EP0294260B1 - Process for immobilizing ion-exchangers by hydraulic binding-material - Google Patents

Process for immobilizing ion-exchangers by hydraulic binding-material Download PDF

Info

Publication number
EP0294260B1
EP0294260B1 EP88401175A EP88401175A EP0294260B1 EP 0294260 B1 EP0294260 B1 EP 0294260B1 EP 88401175 A EP88401175 A EP 88401175A EP 88401175 A EP88401175 A EP 88401175A EP 0294260 B1 EP0294260 B1 EP 0294260B1
Authority
EP
European Patent Office
Prior art keywords
rei
reis
ions
solution
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88401175A
Other languages
German (de)
French (fr)
Other versions
EP0294260A1 (en
Inventor
Guy Magnin
Marie-Françoise Magnin
Véronique Aubert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Societe Generale pour les Techniques Nouvelles SA SGN
Original Assignee
Societe Generale pour les Techniques Nouvelles SA SGN
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Societe Generale pour les Techniques Nouvelles SA SGN filed Critical Societe Generale pour les Techniques Nouvelles SA SGN
Publication of EP0294260A1 publication Critical patent/EP0294260A1/en
Application granted granted Critical
Publication of EP0294260B1 publication Critical patent/EP0294260B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/16—Processing by fixation in stable solid media
    • 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
    • G21F9/301—Processing by fixation in stable solid media
    • G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
    • G21F9/304—Cement or cement-like matrix

Definitions

  • the invention relates to a method for immobilizing radioactive ion exchange resins (REIs) with a hydraulic binder.
  • REIs radioactive ion exchange resins
  • the radioactive REIs to be treated come essentially from nuclear reactors in which they are used to purify the water of various reactor circuits and sometimes the water of the storage pools for irradiated fuel elements.
  • anionic REIs are placed on the primary circuit, the water of which is supplemented with boric acid playing the role of moderator.
  • the anionic REIs can then serve as a "boron lung" to maintain the desired boron concentration in the circuit.
  • these REIs can contain the lithium, ammonium, iron, cobalt, chromium, nickel, cesium cations and the hydroxide, sulphate, phosphate, silicate, fluoride, chloride, bicarbonate anions.
  • REIs are also used in installations for reprocessing irradiated fuel elements for the purification of water in storage pools and for the treatment of liquids.
  • REIs are placed in columns or cartouches.
  • the first problem is that of the ion exchange between the REIs and the medium containing the hydraulic binder.
  • the ions in the medium which have a greater affinity for the REIs than that which the ions contained in these REIs have for them, attach themselves to the REIs in place of the ions which they contained, these ions being released into the medium. There is ion fixation and simultaneously salting out of other ions. So that the medium is depleted in ions of the hydraulic binder (Ca++ and SO4 ⁇ essentially) and on the other hand is enriched in ions coming from nuclear installations (active metal cations, phosphates, sulfates .. H+, OH ⁇ and borates).
  • Ion exchanges can continue after setting, in particular during leaching tests, between the leaching medium and the REI made accessible in the mix by various causes (permeable matrix, poor homogeneity, high porosity, etc.).
  • the released ions can generate harmful reactions for the mix, for example sulfates.
  • the second type of difficulty encountered in the treatment of REIs specifically results from the migration of water from REIs to the medium containing the hydraulic binder.
  • the REI sell a fraction of their water according to the principle of the balance between the water of the REI and the water of the environment. As the hydration reactions of the binder are exothermic, the outflow of water continues during setting. At the end of the setting, the partially dehydrated REI grains can, if the final product is placed in contact with water, take up water.
  • additives having the function of preventing the penetration of water into the grains of REI.
  • additive substances form a protective layer around the grain of REI.
  • organic compounds organic ester, polyvinyl propionate
  • minerals alkali silicate
  • the eluting solution is a solution of sodium hydroxide, ammonia, lime aluminum chloride, citrate, oxalate or sodium acetate, or else an amine.
  • the REIs obtained are decanted or drained and then mixed with the thermosetting resin which caused the polymerization.
  • Such pretreatment makes it possible to eliminate the H+ ions from the cationic REIs, these ions acting on the crosslinking accelerator added to the thermosetting resin: the H+ ions are extracted from the REIs, put in solution then separated from the REIs.
  • the pretreatment has the function of replacing the H+, Na+, OH ⁇ , Cl ⁇ ions of the REIs by the ions of the larger eluting solution which modify the three-dimensional network of the REIs so as to prevent the penetration of water into the bituminous mixes immersed in the leaching medium.
  • the risk of swelling is extremely reduced.
  • the present application proposes a process on an industrial scale for treating REIs possibly loaded with borates by a hydraulic binder all at once, on the same place, at the same time and this in order to obtain mixes meeting the safety standards in force in the country.
  • Said method comprises a stage of pretreatment by elution followed by a stage of solidification by taking of hydraulic binder, the conditions of elution making it possible to surprisingly obtain a solidifiable medium, as obtained, by a hydraulic binder although being charged with various ions, in particular with borates.
  • the subject of the invention is a process for immobilizing radioactive ion-exchange resins (REIs) which can contain borates in a quantity which can range up to the equivalent of 1000 g H3 using a hydraulic binder.
  • REIs radioactive ion-exchange resins
  • Ion exchange resins from nuclear installations are collected, stored and then sent to the processing unit. It is therefore not known, in a precise manner, in general before treating it, their composition, the nature and the quantity of the ions which they contain.
  • the stored REIs are in the form of a suspension.
  • the REI to be treated are initially left to settle, the supernatant is removed (pumping, ).
  • the water-saturated REIs obtained are then weighed.
  • the weight of 100% decanted REI introduced for treatment will be the reference from which the quantities of material added subsequently will be calculated.
  • the precipitation combines with the elution so that the efficiency of the elution is clearly improved: the eluted ions precipitating, their concentration in the solution decreasing, the balance between the borates in the REI and the borates in solution is moved.
  • the eluting solution chosen is an aqueous solution of calcium nitrate causing calcium borates to precipitate.
  • the favorable effect on the elution of the precipitation allows a rapid contact time: less than 3 h, and preferably 1 h.
  • This contact time was determined, as well as the amount of equivalents -g cation or anion and the amount of water provided by the eluting solution per kg of REI from numerous tests carried out by the applicant.
  • the volume of eluting solution introduced for this elution has a direct influence on the next step of treatment with the hydraulic binder, because the entire volume is kept for this treatment.
  • the water ratio of the eluting solution (by weight) / binder (by weight) must be included within strict limits.
  • the weight of the added binder depends on the volume of the eluting solution, so the weight of the mix (binder + eluting solution + REI) also depends on it.
  • concentration of the eluting solution approximately 200 g / l; about 1 l / kg REI 100% decanted; 1 hour contact time.
  • the operator can choose other values in the given ranges according to the standards he will have to respect: for less restrictive standards, he can advantageously reduce the contact time. It is certain that the longer the contact time, the greater the elution, therefore the annoying ions are blocked in the solution by precipitation.
  • the eluting solution of lime (preferably in solid form so as not to add water) at a rate of less than 200 g / kg of REI 100 % decanted.
  • the elution therefore takes place according to a discontinuous process in a single step: to the 100% decanted REI is added, with stirring, the eluting solution.
  • decantation, elution and treatment with the hydraulic binder take place in the same device (a kneader-mixer).
  • the hydraulic binder with low heat of hydration is therefore added to the mixture obtained with stirring, the medium being at a pH at least equal to 9.
  • the final matrix in which the REI are immobilized is based on hydraulic binder but can contain other elements in less quantity.
  • the weight of the mix will be equal to the sum of the weight of the eluting solution plus that of the 100% decanted REIs plus that of the binder.
  • the batch of REI is brought into a mixing mixer built by the company GUEDU, said device is associated with a weighing device. After standing during which the REI decant, the supernatant solution is pumped.
  • the device is weighed, the weight of the 100% decanted REI is determined.
  • the whole is kneaded, poured into a container according to the usual conditions for the treatment of waste with a hydraulic binder.
  • the mechanical resistance to compression is more than 100 bars at 7 days, more than 200 bars at 14 days, and more than 300 bars at 2 x 28 days.
  • the process which is the subject of the invention therefore has several essential advantages for industrial exploitation in a nuclear environment.
  • the first is to avoid transfers of active materials: it suffices to bring the waste to be treated. No racking, except pouring the final product into a container, is necessary, nor parallel treatments of extracted effluents.
  • the second advantage is the simplicity of implementing the method.
  • a third advantage is to be able to process any REI coming from a nuclear installation, whether or not it contains borates and even in large quantities. There is again a uniqueness in the treatment.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Surgical Instruments (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Paints Or Removers (AREA)

