CN107735199A - The manufacture method of cobalt powder - Google Patents
The manufacture method of cobalt powder Download PDFInfo
- Publication number
- CN107735199A CN107735199A CN201680039447.7A CN201680039447A CN107735199A CN 107735199 A CN107735199 A CN 107735199A CN 201680039447 A CN201680039447 A CN 201680039447A CN 107735199 A CN107735199 A CN 107735199A
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- Prior art keywords
- cobalt
- cobalt powder
- mixed slurry
- crystal seed
- amount
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Classifications
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The method that the present invention provides manufacture cobalt powder, it obtains high reaction efficiency when manufacturing cobalt powder by the solution containing cobaltous sulfate ammino-complex by controlling the addition of crystal seed.The manufacture method of cobalt powder, it is characterised in that undergo following processes successively to make cobalt powder:Mixed processes, the cobalt dust of more than 1.5 times of the cobalt amount that contains and less than 3.0 times of amount is wherein added in above-mentioned solution in the solution for containing cobaltous sulfate ammino-complex as crystal seed, next the weight % of 1.5 weight % of added crystal seed amount~3.0 dispersant is added, forms mixed slurry;Process is separated out with reduction, wherein after the mixed slurry is loaded in reactive tank, hydrogen is blown into mixed slurry, cobalt complex ion contained in mixed slurry is reduced, cobalt precipitate is formed in seed surface.
Description
Technical field
The present invention relates to cobalt powder manufacture when manufacturing cobalt powder by the solution containing cobaltous sulfate ammino-complex with high reaction efficiency
Method, can be especially suitable for the processing of the middle generation solution of in-process as caused by wet type cobalt smelting process.
Background technology
As the method for manufacturing small cobalt powder, it is known that the cobalt of melting is scattered in gas or water and is obtained fine powder
It is dry to obtain CVD of cobalt powder etc. by making cobalt volatilize, being reduced in the gas phase disclosed in atomization, patent document 1
Method.
In addition, being taken as the method for wet method manufacture cobalt powder, there is the side generated using reducing agent disclosed in patent document 2
Disclosed in method, patent document 3 by the way that cobalt liquor is sprayed so as to be obtained by pyrolysis into reducing atmosphere at high temperature
Spray heating decomposition to cobalt powder etc..
But these methods are due to needing the high reagent class of price, substantial amounts of energy, therefore it can not be said to be economic side
Method.
On the other hand, hydrogen will be supplied as shown in non-patent literature 1, into cobaltous sulfate ammino-complex solution to be complexed
Cobalt ions reduction in thing solution and obtain the method for cobalt powder industrially price be low, be useful.But have in this method
The problem of obtained cobalt powder particle easy coarsening.
Especially, in the case of producing particle from the aqueous solution and making its growth, with the following method:Make referred to as brilliant
The fine crystallization of kind coexists on a small quantity, supplies reducing agent thereto, makes seeded growth and obtains the powder of defined particle diameter.
In the method, due to the cobalt concentration in the aqueous solution that uses, species of crystal seed etc., it is impossible to obtain high reaction effect
Rate, yield is reduced, therefore causes cost to increase.
Typically in this case, can by reducing the particle diameter of crystal seed, reacting field increase is improved reaction efficiency,
But in order that the particle diameter of crystal seed diminishes, can take time and energy, in addition using dissimilar metal crystal seed in the case of, due to the crystal seed into
The problems such as dividing residual, therefore producing the purity reduction of product.
Therefore, it is necessary to have without using dissimilar metal as crystal seed and in the case where the small crystal seed of particle diameter may not be used
The method of high reaction efficiency.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2005-505695 publications
Patent document 2:No. 5407495 publications of Japan Patent
Patent document 3:No. 4286220 publications of Japan Patent
Non-patent literature
Non-patent literature 1:“The Manufacture and properties of Metal powder produced
By the gaseous reduction of aqueous solutions ", Powder metallurgy, No.1/2
(1958), the 40-52 pages.
The content of the invention
The invention problem to be solved
In such a case, the method that the present invention provides manufacture cobalt powder, it is by the solution containing cobaltous sulfate ammino-complex
When manufacturing cobalt powder high reaction efficiency is obtained by controlling the addition of crystal seed.
