CN103624251A - Half-micron cobalt powder, preparation method thereof, cobalt hydroxide powder and preparation method thereof - Google Patents
Half-micron cobalt powder, preparation method thereof, cobalt hydroxide powder and preparation method thereof Download PDFInfo
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Abstract
The invention provides a half-micron cobalt powder, the morphology of the half-micron cobalt powder is spherical or sphere-like, the Fisher particle size is 0.5Mu m to 0.8Mu m, the impurity content of the half-micron cobalt powder is low, and the half-micron cobalt powder has the advantages of both ultrafine cobalt powder and sphere-like cobalt powder. Secondly, the invention also provides a preparation method for the half-micron cobalt powder, the method adopts cobalt salt solution and sodium hydroxide or potassium hydroxide solution to react to produce cobalt hydroxide precipitate, the precipitate undergoes hydrogen reduction under 340 DEG C to 370 DEG C after being slurried, centrifuged, washed, dried and broken, so that cobalt powder is obtained, and the cobalt powder is broken, so that the half-micron cobalt powder is obtained; the method has the advantages of product morphology and particle size controllability and environment-friendliness. In addition, the invention provides a cobalt hydroxide powder and a preparation method thereof, the morphology of the cobalt hydroxide powder is granular or rod-like, and the Fisher particle size is 0.33Mu m to 0.58Mu m.
Description
Technical field
The invention belongs to metal particle preparing technical field, relate in particular to a kind of half micron of 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 scientific and technical development, different applications improves constantly the requirement of dusty material performance, in the preparation of ultra-fine cemented carbide, require cobalt powder Fisher particle size (Fsss) to be less than 0.8um and just can obtain better serviceability, therefore, provide Fsss particle diameter to seem very important lower than the cobalt powder of 0.8 μ m.
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 and prepares metal cobalt powder under hot conditions, but traditional metal-precipitator is carbonic hydroammonium or ammonium oxalate, the cobalt salt precursor of producing is cobalt carbonate and cobalt oxalate, the cobalt powder Fsss particle diameter of preparing is thus generally more than 0.8 μ m, and the use of carbonic hydroammonium or ammonium oxalate can cause a large amount of ammonia and nitrogen pollutions.
Summary of the invention
For addressing the above problem, first aspect present invention provides a kind of half micron of cobalt powder, and the pattern of described half micron of cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5～0.8 μ m.Second aspect present invention provides a kind of preparation method of half micron of cobalt powder, and product pattern and particle diameter are controlled, and low cost, without ammonia and nitrogen pollution problem.Third aspect present invention and fourth aspect also provide cobalt hydroxide powder and preparation method thereof.
First aspect, the invention provides a kind of half micron of cobalt powder, and the pattern of described half micron of cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5～0.8 μ m.
Preferably, the D of described half micron of cobalt powder
50particle diameter is 4.04～4.36 μ m.
Preferably, in described half micron of cobalt powder the content of sodium lower than 80ppm.
Preferably, in described half micron of cobalt powder the content of calcium lower than 80ppm.
Preferably, in described half micron of cobalt powder oxygen content lower than 1.15%.
The advantage particle diameter that half micron of 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 of cobalt powder, comprises the following steps:
(1) preparation cobalt salt solution and precipitant solution, 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 concentration of cobalt ions in described cobalt salt solution, and described precipitating reagent is alkali metal hydroxide;
(2) cobalt salt solution of step (1) preparation and precipitant solution are joined and in reactor, carry out precipitation reaction in the mode of bottom feed, 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 to cobalt hydroxide precipitation after the solution centrifugal separation containing cobalt hydroxide precipitation, gained cobalt hydroxide being deposited in to pulp at 40～70 ℃ processes 0.5～4 hour again, wash subsequently, be dried, 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 μ m;
(4), the cobalt hydroxide powder of step (3) gained is placed in to reduction furnace, pass into reducibility gas, at 340～370 ℃, reduce 16.5～17.5 hours, obtain cobalt powder;
(5), step (4) gained cobalt powder is carried out to airflow crash, obtain half micron of cobalt powder, the pattern of described half micron of cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5～0.8 μ m.