Description

L'invention concerne un procédé d'immobilisation de résines échangeuses d'ions (REI) radioactives, par un liant hydraulique.The invention relates to a method for immobilizing radioactive ion exchange resins (REIs) with a hydraulic binder.

Les REI radioactives à traiter proviennent essentiellement des réacteurs nucléaires dans lesquels elles sont utilisées pour purifier l'eau de divers circuits du réacteur et quelquefois l'eau des piscines de stockage des éléments combustibles irradiés. En particulier, dans les réacteurs à eau pressurisée PWR, des REI anioniques sont placées sur le circuit primaire dont l'eau est additionnée d'acide borique jouant le rôle de modérateur.The radioactive REIs to be treated come essentially from nuclear reactors in which they are used to purify the water of various reactor circuits and sometimes the water of the storage pools for irradiated fuel elements. In particular, in PWR pressurized water reactors, anionic REIs are placed on the primary circuit, the water of which is supplemented with boric acid playing the role of moderator.

Les REI anioniques peuvent servir alors de "poumon de bore" pour maintenir dans le circuit la concentration en bore désirée.The anionic REIs can then serve as a "boron lung" to maintain the desired boron concentration in the circuit.

Les exploitants de centrales estiment que les REI usées à traiter peuvent contenir en borates jusqu'à l'équivalent de 1000 g d'acide borique par kg de REI sèches.Plant operators estimate that the used REI to be treated can contain borates up to the equivalent of 1000 g of boric acid per kg of dry REI.

Outre les borates, ces REI (cationiques, anioniques, lit mélangé) peuvent contenir les cations lithium, ammonium, fer, cobalt, chrome, nickel, césium et les anions hydroxyde, sulfate, phosphate, silicate, fluorure, chlorure, bicarbonate.In addition to the borates, these REIs (cationic, anionic, mixed bed) can contain the lithium, ammonium, iron, cobalt, chromium, nickel, cesium cations and the hydroxide, sulphate, phosphate, silicate, fluoride, chloride, bicarbonate anions.

Des REI sont également employées dans les installations de retraitement des éléments combustibles irradiés pour la purification de l'eau des piscines de stockage et pour le traitment des liquides.REIs are also used in installations for reprocessing irradiated fuel elements for the purification of water in storage pools and for the treatment of liquids.

Les REI sont placées dans des colonnes ou des cartouches.REIs are placed in columns or cartouches.

Actuellement, elles sont régénérées en place avant immobilisation. Elles contiennent alors essentiellement H⁺, OH⁻ et des cations métalliques actifs non élués.Currently, they are regenerated in place before immobilization. They then essentially contain H⁺, OH⁻ and non-eluted active metal cations.

Pour éviter la dissémination dans l'environnement des substances radioactives, on cherche à immobiliser les déchets les contenant dans une matrice résistante aux agents mécaniques, chimiques ... susceptibles de l'endommager lors du stockage de ces déchets.To avoid the dissemination in the environment of radioactive substances, we seek to immobilize the waste containing them in a matrix resistant to mechanical, chemical agents ... likely to damage it during storage of these waste.

Un moyen pour ce faire, consiste à mélanger lesdits déchets à un liant hydraulique qui, par sa prise suivie de durcissement, confère une certaine résistance mécanique au mélange et une certaine résistance aux attaques chimiques.One way to do this is to mix said waste with a hydraulic binder which, by setting followed by hardening, gives a certain mechanical resistance to the mixture and a certain resistance to chemical attack.

Les valeurs de ces résistances mécanique et chimique que doit atteindre le déchet immobilisé (encore appelé produit final ou enrobé) pour que son stockage assure une sécurité suffisante pour l'homme et l'environnement, sont fixées par des normes de sûreté nucléaire.The values of these mechanical and chemical resistances that immobilized waste (also called final or coated product) must reach in order for its storage to ensure sufficient safety for man and the environment, are set by nuclear safety standards.

Celles-ci sont établies par les autorités nationales et peuvent par conséquent varier d'un pays à l'autre.These are established by national authorities and may therefore vary from country to country.

Les normes de sûreté françaises pour les déchets immobilisés dans un liant hydraulique sont parmi les plus contraignantes : peu de pays ont réussi à atteindre de telles normes avec des déchets contenant des REI. En France, depuis 1982, le traitement des REI par bétonnage a d'ailleurs été interrompu, les procédés utilisés ne conduisent pas à des enrobés acceptables selon les critères de sûreté.French safety standards for waste immobilized in a hydraulic binder are among the most restrictive: few countries have succeeded in reaching such standards with waste containing REI. In France, since 1982, the treatment of REI by concreting has also been interrupted, the processes used do not lead to acceptable mixes according to safety criteria.

Le traitement des REI par un liant hydraulique pose en effet deux problèmes essentiels qu'on ne rencontre pas avec d'autres types de déchets nucléaires.The treatment of REI with a hydraulic binder poses two essential problems that are not encountered with other types of nuclear waste.

