CN110540249A - Preparation method of high-tap-density aluminum-doped cobaltosic oxide - Google Patents
Preparation method of high-tap-density aluminum-doped cobaltosic oxide Download PDFInfo
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Abstract
The invention discloses a preparation method of high tap density aluminum-doped cobaltosic oxide, which specifically comprises the following steps: step 1, preparing an aluminum salt solution and an ammonium bicarbonate solution; step 2, adding a cobalt solution into the aluminum salt solution obtained in the step 1 to obtain an aluminum cobalt solution; step 3, carrying out synthesis reaction and concentration on the ammonium bicarbonate solution obtained in the step 1 and the aluminum cobalt solution obtained in the step 2, and controlling the pH value in the reaction process to be 7.0 +/-0.3 to obtain a cobalt carbonate crude product; step 4, carrying out circulating iron removal, washing and drying on the cobalt carbonate crude product obtained in the step 3 to obtain a cobalt carbonate dry material; step 5, calcining the cobalt carbonate dry material obtained in the step 4 to obtain cobaltosic oxide; the invention prepares the cobalt carbonate doped with aluminum, and then calcines the cobalt carbonate doped with aluminum, so that the prepared cobaltosic oxide has uniform particle size distribution and higher tap density.
Description
Technical Field
The invention belongs to the technical field of metal powder material preparation processes, and particularly relates to a preparation method of high-tap-density aluminum-doped cobaltosic oxide
Background
The cobaltosic oxide is used as an important chemical raw material and a material precursor, and is widely applied to colorants in the ceramic industry, mineral processing agents in the mining industry, catalysts in the organic industry, hard alloys, battery material precursors and the like.
the common cobaltosic oxide has larger grain diameter, although the cobaltosic oxide with the specification is very easy to synthesize, the overcharge resistance is poorer, the cycle performance is lower, and the cobaltosic oxide with small grain diameter can obviously improve the compaction density of lithium cobaltate and greatly improve the performance of a battery; in addition, as the world's cobalt price has increased, it is undoubtedly the best choice to seek an alternative or reduced amount of cobalt metal, doping being one of the most efficient methods.
Disclosure of Invention
The invention aims to provide a preparation method of high-tap-density aluminum-doped cobaltosic oxide, which is characterized in that the prepared cobaltosic oxide has uniform particle size distribution and higher tap density by preparing aluminum-doped cobalt carbonate and then calcining the aluminum-doped cobalt carbonate.
the technical scheme adopted by the invention is that the preparation method of the high tap density aluminum-doped cobaltosic oxide is implemented according to the following steps:
Step 1, preparing an aluminum salt solution and an ammonium bicarbonate solution;
Step 2, adding a cobalt solution into the aluminum salt solution obtained in the step 1 to obtain an aluminum cobalt solution;
Step 3, carrying out synthesis reaction and concentration on the ammonium bicarbonate solution obtained in the step 1 and the aluminum cobalt solution obtained in the step 2, and controlling the pH value in the reaction process to be 7.0 +/-0.3 to obtain a cobalt carbonate crude product;
Step 4, carrying out circulating iron removal, washing and drying on the cobalt carbonate crude product obtained in the step 3 to obtain a cobalt carbonate dry material;
and 5, calcining the cobalt carbonate dry material obtained in the step 4 to obtain cobaltosic oxide.
the present invention is also characterized in that,
the specific method for preparing the aluminum salt solution in the step 1 comprises the following steps: putting pure water into a configuration tank, heating the pure water through a steam coil pipe in the configuration tank, adding aluminum salt into the pure water according to the volume ratio of 1: 25-30 when the temperature is raised to 80-85 ℃, simultaneously stirring until the aluminum salt is completely dissolved in the pure water, and standing to obtain an aluminum salt solution.
the specific method for preparing the ammonium bicarbonate solution in the step 1 comprises the following steps: putting pure water into a configuration tank, heating the pure water through a steam coil pipe in the configuration tank, adding ammonium bicarbonate solid into the pure water according to the volume ratio of 1: 4.25-4.65 when the temperature is raised to 45-60 ℃, simultaneously stirring until the ammonium bicarbonate is completely dissolved in the pure water, and standing to obtain an ammonium bicarbonate solution.
