US20190061006A1 - Method for producing seed crystal of cobalt powder - Google Patents

Method for producing seed crystal of cobalt powder Download PDF

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Publication number
US20190061006A1
US20190061006A1 US15/770,546 US201615770546A US2019061006A1 US 20190061006 A1 US20190061006 A1 US 20190061006A1 US 201615770546 A US201615770546 A US 201615770546A US 2019061006 A1 US2019061006 A1 US 2019061006A1
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United States
Prior art keywords
cobalt
solid
powder
solution
reduction
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Abandoned
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US15/770,546
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English (en)
Inventor
Osamu Ikeda
Ryo-ma Yamaguma
Yoshitomo Ozaki
Kazuyuki Takaishi
Shin-ichi Heguri
Yohei Kudo
Yasuo Doi
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Publication date
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Assigned to SUMITOMO METAL MINING CO., LTD. reassignment SUMITOMO METAL MINING CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DOI, YASUO, HEGURI, SHIN-ICHI, IKEDA, OSAMU, KUDO, Yohei, OZAKI, YOSHITOMO, TAKAISHI, KAZUYUKI
Publication of US20190061006A1 publication Critical patent/US20190061006A1/en
Abandoned legal-status Critical Current

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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

Definitions

  • the present invention relates to a method for producing cobalt powder from a solution containing a cobalt ammine sulfate complex, and particularly relates to a method for obtaining seed crystals to use for crystal growth.
  • the cobalt salts are generally produced by dissolving a cobalt metal in an acid.
  • sheet-shaped and massive forms such as conventionally common electrolytic cobalt are easily handled, but are extremely slowly dissolved in an acid. Meanwhile, the form of fine powder is easily dissolved in an acid, but has the handling disadvantage of being easily scattered and the like.
  • Ones called briquets and obtained by consolidating or sintering grains or powder are preferred to make good use of the advantages of the both.
  • an atomizing method for dispersing melted cobalt in gas or water to obtain fine powder and a dry method such as CVD for obtaining cobalt powder by volatilizing cobalt and reducing it in a gas phase as shown in Japanese Patent Laid-Open No. 2005-505695 are known.
  • a method for feeding a reducing agent to a slurry in which a small amount of fine crystals called seed crystals coexist, and growing objects on the surfaces of the seed crystals to obtain powder having a predetermined particle size is commonly used.
  • the seed crystals added in the above are often used by conducting treatment such as grinding a portion of a product repeatedly.
  • the processing also took time and effort and the yield decreased as the processing is repeated more times and therefore this lead to an increase in cost.
  • There has' also remained the problem of seed crystals having the optimal particle size and properties being capable of necessarily being obtained stably only by grinding simply, or the like.
  • the present invention provides a production method for obtaining cobalt powder efficiently by a way for increasing reduction reaction efficiency to produce the cobalt powder from a solution containing a cobalt ammine sulfate complex.
  • a first aspect of the present invention to solve such a problem is a method for producing seed crystals of cobalt powder, sequentially including: a complexing step of adding ammonia, an ammonia compound solution, or both of ammonia and an ammonia compound solution to a cobalt sulfate solution to obtain a solution containing a cobalt ammine sulfate complex; a mixing step of adding nickel powder as a solid that is insoluble or slightly soluble in the solution containing the cobalt ammine sulfate complex, to the solution containing the cobalt ammine sulfate complex obtained in the complexing step to form a mixture slurry; a reduction and precipitation step of charging a reaction vessel with the mixture slurry obtained in the mixing step, and blowing hydrogen gas into the reaction vessel to reduce cobalt contained in the mixture slurry and obtain a cobalt powder slurry containing cobalt precipitate with a cobalt component precipitated on the surface of the solid as cobalt powder; and a
  • a second aspect of the present invention is the method for producing seed crystals of cobalt powder, wherein the nickel powder of the solid in the first aspect has an average particle size of 0.1 ⁇ m or more and 5 ⁇ m or less.
  • a third aspect of the present invention is the method for producing seed crystals 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.
  • seed crystals having a size suitable to be add to a cobalt ammine sulfate complex solution as seed crystals to form cobalt powder can be obtained efficiently when a cobalt ammine sulfate complex solution is reduced with hydrogen gas to produce cobalt powder.
  • FIG. 1 is a production flow chart of the method for producing cobalt powder according to the present invention.
  • the present invention is a method for efficiently producing seed crystals to be add when hydrogen gas is blown into a cobalt ammine sulfate complex solution to produce cobalt powder.
  • cobalt powder is obtained by subjecting a cobalt sulfate solution serving as an original solution to a complexing step, a mixing step, a reduction and precipitation step and a solid-liquid separation step.
  • the reduction rate mentioned in the present invention is defined as a rate obtained by dividing the weight (g) of the obtained cobalt powder by the cobalt amount (g/L) contained in the fed cobalt sulfate solution
  • a cobalt sulfate solution that can be used in the present invention is not particularly limited, but a cobalt leachate obtained by leaching/dissolving a cobalt-containing material such as an industrial intermediate comprising one or a mixture of two or more selected from mixed sulfide containing cobalt, crude cobalt sulfate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt powder, and the like with sulfuric acid or ammonia can be used.
  • various impurities are also industrially contained in the cobalt leachate.
  • the leachate is generally used by removing impurity elements in the leachate by subjecting the leachate to a purification step such as solvent extraction, ion exchange, or neutralization.
  • aqueous ammonia and ammonium sulfate are added to the cobalt leachate to obtain a cobalt ammine sulfate complex solution.
  • the concentration of ammonium sulfate in the solution is preferably in the range of 10 to 500 g/L. If the concentration is more than 500 g/L, it is higher than the solubility, and crystals may be precipitated. This is not preferable since an operational trouble occurs. If the concentration is less than 10 g/L, since ammonium sulfate is newly produced by the reaction, it is industrially difficult to keep the concentration at a level of less than 10 g/L.
