CN104625082A - Nanometer nickel powder preparation method - Google Patents
Nanometer nickel powder preparation method Download PDFInfo
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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, be specifically related to a kind of method preparing nanoscale nickel powder, the method for raw material, adopts Moist chemical synthesis fire reduction legal system for nanoscale nickel powder with metallic nickel crystal.
Background technology
Current nickel powder production technology mainly comprises carbonyl process, gas phase reduction process, normal pressure liquid phase reduction, solid phase reduction method, gamma Rays method, wherein conventional with carbonyl process.Carbonyl process, namely makes Ni (CO) in decomposer under 573-673K
4decompose, by adjusting process parameter, control the forming core of metal nickel powder, growth, reunion and sintering behavior, prepare the extra-fine nickel powder of " chain pearl " shape pattern, in further processing, be easy to form tridimensional network, be specially adapted to the fields such as electrodes conduct additive.The method is mainly divided into two steps to carry out, and first makes CO and nickel reactant generate carbonyl nickel (CO)
4, in thermal decomposition furnace, then make carbonyl nickel decompose obtain nickel powder.The nickel powder granularity that different thermal decomposition furnaces obtains is different with pattern, and the nickel powder that nickel powder shows near-spherical, Recuperative heat type pyrolysis oven is produced that the nickel powder as the production of wall heating type pyrolysis oven shows the production of spherical, pre-heated pyrolysis oven is chain pearl; Gained nickel powder granularity, generally more than 1 μm, has good application performance, is specially adapted to the fields such as electrodes conduct additive.The carbonyl process that International Nickel company of Canada Ltd. (INCO) and Russia north nickel company (Norisk) have nickel extracts and process technology, occupy rank first, it is low that carbonyl process production technology has cost, product purity is high, pattern and granularity are easy to advantages such as regulating, but carbonyl nickel belongs to extremely toxic substance, equipment requirement is high, control difficulty is large, and foreign technology blocks in addition, and China fails to grasp always comprehensively.
Gas phase reduction process is by nickel metallic solution and is placed in containing the hydrocarbon of oxygen atom the reactor decomposition-reduction that hydrocarbon burning and prepares extra-fine nickel powder.This method realizes industrialization, and prepared nickel powder has the feature such as good sphericity and narrow particle size distribution, replaces precious metal palladium in extensive use and ceramic capacitor.Vapor phase method mainly comprises wire electric blasting method, carbonyl nickel thermal decomposition method and vaporize-condensation law.The powder granularity wider distribution that wire electric blasting legal system is standby, nickel powder purity prepared by carbonyl nickel thermal decomposition method is high, dispersed, chemism is high, but poisonous, unfriendly to environment.Vapor-condensate method production efficiency is low, and particle is oxidizable and equipment complicated, and cost intensive is difficult to realize industrialization.
Normal pressure liquid phase reduction nickel ion, nickel coordination ion solution or insoluble compound is reduced in the aqueous solution or organic system with reducing agent at ambient pressure, obtains the method for nano nickel particles.Solid phase reduction method directly prepares extra-fine nickel powder with reduction simple substance generation solid-state displacement reaction by metallic nickel.Gamma Rays method is that water produces Primary product through gamma Rays, and wherein reproducibility particle can by metallic nickel ions gradual deoxidizing, and newly-generated nickle atom assembles nucleation, finally generates nano particle.
Chinese invention patent CN02147855 discloses a kind of preparation method of fibrous nickel powder, adopts precipitation critical heat decomposition method Ni at normal temperatures
2+-NH
3-NH
4+-Cl
--C
2o
4 2--H
2carry out precursor synthesis process prepared by nickel powder in O system, and presoma is resolved into nickel powder by follow-up thermal decomposition process, the nickel powder prepared of this invention in threadiness, granularity is that nanoscale, porous, specific area are large, can meet the requirement of multiple serviceability.Chinese invention patent CN03159577 discloses the preparation method of fibrous nickel powder and nickel protoxide powder, adopts precipitation critical heat decomposition method, at Ni under normal temperature and pressure conditions
2+-NH
3-NH
4+-Cl
--SG
n--C
2o
4 2--H
2nickel powder or nickel protoxide powder presoma is synthesized, thermal decomposition presoma finally obtained fibrous nickel protoxide powder and fibrous nickel powder under oxidation with non-oxidizing conditions in O system.This invention safe preparation process is reliable, nontoxic pollution-free, nickel powder and nickel protoxide powder all in fibrous, granularity be nanoscale, porous, specific area greatly, nickel powder anti-aging capability is strong.