For solving the scheme of problem
For the manufacture method solving such problem, 1st invention of the invention is cobalt powder, it is characterised in that successively
Following processes are undergone to make cobalt powder:Mixed processes, wherein adding above-mentioned initial liquid in the solution containing cobaltous sulfate ammino-complex
In contain more than 1.5 times of cobalt amount and the cobalt dust of less than 3.0 times of amount as crystal seed, next add added crystal seed
The weight % of 1.5 weight %~3.0 of amount dispersant, forms mixed slurry;Process is separated out with reduction, wherein by the mixing slurry
After material loads in reactive tank, hydrogen is blown into mixed slurry, cobalt complex ion contained in the mixed slurry is reduced, in crystal seed
Surface forms cobalt precipitate.
The 2nd invention of the present invention is the manufacture method of cobalt powder, it is characterised in that contains cobaltous sulfate ammino in the 1st invention
The scope that ammonium sulfate concentrations in the solution of thing are 10~500g/L.
The 3rd invention of the present invention is the manufacture method of cobalt powder, it is characterised in that in the reduction process in the 1st and the 2nd invention
The temperature of mixed slurry when being blown into hydrogen be 150~200 DEG C.
The 4th invention of the present invention is the manufacture method of cobalt powder, it is characterised in that in the reduction process in the 1st to the 3rd invention
Reactive tank when being blown into hydrogen in gas phase portion pressure be 1.0~4.0MPa scope.
The effect of invention
According to the present invention, dispersant is added in cobalt ammino-complex solution, hydrogen reduction is carried out at high temperature under high pressure and manufactures cobalt
It is possibly realized in the method for powder with high reaction efficiency manufacture cobalt powder.
Brief description of the drawings
Fig. 1 is the manufacturing flow chart of the manufacture method of cobalt powder of the present invention.
Fig. 2 is the SEM pictures of the outward appearance of the cobalt powder generated in expression embodiment 1.
Embodiment
The manufacture method of the high-purity cobalt powder of the present invention is the manufacture method of cobalt powder, it is characterised in that is using autoclave
Crystal seed is added in cobaltous sulfate ammino-complex solution Deng high-pressure bottle, is carried out using the reduction treatment of hydrogen at high temperature under high pressure
During pressurized hydrogen reduction treatment, add more than 1.5 times and less than 10.0 times, preferably more than 1.5 times and 3.0 times of initial liquid cobalt amount with
Under amount, more preferably 2.0 times of cobalt dust as crystal seed, manufacture cobalt powder.
The manufacture method of the cobalt powder of the present invention is illustrated referring to the manufacturing flow chart shown in Fig. 1.
[cobaltous sulfate ammino-complex solution]
The cobaltous sulfate ammino-complex solution used in the present invention is not particularly limited, by choosing will be included with sulfuric acid or ammonia
From one kind in cobalt and cobalt mixed sulfides, thick cobaltous sulfate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt powder etc. or a variety of
The cobalts such as the industrial intermediate of mixture contain thing dissolving obtained from cobalt leachate (solution containing cobalt) implement solvent extraction method, from
The net liquid such as sub- exchange process, neutralization process and by solution impurity element remove, in obtained solution add ammonia and be made
Solution of cobaltous sulfate ammino-complex solution etc. is suitable, contains cobalt in the form of cobalt complex ion.
[mixed processes]
In the process, crystal seed is added in the cobaltous sulfate ammino-complex solution of above-mentioned making, adds the crystal seed with the addition
Measure the dispersant being consistent and mixed slurry is made.
The crystal seed that the powder of cobalt is used to add herein.
As the powder of the cobalt for being used for crystal seed, commercially available product can be used, but more preferably by using the manufacture method of the present invention
The part reuse of obtained product.
The particle diameter of the cobalt dust preferably turns into 0.1~5 μm or so of average grain diameter, and particularly preferred particle diameter is with 1 μm or so
Size is neatly without fluctuating.
Excessively fine by reacting obtained cobalt powder if meticulous, disposal has difficulties without preferred.On the other hand,
If excessive, the problem of easily settling when stirring be present and be difficult to obtain uniform cobalt powder.
