CN105798318B - A kind of cobalt powder and preparation method thereof and oxalic acid cobalt precursor and preparation method thereof - Google Patents
A kind of cobalt powder and preparation method thereof and oxalic acid cobalt precursor and preparation method thereof Download PDFInfo
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- CN105798318B CN105798318B CN201410837106.7A CN201410837106A CN105798318B CN 105798318 B CN105798318 B CN 105798318B CN 201410837106 A CN201410837106 A CN 201410837106A CN 105798318 B CN105798318 B CN 105798318B
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Abstract
The present invention provides a kind of cobalt powder, the cobalt powder is corynebacterium and/or near-spherical, and the apparent density of the cobalt powder is 0.85 1.1g/cm3, tap density is 1.6 1.8g/cm3.The apparent density and tap density of the cobalt powder are close, and specific surface area is also higher, when applied to hard alloy field, are conducive to the hard alloy for obtaining high-quality；The present invention also provides a kind of preparation method of cobalt powder, which uses continuous synthesis technology, and cobalt powder grain size is stably and controllable, is suitble to industrialized production.The present invention also provides a kind of oxalic acid cobalt precursor, the oxalic acid cobalt precursor is the spheroidal aggravation of the cobalt oxalate particle aggregation formation of corynebacterium and/or near-spherical, and the apparent density of the oxalic acid cobalt precursor is 0.5g/cm3‑0.7g/cm3, tap density 0.6g/cm3‑1.0g/cm3.The present invention also provides a kind of preparation methods of oxalic acid cobalt precursor.
Description
Technical field
Before metal particle preparing technical field more particularly to a kind of cobalt powder and preparation method thereof and cobalt oxalate
Drive body and preparation method thereof.
Background technology
Cobalt powder has a wide range of applications in field of metallurgy and chemical engineering, is production battery electrode, high hardness alloy and Buddha's warrior attendant lapicide
The important raw and processed materials of the chemical metallurgies product such as tool and catalyst carrier.
Prior art generally use cobalt oxalate as production cobalt powder presoma, oxalic acid cobalt precursor have oxygen content compared with
It is low, the better simply advantage of technique and condition of synthesis, but the pattern of oxalic acid cobalt precursor is dendroid, the cobalt powder of generation is also
Threadiness, appearance is bad, is difficult to reach the index of high quality cobalt powder in terms of specific area, activity and mobility etc..Publication number
A kind of spherical cobalt oxalate powder and preparation method thereof is disclosed for the application of CN101570478A, although oxalic acid made from this application
Cobalt is spherical shape, but cobalt oxalate structure is more open, will certainly influence the density of finally obtained cobalt powder, cause in hard alloy
In press molding and sintering process, cobalt powder volume can change greatly, and influence the quality of hard alloy.In addition, preparing oxalic acid cobalt powder
The precipitating reagent being added during body is potassium oxalate, and potassium ion not uncomplicated laundering affects production efficiency and product purity.
Invention content
To solve the above problems, first aspect present invention provides a kind of cobalt powder, which is corynebacterium and/or class ball
The density of shape, cobalt powder is higher, while the apparent density of cobalt powder and tap density numerical value are more close, solve cobalt in the prior art
Powder larger problem of volume change in the press molding of hard alloy and sintering process；Second aspect of the present invention provides cobalt powder
Preparation method；Third aspect present invention and fourth aspect each provide a kind of oxalic acid cobalt precursor and preparation method thereof.
In a first aspect, the present invention provides a kind of cobalt powder, the cobalt powder is corynebacterium and/or near-spherical, the cobalt powder
Apparent density is 0.85g/cm3-1.1g/cm3, tap density 1.6g/cm3-1.8g/cm3。
The apparent density of the cobalt powder is higher, can be applied to high apparent density, high performance hard alloy.The prior art
Apparent density be 0.85g/cm3-1.1g/cm3When, tap density is generally higher than 1.8g/cm3, and tap density of the present invention is
1.6g/cm3-1.8g/cm3, the value of tap density and apparent density is more close, when the cobalt powder is applied to hard alloy field
When, hard alloy volume shrinks very little in press molding and sintering process, is conducive to the hard alloy for obtaining high-quality.
