CN101376174B - Method for preparing superfine spherical cobalt powder - Google Patents
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- CN101376174B CN101376174B CN2008101211216A CN200810121121A CN101376174B CN 101376174 B CN101376174 B CN 101376174B CN 2008101211216 A CN2008101211216 A CN 2008101211216A CN 200810121121 A CN200810121121 A CN 200810121121A CN 101376174 B CN101376174 B CN 101376174B
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Abstract
The invention relates to a method for preparing ultrafine spherical cobalt powder. The method adopts the cobalt ore as the raw material and the homogeneous precipitation-thermal reduction method to continuously prepare the mono-disperse ultra-fine spherical cobalt powder, processes the tail liquid generated during the synthesis process, and returns the tail liquid to the production system for recycling, thereby reducing the wastewater discharge, saving the production water supply and realizing the environment-friendly industrialized mass production of the ultrafine spherical cobalt powder. The prepared product of the ultrafine cobalt powder is in the shape of spherical particle with uniform particle size and intensive distribution. The method has the advantages of simple process, low production cost, high production efficiency, no environmental pollution and suitability for industrialized mass production.
Description
Technical field
The present invention relates to the preparation of cobalt powder, relate in particular to method for preparing ultrafine spherical cobalt powder.
Background technology
Super-fine cobalt powder has obtained using widely at carbide alloy, diamond tool and battery industry.Carbide alloy is that purity height, fine size, grain shape subglobular, reunion degree are low to the basic demand of cobalt powder.This is because spherical cobalt powder has good flowability, very high packed density, the minimum porosity and the relative coefficient of sliding friction, have superior autgmentability and extensibility, when mixing, show good intersolubility, make cemented carbide structure more even, fine and close with other materials.In addition, at diamond composition and battery industry, spherical cobalt powder helps the uniformity of batch mixing, makes consistency of product better.
At present, the main method of preparation super-fine cobalt powder has high-pressure water mist method, hydrogen reduction method, gamma-ray irradiation method, precipitation-thermal decomposition method, polyol reduction method, electrolysis and microemulsion method.
1) hydraulic atomized method is a kind of physical method, is about to the cobalt piece and puts into the induction melting furnace heat fused, makes motlten metal outflow from let slip a remark then, enter atomising device, under the High-Pressure Water from the annular distance nozzle impacts, be crashed to pieces into little molten drop and condensation rapidly, form super-fine cobalt powder.The thick 20-50 μ m of the cobalt powder granularity that this method is produced.
2) hydrogen reduction method is earlier to cobalt complex ([Co (NH
3)
5])
3+) feed carbon dioxide in the solution, be settled out CoCO
3Powder is at high temperature used hydrogen reducing again, can make oxygen content and be less than 2%, and granularity is less than 1 μ m, non-ignitability magnetic superfine cobalt powder.Also can in cobalt complex solution, add ammoniacal liquor, with Co
2+Be precipitated as Co (OH)
2, in autoclave, use hydrogen reducing under the pressure of 2.06MPa again, can obtain that purity height, granularity are little, the cobalt powder of narrow diameter distribution, powder shape is the class sphere, particle size range is 0.1～0.5 μ m.
3) the gamma-ray irradiation method is to use gamma-ray irradiation, directly prepares the method for superfine metal or metal oxide from the aqueous solution.The gamma-ray irradiation aqueous solution can produce aqueous electron eaq-, and aqueous electron is very active and have very strong reducing power, at room temperature can reduce cobalt ions.Technology is: prepare certain density cobalt liquor earlier, add an amount of isopropyl alcohol and polyvinyl alcohol respectively as free radical scavenger and dispersant, regulate the pH value with acetic acid (HAc) and NaOH, again the solution for preparing is carried out the oxygen content in ultrasonic degas processing and the feeding nitrogen reduction solution, carry out gamma-ray irradiation then.The gamma-ray irradiation close rate is the cobalt source of 70Gy/min, collects according to a conventional method behind the irradiation.This method makes pure α-Co polycrystalline superfines easily, and average grain diameter is 30nm.But this method equipment investment is big, and cost is higher.
4) to prepare the used raw material of cobalt powder be high-purity electrolytic cobalt sheet or cobalt button to precipitation-thermal decomposition method, behind dissolving with hydrochloric acid, makes CoCl with oxalic acid or ammonium oxalate solution again
2Solution changes cobalt oxalate precipitation into, carries out thermal decomposition in 500 ℃ then under protective atmosphere, can obtain the cobalt powder that particle mean size is 1-1.5 μ m.This method is easy to obtain irregular cobalt powder, and oxalic acid has toxicity.
