WO2020063035A1 - Procédé d'enrichissement de scandium - Google Patents

Procédé d'enrichissement de scandium Download PDF

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WO2020063035A1
WO2020063035A1 PCT/CN2019/095692 CN2019095692W WO2020063035A1 WO 2020063035 A1 WO2020063035 A1 WO 2020063035A1 CN 2019095692 W CN2019095692 W CN 2019095692W WO 2020063035 A1 WO2020063035 A1 WO 2020063035A1
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organic
solution
extractant
extraction
acid
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PCT/CN2019/095692
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English (en)
Chinese (zh)
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王玮玮
孙宁磊
付国燕
刘召波
刘国
杜尚超
李诺
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中国恩菲工程技术有限公司
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Priority claimed from CN201811141713.4A external-priority patent/CN109022839A/zh
Priority claimed from CN201811143127.3A external-priority patent/CN109266870A/zh
Priority claimed from CN201811143122.0A external-priority patent/CN109179480A/zh
Application filed by 中国恩菲工程技术有限公司 filed Critical 中国恩菲工程技术有限公司
Publication of WO2020063035A1 publication Critical patent/WO2020063035A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • 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
    • 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
    • C22B59/00—Obtaining rare earth metals
    • 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

Definitions

  • the invention relates to the field of metallurgical technology, in particular to a method for enriching thorium.
  • Thallium is a metal with high commercial value.
  • thorium fluoride can be used as an optical material, and it is also an important raw material for the preparation of thallium metal and its alloys by molten salt electrolysis and metal thermal reduction methods.
  • Thallium oxide has a cube of rare earth sesquioxide. Structure, insoluble in water, soluble in hot acid, can be used as a vapor deposition material for semiconductor coatings, to make solid-state lasers with variable wavelengths, high-definition television electron guns, metal halide lamps, etc.
  • a traditional method of enriching thorium first uses an organic phase to extract the thorium-containing material solution to extract the thorium into the organic phase; after washing the obtained thorium-containing supported organic phase, adding an inorganic acid solution Back-extract with iso-extractive agent solution, strip the tritium in the supported organic phase from the organic phase, and back-extract it into the back-extract liquid; then add precipitant such as oxalic acid solution, alkaline solution, etc. Precipitate out and complete the enrichment of tritium.
  • the method has a long operation process, large consumption of raw materials such as back-extracting agent and water, and high operation cost.
  • Acidic organic phosphorus extractant has a good extraction effect on thorium (Sc), high extraction efficiency, and can well separate thorium from impurity elements, but thorium (Sc) is difficult to extract from organic solutions containing acidic organic phosphorus extractant
  • Sc thorium
  • Medium back extraction often requires very high acidity (such as sulfuric acid solution above 600g / L) and multiple back extraction operations.
  • concentration of impurity ions in the high-acidity radon solution obtained by back-extraction is high, and further purification operations are required.
  • a commonly used method is to add an oxalic acid solution to precipitate at a lower acidity to form an oxalate oxalate precipitate, and then calcinate the oxalate oxalate precipitate to generate oxidation.
  • Alas therefore, a large amount of alkaline solution is needed for neutralization, and a large amount of expensive oxalic acid reagent is consumed.
  • Organic carboxylic acid extractants have a good extraction effect on Sc (Sc).
  • the extraction mechanism is a cation exchange mechanism.
  • the extraction efficiency is high when the extraction is performed at a lower solution acidity.
  • impurity ions such as Ca 2+ and Mg) 2+ , Mn 2+ , Ni 2+ , Al 3+ , Fe 3+ , Cr 3+ ) are simultaneously extracted to a certain extent, which interferes with the separation of radon from these ions.
  • the commonly used method is to wash the loaded organic solution with an acid solution multiple times, but on the one hand, the effect of washing impurities is poor, on the other hand, it is easy to cause the loss of tritium, and the tritium (Sc) is difficult to load from it.
  • Back-extraction in organic solutions often requires high acidity (such as 4mol / L HCl solution) and multiple back-extraction operations, and the concentration of impurity ions in the high-acidity radon solution obtained by back-extraction is higher, which requires further purification operations.
  • the method is to add an oxalic acid solution to precipitate at a lower acidity to form a lutetium oxalate precipitate, and then calcine the acid ytterbium precipitate to generate ytterbium oxide. Therefore, a large amount of an alkaline solution needs to be neutralized, and a large amount of expensive oxalic acid reagent is consumed.
  • the invention aims to provide a method for enriching thorium to solve the technical problems of long enrichment operation flow and large raw material consumption in the prior art.
  • a method for enriching thorium includes the following steps: S1, using an organic extractant or an organic solvent solution containing an organic extractant to perform a rhenium extraction of a rhenium-containing inorganic acid solution to obtain an rhenium-containing organic phase; S2, using a precipitant solution to erbium-containing organic phase After performing precipitation back extraction treatment, solid-liquid separation and liquid-liquid separation, a precipitate containing thorium is obtained, as well as a precipitation mother liquor and an unloaded organic phase.
  • the organic extractant is one or more selected from the group consisting of an acidic organic extractant, a neutral organic extractant, a basic organic extractant, and an organic chelate extractant;
  • the acidic organic extractant includes an acidic organic phosphorus extractant and / or an organic carboxylic acid extractant; more preferably, the acidic organic phosphorus extractant is bis (2-ethylhexyl) phosphoric acid and / or 2-ethylhexyl phosphoric acid. Mono-2-ethylhexyl ester; more preferably, the organic carboxylic acid extractant is any one or more of an alkane carboxylic acid, an aromatic carboxylic acid and a naphthenic acid; further preferably, the alkane carboxylic acid is N-hexanoic acid, the aromatic hydrocarbon carboxylic acid is sec-octylphenoxyacetic acid;
  • the neutral organic extractant includes a neutral organic phosphorus (oxy) extractant and / or a long-chain alkyl ester; more preferably, the neutral organic phosphorus (oxy) extractant is tributyl phosphate, methylphosphonic acid Any one or more of dimethylheptyl ester and trialkylphosphine oxide;
  • the alkaline extractant includes an organic amine extractant; more preferably, the organic amine extractant is any one or more of an alkyl quaternary amine, a tertiary amine, a secondary amine, and a primary amine; further preferably, an alkyl amine
  • the quaternary amine is methyltrialkylammonium chloride
  • the tertiary amine is trioctylamine N235
  • the secondary amine is N-dodecenyltrialkylmethylamine
  • the primary amine is 1,1 ′, 1 ′′ -trialkylmethyl amine.
  • the organic chelating extractant includes a ⁇ -diketone extractant; more preferably, the ⁇ -diketone extractant is thienyltrifluoroacetone and / or 4-benzoyl-3-methyl-1-benzene 5--5-pyrazolone.
  • the organic solvent in the organic solvent solution containing the organic extractant is at least one of alkanes or mixtures thereof, aromatic hydrocarbons, organic alcohols, organic ethers, or organic esters having a density less than water;
  • the alkanes or mixtures thereof include n-heptane, n-hexane and kerosene;
  • the aromatic hydrocarbons include benzene and toluene;
  • the organic alcohol includes n-hexanol and isooctanol;
  • the organic ether includes diethyl ether
  • the organic ester includes ethyl acetate.
  • the concentration of the organic extractant in the organic solvent solution containing the organic extractant is 0.01 mol / L to 10 mol / L.
  • the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution; optionally, the scandium-containing inorganic acid solution contains other metal ions.
  • the precipitant solution is one or more of sodium hydroxide, ammonia, oxalic acid, hydrofluoric acid, phosphoric acid, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium fluoride, ammonium oxalate, and ammonium phosphate.
  • Aqueous solution is one or more of sodium hydroxide, ammonia, oxalic acid, hydrofluoric acid, phosphoric acid, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium fluoride, ammonium oxalate, and ammonium phosphate.
  • the concentration of the precipitating agent in the precipitating agent solution is 0.01 mol / L to 15 mol / L.
  • the volume ratio of the organic solvent solution containing the organic extractant to the rhenium-containing inorganic acid solution is (1:20) to (1: 1).
  • volume ratio of the organic phase containing rhenium to the precipitant solution is (1:20) to (20: 1).
