CN113753969B - Preparation method of superfine particle size spherical cobalt carbonate particles - Google Patents

Preparation method of superfine particle size spherical cobalt carbonate particles Download PDF

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CN113753969B
CN113753969B CN202111150849.3A CN202111150849A CN113753969B CN 113753969 B CN113753969 B CN 113753969B CN 202111150849 A CN202111150849 A CN 202111150849A CN 113753969 B CN113753969 B CN 113753969B
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cobalt
solution
carbonate
stirring
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CN113753969A (en
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张荣洲
田礼平
刘人生
秦才胜
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Quzhou Huayou Cobalt New Material Co ltd
Zhejiang Huayou Cobalt Co Ltd
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Quzhou Huayou Cobalt New Material Co ltd
Zhejiang Huayou Cobalt Co Ltd
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    • C01G51/00—Compounds of cobalt
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    • C01—INORGANIC CHEMISTRY
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    • 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
    • C01P2004/32—Spheres
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    • 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
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract

The invention discloses a preparation method of superfine particle size spherical cobalt carbonate particles, which comprises the following steps: (1) Taking cobalt salt solution as base solution, controlling the temperature to be 15-30 ℃, adding carbonate source solution into a reaction kettle under the stirring condition, and controlling the molar quantity of carbonate ions added to be more than twice of that of cobalt ions in the base solution, wherein the feeding time is 3-6 minutes; (2) Reducing the stirring speed, continuously adding a 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 mixture so that the generated cobalt carbonate particles float and flow without sinking for more than 60 minutes to obtain spherical cobalt carbonate particles. According to the embodiment of the invention, the preparation of the superfine particle size cobalt carbonate particles is realized, and good particle dispersibility and sphericity are obtained.

Description

Preparation method of superfine particle size spherical cobalt carbonate particles
Technical Field
The invention belongs to the field of metal powder material preparation, and particularly relates to a preparation method of superfine particle size spherical cobalt carbonate.
Background
Cobalt powder is widely used in the aerospace, electrical, mechanical manufacturing, chemical and ceramic industries. Cobalt-based alloys or cobalt-containing alloy steels are used as important metallic materials in the gas turbine blades, impellers, ducts, jet engines, rocket engines, missile components and various high-load heat-resistant components in chemical plants and in the nuclear industry. Cobalt is used as a binder in powder metallurgy to ensure that the hard alloy has certain toughness. Magnetic alloys are an indispensable material in the modern electronics and electromechanical industry for the manufacture of various components of acoustic, optical, electrical and magnetic devices. Cobalt is also an important component of permanent magnetic alloys.
The cobalt carbonate with small apparent density is used as one of the 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, particle size distribution shape and 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 on physical indexes such as particle size, morphology, particle size distribution and the like of the precursor cobalt carbonate, and the quality of the cobalt carbonate has direct influence on the quality of the cobalt powder. At present, the particle size of the superfine particle size cobalt carbonate is generally controlled to be between 0.5 and 2 mu m, the process technology is still imperfect, the particle size is small, the particle dispersibility is good, the sphericity is good, the contradiction is realized, and the particle dispersibility and sphericity are poorer as the particle size is smaller.
Disclosure of Invention
The invention provides a preparation method of superfine particle size spherical cobalt carbonate, which aims to prepare cobalt carbonate particles with small particle size and obtain good particle dispersibility and sphericity.
