WO2016084830A1 - Method for recovering high-purity scandium - Google Patents
Method for recovering high-purity scandium Download PDFInfo
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- WO2016084830A1 WO2016084830A1 PCT/JP2015/083020 JP2015083020W WO2016084830A1 WO 2016084830 A1 WO2016084830 A1 WO 2016084830A1 JP 2015083020 W JP2015083020 W JP 2015083020W WO 2016084830 A1 WO2016084830 A1 WO 2016084830A1
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- scandium
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- extractant
- oxalate
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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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- 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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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 using solvent extraction with an amine-based extractant.
- 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 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.
- the obtained nickel-recovered solution is brought into contact with a chelate resin to adsorb scandium, the chelate resin is washed with dilute acid, and then the washed chelate resin is brought into contact with a strong acid to elute scandium from the chelate resin. To do.
- 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
- 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 ores there are variations in size and quantity depending on the region where they are produced, but in addition to iron and aluminum, manganese and magnesium, and in some cases, trace amounts of uranium and thorium, etc.
- impurity elements are contained, including actinide elements.
- scandium hydroxide when scandium is recovered in the form of hydroxide by adding alkali, some or most of impurities such as aluminum and iron contained in the solution are also precipitated at the same time, so scandium is selectively separated. Difficult to do. Furthermore, scandium hydroxide is in a gel form with poor filterability, and there is a problem that handling properties are lowered, for example, it takes time for filtration.
- 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. As a result, it was found that high-purity scandium can be easily and efficiently recovered from nickel oxide ore by subjecting an acidic solution containing scandium to solvent extraction using an amine-based extractant. It came to be completed. That is, the present invention provides the following.
- a solution containing scandium is passed through an ion exchange resin, and then the eluate eluted from the ion exchange resin is subjected to solvent extraction to extract a residual solution and extract
- the oxalic acid is added to the extractant and then oxalic acid is added to obtain a precipitate of scandium oxalate, and the precipitate is roasted to obtain scandium oxide.
- a method for recovering scandium characterized in that an amine-based extractant is used as an extractant for extraction.
- a sulfuric acid solution having a concentration of 1.0 mol / L or more and 3.0 mol / L or less as a cleaning liquid is mixed with the extractant after the solvent extraction.
- the scandium recovery method includes scrubbing to separate scandium contained in the extractant into the cleaning liquid and recovering scandium from the scrubbing cleaning liquid.
- the extractant and back extract after back extraction are performed by adding carbonate to the extractant after solvent extraction and performing back extraction. Is a method for recovering scandium.
- the fourth invention according to the present invention is the scandium recovery method according to the third invention, wherein the extractant after back extraction is repeatedly used as the extractant for the solvent extraction.
- the solution containing scandium that is subjected to the solvent extraction is obtained by using the nickel oxide ore with sulfuric acid under high temperature 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 adding a sulfurizing agent to the post-neutralization solution
- a neutralizing agent is added to the eluent eluted from the ion exchange resin so that the pH is in the range of 5-6.
- This is a method for recovering scandium by adjusting, obtaining a neutralized starch and a neutralized filtrate by solid-liquid separation, and subjecting the redissolved solution obtained by adding an acid to the neutralized starch to the solvent extraction. .
- a neutralizing agent is added to the eluent eluted from the ion exchange resin to adjust the pH to 3.5-4.
- a neutralizing agent is further added to the primary neutralized filtrate to adjust the pH to 5.5 to A re-dissolved solution obtained by adjusting the range to 6.5, obtaining a secondary neutralized starch and a secondary neutralized filtrate by solid-liquid separation, and adding an acid to the secondary neutralized starch Is a method for recovering scandium, which is subjected to solvent extraction.
- an eighth invention in any one of the first to seventh inventions, when the extraction residue is subjected to an oxalate treatment to obtain a scandium oxalate precipitate, the pH of the extraction liquid is adjusted to a range of ⁇ 0.5 or more and less than 1, and the solution after the pH adjustment is added to a solution containing oxalic acid to form a scandium oxalate precipitate. This is a method for recovering scandium.
- the present embodiment will be described in detail with reference to the drawings.
- the present invention is not limited to the following embodiments.
- the present invention can be implemented with appropriate modifications within a range not changing the gist of the present invention.
- the notation “X to Y” (X and Y are arbitrary numerical values) means “X or more and Y or less”.
- FIG. 1 is a flowchart showing an example of a scandium recovery method according to the present embodiment.
- scandium and other impurities are separated from an acidic solution containing scandium obtained by leaching nickel oxide ore with an acid such as sulfuric acid, whereby high-purity scandium can be easily and It is efficiently recovered.
- an acidic solution containing scandium is subjected to solvent extraction using an amine-based extractant to extract impurities contained in the acidic solution, particularly thorium (Th), which is an actinoid element, as an extractant. Extract into and separate from scandium which will remain in the acidic solution after extraction.
- thorium thorium
- scandium that is contained in the extraction residue by solvent extraction it is made into a solid form suitable for product use by a method of collecting it as an oxalate precipitate by oxalate treatment using oxalic acid.
- impurities such as uranium remaining can be separated, and scandium can be recovered as highly pure scandium oxalate crystals.
