EP0274927B1 - Block mit Abfällen zur Endlagerung derselben und Verfahren zur Herstellung eines solchen Blocks - Google Patents
Block mit Abfällen zur Endlagerung derselben und Verfahren zur Herstellung eines solchen Blocks Download PDFInfo
- Publication number
- EP0274927B1 EP0274927B1 EP87402698A EP87402698A EP0274927B1 EP 0274927 B1 EP0274927 B1 EP 0274927B1 EP 87402698 A EP87402698 A EP 87402698A EP 87402698 A EP87402698 A EP 87402698A EP 0274927 B1 EP0274927 B1 EP 0274927B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- waste
- cement
- stage
- resin
- weight
- 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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Images
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
- G21F9/302—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
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/16—Processing by fixation in stable solid media
- G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
- G21F9/165—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
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/16—Processing by fixation in stable solid media
- G21F9/167—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
- G21F9/307—Processing by fixation in stable solid media in polymeric matrix, e.g. resins, tars
Definitions
- the subject of the present invention is a block containing waste as well as a process for producing such a block which can be used in particular in the field of storage of low and medium activity radioactive waste.
- Waste from the nuclear industry can take three main forms. It can firstly be wet waste such as liquid effluent co-precipitation sludge whose water content is of the order of 20 to 40%.
- a second category of waste is that of pulverulent dry waste constituted for example by the incineration ashes of combustible materials such as cellulose, polyvinyl chloride, rubber, neoprene, polyethylene, etc.
- the third category is that of solid waste called "technological waste". This designation includes the waste mentioned above as well as non-combustible waste such as glass and metals.
- Cement coating is a method whose implementation is simple and inexpensive. However, the quality of containment is unsatisfactory when the mix contains radioelements such as cesium or strontium. The tests for resistance to leaching by industrial water show that the leaching speed of these radioelements presents high values.
- document DE-A-2 717 656 describes a process for coating waste in cement, according to which the waste is mixed with cement and water and an organic or inorganic substance is used to produce the waste. make the mixture hydrophobic, for example 3% by weight of latex.
- Bitumen coating is mainly applied to waste such as sludge and concentrates of liquid effluents. This process makes it possible to obtain a stable product, but the mechanical strength of the coated materials is unsatisfactory.
- the product may be subject to the emission of radiolysis gas, which may cause swelling of the mix.
- the coating in polymers consists in coating the waste in resins, for example polyester or epoxy thermosetting resins.
- the physical and mechanical properties of the product obtained as well as the containment are better than with the methods of coating in cement or bitumen.
- problems of compatibility between the resin matrix and the waste may be encountered, in particular in the case where it is desired to coat waste with a high water content. In particular, if radiolysis gases are released, this leads to the production of pores during polymerization.
- the object of the present invention is to remedy these drawbacks by proposing a block containing radioactive waste as well as a method for preparing this block applicable to all types of waste and which makes it possible to obtain effective and safe containment of the latter. .
- the waste is coated in a composite matrix consisting of epoxy resin and hardened cement.
- the proportion of waste is between 35 and 45% by weight, the proportion of cement between 25 and 35% by weight and the proportion of resin between 20 and 40% by weight.
- waste it can consist of all types of waste and in particular that mentioned above, namely wet waste, pulverulent waste and non-combustible solids.
- An additional step (5) can be provided, carried out after step (2) and before step (3), consisting in transforming the product obtained in step (2) into granules.
- an additional step (6) can also be carried out after step (5) and before step (3), consisting in drying the granules.
- an additional step can be carried out consisting in subjecting the product obtained to a degassing treatment and / or another step consisting in subjecting the product obtained to a vibration.
- this product was subjected to granulation by pressing through a grid and the granules obtained were then immersed in a mixture consisting of an epoxy resin and its hardener.
- the mixture comprised 100 parts by weight of resin per 60 parts by weight of hardener.
- the quantities of granules and resin / hardener mixture are calculated so that the apparent volume of the granules is substantially equal to the volume of the resin and hardener mixture.
