CN113371764A - Preparation method of flower-rod-shaped cobalt carbonate - Google Patents
Preparation method of flower-rod-shaped cobalt carbonate Download PDFInfo
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- 229910021446 cobalt carbonate Inorganic materials 0.000 title claims abstract description 128
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 123
- 239000002002 slurry Substances 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000001868 cobalt Chemical class 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 41
- 239000001099 ammonium carbonate Substances 0.000 claims description 41
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 40
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 40
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 22
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 abstract description 10
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002245 particle Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/06—Carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of cobalt carbonate preparation, and particularly discloses a preparation method of flower-rod-shaped cobalt carbonate, which comprises the following steps: respectively preparing a cobalt salt solution and a carbonate solution for later use; adding a certain volume of the carbonate solution into a reactor as a base solution; then adding the cobalt salt solution and the carbonate solution into a reactor containing a base solution at the same time at a specified feeding flow rate to react to obtain cobalt carbonate intermediate slurry; respectively adding the cobalt salt solution and the carbonate solution into the cobalt carbonate intermediate slurry at the same time according to the regulated and specified feeding flow rates for reaction, and aging after the reaction is finished to obtain cobalt carbonate slurry; and (3) carrying out solid-liquid separation on the cobalt carbonate slurry, slurrying and washing, dehydrating, flashing and drying to obtain the flower-stick-shaped cobalt carbonate. The detection of the target cobalt carbonate prepared by the method shows that the target cobalt carbonate prepared by the method is in a flower-stick-shaped morphology structure.
Description
Technical Field
The invention belongs to the technical field of cobalt carbonate preparation, and particularly relates to a preparation method of flower-rod-shaped cobalt carbonate.
Background
At present, in the production process of preparing the large FSSS cobalt powder, the branched large FSSS cobalt powder is prepared by adopting cobalt carbonate by increasing the reduction temperature or prolonging the retention time, but the preparation of the large FSSS cobalt powder by the method has high energy consumption, and the produced branched large FSSS cobalt powder has poor shape uniformity and wide particle size distribution, so that the branched large FSSS cobalt powder cannot be well applied to the manufacture of hard alloys.
Disclosure of Invention
In view of the above, the invention aims to provide a method for preparing flower-rod-shaped cobalt carbonate, which solves the problem that the cobalt carbonate obtained in the prior art cannot meet the requirement of preparing large FSSS cobalt powder with uniform particle size and narrow distribution peak, so that the cobalt carbonate cannot be better applied to the manufacture of high-end hard alloys.
In order to solve the problems, the invention adopts the technical scheme that the preparation method of the flower-rod-shaped cobalt carbonate comprises the following steps:
s1, respectively preparing a cobalt salt solution with the concentration of 120-140 g/L and a carbonate solution with the concentration of 260-280 g/L for later use;
s2, adding a certain volume of the carbonate solution in the S1 into the reactor to serve as a base solution;
s3, stirring the cobalt salt solution and the carbonate solution in the S1 at a stirring speed of 1600-2200 r/min to form a mixture, wherein the stirring speed is 0.3-0.4 m3/h、0.8～1.2m3Simultaneously adding the feed flow of the mixture/h into a reactor containing the base solution in S2, and reacting for 1-3 h at 50-55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, mixing the cobalt salt solution and the carbonate solution of S1 in a ratio of 0.4-0.6 m3/h、1.2～1.8m3Simultaneously adding the feed flow of the/h into the cobalt carbonate intermediate slurry obtained in the step S3, reacting for 1-3 h at 50-55 ℃, and aging after the reaction to obtain cobalt carbonate slurry;
s5, carrying out solid-liquid separation on the cobalt carbonate slurry obtained in the S4, and pulping and washing the solid obtained after the solid-liquid separation to obtain purified cobalt carbonate;
s6, dehydrating, flashing and drying the purified cobalt carbonate obtained in the S5 in sequence to obtain the flower-stick-shaped cobalt carbonate.
Preferably, in the step S2, the temperature of the base solution is controlled to be 50-55 ℃.
Preferably, in the S2, the ratio of the volume of the carbonate solution to the volume of the reactor is (0.5/12-1/12): 1.
preferably, in the S3, the feed flow rate of the cobalt chloride solution is 0.35m3The feed flow rate of the ammonium bicarbonate solution is 1.0m3/h。
Preferably, in the S4, the feed flow rate of the cobalt chloride solution is 0.5m3The feed flow rate of the ammonium bicarbonate solution is 1.5m3/h。
Preferably, in the step S4, the aging time is 10-20 min.
