CN106555054B - A kind of separation and recovery method of thorium and uranium - Google Patents

A kind of separation and recovery method of thorium and uranium Download PDF

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CN106555054B
CN106555054B CN201510631309.5A CN201510631309A CN106555054B CN 106555054 B CN106555054 B CN 106555054B CN 201510631309 A CN201510631309 A CN 201510631309A CN 106555054 B CN106555054 B CN 106555054B
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uranium
thorium
acid
extraction
cleaning solution
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CN106555054A (en
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张岚
李峥
李瑞芬
刘春霞
何淑华
赵皓贵
李晴暖
于婷
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Shanghai Institute of Applied Physics of CAS
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Shanghai Institute of Applied Physics of CAS
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    • 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
    • C22B60/0291—Obtaining thorium, uranium, or other actinides obtaining thorium
    • 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
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
    • C22B60/026—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries liquid-liquid extraction with or without dissolution in organic solvents
    • 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

Abstract

The invention discloses the separation and recovery methods of a kind of thorium and uranium.Comprising: 1) organic solvent of methylphosphonic acid two (1- methyl) heptyl ester will be contained as extractant, aqueous acid carries out fractional extraction as cleaning solution using the aqueous acid for containing thorium and uranium as feed liquid；2) organic solvent of methylphosphonic acid two (1- methyl) heptyl ester will be contained as extraction agent is mended, for aqueous acid as cleaning solution, the organic extraction phase containing thorium and uranium that step 1) is obtained, benefit extraction agent and cleaning solution carry out fractional extraction；3) the organic extraction phase for the uranium-bearing that step 2) obtains and strip liquor are stripped in a manner of multi-stage countercurrent.Separation and recovery method of the invention can realize thorium, uranium separation and recovery, and obtain higher thorium, the uranium rate of recovery and foreign metal ion decontamination factor in the case where lower charging acidity, organic phase/aqueous phase stream when less extraction series.

Description

A kind of separation and recovery method of thorium and uranium
Technical field
The present invention relates to the separation and recovery methods of a kind of thorium and uranium.
Background technique
Thorium element is one of the important element in nuclear energy research and development, and neutron can be absorbed and be transformed into fissilenuclide U-233 carries out nuclear fission reaction, therefore thorium element is a kind of extremely promising nuclear fuel.Post-processing for thorium base nuclear fuel, It seeks to recycle and separates wherein unburned complete thorium, uranium, to realize making full use of for resource.
Up to the present, usually use TBP as extractant with Thorex process come carry out thorium, uranium recycling and point From.But in practical applications, TBP Shortcomings and defect, if extraction ability of the TBP to thorium is relatively low, in order to guarantee thorium Yield, needs plus the concentrated nitric acid of 12-13mol/L is as acid of saltouing, and causes the acidity of whole flow process system higher, subseries acid Degree can reach 6mol/L；TBP is not high to the loading capacity of thorium, is easy to appear third phase, and requirements of process height stream is than (organic phase/water Make an appointment 8/1-9/1)；TBP is lower to thorium uranium separation, while realizing the separation of thorium uranium, increases multi-stage counter current extraction series, uranium Yield still decrease；Solubility of the TBP in water phase is higher, while cause extractant to lose, and increases liquid waste processing Difficulty, limit its practical application value etc..
Summary of the invention
Technical problem to be solved by the present invention lies in order to overcome existing separation and recovery thorium and uranium from thorium base spentnuclear fuel Method in thorium yield it is lower, need the fractional extraction grade when more using higher charging acidity, organic phase/aqueous phase stream The defects of number, and provide the separation and recovery method of a kind of thorium and uranium.Separation and recovery method of the invention can be in lower charging In the case where the when less fractional extraction series of acidity, organic phase/aqueous phase stream, the separation and recycling of thorium, uranium are realized, and can be with It obtains higher thorium, the uranium rate of recovery, go in uranium and uranium to remove thorium separation and foreign metal ion decontamination factor in thorium.