- the hardening time of the resin is 48 hours and the setting time of the cement is 28 days. It therefore takes 28 days for the block obtained to be perfectly hardened, but it can be handled as soon as the resin is polymerized, that is to say after 48 hours, because the polymerization of the resin constitutes a first hardening.
- the probability of cracking of the cement granules is reduced thanks to the high adhesiveness of the resin which constitutes the second barrier.
- the radiolytic degradation of the resin by the radioelements is reduced because the ⁇ particles are absorbed, in large part, in the granules.
- Example 1 the granules were introduced into the mixture of resin and hardener practically immediately after their production, that is to say the state still wet. Optionally, they can be subjected to hot drying in order to harden them before pouring them into the mixture of resin and hardener.
- incinerator ash from the incineration of combustible waste contaminated with ⁇ emitters or ⁇ ⁇ emitters.
- These ashes consist essentially of a mixture of metal oxides (silica, iron oxide, alumina, etc.).
- the ash treated in this example had an activity ⁇ of the order of 50 Ci per tonne and their weight composition was as follows: - SiO2 32 to 40% - Al2O3 18 to 19% - Fe2O3 4% - TiO2 1 to 3% - CaO 19% - MgO 3.7% - Na2O + K2O 5% - SO3 1 to 2% - Cl ⁇ 2.4 to 5.1%
- Example 2 The same waste as in Example 2 was first mixed with dry cement in the proportion of 40 parts of ash for approximately 20 parts of cement.
- Example 2 In parallel, a mixture containing water, epoxy resin and a hardener containing 7 to 10 parts by weight of water was prepared for 30 parts by weight of the resin / hardener mixture. In the latter, the proportion by weight of hardener is of the order of 0.6.
- the two products are mixed and vigorously stirred in order to obtain a soft dough similar to that which was obtained in Example 2.
- it is possible to brew in a mixer equipped with a turbine. homogenization and, if desired, carry out the mixing under vacuum or under reduced pressure in order to degas and / or subject this product to vibration. In both cases, the hardening of the final block is obtained in 48 hours.
- the process which is the subject of the invention has particularly advantageous advantages since it applies to all types of waste and a block is obtained which has good mechanical properties and resistance to leaching and which ensures efficient confinement and sustainable waste.
- the coating of certain qualities of ash proves difficult in epoxy resins.
- gases such as hydrogen or ammonia.
- the quantities of gas collected show that it is a partial neutralization reaction on the amine constituting the hardener. This results in a swelling phenomenon and a polymerization, therefore a slowed down curing, or even inhibited.
- the use of the cement / resin composite according to the invention overcomes these drawbacks. Indeed, the alkalinity of the cement allows a quick neutralization of the acidity of the ashes and suppresses the consumption reaction of the hardener.
- curves 1 and 2 present a peak at values of the order of 170 ° C. while curve 3 presents, at after 10 hours, a peak which is only around 90 ° C.
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Refuse Collection And Transfer (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
Claims (7)
- Block mit Abfällen zur Endlagerung derselben, in dem die Abfälle von einer Verbundmatrix umhüllt sind, die aus Epoxydharz und gehärtetem Zement besteht, dadurch gekennzeichnet, daß der Anteil der Abfälle zwischen 35 und 45 Gewichtsprozent beträgt, der Anteil an Zement zwischen 25 und 35 Gewichtsprozent und der Anteil an Harz zwischen 20 und 40 Gewichtsprozent liegt.
- Block nach Anspruch 1, dadurch gekennzeichnet, daß die Abfälle zu der Gruppe gehören, die gebildet wird von den feuchten Abfällen, den feinpulvrigen Abfällen und den unbrennbaren, festen Abfällen.
