EP0522931B1 - Block kontaminierte Ionenaustauschharze enthaltend und Herstellung davon - Google Patents

Block kontaminierte Ionenaustauschharze enthaltend und Herstellung davon Download PDF

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Publication number
EP0522931B1
EP0522931B1 EP19920401879 EP92401879A EP0522931B1 EP 0522931 B1 EP0522931 B1 EP 0522931B1 EP 19920401879 EP19920401879 EP 19920401879 EP 92401879 A EP92401879 A EP 92401879A EP 0522931 B1 EP0522931 B1 EP 0522931B1
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EP
European Patent Office
Prior art keywords
exchange resins
cement
resins
epoxy resin
ion
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
EP19920401879
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English (en)
French (fr)
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EP0522931A1 (de
Inventor
Claude Kertesz
Patrice Da Silva
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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    • 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
    • G21F9/28—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 block containing ion exchange resins contaminated, for example by toxic or radioactive elements, as well as a process for preparing such a block. It is particularly applicable in the field of storage of ion exchange resins contaminated by radioactive elements of low and medium activity.
  • Ion exchange resins used to purify water in nuclear installations undergo degradation phenomena after a certain time and, consequently, lose their effectiveness. It is then a question of storing these used ion exchange resins which, during their use, have fixed various radioelements giving them a certain radioactivity.
  • thermosetting resins such as those described in documents FR-A- 2 251 081, FR-A- 2 361 724 and EP-A- 0 127 490 are satisfactory because they allow to ensure good retention of radioactivity, but they nevertheless have certain drawbacks.
  • EP-A-0 127 490 also makes it possible to incorporate cationic resins which still have active sites into an epoxy resin, but it has the disadvantage of requiring the use of particular amine hardeners which are relatively expensive products. .
  • thermosetting resins are sensitive to the initial temperature which accelerates the polymerization and / or leads to a release of heat detrimental to the quality of the block formed.
  • radioactive waste consists of sludge chemical coprecipitation which may contain from 20 to 40% of water, dry pulverulent waste such as the incineration ashes of combustible materials or technological, non-combustible waste such as glass and metals.
  • Document EP-A-0 124 825 also describes the coating of radioactive waste in a composite matrix obtained from unsaturated polyester, monomers, Portland cement and pozzolans.
  • the present invention specifically relates to a block containing ion exchange resins contaminated for storage, which overcomes the drawbacks mentioned above of the known methods.
  • the block containing ion exchange resins contaminated for storage is characterized in that the ion exchange resins are incorporated in a composite matrix consisting of a hardened hydrophilic epoxy resin and a cement. hardened chosen from Clinker's slag cements and slag and ash cements.
  • the choice of a hydrophilic epoxy resin and of a cement with low heat of hydration constituted by a cement with slag from Clinker (CLK) and / or a cement with slag and with fly ash ( CLC) provides a matrix compatible with ion exchange resins, even when these are saturated with water and contain, for example, 50 to 55% by weight of water, and / or contain active sites usually requiring pretreatment.
  • this matrix makes it possible to obtain a high coating coefficient and a block having very interesting physical and mechanical properties, in particular better resistance to compression.
  • CLC and CLK cements have very different compositions from those of Portland cements and aluminous cements.
  • CLK and CLC cements have lower hydration heats than those of Portland and aluminous cements and a slower hydration kinetics.
  • the temperature can reach 120 ° C at the core, which causes the distillation of the water included in the exchange resins d 'ions and a degradation of the properties of the barrel.
  • the proportions by weight of hardened cement and epoxy resin used in the constitution of the matrix are chosen so as to obtain the desired characteristics of radioelement retention, resistance to leaching and mechanical resistance for storage. of the block with a high degree of safety.
  • ion exchange resins With this matrix, relatively large amounts of ion exchange resins can be included in the block; it can thus contain up to 45% by weight of contaminated ion exchange resins, saturated with water, whereas in the in the case of CLK cement alone, only 15 to 20% by weight of ion exchange resins could be coated.
  • ion exchange resins can consist of cationic exchange resins, anionic resins or mixtures of these resins, in the form of grains or particles obtained by grinding.
  • organic ion exchange resins such as polystyrene resins crosslinked with divinyl benzene which contain, for example, sulfonic groups or hydroxyl groups.
  • a hydrophilic epoxy resin is used, compatible both with the cement used and with the ion exchange resin to be conditioned.
  • hydrophilic epoxy resins By way of example of such hydrophilic epoxy resins, mention may be made of the bis-phenol-A diglycidyl ether and the bis-phenol-F diglycidyl ether hardened by reaction with an amino hardener.
  • the diglycidyl ether of bis phenol A corresponds to the formula:
  • the bis-phenol F diglycidyl ether corresponds to the formula:
  • the use of a hydrophilic epoxy resin is advantageous because it facilitates obtaining a homogeneous mixture with the cement, in the presence of water.
  • the invention also relates to a process for the preparation of the block containing the contaminated ion exchange resins, described above.