D50 is the index of the particle swarm size distribution detected by laser particle analyzer, which can reflect particle
Whole size.Preferably, the D50 of cobalt powder of the present invention is 10 μm -23 μm, and under the preferable case, the cobalt powder is averaged
Grain size is larger, while particle diameter distribution is narrow, uniform particle diameter, can tungsten carbide preferably similar with grain size mix, after being conducive to raising
Batch mixing uniformity during continuous CEMENTED CARBIDE PRODUCTION reduces compacting deformation etc., keeps the consistency of product more preferable, prevents cobalt pond existing
As generation etc., the diversified demand to cobalt powder in industry is met.
Fisher particle size is tested using Fishe subsieve-sizes tester (Fisher Sub-sieve sizer), it is
Two pipe liquid level difference h of differential manometer caused by the pressure difference generated by powder bed according to air obtains specific grain surface
Product, it may be said that survey be individual particle size.Preferably, the Fisher particle size of the cobalt powder is 1.0 μm -1.5 μm, particle diameter distribution
Narrow, under the preferable case, the Fisher particle size of the cobalt powder is smaller, therefore has both the performance of super-fine cobalt powder.
Preferably, the specific surface area of the cobalt powder is 1.3m2/g-2.5m2/g.The specific surface area of the cobalt powder is larger.
The tap density of cobalt powder made from first aspect present invention and the value of apparent density are more close, are conducive to obtain height
The hard alloy of quality.
Second aspect, the present invention provides a kind of preparation methods of cobalt powder, include the following steps：
(1), reaction bottom liquid is added in a kettle, ammonium oxalate solution and cobalt salt solution cocurrent are added to the reaction bottom
In liquid, mixed solution is obtained, the pH for adjusting the mixed solution is 2.5-3.5, and reaction 2h- is stirred at 40 DEG C -55 DEG C
8h generates cobalt oxalate precipitation, mixing speed 100r/min-200r/min；The cobalt oxalate precipitation overflow is gone out into reaction kettle, into
Enter in aging reactor and is aged；
(2), treated that the cobalt oxalate precipitation is separated by solid-liquid separation, is dried and is sieved by aged, obtains cobalt oxalate
Presoma；The oxalic acid cobalt precursor is the spheroidal aggravation of the cobalt oxalate particle aggregation formation of corynebacterium and/or near-spherical, institute
The apparent density for stating oxalic acid cobalt precursor is 0.5g/cm3-0.7g/cm3, tap density 0.6g/cm3-1.0g/cm3；
(3), the oxalic acid cobalt precursor obtained by step (2) is placed in reduction furnace, is passed through reducibility gas, in 360 DEG C-
Reductase 12 h-3h at 460 DEG C, is then crushed, is sieved, obtain cobalt powder；The cobalt powder be corynebacterium and/or near-spherical, it is described
The apparent density of cobalt powder is 0.85g/cm3-1.1g/cm3, tap density 1.6g/cm3-1.8g/cm3。
Preferably, the Fisher particle size of the cobalt powder is 1.0 μm -1.5 μm.
Preferably, the laser particle size D50 of the cobalt powder is 10 μm -23 μm.
Preferably, the specific surface area of the cobalt powder is 1.3m2/g-2.5m2/g。
Preferably, in step (1), reaction bottom liquid is deionized water.
Preferably, in step (1), the cobalt salt is at least one of cobalt chloride, cobaltous sulfate, cobalt nitrate and cobalt acetate.
Preferably, in step (1), a concentration of 60g/L-140g/L of the cobalt salt solution.
Preferably, in step (1), a concentration of 100g/L-210g/L of the ammonium oxalate solution.
Preferably, in step (1), the preparation method of the ammonium oxalate solution is：By in dissolving oxalic acid water, then filter,
It is configured to oxalic acid solution, then the oxalic acid solution is heated to 75-95 DEG C, liquefied ammonia is then added and obtains mixed solution, and adjusts institute
It is 1.0-4.8 to state mixed solution pH value, is made into the ammonium oxalate solution.
Preferably, described that ammonium oxalate solution and the cobalt salt solution cocurrent are added to reaction bottom liquid in step (1)
When middle, the addition speed of the ammonium oxalate solution is 200L/h-500L/h, and the addition speed of the cobalt salt solution is 100L/h-
200L/h。
Preferably, in step (1), the Aging Temperature is 40 DEG C -60 DEG C, digestion time 2-3h.
Preferably, in step (2), the solid-liquid separation method is centrifugation, by the cobalt oxalate solid after separation of solid and liquid with 50
The washing of DEG C hot water, 120 DEG C of dryings after being crushed, are crossed 200 mesh and are sieved, obtain oxalic acid cobalt precursor.