The specific method for preparing the aluminum-cobalt solution in the step 2 comprises the following steps: adding a cobalt solution with the concentration of 145-150g/L into the aluminum-cobalt preparation tank; and then adding the aluminum salt solution obtained in the step 1 into a cobalt solution, and stirring simultaneously to obtain an aluminum-cobalt solution.
the specific implementation steps of the step 3 are as follows:
step 3.1, putting pure water into a reaction kettle to be used as a base solution and heating the base solution to 30-50 ℃;
step 3.2, simultaneously adding an aluminum cobalt solution and an ammonium bicarbonate solution into the base solution obtained in the step 3.1 to carry out a synthesis reaction;
3.3, after the synthetic reaction in the step 3.2 is carried out for 4-6 hours, the solution in the reaction kettle begins to overflow into an overflow standing groove, and the settled material is pumped back to the reaction kettle by a circulating pump at the bottom of the overflow groove for continuous reaction;
and 3.4, after the reaction is continued for 1.5 to 2.5 hours, the solution overflowing the standing tank begins to overflow into a concentration filter, supernatant liquid is extracted, and the residual materials are returned to the reaction kettle to continue the precipitation reaction to obtain a cobalt carbonate crude product.
And iron is removed in the step 4 for 2-3 hours in a circulating manner.
the dehydration and the washing in the step 4 are carried out in a centrifuge, and the rotation speed of the centrifuge is 300-350 r/min.
the specific method for drying in the step 4 comprises the following steps: and (3) putting the crude cobalt carbonate into a flash evaporation machine by hoisting, and drying until the moisture content is below 0.5%.
the calcination of step 5 is carried out in a rotary kiln.
the rotary kiln is provided with 5 temperature zones, and the temperatures are respectively as follows: 600 ℃ for 480 ℃, 660 ℃ for 600 ℃, 660 ℃ for 700 ℃, 720 ℃ for 700 ℃ and 750 ℃ for 720 ℃.
the invention has the beneficial effects that the aluminum is doped in the cobaltosic oxide, so that the cost is reduced, and the cycle performance of the cobalt carbonate as a battery material is improved; in addition, the pH value in the process is controlled, the uniformity of nucleation and growth conditions among cobaltosic oxide particle particles is maintained, and the precipitate and the solution are isotropic, so that the cobaltosic oxide particles can grow outwards uniformly and spherically on the basis of nucleation to form spherical cobalt carbonate; and finally, the cobaltosic oxide is prepared by calcining the cobalt carbonate, so that the production efficiency can be improved, the production power consumption cost can be reduced, and meanwhile, the parameters of the calcining reaction process can be flexibly controlled, and the method is suitable for batch production.
Drawings
FIG. 1 is an electron micrograph of aluminum-doped cobaltosic oxide prepared in example 1 according to the present invention magnified 10000 times;
FIG. 2 is an electron microscope image of 5000 times magnification of the aluminum-doped cobaltosic oxide prepared in example 1 provided by the present invention;
FIG. 3 is an electron micrograph of the aluminum-doped cobaltosic oxide prepared in example 1 magnified 3000 times;
FIG. 4 is an electron micrograph of aluminum-doped cobaltosic oxide prepared in example 2 magnified 10000 times;
FIG. 5 is an electron microscope image of 5000 times magnification of aluminum-doped cobaltosic oxide prepared in example 2 provided by the present invention;
FIG. 6 is an electron micrograph at 3000 times magnification of aluminum-doped cobaltosic oxide prepared in example 2 according to the present invention;
FIG. 7 is an electron micrograph of aluminum-doped cobaltosic oxide prepared in example 3 magnified 10000 times;
FIG. 8 is an electron microscope image of 5000 times magnification of aluminum-doped cobaltosic oxide prepared in example 3 according to the present invention;
FIG. 9 is an electron micrograph at 3000 times magnification of aluminum-doped cobaltosic oxide prepared in example 3 according to the present invention;
FIG. 10 is an electron micrograph of aluminum-doped cobaltosic oxide prepared in example 4 magnified 10000 times;
FIG. 11 is an electron microscope image of 5000 times magnification of aluminum-doped cobaltosic oxide prepared in example 4 provided by the present invention;
FIG. 12 is an electron micrograph of the aluminum-doped cobaltosic oxide prepared in example 4 according to the present invention magnified 3000 times.