  • the contaminated ion exchange resins are saturated with water, which is carried out by immersing these resins in water for a sufficient time, for example for 24 hours. After this operation, the ion exchange resins are drained until disappearance of the water flow so as to ensure that the ion exchange resins contain only their saturation water which generally represents approximately 50 to 55% by weight of the saturated ion exchange resins, but can go in certain case up to 65% by weight.
  • the water necessary for the hydration of the cement is then added to the resins by carrying out this operation with stirring.
  • the amount of water of hydration required for curing Clinker's slag cements or slag and fly ash cements depends on the amount of cement that will be introduced into the block. It is generally such that the weight ratio of hydration water / cement is from 0.25 to 0.35.
  • the cement After introduction of the water, the cement is added with stirring and this stirring is continued until a fluid paste is obtained, then the epoxy resin in the liquid state and its amine hardener are added, continuing the agitation.
  • the operations of adding water, cement and epoxy resin are carried out in a mixer.
  • the mixture After adding the epoxy resin and its hardener, the mixture can be emulsified by rotation at high speed, left to stand and poured into a mold having the dimensions of the block to be manufactured.
  • the block is allowed to harden in the mold, which can be obtained relatively quickly, for example in 12 hours.
  • the choice of the amine hardener is also important, because by choosing an appropriate amine hardener, the epoxy resin is allowed to harden in the presence of large amounts of water.
  • amine hardeners containing a combination of aromatic and aliphatic amines it is possible to use amine hardeners containing a combination of aromatic and aliphatic amines, and by varying the amounts of these different amines, an optimized hardener can be obtained, suitable for the preparation of an epoxy composite matrix. cement suitable for coating ion exchange resins saturated with water to be conditioned.
  • the proportion of amine hardener is such that the hardener / epoxy resin weight ratio is preferably from 0.5 to 0.6.
  • the contaminated water exchange resins are saturated with water by swelling them in water for 24 h and then subjected to a spin. 400 g of drained anionic resins are then weighed and the 78 g of water added to them, that is to say the amount sufficient to hydrate the 222 g of CLK 45 cement.
  • the resins are mixed with water, then the CLK 45 cement is added to the suspension and the mixture is kneaded so as to obtain a very fluid paste.
  • the epoxy resin SL MN 201 T and the hardener SL D6 M5 are added.
  • the mixture is then poured into a mold and allowed to harden for 36 hours.
  • the block obtained is also subjected to a water absorption test by immersing it for one month in water. After this period, it is found that the mass coefficient of water absorption is of the order of 1 to 3%.
  • the block obtained therefore has very satisfactory characteristics for the storage of anion exchange resins.
  • Example 2 The same contaminated anion exchange resins and the same matrix constituents are used as in Example 1, except the hardener which in this example is the product sold by Spado Lassailly under the reference SL D 2005.
  • Example 2 The same procedure is followed as in Example 1, using the same proportions for coating 400 g of anion exchange resins in the composite matrix.
  • a solid block is thus obtained having properties practically identical to those of the block obtained in Example 1, except that its external appearance is more shiny.
  • Example 2 The same procedure is followed and the same matrix is used as in Example 1 to coat 400 g of cationic ion exchange resins of the Rohm and Haas IR 120 type.
  • the block obtained also has very good properties.
  • the coating of contaminated ion exchange resins is carried out using only as coating component an epoxy resin and its hardener.
  • an epoxy-cement composite matrix makes it possible, during polymerization, to limit the core temperature of the block to a value lower than that which is obtained with an epoxy resin alone.
  • the core temperature is limited to 58-63 ° C, while in the case of an epoxy resin alone, it can reach 78 ° C for a block of 0.5 l. Also, for blocks of larger volume, the core temperature can become higher than 100 ° C with an epoxy resin alone. However, at this temperature, the water contained in the ion-exchange resins saturated with water is brought to the boil and the water vapor generated in the block is the cause of more or less significant damage.
  • the enthalpy corresponding to the setting of the binder is very substantially lower than the enthalpy of polymerization of the epoxy part.
  • the core temperature (in ° C.) of 2 blocks according to the invention is shown weighing 640 g, as a function of time (in h) during their hardening.
  • curve A corresponds to the average values of the two curves of FIG. 2
  • curve B corresponds to the average values of the two curves of FIG. 3.
  • the reduction of the peak of the polymerization exotherm is particularly sought after, because it increases the intrinsic safety of the process, in particular in the event of acceleration of the polymerization rate observed in hot weather: in this case, in Indeed, the polymerization kinetics is increased, and the temperature obtained at the core of the mix must imperatively be below the vaporization temperature of the REI water.
  • the lengthening of the hardening time is an interesting phenomenon at the industrial stage because it allows increased possibilities of intervention on the process.
  • Another important advantage of the process of the invention is that it allows the coating of anionic, cationic or mixed ion exchange resins without requiring pretreatment. Indeed, the use of a hydraulic binder which releases dissociated ions into the aqueous medium, avoids prior saturation of any active sites of cation exchange resins since the ions released by the cement are capable of achieving this saturation.

