WO2017006795A1 - Procédé de production de poudre de cobalt - Google Patents

Procédé de production de poudre de cobalt Download PDF

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Publication number
WO2017006795A1
WO2017006795A1 PCT/JP2016/069030 JP2016069030W WO2017006795A1 WO 2017006795 A1 WO2017006795 A1 WO 2017006795A1 JP 2016069030 W JP2016069030 W JP 2016069030W WO 2017006795 A1 WO2017006795 A1 WO 2017006795A1
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WO
WIPO (PCT)
Prior art keywords
cobalt
seed crystal
powder
cobalt powder
amount
Prior art date
Application number
PCT/JP2016/069030
Other languages
English (en)
Japanese (ja)
Inventor
龍馬 山隈
佳智 尾崎
高石　和幸
伸一 平郡
修 池田
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 CN201680039447.7A priority Critical patent/CN107735199A/zh
Priority to EP16821264.5A priority patent/EP3321015A4/fr
Priority to AU2016291485A priority patent/AU2016291485A1/en
Priority to CA2990568A priority patent/CA2990568A1/fr
Priority to US15/738,244 priority patent/US20180169764A1/en
Publication of WO2017006795A1 publication Critical patent/WO2017006795A1/fr
Priority to PH12018500025A priority patent/PH12018500025A1/en
Priority to AU2019275612A priority patent/AU2019275612A1/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
    • 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 a high reaction efficiency when producing cobalt powder from a solution containing a cobalt sulfate ammine complex, and in particular, an intermediate product solution in a process generated from a wet cobalt smelting process. Applicable to processing.
  • Non-Patent Document 1 a method of supplying cobalt gas to a cobalt sulfate ammine complex solution to reduce cobalt ions in the complex solution to obtain cobalt powder is industrially inexpensive and useful. .
  • this method there is a problem that the cobalt powder particles obtained are easily coarsened.
  • seed crystals when generating and growing particles from an aqueous solution, a small amount of fine crystals called seed crystals coexist in a small amount, a reducing agent is supplied thereto, and seed crystals are grown to obtain a powder having a predetermined particle size. The method is used.
  • the present invention obtains high reaction efficiency by controlling the amount of seed crystals added when producing cobalt powder from a solution containing a cobalt sulfate ammine complex, and produces cobalt powder.
  • a method is provided.
  • the first invention of the present invention provides a solution containing a cobalt sulfate ammine complex at least 1.5 times the amount of cobalt contained in the starting solution as a seed crystal.
  • a mixing step in which cobalt powder in an amount of 0 times or less is added, and then a dispersant of 1.5 wt% to 3.0 wt% of the added seed crystal is added to form a mixed slurry; Then, hydrogen gas is blown into the mixed slurry, and cobalt complex ions contained in the mixed slurry are reduced to form cobalt precipitates on the seed crystal surface. It is a manufacturing method of the cobalt powder characterized by producing powder.
  • the second invention of the present invention is a method for producing cobalt powder, wherein the concentration of ammonium sulfate in the solution containing the cobalt ammine sulfate complex in the first invention is in the range of 10 to 500 g / L.
  • the third invention of the present invention is a method for producing cobalt powder, characterized in that the temperature of the mixed slurry when hydrogen gas is blown in the reduction step of the first and second inventions is 150 to 200 ° C. .
  • the fourth invention of the present invention is characterized in that the pressure in the gas phase portion in the reaction tank when hydrogen gas is blown in the reduction steps of the first to third inventions is in the range of 1.0 to 4.0 MPa. It is a manufacturing method of cobalt powder made into.
  • the high purity cobalt powder production method of the present invention uses a high pressure vessel such as an autoclave to add a seed crystal to a cobalt sulfate ammine complex solution, and performs a hydrogen reduction treatment with hydrogen at a high temperature and high pressure. Add 1.5 times or more and 10.0 times or less, preferably 1.5 times or more and 3.0 times or less, more preferably 2.0 times as much cobalt powder as the seed solution cobalt amount. It is a manufacturing method of cobalt powder characterized by manufacturing cobalt powder. Hereinafter, the manufacturing method of the cobalt powder of this invention is demonstrated with reference to the manufacturing flowchart shown in FIG.
  • the cobalt sulfate ammine complex solution used in the present invention is not particularly limited, but one or a mixture selected from cobalt and cobalt mixed sulfide, crude cobalt sulfate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt powder and the like.
  • Cobalt leachate obtained by dissolving cobalt-containing materials such as industrial intermediates composed of sulfuric acid or ammonia, and subjecting it to liquid purification processes such as solvent extraction, ion exchange, and neutralization
  • a solution obtained by removing the impurity elements in the solution and adding ammonia to form a cobalt ammine sulfate complex solution is suitable, and cobalt is contained in the form of cobalt complex ions.
  • the cobalt powder preferably has an average particle size of about 0.1 to 5 ⁇ m, particularly preferably a size of about 1 ⁇ m with uniform particle size. If it is too fine, the cobalt powder obtained by the reaction is too fine and difficult to handle, which is not preferable. On the other hand, if it is too large, there is a problem that it is easy to settle during stirring, and it becomes difficult to obtain uniform cobalt powder.
