EP0054604B1 - Procédé de préparation de corps résiduaires solidifiés pour le stockage définitif de déchets radioactifs - Google Patents

Procédé de préparation de corps résiduaires solidifiés pour le stockage définitif de déchets radioactifs Download PDF

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Publication number
EP0054604B1
EP0054604B1 EP19810100979 EP81100979A EP0054604B1 EP 0054604 B1 EP0054604 B1 EP 0054604B1 EP 19810100979 EP19810100979 EP 19810100979 EP 81100979 A EP81100979 A EP 81100979A EP 0054604 B1 EP0054604 B1 EP 0054604B1
Authority
EP
European Patent Office
Prior art keywords
radioactive
cement
waste
molded bodies
heat treatment
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
Application number
EP19810100979
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German (de)
English (en)
Other versions
EP0054604A3 (en
EP0054604A2 (fr
Inventor
Rainer Dr. Dipl.-Chem. Köster
Peter Dipl. Chem Vejmelka
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.)
Forschungszentrum Karlsruhe GmbH
Original Assignee
Kernforschungszentrum Karlsruhe GmbH
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 Kernforschungszentrum Karlsruhe GmbH filed Critical Kernforschungszentrum Karlsruhe GmbH
Publication of EP0054604A2 publication Critical patent/EP0054604A2/fr
Publication of EP0054604A3 publication Critical patent/EP0054604A3/de
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Publication of EP0054604B1 publication Critical patent/EP0054604B1/fr
Expired legal-status Critical Current

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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
    • 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
    • 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
    • G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
    • G21F9/165—Cement or cement-like matrix

Definitions

  • the invention relates to a process for the production of waste solidification products that are ready for disposal and contain radioactive substances with high radiation resistance or low radiolysis gas formation from the category of the radioactive waste moldings consolidated with hydraulically setting, hardening, inorganic materials, with soft radioactive, liquid, aqueous and / or radioactive solid wastes are mixed or coated with a cement-water slurry, allowed to harden and subjected to a heat treatment.
  • Cement mixtures are currently used to solidify solid, lumpy waste such as fuel element sleeves or core components.
  • the products are not post-treated thermally.
  • the disadvantages of cemented high-level radioactive or medium-level radioactive waste, ash, fuel element sleeves and core component products are that, due to the comparatively high water content under the influence of the radioactive radiation emanating from the waste, the radiation-chemical decomposition of the water causes large amounts of hydrogen and Oxygen are formed. This could have disadvantages for the operational safety of the intermediate and final storage.
  • the temperatures of the products during storage must be regulated so that they do not exceed 100 ° C. At higher temperatures, water is released from the products, which leads to significant pressure build-up in the product itself and in the container. If the container is corroded, this can lead to the release of activity from the container.
  • the invention is based on the object of creating a process for the production of waste solidification products ready for disposal, containing radioactive substances, with high radiation resistance or less radiolysis gas formation from the category of the radioactive waste moldings solidified with hydraulically setting, hardening, inorganic materials , which all or almost all positive properties of the known solidification products also have, but the disadvantages of the known products, in particular the formation of radiolysis gas, the pressure build-up in the product or in the container, the risk of activity being released from the container or the volatilization of radioactive nuclides in the manufacture during the high temperature steps etc.
  • the object is achieved in a surprisingly simple manner according to the invention in that the mixtures of waste and cement-water slurry are hardened with a cement containing Portland cement clinker in closed containers at a temperature between room temperature and 150.degree. C. to give shaped bodies and in that the hardened moldings are added Normal pressure or at a negative pressure, a heat treatment at temperatures from 100 ° C to a maximum of 250 ° C to remove the pores of the molded bodies from free water.
  • the cement used can also contain additives such as bentonite.
  • An advantageous embodiment of the invention is characterized in that the heat treatment of the shaped bodies (step c) is carried out at a temperature between 150 ° and 250 ° C and over a period of between 12 hours and 4 days.
  • the resulting aqueous solutions or aqueous slurries are mixed directly with the cement according to the invention with stirring in a container, which may also be the final storage container, or mixed indirectly in a mixing vessel and then filled into the container.
  • the solid, lumpy waste is poured over with a mixture made of cement according to the invention and water (W / Z value advantageously 0.3 to 0.6), possibly using low pressures.
  • the hydration (process step b)) is advantageously carried out at temperatures between room temperature and 100 ° C.
  • the removal of the excess water (process step c)) is advantageously carried out at temperatures between 100 ° C and 200 ° C.
  • the temperature and the duration of the heat treatment are strongly dependent on the composition and dimensions of the products.
  • the products should be heated up relatively slowly to avoid cracking.
  • the optimal heating and drying times must be adapted to the respective product composition and size. Heating rates in the range between 0.5 ° C./min and 2 ° C./min have proven to be advantageous.
  • the inventive method Compared to the previous known methods for solidifying the waste solutions or slurries, such as. B. solidification in a glass matrix, etc., the inventive method has a number of significant advantages.
  • the process technology for producing the waste products is very simple compared to glazing (mixing in the container by stirring in a separate mixing vessel and filling into the container).
  • the hydration of the products and the removal of the excess water (of the water present in the pores of the solidification product) takes place at comparatively low temperatures, and therefore no radioactive elements escaping via the gas phase, such as e.g. B. cesium and ruthenium.
  • the products By lowering the water content, the products can be stored at temperatures that are above 100 ° C to 150 ° C, since there is no longer any free water and therefore no increased water vapor partial pressure can build up and no activity can be released.
  • Half of the samples from a), b) and c) were produced in accordance with the prior art, ie without heat treatment, only stored for 28 days at room temperature.
  • the other half of the samples were heat-treated by the method according to the invention, ie dewatered at 200 ° C. and normal pressure.
  • all samples were irradiated with 10 MeV electrons up to 10 8 rad and the gas yield measured in ml / g and Mrad.
  • the weight loss of the dewatered samples was 23% by weight both in the samples under a) and in the samples under b) and under c). This corresponds to a residual water content of approx. 7 to 9% by weight in the product.
  • Radiolysis gas formation for all samples is shown in the table below.
  • Example 1 laboratory blocks were produced, but using a deep drilling cement, which has no Portland cement clinker content and is to be included in the group of cements, the main components of which are in the ranges 20 to 30% by weight SiO 2 and 40 to 70% by weight CaO fall, instead of the PZ 35. Only samples corresponding to a) in Example 1 were produced. The water-cement ratio was also 0.4, the type of irradiation and duration was the same as in Example 1. The hydrogen production rate was at 28 days stored at room temperature, the sample (prior art) 2.5 - 10- 3 ml / g and Mrad and dewatered in the group treated by the inventive process (at 200 ° C and atmospheric pressure sample only 3.7. 10- 4 ml / g and Mrad.
  • M means the weight weighed for certain samples after a certain time interval
  • 4M the weight change in percent of the starting weight. From the table it can easily be seen that after a certain period of time the weight change of the sample with the special cement becomes practically zero, i. H. after taking up a certain amount of the quinary solution, the mass of the sample remains the same. In contrast, the Portland cement sample (which corresponds to the prior art) swells, exhibits a significant increase in mass during increasing storage in the quinary solution and is therefore exposed to increased corrosion.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Processing Of Solid Wastes (AREA)

