en aval de la boîte à gants par chromatographie en phase gazeuse afin de déterminer la teneur des gaz suivants : N2, CO2, 02, H2. La teneur en vapeur d'eau introduite est quant à elle mesurée avec un hygromètre à miroir de type Peltier. Its composition is analyzed upstream and downstream of the glove box by gas chromatography to determine the content of the following gases: N 2 , CO 2 , O 2 , H 2 . The The amount of water vapor introduced is measured with a Peltier-type mirror hygrometer.
Par mesure de sécurité, la teneur en hydrogène produit est également contrôlée en permanence par un explosimètre . En cas de franchissement du seuil fixé par ce détecteur (60 % de la LIE, à savoir la Limite Inférieure d' Explosivité de l'hydrogène dans l'air), la réaction de carbonatation peut être stoppée en arrêtant l'introduction du mélange réactionnel et en le remplaçant en totalité par du gaz inerte.  As a safety measure, the hydrogen content produced is also constantly monitored by an explosimeter. In case of crossing the threshold set by this detector (60% of the LEL, ie the lower limit of Explosivity of hydrogen in the air), the carbonation reaction can be stopped by stopping the introduction of the reaction mixture. and replacing it entirely with inert gas.
La réaction de carbonatation peut être reprise selon son régime initial par réintroduction de vapeur d'eau et de dioxyde de carbone dans la boîte à gants sans que cela n'affecte l'efficacité globale du procédé de traitement.  The carbonation reaction can be resumed according to its initial regime by reintroduction of steam and carbon dioxide in the glove box without this affecting the overall efficiency of the treatment process.
Le procédé de l'invention permet donc un traitement maîtrisé et sécurisé.  The method of the invention thus allows a controlled and secure treatment.
La mise en contact du mélange réactionnel avec l'hydrure de calcium fritté se produit principalement au niveau de la face externe de la première et de la dernière galette, mais également, dans une moindre mesure, sur le périmètre interne et externe des galettes qui est espacé de 0,5 mm des surfaces en regard de la gaine.  The reaction mixture is brought into contact with the sintered calcium hydride mainly at the outer face of the first and the last slab, but also, to a lesser extent, on the inner and outer perimeter of the slabs, which is spaced 0.5 mm from the facing surfaces of the sheath.
Le déroulement du traitement est suivi visuellement. Les Figures 1, 2, 3 et 4 reproduisent les photographies prises respectivement aux moments suivants : introduction dans la boîte à gants du mélange réactionnel (temps to) , to + 2 jours, to + 4 jours, to + 14 jours.  The course of treatment is followed visually. Figures 1, 2, 3 and 4 reproduce the photographs taken respectively at the following times: introduction in the glove box of the reaction mixture (time to), to + 2 days, to + 4 days, to + 14 days.
Ces figures montrent que les galettes d'hydrure de calcium fritté se désagrègent progressivement sous forme de poudre de carbonate de calcium. Cette transformation provoque une expansion volumique limitée, ce qui permet de ne pas altérer ou détruire la gaine.  These figures show that the sintered calcium hydride wafers gradually disintegrate in the form of calcium carbonate powder. This transformation causes a limited volume expansion, which makes it possible not to alter or destroy the sheath.
La position verticale de la gaine permet la chute spontanée de la poudre de carbonate de calcium et de toute autre matière qu'elle contient, comme par exemple les impuretés initialement présentes dans les galettes. The vertical position of the sheath allows the spontaneous fall of the calcium carbonate powder and any other material it contains, such as the impurities initially present in the patties.
Il s'ensuit une augmentation naturelle de la surface de contact de l'hydrure de calcium fritté non encore traité avec le mélange réactionnel. De façon concomitante et temporaire, les mesures chromatographiques montrent que la consommation de vapeur d'eau et la production d'hydrogène augmentent à cause de l'accélération de la cinétique de la réaction de carbonatation . La chute de la poudre permet de faciliter et de maintenir le contact entre le mélange réactionnel et l'hydrure de calcium.  This results in a natural increase in the contact area of the sintered calcium hydride not yet treated with the reaction mixture. Concomitantly and temporarily, the chromatographic measurements show that the consumption of water vapor and the production of hydrogen increase because of the acceleration of the kinetics of the carbonation reaction. The falling of the powder facilitates and maintains contact between the reaction mixture and the calcium hydride.
Le suivi de la teneur en hydrogène dégagé pendant la réaction de carbonatation permet, à partir des coefficients stœchiométriques de la réaction de carbonatation, de calculer la masse d'hydrure de calcium fritté qui est transformée .  The monitoring of the hydrogen content evolved during the carbonation reaction makes it possible, from the stoichiometric coefficients of the carbonation reaction, to calculate the mass of sintered calcium hydride which is converted.
Ces calculs et l'observation de la progression du traitement indiquent que la quasi-totalité de l'hydrure de calcium fritté (926 g sur 980 g) est transformée au bout de 18 jours en poudre de carbonate de calcium.  These calculations and the observation of the progress of the treatment indicate that almost all of the sintered calcium hydride (926 g on 980 g) is transformed after 18 days into a powder of calcium carbonate.
La masse résiduelle d'hydrure de calcium est dans le bac de récupération. Elle peut être transformée à son tour en allongeant la durée de traitement.  The residual mass of calcium hydride is in the recovery tank. It can be transformed in turn by extending the duration of treatment.
A l'issue de ce traitement, la gaine métallique vidée de son contenu, la poudre de carbonate de calcium et l'hydrogène sont évacués selon des filières séparées.  At the end of this treatment, the metal sheath emptied of its contents, the calcium carbonate powder and the hydrogen are evacuated according to separate channels.
Il ressort de la description qui précède que le procédé de traitement de 1 ' invention permet de traiter complètement une gaine, dans laquelle se trouve un matériau fritté qui est constitué en tout ou partie d'hydrure de calcium fritté et qui contient éventuellement au moins une matière radioactive, tout en limitant le volume des déchets obtenus, et en autorisant l'évacuation voir la valorisation de ces déchets par des filières adaptées. It follows from the foregoing description that the treatment method of the invention makes it possible to completely treat a sheath, in which there is a sintered material which consists wholly or partly of sintered calcium hydride and which optionally contains at least one radioactive material, while limiting the volume of waste obtained, and by authorizing the evacuation see the valorization of this waste by adapted channels.

