WO2013061848A1 - 高純度硫酸コバルト水溶液の製造方法 - Google Patents
高純度硫酸コバルト水溶液の製造方法 Download PDFInfo
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- WO2013061848A1 WO2013061848A1 PCT/JP2012/076851 JP2012076851W WO2013061848A1 WO 2013061848 A1 WO2013061848 A1 WO 2013061848A1 JP 2012076851 W JP2012076851 W JP 2012076851W WO 2013061848 A1 WO2013061848 A1 WO 2013061848A1
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- 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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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Definitions
- the present invention relates to a method for separating manganese from a sulfuric acid solution containing manganese and cobalt to obtain a high-purity cobalt sulfate aqueous solution having a low manganese concentration that can be used as a raw material for a lithium ion secondary battery.
- Cobalt is a valuable metal used for heat-resistant alloys and the like, and recently, its use is expanding as a raw material for lithium ion secondary batteries. Cobalt is mostly contained in nickel ore such as nickel oxide ore, so after separation of nickel through processes such as dry or wet smelting and extraction, cobalt metal or salt, etc. As obtained.
- nickel ore when cobalt is obtained by dry smelting, nickel ore is smelted to produce nickel matte enriched with nickel or cobalt. Next, this nickel matte is leached with a mineral acid to form an acid solution containing nickel and cobalt, and then nickel is separated and recovered from this acid solution by a method such as solvent extraction to obtain cobalt as cobalt metal or cobalt sulfate. Have gained.
- nickel ore is leached with sulfuric acid under high temperature and high pressure, and a sulfiding agent is added to the leaching solution to form a mixed sulfide containing nickel and cobalt.
- This mixed sulfide is similar to the above nickel matte.
- the method of obtaining cobalt as a cobalt sulfate aqueous solution is also performed.
- the hydrometallurgical method using this high temperature and high pressure has the advantage that low-grade ore can be treated compared to the dry smelting method using the above smelting.
- the nickel oxide ore contains impurities such as manganese, magnesium, aluminum, zinc, and chromium in addition to nickel and cobalt, but there is a problem with the hydrometallurgical method for the separation of these impurities.
- impurities such as manganese, magnesium, aluminum, zinc, and chromium in addition to nickel and cobalt
- the hydrometallurgical method for the separation of these impurities for example, with respect to manganese, in the above-described hydrometallurgical process, manganese is leached into an acid solution together with nickel and cobalt, and is also distributed to sulfides, and the same behavior as cobalt is obtained by solvent extraction that separates nickel and cobalt. Thus, an aqueous solution containing manganese together with cobalt is obtained.
- the cobalt sulfate aqueous solution obtained when nickel is separated and recovered by the hydrometallurgical process contains manganese, which is an impurity, in a considerable concentration, so it can be used as a raw material for alloy addition and lithium ion secondary batteries. It was difficult to use. In the case of the dry smelting method, manganese can be effectively separated as slag generated by smelting, so that there is little influence on subsequent processes.
- a neutralization method As a method for removing manganese from an aqueous solution, various methods such as a neutralization method, a sulfide method, a contact filtration method, an ion exchange method, and an adsorption method are known. Among these methods, a neutralization method is easy and reliable as a method for industrial treatment, and thus has been widely used.
- an alkaline neutralizing agent such as sodium hydroxide, potassium hydroxide or slaked lime is added to an aqueous solution containing manganese to adjust the pH to 9 to 10, and manganese ions are converted into hydroxide form in this alkaline region. It is a method of removing by.
- Patent Document 1 discloses that permanganate is added as an oxidizing agent to water containing manganese and maintained at pH 3 to 8 to oxidize divalent manganese ions to tetravalent.
- a method of forming precipitates as manganese dioxide and insolubilizing them is shown.
- chlorine-based oxidizers such as chlorine gas and sodium hypochlorite are inexpensive, there is a concern that chlorine may remain in the cobalt sulfate solution when a chlorine-based oxidizer is used. As a result, since the chlorine is also mixed into the cobalt sulfate crystallized from the solution in which the chlorine remains, it cannot be used for applications requiring high-purity quality such as a secondary battery material.
- a method for separating nickel and cobalt from a leachate by an extraction method is also known.
- organic phosphoric acid, carboxylic acid, and organic phosphinic acid are used to extract manganese in an acidic solution to obtain cobalt. And how to separate them.
