EP3321015A1 - Verfahren zur herstellung von kobaltpulver - Google Patents

Verfahren zur herstellung von kobaltpulver Download PDF

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Publication number
EP3321015A1
EP3321015A1 EP16821264.5A EP16821264A EP3321015A1 EP 3321015 A1 EP3321015 A1 EP 3321015A1 EP 16821264 A EP16821264 A EP 16821264A EP 3321015 A1 EP3321015 A1 EP 3321015A1
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EP
European Patent Office
Prior art keywords
cobalt
seed crystals
amount
mixture slurry
cobalt powder
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP16821264.5A
Other languages
English (en)
French (fr)
Other versions
EP3321015A4 (de
Inventor
Ryo-ma YAMAGUMA
Yoshitomo Ozaki
Kazuyuki Takaishi
Shin-ichi HEGURI
Osamu Ikeda
Yohei Kudo
Yasuo Doi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Metal Mining Co Ltd
Original Assignee
Sumitomo Metal Mining Co Ltd
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 Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd
Publication of EP3321015A1 publication Critical patent/EP3321015A1/de
Publication of EP3321015A4 publication Critical patent/EP3321015A4/de
Withdrawn legal-status Critical Current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
    • 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
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • 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
    • C22B23/0407—Leaching processes
    • C22B23/0446—Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • 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 having high reaction efficiency when cobalt powder is produced from a solution containing a cobalt ammine sulfate complex, and particularly, the present invention can be applied to the treatment of an in-process intermediate solution generated from a cobalt hydrometallurgical process.
  • Examples of known methods for producing fine cobalt powder include dry methods such as an atomizing method of dispersing molten cobalt in a gas or in water to obtain fine powder and a CVD method of volatilizing cobalt and reducing it in a vapor phase to thereby obtain cobalt powder as disclosed in Patent Literature 1.
  • examples of methods for producing cobalt powder by a wet process include a method of producing cobalt powder using a reducing agent as disclosed in Patent Literature 2 and a spray pyrolysis method in which cobalt powder is obtained by pyrolysis reaction by spraying a cobalt solution into a reducing atmosphere at high temperatures as disclosed in Patent Literature 3.
  • Non Patent Literature 1 a method of obtaining cobalt powder by feeding hydrogen gas into a cobalt ammine sulfate complex solution to reduce cobalt ions in the complex solution as shown in Non Patent Literature 1 is industrially inexpensive and useful. However, there has been a problem that cobalt powder particles obtained by this method are easily coarsened.
  • the present invention provides a method for producing cobalt powder by obtaining high reaction efficiency by controlling the amount of added seed crystals when cobalt powder is produced 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 cobalt powder, sequentially including: a mixing step of adding, to a solution containing a cobalt ammine sulfate complex, cobalt powder as seed crystals in an amount of 1.5 times or more and 3.0 times or less the amount of cobalt contained in the starting solution and then adding a dispersant in an amount of 1.5% by weight to 3.0% by weight of the added seed crystals to form a mixture slurry; and a reduction and precipitation step of charging a reaction vessel with the mixture slurry and then blowing hydrogen gas into the mixture slurry to reduce cobalt complex ions contained in the mixture slurry to form cobalt precipitate on a surface of the seed crystals.
  • a second aspect of the present invention is a method for producing cobalt powder according to the first aspect of the invention, wherein the concentration of ammonium sulfate in the solution containing a cobalt ammine sulfate complex is in the range of 10 to 500 g/L.
  • a third aspect of the present invention is a method for producing cobalt powder according to the first and second aspects of the invention, wherein, in the reduction step, the temperature of the mixture slurry when hydrogen gas is blown is 150 to 200°C.
  • a fourth aspect of the present invention is a method for producing cobalt powder according to the first to third aspects of the invention, wherein, in the reduction step, the pressure of the gas phase part in the reaction vessel when hydrogen gas is blown is in the range of 1.0 to 4.0 MPa.
  • cobalt powder in the method of adding a dispersant to a cobalt ammine complex solution and subjecting the resulting mixture to hydrogen reduction under high temperatures and high pressures, cobalt powder can be produced at high reaction efficiency.
  • the method for producing high purity cobalt powder according to the present invention is a method for producing cobalt powder in which, when seed crystals are added to a cobalt ammine sulfate complex solution using a high-pressure vessel such as an autoclave and the resulting mixture is subjected to pressurized hydrogen reduction treatment including reduction treatment with hydrogen at high temperatures and high pressures, cobalt powder is produced by adding cobalt powder as seed crystals in an amount 1.5 times or more and 10.0 times or less the amount of cobalt in the starting solution, preferably 1.5 times or more and 3.0 times or less, and more preferably 2.0 times.
  • Examples of a suitable cobalt ammine sulfate complex solution used in the present invention include, but are not limited to, a cobalt ammine sulfate complex solution obtained by dissolving a cobalt-containing material such as an industrial intermediate including one or a mixture of two or more selected from cobalt and cobalt mixed sulfide, crude cobalt sulfate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt powder, and the like with sulfuric acid or ammonia to obtain a cobalt leaching solution (solution containing cobalt), subjecting the cobalt leaching solution to a purification step such as solvent extraction, ion exchange, and neutralization to obtain a solution from which impurity elements in the cobalt leaching solution have been removed, and adding ammonia to the resulting solution to form the cobalt ammine sulfate complex solution, in which cobalt is contained in the form of cobalt complex ions.
