EP0703586B1 - Bloc de conditionnement de déchets en poudre et procédé de fabrication d'un tel bloc - Google Patents
Bloc de conditionnement de déchets en poudre et procédé de fabrication d'un tel bloc Download PDFInfo
- Publication number
- EP0703586B1 EP0703586B1 EP19950402107 EP95402107A EP0703586B1 EP 0703586 B1 EP0703586 B1 EP 0703586B1 EP 19950402107 EP19950402107 EP 19950402107 EP 95402107 A EP95402107 A EP 95402107A EP 0703586 B1 EP0703586 B1 EP 0703586B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cement
- waste
- block
- polymer
- water
- 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
Links
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
-
- 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
- G21F9/34—Disposal of solid waste
Definitions
- the subject of the invention is a block of packaging of powdered waste for disposal storage as well as a method of manufacturing such block.
- thermosetting polymer and hardened cement More specifically, it concerns the packaging of waste in a composite matrix of thermosetting polymer and hardened cement. She applies to the packaging of waste from different types, such as radioactive waste from industry nuclear, chemical industry waste and more usually all the waste that needs to be stored in a leach-resistant matrix.
- thermosetting polymers there are currently several radioactive waste conditioning processes using matrices such as cements, bitumens, thermosetting polymers and more recently composite matrices comprising both thermosetting polymers and cements.
- document EP-A-0 274 927 describes the packaging of waste in a composite matrix made of hardened epoxy resin and cement.
- this conditioning we first mix with dry the waste and the cement then at the temperature ambient, this mixture is added to an emulsion formed by epoxy resin, cement mixing water and hardener. This produces a packaging block containing 35 to 45% by weight of waste, 20 to 40% by weight of epoxy resin and 25 to 35% by weight of cement with its hydration water.
- Document FR-A-2 290 745 illustrates a process for coating materials with cement organic ion exchange, whereby to cement before it solidifies a substance such than a polymeric material to block penetration of water in the solidified block and prevent grains ion exchange material reabsorb water after the setting of the cement.
- 0.1 to 20 are used parts by weight of the substance per 100 parts by weight of cement.
- the present invention has precisely for object a packaging block for powdered waste, which may contain a higher proportion of waste, while ensuring effective containment and more on this waste.
- the mineral part made up of cement and its water of hydration constitutes the rigid skeleton of the block while the thermosetting polymer that creates a gangue around of waste powder, has an elastic behavior.
- the amount of waste conditioned may be larger and reach 55% in weight.
- Powdery waste can be constituted in particular by ashes incineration of combustible radioactive waste such as that low and intermediate level waste contaminated with ⁇ emitters or ⁇ - ⁇ emitters.
- These ashes consist essentially of a mixture metal oxides such as silica, iron, alumina, etc.
- Thermosetting polymers from composite matrix can be of different types. AT As examples of such polymers, mention may be made of unsaturated polyesters, epoxy resins, etc. Of preferably, epoxy resins are used.
- the cements used in the block can be of various types. We can use for example pozzolanic cements. Preferably, a cement with low heat of hydration such as CLK, CLC cements, etc.
- step b introducing late (step b) the water necessary for hydration cement allows the waste to be well coated with powder in the thermosetting polymer and avoid put in contact with water.
- the presence of water is not favorable for good powder coating in the polymer because water forms a thin layer on the whole waste, which is harmful to obtain the adhesion of the polymer to the powder.
- the waste may exhibit a hydrophilic affinity harmful to good hydration of the cement.
- step a) of the process of the invention partial hardening of the polymer is carried out. This is preferably carried out at a temperature above room temperature but below 100 ° C. This temperature is chosen according to the polymer used, the reaction kinetics of the polymer, rheological properties of the global system and surface tensions.
- step b) the introduction of water into the mixture makes it possible to cool the medium before add the cement to form the final block.
- the amount of water added is chosen from appropriate way to control the hydration of the cement and limit the water / cement ratio by promoting this makes the quality of the concrete thus obtained. Indeed, when this ratio increases, it promotes hydration cement that gets better but puts quality at a disadvantage of the structure of the concrete thus obtained by creating larger pores.
