CN100484668C - Production method and apparatus for super fine cobalt powder by circulating technology - Google Patents

Abstract

A process for preparing superfine spherical or fibrous Co particles from used battery by the circulation technique includes such steps as extracting twice for purifying, atomizing, hydrolyzing, depositing to obtain the Co compound precursor, and exploding for thermal reduction at multiple temp segments to obtain the superfine Co particles (0.1-0.2 microns) used for power battery and powder metallurgy. Its apparatus is also disclosed.

Description

Circulating technology is produced the manufacture method and the equipment of super-fine cobalt powder

Technical field

The invention provides a kind of manufacture method of cobalt powder, especially a kind of circulating technology is produced the manufacture method of super-fine cobalt powder; The equipment that provides above-mentioned manufacture method used is provided further aim of the present invention.

Background technology

Metal cobalt powder is universally acknowledged strategy metal material, in decades, is the guest of honor of metal futures exchange, London always.Over nearly 5 years, because metal cobalt powder causes global cobalt anxiety in a large amount of uses in fields such as high-energy battery, carbide alloy, military project.We can say that who grasps the resource of cobalt and the manufacturing technology of Related product thereof, who has just grasped the initiative in numerous key industries fields such as chemical energy source, communication, military project.

The super-fine cobalt powder material is one of the advanced person representative of field of new in this century.Super-fine cobalt powder is the critical material of producing as high-energy battery, high strength cemented carbide and military project apparatus, is described as the modern industry monosodium glutamate.

Lithium ion battery contains cobalt and reaches more than 40%, and Ni-MH battery contains cobalt and reaches more than 10%, and therefore, cobalt becomes the critical material that determines new chemical energy costs such as lithium ion battery.

There is data to show that the reserves of tellurian cobalt resource are limited, estimate available 60-70.China is poor cobalt country, and 80% of China's use amount derives from South Africa, in recent years, along with China in a large number from the resource of South Africa import cobalt, Government of South Africa has begun restriction, therefore, as oil, the cobalt resource critical shortage.A year and a half, the cobalt valency madly increases to 350,000 yuan/ton from 150,000 yuan/ton.

Now each country all utilizes the technical research of secondary resource carrying out circulating technology.The economy of China is with the economy as the high speed development of world manufacturing center, China is not only the commentaries on classics exported country of the resource use of world's cobalt, and along with the market development of China domestic communications industry, car industry, the actual market that industry becomes world's cobalt resource uses big country.The China domestic annual cobalt resource amount that consumes is more than ten thousand tons, therefore, the development circulating technology, the secondary resource of exploitation cobalt recycling is to the poor problem that solves Chinese cobalt resource with promote that the modern industry sustainable growth is most important.

China is becoming the manufacture base of world's high-energy battery and carbide alloy, to 2006, China's lithium ion battery, the production of Ni-MH battery will reach more than 60% of the world, comply with the development of China's mobile communication and ev industry, reached 10000 ton or more with the cobalt amount every year, annual growth rate reaches more than 20%, yet for a long time, this super-fine cobalt powder has only a few countries productions such as Belgium, seriously restricting the development of China's high-energy battery and high strength cemented carbide, must develop the low-cost manufacturing technique of developing one's own intellectual property,, realize production domesticization to reduce the cost of super-fine cobalt powder.

At present, the method for manufacturing cobalt powder has four big class methods such as carbonyl process, electrolysis, reducing process, atomization in the prior art.

Carbonyl process is a conventional method, and particle diameter can reach in the 5-10 μ m, and pattern is spherical or chain is spherical.The advantage of this method is that chondritic is stable, and electric conductivity and super-charge super-discharge good electrical property can well be used for the manufacturing of power nickel-hydrogen cell; Shortcoming is a phosphorus content height (0.2-0.3%), and capacity and this production method that can reduce battery are carcinogenic, is non-environment protection method, produces equipment strictness, investment greatly.

Electrolysis, its cobalt powder that generates out is a dendritic powder, is used for powder metallurgy industry.The shortcoming of this method is energy consumption height, cost height, particle diameter thick (generally about 30 μ m), and this cobalt powder can only be used for general sintered metal product, can not be used for battery and high-strength powder metallurgical goods.

Atomization has water atomization and gas atomization, and this law is the same with electrolysis, has energy consumption height, cost height, the thick shortcomings such as (generally about 30 μ m) of particle diameter, and industrial value is little.

Reducing process comprises liquid phase reduction and high temperature solid-state reducing process, among liquid phase reduction was developing, the high temperature reduction method that with the cobalt oxalate is material was the main method that present cobalt powder is produced, and is representative with companies such as Belgian five ore deposit companies, form scale, accounted for more than 90% of cobalt powder output.But it is irregularly shaped that existing this class cobalt powder is shaped as, and the method that does not also have a cover can control the granularity of product and granular size well and can stably produce in batches on technology also exists a lot of problems to need to solve on its use equipment.

Summary of the invention

The objective of the invention is to improve deficiency of the prior art, provide a kind of and adopt that secondary resource, manufacturing process are simple, environmental protection, small investment, be suitable for the manufacture method that the circulating technology of suitability for industrialized production is produced super-fine cobalt powder;

Further aim of the present invention is to provide a kind of equipment that uses said method.

The object of the present invention is achieved like this:

The manufacture method that circulating technology provided by the invention is produced super-fine cobalt powder is, adopt secondary to contain cobalt raw material (also can be described as cobaltiferous waste material), make the super-fine cobalt powder that the Fei Shi particle diameter is 0.1-2.0 micron, oxygen content＜0.6%, carbon content＜0.05%, sulfur content＜0.05% through dissolving, purification, atomizing hydrolytic precipitation and reduction process.

Described course of dissolution is to make cobalt in the described secondary cobaltiferous waste material be dissolved in process in hydrochloric acid or the sulfuric acid, and the part of other material in waste material described in this process also is dissolved in wherein, forms thick cobalt salt solution thus;

Described purification is the mixed liquor that contains P2045-50%+ sulfonated kerosene 95-50% (volume ratio .) by extractant and described thick cobalt salt solution is carried out single extraction and contain raffinate phase that the mixed liquor of P50710-50%+ sulfonated kerosene 95-50% (volume ratio .) obtains single extraction with extractant carrying out reextraction and obtaining refining cobalt chloride solution or the cobalt sulfate solution that cobalt content is higher than described thick cobalt salt solution; Perhaps

Described purification process is a chemical precipitation process, kind and precipitation characteristic selective precipitation agent according to one or more impurity in the described thick cobalt salt solution add in the described thick cobalt salt solution, and adjustment pH value of solution value, make described contamination precipitation and, make refining cobalt chloride or cobalt sulfate solution by filtering; Perhaps

Described purification process also can be an electrochemical deposition process, kind and sedimentation potential characteristic according to one or more impurity in the described thick cobalt salt solution, select suitable current density, with graphite is anode, with the titanium plate is negative electrode, with described thick cobalt salt solution is that electrolyte carries out electrolysis, makes impurity separate out on negative electrode and remove, and makes refining cobalt chloride or cobalt sulfate solution.

Described atomizing hydrolysis is one or more in adding precipitating reagent ammonium oxalate, ammonium carbonate, NaOH and the ammoniacal liquor in described refining cobalt chloride or cobalt sulfate solution, several raw materials feed intake with spray pattern, stir, the pH of control solution obtains cobalt oxalate, or cobalt carbonate, or the compound cobalt salt of cobalt hydroxide or cobalt hydroxide and cobalt oxalate mixing;

Described reduction process is to place reducibility gas to make fibrous or fibre-like or spherical or near-spherical super-fine cobalt powder in 1-8 hour 200-700 ℃ of heating described presoma.

Secondary cobaltiferous waste material of the present invention be wherein cobalt content be 0.1-55% or more than, contain the secondary slugs of one or more impurity among Ni, Fe, Cd, Cu, Pb, Mg, Ca, Cr, Zr, Si, Zn, Li, Mn, Fe, the Al in addition; Concrete, it can be:

1, waste material, the rim charge in waste nickel-hydrogen/nickel-cadmium cell and the production process thereof, containing cobalt in this class waste material is that 0.01-15% does not wait; Other composition is Ni, Fe, Cd, Zn etc., Ni:5-70%, Fe:0.01-10%.Cd：0.01-10％，Zn：0.01-10％

2, waste material, the rim charge in used Li ion cell and the production process thereof, in this class waste material, containing Co is 5-60%, other composition is Ni, Li, graphite, Mn etc., Ni:0.1-50%, Li:1-20%.Graphite: 1-30%, Mn:0.1-50%

3, the waste material of hard alloy scraps product and hard alloy scraps industry generation contains Co:1-30%, Ni:0.1-10% in this class waste material

4, the disabled person makes waste material, rim charge and the useless catalyst etc. in diamond product and the diamond industry, contains Co:1-10% in this class waste material, Ni:1-40%, Mn:1-30%, micro Fe, Al, Cu, Mg, Ca, Cr etc.

5, the catalyst of chemical industry and automobile industry contains Co:1-50% in this class waste material, and all the other are Ni, Al, Si etc.

In described course of dissolution, add hydrochloric acid or sulfuric acid, its concentration percetage by weight is: hydrochloric acid 5-37%, sulfuric acid 10-98%, addition is stoichiometric 100%-200% of described waste material weight, or calculates with all total metal contents in the described waste material, is stoichiometric 1.1-3.0 times, make it dissolving, the cobalt in the waste material forms the cobalt chloride CoCl of solubility ₂Or cobaltous sulfate CoSO ₄The solvable composition of in the waste material other also is dissolved in and forms soluble chloride or sulfate in hydrochloric acid or the sulfuric acid, forms thick cobalt chloride CoCl thus ₂Or cobaltous sulfate CoSO ₄Solution; Or:

In described course of dissolution, with described secondary slugs is anode, with the corrosion resistance conductive material is negative electrode, with sulfuric acid or hydrochloric acid is electrolyte, connect direct current, adjust the voltage and current intensity of electrolysis, make cobalt optimum solvation in described electrolyte according to the kind of cobalt and impurity in the described secondary slugs, the solvable composition of in the waste material other is being dissolved in this electrolyte of part also, forms thick cobalt chloride or cobalt sulfate solution thus.

