WO2017073392A1 - Procédé de production de cristal de germe de cobalt - Google Patents

Procédé de production de cristal de germe de cobalt Download PDF

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Publication number
WO2017073392A1
WO2017073392A1 PCT/JP2016/080690 JP2016080690W WO2017073392A1 WO 2017073392 A1 WO2017073392 A1 WO 2017073392A1 JP 2016080690 W JP2016080690 W JP 2016080690W WO 2017073392 A1 WO2017073392 A1 WO 2017073392A1
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WO
WIPO (PCT)
Prior art keywords
cobalt
solid
powder
solution
cobalt powder
Prior art date
Application number
PCT/JP2016/080690
Other languages
English (en)
Japanese (ja)
Inventor
修 池田
龍馬 山隈
佳智 尾崎
高石　和幸
伸一 平郡
陽平 工藤
安夫 土居
Original Assignee
住友金属鉱山株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to CA3003239A priority Critical patent/CA3003239C/fr
Priority to EP16859622.9A priority patent/EP3369499A4/fr
Priority to AU2016345951A priority patent/AU2016345951B2/en
Priority to CN201680062357.XA priority patent/CN108349011A/zh
Priority to US15/770,546 priority patent/US20190061006A1/en
Publication of WO2017073392A1 publication Critical patent/WO2017073392A1/fr
Priority to PH12018500896A priority patent/PH12018500896A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys

Definitions

  • the present invention relates to a method for producing cobalt powder from a solution containing a cobalt sulfate ammine complex.
  • the present invention relates to a method for obtaining a seed crystal used for crystal growth.
  • cobalt salts used as electronic materials and heat-resistant alloys.
  • These cobalt salts are generally produced by dissolving cobalt metal in an acid, but the conventional sheet and block form such as general electric cobalt are easy to handle, but dissolution in acid is extremely slow.
  • the shape of the fine powder is difficult to handle because it is easy to dissolve in acid, but it is difficult to handle, and in order to take advantage of both, it is preferable to obtain a powder or powder obtained by compacting or sintering briquettes. It is rare.
  • Non-Patent Document 1 a method of obtaining cobalt powder by supplying hydrogen gas to a cobalt sulfate ammine complex solution in which cobalt is in the form of an ammonia complex to reduce cobalt ions in the complex solution.
  • Industrially inexpensive and useful since particles are generated and grown from an aqueous solution by a wet reaction, a large number of crystal nuclei are generated non-uniformly and the growth is hindered in the same manner as each of the prior arts described above. There is. In other words, it is indispensable to control the number of derived crystal nuclei within an appropriate range for efficient growth.
  • a method is generally used in which a reducing agent is supplied to a slurry in which a small amount of fine crystals called seed crystals coexist and a target product is grown on the surface of the seed crystals to obtain a powder having a predetermined particle size.
  • the seed crystals added in the above are often used after being subjected to a treatment such as pulverizing a part of the product repeatedly.
  • a treatment such as pulverizing a part of the product repeatedly.
  • the optimum grain size and properties of the seed crystal cannot always be obtained simply by pulverization. That is, a method for stably obtaining a seed crystal used for crystal growth has been demanded.
  • the present invention provides a production method for efficiently obtaining cobalt powder by a method for increasing the reduction reaction efficiency in producing cobalt powder from a solution containing a cobalt ammine sulfate complex.
  • the first invention of the present invention that solves such problems is to add a solution containing a cobalt sulfate ammine complex by adding ammonia, an ammonia compound solution, or both ammonia and an ammonia compound solution to a cobalt sulfate solution.
  • a complexing step to be obtained, a mixing step in which a solid is added to the solution containing the cobalt ammine sulfate complex obtained in the complexing step to form a mixed slurry, and the mixed slurry obtained in the mixing step are placed in a reaction vessel.
  • the obtained cobalt powder slurry is subjected to a solid-liquid separation process to obtain a cobalt precipitate and a post-reduction liquid in order.
  • the solid material in the first invention is made of a material insoluble or hardly soluble in the solution containing the cobalt ammine sulfate complex, and the average particle size thereof is 0.1 ⁇ m or more and 5 ⁇ m or less. It is the manufacturing method of the seed crystal of cobalt powder characterized by these.
  • a method for producing a seed crystal of cobalt powder wherein the cobalt concentration in the solution containing the cobalt ammine sulfate complex in the first and second aspects is 75 g / L or less. It is.
  • the fourth invention of the present invention is a method for producing a seed crystal of cobalt powder, characterized in that the solid material in the first to third inventions is nickel powder.
  • the solid-liquid separation step in the first to fourth inventions comprises a solid-liquid separation process for separating the cobalt deposit and the post-reduction liquid from the cobalt powder slurry, and the obtained cobalt deposit.
  • a seed of cobalt powder characterized by having a solids separation treatment for separating the added solids and cobalt powder deposited on the surface of the solids, and forming the post-reduction liquid and solids and cobalt powders It is a manufacturing method of a crystal.
  • a seed of an appropriate size is added to the cobalt sulfate ammine complex solution as a seed crystal to form the cobalt powder. Crystals can be obtained efficiently.
  • the present invention is a method for efficiently producing a seed crystal to be added when producing cobalt powder by blowing hydrogen gas into a cobalt sulfate ammine complex solution.
  • cobalt powder is obtained by passing the cobalt sulfate solution used as an original liquid through a complexing process, a mixing process, a reduction / precipitation process, and a solid-liquid separation process.
  • the reduction rate as used in the field of this invention was defined by the ratio which remove
  • the cobalt sulfate solution that can be used in the present invention is not particularly limited, but is a kind selected from cobalt and cobalt-containing mixed sulfide, crude cobalt sulfate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt powder, and the like, Alternatively, a cobalt leaching solution obtained by leaching and dissolving a cobalt-containing material such as an industrial intermediate composed of a plurality of mixtures with sulfuric acid or ammonia can be used.
  • the cobalt leachate generally contains various impurities, and the leachate described above is contained in the leachate by performing a liquid purification process such as solvent extraction, ion exchange, and neutralization. In general, it is used after removing the impurity element.
  • aqueous ammonia or ammonium sulfate is added to the cobalt leaching solution to obtain a cobalt sulfate ammine complex solution.
  • the ammonium sulfate concentration in the solution is preferably in the range of 10 to 500 g / L. If the concentration is 500 g / L or more, the solubility may be exceeded and crystals may be deposited, which may cause operational troubles. Moreover, since ammonium sulfate newly produces
  • the cobalt concentration in the cobalt sulfate ammine complex solution is 75 g / L or less. This is because, when adding and reacting a solid in the subsequent step, if the cobalt concentration in the cobalt sulfate ammine complex solution is too high, the reaction field is insufficient and the reduction rate is lowered.
  • a solid substance that serves as a base material for precipitation is added to the cobalt sulfate ammine complex solution prepared above.
  • the solid substance to be added is not particularly limited as long as it is insoluble in the cobalt sulfate ammine complex solution, the ammonium sulfate aqueous solution, or the alkali solution, or is hardly soluble and has low solubility.
  • nickel powder When cobalt powder is used as a solid substance, it is the same as cobalt precipitate, so it is not necessary to peel them off in the subsequent process and is optimal for use as a seed crystal, but industrially fine cobalt powder is inexpensive and stable. It is difficult to obtain.
  • Iron powder has the advantage of being inexpensive and easily available, but has the disadvantage of being easily dissolved in an acidic solution and difficult to form crystal nuclei. Also, the dissolved iron ion is not suitable because it causes new contamination. Also, in the method of depositing cobalt on a hardly soluble or insoluble solid as in the present invention, a method of depositing cobalt using a seed crystal that has been conventionally used to produce a product together with the seed crystal. Unlike the process, the effect of redissolving is negligibly avoided and there is no need to repeat a part of the product, so that the cobalt complex ions contained in the ammine complex solution can be reduced almost completely in terms of the process quantity balance. There are features that can be done.
  • the solid has a gentle shape so that the precipitated cobalt powder can be effectively separated, and the amount added is an amount that is equal to or more than the amount of cobalt present in the solution, as described above. More specifically, when nickel powder is used as a solid material, 75 g / L or more must be added.
  • the temperature of the mixed slurry at this time is preferably in the range of 150 to 200 ° C. If it is less than 150 degreeC, reduction
  • the pressure in the gas phase which is a gap with the solution in the reaction vessel, is preferably maintained in the range of 1.0 to 4.0 MPa by supplying hydrogen gas.
  • the pressure is less than 1.0 MPa, the reaction efficiency is lowered because the amount of gas mixed into the solution from the gas phase is small.
  • the pressure exceeds 4.0 MPa, there is no influence such as that the reaction is promoted. Rather, the loss of hydrogen gas only increases, which is not advantageous.
  • the hydrogen gas may be blown into the gas phase portion in the reaction tank or directly into the slurry.
  • Solid-liquid separation process The solid matter having cobalt precipitates on the surface obtained in the reduction / precipitation step is taken out from the pressure vessel together with the post-reduction liquid in the pressure vessel, and solid-liquid separated from the post-reduction solution.
  • This solid-liquid separation may be any method such as a method using Nutsche and a filter bottle, a method using a centrifuge, or a method using a filter press.
  • an operation of separating the solid and the cobalt deposit on the surface may be performed.
  • the method of specifically separating can be appropriately performed by giving an impact to the solid and the cobalt precipitate.
  • the size of the cobalt precipitate containing the solid matter and the cobalt precipitate after being separated from the solid matter is too small for the use to be used as a seed crystal, repeat the above mixing step again to precipitate cobalt.
  • the size of the object can be increased.
  • recovered here can be repeatedly used for the said mixing process again.
  • the solution after reduction can be regenerated to ammonia as it is or by treatment such as heating / distillation and repeatedly used as a complexing agent in the complexing step.
  • generates the seed crystal for obtaining the cobalt powder of this invention below is demonstrated.
  • the average particle size was measured using a commercially available laser diffraction / scattering particle size distribution measuring device (Microtrack).
  • a solution containing a cobalt sulfate ammine complex was obtained by adding 191 ml of 25% aqueous ammonia to 330 g of cobalt sulfate and 75 g of cobalt corresponding to 75 g of cobalt and dissolving the solution, and adjusting the total liquid volume to 1000 ml.
  • 75 g of nickel powder having a particle size of 1 ⁇ m serving as a precipitation matrix was added to obtain a mixed slurry.
  • the mixed slurry in the inner cylinder can was filtered to take out an insoluble solid having a cobalt precipitate formed on the surface, and then solid-liquid separation was performed by suction filtration using a filter bottle and Nutsche.
  • the reduction reaction rate of cobalt at this time was 99%.
  • the hydrogen gas was blown in a state where the temperature was raised and maintained at 185 ° C. while stirring, and the pressure in the inner cylinder can of the autoclave was changed. Hydrogen gas was supplied so as to maintain the pressure at 3.5 MPa. After 60 minutes had passed since the supply of hydrogen gas, the supply of hydrogen gas was stopped and the inner cylinder can was cooled.
  • the mixed slurry in the inner cylinder can was filtered to take out an insoluble solid with a cobalt precipitate formed on the surface, and then solid-liquid separation was performed by suction filtration using a filter bottle and Nutsche. At this time, the cobalt reduction reaction rate was 72%, which was not as efficient as the examples of the present invention.
  • Example 2 After the prepared mixed slurry was charged into the inner can of the autoclave used in Example 1, the temperature was raised to 185 ° C. while being stirred, and hydrogen gas was blown into the autoclave so that the pressure in the inner can of the autoclave was increased. Hydrogen gas was supplied so as to maintain the pressure at 3.5 MPa. After 60 minutes had passed since the supply of hydrogen gas, the supply of hydrogen gas was stopped and the inner cylinder can was cooled.
  • the mixed slurry in the inner cylinder can was filtered to take out iron powder with cobalt precipitates formed on the surface, and then solid-liquid separation was performed by suction filtration using a filter bottle and Nutsche.

