CN112593099A - Method for extracting and preparing nuclear pure ThO from rare earth waste residues2Method for producing powder - Google Patents
Method for extracting and preparing nuclear pure ThO from rare earth waste residues2Method for producing powder Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 89
- 239000002699 waste material Substances 0.000 title claims abstract description 55
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 46
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 43
- 239000000843 powder Substances 0.000 title claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 86
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 41
- SFKTYEXKZXBQRQ-UHFFFAOYSA-J thorium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Th+4] SFKTYEXKZXBQRQ-UHFFFAOYSA-J 0.000 claims abstract description 24
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 238000005406 washing Methods 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 42
- -1 cerium ion Chemical class 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000012065 filter cake Substances 0.000 claims description 30
- 239000012074 organic phase Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 17
- 239000003350 kerosene Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 14
- 238000006073 displacement reaction Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910052770 Uranium Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005457 optimization Methods 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229910004369 ThO2 Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 150000003983 crown ethers Chemical class 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- ITLVEWNVLPRTAW-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Th+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Th+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] ITLVEWNVLPRTAW-UHFFFAOYSA-N 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- KTFKDIPXTYWTDK-UHFFFAOYSA-L thorium(2+);dihydroxide Chemical compound [OH-].[OH-].[Th+2] KTFKDIPXTYWTDK-UHFFFAOYSA-L 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 abstract description 14
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000003113 alkalizing effect Effects 0.000 abstract description 2
- 239000002901 radioactive waste Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 9
- 238000001354 calcination Methods 0.000 description 6
- 239000000284 extract Substances 0.000 description 4
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- 239000002354 radioactive wastewater Substances 0.000 description 1
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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
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
- 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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- 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
- C22B7/007—Wet processes by acid leaching
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- 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
- C22B7/04—Working-up slag
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Abstract
The invention belongs to the technical field of radioactive waste treatment, and particularly relates to a method for extracting and preparing nuclear pure ThO from rare earth waste residues2The powder method is used for alkalizing the rare earth waste residues, so that preliminary separation of thorium elements and partial impurity elements can be realized, the problem of equipment corrosion can be effectively solved, and meanwhile, the generated thorium hydroxide is easily converted into a thorium nitrate solution for next extraction and purification treatment. The method adopts centrifugal extraction technology to carry out nitric acid treatmentThe thorium is extracted and purified, the method has the characteristics of high recovery rate, continuous operation, low energy consumption and the like, and realizes the high-efficiency separation of the thorium element and other rare earth elements, so that the method is used for extracting and preparing the nuclear pure ThO from the rare earth waste residue2Powders are of great significance.
Description
Technical Field
The invention belongs to the technical field of radioactive waste treatment, and particularly relates to a method for extracting and preparing nuclear pure ThO from rare earth waste residues2A method of powdering.
Background
In the rare earth dressing and smelting process, thorium is mined as an accompanying object, the utilization rate of thorium resources is low, a large amount of thorium resources are finally stored separately in the form of rare earth waste residues, the rare earth waste residues can cause radioactive pollution, precious thorium resources can be seriously wasted, and therefore thorium needs to be recycled.
In the traditional recovery process, the ThO is extracted and prepared by adopting the processes of acid mixing, extraction, precipitation, burning and the like2The process has the advantages that the dosage of reagents is large, the equipment is easy to corrode by using the fluorine-containing acid liquid, the amount of radioactive wastewater generated is large, and the problems of low recovery efficiency, high energy consumption and the like of the traditional extraction equipment exist.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a method for extracting and preparing nuclear pure ThO from rare earth waste residues2The powder method is used for alkalizing the rare earth waste residues, so that preliminary separation of thorium elements and partial impurity elements can be realized, the problem of equipment corrosion can be effectively solved, and meanwhile, the generated thorium hydroxide is easily converted into a thorium nitrate solution for next extraction and purification treatment. The method adopts centrifugal extraction technology to extract and purify thorium nitrate, and has recovery rateHigh efficiency separation of thorium element from other rare earth elements, continuous operation, low energy consumption, etc. therefore, the invention extracts and prepares nuclear pure ThO from rare earth waste residue2Powders are of great significance.
