CN101428348A - Process for producing spherical submicron metal with hydro-thermal treatment - Google Patents
Process for producing spherical submicron metal with hydro-thermal treatment Download PDFInfo
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Abstract
The invention discloses a technological method for preparation of sphere-shaped ultrafine metallic powders through hydro-thermal treatment, which relates to a technological method for preparation of sphere-shaped ultrafine nickel powders or ultrafine cobalt powders through the procedures such as precipitation, dispersing agent surface finish, high-pressure hydro-thermal treatment, washing, drying and high-temperature hydrogen reduction and the like, and which belongs to the technical field for preparation of metal powder materials. The technological method adopts water soluble salts with nickel and cobalt, cobalt oxide, sub-carbonate, carbonate or hydroxide as raw materials, which are prepared into water solution after processing, the dispersing agent is added, then nickel ion and cobalt ion in the water solution are precipitated through alkali, carbonate, oxalic acid or ammonium oxalate and the like, the hydro-thermal treatment of water pulp of the precipitate is performed in an autoclave, and products of sphere-shaped ultrafine nickel powders or ultrafine cobalt powders with even graininess and good dispersibility can be obtained through washing, drying and high-temperature hydrogen reduction. The technological method is not only suitable for medium- and small-scale discontinuous-type manufacture, but also used for large-scale continuous manufacture, and the manufacturing cost is low.
Description
Technical field
A kind of process of producing spherical submicron metal with hydro-thermal treatment, relate to the process that operations such as adopting precipitation, dispersant finishing, water under high pressure heat treatment, washing, drying, high-temperature hydrogen reduction prepares spherical super fine nickel powder or super-fine cobalt powder, belong to the metal powder material preparing technical field.
Technical background
Extra-fine nickel powder or super-fine cobalt powder (hereinafter to be referred as extra-fine nickel powder, cobalt powder) have the special physicochemical performance, have great skin effect and bulk effect.Along with science and technology development, different applications improves constantly the dusty material performance demands, and extra-fine nickel powder, cobalt powder progressively replace conventional 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.In recent years, extra-fine nickel powder, the cobalt powder market demand increase very fast, constantly enlarge the production of extra-fine nickel powder, cobalt powder both at home and abroad.China is because the developing rapidly of industries such as battery, catalyst, carbide alloy, and the demand of extra-fine nickel powder, cobalt powder is heightened, and particularly has property and can satisfy the globular powdered nickel, cobalt powder etc. of multiple application.
Metallic element nickel, cobalt have many similar physicochemical properties, and therefore, the preparation method of nickel powder and cobalt powder is also identical or similar.For ultra-fine nickel, cobalt dust preparation methods,, many different sorting techniques are arranged because it is multidisciplinary to relate to physics, chemistry and material etc.By preparation system and state, it can be divided into vapor phase method, liquid phase reduction, electrolysis and solid phase reduction method.At present, the main preparation methods of extra-fine nickel powder has:
(1) vapor phase method
Vapor phase method is divided into carbonyl nickel thermal decomposition method, gas phase hydrogen reduction method, using vaporization condensation process again.(a) carbonyl nickel thermal decomposition method.Utilize carbonyl nickel (CO)
4The thermal instability of compound, heating make it to decompose.Slowly grow into submicron metal.More than 50 ℃, when active nickel contacted with carbon monoxide, 1 nickle atom combined with 4 gas molecules, generated nickel carbonyl compound N i (CO)
4Be controlled at the temperature more than 100 ℃ then, carbonyl nickel can be decomposed into metallic nickel and carbon monoxide (CO) again, obtains extra-fine nickel powder.(b) gas phase hydrogen reduction method.With hydrogen reducing gaseous metal halide, mainly be the reducing metal chloride.The prepared powder of this method generally all is a nanometer or ultra-fine.(Tokyo) company is with solid NiCl for Toho Titanium Co., Ltd. for Japanese eastern nation titanium at present
2Gasification about 950～1150 ℃, steam NiCl
2With H
2The adverse current reduction makes the spherical super fine nickel powder that particle diameter is 0.1～1.0 μ m, the said firm has applied for the related invention patent (US2003196516A1, US6235077B1, US6500227B1, JP2001073001A, JP2001062332A) of this production technology, puts into serial production in October, 1999.Japan Jfe Mineral Company Ltd. (JPE MINERAL COMPANY LTD.) method with hydrogen reducing gas chlorination nickel of also having applied for prepares the patent of invention of nickel based ultrafine powder (US2006191608A1, CN1758973A).Prepare the method for nanometer or extra-fine nickel powder based on hydrogen reducing gas chlorination nickel principle, another company of Japan (kawatesu MiningCo., Ltd., Tokyo) also applied for patent (US6402803B1, US6312496B1).(c) using vaporization condensation process.Utilize elevated temperature heat sources such as electric arc, high-frequency electric field or plasma with nickel raw material heating and gasifying, cooling makes it to condense into extra-fine nickel powder fast then.The extensive nano material of domestic Ningbo of Zhejiang Co., Ltd uses this method to produce.
