CN104625082B - Nanometer nickel powder preparation method - Google Patents
Nanometer nickel powder preparation method Download PDFInfo
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- CN104625082B CN104625082B CN201510084027.8A CN201510084027A CN104625082B CN 104625082 B CN104625082 B CN 104625082B CN 201510084027 A CN201510084027 A CN 201510084027A CN 104625082 B CN104625082 B CN 104625082B
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Abstract
The invention belongs to the technical field of material processing, and particularly relates to a nanometer nickel powder preparation method. The nanometer nickel powder preparation method comprises the following six steps of burdening, combining, filtering, drying, fluidized bed reduction and breaking. The ratio and the concentration of raw materials in a burdening process, the ratio and the concentration of additives and surface active agents and the reaction pH (potential of hydrogen) and the reaction temperature in the step of combining are controlled, so that precursors of nickel powders with different shapes and different grain diameters are prepared. The precursors of the nickel powders with the different shapes are dried, reduced and broken to obtain nickel powder particles with different shapes. In a reduction process, the nickel powder is protected by inert gas, and the low oxygen content of the nickel powder is guaranteed; by a fluidized bed technology, reduction is sufficient, hydrogen use ratio is increased, and investment on equipment is reduced; and a filtering technological process is used in a filtering fluid circulating technology, waste fluid is circulated, environmental pollution is reduced, and energy consumption is also reduced. The prepared nickel powder can be spherical, similarly spherical, platy, branch-shaped, fibrous and the like; the shape of the prepared nickel powder is controllable; and the grain sizes of the nanometer nickel powder are 50-800 nanometers.
Description
Technical field
The invention belongs to materials processing technology field, and in particular to a kind of method for preparing nanoscale nickel powder, the method with
Metallic nickel crystal is raw material, and using Moist chemical synthesis fire reduction method nanoscale nickel powder is prepared.
Background technology
Current nickel powder production technology mainly includes carbonyl process, gas phase reduction process, normal pressure liquid phase reduction, solid phase reduction
Method, gamma Rays method, wherein the most commonly used with carbonyl process.Carbonyl process, i.e., make under 573-673K Ni (CO) in decomposer4
Decompose, by adjusting technological parameter, control forming core, growth, reunion and the sintering behavior of metal nickel powder, prepare " chain pearl " shape shape
The extra-fine nickel powder of looks, in being processed further, it is easy to form tridimensional network, is particularly well-suited to the neck such as electrodes conduct additive
Domain.The method is broadly divided into two steps and carries out, and makes CO generate carbonyl nickel (CO) with nickel reactant first4, then in thermal decomposition furnace
Decompose carbonyl nickel and obtain nickel powder.Nickel powder granularity obtained by different thermal decomposition furnaces is different with pattern, such as wall heating type pyrolysis oven
It is in chain pearl that the nickel powder of production shows the aobvious near-spherical of nickel powder of spherical, pre-heated pyrolysis oven production, the nickel powder of Recuperative heat type pyrolysis oven production
Shape；Gained nickel powder granularity has preferable application performance typically more than 1 μm, is particularly well-suited to the fields such as electrodes conduct additive.
International Nickel company of Canada Ltd. (INCO) and Russia north nickel company (Norisk) possess the carbonyl process of nickel and extract and process technology,
Occupy rank first, carbonyl process production technology has low cost, it is excellent that product purity is high, pattern and granularity can easily be accommodated etc.
Point, but carbonyl nickel belongs to extremely toxic substance, and equipment requirement is high, control difficulty is big, and foreign technology block in addition, China fails always comprehensively
Grasp.
Gas phase reduction process is that nickel metallic solution and hydrocarbon containing oxygen atom are placed in into hydrocarbon to burn
Reactor in decomposition-reduction prepare extra-fine nickel powder.The method realize industrialization, prepared nickel powder have good sphericity and
The features such as narrow particle size distribution, have been widely used and replace precious metal palladium in ceramic capacitor.Vapor phase method mainly includes wire electricity
Blasting procedure, carbonyl nickel thermal decomposition method and vaporize-condensation law.Powder granularity wider distribution prepared by wire electric blasting method, carbonyl
Nickel powder purity height, dispersiveness, chemism height prepared by nickel thermal decomposition method, but it is poisonous, it is unfriendly to environment.Vapor-condensate method
Low production efficiency, particle is oxidizable and equipment is complicated, and cost intensive is difficult to industrialization.
