CN106077692A - A kind of preparation method of metallic cobalt microsphere - Google Patents
A kind of preparation method of metallic cobalt microsphere Download PDFInfo
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- CN106077692A CN106077692A CN201610379557.XA CN201610379557A CN106077692A CN 106077692 A CN106077692 A CN 106077692A CN 201610379557 A CN201610379557 A CN 201610379557A CN 106077692 A CN106077692 A CN 106077692A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
Abstract
The present invention relates to the preparation method of a kind of metallic cobalt microsphere, step is as follows: (1) is prepared cobalt source mother solution by cobalt nitrate and EDTA, then adds ammonia and water, and the pH value making solution is 12.4；Then above-mentioned solution is transferred in reactor, add high purity metal cobalt plate as substrate, hydro-thermal reaction at 90 120 DEG C, then rinsing, drying；(2) being sent directly in Muffle furnace together with metallic cobalt plate by above-mentioned micron-size spherical cobalt hydroxide, programming rate controls at 1 10 DEG C per minute, and final temperature controls at 250 350 DEG C, temperature retention time 35 hours；(3) the micron-size spherical Cobalto-cobaltic oxide that will be cooled to about 200 DEG C is sent directly into reduction furnace together with metallic cobalt plate, air pressure controls at 0.24 0.35Mpa, programming rate controls at 10 20 DEG C per minute, and final temperature controls at 600 800 DEG C, temperature retention time 23 hours；(4) after using ion blower elimination to cool down, the electrostatic of metallic cobalt microsphere, then carries out Multi-stage airflow selecting crude drugs with winnower by metallic cobalt microsphere and eliminates the bulky grain of more than 20 μm.
Description
Technical field
The present invention relates to the preparation method of a kind of metallic cobalt microsphere.
Background technology
The existing application of globular metallic powder has powder metallurgy, 3D metallic print, battery, Electronic Packaging, accurate system
Standby etc..The preparation method of metal current spheroidal particle, mainly comminuting method (pulverized by coarse granule or melt liquid and obtain fine powder)
With synthetic method (by ion, atom, molecule, obtain fine powder body method by reaction, nucleation and growth, collection, post processing) two
Big class.The former, comminuting method substantially can be divided three classes: gas atomization based on droplet jet solidification balling-up and centrifugal atomizing
Method；The shredding of mechanically-based shearing balling-up or punching remelting process；Symmetrical liquid drop injecting method and pulse small hole spurt method.Said method
Major defect be that under electrostatic interaction, particle aggregation is very serious, impurity is many, and particle diameter distribution is excessive, and micropartical is spherical
Spend the highest, it is difficult to preparation is smaller in size than the metal ball of below 100 μm.It is thus desirable to subsequent treatment such as further screenings, increase
The cost of said method.
And synthetic method is in preparation spherical ultrathin cobalt powder, the most relatively effective is hydrogen reduction method, the cobalt prepared by the method
Powder Particle Size is little, uniform, mobility and mixed effect preferable, so the cobalt powder of domestic production substantially belongs to hydrogen reduction cobalt powder.Hydrogen is also
Former method includes high temperature solid-state hydrogen reduction method and High Pressure Hydrogen reducing process two kinds.High temperature solid-state hydrogen reduction method is by the oxide or heavy of cobalt
Shallow lake product with hydrogen at high temperature reduces, and prepares metal cobalt powder, and this is the industrialization method preparing cobalt powder at present, but its product one
As reunite serious, granule is relatively thick, and oxygen content is higher, it is more difficult to obtain super-fine cobalt powder.High Pressure Hydrogen reducing process is under elevated pressure conditions, uses
Solution or the slurry of hydrogen reducing cobalt prepare super-fine cobalt powder.The hydrogen pressure that this method requires is higher, and purity also can only achieve about 95%,
Being extremely difficult to the requirement of super-fine cobalt powder product, and pattern is dendroid, spherical cobalt powder is few.
Carry out a lot of trials for the problems referred to above, business circles and University Scientific Research mechanism from the following aspects and ground
Study carefully.
