CN113371764B - 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 125
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 120
- 239000002002 slurry Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 34
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000001868 cobalt Chemical class 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000001704 evaporation Methods 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
- 238000004537 pulping Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 12
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 34
- 239000001099 ammonium carbonate Substances 0.000 description 34
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 33
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 33
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 31
- 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 9
- -1 for example Substances 0.000 description 6
- 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
- 239000000203 mixture Substances 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 238000001878 scanning electron micrograph Methods 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
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000003839 salts Chemical class 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
-
- 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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- 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: preparing cobalt salt solution and carbonate solution respectively for later use; adding a certain volume of the carbonate solution into a reactor to serve as a base solution; then the cobalt salt solution and the carbonate solution are respectively added into a reactor containing base solution at the specified feeding flow rate for reaction to obtain cobalt carbonate intermediate slurry; then respectively adding the cobalt salt solution and the carbonate solution into the cobalt carbonate intermediate slurry at the same time according to the regulated specified feed flow rate to react, and aging after the reaction is finished to obtain cobalt carbonate slurry; and (3) carrying out solid-liquid separation on the cobalt carbonate slurry, pulping, washing, dehydrating, flash evaporating and drying to obtain the flower-rod-shaped cobalt carbonate. Through detection of the target cobalt carbonate prepared by the method, the target cobalt carbonate prepared by the method is found to have a flower-rod-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 large FSSS cobalt powder, the cobalt carbonate is generally used for preparing the branched large FSSS cobalt powder by increasing the reduction temperature or prolonging the residence time, but the method is used for preparing the large FSSS cobalt powder, so that the energy consumption is high, the shape uniformity of the generated branched large FSSS cobalt powder is poor, and the particle size distribution is wide, so that the branched large FSSS cobalt powder cannot be well applied to the manufacture of hard alloy.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of flower-rod-shaped cobalt carbonate, which solves the problems that the cobalt carbonate obtained by the prior art cannot meet the requirements of preparing large FSSS cobalt powder with uniform particle size and narrow distribution peak, and cannot be better applied to manufacturing of high-end hard alloy.
In order to solve the problems, the technical scheme adopted by the invention is that the preparation method of the flower-rod-shaped cobalt carbonate comprises the following steps:
s1, 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 respectively for later use;
s2, adding a certain volume of the carbonate solution in the step S1 into a reactor to serve as base solution;
s3, respectively mixing the cobalt salt solution and the carbonate solution in S1 at a stirring speed of 1600-2200 r/min at a ratio of 0.3-0.4 m 3 /h、0.8～1.2m 3 The feed flow rate of/h is simultaneously added into a reactor containing the base solution in the step S2, and the reaction is carried out for 1 to 3 hours at the temperature of 50 to 55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, respectively mixing the cobalt salt solution and the carbonate solution in the S1 by 0.4-0.6 m 3 /h、1.2～1.8m 3 Adding the feeding flow rate of/h into the cobalt carbonate intermediate slurry obtained in the step S3 at the same time, reacting for 1-3 h at 50-55 ℃, and aging after the reaction is finished 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;
and S6, sequentially dehydrating, flash evaporating and drying the purified cobalt carbonate obtained in the step S5 to obtain the flower-rod-shaped cobalt carbonate.
Preferably, in S2, the temperature of the base solution is controlled to be 50-55 ℃.
Preferably, in S2, the ratio of the volume of the carbonate solution to the volume of the reactor is (0.5/12 to 1/12): 1.
preferably, in the step S3, the feeding flow rate of the cobalt chloride solution is 0.35m 3 And/h, the feeding flow rate of the ammonium bicarbonate solution is 1.0m 3 /h。
Preferably, in the step S4, the feeding flow rate of the cobalt chloride solution is 0.5m 3 And/h, the feeding flow rate of the ammonium bicarbonate solution is 1.5m 3 /h。
Preferably, in the step S4, the aging time is 10 to 20 minutes.