Detailed Description
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
the embodiment of the invention provides a preparation method of high-tap-density aluminum-doped cobaltosic oxide, which is implemented according to the following steps:
step 1, preparing an aluminum salt solution and an ammonium bicarbonate solution;
the specific method for preparing the aluminum salt solution comprises the following steps: putting pure water into a configuration tank, heating the pure water through a steam coil pipe in the configuration tank, adding aluminum salt into the pure water according to the volume ratio of 1: 25-30 when the temperature is raised to 80-85 ℃, simultaneously stirring until the aluminum salt is completely dissolved in the pure water, and standing to obtain an aluminum salt solution;
The concrete method for preparing the ammonium bicarbonate solution comprises the following steps: putting pure water into a configuration tank, heating the pure water through a steam coil pipe in the configuration tank, adding ammonium bicarbonate solid into the pure water according to the volume ratio of 1: 4.25-4.65 when the temperature is raised to 45-60 ℃, simultaneously stirring until the ammonium bicarbonate is completely dissolved in the pure water, and standing to obtain an ammonium bicarbonate solution;
Step 2, adding a cobalt solution with the concentration of 145-150g/L into the aluminum-cobalt preparation tank; then adding the aluminum salt solution obtained in the step 1 into a cobalt solution, and stirring simultaneously to obtain an aluminum-cobalt solution;
and 3, carrying out synthesis reaction and concentration on the ammonium bicarbonate solution obtained in the step 1 and the aluminum cobalt solution obtained in the step 2, and controlling the pH value in the reaction process to be 7.0 +/-0.3 to obtain a cobalt carbonate crude product, wherein the specific method comprises the following steps:
step 3.1, putting pure water into a reaction kettle to be used as a base solution and heating the base solution to 30-50 ℃;
Step 3.2, simultaneously adding an aluminum cobalt solution and an ammonium bicarbonate solution into the base solution obtained in the step 3.1 to carry out a synthesis reaction;
3.3, after the synthetic reaction in the step 3.2 is carried out for 4-6 hours, the solution in the reaction kettle begins to overflow into an overflow standing groove, and the settled material is pumped back to the reaction kettle by a circulating pump at the bottom of the overflow groove for continuous reaction;
step 3.4, after the reaction is continued for 1.5 to 2.5 hours, the solution overflowing the standing tank begins to overflow into a concentration filter, supernatant liquid is extracted, and the residual materials are returned to the reaction kettle to continue the precipitation reaction to prepare a cobalt carbonate crude product;
Step 4, circularly removing iron for 2-3h from the cobalt carbonate crude product obtained in the step 3, washing and drying to obtain a cobalt carbonate dry material; wherein, the dehydration and the washing are carried out in a centrifuge, and the rotating speed of the centrifuge is 300-350 r/min; the drying method comprises the following specific steps: putting the cobalt carbonate crude product into a flash evaporation machine by crane, and drying until the moisture content is below 0.5%;
And 5, calcining the cobalt carbonate dry material obtained in the step 4 in a rotary kiln to obtain cobaltosic oxide, wherein the rotary kiln is provided with 5 temperature zones, and the temperature is respectively as follows: 600 ℃ for 480 ℃, 660 ℃ for 600 ℃, 660 ℃ for 700 ℃, 720 ℃ for 700 ℃ and 750 ℃ for 720 ℃.
compared with the existing preparation method, the invention mainly has the following technical advantages: by doping aluminum in the cobaltosic oxide, the cost is reduced, and the cycle performance of the cobalt carbonate as a battery material is improved; in addition, the pH value in the process is controlled, the uniformity of nucleation and growth conditions among cobaltosic oxide particle particles is maintained, and the precipitate and the solution are isotropic, so that the cobaltosic oxide particles can grow outwards uniformly and spherically on the basis of nucleation to form spherical cobalt carbonate; and finally, the cobaltosic oxide is prepared by calcining the cobalt carbonate, so that the production efficiency can be improved, the production power consumption cost can be reduced, and meanwhile, the parameters of the calcining reaction process can be flexibly controlled, and the method is suitable for batch production.