- scandium oxalate crystals were used as a material for the fuel cell electrolyte in the form of scandium oxide by firing by a known method, or scandium metal was obtained by a method such as molten salt electrolysis. Later, it can be added to aluminum for use as an alloy.
- nickel obtained by leaching nickel oxide ore with an acid such as sulfuric acid to obtain an acidic solution containing scandium.
- Oxide ore hydrometallurgy treatment step S1 scandium elution step S2 for obtaining scandium eluate in which scandium is concentrated by removing impurities from the acidic solution, and scandium eluent for solvent extraction using an amine-based extractant
- solvent extraction process S4 which extracts an impurity in an extracting agent, and isolate
- recovery process S5 which collect
- a neutralization step S3 for obtaining a solution (extraction starting solution) containing high-concentration scandium by adding a neutralizing agent to the scandium eluent to perform neutralization treatment is provided. be able to.
- 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 obtains the neutralized starch containing an impurity element, and the liquid after neutralization It is a process.
- 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 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.
- 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.
- the normality of sulfuric acid used in the eluent is preferably maintained in the range of 0.3N to less than 3N, and more preferably maintained in the range of 0.5N to less than 2N.
- 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 more the amount of extractant used as a result. Less is enough.
- 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 eluate eluted from the chelate resin in the scandium elution step S2 is neutralized.
- a solution having a high scandium concentration (extraction) is obtained by adjusting the pH by adding an agent to form a precipitate of scandium hydroxide, adding an acid to the obtained scandium hydroxide precipitate and dissolving it again. (Starting solution).
- 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. It has neutralization process S31, and the hydroxide melt
- a neutralizing agent is added to the scandium eluent to adjust the pH of the solution to a range of 5 to 6, 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.
- pH adjustment by neutralization using a neutralizing agent may be performed in two stages, whereby impurities can be more efficiently separated.
- a neutralizing agent such as sodium hydroxide is added to the scandium eluent, and the pH of the solution is preferably in the range of 3.5 to 4.5.
- 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.
- a neutralizing agent such as sodium hydroxide is further added to the primary neutralized filtrate obtained by neutralization in the first stage, and the pH of the filtrate is in the range of 5.5 to 6.5.
- the second stage of neutralization is performed so that the pH is adjusted to about 6.
- 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 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 In the hydroxide dissolution step S32, an acid is added to the neutralized starch mainly composed of scandium hydroxide recovered through the one-step or two-step neutralization treatment in the neutralization step S31 described above. To obtain a redissolved solution. In this Embodiment, it is preferable to use for the solvent extraction process mentioned later by using the redissolved solution obtained in this way as an extraction start liquid.
- 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 it is preferable to maintain the pH of the solution to be 1, so that the dissolution of scandium hydroxide is efficient by dissolving so as to maintain this pH. This can be carried out automatically, and the loss of scandium recovery due to undissolution can be suppressed.
- 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, particularly thorium (Th), is selectively extracted into the organic solvent. A solvent and a residue solution are obtained.
- the scandium recovery method according to the present embodiment is characterized in that a solvent extraction process using an amine-based extractant is performed in the extraction step S41. By performing a solvent extraction process using an amine-based extractant, impurities such as thorium can be extracted more efficiently and effectively and separated from scandium.
- 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 post-extraction solution containing impurities.
- a reverse extraction solution back extraction start liquid
- a solution containing a carbonate such as sodium carbonate or potassium carbonate may be used as the back extraction solution. preferable.
- 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 scandium recovery method is not particularly limited, and a known method can be used.
- the oxalate solution can be obtained by using an oxalic acid solution rather than a method of neutralizing by adding an alkali and recovering it as a scandium hydroxide starch.
- a method of recovering as a precipitate (oxalate treatment) impurities can be more effectively separated, which is preferable.
- scandium oxalate precipitates are formed by adding oxalic acid to the extracted residue and washing solution, and then scandium oxalate is dried and roasted to obtain scandium oxide. to recover. More specifically, a method for recovering scandium as scandium oxide by performing a roasting process after oxalate will be described with reference to the flowchart of FIG.
- the amount of oxalic acid added is not particularly limited, but it may be 1.05 to 1.2 times the equivalent amount required for precipitating scandium contained in the extraction residual liquid as oxalate. preferable.
- the amount of oxalic acid ((COOH) 2 ) necessary to convert scandium (Sc) to scandium oxalate (Sc 2 (C 2 O 4 )) is defined as 1 equivalent.
- the added amount is less than 1.05 times the equivalent amount required for precipitation, there is a possibility that the entire amount of scandium cannot be recovered.
- the addition amount exceeds 1.2 times the equivalent amount required for precipitation, the solubility of the obtained scandium oxalate increases, so that scandium is redissolved and the recovery rate decreases, or excess oxalic acid is removed.
- the amount of oxidizing agent such as sodium hypochlorite increases due to decomposition.
- this oxalate formation step S51 sulfuric acid or the like is added to a scandium-containing solution such as a residual extract to obtain a scandium-containing solution in which the pH of the solution is adjusted to a range of ⁇ 0.5 or more and less than 1. . Subsequently, the scandium-containing solution after pH adjustment and the oxalic acid solution are mixed to obtain scandium oxalate crystals.