Normal pressure liquid phase reduction is at ambient pressure to be coordinated in nickel ion, nickel in the aqueous solution or organic system with reducing agent
Solion or insoluble compound are reduced, the method for obtaining nano nickel particles.Solid phase reduction method be by metallic nickel directly with
There is solid-state displacement reaction to prepare extra-fine nickel powder in reduction simple substance.Gamma Rays method is that water Jing gamma Rays produce primary producing
Metallic nickel ions gradual deoxidizing, newly-generated nickle atom aggregation nucleation can be ultimately generated nanometer by thing, wherein reproducibility particle
Grain.
Chinese invention patent CN02147855 discloses a kind of preparation method of fibrous nickel powder, using precipitation critical heat point
Solution Ni at normal temperatures2+-NH3-NH4+-Cl--C2O4 2--H2The precursor synthesis process of nickel powder preparation, Yi Jihou are carried out in O systems
Presoma is resolved into nickel powder by continuous thermal decomposition process, nickel powder prepared by the invention in threadiness, granularity be nanoscale, porous,
Specific surface area is big, can meet the requirement of various performances.Chinese invention patent CN03159577 disclose fibrous nickel powder with
The preparation method of nickel protoxide powder, using precipitation conversion thermal decomposition method, in Ni under normal temperature and pressure conditionses2+-NH3-NH4+-Cl--
SGn--C2O4 2--H2Synthesize nickel powder or nickel protoxide powder presoma in O systems, under oxidation with non-oxidizing conditions forerunner is thermally decomposed
Body is finally obtained threadiness nickel protoxide powder and fibrous nickel powder.The invention safe preparation process reliability, nontoxic pollution-free, nickel powder
With nickel protoxide powder in threadiness, granularity is nanoscale, porous, specific surface area are big, and nickel powder anti-aging capability is strong.
But fibrous nickel powder can only be produced in above-mentioned prior art, for remaining shape such as spherical, beaded, dendroid,
According to production Reasonable Regulation And Control selection cannot be needed to prepare nickel powder pattern, grain graininess.Multi items, many specifications, small grain size little Song ratio,
Small grain size great Song ratio, big granularity great Song represent the developing direction in nickel powder later stage than nickel powder, therefore, we should actively study difference
Kind nickel powder new technology, develops the new product of these high technology contents, high added value, and steps up product technology content,
Nickel powder product diversification is made, the different application of nickel powder is opened up.
The content of the invention
To solve above-mentioned deficiency of the prior art, it is an object of the invention to provide spherical, fiber can be produced as needed
The method of shape, a shape nickel powder, nickel powder prepared by the method is complete in specifications, numerous in variety, and oxygen content is low, is capable of achieving industrialization stable
Continuously run, energy consumption is low, industrial water circulation is utilized, environmental pollution is little.For achieving the above object the present invention is by following technology
Scheme is realized：
A kind of preparation method of nanoscale nickel powder, it is characterised in that comprise the following steps：
(1) dispensing：By complexing agent, additive, water three mixing, mother liquor is obtained；Metallic nickel crystal is added into mother liquor,
Metallic nickel crystal is completely dissolved in mother liquor, obtain nickel metallic solution；The metallic nickel crystal is nickel sulfate hexahydrate crystal, nickel chloride crystalline substance
Body, nickel acetate, nickel nitrate；
(2) synthesize：Deionized water and surfactant are first added in reactor, afterwards nickel metallic solution is added to anti-
In answering device, the pH value for controlling solution in reactor with the precipitating reagent that molar concentration is 0.1～10.0mol/L is 7～12, and control is anti-
Temperature is answered for 20～100 DEG C, the reaction time is 2～40h；
(3) filter, be dried：The reacted solution of Jing steps (2) is filtered, wherein filtrate centralized collection is used as mother liquor
In the preparation of nickel metallic solution；Powdered nickel precursor body is obtained after Washing of Filter Cake, drying；
(4) fluid bed reduction：Powdered nickel precursor body is placed in fluid bed dynamic reduction furnace and is reduced, control temperature 300～950
DEG C, the recovery time is 3-6 hours；
(5) crush：By the nickel powder after reduction, inlet air flow disintegrating apparatus is crushed under inert atmosphere protection, you can prepared
Go out Fisher particle size in 50～800 nanoscale nickel powders, the inert gas is high pure nitrogen, argon gas or their mixture.