Preferably, by controlling the speed that described in concrete reaction system course of reaction, precipitant solution adds, the i.e. flow of flux of alkaline liquor, or cobalt salt, regulate the pH value of reaction solution, thereby change the particle diameter, pattern, reunion situation etc. of synthetic cobalt hydroxide presoma.
Preferably, in described step (1), described cobalt salt is solubility cobalt salt.
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), in described precipitant solution, contain sodium carbonate liquor or solution of potassium carbonate that molar concentration is 0.1～0.5mol/L.
Further preferably, in described step (1), in described precipitant solution, contain the sodium carbonate liquor that molar concentration is 0.1～0.5mol/L.
Still more preferably, in described step (1), in described precipitant solution, contain the sodium carbonate liquor that molar concentration is 0.25mol/L.
Sodium carbonate liquor or solution of potassium carbonate, as conditioning agent, affect particle diameter, pattern, the reunion situation of synthetic cobalt hydroxide presoma.
Preferably, in described step (2), before described cobalt salt solution and precipitant solution add reactor, in described reactor, be provided with water at the bottom of the reaction of covering paddle 5～30cm on reactor.
Further preferably, in described step (2), before described cobalt salt solution and precipitant solution add reactor, in described reactor, be provided with water at the bottom of the reaction of covering paddle 15cm on reactor.
Preferably, the reaction temperature of described precipitation reaction is 44～70 ℃.
Further preferably, the reaction temperature of concrete reaction system fluctuates in the scope of ± 3 ℃.
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 is finely tuned, affect particle diameter, pattern, the reunion situation of synthetic cobalt hydroxide presoma.
Preferably, in described step (3), in described pulp processing procedure, cobalt hydroxide precipitation is stirred, 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 is as oxidant, and can make part low price cobalt oxidation is high price.
Preferably, in described step (2), the flow velocity that adopts 1～10L/h is 10%～20% ammoniacal liquor to adding concentration in reactant liquor.
Further preferably, in described step (2), the flow velocity that adopts 3L/h is 13% ammoniacal liquor to adding concentration in reactant liquor.
Ammoniacal liquor is as conditioning agent, and the complexing of energy intensified response system, slows down nucleation rate, slows down particle diameter 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 for adopting the pure water of 40～70 ℃ by described solids wash 3～6 times.
Preferably, in described step (3), the mode of described dry processing be at 80～150 ℃ 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 inventor adopts is preferably 0.5～0.85 times of boat volume.If the throughput of the reducing gas of boat charge Duo， unit cobalt powder contact is just little, the grain diameter restoring is large; The throughput of the reducing gas of cobalt powder contact is too small also there will be reduction insufficient, the phenomenon that causes oxygen content to exceed standard, and 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 of cobalt powder provided by the invention can prepare pattern or class is spherical and Fsss granularity is the cobalt powder of half micron of 0.5～0.8 μ m, and product pattern and particle diameter are controlled, and 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 μ m.
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 μ m.
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 be for the preparation of half micron of cobalt powder.
Fourth aspect, the invention provides a kind of preparation method of cobalt hydroxide powder, comprises the following steps:
(1) preparation cobalt salt solution and precipitant solution, 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 concentration of cobalt ions in described cobalt salt solution, and described precipitating reagent is alkali metal hydroxide;
(2) cobalt salt solution of step (1) preparation and precipitant solution are joined and in reactor, carry out precipitation reaction in the mode of bottom feed, 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 to cobalt hydroxide precipitation after the solution centrifugal separation containing cobalt hydroxide precipitation, gained cobalt hydroxide being deposited in to pulp at 40～70 ℃ processes 0.5～4 hour again, wash subsequently, be dried, 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 μ m.
