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WO2024262506A1 - Procédé de production d'une solution de lixiviation à partir d'hydroxyde comprenant du nickel et du cobalt - Google Patents

Procédé de production d'une solution de lixiviation à partir d'hydroxyde comprenant du nickel et du cobalt Download PDF

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Publication number
WO2024262506A1
WO2024262506A1 PCT/JP2024/022137 JP2024022137W WO2024262506A1 WO 2024262506 A1 WO2024262506 A1 WO 2024262506A1 JP 2024022137 W JP2024022137 W JP 2024022137W WO 2024262506 A1 WO2024262506 A1 WO 2024262506A1
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WIPO (PCT)
Prior art keywords
nickel
cobalt
hydroxide
ammonium sulfate
leaching
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PCT/JP2024/022137
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English (en)
Japanese (ja)
Inventor
祐輔 仙波
雅俊 高野
研哉 伊藤
聡 浅野
寛人 渡邉
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Publication date
Application filed by Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd
Publication of WO2024262506A1 publication Critical patent/WO2024262506A1/fr
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for producing a leachate containing nickel ions and cobalt ions from a hydroxide containing nickel and cobalt.
  • Lithium-ion secondary batteries which charge and discharge by the movement of lithium ions between the positive and negative electrodes, have a high energy density and do not deteriorate easily even when repeatedly charged and discharged, so in recent years demand has been increasing for them as power sources for electric vehicles and smart grid storage batteries, as well as for electronic devices such as mobile phones and laptops.
  • Lithium-ion secondary batteries have a structure in which an electrolyte is filled between the positive and negative electrodes that face each other with a separator in between, and lithium nickel oxide is used as the active material for the positive electrode, which is the main component.
  • Lithium nickel oxide can be manufactured by mixing lithium hydroxide with nickel hydroxide as a precursor and firing the mixture.
  • the above-mentioned nickel hydroxide as a precursor can be produced by a neutralization reaction caused by adding an aqueous sodium hydroxide solution to an aqueous nickel sulfate solution as a raw material.
  • sodium sulfate (mirabilite) produced as a by-product in an equimolar amount with nickel hydroxide as shown in the following formula 1 can be problematic. That is, since total wastewater volume regulations are set for sodium sulfate in some regions, there have been cases where it has been necessary to install costly treatment facilities to meet the wastewater standards, or to limit the production volume of nickel hydroxide in order to suppress the discharge of sodium sulfate.
  • Patent Document 1 proposes a technology in which oxygen is introduced into an aqueous ammonia solution containing powder of metallic nickel to leach the metallic nickel into the aqueous ammonia solution, and then seed crystals are added as necessary to the aqueous ammonia solution containing nickel and hydroxyl ions, and the aqueous ammonia solution is evaporated under atmospheric pressure or reduced pressure to precipitate and recover nickel hydroxide.
  • nickel hydroxide can be produced without producing sodium sulfate as a by-product, but this technology uses metallic nickel as the precursor raw material, and therefore is not economically advantageous.
  • metallic nickel is generally produced by leaching nickel from intermediate raw materials such as matte, sulfide, or hydroxide obtained by processing nickel ore using acid or chlorine, and then separating the impurities leached together with the nickel through a refining process before electrolytic winning, so that the metallic nickel finally obtained is in the form of a plate or lump. Therefore, a process is required to process metallic nickel into powder so that it can be efficiently leached with an aqueous ammonia solution.
  • cobalt may be added to the precursor during the manufacturing stage of the lithium nickel oxide.
  • the nickel used as the raw material for the precursor contains cobalt, and it is preferable that it contains a certain amount of cobalt.
  • a process is carried out to separate and remove cobalt from nickel by a refining process such as a solvent extraction process prior to electrowinning, which results in unnecessary separation costs.
  • the method of manufacturing nickel hydroxide using metallic nickel as a raw material requires many processes that increase costs, so there is a demand for an alternative method of manufacturing nickel hydroxide using unrefined intermediate raw materials containing a wide variety of impurities obtained, for example, by processing nickel oxide ore or scrap.
  • the present invention was made in consideration of the above circumstances, and aims to provide a method for producing a leachate containing nickel ions and cobalt ions using raw materials containing nickel and cobalt, which are cheaper than metallic nickel.
  • the method for producing a leachate according to the present invention is characterized in that a slurry is obtained by mixing hydroxide particles containing nickel and cobalt with ammonia water containing ammonium sulfate, and the slurry is subjected to a leaching treatment under a specified temperature condition to obtain a leachate containing nickel ions and cobalt ions leached from the hydroxide particles.
