WO2007071108A1 - Procede de production de poudre de cobalt superfine par circulation et appareil - Google Patents

Procede de production de poudre de cobalt superfine par circulation et appareil Download PDF

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Publication number
WO2007071108A1
WO2007071108A1 PCT/CN2005/002265 CN2005002265W WO2007071108A1 WO 2007071108 A1 WO2007071108 A1 WO 2007071108A1 CN 2005002265 W CN2005002265 W CN 2005002265W WO 2007071108 A1 WO2007071108 A1 WO 2007071108A1
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Prior art keywords
cobalt
solution
extraction
crude
temperature
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PCT/CN2005/002265
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English (en)
Chinese (zh)
Inventor
Kaihua Xu
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Shenzhen Gem High-Tech Joint-Stock Co., Ltd.
Jingmen Gem New Material Co., Ltd.
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Priority to PCT/CN2005/002265 priority Critical patent/WO2007071108A1/fr
Publication of WO2007071108A1 publication Critical patent/WO2007071108A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds

Definitions

  • the present invention provides a method for producing cobalt powder, and more particularly to a method for producing ultrafine cobalt powder by a recycling technique; it is a further object of the present invention to provide an apparatus for the above manufacturing method.
  • Metallic cobalt powder is recognized as a strategic metal material in the world and has been a guest of the London Metal Futures Exchange for decades. In the past five years, due to the large-scale use of metallic cobalt powder in high-energy batteries, cemented carbide, military and other fields, the world's cobalt has been strained. It can be said that whoever masters the manufacturing technology of cobalt resources and related products, who has mastered the initiative in many key industrial fields such as chemical energy, communications, and military industry.
  • Ultrafine cobalt powder material is one of the advanced representatives in the field of new materials in this century. Ultrafine cobalt powder is used as a key material in the production of high-energy batteries, high-strength cemented carbide and military equipment, and is known as modern industrial MSG.
  • Lithium-ion batteries contain more than 40% cobalt, and nickel-hydrogen batteries contain more than 10% cobalt. Therefore, cobalt is a key material for determining the cost of new chemical energy sources such as lithium-ion batteries.
  • China's economy is a fast-growing economy as a world manufacturing center.
  • China is not only a transit country for the use of cobalt resources in the world, but with the development of China's domestic communications and automotive industries, the industry has become the real market for cobalt resources in the world. Use a big country.
  • China's domestic consumption of cobalt resources is more than 10,000 tons per year. Therefore, the development of recycling technology and the recycling of secondary resources for the development of cobalt are crucial to solving the problem of poor cobalt resources in China and promoting the continued growth of modern industries.
  • the methods for producing cobalt powder in the prior art include a carbonyl method, an electrolysis method, a reduction method, and an atomization method.
  • the carbonyl method is a conventional method, and the particle size can be within 5-10 ⁇ m, and the morphology is spherical or chain-like.
  • the method has the advantages of stable spherical structure, good electrical conductivity and over-discharge and discharge performance, and can be well used for the manufacture of a power nickel-hydrogen battery; the disadvantage is that the carbon content is high (0.2-0.3%), which will reduce the capacity of the battery and
  • the production method is carcinogenic, non-environmental, with strict production equipment and large investment.
  • the cobalt powder produced is a dendritic powder and is used in the powder metallurgy industry.
  • the disadvantages of this method are high energy consumption, high cost, and large particle size (generally around 30 m).
  • This cobalt powder can only be used in general powder metallurgy products and cannot be used in batteries and high-strength powder metallurgy products.
  • the atomization method has water atomization and gas atomization. This method has the same disadvantages as the electrolysis method, such as high energy consumption, high cost, and large particle size (generally around 30 u m), and the industrial value is not large.
