WO2016031699A1 - Method for separating scandium - Google Patents
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- WO2016031699A1 WO2016031699A1 PCT/JP2015/073491 JP2015073491W WO2016031699A1 WO 2016031699 A1 WO2016031699 A1 WO 2016031699A1 JP 2015073491 W JP2015073491 W JP 2015073491W WO 2016031699 A1 WO2016031699 A1 WO 2016031699A1
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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
- C22B59/00—Obtaining rare earth metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- the present invention relates to a method for separating scandium, titanium and zirconium from an aqueous stock solution containing at least scandium, titanium and zirconium and recovering crude scandium. Furthermore, the present invention relates to a method for producing high purity scandium using this crude scandium through a chelate resin adsorption step and an organic solvent extraction step.
- Scandium is one of the transition metal elements and is classified as a rare earth element together with yttrium.
- scandium can be used by encapsulating scandium iodide in metal halide lamps, zirconium oxide stabilizers, etc. Zirconia is used as an electrolyte for solid oxide fuel cells.
- Scandium is a relatively rare metal and is contained in tortbaitite, but it is produced in small quantities, so it is separated and recovered from residues such as titanium ore and nickel oxide ore.
- a solid residue obtained by chlorinating titanium ore is leached in an acid solution and filtered to obtain a scandium-containing solution from which insoluble residues have been removed, and then the scandium-containing solution is converted to TBP (tributyl phosphate).
- scandium is selectively extracted by contacting with an organic solvent containing a), back-extracted with hydrochloric acid, ammonia solution is added and precipitated to recover high-purity scandium (Example 1).
- Patent Document 2 discloses a method for recovering nickel and scandium from an oxide ore containing nickel and scandium.
- a first neutralization step of removing iron and aluminum in the leachate as precipitates by adding a neutralizing agent to the leachate and adjusting the pH to a range of 2 to 4 and (3) first A second neutralization step for recovering scandium in the solution as a precipitate by adding a neutralizing agent to the solution after removing the precipitate in the neutralization step and adjusting the pH to a range of more than 4 to 7.5.
- Patent Document 1 discloses a method of selectively extracting scandium by leaching a solid residue obtained by chlorinating titanium ore in an acid solution and then contacting with an organic solvent containing TBP (tributyl phosphate).
- TBP tributyl phosphate
- the scandium-containing liquid contains impurities such as titanium and zirconium derived from titanium ore, scandium cannot be selectively extracted into an organic solvent.
- a neutralizing agent is added to the leachate to adjust the pH to a range of 2 to 4, thereby precipitating iron and aluminum, and then adjusting the pH to a range of more than 4 to 7.5.
- the present inventors have mixed an aqueous stock solution containing at least scandium, titanium, and zirconium ions with an alkali.
- the pH is adjusted to 1.0 to 2.0 to precipitate titanium and zirconium, or an aqueous stock solution containing at least scandium, titanium and zirconium precipitates is mixed with an acid to adjust the pH to 1. It has been found that when scandium is dissolved in a range of 0 to 2.0 (titanium and zirconium separation step), scandium and titanium and zirconium can be efficiently separated.
- a suspension obtained by the titanium / zirconium separation step (a suspension containing scandium in the liquid phase and titanium and zirconium in the solid phase) may be referred to as a scandium-containing suspension.
- the scandium-containing suspension is subjected to solid-liquid separation, and alkali is added to the separated solution (an acidic solution containing scandium) to adjust the pH to a range of 3.5 to 7.0, thereby precipitating scandium.
- alkali is added to the separated solution (an acidic solution containing scandium) to adjust the pH to a range of 3.5 to 7.0, thereby precipitating scandium.
- solid-liquid separation first scandium precipitation / separation step
- the aqueous solution (first aqueous solution) in which the scandium-containing aqueous suspension obtained in the above step, the acidic solution containing scandium or the scandium precipitate is dissolved is low in selectivity with scandium like titanium and zirconium. Since the adsorbed species are separated, it is found that by adhering any one of these to a chelate resin and adsorbing scandium, the adsorption of scandium to the chelate resin can be promoted and the purity of scandium can be increased. It was.
- the scandium-containing aqueous suspension obtained in the above step or the aqueous solution (first aqueous solution) in which the scandium-containing acidic solution or scandium precipitate is dissolved is brought into contact with the chelate resin, and scandium is adsorbed.
- a step of eluting the adsorbed scandium into an aqueous solvent to obtain a second aqueous solution (chelate resin adsorption / elution step), an aqueous solution containing scandium obtained in each of the above steps, or an acidic solution or various aqueous solutions containing scandium Is contacted with an organic solvent containing an extractant, scandium is extracted into the organic solvent to obtain a scandium-containing organic solution (organic solvent extraction step), and scandium in the scandium-containing organic solution is back-extracted into an aqueous solvent.
- a step of obtaining an aqueous solution (back extraction step), and further a scandium-containing aqueous suspension or scandi obtained in each of the above steps
- the present invention (1) A step of preparing an aqueous stock solution containing at least scandium, titanium, and zirconium; and mixing the acid or alkali with the aqueous stock solution to adjust the pH to a range of 1.0 to 2.0.
- a method for separating scandium comprising the steps of: obtaining a scandium-containing aqueous suspension comprising a phase and titanium and zirconium in the solid phase; (2) Preferred Embodiment 1
- the pH is adjusted to a range of 3.5 to 7.0 by mixing an alkali with an acidic liquid obtained by solid-liquid separation of the scandium-containing aqueous suspension to remove titanium and zirconium.
- the method of separating scandium further comprising the step of precipitating scandium and the step of separating the precipitated scandium by solid-liquid separation, (3) Preferred Embodiment 2
- the chelate resin is scandium.
- a method for separating scandium further comprising: adsorbing scandium adsorbed on the chelate resin; and eluting the scandium adsorbed on the chelate resin into an aqueous solvent to obtain a second aqueous solution;
- Preferred embodiment 3 The above-mentioned scandium-containing aqueous suspension, an acidic liquid obtained by solid-liquid separation thereof, a first aqueous solution in which the precipitated scandium is dissolved, or a second aqueous solution containing the eluted scandium
- a method for separating scandium further comprising: (5) Preferred Embodiment 4 An acidic liquid obtained by solid-liquid separation of the scandium-containing aqueous suspension, a first aqueous solution in which the precipitated scandium is dissolved, a second aqueous solution containing the eluted scandium, or the scandium
- the scandium is recovered by bringing the scandium into contact with an organic solution containing the extracted scandium or a third aqueous solution obtained by back-extracting the scandium and an aqueous solvent containing a precipitating agent, and solid-liquid separation. And a process for separating scandium.
- the method for separating scandium of the present invention can efficiently separate scandium from titanium and zirconium using an aqueous stock solution containing at least scandium, titanium and zirconium. Thereby, contamination of titanium and zirconium as impurities can be kept low, and scandium can be separated easily and efficiently. Further, alkali is mixed with the above-mentioned acidic liquid containing scandium that has been separated into solid and liquid to adjust the pH to a range of 3.5 to 7.0, thereby precipitating scandium. Thus, it is possible to keep impurities such as iron (ferrous iron) and manganese from being mixed low, and scandium can be recovered efficiently and easily.
- the crude scandium obtained by these methods has a low impurity content, it removes impurities during the subsequent chelate resin adsorption / elution step, organic solvent extraction step, back extraction step, scandium precipitation step, etc. Each process can be performed efficiently. In particular, removal of impurities such as titanium and zirconium can promote the adsorption of scandium to the chelate resin, and as a result, the purity of scandium can be increased.
- the method of the present invention is optimal for separating and recovering scandium using a solution obtained by suspending a residue obtained by chlorinating titanium ore in water and a solution obtained by suspending a residue obtained by leaching titanium ore with an acid. is there.
- FIG. 4 is a diagram showing scandium adsorption isotherms in Example 3 and Comparative Example 1.
- FIG. 4 is a diagram showing scandium adsorption isotherms in Example 3 and Comparative Example 1.
- an aqueous stock solution containing at least scandium, titanium and zirconium is mixed with an acid or alkali to adjust the pH to a range of 1.0 to 2.0, scandium is contained in the liquid phase, and titanium and zirconium are mixed in the solid phase.
- an acid or alkali to adjust the pH to a range of 1.0 to 2.0
- scandium is contained in the liquid phase
- titanium and zirconium are mixed in the solid phase.
- the aqueous stock solution is an aqueous solution containing scandium such as a solution containing scandium ions, a slurry containing scandium hydroxide or scandium oxide, and contains titanium and zirconium in addition to scandium. It is out. Titanium and zirconium may be in an ionic state or a compound such as a hydroxide or an oxide.
- Periodic Table Group 15 elements such as phosphorus, arsenic, antimony, and bismuth
- Periodic Table Group 16 elements such as selenium and tellurium
- Periodic Group 17 elements such as fluorine and chlorine May be.
- titanium and zirconium those containing at least one metal selected from rare earth elements other than vanadium and scandium are preferable because the effects of the present invention can be easily obtained.
- concentration of scandium in the aqueous stock solution there is no particular limitation on the concentration of scandium in the aqueous stock solution, and an aqueous stock solution having an arbitrary concentration can be used. In general, if a high-concentration aqueous stock solution (about 500 to 50000 mg / L) is used, scandium can
- the scandium concentration is low (about 1 to 500 mg / L)
- scandium can be sufficiently purified, separated and recovered.
- concentration of elements other than scandium there is no particular limitation on the concentration of elements other than scandium.
- the concentration of impurity components titanium, zirconium, and vanadium are each about 1000 mg / L or less
- scandium is easily purified.
- the concentration of impurity components titanium, zirconium, vanadium, etc.
- the concentration of rare earth elements other than scandium is not particularly limited, but is preferably about 0 to 1000 mg / L.