- a scandium-containing solution such as a residual extract
- the scandium-containing solution after pH adjustment which is the solution to be treated
- the scandium-containing solution after pH adjustment which is the solution to be treated
- the scandium-containing solution after pH adjustment is used as a reaction vessel, as is conventionally performed.
- a so-called reverse addition method of adding a scandium-containing solution after pH adjustment into a large amount of oxalic acid solution filled in the reaction vessel A method of obtaining scandium oxalate crystals can also be used.
- the scandium oxalate crystals obtained by the oxalate treatment are washed after solid-liquid separation, and then subjected to a treatment in a roasting step S53, which will be described later, to obtain high-purity scandium oxide. it can.
- the roasting step S52 is a step in which the precipitate of scandium oxalate obtained in the oxalate forming step S51 is 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.
- Example 1 [Preparation of scandium-containing solution (original solution before extraction)] Based on a known method such as the method described in Patent Document 1, nickel oxide ore is subjected to pressure acid leaching using sulfuric acid, and the pH of the obtained leachate is adjusted to remove impurities, and then a sulfurizing agent is added. Then, nickel was separated and a solution after sulfidation was prepared. Table 1 below shows the main composition of the solution after sulfidation.
- “Others” in the component column in Table 2 and the subsequent tables is an element contained in nickel oxide ores such as nickel, magnesium, chromium, manganese, calcium, cobalt, etc., and is added when processing nickel oxide ores. This is a general term for various elements such as elements derived from neutralizing agents, etc., elements that are usually not present or prepared in a very small amount in this example, and analytical values of these detected components. It is written in total. In this embodiment, aluminum and iron are not included in “Others”.
- Example 1 The same ore as in Example 1 was leached with sulfuric acid, the leachate was neutralized, and then passed through an ion exchange resin to obtain a pre-extraction original solution having the composition shown in Table 2 above. The solution was directly subjected to the treatment in the oxalate formation step described above without being subjected to the solvent extraction step. Otherwise, the same method as in Example 1 was used.
- Example 2 The post-sulfurization solution having the same composition shown in Table 1 used in Example 1 was subjected to an ion exchange treatment in the same manner as in Example 1. Then, sodium hydroxide is added to the obtained scandium eluent to adjust to pH 6 and neutralized to produce a neutralized starch, and then the obtained neutralized starch (scandium hydroxide) is subjected to sulfuric acid. Is added and dissolved again, and if necessary, a reagent is added in the same manner as in Example 1 to obtain a chelate eluent (hydroxide solution) having the composition shown in Table 6 below, followed by solvent extraction The former liquid was used.
- a chelate eluent hydrooxide solution
- a chelate eluent (hydroxide solution) having the composition shown in Table 6 was used as an extraction start solution, and this was subjected to solvent extraction using an amine-based extractant.
- amine-based extractant As the amine-based extractant, Primene JM-T (manufactured by Dow Chemical Company) was used in the same manner as in Example 1, and this was diluted to 5% by volume with a solvent (manufactured by Shell Chemicals Japan, Shellzol A150). .
- the extraction equilibrium pH was set to 1, and based on the ratio between the amount of organic and the amount of metal in the solution, the amounts of organic amount (O) and extraction start solution (A) were selected as in the extraction conditions shown in Table 7 below.
- FIG. 3 is a graph showing the results of extraction rates (%) of Sc, Al, Fe, and Th contained in the organic solvent after solvent extraction.
- the extraction rate was a percentage of a value obtained by dividing the amount of each element contained in the extracted organic phase by the amount of each element contained in the original solution before extraction.
- the organic amount / metal amount is less than 0.01 times because the phase separation between the organic phase and the aqueous phase deteriorates. On the other hand, if the organic amount / metal amount exceeds 0.1 times, a large amount of scandium is contained in the organic phase, which is not preferable.
- FIG. 4 is a graph showing the relationship between the cleaning rate of scandium and thorium with respect to the concentration of sulfuric acid used for cleaning.
- the washing rate refers to the proportion of the metal that has been separated from the organic solvent and contained in the sulfuric acid.
- scandium could be separated and recovered from the organic solvent at any sulfuric acid concentration, particularly when the sulfuric acid concentration was 1 mol / L or more and 3 mol / L or less. While only thorium was left in the organic solvent, only scandium could be efficiently separated and recovered from the organic solvent.
- Example 3 To the post-sulfurization solution having the same composition shown in Table 1 used in Example 1, various impurities were added as necessary with a reagent as in Example 1, and a chelate resin was further used in the same manner. Ion exchange treatment was performed, and sulfuric acid was passed through the chelate resin after the ion exchange treatment to obtain a scandium eluent having the composition shown in Table 9 below.
- the obtained scandium eluent was placed in a container, and a 4N sodium hydroxide solution was added with stirring to adjust the pH of the solution to 1.
- the stirring is stopped, the mixture is left to stand, the amount of the liquid is measured, and the supernatant liquid is collected.
- the stirring is restarted, and the 4N sodium hydroxide solution is added again.
- the pH was adjusted to 2.
- the stirring was stopped, the liquid was measured, the supernatant liquid was collected, and the stirring was repeated again to prepare samples of each scandium eluent in the range where the pH of the solution was 1 to 6. .
- the components shown in Table 9 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 quantity of the components present in the solution and the initial quantity calculated from the analysis value of the scandium eluent and the initial quantity shown in Table 9 corresponds to the amount of precipitation generated by pH adjustment (neutralization).
