EP0318367B1 - Verfahren zur Konditionierung von radioaktiven oder toxischen Abfällen in wärmehärtbaren Harzen - Google Patents

Verfahren zur Konditionierung von radioaktiven oder toxischen Abfällen in wärmehärtbaren Harzen Download PDF

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Publication number
EP0318367B1
EP0318367B1 EP88402916A EP88402916A EP0318367B1 EP 0318367 B1 EP0318367 B1 EP 0318367B1 EP 88402916 A EP88402916 A EP 88402916A EP 88402916 A EP88402916 A EP 88402916A EP 0318367 B1 EP0318367 B1 EP 0318367B1
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EP
European Patent Office
Prior art keywords
waste
hardening agent
water
hardener
liquid hardening
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP88402916A
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English (en)
French (fr)
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EP0318367A1 (de
Inventor
André Barlou
Alexandre Beltritti
Patrick Gramondi
Hugues Vidal
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.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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Publication of EP0318367A1 publication Critical patent/EP0318367A1/de
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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
    • G21F9/307—Processing by fixation in stable solid media in polymeric matrix, e.g. resins, tars

Definitions

  • the present invention relates to a process for packaging radioactive or toxic waste in thermosetting resins.
  • radioactive or toxic waste stored in water, in particular radioactive waste comprising ion exchange resins and / or acidic compounds.
  • ion exchange resins are used in particular to purify contaminated water, in particular the effluents from these installations. After a certain time, these resins undergo degradation phenomena and consequently lose their effectiveness. Since these used resins have fixed a certain number of radioelements during their use, it is then necessary to condition them in an appropriate material to ensure good retention of their radioactivity.
  • thermosetting resins such as epoxy resins.
  • processes for conditioning in thermosetting resins are described in particular in French patents FR-A-2 251 081, FR-A-2 361 724, FR-A-2 544 909 and FR-A-2 577 709.
  • this preliminary spin step leads to certain drawbacks. Indeed, during the final mixing of the dewatered waste with the resin and the hardener, it is difficult to avoid that air is included in the mixture due to the viscosity of the products used and the increase in temperature resulting from the exothermicity of the reactions. This presence of air is harmful because it lowers, on the one hand, the density of the solid block, and it increases, on the other hand, the porosity at the expense of the confining power.
  • the subject of the present invention is precisely a process for packaging waste stored in water in a thermosetting resin which makes it possible to avoid this drawback.
  • the resin hardener is thus used as the liquid phase for transferring the waste into the thermosetting resin.
  • thermosetting resins suitable for coating radioactive or toxic waste can be used, provided that these can be hardened by a liquid hardener having a density greater than that of water.
  • thermosetting resins By way of example of such thermosetting resins, mention may be made of unsaturated polyester resins, vinyl resins, epoxy resins and phenoplast resins.
  • an epoxy resin which can be hardened by hardeners with active hydrogen such as amines, phenols, polyacids and polyalcohols.
  • an amino hardener which can be introduced in the pure state or in the form of a solution in a suitable diluent, or alternatively in the form of an adduct, that is to say the product of the reaction of low amount of the epoxy resin with an amino compound, to which a diluent can also be added if necessary to obtain a liquid phase having the desired viscosity.
  • the method of the invention can be used for the treatment of different types of radioactive or toxic waste stored in water.
  • the radioactive waste can be used ion exchange resins, precipitation sludge originating for example from the chemical treatment of radioactive waste water, activated carbon originating from filtration and purification installations, precipitates forming. for example during storage of radioactive residual solutions and residual deposits forming for example in storage containers.
  • toxic waste By way of example of toxic waste, mention may be made of cadmium and arsenic derivatives, cyanides, chromium derivatives, mercury and its salts, tin and antimony derivatives, thallium derivatives, solid residues containing plant protection agents, insecticides, fungicides, etc.
  • the method of the invention applies in particular to the treatment of radioactive waste comprising ion exchange resins and / or acidic compounds.
  • the amino hardener may comprise at least one amino compound chosen from the group consisting of cycloaliphatic and aromatic amines, aromatic and cycloaliphatic polyamines, propylene amine derivatives and polyaminoamides.
  • the amino hardener consists of an adduct which is the product of the reaction of a small amount of the epoxy resin with one of the amino compounds mentioned above.
