WO2015122397A1 - Procédé de séparation de scandium - Google Patents

Procédé de séparation de scandium Download PDF

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WO2015122397A1
WO2015122397A1 PCT/JP2015/053606 JP2015053606W WO2015122397A1 WO 2015122397 A1 WO2015122397 A1 WO 2015122397A1 JP 2015053606 W JP2015053606 W JP 2015053606W WO 2015122397 A1 WO2015122397 A1 WO 2015122397A1
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scandium
organic solvent
aqueous solution
acidic aqueous
acid
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PCT/JP2015/053606
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English (en)
Japanese (ja)
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芝田　隼次
祐介 植薄
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学校法人 関西大学
石原産業株式会社
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Priority to CN201580002785.9A priority Critical patent/CN105793447B/zh
Priority to AU2015216225A priority patent/AU2015216225A1/en
Publication of WO2015122397A1 publication Critical patent/WO2015122397A1/fr

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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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/32—Carboxylic acids
    • 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 present invention relates to a method for separating scandium (Sc).
  • Scandium is one of the transition metal elements and is classified as a rare earth element together with yttrium (Y).
  • Y 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 it is contained in tortite, etc., but its output is low, so a small amount of scandium is contained in the leachate that has been leached under pressure by adding sulfuric acid to nickel oxide ore of laterite ore. Are separated.
  • An example of such a scandium separation method is Japanese Patent No. 3428292 (Patent Document 1).
  • Patent Document 1 an organic solvent obtained by diluting 2-ethylhexylsulfonic acid-mono-2-ethylhexyl with kerosene is added to a scandium-containing solution in an aqueous phase, and the scandium component is extracted into the organic solvent. Then, in order to separate the impurity component extracted together with scandium in the organic solvent, scrubbing by adding aqueous hydrochloric acid solution, removing the impurity component, stripping by adding aqueous sodium hydroxide solution in the organic solvent. It is disclosed that the slurry is recovered as a slurry containing scandium hydroxide.
  • Patent Document 1 the recovered scandium hydroxide is dissolved with hydrochloric acid to obtain an aqueous scandium chloride solution, and oxalic acid is added to this to form a scandium oxalate precipitate, the precipitate is filtered, and impurities are separated into the filtrate. Thereafter, it is disclosed that high-purity scandium oxide is obtained by calcination.
  • Patent Document 2 an aqueous solution containing scandium is mixed with an organic solvent containing trioctylphosphine oxide, and scandium is extracted into the organic solvent. Then, the organic solvent is mixed with water, hydrochloric acid, sulfuric acid, oxalic acid.
  • a method for separating and purifying scandium is disclosed in which one or more selected from the above is mixed to back-extract scandium from an organic solvent.
  • Non-Patent Document 1 for various metal elements, by mixing metal nitrate, sodium nitrate and nitric acid and using a carboxylic acid-based extractant such as versatic acid or naphthenic acid, Extraction characteristics of carboxylic acid-based extractants for various metal elements are disclosed.
  • Non-Patent Document 1 mentions scandium as one of various metal elements.
  • Patent Document 1 2-ethylhexylsulfonic acid-mono-2-ethylhexyl is used as an extractant.
  • This extractant extracts many impurities other than scandium. Therefore, in the method of Patent Document 1, a scrubbing process for separating impurities such as yttrium, iron, manganese, chromium, magnesium, aluminum, and calcium is performed.
  • the extractant which extracts many impurities other than scandium is used, since the scrubbing process for isolate
  • the trioctylphosphine oxide used as the extractant in Patent Document 2 has high scandium selectivity, but when a large excess of impurities coexists in the scandium-containing aqueous solution, the scrubbing process is still required, and thus the productivity is high. bad.
  • the coexisting impurity is zirconium, it cannot be sufficiently separated by scrubbing, and it is necessary to remove the zirconium from the scandium-containing aqueous solution in advance using tenoyltrifluoroacetone as an extractant. , Productivity further decreases.
  • Non-Patent Document 1 discloses that scandium nitrate is used as a scandium raw material, scandium nitrate is mixed with sodium nitrate and nitric acid, and a carboxylic acid-based extractant is used. Since scandium nitrate is water soluble, scandium dissolves in sodium nitrate and nitric acid. However, the hardly soluble scandium raw material is difficult to dissolve in sodium nitrate and nitric acid. For this reason, when a hardly soluble material is used as the scandium raw material, even if the poorly soluble scandium raw material is mixed with sodium nitrate and nitric acid, the amount of scandium eluted is small. Therefore, even if a carboxylic acid-based extractant is used, the amount of scandium that can be extracted is small in the first place, and there is a problem that productivity is poor.
