EP0241365A1 - Verfahren zur Herstellung von radioaktive Abfälle enthaltendem Borsilikatglas - Google Patents

Verfahren zur Herstellung von radioaktive Abfälle enthaltendem Borsilikatglas Download PDF

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Publication number
EP0241365A1
EP0241365A1 EP87400752A EP87400752A EP0241365A1 EP 0241365 A1 EP0241365 A1 EP 0241365A1 EP 87400752 A EP87400752 A EP 87400752A EP 87400752 A EP87400752 A EP 87400752A EP 0241365 A1 EP0241365 A1 EP 0241365A1
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EP
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Prior art keywords
solution
waste
matrix
calcined
glass
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EP87400752A
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English (en)
French (fr)
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EP0241365B1 (de
Inventor
Bruno Aubert
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Societe Generale pour les Techniques Nouvelles SA SGN
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Societe Generale pour les Techniques Nouvelles SA SGN
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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
    • G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
    • G21F9/305—Glass or glass 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

Definitions

  • High-level nuclear waste - such as fission products - or long-lived waste such as actinides is currently immobilized in borosilicate glasses which offer sufficient guarantees of safety for man and the environment.
  • the French Atomic Energy Commission has developed an industrial vitrification process for fission products (PF).
  • This process (known as AVM) consists in calcining the solution of the fission products, and in sending the calcinate obtained, simultaneously with a glass frit, to a melting furnace.
  • the glass frit is mainly composed of silica and boric anhydride, plus the other oxides (sodium aluminum etc.) necessary for the total formulation calcinate + frit to give a glass which can be produced by known glass techniques and fulfilling the safety conditions for storage (condition on leaching, mechanical strength, etc.).
  • the temperature should be chosen high enough to hasten digestion but without having a detrimental effect on the life of the oven.
  • the applicant instead of preparing the glass from solid constituents in the form of oxides, has developed a process in which the constituents of the glass are mixed in an aqueous medium so as to form a gelled solution.
  • obtaining a glass from a gelled solution can be done at temperatures lower than those necessary with the oxides (“oxide route”).
  • the main objective is to manufacture by the gels of glasses having the same formulation as those currently prepared by the oxide route, as the examples will show, but any borosilicate formulation acceptable for packaging waste can be prepared.
  • vitrification adjuvant it is all the constituents of the final glass other than the constituents originating from nuclear waste and except B and Si. This adjuvant therefore does not contain active nuclear elements.
  • AVM process it is included in a glass frit; in the process which is the subject of the invention, it is an aqueous solution, . final glass : This is the glass in which nuclear waste is immobilized, . soil : it is a solution of orthosilicic acid; this unstable evolves by polymerizing.
  • gelled solution or gel it is a homogeneous solution, of variable viscosity which goes from a flowing solution to a fixed mass, according to the progress of the polymerization.
  • a way is known for preparing the gels in an aqueous medium known as the sol-gel method, consisting in using a sol in water and in de-establishing it by modifying the pH, thus causing this solution to gel.
  • the literature describes the preparation of a SiO2-B2O3 glass by the sol-gel method: - addition of a Ludox solution brought to pH: 2 to an aqueous solution of aqueous ammonium tetraborate also brought to pH: 2 - mixing with stirring for 1 hour (with possible addition of ammonia to bring the medium to pH: 3.5 very favorable for gelling) if the solution obtained is free of precipitation or flocculation, it is considered to be a satisfactory gel - drying 8 hours at 100 ° C then 15 h at 175 ° C under vacuum of 0.1 mm Hg - hot pressing (450 bars-500 at 900 ° - 15 min to 5 hours) to densify and vitrify (fusion is another means).
  • boron makes gelation very difficult (in the HITACHI process described below, boron is added, moreover, after gel formation), in particular due to the high insolubility of many boron compounds and promotes recrystallization in mixed gels aluminum promotes precipitation at the expense of gelling, which is opposed to the desired result sodium, calcium and zirconium lead to the formation of crystals which later constitute fragile points which can cause local destruction.
