CN113753969A - Preparation method of spherical cobalt carbonate particles with superfine particle size - Google Patents
Preparation method of spherical cobalt carbonate particles with superfine particle size Download PDFInfo
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Abstract
The invention discloses a preparation method of spherical cobalt carbonate particles with superfine particle size, which comprises the following steps: (1) taking a cobalt salt solution as a base solution, controlling the temperature to be 15-30 ℃, adding a carbonate source solution into a reaction kettle under the condition of stirring, controlling the molar weight of the added carbonate ions to be more than twice of that of cobalt ions in the base solution, and feeding for 3-6 minutes; (2) reducing the stirring speed, continuously adding the carbonate source solution into the reaction solution, and heating at the speed of 0.2-0.5 ℃/min for more than 60 minutes; and (3) stopping the temperature rise, and stirring the generated cobalt carbonate particles in a manner that the generated cobalt carbonate particles float and flow without sinking to the bottom for more than 60 minutes to obtain spherical cobalt carbonate particles. According to the embodiment of the invention, the preparation of the cobalt carbonate particles with the ultrafine particle size is realized, and good particle dispersibility and sphericity are obtained.
Description
Technical Field
The invention belongs to the field of metal powder material preparation, and particularly relates to a preparation method of spherical cobalt carbonate with ultrafine particle size.
Background
Cobalt powders are widely used in the aerospace, electrical, mechanical manufacturing, chemical and ceramic industries. Cobalt-based alloys or alloys containing cobalt are used as parts of gas turbine blades, vanes, ducts, jet engines, rocket engines, missiles and various high-load heat-resistant parts in chemical equipment and important metal materials for the atomic energy industry. Cobalt is used as a binder in powder metallurgy, and can ensure that the hard alloy has certain toughness. Magnetic alloys are indispensable materials in the modern electronic and electromechanical industries for manufacturing various elements of devices such as acoustic, optical, electrical, and magnetic. Cobalt is also an important component of permanent magnetic alloys.
The cobalt carbonate with small apparent density is used as one of precursors for preparing cobalt powder and is mainly used in the fields of diamond tools and hard alloy materials. In order to prepare high-end hard alloy and high-end diamond tools, manufacturers put higher requirements on the shape, the particle size distribution form and the impurity content of cobalt powder. The development direction of cobalt powder is small in particle size, good in sphericity and good in particle dispersibility. The cobalt powder has great inheritance to physical indexes of the precursor cobalt carbonate such as particle size, morphology, particle size distribution and the like, and the quality of the cobalt carbonate has direct influence on the quality of the cobalt powder. At present, the particle size of cobalt carbonate with superfine particle size is generally controlled to be 0.5-2 μm, the process technology is still incomplete, the particle size is small, the particle dispersibility and the sphericity are mutually contradictory, and the smaller the particle size is, the worse the particle dispersibility and the sphericity are.
Disclosure of Invention
The invention provides a preparation method of spherical cobalt carbonate with superfine particle size, which aims to prepare cobalt carbonate particles with fine particle size and obtain good particle dispersibility and sphericity.
According to an embodiment of the present invention, there is provided a method for preparing spherical cobalt carbonate particles having an ultra-fine particle size, the method comprising the steps of:
(1) taking the cobalt ion content as M1Taking a molar cobalt salt solution as a base solution, controlling the temperature to be 15-30 ℃, putting a carbonate source solution into a reaction kettle under the condition of stirring, and controlling the carbonate ions put into the reaction kettleAmount is M2Mole, M2≥2M1Feeding for 3-6 minutes to generate unstable amorphous cobalt carbonate;
(2) reducing the stirring speed, continuously adding the carbonic acid source solution into the reaction kettle, slowly heating at the speed of 0.2-0.5 ℃/min, controlling unstable amorphous cobalt carbonate to carry out crystal form recombination to form crystalline cobalt carbonate particles, and lasting for more than 60 minutes; and
(3) the temperature was stopped, and the resulting cobalt carbonate fine particles were stirred so as to float and flow without settling for 60 minutes or longer, thereby obtaining spherical cobalt carbonate particles.