But can only producd fibers shape nickel powder in above-mentioned prior art, for all the other shapes such as spherical, beaded, dendroid, cannot select prepare nickel powder pattern, grain graininess according to need of production Reasonable Regulation And Control.Multi items, many specifications, small grain size little Song ratio, small grain size great Song ratio, coarsegrain great Song represent the developing direction in nickel powder later stage than nickel powder, therefore, we answer active research different cultivars nickel powder new technology, develop the new product of these high technology contents, high added value, and progressively improve product technology content, make nickel powder product diversification, the application that developing nickel powder is different.
Summary of the invention
For solving above-mentioned deficiency of the prior art, the object of this invention is to provide and can produce method that is spherical, fibrous, a shape nickel powder as required, nickel powder prepared by the method is complete in specifications, numerous in variety, oxygen content is low, can realize that industrialization steady and continuous is run, low, the industrial water circulation of energy consumption utilizes, environmental pollution is little.The present invention is achieved through the following technical solutions for achieving the above object:
A preparation method for nanoscale nickel powder, is characterized in that comprising the following steps:
(1) prepare burden: by complexing agent, additive, water three mixing, obtain mother liquor; Metallic nickel crystal is added in mother liquor, metallic nickel crystal is dissolved in mother liquor completely, obtains nickel metallic solution; Described metallic nickel crystal is nickel sulfate hexahydrate crystal, nickel chloride crystal, nickel acetate, nickel nitrate;
(2) synthesize: first in reactor, add deionized water and surfactant, afterwards nickel metallic solution is added in reactor, the pH value controlling solution in reactor with the precipitating reagent that molar concentration is 0.1 ~ 10.0mol/L is 7 ~ 12, controlling reaction temperature is 20 ~ 100 DEG C, and the reaction time is 2 ~ 40h;
(3) filtration, drying: will filter through the reacted solution of step (2), wherein filtrate centralized collection is as mother liquor, for 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 the dynamic reduction furnace of fluid bed and reduces, control temperature 300 ~ 950 DEG C, the recovery time is 3-6 hour;
(5) broken: the nickel powder inlet air flow disintegrating apparatus under inert atmosphere protection after reduction is carried out fragmentation, and can prepare Fisher particle size at 50 ~ 800 nanoscale nickel powders, described inert gas is high pure nitrogen, argon gas or their mixture.
Wherein, described in step (1), the volume ratio of additive and water is 1: 1 ~ 1: 30, and optimum ratio is 1: 5 ~ 1: 20, and more excellent ratio is 1: 5 ~ 1: 10.
Wherein, surfactant described in step (2) is that neopelex, aliphatic acid sorb are smooth, the mixture of one or more of dodecyl sodium sulfate, polyvinylpyrrolidone.
Wherein, described in step (1), complexing agent is ammoniacal liquor; Described additive is the mixture of one or more in ethanol, tartaric acid, citric acid, disodium ethylene diamine tetraacetate.
Wherein, in step (1), in metallic nickel mixed solution, the mol ratio of metallic nickel concentration and ammonia concn is 1: 1 ~ 1: 15, and optimum ratio is 1: 5 ~ 1: 15, and more excellent ratio is 1: 10 ~ 1: 15.
Wherein, in step (2), precipitating reagent is the one in oxalic acid, oxalates, carbonate, bicarbonate, NaOH, potassium hydroxide, and the concentration of precipitating reagent optimum 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 DEG C.
Preferably, reduction temperature optimum in step (4) is 650 ~ 950 DEG C, and more excellent reduction temperature is 800-950 DEG C.
Compared to the prior art, main manifestations is for advantage of the present invention and good effect: (1) adopts the enclosed air-stream breaking method under inert atmosphere protection, and nickel powder oxygen content in shattering process can not be changed; (2) the nickel powder granularity prepared is 50-800 nanometer, and according to different need of production and application, can prepare the nickel powder of different grain size, different size, accomplishes that nickel powder granularity is controlled; (3) utilize Moist chemical synthesis to prepare powdered nickel precursor body, according to the pattern of the Morphological control nickel powder of presoma, have spherical, dendritic to different morphologies such as polyhedrals, morphology controllable; (4) after filtrate centralized collection for the preparation of molten metal, recycle, realize zero-emission, environmental pollution is little.
