WO2019146619A1 - 高純度酸化スカンジウムの製造方法 - Google Patents
高純度酸化スカンジウムの製造方法 Download PDFInfo
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- WO2019146619A1 WO2019146619A1 PCT/JP2019/002012 JP2019002012W WO2019146619A1 WO 2019146619 A1 WO2019146619 A1 WO 2019146619A1 JP 2019002012 W JP2019002012 W JP 2019002012W WO 2019146619 A1 WO2019146619 A1 WO 2019146619A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/282—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
- C01F17/13—Preparation or treatment, e.g. separation or purification by using ion exchange resins, e.g. chelate resins
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/212—Scandium oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—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
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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
- C22B3/065—Nitric acids or salts thereof
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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
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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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
Definitions
- the present invention relates to a method of producing scandium oxide, and more particularly to a method of producing high purity scandium oxide with reduced impurity quality.
- Patent Document 1 low-grade scandium oxide is heated and dissolved with nitric acid, the nitric acid solution is brought into contact with an anion exchange resin to adsorb impurities dissolved in the solution, and hydrochloric acid is added to the solution.
- a method of separating scandium and impurities by contacting with an anion exchange resin and adsorbing the other impurities to the resin it is shown that high purity scandium oxide can be obtained by further adding oxalic acid or hydrofluoric acid and calcining the obtained precipitate.
- the present invention has been proposed in view of such circumstances, and it is an object of the present invention to provide a method for efficiently obtaining high purity scandium oxide from a solution containing scandium.
- a solution containing scandium is subjected to an oxalic acid oxidation treatment using oxalic acid, and the obtained scandium oxalate crystals are fired at a temperature of 400 ° C. to 600 ° C.
- the second invention of the present invention is the high-purity scandium oxide oxide according to the first invention, wherein the temperature of the solution is adjusted to 40 ° C. or more and less than 100 ° C. to perform oxalic acid oxidation treatment in the reprecipitation step. Manufacturing method.
- the third invention of the present invention is the method for producing high purity scandium oxide according to the first or second invention, wherein the baking is performed at a baking temperature of 900 ° C. or more in the second baking step.
- the scandium-containing solution is subjected to an ion exchange treatment and / or a solvent extraction treatment on the scandium-containing solution. It is a manufacturing method of high purity scandium oxide which is obtained by carrying out.
- high purity scandium oxide can be efficiently obtained from a solution containing scandium.
- the present embodiment is not limited to the following embodiment, A various change is possible in the range which does not change the summary of this invention.
- the notation “X to Y” (X and Y are arbitrary numerical values) means “more than X and less than Y”.
- the method for producing scandium oxide according to this embodiment is a method of obtaining a scandium oxide from a crystal of scandium oxalate obtained by subjecting a solution containing scandium to oxalic acid oxidation treatment using oxalic acid. And, in this production method, scandium oxalate obtained by oxalic acid treatment from a solution containing scandium is fired in two steps to obtain high purity scandium oxide with few impurities. .
- a solution containing scandium is subjected to an oxalic acid oxidation treatment using oxalic acid, and the obtained scandium oxalate crystal is fired at a predetermined temperature.
- a baking step a dissolving step of dissolving a scandium compound obtained by firing in one or more solutions selected from hydrochloric acid and nitric acid to obtain a solution, and performing an oxalic acid oxidation treatment on the solution using oxalic acid, It has a reprecipitation step of forming a reprecipitate of scandium oxalate, and a second baking step of firing the obtained reprecipitate of scandium oxalate to obtain scandium oxide.
- scandium-containing solution a solution containing scandium as a raw material
- HPAL high pressure acid leaching
- the solution after sulfurization may be separated into impurities by ion exchange treatment and / or solvent extraction treatment, and a solution in which scandium is concentrated (sulfuric acid solution) can be used.
- a chelate resin treatment using a resin having iminodiacetic acid as a functional group can be mentioned.
- an adsorption process in which the after-sulfiding solution is brought into contact with a chelate resin to adsorb scandium onto the chelate resin, and the chelate resin is brought into contact with sulfuric acid.