- manganese in this extraction method, in the case of an acidic solution obtained by leaching the above-mentioned nickel oxide ore with sulfuric acid, manganese is also contained in a high concentration, so that part of cobalt is extracted together with manganese due to variations in operating conditions. There are problems such as loss, or a part of manganese generates precipitates of oxides and hinders the operation of the solvent extraction process.
- the present invention can easily and efficiently remove manganese from a sulfuric acid aqueous solution containing cobalt and manganese at low cost, and can be used as a raw material for a lithium ion secondary battery.
- An object of the present invention is to provide a method for obtaining a highly pure aqueous cobalt sulfate solution.
- a method for producing a high-purity cobalt sulfate aqueous solution is a method for producing a cobalt sulfate aqueous solution from a sulfuric acid aqueous solution containing cobalt and manganese, which contains cobalt and manganese. While adjusting the pH of the sulfuric acid aqueous solution to a range of 2 to 4, the acidic organic extractant is mixed with the sulfuric acid aqueous solution to extract manganese into the organic phase.
- the acidic organic extractant is characterized in that a main component is di-2-ethylhexyl phosphate.
- the di-2-ethylhexyl phosphate in the acidic organic extractant is preferably diluted with a diluent so as to have a concentration of 10 to 30% by volume.
- the acidic organic extractant is adjusted to pH 2.1 or higher. By washing with water, the cobalt extracted in the acidic organic extractant can be back-extracted into the aqueous phase and recovered.
- At least one pH selected from sodium hydroxide, potassium hydroxide, magnesium oxide, magnesium hydroxide and an aqueous ammonia solution is used to adjust the pH of the acidic sulfuric acid aqueous solution. It is preferable to use a regulator.
- the sulfuric acid aqueous solution preferably has a cobalt concentration in the range of 70 to 100 g / l and a manganese concentration in the range of 0.05 to 1.0 g / l.
- manganese which is an impurity
- an acidic sulfuric acid aqueous solution containing cobalt and manganese by a simple method.
- manganese can be easily separated and removed from a sulfuric acid aqueous solution containing a high concentration of cobalt without using an expensive oxidizing agent or a chlorine-based oxidizing agent, and the loss of cobalt due to coprecipitation can be suppressed. it can.
- the high-purity cobalt sulfate aqueous solution obtained by the present invention has a very low manganese concentration and does not contain chlorine, and is therefore suitable as a raw material for a lithium ion secondary battery. Further, cobalt slightly extracted into the organic phase together with impurities such as manganese can be washed and back-extracted into the aqueous phase, so that the amount of cobalt that cannot be recovered and lost can be reduced.
- a pH adjuster is added to the aqueous phase.
- the manganese in the aqueous phase is selectively extracted into the organic phase by adjusting the pH of the aqueous solution in the range of 2 to 4, and a high-purity cobalt sulfate aqueous solution having a low manganese concentration is recovered as the aqueous phase.
- the pH adjusting agent used for adjusting the pH for example, sodium hydroxide, potassium hydroxide, magnesium oxide, magnesium hydroxide, an aqueous ammonia solution, or the like that generates a water-soluble sulfate after pH adjustment is suitable.
- Sodium hydroxide, potassium hydroxide, magnesium oxide, and magnesium hydroxide may be used in solid form, but are preferably used as an aqueous solution.
- Magnesium oxide dissolves in water to form a magnesium hydroxide aqueous solution.
- an aqueous ammonia solution is used as the pH adjuster, the amount of the drug used can be suppressed by installing an ammonia recovery step in the subsequent step, which is an economically excellent process.
- an organic phosphate-based acidic organic extractant is preferable, and an extractant mainly composed of di-2-ethylhexyl phosphate having high extractability with respect to zinc, iron, calcium and the like is particularly preferable.
- Examples of commercially available acidic organic extractants mainly composed of di-2-ethylhexyl phosphate include DP-8R (trade name) manufactured by Daihachi Chemical Co., Ltd.
- the diluent is not particularly limited, and various hydrocarbon-based diluents such as Teclean N-20 (trade name) manufactured by Nippon Oil Corporation can be used.