According to an embodiment of the present invention, there is provided a method for preparing ultra-fine particle size spherical cobalt carbonate particles, the method comprising the steps of:
(1) With cobalt ion content M 1 Adding a carbonate source solution into a reaction kettle under the stirring condition with the molar cobalt salt solution as a base solution and the temperature controlled at 15-30 ℃, wherein the amount of carbonate ions added is controlled at M 2 Molar, M 2 ≥2M 1 The feeding time is 3-6 minutes, and unstable amorphous cobalt carbonate is generated;
(2) Reducing the stirring speed, continuously adding a carbonate source solution into the reaction kettle, slowly heating at the speed of 0.2-0.5 ℃/min, and controlling unstable amorphous cobalt carbonate to carry out crystal form recombination to form crystalline cobalt carbonate particles, wherein the duration is more than 60 minutes; and
(3) The temperature rise was stopped, and the resultant cobalt carbonate particles were stirred so as to float and flow without sinking, for a period of 60 minutes or longer, to obtain 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 to 150g/L; and the carbonate source solution may include one or more selected from ammonium bicarbonate solution, ammonium carbonate solution, sodium bicarbonate solution, and sodium carbonate solution, and the carbonate concentration in the carbonate source solution may be 120 to 180g/L.
Preferably, in step (1), M 1 :M 2 Is 1:5-1:2.
Preferably, in the step (1), stirring is performed by using a propeller type stirrer, and the linear velocity of the tail end of the stirring blade is controlled to be 4-5 m/s.
Preferably, in step (2), the rate of temperature increase is 0.3 to 0.4 ℃/min.
Preferably, in the step (2), the amount of carbonate ions charged is controlled to be M 3 Molar, M 1 :M 3 1:4 to 1:1.5.
Preferably, in the step (2), stirring is performed by adopting a push-type stirrer, 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 step (3), the temperature is maintained at 45 to 55℃for a period of 60 to 120 minutes.
Preferably, in the step (3), stirring is performed by using an anchor frame type stirrer or a spiral belt type stirrer, 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, the preparation of the ultra-fine particle size cobalt carbonate particles is realized by firstly rapidly forming unstable cobalt carbonate amorphous, then promoting the recombination of cobalt carbonate crystal forms, and after the material feeding is completed, carrying out mild repair growth on the cobalt carbonate particles under low stirring intensity, thereby obtaining good particle dispersibility and sphericity.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the accompanying drawings in which:
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 product 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 is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
The method for preparing ultra-fine particle size spherical cobalt carbonate particles of the present invention can be used to prepare, for example, cobalt carbonate particles having a particle size of 0.5 to 2.6. Mu.m. Specifically, the preparation method comprises the following steps:
(1) With cobalt ion content M 1 Taking cobalt salt solution with mole as base solution, controlling the temperature at 15-30 ℃, stirringUnder the condition that the carbonate source solution is put into a reaction kettle, the amount of carbonate ions put into the reaction kettle is controlled to be M 2 Molar, M 2 ≥2M 1 The feeding time is 3-6 minutes, and unstable amorphous cobalt carbonate is generated;
(2) Reducing the stirring speed, continuously adding a carbonate source solution into the reaction kettle, slowly heating at the speed of 0.2-0.5 ℃/min, and controlling unstable amorphous cobalt carbonate to carry out crystal form recombination to form crystalline cobalt carbonate particles, wherein the duration is more than 60 minutes; and
(3) The temperature rise was stopped, and the resultant cobalt carbonate particles were stirred so as to float and flow without sinking, for a period of 60 minutes or longer, to obtain spherical cobalt carbonate particles.
In the preparation method, all cobalt salt solution is adopted as base solution, and alkali liquor is rapidly added at a lower temperature and under a stronger stirring condition in the first-stage feeding process (namely, step (1)), so that cobalt ions rapidly form amorphous and unstable cobalt carbonate, and the subsequent realization of directional and accurate control on the crystal form recombination process is facilitated; in the second-stage feeding process (i.e. step (2)), the carbonate source solution is slowly fed, and at the moment, along with strict temperature rising control, the purpose is to control unstable amorphous cobalt carbonate to carry out crystal form recombination, and the amorphous cobalt carbonate is recombined into a growth framework unit, so that the problem of later-stage particle adhesion is solved; after the material is fed, the cobalt carbonate particles are subjected to repair growth (namely, step (3)), wherein 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 are polymerized into balls on the surfaces of the cobalt carbonate particles, so that the purpose of improving the sphericity of the particles is achieved, and meanwhile, the particles are uniform in size, narrow in distribution and good in dispersibility.