Le premier problème est celui de l'échange ionique entre les REI et le milieu contenant le liant hydraulique.The first problem is that of the ion exchange between the REIs and the medium containing the hydraulic binder.

Les ions du milieu qui présentent pour les REI une affinité supérieure à celle qu'ont des ions contenus dans ces REI pour elles, se fixent sur les REI à la place des ions qu'elles contenaient, ces ions étant relargués dans le milieu. Il y a fixation d'ions et simultanément relargage d'autres ions. De sorte que le milieu s'appauvrit en ions du liant hydraulique (Ca⁺⁺ et SO₄⁻⁻ essentiellement) et par contre s'enrichit en ions provenant des installations nucléaires (cations métalliques actifs, phosphates, sulfates .. H⁺, OH⁻ et borates).The ions in the medium which have a greater affinity for the REIs than that which the ions contained in these REIs have for them, attach themselves to the REIs in place of the ions which they contained, these ions being released into the medium. There is ion fixation and simultaneously salting out of other ions. So that the medium is depleted in ions of the hydraulic binder (Ca⁺⁺ and SO₄⁻⁻ essentially) and on the other hand is enriched in ions coming from nuclear installations (active metal cations, phosphates, sulfates .. H⁺, OH⁻ and borates).

L'appauvrissement en ions du liant, notamment en Ca⁺⁺ et SO₄⁻⁻, provoque une mofidication de la prise (retard, incontrôlabilité, prise incomplète). Par ailleurs, les ions amenés par les REI et relargués dans le milieu peuvent gêner la prise, le durcissement ou influencer la tenue dans le temps des déchets immobilisés.

  • Zn⁺⁺ a une action de retardateur ou même d'inhibiteur de prise ;
  • Mg⁺⁺ peut s'échanger avec Ca⁺⁺ des hydrates de calcium, après la prise et donc modifie la tenue dans le temps du produit ;
  • H⁺ les réactions d'hydratation du liant ont lieu en milieu basique, un abaissement du pH à des valeurs acides, retarde la prise voir l'inhibe ;
  • les phosphates ont également un effet retardateur sur la prise.
The depletion of ions in the binder, in particular of Ca⁺⁺ and SO₄⁻⁻, causes a change in the setting (delay, uncontrollability, incomplete intake). In addition, the ions brought in by the REIs and released into the medium can hinder setting, hardening or influence the behavior over time of immobilized waste.
  • Zn⁺⁺ acts as a retarder or even as a setting inhibitor;
  • Mg⁺⁺ can be exchanged with Ca⁺⁺ calcium hydrates, after setting and therefore modifies the behavior over time of the product;
  • H⁺ the hydration reactions of the binder take place in basic medium, a lowering of the pH to acid values, delays the setting see the inhibits;
  • phosphates also have a delaying effect on setting.

Les ions de loin les plus gênants sont les borates. Leur effet est connu sur les liants hydrauliques, et selon leur concentration dans le milieu ils retardent ou inhibent la prise, qu'ils soient sous forme libre ou associés à certains ions tels que le lithium pour former Li₂B₄O₇.By far the most troublesome ions are the borates. Their effect is known on hydraulic binders, and depending on their concentration in the medium they delay or inhibit setting, whether in free form or associated with certain ions such as lithium to form Li₂B₄O₇.

Les échanges ioniques peuvent se poursuivre après la prise, notamment lors des essais de lixiviation, entre le milieu lixiviant et les REI rendues accessibles dans l'enrobé par diverses causes (matrice perméable, mauvaise homogénéité, porosité importante ...). Les ions libérés peuvent générer des réactions nocives pour l'enrobé, c'est le cas par exemple des sulfates.Ion exchanges can continue after setting, in particular during leaching tests, between the leaching medium and the REI made accessible in the mix by various causes (permeable matrix, poor homogeneity, high porosity, etc.). The released ions can generate harmful reactions for the mix, for example sulfates.

Le second type de difficulté rencontré dans le traitement des REI spécifiquement résulte de la migration d'eau des REI vers le milieu contenant le liant hydraulique. Les REI cèdent une fraction de leur eau selon le principe de l'équilibre entre l'eau des REI et l'eau du milieu. Les réactions d'hydratation du liant étant exothermiques,le départ d'eau se poursuit pendant la prise. A l'issue de la prise, les grains de REI partiellement déshydratés peuvent, si le produit final est mis au contact d'eau, reprendre de l'eau.The second type of difficulty encountered in the treatment of REIs specifically results from the migration of water from REIs to the medium containing the hydraulic binder. The REI sell a fraction of their water according to the principle of the balance between the water of the REI and the water of the environment. As the hydration reactions of the binder are exothermic, the outflow of water continues during setting. At the end of the setting, the partially dehydrated REI grains can, if the final product is placed in contact with water, take up water.

C'est le phénomène bien connu de gonflement et de fissuration des enrobés immergés après prise et même durcissement : le gonflement dû à la reprise d'eau provoque la fissuration du matériau et peut se traduire par un délitage total de la matière.This is the well-known phenomenon of swelling and cracking of submerged coated materials after setting and even hardening: swelling due to the uptake of water causes cracking of the material and can result in total disintegration of the material.

A ces deux catégories de problème, des solutions industrielles doivent être apportées dans lesquelles :

  • 1) le volume des enrobés à stocker à long terme doit être aussi réduit que possible pour minimiser les coûts des installations de stockage ;
  • 2) la mise en oeuvre du procédé d'immobilisation doit être technologiquement faisable par des moyens aussi simples que possible, fiable et rapide;
To these two categories of problem, industrial solutions must be provided in which:
  • 1) the volume of asphalt mix to be stored in the long term should be as small as possible to minimize the costs of storage facilities;
  • 2) the implementation of the immobilization process must be technologically feasible by means as simple as possible, reliable and rapid;

Dans le brevet FR-A-75 33 518 sont ajoutés des additifs ayant pour fonction d'empêcher la pénétration de l'eau dans les grains de REI. De telles substances additives forment une couche protectrice autour du grain de REI. Ce sont des composés organiques (ester organique, propionate de polyvinyle) ou minéraux (silicate alcalin).In the patent FR-A-75 33 518 are added additives having the function of preventing the penetration of water into the grains of REI. Such additive substances form a protective layer around the grain of REI. These are organic compounds (organic ester, polyvinyl propionate) or minerals (alkali silicate).

Mais il n'est pas sûr que les ions borates contenus éventuellement dans les REI ne puissent pas passer dans le milieu aqueux. De plus, la mise en oeuvre et le coût rendent ce procédé peu intéressant.However, it is not certain that the borate ions possibly contained in the REIs cannot pass into the aqueous medium. In addition, the implementation and the cost make this process unattractive.