- the aqueous stock solution can be used in any pH range. If the pH of the stock solution is 6 or more, it is preferable to adjust the pH to 6 or less by mixing an acid in advance, and more preferably to adjust the pH to 2 or less. When the pH is 2 or more, scandium, titanium, and zirconium are in a slurry state of precipitates such as hydroxide, but when the pH is 2 or less, scandium, titanium, and zirconium are dissolved. Since it is a solution, it is easy to handle, and it is more preferable that the pH is 1 or less, and a pH of 0.5 or less is more preferable because the quality is stable.
- the aqueous stock solution contains at least scandium, titanium, and zirconium.
- the acidic liquid has a pH of about 6 or less
- the neutral liquid has a pH of about 6 to 8
- the alkaline liquid has a pH of about 8 or more.
- a solution obtained by dissolving an ore with an acid specifically, a solution obtained by suspending a residue obtained by chlorinating a titanium ore in water
- a solution obtained by dissolving an ore residue with an acid specifically, a titanium ore by an acid. It is more preferable to use a liquid obtained by suspending the residue leached in step (b) in water.
- An acidic liquid obtained by dissolving a material such as ore containing scandium with an acid, an acidic liquid obtained by mixing an alkali with this acidic liquid, a neutral liquid or an alkaline liquid 2) A liquid obtained by dissolving a material such as ore containing scandium with an acid Acidic liquid after hydrolysis or neutralization to purify other metal components, or acidic liquid in which the residue after purifying other metal components is dissolved with acid, acidic liquid in which alkali is mixed with this acidic liquid, 3) An alkaline solution obtained by dissolving a material such as an ore containing scandium with an alkali, an acidic solution obtained by mixing an acid with the alkaline solution, a neutral solution or an alkaline solution 4) an alkali such as an ore containing scandium.
- the alkaline solution after hydrolyzing or neutralizing the solution dissolved in step 2 to purify other metal components an acidic solution obtained by mixing an acid with this alkaline solution, a neutral solution or an alkaline solution 5) Scandium An alkaline solution, neutral solution or acidic solution obtained by dissolving the residue obtained by hydrolyzing or neutralizing a solution in which a material such as ore is dissolved with an alkali and purifying other metal components with an alkali or an acid 6) 1) to 5) Acidic, neutral or alkaline liquids after scandium is roughly purified by adsorbing and eluting the scandium contained in the acidic or alkaline liquids with an ion exchange resin (chelate resin) or by precipitation separation.
- an ion exchange resin chelate resin
- Slurry containing scandium hydroxide, scandium oxide, etc. obtained by roughly purifying scandium by adsorbing and eluting the scandium contained in the acidic and alkaline liquids of 1) to 5) with an ion exchange resin (chelate resin) or by precipitation separation.
- Alkaline liquid, neutral liquid or acidic liquid obtained by mixing alkali or acid with
- materials containing scandium various ores, residues after refining other metal components from ores, aluminum alloys containing scandium, anodes of nickel / alkali storage batteries, metal halide lamps, electrolytes of solid oxide fuel cells
- materials such as ceramics such as scandia-stabilized zirconia and wastes can be used.
- ores for example, tortue bait, gold ore, silver ore, copper ore, lead ore, bismuth ore, tin ore, antimony ore, mercury ore, zinc ore, iron ore, chromium ore, manganese ore, tungsten ore, molybdenum ore, Arsenic ore, nickel ore, cobalt ore, uranium ore, thorium ore, phosphorus ore, sulfur ore slag, barium ore, calcium ore, magnesium ore, strontium ore slag, beryllium ore, aluminum ore, titanium ore etc., iron ore, nickel Ores containing a large amount of scandium such as ores, titanium ores, manganese ores, tin ores, and aluminum ores are preferred.
- An acid that dissolves materials such as ores or an acid that is adjusted to be acidic can be used without limitation, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and aqua regia, and organic acids such as acetic acid can be used.
- a liquid obtained by refining other metal components by hydrolyzing or neutralizing a liquid obtained by dissolving a material such as ore with an acid can also be used.
- a leachate obtained by adding sulfuric acid to a nickel oxide ore of laterite ore and leaching under pressure, or a solution obtained by removing nickel from the leachate can be used.
- an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, or aqua regia
- an organic acid such as acetic acid
- Titanium chloride the residue after taking out iron chloride is dissolved in an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, aqua regia, etc., an organic acid such as acetic acid, The liquid etc. after taking out iron content can be used.
- an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, aqua regia, etc.
- an organic acid such as acetic acid
- alkali used for pH adjustment can be used without limitation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, calcium hydroxide (slaked lime), water Alkaline earth metal hydroxides such as magnesium oxide and barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide and barium oxide, and alkaline earth metals such as calcium carbonate, magnesium carbonate and barium carbonate Compounds, ammonia, amines and the like can be used.
- a solution obtained by dissolving a material such as ore with an alkali or a solution obtained by refining other metal components by hydrolyzing or neutralizing the same can also be used.
- the alkaline solution when materials such as ores are dissolved with alkali, the alkaline solution, the alkaline solution after hydrolysis or neutralization of the alkaline solution and taking out other metals can be used.
- Alkalis for dissolving materials such as ores or alkalis used for pH adjustment can be used without limitation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, water Alkaline earth metal hydroxides such as calcium oxide (slaked lime), magnesium hydroxide, barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide, barium oxide, calcium carbonate, magnesium carbonate, carbonic acid Alkaline earth metal compounds such as barium, ammonia, amines and the like can be used.
- alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
- alkali metal compounds such as sodium carbonate and potassium carbonate
- water Alkaline earth metal hydroxides such as calcium oxide (slaked lime), magnesium hydroxide, barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide, barium oxide, calcium carbonate, magnesium carbonate, carbonic acid Alkaline
- a solution obtained by dissolving a material such as ore with an alkali or a solution obtained by refining other metal components by hydrolyzing or neutralizing the same can also be used.
- the acid that adjusts the pH to acid can be used without limitation, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and aqua regia, and organic acids such as acetic acid can be used.
- a dissolved acidic solution may be used.
- the aqueous stock solution may be prepared by roughly purifying scandium in advance.
- the rough purification of scandium is performed by adsorbing scandium contained in the acidic solution and the alkaline solution obtained for preparing the same in a conventional manner, for example, with an ion exchange resin (chelate resin),
- the concentration of scandium can be increased by dispersing scandium hydroxide, scandium oxide, etc. obtained by elution from an ion exchange resin (chelate resin) or by precipitation separation treatment by adjusting pH, etc. in water. it can.
- a solution whose pH is adjusted by adding the roughly purified solution and acid or alkali can be used as the aqueous stock solution.
- the scandium-containing liquid once has a pH of 7 or more to precipitate scandium hydroxide
- the slurry can be mixed with an acid or alkali to adjust the pH as an aqueous stock solution.
- the stock solution is preferably used separately.
- an aqueous stock solution containing at least scandium, titanium and zirconium is mixed with an alkali to adjust the pH to a range of 1.0 to 2.0, and the titanium and zirconium are solid-phased. And an aqueous suspension containing scandium containing scandium in the liquid phase.
- an aqueous suspension containing scandium containing scandium in the liquid phase By setting the pH of the aqueous stock solution to less than 1.0 to 1.0 to 2.0, titanium and zirconium precipitates can be deposited. When the pH adjustment is lower than 1.0, precipitation of titanium and zirconium is insufficient, and much titanium and zirconium remain in the aqueous stock solution.
- the alkali for pH adjustment can be used without limitation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, calcium hydroxide (slaked lime), magnesium hydroxide, Alkaline earth metal hydroxides such as barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide and barium oxide, alkaline earth metal compounds such as calcium carbonate, magnesium carbonate and barium carbonate, ammonia , Amines and the like can be used.
- a liquid obtained by refining other metal components by hydrolyzing or neutralizing a liquid obtained by dissolving a material such as ore with an alkali can also be used.
- the temperature at the time of pH adjustment can be appropriately set. For example, it is preferably about 2 to 100 ° C., more preferably about 5 to 70 ° C.
- an aqueous stock solution containing at least scandium, titanium, and zirconium is mixed with an acid to adjust the pH to a range of 1.0 to 2.0 and dissolve scandium.
- the pH of the aqueous stock solution By adjusting the pH of the aqueous stock solution from greater than 2.0 to 1.0 to 2.0, the scandium can be dissolved, and the precipitate of titanium and zirconium can be maintained as it is. it can.
- the pH adjustment is lower than 1.0, titanium and zirconium precipitates are dissolved, and a large amount of titanium and zirconium are dissolved in the aqueous stock solution. Further, when the pH adjustment is higher than 2.0, scandium precipitates remain and are mixed into titanium and zirconium precipitates, so that the scandium recovery rate decreases.
- the acid that adjusts the pH to acid can be used without limitation, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and aqua regia, and organic acids such as acetic acid can be used.
- a dissolved acidic solution may be used.
- the temperature at the time of pH adjustment can be appropriately set. For example, it is preferably about 2 to 100 ° C., more preferably about 5 to 70 ° C.
- Each step of first scandium precipitation / separation (preferred embodiment 1)
- the aqueous suspension containing scandium obtained in the titanium and zirconium separation step is subjected to solid-liquid separation to remove titanium and zirconium, and an alkali is mixed with the aqueous solution (acid solution) after removal to adjust the pH to 3.5 to It is preferable to adjust to the range of 7.0.
- an alkali is mixed with the aqueous solution (acid solution) after removal to adjust the pH to 3.5 to It is preferable to adjust to the range of 7.0.
- the alkali for pH adjustment can be used without limitation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, calcium hydroxide (slaked lime), magnesium hydroxide, Alkaline earth metal hydroxides such as barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide and barium oxide, alkaline earth metal compounds such as calcium carbonate, magnesium carbonate and barium carbonate, ammonia , Amines and the like can be used.
