CN1254337C - Preparation method of nanometer sized superfine ferro nickel alloy powder - Google Patents
Preparation method of nanometer sized superfine ferro nickel alloy powder Download PDFInfo
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- CN1254337C CN1254337C CN 200410009274 CN200410009274A CN1254337C CN 1254337 C CN1254337 C CN 1254337C CN 200410009274 CN200410009274 CN 200410009274 CN 200410009274 A CN200410009274 A CN 200410009274A CN 1254337 C CN1254337 C CN 1254337C
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Abstract
The present invention provides a method for manufacturing ultra-fine ferronickel alloy powder. In the method, a ferronickel sulfate or nitrate water solution is adopted to be prepared into nano-grade NiO. FeO composite oxide powder by a low-temperature ultrasonic spraying thermal conversion method; through repeated cleaning and centrifugal separation, or direct calcination for the removal of acid radicals and residual water in precursor powder, dried composite oxide powder is obtained; through H2 reduction by a tube furnace at the low temperature of 650 to 700 DEG C, the nano-grade ferronickel alloy powder can be manufactured. The present invention has the advantages of optional matching of ferronickel alloy components by solution components, uniform alloy component, average grain size of the alloy powder of no larger than 80 nm, spherical grain and large-scale industrial production.
Description
Technical field
The invention belongs to the preparing technical field of metal dust in the metal material, a kind of preparation method of nano level superfine dilval powder particularly is provided, be applicable to nanoscale, the suitability for industrialized production of dilval powder.
Background technology
Nano-nickel powder and nanometer dilval powder are applied in nickel one hydrogen fuel cell, the ultra micro metallic filter material widely, invisible coating, the chemical industry catalyzer contact agent, memorial alloy, superconducting alloy, magnetic material, the spraying alloy, carbide alloy, artificial diamond catalyst alloy, the diamond cut tool materials, cermet material etc.Along with the new and high technology develop rapidly, more and more big to the demand of nanometer dilval powder both at home and abroad in recent years, annual growth rate with 23% increases fast.By nearly 15 years literature search, the production method of existing as can be known nickel powder and dilval powder mainly contains the aqueous solution electrolysis method, the oxide hydrogen reduction method, aqueous solution reducing process (containing the High Pressure Hydrogen reduction), carbonyl process, atomization (aerosolization, hydraulic atomized), Hami tower Cyclone mill method etc.Preceding four kinds of methods, the powder size of production is thinner, as the aqueous solution electrolysis method, can produce the pure nickel powder of 30～180 μ m, can not produce ferronickel powder.Oxide H
2Reducing process and aqueous solution high pressure H
2Reducing process can be produced the pure nickel powder of 2.5～20 μ m, also can produce ferronickel powder, and granularity is about 2～15 μ m.Aqueous solution reducing process can be produced nanoscale, and (＜100nm) nickel powder, but cost is too high can not large-scale production.Carbonyl process is the nickel powder of producing ultra-fine (0.5～6 μ m) of generally acknowledging in the world and the Perfected process of ferronickel powder, but its operation is complicated, equipment investment is big, environmental pollution is serious, atomization (aerosolization, hydraulic atomized), with Hami tower Cyclone mill method, nickel powder and the dilval powder of 50～200 can only the production granularity thicker μ m.More than all methods all can not produce nanoscale nickel powder and dilval powder at an easy rate.Nearly 10 years literature search as can be known, adopt nanoscale pure nickel and ferronickel powder last reign of a dynasty for existing thick nickel and dilval powder, in a lot of materials and alloy field, show very excellent performance, particularly in the chemical industry catalyzer contact agent, use nanometer nickel and dilval powder, the catalyst conversion efficiency is significantly improved.At diamond synthesis catalyzer contact agent, diamond cut instrument, nickel-hydrogen battery pole plate, magnetic material, superconducting alloy, fields such as carbide alloy, nanometer nickel and ferronickel powder also demonstrate splendid performance, therefore over nearly 5 years to the demand rapid growth of nanometer nickel and ferronickel powder.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of nano level superfine dilval powder, realized the suitability for industrialized production of nano level superfine dilval powder, improved powder purity, and reduced cost.