The technical scheme of the invention is as follows:
method for extracting and preparing nuclear pure ThO from rare earth waste residues2The powder preparation method comprises the following steps of firstly, pretreating the rare earth waste residue, determining the components of the rare earth waste residue, and adding water to make slurry of the rare earth waste residue;
step two, heating the waste residue slurry to a proper temperature, adding alkali liquor to perform an alkalization displacement reaction to obtain a thorium hydroxide filter cake, and filtering and washing the filter cake;
performing acid dissolution on the thorium hydroxide filter cake to obtain a thorium nitrate solution, and adding an oxidant to perform cerium ion reduction conversion treatment;
screening a proper extracting agent, removing uranium ions in the solution by adopting a centrifugal extraction technology, and then performing extraction and back extraction of thorium ions;
step five, after extraction and purification, adding a precipitator to precipitate, dry and roast thorium ions to prepare the generated nuclear pure-grade ThO2And (3) powder.
In the first step, water is added into the rare earth waste residue to prepare slurry, and the adding amount of the water is adjusted to be within the range of 5-12L/kg of the waste residue.
In the step two alkalization displacement process, sodium hydroxide, potassium hydroxide and ammonia water are selected to carry out alkaline displacement reaction.
In the second alkalization and replacement process, the concentration of an alkaline solution is adjusted to 2.5-4 mol/L, and the reaction temperature is controlled within the range of 60-90 ℃;
in the alkalization replacement process, the adding amount of an alkaline solution is 120-200% of the amount required by normal reaction;
in the alkalization displacement process, the reaction time of displacement by using alkali liquor is not less than 3 h;
in the alkalization replacement process, after replacement is finished, the precipitate is filtered by using nylon filter cloth.
In the washing process of the thorium dihydroxide filter cake, deionized water is used for hot washing, and the washing temperature of the deionized water is 50-70 ℃;
in the washing process of the thorium hydroxide filter cake, the washing times of deionized water are not less than 3-5 times, and the washing dosage is 10-15L/kg of precipitate every time.
In the thorium hydroxide filter cake dissolving process, nitric acid is selected as an acid solution, and the dissolving temperature is controlled within the range of 60-90 ℃.
In the preparation process of the thorium trinitrate solution, the concentration of thorium ions in the solution is adjusted to be 50-300 g/L, and the acidity of the solution is adjusted to be 1-4 mol/L.
Step three, during the reduction and conversion process of cerium ions, H is selected2O2Reductive conversion as an oxidant, H2O2The adding amount is 3-12% of the volume of the thorium nitrate solution.
Selecting carboxylic acid, sulfonic acid, organic phosphoric acid, crown ether and primary amine extractant to perform screening test in the extractant optimization process in the fourth step; in the extraction agent optimization process, tributyl phosphate is selected as an extraction agent, and kerosene is adopted as a diluent;
in the extraction process, extraction equipment such as a mixer-settler, an ion extractor and a jet extractor is selected, the extraction material is stainless steel, PP, PMMA and the like, and the treatment capacity of the extraction equipment is 1-10L/h;
in the extraction and back extraction processes, a centrifugal extractor is preferably selected, 10-20 stages of extractors are adopted for series coupling, and the rotation number of the extractors is selected to be 3000-6000 r/min;
in the uranium removing process of the thorium nitrate solution, the extraction system is 3-10% of TBP-kerosene;
in the extraction process of the thorium ions, the extraction system is 20-40% of TBP-kerosene;
in the extraction process, a countercurrent extraction mode is adopted, and the flow ratio of a water phase inlet to an organic phase inlet is 1: 2-4: 1;
in the washing process, 0.5-1.5 mol/L nitric acid solution is selected as washing liquid, and the using amount of the washing liquid is 0.5-1 time of the volume of the loaded organic phase;
in the back extraction process, hot water is selected as a back extractant, and the temperature of the hot water is controlled to be 55-85 ℃;
in the back extraction process, the flow ratio of a water phase inlet to an organic phase inlet in the experiment process is 1: 3-2: 1;
and in the back extraction process and the experimental process, liquid at the water phase outlet is collected, and the impurity content is analyzed and detected.