- the ratio obtained by dividing the amount of precipitation by the above-mentioned initial amount was defined as the precipitation rate (%).
- FIG. 5 shows each pH and the precipitation rate of the components shown in Table 9.
- 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.
- the precipitation rate of aluminum increases when the pH exceeds 4.5.
- 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.
- a sodium hydroxide solution having a concentration of 4N was added to the scandium eluent having the composition shown in Table 9 so that the pH of the solution was between 5 and 6.
- a precipitate was formed by mixing, and then solid-liquid separation was performed to obtain a scandium hydroxide precipitate.
- Example 2 the obtained redissolved solution is subjected to solvent extraction in the same manner as in Example 1, using the obtained redissolved solution as the starting solution, and scandium oxalate is produced from the obtained extracted residue, and then roasted to obtain scandium oxide. Obtained. As a result, scandium oxide having a lower iron quality than Example 1 could be obtained.
- Example 4 To the post-sulfurization solution having the same composition shown in Table 1 used in Example 1, various impurities were added as necessary with a reagent as in Example 1, and a chelate resin was further used in the same manner. Ion exchange treatment was performed, and sulfuric acid was passed through the chelate resin after the ion exchange treatment to obtain a scandium eluent having the composition shown in Table 9 above.
- the obtained scandium eluent was placed in a container, and a 4N sodium hydroxide solution was added with stirring to perform first-stage neutralization to adjust the pH of the solution to 4. Thereafter, solid-liquid separation was performed using a filter paper and Nutsche to obtain a primary neutralized starch and a primary neutralized filtrate. Next, using ICP, the ratio (partition) of the amount of precipitation in which the amount of the precipitate contained in the scandium eluent (Table 9) before pH adjustment was analyzed was analyzed as the precipitation rate (%).
- Table 11 shows the precipitation rate (distribution) by the first stage neutralization. As shown in Table 11, by neutralizing until the pH of the solution becomes 4, iron and chromium that are impurities in the solution can be effectively precipitated and distributed to the primary neutralized filtrate. It was separated from scandium.
- the obtained primary neutralized filtrate was put in a container, and 4N sodium hydroxide was added thereto, and second-stage neutralization was performed so that the pH of the solution was adjusted to 6. Thereafter, solid-liquid separation was performed in the same manner as in the first-stage neutralization to obtain a secondary neutralized starch and a secondary neutralized filtrate. Subsequently, using ICP, the ratio (partition) of the amount of precipitation in the amount contained in the primary neutralized filtrate was analyzed as the precipitation rate (%).
- Table 12 below shows the precipitation rate (distribution) by the second stage neutralization. As shown in Table 12, almost 90% of the scandium remaining in the filtrate without precipitating most in the first stage neutralization was distributed to the secondary neutralized starch by the second stage neutralization. On the other hand, nickel, which is more basic than scandium, remained in the secondary neutralized filtrate without being precipitated by neutralization in both the first and second stages, and could be effectively separated from scandium. .
- the ratio (precipitation rate) distributed in the secondary neutralized starch among the components contained in the scandium eluent by performing such a two-step neutralization treatment is as shown in Table 13 below.
- aluminum was conspicuous, and other iron, chromium, nickel, etc. were effectively separated.
- Example 2 the obtained redissolved solution is subjected to solvent extraction in the same manner as in Example 1, using the obtained redissolved solution as the starting solution, and scandium oxalate is produced from the obtained extracted residue, and then roasted to obtain scandium oxide. Obtained. As a result, scandium oxide having a lower iron quality than Example 1 could be obtained.
- Example 5 To the post-sulfurization solution having the same composition shown in Table 1 used in Example 1, various impurities were added as necessary with a reagent as in Example 1, and a chelate resin was further used in the same manner. Ion exchange treatment was performed, and sulfuric acid was passed through the chelate resin after the ion exchange treatment to obtain a scandium eluent. Thereafter, as shown in Example 4, the scandium eluent was subjected to a two-step neutralization treatment, and the obtained redissolved solution was subjected to solvent extraction as an extraction starting solution, and the composition shown in Table 15 below was used. The extract was obtained.
- the obtained extraction residual liquid was used as an oxidation starter solution, sulfuric acid was added to adjust the pH of the solution to 0, and the temperature was maintained in the room temperature range of 25 ° C to 30 ° C.
- the pH value of the oxalic oxidation starting solution before pH adjustment was 1, and the oxidation-reduction potential (ORP) was a value measured from a silver-silver chloride electrode as a reference electrode and was in the range of 500 mV to 550 mV.
- oxalic acid treatment was performed by mixing oxalic acid into the oxalic oxidation starting solution after pH adjustment.
- a reagent causing a reaction is usually added to the solution and mixed.
- oxalic acid crystals or solutions are conventionally added to the oxalate oxidation starting solution.
- the addition method opposite to the conventional method that is, the oxalate oxidation start solution in which the oxalate start solution is added to the reaction tank filled with the oxalic acid solution having an oxalate concentration of 100 g / L.
- the solution was added in an amount ranging from 1.4 equivalents to 2.0 equivalents of scandium contained in the liquid, and allowed to react for 1 hour with stirring at room temperature.