- the amounts of water and added cement are such that the water / cement ratio is 0.4 to 0.6.
- a ratio is used about 0.5, which corresponds to an energy maximum cement hydration.
- hydration of the cement leads to a increase in the temperature of the mixture, which causes post-curing of the thermosetting polymer and improves its physico-chemical properties by increasing its cross-linking rate.
- the temperatures used in the different stages therefore play a very important role.
- step a the increase temperature due to partial hardening of the polymer leads to an increase in wetting power polymer for powdered waste, while the absence of water improves the adhesion of the polymer to the powdered waste.
- Plastic behavior of polymer is preferred to viscous behavior for coat the grains with waste powder in the form of marbles.
- the mixing phase optimizes, first time, the wetting of the waste powder by the polymer and hardener in the absence of water, and allows to control the release of crosslinking energy in order to obtain a polymerized three-dimensional network which forms an envelope on the waste powder grains.
- Steps a), b), and c) can be take place in a mixing reactor, so that the amount of energy released by polymerization is not not produced in the final storage barrel.
- step a) in performing step a) at a temperature above ambient, enthalpy resulting from polymerization in the waste package is lower.
- thermosetting polymer They have better resistance to leaching due to grain encapsulation waste powder in the thermosetting polymer and the ability to use the right amount of water necessary to hydrate the cement, which avoids to include in the block water not bound to the cement, likely to be rejected later on block storage.
- the crosslinking rate of the polymer is high, which makes it more waterproof; this is due in particular to the fact of hardening the cement after curing of the polymer.
- thermosetting polymer an epoxy resin and a hardener consisting of a diamine (the diamino-diphenylmethane)
- the cement used is a ORIGNY CLC 45 cement of the marine type.
- incineration ash having the following composition is conditioned: CaO 28% by weight SiO 2 30 % " CuO 7.8% " Al 2 O 3 9.4% " TiO 3.1% " MgO 2.8% " Fe 2 O 3 0.7% " CO 2 17.4% " Cl 2.3% " SO 3 1.3% "
- the rate progress of the polymerization is of the order of 92%.
- the hydration of the cement causes the increase the temperature of the mixture in the barrel, which leads to annealing of the polymer and increases the rate of crosslinking of the order of 2.5%.
- Compressive strength of blocks obtained is 50 to 60 MPa.
- the increase in temperature due to the hydration of the cement causes the annealing of the polymer and increases the crosslinking rate by around 8%.
- the compressive strength of the block obtained is 45 to 55 MPa
- incineration ash having the following composition is coated: CaO 41.1 by weight SiO 2 4.3 " CuO 0.1 " Al 2 O 3 28.3 " TiO 6.7 " MgO 4.0 " Fe 2 O 3 1.4 " CO 2 10.6 “ Cl 2.3 " SO 3 1.2 "
- the degree progress of the polymerization is of the order of 91%.
- the increase in temperature due to the hydration of the cement causes the annealing of the polymer and increases the crosslinking rate by around 3%.
- the compressive strength of the block obtained is from 50 to 65 MPa.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Description
- 45 à 55 % de déchet,
- 18 à 36 % de polymère thermodurcissable, et
- 14 à 32 % de ciment.
- 45 à 55 % de déchet,
- 18 à 36 % de polymère thermodurcissable, et
- 14 à 32 % de ciment.
CaO | 28 % en poids |
SiO2 | 30 % " |
CuO | 7,8 % " |
Al2O3 | 9,4 % " |
TiO | 3,1 % " |
MgO | 2,8 % " |
Fe2O3 | 0,7 % " |
CO2 | 17,4 % " |
Cl | 2,3 % " |
SO3 | 1,3 % " |
CaO | 41,1 en poids |
SiO2 | 4,3 " |
CuO | 0,1 " |
Al2O3 | 28,3 " |
TiO | 6,7 " |
MgO | 4,0 " |
Fe2O3 | 1,4 " |
CO2 | 10,6 " |
Cl | 2,3 " |
SO3 | 1,2 " |
Claims (8)
- Bloc de conditionnement d'un déchet en poudre dans une matrice composite de polymère thermodurcissable et de ciment durcis, dans lequel la poudre de déchet est enrobée dans le polymère thermodurcissable, la poudre enrobée est dispersée dans le ciment, et le bloc comprend en poids :45 à 55 % de déchet,18 à 36 % de polymère thermodurcissable, et14 à 32 % de ciment.