  • the reduction method includes liquid phase reduction method and high temperature solid phase reduction method, liquid phase reduction method is developing, and high temperature reduction method using cobalt oxalate as material is the main method of current cobalt powder production, represented by companies such as Belgian Minmetals Corporation. , has formed a scale, accounting for more than 90% of the production of cobalt powder. But the existing cobalt powder of this type The shape is irregular, and there is no set of methods for controlling the particle size and particle size of the product well, and it can be stably mass-produced in the process. There are also many problems to be solved in the equipment for use. Summary of the invention
  • the object of the present invention is to improve the deficiencies in the prior art, and to provide a manufacturing method for producing ultrafine cobalt powder by using a recycling technique with secondary resources, simple manufacturing process, environmental protection, low investment, and suitable for industrial production;
  • the object of the present invention is achieved by the method of the present invention for producing a superfine cobalt powder by using a secondary cobalt-containing raw material (also referred to as cobalt-containing waste), which is dissolved, purified, atomized and hydrolyzed. And the reduction process is made into an ultrafine cobalt powder having a particle diameter of 0.1 to 2.0 ⁇ m, an oxygen content of ⁇ 0.6%, a carbon content of ⁇ 0.05%, and a sulfur content of ⁇ 0.05%.
  • a secondary cobalt-containing raw material also referred to as cobalt-containing waste
  • the reduction process is made into an ultrafine cobalt powder having a particle diameter of 0.1 to 2.0 ⁇ m, an oxygen content of ⁇ 0.6%, a carbon content of ⁇ 0.05%, and a sulfur content of ⁇ 0.05%.
  • the dissolution process is a process of dissolving cobalt in the secondary cobalt-containing waste in hydrochloric acid or sulfuric acid, in which a part of other substances in the waste are also dissolved therein, thereby forming a crude cobalt salt solution. ;
  • the purification is carried out by extracting the crude cobalt salt solution once by using a mixture of P204 5-50%+sulfonated kerosene 95-50% (volume ratio) and containing P507 10-50% with the extractant. + sulfonated kerosene 95-50% (volume ratio.) of the mixture is subjected to secondary extraction of the raffinate phase obtained by one extraction to obtain a purified cobalt chloride solution or a cobalt sulfate solution having a cobalt content higher than the crude cobalt salt solution; Or
  • the purification process is a chemical precipitation process, selecting a precipitant to be added to the crude cobalt salt solution according to the kind and precipitation characteristics of one or more impurities in the crude cobalt salt solution, and adjusting the pH value of the solution, so that the The impurities are precipitated and filtered to prepare a purified cobalt chloride or cobalt sulfate solution; or
  • the purification process may also be an electrochemical deposition process, selecting a suitable current density according to the type and deposition potential characteristics of one or more impurities in the crude cobalt salt solution, using graphite as the anode and titanium plate as the cathode.
  • the crude cobalt salt solution is electrolyzed as an electrolytic solution, and impurities are deposited on the cathode to be removed, thereby preparing a purified cobalt chloride or cobalt sulfate solution.
  • the atomization hydrolysis is one or several kinds of precipitating agent oxalic acid, sodium hydroxide and ammonia water added to the refined cobalt chloride or cobalt sulfate solution, and several raw materials are sprayed, stirred, and the solution is controlled.
  • the reduction process is carried out by placing the precursor in a reducing gas at 200-700 Torr for 1-8 hours to form a fibrous or fibrillar-like or spherical or spheroidal ultrafine cobalt powder.
  • the secondary cobalt-containing waste according to the present invention has a cobalt content of 0.1-55 % or more, and further contains Ni, Fe, Cd, Cu, Pb, Mg, Ca, Cr, Zr, Si, Zn, Li, Mn, a secondary waste of one or more of Fe, Al; specifically, it may be:
  • Scrap nickel-hydrogen/nickel-cadmium batteries and scraps and trimming materials in the production process contain 0.01-15% cobalt; other components are Ni, Fe, Cd, Zn, etc., Ni: 5- 70%, Fe: 0.01-10%. Cd: 0.01-10%, Zn: 0.01-10%
  • Waste lithium ion battery and waste material and edge material in the production process such waste contains 5-60% Co, other components are Ni, Li, graphite, Mn, etc., Ni: 0.1-50%, Li : 1-20%. Graphite: 1-30%, Mn: 0.1-50%
  • Scrap, trim and waste catalyst in waste synthetic diamond products and synthetic diamond industry such as Co: 1-10%, Ni: 1-40%, Mn: 1-30%, trace Fe, Al, Cu, Mg, Ca, Gr et al.