  • an object of the present invention is to provide a scandium separation method that improves productivity.
  • the amount of the scandium raw material increased when dissolved in an acidic aqueous solution having a pH of less than 4.
  • the pH was adjusted by mixing with an alkali, and performing contact with an organic solvent containing a carboxylic acid-based extractant, the amount of impurities extracted into the organic solvent is reduced.
  • the present invention was completed by finding that it can be kept low and that scandium can be mainly extracted.
  • the method for separating scandium comprises a step of preparing an acidic aqueous stock solution containing scandium and having a pH of less than 4; By adjusting to the following ranges, the first acidic aqueous solution is brought into contact with the first acidic aqueous solution and an organic solvent containing a carboxylic acid and / or a carboxylate as an extractant.
  • the scandium in the scandium-containing organic solvent is brought into contact by bringing the scandium-containing organic solvent into contact with the second acidic aqueous solution by transferring the scandium in the organic solvent to the scandium-containing organic solvent. To generate a scandium-containing aqueous solution.
  • the method for separating scandium according to one aspect of the present invention further includes a step of bringing a scandium-containing aqueous solution into contact with a precipitation agent to precipitate a scandium compound.
  • the method for separating scandium includes a step of preparing an acidic aqueous stock solution containing scandium and having a pH of less than 4, and an acidic aqueous stock solution and an alkali, so that the pH is 4 or more and 7
  • the first acidic aqueous solution is brought into contact with the first acidic aqueous solution and an organic solvent containing a carboxylic acid and / or a carboxylate as an extractant.
  • the method includes a step of generating a scandium-containing organic solvent by moving scandium therein to an organic solvent, and a step of bringing a scandium-containing organic solvent into contact with a precipitation agent to generate a scandium compound.
  • the precipitating agent is a carboxylic acid and / or a carboxylate.
  • the method for separating scandium according to one aspect and the other aspect of the present invention further includes a step of drying and / or firing the scandium compound.
  • the extractant is naphthenic acid and / or neodecanoic acid.
  • the organic solvent preferably further includes a modifier.
  • the modifier is tributyl phosphate.
  • the acidic aqueous solution further contains at least one metal ion selected from rare earth elements other than titanium, zirconium, vanadium, and scandium.
  • the acidic aqueous stock solution is preferably an aqueous solution in which ore and / or residue of the ore are dissolved with an acid.
  • the acidic aqueous stock solution is an aqueous solution in which an aqueous slurry containing scandium and an acid are mixed to adjust the pH to 2 or less.
  • the scandium separation method of the present invention by preparing an acidic aqueous stock solution having a pH of less than 4, the amount of elution of the scandium raw material can be increased, and the acidic aqueous stock solution and alkali are mixed to adjust the pH. After adjusting to the range of 4 or more and 7 or less, by contacting with an organic solvent containing carboxylic acid and / or carboxylate as an extractant, scandium is transferred to the organic solvent to reduce impurities in the organic solvent. be able to. Therefore, the present invention can provide a scandium separation method that improves productivity.
  • Embodiment 1 of this invention It is a flowchart which shows the separation method of the scandium of Embodiment 1 of this invention. It is the schematic diagram in each process in the separation method of scandium of Embodiment 1 of this invention.
  • Embodiment 2 of the present invention is a flowchart showing a method for separating scandium. It is the schematic diagram in each process in the separation method of scandium of Embodiment 2 of this invention.
  • an acidic aqueous stock solution containing scandium and having a pH of less than 4 is prepared (step S1: preparation step).
  • the acidic aqueous stock solution is not particularly limited as long as it contains scandium, and examples thereof include an acidic aqueous solution containing scandium ions, an acidic aqueous solution containing scandium such as a slurry containing scandium hydroxide and scandium oxide, and the like.
  • the pH of the acidic aqueous stock solution is less than 4, preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less from the viewpoint of quality stability.
  • the acidic aqueous stock solution contains rare earth elements other than scandium (yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium).
  • rare earth elements other than scandium yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
  • transition metal elements such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, thorium
  • radioactive elements such as uranium, other alkali metal elements, alkaline earth metal elements, group 12 elements of the periodic table such as zinc and cadmium, boron, aluminum, gallium, indium, etc.