- An aluminum removal step of removing aluminum adsorbed to the chelate resin a scandium elution step of obtaining a scandium elution solution by contacting sulfuric acid with the chelate resin subjected to the aluminum removal step, and contacting the sulfuric acid with the chelate resin subjected to the scandium elution step
- the chromium removal step of removing the chromium adsorbed to the chelate resin in the adsorption step.
- the solvent extraction process is also not particularly limited, and the scandium eluate obtained through the above-described ion exchange process is subjected to a solvent extraction process using an amine-based extractant, a phosphate-based extractant, etc. be able to.
- the scandium eluent and the extractant are mixed to extract impurities, and then the extract is separated into the organic solvent and the extract containing scandium, and the extracted organic solvent is mixed with a hydrochloric acid solution or a sulfuric acid solution.
- Extraction and scrubbing step of separating scandium contained in the organic solvent by trace amount, and mixing the back extraction starting solution into the organic solvent after washing, back extracting the impurities from the organic solvent after washing, and obtaining the back extraction solution Can be illustrated.
- the oxidation obtained using the scandium-containing solution as a raw material Scandium has an even higher scandium grade.
- FIG. 1 is a process diagram showing an example of the flow of a method for producing scandium oxide.
- an oxalic acid oxidation step S11 of subjecting a scandium-containing solution to oxalic acid oxidation treatment, and a first firing step of firing the obtained scandium oxalate crystals at a predetermined temperature S12 and a scandium compound which is a baked product are dissolved in a mineral acid to obtain a solution, and the solution is subjected to oxalic acid oxidation treatment to obtain a reprecipitate of scandium oxalate crystals.
- S14, and a second firing step of firing a reprecipitate of scandium oxalate to obtain scandium oxide are examples of scandium oxide.
- the oxalic acid oxidation process S11 is a process of subjecting the scandium-containing solution to an oxalic acid oxidation process. Specifically, in the oxalic acid oxidation step S11, a reaction of scandium into oxalate (scandium oxalate) using oxalic acid is caused to the scandium-containing solution.
- the scandium-containing solution is not particularly limited, but is preferably adjusted to have a scandium concentration of 5 g / L to 10 g / L, more preferably about 5 g / L, using an acid such as sulfuric acid PH adjusted to about 0 is used.
- oxalic acid may be added to the scandium-containing solution to precipitate and form solid crystals of scandium oxalate based on scandium in the scandium-containing solution.
- the oxalic acid used may be solid or solution.
- a method of causing solid crystals of scandium oxalate to precipitate is generated (so-called reverse addition method) by gradually adding a scandium-containing solution into an oxalic acid solution filled in a reaction vessel as a method of oxalic acid oxidation treatment be able to.
- precipitation of iron (II) oxalate and the like can be prevented, and scandium of higher purity can be recovered without using an expensive oxidizing agent and the like.
- the temperature of the scandium-containing solution to be treated is preferably adjusted to a range of 10 ° C. or more and 30 ° C. or less, and more preferably adjusted to a range of 15 ° C. or more and 25 ° C. or less.
- the oxalic acid used for the treatment it is preferable to use an amount in the range of 1.05 times to 1.2 times the equivalent necessary for depositing scandium in the scandium-containing solution as an oxalate salt. If the amount used is less than 1.05 times the required equivalent, the entire amount of scandium may not be recovered effectively. On the other hand, if the amount used exceeds 1.2 times the required equivalent, the solubility of scandium oxalate increases and scandium re-dissolves to lower the recovery rate, and also to decompose excess oxalic acid. It is not preferable because the amount of oxidizing agent such as sodium hypochlorite increases.
- the crystals of scandium oxalate obtained by such an oxalic acid oxidation treatment can be recovered by filtration and washing treatment.
- the first firing step S12 is a step of firing the crystals of scandium oxalate obtained in the oxalic acid oxidation step S11 at a predetermined temperature. By the baking treatment at such a predetermined temperature, a scandium compound which is a baked product can be obtained.