It is highly preferred that in step (2), the mode of the break process is Mechanical Crushing.
Preferably, in step (2), 5 μm -20 μm of the Fisher particle size of the oxalic acid cobalt precursor.
Preferably, in step (2), the laser particle size D50 of the oxalic acid cobalt precursor is 60 μm -100 μm.
Preferably, in step (2), the D10 of the oxalic acid cobalt precursor is 25 μm -60 μm.
Preferably, in step (2), the D90 of the oxalic acid cobalt precursor is 85 μm -125 μm.
Preferably, in step (3), the reducibility gas is hydrogen or hydrogen and nitrogen mixture.
It is highly preferred that in step (3), the mode of the break process is Mechanical Crushing.
Preferably, in step (3), 200 mesh is crossed and are sieved.
It is 2.5-3.5 that the present invention, which maintains the pH value of reaction, and reaction is carried out under acidic environment and generates cobalt oxalate, anti-in synthesis
Should be in the process through strong mixing, long fibrous cobalt oxalate is broken into corynebacterium and/or near-spherical oxalic acid cobalt granule, corynebacterium
And/or near-spherical oxalic acid cobalt granule is under strong stirring force effect, is slowly gathered into spherical shape, the reaction time several hours with
On, oxalic acid cobalt precursor is obtained, the oxalic acid cobalt precursor is the cobalt oxalate particle aggregation formation of corynebacterium and/or near-spherical
The value of spheroidal aggravation, tap density and apparent density is more close.The oxalic acid cobalt precursor is by reduction, broken and screening
Afterwards, cobalt powder is obtained, the cobalt powder is corynebacterium and/or the cobalt granule of near-spherical, meanwhile, the tap density of the cobalt powder and pine fill
The value of density is more close.And the synthesis of prior art routine cobalt oxalate is generally using rapid reaction and stirring at low speed technique, reaction
Time in several minutes or dozens of minutes, maintains the fibrous morphology of cobalt oxalate most original.Therefore, the present invention is anti-by adjusting
The pattern, grain size and apparent density etc. for answering condition such as to react pH, reaction temperature, reaction time and mixing speed to control cobalt powder
The controllable of cobalt oxalate and cobalt powder morphology and grain size may be implemented in physical index numerical value, this method.
The preparation method for the cobalt powder that second aspect of the present invention provides, cobalt powder density obtained is higher, while the pine dress of cobalt powder
Density and tap density numerical value are more close, solve in the prior art cobalt powder in the press molding and sintering process of hard alloy
The larger problem of middle volume change；In addition, the precipitating reagent that this method uses for ammonium oxalate, is avoided using potassium oxalate as precipitation
Agent, it is possible to reduce washing water reduces production cost, improves production efficiency.
Preparation method of the present invention is using continuous synthesis technology, and first, ammonium oxalate solution and cobalt salt solution cocurrent are connected
It is continuous to be added in the liquid of the reaction bottom, after obtaining cobalt oxalate precipitation, by stirring, the cobalt oxalate precipitation in mixed solution is led to
Reaction kettle is isolated in the overflow port overflow for crossing reaction kettle, is then entered in aging reactor the cobalt oxalate precipitation and is aged；It will be through
The cobalt oxalate precipitation of ripening is separated by solid-liquid separation, is dried and is sieved, and oxalic acid cobalt precursor is obtained；The present invention uses one
Platform reaction kettle may be implemented on one side into material liquid, while go out the continuous preparation of cobalt oxalate precipitation, can effectively control reaction item
The oxalic acid cobalt precursor grain size of the variation of part, production is stably and controllable, and it is good that production efficiency can improve several times, the consistency of product,
It is at low cost, it is suitble to industrialized production.
The third aspect, the present invention provides a kind of oxalic acid cobalt precursor, the oxalic acid cobalt precursor is corynebacterium and/or class
The apparent density of the spheroidal aggravation that spherical cobalt oxalate particle aggregation is formed, the oxalic acid cobalt precursor is 0.5g/cm3-
0.7g/cm3, tap density 0.6g/cm3-1.0g/cm3。
Preferably, 5 μm -20 μm of the Fisher particle size of the oxalic acid cobalt precursor.
Preferably, the laser particle size D50 of the oxalic acid cobalt precursor is 60 μm -100 μm.
