CN101994132B - Molten salt system based on oxide spent fuel dry-process aftertreatment - Google Patents

Molten salt system based on oxide spent fuel dry-process aftertreatment Download PDF

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CN101994132B
CN101994132B CN201010555928A CN201010555928A CN101994132B CN 101994132 B CN101994132 B CN 101994132B CN 201010555928 A CN201010555928 A CN 201010555928A CN 201010555928 A CN201010555928 A CN 201010555928A CN 101994132 B CN101994132 B CN 101994132B
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molten salt
lif
salt
spent fuel
salt system
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CN101994132A (en
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叶国安
欧阳应根
王长水
刘利生
常尚文
常利
何虎
郭建华
李瑞雪
高巍
高繁星
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China Institute of Atomic of Energy
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00Energy generation of nuclear origin
    • Y02E30/30Nuclear fission reactors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies

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Abstract

The invention discloses and a method for indissolvatingThe molten salt system of metal oxide dry post-treatment is LiF-AlF3A molten salt system, the fluxing salt being Li2CO3Wherein the molar ratio of LiF to AlF3 is 3-4.5: 1, the addition amount of the fluxing salt is 0.1-5% of the total mass of the molten salt. In this system F-Has the function of a buffering agent, and F is used for realizing the melting of oxides by molten salt-The corrosion rate to the associated equipment is reduced to an industrially acceptable level.