- the reason for adjusting the concentration of di-2-ethylhexyl phosphate in the organic phase (acidic organic extractant) to 10 to 30% by volume when using the acidic organic extractant di-2-ethylhexyl phosphate is 10 vol. If it is less than%, the amount of manganese extracted per extractant will decrease, and it will be necessary to increase the installed capacity accordingly. On the other hand, if it exceeds 30% by volume, the viscosity of the organic phase increases, the separability of the organic phase and the aqueous phase deteriorates, the operation becomes unstable, and the productivity decreases, which is not preferable. In order to reliably and stably perform the treatment, the range of 15 to 25% by volume is more preferable.
- impurities such as manganese can be extracted into an organic phase (acidic organic extractant) from a sulfuric acid aqueous solution containing cobalt and manganese while suppressing extraction of cobalt.
- organic phase acidic organic extractant
- cobalt in the sulfuric acid aqueous solution is partially extracted into the organic phase, it may be lost as it is and the recovery rate of cobalt may be reduced.
- the cobalt extracted in the acidic organic extractant is selectively removed by washing with water while adjusting the extracted acidic organic extractant (organic after extraction) to pH 2.1 or higher. It can be recovered by back extraction into the aqueous phase.
- the acidic organic extractant is mixed with the acidic aqueous sulfuric acid solution while adjusting the pH of the acidic aqueous sulfuric acid solution to a range of 2.6 to 4.
- the acidic organic extractant after extraction is washed with water and cobalt is selectively back-extracted into the aqueous phase, if the pH is reduced to 2.1 or less, the copper recovery rate can be increased. Since it goes up, it seems to be preferable at first glance. However, in many actual operations, the recovered liquid is generally repeated in the extraction stage and processed so as to achieve a water balance. Therefore, copper may accumulate unless the copper is discharged out of the system. There is a caution.
- O / A organic extractant
- the optimal range may be selected as appropriate through demonstration tests and actual operations.
- the O / A for extraction and back-extraction varies depending on the concentration of the solution to be obtained, but about 10 to 0.1 centering on 1 is appropriate.
- the reaction can proceed smoothly if the temperature is about 30 to 45 ° C. and the contact time is about several minutes to 1 hour.
- the acidic sulfuric acid aqueous solution used as a starting material in the present invention contains cobalt and manganese, and the composition thereof has a cobalt concentration of 70 to 100 g / l and a manganese concentration of 0.05 to 1.0 g / l. Those are preferred.
- Such an acidic sulfuric acid aqueous solution is not particularly limited.
- a mixed sulfide obtained by leaching nickel ore or a waste lithium ion secondary battery with sulfuric acid and sulfidizing the leached solution is sulfated.
- sulfuric acid acidic solution in which nickel is separated from the resulting solution by solvent extraction is sulfated.
- the reaction apparatus used for carrying out the above-described method of the present invention is not particularly limited, but various types of multistage counter-current reaction tanks capable of efficiently contacting and separating the organic phase and the aqueous phase are suitable. In view of industrial efficiency, it is preferable to use a continuous multistage countercurrent extraction tank such as a multistage countercurrent mixer settler.
- an organic phase composed of an acidic organic extractant is supplied to the first stage, an aqueous phase composed of a sulfuric acid aqueous solution to be purified is supplied to the final stage, and water is added to each stage.
- the organic phase and the aqueous phase are brought into countercurrent contact while supplying an alkali such as sodium oxide to maintain the pH in the multistage countercurrent extraction tank in the range of 2 to 4.
- the required number of extraction stages may be appropriately selected from the manganese concentration and the target concentration of the sulfuric acid aqueous solution. Accordingly, the purified high-purity cobalt sulfate aqueous solution is obtained from the first stage, and the organic phase containing manganese after the reaction is finished is obtained from the final stage.
- Example 1 A sulfuric acid aqueous solution containing cobalt and manganese was contacted with an acidic organic extractant, and distribution of manganese and other impurities into the aqueous phase and the organic phase was confirmed.
- An aqueous sulfuric acid aqueous solution was prepared using a sulfate reagent for each metal so as to have the composition shown in Table 1 below as a starting solution, and the pH was adjusted to 2.5 using an aqueous sodium hydroxide solution.
- Di-2-ethylhexyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name DP-8R) is used as an acidic organic extractant in the organic phase, and diluent (trade name Teclean N20, produced by Shin Nippon Oil Co., Ltd.) is used. It was used after diluting to a concentration of 20% by volume.