- the temperature at the time of pH adjustment can be appropriately set.
- any ordinary method can be used.
- a machine or the like can be used.
- the collected precipitate is dried and / or calcined as necessary.
- titanium oxide, zirconium oxide powder, etc. can be recovered by drying and / or firing the precipitate.
- the object of solid-liquid separation is a liquid containing scandium precipitates
- the scandium oxide powder can be recovered by drying and / or firing the precipitates.
- Each step of chelate resin adsorption / elution (Preferred embodiment 2) An aqueous suspension containing scandium obtained in the titanium and zirconium separation step, or an acidic solution obtained by solid-liquid separation of the suspension, and a first aqueous solution in which the scandium precipitate obtained in the scandium precipitation step is dissolved in an aqueous solvent.
- the second aqueous solution can be obtained by contacting the chelate resin to adsorb scandium and then eluting the adsorbed scandium into the aqueous solvent.
- aqueous solvent for dissolving the scandium precipitate a known acid such as a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, or a nitric acid aqueous solution, or a known alkali such as a sodium carbonate aqueous solution or an ammonium carbonate aqueous solution can be used.
- Acid is preferable from the viewpoint of cost and handling, and the concentration is not particularly limited as long as the solubility of scandium is sufficiently high. However, if scandium is recovered at a higher concentration, a higher concentration is preferable, for example, 70% sulfuric acid is more preferable. preferable.
- a conventionally well-known chelate resin can be used, and a chelate resin with a large amount of scandium adsorption is preferable.
- the functional group of the chelate resin with a large amount of scandium adsorption includes iminodiacetic acid, thiourea, polyamine, aminophosphoric acid, methylglucamine, aminooxime, phosphonic acid, sulfonic acid, carboxylic acid, and the like.
- the resin which has can be used.
- the chelate resin adsorbed with scandium is transferred to an elution tank as necessary, and is contacted with a known eluent such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, sodium carbonate or ammonium carbonate to elute scandium in an aqueous solvent.
- a known eluent such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, sodium carbonate or ammonium carbonate to elute scandium in an aqueous solvent.
- a known eluent such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, sodium carbonate or ammonium carbonate.
- a known eluent such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, sodium carbonate or ammonium carbonate.
- the liquid temperature in the adsorption tank and elution tank can be appropriately set, and is preferably about 2 to
- an acid or alkali is mixed with the aqueous solution to adjust the pH to 4.0 to Adjustment to a range of 7.0 is preferable because the amount of extraction increases.
- the pH of the aqueous solution is in the above range, scandium is mainly extracted, and the impurity element is hardly extracted and can be separated.
- the pH is lower than 4.0, the amount of scandium extracted is decreased, and the yield is lowered. If it is higher than 7.0, the extraction amount of the impurity element is increased, and the separation efficiency is deteriorated.
- a preferred pH is 5.0 to 6.5.
- the acid that adjusts the pH to acid can be used without limitation, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and aqua regia, and organic acids such as acetic acid can be used. You may use the acidic liquid which melt
- the alkali for adjusting the pH can be used without limitation as long as it exhibits alkalinity, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, etc.
- Alkaline earth metal hydroxides such as calcium hydroxide (slaked lime), magnesium hydroxide, barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide, barium oxide, calcium carbonate, magnesium carbonate
- alkaline earth metal compounds such as barium carbonate, ammonia, amines and the like can be used, and a solution obtained by dissolving a material such as ore with an alkali may be used.
- An aqueous solution containing scandium and an organic solvent containing an extractant are mixed to extract a complex formed from scandium and the extractant into the organic solvent.
- a conventionally well-known thing can be used for an extractant,
- carboxylic acid and / or its salt (Hereinafter, it may be called a carboxylic acid type extractant.) Is preferable.
- Carboxylic acid is an organic acid having a carboxy group, and examples of the carboxylate include salts such as sodium, potassium, and ammonium, and any salt that forms a complex with scandium can be used.
- extractants such as neodecanoic acid, versatic acid, naphthenic acid, oleic acid, and lauric acid can be used as the carboxylic acid-based extractant, and naphthenic acid and / or neodecanoic acid are preferred. Used.
- the ratio of the extractant can be appropriately set, and the ratio of the carboxylic acid-type extractant is preferably 1 to 50% by mass, more preferably 5 to 20% by mass with respect to the organic solvent.
- the surface modifier examples include long-chain alkyl compounds such as nonylphenol, 1-decanol, isodecanol, 1-octanol and 2-ethylhexanol, and alkyl phosphate compounds such as tributyl phosphate (TBP).
- the addition amount of the interfacial modifier can be appropriately set, and is usually preferably 1 to 50% by mass and more preferably 5 to 40% by mass with respect to the organic solvent.
- the solvent extraction operation of scandium is performed by using any liquid-liquid contact device and extracting a solution containing scandium (the aqueous suspension, the acidic liquid, the first aqueous solution, or the second aqueous solution) and A liquid-liquid contact with an agent and, if necessary, an organic solvent containing a surface modifier at a suitable temperature for a certain period of time by a known procedure, and then separating into an extractant phase and a liquid phase by stationary separation or centrifugation.
- the liquid-liquid contact device include a centrifugal extractor, a mixer, a shaker, a separatory funnel, a multistage liquid-liquid contact device, more specifically, a countercurrent mixer settler, a continuous method, a batch method.
- the treatment temperature is preferably set so as to maintain the temperature of the organic solvent containing various aqueous solutions and the extractant before the extraction operation, but the flash point of the organic solvent, the phase separation rate, and the stability of the extractant phase. In general, it is preferable to keep the temperature at 20 to 70 ° C.
- the solvent extraction is not limited to once, and may be performed in several steps.
- the organic solvent can be used without any particular limitation.
- Aromatic hydrocarbon compounds such as toluene and p-chlorotoluene; kerosene, n-pentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, n-dodecane, cyclohexane, Chloroform, tetrachloromethane, chloroethane, 1,1-dichloroethane, 1,2-
- the scandium-containing organic solution containing the extracted scandium and the aqueous solvent are mixed, and the scandium in the scandium-containing organic solution is back-extracted into the aqueous solvent to obtain a third aqueous solution.
- the aqueous solvent used for the back extraction is water or a mixture of water and an organic solvent such as alcohol as necessary, and the content of the organic solvent is preferably about 10% by mass or less.
- the aqueous solvent used for back extraction is preferably acidified using an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid.
- the scandium back-extraction operation is performed by bringing the organic solvent and the aqueous solvent into contact with each other at a suitable temperature for a certain period of time by a known procedure using the above-described liquid-liquid contact device, and then by means of stationary separation or centrifugation. It can be performed by separating into a phase and a liquid phase.
- the liquid-liquid contact device include a centrifugal extractor, a mixer, a shaker, a separatory funnel, a multi-stage liquid-liquid contact device, more specifically, a counter-current mixer settler and a centrifugal extractor. Either the method or the batch method may be used.
- the back extraction is not limited to once, and may be performed in several steps.
- the organic solvent extraction step and the back extraction step are not limited to once, and it is preferable because the concentration of scandium can be increased by repeating several times.
- the purity of scandium is 99.0% by mass or more, and preferably 99.5% by mass or more.
- Each step of second scandium precipitation / recovery (preferred embodiment 4)
- a solution containing scandium obtained in the above steps (2) to (5) (an acid solution obtained by solid-liquid separation of a scandium-containing aqueous suspension, a first aqueous solution, a second aqueous solution, or a scandium-containing organic material)
- This is a step of mixing a solution or a back-extracted third aqueous solution) and a liquid containing a precipitating agent (aqueous solvent) to precipitate scandium and recovering scandium as a precipitate by solid-liquid separation.
- the purity of scandium is 99.0% by mass or more. And preferably 99.5% by mass or more.
- carboxylic acid and / or a salt thereof (hereinafter sometimes referred to as a carboxylic acid precipitating agent) is preferable.
- carboxylic acid is a carboxylic acid having a carboxy group
- examples of the carboxylate include salts such as sodium, potassium, and ammonium, and any salt that precipitates scandium can be used.
- formic acid methanoic acid
- acetic acid ethanoic acid
- propionic acid propanoic acid
- butyric acid butanoic acid
- valeric acid penentanoic acid
- caproic acid hexanoic acid
- enanthate Acids heptanoic acid
- fatty acids such as caprylic acid (octanoic acid)
- hydroxy acids such as lactic acid (2-hydroxypropanoic acid
- malic acid (2-hydroxybutanedioic acid
- citric acid (2-hydroxypropanetricarboxylic acid
- Oxalic acid ethanedioic acid
- malonic acid propanedioic acid
- succinic acid butanedioic acid
- glutaric acid pentanedioic acid
- adipic acid hexanedioic acid
- fumaric acid ((E) -buta-2) -Didioic acid)
- the ratio of the precipitating agent can be appropriately set, and the ratio of the carboxylic acid-based precipitating agent to scandium is preferably 1.0 to 5.0 mol, more preferably 1.5 to 3.0 mol.
- a precipitation apparatus is used to cause scandium and a precipitating agent to come into contact with each other at a suitable temperature for a certain period of time by a known procedure for reaction precipitation.
- the obtained precipitate is a compound such as scandium carboxylate, and is collected by separation as necessary.
- the fractionation operation can be performed with a normal apparatus, and a filter, a stationary separator, a centrifuge, or the like can be used.
- the recovered precipitate is preferably dried and / or calcined as necessary because it can be recovered as a powder of scandium oxide or the like.
- the drying conditions and firing conditions can be set as appropriate.
- the drying temperature is suitably about 80 to 150 ° C.
- the drying time is suitably about 1 to 24 hours.