  • the unloaded organic phase is returned to S1 in the tritium extraction treatment step for use;
  • a step of washing the organic phase containing rhenium is further included between S1 and S2.
  • the equipment used in the method for enriching thorium is a reaction kettle with agitation and mixing, a clarification extraction tank or a tube extractor, and a centrifuge, a vacuum filter or a filter press, or a centrifugal extraction and mixing integrated equipment
  • a reaction kettle with agitation and mixing a clarification extraction tank or a tube extractor
  • a centrifuge a vacuum filter or a filter press
  • a centrifugal extraction and mixing integrated equipment The above equipment is used alone or in combination.
  • the method includes the following steps: S11, using an organic solvent solution containing an acidic organic phosphorus extractant to perform a rhenium extraction of the rhenium-containing inorganic acid solution to obtain an organic phase containing rhenium; S12, performing a washing treatment on the organic phase containing rhenium To remove impurities; S13, add concentrated NaOH or KOH solution to the organic phase containing tritium after removing the impurities for back extraction, and obtain the complex anion solution and unloaded organic phase after liquid-liquid separation; S14, add the complex anion solution Hydrochloric acid was added to adjust the pH of the solution to generate Sc (OH) 3 precipitates. After solid-liquid separation, Sc (OH) 3 precipitates and mother liquors were obtained. S15, Sc (OH) 3 precipitates were calcined to obtain hafnium oxide.
  • the concentration of the NaOH or KOH solution in S13 is 4 mol / L to 8 mol / L.
  • the acidic organic phosphorus extractant is one or more selected from the group consisting of bis (2-ethylhexyl) phosphoric acid, 2-ethylhexyl phosphate mono-2-ethylhexyl ester, and Cyanex272 extractant.
  • the organic extractant in the organic solvent solution containing the acidic organic phosphorus extractant is at least one of alkanes or their mixtures, aromatic hydrocarbons, organic alcohols, organic ethers, or organic esters with a density less than water; , Alkanes or mixtures thereof include n-heptane, n-hexane and kerosene; preferably, aromatic hydrocarbons include benzene and toluene; preferably, organic alcohols include n-hexanol and isooctanol; preferably, organic ethers include diethyl ether; preferred Organic esters include ethyl acetate.
  • the concentration of the acidic organic phosphorus extractant in the organic solvent solution containing the acidic organic phosphorus extractant is 0.01 mol / L to 4 mol / L.
  • the rhenium-containing inorganic acid solution is a rhenium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution.
  • the volume ratio of the organic solvent solution containing the acidic organic phosphorus extractant to the rhenium-containing inorganic acid solution is (1:20) to (1: 1).
  • the volume ratio of the organic solvent solution containing the acidic organic phosphorus extractant to the NaOH or KOH solution in S13 is (1:20) to (20: 1).
  • S14 and S15 further include: washing the Sc (OH) 3 precipitate with ethanol and water, respectively.
  • the temperature for washing with ethanol is 20 to 40 ° C
  • the temperature for washing with water is 50 to 90 ° C.
  • the washing liquid used for the washing treatment is a 0.1 to 4 mol / L hydrochloric acid aqueous solution or a 0.1 to 1 mol / L sulfuric acid aqueous solution.
  • the unloaded organic phase is returned to the step S11 of the tritium extraction treatment step for use.
  • reaction temperature of the back extraction is 20 to 90 ° C, and preferably 50 to 70 ° C.
  • hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to form a Sc (OH) 3 precipitate, and the pH of the precipitation end point is 5.0 to 8.0.
  • the temperature of Sc (OH) 3 precipitation and calcination in S15 to generate hafnium oxide is 400-650 ° C.
  • the method includes the following steps: S21, using an organic solvent solution containing an organic carboxylic acid extractant to perform a rhenium extraction of the rhenium-containing inorganic acid solution to obtain an organic phase containing rhenium; S22, adding a concentrated organic phase to the organic phase containing rhenium NaOH or KOH solution is subjected to back extraction. After the liquid-liquid separation, a complex anion solution and an unloaded organic phase are obtained; S23, hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to form a Sc (OH) 3 precipitate.
  • Sc (OH) 3 precipitation and precipitation mother liquor are obtained;
  • S24, Sc (OH) 3 precipitation is calcined to obtain crude hafnium oxide;
  • S25, crude hafnium oxide is washed with a hydrochloric acid aqueous solution to remove impurity elements to obtain hafnium oxide.
  • the concentration of the NaOH or KOH solution in S22 is 4 mol / L to 8 mol / L.
  • the organic carboxylic acid extractant is one or more selected from the group consisting of an alkane carboxylic acid, an aromatic carboxylic acid, and a naphthenic acid; preferably, the alkane carboxylic acid is n-hexanoic acid; preferably, an aromatic hydrocarbon group
  • the carboxylic acid is sec-octylphenoxyacetic acid.
  • the organic extractant in the organic solvent solution containing the organic carboxylic acid extractant is at least one of alkanes or their mixtures, aromatic hydrocarbons, organic alcohols, organic ethers, or organic esters with a density less than water; , Alkanes or mixtures thereof include n-heptane, n-hexane and kerosene; preferably, aromatic hydrocarbons include benzene and toluene; preferably, organic alcohols include n-hexanol and isooctanol; preferably, organic ethers include diethyl ether; preferred Organic esters include ethyl acetate.
  • the concentration of the organic carboxylic acid extractant in the organic solvent solution containing the organic carboxylic acid extractant is 0.01 mol / L to 4 mol / L.
  • the rhenium-containing inorganic acid solution is a rhenium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution.
  • the rhenium-containing inorganic acid solution contains other metal ions, and the other metal ions are Ca 2+ , Mg 2+ , and Mn 2 One or more of + , Ni2 + , Al3 + , Fe3 + , and Cr3 + .
  • the volume ratio of the organic solvent solution containing the organic carboxylic acid extractant to the rhenium-containing inorganic acid solution is (1:10) to (1: 1); preferably, the organic solvent solution containing the organic carboxylic acid extractant is used to
  • the tritium-containing inorganic acid solution was subjected to tritium extraction, and the end pH of the tritium-containing inorganic acid solution was controlled by NaOH to be 2 to 4.
  • volume ratio of the organic solvent solution containing the organic carboxylic acid extractant to the NaOH or KOH solution in S22 is (1:10) to (10: 1).
  • S23 and S24 further include: washing the Sc (OH) 3 precipitate with ethanol and water, respectively.
  • the temperature for washing with ethanol is 20 to 40 ° C
  • the temperature for washing with water is 50 to 90 ° C.
  • the concentration of the aqueous hydrochloric acid solution used is 0.01 to 0.5 mol / L; preferably, the crude hafnium oxide is washed with an aqueous hydrochloric acid solution at a temperature of 10 to 30 ° C; preferably, the crude hafnium oxide is washed with an aqueous hydrochloric acid solution. After washing, it was washed with water and then dried.
  • the no-load organic phase is returned to the step S21 in the extraction treatment step; after adding NaOH to the precipitation mother liquor, it is returned to the step S22 in the extraction treatment step.
  • reaction temperature of the back extraction is 20 to 90 ° C, and preferably 40 to 60 ° C.
  • hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to form a Sc (OH) 3 precipitate, and the pH of the precipitation end point is 5.0 to 8.0.
  • the temperature of Sc (OH) 3 precipitation and calcination in S25 to generate hafnium oxide is 400-650 ° C.
  • a method for enriching metals includes the following steps: S1, performing a metal extraction on a metal-containing inorganic acid solution using an organic extractant or an organic solvent solution containing an organic extractant to obtain a metal-containing organic phase; S2, using a precipitant solution to the metal-containing organic phase Precipitation back-extraction treatment, solid-liquid separation and liquid-liquid separation are used to obtain a metal-containing precipitate, as well as the mother liquor of precipitation and the unloaded organic phase.
  • the tritium in the supported organic phase is added to the precipitant solution to simultaneously perform back-extraction and precipitation to directly obtain the precipitate of the tritium from the organic phase. This shortens the operation process and uses a precipitant. No back-extracting agent is used, reducing the consumption of back-extracting agent, water and other raw materials, and reducing operating costs.