- the obtained scandium oxide was washed with pure water, dried, and analyzed for metal components by ICP atomic absorption spectrophotometry. The measurement results are shown in Table 16 below.
- the iron grade and aluminum grade could be kept low, and high-purity scandium oxide containing scandium exceeding 99.9% grade could be obtained.
- the uranium quality was below the detection limit of 1 ppm.
- the iron quality is particularly high compared to the scandium oxide obtained in Example 5, and as a result, the purity of scandium oxide may not reach 99.9%. Slightly decreased.
- Example 2 Using the same oxalate starting solution as in Example 5, leaving the pH at 1, and performing the oxalate treatment in the same manner as in Example 5 except that the pH was not adjusted by adding sulfuric acid, The scandium oxalate was roasted in the same manner, washed to produce scandium oxide, and the metal component was analyzed by ICP atomic absorption spectrophotometry. Table 18 below shows the measurement results.
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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、スカンジウムとその他の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。 << 1. Scandium recovery method >>
FIG. 1 is a flowchart showing an example of a scandium recovery method according to the present embodiment. In this scandium recovery method, scandium and other impurities are separated from an acidic solution containing scandium obtained by leaching nickel oxide ore with an acid such as sulfuric acid, whereby high-purity scandium can be easily and It is efficiently recovered.
<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。 ≪2. About each step of the scandium recovery method >>
<2-1. 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.
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。 (1) 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. In addition, what is necessary is just to perform the process in leaching process S11 according to the conventionally known HPAL process, for example, it describes in
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。 (2) Neutralization process Neutralization process S12 adjusts pH by adding a neutralizing agent to the leachate obtained by leaching process S11 mentioned above, and obtains the neutralized starch containing an impurity element, and the liquid after neutralization It is a process. By the neutralization treatment in this neutralization step S12, valuable metals 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. .
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。 (3) 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. By the sulfiding treatment in the sulfiding step S13, nickel, cobalt, zinc and the like become sulfides, and scandium and the like are included in the solution after sulfiding.
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。 <2-2. Scandium (Sc) elution step>
As described above, 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. However, in 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. Therefore, 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.
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。 [Adsorption process]
In the adsorption step S21, 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.
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。 [Aluminum removal process]
In the aluminum 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. In addition, when removing aluminum, it is preferable to maintain pH in the range of 1 or more and 2.5 or less, and it is more preferable to maintain in the range of 1.5 or more and 2.0 or less.
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、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。 [Scandium elution step]
In the scandium elution step S23, 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. When obtaining a scandium eluent, the normality of sulfuric acid used in the eluent is preferably maintained in the range of 0.3N to less than 3N, and more preferably maintained in the range of 0.5N to less than 2N.
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。クロムを除去する際に、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。 [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. When removing chromium, if 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.
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。また、トリウム等のアクチノイド元素は、スカンジウムと挙動が同一であり、分離が困難となる。 <2-3. Neutralization process>
As described above, in the scandium elution step S2, scandium and impurities are separated by the selectivity of the chelate resin, and the scandium separated from the impurities is recovered as a scandium eluent. However, due to the characteristics of the chelate resin used, not all impurities can be completely separated from scandium. In addition, actinide elements such as thorium have the same behavior as scandium and are difficult to separate.
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5~6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。 [Neutralization process]
In the neutralization step S31, a neutralizing agent is added to the scandium eluent to adjust the pH of the solution to a range of 5 to 6, and the scandium contained in the scandium eluent is used as a precipitate of scandium hydroxide. . In the neutralization step S31, a neutralized starch composed of scandium hydroxide and a neutralized filtrate are thus generated.
水酸化物溶解工程S32では、上述した中和工程S31における1段階又は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に対して、酸を添加することによって溶解し、再溶解液を得る。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抽出始液として後述する溶媒抽出処理に供することが好ましい。 [Hydroxide dissolution process]
In the hydroxide dissolution step S32, an acid is added to the neutralized starch mainly composed of scandium hydroxide recovered through the one-step or two-step neutralization treatment in the neutralization step S31 described above. To obtain a redissolved solution. In this Embodiment, it is preferable to use for the solvent extraction process mentioned later by using the redissolved solution obtained in this way as an extraction start liquid.
次に、溶媒抽出工程S4では、スカンジウム溶離工程S2により得られたスカンジウム含有溶液(スカンジウム溶離液)、又は、スカンジウム溶液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、溶媒抽出に供するスカンジウム溶離液や再溶解液は、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。 <2-4. Solvent extraction process>
Next, in the solvent extraction step S4, the scandium-containing solution (scandium eluent) obtained in the scandium elution step S2 or the redissolution obtained through the neutralization step S3 for neutralizing the scandium solution. The liquid is brought into contact with an extractant to obtain an extraction residual liquid containing scandium. The scandium eluent and redissolved solution used for solvent extraction are acidic solutions containing scandium and other impurity elements as described above, and these are referred to as “scandium-containing solutions”.
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、特にトリウム(Th)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、アミン系の抽出剤を用いた溶媒抽出処理を行うことを特徴としている。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トリウム等の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。 (1) Extraction step In the extraction step S41, a scandium-containing solution and an organic solvent containing an extractant are mixed, and impurities, particularly thorium (Th), is selectively extracted into the organic solvent. A solvent and a residue solution are obtained. The scandium recovery method according to the present embodiment is characterized in that a solvent extraction process using an amine-based extractant is performed in the extraction step S41. By performing a solvent extraction process using an amine-based extractant, impurities such as thorium can be extracted more efficiently and effectively and separated from scandium.