(2) liquid phase reduction
Liquid phase reduction is meant and adds reducing agents such as polyalcohol, hydrazine hydrate, aldehydes in the solution of nickelous sulfate, nickelous carbonate, nickel nitrate, produces extra-fine nickel powder by redox reaction.According to selected reducing agent difference, can be divided into methods such as polyalcohol, hydrazine hydrate reduction, the reduction of water soluble nickel salt pressurized hydrogen, sol-gel processing and micro emulsion liquid phase method again.(a) polyalcohol method.Polyalcohol (as ethylene glycol) method is to adopt to add nickel hydroxide precipitate in polyalcohol, and adds proper amount of surfactant and NaOH, adds hot reflux, makes it reduction and generates extra-fine nickel powder.This method can be used to prepare submicron metals such as cobalt, copper, silver, gold, platinum, palladium, as patent CN1381328A.(b) hydrazine hydrate reduction method.With hydrazine hydrate (or claiming hydrazine hydrate, hydrazine) is reducing agent, adds thermal reduction nickel hydroxide precipitate thing, obtains extra-fine nickel powder; Or under alkali condition, hydrazine hydrate is joined NiSO
4, Ni (NO
3)
2, NiCl
2Deng preparing nickel powder in the solution.By control process conditions, can also prepare nano-nickel powder with this method, application at home and abroad the patent of invention of more this method.But hydrazine hydrate costs an arm and a leg, and reduzate nickel powder purity is not high.(c) hydrothermal high-temperature pressurized hydrogen reducing process.Comprise precipitation reducing process and aqueous solution reducing process.The precipitation reducing process is to be raw material with sediments such as nickel hydroxide, nickel oxalate, basic nickel carbonates, furnishing aqueous slurry in autoclave, under high temperature (120～200 ℃) with the high pressure hydrogen reduction, the preparation extra-fine nickel powder.Make catalyst as chemical industry metallurgical research institute of the Chinese Academy of Sciences (existing process study institute) with anthraquinone, palladium bichloride, hydro-thermal pressurized hydrogen reduction from nickel hydroxide or basic nickel carbonate water slurry, prepared nanometer or extra-fine nickel powder, but the purity of reduzate nickel powder can not reach promising result.The patent of invention of having applied for has CN1034689A and a CN85100739A.Aqueous solution reduction rule is to add ferrous sulfate, chromous sulfate etc. as nucleating agent in the mixed solution of nickelous sulfate, ammonium sulfate and ammoniacal liquor, pressurized hydrogen reduction under 180～200 ℃ of hydrothermal conditions, obtain nickel powder (heavy non-ferrous metal smelting design manual, copper nickel volume, metallurgical industry publishing house, 1996, p754～764), but the nickel powder that this method obtains is generally thicker, and easily forms in autoclave and scab, and is difficult to clear up.(d) sol-gel processing.Metal alkoxide or inorganic salts are dissolved in the organic solvent, form uniform sol, further react and lose most of organic solvent and change into gel, prepare superfine powder, fiber and film by heat treatment by hydrolysis-polymerisation.(e) micro emulsion liquid phase method.In the reverse microemulsion liquid system, the interfacial film that small water droplet is formed by surfactant and cosurfactant surrounds, and is separated from one another.As with NiCl
2, N
2H
4The aqueous solution, additive and kerosene mix, form micro emulsion, reaction at a certain temperature obtains nano-nickel powder.
(3) electrolysis
Adopt sheet nickel to make anode, stainless steel, titanium plate, noble metal or graphite are made negative electrode, put into nickel chloride or nickel sulfate solution in the electrolytic cell, connect the power supply and the of short duration change sense of current of periodicity, the nickel powder that generates constantly falls into bottom of electrolytic tank, with magnetic material nickel powder is collected then.At present, industrial nickel powder output of producing with electrolysis is big, but nickel powder is dendroid, and granularity is thicker, generally is unsuitable for producing extra-fine nickel powder.In electrolytic process, be aided with ultrasonic wave etc., can improve product quality.
(4) solid phase reduction method
(a) nickel oxalate thermal decomposition method.Utilize the pyrolysis mechanism of oxalates, control reaction process technical conditions prepare superfine powder.Employing such as CN1600480A, CN1491762A oxalate precipitation legal system is equipped with fibrous nano powdered nickel precursor body powder; then in the heating furnace of protective atmosphere; control suitable temperature, resolving time and carry out thermal decomposition, obtain being fibrous ultra-fine or nano-nickel powder, now industrialization as the knitting wool.The thermal decomposition in nitrogen atmosphere of nickel oxalate presoma can obtain highly purified simple substance nano-nickel powder, and different with presoma preparation method and heat decomposition temperature, and the performance of product nano-nickel powder is also different with specific area.(b) vacuum reduction method.Adopt solid-state charcoal vacuum reduction, under 1100～1200 ℃, the condition of vacuum 5～10Pa, made metal nickel powder by nickel protoxide, wherein carbon content is less than 0.02%.(c) high-temperature hydrogen reduction method.With nickel oxalate, nickel protoxide etc. is raw material, uses hydrogen reducing down at 400～1000 ℃, and the nickel powder granularity that obtains is thicker, skewness, and it is serious to reunite, or oxygen content is higher.
The main preparation methods of super-fine cobalt powder then has:
(1) high temperature reduction method
Adopt hydrogen or decomposed ammonia reduction nickel oxalate, cobalt oxide etc., reduce under 200～900 ℃ of temperature, become the reduction cobalt powder, this is industrial common cobalt powder preparation method commonly used.Its product is reunited serious, and granularity is thicker, and oxygen content is higher, the difficult super-fine cobalt powder that obtains.
(2) high-pressure water spray method
The reguline metal cobalt is placed the intermediate frequency furnace heat fused, pour the bottom pour ladle stove then into, under the impact of hydraulic atomized fuel pulverizing plant inner high voltage current, be crashed to pieces into countless tiny liquid pearls and rapidly condensation, will make super-fine cobalt powder after water and powder separation, the drying.The cobalt powder oxygen content of this method preparation is higher, and the superfine powder productive rate is very low.
(3) precipitation reducing process
Be at least 2 cobalt ammonia complex, ammonium sulfate solution with ammonia cobalt mol ratio, in airtight reaction vessel, in 50～120 ℃ temperature range, heat strong agitation, in solution, feed carbon dioxide and cobalt reaction then, in solution, generate the cobalt carbonate sediment and separate, add a spot of fire resistance oxide then and form compound and be deposited on the cobalt carbonate precipitation particles with solution.This cobalt carbonate is deposited under the hydrogen atmosphere in 400～700 ℃ of temperature ranges, and fully heating is reduced into and contains oxygen and be less than 2% superfine metal cobalt powder.
