CN101745644B - Method for preparing cobalt powder - Google Patents
Method for preparing cobalt powder Download PDFInfo
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- CN101745644B CN101745644B CN2010101208954A CN201010120895A CN101745644B CN 101745644 B CN101745644 B CN 101745644B CN 2010101208954 A CN2010101208954 A CN 2010101208954A CN 201010120895 A CN201010120895 A CN 201010120895A CN 101745644 B CN101745644 B CN 101745644B
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- oxalate
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Abstract
The invention relates to a method for preparing cobalt powder, and super-fine cobalt powder can be prepared, the Fsss of which is not less than 3.0Mu m. The method for preparing the cobalt powder is as follows: hydrogen reduction is carried out on cobalt oxalate at 550-600 DEG C, thus obtaining the cobalt powder, the Fisher particle size of the cobalt oxalate is 4.0-5.5 mu m, the water content is 5 percent to 10 percent, and when the hydrogen reduction is carried out, the water content of reducing gas is 0.25 percent to 0.65 percent (by volume). As a preferred scheme, the ratio of the compositions of the reducing gas is that H2: N2: H2O is equal to 3: 1: (0.01-0.025) (by volume ratio). The preferred reducing gas flow is 4.0-4.5m3/h, and the preferred reducing time is 20-25 minutes. As the preferred scheme of the invention, the cobalt oxalate is doped with tungsten, the proportion of the doped tungsten is 1.0 percent to 2.0 percent, and the proportion of the doped tungsten is the molar ratio of tungsten to cobalt. The method has simple operation, and the super-fine cobalt powder of which the Fsss is not less than 3.0 mu m can be prepared, a mechanical crushing device is saved, oversize products are less, and the actual yield is high.
Description
Technical field
The present invention relates to a kind of production method of cobalt powder.
Background technology
In the powder metallurgy industry, cobalt powder production method commonly used is to prepare cobalt powder with the cobalt oxalate hydrogen reduction, and its chemical equation is:
2CoC
2O
4·2H
2O+3H
2＝2Co+3CO+CO
2+7H
2O
In the hydrogen reduction process, the influence factor that influences the granularity of cobalt powder has a lot: cobalt oxalate granularity, dress boat thickness, hydrogen flowing quantity, hydrogen purity, hydrogen atmosphere composition, reduction temperature, recovery time, logical hydrogen mode etc.
Cobalt oxalate is the cobalt oxalate crystal grain that is generated by solubility cobalt salt solution such as cobalt chloride, cobalt nitrate and ammonium oxalate generation chemical reaction:
CoCl
2+(NH
4)
2C
2O
4＝CoC
2O
4↓+2NH
4Cl
Co(NO
3)
2+(NH
4)
2C
2O
4＝CoC
2O
4↓+2NH
4NO
3
In the process of chemical precipitation, the factor that influences the granule size of cobalt oxalate has a lot:
(1) cobalt salt solution: cobalt concentration, temperature;
(2) ammonium oxalate solution: concentration, pH value, temperature;
(3) other: feed way, charging rate, alr mode, mixing speed;
(4) additive: additive types, addition, adding mode;
(5) crystal seed.
At present domestic more to thin cobalt salt powder (like cobalt oxalate, cobalt carbonate, cobalt hydroxide powder etc.) and the research of thin cobalt powder; In Chinese patent ZL200610061030.9; Liu Sha etc. have invented a kind of cobalt powder that contains the rare-earth nano-crystal wild phase and preparation method thereof; Cobalt powder comprises the respective alloy that made by main material part and auxiliary material part mutually, and main material part comprises cobalt oxide component, tungsten component and rare earth component, and the crystallite dimension of the nanocrystalline wild phase of cobalt powder middle rare earth is 2-10nm.Zhuzhou Hard Alloy Group Co Ltd discloses a kind of preparation method of tungsten-cobalt hard alloy in Chinese patent ZL2003124870.5; Comprise batching, wet-milling, drying, mix binder, press forming, take off binder, step such as sintering; The Co powder that adds (7.5-8.0) wt% during batching; (0.35-0.45) NbC of the TaC of wt%, (0.3-0.4) wt% and the WC powder of surplus, WC powder Fisher particle size (hereinafter to be referred as Fsss) is 3.0-3.5 μ m, Co powder Fisher particle size is 1.0-2.5 μ m.(tungsten mixes to the structure of cobalt powder and the influence of pattern [J] Chen Qinglin etc., carbide alloy, 2002,19 (1): P10) studied tungsten and mixed to the pattern and the effect on structure of cobalt powder; Tungsten mixes and in the chemical precipitation process, realizes, through the microscopic appearance of scanning electron microscopic observation powder, with the phase constituent of X-ray diffraction analysed for powder; And the granularity of Yong Feishi appearance measurement powder, the result shows, mixes through tungsten and can produce the spherical cobalt powder that Fsss is 1.0-1.5 μ m; Its preparation process is mixed tungsten according to a certain percentage for cobalt chloride solution is made into needed concentration, controls certain temperature; Under stirring condition, add ammonium oxalate solution, after reaction finishes; Filter, washing obtains the cobalt oxalate powder after oven dry is sieved.Cobalt oxalate is crossed 120 mesh sieves and is promptly got cobalt powder after hydrogen reduction.Li Wei etc. have studied tungsten and have mixed that (the tungsten doping is to the influence [J] of cobalt oxalates structure and pattern, China YouSe Acta Metallurgica Sinica, 1997,7 (3): P47 for influence to cobalt oxalates structure and pattern; Mix the characteristic research [J] of tungsten cobalt powder, carbide alloy, 1997; 14 (4): P204), research shows that it is beta-crystal by α-crystal transfer that the tungsten doping makes cobalt oxalate, mixes the structure in pelletized form of tungsten cobalt oxalate; Even particle size increases when mixing the tungsten amount, and the particle mean size of the primary particle of cobalt oxalate diminishes; When mixing the tungsten amount when reaching 7.5%, the specific area of cobalt oxalate is 3.14m
2/ g.
