CN110373556A - The method of radioactive element is recycled from zirconium industrial residue - Google Patents
The method of radioactive element is recycled from zirconium industrial residue Download PDFInfo
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- CN110373556A CN110373556A CN201910604303.7A CN201910604303A CN110373556A CN 110373556 A CN110373556 A CN 110373556A CN 201910604303 A CN201910604303 A CN 201910604303A CN 110373556 A CN110373556 A CN 110373556A
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- thorium
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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
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0208—Obtaining thorium, uranium, or other actinides obtaining uranium preliminary treatment of ores or scrap
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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
- C22B60/0204—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
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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
- 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
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- 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 method that the present invention relates to a kind of to recycle radioactive element from zirconium industrial residue, comprising the following steps: roast zirconium industrial residue with alkali, obtain roasting waste residue；The zirconium industrial residue contains thorium element and uranium element；The roasting waste residue is leached with water, is filtered, washed, filter residue is obtained；The filter residue is dissolved with concentrated nitric acid, obtains feed liquid；Salting-out agents are added into the feed liquid and extractant is extracted, obtain raffinate I and organic phase I；Contain tri-n-octyl amine and organic solvent in the extractant, organic solvent is selected from least one of ethyl acetate, acetone, n-octyl alcohol and hexamethylene, the acidity of extractant is 1mol/L~3mol/L, and in the extractant, the volumetric concentration of tri-n-octyl amine is 5%~30%；The organic phase I is washed with saturation ammonium nitrate solution, obtains organic phase II；The organic phase II is subjected to first time back extraction with the hydrochloric acid solution of 2.4mol/L~9.6mol/L, obtains thorium enriched solution.This method condition is easy to control, and the radioactive element rate of recovery is high.
Description
Technical field
The present invention relates to non-ferrous metal technical fields, more particularly to a kind of side for recycling thorium, uranium from zirconium industrial residue
Method.
Background technique
Zirconium ore is one of concomitant radioactivity mine, usually with the natural radioactive elements symbiosis such as thorium, uranium, radionuclide concentration
It is higher.During zirconium development and utilization, during each production link, fraction enters in waste water for thorium and uranium, most of to be enriched with
In various waste residues, and a large amount of waste residue is not dealt carefully with, and radionuclide amount is caused to be much higher than local natural radiation
Property background level；Along with most enterprises environmental protection and Radiation Exposure are not perfect, difference is caused to ambient enviroment
The radioactive pollution of degree.Ministry of Environmental Protection's door pays much attention to always radioactive pollution during zirconium ore resources development and utilization
Situation, scientific and technical personnel also adapt to the recycle utilization of China's solid waste in research energetically, it is comprehensive to form solid waste
Solution, the solid waste resource recovery science and technology support of General Promotion China and supportability promote resoures recycling based industry
Scale, to increase substantially china natural resources utilization efficiency, support ecological environment civilization construction provides technology guarantee.
Positive thorium (232) Th is that one kind is present in natural radioactive element in nature, very rich in the content of nature
Richness, about more than the 3 of uranium reserve times.(232) Th itself is not easy to fission, but can pass through a series of nuclear reaction by absorbing neutron
Artificial fissile nuclide (233) U (uranium) is generated, there is good nuclearity energy.Therefore, the utilization of thorium resources is to be expected the following nuclear energy
Develop one of the effective way of center fuel crunch.
National zirconium industrial development is rapid, and a large amount of zirconium industrial residue, zirconium industrial residue are generated and had accumulated in production process
Containing zirconium, aluminium oxide, silicate, 0.1wt%~1wt% U, 0.5wt%~5wt% Th, uranium thorium content in this kind of waste residue
It is higher, corresponding uranium thorium purification Technology's Study should be carried out, as the resource circulation utilization for extracting uranium, thorium, realize concomitant radioactivity
Solid waste circular economy.
Summary of the invention
Based on this, it is necessary to provide a kind of method for recycling radioactive element from zirconium industrial residue, this method technique item
Part is easy to control, and the rate of recovery is high.
