WO2017130692A1 - 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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- WO2017130692A1 WO2017130692A1 PCT/JP2017/000601 JP2017000601W WO2017130692A1 WO 2017130692 A1 WO2017130692 A1 WO 2017130692A1 JP 2017000601 W JP2017000601 W JP 2017000601W WO 2017130692 A1 WO2017130692 A1 WO 2017130692A1
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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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- 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
- C22B3/42—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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- 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 particularly, to a scandium recovery method for easily and efficiently recovering scandium contained in nickel oxide ore.
- 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 has not been industrially used as a nickel raw material for a long time because of its low nickel-containing grade. Therefore, there has been little research on industrially recovering 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 is recovered as nickel sulfide by adding a sulfiding agent to the leachate from which impurities have been separated.
- electric nickel and a nickel salt compound can be obtained.
- Patent Document 2 there is a method in which scandium is separated using a chelate resin (see Patent Document 2). Specifically, in the method disclosed in Patent Document 2, first, nickel-containing oxide ore is selectively leached into an acidic aqueous solution under high temperature and high pressure in an oxidizing atmosphere to obtain an acidic solution. Then, after adjusting the pH of the acidic solution to a range of 2 to 4, nickel is selectively precipitated and recovered as a sulfide by using a sulfurizing agent. Next, scandium is adsorbed by bringing the solution after nickel recovery obtained into contact with the chelate resin, washing the chelate resin with a dilute acid, and then contacting the chelate resin after washing with a strong acid from the chelate resin. Elute scandium.
- Patent Documents 3 and 4 As a method for recovering scandium from the above acidic solution, a method of recovering scandium using solvent extraction has also been proposed (see Patent Documents 3 and 4). Specifically, in the method disclosed in Patent Document 3, first, in addition to scandium, an aqueous phase scandium-containing solution containing at least one of iron, aluminum, calcium, yttrium, manganese, chromium, and magnesium is added to 2 -An organic solvent obtained by diluting ethylhexylsulfonic acid-mono-2-ethylhexyl with kerosene is added, and the scandium component is extracted into the organic solvent.
- an aqueous phase scandium-containing solution containing at least one of iron, aluminum, calcium, yttrium, manganese, chromium, and magnesium is added to 2 -An organic solvent obtained by diluting ethylhexylsulfonic acid-mono-2-ethylhexyl with keros
- oxalic acid is added to the obtained scandium chloride aqueous solution to form a scandium oxalate precipitate, and the precipitate is filtered to separate iron, manganese, chromium, magnesium, aluminum, and calcium into the filtrate, followed by calcination As a result, high-purity scandium oxide is obtained.
- Patent Document 4 describes a method of selectively separating and recovering scandium from a scandium-containing supply liquid by bringing the scandium-containing supply liquid into contact with an extractant at a constant rate by batch processing.
- nickel oxide ore described above contains various impurity elements such as manganese and magnesium in addition to iron and aluminum, although the types and amounts vary depending on the region where they are produced.
- the present invention has been proposed in view of the above-described circumstances, and an object of the present invention is to provide a scandium recovery method capable of easily and efficiently recovering high-purity scandium from nickel oxide ore. .
- the present inventors have made extensive studies to solve the above-described problems.
- nickel oxide was obtained by subjecting the eluate obtained by passing an acidic solution containing scandium through the ion exchange resin to solvent extraction of the solution obtained through the two-step neutralization treatment. It has been found that high-purity scandium can be easily and efficiently recovered from ore, and the present invention has been completed. That is, the present invention provides the following.
- a solution containing scandium is passed through an ion exchange resin, a neutralizing agent is added to an eluent eluted from the ion exchange resin, and neutralization is performed.
- a method for recovering scandium comprising: a solvent extraction step for subjecting the hydroxide solution to solvent extraction; and a scandium recovery step for recovering scandium oxide from the extracted residue separated in the solvent extraction step.
- the second invention of the present invention is the scandium recovery method according to the first invention, wherein in the first neutralization step, the pH of the eluent is adjusted to a range of 3.5 to 4.5. It is.
- the pH of the primary neutralized filtrate is adjusted to a range of 5.5 to 6.5. This is a method for recovering scandium.
- any one of the first to third aspects in the hydroxide dissolution step, sulfuric acid is used as the acid, and the pH of the resulting hydroxide solution is 0.
- the solution containing scandium used for the ion exchange resin is made of sulfuric acid at high temperature and high pressure under high pressure and high pressure.
- a leaching step of leaching to obtain a leachate, a neutralization step of adding a neutralizing agent to the leachate to obtain a neutralized starch containing impurities and a post-neutralization solution, and a sulfidizing agent to the post-neutralization solution This is a method for recovering scandium, which is the post-sulfurized liquid obtained by wet smelting treatment of nickel oxide ore having a sulfidation step of adding nickel sulfide and a post-sulfurized liquid.