  • the gel prepared from compounds X (OR) n in alcoholic medium can be obtained more easily because there is no problem of solubility and moreover the peptizing effect of water at high temperature is eliminated by using l 'alcohol.
  • the Applicant has developed a method for immobilizing nuclear waste, which does not have the drawbacks of the Westinghouse and Hitachi processes, and in which a borosilicate matrix is prepared in an aqueous medium, the nuclear waste is subsequently added to said matrix at any stage of its treatment, this mixture then being heat treated to obtain a borosilicate glass.
  • This process therefore has the advantages of working in an aqueous medium and of adding boron at the same time as the formation of the gelled matrix. boron therefore participating in the structure of the gelled matrix, for this so-called borosilicate.
  • the process which is the subject of the invention is characterized in that the borosilicate matrix is prepared by mixing: - a silica-based gel precursor - a concentrated aqueous solution of a boron compound - a concentrated aqueous solution of the vitrification aid.
  • a substance containing silica particles, optionally partially hydrolyzed which is either in the form of a powder which, when put in acid solution, can produce a sol, or directly in the form of a gel, will be called a gel precursor. 'a floor.
  • Gel precursors sold commercially and advantageously used in the process can be, for example, a soil such as Ludox R (from Pont de Nemours) or Aerosil R (Degussa) which is formed by hydrolysis in the gas phase of silicon tetrachloride. In an acidic environment, the Aerosil leads to a soil then to a firm gelled mass.
  • Ludox R from Pont de Nemours
  • Aerosil R Degussa
  • the Ludox is brought into solution as it is, the Aerosil on the other hand can be used either directly in the form of powder introduced into the mixture (depending on the technology used in particular for stirring) or in solution.
  • the gel precursor can consist of a mixture of gel precursor, for example in the same operation the silica will be supplied by Ludox and Aerosil.
  • the gel precursor is placed, in an acidic aqueous medium, according to the process which is the subject of the invention, so that it is transformed into a gelled solution by polymerization from the Si-OH- bonds.
  • the boron necessary to form the borosilicate structure is supplied by the aqueous solution of a boron compound which is sufficiently soluble. It may for example be ammonium tetraborate (TBA) which has a satisfactory solubility between 50 and 80 ° C (about 300 g / l or 15.1% B2O3). Preferably, the solution is prepared and used at 65-70 ° C. Boric acid is just as suitable: solubility of 130 g / l at 65 °, ie 6.5% B2O3.
  • TSA ammonium tetraborate
  • the solutions used are concentrated prepared solutions with the aim of rapidly manufacturing a gel and minimizing the amount of water to be evaporated, as will be explained in the description and the examples. It is difficult to give an exact concentration limit for each of the compounds, but one can reasonably locate the concentration of solutions to at least 75% of the saturation concentration.
  • the solution of the adjuvant it is necessary to use compounds containing the desired elements which are soluble in water, at the process temperature, which are compatible with each other, which do not unnecessarily add other ions and whose ions not participating in the structure of the final glass are easily removed by heating.
  • They are, for example, nitrate solutions when nitric FP solutions are treated.
  • the solid compounds are preferably dissolved in the minimum quantity of water so as to minimize the volumes treated and the quantities of water to be evaporated.
  • the mixing is carried out between 20 and 80 ° C.
  • the concentrated solution of the boron compound is maintained to avoid precipitation between 50 and 80 ° C.
  • the other solutions are developed at room temperature. It is then possible either to mix the solutions at the temperature at which they are prepared or brought, or to bring all the solutions to a higher temperature.
  • the latter has the following advantage. After mixing has taken place and the gelled solution has started to form, the polymerization (gelling) takes place during a so-called maturation time. The rise in temperature favors it. It is therefore very advantageous to prepare the mixture between 50 ° C and 80 ° C.
  • the gelling solution matures in the process which is the subject of the invention, during drying, preferably at 100-105 ° C.