Claims (3)

1. Procédé pour la fabrication de produits de la solidification de déchets, contenant des substances radioactives prêtes au stockage définitif, avec une résine élevée à l'irradiation et une faible avec une résistance de gaz de radiolyse, de la catégorie des corps moulés à base de déchets radioactifs solidifiés au moyen de matières minérales faisant prise hydraulique, durcissantes, dans lesquels on enrobe ou mélange des déchets aqueux liquides, radioactifs et/ou des déchets solides radioactifs avec une suspension de ciment et d'eau, laisse durcir, et soumet à un traitement thermique, procédé caractérisé en ce qu'on laisse durcir les mélanges de déchets et de suspension de ciment et d'eau faits avec un ciment contenant des clinkers de ciment Portland dans des récipients fermés, à une température entre la température ambiante et 150°C, en corps moulés, et que ces corps moulés durcis sont soumis, à la pression normale ou sous une pression réduite à un traitement thermique à des températures pouvant aller de 100°C jusqu'à 250°C au maximum, pour éliminer l'eau présente sans être combinée dans les pores des corps moulés.
2. Procédé pour la fabrication de produits de la solidification de déchets, contenant des substances radioactives prêtes au stockage définitif, avec une résistance élevée à l'irradiation et une faible formation de gaz de radiolyse, de la catégorie des corps moulés à base de déchets radioactifs solidifiés au moyen de matières minérales faisant prise hydraulique, durcissantes, dans lesquels on enrobe ou mélange des déchets aqueux liquides, radioactifs et/ou des déchets solides radioactifs avec une suspension de ciment et d'eau, laisse durcir, et soumet à un traitement thermique, caractérisé en ce que:
a) on mélange ou enrobe les décets radioactifs avec une émulsion d'un ciment exempt de clinker de ciment Portland qui contient ou bien 20 à 30% en poids de Si02 et 40 à 70% en poids de CaO, ou bien 25 à 35% en poids de Si02,10 à 25% en poids de CaO et 30 à 50% en poids d'A1203;
b) laisse durcir les mélanges obtenus suivant a), dans des récipients fermés, à al température ambiante ou plus jusqu'à 150° C, en corps moulés,
c) soumet les corps moulés durcis, à la pression normale ou sous une pression réduite, à un traitement thermique, à des températures de 100°C jusqu'à 250°C au maximum, afin d'éliminer l'eau qui se trouve, non combinée, dans les pores des corps moulés.
3. Procédé suivant les revendications 1 ou 2, caractérisé en ce que le traitement thermique des corps moulés est effectué (étape c), à une température qui se situe entre 150 et 250° C, et pendant une durée qui peut aller de 12 heures à 4 jours.
EP19810100979 1980-12-19 1981-02-12 Procédé de préparation de corps résiduaires solidifiés pour le stockage définitif de déchets radioactifs Expired EP0054604B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803048001 DE3048001A1 (de) 1980-12-19 1980-12-19 Verfahren zur herstellung von endlagerreifen, radioaktive stoffe enthaltenden abfall-verfestigungsprodukten mit erhoehter strahlenbestaendigkeit bzw. verringerter radiolysegas-bildung aus der kategorie der mit hydraulisch abbindenden, aushaertenden, anorganischen materialien verfestigten, radioaktiven abfall-formkoerpern
DE3048001 1980-12-19

