CN105913887B - It is a kind of to use formaldoxime to be stripped the plutonium purification cycle technique of reagent - Google Patents

It is a kind of to use formaldoxime to be stripped the plutonium purification cycle technique of reagent Download PDF

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CN105913887B
CN105913887B CN201610232040.8A CN201610232040A CN105913887B CN 105913887 B CN105913887 B CN 105913887B CN 201610232040 A CN201610232040 A CN 201610232040A CN 105913887 B CN105913887 B CN 105913887B
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plutonium
concentration
formaldoxime
purification cycle
stripped
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CN105913887A (en
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肖松涛
刘协春
罗方祥
李丽
杨贺
兰天
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China Institute of Atomic of Energy
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    • 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
    • G21C19/50—Reprocessing of irradiated fuel of irradiated fluid fuel, e.g. regeneration of fuels while the reactor is in operation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/04—Obtaining plutonium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
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  • High Energy & Nuclear Physics (AREA)
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Abstract

The invention belongs to nuclear fuel to post-process field.To solve the problems such as existing Purex flow plutonium purification cycle plutonium enriched level using salt-free go back original reagent is relatively low, security is poor, formaldoxime is used to be stripped the plutonium purification cycle technique of reagent the invention provides a kind of.The technique includes：2BX formaldoxime concentration is 0.5 0.7mol/L, and 2BF concentration of nitric acid is 0.15 0.3mol/L, and 2BS concentration of nitric acid is 0.1 0.5mol/L, and stream compares 2BF:2BX=3 5:1, series >=10 grade are stripped, mend 35 grades of series of extraction.The plutonium purification cycle technique of the present invention can realize that stripping process plutonium concentrates more than 5 times, the plutonium concentration of gained plutonium product liquid reaches as high as 60g/L, higher plutonium yield and good uranium removal effect are achieved, operation stability is good in process condition range, has preferable economy.