The present invention provides the separation and recovery methods of a kind of thorium and uranium comprising following steps:
1) using the aqueous acid for containing thorium and uranium as feed liquid, the organic solvent of methylphosphonic acid two (1- methyl) heptyl ester will be contained As extractant, aqueous acid B carries out multi-stage counter current extraction, obtains the organic extraction phase containing thorium and uranium as cleaning solution I； The volumetric concentration of methylphosphonic acid two (1- methyl) heptyl ester is 10%-35% in the extractant；It is acid in the cleaning solution I The molar concentration of substance is 0.2-0.8mol/L；
2) organic solvent of methylphosphonic acid two (1- methyl) heptyl ester will be contained as extraction agent is mended, aqueous acid C is as cleaning solution II, the organic extraction phase containing thorium and uranium, benefit extraction agent and the cleaning solution II that step 1) is obtained carry out multi-stage counter current extraction, obtain To the water phase of thoriated and the organic extraction phase of uranium-bearing；The volumetric concentration of methylphosphonic acid two (1- methyl) heptyl ester in the benefit extraction agent For 20%-30%；The molar concentration of II middle acid substance of cleaning solution is 0.05-0.1mol/L；
3) the organic extraction phase for the uranium-bearing that step 2) obtains and strip liquor are stripped in a manner of multi-stage countercurrent, are obtained The water phase of uranium-bearing.
In step 1), in the aqueous acid containing thorium and uranium, the acid of use preferably hydrochloric acid, sulfuric acid, phosphoric acid and nitre One or more of acid, sour molar concentration preferred 0.5-2mol/L, preferably 0.6-1mol/L, more preferable 0.8mol/L, thorium It is not particularly limited with the molar concentration of uranium, general thorium is 0.86-2.0mol/L, preferably 1.0mol/L, uranium 0.008- 0.02mol/L, preferably 0.01mol/L, wherein the mass ratio of thorium and uranium preferred 10:1~5000:1, more preferable 100:1.
In step 1), the feed liquid can be the aqueous solution of thorium base spentnuclear fuel conventional in the art, in addition to containing thorium Other than uranium, also contain Zr4+、Nb5+、Ru(RuNO3+)、Rh3+、Sr2+、Cs+、Ce3+、Ce4+、Gd3+、Dy3+Etc. other sliver members Element, and extractant of the invention is lower for other fission product distribution coefficients in addition to thorium and uranium, therefore, remaining element Concentration will not influence the recycling to uranium, general molar concentration of other fission products in feed liquid is 20ppm.The thorium base Spentnuclear fuel become the feed liquid before, it usually needs shelling, dissolution, flocculation, filtering, condiment and etc. processing.
In step 1), in the preferred chloroform of organic solvent, n-dodecane, kerosene and the toluene in the extractant It is one or more of.The preferred 20%-30% of volumetric concentration of methylphosphonic acid two (1- methyl) heptyl ester in the extractant.
In step 1), the cleaning solution I can be the aqueous acid of this field routine, wherein the acidic materials used can be for One or more of acidic materials conventional in the art, preferably hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and ferrous sulfamate.Institute The molar concentration preferred 0.2-0.6mol/L, more preferable 0.3-0.5mol/L for I middle acid substance of cleaning solution stated.
In step 1), the fractional extraction process is multi-stage counter current extraction-washing process conventional in the art, with While the mode of multi-stage countercurrent is extracted, adding one again still in organic phase outlet one end is the washing of multi-stage countercurrent mode Process.The extraction section is from organic phase entrance to feed liquid port, i.e. organic phase and feed liquid, I reverse flow of cleaning solution extracts Lever piece, the washing section be from I entrance of cleaning solution, that is, washing section first order and the organic phase Jing Guo extraction section it is reverse Flowing, and the lever piece converged in feed liquid feed inlet and feed liquid.The extraction section and washing section is respectively multi-stage countercurrent operation Section.In the present invention, the operating procedure and condition of the fractional extraction can be operating procedure conventional in the art and condition, The equipment used can be centrifugal extractor conventional in the art, mixer-settler, pulse extraction column.The series, which refers to, to be reached The unit number of required equipment when to separation requirement, such as the number of tower, the series of trough (can be regarded as by a mixing chamber and a clarifying chamber Level-one).In step 1) of the present invention, in the fractional extraction, extraction series preferably >=6 grades, it is 8-10 grade more preferable, washing series It is preferred that >=6 grades, it is 7-8 grades more preferable.
In step 1), the stream of the feed liquid, extractant and cleaning solution I is than preferred 1:(4-7): (0.5-1), more preferable 1: (5-6):(0.8-1).The stream compares for velocity ratio, dimension mL/min.
In step 2), the aqueous acid C of use is different from aqueous acid B concentration in step 1).In the aqueous acid C The acidic materials used can be the acidic materials of this field routine, preferably hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and ferrous sulfamate One or more of.The preferred 0.08mol/L of molar concentration of the aqueous acid C middle acid substance.
In step 2), in the organic extraction phase containing thorium and uranium that the step 1) obtains, after being fractionated extraction, thorium turns Water phase is moved to, uranium remains in organic phase, is somebody's turn to do the organic extraction phase containing uranium, then through step 3) back extraction to water phase.