example 1
step 1, preparing an aluminum salt solution and an ammonium bicarbonate solution: adding 2m3 of pure water into a 3m3 aluminum salt preparation tank, heating the pure water through a built-in steam coil pipe, heating the temperature to 80 ℃, starting stirring at a rotating speed, controlling the rotating speed of a motor to be 400r/min, adding aluminum salt into the pure water according to the volume ratio of 1: 25 in the hot water of the preparation tank, stirring the whole solution for 1 hour, stopping stirring, standing for 30 minutes, and sampling to detect that the concentration of aluminum ions is 8.1 g/L; adding 10m3 pure water into an ammonium bicarbonate preparation tank, heating the pure water in the tank through a steam coil, controlling the temperature at 45 ℃, starting stirring, controlling the rotating speed of an electrode at 600r/min, starting stirring for 1 hour in the preparation tank according to the volume ratio of 1: 4.25, completely dissolving, stopping stirring, standing for 10 minutes, obtaining ammonium bicarbonate concentration of 215g/L by sampling analysis, and beating the ammonium bicarbonate to a high-level barrel through a centrifugal pump after preparation for reaction;
step 2, preparing an aluminum cobalt solution: accurately adding 10m3 cobalt unit solution with the concentration of 145g/L into an aluminum cobalt preparation tank through a mass flow meter, then accurately adding 1.14m3 aluminum salt solution into the prepared aluminum salt through the mass flow meter, opening the stirring of the aluminum cobalt preparation tank, controlling the rotating speed of a motor at 800r/min, controlling the stirring time at 30 minutes, closing the stirring and standing for 10 minutes, sampling and detecting that the concentration of cobalt is 125g/L and the concentration of aluminum is 680mg/L, and pumping the prepared solution to a high-level barrel through a centrifugal pump to prepare for feeding reaction;
Step 3, preparing a cobalt carbonate crude product: adding 4m3 pure water into an 8m3 reaction kettle as bottom water, starting to heat to 40 ℃,
adding 30 minutes of ammonium bicarbonate solution (the concentration of the ammonium bicarbonate solution is 230g/L) as a base solution, starting a reaction kettle motor to stir, controlling the rotating speed at 1200r/min, controlling the speed reducer speed ratio to be 3, simultaneously pumping the raw material of the high-level barrel of the aluminum cobalt solution and the auxiliary material of the high-level barrel of the ammonium bicarbonate into the reaction kettle of 8m3, starting a metering pump, and respectively adding the aluminum cobalt solution and the ammonium bicarbonate solution into the reaction kettle at the flow rates of 300L/h and 900L/h to perform neutralization and precipitation reaction, wherein the cobalt content in the cobalt solution is 130g/L, the aluminum concentration is 800mg/L, the temperature is kept unchanged during the reaction process, and the pH value is controlled at 7.0; when the reaction kettle is continuously fed, starting to overflow to an overflow groove after 5 hours, simultaneously starting an overflow groove circulating pump, continuously pumping the materials overflowing to the overflow groove back to the reaction kettle, starting to overflow from the overflow groove after about 2 hours, continuously overflowing to a thickener, pumping clear liquid by the thickener, returning the materials to the reaction kettle for continuous reaction, stopping feeding until the particle size D50 of the cobalt carbonate is 4.5-5.5 mu m, and finishing the synthesis reaction;
Step 4, pumping the materials in the reaction kettle to a finished product tank of 20m3, circularly removing iron for 2 hours, filtering and washing the materials in an integrated centrifuge, dehydrating, washing with hot pure water for 4 times and 7 minutes, then putting the semi-dry cobalt carbonate into a flash evaporation machine by a crane, and drying until the moisture content is below 0.5% to obtain a pink powder cobalt carbonate dry material;
And 5, conveying the cobalt carbonate into a rotary kiln through a bolt feeding device, wherein the rotary kiln is at a rotating speed of 10Hz, 5 temperature zones are arranged at an inclination angle of 2 degrees, the temperature is 490 ℃, 600 ℃, 660 ℃, 700 ℃ and 720 ℃, the feeding frequency is 1.4Hz, a fan is controlled at 4Hz, the retention time of the materials in the rotary kiln is 3 hours, sufficient air is ensured, the calcination is fully carried out, and the discharged materials are black powder, namely the aluminum-doped cobaltosic oxide.
the cobaltosic oxide prepared in this example had a tap density of 2.62g/cm3, an aluminum content of 0.4211%, a D10 of 3.2, a D50 of 4.9, and a D90 of 7.8, and had a normal particle size distribution, as shown in fig. 1 to 3.