  • Periodic group 13 element, periodic table group 14 element such as silicon, germanium, tin, periodic table group 15 element such as phosphorus, arsenic, antimony, bismuth, periodic table group 16 element such as selenium, tellurium, fluorine
  • a typical element such as a group 17 element of the periodic table such as chlorine may be included.
  • an acidic aqueous stock solution containing at least one metal ion selected from titanium, zirconium, vanadium, and a rare earth element other than scandium is preferably used because the effect is easily obtained.
  • the concentration of scandium in the acidic aqueous stock solution is not particularly limited, and is preferably high in terms of yield, more preferably about 500 to 50,000 mg / L.
  • the scandium concentration may be low.
  • scandium can be separated by the separation method of the present embodiment even at about 10 to 500 mg / L.
  • the concentration of elements (impurities) other than scandium in the acidic aqueous stock solution there is no particular limitation on the concentration of elements (impurities) other than scandium in the acidic aqueous stock solution, but in order to facilitate the separation of scandium, there are few impurity components and those with low concentrations are preferred.
  • the acidic aqueous stock solution contains titanium, zirconium and vanadium, each is preferably about 1000 mg / L or less, and more preferably 0 mg / L.
  • the acidic aqueous solution contains a rare earth element other than scandium, it is more preferably about 1000 mg / L or less, and even more preferably 0 mg / L.
  • the acidic aqueous stock solution is prepared by using an acidic aqueous solution containing scandium, using an acidic aqueous solution obtained by roughly purifying the solution, or preparing an acidic aqueous solution by mixing an acid with a slurry containing scandium hydroxide, scandium oxide, or the like. Ready.
  • the acidic aqueous stock solution for example, the following acidic aqueous solution can be used. From the viewpoint of containing a large amount of scandium, an aqueous solution obtained by dissolving ore with an acid and / or an aqueous solution obtained by dissolving an ore residue with an acid is preferable.
  • An aqueous solution prepared by mixing the aqueous slurry containing the acid and adjusting the pH to 2 or less is more preferable.
  • Acidic aqueous solution in which materials such as ores containing scandium are dissolved with acid (2) After refining other metal components by hydrolyzing or neutralizing a solution in which materials such as ores containing scandium are dissolved in acids Acidic aqueous solution or acidic aqueous solution in which the residue after refining other metal components is dissolved with acid (3) After reducing impurities by dissolving materials such as ores containing scandium with alkali in advance, the material with reduced impurities (4) Acidic aqueous solution obtained by roughly purifying scandium by adsorbing and eluting the scandium contained in the acidic aqueous solutions (1) to (3) above with an ion exchange resin or by separating the precipitates by precipitation.
  • the scandium contained in the acidic aqueous solution of (1) to (3) above is adsorbed and eluted with an ion exchange resin, or precipitated and separated.
  • Acidic aqueous solution obtained by mixing acid with slurry containing indium, scandium oxide, etc.
  • the material containing scandium may be water-soluble or sparingly soluble (including insoluble). Ores, other residues after refining other metal components from ores, aluminum alloys containing scandium, anodes of nickel / alkaline batteries, metal halide lamps, solid oxide fuel cell electrolytes, scandia stabilized zirconia ceramics, etc.
  • Various materials and wastes such as can be used.
  • 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, barium ore, calcium ore, magnesium ore, strontium ore, beryllium ore, aluminum ore, titanium ore etc., iron ore, Ores containing a large amount of scandium such as nickel ore, titanium ore, manganese ore, tin ore and aluminum ore are preferred.
  • An acid that dissolves a material such as ore 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.
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and aqua regia
  • organic acids such as acetic acid
  • the liquid after refining other metal components by hydrolyzing or neutralizing the liquid in which the material such as ore is dissolved with an acid is used as the acid that dissolves the material such as ore or the acid that is adjusted to be acidic. It can also be used.
  • a liquid after refining such other metal components for example, a leachate obtained by adding sulfuric acid to a nickel oxide ore of laterite ore and leaching under pressure
  • a liquid after taking out the nickel component from the leachate Can be used.
  • the liquid after neutralizing and taking out the titanium component and the iron component can be used as an acid for dissolving materials such as ore or an acid for adjusting the acidity.
  • dissolved the residue after chlorinating and extracting other metals in an ore with an acid can be used as an acid which dissolves materials, such as an ore, or an acid which adjusts to acidity, for example, a rutile ore Titanium ores such as iron ore and iron ore are chlorinated with chlorine gas, and the residue after taking out titanium chloride and iron chloride is made of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, aqua regia, and organic acids such as acetic acid.
