CN103624251B - A kind of half micron cobalt powder and preparation method thereof and cobalt hydroxide powder and preparation method thereof - Google Patents
A kind of half micron cobalt powder and preparation method thereof and cobalt hydroxide powder and preparation method thereof Download PDFInfo
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- CN103624251B CN103624251B CN201310638363.3A CN201310638363A CN103624251B CN 103624251 B CN103624251 B CN 103624251B CN 201310638363 A CN201310638363 A CN 201310638363A CN 103624251 B CN103624251 B CN 103624251B
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Abstract
The invention provides a kind of half micron cobalt powder, the pattern of this half micron cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5 ~ 0.8 μm, and its impurity content is low, has the advantage of super-fine cobalt powder and class ball cobalt powder concurrently.Secondly, present invention also offers the preparation method of this half micron cobalt powder, the method adopts cobalt salt solution and NaOH or potassium hydroxide solution to react to produce cobalt hydroxide and precipitates, precipitate after pulp, centrifugal, washing, dry, fragmentation, at 340 ~ 370 DEG C, carry out hydrogen reduction obtain cobalt powder, namely described cobalt powder obtains half micron cobalt powder after fragmentation, and the method has the advantage of product pattern and size tunable, environmental protection.In addition, the invention provides a kind of cobalt hydroxide powder and preparation method thereof, the pattern of this cobalt hydroxide powder is granular or bar-shaped, and Fisher particle size is 0.33 ~ 0.58 μm.
Description
Technical field
The invention belongs to metal particle preparing technical field, particularly relate to a kind of half micron cobalt powder and preparation method thereof and cobalt hydroxide powder and preparation method thereof.
Background technology
Cobalt powder is the irregular powder of grey, be dissolved in acid, be magnetic, oxidizable in humid air, can be used as the metallurgic products such as carbide alloy, diamond tool, high temperature alloy, magnetic material, and the chemicals such as chargeable battery, industrial blasting agent, rocket fuel and medicine.In general industry application, common cobalt powder is divided into standard type cobalt powder, near-spherical cobalt powder and ultra-fine near-spherical cobalt powder.Super-fine cobalt powder has special physical and chemical performance, there is great skin effect and bulk effect, along with the development of science and technology, the requirement of different applications to dusty material performance improves constantly, as in the preparation of ultra-fine cemented carbide, require that cobalt powder Fisher particle size (Fsss) is less than 0.8um and just can obtains better serviceability, therefore, provide Fsss particle diameter to seem very important lower than the cobalt powder of 0.8 μm.
Cobalt powder suitability for industrialized production two-step method adopts Cobalt salts solution and precipitating reagent reaction to prepare cobalt salt precursor, then cobalt salt precursor reduces under the high temperature conditions and prepares metal cobalt powder, but traditional metal-precipitator is carbonic hydroammonium or ammonium oxalate, the cobalt salt precursor produced is cobalt carbonate and cobalt oxalate, the cobalt powder Fsss particle diameter prepared thus is generally more than 0.8 μm, and the use of carbonic hydroammonium or ammonium oxalate can cause a large amount of ammonia and nitrogen pollutions.
Summary of the invention
For solving the problem, first aspect present invention provides a kind of half micron cobalt powder, and the pattern of described half micron cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5 ~ 0.8 μm.Second aspect present invention provides a kind of preparation method of half micron cobalt powder, product pattern and size tunable, low cost, without ammonia and nitrogen pollution problem.Third aspect present invention and fourth aspect additionally provide cobalt hydroxide powder and preparation method thereof.
First aspect, the invention provides a kind of half micron cobalt powder, and the pattern of described half micron cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5 ~ 0.8 μm.
Preferably, the D of described half micron cobalt powder
50particle diameter is 4.04 ~ 4.36 μm.
Preferably, in described half micron cobalt powder the content of sodium lower than 80ppm.
Preferably, in described half micron cobalt powder the content of calcium lower than 80ppm.
Preferably, in described half micron cobalt powder oxygen content lower than 1.15%.
The advantage particle diameter that half micron cobalt powder provided by the invention has super-fine cobalt powder and class ball cobalt powder concurrently is little and even, can be widely used in hart metal product and the battery industries such as digital cuttings, bar, top hammer, drill bit.