- the firing temperature may be about 300 to 1200 ° C., and the firing time is suitably about 1 to 24 hours.
- the purity of scandium can be set to 99.3% by mass or more, preferably 99.7% by mass or more, more preferably It can be 99.9 mass%.
- scandium can be highly separated from an aqueous stock solution containing thorium and uranium.
- the scandium recovered in this way is scandium carboxylate, it can be further dissolved in an acid to form a coprecipitate with the zirconium compound, which can be fired to produce scandia-stabilized zirconia.
- scandia hydroxide and scandium oxide powder recovered by drying or firing can be mixed with zirconium oxide and fired to produce scandia-stabilized zirconia. Since the recovered scandium has few impurities and high purity, scandia-stabilized zirconia using the scandium is useful as an electrolyte for a solid oxide fuel cell. Further, scandium oxide can be reduced to a metal, or iodinated to be used as a compound such as scandium iodide.
- Example 1 Residue obtained by chlorinating titanium ore was suspended in water to a pH of less than 1, and 13 L of an aqueous stock solution in which scandium was dissolved was obtained (Sample A). Next, sodium hydroxide is mixed to pH 1.5 and stirred at 70 ° C. for 15 minutes, and then cooled to room temperature to obtain an aqueous suspension containing scandium. The scandium-containing aqueous suspension is filtered under reduced pressure to form a solid The portion was removed to obtain 14 L of an acidic liquid containing scandium (Sample B). Sodium hydroxide was added to an acidic liquid containing scandium (sample B) at room temperature to adjust the pH to 4, followed by stirring for 1 hour. This was filtered under reduced pressure with a Nutsche to recover the solid content, and pure water was added to the Nutsche to continue the filtration, and the solid content was washed until the conductivity of the filtrate was less than 1 mS / cm.
- An aqueous solution containing scandium (sample C) is prepared by adding the washed solid content to 70% sulfuric acid and dissolving it, and finely adjusting it with sulfuric acid so that the final pH is 0.7. 3 L was obtained.
- Example 2 The residue obtained by chlorinating titanium ore was suspended in water to a pH of less than 1 to obtain 10 L of an aqueous stock solution in which scandium was dissolved (sample D). Next, calcium carbonate is mixed to pH 4, and hydrochloric acid (10%) is added at 40 ° C. to pH 1.0, and then cooled to room temperature to obtain an aqueous suspension containing scandium. The turbid liquid was filtered under reduced pressure to remove solids, and 15 L of acidic liquid containing scandium was obtained (Sample E). After adjusting the pH to 4 by adding calcium hydroxide to an acidic solution (sample E) containing scandium at room temperature, the mixture was stirred for 1 hour. This was filtered under reduced pressure with a Nutsche to recover the solid content, and pure water was added to the Nutsche to continue the filtration, and the solid content was washed until the conductivity of the filtrate was less than 1 mS / cm.
- the washed solid content is added to hydrochloric acid to be dissolved, and finely adjusted with hydrochloric acid so that the final pH is 0.7, thereby obtaining 1 L of an aqueous solution (first aqueous solution) (sample F) containing scandium. It was.
- Example 3 The scandium-containing aqueous solution (first aqueous solution) (sample F) obtained in Example 2 and a known chelate resin (functional group: aminophosphoric acid) were placed in a sealed container at a volume ratio shown in Table 3 for 24 hours. Mixing with a bottle roller adsorbed scandium and the like. After the adsorption treatment, the solution and the chelate resin were separated, and the scandium concentration in the solution was analyzed with an inductively coupled plasma emission spectrometer (ICP-AES or MP-AES). The scandium adsorption capacity per liter of the chelate resin was calculated from the scandium concentration of the solution before and after the adsorption treatment. The results are shown in Table 3.
- ICP-AES inductively coupled plasma emission spectrometer
- Example 4 In Example 2, a scandium-containing acidic solution (sample) was used in the same manner as in Example 2 except that an aqueous stock solution (sample G, pH less than 1) in which scandium, titanium, zirconium and the like were dissolved was used instead of sample D. H) was obtained. Sample H does not go through the steps of scandium precipitation by pH adjustment, filtration, washing, and re-dissolution in acid, and corresponds to Sample E described in Example 2.
- sample H and various known chelate resins shown in Table 4 were placed in a sealed container at a volume ratio of 20: 1 and mixed with a bottle roller for 24 hours to adsorb scandium or the like (samples I, J, K).
- samples I, J, K adsorb scandium or the like
- the solution and the chelate resin were separated, and the scandium concentration in the solution was analyzed with an inductively coupled plasma emission spectrometer (ICP-AES or MP-AES).
- ICP-AES inductively coupled plasma emission spectrometer
- the scandium adsorption capacity per liter of the chelate resin was calculated from the scandium concentration of the solution before and after the adsorption treatment. The results are shown in Table 5.
- Table 6 shows the scandium aqueous stock solution (sample D) not subjected to the separation treatment of the present invention in Example 2 and a known chelate resin (functional group: aminophosphoric acid, the same as that used in Example 3). It put into the airtight container by volume ratio, and it mixed with the bottle roller for 24 hours, and adsorb
- ICP-AES or MP-AES inductively coupled plasma emission spectrometer
- the maximum adsorption amount of the target element (here, scandium) to the resin is one index indicating the concentration efficiency.
- the scandium adsorption isotherms of Example 3 and Comparative Example 1 are shown in FIG.
- the maximum amount of scandium adsorbed was 2.8 g / L RESIN.
- the scandium adsorption capacity is saturated at 0.1 g / L RESIN unless the titanium and zirconium removal step of the present invention is performed. This is because scandium and a low-selectivity adsorption species (titanium and zirconium) are contained in a large amount, thereby inhibiting scandium adsorption on the chelate resin.
- the Sc adsorption capacity per 1 L of the three types of resins of Samples I, J, and K was 0.2 g / L RESIN or more. This is sufficiently higher than the adsorption capacity of 0.1 g / L RESIN shown in Comparative Example 1, and the titanium / zirconium separation step of the present invention can be applied to purification treatments using various chelate resins. This indicates that it contributes to the improvement of purification efficiency.
- a step of eluting the adsorbed scandium into an aqueous solvent (elution step), and further, an aqueous suspension or acidic liquid containing scandium obtained in each of the above steps or
- Various aqueous solutions are brought into contact with an organic solvent containing an extractant and scandium is extracted into the organic solvent (organic solvent extraction step), then back extracted into the aqueous solvent (back extraction step),
- organic solvent extraction step aqueous solutions
- back extraction step A step of contacting the acidic liquid or various aqueous solutions or scandium-containing organic solutions obtained in the step with an aqueous solvent containing a precipitating agent to precipitate scandium, followed by solid-liquid separation (second scandium precipitation / recovery It was confirmed that the purity of scandium can be further increased by selectively performing the step (step).
- scandium recovered by the method of the present invention is concentrated and impurities such as titanium and zirconium can be reduced, high purity scandium is obtained by applying various purification processes from such crude scandium liquid. It is suitable for.
Abstract
Description
(1)少なくともスカンジウム、チタン、ジルコニウムを含む水性原液を準備する工程と、前記水性原液に酸又はアルカリを混合してpHを1.0~2.0の範囲に調整することにより、スカンジウムを液相に含み、チタン及びジルコニウムを固相に含む、スカンジウム含有水性懸濁液を得る工程とを備えるスカンジウムの分離方法、
(2)好ましい実施態様1 前記スカンジウム含有水性懸濁液を固液分離してチタン及びジルコニウムを除去した酸性液に、アルカリを混合してpHを3.5~7.0の範囲に調整することにより、スカンジウムを析出させる工程と、固液分離により、析出したスカンジウムを分離する工程とをさらに備える、スカンジウムの分離方法、
(3)好ましい実施態様2 前記スカンジウム含有水性懸濁液又はこれを固液分離した酸性液又は前記析出したスカンジウムを溶解した第1水系溶液と、キレート樹脂とを接触させることにより、キレート樹脂にスカンジウムを吸着させる工程と、キレート樹脂に吸着したスカンジウムを水系溶媒に溶離して第2水系溶液を得る工程とをさらに備える、スカンジウムの分離方法、
(4)好ましい実施態様3 前記スカンジウム含有水性懸濁液、又はこれを固液分離した酸性液、又は前記析出したスカンジウムを溶解した第1水系溶液、又は前記溶離したスカンジウムを含む第2水系溶液と、抽出剤を含む有機溶媒とを接触させることにより、スカンジウムを有機溶媒に抽出してスカンジウム含有有機溶液を得る工程と、スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して第3水系溶液を得る工程とをさらに備える、スカンジウムの分離方法、
(5)好ましい実施態様4 前記スカンジウム含有水性懸濁液を固液分離した酸性液、又は前記析出したスカンジウムを溶解した第1水系溶液、又は前記溶離したスカンジウムを含む第2水系溶液、又は前記スカンジウムを抽出したスカンジウム含有有機溶液、又は前記スカンジウムを逆抽出した第3水系溶液と、析出剤を含む水系溶媒とを接触させることにより、スカンジウムを析出させる工程と、固液分離により、スカンジウムを回収する工程とをさらに備える、スカンジウムの分離方法、などである。 That is, the present invention
(1) A step of preparing an aqueous stock solution containing at least scandium, titanium, and zirconium; and mixing the acid or alkali with the aqueous stock solution to adjust the pH to a range of 1.0 to 2.0. A method for separating scandium comprising the steps of: obtaining a scandium-containing aqueous suspension comprising a phase and titanium and zirconium in the solid phase;
(2) Preferred Embodiment 1 The pH is adjusted to a range of 3.5 to 7.0 by mixing an alkali with an acidic liquid obtained by solid-liquid separation of the scandium-containing aqueous suspension to remove titanium and zirconium. The method of separating scandium, further comprising the step of precipitating scandium and the step of separating the precipitated scandium by solid-liquid separation,
(3) Preferred Embodiment 2 By contacting the chelate resin with the scandium-containing aqueous suspension, the acidic solution obtained by solid-liquid separation of the scandium-containing aqueous suspension, or the first aqueous solution in which the precipitated scandium is dissolved, the chelate resin is scandium. A method for separating scandium, further comprising: adsorbing scandium adsorbed on the chelate resin; and eluting the scandium adsorbed on the chelate resin into an aqueous solvent to obtain a second aqueous solution;
(4) Preferred embodiment 3 The above-mentioned scandium-containing aqueous suspension, an acidic liquid obtained by solid-liquid separation thereof, a first aqueous solution in which the precipitated scandium is dissolved, or a second aqueous solution containing the eluted scandium A step of extracting scandium into an organic solvent by contacting with an organic solvent containing an extractant to obtain a scandium-containing organic solution; and a third aqueous solution by back-extracting scandium in the scandium-containing organic solution into an aqueous solvent. A method for separating scandium, further comprising:
(5) Preferred Embodiment 4 An acidic liquid obtained by solid-liquid separation of the scandium-containing aqueous suspension, a first aqueous solution in which the precipitated scandium is dissolved, a second aqueous solution containing the eluted scandium, or the scandium The scandium is recovered by bringing the scandium into contact with an organic solution containing the extracted scandium or a third aqueous solution obtained by back-extracting the scandium and an aqueous solvent containing a precipitating agent, and solid-liquid separation. And a process for separating scandium.