- Verfahren zum Herstellen eines Blocks nach Anspruch 1, dadurch gekennzeichnet, daß es folgende Verfahrensschritte umfaßt, die darin bestehen:(1) die Abfälle mit wenigstens einem Zement zu mischen,(2) zu der im Schritt (1) erhaltenen Mischung Wasser in hinreichender Menge hinzuzufügen, um eine Hydrierung des Zements oder der Zemente zu erreichen,(3) die in Schritt (2) erhaltene Mischung mit dem Epoxydharz zu mischen, und(4) den Zement oder die Zemente und den Harz aushärten lassen,wobei die Mengen an Abfällen, an verwendetem Zement und Harz derart sind, daß die Abfälle zwischen 35 und 45 Gewichtsprozent der von den Abfällen, dem Zement und dem Harz gebildeten Anordnung darstellen, der Zement zwischen 25 und 35 Gewichtsprozent dieser Anordnung und der Harz zwischen 20 und 40 Gewichtsprozent dieser Anordnung darstellen.
- Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß es einen zusätzlichen Verfahrensschritt (5) umfaßt, der nach dem Schritt (2) und vor dem Schritt (3) durchgeführt wird und darin besteht, das in Schritt (2) erhaltene Produkt in Granulat umzuwandeln.
- Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß es einen zusätzlichen Verfahrensschritt (6) umfaßt, der nach dem Schritt (5) und vor dem Schritt (3) durchgeführt wird und darin besteht, das Granulat zu trocknen.
- Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß es einen zusätzlichen Verfahrensschritt (7) umfaßt, der unmittelbar vor dem Schritt (4) durchgeführt wird und darin besteht, das erhaltene Produkt einer Entgasungsbehandlung zu unterwerfen.
- Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß es einen zusätzlichen Verfahrensschritt (8) umfaßt, der unmittelbar vor dem Schritt (4) durchgeführt wird und darin besteht, das erhaltene Produkt einer Vibration zu unterwerfen.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8617081A FR2607957A1 (fr) | 1986-12-05 | 1986-12-05 | Bloc contenant des dechets en vue de leur stockage et procede de realisation d'un tel bloc |
FR8617081 | 1986-12-05 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0274927A1 EP0274927A1 (de) | 1988-07-20 |
EP0274927B1 true EP0274927B1 (de) | 1992-07-15 |
Family
ID=9341629
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87402698A Expired - Lifetime EP0274927B1 (de) | 1986-12-05 | 1987-11-30 | Block mit Abfällen zur Endlagerung derselben und Verfahren zur Herstellung eines solchen Blocks |
Country Status (7)
Country | Link |
---|---|
US (1) | US4839102A (de) |
EP (1) | EP0274927B1 (de) |
JP (1) | JPS63150696A (de) |
CA (1) | CA1282503C (de) |
DE (1) | DE3780436T2 (de) |
ES (1) | ES2033908T3 (de) |
FR (1) | FR2607957A1 (de) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2623655B1 (fr) * | 1987-11-23 | 1990-03-02 | Commissariat Energie Atomique | Procede de conditionnement de dechets radioactifs ou toxiques dans des resines thermodurcissables |
FR2678761B1 (fr) * | 1991-07-03 | 1994-07-01 | Commissariat Energie Atomique | Bloc contenant des resines echangeuses d'ions contaminees et son procede de preparation. |
US5414197A (en) * | 1994-06-03 | 1995-05-09 | The United States Of America As Represented By The Secretary Of The Army | Method of containing and isolating toxic or hazardous wastes |
FR2724757B1 (fr) * | 1994-09-21 | 1996-12-06 | Commissariat Energie Atomique | Bloc de conditionnement de dechets en poudre et procede de fabrication d'un tel bloc |
US5595561A (en) * | 1995-08-29 | 1997-01-21 | The United States Of America As Represented By The Secretary Of The Army | Low-temperature method for containing thermally degradable hazardous wastes |