The nanoscale nickel powder that the present invention produces be spherical, class is spherical, sheet, bar-shaped, dendritic, fibrous; Granularity is at 50-800 nanoscale nickel powder (granularity is adjustable); Metallic impurity elements total amount≤0.07%, carbon≤0.035%, specific area 3-20m
2/ g, apparent density 0.3-1.2g/cm
3, iron≤0.01%, sulphur≤0.01%, oxygen≤0.4%, and according to different applications, different customer demands produce different size, different series nickel powder, meet the need of market.
Accompanying drawing explanation
Fig. 1 is the process chart of the nickel powder adopting the inventive method to prepare;
Fig. 2 embodiment 1 powdered nickel precursor body and nickel powder form;
Fig. 3 embodiment 2 powdered nickel precursor body and nickel powder form;
Fig. 4 embodiment 3 powdered nickel precursor body and nickel powder form;
Fig. 5 embodiment 4 powdered nickel precursor body and nickel powder form;
Fig. 6 embodiment 5 powdered nickel precursor body and nickel powder form;
Fig. 7 embodiment 6 powdered nickel precursor body and nickel powder form;
Fig. 8 embodiment 7 powdered nickel precursor body and nickel powder form;
Fig. 9 embodiment 8 powdered nickel precursor body and nickel powder form;
Figure 10 embodiment 9 powdered nickel precursor body and nickel powder form;
Figure 11 embodiment 10 powdered nickel precursor body and nickel powder form;
Figure 12 embodiment 11 powdered nickel precursor body and nickel powder form.
Detailed description of the invention
Below in conjunction with specific embodiment, explanation is further explained to the present invention, but protection scope of the present invention is not limited to following examples.
Embodiment 1
This routine processing process figure as shown in Figure 1.According to ethanol: tartaric acid: the volume ratio of water is 1: 1: 7, the mol ratio of metallic nickel concentration and ammonia concn is 1: 11, nickel sulfate hexahydrate crystal is dissolved in completely in the mixed solution of ammonia water-ethanol-tartaric acid-water, ammoniacal liquor is made into the solution that concentration is 1.5mol/L, in reactor, add deionized water 3L, add surfactant dodecyl sodium sulfate 46g.
By 3L metallic nickel solution, oxalic acid ammonia solution joins in 30L reactor by measuring pump, adjustment pH value is 10.8 ± 0.05, temperature remains on 55 ± 1 DEG C, after dropping terminates, through Filter Press, washing, filtrate collect separately after for the preparation of metallic nickel mixed solution, filter cake is obtained powdered nickel precursor body nickel oxalate after oven drying.The presoma of nickel powder is placed in the dynamic reduction furnace of fluid bed to reduce, controls reduction temperature 800 DEG C, adopt the argon shield enclosed air-stream disintegrating apparatus of 99.99% to carry out fragmentation the nickel powder after reduction.
Analytical test nickel powder Fisher particle size 50 nanometer.Electricity Microscopic observation powdered nickel precursor body and nickel powder pattern are threadiness, as shown in Figure 2.
Embodiment 2
This routine processing process figure as shown in Figure 1.Be 1: 1 according to the volume ratio of citric acid and water, the mol ratio of metallic nickel concentration and ammonia concn is 1: 1, nickel nitrate crystal is dissolved in completely in the mixed solution of ammoniacal liquor-citric acid-water, in solution, nickel ion concentration is 2.0mol/L, precipitating reagent is made into the solution that concentration is 0.1mol/L, in reactor, add 3L deionized water, and add the smooth 33g of surfactant fatty acid sorb.
By 3L metallic nickel solution; sodium carbonate liquor joins in 30L reactor by measuring pump; temperature remains on 100 ± 1 DEG C; pH value controls 7.0 ± 0.05; dropping terminates rear filtration; for the preparation of nickel metallic solution after filtrate collection; filter cake is obtained powdered nickel precursor body nickelous carbonate after centrifuge washing, microwave drying; the presoma of nickel powder is placed in the dynamic reduction furnace of fluid bed to reduce; control reduction temperature 300 DEG C, adopt the nitrogen protection enclosed air-stream disintegrating apparatus of 99.99% to carry out fragmentation the nickel powder after reduction.