In different embodiments, the cobalt salt solution may include one or more selected from a cobalt sulfate solution, a cobalt chloride solution, a cobalt nitrate solution, and a cobalt oxalate solution, and the cobalt ion concentration in the cobalt salt solution may be 80-150 g/L; and the carbonate source solution may include one or more selected from an ammonium bicarbonate solution, an ammonium carbonate solution, a sodium bicarbonate solution, and a sodium carbonate solution, and the carbonate concentration in the carbonate source solution may be 120 to 180 g/L.
Preferably, in step (1), M1:M2Is 1:5 to 1: 2.
Preferably, a propeller stirrer is adopted for stirring in the step (1), and the linear velocity of the tail end of the stirring blade is controlled to be 4-5 m/s.
Preferably, in the step (2), the temperature rise speed is 0.3-0.4 ℃/min.
Preferably, in the step (2), the amount of the carbonate ion to be charged is controlled to M3Mole, M1:M3Is 1:4 to 1: 1.5.
Preferably, in the step (2), a propeller stirrer is adopted for stirring, and the linear velocity of the tail end of the stirring blade is controlled to be 0.5-0.7 m/s.
Preferably, the duration of step (2) is 60 to 90 minutes.
Preferably, in the step (3), the temperature is kept at 45-55 ℃ for 60-120 minutes.
Preferably, in the step (3), an anchor frame type stirrer or a spiral ribbon type stirrer is adopted for stirring, and the linear velocity of the tail end of the stirring blade is controlled to be 0.2-0.3 m/s.
According to the embodiment of the invention, unstable amorphous cobaltous carbonate is quickly formed, then the crystal form recombination of the cobaltous carbonate is promoted, and the cobalt carbonate particles are subjected to mild repair growth under low stirring strength after the feeding is finished, so that the preparation of the cobalt carbonate particles with ultra-fine particle size is realized, and good particle dispersibility and sphericity are obtained.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments made with reference to the following drawings:
FIG. 1 is a scanning electron micrograph (1000 times) of cobalt carbonate obtained in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph (3000 times) of cobalt carbonate obtained in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph (10000 times) of cobalt carbonate obtained in example 1 of the present invention;
FIG. 4 is a scanning electron micrograph (1000 times) of cobalt carbonate obtained in example 2 of the present invention;
FIG. 5 is a scanning electron micrograph (3000 times) of cobalt carbonate obtained in example 2 of the present invention;
FIG. 6 is a scanning electron micrograph (10000 times) of cobalt carbonate obtained in example 2 of the present invention;
FIG. 7 is a scanning electron micrograph (1000 times) of cobalt carbonate obtained in example 3 of the present invention;
FIG. 8 is a scanning electron micrograph (3000 times) of cobalt carbonate obtained in example 3 of the present invention;
FIG. 9 is a scanning electron micrograph (12000 times) of cobalt carbonate obtained in example 3 of the present invention;
FIG. 10 is a scanning electron micrograph (1000 times) of amorphous cobalt carbonate as an intermediate obtained in example 1 of the present invention;
FIG. 11 is an XRD diffraction pattern of amorphous cobalt carbonate as an intermediate product and crystalline cobalt carbonate as a final product obtained in examples 1 to 3 of the present invention;
FIG. 12 is a scanning electron micrograph (8000 times) of cobalt carbonate obtained in comparative example 1 of the present invention;
FIG. 13 is a scanning electron micrograph (5000 times) of cobalt carbonate obtained in comparative example 2 of the present invention;
FIG. 14 is a scanning electron micrograph (5000 times) of cobalt carbonate obtained in comparative example 3 of the present invention;
FIG. 15 is a scanning electron micrograph (5000 times) of cobalt carbonate obtained in comparative example 4 of the present invention.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
The preparation method of the spherical cobalt carbonate particles with the superfine particle size can be used for preparing the cobalt carbonate particles with the particle size of 0.5-2.6 mu m. Specifically, the preparation method comprises the following steps:
(1) taking the cobalt ion content as M1Taking a molar cobalt salt solution as a base solution, controlling the temperature to be 15-30 ℃, putting a carbonate source solution into a reaction kettle under the condition of stirring, and controlling the amount of carbonate ions to be M2Mole, M2≥2M1Feeding for 3-6 minutes to generate unstable amorphous cobalt carbonate;
(2) reducing the stirring speed, continuously adding the carbonic acid source solution into the reaction kettle, slowly heating at the speed of 0.2-0.5 ℃/min, controlling unstable amorphous cobalt carbonate to carry out crystal form recombination to form crystalline cobalt carbonate particles, and lasting for more than 60 minutes; and
(3) the temperature was stopped, and the resulting cobalt carbonate fine particles were stirred so as to float and flow without settling for 60 minutes or longer, thereby obtaining spherical cobalt carbonate particles.