  • a diluent can also be added to obtain a liquid phase having the desired viscosity.
  • amino hardeners constituted by a mixture of an aromatic amine or polyamine and an aliphatic or cycloaliphatic amine or polyamine, as described in FR-A-2,544 909.
  • the aromatic amine or polyamine can be present in the form of an adduct with a small amount of the epoxy resin.
  • a non-reactive diluent such as benzyl alcohol.
  • the liquid hardener may further comprise a hardening accelerator, consisting for example of the reaction product of acrylic acid, benzoic acid, salicylic acid, or phenol resorcinol with a amino compound, for example diaminodiphenylmethane.
  • a hardening accelerator consisting for example of the reaction product of acrylic acid, benzoic acid, salicylic acid, or phenol resorcinol with a amino compound, for example diaminodiphenylmethane.
  • Other additives for example compounds capable of preventing the decantation of radioactive or toxic waste in the resin during hardening, can also be added to the liquid hardener, for example a thixotropic agent, or a product such as pitch solution, as described in French patent FR-A-2,577,709.
  • the fact of adding the liquid amine hardener before mixing the waste with the epoxy resin makes it possible to limit the exothermicity of the hardening reaction.
  • the amino hardener reacts with the active sites of the resins to neutralize these, and a temperature rise is generally obtained due to the exothermicity of the neutralization reaction which is added to the temperature increase due to neutralization which is added to the temperature increase due to the curing reaction which is also exothermic.
  • it is necessary not to exceed 100 ° C., which poses certain problems.
  • this neutralization reaction is carried out in water, before the actual hardening reaction, and the heat produced during this neutralization reaction is diluted or eliminated by water. Therefore, the initial temperature of the polymerization reaction is no longer influenced by this neutralization reaction, and the maximum temperature reached during the curing of the epoxy resin is lower, by at least 10 ° C, than that reached when the dewatered waste is directly mixed with the resin and the hardener.
  • the fact of adding the liquid hardener to the waste stored in the water makes it possible to simplify the operation of kneading the resin with the waste. Indeed the mixture of waste and hardener is more fluid than waste alone, and less energy is used for the mixing operation.
  • ion exchange resins in the form of beads are conditioned in an epoxy resin which are constituted by a mixture of 60% by weight of anion exchange resins in OH-) RA400 form sold by ROHM and HAAS and by 40%. by weight of cationic resins in Na + IR 120 form sold by ROHM and HAAS.
  • an epoxy resin consisting of a diglycidyl ether of bisphenol A having an epoxide equivalent of approximately 190 diluted with neopentyl diglycidyl ether and marketed by CDF Chimie under the reference MN 201T, and a hardener consisting of the product are used.
  • CDF Chimie sold under the reference D6M5 by CDF Chimie, which is composed of a cycloaliphatic polyamine having an amine equivalent of approximately 63 and a diaminodiphenylmethane adduct and epoxy resin MN 201 T having an amine equivalent of approximately 130.
  • the amounts of resin and hardener used are respectively 100 and 60 parts by weight with a weight ratio, ion exchange resins / (thermosetting resin + hardener), equal to 1.
  • the mixture is then left to harden for 24 hours at room temperature, and the density of the product obtained is determined.
  • the same mixture of ion exchange resin is packaged in the same epoxy resin using the method of the prior art described in FR-A-2,544,909.
  • the mixture of ion exchange resins is first filtered for 8 minutes to remove the storage water, then 100 kg of the mixture of drained ion exchange resins are introduced. in the 2251 container. 62.5 kg of MN 201T epoxy resin and 37.5 kg of hardener D6 M5 are then added and the mixture is kneaded also using a stirring paddle driven by an electric motor and then the product is allowed to harden. at room temperature. The density of the product obtained after hardening is then determined.
  • the method of the invention makes it possible to obtain a density gain of 10%, a time saving of 160% over the pumping time of the water, a gain of 12% over the maximum temperature reached during hardening and a gain of 360% on the intensity necessary to achieve agitation of the mixture.
  • Example 2 The procedure is the same as in Example 1 but using the quantities of ion exchange resin, epoxy resin, hardener and thixotropic agent given in Table 2 attached.
  • Example 2 the same mixture of ion exchange resin and the same epoxy resin, the same hardener and the same thixotropic agent as in Example 2 are used, but the packaging is carried out using the process of the prior art as in Comparative Example 1.
  • the method of the invention thus allows many advantages to be obtained compared to the method of the prior art.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Epoxy Resins (AREA)
  • Processing Of Solid Wastes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Claims (10)