Preferably, the specific steps of S5 are: and transferring the cobalt carbonate slurry obtained in the step S4 into a plate-and-frame filter press for solid-liquid separation, and then transferring the separated solid into a washing kettle for slurrying and washing to obtain the purified cobalt carbonate.
Preferably, the ratio of the volume of the washing water in the washing kettle to the volume of the washing kettle is (0.45-0.5): 1.
preferably, the time for slurrying and washing is 20-30 min.
Preferably, in the step S6, the temperature during the flash evaporation is 120-150 ℃.
Compared with the prior art, 1) the method comprises the steps of adding a certain amount of carbonate solution into a reactor as a base solution, and then simultaneously adding a cobalt salt solution with a certain concentration and a carbonate solution with a certain concentration into the reactor at specified flow rates to perform neutralization and precipitation reaction to prepare intermediate slurry; adjusting the flow rates of the cobalt salt solution and the carbonate solution, adding the cobalt salt solution and the carbonate solution into the intermediate slurry, and continuing to perform a neutralization precipitation reaction to prepare cobalt carbonate slurry; finally, successfully preparing the target cobalt carbonate through slurrying, washing, flash evaporation and drying; and detection shows that the target cobalt carbonate prepared by the method is the flower-stick-shaped cobalt carbonate.
2) The invention successfully controls the growth direction of the cobalt carbonate crystal seed in the preparation process by accurately controlling the flow and concentration of the carbonate solution and the cobalt salt solution and the stirring speed of the reaction system, thereby effectively regulating and controlling the structural appearance of the cobalt carbonate in a flower-rod shape; the porosity of the flower-like cobalt carbonate obtained by the invention is relatively high, so that an energy-saving and environment-friendly precursor is provided for preparing the cobalt powder with large FSSS, and in addition, the reduced cobalt powder has inheritance, so that the flower-like cobalt carbonate obtained by the invention can also obtain the large FSSS cobalt powder with uniform particle size and narrow distribution peak, and the prepared cobalt powder can also be better applied to the manufacturing of high-end hard alloys; the preparation process is simple, mild in condition, beneficial to green and environment-friendly production and worthy of great popularization and application.
Drawings
FIG. 1 is an SEM photograph of a flower-like cobalt carbonate rod prepared in example 1 of the present invention;
fig. 2 is an SEM image of cobalt carbonate prepared in comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, when preparing a cobalt salt solution, the cobalt salt used may be a cobalt salt solution that can be completely ionized in water, such as cobalt chloride, cobalt sulfate, or cobalt nitrate, preferably a cobalt chloride solution;
when the carbonate solution is prepared in the following examples, the solute used is a salt capable of ionizing carbonate ions in water, and may be, for example, an ammonium bicarbonate solution, an ammonium carbonate solution, or a sodium bicarbonate solution, and preferably is ammonium bicarbonate;
the reactors used in the following examples are all reaction vessels.
The embodiment of the invention provides a preparation method of flower-rod-shaped cobalt carbonate, which comprises the following steps:
s1, respectively preparing a cobalt chloride solution with the concentration of 120-140 g/L and an ammonium bicarbonate solution with the concentration of 260-280 g/L for later use;
s2, moving to 12m3Adding 0.5-1.0 m into a reaction kettle3Taking the ammonium bicarbonate solution in the S1 as a base solution, and controlling the temperature of the base solution to be 50-55 ℃;
s3, stirring the cobalt chloride solution and the ammonium bicarbonate solution in the S1 at a stirring speed of 1600-2200 r/min by 0.3-0.4 m3/h、0.8～1.2m3Simultaneously adding the feed flow of the mixture/h into a reaction kettle containing the base solution in S2, and reacting for 1-3 h at 50-55 ℃ to obtain cobalt carbonate intermediate slurry
S4, mixing the cobalt chloride solution and the ammonium bicarbonate solution in the S1 by 0.4-0.6 m respectively3/h、1.2～1.8m3Simultaneously adding the feed flow of per hour into the cobalt carbonate intermediate slurry obtained in the step S3, reacting at 50-55 ℃ for 1-3 hours, and aging for 10-20 min after the reaction is finished to obtain cobalt carbonate slurry;
s5, transferring the cobalt carbonate slurry obtained in the step S4 into a plate-and-frame filter press for solid-liquid separation, and transferring the separated solid to a filter press with the thickness of 20m3And contains 9 to 10m3And slurrying and washing for 20-30 min in a washing kettle of washing water to obtain the purified cobalt carbonate.