  • the amount 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. Is preferred. If the addition amount is less than 1.5 times, the number of seed crystals is insufficient and the reaction field decreases, so that high reaction efficiency cannot be obtained. Also. Even if it exceeds 3.0 times, the reaction efficiency is not improved, and the efficiency is not improved although it takes too much time and cost. On the contrary, the growth of cobalt powder obtained by too many seed crystals is insufficient and the particle size becomes small, so when using it as a product, problems such as handling and handling are likely to occur, In addition, it is not preferable because of problems in characteristics such as easy melting and oxidation.
  • the amount of the dispersant added is more added by including the concentration in the range of 1.5 wt% or more and 3.0 wt% or less with respect to the seed crystal amount added to the cobalt sulfate ammine complex solution. This is desirable because the seed crystals are uniformly dispersed and the desired nickel powder is easily obtained.
  • the ammonium sulfate concentration in the solution is preferably in the range of 10 to 500 g / L. If it is 500 g / L or more, the solubility is exceeded and crystals are deposited. The lower limit is difficult to achieve less than 10 g / L because ammonium sulfate is newly generated by the reaction.
  • 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 efficiency will fall, and even if it is 200 degreeC or more, there is no influence on reaction, rather, since loss, such as a heat energy, increases, it is not suitable.
  • the pressure of the gas phase part in the reaction tank (representing the space in the reaction tank remaining after storing the solution in the reaction tank) during the reaction is controlled by controlling the supply amount of hydrogen gas to 1.0 to 4. It is preferable to maintain in the range of 0 MPa. If the pressure is less than 1.0 MPa, the reaction efficiency is lowered, which is not preferable. Moreover, even if it exceeds 4.0 Mpa, there is no influence on reaction efficiency and the loss of hydrogen gas increases.
  • blowing hydrogen gas into the mixed slurry can reduce cobalt complex ions in the slurry by blowing directly into the liquid in the reaction tank or blowing into the gas phase portion.
  • a cobalt precipitate is formed on the seed crystal, and the cobalt contained in the solution can be collected and used repeatedly as a fine powdery cobalt precipitate.
  • the cobalt slurry collected by filtering the mixed slurry in the inner cylinder can was observed using an electron microscope (SEM), and it was confirmed that fine cobalt powder was produced as shown in FIG. Further, the cobalt powder production reaction rate obtained by subtracting the amount of precipitated cobalt obtained by subtracting the amount of seed crystals from the amount of cobalt recovered by the amount of cobalt contained in the original solution, that is, the reduction production rate was 72%. .
  • Comparative Example 1 A base solution containing cobalt was prepared under the same conditions and method as in Example 1 above, 75 g of cobalt powder as a seed crystal was added 1.0 g of the original solution as a seed crystal, and the liquid volume was 1000 ml. Thus, a mixed slurry according to Comparative Example 1 was prepared. Next, after charging the prepared solution into an inner cylinder can of the autoclave, 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 to 3. Hydrogen gas was supplied to maintain the pressure at 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne un procédé de production d'une poudre de cobalt selon lequel, pour produire une poudre de cobalt à partir d'une solution contenant un complexe d'ammine de cobalt et d'acide sulfurique, la quantité d'ajout d'un cristal germe est régulée de manière à obtenir une efficacité de réaction élevée. L'invention concerne un procédé de production d'une poudre de cobalt caractérisé en ce que la poudre de cobalt est produite en réalisant successivement les étapes suivantes: une étape de mélange pour ajouter, à une solution contenant un complexe d'ammine de cobalt et d'acide sulfurique, une poudre de cobalt comme cristal germe dans une quantité de 1,5 à 3,0 fois, inclus, la quantité de cobalt contenue dans ladite solution puis d'ajout de 1,5 à 3,0% en poids, par rapport à la quantité de cristal germe ajoutée, d'un dispersant pour obtenir un mélange de boue; et une étape de réduction et de dépôt destinée à introduire le mélange de boue dans un réservoir de réaction, souffler de l'hydrogène gazeux dans le mélange de boue de manière à réduire un ion complexe de cobalt contenu dans le mélange de boue et former ainsi des dépôts de cobalt sur la surface du cristal germe.
PCT/JP2016/069030 2015-07-03 2016-06-27 Procédé de production de poudre de cobalt WO2017006795A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CN201680039447.7A CN107735199A (zh) 2015-07-03 2016-06-27 钴粉的制造方法
EP16821264.5A EP3321015A4 (fr) 2015-07-03 2016-06-27 Procédé de production de poudre de cobalt
AU2016291485A AU2016291485A1 (en) 2015-07-03 2016-06-27 Method for producing cobalt powder
CA2990568A CA2990568A1 (fr) 2015-07-03 2016-06-27 Procede de production de poudre de cobalt
US15/738,244 US20180169764A1 (en) 2015-07-03 2016-06-27 Method for producing cobalt powder
PH12018500025A PH12018500025A1 (en) 2015-07-03 2018-01-03 Method for producing cobalt powder
AU2019275612A AU2019275612A1 (en) 2015-07-03 2019-12-05 Method for producing cobalt powder