- the firing is performed in the range of 400 ° C. or more and 600 ° C. or less in the first firing step S12.
- the present inventor performed a scan process on a scandium oxalate crystal under conditions of a temperature range of 400 ° C. to 600 ° C., which is a lower temperature range than conventional, to easily scandium scandium which is easily soluble in an aqueous solution such as acid. It was found that a compound was obtained.
- the easily soluble scandium compound thus obtained has a weight loss ratio of 53% to 65%, preferably 55% to 65%, and more preferably 53% to 65%, based on the weight of the scandium oxalate crystals before the baking treatment. It is in the range of 55% to 60%.
- the present inventors have a weight loss ratio having a range of 55% or more and 65% or less From this, it was found that there is a region exhibiting a form of easy solubility when the poorly soluble scandium oxalate is heated to be decomposed into the hardly soluble scandium oxide.
- the crystal of scandium oxalate which is the raw material, is not completely decomposed by firing and the whole amount becomes scandium oxide, but some scandium oxalate remains. Or, it is considered to be a compound in which CO 2 or CO generated by decomposition remains.
- the easily soluble scandium compound obtained by firing under temperature conditions in the range of 400 ° C. to 600 ° C. contains more carbon (C) than scandium oxide obtained by firing at a conventional high temperature. ing.
- scandium compounds in the easily soluble region are simply referred to simply as "scandium compounds".
- the peak of scandium oxalate is not observed, and the peak intensity corresponding to the peak of scandium oxide is also 11,000 counts It becomes below. From this, it is considered that the scandium compound obtained by firing at a temperature of 400 ° C. or more and 600 ° C. or less has a low degree of crystallinity and has a property of easy solubility.
- the scandium compound exhibiting this solubility has the property of being a fine one having a BET specific surface area of 70 m 2 / g or more.
- the scandium compound obtained at a firing temperature of 400 ° C. is 250 m 2 / g or more.
- the specific surface area of the scandium compound more preferably 100 m 2 / g or more, more preferably 200 meters 2 / g or more, particularly preferably 250 meters 2 / g or more.
- the conditions for producing the easily soluble scandium compound in this way are to fire under the temperature conditions in the range of 400 ° C. to 600 ° C., and more preferably, the temperature in the range of 400 ° C. to 500 ° C. It is to bake on conditions. Also, in other words, such a readily soluble scandium compound has a weight loss ratio of 53% or more and 65% or less, preferably 55% or more and 65% or less, and more preferably 55% or more and 60% or less. It can be obtained by firing under the following conditions.
- the crystals of scandium oxalate obtained by the oxalic acid oxidation treatment are washed with water, dried, and then fired using a predetermined furnace.
- the furnace is not particularly limited, but may be a tubular furnace or the like, and industrially, using a continuous furnace such as a rotary kiln is preferable because drying and firing can be performed continuously by the same apparatus.
- the holding time when firing is performed at a firing temperature of 400 ° C. to 600 ° C. is not particularly limited, but is preferably 0.5 hours to 12 hours, and is 1 hour to 12 hours More preferably, it is particularly preferably 1 hour or more and 6 hours or less. If the holding time is less than 0.5 hours, the firing may not proceed sufficiently, and a large amount of poorly soluble scandium oxalate may remain. On the other hand, when the holding time exceeds 12 hours, the easily soluble property of the obtained scandium compound may hardly change or may gradually decrease, and the heat energy increases, resulting in an increase in processing cost.
- the scandium compound which is a calcined product obtained by the calcination treatment in the first calcination step S12 is totally dissolved in one or more solutions selected from hydrochloric acid and nitric acid which are mineral acids to obtain a solution. It is a process.
- the firing step S12 by performing the firing at the firing temperature in the range of 400 ° C. or more and 600 or less in the first firing step S12, it is possible to obtain a scandium compound having easy solubility in an aqueous solution such as an acid. Therefore, in the dissolution step S13, a so-called re-dissolution solution in which scandium is eluted in a solution by dissolving the easily soluble scandium compound thus obtained in one or more solutions selected from hydrochloric acid and nitric acid. Thus, it is possible to obtain a solution in which scandium is concentrated.