In step 2), in the preferred chloroform of organic solvent, n-dodecane, kerosene and toluene in the benefit extraction agent It is one or more of.The preferred 25%-30% of volumetric concentration of methylphosphonic acid two (1- methyl) heptyl ester in the benefit extraction agent.
In step 2), the extraction series of the fractional extraction preferably >=3 grades, it is 4-5 grade more preferable, washing series is preferred >= It is 5 grades, 6-7 grades more preferable.
In step 2), the organic extraction phase containing thorium and uranium, the stream ratio preferably 1 for mending extraction agent and cleaning solution II: (0.2-0.8): (0.4-1), more preferable 1:(0.3-0.6): (0.5-0.8), most preferably 1:(0.4-0.6): (0.5-0.6).
In step 3), the strip liquor can be water conventional in the art or aqueous acid.When the strip liquor is When aqueous acid, the acid used can be the acid of this field routine, preferably one or more of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, The preferred 0.05mol/L of molar concentration of acid is hereinafter, it is preferred that 0.001-0.01mol/L.
In step 3), the series of the back extraction preferably >=4 grades, it is 6-8 grades more preferable.
In step 3), in the back extraction, the organic extraction phase of the uranium-bearing and the stream of strip liquor are than preferred (2-5): 1, more preferable (2-3): 1.The stream compares for velocity ratio, dimension mL/min.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can any combination to get the present invention it is each preferably Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that: separation and recovery method of the invention can be in lower charging acidity, organic Phase/aqueous phase stream when in the case where less fractional extraction series, realizes the separation and recycling of thorium, uranium, and can obtain higher Thorium, the uranium rate of recovery remove uranium separation in thorium, remove thorium separation and foreign metal ion decontamination factor in uranium.
Detailed description of the invention
The separation and recovery method flow chart of Fig. 1 thorium of the present invention and uranium
Thorium, uranium concentration distribution in thorium and uranium coextraction section organic phase at different levels and water phase in Fig. 2 embodiment 1
Thorium, uranium concentration distribution in thorium and uranium segregation section organic phase at different levels and water phase in Fig. 3 embodiment 1
Thorium, uranium concentration distribution in uranium stripping section organic phase at different levels and water phase in Fig. 4 embodiment 1
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient The selection of product specification.
Embodiment 1
1) using kerosene as organic solvent, prepare (1- methyl) the heptyl ester volumetric concentration of methylphosphonic acid two be 25% it is organic molten Liquid is prepared as extractant and contains Th4+、UO2 2+、Zr4+、Nb5+、Ru(RuNO3+)、Rh3+、Sr2+、Cs+、Ce3+、Ce4+、Gd3+、Dy3+ 1M aqueous solution of nitric acid, wherein Th4+、UO2 2+Concentration is 200g/L, 2g/L, and other concentration of metal ions are 20ppm, as material Liquid prepares the aqueous solution of nitric acid of 0.2M, as cleaning solution I, the above solution is carried out fractional extraction, extraction series is 10 grades, is washed Washing series is 8 grades, and feed liquid, extractant, the stream of cleaning solution I are than being 1:5:0.5, and thorium and uranium are extracted in organic phase, and impurity is golden Belong to ion and be retained in water phase, organic phase and water phase thorium at different levels, uranium concentration distribution are as shown in Figure 2；
Dotted line position is multi-stage counter current extraction starting position in Fig. 2, is washed as can be seen from Fig. 2 by 10 grades of extractions and 8 grades It washs.
2) using kerosene as organic solvent, prepare (1- methyl) the heptyl ester volumetric concentration of methylphosphonic acid two be 25% it is organic molten Liquid extracts agent as mending, prepares the aqueous solution of nitric acid of 0.05M, as cleaning solution II, will mend extraction agent, cleaning solution II and step 1) and obtain The thoriated and uranium organic phase arrived carries out the separation of thorium uranium by fractional extraction, and mending extraction series is 5 grades, and washing series is 7 grades, step 1) The organic phase of obtained thoriated and uranium mends extraction agent, the stream of cleaning solution II than being 1:0.4:1, and thorium arrives water phase by back extraction at this time, is contained The water phase product of thorium, and uranium remains in organic phase, organic phase and water phase thorium at different levels, uranium concentration distribution are as shown in Figure 3；
Dotted line position is multi-stage counter current extraction feed entrance point in Fig. 3, as can be seen from Fig. 3 by the benefit extraction of 5 grades of uranium and 7 grades The back extraction of thorium.In Fig. 3 in stripping section, that is, step 2 of thorium, thorium back extraction to water phase, uranium is mended the process that extraction is retained in organic phase.