- aqueous phase Four sulfuric acid aqueous solutions (aqueous phase) and four acidic organic extractants (organic phases) were prepared, and the aqueous phase and the organic phase were extracted by a method simulating four-stage countercurrent extraction.
- the mixture was stirred at a stirrer while maintaining the temperature at 40 ° C. to obtain one stage of extraction. Stirring extraction was continued for 20 minutes, then stirring was stopped and the mixture was allowed to stand to separate an organic phase and an aqueous phase.
- the obtained aqueous phase and organic phase were sampled, and metal ions were analyzed by ICP.
- the sampled aqueous phase was contacted with the next new organic phase as a two-stage extraction, while the sampled organic phase was contacted with the new aqueous phase and subjected to the same treatment as above. By repeating this operation four times, a process simulating four-stage countercurrent extraction was performed. As a result of this treatment, the aqueous phase in the first extraction stage is in contact with the organic phase only once, but the aqueous phase in the second extraction stage is twice, the aqueous phase in the third extraction stage is three times, and the fourth extraction stage. In this case, the water phase in contact with the organic phase four times.
- Concentrations of cobalt, manganese, and other impurity components obtained by the ICP analysis for each aqueous phase obtained in the first to fourth extraction steps are shown in Table 1 as extraction first to fourth extraction steps. .
- concentrations of cobalt, manganese and other impurity components obtained in the ICP analysis are shown in the following Table 2 as extraction first to fourth extraction stages. It was.
- the organic phase of the acidic organic extractant from which manganese and other impurities and a part of cobalt are extracted is separated from the organic phase by scrubbing or back extraction treatment with pure water or sulfuric acid, etc., and repeated for new extraction. Can be used.
- Example 2 A sulfuric acid aqueous solution containing cobalt and manganese was brought into contact with an acidic organic extractant, and the extraction rate of manganese and other impurities into the organic phase was confirmed.
- Aqueous sulfuric acid aqueous solution was prepared using each metal sulfate reagent so as to have the composition shown in Table 3 below, and the pH was adjusted in the range of 2.0 to 4.0 using sodium hydroxide aqueous solution. Then, five starting solutions of the sulfuric acid aqueous solution adjusted to each pH were prepared.
- the organic organic acidic organic extractant di-2-ethylhexyl phosphate was diluted with a diluent to a concentration of 20% by volume as in Example 1 above.
- the water phase and the organic phase are charged into a beaker having a volume of 300 ml so that the volume ratio is 1: 1, and extraction is performed by stirring with a stirrer while maintaining the liquid temperature at 40 ° C. using a water bath. It was. Stirring extraction was continued for 20 minutes, then stirring was stopped and the mixture was allowed to stand to separate an organic phase and an aqueous phase. The obtained aqueous phase and organic phase were sampled, each metal ion was analyzed by ICP, and the extraction rate for each pH was determined and shown in FIG.
- the extraction rate is the difference between the analysis value of the aqueous phase after the extraction process and the amount calculated from the liquid amount in the amount of the starting liquid that is the aqueous phase, that is, the proportion extracted from the aqueous phase into the organic phase by extraction.
- the extraction rate of manganese greatly increases as the pH is increased from 2, whereas the extraction rate of cobalt is suppressed to a low level and slightly increases from around pH 4. Therefore, it was confirmed that the cobalt and manganese in the sulfuric acid aqueous solution can be efficiently separated by adjusting the pH to 2 or more and 4 or less.
- Example 3 A sulfuric acid aqueous solution containing cobalt and manganese was brought into contact with an acidic organic extractant, and the extraction rate of manganese and other impurities into the organic phase was confirmed.
- An aqueous sulfuric acid aqueous solution was prepared using a sulfate reagent for each metal so as to have the composition shown in Table 4 below, and the pH was adjusted to a range of 2.0 to 4.0 using an aqueous ammonia solution.
- a starting solution of sulfuric acid aqueous solution adjusted to each pH was prepared.
- di-2-ethylhexyl phosphate was diluted with a diluent to a concentration of 20% by volume as in Example 1 above.
- the obtained aqueous phase and organic phase were sampled, each metal ion was analyzed by ICP, and the extraction rate for each pH was determined and shown in FIG.