5) the used polyalcohol of polyol reduction method be solvent be again reducing agent.At first will contain cobalt precursor (Co (OH)
2, CoC
2O
4, Co
3O
4, Co
2O
3) be distributed in the polyalcohol, presoma is middle mutually with the polyol reaction generation, then middle phased soln, and then, cobalt is reduced out, obtains cobalt powder.Because mechanism that polyol reduction method is special and low reduction temperature, product is spherical in shape, and granularity is little, narrow particle size distribution.But the polyalcohol cost that this method is used is higher, and is easy to decompose, and is difficult to large-scale industrial production.
6) electrolysis is to do anode with electrolytic cobalt, and the stainless steel water jacket is done negative electrode, and the electrolysis cobalt sulfate solution adds colloidal additive and prevents the ultra-fine grain reunion in the solution, obtain superfines.Electrolysis generally is used to prepare common cobalt powder, is difficult to obtain highly purified product.
7) microemulsion method is to prepare superfines and nano powder method commonly used.Earlier with in the molten isooctane of surfactant diethylhexyl sulfonic acid fourth diester sodium, again with CoCl
2And NaBH
4(sodium borohydride) is dissolved in respectively in this solution and obtains microemulsion.Two kinds of microemulsions are mixed, make coacervation of colloid as the agent of wadding a quilt with cotton with fixed attention with acetone and water, after filtration with washing after, drying just can obtain super-fine cobalt powder at low temperatures.The cobalt powder particle diameter that this method is produced is all less than 100nm.
Patent " precipitation-reduction prepares the method for nano-cobalt powder " (publication number is: the employing NaOH or the KOH that mention CN1686650) do precipitating reagent, but the intermediate product Co (OH) that makes
2Be colloid, and in the process of precipitation, be easy to bring into foreign ions such as Na, K, need to consume a large amount of water and wash.
Summary of the invention
Technical problem to be solved by this invention provides a kind of large-scale production and method of preparing superfine spherical cobalt powder little to ambient influnence of being suitable for.
For this reason, the present invention adopts following scheme: it comprises the step that 60-160g/L cobalt salt solution and precipitant solution are provided, described precipitating reagent is selected a kind of in carbonic hydroammonium, the ammonium carbonate for use, is made into the solution of mass concentration 80-200g/L through dissolving, after filtering, and carries out according to the following steps:
(a). in above-mentioned cobalt liquid, add in PVP (PVP), polyvinyl alcohol (PVA), softex kw (CTAB), polyethylene glycol PEG (1000), the water soluble starch one or more, as the homogeneous cobalt salting liquid;
(b). the precipitant solution of 1.1～1.3 times of homogeneous cobalt salting liquid and theoretical reacting doses is added reactor with the cocurrent adding material method, the control synthesis reaction temperature is 40-90 ℃, pH value in reaction is 6.0-8.5, charging rate is 200-1000L/h, mixing speed is 500-1500rpm, makes superfine spherical cobalt carbonate sediment with homogeneous precipitation method;
(c). sediment washs after filtration, obtain the superfine spherical cobaltous carbonate powder behind the expansion drying, and granularity is 0.6～1.0 μ m; Tail washings after the filtration, adopt integrated film+evaporative crystallization integrated treatment after, fresh water returns and produce to use, accessory substance reclaims with crystalline salt form, described integrated film is treated to counter-infiltration+electrodialysis process;
(d). with above-mentioned cobaltous carbonate powder, send in the reduction furnace, under 400-550 ℃, carry out the Continuous Heat reduction and obtain superfine spherical cobalt powder.
Compare with existing method, the present invention has the following advantages:
1. the product super-fine cobalt powder that makes of the present invention is a spheric granules, and granularity is 0.6～1.0 μ m, its epigranular, distribute concentrate, good dispersion;
2. the cobalt liquid after directly employing purifies is as raw material, and crystallization, course of dissolution that this has been avoided cobalt salt help reducing product cost;
3. select carbonic hydroammonium for use, or ammonium carbonate compares with NaOH, KOH as precipitating reagent, reduced bringing into of foreign ion sodium, potassium etc. in the precipitation process;
4. adopt the superfine spherical cobalt carbonate of the present invention's preparation to do precursor, this provides reliable assurance for preparing spherical cobalt powder;
5. adopt quick flash distillation mode to carry out drying and compare efficient height, automaticity height with the traditional drying method;
6. handle producing tail washings in the building-up process, fresh water returns makes the technology water, and the accessory substance of generation is sold as product after crystallization, and the whole system non-wastewater discharge had both helped reducing production costs, and helped environmental protection again;
7. the present invention has that technology is simple, production cost is low, production efficiency is high, is suitable for large-scale industrial production.