- a re-dissolution solution is prepared utilizing the easily soluble property of the obtained scandium compound, and based on this re-dissolution solution again in the subsequent step.
- the dissolution treatment in the dissolution step S13 is not particularly limited, and pure water is added to the scandium compound, and one or more solutions selected from hydrochloric acid and nitric acid are further added thereto and stirred. Can. Moreover, as temperature conditions in the dissolution treatment, the temperature can be adjusted to a range of about 40 ° C. or more and 80 ° C. or less.
- the pH condition of the solution selected from hydrochloric acid and nitric acid used for dissolution is not particularly limited, and for example, one adjusted to about pH 0 to 2 may be used. Since scandium compounds to be dissolved in these acid solutions exhibit solubility as described above in aqueous solutions such as acids, they can be easily dissolved even under conditions of pH 0 to 2 and high concentration It is possible to effectively reduce the drug cost required for As the acid solution, sulfuric acid which is the same mineral acid can be used other than the above-mentioned hydrochloric acid and nitric acid. However, according to the experiments of the present inventor, it was found that although the mechanism is not clear, by dissolving using hydrochloric acid, scandium oxalate having higher purity than that obtained using sulfuric acid can be obtained.
- the scandium concentration can be increased to about 50 g / L and adjusted to an arbitrary value, thereby reducing the amount of liquid and, in turn, reducing the amount of equipment. Capacity can be reduced.
- re-precipitation process In the re-precipitation step S14, re-precipitation of the scandium oxalate crystals is carried out by subjecting the solution obtained by re-dissolving the scandium compound in the dissolution step S13 (re-dissolution solution) to an oxalic acid oxidation treatment again. It is a process to obtain.
- a second solution of oxalic acid oxidation is performed using the redissolved solution as a raw material.
- the method of re-dissolving the easily soluble scandium compound and re-producing scandium oxalate crystals from the re-dissolution solution it coexists with the scandium oxalate crystals obtained by the second oxalic acid oxidation.
- the amount of impurities can be significantly reduced.
- the method of the Shu oxidation treatment in the reprecipitation step S14 can be performed in the same manner as the treatment performed in the Shu oxidation step S11. For example, it is adjusted to have a scandium concentration of 5 g / L to 10 g / L, more preferably about 5 g / L, and pH is further adjusted using a mineral acid such as hydrochloric acid or nitric acid.
- the Shu oxidation treatment is performed using one adjusted to about 0.
- oxalic acid oxidation treatment by setting the solution temperature of the solution (re-dissolution solution) at the time of reaction to 40 ° C. or higher, oxalic acid obtained as compared with the case where the reaction occurs at normal temperature (25 ° C.)
- the particles of scandium can be coarsened, and handling at the time of charging to the firing furnace in the next firing step (second firing step) becomes easy.
- the impurities may be caught in the gaps between the particles and the quality may be lowered simply by coarsening.
- the easily soluble scandium compound is redissolved, and crystals of scandium oxalate are generated again from the redissolved solution, the crystals of scandium oxalate for the second time Since the impurities coexisting in the above can be significantly reduced, the particles can be effectively coarsened. From this, the handling property can be effectively enhanced.
- the temperature conditions in the oxalic acid oxidation treatment are preferably in the range of 40 ° C. or higher and less than 100 ° C. It is more preferable to set it as the range of 40 degreeC or more and 60 degrees C or less.
- the second firing step S15 is a step of firing the reprecipitate of scandium oxalate obtained in the reprecipitation step S14 at a predetermined temperature. That is, in the second baking step S15, a second baking process of baking the crystal of scandium oxalate obtained from the re-dissolution is performed to obtain scandium oxide by this baking process.
- the firing temperature condition is preferably 900 ° C. or higher, more preferably 1000 ° C. or higher, and particularly preferably about 1100 ° C.
- the crystal of scandium oxalate is fired at a high temperature of 900 ° C. or more to form a compound having a form of scandium oxide as a fired product.
