EP3065140B1 - Verfahren zur auflösung eines metalls, und umsetzung zur einbindung dieses metalls in ein geopolymer - Google Patents

Verfahren zur auflösung eines metalls, und umsetzung zur einbindung dieses metalls in ein geopolymer Download PDF

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Publication number
EP3065140B1
EP3065140B1 EP16158296.0A EP16158296A EP3065140B1 EP 3065140 B1 EP3065140 B1 EP 3065140B1 EP 16158296 A EP16158296 A EP 16158296A EP 3065140 B1 EP3065140 B1 EP 3065140B1
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EP
European Patent Office
Prior art keywords
metal
medium
hydroxide
zero
magnesium
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English (en)
French (fr)
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EP3065140A1 (de
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David Lambertin
Frédéric GOETTMANN
Fabien Frizon
Adrien Blachere
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives 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
    • 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
    • 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

Definitions

  • the present invention provides a method of stabilizing a metal at an optionally radioactive zero oxidation state such as optionally radioactive metal magnesium by an oxidation step in a molten salt such as a hydroxide medium.
  • the mixture thus obtained can be subsequently used for conditioning in a geopolymeric mineral matrix.
  • the carbonic dissolution process is, however, a slow process that generates effluents that are not rich in magnesium and therefore a large volume of effluents.
  • the dissolution of magnesium hydroxide and magnesium carbonate is very limited.
  • the present invention solves the technical problems of magnesium metal stabilization processes and achieve the goals set by the inventors.
  • the present invention is remarkable because, from the results obtained for the stabilization of magnesium metal, it is generalizable to many other metals.
  • the medium used during the pyrochemical process is an oxidizing medium for treating many metals more reducing than said medium.
  • this conditioning can be performed on many metals.
  • the present invention relates to a method for preparing a medium comprising at least one metal hydroxide comprising putting a metal at a zero oxidation state in contact with a medium comprising at least one molten salt of the hydroxide type, in the presence a more oxidizing element than said metal at an oxidation state of zero, whereby a medium comprising at least one metal hydroxide is obtained.
  • This process is also defined herein as a pyrochemical process. Similarly, this process can be defined as a method of dissolving or solubilizing a metal at an oxidation state of zero.
  • this metal with an oxidation state of zero is usable in the context of the process according to the present invention.
  • this metal with a degree of oxidation of zero typically belongs to the elements that it is desired to stabilize and condition, especially in the context of the disposal and treatment of metallic nuclear waste.
  • the metal at an oxidation state of zero is selected from the group consisting of magnesium metal, aluminum metal, a metal actinide, one of their alloys or a mixture thereof.
  • the metal with a zero oxidation state is selected from the group consisting of magnesium metal, aluminum metal, uranium metal, neptunium metal, actinium metal, thorium metal, plutonium metal , americium metal, curium metal, one of their alloys or a mixture thereof.
  • alloy is meant both an alloy of two different metals mentioned in any of the above lists than an alloy of a metal cited in any of the above lists with a metal not present. in these lists.
  • mixing is meant a mixture of at least two different metals mentioned in any of the above lists.
  • a magnesium metal alloy is more particularly selected from the group consisting of magnesium / aluminum, magnesium / zirconium and magnesium / manganese. In these alloys, the amount of magnesium is greater than 80%, 90% and 95% expressed by weight relative to the total mass of the alloy.
  • the medium comprising at least one molten salt of the hydroxide type used in the process according to the present invention consists only of a molten salt of the hydroxide type such as, for example, potassium hydroxide (KOH), sodium hydroxide (NaOH) or lead hydroxide (Pb (OH) 2 ).