When described purification was extraction process, it carried out single extraction for the mixed liquor that contains P204 5-50%+ sulfonated kerosene 95-50% (volume ratio .) by extractant to described thick cobalt salt solution and contains raffinate phase that the mixed liquor of P50710-50%+ sulfonated kerosene 95-50% (volume ratio .) obtains single extraction with extractant carrying out reextraction and obtaining refining cobalt chloride solution or the cobalt sulfate solution that cobalt content is higher than described thick cobalt salt solution;

Described atomizing hydrolysis is one or more in adding precipitating reagent ammonium oxalate, ammonium carbonate, NaOH and the ammoniacal liquor in described refining cobalt chloride or cobalt sulfate solution, several raw materials feed intake with spray pattern, stir, the pH of control solution obtains cobalt oxalate, or cobalt carbonate, or cobalt hydroxide or cobalt hydroxide and cobalt oxalate mixing cobalt salt presoma;

Described reduction process is to place reducibility gas to make fibrous or fibre-like or spherical or near-spherical super-fine cobalt powder in 1-8 hour 200-700 ℃ of heating described presoma.

When other metal impurities amount in the nickeliferous thick cobalt salt solution is big, can between described molten cobalt and purification process, be provided with a removal of impurities process, to alleviate the removal of impurities pressure of back purification by liquid extraction operation.

Described removal of impurities process is can be a chemical precipitation process, adds in the described thick cobalt salt solution according to the kind of one or more impurity in the described thick cobalt salt solution and precipitation characteristic selective precipitation agent, and adjusts the pH value of solution value, makes described contamination precipitation and by filtering; Perhaps

Described removal of impurities process also can be an electrochemical deposition process, kind and sedimentation potential characteristic according to one or more impurity in the described thick cobalt salt solution, select suitable current density, with graphite is anode, with the titanium plate is negative electrode, with described thick cobalt salt solution is that electrolyte carries out electrolysis, makes impurity separate out on negative electrode and remove.

In described extraction process,

(1) in described single extraction, extractant is that to contain the thick cobalt salt solution that obtains in the mixed liquor of P204+ sulfonated kerosene and the described course of dissolution be 2-15l/min with the flow of P204, saponification is 75-190mol/min with the flow of alkali, making saponification rate is 60-65%, the flow of thick cobaltous sulfate liquid or cobalt chloride be 2-15l/min, pH be 2-4, temperature be mix under 10-40 ℃ the adjusting, layering, acquisition contains the raffinate phase that the cobalt amount is higher than described thick cobalt salt solution, makes half refining cobalt salt solution;

(2) in described reextraction, it is 0.8-15l/min with the cobalt sulfate solution flow that extractant contains the thick cobalt salt solution that obtains in the mixed liquor of P507+ sulfonated kerosene and the described course of dissolution, P507 reextraction agent flux is 2-20l/min, saponification is 200-1000ml/min with the alkali flow, to make saponification rate be the mixed proportion of 20-50%, in temperature be mix under 10-40 ℃ the adjusting, layering; Stay extraction phase, this extraction phase and concentration be mix under the sulfuric acid of 0.1-0.8mol/L or the adjusting that hydrochloric acid with 1-41/ branch ratio, in temperature is 10-40 ℃, layering, getting strip liquor becomes refining cobalt chloride or cobalt sulfate solution.

Circulating technology of the present invention is produced the manufacture method of super-fine cobalt powder: for not nickeliferous, the thick cobalt salt solution that only contains impurity such as Cu/Fe/Pb/Mg/Ca, the impurity of can be as described above selecting with electrochemistry or chemical precipitation method of removing is about to above-mentioned pass through reextraction that extractant carries out and replace to other electrochemistry or chemical precipitation method process.

Described atomizing hydrolytic process can for:

It is 50-140g/L and to be prepared into concentration be that 100-300g/L, pH are the precipitating reagent of 3.0-5.5 (best be 4.0-4.5) that described refining cobalt chloride or cobalt sulfate solution are adjusted its concentration---ammonium oxalate solution with atomized spray in reactor, mix and stir, temperature is between 45-70 ℃ during reaction, flow is during reaction: the 30-100L/ branch, reaction time is 2 minutes-60 minutes, and the best is 22-25 minutes; Reaction end pH value: 1.0-2.8, the best is 1.7-1.9; Isolate presoma cobalt oxalate crystal then; Or be:

With described refining cobalt chloride or cobalt sulfate solution adjust its concentration be 50-140g/l and be prepared into concentration be the ammonium bicarbonate solution of 50-300g/L with atomized spray in reactor, described refining cobalt chloride or cobalt sulfate solution control addition are 50L～300L/hr, pH value: 7.0-10, best 7.5-9.0, ammonium carbonate is pressed Co ^{+ 2}1.1～2.0 of metering is extraordinarily gone into, and stablizes the pH value by the adding speed of regulating ammonium carbonate, mixes and stirs, average reaction time: 1-10 hours, and reaction temperature: 50-70 ℃,, isolate the spherical or near-spherical cobalt carbonate crystal of presoma then; Or be:

With described refining cobalt chloride or cobalt sulfate solution adjust concentration be 50-140g/l and be prepared into concentration be the NaOH solution of 15-35% (percentage by weight) with atomized spray in reactor, mix and stir, add 10-30% (percentage by weight simultaneously?) NH of concentration ₃Solution or feeding purity are the above NH of 98% (percentage by weight) ₃Gas, its addition is with free Co in the solution ²⁺Concentration is tolerance, control NH ₃Addition makes free Co ²⁺Concentration is 0.5-200 milligrams/l, and the pH of reactant liquor is 7-14, Co ²⁺The charging rate of liquid is 50-300L/hr, and the charging rate of NaOH solution is mated by the pH of control, and reaction temperature is 40-70 ℃, and mixing speed is 70-250 rev/min, and the average grain diameter of crystallization control crystal is the 2-15 micron; Average reaction time is 2-50 hour, makes spherical or near-spherical presoma cobalt hydroxide crystal; Or be:

It is 20-100g/L that described refining cobalt chloride or cobalt sulfate solution are adjusted concentration, and precipitating reagent is that concentration is the ammonium oxalate of 0.1-3.0mol/L and the NH of proportion d=0.5-0.95 ₃H ₂O and weight percent concentration are the mixture of any one or two kinds among two of the NaOH of 10-35%,, mix and stir, Co in reactor with atomized spray ²⁺The charging rate of liquid is 30-300L/hr, and the pH of reactant liquor is 7-12, and optimum value is 7.5-9.5, and reaction temperature is 50-75 ℃, and optimum value is 60-70 ℃, by regulating NH ₃H ₂The addition of O and/or NaOH keeps pH stable, keeps temperature, charging rate to stablize in the reaction, and charging rate is equally by keeping constant with the constant displacement pump feed way; Average reaction time is 5-1200 minute, and optimum value is 20-40 minute, generates the cobalt oxalate of fibrous or fibre-like and the compound cobalt salt that cobalt hydroxide mixes by controlling each reaction condition.In order to improve the dispersive property of complicated cobalt salt, can add the PVP high molecular surfactant of 0.01-0.5% (percentage by weight)..

Concrete, the method for hydrolysis of preparation cobalt oxalate can be:

A, preparation ammonium oxalate solution:

Oxalic acid is dissolved with warm water (water temperature is at 45-65 ℃), and it is filtered, remove the solid impurity in the solution, feed liquefied ammonia again in oxalic acid solution, being mixed with pH is 4.1-4.5, and concentration is the ammonium oxalate solution of 130-150g/L.

B, the crystallization of preparation cobalt/cobalt oxide presoma cobalt oxalate:

With refining cobalt chloride or cobalt sulfate solution adjust its concentration be 50-140g/L and be prepared into concentration be the ammonium oxalate solution of 130-150g/L with atomized spray in reactor, mix and stir, temperature is between 50-52 ℃ during reaction, flow is during reaction: the 35-45L/ branch, reaction time is 5 minutes-7 minutes, reaction end pH value: 1.6-1.8; Isolate crystal then;

The method for hydrolysis of preparation cobalt carbonate can be:

A, preparation sal volatile:

Carbonic hydroammonium is dissolved with warm water (45-65 ℃ of water temperatures), and its solution is filtered, remove solid impurity in the solution, the concentration that is mixed with the carbon ammonium is 50-300g/L, is preferably 200-230g/L

B, will making with extra care cobalt chloride or cobalt sulfate solution, to adjust its concentration be 50-140g/l, and in reactor, Co hydraulic control system addition is 50L～300L/hr to the ammonium bicarbonate solution that is preferably 100g/l and concentration and is 100-300g/L with atomized spray, and ammonium carbonate is pressed Co ^{+ 2}1.1～2.0 extraordinarily going into of metering, pH value: 7.5-8.5 stablizes Co hydraulic control system addition, adjusts the addition of ammonium carbonate according to the pH value, makes the pH value stabilization; Mix and stir mixing speed: 85-150 commentaries on classics/min, average reaction time: 1-10 hours, reaction temperature: 50-60 ℃;

By above-mentioned atomizing hydrolysis, can make cobalt oxalate or cobalt carbonate crystal.If wherein cobalt liquid is cobalt chloride solution, then can generate fibrous or needle-like or fibre-like or class needle-like cobalt oxalate or cobalt carbonate crystal, if cobalt liquid is cobalt sulfate solution, then can generate spherical or near-spherical cobalt carbonate or cobalt oxalate crystal, hydrolysis crystallization by above-mentioned condition, the crystal grain of the crystal that produces all can be satisfactory, and like this, the index of the granularity of the cobalt powder of making in the operation of back also just can meet the demands.