水性原液は、スカンジウムイオンを含む溶液や水酸化スカンジウム、酸化スカンジウムを含むスラリー等のスカンジウムを含む水性液であって、スカンジウムのほかに、チタン、ジルコニウムを含んでいる。チタン、ジルコニウムはイオンの状態であってもよく、水酸化物や酸化物等の化合物の状態であってもよい。また、スカンジウム以外の希土類元素(イットリウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウム)を含んでいてもよく、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、ニオブ、モリブデン、テクネチウム、ルテニウム、ロジウム、パラジウム、銀等の遷移金属元素を含んでいてもよく、トリウム、ウラン等の放射性元素を含んでいてもよく、そのほかのアルカリ金属元素、アルカリ土類金属元素、亜鉛、カドミウム等の周期表第12族元素、ホウ素、アルミニウム、ガリウム、インジウム等の周期表第13族元素、ケイ素、ゲルマニウム、スズ等の周期表第14族元素、リン、ヒ素、アンチモン、ビスマス等の周期表第15族元素、セレン、テルル等の周期表第16族元素、フッ素、塩素等の周期表第17族元素等の典型元素を含んでいてもよい。チタン、ジルコニウムのほかに、バナジウム及びスカンジウム以外の希土類元素から選ばれる少なくとも一種の金属を含むものが本発明の効果が得られやすいため好ましい。水性原液中のスカンジウムの濃度には特段の制限はなく、任意の濃度の水性原液を用いることができる。一般に、高濃度の水性原液(500~50000mg/L程度)を用いれば、高い収率でスカンジウムを回収しやすい。本発明の方法によれば、スカンジウム濃度が低いもの(1~500mg/L程度)であっても、十分にスカンジウムを精製し、分離し、回収することができる。一方、スカンジウム以外の元素の濃度についても特段の制限はない。一般に、不純物成分が少なく、その濃度が低ければ(例えば、チタン、ジルコニウム、バナジウムがそれぞれ1000mg/L以下程度であれば)、スカンジウムの精製は行い易い。本発明の方法によれば、不純物成分(チタン、ジルコニウム、バナジウム等)の濃度が比較的高い場合(1000mg/Lを超える場合)でも、十分にスカンジウムを精製し、分離し、回収することができる。更に、スカンジウム以外の希土類元素の濃度についても特段の制限はないが、それぞれ0~1000mg/L程度であると好ましい。水性原液は、どのようなpH域のものでも使用できる。原液のpHが6以上であれば予め酸を混合して6以下に調整するのが好ましく、pHが2以下に調整しておくのがより好ましい。pHが2以上であると、スカンジウム、チタン、ジルコニウムは水酸化物等の沈殿析出物のスラリーの状態であるが、pHが2以下の強酸性域であると、スカンジウム、チタン、ジルコニウム等は溶解し溶液になっているため取り扱い易く、pHが1以下であるとより好ましく、0.5以下のものが品質の安定性がよいため更に好ましい。 (1) Step of preparing an aqueous stock solution The aqueous stock solution is an aqueous solution containing scandium such as a solution containing scandium ions, a slurry containing scandium hydroxide or scandium oxide, and contains titanium and zirconium in addition to scandium. It is out. Titanium and zirconium may be in an ionic state or a compound such as a hydroxide or an oxide. It may also contain rare earth elements other than scandium (yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium), vanadium, chromium May contain transition metal elements such as manganese, iron, cobalt, nickel, copper, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, and may contain radioactive elements such as thorium, uranium, Other Periodic Table Group 12 Elements such as Alkali Metal Elements, Alkaline Earth Metal Elements, Zinc, Cadmium, etc., Periodic Table Group 13 Elements such as Boron, Aluminum, Gallium, Indium, Periodic Tables of Silicon, Germanium, Tin, etc. Including typical elements such as Group 4 elements, Periodic Table Group 15 elements such as phosphorus, arsenic, antimony, and bismuth, Periodic Table Group 16 elements such as selenium and tellurium, and Periodic Group 17 elements such as fluorine and chlorine May be. In addition to titanium and zirconium, those containing at least one metal selected from rare earth elements other than vanadium and scandium are preferable because the effects of the present invention can be easily obtained. There is no particular limitation on the concentration of scandium in the aqueous stock solution, and an aqueous stock solution having an arbitrary concentration can be used. In general, if a high-concentration aqueous stock solution (about 500 to 50000 mg / L) is used, scandium can be easily recovered in a high yield. According to the method of the present invention, even if the scandium concentration is low (about 1 to 500 mg / L), scandium can be sufficiently purified, separated and recovered. On the other hand, there is no particular limitation on the concentration of elements other than scandium. Generally, when there are few impurity components and the concentration is low (for example, when titanium, zirconium, and vanadium are each about 1000 mg / L or less), scandium is easily purified. According to the method of the present invention, even when the concentration of impurity components (titanium, zirconium, vanadium, etc.) is relatively high (over 1000 mg / L), scandium can be sufficiently purified, separated, and recovered. . Further, the concentration of rare earth elements other than scandium is not particularly limited, but is preferably about 0 to 1000 mg / L. The aqueous stock solution can be used in any pH range. If the pH of the stock solution is 6 or more, it is preferable to adjust the pH to 6 or less by mixing an acid in advance, and more preferably to adjust the pH to 2 or less. When the pH is 2 or more, scandium, titanium, and zirconium are in a slurry state of precipitates such as hydroxide, but when the pH is 2 or less, scandium, titanium, and zirconium are dissolved. Since it is a solution, it is easy to handle, and it is more preferable that the pH is 1 or less, and a pH of 0.5 or less is more preferable because the quality is stable.
1)スカンジウムを含む鉱石等の材料を酸で溶解した酸性液、この酸性液にアルカリを混合した酸性液、中性液又はアルカリ性液
2)スカンジウムを含む鉱石等の材料を酸で溶解した液を加水分解又は中和して他の金属成分を精製した後の酸性液、あるいは他の金属成分を精製した後の残滓を酸で溶解した酸性液、この酸性液にアルカリを混合した酸性液、中性液又はアルカリ性液
3)スカンジウムを含む鉱石等の材料をアルカリで溶解したアルカリ性液、このアルカリ性液に酸を混合した酸性液、中性液又はアルカリ性液
4)スカンジウムを含む鉱石等の材料をアルカリで溶解した液を加水分解又は中和して他の金属成分を精製した後のアルカリ性液、このアルカリ性液に酸を混合した酸性液、中性液又はアルカリ性液
5)スカンジウムを含む鉱石等の材料をアルカリで溶解した液を加水分解又は中和して他の金属成分を精製した後の残滓をアルカリ又は酸で溶解したアルカリ性液、中性液又は酸性液
6)1)~5)の酸性液やアルカリ性液に含まれるスカンジウムをイオン交換樹脂(キレート樹脂)で吸着溶離したり、沈殿分離するなどしてスカンジウムを粗精製した後の酸性液、中性液又はアルカリ性液
7)1)~5)の酸性液やアルカリ性液に含まれるスカンジウムをイオン交換樹脂(キレート樹脂)で吸着溶離したり、沈殿分離するなどしてスカンジウムを粗精製した水酸化スカンジウム、酸化スカンジウム等を含むスラリーにアルカリ又は酸を混合して得られたアルカリ性液、中性液又は酸性液 The aqueous stock solution contains at least scandium, titanium, and zirconium. For example, the following aqueous solution can be used. The acidic liquid has a pH of about 6 or less, the neutral liquid has a pH of about 6 to 8, and the alkaline liquid has a pH of about 8 or more. In the present invention, a solution obtained by dissolving an ore with an acid, specifically, a solution obtained by suspending a residue obtained by chlorinating a titanium ore in water, a solution obtained by dissolving an ore residue with an acid, specifically, a titanium ore by an acid. It is more preferable to use a liquid obtained by suspending the residue leached in step (b) in water.
