EP0321352B1 - Process for immobilizing the ion-exchange resins proceeding from the secondary loops of pressurized-water and graphite-gas reactors - Google Patents

Process for immobilizing the ion-exchange resins proceeding from the secondary loops of pressurized-water and graphite-gas reactors Download PDF

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Publication number
EP0321352B1
EP0321352B1 EP88403208A EP88403208A EP0321352B1 EP 0321352 B1 EP0321352 B1 EP 0321352B1 EP 88403208 A EP88403208 A EP 88403208A EP 88403208 A EP88403208 A EP 88403208A EP 0321352 B1 EP0321352 B1 EP 0321352B1
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EP
European Patent Office
Prior art keywords
resins
exchange resins
ion
water
graphite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP88403208A
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German (de)
French (fr)
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EP0321352A1 (en
Inventor
Guy Magnin
Claude Jaouen
Marie-Françoise épouse Magnin Champeaud
Véronique Aubert
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Societe Generale pour les Techniques Nouvelles SA SGN
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Societe Generale pour les Techniques Nouvelles SA SGN
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Classifications

    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • G21F9/16Processing by fixation in stable solid media
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28Treating solids
    • G21F9/30Processing
    • G21F9/301Processing by fixation in stable solid media
    • G21F9/302Processing by fixation in stable solid media in an inorganic matrix
    • G21F9/304Cement or cement-like matrix
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28Treating solids
    • G21F9/30Processing

Definitions

  • the present invention relates to a method for immobilizing ion exchange resins originating from the secondary circuits of pressurized water nuclear reactors and graphite-gas reactors.
  • the present invention relates to a process for the immobilization, with a view to their storage, of said resins.
  • the immobilization process chosen according to the invention is that of concreting, that is to say the general process - known in itself - consisting of coating the products to be immobilized in a hydraulic binder.
  • the problem consists in carrying out a pretreatment of the resins making it possible to implement this immobilization process and, if possible, to obtain a product having the best properties.
  • the pretreatment method according to the invention is characterized in that the ion exchange resins are saturated with a base, preferably sodium hydroxide, under conditions such that the pH of the medium is greater than approximately 9 and that the release of ammonia is favored.
  • a base preferably sodium hydroxide
  • base a compound such as sodium, potassium, calcium or barium hydroxides.
  • sodium hydroxide is preferred. This product can be used in solid form or in solution.
  • the base used in the present invention is intended to ensure, by ion exchange, saturation of all the sites of the resins comprising an NH4+ ion, it is obviously necessary to carry out this exchange in an aqueous medium which can be consisting wholly or in part of the water which is generally present in the charge of the resins which have to be treated.
  • the pH of the (aqueous) medium should be above about 9; in fact, the pH must be high enough for the NH4+ ions released from the resins by exchange with the basic cation (Na+) not to remain in the dissolved state in said medium but to give rise to gaseous ammonia which will emerge from said medium
  • the amount of "base” used must be at least that which allows total displacement of the NH4+ ions by the cation of said base.
  • an amount of "base” is used which is at least sufficient for the cation of said base to saturate all the sites of the resins, assuming that all the resins treated are cationic it will be noted that the use of a quantity of base greater than that necessary to ensure the saturation of the sites can, to a certain extent, promote and accelerate the phenomenon of saturation.
  • the process as described above only causes ionic exchanges on the cationic resins contained in the resins to be treated. It turns out that, given the very low radioactivity of the treated resins and the specifications current to be respected, it has been determined that the anionic resins did not have too great harmful effects on the phenomena of setting of the hydraulic binder.
  • the process according to the invention can be improved by also stabilizing, by ion exchange, the anionic resins present in the resins to be treated.
  • This stabilization can be done by carrying out the ion exchange of OH ⁇ contained in the anionic resins with ions such as NO4 ⁇ , SO4 ⁇ , CH3COO ⁇ ...
  • ions such as NO4 ⁇ , SO4 ⁇ , CH3COO ⁇ ...
  • NO3 ⁇ ion the most interesting, because of the stability obtained, because of the ease of its use and because of its inertia with respect to the anions present during concreting, is the NO3 ⁇ ion.
  • the amount of this anion (NO3 ⁇ preferably) to be used can advantageously be calculated by assuming that all of the treated resin is of the anionic type and that the aim is to saturate all the sites of this resin.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Ceramic Products (AREA)

Description

La présente invention concerne un procédé d'immobilisation de résines échangeuses d'ions provenant des circuits secondaires des réacteurs nucléaires à eau pressurisée et des réacteurs graphite-gaz.The present invention relates to a method for immobilizing ion exchange resins originating from the secondary circuits of pressurized water nuclear reactors and graphite-gas reactors.

