EP2537162B1 - Procede de traitement avant calcination d'une solution aqueuse nitrique comprenant au moins un radionucleide et eventuellement du ruthenium - Google Patents

Procede de traitement avant calcination d'une solution aqueuse nitrique comprenant au moins un radionucleide et eventuellement du ruthenium Download PDF

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Publication number
EP2537162B1
EP2537162B1 EP11703881.0A EP11703881A EP2537162B1 EP 2537162 B1 EP2537162 B1 EP 2537162B1 EP 11703881 A EP11703881 A EP 11703881A EP 2537162 B1 EP2537162 B1 EP 2537162B1
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EP
European Patent Office
Prior art keywords
solution
ruthenium
radionuclide
calcination
effluents
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
EP11703881.0A
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German (de)
English (en)
French (fr)
Other versions
EP2537162A1 (fr
Inventor
Virginie Labe
Frédéric GOETTMANN
Camille Carrignon
Agnès GRANDJEAN
Alain Ledoux
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
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Classifications

    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • G21F9/08Processing by evaporation; by distillation
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • G21F9/14Processing by incineration; by calcination, e.g. desiccation
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28Treating solids
    • G21F9/30Processing
    • G21F9/301Processing by fixation in stable solid media
    • G21F9/302Processing by fixation in stable solid media in an inorganic matrix
    • G21F9/305Glass or glass like matrix

Definitions

  • the invention relates to a method of treating a nitric aqueous solution comprising at least one radionuclide and optionally ruthenium before calcination and vitrification.
  • Such a method finds particular application in the reprocessing of radioactive aqueous liquid effluents, which can be loaded with ruthenium, which effluents are intended to be conditioned by vitrification.
  • aqueous effluents because of their high radiological activity, can not be released into the environment and are, therefore, intended to be packaged so that the radioactive elements and the radioactivity emanating from these are trapped.
  • vitrification which consists of solidifying said effluent in a glassy matrix, the resulting product thus constituting a final conditioned waste. suitably for long-term storage.
  • the aqueous effluents containing the radionuclides are brought, before the vitrification as such, to be preconcentrated, so as to eliminate the water present in these effluents and also denitrer them.
  • a calcination reactor which may be for example, an aerosol reactor, a rotating drum calciner type reactor or a fluidized bed reactor.
  • nitrates resulting from the action of nitric acid on the chemical elements present in the effluents, as is the case of sodium nitrate, have a very low melting point, which generates, in the end calcination operation, a viscous and sticky calcination that can cause clogging of the reactor in which the calcination is carried out.
  • the addition of glucose to the effluents, as mentioned in the document US 4,943,395 can help to promote denitration and thus to limit, in part, the aforementioned problem of clogging.
  • the ruthenium potentially present in the radioactive aqueous liquid effluents can be brought under the conditions of implementation of the calcination, to be oxidized to volatile species and to escape into the environment.
  • a reducing agent in particular glucose, as proposed in the aforementioned document.
  • the authors of the present invention thus proposed to develop a new process for the treatment of radioactive aqueous nitrate effluents possibly comprising ruthenium, so that, during the subsequent calcination, the problems related to the tackiness of calcinat and the possible formation of volatile ruthenium oxide are solved, without the need to resort to the use of inorganic additives as mentioned above.
  • the invention relates, according to a first object, to a process for treating an aqueous nitric solution comprising at least one radionuclide and optionally ruthenium comprising a step of adding to said solution a compound chosen from lignins lignocelluloses, optionally in the form of salts and mixtures thereof.
  • lignin is meant, conventionally, a condensation product comprising units resulting from the polymerization and / or condensation of at least one of the compounds of formulas (I) , (II) and (III): these compounds are also known respectively as coumaryl alcohol, coniferyl alcohol and sinapyl alcohol.
  • Lignin has motifs from the opening of the double bond carried by the above-mentioned compounds, at least one of the carbon atoms of this double bond may allow the bonding with another compound via a carbon atom of a double bond or via an atom carried by the phenyl ring (oxygen or carbon) or be oxidized to give an -OH function which itself can then recombine with another group.
  • radionuclide a radioactive element, which may be, for example, a fission element from nuclear fuels.
  • these compounds may exist under form of salts, such as, for example, lignosulfonates.
  • Lignins and lignocelluloses may be used in combination with organic or optionally inorganic additives, the resulting mixture preferably having a lignin or lignocellulose content of greater than 70% by weight relative to the mass. of the mixture.
  • the solution thus treated is intended to undergo calcination, such as to eliminate the water present therein and also to denitrate said solution.
  • the above-mentioned calcination step b) consists, in the conventional way, in removing the water present in the solution, this calcination step being able to be carried out by heating at a temperature ranging from 200 to 650 ° C.
  • This calcination step can be carried out in a rotary kiln heated by electric resistances.
  • the calcinate is then brought into contact with a glass frit, which may comprise SiO 2 and optionally one or more oxides selected from B 2 O 3 , Na 2 O, Al 2 O 3 , CaO, Fe 2 O 3 , NiO, CoO, ZrO 2 and mixtures thereof.
  • a glass frit which may comprise SiO 2 and optionally one or more oxides selected from B 2 O 3 , Na 2 O, Al 2 O 3 , CaO, Fe 2 O 3 , NiO, CoO, ZrO 2 and mixtures thereof.
  • the melt mixture from step e) Before being cooled in accordance with step f), the melt mixture from step e) can be placed in a container for storage after cooling.
  • the cooling step f) is a step which may consist of placing the molten mixture at rest without heating, for example for at least 24 hours, so that the mixture reaches a temperature below the recrystallization temperature of the glass.
  • the glass when the glass is contained in a container, the latter can be closed by a welded lid, for example, by means of an automatic plasma torch.
  • the resulting solution contains 7 mol / L nitrate ions NO 3 - .
  • model solution For the rest of the presentation, this solution is called “model solution”.