(4) precipitation heat decomposition method
With high-purity electrolytic cobalt sheet of dissolving with hydrochloric acid or cobalt button; obtain cobalt chloride solution; make cobalt chloride solution change cobalt oxalate precipitation into oxalic acid or ammonium oxalate solution; precipitation is through fully washing; after drying under 120～150 ℃ of vacuum conditions; under protective atmosphere, in about 500 ℃, carry out thermal decomposition again, obtain spherical super fine cobalt powder or needle-like cobalt powder.
(5) hydrothermal high-temperature pressurized hydrogen reducing process
Comprise precipitation reducing process and aqueous solution reducing process.The precipitation reducing process is to add excess base or carbonate (ammoniacal liquor, NaOH, sodium carbonate or carbonic hydroammonium etc.) at the aqueous solution that contains the divalent metal cobalt salt, obtain hydroxide, oxide or the subcarbonate precipitation of cobalt, needn't filter and wash, add a small amount of palladium bichloride or super-fine cobalt powder and make catalyst, directly carry out the hydro-thermal hydrogen reduction, can obtain the cobalt powder (CN1034689A, and analogy gram is peaceful etc., Co (OH) of thin and pure homogeneous
2The alkalescence slurry hydrogen reduction prepares ultra-fine Co powder, process engineering journal, calendar year 2001, Vol.1, No.1, p62～65).Aqueous solution reduction rule is to add ferrous sulfate, chromous sulfate, sodium borohydride (US4761177A1), silver sulfate, silver nitrate (US5246481A1) or Cymag and vulcanized sodium (EP0047076A1) etc. as nucleating agent in the mixed solution of cobaltous sulfate, ammonium sulfate and ammoniacal liquor, 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, p764～772; And Liu Jinshan, produce cobalt powder, China YouSe metallurgy,, the 5th phase, p24～30 in 1979 with the pressurized hydrogen reducing process).Suitability for industrialized production has abroad been arranged, and (Canada), but this method easily forms in autoclave and scabs, and is difficult to cleaning for US5246481A1, Sherritt Gordon Limited.
(6) polyol reduction method
To contain cobalt precursor (as cobalt hydroxide, cobalt oxalate and cobalt oxide) is distributed in the polyalcohol (as ethylene glycol), add an amount of NaOH and other additive, add hot reflux, polyalcohol is as solvent and reducing agent, by the control reaction condition, can make particle diameter less than 1 micron spherical cobalt powder.But the cobalt powder purity of this method preparation is generally not high.
(7) electrolysis
In the aqueous solution that contains the metallic cobalt ion, feed direct current, the metallic cobalt ion will be on negative electrode discharge depositing.Conditions such as control current density can obtain metal cobalt powder.But it is uneconomical that this method is used to prepare super-fine cobalt powder.
(8) gas phase hydrogen reduction reaction method
Korean Patent KR20020029888A discloses the method that a kind of gas phase reduction process prepares super-fine cobalt powder.At high temperature the halide of cobalt is (as CoCl
2) steam and hydrogen reaction, hydrogen ratio in the temperature of conditioned reaction, the mist, the granularity at controlled powder process end, but the byproduct hydrogen chloride of reaction is adsorbed on the surface of powder particle easily, and unreacted chloride also sneaks in the product easily, influences degree of purity of production.
(9) plasma method
In plasma generator, feed propane and air, under action of plasma, be converted into carbon monoxide and hydrogen, cobalt oxide powder is sent in the plasma flow by dispenser, processes such as cobalt oxide melts, the reaction of evaporation, vapour phase reduction, steam condensation and metallic particles crystallization generate super-fine cobalt powder.Also available in addition thick cobalt powder is a raw material, through the plasma heating evaporation, obtains super-fine cobalt powder after the condensation.This method production cost is higher, and production scale is less.
(10) gamma-ray irradiation preparation method
After preparing certain density cobalt liquor, add an amount of isopropyl alcohol and polyvinyl alcohol respectively as free radical scavenger and dispersant, regulate the pH value with acetic acid and NaOH, again the solution for preparing is carried out ultrasonic degas, carry out gamma-ray irradiation after feeding the oxygen content in the nitrogen reduction solution, can obtain nano-cobalt powder.
(11) microemulsion method
Anion surfactant is dissolved in the organic liquids such as isooctane, then cobalt chloride and sodium borohydride are dissolved in this solution with certain concentration respectively, make coacervation of colloid with acetone and water as flocculant again, after filtration, the washing remove unnecessary surfactant after, the colloid drying is obtained nanometer or super-fine cobalt powder.
There are many above-mentioned extra-fine nickel powders of mentioning, cobalt powder preparation method also to be in the experimental study stage, do not enter industrialization production.And other preparation method's equipment investments are big, and environmental protection auxiliary facility and automaticity require high, and the adaptability of raw material is not strong, is not suitable for medium-sized and small enterprises production.Perhaps employed additive is poisonous, contaminated environment.
Early-stage Study of the present invention is found, the sediment crystallinity of most nickel, cobalt is bad under the normal condition, amorphous state (or unformed shape) product is many, and the difficult washing of impurity removes in the sediment, reunite easily when heat drying or calcining and lump, nickel powder is grown up when causing the high-temperature hydrogen reduction, can not get extra-fine nickel powder, cobalt powder product, and product quality is low.
At the different problems in above-mentioned extra-fine nickel powder, the cobalt powder preparation process, the present invention is a raw material with the water soluble salt of various nickeliferous, cobalt or oxide, hydroxide, all kinds of carbonate, through dissolving, batching, adopt then that pressurized thermal water transforms in precipitation, dispersant finishing, the autoclave, the process of washing, dry, high-temperature hydrogen reduction, the result obtained specific area greatly, good dispersion, the extra-fine nickel powder of even particle distribution, cobalt powder.The preparation method is simple, flexible, and adaptability to raw material is strong, is suitable for different production scales.Particularly adopted crucial pressurized thermal water to handle the sediment material process, can increase substantially the degree of crystallinity of material, further reduced impurity content, made the presoma of extra-fine nickel powder, cobalt powder be difficult for reunion, favorable dispersibility.Up to the present, also do not find to adopt this process to prepare the open or report of extra-fine nickel powder, cobalt powder.