  • the cobalt concentration in the cobalt ammine sulfate complex solution is 75 g/L or less. It is because in the reaction of a solid after the addition in later steps, if the cobalt concentration in the cobalt ammine sulfate complex solution is too high, the reduction rate will be decreased due to the shortage of reaction sites.
  • the solid to be added is not particularly limited as long as it is insoluble or sparingly soluble with a low solubility in a cobalt ammine sulfate complex solution, an aqueous ammonium sulfate solution, or an alkali solution.
  • nickel powder it is preferable to use nickel powder.
  • Cobalt powder When cobalt powder is used for a solid, it is the same as cobalt precipitate, and therefore these do not need to be separated. Cobalt powder is thus the most suitable to be used as seed crystals, but it is difficult to industrially obtain fine cobalt powder at a low price stably.
  • iron powder Although there is an advantage of iron powder being available at a low price easily, there is a disadvantage of iron powder being easily dissolved in an acidic solution and hardly serving as crystal nuclei. Because dissolved iron ions becomes a new cause of contamination, and the like, iron powder is not suitable.
  • the solid have a smooth surface so that the precipitated cobalt powder can be separated effectively.
  • the amount of the solid added equivalent to the amount of cobalt existing in the solution or more is required. Specifically, when nickel powder is used for a solid, 75 g/L or more need to be added.
  • reaction vessel of a pressure vessel is charged with the slurry formed by adding nickel powder in the mixing step, and cobalt complex ions in the slurry is reduced by blowing a reducing agent such as hydrogen gas into the reaction vessel to precipitate cobalt on the surface of the solid.
  • a reducing agent such as hydrogen gas
  • the temperature of the mixture slurry namely, the reaction temperature
  • the reaction temperature is preferably in the range of 150 to 200° C. If the reaction temperature is less than 150° C., reduction efficiency is decreased, and even if the reaction temperature is higher than 200° C., the reaction is not affected, but the loss of thermal energy increases.
  • the pressure of the gas phase part which is a space other than the solution in the reaction vessel, is preferably maintained in the range of 1.0 to 4.0 MPa by feeding hydrogen gas. If the pressure is less than 1.0 MPa, reaction efficiency is reduced since the amount of gas migrating from the gas phase part into the solution is little. Meanwhile, even if the pressure is higher than 4.0 MPa, there is no influence such as the reaction being enhanced, but the loss of hydrogen gas just increases, resulting in no advantage.
  • Hydrogen gas may be blown into the gas phase part in the reaction vessel or blown directly into the slurry.
  • the solid having cobalt precipitate on the surface obtained in the reduction and precipitation step is taken out of the pressure vessel with the solution after reduction in the pressure vessel and subjected to solid-liquid separation from the solution after reduction.
  • This solid-liquid separation may be any of, for example, a method using a nutsche and a vacuum flask, a method using a centrifuge, a method using a filter press.
  • Specific separation method can be properly performed by applying a shock to the solid and the cobalt precipitate, or the like.
  • the size of the cobalt precipitate still including the solid or the cobalt precipitate after separation from the solid is still smaller than that used for seed crystals, the size of the cobalt precipitate can be increased by repeating the mixing step again.
  • the solid collected here can be reused for the mixing step repeatedly.
  • the solution after reduction can be used repeatedly as a complexing agent in the complexing step without any treatment or by the recycling thereof into ammonia by treatment such as heating and distillation.
  • the average particle size was measured using a commercial laser particle size analyzer (Microtrac).
  • a solution containing a cobalt ammine sulfate complex was prepared by adding 191 ml of 25% aqueous ammonia to cobalt sulfate equivalent to 75 g of cobalt and 330 g of ammonium sulfate, dissolving them and adjusting the total volume of the solution to 1000 ml.
  • an inner cylinder of an autoclave having a volume of 3 L was charged with the mixture slurry, the mixture slurry was then heated to 185° C. with stirring, hydrogen gas was blown into the mixture slurry while keeping the temperature, and hydrogen gas was further fed so as to maintain the pressure in the inner cylinder of the autoclave at 3.5 MPa. After a lapse of 60 minutes from the start of the feeding of hydrogen gas, the feeding of hydrogen gas was stopped, and the inner cylinder was cooled.
  • the reduction reaction rate of cobalt at this time was 99%.
  • a solution containing a cobalt ammine sulfate complex was prepared by obtaining a solution containing 75 g of cobalt, 330 g of ammonium sulfate and 191 ml of 25% aqueous ammonia, adding 3.73 g of polyacrylic acid having a concentration of 40 wt % as a dispersant instead of a solid of seed crystals of the present invention thereto, and adjusting the total volume of the solution to 1000 ml.
  • Example 2 The same inner cylinder of the autoclave as Example 1 was charged with the prepared solution, which was then heated to 185° C. with stirring, hydrogen gas was blown into the mixture slurry while keeping the temperature, and hydrogen gas was further fed so as to maintain the pressure in the inner cylinder of the autoclave at 3.5 MPa.
  • a solution containing a cobalt ammine sulfate complex was prepared by adding a solution containing 330 g of ammonium sulfate to a cobalt sulfate solution containing 75 g of cobalt, adding 191 ml of 25% aqueous ammonia to the resulting solution, and adjusting the total volume of the solution to 1000 ml.
  • the inner cylinder of the autoclave used in Example 1 was charged with the prepared mixture slurry, the mixture slurry was then heated to 185° C. with stirring, hydrogen gas was blown into the mixture slurry while keeping the temperature, and hydrogen gas was further fed so as to maintain the pressure in the inner cylinder of the autoclave at 3.5 MPa. After a lapse of 60 minutes from the start of the feeding of hydrogen gas, the feeding of hydrogen gas was stopped, and the inner cylinder was cooled.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
US15/770,546 2015-10-26 2016-10-17 Method for producing seed crystal of cobalt powder Abandoned US20190061006A1 (en)

