WO2017146034A1 - スカンジウムの回収方法 - Google Patents
スカンジウムの回収方法 Download PDFInfo
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- WO2017146034A1 WO2017146034A1 PCT/JP2017/006327 JP2017006327W WO2017146034A1 WO 2017146034 A1 WO2017146034 A1 WO 2017146034A1 JP 2017006327 W JP2017006327 W JP 2017006327W WO 2017146034 A1 WO2017146034 A1 WO 2017146034A1
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- scandium
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- chelate resin
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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
- 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
- C01F17/10—Preparation or treatment, e.g. separation or purification
- C01F17/17—Preparation or treatment, e.g. separation or purification involving a liquid-liquid extraction
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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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
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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
- C22B3/08—Sulfuric acid, other sulfurated 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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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 scandium recovery method, and more specifically, scandium contained in nickel oxide ore is efficiently recovered by combining ion exchange treatment with a chelate resin and solvent extraction treatment with a neutral extractant. It relates to a recovery method.
- Scandium is extremely useful as an additive for high-strength alloys and as an electrode material for fuel cells. However, since the production amount is small and expensive, it has not been widely used.
- nickel oxide ores such as laterite or limonite ore contain a small amount of scandium.
- nickel oxide ore since nickel oxide ore has a low nickel-containing grade, it has not been industrially used as a nickel raw material for a long time. Therefore, there has been little research on industrial recovery of scandium from nickel oxide ore.
- an HPAL process has been put into practical use, in which nickel oxide ore is charged into a pressure vessel together with sulfuric acid and heated to a high temperature of about 240 ° C. to 260 ° C. to solid-liquid separate into a leachate containing nickel and a leach residue. ing.
- impurities are separated by adding a neutralizing agent to the obtained leachate, and then nickel can be recovered as nickel sulfide by adding a sulfurizing agent.
- the nickel nickel compound can be obtained by processing the obtained nickel sulfide in the existing nickel smelting process.
- Patent Document 5 a method of recovering scandium from an acidic solution obtained by a hydrometallurgical treatment of nickel oxide ore by a solvent extraction process has also been proposed (see Patent Document 5).
- 2-ethylhexyl sulfone is added to a scandium-containing solution in an aqueous phase containing at least one of iron, aluminum, calcium, yttrium, manganese, chromium, and magnesium.
- An organic solvent obtained by diluting acid-mono-2-ethylhexyl with kerosene is added, and the scandium component is extracted into the organic solvent.
- the chelating resin is used alone, the distribution of iron, aluminum, chromium, etc. into the eluent is very small, but these impurities are contained in the raw material in large quantities, so that separation is necessary. Multiple adsorption and elution operations are required.
- the adsorption and elution behavior of a plurality of impurities contained in a very small amount is inferior to that of scandium, it is very difficult to separate due to high distribution in the eluent.
- the present invention has been proposed in view of the above situation, and an object of the present invention is to provide a scandium recovery method that enables simple and efficient recovery of high-grade scandium from nickel oxide ore.
- the inventors of the present invention have made extensive studies to solve the above-described problems.
- scandium contained in nickel oxide ore was separated with chelate resin, and scandium acid solution obtained by dissolving hydroxide precipitate obtained from scandium eluate with acid solution was subjected to solvent extraction, and produced by the solvent extraction. It has been found that high-quality scandium can be easily and efficiently obtained by roasting the scandium-containing material obtained from the extracted residue, and the present invention has been completed. That is, the present invention provides the following.
- the first invention of the present invention is a leaching step of leaching a nickel oxide ore containing scandium with sulfuric acid under high temperature and high pressure to obtain a leaching solution and a leaching residue, and adding a neutralizing agent to the leaching solution.
- the chelate resin is a resin having iminodiacetic acid as a functional group
- the ion exchange step contacts the post-sulfurization solution with the chelate resin.
- An adsorption step for adsorbing the scandium to the chelate resin, and contacting the chelate resin that adsorbs scandium in the adsorption step with a sulfuric acid solution of 0.1N or less to remove aluminum adsorbed on the chelate resin in the adsorption step An aluminum removal step, a scandium elution step of contacting the chelate resin that has undergone the aluminum removal step with a sulfuric acid solution of 0.3N or more and less than 3N to obtain the scandium eluent, and a chelate resin that has undergone the scandium elution step with 3N or more To remove the chromium adsorbed on the chelate resin in the adsorption step.
- a chromium removal process for adsorbing the scandium to the chel
- the pH of the scandic acid solution is maintained in the range of 1.0 to 2.5, This is a method for recovering scandium, wherein the scandium acid solution is brought into contact with the neutral extractant.
- the solvent extraction step comprises mixing the scandate solution and an organic solvent containing the neutral extractant.
- An extraction step in which an impurity element other than scandium is extracted and separated into an extracted organic solvent and an extraction residue, and an acid solution having a concentration of 1.0 mol / l to 5.0 mol / l is mixed in the extracted organic solvent
- a method for recovering scandium comprising a back extraction step of obtaining an extract.
- a scandium acid solution is obtained by adding a nitric acid solution to the scandium hydroxide and dissolving the acid. This is a scandium recovery method for obtaining a scandium nitric acid solution.
- a scandic acid solution is obtained by adding a hydrochloric acid solution to the scandium hydroxide and dissolving the acid. This is a scandium recovery method for obtaining a scandium hydrochloric acid solution.
- the chloride concentration of the scandium hydrochloric acid solution obtained in the dissolution step is 2.0 mol / l or more and 6.0 mol. This is a method for recovering scandium, which is adjusted to be not more than 1 / l and the scandium hydrochloric acid solution is brought into contact with the neutral extractant.
- the eighth invention of the present invention is the invention according to any one of the first to seventh inventions, wherein the scandium recovery step is performed at a rate of 5.0 mol / l or more to the extraction residual liquid obtained in the solvent extraction step. Obtained by adding sodium hydroxide at a concentration of 0.0 mol / l or less to obtain a scandium hydroxide precipitate and dissolving the obtained scandium hydroxide precipitate with sulfuric acid or hydrochloric acid.
- a scandium recovery method comprising a step of adding oxalic acid to a solution to obtain scandium oxalate crystals and a step of firing the scandium oxalate crystals.
- high-quality scandium can be easily and efficiently recovered from nickel oxide ore.
- actinide elements when actinide elements are contained in the raw material nickel oxide ore, these can be effectively separated from scandium.
- present embodiments specific embodiments of the present invention (hereinafter referred to as “present embodiments”) will be described in detail with reference to the drawings.
- present invention is not limited to the following embodiments, and The present invention can be implemented with appropriate modifications within the scope not changing the gist of the invention.
- FIG. 1 is a flowchart for explaining a scandium recovery method according to the present embodiment.
- This scandium recovery method neutralizes the leachate obtained by leaching nickel oxide ore with an acid such as sulfuric acid, and from the hydroxide containing scandium, uranium, and thorium obtained by the neutralization treatment.
- the scandium is separated from uranium and thorium, and only scandium is recovered simply and efficiently with high purity.
- the scandium recovery method includes a leaching step S1 in which nickel oxide ore containing scandium is leached with an acid such as sulfuric acid under high temperature and high pressure to obtain a leaching solution and a leaching residue.