  • hydrochloric acid or sulfuric acid is added, and the concentration percentage by weight is: 5 - 37 % of hydrochloric acid, 10 - 98 % of sulfuric acid, and the amount is 100% - 200% of the chemical equivalent of the weight of the waste, or Calculate the total amount of all metals in the waste, which is 1.1-3.0 times the chemical equivalent, so that it dissolves, and the cobalt in the waste forms soluble cobalt chloride ( 0 (1 2 or cobalt sulfate CoS0 4 ; other soluble in the waste)
  • the component is also dissolved in hydrochloric acid or sulfuric acid to form a soluble chloride or sulfate, thereby forming a crude cobalt chloride 0 ⁇ 1 2 or a cobalt sulfate CoS0 4 solution; or:
  • the secondary waste is used as an anode
  • the corrosion-resistant conductive material is used as a cathode
  • sulfuric acid or hydrochloric acid is used as an electrolyte
  • direct current is turned on, and the cobalt and impurities are adjusted according to the type of the secondary waste.
  • the voltage and current intensity of the electrolysis preferentially dissolve cobalt in the electrolyte, and other soluble components in the scrap are also partially dissolved in the electrolyte, thereby forming a crude cobalt chloride or cobalt sulfate solution.
  • the crude cobalt salt solution is extracted once and extracted with an extractant by a mixture containing P204 5-50%+sulfonated kerosene 95-50% (volume ratio).
  • P507 10-50%+ sulfonated kerosene 95-50% (volume ratio) mixture is subjected to secondary extraction of the raffinate phase obtained by one extraction to obtain a purified cobalt chloride solution having a cobalt content higher than that of the crude cobalt salt solution.
  • the atomized hydrolysis is one or more of adding a precipitating agent of oxalic acid, sodium hydroxide and ammonia in the refined cobalt chloride or cobalt sulfate solution, and several raw materials are sprayed by spraying.
  • Stirring controlling the pH of the solution to obtain cobalt oxalate, or cobalt carbonate, or a composite cobalt salt precursor of cobalt hydroxide or cobalt hydroxide and cobalt oxalate;
  • the reduction process is carried out by placing the precursor in a reducing gas at 200 to 700 ° C for 1 to 8 hours to form a fibrous or fibrillar-like or spherical or spheroidal ultrafine cobalt powder.
  • a dedusting process may be provided between the cobalt-dissolving process and the purification process to reduce the dedusting pressure of the subsequent extraction and purification process.
  • the impurity removing process may be a chemical precipitation process, selecting a precipitant to be added to the crude cobalt salt solution according to the kind and precipitation characteristics of the one or more impurities in the crude cobalt salt solution, and adjusting the pH value of the solution. Allowing the impurities to precipitate and being filtered out; or
  • the impurity removing process may also be an electrochemical deposition process, selecting a suitable current density according to the kind and deposition potential characteristics of one or more impurities in the crude cobalt salt solution, using graphite as an anode and titanium plate as The cathode is electrolyzed by using the crude cobalt salt solution as an electrolytic solution, and impurities are deposited on the cathode to be removed.
  • an electrochemical deposition process selecting a suitable current density according to the kind and deposition potential characteristics of one or more impurities in the crude cobalt salt solution, using graphite as an anode and titanium plate as The cathode is electrolyzed by using the crude cobalt salt solution as an electrolytic solution, and impurities are deposited on the cathode to be removed.
  • the extractant is a mixture of P204+sulfonated kerosene and a crude cobalt salt solution obtained during the dissolution process, and the flow rate of P204 is 2-15 1/min, and the flow rate of the alkali for saponification 75-190mol/min, the saponification rate is 60-65%, the flow rate of crude cobalt sulfate or cobalt chloride is 2-15 l/min, and the mixture is adjusted under the condition of pH 2-4 and temperature 10-40 ⁇ . And stratifying, obtaining a raffinate phase having a cobalt content higher than the crude cobalt salt solution, and preparing a semi-refined cobalt salt solution;
  • the extractant contains a mixture of P507+sulfonated kerosene and the crude cobalt salt solution obtained in the dissolution process with a flow rate of cobalt sulfate solution of 0.8-15 1 / min, P507 secondary extraction
  • the flow rate of the agent is 2-20 1/min
  • the flow rate of the alkali for saponification is 200-1000 ml/min
  • the saponification rate is 20-50%.
