CN101428349B

CN101428349B - Method for producing nickel-cobalt metal powder

Info

Publication number: CN101428349B
Application number: CN2008101350365A
Authority: CN
Inventors: 张建玲
Original assignee: Individual
Current assignee: Individual
Priority date: 2008-07-29
Filing date: 2008-07-29
Publication date: 2011-06-22
Anticipated expiration: 2028-07-29
Also published as: CN101428349A

Abstract

The invention discloses a preparation method for nickel cobalt metal powders, which belongs to the technical field for preparation of non-ferrous metal metallurgy, powder metallurgy and material preparation. The preparation method is characterized in that nanometer or ultrafine nickel and cobalt metal powders is adopted as a seed crystal, which is mixed with ammoniacal water solution with nickel sulfate, cobalt sulfate, ammonia and ammonium sulfate, the preparation method adopts a hydrometallurgical hydrothermal hydrogen reducing technology and a device thereof, and the nanometer, ultrafine or tenuous nickel powder, cobalt powder and nickel cobalt alloy powder are prepared through the procedures such as ingredient, high-pressure hydrothermal hydrogen reduction, filtration, washing, drying and the like. The preparation method can be used for the field such as hydrogen storage alloy, galvanization, catalyst, sintering activating agent, magnetic materials, electric conduction slurry, battery materials, wave-absorbing materials, hard alloy, multi-layer porcelain capacitor, powder metallurgy and the like. The preparation method has the advantages of simple raw materials, simple process, short technological process, low manufacturing cost, controllable manufacturing process, high production efficiency, even graininess of metal powders, controllable size and composition and good quality of products.

Description

A kind of preparation method of nickel-cobalt metal powder

Technical field

A kind of preparation method of nickel-cobalt metal powder belongs to Non-ferrous Metallurgy, powder metallurgy and technical field of material.Relating to a kind of is crystal seed with nanometer or ultra-fine nickel, cobalt metal powder, adopts hydrometallurgy hydro-thermal hydrogen reduction process to prepare the process of nickel powder or cobalt powder or nickel cobalt (alloy) powder.

Technical background

Nickel cobalt (Ni-Co) alloy powder has special performances, be different from physics, chemistry, magnetic and the mechanical performance of general simple nickel, cobalt metal powder, be with a wide range of applications in industries such as carbide alloy, hydrogen-storage alloy, magnetic material, catalyst, plating, batteries.In addition; aspect carbide alloy prepares; cobalt metal price costliness; scarcity of resources, people are studying the substitute of cobalt always, as nickel and iron; but it is very low as the common mechanical strength of the carbide alloy of binding agent with iron powder; with the bonding phase of pure nickel as carbide alloy, the physical and mechanical properties of resulting carbide alloy is not so good as the performance that cobalt is made binding agent, and technology controlling and process is difficult.The nickel cobalt (alloy) that replaces the part cobalt with nickel then can be obtained effect preferably, and reduces production costs.

The preparation method of nickel cobalt (alloy) powder mainly contains solid phase method, vapor phase method, liquid phase method, can be subdivided into machine-alloying, carbonyl process, ultrasonic irradiation method, hydrothermal reduction method, polyol reduction method, electrodeposition process, co-precipitation-thermal decomposition method, halide gas phase reduction process or the like again.The hydrothermal reduction method of having reported is to use NiSO ₄, CoSO ₄Reaching hydrazine is feedstock production nickel cobalt (alloy) powder, and its technology is earlier with the hydrazine (being hydrazine hydrate) of 10M and the NiSO of 0.05M ₄, CoSO ₄Solution mixes, and pours into then in the autoclave and reacts under uniform temperature.In course of reaction, Ni ²⁺, Co ²⁺At room temperature form intermediate compound [Ni (N with hydrazine earlier ₂H ₄) ₃] ²⁺, [Co (N ₂H ₄) ₃] ²⁺, along with the rising of temperature, intermediate compound begins to be decomposed to form the nickel cobalt (alloy) powder.Experimental study shows that only in pH 〉=13, temperature is greater than just obtaining nickel cobalt (alloy) powder (profound cyanines, Zhang Chuanfu, Li Changjun etc., the preparation of cobalt nickel powder and application present situation thereof, carbide alloy,, the 19th the 4th phase of volume, p206～210 in 2002) under 120 ℃ the condition.This hydrothermal reduction method has been used expensive hydrazine, the production cost height; React under high pH value, preparation condition is harsh.And hydro-thermal hydrogen reduction rule employing hydrogen is reducing agent, and is different with this hydrothermal reduction method.Up to the present, yet there are no and use the hydro-thermal hydrogen reduction method, particularly prepare the open report of nickel cobalt (alloy) powder as crystal seed with nano-nickel powder, cobalt powder.

Extra-fine nickel powder demonstrates good performance in catalyst, sintering activator, magnetic material, electrocondution slurry, battery material, absorbing material, carbide alloy, multilayer ceramic capacitor and field of powder metallurgy.Super-fine cobalt powder then is mainly used in carbide alloy, battery material, catalyst, permanent magnet material and ceramic industry etc.Developing rapidly of industries such as domestic because battery, catalyst, carbide alloy heightened to the demand of extra-fine nickel powder, super-fine cobalt powder.

The preparation method of extra-fine nickel powder and super-fine cobalt powder (hereinafter referred to as extra-fine nickel powder, cobalt powder) mainly contains vapor phase method, liquid phase reduction, electrolysis and solid phase method, the domestic relevant patent of invention that discloses is a lot of, but the technical method that has been used for suitability for industrialized production mainly still vapor phase method, liquid phase reduction.Wherein the hydrothermal high-temperature pressurized hydrogen reducing process in the liquid phase reduction (being called for short the hydro-thermal hydrogen reduction method) is that the sediment (as oxide, hydroxide, subcarbonate etc.) with nickel, cobalt is a raw material, the furnishing water slurry, and add catalyst (as palladium bichloride etc.), in autoclave under the hot conditions, feed high pressure hydrogen, the reduction of control reaction condition obtains extra-fine nickel powder or super-fine cobalt powder (CN1034689A, CN85100739A, GB744563A, US2805149A1).Perhaps in the ammonia solution of nickelous sulfate (cobalt), ammonium sulfate and ammoniacal liquor, add ferrous sulfate, chromous sulfate, sodium borohydride (US4761177A1), silver sulfate, silver nitrate (US5246481A1) or Cymag and vulcanized sodium (EP0047076A1) etc. as nucleating agent, pressurized hydrogen reduction under 120～200 ℃ of hydrothermal conditions, obtain cobalt powder (heavy non-ferrous metal smelting design manual, copper nickel volume, metallurgical industry publishing house, 1996, p754～772; And Liu Jinshan, produce cobalt powder, China YouSe metallurgy,, the 5th phase, p24～30 in 1979 with the pressurized hydrogen reducing process).The mode of nucleating agent with the aqueous solution joined in the ammonia solution of sulfur acid nickel (cobalt), and then, can directly prepare extra-fine nickel powder or super-fine cobalt powder, but this method needs long induction period usually, influences production efficiency through repeatedly growing up; Because induction period is long, causes that especially easily the inwall of equipment scabs, the method that needs subsequently to spend the plenty of time to adopt chemistry or hyperbaric oxygen to soak is removed, and increases production cost.Other metallic element has been introduced in the interpolation of nucleating agent, reduces product purity, influences the performance of product; Nucleating agent itself costs an arm and a leg (as silver nitrate, palladium bichloride etc.), increases production cost; Extremely toxic substance (as the cyanide) contaminated environment of adding.

In recent years, nanometer technology has obtained great development, developed the preparation method of many preparation nano-nickel powders and nano-cobalt powder (to call nano-nickel powder, cobalt powder in the following text), for the improvement of the hydrothermal high-temperature pressurized hydrogen of extra-fine nickel powder, cobalt powder reduction preparation technology method provides the foundation.The present invention is by discovering, directly replace nucleating agent with nano-nickel powder, cobalt powder, can shorten the time of decomposition induction time greatly, be reduced to 2～5 minute from 40～80 minutes induction period, the rate that scabs also only is 5～10% when adding conventional additives, improve equipment service efficiency and product purity greatly, and can prepare the nickel cobalt (alloy) powder of heterogeneity scope easily.

Summary of the invention

The objective of the invention is: a kind of process that adopts hydro-thermal hydrogen reduction process to prepare nickel powder or cobalt powder or nickel cobalt (alloy) powder is provided, mainly comprises following process and purpose:

(1) make crystal seed with nano-nickel powder, cobalt powder, adopt hydro-thermal hydrogen reduction process, bag cobalt plating on the nano-nickel powder or on nano-cobalt powder plating nickel, thereby obtain to comprise simultaneously the nanometer nickel-cobalt alloy powder of metallic nickel and metallic cobalt; Divide two kinds of methods to handle with the acquisition product, the one, directly make crystal seed with this nanometer nickel-cobalt alloy powder, prepare ultra-fine or fine nickel cobalt (alloy) powder.After containing the mixed solution filtration of nanometer nickel-cobalt alloy powder after the hydro-thermal hydrogen reduction soon, do not wash, again with the ammonia aqueous solution of nickeliferous, cobalt sulfate and ammonia, ammonium sulfate, adopt hydro-thermal hydrogen reduction process, on the nanometer nickel-cobalt alloy powder, wrap cobalt plating or plating nickel again, prepare ultra-fine or fine nickel cobalt (alloy) powder; The 2nd, the mixed solution that contains the nanometer nickel-cobalt alloy powder after the hydro-thermal hydrogen reduction is filtered, through washing, oven dry, obtain nanometer nickel-cobalt alloy powder product.