  • a solution dissolved with an acid, a solution obtained by hydrolyzing the solution and taking out a titanium component and an iron component, and the like can be used.
  • alkali that dissolve materials such as ores can be used without limitation, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, ammonia, amines Etc. can be used.
  • Acids that adjust the pH to acidic after dissolving materials such as ores with alkali can be used without limitation, and use inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, aqua regia, and organic acids such as acetic acid.
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, aqua regia, and organic acids such as acetic acid.
  • An acidic aqueous solution in which materials such as the above ores are dissolved may be used.
  • the above-mentioned acidic aqueous solution is used to adsorb the scandium contained in the conventional method, for example, with an ion exchange resin, and then precipitate by elution from the ion exchange resin or pH adjustment.
  • the concentration of scandium can be increased by dispersing scandium hydroxide, scandium oxide, or the like obtained by the separation treatment in water.
  • a solution whose pH is adjusted to less than 4 by adding the roughly purified solution and the acid can also be used as the acidic aqueous stock solution.
  • Step S2 pH). Adjustment process
  • the first acidic aqueous solution obtained by carrying out this step is composed of Sc (OH) 3 present as hydroxide, Sc 3+ present as ions, and an acidic aqueous stock solution. And impurities from.
  • step S2 by setting the pH to 4 or more and 7 or less, scandium is mainly extracted in the organic solvent extraction step (step S3) described later, and impurity extraction can be reduced. If the pH is less than 4, the amount of scandium extracted is greatly reduced, and the yield of separable scandium is reduced. If the pH is higher than 7, the amount of extracted impurities increases in the organic solvent extraction step (step S3) described later, and the scandium separation efficiency decreases. From this viewpoint, it is preferable to adjust the pH to a range of 5 or more and 7 or less. Specifically, it is preferable to adjust the pH to a range of 5.0 or more and 6.5 or less, and 6.0 or more and 6.5 or less. It is more preferable to adjust to this range.
  • the alkali for adjusting the pH can be used without limitation as long as it exhibits alkalinity, and may be solid or liquid.
  • alkalis include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide and barium hydroxide, ammonia and amines. be able to.
  • step S3 organic solvent extraction step. Specifically, in this step S3, an organic solvent containing carboxylic acid and / or a salt thereof as an extractant is mixed with a first acidic aqueous solution, and a complex formed from scandium and the extractant is used as the organic solvent. Extract.
  • Step S3 an organic solvent containing scandium (scandium-containing organic solvent) and a first acidic aqueous solution that no longer contains scandium (first acidic aqueous solution after extraction) are generated. Since the scandium in the organic solvent and the carboxylic acid-based extractant form a complex of scandium carboxylate, and this complex is soluble in the organic solvent, the complex moves to the organic solvent.
  • the scandium-containing organic solvent contains scandium carboxylate produced by the extractant in the organic solvent and the scandium ions in the first acidic aqueous solution, and impurities. However, most of the impurities remain in the first acidic aqueous solution after extraction, and the impurities that move into the scandium-containing organic solvent are less than the impurities in the first acidic aqueous solution in the pH adjustment step (step S2).
  • Carboxylic acid is an organic compound having a carboxy group, and carboxylate is formed by reaction of a salt such as sodium, potassium or ammonium with the carboxyl group of carboxylic acid.
  • the carboxylic acid-based extractant is not particularly limited as long as it forms a complex with scandium.
  • known extractants such as neodecanoic acid (versaic acid-based), naphthenic acid-based, oleic acid-based, and lauric acid-based extractants From the viewpoint that scandium can be extracted more effectively, naphthenic acid and / or neodecanoic acid is preferably used.
  • the proportion of the carboxylic acid-based extractant can be appropriately set, and is preferably 1 to 50% by mass, more preferably 5 to 20% by mass with respect to the organic solvent.
  • a modifier may be added to the organic solvent.
  • the modifying agent include long-chain alkyl compounds such as nonylphenol, 1-decanol, isodecanol, 1-octanol, 2-ethylhexanol, tributyl phosphate (TBP), trioctyl phosphate (TOP), trioctylphosphine oxide (TOPO).
  • alkyl phosphate compounds such as), amines such as primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Since not only the third phase generation can be suppressed but also the back-extraction step (step S4) described later can improve the recovery rate of scandium, tributyl phosphate is preferably used.
  • the addition amount of the modifier can be appropriately set and is preferably 1 to 50% by mass, more preferably 5 to 40% by mass with respect to the organic solvent.
