CN1248813C - Process for preparing nano grade super fine cobalt powder - Google Patents

Process for preparing nano grade super fine cobalt powder Download PDF

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CN1248813C
CN1248813C CN 200410068855 CN200410068855A CN1248813C CN 1248813 C CN1248813 C CN 1248813C CN 200410068855 CN200410068855 CN 200410068855 CN 200410068855 A CN200410068855 A CN 200410068855A CN 1248813 C CN1248813 C CN 1248813C
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powder
cobalt
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CN1586772A (en
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吴成义
张丽英
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Abstract

The present invention relates to a method for preparing nano-grade ultrafine cobalt powder. In the method, an airflow ultrasonic spraying thermal conversion method is adopted to prepare nano-grade CoOx precursor powder with the average crystal grain of less than 60 nm, and the powder is treated by calcination, cutting breaking, centrifugation, air drying and H2 reduction by a tube furnace at the low temperature of 520 to 550 DEG C to be prepared into the nano-grade Co powder with the average crystal grain of less than 80 nm. The used cobalt oxide powder is the nano-grade CoOx precursor powder with the average crystal grain of less than 60 nm prepared by the airflow ultrasonic spraying thermal conversion method at the low temperature of 68 to 128 DEG C. The present invention has the advantages of simple process, low cost and large-scale production by using the original reducing furnace; the grain size distribution interval of the cobalt powder is narrow, the average grain size of the powder is less than or equal to 80 nm, and the grains are spherical.

Description

A kind of preparation method of nano-grade superfine cobalt powder
Technical field
The invention belongs to the preparing technical field of metal dust in the metal material, the preparation method at a kind of nano-grade superfine cobalt powder end particularly is provided, be applicable to nanoscale, the suitability for industrialized production of cobalt dust.
Background technology
Metallic cobalt is applied in fields such as high-temperature alloy material, Hardmetal materials, functional material, corrosive wear resistant alloys material, chemical industry catalysis-catalyst material, diamond tool material widely, direct applied industry of these materials and technical field all are most important departments in the national economy, all need a large amount of metallic cobalts as the probing exploitation instrument in space flight and aviation engine, gas turbine generator, heavy artillery fire equipment, traffic, flint road, oil, colliery etc. etc.
Hard carbide industry almost is all industrial basic industries, only the industry China needs 700 tons of cobalt powders every year approximately, also will consume 300 tons/year every year in functional material, countries in the world increase year by year to the demand of cobalt, and the cobalt valency rises suddenly and sharply always on the international market, since World War II, each industrial power of the world all classifies metallic cobalt as strategy metal and lays in, this mainly is because the cobalt ore resource seldom focuses mostly on again in the economically less developed region, as areas such as Zaire and Africa in the world.China be poor cobalt state up to the later stage eighties, just finding has less cobalt ore resource, and reserves are very low, thus China every year except recovery section cobalt from alloy from waste, still want a large amount of cobalt of import.
The annual required cobalt powder of hard carbide industry is by the metal cobalt button of import mostly, makes Co (NO through nitric acid dissolve 3) 26H 2The O cobalt nitrate is made Co through oxalic acid treatment and roasting again 2O 3, use H again 2Reduce, make the cobalt powder of ultra-fine (0.8～2 μ m).Countries in the world all adopt this technology to prepare cobalt powder over nearly 80 years, in recent years along with the develop rapidly of material science, particularly the literature search in nearly ten years in the production technology of carbide alloy, is adopted the cobalt powder and the tungsten carbide powder of nano level superfine as can be known, can make the bending strength of carbide alloy double many, hardness and wearability also increase substantially, so countries in the world are to nano-cobalt powder, the technology of preparing of tungsten carbide powder, show great interest, compete very violent.
Nearly 5 years literature search as can be known, the method for preparing nano-grade superfine cobalt powder mainly contains, aqueous solution reducing process, sol-gel process, microemulsion method, (CVD) vapour deposition process, evaporation-condensation method (containing plasma evaporation, laser evaporation, electron beam evaporation cohesion).But though the nanoscale cobalt powder of first three methods production average grain diameter≤100nm, but production cost is too high, and production efficiency is very low, thereby over a long time can not large-scale industrial production, the cobalt powder average grain diameter that vapour deposition process is produced is thick, be generally 0.1～1.5 μ m, and equipment investment is big, production efficiency is low, the evaporation-condensation method, can produce the cobalt powder of 0.1～3 μ m, its equipment investment is big, and production efficiency is also very low.The ancient technology of original preparation cobalt powder, the cobalt powder though can be mass-produced, but the particle mean size of powder is thick (0.8～2 μ m), can not satisfy the needs of the scientific research and the new product development of ultrafine gain size far away, patent purpose of the present invention is to provide a kind of and directly prepares nano level superfine with the hot transformation approach of ullrasonic spraying (cobalt oxide powder of average grain diameter≤60nm) is through low temperature H 2Reduce, can directly make the technology of preparing of nano-cobalt powder.