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 any combination of 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 adopted can be 120-180 g/L.
In the above step (1), M is preferably selected 1 :M 2 Is 1:5-1:2. On the one hand, the carbonate source solution is added in the proportion, so that cobalt ions in the reaction solution can be rapidly and fully precipitated to form unstable amorphous cobalt carbonate, and on the other hand, the carbonate source solution can be saved.
In the step (1), stirring is preferably performed by a propeller type stirrer, and the linear velocity of the end of the stirring blade is controlled to be 4 to 5m/s. In this way, the stirring with higher intensity can be provided, so that a large amount of carbonate source solution which is fed into the reaction kettle in a short time can be quickly and fully mixed with cobalt salt solution which is used as base solution. In the case of stirring by a propeller stirrer in the step (2), the linear velocity of the stirring blade tip is preferably controlled to be 0.5 to 0.7m/s.
Preferably, in step (2), the rate of temperature increase is 0.3 to 0.4 ℃/min.
Preferably, in the step (2), the amount of carbonate ions charged is controlled to be M 3 Molar, M 1 :M 3 1:4 to 1:1.5. The duration of step (2) is preferably 60 to 90 minutes. Thus, slow feeding at a low rate in the step (2) can be realized to precisely control the progress of crystal form recombination.
Preferably, in step (3), the temperature is maintained at 45 to 55℃for a period of 60 to 120 minutes.
Preferably, in the step (3), the anchor frame type stirrer or the spiral belt type stirrer is adopted for stirring, and the linear speed of the tail end of the stirring blade is controlled to be 0.2-0.3 m/s, so that the state of a fluid field in a reaction system is favorably controlled, and the sphericity is improved.
The following describes examples and comparative examples of the present invention. It should be understood that the present invention is not limited to any of these embodiments.
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 ammonium bicarbonate solution with carbonate concentration of 125.6 g/L.
And (3) adding all the prepared cobalt sulfate solution into the reaction kettle A to serve as base solution. According to the mole amount M of cobalt ions in the base solution 1 Molar mass M with carbonate ions in ammonium bicarbonate solution 2 The ratio of (1): 5, firstly measuring ammonium bicarbonate solution, and pumping the ammonium bicarbonate solution into the reaction kettle A for 3 minutes under the condition that the temperature is 17+/-1 ℃ and the linear speed of the tail end of a stirring blade of a push-type stirrer is 4 m/s.
Then, according to the mole amount M of cobalt ions 1 Molar mass M with carbonate ions in ammonium bicarbonate solution 3 The ratio of (1): and 4, measuring 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 speed of the tail end of a stirring blade of a push-type stirrer is 0.5m/s, and controlling the temperature rising gradually in the feeding process, wherein the end temperature is 46+/-1 ℃.
After the ammonium bicarbonate solution is completely added, the materials are all transferred into a reaction kettle B adopting a frame stirrer, the temperature is kept at 46+/-1 ℃, and the materials are stirred for 60 minutes under the condition that the linear speed at the tail end of a stirring blade is 0.2m/s, so as to control the particles to polymerize into balls.
The final slurry was subjected to solid-liquid separation, washing to remove impurities, and drying to obtain cobalt carbonate particles having a particle diameter d50=0.886 μm and a distribution width qd= (d90—d10)/d50=1.49, and an impurity S content of 0.0059%. As can be seen from the scanning electron microscope images of different magnifications shown in fig. 1 and 2, the cobalt carbonate particles obtained in example 1 were excellent in dispersibility. As can be seen from the higher magnification scanning electron microscope image shown in fig. 3, the cobalt carbonate particles obtained in example 1 have a very good sphericity.
Example 2 ]
Mixing cobalt chloride with pure water to prepare cobalt chloride solution with cobalt ion concentration of 123.5 g/L; ammonium carbonate is mixed with pure water to prepare an ammonium carbonate solution with the carbonate concentration of 148.4 g/L.