Second aspect, the invention provides a kind of preparation method of half micron cobalt powder, comprises the following steps:
(1) cobalt salt solution and precipitant solution is prepared, in described cobalt salt solution, the concentration of cobalt ions is 0.37 ~ 0.62mol/L, the concentration of described precipitant solution is 8 ~ 15 times of the concentration of cobalt ions in described cobalt salt solution, and described precipitating reagent is alkali metal hydroxide;
(2) cobalt salt solution step (1) prepared and precipitant solution join in reactor in the mode of bottom feed carries out precipitation reaction, obtain the solution containing cobalt hydroxide precipitation, wherein, the speed that described cobalt salt solution adds is 64 ~ 74L/h, and the speed that described precipitant solution adds is 1.3 ~ 3 times that described cobalt salt solution adds speed;
(3) step (2) gained is obtained cobalt hydroxide precipitation containing after the solution centrifugal separation of cobalt hydroxide precipitation, pulp process 0.5 ~ 4 hour at again gained cobalt hydroxide being deposited in 40 ~ 70 DEG C, carry out subsequently washing, dry, broken, obtain cobalt hydroxide powder, the pattern of described cobalt hydroxide powder is granular or bar-shaped, and Fisher particle size is 0.33 ~ 0.58 μm;
(4), by the cobalt hydroxide powder of step (3) gained be placed in reduction furnace, pass into reducibility gas, reduce 16.5 ~ 17.5 hours at 340 ~ 370 DEG C, obtain cobalt powder;
(5), by step (4) gained cobalt powder carry out airflow crash, obtain half micron cobalt powder, the pattern of described half micron cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5 ~ 0.8 μm.
Preferably, by controlling the speed that described in concrete reaction system course of reaction, precipitant solution adds, i.e. flux of alkaline liquor, or the flow of cobalt salt, regulate the pH value of reaction solution, thus change the particle diameter, pattern, reunion situation etc. of synthesis cobalt hydroxide presoma.
Preferably, in described step (1), described cobalt salt is soluble cobalt.
Preferably, in described step (1), described alkali metal hydroxide is NaOH or potassium hydroxide.
Further preferably, in described step (1), described alkali metal hydroxide is NaOH.
Preferably, in described step (1), described cobalt salt is cobalt chloride, cobalt nitrate, cobaltous sulfate or cobalt acetate.
Preferably, in described step (1), be sodium carbonate liquor or the solution of potassium carbonate of 0.1 ~ 0.5mol/L containing molar concentration in described precipitant solution.
Further preferably, in described step (1), containing molar concentration in described precipitant solution is the sodium carbonate liquor of 0.1 ~ 0.5mol/L.
Still more preferably, in described step (1), containing molar concentration in described precipitant solution is the sodium carbonate liquor of 0.25mol/L.
Sodium carbonate liquor or solution of potassium carbonate, as conditioning agent, affect particle diameter, pattern, the reunion situation of synthesis cobalt hydroxide presoma.
Preferably, in described step (2), before described cobalt salt solution and precipitant solution add reactor, in described reactor, water at the bottom of the reaction of covering paddle 5 ~ 30cm on reactor is provided with.
Further preferably, in described step (2), before described cobalt salt solution and precipitant solution add reactor, in described reactor, water at the bottom of the reaction of covering paddle 15cm on reactor is provided with.
Preferably, the reaction temperature of described precipitation reaction is 44 ~ 70 DEG C.
Further preferably, the reaction temperature of concrete reaction system fluctuates in the scope of ± 3 DEG C.
Preferably, in described precipitation reaction process, the pH value of reaction solution is 11.0 ~ 11.6.
Preferably, by controlling the pH of reaction solution described in concrete reaction system course of reaction, the pH of reaction solution being finely tuned, affecting particle diameter, pattern, the reunion situation of synthesis cobalt hydroxide presoma.
Preferably, in described step (3), stir cobalt hydroxide precipitation in described pulp processing procedure, the speed of described stirring is 100 ~ 175 rpms.
Further preferably, the mixing speed of concrete reaction system fluctuates in the scope of ± 12.5 rpms.
Preferably, in described step (2), in the process of described precipitation reaction, adopt 3 ~ 8m
3the gas flow of/h blasts air in reactant liquor.
Air, as oxidant, can make part low price cobalt oxidation be high price.
Preferably, in described step (2), adopting the flow velocity of 1 ~ 10L/h in reactant liquor, add concentration is 10% ~ 20% ammoniacal liquor.
Further preferably, in described step (2), adopting the flow velocity of 3L/h in reactant liquor, add concentration is 13% ammoniacal liquor.
Ammoniacal liquor is as conditioning agent, and the complexing of energy intensified response system, slows down nucleation rate, slow down particle size growth, can regulate the particle diameter of cobalt hydroxide.
Preferably, in described step (3), the mode of described Separation of Solid and Liquid is centrifugation.