In the precipitation process of the thorium ions in the step five, oxalic acid, hydrogen peroxide and NaOH can be selected to carry out precipitation of the thorium ions;
in the precipitation process of the thorium ions, the precipitation temperature is controlled within the range of 60-90 ℃, precipitates are filtered while being hot, and are washed for 3 times by deionized water;
in the drying and roasting process, a muffle furnace is selected for drying and roasting, the drying temperature is 250-350 ℃, the time is 2-3 hours, the roasting temperature is 700-850 ℃, and the time is 1-2 hours.
The invention has the beneficial effects that:
the method adopts the technologies of alkalization treatment, centrifugal extraction and the like to realize the treatment and purification processes of the rare earth waste residue, has simple process flow, less reagent consumption and less corrosion to equipment, is easy to extract thorium element from the rare earth waste residue, has good extraction and back extraction effects by using the centrifugal extraction technology, has no impurity introduction in the processes of precipitation and calcination, can prepare thorium dioxide powder with the purity of over 99.9 percent, and has lower content of radioactive elements after the extraction tail water is treated, thereby meeting the emission standard.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
FromExtraction and preparation of nuclear pure ThO from rare earth waste residue2The powder preparation method comprises the following specific steps:
the method comprises the following steps of firstly, pretreating the rare earth waste residue, determining the components of the rare earth waste residue, and adding water to make slurry of the rare earth waste residue;
step two, heating the waste residue slurry to a proper temperature, adding alkali liquor to perform an alkalization displacement reaction to obtain a thorium hydroxide filter cake, and filtering and washing the filter cake;
performing acid dissolution on the thorium hydroxide filter cake to obtain a thorium nitrate solution, and adding an oxidant to perform cerium ion reduction conversion treatment;
screening a proper extracting agent, removing uranium ions in the solution by adopting a centrifugal extraction technology, and then performing extraction and back extraction of thorium ions;
step five, after extraction and purification, adding a precipitator to precipitate, dry and roast thorium ions to prepare the generated nuclear pure-grade ThO2And (3) powder.
Step one, adding water into the rare earth waste residues to prepare slurry, wherein the adding amount of the water is adjusted to be within the range of 5-12L/kg of the waste residues.
And step two, in the alkalization replacement process, sodium hydroxide, potassium hydroxide, ammonia water and the like are selected for carrying out alkaline replacement reaction.
And step two, in the alkalization replacement process, the concentration of the alkaline solution is adjusted to 2.5-4 mol/L, and the reaction temperature is controlled within the range of 60-90 ℃.
And step two, in the alkalization and replacement process, the adding amount of the alkaline solution is 120-200% of the amount required by the normal reaction.
In the alkalization and replacement process, the reaction time of replacement by using alkali liquor is not less than 3 h.
And step two, in the alkalization and replacement process, filtering the precipitate by using nylon filter cloth after replacement is finished.
And step two, washing the thorium hydroxide filter cake by using deionized water at 50-70 ℃ while the thorium hydroxide filter cake is hot.
And in the washing process of the thorium hydroxide filter cake in the second step, the washing times of deionized water are not less than 3-5 times, and the washing dosage is 10-15L/kg of precipitate every time.
In the thorium hydroxide filter cake dissolving process, nitric acid is preferably used as an acid solution, and the dissolving temperature is controlled within the range of 60-90 ℃.