Wherein, additive described in step (1) and the volume ratio of water are 1: 1～1: 30, and optimum ratio is 1: 5～1:
20, more excellent ratio is 1: 5～1: 10.
Wherein, surfactant described in step (2) is neopelex, fatty acid sorbitan, lauryl sulphur
The mixture of one or more of sour sodium, polyvinylpyrrolidone.
Wherein, complexing agent described in step (1) is ammoniacal liquor；The additive is ethanol, tartaric acid, citric acid, ethylenediamine
The mixture of one or more in tetraacethyl disodium.
Wherein, metal nickel concentration and the mol ratio of ammonia concn are 1: 1～1 in metallic nickel mixed solution in step (1):
15, optimum ratio is 1: 5～1: 15, and more excellent ratio is 1: 10～1: 15.
Wherein, precipitating reagent is in oxalic acid, oxalates, carbonate, bicarbonate, NaOH, potassium hydroxide in step (2)
One kind, the optimum concentration of precipitating reagent is 3.0～7.0mol/L, and more excellent concentration is 5.0～6.0mol/L.
Preferably, pH value in reaction optimum in step (2) is 9.0～11.0, and more excellent pH is 9.0-10.0.
Preferably, reaction temperature optimum in step (2) is 85～100 DEG C, and more excellent reaction temperature is 95-
100℃。
Preferably, reduction temperature optimum in step (4) is 650～950 DEG C, and more excellent reduction temperature is 800-
950℃。
Compared to the prior art advantages of the present invention and good effect, are mainly shown as：(1) using under inert atmosphere protection
Enclosed air-stream breaking method, make nickel powder oxygen content in shattering process not change；(2) the nickel powder granularity prepared is
50-800 nanometers, and can be needed and application according to different productions, the nickel powder of different grain size, different size is prepared, accomplish nickel
Powder Particle Size is controllable；(3) powdered nickel precursor body is prepared using Moist chemical synthesis, according to the pattern of the Morphological control nickel powder of presoma, there is ball
It is shape, dendritic to the different morphologies such as polyhedral, morphology controllable；(4) it is used for the preparation of molten metal, circulation profit after filtrate centralized collection
With realizing that zero-emission, environmental pollution are little.
The nanoscale nickel powder of present invention production is spherical, spherical, sheet, bar-shaped, dendritic, threadiness；Granularity is in 50-
800 nanoscale nickel powders (granularity is adjustable)；Metallic impurity elements total amount≤0.07%, carbon≤0.035%, specific surface area 3-20m2/
G, apparent density 0.3-1.2g/cm3, iron≤0.01%, sulphur≤0.01%, oxygen≤0.4%, and according to different applications,
Different customer demand production different size, the nickel powders of different series, meets the market demand.
Description of the drawings
Fig. 1 is the process chart of the nickel powder prepared using the inventive method；
The powdered nickel precursor body of Fig. 2 embodiments 1 and nickel powder form；
The powdered nickel precursor body of Fig. 3 embodiments 2 and nickel powder form；
The powdered nickel precursor body of Fig. 4 embodiments 3 and nickel powder form；
The powdered nickel precursor body of Fig. 5 embodiments 4 and nickel powder form；
The powdered nickel precursor body of Fig. 6 embodiments 5 and nickel powder form；
The powdered nickel precursor body of Fig. 7 embodiments 6 and nickel powder form；
The powdered nickel precursor body of Fig. 8 embodiments 7 and nickel powder form；
The powdered nickel precursor body of Fig. 9 embodiments 8 and nickel powder form；
The powdered nickel precursor body of Figure 10 embodiments 9 and nickel powder form；
The powdered nickel precursor body of Figure 11 embodiments 10 and nickel powder form；
The powdered nickel precursor body of Figure 12 embodiments 11 and nickel powder form.