Example 2
step 1, preparing an aluminum salt solution and an ammonium bicarbonate solution: adding 2m3 of pure water into a 3.2m3 aluminum salt preparation tank, heating the pure water through a built-in steam coil, heating the pure water to 83 ℃, starting stirring at a rotating speed, controlling the rotating speed of a motor to be 400r/min, adding aluminum salt into the pure water in a volume ratio of 1: 27 in the hot water in the preparation tank, stirring the whole solution for 1 hour, stopping stirring, standing for 35 minutes, and sampling to detect that the concentration of aluminum ions is 8.4 g/L; adding 10m3 pure water into an ammonium bicarbonate preparation tank, heating the pure water in the tank through a steam coil, controlling the temperature at 50 ℃, starting stirring, controlling the rotating speed of an electrode at 600r/min, starting stirring for 1 hour in the preparation tank according to the volume ratio of 1: 4.5, completely dissolving, stopping stirring, standing for 15 minutes, obtaining ammonium bicarbonate with the concentration of 223g/L by sampling analysis, and beating the ammonium bicarbonate into a high-level barrel through a centrifugal pump after preparation for reaction;
Step 2, preparing an aluminum cobalt solution: accurately adding 10m3 cobalt unit solution with the concentration of 148g/L into an aluminum cobalt preparation tank through a mass flow meter, then accurately adding 1.14m3 aluminum salt solution into the prepared aluminum salt through the mass flow meter, opening the stirring of the aluminum cobalt preparation tank, controlling the rotating speed of a motor at 860r/min, controlling the stirring time at 30 minutes, closing the stirring and standing for 10 minutes, sampling and detecting that the concentration of cobalt is 130g/L and the concentration of aluminum is 700mg/L, and pumping the prepared solution to a high-level barrel through a centrifugal pump to prepare for feeding reaction;
step 3, preparing a cobalt carbonate crude product: adding 4.2m3 pure water into an 8m3 reaction kettle as bottom water, starting to heat to 43 ℃, adding the pure water as a bottom liquid, starting a motor of the reaction kettle to stir, controlling the rotating speed at 1200r/min, wherein the speed ratio of the speed reducer is 3, simultaneously pumping an aluminum-cobalt solution high-level barrel raw material and an ammonium carbonate high-level barrel auxiliary material into the 8m3 reaction kettle, starting a metering pump, and respectively adding the aluminum-cobalt solution and the ammonium carbonate solution into the reaction kettle at the flow rates of 300L/h and 800L/h to perform neutralization and precipitation reaction, wherein the cobalt content in the cobalt solution is 130g/L, the aluminum concentration is 800mg/L, the temperature is kept unchanged during the reaction process, and the pH value is controlled at 7.2; when the reaction kettle is continuously fed, starting to overflow to an overflow groove after 5 hours, simultaneously starting an overflow groove circulating pump, continuously pumping the materials overflowing to the overflow groove back to the reaction kettle, starting to overflow from the overflow groove after about 2 hours, continuously overflowing to a thickener, pumping clear liquid by the thickener, returning the materials to the reaction kettle for continuous reaction, stopping feeding until the particle size D50 of the cobalt carbonate is 4.5-5.5 mu m, and finishing the synthesis reaction;
step 4, pumping the materials in the reaction kettle to a finished product tank of 20m3, circularly removing iron for 2-3 hours, putting the materials into a centrifuge integrating filtration and washing, dehydrating, washing with hot pure water for 4 times and 7 minutes, then putting the semi-dry cobalt carbonate into a flash evaporation machine by hanging, and drying until the moisture content is below 0.5% to obtain a pink powder cobalt carbonate dry material;
And 5, conveying the cobalt carbonate into a rotary kiln through a bolt feeding device, wherein the rotary kiln is provided with 5 temperature zones at the rotation speed of 10Hz and the inclination angle of 2 degrees, the temperatures are 550 ℃, 620 ℃, 680 ℃, 710 ℃ and 735 ℃, the feeding frequency is 1.4Hz, a fan is controlled at 4Hz, the retention time of the materials in the rotary kiln is 3-4 hours, sufficient air is ensured, the calcination is fully carried out, and the discharged materials are black powder, namely the aluminum-doped cobaltosic oxide.
the cobaltosic oxide prepared in this example had a tap density of 2.68g/cm3, an aluminum content of 0.4188%, a D10 of 3.52, a D50 of 5.1, and a D90 of 8.2, and had a normal particle size distribution, as shown in fig. 4 to 6.
