WO2013099551A1 - 硫酸コバルトの製造方法 - Google Patents
硫酸コバルトの製造方法 Download PDFInfo
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- WO2013099551A1 WO2013099551A1 PCT/JP2012/081631 JP2012081631W WO2013099551A1 WO 2013099551 A1 WO2013099551 A1 WO 2013099551A1 JP 2012081631 W JP2012081631 W JP 2012081631W WO 2013099551 A1 WO2013099551 A1 WO 2013099551A1
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0476—Separation of nickel from cobalt
- C22B23/0484—Separation of nickel from cobalt in acidic type solutions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention can be used in the field of obtaining high-purity cobalt sulfate that can be used for battery materials with few impurities, particularly calcium, magnesium, and sodium, from an acidic hydrochloric acid solution containing cobalt.
- Cobalt is often contained in ore in coexistence with nickel, and is obtained as a joint product in nickel smelting.
- nickel and cobalt There are various methods for smelting nickel and cobalt, but in the smelting method called the dry method in which the ore is put into the furnace together with the reducing agent, cobalt is not separated from nickel and is directly used as a raw material for stainless steel. Since it is smelted to a loss of cobalt, it is not preferable.
- electrowinning with a chloride bath is more conductive than a sulfuric acid bath, so it is possible to save electrolysis power, and chloride ions after recovering cobalt metal are leached again. It is known that it can be repeated and is efficient and saves costs and labor.
- cobalt salts particularly cobalt sulfate.
- cobalt sulfate has recently been used in large quantities as a material for secondary batteries and the like, but cobalt sulfate for batteries has specifications for ensuring battery characteristics and ensuring safety.
- chloride ions in cobalt sulfate crystals are generally required to be maintained at a level of 0.1% or less.
- a method has been considered in which a cobalt-containing chloride solution is extracted with a solvent to extract cobalt ions, and this is back-extracted with a sulfuric acid solution to obtain a cobalt sulfate solution.
- extractants capable of separating this cobalt extractants such as phosphonic acid and phosphinic acid are known.
- the phosphonic acid and phosphinic acid 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester and di- (2,4,4-trimethylpentyl) phosphinic acid generally have good extractability of cobalt. It is used.
- an alloy scrap containing nickel and cobalt and containing no other elements as a compound is electrolytically dissolved while maintaining a cathode current density of 2 A / dm 2 or less using an aqueous sulfuric acid solution as an electrolytic solution. Then, the obtained nickel sulfate and cobalt sulfate-containing aqueous solution is purified, nickel ions and cobalt ions are extracted from the purified aqueous solution into organic substances, and nickel and cobalt ions are extracted back from the extract with hydrochloric acid or sulfuric acid. A nickel chloride and cobalt chloride mixed aqueous solution or a nickel sulfate and cobalt sulfate mixed aqueous solution to recover nickel and cobalt from nickel and cobalt alloy scrap.
- an aqueous solution of cobalt in a chloride bath or sulfuric acid bath can be obtained from cobalt in a sulfuric acid bath.
- impurities such as calcium, magnesium and sodium coexist in the chloride solution containing cobalt.
- the extraction behavior of these impurities in the above extractant has properties similar to the extraction behavior of cobalt, and it has been difficult to remove impurities such as calcium, magnesium and sodium from a solution containing cobalt.
- Patent Document 2 discloses a method for improving the extraction ability of copper when solvent is extracted from a chloride bath. This method is a method of recovering copper from an acidic aqueous solution containing copper chloride and an alkali and / or alkaline earth metal chloride by solvent extraction using a cation exchange type extractant. In the presence of sulfate ions. A sulfuric acid compound selected from the group consisting of sodium sulfate, magnesium sulfate, calcium sulfate, potassium sulfate and ammonium sulfate is added to the acidic aqueous solution so that the sulfate ion content is in the range of 10 to 100 g / L.
- the chlorine ion concentration and the bromine ion concentration in the acidic aqueous solution are within a predetermined range, and an acidic chelate extractant can be used as a cation exchange type extractant. Further, it is disclosed that the copper extraction capability is increased, the amount of solution handled in the copper leaching process performed in the previous stage can be reduced, and the equipment cost, the operation cost, etc. can be reduced. However, no method has been found for industrially and easily separating impurities such as calcium, magnesium and sodium from a solution containing mainly cobalt.