Summary of the invention
The objective of the invention is: according to the performance requirement of different industries nickel powder, cobalt powder, the preparation method that a kind of adaptability to raw material is strong, be suitable for medium and small production-scale high-quality superfine spherical nickel powder, cobalt powder is provided, and the extra-fine nickel powder of being produced, cobalt powder can satisfy the specific (special) requirements in fields such as battery material, powder metallurgy, multilayer ceramic capacitor, magnetic material.Employed raw material is the water soluble salt of nickel, cobalt such as sulfate, nitrate, chloride, acetate, perhaps with sulfuric acid, nitric acid, hydrochloric acid, acetic acid oxide, subcarbonate or the hydroxide dissolving of nickel, cobalt is made corresponding sulfate, nitrate, chloride, acetate; Be made into the aqueous solution then, add dispersant, with the aqueous solution of alkali (NaOH, potassium hydroxide), sodium carbonate, sodium acid carbonate, potash, saleratus, carbonic hydroammonium, ammonium carbonate or precipitating reagents such as oxalic acid, ammonium oxalate, change the sediment that the surface is adsorbed with dispersant into again; Carrying out hydrothermal crystallizing in autoclave handles, behind the insulation certain hour, extract water slurry out, with its filtration, washing, drying, after high-temperature hydrogen reduction, fragmentation, obtain good dispersion, epigranular, specific area is big, non-oxidizability is strong superfine spherical nickel powder, cobalt powder.
The objective of the invention is to be achieved through the following technical solutions, may further comprise the steps:
(1) is raw material with the water soluble salt of nickeliferous, cobalt such as sulfate, nitrate, chloride, acetate, is made into the aqueous solution of single salt; Perhaps oxide, subcarbonate, carbonate or the hydroxide dissolving of nickel, cobalt made the aqueous solution of corresponding sulfate, nitrate, chloride, acetate with sulfuric acid, nitric acid, hydrochloric acid, acetic acid; Concentration of metal ions is controlled at nickeliferous or cobalt 30～70g/L in the aqueous solution of the single salt of being prepared.
(2) add one or more (being no more than three kinds at most) in polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PBG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), tween-80, the oleic acid as dispersant in the nickel of preparation or the cobalt aqueous solution, various dispersants add and add up to 6～12g/L.These reactants can be adsorbed on the sediment surface when precipitation reaction, play the effect of finishing, stop further growing up or reuniting of deposit seed, make deposit seed have good dispersiveness.
(3) precipitating reagent is alkali (NaOH, potassium hydroxide), sodium carbonate, sodium acid carbonate, potash, saleratus, carbonic hydroammonium, ammonium carbonate or oxalic acid, ammonium oxalate etc., selects wherein a kind of, by the aqueous solution of 0.7～4.0mol/L concentration preparation precipitating reagent.
(4) get the aqueous solution of required theoretical amount 102%～106% precipitating reagent, the aqueous solution with nickeliferous or cobalt and dispersant under normal temperature condition adds wherein, and constantly stirs, and solution is fully mixed, homogeneous reaction.After two kinds of solution mix fully, continue to stir 10～15 minutes; Leave standstill after 6～10 hours the elimination of part supernatant, water slurry is changed in the autoclave of lining titanium; Filtrate then discards after treatment.
(5) speed of agitator with autoclave is made as 450～550r/min, and heating-up temperature is limited to 135～190 ℃, charges into a kind of in pressure-air, oxygen, nitrogen or the hydrogen, makes the still internal pressure reach 3.0～4.2MPa.With water slurry heating in the still, when temperature rises to assigned temperature, be incubated 1～3 hour, carry out hydrothermal treatment consists.When being cooled to water slurry below 90 ℃, utilize the pressure in the still, discharge water slurry wherein, and emit the gas in the autoclave, reduce to normal pressure.Filter repeatedly, Xian Di 3～5 times, filter residue is wetting slightly afterwards at 115～140 ℃ of following vacuum dryings with a small amount of alcohol (filter residue: alcohol=100:5～10 weight ratios, or with n-butanol, n-octyl alcohol substituted alcohol).Do not increase the autoclave internal pressure if do not charge into gases at high pressure, when carrying out hydrothermal treatment consists, should extend to 6～10 hours 145～200 ℃ insulation processing time.
(6) material after the oven dry is put into hydrogen reducing furnace in 350～550 ℃ of reduction 3～8 hours then through 20～30 minutes mixings of ball milling, and the product that reduction obtains is preserved in nitrogen atmosphere and become final extra-fine nickel powder or cobalt powder product after 16～24 hours.
Advantage of the present invention and good effect compared with prior art mainly show as: available various nickeliferous, cobalt metal soluble salt classes, oxide, subcarbonate or hydroxide are as raw material, and adaptability is strong.As precipitating reagent, range of choice is wide with alkali (NaOH, potassium hydroxide), sodium carbonate, sodium acid carbonate, potash, saleratus, carbonic hydroammonium, ammonium carbonate or oxalic acid, ammonium oxalate etc.Add dispersant during precipitation, be adsorbed on tiny precipitate particles surface, be difficult for reuniting the particle good dispersion; A most important operation is to adopt the method for pressurized thermal water to handle sediment, sedimentary physicochemical properties have been changed, improved sedimentary degree of crystallinity greatly, thereby material produces the possibility of reuniting when reducing drying or roasting significantly, be easy to washing and filter; And enough high-temperature water heat treatment times are provided, the small amount of impurities that is mingled with in the sediment is fully removed.When drying, calcination process, the dispersant of surface absorption plays the effect of isolation, suppresses the material crystal growth when heat treatment, the nickel that obtains, cobalt/cobalt oxide uniform particles are tiny, reducing activity is good, and dispersant is also removed by heat treatment at last, does not influence product purity.The hydrogen reducing temperature is low, speed fast, reduction is thorough, final extra-fine nickel powder, cobalt powder product epigranular, spherical in shape, and antioxygen is good behind the absorption nitrogen.Both be suitable for the discontinuous production of middle and small scale, can have carried out large-scale continuous production again, manageability, production cost is low.