The concrete grammar of preparation presoma cobalt hydroxide crystal can be:

With described refining cobalt chloride or cobalt sulfate solution adjust concentration be 120g/l and be prepared into concentration be 25% NaOH solution with atomized spray in reactor, mix and stir, feed purity simultaneously and be the NH more than 98% ₃Gas is regulated NH ₃Addition makes free Co ²⁺Concentration is 10-15 milligrams/l, and the pH of reactant liquor is 9.8-10.5, Co ²⁺The charging rate of liquid is 160L/hr, and the charging rate of NaOH solution is mated by the pH of control, realizes feeding in raw material constant Co with constant displacement pump ²⁺The charging rate of liquid, it is 9.8-10.5 that the charging rate of adjusting NaOH solution makes pH; Reaction temperature is 60 ℃, and mixing speed is 130-140 rev/mins, and the average grain diameter of crystallization control crystal is the 5-8 micron; Average reaction time is 5-8 hour, makes presoma cobalt hydroxide crystal;

The concrete grammar of the mixed crystal of preparation presoma cobalt hydroxide and cobalt oxalate can be:

To make with extra care cobalt chloride or cobalt sulfate solution adjustment concentration is the best 30-50g/L of being of 20-100g/L, and precipitating reagent is that concentration is the ammonium oxalate of 0.1-3.0mol/L and the NH of proportion d=0.5-0.95 ₃H ₂O and weight percent concentration are the mixture of any one or two kinds among two of the NaOH of 10-35%,, mix and stir, Co in reactor with atomized spray ²⁺The charging rate of liquid is 30-200L/hr, and the pH of reactant liquor is 7-12, and optimum value is 8-9, and reaction temperature is 50-75 ℃, and optimum value is 60-70 ℃, passes through NH ₃H ₂The addition of O and/or NaOH keeps pH stable simultaneously, keeps temperature, charging rate to stablize in the reaction, and charging rate is equally by keeping constant with the constant displacement pump feed way; Average reaction time is 5-60 minute, and optimum value is 20-40 minute, generates the cobalt oxalate of fibrous or fibre-like and the complicated cobalt salt that cobalt hydroxide mixes by each reaction condition control.

The preferred plan of described reduction process is the explosion thermal reduction, its minute prereduction, reduction and cooling three phases:

(1) prereduction:

With described presoma at reducing gas protective gas N ₂Or CO ₂Protective atmosphere in, temperature is 200-500 ℃, reduced 1-5 hour, make the crystal dehydration and carry out prereduction at this reduction phase, the mist of cobalt oxalate or cobalt carbonate crystal cracking release of carbon dioxide and carbon monoxide has reducing property, and the carbon dioxide in cobalt oxalate or the cobalt carbonate crystal is overflowed, it can make the crystal heap become loose, promptly carries out so-called explosion;

(2) reduction:

Crystal after the prereduction was reduced 1-10 hour at 400-650 ℃, reduction process is carried out in hydrogen and nitrogen formation reducing atmosphere, the volume ratio of hydrogen and nitrogen is 3: 1, and the feeding amount of reducing gas is decided by the amount of presoma, and its proportionate relationship satisfies reduction reaction with wherein hydrogen and is as the criterion;

(3) cooling

At N ₂Or CO ₂Protective atmosphere in crystal cooling, inerting to room temperature, promptly can be made into fibrous or the spherical or near-spherical super-fine cobalt powder of particle diameter at 0.1～2.0 μ m.

Described reduction phase can be divided into a plurality of temperature rise periods again: preceding low-temperature zone, high temperature section, preceding low-temperature zone is hanged down 30-50 ℃ than the temperature of high temperature section.Described cooling stage can be divided into several temperature drop ladders, and the temperature difference of each ladder is at 40-80 ℃.

It can be as follows that concrete explosion thermal reduction prepares super-fine cobalt powder:

(1) prereduction:

With the cobalt oxalate made or cobalt carbonate crystal at reducing gas N ₂Or CO ₂Protective atmosphere in heat, temperature is 200-400 ℃ of reduction 1-3 hour, makes crystal dehydration and carries out prereduction at this reduction phase, and the carbon dioxide in cobalt oxalate or the cobalt carbonate crystal is overflowed, it can make the crystal heap become loose, promptly carries out so-called explosion;

(2) reduction:

Crystal after the prereduction was reduced 1-6 hour at 400-650 ℃; reduction process is carried out in hydrogen and nitrogen formation reducing atmosphere; the volume ratio of hydrogen and nitrogen is 3: 1; in the application of reality, can easily liquefied ammonia be decomposed and obtain reducing gas: 2NH3 → 3H2+N2; like this, both obtained reducing required hydrogen easily, also added nitrogen with protective effect; hydrogen is convenient, safe and inexpensive compared with using, and has industrial applicibility preferably.The feeding amount of reducing gas is decided by the amount of presoma, and its proportionate relationship satisfies reduction reaction with wherein hydrogen and is advisable.

To reducing through the crystal after what is called " explosion " process in prereduction stage, contact with reducing gas, loose powdered can contact more fully with reducing gas, and therefore, the segmentation heating helps powder in this super-fine cobalt powder of preparation loose, pine is than low, and be beneficial to the carrying out of reduction reaction, can also shorten the reaction time, enhance productivity, and make device structure become compact, reduce floor space.

Reduction phase can be divided into a plurality of temperature rise periods again: preceding low-temperature zone, high temperature section, and preceding low-temperature zone can be low 30-50 ℃ than the temperature of high temperature section, for example, preceding low-temperature zone is 460 ℃, is incubated 40 minutes therein, is warmed up to 500 ℃ of high temperature section again, being incubated 40 minutes, can be homogeneous heating like this;

(3) cooling

At N ₂Or CO ₂Protective atmosphere in crystal cooling, inerting to room temperature, promptly can be made into the fibrous or spherical super-fine cobalt powder of particle diameter at 0.1～2 μ m.

Back cooling stage can also be divided into several temperature drop ladders, and the temperature difference of each ladder can be at 100-150 ℃, as cools to 460 ℃ of insulations 20 minutes, continues to cool to 300 ℃ of insulations 20 minutes, naturally cools to room temperature at last.Multistage is lowered the temperature and can be reduced the cooling velocity of crystal, avoids the performance of crystal caking and reduction crystal.

In above-mentioned reduction process, if heating-up temperature is too low, reduce not thorough, the oxygen content height in the crystal, if temperature is too high, then particle diameter is grown up, proportion is excessive.

Be preferably carbon dioxide at protective gas pre-cooled and that reduction phase uses, because it is heavier than air, the protection effect is better than nitrogen.

The manufacturing equipment that circulating technology provided by the invention is produced super-fine cobalt powder comprises dissolution equipment, equipment for purifying, atomizing hydrolysis reactor and reduction apparatus, described dissolution equipment is to have the reactor of heater or have heater and the reactor of electrolysis unit, and described purifying plant is extraction box or has heater and the reactor of electrolysis unit, described reduction apparatus are hydraulic pressure and mechanically operated multiple stage boat.

Described extraction box is the adverse current box-type extractor preferably.

Described multisection type pushes away boat, comprise three passage housings, be connected to form a long and narrow passage by transfer pipeline therebetween, be provided with import and outlet at the two ends of this passage, described three housings form three zones in proper order from the outlet that enters the mouth: be prereduction zone, reduced zone and cooled region, describedly push away each zone of boat separates or be provided with automatic control by the stainless steel curtain fire door or flashboard, flow mutually with the gas in each district of restriction; This curtain is located in the connecting line between each zone and in the outlet, the upper end and the tube wall of described curtain are articulated and connected, its lower end is a free end, each zone links together, forming one in pushing away boat can be by the tubular conduit of each chamber, in this tubular conduit, be provided with several material boats each other in contact, be provided with the material boat propulsion plant that the material boat can be pushed in the described tubular conduit in the import department that pushes away boat, in described heater and temperature detection and the adjusting device of in each sintering chamber, being provided with, provide required temperature in order to give each chamber; In described each chamber, also be provided with one or more air inlets and exhaust outlet; Be provided with cooling device in the described cooling chamber.

Be provided with air inlet and exhaust outlet at the top of each regional casing, in described prereduction zone and reduced zone, described air inlet and exhaust outlet be located at these regional two ends and air inlet/outlet opposite with the direct of travel that pushes away boat; Be separated into the plurality of segments space by dividing plate again in each zone, this dividing plate thereunder is provided with access opening makes each segment space connection make the described boat that pushes away pass through; In prereduction zone and reduced zone, be respectively equipped with several segment space, heater is set to form different temperature respectively in different segment space in each segment space, also be provided with several segment space at cooled region, in each segment space, be respectively equipped with cooler; Casing top, middle part in the several segment space in the front of cooled region is provided with air inlet, and in the end casing top, a segment space middle part is provided with exhaust outlet.

Described atomizing hydrolysis reactor comprises a retort, comprise heater, agitating device and feed arrangement on it, described feed arrangement comprises some charging jet pipes, the nozzle of some of them charging jet pipe is located at the top of retort tank body, and the nozzle of other charging jet pipes is located at the middle part or the bottom of retort tank body;

Circulating technology provided by the invention produces the technology of the manufacture method of super-fine cobalt powder by effective stripping cobalt, separates cobalt with impurity purifying technique such as chemical precipitation, electrochemistry precipitation and reextraction technology and can from the various waste materials that contain cobalt, efficiently make super-fine cobalt powder by atomize hydrolysis process and specific process conditions and explosion reducing process thereof.

Core of the present invention is removal of impurities purification technique, the synthetic cobalt compound presoma of atomizing hydrolysis deposition of secondary cobaltiferous waste material, carries out the explosion thermal reduction then and generate super-fine cobalt powder under the multistage temperature.

The employing of atomizing hydrolysis deposition can essence be eliminated the colloidal substance deposition, keeps stable crystalline growth environment, thereby, can synthesize crystal with given shape and particle diameter.Mode and stable pH technology implement the atomize hydrolysis deposition of the present invention by pressure atomization, synthetic oxide precursor is under given shape, evenly distribute, under the multistage temperature, carry out the explosion thermal reduction thus and generate the given shape super-fine cobalt powder, to satisfy battery and the different demands of powder metallurgy different industries product.

This method can prepare the product of different-grain diameter and shape.

Molten cobalt that the present invention is special and purifying technique combination make this technology can be suitable for multiple composition, the different various recyclings that contain the cobalt secondary slugs of content.

