WO2013077296A1 - 高純度硫酸ニッケルの製造方法 - Google Patents
高純度硫酸ニッケルの製造方法 Download PDFInfo
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- WO2013077296A1 WO2013077296A1 PCT/JP2012/079985 JP2012079985W WO2013077296A1 WO 2013077296 A1 WO2013077296 A1 WO 2013077296A1 JP 2012079985 W JP2012079985 W JP 2012079985W WO 2013077296 A1 WO2013077296 A1 WO 2013077296A1
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- nickel
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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
- C22B23/0453—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
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
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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
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Definitions
- the present invention is a method for producing high-purity nickel sulfate that can be used in the field of obtaining high-purity nickel sulfate that can be used for battery materials that are low in impurities, particularly magnesium, manganese, and calcium, from an acidic solution containing nickel. .
- Nickel is widely used as a material for stainless steel and corrosion resistant alloys, and recently, it is also widely used as a material for nickel metal hydride batteries and lithium ion batteries used in hybrid electric vehicles, mobile phones, personal computers, and the like. Nickel used for such a material is produced by mining ore existing as sulfide ore or oxide ore and smelting it.
- one method for treating sulfide ore is to put the ore into a furnace and melt it, to separate impurities as slag to obtain a nickel-concentrated mat, dissolve this mat with sulfuric acid or hydrochloric acid, dissolve it Impurities are separated from the solution to obtain a nickel solution, and nickel salts such as nickel sulfate and nickel oxide are produced by means such as neutralization and crystallization.
- nickel metal may be produced by performing electrolytic collection or the like.
- ferronickel which is an alloy of nickel and iron, and used as a raw material for stainless steel. It is.
- nickel sulfate which is one of nickel salts with high purity
- nickel is obtained as a metal once by a method such as electrowinning, this metal is dissolved again in sulfuric acid, and then the dissolved liquid is concentrated.
- a method of crystallizing nickel sulfate is also conceivable.
- obtaining metal requires a considerable amount of electric power and equipment of an appropriate scale, which is not an advantageous method in view of energy efficiency and cost.
- nickel-containing minerals often contain cobalt at the same time. Since cobalt is also a valuable metal and does not need to coexist with nickel, it is separated and recovered.
- Patent Document 1 shows an example in which cobalt is extracted by solvent extraction using a trade name PC88A (manufactured by Daihachi Chemical Industry Co., Ltd.) as an extractant to separate nickel and cobalt.
- PC88A manufactured by Daihachi Chemical Industry Co., Ltd.
- Patent Document 2 from an aqueous nickel solution containing calcium, magnesium, cobalt and the like as impurities, an alkylphosphonic acid ester containing nickel or an alkylphosphinic acid is used as an extractant, and the impurities in the aqueous nickel solution are extracted and separated.
- a method for producing a high-purity nickel aqueous solution that does not contain sodium or ammonia is shown.
- the nickel-containing material used as a raw material contains a large amount of impurities such as iron and aluminum, a large amount of neutralizing agent is required to separate them by a method such as neutralization, and impurities are further precipitated.
- valuable materials such as nickel and cobalt may co-precipitate and cause loss, and it has been difficult to operate efficiently.
- the present invention is a process for obtaining a nickel sulfate solution having a high nickel concentration by solvent extraction using an acidic organic extractant.
- the present invention provides a production method for obtaining high-purity nickel sulfate having a low metal ion such as magnesium or a chlorinated article.
- a first invention of the present invention for solving such problems is a high-purity nickel sulfate characterized in that an acidic solution containing nickel is treated through at least the following steps (1) to (4): It is a manufacturing method.
- Sulfurization process Sulfurization process in which a sulfurizing agent is added to an acidic solution containing nickel to obtain a precipitate of nickel sulfide and a liquid after sulfidation.
- Remelting step (1) A remelting step of preparing a nickel sulfide slurry obtained in the sulfurization step and adding an oxidizing agent to the slurry to obtain a nickel concentrate.
- Liquid purification step (2) A liquid purification step in which the nickel concentrate obtained in the re-dissolution step is neutralized by the addition of a neutralizing agent and a neutralized starch produced and a nickel concentrate after deironing are obtained.