  • the solutions of the glass constituents have different pH values: the gel precursor in solution is alkaline (Ludox) or acid (Aerosil in nitric solution), the solution of acid vitrification adjuvant, the solution of the acidic boron compound (boric acid) or alkaline (TBA).
  • the pH of the mixture must be less than 7 and preferably between 2.5 and 3.5. An adjustment of the pH can be undertaken if necessary.
  • the mixing of the components takes place by simultaneously bringing these components together and agitating them with "a high rate of shear".
  • These components can be brought separately or possibly grouped when they do not react with each other.
  • a high shear rate is defined as agitation delivered by a device rotating at at least 500 rpm and preferably 2000 rpm and for which the thickness of the agitated layer (distance between the agitation blade and the wall of the mixing zone) does not exceed 10% of the diameter of the blade.
  • This device can be a turbine, for example, for application on an industrial scale. Laboratory tests with a mixer or mechanical stirrer in a narrow beaker have shown sufficient mixing capacity.
  • an important advantage not previously obtained by the other gelling techniques is that large amounts of gel can be prepared without difficulty. With a turbine, without being at the limit we reached 40 kg / h of gel very easily.
  • a solution called a gelled solution By mixing, a solution called a gelled solution is obtained, its viscosity and its texture changing over time and going from a fluid solution to a gel.
  • the inactive borosilicate matrix thus obtained in the form of a gelled solution is then heat treated, the nuclear waste being added at any stage of said treatment.
  • the method can be applied to various types of solid and / or liquid nuclear waste. It is particularly suitable for the vitrification of FP solutions alone or with other active effluents, for example the soda washing solution of tributylphosphate used for the extraction of uranium and plutonium, the soda washing solution possibly being even be treated alone by this process.
  • active effluents for example the soda washing solution of tributylphosphate used for the extraction of uranium and plutonium, the soda washing solution possibly being even be treated alone by this process.
  • FP solutions are nitric solutions resulting from the reprocessing of fuels, they contain a large number of elements in various chemical forms and a certain amount of insolubles.
  • An example of composition is given below.
  • the soda effluent is based on sodium carbonate and contains degradation products of tributylphosphate (TBP) caused by washing (example 2).
  • TBP tributylphosphate
  • the high sodium content of this effluent must be taken into account when determining the composition of the borosilicate matrix.
  • Case 1 nuclear waste in solution is added to an inactive borosilicate matrix whose volume has been reduced.
  • the gelled solution obtained by mixing the constituents under the conditions described is subjected to drying, between 100 and 200 ° C at 100-105 ° C preferably. During this operation, the water evaporates and the volume is reduced. It is possible, for the following of the process either to do a thorough drying so as to be able to obtain a friable solid product, or to simply be satisfied with a reduction in volume - more quickly obtained - of 25 to 75% of the initial volume so as to obtain a paste.
  • the reduced volume matrix obtained is dispersed and mixed with stirring with the solution of nuclear waste to be treated. It may be advantageous to mix at a temperature between 60 and 100 ° C to reduce the volume of water while mixing.
  • the dried matrix is introduced into the calciner, the waste solution is brought simultaneously to this calciner, the mixing takes place in the calciner which rotates around its longitudinal axis.
  • the product obtained is sent directly to the melting furnace.
  • the process has the same characteristics: preparation of the matrix-drying-addition of waste ⁇ heat treatment going from a drying temperature to a melting temperature (drying-calcination-melting).
  • the mixture obtained is dried if necessary (between 100 and 200 ° C at 100-105 ° C preferably) in an oven for example, drying under vacuum is also possible. After drying, a calcination is then carried out between 300 and 500 ° C (350 to 400 ° C preferably) during which the water finishes evaporating and the nitrates decompose in part.
  • the calcination can be carried out either in a conventional calciner (of the type used in the AVM process) or in a melting furnace of the ceramic melter type for example.