1. Verfahren zur Konditionierung in Wasser eingelagerter Abfälle in einem wärmehärtbaren Harz, bestehend aus dem Vermischen der Abfälle mit dem Harz und einem flüssigen Härter, dadurch gekennzeichnet, daß man einen flüssigen, mit Wasser nicht mischbaren Härter verwendet, welcher eine höhere Dichte als die von Wasser besitzt, und daß das Verfahren nach folgenden aufeinanderfolgenden Schritten verläuft:
a) Zugabe und Vermischen des flüssigen Härters mit den in Wasser eingelagerten Abfällen,
b) Absitzen der Abfälle mit dem flüssigen Härter,
c) Abziehen des über den abgesetzten und in den flüssigen Härter überführten Abfällen vorhandenen Wassers und
d) Vermischen der in den flüssigen Härter überführten Abfälle mit dem wärmehärtbaren Harz.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß das wärmehärtbare Harz ein Epoxidharz ist.
3. Verfahren gemäß einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die Abfälle lonenaustauscherharze und/oder saure Verbindungen enthalten.
4. Verfahren gemäß einem der Ansprüche 2 und 3, dadurch gekennzeichnet, daß der flüssige Härter ein Amin-Härter ist.
5. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß der Amin-Härter wenigstens ein aus der aus cycloaliphatischen und aromatischen Aminen, cycloaliphatischen und aromatischen Polyaminen, Propylenamin-Derivaten und Polyaminoamiden bestehenden Gruppe ausgewähltes Amin enthält.
6. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daßderAmin-Härteraus einem Addukt besteht, welches das Reaktionsprodukt einer geringen Menge des Epoxidharzes mit der Amin-Verbindung ist.
7. Verfahren gemäß den Ansprüchen 2 und 3, dadurch gekennzeichnet, daß der flüssige Härter aus einem Gemisch eines aromatischen Amins oder Polyamins mit einem aliphatischen odercycloaliphatischen Amin oder Polyamin besteht.
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß das aromatische Amin oder Polyamin in Form des Addukts mit einer geringen Menge des Epoxidharzes vorliegt.
9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß der flüssige Härter ein Thixotropie-Mittel enthält.
10. Verfahren gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß derflüssige Härter Teer enthält.
EP88402916A 1987-11-23 1988-11-21 Verfahren zur Konditionierung von radioaktiven oder toxischen Abfällen in wärmehärtbaren Harzen Expired - Lifetime EP0318367B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8716199A FR2623655B1 (fr) 1987-11-23 1987-11-23 Procede de conditionnement de dechets radioactifs ou toxiques dans des resines thermodurcissables
FR8716199 1987-11-23

Publications (2)

Publication Number Publication Date
EP0318367A1 EP0318367A1 (de) 1989-05-31
EP0318367B1 true EP0318367B1 (de) 1992-07-08