3) aqueous solution of nitric acid for preparing 0.005M, as strip liquor, by the organic phase of uranium-bearing and strip liquor with multi-stage countercurrent Mode be stripped, back extraction series is 8 grades, and the organic phase of uranium-bearing, back extraction liquid flowing ratio are 3:1, obtain the water phase product of uranium-bearing, Organic phase and water phase thorium at different levels, uranium concentration distribution are as shown in Figure 4；.
Through detecting, under this condition, thorium, the uranium rate of recovery go uranium separation up to 2.3 × 10 up to 99.99% in thorium4, Go thorium separation up to 1.2 × 10 in uranium5, foreign metal ion decontamination factor is up to 1.6 × 103。
Embodiment 2
1) using n-dodecane as organic solvent, preparing methylphosphonic acid two (1- methyl) heptyl ester volumetric concentration is 15% to have Machine solution is prepared as extractant and contains Th4+、UO2 2+、Zr4+、Nb5+、Ru(RuNO3+)、Rh3+、Sr2+、Cs+、Ce3+、Ce4+、Gd3 +、Dy3+2M aqueous solution of nitric acid, wherein Th4+、UO2 2+Concentration is 200g/L, 2g/L, and other concentration of metal ions are 20ppm, is made For feed liquid, the aqueous solution of nitric acid of 0.2M is prepared, as cleaning solution I, extractant, feed liquid and cleaning solution I are subjected to fractional extraction, extraction Taking series is 10 grades, and washing series is 6 grades, and than being 1:7:1, thorium and uranium are extracted to organic for feed liquid, extractant, the stream of cleaning solution I Xiang Zhong, and foreign metal ion is retained in water phase；
2) using kerosene as organic solvent, prepare (1- methyl) the heptyl ester volumetric concentration of methylphosphonic acid two be 30% it is organic molten Liquid extracts agent as mending, prepares the aqueous solution of nitric acid of 0.05M, as cleaning solution II, will mend extraction agent, cleaning solution II and step 1) and obtain The organic phase of the thoriated and uranium that arrive carries out the separation of thorium uranium by fractional extraction, and mending extraction series is 3 grades, and washing series is 5 grades, thoriated It is 1:0.8:0.6 with the organic phase of uranium, the agent of benefit extraction, the stream ratio of cleaning solution II, thorium, which is stripped, at this time arrives water phase, obtains the water phase of thoriated Product, and uranium remains in organic phase；
3) nitric acid solution for preparing 0.005M, as strip liquor, by the organic phase of uranium-bearing and strip liquor with multi-stage countercurrent Mode is stripped, and back extraction series is 6 grades, and the organic phase of uranium-bearing, back extraction liquid flowing ratio are 4:1, obtains the water phase product of uranium-bearing.
Through detecting, under this condition, thorium, the uranium rate of recovery go uranium separation up to 3.6 × 10 up to 99.99% in thorium4, Go thorium separation up to 1.1 × 10 in uranium5, foreign metal ion decontamination factor is up to 1.2 × 103。
Embodiment 3
1) using n-dodecane as organic solvent, preparing methylphosphonic acid two (1- methyl) heptyl ester volumetric concentration is 20% to have Machine solution is prepared as extractant and contains Th4+、UO2 2+、Zr4+、Nb5+、Ru(RuNO3+)、Rh3+、Sr2+、Cs+、Ce3+、Ce4+Gd3+、 Dy3+0.6M aqueous solution of nitric acid, wherein Th4+、UO2 2+Concentration is 200g/L, 2g/L, and other concentration of metal ions are 20ppm, is made For feed liquid, the aqueous solution of nitric acid of 1.0M is prepared, as cleaning solution I, extractant, feed liquid and cleaning solution I are subjected to fractional extraction, extraction Taking series is 9 grades, and washing series is 7 grades, and than being 1:4:0.8, thorium and uranium are extracted to organic for feed liquid, extractant, the stream of cleaning solution I Xiang Zhong, and foreign metal ion is retained in water phase；
2) using kerosene as organic solvent, prepare (1- methyl) the heptyl ester volumetric concentration of methylphosphonic acid two be 20% it is organic molten Liquid extracts agent as mending, prepares the aqueous solution of nitric acid of 0.1M, as cleaning solution II, will mend extraction agent, cleaning solution II and step 1) and obtains Thoriated and uranium organic phase by fractional extraction carry out the separation of thorium uranium, mend extraction series be 4 grades, washing series be 6 grades, thoriated and The organic phase of uranium mends extraction agent, the stream of cleaning solution II than being 1:0.4:0.5, and thorium arrives water phase by back extraction at this time, and the water phase for obtaining thoriated produces Product, and uranium remains in organic phase；
3) using pure water as strip liquor, the organic phase of uranium-bearing and strip liquor are stripped in a manner of multi-stage countercurrent, Being stripped series is 6 grades, and the organic phase of uranium-bearing, back extraction liquid flowing ratio are 3:1, obtains the water phase product of uranium-bearing.