And (3) adding all the prepared cobalt chloride solution into the reaction kettle A to serve as base solution. According to the mole amount M of cobalt ions in the base solution 1 With ammonium carbonateMolar amount of carbonate ions M in solution 2 The ratio of (1): 3, firstly measuring the ammonium carbonate solution, and pumping the ammonium carbonate solution into the reaction kettle A for 4 minutes under the condition that the temperature is 20+/-1 ℃ and the linear speed of the tail end of the stirring blade of the push-type stirrer is 4.5 m/s.
Then, according to the mole amount M of cobalt ions 1 Molar mass M with carbonate ions in ammonium carbonate solution 3 The 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 speed of the tail end of a stirring blade of a push-type stirrer is 0.6m/s, and controlling the temperature rising gradually in the feeding process, wherein the end temperature is 49+/-1 ℃.
After the ammonium carbonate solution is completely added, the materials are all transferred into a reaction kettle B adopting a spiral belt stirrer, the temperature is kept at 49+/-1 ℃, and the mixture is stirred for 80 minutes under the condition that the linear speed at the tail end of a stirring blade is 0.25m/s, so as to control the particles to polymerize into balls.
And (3) carrying out solid-liquid separation, washing, impurity removal and drying on the end-point slurry, wherein the particle size D50=1.267 mu m of the finally obtained cobalt carbonate particles is distributed to have a width QD= (D90-D10)/D50=1.52, and the content of impurity Cl is 0.0031%. As can be seen from the scanning electron microscope images of different magnifications shown in fig. 4 and 5, the cobalt carbonate particles obtained in example 2 were excellent in dispersibility. As can be seen from the higher magnification scanning electron microscope image shown in fig. 6, the cobalt carbonate particles obtained in example 2 had good sphericity.
Example 3 ]
Mixing cobalt nitrate with pure water to prepare a cobalt nitrate solution with the cobalt ion concentration of 143.1 g/L; sodium bicarbonate was mixed with pure water to prepare a sodium bicarbonate solution having a carbonate concentration of 169.7 g/L.
And (3) adding all the prepared cobalt nitrate solution into the reaction kettle A to serve as base solution. According to the mole amount M of cobalt ions in the base solution 1 Molar mass M with carbonate ions in sodium bicarbonate solution 2 The ratio of (1): 2 the sodium bicarbonate solution is measured for the first time, and the sodium bicarbonate solution is pumped into the reaction kettle A for 6 minutes under the condition that the temperature is 27+/-1 ℃ and the linear speed of the tail end of a stirring blade of a push-type stirrer is 5m/s.
Then press downMolar mass M of cobalt ions 1 Molar mass M with carbonate ions in sodium bicarbonate solution 3 The ratio of (1): 2.5 measuring 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 speed of the tail end of a stirring blade of a push-type stirrer is 0.7m/s, and controlling the temperature to rise slowly in the feeding process, wherein the end temperature is 53+/-1 ℃.
After the sodium bicarbonate solution is completely added, the materials are all transferred into a reaction kettle B adopting a spiral belt stirrer, the temperature is kept at 53+/-1 ℃, and the mixture is stirred for 115 minutes under the condition that the linear speed at the tail end of a stirring blade is 0.3m/s, so as to control the polymerization of particles into balls.
The final slurry was subjected to solid-liquid separation, washing to remove impurities, and drying to obtain cobalt carbonate particles having a particle diameter d50=1.974 μm and a distribution width qd= (d90—d10)/d50=1.59, and an impurity N content of 0.0046%. As can be seen from the scanning electron microscope images of different magnifications shown in fig. 7 and 8, the cobalt carbonate particles obtained in example 3 were excellent in dispersibility. As can be seen from the higher magnification scanning electron microscope image shown in fig. 9, the cobalt carbonate particles obtained in example 3 had good sphericity.