- a neutralization step S2 to obtain a neutralized starch and a neutralized solution by adding a neutralizing agent; and a sulfurization step S3 to obtain a nickel sulfide and a post-sulfurized solution by adding a sulfiding agent to the neutralized solution;
- the scandium in the post-sulfurization solution is adsorbed on the chelate resin, and an ion exchange step S4 to obtain a scandium eluate, and alkali is added to the scandium eluate and the scandium hydroxide
- a dissolution step S5 in which an acid solution of hydrochloric acid or nitric acid solution is added to the scandium
- Extracting and separating impurity elements other than scandium by contacting them to obtain a solvent extraction step S6 for obtaining an extract residue containing scandium, and generating scandium oxalate contained in the extract solution, and roasting the scandium oxalate And a scandium recovery step S7 for obtaining scandium oxide.
- ion exchange step ion exchange step
- solvent extraction step solvent extraction step
- a scandium-containing starch is produced from the scandium eluent, and the starch is dissolved with an acid solution of hydrochloric acid or nitric acid to obtain a scandium acid solution (dissolution step).
- the acid-dissolved solution is subjected to solvent extraction, and oxalic acid is added to the extracted residue that has not been extracted by solvent extraction to obtain scandium oxalate crystals.
- impurities including uranium and thorium can be separated with higher quality, and even from a raw material containing many impurities such as nickel oxide ore, it is easy to use with compact equipment.
- stable scandium recovery operation can be performed.
- leaching step S1 nickel oxide ore containing scandium is charged together with an acid such as sulfuric acid into a high-temperature pressurized container (autoclave) or the like in a high-temperature and high-pressure environment of 240 ° C to 260 ° C. Then, the nickel oxide ore is leached with an acid while performing a stirring treatment to produce a leaching slurry containing a leaching solution and a leaching residue.
- an acid such as sulfuric acid into a high-temperature pressurized container (autoclave) or the like in a high-temperature and high-pressure environment of 240 ° C to 260 ° C.
- nickel oxide ore examples include so-called laterite ores such as limonite ore and saprolite ore.
- Laterite ore usually has a nickel content of 0.8% to 2.5% by weight and is contained as a hydroxide or siliceous clay (magnesium silicate) mineral.
- These nickel oxide ores contain many components such as aluminum, chromium and iron in addition to valuable metals such as nickel, cobalt and scandium.
- the leaching slurry comprising the obtained leaching solution and the leaching residue is washed, and solid-liquid separation is performed into the leaching solution containing nickel, cobalt, scandium, and the like and the leaching residue that is hematite.
- the solid-liquid separation process for example, after the leaching slurry is mixed with a cleaning liquid, the solid-liquid separation process is performed by a solid-liquid separation facility such as a thickener using a flocculant supplied from a flocculant supply facility or the like. Specifically, the leaching slurry is first diluted with a cleaning liquid, and then the leaching residue in the slurry is concentrated as a thickener sediment.
- solid-liquid separation tanks such as thickeners connected in multiple stages and perform solid-liquid separation while washing the leaching slurry in multiple stages.
- Neutralization step S2 a neutralizing agent is added to the leachate obtained in the above-described leaching step S1 to adjust the pH, and the neutralized starch containing the impurity element and the post-neutralization solution are added. obtain. Due to the neutralization treatment in the neutralization step S2, valuable metals such as scandium and nickel are included in the post-neutralization solution, and most of impurities such as iron and aluminum become neutralized starch.
- neutralizing agent conventionally known neutralizing agents can be used, and examples thereof include calcium carbonate, slaked lime, and sodium hydroxide.
- the pH is adjusted to a range of 1 to 4 and more preferably to a range of 1.5 to 2.5 while suppressing oxidation of the separated leachate. preferable. If the pH is less than 1, neutralization becomes insufficient, and there is a possibility that the neutralized starch and the liquid after neutralization cannot be separated. On the other hand, when the pH exceeds 4, not only impurities such as aluminum but also valuable metals such as scandium and nickel may be contained in the neutralized starch.
- a sulfide containing nickel and cobalt with a small amount of impurity components is blown into the obtained post-neutralized solution by blowing a sulfiding agent such as hydrogen sulfide gas, sodium sulfide or sodium hydrogen sulfide. (Nickel / cobalt mixed sulfide) and a post-sulfurization solution containing scandium and the like by stabilizing the nickel concentration at a low level.
- a sulfiding agent such as hydrogen sulfide gas, sodium sulfide or sodium hydrogen sulfide.
- the nickel / cobalt mixed sulfide slurry is subjected to a sedimentation separation process using a sedimentation apparatus such as a thickener, and the nickel / cobalt mixed sulfide is separated and recovered from the bottom of the thickener.
- the post-sulfurization solution is overflowed and recovered.
- the obtained post-sulfurization solution is a sulfuric acid solution.
- a scandium salt or oxide is obtained, and this is roasted. It is also possible to obtain a scandium oxide solid.
- the concentration of scandium contained in the above-described leachate and post-sulfurization solution is generally several tens to 100 mg / l, which is generally dilute, in order to separate other impurities present at a higher concentration than scandium.
- the scandium contained in the post-sulfurization solution is converted to the chelate resin by contacting the post-sulfurization solution obtained by the above-described wet smelting treatment of nickel oxide ore with the chelate resin. To obtain a scandium eluent from which impurity components are removed.
- the liquid after sulfidation in addition to the target scandium, there are aluminum and chromium remaining in the solution (the liquid after sulfidation) without being sulfidized by the sulfidation treatment in the sulfidation step S3, and in some cases, a small amount of uranium and thorium. include. From this, it is preferable to remove the impurities and concentrate scandium to produce a scandium eluent when neutralizing the post-sulfurization solution, which is an acidic solution, to produce a hydroxide.
- ion-exchange process S4 which makes a post-sulfurization liquid contact chelate resin, and adsorb
- a 0.1N or lower sulfuric acid solution is brought into contact with the chelate resin, an aluminum removal step S42 for removing the aluminum adsorbed on the chelate resin in the adsorption step S41, and a sulfuric acid of 0.3N or more and 3N or less on the chelate resin that has undergone the aluminum removal step S42
- Scandium elution step S43 for obtaining a scandium eluent by contacting the solution, and removal of chromium adsorbed on the chelate resin in the adsorption step S41 by bringing a sulfuric acid solution of 3N or more into contact with the chelate resin that has undergone the scandium elution step S43 It is preferable that step S44 is included.
- the sulfidized solution is brought into contact with the chelate resin to adsorb scandium to the chelate resin.
- chelate resin it does not specifically limit as chelate resin,
- resin which has iminodiacetic acid it is preferable to use resin which has iminodiacetic acid as a functional group.
- the lower the pH range of the solution the smaller the amount of impurities contained in the nickel oxide ore. Therefore, the adsorption
- the pH of the solution is less than 2, not only the amount of impurities adsorbed but also the amount of scandium adsorbed may be reduced.
- the chelate resin that has adsorbed scandium in the adsorption step S41 is preferably brought into contact with a sulfuric acid solution of 0.1 N or less to remove the aluminum adsorbed on the chelate resin.
- the pH of the sulfuric acid solution When removing aluminum adsorbed on the chelate resin, it is preferable to maintain the pH of the sulfuric acid solution in the range of 1 to 2.5, and more preferably in the range of 1.5 to 2.0. If the pH of the sulfuric acid solution is less than 1, not only aluminum but also scandium may be removed from the chelate resin. On the other hand, if the pH of the sulfuric acid solution exceeds 2.5, aluminum may not be properly removed from the chelate resin.