Analytical test nickel powder Fisher particle size 520 nanometer.Electricity Microscopic observation powdered nickel precursor body and nickel powder pattern shape spherical in shape, as shown in Figure 3.
Embodiment 3
This routine processing process figure as shown in Figure 1.Be 1: 30 according to the volume ratio of ethanol and water, the mol ratio of metallic nickel concentration and ammonia concn is 1: 15, nickel chloride crystal is dissolved in completely in the mixed solution of ammoniacal liquor-alcohol-water, in solution, nickel ion concentration is 0.6mol/L, precipitating reagent is made into the solution that concentration is 10.0mol/L, in reactor, add 3L deionized water, and add surfactant sodium dodecyl base benzene sulfonic acid sodium salt 27g.
By 3L metallic nickel solution, Potassium Oxalate Solution joins in 30L reactor by measuring pump, temperature remains on 20 ± 1 DEG C, pH value controls 12 ± 0.05, after dropping terminates, filter, mother liquor collect separately and recruit after for the preparation of metallic nickel mixed solution, filter cake is obtained powdered nickel precursor body nickel oxalate after centrifuge washing, microwave drying.The presoma of nickel powder is placed in the dynamic reduction furnace of fluid bed to reduce, controls reduction temperature 650 DEG C, adopt the nitrogen protection enclosed air-stream disintegrating apparatus of 99.99% to carry out fragmentation the nickel powder after reduction.
Analytical test nickel powder Fisher particle size 350 nanometer, electric Microscopic observation powdered nickel precursor body and nickel powder pattern are polyhedral, as shown in Figure 4.
Embodiment 4
This routine processing process figure as shown in Figure 1.Be 1: 20 according to the volume ratio of disodium ethylene diamine tetraacetate and water, the mol ratio of metallic nickel concentration and ammonia concn is 1: 10, nickel acetate crystal is dissolved in completely in the mixed solution of ammoniacal liquor-disodium ethylene diamine tetraacetate-water, in solution, nickel ion concentration is 0.8mol/L, precipitating reagent is made into the solution that concentration is 5.0mol/L, in reactor, add 3L deionized water, and add surfactant polyvinylpyrrolidone 45g.
By 3L metallic nickel solution, potassium hydroxide solution joins in 30L reactor by measuring pump, and temperature remains on 50 ± 1 DEG C, and pH value controls 11.0 ± 0.05, drips after terminating, filtration, washing, dry rear obtained powdered nickel precursor body nickel hydroxide.The presoma of nickel powder is placed in the dynamic reduction furnace of fluid bed to reduce, controls reduction temperature 450 DEG C, adopt the nitrogen protection enclosed air-stream disintegrating apparatus of 99.99% to carry out fragmentation the nickel powder after reduction.
Analytical test nickel powder Fisher particle size 250 nanometer, under Electronic Speculum, powdered nickel precursor body and nickel powder pattern are class spherical " like a chain of pearls or a string of beads " shape, as shown in Figure 5.
Embodiment 5
This routine processing process figure as shown in Figure 1.Be 1: 15 according to the volume ratio of ethanol and water, the mol ratio of metallic nickel concentration and ammonia concn is 1: 13, nickel nitrate crystal is dissolved in completely in the mixed solution of ammoniacal liquor-alcohol-water, in solution, nickel ion concentration is 1.0mol/L, precipitating reagent is made into the solution that concentration is 6mol/L, in reactor, add 3L deionized water, and add surfactant polyvinylpyrrolidone 23g.
By 3L metallic nickel solution; sodium oxalate solution joins in 30L reactor by measuring pump; temperature remains on 85 ± 1 DEG C; pH value controls 9.0 ± 0.05; after dropping terminates, filtration, washing, dry rear obtained powdered nickel precursor body nickel oxalate, be placed in the dynamic reduction furnace of fluid bed and reduce by the presoma of nickel powder; control reduction temperature 950 DEG C, adopt the nitrogen protection enclosed air-stream disintegrating apparatus of 99.99% to carry out fragmentation the nickel powder after reduction.