Preferably, in described step (3), the mode of described Separation of Solid and Liquid is that micro porous filtration is separated.
Preferably, in described step (3), the mode of described carrying out washing treatment is that the pure water of employing 40 ~ 70 DEG C is by described solids wash 3 ~ 6 times.
Preferably, in described step (3), described drying process mode be at 80 ~ 150 DEG C by described solid drying to weight.
Preferably, in described step (3), the mode of described break process is airflow crash or Mechanical Crushing.
Further preferably, in described step (3), the mode of described break process is airflow crash.
Preferably, in described step (3), the atmosphere of described airflow crash is inert gas atmosphere.
Preferably, in described step (4), in During Hydrogen Reducing, the gas flow of described reducibility gas is 5 ~ 15m
3/ h.
Preferably, in described step (4), in During Hydrogen Reducing, described reducibility gas is hydrogen.
Further preferably, in described step (4), in During Hydrogen Reducing, the gas flow of described reducibility gas is 8m
3/ h.
In described step (4), in During Hydrogen Reducing, the gas flow of described reducibility gas is excessive.
Preferably, in described step (4), in During Hydrogen Reducing, the boat charge of described cobalt hydroxide powder is 0.5 ~ 0.85 times of boat volume.
The boat charge that the present inventor adopts is preferably 0.5 ~ 0.85 times of boat volume.If boat charge is many, the throughput of the reducing gas of unit cobalt powder contact is just little, and the grain diameter restored is large; The throughput of reducing gas of cobalt powder contact is too small, and also to there will be reduction insufficient, and cause the phenomenon that oxygen content exceeds standard, therefore suitable boat charge also can affect the quality of cobalt powder.
Preferably, in described step (4), in During Hydrogen Reducing, the boat time that pushes away of described cobalt hydroxide powder is 15 ~ 40 minutes.
Preferably, in described step (4), in During Hydrogen Reducing, described reducibility gas is hydrogen.
Preferably, in described step (5), the atmosphere of described airflow crash is inert gas atmosphere.
Preferably, in described step (5), the gas flow that described airflow crash adopts is 4 ~ 6MPa.
Preferably, in described step (5), the frequency of described airflow crash is 10 ~ 50HZ.
Further preferably, in described step (5), the frequency of described airflow crash is 27HZ.
It is spherical that the preparation method of half micron cobalt powder provided by the invention can prepare pattern or class is spherical and Fsss granularity is the cobalt powder of 0.5 ~ 0.8 μm half micron, and product pattern and size tunable, low cost, without ammonia and nitrogen pollution problem.
The third aspect, the invention provides a kind of cobalt hydroxide powder, and the pattern of described cobalt hydroxide powder is granular or bar-shaped, and Fisher particle size is 0.33 ~ 0.58 μm.
Preferably, the pattern of described cobalt hydroxide powder is thin spheric granules.
Preferably, the D of described cobalt hydroxide powder
50particle diameter is 0.52 ~ 1.26 μm.
Preferably, in described cobalt hydroxide powder the content of cobalt at 67.89% ~ 71.42%(wt).
Preferably, in described cobalt hydroxide powder the content of impurity natrium lower than 78ppm.
Preferably, in described cobalt hydroxide powder the content of impurity calcium respectively lower than 59ppm.
Preferably, in described cobalt hydroxide powder the content of impurity iron respectively lower than 58ppm.
Cobalt hydroxide powder solubility product constant provided by the invention is very little, and particle is little, and impurity content is low, can for the preparation of half micron cobalt powder.
Fourth aspect, the invention provides a kind of preparation method of cobalt hydroxide powder, comprises the following steps:
(1) cobalt salt solution and precipitant solution is prepared, in described cobalt salt solution, the concentration of cobalt ions is 0.37 ~ 0.62mol/L, the concentration of described precipitant solution is 8 ~ 15 times of the concentration of cobalt ions in described cobalt salt solution, and described precipitating reagent is alkali metal hydroxide;
(2) cobalt salt solution step (1) prepared and precipitant solution join in reactor in the mode of bottom feed carries out precipitation reaction, obtain the solution containing cobalt hydroxide precipitation, wherein, the speed that described cobalt salt solution adds is 64 ~ 74L/h, and the speed that described precipitant solution adds is 1.3 ~ 3 times that described cobalt salt solution adds speed;
(3) step (2) gained is obtained cobalt hydroxide precipitation containing after the solution centrifugal separation of cobalt hydroxide precipitation, pulp process 0.5 ~ 4 hour at again gained cobalt hydroxide being deposited in 40 ~ 70 DEG C, carry out subsequently washing, dry, broken, obtain cobalt hydroxide powder, the pattern of described cobalt hydroxide powder is granular or bar-shaped, and Fisher particle size is 0.33 ~ 0.58 μm.