- FIG. 1 is a flowchart showing an example of a scandium recovery method according to the present embodiment.
- scandium and impurities are separated from an acidic solution containing scandium obtained by leaching nickel oxide ore with an acid such as sulfuric acid. It is to be collected.
- an acidic solution containing scandium is passed through an ion exchange resin to adsorb scandium, and then an eluent (scandium eluent) obtained by contacting the acid solution with the ion exchange resin is used.
- an eluent scandium eluent obtained by contacting the acid solution with the ion exchange resin
- impurities are separated and scandium is concentrated by performing a two-step neutralization treatment.
- an extracting agent such as an amine-based extracting agent
- impurities contained in the acidic solution are extracted into the extracting agent, and the acidic solution is extracted after extraction. Separated from scandium that will remain in solution (extracted residue).
- scandium that is contained in the extraction residual liquid by this solvent extraction for example, an alkali is added to neutralize to obtain a hydroxide precipitate, or oxalic acid using oxalic acid.
- an alkali is added to neutralize to obtain a hydroxide precipitate, or oxalic acid using oxalic acid.
- oxalate precipitates by chlorination solid forms suitable for product use and residual impurities are separated to convert scandium into high-purity scandium hydroxide and scandium oxalate crystals. to recover.
- the obtained scandium hydroxide or scandium oxalate crystal is made into a form of scandium oxide by firing by a known method.
- the scandium oxide produced in this way can be used as an electrolyte material for fuel cells, or can be used for applications such as obtaining a scandium metal by a method such as molten salt electrolysis and then adding it to aluminum to form an alloy. it can.
- a two-stage neutralization process is performed on a solution (eluent) in which scandium is concentrated through an ion exchange process. Is characterized by further concentrating scandium, followed by solvent extraction using a solvent extractant such as an amine-based extractant. According to such a method, impurities can be more effectively separated, and even from a raw material containing many impurities such as nickel oxide ore, high purity scandium can be obtained under stable operation. Can be efficiently recovered.
- Nickel oxide ore hydrometallurgical treatment process An acidic solution obtained by treating nickel oxide ore with sulfuric acid can be used as the acidic solution containing scandium to be treated for scandium recovery.
- a leaching step S11 in which nickel oxide ore is leached with an acid such as sulfuric acid under high temperature and high pressure to obtain a leachate, and a neutralizer is added to the leachate to add impurities.
- the post-sulfurization solution obtained by the hydrometallurgical treatment step S1 can be used. Below, the flow of the hydrometallurgical treatment process S1 of nickel oxide ore will be described.
- Leaching step In the leaching step S11, for example, using a high-temperature pressurized container (autoclave) or the like, sulfuric acid is added to the slurry of nickel oxide ore, and the mixture is stirred at a temperature of 240 ° C to 260 ° C. It is a step of forming a leaching slurry comprising leaching residues.
- the process in leaching process S11 according to the conventionally known HPAL process, for example, it describes in patent document 1.
- 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 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 is performed by a solid-liquid separation facility such as a thickener using a flocculant supplied from a flocculant supply facility or the like.
- 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 process S12 adjusts pH by adding a neutralizing agent to the leachate obtained by leaching process S11 mentioned above, and neutralized starch containing an impurity element and the liquid after neutralization It is a process to obtain.
- a neutralizing agent such as nickel, cobalt, and scandium 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 it is preferable to adjust the pH to the range of 1 to 4 while suppressing the oxidation of the separated leachate, and more preferably to the range of 1.5 to 2.5. 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.
- Sulfurization step Sulfurization step S13 is a step of obtaining a nickel sulfide and a post-sulfurization solution by adding a sulfiding agent to the post-neutralization solution obtained by the above-described neutralization step S12.
- a sulfiding agent to the post-neutralization solution obtained by the above-described neutralization step S12.
- a sulfide containing nickel and cobalt with a small amount of impurity components is added to the obtained post-neutralization solution by adding a sulfiding agent such as hydrogen sulfide gas, sodium sulfide, 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, 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.
- the nickel / cobalt mixed sulfide slurry is subjected to a settling separation process using a settling separator such as a thickener to separate and recover the nickel / cobalt mixed sulfide from the bottom of the thickener.
- a settling separator such as a thickener to separate and recover the nickel / cobalt mixed sulfide from the bottom of the thickener.
- the post-sulfurization solution that is an aqueous solution component is recovered by overflowing.
- the post-sulfurization solution obtained through each step of the above-described nickel oxide ore hydrometallurgical treatment step S1, scandium and other target for scandium recovery treatment can be used as an acidic solution containing impurities.