  • FIG. 1 shows a schematic flowchart of a conventional enriched plutonium
  • FIG. 2 is a schematic flowchart of enriched radon according to an embodiment of the present invention
  • FIG. 3 is a schematic flowchart of enriched radon according to another embodiment of the present invention.
  • FIG. 4 is a schematic flowchart of enriched radon according to another embodiment of the present invention.
  • a method for enriching thorium includes the following steps: S1, using an organic extractant or an organic solvent solution containing an organic extractant to perform a rhenium extraction of a rhenium-containing inorganic acid solution to obtain an rhenium-containing organic phase; S2, using a precipitant solution to erbium-containing organic phase After performing precipitation back extraction treatment, solid-liquid separation and liquid-liquid separation, a precipitate containing thorium is obtained, as well as a precipitation mother liquor and an unloaded organic phase.
  • the tritium in the supported organic phase is added to the precipitant solution to simultaneously perform back-extraction and precipitation to directly obtain the precipitate of the tritium from the organic phase. This shortens the operation process and uses a precipitant. No back-extracting agent is used, reducing the consumption of back-extracting agent, water and other raw materials, and reducing operating costs.
  • the organic extractant is one or more selected from the group consisting of an acidic organic extractant, a neutral organic extractant, a basic organic extractant, and an organic chelate extractant; preferably
  • the acidic organic extractant includes an acidic organic phosphorus extractant and / or an organic carboxylic acid extractant; more preferably, the acidic organic phosphorus extractant is bis (2-ethylhexyl) phosphoric acid (P204 extractant) and / or 2- Ethylhexyl phosphate mono-2-ethylhexyl ester (P507 extractant); more preferably, the organic carboxylic acid extractant is any one or more of an alkane carboxylic acid, an aromatic carboxylic acid and a naphthenic acid; Further preferably, the alkane carboxylic acid is n-hexanoic acid, and the aromatic hydrocarbon carboxylic acid is sec-octylphenoxyacetic acid.
  • the neutral organic extractant includes a neutral organic phosphorus (oxygen) extractant and / or a long-chain alkyl group. Esters, etc .; more preferably, the neutral organic phosphorus (oxygen) extractant is tributyl phosphate (TBP extractant), dimethylheptyl methylphosphonate (P350 extractant), and trialkylphosphine oxide (Cyanex923) Any one or more of them; preferably, the alkaline extractant includes an organic amine extractant; more preferred The organic amine extractant is any one or more of a quaternary alkyl amine, a tertiary amine, a secondary amine, and a primary amine; more preferably, the quaternary alkyl amine is methyltrialkylammonium chloride, and the tertiary amine is trioctyl The amine N235, the secondary amine is N-dodecenyltrialkylmethylamine, and the primary amine
  • the organic chelating extractant includes a ⁇ -diketone extractant ; More preferably, the ⁇ -diketone extractant is thenoyl-trifluoroacetone (HTTA) and / or 4-benzoyl-3-methyl-1-phenyl-5-pyrazolinone ( 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5).
  • HTTA thenoyl-trifluoroacetone
  • 4-benzoyl-3-methyl-1-phenyl-5-pyrazolinone 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5.
  • the organic solvent in the organic solvent solution containing the organic extractant is at least one of alkanes or their mixtures, aromatic hydrocarbons, organic alcohols, organic ethers, or organic esters with a density less than water.
  • alkanes or mixtures thereof include n-heptane, n-hexane, and kerosene;
  • aromatic hydrocarbons include benzene and toluene;
  • organic alcohols include n-hexanol and isooctanol;
  • organic ethers include Diethyl ether; preferably, the organic ester includes ethyl acetate.
  • the concentration of the organic extractant in the organic solvent solution containing the organic extractant is 0.01 mol / L to 10 mol / L.
  • the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution; optionally, the scandium-containing inorganic acid solution contains other metal ions.
  • the precipitant solution is sodium hydroxide, ammonia, oxalic acid, hydrofluoric acid, phosphoric acid, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium phosphate, sodium fluoride, ammonium oxalate, ammonium phosphate
  • concentration of the precipitant in the precipitant solution is 0.01 mol / L to 15 mol / L.
  • the volume ratio of the organic solvent solution containing the organic extractant to the rhenium-containing inorganic acid solution is (1:20) to (1: 1), and the rhenium is fully and efficiently extracted in this ratio range; further Preferably, the volume ratio of the organic phase containing rhenium to the precipitant solution is (1:20) to (20: 1).
  • the unloaded organic phase is returned to S1 for use in the plutonium extraction treatment step, which is conducive to the full recycling of raw materials and reduces the production cost.
  • S1 and S2 also include organic compounds containing plutonium.
  • the phases are subjected to a washing step to remove impurities that are simultaneously extracted.
  • a mechanical stirring mixing method is used in both the mash extraction and the precipitation back extraction process to accelerate the reaction progress.
  • the equipment used in the method for enriching thorium may be a mixing device such as a reaction kettle with stirring function, a mixing and clarifying extraction tank, a tubular extractor, and a centrifuge, a vacuum filter, Separation equipment such as filter presses, or hybrid separation and integration equipment such as centrifugal extractors, these equipment can be used alone or in combination.
  • a mixing device such as a reaction kettle with stirring function, a mixing and clarifying extraction tank, a tubular extractor, and a centrifuge, a vacuum filter, Separation equipment such as filter presses, or hybrid separation and integration equipment such as centrifugal extractors, these equipment can be used alone or in combination.
  • the method includes the following steps: using an organic extractant or an organic solvent solution containing an organic extractant to perform a rhenium extraction of a rhenium-containing inorganic acid solution to obtain a rhenium-containing Organic phase (containing rhenium-supported organic phase); washing the organic phase containing rhenium to remove impurities extracted at the same time, using a precipitant solution to carry out precipitation back extraction treatment of the organic phase containing rhenium, solid-liquid separation and liquid After the liquid separation, a precipitate containing thallium was obtained.
  • a method for enriching metals includes the following steps: S1, performing a metal extraction on a metal-containing inorganic acid solution using an organic extractant or an organic solvent solution containing an organic extractant to obtain a metal-containing organic phase; S2, using a precipitant solution to the metal-containing The organic phase is subjected to precipitation back-extraction treatment. After solid-liquid separation and liquid-liquid separation, a metal-containing precipitate is obtained, as well as a mother liquor and an unloaded organic phase.
  • the method and equipment of the present invention can be universally used in any process including liquid-liquid-solid three-phase reaction and gas-liquid-solid three-phase reaction;
  • the metal is not limited to rare earths (lanthanum (La), europium (Sm), europium (Eu), Thorium (Gd), Thorium (Tb), Thorium (Dy), Thorium (Ho), Thorium (Er), Thorium (Tm), Thorium (Yb), Thorium (Lu), and Thorium (Sc) and Yttrium (Y)
  • a total of 17 elements, called rare earth elements) can also be magnesium (Mg), (Al), calcium (Ca), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt ( Co), nickel (Ni), copper (Cu), zinc (Zn), titanium (Ti), zirconium (Zr), hafnium (Hf), barium (Ba), lead (Pb), tin (Sn), silver ( Ag), thorium
  • a method for extracting thorium oxide includes the following steps: S11, using an organic solvent solution containing an acidic organic phosphorus extractant to perform thorium extraction on a thorium-containing inorganic acid solution to obtain a thallium-containing organic phase; S12, performing a washing treatment on the thallium-containing organic phase to remove impurities ; S13, adding concentrated NaOH or KOH solution to the organic phase containing tritium after removing impurities for back extraction, liquid-liquid separation to obtain tritium anion solution and unloaded organic phase; S14 adding hydrochloric acid to the tritium anion solution to adjust the solution PH to produce Sc (OH) 3 precipitates. After solid-liquid separation, Sc (OH) 3 precipitates and precipitated mother liquor; S15, Sc (OH) 3 precipitates are calcined to obtain hafnium oxide.
  • concentrated NaOH or KOH solution refers to a concentrated NaOH or KOH solution in the ordinary sense in the art, and the preferred concentration of the NaOH solution in S13 is 4 mol / L to 8 mol / L.