In the preparation method, all cobalt salt solution is used as base solution, and alkali liquor is rapidly added under the conditions of lower temperature and stronger stirring in the feeding process of the first stage (namely step (1)), so that cobalt ions rapidly form amorphous and unstable cobalt carbonate, and the oriented and accurate control on the crystal form recombination process is conveniently realized in the follow-up process; in the second stage feeding process (namely step (2)), slowly feeding the carbonate source solution, wherein strict temperature rise control is carried out at the moment, so that unstable amorphous cobalt carbonate is controlled to carry out crystal form recombination and recombine into a growth skeleton unit, and the problem of particle adhesion in the later stage is solved; and (3) after the feeding is finished, repairing and growing the cobalt carbonate particles (namely step (3)), wherein the low-intensity stirring provides a mild growth condition, cobalt ions and fine grains which do not participate in the reaction in the system are dissolved and recrystallized, and the cobalt ions and the fine grains are polymerized to form balls on the surfaces of the cobalt carbonate particles, so that the aim of improving the sphericity of the particles is fulfilled, and meanwhile, the particles are enabled to be uniform in size, narrow in distribution and good in dispersity.
The cobalt salt solution may include one or more selected from a cobalt sulfate solution, a cobalt chloride solution, a cobalt nitrate solution, and a cobalt oxalate solution. The carbonate source solution comprises one or more selected from ammonium bicarbonate solution, ammonium carbonate solution, sodium bicarbonate solution, and sodium carbonate solution. Furthermore, the invention is not limited in this respect and the cobalt salt fusion and carbonate source solution described above may be a combination of any solutions suitable for reaction to form cobalt carbonate.
The cobalt ion concentration in the cobalt salt solution adopted in the preparation method can be 80-150 g/L, and the carbonate concentration in the carbonate source solution can be 120-180 g/L.
In the above step (1), M is preferred1:M2Is 1:5 to 1: 2. On one hand, the carbonic acid source solution is added according to the proportion, so that cobalt ions in the reaction solution can be rapidly and sufficiently precipitated to form unstable amorphous cobalt carbonate, and on the other hand, the carbonic acid source solution can be saved.
In the step (1), a push type stirrer is preferably adopted for stirring, and the linear velocity of the tail end of a stirring blade is controlled to be 4-5 m/s. This provides a higher intensity of agitation, thereby enabling a large amount of the carbonate source solution to be put into the reaction vessel in a short time and the cobalt salt solution as a base solution to be mixed quickly and sufficiently. In the step (2), when the propeller stirrer is used for stirring, the linear velocity of the end of the stirring blade is preferably controlled to be 0.5 to 0.7 m/s.
Preferably, in the step (2), the temperature rise speed is 0.3-0.4 ℃/min.
Preferably, the first and second electrodes are formed of a metal,in the step (2), the amount of the carbonate ion to be fed is controlled to be M3Mole, M1:M3Is 1:4 to 1: 1.5. The duration of the step (2) is preferably 60 to 90 minutes. Thus, slow feeding at a low rate in the step (2) can be realized, so that the process of crystal form recombination can be accurately controlled.
Preferably, in the step (3), the temperature is kept at 45-55 ℃ for 60-120 minutes.
Preferably, in the step (3), an anchor frame type stirrer or a spiral ribbon type stirrer is adopted for stirring, and the linear velocity of the tail end of a stirring blade is controlled to be 0.2-0.3 m/s, so that the fluid field state in the reaction system is favorably controlled, and the sphericity is improved.
Examples of the present invention and comparative examples are described below. It should be understood that the present invention is not limited to these examples.
< example 1>
Mixing cobalt sulfate with pure water to prepare a cobalt sulfate solution with the cobalt ion concentration of 82.3 g/L; ammonium bicarbonate and pure water are mixed to prepare an ammonium bicarbonate solution with the carbonate concentration of 125.6 g/L.