Claims (10)

  1. Block, kontaminierte Ionenaustauscherharze zum Zweck ihrer Lagerung enthaltend, dadurch gekennzeichnet, daß die Ionenaustauscherharze eingebaut sind in eine Verbundmatrix, die aus einem gehärteten hydrophilen Epoxidharz und aus einem erhärteten Zement besteht, der unter den Schlacken-Klinkerzementen und den Schlacken-Aschen-Zementen gewählt ist.
  2. Block nach Anspruch 1, dadurch gekennzeichnet, daß die Verbundmatrix
    - 35 bis 65 Gew.-% gehärtetes Epoxidharz und
    - 35 bis 65 Gew.-% erhärteten Schlacke-Klinkerzement und/oder erhärteten Schlacken-Flugaschen-Zement enthält.
  3. Block nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß er bis zu 45 Gew.-% kontaminierte Ionenaustauscherharze enthält.
  4. Block nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Ionenaustauscherharze gewählt sind unter den kationischen Harzen, den anionischen Harzen und den Mischungen von kationischen und anionischen Harzen.
  5. Block nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Epoxidharz ein Diglycid-Ether von Bisphenol-A und/oder ein Diglycid-Ether von Bisphenol-F ist, jeweils durch Härtung mit einem Aminohärter gehärtet.
  6. Verfahren zur Herstellung eines Blocks, welcher kontaminierte Ionenaustauscherharze zum Zweck ihrer Lagerung enthält, das darin besteht, die Harze in eine Verbundmatrix, bestehend aus einem gehärteten hydrophilen Epoxidharz und aus einem erhärteten Zement, einzubauen, und das dadurch gekennzeichnet ist, daß es nacheinander die folgenden Schritte umfaßt:
    1) Sättigung der kontaminierten Ionenaustauscherharze mit Wasser,
    2) Zugabe einer zusätzlichen Menge Wasser unter Rühren zu den mit Wasser gesättigten Ionenaustauscherharzen,
    3) Zugabe eines Zements, der unter den Schlacken-Klinkerzementen und den Schlacken-Aschen-Zementen gewählt ist, unter Rühren zu der in 2) erhaltenen Suspension,
    4) Zugabe von Epoxidharz und dem dazugehörigen Härter zu der in 3) erhaltenen Mischung,
    wobei die Menge des in 2) zugefügten Wassers die für die Hydratisierung des in 3) zugefügten Zements benötigte Menge ist.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die zugefügten Mengen von Epoxidharz und von Zement derart sind, daß die erhärtete Verbundmatrix
    - 35 bis 65 Gew.-% Epoxidharz und
    - 35 bis 65 Gew.-% Schlacken-Klinkerzement und/oder Schlacken-Flugaschen-Zement umfaßt.
  8. Verfahren nach einem der Ansprüche 6 und 7, dadurch gekennzeichnet, daß die Menge der Ionenaustauscherharze derart ist, daß der Block bis zu 45 Gew.-% kontaminierte Ionenaustauscherharze enthält.
  9. Verfahren nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, daß das Epoxidharz ein Diglycid-Ether von Bisphenol-A und/oder ein Diglycid-Ether von Bisphenol-F ist und daß der Härter ein Aminohärter ist.
  10. Verfahren nach einem der Ansprüche 6 bis 9, dadurch gekennzeichnet, daß die Ionenaustauscherharze unter den kationischen Harzen, den anionischen Harzen und den Mischungen von kationischen und anionischen Harzen gewählt sind.
EP19920401879 1991-07-03 1992-07-01 Block kontaminierte Ionenaustauschharze enthaltend und Herstellung davon Expired - Lifetime EP0522931B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9108309 1991-07-03
FR9108309A FR2678761B1 (fr) 1991-07-03 1991-07-03 Bloc contenant des resines echangeuses d'ions contaminees et son procede de preparation.