Analytical test nickel powder Fisher particle size 50 nanometer, under Electronic Speculum, powdered nickel precursor body and nickel powder pattern are dendroid, as shown in Figure 6.
Embodiment 6
This routine processing process figure as shown in Figure 1.Be 1: 10 according to the volume ratio of tartaric acid and water, the mol ratio of metallic nickel concentration and ammonia concn is 1: 10, nickel acetate crystal is dissolved in completely in the mixed solution of ammoniacal liquor-tartaric acid-water, in solution, nickel ion concentration is 1.5mol/L, precipitating reagent is made into the solution that concentration is 7.0mol/L, in reactor, add 3L deionized water, and add surfactant dodecyl sodium sulfate 36g.
By 3L metallic nickel solution; ammonium bicarbonate soln joins in 30L reactor by measuring pump; temperature remains on 85 ± 1 DEG C; pH value controls 8.0 ± 0.05, and drip after terminating, filter cake is through Filter Press, washing; obtained powdered nickel precursor body nickelous carbonate after oven drying; the presoma of nickel powder is placed in the dynamic reduction furnace of fluid bed to reduce, controls reduction temperature 650 DEG C, adopt the argon shield enclosed air-stream disintegrating apparatus of 99.99% to carry out fragmentation the nickel powder after reduction.
Analytical test nickel powder Fisher particle size 720 nanometer.Powdered nickel precursor body and nickel powder pattern are ball sheet, as shown in Figure 7.
Embodiment 7
This routine processing process figure as shown in Figure 1.Be 1: 10 according to the volume ratio of tartaric acid and water, the mol ratio of metallic nickel concentration and ammonia concn is 1: 5, nickel sulfate hexahydrate crystal is dissolved in completely in the mixed solution of ammoniacal liquor-tartaric acid-water, in solution, nickel ion concentration is 0.1mol/L, precipitating reagent is made into the solution that concentration is 8.0mol/L, in reactor, add 3L deionized water, and add surfactant dodecyl sodium sulfate and each 13.5g of polyvinylpyrrolidone.
By 3L metallic nickel solution, oxalic acid solution joins in 30L reactor by measuring pump, temperature remains on 45 ± 1 DEG C, pH value controls 10 ± 0.05, after dropping terminates, filter, filtrate collect separately and recruit after for the preparation of metallic nickel mixed solution, filter cake is obtained powdered nickel precursor body nickel oxalate after centrifuge washing, microwave drying.The presoma of nickel powder is placed in the dynamic reduction furnace of fluid bed to reduce, controls reduction temperature 450 DEG C, adopt the nitrogen protection enclosed air-stream disintegrating apparatus of 99.99% to carry out fragmentation the nickel powder after reduction.
Analytical test nickel powder Fisher particle size 760 nanometer.Under Electronic Speculum, powdered nickel precursor body and nickel powder pattern are bar-shaped, as shown in Figure 8.
Embodiment 8
This routine processing process figure as shown in Figure 1.According to ethanol: citric acid: water be 1: 1: 10 volume ratio mix, the mol ratio of metallic nickel concentration and ammonia concn is 1: 6, nickel acetate crystal is dissolved in completely in the mixed solution of ammonia water-ethanol-citric acid-water, in solution, nickel ion concentration is 0.6mol/L, precipitating reagent is made into the solution that concentration is 9.0mol/L, in reactor, add 3L deionized water, and add surfactant sodium dodecyl base benzene sulfonic acid sodium salt, the smooth each 13.5g of aliphatic acid sorb.
By 3L metallic nickel solution, sodium carbonate liquor joins in 30L reactor by measuring pump, temperature remains on 95 ± 1 DEG C, pH value controls 9.0 ± 0.05, dropping terminates rear filtration, filtrate collect separately and recruit after for the preparation of metallic nickel mixed solution, filter cake is obtained powdered nickel precursor body nickelous carbonate after centrifuge washing, microwave drying.The presoma of nickel powder is placed in the dynamic reduction furnace of fluid bed to reduce, controls reduction temperature 530 DEG C, adopt the nitrogen protection enclosed air-stream disintegrating apparatus of 99.99% to carry out fragmentation the nickel powder after reduction.