And adding the prepared cobalt sulfate solution into the reaction kettle A to be used as a base solution. According to the molar quantity M of cobalt ions in the base solution1With the molar amount M of carbonate ions in the ammonium bicarbonate solution2The ratio of (1): 5 measuring the ammonium bicarbonate solution for the first time, and pumping the ammonium bicarbonate solution into the reaction kettle A for 3 minutes under the conditions that the temperature is 17 +/-1 ℃ and the linear velocity of the tail end of a stirring blade of the push type stirrer is 4 m/s.
Then, according to the molar amount M of cobalt ions1With the molar amount M of carbonate ions in the ammonium bicarbonate solution3The ratio of (1): 4 measuring the ammonium bicarbonate solution for the second time, pumping the ammonium bicarbonate solution into the reaction kettle A for 90 minutes under the condition that the linear velocity of the tail end of a stirring blade of the push type stirrer is 0.5m/s, and controlling the gradual temperature rise in the feeding process, wherein the end point temperature is 46 +/-1 ℃.
After the ammonium bicarbonate solution is added, the materials are completely transferred into a reaction kettle B adopting a frame type stirrer, the temperature is kept at 46 +/-1 ℃, the materials are stirred for 60 minutes under the condition that the linear velocity of the tail end of a stirring paddle is 0.2m/s, and the particles are controlled to be polymerized into balls.
And (3) carrying out solid-liquid separation, washing to remove impurities and drying on the final slurry, wherein the particle size D50 of the finally obtained cobalt carbonate particles is 0.886 mu m, the distribution width QD (D90-D10)/D50 is 1.49, and the content of the impurity S is 0.0059%. As can be seen from the scanning electron micrographs with different magnifications shown in fig. 1 and 2, the dispersibility of the cobalt carbonate particles obtained in example 1 was good. As can be seen from the higher magnification scanning electron micrograph shown in fig. 3, the cobalt carbonate particles obtained in example 1 had a very good sphericity.
< example 2>
Mixing cobalt chloride with pure water to prepare a cobalt chloride solution with the cobalt ion concentration of 123.5 g/L; ammonium carbonate was mixed with pure water to prepare an ammonium carbonate solution having a carbonate concentration of 148.4 g/L.
And adding the prepared cobalt chloride solution into the reaction kettle A to be used as a base solution. According to the molar quantity M of cobalt ions in the base solution1With the molar amount M of carbonate ions in the ammonium carbonate solution2The ratio of (1): 3 measuring the ammonium carbonate solution for the first time, and pumping the ammonium carbonate solution into the reaction kettle A for 4 minutes under the conditions that the temperature is 20 +/-1 ℃ and the terminal linear velocity of a stirring blade of the propelling stirrer is 4.5 m/s.
Then, according to the molar amount M of cobalt ions1With the molar amount M of carbonate ions in the ammonium carbonate solution3The ratio of (1): 2.5 measuring the ammonium carbonate solution for the second time, pumping the ammonium carbonate solution into the reaction kettle A for 83 minutes under the condition that the linear velocity of the tail end of a stirring blade of the propelling type stirrer is 0.6m/s, and controlling the gradual temperature rise in the feeding process, wherein the final temperature is 49 +/-1 ℃.
After the ammonium carbonate solution is added, all the materials are transferred into a reaction kettle B adopting a ribbon stirrer, the temperature is kept at 49 +/-1 ℃, the stirring is carried out for 80 minutes under the condition that the linear speed of the tail end of a stirring paddle is 0.25m/s, and the particles are controlled to polymerize into balls.
And (3) carrying out solid-liquid separation, washing to remove impurities and drying on the final slurry, wherein the particle diameter D50 of the finally obtained cobalt carbonate particles is 1.267 mu m, the distribution width QD is (D90-D10)/D50 is 1.52, and the content of the impurity Cl is 0.0031%. As can be seen from the scanning electron micrographs with different magnifications shown in fig. 4 and 5, the dispersibility of the cobalt carbonate particles obtained in example 2 was good. As can be seen from the higher magnification scanning electron micrograph shown in fig. 6, the cobalt carbonate particles obtained in example 2 had good sphericity.