The present invention adopts the hot transformation approach of air-flow ullrasonic spraying to prepare the NiOFeO precursor powder of nanoscale average crystal grain＜60nm, through roasting, and shearing-crushing, centrifugal, air-dry, hydrogen reduction is prepared into the Ni-Fe alloy powder of nanoscale average crystal grain＜100nm.Concrete preparation technology is:
1, ferronickel deionized water solution preparation
The preparation of ferronickel deionized water solution can be adopted the water-soluble ferronickel salt of any energy, as Sulfates NiSO is arranged
46H
2O, FeSO
47H
2O; Nitrates has Ni (NO
3)
26H
2O, Fe (NO
3)
39H
2O etc., Sulfates and Nitrates are by certain composition proportion, these salts directly are dissolved in promptly can be made into the ferronickel deionized water solution 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.Concrete computational methods are as follows:
The preparation of ferronickel deionized water solution should be calculated by following relational expression with the alloying component of dilval powder:
When adopting sulfate:
Wherein: M
1-(NiSO
46H
2O) molecular weight=262.85
M
2-(FeSO
47H
2O) molecular weight=278.01
M
(Ni)-Ni molecular weight=58.71
M
(Fe)-Fe molecular weight=55.847
As preparation 1kg, during the chemical machining nano Ni-Fe alloy powder, Ni/Fe=K/1 in the alloy.If when needing K=3, ask required nickel quality Ni and (NiSO
46H
2O) quality Y
1, (FeSO
47H
2O) quality Y
2, because of Ni/Fe=k/1 in the alloy, so
Need NiSO
46H
2The O quality is pressed following formula:
In like manner need FeSO
47H
2The O quality is calculated as follows:
With above-mentioned nickelous sulfate, the ferrous sulfate crystal powder amounts to 4602.3 grams, join and heat 50～60 ℃ of constantly stirrings in 10 liters of distilled water, fully after the dissolving, with 44 μ m screen cloth sieving exogenous impurities, change ullrasonic spraying heat conversion flow container over to, carry out the conversion of ullrasonic spraying heat.
When adopting nitrate
Wherein: M
3-Ni (NO
3)
26H
2O molecular weight=290.80
M
4-Fe (NO
3)
39H
2O molecular weight=404
M
(Ni)-Ni molecular weight=58.71
M
(Fe)-Fe molecular weight=55.847
During preparation 1kg nanoscale Ni-Fe alloy powder, Ni/Fe=K/1 in the alloy if need K=3, asks the nickel quality Ni that needs, and Ni (NO
3)
26H
2O quality Y
3, Fe (NO
3)
39H
2O quality Y
4, because of Ni/Fe=k/1 in the alloy; K=3, so
Need Ni (NO
3)
2.6H
2O quality Y
3
Need
Fe (NO
3)
3.9H
20Quality Y
4 
Above-mentioned nickel nitrate, ferric nitrate crystal powder are amounted to 5523.38 grams, join in 12 liters of distilled water, heat 50～60 ℃, constantly stir, after the dissolving,, change the conversion of ullrasonic spraying heat over to fully with 44 μ m screen filtration exogenous impurities.
2, air-flow ullrasonic spraying heat conversion preparation precursor powder
Change the ferronickel deionized water solution of preparation over to ullrasonic spraying hot transfer column and carry out the air-flow ultrasonic atomizatio and prepare NiOFeO nanoscale amorphous state precursor powder, the nozzle that uses is circumferential weld resonant mode air-flow ultrasonic atomizing nozzle.Nozzle 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, the heat conversion of air-flow ullrasonic spraying can be made into the pure nickel of average grain diameter＜60nm or nickel oxide, iron oxide composite oxides nanometer precursor powder.