- Solvent extraction step (3) A solvent extraction step in which the nickel concentrate after iron removal obtained in the liquid purification step is subjected to solvent extraction to obtain a reverse extraction solution and a nickel sulfate solution.
- the second invention of the present invention is a method for producing high-purity nickel sulfate, characterized in that the remelting in the remelting step in the first invention is performed in a temperature range of 60 ° C. or higher and 180 ° C. or lower.
- the oxidant added in the redissolving step in the first and second aspects is one or more oxidants selected from air, oxygen, hydrogen peroxide solution and ozone gas. This is a method for producing high-purity nickel sulfate.
- neutralization of the liquid purification process in the first to third inventions is performed by adding an alkali as a neutralizing agent and adjusting the pH to a range of 5.0 or more and 6.0 or less. This is a method for producing high-purity nickel sulfate.
- the fifth invention of the present invention is characterized in that the solvent extraction of the nickel concentrate after iron removal in the solvent extraction step in the first to fourth inventions is performed using an acidic phosphate ester extractant as the extractant. This is a method for producing high-purity nickel sulfate.
- the sixth invention of the present invention is a method for producing high purity nickel sulfate, characterized in that the nickel sulfate solution obtained in the solvent extraction step in the first to fifth inventions is converted into nickel sulfate crystals through a crystallization step. is there.
- the seventh invention of the present invention is a method for producing high-purity nickel sulfate, characterized in that the preliminary sulfidation step of the following step (1a) is performed before the sulfidation step in the first to sixth inventions.
- the nickel-containing acidic solution (also referred to as nickel-containing acidic solution) in the first to seventh aspects is a nickel oxide ore, nickel matte, nickel sulfide, a mixture of nickel and cobalt. Sulfides, crude nickel sulfate produced in the copper smelting process, as well as nickel oxide, nickel hydroxide, nickel carbonate, nickel powder, nickel metal, nickel metal hydride batteries, lithium ion batteries, and defective or in-process products generated in these manufacturing processes A method for producing high-purity nickel sulfate, which is a solution obtained by leaching nickel by adding sulfuric acid or hydrochloric acid to one or more of the above.
- FIG. 1 is a process diagram showing an example of a method for producing high-purity nickel sulfate. Usually, the process proceeds from sulfurization by adding a sulfiding agent to nickel-containing nickel solution according to the white arrow 1 to produce a high-purity nickel sulfate solution. Manufactured.
- the impurity element is removed from the nickel-containing material through the process of the “dashed line” frame and discharged out of the system as wastewater or wastewater starch.
- the reaction behavior was similar to that of nickel, and removal of magnesium from a solution containing nickel was insufficient.
- the acidic solution containing nickel as a raw material used in the present invention includes nickel oxide ore, nickel matte, nickel sulfide, mixed sulfide of nickel and cobalt, and crude nickel sulfate produced in the copper smelting process.
- nickel chemical products such as nickel oxide, nickel hydroxide, nickel carbonate, nickel powder, nickel metal, etc.
- batteries such as nickel metal hydride batteries and lithium ion batteries, and batteries such as nickel metal hydride batteries and lithium ion batteries.
- a solution obtained by leaching nickel by adding a mineral acid such as sulfuric acid or hydrochloric acid to a material containing nickel widely such as surplus products and defective products generated in the process can be used.
- the solutions obtained by leaching nickel it is particularly effective to use a solution in which magnesium, manganese and calcium are accumulated or concentrated, or a solution thereof as a part of the acidic solution. Furthermore, when the present invention is applied to a solution having a high magnesium, manganese and calcium concentration and a low nickel concentration, the sulfurizing agent for precipitating nickel as a sulfide can be reduced, which is more economical.
- the present invention is characterized in that it is produced through at least the following steps (1) to (4). Further, depending on the state of the acidic solution of the raw material, when the step (1a) is added, This makes it possible to produce highly efficient high-purity nickel.
- FIG. 2 is a smelting process diagram of the present invention.