Abstract

La présente invention concerne un procédé de production pour obtenir efficacement une poudre de cobalt au moyen d'un procédé qui augmente l'efficacité de la réaction de réduction pendant la production de la poudre de cobalt à partir d'une solution qui contient un complexe d'acide sulfurique-cobalt-amine. Un procédé de production d'un cristal de germe d'une poudre de cobalt, qui est caractérisé par la conduite séquentielle de : une étape de complexation pour obtenir une solution contenant un complexe d'acide sulfurique-cobalt-amine par ajout d'ammoniac et/ou d'une solution d'un composé d'ammoniac dans une solution de sulfate de cobalt, une étape de mélange pour obtenir une suspension concentrée mélangée par ajout d'un matériau solide dans la solution contenant un complexe d'acide sulfurique-cobalt-amine obtenue dans l'étape de complexation; une étape de réduction/dépôt pour obtenir une suspension concentrée de poudre de cobalt contenant un dépôt de cobalt, dans laquelle le composant de cobalt est déposé, sous la forme d'une poudre de cobalt, sur la surface du matériau solide, par introduction de la suspension concentrée mélangée obtenue dans les tables de mélange dans un réacteur et réduction du cobalt contenu dans la suspension concentrée mélangée par soufflage d'un gaz d'hydrogène dans le réacteur; une étape de séparation solide-liquide pour obtenir le dépôt de cobalt et le liquide après la réduction par soumission de la suspension concentrée de poudre de cobalt obtenue dans l'étape de réduction/dépôt à une séparation solide-liquide.
PCT/JP2016/080690 2015-10-26 2016-10-17 Procédé de production de cristal de germe de cobalt WO2017073392A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA3003239A CA3003239C (fr) 2015-10-26 2016-10-17 Procede de production de cristal de germe de cobalt
EP16859622.9A EP3369499A4 (fr) 2015-10-26 2016-10-17 Procédé de production de cristal de germe de cobalt
AU2016345951A AU2016345951B2 (en) 2015-10-26 2016-10-17 Method for producing seed crystal of cobalt powder
CN201680062357.XA CN108349011A (zh) 2015-10-26 2016-10-17 钴粉的晶种的制造方法
US15/770,546 US20190061006A1 (en) 2015-10-26 2016-10-17 Method for producing seed crystal of cobalt powder
PH12018500896A PH12018500896A1 (en) 2015-10-26 2018-04-26 Method for producing seed crystal of cobalt powder