Unique technique such as employing atomized water solution provided by the invention and controlled atmospher decomposition method are produced the super-fine cobalt powder material, it is a kind of eco-friendly method, can produce spherical and two kinds of super-fine cobalt powders of needle-like, have that cost is low, particle diameter is thin, pine is than rational characteristics, can be used for the manufacturing of electrokinetic cell and high-performance powder metallurgy goods.When control generate spherical/during near-spherical, particle diameter: 0.1～1.5 μ m, pine ratio: 0.3～1.0g/cm3 is evenly distributed, good product consistency, can be used for electrokinetic cell, obviously improves electric conductivity, the high rate during charging-discharging of battery, prolongs battery cycle life; When being controlled to needle-like, the horizontal diameter of axle 0.1～0.5 μ m, vertically axial length 0.5～10 μ m as the skeleton of superhard materials such as powder metallurgy smear metal cutter, carbide alloy, improves the hardness and wear resistance energy of these sintered metal products, thereby reach the existing cobalt powder of comprehensive replacement, have, the phosphorus content of the cobalt powder of method preparation of the present invention is low, good product quality again, cost is low, has very excellent cost performance.This method can be controlled the granularity of product and granular size well and can stably produce ultra-fine spherical and fibrous cobalt powder in batches.Making apparatus provided by the invention can provide reliable assurance for said method, and this device structure is simple simultaneously, low cost of manufacture.

Description of drawings

The invention will be further described below in conjunction with accompanying drawing.

Fig. 1 is the process chart that is used to prepare the super-fine cobalt powder of making electrokinetic cell of the present invention;

Fig. 2 is for obtaining thick cobalt salt solution with waste hand alloy material by electrodissolution and preparing the process chart of super-fine cobalt powder;

Fig. 3 is the structural representation of explosion reduction furnace.

The specific embodiment

Embodiment 1:

The circulating technology of present embodiment is produced the process chart of ultra-fine spherical manufacture method and is seen Fig. 1.Employed in the present embodiment waste material (the thick cobalt material of secondary) is:

1, waste material, the rim charge in waste nickel-hydrogen/nickel-cadmium cell and the production process thereof, containing cobalt in this class waste material is that 1.0-15% does not wait; Other composition is Ni, Fe, Cd, Zn etc., Ni:10-60%, Fe:1-10%.Cd：0.1-10％，Zn：0.1-10％

2, waste material, the rim charge in used Li ion cell and the production process thereof, in this class waste material, containing Co is 5-50%, other composition is Ni, Li, graphite, Mn etc., Ni:1-20%, Li:1-20%.Graphite: 1-30%, Mn:1-30%

Step 1: dissolving

In described secondary cobaltiferous waste material or cobalt slag, add sulfuric acid or hydrochloric acid, its concentration is: sulfuric acid 10-98% or hydrochloric acid 5-37% (percetage by weight), sulfuric acid or hydrochloric acid addition are calculated with all total metal contents in the waste material, chemical equivalent 100%-200%, make the waste material dissolving, the cobalt in the waste material forms the cobaltous sulfate CoSO of solubility ₄Other compositions in the waste material also are dissolved in and form sulfate in the sulfuric acid, form thick cobaltous sulfate CoSO thus ₄Solution or thick cobalt chloride CoCl ₂Solution;

Step 2: purify

Thick cobaltous sulfate or thick cobalt chloride solution that step 1 is obtained carry out the pre-removal of impurities of chemistry before entering extraction: with CoSO ₄The solution removal of impurities is an example:

1, Ca/Mg removes: with CoSO ₄Solution carries out Ca/Mg and removes, to reach [the Ca in the solution ²⁺]＜1g/l, [Mg ²⁺]＜2g/l.

Operate as follows:

The preparation Fluorinse: the NaF solution of preparation 20%, at 1M ³Container in, add pure water 800L, add NaF200Kg, stirring and dissolving;

Transfer pH: will wait that the CoSO4 solution that removes Ca/Mg pumps into the groove except that Ca/Mg, and be added to 70% of volume, and transfer pH5---5.5;

Heat up: under keeping warm mode, be warming up to 90-100 ℃;

The heavy Ca/Mg of reaction: the content of pressing earlier Ca/Mg in the CoSO4 solution, calculate the addition of good theoretical NaF solution, actual excessive 100%--150%, under stirring, slowly add in 60 minutes and prepare NaF solution, keep 90 ℃-100 ℃, add material after, stirred sample analysis Ca/Mg 30-60 minutes.

Filter: filter while hot, filtrate deposits the medial launder cooling in, looks the filtration situation, takes one or many to filter.

2, purify except that Fe

CoSO to above-mentioned iron content ₄Solution purify except that Fe, to reach the requirement of extraction: [Fe3+]＜400mg/l

Operate as follows:

Get the raw materials ready: pending CoSO ₄Solution must be filtered clear solution, removes the Fe groove with the pump suction and is added to 70% of reactive tank.

Prepare CoCO ₃Dry powder

Add oxidant: add oxidant H ₂O ₂, extraordinarily go into 1 hour reaction time by 1.2-2 of the theoretical consumption of deironing.

Heat up, transfer pH: be warming up to 70-80 ℃, add ready CoCO ₃Dry powder was sprinkled into dry powder several times in 4 hours, each 3-5Kg is up to PH=3.8-4.5;

Stirring reaction: stirring reaction 1-2 hours, sample analysis filters while hot, and filtrate deposits the medial launder cooling in, looks the filtration situation, takes one or many to filter.

3, copper removal, lead, cadmium

To COSO ₄Cupric, lead, cadmium, the solution that exceeds standard purify copper removal, lead, cadmium, require to reach extraction: [Cu]＜10g/l, [Pb]＜10mg/l, [Cd]＜2g/l;

The formulating vulcanization sodium solution: the sodium sulfide solution of preparation 100-120g/l, thick cobaltous sulfate or nickel sulfate solution are heated to 65-75 ℃, use Na ₂CO ₃Solution transfers to 2-2.2 with pH, slowly adds Na under stirring ₂S solution, addition are stoichiometric 1.5 times of cupric in the solution, lead, cadmium total amount, and stirring reaction 1-2hr, reaction end pH are 2.2, filter.

Certainly, at [Ca ²⁺]＜1g/l, [Mg ²⁺]＜2g/l, [Cu]＜10g/l, [Pb]＜10mg/l, [Cd]＜2g/l[Fe3+]＜during 400mg/l, can save the pre-removal of impurities process of above chemistry.

4, reextraction obtains pure cobalt sulfate solution; In extraction process, can remove micro Fe, Cd, Zn, Li, Mn in the solution by reextraction.And realize separating of Ni and Co.

Concrete is:

(1) add the sulfuric acid acid adjustment in thick cobalt sulfate solution, the pH value of regulator solution is that 2-4 is standby;

(2) preparation extractant (liquid), wash acid and strippant (liquid)

Single extraction agent (liquid) is for containing the mixed liquor of P20410% and sulfonated kerosene 90% (volume ratio); P204 is [2 1 (2-ethylhexyl) phosphoric acid] (being called D2EHPA abroad);

Reextraction agent (liquid) is for containing the mixed liquor of P50720%+ sulfonated kerosene 80% (volume ratio); P507[2-ethylhexyl phosphoric acid list (2-ethylhexyl) ester] (being called PC88A abroad);

Strippant (liquid) is the pure water solution of sulfur acid or hydrochloric acid 1.0-1.5mol/L, is the pure water solution of sulfur acid 1.3mol/L in the present embodiment;

Washing the solution of acid 1 for sulfur acid or hydrochloric acid 0.30-1.0mol/L, is the pure water solution of sulfur acid 0.45mol/L in the present embodiment;

Wash the solution of acid 2 for sulfur acid or hydrochloric acid 0.10-0.8mol/L; It in the present embodiment pure water solution of sulfur acid 0.2mol/L;

Saponification alkali is the sodium hydroxide solution of 2-10mol/L; It in the present embodiment sodium hydroxide solution of 5.5mol/L;

(3) extraction: single extraction and reextraction are two continuous operating process, and each extraction process carries out in several extraction boxes that are interconnected.

Single extraction (fractional extraction):

A, abstraction impurity removal:

To in (1), feed in the extractor with alkali through the thick cobaltous sulfate of acid adjustment, the single extraction agent and the saponification of (2) middle preparation, wherein, the flow of single extraction agent P204 is 2-151/min, saponification is that to make saponification rate be 60-65% to 50-190mol/min with the flow of alkali, the flow of thick cobaltous sulfate liquid or cobalt chloride is 2-151/min, fully stir, static layering, carry out single extraction at normal temperature, the raffinate phase of drawing is standby as half POV cobalt or cobalt chloride solution, impurity enters load organic phases, and enters the next stage washing section.

B, wash cobalt:

Load organic phases is fed washing section, with washing in the flow adding extractor of acid 1 with 50-150ml/min of preparation in (2), fully stir, static layering, the wash load organic facies, from extractant, further extract remaining cobalt, with raffinate phase in the A step promptly half POV cobalt or cobalt chloride solution merge standbyly, this process can further reclaim the remaining cobalt ions of extraction phase;

C, back extraction impurity:

Load organic phases enters stripping section, feeds strippant of preparation in (2) simultaneously, and the flow of anti-stripping agent is 100-500ml/min, fully stirs, and the extractant of regeneration is drawn in static phase-splitting, recycles, and impure strip liquor enters sewage disposal system;

In this single extraction, can remove thick CoSO ₄Or CoCl ₂In most of impurity element: Fe, Cu, Zn, Mn, Cr, Cd, Ca, etc.In the present embodiment, can remove thick CoSO ₄In most of impurity element: Fe, Cd, Zn, Ca, Li, Mn.

Use the adverse current box-type extractor in extraction, thick cobalt sulfate solution flow is decided on extractor production capacity and impurity content, above a kind of technological parameter that just proposes with regard to a kind of concrete technology.

Reextraction:

A, extraction cobalt:

The reextraction agent of preparation and saponification feed in the extractor with alkali in the half POV cobalt liquor that will obtain in single extraction, (2), wherein the cobalt sulfate solution flow is 0.8-15l/min, the reextraction agent flux is 2-20l/min, saponification is 200-1000ml/min with the alkali flow, making saponification rate is 20-40%, fully stirs static layering, carry out reextraction at normal temperature, cobalt enters load organic phases; Draw raffinate, according to nickel content otherwise processed.

B, wash impurity:

The load organic phases of reextraction and the acid 2 of washing of (2) middle preparation are fed washing sections, and washing sour 2 flows is 0.1-3.01/min, fully stirring, static phase-splitting, load organic phases enters the next stage stripping section, and washing merges with the raffinate in the A step, also has some nickel elements in raffinate;

C, back extraction cobalt:

Load organic phases enters the next stage stripping section, feeds strippant of preparation in (2) simultaneously, and the strippant flow is 100-200mgl/min, fully stirs, and the extractant of regeneration is drawn in static phase-splitting, recycles, and strip liquor is refining cobalt liquid.