And step three, in the preparation process of the thorium nitrate solution, the concentration of thorium ions in the solution is adjusted to be within the range of 50-300 g/L, and the acidity of the solution is adjusted to be within the range of 1-4 mol/L.
Step three the cerium ion reduction conversion process, preferably H2O2Reductive conversion as an oxidant, H2O2The adding amount is 3-12% of the volume of the thorium nitrate solution.
And step four, selecting the extracting agents such as carboxylic acid, sulfonic acid, organic phosphoric acid, crown ether, primary amine and the like for screening test in the extracting agent optimization process.
And step four, optimizing the extractant process, and finally selecting tributyl phosphate (TBP) as the extractant and adopting kerosene as the diluent.
And step four, in the extraction process, extraction equipment such as a mixer-settler, an ion extractor and a jet extractor is selected, the extraction material is stainless steel, PP, PMMA and the like, and the treatment capacity of the extraction equipment is 1-10L/h.
And step four, in the extraction and back extraction processes, a centrifugal extractor is preferably selected, 10-20 stages of extractors are adopted for series coupling, and the rotation number of the extractors is selected to be 3000-6000 r/min.
And step four, in the uranium removing process of the thorium nitrate solution, the extraction system is 3% -10% of TBP-kerosene.
And step four, in the extraction process of the thorium ions, the extraction system is 20-40% of TBP-kerosene.
And step four, in the extraction process, a countercurrent extraction mode is adopted, and the flow ratio of a water phase inlet to an organic phase inlet is 1: 2-4: 1.
And step four, in the washing process, 0.5-1.5 mol/L nitric acid solution is selected as a washing liquid, and the using amount of the washing liquid is 0.5-1 time of the volume of the loaded organic phase.
And step four, in the back extraction process, hot water is selected as a back extractant, and the temperature of the hot water is controlled to be 55-85 ℃.
And step four, performing a back extraction process, wherein the flow ratio of the water phase inlet to the organic phase inlet in the experimental process is 1: 3-2: 1.
And step four, a back extraction process, namely collecting liquid at the water phase outlet in the experimental process, and analyzing and detecting the content of impurities.
And fifthly, in the precipitation process of the thorium ions, oxalic acid, hydrogen peroxide, NaOH and the like can be selected for precipitation of the thorium ions.
And fifthly, in the precipitation process of the thorium ions, the precipitation temperature is controlled within the range of 60-90 ℃, the precipitate is filtered while being hot, and is washed for 3 times by deionized water.
And fifthly, in the drying and roasting process, a muffle furnace is selected for drying and roasting, the drying temperature is 250-350 ℃, the time is 2-3 hours, the roasting temperature is 700-850 ℃, and the time is 1-2 hours.
Example 1:
step one, pretreating the rare earth waste residues, measuring the components of the rare earth waste residues, adding 5-12L of deionized water into each kilogram of waste residues to make slurry, controlling the temperature of the slurry of the waste residues to be 60-90 ℃,
and step two, adding 2.5-4 mol/L alkali liquor to perform an alkaline displacement reaction, wherein the addition amount of the alkali liquor is 120-180% of the normal reaction amount, and the displacement reaction is not less than 3 h. And washing the generated thorium hydroxide filter cake at 50-70 ℃ for not less than 3-5 times.
And step three, dissolving the thorium hydroxide filter cake by using nitric acid, controlling the dissolving temperature to be 60-90 ℃, and adjusting the thorium ion concentration in the solution to be 50-300 g/L and the acidity to be 1-4 mol/L. Adding H with the volume of 3-12 percent into thorium nitrate solution2O2Reducing and converting cerium ions to obtain an extract stock solution for later use.