As its addition, in order to maintain high reaction efficiency, preferably add 1.5 times of the cobalt amount contained in stoste with
Upper and less than 3.0 times of amount, preferably 2.0 times of amount.
If addition, less than 1.5 times, the number deficiency of crystal seed, the place reacted is reduced, therefore can not obtain height
Reaction efficiency.In addition, even more than 3.0 times, reaction efficiency also no longer improves, and excessively spends time, cost, and efficiency does not carry but
It is high.The growth of cobalt powder is insufficient on the contrary obtained from the number of crystal seed is excessive, and particle diameter diminishes, therefore as product in use, easily
Produce disposal, spend in processing time etc. using it is upper the problem of, or produce and easy dissolve or be oxidized easily etc. in characteristic
The problem of without preferred.
And then for the amount of the dispersant with regard to adding, relative to the crystal seed amount added in cobaltous sulfate ammino-complex solution, lead to
The concentration for crossing the scope with more than 1.5 weight % and below 3.0 weight % contains, so as to divide with being more uniformly distributed the crystal seed of addition
Dissipate, be readily obtained required nickel powder, therefore preferably.
In addition, the ammonium sulfate concentrations in solution are preferably set to 10~500g/L scope.
If more than 500g/L, then separated out more than solubility, crystallization.For its lower limit, due to by reacting newborn
Into ammonium sulfate, therefore realize difficult less than 10g/L.
[reduction separates out process]
Next, the slurry that crystal seed is with the addition of in preceding process is loaded in the reactive tank of high pressure resistant elevated temperature vessel, it is anti-to this
Answer in groove and be blown into hydrogen in the slurry of storage, the cobalt complex ion in the slurry is reduced, cobalt is separated out on contained crystal seed.
The scope that preferably 150~200 DEG C of the temperature of mixed slurry now, i.e. reaction temperature.If less than 150 DEG C,
Reduction efficiency reduces, even if becoming more than 200 DEG C, on reacting the loss increase also without influence, on the contrary heat energy etc., therefore not
It is adapted to.
And then gas phase portion (refers to store the reactive tank remained after solution in reactive tank in reactive tank when just reacting
Interior spatial portion) pressure for, preferably control hydrogen quantity delivered and maintain 1.0~4.0MPa scope.If pressure
Less than 1.0MPa, then reaction efficiency reduction is without preferred.In addition, even more than 4.0MPa, on reaction efficiency also without influence, hydrogen
Loss increase.
Further, for hydrogen being blown into mixed slurry, no matter be directly blown into the liquid into the reactive tank or
Person is blown into gas phase portion, can reduce the cobalt complex ion in slurry.
Handled by the reduction precipitation of the present invention, the precipitate of cobalt, the cobalt as fine powdery are formed on crystal seed
Precipitate cobalt contained in solution is reclaimed, being capable of Reusability.
By making the crystal seed for the cobalt dust that can be used as the fine powdery that crystal seed uses as described above, it is repeated
Hydrogen reduction, so as to form the particle that the precipitate of cobalt is provided with the seed surface, make the particle growth, high-purity can be manufactured
Cobalt metal.
Embodiment
The present invention will be described for embodiment used below.
Embodiment 1
[mixed processes]
Ammonium sulfate 465g is added in the cobalt sulfate solution comprising cobalt 75g, and then adds 191ml 25% ammoniacal liquor, by this
For solution as stoste, 2.0 times of amounts for adding stoste thereto are the cobalt powder conduct of 0.1~5 μm of 150g or so of average grain diameter
Crystal seed, and then addition turns into the 40wt% polyacrylic acid of 2.0 weight % amount relative to crystal seed amount as dispersant, and then carry out
So that liquid measure turns into 1000ml, making includes the mixed slurry containing cobaltous sulfate ammino-complex of crystal seed for adjustment.
[reduction separates out process]
Next, by the mixed slurry load autoclave interior canister in, closed and warming while stirring to 185 DEG C simultaneously
Kept, after becoming the state, hydrogen is blown into mixed slurry, supply hydrogen from gas bomb so that by autoclave
Pressure in interior canister is maintained at 3.5MPa.