Preferably, in described step (1), described cobalt salt is soluble cobalt.
Preferably, in described step (1), described alkali metal hydroxide is NaOH or potassium hydroxide.
Further preferably, in described step (1), described alkali metal hydroxide is NaOH.
Preferably, in described step (1), described cobalt salt is cobalt chloride, cobalt nitrate, cobaltous sulfate or cobalt acetate.
Preferably, in described step (1), be sodium carbonate liquor or the solution of potassium carbonate of 0.1 ~ 0.5mol/L containing molar concentration in described precipitant solution.
Further preferably, in described step (1), containing molar concentration in described precipitant solution is the sodium carbonate liquor of 0.1 ~ 0.5mol/L.
Still more preferably, in described step (1), containing molar concentration in described precipitant solution is the sodium carbonate liquor of 0.25mol/L.
Sodium carbonate liquor or solution of potassium carbonate, as conditioning agent, affect particle diameter, pattern, the reunion situation of synthesis cobalt hydroxide presoma.
Preferably, in described step (2), before described cobalt salt solution and precipitant solution add reactor, in described reactor, water at the bottom of the reaction of covering paddle 5 ~ 30cm on reactor is provided with.
Further preferably, in described step (2), before described cobalt salt solution and precipitant solution add reactor, in described reactor, water at the bottom of the reaction of covering paddle 15cm on reactor is provided with.
Preferably, the reaction temperature of described precipitation reaction is 44 ~ 70 DEG C.
Further preferably, the reaction temperature of concrete reaction system fluctuates in the scope of ± 3 DEG C.
Preferably, in described precipitation reaction process, the pH value of reaction solution is 11.0 ~ 11.6.
Preferably, by controlling the pH of reaction solution described in concrete reaction system course of reaction, the pH of reaction solution being finely tuned, affecting particle diameter, pattern, the reunion situation of synthesis cobalt hydroxide presoma.
Preferably, in described step (3), stir cobalt hydroxide precipitation in described pulp processing procedure, described mixing speed is 100 ~ 175 rpms.
Further preferably, the speed that concrete reaction system stirs fluctuates in the scope of ± 12.5 rpms.
Preferably, in described step (2), in the process of described precipitation reaction, adopt 3 ~ 8m
3the gas flow of/h blasts air in reactant liquor.
Air, as oxidant, can make part low price cobalt oxidation be high price.
Preferably, in described step (2), adopting the flow velocity of 1 ~ 10L/h in reactant liquor, add concentration is 10% ~ 20% ammoniacal liquor.
Further preferably, in described step (2), adopting the flow velocity of 3L/h in reactant liquor, add concentration is 13% ammoniacal liquor.
Ammoniacal liquor is as conditioning agent, and the complexing of energy intensified response system, slows down nucleation rate, slow down particle size growth, can regulate the particle diameter of cobalt hydroxide.
Preferably, in described step (3), the mode of described Separation of Solid and Liquid is centrifugation.
Preferably, in described step (3), the mode of described Separation of Solid and Liquid is that micro porous filtration is separated.
Preferably, in described step (3), the mode of described carrying out washing treatment is that the pure water of employing 40 ~ 70 DEG C is by described solids wash 3 ~ 6 times.
Preferably, in described step (3), described drying process mode be at 80 ~ 150 DEG C by described solid drying to weight.
Preferably, in described step (3), the mode of described break process is airflow crash or Mechanical Crushing.
Preferably, the frequency of described airflow crash is 10 ~ 50HZ.
Preferably, the atmosphere of described airflow crash is inert gas atmosphere.
Cobalt hydroxide powder preparation provided by the invention, add as: cobalt salt and precipitating reagent pattern and the particle diameter that speed, flow, reaction temperature, the pH of reaction solution and mixing speed etc. control cobalt hydroxide powder by the condition that controls synthesis cobalt hydroxide powder, there is the advantage of controlled, low cost easy and simple to handle; Secondly, adopt NaOH or potassium hydroxide to replace carbonic hydroammonium or ammonium oxalate as precipitating reagent, Traditional Industrialization can be overcome and produce the problem that in cobalt powder process, ammonia and nitrogen pollution is serious; In addition, by strengthening washing, amplitude peak ground reduces the impurity content in cobalt hydroxide, is conducive to the cobalt powder that follow-up preparation purity is high.