(2) make crystal seed with nano-nickel powder, cobalt powder, adopt hydro-thermal hydrogen reduction process to prepare extra-fine nickel powder, cobalt powder; Divide two kinds of methods to handle with the acquisition product, the one, directly make crystal seed with this extra-fine nickel powder or cobalt powder, prepare ultra-fine or fine nickel cobalt (alloy) powder.After containing the mixed solution filtration of extra-fine nickel powder or cobalt powder after the hydro-thermal hydrogen reduction soon, do not wash, with the ammonia aqueous solution of new nickeliferous or cobalt sulfate, adopt hydro-thermal hydrogen reduction process again, on the nickel powder bag cobalt plating or on cobalt powder plating nickel, prepare ultra-fine or fine nickel cobalt (alloy) powder; The 2nd, the mixed solution that contains extra-fine nickel powder or cobalt powder after the hydro-thermal hydrogen reduction is filtered, through washing, oven dry, obtain ultra-fine pure nickel powder or pure cobalt powder product.

(3) make crystal seed with extra-fine nickel powder, cobalt powder, adopt hydro-thermal hydrogen reduction process,, thereby obtain fine nickel powder or fine cobalt powder product at plating nickel or on cobalt powder, wrap cobalt plating more again on the extra-fine nickel powder.

The objective of the invention is to realize: nickelous sulfate or/and cobaltous sulfate, ammoniacal liquor, ammonium sulfate are made into the certain density ammonia aqueous solution in proportion, is added a small amount of anthraquinone, gelatine by following technical matters scheme; Get certain amount of nano or extra-fine nickel powder or cobalt powder and make crystal seed, join in the ammonia aqueous solution for preparing, stirring and evenly mixing, the mixed solution that will contain nickel powder or cobalt powder then changes in the autoclave sealing autoclave over to.Open the autoclave stirring motor, nickel powder or cobalt powder are suspended in the mixed solution; With the heating of the solution in the autoclave, when solution temperature reaches more than 120 ℃, charge into high pressure hydrogen, make the still internal pressure reach 2～6MPa; Keep the interior pressure of autoclave and the temperature of solution, hydrogen is with solution metal nickel ion or cobalt ions reduction, and metallic nickel or metallic cobalt are constantly separated out, and are deposited on nanometer or extra-fine nickel powder or cobalt powder seed surface; Along with the prolongation of recovery time, the metallic nickel of separating out or metallic cobalt amount increase, and when the metallic nickel that is reduced or metallic cobalt amount were abundant, seed surface was covered by metallic nickel or metallic cobalt, forms the metallic nickel or the metallic cobalt bag coating of one deck densification; And when the deposition metallic nickel of separating out or metallic cobalt amount more after a little while, the part surface of original crystal seed exposes to the open air outside, the metal of deposition is interspersed on its surface.After the nickel ion in the solution or cobalt ions are reduced fully by hydrogen, bag plating reaction stops, solution in the autoclave is cooled to below 90 ℃, discharge the surface and wrap nickel powder or cobalt powder or the nickel cobalt (alloy) powder and the aqueous solution that has plated metallic nickel or metallic cobalt, after filtration, drying, can obtain a kind of in the ultra-fine or fine metal nickel powder of needed nanometer, cobalt powder, the nickel cobalt (alloy) powder.Filtrate is through evaporation, concentrated, crystallization, reclaim sulfuric acid ammonium.

The preparation process of above-mentioned metal dust can be according to the material property needs, difference according to metal cation component in the sulfur acid nickel that is adopted or the sulfur acid cobalt ammonia aqueous solution, both can be on nickel powder coated metal nickel, but also coated metal cobalt, perhaps coated metal nickel or metallic cobalt on cobalt powder, nickel cobalt (alloy) powder.The ammonia aqueous solution by selecting sulfur acid nickel or sulfur acid cobalt is as raw material, and control solution metal content, decide the metal species or the amount of metal that need the bag plating, as the ammonia aqueous solution that alternately adopts these two kinds of metals is raw material, and control the wherein content of metal ion, after each bag has plated a kind of metal, the aqueous solution is filtered, powder and another kind of ammonia aqueous solution, in autoclave, deposit second kind of metal through the hydro-thermal hydrogen reduction, metal dust can be on a kind of crystal seed, deposited, and metal layer thickness can be controlled with sandwich.Because of containing nickel, cobalt ions in the ammonia aqueous solution simultaneously, nickel is preferentially separated out in the hydrogen reduction process, and after nickel ion was finished by basic reduction, cobalt began deposition, so when preparation nickel cobalt (alloy) powder, can adopt the ammonia aqueous solution that contains nickel, cobalt ions simultaneously is raw material.

Processing step and feature that the present invention is concrete are as follows:

1, measures the deionized water of certain volume, in the suction tank diameter, add hot deionized water to 40～90 ℃, add nickelous sulfate or cobaltous sulfate, add ammoniacal liquor, ammonium sulfate, being made into that to contain single metallic nickel or concentration of cobalt ions be 15～130g/L, ammonium sulfate concentrations 50～230g/L, ammonia metal than the ratio of ammonia in the ie in solution and nickel ion or ammonia and the molal quantity of cobalt ions is 2.1～4.5 the ammonia aqueous solution, wherein nickel, cobalt metal ion are not present in simultaneously with in a kind of solution, i.e. the ammonia aqueous solution of single metal.

2, measure the deionized water of certain volume, in the suction tank diameter, add hot deionized water to 40～90 ℃, add nickelous sulfate, cobaltous sulfate simultaneously, add ammoniacal liquor, ammonium sulfate again, be made into that to contain that to contain nickel ion and cobalt ions, total concentration simultaneously be 40～130g/L, ammonium sulfate concentrations 50～230g/L, ammonia metal than the ratio of ammonia in the ie in solution and the total mole number of nickel and cobalt ions be 2.1～4.5 the ammonia aqueous solution, wherein nickel, cobalt metal ion are present in simultaneously with in a kind of solution, i.e. the ammonia aqueous solution of while sulfur acid nickel and two kinds of metals of cobaltous sulfate.

3,, be metered into anthraquinone, 0.01～0.02g/L gelatine by 0.1～0.2g/L the single of nickelous sulfate or cobaltous sulfate or contain simultaneously in the ammonia aqueous solution of two kinds of metals.

4, the single of nickelous sulfate or cobaltous sulfate or contain simultaneously add anthraquinone and gelatine in the ammonia aqueous solution of two kinds of metals after, add nanometer or extra-fine nickel powder or cobalt powder or cobalt nickel powder crystal seed again; Nano level metal powder crystal seed average diameter is about 5～90nm, and ultra-fine level metal dust crystal seed average diameter is about 200～950nm; When the preparation cobalt nickel powder, the crystal seed addition requires to determine that amount nickeliferous or cobalt is adjustable in 5～50% scopes according to last product component.

5, the ammonia aqueous solution that will contain the single of crystal seed or two kinds of metals changes in the autoclave, behind the sealing autoclave, open the autoclave stirring motor, 300～1100 rev/mins of mixing speeds, make crystal seed be suspended in single or the two metal ammonia aqueous solution in, wrap plating reaction.The heating high-pressure still makes solution temperature rising in the still, after temperature rises to 120 ℃, high pressure hydrogen is imported from high pressure storage tank in the pressure-reducing cushioning jar, charges into then in the autoclave, makes the interior Hydrogen Vapor Pressure of still reach 2.5～6MPa; The hydrogen that charges into reduces solution metal nickel, cobalt ions, and is deposited on seed surface, and deposition reaction continues to carry out, and hydrogen-pressure constantly descends; When Hydrogen Vapor Pressure is reduced to 2MPa, charge into hydrogen again to certain pressure, the temperature that keeps solution is in 120～200 ℃ of scopes, and till finishing to metallic nickel, cobalt ions reduction reaction, deposition reaction finishes.

6, with cooling water the aqueous solution in the autoclave is cooled to below 90 ℃, in autoclave, discharge the aqueous solution that contains metal nickel powder or cobalt powder or cobalt nickel powder, washing after filtration,, it is dry under 40～80 ℃ of temperature that metal dust is put into vacuum drying oven, obtains needed nanometer, ultra-fine or superfine metallic nickel powder or cobalt powder or cobalt nickel powder product; Filtrate is through evaporation, concentrated, crystallization, reclaim sulfuric acid ammonium.

