EP0318367A1 - 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
EP0318367A1
EP0318367A1 EP88402916A EP88402916A EP0318367A1 EP 0318367 A1 EP0318367 A1 EP 0318367A1 EP 88402916 A EP88402916 A EP 88402916A EP 88402916 A EP88402916 A EP 88402916A EP 0318367 A1 EP0318367 A1 EP 0318367A1
Authority
EP
European Patent Office
Prior art keywords
hardener
water
waste
liquid hardener
liquid
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.)
Granted
Application number
EP88402916A
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English (en)
French (fr)
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EP0318367B1 (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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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 wrung 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 cured by active hydrogen hardeners 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 a weak 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. You can also add a thinner to obtain a liquid phase with 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 can also be added to the liquid hardener, for example compounds capable of preventing the decantation of radioactive or toxic waste in the resin during hardening, for example a thixotropic agent, or a product such as a solution pitch, 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 increase in temperature due to the curing reaction which is also exothermic.
  • 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 water makes it possible to simplify the operation of kneading the resin with the waste.
  • 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 consist of a mixture of 60% by weight of anion exchange resins in OH-IRA 400 form sold by ROHM and HAAS and of 40%. by weight of cationic resins in Na+ IR 120 form sold by ROHM and HAAS.
  • an epoxy resin constituted by 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 wrung for 8 minutes to remove the storage water, then 100 kg of the mixture of wrought ion exchange resins are introduced. in the 225l container. Then added 62.5 kg of the epoxy resin MN 201T and 37.5 kg of hardener D6 M5 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.
  • a mixture of ion exchange resins in the form of beads is conditioned, identical to that of Example 1, but using: - an epoxy resin from Ciba Geigy referenced LMB 4203, - a Ciba Geigy hardener referenced LMB 4278, - a thixotropic agent also from Ciba Geigy referenced LMB 4212.
  • the thixotropic agent is added to the hardener and the amounts of resin, hardener and thixotropic agent are respectively 90, 60 and 10 parts by weight.
  • the weight ratio, ion exchange resins / is equal to 1.
  • 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 process of the invention makes it possible to obtain: - a gain of 9% on the density of the finished product, - a gain of 18% on the maximum temperature reached during polymerization, - a gain of 320% on the intensity necessary to carry out the agitation, and - a gain of 100% on the pumping time of the water.
  • the method of the invention thus allows many advantages to be obtained compared to the method of the prior art.

Landscapes

  • 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)
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 true EP0318367A1 (de) 1989-05-31
EP0318367B1 EP0318367B1 (de) 1992-07-08

Family

ID=9357058

Family Applications (1)

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)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2678761A1 (fr) * 1991-07-03 1993-01-08 Commissariat Energie Atomique Bloc contenant des resines echangeuses d'ions contaminees et son procede de preparation.
FR2977894A1 (fr) * 2011-07-11 2013-01-18 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
WO2015049521A1 (en) * 2013-10-02 2015-04-09 National Nuclear Laboratory Limited Encapsulation of waste materials

Families Citing this family (6)

* 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
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2471030A1 (fr) * 1979-11-29 1981-06-12 Tokyo Shibaura Electric Co Installation de fabrication de corps solidifies a partir de dechets radioactifs
FR2544909A1 (fr) * 1983-04-21 1984-10-26 Commissariat Energie Atomique Procede de conditionnement de dechets contamines en milieu acide, notamment de materiaux echangeurs de cations
EP0192543A1 (de) * 1985-02-14 1986-08-27 Commissariat A L'energie Atomique Verfahren zum Konditionieren radioaktiven oder giftigen Abfalls in ein Epoxydharz und polymerisierbare Mischung mit zwei Bestandteilen zur Verwendung in diesem Verfahren

Family Cites Families (5)

* 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
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2471030A1 (fr) * 1979-11-29 1981-06-12 Tokyo Shibaura Electric Co Installation de fabrication de corps solidifies a partir de dechets radioactifs
FR2544909A1 (fr) * 1983-04-21 1984-10-26 Commissariat Energie Atomique Procede de conditionnement de dechets contamines en milieu acide, notamment de materiaux echangeurs de cations
EP0192543A1 (de) * 1985-02-14 1986-08-27 Commissariat A L'energie Atomique Verfahren zum Konditionieren radioaktiven oder giftigen Abfalls in ein Epoxydharz und polymerisierbare Mischung mit zwei Bestandteilen zur Verwendung in diesem Verfahren

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2678761A1 (fr) * 1991-07-03 1993-01-08 Commissariat Energie Atomique Bloc contenant des resines echangeuses d'ions contaminees et son procede de preparation.
EP0522931A1 (de) * 1991-07-03 1993-01-13 Commissariat A L'energie Atomique Block kontaminierte Ionenaustauschharze enthaltend und Herstellung davon
FR2977894A1 (fr) * 2011-07-11 2013-01-18 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
WO2015049521A1 (en) * 2013-10-02 2015-04-09 National Nuclear Laboratory Limited Encapsulation of waste materials

Also Published As

Publication number Publication date
ES2033454T3 (es) 1993-03-16
JPH01156699A (ja) 1989-06-20
US4927564A (en) 1990-05-22
DE3872674D1 (de) 1992-08-13
FR2623655B1 (fr) 1990-03-02
JP2634212B2 (ja) 1997-07-23
FR2623655A1 (fr) 1989-05-26
EP0318367B1 (de) 1992-07-08
DE3872674T2 (de) 1993-01-21
CA1331225C (en) 1994-08-02

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