In this reextraction, can remove sodium in oneself deimpurity half refining cobalt chloride or the cobalt sulfate solution, nickel, magnesium etc.

In the present embodiment, sodium and a spot of nickel that can remove in the reextraction in the half POV cobalt liquor is made the POV cobalt liquor;

Also there are some nickel elements in described raffinate of in described reextraction, drawing in A and the B step and the washing lotion, it handled:

Described solution containing nickel is handled respectively according to nickel content, to reclaim nickel, contained the low sewerage that can enter of nickel concentration and reclaim nickel, contain the nickel concentration height, available chemical precipitation method or extraction reclaim nickel.

Same, in this reextraction, using the adverse current box-type extractor, present embodiment uses box-type extractor, and wherein the flow of cobalt sulfate solution is decided on extractor production capacity and impurity content.

Saponification alkali is the acid (H for producing in the balance extraction process ⁺) and the preneutralization effect carried out;

In described reextraction process, prepare extractant according to the requirement of operational procedure, thick cobalt liquid (feed liquid) is washed cobalt liquid (washing acid), strip liquor (sour regurgitation), saponification alkali, by the flow of setting carry out abstraction impurity removal, wash cobalt, back extraction impurity three section operation.Abstraction impurity removal is the extraction of the impurity in the thick cobalt liquid to be entered the extractant cobalt then stay in the feed liquid (raffinate), thereby realizes cobalt and separate impurities; Extractant after collection is assorted is washed acid elution washing the cobalt section, make the cobalt wash-out that part is carried secretly in the extractant enter raffinate, and impurity is not by wash-out, to improve the rate of recovery of Co; Stripping section then is that the impurity that extractant extracts is got off by strip liquor (sour regurgitation) back extraction, enters in the strip liquor, effluxes and enters sewage disposal system, and extractant obtains regeneration, enters next extracting operation circulation, and process is carried out continuously.

Step 3: oxide precursor-cobalt carbonate crystal is produced in the atomizing hydrolysis

A, the crystallization of preparation cobalt/cobalt oxide presoma cobalt carbonate:

Carbonic hydroammonium is dissolved with warm water (water temperature=45-50 ℃), and its solution is filtered, remove solid impurity in the solution, the concentration that is mixed with the carbon ammonium is the solution of 225g/L ± 5.

With the POV cobalt liquor adjust its concentration be 85g/L and concentration be the ammonium bicarbonate solution of 225g/L with atomized spray in reactor, cobalt sulfate solution control addition is 200L～250L/hr, ammonium carbonate is pressed Co ^{+ 2}1.5～2.0 of metering is extraordinarily gone into, and mix and stir, mixing speed: 120r/min, reaction temperature: 55-60 ℃, pH value in reaction: 7.5 ± 0.1, in the course of reaction, keep the stable of pH, when D50=8-15um, isolate crystal; Reactive mode: liquidate, promptly the upper and lower in reactor is set up two feed nozzles separately, above a nozzle spout downward, below a nozzle spout upwards spray material.Preferably the cobalt nozzle for liquid is last, and the carbonic hydroammonium nozzle is following.

By above-mentioned atomizing hydrolysis, can make spherical cobalt carbonate crystal.

Described atomizing hydrolysis reactor comprises a retort, comprise heater, agitating device and feed arrangement on it, described feed arrangement comprises some charging jet pipes, preferably the nozzle of some of them charging jet pipe is located at the top of retort tank body, and the nozzle of other charging jet pipes is located at the bottom of retort tank body;

In described atomizing hydrolytic process, feeding intake of described reactant is the mode of liquidating, and promptly the upper and lower in reactor is set up separately and all is provided with feed nozzle, above a nozzle spout downward, below a nozzle spout upwards spray material.Described cobalt liquid is from spraying downwards at last nozzle, described precipitating reagent under upwards ejection of nozzle.

In reactor, very pure described cobalt liquid and other reactant add the reactor hydrolysis that atomizes by the recoil mode and form crystallization---cobalt/cobalt oxide presoma.Then, this presoma is carried out drying for standby.

Step 4: the explosion thermal reduction prepares spherical super-fine cobalt powder

Divide prereduction, reduction and cooling three phases:

(1) prereduction:

The cobalt carbonate crystal that step 3 is made drops in the inlet of hydraulic pressure multiple stage boat reduction furnace 1 (as shown in Figure 4), reduction furnace 1 comprises three passage housings, be connected to form a long and narrow passage by transfer pipeline therebetween, be provided with import and outlet at the two ends of this passage, in this passage, be provided with some material box that are used to hold presoma---push away boat.Described three housings form three zones in proper order from the outlet that enters the mouth: be prereduction zone 11, reduced zone 12 and cooled region 13, each zone separates by stainless steel curtain 2, this curtain is located in the connecting line between each zone and in the outlet, the upper end and the tube wall of described curtain 2 are articulated and connected, its lower end is a free end, push away boat under the electric pushrod of being located at channel entrance end outside promotes successively in the admission passage,, make the boat that pushes away of front be pushed and move ahead along with the back pushes away pushing of boat.Be provided with air inlet and exhaust outlet at the top of each regional casing, in described prereduction zone and reduced zone, described air inlet and exhaust outlet be located at these regional two ends and air inlet/outlet opposite with the direct of travel that pushes away boat; Be separated into the plurality of segments space by dividing plate again in each zone, this dividing plate thereunder is provided with access opening makes each segment space connection make the described boat that pushes away pass through; In prereduction zone 11 and reduced zone 12, be respectively equipped with 4 and 6 segment space, heater is set to form different temperature respectively in different segment space in each segment space, be provided with 3 segment space at cooled region liquid, in each segment space, be respectively equipped with cooler; Casing top, middle part in the several segment space in the front of cooled region is provided with air inlet, and in the end a segment space middle part can be provided with exhaust outlet in the top.

In prereduction zone 11, feed protective gas CO ₂Heating cobalt carbonate crystal in this protective atmosphere, heating-up temperature is 200-400 ℃, heat time heating time 30min, and then be incubated 1 hour, and make the crystal dehydration and carry out prereduction at this reduction phase, the carbon dioxide in the cobalt carbonate crystal is overflowed, it can make the crystal heap become loose, promptly carries out so-called explosion;

(2) reduction:

Crystal after the prereduction continues to move ahead in pushing away boat, enter reduced zone 12, in 4 compartments, pass through successively, first space is a low-temperature space, 3 spaces of back are the high-temperature region, and it is divided into preceding low-temperature space, high-temperature region and back low-temperature space, 300-400 ℃ of low-temperature space temperature again, the high-temperature region temperature is 400-550 ℃, and the temperature of preceding low-temperature zone and back low-temperature zone is hanged down 30-50 ℃ than the temperature of high temperature section.The time that stops at each space material is 10-60min.Such mode of heating can make crystal grain continue to be warmed up to high temperature section again after being heated evenly and reduce.Reduction process is carried out in hydrogen and nitrogen formation reducing atmosphere, and the volume ratio of hydrogen and nitrogen is 3: 1, liquefied ammonia is decomposed obtain reducing gas: 2NH ₃→ 3H ₂+ N ₂

(3) cooling

Material after the reduction enters cooled region, at CO ₂Protective atmosphere in crystal cooling, inerting to room temperature, promptly can be made into the spherical super-fine cobalt powder of particle diameter at 0.1～2 μ m.Cooled region is divided into 3 temperature drop ladder compartments, and the temperature difference of each ladder can be at 40-80 ℃, as cools to 460 ℃ of insulations 40 minutes, continues to cool to 400 ℃ of insulations 40 minutes, naturally cools to room temperature at last.Multistage is lowered the temperature and can be reduced the cooling velocity of crystal, avoids the performance of crystal caking and reduction crystal.

The manufacturing equipment that circulating technology is produced super-fine cobalt powder comprises dissolution equipment, equipment for purifying, atomizing hydrolysis reactor and reduction apparatus, described dissolution equipment is to have the reactor of heater or have heater and the reactor of electrolysis unit, and described purifying plant is extraction box or has heater and the reactor of electrolysis unit, described reduction apparatus are aforesaid hydraulic pressure and mechanically operated multiple stage boat.

Described extraction box is the adverse current box-type extractor.

Embodiment 2:

Present embodiment provides circulating technology to produce ultra-fine spherical manufacture method.Employed in the present embodiment waste material is:

1, the useless catalyst in the diamond industry contains Co:1-10% in this class waste material, Ni:10-40%, Mn:10-50%, micro Fe, Al etc.

Step 1: dissolving

In described secondary cobaltiferous waste material or cobalt slag, add hydrochloric acid, its concentration is 5-30%, (percetage by weight), it is different and different that addition is looked raw material, be 100%-150% (percentage by weight) (coming the chemistry equivalent by all total metal contents) for waste material, make it dissolving, the cobalt in the waste material forms the cobalt chloride CoCl of solubility ₂Other compositions in the waste material also are dissolved in and form soluble chloride in the hydrochloric acid, form thick cobalt chloride CoCl thus ₂Solution;

Because raw materials used impurity is more in the present embodiment, and outstanding be that the content of Mn is higher.The process of a chemical subtraction was set before extraction for this reason.

Step 2: chemical purification

Adopt the method for ammonium sulfate partly precipitated nickel and ammonium sulfate, carbon ammonium, the heavy manganese two-step precipitation of ammoniacal liquor mixed solution.

The concentration that GOLD FROM PLATING SOLUTION belongs to ion is: Ni is 50g/L, and Co is 4g/L, and Mn is 20g/L.This solution is added ammonium sulfate (percentage by weight 30%-70%), and the addition of ammonium sulfate is 1.1 times of amount of substance of nickel in the solution, and stirring reaction 20 minutes filters, and analyzes filtrate component; The mixed solution that adds ammonium sulfate (percentage by weight 30%-70%), carbon ammonium (percentage by weight 30%-70%) and ammoniacal liquor (10-30%) in the filtrate, stirring reaction 30 minutes filters, and analyzes metallic nickel, cobalt and manganese concentration in the filtrate.Total ammonia concentration is controlled at about 4mol/L in the reaction solution, and reaction end pH value is controlled at about 10 by the proportioning of regulating ammonium sulfate and ammoniacal liquor.The consumption of carbon ammonium is 0.8 times of amount of substance of manganese.