A method of recycling radioactive element from zirconium industrial residue, comprising the following steps:
Zirconium industrial residue is roasted with alkali, obtains roasting waste residue；The zirconium industrial residue contains thorium element and uranium element；
The roasting waste residue is leached with water, is filtered, washed, filter residue is obtained；
The filter residue is dissolved with concentrated nitric acid, obtains feed liquid；
Salting-out agents are added into the feed liquid and extractant is extracted, obtain raffinate I and the load containing zr element
The organic phase I of thorium element and uranium element；Contain tri-n-octyl amine and organic solvent in the extractant, the organic solvent is selected from second
At least one of acetoacetic ester, acetone, n-octyl alcohol and hexamethylene；The acidity of the extractant is 1mol/L~3mol/L, in institute
It states in extractant, the volumetric concentration of the tri-n-octyl amine is 5%~30%；
The organic phase I is washed with saturation ammonium nitrate solution, obtains washing miscellaneous rear, load uranium element and thorium element organic phase
II；
The organic phase II is subjected to first time back extraction with the hydrochloric acid of 2.4mol/L~9.6mol/L, is obtained thorium enriched molten
Liquid.
It should be noted that acidity refers to hydrionic molar concentration in solution.
The first time back extraction also obtains the organic phase III of load uranium element in one of the embodiments,；
It is anti-for the second time the method also includes being carried out to the organic phase III with the nitric acid solution of 0.1mol/L~1mol/L
Extraction, obtains uranium enrichment solution.
The volume ratio of the organic phase III and the nitric acid solution is (1~2): (1~2) in one of the embodiments,.
The mass ratio of alkali used in the zirconium industrial residue Yu the zirconium industrial residue is roasted in one of the embodiments,
For (1.5~3): 1, the temperature for roasting the zirconium industrial residue is 300 DEG C~700 DEG C, and the time of roasting is 0.5h~2h.
The temperature of the leaching is 90 DEG C~100 DEG C in one of the embodiments, the roasting waste residue and the water
Mass ratio is 1:(3~5).
The acidity of the feed liquid is 0.1mol/L~6mol/L in one of the embodiments,.
The salting-out agents are the solution containing ammonium hydroxide and nitrate in one of the embodiments,.
The extractant is before extraction through overpickling Balance Treatment, the pickling balance in one of the embodiments,
Processing uses 1mol/L~3mol/L nitric acid solution with the extractant by volume for (1~2): (1~2), which mixes, to be extracted
It takes, after static layering balance, takes upper solution.
The volume ratio of the organic extractant and the feed liquid is (1~2): (1~2) in one of the embodiments,.
The volume ratio of the organic phase II and the hydrochloric acid is (1~2): (1~3) in one of the embodiments,.
The invention has the following advantages:
1) zirconium industrial residue is first roasted by alkali and carries out alkaline hydrolysis by method of the invention, convenient for water logging, is filtered, washed removing
The impurity such as aluminium, silicon, can be same with specific extractant under the facilitation of salting-out agents after gained filter residue is dissolved with concentrated nitric acid
When extract thorium and uranium from feed liquid, impurity such as removal zirconium, silicon, then have thorium element and uranium element to load with the hydrochloric acid of highly acidity
Organic phase II carry out first time back extraction, using thorium in hydrochloric acid system the highly selective back extraction thorium of solubility, and the nitric acid of uranium be complexed
Object is changed into chloride ion complex compound and is retained in organic phase, effectively separates thorium and uranium, obtains thorium；This method not only technique item
Part is easy to control, and by the cooperation of each step, the rate of recovery of thorium is high.
2) method of the invention is by the cooperation of each step, and controls the process conditions of each step, can be to zirconium industry
Thorium and uranium in waste residue are separated and recovered well, and the rate of recovery of thorium and uranium is up to 99.99%.
3) in method of the invention by extractant raffinate I extracted after alkali neutralization slag making, can directly make
It is utilized for zirconium raw materials recovery, and the content of radioactive element reaches industrial discharge standard in the waste water after extraction thorium and uranium, energy
Enough direct emissions are without will cause radioactive element bring environmental pollution.
Detailed description of the invention
Fig. 1 is the flow diagram of an embodiment of the present invention.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
An embodiment of the present invention provides a kind of method that radioactive element is recycled from zirconium industrial residue, referring to Figure 1,
Including with step S1~S7.
S1, basic roasting: roasting zirconium industrial residue with alkali, obtains roasting waste residue；In zirconium industrial residue containing thorium element and
Uranium element.
Specifically, the temperature of roasting is 300 DEG C~700 DEG C, and the time of roasting is 0.5h~2h.
In one embodiment, the mass ratio for roasting alkali used in industrial residue and zirconium industrial residue is (1.5~3): 1.
In one embodiment, alkali used is the basic species such as soda ash, lime stone, sodium hydroxide, potassium hydroxide, calcium hydroxide
Matter.More preferably, alkali used is the mixture of sodium hydroxide, potassium hydroxide or sodium hydroxide and potassium hydroxide.