Afin de limiter le transfert d'eau entre les REI et le liant lors de la prise, un autre brevet FR-A-80 21 524 préconise l'emploi de ciment de haut-fourneau dans des conditions précises et la saturation par l'eau des REI. Les conditions : Eau de gâchage/ciment (en poids) = 0,20 à 0,40 et taux d'incorporation = Résine sèche/Enrobé (en poids) ≦ 15 % pour une REI en poudre et ≦ 25 % pour une REI en grains. Précisons que l'eau de gâchage est l'eau ajoutée aux REI saturées d'eau pour assurer la prise du ciment.In order to limit the transfer of water between the REI and the binder during setting, another patent FR-A-80 21 524 recommends the use of blast furnace cement under precise conditions and water saturation REIs. Conditions: Mixing water / cement (by weight) = 0.20 to 0.40 and incorporation rate = Dry resin / Asphalt (by weight) ≦ 15% for REI powder and ≦ 25% for REI in grains. Note that the mixing water is the water added to the REI saturated with water to ensure the setting of the cement.

Il n'est absolument pas tenu compte dans un tel procédé des échanges ioniques susceptibles d'intervenir entre le ciment et les REI. un tel procédé ne peut pas être appliqué aux REI boratées : les ions boratés relargués inhibent la prise du ciment dans les conditions ci-dessus.In such a process, ion exchanges likely to occur between the cement and the REI are absolutely not taken into account. such a process cannot be applied to borated REIs: the released borated ions inhibit the setting of the cement under the above conditions.

Par ailleurs, la solidification par liant hydraulique des effluents boratés est connu par le brevet FR-A-85 04 222 qui décrit un procédé dans lequel avant l'ajout de ciment, les effluents boratés sont traités par de la chaux pour faire précipiter des borates de calcium de structure déterminés dans des conditions précises.Furthermore, solidification by hydraulic binder of borated effluents is known from patent FR-A-85 04 222 which describes a process in which before adding cement, the borated effluents are treated with lime to precipitate calcium borates of structure determined under precise conditions.

Une solution s'imposait alors pour traiter les REI boratées consistant à les éluer pour extraire des REI les ions boratés et les remettre en solution, puis à séparer les REI de la solution éluante, à rincer pour éliminer au mieux les traces de borates, et enfin à bétonner les REI d'un côté et les effluents boratés de l'autre suivant les procédés décrits plus haut.A solution was then required to treat the borated REIs consisting in eluting them to extract the borated ions from the REIs and putting them back into solution, then separating the REIs from the eluting solution, rinsing to eliminate traces of borates as well as possible, and finally concreting the REI on one side and the borated effluents on the other according to the processes described above.

L'élution des REI radioactives a déjà été employée avant la solidification pour bitumage ou par polymérisation d'une résine thermodurcissable.The elution of radioactive REIs has already been used before solidification for asphalting or by polymerization of a thermosetting resin.

Dans le brevet FR-A-76 24 624, la solution éluante est une solution de soude, ammoniaque, chaux chlorure d'aluminium, citrate, oxalate ou acétate de sodium, ou bien une amine. Les REI obtenues sont décantées ou essorées puis mélangées à la résine thermodurcissable dont ont provoque la polymérisation.In patent FR-A-76 24 624, the eluting solution is a solution of sodium hydroxide, ammonia, lime aluminum chloride, citrate, oxalate or sodium acetate, or else an amine. The REIs obtained are decanted or drained and then mixed with the thermosetting resin which caused the polymerization.

Un tel prétraitement permet d'éliminer les ions H⁺ des REI cationiques, ces ions agissant sur l'accélérateur de réticulation ajouté à la résine thermodurcissable : les ions H⁺ sont extraits des REI, mis en solution puis séparés des REI.Such pretreatment makes it possible to eliminate the H⁺ ions from the cationic REIs, these ions acting on the crosslinking accelerator added to the thermosetting resin: the H⁺ ions are extracted from the REIs, put in solution then separated from the REIs.

Dans le brevet EP-157 683 l'élution s'effectue avec une solution de sels de Ca⁺⁺, Be⁺⁺ ou Sr⁺⁺ (anions nitrates, formiates ou acétates), les REI sont séparées de la solution éluante, rincées, mises en suspension dans l'eau puis bitumées.In patent EP-157 683 the elution is carried out with a solution of Ca⁺⁺, Be⁺⁺ or Sr⁺⁺ salts (nitrates, formates or acetates anions), the REIs are separated from the eluting solution, rinsed, suspended in water and then asphalted.

Le prétraitement a pour fonction de remplacer les ions H⁺, Na⁺, OH⁻ , Cl⁻ des REI par les ions de la solutions éluante plus volumineux qui modifient le réseau tridimensionnel des REI de façon à empêcher la pénétration de l'eau dans les enrobés bitumineux plongés dans le milieu de lixiviation. Ainsi le risque de gonflement est extrêmement réduit.The pretreatment has the function of replacing the H⁺, Na⁺, OH⁻, Cl⁻ ions of the REIs by the ions of the larger eluting solution which modify the three-dimensional network of the REIs so as to prevent the penetration of water into the bituminous mixes immersed in the leaching medium. Thus the risk of swelling is extremely reduced.

Selon ces procédés de traitement des REI employant une élution pour éliminer les ions gênants des REI - ces ions étant gênants ou bien par leur action sur le milieu solidifiant ou bien par leur aptitude à permettre la reprise d'eau par les REI- les REI sont séparées de la solution éluante avant d'être immobilisées.According to these processes for treating REIs using an elution to remove the troublesome ions from the REIs - these ions being troublesome either by their action on the solidifying medium or else by their ability to allow water to be taken up by the REIs - the REIs are separated from the eluting solution before being immobilized.

La présente demande propose un procédé à l'échelle industrielle pour traiter les REI éventuellement chargées en borates par un liant hydraulique en une seule fois, sur le même lieu, au même moment et ce pour obtenir des enrobés répondant aux normes de sûreté en vigueur dans le pays.The present application proposes a process on an industrial scale for treating REIs possibly loaded with borates by a hydraulic binder all at once, on the same place, at the same time and this in order to obtain mixes meeting the safety standards in force in the country.

Ledit procédé comporte une étape de prétraitement par élution suivie d'une étape de solidification par prise de liant hydraulique, les conditions de l'élution permettant d'obtenir de façon surprenante un milieu solidifiable, tel que obtenu, par un liant hydraulique bien qu'étant chargé en divers ions, en particulier en borates.Said method comprises a stage of pretreatment by elution followed by a stage of solidification by taking of hydraulic binder, the conditions of elution making it possible to surprisingly obtain a solidifiable medium, as obtained, by a hydraulic binder although being charged with various ions, in particular with borates.

