EP2101333B1 - Verfahren zur umverarbeitung von flüssigen radioaktiven abfallstoffen - Google Patents

Verfahren zur umverarbeitung von flüssigen radioaktiven abfallstoffen Download PDF

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Publication number
EP2101333B1
EP2101333B1 EP07852046.7A EP07852046A EP2101333B1 EP 2101333 B1 EP2101333 B1 EP 2101333B1 EP 07852046 A EP07852046 A EP 07852046A EP 2101333 B1 EP2101333 B1 EP 2101333B1
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EP
European Patent Office
Prior art keywords
radionuclides
layer
solution
synthesis
oxides
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.)
Not-in-force
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EP07852046.7A
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English (en)
French (fr)
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EP2101333A1 (de
EP2101333A4 (de
Inventor
Valentin Alexandrovich Avramenko
Vitaly Georgievich Dobrzhansky
Valentin Ivanovich Sergienko
Sergei Ivanovich Shmatko
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Obschestvo S Ogranichennoi Otvetstvennostyu "nauka
Original Assignee
Obschestvo S Ogranichennoi Otvetstvennostyu "Nauka - Tekhnologii - Proizvodstvo"
OBSCHESTVO S OGRANICHENNOI OTVETSTVENNOSTYU NAUKA T PROIZV
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Publication of EP2101333A1 publication Critical patent/EP2101333A1/de
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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
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/16—Processing by fixation in stable solid media
    • G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites

Definitions

  • the invention relates to protection of the environment, namely methods for liquid radioactive waste (LRW) reprocessing comprising immobilizing same into a crystal material, acceptable from the viewpoint of ecology and the invention can be used at facilities of atomic power industry and chemical-metallurgical production lines.
  • LRW liquid radioactive waste
  • Liquid radioactive waste reprocessing is connected with the necessity to attain a safe long-term storage of radioactive waste (RAW), for which purpose hard radioactive waste (HRW) change into a state providing for a minimum leaching-out of radionuclides with natural waters.
  • RAW radioactive waste
  • HRW hard radioactive waste
  • This task is solved by conventional methods such as bituminization, cementation and vitrification of RAW (patent RU N 2088986, 27.08.1997 ; patent RU N 2271586, 10,03.2006 ; patent RU N 2131152, 27.05.1999 ; Donald I.W., Metcalfe B.L., Taylor R.N.J. The immobilization of high level radioactive wastes using ceramics and glasses. Review. Journal of Materials Science, 32, 1997. p. 5856-5862 ), The least degree of leaching is provided with RAW vitrification and has a value of about 10 -6 g/cm. day.
  • Such forms of RAW immobilization are ceramic material widely known by the trade name Syncron whose matrix is normally a combination of hollandite (BaAl 2 Ti 2 O 6 or BaAl 2 Ti 6 O) 6 ), perovskite (CaTiO 3 ) and zirconolite (CaZrTi 2 O 7 ).
  • Sorption reactant materials are the new promising materials for the recovery of radionuclides.
  • sorption-reactant materials resides in continuously forming an insoluble compound sorbing radionuclides in a porous matrix of inert material, with a continuous growth of crystals of the insoluble compound concurrently with sorption of the radionuclides.
  • the result there form crystal materials with a very small interface surface and sorbed radionuclides distributed over entire volume of the crystal material; such being the case, the leaching of radionuclides from sorption-reactant materials is by several orders lower than from selective ion - exchange sorbents having a large exchange capacity and, as so, a large interface surface.
  • patent RU No 2185671 20.07.2002 discloses the recovery of strontium radionuclides from solutions with a high content of hardness salts and liquid radioactive wastes of a complex chemical composition.
  • SRMs are formed directly in the process of purification due to reaction of a starting sorption-reactant material comprising barium exchange cations, with a sulfate-ion purifying containing solution with the formation of insoluble barium sulfate crystallzable in the matrix of the sorption-reactant material.
  • An object of the present invention is to provide of a method of reprocessing liquid radioactive wastes containing long-lived radionuclides, preferably cobalt, manganese and strontium in hydrothermal conditions, which provides a high degree of purification of solutions from radionuclides, as required, a high separation coefficient (a ratio of purified LRW/HRW volumes), formation of a strong durable ceramic matrix with a minimum leaching-out of the radionuclides.
  • the problem is solved by a method of reprocessing liquid radioactive wastes containing long-lived radionuclides by synthesis of insoluble compounds immobilizing the long-lived radionuclides into a crystal lattice under hydrothermal conditions in a flow by passing LRWs being treated and reagents required for the synthesis through a layer of transition metal oxides at a rate providing for crystallizing of synthesizable radionuclide-containing compounds on the surface of the particles of the layer of oxides.
  • the transition metal oxides used are represented by iron oxide and/or manganese oxide and/or cobalt oxide and/or zirconium oxide.
  • the conditions for hydrothermal synthesis are a temperature comprised between 180 and 250°C and a pressure between 2.026 to 15.2 MPa (20 and 150 atm).
  • crystallization means the change of a substance from the liquid state to the solid crystal state and the term “crystallization on the surface of particles” is heterogenic formation of a crystal phase on the surface of a solid.
  • phase in the context of the present invention one should imply a generally accepted in the art, uniform in formulation and properties, part of a thermodynamic system separated from other phases by interfaces on which some of the properties of the system change stepwise.
  • immobilization in the present invention one should imply inclusion of radionuclides in a crystal lattice of insoluble compounds crystallizable on the surface of particles of a layer.
  • the speed of passing of LRW solutions through the layer of particles should be such that the formation of crystals on the surface of the layer of immobilizing radionuclide particles provide the desirable degree of purification from the radionuclides.
  • the speed of a flow is greater than a certain value determined experimentally in each and every particular case there occurs crystallization in the volume of a solution but not the surface of particles of the layer and more than that a portion of radionuclides containing crystals are lift out of the layer and no purification occurs whatsoever.
  • a solution being treated should contain ions forming under hydrothermal conditions the crystals of compounds immobilizing radionuclides.