And step four, selecting tributyl phosphate as an extraction medium, using kerosene as an extraction diluent, firstly using TBP-kerosene with the volume ratio of 3-10% to perform solution uranium removal operation, then using TBP-kerosene with the volume ratio of 20-40% to perform thorium extraction operation, adopting a countercurrent extraction mode in the two extraction processes, adopting 10-20 stages of extractors to be coupled in series, selecting the revolution of the extractors to be 3000-6000 r/min, and setting the flow ratio of an aqueous phase inlet to an organic phase inlet to be 1: 2-4: 1. Collecting the organic phase loaded with thorium ions for washing treatment, wherein the concentration of nitric acid in a washing liquid is 0.5-1.5 mol/L, and the using amount of the washing liquid is 0.5-1 time of the volume of the loaded organic phase. And (3) carrying out back extraction treatment on the loaded organic phase by adopting hot water at the temperature of 55-85 ℃, wherein the ratio of the back extraction agent to the loaded organic phase is 1: 3-2: 1, and collecting a water phase outlet solution.
And step five, selecting oxalic acid, hydrogen peroxide, NaOH and the like to precipitate the strip liquor, controlling the temperature of the precipitation solution at 60-90 ℃, filtering the hot precipitate, and washing the hot precipitate for 3 times by using deionized water. And (3) drying and calcining the thorium dioxide filter cake by using a muffle furnace, wherein the drying temperature is 250-350 ℃, the time is 2-3 hours, the calcining temperature is 700-850 ℃, and the time is 1-2 hours.
Example 2:
step one, pretreating the rare earth waste residue, measuring the components of the rare earth waste residue, pulping according to the proportion that 7L of deionized water is added into each kilogram of waste residue,
and step two, controlling the temperature of the waste residue slurry at 70 ℃, adding 3mol/L sodium hydroxide solution to perform alkaline replacement reaction, and performing the reaction for 2 hours to obtain a thorium hydroxide filter cake. Washing the thorium hydroxide filter cake with deionized water at 60 ℃ for 4 times.
Step three, adding nitric acid to dissolve thorium hydroxide filter cakes, controlling the dissolving temperature at 80 ℃, regulating the thorium ion concentration to 150g/L and the acidity to 2mol/L, and adding 5% H2O2Reducing and converting cerium ions to obtain an extract stock solution for later use.
And step four, firstly preparing TBP-kerosene with the volume ratio of 5%, carrying out solution uranium removal operation, then preparing TBP-kerosene with the volume ratio of 30% to carry out thorium extraction operation, adopting a countercurrent extraction mode in the two extraction processes, adopting 15-stage extractors to be coupled in series, selecting the revolution of the extractors to be 4000r/min, and setting the flow ratio of a water phase inlet to an organic phase inlet to be 1: 1.5. Collecting the organic phase loaded with thorium ions for washing treatment, wherein the concentration of nitric acid in a washing liquid is 0.8mol/L, and the using amount of the washing liquid is 0.8 times of the volume of the loaded organic phase. And (3) carrying out back extraction treatment on the loaded organic phase by using hot water at the temperature of 75 ℃, wherein the flow ratio of a back extraction agent to the loaded organic phase is 1:1.8, and collecting a water phase outlet solution.
And step five, selecting oxalic acid, hydrogen peroxide, NaOH and the like to precipitate the strip liquor, controlling the temperature of the precipitation solution at 70 ℃, filtering the hot precipitate, and washing the hot precipitate for 3 times by using deionized water. And (3) drying and calcining the thorium dioxide filter cake by using a muffle furnace, wherein the drying temperature is 260 ℃, the time is 2 hours, the roasting temperature is 750 ℃, and the time is 1.2 hours.
Example 3:
step one, pretreating the rare earth waste residues, measuring the components of the rare earth waste residues, pulping according to the proportion that 10L of deionized water is added into each kilogram of waste residues, controlling the temperature of waste residue pulp liquid at 80 ℃,
and step two, adding 2.5mol/L sodium hydroxide solution to perform alkaline replacement reaction for 3 hours to obtain a thorium hydroxide filter cake. Washing the thorium hydroxide filter cake for 3 times by using deionized water at 70 ℃.