- a post-sulfurization solution that is an acidic solution containing scandium obtained by leaching nickel oxide ore with sulfuric acid can be applied as a target solution for scandium recovery treatment.
- the post-sulfurization solution that is an acidic solution containing scandium in addition to scandium, for example, aluminum, chromium, and other various impurities that remain in the solution without being sulfided by the sulfurization treatment in the above-described sulfurization step S13. It is included.
- a scandium elution step S2 when subjecting this acidic solution to solvent extraction, as a scandium elution step S2, impurities contained in the acidic solution are removed in advance to concentrate scandium (Sc), and a scandium eluent (scandium-containing solution) is used. Preferably, it is generated.
- an ion exchange treatment using a chelate resin is used to separate and remove impurities such as aluminum contained in the acidic solution to obtain a scandium-containing solution in which scandium is concentrated. Can do.
- FIG. 2 is a flowchart showing an example of a method (ion exchange step) performed by an ion exchange reaction using a chelate resin as a method for removing impurities contained in an acidic solution and concentrating and eluting scandium.
- the post-sulfurization solution obtained in the sulfidation step S13 of the nickel oxide ore hydrometallurgy treatment step S1 is brought into contact with the chelate resin so that scandium in the post-sulfurization solution is adsorbed on the chelate resin, and scandium (Sc) An eluent is obtained.
- the ion exchange step as an example of the scandium elution step S2 is referred to as “ion exchange step S2.”
- an adsorption step S21 in which the solution after sulfurization is brought into contact with the chelate resin to adsorb scandium to the chelate resin, and sulfuric acid of 0.1 N or less is brought into contact with the chelate resin in which scandium is adsorbed.
- An example is one having 3N or more sulfuric acid in contact with it and a chromium removal step S24 for removing chromium adsorbed on the chelate resin in the adsorption step S21.
- ion exchange process S2 it is not limited to this.
- the sulfurized solution is brought into contact with the chelate resin to adsorb scandium to the chelate resin.
- the type of chelate resin is not particularly limited, and for example, a resin having iminodiacetic acid as a functional group can be used.
- Al removal step S22 0.1 N or less sulfuric acid is brought into contact with the chelate resin that has adsorbed scandium in the adsorption step S21 to remove aluminum adsorbed on the chelate resin.
- [Scandium elution step] sulfuric acid of 0.3N or more and less than 3N is brought into contact with the chelate resin that has undergone the aluminum removal step S22 to obtain a scandium eluent.
- chromium removal process In the chromium removal step S24, 3N or more sulfuric acid is brought into contact with the chelate resin that has undergone the scandium elution step S23, and the chromium adsorbed on the chelate resin in the adsorption step S21 is removed.
- the normality of sulfuric acid used in the eluent is less than 3N, it is not preferable because chromium is not properly removed from the chelate resin.
- the scandium eluent recovered in the scandium elution step S2 is subjected to solvent extraction using it as an extraction start solution in the solvent extraction step S4, which will be described later, so that the separation of scandium and impurities can be further advanced.
- the higher the concentration of the target component in the extraction starting solution used for solvent extraction the better the separation performance from undesired impurities.
- the higher the concentration of scandium the smaller the amount of solution used for solvent extraction, the smaller the amount of extractant used as a result. I'll do it.
- there are various merits such as improvement in operational efficiency such that the equipment required for the solvent extraction process is more compact.
- the scandium elution eluted from the chelate resin in the scandium elution step S2 (scandium elution step S23).
- a neutralizing agent to the liquid, forming a scandium hydroxide precipitate, adding an acid to the obtained scandium hydroxide precipitate and dissolving it again, a high scandium concentration A solution (extraction starting solution) with
- the scandium eluent is neutralized to concentrate scandium, thereby improving the solvent extraction processing efficiency.
- a neutralizing agent is added to the scandium eluent to adjust to a predetermined pH range to obtain a neutralization residue and a neutralized filtrate.
- a neutralization step S31 composed of two stages, a hydroxide dissolution step S32 that dissolves by adding an acid to the obtained neutralized starch, and obtains a redissolved solution containing a high concentration of scandium;
- a neutralizing agent is added to the scandium eluent to adjust the pH of the solution to a predetermined range, and the scandium contained in the scandium eluent is used as a precipitate of scandium hydroxide.
- a neutralized starch composed of scandium hydroxide and a neutralized filtrate are thus generated.
- the neutralizing agent is not particularly limited, and for example, sodium hydroxide can be used.
- the neutralization treatment in the neutralization step S31 pH adjustment by neutralization using a neutralizer is performed in two stages. Thereby, an impurity can be isolate
- FIG. 3 the figure for demonstrating the flow of the two-step neutralization process in neutralization process S31 is shown.
- the neutralization step S31 includes a first neutralization step for performing the first-stage neutralization and a second neutralization step for performing the second-stage neutralization.
