CN105761770A - Plutonium purification circulation process adopting (hydroxyamino) acetic acid as reverse extraction reagent - Google Patents

Plutonium purification circulation process adopting (hydroxyamino) acetic acid as reverse extraction reagent Download PDF

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CN105761770A
CN105761770A CN201610235580.1A CN201610235580A CN105761770A CN 105761770 A CN105761770 A CN 105761770A CN 201610235580 A CN201610235580 A CN 201610235580A CN 105761770 A CN105761770 A CN 105761770A
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plutonium
concentration
acetic acid
hydroxyamino
reagent
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CN105761770B (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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China Institute of Atomic of Energy
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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
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
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  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

The invention belongs to the field of nuclear fuel reprocessing. In order to solve the problems of relatively low concentration levels of plutonium purification and plutonium circulation and relatively poor safety of an existing Purex process adopting no salt to restore a reagent, the invention provides a plutonium purification circulation process adopting (hydroxyamino) acetic acid as a reverse extraction reagent. The process comprises the following indexes: the concentration of 2BX (hydroxyamino) acetic acid is 0.5 to 0.8 mol/L; the concentration of 2BF plutonium nitrate is 8 to 15g/L; the concentration of 2BS nitric acid is 0 to 0.5 mol/L; the concentration multiple is 3 to 6 times; the reverse extraction series is greater than 9, and the supplementary extraction series is 3 to 5. By adopting the plutonium purification circulation process, plutonium concentration in a reverse extraction process can be increased by 5 times or more than 5 times, maximum plutonium concentration of obtained plutonium product liquid can reach 70 g/L, and higher plutonium yield and good uranium removal effect are achieved; the operational stability in a process condition range is good; better economy is obtained.

Description

A kind of plutonium purification cycle technique using azanol acetic acid to be back extraction reagent
Technical field
The invention belongs to nuclear fuel post processing field, purify particularly to a kind of plutonium using azanol acetic acid to be back extraction reagent Circulation technology.
Background technology
Purex flow is the flow process that current reprocessing plant mainly uses, and this flow process includes co-decotamination cycle, uranium purification cycle With plutonium purification cycle.Wherein, the purpose of plutonium purification cycle is thick to obtained by co-decotamination cycle by extraction and stripping process Plutonium product is purified and concentrates, and finally gives qualified plutonium product, sees accompanying drawing 1.
For ensureing the plutonium yield of whole post processing flow process, usually require that the plutonium yield of plutonium purification cycle must reach 99.9%.Owing to plutonium purification cycle has the feature of organic phase plutonium concentration relatively big (more than 10g/L), therefore the back extraction at plutonium concentrates During, along with the raising of back extraction cycles of concentration, it is achieved the difficulty of 99.9% yield is that geometric progression increases, form plutonium purifying and follow The difficult point of ring process.
In plutonium purification cycle, the salt-free employing going back original reagent can reduce the radwaste volume of last handling process, Simplifying Purex flow technique, improve the economic benefit of post processing, the most salt-free research and development going back original reagent are the masters of Purex flow Want one of research contents.At present, the salt-free original reagent of going back being usually used in plutonium purification cycle mainly has two groups, is respectively as follows: 1. azanols-hydrazine System, 2. dimethyl hydroxylamine-hydrazine system.
Azanol (NH2OH) there is great reproducibility, so being closed widely in the salt-free research going back original reagent Note.Barney have studied azanol at HNO3The reaction of reduction Pu (IV) in solution, from reaction rate equation it can be seen that reaction is subject to Effect of Acidity On Absorption is relatively big, and along with acidity increases, reaction speed significantly slows down, therefore azanol under low acid, hot conditions to Pu (IV) Reduction effect preferable.Azanol is completely broken down into nitrogen, nitrous oxide etc. relatively as major advantage is that of reducing agent The gas of safety, but the speed of hydroxylamine reduction Pu (IV) is relatively slow, takes long enough to react complete.Same with this Time, realize plutonium yield with azanol-hydrazine as plutonium reduction reextraction reagent and reach the general technology condition of 99.9% as 2BF:2BX:2BS =2:1:0.3,12 grades of back extractions, mend extraction for 2 grades, wherein back extraction cycles of concentration maximum not can exceed that 2.3, mends extraction progression and not can exceed that 3 Level, otherwise plutonium yield can not reach 99.9%, and the enriched level causing plutonium is relatively low, and 2BP plutonium concentration is the highest.
And for dimethyl hydroxylamine, Koltunov et al. have studied N, N-dimethyl hydroxylamine and goes back Pu (IV), Np (VI) Former behavior, result shows, Pu (IV) can be quickly reduced into Pu (III) by it.China Atomic Energy Science Research Institute Zhang Xianye etc. With salt-free reduction reagent N, based on N-dimethyl hydroxylamine-monomethyl hydrazine, the advanced person's two recycle streams+journey of exploitation is complete key The heat test of process section, its advantage is can to obtain than azanol-hydrazine system higher back extraction multiple.But, dimethyl hydroxylamine and Monomethyl hydrazine is the most sufficiently stable, and security is poor；Meanwhile, reacted product can occur in plutonium nitrate solution Polymerization, therefore has the biggest danger.Plutonium yield is realized as plutonium reduction reextraction reagent using dimethyl hydroxylamine and monomethyl hydrazine The general technology condition reaching 99.9% is 2BF:2BX:2BS=3.5:1:0.3,10 grades of back extractions, mends extraction for 3 grades, and wherein back extraction is dense Demagnification number maximum not can exceed that 4.0, mends extraction progression and not can exceed that 3 grades, and otherwise plutonium yield can not reach 99.9%.
Summary of the invention
In order to solve, the salt-free Purex flow plutonium purification cycle plutonium enriched level going back original reagent of existing employing is relatively low, security The problem such as poor, takes into account plutonium concentrated effect and process safety, the invention provides that a kind of to use azanol acetic acid be back extraction reagent Plutonium purification cycle technique.This technique includes:
(1) the azanol acetic acid concentration of 2BX is 0.5-0.8mol/L, and concentration of nitric acid is 0.3-0.7mol/L；
(2) the plutonium nitrate concentration of 2BF is 8-15g/L；
(3) concentration of nitric acid of 2BS is 0-0.5mol/L；
(4) cycles of concentration is 3-6 times；
(5) back extraction progression >=9 grade, mend extraction progression 3-5 level.
The azanol acetic acid concentration of described 2BX is preferably 0.7mol/L.
Described cycles of concentration is preferably 5 times.
This technique uses azanol acetic acid to go back original reagent as salt-free, it is achieved that the purified concentration of plutonium product.The weight of this technique Point is the selection of process conditions, owing to the technological parameter related to is more, and does not the most provide relevant technique in existing document The choice direction of condition, in the case, it is contemplated that the high radioactivity of plutonium purification cycle technological operation and high toxicity, therefore this Bright plutonium purification cycle technique overcomes substantial amounts of difficulty in the selection of process conditions, the most just determines suitable technique bar Part scope.
The plutonium purification cycle technique of the present invention can realize stripping process plutonium and concentrate more than 5 times, and the plutonium of gained plutonium product liquid is dense Degree reaches as high as 70g/L, achieves higher plutonium yield and good uranium removal effect；Operation stability in process condition range Well；Stripping process need not add holding reductant simultaneously, decrease the usage amount of reagent, improve economy, to follow-up Plutonium depositing technology is without impact.
Accompanying drawing explanation
Fig. 1 Purex flow plutonium purification cycle process diagram.
Detailed description of the invention
Below in conjunction with embodiment, embodiments of the present invention are described further.
Embodiment 1
The plutonium purifying products that the plutonium purification cycle technique of the present invention is applied to Purex flow concentrates, and uses following technique Condition:
(1) the azanol acetic acid concentration of 2BX is 0.6mol/L, and concentration of nitric acid is 0.6mol/L；
(2) the plutonium nitrate concentration of 2BF is 12g/L；
(3) concentration of nitric acid of 2BS is 0.3mol/L；
(4) cycles of concentration is 5.5 times；
(5) back extraction progression 12 grades, mend extraction progression 4 grades.
The plutonium concentration of gained plutonium product liquid is 71.4g/L, remains plutonium concentration and be about 0.4mg/L in organic phase, and plutonium yield is big In 99.99%.
Embodiment 2
The plutonium purifying products that the plutonium purification cycle technique of the present invention is applied to Purex flow concentrates, and uses following technique Condition:
(1) the azanol acetic acid concentration of 2BX is 0.8mol/L, and concentration of nitric acid is 0.4mol/L；
(2) the plutonium nitrate concentration of 2BF is 9g/L；
(3) concentration of nitric acid of 2BS is 0.1mol/L；
(4) cycles of concentration is 6 times；
(5) back extraction progression 10 grades, mend extraction progression 5 grades.
The plutonium concentration of gained plutonium product liquid is 60.8g/L, remains plutonium concentration and be about 0.3mg/L in organic phase, and plutonium yield is big In 99.99%.

