CN101570478B - Spherical cobalt oxalate powder and production method thereof - Google Patents
Spherical cobalt oxalate powder and production method thereof Download PDFInfo
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- CN101570478B CN101570478B CN200910107586.0A CN200910107586A CN101570478B CN 101570478 B CN101570478 B CN 101570478B CN 200910107586 A CN200910107586 A CN 200910107586A CN 101570478 B CN101570478 B CN 101570478B
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Abstract
The invention relates to a production method of a spherical cobalt oxalate powder. The average Riley sphericity value of the cobalt oxalate powder is above 0.9, the average grain diameter of the cobalt oxalate powder is 0.5-20mum, and the spherical cobalt oxalate powder is prepared by the liquid phase deposition of potassium oxalate and water soluble cobalt salt in a solution with the pH value over 1.5-8. The producing method of the spherical cobalt oxalate powder has fewer impurities and better appearance, and can be prepared by a simple and efficient production method.
Description
Technical field
The present invention relates to field of metallurgy and chemical engineering, more particularly, the present invention relates to a kind of metal-powder and manufacture method thereof.
Background technology
Cobalt powder and oxide powder thereof are the important raw and processed materials of producing the products such as battery electrode, high hardness alloy and diamond tool, support of the catalyst, have a wide range of applications in field of metallurgy and chemical engineering.And the cobalt salt of carbon elements acid group is the important presoma of producing cobalt powder and oxide powder thereof, these presomas comprise cobalt oxalate, cobaltous carbonate.In addition,, in smelting field, cobalt oxalate also has some other purposes.
The Traditional Industrialization production method of cobalt oxalate is to adopt (NH
4)
2c
2o
4and CoCl
2for raw material, mix and prepared by intermediate processing by solution.The precipitin reaction of conventional production methods completes in sour environment, maintains the pH of reaction environment in 2 left and right, and the cobalt oxalate of generation is generally β-CoC
2o
42H
2o, pattern is bar-shaped or dendritic, wherein, the scanning electron microscope pattern of the cobalt oxalate of domestic two well-known producers use produced in conventional processes is as shown in Figure 1,2,3, 4.The cobalt powder being made by the follow-up reduction reaction of cobalt oxalate, due to the inheritance of pattern, subsequent product is also generally dendroid.Although dendritic cobalt oxalate impurity is less, react contral ripening in producing, but, compare spheroidal particle and there is the excellent properties such as good fluidity, tamped density is high, specific surface area is large and have again inferior.In fact, domestic and international high-quality cobalt is that powder is generally spherical or near-spherical, and spherical presoma and powder are all more welcome on market.
Therefore, explore new simple and direct efficient production method, manufacture impurity still less, the presoma of the better spherical cobalt powder of pattern is the significant challenge that industry faces.
Summary of the invention
For the above-mentioned shortcoming of prior art, the object of the invention is to provide a kind of spherical cobalt oxalate powder and manufacture method thereof, and its tool has the following advantages: the impurity of this spherical cobalt oxalate still less, pattern is better, and can make by simple and direct efficient production method.
For this reason, one of technical solution of the present invention is a kind of spherical cobalt oxalate powder, and the average Riley sphericity value of this cobalt oxalate powder is more than 0.9, and the median size of this cobalt oxalate powder is 0.5-20 μ m.In the solution that described spherical cobalt oxalate body is is 1.5-8 with water soluble cobaltous salt in pH value by potassium oxalate, react and make through liquid-phase precipitation.Compare traditional oxalic acid cobalt powder presoma, spherical cobalt oxalate powder of the present invention comprises following optimization and improvement aspect purity: be≤10ppm of the content of impurity elements of ferrum, calcium, sodium, silicon, aluminium in described spherical cobalt oxalate powder.