Analytical test nickel powder Fisher particle size 80 nanometer.Under Electronic Speculum, powdered nickel precursor body nickel powder pattern is class ball shape, as shown in Figure 9.
Embodiment 9
This routine processing process figure as shown in Figure 1.Mixing volume ratio that is rear and water according to ethanol and disodium ethylene diamine tetraacetate equal proportion is 1: 1: 18, the mol ratio of metallic nickel concentration and ammonia concn is 1: 15, nickel acetate crystal is dissolved in completely in the mixed solution of ammonia water-ethanol-disodium ethylene diamine tetraacetate-water, in solution, nickel ion concentration is 0.8mol/L, precipitating reagent is made into the solution that concentration is 2.0mol/L, in reactor, add 3L deionized water, and add surfactant sodium dodecyl base benzene sulfonic acid sodium salt 45g.
By 3L metallic nickel solution, sodium hydroxide solution joins in 30L reactor by measuring pump, and temperature remains on 100 ± 1 DEG C, and pH value controls 11.0 ± 0.05, after dropping terminates, filter cake is obtained powdered nickel precursor body nickel hydroxide after Filter Press, washing, the static drying of baking oven.The presoma of nickel powder is placed in the dynamic reduction furnace hydrogen reducing of fluid bed, controls reduction temperature 550 DEG C, adopted by the nickel powder after reduction the nitrogen of 99.99% and argon gas 1: 1 mixture protection enclosed air-stream disintegrating apparatus to carry out fragmentation.
Analytical test nickel powder Fisher particle size 120 nanometer, under Electronic Speculum, powdered nickel precursor body and nickel powder pattern are spherical, as shown in Figure 10.
Embodiment 10
This routine processing process figure as shown in Figure 1.Be 1: 25 according to the volume ratio of ethanol and water, the mol ratio of metallic nickel concentration and ammonia concn is 1: 5, nickel nitrate crystal is dissolved in completely in the mixed solution of ammoniacal liquor-alcohol-water, in solution, nickel ion concentration is 1.0mol/L, precipitating reagent is made into the solution that concentration is 4.5mol/L, in reactor, add 3L deionized water, and add that surfactant fatty acid sorb is smooth, each 15g of dodecyl sodium sulfate.
By 3L metallic nickel solution, sodium oxalate solution joins in 30L reactor by measuring pump, and temperature remains on 97 ± 1 DEG C, and pH value controls 12.0 ± 0.05, drips after terminating, filtration, washing, dry rear obtained powdered nickel precursor body nickel oxalate.The presoma of nickel powder is placed in the dynamic reduction furnace of fluid bed to reduce, controls reduction temperature 900 DEG C, adopt the argon shield enclosed air-stream disintegrating apparatus of 99.99% to carry out fragmentation the nickel powder after reduction.
Analytical test nickel powder Fisher particle size 110 nanometer.Powdered nickel precursor body pattern is dendroid, and the nickel powder of reduction is " like a chain of pearls or a string of beads " shape, as shown in figure 11.
Embodiment 11
This routine processing process figure as shown in Figure 1.Volume ratio that is rear and water is mixed: 1: 1: 30 according to ethanol and disodium ethylene diamine tetraacetate equal proportion, the mol ratio of metallic nickel concentration and ammonia concn is 1: 15, nickel chloride crystal is dissolved in completely in the mixed solution of ammonia water-ethanol-disodium ethylene diamine tetraacetate-water, in solution, nickel ion concentration is 1.5mol/L, precipitating reagent is made into the solution that concentration is 3.0mol/L, in reactor, add 3L deionized water, and add surfactant dodecyl sodium sulfate 36g.
By 3L metallic nickel solution, ammonium bicarbonate soln joins in 30L reactor by measuring pump, and temperature remains on 90 ± 1 DEG C, and pH value controls 9.3 ± 0.05, drips after terminating, obtained powdered nickel precursor body nickelous carbonate after Filter Press, washing, oven drying.The presoma of nickel powder is placed in the dynamic reduction furnace of fluid bed to reduce, controls reduction temperature 530 DEG C, adopt the nitrogen protection enclosed air-stream disintegrating apparatus of 99.99% to carry out fragmentation the nickel powder after reduction.
Analytical test nickel powder Fisher particle size 150 nanometer.Powdered nickel precursor body and nickel powder pattern shape spherical in shape, as shown in figure 12.
