WO2020040668A1 - Procédé de retraitement de combustible nucléaire oxydé - Google Patents

Procédé de retraitement de combustible nucléaire oxydé Download PDF

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Publication number
WO2020040668A1
WO2020040668A1 PCT/RU2019/000717 RU2019000717W WO2020040668A1 WO 2020040668 A1 WO2020040668 A1 WO 2020040668A1 RU 2019000717 W RU2019000717 W RU 2019000717W WO 2020040668 A1 WO2020040668 A1 WO 2020040668A1
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WO
WIPO (PCT)
Prior art keywords
oxide
nuclear fuel
electrolysis
lithium
anode
Prior art date
Application number
PCT/RU2019/000717
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English (en)
Russian (ru)
Inventor
Юрий Павлович ЗАЙКОВ
Владимир Юрьевич ШИШКИН
Вадим Анатольевич КОВРОВ
Альберт Рафаэльевич МУЛЛАБАЕВ
Андрей Викторович СУЗДАЛЬЦЕВ
Original Assignee
Акционерное общество "Прорыв"
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Application filed by Акционерное общество "Прорыв" filed Critical Акционерное общество "Прорыв"
Publication of WO2020040668A1 publication Critical patent/WO2020040668A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C19/00—Arrangements for treating, for handling, or for facilitating the handling of, fuel or other materials which are used within the reactor, e.g. within its pressure vessel
    • G21C19/42—Reprocessing of irradiated fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors

Definitions

  • the invention relates to nuclear energy, in particular, to methods for processing oxide nuclear fuel, and can be used mainly in a closed nuclear fuel cycle (NFC).
  • NFC closed nuclear fuel cycle
  • This method involves the electrolysis of a melt based on lithium chloride with the addition of May 1.0. % lithium oxide, while electrolysis is carried out at an anode current density of 0.3 A / cm 2 and a temperature of not higher than 700 ° C, and Pt, Rh, Pd, Ir, Au are used as an anode.
  • the objective of the present invention is to develop a method for processing spent and rejected oxide nuclear fuel, which can simultaneously reduce the fuel exposure before reprocessing and carry out a stable and lengthy reprocessing to produce pure metals - components of nuclear fuel.
  • a method for processing oxide nuclear fuel which, like the prototype method, includes the recovery of components of oxide nuclear fuel during the electrolysis of molten lithium chloride with the addition of lithium oxide in an amount of at least May 1. % using an oxygen-releasing anode, while electrolysis is carried out at the anode current density not higher than 0.3 A / cm 2 and temperature not higher than 700 ° C.
  • the claimed method is characterized in that during electrolysis, anodes of NiO or TiO 2 are used , doped with lithium oxide Li 2 0 in an amount of not less than 1 wt.%.
  • NiO anodes are used as an oxygen-releasing anode or TU 2 doped with lithium oxide in an amount of not less than 1 wt.%.
  • lithium is released during electrolysis at the cathode, which reacts with oxide components to form metals and oxygen-containing ions.
  • anodes of NiO or TU 2 doped with lithium oxide in an amount of at least May 1. %, leads to the fact that during the electrolysis of the molten lithium chloride with additives of at least May 1. % Of lithium oxide, an anode current density not higher than 0.3 A / cm 2 and a temperature of not higher than 700 ° C at the anodes of the NiO-Li 2 0 or Ti0 2 -Li 2 0 occurs the formation of new compounds with lithium oxide as in the prior art. Moreover, even with an increase in the anode current density above 0.3 A / cm 2, such anodes are not prone to anodic dissolution; the limitation of the anode density to 0.3 A / cm 2 is caused only by difficulties in the melt.
  • lithium oxide is sufficient for oxygen evolution at the anodes without significant diffusion difficulties. This is achieved with a higher content, however, an increase in the content of lithium oxide in the melt more than May 3. % is not recommended because negatively affects the removal of oxygen-containing ions from the cathode space and the completeness of recovery of the components of oxide nuclear fuel. Because oxide doped with lithium anodes NiO-Li 2 0 or Ti0 2 -Li 2 0, with the electrolysis conditions necessary for the reduction of lithium at the cathode and the processing of oxide nuclear fuel are not subjected to anodic or chemical oxidation, the resource of use of the anodes is significantly increased, which leads to the possibility of complete processing of the components of oxide nuclear fuel without stopping the electrolysis. The fact that the electrolysis of lithium chloride melt with the addition of lithium oxide is recommended to be carried out at a temperature not exceeding 700 ° C is due to a sharp increase in the vapor pressure of the components of the melt.
  • Doping of NiO and TIG with lithium oxide L12O in an amount of at least May 1. % allows, firstly, to reduce the electrical resistance of these oxide mixtures, and secondly, eliminates the occurrence of unsteady side processes of uneven incorporation of lithium oxide in the crystal lattices of NiO and T1O2. Both factors are essential for the stable operation of the anodes of NiO-L ⁇ O and Tyb-L ⁇ O during electrolysis. It should be noted that the increase in lithium oxide in the anodes of NiO and T1O2 over May 2. % is inefficient, and can lead to destruction of the anodes.
  • the claimed method allows for the complete processing of oxide nuclear fuel without stopping the electrolysis and the need to replace the anode.
  • the technical result achieved by the claimed method is to increase the resource use of anodes in the complete processing of oxide nuclear fuel.
  • FIG. 1 shows photographs of the anode of lithium oxide doped NiO-L O before and after electrolysis of the melt; in FIG. 2 - reduced uranium; in FIG. 3 - x-ray of reduced uranium.
  • uranium oxide UO2 which is one of the main components of oxide nuclear fuel.
  • a laboratory electrolyzer was constructed, which is a crucible of MgO oxide, in which was loaded with pre-prepared reagents: lithium chloride weighing 120.2 g and lithium oxide weighing 1.22 g (May 1.0.%).
  • the reagent crucible was placed in a quartz tube, the upper part of which was closed with a special fluoroplastic cap with gas ducts and holes for electrodes and thermocouples.
  • the laboratory electrolyzer in a closed quartz tube was placed in a resistance furnace and heated to a temperature of 625 ° C. After melting the mixture of lithium chloride and lithium oxide, the electrodes were immersed in the melt and the molten mixture was electrolyzed at an anode current density of 0.3 A / cm 2 and a cathodic current density of at least 0.5 A / cm 2 .
  • the anode overvoltage was recorded and the end of the process was determined by its sharp increase.
  • the anode overvoltage was 0.35 ⁇ 0.04 V, and the voltage between the anode and cathode was 3.7 ⁇ 0.06 V, which indicates the stability of the electrolysis parameters.
  • the electrodes were removed from the melt and the electrolyzer with a quartz tube was cooled to room temperature. After cooling, the anode and the obtained uranium powder were washed from the melt, weighed, and analyzed. The mass of the anode from NiO-LbO did not change, and the mass of the obtained uranium was 11.2 g, which corresponds to the complete reduction of UO2 oxide. In this case, impurities of Ni and other elements in uranium were not detected.
  • a similar result was obtained during the processing of 1yr oxide by electrolysis of a lithium chloride melt with the addition of May 2.23. % LhO and using an anode Tyb-bO. This is due to the similarity of the main regularities of the anode process at the anodes of lithium oxide doped NiO-LhO and Tyr-LiO in the electrolysis of molten lithium chloride with the addition of lithium oxide.
  • alkali and / or alkaline-earth metal chlorides and / or oxides can be introduced into the melt based on lithium chloride with the addition of lithium oxide, which do not affect the overall recovery mechanism of the components of oxide nuclear fuel.
  • the claimed method of processing oxide nuclear fuel allows both to reduce the exposure of fuel before processing and to carry out a stable and lengthy processing process to produce pure metals - components of nuclear fuel.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention se rapport au domaine de l'énergie nucléaire et peut être utilisée essentiellement dans un cycle de combustible nucléaire fermé. Le procédé consiste à restaurer les composants du combustible nucléaire oxydé lors d'une électrolyse d'un bain de fusion de chlorure de lithium avec un ajout d'oxde de lithium dans une quantité d'au moins 1 % en poids en utilisant une anode dégageant de l'oxygène faite de NiO ou TiO2 dopés par par de l'oxyde de lithium dans une quantité d'au moins 1 % en poids, et l'électrolyse se fait selon une densité anodique de courant ne dépassant pas 0,3 А/сm2 et à une température ne dépassant pas 700°C. Ce procédé permet simultanément de réduire la mise en attente du combustible avant le retraitement et d'effectuer un processus stable et en longueur de retraitement afin d'obtenir des métaux purs qui sont des composants du réacteur nucléaire.
PCT/RU2019/000717 2018-08-22 2019-10-08 Procédé de retraitement de combustible nucléaire oxydé WO2020040668A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2018130442 2018-08-22
RU2018130442A RU2700934C1 (ru) 2018-08-22 2018-08-22 Способ переработки оксидного ядерного топлива