Description

Molten salt system based on the aftertreatment of oxide compound spent fuel dry method
Technical field
The invention belongs to fuel assembly behind the irradiation through the non-aqueous solution technical field of treatment scheme again, be specifically related to a kind of molten salt system that is used for the aftertreatment of insoluble metal oxide compound dry method.
Background technology
The dry method post-processing technology is to be grown up by the ANL of the U.S. and Muscovite RIAR, RICT.Russia carries out dry method electrolysis aftertreatment with several kilograms oxide compound spent fuel, proves that this technology is feasible on principle.The U.S. carries out the dry method electrolysis aftertreatment laboratory amplification test of metal spent fuel and also achieves success.At present, the fused salt process is to study one of four kinds of the most active dry method post-processing technologies.The principle of handling the oxide ceramics element be with contain uranium, plutonium are had strong complex performance complex anion salt (like Cl -, F -, SO 4 2-Deng) after the fusion, the oxide compound spent fuel is dissolved in this fused salt.The subject matter that this method exists is that the fused complex anion has serious corrodibility to material in the electrolytic system (like container, electrode etc.).
The Chinese nuclear science echnology report of publishing in calendar year 2001 " dry method post-processing technology typical process summary " is (CNIC-01638/38) in the literary composition; Ou Yangyinggen has summarized the molten salt system that multiple fused salt process is adopted; Wherein relatively be typically the metallic lithium reduced oxide electrorefining flow process that laboratory, U.S. Argonne proposes; In the LiCl fused salt, earlier the spent fuel oxide compound is reduced into corresponding metal, and then carries out electrorefining and reclaim the uranium plutonium.But the dissolving power to the oxide compound spent fuel of molten chloride is lower, and the spent fuel amount of fusing in the fused salt is very little, is not enough to be supported in carry out electrowinning in the fused salt.The Russian is oxidized to the sexavalence fusion with the uranium in the MOX powder, plutonium oxide direct chlorination in fused salt, makes the uranium plutonium that Cl is being arranged then 2+ O 2The cathodic reduction galvanic deposit of atmosphere is a uranium plutonium mixed oxide.The chloride oxidation fusion processes of MOX depends on fused salt composition and fused salt working temperature.What this flow process was used the earliest is the LiCl+KCl molten salt system, about 500 ℃ of working temperatures.For improving the fused salt working temperature, change the molten salt system that contains NaCl, CsCl at present.Using NaCl (800 ℃ of fusing points) mainly is in order to improve the working temperature of fused salt, and using CsCl is in order to improve the generation per-cent of sexavalence plutonium.Experiment finds that the interpolation of CsCl can improve the melting degree and the fusing speed of plutonium greatly.However, the recovery of plutonium still is difficult to reach satisfied index.
Summary of the invention
(1) goal of the invention
To the existing defective of molten salt system in the present dry method post-processing technology, the present invention aims to provide a kind of when the oxide compound spent fuel is had certain melting degree, reduces again the corrosive molten salt system of equipment and materials.
(2) technical scheme
A kind of molten salt system based on the aftertreatment of oxide compound spent fuel dry method is LiF-AlF 3Molten salt system, the salt of fluxing is Li 2CO 3, wherein LiF and AlF 3The mole proportioning be 3~4.5: 1, the salt addition of fluxing is 0.1~5% of a fused salt total mass.
As a kind of prioritization scheme, this molten salt system directly uses lithium type sodium aluminum fluoride and LiF, and the mol ratio of lithium type sodium aluminum fluoride and LiF is l: 0.02~l; The salt of fluxing is Li 2CO 3, addition is 0.1~5% of a fused salt total mass.
As a kind of further prioritization scheme, in the process of molten salt system operation, add the LiF that accounts for fused salt total mass 0.1~3%.
(3) invention effect
LiF-AlF 3Or lithium type sodium aluminum fluoride (the sodium aluminum fluoride molecular composition is Na 3AlF 6, have another name called sodium fluoroaluminate, hexafluoro closes sodium aluminate) during fusion, part is dissociated, and contains A1 in the melt 2F 7 -And F -, under the high temperature, with UO 2Form complex ion.The radius of oxonium ion and fluorion is more or less the same, and fluorion might replace oxonium ion and get into UO 2In the lattice, reaction as follows takes place:
O 2 -Displacement Al 2F 7 -The fluorine of middle fluorine bridged bond makes fused salt further dissociate F -Come, thereby reaction is moved to right, facilitate UO 2Fusion.In the high-temperature liquid state medium, O 2-Exchange is that mouthful j is contrary.Al 3+Be O 2-The strong cohesiveness acceptor, to O 2-Very strong avidity is arranged, and therefore, molten cryolitic has melting ability preferably to MOX.Al 3+Further with UO 2Dissociation product UOF 2Exchange 0 2-And generation UF 5 -, UF 6 2-Deng.Therefore, at LiF-AlF provided by the present invention 3Molten salt system, F -Effect with buffer reagent, when realizing fused salt fusion oxide compound, F -Erosion rate to relevant device is reduced to industrial acceptable degree.
Embodiment
Below by embodiment, technical scheme provided by the present invention is further elaborated.
Embodiment 1
The used reagent of present embodiment is following:
Lithium fluoride (analytical pure; Chemical Reagent Co., Ltd., Sinopharm Group), three hydration ALUMNIUM FLUORIDE (CPs; Chemical Reagent Co., Ltd., Sinopharm Group), Quilonum Retard (analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group), platinum filament (Φ 1mm, 99.9%; Alfa Aesar), uranous oxide (Baotou rare earth emtallurgy research institute), graphite rod (6mm, three high graphite, Beijing three industry graphite companies).
Take by weighing 41g LiF and 42g AlF 3, take by weighing 3g Li 2CO 3In this molten system, LiF and AlF 3The mole proportioning be 3.3:1, salt Li fluxes 2CO 3Addition be that the per-cent of total mass is 3.6%.Salt Li fluxes 2CO 3Play the effect of fluxing with excessive LiF with reduction melt fusing point.
Load weighted salt mixed be placed in the plumbago crucible, crucible is placed in the quartz sleeve, takes by weighing the UO of about 6g 2Powder joins in the dried salt.Logical argon gas transfers to 900 ° of C~950 ° C with the electric furnace preset temp in sleeve, when salt melts, adds the LiF of 0.09g again.Stir melt with stainless steel strip, get supernatant liquid then, analyze UO 2Solubleness.After sampling is accomplished, carry out CV scanning, carry out potentiostatic electrodeposition based on the information of CV scanning gained.The result shows, obtains dendritic settling on the stainless steel cathode, and the content of U is 49 times in the fused salt in this settling.
Embodiment 2
Operation is like embodiment 1.Each drug dosage is following:
LiF 36g and AlF 340g, Li 2CO 30.08g.The add-on of LiF is 1.5g.
Embodiment 3
Operation is like embodiment 1.Each drug dosage is following:
LiF 36g and AlF 326.7g, Li 2CO 33.1g.The add-on of LiF is 2.0g.
Embodiment 4
Experiment condition such as embodiment 1.
Take by weighing the lithium type sodium aluminum fluoride of 73g, the LiF of 12g and the Li of 0.09g 2CO 3Load weighted salt mixed be placed in the plumbago crucible, crucible is placed in the quartz sleeve, takes by weighing the UO of about 12g 2Powder joins in the dried salt.Logical argon gas transfers to 900 ° of C~950 ° C with the electric furnace preset temp in sleeve, when salt melts, adds the LiF of 0.09g again.Stir melt with stainless steel strip, get supernatant liquid then, analyze UO 2Solubleness.After sampling is accomplished, carry out CV scanning, carry out potentiostatic electrodeposition based on the information of CV scanning gained.The result shows that the content of U is 41 times in the fused salt in the dendritic settling of stainless steel cathode.
Embodiment 5
Experiment condition such as embodiment 4.Each drug dosage is following:
Lithium type sodium aluminum fluoride 146g, LiF 12g, Li 2CO 33.2g.The LiF that adds again is 3.2g.
Embodiment 6
Experiment condition such as embodiment 4.Each drug dosage is following:
Lithium type sodium aluminum fluoride 180g, LiF 0.6g, Li 2CO 39.3g.The LiF that adds again is 5.7g.
Obviously those skilled in the art can carry out various modifications and modification and not break away from the spirit and scope of the present invention the present invention.Like this, if of the present invention these revise and modification belongs in the scope of its equivalent technologies of claim of the present invention, then the present invention also is intended to comprise these modifications and modification.