< example 3>
Mixing cobalt nitrate and pure water to prepare a cobalt nitrate solution with the cobalt ion concentration of 143.1 g/L; sodium bicarbonate and pure water were mixed to prepare a sodium bicarbonate solution having a carbonate concentration of 169.7 g/L.
And adding the prepared cobalt nitrate solution into the reaction kettle A to be used as a base solution. According to the molar quantity M of cobalt ions in the base solution1With the molar amount M of carbonate ions in the sodium bicarbonate solution2The ratio of (1): 2, measuring sodium bicarbonate solution for the first time, and pumping the sodium bicarbonate solution into the reaction kettle A for 6 minutes under the conditions that the temperature is 27 +/-1 ℃ and the terminal linear velocity of a stirring blade of the push type stirrer is 5 m/s.
Then, according to the molar amount M of cobalt ions1With the molar amount M of carbonate ions in the sodium bicarbonate solution3The ratio of (1): 2.5 taking the sodium bicarbonate solution for the second time, pumping the sodium bicarbonate solution into the reaction kettle A for 70 minutes under the condition that the linear velocity of the tail end of a stirring blade of the propelling type stirrer is 0.7m/s, and controlling the gentle temperature rise in the feeding process, wherein the final temperature is 53 +/-1 ℃.
After the sodium bicarbonate solution is added, the materials are all transferred into a reaction kettle B adopting a helical ribbon type stirrer, the temperature is kept at 53 +/-1 ℃, the materials are stirred for 115 minutes under the condition that the linear velocity of the tail end of a stirring blade is 0.3m/s, and the particles are controlled to be polymerized into balls.
And (3) carrying out solid-liquid separation, washing to remove impurities and drying on the final slurry, wherein the particle size D50 of the finally obtained cobalt carbonate particles is 1.974 mu m, the distribution width QD is (D90-D10)/D50 is 1.59, and the content of the impurity N is 0.0046%. As can be seen from the scanning electron micrographs with different magnifications shown in fig. 7 and 8, the dispersibility of the cobalt carbonate particles obtained in example 3 was good. As can be seen from the higher magnification scanning electron micrograph shown in fig. 9, the cobalt carbonate particles obtained in example 3 had good sphericity.
To further clearly show that in the preparation method of cobalt carbonate particles according to the present invention, unstable amorphous cobalt carbonate is first synthesized, and then crystalline cobalt carbonate is obtained by crystal form reforming of cobalt carbonate, a scanning electron microscope image of cobalt carbonate precipitate obtained after rapid plunge of ammonium bicarbonate solution in the first stage of example 1 is shown in fig. 10, an XRD diffraction pattern of cobalt carbonate precipitate shown in fig. 10 (as shown by the lowermost curve in the figure) and XRD diffraction patterns of final product cobalt carbonate obtained in examples 1 to 3 (as shown by the upper three curves in the figure) are shown in fig. 11. The irregular shape of the cobalt carbonate precipitate formed after the first-stage rapid dosing is clearly seen in fig. 10, which in comparison with the regular spherical particles of the final product cobalt carbonate shown in fig. 1 to 9, illustrates that a recombination from amorphous cobalt carbonate to crystalline cobalt carbonate is achieved during the preparation process. The XRD diffractogram of fig. 11 more definitively indicates that amorphous cobalt carbonate (corresponding to the characteristic peaks of amorphous cobalt carbonate in the curve) is formed in the early stage of the preparation process, while the final product is crystalline cobalt carbonate (corresponding to the curve having the characteristic peaks of crystalline cobalt carbonate).
< comparative example 1>
Mixing cobalt sulfate with pure water to prepare a cobalt sulfate solution with the cobalt ion concentration of 82.3 g/L; ammonium bicarbonate and pure water are mixed to prepare an ammonium bicarbonate solution with the carbonate concentration of 125.6 g/L.
Adding pure water into the reaction kettle A as a base solution according to the molar weight M of cobalt ions1Molar amount M with carbonate ion2The ratio of (1): 5, measuring a cobalt sulfate solution and an ammonium bicarbonate solution, and pumping the cobalt sulfate solution and the ammonium bicarbonate solution into the reaction kettle A for 3 minutes under the conditions that the temperature is 17 +/-1 ℃ and the linear velocity of the tail end of a stirring blade of the push type stirrer is 4 m/s.