Summary of the invention
The object of the present invention is to provide the preparation method at a kind of nano-grade superfine cobalt powder end, realized the suitability for industrialized production at nano-grade superfine cobalt powder end, improved powder purity, and reduced cost.
The present invention adopts the hot transformation approach of air-flow ullrasonic spraying to prepare the CoOx precursor powder of nanoscale average crystal grain＜60nm, through roasting, and shearing-crushing, centrifugal, air-dry, hydrogen reduction is prepared into the Co powder of nanoscale average crystal grain＜100nm in tube furnace.Employed cobalt oxide powder is to adopt 68～128 ℃ of hot transformation approach of air-flow ullrasonic spraying of low temperature, the CoOx precursor powder of the nanoscale average crystal grain＜60nm of preparation.Concrete preparation technology is:
1, cobalt ions aqueous solution preparation:
The preparation of the cobalt ions aqueous solution is pressed following relational expression with the relationship between quality of cobalt powder and is calculated:
When employing nitrate, during preparation 1kg nano Co powder,
Co (NO 3) 26H 2The molecular weight M=291.03 of O,
Wherein: cobalt content X 1= 58.933/ 291.03=20.249%,
Need Co (NO 3) 26H 2The quality Y of O 1= 291.03 * 1000/ 58.933=4938.32 grams (16.968mol) join crystal powder 4938.3 grams of above-mentioned cobalt nitrate in 4 liters of distilled water, constantly stir, fully after the dissolving, with 44 μ m screen filtration exogenous impurities, make the cobalt nitrate solution of 4.242mol/L concentration, change the conversion of ullrasonic spraying heat over to.
When selecting sulfate for use, except that the relationship between quality of pressing aqueous solution preparation of sulfate molecular formula calculating cobalt ions and cobalt powder, also the precursor powder of spraying gained should be cleaned repeatedly with distilled water before roasting, remove SO 4 2-Sulfate radical.
The preparation of the cobalt ions aqueous solution can be adopted the water-soluble cobalt salt class of any energy, as Sulfates CoSO is arranged 46H 2O; Nitrates has Co (NO 3) 26H 2O etc.By certain concentration proportioning, these salts directly are dissolved in promptly can be made into the aqueous solution that contains cobalt ions in the distilled water, acid group residual when considering follow-up roasting with reduction is different to the corrosiveness of equipment, when selecting sulfate for use, the precursor powder of spraying gained should be cleaned repeatedly with distilled water before roasting, remove SO 4 2-Sulfate radical.When selecting nitrate for use, residual NO in the precursor powder 3 -Nitrate ion can major part resolve into NO in roasting process 2Its to the corrosivity of equipment a little less than, therefore before roasting, can not adopt distilled water to clean the operation of acid group.
The present invention mainly adopts Co (NO 3) 26H 2O is a raw material.Because of Co (NO 3) 26H 2The molecular weight M=291.03 of O wherein contains cobalt amount X 1= 58.933/ 291.03=20.249%, so during preparation 1Kg nano-cobalt powder, need Co (NO 3) 26H 2The quality of O is Y 1= 291.03 * 1000/ 58.933=4938.32 grams (16.968mol) join crystal powder total 4938.3 grams of above-mentioned cobalt nitrate in 4 liters of distilled water, constantly stir, and after the dissolving, with 44 μ m screen filtration exogenous impurities, make the cobalt nitrate solution of 4.242mol/L concentration fully.Change the conversion of ullrasonic spraying heat over to.
2, air-flow ullrasonic spraying heat conversion preparation precursor powder:
Change the cobalt nitrate solution of preparation over to ullrasonic spraying hot transfer column and carry out the air-flow ultrasonic atomizatio and prepare the nanometer grade cobalt oxide precursor powder, the nozzle that uses is circumferential weld resonant mode air-flow ultrasonic atomizing nozzle.Nozzle spray angle α=45 °, whiff pressure (air) 2.5～3.5MPa, air-flow jet velocity 2～2.5 Mach numbers, 68～128 ℃ of hot blast temperatures, liquid stream transporting velocity 200ml/ branch, air-flow ullrasonic spraying heat is changed, and can be made into the cobalt oxide precursor powder of average grain diameter＜60m.