Through detecting, under this condition, thorium, the uranium rate of recovery go uranium separation up to 5.0 × 10 up to 99.99% in thorium4, Go thorium separation up to 3.5 × 10 in uranium5, foreign metal ion decontamination factor is up to 1.0 × 103。
Embodiment 4
1) using n-dodecane as organic solvent, preparing methylphosphonic acid two (1- methyl) heptyl ester volumetric concentration is 25% to have Machine solution is prepared as extractant and contains Th4+、UO2 2+、Zr4+、Nb5+、Ru(RuNO3+)、Rh3+、Sr2+、Cs+、Ce3+、Ce4+、Gd3 +、Dy3+1.0M aqueous solution of nitric acid, wherein Th4+、UO2 2+Concentration is 200g/L, 2g/L, and other concentration of metal ions are 20ppm, As feed liquid, the aqueous solution of nitric acid of 0.8M is prepared, as cleaning solution I, extractant, feed liquid and cleaning solution I are subjected to fractional extraction, Extracting series is 8 grades, and washing series is 7 grades, and than being 1:5:1, thorium and uranium are extracted to organic for feed liquid, extractant, the stream of cleaning solution I Xiang Zhong, and foreign metal ion is retained in water phase；
2) using kerosene as organic solvent, prepare (1- methyl) the heptyl ester volumetric concentration of methylphosphonic acid two be 20% it is organic molten Liquid extracts agent as mending, prepares the aqueous solution of nitric acid of 0.08M, as cleaning solution II, will mend extraction agent, cleaning solution II and step 1) and obtain The organic phase of the thoriated and uranium that arrive carries out the separation of thorium uranium by fractional extraction, and mending extraction series is 5 grades, and washing series is 7 grades, thoriated It is 1:0.6:0.5 with the organic phase of uranium, the agent of benefit extraction, the stream ratio of cleaning solution II, thorium, which is stripped, at this time arrives water phase, obtains the water phase of thoriated Product, and uranium remains in organic phase；
3) using the nitric acid solution of 0.001M as strip liquor, by the organic phase of uranium-bearing and strip liquor with the side of multi-stage countercurrent Formula is stripped, and back extraction series is 8 grades, and the organic phase of uranium-bearing, back extraction liquid flowing ratio are 3:1, obtains the water phase product of uranium-bearing.
Through detecting, under this condition, thorium, the uranium rate of recovery go uranium separation up to 6.1 × 10 up to 99.99% in thorium4, Go thorium separation up to 4.5 × 10 in uranium5, foreign metal ion decontamination factor is up to 1.1 × 103。
Embodiment 5
1) using n-dodecane as organic solvent, preparing methylphosphonic acid two (1- methyl) heptyl ester volumetric concentration is 30% to have Machine solution is prepared as extractant and contains Th4+、UO2 2+、Zr4+、Nb5+、Ru(RuNO3+)、Rh3+、Sr2+、Cs+、Ce3+、Ce4+、Gd3 +、Dy3+0.8M aqueous solution of nitric acid, wherein Th4+、UO2 2+Concentration is 200g/L, 2g/L, and other concentration of metal ions are 20ppm, As feed liquid, the aqueous solution of nitric acid of 0.8M is prepared, as cleaning solution I, extractant, feed liquid and cleaning solution I are subjected to fractional extraction, Extracting series is 7 grades, and washing series is 8 grades, and than being 1:4:0.8, thorium and uranium have been extracted to for feed liquid, extractant, the stream of cleaning solution I In machine phase, and foreign metal ion is retained in water phase；
2) using kerosene as organic solvent, prepare (1- methyl) the heptyl ester volumetric concentration of methylphosphonic acid two be 20% it is organic molten Liquid extracts agent as mending, prepares the aqueous solution of nitric acid of 0.1M, as cleaning solution II, will mend extraction agent, cleaning solution II and step 1) and obtains Thoriated and uranium organic phase by fractional extraction carry out the separation of thorium uranium, mend extraction series be 5 grades, washing series be 6 grades, thoriated and The organic phase of uranium mends extraction agent, the stream of cleaning solution II than being 1:0.3:0.8, and thorium arrives water phase by back extraction at this time, and the water phase for obtaining thoriated produces Product, and uranium remains in organic phase；
3) using the nitric acid solution of 0.001M as strip liquor, by the organic phase of uranium-bearing and strip liquor with the side of multi-stage countercurrent Formula is stripped, and back extraction series is 7 grades, and the organic phase of uranium-bearing, back extraction liquid flowing ratio are 4:1, obtains the water phase product of uranium-bearing.