According to the molar weight M of cobalt ions in the added cobalt sulfate solution1With the molar amount M of carbonate ions in the ammonium bicarbonate solution3The ratio of (1): 4 measuring the ammonium bicarbonate solution again, pumping the ammonium bicarbonate solution into the reaction kettle A for 90 minutes under the condition that the linear velocity of the tail end of a stirring blade of the push type stirrer is 0.5m/s, and controlling the gradual temperature rise in the feeding process to be 46 +/-1 ℃.
After the ammonium bicarbonate solution is added, the materials are completely transferred into a reaction kettle B adopting a frame type stirrer, the temperature is kept at 45 ℃, and the materials are stirred for 60 minutes under the condition that the linear velocity of the tail end of a stirring blade is 0.2 m/s.
In short, comparative example 1 employed substantially the same treatment manner and conditions as in example 1, except that pure water was used as a base solution instead of the cobalt sulfate solution and the ammonium hydrogencarbonate solution were fed in parallel during the first-stage feeding.
And (3) carrying out solid-liquid separation, washing to remove impurities and drying on the final slurry, wherein the particle diameter D50 of the finally obtained cobalt carbonate particles is 6.211 mu m, and the distribution width QD is (D90-D10)/D50 is 1.12. As can be seen from the scanning electron microscope image of the cobalt carbonate particles obtained in comparative example 1 shown in fig. 12, the cobalt carbonate particles were not uniformly crystallized, were irregular in shape, and did not form spherical particles.
< comparative example 2>
Mixing cobalt sulfate with pure water to prepare a cobalt sulfate solution with the cobalt ion concentration of 81.6 g/L; the ammonium bicarbonate and pure water are mixed to prepare an ammonium bicarbonate solution with the carbonate concentration of 125.5 g/L.
And adding the prepared cobalt sulfate solution into the reaction kettle A to be used as a base solution. According to the molar quantity M of cobalt ions in the base solution1With the molar amount M of carbonate ions in the ammonium bicarbonate solution2The ratio of (1): 5, measuring the ammonium bicarbonate solution for the first time, and pumping the ammonium bicarbonate solution into the reaction kettle A for 3 minutes under the conditions that the temperature is 35-38 ℃ and the linear velocity of the tail end of a stirring blade of the push type stirrer is 4 m/s.
Then, according to the molar amount M of cobalt ions1With the molar amount M of carbonate ions in the ammonium bicarbonate solution3The ratio of (1): 4 measuring the ammonium bicarbonate solution for the second time, pumping the ammonium bicarbonate solution into the reaction kettle A for 90 minutes under the condition that the linear velocity of the tail end of a stirring blade of the push type stirrer is 0.5m/s, and controlling the gradual temperature rise in the feeding process, wherein the end point temperature is 46 +/-1 ℃.
After the ammonium bicarbonate solution is added, the materials are completely transferred into a reaction kettle B adopting a frame type stirrer, the temperature is kept at 46 +/-1 ℃, and the materials are stirred for 60 minutes under the condition that the linear velocity of the tail end of a stirring blade is 0.2 m/s.
In brief, comparative example 2 employed substantially the same treatment and conditions as example 1, except that the temperature was controlled to 35-38 ℃ during the first stage charging.
And (3) carrying out solid-liquid separation, washing to remove impurities and drying on the final slurry, wherein the particle diameter D50 of the finally obtained cobalt carbonate particles is 2.218 mu m, and the distribution width QD is (D90-D10)/D50 is 2.68. From the scanning electron micrograph of the cobalt carbonate particles obtained in comparative example 2 shown in fig. 13, it can be seen that the sphericity of cobalt carbonate is poor, the blocking and agglomeration are severe, and the dispersibility is poor.
< comparative example 3>
Mixing cobalt sulfate with pure water to prepare a cobalt sulfate solution with the cobalt ion concentration of 83.3 g/L; ammonium bicarbonate and pure water are mixed to prepare ammonium bicarbonate solution with the carbonate concentration of 142.6 g/L.