  • KOH potassium hydroxide
  • NaOH sodium hydroxide
  • Pb (OH) 2 lead hydroxide
  • the medium comprising at least one molten salt of the hydroxide type used in the process according to the present invention may be an eutectic mixture.
  • eutectic mixing is meant a mixture of at least two products in defined proportions having physico-chemical characteristics essentially identical to those of a single product or “pure body”.
  • Such a eutectic mixture may be binary and therefore consist of a mixture of two products but may also contain more than two products. Note that It may be advantageous to use such a eutectic mixture to obtain a melting temperature below the melting temperature of at least one of the products present in the mixture and used alone.
  • a eutectic mixture that may be used in the context of the present invention may comprise at least two different molten salts of hydroxide type.
  • such a eutectic mixture may be a mixture of potassium hydroxide (KOH) and magnesium hydroxide (Mg (OH) 2 ), in particular a mixture of KOH + Mg (OH) 2 with the KOH present in a weight percentage of 65 to 95%, advantageously 70 to 90% and the Mg (OH) 2 present in a weight percentage of 5 to 35%, advantageously 10 to 30%, the mass percentages being expressed relative to to the total mass of the mixture.
  • KOH potassium hydroxide
  • Mg (OH) 2 magnesium hydroxide
  • a more particular example of hydroxide mixtures that can be used in the context of the present invention is a mixture of KOH at 80% by weight and Mg (OH) 2 at 20% by weight, the mass percentages being expressed relative to the total mass of the product. mixed.
  • an eutectic mixture that may be used in the context of the present invention may comprise at least one molten salt of the hydroxide type and at least one other molten salt different from a hydroxide and in particular such as a salt.
  • melted chloride, fluoride, nitrate or carbonate melted chloride, fluoride, nitrate or carbonate.
  • the mixture obtained should remain compatible with a subsequent use to prepare an immobilization matrix.
  • the contacting of the metal at an oxidation state of zero with the medium comprising at least one molten salt of the hydroxide type is in the presence of a more oxidizing element than said metal at an oxidation state of zero.
  • the metal with a degree of oxidation of zero is oxidized and converted into a metal having a degree of oxidation greater than zero and typically a degree of oxidation of 1, 2 , 3 or 4.
  • the metal having a degree of oxidation greater than zero is therefore in ionic form in the medium comprising at least one molten hydroxide salt and is capable of forming a metal hydroxide salt with the hydroxide ions present in said medium.
  • the more oxidizing said metal element to a degree of zero oxidation is water.
  • This water may be in the form of a moist, neutral gas.
  • moist neutral gas is meant a neutral or inert gas, i.e. a gas not reacting with the various compounds with which it is in contact, charged with water vapor.
  • the neutral gas may be a rare gas, i.e. a gas consisting of a member selected from helium, neon, argon, krypton, xenon, radon and a mixture thereof.
  • the neutral gas is a rare gas, the latter is advantageously argon.
  • the rare gases are particularly advantageous in that they do not dissolve in the medium comprising at least one molten salt of the hydroxide type, and therefore do not bring new elements into this medium, which does not increase the volume of this medium. It is understood that for the purposes of the invention, this rare gas is charged with water vapor.
  • the neutral gas charged with water vapor may also be nitrogen charged with water vapor.
  • the water vapor content contained in the neutral gas and the flow rate with which it is brought into contact with the medium comprising at least one molten salt of the hydroxide type so that inducing the oxidation of the metal to an oxidation state of zero and, from this oxidized metal, the formation of metal hydroxide.
  • the water used as a more oxidizing element than the metal at an oxidation state of zero may be added to the medium containing at least one molten salt of the hydroxide type.