- First neutralization step Specifically, in the neutralization treatment by two-stage pH adjustment, as a first neutralization step, a neutralizing agent such as sodium hydroxide is added to the scandium eluent so that the pH of the solution falls within a predetermined range.
- the first stage of neutralization is adjusted as follows. By this first stage neutralization, most of the impurities such as iron and chromium, which are components having a lower basicity than scandium, become precipitates in the form of hydroxides. The sum filtrate is separated. Scandium is concentrated in the primary neutralized filtrate.
- the pH of the solution is preferably adjusted to a range of 3.5 to 4.5 by adding a neutralizing agent. More preferably, the pH of the solution is adjusted to about 4.0. By adding a neutralizing agent and neutralizing so that the pH of the solution falls within this range, scandium can be more efficiently concentrated in the primary neutralized filtrate.
- a neutralizing agent such as sodium hydroxide is further added to the primary neutralized filtrate obtained by the first neutralization, and the pH of the solution is within a predetermined range.
- the second stage of neutralization is adjusted so that By this second stage neutralization, scandium hydroxide is obtained as a secondary neutralized starch, and nickel, which is a basic component higher than scandium, does not precipitate, so it remains in the secondary neutralized filtrate.
- a secondary neutralized starch that is, a hydroxide of scandium from which impurities are separated can be obtained.
- the pH of the primary neutralized filtrate is preferably adjusted to a range of 5.5 to 6.5 by adding a neutralizing agent. More preferably, the pH of the primary neutralized filtrate is adjusted to about 6.0. By neutralizing by adding a neutralizing agent so that the pH of the solution falls within this range, a scandium hydroxide precipitate can be generated more efficiently.
- the concentration of sodium hydroxide or the like used as a neutralizing agent in the neutralization treatment may be determined as appropriate. For example, when a high concentration neutralizing agent exceeding 4 N is added, the pH locally increases in the reaction vessel. In some cases, the pH may partially exceed 4.5. In such a case, adverse effects such as coprecipitation of scandium and impurities may occur, and high-purity scandium may not be obtained. For this reason, it is preferable to use a solution diluted to 4N or less as the neutralizing agent, so that the neutralization reaction in the reaction vessel may occur as uniformly as possible.
- the concentration of the neutralizing agent such as sodium hydroxide solution is too low, the amount of solution required for the addition increases correspondingly, which increases the amount of liquid to be handled, resulting in an increase in equipment scale and cost. It is not preferable because it causes an increase. For this reason, it is preferable to use a neutralizing agent having a concentration of 1N or more.
- the precipitate obtained by adding an alkali neutralizing agent such as sodium hydroxide has very poor filterability. Is normal. For this reason, in neutralization, filterability may be improved by adding seed crystals.
- the seed crystal is preferably added in an amount of about 1 g / L or more with respect to the solution before the neutralization treatment.
- hydroxide dissolution process for the neutralized starch (secondary neutralized starch) mainly composed of scandium hydroxide recovered through the two-step neutralization treatment in the neutralization step S31 described above, It dissolves by adding an acid to obtain a hydroxide solution that becomes a redissolved solution.
- the redissolved solution thus obtained is used as an extraction starting solution for solvent extraction processing in a solvent extraction step S4 described later.
- the acid for dissolving the neutralized starch is not particularly limited, but sulfuric acid is preferably used. When sulfuric acid is used, the redissolved solution becomes a scandium sulfate solution.
- the concentration is not particularly limited, but it is preferable to use a sulfuric acid solution having a concentration of 2N or more in view of industrial reaction rate.
- an extraction starting solution having an arbitrary scandium concentration can be obtained by adjusting the slurry concentration during dissolution with sulfuric acid or the like.
- the pH of the solution is preferably maintained in the range of 0.8 to 1.5, more preferably about 1.0, and this pH is maintained.
- scandium hydroxide can be efficiently dissolved, and loss of scandium recovery due to undissolution can be suppressed.
- pH range mentioned above when pH exceeds 1.5 and there exists a possibility that melt
- the pH is low, such as less than 0.8, a strongly acidic solution is obtained, and the amount of neutralizing agent added in the wastewater treatment to neutralize and dispose of the solution after recovering scandium increases. This is not preferable because it is costly and troublesome.
- solvent extraction step S4 the redissolved solution (hydroxide solution) obtained through the neutralization step S3 in which the scandium eluent is neutralized is used as an extraction starting solution, and this is used as an extractant. Contact is made to obtain an extraction liquid containing scandium.
- the redissolved solution used for solvent extraction is an acidic solution containing scandium and other impurity elements as described above, and these are referred to as “scandium-containing solutions”.