- a scandium eluate is obtained by bringing the chelate resin that has undergone the aluminum removal step S42 into contact with a sulfuric acid solution that is preferably 0.3 N or more and less than 3 N.
- the normality of the sulfuric acid solution used as the eluent in the range of 0.3N or more and less than 3N, more preferably in the range of 0.5N or more and less than 2N. preferable. If the normality of the sulfuric acid solution is 3N or more, not only scandium but also chromium may be included in the scandium eluent. On the other hand, if the normality of the sulfuric acid solution is less than 0.3 N, scandium may not be appropriately removed from the chelate resin.
- the chelate resin that has undergone the scandium elution step S43 is preferably brought into contact with a 3N or higher sulfuric acid solution to remove chromium adsorbed on the chelate resin.
- iron may be contained as an impurity in the leachate obtained from nickel oxide ore.
- the chelate resin adsorbed with scandium was adsorbed to the chelate resin by bringing a sulfuric acid solution having a normality smaller than that of the sulfuric acid solution used in the aluminum removal step S42 into contact therewith. It is preferable to remove iron.
- the pH of the sulfuric acid solution When removing iron adsorbed on the chelate resin, it is preferable to maintain the pH of the sulfuric acid solution in the range of 1 to 3. If the pH of the sulfuric acid solution is less than 1, not only iron but also scandium may be removed from the chelate resin. On the other hand, if the pH of the sulfuric acid solution exceeds 3, iron may not be properly removed from the chelate resin.
- a neutralizing agent is added to the scandium eluent obtained in the scandium elution step S43, and the pH is preferably in the range of 2 to 4, more preferably 2.7 to 3.
- the pH is preferably in the range of 1 to 2.5, more preferably pH 2. In the range of 1.7 or more and 2.3 or less centering on (step S103).
- a pH-adjusted solution of the scandium eluent is obtained, and the treatment in the ion exchange step S4 described above is performed again using the pH-adjusted solution.
- the quality of the recovered scandium can be further enhanced by re-adsorbing the obtained scandium eluent to the chelate resin and repeating the treatment in the ion exchange step S4.
- the redox potential (ORP) exceeds 200 mV and is 300 mV or less with the silver / silver chloride electrode as the reference electrode. It is preferable to carry out so that it may be maintained in the range. If the ORP is 200 mV or less, the sulfur content derived from the added sulfiding agent may be precipitated as a fine solid. Then, the filter cloth is clogged by the filtration treatment after sulfidation, causing the efficiency of solid-liquid separation to deteriorate and reducing productivity, and clogging and liquid in the resin tower when re-flowing through the chelate resin. This may cause uneven flow and prevent uniform liquid flow. On the other hand, if the ORP exceeds 300 mV, there may be a problem that the remaining iron ions and the like are adsorbed on the resin and inhibit the adsorption of scandium.
- neutralizing agent added to the scandium eluent a conventionally known neutralizing agent can be used, and examples thereof include calcium carbonate.
- conventionally well-known thing can be used also about the reducing agent added after pH adjustment, For example, sulfur dioxide, hydrogen sulfide gas, sodium sulfide, sulfur dioxide gas, hydrazine, metallic iron etc. are mentioned.
- the chelate resin When the scandium eluent is re-adsorbed on the chelate resin, the chelate resin may be reused one already used or a new chelate resin. From the viewpoint of preventing impurity contamination, it is preferable to reuse the chelate resin that has undergone the chromium removal step S44 or to use a new chelate resin. In particular, by reusing the chelate resin that has undergone the chromium removal step S44, it is possible not only to prevent contamination of impurities, but also to reduce the amount of chelate resin used.
- the scandium eluent obtained in the scandium elution step S43 is treated again in the scandium elution step S43, that is, the treatment in which the obtained scandium eluent is brought into contact with the chelate resin that has undergone the aluminum removal step S42. It can also be done.
- the concentration of the scandium eluent can be increased by repeatedly performing the scandium elution step S43 using the scandium eluent.
- the number of times of repeating the scandium elution step S43 is preferably about 8 times or less.
- a dissolution step S5 is provided to generate a scandium precipitate contained in the scandium eluent to separate it from impurities.
- generates the extraction start liquid which uses for the solvent extraction of the following process is performed.
- a method for neutralizing hydroxide can be used as a method for concentrating scandium in the dissolution step S5, that is, a method for generating a scandium precipitate and separating it from impurities.
- neutralizing agent added to the scandium eluent conventionally known neutralizers can be used, and examples thereof include alkalis such as slaked lime and sodium hydroxide.
- alkalis such as slaked lime and sodium hydroxide.
- sodium hydroxide or the like it is preferable to use sodium hydroxide or the like as the neutralizing agent because gypsum is generated with the neutralizing agent containing Ca.
- pH when a neutralizing agent is added, It is preferable to adjust to the range of 8-9. If the pH is less than 8, neutralization becomes insufficient, and scandium in the scandium eluent may not be sufficiently recovered as a precipitate. On the other hand, when pH exceeds 9, since the usage-amount of a neutralizing agent increases, it is unpreferable at the point which increases cost.
- neutralization in the first stage is performed to precipitate only iron during the neutralization treatment with hydroxide, and the resulting precipitate is filtered and then neutralized in the second stage. It is effective to carry out stage neutralization.
- an acid solution specifically, an acid solution of either nitric acid or hydrochloric acid is added to the scandium hydroxide precipitate obtained by the hydroxylation neutralization treatment.
- the precipitate is dissolved to produce an acid solution of scandium.
- the scandium acid solution thus obtained is a processing target (extraction start solution) of the solvent extraction process in the solvent extraction step S6 of the next step.
- the concentration of the nitric acid solution is not particularly limited, but is 2.0 mol / l or more and 5.0 mol / l.
- the following range is preferable, and a range of 3.0 mol / l or more and 4.0 mol / l or less is more preferable.
- concentration of the hydrochloric acid solution is not specifically limited, What is necessary is just to set it as the density
- the precipitate when dissolving the precipitate with the acid solution, it is preferable to dissolve the precipitate in the vicinity of the solubility of the obtained precipitate.
- the scandium concentration can be arbitrarily selected, and the amount of liquid in the subsequent solvent extraction step S6, and thus the equipment scale can be reduced. In this respect, it is extremely preferable industrially.
- the dissolution step S5 subsequent to the ion exchange step S4
- impurities contained in the scandium eluent can be significantly removed, and the ion exchange step S4 and the next step can be performed.
- the man-hour concerning the solvent extraction step S6 can be reduced.
- the concentration of the extraction starting solution to be subjected to solvent extraction can be arbitrarily adjusted, the operation can be further improved by reducing the equipment investment by stabilizing the equipment scale in the solvent extraction step S6 and stabilizing the starting solution concentration. It can be further stabilized.
- Solvent extraction step S6 the scandium acid solution (extraction start solution) obtained by dissolving scandium hydroxide in hydrochloric acid or nitric acid solution in the dissolution step S5 described above is used as a neutral extractant. Solvent extraction treatment is performed by bringing them into contact with each other to obtain an organic solvent from which impurities have been extracted and an extraction residue containing scandium.
- solvent extraction process S6 for example, as shown in an example in FIG. 1, after mixing and mixing an organic solvent containing a scandium acid solution and an organic solvent containing a neutral extractant, extraction residue An extraction step S61 for obtaining a liquid, a scrubbing step S62 for separating and recovering scandium extracted into the extractant by mixing a hydrochloric acid or nitric acid solution of a predetermined concentration with the organic solvent after this extraction, and an organic solvent after washing It is preferable to have a back extraction step S63 in which a back extractant is added and the impurity element is back extracted from the organic solvent after the washing.