  • the solvent extraction operation of scandium is carried out by using a known liquid-liquid contact apparatus, a carboxylic acid-based extractant and, if necessary, an organic solvent containing a modifier and an acidic aqueous undiluted solution at a suitable temperature for a certain period of time.
  • a known liquid-liquid contact apparatus a carboxylic acid-based extractant and, if necessary, an organic solvent containing a modifier and an acidic aqueous undiluted solution at a suitable temperature for a certain period of time.
  • 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 multistage mixer-settler extractor, a continuous method and Any of batch methods may be used.
  • the treatment temperature is preferably set so as to maintain the temperature of the acidic aqueous undiluted solution and the extractant before the extraction operation, but from the viewpoint of the flash point of the organic solvent, the phase separation rate, the stability of the extractant phase, etc.
  • the temperature is preferably maintained 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-
  • Step S4 back extraction step. Specifically, in step S4, an organic solvent containing scandium (scandium-containing solvent) extracted in the organic solvent extraction step (step S3) and the second acidic aqueous solution are mixed, and the scandium is converted into the second acidic aqueous solution. Extract and purify and concentrate.
  • the 2nd acidic aqueous solution (scandium containing aqueous solution) containing scandium and the organic solvent (organic solvent after back extraction) which no longer contains scandium are produced
  • the scandium-containing aqueous solution contains scandium ions generated from scandium in the scandium-containing organic solvent by the second acidic aqueous solution and some impurities in the scandium-containing organic solvent. Impurities in the scandium-containing aqueous solution are less than or comparable to those in the scandium-containing organic solvent in the organic solvent extraction step (step S3). That is, the impurities in the scandium-containing aqueous solution are less than the impurities in the acidic aqueous stock solution in the preparation step (step S1) and the first acidic aqueous solution in the pH adjustment step (step S2).
  • 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 uses a liquid-liquid contact device to bring the organic solvent and the second acidic aqueous solution into contact with each other at a suitable temperature for a certain period of time using a known procedure, and then to the aqueous phase by stationary separation or centrifugation. It can be performed by separating into (scandium-containing aqueous solution) and an organic phase (an organic solvent after back extraction).
  • liquid-liquid contact apparatus examples include a centrifugal extractor, a mixer, a shaker, a separatory funnel, a multistage liquid-liquid contact apparatus, and more specifically, a countercurrent multistage mixer-settler extractor and a centrifugal extractor. Any of a continuous method and a 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 (step S3) and the back extraction step (step S4) 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, for example, 99.0% by mass or more, and preferably 99.5% by mass or more. it can.
  • a scandium containing aqueous solution and a precipitation agent are made to contact, and a scandium compound is deposited (step S5: precipitation process).
  • scandium is precipitated by mixing the scandium-containing aqueous solution back-extracted in the back extraction step (step S4) and the aqueous solution containing the precipitation agent, and scandium is recovered as a precipitate.
  • the scandium in the scandium-containing aqueous solution reacts with the precipitation agent, and a scandium compound as a precipitate is generated.
  • Impurities in the scandium-containing aqueous solution are maintained in the mixed solution, the impurities contained in the scandium-containing aqueous solution are reduced, so that the impurities contained in the precipitate can be reduced.
  • Impurities are basically present as ions in the mixed solution.
  • the precipitating agent is not particularly limited as long as it precipitates scandium. From the viewpoint of easy precipitation of scandium, it may be a carboxylic acid and / or a carboxylate salt (hereinafter also referred to as a carboxylic acid-based precipitating agent). preferable.
  • the precipitation agent made to contact with a scandium containing aqueous solution may be used in a solid state, and may be used as an aqueous solution containing a precipitation agent.
  • carboxylic acid-based precipitants include formic acid (methanoic acid), acetic acid (ethanoic acid), propionic acid (propanoic acid), butyric acid (butanoic acid), valeric acid (pentanoic acid), caproic acid (hexanoic acid), and enanthic acid (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) -but-2- Dicarboxylic acids such as enedi
  • the precipitating agent is not particularly limited to a carboxylic acid precipitant, and may be a carbonate such as carbon dioxide, ammonium carbonate, or sodium carbonate, or an alkali salt such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide. .
  • the ratio of the carboxylic acid type precipitation agent to scandium is preferably 1.0 to 5.0 mol, and more preferably 1.5 to 3.0 mol.
  • the scandium and the precipitating agent are brought into contact with each other at a suitable temperature for a certain period of time by a known procedure using a precipitation apparatus.
  • the obtained precipitate is a scandium compound
  • the precipitate when a carboxylic acid type precipitation agent is used is a compound of scandium carboxylate.