Description of drawings
Fig. 1 is a process chart of the present invention.
Fig. 2 is the super-fine cobalt powder shape appearance figure of embodiment 1.
Fig. 3 is the super-fine cobalt powder shape appearance figure of embodiment 2.
Fig. 4 is the super-fine cobalt powder shape appearance figure of embodiment 3.
The specific embodiment
Embodiment 1, with reference to accompanying drawing 1,2.
It is raw material that employing contains the cobalt ore material, after leaching purification, obtaining the highly purified cobalt that contains is 60～160g/L cobalt chloride solution, the 0.05-5% that presses the cobalt quality in above-mentioned cobalt liquid adds two kinds of a kind of or any proportioning of PVP (PVP), polyvinyl alcohol (PVA), as the homogeneous cobalt salting liquid; With carbonic hydroammonium is precipitating reagent, is made into the 80-200g/L precipitant solution after dissolving, filtration.The precipitant solution of 1.1～1.3 times of homogeneous cobalt salting liquid and theoretical reacting doses is added reactor with the cocurrent adding material method, adopting Distributed Control System (DCS) control reaction temperature is 40～90 ℃, pH value in reaction is 6.0～8.5, charging rate is 200-1000L/h, mixing speed is 800-1200rpm, make the sediment of superfine spherical cobalt carbonate continuously with homogeneous precipitation method, sediment washs after filtration, obtains the superfine spherical cobaltous carbonate powder behind the expansion drying fast, and Fisher particle size is 0.6～0.7 μ m.The tail washings that produces in the building-up process, after integrated film and evaporative crystallization processing, fresh water returns to produce and uses, and dense water is sold as byproduct through condensing crystallizing output ammonium chloride crystals body, and integrated film is treated to counter-infiltration+electrodialysis process.The cobalt carbonate of preparation is sent into reduction furnace, obtain the superfine spherical cobalt powder of Fisher particle size for～0.65 μ m 400-550 ℃ of following Continuous Heat reduction, its pattern as shown in Figure 2.
Embodiment 2, with reference to accompanying drawing 1,3.
It is raw material that employing contains the cobalt ore material, after leaching purification, obtaining the highly purified cobalt that contains is 60～160g/L cobalt sulfate solution, the 0.05-5% that presses the cobalt quality in above-mentioned cobalt liquid adds two kinds of a kind of or any proportioning among softex kw (CTAB), the polyethylene glycol PEG (1000), as cobalt salt solution; With carbonic hydroammonium is precipitating reagent, is made into the 80-200g/L precipitant solution after dissolving, filtration.The precipitant solution of 1.1～1.3 times of homogeneous cobalt salting liquid and theoretical reacting doses is added reactor with the cocurrent adding material method, adopting Distributed Control System (DCS) control reaction temperature is 40-90 ℃, pH value in reaction is 6.0～8.5, charging rate is 200-1000L/h, mixing speed is 800-1200rpm, make the sediment of superfine spherical cobalt carbonate continuously with homogeneous precipitation method, sediment washs after filtration, obtains the superfine spherical cobaltous carbonate powder behind the expansion drying fast, and Fisher particle size is 0.7～0.85 μ m.The tail washings that produces in the building-up process, after integrated film and evaporative crystallization processing, fresh water returns to produce and uses, and dense water condensing crystallizing generates ammonia sulfate crystal and sells as byproduct, and integrated film is treated to counter-infiltration+electrodialysis process.Send reduction furnace with the cobalt carbonate of preparation, obtain the superfine spherical cobalt powder of Fisher particle size for～0.8 μ m 400-550 ℃ of following Continuous Heat reduction, its pattern as shown in Figure 3.
Embodiment 3, with reference to accompanying drawing 1,4.