Analysis result table 1

From the analysis result of table 1, after the first step added ammonium sulfate in solution, most nickel got off so that the form of ammonium nickel sulfate double salt is precipitated from solution, tentatively realizes separating of nickel cobalt and manganese, wherein had a spot of cobalt and manganese to get off so that the form of absorption is precipitated.Second step added the mixed solution of carbon ammonium, ammoniacal liquor and ammonium sulfate, and a large amount of manganese is precipitated to get off, and cobalt is then stayed in the solution, thereby realized separating of cobalt and manganese.

The rate of recovery of nickel, cobalt and the rate of deposition of manganese are:

The rate of recovery η of nickel _Ni=99.13%

The rate of recovery η of cobalt _Co=94.83%

The rate of deposition D=87% of manganese

For the purification process that directly substitutes extraction, basic identical with said process with chemical precipitation method.

About the described purification process of electrochemical deposition process is kind and sedimentation potential characteristic according to one or more impurity in the described thick cobalt salt solution, select suitable current density, with graphite is anode, with the titanium plate is negative electrode, with described thick cobalt salt solution is that electrolyte carries out electrolysis, impurity is separated out on negative electrode and remove, make refining cobalt chloride or cobalt sulfate solution; This technology can determine that according to the kind and the content of impurities relevant parameter carries out with method of the prior art, and this is well known to those skilled in the art, so, here just repeat no more.

Step 2: extraction

Step 2 is carried out reextraction through the thick cobalt chloride solution after the chemical purification, obtain pure cobalt chloride solution; In extraction process, can remove Ni, Mn, Determination of Multi-Impurities such as Fe, Al in the solution by reextraction.

Concrete is:

(1) add the hydrochloric acid acid adjustment in thick cobalt chloride solution, the pH value of regulator solution is that 2-4 is standby;

(2) preparation extractant (liquid) and strippant (liquid):

Single extraction agent (liquid) is for containing the mixed liquor of P2048% and sulfonated kerosene 92% (volume ratio .);

Reextraction agent (liquid) is for containing the mixed liquor of P50725%+ sulfonated kerosene 75% (volume ratio);

Strippant (liquid) is for containing the pure water solution of HCl1.2-1.5mol/L;

Wash acid 1 for containing the solution of HCl0.35-1.0mol/L;

Wash acid 2 and be the solution of sulfur acid 0.15-0.8mol/L;

Saponification alkali is the sodium hydroxide solution of 3-8.5mol/L;

(3) extraction:

Two extraction section device therefors in the present embodiment are identical with embodiment 1, and process liquid is basic identical.

Step 3: oxide precursor-cobalt oxalate cobalt crystal is produced in the atomizing hydrolysis

A, preparation ammonium oxalate solution:

Ammonium oxalate is dissolved with warm water (water temperature is at 45-55 ℃), and it is filtered, remove the solid impurity in the solution, feed liquefied ammonia again in oxalic acid solution, being mixed with pH is 4.3-4.5, and concentration is the ammonium oxalate solution of 130-150g/L.

B, the crystallization of preparation cobalt/cobalt oxide presoma cobalt oxalate:

To make with extra care cobalt chloride solution adjust its concentration be 85 ± 5g/L (temperature is that 25-28 ℃, pH are 0.7 ± 0.1) and be prepared into concentration be the ammonium oxalate solution of 139 ± 2g/L (temperature is 65-70 ℃) with atomized spray in reactor.Mix and stir, mixing speed is 90-250 commentaries on classics/min, and temperature is between 50-52 ℃ during reaction, and it is 2 minutes-5 minutes that the control charging rate makes the reaction time, isolates crystal then;

Perhaps:

A, preparation ammonium oxalate solution:

Oxalic acid is dissolved with warm water (water temperature is at 45-65 ℃), and it is filtered, remove the solid impurity in the solution, feed liquefied ammonia again in oxalic acid solution, being mixed with pH is 4.1-4.5, and concentration is the ammonium oxalate solution of 130-150g/L.

B, the crystallization of preparation cobalt/cobalt oxide presoma cobalt oxalate:

The crystallization of preparation cobalt oxalate:

With refining cobalt chloride solution adjust its concentration be 50-140g/L and be prepared into concentration be the ammonium oxalate solution of 130-150g/L with atomized spray in reactor, mix and stir, temperature is between 50-52 ℃ during reaction, flow is during reaction: the 35-45L/ branch, reaction time is 5-7 minute, reaction end pH value: 1.6-1.8; Isolate crystal then;

By above-mentioned atomizing hydrolysis, can make the needle-like cobalt oxalate.

Step 4: the explosion thermal reduction prepares super-fine cobalt powder

The cobalt oxalate crystal of step 3 preparation is reduced into super-fine cobalt powder pushing away as shown in Figure 3 in the boat, same through preheating, the heating and cooling three phases carries out.In the prereduction zone, feed protective gas CO ₂Heating cobalt oxalate crystal in this protective atmosphere, heating-up temperature is 250-350 ℃, heat time heating time 40min, and then be incubated 1 hour, and make the crystal dehydration and carry out prereduction at this reduction phase, the carbon dioxide in the cobalt oxalate crystal is overflowed, it can make the crystal heap become loose, promptly carries out so-called explosion;

(2) reduction:

Crystal after the prereduction continues to move ahead in pushing away boat, enters reduced zone, passes through successively in 4 compartments, and 400 ℃ of low-temperature space temperature, high-temperature region temperature are 500-550 ℃, and the temperature of preceding low-temperature zone and back low-temperature zone is hanged down 30-50 ℃ than the temperature of high temperature section.The time that stops at each space material is 40-60min.Reduction process is carried out in hydrogen and nitrogen formation reducing atmosphere, and the volume ratio of hydrogen and nitrogen is 3: 1, liquefied ammonia is decomposed obtain reducing gas: 2NH ₃→ 3H ₂+ N ₂

(3) cooling

Material after the reduction enters cooled region, at CO ₂Protective atmosphere in crystal cooling, inerting to room temperature, promptly can be made into the super-fine cobalt powder of particle diameter at 0.1～2 μ m.Cooled region is divided into 3 temperature drop ladder compartments, and the temperature difference of each ladder can be at 40-80 ℃, as cools to 460 ℃ of insulations 40 minutes, continues to cool to 400 ℃ of insulations 40 minutes, naturally cools to room temperature at last.

Embodiment 3:

Employed secondary raw material is the waste hand alloy material piece in the present embodiment, and its process chart is seen shown in Figure 3, and what its dissolution process used is the electrodissolution method.

Implantation concentration is a 1.5-5 gram equivalent/rise hydrochloric acid solution in an electrolytic cell, and the anode basket of being made by the polyvinyl chloride orifice plate is set therein, and the waste hand alloy material piece of packing in this basket is as anode.Insert conductive plate as negative electrode in electrolytic cell, it can be a graphite cake, preferably adopts titanium mesh.This negative electrode is connected dc source with anode.Tank voltage is controlled at 1.5-4.0V, and current density is the 50-300 amperes per meter ²The time, the concentration of the hydrochloric acid in the electrolytic cell remain at the 1.5-5 gram equivalent/liter, when its concentration in electrolytic process descends, in time replenish hydrochloric acid.

Contain more tungsten carbide in the Hardmetal materials, in the molten cobalt of electrolysis therefrom, tungsten carbide does not dissolve, and can reclaim, and is reprocessed into tungsten-carbide powder, is reused for the making of Hardmetal materials.In electrolytic process, can form one deck tungsten carbide shell on the carbide surface, it can cause anodic passivity.Therefore, in electrolytic process, should in time shell.Can insert grinding in ball grinder by the carbide alloy that will form the tungsten carbide shell and shell, regularly artificial vibration is contained in the effect that alloy in the polyvinyl chloride basket also has broken shell.

When the concentration of cobalt in the electrolyte reaches 70 grams per liters when above, it is drawn electrolytic cell be thick cobalt chloride salting liquid.Refill new hydrochloric acid solution.The electrolytic solution operation is proceeded.Next see figure for the processing of electrolyte, and substantially the same manner as Example 1.

Embodiment 4:

Provide several atomizing hydrolysis in the present embodiment and make the concrete grammar of presoma.Its raw material is as refining cobalt chloride or the cobalt sulfate solution made among the embodiment of front.

(1) atomizing hydrolysis system presoma cobalt oxalate crystal

With described refining cobalt chloride or cobalt sulfate solution adjust its concentration be 50-140g/L and be prepared into concentration be 100-300g/L, pH be the ammonium oxalate solution of 4.3-4.5 with atomized spray in reactor, mix and stir, temperature is between 45-70 ℃ during reaction, flow is during reaction: the 35-45L/ branch, reaction time is 2 minutes-8 minutes, reaction end pH value: 1.6-1.8; Isolate presoma cobalt oxalate crystal then.

(2) atomizing hydrolysis system presoma cobalt carbonate crystal

With described refining cobalt chloride or cobalt sulfate solution adjust its concentration be 50-140g/l and be prepared into concentration be the ammonium bicarbonate solution of 100-300g/L with atomized spray in reactor, described refining cobalt chloride or cobalt sulfate solution control addition are 80L～300L/hr, and ammonium carbonate is pressed Co ^{+ 2}1.1～2.0 of metering is extraordinarily gone into, and mixes and stirs, and average reaction time: 1-5 hours, reaction temperature: 50-70 ℃, pH value: 7.0-9 isolated presoma cobalt carbonate crystal then.

(3) atomizing hydrolysis system presoma cobalt hydroxide crystal

With described refining cobalt chloride or cobalt sulfate solution adjust concentration be 50-140g/l and be prepared into concentration be the NaOH solution of 15-35% with atomized spray in reactor, mix and stir, add the NH of 98% concentration simultaneously ₃Gas is regulated NH ₃Addition makes free Co ²⁺Concentration is 0.5-100 milligrams/l, and the best is 10-15 milligram/l, and the pH of reactant liquor is 8-11, and its optimum value is 9.8-10.5; Stablize Co ²⁺The charging rate of liquid is a value among the 70-300L/hr, as 160L/hr, adopts dosing device realization quantifying feeds such as measuring pump.The charging rate of NaOH solution is mated with control pH, and reaction temperature is 40-65 ℃, and optimum value is 50-60 ℃; Mixing speed is 90-150 rev/min, and the average grain diameter of crystallization control crystal is the 3-15 micron, and the optimum value of granularity is the 5-10 micron; This reaction can be continuous, continuous charging, and continuous pulp discharge also can be that intermittently being a reactor is one-period; No matter be continous way or intermittent reaction, its average reaction time is 2-50 hour, and the best is 5-8 hour.