  • the present invention uses an organic phase containing an acidic organic phosphorus extractant (an organic solvent solution containing an acidic organic phosphorus extractant) to perform a tritium extraction treatment on a tritium-containing material solution (a tritium-containing inorganic acid solution), so as to obtain a supported organic phase containing tritium;
  • the organic phase containing tritium is washed to remove impurities that are extracted at the same time;
  • the above-removed organic phase is added to a concentrated NaOH solution for back extraction to generate a soluble tritium anion solution, and hydrochloric acid is added to the tritium anion solution to adjust the solution Acidity to produce Sc (OH) 3 precipitates; the generated Sc (OH) 3 precipitates are calcined to form osmium oxide.
  • This method can effectively enrich and extract thorium oxide from thorium-containing solution.
  • the method has high back-extraction efficiency, high precipitation efficiency, shortened operation process, reduced consumption of back-extracted acid, neutralized alkali, water, oxalic acid and other raw materials, and reduced operating costs, which is beneficial to industrial production.
  • the acidic organic phosphorus extractant is selected from the group consisting of bis (2-ethylhexyl) phosphoric acid (P204 extractant), 2-ethylhexyl phosphate mono-2-ethylhexyl phosphate (P507 extractant), and Cyanex272 extractant.
  • the organic extractant in the organic solvent solution containing the acidic organic phosphorus extractant is an alkane or its mixture, aromatic hydrocarbon, organic alcohol, organic ether or organic ester with a density less than water
  • alkanes or mixtures thereof include n-heptane, n-hexane, and kerosene
  • aromatic hydrocarbons include benzene and toluene
  • organic alcohols include n-hexanol and isooctanol
  • the organic ether includes diethyl ether; more preferably, the organic ester includes ethyl acetate.
  • the concentration of the acidic organic phosphorus extractant in the organic solvent solution (also referred to as the extractant) containing the acidic organic phosphorus extractant is 0.01 mol / L to 4 mol / L.
  • the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution.
  • the scandium-containing inorganic acid solution may contain other metal ions.
  • the volume ratio of the organic solvent solution containing the acidic organic phosphorus extractant to the osmium-containing inorganic acid solution is (1:20) to (1: 1), and in this range of ratio, the rhenium is fully and efficiently extracted.
  • the volume ratio of the organic solvent solution containing the acidic organic phosphorus extractant to the NaOH solution in S13 is (1:20) to (20: 1), and in this range of ratio, it is favorable for the radon to be fully and efficiently back-extracted. .
  • S14 and S15 further include: washing the Sc (OH) 3 precipitate with ethanol and water, respectively, so as to remove organic matters adsorbed on the surface and water-soluble impurities, respectively.
  • the ethanol washing temperature is 20-40 ° C
  • the water washing temperature is 50-90 ° C.
  • the washing solution used is a 0.1 to 4 mol / L hydrochloric acid aqueous solution or a 0.1 to 1 mol / L sulfuric acid aqueous solution.
  • the precipitated mother liquor in S13 is added to NaOH and returned to the back-extraction treatment step, and the unloaded organic phase is returned to S11 to be used in the radon extraction treatment step, which is conducive to the full recovery of raw materials and reduces production costs.
  • the mixing process of mechanical stirring is used in both the mash extraction and the back extraction process to accelerate the reaction progress.
  • the reaction temperature of the back extraction is 20 to 90 ° C, and more preferably 50 to 70 ° C.
  • hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to generate a Sc (OH) 3 precipitate, and the pH of the end point of the precipitation is 5.0-8.0.
  • the temperature at which Sc (OH) 3 is precipitated and calcined in S14 to generate hafnium oxide is 400-650 ° C.
  • the method includes: performing an rhenium extraction treatment using an organic relative to a rhenium-containing feed liquid containing an acidic organic phosphorus extractant in order to obtain a supported organic phase containing rhenium and controlling the extraction Reaction conditions such as agent concentration, and the volume of the organic phase is smaller than the volume of the aqueous phase, so that the plutonium is enriched and reacted with impurity ions (such as Ca 2+ , Mg 2+ , Zn 2+ , Mn 2+ , Ni 2+ , Co 2 + , Al 3+ , Fe 3+ , Cr 3+, etc.); washing the organic phase containing rhenium by washing can remove a small amount of impurity ions that are extracted or entrained at the same time, so that the rhenium is further purified; Add concentrated NaOH solution for back extraction, control the reaction conditions such as the concentration of back extractant, temperature, volume ratio of organic phase: water phase
  • Sc (OH) 3 precipitate was washed at a selected temperature of ethanol and water, respectively to remove surface adsorbed organic matter and water-soluble impurities, scandium further purification, and after washing Sc (OH ) 3 precipitate has better filtration performance; the Sc (OH) 3 precipitate is calcined to generate ytterbium oxide, the calcination temperature (400-650 ° C) is lower than the calcination temperature of osmium oxalate (700-800 ° C), and the Water vapor instead of the greenhouse gas CO 2 .
  • This method can effectively enrich and extract thorium oxide from thorium-containing solution.
  • a method for extracting thorium oxide includes the following steps: S21, using an organic solvent solution containing an organic carboxylic acid extractant to perform thorium extraction on a thorium-containing inorganic acid solution to obtain a thallium-containing organic phase; S22, adding concentrated NaOH or KOH to the thallium-containing organic phase The solution is back-extracted, and the complex anion solution and the unloaded organic phase are obtained after liquid-liquid separation. S23, hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to generate Sc (OH) 3 precipitate. Sc is obtained after solid-liquid separation.
  • the stripping efficiency is high, the precipitation efficiency is high, the operation process is shortened, the consumption of raw materials such as stripping acid, neutralizing alkali, water, and oxalic acid is reduced, and the operating cost is reduced, which is beneficial to the application in industrial production.
  • concentrated NaOH or KOH solution refers to a concentrated NaOH or KOH solution in the ordinary sense in the art, and the preferred concentration of the NaOH solution in S22 is 4 mol / L to 8 mol / L.
  • the present invention uses an organic phase containing an organic carboxylic acid extractant (an organic solvent solution containing an organic carboxylic acid extractant) to perform a rhenium extraction treatment on a mash-containing liquid (a fluorene-containing inorganic acid solution) to obtain a supported organic phase containing rhenium;
  • the organic phase is added to a concentrated NaOH solution for back extraction to generate a soluble complex anion solution, and hydrochloric acid is added to the complex anion solution to adjust the acidity of the solution to form a Sc (OH) 3 precipitate; the generated Sc (OH) 3
  • the precipitate is calcined to generate crude ytterbium oxide, and the crude ytterbium oxide is washed with an aqueous hydrochloric acid solution to remove impurity elements to obtain ytterbium oxide.
  • This method can effectively enrich and extract thorium oxide from thorium-containing solution.
  • the method has high back-extraction efficiency, high precipitation efficiency, shortened operation process, reduced consumption of back-extracted acid, neutralized alkali, water, oxalic acid and other raw materials, and reduced operating costs, which is beneficial to industrial production.
  • the calcined crude ytterbium oxide is soluble in hot concentrated hydrochloric acid but insoluble or very slightly soluble in dilute hydrochloric acid. Washing is performed at a temperature to dissolve and remove the impurity elements therein, and the rhenium and the impurity elements can be well separated to obtain purified erbium oxide.
  • the concentration of the aqueous hydrochloric acid solution used in S25 is 0.01 to 0.5 mol / L; more preferably, the crude holmium oxide is washed with an aqueous hydrochloric acid solution at a temperature of 10 to 30 ° C; more preferably, the crude holmium oxide is washed with hydrochloric acid.
  • the aqueous solution was washed with water and then dried.
  • the organic carboxylic acid extractant is one or more selected from the group consisting of an alkane carboxylic acid, an aromatic carboxylic acid, and a naphthenic acid; preferably, the alkane carboxylic acid is n-hexane Acid; preferably, the aromatic hydrocarbon carboxylic acid is sec-octylphenoxyacetic acid.
  • the organic extractant in the organic solvent solution containing the organic carboxylic acid extractant is at least one of alkanes or mixtures thereof, aromatic hydrocarbons, organic alcohols, organic ethers, or organic esters having a density less than water; more preferably Of these, alkanes or mixtures thereof include n-heptane, n-hexane and kerosene; more preferably, aromatic hydrocarbons include benzene and toluene; more preferably, organic alcohols include n-hexanol and isooctanol; more preferably, organic ethers include Diethyl ether; more preferably, the organic ester includes ethyl acetate.