1) An acidic liquid obtained by dissolving a material such as ore containing scandium with an acid, an acidic liquid obtained by mixing an alkali with this acidic liquid, a neutral liquid or an alkaline liquid 2) A liquid obtained by dissolving a material such as ore containing scandium with an acid Acidic liquid after hydrolysis or neutralization to purify other metal components, or acidic liquid in which the residue after purifying other metal components is dissolved with acid, acidic liquid in which alkali is mixed with this acidic liquid, 3) An alkaline solution obtained by dissolving a material such as an ore containing scandium with an alkali, an acidic solution obtained by mixing an acid with the alkaline solution, a neutral solution or an alkaline solution 4) an alkali such as an ore containing scandium. The alkaline solution after hydrolyzing or neutralizing the solution dissolved in step 2 to purify other metal components, an acidic solution obtained by mixing an acid with this alkaline solution, a neutral solution or an alkaline solution 5) Scandium An alkaline solution, neutral solution or acidic solution obtained by dissolving the residue obtained by hydrolyzing or neutralizing a solution in which a material such as ore is dissolved with an alkali and purifying other metal components with an alkali or an acid 6) 1) to 5) Acidic, neutral or alkaline liquids after scandium is roughly purified by adsorbing and eluting the scandium contained in the acidic or alkaline liquids with an ion exchange resin (chelate resin) or by precipitation separation. Slurry containing scandium hydroxide, scandium oxide, etc. obtained by roughly purifying scandium by adsorbing and eluting the scandium contained in the acidic and alkaline liquids of 1) to 5) with an ion exchange resin (chelate resin) or by precipitation separation. Alkaline liquid, neutral liquid or acidic liquid obtained by mixing alkali or acid with
本発明では、少なくともスカンジウム、チタン、ジルコニウムを含む水性原液とアルカリを混合してpHを1.0~2.0の範囲に調整し、チタン、ジルコニウムを固相に含み、スカンジウムを液相に含む、スカンジウムを含む水性懸濁液を得る。水性原液のpHを1.0未満から1.0~2.0にすることにより、チタン、ジルコニウムの沈殿を析出させることができる。pH調整を1.0より低くすると、チタン、ジルコニウムの沈殿が不十分で、多くのチタン、ジルコニウムが水性原液中に残留する。また、pH調整を2.0より高くするとチタン、ジルコニウムの沈殿にスカンジウムの沈殿が混入してしまうため、スカンジウムの回収率が低下する。pH調整するアルカリは、制限なく用いることができ、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属化合物、水酸化カルシウム(消石灰)、水酸化マグネシウム、水酸化バリウム等のアルカリ土類金属水酸化物、酸化カルシウム(生石灰)、酸化マグネシウム、酸化バリウム等のアルカリ土類金属酸化物、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等のアルカリ土類金属化合物、アンモニア、アミン類等を用いることができる。鉱石等の材料をアルカリで溶解した液を加水分解したり中和したりして他の金属成分を精錬した後の液を用いることもできる。pH調整の際の温度は、適宜設定することができ、例えば、2~100℃程度が好ましく、5~70℃程度がより好ましい。 (2) Titanium and zirconium separation step In the present invention, an aqueous stock solution containing at least scandium, titanium and zirconium is mixed with an alkali to adjust the pH to a range of 1.0 to 2.0, and the titanium and zirconium are solid-phased. And an aqueous suspension containing scandium containing scandium in the liquid phase. By setting the pH of the aqueous stock solution to less than 1.0 to 1.0 to 2.0, titanium and zirconium precipitates can be deposited. When the pH adjustment is lower than 1.0, precipitation of titanium and zirconium is insufficient, and much titanium and zirconium remain in the aqueous stock solution. Further, when the pH adjustment is higher than 2.0, scandium precipitates are mixed into titanium and zirconium precipitates, and the scandium recovery rate is lowered. The alkali for pH adjustment can be used without limitation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, calcium hydroxide (slaked lime), magnesium hydroxide, Alkaline earth metal hydroxides such as barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide and barium oxide, alkaline earth metal compounds such as calcium carbonate, magnesium carbonate and barium carbonate, ammonia , Amines and the like can be used. A liquid obtained by refining other metal components by hydrolyzing or neutralizing a liquid obtained by dissolving a material such as ore with an alkali can also be used. The temperature at the time of pH adjustment can be appropriately set. For example, it is preferably about 2 to 100 ° C., more preferably about 5 to 70 ° C.
前記のチタン、ジルコニウム分離工程で得たスカンジウムを含む水性懸濁液を固液分離してチタン及びジルコニウムを除去し、除去後の水溶液(酸性液)にアルカリを混合してpHを3.5~7.0の範囲に調整するのが好ましい。スカンジウムを含む酸性液のpHを3.5~7.0にすることにより、スカンジウムの沈殿が析出し、それを固液分離することができる。pH調整を3.5より低くすると、スカンジウムの沈殿が不十分で、多くのスカンジウムが酸性液中に残留する。また、pH調整を7.0より高くすると鉄(第一鉄)、マンガン等の沈殿が析出し、スカンジウムの沈殿に混入してしまうため、スカンジウムの純度が低下するので、上記pH範囲が好ましい。pH調整するアルカリは、制限なく用いることができ、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属化合物、水酸化カルシウム(消石灰)、水酸化マグネシウム、水酸化バリウム等のアルカリ土類金属水酸化物、酸化カルシウム(生石灰)、酸化マグネシウム、酸化バリウム等のアルカリ土類金属酸化物、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等のアルカリ土類金属化合物、アンモニア、アミン類等を用いることができる。pH調整の際の温度は、適宜設定することができ、例えば、2~100℃程度が好ましく、5~70℃程度がより好ましい。スカンジウムを含む水性懸濁液の固液分離、又は、スカンジウムの析出物を含む液の固液分離は、何れも通常の方法を用いることができ、例えば、濾過機、静置分離機、遠心分離機等を用いることができる。回収した沈殿物は、必要に応じて乾燥し、及び/又は焼成する。固液分離の対象が前記水性懸濁液の場合、沈殿物の乾燥、及び/又は焼成によって酸化チタン、酸化ジルコニウムの粉末等を回収できる。また、固液分離の対象がスカンジウム析出物を含む液の場合、沈殿物の乾燥、及び/又は焼成によって酸化スカンジウムの粉末を回収することができる。 (3) Each step of first scandium precipitation / separation (preferred embodiment 1)
The aqueous suspension containing scandium obtained in the titanium and zirconium separation step is subjected to solid-liquid separation to remove titanium and zirconium, and an alkali is mixed with the aqueous solution (acid solution) after removal to adjust the pH to 3.5 to It is preferable to adjust to the range of 7.0. By setting the pH of the acidic solution containing scandium to 3.5 to 7.0, scandium precipitates and can be separated into solid and liquid. When the pH adjustment is lower than 3.5, precipitation of scandium is insufficient and much scandium remains in the acidic liquid. Moreover, since the precipitation of iron (ferrous iron), manganese, etc. will precipitate and it will mix in scandium precipitation when pH adjustment is made higher than 7.0, since the purity of scandium falls, the said pH range is preferable. The alkali for pH adjustment can be used without limitation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal compounds such as sodium carbonate and potassium carbonate, calcium hydroxide (slaked lime), magnesium hydroxide, Alkaline earth metal hydroxides such as barium hydroxide, alkaline earth metal oxides such as calcium oxide (quick lime), magnesium oxide and barium oxide, alkaline earth metal compounds such as calcium carbonate, magnesium carbonate and barium carbonate, ammonia , Amines and the like can be used. The temperature at the time of pH adjustment can be appropriately set. For example, it is preferably about 2 to 100 ° C., more preferably about 5 to 70 ° C. For solid-liquid separation of an aqueous suspension containing scandium, or solid-liquid separation of a liquid containing scandium precipitates, any ordinary method can be used. For example, a filter, a stationary separator, or a centrifugal separator. A machine or the like can be used. The collected precipitate is dried and / or calcined as necessary. When the target of solid-liquid separation is the aqueous suspension, titanium oxide, zirconium oxide powder, etc. can be recovered by drying and / or firing the precipitate. Moreover, when the object of solid-liquid separation is a liquid containing scandium precipitates, the scandium oxide powder can be recovered by drying and / or firing the precipitates.
前記のチタン、ジルコニウム分離工程で得たスカンジウムを含む水性懸濁液、又はこれを固液分離した酸性液や、スカンジウム析出工程で得たスカンジウム析出物を水系溶媒に溶解した第1水系溶液を、キレート樹脂に接触させ、スカンジウムを吸着させ、次いで、吸着したスカンジウムを水系溶媒に溶離して、第2水系溶液を得ることができる。スカンジウム析出物を溶解する水系溶媒は、硫酸水溶液、塩酸水溶液、硝酸水溶液などの公知の酸や、炭酸ナトリウム水溶液、炭酸アンモニウム水溶液などの公知のアルカリを用いることができる。コストやハンドリング面から酸が好ましく、濃度はスカンジウムの溶解度が十分高ければ特に限定はされないが、スカンジウムをより高濃度で回収したければ、より高濃度であることが好ましく、例えば70%硫酸がより好ましい。 (4) Each step of chelate resin adsorption / elution (Preferred embodiment 2)
An aqueous suspension containing scandium obtained in the titanium and zirconium separation step, or an acidic solution obtained by solid-liquid separation of the suspension, and a first aqueous solution in which the scandium precipitate obtained in the scandium precipitation step is dissolved in an aqueous solvent. The second aqueous solution can be obtained by contacting the chelate resin to adsorb scandium and then eluting the adsorbed scandium into the aqueous solvent. As the aqueous solvent for dissolving the scandium precipitate, a known acid such as a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, or a nitric acid aqueous solution, or a known alkali such as a sodium carbonate aqueous solution or an ammonium carbonate aqueous solution can be used. Acid is preferable from the viewpoint of cost and handling, and the concentration is not particularly limited as long as the solubility of scandium is sufficiently high. However, if scandium is recovered at a higher concentration, a higher concentration is preferable, for example, 70% sulfuric acid is more preferable. preferable.