- Sulfurization step includes description of (1a) preliminary sulfidation step
- a nickel component in the acidic solution is precipitated as nickel sulfide by adding a sulfiding agent to the acidic solution containing nickel described above and sulfiding.
- a known method can be used for this sulfurization. For example, it can be carried out by adding a gas or liquid sulfiding agent while measuring the oxidation-reduction potential (ORP) and pH of the acidic solution.
- ORP oxidation-reduction potential
- the amount of sulfiding agent added should be limited to the extent that nickel does not precipitate prior to the sulfiding step of sulfiding nickel. Or by applying a preliminary sulfidation step (1a) in which only impurities such as copper, zinc and lead are selectively separated in advance by strictly controlling the oxidation-reduction potential of the acidic solution. Is preferable.
- nickel when nickel is precipitated as sulfide, magnesium, manganese, calcium, chromium, aluminum, sodium, potassium, etc. do not form sulfide and remain in the solution except for part due to entrainment and adhesion. Therefore, most can be separated from nickel.
- the sulfurizing agent to be used is not particularly limited, but a hydrogen sulfide gas, sodium hydrosulfide, sodium sulfide and the like which can be easily obtained in large quantities can be used.
- the sulfiding temperature in the sulfiding step and pre-sulfiding step is not particularly limited, but is preferably 40 to 80 ° C. If it is less than 40 degreeC, reaction time will become long too much and the installation capacity
- the nickel sulfide and the sulfidized liquid are separated into solid and liquid.
- the solid-liquid separation method is not particularly limited, and the solid-liquid separation device to be used is not particularly limited, and a pressure filtration device, a suction filtration device, a decanter, and the like can be used.
- a part of the collected nickel sulfide containing nickel as a main component can be repeated as a seed crystal in the sulfidation step, so that the particle size of the sulfide can be expanded and the adhesion and entrainment of impurities can be suppressed.
- a pressurized container such as an autoclave and giving a temperature of 160 ° C. or higher, for example, is advantageous because it can dissolve quickly.
- the sulfur of the sulfide is oxidized to generate sulfuric acid without adding sulfuric acid as described above, and nickel sulfate is easily obtained. be able to.
- the leaching temperature exceeds 200 ° C. the reaction proceeds more rapidly, and the remaining or mixed iron forms insoluble iron oxide and can be efficiently separated from nickel.
- a container made of a material that can withstand temperatures exceeding 200 ° C. is extremely expensive, increases investment, and requires cost and labor for heating and maintenance. Therefore, it is desirable to operate at a temperature of about 160 to 180 ° C., which can be handled more inexpensively and easily.
- the target pH for neutralization is preferably in the range of 5.0 to 6.0. If the pH is less than 5.0, the removal of aluminum is insufficient. On the other hand, if the pH exceeds 6.0, precipitation starts up to nickel, resulting in a loss.
- the neutralizing agent to be used is not specifically limited, Sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, etc. can be used.
- the acidic solution obtained by acid leaching of nickel sulfide contains cobalt that is similar in chemical behavior to nickel, but cobalt is still present after the purification step. Therefore, the separation is necessary.
- the extractant used for solvent extraction an acidic phosphate ester-based extractant can be used.
- Nickel sulfate can be produced.
- the high-purity nickel sulfate produced according to the present invention should be provided in the form of a nickel sulfate solution or as nickel sulfate crystals formed using a general crystallization method such as crystallization or spray drying. Can do.
- the neutralization in the waste water treatment step is preferably adjusted to a pH of about 7.5 to 9.
- a method of adding an alkali to a post-sulfurization solution obtained after sulfiding an acidic solution, separating impurities that did not produce starch in the sulfidation step, and draining the resulting post-neutralization solution can also be used.
- nickel sulfide obtained in the sulfiding step (its composition is shown in Table 2) is fractioned at 200 Dry-g, and pure water is added to this to obtain a mixed sulfide slurry having a slurry concentration of about 200 g / L. 1 liter of was prepared.