In order to further clearly show that in the method for preparing cobalt carbonate particles of the present invention, firstly unstable amorphous cobalt carbonate is synthesized and then crystalline cobalt carbonate is obtained by reforming the cobalt carbonate crystal form, a scanning electron microscope image of the cobalt carbonate precipitate obtained after example 1 is rapidly fed with an ammonium bicarbonate solution in the first stage is shown in fig. 10, and an XRD diffraction pattern of the cobalt carbonate precipitate shown in fig. 10 (as shown in the lowermost curve) and XRD diffraction patterns of the cobalt carbonate final products obtained in examples 1 to 3 (as shown in the upper three curves) are shown in fig. 11. The irregular shape of the cobalt carbonate precipitate formed after the first stage of rapid dosing can be clearly seen from fig. 10, comparing the regular spherical particles of the final product cobalt carbonate shown in fig. 1 to 9, illustrating the realization of the recombination from amorphous cobalt carbonate to crystalline cobalt carbonate during the preparation. The XRD diffractogram of fig. 11 more clearly shows that amorphous cobalt carbonate (corresponding to the curve without characteristic peaks of crystalline cobalt carbonate) is formed earlier in the preparation process, and the final product is crystalline cobalt carbonate (corresponding to the curve with 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 ammonium bicarbonate solution with carbonate concentration of 125.6 g/L.
Adding pure water into the reaction kettle A to prepare base solution according to the molar weight M of cobalt ions 1 Molar mass with carbonate ion M 2 The ratio of (1): and 5, measuring the cobalt sulfate solution and the ammonium bicarbonate solution, and pumping the cobalt sulfate solution and the ammonium bicarbonate solution into the reaction kettle A for 3 minutes under the condition that the temperature is 17+/-1 ℃ and the linear speed of the tail end of the stirring blade of the push-type stirrer is 4 m/s.
In the molar amount M of cobalt ions in the added cobalt sulfate solution 1 Molar mass M with carbonate ions in ammonium bicarbonate solution 3 The ratio of (1): 4, measuring ammonium bicarbonate solution again, pumping the ammonium bicarbonate solution into the reaction kettle A for 90 minutes under the condition that the linear speed of the tail end of a stirring blade of the push-type stirrer is 0.5m/s, and controlling the temperature to rise slowly in the feeding process, wherein the end temperature is 46+/-1 ℃.
After the ammonium bicarbonate solution is added, all the materials are transferred into a reaction kettle B adopting a frame stirrer, the temperature is kept at 45 ℃, and the materials are stirred for 60 minutes under the condition of the linear speed of the tail end of a stirring blade of 0.2 m/s.
In short, comparative example 1 employed substantially the same treatment 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 bicarbonate solution were fed in parallel during the first stage feeding.
And (3) carrying out solid-liquid separation, washing, impurity removal and drying on the end-point slurry, wherein the particle size D50= 6.211 μm of the finally obtained cobalt carbonate particles is distributed with the width QD= (D90-D10)/D50=1.12. As can be seen from the scanning electron micrograph of the cobalt carbonate particles obtained in comparative example 1 shown in fig. 12, the cobalt carbonate particles were not crystallized uniformly and irregularly shaped, and no spherical particles were formed.
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; ammonium bicarbonate and pure water are mixed to prepare ammonium bicarbonate solution with carbonate concentration of 125.5 g/L.
And (3) adding all the prepared cobalt sulfate solution into the reaction kettle A to serve as base solution. According to the mole amount M of cobalt ions in the base solution 1 Molar mass M with carbonate ions in ammonium bicarbonate solution 2 The ratio of (1): 5, firstly measuring ammonium bicarbonate solution, and pumping the ammonium bicarbonate solution into the reaction kettle A for 3 minutes under the condition that the temperature is 35-38 ℃ and the linear speed of the tail end of a stirring blade of a push-type stirrer is 4 m/s.
Then, according to the mole amount M of cobalt ions 1 Molar mass M with carbonate ions in ammonium bicarbonate solution 3 The ratio of (1): and 4, measuring 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 speed of the tail end of a stirring blade of a push-type stirrer is 0.5m/s, and controlling the temperature rising gradually in the feeding process, wherein the end temperature is 46+/-1 ℃.