- solvent extraction process S4 for example, as shown in FIG.1 and FIG.2, extraction which mixed the scandium containing solution and the extractant which is an organic solvent, and extracted a little scandium
- An extraction step S41 for separating the post-organic solvent and the extraction liquid leaving the scandium, and mixing the sulfuric acid solution with the post-extraction organic solvent to separate the slight scandium extracted into the organic solvent into the aqueous phase. It is preferable to perform a solvent extraction process including a scrubbing step S42 for obtaining a post-washing solution, and a back extraction step S43 for backextracting impurities from the washed organic solvent by adding a back extractant to the washed organic solvent.
- Extraction step S41 a scandium-containing solution and an organic solvent containing an extractant are mixed, and impurities are selectively extracted into the organic solvent. Get.
- a solvent extraction process using an amine-based extractant is preferably performed in the extraction step S41.
- the amine-based extractant has characteristics such as low selectivity with scandium and no need for a neutralizing agent at the time of extraction.
- PrimeneJM-T which is a primary amine, secondary amine.
- An amine-based extractant known under a trade name such as LA-1, a tertiary amine TNOA (Tri-n-octylamine), TIOA (Tri-i-octylamine), or the like can be used.
- the amine-based extractant diluted with, for example, a hydrocarbon-based organic solvent.
- concentration of the amine-based extractant in the organic solvent is not particularly limited, but is preferably about 1% by volume or more and 10% by volume or less in consideration of phase separation during extraction and back-extraction described later, In particular, it is more preferably about 5% by volume.
- the volume ratio between the organic solvent and the scandium-containing solution at the time of extraction is not particularly limited, but the organic solvent molar amount is about 0.01 to 0.1 times the metal molar amount in the scandium-containing solution. It is preferable to make it.
- the scrubbing step S42 is provided to wash the organic solvent and to separate the slight amount of scandium extracted by the extractant, whereby the scandium can be separated in the washing liquid, and the scandium recovery rate is further enhanced. be able to.
- a solution (cleaning solution) used for scrubbing a sulfuric acid solution, a hydrochloric acid solution, or the like can be used. Moreover, what added the soluble chloride and sulfate to water can also be used. Specifically, when a sulfuric acid solution is used as the cleaning solution, it is preferable to use one having a concentration range of 1.0 mol / L or more and 3.0 mol / L or less.
- back extraction process S43 an impurity is back-extracted from the organic solvent which extracted the impurity in extraction process S41. Specifically, in the back extraction step S43, 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 S41. Impurities are back-extracted to obtain a back-extracted solution containing impurities.
- a reverse extraction solution back extraction start liquid
- an amine-based extractant is used as an extractant to selectively extract impurities.
- the back extraction solution contains carbonates such as sodium carbonate and potassium carbonate. It is preferable to use a solution to be used.
- the concentration of the carbonate-containing solution that is the back extraction solution is preferably about 0.5 mol / L or more and 2 mol / L or less, for example, from the viewpoint of suppressing excessive use.
- the extractant after adding the carbonate solution such as sodium carbonate to the extractant after extraction or the extractant after scrubbing and performing the back extraction process to separate impurities is again in the extraction step S41. It can be used repeatedly as an extractant.
- the crystallization step S51 is a step of recovering the scandium contained in the extraction residual liquid by crystallizing it into a scandium salt precipitate.
- the method for crystallizing and recovering scandium is not particularly limited, and a known method can be used.
- a method of recovering scandium hydroxide precipitates by adding an alkali to neutralize and recovering it.
- recovers the precipitate of an oxalate with an oxalic acid solution can also be used. These methods are preferable because they can more effectively separate impurities and obtain scandium crystals.
- the roasting step S52 is a step in which precipitates such as scandium hydroxide and scandium oxalate obtained in the crystallization step S51 are washed with water and dried, and then roasted. Through this roasting treatment, scandium can be recovered as extremely high-purity scandium oxide.
- the conditions for the roasting treatment are not particularly limited.
- the baking may be performed in a tubular furnace 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.
- the obtained scandium eluent (composition of Table 2) was collected and placed in a container, and a 4N sodium hydroxide solution was added with stirring to adjust the pH of the solution to 1. .
- each prepared sample components, such as a scandium, iron, aluminum, nickel, were analyzed using ICP.
- the quantity calculated from the analysis value of each component and the liquid volume of each sampling is the quantity of the component present in the solution at each pH.
- the difference between the amount of components present in the solution and the initial amount calculated from the analysis value of the scandium eluent shown in Table 2 above and the initial amount is the amount of precipitate generated by pH adjustment (neutralization). Equivalent to.
- the ratio obtained by dividing the amount of precipitation by the above-mentioned initial amount was defined as the precipitation rate (%).