  • This variant can be implemented using at least one of the salts used to prepare the medium comprising at least one molten salt of hydroxide type, under form of a hydrated salt and / or adding water to the medium comprising at least one molten salt hydroxide type, once the latter prepared.
  • This water can also be tap water, deionized water, distilled water or ultrapure water (18.2 M ⁇ ).
  • the amount of salt (s) hydrated (s) and / or the amount of water to be used in the medium comprising at least one molten salt of hydroxide type so as to induce the oxidation of the metal to an oxidation state of zero and, from this oxidized metal, the formation of metal hydroxide.
  • the element that is more oxidizing than said metal at an oxidation state of zero is a metal cation that is more oxidizing than the metal at an oxidation degree of zero, said metal cation being present in the medium. comprising at least one molten salt of hydroxide type.
  • more oxidant means a metal element or cation belonging to a redox couple more oxidizing than the redox couple formed by the metal at an oxidation state of zero and its corresponding cation.
  • the metal cation when the metal at an oxidation state of zero is magnesium metal, the metal cation may be Zn 2+ , Fe 2+ , Pb 2+ or Cu 2+ .
  • This metal cation may be present in the medium in the form of a molten salt of hydroxide, chloride, fluoride, nitrate or carbonate.
  • the pyrochemical process is carried out in the context of the present invention at atmospheric pressure (i.e. at 1013 hPa) and at a moderate temperature.
  • “Moderate temperature” means a temperature between 100 ° C and 400 ° C, and in particular between 150 ° C and 350 ° C.
  • the temperature is chosen so that the salt (s) present in the reaction medium are in the form of salt (s) melt (s). So the man from profession will determine the most suitable reaction temperature depending on the salt (s) present (s) in this medium.
  • the pyrochemical process is carried out for a time sufficient to obtain complete dissolution of the metal at a zero oxidation state in the medium comprising at least one molten salt of hydroxide type.
  • This duration is therefore a function of the size of the powders, the fines, the deposit, the fragment or the piece of the metal at an oxidation degree of zero. It can be determined macroscopically by following the disappearance of said powders, fines, deposit, fragment is piece in said medium. Alternatively, this time can be extrapolated by routine tests as presented in Example 1 below and used to determine the corrosion rate of said metal at an oxidation state of zero in said reaction medium.
  • the medium obtained as a result of the pyrochemical process according to the invention may comprise, in addition to a salt of the metal hydroxide type (ie hydroxide of the cation corresponding to the metal at an oxidation degree of zero), one or more other element (s).
  • (S) such (s) as a molten salt of the hydroxide type initially present in said medium and optionally a molten salt of the chloride, fluoride, nitrate or carbonate type.
  • the process for conditioning a metal having a degree of oxidation of zero involves the use of a pyrochemical process as defined above to prepare a medium comprising at least one salt of the metal hydroxide type, ie the hydroxide of the metal. in oxidized form and use of this medium to prepare an activation solution as defined in the field of geopolymers.
  • geopolymer or “geopolymer matrix” is meant in the context of the present invention a solid and porous material in the dry state, obtained following the hardening of a mixture containing finely ground materials (ie the alumino-silicate source ) and a saline solution (ie the activating solution), said plastic mixture being able to set and harden over time.
  • This mixture may also be referred to as "geopolymeric mixture” or “geopolymeric composition”.
  • the hardening of the geopolymer is the result of the dissolution / polycondensation of the finely ground materials of the geopolymeric mixture in a saline solution such as a high pH salt solution (i.e. the activating solution).
  • step (a) corresponds to a pyrochemical process as defined above.
  • step (a) of the packaging process corresponds to step (a) of the packaging process.
  • an alkaline solution and in particular a strongly alkaline solution ie a high-pH salt solution is prepared from the cooled solid medium obtained following the step ( b) the method, by putting said medium in contact with water.