Half micron cobalt powder provided by the invention and preparation method thereof and cobalt hydroxide powder and preparation method thereof, have following beneficial effect:
(1) the invention provides a kind of half micron cobalt powder, the pattern of this half micron cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5 ~ 0.8 μm, has the advantage of super-fine cobalt powder and class ball cobalt powder concurrently;
(2) the invention provides a kind of preparation method of half micron cobalt powder, the method can realize the advantage of the low and environmental protection of product pattern and size tunable, cost;
(3) the invention provides a kind of cobalt hydroxide powder, the pattern of this cobalt hydroxide powder is granular or bar-shaped, and Fisher particle size is 0.33 ~ 0.58 μm, is suitable as the presoma of the cobalt powder of suitability for industrialized production half micron;
(4) cobalt hydroxide powder preparation provided by the invention, can realize the advantage of the low and environmental protection of the pattern of cobalt hydroxide powder and size tunable, cost.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of the present invention half micron cobalt powder;
Fig. 2 is the SEM figure of half micron cobalt powder prepared by the embodiment of the present invention 1.
Detailed description of the invention
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Embodiment 1
Fig. 1 is preparation technology's flow chart of the present invention half micron cobalt powder, as shown in Figure 1, and a kind of half micron of cobalt
The preparation method of powder, comprises the following steps:
(1) prepare 0.37mol/L(48g/L) cobalt chloride solution and 5.48mol/L(219g/L) sodium hydroxide solution;
(2) reaction end water is added in a kettle., covered paddle 15cm on it, then the sodium hydroxide solution (1) prepared and cobalt chloride solution join in reactor with the flow of 25 ~ 40L/h and 72L/h respectively in the mode of bottom feed and carry out precipitation reaction, the temperature arranging reaction is 46 DEG C, the pH value of reaction solution is 11.45 ~ 11.60, the mixing speed of reaction solution is 125 rpms, reaction terminates and carry out centrifugal after obtain cobalt hydroxide precipitate;
(3) pulp process 4 hours at (2) gained cobalt hydroxide being deposited in 40 DEG C, carries out centrifugation subsequently and obtains solid, and described solid, after the pure water 5 times of 40 DEG C, is dried to weight at 80 DEG C, with after obtain cobalt hydroxide powder through airflow crash;
(4) (3) gained cobalt hydroxide powder is placed in hydrogen reduction furnace, passes into hydrogen, arranging gas flow is 8m
3/ h, reduce 16.5 hours at 370 DEG C, obtain cobalt powder, wherein, the boat charge of cobalt hydroxide powder is 2kg/ boat (boat charge of 0.5 times), and pushing away the boat time is 40 minutes;
(5), after (4) gained cobalt powder being carried out airflow crash (the broken frequency adopted is 27HZ), obtain half micron cobalt powder, the pattern of described half micron cobalt powder is spherical or class is spherical, and Fisher particle size is 0.54 μm, D
50particle diameter is 4.3 μm, and oxygen content is 1.03%, is 53.75ppm containing sodium amount, and calcium content is 61.4ppm.
Fig. 2 be the embodiment of the present invention 1 prepare half micron cobalt powder SEM figure, as shown in Figure 2, the pattern of this half micron cobalt powder mostly be spherical or class spherical, only have a little agglomeration; Secondly, its particle diameter is smaller, and mean F sss granularity is at 0.48 μm; In addition, this half micron cobalt powder impurity content is few, has the advantage of super-fine cobalt powder and class ball cobalt powder concurrently, and particle diameter is little and even.