- the present invention effectively removes impurities such as calcium, magnesium and sodium in a process of obtaining a cobalt sulfate solution having a high cobalt concentration by solvent extraction using an acidic organic extractant, and produces high purity cobalt sulfate. With the goal.
- a first invention of the present invention that solves such problems is a cobalt sulfate production method for producing cobalt sulfate from a cobalt-containing chloride solution, wherein the cobalt-containing chloride solution is converted into the following first step.
- the second invention of the present invention is a method for producing cobalt sulfate, wherein the extractant in the first invention is an acidic phosphate ester type extractant.
- a 0 ) is maintained in the range of 5.0 to 7.0.
- the volume ratio (O / A 1 ) of the amount of the washing liquid (A 1 ) containing cobalt-containing organic phase (O) and cobalt is characterized in that the impurity ions contained in the cobalt-carrying organic phase are transferred to the washing solution containing cobalt while maintaining the pH at 5 to 10 and maintaining the pH in the range of 4.0 to 4.5. It is a manufacturing method of cobalt.
- a cobalt-retaining organic phase so that the cobalt concentration in the cobalt sulfate solution obtained by the third step in the first to fourth aspects is maintained in the range of 60 to 100 g / L. It is a manufacturing method of cobalt sulfate characterized by adjusting the amount of sulfuric acid contained in the back extraction starting liquid to be added.
- the sixth invention of the present invention is a method for producing cobalt sulfate, wherein the impurities in the first to fifth inventions are any one or more of calcium, magnesium and sodium ions.
- the chloride solution containing cobalt in the first to sixth inventions contains nickel and cobalt obtained by leaching a sulfide containing nickel with chloride and chlorine gas.
- a method for producing cobalt sulfate which is a solution obtained by separating a chloride solution by solvent extraction.
- the present invention produces high-purity cobalt sulfate from a chloride solution containing cobalt, and in particular, a chloride solution containing nickel and cobalt obtained by leaching a sulfide containing nickel with chloride and chlorine gas. It is suitable for a chloride solution containing cobalt obtained by separation by solvent extraction.
- a diluent is added to the extractant to be used, and 10 to 30% by volume is added. And preferably diluted to a concentration of 15-25% and the operating pH of the first step is in the range of 4.0-5.0, preferably in the range of 4.3-4.7, expressed in organic / liquid phase.
- the volume ratio of the liquid volume is in the range of 5.0 to 7.0, the operating pH of the second step is 4.0 to 4.5, and the volume ratio of the liquid volume expressed in organic phase / liquid phase is 5.0 to 10 0.0, maintaining the pH of the third step in the range of 0.5 to 1.0, the calcium, magnesium and sodium concentration ratios to the cobalt concentration of the resulting cobalt sulfate solution are 0.0001, 0.0001, Which reduces to below 0.00005 That.
- the solvent extraction step of the present invention is specifically composed of the following three steps.
- first step an extraction solvent diluted to contain the extractant main body at a concentration of 10 to 30% by volume, preferably 15 to 25% by volume, and a chloride solution containing impurities such as cobalt, calcium, magnesium and sodium Is extracted in the pH range of 4.0 to 5.0 to extract cobalt to obtain a cobalt-retaining organic phase.
- pH is added and adjusted while measuring during extraction to maintain a predetermined range. If the amount of the extractant is less than 10% by volume, the amount of the organic solvent required for the same amount of the starting liquid for extraction is increased, so that the equipment needs to be enlarged. If the concentration exceeds 30% by volume, the organic solvent after dilution The viscosity of the oil is so high that poor oil-water separation tends to occur, and stable operation becomes difficult.
- FIG. 1 shows the relationship between the extraction pH and the extraction rate of each element. From FIG. 1, in order to ensure the extraction rate of cobalt, it is necessary that pH is 4.0 or more. However, since the extraction rate of impurity elements such as magnesium also increases, the pH is preferably in the range of 4.3 to 4.7 in consideration of the extraction of cobalt and the separability of impurities.
- the pH is set to an acidic region of 1.0 or less, preferably in the range of 0.5 to 0.8. Is desirable.