Through detecting, under this condition, thorium, the uranium rate of recovery go uranium separation up to 5.2 × 10 up to 99.99% in thorium4, Go thorium separation up to 5.5 × 10 in uranium5, foreign metal ion decontamination factor is up to 1.6 × 103。
Embodiment 6
1) using n-dodecane as organic solvent, preparing methylphosphonic acid two (1- methyl) heptyl ester volumetric concentration is 35% to have Machine solution is prepared as extractant and contains Th4+、UO2 2+、Zr4+、Nb5+、Ru(RuNO3+)、Rh3+、Sr2+、Cs+、Ce3+、Ce4+、Gd3 +、Dy3+0.5M aqueous solution of nitric acid, wherein Th4+、UO2 2+Concentration is 200g/L, 2g/L, and other concentration of metal ions are 20ppm, As feed liquid, the aqueous solution of nitric acid of 0.6M is prepared, as cleaning solution I, extractant, feed liquid and cleaning solution I are subjected to fractional extraction, Extracting series is 7 grades, and washing series is 8 grades, and than being 1:4:1, thorium and uranium are extracted to organic for feed liquid, extractant, the stream of cleaning solution I Xiang Zhong, and foreign metal ion is retained in water phase；
2) using kerosene as organic solvent, prepare (1- methyl) the heptyl ester volumetric concentration of methylphosphonic acid two be 20% it is organic molten Liquid extracts agent as mending, prepares the aqueous solution of nitric acid of 0.1M, as cleaning solution II, will mend extraction agent, cleaning solution II and step 1) and obtains Thoriated and uranium organic phase by fractional extraction carry out the separation of thorium uranium, mend extraction series be 5 grades, washing series be 6 grades, thoriated and The organic phase of uranium mends extraction agent, the stream of cleaning solution II than being 1:0.5:1, and thorium arrives water phase by back extraction at this time, and the water phase for obtaining thoriated produces Product, and uranium remains in organic phase；
3) using the nitric acid solution of 0.005M as strip liquor, by the organic phase of uranium-bearing and strip liquor with the side of multi-stage countercurrent Formula is stripped, and back extraction series is 6 grades, and the organic phase of uranium-bearing, back extraction liquid flowing ratio are 4:1, obtains the water phase product of uranium-bearing.
Through detecting, under this condition, thorium, the uranium rate of recovery go uranium separation up to 5.2 × 10 up to 99.99% in thorium4, Go thorium separation up to 5.5 × 10 in uranium5, foreign metal ion decontamination factor is up to 1.6 × 103。
Embodiment 7
1) using n-dodecane as organic solvent, preparing methylphosphonic acid two (1- methyl) heptyl ester volumetric concentration is 20% to have Machine solution is prepared as extractant and contains Th4+、UO2 2+、Zr4+、Nb5+、Ru(RuNO3+)、Rh3+、Sr2+、Cs+、Ce3+、Ce4+、Gd3 +、Dy3+0.6M aqueous solution of nitric acid, wherein Th4+、UO2 2+Concentration is 200g/L, 2g/L, and other concentration of metal ions are 20ppm, As feed liquid, the aqueous solution of nitric acid of 0.8M is prepared, as cleaning solution I, extractant, feed liquid and cleaning solution I are subjected to fractional extraction, Extracting series is 8 grades, and washing series is 6 grades, and than being 1:5:1, thorium and uranium are extracted to organic for feed liquid, extractant, the stream of cleaning solution I Xiang Zhong, and foreign metal ion is retained in water phase；
2) using kerosene as organic solvent, prepare (1- methyl) the heptyl ester volumetric concentration of methylphosphonic acid two be 20% it is organic molten Liquid extracts agent as mending, prepares the aqueous solution of nitric acid of 0.1M, as cleaning solution II, will mend extraction agent, cleaning solution II and step 1) and obtains Thoriated and uranium organic phase by fractional extraction carry out the separation of thorium uranium, mend extraction series be 4 grades, washing series be 6 grades, thoriated and The organic phase of uranium mends extraction agent, the stream of cleaning solution II than being 1:0.6:0.5, and thorium arrives water phase by back extraction at this time, and the water phase for obtaining thoriated produces Product, and uranium remains in organic phase；
3) using 0.001M nitric acid as strip liquor, the organic phase of uranium-bearing and strip liquor are carried out in a manner of multi-stage countercurrent Back extraction, back extraction series are 4 grades, and the organic phase of uranium-bearing, back extraction liquid flowing ratio are 3:1, obtain the water phase product of uranium-bearing.