S2, water logging removal of impurities: the resulting roasting waste residue of step S1 is leached with water and then is filtered, washed, is contained
The filter residue of thorium element and uranium element.
Specifically, the roasting waste residue that step S1 is obtained is put into the hot water of pre- boiling and is leached, then filtered, washed with hot water
Filter cake 1~5 time, the impurity such as removal aluminium, silicon obtain the filter residue containing thorium and uranium.Meanwhile the filtrate containing impurity such as aluminium, silicon is in
Alkalinity can be used for neutralizing the raffinate generated in subsequent step.
In one embodiment, the temperature of water is 90 DEG C~100 DEG C when leaching, roast waste residue and water mass ratio be 1:(3~
5).In this way, the alkaline matter in waste residue after basic roasting can be leached well, through filtering, hot water washing removal aluminium and silicon
Equal impurity.
Preferably, the mass ratio for roasting waste residue and water is 1:(3.5~4.5).In this way, can reach impurity such as aluminium, silicon
It leaches, and energy consumption can be saved and use water.
S3, acid dissolution: the resulting filter residue of step S2 is dissolved with concentrated nitric acid, obtains feed liquid.
Specifically, it is slowly added to concentrated nitric acid while stirring into filter residue, and heats, until stopping when filter residue just dissolves complete
Concentrated nitric acid is only added.
In one embodiment, the acidity of feed liquid is 0.1mol/L~6mol/L.
Present inventor has found by numerous studies, when the acidity of feed liquid is lower than 0.1mol/L, in subsequent extraction
In step, the phenomenon that thorium, the extraction yield of uranium are relatively low, while feed liquid will appear hydrolysis, extractant organic phase serious emulsification is caused, hindered
The purpose of extraction thorium, uranium is not achieved in the only when row of extraction process；And when the acidity of feed liquid is higher than 6mol/L, subsequent extraction step
In rapid, thorium, uranium extraction yield can also reduce, cause thorium in feed liquid, uranium extraction incomplete, the mesh of thoroughly recycling thorium, uranium be not achieved
, the raffinate of discharge still can cause environmental pollution.It, can be with only when the acidity of feed liquid is 0.1mol/L~6mol/L
Effectively extraction thorium and uranium.
Further, the acidity of feed liquid is 2mol/L~3mol/L.
S4, extraction: being added salting-out agents and extractant into feed liquid and extracted, obtain the raffinate I containing zr element and
Load has the organic phase I of thorium element and uranium element.Wherein, tri-n-octyl amine and organic solvent are contained in extractant, it is described organic molten
Agent is selected from least one of ethyl acetate, acetone, n-octyl alcohol and hexamethylene, and the acidity of extractant is 1mol/L~3mol/L,
In extractant, the volumetric concentration of the tri-n-octyl amine is 5%~30%.
In this way, thorium and uranium can be extracted in extractant from feed liquid by above-mentioned extraction.It is found in research, extractant
Middle tri-n-octyl amine concentration is lower than 5%, and thorium and uranium extraction are incomplete；Tri-n-octyl amine concentration is higher than 30%, and the viscosity of organic phase is significant
Increase, in extraction process can not split-phase, cause extraction process that can not carry out, therefore, it is necessary to guarantee tri-n-octyl amine in extractant
Volumetric concentration is 5%~30%.
Specifically, suitable salting-out agents are added into feed liquid, and by the extraction of extractant, by the thorium and uranium extraction in feed liquid
It takes enrichment into extractant, after static layering, obtains organic phase I and raffinate I that load has thorium and uranium.Raffinate I passes through alkali
It neutralizes, after slag making, utilization can be added directly as zirconium raw material, and waste water reaches industrial discharge standard, it can be with direct emission；And
Raffinate I can be neutralized with the filtrate of step S2, save resource.
In one embodiment, salting-out agents are the solution containing ammonium hydroxide and nitrate.
Further, nitrate is selected from least one of ammonium nitrate, aluminum nitrate, calcium nitrate and magnesium nitrate.
Specifically, the preparation of salting-out agents are as follows: weigh 100g~1500g nitrate, add a small amount of water and 10mL~100mL ammonia
Water is diluted with water to 800mL~1500mL after heating dissolves nitrate, spare after filtering.
In this way, salting-out agents are added in the form of a solution, and the pH value of salting-out agents is adjusted by ammonium hydroxide, can exist to avoid nitrate
It is precipitated in feed liquid with crystal form, it is easily controllable.
Preferably, in salting-out agents, the concentration of nitrate is 150g/mL~190g/mL.
Further, feed liquid and the volume ratio of salting-out agents are 1:(1~2).