Description of drawings
Fig. 1 process chart of the present invention.
SEM (SEM) photo of the extra-fine nickel powder surface topography of Fig. 2 the present invention preparation.
SEM (SEM) photo of super-fine cobalt powder 1 surface topography of Fig. 3 the present invention preparation.
SEM (SEM) photo of super-fine cobalt powder 2 surface topographies of Fig. 4 the present invention preparation
The specific embodiment
Embodiment 1
The employing nickelous sulfate is that raw material, carbonic hydroammonium are that precipitating reagent prepares extra-fine nickel powder.In tank diameter A, add deionized water 150L, be warming up to 55 ℃; Take by weighing technical pure nickelous sulfate 50kg, add in the tank diameter A, stir and make the nickelous sulfate dissolving; Add dispersant polyethylene glycol 1200g, oleic acid 700g subsequently, and nickel sulfate solution is diluted to volume 210L.Add deionized water 145L earlier in tank diameter B, be warming up to 50 ℃, add technical pure carbonic hydroammonium 30.3Kg then, stirring makes it to dissolve fully, is diluted to the volume 205L aqueous solution (the about 1.8mol/L of concentration).The nickel sulfate solution rapid (in 3～4 minutes) that will contain dispersant under stirring condition joins in the ammonium bicarbonate aqueous solution, continues to stir 12 minutes; Leave standstill after 6 hours part supernatant suction strainer is removed.To remain the sediment water slurry and change in the 500L lining titanium autoclave, and charge into air to pressure to 3.5MPa, mixing speed transfers to 450r/min, begins then to heat up.After 2 hours, the temperature of autoclave reaches 165 ℃, is incubated 2.2 hours; Then open cooling water and make the water slurry cooling, when water slurry in the still was cooled to 80 ℃, the control velocity of discharge was discharged water slurry wherein, simultaneously the gas in the autoclave is discharged, and reduces to normal pressure.The water slurry of discharging uses 15kg alcohol that filter residue is wetting after washing through 4 filtration, deionized waters repeatedly again, puts into electrically heated vacuum drying chamber and dehydrates 6 hours for inherent 120 ℃.The dried material ball milling after 20 minutes, is sent in the tubular type reduction furnace,, taken out from the discharge end cooling back of tubular type reduction furnace 500 ℃ of constant temperature reduction 7 hours with hydrogen, pour in the metal bucket, sealing charged into nitrogen treatment 18～20 hours, obtained the extra-fine nickel powder product.By analysis, the nickel powder apparent density is 1.2g/cm
3, oxygen content 0.21%, nickel content reaches 99.59% (adopt the percetage by weight minusing to calculate, wherein do not comprise gaseous impurity).Analyze through SEM (SEM), extra-fine nickel powder uniform particles, size are about 500nm～1 μ m.
Above-mentioned example also is not limited to this.The raw material of nickel is not a nickelous sulfate, can also use nickel nitrate, nickel chloride, nickel acetate to replace nickelous sulfate; Dispersant replaces polyethylene glycol, oleic acid with one or more (being no more than three kinds at most) in polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PBG), polyvinyl alcohol (PVA) polyvinylpyrrolidone (PVP), tween-80, the oleic acid; Precipitating reagent is then with a kind of replacement carbonic hydroammonium wherein such as NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, potash, saleratus, ammonium carbonate or oxalic acid, ammonium oxalate etc.; The specific requirement that provides by technical scheme then adopts said method can prepare the spherical super fine nickel powder equally.
Embodiment 2
The employing nickel oxide is that raw material, NaOH are that precipitating reagent prepares extra-fine nickel powder.In tank diameter A, add deionized water 100L, be warming up to 50 ℃; Take by weighing nickel oxide 14.5kg (nickeliferous 76.3%), add in the tank diameter A, stirring makes nickel oxide wetting; With 100L concentration is that the aqueous solution of nitric acid of 245.4g/L joins in the tank diameter A, constantly stirs, and makes the dissolving of nickel oxide water slurry.After nickel oxide has dissolved, nickel nitrate aqueous solution is filtered, remove insoluble matter, and liquor capacity is diluted to 260L with the acidproof filter cloth of 400 purposes.Add polyethylene of dispersing agent pyrrolidones 2000g, tween-80 600g subsequently.Add deionized water 160L earlier in tank diameter B, slowly add technical pure NaOH 15.8kg then, stirring makes it to dissolve fully.The nickel nitrate aqueous solution that will contain dispersant under stirring condition joined in the sodium hydrate aqueous solution in 5～6 minutes, continued to stir 10 minutes; Leave standstill after 7 hours the part supernatant is absorbed.To remain the sediment water slurry and change in the 500L lining titanium autoclave, and charge into nitrogen to pressure to 3.6MPa, mixing speed transfers to 500r/min, begins then to heat up.When the temperature in the autoclave reaches 160 ℃, be incubated 2.5 hours; Then open cooling water and make the water slurry cooling, when water slurry in the still was cooled to 82 ℃, the control velocity of discharge was discharged water slurry wherein, simultaneously the residual gas in the autoclave is discharged, and reduces to normal pressure.The water slurry of discharging uses 12kg alcohol that filter residue is wetting after washing through 5 filtration, deionized waters repeatedly again, puts into electrically heated vacuum drying chamber, dehydrates 6 hours at 130 ℃.The dried material ball milling after 25 minutes, is sent in the tubular type reduction furnace, reduced 6 hours at 450 ℃ of constant temperature with hydrogen.Take out from the discharge end cooling back of tubular type reduction furnace, pour in the metal bucket, sealing charged into nitrogen treatment 18～20 hours, obtained the extra-fine nickel powder product.By analysis, the nickel powder apparent density is 0.8g/cm
3, oxygen content 0.32%, nickel content reaches 99.65% (adopt the percetage by weight minusing to calculate, wherein do not comprise gaseous impurity).The extra-fine nickel powder uniform particles, spherical in shape, granularity is about 300nm～800nm.