On sait que l'eau des circuits secondaires des réacteurs nucléaires à eau pressurisée contient de l'ammoniaque et que cette eau ammoniaquée est traitée au moyen de résines échangeuses d'ions. Ces résines sont de type cationique mais on utilise également, pour assurer une bonne purification de cette eau, des résines de type anionique.It is known that the water in the secondary circuits of nuclear pressurized water reactors contains ammonia and that this ammonia water is treated with ion exchange resins. These resins are of cationic type, but anionic type resins are also used to ensure good purification of this water.

On aura donc généralement à immobiliser en vue d'un stockage un mélange de résines cationiques ayant essentiellement fixé des ions NH₄⁺ et de résines anioniques dons les sites sont sous forme de OH⁻.It will therefore generally be necessary to immobilize for storage a mixture of cationic resins having essentially fixed NH₄⁺ ions and anionic resins don the sites are in the form of OH⁻.

Ces résines présentent une radioactivité relativement faible et, cependant, certaines spécifications actuelles ou prévues pour un futur assez proche impliquent que ces résines soient immobilisées et stockées dans des conditions spécifiques, voisines de celles que l'on utilisait à ce jour pour l'immobilisation et le stockage de produits dits de faible et moyenne activité.These resins have a relatively low radioactivity and, however, certain current or planned specifications for the fairly near future imply that these resins are immobilized and stored under specific conditions, similar to those used to date for immobilization and storage of so-called low and medium activity products.

La présente invention vise à un procédé pour l'immobilisation, en vue de leur stockage, desdites résines.The present invention relates to a process for the immobilization, with a view to their storage, of said resins.

On a proposé, selon l'art antérieur, divers types de conditionnement de déchets nucléaires et notamment, selon les demandes FR-A-2.361.724 et FR-A-2.505.539 leur conditionnement dans des résines, selon les demandes FR-A-2.356.246 et EP-A-0.157.683 leur conditionnement dans du bitume.Various types of packaging for nuclear waste have been proposed, according to the prior art, and in particular, according to applications FR-A-2,361,724 and FR-A-2,505,539, their packaging in resins, according to applications FR-A -2,356,246 and EP-A-0.157.683 their packaging in bitumen.

Le procédé d'immobilisation choisi selon l'invention est celui du bétonnage c'est-à-dire le procédé général - connu en lui-même - consistant à enrober les produits à immobiliser dans un liant hydraulique. Le problème consiste à réaliser un pré-traitement des résines permettant de mettre en oeuvre ce procédé d'immobilisation et, si possible, d'obtenir un produit présentant les meilleures propriétés.The immobilization process chosen according to the invention is that of concreting, that is to say the general process - known in itself - consisting of coating the products to be immobilized in a hydraulic binder. The problem consists in carrying out a pretreatment of the resins making it possible to implement this immobilization process and, if possible, to obtain a product having the best properties.

Le procédé de pré-traitement selon l'invention est caractérisé en ce que les résines échangeuses d'ions sont saturées par une base, de préférence de la soude, dans des conditions telles que le pH du milieu est supérieur à environ 9 et que l'on favorise le dégagement d'ammoniac.The pretreatment method according to the invention is characterized in that the ion exchange resins are saturated with a base, preferably sodium hydroxide, under conditions such that the pH of the medium is greater than approximately 9 and that the release of ammonia is favored.

Par base, on entend un composé tel que les hydroxydes de sodium, potassium, calcium ou baryum. Pour des raisons économiques, de solubilité et de facilité d'emploi, on préfère l'hydroxyde de sodium. Ce produit peut être employé sous forme solide ou en solution.By base is meant a compound such as sodium, potassium, calcium or barium hydroxides. For economic reasons, solubility and ease of use, sodium hydroxide is preferred. This product can be used in solid form or in solution.