Be mainly used in cobalt powder ingredient requirement Fsss in the diamond tool and be not less than the ultra thick cobalt powder of 3.0 μ m, adopt the present ultra thick cobalt powder of cobalt oxalate hydrogen reduction explained hereafter, need through improving reduction temperature, prolonging means such as recovery time; Reduction come out of the stove the back cobalt can be harden, cobalt really up to the mark is block; Be the burning state, just can cross 200 eye mesh screens after must smashing by force with mechanical crusher and obtain Fsss and be not less than the cobalt powder more than the 3.0 μ m, but cause the cobalt burning because temperature is too high; Harden after coming out of the stove, really up to the mark; Be difficult to be dispersed into powdery, though oversize ratio height is to 40-50% after mechanical crusher is smashed by force, casting yield is low.
Summary of the invention
The present invention provides a kind of production method of cobalt powder, can produce the ultra thick cobalt powder that Fsss is not less than 3.0 μ m, and production operation is simple, can save mechanical crushing appliance, and oversize is few, and casting yield is high.
The production method of said cobalt powder is that cobalt oxalate 550～600 ℃ of following hydrogen reductions, is obtained cobalt powder; The Fisher particle size of said cobalt oxalate is 4.0～5.5 μ m; Moisture is 5%～10%, and during hydrogen reduction, the water content of reducing gas is 0.25%～0.65% (volume).
The granularity of cobalt powder and pattern have certain inheritance to its raw material cobalt oxalate, therefore want the above ultra thick cobalt powder of prepared sizes 3.0 μ m, and producing Fsss＞3.5 μ m cobalt oxalates is the basis as presoma.
In the hydrogen reduction technology of cobalt powder, what reducing gas adopted usually is that dew point is below-40 ℃, and hydrogen content is below-40 ℃ at pure hydrogen more than 99% or dew point, H
2: N
2Be the gaseous mixture of 3: 1 (volume) ratios, water content is had strict restriction.The applicant finds after deliberation, the granularity and the water content of control cobalt oxalate, and the water content of assurance proper proportion in reducing gas need not to improve reduction temperature simultaneously, and can obtain Fsss is the above cobalt powders of 3.0 μ m.Because reduction temperature is not very high, the reduction back cobalt of coming out of the stove is more open spongy, and direct mistake 200 mesh sieves can obtain the cobalt powder that Fsss is not less than 3.0 μ m, and the oversize ratio is few to below 10%, and casting yield improves greatly.As preferred version, reducing gas consist of H
2: N
2: H
2O is 3: 1: (0.01～0.025) (volume ratio).The flow of reducing gas and hydrogen reduction time are adopted conventional process, and preferred reducing gas flow is 4.0-4.5m
3/ h, the recovery time is 20-25 minute.
As preferred version of the present invention, said cobalt oxalate is a cobalt oxalate of mixing tungsten, and mixing the tungsten ratio is 1.0%～2.0%, saidly mixes the mol ratio that the tungsten ratio is tungsten and cobalt.The said cobalt oxalate of mixing tungsten is obtained by following steps:
(1) the solubility cobalt salt solution of tungsten salt is mixed in preparation, and mixing the tungsten ratio is 1.0%～2.0%;
(2) under stirring condition, ammonium oxalate solution is joined in the solubility cobalt salt solution of mixing tungsten salt, the reinforced time of control is 40～50min, behind reinforced the end, ageing 1～1.5h;
(3) filtration, washing, drying obtain mixing the cobalt oxalate of tungsten.