Claims (3)

1. the plutonium purification cycle technique that one kind uses azanol acetic acid to be back extraction reagent, it is characterised in that this technique includes:
(1) the azanol acetic acid concentration of 2BX is 0.5-0.8mol/L, and concentration of nitric acid is 0.3-0.7mol/L；
(2) the plutonium nitrate concentration of 2BF is 8-15g/L；
(3) concentration of nitric acid of 2BS is 0-0.5mol/L；
(4) cycles of concentration is 3-6 times；
(5) back extraction progression >=9 grade, mend extraction progression 3-5 level.
2. the plutonium purification cycle technique using azanol acetic acid to be back extraction reagent as claimed in claim 1, it is characterised in that: described The azanol acetic acid concentration of 2BX is 0.7mol/L.
3. the plutonium purification cycle technique using azanol acetic acid to be back extraction reagent as claimed in claim 1, it is characterised in that: described Cycles of concentration is 5 times.
CN201610235580.1A 2016-04-15 2016-04-15 It is a kind of to use azanol acetic acid to be stripped the plutonium purification cycle technique of reagent Active CN105761770B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023155278A1 (en) * 2022-02-17 2023-08-24 中国原子能科学研究院 Method for treating retained plutonium in waste organic phase in purex process

Citations (4)

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Publication number Priority date Publication date Assignee Title
US4656011A (en) * 1984-02-13 1987-04-07 British Nuclear Fuel Plc Process of treating nuclear fuel
US4839101A (en) * 1986-01-29 1989-06-13 Kernforschungszentrum Karlsruhe Gmbh Process for improving the effectiveness of the removal of zirconium from a nuclear fuel and/or fertile material solution
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
CN104004928A (en) * 2014-05-30 2014-08-27 中国原子能科学研究院 Plutonium purification and concentration method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4656011A (en) * 1984-02-13 1987-04-07 British Nuclear Fuel Plc Process of treating nuclear fuel
US4839101A (en) * 1986-01-29 1989-06-13 Kernforschungszentrum Karlsruhe Gmbh Process for improving the effectiveness of the removal of zirconium from a nuclear fuel and/or fertile material solution
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
CN104004928A (en) * 2014-05-30 2014-08-27 中国原子能科学研究院 Plutonium purification and concentration method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023155278A1 (en) * 2022-02-17 2023-08-24 中国原子能科学研究院 Method for treating retained plutonium in waste organic phase in purex process

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