  • alkanes or mixtures thereof include n-heptane, n-hexane and kerosene; more preferably, aromatic hydrocarbons include benzene and toluene; more preferably, organic alcohols include n-hexanol and isooctanol
  • the concentration of the organic carboxylic acid extractant in the organic solvent solution (also known as the extractant) containing the organic carboxylic acid extractant is 0.01 mol / L to 4 mol / L.
  • the scandium-containing inorganic acid solution is a scandium-containing sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution.
  • the scandium-containing inorganic acid solution may further contain other metal ions, and the other metal ions are Ca.
  • the other metal ions are Ca.
  • the volume ratio of the organic solvent solution containing the organic carboxylic acid extractant to the rhenium-containing inorganic acid solution is (1:10) to (1: 1), and the rhenium is fully and efficiently extracted in this ratio range.
  • the rhenium-containing inorganic acid solution is subjected to holmium extraction using an organic solvent solution containing an organic carboxylic acid extractant, and the end pH of the holmium-containing inorganic acid solution is controlled by NaOH to be 2 to 4.
  • the volume ratio of the organic solvent solution containing the organic carboxylic acid extractant to the NaOH or KOH solution in S22 is (1:10) to (10: 1). Within this range of ratio, it is favorable for the tritium to be fully and efficiently reacted. Extracted.
  • S23 and S24 further include: washing the Sc (OH) 3 precipitate with ethanol and water, respectively, so as to remove the organic matters and water-soluble impurities adsorbed on the surface, respectively.
  • the ethanol washing temperature is 20-40 ° C
  • the water washing temperature is 50-90 ° C.
  • the no-load organic phase is returned to the S21 ⁇ extraction treatment step for use; the precipitated mother liquor is added to NaOH and returned to the S22 ⁇ extraction treatment step, which is beneficial to the full recovery of raw materials and reduces production costs.
  • the mixing process of mechanical stirring is used in both the mash extraction and the back extraction process to accelerate the reaction progress.
  • the reaction temperature of the back extraction is 20 to 90 ° C, and preferably 40 to 60 ° C.
  • hydrochloric acid is added to the complex anion solution to adjust the pH of the solution to form a Sc (OH) 3 precipitate, and the pH of the precipitation end point is 5.0-8.0.
  • the temperature at which Sc (OH) 3 is precipitated and calcined in S25 to generate hafnium oxide is 400-650 ° C.
  • the method includes: using an organic organic carboxylic acid extractant to perform a tritium extraction treatment on a tritium-containing feed liquid, so as to obtain a supported organic phase containing tritium and control the extractant Concentration and other reaction conditions, and the volume of the organic phase is smaller than the volume of the aqueous phase, so that the plutonium is enriched and with impurity ions (such as Ca 2+ , Mg 2+ , Zn 2+ , Mn 2+ , Ni 2+ , Co 2+ , Al 3+ , Fe 3+ , Cr 3+, etc.) preliminary separation; add the above organic phase to a concentrated NaOH solution for back extraction, and control the reaction conditions such as the concentration of the back extractant, temperature, and volume ratio of the organic phase to the water phase to Generates a soluble complex anion Sc (OH) 6 3- solution, with high back extraction efficiency, good separation of organic and water phases, and further separation from the impurity
  • impurity ions such as Ca 2+ , Mg
  • the resulting crude dysprosium oxide is washed with a dilute aqueous hydrochloric acid solution at a lower temperature to dissolve and remove the impurity elements therein, which can well separate the dysprosium and the impurity elements, and obtain purified Thorium oxide.
  • This method can effectively enrich and extract thorium oxide from thorium-containing solution.
  • a kerosene solution containing 3 mol / L tributyl phosphate extractant (TBP extractant) was used from a solution containing 0.1 mol / L rhenium hydrochloric acid according to the volume ratio of the organic solution and the rhenium-containing solution to 1: 1.
  • Extraction ⁇ ; washing the organic phase containing ⁇ with 1 mol / L hydrochloric acid aqueous solution, according to the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the precipitation back-extractant solution is 1: 1.
  • the organic phase of rhenium is mixed with an aqueous solution (precipitation phase) of a precipitation and stripping agent containing 1 mol / L NaOH, and the mother liquid of the organic phase of lutetium and the aqueous solution of the precipitation and stripping agent is separated in a mixing and clarifying extraction tank, and the rhenium hydroxide precipitate is formed.
  • the aqueous phase flows out from the aqueous phase outlet together with the precipitation mother liquor; the generated thorium hydroxide precipitate is separated from the precipitation mother liquor by vacuum filtration to obtain an enriched thorium hydroxide precipitate, and the thorium extraction rate is above 80%.
  • a positive solution containing 1 mol / L (bis (2-ethylhexyl) phosphate) extractant (P204 extractant) was used.
  • the heptane solution was used to extract rhenium from a sulfuric acid solution containing 0.05 mol / L of rhenium; the organic phase containing rhenium was washed with a 0.01 mol / L sulfuric acid aqueous solution, and the volume ratio of the organic solution of the extractant and the solution of the precipitation back-extracting agent (organic solution: The volume ratio of the aqueous solution) was 10: 1.
  • the washed organic phase containing tritium was mixed with a 5 mol / L NaOH precipitated stripping agent aqueous solution (aqueous phase), and the empty tritium organic phase and the precipitated stripping agent aqueous solution mother liquor were mixed.
  • a mixed clarification extraction tank Separated in a mixed clarification extraction tank, the generated dysprosium hydroxide precipitate is in the water phase, and flows out from the aqueous phase outlet with the precipitation mother liquor; the generated dysprosium hydroxide precipitate and the precipitation mother liquor are separated by a centrifuge to obtain enriched hydroxide
  • the osmium is precipitated and the extraction rate of osmium is more than 70%.
  • a toluene solution containing 0.1 mol / L of the extractant naphthenic acid was extracted from a 0.1 mol / L hydrazone hydrochloric acid solution;
  • the organic phase was extracted according to the volume ratio (organic solution, aqueous solution volume ratio) of the extractant organic solution and the precipitation back-extractant solution to 5: 1.
  • the washed organic phase loaded with tritium was back-extracted with the precipitate containing 0.3 mol / L oxalic acid.
  • aqueous solution (aqueous phase) is mixed, the organic phase of no-loaded tritium is separated from the mother liquor of the precipitation back-extractant aqueous solution in a mixed clarification extraction tank, and the tritium oxalate precipitate is in the aqueous phase and flows out from the aqueous phase outlet together with the precipitated mother liquid;
  • the generated lutetium oxalate precipitate and the precipitation mother liquor were separated by vacuum filtration to obtain an enriched lutetium oxalate precipitate, and the ytterbium extraction rate was above 90%.
  • the organic phase containing tritium is mixed with a 10 mol / L sodium fluoride precipitated stripping agent aqueous solution (aqueous phase).
  • aqueous phase a 10 mol / L sodium fluoride precipitated stripping agent aqueous solution
  • the no-loaded tritium organic phase and the precipitated stripping agent aqueous solution mother liquor are separated in a mixed clarification extraction tank to generate fluorination.
  • the rhenium precipitate is in the water phase and flows out from the aqueous phase outlet together with the precipitation mother liquor; the generated rhenium fluoride precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched rhenium fluoride precipitate, and the rhenium extraction rate is above 90%.
  • the organic phase containing tritium is mixed with an aqueous solution (precipitation phase) of a precipitated stripping agent containing 1 mol / L ammonium phosphate, and the mother liquid of the organic phase containing no tritium and the aqueous solution of the precipitated stripping agent is separated in a reaction kettle with stirring and mixing.
  • the generated europium phosphate precipitate is in the aqueous phase and flows out from the aqueous phase outlet together with the precipitation mother liquor; the generated europium phosphate precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched europium phosphate precipitate, and the europium extraction rate is above 70%.
  • an n-hexanol solution containing 1 mol / L trioctylamine (N235 extractant) and 1 mol / L ⁇ -diketone extractant (HTTA) was used in accordance with the volume ratio of the organic solution and the rhenium-containing solution to 1: 5.