After the ammonium bicarbonate solution is added, all materials are transferred into a reaction kettle B adopting a frame stirrer, the temperature is kept at 46+/-1 ℃, and stirring is carried out for 60 minutes under the condition that the linear speed at the tail end of a stirring blade is 0.2 m/s.
In short, comparative example 2 used substantially the same treatment and conditions as in example 1, except that the temperature was controlled at 35 to 38℃during the first stage of feeding.
And (3) carrying out solid-liquid separation, washing, impurity removal and drying on the end-point slurry, wherein the particle size D50= 2.218 mu m of the finally obtained cobalt carbonate particles is obtained, and the distribution width QD= (D90-D10)/D50=2.68. As can be seen from the scanning electron microscope image of the cobalt carbonate particles obtained in comparative example 2 shown in FIG. 13, the cobalt carbonate has poor sphericity, severe blocking and agglomeration, and poor dispersibility.
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 carbonate concentration of 142.6 g/L.
And (3) adding all the prepared cobalt sulfate solution into the reaction kettle A to serve as base solution. Press bottomMolar mass M of cobalt ions in the liquid 1 Molar mass M with carbonate ions in ammonium bicarbonate solution 2 The ratio of (1): 5, measuring ammonium bicarbonate solution for the first time, and pumping the ammonium bicarbonate solution into the reaction kettle A for 20 minutes under the condition that the temperature is 17+/-1 ℃ and the linear speed of the tail end of a stirring blade of a push-type stirrer is 4 m/s.
Then, according to the mole amount M of cobalt ions 1 Molar mass M with carbonate ions in ammonium bicarbonate solution 3 The ratio of (1): and 4, measuring 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 speed of the tail end of a stirring blade of a push-type stirrer is 0.5m/s, and controlling the temperature rising gradually in the feeding process, wherein the end temperature is 46+/-1 ℃.
After the ammonium bicarbonate solution is completely added, the materials are all transferred into a reaction kettle B adopting a frame stirrer, the temperature is kept at 46+/-1 ℃, and the materials are stirred for 60 minutes under the condition that the linear speed at the tail end of a stirring blade is 0.2 m/s.
In short, comparative example 3 used essentially the same treatments and conditions as example 1, except that the first stage feed time/reaction time was 20 minutes.
And (3) carrying out solid-liquid separation, washing, impurity removal and drying on the end-point slurry, wherein the particle size D50= 4.363 μm of the finally obtained cobalt carbonate particles is obtained, and the distribution width QD= (D90-D10)/D50=3.64. As can be seen from the scanning electron micrograph of the cobalt carbonate particles obtained in comparative example 3 shown in FIG. 14, the cobalt carbonate was severe in blocking and agglomeration, poor in dispersibility, and not formed into spherical particles.
Comparative example 4 ]
Mixing cobalt chloride with pure water to prepare cobalt chloride solution with cobalt ion concentration of 123.1 g/L; ammonium carbonate and pure water are mixed to prepare alkali liquor with 143.4g/L carbonate radical.
And (3) adding all the prepared cobalt chloride solution into the reaction kettle A to serve as base solution. According to the mole amount M of cobalt ions in the base solution 1 Molar mass M with carbonate ions in ammonium carbonate solution 2 The ratio of (1): 3 firstly measuring ammonium carbonate solution, pumping alkali liquor into the reaction kettle for 4 minutes under the condition that the temperature is 20+/-1 ℃ and the linear speed of the tail end of a stirring blade of a push-type stirrer is 4.5m/sAnd A is in.
Then, according to the mole amount M of cobalt ions 1 Molar mass M with carbonate ions in ammonium carbonate solution 3 The 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 linear speed of the tail end of a stirring blade of a push-type stirrer is 0.6m/s, and controlling the temperature to rise slowly in the feeding process, wherein the end temperature is 49+/-1 ℃.