- the prepared mixed sulfide slurry was charged into an autoclave apparatus, and stirred from 750 to 1000 revolutions per minute while being heated to maintain the temperature in the container at 160 to 170 ° C., from an oxygen cylinder. Pure oxygen was blown in at a flow rate of 0.43 liters per minute for 4 hours to redissolve the mixed sulfide. A small sample was taken out from the container after 2.5 hours and 3.3 hours had elapsed. After completion of the 4-hour blowing and re-dissolution reaction, the autoclave was cooled, the leached slurry was taken out, filtered through Nutsche, and separated into a leaching residue and a nickel concentrate.
- the composition of the obtained nickel concentrate was Ni: 120 g / L, Co: 8 g / L, Fe: 210 mg / L.
- the leaching rate of nickel in the mixed sulfide charged from the analytical value of the residue it was well leached to 99% or more, and 99.9% could be leached especially by leaching at 170 ° C. for 4 hours.
- Table 3 shows the change in nickel leaching rate depending on the reaction time for each temperature and applied pressure. As shown in Table 3, it can be seen that a nickel leaching rate of 99% or more can be obtained even in about 2.5 to 3.3 hours.
- the separatory funnel containing the organic solvent and the post-purification liquid was shaken for 10 minutes, allowed to stand, extracted, and then separated into an organic phase and an aqueous phase.
- components other than nickel, such as magnesium and cobalt are extracted into an organic solvent, and nickel corresponding to that component is transferred to the nickel sulfate solution in advance.
- Pre-sulfurization process 1800 ml of a nickel-containing sulfuric acid acidic solution containing copper, zinc, and a composition shown in Table 6 was collected, and the liquid temperature was kept at 60 ° C. using a heater. The sulfurizing agent was added while stirring at 300 rpm using a stirrer. Hydrogen sulfide gas was used as the sulfiding agent. A sealed container was used for the reaction.
- Hydrogen sulfide was added in an amount of 2.3 equivalents with respect to copper and zinc contained in the solution.