Claims

REVENDICATIONS
1) Procédé de traitement d'une gaine, dans laquelle se trouve un matériau fritté qui est constitué en tout ou partie d'hydrure de calcium fritté, le procédé comprenant une étape au cours de laquelle le matériau fritté est mis en contact avec un mélange réactionnel contenant en pourcentage molaire 0,5 de vapeur d' à 25 % de dioxyde de carbone et 74,5 % à 94,5 % d'un gaz inerte chimiquement, la mise en contact étant effectuée pendant une durée permettant de transformer l'hydrure de calcium fritté en une poudre de carbonate de calcium. 1) A process for treating a sheath, in which there is a sintered material which consists wholly or partly of sintered calcium hydride, the process comprising a step during which the sintered material is brought into contact with a mixture reaction containing 0.5% steam of 25% carbon dioxide and 74.5% to 94.5% of a chemically inert gas, the contacting being carried out for a time to transform the Sintered calcium hydride to a calcium carbonate powder.
2) Procédé de traitement selon la revendication 1, dans lequel le matériau fritté contient au moins une matière radioactive . 2) A treatment method according to claim 1, wherein the sintered material contains at least one radioactive material.
3) Procédé de traitement selon la revendication 2, dans lequel la matière radioactive est une matière contenant l'élément tritium. 3) A method of treatment according to claim 2, wherein the radioactive material is a material containing the tritium element.
4) Procédé de traitement selon l'une quelconque des revendications précédentes, dans lequel la gaine est constituée de métal, de matière plastique ou de céramique. 5) Procédé de traitement selon l'une quelconque des revendications précédentes, dans lequel le gaz inerte est choisi parmi l'azote, l'argon, ou leurs mélanges. 4) A method of treatment according to any one of the preceding claims, wherein the sheath is made of metal, plastic or ceramic. 5) A method of treatment according to any one of the preceding claims, wherein the inert gas is selected from nitrogen, argon, or mixtures thereof.
6) Procédé de traitement selon l'une quelconque des revendications précédentes, dans lequel la mise en contact est effectuée à une température comprise entre 40 °C et 55 °C. 6) A method of treatment according to any preceding claim, wherein the contacting is carried out at a temperature between 40 ° C and 55 ° C.
7) Procédé de traitement selon l'une quelconque des revendications précédentes, dans lequel le procédé est réalisé dans une enceinte de confinement telle qu'une boîte à gants ou une cellule blindée. 7) A method of treatment according to any one of the preceding claims, wherein the method is carried out in a confinement enclosure such as a glove box or a shielded cell.
8) Procédé de traitement selon la revendication 7, dans lequel le mélange réactionnel est introduit dans l'enceinte de confinement selon un débit permettant son renouvellement en continu au moins une fois par heure. 8) Treatment process according to claim 7, wherein the reaction mixture is introduced into the confinement chamber at a rate allowing its continuous renewal at least once an hour.
9) Procédé de traitement selon l'une quelconque des revendications précédentes, dans lequel la gaine est en position inclinée ou verticale, afin de favoriser l'extraction par gravité de la poudre de carbonate de calcium. 9) A method of treatment according to any one of the preceding claims, wherein the sheath is in an inclined or vertical position, to promote the extraction by gravity of the calcium carbonate powder.
10) Procédé de traitement selon l'une quelconque des revendications précédentes, dans lequel on extrait un effluent gazeux au cours ou à l'issue du procédé de traitement . 11) Procédé de traitement selon la revendication 10, dans lequel l'effluent gazeux est radioactif. 10) A method of treatment according to any one of the preceding claims, wherein a gaseous effluent is extracted during or after the treatment process. 11) A method of treatment according to claim 10, wherein the gaseous effluent is radioactive.
EP12794429.6A 2011-11-03 2012-11-02 Method for treating a cladding containing sintered calcium hydride Active EP2774155B1 (en)

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