The raw material of nickel is not only limited to nickel oxide, can also replace nickel oxide with basic nickel carbonate or nickel hydroxide; A kind of replacement in nitric acid sulfuric acid, hydrochloric acid, the acetic acid; Dispersant replaces polyvinylpyrrolidone, tween-80 with one or more (being no more than three kinds at most) in polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PBG), polyvinyl alcohol (PVA) polyvinylpyrrolidone (PVP), tween-80, the oleic acid; Precipitating reagent is then with a kind of replacement NaOH in potassium hydroxide, sodium carbonate, sodium acid carbonate, potash, saleratus, carbonic hydroammonium, ammonium carbonate or oxalic acid, the ammonium oxalate etc.; The specific requirement that provides by technical scheme then adopts said method can prepare the spherical super fine nickel powder equally.
Embodiment 3
The employing cobaltous sulfate is that raw material, oxalic acid are that precipitating reagent prepares super-fine cobalt powder.In tank diameter A, add deionized water 150L, be warming up to 50 ℃; Take by weighing technical pure cobaltous sulfate 56.3kg, add in the tank diameter A, stir and make the cobaltous sulfate dissolving; Add polyethylene of dispersing agent alcohol 1100g, polypropylene glycol 800g, oleic acid 300g subsequently, and cobalt sulfate solution is diluted to volume 220L.In tank diameter B, add deionized water 220L earlier, add technical pure oxalic acid 24.8Kg then, be heated with stirring to 50 ℃ and make it to dissolve fully, be diluted to the volume 245L aqueous solution.The cobalt sulfate solution that will contain dispersant under stirring condition joins rapidly in the oxalic acid aqueous solution, continues to stir 14 minutes; Leave standstill after 6 hours part supernatant suction strainer is removed.To remain the sediment water slurry and change in the 500L lining titanium autoclave, and charge into oxygen and reach 3.3MPa until pressure, mixing speed transfers to 500r/min, begins then to heat up.When the temperature in the autoclave reaches 160 ℃, be incubated 2.8 hours; Then open cooling water and make the water slurry cooling, when water slurry in the still was cooled to 85 ℃, the control velocity of discharge was discharged water slurry wherein, simultaneously the gas in the autoclave is discharged, and reduces to normal pressure.The water slurry of discharging uses 12kg alcohol that filter residue is wetting after washing through 4 filtration, deionized waters repeatedly again, puts into electrically heated vacuum drying chamber and dehydrates 6 hours for inherent 130 ℃.The dried material ball milling after 20 minutes, is sent in the tubular type reduction furnace,, taken out from the discharge end cooling back of tubular type reduction furnace 480 ℃ of constant temperature reduction 6.5 hours with hydrogen, pour in the metal bucket, sealing charged into nitrogen treatment 20 hours, obtained the super-fine cobalt powder product.By analysis, the cobalt powder apparent density is 1.3g/cm
3, oxygen content 0.63% contains the cobalt amount and reaches 99.53% (adopt the percetage by weight minusing to calculate, wherein do not comprise gaseous impurity).Super-fine cobalt powder uniform particles, size are about 600nm～1 μ m.
Above-mentioned only is example, and the water-soluble material of cobalt is not limited to cobaltous sulfate, can also use cobalt nitrate, cobalt chloride, cobalt acetate to replace cobaltous sulfate; Dispersant replaces polyvinyl alcohol, polypropylene glycol, oleic acid with any one or more (being no more than three kinds at most) in polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PBG), polyvinyl alcohol (PVA) polyvinylpyrrolidone (PVP), tween-80, the oleic acid; Precipitating reagent is then with a kind of replacement oxalic acid in NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, potash, saleratus, carbonic hydroammonium, ammonium carbonate or the ammonium oxalate etc.; The specific requirement that provides by technical scheme then adopts said method can prepare the spherical super fine cobalt powder equally.
Embodiment 4
The employing cobalt hydroxide is that raw material, sodium carbonate are that precipitating reagent prepares super-fine cobalt powder.In tank diameter A, add deionized water 120L, be warming up to 40 ℃; Take by weighing cobalt hydroxide 18.5kg (containing cobalt 61.3%), add in the tank diameter A, stirring makes cobalt hydroxide wetting; With 110L concentration is that the aqueous hydrochloric acid solution of 128g/L joins in the tank diameter A, constantly stirs, and makes the dissolving of cobalt hydroxide water slurry.After cobalt hydroxide has dissolved, cobalt chloride solution is filtered, remove insoluble matter, and liquor capacity is diluted to 270L with the acidproof filter cloth of 400 purposes.Add polyethylene of dispersing agent alcohol 800g, polypropylene glycol 1360g subsequently.In tank diameter B, add deionized water 150L earlier, slowly add technical pure sodium carbonate 20.5kg then, add thermal agitation and make it to dissolve fully.The cobalt chloride solution that will contain dispersant under stirring condition joined in the aqueous sodium carbonate in 5～6 minutes, continued to stir 15 minutes; Leave standstill after 7 hours part supernatant suction strainer is removed.To remain the sediment water slurry and change in the 500L lining titanium autoclave, and end when charging into hydrogen to pressure 3.5MPa, mixing speed transfers to 550r/min, begins then to heat up.When the temperature in the autoclave reaches 180 ℃, be incubated 2.6 hours; Then open cooling water and make the water slurry cooling, when water slurry in the still was cooled to 80 ℃, the speed of material was discharged in control, and water slurry is wherein discharged, and simultaneously the residual gas in the autoclave was discharged, and reduced to normal pressure.The water slurry of discharging uses 14kg alcohol that filter residue is wetting after washing through 5 filtration, deionized waters repeatedly again, puts into electrically heated vacuum drying chamber and dehydrates 6 hours for inherent 135 ℃.The dried material ball milling after 20 minutes, is sent in the tubular type reduction furnace, reduced 7.5 hours at 480 ℃ of constant temperature with hydrogen.Take out from the discharge end cooling back of tubular type reduction furnace, pour in the metal bucket, sealing charged into nitrogen treatment after 20 hours, obtained the super-fine cobalt powder product.By analysis, the cobalt powder apparent density is 0.8g/cm
3, oxygen content 0.56% contains the cobalt amount and reaches 99.52% (adopt the percetage by weight minusing to calculate, wherein do not comprise gaseous impurity).The super-fine cobalt powder uniform particles, spherical in shape, granularity is about 300nm～800nm.