Comme la "base" utilisée dans la présente invention est destinée à assurer, par échange ionique, une saturation de tous les sites des résines comportant un ion NH₄⁺ il convient, bien évidemment, d'opérer cet échange dans un milieu aqueux qui peut être constitué en totalité ou en partie par l'eau qui est généralement présente dans la charge des résines que l'on doit traiter.As the "base" used in the present invention is intended to ensure, by ion exchange, saturation of all the sites of the resins comprising an NH₄⁺ ion, it is obviously necessary to carry out this exchange in an aqueous medium which can be consisting wholly or in part of the water which is generally present in the charge of the resins which have to be treated.

On a indiqué que le pH du milieu (aqueux) doit être supérieur à environ 9 ; il faut en fait que le pH soit suffisamment élevé pour que les ions NH₄⁺ libérés des résines par échange avec le cation basique (Na⁺) ne restent pas à l'état dissous dans ledit milieu mais donnent naissance à de l'ammoniac gazeux qui se dégagera dudit milieuIt has been stated that the pH of the (aqueous) medium should be above about 9; in fact, the pH must be high enough for the NH₄⁺ ions released from the resins by exchange with the basic cation (Na⁺) not to remain in the dissolved state in said medium but to give rise to gaseous ammonia which will emerge from said medium

Enfin, on a indiqué qu'il était souhaitable d'utiliser au moins un moyen favorisant le dégagement de l'ammoniac. On entend par là qu'il convient de faire en sorte que l'ammoniac gazeux qui se dégage du milieu ne demeure pas en contact prolongé avec la surface dudit milieu. En effet, si ce contact existait, on sait que ledit ammoniac aurait tendance à se redissoudre dans ledit milieu, ce qui freinerait - du fait de l'équilibre - le dégagement de nouvelles quantités d'ammoniac. On peut, bien évidemment, utiliser n'importe quel moyen connu pour favoriser ce dégagement ; on peut citer, par exemple, le balayage de la surface du milieu par un courant d'air ou l'évacuation (grâce à un vide partiel) de l'atmosphère située au-dessus dudit milieu, ou encore l'élévation de la température à un niveau suffisant ne provoquant pas toutefois la dégradation des résines.Finally, it was indicated that it was desirable to use at least one means promoting the release of ammonia. By this is meant that it is necessary to ensure that the gaseous ammonia which emerges from the medium does not remain in prolonged contact with the surface of said medium. Indeed, if this contact existed, we know that said ammonia would tend to redissolve in said medium, which would slow - due to the balance - the release of new amounts of ammonia. One can, of course, use any known means to promote this release; one can cite, for example, the sweeping of the surface of the medium by a current of air or the evacuation (thanks to a partial vacuum) of the atmosphere located above said medium, or even the rise in temperature at a sufficient level, however, not causing the degradation of the resins.

La quantité de "base" utilisée doit être au moins celle qui permet un déplacement total des ions NH₄⁺par le cation de ladite base. En pratique comme on ignore souvent la proportion des résines cationiques contenues dans les résines à traiter, on utilise une quantité de "base" au moins suffisante pour que le cation de ladite base sature tous les sites des résines en supposant que toutes les résines traitées sont cationiques on notera que l'emploi d'une quantité de base supérieure à celle nécessaire pour assurer la saturation des sites peut, dans une certaine mesure, favoriser et accélérer le phénomène de saturation.The amount of "base" used must be at least that which allows total displacement of the NH₄⁺ ions by the cation of said base. In practice, as the proportion of cationic resins contained in the resins to be treated is often ignored, an amount of "base" is used which is at least sufficient for the cation of said base to saturate all the sites of the resins, assuming that all the resins treated are cationic it will be noted that the use of a quantity of base greater than that necessary to ensure the saturation of the sites can, to a certain extent, promote and accelerate the phenomenon of saturation.

