EP0241364B1 - Verfahren zur Verfestigung von nuklearen Abfällen in Borsilikatglas - Google Patents

Verfahren zur Verfestigung von nuklearen Abfällen in Borsilikatglas Download PDF

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Publication number
EP0241364B1
EP0241364B1 EP87400751A EP87400751A EP0241364B1 EP 0241364 B1 EP0241364 B1 EP 0241364B1 EP 87400751 A EP87400751 A EP 87400751A EP 87400751 A EP87400751 A EP 87400751A EP 0241364 B1 EP0241364 B1 EP 0241364B1
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EP
European Patent Office
Prior art keywords
solution
glass
solutions
gel
waste
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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EP87400751A
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English (en)
French (fr)
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EP0241364A1 (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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Priority to AT87400751T priority Critical patent/ATE64669T1/de
Publication of EP0241364A1 publication Critical patent/EP0241364A1/de
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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
    • G21F9/04—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
    • 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

Definitions

  • the present invention relates to a method for immobilizing nuclear waste in a borosilicate glass. This process is particularly suitable for treating high-level waste.
  • 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 FP solution and in sending the calcinate obtained, simultaneously with a glass frit, to a melting furnace. In a few hours, at a temperature of the order of 1100 ° C., a glass is obtained which is poured into metal containers.
  • the glass frit is composed mainly of silica and boric anhydride, plus the other oxides (sodium, aluminum, etc.) necessary for the total formulation of calcinate + frit to give a glass which can be produced by known glass techniques and fulfilling the conditions of safety for storage (conditions on leaching, mechanical strength, etc.).
  • the temperature should be chosen high enough to hasten digestion but without having an adverse effect on the life of the oven.
  • the applicant has developed a process in which the constituents of the glass are mixed in an aqueous medium so as to form a gelled solution.
  • the main objective is the manufacture by 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.
  • sol-gel method A way is known for preparing the gels in an aqueous medium, known as the sol-gel method, which consists in using a sol in water and in destabilizing it by modifying the pH, thus causing this solution to gel.
  • Said mixing can be carried out in a turbine, a mixer or more simply with a mechanical agitator rotating in a narrow section.
  • the solutions used are concentrated 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 the concentration of the solutions can reasonably be situated at least 75% of the saturation concentration.
  • the method can be applied to various nuclear waste solutions. It is particularly suitable for the vitrification of FP solutions alone or with other active effluents, for example the soda solution for washing tributylphosphate used for the extraction of uranium and plutonium; the sodium washing solution can 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 possibly contains organic phosphorus traces entrained by washing (example 3).
  • a substance containing silica particles, possibly partially hydrolyzed, which is either in the form of a powder which, when dissolved in acid, 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 for example be a sol such as Ludox® or else Aerosil® 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.
  • the Ludox is brought in as is solution. Aerosil on the other hand can be taken either in solution or directly in the form of powder, depending on the technology used.
  • the gel precursor is placed in an acidic aqueous medium, according to the process which is the subject of the invention, so that it becomes a gelled solution by polymerization from Si-OH- bonds.
  • the boron necessary to form the borosilicate structure is brought by the aqueous solution of a boron compound sufficiently soluble such as ammonium tetraborate (TBA) which has a solubility of approximately 3OO g / l or 15.1% B2O3.
  • TSA ammonium tetraborate
  • the solution is prepared and used at 65-7O ° C.
  • Boric acid can just as easily be used, its solubility is around 13O g / l at 65 ° C or 6.5% B2O3, it is increased in the presence of Na+ ions when Na / B ⁇ O, 23 .
  • the vitrification aid To prepare the solution of the vitrification aid, it is necessary to use compounds containing the desired elements which are soluble in water, at 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 always 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 solutions to be treated are taken at the temperature at which they are; the FP solution, due to the fact that its activity arrives at the treatment unit between 20 ° and 40 ° 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 developed or brought, either to bring all the solutions (except those of the waste taken as is) to a higher temperature before mixing them.
  • 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 100-150 ° C.
  • the solutions of the glass constituents have different pH values: the gel precursor in solution is acid (such as Aerosil in nitric solution) or alkaline (Ludox), the solution of acidic vitrification adjuvant, the solution of acid waste ( in the case of FP) or alkaline (non-neutralized washing effluent) solutions, the solution of the boron acid (boric acid) or alkaline (ammonium tetraborate) compound.
  • 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 mixture - from which the final glass is obtained by heating - is prepared from all the components in aqueous solution introduced simultaneously into the mixing zone.
  • a so-called solution is obtained gelled, its viscosity and its texture changing over time and going from a fluid solution to a gel.
  • the mixture obtained is dried (at 1OO-1O5 ° C preferably) in an oven for example, drying under vacuum is also possible. During this operation, the gel continues to form.