- FIG. 4 shows the precipitation rate of each pH and the components shown in Table 2. As shown in the graph of FIG. 4, it can be seen that the precipitation rate of iron increases in the region where the pH is 3 or higher, and almost completely precipitates in the range of 4.5 to 5 or higher. It can also be seen that the precipitation rate of aluminum increases when the pH exceeds 4.5. On the other hand, it can be seen that scandium also increases in precipitation rate when the pH exceeds 4.5, but the increase is slower than aluminum. Nickel begins to precipitate when the pH starts to exceed 6.
- Example 2 Two-stage neutralization treatment >> [Example 1] (First stage neutralization) According to the results shown in FIG. 4, the scandium eluent having the composition shown in Table 2 above is placed in a container, and a 4N sodium hydroxide solution is added with stirring to adjust the pH of the solution to 1. Stage neutralization was performed.
- the scandium was distributed into the secondary neutralized starch recovered by solidification.
- the ratio (precipitation rate) was such that aluminum was conspicuous in addition to scandium, and other iron, chromium, nickel, and the like were effectively separated.
- a sulfuric acid solution having a concentration of 1 mol / L is added to 50 liters of an organic solvent (extracted organic phase) slightly containing scandium obtained after the extraction treatment so that the phase ratio (O / A) is 1. 50 liters was mixed and stirred for 60 minutes for washing. Thereafter, the mixture was allowed to stand to separate the aqueous phase, and the organic phase was again mixed with 50 liters of a new sulfuric acid solution having a concentration of 1 mol / L and washed, and the aqueous phase was similarly separated. Such washing operation was repeated a total of 5 times.
- oxalic acid dihydrate manufactured by Mitsubishi Gas Chemical Co., Inc.
- crystals which is twice the calculated amount of scandium contained in the extracted residual liquid, is obtained from the extracted residual liquid. Dissolved and stirred and mixed for 60 minutes to form a white crystalline precipitate of scandium oxalate.
- the re-dissolved solution obtained by the conventional method (composition shown in Table 10) and the re-dissolved solution obtained in Example 1, that is, the re-dissolved solution obtained after two-step neutralization treatment (composition shown in Table 6) The scandium concentration was the same, but there was a large difference in the aluminum concentration and the iron concentration. That is, as in Example 1, it was confirmed that the two steps of neutralization treatment can effectively separate aluminum and iron as impurities.
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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の一例を示すフロー図である。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、スカンジウムを含有する酸性溶液から、スカンジウムと不純物とを分離して、高純度のスカンジウムを簡便に且つ効率よく回収するものである。
<2-1.ニッケル酸化鉱石の湿式製錬処理工程>