Preferably, in described step (1), described cobalt salt is solubility cobalt salt.
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), in described precipitant solution, contain sodium carbonate liquor or solution of potassium carbonate that molar concentration is 0.1～0.5mol/L.
Further preferably, in described step (1), in described precipitant solution, contain the sodium carbonate liquor that molar concentration is 0.1～0.5mol/L.
Still more preferably, in described step (1), in described precipitant solution, contain the sodium carbonate liquor that molar concentration is 0.25mol/L.
Sodium carbonate liquor or solution of potassium carbonate, as conditioning agent, affect particle diameter, pattern, the reunion situation of synthetic cobalt hydroxide presoma.
Preferably, in described step (2), before described cobalt salt solution and precipitant solution add reactor, in described reactor, be provided with water at the bottom of the reaction of covering paddle 5～30cm on reactor.
Further preferably, in described step (2), before described cobalt salt solution and precipitant solution add reactor, in described reactor, be provided with water at the bottom of the reaction of covering paddle 15cm on reactor.
Preferably, the reaction temperature of described precipitation reaction is 44～70 ℃.
Further preferably, the reaction temperature of concrete reaction system fluctuates in the scope of ± 3 ℃.
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 is finely tuned, affect particle diameter, pattern, the reunion situation of synthetic cobalt hydroxide presoma.
Preferably, in described step (3), in described pulp processing procedure, cobalt hydroxide precipitation is stirred, described mixing speed is 100～175 rpms.
Further preferably, the speed of concrete reaction system stirring 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 is as oxidant, and can make part low price cobalt oxidation is high price.
Preferably, in described step (2), the flow velocity that adopts 1～10L/h is 10%～20% ammoniacal liquor to adding concentration in reactant liquor.
Further preferably, in described step (2), the flow velocity that adopts 3L/h is 13% ammoniacal liquor to adding concentration in reactant liquor.
Ammoniacal liquor is as conditioning agent, and the complexing of energy intensified response system, slows down nucleation rate, slows down particle diameter 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 for adopting the pure water of 40～70 ℃ by described solids wash 3～6 times.
Preferably, in described step (3), the mode of described dry processing be at 80～150 ℃ 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 method provided by the invention, condition by controlling synthetic cobalt hydroxide powder as: the pH that adds speed, flow, reaction temperature, reaction solution of cobalt salt and precipitating reagent and mixing speed etc. are controlled pattern and the particle diameter of cobalt hydroxide powder, have controlled, advantage cheaply easy and simple to handle; Secondly, adopt NaOH or potassium hydroxide to replace carbonic hydroammonium or ammonium oxalate as precipitating reagent, can overcome Traditional Industrialization and produce the serious problem of ammonia and nitrogen pollution in cobalt powder process; In addition, by strengthening, wash, amplitude peak ground reduces the impurity content in cobalt hydroxide, is conducive to the high cobalt powder of follow-up preparation purity.
Half micron of 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 of cobalt powder, the pattern of this half micron of cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5～0.8 μ m, 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 of cobalt powder, the method can realize product pattern and particle diameter is controlled, cost is low and the advantage of environmental protection;
(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 μ m, is suitable as the presoma of the cobalt powder of half micron of suitability for industrialized production;
(4) cobalt hydroxide powder preparation method provided by the invention, can realize the pattern of cobalt hydroxide powder and particle diameter is controlled, cost is low and the advantage of environmental protection.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of half micron of cobalt powder of the present invention;
Fig. 2 is the SEM figure of half micron of cobalt powder of the embodiment of the present invention 1 preparation.