  • a calcination is then carried out between 3OO and 5OO ° C (35O to 4OO ° C preferably) during which the water finishes evaporating and the nitrates decompose in part, the analysis shows that after 2 h at 4OO ° C 30% of the nitrates are still present under the conditions of the example.
  • the calcination can be done either in a conventional calciner (of the type used in the AVM vitrification process) or in a melting furnace of the ceramic melter type for example.
  • drying-calcination-melting steps described correspond to heat treatments in defined temperature zones and in different equipment. It is obvious that similar heat treatments in other devices are suitable, for example drying in an oven followed by introduction into a melting furnace designed in several zones, in general any technique for making glass from a gel can be used.
  • the composition of the borosilicate matrix prepared in an aqueous medium is adjusted to the type of waste treated.
  • a borosilicate matrix low in sodium (or even possibly without sodium) can be developed, as the examples will show.
  • Example 1 A conventional method for preparing gels applied to the treatment of a simulated FP solution .
  • Group 1 represents the inactive elements of the fission product solution and group 2 the PF and insolubles of the same solution.
  • the simulated FP solution has a pH: 1.3.
  • the final glass composition to be obtained is:
  • the solutions of the vitrification aid are prepared according to the composition of the glass to be obtained and that of the waste solution to be treated.
  • the separate vitrification aid solutions are thus prepared at room temperature:
  • Ludox In another beaker, 56 cm3 of Ludox are acidified to pH 2, to avoid the subsequent precipitation of hydroxides such as Al (OH) 3 at pH: 5-6 or Zn (OH) 2 at pH: 4.8.
  • the Ludox solution is introduced, with stirring, into the ammonium tetraborate, the reaction taking place at 65 ° C.-70 ° C. Stirred (magnetic or mechanical stirrer) 30 min while maintaining the temperature. To accelerate the gelation, a small amount of dilute ammonia (0.15 N) is added to obtain pH: 3. There is gel formation.
  • the mixture is left to stand at 65 ° C.-70 ° C., it takes at least 20 h to obtain a mass which is dried in the oven (90 h at 110 ° C.) immediately after its obtaining, then melted between 1OOO and 115O ° C.
  • a glass of good quality was defined as being a homogeneous glass, not presenting any unfused 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.
  • Example 2 Treatment of a solution of fission products according to the invented method .
  • 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.
  • 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 2OOO rpm.
  • the turbine used for the tests is manufactured by the company STERMA, the mixing zone has a volume of 1 cm3, the thickness of the agitated layer is of the order of mm.
  • the mixing zone has a volume of 1 cm3
  • the thickness of the agitated layer is of the order of mm.
  • the vitrification and PF adjuvant solutions are pumped at the indicated flow rate, and it is their mixture at the overall flow rate of 25.4 kg / h which is sent to the turbine. Thus, there is a flow rate of 36 kg / h in gel.
  • the pH of the gelled solution leaving the turbine is 3.
  • Example 3 Treatment of a soda wash effluent.
  • This composition limits the amount of admissible sodium in the effluent to be vitrified, since the sodium content cannot be increased too much which lowers the resistance to leaching.
  • 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:
  • Each of the solutions is kept in a thermostatically controlled bath (temperature 65 ° C).
  • thermostatically controlled bath temperature 65 ° C.
  • diaphragm pumps that have been adjusted beforehand to obtain the desired flow rates.
  • the debits set are:
  • the operation is carried out for 1.5 h still in the form of agitation.
  • the contents of the mixer bowl are poured into a beaker and left to stand for 2 hours.
  • a homogeneous, practically solid mass of opalescent color is formed. This mass is distributed on a plate to form a layer of approximately 20 to 30 mm thick and the plate is placed in an oven heated to 105 ° C. for 24 h.
  • Dry particles of the order of cm3 are thus obtained. It is placed in an oven to calcine, the temperature is regularly raised over 3 hours to 400 ° C. and it is maintained for 3 hours. The calcinate obtained is crushed into particles of 1 to 3 mm.
  • a Joule effect electric oven with sufficient capacity is set at 115O ° C.
  • This example shows how the composition of the vitrification aid can be adjusted.
  • Example 4 Treatment of the soda effluent with Aerosil .
  • the vitrification adjuvant, TBA and waste solution solutions are the same.
  • the Aerosil ® sold 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 of 150 g of silica per liter.
  • the two examples 3 and 4 illustrate the invention for the treatment of soda effluent with different gel precursors, but they do not constitute a limitation thereof.
  • the neutralized soda effluent was treated alone. It is obviously advantageous to simultaneously treat the non-neutralized soda effluent (therefore as it leaves the extraction units) and the FP solutions which are nitric, so as not to consume nitric acid and increase the volumes of waste. For this, the washing water of the nitrous vapors, loaded with nitric acid, is added to the soda effluent to neutralize it, the resulting liquid being mixed with the FP solution in predetermined proportions. The vitrification adjuvant solution will then be suitable for this treatment.
  • the boron compound used is ammonium tetraborate tetrahydrate, this to allow comparison with the prior art easier.
  • TBA in existing vitrification plants, the use of TBA poses problems in the treatment of gaseous effluents rich in ammonia and nitrous vapors which are capable of recombining to produce dangerous ammonium nitrate under certain conditions.
  • boric acid is preferred under the conditions of the process which is the subject of the invention.
  • the Applicant believes that the gelled solution produced according to the invented process forms more quickly than the compounds react with one another to precipitate.
  • the gelled solution obtained has the structure of the desired final glass and in this solution the ions can no longer migrate.