- carbon (C) derived from oxalic acid remains by baking on high temperature conditions in this way.
- the obtained crystals of scandium oxalate are washed with water and dried, as in the treatment in the first firing step S12. Use and bake.
- the holding time when firing at a firing temperature of 900 ° C. or higher is not particularly limited, but is preferably 0.5 hours to 12 hours, and more preferably 1 hour to 12 hours. It is preferable that it is preferably 1 hour or more and 6 hours or less. If the holding time is less than 0.5 hours, the firing may not proceed sufficiently, and a fired product in the form of scandium oxide may not be obtained effectively. On the other hand, if the holding time exceeds 12 hours, the heat energy increases and the processing cost becomes high.
- Example 1 ⁇ Formation of scandium-containing solution> (Wet smelting process of nickel oxide ore) Nickel oxide ore was leached with sulfuric acid using an autoclave, and the obtained leachate was neutralized by adding slaked lime. Next, a sulfurizing agent is added to the obtained neutralized solution to cause a sulfurization reaction, nickel, cobalt and the like are separated as sulfides, and a scandium-containing sulfurized solution is obtained.
- the entire amount of the solution was filtered to separate out scandium oxalate crystals, and 50 g of the separated crystals were repeatedly washed three times with 1 liter of pure water using 1 liter of pure water.
- the obtained scandium solution was diluted to have a scandium concentration of 5 g / L, and hydrochloric acid was added to adjust the pH to 0 to prepare a solution of 3.5 liters.
- ⁇ Second firing step> the washed crystal of scandium oxalate was placed in a furnace, and a second baking was performed at a baking temperature of 900 ° C. for 2 hours to generate scandium oxide. Then, scandium oxide taken out of the furnace was analyzed.