スカンジウム回収の処理対象となるスカンジウムを含有する酸性溶液としては、ニッケル酸化鉱石を硫酸により処理して得られる酸性溶液を用いることができる。
浸出工程S11は、例えば高温加圧容器(オートクレーブ)等を用いて、ニッケル酸化鉱石のスラリーに硫酸を添加して240℃~260℃の温度下で撹拌処理を施し、浸出液と浸出残渣とからなる浸出スラリーを形成する工程である。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S12は、上述した浸出工程S11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工程である。この中和工程S12における中和処理により、ニッケルやコバルト、スカンジウム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S13は、上述した中和工程S12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工程である。この硫化工程S13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。
上述したように、ニッケル酸化鉱石を硫酸により浸出して得られた、スカンジウムを含有する酸性溶液である硫化後液を、スカンジウム回収処理の対象溶液として適用することができる。ところが、スカンジウムを含有する酸性溶液である硫化後液には、スカンジウムの他に、例えば上述した硫化工程S13における硫化処理で硫化されずに溶液中に残留したアルミニウムやクロム、その他の多種多様な不純物が含まれている。このことから、この酸性溶液を溶媒抽出に付すにあたり、スカンジウム溶離工程S2として、予め、酸性溶液中に含まれる不純物を除去してスカンジウム(Sc)を濃縮し、スカンジウム溶離液(スカンジウム含有溶液)を生成させることが好ましい。
吸着工程S21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。キレート樹脂の種類は特に限定されず、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できる。
アルミニウム除去工程S22では、吸着工程S21でスカンジウムを吸着したキレート樹脂に0.1N以下の硫酸を接触させ、キレート樹脂に吸着したアルミニウムを除去する。なお、アルミニウムを除去する際、pHを1以上2.5以下の範囲に維持することが好ましく、1.5以上2.0以下の範囲に維持することがより好ましい。
スカンジウム溶離工程S23では、アルミニウム除去工程S22を経たキレート樹脂に0.3N以上3N未満の硫酸を接触させ、スカンジウム溶離液を得る。スカンジウム溶離液を得るに際しては、溶離液に用いる硫酸の規定度を0.3N以上3N未満の範囲に維持することが好ましく、0.5N以上2N未満の範囲に維持することがより好ましい。
クロム除去工程S24では、スカンジウム溶離工程S23を経たキレート樹脂に3N以上の硫酸を接触させ、吸着工程S21でキレート樹脂に吸着したクロムを除去する。クロムを除去するに際して、溶離液に用いる硫酸の規定度が3Nを下回ると、クロムが適切にキレート樹脂から除去されないため、好ましくない。
上述したように、スカンジウム溶離工程S2では、キレート樹脂の選択性によってスカンジウムと不純物との分離が行われ、不純物と分離したスカンジウムがスカンジウム溶離液として回収される。しかしながら、使用するキレート樹脂の特性上、すべての不純物を完全にスカンジウムと分離できるわけではない。
中和工程S31では、スカンジウム溶離液に対して中和剤を添加してその溶液のpHを所定の範囲に調整し、スカンジウム溶離液中に含まれるスカンジウムを水酸化スカンジウムの沈殿物とする。中和工程S31では、このように、水酸化スカンジウムから構成される中和澱物と中和濾液とを生成させる。
具体的に、2段階のpH調整による中和処理では、第1の中和工程として、スカンジウム溶離液に対して水酸化ナトリウム等の中和剤を添加し、溶液のpHが所定の範囲となるように調整する1段目の中和を行う。この1段目の中和によって、スカンジウムより塩基性が低い成分である鉄、クロム等の不純物の大部分が水酸化物の形態の沈殿物となり、濾過により1次中和澱物と1次中和濾液とが分離される。なお、スカンジウムは、1次中和濾液中に濃縮される。
次に、第2の中和工程として、1段目の中和により得られた1次中和濾液に対して、さらに水酸化ナトリウム等の中和剤を添加し、溶液のpHが所定の範囲となるように調整する2段目の中和を行う。この2段目の中和によって、水酸化スカンジウムを2次中和澱物として得るとともに、スカンジウムより塩基性が高い成分であるニッケルは沈殿とならないために2次中和濾液に残留するようになり、固液分離することで、2次中和澱物、すなわち不純物を分離したスカンジウムの水酸化物を得ることができる。
水酸化物溶解工程S32では、上述した中和工程S31における2段階の中和処理を経て回収された水酸化スカンジウムを主成分とする中和澱物(2次中和澱物)に対して、酸を添加することによって溶解し、再溶解液となる水酸化物溶解液を得る。本実施の形態においては、このようにして得られた再溶解液を、後述する溶媒抽出工程S4における溶媒抽出処理の抽出始液として用いる。
次に、溶媒抽出工程S4では、スカンジウム溶離液に対して中和処理を施す中和工程S3を経て得られた再溶解液(水酸化物溶解液)を抽出始液とし、それを抽出剤に接触させてスカンジウムを含有する抽残液を得る。なお、溶媒抽出に供する再溶解液は、上述したようにスカンジウムとその他の不純物元素を含有する酸性溶液であり、これらを「スカンジウム含有溶液」と称する。
抽出工程S41では、スカンジウム含有溶液と、抽出剤を含む有機溶媒とを混合して、有機溶媒中に不純物を選択的に抽出し、不純物を含有する有機溶媒と抽残液とを得る。本実施の形態に係るスカンジウムの回収方法では、この抽出工程S41において、好ましくはアミン系抽出剤を用いた溶媒抽出処理を行う。このようにアミン系抽出剤を用いて溶媒抽出処理を行うことにより、より効率的に且つ効果的に不純物を抽出してスカンジウムと分離することができる。
上述した抽出工程S41においてスカンジウム含有溶液から不純物を抽出させた溶媒中にスカンジウムが僅かに共存する場合には、抽出工程S41にて得られた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して抽出剤中から回収する(スクラビング工程S42)。
逆抽出工程S43では、抽出工程S41にて不純物を抽出した有機溶媒から、不純物を逆抽出する。具体的に、逆抽出工程S43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S41における抽出処理とは逆の反応を生じさせて不純物を逆抽出し、不純物を含む逆抽出後液を得る。