- the slurry after the reaction was sampled, filtered, and quantitative analysis of each element was performed by ICP emission spectrometry.
- a nickel sulfate solution having a composition shown in Table 6 was prepared by the same procedure as in Example 1.
- Table 6 shows that a high-purity nickel sulfuric acid solution can be obtained from a nickel-containing acidic solution containing a large amount of raw materials copper and zinc.
- Example 1 A hydrochloric acid acidic solution obtained by leaching a mixed sulfide obtained by sulfidation roasting of nickel and cobalt with sulfur using chlorine gas, which is a known method, is subjected to a solvent extraction step under the same conditions as in Example 1 and back-extracted. Thus, a nickel sulfate solution having the composition shown in Table 7 was obtained. All impurity grades such as copper, magnesium and chloride ions were higher than in the case of the present invention shown in Table 4.
- the present invention using the sulfidation process can provide a high-purity nickel sulfate solution with low impurity quality.
Abstract
Description
このような材料に用いられるニッケルは、硫化物鉱や酸化物鉱として存在する鉱石を採掘し、製錬して製造される。
特に、高品質な鉱石が枯渇しつつある近年は、その確保が困難となり、その結果入手できる鉱石中のニッケル品位は低下傾向となり、これらの低品位原料からニッケルを得るのには、さらにコストと手間を要するようになってきた。
この方法は、低品位の資源を有効かつ比較的少ないエネルギーで有効に利用できる技術であるが、上記のようなニッケル塩類を得ようとする場合、従来の製錬方法では見られなかった新たな課題も生じてきている。
これに対して、高温加圧浸出を用いた製錬方法では、マグネシウムやマンガンは酸によってよく浸出され、その結果ニッケル塩類への混入も増加する。また高温加圧浸出では、得た浸出スラリーにアルカリを添加してpHを調整する操作が行われるが、中和剤に使われるカルシウムのニッケル塩類への混入の影響も無視できない。
特に、ニッケルをリチウムイオン電池やニッケル水素電池の材料に用いる場合、マグネシウムやカルシウムや塩化物イオンが共存すると、製品に仕上げた電池の特性に大きく影響するため、ニッケル塩を製造する段階から混入をできるだけ排除した高純度ニッケル塩が望ましいとされる。
また、pH調整剤に含まれるナトリウムなどの不純物元素がニッケル溶液へ混入し、製品を汚染することを防止する方法としても有効である。
[工程]
(1)硫化工程
ニッケルを含有する酸性溶液に硫化剤を添加し、ニッケル硫化物の沈澱と硫化後液とを得る硫化工程。
(2)再溶解工程
(1)硫化工程で得たニッケル硫化物のスラリーを作製し、前記スラリーに酸化剤を添加して、ニッケル濃縮液を得る再溶解工程。
(3)浄液工程
(2)再溶解工程で得たニッケル濃縮液に、中和剤の添加による中和を施して生成した中和澱物と脱鉄後ニッケル濃縮液を得る浄液工程。
(4)溶媒抽出工程
(3)浄液工程で得た脱鉄後ニッケル濃縮液を溶媒抽出し、逆抽液と硫酸ニッケル溶液とを得る溶媒抽出工程。
工程(1a);ニッケルを含有する酸性溶液に硫化剤を添加し、ニッケルより硫化しやすい不純物を予め硫化して分離する予備硫化工程。
(b)ニッケル酸化鉱石を酸浸出して得た酸性溶液からも高純度な硫酸ニッケルを直接得ることができる。
(c)原料品位や操業負荷が変動しても得られる硫酸ニッケルの品質が安定する。
本発明は、ニッケルやマグネシウムなどの金属イオンを含有する硫化物からニッケル水素電池やリチウムイオン電池の原材料にも使用できる高純度な硫酸ニッケルを得るものである。