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)。 (2) Scrubbing (washing) step When the scandium is slightly present in the solvent in which impurities are extracted from the scandium-containing solution in the extraction step S41 described above, the extract obtained in the extraction step S41 is back-extracted. Before that, the organic solvent (organic phase) is subjected to scrubbing (washing) treatment, and scandium is separated into an aqueous phase and recovered from the extractant (scrubbing step 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。 (3) Back extraction process In 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 post-extraction solution containing impurities.
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。 <2-5. Scandium recovery process>
Next, in the scandium recovery step S5, scandium is recovered from the extraction residual liquid obtained in the extraction step S41 in the solvent extraction step S4 and, if scrubbing is performed in the scrubbing step S42, the scrubbing cleaning liquid. To do.
シュウ酸塩化工程S51では、溶媒抽出工程S4で得られた抽残液及び洗浄液と所定量のシュウ酸とを混合させてシュウ酸スカンジウムの固体として析出させて分離する。 [Oxalization step]
In the oxalate forming step S51, the extraction residual liquid and the cleaning liquid obtained in the solvent extraction step S4 are mixed with a predetermined amount of oxalic acid, and precipitated and separated as a scandium oxalate solid.
焙焼工程S52は、シュウ酸塩化工程S51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。 [Roasting process]
The roasting step S52 is a step in which the precipitate of scandium oxalate obtained in the oxalate forming step S51 is washed with water and dried, and then roasted. Through this roasting treatment, scandium can be recovered as extremely high-purity scandium oxide.
[スカンジウム含有溶液(抽出前元液)の調製]
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。なお、下記表1に硫化後液の主要な組成を示す。 <Example 1>
[Preparation of scandium-containing solution (original solution before extraction)]
Based on a known method such as the method described in
〔抽出工程〕
次に、表2に示す組成の溶解液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て室温で60分間撹拌して溶媒抽出処理を施し、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。 [Solvent extraction]
[Extraction process]
Next, 100 liters of a solution having the composition shown in Table 2 was used as an extraction starting solution, and an amine-based extractant (manufactured by Dow Chemical Co., Primene JM-T) and a solvent (manufactured by Shell Chemicals Japan Co., Ltd., Shellsol A150) 50 liters of an organic solvent adjusted to 5% by volume was mixed and stirred at room temperature for 60 minutes to perform a solvent extraction treatment to obtain an extraction residue containing scandium. During extraction, no clad was formed, and phase separation after standing proceeded rapidly.
続いて、抽出工程で得られたスカンジウムを含む50リットルの有機溶媒(抽出有機相)に、濃度1mol/Lの硫酸溶液を、相比(O/A)が1の比率となるように50リットル混合し、60分間撹拌して洗浄した。その後、静置して水相を分離し、有機相は再び濃度1mol/Lの新たな硫酸溶液50リットルと混合して洗浄し、同様に水相を分離した。このような洗浄操作を合計5回繰り返した。 [Scrubbing (cleaning) process]
Subsequently, a 50 liter organic solvent (extracted organic phase) containing scandium obtained in the extraction step is mixed with a sulfuric acid solution having a concentration of 1 mol / L and 50 liter so that the phase ratio (O / A) is 1. Mix and wash with stirring for 60 minutes. 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 5 times in total.
続いて、洗浄後の抽出有機相に、濃度1mol/Lの炭酸ナトリウムを、相比O/A=1/1の比率となるように混合して60分間撹拌して逆抽出処理を施し、不純物を水相に逆抽出した。 [Back extraction process]
Subsequently, sodium carbonate having a concentration of 1 mol / L is mixed with the extracted organic phase after washing so as to have a phase ratio of O / A = 1/1, and the mixture is stirred for 60 minutes to perform a reverse extraction process. Was back extracted into the aqueous phase.
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。 [Oxalization step S7]
Next, 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.
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。 [Roasting step S8]
Next, the obtained scandium oxalate precipitate was subjected to suction filtration, washed with pure water, and dried at 105 ° C. for 8 hours. Subsequently, the dried scandium oxalate was put in a tube furnace and maintained at 850 to 900 ° C. and baked (fired) to obtain scandium oxide.
実施例1と同じ鉱石を用いて硫酸により浸出し、浸出液に対して中和処理を行い、次いでイオン交換樹脂に通液して上記表2に示す組成の抽出前元液を得た。この溶液を溶媒抽出工程に付さずに、直接、上述したシュウ酸塩化工程における処理を施した。それ以外は、実施例1と同じ方法を用いた。 <Comparative Example 1>
The same ore as in Example 1 was leached with sulfuric acid, the leachate was neutralized, and then passed through an ion exchange resin to obtain a pre-extraction original solution having the composition shown in Table 2 above. The solution was directly subjected to the treatment in the oxalate formation step described above without being subjected to the solvent extraction step. Otherwise, the same method as in Example 1 was used.