7 or through after the above-mentioned steps 5, after the aqueous solution that will contain metal nickel powder or cobalt powder or cobalt nickel powder is discharged in the autoclave, different with step 6, only metal dust is filtered out from solution, do not wash, metal dust is not as final products, but once more as crystal seed, mix by a certain percentage with the ammonia aqueous solution single or that contain two kinds of metals simultaneously, change in the autoclave, set by step 5 repeated hydrogen reduce deposition metals.So through repeating step 5,7 repeatedly, after reaching requirement, in autoclave, discharge the aqueous solution that contains metal nickel powder or cobalt powder or cobalt nickel powder, washing after filtration,, it is dry under 40～80 ℃ of temperature that metal dust is put into vacuum drying oven, obtains needed ultra-fine or superfine metallic nickel powder or cobalt powder or cobalt nickel powder product.

8, the metal dust that at every turn filters out in the above-mentioned steps 5,7, always only with a kind of ammonia aqueous solution of single metal, wrap the plating reaction, then obtain the metal dust of single component; Perhaps, wrap the plating reaction, then obtain the nickel cobalt (alloy) powder with the ammonia aqueous solution of another kind of metal; Perhaps alternately adopt the ammonia aqueous solution nickeliferous or that contain the single metal of cobalt to mix, wrap the plating reaction, the nickel cobalt (alloy) powder that then obtains having sandwich with the metal dust that filters out; Perhaps adopt the ammonia aqueous solution that contains two kinds of metals simultaneously to mix, deposit bag plating reaction, the nickel cobalt (alloy) powder that also obtains having sandwich with the metal dust that filters out.

9, above-mentioned nickel cobalt (alloy) powder through the preparation of hydro-thermal hydrogen reduction method; when the nickel that it is inner, cobalt distributed components; promptly under hydrogen or nitrogen protection condition, heat treatment is 16～30 hours under 500～950 ℃ temperature, obtains nickel, the uniform product of cobalt composition.

10, nanoscale alloy powder product average diameter is about 30～90nm, and ultra-fine level metal dust product average diameter is about 200～950nm, and fine level metal dust product average diameter is about 2～20 μ m.

The present invention has following advantage and good effect: the process that adopts the hydro-thermal hydrogen reduction, with nickelous sulfate, cobaltous sulfate is raw material, with ammonium sulfate, the ammoniacal liquor preparation ammonification aqueous solution, add a small amount of anthraquinone, as reducing agent, in autoclave, can prepare nanometer, ultra-fine or superfine metallic nickel powder or cobalt powder or cobalt nickel powder product with hydrogen.Raw material is easy to get, and technology is simple, flow process is short, and production cost is low, and production process is easy to control, production efficiency height.The epigranular of metal dust, size and composition are controlled, good product quality, the preparation condition scope is wide.The recyclable utilization of ammonium sulfate tail washings that bag plating back produces, environmentally safe.

The specific embodiment

Embodiment 1

Nano-nickel powder is made crystal seed, and the ammonia aqueous solution of nickelous sulfate is the feedstock production extra-fine nickel powder.Take by weighing nickelous sulfate 30kg and ammonium sulfate 15.3kg, add in the tank diameter, pour deionized water 60L into, be heated to 60 ℃, stirring and dissolving is measured concentration and is 25% ammoniacal liquor 18.45L, add in the tank diameter, with the nickelous sulfate in the groove and the aqueous solution of ammonium sulfate, with deionized water solution is diluted to cumulative volume 100L again, be made into nickeliferous about 63g/L, ammonia nickel than be 2.3, ammonium sulfate concentrations is the mixed solution of 150g/L; In mixed solution, add anthraquinone 10g, gelatine 1.5g, add and contain the aqueous solution that granularity is about the nano-nickel powder 2.1kg of 30～50nm, the mixed solution that will contain anthraquinone, gelatine, nano-nickel powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, nano-nickel powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 125 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 2.5MPa, and maintenance communicate with autoclave.After 3 minutes, Hydrogen Vapor Pressure descends rapidly, and the nickel ion in the ie in solution is deposited on the nano-nickel powder surface by hydrogen reducing, and nano-nickel powder is constantly grown up; After 15 minutes, temperature in the kettle rises to 148 ℃, and Hydrogen Vapor Pressure descends slowly; Through after 3 minutes, Hydrogen Vapor Pressure no longer descends again, and the nickel ion in the still in the solution is fully by hydrogen reducing, and bag is plated in the surface of nano-nickel powder, grows up into extra-fine nickel powder at last.Open cooling water, flow through in the cooler in the autoclave, the outside contains the aqueous solution of extra-fine nickel powder and lowers the temperature gradually; When the aqueous solution in the autoclave is cooled to 86 ℃, discharge the aqueous solution of extra-fine nickel powder; Filtering means dehydration, and spend deionised water, filtering powder, repeat 4 times; In vacuum drying chamber in 60 ℃ of dryings 6 hours; Take out the cooling back, obtains the extra-fine nickel powder product, and weight is about 8.1kg, and granularity is about 450～820nm.Bag plating tail washings is through evaporation, concentrated, crystallization, reclaim sulfuric acid ammonium.

Embodiment 2

Nano-cobalt powder is made crystal seed, and the ammonia aqueous solution of cobaltous sulfate is the feedstock production super-fine cobalt powder.Take by weighing cobaltous sulfate 31.3kg and ammonium sulfate 12.2kg, add in the tank diameter, pour deionized water 70L into, be heated to 40 ℃, stirring and dissolving is measured concentration and is 25% ammoniacal liquor 27.8L, add in the tank diameter, with the cobaltous sulfate in the groove and the aqueous solution of ammonium sulfate, with deionized water solution is diluted to cumulative volume 120L again, be made into contain the about 52.1g/L of cobalt, ammonia cobalt than 3.5, the mixed solution of ammonium sulfate 99.6g/L; Add anthraquinone 18g, gelatine 2g in mixed solution, add the nano-cobalt powder 2.3kg that granularity is about 53～85nm, the mixed solution that will contain anthraquinone, gelatine, nano-cobalt powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, nano-cobalt powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 135 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 4.5MPa, and maintenance communicate with autoclave.After 4 minutes, Hydrogen Vapor Pressure descends rapidly, and the cobalt ions in the ie in solution is deposited on the nano-cobalt powder surface by hydrogen reducing, and nano-cobalt powder is constantly grown up; After 18 minutes, temperature in the kettle rises to 151 ℃, and Hydrogen Vapor Pressure descends slowly; Through after 4 minutes, Hydrogen Vapor Pressure no longer descends again, and the cobalt ions in the still in the solution is reduced fully by hydrogen, and bag is plated in the surface of nano-cobalt powder, grows up into super-fine cobalt powder at last.Open cooling water, will contain the aqueous solution cooling of super-fine cobalt powder with the chimney cooler in the autoclave; When the aqueous solution in the autoclave is cooled to 89 ℃, discharge the aqueous solution that contains super-fine cobalt powder; Filtering means dehydration, and spend deionised water, filtering powder, repeat 3 times; In vacuum drying chamber in 70 ℃ of dryings 6 hours; Take out the cooling back, obtains the super-fine cobalt powder product, and weight is about 8.3kg, and granularity is about 300～730nm.Bag plating tail washings is through evaporation, concentrated, crystallization, reclaim sulfuric acid ammonium.

Embodiment 3

Nano-cobalt powder is made crystal seed, and the ammonia aqueous solution of nickelous sulfate is feedstock production nanometer nickel-cobalt alloy powder.Take by weighing nickelous sulfate 30kg and ammonium sulfate 27.9kg, add in the tank diameter, pour deionized water 80L into, be heated to 50 ℃, stirring and dissolving is measured concentration and is 25% ammoniacal liquor 25.7L, add in the tank diameter, ammonia aqueous solution with nickelous sulfate in the groove is diluted to cumulative volume 130L with deionized water with solution again, be made into nickeliferous about 48.5g/L, ammonia nickel than 3.2, the mixed solution of ammonium sulfate 210.3g/L; Add anthraquinone 14.3g, gelatine 1.8g in mixed solution, add the nano-cobalt powder 5.8kg that granularity is about 15～45nm, the mixed solution that will contain anthraquinone, gelatine, nano-cobalt powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, nano-cobalt powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 130 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 3MPa, and maintenance communicate with autoclave.After 2 minutes, Hydrogen Vapor Pressure descends, and the nickel ion in the solution is deposited on the nano-cobalt powder surface by hydrogen reducing, and nano-cobalt powder is constantly grown up; After 12 minutes, temperature in the kettle rises to 142 ℃, and Hydrogen Vapor Pressure descends slowly; Through after 3 minutes, Hydrogen Vapor Pressure no longer descends again, and the nickel ion in the still in the solution is fully by hydrogen reducing, and bag is plated in the surface of nano-cobalt powder, grows up into the nanometer nickel-cobalt alloy powder at last.Open cooling water, flow through in the chimney cooler in the autoclave, the aqueous solution that contains the nanometer nickel-cobalt alloy powder is lowered the temperature gradually; When the aqueous solution in the autoclave is cooled to 85 ℃, discharge the aqueous solution that contains the nanometer nickel-cobalt alloy powder; Filtering means dehydration, and spend deionised water, filtering powder, repeat 4 times; In vacuum drying chamber in 60 ℃ of dryings 6 hours; Take out cooling back, obtains nanometer nickel-cobalt alloy powder product, and weight is about 11.5kg, and it is about 46.7% to contain cobalt, and granularity is about 70～90nm.Bag plating tail washings is through evaporation, concentrated, crystallization, reclaim sulfuric acid ammonium.