- FIG. 2 shows the relationship between the volume ratio (O / A 0 ) of the organic solvent (O) and aqueous solution (A 0 ) in the first step (extraction step) and the extraction rate of cobalt, magnesium, and calcium. is there. From FIG. 2, the extraction rate of each component increases as the volume ratio of the liquid amount increases, and the extraction rate of cobalt is about 90% at the liquid volume ratio of 4.0.
- the volume ratio of the amount of the organic solvent (O) and the aqueous solution (A 0 ) needs to be 5.0 or more, and the organic solvent ( It is desirable that the volume ratio of the liquid volume of O) and the aqueous solution (A 0 ) is small.
- the optimal volume ratio of the liquid amount is preferably in the range of 5.0 to 7.0.
- the aqueous solution (A 0 ) in the first step (extraction step) is a chloride solution (A 0 ) containing cobalt.
- Table 1 shows the volume ratio (O / A 1 ) of the amount of the organic solvent (O) in the second step (cleaning step) and the cleaning solution (A 1 ) containing cobalt, and the cleaning efficiency of magnesium, calcium, and sodium (unit: %)
- lowering the volume ratio (O / A 1 ) of the liquid volume improves the calcium washing efficiency, but the ratio of the washing liquid volume to the back-extracted liquid volume increases, which is problematic in terms of productivity. It becomes. Therefore, it can be seen that the volume ratio (O / A 1 ) of the liquid amount is preferably in the range of 5 to 10 in order to obtain a calcium cleaning efficiency higher than 95%.
- Table 2 shows the relationship between the pH in the second step (washing step) and the calcium concentration in the organic solvent after the washing step.
- the pH of the washing step is preferably in the range of 4.0 to 4.5 because the calcium washing ability is lowered at pH 4.6 or higher.
- the cobalt concentration in the manufactured cobalt sulfate solution is maintained in the range of 60 to 100 g / L. If the cobalt concentration is low, the production efficiency is lowered. It is because it becomes easy to make it.
- the cobalt concentration in the cobalt sulfate solution is maintained within a predetermined range by adjusting the amount of sulfuric acid contained in the back extraction starting solution added to the cobalt-retaining organic phase. For example, the back extraction starting solution to which dilute sulfuric acid is added. Is used by adjusting the concentration of the diluted sulfuric acid.
- the present invention will be described using examples.
- the first step (extraction step) of solvent extraction is the second stage
- the second step (washing step) is the third stage
- the third step (back extraction step) is the second stage mixer settler (manufactured by Japan FP Corporation 3L FRP Mixer mixer) was used.
- the mixer settler used was 0.5 liters in the effective volume of the mixer part of the mixer settler, and 3 liters in the effective volume of the settler part.
- the first step (extraction step) and the third step (back extraction step) were performed so that the organic solvent and the aqueous solution were countercurrent.
- the organic solvent enters from the first-stage mixer and exits from the third-stage settler, but the aqueous solution is sulfuric acid as a cleaning solution containing cobalt in order to improve the cleaning efficiency of impurities in the organic solvent.
- a cobalt solution was used and poured into the mixer at each stage of the cleaning process, and discharged from the settler outlet at each stage.
- an extractant (trade name: PC88A, manufactured by Daihachi Chemical Industry Co., Ltd.) whose functional group is 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester is used, and this is used as an alkylbenzene-based diluent.
- Teclean N20 manufactured by Nippon Oil Corporation
- the feed rate of the mixed organic solvent is 112 ml / min
- the feed rate of the cobalt chloride solution in the first step is 22 ml / min
- the feed rate of the cobalt sulfate solution in the second step is 10.5 ml / min.
- the flow rate of dilute sulfuric acid in the third step was set to 15 ml / min at 3.5 ml / min in each stage.
- a cobalt chloride solution (starting solution) shown in Table 3 was used as the starting solution for solvent extraction, and a cobalt sulfate solution was prepared using the solvent extraction conditions shown in Table 4. The results are also shown in Table 3.
- the chloride ion concentration in the cobalt sulfate solution obtained by the present invention is less than 0.1 g / L, and from the abundance ratio with cobalt, the chloride product level in the cobalt sulfate crystal is suppressed to 0.02% or less. It was.
- Comparative Example 1 Using the same cobalt chloride solution shown in Table 3 as in Example 1 and using the solvent extraction conditions shown in Table 4, a cobalt sulfate solution (final solution) was prepared. The results are also shown in Table 3.