  • a mixture slurry is produced by adding seed crystals to the cobalt ammine sulfate complex solution produced above and adding a dispersant thereto depending on the amount of the added seed crystals.
  • Cobalt powder is used as the seed crystals to be added here.
  • the particle size of the cobalt powder preferably has an average particle size of about 0.1 to 5 ⁇ m, and particularly preferably has a particle size of around 1 ⁇ m, where the particle size does not vary but is uniform.
  • the particle size is too small, the cobalt powder obtained in the reaction will be too small, which has difficulty in handling and is not preferred. On the other hand, if the particle size is too large, the cobalt powder will easily settle during stirring, which poses a problem that uniform cobalt powder is not easily obtained.
  • the amount of cobalt powder to be added is 1.5 times or more and 3.0 times or less, preferably 2.0 times the amount of cobalt contained in the original solution, in order to maintain reaction efficiency.
  • the amount of cobalt powder added is less than 1.5 times of the amount of cobalt contained in the original solution, high reaction efficiency cannot be obtained because the number of seed crystals is insufficient, reducing reaction fields. Further, even if the amount of cobalt powder added is more than 3.0 times, reaction efficiency will not be improved, and the efficiency will not be improved considering that too much time and effort and cost are required. The number of seed crystals will be rather too large, and the growth of the cobalt powder obtained will be insufficient, reducing the particle size. Therefore, when the cobalt powder is used as products, a problem in use will easily occur, such as requiring time and effort in handling thereof. Further, a problem of properties, such as being easily dissolved or oxidized, will occur, which is not preferred.
  • a dispersant when added so that it is contained at a concentration in the range of 1.5% by weight or more and 3.0% by weight or less relative to the amount of seed crystals added to the cobalt ammine sulfate complex solution, the added seed crystals are dispersed more uniformly, and desired nickel powder is thus more easily obtained, which is desirable.
  • the concentration of ammonium sulfate in the solution is preferably in the range of 10 to 500 g/L.
  • the concentration is 500 g/L or more, the solubility will be exceeded, and crystals will be precipitated. With respect to the lower limit, since ammonium sulfate is newly produced by reaction, it is difficult to achieve a concentration of less than 10 g/L.
  • reaction vessel resistant to high pressure and high temperature is charged with the slurry formed by adding seed crystals in the previous step, and hydrogen gas is blown into the slurry stored in the reaction vessel to reduce cobalt complex ions in the slurry to precipitate cobalt on the seed crystals contained.
  • reaction temperature is preferably in the range of 150 to 200°C. If the reaction temperature is less than 150°C, reduction efficiency will be reduced, and even if it is 200°C or more, the reaction will not be affected, but the loss of thermal energy will increase. Therefore, these temperatures are not suitable.
  • the pressure of the gas phase part in the reaction vessel (refers to a space in the reaction vessel remaining after the solution is stored in the reaction vessel) during the reaction is preferably maintained in the range of 1.0 to 4.0 MPa by controlling the feed rate of hydrogen gas. If the pressure is less than 1.0 MPa, reaction efficiency will be reduced, which is not preferred. Further, even if the pressure is higher than 4.0 MPa, the reaction efficiency will not be affected, but the loss of hydrogen gas will increase.
  • the cobalt complex ions in the slurry can also be reduced either by directly blowing hydrogen gas into the liquid in the reaction vessel or by blowing hydrogen gas into the gas phase part in the reaction vessel.
  • a precipitate of cobalt is formed on the seed crystals by reduction and precipitation treatment of the present invention, and the cobalt contained in the solution can be recovered and repeatedly used as a precipitate of fine powdered cobalt.
  • the seed crystals of cobalt powder in fine powder form which can be used as seed crystals and repeating hydrogen reduction, particles in which cobalt precipitate is provided on the surface of the seed crystals are formed, and the particles can be grown up to produce high purity cobalt metal.
  • a mixture slurry containing a cobalt ammine sulfate complex containing seed crystals was prepared by adding, to the original solution, cobalt powder having an average particle size of about 0.1 to 5 ⁇ m, as seed crystals, in an amount of 150 g which is 2.0 times the amount of cobalt in the original solution, further adding 40 wt% polyacrylic acid, as a dispersant, in an amount 2.0% by weight relative to the amount of the seed crystals, and then adjusting the total volume of the solution to 1000 ml.
  • an inner cylinder of an autoclave was charged with the mixture slurry; the mixture slurry was heated to 185°C with stirring after the autoclave was sealed; hydrogen gas was blown into the mixture slurry while keeping the temperature; and hydrogen gas was fed from its cylinder so as to maintain the pressure in the inner cylinder of the autoclave at 3.5 MPa.
  • the amount of precipitated cobalt obtained by deducting the amount of seed crystals from the amount of cobalt that was able to be recovered was divided by the amount of cobalt contained in the original solution to determine the yield of the cobalt powder produced by the reaction, that is, by reduction, which was found to be 72%.
  • An original solution containing cobalt was prepared under the same conditions and in the same manner as in Example 1 above.
  • a mixture slurry according to Comparative Example 1 was prepared by adding, to the original solution, cobalt powder as seed crystals in an amount of 75 g which is 1.0 times the amount of cobalt in the original solution and adjusting the total volume of the solution to 1000 ml.
  • an inner cylinder of an autoclave 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 fed so as to maintain the pressure in the inner cylinder of the autoclave at 3.5 MPa.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
EP16821264.5A 2015-07-03 2016-06-27 Verfahren zur herstellung von kobaltpulver Withdrawn EP3321015A4 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015134743A JP6489315B2 (ja) 2015-07-03 2015-07-03 コバルト粉の製造方法
PCT/JP2016/069030 WO2017006795A1 (ja) 2015-07-03 2016-06-27 コバルト粉の製造方法