3, acid ion is removed in roasting, cleaning
In the precursor powder of sulfate preparation because of containing residual sulfate radical SO
4 2-So precursor powder need be cleaned in distilled water repeatedly, separates waste liquid with continuous centrifuge, until using BaCl
2Aqueous assay did not have till when precipitation.Precursor powder with the nitrate preparation is identical then, low-temperature bake.
In the precursor powder of nitrate preparation, because of containing NO
3 -Nitrate ion, at 350～450 ℃, 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 nanometer ferronickel composite oxide power.
4, shearing-crushing
With the high speed shear crusher machine of the composite oxide power after the roasting, press oxidate powder: industrial alcohol=1: 5 mass ratio, add 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.Industrial alcohol is separated the industrial alcohol natural air drying of residual minute quantity in the precursor powder with continuous centrifuge with the nanoscale precursor powder.This operation is the bridged particle that forms in the broken roasting process, prevents that the Ni-Fe particle is grown up in reduction process.
Oxide slurry after the fragmentation is isolated industrial alcohol through supercentrifuge, and slip changes the hydrogen reducing furnace reduction over to through the air-dry composite oxide power of drying that obtains
5, hydrogen reduction prepares nanometer dilval powder
With the nano composite oxide powder of drying, put into stainless steel tubular type reduction furnace, at 650～700 ℃, 45～60 minutes, use H
2The gas reduction, H
2Gas cross section flow, 30～50ml/cm
2Powder after the reduction is put into acetone-oleic acid liquid immediately when coming out of the stove, prevent spontaneous combustion.Make the Ni-Fe alloy powder of average grain diameter≤80nm after coming out of the stove.
6, properties of product detect
Mainly carry out XRD, BET specific surface, TEM granule-morphology and granularity
Advantage of the present invention:
(1) on the production technology and equipment provide a kind of can serialization large-scale production nano level superfine nickel and the new technology of dilval powder.Cost is lower.
(2) composition of dilval can be allocated arbitrarily by the concentration of metal ions proportioning of two kinds of salt, obviously also can produce pure nickel or pure iron nanometer powder.
(3) 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.
(4) the nanoscale dilval powder of Sheng Chaning, alloying component is very even, the narrow diameter distribution of powder, average grain diameter＜80nm, grain shape almost spherical.
Description of drawings
The present invention is further described below in conjunction with accompanying drawing.
Fig. 1 is preparation technology's flow chart of the present invention, wherein, and ferronickel deionized water solution preparation 1; The ferronickel deionized water solution is carried out the conversion of ullrasonic spraying heat, preparation precursor powder 2; Roasting precursor powder, this operation only are suitable for 3 when adopting nitrate raw material; Clean with distilled water repeatedly, remove SO
4 2-Sulfate radical 4, this operation are suitable for when adopting the sulfate raw material; Shearing-crushing 5 is with the bridged particle fragmentation in the precursor powder; Centrifugation 6 is to adopt continuous centrifugal machine that washing lotion is separated fast with powder; Air-dry 7; H
2Gas reduction 8 is reduced into nanoscale dilval powder with composite oxide power; Properties of product detect 9, and powder-product is carried out the BET specific surface, and XRD, TEM measure; Product vacuum packaging 10.
The specific embodiment
Embodiment 1: preparation 1kg nanometer dilval powder, composition is Ni: Fe=3: 1 o'clock, should follow these steps to finish.
1, takes by weighing 1244.52 gram FeSO respectively
47H
2O and 3357.8 gram NiSO
46H
2The O powder joins in 10 liters of distilled water, is heated to 60 ℃ and constantly stirs, and the dissolving back is transferred to solution in the atomizing flow container with behind the 40 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 jet angle α=45 °, whiff pressure (air) 2.5MPa, 128 ℃ of hot blast temperatures, air-flow jet velocity 2～2.5 Mach numbers, liquid stream transporting velocity 200ml/ branch, solution can obtain the dry precursor powder after all having atomized, and changes wash phase repeatedly over to.