Embodiment 2
A preparation method for half micron cobalt powder, comprises the following steps:
(1) configure the cobalt nitrate solution of 0.37mol/L, then prepare the mixed solution of potassium hydroxide-sodium carbonate, in described mixed solution, the concentration of potassium hydroxide is the solution of 5.53mol/L, and the concentration of sodium carbonate is 0.25mol/L;
(2) reaction end water is added in a kettle., covered paddle 5cm on it, then NaOH-the sodium carbonate mixture (1) prepared and cobalt nitrate solution join in reactor with the flow of 35 ~ 50L/h and 64L/h respectively in the mode of bottom feed and carry out precipitation reaction, the temperature arranging reaction is 55 ~ 70 DEG C, the pH value of reaction solution is 11.10 ~ 11.50, the mixing speed of reaction solution is 175 rpms, reaction terminates and carry out centrifugal after obtain cobalt hydroxide precipitate;
(3) pulp process 0.5 hour at (2) gained cobalt hydroxide being deposited in 70 DEG C, carry out micro porous filtration separation subsequently and obtain solid, described solid, after the pure water 4 times of 40 DEG C, is dried to weight at 150 DEG C, with after obtain cobalt hydroxide powder through airflow crash;
(4) (3) gained cobalt hydroxide powder is placed in hydrogen reduction furnace, passes into hydrogen, arranging gas flow is 15m
3/ h, at 340 DEG C, reductase 12 0 hour, obtains cobalt powder, and wherein, the boat charge of cobalt hydroxide powder is 0.35 ~ 0.7kg/ boat (boat charge of 0.5 times), and pushing away the boat time is 15 minutes;
(5), after (4) gained cobalt powder being carried out airflow crash (the broken frequency adopted is 10HZ), obtain half micron cobalt powder, the Fisher particle size of described half micron cobalt powder is 0.48 μm, D50 particle diameter is 4.15 μm, oxygen content is 1.15%, is 79ppm containing sodium amount, and calcium content is 30ppm.
Embodiment 3
A preparation method for half micron cobalt powder, comprises the following steps:
(1) the cobalt acetate solution of 0.62mol/L is configured, the sodium hydroxide solution of 5.48mol/L;
(2) reaction end water is added in a kettle., covered paddle 15cm on it, then the sodium hydroxide solution (1) prepared and cobalt acetate solution join in reactor with the flow of 30 ~ 40L/h and 73L/h respectively in the mode of bottom feed, and simultaneously in reactant liquor with 3 ~ 8m
3the gas flow of/h blasts air, carries out precipitation reaction, and the temperature arranging reaction is 64 DEG C, and the pH value of reaction solution is 11.10 ~ 11.50, and the mixing speed of reaction solution is 125 rpms, reaction terminates and carry out centrifugal after obtain cobalt hydroxide precipitate;
(3) pulp process 3 hours at (2) gained cobalt hydroxide being deposited in 50 DEG C, carries out centrifugation subsequently and obtains solid, and described solid, after the pure water 3 times of 50 DEG C, is dried to weight at 100 DEG C, with after obtain cobalt hydroxide powder through Mechanical Crushing;
(4) (3) gained cobalt hydroxide powder is placed in hydrogen reduction furnace, passes into hydrogen, arranging gas flow is 5m
3/ h, reduce 10 hours at 370 DEG C, obtain cobalt powder, wherein, the boat charge of cobalt hydroxide powder is 2 ~ 2.5kg/ boat (boat charge of 0.5 times), and pushing away the boat time is 40 minutes;
(5), after (4) gained cobalt powder being carried out airflow crash (the broken frequency adopted is 50HZ), obtain half micron cobalt powder, the Fisher particle size of described half micron cobalt powder is 0.54 μm, D
50particle diameter is 4.04 μm, and oxygen content is 1.15%, is 65.92ppm containing sodium amount, and calcium content is 76.54ppm.
Embodiment 4
A preparation method for half micron cobalt powder, comprises the following steps:
(1) configure the cobalt sulfate solution of 0.29mol/L, the sodium hydroxide solution of 5.48mol/L, mass fraction is 13%(wt) ammoniacal liquor;
(2) reaction end water is added in a kettle., covered paddle 30cm on it, then hydrogen-oxygen sodium solution, cobalt sulfate solution and ammoniacal liquor that (1) prepares are joined in reactor with the flow of 30 ~ 40L/h, 74L/h and 3L/h in the mode of bottom feed respectively, carry out precipitation reaction, the temperature arranging reaction is 50 ~ 55 DEG C, the pH value of reaction solution is 11.10 ~ 11.40, and the mixing speed of reaction solution is 100 rpms, reaction terminates and carry out centrifugal after obtain cobalt hydroxide precipitate;
(3) pulp process 3 hours at (2) gained cobalt hydroxide being deposited in 50 DEG C, carry out centrifugation subsequently and obtain solid, described solid is after the pure water 6 times of 50 DEG C, at 120 DEG C, be dried to weight, with after obtain cobalt hydroxide powder through Mechanical Crushing (broken adopt frequency be 70HZ);
(4) (3) gained cobalt hydroxide powder is placed in hydrogen reduction furnace, passes into hydrogen, arranging gas flow is 8m
3/ h, reduce 16.5 hours at 370 DEG C, obtain cobalt powder, wherein, the boat charge of cobalt hydroxide powder is 2 ~ 2.5kg/ boat (boat charge of 0.5 times), and pushing away the boat time is 40 minutes;
(5), after (4) gained cobalt powder being carried out airflow crash (the broken frequency adopted is 27HZ), obtain half micron cobalt powder, the Fisher particle size of described half micron cobalt powder is 0.62 μm, D
50particle diameter is 4.36 μm, and oxygen content is 0.90%, is 31.20ppm containing sodium amount, and calcium content is 48.20ppm.