The oxalic acid cobalt precursor provided by the invention is the spheroidal aggravation that cobalt oxalate particle aggregation is formed, with individual particle
Spherical cobalt oxalate compare, density is higher.Meanwhile the pattern of spheroidal aggravation makes the specific surface area bigger of the cobalt oxalate,
Help to reduce sintering temperature.
The present invention provides a kind of sphere aggregates oxalic acid cobalt precursor for the first time, and the oxalic acid cobalt precursor is conglobulation
The numerical value of body, apparent density and tap density is more close, is suitable as the presoma of industrialized production cobalt powder, is conducive to obtain
The more similar cobalt powder of the numerical value of apparent density and tap density.
Fourth aspect, the present invention provides a kind of preparation methods of oxalic acid cobalt precursor, include the following steps：
(1), reaction bottom liquid is added in a kettle, ammonium oxalate solution and cobalt salt solution cocurrent are added to the reaction bottom
In liquid, mixed solution is obtained, the pH for adjusting the mixed solution is 2.5-3.5, and reaction 2h- is stirred at 40 DEG C -55 DEG C
8h generates cobalt oxalate precipitation, mixing speed 100r/min-200r/min；The cobalt oxalate precipitation overflow is gone out into reaction kettle, into
Enter in aging reactor and is aged；
(2), treated that the cobalt oxalate precipitation is separated by solid-liquid separation, is dried and is sieved by aged, obtains cobalt oxalate
Presoma；The oxalic acid cobalt precursor is the spheroidal aggravation of the cobalt oxalate particle aggregation formation of corynebacterium and/or near-spherical, institute
The apparent density for stating oxalic acid cobalt precursor is 0.5g/cm3-0.7g/cm3, tap density 0.6g/cm3-1.0g/cm3。
Preferably, 5 μm -20 μm of the Fisher particle size of the oxalic acid cobalt precursor.
Preferably, the laser particle size D50 of the oxalic acid cobalt precursor is 60 μm -100 μm.
The oxalic acid cobalt precursor preparation method that fourth aspect present invention provides, before realizing sphere aggregates cobalt oxalate for the first time
The preparation of body is driven, the pattern and size tunable of oxalic acid cobalt precursor obtained, manufacturing cost is low, and production efficiency is high.
Cobalt powder provided by the invention and preparation method thereof and oxalic acid cobalt precursor and preparation method thereof have following beneficial to effect
Fruit：
(1) the present invention provides a kind of cobalt powders, and the cobalt powder apparent density and tap density are close, which is applied to hard
When alloy, volume contraction is minimum in press molding and sintering process, is conducive to the hard alloy for obtaining high-quality；The cobalt powder
Laser particle size it is larger, can preferably tungsten carbide similar with grain size mix, specific surface area is high, is conducive to follow-up hard alloy life
Batch mixing uniformity during production reduces compacting deformation, prevents cobalt pond phenomenon generation etc.；The cobalt powder has both super-fine cobalt powder and class ball cobalt
The advantages of powder；
(2) the present invention provides a kind of preparation method of cobalt powder, preparation method uses continuous synthesis technology, and grain size stabilization can
Control, the consistency of product is good, and production efficiency is high, at low cost, is suitble to industrialized production；
(3) the present invention provides a kind of oxalic acid cobalt precursor, which is spheroidal aggravation, and grain size is larger,
The numerical value of apparent density and tap density is more close, is suitable as the presoma of industrialized production cobalt powder；
(4) oxalic acid cobalt precursor preparation method provided by the invention can realize that the pattern of oxalic acid cobalt precursor can with grain size
Control, manufacturing cost is low, and production efficiency is high.
Description of the drawings
Fig. 1 is the flow diagram of cobalt powder preparation method in one embodiment of the invention；
Fig. 2 is scanning electron microscope (SEM) figure of oxalic acid cobalt precursor prepared by the embodiment of the present invention 1；
Fig. 3 is the SEM enlarged drawings of oxalic acid cobalt precursor prepared by the embodiment of the present invention 1；
Fig. 4 is the SEM figures of cobalt powder prepared by the embodiment of the present invention 6.