  • the scandium compound 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 purity of scandium can be set to 99.3% by mass or more, for example. May be 99.7% by mass or more, more preferably 99.9% by mass.
  • scandium can be separated with high purity from an acidic aqueous stock solution containing thorium, uranium and the like.
  • step S6 drying / baking step
  • the precipitate obtained in the precipitation step (step S5) can be recovered as a powder such as scandium oxide by drying and / or firing. Note that this step (step S6) may be omitted.
  • the drying conditions and / or 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 is about 300 to 1200 ° C., and the firing time is about 1 to 24 hours.
  • step S2 the reaction mechanism in the pH adjustment step (step S2) and the organic solvent extraction step (step S3) will be described.
  • step S2 when an acidic aqueous stock solution and an alkali are mixed to adjust the pH to 4 or more and 7 or less, a precipitation reaction to the right side of the following chemical formula 1 occurs.
  • step S3 In the extraction of scandium using a carboxylic acid-based extractant in the organic solvent extraction step (step S3), as shown in the following chemical formula 2, the scandium ion and the carboxylic acid-based extractant form a complex.
  • Sc 3+ + 3HA ⁇ ScA 3 + 3H + (chemical formula 2)
  • HA is an extractant having a proton (H + )
  • A is an alkyl group containing carbon
  • a ⁇ in the case of neodecanoic acid is C 9 H 19 COO ⁇ .
  • the first acidic aqueous solution and alkali are mixed to adjust the pH of the first acidic aqueous solution to 4 or more, so that the right side in Chemical Formula 2 Promotes reaction to
  • the first acidic aqueous solution and alkali are mixed to adjust the pH of the first acidic aqueous solution to 7 or less.
  • the method for separating scandium in the present embodiment includes a step of preparing an acidic aqueous stock solution containing scandium and having a pH of less than 4 (step S1), and mixing the acidic aqueous stock solution and an alkali.
  • producing a scandium-containing aqueous solution by moving scandium in the scandium-containing organic solvent to the second acidic aqueous solution.
  • an acidic aqueous stock solution having a pH of less than 4 is prepared as a raw material containing scandium in the preparation step (step S1). For this reason, even if a sparingly soluble scandium raw material is used, it can be dissolved as scandium ions in the acidic aqueous stock solution, so that a decrease in the content of scandium in the acidic aqueous stock solution can be suppressed.
  • the pH is adjusted to a range of 4 to 7 using an alkali before the organic solvent extraction step (step S3), and naphthenic acid,
  • a carboxylic acid such as neodecanoic acid and / or a salt thereof
  • extraction of impurities such as titanium, zirconium, vanadium, and rare earth elements other than scandium can be suppressed to a low level.
  • this effect is an effect found by conceiving the knowledge of the reaction mechanism in the pH adjustment step (step S2) and the organic solvent extraction step (step S3) described above.
  • scandium can be transferred to the second acidic aqueous solution by bringing the extracted scandium-containing organic solvent containing scandium into contact with the second acidic aqueous solution such as sulfuric acid or hydrochloric acid. Therefore, productivity can be improved and scandium can be separated.
  • the scandium separation method of the present embodiment preferably further includes a step (step S5) of bringing a scandium-containing aqueous solution and a precipitating agent into contact with each other to precipitate a scandium compound.
  • step S5 the scandium-containing aqueous solution obtained in the back extraction step (step S4) can be mixed with a carboxylic acid such as oxalic acid and / or a salt thereof as a precipitating agent to precipitate a scandium compound. It can improve and separate scandium.
  • the scandium separation method of the present embodiment preferably further includes a step of drying and / or firing the scandium compound (step S6). Thereby, it can collect
  • a coprecipitate can be formed by mixing the scandium-containing aqueous solution separated by performing the back extraction step (step S4) and the zirconium aqueous solution, and calcined to produce scandia-stabilized zirconia.
  • the scandium separated by carrying out the drying / firing step (step S6) is a powder such as scandium hydroxide or scandium oxide
  • the powder is mixed with zirconium oxide and fired to obtain scandia-stabilized zirconia.
  • scandium separation method of the present embodiment scandium can be separated so as to increase the purity by reducing impurities while improving productivity. That is, according to the scandium separation method of the present embodiment, scandium can be purified with high efficiency and ease.
  • scandia-stabilized zirconia using scandium obtained according to the present embodiment is useful for an electrolyte of a solid oxide fuel cell. Further, scandium oxide can be reduced to a metal, and iodide can be obtained. It can also be used as a compound such as scandium iodide.