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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)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Glass Compositions (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
EP11703881.0A 2010-02-17 2011-02-15 Procede de traitement avant calcination d'une solution aqueuse nitrique comprenant au moins un radionucleide et eventuellement du ruthenium Active EP2537162B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1051132A FR2956517B1 (fr) 2010-02-17 2010-02-17 Procede de traitement avant calcination d'une solution aqueuse nitrique comprenant au moins un radionucleide et eventuellement du ruthenium
PCT/EP2011/052245 WO2011101358A1 (fr) 2010-02-17 2011-02-15 Procede de traitement avant calcination d'une solution aqueuse nitrique comprenant au moins un radionucleide et eventuellement du ruthenium

Publications (2)

Publication Number Publication Date
EP2537162A1 EP2537162A1 (fr) 2012-12-26
EP2537162B1 true EP2537162B1 (fr) 2013-12-11

Family

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Application Number Title Priority Date Filing Date
EP11703881.0A Active EP2537162B1 (fr) 2010-02-17 2011-02-15 Procede de traitement avant calcination d'une solution aqueuse nitrique comprenant au moins un radionucleide et eventuellement du ruthenium

Country Status (6)

Country Link
US (1) US9922741B2 (zh)
EP (1) EP2537162B1 (zh)
JP (1) JP5820824B2 (zh)
CN (1) CN102763168B (zh)
FR (1) FR2956517B1 (zh)
WO (1) WO2011101358A1 (zh)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2996149B1 (fr) 2012-09-28 2014-10-31 Commissariat Energie Atomique Membrane supportee fonctionalisee par des hexa- et octacyanometallates, son procede de preparation et procede de separation la mettant en oeuvre.
FR3003869B1 (fr) 2013-03-29 2015-05-01 Commissariat Energie Atomique Gel de decontamination pigmente et procede de decontamination de surfaces utilisant ce gel.
FR3003763B1 (fr) 2013-03-29 2015-05-15 Commissariat Energie Atomique Gel alcalin oxydant de decontamination biologique et procede de decontamination biologique de surfaces utilisant ce gel.
FR3014336B1 (fr) 2013-12-05 2016-01-22 Commissariat Energie Atomique Utilisation d'un gel alcalin oxydant pour eliminer un biofilm sur une surface d'un substrat solide.
FR3025115B1 (fr) 2014-09-03 2018-12-07 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede d'extraction selectif de platinoides, a partir d'un support les contenant, avec un milieu d'extraction comprenant un fluide supercritique et un ligand organique.
FR3025799B1 (fr) 2014-09-12 2016-10-14 Commissariat Energie Atomique Procede de preparation d'un materiau solide nanocomposite a base d'hexa- et octacyanometallates de metaux alcalins.
FR3054839B1 (fr) * 2016-08-05 2020-06-26 Commissariat A L'energie Atomique Et Aux Energies Alternatives Gel aspirable et procede pour eliminer une contamination radioactive contenue dans une couche organique en surface d'un substrat solide.

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249551A (en) * 1963-06-03 1966-05-03 David L Neil Method and product for the disposal of radioactive wastes
DK171737B1 (da) * 1987-03-09 1997-04-21 Metsae Serla Oy Fremgangsmåde til fremstilling af produkter af lignincellulosemateriale
JPH0721556B2 (ja) 1988-03-28 1995-03-08 動力炉・核燃料料開発事業団 気体状ルテニウムの生成を抑制した放射性廃液のガラス溶融固化処理方法
JPH06331793A (ja) * 1993-05-21 1994-12-02 Hitachi Ltd 硝酸溶液からのルテニウムの除去方法
US5960368A (en) * 1997-05-22 1999-09-28 Westinghouse Savannah River Company Method for acid oxidation of radioactive, hazardous, and mixed organic waste materials
RU2163505C1 (ru) * 2000-02-29 2001-02-27 Институт химии Коми научного центра Уральского отделения РАН Способ получения сорбентов радионуклидов
DE10045788A1 (de) * 2000-09-07 2002-04-04 Atc Dr Mann Verfahren zur Volumenreduzierung von radioaktiv belasteten Abfällen
EP1618067A2 (en) * 2003-04-21 2006-01-25 Manufacturing and Technology Conversion, Inc. Process for the treatment of waste or gaseous streams
UA78704C2 (en) * 2003-12-22 2007-04-25 Oleksandr Oleksandro Kapitonov Method for cleaning liquid radioactive waste and wastewater
WO2009155417A1 (en) * 2008-06-18 2009-12-23 Board Of Trustees Of The University Of Arkansas Microwave-assisted synthesis of carbon and carbon-metal composites from lignin, tannin and asphalt derivatives and applications of same

Also Published As

Publication number Publication date
JP2013519890A (ja) 2013-05-30
JP5820824B2 (ja) 2015-11-24
CN102763168A (zh) 2012-10-31
US20130023713A1 (en) 2013-01-24
WO2011101358A1 (fr) 2011-08-25
EP2537162A1 (fr) 2012-12-26
CN102763168B (zh) 2015-07-22
US9922741B2 (en) 2018-03-20
FR2956517A1 (fr) 2011-08-19
FR2956517B1 (fr) 2012-03-09

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