  • reagents which would supply presence with ions required for the synthesis in the solution are added to the solution of LRW, said reagents being represented by oxidants such as hydrogen peroxide or potassium permanganate, oxidizing ions within the LRWs to an oxidation state of formation of insoluble compounds, and/or metal salts.
  • Fig. 1 shows the ASM-pictures of particles of a layer before hydrothermal synthesis (initial particle), Fig. 2 - in the process of synthesis, Fig. 3 - upon completion of hydrothermal synthesis.
  • a method for any one of the alternative embodiments is realized as followings.
  • Reagents as required depending on the type of the LRWs being processed are added to the feeding LRW followed by feeding LRWs to the flow reactor for hydrothermal synthesis in which a layer of particles of insoluble compounds is placed.
  • Synthesis is carried out in a temperature range of 180 to 250°C, at a pressure of 2.026-15.2MPa (20 to 150 atm), which corresponds to the sufficient rate of crystal growth and the desirable degree of purification from radionuclides.
  • the compounds resulting from hydrothermal synthesis are deposited on insoluble particles forming the layer.
  • a radionuclide-free solution is a process radioactive-free waste material.
  • the layered structure of a synthesized compound which grows on an initial globular structure is seen on the pictures.
  • EXAMPLE 1 (not forming part of the claimed invention; Variant 1).
  • LRWs containing 2 g/l Trilon B and 0.5 g/l trisodium phosphate having a 0.1 g/l concentration of calcium ions and comprising strontium-90 radionuclides (1.5 ⁇ 10 -6 Ci/l) are passed through a layer of hydroxylapatite Ca 3 PO 4 ⁇ Ca(OH) 2 having a particle size of 0.1-0.3 mm, charged into a heated cylindrical reactor dimensioned 100 x 10 mm.
  • the process is carried out at the flow speed of I ml/min., at the temperature of 200°C and pressure of 100 atm (10.13 MPa).
  • a solution flow is provided with a chromatographic high pressure pump.
  • EXAMPLE 2 (Variant 2).
  • the bottoms of a nuclear waste evaporators which are purified from cesium radionuclides by filtration through ferrocyanide sorbents and contained cobalt-60 radionuclides (1 ⁇ 10 -5 Ci/l) and manganese-54 (1 ⁇ 10 -8 Ci/l) are passed through a layer of iron-cobalt ferrite (iron-cobalt oxides) with an iron to cobalt molar ratio of 1:01 and a particle size of 0.2-0.5 mm charged into a heated cylindrical reactor dimensioned 100 x10 mm.
  • the process is carried out at the flow speed of 2 ml/min., at the temperature of 220°C and pressure of 100 atm (10.13 MPa).
  • a solution flow is provided with a high pressure chromatographic pump. Simultaneously 6% solution of hydrogen peroxide is added to the reactor by the second high pressure pump at the rate of 0.6 ml/min.
  • Activity of the effluent solution and the leaching coefficients of cobalt radionuclides from the charge of oxides formed, as specified upon completion of a test are given in Table 2.
  • EXAMPLE 3 (Variant 3). LRWs containing 2 g/l Trilon B and 0.5 g/l trisodium phosphate having a concentration of calcium ions of 0,1 g/l and comprising strontium-90 radionuclides (1.5 ⁇ 10 -6 Ci/l) are passed through a layer of zirconium oxide having a particle size of 0.1-0.3 mm, charged into a heated cylindrical reactor dimensioned 100 x 10 mm. The process proceeds at the speed of a flow of 1 ml/min., at 200°C and the pressure of 10.13 MPa (100 atm). A solution flow is provided with a chromatographic high pressure pump.
  • EXAMPLE 4 Sea water contaminated with strontium-90 radionuclides, 2 ⁇ 10 -6 Ci activity, is passed through a layer of manganese dioxide having a particle size of 0.05-0.1 mm, charged in a heated cylindrical reactor dimensioned 100 x 10 mm. The process is carried out at the speed of a flow of 1 ml/min. at 220°C and the pressure of 10.13 MPa (100 atm). A solution flow is provided with a high pressure chromatographic pump. A solution 0.1 n manganese (II) chloride and 0.1 n potassium permanganate solution were added to the reactor by high pressure pumps at the rate of 0.6 ml/min.
  • EXAMPLE 5 LRWs being decontaminated containing 2 g/l sodium oxalate and 0.5 g/l Trilon B purified from cesium radionuclides by filtration through ferrocyanide sorbents and comprising cobalt - 60 (1 ⁇ 10 -7 Ci/l) and strontium-90 (4 ⁇ 10 -7 Ci/l) radionuclides are successively passed through a layer of iron-cobalt ferrite with a molar ratio of iron: cobalt of 1: 0.1 and a particle size of 0.2-0.5 mm, charged in a heated cylindrical reactor dimensioned 100 x 10 mm and through a layer of manganese dioxide having a particle size of 0.05-0.1 mm, charged in the heated cylindrical reactor dimensioned 100 x 10 mm.
  • the process proceeds at the speed of a flow of 1 ml/min, at 200°C and pressure of 100 bar.
  • a solution flow is provided a high pressure chromatographic pump.
  • Simultaneously 6% hydrogen peroxide solution at the rate of 0.6 ml/min is added to the first reactor and 0.1 n manganese (II) chloride solution is added to the second reactor by the high-pressure pump.
  • EXAMPLE 6 Alkali LRWs containing 0.3 g/l sodium hydroxide cobalt-60 (1 ⁇ 10 -7 Ci/l) and cesium - 137 (6 ⁇ 10 -7 Ci/l) radionuclides are passed through a layer of perlite-filter with the contained 3.4% iron, charged in a heated cylindrical reactor dimensioned 100 x 10 mm. The process is conducted at the speed of a flow of 0.3 ml/min. at 170°C and the pressure of 10.13 MPa (100 atm). A solution flow is provided with the high - pressure chromatographic pump.