The raw material of cobalt can also use basic cobaltous carbonate, cobalt carbonate or cobalt oxide to replace cobalt hydroxide; A kind of replacement in hydrochloric acid sulfuric acid, nitric acid, the acetic acid; Dispersant replaces polyvinyl alcohol, polypropylene glycol with one or more (being no more than three kinds at most) in polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PBG), polyvinyl alcohol (PVA) polyvinylpyrrolidone (PVP), tween-80, the oleic acid; Precipitating reagent is then with a kind of replacement sodium carbonate in NaOH, potassium hydroxide, sodium acid carbonate, potash, saleratus, carbonic hydroammonium, ammonium carbonate or oxalic acid, the ammonium oxalate etc.; The specific requirement that provides by technical scheme then adopts said method can prepare the spherical super fine cobalt powder equally.
Embodiment 5
A kind of gas that does not charge into during hydrothermal treatment consists in pressure-air, oxygen, nitrogen or the hydrogen increases the autoclave internal pressure, and the employing nickel chloride is that raw material, potassium hydroxide are that precipitating reagent prepares extra-fine nickel powder.In tank diameter A, add deionized water 160L, be warming up to 50 ℃; Take by weighing technical pure nickel chloride 46kg, add in the tank diameter A, stir and make the nickel chloride dissolving; Add polyethylene of dispersing agent alcohol 1100g, oleic acid 400g, tween-80400g subsequently, and nickel chloride aqueous solution is diluted to volume 220L.Add deionized water 140L earlier in tank diameter B, add technical pure potassium hydroxide 22Kg then, stirring makes it to dissolve fully, is diluted to the volume 205L aqueous solution.The nickel chloride aqueous solution rapid (in 5～6 minutes) that will contain dispersant under stirring condition joins in the potassium hydroxide aqueous solution, continues to stir 13 minutes; Leave standstill after 10 hours part supernatant suction strainer is removed.To remain the sediment water slurry and change in the 500L lining titanium autoclave, mixing speed transfers to 520r/min, begins then to heat up.When the temperature in the autoclave reaches 165 ℃, be incubated 9 hours; Then open cooling water and make the water slurry cooling, when water slurry in the still is cooled to 89 ℃, water slurry is wherein discharged.The water slurry of discharging uses the 12kg n-butanol with the filter residue mixing after washing through 5 filtration, deionized waters repeatedly again, puts into electrically heated vacuum drying chamber and dehydrates 6 hours for inherent 120 ℃.The dried material ball milling after 20 minutes, is sent in the tubular type reduction furnace,, taken out from the discharge end cooling back of tubular type reduction furnace 480 ℃ of constant temperature reduction 6 hours with hydrogen, pour in the metal bucket, sealing charged into nitrogen treatment 20 hours, obtained the extra-fine nickel powder product.By analysis, the nickel powder apparent density is 1.0g/cm
3, oxygen content 0.17%, nickel content reaches 99.65% (adopt the percetage by weight minusing to calculate, wherein do not comprise gaseous impurity).Analyze through SEM (SEM), the extra-fine nickel powder uniform particles, size is about 400nm～950nm.
The raw material of nickel can also use nickel nitrate, nickelous sulfate, nickel acetate to replace nickel chloride; Dispersant replaces polyvinyl alcohol, tween-80, oleic acid with one or more (being no more than three kinds at most) in polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PBG), polyvinyl alcohol (PVA) polyvinylpyrrolidone (PVP), tween-80, the oleic acid; Precipitating reagent is then with a kind of replacement potassium hydroxide in NaOH, sodium carbonate, sodium acid carbonate, potash, saleratus, carbonic hydroammonium, ammonium carbonate or oxalic acid, the ammonium oxalate etc.; The specific requirement that provides by technical scheme then, not charging into pressure-air, oxygen, nitrogen or hydrogen during the sediment hydrothermal treatment consists increases the autoclave internal pressure, adopts said method can prepare the spherical super fine nickel powder equally.