Specific embodiment
Explanation is further explained to the present invention with reference to specific embodiment, but protection scope of the present invention is not limited to
Following examples.
Embodiment 1
This example processing process figure is as shown in Figure 1.According to ethanol: tartaric acid: the volume ratio of water is 1: 1: 7, metallic nickel
Concentration is 1: 11 with the mol ratio of ammonia concn, and the mixing that nickel sulfate hexahydrate crystal is completely dissolved in into ammonia water-ethanol-tartaric acid-water is molten
In liquid, ammoniacal liquor is made into into the solution that concentration is 1.5mol/L, deionized water 3L is added in reactor, add the surfactant moon
Osmanthus base sodium sulfonate 46g.
3L metal nickel solutions, oxalic acid ammonia solution are added in 30L reactors by measuring pump, adjustment pH value 10.8 ±
0.05, temperature is maintained at 55 ± 1 DEG C, after completion of dropwise addition, and through Filter Press, washing, filtrate is used for metal after being collected separately
The preparation of nickel mixed solution, filter cake is obtained powdered nickel precursor body nickel oxalate after oven drying.The presoma of nickel powder is placed in into stream
Change and reduced in bed dynamic reduction furnace, control 800 DEG C of reduction temperature, the nickel powder after reduction is close using 99.99% argon gas protection
Enclosed airflow crash equipment is crushed.
50 nanometers of analysis test nickel powder Fisher particle size.Electric Microscopic observation powdered nickel precursor body and nickel powder pattern are in threadiness, such as
Shown in Fig. 2.
Embodiment 2
This example processing process figure is as shown in Figure 1.Volume ratio according to citric acid and water is 1: 1, metal nickel concentration with
The mol ratio of ammonia concn is 1: 1, nickel nitrate crystal is completely dissolved in the mixed solution of ammoniacal liquor-citric acid-water, nickel in solution
Ion concentration is 2.0mol/L, and precipitating reagent is made into into the solution that concentration is 0.1mol/L, and 3L deionized waters are added in reactor,
And add the smooth 33g of surfactant fatty acid sorb.
3L metal nickel solutions, sodium carbonate liquor are added in 30L reactors by measuring pump, temperature is maintained at 100 ± 1
DEG C, pH value control 7.0 ± 0.05, after completion of dropwise addition filter, filtrate collect after for nickel metallic solution preparation, filter cake Jing from
Powdered nickel precursor body nickelous carbonate is obtained after heart washing, microwave drying, the presoma of nickel powder is placed in fluid bed dynamic reduction furnace also
Original, controls 300 DEG C of reduction temperature, and the nickel powder after reduction is entered using 99.99% nitrogen protection enclosed air-stream disintegrating apparatus
Row is broken.
520 nanometers of analysis test nickel powder Fisher particle size.Electric Microscopic observation powdered nickel precursor body and nickel powder pattern shape spherical in shape, such as
Shown in Fig. 3.
Embodiment 3
This example processing process figure is as shown in Figure 1.Volume ratio according to ethanol and water is 1: 30, metal nickel concentration and ammonia
The mol ratio of water concentration be 1: 15, nickel chloride crystal is completely dissolved in the mixed solution of ammoniacal liquor-alcohol-water, in solution nickel from
Sub- concentration is 0.6mol/L, and precipitating reagent is made into into the solution that concentration is 10.0mol/L, and 3L deionized waters are added in reactor,
And add surfactant sodium dodecyl base benzene sulfonic acid sodium salt 27g.
3L metal nickel solutions, Potassium Oxalate Solution are added in 30L reactors by measuring pump, temperature is maintained at 20 ± 1
DEG C, pH value is controlled 12 ± 0.05, and after completion of dropwise addition, filtration, mother liquor are collected separately after recruiting is used for metallic nickel mixed solution
Prepare, filter cake is obtained powdered nickel precursor body nickel oxalate Jing after centrifuge washing, microwave drying.The presoma of nickel powder is placed in into fluid bed to move
Reduce in state reduction furnace, control 650 DEG C of reduction temperature, the nickel powder after reduction is protected into closed gas using 99.99% nitrogen
Stream disintegrating apparatus is crushed.