Cobalt content is that 30～40g/l, temperature are 60-70 ℃ in the said solubility cobalt salt solution of mixing tungsten salt, and the density of said ammonium oxalate solution is that 1.04-1.045, pH value are that 3.0-4.5, temperature are 75-80 ℃.
The said solubility cobalt salt solution of mixing tungsten salt is under stirring condition, the tungsten salt of solubility or tungsten salt solution to be joined in the solubility cobalt salt to obtain.
Said solubility cobalt salt is cobalt chloride, cobalt nitrate or cobalt acetate.
The Fsss of gained cobalt powder is 3.0-5.0 μ m.
The production equipment that uses the ultra thick cobalt oxalate hydrogen reduction of gained to produce ultra thick cobalt powder is two pipe reduction furnaces, and detailed process is:
The Fsss of ultra thick cobalt oxalate is 4.0-5.5 μ m, and water content is 5-10%.With this cobalt oxalate boat of packing into, every boat 2-4kg that packs into.550-600 ℃ of control one, two, three, four-tape temperature, the gas flow of reducing gas is 4.0-4.5m
3/ h; Advanced a boat in every separated 20-25 minute; In having the atmosphere of certain water vapour (the water vapour is here brought by the water content of reducing gas and cobalt oxalate), cobalt crystal grain in reduction process again crystallization reach the coarse-grain purpose, making the cobalt powder Fsss that produces is 3.0-5.0 μ m.
The present invention can produce the ultra thick cobalt powder that Fsss is not less than 3.0 μ m, and production operation is simple, can save mechanical crushing appliance, and oversize is few, and casting yield is high, and production cost is low, constant product quality.
The specific embodiment
Embodiment 1:
1, mix the cobalt chloride solution of tungsten: mixing the tungsten ratio is 1.0%, and cobalt content is 35g/l, and temperature is 65 ℃;
2, ammonium oxalate solution: density is 1.045, pH value is 4.0, temperature is 80 ℃ and keeps free from admixture.
Add ammonium oxalate solution while stirring, the reinforced time of control is 48min, behind the arrival deposition terminal point (promptly reinforced the end), and ageing 1.2h;
Filter, wash, drying, the Fsss that obtains ultra thick cobalt oxalate is 4.2 μ m, water content 7%.
The cobalt oxalate 3kg that packs in each boat, H in the reducing gas
2: N
2: H
2O is 3: 1: 0.025 (volume ratio), and the control gas flow is 4.8m
3/ h, one, two, three, four-tape reduction temperature is 570 ℃, the recovery time is 25min.The cobalt powder Fsss of output is 4.5 μ m.
Embodiment 2:
1, mix the cobalt nitrate solution of tungsten: mixing the tungsten ratio is 1.2%, and cobalt content is 32g/l, and temperature is 67 ℃;
2, ammonium oxalate solution: density is 1.04, pH value is 3.5, temperature is 78 ℃ and keeps free from admixture.
Add ammonium oxalate solution while stirring, the reinforced time of control is 45min, behind the arrival deposition terminal point, and ageing 1.4h;
Filter, wash, drying, the Fsss that obtains ultra thick cobalt oxalate is 4.2 μ m, water content 8%.
The cobalt oxalate 3.5kg that packs in each boat, H in the reducing gas
2: N
2: H
2O is 3: 1: 0.025 (volume ratio), and the control gas flow is 4.4m
3/ h, one, two, three, four-tape reduction temperature is 580 ℃, the recovery time is 25min.The cobalt powder Fsss of output is 4.2 μ m.
Embodiment 3:
1, mix the cobalt chloride solution of tungsten: mixing the tungsten ratio is 1.3%, and cobalt content is 30g/l, and temperature is 69 ℃;
2, ammonium oxalate solution: density is 1.04, the pH value is 3.5, temperature is 79 ℃ and keeps free from admixture.
Add ammonium oxalate solution while stirring, the reinforced time of control is 50min, behind the arrival deposition terminal point, and ageing 1.4h;
Filter, wash, drying, the Fsss that obtains ultra thick cobalt oxalate is 5.0 μ m, water content 7%.
The cobalt oxalate 2.5kg that packs in each boat, H in the reducing gas
2: N
2: H
2O is 3: 1: 0.01 (volume ratio), and the control gas flow is 4.2m
3/ h, one, two, three, four-tape reduction temperature is 590 ℃, the recovery time is 25min.The cobalt powder Fsss of output is 4.9 μ m.