In above-mentioned batching, 30Kg changes 9.3kg into the nickelous sulfate consumption, 25% ammonia volume 25.7L changes 8L into, other composition and nano-cobalt powder consumption are constant, repeat above-mentioned preparation process, obtain the nanometer nickel-cobalt alloy powder of nickeliferous about 25.9% (wherein contain cobalt about 74.1%), granularity is about 30～65nm.

Embodiment 4

Nano-nickel powder is made crystal seed, and the ammonia aqueous solution of cobaltous sulfate is feedstock production nanometer nickel-cobalt alloy powder.Take by weighing cobaltous sulfate 12.5kg and ammonium sulfate 8.2kg, add in the tank diameter, pour deionized water 80L into, be heated to 55 ℃, stirring and dissolving is measured concentration and is 25% ammoniacal liquor 12.1L, add in the tank diameter, with the cobaltous sulfate in the groove and the aqueous solution of ammonium sulfate, with deionized water solution is diluted to cumulative volume 125L again, be made into contain the about 20g/L of cobalt, ammonia cobalt than 3.8, the mixed solution of ammonium sulfate 64.0g/L; Add anthraquinone 13g, gelatine 1.5g in mixed solution, add the nano-nickel powder 14.6kg that granularity is about 45～65nm, the mixed solution that will contain anthraquinone, gelatine, nano-nickel powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, nano-nickel powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 130 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 3.3MPa, and maintenance communicate with autoclave.After 2 minutes, Hydrogen Vapor Pressure descends, and the cobalt ions in the solution is deposited on the nano-nickel powder surface by hydrogen reducing; After 6 minutes, the high pressure temperature in the kettle rises to 136 ℃, and Hydrogen Vapor Pressure descends slowly; Through after 2 minutes, Hydrogen Vapor Pressure no longer descends again, and the nickel ion in the still in the solution is deposited on the surface of nano-nickel powder fully by hydrogen reducing, forms the nanometer nickel-cobalt alloy powder at last.Open cooling water, autoclave is included the aqueous solution cooling of nanometer nickel-cobalt alloy powder; When the aqueous solution in the autoclave was cooled to 85 ℃, discharge contained the nanometer nickel-cobalt alloy powder aqueous solution; Filtering means dehydration, and spend deionised water, filtering powder, repeat 3 times; In vacuum drying chamber in 75 ℃ of dryings 5 hours; Take out the cooling back, obtains nanometer nickel-cobalt alloy powder product, and weight is about 11.2kg, contains about 14.9% (wherein nickeliferous about 85.1%) of cobalt, and granularity is about 55～80nm.Filter tail washings through evaporation, concentrated, crystallization, reclaim sulfuric acid ammonium.

In above-mentioned preparation process, change into as the addition 14kg of the nano-nickel powder crystal seed that granularity is about 45～65nm and to add 34.8kg, other condition is constant, repeat above-mentioned preparation process, can obtain nanometer nickel-cobalt alloy powder product weight 36.5kg, contain cobalt about 6.5% (wherein nickeliferous about 93.4%, tenor contains oxygen by removal and amounts to), granularity is about 50～80nm.

As replacing the nano-nickel powder crystal seed with the nano-cobalt powder crystal seed, the ammonia aqueous solution that replaces cobaltous sulfate with the ammonia aqueous solution of nickelous sulfate, with the ammonia aqueous solution of nano-cobalt powder with the nickelous sulfate of being prepared, adopt said method, can prepare the nanometer nickel-cobalt alloy powder equally.

Embodiment 5

Nano-cobalt powder is made crystal seed, and the ammonia aqueous solution of nickelous sulfate is the ultra-fine nickel cobalt (alloy) powder of feedstock production.Take by weighing nickelous sulfate 50kg and ammonium sulfate 25.7kg, add in the tank diameter, pour deionized water 90L into, be heated to 60 ℃, stirring and dissolving is measured concentration and is 25% ammoniacal liquor 29.4L, add in the tank diameter, with the nickelous sulfate in the groove and the aqueous solution of ammonium sulfate, with deionized water solution is diluted to cumulative volume 140L again, be made into nickeliferous about 75g/L, ammonia nickel than 2.2, the mixed solution of ammonium sulfate 180g/L; Add anthraquinone 15g, gelatine 2g in mixed solution, add the nano-cobalt powder 0.8kg that granularity is about 15～45nm, the mixed solution that will contain anthraquinone, gelatine, nano-cobalt powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, nano-nickel powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 130 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 3.8MPa, and maintenance communicate with autoclave.After 3 minutes, Hydrogen Vapor Pressure descends, and the nickel ion in the solution is deposited on the nano-cobalt powder surface by hydrogen reducing, and nano-cobalt powder is constantly grown up; After 16 minutes, temperature in the kettle rises to 155 ℃, and Hydrogen Vapor Pressure begins slow decline; Through after 3 minutes, Hydrogen Vapor Pressure no longer descends again, and the nickel ion in the autoclave in the solution is reduced fully by hydrogen, and bag is plated in the surface of nano-cobalt powder, grows up into ultra-fine nickel cobalt (alloy) powder at last.Open cooling water, will contain the aqueous solution cooling of ultra-fine nickel cobalt (alloy) powder by the chimney cooler in the autoclave; When the aqueous solution in the autoclave is cooled to 86 ℃, discharge the aqueous solution that contains the nanometer nickel-cobalt alloy powder; Filtering means dehydration, and spend deionised water, filtering powder, repeat 3 times; In vacuum drying chamber in 60 ℃ of dryings 7 hours; Take out cooling back, obtains ultra-fine nickel cobalt (alloy) powder product, and weight is about 10.8kg, and it is about 6.9% to contain cobalt, and granularity is about 9～14 μ m.Tail washings is through evaporation, concentrated, crystallization, reclaim sulfuric acid ammonium.

In above-mentioned preparation process as with the nano-nickel powder crystal seed, replace the nano-cobalt powder crystal seed, the ammonia aqueous solution that replaces nickelous sulfate with the ammonia aqueous solution of cobaltous sulfate, with the ammonia aqueous solution of nano-nickel powder with the cobaltous sulfate of being prepared, adopt said method, can prepare ultra-fine nickel cobalt (alloy) powder equally.

Embodiment 6

Nano-nickel powder is made crystal seed, and the ammonia aqueous solution of nickelous sulfate is the fine nickel powder of feedstock production.Take by weighing nickelous sulfate 50kg and ammonium sulfate 22.3kg, add in the tank diameter, pour deionized water 70L into, be heated to 85 ℃, stirring and dissolving is measured concentration and is 25% ammoniacal liquor 33.4L, add in the tank diameter, with the nickelous sulfate in the groove and the aqueous solution of ammonium sulfate, with deionized water solution is diluted to cumulative volume 115L again, be made into nickeliferous about 91.3g/L, ammonia nickel than 2.5, the mixed solution of ammonium sulfate 180g/L; Add anthraquinone 20g, gelatine 1.5g in mixed solution, add and contain the nano-nickel powder 1.2kg that granularity is about 50～85nm, the mixed solution that will contain anthraquinone, gelatine, nano-nickel powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, nano-nickel powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 130 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 2.8MPa, and maintenance communicate with autoclave.After 4 minutes, Hydrogen Vapor Pressure descends rapidly, and the nickel ion in the solution is deposited on the nano-nickel powder surface by hydrogen reducing, and nano-nickel powder is constantly grown up; After 20 minutes, temperature in the kettle rises to 156 ℃, and Hydrogen Vapor Pressure begins to descend slowly; Through after 5 minutes, Hydrogen Vapor Pressure no longer descends again, and the nickel ion in the still in the solution is reduced fully by hydrogen, and bag is plated in the surface of nano-nickel powder, grows up into fine nickel powder at last.Open cooling water,, will contain the aqueous solution cooling of fine nickel powder by the chimney cooler in the autoclave; When the aqueous solution in the autoclave is cooled to 85 ℃, discharge the aqueous solution that contains fine nickel powder; Filtering means dehydration, and spend deionised water, filtering powder, repeat 3 times; In vacuum drying chamber in 50 ℃ of dryings 3 hours; Take out the cooling back, obtains fine nickel powder product, and weight is about 10.3kg, and granularity is about 6～10 μ m, and nickeliferous about 99.6%.