350 nanometers of analysis test nickel powder Fisher particle size, electric Microscopic observation powdered nickel precursor body and nickel powder pattern are in polyhedral,
As shown in Figure 4.
Embodiment 4
This example processing process figure is as shown in Figure 1.Volume ratio according to disodium ethylene diamine tetraacetate and water is 1: 20, gold
Category nickel concentration is 1: 10 with the mol ratio of ammonia concn, and nickel acetate crystal is completely dissolved in into ammoniacal liquor-disodium ethylene diamine tetraacetate-water
Mixed solution in, nickel ion concentration is 0.8mol/L in solution, precipitating reagent is made into into the solution that concentration is 5.0mol/L, to anti-
Addition 3L deionized waters in device are answered, and adds surfactant polyvinylpyrrolidone 45g.
3L metal nickel solutions, potassium hydroxide solution are added in 30L reactors by measuring pump, temperature is maintained at 50 ±
1 DEG C, pH value is controlled 11.0 ± 0.05, after completion of dropwise addition, filter, washing, be dried after powdered nickel precursor body nickel hydroxide is obtained.Will
The presoma of nickel powder is placed in fluid bed dynamic reduction furnace and reduces, and controls 450 DEG C of reduction temperature, and the nickel powder after reduction is adopted
99.99% nitrogen protection enclosed air-stream disintegrating apparatus is crushed.
250 nanometers of analysis test nickel powder Fisher particle size, powdered nickel precursor body and nickel powder pattern are in spherical " like a chain of pearls or a string of beads " under Electronic Speculum
Shape, as shown in Figure 5.
Embodiment 5
This example processing process figure is as shown in Figure 1.Volume ratio according to ethanol and water is 1: 15, metal nickel concentration and ammonia
The mol ratio of water concentration be 1: 13, nickel nitrate crystal is completely dissolved in the mixed solution of ammoniacal liquor-alcohol-water, in solution nickel from
Sub- concentration is 1.0mol/L, and precipitating reagent is made into into the solution that concentration is 6mol/L, and 3L deionized waters are added in reactor, and is added
Enter surfactant polyvinylpyrrolidone 23g.
3L metal nickel solutions, sodium oxalate solution are added in 30L reactors by measuring pump, temperature is maintained at 85 ± 1
DEG C, pH value is controlled 9.0 ± 0.05, after completion of dropwise addition, filter, washing, be dried after powdered nickel precursor body nickel oxalate is obtained, by nickel powder
Presoma be placed in fluid bed dynamic reduction furnace in reduce, control 950 DEG C of reduction temperature, by after reduction nickel powder adopt
99.99% nitrogen protection enclosed air-stream disintegrating apparatus is crushed.
50 nanometers of analysis test nickel powder Fisher particle size, powdered nickel precursor body and nickel powder pattern are in dendroid under Electronic Speculum, such as Fig. 6 institutes
Show.
Embodiment 6
This example processing process figure is as shown in Figure 1.Volume ratio according to tartaric acid and water is 1: 10, metal nickel concentration with
The mol ratio of ammonia concn is 1: 10, and nickel acetate crystal is completely dissolved in the mixed solution of ammoniacal liquor-tartaric acid-water, in solution
Nickel ion concentration is 1.5mol/L, and precipitating reagent is made into into the solution that concentration is 7.0mol/L, and 3L deionizations are added in reactor
Water, and add surfactant dodecyl sodium sulfate 36g.
3L metal nickel solutions, ammonium bicarbonate soln are added in 30L reactors by measuring pump, temperature is maintained at 85 ±
1 DEG C, pH value is controlled 8.0 ± 0.05, and after completion of dropwise addition, filter cake is obtained nickel powder through Filter Press, washing, after oven drying
Presoma nickelous carbonate, the presoma of nickel powder is placed in fluid bed dynamic reduction furnace and is reduced, and 650 DEG C of reduction temperature is controlled, by also
Nickel powder after original is crushed using 99.99% argon gas protection enclosed air-stream disintegrating apparatus.