3, clean repeatedly, centrifugation is pressed powder with precursor powder: water=1: 5 mass ratio, add distilled water, and constantly stir, with SO
4 2-Sulfate ion is dissolved in the water, then, muddy liquid is constantly joined in the continuous centrifugal machine waste liquid is constantly got rid of, and then add fresh distilled water, stirs repeatedly in centrifuge, cleaning, centrifugation be until waste liquid BaCL
2Be cleaning when test, no white precipitate and finish, powder agglomates is taken out natural air drying from centrifuge, change reduction over to.
4, with the precursor powder after air-dry, in roaster 360 ℃, roasting under 50 fens air atmospheres is further decomposed eliminating with residual water in the precursor powder and micro-acid group.
5, shearing-crushing, press the presoma powder: industrial alcohol=1: 5 mass ratio, add industrial alcohol and together pour the flow container of cutter into, under 10000 rev/mins of rotating speeds, calculate shear time by (15 minutes/100 gram powder), emit slip after the shearing, isolate industrial alcohol with continuous centrifuge, but the slip natural air drying.
6, in the tubular type reduction furnace 650 ℃, 60 minutes, use H
2The gas reduction, H
2Gas cross section flow 30ml/cm
2, can obtain the nanometer dilval powder of 1kg after the operation through reduction, the powder after the reduction should be put into acetone-oleic acid liquid immediately and prevent spontaneous combustion when coming out of the stove.
7, the gained powder is carried out BET specific surface XRD phase composition, the every detection of TEM granularity and granule-morphology.
8, product vacuum aluminium bag packing.
Embodiment 2 preparation 10kg nanometer dilval powder, alloying component is Ni: Fe=3: 1 o'clock, should follow these steps to finish.
1, takes by weighing Ni (NO respectively
3)
26H
2O, 37.1487kg; Fe (NO
3)
39H
2O, 18.0851kg, crystal powder joins in 120 liters of distilled water and be heated to 50 ℃ in the stainless steel reaction jar, 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, solution can obtain the dry precursor powder after all having atomized, and changes calcining process over to.
3, with the precursor powder that obtains in above-mentioned 2, directly put into the roaster roasting, temperature is 450 ℃, and 30 minutes air atmospheres can obtain dry composite oxide power after the cooling of coming out of the stove, and should change the shearing-crushing operation.
4, press composite oxide powder: industrial alcohol=1: 5 mass ratio, add industrial alcohol and together pour in the cutter flow container, calculate shear time, emit slip after the shearing by (15 minutes/100 gram powder), isolate industrial alcohol with continuous centrifuge, treat to change the reduction operation over to behind the slip natural air drying
5, in the tubular type reduction furnace, 700 ℃, used H in 45 minutes
2The gas reduction, H
2Cross section flow 50ml/cm
2, 5 identical among all the other and the embodiment 1.
6,7 and embodiment 1 in 7,8 identical.
Claims (1)
1, a kind of preparation method of nano level superfine ferronickel powder, adopt the hot transformation approach of air-flow ullrasonic spraying to prepare the NiOFeO precursor powder of nanoscale average crystal grain＜60nm, through roasting, shearing-crushing, centrifugation, air-dry, in tube furnace, use hydrogen reducing, be prepared into the Ni-Fe alloy powder of nanoscale average crystal grain＜100nm; It is characterized in that:
The water-soluble ferronickel salt of a kind of energy is adopted in a, the preparation of ferronickel deionized water solution, and Sulfates has NiSO
46H
2O, FeSO
47H
2O; Nitrates has Ni (NO
3)
26H
2O, Fe (NO
3)
39H
2O, Sulfates and Nitrates are pressed certain composition proportion, these salts directly are dissolved in make the ferronickel deionized water solution in the distilled water, 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;
B, air-flow ullrasonic spraying heat conversion preparation precursor powder
Changing the ferronickel deionized water solution of preparation over to ullrasonic spraying hot transfer column carries out the air-flow ultrasonic atomizatio and prepares NiOFeO nanoscale amorphous state precursor powder, the nozzle that uses is circumferential weld resonant mode air-flow ultrasonic atomizing nozzle, jet angle α=45 °, jet air pressure 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;
Acid ion is removed in C, roasting, cleaning
In the precursor powder of sulfate preparation because of containing residual sulfate radical SO
4 2-So precursor powder need be cleaned in distilled water repeatedly, separates waste liquid with continuous centrifuge, until using BaCl
2Aqueous assay did not have till when precipitation; Precursor powder with the nitrate preparation is identical then, low-temperature bake.