For absolutely proving beneficial effect of the present invention, additionally providing the physical and chemical indexes of intermediate product cobalt hydroxide powder body prepared by the embodiment of the present invention 1 ~ 4, comprising Fisher particle size, D
50particle diameter, apparent density, tap density and impurity content, see table 1:
The physical and chemical indexes of cobalt hydroxide powder prepared by table 1 embodiment 1 ~ 4
As shown in table 1, the Fisher particle size of intermediate product cobalt hydroxide powder body prepared by the embodiment of the present invention 1 ~ 4 is between 0.33 ~ 0.58 μm, and D50 is between 0.8 ~ 1.26 μm, and apparent density (HB) is at 0.32 ~ 0.6g/cm
3between, tap density (TD) is at 0.61 ~ 1.02g/cm
3between, cobalt content is at 67.89% ~ 71.42%(wt), the impurity contents such as Na, Ca, Fe and S are lower, illustrate that preparation method of the present invention can provide particle diameter comparatively thin and the cobalt hydroxide powder that impurity content is lower.Wherein, the particle diameter of the cobalt hydroxide powder that embodiment 4 provides is slightly large, because precipitation reaction process adds ammoniacal liquor, due to complexing, cobalt hydroxide nucleation rate slows down, and particle diameter is slightly large; The particle diameter of the cobalt hydroxide powder that embodiment 3 provides is comparatively large, and in addition, cobalt content is higher than other embodiments, is that part cobalt hydroxide is oxidized, improves the content of cobalt because it has blasted air in the reactant liquor of precipitation reaction.Therefore, the mode that the present invention adopts carbonate and NaOH (potassium hydroxide) to mix, in reactant liquor, blast the mode of air or pass into the mode of ammoniacal liquor, all can affect the physical and chemical indexes of cobalt hydroxide presoma, especially can be used for regulating the size of presoma particle diameter.
In a word, the mode that the present invention adopts interval reinforced according to the flow of the characteristic change reactant such as particle diameter, pattern of cobalt hydroxide in course of reaction thus continuous accurate control pH, in addition, the present invention also adopts other conditions, such as: in precipitation reaction process, blast air, pass into ammoniacal liquor or use the mode of the mixed alkali liquor of hydroxide and carbonate to regulate the features such as the particle diameter of gained cobalt hydroxide, pattern and oxidizability, therefore, the pattern that the cobalt hydroxide that the present invention obtains reduces than the cobalt carbonate in existing production is good.Adopt cobalt hydroxide provided by the invention to reduce and prepare cobalt powder, particle diameter can be obtained at 0.5 ~ 0.8 μm, half micron cobalt powder of pattern and size tunable.The cobalt hydroxide that the present invention obtains and cobalt powder can be widely used in hart metal product and the battery industries such as digital cuttings, bar, top hammer, drill bit.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a preparation method for half micron cobalt powder, is characterized in that, comprises the following steps:
(1) cobalt salt solution and precipitant solution is prepared, in described cobalt salt solution, the concentration of cobalt ions is 0.37 ~ 0.62mol/L, the concentration of described precipitant solution is 8 ~ 15 times of the concentration of cobalt ions in described cobalt salt solution, and described precipitating reagent is alkali metal hydroxide;
(2) cobalt salt solution step (1) prepared and precipitant solution join in reactor in the mode of bottom feed carries out precipitation reaction, obtain the solution containing cobalt hydroxide precipitation, wherein, the speed that described cobalt salt solution adds is 64 ~ 74L/h, and the speed that described precipitant solution adds is 1.3 ~ 3 times that described cobalt salt solution adds speed;
(3) step (2) gained is obtained cobalt hydroxide precipitation containing after the solution centrifugal separation of cobalt hydroxide precipitation, pulp process 0.5 ~ 4 hour at again gained cobalt hydroxide being deposited in 40 ~ 70 DEG C, carry out subsequently washing, dry, broken, obtain cobalt hydroxide powder, the pattern of described cobalt hydroxide powder is granular or bar-shaped, and Fisher particle size is 0.33 ~ 0.58 μm;
(4), by the cobalt hydroxide powder of step (3) gained be placed in reduction furnace, pass into reducibility gas, reduce 12 ~ 20 hours at 340 ~ 370 DEG C, obtain cobalt powder;
(5), by step (4) gained cobalt powder carry out airflow crash, obtain half micron cobalt powder, the pattern of described half micron cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5 ~ 0.8 μm.