Specific implementation mode
As described below is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Referring to FIG. 1, Fig. 1 is the flow diagram of cobalt powder preparation method in one embodiment of the invention, include the following steps：
S01, reaction bottom liquid is added in a kettle, ammonium oxalate solution and cobalt salt solution cocurrent is added to the reaction bottom
In liquid, mixed solution is obtained, the pH for adjusting the mixed solution is 2.5-3.5, and reaction 2h- is stirred at 40 DEG C -55 DEG C
8h generates cobalt oxalate precipitation, mixing speed 100r/min-200r/min；The cobalt oxalate precipitation overflow is gone out into reaction kettle, into
Enter in aging reactor and is aged；
S02, treated that the cobalt oxalate precipitation is separated by solid-liquid separation, is dried and is sieved by aged, obtains cobalt oxalate
Presoma；The oxalic acid cobalt precursor is the spheroidal aggravation of the cobalt oxalate particle aggregation formation of corynebacterium and/or near-spherical, institute
The apparent density for stating oxalic acid cobalt precursor is 0.5g/cm3-0.7g/cm3, tap density 0.6g/cm3-1.0g/cm3；
S03, the oxalic acid cobalt precursor obtained by step (2) is placed in reduction furnace, is passed through reducibility gas, in 360 DEG C-
Reductase 12 h-3h at 460 DEG C, is then crushed, is sieved, obtain cobalt powder；The cobalt powder be corynebacterium and/or near-spherical, it is described
The apparent density of cobalt powder is 0.85g/cm3-1.1g/cm3, tap density 1.6g/cm3-1.8g/cm3。
Embodiment 1
A kind of preparation method of oxalic acid cobalt precursor, includes the following steps：
(1), deionized water is added in a kettle, by the ammonium oxalate solution of a concentration of 150g/L and a concentration of 140g/L
Cobalt chloride solution cocurrent is added in reaction kettle, and the addition speed of ammonium oxalate solution is 380L/h, the addition speed of cobalt chloride solution
Degree is 100L/h, obtains mixed solution, and the pH for adjusting mixed solution is 3.5, and reaction 2h is stirred at 55 DEG C, generates oxalic acid
Cobalt precipitates, mixing speed 100r/min；Cobalt oxalate precipitation overflow is gone out into reaction kettle, into aging reactor in be aged；Ageing
Temperature is 40 DEG C, digestion time 3h；
(2), treated that cobalt oxalate precipitation is centrifuged by aged, cobalt oxalate solid is obtained, then with 50 DEG C of hot water
Cobalt oxalate solid is washed, 120 DEG C of dryings after being crushed, are crossed 200 mesh and sieved, obtain oxalic acid cobalt precursor；Oxalic acid cobalt precursor
The physical index parameter of body see the table below 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of oxalic acid cobalt precursor made from embodiment 1, and Fig. 3 is grass prepared by the embodiment of the present invention 1
The SEM enlarged drawings of sour cobalt precursor (Fig. 3 amplification factors are 5 times of Fig. 2).
As can be seen that oxalic acid cobalt precursor assembles to be formed for the cobalt granule of corynebacterium and/or near-spherical from Fig. 2 and Fig. 3
Spheroidal aggravation, oxalic acid cobalt precursor particle size is uniform.
Embodiment 2
A kind of preparation method of oxalic acid cobalt precursor, includes the following steps：
(1), deionized water is added in a kettle, by the ammonium oxalate solution of a concentration of 150g/L and a concentration of 60g/L
Cobalt sulfate solution cocurrent is added in reaction kettle, and the addition speed of ammonium oxalate solution is 200L/h, the addition speed of cobalt chloride solution
Degree is 150L/h, obtains mixed solution, and the pH for adjusting mixed solution is 3, and reaction 3h is stirred at 55 DEG C, generates cobalt oxalate
Precipitation, mixing speed 200r/min；Cobalt oxalate precipitation overflow is gone out into reaction kettle, into aging reactor in be aged；Ageing temperature
Degree is 60 DEG C, digestion time 2h；
(2), treated that cobalt oxalate precipitation is centrifuged by aged, cobalt oxalate solid is obtained, then with 50 DEG C of hot water
Cobalt oxalate solid is washed, 120 DEG C of dryings after being crushed, are crossed 200 mesh and sieved, obtain oxalic acid cobalt precursor；Oxalic acid cobalt precursor
The physical index parameter of body see the table below 1.