  • FIG. 1 is a block flow diagram of a method for producing nickel hydroxide containing cobalt, which preferably includes the method for producing a leachate of the present invention.
  • the method for producing a leachate according to this embodiment of the present invention is included in the method for producing nickel hydroxide containing cobalt as a precursor by subjecting a raw material nickel-cobalt mixed hydroxide to a series of treatments, as shown in Figure 1.
  • This raw material nickel-cobalt mixed hydroxide contains impurities such as calcium, magnesium, zinc, sulfur, silicon, manganese, iron, and aluminum.
  • Nickel-cobalt mixed hydroxide containing such various impurities is sometimes called a mixed hydroxide precipitate (MHP).
  • the method for producing nickel hydroxide containing cobalt in FIG. 1 includes a water washing step in which nickel-cobalt mixed hydroxide particles (MHP) are washed, preferably with water at room temperature, to mainly remove calcium and magnesium, an alkaline washing reduction step in which the nickel-cobalt mixed hydroxide particles washed in the water washing step are washed and reduced with an alkaline washing solution consisting of an aqueous caustic soda solution at room temperature and preferably with a concentration of about 8 mol/L, which contains a reducing agent such as sodium sulfite, to mainly remove zinc, sulfur, and silicon, and a process for reducing the nickel-cobalt mixed hydroxide particles washed in the water washing step.
  • MHP nickel-cobalt mixed hydroxide particles
  • the process includes a leaching process in which the reduced nickel-cobalt mixed hydroxide particles are leached with an ammonia-containing aqueous solution containing ammonium sulfate, a thermal decomposition precipitation process in which the leaching solution obtained by the leaching process is heated to thermally decompose the ammonium sulfate into ammonia and sulfur trioxide and precipitate the precursors nickel hydroxide and cobalt hydroxide, and an alkaline washing process in which the precipitated nickel hydroxide and cobalt hydroxide are washed with an alkaline washing solution, preferably an aqueous caustic soda solution at room temperature with a concentration of about 4 mol/L, to mainly remove the carbon content.
  • an alkaline washing solution preferably an aqueous caustic soda solution at room temperature with a concentration of about 4 mol/L
  • the water washing step is a step of removing mainly calcium and magnesium as impurities contained in the raw material nickel-cobalt mixed hydroxide using washing water preferably at a liquid temperature of 10 to 90°C, more preferably at room temperature.
  • this water washing step although there is no limitation, it is preferable to adopt a method in which the nickel-cobalt mixed hydroxide is introduced into washing water previously charged in a container equipped with a stirrer, and washed for 0.50 to 1.0 hours while stirring with the stirrer.
  • the slurry containing the nickel-cobalt mixed hydroxide particles is introduced into a solid-liquid separation device such as a centrifuge or a filter for solid-liquid separation, whereby the washed wet nickel-cobalt mixed hydroxide can be recovered.
  • a solid-liquid separation device such as a centrifuge or a filter for solid-liquid separation
  • the alkaline washing reduction step is a step for removing impurities that are difficult to remove in the previous water washing step, mainly zinc, sulfur, and silicon, by washing with an alkaline washing solution such as a caustic soda solution with a concentration of 1.0 to 8.0 mol/L.
  • the washing wastewater discharged after this washing contains impurities such as zinc, sulfur, and silicon, and is then repeatedly used as an alkaline washing solution after removing these impurities by a precipitation method or the like.
  • the precipitation method refers to a method for extracting solutes dissolved in a solution as precipitate particles, and for example, the above-mentioned precipitate particles can be obtained by changing the above-mentioned solution from an unsaturated state to a supersaturated state and promoting the generation and growth of crystal nuclei.
  • manganese, iron, and aluminum that are not leached in the above-mentioned leaching step remain as leaching residue, and are separated and removed from the leaching solution by solid-liquid separation means such as filtration.
  • the ammonia and sulfur trioxide generated by the thermal decomposition in the thermal decomposition precipitation means are recovered and reused as the ammonia water containing ammonium sulfate in the previous leaching step, and the carbon content in the cleaning solution discharged after cleaning in the alkaline cleaning step is reduced in solubility as the temperature of the cleaning wastewater drops, so in this case too, it is possible to precipitate the carbon content as sodium carbonate by using the precipitation method in the same manner as above. After removing the sodium carbonate in this way, the cleaning wastewater is repeatedly used as the alkaline cleaning solution.
  • the leaching process is a process in which the nickel-cobalt mixed hydroxide washed in the previous alkaline washing and reduction process is leached with an ammonium sulfate aqueous solution.