Step three, adding nitric acid to dissolve thorium hydroxide filter cakes, controlling the dissolving temperature at 75 ℃, regulating the thorium ion concentration to 200g/L and the acidity to 2.5mol/L, and adding 8% H2O2Reducing and converting cerium ions to obtain an extract stock solution for later use.
And step four, firstly preparing 9% TBP-kerosene, carrying out solution uranium removal operation, then preparing 40% TBP-kerosene, carrying out thorium extraction operation, adopting a countercurrent extraction mode in the two extraction processes, adopting 16-stage extractors for series coupling, selecting the rotation number of the extractors to be 4500r/min, and setting the flow ratio of the water phase inlet to the organic phase inlet to be 1: 2.2. Collecting the organic phase loaded with thorium ions for washing treatment, wherein the concentration of nitric acid in a washing liquid is 0.5mol/L, and the using amount of the washing liquid is 1 time of the volume of the loaded organic phase. And (3) carrying out back extraction treatment on the loaded organic phase by adopting hot water at 70 ℃, wherein the flow ratio of a back extraction agent to the loaded organic phase is 1:1, and collecting a water phase outlet solution.
And step five, selecting oxalic acid, hydrogen peroxide, NaOH and the like to precipitate the strip liquor, controlling the temperature of the precipitation solution at 80 ℃, filtering the hot precipitate, and washing the hot precipitate for 3 times by using deionized water. And (3) drying and calcining the thorium dioxide filter cake by using a muffle furnace, wherein the drying temperature is 300 ℃, the time is 2.2 hours, the calcining temperature is 800 ℃, and the time is 1 hour.
In the drawings of the disclosed embodiments of the invention, only methods related to the disclosed embodiments are referred to, other methods can refer to common design, and the same embodiment and different embodiments of the invention can be combined with each other without conflict;
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. Method for extracting and preparing nuclear pure ThO from rare earth waste residues2A method of powdering, characterized by:
the method comprises the following steps of firstly, pretreating the rare earth waste residue, determining the components of the rare earth waste residue, and adding water to make slurry of the rare earth waste residue;
step two, heating the waste residue slurry to a proper temperature, adding alkali liquor to perform an alkalization displacement reaction to obtain a thorium hydroxide filter cake, and filtering and washing the filter cake;
performing acid dissolution on the thorium hydroxide filter cake to obtain a thorium nitrate solution, and adding an oxidant to perform cerium ion reduction conversion treatment;
screening a proper extracting agent, removing uranium ions in the solution by adopting a centrifugal extraction technology, and then performing extraction and back extraction of thorium ions;
step five, after extraction and purification, adding a precipitator to precipitate, dry and roast thorium ions to prepare the generated nuclear pure-grade ThO2And (3) powder.
2. The method of claim 1, wherein the nuclear pure ThO is prepared by extracting rare earth waste residue2A method of powdering, characterized by: in the first step, water is added into the rare earth waste residue to prepare slurry, and the adding amount of the water is adjusted to be within the range of 5-12L/kg of the waste residue.
3. A process for reclaiming the rare-earth elements contained in the waste material of claim 1Extracting and preparing nuclear pure ThO from slag2A method of powdering, characterized by: in the step two alkalization displacement process, sodium hydroxide, potassium hydroxide and ammonia water are selected to carry out alkaline displacement reaction.
4. The method of claim 3, wherein the nuclear pure ThO is prepared by extracting rare earth waste residue2A method of powdering, characterized by: in the second alkalization and replacement process, the concentration of an alkaline solution is adjusted to 2.5-4 mol/L, and the reaction temperature is controlled within the range of 60-90 ℃;
in the alkalization replacement process, the adding amount of an alkaline solution is 120-200% of the amount required by normal reaction;
in the alkalization displacement process, the reaction time of displacement by using alkali liquor is not less than 3 h;
in the alkalization replacement process, after replacement is finished, the precipitate is filtered by using nylon filter cloth.