Under scanning electron microscope (SEM), obtain after the photo of crystal morphology of spherical cobalt oxalate of the present invention, adopt on computers the more similar image processing softwares such as Imagetool to process the crystal morphology photo of spherical cobalt oxalate of the present invention, according to the Riley sphericity formula (Di/Dc) of " PETROLOGY OF SEDIMENTARY ROCKS " (" sedimentogeneous rock ") book promotion of U.S.'s publication in 1974
1/2calculate to such an extent that the average sphericity value of powder of spherical cobalt oxalate of the present invention reaches more than 0.9; And adopt same instrument and method calculate the average sphericity value of Riley of cobalt oxalate part body of making of traditional technology all lower than below 0.6.Known for the succession impact of the pattern of follow-up powder according to precursor powder, adopt spherical cobalt powder presoma of the present invention can make cobalt powder/cobalt oxide powder that sphericity value significantly improves; Therefore, than traditional cobalt oxalate powder, spherical cobalt oxalate powder of the present invention and follow-up go back original product cobalt powder and cobalt oxide powder all has the excellent properties such as mobility is better, tamped density is higher, specific surface area is large, all has significant advantage and progress technically and economically.And, spherical cobalt oxalate of the present invention have impurity still less, the better advantage of pattern, and can manufacture by simple and direct efficient production method.
In fact, at metal agent CoCl
2with precipitation agent K
2c
2o
4concentration equate, test product from many kinds of situations of 0.04～1mol/L proves, spherical cobalt oxalate structure of the present invention is from loose to compacting, and mean particle size can controllably change from 0.5 to 10-20um, and balling-up is fabulous, dispersiveness is very good, and size distribution can be adjusted and change under controlling.
Correspondingly, another technical solution of the present invention is a kind of manufacture method of spherical cobalt oxalate powder described above, and described manufacture method comprises the steps: A) potassium oxalate and water soluble cobaltous salt are dissolved in water respectively and obtain Potassium Oxalate Solution and cobalt salt solution; B) control Potassium Oxalate Solution is identical with the temperature of cobalt salt solution, fast Potassium Oxalate Solution is added in cobalt salt solution, and constant temperature stirs and impels mixing solutions generation precipitin reaction; C) solution of abundant precipitin reaction is carried out to solid-liquid separation, obtain the powder of precipitation; D) washing gained powder is dried again, makes described spherical cobalt oxalate powder.
In tradition cobalt oxalate powder technique, for water soluble cobaltous salt is carried out precipitin reaction and always adopts oxalic acid ammonium salt as precipitation agent, habitual thinking is wherein to consider that ammonium salt system is convenient to the purification separation in later stage and removes positively charged ion, can relatively easily obtain highly purified oxalic acid cobalt powder.The thinking of the confrontational cobalt oxalate technique of manufacture method one of spherical cobalt oxalate powder of the present invention, creatively find: adopt potassium oxalate to replace traditional precipitation agent, water soluble cobaltous salt is carried out to precipitin reaction, the cobalt oxalate powder making like this, its later stage purification separation also can be done very thoroughly, the impurity of its powder does not increase, and its average Riley sphericity value but can significantly promote and reach more than 0.9, substantially exceeds the average Riley sphericity value of traditional cobalt oxalate powder below 0.6.Meanwhile, method of the present invention can produce simple and direct, efficiently, at low cost impurity still less, pattern is better, quality is higher spherical cobalt oxalate powder, to prepare follow-up cobalt powder and cobalt oxide powder.
For promoting the speed of precipitin reaction, ensure fully reaction balling-up and keep balance between globosity and the concentrated distribution of granularity, and for promoting the practicality of technique, be convenient to promote in production practice, method of the present invention also comprises following optimization and concrete improvement:
In described steps A, the molar weight of water soluble cobaltous salt equates with the molar weight of described oxalate, and the volumetric molar concentration of two kinds of solution is 0.2-2.5M; Described water soluble cobaltous salt be cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous acetate one of them.
In described steps A and B, the temperature of solution remains on 15-60 DEG C.