Plus précisément, l'objet de l'invention est un procédé d'immobilisation par un liant hydraulique de résines échangeuses d'ions (REI) radioactives pouvant contenir des borates dans une quantité pouvant aller jusqu'à l'équivalent de 1000 en g H₃ BO₃/kg de REI sèche, caractérisé en ce que les REI sont décantées puis mises au contact pendant 3 h au plus, avec une solution éluante de 100 à 300 g/l en Ca (NO₃)₂ à raison de 1 à 2 l/kg REI décantées et que, au milieu de pH ≧ 9 est ajouté un liant hydraulique à faible chaleur d'hydratation de façon à ce que le rapport Eau de la solution éluante/liant (en poids) soit compris entre 0,3 et 0,5. Dans de telles conditions, le taux d'incorporation F = REI décantées/Enrobé (en poids) est compris entre environ 10 % et 25 %.More specifically, the subject of the invention is a process for immobilizing radioactive ion-exchange resins (REIs) which can contain borates in a quantity which can range up to the equivalent of 1000 g H₃ using a hydraulic binder. BO₃ / kg of dry REI, characterized in that the REI are decanted and then brought into contact for 3 hours at most, with an eluting solution of 100 to 300 g / l of Ca (NO₃) ₂ at a rate of 1 to 2 l / kg decanted REI and that, in the middle of pH ≧ 9, is added a hydraulic binder with low hydration heat so that the water ratio of the eluting solution / binder (by weight) is between 0.3 and 0, 5. Under such conditions, the incorporation rate F = settled decanted / coated REI (by weight) is between approximately 10% and 25%.

Les résines échangeuses d'ions issues des installations nucléaires (cationiques, anioniques ou en lit mélangé) sont collectées, stockées puis envoyées à l'unité de traitement. On ne connait donc pas, de façon précise, en général avant de la traiter, leur composition, la nature et la quantité des ions qu'elles contiennent.Ion exchange resins from nuclear installations (cationic, anionic or mixed bed) are collected, stored and then sent to the processing unit. It is therefore not known, in a precise manner, in general before treating it, their composition, the nature and the quantity of the ions which they contain.

De toute façon, il n'est pas facile d'indiquer une limite précise de la quantité de borates pouvant être fixée puisque des molécules condensées peuvent se former et se fixer. On a estimé à 1000 g eq H₃ BO₃ une quantité importante, une quantité moyenne serait de 500 g eq H₃ BO₃.In any case, it is not easy to indicate a precise limit of the quantity of borates which can be fixed since condensed molecules can form and fix. It has been estimated that 1000 g eq H₃ BO₃ is significant, an average quantity would be 500 g eq H₃ BO₃.

Les REI stockées sont sous forme de suspension. Selon le procédé objet de l'invention, les REI à traiter sont dans un premier temps laissées à décanter, le surnageant est ôté (pompage, ...). Les REI saturées en eau obtenues (dites 100 % décantées) sont alors pesées. Le poids de REI 100 % décantées introduites pour le traitement sera la référence à partir de laquelle seront calculées les quantités de matière ajoutées par la suite.The stored REIs are in the form of a suspension. According to process object of the invention, the REI to be treated are initially left to settle, the supernatant is removed (pumping, ...). The water-saturated REIs obtained (called 100% decanted) are then weighed. The weight of 100% decanted REI introduced for treatment will be the reference from which the quantities of material added subsequently will be calculated.

La mise en contact des REI avec la solution éluante a pour but :

  • de fixer sur les REI les ions de la solution éluante, ions favorables à l'immobilisation par le liant hydraulique ;
  • de mettre en solution les ions des REI parmi lesquels des ions gênants pour l'immobilisation par le liant hydraulique ;
  • de faire précipiter dans la solution lesdits ions gênants sous forme de solides insolubles dans les conditions de l'immobilisation par le liant hydraulique.
The aim of bringing REIs into contact with the eluting solution is:
  • to fix on the REI the ions of the eluting solution, ions favorable to immobilization by the hydraulic binder;
  • to put the REI ions in solution, including ions which are troublesome for immobilization by the hydraulic binder;
  • to cause said troublesome ions to precipitate from the solution in the form of insoluble solids under the conditions of immobilization by the hydraulic binder.

La précipitation se combine à l'élution de telle sorte que l'efficacité de l'élution est nettement améliorée : les ions élués précipitant, leur concentration dans la solution diminuant, l'équilibre entre les borates dans les REI et les borates en solution est déplacé.The precipitation combines with the elution so that the efficiency of the elution is clearly improved: the eluted ions precipitating, their concentration in the solution decreasing, the balance between the borates in the REI and the borates in solution is moved.

La solution éluante choisie est une solution aqueuse de nitrate de calcium faisant précipiter des borates de calcium.The eluting solution chosen is an aqueous solution of calcium nitrate causing calcium borates to precipitate.

L'effet favorable sur l'élution de la précipitation permet un temps rapide de contact : moins de 3 h, et de préférence 1 h.The favorable effect on the elution of the precipitation allows a rapid contact time: less than 3 h, and preferably 1 h.

Ce temps de contact a été déterminé, ainsi que la quantité d'équivalents -g cation ou anion et la quantité d'eau apportées par la solution éluante par kg de REI à partir de nombreux essais effectués par la demanderesse.This contact time was determined, as well as the amount of equivalents -g cation or anion and the amount of water provided by the eluting solution per kg of REI from numerous tests carried out by the applicant.

Il n'était en effet pas possible de choisir des valeurs de procédé ne connaissant ni la composition, ni la capacité d'échange théorique des REI de départ, ni leur teneur en borates.It was indeed not possible to choose process values knowing neither the composition nor the theoretical exchange capacity of the starting REIs, nor their borate content.

Par ailleurs, le volume de solution éluante introduit pour cette élution a une influence directe sur l'étape suivante de traitement par la liant hydraulique, car tout le volume est conservé pour ce traitement.Furthermore, the volume of eluting solution introduced for this elution has a direct influence on the next step of treatment with the hydraulic binder, because the entire volume is kept for this treatment.

En effet, le rapport Eau de la solution éluante (en poids)/liant (en poids) doit être compris dans des limites strictes.Indeed, the water ratio of the eluting solution (by weight) / binder (by weight) must be included within strict limits.

De sorte que le poids du liant ajouté dépend du volume de la solution éluante, donc le poids de l'enrobé (liant+solution éluante+REI) en dépend également.So that the weight of the added binder depends on the volume of the eluting solution, so the weight of the mix (binder + eluting solution + REI) also depends on it.

Or, il n'est pas possible d'augmenter inconsidérément le poids de l'enrobé, des problèmes de manutention et de stockage se posent.However, it is not possible to inconsiderately increase the weight of the mix, handling and storage problems arise.