Stop the supply of hydrogen after having been begun to pass through 60 minutes from the supply of hydrogen, interior canister is cooled down.
After cooling, the cobalt powder that the mixed slurry in interior canister is filtered and reclaimed, knot are observed using electron microscope (SEM)
Fruit confirms to generate fine cobalt powder as illustrated in fig. 2.
In addition, with the cobalt contained in cobalt amount of precipitation divided by the stoste subtracted from the amount for the cobalt that can be reclaimed obtained by the amount of crystal seed
The reaction of formation rate for the cobalt powder that amount is obtained, which reduces production rate, becomes 72%.
(comparative example 1)
Stoste containing cobalt is made using the condition same with above-described embodiment 1 and method, stoste is added in the stoste
1.0 times of amounts be 75g cobalt powder as crystal seed, be adjusted so that liquid measure turns into 1000ml, made comparative example 1 be related to it is mixed
Close slurry.Next, after the solution of the making is loaded in the interior canister of autoclave, warming while stirring is to 185 DEG C and carries out
Keep, be blown into hydrogen in this condition, supply hydrogen by the pressure in the interior canister of autoclave so that maintain 3.5MPa.
Stop the supply of hydrogen after having been begun to pass through 60 minutes from the supply of hydrogen, interior canister is cooled down.
After cooling, the solution in interior canister is filtered, generates fine cobalt powder.
But the reaction of formation rate of cobalt powder rests on 36%, there is no the so high efficiency of embodiments of the invention 1.
Claims (4)
1. the manufacture method of cobalt powder, it is characterised in that undergo following processes successively to make cobalt powder:
Mixed processes, wherein added in the solution containing cobaltous sulfate ammino-complex in above-mentioned solution 1.5 times of the cobalt amount contained with
Upper and less than 3.0 times of amount cobalt dust is used as crystal seed, next the weight of 1.5 weight % of the added crystal seed amount of addition~3.0
% dispersant is measured, forms mixed slurry;With
Reduction, process is separated out, wherein after above-mentioned mixed slurry is loaded in reactive tank, hydrogen is blown into above-mentioned mixed slurry,
Cobalt complex ion contained in above-mentioned mixed slurry is reduced, cobalt precipitate is formed in above-mentioned seed surface.
2. the manufacture method of the cobalt powder described in claim 1, it is characterised in that in the above-mentioned solution containing cobaltous sulfate ammino-complex
Ammonium sulfate concentrations are 10~500g/L scope.
3. the manufacture method of the cobalt powder described in claim 1 or 2, it is characterised in that when being blown into hydrogen in above-mentioned reduction process
The temperature of mixed slurry is 150~200 DEG C.
4. the manufacture method of the cobalt powder described in any one of claims 1 to 3, it is characterised in that be blown into above-mentioned reduction process
The pressure in gas phase portion is 1.0~4.0MPa scope in reactive tank during hydrogen.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015134743A JP6489315B2 (en) | 2015-07-03 | 2015-07-03 | Method for producing cobalt powder |
JP2015-134743 | 2015-07-03 | ||
PCT/JP2016/069030 WO2017006795A1 (en) | 2015-07-03 | 2016-06-27 | Method for producing cobalt powder |
Publications (1)
Publication Number | Publication Date |
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CN107735199A true CN107735199A (en) | 2018-02-23 |
Family
ID=57685569
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN201680039447.7A Pending CN107735199A (en) | 2015-07-03 | 2016-06-27 | The manufacture method of cobalt powder |
Country Status (8)
Country | Link |
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US (1) | US20180169764A1 (en) |