Preferably, the specific step of S5 is: and (3) 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 into a washing kettle for slurrying washing to obtain purified cobalt carbonate.
Preferably, the ratio of the volume of the washing water in the washing tank to the volume of the washing tank is (0.45 to 0.5): 1.
preferably, the slurrying washing time is 20-30 min.
Preferably, in S6, the temperature at the time of the flash evaporation is 120 to 150 ℃.
Compared with the prior art, 1) adding a certain amount of carbonate solution into a reactor as base solution, and then respectively adding a cobalt salt solution with a certain concentration and a carbonate solution with a certain concentration into the reactor at a specified flow rate for neutralization and precipitation reaction to prepare intermediate slurry; then adjusting the flow rates of the cobalt salt solution and the carbonate solution, and simultaneously adding the cobalt salt solution and the carbonate solution into the intermediate slurry, and continuously carrying out neutralization precipitation reaction to prepare cobalt carbonate slurry; finally, pulping, washing, flash evaporating and drying are carried out to obtain the target cobalt carbonate successfully; and the detection shows that the target cobalt carbonate prepared by the method is flower-rod-shaped cobalt carbonate.
2) According to the invention, the flow and the 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 morphology of the cobalt carbonate in a flower rod shape is effectively regulated and controlled; the porosity of the flower-shaped cobalt carbonate obtained by the method is relatively high, so that an energy-saving and environment-friendly precursor is provided for preparing the cobalt powder of the large FSSS, and in addition, the flower-shaped cobalt carbonate obtained by the method can also obtain the large FSSS cobalt powder with uniform particle size and narrow distribution peak due to inheritance of the reduced cobalt powder, and the prepared cobalt powder can also be better applied to the manufacture of high-end hard alloy; the preparation method has the advantages of simple process, mild condition, contribution to green and environment-friendly production and great popularization and application value.
Drawings
FIG. 1 is an SEM image of a flower-like cobalt carbonate 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 further described in detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, cobalt salt solutions, preferably cobalt chloride solutions, which are cobalt chloride, cobalt sulfate, cobalt nitrate, or the like, capable of complete ionization in water, are used in preparing the cobalt salt solutions;
when the carbonate solution is prepared in the following embodiments, the solute used is a salt capable of ionizing carbonate ions in water, for example, ammonium bicarbonate solution, ammonium carbonate solution or sodium bicarbonate solution, etc., preferably ammonium bicarbonate;
the reactors used in the examples below were 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, direction 12m 3 Adding 0.5-1.0 m into a reaction kettle 3 The ammonium bicarbonate solution in the step S1 is used as base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, respectively mixing the cobalt chloride solution and the ammonium bicarbonate solution in S1 at a stirring speed of 1600-2200 r/min at a ratio of 0.3-0.4 m 3 /h、0.8～1.2m 3 The feed flow rate of/h is simultaneously added into a reaction kettle containing the base solution in S2, and the reaction is carried out for 1 to 3 hours at 50 to 55 ℃ to obtain cobalt carbonate intermediate slurry
S4, respectively mixing the cobalt chloride solution and the ammonium bicarbonate solution in the S1 by 0.4-0.6 m 3 /h、1.2～1.8m 3 Adding the feed flow of/h into the cobalt carbonate intermediate slurry obtained in the step S3 at the same time, reacting for 1-3 h 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 S4 into a plate-and-frame filter press for solid-liquid separation, and then transferring the separated solid to 20m 3 And contains 9-10 m 3 Pulping and washing the mixture in a washing kettle of washing water for 20-30 min to obtain purified cobalt carbonate.