First being high temperature solid-state hydrogen reduction method aspect, the previous majority that is usually is the oxidation using cobalt oxalate to obtain after aoxidizing
Cobalt carries out the method for hydrogen reduction again and produces, and the cobalt powder of cobalt oxalate direct-reduction preparation is the most universal.Zhuzhou Hard Alloy Plant Yuan Ping
At " research to cobalt powder particle size influences of the cobalt oxalate precipitation technique " (hard alloy, calendar year 2001, volume 18, the 1st phase) mesoxalic acid cobalt
Pattern determine cobalt powder pattern, the crystal grain of cobalt oxalate is rod-like fibre structure, and the chain of cobalt powder is shorter, in the most granular；
Cobalt oxalate precipitation technique is CoCl to the major influence factors of cobalt powder particle size influences2Temperature when solution density and reaction, secondly
It it is the flow velocity adding ammonium oxalate；The condition producing fine grained cobalt oxalate and cobalt powder is that solution density is little, and reaction temperature is low, flow velocity
Greatly, on the contrary granule is just thick.Jinchuan non-ferrous metal group nickel cobalt new product company Wang Jinrui et al. is " cobalt powder is prepared in cobalt oxalate reduction
Experimental study " (Gansu metallurgical, in JIUYUE, 2004 the 3rd phase of volume 26) proposes to use shaft furnace device, with hydrogen and nitrogen be
Mixing reducing atmosphere reduction, in the case of controlling temperature, recovery time and reducing gas flow, makes the pine ratio of cobalt powder control
0.4～0.6g/cm3, hydrogen loss is less than 0.3%, and the pattern of cobalt powder is in the best dendritic structure.Beijing mining and metallurgy research is total
Institute Huang profit is big et al. in " oxidizing condition of cobalt oxalate is on cobalt oxide and the impact of reduction cobalt powder performance " (non-ferrous metal (smelting portion
Point), 2 phases in 2005) in propose cobalt oxalate and be oxidized to cobalt oxide and carry out the cobalt powder of hydrogen reduction, its powder size and oxalic acid again
The oxidizing temperature of cobalt is relevant, relevant with oxidizing process equipment, operational approach.The cobalt powder that cobalt oxalate direct-reduction obtains compares cobalt oxalate
The cobalt powder obtained is restored thinner after oxidation.In production process, output β-Co phase cobalt powder naturally, but can produce under proper condition
Going out principal phase is α-Co cobalt powder.Additionally, also someone changes predecessor, such as powder metallurgy National Key Laboratory of Central South University Luo Chong
Tinkling of pieces of jade et al. uses steel band type even in the craft discussion of superfine spherical cobalt powder " cobalt carbonate prepare " (hard alloy, 02 phase in 2007)
Continuous reduction furnace, with cobalt carbonate as raw material, prepares cobalt powder with hydrogen reduction method；This cobalt powder prepared is spherical in shape or class is spherical, rather than
Dendroid；Sichuan University shuts out little China et al. in " room-temperature ball-milling solid state reaction method-hydrogen reduction method prepares superfine spherical cobalt powder "
Proposing in (heat processing technique, volume 2013,42,24 phases) to use room-temperature ball-milling solid state reaction method to prepare predecessor is CoCO3,
Then medium temperature roast, prepares superfine spherical cobalt powder with hydrogen reducing, uses ball milling to cause its reunion extremely serious in the method.
In terms of actual production, Zhejiang Province Huayou cobalt industry Co., Ltd is the cobalt chemicals production of current Largest In China
Business, applies for and has multinomial relevant cobalt industry producing patent.One of its core patent is " a kind of side preparing superfine spherical cobalt powder
Method " (ZL200810121121.6) proposition is with cobalt ore as raw material, and employing precipitation from homogeneous solution-thermal reduction produces single dispersing continuously, surpasses
The method of thin spherical cobalt powder, it is characterised in that it includes providing 60-160g/L cobalt salt solution and the step of precipitant solution, described
The one in ammonium hydrogen carbonate, ammonium carbonate selected by precipitant, is made into the solution of mass concentration 80-200g/L after dissolving, filtering, and
Perform according to the following steps: (a). in above-mentioned cobalt liquid, add polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), hexadecane
One or more in base trimethylammonium bromide (CTAB), Polyethylene Glycol PEG (1000), water soluble starch, as homogeneous cobalt salt
Solution；(b). the precipitant solution of homogeneous cobalt saline solution with theoretical response magnitude 1.1～1.3 times is added reaction by cocurrent adding material method
Still, controls synthesis reaction temperature and is 40-90 DEG C, and pH value in reaction is 6.0-8.5, and charging rate is 200-1000L/h, mixing speed
