EP0327691B1 - Procédé d'élimination définitive de déchets radioactifs - Google Patents

Procédé d'élimination définitive de déchets radioactifs Download PDF

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Publication number
EP0327691B1
EP0327691B1 EP88119450A EP88119450A EP0327691B1 EP 0327691 B1 EP0327691 B1 EP 0327691B1 EP 88119450 A EP88119450 A EP 88119450A EP 88119450 A EP88119450 A EP 88119450A EP 0327691 B1 EP0327691 B1 EP 0327691B1
Authority
EP
European Patent Office
Prior art keywords
potassium permanganate
cement
carrier material
hydrogen
samples
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
EP88119450A
Other languages
German (de)
English (en)
Other versions
EP0327691A3 (en
EP0327691A2 (fr
Inventor
Herbert Lammertz
Kornelius Dr. Kroth
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 Juelich GmbH
Original Assignee
Forschungszentrum Juelich 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 Forschungszentrum Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Priority to JP1017809A priority Critical patent/JPH01267499A/ja
Publication of EP0327691A2 publication Critical patent/EP0327691A2/fr
Publication of EP0327691A3 publication Critical patent/EP0327691A3/de
Application granted granted Critical
Publication of EP0327691B1 publication Critical patent/EP0327691B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • G21F9/04—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S376/00—Induced nuclear reactions: processes, systems, and elements
    • Y10S376/90—Particular material or material shapes for fission reactors
    • Y10S376/901—Fuel
    • Y10S376/902—Fuel with external lubricating or absorbing material

Definitions

  • the invention relates to a method for the storage of radioactive waste materials, in which the waste materials are solidified or pressed and then enclosed in a container.
  • Radioactive waste - solidified or compressed - is enclosed in containers for storage in order to avoid radioactive contamination of the environment. It has been shown that hydrogen is generated in the waste material by chemical and radiolytic processes, which is undesirable for reasons of final storage.
  • radioactive wastes for example those from the reprocessing of fuel elements, such as structural parts, Zirkaloy cladding tubes and insoluble residues from the fuel solution (feed sewage sludge) are cemented into containers for final storage.
  • the waste / cement mixture is usually placed in 140 l so-called insert drums, which in turn are placed in 200 l drums. After the cement has set, these insert drums are placed in 200-liter drums and sealed with rubber seals and lids.
  • the water contained in the cement matrix is broken down into hydrogen and oxygen by radiolysis.
  • the oxygen reacts with the materials of the waste container and is therefore usually not found in the empty space of the 200 l drums, which contains about 70 l of free gas volume.
  • the potassium permanganate is expediently used in dissolved form. To do this, to apply the potassium permanganate to the surface of the carrier material, proceed according to the procedure of claim 3.
  • a particularly simple and yet effective embodiment of the method according to the invention consists in that the potassium permanganate in solid form is added to the cement before it sets (claim 2) or is added to the carrier material (claim 4).
  • Ceramic materials such as Al2O3 or chamotte, are suitable as carrier material.
  • oxidizing agent used Since the oxidizing agent used is consumed in the conversion of the hydrogen, a sufficient amount thereof must be used to convert the total hydrogen produced during the storage period.
  • the amount of oxidizing agent used on the other hand, in the event that it is added to the cement, must not lead to a reduction in the strength of the cement. In this regard, potassium permanganate has been found to be suitable.
  • potassium permanganate 10 g to 100 g of potassium permanganate are expediently used per liter of cement stone, concrete and / or carrier material used. If you mix the cement with saturated potassium permanganate solution, then about 35 g KMnO4 / liter cement stone are reached. In total, more potassium permanganate can be contained in the wrapping material, which is filled into the annular gap volume of the 200 l drums (up to 100 g / liter) can be used. If aluminum oxide is used as a carrier material for the coating material, approximately 15-30 g of potassium permanganate per kg of aluminum oxide will be applied to it. With a uniform mixture of aluminum oxide and solid potassium permanganate, 100 g per liter of carrier material can be easily adjusted.
  • the H2-reactivity of potassium permanganate was compared in parallel on two samples of the same composition with and without radiation.
  • two samples were made from cement stone bodies and two samples from Al2O3 (each mixed with potassium permanganate).
  • the cement stone samples and the Al2O3 samples were sealed gas-tight in the 1.65-liter vessels, evacuated and charged with a gas mixture consisting of 20% H2 and 80% Kr.
  • sample 1 and 2 Portland cement 35; pH 12.5
  • 1270 g of cement, 575 g of water and 15 g of KMnO4 0.095 mol
  • the mass of sample 1 was 1755 g
  • the mass of sample 2 was 1765 g.
  • One of the parallel samples was irradiated for 5 days up to a dose of 1.5 - 2.5 x 106 rad.
  • the other parallel sample was stored in the laboratory at room temperature without irradiation.
  • samples No. 1 and 2 practically completely devour the H2 volume and the hydrogen released in sample 2 by irradiation during the test period. At the same time, there is presumably a certain release of O2 by elimination from the KMnO4, the O2 elimination being increased in the irradiated sample.
  • insert drums (140 l) with cemented radioactive structural parts, fuel element sleeves and feed sewage sludge were removed from the larger containers (200 l drum) and sealed in specially made measuring containers.
  • the empty volume of the measuring container was approx. 47 l.
  • the release of radiolysis hydrogen from the cemented waste was determined by observing the internal pressure of the container and by taking gas samples with subsequent gas chromatographic analysis of the gas components.
  • the H2 release was first observed over a period of 300 days and an average release rate of approx. 77 Nml H2 / day was determined.
  • the measuring container was then opened and a drip tray with approx. 2.5 kg Al2O3, which had been impregnated with approx. 40 g KMnO4 in the manner indicated in Example 1, admitted.
  • the measuring container was closed again gas-tight and flushed with synthetic air before the measuring phase.
  • the internal pressure after the addition of the Al2O3 sample fell continuously from about 1000 mbar to about 860 mbar within 120 days.
  • gas samples were taken after 56 and 120 days.
  • the analyzes showed 0.4% H2, 7.2% O2, 89.5% N2 and 0.5% CH4 for the first sample, and 2.5% H2, 1.0% O2, 91, for the second sample. 4% N2 and 1.2% CH4.
  • the increased H2 content at the end of the service life is due to the fact that the potassium permanganate was almost exhausted.
  • 100 g KMnOprobe in crystal form was added to a freshly mixed cement sample of approx. 1 liter, with a water / cement ratio of 0.43, and mixed in evenly.
  • the cylindrical sample was shaped after 24 hours, placed in a sealed vessel and kept under a hydrogen partial pressure of 500-600 mbar for 32 days. During this time the vessel was in a thermostat at 50 ° C.
  • the whole container was tightly closed and was kept at 50 ° C under 500 - 600 mbar hydrogen partial pressure for 8 days.