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及を行った。そして、得られたスカンジウム溶離液に水酸化ナトリウムを添加してpH6に調整して中和処理を施して中和澱物を生成させ、次いで得られた中和澱物(水酸化スカンジウム)に硫酸を添加して再び溶解し、必要に応じて実施例1と同じように試薬を添加する等して、下記表6に示す組成のキレート溶離液(水酸化物溶解液)を得て、溶媒抽出前元液とした。 <Example 2>
The post-sulfurization solution having the same composition shown in Table 1 used in Example 1 was subjected to an ion exchange treatment in the same manner as in Example 1. Then, sodium hydroxide is added to the obtained scandium eluent to adjust to
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と同様に様々な不純物を必要に応じて試薬で添加し、さらに同じ手法でキレート樹脂を用いたイオン交換処理を行い、イオン交換処理後のキレート樹脂に硫酸を通液して、下記表9に示す組成のスカンジウム溶離液を得た。 <Example 3>
To the post-sulfurization solution having the same composition shown in Table 1 used in Example 1, various impurities were added as necessary with a reagent as in Example 1, and a chelate resin was further used in the same manner. Ion exchange treatment was performed, and sulfuric acid was passed through the chelate resin after the ion exchange treatment to obtain a scandium eluent having the composition shown in Table 9 below.
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と同様に様々な不純物を必要に応じて試薬で添加し、さらに同じ手法でキレート樹脂を用いたイオン交換処理を行い、イオン交換処理後のキレート樹脂に硫酸を通液して、上記表9に示す組成のスカンジウム溶離液を得た。 <Example 4>
To the post-sulfurization solution having the same composition shown in Table 1 used in Example 1, various impurities were added as necessary with a reagent as in Example 1, and a chelate resin was further used in the same manner. Ion exchange treatment was performed, and sulfuric acid was passed through the chelate resin after the ion exchange treatment to obtain a scandium eluent having the composition shown in Table 9 above.
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と同様に様々な不純物を必要に応じて試薬で添加し、さらに同じ手法でキレート樹脂を用いたイオン交換処理を行い、イオン交換処理後のキレート樹脂に硫酸を通液して、スカンジウム溶離液を得た。その後、実施例4に示したように、スカンジウム溶離液に対して2段階の中和処理を施し、得られた再溶解液を抽出始液として溶媒抽出に付して、下記表15に示す組成の抽残液を得た。 <Example 5>
To the post-sulfurization solution having the same composition shown in Table 1 used in Example 1, various impurities were added as necessary with a reagent as in Example 1, and a chelate resin was further used in the same manner. Ion exchange treatment was performed, and sulfuric acid was passed through the chelate resin after the ion exchange treatment to obtain a scandium eluent. Thereafter, as shown in Example 4, the scandium eluent was subjected to a two-step neutralization treatment, and the obtained redissolved solution was subjected to solvent extraction as an extraction starting solution, and the composition shown in Table 15 below was used. The extract was obtained.
実施例5と同じシュウ酸塩化始液を用い、硫酸を添加して溶液のpH0に調整した。この参照例1では、シュウ塩化処理に際して、シュウ酸化始液が満たされた容器にシュウ酸溶液を添加して反応させた。そして、得られたシュウ酸スカンジウムを同様にして焙焼し、洗浄して酸化スカンジウムを生成させ、ICP原子吸光光度法によって金属成分を分析した。下記表17に、測定結果を示す。 <Reference Example 1>
Using the same oxalate conversion starting solution as in Example 5, sulfuric acid was added to adjust the pH of the solution to 0. In this reference example 1, during the oxalic acid chlorination treatment, the oxalic acid solution was added to the container filled with the oxalic oxidation starting solution and reacted. The obtained scandium oxalate was roasted in the same manner and washed to produce scandium oxide, and the metal component was analyzed by ICP atomic absorption spectrophotometry. Table 17 below shows the measurement results.
実施例5と同じシュウ酸塩化始液を用い、そのpHを1のままとして、硫酸添加によるpH調整を行わなかったこと以外は、実施例5と同様にしてシュウ酸塩化処理を行い、得られたシュウ酸スカンジウムを同様にして焙焼し、洗浄して酸化スカンジウムを生成させ、ICP原子吸光光度法によって金属成分を分析した。下記表18に、測定結果を示す。 <Reference Example 2>
Using the same oxalate starting solution as in Example 5, leaving the pH at 1, and performing the oxalate treatment in the same manner as in Example 5 except that the pH was not adjusted by adding sulfuric acid, The scandium oxalate was roasted in the same manner, washed to produce scandium oxide, and the metal component was analyzed by ICP atomic absorption spectrophotometry. Table 18 below shows the measurement results.
Claims (8)
- 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、次いで該イオン交換樹脂から溶離した溶離液を溶媒抽出に付して抽残液と抽出後抽出剤とに分離し、次いで該抽残液に対してシュウ酸塩化処理を施しシュウ酸スカンジウムの沈殿物を得て、該沈殿物を焙焼することによって酸化スカンジウムを得るスカンジウムの回収方法において、
前記溶媒抽出の抽出剤にアミン系抽出剤を用いる
スカンジウムの回収方法。 A solution containing scandium is passed through the ion exchange resin, and then the eluate eluted from the ion exchange resin is subjected to solvent extraction to separate the extraction residue and the extraction agent after extraction. In the method for recovering scandium, a scandium oxalate precipitate is obtained by oxalate treatment, and the precipitate is roasted to obtain scandium oxide.