And adding the prepared cobalt sulfate solution into the reaction kettle A to be used as a base solution. According to the molar quantity M of cobalt ions in the base solution1With the molar amount M of carbonate ions in the ammonium bicarbonate solution2The ratio of (1): 5 measuring the ammonium bicarbonate solution for the first time, and pumping the ammonium bicarbonate solution into the reaction kettle A for 20 minutes under the conditions that the temperature is 17 +/-1 ℃ and the linear velocity of the tail end of a stirring blade of the push type stirrer is 4 m/s.
Then, according to the molar amount M of cobalt ions1With the molar amount M of carbonate ions in the ammonium bicarbonate solution3The ratio of (1): 4 measuring the ammonium bicarbonate solution for the second time, pumping the ammonium bicarbonate solution into the reaction kettle A for 90 minutes under the condition that the linear velocity of the tail end of a stirring blade of the push type stirrer is 0.5m/s, and controlling the gradual temperature rise in the feeding process, wherein the end point temperature is 46 +/-1 ℃.
After the ammonium bicarbonate solution is added, the materials are completely transferred into a reaction kettle B adopting a frame type stirrer, the temperature is kept at 46 +/-1 ℃, and the stirring is carried out for 60 minutes under the condition that the linear velocity of the tail end of a stirring blade is 0.2 m/s.
In brief, comparative example 3 employed substantially the same treatment and conditions as example 1, except that the first stage charge time/reaction time was 20 minutes.
And (3) carrying out solid-liquid separation, washing to remove impurities and drying on the final slurry, wherein the particle diameter D50 of the finally obtained cobalt carbonate particles is 4.363 mu m, and the distribution width QD is (D90-D10)/D50 is 3.64. From the scanning electron micrograph of the cobalt carbonate particles obtained in comparative example 3 shown in fig. 14, it can be seen that the cobalt carbonate was strongly adhered and agglomerated, had poor dispersibility, and did not form spherical particles.
< comparative example 4>
Mixing cobalt chloride with pure water to prepare a cobalt chloride solution with the cobalt ion concentration of 123.1 g/L; ammonium carbonate and pure water are mixed to prepare 143.4g/L carbonate lye.
And adding the prepared cobalt chloride solution into the reaction kettle A to be used as a base solution. According to the molar quantity M of cobalt ions in the base solution1With the molar amount M of carbonate ions in the ammonium carbonate solution2The ratio of (1): 3 measuring ammonium carbonate solution for the first time, and pumping the alkali liquor into the reaction kettle A for 4 minutes under the conditions that the temperature is 20 +/-1 ℃ and the terminal linear velocity of a stirring blade of the propelling type stirrer is 4.5 m/s.
Then, according to the molar amount M of cobalt ions1With the molar amount M of carbonate ions in the ammonium carbonate solution3The ratio of (1): 2.5 measuring the ammonium carbonate solution for the second time, pumping the ammonium carbonate solution into the reaction kettle A for 40 minutes under the condition that the terminal linear speed of a stirring blade of the propelling type stirrer is 0.6m/s, and controlling the gradual temperature rise in the feeding process to be 49 +/-1 ℃.
After the ammonium carbonate solution is added, all the materials are transferred into a reaction kettle B adopting a ribbon stirrer, the temperature is kept at 49 +/-1 ℃, and the stirring is carried out for 80 minutes under the condition that the linear velocity of the tail end of a stirring blade is 0.25 m/s.
Briefly, comparative example 4 employed substantially the same treatment and conditions as example 2, except that the second stage feed time/reaction time was 40 minutes.
And (3) carrying out solid-liquid separation, washing to remove impurities and drying on the final slurry, wherein the particle diameter D50 of the finally obtained cobalt carbonate particles is 6.351 mu m, and the distribution width QD is (D90-D10)/D50 is 2.59. From the scanning electron micrograph of the cobalt carbonate particles obtained in comparative example 4 shown in fig. 15, it can be seen that the sphericity of cobalt carbonate is poor, the blocking and agglomeration are severe, and the dispersibility is poor.