The specific embodiment
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 half micron of cobalt powder of the present invention, as shown in Figure 1, and a kind of half micron of cobalt
The preparation method of powder, comprises the following steps:
(1) preparation 0.37mol/L(48g/L) cobalt chloride solution and 5.48mol/L(219g/L) sodium hydroxide solution;
(2) in reactor, add reaction end water, covered paddle 15cm on it, then the sodium hydroxide solution of (1) preparation and cobalt chloride solution are joined and in reactor, carry out precipitation reaction with the flow of 25～40L/h and 72L/h respectively in the mode of bottom feed, the temperature that reaction is set is 46 ℃, the pH value of reaction solution is 11.45～11.60, the mixing speed of reaction solution is 125 rpms, and reaction finishes and carry out obtaining cobalt hydroxide after centrifugal to precipitate;
(3) (2) gained cobalt hydroxide is deposited in to pulp at 40 ℃ and processes 4 hours, carry out subsequently centrifugation and obtain solid, described solid washs after 5 times through the pure water of 40 ℃, is dried to weight, with obtain cobalt hydroxide powder by airflow crash at 80 ℃;
(4) (3) gained cobalt hydroxide powder is placed in to hydrogen reduction furnace, passes into hydrogen, it is 8m that gas flow is set
3/ h reduces 16.5 hours at 370 ℃, obtains cobalt powder, and 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) (4) gained cobalt powder is carried out to (the broken frequency adopting is 27HZ) after airflow crash, obtain half micron of cobalt powder, the pattern of described half micron of cobalt powder is spherical or class is spherical, and Fisher particle size is 0.54 μ m, D
50particle diameter is 4.3 μ m, and oxygen content is 1.03%, containing sodium amount, is 53.75ppm, and calcium content is 61.4ppm.
Fig. 2 is the SEM figure of half micron of cobalt powder of the embodiment of the present invention 1 preparation, and as shown in Figure 2, the pattern of this half micron of cobalt powder mostly is spherical or class is spherical, only has a little agglomeration; Secondly, its particle diameter is smaller, and mean F sss granularity is at 0.48 μ m; In addition, this half micron of 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 of 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, the solution that in described mixed solution, the concentration of potassium hydroxide is 5.53mol/L, the concentration of sodium carbonate is 0.25mol/L;
(2) in reactor, add reaction end water, covered paddle 5cm on it, then NaOH-the sodium carbonate mixture of (1) preparation and cobalt nitrate solution are joined and in reactor, carry out precipitation reaction with the flow of 35～50L/h and 64L/h respectively in the mode of bottom feed, the temperature that reaction is set is 55～70 ℃, the pH value of reaction solution is 11.10～11.50, the mixing speed of reaction solution is 175 rpms, and reaction finishes and carry out obtaining cobalt hydroxide after centrifugal to precipitate;
(3) (2) gained cobalt hydroxide being deposited in to pulp at 70 ℃ processes 0.5 hour, carry out subsequently micro porous filtration separation and obtain solid, described solid washs after 4 times through the pure water of 40 ℃, is dried to weight, with obtain cobalt hydroxide powder by airflow crash at 150 ℃;
(4) (3) gained cobalt hydroxide powder is placed in to hydrogen reduction furnace, passes into hydrogen, it is 15m that gas flow is set
3/ h, at 340 ℃, reductase 12 is 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) (4) gained cobalt powder is carried out to (the broken frequency adopting is 10HZ) after airflow crash, obtain half micron of cobalt powder, the Fisher particle size of described half micron of cobalt powder is 0.48 μ m, D50 particle diameter is 4.15 μ m, oxygen content is 1.15%, containing sodium amount, is 79ppm, and calcium content is 30ppm.