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015210258A JP6350830B2 (ja) 2015-10-26 2015-10-26 コバルト粉の種結晶の製造方法
JP2015-210258 2015-10-26

Publications (1)

Publication Number Publication Date
WO2017073392A1 true WO2017073392A1 (fr) 2017-05-04

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PCT/JP2016/080690 WO2017073392A1 (fr) 2015-10-26 2016-10-17 Procédé de production de cristal de germe de cobalt

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US (1) US20190061006A1 (fr)
EP (1) EP3369499A4 (fr)
JP (1) JP6350830B2 (fr)
CN (1) CN108349011A (fr)
AU (1) AU2016345951B2 (fr)
CA (1) CA3003239C (fr)
PH (1) PH12018500896A1 (fr)
WO (1) WO2017073392A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020183728A1 (fr) * 2019-03-14 2020-09-17 住友金属鉱山株式会社 Procédé de production de poudre de nickel
CN116199270B (zh) * 2022-12-20 2023-08-11 科立鑫(珠海)新能源有限公司 一种减少钴氧化物生产过程废水的处理工艺
CN116177614B (zh) * 2023-03-23 2023-11-21 科立鑫(珠海)新能源有限公司 一种钴氧化物制备过程降低废料率的工艺方法

Citations (3)

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US3775098A (en) * 1971-12-27 1973-11-27 Sherritt Gordon Mines Ltd Cobalt precipitation from aqueous solutions
US4761177A (en) * 1987-06-26 1988-08-02 Amax Inc. Production of cobalt and nickel powder
JPH08503999A (ja) * 1992-10-26 1996-04-30 シェリット インコーポレイテッド 金属コバルト粉の製造方法

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US4545814A (en) * 1984-05-23 1985-10-08 Amax Inc. Production of cobalt and nickel powder
CN1060703C (zh) * 1996-05-30 2001-01-17 北京有色金属研究总院 纳米级金属粉的制备方法
CN100374231C (zh) * 2006-04-06 2008-03-12 北京工业大学 一种纳米钴粉的制备方法
CN101298102B (zh) * 2008-06-13 2011-03-23 上海师范大学 一种纳米钴颗粒的制备方法
CN101428349B (zh) * 2008-07-29 2011-06-22 张建玲 一种镍钴金属粉末的制备方法
JP6099601B2 (ja) * 2014-02-17 2017-03-22 国立大学法人高知大学 ニッケル粉の製造方法
CN104439280A (zh) * 2014-12-09 2015-03-25 英德佳纳金属科技有限公司 一种同时制备氢氧化钴和钴粉的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775098A (en) * 1971-12-27 1973-11-27 Sherritt Gordon Mines Ltd Cobalt precipitation from aqueous solutions
US4761177A (en) * 1987-06-26 1988-08-02 Amax Inc. Production of cobalt and nickel powder
JPH08503999A (ja) * 1992-10-26 1996-04-30 シェリット インコーポレイテッド 金属コバルト粉の製造方法

Non-Patent Citations (2)

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Title
See also references of EP3369499A4 *
W.KUNDA ET AL.: "THE REDUCTION OF COBALT FROM ITS AQUEOUS AMMINE AMMONIUM SULPHATE SYSTEM USING HYDROGEN UNDER PRESSURE", HYDROMETALLURGY, vol. 4, no. 4, 1979, pages 347 - 375, XP055380158 *

Also Published As

Publication number Publication date
JP6350830B2 (ja) 2018-07-04
CA3003239A1 (fr) 2017-05-04
PH12018500896B1 (en) 2018-10-29
US20190061006A1 (en) 2019-02-28
EP3369499A4 (fr) 2019-03-20
PH12018500896A1 (en) 2018-10-29
EP3369499A1 (fr) 2018-09-05
AU2016345951B2 (en) 2019-01-17
CN108349011A (zh) 2018-07-31
AU2016345951A1 (en) 2018-05-17
CA3003239C (fr) 2019-11-26
JP2017082270A (ja) 2017-05-18

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