- the extraction rate is the difference between the analysis value of the aqueous phase after the extraction process and the amount calculated from the liquid amount in the amount of the starting liquid that is the aqueous phase, that is, the proportion extracted from the aqueous phase into the organic phase by extraction.
- Example 4 A sulfuric acid aqueous solution containing cobalt and manganese was contacted with an acidic organic extractant, and distribution of manganese and other impurities into the aqueous phase and the organic phase was confirmed.
- the aqueous sulfuric acid aqueous solution serving as the original solution was prepared using a sulfate reagent for each metal so as to have the composition shown in Table 5 below, and the pH was adjusted using an aqueous sodium hydroxide solution.
- Di-2-ethylhexyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name DP-8R) is used as an acidic organic extractant in the organic phase, and diluent (trade name Teclean N20, produced by Shin Nippon Oil Co., Ltd.) is used. It was used after diluting to a concentration of 20% by volume.
- the obtained aqueous phase and organic phase were sampled, and metal ions were analyzed by ICP.
- the extraction rate was calculated using the concentration of each metal in the obtained aqueous phase and organic phase, and the relationship between the obtained extraction rate and pH is shown in Table 6 and FIG.
- the extraction rate was calculated by dividing the amount extracted by the amount contained in the starting liquid.
- FIG. 3 which shows the result in this Example 4 is a result of the continuous test by 4 steps
- Example 5 An acidic organic extractant obtained by extracting cobalt from a sulfuric acid aqueous solution containing cobalt and manganese was brought into contact with water, and distribution of manganese and other impurities into the aqueous phase and the organic phase by back extraction was confirmed.
- the extracted organic organic extractant used as the original solution was extracted organic (organic before back extraction) obtained in Example 4 and having a composition range shown in Table 7 below.
- the obtained aqueous phase and organic phase were sampled, and metal ions were analyzed by ICP. Using the concentration of each metal in the obtained aqueous phase and organic phase, the recovery rate of cobalt, manganese and other impurity components to the aqueous phase was calculated, and the relationship between the obtained recovery rate and pH was shown in Table 8 below. This is shown in FIG. 4 containing cobalt and manganese. The recovery rate was calculated as a ratio obtained by dividing the amount of metal in the washing final solution by the sum of the amount of metal in the washed organic solution and the washed final solution.