3, nitrate ion is removed in roasting:
In the precursor powder of nitrate preparation, because of containing NO 3 -Nitrate ion, at 450～500 ℃, low-temperature bake is 30～50 minutes in the air, can be with NO 3 -The nitrate anion branch is taken off, and obtains dry nano Co 2O 3Cobalt oxide powder.
4, shearing-crushing
With the high speed shear crusher machine of the cobalt oxide powder after the roasting, press cobalt oxide powder: industrial alcohol=1: 5 mass ratio adds industrial alcohol, together put in the batch can of cutter, under 10000 rev/mins of rotating speeds, calculate shear time by 15 minutes/100 gram powder, after shearing, emit slip.This operation is the bridged particle that forms in the broken roasting process, prevents that the cobalt powder particle is grown up in reduction process.
5, high speed centrifugation separates alcohol
Oxide slurry after the fragmentation is isolated industrial alcohol through high-speed continuous centrifuge, and slightly alcoholic cobalt oxide slip changes over to air-dry
6, air-dry:
Slightly alcoholic cobalt oxide slip is through the air-dry nanoscale Co that obtains drying 2O 3Powder changes the hydrogen reducing furnace reduction over to
7, hydrogen reduction prepares nano-cobalt powder
With the nano oxidized cobalt dust of drying, put into stainless steel tubular type reduction furnace, at 520～560 ℃, 45～60 minutes, use H 2The gas reduction, H 2Gas cross section flow, 80～100ml/cm 2Powder after the reduction is put into acetone-oleic acid liquid immediately after coming out of the stove, prevent spontaneous combustion.Make the 1Kg cobalt powder of average grain diameter≤80nm after coming out of the stove.
8, properties of product detect
Mainly carry out XRD, BET specific surface, TEM granule-morphology and granularity
9, product vacuum packaging
The product that performance is qualified carries out vacuum packaging
Advantage of the present invention:
(1) on the production technology and equipment a kind of new technology that can serialization large-scale production nano-grade superfine cobalt powder is provided.Technology is simple, and cost is lower.
(2) adopt shearing-crushing and continuous centrifugal isolation technics not only can eliminate bridged particle in the powder, and solved the problem of nano powder precipitate and separate difficulty in solution, thereby can guarantee that large-scale production normally carries out.
(3) the nanoscale cobalt powder of Sheng Chaning, good dispersion, narrow diameter distribution, average grain diameter＜80nm, grain shape almost spherical.
Description of drawings
Fig. 1 is preparation technology's flow chart of the present invention.Wherein, the cobalt nitrate aqueous solution preparation 1; Cobalt nitrate aqueous solution is carried out the conversion of ullrasonic spraying heat, preparation precursor powder 2; The roasting precursor powder is removed nitrate anion 3; Shearing-crushing 4 is with the bridged particle fragmentation in the precursor powder; High speed centrifugation separates alcohol 5, adopts high-speed continuous centrifuge that alcohol is separated fast with powder; Air-dry 6; Nanoscale Co with drying 2O 3Powder H 2Gas is reduced into nanoscale cobalt powder 7; Properties of product detect 8, and powder-product is carried out the BET specific surface, and XRD, TEM measure; Product vacuum packaging 9.
The specific embodiment
Embodiment 1: preparation 1kg nano-cobalt powder end should follow these steps to finish.
1, weighing:
Take by weighing 4938.32 gram Co (NO 3) 26H 2The O crystal powder joins in 4 liters of distilled water, constantly stirs, and the dissolving back is transferred to solution in the atomizing flow container with behind the 44 μ m screen filtration exogenous impurities fully.
2, air-flow ullrasonic spraying heat conversion:
Use the circumferential weld resonant mode air-flow ultrasonic atomizing nozzle of spray angle α=45 °, whiff pressure (air) 2.5MPa, 128 ℃ of hot blast temperatures, air-flow jet velocity 2 Mach numbers, liquid stream transporting velocity 200ml/ branch, solution can obtain the dry precursor powder after all having atomized, and changes the roasting stage over to.
3, roasting:
With precursor powder, in roaster 450 ℃, roasting under 50 fens air atmospheres is further decomposed eliminating with residual water in the precursor powder and micro-acid group.Obtain dry nanoscale Co 2O 3Cobalt oxide powder
4, shearing-crushing:
Press cobalt oxide powder: industrial alcohol=1: 5 mass ratio, add industrial alcohol and together pour in the flow container of cutter, under 10000 rev/mins of rotating speeds, calculate shear time by (15 minutes/100 gram powder), emit slip after the shearing.