Replace nano-nickel powder to make crystal seed with nano-cobalt powder, replace the nickelous sulfate preparation ammonia aqueous solution,, adjust batching, press the aforesaid operations process, can prepare fine cobalt powder equally the ammonia aqueous solution of nano-cobalt powder and cobaltous sulfate with cobaltous sulfate.

Adopt the nanometer nickel-cobalt alloy powder to make crystal seed, adjust batching, press the aforesaid operations process,, can prepare fine nickel cobalt (alloy) powder equally with the ammonia aqueous solution of cobaltous sulfate or nickelous sulfate.

Embodiment 7

Extra-fine nickel powder is made crystal seed, and the ammonia aqueous solution of nickelous sulfate is the fine nickel powder of feedstock production.Take by weighing nickelous sulfate 50kg and ammonium sulfate 11.7kg, add in the tank diameter, pour deionized water 60L into, be heated to 60 ℃, stirring and dissolving; Add concentration and be 25% ammoniacal liquor 37.4L, nickelous sulfate is dissolved fully, with deionized water solution is diluted to cumulative volume 115L again, be made into nickeliferous about 91.3g/L, ammonia nickel than 2.8, the mixed solution of ammonium sulfate 100g/L; Add anthraquinone 20g, gelatine 1.5g in mixed solution, add and contain the extra-fine nickel powder 3.2kg that granularity is about 450～820nm, the mixed solution that will contain anthraquinone, gelatine, extra-fine nickel powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, extra-fine nickel powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 130 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 3MPa, and maintenance communicate with autoclave.After 3 minutes, Hydrogen Vapor Pressure descends rapidly, and the nickel ion in the solution is deposited on the extra-fine nickel powder surface by hydrogen reducing, and extra-fine nickel powder is constantly grown up; After 10 minutes, temperature in the kettle rises to 152 ℃, and Hydrogen Vapor Pressure begins to descend slowly; Through after 4 minutes, Hydrogen Vapor Pressure no longer descends again, and the nickel ion in the autoclave in the solution is reduced fully by hydrogen, and bag is plated in the surface of extra-fine nickel powder, grows up into fine nickel powder at last.Open cooling water,, will contain the aqueous solution cooling of fine nickel powder by the chimney cooler in the autoclave; When the aqueous solution in the autoclave is cooled to 85 ℃, discharge the aqueous solution that contains fine nickel powder; Filtering means dehydration, and spend deionised water, filtering powder, repeat 3 times; In vacuum drying chamber in 60 ℃ of dryings 3 hours; Take out the cooling back, obtains fine nickel powder product, and weight is about 13.1kg, and granularity is about 3～8 μ m, and nickeliferous about 99.7%.

Replace extra-fine nickel powder to make crystal seed with super-fine cobalt powder, replace the nickelous sulfate preparation ammonia aqueous solution,, adjust batching, press the aforesaid operations process, can prepare fine cobalt powder equally the ammonia aqueous solution of super-fine cobalt powder and cobaltous sulfate with cobaltous sulfate.

Adopt ultra-fine nickel cobalt (alloy) powder to make crystal seed, adjust batching, press the aforesaid operations process,, can prepare fine nickel cobalt (alloy) powder equally with the ammonia aqueous solution of cobaltous sulfate or nickelous sulfate.

Embodiment 8

Nano-cobalt powder is made crystal seed, is the fine cobalt powder of feedstock production with the ammonia aqueous solution of cobaltous sulfate, takes by weighing cobaltous sulfate 40kg and ammonium sulfate 22.9kg, adds in the tank diameter, pours deionized water 80L into, is heated to 60 ℃, stirring and dissolving; Add concentration and be 25% ammoniacal liquor 30.5L, with deionized water solution is diluted to cumulative volume 140L again, be made into nickeliferous about 57.1g/L, ammonia cobalt than 3, the mixed solution of ammonium sulfate 160g/L; Add anthraquinone 18g, gelatine 1.5g in mixed solution, add the nano-cobalt powder 0.6kg that granularity is about 53～85nm, the mixed solution that will contain anthraquinone, gelatine, nano-cobalt powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, nano-cobalt powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 130 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 3.2MPa, and maintenance communicate with autoclave.After 4 minutes, Hydrogen Vapor Pressure descends rapidly, and the cobalt ions in the solution is deposited on the nano-cobalt powder surface by hydrogen reducing, grows up into super-fine cobalt powder, and continues to grow up into fine cobalt powder; After 16 minutes, temperature in the kettle rises to 149 ℃, and Hydrogen Vapor Pressure begins to descend slowly; Through after 3 minutes, Hydrogen Vapor Pressure no longer descends again, and the cobalt ions in the autoclave in the solution is reduced fully by hydrogen, and bag is plated in the surface of nano-cobalt powder, grows up into fine cobalt powder at last.Open cooling water,, will contain the aqueous solution cooling of fine cobalt powder by the chimney cooler in the autoclave; When the aqueous solution in the autoclave is cooled to 85 ℃, discharge the aqueous solution that contains fine cobalt powder; Filtering means dehydration, and spend deionised water, filtering powder, repeat 3 times; In vacuum drying chamber in 50 ℃ of dryings 5 hours; Take out the cooling back, obtains fine cobalt powder product, and weight is about 8.1kg, and granularity is about 7～11 μ m.

Replace nano-cobalt powder to make crystal seed with nano-nickel powder, replace the cobaltous sulfate preparation ammonia aqueous solution,, adjust batching, press the aforesaid operations process, can prepare fine nickel powder equally the ammonia aqueous solution of nano-nickel powder and nickelous sulfate with nickelous sulfate.Perhaps the ammonia aqueous solution of ammonia aqueous solution, nano-cobalt powder and the nickelous sulfate of nano-nickel powder and cobaltous sulfate is adjusted batching, presses the aforesaid operations process, can prepare the bigger fine nickel cobalt (alloy) powder of nickel and cobalt composition difference.

Embodiment 9

The aqueous solution that contains metal nickel powder (or cobalt powder, cobalt nickel powder) in the foregoing description filters out metal dust after discharging in the autoclave from solution, do not wash, and once more as crystal seed, is used to prepare ultra-fine or micro-fine metal powder.

After cobalt is about 46.7% containing of obtaining, granularity is about 70～90nm nanometer nickel-cobalt alloy powder and filters out from solution with the foregoing description 3, do not wash, it is standby to measure 5kg by its dry weight.Take by weighing nickelous sulfate 50kg and 15.9kg ammonium sulfate, add in the tank diameter, pour deionized water 80L into, be heated to 70 ℃, stirring and dissolving is measured concentration and is 25% ammoniacal liquor 34.8L, add in the tank diameter, with the nickelous sulfate in the groove and the aqueous solution of ammonium sulfate, with deionized water solution is diluted to cumulative volume 130L again, be made into nickeliferous approximately about 80.8g/L, ammonia nickel than 2.6, the mixed solution of ammonium sulfate 120g/L; Add anthraquinone 15g, gelatine 1.5g in mixed solution, the nanometer nickel-cobalt alloy powder 5kg that the foregoing description 3 is obtained mixes with it then, and is transferred in the autoclave that volume is 300L sealing autoclave together.

Open the autoclave stirring motor, the nanometer nickel-cobalt alloy powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 120 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 3.2MPa, and maintenance communicate with autoclave.After 3 minutes, Hydrogen Vapor Pressure descends, and the nickel ion in the solution is deposited on the nano-cobalt powder surface by hydrogen reducing, and the nanometer nickel-cobalt alloy powder is constantly grown up; After 10 minutes, temperature in the kettle rises to 141 ℃, and Hydrogen Vapor Pressure descends slowly; Through after 3 minutes, Hydrogen Vapor Pressure no longer descends again, and the nickel ion in the still in the solution is fully by hydrogen reducing, and bag is plated in the surface of nanometer nickel-cobalt alloy powder, grows up into ultra-fine nickel cobalt (alloy) powder at last.Open cooling water, the aqueous solution that will be contained ultra-fine nickel cobalt (alloy) powder by the chimney cooler in the autoclave is lowered the temperature gradually; When the aqueous solution in the autoclave was cooled to 85 ℃, discharge contained the ultra-fine nickel cobalt (alloy) powder aqueous solution; Filtering means dehydration, and spend deionised water, filtering powder, repeat 4 times; In vacuum drying chamber in 55 ℃ of dryings 6 hours; Take out cooling back, obtains ultra-fine nickel cobalt (alloy) powder product, and weight is about 14.8kg, and it is about 14.8% to contain cobalt, and granularity is about 280～420nm.

Replace the nanometer nickel-cobalt alloy powder to make crystal seed with nano-nickel powder, nano-cobalt powder, with the ammonia aqueous solution of nickelous sulfate, the single metal of cobaltous sulfate or simultaneously a kind of in the two metal ammonia aqueous solution of sulfur acid nickel and cobaltous sulfate mix mutually, adjust batching, press the aforesaid operations process, can prepare ultra-fine pure nickel powder, ultra-fine pure cobalt powder or ultra-fine nickel cobalt (alloy) powder equally.Extra-fine nickel powder, super-fine cobalt powder or the ultra-fine nickel cobalt (alloy) powder of perhaps above-mentioned each example preparation once more as crystal seed, are adjusted batching without washing, press the aforesaid operations process, can prepare fine pure nickel powder, fine pure cobalt powder or fine nickel cobalt (alloy) powder.