720 nanometers of analysis test nickel powder Fisher particle size.Powdered nickel precursor body and nickel powder pattern are in ball sheet, as shown in Figure 7.
Embodiment 7
This example processing process figure is as shown in Figure 1.Volume ratio according to tartaric acid and water is 1: 10, metal nickel concentration with
The mol ratio of ammonia concn is 1: 5, nickel sulfate hexahydrate crystal is completely dissolved in the mixed solution of ammoniacal liquor-tartaric acid-water, nickel in solution
Ion concentration is 0.1mol/L, and precipitating reagent is made into into the solution that concentration is 8.0mol/L, and 3L deionized waters are added in reactor,
And add surfactant dodecyl sodium sulfate and each 13.5g of polyvinylpyrrolidone.
3L metal nickel solutions, oxalic acid solution are added in 30L reactors by measuring pump, temperature is maintained at 45 ± 1 DEG C,
PH value is controlled 10 ± 0.05, and after completion of dropwise addition, filtration, filtrate are collected separately after recruiting the system for being used for metallic nickel mixed solution
Standby, filter cake is obtained powdered nickel precursor body nickel oxalate Jing after centrifuge washing, microwave drying.The presoma of nickel powder is placed in into fluid bed dynamic
Reduce in reduction furnace, control 450 DEG C of reduction temperature, the nickel powder after reduction is protected into enclosed air-stream using 99.99% nitrogen
Disintegrating apparatus is crushed.
760 nanometers of analysis test nickel powder Fisher particle size.Powdered nickel precursor body and nickel powder pattern are in bar-shaped under Electronic Speculum, such as Fig. 8 institutes
Show.
Embodiment 8
This example processing process figure is as shown in Figure 1.According to ethanol: citric acid: water is that 1: 1: 10 volume ratio is mixed
Close, metal nickel concentration is 1: 6 with the mol ratio of ammonia concn, and nickel acetate crystal is completely dissolved in into ammonia water-ethanol-citric acid-water
Mixed solution in, nickel ion concentration is 0.6mol/L in solution, precipitating reagent is made into into the solution that concentration is 9.0mol/L, to anti-
Addition 3L deionized waters in device are answered, and adds surfactant sodium dodecyl base benzene sulfonic acid sodium salt, each 13.5g of fatty acid sorbitan.
3L metal nickel solutions, sodium carbonate liquor are added in 30L reactors by measuring pump, temperature is maintained at 95 ± 1
DEG C, pH value is controlled 9.0 ± 0.05, is filtered after completion of dropwise addition, and filtrate is collected separately after recruiting is used for metallic nickel mixed solution
Prepare, filter cake is obtained powdered nickel precursor body nickelous carbonate Jing after centrifuge washing, microwave drying.The presoma of nickel powder is placed in into fluid bed to move
Reduce in state reduction furnace, control 530 DEG C of reduction temperature, the nickel powder after reduction is protected into closed gas using 99.99% nitrogen
Stream disintegrating apparatus is crushed.
80 nanometers of analysis test nickel powder Fisher particle size.Powdered nickel precursor body nickel powder pattern is in spherical shape under Electronic Speculum, such as Fig. 9 institutes
Show.
Embodiment 9
This example processing process figure is as shown in Figure 1.According to ethanol and disodium ethylene diamine tetraacetate equal proportion mixing after with
The volume ratio of water is 1: 1: 18, and metal nickel concentration is 1: 15 with the mol ratio of ammonia concn, and nickel acetate crystal is completely dissolved in into ammonia
In the mixed solution of water-ethanol-disodium ethylene diamine tetraacetate-water, nickel ion concentration is 0.8mol/L in solution, and precipitating reagent is matched somebody with somebody
It is the solution of 2.0mol/L into concentration, 3L deionized waters is added in reactor, and adds surfactant sodium dodecyl base benzene sulphur
Sour sodium 45g.
3L metal nickel solutions, sodium hydroxide solution are added in 30L reactors by measuring pump, temperature is maintained at 100
± 1 DEG C, pH value is controlled 11.0 ± 0.05, and after completion of dropwise addition, filter cake is after Filter Press, washing, baking oven static state are dried
Prepared powdered nickel precursor body nickel hydroxide.The presoma of nickel powder is placed in fluid bed dynamic reduction furnace and is gone back with hydrogen reducing, control
550 DEG C of former temperature, adopts 99.99% nitrogen and the mixture of argon gas 1: 1 protection enclosed air-stream to crush the nickel powder after reduction
Equipment is crushed.