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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)
  • Processing Of Solid Wastes (AREA)

Claims (7)

  1. Verfahren zur Verfestigung von nuklearen Abfällen in Borsilikatglas, dadurch gekennzeichnet, daß:
    - in einem Behälter, der mit einer Ausschüttelvorrichtung versehen ist, die sich mit mehr als 500 min⁻¹ und vorzugsweise mit 2000 min⁻¹ dreht und in der die Dicke der ausgeschüttelten Schicht 10% des Durchmessers der Ausschüttelvorrichtung nicht übersteigt, gleichzeitig gemischt werden:
    · ein Gel-Zwischenstoff auf Kieselerdebasis,
    · eine konzentrierte wäßrige Lösung einer Borverbindung,
    · die konzentrierten wäßrigen Lösungen der anderen Stoffe des endgültigen Glases, die die Lösung(en) der zu bearbeitenden Abfälle und die Lösung des Verglasungszusatzstoffes enthalten,
    wobei die Mischung zwischen 20° und 80°C, vorzugsweise zwischen 65° und 70°C in den Verhältnissen, die der Zusammensetzung des erforderlichen Glases entsprechen, stattfindet, wobei das Gemisch einen sauren pH-Wert, vorzugsweise zwischen 2,5 und 3,5, besitzt;
    - das Gemisch anschließend getrocknet, zwischen 300° und 500°C geglüht und anschließend geschmolzen wird.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die Mischung in einem Gerät ausgeführt wird, das entweder eine Turbine oder eine Rührmaschine ist.
  3. Verfahren gemäß einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß der Gel-Zwischenstoff ein Sol ist.
  4. Verfahren gemäß einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß der Gel-Zwischenstoff ein Ludox® ist.
  5. Verfahren gemäß einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß der Gel-Zwischenstoff Aerosil® ist.
  6. Verfahren gemäß einem der Ansprüche 1 oder 5, dadurch gekennzeichnet, daß die Borverbindung Amonium-Tetraborat ist.
  7. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Borverbindung Borsäure ist.
EP87400751A 1986-04-08 1987-04-06 Verfahren zur Verfestigung von nuklearen Abfällen in Borsilikatglas Expired - Lifetime EP0241364B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87400751T ATE64669T1 (de) 1986-04-08 1987-04-06 Verfahren zur verfestigung von nuklearen abfaellen in borsilikatglas.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8605009A FR2596909B1 (fr) 1986-04-08 1986-04-08 Procede d'immobilisation de dechets nucleaires dans un verre borosilicate
FR8605009 1986-04-08

Publications (2)

Publication Number Publication Date
EP0241364A1 EP0241364A1 (de) 1987-10-14
EP0241364B1 true EP0241364B1 (de) 1991-06-19

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EP87400751A Expired - Lifetime EP0241364B1 (de) 1986-04-08 1987-04-06 Verfahren zur Verfestigung von nuklearen Abfällen in Borsilikatglas

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Country Link
US (1) US4772431A (de)
EP (1) EP0241364B1 (de)
JP (1) JPH0833493B2 (de)
AT (1) ATE64669T1 (de)
CA (1) CA1332504C (de)
DE (1) DE3770855D1 (de)
ES (1) ES2023920B3 (de)
FR (1) FR2596909B1 (de)

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US6145343A (en) * 1998-05-02 2000-11-14 Westinghouse Savannah River Company Low melting high lithia glass compositions and methods
RU2168225C1 (ru) * 1999-10-28 2001-05-27 Московское государственное предприятие - объединенный эколого-технологический и научно-исследовательский центр по обезвреживанию РАО и охране окружающей среды (Мос НПО "Радон") Способ остекловывания радиоактивных отходов в охлаждаемом металлическом индукционном плавителе
RU2168226C1 (ru) * 1999-10-28 2001-05-27 Московское государственное предприятие - объединенный эколого-технологический и научно-исследовательский центр по обезвреживанию РАО и охране окружающей среды (Мос НПО "Радон") Способ остекловывания радиоактивных отходов в охлаждаемом металлическом индукционном плавителе
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FR2943835B1 (fr) * 2009-03-31 2011-04-29 Onectra Procede de conditionnement de dechets radioactifs sous forme de roche synthetique
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Also Published As

Publication number Publication date
ES2023920B3 (es) 1992-02-16
CA1332504C (en) 1994-10-18
US4772431A (en) 1988-09-20
DE3770855D1 (de) 1991-07-25
JPS632000A (ja) 1988-01-06
FR2596909A1 (fr) 1987-10-09
EP0241364A1 (de) 1987-10-14
ATE64669T1 (de) 1991-07-15
JPH0833493B2 (ja) 1996-03-29
FR2596909B1 (fr) 1993-05-07

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