DE19832668A1 (de) * | 1998-07-21 | 2000-01-27 | Hilti Ag | Organisch-anorganischer Mörtel |
US6743963B2 (en) * | 1998-12-21 | 2004-06-01 | Perma-Fix Environmental Services, Inc. | Methods for the prevention of radon emissions |
US6537350B2 (en) * | 2001-02-13 | 2003-03-25 | The Regents Of The University Of California | HEPA filter encapsulation |
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 |
GB0215341D0 (en) * | 2002-07-03 | 2002-08-14 | British Nuclear Fuels Plc | Storage of hazardous materials |
RU2613161C1 (ru) * | 2015-12-29 | 2017-03-15 | Федеральное государственное бюджетное учреждение науки Ордена Ленина и Ордена Октябрьской революции Институт геохимии и аналитической химии им. В.И. Вернадского Российской академии наук (ГЕОХИ РАН) | Способ остекловывания радиоактивного шлака |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB159683A (en) * | 1919-12-17 | 1921-03-10 | James Robinson | Improvements in or relating to wireless reception apparatus |
NL235423A (de) * | 1959-01-19 | |||
FR1246848A (fr) * | 1959-10-13 | 1960-11-25 | Commissariat Energie Atomique | Procédé d'élimination de déchets radioactifs et produits obtenus suivant ce procédé |
US4119560A (en) * | 1977-03-28 | 1978-10-10 | United Technologies Corporation | Method of treating radioactive waste |
DE2717656A1 (de) * | 1977-04-21 | 1978-10-26 | Nukem Gmbh | Verfahren zur herstellung auslaugfester und salzlaugebestaendiger bloecke aus zement und radioaktiven abfaellen |
DE2741661C2 (de) * | 1977-09-16 | 1986-12-11 | Gesellschaft für Strahlen- und Umweltforschung mbH, 8000 München | Verfahren zur Umkleidung von Abfallfässern mit einer auslaugsicheren, geschlossenen Hülle |
US4174293A (en) * | 1977-10-12 | 1979-11-13 | The United States Of America As Represented By The United States Department Of Energy | Process for disposal of aqueous solutions containing radioactive isotopes |
GB1603729A (en) * | 1978-05-23 | 1981-11-25 | B & R Eng Ltd | Apparatus and method for treating waste material |
JPS55500406A (de) * | 1978-06-08 | 1980-07-10 | ||
DE2945007A1 (de) * | 1979-11-08 | 1981-05-21 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Verfahren zur endlagerreifen, umweltfreundlichen verfestigung von radioaktiven ionenaustauscherharzen |
GB2107917A (en) * | 1981-10-20 | 1983-05-05 | Chapman Brian Cope | Immobilisation of hazardous waste |
JPS58213300A (ja) * | 1982-06-04 | 1983-12-12 | 株式会社日立製作所 | 放射性廃棄物の処理方法 |
CH654436A5 (fr) * | 1983-04-29 | 1986-02-14 | Syncrete Sa | Procede d'enrobage de dechets radioactifs. |
ES2001160A4 (es) * | 1985-10-04 | 1988-05-01 | Somafer Sa | Tratamiento de liquido reactivo |
-
1986
- 1986-12-05 FR FR8617081A patent/FR2607957A1/fr active Pending
-
1987
- 1987-11-30 ES ES198787402698T patent/ES2033908T3/es not_active Expired - Lifetime
- 1987-11-30 US US07/126,855 patent/US4839102A/en not_active Expired - Fee Related
- 1987-11-30 EP EP87402698A patent/EP0274927B1/de not_active Expired - Lifetime
- 1987-11-30 DE DE8787402698T patent/DE3780436T2/de not_active Expired - Fee Related
- 1987-12-01 CA CA000553225A patent/CA1282503C/en not_active Expired - Lifetime
- 1987-12-02 JP JP62305499A patent/JPS63150696A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
ES2033908T3 (es) | 1993-04-01 |
DE3780436D1 (de) | 1992-08-20 |
DE3780436T2 (de) | 1993-01-21 |
CA1282503C (en) | 1991-04-02 |
US4839102A (en) | 1989-06-13 |
JPS63150696A (ja) | 1988-06-23 |
FR2607957A1 (fr) | 1988-06-10 |
EP0274927A1 (de) | 1988-07-20 |
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