前記の(2)~(4)の各工程で得たスカンジウムを含む水系溶液(前記のチタン、ジルコニウム分離工程で得られたスカンジウムを含む水性懸濁液、又はこれを固液分離した酸性液、又は第1水系溶液、又は第2水系溶液)を、抽出剤を含む有機溶媒に接触させ、スカンジウムを有機溶媒に抽出してスカンジウム含有有機溶液を得た後に、スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して、第3水系溶液を得る工程である。 (5) About each process of an organic-solvent extraction process and a back extraction process (Preferred embodiment 3)
An aqueous solution containing scandium obtained in each of the above steps (2) to (4) (an aqueous suspension containing scandium obtained in the titanium or zirconium separation step, or an acidic solution obtained by solid-liquid separation of this, Or the first aqueous solution or the second aqueous solution) is brought into contact with an organic solvent containing an extractant to extract scandium into the organic solvent to obtain a scandium-containing organic solution, and then the scandium in the scandium-containing organic solution is converted into an aqueous solution. This is a step of obtaining a third aqueous solution by back extraction into a solvent.
前記の(2)~(5)の各工程で得たスカンジウムを含む溶液(スカンジウム含有水性懸濁液を固液分離した酸性液、又は第1水系溶液、又は第2水系溶液、又はスカンジウム含有有機溶液又は逆抽出した第3水系溶液)と析出剤を含む液(水系溶媒)とを混合しスカンジウムを析出させ、固液分離によりスカンジウムを沈殿物として回収する工程である。例えば、スカンジウム含有有機溶液と析出剤とを混合して、スカンジウムを析出させるのが好ましく、このように有機溶媒抽出工程の後に直ぐに析出工程を行っても、スカンジウムの純度は99.0質量%以上となり、好ましくは99.5質量%以上とすることができる。 (6) Each step of second scandium precipitation / recovery (preferred embodiment 4)
A solution containing scandium obtained in the above steps (2) to (5) (an acid solution obtained by solid-liquid separation of a scandium-containing aqueous suspension, a first aqueous solution, a second aqueous solution, or a scandium-containing organic material) This is a step of mixing a solution or a back-extracted third aqueous solution) and a liquid containing a precipitating agent (aqueous solvent) to precipitate scandium and recovering scandium as a precipitate by solid-liquid separation. For example, it is preferable to mix scandium-containing organic solution and a precipitating agent to precipitate scandium. Thus, even when the precipitation step is performed immediately after the organic solvent extraction step, the purity of scandium is 99.0% by mass or more. And preferably 99.5% by mass or more.
チタン鉱石を塩素化した残滓を水に懸濁してpH1未満とし、スカンジウムを溶解させた水性原液13Lを得た(試料A)。次いで、水酸化ナトリウムを混合してpH1.5とし、70℃で15分撹拌した後、室温まで冷却してスカンジウムを含む水性懸濁液とし、このスカンジウム含有水性懸濁液を減圧濾過して固形分を取り除き、スカンジウムを含有する酸性液14Lを得た(試料B)。スカンジウムを含有する酸性液(試料B)に室温で水酸化ナトリウムを添加してpH4に調整した後、1時間撹拌した。これをヌッチェで減圧濾過して固形分を回収し、ヌッチェに純水を追加して濾過を続け、濾液の導電率が1mS/cm未満となるまで固形分の洗浄を行った。 Example 1
Residue obtained by chlorinating titanium ore was suspended in water to a pH of less than 1, and 13 L of an aqueous stock solution in which scandium was dissolved was obtained (Sample A). Next, sodium hydroxide is mixed to pH 1.5 and stirred at 70 ° C. for 15 minutes, and then cooled to room temperature to obtain an aqueous suspension containing scandium. The scandium-containing aqueous suspension is filtered under reduced pressure to form a solid The portion was removed to obtain 14 L of an acidic liquid containing scandium (Sample B). Sodium hydroxide was added to an acidic liquid containing scandium (sample B) at room temperature to adjust the pH to 4, followed by stirring for 1 hour. This was filtered under reduced pressure with a Nutsche to recover the solid content, and pure water was added to the Nutsche to continue the filtration, and the solid content was washed until the conductivity of the filtrate was less than 1 mS / cm.
チタン鉱石を塩素化した残滓を水に懸濁してpH1未満とし、スカンジウムを溶解させた水性原液10Lを得た(試料D)。次いで、炭酸カルシウムを混合してpH4とし、更に塩酸(10%)を40℃で添加してpH1.0とした後、室温まで冷却してスカンジウムを含む水性懸濁液とし、このスカンジウム含有水性懸濁液を減圧濾過して固形分を取り除き、スカンジウムを含有する酸性液15Lを得た(試料E)。スカンジウムを含有する酸性液(試料E)に室温で水酸化カルシウムを添加してpH4に調整した後、1時間撹拌した。これをヌッチェで減圧濾過して固形分を回収し、ヌッチェに純水を追加して濾過を続け、濾液の導電率が1mS/cm未満となるまで固形分の洗浄を行った。 Example 2
The residue obtained by chlorinating titanium ore was suspended in water to a pH of less than 1 to obtain 10 L of an aqueous stock solution in which scandium was dissolved (sample D). Next, calcium carbonate is mixed to pH 4, and hydrochloric acid (10%) is added at 40 ° C. to pH 1.0, and then cooled to room temperature to obtain an aqueous suspension containing scandium. The turbid liquid was filtered under reduced pressure to remove solids, and 15 L of acidic liquid containing scandium was obtained (Sample E). After adjusting the pH to 4 by adding calcium hydroxide to an acidic solution (sample E) containing scandium at room temperature, the mixture was stirred for 1 hour. This was filtered under reduced pressure with a Nutsche to recover the solid content, and pure water was added to the Nutsche to continue the filtration, and the solid content was washed until the conductivity of the filtrate was less than 1 mS / cm.
前記の方法によってスカンジウムと共存する不純物を低減することで、キレート樹脂や溶媒抽出などの公知の分離工程の効率が向上する。一例としてキレート樹脂へのスカンジウム吸着特性を実施例3に示す。 Effect of chelate resin on scandium concentration treatment By reducing impurities coexisting with scandium by the above-described method, the efficiency of known separation processes such as chelate resin and solvent extraction is improved. As an example, the scandium adsorption property to the chelate resin is shown in Example 3.
実施例2で得た、スカンジウム含有水系溶液(第1水系溶液)(試料F)と、公知のキレート樹脂(官能基:アミノリン酸)とを表3に示す体積比で密閉容器に入れ、24時間ボトルローラーで混合してスカンジウム等の吸着を行った。吸着処理後に溶液とキレート樹脂を分離し、溶液中のスカンジウム濃度を、誘導結合プラズマ発光分光分析装置(ICP-AES若しくはMP-AES)で分析した。吸着処理の前後の溶液のスカンジウム濃度から、キレート樹脂1Lあたりのスカンジウム吸着容量を算出した。その結果を表3に示す。 Example 3
The scandium-containing aqueous solution (first aqueous solution) (sample F) obtained in Example 2 and a known chelate resin (functional group: aminophosphoric acid) were placed in a sealed container at a volume ratio shown in Table 3 for 24 hours. Mixing with a bottle roller adsorbed scandium and the like. After the adsorption treatment, the solution and the chelate resin were separated, and the scandium concentration in the solution was analyzed with an inductively coupled plasma emission spectrometer (ICP-AES or MP-AES). The scandium adsorption capacity per liter of the chelate resin was calculated from the scandium concentration of the solution before and after the adsorption treatment. The results are shown in Table 3.
実施例2において、試料Dに代えて、スカンジウム、チタン、ジルコニウム等を溶解させた水性原液(試料G、pH1未満)を用いたこと以外は実施例2と同様にして、スカンジウム含有酸性液(試料H)を得た。尚、試料Hは、pH調整によるスカンジウムの析出、濾過、洗浄、酸への再溶解の工程を経ていないものであり、実施例2に記載の試料Eに対応する。 Example 4
In Example 2, a scandium-containing acidic solution (sample) was used in the same manner as in Example 2 except that an aqueous stock solution (sample G, pH less than 1) in which scandium, titanium, zirconium and the like were dissolved was used instead of sample D. H) was obtained. Sample H does not go through the steps of scandium precipitation by pH adjustment, filtration, washing, and re-dissolution in acid, and corresponds to Sample E described in Example 2.
実施例2で本発明の分離処理を行っていない、スカンジウム水性原液(試料D)と、公知のキレート樹脂(官能基:アミノリン酸、実施例3で使用したものと同じ)とを表6に示す体積比で密閉容器に入れ、24時間ボトルローラーで混合してスカンジウム等の吸着を行った。吸着処理後に溶液とキレート樹脂を分離し、溶液中のスカンジウム濃度を、誘導結合プラズマ発光分光分析装置(ICP-AES若しくはMP-AES)で分析した。吸着処理の前後の溶液のスカンジウム濃度から、キレート樹脂1Lあたりのスカンジウム吸着容量を算出した。その結果を表6に示す。 Comparative Example 1
Table 6 shows the scandium aqueous stock solution (sample D) not subjected to the separation treatment of the present invention in Example 2 and a known chelate resin (functional group: aminophosphoric acid, the same as that used in Example 3). It put into the airtight container by volume ratio, and it mixed with the bottle roller for 24 hours, and adsorb | sucked scandium etc. was performed. After the adsorption treatment, the solution and the chelate resin were separated, and the scandium concentration in the solution was analyzed with an inductively coupled plasma emission spectrometer (ICP-AES or MP-AES). The scandium adsorption capacity per liter of the chelate resin was calculated from the scandium concentration of the solution before and after the adsorption treatment. The results are shown in Table 6.