  • water is first charged into a container equipped with a stirrer, and ammonia (NH 3 ) water and ammonium sulfate ((NH 4 ) 2 SO 4 ) are added thereto to prepare an ammonium sulfate aqueous solution.
  • nickel-cobalt mixed hydroxide particles are charged into the container containing the prepared ammonium sulfate solution, and a slurry having a homogeneous concentration is prepared by stirring and mixing with the stirrer.
  • the temperature of the slurry is preferably maintained under a temperature condition of 20°C or higher and 60°C or lower to perform the leaching process. This allows nickel ions and cobalt ions to be leached from the nickel-cobalt mixed hydroxide particles. If the slurry temperature is lower than 20°C, the reaction rate is too slow and the production efficiency is reduced, and conversely, if it exceeds 60°C, ammonium sulfate is easily thermally decomposed, making it difficult to leach it well. If the slurry temperature is below 0° C., the water will freeze, making it difficult to prepare the ammonium sulfate solution.
  • the ammonium sulfate concentration in the ammonium sulfate aqueous solution is preferably adjusted to a range of 0.50 mol/L to 4.1 mol/L, more preferably 1.5 mol/L to 3.5 mol/L, and most preferably 2.0 mol/L to 3.0 mol/L. If the ammonium sulfate concentration is less than 1.5 mol/L, the leaching rate may decrease, and especially if it is less than 0.50 mol/L, the effect of the present invention may not be exhibited well.
  • ammonium sulfate concentration can be measured by absorptiometry, ion chromatography, etc. If the ammonium sulfate concentration is outside the above range, it can be adjusted by the amount of ammonium sulfate added.
  • free ammonia concentration in the slurry it is preferable to adjust the free ammonia concentration in the slurry to within the range of 0.1 to 1.3 mol/L. If the free ammonia concentration is within this range, nickel and cobalt can be leached stably in the form of ammine complexes. Even if the free ammonia concentration exceeds 1.3 mol/L, it has almost no effect on the stable leaching in the form of the above amine complexes, and it is not preferable because it increases costs and increases the load on wastewater treatment.
  • free ammonia refers to molecular ammonia (NH 3 ), and its concentration can be measured by absorptiometry after separating it by distillation and converting it to NH 4 + . If the free ammonia concentration is outside the above range, it can be adjusted by adding an amount of ammonia water.
  • the pyrolysis precipitation step is a step in which the leachate produced in the previous leaching step is heated by preferably maintaining the temperature at 60°C to 100°C for 0.50 to 2.0 hours, thereby pyrolyzing the ammine complexes of nickel and cobalt, precipitating the nickel and cobalt as hydroxides, and recovering them as precipitates.
  • this pyrolysis precipitation step it is preferable to stir while blowing in an oxidizing agent such as air, which promotes the oxidation of cobalt, making it possible to recover both nickel and cobalt as hydroxides at a high recovery rate.
  • ammine complex of cobalt is usually converted to divalent cobalt by pyrolysis, but by oxidizing it to trivalent cobalt, recovery as hydroxides is promoted. It is preferable to recover the ammonia and sulfur trioxide generated by pyrolysis in this pyrolysis precipitation step and reuse them as ammonia water containing ammonium sulfate in the previous leaching step.
  • the alkaline washing step is a step in which the nickel-cobalt mixed hydroxide recovered in the preceding thermal decomposition precipitation step is washed, preferably with the same alkaline washing solution as that used in the alkaline washing and reduction step described above. This removes zinc, sulfur, and silicon that could not be completely removed in the alkaline washing and reduction step, as well as carbon derived from ammonium sulfate added in the leaching step, and makes it possible to produce a high-purity precursor with extremely few impurities that can be suitably used as a positive electrode active material for lithium-ion secondary batteries.
  • the method for producing a leachate according to an embodiment of the present invention makes it possible to produce a leachate containing nickel and cobalt from the raw material nickel-cobalt mixed hydroxide particles without by-producing sodium sulfate, and also makes it possible to easily separate and remove impurities such as manganese, iron, and aluminum contained in the raw material, so that the leachate can be produced more inexpensively than when expensive metallic nickel is used as the raw material.
  • MHP nickel-cobalt mixed hydroxide
  • the nickel leaching rate was 45.6% and the cobalt leaching rate was 15.4%, and a leachate consisting of an aqueous ammonia solution containing a large amount of nickel ions and cobalt ions was produced.
  • Comparative Example 200 mL of 25% ammonia water was placed in a container, and 20 g of powdered nickel-cobalt mixed hydroxide (MHP) having the composition shown in Table 1 was mixed to form a slurry, which was stirred with a stirrer and held for 2 hours while adjusting the liquid temperature to 50° C., to carry out a leaching treatment. Thereafter, solid-liquid separation was carried out in the same manner as in the examples, and 200 mL of leachate was obtained. The element concentrations of this leachate were measured in the same manner as in the examples, and the leaching rate of each element was determined.
  • MHP powdered nickel-cobalt mixed hydroxide