120 nanometers of analysis test nickel powder Fisher particle size, powdered nickel precursor body and nickel powder pattern are in spherical under Electronic Speculum, such as Figure 10 institutes
Show.
Embodiment 10
This example processing process figure is as shown in Figure 1.Volume ratio according to ethanol and water is 1: 25, metal nickel concentration and ammonia
The mol ratio of water concentration is 1: 5, nickel nitrate crystal is completely dissolved in the mixed solution of ammoniacal liquor-alcohol-water, nickel ion in solution
Concentration is 1.0mol/L, and precipitating reagent is made into into the solution that concentration is 4.5mol/L, and 3L deionized waters are added in reactor, and is added
Enter that surfactant fatty acid sorb is smooth, each 15g of dodecyl sodium sulfate.
3L metal nickel solutions, sodium oxalate solution are added in 30L reactors by measuring pump, temperature is maintained at 97 ± 1
DEG C, pH value is controlled 12.0 ± 0.05, after completion of dropwise addition, filter, washing, be dried after powdered nickel precursor body nickel oxalate is obtained.By nickel
The presoma of powder is placed in fluid bed dynamic reduction furnace and reduces, and controls 900 DEG C of reduction temperature, and the nickel powder after reduction is adopted
99.99% argon gas protection enclosed air-stream disintegrating apparatus is crushed.
110 nanometers of analysis test nickel powder Fisher particle size.Powdered nickel precursor body pattern is dendroid, and the nickel powder of reduction is in " like a chain of pearls or a string of beads "
Shape, as shown in figure 11.
Embodiment 11
This example processing process figure is as shown in Figure 1.According to ethanol and disodium ethylene diamine tetraacetate equal proportion mixing after with
The volume ratio of water：1: 1: 30, metal nickel concentration is 1: 15 with the mol ratio of ammonia concn, and nickel chloride crystal is completely dissolved in into ammonia
In the mixed solution of water-ethanol-disodium ethylene diamine tetraacetate-water, nickel ion concentration is 1.5mol/L in solution, and precipitating reagent is matched somebody with somebody
It is the solution of 3.0mol/L into concentration, 3L deionized waters is added in reactor, and adds surfactant dodecyl sodium sulfate
36g。
3L metal nickel solutions, ammonium bicarbonate soln are added in 30L reactors by measuring pump, temperature is maintained at 90 ±
1 DEG C, pH value is controlled 9.3 ± 0.05, after completion of dropwise addition, nickel powder forerunner is obtained after Filter Press, washing, oven drying
Body nickelous carbonate.The presoma of nickel powder is placed in fluid bed dynamic reduction furnace and is reduced, 530 DEG C of reduction temperature is controlled, after reduction
Nickel powder using 99.99% nitrogen protection enclosed air-stream disintegrating apparatus crushed.
150 nanometers of analysis test nickel powder Fisher particle size.Powdered nickel precursor body and nickel powder pattern shape spherical in shape, as shown in figure 12.
Claims (9)
1. a kind of preparation method of nanoscale nickel powder, it is characterised in that comprise the following steps：
(1) dispensing：By complexing agent, additive, water three mixing, mother liquor is obtained；Metallic nickel crystal is added into mother liquor, gold is made
Category nickel crystal is completely dissolved in mother liquor, obtains metal nickel solution；The metallic nickel crystal be nickel sulfate hexahydrate crystal, nickel chloride crystal,
Nickel acetate crystal, nickel nitrate crystal；
(2) synthesize：Deionized water and surfactant are first added in reactor, afterwards metal nickel solution is added to reactor
In, the pH value for controlling solution in reactor with the precipitating reagent that molar concentration is 0.1～10.0mol/L is 7～12, control reaction temperature
Spend for 20～100 DEG C, the reaction time is 2～40h；
(3) filter, be dried：The reacted solution of Jing steps (2) is filtered, wherein filtrate centralized collection as mother liquor, for gold
The preparation of category nickel solution；Powdered nickel precursor body is obtained after Washing of Filter Cake, drying；
(4) fluid bed reduction：Powdered nickel precursor body is placed in fluid bed dynamic reduction furnace and is reduced, control 300～950 DEG C of temperature,
Recovery time is 3-6 hours；
(5) crush：By the nickel powder after reduction, inlet air flow disintegrating apparatus is crushed under inert atmosphere protection, you can prepare expense
In 50～800 nanoscale nickel powders, the inert gas is high pure nitrogen, argon gas or their mixture to family name's granularity.