  • step S1 preparation step. Since this step S1 is the same as that of Embodiment 1, the description thereof will not be repeated.
  • a first acidic aqueous solution is generated by mixing the acidic aqueous stock solution and the alkali and adjusting the pH to a range of 4 or more and 7 or less (step S2: pH). Adjustment process). Since this step S2 is the same as that of Embodiment 1, the description thereof will not be repeated.
  • step S3 organic solvent extraction step
  • the back extraction step (step S4: back extraction step) of Embodiment 1 is omitted, and then, as shown in FIGS. 3 and 4, the scandium-containing organic solvent is contacted with the precipitation agent.
  • step S5 precipitation step
  • an organic solvent containing extracted scandium and a precipitant are mixed to precipitate scandium.
  • the scandium in the scandium-containing organic solvent reacts with the precipitation agent to obtain a scandium compound.
  • the back extraction process (step S4) of the present embodiment is different from the first embodiment in that the object to be contacted with the precipitation agent is a scandium-containing organic solvent, and the other processes are the same as in the first embodiment.
  • step S6 drying / baking step. Since this step S6 is the same as that of Embodiment 1, the description thereof will not be repeated. This step S6 may be omitted.
  • step S6 By performing the above steps (steps S1 to S3, S5, S6), productivity can be improved and scandium can be separated.
  • the purity of scandium is, for example, 99.0% by mass or more. , Preferably it can be 99.5 mass% or more.
  • step S1 an acidic aqueous undiluted solution in which scandium hydroxide containing impurities is dispersed in water, sulfuric acid is added to adjust the pH to 1.0, and the scandium is dissolved by heating at 90 ° C. for 3 hours.
  • step S2 sodium hydroxide was added to the acidic aqueous stock solution to adjust to pH 6.5 (first acidic aqueous solution: sample A).
  • step S3 100 mL of this acidic aqueous stock solution (aqueous phase), neodecanoic acid (extractant), and tributyl phosphate (modifier) at concentrations of 10% by mass and 30% by mass, respectively. Then, 100 mL of an organic solvent dissolved in kerosene was placed in a 500 mL separatory funnel and mixed with a vertical shaker for 20 minutes to extract scandium. After shaking, the separatory funnel was allowed to stand to separate into an organic phase (scandium-containing organic solvent) and an aqueous phase (first acidic aqueous solution after extraction).
  • organic phase scandium-containing organic solvent
  • aqueous phase first acidic aqueous solution after extraction
  • step S4 As a back extraction step (step S4), 80 mL of the organic phase from which scandium was extracted (scandium-containing organic solvent) and 20 mL of 2M sulfuric acid (second acidic aqueous solution) were placed in a 500 mL separatory funnel, and a vertical shaker for 20 minutes And back-extracted scandium. After shaking, the separatory funnel was allowed to stand, and the organic phase (organic solvent after back extraction) and the aqueous phase (scandium-containing aqueous solution: sample B) were separated.
  • the organic phase organic solvent after back extraction
  • aqueous phase scandium-containing aqueous solution: sample B
  • step S1 an acidic aqueous stock solution in which scandium hydroxide containing impurities is dispersed in water, hydrochloric acid is added to adjust the pH to 1.0, and the scandium is dissolved by heating at 90 ° C. for 3 hours.
  • step S2 sodium hydroxide was added to the aqueous solution to adjust to pH 6.0.
  • the organic solvent extraction step (step S3) and the back extraction step (step S4) are performed to extract scandium and back extract, and the aqueous phase (first acidic aqueous solution before extraction) is extracted.
  • Sample C) and an aqueous phase after back extraction were obtained.
  • Elemental concentrations were analyzed with an inductively coupled plasma emission spectrometer (ICP-AES) and an inductively coupled plasma mass spectrometer (ICP-MS), respectively. The results are shown in Table 3 and Table 4, respectively.
  • Example 3 In Example 3, the precipitation step (Step S5) was further performed. Specifically, the scandium-containing aqueous solution of Sample B of Example 1 and Sample D of Example 2 and oxalic acid (1.5 mol times with respect to scandium) as a precipitating agent were mixed in a reaction vessel to obtain a scandium compound. As a result, scandium oxalate was deposited.
  • scandia-stabilized zirconia can be produced by treating the scandium oxalate precipitate obtained in Example 3, its dried product, and calcined scandium oxide by a known method. Furthermore, they have been confirmed to act as electrolytes for solid oxide fuel cells.