S6, dehydrating the purified cobalt carbonate obtained in the step S5, flash evaporating 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-rod-shaped cobalt carbonate provided by the embodiment is obtained through the following steps:
s1, respectively preparing a cobalt chloride solution with the concentration of 130g/L and an amine bicarbonate solution with the concentration of 270g/L for later use;
s2, direction 12m 3 Adding 0.8m into a reaction kettle 3 The ammonium bicarbonate solution in the step S1 is used as a base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, dissolving cobalt chloride in S1 at a stirring speed of 2000r/minThe liquid and the ammonium bicarbonate solution were each at 0.35m 3 /h、1.0m 3 The feed flow rate of/h is added into a reaction kettle containing the base solution in the step S2 at the same time, and the reaction is carried out for 2h at 50-55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, respectively mixing the cobalt chloride solution and the ammonium bicarbonate solution in S1 by 0.5m 3 /h、1.5m 3 Adding the feeding flow rate of/h into the cobalt carbonate intermediate slurry obtained in the step S3 at the same time, 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 S4 into a plate-and-frame filter press for solid-liquid separation, and then transferring the separated solid to 20m 3 And contains 9-10 m 3 Pulping and washing the mixture in a washing kettle of washing water for 20-30 min to obtain purified cobalt carbonate.
S6, dehydrating the purified cobalt carbonate obtained in the step S5, flash evaporating and drying at 120-150 ℃, and finally screening and packaging to obtain the target cobalt carbonate.
In order to verify whether the morphology of the carbonic acid obtained in the invention is in a floral rod shape, the target cobalt carbonate obtained in the embodiment 1 is subjected to electron microscopy scanning detection, the detection result is shown in fig. 1, and it is clear from fig. 1 that the morphology of the cobalt carbonate obtained in the embodiment is in a floral rod shape.
Example 2
The flower-rod-shaped cobalt carbonate provided by the embodiment is obtained through the following steps:
s1, respectively preparing a cobalt chloride solution with the concentration of 120g/L and an amine bicarbonate solution with the concentration of 260g/L for later use;
s2, direction 12m 3 Adding 0.5m into a reaction kettle 3 The ammonium bicarbonate solution in the step S1 is used as a base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, respectively mixing the cobalt chloride solution and the ammonium bicarbonate solution in S1 at a stirring speed of 1600r/min at a speed of 0.3m 3 /h、0.8m 3 The feed flow rate of/h is added into a reaction kettle containing the base solution in the step S2 at the same time, and the reaction is carried out for 1h at 50-55 ℃ to obtain cobalt carbonate intermediate slurry;
S4、the cobalt chloride solution and the ammonium bicarbonate solution in S1 are respectively mixed at 0.4m 3 /h、1.2m 3 Adding the feeding flow rate of/h into the cobalt carbonate intermediate slurry obtained in the step S3 at the same time, 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 S4 into a plate-and-frame filter press for solid-liquid separation, and then transferring the separated solid to 20m 3 And contains 9-10 m 3 Pulping and washing the mixture in a washing kettle of washing water for 20-30 min to obtain purified cobalt carbonate.
S6, dehydrating the purified cobalt carbonate obtained in the step S5, flash evaporating and drying at 120-150 ℃, and finally screening and packaging to obtain the target cobalt carbonate.
Example 3
The flower-rod-shaped cobalt carbonate provided by the embodiment is obtained through the following steps:
s1, respectively preparing a cobalt chloride solution with the concentration of 140g/L and an amine bicarbonate solution with the concentration of 280g/L for later use;
s2, direction 12m 3 Adding 1.0m into a reaction kettle 3 The ammonium bicarbonate solution in the step S1 is used as a base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, respectively mixing the cobalt chloride solution and the ammonium bicarbonate solution in S1 at a stirring speed of 2200r/min at a speed of 0.4m 3 /h、1.2m 3 The feed flow rate of/h is simultaneously added into a reaction kettle containing base solution in S2, and the reaction is carried out for 3h at 50-55 ℃ to obtain cobalt carbonate intermediate slurry
S4, respectively mixing the cobalt chloride solution and the ammonium bicarbonate solution in S1 by 0.6m 3 /h、1.8m 3 Adding the feeding flow rate of/h into the cobalt carbonate intermediate slurry obtained in the step S3 at the same time, 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 S4 into a plate-and-frame filter press for solid-liquid separation, and then transferring the separated solid to 20m 3 And contains 9-10 m 3 Pulping and washing the water in a washing kettle for 20-30 min to obtain purified waterCobalt carbonate.