Embodiment 3
A kind of preparation method of oxalic acid cobalt precursor, includes the following steps：
(1), deionized water is added in a kettle, by the ammonium oxalate solution of a concentration of 100g/L and a concentration of 60g/L
Cobalt nitrate solution cocurrent is added in reaction kettle, and the addition speed of cobalt chloride solution is 200L/h, the addition speed of ammonium oxalate solution
Degree is 500L/h, obtains mixed solution, and the pH for adjusting mixed solution is 2.8, and reaction 3h is stirred at 55 DEG C, generates oxalic acid
Cobalt precipitates, mixing speed 150r/min；Cobalt oxalate precipitation overflow is gone out into reaction kettle, into aging reactor in be aged；Ageing
Temperature is 50 DEG C, digestion time 2.5h；
(2), treated that cobalt oxalate precipitation is centrifuged by aged, cobalt oxalate solid is obtained, then with 50 DEG C of hot water
Cobalt oxalate solid is washed, 120 DEG C of dryings after being crushed, are crossed 200 mesh and sieved, obtain oxalic acid cobalt precursor；Oxalic acid cobalt precursor
The physical index parameter of body see the table below 1.
Embodiment 4
A kind of preparation method of oxalic acid cobalt precursor, includes the following steps：
(1), deionized water is added in a kettle, by the ammonium oxalate solution of a concentration of 210g/L and a concentration of 140g/L
Cobalt chloride solution cocurrent is added in reaction kettle, and the addition speed of ammonium oxalate solution is 300L/h, the addition speed of cobalt chloride solution
Degree is 100L/h, obtains mixed solution, and the pH for adjusting mixed solution is 3.2, and reaction 6h is stirred at 45 DEG C, generates oxalic acid
Cobalt precipitates, mixing speed 150r/min；Cobalt oxalate precipitation overflow is gone out into reaction kettle, into aging reactor in be aged；Ageing
Temperature is 50 DEG C, digestion time 2.5h；
(2), treated that cobalt oxalate precipitation is centrifuged by aged, cobalt oxalate solid is obtained, then with 50 DEG C of hot water
Cobalt oxalate solid is washed, 120 DEG C of dryings after being crushed, are crossed 200 mesh and sieved, obtain oxalic acid cobalt precursor；Oxalic acid cobalt precursor
The physical index parameter of body see the table below 1.
Embodiment 5
A kind of preparation method of oxalic acid cobalt precursor, includes the following steps：
(1), deionized water is added in a kettle, by the ammonium oxalate solution of a concentration of 150g/L and a concentration of 100g/L
Cobalt sulfate solution cocurrent is added in reaction kettle, and the addition speed of ammonium oxalate solution is 300L/h, the addition speed of cobalt chloride solution
Degree is 150L/h, obtains mixed solution, and the pH for adjusting mixed solution is 2.5, and reaction 8h is stirred at 40 DEG C, generates oxalic acid
Cobalt precipitates, mixing speed 150r/min；Cobalt oxalate precipitation overflow is gone out into reaction kettle, into aging reactor in be aged；Ageing
Temperature is 50 DEG C, digestion time 2.5h；
(2), treated that cobalt oxalate precipitation is centrifuged by aged, cobalt oxalate solid is obtained, then with 50 DEG C of hot water
Cobalt oxalate solid is washed, 120 DEG C of dryings after being crushed, are crossed 200 mesh and sieved, obtain oxalic acid cobalt precursor；Oxalic acid cobalt precursor
The physical index parameter of body see the table below 1.
Embodiment 6
A kind of preparation method of cobalt powder, includes the following steps：
Step (1), (2) are the same as embodiment 1；
(3) the oxalic acid cobalt precursor obtained by step (2) is placed in reduction furnace, is passed through hydrogen, reductase 12 is small at 430 DEG C
When, then progress Mechanical Crushing, 200 mesh excessively are sieved, and are vacuum-packed, are obtained cobalt powder；The physical index parameter of cobalt powder is joined
It see the table below 2.
Fig. 4 is the SEM figures of cobalt powder prepared by the embodiment of the present invention 6；Figure 4, it is seen that cobalt powder be corynebacterium and/or
The particle of near-spherical, particle diameter distribution are more single.
Embodiment 7
A kind of preparation method of cobalt powder, includes the following steps：
Step (1), (2) are the same as embodiment 2；
(3) the oxalic acid cobalt precursor obtained by step (2) is placed in reduction furnace, is passed through hydrogen, reductase 12 is small at 460 DEG C
When, then progress Mechanical Crushing, 200 mesh excessively are sieved, and are vacuum-packed, are obtained cobalt powder；Cobalt powder is corynebacterium and/or class ball
The particle of shape, the physical index parameter of cobalt powder is referring to the following table 2.