The following table shows a comparison table of some parameters and particle size indexes of the obtained cobalt carbonate particles in examples 1 to 3 and comparative examples 1 to 4.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (10)
1. A preparation method of spherical cobalt carbonate particles with superfine particle sizes comprises the following steps:
(1) taking the cobalt ion content as M1Taking a molar cobalt salt solution as a base solution, controlling the temperature to be 15-30 ℃, putting a carbonate source solution into a reaction kettle under the condition of stirring, and controlling the amount of carbonate ions to be M2Mole, M2≥2M1Feeding for 3-6 minutes to generate unstable amorphous cobalt carbonate;
(2) reducing the stirring speed, continuously adding the carbonic acid source solution into the reaction kettle, slowly heating at the speed of 0.2-0.5 ℃/min, controlling unstable amorphous cobalt carbonate to carry out crystal form recombination to form crystalline cobalt carbonate particles, and lasting for more than 60 minutes; and
(3) the temperature was stopped, and the resulting cobalt carbonate fine particles were stirred so as to float and flow without settling for 60 minutes or longer, thereby obtaining spherical cobalt carbonate particles.
2. The preparation method according to claim 1, wherein the cobalt salt solution comprises one or more selected from a cobalt sulfate solution, a cobalt chloride solution, a cobalt nitrate solution and a cobalt oxalate solution, and the cobalt ion concentration in the cobalt salt solution is 80-150 g/L; and is
The carbonate source solution comprises one or more of ammonium bicarbonate solution, ammonium carbonate solution, sodium bicarbonate solution and sodium carbonate solution, and the concentration of carbonate in the carbonate source solution is 120-180 g/L.
3. The process according to claim 1, wherein, in the step (1), M is1:M2Is 1:5 to 1: 2.
4. The production method according to claim 1 or 3, wherein the stirring is performed by a propeller stirrer in the step (1), and a linear velocity of a tip of the stirring blade is controlled to be 4 to 5 m/s.
5. The method according to claim 1, wherein the temperature is increased at a rate of 0.3 to 0.4 ℃/min in the step (2).
6. The preparation method according to claim 1, wherein in the step (2), the amount of carbonate ions charged is controlled to M3Mole, M1:M3Is 1:4 to 1: 1.5.
7. The production method according to claim 1 or 6, wherein in the step (2), the stirring is performed by using a propeller stirrer, and the linear velocity of the tip of the stirring blade is controlled to be 0.5 to 0.7 m/s.
8. The method of claim 1 or 6, wherein the duration of step (2) is 60 to 90 minutes.
9. The method according to claim 1, wherein in the step (3), the temperature is maintained at 45 to 55 ℃ for 60 to 120 minutes.
10. The production method according to claim 1 or 9, wherein in the step (3), the stirring is performed by using an anchor frame type stirrer or a ribbon type stirrer, and a linear velocity of a tip of the stirring blade is controlled to be 0.2 to 0.3 m/s.
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| JP2002003222A (en) * | 2000-06-16 | 2002-01-09 | Sumitomo Metal Mining Co Ltd | Basic cobalt carbonate and method for manufacturing it |
| CN104556248A (en) * | 2013-10-12 | 2015-04-29 | 中国电子科技集团公司第十八研究所 | Method for continuously producing large-particle spherical cobalt carbonate |
| CN110540248A (en) * | 2018-05-28 | 2019-12-06 | 荆门市格林美新材料有限公司 | Preparation method of small-particle-size cobalt oxide |
| CN113044888A (en) * | 2019-12-26 | 2021-06-29 | 荆门市格林美新材料有限公司 | Preparation method of amorphous cobalt carbonate |
| CN113149084A (en) * | 2021-02-09 | 2021-07-23 | 荆门市格林美新材料有限公司 | Preparation method of superfine cobalt oxide |
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| JP2002003222A (en) * | 2000-06-16 | 2002-01-09 | Sumitomo Metal Mining Co Ltd | Basic cobalt carbonate and method for manufacturing it |
| CN104556248A (en) * | 2013-10-12 | 2015-04-29 | 中国电子科技集团公司第十八研究所 | Method for continuously producing large-particle spherical cobalt carbonate |
| CN110540248A (en) * | 2018-05-28 | 2019-12-06 | 荆门市格林美新材料有限公司 | Preparation method of small-particle-size cobalt oxide |
| CN113044888A (en) * | 2019-12-26 | 2021-06-29 | 荆门市格林美新材料有限公司 | Preparation method of amorphous cobalt carbonate |
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