Publications (2)

Publication Number Publication Date
EP3321015A1 true EP3321015A1 (de) 2018-05-16
EP3321015A4 EP3321015A4 (de) 2019-03-20

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EP16821264.5A Withdrawn EP3321015A4 (de) 2015-07-03 2016-06-27 Verfahren zur herstellung von kobaltpulver

Country Status (8)

Country Link
US (1) US20180169764A1 (de)
EP (1) EP3321015A4 (de)
JP (1) JP6489315B2 (de)
CN (1) CN107735199A (de)
AU (2) AU2016291485A1 (de)
CA (1) CA2990568A1 (de)
PH (1) PH12018500025A1 (de)
WO (1) WO2017006795A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3527306A1 (de) * 2018-02-14 2019-08-21 H.C. Starck Tungsten GmbH Pulver umfassend beschichtete hartstoffpartikel
CN113292106B (zh) * 2020-02-24 2023-07-25 荆门市格林美新材料有限公司 一种大粒径掺铝四氧化三钴的三次煅烧制备方法
CN112195350A (zh) * 2020-08-19 2021-01-08 衢州华友钴新材料有限公司 一种粗颗粒钴团的制备方法
CN112371990A (zh) * 2020-10-22 2021-02-19 宁波互邦新材料有限公司 一种无氨化金属钴粉制备工艺
CN113500203A (zh) * 2021-06-23 2021-10-15 安徽寒锐新材料有限公司 一种纳米钴粉的制备工艺
CN116197405A (zh) * 2022-11-21 2023-06-02 安徽寒锐新材料有限公司 超细钴粉的制备方法、超细钴粉及中试生产线

Family Cites Families (7)

* 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
GB1436595A (en) * 1973-03-30 1976-05-19 Sherritt Gordon Mines Ltd Process for the production of finely divided cobalt powders
CA1151881A (en) * 1980-08-21 1983-08-16 Eric A. Devuyst Cobalt metal powder by hydrogen reduction
US4545814A (en) * 1984-05-23 1985-10-08 Amax Inc. Production of cobalt and nickel powder
US5246481A (en) * 1992-10-26 1993-09-21 Sherritt Gordon Limited Production of metallic powder
CN1297364C (zh) * 2005-05-18 2007-01-31 北京科技大学 沉淀－还原制备纳米钴粉的方法
CN101428349B (zh) * 2008-07-29 2011-06-22 张建玲 一种镍钴金属粉末的制备方法

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Publication number Publication date
JP6489315B2 (ja) 2019-03-27
PH12018500025A1 (en) 2018-07-09
AU2019275612A1 (en) 2020-01-02
CN107735199A (zh) 2018-02-23
JP2017014593A (ja) 2017-01-19
WO2017006795A1 (ja) 2017-01-12
EP3321015A4 (de) 2019-03-20
AU2016291485A1 (en) 2018-01-18
CA2990568A1 (en) 2017-01-12
US20180169764A1 (en) 2018-06-21

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