Embodiment 8
A kind of preparation method of cobalt powder, includes the following steps：
Step (1), (2) are the same as embodiment 3；
(3) the oxalic acid cobalt precursor obtained by step (2) is placed in reduction furnace, is passed through hydrogen, it is small that 3 are restored at 360 DEG C
When, then progress Mechanical Crushing, 200 mesh excessively are sieved, and are vacuum-packed, are obtained cobalt powder；Cobalt powder is corynebacterium and/or class ball
The particle of shape, the physical index parameter of cobalt powder is referring to the following table 2.
Embodiment 9
A kind of preparation method of cobalt powder, includes the following steps：
Step (1), (2) are the same as embodiment 4；
(2) the oxalic acid cobalt precursor obtained by step (2) is placed in reduction furnace, is passed through hydrogen, reductase 12 is small at 410 DEG C
When, then progress Mechanical Crushing, 200 mesh excessively are sieved, and are vacuum-packed, are obtained cobalt powder；Cobalt powder is corynebacterium and/or class ball
The particle of shape, the physical index parameter of cobalt powder is referring to the following table 2.
Embodiment 10
A kind of preparation method of cobalt powder, includes the following steps：
Step (1), (2) are the same as embodiment 5；
(2) the oxalic acid cobalt precursor obtained by step (2) is placed in reduction furnace, is passed through the gaseous mixture of hydrogen and nitrogen, in
Reductase 12 hour at 410 DEG C, then carry out Mechanical Crushing, cross 200 mesh sieved, vacuum packaging, obtain cobalt powder；Cobalt powder is
The particle of corynebacterium and/or near-spherical, the physical index parameter of cobalt powder is referring to the following table 2.
Comparative example 1
A kind of preparation method of cobalt powder, includes the following steps：
(1), deionized water is added in a kettle, by the ammonium oxalate solution of a concentration of 150g/L and a concentration of 100g/L
Cobalt chloride solution cocurrent is added in reaction kettle, and the cocurrent adding material time is 10 minutes, and the addition speed of ammonium oxalate solution is 250L/
H, the addition speed of cobalt chloride solution are 150L/h, obtain mixed solution, and the pH for adjusting mixed solution is 2.5, at 40 DEG C into
Row is stirred to react 30min, generates cobalt oxalate precipitation, mixing speed 150r/min；Cobalt oxalate precipitation overflow is gone out into reaction kettle；
(2), the cobalt oxalate that overflow goes out washs cobalt oxalate solid with 50 DEG C of hot water, and 120 DEG C of dryings after being crushed, cross 200 mesh sieve
It is sieved, obtains oxalic acid cobalt precursor；The nature parameters of oxalic acid cobalt precursor see the table below 1.
(3), the oxalic acid cobalt precursor obtained by step (2) is placed in reduction furnace, is passed through reducibility gas, at 410 DEG C
Reductase 12 hour, then carry out Mechanical Crushing, cross 200 mesh sieved, vacuum packaging, obtain cobalt powder；The nature parameters of cobalt powder
Referring to the following table 2.
Table 1 is embodiment 1-5 and the reaction condition and physical index of the oxalic acid cobalt precursor in comparative example 1.
The reaction condition and physical index of 1 oxalic acid cobalt precursor of table
From table 1 it follows that the apparent density AD of the oxalic acid cobalt precursor of embodiment 1-5 is 0.5g/cm3-0.7g/
cm3, tap density TD is 0.6g/cm3-1.0g/cm3, Fisher particle size Fsss is 5 μm -20 μm, and laser particle size D50 is 60 μm -100
μm, D10 is 25 μm -60 μm, and D90 is 85 μm -125 μm.The present invention, can be with by controlling reaction condition (reaction temperature, pH etc.)
The physical index parameter of cobalt oxalate is controlled, therefore, cobalt oxalate physical index of the present invention is controllable.Before cobalt oxalate made from comparative example 1
It is 0.26g/cm to drive body AD3, TD 0.60g/cm3, apparent density and vibration density angle value difference are larger.
Table 2 is the physical index of embodiment 6-10 and the cobalt powder in comparative example 1, and the cobalt powder of embodiment 6-10 is real respectively
Apply what oxalic acid cobalt precursor reduction calcining made from 1-5 obtained.