5, high speed centrifugation separates alcohol
Oxide slurry after the shearing is isolated industrial alcohol with high-speed continuous centrifuge, and slightly alcoholic cobalt oxide slip changes air-dry operation over to.
6, air-dry
Slightly alcoholic cobalt oxide slip obtains dry nanoscale Co through natural air drying 2O 3Powder changes the hydrogen reducing furnace reduction over to.
7, hydrogen reducing prepares nano-cobalt powder
In stainless steel tubular type reduction furnace,, 60 minutes, use H at 520 ℃ 2The dry nanoscale Co of gas reduction 2O 3Powder, H 2Gas cross section flow, 80ml/cm 2Put into acetone-oleic acid liquid when the powder after the reduction is come out of the stove immediately, prevent spontaneous combustion.Promptly make the 1Kg cobalt powder of average grain diameter≤80nm.
8, properties of product detect
Mainly carry out XRD, BET specific surface, TEM granule-morphology and granularity
9, product vacuum aluminium bag packing
The product that performance is qualified carries out vacuum packaging
Embodiment 2 preparation 10kg nano-cobalt powder ends should follow these steps to finish.
1, weighing
Take by weighing 49.384kg Co (NO 3) 26H 2The O crystal powder joins in 40 liters of distilled water in the stainless steel NaOH solution tank NaOH, constantly stir dissolving fully after, the heat conversion of in 44 μ m screen filtration pipelines are injected into solution with liquid pump the flow container of atomisation tower, spraying.
2, air-stream spraying heat conversion
Use the circumferential weld resonant mode air-flow ultrasonic atomizing nozzle of jet angle α=45 °, whiff pressure (air) 3.5MPa, 68 ℃ of hot blast temperatures, liquid stream transporting velocity 200ml/ branch, air-flow jet velocity 2.5 Mach numbers, solution can obtain the dry precursor powder after all having atomized, and change calcining process over to.
3, roasting
With the precursor powder that obtains in above-mentioned 2, directly put into roaster, under the air atmosphere, temperature is 500 ℃, roasting 30 minutes can obtain dry cobalt oxide powder after the cooling of coming out of the stove, and changes the shearing-crushing operation over to.
4, shearing-crushing
Press cobalt oxide powder: industrial alcohol=1: 5 mass ratio, add industrial alcohol and together pour in the cutter flow container, calculate shear time by (15 minutes/100 gram powder), emit slip after the shearing.
5, high speed centrifugation separates
Cobalt oxide slurry after the shearing is isolated industrial alcohol with high-speed continuous centrifuge, and slightly alcoholic cobalt oxide slip changes air-dry operation over to.
6, air-dry
Slightly alcoholic cobalt oxide slip obtains dry nanoscale Co through natural air drying 2O 3Powder changes H over to 2The reduction operation
7, H 2The gas reduction
In stainless steel tubular type reduction furnace, 560 ℃, 45 minutes, use H 2The dry nanoscale Co of gas reduction 2O 3Powder, H 2Cross section flow 100ml/cm 2, 7 identical among all the other and the embodiment 1.Make the 10Kg cobalt powder of average grain diameter≤80nm after coming out of the stove
8,9 and embodiment 1 in 8,9 identical.

Claims (2)

1, a kind of preparation method of nano-grade superfine cobalt powder, the hot transformation approach of employing air-flow ullrasonic spraying prepares the CoOx precursor powder of nanoscale average grain diameter＜60nm, through roasting, shearing-crushing, centrifugal, air-dry, hydrogen reduction is prepared into the Co powder of nanoscale average grain diameter＜100nm in tube furnace; Employed cobalt oxide powder is to adopt 68～128 ℃ of hot transformation approach of air-flow ullrasonic spraying of low temperature, the CoOx precursor powder of the nanoscale average grain diameter＜60nm of preparation; Concrete technology is:
A, the preparation of the cobalt ions aqueous solution:
The preparation of the cobalt ions aqueous solution is pressed following relational expression with the relationship between quality of cobalt powder and is calculated:
When employing nitrate, during preparation 1kg nano Co powder,
Co (NO 3) 26H 2The molecular weight M=291.03 of O,
Wherein: cobalt content X 1= 58.933/ 291.03=20.249%,
Need Co (NO 3) 26H 2The quality Y of O 1= 291.03 * 1000/ 58.933=4938.32 grams (16.968mol) join crystal powder 4938.3 grams of above-mentioned cobalt nitrate in 4 liters of distilled water, constantly stir, fully after the dissolving, with 44 μ m screen filtration exogenous impurities, make the cobalt nitrate solution of 4.242mol/L concentration, change the conversion of ullrasonic spraying heat over to;