  • activating solution high pH saline solution
  • high alkaline solution high alkaline solution
  • Step (c) of the packaging process according to the invention can be carried out with stirring using a kneader, a stirrer, a magnetic bar, an ultrasonic bath or a homogenizer, in order to facilitate the dissolution of the solid cooled medium. and any mixing with the silicate components.
  • the dissolution / mixing / kneading process during the sub-step (c) of the process according to the invention is carried out at a relatively high speed.
  • relatively high speed means, in the context of the present invention, a speed greater than 250 rpm, especially greater than or equal to 350 rpm.
  • Step (d) of the process according to the invention consists in bringing into contact the alkaline solution prepared in step (c) and an aluminosilicate source.
  • step (d) of the process according to the invention is carried out in a kneader in which the alkaline solution has been introduced beforehand.
  • a kneader known to those skilled in the art can be used in the context of the present invention.
  • Step (d) of the process according to the invention is carried out at a temperature of between 10 ° C. and 40 ° C., advantageously between 15 ° C. and 30 ° C. and, more particularly, at room temperature for a duration greater than 2 ° C. min, especially between 4 min and 1 h and in particular between 5 min and 30 min.
  • sand, granulate and / or fines may optionally be added to the alkaline solution during said step (d) of the process according to the invention.
  • granulate is meant a granular material, natural, artificial or recycled, the average grain size is advantageously between 10 and 125 mm.
  • the fines also called “fillers” or “addition fines” is a dry product, finely divided, resulting from the size, sawing or work of natural rocks, aggregates as previously defined and ornamental stones.
  • the fines have an average grain size in particular of between 5 and 200 ⁇ m.
  • the sand possibly added during step (d) may be calcareous sand or siliceous sand.
  • it is a siliceous sand that achieves the best results in terms of optimizing the physical and mechanical properties of the geopolymer obtained.
  • the term "siliceous sand” is intended to mean sand that is more than 90%, in particular more than 95%, in particular greater than 98%, and more particularly more than 99%. of silica (SiO 2 ).
  • the siliceous sand used in the present invention advantageously has a mean grain size in particular of less than 10 mm, in particular less than 7 mm and in particular less than 4 mm.
  • a siliceous sand having a mean grain size of between 0.2 and 2 mm can be used.
  • Step (e) of the process according to the invention consists in subjecting the mixture obtained in step (d) to conditions allowing the geopolymeric mixture to harden.
  • the curing step may optionally include a drying step, in addition to the curing step.
  • This drying can be carried out at a temperature of between 30 and 90 ° C., in particular between 40 and 80 ° C. and in particular between 50 and 70 ° C., and can last between 6 hours and 10 days, in particular between 12 hours and 5 hours. days and, in particular, between 24 and 60 h.
  • the latter prior to the hardening of the geopolymeric mixture, the latter can be placed in molds so as to give it a predetermined shape following this hardening.
  • the Figure 1 is a top view of the reactor in which the MgZr fin is immersed in the molten hydroxide during oxidation. Gas bubbles that emanate uniformly from the melt are visible, probably from hydrogen evolution and wet argon bubbling.
  • magnesium metal chips After determining the dissolution kinetics of massive MgZr, a dissolution and immobilization test of magnesium metal chips was carried out in the KOH + Mg (OH) 2 hydroxide mixture (80/20% by mass) at 230 ° C. while maintaining a low pH 2 O (acid medium) by bubbling argon saturated with water.
  • the magnesium chips have a specific surface area of 0.028 m 2 / g.
  • test pieces ( Figure 4F ) were kept with the three modes of preservation (water, air, bag) for 28 days.
  • the results in compression and dimensional variations are reported in Table 1. It appears that the geopolymer pastes have very good mechanical properties at 28 days and are well above the requirements of 8MPa requested by ANDRA for the packaging of homogeneous waste.