(4) the complicated cobalt salt of atomizing hydrolysis system presoma cobalt oxalate and cobalt hydroxide mixing

It is the best 30-50g/L of being of 20-100g/L that described refining cobalt chloride or cobalt sulfate solution are adjusted concentration, and precipitating reagent is that concentration is the ammonium oxalate of 0.1-2.0mol/L and the NH of proportion d=0.5-0.95 ₃H ₂O and weight percent concentration are the mixture of any one or two kinds among two of the NaOH of 10-35%,, mix and stir, Co in reactor with atomized spray ²⁺The charging rate of liquid is 30-200L/hr, and the pH of reactant liquor is 7-12, and optimum value is 8-9, and reaction temperature is 50-75 ℃, and optimum value is 60-70 ℃, passes through NH ₃H ₂The addition of O and/or NaOH keeps pH stable simultaneously, keeps temperature, charging rate to stablize in the reaction, and charging rate is equally by keeping constant with the constant displacement pump feed way; Average reaction time is 5-60 minute, and optimum value is 20-40 minute, generates the cobalt oxalate of fibrous or fibre-like and the complicated cobalt salt that cobalt hydroxide mixes by each reaction condition control.

Claims (13)

1, a kind of circulating technology is produced the manufacture method of super-fine cobalt powder, it is characterized in that: adopt the secondary cobaltiferous waste material, make the super-fine cobalt powder that Fisher particle size is 0.1-2.0 micron, oxygen content＜0.6%, carbon content＜0.05%, sulfur content＜0.05% through dissolving, purification, atomizing hydrolytic precipitation and reduction process;

Described secondary cobaltiferous waste material be wherein cobalt content be 0.5-55% or more than, contain the secondary slugs of one or more impurity among Ni, Fe, Cd, Cu, Pb, Mg, Ca, Cr, Zr, Si, Zn, Li, Mn, Fe, the Al in addition;

Described course of dissolution is to make cobalt in the described secondary cobaltiferous waste material be dissolved in process in hydrochloric acid or the sulfuric acid, and the part of other material in waste material described in this process also is dissolved in wherein, forms thick cobalt salt solution thus;

Described purification is and contains P2045-50%+ sulfonated kerosene 95-50% volume ratio mixed liquor by extractant described thick cobalt salt solution is carried out single extraction and contain raffinate phase that the mixed liquor of P507 10-50%+ sulfonated kerosene 90-50% volume ratio obtains single extraction with extractant carrying out reextraction and obtaining refining cobalt chloride solution or the cobalt sulfate solution that cobalt content is higher than described thick cobalt salt solution; Perhaps

Described purification process is a chemical deposition process, kind and precipitation characteristic selective precipitation agent according to one or more impurity in the described thick cobalt salt solution add in the described thick cobalt salt solution, and adjustment pH value of solution value, make described contamination precipitation and, make refining cobalt chloride or cobalt sulfate solution by filtering; Perhaps

Described purification process is an electrochemical deposition process, kind and sedimentation potential characteristic according to one or more impurity in the described thick cobalt salt solution, select suitable current density, with graphite is anode, with the titanium plate is negative electrode, with described thick cobalt salt solution is that electrolyte carries out electrolysis, makes impurity separate out on negative electrode and remove, and makes refining cobalt chloride or cobalt sulfate solution;

Described atomizing hydrolysis is in described refining cobalt chloride or cobalt sulfate solution that to add precipitating reagent be in ammonium oxalate, ammonium carbonate, NaOH and the ammoniacal liquor one or more, several raw materials feed intake with spray pattern, stir, the pH of control solution obtains cobalt oxalate, or cobalt carbonate, or the compound cobalt salt presoma of cobalt hydroxide or cobalt hydroxide and cobalt oxalate mixing;

Described reduction process is to place reducibility gas to make fibrous or fibre-like or spherical or near-spherical super-fine cobalt powder in 1-8 hour 200-700 ℃ of heating described compound cobalt salt presoma.

2, circulating technology according to claim 1 is produced the manufacture method of super-fine cobalt powder, it is characterized in that, in described course of dissolution, add hydrochloric acid or sulfuric acid, its concentration percetage by weight is: hydrochloric acid 5-37%, sulfuric acid 10-98%, or hydrochloric acid 5-30%, sulfuric acid 10-98%, addition is stoichiometric 100%-200% of described waste material weight, or calculates with all total metal contents in the described waste material, is stoichiometric 1.1-3.0 times, make it dissolving, the cobalt in the waste material forms the cobalt chloride CoCl of solubility ₂Or cobaltous sulfate CoSO ₄The solvable composition of in the waste material other also is dissolved in and forms soluble chloride or sulfate in hydrochloric acid or the sulfuric acid, forms thick cobalt chloride CoCl thus ₂Or cobaltous sulfate CoSO ₄Solution; Or:

In described course of dissolution, with described secondary slugs is anode, with the corrosion resistance conductive material is negative electrode, with sulfuric acid or hydrochloric acid is electrolyte, connect direct current, adjust the voltage and current intensity of electrolysis, make cobalt optimum solvation in described electrolyte according to the kind of cobalt and impurity in the described secondary slugs, the solvable composition of in the waste material other is being dissolved in this electrolyte of part also, forms thick cobalt chloride or cobalt sulfate solution thus.

3, circulating technology according to claim 1 is produced the method for super-fine cobalt powder, it is characterized in that, and when described purification is extraction process, in described extraction process,

(1) in described single extraction, the single extraction agent is that to contain the thick cobalt salt solution that obtains in the mixed liquor of P204+ sulfonated kerosene and the described course of dissolution be 2-15l/min with the flow of single extraction agent, saponification is 75-190mol/min with the flow of alkali, making saponification rate is 60-65%, the flow of thick cobaltous sulfate liquid or thick cobalt chloride liquid be 2-15l/min, the pH of solution be 2-4, temperature be mix under 10-40 ℃ the adjusting, layering, acquisition contains the raffinate phase that the cobalt amount is higher than described thick cobalt salt solution, makes half refining cobalt salt solution;

(2) in described reextraction, the reextraction agent is to contain the mixed liquor of P507+ sulfonated kerosene and described half refining cobalt salt solution is 0.8-15l/min with the cobalt sulfate solution flow, the reextraction agent flux is 2-20l/min, saponification is 200-1000ml/min with the alkali flow, to make saponification rate be the mixed proportion of 20-50%, in temperature be mix under 10-40 ℃ the adjusting, layering; Stay extraction phase, this extraction phase and concentration be mix under the sulfuric acid of 0.1-0.8mol/L or the adjusting that hydrochloric acid with 1-4l/min, in temperature is 10-40 ℃, layering, getting strip liquor becomes refining cobalt chloride or cobalt sulfate solution.

4, circulating technology according to claim 1 is produced the manufacture method of super-fine cobalt powder, it is characterized in that: several raw materials in the described atomizing hydrolysis feed intake with spray pattern, stir, the pH value of control solution obtains cobalt oxalate, or the compound cobalt salt presoma of cobalt carbonate or cobalt hydroxide or cobalt hydroxide and cobalt oxalate mixing.

5, circulating technology according to claim 1 is produced the manufacture method of super-fine cobalt powder, it is characterized in that: between described dissolving and purification process, be provided with a removal of impurities process,

Described removal of impurities process is a chemical precipitation process, adds in the described thick cobalt salt solution according to the kind of one or more impurity in the described thick cobalt salt solution and precipitation characteristic selective precipitation agent, and adjusts the pH value of solution value, makes described contamination precipitation and by filtering; Perhaps

Described removal of impurities process is an electrochemical deposition process, kind and sedimentation potential characteristic according to one or more impurity in the described thick cobalt salt solution, select suitable current density, with the corrosion resistance conductive material is male or female, or be anode with graphite, with the titanium plate is negative electrode, is that electrolyte carries out electrolysis with described thick cobalt salt solution, makes impurity separate out on negative electrode and remove.

6, circulating technology according to claim 3 is produced the manufacture method of super-fine cobalt powder, it is characterized in that described extraction process is:

A. thick cobalt salt solution acid adjustment: add hydrochloric acid or add sulfuric acid in described thick cobalt chloride liquid in described thick cobaltous sulfate liquid, the pH value of regulator solution is that 2-4 is standby;

B. prepare extractant and strippant

The single extraction agent is that volume ratio is the mixed liquor of P204 5-20%+ sulfonated kerosene 95-80%;

The reextraction agent is that volume ratio is the mixed liquor of P50710-30%+ sulfonated kerosene 90-70%;

Strippant is the pure water solution of sulfur acid or hydrochloric acid 1.0-5mol/L;

Wash the pure water solution of acid 1 for sulfur acid or hydrochloric acid 0.30-0.8mol/L;

Wash the pure water solution of acid 2 for sulfur acid or hydrochloric acid 0.10-0.8mol/L;

Saponification alkali is the sodium hydroxide solution of 1-10mol/L;

C. extraction:

Single extraction is fractional extraction:

A, abstraction impurity removal:

Will be in (1) feed in the extractor with alkali through single extraction agent and the saponification for preparing among the thick cobalt chloride of acid adjustment or thick cobaltous sulfate, the B, wherein, the flow of single extraction agent is 2-15l/min, saponification is that to make saponification rate be 60-65% to 50-300mol/min with the flow of alkali, the flow of thick cobaltous sulfate liquid or thick cobalt chloride liquid is 2-15l/min, fully stir, leave standstill, phase-splitting, carry out single extraction at normal temperature, the raffinate phase of drawing is standby as half refining cobalt chloride or cobalt sulfate solution, and load organic phases enters the next stage washing section;

B, wash cobalt:

Load organic phases in the last a step is fed in the next stage washing section with the 2-15L/min flow, with washing in the flow adding extractor of acid 1 with 80-120ml/min of preparing among the B, fully stir, leave standstill the 10-20min phase-splitting, wash described load organic phases, further extract remaining cobalt from load organic phases, promptly partly refining cobalt chloride of the raffinate phase in washing lotion and a step or cobalt sulfate solution merge standby, and this process can further reclaim the remaining cobalt ions of load organic phases;

C, back extraction impurity:

The load organic phases that process is washed behind the cobalt enters the next stage stripping section with the 2-15L/min flow, feed the strippant of preparing among the B simultaneously, the flow of strippant is 100-200ml/min, fully stir, leave standstill phase-splitting, draw the extractant of regeneration, recycle, impure strip liquor enters sewage disposal system;

Reextraction is fractional extraction:

A, extraction cobalt:

The reextraction agent and the saponification of preparing among half refining cobalt chloride solution that will obtain in single extraction or half POV cobalt liquor, the B feed in the extractor with alkali, wherein said cobalt sulfate solution or cobalt chloride solution flow are 0.8-4l/min, the reextraction agent flux is 5-20l/min, saponification is 200-700ml/min with the alkali flow, making saponification rate is 35% or 20-40%, fully stirs, and leaves standstill the 10-20min phase-splitting, carry out reextraction at normal temperature, cobalt enters load organic phases; Draw raffinate phase.