In described step B, control the pH value of mixing solutions at 1.5-8, the reaction times is controlled at 15-30 minute.As preferably, in described step B, control the pH value of mixing solutions in 6-7 scope.
In described step B, in mixing solutions, be also added with the pH value of ionogen and/or adjusting mixing solutions; Described ionogen is KCl, H
2c
2o
4, CoCl
2one of them.
In described step B, control Potassium Oxalate Solution and added in cobalt salt solution in 5 seconds.
In described step D, controlling dry temperature is 100～150 DEG C, and be 4 hours time of drying.
The method K that we are bright
2c
2o
4solution precipitation cobalt oxalate, with utmost point simple reaction prepare pattern and structure is controlled, particle diameter at 0.5-20 μ m, be evenly distributed, the standard spherical cobalt oxalate of good dispersity.And can, by regulating concentration, temperature, ionogen, pH value, the performance of particle be exerted one's influence; By the above all kinds of processing condition of appropriate combination and raw materials technology, the mass parameter such as median size, size distribution, granule interior structure, dispersiveness that can effectively control spherical cobalt oxalate powder, ensures to regulate and control to produce marketable spherical cobalt oxalate powder according to the market requirement.
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Brief description of the drawings
Fig. 1-4 are respectively Electronic Speculum (SEM) schematic diagram of 4 kinds of traditional cobalt oxalates.
Fig. 5-8 are respectively Electronic Speculum (SEM) schematic diagram of spherical cobalt oxalate powder embodiment 1,2,3,4 of the present invention.
Fig. 9 is X-ray diffraction (XRD) spectrogram of spherical cobalt oxalate powder embodiment 1,2,4 of the present invention.
Figure 10,11 is respectively Electronic Speculum (SEM) schematic diagram of spherical cobalt oxalate powder embodiment 5,6 of the present invention.
As Fig. 1-4, shown in be respectively Electronic Speculum (SEM) schematic diagram of 4 kinds of traditional cobalt oxalates.Wherein, 4 kinds of traditional cobalt oxalates are by (NH
4)
2c
2o
4and CoCl
2precipitation, respectively as shown in Figure 1, Figure 2, Figure 3, Figure 4, reaction completes pattern in sour environment, maintains the pH of reaction environment in 2 left and right separately.From Electronic Speculum (SEM) schematic diagram, these 4 kinds of traditional cobalt oxalates are β-CoC
2o
42H
2o, particle diameter is in 5um left and right, and its pattern is bar-shaped or dendroid.
To above-mentioned scanning electron microscope (SEM) photo of these 4 kinds of traditional cobalt oxalates, after adopting on computers Imagetool etc. similarly image processing software being processed, calculate the average Riley sphericity value of powder of these 4 kinds of traditional cobalt oxalates as following table 1:
Table 1
| Sequence number | Average Riley sphericity value |
| Fig. 1 | 0.5647 |
| Fig. 2 | 0.5757 |
| Fig. 3 | 0.5591 |
| Fig. 4 | 0.5786 |
Embodiment
Embodiment 1:
Make 0.5MCoCl
2solution and 0.5M K
2c
2o
4solution, reaction before each solution of equimolar amount is preheating to 25 DEG C, within 5 seconds by K
2c
2o
4add CoCl
2in solution, regulate pH value 6-7, constant temperature stirs, reaction 15-30 minute, will precipitate the filtration of powder and solution separating, wash with water purification, at dry 4 hours of 100～150 DEG C, obtain particle diameter 7um left and right spherical cobalt oxalate, be applicable to general Powder Metallurgy Industry, battery industry etc.
Embodiment 2:
Make 0.5MCoCl
2solution and 0.5M K
2c
2o
4solution, reaction before each solution of equimolar amount is preheating to 40 DEG C, within 5 seconds by K
2c
2o
4add CoCl
2in solution, regulate pH value 6-7, constant temperature stirs, reaction 15-30 minute, will precipitate the filtration of powder and solution separating, wash with water purification, at dry 4 hours of 100～150 DEG C, obtain the spherical cobalt oxalate of particle diameter 6um, be applicable to general Powder Metallurgy Industry, battery industry etc.