Claims (9)
1. a preparation method for nanoscale nickel powder, is characterized in that comprising the following steps:
(1) prepare burden: by complexing agent, additive, water three mixing, obtain mother liquor; Metallic nickel crystal is added in mother liquor, metallic nickel crystal is dissolved in mother liquor completely, obtains nickel metallic solution; Described metallic nickel crystal is nickel sulfate hexahydrate crystal, nickel chloride crystal, nickel acetate crystal, nickel nitrate crystal;
(2) synthesize: first in reactor, add deionized water and surfactant, afterwards nickel metallic solution is added in reactor, the pH value controlling solution in reactor with the precipitating reagent that molar concentration is 0.1 ~ 10.0mol/L is 7 ~ 12, controlling reaction temperature is 20 ~ 100 DEG C, and the reaction time is 2 ~ 40h;
(3) filtration, drying: will filter through the reacted solution of step (2), wherein filtrate centralized collection is as mother liquor, for 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 the dynamic reduction furnace of fluid bed and reduces, control temperature 300 ~ 950 DEG C, the recovery time is 3-6 hour;
(5) broken: the nickel powder inlet air flow disintegrating apparatus under inert atmosphere protection after reduction is carried out fragmentation, and can prepare Fisher particle size at 50 ~ 800 nanoscale nickel powders, described inert gas is high pure nitrogen, argon gas or their mixture.
2. the preparation method of a kind of nanoscale nickel powder as claimed in claim 1, is characterized in that additive described in step (1) is the equal amount of mixture of one or more in ethanol, tartaric acid, citric acid, disodium ethylene diamine tetraacetate; The volume ratio of described additive and water is 1: 1 ~ 1: 30, and optimum ratio is 1: 5 ~ 1: 20, and more excellent ratio is 1: 5 ~ 1: 10.
3. the preparation method of a kind of nanoscale nickel powder as claimed in claim 1, is characterized in that surfactant described in step (1) is that neopelex, aliphatic acid sorb are smooth, the mixture of one or more of dodecyl sodium sulfate, polyvinylpyrrolidone.
4. the preparation method of a kind of nanoscale nickel powder as claimed in claim 1, is characterized in that described in step (1), complexing agent is ammoniacal liquor.
5. the preparation method of a kind of nanoscale nickel powder as claimed in claim 1, it is characterized in that the mol ratio that described metallic nickel GOLD FROM PLATING SOLUTION belongs to nickel concentration and ammonia concn is 1: 1 ~ 1: 15, optimum ratio is 1: 5 ~ 1: 15, and more excellent ratio is 1: 10 ~ 1: 15.
6. the preparation method of a kind of nanoscale nickel powder as claimed in claim 1, it is characterized in that step (2) described precipitating reagent is the one in oxalic acid, oxalates, carbonate, bicarbonate, NaOH, potassium hydroxide, the concentration of precipitating reagent optimum is 3.0 ~ 7.0mol/L, and more excellent concentration is 5.0 ~ 6.0mol/L.
7. the preparation method of a kind of nanoscale nickel powder as claimed in claim 1, it is characterized in that ph value of reaction optimum in step (2) is 9.0 ~ 11.0, more excellent PH is 9.0-10.0.
8. the preparation method of a kind of nanoscale nickel powder as claimed in claim 1, it is characterized in that reaction temperature optimum in step (2) is 85 ~ 100 DEG C, more excellent reaction temperature is 95-100 DEG C.
9. the preparation method of a kind of nanoscale nickel powder as claimed in claim 1, it is characterized in that reduction temperature optimum in step (4) is 650 ~ 950 DEG C, more excellent reduction temperature is 800-950 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 |
| CN112317758A (en) * | 2019-08-05 | 2021-02-05 | 涂传鉷 | Preparation method of nano nickel |
| CN115401208A (en) * | 2022-09-02 | 2022-11-29 | 江苏大学 | Preparation method of nickel-based nano powder with controllable morphology |
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| CN112317758B (en) * | 2019-08-05 | 2023-05-19 | 涂传鉷 | Preparation method of nano nickel |
| CN115401208A (en) * | 2022-09-02 | 2022-11-29 | 江苏大学 | Preparation method of nickel-based nano powder with controllable morphology |
| 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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