After the ammonium carbonate solution is completely added, the materials are all transferred into a reaction kettle B adopting a spiral belt stirrer, the temperature is kept at 49+/-1 ℃, and the stirring is carried out for 80 minutes under the condition that the linear speed of the tail end of a stirring blade is 0.25 m/s.
In short, comparative example 4 used essentially the same treatments 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, impurity removal and drying on the end-point slurry, wherein the particle size D50= 6.351 mu m of the finally obtained cobalt carbonate particles is obtained, and the distribution width QD= (D90-D10)/D50=2.59. As can be seen from the scanning electron microscope image of the cobalt carbonate particles obtained in comparative example 4 shown in FIG. 15, the cobalt carbonate has poor sphericity, severe blocking and agglomeration, and poor dispersibility.
The following table shows the comparative examples 1-3 with respect to the partial parameters and particle size index of the resultant cobalt carbonate particles.
Figure BDA0003287041910000101
The foregoing description is only of the preferred embodiments of the present application and is presented as a description of the principles of the technology being utilized. It will be appreciated by persons skilled in the art that the scope of the invention referred to in this application is not limited to the specific combinations of features described above, but it is intended to cover other embodiments in which any combination of features described above or equivalents thereof is possible without departing from the spirit of the invention. Such as the above-described features and technical features having similar functions (but not limited to) disclosed in the present application are replaced with each other.

Claims (9)

1. A preparation method of superfine particle size spherical cobalt carbonate particles comprises the following steps:
(1) With cobalt ion content M 1 The molar cobalt salt solution is used as base solution, the temperature is controlled to be 15-30 ℃, the carbonate source solution is put into a reaction kettle, and the amount of carbonate ions put into the reaction kettle is controlled to be M 2 Molar, M 2 ≥2M 1 The feeding time is 3-6 minutes, and stirring is carried out in a manner that the carbonate source solution and the cobalt salt solution serving as the base solution can be quickly and fully mixed in the feeding time, so as to generate unstable amorphous cobalt carbonate;
(2) Reducing the stirring speed, continuously adding carbonate source solution into the reaction kettle, and controlling the amount of carbonate ions added to be M 3 Molar, M 1 :M 3 1:4-1:1.5, and slowly heating at a speed of 0.2-0.5 ℃ per minute, and controlling unstable amorphous cobalt carbonate to carry out crystal form recombination to form crystalline cobalt carbonate particles with a duration of more than 60 minutes; and
(3) The temperature rise was stopped, and the resultant cobalt carbonate particles were stirred so as to float and flow without sinking, for a period of 60 minutes or longer, to obtain spherical cobalt carbonate particles.
2. The preparation method of 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 also provided with
The carbonate source solution comprises one or more selected from ammonium bicarbonate solution, ammonium carbonate solution, sodium bicarbonate solution and sodium carbonate solution, and the carbonate concentration in the carbonate source solution is 120-180 g/L.
3. The process according to claim 1, wherein in the step (1), M 1 :M 2 Is 1:5-1:2.
4. The production method according to claim 1 or 3, wherein the stirring is performed in the step (1) by using a propeller type stirrer, and the linear velocity of the stirring blade tip is controlled to be 4 to 5m/s.
5. The process according to claim 1, wherein in the step (2), the temperature is raised at a rate of 0.3 to 0.4 o C/min.
6. The production method according to claim 1, wherein in the step (2), stirring is performed by a propeller type stirrer, and the linear velocity of the tip of the stirring blade is controlled to be 0.5 to 0.7m/s.
7. The preparation method as claimed in claim 1, wherein the duration of the step (2) is 60 to 90 minutes.
8. The process according to claim 1, wherein in the step (3), the temperature is maintained at 45 to 55 o And C, the duration is 60-120 minutes.
9. The production method according to claim 1 or 8, wherein in the step (3), stirring is performed by using an anchor frame type stirrer or a ribbon type stirrer, and the terminal linear velocity of the stirring blade is controlled to be 0.2 to 0.3m/s.
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