Claims (3)

1. the molten salt system based on the aftertreatment of oxide compound spent fuel dry method is LiF-AlF 3Molten salt system, LiF and AlF 3The mole proportioning be 3~4.5:1; Perhaps this molten salt system directly uses lithium type sodium aluminum fluoride and LiF, and the mol ratio of lithium type sodium aluminum fluoride and LiF is 1:0.02~1;
The salt of fluxing is Li 2CO 3, the salt addition of fluxing is 0.1~5% of a fused salt total mass.
2. the molten salt system based on the aftertreatment of oxide compound spent fuel dry method according to claim 1 is characterized in that: in the process of molten salt system operation, add the LiF that accounts for fused salt total mass 0.1~3%.
3. the molten salt system based on the aftertreatment of oxide compound spent fuel dry method according to claim 1 and 2 is characterized in that: fused salt dissolved temperature is 900 ° of C~950 ° C.
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Publication number Priority date Publication date Assignee Title
CN104562089B (en) * 2014-10-17 2017-03-22 中国原子能科学研究院 Method for preparing initial molten salt system in molten salt electrolysis dry after-treatment process
CN105132953B (en) * 2015-07-24 2017-11-21 中国原子能科学研究院 A kind of spentnuclear fuel dry method post-processing approach for being used to directly obtain zircaloy fuel
JP6839719B2 (en) * 2016-03-16 2021-03-10 リチャード スコット,イアン Conversion of used uranium oxide fuel to molten salt reactor fuel
CN109637682B (en) * 2018-11-05 2020-09-04 中国科学院上海应用物理研究所 Method for reconstructing molten salt reactor fuel
CN110444312B (en) * 2019-09-03 2020-12-29 中国科学院近代物理研究所 Separation of medical isotopes from uranium fission products by dry distillation131Method of I

Non-Patent Citations (2)

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M. Ambrova´et al.Solubilities of lanthanum oxide in fluoride melts Part I. Solubility in M3AlF6 (M = Li, Na, K).《Thermochimica Acta》.2006,第443卷第105-108页. *
邱竹贤.铝电解质体系及其性质.《铝电解》.冶金工业出版社,1995,第46,80-81页. *

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