In this way, the rate of extraction of thorium, uranium can be promoted, and guarantee that thorium, uranium extraction are complete.Applicant has found under study for action,
The dosage of salting-out agents influences thorium extraction yield little；But the dosage of salting-out agents influences very big, the extraction of uranium to the extraction yield of uranium
Rate is reduced with the reduction of salting-out agents dosage, however, the dosage of salting-out agents is excessive, it is excessively high to will cause salt concentration in liquid phase, is increased
The viscosity for adding extractant causes grease split-phase unclear, and organic phase of the meeting containing fractional load thorium and uranium, not only reduces in raffinate
The extraction yield of thorium, uranium, raffinate discharge also pollute the environment.
In one embodiment, before extraction through overpickling Balance Treatment, the pickling Balance Treatment uses extractant
The nitric acid solution of 1mol/L~3mol/L is (1~2) with extractant by volume: (1~2), which mixes, to be extracted, static layering
After balance, upper solution is taken.
In this way, the extractant by above-mentioned pickling Balance Treatment, acidity can match with the acidity of feed liquid, be conducive to
The extraction of thorium and uranium.If extractant is too low without acidity after overpickling Balance Treatment or pickling, it is unfavorable for the extraction of thorium and uranium
It takes, causes the extraction yield of thorium and uranium low, otherwise acidity is excessively high, will increase extraction cost.
Specifically, be by volume (1~2) by extractant and nitric acid solution: (1~2) progress extraction equilibrium is primary, extraction
Static 20min~40min after 3~7 minutes, after layering, takes upper solution, spare as extractant；Lower layer's solution is by alkali
It can be with direct emission with after.
In one embodiment, the volume ratio of extractant and feed liquid is (1~2): (1~2).
In one embodiment, extraction series is 1~3 grade, and extraction time is 10min~20min.
Specifically, being (1~2) according to the volume ratio of extractant and feed liquid: feed liquid is added in organic phase by (1~2),
1~3 grade of extraction is carried out, extraction time is 10min~20min, after static layering 20min~40min, releases raffinate I, obtains
Load has the organic phase I of thorium element and uranium element.Wherein, raffinate I can be after alkali neutralization slag making, as zirconium raw materials recovery benefit
With direct discharging of waste water.
S5, washing impurity-removing: washs the organic phase I with saturation ammonium nitrate solution, obtain washing it is miscellaneous after, load have uranium element and
The organic phase II of thorium element.
Specifically, organic phase I1~3 time, organic phase I and used saturation ammonium nitrate are washed with saturation ammonium nitrate solution
The volume ratio of solution is 1:(1~2), the impurity such as nitrate can be not only washed away, but also can prevent thorium or uranium element from organic phase I
Middle rinse takes off, and obtains the organic phase II that load has thorium element and uranium element.The wash water generated in washing process can enter recovery ammonia
System recycles ammonia, direct discharging of waste water.
It is appreciated that by the volume ratio of organic phase I in control washing times and washing process and saturation ammonium nitrate solution,
While guaranteeing impurity elimination effect, and control production cost.
S6, be stripped for the first time: organic phase II resulting to step S5 with the hydrochloric acid solution of 2.4mol/L~9.6mol/L into
Row is stripped for the first time, is obtained thorium enriched solution and is loaded the organic phase III of uranium element.
Specifically, 2.4mol/L~9.6mol/L is added in batches in the organic phase II for having thorium element and uranium element to load
Hydrochloric acid solution carry out back extraction thorium, obtain thorium enriched solution and load uranium element organic phase III.
In one embodiment, the volume ratio of organic phase II and hydrochloric acid solution is (1~2): (1~3).
It should be understood that extractant effectively can extract thorium and uranium simultaneously from nitric acid solution in the presence of salting-out agents, and
Nitric acid complex compound is formed, and then is selectively stripped thorium using the highly acidity hydrochloric acid solution of 2.4mol/L~9.6mol/L, thorium is rich
Collection is into hydrochloric acid solution, and the nitric acid complex compound of uranium transformation chloride ion complex compound is retained in organic phase, after static layering, is obtained
Thorium enriched solution and load have the organic phase III of uranium and a small amount of thorium.If the acidity of hydrochloric acid solution is lower than 2.4mol/L, the nitre of uranium
Acid complex is changed into that chloride ion complex compound is incomplete, and organic phase cannot be then retained in the uranium of chloride ion complex compound by not changing
In, but as thorium enters water phase, so that thorium uranium separation is relatively low, the proportion of goods damageds of uranium increase, simultaneously as hydrochloric acid solution
Sour bottom is relatively low, and the nitric acid complex compound of thorium cannot be completely reformed into chloride ion complex compound and enter water phase, leads to the nitric acid of part thorium
Complex compound remains in organic phase, causes the yield of thorium relatively low., whereas if hydrochloric acid solution acidity is higher than 9.6mol/L,
Then the nitric acid complex compound of uranium is completely transformed into chloride ion complex compound, has all been retained in camera, cannot enter water phase by back extraction,
And viscosity increases when extracting, split-phase is unclear, to not only the production cycle be caused to extend, it is excessive to also result in thorium loss, causes to give birth to
It is excessively high to produce cost.