Example 3
Step 1, preparing an aluminum salt solution and an ammonium bicarbonate solution: adding 2m3 of pure water into a 3m3 aluminum salt preparation tank, heating the pure water through a built-in steam coil pipe, heating the temperature to 85 ℃, starting stirring at a rotating speed, controlling the rotating speed of a motor to be 400r/min, adding aluminum salt into the pure water according to the volume ratio of 1: 30 into the hot water in the preparation tank, stirring the whole solution for 1 hour, stopping stirring, standing for 30 minutes, and sampling to detect that the concentration of aluminum ions is 8.6 g/L; adding 10m3 pure water into an ammonium bicarbonate preparation tank, heating the pure water in the tank through a steam coil, controlling the temperature at 60 ℃, starting stirring, controlling the rotating speed of an electrode at 600r/min, starting stirring for 1 hour in the preparation tank according to the volume ratio of 1: 4.65, completely dissolving, stopping stirring, standing for 10 minutes, obtaining ammonium bicarbonate with the concentration of 230g/L by sampling analysis, and beating the ammonium bicarbonate into a high-level barrel through a centrifugal pump after preparation for reaction;
Step 2, preparing an aluminum cobalt solution: accurately adding 10m3 cobalt unit solution with the concentration of 145-150g/L into an aluminum-cobalt preparation tank through a mass flow meter, then accurately adding the prepared aluminum salt into 1.14m3 aluminum salt solution through the mass flow meter, starting the stirring of the aluminum-cobalt preparation tank, controlling the rotating speed of a motor at 800r/min, controlling the stirring time at 30 minutes, stopping stirring and standing for 10 minutes, sampling and detecting that the concentration of cobalt is 135g/L and the concentration of aluminum is 740mg/L, and pumping the prepared solution to a high-level barrel through a centrifugal pump to prepare for feeding reaction;
Step 3, preparing a cobalt carbonate crude product: adding 4m3 pure water into an 8m3 reaction kettle as bottom water, heating to 40 ℃, adding the pure water as a bottom liquid, starting a motor of the reaction kettle to stir, controlling the rotating speed at 1200r/min, wherein the speed ratio of the speed reducer is 3, simultaneously adding an aluminum-cobalt solution high-level barrel raw material and an ammonium carbonate high-level barrel auxiliary material into the 8m3 reaction kettle, starting a metering pump, and adding the aluminum-cobalt solution and the ammonium carbonate solution into the reaction kettle at the flow rates of 300L/h and 900L/h respectively to perform neutralization and precipitation reaction, wherein the cobalt content in the cobalt solution is 130g/L, the aluminum concentration is 800mg/L, the temperature is kept unchanged during the reaction, and the pH value is controlled at 7.3; when the feeding is continuously carried out in the reaction kettle, starting to overflow to an overflow groove after 4 hours, simultaneously starting an overflow groove circulating pump, continuously pumping the materials overflowing to the overflow groove back to the reaction kettle, starting to overflow from the overflow groove after about 1.5 hours, continuously overflowing to a thickener, pumping clear liquid by the thickener, returning the materials to the reaction kettle for continuous reaction, stopping feeding when the particle size D50 of the cobalt carbonate is 4.5-5.5 mu m, and finishing the synthesis reaction;
Step 4, pumping the materials in the reaction kettle to a finished product tank of 20m3, circularly removing iron for 3 hours, filtering and washing the materials in an integrated centrifuge, dehydrating, washing with hot pure water for 4 times and 7 minutes, then putting the semi-dry cobalt carbonate into a flash evaporation machine by a crane, and drying until the moisture content is below 0.5% to obtain a pink powder cobalt carbonate dry material;
and 5, conveying the cobalt carbonate into a rotary kiln through a bolt feeding device, wherein the rotary kiln is at a rotating speed of 10Hz, 5 temperature zones are arranged at an inclination angle of 2 degrees, the temperatures are 600 ℃, 660 ℃, 700 ℃, 720 ℃ and 750 ℃, the feeding frequency is 1.4Hz, a fan is controlled at 4Hz, the retention time of the materials in the rotary kiln is 4 hours, sufficient air is ensured, the calcination is fully carried out, and the discharged materials are black powder, namely the aluminum-doped cobaltosic oxide.