2. the preparation method of half micron cobalt powder as claimed in claim 1, is characterized in that, in described step (1), described cobalt salt is cobalt chloride, cobalt nitrate, cobaltous sulfate or cobalt acetate.
3. the preparation method of half micron cobalt powder as claimed in claim 1, it is characterized in that, in described step (2), the reaction temperature of described precipitation reaction is 44 ~ 70 DEG C, the pH value of reaction solution is 11.0 ~ 11.6, and the mixing speed of reaction solution is 100 ~ 175 rpms.
4. the preparation method of half micron cobalt powder as claimed in claim 1, is characterized in that, in described step (2), in the process of described precipitation reaction, adopts 3 ~ 8m
3the gas flow of/h blasts air in reactant liquor.
5. the preparation method of half micron cobalt powder as claimed in claim 1, is characterized in that, in described step (2), in the process of described precipitation reaction, adopting the flow velocity of 1 ~ 10L/h in reactant liquor, add concentration is 10% ~ 20% ammoniacal liquor.
6. the preparation method of half micron cobalt powder as claimed in claim 1, is characterized in that, in described step (3), the mode of described carrying out washing treatment is that the pure water of employing 40 ~ 70 DEG C is by the cobalt hydroxide washing of precipitate after described pulp 3 ~ 6 times.
7. the preparation method of half micron cobalt powder as claimed in claim 1, is characterized in that, in described step (4), in During Hydrogen Reducing, the gas flow of described reducibility gas is 5 ~ 15m
3/ h, the boat charge of described cobalt hydroxide powder is 0.5 ~ 0.85 times of boat volume, and pushing away the boat time is 15 ~ 40 minutes.
8. half micron cobalt powder, is characterized in that, the pattern of described half micron cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5 ~ 0.8 μm; Described half micron cobalt powder is prepared by the method for claim 1.
9. a preparation method for cobalt hydroxide powder, is characterized in that, comprises the following steps:
(1) cobalt salt solution and precipitant solution is prepared, in described cobalt salt solution, the concentration of cobalt ions is 0.37 ~ 0.62mol/L, the concentration of described precipitant solution is 8 ~ 15 times of the concentration of cobalt ions in described cobalt salt solution, and described precipitating reagent is NaOH or potassium hydroxide;
(2) cobalt salt solution step (1) prepared and precipitant solution join in reactor in the mode of bottom feed carries out precipitation reaction, obtain the solution containing cobalt hydroxide precipitation, wherein, the speed that described cobalt salt solution adds is 64 ~ 74L/h, and the speed that described precipitant solution adds is 1.3 ~ 3 times that described cobalt salt solution adds speed;
(3) step (2) gained is obtained cobalt hydroxide precipitation containing after the solution centrifugal separation of cobalt hydroxide precipitation, pulp process 0.5 ~ 4 hour at again gained cobalt hydroxide being deposited in 40 ~ 70 DEG C, carry out subsequently washing, dry, broken, obtain cobalt hydroxide powder, the pattern of described cobalt hydroxide powder is granular or bar-shaped, and Fisher particle size is 0.33 ~ 0.58 μm.
10. a cobalt hydroxide powder, is characterized in that, the pattern of described cobalt hydroxide powder is granular or bar-shaped, and Fisher particle size is 0.33 ~ 0.58 μm; Described cobalt hydroxide powder is prepared by method as claimed in claim 9.
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| CN103878389B (en) * | 2014-03-29 | 2016-03-30 | 宇辰新能源材料科技无锡有限公司 | A kind of production method of coarse granule cobalt powder |
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| CN104439280A (en) * | 2014-12-09 | 2015-03-25 | 英德佳纳金属科技有限公司 | Simultaneous preparing method of cobalt hydroxide and cobalt powder |
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| CN105923659B (en) * | 2016-05-30 | 2017-11-10 | 衢州华友钴新材料有限公司 | A kind of preparation method of LITHIUM BATTERY superfine sheet cobalt hydroxide |
| CN107030293A (en) * | 2016-11-28 | 2017-08-11 | 荆门市格林美新材料有限公司 | A kind of preparation method of utilization secondary reduction high-purity nickel powder |
| CN111115704A (en) * | 2018-10-31 | 2020-05-08 | 格林美（江苏）钴业股份有限公司 | Preparation method of cobaltosic oxide |
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