  • the melting temperature of the mixture depends on the composition of said mixture. Sodium improves the fusibility of glasses, but it does have the disadvantage of lowering their resistance to leaching.
  • the CEA has developed a formulation of glass that meets the nuclear safety conditions and can be treated by known glass techniques according to the so-called oxide route.
  • the process which is the subject of the invention makes it possible to vitrify various wastes, in particular wastes rich in sodium, since the composition of the borosilicate matrix is adjusted to the type of wastes treated.
  • a borosilicate matrix low in sodium (or even without sodium) is prepared as will be shown in the examples.
  • drying-calcination-melting steps described correspond to heat treatments in certain temperature zones. It is obvious that similar heat treatments in other devices are suitable, as is generally any technique for making glass from the gel. 2nd case : nuclear waste in solution is added to a calcined borosilicate matrix
  • the borosilicate matrix in the form of a gelled solution is dried (between 100 and 200 ° C, preferably at 100-105 ° C) and then calcined between 300 and 500 ° C, temperature below 400 ° C preferred, in devices similar to those described for the 1st case.
  • the calcined matrix obtained is dispersed and mixed with the solution of the waste to be treated.
  • This operation of mixing the calcined matrix with the waste solution can be carried out in a reactor or else in the calciner itself.
  • the calciner is supplied with the solution of the FPs and the calcined matrix separately brought into the desired proportions. From then on, the operation takes place at nearly 200 ° C at the entrance to the calciner to progress to 400 ° C.
  • a stirring device makes it possible to mix the substances, in the calciner it is its own rotation around its longitudinal axis which ensures the mixing.
  • the mixture obtained (calcined matrix + waste) is subjected to a heat treatment (drying, calcination, fusion) under the conditions already described to form a glass.
  • a heat treatment drying, calcination, fusion
  • This process has the advantage of being able to be implemented immediately in current production chains by allowing the adaptation of the vitrification adjuvant to the treated waste (as will be shown in Example 3).
  • Group 1 represents the inactive elements of the FP solution and group 2 simulates the active elements of this same solution and the insolubles.
  • the simulated FP solution has a pH: 1.3.
  • the final glass composition to be obtained is:
  • the solution of the vitrification aid is prepared according to the composition of the glass to be obtained and that of the waste solution to be treated.
  • the vitrification aid solution is prepared as follows:
  • Each of the compounds is dissolved in the minimum amount of water, ie a total of 640 g of water at 65 ° C; pH: 0.6.
  • the precursor agent is Ludox AS40: 40% SiO2 - 60% H2O ⁇ of particles: 21 nm d 25 ° C : 1.30 - pH 9.3 used at room temperature
  • the TBA solution (NH4) 2O, 2B2O3, 4H2O, 265.2 g dissolved in 663 g of water at 65 ° C - pH: 9.2.
  • a conventional turbine comprising a mixing zone of small volume in which a propeller with several blades rotates so that a mixture with a high rate of shear is produced. In this example, it rotates at 2000 rpm.
  • the turbine used for the tests is manufactured by the company STERMA, the mixing zone has a volume of 1 cm3 and the thickness of the agitated layer is of the order of mm.
  • the mixture obtained is stirred for approximately 30 min then dried at 100-105 ° C in an oven, on a plate, calcined for 2 h at 400 ° C and finally melted for 5 h at 1050 ° C.
  • the glass obtained (0.5 kg) obeys the acceptability criteria.
  • a glass of good quality was defined as being a homogeneous glass, not presenting unfonders and bubbles and moreover not showing on the surface traces of molybdate.
  • molybdate coming from FP solutions poses a major problem: part of the active Mo tends to separate from the solution and sediment so that this phase is not completely dispersed in the mixture therefore it is not fully included in the gelled solution.
  • the chemical analysis of the glass obtained also shows that the components have practically not volatilized, so that one can consider that the composition of the mixtures (borosilicate matrix then matrix + waste) practically corresponds to that of the final glass.
  • the calcined (1 kg) and ground ( ⁇ 300 - 400 ⁇ ) matrix is dispersed in the FP solution (3 kg) with simple stirring (magnetic stirrer 30-45 min).
  • the mixture is calcined for 4 hours at 400 ° C. after baking for 34 hours at 120 ° C., then melted at 1125 ° C.