Through detecting, under this condition, thorium, the uranium rate of recovery go uranium separation up to 2.6 × 10 up to 99.99% in thorium4, Go thorium separation up to 1.8 × 10 in uranium5, foreign metal ion decontamination factor is up to 1.0 × 103。
Embodiment 8
1) using n-dodecane as organic solvent, preparing methylphosphonic acid two (1- methyl) heptyl ester volumetric concentration is 30% to have Machine solution is prepared as extractant and contains Th4+、UO2 2+、Zr4+、Nb5+、Ru(RuNO3+)、Rh3+、Sr2+、Cs+、Ce3+、Ce4+、Gd3 +、Dy3+0.6M aqueous solution of nitric acid, wherein Th4+、UO2 2+Concentration is 200g/L, 2g/L, and other concentration of metal ions are 20ppm, As feed liquid, the aqueous solution of nitric acid of 0.5M is prepared, as cleaning solution I, extractant, feed liquid and cleaning solution I are subjected to fractional extraction, Extracting series is 8 grades, and washing series is 6 grades, and than being 1:4:1, thorium and uranium are extracted to organic for feed liquid, extractant, the stream of cleaning solution I Xiang Zhong, and foreign metal ion is retained in water phase；
2) using kerosene as organic solvent, prepare (1- methyl) the heptyl ester volumetric concentration of methylphosphonic acid two be 30% it is organic molten Liquid extracts agent as mending, prepares the aqueous solution of nitric acid of 0.1M, as cleaning solution II, will mend extraction agent, cleaning solution II and step 1) and obtains Thoriated and uranium organic phase by fractional extraction carry out the separation of thorium uranium, mend extraction series be 4 grades, washing series be 6 grades, thoriated and The organic phase of uranium mends extraction agent, the stream of cleaning solution II than being 1:0.2:0.5, and thorium arrives water phase by back extraction at this time, and the water phase for obtaining thoriated produces Product, and uranium remains in organic phase；
3) using 0.001M nitric acid as strip liquor, the organic phase of uranium-bearing and strip liquor are carried out in a manner of multi-stage countercurrent Back extraction, back extraction series are 4 grades, and the organic phase of uranium-bearing, back extraction liquid flowing ratio are 3:1, obtain the water phase product of uranium-bearing.
Through detecting, under this condition, thorium, the uranium rate of recovery go uranium separation up to 1.9 × 10 up to 99.99% in thorium4, Go thorium separation up to 2.6 × 10 in uranium5, foreign metal ion decontamination factor is up to 1.3 × 103。

Claims (10)

1. the separation and recovery method of a kind of thorium and uranium comprising following steps:
1) using the aqueous acid for containing thorium and uranium as feed liquid, the organic solvent conduct of methylphosphonic acid two (1- methyl) heptyl ester will be contained Extractant, aqueous acid B carry out fractional extraction, obtain the organic extraction phase containing thorium and uranium as cleaning solution I；The extraction The volumetric concentration for taking methylphosphonic acid two in agent (1- methyl) heptyl ester is 10%-35%；I middle acid substance of cleaning solution rubs Your concentration is 0.2-0.8mol/L；
2) organic solvent of methylphosphonic acid two (1- methyl) heptyl ester will be contained as benefit extraction agent, aqueous acid C, will as cleaning solution II The organic extraction phase containing thorium and uranium, benefit extraction agent and the cleaning solution II that step 1) obtains carry out fractional extraction, obtain thoriated The organic extraction phase of water phase and uranium-bearing；The volumetric concentration of methylphosphonic acid two (1- methyl) heptyl ester is 20%- in the benefit extraction agent 30%；The molar concentration of II middle acid substance of cleaning solution is 0.05-0.1mol/L；
3) the organic extraction phase for the uranium-bearing that step 2) obtains and strip liquor are stripped in a manner of multi-stage countercurrent, obtain uranium-bearing Water phase.
2. the separation and recovery method of thorium as described in claim 1 and uranium, it is characterised in that:
In step 1), in the aqueous acid containing thorium and uranium, the acid used is in hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid It is one or more of；
And/or in step 1), in the aqueous acid containing thorium and uranium, sour molar concentration is 0.5-2mol/L；
And/or in step 1), in the aqueous acid containing thorium and uranium, the concentration of thorium is 0.86-2.0mol/L, uranium Concentration is 0.008-0.02mol/L；
And/or in step 1), in the aqueous acid containing thorium and uranium, the mass ratio of thorium and uranium is 10:1~5000:1.