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  • 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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Catalysts (AREA)

Claims (11)

  1. Verfahren zur Herstellung eines Mediums, das mindestens ein Metallhydroxid enthält, umfassend das Inkontaktbringen eines Metalls mit einer Oxidationsstufe von null mit einem Medium, das mindestens ein geschmolzenes Salz vom Typ Hydroxid umfasst, in Gegenwart eines stärker oxidierenden Elements als das Metall mit einer Oxidationsstufe von Null, wodurch ein Medium erhalten wird, das mindestens ein Hydroxid des genannten Metalls enthält.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Metall mit einer Oxidationsstufe von null ausgewählt ist aus der Gruppe bestehend aus Magnesium-Metall, Aluminium-Metall, Uran-Metall, Neptunium-Metall, Actinium-Metall, Thorium-Metall, Plutonium-Metall, Americium-Metall, Curium-Metall, einer ihrer Legierungen oder eines ihrer Gemische.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Medium nur aus einem geschmolzenen Salz vom Typ Hydroxid besteht.
  4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Medium zumindest zwei unterschiedliche geschmolzene Salze vom Typ Hydroxid enthält.
  5. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Medium zumindest ein geschmolzenes Salz vom Typ Hydroxid und zumindest ein weiteres geschmolzenes Salz enthält, das sich von Hydroxid unterscheidet.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das stärker oxidierende Element als das Metall mit einer Oxidationsstufe von null ein neutrales Nassgas ist.
  7. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das stärker oxidierende Element als das Metall mit einer Oxidationsstufe von null Wasser ist, das dem Medium zugesetzt wird, das zumindest ein geschmolzenes Salz vom Typ Hydroxid enthält.
  8. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das stärker oxidierende Element als das Metall mit einer Oxidationsstufe von null ein Metallkation ist, das stärker oxidierend ist als das Metall mit einer Oxidationsstufe von null, wobei das Metallkation in dem Medium vorhanden ist, das mindestens ein geschmolzenes Salz vom Typ Hydroxid enthält.
  9. Verfahren zum Einbinden eines Metalls mit einer Oxidationsstufe von null, umfassend die nachfolgenden Schritte:
    a) Herstellen eines Mediums, das zumindest ein Hydroxid des Metalls enthält, nach einem Verfahren, wie es nach einem der Ansprüche 1 bis 8 definiert ist;
    b) Abkühlen des aus Schritt (a) erhaltenen Mediums;
    c) Inkontaktbringen des aus Schritt (b) erhaltenen abgekühlten Mediums mit Wasser, wodurch eine alkalische Lösung erhalten wird;
    d) Zugeben von zumindest einer Aluminosilikatquelle zur in Schritt (c) erhaltenen alkalischen Lösung;
    c) Unterwerfen des in Schritt (d) erhaltenen Gemischs Bedingungen, die das Härten eines Geopolymers gestatten.
  10. Verfahren zum Einbinden nach Anspruch 9, dadurch gekennzeichnet, dass ein bzw. mehrere Silikatkomponenten, insbesondere ausgewählt aus der Gruppe bestehend aus Siliciumdioxid, kolloidalem Siliciumdioxid und Quarzglas, in Schritt (c) zugegeben wird bzw. werden.
  11. Verfahren zum Einbinden nach Anspruch 9 oder 10, dadurch gekennzeichnet, dass die Aluminosilikatquelle eine feste Quelle ist, die amorphe Aluminosilikate enthält, ausgewählt insbesondere aus natürlichen Aluminosilikatmineralien wie Illit, Stilbit, Kaolinit, Pyrophyllit, Andalusit, Bentonit, Kyanit, Milanit, Grovenit, Amesit, Cordierit, Feldspat, Allophan, usw; aus natürlichen kalzinierten Aluminosilikatmineralien wie Metakaolin; synthetischen Gläsern auf Basis reiner Alumosilikate; Tonerdezement; Bims; kalzinierten Nebenprodukten oder Rückständen aus Industriebetrieben wie Flugasche und Hochofenschlacken, die jeweils aus dem Verbrennen von Kohle und während der Verarbeitung von Eisenerzschmelze in einem Hochofen erhalten werden; und deren Gemischen.
EP16158296.0A 2015-03-05 2016-03-02 Verfahren zur auflösung eines metalls, und umsetzung zur einbindung dieses metalls in ein geopolymer Active EP3065140B1 (de)

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FR1551877A FR3033444B1 (fr) 2015-03-05 2015-03-05 Procede de dissolution d'un metal et mise en œuvre pour conditionner ledit metal dans un geopolymere.

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CN115011957B (zh) * 2022-05-09 2023-05-16 桂林理工大学 利用碱热法在镁合金表面制备氢氧化镁与二氧化硅复合薄膜的方法及得到的镁合金材料

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RU2316387C2 (ru) 2005-04-04 2008-02-10 Федеральное государственное унитарное предприятие "Производственное объединение "Маяк" Способ растворения твэл, содержащих металлический магний
GB0705289D0 (en) * 2007-03-20 2007-04-25 Entwistle Tim The rapid and selective dissolution of magnox from magnox,nimonic alloy mixtures and other metals
GB2508010A (en) * 2012-11-19 2014-05-21 Bradtec Decon Technologies Ltd Treatment of Radioactive Material

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FR3033444A1 (fr) 2016-09-09
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