  • This test relates to the treatment of subsequently acidified washing soda effluent.
  • this AVM process uses the vitrification adjuvant in a form of solid glass frit, a known composition is: SiO2 55-60% by weight B2O3 16-18% by weight Al2O3 6-7% by weight Na2O 6-7% by weight CaO 4.5-6% by weight ZnO 2.5-3.5% by weight Li2O 2-3
  • the present invention makes it possible to manufacture a borosilicate glass with the soda effluent having a composition close to that giving any satisfaction in the AVM process.
  • the ripening temperature can be significantly lowered or the ripening times shortened.
  • the following vitrification aid solution is prepared for one liter of aqueous solution: Al (NO3) 3, 9H2O 209.0 g Ca (NO3) 2, 3H2O 98.5 g LiNO3 53.7 g Zn (NO3) 2, 6H2O 49.7 g Fe (NO3) 3, 6H2O 73.5 g Mn (NO3) 3, 6H2O 18.2 g Ba (NO3) 2 5.5 g Co (NO3) 2, 6H2O 11.3 g Sr (NO3) 2 4.1 g CsNO3 8.0 g Y (NO3) 3, 4H2O 71.0 g Na2MoO4, 2H2O 16.6 g Monoammonium phosphate 2.8 g
  • the Aerosil R marketed by the company DEGUSSA.
  • the gel precursor is formed by gradually pouring, with stirring, the Aerosil into water acidified with HNO33N (pH: 2.5) so as to obtain a solution containing 150 g of silica per liter.
  • Adjuvant solution 1.15 l / h 65 ° C .
  • Aerosil solution ... 2 l / h 20 ° C
  • the borosilicate matrix obtained in the form of a gelled solution is dried for 24 hours at 105 ° C. and then calcined for 3 hours at 350 ° C. Solid particles are removed from the oven having a large specific surface area, varying from one test to another but always close to 50m2 / g. After cooling, these particles are poured into the effluent to be treated and stirred for 2 h. A gelatinous mass is formed which is dried at 105 °, calcined at 400 ° C and finally melts at 1150 ° C.
  • This example shows that one can prepare a calcined gel having the same composition as the glass frit used in the AVM process.
  • a calcined matrix is prepared having a composition similar to the glass frit of the AVM process except for sodium: the sodium oxide content is reduced from 7% to 2.6%.
  • the vitrification aid solution will have the following composition:
  • Ludox AS 40 - as a source of boron: a boric acid solution containing 130.5 g per 1000 g of water, maintained at 60 ° C.
  • the silica to boric anhydride ratio is equal to 3.244 in the theoretical formula and to 3.242 in the calcined gel.
  • the silica to alumina ratio is 13.75 in the theoretical formulation and 13.69 in the calcined gel.
  • silica / sodium ratio is equal to 8.407 in the theoretical formulation and to 22.82 in the calcined gel.
  • the sodium content is 7% in the theoretical formula and 2.7% in the calcined gel.
  • This example shows the possibility of producing at will a calcined gel having a composition which is difficult to obtain in the form of a glass frit, and in particular the possibility of manufacturing a calcined gel low in sodium making it possible to vitrify at the same time the solution of the FPs and the soda effluent.
  • the concentrated solutions have been prepared, some are even close to saturation, so as not to increase the drying times and the volumes of liquid to be handled. It may be necessary, without damage to the process, to further dilute these solutions, in particular for pumping and flow issues.
  • the Applicant believes that it has succeeded in preparing in an aqueous medium a borosilicate matrix ready to be used for the treatment of nuclear waste by the solutions used and the method of agitation used.
  • the process which is the subject of the invention has an important advantage during its industrial exploitation in a nuclear environment: the matrix is prepared in an inactive environment, so that this whole part of the process is outside the rigid constraints which are essential to observe in an active environment, conventional technologies in the chemical industry can be used as they are.
  • the second part of the process heat treatment with introduction of waste
  • the second part of the process can use virtually as is the current production lines already installed and working with oxides.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Glass Compositions (AREA)
  • Glass Melting And Manufacturing (AREA)
EP87400752A 1986-04-08 1987-04-06 Verfahren zur Herstellung von radioaktive Abfälle enthaltendem Borsilikatglas Expired - Lifetime EP0241365B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87400752T ATE58446T1 (de) 1986-04-08 1987-04-06 Verfahren zur herstellung von radioaktive abfaelle enthaltendem borsilikatglas.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8605010A FR2596910A1 (fr) 1986-04-08 1986-04-08 Procede pour la preparation d'un verre borosilicate contenant des dechets nucleaires
FR8605010 1986-04-08