And S6, dehydrating the purified cobalt carbonate obtained in the S5, carrying out flash evaporation and drying at 120-150 ℃, and finally, screening and packaging to obtain the target cobalt carbonate.
The following are specific examples
Example 1
The flower-like rod-shaped cobalt carbonate provided by the embodiment is obtained by the following steps:
s1, respectively preparing a 130g/L cobalt chloride solution and a 270g/L ammonium bicarbonate solution for later use;
s2, moving to 12m3Adding 0.8m into a reaction kettle3The ammonium bicarbonate solution in S1 is used as a base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, stirring the cobalt chloride solution and the ammonium bicarbonate solution in the S1 at a stirring speed of 2000r/min respectively at 0.35m3/h、1.0m3Simultaneously adding the feed flow of the mixture/h into a reaction kettle containing the base solution in S2, and reacting for 2h at the temperature of 50-55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, mixing the cobalt chloride solution and the ammonium bicarbonate solution in the S1 by 0.5m respectively3/h、1.5m3Simultaneously adding the feed flow of/h into the cobalt carbonate intermediate slurry obtained in S3, reacting for 2h at 50-55 ℃, and aging for 10-20 min after the reaction is finished to obtain cobalt carbonate slurry;
s5, transferring the cobalt carbonate slurry obtained in the step S4 into a plate-and-frame filter press for solid-liquid separation, and transferring the separated solid to a filter press with the thickness of 20m3And contains 9 to 10m3And slurrying and washing for 20-30 min in a washing kettle of washing water to obtain the purified cobalt carbonate.
And S6, dehydrating the purified cobalt carbonate obtained in the S5, carrying out flash evaporation and drying at 120-150 ℃, and finally, screening and packaging to obtain the target cobalt carbonate.
In order to verify whether the morphology structure of the obtained carbonic acid is in a flower-stick shape, the detection result of scanning a surface of the target cobalt carbonate obtained in example 1 is shown in fig. 1, and it can be clearly seen from fig. 1 that the morphology of the cobalt carbonate obtained in this example is in a flower-stick shape.
Example 2
The flower-like rod-shaped cobalt carbonate provided by the embodiment is obtained by the following steps:
s1, respectively preparing a cobalt chloride solution with the concentration of 120g/L and an ammonium bicarbonate solution with the concentration of 260g/L for later use;
s2, moving to 12m3Adding 0.5m into a reaction kettle3The ammonium bicarbonate solution in S1 is used as a base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, stirring the cobalt chloride solution and the ammonium bicarbonate solution in the S1 at a stirring speed of 1600r/min respectively at 0.3m3/h、0.8m3Simultaneously adding the feed flow of the mixture/h into a reaction kettle containing the base solution in S2, and reacting for 1h at the temperature of 50-55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, mixing the cobalt chloride solution and the ammonium bicarbonate solution in the S1 at a ratio of 0.4m3/h、1.2m3Simultaneously adding the feed flow of/h into the cobalt carbonate intermediate slurry obtained in S3, reacting for 1h at 50-55 ℃, and aging for 10-20 min after the reaction is finished to obtain cobalt carbonate slurry;
s5, transferring the cobalt carbonate slurry obtained in the step S4 into a plate-and-frame filter press for solid-liquid separation, and transferring the separated solid to a filter press with the thickness of 20m3And contains 9 to 10m3And slurrying and washing for 20-30 min in a washing kettle of washing water to obtain the purified cobalt carbonate.
And S6, dehydrating the purified cobalt carbonate obtained in the S5, carrying out flash evaporation and drying at 120-150 ℃, and finally, screening and packaging to obtain the target cobalt carbonate.
Example 3
The flower-like rod-shaped cobalt carbonate provided by the embodiment is obtained by the following steps:
s1, respectively preparing a cobalt chloride solution with the concentration of 140g/L and an ammonium bicarbonate solution with the concentration of 280g/L for later use;
s2, moving to 12m31.0m is added into a reaction kettle3The ammonium bicarbonate solution in S1 is used as a base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, stirring the cobalt chloride solution and the ammonium bicarbonate solution in the S1 at a stirring speed of 2200r/min respectively at 0.4m3/h、1.2m3Simultaneously adding the feed flow of the mixture/h into a reaction kettle containing the base solution in S2, and reacting for 3h at the temperature of 50-55 ℃ to obtain cobalt carbonate intermediate slurry
S4, mixing the cobalt chloride solution and the ammonium bicarbonate solution in the S1 at 0.6m respectively3/h、1.8m3Simultaneously adding the feed flow of/h into the cobalt carbonate intermediate slurry obtained in S3, reacting for 3h at 50-55 ℃, and aging for 10-20 min after the reaction is finished to obtain cobalt carbonate slurry;
s5, transferring the cobalt carbonate slurry obtained in the step S4 into a plate-and-frame filter press for solid-liquid separation, and transferring the separated solid to a filter press with the thickness of 20m3And contains 9 to 10m3And slurrying and washing for 20-30 min in a washing kettle of washing water to obtain the purified cobalt carbonate.