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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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Claims (2)

  1. Verfahren zur Aufbereitung von flüssigen radioaktiven Abfällen LRW, die langlebige Radionuklide enthalten durch die Synthese von unlöslichen Verbindungen, die die langlebigen Radionuklide in einem Kristallgitter immobilisieren, dadurch gekennzeichnet, dass die Synthese einer Kristallphase unter hydrothermalen Bedingungen in einem Temperaturbereich von 180°C bis 250°C und einem Druckbereich von 2,026 bis 15,2 MPa (20 bis 150 Atm) in einem Strom durchgeführt wird, indem die zu verarbeitenden LRW und die für die Synthese benötigten Reagenzien durch eine Schicht aus Eisenoxid und/oder Manganoxid und/oder Kobaltoxid und/oder Zirkoniumoxid mit einer Geschwindigkeit geleitet werden, die die Kristallisation von synthetisierbaren Radionuklid-haltigen Verbindungen auf der Partikeloberfläche der Oxidschicht gewährleistet.
  2. Verfahren zur Aufbereitung gemäß Anspruch 1, dadurch gekennzeichnet, dass die Kristallphase als Oxide synthetisiert wird und dass die synthetisierbaren Radionuklid-haltigen Verbindungen Oxide sind.
EP07852046.7A 2006-12-06 2007-11-07 Verfahren zur umverarbeitung von flüssigen radioaktiven abfallstoffen Not-in-force EP2101333B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2006143293/06A RU2321909C1 (ru) 2006-12-06 2006-12-06 Способ переработки жидких радиоактивных отходов (варианты)
PCT/RU2007/000614 WO2008069694A1 (fr) 2006-12-06 2007-11-07 Procédé de transformation de déchets radioactifs liquides (et variantes)

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EP2101333A1 EP2101333A1 (de) 2009-09-16
EP2101333A4 EP2101333A4 (de) 2011-04-13
EP2101333B1 true EP2101333B1 (de) 2014-04-30

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WO (1) WO2008069694A1 (de)

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RU2537391C1 (ru) * 2013-07-01 2015-01-10 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Дальневосточный федеральный университет (ДВФУ) Способ переработки жидких радиоактивных отходов
RU2643362C1 (ru) * 2017-01-16 2018-02-01 Российская Федерация, от имени которой выступает Госкорпорация "Росатом" Способ обращения с радиоактивными растворами после дезактивации поверхностей защитного оборудования
DE102018114550A1 (de) * 2018-06-18 2019-12-19 Nukem Technologies Engineering Services Gmbh Verfahren zum Vorreinigen von Radionuklide enthaltenden Lösungen

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DE3833676A1 (de) * 1988-10-04 1990-04-05 Petri Juergen Dipl Ing Dr Verfahren zur endlagerung von eingebundenen abfallstoffen
JP3074079B2 (ja) * 1992-11-24 2000-08-07 株式会社東芝 放射性廃溶媒の固化処理方法
US5678233A (en) * 1994-09-14 1997-10-14 Brown; Paul W. Method of immobilizing toxic or radioactive inorganic wastes and associated products
RU2088986C1 (ru) 1994-12-15 1997-08-27 Всероссийский научно-исследовательский институт неорганических материалов им.акад.А.А.Бочвара Способ отверждения фильтроперлитных пульп
RU2131152C1 (ru) 1998-02-24 1999-05-27 Чечельницкий Геннадий Моисеевич Способ обработки жидких радиоактивных отходов ядерной энергетической установки
IL136685A0 (en) * 2000-06-12 2001-06-14 Gribbitz Arthur Process for treatment of radioactive waste
RU2185671C1 (ru) * 2001-01-10 2002-07-20 Государственное учреждение - Институт химии Дальневосточного отделения РАН Способ извлечения радионуклида стронция из водных растворов (варианты)
RU2212069C2 (ru) * 2001-04-17 2003-09-10 Производственное объединение "МАЯК" Способ отверждения растворов долгоживущих радионуклидов
RU2271586C2 (ru) 2004-04-01 2006-03-10 Федеральное государственное унитарное предприятие "Государственный научный центр Российской Федерации - Физико-энергетический институт им. А.И. Лейпунского" Способ иммобилизации концентрированных жидких радиоактивных отходов (варианты)

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RU2321909C1 (ru) 2008-04-10
EP2101333A1 (de) 2009-09-16
EP2101333A4 (de) 2011-04-13
WO2008069694A1 (fr) 2008-06-12

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