The cobaltosic oxide prepared in this example had a tap density of 2.60g/cm3, an aluminum content of 0.4012%, D10 ═ 3.47, D50 ═ 4.85, D90 ═ 8.5, and a normal particle size distribution, as shown in fig. 7 to 9.
example 4
Step 1, preparing an aluminum salt solution and an ammonium bicarbonate solution: adding 2m3 of pure water into a 3m3 aluminum salt preparation tank, heating the pure water through a built-in steam coil pipe, heating the temperature to 84 ℃, starting stirring at a rotating speed, controlling the rotating speed of a motor to be 400r/min, adding aluminum salt into the pure water according to the volume ratio of 1: 29 in the hot water of the preparation tank, stirring the whole solution for 1 hour, stopping stirring, standing for 30 minutes, and sampling to detect that the concentration of aluminum ions is 8.2 g/L; adding 10m3 pure water into an ammonium bicarbonate preparation tank, heating the pure water in the tank through a steam coil, controlling the temperature at 47 ℃, starting stirring, controlling the rotating speed of an electrode at 600r/min, starting stirring for 1 hour in the preparation tank according to the volume ratio of 1: 4.3, completely dissolving, stopping stirring, standing for 10 minutes, obtaining ammonium bicarbonate with the concentration of 219g/L by sampling analysis, and beating the ammonium bicarbonate into a high-level barrel through a centrifugal pump after preparation for reaction;
Step 2, preparing an aluminum cobalt solution: accurately adding 10m3 cobalt unit solution with the concentration of 146g/L into an aluminum cobalt preparation tank through a mass flow meter, then accurately adding 1.14m3 aluminum salt solution into the prepared aluminum salt through the mass flow meter, opening the stirring of the aluminum cobalt preparation tank, controlling the rotating speed of a motor at 800r/min, controlling the stirring time at 30 minutes, closing the stirring and standing for 10 minutes, sampling and detecting that the concentration of cobalt is 126g/L and the concentration of aluminum is 690mg/L, and beating the prepared solution to a high-level barrel through a centrifugal pump to prepare for feeding reaction;
step 3, preparing a cobalt carbonate crude product: adding 4m3 pure water into an 8m3 reaction kettle as bottom water, heating to 40 ℃, adding the pure water as a bottom liquid, starting a motor of the reaction kettle to stir, controlling the rotating speed at 1200r/min, wherein the speed ratio of the speed reducer is 3, simultaneously adding an aluminum-cobalt solution high-level barrel raw material and an ammonium carbonate high-level barrel auxiliary material into the 8m3 reaction kettle, starting a metering pump, and adding the aluminum-cobalt solution and the ammonium carbonate solution into the reaction kettle at the flow rates of 300L/h and 900L/h respectively to perform neutralization and precipitation reaction, wherein the cobalt content in the cobalt solution is 130g/L, the aluminum concentration is 800mg/L, the temperature is kept unchanged during the reaction, and the pH value is controlled at 6.8; when the feeding is continuously carried out in the reaction kettle, starting to overflow to an overflow groove after 4.8 hours, simultaneously starting an overflow groove circulating pump, continuously pumping the materials overflowing to the overflow groove back to the reaction kettle, starting to overflow from the overflow groove after about 1.6 hours, continuously overflowing to a thickener, pumping clear liquid by the thickener, returning the materials to the reaction kettle for continuous reaction, stopping feeding when the particle size D50 of the cobalt carbonate is 4.5-5.5 mu m, and finishing the synthesis reaction;
step 4, pumping the materials in the reaction kettle to a finished product tank of 20m3, circularly removing iron for 2.9 hours, putting the materials into a centrifuge integrating filtration and washing, dehydrating, washing with hot pure water for 4 times and 7 minutes, then putting the semi-dry cobalt carbonate into a flash evaporation machine by crane, and drying until the moisture content is below 0.5% to obtain a pink powder cobalt carbonate dry material;
And 5, conveying the cobalt carbonate into a rotary kiln through a bolt feeding device, wherein the rotary kiln is at a rotating speed of 10Hz, 5 temperature zones are arranged at an inclination angle of 2 degrees, the temperature is 490 ℃, 610 ℃, 670 ℃, 710 ℃ and 730 ℃, the feeding frequency is 1.4Hz, a fan is controlled at 4Hz, the retention time of the materials in the rotary kiln is 3-4 hours, sufficient air is ensured, the calcination is fully carried out, and the discharged materials are black powder, namely the aluminum-doped cobaltosic oxide.