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-134743 2015-07-03
JP2015134743A JP6489315B2 (ja) 2015-07-03 2015-07-03 コバルト粉の製造方法

Publications (1)

Publication Number Publication Date
WO2017006795A1 true WO2017006795A1 (fr) 2017-01-12

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Application Number Title Priority Date Filing Date
PCT/JP2016/069030 WO2017006795A1 (fr) 2015-07-03 2016-06-27 Procédé de production de poudre de cobalt

Country Status (8)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292106A (zh) * 2020-02-24 2021-08-24 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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3527306A1 (fr) * 2018-02-14 2019-08-21 H.C. Starck Tungsten GmbH Particules de matériau dur revêtues contenant de la poudre
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

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JPS5026750A (fr) * 1973-03-30 1975-03-19
JPH0351764B2 (fr) * 1980-08-21 1991-08-07 Inco Ltd
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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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
US4545814A (en) * 1984-05-23 1985-10-08 Amax Inc. Production of cobalt and nickel 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5026750A (fr) * 1973-03-30 1975-03-19
JPH0351764B2 (fr) * 1980-08-21 1991-08-07 Inco Ltd
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 (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3321015A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292106A (zh) * 2020-02-24 2021-08-24 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
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

Also Published As

Publication number Publication date
AU2019275612A1 (en) 2020-01-02
PH12018500025A1 (en) 2018-07-09
EP3321015A4 (fr) 2019-03-20
AU2016291485A1 (en) 2018-01-18
CA2990568A1 (fr) 2017-01-12
JP6489315B2 (ja) 2019-03-27
US20180169764A1 (en) 2018-06-21
EP3321015A1 (fr) 2018-05-16
CN107735199A (zh) 2018-02-23
JP2017014593A (ja) 2017-01-19

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