Embodiment 3:
Make 1MCoCl
2solution and 1M K
2c
2o
4solution, reaction before each solution of equimolar amount is preheating to 25 DEG C, within 5 seconds by K
2c
2o
4add CoCl
2in solution, regulate pH value 6-7, constant temperature stirs, reaction 15-30 minute, will precipitate the filtration of powder and solution separating, wash with water purification, at dry 4 hours of 100～150 DEG C, obtain the spherical cobalt oxalate of particle diameter 10um left and right, be applicable to general Powder Metallurgy Industry, battery industry etc.
Embodiment 4:
Make 1MCoCl
2solution and 1M K
2c
2o
4solution, reaction before each solution of equimolar amount is preheating to 40 DEG C, within 5 seconds by K
2c
2o
4add CoCl
2in solution, regulate pH value 6-7, constant temperature stirs, reaction 15-30 minute, will precipitate the filtration of powder and solution separating, wash with water purification, at dry 4 hours of 100～150 DEG C, obtain the spherical cobalt oxalate of particle diameter 8um left and right, be applicable to general Powder Metallurgy Industry, battery industry etc.
As Fig. 5-8, shown in be respectively Electronic Speculum (SEM) schematic diagram of spherical cobalt oxalate powder embodiment 1,2,3,4 of the present invention.From (SEM) schematic diagram: the size distribution of spherical cobalt oxalate powder embodiment 1,2,3,4 of the present invention is even, and the sphericity of pattern is obviously better than traditional cobalt oxalate.
As Fig. 9, be depicted as X-ray diffraction (XRD) spectrogram of spherical cobalt oxalate powder embodiment 1,2,4 of the present invention.Be respectively from top to bottom the XRD spectra of embodiment 1,2,4 powders and standard cobalt oxalate powder, embodiment XRD spectra shows, the chemical constitution of spherical cobalt oxalate powder of the present invention and crystalline structure are consistent with standard cobalt oxalate powder.
To above-mentioned scanning electron microscope (SEM) photo of these 4 cobalt oxalate embodiment, after adopting on computers Imagetool etc. similarly image processing software being processed, the average Riley sphericity value that calculates these 4 spherical cobalt oxalate powder embodiment is as following table 2:
Table 2
| Sequence number | Average Riley sphericity value |
| Embodiment 1 | 0.9382 |
| Embodiment 2 | 0.9060 |
| Embodiment 3 | 0.9264 |
| Embodiment 4 | 0.9250 |
Embodiment 5:
Make 0.5MCoCl
2solution, and at K
2c
2o
4in solution, add H
2c
2o
4, make 0.5M precipitant solution (90%K
2c
2o
4+ 10%H
2c
2o
4), cobalt salt equates with the molar weight of oxalate herein, before reaction, solution is preheating to 25 DEG C, within 5 seconds, precipitation agent is added to CoCl
2in solution, pH value 2 left and right, constant temperature stirs, reaction 15-30 minute, will precipitate the filtration of powder and solution separating, wash with water purification, at dry 4 hours of 100～150 DEG C, obtain the loose porous spherical cobalt oxalate of particle diameter internal structure, can be used for the preparation of high quality catalyzer.
Embodiment 6:
Make 0.5MCoCl
2solution, and at K
2c
2o
4in solution, add the ionogen KCl that regulates pH value, make 0.5M precipitant solution (0.5M K
2c
2o
4+ 1M KCl), cobalt salt equates with the molar weight of oxalate herein, before reaction, solution is preheating to 25 DEG C, within 5 seconds, precipitation agent is added to CoCl
2in solution, pH value 2 left and right, constant temperature stirs, reaction 15-30 minute, will precipitate the filtration of powder and solution separating, wash with water purification, at dry 4 hours of 100～150 DEG C, obtain the spherical cobalt oxalate of solidization of particle diameter internal structure, can be used for the fields such as highdensity battery material and diamond tool.