- extraction process In the extraction step S61, a scandium acid solution and an organic solvent containing a neutral extractant are mixed to selectively extract impurity elements other than scandium. By this extraction treatment, an organic solvent containing impurities and an extraction residual liquid with increased scandium purity are obtained.
- TBP tri-n-butyl phosphate
- uranium and thorium contained in the acid-dissolved acid solution with a nitric acid can be extracted and efficiently separated from scandium.
- uranium contained mainly in the solution can be extracted and efficiently separated from scandium.
- the extractant is preferably diluted with a hydrocarbon-based organic solvent or the like.
- a hydrocarbon-based organic solvent or the like for example, when TBP described above is used as a neutral extractant, the concentration of TBP in the organic solvent is 10% by volume or more and 50% by volume or less in consideration of the phase separation during extraction and back extraction. In particular, it is more preferably 15% by volume or more and 25% by volume or less, which is around 20% by volume.
- the volume ratio of the scandium acid solution and the organic solvent at the time of extraction is not particularly limited, but the organic solvent molar amount is 0.4 to 1.0 times the molar amount of metal in the scandium acid solution. It is preferable to be in the range of less than twice.
- the extraction treatment it is preferable to adjust and maintain the pH of the scandate solution in the range of 1.0 to 2.5. If the pH of the scandate solution to be extracted is less than 1.0, when uranium is contained in the solution, extraction of the uranium hardly progresses and the extraction and separation effect may be significantly reduced. There is. Moreover, there is a concern that the acidity of the scandic acid solution is too strong and the equipment is easily corroded.
- the pH of the scandate solution in the extraction treatment is more preferably adjusted and maintained in the range of 1.5 or more and 2.0 or less, whereby uranium contained in the solution more efficiently and effectively. Can be extracted.
- the chloride concentration (T-Cl concentration) of the hydrochloric acid solution during extraction is 2.0 mol / l or more. It is preferable to do.
- the extraction rate of uranium can be increased by performing the extraction treatment with a chloride concentration of 2.0 mol / l or more.
- the upper limit value of the chloride concentration is preferably 6.0 mol / l or less. If the chloride concentration of the hydrochloric acid acidic solution exceeds 6.0 mol / l, the coexisting chlorides such as iron ions become supersaturated and crystals are deposited, which may cause clad formation and hinder operation.
- Adjustment of the chloride concentration in the hydrochloric acid acidic solution is preferably performed by adding an alkali metal salt such as sodium chloride or potassium chloride.
- an alkali metal salt such as sodium chloride or potassium chloride.
- the chloride concentration is adjusted using hydrochloric acid, the acidity of the hydrochloric acid acidic solution is too strong, and the pH deviates below the preferred range (pH 1.0 or more and 2.5 or less) as described above. There is a possibility that the extraction / separation effect is reduced.
- the temperature condition in the extraction process is not particularly limited, and a relatively high temperature is preferable in terms of extraction efficiency, but if it is too high, hydrochloric acid and nitric acid constituting the acid solution will volatilize or ignite. There is also the danger of doing. Therefore, it is preferable to set the temperature in the range of about 40 ° C. to 50 ° C.
- the scrubbing step S62 is provided to wash the organic solvent, and by separating the slight scandium extracted by the extractant, scandium can be separated in the washing liquid, and the recovery rate of scandium is further increased. Can be increased.
- the solution (cleaning solution) used for scrubbing is not particularly limited, and for example, a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, or the like can be used.
- the cleaning solution recovered by scrubbing is purified together with the extraction residue after extraction. Used for scandium recovery. Therefore, for scrubbing, it is preferable to use a nitric acid solution or a hydrochloric acid solution of the same liquid type as the scandiacid solution that is the extraction source solution as the cleaning solution.
- a hydrochloric acid-based cleaning solution for the hydrochloric acid acidic solution
- a nitric acid-based cleaning solution for the nitric acid acidic solution
- cleaning solutions also from a viewpoint of preventing the hydrolysis of scandium by the raise of pH.
- a solution in which a sulfate soluble in water is added can also be used.
- cleaning solution It is preferable to set it as the range of 1.0 mol / l or more and 5.0 mol / l or less. More specifically, for example, when a nitric acid solution is used as the cleaning solution, a concentration range of 2.0 mol / l or more and 5.0 mol / l or less is preferable, and a concentration range of 3.0 mol / l or more and 4.0 mol / l or less is preferable. A concentration range is more preferred.
- the impurity element is back extracted from the organic solvent from which the impurity element has been extracted. Specifically, in the back extraction process, a reverse extraction solution (back extraction start liquid) is added to and mixed with an organic solvent containing an extractant, thereby causing a reaction opposite to the extraction process in the extraction step S61 to cause impurities. The element is back-extracted to obtain a back-extracted solution containing the impurity element.
- a reverse extraction solution back extraction start liquid
- the impurity element is selectively extracted using a neutral extractant such as TBP as the extractant.
- a neutral extractant such as TBP
- the reverse extraction solution is similarly added to the extractant after the scrubbing and mixed. An extraction process can be performed.
- the neutral extractant after separating the impurity elements by adding a back-extraction solution such as pure water to the extractant after extraction or after scrubbing in this way and performing back-extraction treatment is again
- the extractant used in the extraction process in the extraction step S61 can be used repeatedly.
- scandium recovery step S7 scandium is recovered from the extracted residue containing scandium obtained in the solvent extraction step S6.
- the scandium recovery step S7 after the scandium salt contained in the extraction residual liquid is generated, the solid scandium salt is roasted to generate scandium oxide to recover scandium.
- the scandium recovery step S7 includes an oxalate formation step S71 in which oxalic acid is added to the extraction residual liquid obtained in the solvent extraction step S6 to obtain scandium oxalate crystals, And roasting step S72 for firing scandium oxalate crystals.
- a hydrochloric acid acidic solution (scandium hydrochloric acid solution) is used as a scandium solution
- uranium is mainly extracted by a solvent extraction process using a neutral extractant, and the separation between thorium and scandium is slightly insufficient. It becomes.
- oxalic acid is added to the obtained extracted residue to precipitate scandium as oxalate, thereby effectively separating it from thorium that does not form the oxalate precipitate. it can.
- the oxalate forming step S71 is a step of generating a scandium precipitate as described above, and oxalic acid is added to the extraction residue (post-extraction solution) obtained in the solvent extraction step S6 to obtain white crystals of scandium oxalate. It is the process of depositing and precipitating as a solid and separating.
- the amount of oxalic acid added is not particularly limited, but it is preferably added in an amount that is 1 to 2.5 times the equivalent amount required to precipitate scandium in the extraction liquid as oxalate, More preferably, the amount is 1.05 times or more and 2.0 times or less. If the amount added is less than 1 times the equivalent amount required for precipitation, there is a possibility that the entire amount of scandium in the extracted residue cannot be recovered. On the other hand, when the added amount exceeds 2.5 times the equivalent amount required for precipitation, the solubility of scandium oxalate increases, so that scandium is re-dissolved to lower the recovery rate or decompose excess oxalic acid. For this reason, the amount of oxidizing agent such as sodium hypochlorite increases.