- Example 2 ⁇ Formation of scandium-containing solution> (Wet smelting process of nickel oxide ore) Nickel oxide ore was leached with sulfuric acid using an autoclave, and the obtained leachate was neutralized by adding slaked lime. Next, a sulfurizing agent is added to the obtained neutralized solution to cause a sulfurization reaction, nickel, cobalt and the like are separated as sulfides, and a scandium-containing sulfurized solution is obtained.
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Abstract
Description
本実施の形態に係る酸化スカンジウムの製造方法は、スカンジウムを含有する溶液にシュウ酸を用いてシュウ酸化処理を施し、得られたシュウ酸スカンジウムの結晶から酸化スカンジウムを得る方法である。そして、この製造方法では、スカンジウムを含有する溶液からシュウ酸処理により得られるシュウ酸スカンジウムを、2段階で焼成することで、不純物の少ない高純度な酸化スカンジウムを得ることを特徴とするものである。
図1は、酸化スカンジウムの製造方法の流れの一例を示す工程図である。図1に示すように、この製造方法は、スカンジウム含有溶液に対してシュウ酸化処理を施すシュウ酸化工程S11と、得られたシュウ酸スカンジウムの結晶に対して所定の温度で焼成する第1焼成工程S12と、焼成物であるスカンジウム化合物を鉱酸に溶解させて溶解液を得る溶解工程S13と、溶解液に対してシュウ酸化処理を施してシュウ酸スカンジウムの結晶の再沈殿物を得る再沈殿工程S14と、シュウ酸スカンジウムの再沈殿物を焼成して酸化スカンジウムを得る第2焼成工程と、を有する。
シュウ酸化工程S11は、スカンジウム含有溶液に対してシュウ酸化処理を施す工程である。具体的に、シュウ酸化工程S11では、スカンジウム含有溶液に対してシュウ酸を用いてスカンジウムをシュウ酸塩(シュウ酸スカンジウム)とする反応を生じさせる。
第1焼成工程S12は、シュウ酸化工程S11で得られたシュウ酸スカンジウムの結晶に対して所定の温度で焼成する工程である。このような所定の温度での焼成処理により、焼成物であるスカンジウム化合物を得ることができる。
減量率(%)=(1-焼成後物量/焼成前物量)×100
・・・[1]
溶解工程S13は、第1焼成工程S12での焼成処理により得られた焼成物であるスカンジウム化合物を、鉱酸である塩酸及び硝酸から選ばれる1種以上の溶液に全溶解させて溶解液を得る工程である。
再沈殿工程S14は、溶解工程S13においてスカンジウム化合物を再溶解して得られた溶解液(再溶解液)を用い、再度、シュウ酸化処理を施すことによって、シュウ酸スカンジウムの結晶の再沈殿物を得る工程である。
第2焼成工程S15は、再沈殿工程S14で得られたシュウ酸スカンジウムの再沈殿物を所定の温度で焼成する工程である。すなわち、第2焼成工程S15では、再溶解液から得られたシュウ酸スカンジウムの結晶を焼成する2回目の焼成処理を行い、この焼成処理により酸化スカンジウムを得る。
<スカンジウム含有溶液の生成>
(ニッケル酸化鉱石の湿式製錬プロセス)
オートクレーブを用いてニッケル酸化鉱石を硫酸で浸出し、得られた浸出液に消石灰を添加して中和した。次いで、得られた中和後液に硫化剤を添加して硫化反応を生じさせ、ニッケルやコバルト等を硫化物として分離し、スカンジウムを含有する硫化後液を得た。
次に、得られた硫化後液に対してキレート樹脂を用いたイオン交換処理に付し、溶液中の不純物を分離するとともに、キレート樹脂から溶離したスカンジウムを含む溶離液(スカンジウム溶離液)を得た。その後、スカンジウム溶離液に対して中和剤を添加して、水酸化スカンジウムの沈殿物を生成させた。
次に、水酸化スカンジウムの沈殿物に硫酸を添加して再度溶解して溶解液(スカンジウム溶解液)とし、このスカンジウム溶解液に対してアミン系抽出剤を用いた溶媒抽出処理に付し、抽残液として硫酸スカンジウム溶液(スカンジウム含有溶液)を得た。
得られた硫酸スカンジウム溶液を、スカンジウム濃度が5g/L程度となるまで水を加えて希釈し、硫酸でpHが0になるように調整した。そして、この調整後の溶液をシュウ酸化始液とし、合計65リットルを準備した。
次に、シュウ酸化処理により得られたシュウ酸スカンジウムの結晶の一部を分取し、これを炉に入れて1100℃の温度で2時間かけて焼成し、得られた焼成物を分析した。なお、下記表5に、焼成温度1100℃として得られた焼成物の分析結果を示す(表5中の「1回目の焼成処理後の酸化スカンジウム」)。