For 500-1500rpm, prepare superfine spherical Cobalt carbonate sediment with homogeneous precipitation method；(c). precipitate is through filtration washing, flash distillation
Obtaining superfine spherical cobaltous carbonate powder after drying, granularity is 0.6～1.0 μm；Tail washings after filtration, uses Integrated Films and evaporation knot
After brilliant integrated treatment, fresh water returns production and application, and by-product reclaims with crystalline salt form, described Integrated Films be processed as reverse osmosis+
Electrodialysis process；(d). by above-mentioned cobaltous carbonate powder, send in reduction furnace, at 400-550 DEG C, carry out Continuous Heat reduction obtain
Superfine spherical cobalt powder.The followed by related invention patent to predecessor, such as carbonate " preparation method of a kind of spherical carbonate "
(ZL 201010209990.1) and " a kind of continuous method preparing big particle diameter spherical cobaltous carbonate " (application number:
201510151958.5)；Hydroxy cobalt oxide " preparation method of spherical hydroxy cobalt oxide-cobaltosic oxide composite material " (application
Number: 201510152081.1)；Cobalt hydroxide etc..Wherein cobalt hydroxide relative skill is ripe, has " a kind of without chelating agent body
The method preparing spherical cobalt hydroxide under system " (ZL200910307676.4) middle proposition is with pure water for end liquid, under agitation by cobalt
Liquid and sodium hydroxide solution are simultaneously introduced in the end liquid generation precipitation, solution during also drip adds cobalt liquid and sodium hydroxide
PH value be maintained at 5-7, during terminal, the pH value of solution is 10.5-13.5；Then prevent that it aoxidizes toward interpolation antioxidant in solution,
Cobalt hydroxide slurry is scrubbed and dried, obtains spherical cobalt hydroxide product；" the high pine of a kind of serialization preparation is than cobalt hydroxide
Method " (ZL 201310290589.9) propose use containing cobalt ore material be raw material, through leach purify, obtain cobalt chloride solution；With
NaOH is end liquid, by NaOH, cobaltous chloride and enveloping agent solution and flow addition reactor, is controlled by pH value rapidly in co-current process
8～12, temperature controls at 30～90 DEG C, and mixing speed, 200～1000rpm, after reaction 6～40h, opens the overflow of reactor
Valve, starts continuous prodution, and product fine, pattern is porous spherical, and granularity is normal distribution.
And High Pressure Hydrogen reducing process aspect, Sherritt company is the initiator that metal cobalt powder is prepared in High Pressure Hydrogen reduction, from upper
The fifties beginning in century, the most successfully use wet method pressurized hydrogen reduction technique, from cobaltous ammonium sulfate solution, directly produce High Purity Gold
Belonging to cobalt powder, the product granularity obtained is thicker.Shanghai Smeltery of China, starts that from 1985 this technique is also used for cobalt powder and produces.
Its predecessor of Westaim company is a part for Sherritt company, and 1992 start, and are improved this technology, to produce Asia
The super-fine cobalt powder of the narrow grain class distribution of micron order.Technical process after improvement is, is first dissolved in sulphuric acid by metallic cobalt, generates
CoSO4Solution, is subsequently adding liquefied ammonia and is converted into cobaltous ammonium sulfate, during adding ammonia, also creates part alkali formula sulfur simultaneously
Acid cobalt.The generation of part alkali formula cobaltous sulfate can promote that forming core reaction occurs.Final step is displacement precipitation from supersaturated solution
Go out super-fine cobalt powder.The cobalt powder granularity of High Pressure Hydrogen also original production can regulate between submicron to micron, with oxalate precipitation-thermal decomposition
Technics comparing, can produce the cobalt powder that class is spherical, ultra-fine, tap density is high is its advantage.At present, UMICORE company is also adopted by height
Pressure hydrogen reduction method, produces high-quality cobalt powder and supplies high-end hard alloy market.The cobalt powder that two kinds of methods produce, except crystal structure is different
Outward, its hardness of the cobalt powder of chemical precipitation is higher than oxalates thermal decomposition method.The domestic research carrying out this respect is less.Kunming science and engineering
University material scientific and engineering institute Zan Lin Han etc. deliver in " Materials Science and Engineering journal " (2010, volume 28,126 phases)
" hydrogen reduction method prepares super-fine cobalt powder ", it is proposed that use CoSO4Add the Co (OH) that excess NaOH produces2Serosity, at low hydrogen edema caused by disorder of QI
Under pressure (1MPa), Hydrothermal Pressure Hydrogen Reduction method has prepared particle mean size 120nm, the class spherical ultrathin cobalt powder of purity 96%；And to ultra-fine