Publications (2)

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EP0241365A1 true EP0241365A1 (de) 1987-10-14
EP0241365B1 EP0241365B1 (de) 1990-11-14

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EP87400752A Expired - Lifetime EP0241365B1 (de) 1986-04-08 1987-04-06 Verfahren zur Herstellung von radioaktive Abfälle enthaltendem Borsilikatglas

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Country Link
US (1) US4797232A (de)
EP (1) EP0241365B1 (de)
JP (1) JP2532087B2 (de)
AT (1) ATE58446T1 (de)
CA (1) CA1332503C (de)
DE (1) DE3766144D1 (de)
FR (1) FR2596910A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2659784A1 (fr) * 1990-03-15 1991-09-20 Doryokuro Kakunenryo Procede de traitement de dechets fortement radioactifs.
FR2677798A1 (fr) * 1991-06-13 1992-12-18 Doryokuro Kakunenryo Procede de vitrification reductrice de volume de dechets hautement radioactifs.

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3811185A1 (de) * 1988-03-31 1989-10-12 Fraunhofer Ges Forschung Verfahren zur herstellung von zu glas verarbeitbaren kondensationsprodukten
US7108808B1 (en) * 1990-04-18 2006-09-19 Stir-Melter, Inc. Method for waste vitrification
US7120185B1 (en) 1990-04-18 2006-10-10 Stir-Melter, Inc Method and apparatus for waste vitrification
US5205864A (en) * 1991-12-20 1993-04-27 Westinghouse Electric Corp. Inorganic based strippable coatings for isolating hazardous materials and method for making and using the same
US5319669A (en) * 1992-01-22 1994-06-07 Stir-Melter, Inc. Hazardous waste melter
JP2989508B2 (ja) * 1995-02-28 1999-12-13 核燃料サイクル開発機構 高レベル放射性廃液のガラス固化方法
US6145343A (en) 1998-05-02 2000-11-14 Westinghouse Savannah River Company Low melting high lithia glass compositions and methods
US6329563B1 (en) * 1999-07-16 2001-12-11 Westinghouse Savannah River Company Vitrification of ion exchange resins
RU2249268C2 (ru) * 2003-02-03 2005-03-27 ФГУП "Производственное объединение "Маяк" Способ переработки радиоактивных коагуляционных пульп
US7503594B2 (en) * 2003-09-09 2009-03-17 Westinghouse Savannah River Company Expanding hollow metal rings
US7550645B2 (en) * 2004-02-23 2009-06-23 Geomatrix Solutions, Inc. Process and composition for the immobilization of radioactive and hazardous wastes in borosilicate glass
CN101448752B (zh) 2006-03-20 2012-05-30 地理矩阵解决方案公司 在硅酸盐基玻璃中固定高碱性的放射性和有害废料的方法和组合物
US20080161629A1 (en) * 2007-01-03 2008-07-03 Oleg Naljotov Radioactive waste processing
JP4406451B2 (ja) * 2007-09-20 2010-01-27 株式会社Ｉｈｉ 高レベル放射性廃液のガラス溶融方法
US9245655B2 (en) 2012-05-14 2016-01-26 Energysolutions, Llc Method for vitrification of waste
US10364176B1 (en) * 2016-10-03 2019-07-30 Owens-Brockway Glass Container Inc. Glass precursor gel and methods to treat with microwave energy
KR20210121257A (ko) 2019-02-20 2021-10-07 코닝 인코포레이티드 철- 및 망간-도프된 텅스텐산염 및 몰리브덴산염 유리 및 유리-세라믹 물품