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  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Le problème à résoudre par la présente invention est de fournir un procédé de production d'une solution de lixiviation qui comprend des ions nickel et des ions cobalt, à l'aide d'une matière première qui comprend du nickel et du cobalt et qui est moins coûteuse que la poudre de nickel métallique. La solution de l'invention porte sur une solution de lixiviation comprenant des ions nickel et des ions cobalt lixiviés à partir de particules d'hydroxyde qui est obtenue par la soumission d'une suspension à un processus de lixiviation dans des conditions de température prescrites, ladite suspension ayant été obtenue par le mélange des particules d'hydroxyde, qui comprennent du nickel et du cobalt, et d'ammoniac aqueux qui comprend du sulfate d'ammonium et a de préférence été régulé de telle sorte que la concentration en sulfate d'ammonium s'inscrive dans la plage de 0,5 à 4,1 mol/l.
PCT/JP2024/022137 2023-06-22 2024-06-18 Procédé de production d'une solution de lixiviation à partir d'hydroxyde comprenant du nickel et du cobalt Pending WO2024262506A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023-102876 2023-06-22
JP2023102876A JP2025002589A (ja) 2023-06-22 2023-06-22 ニッケル及びコバルトを含有する水酸化物からの浸出液の製造方法

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WO2024262506A1 true WO2024262506A1 (fr) 2024-12-26

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001062989A1 (fr) * 2000-02-22 2001-08-30 Anaconda Nickel Ltd Procede de recuperation de nickel et/ou de cobalt
WO2015081368A1 (fr) * 2013-12-03 2015-06-11 Bhp Billiton Nickel West Pty Ltd Procédé de production de nickel raffiné et d'autres produits à partir d'un intermédiaire hydroxyde mixte

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001062989A1 (fr) * 2000-02-22 2001-08-30 Anaconda Nickel Ltd Procede de recuperation de nickel et/ou de cobalt
WO2015081368A1 (fr) * 2013-12-03 2015-06-11 Bhp Billiton Nickel West Pty Ltd Procédé de production de nickel raffiné et d'autres produits à partir d'un intermédiaire hydroxyde mixte

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