Embodiment 3
A preparation method for half micron of cobalt powder, comprises the following steps:
(1) the cobalt acetate solution of configuration 0.62mol/L, the sodium hydroxide solution of 5.48mol/L;
(2) in reactor, add reaction end water, covered paddle 15cm on it, then the sodium hydroxide solution of (1) preparation and cobalt acetate solution are joined 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 that reaction is set is 64 ℃, and the pH value of reaction solution is 11.10～11.50, and the mixing speed of reaction solution is 125 rpms, and reaction finishes and carry out obtaining cobalt hydroxide after centrifugal to precipitate;
(3) (2) gained cobalt hydroxide is deposited in to pulp at 50 ℃ and processes 3 hours, carry out subsequently centrifugation and obtain solid, described solid washs after 3 times through the pure water of 50 ℃, is dried to weight, with obtain cobalt hydroxide powder by Mechanical Crushing at 100 ℃;
(4) (3) gained cobalt hydroxide powder is placed in to hydrogen reduction furnace, passes into hydrogen, it is 5m that gas flow is set
3/ h reduces 10 hours at 370 ℃, obtains cobalt powder, and 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) (4) gained cobalt powder is carried out to (the broken frequency adopting is 50HZ) after airflow crash, obtain half micron of cobalt powder, the Fisher particle size of described half micron of cobalt powder is 0.54 μ m, D
50particle diameter is 4.04 μ m, and oxygen content is 1.15%, containing sodium amount, is 65.92ppm, and calcium content is 76.54ppm.
Embodiment 4
A preparation method for half micron of cobalt powder, comprises the following steps:
(1) cobalt sulfate solution of configuration 0.29mol/L, the sodium hydroxide solution of 5.48mol/L, mass fraction is 13%(wt) ammoniacal liquor;
(2) in reactor, add reaction end water, covered paddle 30cm on it, then by hydrogen-oxygen sodium solution, cobalt sulfate solution and the ammoniacal liquor of (1) preparation, the mode with bottom feed joins in reactor with the flow of 30～40L/h, 74L/h and 3L/h respectively, carry out precipitation reaction, the temperature that reaction is set is 50～55 ℃, the pH value of reaction solution is 11.10～11.40, and the mixing speed of reaction solution is 100 rpms, and reaction finishes and carry out obtaining cobalt hydroxide after centrifugal to precipitate;
(3) (2) gained cobalt hydroxide being deposited in to pulp at 50 ℃ processes 3 hours, carry out subsequently centrifugation and obtain solid, described solid washs after 6 times through the pure water of 50 ℃, at 120 ℃, be dried to weight, with obtaining cobalt hydroxide powder by Mechanical Crushing (the broken frequency adopting is 70HZ);
(4) (3) gained cobalt hydroxide powder is placed in to hydrogen reduction furnace, passes into hydrogen, it is 8m that gas flow is set
3/ h reduces 16.5 hours at 370 ℃, obtains cobalt powder, and 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) (4) gained cobalt powder is carried out to (the broken frequency adopting is 27HZ) after airflow crash, obtain half micron of cobalt powder, the Fisher particle size of described half micron of cobalt powder is 0.62 μ m, D
50particle diameter is 4.36 μ m, and oxygen content is 0.90%, containing sodium amount, is 31.20ppm, and calcium content is 48.20ppm.
For absolutely proving beneficial effect of the present invention, the physical and chemical indexes of the intermediate product cobalt hydroxide powder body of the embodiment of the present invention 1～4 preparation is also provided, comprise Fisher particle size, D
50particle diameter, apparent density, tap density and impurity content, referring to table 1:
The physical and chemical indexes of the cobalt hydroxide powder of table 1 embodiment 1～4 preparation
As shown in table 1, the Fisher particle size of the intermediate product cobalt hydroxide powder body of the embodiment of the present invention 1～4 preparation is between 0.33～0.58 μ m, and D50 is between 0.8～1.26 μ m, 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 carefully and the lower cobalt hydroxide powder of impurity content.Wherein, the particle diameter of the cobalt hydroxide powder that embodiment 4 provides is slightly large, because precipitation reaction process has added 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 larger, and in addition, cobalt content is higher than other embodiment, is that part cobalt hydroxide is oxidized, has improved the content of cobalt because it has blasted air in the reactant liquor of precipitation reaction.Therefore, the present invention adopts mode that carbonate and NaOH (potassium hydroxide) mixes, toward blasting the mode of air in reactant liquor or passing 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, thereby the present invention adopts intermittently reinforced mode and accurately controls continuously pH according to the flow of the characteristic change reactants such as the particle diameter of cobalt hydroxide in course of reaction, pattern, in addition, the present invention also adopts other conditions, such as: in precipitation reaction process, blast air, pass into ammoniacal liquor or by the mode of the mixed alkali liquor of hydroxide and carbonate, regulate the features such as particle diameter, pattern and oxidizability of gained cobalt hydroxide, therefore the cobalt hydroxide that, the present invention makes is better than the pattern of the cobalt carbonate reduction in existing production.Adopt cobalt hydroxide provided by the invention to reduce and prepare cobalt powder, can obtain particle diameter at half micron of controlled cobalt powder of 0.5～0.8 μ m, pattern and particle diameter.The cobalt hydroxide that the present invention makes 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. half micron of cobalt powder, is characterized in that, the pattern of described half micron of cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5～0.8 μ m.