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1050818A (de) * 1963-09-17 1900-01-01
DE2611689A1 (de) * 1976-03-19 1977-09-29 Kernforschungsanlage Juelich Verfahren zum einschliessen von radioaktiven spaltprodukten
FR2485243A1 (fr) * 1980-06-20 1981-12-24 Kraftwerk Union Ag Procede de stockage definitif, par vitrification, de dechets radioactifs contenant des borates
EP0168218A1 (de) * 1984-07-10 1986-01-15 Westinghouse Electric Corporation Verfahren zur Verfestigung von schlammigen Abfällen die eine hohe Konzentration von Borsäure enthalten

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US32107A (en) * 1861-04-16 William m
DE2657265C2 (de) * 1976-12-17 1984-09-20 Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe Verfahren zur Verfestigung von aus der Wiederaufarbeitung von Kernbrenn- und/oder Brutstoffen stammenden radioaktiven Abfallflüssigkeiten in einer Matrix aus Borsilikatglas
US4377507A (en) * 1980-06-25 1983-03-22 Westinghouse Electric Corp. Containing nuclear waste via chemical polymerization
US4376070A (en) * 1980-06-25 1983-03-08 Westinghouse Electric Corp. Containment of nuclear waste
US4422965A (en) * 1980-08-11 1983-12-27 Westinghouse Electric Corp. Nuclear waste encapsulation in borosilicate glass by chemical polymerization
JPS6046394B2 (ja) * 1981-07-06 1985-10-15 工業技術院長 高レベル放射性廃液のガラスによる固化処理方法
USRE32107E (en) 1982-12-23 1986-04-08 Dow Corning Corporation Carbon-containing monolithic glasses and ceramics prepared by a sol-gel process
US4472510A (en) * 1982-12-23 1984-09-18 Dow Corning Corporation Carbon-containing monolithic glasses and ceramics prepared by a sol-gel process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1050818A (de) * 1963-09-17 1900-01-01
DE2611689A1 (de) * 1976-03-19 1977-09-29 Kernforschungsanlage Juelich Verfahren zum einschliessen von radioaktiven spaltprodukten
FR2485243A1 (fr) * 1980-06-20 1981-12-24 Kraftwerk Union Ag Procede de stockage definitif, par vitrification, de dechets radioactifs contenant des borates
EP0168218A1 (de) * 1984-07-10 1986-01-15 Westinghouse Electric Corporation Verfahren zur Verfestigung von schlammigen Abfällen die eine hohe Konzentration von Borsäure enthalten

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2659784A1 (fr) * 1990-03-15 1991-09-20 Doryokuro Kakunenryo Procede de traitement de dechets fortement radioactifs.
FR2677798A1 (fr) * 1991-06-13 1992-12-18 Doryokuro Kakunenryo Procede de vitrification reductrice de volume de dechets hautement radioactifs.

Also Published As

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JPS63106599A (ja) 1988-05-11
ATE58446T1 (de) 1990-11-15
CA1332503C (en) 1994-10-18
DE3766144D1 (de) 1990-12-20
US4797232A (en) 1989-01-10
JP2532087B2 (ja) 1996-09-11
FR2596910A1 (fr) 1987-10-09
EP0241365B1 (de) 1990-11-14

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