In one embodiment, the series of back extraction is 2~3 grades for the first time, and Stripping times are 10min~20min.
Specifically, by hydrochloric acid solution be added in load organic phases II carry out 2~3 grades back extraction, Stripping times be 10min~
20min, static layering 20min~40min obtain thorium enriched solution and load the organic phase III of uranium element.
S7, second are stripped: to the resulting organic phase of step S6 III with acidity be 0.1mol/L~1mol/L nitric acid it is molten
Liquid carries out second and is stripped, and obtains uranium enrichment solution.
In one embodiment, the volume ratio of organic phase III and nitric acid solution is (1~2): (1~2).
Specifically, it is (1~2): (1~2) according to the volume ratio of organic phase III and nitric acid solution, is 0.1mol/L by acidity
The nitric acid solution of~1mol/L be added to load have in the organic phase III of uranium, carry out 2~3 grades back extraction, extraction time be 10min~
20min, static layering 20min~40min obtain uranium enrichment solution.
The following are specific embodiments
Embodiment 1:
1, it roasts: weighing 100g zirconium industrial residue and be placed in corundum crucible, through detecting, the content of Th in the zirconium industrial residue
For 3.4wt%, U 0.045wt%；Sodium hydroxide 150g is added into crucible by solid caustic soda ratio 1:1.5, mixes, roasting, control roasting
Burning temperature is 300 degree, calcining time 0.5 hour.
2, water logging cleans: roasting waste material crucible being put into the hot water that 400mL boils in advance and is leached, then filters, use hot water wash
Wash filter cake 1 separation aluminium, silicon.Alkaline filtrate is for neutralizing subsequent raffinate.
3, acid dissolution: appropriate concentrated nitric acid being added into the filter cake after washing, and is heated to just dissolving, and controls feed acidity
For 0.1mol/L.
4, pickling balances: the volume ratio with organic phase and acidity for the nitric acid solution of 1mol/L is that O:A=2:1 is extracted
Balance is primary, extracts after five minutes, static layering 30min, the extraction raffinate of releasing direct emission after alkali neutralization, and upper liquid is used as
Subsequent extractant.
5, it extracts: weighing 500g aluminum nitrate, add a small amount of water and 50mL ammonium hydroxide, be diluted with water to 1000mL after heating for dissolving,
After filtering, salting-out agents are obtained.
It is 1:1 by feed liquid and the volume ratio of salting-out agents, salting-out agents is added in feed liquid, with (N235) containing 5% tri-n-octyl amine
Organic phase ethyl acetate extracting and enriching feed liquid in thorium, uranium.Extraction series 1 time, static layering obtain load uranium element and thorium
The organic phase I of element and raffinate I containing zr element.For raffinate I after alkali neutralization slag making, slag can be directly placed into slag library
It is utilized as zirconium raw materials recovery, waste water reaches industrial discharge standard direct emission.
6, washing impurity-removing: by compared to O:A=2:1 saturation ammonium nitrate solution wash load organic phase I, washing times 1
It is secondary, the organic phase II of load thorium element and uranium element is obtained after washing impurity-removing.Wash water enter ammonia recovery system recycling ammonia, waste water with
Raffinate I merges to be handled for alkali neutralization slag making together.
7, it is stripped for the first time: by the hydrochloric acid that 2.4mol/L is added in the load organic phases II after washing compared to O:A=1:2 to extraction
Solution is stripped thorium, is stripped series 2 times, extraction time 15min, static layering 30min, obtains the aqueous solution of thoriated and bears
Carry the organic phase III of uranium element.
8, it is stripped for second: by the 0.1mol/L nitric acid solution of organic phase III after being stripped thorium compared to O:A=2:1
It is stripped uranium therein, is stripped series 2 times, extraction time 15min, static layering 30min, the aqueous solution and zero load for obtaining uranium-bearing have
Machine phase.