S6, dehydrating the purified cobalt carbonate obtained in the step S5, flash evaporating and drying at 120-150 ℃, and finally screening and packaging to obtain the target cobalt carbonate.
Example 4
The flower-rod-shaped cobalt carbonate provided by the embodiment is obtained through the following steps:
s1, respectively preparing a cobalt chloride solution with the concentration of 120g/L and an amine bicarbonate solution with the concentration of 260g/L for later use;
s2, direction 12m 3 Adding 0.5m into a reaction kettle 3 The ammonium bicarbonate solution in the step S1 is used as a base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, respectively mixing the cobalt chloride solution and the ammonium bicarbonate solution in S1 at a stirring speed of 2000r/min at a speed of 0.35m 3 /h、1.0m 3 The feed flow rate of/h is added into a reaction kettle containing the base solution in the step S2 at the same time, and the reaction is carried out for 2h at 50-55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, respectively mixing the cobalt chloride solution and the ammonium bicarbonate solution in S1 by 0.5m 3 /h、1.5m 3 Adding the feeding flow rate of/h into the cobalt carbonate intermediate slurry obtained in the step S3 at the same time, 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 S4 into a plate-and-frame filter press for solid-liquid separation, and then transferring the separated solid to 20m 3 And contains 9-10 m 3 Pulping and washing the mixture in a washing kettle of washing water for 20-30 min to obtain purified cobalt carbonate.
S6, dehydrating the purified cobalt carbonate obtained in the step S5, flash evaporating and drying at 120-150 ℃, and finally screening and packaging to obtain the target cobalt carbonate.
Example 5
The flower-rod-shaped cobalt carbonate provided by the embodiment is obtained through the following steps:
s1, respectively preparing a cobalt chloride solution with the concentration of 140g/L and an amine bicarbonate solution with the concentration of 280g/L for later use;
s2, direction 12m 3 Adding 1.0m into a reaction kettle 3 The ammonium bicarbonate solution in the step S1 is used as a base solution, and the temperature of the base solution is controlled to be 50-55 ℃;
s3, respectively mixing the cobalt chloride solution and the ammonium bicarbonate solution in S1 at a stirring speed of 2000r/min at a speed of 0.35m 3 /h、1.0m 3 The feed flow rate of/h is added into a reaction kettle containing the base solution in the step S2 at the same time, and the reaction is carried out for 2h at 50-55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, respectively mixing the cobalt chloride solution and the ammonium bicarbonate solution in S1 by 0.5m 3 /h、1.5m 3 Adding the feeding flow rate of/h into the cobalt carbonate intermediate slurry obtained in the step S3 at the same time, 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 S4 into a plate-and-frame filter press for solid-liquid separation, and then transferring the separated solid to 20m 3 And contains 9-10 m 3 Pulping and washing the mixture in a washing kettle of washing water for 20-30 min to obtain purified cobalt carbonate.
S6, dehydrating the purified cobalt carbonate obtained in the step S5, flash evaporating and drying at 120-150 ℃, and finally screening and packaging to obtain the target cobalt carbonate.
In order to verify whether the morphology of the carbonic acid obtained in the invention is in a flower-bar shape, the electron microscope scanning detection is continuously carried out on the target cobalt carbonate obtained in the examples 2-5, and the detection results show that the morphology of the cobalt carbonate obtained in the examples 2-5 is also in a flower-bar shape.
Comparative example 1
The same preparation as in example 1, except that the concentration of the cobalt chloride solution in S1 was 150g/L; the concentration of the ammonium bicarbonate solution was 290g/L.
The cobalt carbonate obtained in comparative example 1 is subjected to electron microscope scanning detection, and the detection result is shown in fig. 2, wherein the cobalt carbonate obtained in comparative example 1 has a non-flower-rod-shaped morphology structure.