And S6, dehydrating the purified cobalt carbonate obtained in the S5, carrying out flash evaporation and drying at 120-150 ℃, and finally, screening and packaging to obtain the target cobalt carbonate.
Example 4
The flower-like rod-shaped cobalt carbonate provided by the embodiment is obtained by the following steps:
s1, respectively preparing a cobalt chloride solution with the concentration of 120g/L and an ammonium bicarbonate solution with the concentration of 260g/L for later use;
s2, moving to 12m3Adding 0.5m into a reaction kettle3The ammonium bicarbonate solution in S1 is used as a base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, stirring the cobalt chloride solution and the ammonium bicarbonate solution in the S1 at a stirring speed of 2000r/min respectively at 0.35m3/h、1.0m3Simultaneously adding the feed flow of the mixture/h into a reaction kettle containing the base solution in S2, and reacting for 2h at the temperature of 50-55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, mixing the cobalt chloride solution and the ammonium bicarbonate solution in the S1 by 0.5m respectively3/h、1.5m3Simultaneously adding the feed flow of/h into the cobalt carbonate intermediate slurry obtained in S3, reacting for 2h at 50-55 ℃, and aging for 10-20 min after the reaction is finished to obtain cobalt carbonate slurry;
s5, transferring the cobalt carbonate slurry obtained in the step S4 into a plate-and-frame filter press for solid-liquid separation, and transferring the separated solid to a filter press with the thickness of 20m3And contains 9 to 10m3Pulping and washing 20-30 mi in washing kettle of washing waterAnd n, obtaining the purified cobalt carbonate.
And S6, dehydrating the purified cobalt carbonate obtained in the S5, carrying out flash evaporation and drying at 120-150 ℃, and finally, screening and packaging to obtain the target cobalt carbonate.
Example 5
The flower-like rod-shaped cobalt carbonate provided by the embodiment is obtained by the following steps:
s1, respectively preparing a cobalt chloride solution with the concentration of 140g/L and an ammonium bicarbonate solution with the concentration of 280g/L for later use;
s2, moving to 12m31.0m is added into a reaction kettle3The ammonium bicarbonate solution in S1 is used as a base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, stirring the cobalt chloride solution and the ammonium bicarbonate solution in the S1 at a stirring speed of 2000r/min respectively at 0.35m3/h、1.0m3Simultaneously adding the feed flow of the mixture/h into a reaction kettle containing the base solution in S2, and reacting for 2h at the temperature of 50-55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, mixing the cobalt chloride solution and the ammonium bicarbonate solution in the S1 by 0.5m respectively3/h、1.5m3Simultaneously adding the feed flow of/h into the cobalt carbonate intermediate slurry obtained in S3, reacting for 2h at 50-55 ℃, and aging for 10-20 min after the reaction is finished to obtain cobalt carbonate slurry;
s5, transferring the cobalt carbonate slurry obtained in the step S4 into a plate-and-frame filter press for solid-liquid separation, and transferring the separated solid to a filter press with the thickness of 20m3And contains 9 to 10m3And slurrying and washing for 20-30 min in a washing kettle of washing water to obtain the purified cobalt carbonate.
And S6, dehydrating the purified cobalt carbonate obtained in the S5, carrying out flash evaporation and drying at 120-150 ℃, and finally, screening and packaging to obtain the target cobalt carbonate.
In order to verify whether the morphology structure of the carbonic acid obtained by the present invention is in a flower-stick shape, the electron microscope scanning detection of the target cobalt carbonate obtained in examples 2 to 5 is continued, and the detection result shows that the morphology structure of the cobalt carbonate obtained in examples 2 to 5 is also in a flower-stick shape.
Comparative example 1
The same preparation method as in example 1 was conducted except that the concentration of the cobalt chloride solution in S1 was 150 g/L; the concentration of the ammonium bicarbonate solution was 290 g/L.