5. The method of claim 3, wherein the nuclear pure ThO is prepared by extracting rare earth waste residue2A method of powdering, characterized by: in the washing process of the thorium dihydroxide filter cake, deionized water is used for hot washing, and the washing temperature of the deionized water is 50-70 ℃;
in the washing process of the thorium hydroxide filter cake, the washing times of deionized water are not less than 3-5 times, and the washing dosage is 10-15L/kg of precipitate every time.
6. The method of claim 1, wherein the nuclear pure ThO is prepared by extracting rare earth waste residue2A method of powdering, characterized by: in the thorium hydroxide filter cake dissolving process, nitric acid is selected as an acid solution, and the dissolving temperature is controlled within the range of 60-90 ℃.
7. The method of claim 1, wherein the nuclear pure ThO is prepared by extracting rare earth waste residue2A method of powdering, characterized by: in the preparation process of the thorium trinitrate solution, the concentration of thorium ions in the solution is adjusted to be 50-300 g/L, and the acidity of the solution is adjusted to be 1-4 mol/L.
8. The method of claim 1, wherein the nuclear pure ThO is prepared by extracting rare earth waste residue2A method of powdering, characterized by: step three, during the reduction and conversion process of cerium ions, H is selected2O2Reductive conversion as an oxidant, H2O2The adding amount is 3-12% of the volume of the thorium nitrate solution.
9. The method of claim 1, wherein the nuclear pure ThO is prepared by extracting rare earth waste residue2A method of powdering, characterized by: selecting carboxylic acid, sulfonic acid, organic phosphoric acid, crown ether and primary amine extractant to perform screening test in the extractant optimization process in the fourth step; in the extraction agent optimization process, tributyl phosphate is selected as an extraction agent, and kerosene is adopted as a diluent;
in the extraction process, extraction equipment such as a mixer-settler, an ion extractor and a jet extractor is selected, the extraction material is stainless steel, PP, PMMA and the like, and the treatment capacity of the extraction equipment is 1-10L/h;
in the extraction and back extraction processes, a centrifugal extractor is preferably selected, 10-20 stages of extractors are adopted for series coupling, and the rotation number of the extractors is selected to be 3000-6000 r/min;
in the uranium removing process of the thorium nitrate solution, the extraction system is 3-10% of TBP-kerosene;
in the extraction process of the thorium ions, the extraction system is 20-40% of TBP-kerosene;
in the extraction process, a countercurrent extraction mode is adopted, and the flow ratio of a water phase inlet to an organic phase inlet is 1: 2-4: 1;
in the washing process, 0.5-1.5 mol/L nitric acid solution is selected as washing liquid, and the using amount of the washing liquid is 0.5-1 time of the volume of the loaded organic phase;
in the back extraction process, hot water is selected as a back extractant, and the temperature of the hot water is controlled to be 55-85 ℃;
in the back extraction process, the flow ratio of a water phase inlet to an organic phase inlet in the experiment process is 1: 3-2: 1;
and in the back extraction process and the experimental process, liquid at the water phase outlet is collected, and the impurity content is analyzed and detected.
10. The method of claim 1, wherein the nuclear pure ThO is prepared by extracting rare earth waste residue2A method of powdering, characterized by:
in the precipitation process of the thorium ions in the step five, oxalic acid, hydrogen peroxide and NaOH can be selected to carry out precipitation of the thorium ions;
in the precipitation process of the thorium ions, the precipitation temperature is controlled within the range of 60-90 ℃, precipitates are filtered while being hot, and are washed for 3 times by deionized water;
in the drying and roasting process, a muffle furnace is selected for drying and roasting, the drying temperature is 250-350 ℃, the time is 2-3 hours, the roasting temperature is 700-850 ℃, and the time is 1-2 hours.
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