EP (1) | EP3321015A4 (en) |
JP (1) | JP6489315B2 (en) |
CN (1) | CN107735199A (en) |
AU (2) | AU2016291485A1 (en) |
CA (1) | CA2990568A1 (en) |
PH (1) | PH12018500025A1 (en) |
WO (1) | WO2017006795A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112195350A (en) * | 2020-08-19 | 2021-01-08 | 衢州华友钴新材料有限公司 | Preparation method of coarse particle cobalt cluster |
CN116197405A (en) * | 2022-11-21 | 2023-06-02 | 安徽寒锐新材料有限公司 | Preparation method of superfine cobalt powder, superfine cobalt powder and pilot-scale production line |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3527306A1 (en) * | 2018-02-14 | 2019-08-21 | H.C. Starck Tungsten GmbH | Powder comprising coated hard particles |
CN113292106B (en) * | 2020-02-24 | 2023-07-25 | 荆门市格林美新材料有限公司 | Three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide |
CN112371990A (en) * | 2020-10-22 | 2021-02-19 | 宁波互邦新材料有限公司 | Preparation process of ammoniation-free metal cobalt powder |
CN113500203A (en) * | 2021-06-23 | 2021-10-15 | 安徽寒锐新材料有限公司 | Preparation process of nano cobalt powder |
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EP0047076A1 (en) * | 1980-08-21 | 1982-03-10 | Inco Limited | A process of making cobalt metal powder |
US5246481A (en) * | 1992-10-26 | 1993-09-21 | Sherritt Gordon Limited | Production of metallic powder |
CN1686650A (en) * | 2005-05-18 | 2005-10-26 | 北京科技大学 | Precipitation reduction method of preparing nano-cobalt powder |
CN101428349A (en) * | 2008-07-29 | 2009-05-13 | 张建玲 | Method for producing nickel-cobalt metal powder |
CN104117686A (en) * | 2014-08-01 | 2014-10-29 | 宁波雁门新能源有限公司 | Cobalt powder preparation method |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
US4545814A (en) * | 1984-05-23 | 1985-10-08 | Amax Inc. | Production of cobalt and nickel powder |
-
2015
- 2015-07-03 JP JP2015134743A patent/JP6489315B2/en active Active
-
2016
- 2016-06-27 CA CA2990568A patent/CA2990568A1/en not_active Abandoned
- 2016-06-27 CN CN201680039447.7A patent/CN107735199A/en active Pending
- 2016-06-27 US US15/738,244 patent/US20180169764A1/en not_active Abandoned
- 2016-06-27 EP EP16821264.5A patent/EP3321015A4/en not_active Withdrawn
- 2016-06-27 AU AU2016291485A patent/AU2016291485A1/en not_active Abandoned
- 2016-06-27 WO PCT/JP2016/069030 patent/WO2017006795A1/en active Application Filing
-
2018
- 2018-01-03 PH PH12018500025A patent/PH12018500025A1/en unknown
-
2019
- 2019-12-05 AU AU2019275612A patent/AU2019275612A1/en not_active Abandoned
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EP0047076A1 (en) * | 1980-08-21 | 1982-03-10 | Inco Limited | A process of making cobalt metal powder |
US5246481A (en) * | 1992-10-26 | 1993-09-21 | Sherritt Gordon Limited | Production of metallic powder |
JPH08503999A (en) * | 1992-10-26 | 1996-04-30 | シェリット インコーポレイテッド | Method for producing metallic cobalt powder |
CN1686650A (en) * | 2005-05-18 | 2005-10-26 | 北京科技大学 | Precipitation reduction method of preparing nano-cobalt powder |
CN101428349A (en) * | 2008-07-29 | 2009-05-13 | 张建玲 | Method for producing nickel-cobalt metal powder |
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Non-Patent Citations (1)
Title |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112195350A (en) * | 2020-08-19 | 2021-01-08 | 衢州华友钴新材料有限公司 | Preparation method of coarse particle cobalt cluster |
CN116197405A (en) * | 2022-11-21 | 2023-06-02 | 安徽寒锐新材料有限公司 | Preparation method of superfine cobalt powder, superfine cobalt powder and pilot-scale production line |
Also Published As
Publication number | Publication date |
---|---|
EP3321015A4 (en) | 2019-03-20 |
CA2990568A1 (en) | 2017-01-12 |
AU2019275612A1 (en) | 2020-01-02 |
PH12018500025A1 (en) | 2018-07-09 |
WO2017006795A1 (en) | 2017-01-12 |
EP3321015A1 (en) | 2018-05-16 |
JP6489315B2 (en) | 2019-03-27 |
AU2016291485A1 (en) | 2018-01-18 |
US20180169764A1 (en) | 2018-06-21 |
JP2017014593A (en) | 2017-01-19 |
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