2. a preparation method for half micron of cobalt powder, is characterized in that, comprises the following steps:
(1) preparation cobalt salt solution and precipitant solution, 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 concentration of cobalt ions in described cobalt salt solution, and described precipitating reagent is alkali metal hydroxide;
(2) cobalt salt solution of step (1) preparation and precipitant solution are joined and in reactor, carry out precipitation reaction in the mode of bottom feed, 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 to cobalt hydroxide precipitation after the solution centrifugal separation containing cobalt hydroxide precipitation, gained cobalt hydroxide being deposited in to pulp at 40～70 ℃ processes 0.5～4 hour again, wash subsequently, be dried, 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 μ m;
(4), the cobalt hydroxide powder of step (3) gained is placed in to reduction furnace, pass into reducibility gas, at 340～370 ℃, reduce 12～20 hours, obtain cobalt powder;
(5), step (4) gained cobalt powder is carried out to airflow crash, obtain half micron of cobalt powder, the pattern of described half micron of cobalt powder is spherical or class is spherical, and Fisher particle size is 0.5～0.8 μ m.
3. the preparation method of half micron of cobalt powder as claimed in claim 2, is characterized in that, in described step (1), described cobalt salt is cobalt chloride, cobalt nitrate, cobaltous sulfate or cobalt acetate.
4. the preparation method of half micron of cobalt powder as claimed in claim 2, it is characterized in that, in described step (2), the reaction temperature of described precipitation reaction is 44～70 ℃, the pH value of reaction solution is 11.0～11.6, and the mixing speed of reaction solution is 100～175 rpms.
5. the preparation method of half micron of cobalt powder as claimed in claim 2, 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.
6. the preparation method of half micron of cobalt powder as claimed in claim 2, is characterized in that, in described step (2), in the process of described precipitation reaction, the flow velocity that adopts 1～10L/h is 10%～20% ammoniacal liquor to adding concentration in reactant liquor.
7. the preparation method of half micron of cobalt powder as claimed in claim 2, is characterized in that, in described step (3), the pure water that the mode of described carrying out washing treatment is 40～70 ℃ of employings is by the cobalt hydroxide washing of precipitate after described pulp 3～6 times.
8. the preparation method of half micron of cobalt powder as claimed in claim 2, 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 presoma is 0.5～0.85 times of boat volume, pushing away the boat time is 15～40 minutes.
9. 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 μ m.
10. a preparation method for cobalt hydroxide powder, is characterized in that, comprises the following steps:
(1) preparation cobalt salt solution and precipitant solution, 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 concentration of cobalt ions in described cobalt salt solution, and described precipitating reagent is NaOH or potassium hydroxide;
(2) cobalt salt solution of step (1) preparation and precipitant solution are joined and in reactor, carry out precipitation reaction in the mode of bottom feed, 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 to cobalt hydroxide precipitation after the solution centrifugal separation containing cobalt hydroxide precipitation, gained cobalt hydroxide being deposited in to pulp at 40～70 ℃ processes 0.5～4 hour again, wash subsequently, be dried, 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 μ m.
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| 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 |
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