図1は、高純度硫酸ニッケルの製造方法の一例を示す工程図で、ニッケルを含むニッケル溶液への硫化剤添加による硫化から通常、白抜き矢印1に従って工程が進行して高純度硫酸ニッケル溶液が製造される。その製造過程中において、不純物元素は「破線」枠の工程を経ることによって、ニッケル含有物から除去され、排水若しくは排水澱物として系外に排出されるが、不純物元素の中のマグネシウムは、溶液中ではニッケルと反応挙動が似ており、ニッケルを含む溶液からのマグネシウムの除去は不十分な状況であった。
さらに、マグネシウム、マンガン、カルシウム濃度が高く、ニッケル濃度が低い溶液に、本発明を適用するほうが、ニッケルを硫化物として沈殿させるための硫化剤の低減が図れ、経済的でもある。
(1)硫化工程
ニッケルを含有する酸性溶液に硫化剤を添加し、ニッケル硫化物の沈澱と硫化後液とを得る硫化工程。
(2)再溶解工程
(1)の硫化工程で得たニッケル硫化物のスラリーを作製し、前記スラリーに酸化剤を添加して、ニッケル濃縮液を得る再溶解工程。
(3)浄液工程
(2)の再溶解工程で得たニッケル濃縮液に、中和剤の添加による中和工程を施して生成する中和澱物と脱鉄後ニッケル濃縮液を得る浄液工程。
(4)溶媒抽出工程
(3)の浄液工程で得た脱鉄後ニッケル濃縮液を溶媒抽出し、逆抽液と硫酸ニッケル溶液とを得る溶媒抽出工程。
(1a)予備硫化工程
ニッケルを含有する酸性溶液に硫化剤を添加し、ニッケルより硫化しやすい不純物を予め硫化して分離する予備硫化工程。
(1)硫化工程[(1a)予備硫化工程の説明を含む]
第1の硫化工程では、先に示したニッケルを含む酸性溶液に、硫化剤を添加して硫化することで、酸性溶液中のニッケル成分を硫化ニッケルとして沈殿させる。
この硫化は、公知の方法を用いることができる。例えば酸性溶液の酸化還元電位(ORP)とpHを測定しながらガスあるいは液状の硫化剤を添加することで行なうことができる。
40℃未満では反応時間が長くなりすぎ、必要な処理量を確保するための設備容量が増加する。また、80℃を超えると反応容器や配管に用いられる塩ビやFRPなど樹脂系の材料が使用できないため、設備の材質が制限され、設備投資が増加する。
この固液分離の方法は、特に限定せず、使用する固液分離装置は、特に限定されるものではなく、加圧濾過装置、吸引濾過装置、デカンターなどを用いることができる。
回収されたニッケルを主成分とするニッケル硫化物の一部は、硫化工程に種晶として繰り返すことで、硫化物の粒径を拡大し、不純物の付着や巻き込みを抑制することができる。
次に、(1)硫化工程で得た硫化物に、塩酸や硫酸などの鉱酸を加え、スラリー化した後、酸化剤を添加し、ニッケルを再び酸溶解して浸出する。この浸出する際は、例えば硫酸を濃度100~300g/lとなるように調整した溶液に硫化物を入れてスラリーを作製し、そのスラリーに酸化剤を添加しながら60~100℃に加熱することで行うことができる。
しかし、200℃を越える温度に耐える材質の容器は、きわめて高価で投資を増加させ、かつ加熱に要するコストや維持整備に費用と手間を要する。したがって、より安価手軽に取り扱える160~180℃程度の温度で操業することが望ましい。
前工程の(2)再溶解工程では、硫化物に巻き込まれたり、付着したりした不純物も液中へ溶出するが、硫化物は微細なため無視できない量になることが多い。
そのため固液分離後の不純物を含む液は、アルカリを添加する中和処理により鉄、アルミニウムなどの重金属を中和澱物として沈殿させる浄液工程を施す。
使用する中和剤は特に限定されるものではないが、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化マグネシウムなどを用いることができる。
次に、ニッケル硫化物を酸浸出して得られた酸性溶液にはニッケルと化学的な挙動が類似したコバルトが含有されるが、浄液工程を経た後にもコバルトは存在するため、その分離が必要となる。
ニッケルとコバルトとの分離は、浄液工程を経た溶液に溶媒抽出を行うのが効果的である。
溶媒抽出に用いる抽出剤には、酸性燐酸エステル系の抽出剤を用いることができる。
また、本発明により製造される高純度の硫酸ニッケルは、硫酸ニッケル溶液の形での提供や、晶析やスプレードライ等の一般的な結晶化方法を用いて形成した硫酸ニッケル結晶として提供することができる。
排水処理工程での中和は、pHを7.5~9程度の範囲に調整することが好ましい。
表1に示す組成のニッケルを含有する硫酸酸性溶液を400ml分取し、ウォーターバスを用いて液温を40℃に維持した。スターラーを用いて300rpmで撹拌しながら、硫化剤を添加した。なお、硫化剤には硫化ナトリウム9水和物を水に溶解し500g/Lに調整した液を使用した。
次に、硫化工程で得られたニッケル硫化物(その組成を表2に示す。)を200Dry-g分取し、これに純水を加えてスラリー濃度が約200g/Lとなる混合硫化物スラリーを1リットル作製した。
4時間の吹き込み、再溶解の反応が終了後、オートクレーブを冷却して浸出スラリーを取り出し、ヌッチェで濾過し、浸出残渣とニッケル濃縮液とに分離した。