Now, scanning detection of an electron microscope is performed on the cobalt carbonate obtained in the comparative example 1, and the detection result is shown in fig. 2, and the cobalt carbonate obtained in the comparative example 1 has a non-flower-rod-shaped morphology structure.
Comparative example 2
The same preparation method as that of example 1 was adopted, except that the concentration of the cobalt chloride solution in S1 was 110 g/L; the concentration of the ammonium bicarbonate solution was 250 g/L.
Comparative example 3
The same preparation as in example 1 was carried out, except that the feed rate of the cobalt chloride solution in S3 was 0.5m3H; the feed flow of the ammonium bicarbonate solution was 1.5m3/h。。
Comparative example 4
The same preparation as in example 1 was carried out, except that the feed rate of the cobalt chloride solution in S3 was 0.2m3H; the feed flow of the ammonium bicarbonate solution was 0.6m3/h。
Comparative example 5
The same procedure was followed as in example 1, except that the stirring speed of the system in S3 was 2500 r/min.
Comparative example 6
The same procedure was followed as in example 1, except that the stirring speed of the system in S3 was 1500 r/min.
Comparative example 7
The same preparation as in example 1 was carried out, except that the feed rate of the cobalt chloride solution in S4 was 0.8m3H; the feed flow of the ammonium bicarbonate solution was 2.0m3/h。。
Comparative example 8
The same preparation as in example 1 was carried out, except that the feed rate of the cobalt chloride solution in S3 was 0.3m3H; the feed flow of the ammonium bicarbonate solution was 1.0m3/h。
The scanning detection of an electron microscope is carried out on the cobalt carbonate obtained in the comparative examples 2-8, and the detection result shows that the cobalt carbonate obtained in the comparative examples 2-8 also has a non-flower-rod-shaped morphology structure.
The following examples are all specific examples for preparing corresponding cobalt powder from the cobalt carbonate obtained in the above examples or comparative examples, so as to better illustrate the performance of the cobalt carbonate of the present invention.
Example 6
The embodiment provides a preparation method of cobalt powder, which comprises the following steps:
and (3) carrying out reduction treatment on the flower-like cobalt carbonate prepared in the example 1 at the temperature of 300-800 ℃ for 2-4 h to obtain the target cobalt powder.
Example 7
The embodiment provides a preparation method of cobalt powder, which comprises the following steps:
and (3) carrying out reduction treatment on the flower-like cobalt carbonate prepared in the example 2 at the temperature of 300-800 ℃ for 2-4 h to obtain the target cobalt powder.
Example 8
The embodiment provides a preparation method of cobalt powder, which comprises the following steps:
and (3) carrying out reduction treatment on the flower-like cobalt carbonate prepared in the example 3 at the temperature of 300-800 ℃ for 2-4 h to obtain the target cobalt powder.
Example 9
The embodiment provides a preparation method of cobalt powder, which comprises the following steps:
and (3) carrying out reduction treatment on the flower-like cobalt carbonate prepared in the example 5 at the temperature of 300-800 ℃ for 2-4 h to obtain the target cobalt powder.
In order to verify whether the particle size of the cobalt powder prepared by using the cobalt carbonate in the form of a flower stick is uniform and the range value of the fisher particle size, the fisher particle size and D50 of the cobalt powder obtained in examples 6 to 9 were tested, and the specific test results are shown in table 1 below:
TABLE 1 data of particle diameter D50 and FSSS of cobalt powder obtained in examples 6 to 9
| Group of | D50(μm) | Fisher size |
| Example 6 | 11.25 | 3.14 |
| Example 7 | 11.32 | 3.17 |
| Example 8 | 11.23 | 3.12 |
| Example 9 | 11.28 | 3.15 |
As can be seen from the data in Table 1, the cobalt powder prepared by using the flower-stick-shaped cobalt carbonate of the invention has uniform particle size and time-consuming particle size as high as 3.17, meets the requirement of preparing high-end hard alloy and has good application prospect.
In summary, the invention adopts a method that a certain amount of ammonium bicarbonate solution is added into a reactor as a base solution, and then a cobalt chloride solution with a certain concentration and an ammonium bicarbonate solution with a certain concentration are simultaneously added into the reactor at specified flow rates respectively for neutralization and precipitation reaction to prepare an intermediate slurry; then adjusting the flow rates of the cobalt chloride solution and the ammonium bicarbonate solution, simultaneously adding the cobalt chloride solution and the ammonium bicarbonate solution into the intermediate slurry, and continuing to perform a neutralization precipitation reaction to prepare cobalt carbonate slurry; finally, successfully preparing the target cobalt carbonate through slurrying, washing, flash evaporation and drying; and detection shows that the target cobalt carbonate prepared by the method is the flower-stick-shaped cobalt carbonate.