  • step S1 scandium hydroxide containing impurities was dispersed in water, and sulfuric acid was added to adjust the pH to 0.5 to dissolve scandium.
  • aqueous ammonia was added to adjust the pH to 2.5, and the mixture was heated at 90 ° C. for 1 hour to precipitate impurities such as titanium as hydroxides. This was filtered, and the filtrate was collected to obtain an acidic aqueous stock solution.
  • step S2 ammonia water was added to the acidic aqueous stock solution to adjust to pH 6.5 (first acidic aqueous solution: sample G).
  • step S3 As an organic solvent extraction step (step S3), 15 mL of this acidic aqueous stock solution (aqueous phase), neodecanoic acid (extractant), and tributyl phosphate (modifier) at concentrations of 10% by mass and 30% by mass, respectively. Then, 15 mL of an organic solvent dissolved in kerosene was placed in a 50 mL centrifuge tube and mixed with a vertical shaker for 20 minutes to extract scandium. After shaking, the centrifuge tube was allowed to stand and separated into an organic phase (scandium-containing organic solvent) and an aqueous phase (first acidic aqueous solution after extraction: sample H).
  • an organic phase scandium-containing organic solvent
  • aqueous phase first acidic aqueous solution after extraction: sample H.
  • step S4 As a back extraction step (step S4), 10 mL of the organic phase from which scandium was extracted (scandium-containing organic solvent) and 10 mL of 0.4N hydrochloric acid (second acidic aqueous solution) were placed in a 50 mL centrifuge tube and shaken vertically for 20 minutes. Mix in the machine and back-extract scandium. After shaking, the centrifuge tube was allowed to stand, and the organic phase (organic solvent after back extraction) and the aqueous phase (scandium-containing aqueous solution: sample I) were separated.
  • organic phase organic solvent after back extraction
  • aqueous phase scandium-containing aqueous solution: sample I
  • step S3 As in Examples 1 and 2, it was found that by performing the organic solvent extraction step (step S3) and the back extraction step (step S4), the impurity element was separated, and scandium could be separated with high accuracy. Further, the scandium recovery rate in the back extraction process was as high as about 90%.
  • Example 5 In the organic solvent extraction step (step S3), a preparation step (same as in Example 4) except that only neodecanoic acid (extractant) dissolved in kerosene so as to have a concentration of 10% by mass is used as the organic solvent.
  • Step S1 pH adjustment step (Step S2), organic solvent extraction step (Step S3), back extraction step (Step S4) are carried out, first acidic aqueous solution (sample J) after extraction and scandium containing after back extraction An aqueous solution (Sample K) was obtained.
  • ICP-AES inductively coupled plasma emission spectrometer
  • ICP-MS inductively coupled plasma mass spectrometer
  • the scandium separated by the scandium separation method of the present invention can be used in various applications because it is separated with improved productivity and is low in impurities and high in purity. Specifically, scandia-stabilized zirconia and the like useful for an electrolyte of a solid oxide fuel cell can be produced.

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Abstract

L'invention porte sur un procédé de séparation de scandium, comprenant : une étape (étape S1) dans laquelle une solution hydrosoluble acide ayant un pH inférieur à 4 et contenant du scandium est préparée ; une étape (étape S2) dans laquelle un premier fluide hydrosoluble acide est produit par le mélange de la solution hydrosoluble acide et d'une base et le réglage du pH dans une plage de 4 à 7 ; une étape (étape S3) dans laquelle un solvant organique contenant du scandium est produit par la mise en contact l'un avec l'autre du premier fluide hydrosoluble acide et du solvant organique comprenant, en tant qu'agent d'extraction, un acide carboxylique et/ou un carboxylate et le transfert du scandium présent dans le premier fluide hydrosoluble acide vers le solvant organique ; et une étape (étape S4) dans laquelle un fluide hydrosoluble contenant du scandium est produit par la mise en contact l'un avec l'autre du solvant organique contenant du scandium et d'un second fluide hydrosoluble acide et le transfert du scandium présent dans le solvant organique contenant du scandium vers le second fluide hydrosoluble acide.
PCT/JP2015/053606 2014-02-17 2015-02-10 Procédé de séparation de scandium WO2015122397A1 (fr)

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JP7069823B2 (ja) * 2018-02-27 2022-05-18 住友金属鉱山株式会社 スカンジウム化合物
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CN114737056B (zh) * 2021-01-08 2023-11-03 厦门稀土材料研究所 一种有机萃取剂及其回收金属元素的方法和应用
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