Cobalt powder carries out secondary high-temperature (700 degrees Celsius) hydrogen reduction, and particle diameter is only grown up to about 200nm, high purity 99.68%；Pass through
Control secondary reduction temperature and can obtain close-packed hexagonal, the cobalt powder of two kinds of structures of face-centered cubic, to Co (OH)2Slurry hydrogen reduction
Mechanism has carried out desk study.Use for reference the thinking carrying out reduction reaction in the liquid phase, domestic colleges and universities have been also carried out certain tasting
Examination, as Lanzhou University of Science & Technology Liu Peng become " preparation technology of super-fine cobalt powder with process for modifying surface study " (2006, Lanzhou science and engineering
University's Master's thesis) middle proposition polyhydric alcohol liquid phase reduction, achieve a stage reduction method in the liquid phase and prepare super-fine cobalt powder；Different
Presoma Co (OH) prepared by cobalt salt2Subsequent reactions is had a certain impact, but impact is not the biggest；Product have purity high,
Fine size, be evenly distributed, the feature such as spherical in shape.Central South University Bi Dandan is at the research of super-fine cobalt powder " polyol process prepare "
In (2008, Central South University's Master's thesis), with calcining under cobalt oxalate 300 degrees Celsius, obtain is front with cobaltosic oxide powder
Driving the reduction of body glycerol and prepare that purity is higher and the spherical cobalt powder of even particle size distribution, the pattern of its pattern and presoma is without continuing
Holding property.
The production link that technology disclosed in this patent relates to can provide intermediate product as commodity, and economic worth is high,
And the metallic cobalt microsphere that this technique produces is reunited few, bulk density is high.
Summary of the invention
In order to realize above-mentioned purpose, it is an object of the invention to provide the preparation method of a kind of metallic cobalt microsphere, the method is raw
The metallic cobalt microsphere produced, purity is high, reunites few, and particle diameter is reasonably distributed, bulk density and apparent density advantages of higher.
In order to realize above-mentioned purpose, the preparation thinking of the present invention: under thermal and hydric environment, water-soluble metal cobalt salt is in Metal Substrate
Induced growth micron-size spherical cobalt hydroxide on plate；Utilize the principle that pattern is inherited, at a certain temperature spherical cobalt hydroxide heat
Resolve into micron-size spherical Cobalto-cobaltic oxide；Last under reduction furnace, use natural gas reduction Cobalto-cobaltic oxide to obtain metallic cobalt
Microsphere.The advantage of such scheme, the product of each step all can become the raw material of special-purpose, and operation and process are simple
Being easily controlled, the quality of product can be protected.
It is an object of the invention to be achieved through the following technical solutions, the preparation method of a kind of metallic cobalt microsphere, the party
The step that method includes is as follows:
(1) hydro-thermal method prepares micron-size spherical cobalt hydroxide
First being prepared cobalt source mother solution by cobalt nitrate and EDTA, cobalt nitrate substance withdrawl syndrome is 2molL-1, EDTA concentration is
1molL-1, then add ammonia and water, make the pH value about 12.4 of solution；Then above-mentioned solution is transferred in hydrothermal reaction kettle,
The metallic cobalt plate of addition purity ＞ 99.99% is as substrate, and in holding furnace, 90-120 degree Celsius of lower hydro-thermal reaction 5-20 hour, takes
Go out metallic cobalt plate and it is rinsed repeatedly with deionized water and ethanol, is dried 1-2 hour, i.e. can obtain being attached to metal
Micron-size spherical cobalt hydroxide on cobalt plate；
(2) thermal decomposition process obtains micron-size spherical Cobalto-cobaltic oxide
Being sent directly in Muffle furnace together with metallic cobalt plate by above-mentioned micron-size spherical cobalt hydroxide, programming rate controls at 1-
10 DEG C per minute, and final temperature controls at 250-350 DEG C, and then temperature retention time 3-5 hour naturally cools to about 200 DEG C；
(3) natural gas reduction obtains metallic cobalt microsphere
The micron-size spherical Cobalto-cobaltic oxide that will be cooled to about 200 DEG C is sent directly into reduction furnace, gas together with metallic cobalt plate
Voltage-controlled system controls at 10-20 DEG C per minute at 0.24-0.35Mpa, programming rate, and final temperature controls at 600-800 DEG C, insulation
2-3 hour time, hot exhaust gas is directly discharged in the holding furnace of placing response still；
(4) Multi-stage airflow selecting crude drugs with winnower eliminates bulky grain
After using ion blower elimination to cool down, the electrostatic of metallic cobalt microsphere, then carries out Multi-stage airflow wind by metallic cobalt microsphere
Choosing eliminates the bulky grain of more than 20 μm.