2. a kind of preparation method of nanoscale nickel powder as claimed in claim 1, it is characterised in that additive described in step (1)
For the equal amount of mixture of one or more in ethanol, tartaric acid, citric acid, disodium ethylene diamine tetraacetate；The additive with
The volume ratio of water is 1: 1～1: 30.
3. a kind of preparation method of nanoscale nickel powder as claimed in claim 1, it is characterised in that live on surface described in step (2)
Property agent for neopelex, fatty acid sorbitan, dodecyl sodium sulfate, polyvinylpyrrolidone one or more
Mixture.
4. a kind of preparation method of nanoscale nickel powder as claimed in claim 1, it is characterised in that complexing agent described in step (1)
For ammoniacal liquor.
5. a kind of preparation method of nanoscale nickel powder as claimed in claim 4, it is characterised in that the metallic nickel GOLD FROM PLATING SOLUTION
Category nickel concentration is 1: 1～1: 15 with the mol ratio of ammonia concn.
6. a kind of preparation method of nanoscale nickel powder as claimed in claim 1, it is characterised in that step (2) precipitating reagent is
One kind in oxalic acid, oxalates, carbonate, bicarbonate, NaOH, potassium hydroxide, the concentration of precipitating reagent is 3.0～
7.0mol/L。
7. a kind of preparation method of nanoscale nickel powder as claimed in claim 1, it is characterised in that the ph value of reaction in step (2)
For 9.0～11.0.
8. a kind of preparation method of nanoscale nickel powder as claimed in claim 1, it is characterised in that the reaction temperature in step (2)
For 85～100 DEG C.
9. a kind of preparation method of nanoscale nickel powder as claimed in claim 1, it is characterised in that the reduction temperature in step (4)
For 650～950 DEG C.
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| CN106623961A (en) * | 2016-11-28 | 2017-05-10 | 荆门市格林美新材料有限公司 | Preparation method of nickel powder with small FSSS |
| CN106799498A (en) * | 2016-11-28 | 2017-06-06 | 格林美股份有限公司 | A kind of preparation method of globular powdered nickel |
| CN106916965A (en) * | 2017-04-21 | 2017-07-04 | 青海快驴电动汽车科技有限公司 | The method that one kind prepares nickel powder using precipitation conversion-control decomposition method |
| CN112317758B (en) * | 2019-08-05 | 2023-05-19 | 涂传鉷 | Preparation method of nano nickel |
| CN115401208B (en) * | 2022-09-02 | 2024-02-27 | 江苏大学 | Preparation method of nickel-based nano powder with controllable morphology |
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| CN1876291A (en) * | 2005-06-07 | 2006-12-13 | 中南大学 | Liquid phase fluidized reduction method for preparing nanometer nickel powder |
| KR101100297B1 (en) * | 2009-01-09 | 2011-12-28 | 한국과학기술연구원 | Method for preparing metal compound powders |
| CN102179527A (en) * | 2011-05-10 | 2011-09-14 | 湖南省娄底维亚科技有限公司 | Method for preparing nano nickel powder |
| CN102728851B (en) * | 2012-06-26 | 2015-07-08 | 湖南省娄底维亚科技有限公司 | Preparation method of hexagonal phase-containing nano nickel powder |
| CN103962570B (en) * | 2013-02-03 | 2016-03-16 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of nano-nickel powder |
| CN103273072B (en) * | 2013-05-20 | 2016-01-20 | 中国科学院过程工程研究所 | A kind of technique and device preparing extra-fine nickel powder |
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