Comme on le voit, le procédé tel que décrit ci-dessus ne provoque d'échanges ioniques que sur les résines cationiques contenues dans les résines à traiter Il se trouve en effet que, compte tenu de la très faible radioactivité des résines traitées et des spécifications actuelles à respecter, on a pu déterminer que les résines anioniques n'avaient pas d'effets nocifs trop importants sur les phénomènes de prises du liant hydraulique.As can be seen, the process as described above only causes ionic exchanges on the cationic resins contained in the resins to be treated. It turns out that, given the very low radioactivity of the treated resins and the specifications current to be respected, it has been determined that the anionic resins did not have too great harmful effects on the phenomena of setting of the hydraulic binder.

Mais il se trouve que l'on peut améliorer le procédé selon l'invention en stabilisant également, par échange ionique, les résines anioniques présentes dans les résines à traiter. Cette stabilisation peut se faire en réalisant l'échange ionique des OH⁻ contenus dans les résines anioniques avec des ions tels que NO₃⁻, SO₄⁻⁻, CH₃COO⁻ ... Parmi les anions utilisables, le plus intéressant, du fait de la stabilité obtenue, du fait de la facilité de son utilisation et du fait de son inertie vis-à-vis des anions présents lors du bétonnage, est l'ion NO₃⁻. Il est donc possible de mettre en oeuvre la présente invention en utilisant soit successivement, soit simultanément une "base", telle que définie et dans les conditions indiquées ci-dessus, et un composé anionique apportant, par exemple, l'ion NO₃⁻. Il est, par exemple, possible d'utiliser du nitrate de sodium et éventuellement, si le milieu n'est pas à un pH suffisant, de la soude.However, it turns out that the process according to the invention can be improved by also stabilizing, by ion exchange, the anionic resins present in the resins to be treated. This stabilization can be done by carrying out the ion exchange of OH⁻ contained in the anionic resins with ions such as NO₄⁻⁻, SO₄⁻⁻, CH₃COO⁻ ... Among the usable anions, the most interesting, because of the stability obtained, because of the ease of its use and because of its inertia with respect to the anions present during concreting, is the NO₃⁻ ion. It is therefore possible to implement the present invention by using either successively or simultaneously a "base", as defined and under the conditions indicated above, and an anionic compound providing, for example, the NO₃⁻ ion. It is, for example, possible to use sodium nitrate and possibly, if the medium is not at a sufficient pH, soda.

La quantité de cet anion (NO₃⁻ de préférence) à utiliser pourra avantageusement être calculée en supposant que toute la résine traitée est de type anionique et que l'on vise à la saturation de tous les sites de cette résine.The amount of this anion (NO₃⁻ preferably) to be used can advantageously be calculated by assuming that all of the treated resin is of the anionic type and that the aim is to saturate all the sites of this resin.

L'exemple non limitatif suivant illustre l'invention.The following nonlimiting example illustrates the invention.

A 100 l de résine 100 % décantées, 50 l d'une solution à 250 g/l en NaNO₃ sont ajoutés ainsi que 20 kg de NaOH en pastilles.To 100 l of 100% decanted resin, 50 l of a 250 g / l solution of NaNO₃ are added as well as 20 kg of NaOH in pellets.

Après 4 h d'agitation à une température de 60°C sous une pression réduite à 0,2 bar, puis refroidissement à température ambiante, 200 kg de ciment CLK sont ajoutés - 390 kg d'enrobé sont ainsi obtenus avec un taux d'incorporation de 40 % (en volume) de résines 100 % décantées.After 4 h of stirring at a temperature of 60 ° C under a pressure reduced to 0.2 bar, then cooling to room temperature, 200 kg of CLK cement are added - 390 kg of asphalt are thus obtained with a rate of incorporation of 40% (by volume) of 100% decanted resins.

Claims (4)

  1. Process for the immobilization in a hydraulic binder of ion exchange resins originating from the secondary circuits of pressurized water nuclear reactors and gas-cooled graphite-moderated reactors, characterized in that said ion exchange resins are saturated with a base, under conditions such that the pH of the medium is greater than about 9 and in that the release of ammonia is favored, after which the said resins are concreted with said hydraulic binder.
  2. Process according to claim 1, characterized in that said ion exchange resins are saturated with sodium hydroxide.
  3. Process according to claim 1 or 2, characterized in that any anionic resins present in the resins to be treated are stabilized by the addition of a compound providing NO₃⁻ ions.
  4. Process according to claim 3, characterized in that said compound providing NO₃⁻ ions consists in sodium nitrate.
EP88403208A 1987-12-16 1988-12-16 Process for immobilizing the ion-exchange resins proceeding from the secondary loops of pressurized-water and graphite-gas reactors Expired - Lifetime EP0321352B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8717596A FR2624769B1 (en) 1987-12-16 1987-12-16 METHOD OF IMMOBILIZING ION EXCHANGE RESINS FROM SECONDARY CIRCUITS OF PRESSURIZED WATER NUCLEAR REACTORS AND GRAPHITE-GAS REACTORS
FR8717596 1987-12-16