As Figure 10,11, shown in be respectively Electronic Speculum (SEM) schematic diagram of spherical cobalt oxalate powder embodiment 5,6 of the present invention.Contrast Figure 10,11 distinguishes visible, and the powder internal structure of embodiment 5 is loose porous; And the inner solidization high-density of the powder of embodiment 6.
The all be controlled at≤10ppm of content of impurity elements of ferrum, calcium, sodium, silicon, aluminium in above-mentioned spherical cobalt oxalate powder embodiment 1-6.
Claims (7)
1. a manufacture method for spherical cobalt oxalate powder, is characterized in that: described manufacture method comprises the steps: A) potassium oxalate and water soluble cobaltous salt are dissolved in water respectively and obtain Potassium Oxalate Solution and cobalt salt solution; B) control Potassium Oxalate Solution is identical with the temperature of cobalt salt solution, fast Potassium Oxalate Solution is added in cobalt salt solution, and constant temperature stirs and impels mixing solutions generation precipitin reaction; C) solution of abundant precipitin reaction is carried out to solid-liquid separation, obtain the powder of precipitation; D) washing gained powder is dried again, makes described spherical cobalt oxalate powder.
2. the manufacture method of spherical cobalt oxalate powder as claimed in claim 1, is characterized in that: in described steps A, the molar weight of water soluble cobaltous salt equates with the molar weight of described oxalate, and the volumetric molar concentration of two kinds of solution is 0.2-2.5M; Described water soluble cobaltous salt be cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous acetate one of them.
3. the manufacture method of spherical cobalt oxalate powder as claimed in claim 1, is characterized in that: in described steps A and B, the temperature of solution remains on 15-60 DEG C.
4. as the manufacture method of claim 1 spherical cobalt oxalate powder, it is characterized in that: in described step B, control the pH value of mixing solutions at 1.5-8, the reaction times is controlled at 15-30 minute.
5. as the manufacture method of claim 1 spherical cobalt oxalate powder, it is characterized in that: in described step B, control the pH value of mixing solutions in 6-7 scope.
6. as the manufacture method of claim 1 spherical cobalt oxalate powder, it is characterized in that: in described step B, in mixing solutions, be also added with the pH value of ionogen and/or adjusting mixing solutions; Described ionogen is KCl, H
2c
2o
4, CoCl
2one of them.
7. as the manufacture method of claim 1 spherical cobalt oxalate powder, it is characterized in that: in described step D, controlling dry temperature is 100～150 DEG C, and be 4 hours time of drying.
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| CN101570478B true CN101570478B (en) | 2014-09-03 |
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| CN104478699B (en) * | 2014-12-10 | 2017-01-25 | 广东光华科技股份有限公司 | Preparation method of high-purity superfine cobalt oxalate powder |
| CN113416129B (en) * | 2021-06-21 | 2022-07-19 | 温州大学新材料与产业技术研究院 | Preparation method and application of spherical cobalt oxalate |
| CN115229176A (en) * | 2022-06-17 | 2022-10-25 | 北京科技大学 | Preparation method of sphere-like cobalt oxalate particles |
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Non-Patent Citations (2)
| Title |
|---|
| Mohamed A. Mohamed，.A comparative study of the thermal reactivities of some transition metal oxalates in selected atmospheres.《Thermochimica Acta》.2005,第429卷57-72. * |
| 高晋等,.活性球化剂对草酸钻形貌的影响.《稀有金属与硬质合金》.2001,第146卷20-22. * |
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Address after: 518104, Shenzhen, Guangdong Province, Baoan District, Sha Wu Town, West Industrial Zone, No. 50 Patentee after: Limited company of Green U.S. Address before: 518104, Shenzhen, Guangdong Province, Baoan District, Sha Wu Town, West Industrial Zone, No. 50 Patentee before: Shenzhen GEM High-tech Co., Ltd. |