Through detecting, thorium, uranium the rate of recovery reached 99.99%, the separation that uranium is removed in thorium is 3.2 × 104, uranium
The separation of middle removal thorium is up to 4.6 × 104。
It should be noted that referring to oily phase: water phase compared to O:A；Amount/zirconium Industry Waste of thorium element obtained by the thorium rate of recovery=recycling
Amount × 100% of thorium element in slag, the amount of uranium element in amount/zirconium industrial residue of uranium element obtained by the uranium rate of recovery=recycling ×
100%；The content that thorium in content/uranium enrichment solution of uranium in separation=uranium enrichment solution of uranium is removed in thorium, in uranium
Except in separation=uranium enrichment solution of thorium in content/uranium enrichment solution of uranium thorium content.
Embodiment 2:
1, it roasts: weighing 100g zirconium industrial residue and be placed in corundum crucible, through detecting, the content of Th in the zirconium industrial residue
For 3.4wt%, U 0.045wt%；Sodium hydroxide 300g is added into crucible by solid caustic soda ratio 1:3, mixes, roasting, control roasting
Temperature is 700 degree, calcining time 2 hours.
2, water logging cleans: roasting waste material crucible being put into the hot water that 400mL boils in advance and is leached, then filters, use hot water wash
Wash filter cake 1 separation aluminium, silicon.Alkaline filtrate can be used for neutralizing subsequent raffinate.
3, acid dissolution: appropriate concentrated nitric acid being added into the filter cake after washing, and is heated to just dissolving, control feed liquid acid
Degree is 6mol/L.
4, pickling balances: the volume ratio with organic phase and acidity for the nitric acid solution of 3mol/L is that O:A=1:2 is extracted
Balance is primary, extracts after five minutes, static layering 30min, the extraction raffinate of releasing direct emission after alkali neutralization, and upper liquid is used as
Subsequent extractant.
5, it extracts: weighing 500g aluminum nitrate, add a small amount of water and 50mL ammonium hydroxide, be diluted with water to 1000mL after heating for dissolving,
After filtering, aluminum nitrate salting-out agents are obtained.
It is 1:2 by feed liquid and the volume ratio of salting-out agents, aluminum nitrate salting-out agents is added in feed liquid, with containing 30% tri-n-octyl amine
(N235) the thorium in organic phase hexamethylene extracting and enriching feed liquid, uranium.Extraction series 3 times, static layering obtain load uranium element
With the organic phase I and raffinate I of thorium element.For raffinate I after alkali neutralization slag making, slag can be directly placed into slag library as zirconium original
Material recycles, and waste water reaches industrial discharge standard direct emission.
6, washing impurity-removing: by compared to O:A=1:2 saturation ammonium nitrate solution wash load organic phase I, washing times 3
It is secondary, the organic phase II that load has thorium element and uranium element is obtained after washing impurity-removing.Wash water enters ammonia recovery system recycling ammonia, waste water
Merge with a raffinate together for neutralizing slag making processing.
7, it is stripped for the first time: by the hydrochloric acid that 9.6mol/L is added in the load organic phases II after washing compared to O:A=1:1 to extraction
Solution is stripped thorium, is stripped series 3 times, extraction time 15min, static layering 30min, obtains the aqueous solution of thoriated and bears
Carry the organic phase III of uranium element.
8, it is stripped for second: by the 0.1mol/L nitric acid of load organic phases III after being stripped thorium compared to O:A=1:2
Solution is stripped uranium therein, is stripped series 3 times, extraction time 15min, static layering 30min, contained uranium-bearing it is water-soluble
Liquid and unloaded organic phase.
Through detecting, thorium, uranium the rate of recovery reached 99.99%, the separation that uranium is removed in thorium is 3.7 × 104, uranium
The separation of middle removal thorium is 5.2 × 104。
Embodiment 3:
1, it roasts: weighing 100g zirconium industrial residue and be placed in corundum crucible, through detecting, the content of Th in the zirconium industrial residue
For 3.4wt%, U 0.045wt%；Sodium hydroxide 200g is added into crucible by solid caustic soda ratio 1:2, mixes, roasting, control roasting
Temperature is 450 degree, calcining time 1 hour.
2, water logging cleans: roasting waste material crucible being put into the hot water that 500mL boils in advance and is leached, then filters, use hot water wash
Wash filter cake 1 separation aluminium, silicon.Alkaline filtrate is for neutralizing subsequent raffinate.
3, acid dissolution: appropriate concentrated nitric acid being added into the filter cake after washing, and is heated to just dissolving, and controls feed acidity
For 2.5mol/L.