  • the generated dysprosium hydroxide precipitate is in the aqueous phase, and flows out from the aqueous phase outlet with the precipitation mother liquor; the generated dysprosium hydroxide precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain enriched hydroxide
  • the osmium is precipitated and the extraction rate of osmium is more than 89%.
  • the neodymium was extracted from a hydrochloric acid solution containing 2 mol / L neodymium with 10 mol / L of P204 according to the volume ratio of organic solution and neodymium-containing solution of 1: 5; the organic phase loaded with neodymium was 1 mol / l L hydrochloric acid aqueous solution was washed, according to the volume ratio (organic solution, aqueous solution volume ratio) of the extractant organic solution and the precipitation back-extractant solution was 1:20, and the washed organic phase loaded with tritium was precipitated with 6 mol / L oxalic acid.
  • the stripping agent aqueous solution (aqueous phase) was mixed.
  • the organic phase of the unloaded neodymium and the mother liquor of the precipitation back-extractant aqueous solution are separated in a reaction kettle with stirring and mixing to form a precipitate of neodymium oxalate which is in the aqueous phase and flows out from the aqueous phase outlet together with the precipitation mother liquor; the resulting neodymium oxalate is precipitated It is separated from the precipitation mother liquor by vacuum filtration to obtain an enriched neodymium oxalate precipitate.
  • the rare earth neodymium can be back-extracted from the organic phase of P204 with oxalic acid solution, and the back-extraction rate is above 89%.
  • neodymium was extracted from a 0.5 mol / L neodymium hydrochloric acid solution using P204 containing 10 mol / L; 1 mol of the organic phase carrying neodymium was used.
  • / L hydrochloric acid aqueous solution was washed, according to the volume ratio (organic solution, aqueous solution) of the extractant organic solution and the precipitation back-extractant solution was 1:20, and the washed organic phase containing tritium and 15 mol / L oxalic acid was washed.
  • the precipitated stripping agent aqueous solution (aqueous phase) was mixed.
  • the organic phase of the unloaded neodymium and the mother liquor of the precipitation back-extractant aqueous solution are separated in a reaction kettle with stirring and mixing to form a precipitate of neodymium oxalate which is in the aqueous phase and flows out from the aqueous phase outlet together with the precipitation mother liquor; the resulting neodymium oxalate is precipitated It is separated from the precipitation mother liquor by vacuum filtration to obtain an enriched neodymium oxalate precipitate.
  • the rare earth neodymium can be back-extracted from the organic phase of P204 with oxalic acid solution, and the back-extraction rate is about 90%.
  • the above-mentioned embodiments of the present invention achieve the following technical effects:
  • the tritium in the supported organic phase can be simultaneously back-extracted and precipitated by adding a precipitant solution.
  • the effect is to directly obtain the precipitation of tritium from the organic phase, which shortens the operation process, uses a precipitating agent, does not use a back-extracting agent, reduces the consumption of back-extracting agent, water and other raw materials, and reduces operating costs.
  • the 500 mL organic phase containing tritium was washed with 500 mL of a 1 mol / L hydrochloric acid aqueous solution to remove the co-extracted impurity elements, the impurity washing rate was more than 99%, and the elution ratio of tritium was 0.2%;
  • the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the stripping agent solution is 1: 1, 500 mL of the organic phase loaded with tritium and 500 mL of a stripping agent aqueous solution containing 5 mol / L NaOH (water Phase) Mix in a reaction kettle at a reaction temperature of 50 ° C to carry out a back-extraction reaction.
  • the back-extraction rate of osmium is 99.1%.
  • the generated anion complex is in the aqueous phase and flows out from the aqueous phase outlet; The phase is separated from the complex anion solution and returned to the extraction step for recycling;
  • the generated thorium hydroxide precipitate was separated from the precipitation mother liquor by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) 3 precipitate; the Sc (OH) 3 precipitate was washed with ethanol and water, respectively, at a temperature of 20 ° C and 50 ° C. °C to remove organic matter and water-soluble impurities adsorbed on the surface, respectively.
  • the Sc (OH) 3 precipitate was calcined at 600 ° C to generate hafnium oxide.
  • the total yield of rhenium was 98.3%.
  • the purity of europium oxide reached 99.0%.
  • the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the stripping agent solution is 1: 1, the washed organic phase loaded with tritium and 500 mL of the stripping agent aqueous solution (water phase containing 6mol / L HCl) ) Mixing in a reaction kettle at a reaction temperature of 50 ° C. to perform a back extraction reaction to generate a thallium chloride back extraction solution with a back extraction rate of 19.1%;
  • the Sc (OH) 3 precipitate was calcined at 600 ° C to generate hafnium oxide.
  • the total yield of rhenium was 18.7%.
  • the purity of europium oxide was 95.5%.
  • Example 9 The difference from Example 9 is that, according to the volume ratio (volume ratio of organic solution and aqueous solution) of the organic solution of the extractant and the back-extractant solution is 1: 1, the washed organic phase containing tritium and 500 mL contains 6 mol / The LH 2 SO 4 stripping agent aqueous solution (aqueous phase) was mixed in a reaction kettle at a reaction temperature of 50 ° C. to carry out a stripping reaction to generate a tritium sulfate stripping solution with a stripping rate of 15.5%;
  • the Sc (OH) 3 precipitate was calcined at 600 ° C to generate hafnium oxide.
  • the total yield of tritium is 13.8%.
  • the purity of erbium oxide was 92.5%.
  • the Sc 2 (C 2 O 4 ) 3 precipitate was calcined at 800 ° C. to generate hafnium oxide.
  • the total yield of rhenium was 15.0%.
  • Analysis by atomic emission spectrometry revealed that the purity of europium oxide was 98.5%.
  • the organic phase containing tritium is washed with a 0.5 mol / L sulfuric acid aqueous solution to remove co-extracted impurity elements, the impurity washing rate is more than 99%, and the tritium elution rate is 0.2%;
  • the volume ratio (organic solution: water solution volume ratio) of the organic solution of the extractant and the precipitation back-extractant solution is 10: 1, the washed organic phase loaded with tritium and the back-extractant aqueous solution (water phase containing 7 mol / L NaOH) ) Mixing to carry out a back extraction reaction, the back extraction rate of rhenium is 99.9%;
  • the Sc (OH) 3 precipitate was calcined at 500 ° C to generate hafnium oxide.
  • the total yield of rhenium was 99.1%.
  • the purity of europium oxide was 99.5%.
  • Comparative Examples 1, 2, and 3 were much lower than those of Examples 9, 10, mainly because the acid stripping efficiency was lower than that of alkali. Among them, the acid consumption in Comparative Example 1 was higher than that in Example 9, but the back-extraction rate and total ytterbium yield were not as good as those in Example 9; Comparative Examples 2, 3, sulfuric acid back-extraction, the effect of back-extraction was worse.
  • the stripping reaction temperature used is 70 ° C.
  • the back extraction rate of rhenium is 99.5%
  • the total yield of rhenium is 98.7%.
  • Example 9 Compared with Example 9, the difference is that 220 mL of a solution containing 6 mol / L HCl was added to the anion solution of hydrazone to adjust the pH of the solution to 8.0 to generate a Sc (OH) 3 precipitate.
  • the precipitation rate of rhenium was 99.8%; The purity of hafnium oxide reached 99.1%.
  • the total yield of rhenium was 98.6%.
  • the Sc (OH) 3 precipitate was washed with ethanol and water at 30 ° C and 80 ° C, respectively; the Sc (OH) 3 precipitate was washed with ethanol and water at 40 ° C and 90 ° C, respectively, to remove the surface Adsorbed organics and water-soluble impurities.
  • the organic phase containing 500 mL of rhenium was washed with 100 mL of a 4 mol / L hydrochloric acid aqueous solution to remove the co-extracted magazine elements.
  • the impurity washing rate reached 98% and the elution rate of rhenium was 0.3%;
  • the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the stripping agent solution is 1: 1, 500 mL of the organic phase of the washed support phase and 1000 mL of the NaOH stripping agent aqueous solution (aqueous phase)
  • the reaction kettle was mixed at a reaction temperature of 50 ° C to carry out a back-extraction reaction.
  • the back-extraction rate of osmium was 98.9%, and the generated anion complex was in the water phase and flowed out from the aqueous phase outlet.