次に、焼成温度400℃で焼成して得られた焼成物の残りから150gを採取し、それに純水を加えて混合しながら60℃に加熱し、さらに塩酸を添加してpHを1に調整した。この操作により、150gのシュウ酸スカンジウムの結晶の95%以上が溶解したスカンジウム溶解液を得た。下記表3に、溶解処理の条件をまとめて示す。
次に、再溶解液中のスカンジウムに対して2.7当量のシュウ酸を反応させるため、シュウ酸を100g/Lの濃度で溶解した溶液を1.45リットル準備した。そして、そのシュウ酸溶液を反応容器に収容し、そのシュウ酸溶液の中に再溶解液を添加した。再溶解液を全量添加した後、1時間撹拌状態を保持した。なお、反応温度を25℃とし、滞留時間を2時間、添加時間を1時間とする条件とした。下記表4に、シュウ酸化(2回目のシュウ酸化)の処理条件をまとめて示す。
次に、洗浄後のシュウ酸スカンジウムの結晶を炉に入れて2回目の焼成を、焼成温度900℃で2時間かけて行い、酸化スカンジウムを生成させた。そして、炉から取り出した酸化スカンジウムを分析した。
<スカンジウム含有溶液の生成>
(ニッケル酸化鉱石の湿式製錬プロセス)
オートクレーブを用いてニッケル酸化鉱石を硫酸で浸出し、得られた浸出液に消石灰を添加して中和した。次いで、得られた中和後液に硫化剤を添加して硫化反応を生じさせ、ニッケルやコバルト等を硫化物として分離し、スカンジウムを含有する硫化後液を得た。
次に、得られた硫化後液に対してキレート樹脂を用いたイオン交換処理に付し、溶液中の不純物を分離するとともに、キレート樹脂から溶離したスカンジウムを含む溶離液(スカンジウム溶離液)を得た。その後、スカンジウム溶離液に対して中和剤を添加して、水酸化スカンジウムの沈殿物を生成させた。
次に、水酸化スカンジウムの沈殿物に硫酸を添加して再度溶解して溶解液(スカンジウム溶解液)とし、このスカンジウム溶解液に対してアミン系抽出剤を用いた溶媒抽出処理に付し、抽残液として硫酸スカンジウム溶液(スカンジウム含有溶液)を得た。
得られた硫酸スカンジウム溶液を、スカンジウム濃度が5g/L程度となるまで水を加えて希釈し、硫酸でpHが0になるように調整した。そして、この調整後の溶液をシュウ酸化始液とし、合計65リットルを準備した。
次に、シュウ酸化処理により得られたシュウ酸スカンジウムの結晶の一部を分取し、これを炉に入れて1100℃の温度で2時間かけて焼成し、得られた焼成物を分析した。なお、下記表10に、焼成温度1100℃として得られた焼成物の分析結果を示す(表10中の「1回目の焼成処理後の酸化スカンジウム」)。
次に、焼成温度400℃で焼成して得られた焼成物の残りから150gを採取し、それに純水を加えて混合しながら60℃に加熱し、さらに塩酸を添加してpHを1に調整した。この操作により、150gのシュウ酸スカンジウムの結晶の95%以上が溶解したスカンジウム溶解液を得た。下記表8に、溶解処理の条件をまとめて示す。
次に、再溶解液中のスカンジウムに対して2.7当量のシュウ酸を反応させるため、シュウ酸を100g/Lの濃度で溶解した溶液を試験条件毎に1.45リットル準備した。そして、再溶解液を反応容器に収容し、その再溶解液の中にシュウ酸溶液を添加した。シュウ酸溶液を全量添加した後、1時間撹拌状態を保持した。なお、反応温度を25℃とし、滞留時間を2時間、添加時間を1時間とする条件とした。下記表9に、シュウ酸化(2回目のシュウ酸化)の処理条件をまとめて示す。
次に、洗浄後のシュウ酸スカンジウムの結晶を炉に入れて2回目の焼成を、焼成温度900℃で2時間かけて行い、酸化スカンジウムを生成させた。そして、炉から取り出した酸化スカンジウムを分析した。
Claims (4)
- スカンジウムを含有する溶液にシュウ酸を用いてシュウ酸化処理を施し、得られたシュウ酸スカンジウムの結晶を400℃以上600℃以下の温度で焼成する第1焼成工程と、
焼成により得られたスカンジウム化合物を塩酸及び硝酸から選ばれる1種以上の溶液に溶解させて溶解液を得る溶解工程と、
前記溶解液にシュウ酸を用いてシュウ酸化処理を施し、シュウ酸スカンジウムの再沈殿物を生成させる再沈殿工程と、
得られた前記シュウ酸スカンジウムの再沈殿物を焼成して酸化スカンジウムを得る第2焼成工程と、を有する
高純度酸化スカンジウムの製造方法。 - 前記再沈殿工程では、前記溶解液の温度を40℃以上100℃未満に調整してシュウ酸化処理を施す
請求項1に記載の高純度酸化スカンジウムの製造方法。 - 前記第2焼成工程では、焼成温度を900℃以上として焼成する
請求項1又は2に記載の高純度酸化スカンジウムの製造方法。 - 前記スカンジウムを含有する溶液は、スカンジウムを含有する溶液に対してイオン交換処理及び/又は溶媒抽出処理を施して得られたものである
請求項1乃至3のいずれか1項に記載の高純度酸化スカンジウムの製造方法。
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