The gain effect of the present invention is as follows:
1, the preparation method of a kind of metallic cobalt of present invention microsphere is different from the side such as hydrogen reduction method and metallic high temperature annealing solidification
Method, its equipment, technology difficulty and energy consumption cost are greatly reduced, and are conducive to improving product competitiveness.
2, the preparation method of a kind of metallic cobalt of present invention microsphere takes substep to produce, beneficially the quality prison of links
Control, the intermediate product (micron-size spherical cobalt hydroxide and micron-size spherical Cobalto-cobaltic oxide) of each production link can also simultaneously
Carry out production marketing, beneficially enterprise to carry out producing adjustment according to the market demand in time.
3, have employed metal form in the preparation method of a kind of metallic cobalt of present invention microsphere, beneficially the collection of granule, keeps away
Having exempted from secondary pollution, beneficially the raising of product purity, enhances automated production.
4, the heat that in the preparation method of a kind of metallic cobalt of present invention microsphere, the reaction of high temperature reduction is unnecessary is with the form of tail gas
In being supplied to early stage to produce, holding furnace etc., reduce energy consumption, beneficially energy-conserving and environment-protective.
5, the preparation method of a kind of metallic cobalt of present invention microsphere have employed Multi-stage airflow selecting crude drugs with winnower and eliminate bulky grain and ion
Blower fan eliminates the electrostatic of metallic cobalt microsphere after cooling down, and effectively reduces the reunion of product, improves bulk density.
Accompanying drawing explanation
Relation schematic diagram between Fig. 1 pH value in solution and concentration of cobalt ions.
Micron-size spherical Co (OH) on Fig. 2 cobalt plate2XRD diffracting spectrum.(a, 5h；B, 10h；C, 15h；D, 20h)
Fig. 3 micron-size spherical Co (OH)2Average diameter schematic diagram over time.
Fig. 4 micron-size spherical Co (OH)2Thermogravimetric curve.
Fig. 5 thermal decomposition process obtains micron-size spherical Co3O4Electron scanning micrograph.(a, 250 DEG C；B, 300 DEG C；
C, 350 DEG C)
Fig. 6 micron-size spherical Co3O4Power spectrum is tested.
Fig. 7 metallic cobalt microspheres product electron scanning micrograph.
Detailed description of the invention
The preparation method of a kind of metallic cobalt microsphere that the present invention provides, comprises following four critical process step.
The first step is that hydro-thermal method prepares micron-size spherical cobalt hydroxide.Hydro-thermal method prepares the nano-micro level hydrogen-oxygen of various form
Change cobalt and have been obtained for universal accreditation.And prepare spherical cobalt hydroxide it is crucial that the resolution of precipitate of cobalt hydroxide balances in system
Gentleness carry out, the most at a lower temperature, control the concentration of cobalt ion in rational pH value and solution.In this technique, solution is deposited
At cobalt ion, ammonium radical ion, hydroxyl, EDTA, amino molecule, cobalt hydroxide etc. is between material, and above-mentioned molecule or ion
There is all kinds of molecular balance, and generate complex ion.By calculating corresponding coefficient of balance and Ion binding constant, we obtain
Cobalt ion and pH value must be related to, such as Fig. 1, in order in guarantee system cobalt hydroxide homogeneous nucleation and all to growth, maintain
Its relatively low concentration is highly desirable to, and i.e. requires that most cobalt ion exists with complex form, cobalt ion itself in solution
Concentration is reduced to 0.01molL-1(i.e. in figure, concentration of cobalt ions logarithm is the horizontal line of-2), now pH value should be more than 12.38.Institute
Specific as follows with this step: first to be prepared cobalt source mother solution by cabaltous nitrate hexahydrate and EDTA, then add ammonia and water, this solution
Concentration of cobalt ions 2molL is joined at the beginning of in-1, EDTA concentration is 1molL-1, solution ph is about 12.4；Then above-mentioned solution is shifted
In hydrothermal reaction kettle, adding as the metallic cobalt plate of substrate, in holding furnace, several hours of 90 degrees Celsius of lower hydro-thermal reactions, take out
It is also rinsed with deionized water and ethanol, is dried 2 hours by metallic cobalt plate repeatedly, i.e. can obtain being attached to metallic cobalt plate
On micron-size spherical cobalt hydroxide.In view of yield, the time of hydro-thermal reaction is particularly concerned about by we, and Fig. 2 is hydro-thermal reaction
Co (OH) on time cobalt plate2The XRD diffracting spectrum of powder, from 5-20 hour, finds that its cobalt hydroxide crystal formation is not the most sent out
Changing, historical facts or anecdotes takes in trampling 5 hours, finds prolongation over time simultaneously, and cobalt hydroxide microsphere radius is increasing, concrete rule
As shown in Figure 3.