  • the organic phase and rhenium contained no rhenium.
  • the complex anion solution is separated and returned to the extraction step for recycling;
  • the generated thorium hydroxide precipitate was separated from the precipitation mother liquor by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) 3 precipitate; the Sc (OH) 3 precipitate was washed with ethanol and water, respectively, at a temperature of 20 ° C and 50 ° C. °C to remove organic matter and water-soluble impurities adsorbed on the surface, respectively.
  • the Sc (OH) 3 precipitate was calcined at 600 ° C to generate hafnium oxide.
  • the total yield of rhenium was 98.3%.
  • the purity of europium oxide was 99.0%.
  • the 500 mL organic phase containing tritium was washed with 500 mL of a 1 mol / L hydrochloric acid aqueous solution to remove co-extracted magazine elements.
  • the impurity washing rate reached more than 99% and the elution rate of tritium was 0.2%;
  • volume ratio (volume ratio of organic solution and aqueous solution) of the organic solution of the extractant and the back-extractant solution is 1: 1
  • the washed 1000 mL organic phase containing the tritium and 500 mL of the back-extractant aqueous solution containing 5 mol / L NaOH (water Phase) Mix in a reaction kettle at a reaction temperature of 50 ° C to perform a back-extraction reaction.
  • the back-extraction rate of osmium is 99.3%, and the generated anion complex is in the aqueous phase and flows out from the aqueous phase outlet;
  • the phase is separated from the complex anion solution and returned to the extraction step for recycling;
  • the generated thorium hydroxide precipitate was separated from the precipitation mother liquor by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) 3 precipitate; the Sc (OH) 3 precipitate was washed with ethanol and water, respectively, at a temperature of 20 ° C and 50 ° C. °C to remove organic matter and water-soluble impurities adsorbed on the surface, respectively.
  • the Sc (OH) 3 precipitate was calcined at 600 ° C to generate hafnium oxide.
  • the total yield of rhenium was 98.3%.
  • the purity of europium oxide reached 99.2%.
  • the Sc (OH) 3 precipitate was calcined at 600 ° C to generate hafnium oxide. According to atomic emission spectrometry, the purity of europium oxide was 99.5%. The total yield of radon was 97.8%.
  • the osmium and concentrated NaOH solution extracted into the organic phase under optimized conditions (including NaOH concentration, temperature, and organic phase: water phase volume ratio) generate Sc (OH) 6 3- complex anion
  • rhenium enters the aqueous solution in the form of soluble ions, so that the back extraction efficiency is high, and the organic phase is separated from the water phase.
  • the traditional mixed clarification extraction tank can be used for continuous extraction and separation operations, which is conducive to industrial production. .
  • Adding the anion salt solution containing tritium anion to hydrochloric acid to neutralize the hydroxide OH - in the solution can transform the tritium anion into Sc (OH) 3 precipitation, so that the tritium can be enriched, and the Sc (OH) 3 precipitation can be applied.
  • Traditional solid-liquid separation equipment is used for separation, so it is also beneficial to industrial production.
  • thorium was extracted from thorium-containing hydrochloric acid solution with a kerosene solution containing 1 mol / L CA-12 extractant, and the end point of thorium-containing solution was controlled by NaOH
  • the pH is 3; the single-stage extraction rate of rhenium is above 85%.
  • the volume ratio (organic solution, aqueous solution volume ratio) of the organic solution of the extractant and the stripping agent solution is 1: 1, the washed organic phase loaded with tritium and the stripping agent aqueous solution (aqueous phase) containing 5mol / L NaOH Mix in a clarification extraction tank at a reaction temperature of 50 ° C to perform a back-extraction reaction.
  • the generated anion complex is in the aqueous phase and flows out from the aqueous phase outlet.
  • the organic phase of unloaded tritium is separated from the complex anion solution. And return to the extraction step for recycling;
  • the generated thorium hydroxide precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) 3 precipitate; the Sc (OH) 3 precipitation mother liquor is added to NaOH and returned to the thorium back extraction treatment step for use;
  • the (OH) 3 precipitate was washed with ethanol and water at 30 ° C and 80 ° C, respectively, to remove organic matters and water-soluble impurities adsorbed on the surface, respectively.
  • the Sc (OH) 3 precipitate was calcined at 500 ° C to generate crude ytterbium oxide; the crude ytterbium oxide was washed with a 0.01 mol / L aqueous hydrochloric acid solution at a temperature of 20 ° C to remove impurity elements therein to obtain ytterbium oxide; the crude oxidized Rhenium oxide obtained after washing with dilute hydrochloric acid water is washed with water and dried to obtain a ytterbium oxide product, and the extraction rate of the rhenium reaches more than 75%.
  • thorium was extracted from thorium sulfuric acid solution with a n-heptane solution containing 2mol / L naphthenic acid extractant, and controlled by NaOH
  • the final pH of the thorium-containing solution is 3.5; according to the volume ratio (organic solution: water solution volume ratio) of the extractant organic solution and the precipitation back-extractant solution is 10: 1, the washed tritium-containing organic phase and 7 mol / L NaOH
  • the stripping agent aqueous solution (aqueous phase) was mixed to perform a stripping reaction.
  • Hydrochloric acid was added to the complex anion solution to adjust the solution to pH 6.0 to generate a Sc (OH) 3 precipitate; the Sc (OH) 3 precipitate was washed with ethanol and water, respectively, at a washing temperature of 40 ° C and 90 ° C; The (OH) 3 precipitate was calcined at 600 ° C to generate thorium oxide; the crude thorium oxide was washed with a 0.5 mol / L hydrochloric acid aqueous solution at a temperature of 30 ° C to remove the impurity elements therein to obtain thallium oxide. The total recovery of thallium oxide was 85% or more.
  • VerS2atic10 extractant neodecanoic acid
  • tritium was extracted from tritium-containing hydrochloric acid solution using a sulfonated kerosene solution containing 2mol / LVerS2atic10 extractant, and the final equilibrium pH of the tritium-containing solution was controlled to be 3.25 with NaOH;
  • the unipolar extraction rate is over 90%.
  • the organic phase was washed with an acid solution of pH 3.25 at A / O ratio of 1: 1, and the washed organic phase loaded with tritium and a stripping agent aqueous solution (aqueous phase) containing 6mol / L NaOH were mixed in a clarification extraction tank according to A / O compared with 1: 2 for mixed back-extraction, the reaction temperature is 60 ° C, to carry out the back-extraction reaction, the complex anion is in the aqueous phase and flows out from the aqueous phase outlet; The anion solution is separated and recycled back to the extraction step for regeneration. Hydrochloric acid is added to the anion solution to adjust the solution to pH 8 to form a Sc (OH) 3 precipitate.
  • the generated thorium hydroxide precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) 3 precipitate; the Sc (OH) 3 precipitation mother liquor is added to NaOH and returned to the thorium back extraction treatment step for use;
  • the (OH) 3 precipitate was washed with ethanol and water at 30 ° C and 80 ° C, respectively, to remove organic matters and water-soluble impurities adsorbed on the surface, respectively.
  • the Sc (OH) 3 precipitate was calcined at 400 ° C to generate crude ytterbium oxide; the crude ytterbium oxide was washed with a 0.01 mol / L hydrochloric acid aqueous solution at a temperature of 20 ° C to remove impurity elements therein to obtain ytterbium oxide; the crude oxidized Rhenium oxide obtained after washing with dilute hydrochloric acid water is washed with water and dried to obtain a hafnium oxide product. The total recovery of the hafnium is above 85%.
  • tritium was extracted from tritium-containing hydrochloric acid solution with a sulfonated kerosene solution containing 1 mol / L CA100 extractant, and the final equilibrium pH of the tritium-containing solution was controlled to be 3.2 with NaOH;
  • the single-stage extraction rate reaches more than 95%.
  • the organic phase was washed with an acid solution of pH 3.25 according to A / O ratio 1: 1, and the washed organic phase loaded with tritium and a stripping agent aqueous solution (aqueous phase) containing 4mol / L NaOH were mixed in a clarification extraction tank according to A / O compared with 1: 2 for mixed back-extraction, the reaction temperature is 60 ° C, to carry out the back-extraction reaction, the complex anion is in the aqueous phase and flows out from the aqueous phase outlet; The anion solution is separated and returned to the extraction step for regeneration and recycling; a hydrochloric acid solution is added to the complex anion solution to adjust the solution to pH 7.5 to form a Sc (OH) 3 precipitate.