Embodiment 6
A kind of gas that does not charge into during hydrothermal treatment consists in pressure-air, oxygen, nitrogen or the hydrogen increases the autoclave internal pressure, and the employing basic cobaltous carbonate is that raw material, potash are that precipitating reagent prepares super-fine cobalt powder.In tank diameter A, add deionized water 130L, be warming up to 40 ℃; Take by weighing basic cobaltous carbonate 24.6kg, add in the tank diameter A, stirring makes cobalt carbonate wetting, the furnishing water slurry; With 120L concentration is that the aqueous sulfuric acid of 158g/L joins in the tank diameter A, constantly stirs, and makes the dissolving of cobalt carbonate water slurry.After cobalt carbonate has dissolved, cobalt sulfate solution is filtered, remove insoluble matter, and liquor capacity is diluted to 260L with the acidproof filter cloth of 400 purposes.Add dispersant polyethylene glycol 1100g, polyvinyl alcohol 980g subsequently.In tank diameter B, add deionized water 160L earlier, slowly add technical pure potash 26.6kg then, add thermal agitation and make it to dissolve fully.The cobalt sulfate solution that will contain dispersant under stirring condition joined in the wet chemical in 5～6 minutes, continued to stir 15 minutes; Leave standstill after 8 hours part supernatant suction strainer is removed.To remain the sediment water slurry and change in the 500L lining titanium autoclave, mixing speed transfers to 520r/min, begins then to heat up.When the temperature in the autoclave reaches 180 ℃, be incubated 6.5 hours; Then open cooling water and make the water slurry cooling, when water slurry in the still is cooled to 85 ℃, water slurry is wherein discharged.The water slurry of discharging uses the 12kg n-octyl alcohol with the filter residue mixing after washing through 5 filtration, deionized waters repeatedly again, puts into electrically heated vacuum drying chamber and dehydrates 6 hours in 130 ℃.The dried material ball milling after 20 minutes, is sent in the tubular type reduction furnace,, taken out from the discharge end cooling back of tubular type reduction furnace 460 ℃ of constant temperature reduction 7 hours with hydrogen, pour in the metal bucket, sealing charged into nitrogen treatment 22 hours, obtained the super-fine cobalt powder product.By analysis, the cobalt powder apparent density is 0.9g/cm
3, oxygen content 0.7% contains the cobalt amount and reaches 99.55% (adopt the percetage by weight minusing to calculate, wherein do not comprise gaseous impurity).The super-fine cobalt powder uniform particles, size is about 500nm～850nm.
The raw material of cobalt can also use cobalt carbonate, cobalt hydroxide or cobalt oxide to replace basic cobaltous carbonate; With a kind of replacement sulfuric acid in hydrochloric acid, nitric acid, the acetic acid; Dispersant replaces polyethylene glycol, polyvinyl alcohol with one or more (being no more than three kinds at most) in polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PBG), polyvinyl alcohol (PVA) polyvinylpyrrolidone (PVP), tween-80, the oleic acid; Precipitating reagent is then with a kind of replacement potash in NaOH, potassium hydroxide, sodium acid carbonate, sodium carbonate, saleratus, carbonic hydroammonium, ammonium carbonate or oxalic acid, the ammonium oxalate etc.; The specific requirement that provides by technical scheme then, a kind of gas that does not charge into during the sediment hydrothermal treatment consists in pressure-air, oxygen, nitrogen or the hydrogen increases the autoclave internal pressure, adopts said method can prepare the spherical super fine cobalt powder equally.
Claims (2)
1, a kind of process of producing spherical submicron metal with hydro-thermal treatment, adopt operations such as precipitation, dispersant finishing, water under high pressure heat treatment, washing, drying, high-temperature hydrogen reduction to prepare spherical super fine nickel powder or super-fine cobalt powder, it is characterized in that may further comprise the steps:
(1) is raw material with the water soluble salt of nickeliferous, cobalt such as sulfate, nitrate, chloride, acetate, is made into the aqueous solution of single salt; Perhaps oxide, subcarbonate, carbonate or the hydroxide dissolving of nickel, cobalt made the aqueous solution of corresponding sulfate, nitrate, chloride, acetate with sulfuric acid, nitric acid, hydrochloric acid, acetic acid; Concentration of metal ions is controlled at nickeliferous or cobalt 30～70g/L in the aqueous solution of the single salt of being prepared.
(2) add one or more (being no more than three kinds at most) in polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PBG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), tween-80, the oleic acid as dispersant in the nickel of preparation or the cobalt aqueous solution, various dispersants add and add up to 6～12g/L.
(3) precipitating reagent is alkali (NaOH, potassium hydroxide), sodium carbonate, sodium acid carbonate, potash, saleratus, carbonic hydroammonium, ammonium carbonate or oxalic acid, ammonium oxalate etc., selects wherein a kind of, by the aqueous solution of 0.7～4.0mol/L concentration preparation precipitating reagent.
(4) get the aqueous solution of required theoretical amount 102%～106% precipitating reagent, the aqueous solution with nickeliferous or cobalt and dispersant under normal temperature condition adds wherein, and constantly stirs, and solution is fully mixed, homogeneous reaction.After two kinds of solution mix fully, continue to stir 10～15 minutes; Leave standstill after 6～10 hours the elimination of part supernatant, water slurry is changed in the autoclave of lining titanium; Filtrate then discards after treatment.
(5) speed of agitator with autoclave is made as 450～550r/min, and heating-up temperature is limited to 135～190 ℃, charges into a kind of in pressure-air, oxygen, nitrogen or the hydrogen, makes the still internal pressure reach 3.0～4.2MPa.With water slurry heating in the still, when temperature rises to assigned temperature, be incubated 1～3 hour, carry out hydrothermal treatment consists.When being cooled to water slurry below 90 ℃, utilize the pressure in the still, discharge water slurry wherein, and emit the gas in the autoclave, reduce to normal pressure.Filter repeatedly, Xian Di 3～5 times, filter residue is wetting slightly afterwards at 115～140 ℃ of following vacuum dryings with a small amount of alcohol (filter residue: alcohol=100:5～10 weight ratios, or with n-butanol, n-octyl alcohol substituted alcohol).
(6) material after the oven dry is put into hydrogen reducing furnace in 350～550 ℃ of reduction 3～8 hours then through 20～30 minutes mixings of ball milling, and the product that reduction obtains is preserved in nitrogen atmosphere and become final extra-fine nickel powder or super-fine cobalt powder product after 16～24 hours.
2, by the process of the described a kind of producing spherical submicron metal with hydro-thermal treatment of claim 1, it is characterized in that if a kind of gas that does not charge in pressure-air, oxygen, nitrogen or the hydrogen increases the autoclave internal pressure, when carrying out hydrothermal treatment consists, should extend to 6～10 hours 145～200 ℃ insulation processing time.
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