  • the method for producing ultrafine cobalt powder by the recycling technique of the present invention For a crude cobalt salt solution containing no nickel and containing only impurities such as Cu/Fe/Pb/Mg/Ca, it can be electrochemically or chemically precipitated as described above. The selected removed impurities, i.e., the secondary extraction by the extractant described above, is replaced by another electrochemical or chemical precipitation process.
  • the atomization hydrolysis process can be:
  • the purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/L and a precipitant prepared to a concentration of 100-300 g/L and a pH of 3.0-5.5 (optimally 4.0-4.5) - oxalic acid
  • the ammonium solution is sprayed into the reaction vessel in a mist form, mixed and stirred, and the reaction temperature is between 45-70 ° C, the flow rate during the reaction is: 30-100 IJ minutes, the reaction time is 2 minutes - 60 minutes, and the optimum is 22-25 Minute; reaction end point pH: 1.0-2.8, optimally 1.7-1.9; and then separate the precursor cobalt oxalate crystal; or:
  • the purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/l and a solution prepared to a concentration of 50-300 g/L is sprayed into the reaction vessel in a mist, the refined cobalt chloride or
  • the cobalt sulfate solution is controlled to be added in an amount of 50 L to 300 L/hr, pH: 7.0-10, optimally 7.5-9.0, and ammonium carbonate is added in an amount of 1.1 to 2.0 times measured by Co + 2 and stabilized by adjusting the rate of addition of ammonium carbonate. pH value, mixing and stirring, average reaction time: 1 to 10 hours, reaction temperature: 50-70 ° C, and then separating the precursor spherical or spheroidal cobalt carbonate crystal; or:
  • the purified cobalt chloride or cobalt sulfate solution is adjusted to a concentration of 50-140 g / l and a NaOH solution prepared to a concentration of 15 - 35 % by weight is sprayed into the reaction vessel in a mist, mixed and stirred, and simultaneously added 10 — 30% (% by weight?)
  • Concentration of NH 3 solution or > «1 3 gas with a purity of 98% (by weight) or more measured in the amount of free Co 2+ in the solution, controlled by NH 3 addition
  • the amount of free Co 2+ is 0.5-200 mg / 1
  • the pH of the reaction solution is 7-14
  • the feed rate of Co 2+ solution is 50-300 L / hr
  • the feed rate of the NaOH solution is matched by the controlled pH.
  • the reaction temperature is 40-70 ° C
  • the stirring speed is 70-250 rpm
  • the average crystal grain size of the control crystal is 2-15 microns
  • the average reaction time is 2-50 hours
  • the spherical or spheroidal precursor hydrogen is prepared.
  • a composite cobalt salt in which fibrous or fibrillar cobalt oxalate and cobalt hydroxide are mixed is produced by controlling each reaction condition.
  • 0.01 to 0.5% by weight of a PVP polymeric surfactant may be added.
  • the hydrolysis method for preparing cobalt oxalate may be:
  • the oxalic acid is dissolved in warm water (water temperature at 45-65 ° C), and filtered to remove solid impurities in the solution, and then liquid ammonia is introduced into the oxalic acid solution to prepare a pH of 4.1-4.5, and the concentration is 130- 150 g/L ammonium oxalate solution.
  • the purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/L and an ammonium oxalate solution prepared to a concentration of 130-150 g/L is sprayed into the reaction vessel in a mist form, and stirred and stirred at a temperature of 50- Between 52 ° C, the flow rate during the reaction is: 35-45 L / min, the reaction time is 5 minutes - 7 minutes, the reaction end point pH: 1. 6-1. 8; and then the crystal is separated;
  • the hydrolysis method for preparing cobalt carbonate may be - a, preparing ammonium carbonate solution - dissolving ammonium hydrogencarbonate in warm water (water temperature 45-65 ° C), and filtering the solution to remove solid impurities in the solution to prepare ammonium bicarbonate. Concentration 50-300g/L, preferably 200-230 g/L
  • the purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/l, preferably 100 g/1 and a concentration of 100-300 g/L of ammonium bicarbonate solution sprayed into the reaction vessel in a mist, Co liquid
  • the amount of controlled addition is 50L ⁇ 300L/hr, and the ammonium carbonate is 1.1 ⁇ 2 . 0 times added by Co+ 2 , pH value: 7. 5-8. 5, the stable Co liquid is controlled to increase the amount, and the ammonium carbonate is adjusted according to the pH value.