  • the generated thorium hydroxide precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) 3 precipitate; the Sc (OH) 3 precipitation mother liquor is added to NaOH and returned to the thorium back extraction treatment step for use;
  • the (OH) 3 precipitate was washed with ethanol and water at 30 ° C and 80 ° C, respectively, to remove organic matters and water-soluble impurities adsorbed on the surface, respectively.
  • the Sc (OH) 3 precipitate was calcined at 500 ° C to generate crude ytterbium oxide; the crude ytterbium oxide was washed with a 0.01 mol / L aqueous hydrochloric acid solution at a temperature of 25 ° C to remove the impurity elements therein to obtain the ytterbium oxide; the crude oxidized Rhenium oxide obtained after washing with dilute hydrochloric acid water is washed with water and dried to obtain a hafnium oxide product. The total recovery of the hafnium is above 80%.
  • CA-12 extractant (secondary octylphenoxy substituted acetic acid), KOH as back extractant
  • thorium was extracted from thorium-containing hydrochloric acid solution with a kerosene solution containing 4mol / l CA-12 extractant, and thorium-containing solution was controlled by KOH
  • the endpoint pH was 3; the single-stage extraction rate of rhenium reached above 85%.
  • volume ratio (volume ratio of organic solution and aqueous solution) of the extracted organic solution and back-extractant solution is 1: 1, the washed organic phase loaded with tritium and the back-extractant aqueous solution (water phase) containing 8 mol / l KOH Mix in a clarification extraction tank at a reaction temperature of 90 ° C to perform a back-extraction reaction.
  • the generated anion complex is in the aqueous phase and flows out from the aqueous phase outlet; the organic phase with no-loaded tritium is separated from the complex anion solution, and Return to the extraction step for recycling;
  • the generated thorium hydroxide precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) 3 precipitate; the Sc (OH) 3 precipitation mother liquor is added to KOH and returned to the thorium back extraction treatment step for use;
  • the (OH) 3 precipitate was washed with ethanol and water at a washing temperature of 20 ° C and 50 ° C, respectively, to remove organic matters and water-soluble impurities adsorbed on the surface, respectively.
  • the Sc (OH) 3 precipitate was calcined at 500 ° C to generate crude ytterbium oxide; the crude ytterbium oxide was washed with a 0.01 mol / L aqueous hydrochloric acid solution at a temperature of 20 ° C to remove impurity elements therein to obtain ytterbium oxide; the crude oxidized Rhenium oxide obtained after washing with dilute hydrochloric acid water is washed with water and dried to obtain a hafnium oxide product, and the extraction rate of the hafnium reaches more than 80%.
  • CA-12 extractant (secondary octylphenoxy substituted acetic acid), KOH as back extractant
  • thorium was extracted from thorium-containing hydrochloric acid solution with a kerosene solution containing 4mol / l CA-12 extractant, and thorium-containing solution was controlled by KOH
  • the endpoint pH was 3; the single-stage extraction rate of rhenium reached above 85%.
  • volume ratio (volume ratio of organic solution and aqueous solution) of the extracted organic solution and back-extractant solution is 1: 1, the washed organic phase loaded with tritium and the back-extractant aqueous solution (water phase) containing 8 mol / l KOH Mix in a clarification extraction tank with a reaction temperature of 60 ° C to perform a back-extraction reaction.
  • the generated anion complex is in the aqueous phase and flows out from the aqueous phase outlet; the organic phase with no-loaded tritium is separated from the complex anion solution, and Return to the extraction step for recycling;
  • the generated thorium hydroxide precipitate and the precipitation mother liquor are separated by vacuum filtration to obtain an enriched thorium hydroxide Sc (OH) 3 precipitate; the Sc (OH) 3 precipitation mother liquor is added to KOH and returned to the thorium back extraction treatment step for use;
  • the (OH) 3 precipitate was washed with ethanol and water at a washing temperature of 20 ° C and 50 ° C, respectively, to remove organic matters and water-soluble impurities adsorbed on the surface, respectively.
  • the Sc (OH) 3 precipitate was calcined at 500 ° C to generate crude ytterbium oxide; the crude ytterbium oxide was washed with a 0.01 mol / L aqueous hydrochloric acid solution at a temperature of 20 ° C to remove impurity elements therein to obtain ytterbium oxide; the crude oxidized Rhenium oxide obtained after washing with dilute hydrochloric acid water is washed with water and dried to obtain a hafnium oxide product, and the extraction rate of the hafnium reaches more than 76%.
  • the osmium and concentrated NaOH solution extracted into the organic phase under optimized conditions (including NaOH concentration, temperature, and organic phase: water phase volume ratio) generate Sc (OH) 6 3- complex anion
  • rhenium enters the aqueous solution in the form of soluble ions, so that the back extraction efficiency is high, and the organic phase is separated from the water phase.
  • the traditional mixed clarification extraction tank can be used for continuous extraction and separation operations, which is conducive to industrial production. .
  • Adding the anion salt solution containing tritium anion to hydrochloric acid to neutralize the hydroxide OH - in the solution can transform the tritium anion into Sc (OH) 3 precipitation, so that the tritium can be enriched, and the Sc (OH) 3 precipitation can be applied.
  • Traditional solid-liquid separation equipment is used for separation, so it is also beneficial to industrial production.
  • the calcined crude ytterbium oxide is soluble in hot concentrated hydrochloric acid but insoluble or very slightly soluble in dilute hydrochloric acid, and the resulting crude ytterbium oxide is washed with a dilute aqueous hydrochloric acid solution at a lower temperature to dissolve and remove the Impurity elements can well separate rhenium from impurity elements to obtain purified erbium oxide.

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Abstract

L'invention concerne un procédé d'enrichissement de scandium, comprenant les étapes suivantes : S1, extraction du scandium d'une solution d'acide inorganique contenant du scandium à l'aide d'un agent d'extraction organique ou d'une solution de solvant organique contenant un agent d'extraction organique afin d'obtenir une phase organique contenant du scandium ; et S2, réextraction et précipitation de la phase organique contenant du scandium à l'aide d'une solution de précipitant, suivie d'une séparation pour obtenir un précipité contenant du scandium, une liqueur mère de précipitation et une phase organique sans charge. La solution de précipitant joue un rôle à la fois dans la réextraction et la précipitation, raccourcissant ainsi le processus d'opération et réduisant la consommation de matières premières.
PCT/CN2019/095692 2018-09-28 2019-07-12 Procédé d'enrichissement de scandium WO2020063035A1 (fr)

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CN201811143122.0 2018-09-28
CN201811143127.3 2018-09-28
CN201811141713.4A CN109022839A (zh) 2018-09-28 2018-09-28 富集钪的方法
CN201811143127.3A CN109266870A (zh) 2018-09-28 2018-09-28 提取氧化钪的方法
CN201811143122.0A CN109179480A (zh) 2018-09-28 2018-09-28 提取氧化钪的方法
CN201811141713.4 2018-09-28

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US20120207656A1 (en) * 2011-02-11 2012-08-16 Emc Metals Corporation System and Method for Recovery of Scandium Values From Scandium-Containing Ores
CN109022839A (zh) * 2018-09-28 2018-12-18 中国恩菲工程技术有限公司 富集钪的方法
CN109179480A (zh) * 2018-09-28 2019-01-11 中国恩菲工程技术有限公司 提取氧化钪的方法
CN109266870A (zh) * 2018-09-28 2019-01-25 中国恩菲工程技术有限公司 提取氧化钪的方法

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CN101824555A (zh) * 2010-06-09 2010-09-08 攀枝花学院 提取钪的方法
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CN109022839A (zh) * 2018-09-28 2018-12-18 中国恩菲工程技术有限公司 富集钪的方法
CN109179480A (zh) * 2018-09-28 2019-01-11 中国恩菲工程技术有限公司 提取氧化钪的方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113088692A (zh) * 2021-04-06 2021-07-09 鞍山昊旻稀土科技有限公司 一种替代环烷酸萃取用的萃取剂及钇萃取工艺

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