Publications (2)

Publication Number Publication Date
EP0522931A1 EP0522931A1 (de) 1993-01-13
EP0522931B1 true EP0522931B1 (de) 1997-04-02

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EP19920401879 Expired - Lifetime EP0522931B1 (de) 1991-07-03 1992-07-01 Block kontaminierte Ionenaustauschharze enthaltend und Herstellung davon

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EP (1) EP0522931B1 (de)
DE (1) DE69218680T2 (de)
ES (1) ES2102477T3 (de)
FR (1) FR2678761B1 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4324818C2 (de) * 1993-07-23 2002-06-27 Framatome Anp Gmbh Verfahren zum Entsorgen von Ionenaustauscherharz
KR100192126B1 (ko) * 1995-12-11 1999-06-15 김성년 플라이 애쉬와 붕소함유 방사성폐기물을 붕규산유리의 기본원료로 사용하여 방사성폐기물을 유리고화체로 만드는 방법
US6287772B1 (en) 1998-04-29 2001-09-11 Boston Probes, Inc. Methods, kits and compositions for detecting and quantitating target sequences
US6068055A (en) * 1998-06-30 2000-05-30 Halliburton Energy Services, Inc. Well sealing compositions and methods
US6279652B1 (en) 1998-09-23 2001-08-28 Halliburton Energy Services, Inc. Heat insulation compositions and methods
US6244344B1 (en) 1999-02-09 2001-06-12 Halliburton Energy Services, Inc. Methods and compositions for cementing pipe strings in well bores
US6234251B1 (en) 1999-02-22 2001-05-22 Halliburton Energy Services, Inc. Resilient well cement compositions and methods
FR2825182B1 (fr) * 2001-05-23 2004-09-10 Qualia Systeme matriciel pour l'enrobage et le stockage d'un produit dangereux, procede de preparation et utilisation notamment pour les resines echangeuses d'ions faiblement radioactives
DE102008005336A1 (de) * 2008-01-17 2009-07-30 Areva Np Gmbh Verfahren zur Konditionierung radioaktiver Ionenaustauscherharze

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CH654436A5 (fr) * 1983-04-29 1986-02-14 Syncrete Sa Procede d'enrobage de dechets radioactifs.
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
FR2623655B1 (fr) * 1987-11-23 1990-03-02 Commissariat Energie Atomique Procede de conditionnement de dechets radioactifs ou toxiques dans des resines thermodurcissables

Also Published As

Publication number Publication date
DE69218680T2 (de) 1997-10-23
ES2102477T3 (es) 1997-08-01
EP0522931A1 (de) 1993-01-13
DE69218680D1 (de) 1997-05-07
FR2678761A1 (fr) 1993-01-08
FR2678761B1 (fr) 1994-07-01

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