Publications (2)

Publication Number Publication Date
EP0321352A1 EP0321352A1 (en) 1989-06-21
EP0321352B1 true EP0321352B1 (en) 1992-11-25

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EP88403208A Expired - Lifetime EP0321352B1 (en) 1987-12-16 1988-12-16 Process for immobilizing the ion-exchange resins proceeding from the secondary loops of pressurized-water and graphite-gas reactors

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US (1) US4834915A (en)
EP (1) EP0321352B1 (en)
KR (1) KR970004357B1 (en)
DE (1) DE3876224T2 (en)
ES (1) ES2053790T3 (en)
FR (1) FR2624769B1 (en)

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US5545798A (en) * 1992-09-28 1996-08-13 Elliott; Guy R. B. Preparation of radioactive ion-exchange resin for its storage or disposal
TW365009B (en) * 1996-09-24 1999-07-21 Jgc Corp Method of disposal of metallic aluminum-containing radioactive solid waste
US5960368A (en) * 1997-05-22 1999-09-28 Westinghouse Savannah River Company Method for acid oxidation of radioactive, hazardous, and mixed organic waste materials
ES2207479T3 (en) * 2000-03-20 2004-06-01 Institute Of Nuclear Energy Research, Taiwan, R.O.C. PROCEDURE FOR CO-SOLIDIFICATION OF WEAKLY WASTED WASTE RADIOACTIVE PRODUCTS IN NUCLEAR CENTERS OF WATER WATER.
RU2217825C2 (en) * 2001-08-27 2003-11-27 Государственное предприятие Научно-исследовательский технологический институт им. А.П. Александрова Method for inclusion of radioactive ion-exchange resins into portland cement binder
RU2253162C2 (en) * 2003-04-24 2005-05-27 ФГУП "Производственное объединение "Маяк" Method for localizing spent ion-exchange resins
RU2278429C2 (en) * 2004-07-01 2006-06-20 ФГУП "Производственное объединение "Маяк" Method for immobilizing spent ion-exchange resins
RU2353011C1 (en) * 2007-11-19 2009-04-20 Закрытое акционерное общество "ИНТРА" Method of radioactive ion-exchanging resins preparation for immobilisation into bulk structures
RU2381579C1 (en) * 2008-12-08 2010-02-10 Федеральное государственное унитарное предприятие "Научно-исследовательский технологический институт имени А.П. Александрова" Method of processing radioactive ion-exchange resins and industrial toxic liquid wastes
RU2600940C2 (en) * 2015-03-27 2016-10-27 Открытое акционерное общество "Красная Звезда" Method of preparing solid phase of liquid radioactive wastes to burial
RU2735858C1 (en) * 2020-06-02 2020-11-09 Акционерное общество "Научно-исследовательское проектно-технологическое бюро "Онега" (АО "НИПТБ "Онега") Apparatus for drying radioactive ion-exchange resins

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FR2561812B1 (en) * 1984-03-21 1989-02-17 Commissariat Energie Atomique PROCESS FOR BITUMENING RADIOACTIVE WASTE CONSTITUTED BY CATION EXCHANGE RESINS AND / OR ANION EXCHANGE RESINS
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Also Published As

Publication number Publication date
KR970004357B1 (en) 1997-03-27
ES2053790T3 (en) 1994-08-01
FR2624769B1 (en) 1991-04-19
FR2624769A1 (en) 1989-06-23
DE3876224D1 (en) 1993-01-07
DE3876224T2 (en) 1993-05-19
US4834915A (en) 1989-05-30
KR890010932A (en) 1989-08-11
EP0321352A1 (en) 1989-06-21

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