EP0165103B1 - Procédé pour l'enrobage et le stockage de matières dangereuses, notamment radioactives, dans un conteneur monolithique, dispositif pour mettre en oeuvre ledit procédé et produit obtenu - Google Patents

Procédé pour l'enrobage et le stockage de matières dangereuses, notamment radioactives, dans un conteneur monolithique, dispositif pour mettre en oeuvre ledit procédé et produit obtenu Download PDF

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Publication number
EP0165103B1
EP0165103B1 EP85400836A EP85400836A EP0165103B1 EP 0165103 B1 EP0165103 B1 EP 0165103B1 EP 85400836 A EP85400836 A EP 85400836A EP 85400836 A EP85400836 A EP 85400836A EP 0165103 B1 EP0165103 B1 EP 0165103B1
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EP
European Patent Office
Prior art keywords
porcelain
ashes
ceramic
slip
forming composition
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
EP85400836A
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German (de)
English (en)
French (fr)
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EP0165103A1 (fr
Inventor
Bruno Aubert
Serge Carpentier
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
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Publication of EP0165103A1 publication Critical patent/EP0165103A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B30—PRESSES
    • B30B—PRESSES IN GENERAL
    • B30B11/00—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses
    • B30B11/34—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses for coating articles, e.g. tablets
    • 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
    • G21F9/34—Disposal of solid waste