Landscapes

  • 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 (6)

  1. Procédé de stockage de déchets radioactifs, dans lequel les déchets sont solidifiés ou comprimés et ensuite, enfermés dans un conteneur, caractérisé en ce qu'on enveloppe les déchets, au moins partiellement, d'un ciment contenant du permanganate de potassium pour éliminer l'hydrogène formé pendant le stockage ou on utilise, comme matériau d'enrobage, un matériau support non réducteur avec du permanganate de potassium, les déchets et le matériau d'enrobage étant introduits dans un conteneur commun.
  2. Procédé selon la revendication 1, caractérisé en ce que le permanganate de potassium est ajouté au ciment à l'état dissous ou solide avant la prise de celui-ci, pour le cas où les déchets sont solidifiés par enrobage au ciment.
  3. Procédé selon la revendication 1, caractérisé en ce que le permanganate de potassium est appliqué sur le matériau support à l'état dissous et ensuite, le matériau est séché avant son utilisation comme matériau d'enrobage.
  4. Procédé selon la revendication 1, caractérisé en ce que le permanganate de potassium est ajouté au matériau support à l'état solide.
  5. Procédé selon la revendication 1, 3 ou 4, caractérisé en ce qu'on utilise Al₂O₃ comme matériau support.
  6. Procédé selon une des revendications précédentes, caractérisé en ce qu'on utilise, pour le stockage définitif des déchets, de 10 g à 100 g de permanganate de potassium par litre de ciment solidifié, de béton et/ou de matériau support.
EP88119450A 1988-01-30 1988-11-23 Procédé d'élimination définitive de déchets radioactifs Expired - Lifetime EP0327691B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1017809A JPH01267499A (ja) 1988-01-30 1989-01-30 放射性廃棄物の貯蔵方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3802755A DE3802755A1 (de) 1988-01-30 1988-01-30 Verfahren zur einlagerung von radioaktiven abfallstoffen
DE3802755 1988-01-30

Publications (3)

Publication Number Publication Date
EP0327691A2 EP0327691A2 (fr) 1989-08-16
EP0327691A3 EP0327691A3 (en) 1989-09-06
EP0327691B1 true EP0327691B1 (fr) 1993-09-15

Family

ID=6346299

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88119450A Expired - Lifetime EP0327691B1 (fr) 1988-01-30 1988-11-23 Procédé d'élimination définitive de déchets radioactifs