Publications (3)

Publication Number Publication Date
EP0054604A2 EP0054604A2 (fr) 1982-06-30
EP0054604A3 EP0054604A3 (en) 1982-08-18
EP0054604B1 true EP0054604B1 (fr) 1985-11-13

Family

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Family Applications (1)

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EP19810100979 Expired EP0054604B1 (fr) 1980-12-19 1981-02-12 Procédé de préparation de corps résiduaires solidifiés pour le stockage définitif de déchets radioactifs

Country Status (4)

Country Link
EP (1) EP0054604B1 (fr)
JP (1) JPS57128898A (fr)
BR (1) BR8108271A (fr)
DE (1) DE3048001A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3219114A1 (de) * 1982-05-21 1983-11-24 Kernforschungsz Karlsruhe Verfahren zur verbesserung der eingenschaften von verfestigungen radioaktiver festabfaelle
EP0137054B1 (fr) * 1983-09-13 1987-05-27 Kernforschungszentrum Karlsruhe Gmbh Procédé pour la fabrication d'un produit de fixation de boues résiduaires nuisibles et de ciment résistant au lessivage
EP0157771A1 (fr) * 1983-10-17 1985-10-16 Chem-Nuclear Systems, Inc. Solidification amelioree de dechets radioactifs aqueux par l'utilisation de composes insolubles de l'oxyde de magnesium
DE3429412A1 (de) * 1984-08-09 1986-02-20 Kraftwerk Union AG, 4330 Mülheim Mischvorrichtung
DE3833676A1 (de) * 1988-10-04 1990-04-05 Petri Juergen Dipl Ing Dr Verfahren zur endlagerung von eingebundenen abfallstoffen
FR2939700B1 (fr) 2008-12-11 2014-09-12 Commissariat Energie Atomique Materiau pour le piegeage d'hydrogene, procede de preparation et utilisations
CN102646455B (zh) * 2012-04-26 2014-09-17 北京市奥利爱得科技发展有限公司 对放射性废弃物进行放射性去除的方法及其系统
GB2522173A (en) * 2013-10-02 2015-07-22 Nat Nuclear Lab Ltd Encapsulation of Waste Materials

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL235423A (fr) * 1959-01-19
AT325165B (de) * 1971-01-14 1975-10-10 Schoeller Bleckmann Stahlwerke Verfahren zur aufnahme radioaktiver abfalle in einbettmassen
FR2266264A1 (en) * 1974-04-02 1975-10-24 Us Energy Radioactive isotopes entrapped in cancrinite - to protect the environment, by reacting caustic liquor with clay and sodium nitrate
DE2726087C2 (de) * 1977-06-10 1978-12-21 Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe Verfahren zur endlagerreifen, umweltfreundlichen Verfestigung von" und mittelradioaktiven und/oder Actiniden enthaltenden, wäßrigen Abfallkonzentraten oder von in Wasser aufgeschlämmten, feinkörnigen festen Abfällen
JPS54136000A (en) * 1978-04-14 1979-10-22 Hitachi Ltd Cement solidification treating method of radioactive waste

Also Published As

Publication number Publication date
EP0054604A3 (en) 1982-08-18
EP0054604A2 (fr) 1982-06-30
DE3048001A1 (de) 1982-07-01
BR8108271A (pt) 1982-10-05
JPS57128898A (en) 1982-08-10

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