The physical index of 2 cobalt powder of table
| Embodiment | Fsss(um) | AD(g/cm3) | TD(g/cm3) | D50(um) | BET(m2/g) |
| Embodiment 6 | 1.32 | 0.9 | 1.67 | 18.23 | 1.79 |
| Embodiment 7 | 1.41 | 1.08 | 1.75 | 22.61 | 1.35 |
| Embodiment 8 | 1.18 | 0.86 | 1.61 | 15.48 | 2.23 |
| Embodiment 9 | 1.25 | 0.92 | 1.69 | 16.49 | 1.81 |
| Embodiment 10 | 1.04 | 0.85 | 1.63 | 13.47 | 2.49 |
| Comparative example 1 | 1.18 | 0.69 | 1.81 | 6.48 | 0.76 |
From Table 2, it can be seen that the apparent density AD of the cobalt powder of embodiment 6-10 is 0.85g/cm3-1.1g/cm3, jolt ramming
Density T D is 1.6g/cm3-1.8g/cm3, the Fisher particle size of cobalt powder is 1.0 μm -1.5 μm, and laser particle size D50 is 10 μm -23 μm,
The specific surface area of cobalt powder is 1.3m2/g-2.5m2/g.Cobalt powder apparent density AD made from comparative example 1 is 0.69g/cm3, vibration density
Degree TD is 1.81g/cm3, differ larger.
To sum up, the tap density of cobalt powder provided by the invention and the value of apparent density are more close, when the cobalt powder application
When hard alloy field, hard alloy volume shrinks very little in press molding and sintering process, is conducive to obtain high-quality
Hard alloy.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (6)
1. a kind of cobalt powder, which is characterized in that the cobalt powder is corynebacterium and/or near-spherical, and the apparent density of the cobalt powder is
0.85g/cm3-1.1g/cm3, tap density 1.6g/cm3-1.8g/cm3, the specific surface area of the cobalt powder is 1.3m2/g-
2.5m2/g。
2. cobalt powder as described in claim 1, which is characterized in that the laser particle size D50 of the cobalt powder is 10 μm -23 μm.
3. a kind of preparation method of cobalt powder, which is characterized in that include the following steps：
(1), reaction bottom liquid is added in a kettle, ammonium oxalate solution and cobalt salt solution cocurrent are added to reaction bottom liquid
In, mixed solution is obtained, the pH for adjusting the mixed solution is 2.5-3.5, and reaction 2h-8h is stirred at 40 DEG C -55 DEG C,
Generate cobalt oxalate precipitation, mixing speed 100r/min-200r/min；The cobalt oxalate precipitation overflow is gone out into reaction kettle, is entered
It is aged in aging reactor；
(2), treated that the cobalt oxalate precipitation is separated by solid-liquid separation, is dried and is sieved by aged, obtains oxalic acid cobalt precursor
Body；The oxalic acid cobalt precursor is the spheroidal aggravation of the cobalt oxalate particle aggregation formation of corynebacterium and/or near-spherical, the grass
The apparent density of sour cobalt precursor is 0.5g/cm3-0.7g/cm3, tap density 0.6g/cm3-1.0g/cm3；
(3), the oxalic acid cobalt precursor obtained by step (2) is placed in reduction furnace, is passed through reducibility gas, in 360 DEG C -460 DEG C
Lower reductase 12 h-3h, is then crushed, is sieved, obtain cobalt powder；The cobalt powder be corynebacterium and/or near-spherical, the cobalt powder
Apparent density is 0.85g/cm3-1.1g/cm3, tap density 1.6g/cm3-1.8g/cm3。
4. the preparation method of cobalt powder as claimed in claim 3, which is characterized in that in step (1), it is described by ammonium oxalate solution and
When the cobalt salt solution cocurrent is added in the liquid of the reaction bottom, the addition speed of the ammonium oxalate solution is 200L/h-500L/
The addition speed of h, the cobalt salt solution are 100L/h-200L/h.
5. the preparation method of cobalt powder as claimed in claim 3, which is characterized in that in step (1), the cobalt salt be cobalt chloride,
At least one of cobaltous sulfate, cobalt nitrate and cobalt acetate.
6. the preparation method of cobalt powder as claimed in claim 3, which is characterized in that in step (1), the Aging Temperature is 40
DEG C -60 DEG C, digestion time 2h-3h.
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