- the equivalent amount required for precipitating scandium as oxalate is the amount (multiplier) of scandium when oxalic acid and scandium react as shown in the following formula (i) to produce scandium oxalate.
- the pH of the extraction liquid at the time of the oxalate reaction is not particularly limited.
- the pH is preferably in the range of about 0 or more and about 2 or less, and is about 1 or so. More preferably. If the pH is too low, such as less than 0, the solubility of scandium oxalate increases and the scandium recovery rate may decrease. On the other hand, if the pH exceeds 2, impurities contained in the extraction residual liquid also form a precipitate, which causes a decrease in scandium purity.
- the pH is preferably in the range of about 0 or more and 0.5 or less. If the pH is too low, such as less than 0, the solubility of scandium oxalate increases and the scandium recovery rate may decrease.
- the chloride concentration can be adjusted by using an alkali metal salt such as sodium chloride or potassium chloride, but the amount of sodium and potassium adhering to scandium oxalate also increases. It must be removed by washing with water.
- the pH in the case of using an acidic solution of hydrochloric acid is preferably 0.5 or less, which is lower than that in the case of an acidic solution of nitric acid.
- a neutralization treatment is performed on the extraction residue containing scandium obtained in the solvent extraction step S6 to generate scandium precipitates, May be removed.
- a predetermined concentration of sodium hydroxide is added to the extraction residue obtained in the solvent extraction step S6 to form a scandium hydroxide precipitate (in the extraction residue). Sum processing). Next, sulfuric acid or hydrochloric acid is added to the obtained scandium hydroxide precipitate to dissolve the precipitate, thereby obtaining a scandium solution (hydrochloric acid dissolution treatment).
- concentration of the sodium hydroxide added in a extraction liquid neutralization process It is preferable that it is the range of 5 mol / l or more and 8 mol / l or less. Since scandium hydroxide is produced as a precipitate when the pH of the solution (extracted liquid) is 8 or higher, its hydroxylation is taken into consideration when both the formation of the precipitate and the suppression of excess sodium hydroxide are taken into consideration. It is preferable to add sodium so that the pH of the extraction residual liquid is 8 or more and 9 or less. In such a point, when the concentration of sodium hydroxide to be added is in the range of 5 mol / l or more and 8 mol / l or less, a scandium hydroxide precipitate can be efficiently generated.
- the oxalate treatment (oxalate formation step S71) described above can be performed on the scandium solution obtained by performing the neutralization treatment in this manner. Thereby, scandium with higher purity can be recovered.
- roasting step S72 the scandium oxalate precipitate obtained in the oxalate forming step S71 is washed with water, dried and roasted to generate scandium oxide. By performing the roasting treatment in this manner, scandium can be recovered as extremely high-quality scandium oxide.
- the conditions for the baking process in the baking process S72 are not particularly limited.
- the dried scandium oxalate precipitate may be placed in a tubular furnace and heated at about 900 ° C. for about 2 hours.
- a continuous furnace such as a rotary kiln because drying and roasting can be performed in the same apparatus.
- Example 1 [Leaching step S1] First, nickel oxide ore is charged into an autoclave together with concentrated sulfuric acid, and a leaching slurry containing valuable metals such as scandium and nickel is produced over one hour under a temperature condition of 245 ° C. Solid-liquid separation was performed on the leachate contained and the leach residue.
- Neutralization step S2 Next, neutralization was performed by adding calcium carbonate (neutralizing agent) to the leachate obtained by separation. By this neutralization treatment, a post-neutralization solution containing valuable metals such as scandium and nickel and a neutralized starch containing most of impurities including aluminum were obtained.
- calcium carbonate neutralizing agent
- the adsorbent solution having the composition shown in Table 1 was passed through a column packed with a chelate resin (product name: Diaion CR11, manufactured by Mitsubishi Chemical Corporation) having iminodiacetic acid as a functional group.
- the liquid temperature at the time of liquid supply was 60 ° C.
- solvent extraction step S6 extraction step S61
- extraction step S61 solvent extraction treatment was performed using 103 liters of scandium nitric acid solution having the composition shown in Table 3 as an extraction starting solution.
- the extraction starting solution neutral extractant tri-n-butyl phosphate (trade name: TBP, manufactured by Daihachi Chemical Co., Ltd.) and organic solvent Teclean N20 (JX Nippon Mining Corporation) And 20.6 liters of an organic solvent adjusted to 50% by volume using the product, and stirred at room temperature for 60 minutes.
- TBP neutral extractant tri-n-butyl phosphate
- organic solvent Teclean N20 JX Nippon Mining Corporation
- the obtained scandium oxide was analyzed by emission spectroscopic analysis, and the reduction rate of thorium (Th) as an impurity in scandium oxide recovered through the above-described solvent extraction treatment was examined.
- the reduction rate of thorium the scandium eluate obtained in the ion exchange step S4 was treated in the dissolution step S5 to obtain a scandium nitric acid solution without undergoing the above-described solvent extraction treatment. Calculation was made based on the amount of thorium in scandium oxide obtained by the roasting treatment. Table 6 below shows the calculation results of the quality and reduction rate of thorium in scandium oxide.
- Example 2 In the same manner as in Example 1, nickel oxide ore was leached with sulfuric acid, and the resulting sulfidized solution was passed through a chelate resin, sodium hydroxide was added to the scandium eluate eluted from the chelate resin, and the scandium water An oxidized precipitate was obtained.
- Example 2 hydrochloric acid and sodium chloride were added to and dissolved in the obtained scandium hydroxide precipitate to obtain a hydrochloric acid acidic solution (scandium hydrochloric acid solution).
- a hydrochloric acid acidic solution a part of the components was added as a reagent to prepare extraction starting liquids having the compositions shown in Table 7 below, which were designated as starting liquids A to H.
- the chloride concentration (T-Cl) at the time of extraction is the total of the amounts of Cl calculated from the analytical values of scandium, aluminum, iron, uranium, and thorium and the form considered to be present in the hydrochloric acid acidic solution. From the amount of Cl contained in hydrochloric acid and sodium chloride added during the adjustment.
- Table 8 shows the composition of the extracted residue obtained by the solvent extraction treatment of the hydrochloric acid acidic solution.
- the chloride concentration (T-Cl) at the time of extraction is also shown as the concentration (mol / l) in the extraction residual liquid.
- FIG. 2 is a graph showing the relationship of the extraction rate to the chloride concentration in each element.
- the obtained scandium oxalate precipitate was taken out by solid-liquid separation, and the contents of thorium and uranium in the precipitate were analyzed.
- the analysis values are shown in Table 11 below.
- Comparative example 1 As Comparative Example 1, an extraction starting solution having the composition shown in A to D of Table 7 was subjected to solvent extraction in the same manner as in Example 1. Specifically, these extraction starting solutions were mixed with TBP as a neutral extractant under the same conditions as in Example 1, and subjected to extraction treatment by stirring with a stirrer at room temperature for 15 minutes. Next, after completion of stirring, the mixture was allowed to stand and extracted using a separatory funnel, and then separated into an organic solvent and a residual extraction liquid, and each was analyzed by ICP.
- Table 12 below shows the composition of the extracted residue obtained by the solvent extraction treatment.
- the chloride concentration at the time of extraction is also shown as the concentration (mol / l) in the extraction residual liquid.
- Table 13 and FIG. 2 show the extraction rates calculated in the same manner as in Example 1. As described above, FIG. 2 is a graph showing the relationship of the extraction rate to the chloride concentration in each element.