  • oxalic acid can be prepared by the above-mentioned atomization hydrolysis Cobalt or cobalt carbonate crystals.
  • the cobalt solution is a cobalt chloride solution, a fibrous or needle-like or fibrillar-like or needle-like cobalt oxalate or cobalt carbonate crystal can be formed.
  • the cobalt solution is a cobalt sulfate solution, spherical or spheroidal cobalt carbonate can be formed.
  • cobalt oxalate crystals by the hydrolysis crystallization of the above conditions, the crystal grains of the crystals produced are satisfactory, so that the particle size index of the cobalt powder produced in the subsequent process can satisfy the requirements.
  • a specific method for preparing the precursor cobalt hydroxide crystals may be:
  • the purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 120 g/l and a NaOH solution prepared to a concentration of 25% is sprayed into the reaction vessel in a mist form, mixed and stirred, and simultaneously passed into the NH 3 having a purity of 98% or more.
  • the pH of the reaction solution is 9.8 - 10.5
  • the feed rate of Co 2+ solution is 160 L / hr
  • the feed rate of NaOH solution is controlled by The pH is matched, the dosing pump is used to feed, the constant Co 2+ liquid feeding rate is adjusted, the feeding speed of the NaOH solution is adjusted to make the pH 9.8-10.5;
  • the reaction temperature is 60 ° C
  • the stirring speed is 130-140 rpm, control
  • the average crystal grain size of the crystal crystal is 5-8 micrometers; the average reaction time is 5-8 hours, and the precursor cobalt hydroxide crystal is prepared; the specific method for preparing the mixed crystal of the precursor cobalt hydroxide and cobalt oxalate may be:
  • Each reaction condition controls the formation of a complex cobalt salt in which a fibrous or fibrillar-like cobalt oxalate and cobalt hydroxide are mixed.
  • the best solution for the reduction process is blasting thermal reduction, which is divided into three stages of pre-reduction, reduction and cooling:
  • the precursor is in a protective atmosphere of reducing gas protective gas > 1 ⁇ 2 or CO 2 at a temperature of 200 "500 ° C, reduction for 1-5 hours, in this reduction stage, the crystal is dehydrated and pre-reduced, and the crystal of cobalt oxalate or cobalt carbonate crystallizes to release a mixed gas of carbon dioxide and carbon monoxide, which has reducing properties, making cobalt oxalate or cobalt carbonate crystals Carbon dioxide overflow, which can make the crystal pile loose, that is, so-called blasting;
  • the pre-reduced crystal is reduced at 400-650 Torr for 1-10 hours, and the reduction process is carried out in a reducing atmosphere of hydrogen and nitrogen.
  • the volume ratio of hydrogen to nitrogen is 3: 1.
  • the amount of reducing gas introduced is determined by the precursor. Quantity, the proportional relationship is based on which the hydrogen meets the reduction reaction;
  • the crystals are cooled and inerted to room temperature in a N 2 or CO 2 ⁇ protective atmosphere to obtain a fibrous or spherical or spheroidal ultrafine cobalt powder having a particle diameter of 0.1 to 2.0 ⁇ m.
  • the reduction stage can be further divided into a plurality of temperature rising stages: a front low temperature section and a high temperature section, and the front low temperature section is 30-50 degrees lower than the temperature of the high temperature section:
  • the cooling stage can be divided into several steps of temperature drop, and the temperature difference of each step is 40-80 °C.
  • the specific blasting thermal reduction preparation of ultrafine cobalt powder can be as follows:
  • the prepared cobalt oxalate or cobalt carbonate crystal is heated in a protective atmosphere of reducing gas N 2 or CO 2 at a temperature of 200-400 ° C for 1-3 hours, in which the crystal is dehydrated and pre-reduced, so that The carbon dioxide in the crystals of cobalt oxalate or cobalt carbonate overflows, which can make the crystal pile loose, that is, so-called blasting;
  • the pre-reduced crystal is reduced at 400-650 ° C for 1-6 hours, and the reduction process is carried out in a reducing atmosphere of hydrogen and nitrogen.
  • the volume ratio of hydrogen to nitrogen is 3:1, which can be conveniently used in practical applications.