As in embodiment 1, embodiment 2, after each the reaction, solution metal powder (nickel powder or cobalt powder) is filtered out, do not wash, once more as crystal seed, nickel powder is prepared burden with the single metal ammonia aqueous solution of nickelous sulfate always, or cobalt powder is prepared burden with the single metal ammonia aqueous solution of cobaltous sulfate always, press the aforesaid operations process,, also can prepare fine pure nickel powder or fine pure cobalt powder at last through repeatedly preparing extra-fine nickel powder or super-fine cobalt powder respectively after the reaction.If but with the metal dust that filters out and the single metal ammonia aqueous solution that contains another kind of metal ion, or two metal ammonia aqueous solution of while sulfur acid nickel and cobaltous sulfate, adjust batching, press the aforesaid operations process, through repeatedly then preparing ultra-fine or fine nickel cobalt (alloy) powder respectively after the reaction.

Embodiment 10

After the aqueous solution that contains metal nickel powder (or cobalt powder, cobalt nickel powder) in the foregoing description discharged in the autoclave, filter out metal dust wherein, do not wash, once more as crystal seed, the two metal ammonia aqueous solution with while sulfur acid nickel and cobaltous sulfate are raw material, preparation nickel cobalt (alloy) powder.

In the foregoing description 2 preparation process, after hydrogen reduction reaction is finished, when the aqueous solution in the autoclave is cooled to 89 ℃, discharge the aqueous solution that contains super-fine cobalt powder; Filtering means dehydration does not wash, does not dry, and promptly is not as final products, but the super-fine cobalt powder that will filter gained is as crystal seed, again with two metal ammonia aqueous solution of nickelous sulfate and cobaltous sulfate, and preparation nickel cobalt (alloy) powder after hydrogen reduction.

Take by weighing nickelous sulfate 25kg, cobaltous sulfate 30kg and 24.5kg ammonium sulfate, add in the tank diameter, pour deionized water 90L into, be heated to 50 ℃, stirring and dissolving is measured concentration and is 25% ammoniacal liquor 37.2L, add in the tank diameter, with the cobaltous sulfate in the groove and the aqueous solution of ammonium sulfate, with deionized water solution is diluted to cumulative volume 150L again, be made into nickeliferous about 35g/L, cobalt 40g/L, ammonia metal (nickel and cobalt summation) than 2.6, the mixed solution of ammonium sulfate 160g/L; In mixed solution, add anthraquinone 20g, gelatine 2g, the granularity that adds embodiment 2 preparations is about the super-fine cobalt powder 3kg (by dry weight) of 300～730nm, the mixed solution that will contain anthraquinone, gelatine, super-fine cobalt powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, super-fine cobalt powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 130 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 3.6MPa, and maintenance communicate with autoclave.After 3 minutes, Hydrogen Vapor Pressure descends rapidly, and the nickel ion in the solution is earlier by hydrogen reducing, and bag is plated in the super-fine cobalt powder surface, and super-fine cobalt powder is constantly grown up, and becomes the nickel cobalt (alloy) powder; After 8 minutes, temperature in the kettle rises to 143 ℃, and the Hydrogen Vapor Pressure decrease speed slows down slightly; Through after 2 minutes, Hydrogen Vapor Pressure descends rapidly again again, at this moment cobalt ions in the solution and remaining minor amount of nickel ion) by hydrogen reducing, bag is plated in the surface of nickel cobalt (alloy) powder, and the nickel cobalt (alloy) powder is constantly grown up; After 12 minutes, temperature in the kettle rises to 158 ℃, Hydrogen Vapor Pressure no longer descends, nickel, cobalt ions in the still in the solution are reduced fully by hydrogen, and bag is plated in the surface of super-fine cobalt powder, grows up into the nickel cobalt (alloy) powder at last, and has sandwich, be that kernel is a super-fine cobalt powder, the metallic nickel that restores earlier is the intermediate layer, after the metallic cobalt that restores at outermost layer.Open cooling water, will contain the aqueous solution cooling of super-fine cobalt powder with the chimney cooler in the autoclave; When the aqueous solution in the autoclave is cooled to 85 ℃, discharge the aqueous solution of nickel and cobalt containing alloy powder; Filtering means dehydration, and spend deionised water, filtering powder, repeat 3 times; In vacuum drying chamber in 60 ℃ of dryings 5 hours; Take out the cooling back, obtains fine nickel cobalt (alloy) powder product, and weight is about 13.4kg, and granularity is about 2.5～6 μ m.Bag plating tail washings is through evaporation, concentrated, crystallization, reclaim sulfuric acid ammonium.

As replacing super-fine cobalt powder to make crystal seed with nano-nickel powder, nano-cobalt powder, nanometer nickel-cobalt alloy powder, with two metal ammonia aqueous solution of while sulfur acid nickel and cobaltous sulfate, adjust batching, press the aforesaid operations process, can prepare ultra-fine nickel cobalt (alloy) powder.Extra-fine nickel powder, super-fine cobalt powder or the ultra-fine nickel cobalt (alloy) powder of perhaps above-mentioned each example preparation are without washing, once more as crystal seed, adjust batching, two metal ammonia aqueous solution with while sulfur acid nickel and cobaltous sulfate, press the aforesaid operations process, can prepare fine nickel cobalt (alloy) powder, these nickel cobalt (alloy) powder have layer structure, promptly since in the two metal ammonia aqueous solution nickel and cobalt in the hydrogen reduction process, separate out in proper order differently, contain metal nickel dam and layer of metal cobalt in the powder simultaneously.

Embodiment 11

Make crystal seed with super-fine cobalt powder, be used alternatingly the ammonia aqueous feed solution of the ammonia aqueous solution and the cobaltous sulfate of nickelous sulfate, the nickel cobalt (alloy) powder that preparation has sandwich.First plating nickel for the first time, take by weighing nickelous sulfate 30kg and ammonium sulfate 27.9kg, add in the tank diameter, pour deionized water 80L into, be heated to 50 ℃, stirring and dissolving, measure concentration and be 25% ammoniacal liquor 18.5L, add in the tank diameter, with the nickelous sulfate in the groove and the aqueous solution of ammonium sulfate, with deionized water solution is diluted to cumulative volume 130L again, be made into nickeliferous about 48.5g/L, ammonia nickel than 2.3, the mixed solution of ammonium sulfate 210.3g/L; Add anthraquinone 16g, gelatine 1.8g in mixed solution, granularity is about the super-fine cobalt powder 3kg of 350～660nm, and the mixed solution that will contain anthraquinone, gelatine, super-fine cobalt powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, super-fine cobalt powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 130 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 3MPa, and maintenance communicate with autoclave.After 3 minutes, Hydrogen Vapor Pressure descends rapidly, and the nickel ion in the solution is deposited on the super-fine cobalt powder surface by hydrogen reducing, and super-fine cobalt powder is constantly grown up; After 13 minutes, temperature in the kettle rises to 144 ℃, and Hydrogen Vapor Pressure descends slowly; Through after 3 minutes, Hydrogen Vapor Pressure no longer descends again, and the nickel ion in the still in the solution is fully by hydrogen reducing, and bag is plated in the surface of super-fine cobalt powder, grows up into fine nickel cobalt (alloy) powder at last.Open cooling water, because the chimney cooler in the autoclave is lowered the temperature the aqueous solution of nickel cobalt (alloy) powder gradually; When the aqueous solution in the autoclave is cooled to below 90 ℃, discharge the nickel and cobalt containing alloy powder aqueous solution; Filtering means dehydration does not wash the nickel cobalt (alloy) powder, and as crystal seed.