B, air-flow ullrasonic spraying heat conversion preparation precursor powder:
Change the cobalt nitrate solution for preparing over to ullrasonic spraying hot transfer column and carry out ullrasonic spraying heat conversion preparation nanometer grade cobalt oxide precursor powder, the nozzle that uses is circumferential weld resonant mode air-flow ultrasonic atomizing nozzle, nozzle spray angle α=45 °, whiff pressure air 2.5～3.5MPa, air-flow jet velocity 2～2.5 Mach numbers, 68～128 ℃ of hot blast temperatures, liquid flow transporting velocity 200ml/ branch, can be made into the cobalt oxide precursor powder of average grain diameter＜60nm after the conversion of air-flow ullrasonic spraying heat;
Nitrate ion is removed in c, roasting:
In the precursor powder of nitrate preparation, because of containing NO 3 -Nitrate ion, at 450～500 ℃, low-temperature bake is 30～50 minutes in the air, can be with NO 3 -The nitrate anion branch is taken off, and obtains dry nano Co 2O 3Cobalt oxide powder;
D, shearing-crushing:
With the high speed shear crusher machine of the cobalt oxide powder after the roasting, this operation is the bridged particle that forms in the broken roasting process, prevent that the cobalt powder particle is grown up in reduction process, press cobalt oxide powder: industrial alcohol=1: 5 mass ratio adds industrial alcohol, together put in the batch can of cutter, under 10000 rev/mins of rotating speeds,, calculate shear time by 15 minutes/100 gram powder, after the shearing, emit slip;
E, high speed centrifugation separate alcohol:
With industrial alcohol and nanometer grade cobalt oxide powder separation, slightly alcoholic cobalt oxide slip changes over to air-dry oxide slurry after the fragmentation with high-speed continuous centrifuge;
F, air-dry:
Slightly alcoholic cobalt oxide slip obtains dry nanoscale Co through air-dry 2O 3Powder changes the hydrogen reducing furnace reduction over to;
G, hydrogen reducing prepare nano-cobalt powder:
Nanoscale Co with drying 2O 3Powder is put into stainless steel tubular type reduction furnace, at 520～560 ℃, 45～60 minutes, uses H 2The gas reduction, H 2Gas cross section flow 80～100ml/cm 2Powder after the reduction is put into acetone-oleic acid liquid after coming out of the stove, prevent spontaneous combustion, promptly makes the 1Kg cobalt powder of average grain diameter≤80nm;
H, properties of product detect:
Carry out XRD, BET specific surface, TEM granule-morphology and granularity;
I, product vacuum packaging.
2, in accordance with the method for claim 1, it is characterized in that: CoSO is selected in the preparation of the cobalt ions aqueous solution for use 46H 2During O sulfate, except that the relationship between quality of pressing aqueous solution preparation of sulfate molecular formula calculating cobalt ions and cobalt powder, also the precursor powder of spraying gained should be cleaned repeatedly with distilled water before roasting, remove SO 4 2-Sulfate radical.
CN 200410068855 2004-07-09 2004-07-09 Process for preparing nano grade super fine cobalt powder Expired - Fee Related CN1248813C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007071108A1 (en) * 2005-12-21 2007-06-28 Shenzhen Gem High-Tech Joint-Stock Co., Ltd. Process of produceing superfine cobalt powder with circulation technology and its apparatus
CN100439014C (en) * 2006-01-26 2008-12-03 湖南凯丰新材料有限公司 Preparation method and equipment for nano-grade superfine cobalt powder
CN102631882A (en) * 2012-04-23 2012-08-15 常州亚环环保科技有限公司 Preparation method of magnetic nanometer material for treating 2-chlorine-3-pyridinecarbaldehydes waste
CN106077694B (en) * 2016-08-08 2017-11-28 南昌大学 A kind of preparation method of spherical cobalt powder
CN107570723B (en) * 2017-08-10 2019-12-03 湖南工业大学 Method for producing superfine cobalt powder for hard alloy by fluidized reduction of cobalt carbonate and production system thereof
CN111072073A (en) * 2019-12-20 2020-04-28 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of Ni monatomic doped cobaltosic oxide nano material, product and application thereof
CN111689478B (en) * 2020-06-11 2022-01-28 黄湛明 Preparation method and preparation system of high-purity nano selenium powder
CN113909485B (en) * 2021-10-11 2023-11-17 先导薄膜材料（广东）有限公司 Preparation method of superfine cobalt powder
CN115555575B (en) * 2022-09-21 2024-03-29 安徽格派锂电循环科技有限公司 Method for preparing nano cobalt particles by using thermal spraying method

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