B, washing impurity:

Load organic phases is fed the next stage washing section with the acid 2 of washing of preparing among 5-20L/min flow and the B, washing sour 2 flows is 0.1-1.0l/min, fully stirs, and leaves standstill (10-20min) phase-splitting, enter the next stage stripping section through the load organic phases after the washing, washing lotion merges with the raffinate phase in a step;

Cobalt is carried in c, back extraction

This load organic phases enters the next stage stripping section with the 5-20L/min flow, feed the strippant of preparing among the B simultaneously, the strippant flow is 100-200mL/min, fully stir, leave standstill 10-20min, the extractant of regeneration is drawn in phase-splitting, recycle, the strip liquor that contains refining cobalt chloride or cobaltous sulfate uses as finished product.

7, circulating technology according to claim 6 is produced the method for super-fine cobalt powder, it is characterized in that: also have some nickel elements in the described washing lotion of drawing in described raffinate phase of drawing in described reextraction in a step and the b step, it is handled:

With the described washing lotion of drawing in described raffinate phase of drawing in the described a step and the b step is that solution containing nickel is handled respectively according to nickel content, to reclaim nickel, or contain low the entered sewerage recovery nickel of nickel concentration, and contain the nickel concentration height, reclaim nickel with chemical precipitation method or extraction.

8, circulating technology according to claim 4 is produced the manufacture method of super-fine cobalt powder, and it is characterized in that: described atomizing hydrolytic process is:

It is 50-140g/L and to be prepared into concentration be that 100-300g/L, pH are 3.0-5.5 or are the precipitating reagent of 4.0-4.5 that described refining cobalt chloride or cobalt sulfate solution are adjusted its concentration---ammonium oxalate solution with atomized spray in reactor, mix and stir, temperature is between 45-70 ℃ during reaction, flow is during reaction: the 30-100L/ branch, reaction time is 2 minutes-60 minutes, or is 22-25 minutes; Reaction end pH value: 1.0-2.8, or be 1.7-1.9; Isolate cobalt oxalate crystal presoma then; Or be:

With described refining cobalt chloride or cobalt sulfate solution adjust its concentration be 50-140g/l and be prepared into concentration be the sal volatile of 50-300g/L with atomized spray in reactor, described refining cobalt chloride or cobalt sulfate solution control addition are 50L～300L/hr, pH value: 7.0-10, or be 7.5-9.0, ammonium carbonate is pressed Co ²⁺1.1～2.0 of metering is extraordinarily gone into, and stablizes the pH value by the adding speed of regulating ammonium carbonate, mixes and stirs, average reaction time: 1-10 hours, reaction temperature: 50-70 ℃, isolate spherical then or near-spherical cobalt carbonate crystal presoma; Or be:

With described refining cobalt chloride or cobalt sulfate solution adjust concentration be 50-140g/l and be prepared into weight percent concentration be the NaOH solution of 15-35% with atomized spray in reactor, mix and stir, add the NH of percentage by weight 10-30% concentration simultaneously ₃Solution or feed be weight percentage NH more than 98% of purity ₃Gas, its addition is with free Co in the solution ²⁺Concentration is tolerance, control NH ₃Addition makes free Co ²⁺Concentration is 0.5-200 milligrams/I, and the pH of reactant liquor is 7-14, Co ²⁺The charging rate of liquid is 50-300L/hr, and the charging rate of NaOH solution is mated by the pH of control, and reaction temperature is 40-70 ℃, and mixing speed is 70-250 rev/min, and the average grain diameter of crystallization control crystal is the 2-15 micron; Average reaction time is 2-50 hour, makes spherical or near-spherical cobalt hydroxide crystal presoma; Or be:

It is 10-100g/L that described refining cobalt chloride or cobalt sulfate solution are adjusted concentration, and precipitating reagent is that concentration is the ammonium oxalate of 0.1-3.0mol/L and the NH of proportion d=0.5-0.95 ₃H ₂O and weight percent concentration are the mixture of any one or two kinds among two of the NaOH of 10-35%,, mix and stir, Co in reactor with atomized spray ²⁺The charging rate of liquid is 30-300L/hr, and the pH of reactant liquor is 7-12, or is 7.5-9.5, and reaction temperature is 50-75 ℃, or is 60-70 ℃, by regulating NH ₃H ₂The addition of O and/or NaOH keeps pH stable, keeps temperature, charging rate to stablize in the reaction, and charging rate is equally by keeping constant with the constant displacement pump feed way; Average reaction time is 5-1200 minute, or is 20-40 minute, generates the cobalt oxalate of fibrous or fibre-like and the compound cobalt salt presoma that cobalt hydroxide mixes by controlling each reaction condition.

9, circulating technology according to claim 8 is produced the manufacture method of super-fine cobalt powder, it is characterized in that: in described atomizing hydrolytic process, feeding intake of described reactant is the mode of liquidating, promptly the upper and lower in reactor all is provided with feed nozzle respectively, above a nozzle spout downward, below a nozzle spout upwards spray material; Described refining cobalt chloride or cobalt sulfate solution be from spraying downwards at last nozzle, described precipitating reagent under upwards ejection of nozzle.

10, the circulating technology manufacture method of producing super-fine cobalt powder according to claim 1 or 5, it is characterized in that: described reduction process is the explosion thermal reduction, its minute prereduction, reduction and cooling three phases:

(1) prereduction:

With described compound cobalt salt presoma at reducing gas protective gas N ₂Or CO ₂Protective atmosphere in, temperature is 200-500 ℃, reduced 1-5 hour, make the crystal dehydration and carry out prereduction at this reduction phase, the mist of cobalt oxalate or cobalt carbonate crystal cracking release of carbon dioxide and carbon monoxide has reducing property, and the carbon dioxide in cobalt oxalate or the cobalt carbonate crystal is overflowed, it makes the crystal heap become loose, promptly carries out so-called explosion;

(2) reduction:

Crystal after the prereduction was reduced 1-10 hour at 400-650 ℃, reduction process is carried out in hydrogen and nitrogen formation reducing atmosphere, the volume ratio of hydrogen and nitrogen is 3: 1, and the feeding amount of reducing gas is decided by the amount of presoma, and its proportionate relationship satisfies reduction reaction with wherein hydrogen and is as the criterion;

(3) cooling

At N ₂Or CO ₂Protective atmosphere in crystal cooling, inerting to room temperature, promptly make fibrous or the spherical or near-spherical super-fine cobalt powder of particle diameter at 0.1～2.0 μ m.

11, circulating technology according to claim 10 is produced the manufacture method of super-fine cobalt powder, and it is characterized in that: described reduction phase is divided into a plurality of temperature rise periods: preceding low-temperature zone, high temperature section, and described preceding low-temperature zone is hanged down 30-50 ℃ than the temperature of high temperature section; Described cooling stage is divided into several temperature drop ladders, and the temperature difference of each ladder is at 40-80 ℃.

12, circulating technology according to claim 10 is produced the manufacture method of super-fine cobalt powder, and it is characterized in that: described cooling stage is divided into several temperature drop ladders, and the temperature difference of each ladder is at 40-80 ℃.

13, a kind of circulating technology is produced the manufacturing equipment of super-fine cobalt powder, it is characterized in that: comprise dissolution equipment, equipment for purifying, atomizing hydrolysis reactor and reduction apparatus, described dissolution equipment is to have the reactor of heater or have heater and the reactor of electrolysis unit, and described purifying plant is extraction box or has heater and the reactor of electrolysis unit, described reduction apparatus are hydraulic pressure and mechanically operated automatic multiple stage boat;

Described multisection type pushes away boat, comprise three passage housings, be connected to form a long and narrow passage by transfer pipeline therebetween, be provided with import and outlet at the two ends of this passage, described three housings form three zones in proper order from the outlet that enters the mouth: prereduction zone, reduced zone and cooled region, the described chamber that pushes away each zone formation of boat separates or is provided with the fire door or the flashboard of automatic control by the stainless steel curtain, flow mutually with the gas that limits each chamber; This curtain is located in the connecting line between each chamber and in the outlet, the upper end and the tube wall of described curtain are articulated and connected, its lower end is a free end, each zone links together, forming one in pushing away boat can be by the tubular conduit of each chamber, in this tubular conduit, be provided with several material boats each other in contact, be provided with in the import department that pushes away boat the material boat is pushed material boat propulsion plant in the described tubular conduit, in described heater and temperature detection and the adjusting device of in each chamber, being provided with, provide required temperature in order to give each chamber; In described each chamber, also be provided with one or more air inlets and exhaust outlet; Be provided with cooling device in the described cooled region;

Be provided with air inlet and exhaust outlet at the top of each regional casing, in described prereduction zone and reduced zone, described air inlet and exhaust outlet be located at these regional two ends and air inlet/outlet opposite with the direct of travel that pushes away boat; Be separated into the plurality of segments space by dividing plate again in each zone, this dividing plate thereunder is provided with access opening makes each segment space connection make the described boat that pushes away pass through; In prereduction zone and reduced zone, be respectively equipped with several segment space, heater is set to form different temperature respectively in different segment space in each segment space, also be provided with several segment space at cooled region, in each segment space, be respectively equipped with cooler; Casing top, middle part in the several segment space in the front of cooled region is provided with air inlet, and in the end casing top, a segment space middle part is provided with exhaust outlet.

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