Wrap for the second time cobalt plating.Take by weighing cobaltous sulfate 30kg and ammonium sulfate 25kg, add in the tank diameter, pour deionized water 80L into, be heated to 50 ℃, stirring and dissolving is measured concentration and is 25% ammoniacal liquor 19L, add in the tank diameter, with the cobaltous sulfate in the groove and the aqueous solution of ammonium sulfate, with deionized water solution is diluted to cumulative volume 130L again, be made into contain the about 46.1g/L of cobalt, ammonia cobalt than 2.5, the mixed solution of ammonium sulfate 188.5g/L; Add anthraquinone 15g, gelatine 1.5g in mixed solution, and mix with the nickel cobalt (alloy) powder of the acquisition of bag plating for the first time, the mixed solution that will contain anthraquinone, gelatine, nickel cobalt (alloy) powder then is transferred in the autoclave that volume is 300L, sealing autoclave.Open the autoclave stirring motor, the nickel cobalt (alloy) powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 130 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 3.3MPa, and maintenance communicate with autoclave.After 3 minutes, Hydrogen Vapor Pressure descends rapidly, and the cobalt ions in the solution is deposited on nickel cobalt (alloy) powder surface by hydrogen reducing, and the nickel cobalt (alloy) powder is constantly grown up; After 14 minutes, temperature in the kettle rises to 150 ℃, and Hydrogen Vapor Pressure descends slowly; Through after 4 minutes, Hydrogen Vapor Pressure no longer descends again, and the nickel ion in the still in the solution has wrapped the surface that is plated in the nickel cobalt (alloy) powder, grows up into fine nickel cobalt (alloy) powder at last.Open cooling water, the chimney cooler in the autoclave is lowered the temperature the aqueous solution of nickel cobalt (alloy) powder gradually; When the aqueous solution in the autoclave is cooled to below 90 ℃, discharge the aqueous solution of nickel and cobalt containing alloy powder; Filtering means dehydration, and spend deionised water, filtering powder repeats 4 times, in vacuum drying chamber in 55 ℃ of dryings 6 hours; Take out cooling back, obtains fine nickel cobalt (alloy) powder product, and its weight is about 14.3kg, and nickeliferous about 41.3%, granularity is about 3.5～5.6 μ m.It is that metallic cobalt, intermediate layer are that metallic nickel, skin are the sandwich of metallic cobalt that the nickel cobalt (alloy) powder has the center.

After the nickel cobalt (alloy) powder aqueous solution of above-mentioned preparation process output filtered, plating nickel, cobalt formed the nickel cobalt (alloy) powder with multilayer sandwich once more.And, control the thickness of every layer of coated metal by the amount of the each coated metal of control.

The crystal seed that adopts first time nano-nickel powder, nano-cobalt powder, nanometer nickel-cobalt alloyed powder, perhaps use a kind of replacement super-fine cobalt powder in extra-fine nickel powder and the ultra-fine cobalt nickel powder, and cooperate with the single ammonia solution of nickelous sulfate or cobaltous sulfate, adjust batching, press the aforesaid operations process, can prepare nickel cobalt (alloy) powder equally with sandwich.

Embodiment 12

Adopting nano-nickel powder to make crystal seed, is raw material with the two metal ammonia aqueous solution of while sulfur acid nickel and cobaltous sulfate, the ultra-fine or fine nickel cobalt (alloy) powder that preparation has sandwich.

Take by weighing nickelous sulfate 30kg, cobaltous sulfate 35kg and ammonium sulfate 21.2kg, add in the tank diameter, pour deionized water 100L into, be heated to 50 ℃, stirring and dissolving is measured concentration and is 25% ammoniacal liquor 40.5L, add in the tank diameter, aqueous solution with nickelous sulfate, cobaltous sulfate and ammonium sulfate in the groove is diluted to cumulative volume 160L with deionized water with solution again, be made into nickeliferous about 39.4g/L, cobalt 43.8g/L, ammonia metal (nickel and cobalt summation) than 2.4, the mixed solution of ammonium sulfate 130g/L; Add anthraquinone 23g, gelatine 1.8g in mixed solution, add and contain the nano-nickel powder 4.5kg that granularity is about 30～50nm, the mixed solution that will contain anthraquinone, gelatine, nano-nickel powder then is transferred in the autoclave that volume is 300L, sealing autoclave.

Open the autoclave stirring motor, nano-nickel powder is suspended in the mixed solution; With the heating of the solution in the autoclave, when solution reaches 130 ℃, the hydrogen in the pressure-reducing cushioning jar is charged in the autoclave, make the still internal pressure reach 4MPa, and maintenance communicate with autoclave.After 2 minutes, Hydrogen Vapor Pressure descends rapidly, and the nickel ion in the solution is earlier by hydrogen reducing, and bag is plated in the nano-nickel powder surface, and nano-nickel powder is constantly grown up, and wherein has the part nano-nickel powder to grow up and is extra-fine nickel powder; After 6 minutes, temperature in the kettle rises to 145 ℃, and the Hydrogen Vapor Pressure decrease speed slows down slightly; Through after 2 minutes, Hydrogen Vapor Pressure descends rapidly again again, at this moment cobalt ions in the solution and remaining minor amount of nickel ion) by hydrogen reducing, bag is plated in the surface of nickel powder, and the nickel cobalt (alloy) powder is constantly grown up; After 12 minutes, temperature in the kettle rises to 162 ℃, Hydrogen Vapor Pressure no longer descends, nickel, cobalt ions in the still in the solution are reduced fully by hydrogen, bag is plated in the surface of the nano-nickel powder that adds in advance, grow up at last ultra-fine nickel cobalt (alloy) powder, its inside is metallic nickel, after the metallic cobalt that restores at skin.Open cooling water, will contain the aqueous solution cooling of ultra-fine nickel cobalt (alloy) powder with the chimney cooler in the autoclave; When the aqueous solution in the autoclave is cooled to 85 ℃, discharge the aqueous solution of nickel and cobalt containing alloy powder; Filtering means dehydration, wherein a part of nickel cobalt (alloy) powder spends deionised water, filtering powder, repeat 4 times, in vacuum drying chamber in 55 ℃ of dryings 6 hours; Take out cooling back, obtains ultra-fine nickel cobalt (alloy) powder product, and weight is about 11.6kg, and it is about 39.5% to contain cobalt, and granularity is about 230～560nm.The nickel cobalt (alloy) powder that remaining another part filters out does not wash and is dry, once more as crystal seed; In addition preparation and above-mentioned two metal ammonia aqueous solution portions of sulfur acid nickel and cobaltous sulfate with sample ingredient the time mixes with remaining nickel cobalt (alloy) powder without washing and dry another part, is transferred in the autoclave that volume is 300L sealing autoclave.Repeat above-mentioned hydro-thermal hydrogen reduction operating process,, and spend deionised water, filtering powder, repeat 3 times the aqueous solution filtering means dehydration of nickel and cobalt containing alloy powder, in vacuum drying chamber in 55 ℃ of dryings 6 hours; Take out cooling back, obtains fine nickel cobalt (alloy) powder product, and its structure from inside to outside is followed successively by the sandwich of nickel, cobalt, nickel, cobalt, and weight is about 17.9kg, and nickeliferous about 48.6%, granularity is about 2.1～3.7 μ m.Bag plating tail washings is through evaporation, concentrated, crystallization, reclaim sulfuric acid ammonium.

As replacing nano-nickel powder to make crystal seed with nano-cobalt powder, nanometer nickel-cobalt alloyed powder, with two metal ammonia aqueous solution of while sulfur acid nickel and cobaltous sulfate, adjust batching, press the aforesaid operations process, can prepare ultra-fine or fine nickel cobalt (alloy) powder.Perhaps use extra-fine nickel powder, super-fine cobalt powder or ultra-fine nickel cobalt (alloy) powder as crystal seed, adjust batching,, press the aforesaid operations process with two metal ammonia aqueous solution of while sulfur acid nickel and cobaltous sulfate, can prepare fine nickel cobalt (alloy) powder, these nickel cobalt (alloy) powder all have sandwich.

Embodiment 13

The nickel cobalt (alloy) powder is heat-treated to the branch homogenising.It is that metallic cobalt, intermediate layer are that metallic nickel, skin are the sandwich of metallic cobalt that the fine nickel cobalt (alloy) powder of the foregoing description 11 preparations has the center; when the nickel that it is inner, cobalt distributed components; promptly under hydrogen or nitrogen protection condition; get the nickel cobalt (alloy) powder 8kg of embodiment 11 preparations; pack in two boats, and be placed in the tubular type hydrogen reducing furnace.Carry out air-tightness and handle the back and feed hydrogen, the air of reduction furnace inside is driven away, begin heating, not open closely go into hydrogen, the nickel cobalt (alloy) powder is heated under hydrogen shield, hydrogen is discharged and burned removing from overflowing mouth.Tubular type hydrogen reducing furnace temperature reaches 900 ℃ after 2 hours, is incubated 20 hours, and at this moment the metallic nickel in the nickel cobalt (alloy) powder, cobalt make composition even the phase counterdiffusion.Cooling back is taken out broken, and through scanning electron microscope analysis, the nickel cobalt (alloy) powder no longer has sandwich, but metallic nickel, the equally distributed product of cobalt composition.

Replace hydrogen with nitrogen, use above-mentioned processing method, nitrogen constantly feeds the tubular type hydrogen reducing furnace, and enters the air from other end gas outlet, and is not oxidized when making the heating of nickel cobalt (alloy) powder, can obtain the uniform nickel cobalt (alloy) powder of composition product equally.

Nanometer, ultra-fine or fine nickel cobalt (alloy) powder by other embodiment prepares under different condition can adopt above-mentioned identical heat treatment method, under hydrogen or nitrogen protection, reach nickel, the uniform purpose of cobalt metal ingredient.Thinner as nickel cobalt (alloy) powder granularity, then can suitably reduce heat treatment temperature, shorten the processing time.