- the uranium extraction rate becomes as low as 30% or less.
- the uranium extraction rate is 60% or more, and when the T-Cl concentration exceeds 2.5 mol / l, uranium can be extracted at a rate of 92% or more. Can be separated effectively from scandium.
- Thorium in acidic hydrochloric acid solution could not be separated as significantly as uranium by solvent extraction treatment, but by combining oxalate treatment with the extracted residue, scandium was precipitated and was effective as thorium. Can be separated.
- Comparative example 2 As Comparative Example 2, a hydrochloric acid acidic solution having the same composition as the starting solution H shown in Table 7 used in Example 2 was used, and the hydrochloric acid acidic solution was directly treated without subjecting it to solvent extraction. An oxalate treatment was performed by adding an acid. The treatment conditions for oxalation were the same as in Example 1.
- Table 14 below shows analytical values of scandium oxalate obtained by the oxalate treatment.
- Table 14 shows the analysis value of scandium oxalate obtained by the oxalate treatment in Example 2 shown in Table 11 and the residual solution after solvent extraction in Comparative Example 1 (Comparative Example 1-3). The analysis value of scandium oxalate when the oxalate treatment is performed under the same conditions as in Example 2 is also shown.
- Comparative Example 3 As Comparative Example 3, a hydrochloric acid acidic solution having the same composition as the starting solution H whose composition is shown in Table 7 used in Example 2 was used, and the hydrochloric acid acidic solution was not subjected to solvent extraction treatment and directly hydroxylated. Sodium was added to form a precipitate of scandium-containing hydroxide (scandium hydroxide). Thereafter, the scandium hydroxide obtained as it was was analyzed without oxalate treatment. Table 15 below shows analytical values of the scandium hydroxide.
- the thorium quality in scandium hydroxide was 1000 ppm.
- the thorium quality and uranium quality are improved by performing neither solvent extraction nor oxalate treatment. Therefore, scandium could not be efficiently separated, and scandium could not be effectively purified.
- Comparative Example 4 As Comparative Example 4, a hydrochloric acid acidic solution having the same composition as the starting solution H having the composition shown in Table 7 above, which was used in Example 2, was subjected to a solvent extraction treatment under the same conditions as in Example 2, and then obtained. Sodium hydroxide was added to the extracted residual liquid to form a precipitate of scandium-containing hydroxide (scandium hydroxide). Thereafter, the scandium hydroxide obtained as it was was analyzed without performing the oxalate treatment. Table 16 below shows analytical values of the scandium hydroxide.
- the thorium quality in scandium hydroxide was 950 ppm.
- uranium thorium could not be effectively reduced only by solvent extraction treatment, although oxalate treatment was effective for separation of thorium, although it could be reduced to 30 ppm by performing solvent extraction treatment. was found to be necessary.
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Abstract
Description
図1は、本実施の形態に係るスカンジウムの回収方法を説明するためのフロー図である。このスカンジウムの回収方法は、ニッケル酸化鉱石を硫酸等の酸により浸出して得られた浸出液を中和し、その中和処理により得られた、スカンジウム、ウラン、及びトリウムを含有する水酸化物から、スカンジウムと、ウラン及びトリウムとを分離して、スカンジウムのみを簡便に且つ効率よく、かつ高純度に回収するものである。
以下、図1に示すフロー図を参照にしながら、スカンジウムの回収方法の各工程についてより詳細に説明する。
浸出工程S1では、スカンジウムを含有するニッケル酸化鉱石を硫酸等の酸と共に高温加圧容器(オートクレーブ)等に装入し、240℃~260℃の高温で且つ高圧の環境下において、撹拌処理を施しながら酸によりニッケル酸化鉱石を浸出して浸出液と浸出残渣とを含む浸出スラリーを生成する。なお、浸出工程S11における処理は、従来知られているHPALプロセスに従って行えばよく、例えば特許文献1に記載されている。