Il fallait donc choisir la concentration et le volume de solution éluante de façon à ce que :

  • l'élution soit efficace (précipitation effective et fixation) ;
  • il n'y ait pas besoin de rajouter d'eau pour respecter les rapports E/C et F ;
  • le poids de l'enrobé final ne soit pas démesuré ;
  • le volume de solution ne soit pas trop important pour que élution et traitement par le liant puissent avoir lieu dans le même appareil.
It was therefore necessary to choose the concentration and the volume of eluting solution so that:
  • the elution is effective (effective precipitation and fixation);
  • there is no need to add water to respect the E / C and F ratios;
  • the weight of the final mix is not excessive;
  • the volume of solution is not too large for elution and treatment with the binder to take place in the same device.

Simultanément, il fallait déterminer le temps de contact compatible avec les contraites de procédé :

  • élution et précipitation suffisantes pour que l'effet retardant sur la prise des borates ne soit plus sensible.
  • les contraintes industrielles : temps de contact le plus court possible pour pouvoir produire le plus d'enrobés possible par jour.
Simultaneously, it was necessary to determine the contact time compatible with the process constraints:
  • sufficient elution and precipitation so that the effect delaying the setting of borates is no longer noticeable.
  • industrial constraints: shortest possible contact time to be able to produce as much asphalt as possible per day.

Les expériences faites par la demanderesse montrent que l'optimum est atteint avec une solution aqueuse de Ca(NO₃)2 contenant 100 à 300 g/l de nitrate de calcium à raison de 1 à 2 l/Kg de REI 100 % décantées et un temps de contact de 3 h au plus.The experiments carried out by the applicant show that the optimum is reached with an aqueous solution of Ca (NO₃) 2 containing 100 to 300 g / l of calcium nitrate at a rate of 1 to 2 l / Kg of REI 100% decanted and a contact time of 3 hours at most.

Il est bien évident que le temps de contact et la quantité d'ions amenés dépendent de la teneur en borates qui est inconnue en général.It is obvious that the contact time and the quantity of ions brought depend on the borate content which is generally unknown.

Les valeurs préférées correspondent à des enrobés en accord avec les normes de sûreté françaises : concentration de la solution éluante = environ 200 g/l ; environ 1 l/kg REI 100 % décantées ; temps de contact de 1 h.The preferred values correspond to coated materials in accordance with French safety standards: concentration of the eluting solution = approximately 200 g / l; about 1 l / kg REI 100% decanted; 1 hour contact time.

L'exploitant pourra choisir d'autres valeurs dans les plages données selon les normes qu'il aura à respecter : pour des normes moins contraignantes, il pourra avantageusement abaisser le temps de contact. Il est certain que plus le temps de contact se prolonge plus l'élution est importante donc les ions gênants sont bloqués dans la solution par précipitation.The operator can choose other values in the given ranges according to the standards he will have to respect: for less restrictive standards, he can advantageously reduce the contact time. It is certain that the longer the contact time, the greater the elution, therefore the annoying ions are blocked in the solution by precipitation.

Pour augmenter l'efficacité de l'élution, il est avantageusement ajouté en même temps que la solution éluante de la chaux (de préférence sous forme solide pour ne pas rajouter d'eau) à raison de moins de 200 g/kg de REI 100 % décantées.To increase the efficiency of elution, it is advantageously added at the same time as the eluting solution of lime (preferably in solid form so as not to add water) at a rate of less than 200 g / kg of REI 100 % decanted.

L'élution a donc lieu selon un processus discontinu en une seule étape : aux REI 100 % décantées est ajoutée, sous agitation, la solution éluante. Avantageusement, la décantation, l'élution et le traitement par le liant hydraulique ont lieu dans le même appareil (un malaxeur-mélangeur).The elution therefore takes place according to a discontinuous process in a single step: to the 100% decanted REI is added, with stirring, the eluting solution. Advantageously, decantation, elution and treatment with the hydraulic binder take place in the same device (a kneader-mixer).

C'est une caractéristique importante du procédé de traiter la totalité du mélange obtenu à l'issue de l'étape d'élution. En effet, ainsi que le montre l'art antérieur, lorsqu'il y a élution sur des REI, il y a ensuite séparation des REI de la solution.It is an important characteristic of the process to treat the entire mixture obtained at the end of the elution step. Indeed, as the prior art shows, when there is elution on REIs, there is then separation of the REIs from the solution.

Au mélange obtenu est donc ajouté sous agitation le liant hydraulique à faible chaleur d'hydratation, le milieu étant à un pH au moins égal à 9.The hydraulic binder with low heat of hydration is therefore added to the mixture obtained with stirring, the medium being at a pH at least equal to 9.

De préférence, il s'agit d'un ciment de laitier, qui présente de plus lorsqu'il est durci une faible porosité et une faible perméabilité. Les ciments de laitier contiennent des taux variables de clinker (le clinker étant responsable de l'exothermicité de la réaction d'hydratation), citons à titre d'exemple :

En France ciment :
CLK>80 % laitier, < 3 % additifs
CHF 40 à 75 % laitier, < 3 % additifs
CLC 20 à 45 % laitier, < 3% additifs, 20-45 % cendres.
Aux U.S.A. :
Portland Blast furnace 25-65 % laitier
En R.F.A. :
Eisenportland cement > 40 % laitier
Au Japon :
Blast furnace cement type C 60-70 % laitier
Preferably, it is a slag cement, which also exhibits, when it is hardened, a low porosity and a low permeability. Slag cements contain varying amounts of clinker (the clinker being responsible for the exothermicity of the hydration reaction), as an example:
In France cement:
CLK> 80% dairy, <3% additives
CHF 40 to 75% dairy, <3% additives
CLC 20 to 45% dairy, <3% additives, 20-45% ash.
To USA :
Portland Blast furnace 25-65% dairy
In the FRG:
Eisenportland cement> 40% dairy
In Japan :
Blast furnace cement type C 60-70% dairy

Parmi ces ciments, ceux à forte proportion de laitier (> 60%) sont préférés. En France, le chois se portera sur le ciment CLK.Among these cements, those with a high proportion of slag (> 60%) are preferred. In France, the choice will be made on CLK cement.

Avec le liant hydraulique, d'autres additifs peuvent être introduits tels que des charges, des plastifiants... La matrice finale dans laquelle sont immobilisées les REI, est à base de liant hydraulique mais peut contenir d'autres éléments en moindre quantité.With the hydraulic binder, other additives can be introduced such as fillers, plasticizers ... The final matrix in which the REI are immobilized, is based on hydraulic binder but can contain other elements in less quantity.

La quantité de liant ajoutée est telle que le rapport poids d'eau de la solution éluante/poids de liant soit compris entre 0,3 et 0,5 et de préférence 0,4 pour un taux d'incorporation des REI F = poids des REI décantées/poids de l'enrobé compris entre 10 % et 25 %.The amount of binder added is such that the weight ratio of water of the eluting solution / weight of binder is between 0.3 and 0.5 and preferably 0.4 for a rate of incorporation of REI F = weight of Decanted REI / asphalt weight between 10% and 25%.