- Bloc selon la revendication 1, caractérisé en ce que le polymère thermodurcissable est une résine époxyde.
- Bloc selon l'une quelconque des revendications 1 et 2, caractérisé en ce que le ciment est un ciment pouzzolanique.
- Bloc selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le déchet en poudre est constitué par des cendres d'incinération de déchets radioactifs combustibles.
- Procédé de fabrication d'un bloc de conditionnement selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il comprend les étapes suivantes :a) mélanger la poudre de déchet à un polymère thermodurcissable à l'état liquide, y ajouter un durcisseur et laisser durcir en partie le polymère,b) ajouter de l'eau au mélange de poudre de déchet et de polymère partiellement durci, et refroidir à une température allant de 25°C à 40°C,c ajouter du ciment au produit de l'étape b) et homogénéiser le mélange, etd) laisser durcir le ciment.
- Procédé selon la revendication 5, caractérisé en ce que, dans l'étape a), on réalise le durcissement partiel du polymère à une température supérieure à la température ambiante, mais inférieure à 100°C.
- Procédé selon l'une quelconque des revendications 5 et 6, caractérisé en ce que le rapport pondéral polymère thermodurcissable/déchet en poudre est de 0,35 à 0,75.
- Procédé selon l'une quelconque des revendications 5 à 7, caractérisé en ce que les quantités d'eau et de ciment ajoutées sont telles que le rapport eau/ciment soit de 0,4 à 0,6.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9411249 | 1994-09-21 | ||
FR9411249A FR2724757B1 (fr) | 1994-09-21 | 1994-09-21 | Bloc de conditionnement de dechets en poudre et procede de fabrication d'un tel bloc |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0703586A1 EP0703586A1 (fr) | 1996-03-27 |
EP0703586B1 true EP0703586B1 (fr) | 1999-01-13 |
Family
ID=9467130
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19950402107 Expired - Lifetime EP0703586B1 (fr) | 1994-09-21 | 1995-09-19 | Bloc de conditionnement de déchets en poudre et procédé de fabrication d'un tel bloc |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0703586B1 (fr) |
DE (1) | DE69507230T2 (fr) |
ES (1) | ES2129178T3 (fr) |
FR (1) | FR2724757B1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2549195A1 (de) * | 1974-11-05 | 1976-05-06 | Asea Atom Ab | Verfahren, um verbrauchte, kornfoermige, organische ionenaustauschmasse in zement einzubetten |
GB2046499A (en) * | 1979-04-06 | 1980-11-12 | Astor Chemical Ltd | Encapsulation of radioactive waste |
GB2107917A (en) * | 1981-10-20 | 1983-05-05 | Chapman Brian Cope | Immobilisation of hazardous waste |
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 |
-
1994
- 1994-09-21 FR FR9411249A patent/FR2724757B1/fr not_active Expired - Fee Related
-
1995
- 1995-09-19 EP EP19950402107 patent/EP0703586B1/fr not_active Expired - Lifetime
- 1995-09-19 ES ES95402107T patent/ES2129178T3/es not_active Expired - Lifetime
- 1995-09-19 DE DE1995607230 patent/DE69507230T2/de not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
FR2724757A1 (fr) | 1996-03-22 |
EP0703586A1 (fr) | 1996-03-27 |
FR2724757B1 (fr) | 1996-12-06 |
DE69507230T2 (de) | 1999-07-08 |
ES2129178T3 (es) | 1999-06-01 |
DE69507230D1 (de) | 1999-02-25 |
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