Claims (17)
- 少なくともスカンジウム、チタン、ジルコニウムを含む水性原液を準備する工程と、
前記水性原液に酸又はアルカリを混合してpHを1.0~2.0の範囲に調整することにより、スカンジウムを液相に含み、チタン及びジルコニウムを固相に含む、スカンジウム含有水性懸濁液を得る工程とを備えるスカンジウムの分離方法。 Preparing an aqueous stock solution containing at least scandium, titanium, and zirconium;
An aqueous suspension containing scandium containing scandium in the liquid phase and titanium and zirconium in the solid phase by adjusting the pH to a range of 1.0 to 2.0 by mixing acid or alkali with the aqueous stock solution. And a method for separating scandium. - 前記スカンジウム含有水性懸濁液を固液分離してチタン及びジルコニウムを除去した酸性液に、アルカリを混合してpHを3.5~7.0の範囲に調整することにより、スカンジウムを析出させる工程と、
固液分離により、析出したスカンジウムを分離する工程とをさらに備える、請求項1に記載のスカンジウムの分離方法。 A step of precipitating scandium by adjusting the pH to a range of 3.5 to 7.0 by mixing an alkali with an acidic liquid obtained by solid-liquid separation of the scandium-containing aqueous suspension to remove titanium and zirconium. When,
The method for separating scandium according to claim 1, further comprising a step of separating precipitated scandium by solid-liquid separation. - 前記析出したスカンジウムを溶解した第1水系溶液と、キレート樹脂とを接触させることにより、前記キレート樹脂にスカンジウムを吸着させる工程と、
前記キレート樹脂に吸着したスカンジウムを水系溶媒に溶離して第2水系溶液を得る工程とをさらに備える、請求項2に記載のスカンジウムの分離方法。 A step of adsorbing scandium to the chelate resin by bringing the first aqueous solution in which the precipitated scandium is dissolved into contact with the chelate resin;
The method for separating scandium according to claim 2, further comprising a step of eluting scandium adsorbed on the chelate resin into an aqueous solvent to obtain a second aqueous solution. - 前記スカンジウム含有水性懸濁液又はこれを固液分離した酸性液と、キレート樹脂とを接触させることにより、前記キレート樹脂にスカンジウムを吸着させる工程と、
前記キレート樹脂に吸着したスカンジウムを水系溶媒に溶離して第2水系溶液を得る工程とをさらに備える、請求項1に記載のスカンジウムの分離方法。 A step of adsorbing scandium to the chelate resin by contacting the scandium-containing aqueous suspension or an acidic liquid obtained by solid-liquid separation of the suspension and the chelate resin;
The method for separating scandium according to claim 1, further comprising a step of eluting the scandium adsorbed on the chelate resin into an aqueous solvent to obtain a second aqueous solution. - 前記スカンジウム含有水性懸濁液又はこれを固液分離した酸性液と、抽出剤を含む有機溶媒とを接触させることにより、スカンジウムを前記有機溶媒に抽出してスカンジウム含有有機溶液を得る工程をさらに備える、請求項1に記載のスカンジウムの分離方法。 The method further includes a step of extracting scandium into the organic solvent to obtain a scandium-containing organic solution by contacting the scandium-containing aqueous suspension or an acidic liquid obtained by solid-liquid separation of the suspension and an organic solvent containing an extractant. The method for separating scandium according to claim 1.
- 前記析出したスカンジウムを溶解した第1水系溶液と、抽出剤を含む有機溶媒とを接触させることにより、スカンジウムを前記有機溶媒に抽出してスカンジウム含有有機溶液を得る工程をさらに備える、請求項2に記載のスカンジウムの分離方法。 The method further comprises the step of obtaining a scandium-containing organic solution by extracting scandium into the organic solvent by bringing the first aqueous solution in which the precipitated scandium is dissolved into contact with an organic solvent containing an extractant. The method for separating scandium as described.
- 前記溶離したスカンジウムを含む第2水系溶液と、抽出剤を含む有機溶媒とを接触させることにより、スカンジウムを前記有機溶媒に抽出してスカンジウム含有有機溶液を得る工程をさらに備える、請求項3又は4に記載のスカンジウムの分離方法。 The method further comprises a step of extracting scandium into the organic solvent to obtain a scandium-containing organic solution by bringing the second aqueous solution containing the eluted scandium into contact with an organic solvent containing an extractant. The method for separating scandium according to 1.
- 前記スカンジウム含有水性懸濁液又はこれを固液分離した酸性液と、抽出剤を含む有機溶媒とを接触させることにより、スカンジウムを前記有機溶媒に抽出してスカンジウム含有有機溶液を得る工程と、
前記スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して第3水系溶液を得る工程とをさらに備える、請求項1に記載のスカンジウムの分離方法。 A step of extracting scandium into the organic solvent to obtain a scandium-containing organic solution by contacting the scandium-containing aqueous suspension or an acidic liquid obtained by solid-liquid separation of the suspension and an organic solvent containing an extractant; and
The scandium separation method according to claim 1, further comprising a step of back-extracting scandium in the scandium-containing organic solution into an aqueous solvent to obtain a third aqueous solution. - 前記析出したスカンジウムを溶解した第1水系溶液と、抽出剤を含む有機溶媒とを接触させることにより、スカンジウムを前記有機溶媒に抽出してスカンジウム含有有機溶液を得る工程と、
前記スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して第3水系溶液を得る工程とをさらに備える、請求項2に記載のスカンジウムの分離方法。 A step of extracting scandium into the organic solvent to obtain a scandium-containing organic solution by contacting the first aqueous solution in which the precipitated scandium is dissolved and an organic solvent containing an extractant;
The method for separating scandium according to claim 2, further comprising a step of back-extracting scandium in the scandium-containing organic solution into an aqueous solvent to obtain a third aqueous solution. - 前記溶離したスカンジウムを含む第2水系溶液と、抽出剤を含む有機溶媒とを接触させることにより、スカンジウムを前記有機溶媒に抽出してスカンジウム含有有機溶液を得る工程と、
前記スカンジウム含有有機溶液中のスカンジウムを水系溶媒に逆抽出して第3水系溶液を得る工程とをさらに備える、請求項3又は4に記載のスカンジウムの分離方法。 Contacting the eluted second aqueous solution containing scandium with an organic solvent containing an extractant to extract scandium into the organic solvent to obtain a scandium-containing organic solution;
The scandium separation method according to claim 3 or 4, further comprising a step of back-extracting scandium in the scandium-containing organic solution into an aqueous solvent to obtain a third aqueous solution. - 前記スカンジウム含有水性懸濁液を固液分離した酸性液と、析出剤を含む水系溶媒とを接触させることにより、スカンジウムを析出させる工程と、
固液分離により、スカンジウムを回収する工程とをさらに備える、請求項1に記載のスカンジウムの分離方法。 A step of precipitating scandium by contacting an acidic liquid obtained by solid-liquid separation of the scandium-containing aqueous suspension and an aqueous solvent containing a precipitation agent;
The method for separating scandium according to claim 1, further comprising a step of recovering scandium by solid-liquid separation. - 前記析出したスカンジウムを溶解した第1水系溶液と、析出剤を含む水系溶媒とを接触させることにより、スカンジウムを析出させる工程と、
固液分離により、スカンジウムを回収する工程とをさらに備える、請求項2に記載のスカンジウムの分離方法。 A step of precipitating scandium by bringing the first aqueous solution in which the precipitated scandium is dissolved into contact with an aqueous solvent containing a precipitating agent;
The method for separating scandium according to claim 2, further comprising a step of recovering scandium by solid-liquid separation. - 前記溶離したスカンジウムを含む第2水系溶液と、析出剤を含む水系溶媒とを接触させることにより、スカンジウムを析出させる工程と、
固液分離により、スカンジウムを回収する工程とをさらに備える、請求項3又は4に記載のスカンジウムの分離方法。 A step of precipitating scandium by bringing the second aqueous solution containing the eluted scandium into contact with an aqueous solvent containing a precipitating agent;
The method for separating scandium according to claim 3, further comprising a step of recovering scandium by solid-liquid separation. - 前記スカンジウムを抽出したスカンジウム含有有機溶液と、析出剤を含む水系溶媒とを接触させることにより、スカンジウムを析出させる工程と、
固液分離により、スカンジウムを回収する工程とをさらに備える、請求項5~7のいずれか1項に記載のスカンジウムの分離方法。 A step of precipitating scandium by bringing the scandium-containing organic solution extracted from the scandium into contact with an aqueous solvent containing a precipitating agent;
The method for separating scandium according to any one of claims 5 to 7, further comprising a step of recovering scandium by solid-liquid separation. - 前記スカンジウムを逆抽出した第3水系溶液と、析出剤を含む水系溶媒とを接触させることにより、スカンジウムを析出させる工程と、
固液分離により、スカンジウムを回収する工程とをさらに備える、請求項8~10のいずれか1項に記載のスカンジウムの分離方法。 A step of precipitating scandium by contacting a third aqueous solution back-extracted with the scandium and an aqueous solvent containing a precipitating agent;
The method for separating scandium according to any one of claims 8 to 10, further comprising a step of recovering scandium by solid-liquid separation. - 前記水性原液として、チタン鉱石を塩素化した残滓を水に懸濁した液を用いる、請求項1~15のいずれか1項に記載のスカンジウムの分離方法。 The method for separating scandium according to any one of claims 1 to 15, wherein a liquid obtained by suspending a residue obtained by chlorinating titanium ore in water is used as the aqueous stock solution.
- 前記水性原液として、チタン鉱石を酸で浸出した残滓を水に懸濁した液を用いる、請求項1~15のいずれか1項に記載のスカンジウムの分離方法。 The method for separating scandium according to any one of claims 1 to 15, wherein a liquid obtained by suspending a residue obtained by leaching titanium ore with an acid in water is used as the aqueous stock solution.
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