In the precursor powder of nitrate preparation because of containing residual nitric acid root NO
3 -, at 350～450 ℃, low-temperature bake is 30～50 minutes in the air, with NO
3 -The nitrate anion branch is taken off, and obtains dry nanometer ferronickel composite oxide power;
D, shearing-crushing
With the 10000 rev/mins of cutter fragmentations at a high speed of the composite oxide power after the roasting, press oxidate powder: industrial alcohol=1: 5 mass ratio, add industrial alcohol, under 10000 rev/mins of rotating speeds, calculate shear time by 15 minutes/100 gram powder, emit slip after the shearing, industrial alcohol is separated with the nanoscale precursor powder with continuous centrifuge, but the industrial alcohol natural air drying of residual minute quantity in the precursor powder;
E, hydrogen reduction prepare nanometer dilval powder
With the nano composite oxide powder of drying, put into stainless steel tubular type reduction furnace, at 650～700 ℃, 45～60 minutes, use H
2The gas reduction, H
2Gas cross section flow, 30～50ml/cm
2Powder after the reduction is put into acetone-oleic acid liquid immediately when coming out of the stove, prevent spontaneous combustion, makes the Ni-Fe alloy powder of average grain diameter≤80nm after coming out of the stove.
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|---|---|---|---|
| CN 200410009274 CN1254337C (en) | 2004-06-29 | 2004-06-29 | Preparation method of nanometer sized superfine ferro nickel alloy powder |
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| CN100363134C (en) * | 2005-11-25 | 2008-01-23 | 北京科技大学 | Method for preparing nano nickel powder by precipitation-hydrogen reduction process |
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| CN104889415A (en) * | 2015-06-17 | 2015-09-09 | 北京科技大学 | Preparation method of nano nickel powder |
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| CN106166614A (en) * | 2016-08-23 | 2016-11-30 | 金川集团股份有限公司 | A kind of preparation method of high-temperature nickel-base alloy powder |
| CN108568529A (en) * | 2018-05-18 | 2018-09-25 | 海安南京大学高新技术研究院 | The preparation method of spherical Fe-Ni alloy/C powder |
| CN108723380A (en) * | 2018-06-07 | 2018-11-02 | 江西离子型稀土工程技术研究有限公司 | A kind of preparation method of rare earth-iron base pre-alloyed powder |
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| CN110961658A (en) * | 2018-09-28 | 2020-04-07 | 荆门市格林美新材料有限公司 | Preparation method of iron-doped superfine nickel powder |
| CN110961653A (en) * | 2018-09-28 | 2020-04-07 | 荆门市格林美新材料有限公司 | Preparation method of copper-doped superfine nickel powder |
| CN110586950A (en) * | 2019-10-14 | 2019-12-20 | 王敏 | Method for preparing 3D printing material by using titanium dioxide byproduct |
| CN111545767B (en) * | 2020-05-21 | 2021-10-15 | 西北有色金属研究院 | Preparation method of nanoscale multicomponent alloy |
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Assignee: Beijing Shangjia Alloy Co.,Ltd. Assignor: University of Science and Technology Beijing Contract fulfillment period: 2007.6.15 to 2012.6.15 contract change Contract record no.: 2009990000736 Denomination of invention: Preparation method of nanometer sized superfine ferro nickel alloy powder Granted publication date: 20060503 License type: Exclusive license Record date: 2009.7.9 |
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