  • the liquid ammonia is decomposed to obtain a reducing gas: 2NH3—3H2+N2.
  • the hydrogen required for reduction is conveniently obtained, and the protective nitrogen is also added, which is convenient, safer and cheaper than using hydrogen, and has better performance.
  • Industrial applicability The amount of the reducing gas to be introduced is determined by the amount of the precursor, and the proportional relationship is preferably such that the hydrogen therein satisfies the reduction reaction. '
  • the crystal after the so-called "blasting" process in the pre-reduction stage is reduced, and the contact with the reducing gas, the loose powder can be more fully contacted with the reducing gas, therefore, the segment heating is beneficial to the powder in the preparation of the ultra-fine cobalt powder.
  • Loose, low pine ratio, and favorable for the reduction reaction can also shorten the reaction time, improve production efficiency, and make the structure of the device compact and reduce the floor space.
  • the reduction stage can be further divided into a plurality of heating stages: the front low temperature section and the high temperature section, and the temperature of the front low temperature section can be lower than the high temperature section by 30-5 (TC, for example, the former low temperature section is 460 ° C, and the temperature is kept therein for 40 minutes. Then heat up to 500 ° in the high temperature section and keep it for 40 minutes, which can be heated evenly;
  • the crystal is cooled or inerted to room temperature in a protective atmosphere of ⁇ 2 or C0 2 to obtain a fibrous or spherical ultrafine cobalt powder having a particle diameter of 0.1 to 2 m.
  • the post-cooling phase can also be divided into several steps of temperature drop, and the temperature difference of each step can be between 100 and 150. C, if it is cooled to 460 ° C for 20 minutes, continue to cool down to 300 ° C for 20 minutes, and finally naturally cool to room temperature. Multi-stage cooling can reduce the cooling rate of the crystal, avoid crystal agglomeration and reduce the performance of the crystal.
  • the protective gas used in the pre-cooling and reduction stages is preferably carbon dioxide because it is heavier than air and has a better protection than nitrogen.
  • the recycling apparatus for producing ultrafine cobalt powder provided by the present invention comprises a dissolving device, a purifying device, a atomization hydrolysis reactor and a reducing device, and the dissolving device is a reactor with a heating device or a heating device and an electrolyzing device In the reactor, the purification device is an extraction tank or a reactor with a heating device and an electrolysis device, and the reduction device is a multi-stage push boat that is hydraulically and mechanically driven.
  • the extraction tank is preferably a countercurrent tank extractor.
  • the multi-stage push boat comprises three channel shells connected by a conveying pipeline to form an elongated passage, and an inlet and an outlet are arranged at both ends of the passage, and the three shells are arranged from the inlet to the outlet.
  • the upper end of the curtain is hingedly connected to the tube wall, and the lower end is a free end, and the regions are connected together to form a chamber through the chamber.
  • a tubular passage in which a plurality of material boats are placed in contact with each other, and at the inlet of the push boat is provided a material boat propulsion device capable of pushing the material boat into the tubular passage, a heating device and a temperature detecting and regulating device are provided in the sintering chamber for providing the required temperature to each chamber; and one or more air inlets are also provided in each of the chambers And the exhaust port; the cooling chamber is provided with a cold [3 device
  • An air inlet and an exhaust port are provided at the top of each regional cabinet, and in the pre-reduction area and the reduction area, the air inlet and the exhaust port are disposed at both ends of the area, and the air inlet and outlet are pushed and pushed The direction of travel is reversed; in each area, it is divided into a plurality of segmented spaces by a partition plate, and the partition plate is provided with a passage hole below the space for connecting the segments to pass the push boat; in the pre-reduction area and the reduction There are several segment spaces in the area, heaters are respectively arranged in each segment space to form different temperatures in different segment spaces, and several segment spaces are also arranged in the cooling region, in each segment space A cooler is respectively arranged in the middle; a gas inlet is arranged at the top of the middle casing in the first segment space of the cooling zone, and an exhaust port is arranged at the top of the middle casing of the last segment space.