Family

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Application Number Title Priority Date Filing Date
EP88402916A Expired - Lifetime EP0318367B1 (de) 1987-11-23 1988-11-21 Verfahren zur Konditionierung von radioaktiven oder toxischen Abfällen in wärmehärtbaren Harzen

Country Status (7)

Country Link
US (1) US4927564A (de)
EP (1) EP0318367B1 (de)
JP (1) JP2634212B2 (de)
CA (1) CA1331225C (de)
DE (1) DE3872674T2 (de)
ES (1) ES2033454T3 (de)
FR (1) FR2623655B1 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5037560A (en) * 1990-03-09 1991-08-06 Danny Gayman Sludge treatment process
FR2678761B1 (fr) * 1991-07-03 1994-07-01 Commissariat Energie Atomique Bloc contenant des resines echangeuses d'ions contaminees et son procede de preparation.
DE4324818C2 (de) * 1993-07-23 2002-06-27 Framatome Anp Gmbh Verfahren zum Entsorgen von Ionenaustauscherharz
US5434338A (en) * 1993-09-16 1995-07-18 Us Technology Recycling Corporation Process for conditioning waste materials and products therefrom
US5946639A (en) * 1997-08-26 1999-08-31 The United States Of America As Represented By The Department Of Energy In-situ stabilization of radioactive zirconium swarf
EP1301015B1 (de) 2001-10-05 2006-01-04 Matsushita Electric Industrial Co., Ltd. Freisprecheinrichtung zur mobilen Kommunikation im Fahrzeug
FR2933099B1 (fr) * 2008-06-30 2011-11-25 Spado Sa Composition d'enrobage pour le stockage de dechets toxiques pour la sante et/ou l'environnement depourvue d'agent durcisseur aromatique
FR2977894B1 (fr) * 2011-07-11 2013-08-16 Conditionnement Des Dechets Et Effluents Ind Socodei Soc Pour Composition d'enrobage pour le confinement de dechets toxiques pour l'environnement et/ou la sante
GB2522173A (en) * 2013-10-02 2015-07-22 Nat Nuclear Lab Ltd Encapsulation of Waste Materials

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723338A (en) * 1971-04-28 1973-03-27 Atomic Energy Commission Method of reducing the release of mobile contaminants from granular solids
FR2361724A1 (fr) * 1976-08-12 1978-03-10 Commissariat Energie Atomique Procede de stockage de resines echangeuses d'ions contaminees
FR2361725A1 (fr) * 1976-08-13 1978-03-10 Commissariat Energie Atomique Procede de stockage de dechets radioactifs solides de grandes dimensions
US4405512A (en) * 1979-04-25 1983-09-20 The Dow Chemical Company Process for encapsulating radioactive organic liquids in a resin
JPS5677800A (en) * 1979-11-29 1981-06-26 Nippon Atomic Ind Group Co Device of making radioactive solidified waste
FR2544909B1 (fr) * 1983-04-21 1985-06-21 Commissariat Energie Atomique Procede de conditionnement de dechets contamines en milieu acide, notamment de materiaux echangeurs de cations
FR2577709B1 (fr) * 1985-02-14 1987-03-20 Commissariat Energie Atomique Procede de conditionnement de dechets radioactifs ou toxiques dans des resines epoxydes et melange polymerisable a deux constituants liquides utilisable dans ce procede
FR2607957A1 (fr) * 1986-12-05 1988-06-10 Commissariat Energie Atomique Bloc contenant des dechets en vue de leur stockage et procede de realisation d'un tel bloc

Also Published As

Publication number Publication date
ES2033454T3 (es) 1993-03-16
JPH01156699A (ja) 1989-06-20
US4927564A (en) 1990-05-22
EP0318367A1 (de) 1989-05-31
DE3872674D1 (de) 1992-08-13
FR2623655B1 (fr) 1990-03-02
JP2634212B2 (ja) 1997-07-23
FR2623655A1 (fr) 1989-05-26
DE3872674T2 (de) 1993-01-21
CA1331225C (en) 1994-08-02

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