Definitions

  • the present invention relates to a coating process, for storage, of hazardous materials, in particular radioactive materials in a monolithic container and product obtained.
  • Another highly radioactive waste consisting of fission product solutions, is packaged in the form of a glass poured into a metal container.
  • Radioactive iodine 129 in the form of lead iodide is Another delicate storage case.
  • Australian patent 531,250 describes a process of this type in which the waste in powder form is mixed with a synthetic rock in powder and compacted, the core thus formed is then surrounded by a layer of a low density material to absorb the dilations, then this set is itself surrounded by a layer of clean synthetic rock; the assembly obtained is subjected to the action of heat and pressure.
  • a specific device which is a press with graphite walls which can withstand a high temperature.
  • the formation of the rock structure to obtain a compact block from powders of the materials composing said rock is not at all easy: the action of heat and pressure must combine and their values must be sufficiently high.
  • the starting materials being in the form of powders
  • air is included so that, in the final cooking operation, the air included and the gases possibly formed in the waste can practically not escape causing cracking and other damage.
  • the applicant proposes a method for immobilizing and packaging radioactive ash in a mineral matrix which can be implemented with simple equipment, which does not require pressure cooking, which uses the coating materials. in the form of a paste or powder with pressing in stages and final cooking according to a precise program so that the gases escape before the porosity closes and in which the product obtained is a monolithic block, that is to say say airtight.
  • US Patent 4,404,129 describes a container, intended to contain radioactive waste, formed by a molding procedure from a wall and a bottom. Said radioactive waste is incorporated into a molten glass, the mixture obtained is then introduced in the molten state into an inert glass itself contained in a mold.
  • pistons 3 and 4 either together or separately.
  • the strength of the press provides an internal pressure of 3.5 gigapascals.
  • the piston 22 is depressed so as to form by pressing the side wall (raw) 27 of the container.
  • the box 28 is filled with product 29 intended for coating.
  • This product can be wrapped in a thin plastic bag to avoid contamination of the pistons.
  • the piston 22 is brought into contact with the upper part of the box, then the piston 22 is lowered to compress the matrix to be coated which takes the form shown at 30.
  • FIG. 9 shows the piston 23 in the high position, while the piston 22 has not moved and the raw dough intended to form the upper face (cover) was introduced at 31.
  • FIG. 10 shows the phase of compression of the cover taking the form 32 obtained by stopping the piston 23 just at the same low level as the piston 22.
  • the unmolded raw part is cooked in an electric oven, respecting a precise heating program. In the examples given below, this heating program will be detailed.
  • the ash to be coated is mixed with this ceramising agent in proportion such that this new material, after firing, has a coefficient of expansion close to 4.10 -6 / ° C like most porcelains.
  • Example 6 Likewise for Example 6 in which lead iodide is coated.
  • the first two examples relate to the coating of the same ash in two different matrices (and on two different scales).
  • the third example relates to the coating of grains of silicon carbide coming from the post-combustion chamber of a waste incinerator.
  • the fourth example relates to the coating of asbestos fibers which have served as filter media for hot gases.
  • the fifth example relates to the coating of calcinate ⁇ with fission products (by evaporation then calcination at 600 ° C. of solution of fission products).
  • the sixth example relates to the coating of lead iodide.
  • the bottom of the container was also formed with a powder containing little air thanks to the pressure program.
  • Powder is placed in the annular space and compressed according to the previous program to finish at a height of 47.3 mm from the bottom of the matrix.
  • the cylinder is removed from the oven a yellowish white color having a diameter of 63 mm and a height of 58 mm.
  • Zone 1 is a hard, compact ceramic without porosity.
  • Zone 2 is a more or less vitrified ash conglomerate. Between these two zones, the transition is made on less than 0.1 mm.
  • the ash of the same composition is used to coat the mullitic porcelain (called hard porcelain).
  • the starting paste has the approximate composition:
  • this water comprises approximately 70% of constituting water (in particular in the kaolin used to prepare the dough) and 30% of processing water.
  • a material similar to that described above is used for pressing, but of larger dimensions, external diameter of the annular piston 160 mm, internal diameter of the annular piston 113 mm.
  • the pressing force is of the order of 700 kN.
  • the pressing operations take place as in Example 1 for the decompression cycles.
  • the apparent porosity is zero and no cracks appear.
  • sawing it is found that the ashes form a homogeneous mass of approximately 100 mm in diameter, surrounded in all directions by a thickness of approximately 21 mm of very hard porcelain.
  • Grains with a diameter of 1 to 15 mm are available from the coarse grinding of the silicon carbide aggregates in the post-combustion chamber of an incinerator.
  • Example 1 for molding and baking and a solid cylinder is obtained.
  • This heterogeneous mass is perfectly surrounded by sandstone without any visible crack.
  • Asbestos comes from the hot gas filters of an incinerator.
  • a paste is made at equal volume with the asbestos and the sandstone slurry of Example 1 and this mixture is then treated like the ash of Example 1.
  • a cylinder is obtained after molding and cooking without defects. By sawing, we see inside a greener zone corresponding to the sandstone-asbestos mixture practically without transition with the pure sandstone surrounding the central zone.
  • the fission products are separated from uranium and plutonium in the form of a nitric solution.
  • the usual method is to concentrate them by evaporation, to calcine them, then to mix them with a glass frit, to melt this mixture and to pour it in sealed containers.
  • composition of the synthetic calcine is: (% by weight)
  • these calcinates are mixed with 10% by weight of petalite and 10% by weight of sodium silicate and operates according to the procedure of Example 1.
  • the container After cooling, the container is sawn and it is found that the calcinate is transformed into a vitreous mass filling more than 90% (some bubbles remain) the central zone of the shard.
  • This powder is used under the conditions of Example 1 to coat it in sandstone.
  • FIG. 16 shows the number of strokes counted on the ordinate, the displacement along EF on the abscissa.
  • the number of counts counted for the iodine (rai L alpha L beta) has been represented on the ordinate and on the abscissa, the displacements along H, the point K corresponding to the core-coating boundary and the distance KL to 1 mm.
  • the number of strokes that is to say a quantity proportional to the concentration, is constant on average (apart from the porosity fluctuations) in the core, and decreases from K to L over 1 mm of travel, for achieve background noise.
  • This background noise corresponds to a detection threshold can, in fact, be taken as a zero for the concentration of iodine.
  • the same background noise value is in fact obtained on a ceramic of Example 1 not containing iodine.
  • this curve is that the iodine present in the heart has slightly migrated towards the outside but that the migration only interested an area of 1 mm thick around the heart.
  • Figure 19 shows, in the case of cesium, that the migration was only partial since the heart contains a significant part of cesium.
  • lead iodide can be mixed with raw sandstone paste and coated with this mixture as described above.
  • the present invention finds its greatest interest in the definitive coating of contaminated materials, in a material of unlimited lifetime, even in very hostile medium without it being necessary to provide an envelope, metallic or other, around the manufactured block. according to this process.

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Processing Of Solid Wastes (AREA)
EP85400836A 1984-05-04 1985-04-29 Procédé pour l'enrobage et le stockage de matières dangereuses, notamment radioactives, dans un conteneur monolithique, dispositif pour mettre en oeuvre ledit procédé et produit obtenu Expired EP0165103B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8406969A FR2563936B1 (fr) 1984-05-04 1984-05-04 Procede pour l'enrobage et le stockage de matieres dangereuses, notamment radioactives, dans un conteneur monolithique, dispositif pour mettre en oeuvre le procede et produit obtenu
FR8406969 1984-05-04

Publications (2)

Publication Number Publication Date
EP0165103A1 EP0165103A1 (fr) 1985-12-18
EP0165103B1 true EP0165103B1 (fr) 1988-10-19