Description

It is a kind of to use formaldoxime to be stripped the plutonium purification cycle technique of reagent
Technical field
The invention belongs to nuclear fuel to post-process field, more particularly to a kind of to use formaldoxime to be followed for the plutonium purifying of back extraction reagent Ring technique.
Background technology
Purex flow is the flow that current reprocessing plant mainly uses, and the flow includes co-decotamination cycle, uranium purification cycle With plutonium purification cycle.Wherein, the purpose of plutonium purification cycle is thick to being obtained by co-decotamination cycle by extraction and stripping process Plutonium product is purified and concentrated, and qualified plutonium product is finally given, referring to accompanying drawing 1.
To ensure the plutonium yield of whole post processing flow, usually requiring that the plutonium yield of plutonium purification cycle must reach 99.9%.Because plutonium purification cycle has the characteristics of organic phase plutonium concentration larger (more than 10g/L), therefore concentrated in the back extraction of plutonium During, with the raising of back extraction cycles of concentration, realize that the difficulty of 99.9% yield increases in geometric progression, form plutonium purifying and follow The difficult point of ring process.
In plutonium purification cycle, the use of salt-free go back original reagent can reduce the radwaste volume of last handling process, Simplify Purex flow technique, improve the economic benefit of post processing, therefore the research and development of salt-free go back original reagent are the masters of Purex flow Want one of research contents.At present, the salt-free go back original reagent for being usually used in plutonium purification cycle mainly has two groups, is respectively：1. azanol-hydrazine System, 2. dimethyl hydroxylamines-hydrazine system.
Azanol (NH2OH) there is great reproducibility, so widely being closed in the research of salt-free go back original reagent Note.Barney have studied azanol in HNO3In solution reduce Pu (IV) reaction, from reaction rate equation as can be seen that reaction by Effect of Acidity On Absorption is larger, and as acidity increases, reaction speed significantly slows down, thus azanol low acid, under hot conditions to Pu (IV) Reduction effect it is preferable.Azanol major advantage is to be completely broken down as nitrogen, nitrous oxide etc. relatively as reducing agent The gas of safety, but hydroxylamine reduction Pu (IV) speed is relatively slow, it is necessary to be lot more time to reaction completely.It is same with this When, realize that plutonium yield reaches 99.9% general technology condition as 2BF using azanol-hydrazine as plutonium reduction reextraction reagent:2BX:2BS =2:1:0.3,12 grade of back extraction, 2 grades are mended extraction, wherein back extraction cycles of concentration is maximum no more than 2.3, mend extraction series no more than 3 Level, otherwise plutonium yield can not reach 99.9%, cause the enriched level of plutonium relatively low, 2BP plutonium concentration is not high.
And N is have studied for dimethyl hydroxylamine, Koltunov et al., N- dimethyl hydroxylamines are gone back to Pu (IV), Np (VI) Former behavior, as a result shows, Pu (IV) can quickly be reduced into Pu (III) by it.China Atomic Energy Science Research Institute Zhang Xianye etc. With salt-free go back original reagent N, the advanced two recycle streams+journey developed based on N- dimethyl hydroxylamines-monomethyl hydrazine has completed key The heat test of process section, its advantage are can to obtain the back extraction multiple higher than azanol-hydrazine system.However, dimethyl hydroxylamine and Monomethyl hydrazine is not inherently sufficiently stable, and security is poor；Meanwhile reacted reaction product can occur in plutonium nitrate solution Polymerization, therefore there is very big danger.
The content of the invention
To solve, the existing Purex flow plutonium purification cycle plutonium enriched level using salt-free go back original reagent is relatively low, security The problems such as poor, plutonium concentrated effect and process safety are taken into account, formaldoxime is used as back extraction reagent the invention provides a kind of Plutonium purification cycle technique.The technique includes：
(1) 2BX formaldoxime concentration is 0.5-0.7mol/L, concentration of nitric acid 0.3-0.5mol/L；
(2) 2BF plutonium nitrate concentration is 8-15g/L, concentration of nitric acid 0.15-0.3mol/L, uranium concentration 0.5-5g/ L；
(3) 2BS concentration of nitric acid is 0.1-0.5mol/L；
(4) stream compares 2BF:2BX=3-5:1；
(5) series >=10 grade are stripped, mend extraction series 3-5 levels.
The formaldoxime concentration of the 2BX is preferably 0.6mol/L.
The stream ratio preferably 2BF:2BX=4.
This technique, as salt-free go back original reagent, realizes the purifying concentration of plutonium product using formaldoxime.The emphasis of this technique It is the selection of process conditions, because the technological parameter being related to is more, and relevant technique bar is not provided in existing literature yet The choice direction of part, in the case, it is contemplated that the high radioactivity and high toxicity of plutonium purification cycle technological operation, therefore the present invention Plutonium purification cycle technique substantial amounts of difficulty is overcome in the selection of process conditions, suitable process conditions are finally just determined Scope.
The plutonium purification cycle technique of the present invention can realize that stripping process plutonium concentrates more than 5 times, and the plutonium of gained plutonium product liquid is dense Degree reaches as high as 60g/L, achieves higher plutonium yield and good uranium removal effect；Operation stability in process condition range Well；Holding reductant need not be added simultaneously, reduce the usage amount of reagent, improve economy, to follow-up in stripping process Plutonium depositing technology is without influence.
Brief description of the drawings
Fig. 1 Purex flow plutonium purification cycle process diagrams.
Embodiment
Embodiments of the present invention are described further with reference to embodiment.
Embodiment 1
The plutonium purifying products that the plutonium purification cycle technique of the present invention is applied to Purex flow concentrate, using following technique Condition：
(1) 2BX formaldoxime concentration is 0.6mol/L, concentration of nitric acid 0.4mol/L；
(2) 2BF plutonium nitrate concentration is 12g/L, concentration of nitric acid 0.2mol/L, uranium concentration 0.76g/L；
(3) 2BS concentration of nitric acid is 0.2mol/L；
(4) stream compares 2BF:2BX=5:1；
(5) 11 grades of series is stripped, mends 5 grades of series of extraction.
The plutonium concentration of gained plutonium product liquid is 60.3g/L, and it is about 0.4mg/L to remain plutonium concentration in organic phase, and plutonium yield is big The separation SF of uranium is removed in 99.99%, plutoniumU/Pu>104。
Embodiment 2
The plutonium purifying products that the plutonium purification cycle technique of the present invention is applied to Purex flow concentrate, using following technique Condition：
(1) 2BX formaldoxime concentration is 0.5mol/L, concentration of nitric acid 0.5mol/L；
(2) 2BF plutonium nitrate concentration is 15g/L, concentration of nitric acid 0.15mol/L, uranium concentration 1.86g/L；
(3) 2BS concentration of nitric acid is 0.3mol/L；
(4) stream compares 2BF:2BX=3:1；
(5) 12 grades of series is stripped, mends 3 grades of series of extraction.
The plutonium concentration of gained plutonium product liquid is 54.8g/L, and it is about 0.5mg/L to remain plutonium concentration in organic phase, and plutonium yield is big The separation SF of uranium is removed in 99.99%, plutoniumU/Pu>3000。

