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

Info

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
Authority
EP
European Patent Office
Prior art keywords
metal
medium
hydroxide
zero
magnesium
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.)
Active
Application number
EP16158296.0A
Other languages
English (en)
French (fr)
Other versions
EP3065140A1 (de
Inventor
David Lambertin
Frédéric GOETTMANN
Fabien Frizon
Adrien Blachere
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Commissariat a lEnergie Atomique CEA, Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Commissariat a lEnergie Atomique CEA
Publication of EP3065140A1 publication Critical patent/EP3065140A1/de
Application granted granted Critical
Publication of EP3065140B1 publication Critical patent/EP3065140B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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.

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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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.

Publications (2)

Publication Number Publication Date
EP3065140A1 EP3065140A1 (de) 2016-09-07
EP3065140B1 true EP3065140B1 (de) 2018-09-26

Family

ID=53483947

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16158296.0A Active EP3065140B1 (de) 2015-03-05 2016-03-02 Verfahren zur auflösung eines metalls, und umsetzung zur einbindung dieses metalls in ein geopolymer

Country Status (2)

Country Link
EP (1) EP3065140B1 (de)
FR (1) FR3033444B1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP3065140A1 (de) 2016-09-07
FR3033444A1 (fr) 2016-09-09
FR3033444B1 (fr) 2017-04-07

Similar Documents

Publication Publication Date Title
EP2061732B1 (de) Unschädlicher geopolymerzement auf der basis von flugasche
EP2897919B1 (de) Verfahren zur herstellung eines verbundwerkstoffs aus einer organischen flüssigkeit und hergestellter werkstoff
EP2552849B1 (de) Verwendung von korrosionshemmern zur konditionierung von magnesiummetall, auf diese weise hergestelltes konditionierungsmaterial und herstellungsverfahren
EP0241364B1 (de) Verfahren zur Verfestigung von nuklearen Abfällen in Borsilikatglas
EP0241365B1 (de) Verfahren zur Herstellung von radioaktive Abfälle enthaltendem Borsilikatglas
FR2472818A1 (fr) Procede pour la solidification en vue du stockage final respectant l'environnement de resines echangeuses d'ions radioactives dans des blocs de ciment
CN115504712A (zh) 固化有重金属离子的地聚物材料及其制备方法
CN1128802A (zh) 有色合金熔炼用熔剂及其配制方法和使用方法
EP3065140A1 (de) Verfahren zur auflösung eines metalls, und umsetzung zur einbindung dieses metalls in ein geopolymer
EP3523391A1 (de) Geopolymer mit organischem phasenwechselmaterial, herstellungsverfahren dafür und verwendungen davon
EP1466038B9 (de) Herstellung von magnesium-zirconium-legierungen
EP2717270B1 (de) Matrix zur Immobilisierung von radioaktiven Abfällen, die mindestens Alkalisalze beinhalten, und Immobilisierungsverfahren dieser radioaktiven Abfälle um eine Immobilisierungsmatrix zu erhalten
EP3873683B1 (de) Verfahren zur konditionierung eines sauren abfalls durch zementieren
JP7601329B2 (ja) 固化体の作製方法
BE842206R (fr) Procede de traitement de dechets et produits obtenus
FR2568400A1 (fr) Procede de traitement de solidification avec reduction de volume pour une eau residuaire radioactive contenant du bore
FR2691386A1 (fr) Procédé de réduction de nocivité de déchets particulaires ou ioniques.
JP4787998B2 (ja) 放射性廃棄物の固化処理方法
EP3031053A1 (de) Verfahren zur behandlung und/oder inertisierung einer stark salzhaltigen, möglicherweise kontaminierten lösung
FR2527376A1 (fr) Procede pour ameliorer les proprietes de dechets solides radioactifs incorpores dans une matrice et solidifies
CA2597943A1 (fr) Fabrication d'un materiau solide a partir d'un hydroxyde alcalin
FR2998409A1 (fr) Procede et appareil pour le traitement d'une matiere radioactive
WO2026057843A1 (fr) Procédé de synthèse de chlorure(s) d'actinide(s) à partir d'oxyde(s) d'actinide(s) présent(s) dans un sel fondu
JPS5910898A (ja) 金属ナトリウムの不活性化処理方法
FR2882276A1 (fr) Fabrication d'un materiau solide a partir d'un hydroxyde alcalin

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160302

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

17Q First examination report despatched

Effective date: 20160825

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: G21F 9/30 20060101ALI20180320BHEP

Ipc: G21F 9/28 20060101AFI20180320BHEP

INTG Intention to grant announced

Effective date: 20180409

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1046977

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181015

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016005835

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181227

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181226

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181226

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1046977

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190126

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190126

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016005835

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190627

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602016005835

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190302

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190302

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20160302

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180926

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20260324

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20260324

Year of fee payment: 11