A method for recovering scandium, wherein an amine-based extractant is used as an extractant for the solvent extraction. - 前記溶媒抽出後の抽出剤に、洗浄液としての1.0mol/L以上3.0mol/L以下の濃度の硫酸溶液を混合し、該抽出剤中に含まれるスカンジウムを該洗浄液中に分離するスクラビングを行い、スクラビング後の洗浄液からスカンジウムを回収する
請求項1に記載のスカンジウムの回収方法。 A scrubbing for mixing the extractant after the solvent extraction with a sulfuric acid solution having a concentration of 1.0 mol / L or more and 3.0 mol / L or less as a cleaning liquid and separating scandium contained in the extractant into the cleaning liquid. The method for recovering scandium according to claim 1, wherein scandium is recovered from the cleaning liquid after scrubbing. - 前記溶媒抽出後の抽出剤に炭酸塩を添加して逆抽出を行うことにより逆抽出後の抽出剤と逆抽出液とを得る
請求項1に記載のスカンジウムの回収方法。 The method for recovering scandium according to claim 1, wherein an extractant after back extraction and a back extract are obtained by adding carbonate to the extractant after solvent extraction and performing back extraction. - 逆抽出後の抽出剤を、前記溶媒抽出の抽出剤として繰り返し用いる
請求項3に記載のスカンジウムの回収方法。 The method for recovering scandium according to claim 3, wherein the extractant after back extraction is repeatedly used as the extractant for the solvent extraction. - 前記溶媒抽出に付される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。 The solution containing scandium subjected to the solvent extraction is:
A leaching step of leaching the nickel oxide ore with sulfuric acid under high temperature and high pressure to obtain a leachate;
A neutralization step of obtaining a neutralized starch containing impurities and a neutralized solution by adding a neutralizing agent to the leachate;
The post-sulfurization liquid obtained by a hydrometallurgical treatment of nickel oxide ore, comprising: a sulfurization step of obtaining a nickel sulfide and a post-sulfurization liquid by adding a sulfurizing agent to the post-neutralization liquid. The method for recovering scandium according to any one of the above. - 前記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pHを5~6の範囲に調整し、固液分離により中和澱物と中和濾液とを得て、該中和澱物に酸を添加することによって得られた再溶解液を前記溶媒抽出に付す
請求項1乃至5のいずれか1項に記載のスカンジウムの回収方法。 A neutralizing agent is added to the eluent eluted from the ion exchange resin to adjust the pH to a range of 5 to 6, and a neutralized starch and a neutralized filtrate are obtained by solid-liquid separation. The method for recovering scandium according to claim 1, wherein a redissolved solution obtained by adding an acid to the solvent is subjected to the solvent extraction. - 前記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pHを3.5~4.5の範囲に調整し、固液分離により1次中和澱物と1次中和濾液とを得て、次いで該1次中和濾液にさらに中和剤を添加してpHを5.5~6.5の範囲に調整し、固液分離により2次中和澱物と2次中和濾液とを得て、該2次中和澱物に酸を添加することによって得られた再溶解液を前記溶媒抽出に付す
請求項1乃至5のいずれか1項に記載のスカンジウムの回収方法。 A neutralizing agent is added to the eluent eluted from the ion exchange resin to adjust the pH to a range of 3.5 to 4.5, and a primary neutralized starch and a primary neutralized filtrate are separated by solid-liquid separation. Then, a neutralizing agent is further added to the primary neutralized filtrate to adjust the pH to a range of 5.5 to 6.5, and the secondary neutralized starch and the secondary neutralized filtrate are separated by solid-liquid separation. The method for recovering scandium according to any one of claims 1 to 5, wherein the redissolved solution obtained by adding an acid to the secondary neutralized starch is subjected to the solvent extraction. - 前記抽残液に対してシュウ酸塩化処理を施してシュウ酸スカンジウムの沈殿物を得るに際して、該抽残液のpHを-0.5以上1未満の範囲に調整し、そのpH調整後の溶液を、シュウ酸が含有された溶液の中に添加することによってシュウ酸スカンジウムの沈殿物を生成させる
請求項1乃至7のいずれか1項に記載のスカンジウムの回収方法。
When obtaining the precipitate of scandium oxalate by subjecting the extraction residue to oxalate treatment, the pH of the extraction residue is adjusted to a range of −0.5 or more and less than 1, and the solution after the pH adjustment The method for recovering scandium according to any one of claims 1 to 7, wherein a precipitate of scandium oxalate is generated by adding the succinic acid to a solution containing oxalic acid.
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US20180371579A1 (en) | 2015-12-16 | 2018-12-27 | Sumitomo Metal Mining Co., Ltd. | Method for recovering scandium |
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US10196710B1 (en) | 2016-01-25 | 2019-02-05 | Sumitomo Metal Mining Co., Ltd. | Method for recovering scandium |
JP2018035440A (en) * | 2016-08-30 | 2018-03-08 | 住友金属鉱山株式会社 | Production method of scandium compound, and scandium compound |
WO2018043242A1 (en) * | 2016-08-30 | 2018-03-08 | 住友金属鉱山株式会社 | Method for producing scandium compound, and scandium compound |
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