4, pickling balances: the volume ratio with organic phase and acidity for the nitric acid solution of 2mol/L is that O:A=1:1 is extracted
Balance is primary, extracts after five minutes, static layering 30min, the extraction raffinate of releasing direct emission after alkali neutralization, and upper liquid is used as
Subsequent extractant.
5, it extracts: weighing 500g magnesium nitrate, add a small amount of water and 50mL ammonium hydroxide, be diluted with water to 1000mL after heating for dissolving,
After filtering, magnesium nitrate salting-out agents are obtained.
It is 1:1 by feed liquid and the volume ratio of salting-out agents, aluminum nitrate salting-out agents is added in feed liquid, with containing 10% tri-n-octyl amine
(N235) the thorium in organic phase ethyl acetate extracting and enriching feed liquid, uranium.Extraction series 1 time, static layering obtain load uranium member
The organic phase I and raffinate I of element and thorium element.For raffinate I after alkali neutralization slag making, slag can be directly placed into slag library as zirconium
Raw materials recovery utilizes, and waste water reaches industrial discharge standard direct emission.
6, washing impurity-removing: by compared to O:A=2:1 saturation ammonium nitrate solution wash load organic phase I, washing times 1
It is secondary, the organic phase II of thorium element and uranium element is obtained after washing impurity-removing.Wash water enters ammonia recovery system recycling ammonia, waste water and raffinate
Liquid I merges to be handled for alkali neutralization slag making together.
7, it is stripped for the first time: by the hydrochloric acid that 5.5mol/L is added in the load organic phases II after washing compared to O:A=1:2 to extraction
Solution is stripped thorium, is stripped series 2 times, extraction time 15min, static layering 30min, obtains the aqueous solution of thoriated and bears
Carry the organic phase III of uranium element.
8, it is stripped for second: by the 0.5mol/L nitric acid solution of organic phase III after being stripped thorium compared to O:A=1:1
It is stripped uranium therein, is stripped series 2 times, extraction time 15min, static layering 30min, the aqueous solution and zero load for obtaining uranium-bearing have
Machine phase.
Through detecting, thorium, uranium the rate of recovery reached 99.99%, the separation that uranium is removed in thorium is 3.9 × 104, uranium
The separation of middle removal thorium is up to 5.3 × 104。
Embodiment 4:
It is essentially identical with the raw material and operating procedure of embodiment 1, the difference is that calcination steps change is as follows: weighing
100g zirconium industrial residue is placed in corundum crucible, Th 3.4wt%, U 0.045wt% in waste residue；By solid caustic soda ratio 1:1 to crucible
Middle addition sodium hydroxide mixes, roasting, and control maturing temperature is 200 degree, calcining time 20min.
Through detecting, the rate of recovery of thorium is 83.6%, the rate of recovery of uranium is 70.4%, and the separation that uranium is removed in thorium is
3.0×104, to remove the separation of thorium in uranium be 3.5 × 104。
Embodiment 5:
It is essentially identical with the raw material and operating procedure of embodiment 1, the difference is that the change of pickling equilibrium step is as follows: with
The volume ratio of organic phase and 0.1mol/L nitric acid solution is that O:A=1:1 progress extraction equilibrium is primary, static point after five minutes of extraction
After layer 30min, the extraction raffinate of releasing direct emission after alkali neutralization, upper liquid is used as subsequent extractant.
Through detecting, the rate of recovery of thorium is 75.2%, the rate of recovery of uranium is 69.3%, and the separation that uranium is removed in thorium is
2.8×104, to remove the separation of thorium in uranium be 2.5 × 104。
Comparative example 1:
It is essentially identical with the raw material and operating procedure of embodiment 1, the difference is that extraction step change is as follows: in feed liquid
In any salting-out agents are not added, with containing 5% tri-n-octyl amine (N235) organic extractant phase enrichment feed liquid in thorium, uranium.Extract series 1
Secondary, static layering, raffinate is after alkali neutralization slag making, and slag can be directly placed into slag library and utilize as zirconium raw materials recovery, waste water
Reach industrial discharge standard direct emission.
Through detecting, the rate of recovery of thorium is 65.3%, the rate of recovery of uranium is 55.6%, and the separation that uranium is removed in thorium is
2.5×103, the separation of thorium is removed in uranium up to 1.7 × 103。
Comparative example 2:
It is essentially identical with the raw material and operating procedure of embodiment 1, the difference is that the change of first time stripping steps is as follows:
It is stripped thorium by the hydrochloric acid solution that 1.0mol/L is added in the organic phase after washing compared to O:A=1:2 to extraction, is stripped series 1 time.