中和工程S2では、上述した浸出工程S1により得られた浸出液に中和剤を添加してpHを調整し、不純物元素を含む中和澱物と中和後液とを得る。中和工程S2における中和処理により、スカンジウムやニッケル等の有価金属は中和後液に含まれるようになり、鉄、アルミニウムをはじめとした不純物の大部分が中和澱物となる。
硫化工程S3では、中和工程S2により得られた中和後液に硫化剤を添加してニッケル硫化物と硫化後液とを得る。硫化工程S3における硫化処理により、ニッケル、コバルト、亜鉛等は硫化物となり、スカンジウム等は硫化後液に含まれることになる。
イオン交換工程S4では、上述したニッケル酸化鉱石の湿式製錬処理により得られた硫化後液をキレート樹脂に接触させることによって、その硫化後液中に含まれるスカンジウムをキレート樹脂に吸着させ、不純物成分を除去したスカンジウム溶離液を得る。
吸着工程S41では、硫化後液をキレート樹脂に接触させてスカンジウムをキレート樹脂に吸着させる。キレート樹脂としては、特に限定されないが、例えばイミノジ酢酸を官能基とする樹脂を用いることが好ましい。
アルミニウム除去工程S42では、吸着工程S41でスカンジウムを吸着したキレート樹脂に、好ましくは0.1N以下の硫酸溶液を接触させることによって、そのキレート樹脂に吸着したアルミニウムを除去する。
スカンジウム溶離工程S43では、アルミニウム除去工程S42を経たキレート樹脂に、好ましくは0.3N以上3N未満の硫酸溶液を接触させることによって、スカンジウム溶離液を得る。
クロム除去工程S44では、スカンジウム溶離工程S43を経たキレート樹脂に、好ましくは3N以上の硫酸溶液を接触させることによって、キレート樹脂に吸着したクロムを除去する。
また、図示していないが、ニッケル酸化鉱石から得られた浸出液中には不純物として鉄が含まれている場合がある。この場合、アルミニウム除去工程S42に先立ち、スカンジウムが吸着したキレート樹脂に、アルミニウム除去工程S42で使用する硫酸溶液の規定度よりも小さい規定度の硫酸溶液を接触させることによって、そのキレート樹脂に吸着した鉄を除去することが好ましい。
また、必須の態様ではないが、得られたスカンジウム溶離液をキレート樹脂に再吸着させる処理を施すことが好ましい。
また、スカンジウム溶離工程S43によって得られたスカンジウム溶離液に対して、再びスカンジウム溶離工程S43における処理、すなわち、アルミニウム除去工程S42を経たキレート樹脂に対して、得られたスカンジウム溶離液を接触させる処理を行うこともできる。このように、スカンジウム溶離液を用いてスカンジウム溶離工程S43を繰り返し行うことで、スカンジウム溶離液の濃度を高めることができる。
次に、上述したイオン交換工程S4に続いて、溶解工程S5を設けて、スカンジウム溶離液に含まれるスカンジウムの沈殿物を生じさせて不純物と分離し、さらにこの沈殿物を酸溶液で溶解して、次工程の溶媒抽出に供する抽出始液を生成させる処理を行う。
スカンジウム溶離液に対する水酸化中和処理では、上述したイオン交換工程S4で得られたスカンジウム溶離液に対して中和剤を添加することによって中和処理を施し、スカンジウムの水酸化物沈殿と不純物成分を含む中和後液とを生成させる。
次に、本実施の形態においては、水酸化中和処理により得られた水酸化スカンジウムの沈殿物に対して、酸溶液、具体的には、硝酸又は塩酸のいずれかの酸溶液、を添加することによってその沈殿物を溶解し、スカンジウムの酸溶解液を生成させる。本実施の形態に係るスカンジウムの回収方法においては、このようにして得られたスカンジウム酸溶解液が次工程の溶媒抽出工程S6における溶媒抽出処理の処理対象(抽出始液)となる。
溶媒抽出工程S6では、上述した溶解工程S5にて水酸化スカンジウムを塩酸もしくは硝酸溶液で溶解して得られたスカンジウム酸溶解液(抽出始液)を、中性抽出剤に接触させることによって溶媒抽出処理を行い、不純物を抽出した有機溶媒とスカンジウムを含有する抽残液とを得る。
抽出工程S61では、スカンジウム酸溶解液と中性抽出剤を含む有機溶媒とを混合して、スカンジウム以外の不純物元素を選択的に抽出する。この抽出処理により、不純物を含有する有機溶媒と、スカンジウムの純度を高めた抽残液とを得る。
上述した抽出工程S61において、不純物を抽出させた有機溶媒中にスカンジウムが僅かに共存する場合には、抽出液を逆抽出する前に、その有機溶媒(有機相)に対してスクラビング(洗浄)処理を施し、スカンジウムを水相に分離させて抽出剤から回収することが好ましい(スクラビング工程S62)。
逆抽出工程S63では、不純物元素を抽出した有機溶媒から不純物元素を逆抽出する。具体的に、逆抽出処理では、抽出剤を含む有機溶媒に逆抽出溶液(逆抽出始液)を添加して混合することによって、抽出工程S61における抽出処理とは逆の反応を生じさせて不純物元素を逆抽出し、その不純物元素を含む逆抽出後液を得る。
次に、スカンジウム回収工程S7において、溶媒抽出工程S6により得られたスカンジウムを含有する抽残液からスカンジウムを回収する。スカンジウム回収工程S7では、抽残液に含まれるスカンジウムの塩を生成させた後、その固体のスカンジウム塩を焙焼することによって酸化スカンジウムを生成させてスカンジウムを回収する。
シュウ酸塩化工程S71は、上述したようにスカンジウムの沈殿を生成させる工程であって、溶媒抽出工程S6で得られた抽残液(抽出後液)にシュウ酸を加えてシュウ酸スカンジウムの白色結晶の固体として析出、沈殿させて分離する工程である。
Sc2(SO4)3+3C2O4H2・2H2O
⇒Sc2(C2O4)3+3H2SO4 ・・・(i)
焙焼工程S72では、シュウ酸塩化工程S71で得られたシュウ酸スカンジウムの沈殿物を水で洗浄し、乾燥して、焙焼することにより酸化スカンジウムを生成させる。このようにして焙焼処理を施すことで、極めて高品位な酸化スカンジウムとしてスカンジウムを回収することができる。
[浸出工程S1]
先ず、ニッケル酸化鉱石を濃硫酸と共にオートクレーブに装入し、245℃の温度条件下で1時間かけてスカンジウムやニッケル等の有価金属を含有する浸出スラリーを生成させ、このスラリーから各種の有価金属を含有する浸出液と、浸出残渣とに固液分離した。
次に、分離して得られた浸出液に炭酸カルシウム(中和剤)を添加して中和処理を施した。この中和処理により、スカンジウムやニッケル等の有価金属を含有する中和後液と、アルミニウムをはじめとした不純物の大部分を含有する中和澱物とを得た。
次に、得られた中和後液に硫化水素ガス(硫化剤)を吹き込み、ニッケルやコバルト、亜鉛を硫化物とし、この硫化処理後の液である硫化後液と分離した。
(吸着工程S41)
次に、分離して得られた硫化後液に中和剤として消石灰を添加して溶液のpHを1.6に調整した。加えて、消石灰添加後の液には含まれていないか、あるいは含まれているとしてもその含有量がごく微量である元素の挙動を明らかにするため、一部の元素については試薬を添加して、下記表1に示す組成の吸着元液を得た。
次に、吸着処理後のキレート樹脂に、濃度0.1Nの硫酸溶液800リットルを毎分27リットル(SV=40となる)の流量で通液した。カラムから排出され残留したアルミニウムの多い洗浄液は、アルミニウム洗浄液として貯液し一部をサンプリングしてICPで分析した。その結果、分析値としては、Ni:7mg/l、Mg:1mg/l、Mn:4mg/l、Fe:1mg/l、Al:84mg/l、Sc:3mg/lであった。なお、Cr、Caの分析値は、測定可能な下限未満であった。
その後、キレート樹脂に、濃度1Nの硫酸溶液400リットルを毎分80リットル(SV=40となる)の流量で通液した。カラムから排出された溶離液は、スカンジウム溶離液として貯液し一部をサンプリングして分析した。下記表2にスカンジウム溶離液の分析結果を示す。なお、表中の「-」は、未分析又は測定可能な下限未満であったこと示す。
続いて、キレート樹脂に、濃度3Nの硫酸溶液80リットルを毎分2.6リットル(SV=40となる)の流量で通液した。カラムから排出された洗浄液は、クロム洗浄液として貯液し一部をサンプリングして分析した。その結果、分析値としては、Fe:2mg/l、Cr:30mg/lであった。なお、Ni、Mg、Mn、Al、Ca、Scの分析値は、測定可能な下限未満であった。