残渣の分析値から装入した混合硫化物中のニッケルの浸出率を計算するといずれも99%以上とよく浸出されており、特に170℃で4時間浸出することで99.9%を浸出できた。
なお、表3に反応時間によるニッケル浸出率の変化を温度、付与圧力毎に示す。表3に示されるように、2.5時間から3.3時間程度でも99%以上のニッケル浸出率が得られることがわかる。
次に、得られたニッケル濃縮液に消石灰を添加し、pHを5.0~6.0の範囲に調整して浄液後液とした。この調整後、濾瓶とヌッチェを用いて中和後液(脱鉄後ニッケル濃縮液)と中和澱物とに固液分離し、ICPで分析した。
表4に、その結果を示すが、中和によりニッケル濃縮液に共存した鉄、クロム、銅、アルミなどを効果的に低減できることが確認できた。
次いで、pH調整後の浄液後液100mlを分液ロートに分取し、予めニッケルを抽出した有機溶媒を、有機(O)と溶液(A)との体積比率がO/A=3.5となるように添加した。
なお、上記の有機溶媒は、酸性燐酸エステル系の抽出剤(大八化学工業株式会社製「商品名:PC-88A」)を、希釈剤(JX日鉱日石エネルギー株式会社製「商品名:テクリーンN20」)を体積比で20:80となるように混合し、これを硫酸ニッケル溶液と接触させて有機溶媒中のニッケル濃度が15g/Lになるように調整したものを使用した。
その結果、表5に示すように、ニッケルに対するマグネシウムの存在量を6分の1に低減した高純度な硫酸ニッケル溶液を得ることができた。
表6に示す組成の銅、亜鉛、含むニッケル含有硫酸酸性溶液を1800ml分取し、ヒーターを用いて液温を60℃に保持した。攪拌機を用いて300rpmで撹拌しながら、硫化剤を添加した。なお、硫化剤には硫化水素ガスを使用した。反応には密閉型容器を使用した。
表6より、原料の銅、亜鉛を多く含むニッケル含有酸性溶液から高純度のニッケル硫酸溶液が得られることがわかった。
ニッケルとコバルトを硫黄と共に硫化焙焼して得た混合硫化物を公知の方法である塩素ガスを用いて浸出した塩酸酸性溶液を、実施例1と同じ条件で溶媒抽出工程に付し、逆抽出して表7に示す組成の硫酸ニッケル溶液を得た。
銅、マグネシウム、塩化物イオンなどいずれの不純物品位も表4に示す本発明の場合に比べて高くなっていた。
Claims (8)
- ニッケルを含有する酸性溶液を下記(1)~(4)の工程を少なくとも経て処理することを特徴とする高純度硫酸ニッケルの製造方法。
[工程]
(1)硫化工程
ニッケルを含有する酸性溶液に硫化剤を添加し、ニッケル硫化物の沈澱と硫化後液とを得る硫化工程。
(2)再溶解工程
(1)の硫化工程で得たニッケル硫化物のスラリーを作製し、前記スラリーに酸化剤を添加して、ニッケル濃縮液を得る再溶解工程。
(3)浄液工程
(2)の再溶解工程で得たニッケル濃縮液に、中和剤の添加による中和を施して生成する中和澱物と脱鉄後ニッケル濃縮液を得る浄液工程。
(4)溶媒抽出工程
(3)の浄液工程で得た脱鉄後ニッケル濃縮液を溶媒抽出し、逆抽液と硫酸ニッケル溶液とを得る溶媒抽出工程。 - (2)の再溶解工程における再溶解が、60℃以上、180℃以下の温度範囲で行われることを特徴とする請求項1記載の高純度硫酸ニッケルの製造方法。
- (2)の再溶解工程で添加される酸化剤が、空気、酸素、過酸化水素溶液およびオゾンガスから選択される1種類以上の酸化剤であることを特徴とする請求項1又は2に記載の高純度硫酸ニッケルの製造方法。
- (3)の浄液工程における中和が、中和剤のアルカリを添加してpHを5.0以上、6.0以下の範囲に調整して行われることを特徴とする請求項1~3のいずれか1項に記載の高純度硫酸ニッケルの製造方法。
- 工程(4)の溶媒抽出工程における脱鉄後ニッケル濃縮液に対する溶媒抽出が、抽出剤に酸性燐酸エステル系抽出剤を用いて行われることを特徴とする請求項1~4のいずれか1項に記載の高純度硫酸ニッケルの製造方法。
- 工程(4)の溶媒抽出工程で得た硫酸ニッケル溶液を、晶析工程を経て硫酸ニッケル結晶とすることを特徴とする請求項1~5のいずれか1項に記載の高純度硫酸ニッケルの製造方法。
- 工程(1)の硫化工程を施す前に、下記工程(1a)の予備硫化工程を施すことを特徴とする請求項1~6のいずれか1項に記載の高純度硫酸ニッケルの製造方法。
工程(1a);ニッケルを含有する酸性溶液に硫化剤を添加し、ニッケルより硫化しやすい不純物を予め硫化して分離する予備硫化工程。 - 前記ニッケルを含有する酸性溶液が、ニッケル酸化鉱、ニッケルマット、ニッケル硫化物、ニッケルとコバルトの混合硫化物、銅製錬工程で産出する粗硫酸ニッケル、並びに酸化ニッケル、水酸化ニッケル、炭酸ニッケル、ニッケル粉、ニッケルメタル、ニッケル水素電池、リチウムイオン電池およびこれらの製造工程で発生した不良品あるいは仕掛品のいずれか1種類以上のものに、硫酸もしくは塩酸を加えてニッケルを浸出して得られた溶液であることを特徴とする請求項1~7のいずれか1項に記載の高純度硫酸ニッケルの製造方法。