- Comparative Example 1 although the pH value at the time of contact between the extraction solvent of the first step and the chloride solution containing cobalt is lower than the range of the present invention, the extraction of cobalt slightly increases, but calcium, magnesium, etc. It can be seen that the concentration of impurities in the back-extracted solution is high because the impurities are easily extracted.
- Comparative Example 2 Cobalt sulfate was produced in the same manner as in Example 1 except that the solvent extraction conditions shown in Table 4 were outside the scope of the present invention. The results are also shown in Table 3.
- Comparative Example 2 since the concentration of the extractant is higher than 30%, the upper limit value of the cobalt concentration in the organic solvent is increased, but at the same time, impurities are easily extracted into the organic solvent, so that the obtained sulfuric acid is obtained. As a result, the quality of the cobalt solution deteriorates. In contrast to Comparative Example 2, when the concentration of the extractant is too low, the resulting cobalt sulfate solution has a low cobalt concentration and a low impurity concentration. However, productivity was lowered due to the low cobalt concentration.
- the calcium, magnesium, and sodium concentration ratios relative to cobalt are 0.0006, 0.001, and 0.025, respectively.
- Cobalt sulfate manufactured by the solvent extraction process consisting of two processes (washing process) and third process (back extraction process) has a calcium, magnesium and sodium concentration ratio to the cobalt concentration of 0.0001, It turns out that it is reduced to 0.0001 and 0.00005 or less.
- the impurity element concentration ratio to the cobalt concentration is not sufficiently reduced compared to the examples, and high purity cobalt sulfate is not obtained.
- high purity cobalt sulfate is not obtained.
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Abstract
Description
このニッケルやコバルトを製錬するには様々な方法があるが、乾式法と呼ばれる鉱石を還元剤と共に炉に入れる製錬方法では、コバルトはニッケルと分離されずにそのままステンレスの原料となるフェロニッケルに製錬されるために、コバルトのロスとなり、好ましくない。