In addition, the flow and concentration of the carbonate solution and the cobalt salt solution and the stirring speed of the reaction system are accurately controlled, so that the growth direction of the cobalt carbonate seed crystal in the preparation process is successfully controlled, and the structural appearance of the cobalt carbonate in a flower stick shape is effectively regulated and controlled; the porosity of the flower-like cobalt carbonate obtained by the invention is relatively high, so that an energy-saving and environment-friendly precursor is provided for preparing the cobalt powder with large FSSS, and in addition, the reduced cobalt powder has inheritance, so that the flower-like cobalt carbonate obtained by the invention can also obtain the large FSSS cobalt powder with uniform particle size and narrow distribution peak, and the prepared cobalt powder can also be better applied to the manufacturing of high-end hard alloys; the preparation process is simple, mild in condition, beneficial to green and environment-friendly production and worthy of great popularization and application.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the flower-rod-shaped cobalt carbonate is characterized by comprising the following steps of:
s1, respectively preparing a cobalt salt solution with the concentration of 120-140 g/L and a carbonate solution with the concentration of 260-280 g/L for later use;
s2, adding a certain volume of the carbonate solution in the S1 into the reactor to serve as a base solution;
s3, stirring the cobalt salt solution and the carbonate solution in the S1 at a stirring speed of 1600-2200 r/min to form a mixture, wherein the stirring speed is 0.3-0.4 m3/h、0.8～1.2m3Simultaneously adding the feed flow of the mixture/h into a reactor containing the base solution in S2, and reacting for 1-3 h at 50-55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, mixing the cobalt salt solution and the carbonate solution of S1 in a ratio of 0.4-0.6 m3/h、1.2～1.8m3Simultaneously adding the feed flow of the/h into the cobalt carbonate intermediate slurry obtained in the step S3, reacting for 1-3 h at 50-55 ℃, and aging after the reaction to obtain cobalt carbonate slurry;
s5, carrying out solid-liquid separation on the cobalt carbonate slurry obtained in the S4, and pulping and washing the solid obtained after the solid-liquid separation to obtain purified cobalt carbonate;
s6, dehydrating, flashing and drying the purified cobalt carbonate obtained in the S5 in sequence to obtain the flower-stick-shaped cobalt carbonate.
2. The method for preparing flower-like-rod-shaped cobalt carbonate according to claim 1, wherein in the step S2, the temperature of the base solution is controlled to be 50-55 ℃.
3. The method for preparing flower-shaped bar-shaped cobalt carbonate according to claim 2, wherein in the S2, the ratio of the volume of the carbonate solution to the volume of the reactor is (0.5/12-1/12): 1.
4. the method for preparing flower-like-rod-shaped cobalt carbonate according to claim 1, wherein in the S3, the feed flow rate of the cobalt chloride solution is 0.35m3The feed flow rate of the ammonium bicarbonate solution is 1.0m3/h。
5. The method for preparing flower-like-rod-shaped cobalt carbonate according to claim 1, wherein in the S4, the feed flow rate of the cobalt chloride solution is 0.5m3The feed flow rate of the ammonium bicarbonate solution is 1.5m3/h。
6. The method for preparing flower-like-rod-shaped cobalt carbonate according to claim 5, wherein in S4, the aging time is 10-20 min.
7. The method for preparing flower-like cobalt carbonate rod as claimed in claim 1, wherein the specific steps of S5 are as follows: and transferring the cobalt carbonate slurry obtained in the step S4 into a plate-and-frame filter press for solid-liquid separation, and then transferring the separated solid into a washing kettle for slurrying and washing to obtain the purified cobalt carbonate.
8. The method for preparing flower-like-rod-shaped cobalt carbonate according to claim 7, wherein the ratio of the volume of the washing water in the washing kettle to the volume of the washing kettle is (0.45-0.5): 1.
9. the method for preparing flower-like-rod-shaped cobalt carbonate according to claim 8, wherein the time for slurrying and washing is 20-30 min.
10. The method for preparing flower-like-rod-shaped cobalt carbonate according to claim 1, wherein the flash evaporation temperature in the S4 is 120-150 ℃.
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