Comparative example 2
The same preparation method as in example 1, except that the concentration of the cobalt chloride solution in S1 was 110g/L; the concentration of the ammonium bicarbonate solution was 250g/L.
Comparative example 3
The same preparation as in example 1, but with a different feed rate of cobalt chloride solution in S3 of 0.5m 3 /h; the feed flow rate of the ammonium bicarbonate solution was 1.5m 3 /h。。
Comparative example 4
The same preparation as in example 1, but with a different feed rate of cobalt chloride solution in S3 of 0.2m 3 /h; the feed flow rate of the ammonium bicarbonate solution was 0.6m 3 /h。
Comparative example 5
The same procedure as in example 1 was followed except that the stirring speed of the system in S3 was 2500r/min.
Comparative example 6
The same procedure as in example 1 was followed except that the stirring speed of the system in S3 was 1500r/min.
Comparative example 7
The same preparation as in example 1, but with a different feed rate of cobalt chloride solution in S4 of 0.8m 3 /h; the feed flow rate of the ammonium bicarbonate solution was 2.0m 3 /h。。
Comparative example 8
The same preparation as in example 1, but with a different feed rate of cobalt chloride solution in S3 of 0.3m 3 /h; the feed flow rate of the ammonium bicarbonate solution was 1.0m 3 /h。
The cobalt carbonates obtained in comparative examples 2 to 8 were subjected to electron microscopic scanning detection, and the detection results showed that the cobalt carbonates obtained in comparative examples 2 to 8 also had a morphology structure other than a flower-bar shape.
The following examples are specific examples of the preparation of the corresponding cobalt powder by means of the cobalt carbonate obtained in the above examples or comparative examples, in order to be able to better illustrate the properties of the cobalt carbonate according to the invention.
Example 6
The embodiment provides a preparation method of cobalt powder, which comprises the following steps:
the flower-shaped rod-shaped cobalt carbonate prepared in the embodiment 1 is subjected to reduction treatment for 2-4 hours at the temperature of 300-800 ℃ to obtain target cobalt powder.
Example 7
The embodiment provides a preparation method of cobalt powder, which comprises the following steps:
the flower-shaped rod-shaped cobalt carbonate prepared in the example 2 is subjected to reduction treatment for 2-4 hours at the temperature of 300-800 ℃ to obtain target cobalt powder.
Example 8
The embodiment provides a preparation method of cobalt powder, which comprises the following steps:
the flower-shaped rod-shaped cobalt carbonate prepared in the embodiment 3 is subjected to reduction treatment for 2-4 hours at the temperature of 300-800 ℃ to obtain target cobalt powder.
Example 9
The embodiment provides a preparation method of cobalt powder, which comprises the following steps:
the flower-shaped rod-shaped cobalt carbonate prepared in the example 5 is subjected to reduction treatment for 2-4 hours at the temperature of 300-800 ℃ to obtain target cobalt powder.
To verify whether the particle size of the cobalt powder prepared by using the flower-shaped cobalt carbonate of the present invention is uniform and the range of the Fisher size, the Fisher size and D50 of the cobalt powder obtained in examples 6 to 9 were examined, and the specific examination results are shown in Table 1 below:
table 1 detection data of particle diameter D50 and FSSS of cobalt powder obtained in examples 6 to 9
| Group of | D50(μm) | Fisher particle 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-shaped cobalt carbonate disclosed by the invention has uniform particle size, time-consuming particle size of up to 3.17, meets the requirements of preparing high-end hard alloy and has good application prospect.
In summary, the invention adopts the steps that a certain amount of ammonium bicarbonate solution is firstly added into a reactor to serve as base solution, and then cobalt chloride solution with a certain concentration and ammonium bicarbonate solution with a certain concentration are respectively added into the reactor at a specified flow rate to perform neutralization precipitation reaction, so that intermediate slurry is prepared; then adjusting the flow rates of the cobalt chloride solution and the ammonium bicarbonate solution, and simultaneously adding the cobalt chloride solution and the ammonium bicarbonate solution into the intermediate slurry, and continuing the neutralization precipitation reaction to prepare the cobalt carbonate slurry; finally, pulping, washing, flash evaporating and drying are carried out to obtain the target cobalt carbonate successfully; and the detection shows that the target cobalt carbonate prepared by the method is flower-rod-shaped cobalt carbonate.