Le poids de l'enrobé sera égal à la somme du poids de la solution éluante plus celui des REI 100 % décantées plus celui du liant.The weight of the mix will be equal to the sum of the weight of the eluting solution plus that of the 100% decanted REIs plus that of the binder.

Des exemples illustreront mieux l'invention.Examples will better illustrate the invention.

Exemple 1Example 1

Soit un lot de REI boratées en suspension à traiter - Ni la composition de ce lot, ni le type exact de REI, ni leur contenu en borates ne sont connus pour le traitement.Either a batch of borated REI in suspension to be treated - Neither the composition of this batch, nor the exact type of REI, nor their borate content are known for treatment.

En fait ces REI contiennent 350 g. éq H₃ BO₃/kg REI sèches, ce sont des REI anioniques Amberlites IRN 78 LCL.In fact these REI contain 350 g. éq H₃ BO₃ / kg dry REI, these are anionic REI Amberlites IRN 78 LCL.

Le lot de REI est amené dans un malaxeur mélangeur construit par la société GUEDU, audit appareil est associé un dispositif de pesée. Après repos pendant lequel les REI décantent, la solution surnageante est pompée.The batch of REI is brought into a mixing mixer built by the company GUEDU, said device is associated with a weighing device. After standing during which the REI decant, the supernatant solution is pumped.

L'appareil est pesé, le poids des REI 100 % décantées est déterminé.The device is weighed, the weight of the 100% decanted REI is determined.

Aux 16,5 kg de REI 100 % décantées obtenus, 30 l de solution aqueuse de Ca(NO₃)₂ à 200 g/l est ajouté ainsi que 0,8 kg de chaux solide, le tout est agité 1 h.To the 16.5 kg of 100% decanted REI obtained, 30 l of aqueous Ca (NO₃) solution solution at 200 g / l are added as well as 0.8 kg of solid lime, the whole is stirred for 1 h.

75 kg de ciment CLK sont ensuite ajoutées sous agitation.75 kg of CLK cement are then added with stirring.

L'ensemble est malaxé, déversé dans un conteneur selon les conditions habituelles du traitement des déchets par un liant hydraulique.The whole is kneaded, poured into a container according to the usual conditions for the treatment of waste with a hydraulic binder.

Le poids de l'enrobé obtenu est de 120 kg environ, ce qui représente un taux d'incorporation F′ de 4 % en résines sèches, un rapport Eau totale/ciment = 0,5 (eau totale = eau de la solution saturante + eau de constitution des REI + eau interstitielle présente dans les REI 100 % décantées) et un facteur d'augmentation de volume f de 4,7.The weight of the asphalt mix obtained is approximately 120 kg, which represents an incorporation rate F ′ of 4% in dry resins, a total water / cement ratio = 0.5 (total water = water in the saturating solution + REI constitution water + interstitial water present in 100% decanted REIs) and a volume increase factor f of 4.7.

Des carottages sont effectués dans cet enrobé et les échantillons prélevés sont testés en résistance mécanique.Coring is carried out in this asphalt and the samples taken are tested for mechanical strength.

La résistance mécanique à la compression est de plus de 100 bars à 7 jours, plus de 200 bars à 14 jours, et plus de 300 bars à 2 x 28 jours.The mechanical resistance to compression is more than 100 bars at 7 days, more than 200 bars at 14 days, and more than 300 bars at 2 x 28 days.

Exemple 2Example 2

Le même lot que précédemment est décanté, pesé (16,5 kg) et élué par 21,5 l d'une solution aqueuse à 200 g/l de Ca (NO₃)₂ - 51 kg de ciment CLK sont ajoutés.The same batch as above is decanted, weighed (16.5 kg) and eluted with 21.5 l of an aqueous solution containing 200 g / l of Ca (NO₃) ₂ - 51 kg of CLK cement are added.

On a alors

F′
= 8 % (en résines sèches)
f
= 3,5
We have then
F ′
= 8% (in dry resins)
f
= 3.5

En contre-partie d'une meilleure incorporation on a un moindre durcissemment puisque la résistance à la compression est de moins de 10 bars à 7 jours et de plus de 200 bars à 28 jours.In return for better incorporation there is less hardening since the compressive strength is less than 10 bars at 7 days and more than 200 bars at 28 days.

Ce procédé, nécessitant pour être mis en oeuvre un appareillage unique composé d'un malaxeur, applicable à toute REI utilisée en milieu nucléaire, apporte une simplification très importante au niveau industriel dans le bétonnage des REI radioactives.This process, requiring to be implemented a single apparatus composed of a mixer, applicable to any REI used in nuclear environment, brings a very important simplification at the industrial level in the concreting of radioactive REI.

Le procédé objet de l'invention présente donc plusieurs avantages essentiels pour une exploitation industrielle en milieu nucléaire.The process which is the subject of the invention therefore has several essential advantages for industrial exploitation in a nuclear environment.

Le premier est d'éviter les transferts de matériaux actifs : il suffit d'amener les déchets à traiter. Aucun soutirage, hors la coulée du produit final dans un conteneur, n'est nécessaire, ni des traitements parallèles d'effluents extraits.The first is to avoid transfers of active materials: it suffices to bring the waste to be treated. No racking, except pouring the final product into a container, is necessary, nor parallel treatments of extracted effluents.

Ceci parce que tout le traitement peut être effectué dans un seul appareil : le malaxeur.This is because all the treatment can be carried out in a single device: the mixer.

Le second avantage est la simplicité de mise en oeuvre du procédé.The second advantage is the simplicity of implementing the method.

Une REI arrive, on ne connaît rien de son passé. Elle peut être immobilisée de façon à être acceptable selon les critères de sûreté. Il suffit de déterminer son poids à l'état décanté et se placer dans les plages de valeurs indiquées par le procédé objet de l'invention.An REI arrives, we know nothing of its past. It can be immobilized so as to be acceptable according to safety criteria. It suffices to determine its weight in the decanted state and to place itself within the ranges of values indicated by the process which is the subject of the invention.

Par ailleurs, l'élution est une opération facile.Furthermore, elution is an easy operation.

Toutes les opérations faciles, tous les appareillages simples sont recherchés en milieu nucléaire où le moindre problème soulève des difficultés quant à l'invention humaine (la manipulation manuelle sur place) et quant à la décontamination ou confinement des matières radioactives.All the easy operations, all the simple devices are sought in nuclear environment where the least problem raises difficulties as for the human invention (manual handling on the spot) and as for the decontamination or confinement of radioactive materials.

Un troisième avantage est de pouvoir traiter n'importe quelle REI provenant d'une installation nucléaire, qu'elle contienne ou non des borates et même en grande quantité. Il y a là encore une unicité dans le traitement.A third advantage is to be able to process any REI coming from a nuclear installation, whether or not it contains borates and even in large quantities. There is again a uniqueness in the treatment.