Claims (6)
1. the production method of a cobalt powder is characterized in that, with cobalt oxalate 550～600 ℃ of following hydrogen reductions; Obtain cobalt powder; The Fisher particle size of said cobalt oxalate is 4.0～5.5 μ m, and moisture is 5%～10% (weight), during hydrogen reduction; The water content of reducing gas is 0.25%～0.65% (volume), reducing gas consist of H
2: N
2: H
2O is 3: 1: (0.01～0.025) (volume ratio), reducing gas flow are 4.0-4.5m
3/ h, the hydrogen reduction time is 20-25 minute.
2. the production method of cobalt powder as claimed in claim 1 is characterized in that, said cobalt oxalate is a cobalt oxalate of mixing tungsten, and mixing the tungsten ratio is 1.0%～2.0%.
3. the production method of cobalt powder as claimed in claim 2 is characterized in that, the said cobalt oxalate of mixing tungsten is obtained by following steps:
The solubility cobalt salt solution of tungsten salt is mixed in preparation, and mixing the tungsten ratio is 1.0%～2.0%;
Under stirring condition, ammonium oxalate solution is joined in the solubility cobalt salt solution of mixing tungsten salt, the reinforced time of control is 40～50min, behind reinforced the end, ageing 1～1.5h;
Filtration, washing, drying obtain mixing the cobalt oxalate of tungsten.
4. the production method of cobalt powder as claimed in claim 3; It is characterized in that; Cobalt content is that 30～40g/l, temperature are 60-70 ℃ in the said solubility cobalt salt solution of mixing tungsten salt, and the density of said ammonium oxalate solution is that 1.04-1.045, pH value are that 3.0-4.5, temperature are 75-80 ℃.
5. the production method of cobalt powder as claimed in claim 3 is characterized in that, said solubility cobalt salt is cobalt chloride, cobalt nitrate or cobalt acetate.
6. like the production method of each described cobalt powder among the claim 1-5, it is characterized in that the Fisher particle size of gained cobalt powder is 3.0-5.0 μ m.
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| CN102649161B (en) * | 2011-02-23 | 2014-11-05 | 荆门市格林美新材料有限公司 | Nickel powder with large furnace safety supervision system (FSSS) particle size and preparation method thereof |
| CN102886525B (en) * | 2011-07-20 | 2015-04-29 | 深圳市格林美高新技术股份有限公司 | Cobalt powder with large grain size and preparation method thereof |
| CN103624251B (en) * | 2013-12-02 | 2015-09-16 | 格林美股份有限公司 | A kind of half micron cobalt powder and preparation method thereof and cobalt hydroxide powder and preparation method thereof |
| CN103878389B (en) * | 2014-03-29 | 2016-03-30 | 宇辰新能源材料科技无锡有限公司 | A kind of production method of coarse granule cobalt powder |
| CN107649689A (en) * | 2017-11-07 | 2018-02-02 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of super-fine cobalt powder |
| CN108469423A (en) * | 2018-03-12 | 2018-08-31 | 南京寒锐钴业股份有限公司 | The detection method of micro sulfur content in a kind of cobalt carbonate, cobalt oxalate |
| CN109663926A (en) * | 2019-03-04 | 2019-04-23 | 江苏萌达新材料科技有限公司 | A kind of cochrome powder and preparation method thereof |
| CN113909485B (en) * | 2021-10-11 | 2023-11-17 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
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| FR2794672B1 (en) * | 1999-06-10 | 2001-09-07 | Asb Aerospatiale Batteries | PROCESS FOR THE PREPARATION OF METAL POWDERS, METAL POWDERS THUS PREPARED AND COMPACTS INCLUDING SUCH POWDERS |
| DE19962015A1 (en) * | 1999-12-22 | 2001-06-28 | Starck H C Gmbh Co Kg | Compound powder mixtures used, e.g., for particle blasting, are produced using one powder type of a metal with a high melting point, hard material or ceramic together with a bonding metal |
| CN100484668C (en) * | 2004-12-06 | 2009-05-06 | 荆门市格林美新材料有限公司 | Production method and apparatus for super fine cobalt powder by circulating technology |
| CN100374231C (en) * | 2006-04-06 | 2008-03-12 | 北京工业大学 | Preparation method of nano-cobalt powder |
| CN100546740C (en) * | 2007-07-09 | 2009-10-07 | 深圳市格林美高新技术股份有限公司 | A kind of super-fine cobalt powder and manufacturing process thereof |
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Address after: 211100, No. 115, Jing Huai street, Jiangning Economic Development Zone, Jiangsu, Nanjing Patentee after: Nanjing Hanrui Cobalt Co., Ltd. Address before: 211100, No. 115, Jing Huai street, Jiangning Economic Development Zone, Jiangsu, Nanjing Patentee before: Nanjing Hanrui Cobalt Co., Ltd. |