Second step is that thermal decomposition process obtains micron-size spherical Cobalto-cobaltic oxide.From micron-size spherical Co (OH)2To micron
Grade spherical cobaltosic oxide particle is a pyrolysis, wishes to keep original pattern not change, i.e. in course of reaction
The aqueous vapor that thermal decomposition produces can be stablized and discharges slowly, and do not destroys original spherical structure.This step it is crucial that set up
Reasonably temperature schedule.This temperature schedule includes programming rate, maximum temperature and temperature retention time etc., and programming rate is the most right
For this sample, control at 1 DEG C per minute.Maximum temperature can learn its situation thermally decomposed by thermogravimetric analysis.Such as figure
4, TG thermogravimetric curve figures, between 20～175 DEG C, sample there are about the mass loss of 7%, and this is because sample removing absorption water and is drawn
Rise.And along with the rising of temperature, between 45～175 DEG C, rate-of-loss of coolant quickly increases.Occur between 175 DEG C～400 DEG C
A large amount of weightless, about 10.9%, this is because precursor dehydroxylation, be oxidized to oxide.After 400 DEG C, TG curve tends to flat
Surely, show that precursor has reacted complete.Therefore, precursor is calcined at 250 DEG C, 300 DEG C and 350 DEG C and all can be prepared black
Co3O4.Fig. 5 is micron-size spherical Co (OH)2In Muffle furnace under said temperature the heat treatment scanning electron microscope of 5 hours
Photo.Three figures are micro-nano spheroid, there is the inheritance of pattern.Wherein Fig. 5 a finds 250 DEG C of samples being thermally treated resulting in
Good dispersion degree, size is little.Fig. 5 b, the sample dispersion degree of 300 DEG C is good, and nanosphere size occurs a little increasing.And Fig. 5 c, 350
DEG C sample there occurs bonding phenomenon, dispersion greatly reduces size and reaches 2 μm.Thus, it can be seen that high sintering temperature is unfavorable
In the dispersibility of product, too high temperature causes sintering.In view of dispersibility and production problems, 300 DEG C is optimum temperature, simultaneously
The test of power spectrum EDS shows the Co really of this sample3O4, the mass ratio of Co and O is close to chemical formula Co3O4Theoretical value, test position
With result such as Fig. 6.According in non-ferrous metal industry standard YS/T 633-2007 to Co3O4Testing requirement, under this technique prepare
Metallic cobalt Microspheres Technique index as follows:
3rd step is natural gas reduction Co3O4Obtain metallic cobalt microsphere, relate to a set of natural gas reduction furnace equipment.This device
By heating furnace body, reduction furnace tube, material-pulling device, natural gas flowmeter, control the groups such as device, multi-way intelligence temperature control, electric-control system
Become.Different with general hydrogen reducing furnace, owing to using natural gas, its safety and economy increase.Especially heat
Device part, the last period, operation was heat treatment in Muffle furnace, and material-pulling device therefore can be used to will be cooled to about 200 DEG C
Micron-size spherical Cobalto-cobaltic oxide is sent directly in reduction furnace together with metallic cobalt plate.Ensure also at 0.35Mpa by controlling air pressure
CH in former boiler tube4Content so that it is fully reduce, its central segment reduction temperature control 600 DEG C, temperature retention time 3 hours, heat up speed
Degree controls at 10-20 DEG C per minute.At the end of reduction operation, by controlling air pressure, that stove is contained within the hot exhaust gas of higher temperature is straight
Run in the holding furnace of placing response still.