Applications Claiming Priority (3)

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
PCT/JP2016/080690 WO2017073392A1 (ja) 2015-10-26 2016-10-17 コバルト粉の種結晶の製造方法

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US (1) US20190061006A1 (cg-RX-API-DMAC7.html)
EP (1) EP3369499A4 (cg-RX-API-DMAC7.html)
JP (1) JP6350830B2 (cg-RX-API-DMAC7.html)
CN (1) CN108349011A (cg-RX-API-DMAC7.html)
AU (1) AU2016345951B2 (cg-RX-API-DMAC7.html)
CA (1) CA3003239C (cg-RX-API-DMAC7.html)
PH (1) PH12018500896B1 (cg-RX-API-DMAC7.html)
WO (1) WO2017073392A1 (cg-RX-API-DMAC7.html)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN116177614A (zh) * 2023-03-23 2023-05-30 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

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JP3073099B2 (ja) 1992-05-07 2000-08-07 株式会社ミヤデン 誘導加熱装置
WO2020183728A1 (ja) * 2019-03-14 2020-09-17 住友金属鉱山株式会社 ニッケル粉の製造方法
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

Citations (3)

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Publication number Priority date Publication date Assignee Title
US3730756A (en) * 1971-04-28 1973-05-01 Sherritt Gordon Mines Ltd Method of producing cobalt-coated composite powder
US4545814A (en) * 1984-05-23 1985-10-08 Amax Inc. Production of cobalt and nickel powder
CN101428349A (zh) * 2008-07-29 2009-05-13 张建玲 一种镍钴金属粉末的制备方法

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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
US5246481A (en) * 1992-10-26 1993-09-21 Sherritt Gordon Limited Production of metallic 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
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
US3730756A (en) * 1971-04-28 1973-05-01 Sherritt Gordon Mines Ltd Method of producing cobalt-coated composite powder
US4545814A (en) * 1984-05-23 1985-10-08 Amax Inc. Production of cobalt and nickel powder
CN101428349A (zh) * 2008-07-29 2009-05-13 张建玲 一种镍钴金属粉末的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116177614A (zh) * 2023-03-23 2023-05-30 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

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EP3369499A1 (en) 2018-09-05
AU2016345951B2 (en) 2019-01-17
WO2017073392A1 (ja) 2017-05-04
JP2017082270A (ja) 2017-05-18
EP3369499A4 (en) 2019-03-20
CN108349011A (zh) 2018-07-31
PH12018500896B1 (en) 2021-03-03
PH12018500896A1 (en) 2018-10-29
CA3003239C (en) 2019-11-26
CA3003239A1 (en) 2017-05-04
JP6350830B2 (ja) 2018-07-04
AU2016345951A1 (en) 2018-05-17

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