Country Status (4)

Country Link
US (1) US4943394A (fr)
EP (1) EP0327691B1 (fr)
JP (1) JPH01267499A (fr)
DE (2) DE3802755A1 (fr)

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GB9017038D0 (en) * 1990-08-03 1990-09-19 Alcan Int Ltd Controlled hydrogen generation from composite powder material
JP3150445B2 (ja) * 1992-09-18 2001-03-26 株式会社日立製作所 放射性廃棄物の処理方法，放射性廃棄物の固化体及び固化材
US6004522A (en) * 1993-12-15 1999-12-21 Purafil, Inc. Solid filtration media incorporating elevated levels of permanganate and water
DE4343500A1 (de) * 1993-12-20 1995-06-22 Forschungszentrum Juelich Gmbh Vorrichtung zur Vermeidung von Überdrücken in Lagerbehältern mit Wasserstoff entwickelndem Inhalt
US5649323A (en) * 1995-01-17 1997-07-15 Kalb; Paul D. Composition and process for the encapsulation and stabilization of radioactive hazardous and mixed wastes
US5942323A (en) 1995-01-27 1999-08-24 Purafil, Inc. Fiber filter and methods of use thereof
TW365009B (en) * 1996-09-24 1999-07-21 Jgc Corp Method of disposal of metallic aluminum-containing radioactive solid waste
FR2799876B1 (fr) * 1999-10-15 2002-01-04 Tech Et D Entpr S Generales So Procede de conditionnement de dechets metalliques non ferreux radioactifs
WO2002049115A1 (fr) 2000-12-11 2002-06-20 Cree, Inc. Procede de fabrication d'un transistor autoaligne a jonction bipolaire en carbure de silicium et dispositifs correspondants
JP4615749B2 (ja) * 2001-03-22 2011-01-19 日揮株式会社 放射性廃棄物処理方法及びその装置
JP4040854B2 (ja) * 2001-09-28 2008-01-30 株式会社神戸製鋼所 放射性廃棄物の処分容器、処分施設及び処分方法
FR2939700B1 (fr) * 2008-12-11 2014-09-12 Commissariat Energie Atomique Materiau pour le piegeage d'hydrogene, procede de preparation et utilisations
US7758836B1 (en) 2009-04-14 2010-07-20 Huggins Ronald G System and method for removing sulfur-containing contaminants from indoor air
US20130014670A1 (en) * 2010-04-01 2013-01-17 Commissariat a I'Energie Atomique et Aux Energies Altematives Use of anticorrosion agents for conditioning magnesium metal, conditioning material thus obtained and preparation process

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US4056937A (en) * 1976-01-08 1977-11-08 Kyokado Engineering Co. Ltd. Method of consolidating soils
BE838533A (fr) * 1976-02-13 1976-05-28 Procede de sechage des solutions contenant de l'acide borique
US4049545A (en) * 1976-07-08 1977-09-20 Rocky Carvalho Chemical waste water treatment method
CA1100151A (fr) * 1976-07-19 1981-04-28 William L. Prior Procede et composition pour la formation de ciments alveolaires par addition de resines
US4119560A (en) * 1977-03-28 1978-10-10 United Technologies Corporation Method of treating radioactive waste
WO1980000047A1 (fr) * 1978-06-08 1980-01-10 Bp Chem Int Ltd Encapsulation de dechets
DE2910034C2 (de) * 1979-03-14 1985-02-28 Kraftwerk Union AG, 4330 Mülheim Verfahren zur Aufbereitung radioaktiver Lösungen
FR2490865A1 (fr) * 1980-09-19 1982-03-26 Commissariat Energie Atomique Procede de traitement, avant bitumage, de solutions ou suspensions renfermant des ions reducteurs
DE3110491C2 (de) * 1981-03-18 1985-02-14 Rheinisch-Westfälisches Elektrizitätswerk AG, 4300 Essen Verfahren und Anlage zum Einengen eines in einem Kernkraftwerk anfallenden, Borsäure enthaltenden radioaktiven Abwassers
JPS57172299A (en) * 1981-04-16 1982-10-23 Mitsubishi Genshi Nenryo Kk Radioactive liquid waste processing method
BE899598A (fr) * 1984-05-07 1984-08-31 Arklow S A Procede de neutralisation et de solidification de dechets.

Also Published As

Publication number Publication date
US4943394A (en) 1990-07-24
EP0327691A3 (en) 1989-09-06
DE3884180D1 (de) 1993-10-21
JPH01267499A (ja) 1989-10-25
DE3802755A1 (de) 1989-08-10
EP0327691A2 (fr) 1989-08-16

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