特に硫酸を用いて浸出した場合、浸出に時間を要するので設備規模が拡大し、さらにメタルを回収した後に発生した硫酸を系外に払い出さなければプロセスの硫酸バランスが維持できず、一方で上記の硫化焙焼に必要な硫黄を供給する必要があるなどの課題があった。
この方法を用いると塩化物による硫化物の浸出は、迅速に進むので設備が比較的コンパクトで済む利点がある他に、硫化物を塩化物で浸出した後に浸出残渣として得られる硫黄を、硫化剤の原料として繰り返すことができ、さらに塩化物浴による電解採取は硫酸浴よりも伝導度が高いために電解電力の節減が可能であり、またコバルトメタルを回収した後の塩化物イオンを再度浸出工程に繰り返すことができるなど、効率的であり、コストや手間の節約になるメリットが知られている。
特に、硫酸コバルトは、近年では2次電池などの材料として多量に用いられるようになってきているが、電池向けの硫酸コバルトには、電池特性の確保や安全性の確保のためにスペックがあり、中でも硫酸コバルト結晶中の塩化物イオンは、一般に0.1%以下のレベルに維持することが必要とされている。
このコバルトを分離できる抽出剤として、ホスホン酸やホスフィン酸などの抽出剤が知られている。そのホスホン酸やホスフィン酸の具体的なものとして、2-エチルヘキシルホスホン酸モノ2-エチルヘキシルエステル、ジ-(2,4,4-トリメチルペンチル)ホスフィン酸は、コバルトの抽出性が良好なことから一般に使われている。
しかしながら、コバルトを含有する塩化物溶液には、カルシウム、マグネシウム、ナトリウムなどの不純物も共存している。これら不純物の上記の抽出剤における抽出挙動は、コバルトの抽出挙動と似た性質を持っており、コバルトを含有する溶液からカルシウム、マグネシウム、ナトリウムなどの不純物を除去することは困難であった。
この方法は、銅の塩化物と、アルカリ及び/又はアルカリ土類金属の塩化物とを含有する酸性水溶液から、陽イオン交換型抽出剤を用いて溶媒抽出により銅を回収する方法で、溶媒抽出を硫酸イオンの存在下で行う。硫酸ナトリウム、硫酸マグネシウム、硫酸カルシウム、硫酸カリウム及び硫酸アンモニウムよりなる群から選択される硫酸化合物を該酸性水溶液に添加し、硫酸イオンの含有量を10~100g/Lの範囲とする。
しかし、コバルトを主として含有する溶液からカルシウム、マグネシウム、ナトリウムのような不純物を工業的に効果的に容易に分離する方法は見出されていなかった。
(1)抽出剤を10~30体積%の割合で含有する抽出溶媒と、コバルトを含有する塩化物溶液とを、pHが4.0~5.0の範囲で接触させ、コバルトを含有する塩化物溶液からコバルトを抽出して、コバルト保持有機相を形成する第1工程。
(2)第1工程で得られたコバルト保持有機相と、コバルトを含む洗浄液とを混合することによって、コバルト保持有機相に含まれる不純物を、コバルトを含む洗浄液中に移行させた洗浄後コバルト保持有機相を形成する第2工程。
(3)第2工程で得られた洗浄後コバルト保持有機相に、逆抽出始液として希硫酸をpHが0.5~1.0の範囲になるように添加して、洗浄後コバルト保持有機相と希硫酸を接触させることによって、硫酸コバルト溶液を生成する第3工程。
(1)カルシウム、マグネシウム、ナトリウム濃度の低い、高純度な硫酸コバルトを製造できる。
(2)塩化浴を利用する効率の良い製錬方法を使いながら低塩化物品位の硫酸コバルトが得られる。
本発明の溶媒抽出工程は、具体的には以下の3つの工程から構成される。
第1工程では抽出剤本体を10~30体積%、望ましくは15~25体積%の濃度で含有するように希釈した抽出溶媒と、コバルト、カルシウム、マグネシウム、ナトリウムなどの不純物を含有する塩化物溶液とを、pHが4.0~5.0の範囲で接触させ、コバルトを抽出してコバルト保持有機相を得る抽出工程である。なお、pHは抽出中にも測定しながら添加調整して所定範囲を維持する。
抽出剤の量が10体積%未満では、同じ抽出始液量に対して必要な有機溶媒量が多くなる為に設備の大型化が必要となり、30体積%を超える濃度では、希釈後の有機溶媒の粘性が高く油水分離不良が起こりやすくなり、安定操業が困難となる。
第2工程では、第1工程で得たコバルト保持有機相と、予めコバルトを含む洗浄液とを混合し、コバルト保持有機相に含まれるカルシウムイオン、マグネシウムイオン、及びナトリウムイオンを、コバルトを含む洗浄液中に移行し、コバルトと分離する洗浄工程である。
第3工程では、第2工程で得られた洗浄後コバルト保持有機相と逆抽出始液である希硫酸とを、pHが0.5~1.0の維持した範囲で接触させ、硫酸コバルト溶液を得る逆抽出工程である。
図1から、コバルトの抽出率を確保するには、pHが4.0以上であることが必要である。しかし、マグネシウムなどの不純物元素の抽出率も増加するので、コバルトの抽出と不純物の分離性から考え、pHは4.3~4.7の範囲とすることが望ましい。
図2から、液量の容積比の増加に伴い各成分の抽出率は増加し、液量の容積比4.0では、コバルトの抽出率は約90%となる。