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- 2012-11-19 EP EP12851102.9A patent/EP2784166B1/en active Active
- 2012-11-19 WO PCT/JP2012/079985 patent/WO2013077296A1/ja active Application Filing
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Cited By (15)
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JP2015137383A (ja) * | 2014-01-21 | 2015-07-30 | 住友金属鉱山株式会社 | 金属硫化物のスラリー化方法 |
JP2015218075A (ja) * | 2014-05-15 | 2015-12-07 | 住友金属鉱山株式会社 | 高純度硫酸ニッケル水溶液の製造方法 |
JP2016141594A (ja) * | 2015-02-02 | 2016-08-08 | 住友金属鉱山株式会社 | 硫酸ニッケルの製造方法 |
JP2016210648A (ja) * | 2015-05-08 | 2016-12-15 | 住友金属鉱山株式会社 | 硫酸ニッケルの製造方法 |
JP2017025367A (ja) * | 2015-07-21 | 2017-02-02 | 住友金属鉱山株式会社 | 高純度硫酸ニッケル水溶液の製造方法 |
JP2017149609A (ja) * | 2016-02-25 | 2017-08-31 | 住友金属鉱山株式会社 | ニッケル水溶液の製造方法 |
JP2018193588A (ja) * | 2017-05-18 | 2018-12-06 | 住友金属鉱山株式会社 | 硫化物の浸出方法 |
US11959151B2 (en) | 2017-09-29 | 2024-04-16 | Sumitomo Metal Mining Co., Ltd. | Method for separating copper from nickel and cobalt |
WO2019124015A1 (ja) * | 2017-12-18 | 2019-06-27 | 住友金属鉱山株式会社 | 銅とニッケルおよびコバルトの分離方法 |
JP2019108586A (ja) * | 2017-12-18 | 2019-07-04 | 住友金属鉱山株式会社 | 銅とニッケルおよびコバルトの分離方法 |
US11718894B2 (en) | 2017-12-18 | 2023-08-08 | Sumitomo Metal Mining Co., Ltd. | Method for separating copper, and nickel and cobalt |
CN109706319A (zh) * | 2018-12-30 | 2019-05-03 | 温贵能 | 从电镀污泥中低成本回收金属并生产精制硫酸镍的方法 |
CN112573592A (zh) * | 2021-01-30 | 2021-03-30 | 浙江博瓦德新材料科技有限公司 | 一种高纯度氧化亚镍的制备方法 |
CN113528818A (zh) * | 2021-06-22 | 2021-10-22 | 江门市长优实业有限公司 | 一种硫酸镍溶液除杂的方法 |
CN113528818B (zh) * | 2021-06-22 | 2022-11-29 | 江门市长优实业有限公司 | 一种硫酸镍溶液除杂的方法 |
Also Published As
Publication number | Publication date |
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EP2784166B1 (en) | 2019-05-22 |
EP2784166A4 (en) | 2015-08-12 |
JP5904459B2 (ja) | 2016-04-13 |
EP2784166A1 (en) | 2014-10-01 |
AU2012341556A1 (en) | 2014-06-05 |
CN107032417A (zh) | 2017-08-11 |
CA2856341C (en) | 2016-08-09 |
PH12014501159B1 (en) | 2014-08-11 |
JPWO2013077296A1 (ja) | 2015-04-27 |
CN103946401A (zh) | 2014-07-23 |
US9017640B2 (en) | 2015-04-28 |
PH12014501159A1 (en) | 2014-08-11 |
US20140322109A1 (en) | 2014-10-30 |
CA2856341A1 (en) | 2013-05-30 |
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