次に、スカンジウム回収工程S5では、溶媒抽出工程S4における抽出工程S41にて得られた抽残液、及び、スクラビング工程S42にてスクラビングを行った場合にはそのスクラビング後の洗浄液から、スカンジウムを回収する。
結晶化工程S51は、抽残液等に含まれるスカンジウムをスカンジウム塩の沈殿物に結晶化させて回収する工程である。
焙焼工程S52は、結晶化工程S51で得られた水酸化スカンジウムやシュウ酸スカンジウム等の沈殿物を水で洗浄し、乾燥させた後に、焙焼する工程である。この焙焼処理を経ることで、スカンジウムを極めて高純度な酸化スカンジウムとして回収することができる。
ニッケル酸化鉱石を特許文献1に記載の方法等の公知の方法に基づき、硫酸を用いて加圧酸浸出し、得られた浸出液のpHを調整して不純物を除去した後、硫化剤を添加してニッケルを分離して硫化後液を用意した。下記表1に、得られた硫化後液中のスカンジウム、アルミ、鉄の濃度を示す。
[実施例1]
(1段目の中和)
図4に示した結果に従い、上記表2に組成を示すスカンジウム溶離液を容器に入れ、撹拌しながら濃度4Nの水酸化ナトリウム溶液を添加して、溶液のpHが4になるように調整する1段目の中和処理を行った。
次に、得られた1次中和濾液を容器に入れ、これに濃度4Nの水酸化ナトリウムを添加し、溶液のpHが6になるように調整する2段目の中和処理を行った。
(水酸化物溶解処理)
次に、得られた2次中和澱物に濃度2Nの硫酸溶液を添加し、pHを1前後に維持しながら溶解し、下記表6に示す再溶解液(水酸化物溶解液)を得た。
次に、表6に示す組成の再溶解液100リットルを抽出始液とし、これに、アミン系抽出剤(ダウケミカル社製,PrimeneJM-T)を溶剤(シェルケミカルズジャパン社製,シェルゾールA150)を用いて5体積%に調整した有機溶媒50リットルを混合させ、室温で60分間撹拌して溶媒抽出処理を施した。この溶媒抽出処理により、スカンジウムを含む抽残液を得た。なお、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、得られた抽残液に対して、その抽残液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(三菱ガス化学株式会社製)の結晶を溶解し、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を吸引濾過し、純水を用いて洗浄し、105℃で8時間乾燥させた。続いて、乾燥させた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)させ、酸化スカンジウムを得た。
[比較例1]
実施例1にて使用した上記表1に示す同組成の硫化後液に対して、実施例1と同じ手法でイオン交換処理を行い、表2と同じ組成のスカンジウム溶離液を得た。
図4に示した結果をもとに、スカンジウム溶離液に対して濃度4Nの水酸化ナトリウム溶液を添加して、溶液のpHが5~6の範囲内となるように中和し沈殿物を生成させた。その後、固液分離してスカンジウム水酸化物の沈殿を得た。
Claims (5)
- スカンジウムを含有する溶液をイオン交換樹脂に通液し、該イオン交換樹脂から溶離した溶離液に中和剤を添加して中和処理を施し、固液分離により1次中和澱物と1次中和濾液とを得る第1の中和工程と、
前記1次中和濾液にさらに中和剤を添加して中和処理を施し、固液分離により2次中和澱物と2次中和濾液とを得る第2の中和工程と、
前記2次中和澱物に酸を添加して水酸化物溶解液を得る水酸化物溶解工程と、
前記水酸化物溶解液を溶媒抽出に付す溶媒抽出工程と、
前記溶媒抽出工程にて分離された抽残液から酸化スカンジウムを回収す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。 - 前記第1の中和工程では、前記溶離液のpHを3.5~4.5の範囲に調整する
請求項1に記載のスカンジウムの回収方法。 - 前記第2の中和工程では、前記1次中和濾液のpHを5.5~6.5の範囲に調整する
請求項1又は2に記載のスカンジウムの回収方法。 - 前記水酸化物溶解工程では、前記酸として硫酸を用い、得られる水酸化物溶解液のpHが0.8~1.5の範囲に維持されるように前記2次中和澱物を溶解する
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。 - 前記イオン交換樹脂に供される前記スカンジウムを含有する溶液は、
前記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を得る浸出工程と、
前記浸出液に中和剤を添加して不純物を含む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
を有するニッケル酸化鉱石の湿式製錬処理により得られる前記硫化後液である
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。
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JP2021127514A (ja) * | 2019-09-24 | 2021-09-02 | 住友金属鉱山株式会社 | スカンジウムの回収方法 |
JP7327276B2 (ja) | 2019-09-24 | 2023-08-16 | 住友金属鉱山株式会社 | スカンジウムの回収方法 |
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US10196710B1 (en) | 2019-02-05 |
CN108463567B (zh) | 2020-05-19 |
JP6256491B2 (ja) | 2018-01-10 |
CN108463567A (zh) | 2018-08-28 |
CU20180077A7 (es) | 2018-10-04 |
EP3409800A4 (en) | 2019-07-24 |
AU2017213212B2 (en) | 2019-01-24 |
EP3409800A1 (en) | 2018-12-05 |
PH12018501557A1 (en) | 2019-05-20 |
CA3012088C (en) | 2019-01-08 |
AU2017213212A1 (en) | 2018-08-09 |
CU24521B1 (es) | 2021-06-08 |
CA3012088A1 (en) | 2017-08-03 |
JP2017133050A (ja) | 2017-08-03 |
PH12018501557B1 (en) | 2019-05-20 |
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