In addition, the flow and the concentration of the carbonate solution and the cobalt salt solution and the stirring speed of the reaction system are precisely controlled, so that the growth direction of the cobalt carbonate seed crystal in the preparation process is successfully controlled, and the structural morphology of the cobalt carbonate in a flower rod shape is effectively regulated and controlled; the porosity of the flower-shaped cobalt carbonate obtained by the method is relatively high, so that an energy-saving and environment-friendly precursor is provided for preparing the cobalt powder of the large FSSS, and in addition, the flower-shaped cobalt carbonate obtained by the method can also obtain the large FSSS cobalt powder with uniform particle size and narrow distribution peak due to inheritance of the reduced cobalt powder, and the prepared cobalt powder can also be better applied to the manufacture of high-end hard alloy; the preparation method has the advantages of simple process, mild condition, contribution to green and environment-friendly production and great popularization and application value.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (9)
1. The preparation method of the flower-shaped cobalt carbonate is characterized by comprising the following steps of:
s1, 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 respectively for later use;
s2, adding a certain volume of the carbonate solution in the step S1 into a reactor to serve as base solution; the temperature of the base solution is controlled to be 50-55 ℃;
s3, respectively mixing the cobalt salt solution and the carbonate solution in S1 at a stirring speed of 1600-2200 r/min at a ratio of 0.3-0.4 m 3 /h、0.8～1.2m 3 The feed flow rate of/h is simultaneously added into a reactor containing the base solution in the step S2, and the reaction is carried out for 1 to 3 hours at the temperature of 50 to 55 ℃ to obtain cobalt carbonate intermediate slurry;
s4, respectively mixing the cobalt salt solution and the carbonate solution in the S1 by 0.4-0.6 m 3 /h、1.2～1.8m 3 Adding the feeding flow rate of/h into the cobalt carbonate intermediate slurry obtained in the step S3 at the same time, reacting for 1-3 h at 50-55 ℃, and aging after the reaction is finished 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;
and S6, sequentially dehydrating, flash evaporating and drying the purified cobalt carbonate obtained in the step S5 to obtain the flower-rod-shaped cobalt carbonate.
2. The method for producing a flower-like cobalt carbonate according to claim 1, wherein in S2, the ratio of the volume of the carbonate solution to the volume of the reactor is (0.5/12 to 1/12): 1.
3. the method for preparing flower-like cobalt carbonate according to claim 1, wherein in S3, the feeding flow rate of the cobalt salt solution is 0.35m 3 And/h, the feeding flow rate of the carbonate solution is 1.0m 3 /h。
4. The method for preparing flower-like cobalt carbonate according to claim 1, wherein in S4, the feeding flow rate of the cobalt salt solution is 0.5m 3 And/h, the feed rate of the carbonate solution is 1.5m 3 /h。
5. The method for preparing flower-like cobalt carbonate according to claim 4, wherein in S4, the aging time is 10 to 20 minutes.
6. The preparation method of the flower-rod-shaped cobalt carbonate according to claim 1, wherein the specific step of S5 is as follows: and (3) 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 into a washing kettle for slurrying washing to obtain purified cobalt carbonate.
7. The method for preparing flower-like cobalt carbonate according to claim 6, wherein the ratio of the volume of the washing water in the washing tank to the volume of the washing tank is (0.45 to 0.5): 1.
8. the method for preparing flower-like cobalt carbonate according to claim 7, wherein the slurrying and washing time is 20-30 min.
9. The method for preparing flower-like cobalt carbonate according to claim 1, wherein in S4, the temperature at the time of flash evaporation is 120 to 150 ℃.
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