Family

ID=9303707

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Application Number Title Priority Date Filing Date
EP85400836A Expired EP0165103B1 (fr) 1984-05-04 1985-04-29 Procédé pour l'enrobage et le stockage de matières dangereuses, notamment radioactives, dans un conteneur monolithique, dispositif pour mettre en oeuvre ledit procédé et produit obtenu

Country Status (6)

Country Link
US (1) US4726916A (ja)
EP (1) EP0165103B1 (ja)
JP (1) JPS6134499A (ja)
CA (1) CA1263220A (ja)
DE (1) DE3565734D1 (ja)
FR (1) FR2563936B1 (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105175006B (zh) * 2015-08-27 2017-12-26 广东科达洁能股份有限公司 一种轻质保温砖的烧成工艺

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US4932853A (en) * 1985-10-29 1990-06-12 Environmental Protection Polymers,Inc. Staged mold for encapsulating hazardous wastes
US4891165A (en) * 1988-07-28 1990-01-02 Best Industries, Inc. Device and method for encapsulating radioactive materials
WO1990001208A1 (en) * 1988-07-28 1990-02-08 Best Industries, Inc. Device and method for encapsulating radioactive materials
CA2001013C (en) * 1988-10-19 1995-04-18 Toshikiyo Hirata Array antenna system
US4861520A (en) * 1988-10-28 1989-08-29 Eric van't Hooft Capsule for radioactive source
US5683345A (en) 1994-10-27 1997-11-04 Novoste Corporation Method and apparatus for treating a desired area in the vascular system of a patient
US5899882A (en) * 1994-10-27 1999-05-04 Novoste Corporation Catheter apparatus for radiation treatment of a desired area in the vascular system of a patient
AU7110098A (en) * 1997-04-10 1998-10-30 Nucon Systems, Inc. Large size, thick-walled ceramic containers
US6342650B1 (en) * 1999-06-23 2002-01-29 VALFELLS áGUST Disposal of radiation waste in glacial ice
US7531152B2 (en) 2000-10-19 2009-05-12 Studsvik, Inc. Mineralization of alkali metals, sulfur, and halogens
US20060167331A1 (en) * 1999-10-20 2006-07-27 Mason J B Single stage denitration
US7476194B2 (en) * 1999-10-20 2009-01-13 Studsvik, Inc. In-container mineralization
US20080119684A1 (en) * 1999-10-20 2008-05-22 Mason J Bradley In-Container Mineralization
GB0118945D0 (en) * 2001-08-03 2001-09-26 British Nuclear Fuels Plc Encapsulation of waste
US6890913B2 (en) * 2003-02-26 2005-05-10 Food Industry Research And Development Institute Chitosans
GB0716417D0 (en) * 2007-08-23 2007-10-03 Ukaea Ltd Waste encapsulation
US20160379727A1 (en) 2015-01-30 2016-12-29 Studsvik, Inc. Apparatus and methods for treatment of radioactive organic waste
CN105175007B (zh) * 2015-08-27 2017-12-26 广东科达洁能股份有限公司 一种轻质保温砖

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US3358590A (en) * 1966-08-18 1967-12-19 Clyde R Ashworth Waste compressor
DE2747951A1 (de) * 1976-11-02 1978-05-11 Asea Ab Verfahren zur bindung radioaktiver stoffe in einem koerper, der gegen auslaugen durch wasser bestaendig ist
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IL54316A (en) * 1977-04-04 1982-01-31 Macedo Pedro B Fixation of radioactive materials in a glass matrix
US4224177A (en) * 1978-03-09 1980-09-23 Pedro B. Macedo Fixation of radioactive materials in a glass matrix
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
DE2819085C3 (de) * 1978-04-29 1981-04-23 Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe Verfahren zur endlagerreifen, umweltfreundlichen Verfestigung von hoch- und mittelradioaktiven und/oder Actiniden enthaltenden, wäßrigen Abfallkonzentraten oder von in Wasser aufgeschlämmten, feinkörnigen festen Abfällen
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Publication number Priority date Publication date Assignee Title
CN105175006B (zh) * 2015-08-27 2017-12-26 广东科达洁能股份有限公司 一种轻质保温砖的烧成工艺

Also Published As

Publication number Publication date
CA1263220A (en) 1989-11-28
DE3565734D1 (en) 1988-11-24
EP0165103A1 (fr) 1985-12-18
JPS6134499A (ja) 1986-02-18
FR2563936B1 (fr) 1989-04-28
US4726916A (en) 1988-02-23
FR2563936A1 (fr) 1985-11-08

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