the cobaltosic oxide prepared in this example had a tap density of 2.62g/cm3, an aluminum content of 0.4211%, a D10 of 3.2, a D50 of 4.9, and a D90 of 7.8, and had a normal particle size distribution, as shown in fig. 10 to 11.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (10)
1. A preparation method of aluminum-doped cobaltosic oxide with high tap density is characterized by comprising the following steps:
step 1, preparing an aluminum salt solution and an ammonium bicarbonate solution;
Step 2, adding a cobalt solution into the aluminum salt solution obtained in the step 1 to obtain an aluminum cobalt solution;
Step 3, carrying out synthesis reaction and concentration on the ammonium bicarbonate solution obtained in the step 1 and the aluminum cobalt solution obtained in the step 2, and controlling the pH value in the reaction process to be 7.0 +/-0.3 to obtain a cobalt carbonate crude product;
step 4, carrying out circulating iron removal, washing and drying on the cobalt carbonate crude product obtained in the step 3 to obtain a cobalt carbonate dry material;
and 5, calcining the cobalt carbonate dry material obtained in the step 4 to obtain cobaltosic oxide.
2. The method for preparing aluminum-doped cobaltosic oxide with high tap density according to claim 1, wherein the specific method for preparing the aluminum salt solution in the step 1 is as follows: putting pure water into a configuration tank, and heating the pure water through a steam coil inside the configuration tank; when the temperature is raised to 80-85 ℃, adding aluminum salt into pure water according to the volume ratio of 1: 25-30, simultaneously stirring until the aluminum salt is completely dissolved in the pure water, and standing to obtain an aluminum salt solution.
3. the method for preparing the aluminum-doped cobaltosic oxide with high tap density according to claim 2, wherein the specific method for preparing the ammonium bicarbonate solution in the step 1 comprises the following steps: putting pure water into a configuration tank, and heating the pure water through a steam coil inside the configuration tank; when the temperature is raised to 45-60 ℃, adding ammonium bicarbonate solid into pure water according to the volume ratio of 1: 4.25-4.65, simultaneously stirring until the ammonium bicarbonate is completely dissolved in the pure water, and standing to obtain an ammonium bicarbonate solution.
4. the method for preparing the aluminum-doped cobaltosic oxide with the high tap density according to claim 3, wherein the specific method for preparing the aluminum-cobalt solution in the step 2 comprises the following steps: adding a cobalt solution with the concentration of 145-150g/L into the aluminum-cobalt preparation tank; and then adding the aluminum salt solution obtained in the step 1 into a cobalt solution, and stirring simultaneously to obtain an aluminum-cobalt solution.
5. the method for preparing the aluminum-doped cobaltosic oxide with high tap density according to any one of claims 1 to 4, wherein the step 3 is implemented by the following steps:
step 3.1, putting pure water into a reaction kettle to be used as a base solution and heating the base solution to 30-50 ℃;
step 3.2, simultaneously adding an aluminum cobalt solution and an ammonium bicarbonate solution into the base solution obtained in the step 3.1 to carry out a synthesis reaction;
3.3, after the synthetic reaction in the step 3.2 is carried out for 4-6 hours, the solution in the reaction kettle begins to overflow into an overflow standing groove, and the settled material is pumped back to the reaction kettle by a circulating pump at the bottom of the overflow groove for continuous reaction;
and 3.4, after the reaction is continued for 1.5 to 2.5 hours, the solution overflowing the standing tank begins to overflow into a concentration filter, supernatant liquid is extracted, and the residual materials are returned to the reaction kettle to continue the precipitation reaction to obtain a cobalt carbonate crude product.
6. The method for preparing the aluminum-doped cobaltosic oxide with the high tap density according to claim 5, wherein iron is removed in the step 4 for 2-3 hours in a circulating manner.
7. the method as claimed in claim 6, wherein the step 4 of washing is performed in a centrifuge, and the rotation speed of the centrifuge is 300-350 r/min.
8. The method for preparing the aluminum-doped cobaltosic oxide with the high tap density according to claim 7, wherein the drying in the step 4 is carried out by the following specific method: and (3) putting the crude cobalt carbonate into a flash evaporation machine by hoisting, and drying until the moisture content is below 0.5%.
9. the method as claimed in claim 8, wherein the calcination of step 5 is performed in a rotary kiln.
10. The method for preparing the high-tap-density aluminum-doped cobaltosic oxide as claimed in claim 9, wherein the rotary kiln is provided with 5 temperature zones, and the temperatures are respectively as follows: 600 ℃ for 480 ℃, 660 ℃ for 600 ℃, 660 ℃ for 700 ℃, 720 ℃ for 700 ℃ and 750 ℃ for 720 ℃.
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