4th step is that Multi-stage airflow selecting crude drugs with winnower eliminates bulky grain.After front one procedure reduction reaction terminates, go cold and receive
During collection, metallic cobalt microsphere surface temperature is low internal high, and its thermal stress direction is from inside to outside, has the possibility of expansion,
Secondly, during whole reduction reaction, the steam that reaction generates brings substantial amounts of charged group, and these groups are very possible
It is adsorbed in the surface defect point position of metallic cobalt microsphere, causes electrostatic on metallic cobalt microsphere band, cause the metallic cobalt microsphere after cooling
Containing a small amount of reunion, the bulky grain of particle growth or second particle in product.We intend using ion blower-Multi-stage airflow wind
Removing bulky grain associated with choosing-ion blower, the bulky grain for the secondary agglomeration in nodularization cooling procedure and particle growth adds
To remove.The electrostatic of metallic cobalt microsphere after using ion blower elimination to cool down for the first time, for then carrying out many by metallic cobalt microsphere
Level air-flow selecting crude drugs with winnower eliminates the bulky grain of more than 20 μm and creates conditions；Ion blower is to eliminate air-flow selecting crude drugs with winnower collision rift newly to produce for the second time
Raw electrostatic.After this procedure above-mentioned, metallic cobalt microspheres product has completely disengaged from metallic cobalt plate, and essentially eliminates quiet
Electricity, and as it is shown in fig. 7, be more than the granule of 20 μm, entirely without.Metallic cobalt microspheres product median 5 ± 2 μm, particle diameter ＜
4.00 μm account for more than 20wt%, and (＜ 4.00 μm accounts for >=20wt% to the distribution of its particle diameter；＜ 7.0 μm accounts for >=60wt%；＜ 20 μm accounts for
100wt%) substantially conform to the accumulation theory Westman equation of sized particles, the application of the most various closs packing occasions.
As follows by the metallic cobalt Microspheres Technique index of preparation under industry standard YS/T255-2009, this technique:
Claims (1)
1. the preparation method of a metallic cobalt microsphere, it is characterised in that the step that the method includes is as follows:
(1) hydro-thermal method prepares micron-size spherical cobalt hydroxide
First being prepared cobalt source mother solution by cobalt nitrate and EDTA, cobalt nitrate substance withdrawl syndrome is 2molL-1, EDTA concentration is
1molL-1, then adding ammonia and water, the pH value making solution is 12.4；Then above-mentioned solution is transferred in hydrothermal reaction kettle,
The metallic cobalt plate of addition purity ＞ 99.99% is as substrate, and in holding furnace, 90-120 degree Celsius of lower hydro-thermal reaction 5-20 hour, takes
Go out metallic cobalt plate and it is rinsed repeatedly with deionized water and ethanol, is dried 1-2 hour, i.e. can obtain being attached to metal
Micron-size spherical cobalt hydroxide on cobalt plate；
(2) thermal decomposition process obtains micron-size spherical Cobalto-cobaltic oxide
Being sent directly in Muffle furnace together with metallic cobalt plate by above-mentioned micron-size spherical cobalt hydroxide, programming rate controls at 1-10 DEG C
Per minute, final temperature controls at 250-350 DEG C, and then temperature retention time 3-5 hour naturally cools to about 200 DEG C；
(3) natural gas reduction obtains metallic cobalt microsphere
The micron-size spherical Cobalto-cobaltic oxide that will be cooled to about 200 DEG C is sent directly into reduction furnace, air pressure control together with metallic cobalt plate
System is at 0.24-0.35Mpa, and programming rate controls at 10-20 DEG C per minute, and final temperature controls at 600-800 DEG C, temperature retention time
2-3 hour, hot exhaust gas was directly discharged in the holding furnace of placing response still；
(4) Multi-stage airflow selecting crude drugs with winnower eliminates bulky grain
After using ion blower elimination to cool down, the electrostatic of metallic cobalt microsphere, then carries out Multi-stage airflow selecting crude drugs with winnower by metallic cobalt microsphere and disappears
Except bulky grains more than 20 μm.
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| CN110899718A (en) * | 2018-09-14 | 2020-03-24 | 上海铁路通信有限公司 | Preparation method of large-particle-size cobalt particles with shell-core structures |
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