  • the atomization hydrolysis reactor comprises a reaction tank comprising a heating device, a stirring device and a feeding device, the feeding device comprising a plurality of feeding nozzles, wherein some nozzles of the feeding nozzle are arranged in the reaction tank The upper part of the body, the other nozzles of the nozzle are arranged in the middle or the lower part of the reaction tank body;
  • the recycling technology provided by the invention provides a method for producing ultrafine cobalt powder by effectively dissolving cobalt, cobalt and impurities Separate purification processes such as chemical precipitation, electrochemical precipitation, and secondary extraction processes, as well as ultra-fine cobalt powders can be efficiently produced from various cobalt-containing wastes by atomization hydrolysis processes and their specific process conditions and blasting reduction processes.
  • the core of the invention is a depurcation and purification technology of secondary cobalt-containing waste, a precursor of hydrolyzed deposition of a synthetic cobalt compound, and then blasting thermal reduction at a plurality of temperatures to form ultrafine cobalt powder.
  • the use of atomized hydrolysis deposition can fundamentally eliminate the deposition of colloidal substances and maintain a stable crystal growth environment, and thus, crystals having a specific shape and particle diameter can be synthesized.
  • the invention implements atomized hydrolysis deposition by means of pressurized spraying and a stable pH process, and the synthesized oxide precursor is uniformly distributed under a specific shape, thereby performing blasting thermal reduction at a plurality of stages to form ultrafine cobalt powder of a specific shape.
  • the method can produce products of different particle sizes and shapes.
  • the special combination of the dissolved cobalt and the purification process of the invention makes the process suitable for the recovery treatment of various cobalt-containing secondary wastes having different compositions and contents.
  • the invention provides an ultra-fine cobalt powder material by using a unique technology such as atomization hydrolysis method and controlled atmosphere decomposition method, which is an environmentally friendly method, and can produce two kinds of ultrafine cobalt powders, which are spherical and needle-shaped, and have low cost and grain.
  • a unique technology such as atomization hydrolysis method and controlled atmosphere decomposition method, which is an environmentally friendly method, and can produce two kinds of ultrafine cobalt powders, which are spherical and needle-shaped, and have low cost and grain.
  • the characteristics of fine diameter and loose ratio can be used for the manufacture of power batteries and high-performance powder metallurgy products.
  • the particle size 0.1 ⁇ 1.5 ⁇ ⁇ , loose ratio: 0.3 ⁇ ; L0g/cm3, uniform distribution, good product consistency, can be used for power batteries, significantly improve the conductivity and high current of the battery Charge and discharge performance, prolong battery cycle life;
  • the transverse shaft diameter is 0.1 ⁇ 0.5 ⁇ ⁇ , and the longitudinal axis length is 0.5 ⁇ 10 um. It is used as the skeleton of superhard materials such as powder metallurgy chip cutters and hard alloys. The hardness and wear resistance of these powder metallurgical products are improved to completely replace the existing cobalt powder.
  • the cobalt powder prepared by the method of the invention has low carbon content, good product quality, low cost and excellent price. Performance ratio.
  • the method can well control the particle size and particle size of the product, and can stably produce ultrafine spherical and fibrous cobalt powder in batches.
  • the manufacturing device provided by the invention can provide a reliable guarantee for the above method, and the device has the advantages of simple structure and low manufacturing cost.
  • FIG. 1 is a flow chart of a process for preparing an ultrafine cobalt powder for manufacturing a power battery according to the present invention
  • FIG. 2 is a process flow chart for obtaining a crude cobalt salt solution by electrolytic solution of a cemented carbide scrap and preparing an ultrafine cobalt powder
  • Figure 3 is a schematic view showing the structure of the blasting reduction furnace.
  • the process flow of the manufacturing method of the ultra-fine spherical shape by the recycling technique of this embodiment is shown in Fig. 1.
  • the waste (secondary coarse cobalt) used in this embodiment is:
  • Scrap nickel-hydrogen/nickel-cadmium batteries and scraps and trimmings in the production process contain 1.0-15% cobalt; other components are Ni, Fe, Cd, Zn, etc., Ni: 10- 60%, Fe: 1-10%. Cd: 0.1-10%, Zn: 0.1-10%
  • Waste lithium ion battery and waste material and edge material in the production process contains 5-50% Co, other components are Ni, Li, graphite, Mn, etc., Ni: 1-20%, Li : 1-20%. Graphite: 1-30%, Mn: 1-30%
  • the crude cobalt sulfate or crude cobalt chloride solution obtained in step 1 is subjected to chemical pre-decontamination before entering the extraction: taking CoSO 4 solution for impurity removal as an example:
  • Heating In the state of heat preservation, the temperature is raised to 90-100 ° C;
  • Reaction precipitation Ca Mg Firstly, according to the content of Ca/Mg in CoS04 solution, the theoretical NaF solution is calculated. The actual excess is 100%--150%. Under stirring, slowly add NaF solution in 60 minutes. Maintain 90 ° C - 100 ° C, add the material, stir for 30-60 minutes, sample and analyze Ca / Mg.