この第1工程(抽出工程)では、有機溶媒(O)と水溶液(A0)の液量の容積比は5.0以上必要であり、且つ設備の大型化を避ける為には、有機溶媒(O)と水溶液(A0)の液量の容積比は小さいほうが望ましい。このことから、最適な液量の容積比は5.0~7.0の範囲が良い。なお、第1工程(抽出工程)における水溶液(A0)は、コバルトを含有する塩化物溶液(A0)である。
そこで、カルシウムの洗浄効率を95%よりも高い洗浄効率を得るには、液量の容積比(O/A1)は5~10の範囲が望ましいことがわかる。
以下、実施例を用いて本発明を説明する。
使用したミキサーセトラーは、ミキサーセトラーのミキサー部の有効容量は0.5リットル、セトラー部の有効容量は3リットルの物を使用した。
第2工程(洗浄工程)は、有機溶媒が1段目のミキサーから入り3段目のセトラーから出るが、水溶液は有機溶媒中の不純物の洗浄効率を向上させる為に、コバルトを含む洗浄液として硫酸コバルト溶液を用い、洗浄工程の各段のミキサーに注入し、各段のセトラー出口から排出するように行った。
なお、本発明により得た硫酸コバルト溶液中の塩化物イオン濃度は、0.1g/L未満であり、コバルトとの存在比率から硫酸コバルト結晶中の塩化物品位は0.02%以下に抑制された。
実施例1と同じ表3に示す塩化コバルト溶液を用い、表4の溶媒抽出条件を用いて硫酸コバルト溶液(終液)を作製した。その結果を表3に併せて示す。
比較例1では、第1工程の抽出溶媒とコバルトを含有する塩化物溶液との接触時のpHの値が本発明の範囲より低いために、コバルトの抽出もやや増加するが、カルシウム、マグネシウムなどの不純物は簡単に抽出されやすくなる為に逆抽出液中の不純物濃度が高くなっているのがわかる。
表4に示す溶媒抽出条件が本発明の範囲外の条件であること以外は、実施例1と同様にして硫酸コバルトを作製した。その結果を表3に併せて示す。
この比較例2では、抽出剤の濃度が30%を超えて高いために、有機溶媒中のコバルト濃度の上限値は上がるが、同時に不純物も有機溶媒中に簡単に抽出される為、得られる硫酸コバルト溶液の品質が悪化してしまう結果となる。なお、比較例2とは逆に抽出剤の濃度が低すぎる場合には、得られる硫酸コバルト溶液は、コバルト濃度が低下すると共に不純物濃度も低下するために、コバルトに対する不純物の割合はあまり変化しなかったが、コバルト濃度が低いことから生産性の低下を余儀なくされた。
Claims (7)
- コバルトを含有する塩化物溶液から硫酸コバルトを生成する硫酸コバルトの製造方法において、
コバルトを含有する塩化物溶液を、以下の第1工程から第3工程からなる溶媒抽出工程で処理することによって硫酸コバルトを生成する硫酸コバルトの製造方法。
(1)抽出剤を10~30体積%の割合で含有する抽出溶媒と、前記コバルトを含有する塩化物溶液とを、pHが4.0~5.0の範囲で接触させ、前記コバルトを含有する塩化物溶液からコバルトを抽出して、コバルト保持有機相を形成する第1工程。
(2)前記第1工程で得られたコバルト保持有機相と、コバルトを含む洗浄液とを混合することによって、前記コバルト保持有機相に含まれる不純物を、前記コバルトを含む洗浄液中に移行させた洗浄後コバルト保持有機相を形成する第2工程。
(3)前記第2工程で得られた洗浄後コバルト保持有機相に、逆抽出始液として希硫酸をpHが0.5~1.0の範囲になるように添加して、前記洗浄後コバルト保持有機相と希硫酸を接触させることによって、硫酸コバルト溶液を形成する第3工程。 - 前記抽出剤が、酸性燐酸エステル系抽出剤であることを特徴とする請求項1記載の硫酸コバルトの製造方法。
- 前記第1工程におけるコバルト保持有機相(O)とコバルトを含有する塩化物溶液(A0)の液量の容積比(O/A0)が、5.0~7.0の範囲に維持されることを特徴とする請求項1又は2に記載の硫酸コバルトの製造方法。
- 前記第2工程における前記コバルト保持有機相(O)と前記コバルトを含む洗浄液(A1)の液量の容積比(O/A1)が、5.0~10.0に維持され、
pHを4.0~4.5の範囲に維持して、前記コバルト保持有機相中に含まれる不純物イオンを、前記コバルトを含む洗浄液に移行させること特徴とする請求項1~3のいずれか1項に記載の硫酸コバルトの製造方法。 - 前記第3工程により得られる硫酸コバルト溶液中のコバルト濃度が、60~100g/Lの範囲に維持されるように、前記コバルト保持有機相に添加する逆抽出始液の含有硫酸量を調整することを特徴とする請求項1~4のいずれか1項に記載の硫酸コバルトの製造方法。
- 前記不純物が、カルシウム、マグネシウム、ナトリウムイオンのうちいずれか1種類以上であることを特徴とする請求項1~5のいずれか1項に記載の硫酸コバルトの製造方法。
- 前記コバルトを含有する塩化物溶液が、ニッケルを含有する硫化物を塩化物と塩素ガスで浸出して得られるニッケルとコバルトを含有する塩化物溶液を、溶媒抽出によって分離して得た溶液であることを特徴とする請求項1~6のいずれか1項に記載の硫酸コバルトの製造方法。
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