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WO2020040668A1 true WO2020040668A1 (fr) 2020-02-27

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RU2766563C2 (ru) * 2020-08-16 2022-03-15 Акционерное общество «Прорыв» Способ переработки нитридного ОЯТ в солевых расплавах с выделением целевого компонента с помощью осадителя

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RU2497979C1 (ru) * 2012-06-15 2013-11-10 Открытое акционерное общество "Сибирский химический комбинат" Способ получения металлического урана

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KR100593790B1 (ko) * 2003-03-28 2006-07-03 한국원자력연구소 ＬｉＣｌ－Ｌｉ₂Ｏ 용융염계를 이용하여 산화물핵연료로부터 핵연료 금속을 제조하는 방법, 상기 방법을구현하기 위한 환원전극, 및 상기 환원전극을 포함하는환원장치
RU2537622C1 (ru) * 2013-06-21 2015-01-10 Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук Состав шихты для изготовления оксидно-металлического инертного анода

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RU2497979C1 (ru) * 2012-06-15 2013-11-10 Открытое акционерное общество "Сибирский химический комбинат" Способ получения металлического урана

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A. YASINSKIY ET AL.: "Progress of inert anodes in aluminum industry", JOURNAL OF SIBERIAN FEDERAL UNIVERSITY, CHEMISTRY, vol. 1, 3 March 2018 (2018-03-03), pages 18 - 29, XP055687666, DOI: 10.17516/1998-2836-0055 *
SUNG-WOOK K ET AL.: "Electrochemical properties of noble metal anodes for electrolytic reduction of uranium oxide", J RADIOANAL NUCL CHEM., vol. 311, 2017, pages 809 - 814, XP036127862, DOI: 10.1007/s10967-016-5107-8 *

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