次に、表2に示す組成のスカンジウム溶離液に、水酸化ナトリウムを添加してpHを8~9に維持し、スカンジウムの水酸化物沈殿を生成させた。この水酸化物沈殿に硝酸溶液を添加して溶解し、キレート溶離液水酸化物溶解液(スカンジウム硝酸溶解液)を得た。下記表3に溶解液の組成を分析した結果を示す。なお、表中の「-」は、未分析又は測定可能な下限未満であったこと示し、例えば、Mg、Cr、Mn、Caの分析値は測定可能な下限未満であった。
(抽出工程S61)
次に、表3に示す組成のスカンジウム硝酸溶解液103リットルを抽出始液として溶媒出処理を行った。具体的には、その抽出始液と、中性抽出剤であるトリ-n-ブチルホスフェート(商品名:TBP,大八化学株式会社製)と有機溶剤であるテクリーンN20(JX日鉱日石株式会社製)とを用いて50体積%に調整した有機溶媒20.6リットルとを混合して室温で60分撹拌した。この溶媒抽出処理により、スカンジウムを除く不純物を含む抽出有機相と、抽出後液(抽残液)とを得た。なお、この抽出時には、クラッドが形成されることはなく、静置後の相分離も迅速に進行した。
次に、抽出工程S61で得られた20.6リットルの有機溶媒(抽出有機相)に対して、濃度3mol/lの硝酸溶液を、相比(O/A)が0.3の比率となる6.2リットルの量で混合し、10分間撹拌してスクラビング(洗浄)した。その後、静置して水相を分離し、有機相は再び濃度3mol/lの新たな硝酸溶液6.2リットルと混合して洗浄を繰り返し、同様にして水相を分離した。このような洗浄操作を合計3回繰り返した。
次に、洗浄後の抽出有機相に、純水を、相比O/A=1/0.3の比率となるように混合して20分撹拌し、静置して逆抽出後の有機相(有機溶媒)と逆水相(逆抽出後液)とに分離した。
(シュウ酸塩化工程S71)
次に、上述した溶媒抽出工程S6で得られた抽出後液(抽残液)に対して、その抽残液中に含まれるスカンジウム量に対して計算量で2倍となるシュウ酸・2水和物(三菱ガス社製)の結晶を添加して溶解し、60分撹拌混合してシュウ酸スカンジウムの白色結晶性沈殿を生成させた。
次に、得られたシュウ酸スカンジウムの沈殿物を吸引濾過し、純水を用いて洗浄した後、105℃で8時間乾燥させた。続いて、乾燥後のシュウ酸スカンジウムを管状炉に入れて850℃~900℃に維持して焙焼(焼成)処理を施し、酸化スカンジウムを得た。
実施例1と同様にして、ニッケル酸化鉱石を硫酸で浸出し、得られた硫化後液をキレート樹脂に通液し、キレート樹脂から溶離したスカンジウム溶離液に水酸化ナトリウムを添加してスカンジウムの水酸化沈殿物を得た。
比較例1として、上記表7のA~Dに示す組成の抽出始液を、実施例1と同様の方法で溶媒抽出に付した。具体的には、これら抽出始液を、実施例1と同様の条件で中性抽出剤であるTBPと混合し、常温で15分間かけて撹拌機で撹拌して抽出処理を施した。次いで、撹拌終了後、静置して分液ロートを用いて抽出後有機溶媒と抽残液とに分離し、それぞれをICPにより分析した。
比較例2として、実施例2にて用いた、上記表7に組成を示す始液Hと同組成の塩酸酸性溶液を用い、その塩酸酸性溶液に対して溶媒抽出処理を施さずに、直接シュウ酸を添加してシュウ酸塩化の処理を行った。シュウ酸塩化の処理条件は、実施例1と同様とした。
比較例3として、実施例2にて用いた、蒸気表7に組成を示す始液Hと同組成の塩酸酸性溶液を用い、その塩酸酸性溶液に対して溶媒抽出処理を施さず、直接水酸化ナトリウムを添加してスカンジウムを含有する水酸化物(水酸化スカンジウム)の沈殿を生成させた。その後、シュウ酸塩化処理も行わずに、そのまま得られた水酸化スカンジウムを分析した。下記表15に、その水酸化スカンジウムの分析値を示す。
比較例4として、実施例2にて用いた、上記表7に組成を示す始液Hと同組成の塩酸酸性溶液を用い、実施例2と同条件の溶媒抽出処理を施した後、得られた抽残液に水酸化ナトリウムを添加してスカンジウムを含有する水酸化物(水酸化スカンジウム)の沈殿を生成させた。その後、シュウ酸塩化処理は行わずに、そのまま得られた水酸化スカンジウムを分析した。下記表16に、その水酸化スカンジウムの分析値を示す。
Claims (8)
- スカンジウムを含有するニッケル酸化鉱石を高温高圧下で硫酸により浸出して浸出液と浸出残渣とを得る浸出工程と、
前記浸出液に中和剤を加えて中和澱物と中和後液とを得る中和工程と、
前記中和後液に硫化剤を添加してニッケル硫化物と硫化後液とを得る硫化工程と、
前記硫化後液をキレート樹脂に接触させることで該硫化後液中のスカンジウムを該キレート樹脂に吸着させ、スカンジウム溶離液を得るイオン交換工程と、
前記スカンジウム溶離液にアルカリを添加して水酸化スカンジウムの沈殿物を得た後、該水酸化スカンジウムに酸溶液を添加して酸溶解することでスカンジウム酸溶解液を得る溶解工程と、
前記スカンジウム酸溶解液を中性抽出剤に接触させてスカンジウム以外の不純物元素を抽出分離し、スカンジウムを含有する抽残液を得る溶媒抽出工程と、
前記抽残液にシュウ酸を添加してシュウ酸スカンジウムの塩を生成させ、該シュウ酸スカンジウム塩を焙焼して酸化スカンジウムを得るスカンジウム回収工程と
を有するスカンジウムの回収方法。 - 前記キレート樹脂は、イミノジ酢酸を官能基とする樹脂であり、
前記イオン交換工程は、
前記硫化後液を前記キレート樹脂に接触させて前記スカンジウムを前記キレート樹脂に吸着させる吸着工程と、
前記吸着工程でスカンジウムを吸着したキレート樹脂に0.1N以下の硫酸溶液を接触させて前記吸着工程で前記キレート樹脂に吸着したアルミニウムを除去するアルミニウム除去工程と、
前記アルミニウム除去工程を経たキレート樹脂に0.3N以上3N未満の硫酸溶液を接触させて前記スカンジウム溶離液を得るスカンジウム溶離工程と、
前記スカンジウム溶離工程を経たキレート樹脂に3N以上の硫酸溶液を接触させて前記吸着工程で前記キレート樹脂に吸着したクロムを除去するクロム除去工程と
を含む請求項1に記載のスカンジウムの回収方法。 - 前記溶媒抽出工程では、前記スカンジウム酸溶解液のpHを1.0以上2.5以下の範囲に維持して、該スカンジウム酸溶解液と前記中性抽出剤に接触させる
請求項1又は2に記載のスカンジウムの回収方法。 - 前記溶媒抽出工程は、
前記スカンジウム酸溶解液と前記中性抽出剤を含む有機溶媒とを混合して、スカンジウム以外の不純物元素を抽出した抽出後有機溶媒と抽残液とに分離する抽出工程と、
前記抽出後有機溶媒に1.0mol/l以上5.0mol/l以下の濃度の酸溶液を混合して、該抽出後有機溶媒からスカンジウムを回収し洗浄後有機溶媒を得るスクラビング工程と、
前記洗浄後有機溶媒に逆抽出剤を添加し、該洗浄後有機溶媒から不純物元素を逆抽出して逆抽出液を得る逆抽出工程と
を含む請求項1乃至3のいずれか1項に記載のスカンジウムの回収方法。 - 前記溶解工程では、前記水酸化スカンジウムに硝酸溶液を添加して酸溶解することによって、スカンジウム酸溶解液であるスカンジウム硝酸溶解液を得る
請求項1乃至4のいずれか1項に記載のスカンジウムの回収方法。 - 前記溶解工程では、前記水酸化スカンジウムに塩酸溶液を添加して酸溶解することによって、スカンジウム酸溶解液であるスカンジウム塩酸溶解液を得る
請求項1乃至4のいずれか1項に記載のスカンジウムの回収方法。 - 前記溶媒抽出工程では、
前記溶解工程で得られた前記スカンジウム塩酸溶解液の塩化物濃度が2.0mol/l以上6.0mol/l以下となるように調整し、該スカンジウム塩酸溶解液を前記中性抽出剤と接触させる
請求項6に記載のスカンジウムの回収方法。 - 前記スカンジウム回収工程は、
前記溶媒抽出工程で得られた前記抽残液に5.0mol/l以上8.0mol/l以下の濃度の水酸化ナトリウムを添加して、水酸化スカンジウムの沈殿物を得る工程と、
得られた水酸化スカンジウムの沈殿物を硫酸又は塩酸で溶解し、溶解して得られた溶解液にシュウ酸を添加してシュウ酸スカンジウムの結晶を得る工程と、
前記シュウ酸スカンジウムの結晶を焼成する工程と
を含む請求項1乃至7の何れか1項に記載のスカンジウムの回収方法。
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PH12018501725A1 (en) | 2019-05-15 |
JP6409796B2 (ja) | 2018-10-24 |
EP3421627A4 (en) | 2019-07-31 |
JP2017150019A (ja) | 2017-08-31 |
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