Through detecting, the rate of recovery of thorium is 85.2%, the rate of recovery of uranium is 99.99%, and the separation that uranium is removed in thorium is
4.2, the separation that thorium is removed in uranium is 1.5.
Comparative example 3:
It is essentially identical with the raw material and operating procedure of embodiment 1, the difference is that the change of secondary stripping steps is as follows: pressing
Raffinate II after thorium will be stripped compared to O:A=3:1 is stripped uranium therein with 2mol/L nitric acid solution, is stripped series 1 time.
Through detecting, the rate of recovery of thorium is 99.99%, the rate of recovery of uranium is 45.7%, and the separation that uranium is removed in thorium is
3.6×104, to remove the separation of thorium in uranium be 5.6.
Comparative example 4
It is essentially identical with the raw material and operating procedure of embodiment 1, the difference is that extraction step change is as follows: extractant
The content of middle tri-n-octyl amine (N235) is 3%；With containing 3% tri-n-octyl amine (N235) organic extractant phase enrichment feed liquid in thorium,
Uranium.Extraction series 1 time, static layering, after alkali neutralization slag making, slag can be directly placed into slag library and return as zirconium raw material raffinate
It receives and utilizes, waste water reaches industrial discharge standard direct emission.
Through detecting, the rate of recovery of thorium is 56.3%, the rate of recovery of uranium is 52.5%, and the separation that uranium is removed in thorium is
4.5×103, the separation of thorium is removed in uranium up to 5.3 × 103。
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of method for recycling radioactive element from zirconium industrial residue, which comprises the following steps:
Zirconium industrial residue is roasted with alkali, obtains roasting waste residue；The zirconium industrial residue contains thorium element and uranium element；
The roasting waste residue is leached with water, is filtered, washed, filter residue is obtained；
The filter residue is dissolved with concentrated nitric acid, obtains feed liquid；
Salting-out agents are added into the feed liquid and extractant is extracted, obtain the raffinate I containing zr element and load thorium member
The organic phase I of element and uranium element；Contain tri-n-octyl amine and organic solvent in the extractant, the organic solvent is selected from acetic acid second
The acidity of at least one of ester, acetone, n-octyl alcohol and hexamethylene, the extractant is 1mol/L~3mol/L, in the extraction
The volumetric concentration for taking tri-n-octyl amine described in agent is 5%~30%；
The organic phase I is washed with saturation ammonium nitrate solution, obtains washing miscellaneous rear, load uranium element and thorium element organic phase II；
The organic phase II is subjected to first time back extraction with the hydrochloric acid solution of 2.4mol/L~9.6mol/L, is obtained thorium enriched molten
Liquid.
2. the method according to claim 1, wherein first time back extraction also obtains the organic of load uranium element
Phase III；
The method also includes carrying out second with the nitric acid solution of 0.1mol/L~1mol/L to the organic phase III to be stripped, obtain
To uranium enrichment solution.
3. according to the method described in claim 2, it is characterized in that, the organic phase III and the volume ratio of the nitric acid solution are
(1~2): (1~2).
4. the method according to claim 1, wherein roasting alkali used in the zirconium industrial residue and the zirconium work
The mass ratio of industry waste residue is (1.5~3): 1, the temperature for roasting the zirconium industrial residue is 300 DEG C~700 DEG C, the time of roasting
For 0.5h~2h.
5. the method according to claim 1, wherein the temperature of the leaching be 90 DEG C~100 DEG C, the roasting
The mass ratio of waste residue and the water is 1:(3~5).
6. the method according to claim 1, wherein the acidity of the feed liquid is 0.1mol/L~6mol/L.
7. the method according to claim 1, wherein the salting-out agents are the solution containing ammonium hydroxide and nitrate.
8. the method according to claim 1, wherein the extractant before extraction through overpickling balance at
Reason, the pickling Balance Treatment use the nitric acid solution of 1mol/L~3mol/L with the extractant by volume for (1~2):
(1~2) mixing is extracted, and after static layering balance, takes upper solution.
9. the method according to claim 1, wherein the volume ratio of the extractant and the feed liquid be (1~
2): (1~2).
10. described in any item methods according to claim 1~9, which is characterized in that the organic phase II and the hydrochloric acid solution
Volume ratio be (1~2): (1~3).
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| CN115775646A (en) * | 2022-11-18 | 2023-03-10 | 中核第四研究设计工程有限公司 | Method for stabilizing uranium associated zirconium and zirconium oxide neutralization slag and stabilizing agent used in method |
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