Claims

1. the preparation method of a nickel powder or cobalt powder or nickel cobalt (alloy) powder, with nanometer or ultra-fine nickel, cobalt metal powder is crystal seed, ammonia aqueous solution with nickeliferous, cobalt sulfate and ammonia, ammonium sulfate, adopt hydrometallurgy hydro-thermal hydrogen reduction process and equipment, through batching, the hydrogen reduction of high pressure hydro-thermal, filtration, washing, baking operation, preparation nickel powder, cobalt powder and nickel cobalt (alloy) powder, this method is:

(1) make crystal seed with nano-nickel powder, cobalt powder, adopt hydro-thermal hydrogen reduction process bag cobalt plating on the nano-nickel powder or on nano-cobalt powder plating nickel, thereby obtain to comprise simultaneously the nanometer nickel-cobalt alloy powder of metallic nickel and metallic cobalt; Obtain product and divide two kinds of methods to handle, the one, directly make crystal seed with this nanometer nickel-cobalt alloy powder, prepare ultra-fine or fine nickel cobalt (alloy) powder; After containing the mixed solution filtration of nanometer nickel-cobalt alloy powder after the hydro-thermal hydrogen reduction soon, do not wash, again with the ammonia aqueous solution of sulfur acid nickel, cobaltous sulfate and ammonia, ammonium sulfate, adopt hydro-thermal hydrogen reduction process on the nanometer nickel-cobalt alloy powder, to wrap cobalt plating or plating nickel again, prepare ultra-fine or fine nickel cobalt (alloy) powder; The 2nd, the mixed solution that contains nanometer nickel-cobalt alloy powder product after the hydro-thermal hydrogen reduction is filtered, through washing, oven dry, obtain nanometer nickel-cobalt alloy powder product;

(2) make crystal seed with nano-nickel powder, cobalt powder, adopt hydro-thermal hydrogen reduction process to prepare extra-fine nickel powder, cobalt powder; Divide two kinds of methods to handle with the acquisition product, the one, directly make crystal seed with this extra-fine nickel powder or cobalt powder, prepare ultra-fine or fine nickel cobalt (alloy) powder; After containing the mixed solution filtration of extra-fine nickel powder or cobalt powder product after the hydro-thermal hydrogen reduction soon, do not wash, again with the ammonia aqueous solution of new sulfur acid nickel or cobaltous sulfate, adopt hydro-thermal hydrogen reduction process bag cobalt plating on the nickel powder or on cobalt powder plating nickel, prepare ultra-fine or fine nickel cobalt (alloy) powder; The 2nd, the mixed solution that contains extra-fine nickel powder or cobalt powder product after the hydro-thermal hydrogen reduction is filtered, through washing, oven dry, obtain ultra-fine pure nickel powder or pure cobalt powder product;

(3) make crystal seed with extra-fine nickel powder, cobalt powder, adopt hydro-thermal hydrogen reduction process at plating nickel or on cobalt powder, wrap cobalt plating more again on the extra-fine nickel powder, thereby obtain fine nickel powder or fine cobalt powder;

It is characterized in that comprising following concrete steps:

(1) measures the deionized water of certain volume, in the suction tank diameter, add hot deionized water to 40～90 ℃, add nickelous sulfate or cobaltous sulfate, add ammoniacal liquor, ammonium sulfate, being made into that to contain single metallic nickel or concentration of cobalt ions be 15～130g/L, ammonium sulfate concentrations 50～230g/L, ammonia metal than the ratio of ammonia in the ie in solution and nickel ion or ammonia and the molal quantity of cobalt ions is 2.1～4.5 the ammonia aqueous solution, wherein nickel, cobalt metal ion are not present in a kind of solution simultaneously, i.e. the ammonia aqueous solution of single metal;

(2) measure the deionized water of certain volume, in the suction tank diameter, add hot deionized water to 40～90 ℃, add nickelous sulfate, cobaltous sulfate simultaneously, add ammoniacal liquor, ammonium sulfate again, be made into simultaneously nickeliferous and cobalt ions total concentration and be 40～130g/L, ammonium sulfate concentrations 50～230g/L, ammonia metal and be 2.1～4.5 the ammonia aqueous solution than the ratio of ammonia in the ie in solution and the total mole number of nickel and cobalt ions, wherein nickel, cobalt metal ion are present in a kind of solution simultaneously, i.e. two of sulfur acid nickel and cobaltous sulfate kinds of metal ammonia aqueous solution;

(3) in the ammonia aqueous solution of the single of nickelous sulfate or cobaltous sulfate or two metals, add 0.1～0.2g/L anthraquinone and 0.01～0.02g/L gelatine;

(4) in the ammonia aqueous solution of the single of nickelous sulfate or cobaltous sulfate or two metals, behind adding anthraquinone and the gelatine, add nanometer or ultra-fine nickel powder or cobalt powder or cobalt nickel powder crystal seed again; Nano level metal powder crystal seed average diameter is 5～90nm, and ultra-fine level metal dust crystal seed average diameter is 150～950nm; When the preparation cobalt nickel powder, the crystal seed addition requires to determine that the amount of nickel metal or metallic cobalt is adjustable in 5～50% weight ratio scopes according to last product component;

(5) the ammonia aqueous solution that will contain the single of crystal seed or two metals changes in the autoclave, behind the sealing autoclave, opens the autoclave stirring motor, 300～1100 rev/mins of mixing speeds, make crystal seed be suspended in single or the two metal ammonia aqueous solution in, wrap the plating reaction; The heating high-pressure still makes solution temperature rising in the still, after temperature rises to 120 ℃, high pressure hydrogen is imported from high pressure storage tank in the pressure-reducing cushioning jar, charges into then in the autoclave, makes the interior Hydrogen Vapor Pressure of still reach 2.5～6MPa; The hydrogen that charges into reduces solution metal nickel, cobalt ions, and is deposited on seed surface, and deposition reaction continues to carry out, and Hydrogen Vapor Pressure constantly descends; When Hydrogen Vapor Pressure is reduced to 2MPa, charge into hydrogen again to certain pressure, the temperature that keeps solution in the still is in 120～200 ℃ of scopes, and till finishing to metallic nickel, cobalt ions reduction reaction, bag plating reaction finishes;

(6) with cooling water the aqueous solution in the autoclave is cooled to below 90 ℃, in autoclave, discharge the aqueous solution that contains metal nickel powder or cobalt powder or cobalt nickel powder, after filtration, after the washing, it is dry under 40～80 ℃ of temperature that metal dust is put into vacuum drying oven, obtains needed nanometer, ultra-fine or superfine metallic nickel powder or cobalt powder or cobalt nickel powder product; Filtrate is through evaporation, concentrated, crystallization, reclaim sulfuric acid ammonium;

(7) or through after above-mentioned steps (5), after the aqueous solution that will contain metal nickel powder or cobalt powder or cobalt nickel powder is discharged in the autoclave, different with step (6), only metal dust is filtered out from solution, do not wash, metal dust is not as final products, and once more as crystal seed, mix by a certain percentage with the ammonia aqueous solution of single or two metals, change in the autoclave, set by step (5) repeated hydrogen reduce deposition metal; So through repeatedly repeating step (5), (7), after reaching requirement, in autoclave, discharge the aqueous solution that contains metal nickel powder or cobalt powder or cobalt nickel powder, washing after filtration,, it is dry under 40～80 ℃ of temperature that metal dust is put into vacuum drying oven, obtains needed ultra-fine or superfine metallic nickel powder or cobalt powder or cobalt nickel powder product;

(8) metal dust that at every turn filters out in above-mentioned steps (5), (7), always only with a kind of ammonia aqueous solution of single metal, deposit bag plating reaction, then obtain the metal dust of single component; Perhaps, deposit bag plating reaction, then obtain the nickel cobalt (alloy) powder with the ammonia aqueous solution of another kind of metal; Perhaps alternately adopt the ammonia aqueous solution nickeliferous or that contain the single metal of cobalt to mix, wrap the plating reaction, then obtain the nickel cobalt (alloy) powder of sandwich with the metal dust that filters out; Perhaps adopt the ammonia aqueous solution of two metals to mix, deposit bag plating reaction, also obtain the nickel cobalt (alloy) powder of sandwich with the metal dust that filters out.

2. by the preparation method of the described a kind of nickel powder of claim 1 or cobalt powder or nickel cobalt (alloy) powder; it is characterized in that nickel cobalt (alloy) powder through the preparation of hydro-thermal hydrogen reduction method; when the nickel that it is inner, cobalt distributed components; promptly under hydrogen or nitrogen protection condition; heat treatment is 16～30 hours under 500～950 ℃ temperature, obtains nickel, the uniform product of cobalt composition.

3. by the preparation method of claim 1,2 described a kind of nickel powders or cobalt powder or nickel cobalt (alloy) powder, it is characterized in that prepared nanoscale nickel cobalt (alloy) powder product average grain diameter is 30～90nm, ultra-fine level metallic nickel or cobalt or nickel cobalt (alloy) powder product average grain diameter are 150～950nm, and fine level metallic nickel or cobalt or nickel cobalt (alloy) powder product average grain diameter are 2～20 μ m.