3. the separation and recovery method of thorium as claimed in claim 2 and uranium, it is characterised in that:
In step 1), in the aqueous acid containing thorium and uranium, sour molar concentration is 0.6-1.0mol/L；
And/or in step 1), in the aqueous acid containing thorium and uranium, the concentration of thorium is 1.0mol/L, and the concentration of uranium is 0.01mol/L；
And/or in step 1), in the aqueous acid containing thorium and uranium, the mass ratio of thorium and uranium is 100:1.
4. the separation and recovery method of thorium as claimed in claim 3 and uranium, it is characterised in that: in step 1), described contains thorium In the aqueous acid of uranium, sour molar concentration is 0.8mol/L.
5. the separation and recovery method of thorium as described in claim 1 and uranium, it is characterised in that: in step 1), the feed liquid is The aqueous solution of thorium base spentnuclear fuel also contains Zr other than containing thorium and uranium4+、Nb5+、RuNO3+、Rh3+、Sr2+、Cs+、Ce3+、 Ce4+、Gd3+、Dy3+Fission product, molar concentration of the fission product in feed liquid are 20ppm；The thorium base spentnuclear fuel Before becoming the feed liquid, need to shell, dissolution, flocculation, filtering, condiment processing.
6. the separation and recovery method of thorium as described in claim 1 and uranium, it is characterised in that:
In step 1), organic solvent in the extractant be one of chloroform, n-dodecane, kerosene and toluene or It is several；
And/or in step 1), the volumetric concentration of methylphosphonic acid two (1- methyl) heptyl ester is 20%-30% in the extractant；
And/or in step 1), the acidic materials used in the cleaning solution I is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and amino sulphurs One or more of sour ferrous iron；
And/or in step 1), the molar concentration of I middle acid substance of cleaning solution is 0.2-0.6mol/L；
And/or in step 1), in the fractional extraction, series >=6 grade are extracted, wash series >=6 grade；
And/or in step 1), the stream of the feed liquid, extractant and cleaning solution I compares for 1:(4-7): (0.5-1).
7. the separation and recovery method of thorium as claimed in claim 6 and uranium, it is characterised in that:
In step 1), the molar concentration of I middle acid substance of cleaning solution is 0.3-0.5mol/L；
And/or in step 1), in the fractional extraction, extraction series is 8-10 grades, and washing series is 8 grades；
And/or in step 1), the stream of the feed liquid, extractant and cleaning solution I compares for 1:(5-6): (0.8-1).
8. the separation and recovery method of thorium as described in claim 1 and uranium, it is characterised in that:
In step 2), the acidic materials used in the cleaning solution II are sub- for hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and sulfamic acid One or more of iron；
And/or in step 2), the molar concentration of the acidic materials used in the cleaning solution II is 0.08mol/L；
And/or in step 2), the organic solvent in the benefit extraction agent is in chloroform, n-dodecane, kerosene and toluene It is one or more of；
And/or in step 2), the volumetric concentration of methylphosphonic acid two (1- methyl) heptyl ester is 25%-30% in the benefit extraction agent；
And/or in step 2), series >=5 grade are washed in extraction series >=3 grade of the fractional extraction；
And/or in step 2), it is 1 that the stream of the organic extraction phase containing thorium and uranium, benefit extraction agent and cleaning solution II, which compares: (0.2-0.8):(0.4-1)；
And/or in step 3), the strip liquor is water or aqueous acid；When the strip liquor is aqueous acid, use Acid be one or more of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid；Wherein sour molar concentration is 0.05mol/L or less；
And/or in step 3), series >=4 grade are extracted in the back extraction；
And/or in step 3), in the back extraction, the organic extraction phase of the uranium-bearing and the stream of strip liquor compare for (2-5): 1。
9. the separation and recovery method of thorium as claimed in claim 8 and uranium, it is characterised in that:
In step 2), the extraction series of the fractional extraction is 4-5 grades, and washing series is 6-7 grades；
And/or in step 2), it is 1 that the stream of the organic extraction phase containing thorium and uranium, benefit extraction agent and cleaning solution II, which compares: (0.3-0.6):(0.5-0.8)；
And/or in step 3), when the strip liquor is aqueous acid, wherein the molar concentration of acid is 0.001- 0.01mol/L；
It is 6-8 grades that series is stripped and/or in step 3), in the back extraction；
And/or in step 3), in the back extraction, the organic extraction phase of the uranium-bearing and the stream of strip liquor compare for (2-3): 1。
10. the separation and recovery method of thorium as claimed in claim 9 and uranium, it is characterised in that: in step 2), described contains thorium The stream for extracting agent and cleaning solution II with organic extraction phase, the benefit of uranium compares for 1:(0.4-0.6): (0.5-0.6).
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