Claims (3)

1. a kind of use formaldoxime to be stripped the plutonium purification cycle technique of reagent, it is characterised in that the technique includes：
(1) 2BX formaldoxime concentration is 0.5-0.7mol/L, concentration of nitric acid 0.3-0.5mol/L；
(2) 2BF plutonium nitrate concentration is 8-15g/L, concentration of nitric acid 0.15-0.3mol/L, uranium concentration 0.5-5g/L；
(3) 2BS concentration of nitric acid is 0.1-0.5mol/L；
(4) stream compares 2BF:2BX=3-5:1；
(5) series >=10 grade are stripped, mend extraction series 3-5 levels.
2. as claimed in claim 1 use formaldoxime to be stripped the plutonium purification cycle technique of reagent, it is characterised in that：It is described 2BX formaldoxime concentration is 0.6mol/L.
3. as claimed in claim 1 use formaldoxime to be stripped the plutonium purification cycle technique of reagent, it is characterised in that：The stream Than for 2BF:2BX=4.
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CN106893878B (en) * 2017-03-02 2018-11-30 中国原子能科学研究院 A method of recycling plutonium from radioactivity spentnuclear fuel

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GB2118759A (en) * 1982-03-15 1983-11-02 Euratom Process for the recovery of plutonium from aqueous nitric solutions
CN102206753A (en) * 2011-04-01 2011-10-05 中国原子能科学研究院 Method for improving 2A process plutonium concentration multiple in Purex process
CN102352436A (en) * 2011-07-21 2012-02-15 中国原子能科学研究院 Method for separating U (uranium) from Pu (plutonium) in Purex process
CN102776372A (en) * 2012-08-21 2012-11-14 中国原子能科学研究院 Method for coextracting uranium, plutonium and neptunium
CN103451428A (en) * 2012-05-28 2013-12-18 中国原子能科学研究院 Ruthenium purifying technology in plutonium purification cycle of Purex process
CN103451455A (en) * 2012-05-28 2013-12-18 中国原子能科学研究院 Uranium (U) and plutonium (Pu) separation technology in Purex process
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CN102352436A (en) * 2011-07-21 2012-02-15 中国原子能科学研究院 Method for separating U (uranium) from Pu (plutonium) in Purex process
CN103451428A (en) * 2012-05-28 2013-12-18 中国原子能科学研究院 Ruthenium purifying technology in plutonium purification cycle of Purex process
CN103451455A (en) * 2012-05-28 2013-12-18 中国原子能科学研究院 Uranium (U) and plutonium (Pu) separation technology in Purex process
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