It is raw material that employing contains the cobalt ore material, after leaching purification, obtaining the highly purified cobalt that contains is 60～160g/L cobalt nitrate solution, the 0.05-5% that presses the cobalt quality in above-mentioned cobalt liquid adds two kinds of a kind of or any proportioning in PVP (PVP), polyvinyl alcohol (PVA), the water soluble starch, as the homogeneous cobalt salting liquid; With the ammonium carbonate is precipitating reagent, is made into the 80-200g/L precipitant solution after dissolving, filtration.The precipitant solution of 1.1～1.3 times of homogeneous cobalt salting liquid and theoretical reacting doses is added reactor with the cocurrent adding material method, adopting Distributed Control System (DCS) control reaction temperature is 40-90 ℃, pH value in reaction is 6.0～8.5, charging rate is 600-1000L/h, mixing speed is 800-1200rpm, make the sediment of superfine spherical cobalt carbonate continuously with homogeneous precipitation method, sediment washs after filtration, obtains the superfine spherical cobaltous carbonate powder behind the expansion drying fast, and Fisher particle size is 0.85～1.0 μ m.The tail washings that produces in the building-up process, after integrated film and evaporative crystallization processing, fresh water returns to produce and uses, and dense water condensing crystallizing produces the output ammonium nitrate crystals and sells as byproduct, and integrated film is treated to counter-infiltration+electrodialysis process.The cobalt carbonate of preparation is sent into reduction furnace, obtain the superfine spherical cobalt powder of Fisher particle size for～0.9 μ m 400-550 ℃ of following Continuous Heat reduction, its pattern as shown in Figure 4.
Claims (4)
1. method for preparing superfine spherical cobalt powder, it is characterized in that it comprises the step that 60-160g/L cobalt salt solution and precipitant solution are provided, described precipitating reagent is selected a kind of in carbonic hydroammonium, the ammonium carbonate for use, after dissolving, filtration, be made into the solution of mass concentration 80-200g/L, and carry out according to the following steps:
(a). in above-mentioned cobalt salt solution, add in PVP (PVP), polyvinyl alcohol (PVA), softex kw (CTAB), polyethylene glycol PEG (1000), the water soluble starch one or more, as the homogeneous cobalt salting liquid;
(b). the precipitant solution of 1.1～1.3 times of homogeneous cobalt salting liquid and theoretical reacting doses is added reactor with the cocurrent adding material method, the control synthesis reaction temperature is 40-90 ℃, pH value in reaction is 6.0-8.5, charging rate is 200-1000L/h, mixing speed is 500-1500rpm, makes superfine spherical cobalt carbonate sediment with homogeneous precipitation method;
(c). sediment washs after filtration, obtain the superfine spherical cobaltous carbonate powder behind the expansion drying, and granularity is 0.6～1.0 μ m; Tail washings after the filtration, adopt integrated film and evaporative crystallization integrated treatment after, fresh water returns and produce to use, accessory substance reclaims with crystalline salt form, described integrated film is treated to counter-infiltration+electrodialysis process;
(d). with above-mentioned cobaltous carbonate powder, send in the reduction furnace, under 400-550 ℃, carry out the Continuous Heat reduction and obtain superfine spherical cobalt powder.
2. a kind of method for preparing superfine spherical cobalt powder according to claim 1 is characterized in that: cobalt salt solution can be cobalt chloride solution, cobalt sulfate solution or cobalt nitrate solution.
3. a kind of method for preparing superfine spherical cobalt powder according to claim 1 is characterized in that: the synthetic reaction of cobalt carbonate adopts Distributed Control System (DCS) accurately to control the various technological parameters of synthetic reaction.
4. a kind of method for preparing superfine spherical cobalt powder according to claim 1 is characterized in that: it is raw material that employing contains the cobalt ore material, after leaching purification, and the preparation cobalt salt solution.
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Cited By (1)
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|---|---|---|---|---|
| CN102527116A (en) * | 2012-01-11 | 2012-07-04 | 浙江华友钴业股份有限公司 | Washing method of cobalt hydroxide slurry |
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| CN102381958A (en) * | 2011-09-22 | 2012-03-21 | 浙江华友钴业股份有限公司 | Ammonia circulative preparation method for cobaltous oxalate |
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| CN106392093A (en) * | 2015-07-31 | 2017-02-15 | 荆门市格林美新材料有限公司 | Method for preparing superfine cobalt powder at low cost |
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| CN112974823A (en) * | 2021-02-02 | 2021-06-18 | 安徽寒锐新材料有限公司 | Preparation method and preparation equipment of superfine spherical cobalt powder |
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