Claims (4)

1. Process for immobilizing, by a hydraulic binder, radioactive ion exchange resins, which can contain borates in a quantity which can reach up to the equivalent of 1000 g H₃ BO₃/kg of dry resin, characterized in that :
- said resins are decanted;
- then placed in contact for a maximum of three hours with an eluant solution of 100 to 300 g/l in Ca (NO₃)₂ in the proportion of 1 to 2 liters of eluant solution for 1 kg of decanted resins; and in that,
- a hydraulic binder of low hydration heat is added to the medium of pH ≧ 9 in such a quantity that the ratio by weight, E/C = Water of the eluent solution Binder
Figure imgb0003
 is between 0.3 and 0.5.
2. Process according to claim 1, characterized in that lime is added to said decanted resins in the proportion of 200 g/kg of 100% decanted resins, at the same time as the eluant solution.
3. Process according to one of claims 1 or 2, characterized in that the hydraulic binder is a slag cement.
4. Process according to claim 3, characterized in that the cement is CLK cement.
EP88401175A 1987-05-15 1988-05-13 Process for immobilizing ion-exchangers by hydraulic binding-material Expired - Lifetime EP0294260B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8706871 1987-05-15
FR8706871A FR2615315B1 (en) 1987-05-15 1987-05-15 METHOD FOR IMMOBILIZING RESINS EXCHANGING RADIOACTIVE IONS BY A HYDRAULIC BINDER

Publications (2)

Publication Number Publication Date
EP0294260A1 EP0294260A1 (en) 1988-12-07
EP0294260B1 true EP0294260B1 (en) 1992-03-25

Family

ID=9351146

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88401175A Expired - Lifetime EP0294260B1 (en) 1987-05-15 1988-05-13 Process for immobilizing ion-exchangers by hydraulic binding-material

Country Status (7)

Country Link
EP (1) EP0294260B1 (en)
JP (1) JP2683779B2 (en)
KR (1) KR970011261B1 (en)
DE (1) DE3869481D1 (en)
ES (1) ES2031254T3 (en)
FR (1) FR2615315B1 (en)
WO (1) WO1988009040A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4137947C2 (en) * 1991-11-18 1996-01-11 Siemens Ag Processes for the treatment of radioactive waste
DE4324818C2 (en) * 1993-07-23 2002-06-27 Framatome Anp Gmbh Process for the disposal of ion exchange resin
FR2773504B1 (en) * 1998-01-12 2000-03-31 Bouygues Sa METHOD FOR CONDITIONING PARTICLES OF ION EXCHANGE RESINS AND APPLICATION TO THE TREATMENT OF RADIOACTIVE WATER
FR2803942A1 (en) * 2000-01-13 2001-07-20 Patrick Byk Electrical guitar construction having integrated compact sound chain with amplifier/preamplifier/electronic card effects and loudspeakers.
NL2027369B1 (en) * 2021-01-22 2022-08-05 Pkb Top Holding B V Immobilizing chemical species

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2553569C2 (en) * 1975-11-28 1985-09-12 Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe Process for the solidification of radioactive aqueous waste materials by spray calcination and subsequent embedding in a matrix made of glass or glass ceramic
DE2603116C2 (en) * 1976-01-28 1983-01-27 Nukem Gmbh, 6450 Hanau Process for the solidification of radioactive borate-containing aqueous solutions and suspensions
SE412658B (en) * 1977-07-05 1980-03-10 Asea Atom Ab SET IN CEMENT BEDDING ACID OR BORATE-RADIOACTIVE WASTE
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

Also Published As

Publication number Publication date
KR970011261B1 (en) 1997-07-08
FR2615315B1 (en) 1989-08-25
WO1988009040A1 (en) 1988-11-17
JPH01503332A (en) 1989-11-09
DE3869481D1 (en) 1992-04-30
ES2031254T3 (en) 1992-12-01
JP2683779B2 (en) 1997-12-03
FR2615315A1 (en) 1988-11-18
KR890702212A (en) 1989-12-23
EP0294260A1 (en) 1988-12-07

Similar Documents

Publication Publication Date Title
EP0001499B1 (en) Treatment and disposal of heavy metal containing sludge wastes
US4363757A (en) Method for noncontaminating solidification for final storage of aqueous, radioactive waste liquids
NO142213B (en) PROCEDURE FOR IMPROVING THE QUALITY OF WASTE WATER FROM WASTE FILLINGS
FR2542223A1 (en) PROCESS FOR INCORPORATING ION EXCHANGE RESINS IN SOLID MASS
EP0294260B1 (en) Process for immobilizing ion-exchangers by hydraulic binding-material
DE69213419T2 (en) Process for fixing waste materials
US4892685A (en) Process for the immobilization of ion exchange resins originating from radioactive product reprocessing plants
Cioffi et al. Evaluation of mechanical and leaching properties of cement-based solidified materials encapsulating Cd-exchanged natural zeolites
GB1564878A (en) Method of improving the leaching resistance of solidified bitumen products containing radioactive substances
FR2525803A1 (en) METHOD FOR IMPROVING THE RETENTION OF RADIONUCLEIDS BY SOLIDIFIED RADIOACTIVE WASTE
JP2908107B2 (en) Solidification material for radioactive waste and method for treating radioactive waste
JPS6073500A (en) Fixed product of hydrous waste and cement and manufacture thereof
FI129112B (en) Method for treating and solidifying liquid waste
US4582637A (en) Reprocessing of irradiated nuclear fuel
JP2001208896A (en) Method of cosolidifying low-level radioactive wetting waste generated from boiling water nuclear power plant
JPS5815000B2 (en) Radioactive waste disposal method
CN111933326A (en) Method for treating radioactive tritium-containing wastewater
RU2271586C2 (en) Method for immobilizing concentrated liquid radioactive wastes (alternatives)
JPH073475B2 (en) Method for solidifying radioactive waste
RU2763146C1 (en) Method for immobilising liquid radioactive waste
GB2130428A (en) A process for reducing the volume of aqueous radioactive waste
JP7126580B2 (en) Method for treating borate waste liquid
JP4787998B2 (en) Solidification method for radioactive waste
JPS6186692A (en) Method of solidifying spent radioactive ion exchange resin
JP4787997B2 (en) Solidification method for radioactive liquid waste containing sodium dihydrogen phosphate

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE ES FR GB IT LI

17P Request for examination filed

Effective date: 19890111

17Q First examination report despatched

Effective date: 19901026

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE ES FR GB IT LI

ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

REF Corresponds to:

Ref document number: 3869481

Country of ref document: DE

Date of ref document: 19920430

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2031254

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 19940718

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20020514

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20020603

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030531

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030531

BERE Be: lapsed

Owner name: SOC. GENERALE POUR LES TECHNIQUES NOUVELLES *SGN

Effective date: 20030531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20040506

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20040514

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050513

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050514

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051201

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20050514

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070511

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070525

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20080512

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20080512