Abstract
Description
コバルト及びマンガンを含む硫酸酸性水溶液と酸性有機抽出剤とを接触させ、マンガンその他の不純物の水相と有機相への分配を確認した。水相の硫酸酸性水溶液は下記表1中に始液として示す組成となるように各金属の硫酸塩の試薬を用いて調製し、水酸化ナトリウム水溶液を用いてpHを2.5に調整した。有機相の酸性有機抽出剤には、ジ-2-エチルヘキシルホスフェート(大八化学工業(株)製、商品名DP-8R)を希釈剤(新日本石油(株)製、商品名テクリーンN20)を用いて濃度20容量%になるように希釈して使用した。
コバルト及びマンガンを含む硫酸酸性水溶液と酸性有機抽出剤とを接触させ、マンガンその他の不純物の有機相への抽出率を確認した。水相の硫酸酸性水溶液は下記表3に示す組成となるように各金属の硫酸塩の試薬を用いて調製し、水酸化ナトリウム水溶液を用いてpHを2.0~4.0の範囲に調整し、各pHに調整した硫酸酸性水溶液の始液を5つ用意した。一方、有機相の酸性有機抽出剤としては、上記実施例1と同様に、ジ-2-エチルヘキシルホスフェートを希釈剤で濃度20容量%になるように希釈して使用した。
上記実施例2と同様の実験方法を用い、抽出時のpHを1.0、1.5、4.5及び5.0に変化させてコバルト及びマンガンの分配を確認した。尚、始液には上記表3に示す組成の硫酸酸性水溶液を用いた。
コバルト及びマンガンを含む硫酸酸性水溶液と酸性有機抽出剤とを接触させ、マンガンその他の不純物の有機相への抽出率を確認した。水相の硫酸酸性水溶液は下記表4に示す組成となるように各金属の硫酸塩の試薬を用いて調製し、アンモニア水溶液を用いてpHを2.0~4.0の範囲に調整し、各pHに調整した硫酸酸性水溶液の始液を用意した。一方、有機相の酸性有機抽出剤としては、上記実施例1と同様に、ジ-2-エチルヘキシルホスフェートを希釈剤で濃度20容量%になるように希釈して使用した。
コバルト及びマンガンを含む硫酸酸性水溶液と酸性有機抽出剤とを接触させ、マンガンその他の不純物の水相と有機相への分配を確認した。元液となる水相の硫酸酸性水溶液は、下記表5に示す組成となるように各金属の硫酸塩の試薬を用いて調製し、水酸化ナトリウム水溶液を用いてpHを調整した。有機相の酸性有機抽出剤には、ジ-2-エチルヘキシルホスフェート(大八化学工業(株)製、商品名DP-8R)を希釈剤(新日本石油(株)製、商品名テクリーンN20)を用いて濃度20容量%になるように希釈して使用した。
コバルト及びマンガンを含む硫酸酸性水溶液からコバルトなどを抽出した酸性有機抽出剤を水と接触させ、逆抽出によるマンガンその他の不純物の水相と有機相への分配を確認した。元液となる抽出した酸性有機抽出剤には、上記実施例4で得られた下記表7に示す組成の幅を有する抽出有機(逆抽出前有機)を使用した。
Claims (9)
- コバルトとマンガンとを含む硫酸酸性水溶液から硫酸コバルト水溶液を製造する方法であって、該コバルトとマンガンとを含む硫酸酸性水溶液のpHを2以上4以下の範囲に調整しながら、該硫酸酸性水溶液に酸性有機抽出剤を混合してマンガンを抽出することを特徴とする硫酸コバルト水溶液の製造方法。
- 前記酸性有機抽出剤は、主成分がジ-2-エチルヘキシルホスフェートであることを特徴とする、請求項1に記載の硫酸コバルト水溶液の製造方法。
- 前記酸性有機抽出剤中のジ-2-エチルヘキシルホスフェートは、濃度が10~30容量%となるように希釈剤で希釈されていることを特徴とする、請求項2に記載の硫酸コバルト水溶液の製造方法。
- 前記硫酸酸性水溶液が更に銅を含むとき、該硫酸酸性水溶液のpHを2.6以上4以下の範囲に調整しながら、該硫酸酸性水溶液に酸性有機抽出剤を混合してマンガンと共に銅を抽出することを特徴とする、請求項1~3のいずれかに記載の硫酸コバルト水溶液の製造方法。
- 前記コバルトとマンガンとを含む硫酸酸性水溶液から酸性有機抽出剤でマンガンを抽出した後、該酸性有機抽出剤をpH2.1以上に調整しながら水で洗浄することにより、該酸性有機抽出剤中に抽出されたコバルトを水相に逆抽出して回収することを特徴とする、請求項1~4のいずれかに記載の硫酸コバルト水溶液の製造方法。
- 前記硫酸酸性水溶液のpH調整に、水酸化ナトリウム、水酸化カリウム、酸化マグネシウム、水酸化マグネシウム、アンモニア水溶液から選ばれた少なくとも1種のpH調整剤を用いることを特徴とする、請求項1~5のいずれかに記載の硫酸コバルト水溶液の製造方法。
- 前記硫酸酸性水溶液は、コバルト濃度が70~100g/lの範囲及びマンガン濃度が0.05~1.0g/lの範囲であることを特徴とする、請求項1~6のいずれかに記載の硫酸コバルト水溶液の製造方法。
- 前記コバルトとマンガンとを含む硫酸酸性溶液は、ニッケル鉱石や廃リチウムイオン二次電池を硫酸で浸出し、その浸出液を硫化して得られた混合硫化物を硫酸で再度浸出して、得られた溶液から溶媒抽出によってニッケルを分離した硫酸溶液であることを特徴とする、請求項1~7のいずれかに記載の硫酸コバルト水溶液の製造方法。
- 多段向流抽出槽を用い、前記コバルトとマンガンとを含む硫酸酸性水溶液を該抽出槽の最終段に供給し、且つ前記酸性有機抽出剤を該抽出槽の第1段に供給すると共に、該抽出槽の各段にアルカリを供給して多段向流抽出槽内のpHを2以上4以下の範囲に維持することを特徴とする、請求項1~8のいずれかに記載の硫酸コバルト水溶液の製造方法。
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CA2853224A CA2853224C (en) | 2011-10-24 | 2012-10-17 | Method for producing high-purity cobalt sulfate aqueous solution |
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