  • Filtration Filter while hot, store the filtrate in the middle tank for cooling, and take one or more filtrations depending on the filtration.
  • the treated CoSO 4 solution must be a filtered clear solution that is pumped into the removal tank to remove 70% of the reaction tank.
  • Adding oxidizing agent Adding oxidizing agent H 2 0 2 , adding 1.2-2 times of the theoretical amount of iron removal, the reaction time is 1 hour.
  • the primary extractant (liquid) is a mixture containing 10% of P204 and 90% by volume of sulfonated kerosene; P204 is [di(2-ethylhexyl)phosphoric acid] (known abroad as D2EHPA);
  • the secondary extractant (liquid) is a mixture containing P50720%+sulfonated kerosene 80% by volume; P507[2-ethylhexylphosphoric acid*mono(2-ethylhexyl)ester] (known abroad as PC88A) ;
  • the stripping agent (liquid) is a pure aqueous solution containing sulfuric acid or hydrochloric acid 1.0-1.5 mol/L, in this embodiment, a pure aqueous solution containing sulfuric acid 1.3 mol/L;
  • Washing acid 1 is a solution containing sulfuric acid or hydrochloric acid of 0.30-1.0 mol/L, in this embodiment, a pure aqueous solution containing sulfuric acid 0.45 mol/L;
  • the acid washing 2 is a solution containing sulfuric acid or hydrochloric acid of 0.10-0.8 mol/L; in this embodiment, sulfuric acid is contained. 0.2 mol/L of pure aqueous solution;
  • the saponification base is a 2-10 mol/L sodium hydroxide solution; in this embodiment, a 5.5 mol/L sodium hydroxide solution;
  • Cobalt crude cobalt sulfate in (1), primary extractant prepared in (2), and saponification alkali are introduced into the extractor, wherein the flow rate of the primary extractant P204 is 2-151/min, for saponification
  • the flow rate of the base is 50-190 mol/min
  • the saponification rate is 60-65%
  • the flow rate of the crude cobalt sulfate solution or cobalt chloride is 2-151/min, fully stirred, statically layered, and once extracted at room temperature, the extraction is carried out.
  • the raffinate phase is reserved as a semi-refined cobalt sulphate or cobalt chloride solution, and the impurities enter the supported organic phase and enter the next stage of the scrubbing section.
  • the loaded organic phase is passed to the washing section, and the washing acid 1 prepared in (2) is added to the extractor at a flow rate of 50-150 ml/min, stirred thoroughly, statically layered, the organic phase is washed, and the extractant is further extracted.
  • the remaining cobalt is combined with the raffinate phase in the A step, that is, the semi-refined cobalt sulfate or cobalt chloride solution, and the process can further recover the cobalt ions remaining in the extracted phase;
  • the organic phase is loaded into the stripping section, and the stripping agent prepared in (2) is introduced.
  • the flow rate of the stripping solution is 100-500 ml/min, fully stirred, static phase separation, and the regenerated extractant is taken out, recycled, including
  • the stripping solution of impurities enters the sewage treatment system;
  • most of the impurity elements in the crude CoS0 4 or CoCl 2 can be removed: Fe, Cu, Zn, i, Cr, Cd, Ca, and the like.
  • most of the impurity elements in the crude CoS0 4 can be removed: Fe, Cd, Zn, Ca, Li, Mn.
  • a countercurrent box extractor is used in the extraction.
  • the flow rate of the crude cobalt sulfate solution depends on the capacity of the extractor and the amount of impurities. The above is only one process parameter proposed for a specific process.
  • the semi-refined cobalt sulfate solution obtained in one extraction, the secondary extractant prepared in (2), and the alkali for saponification are introduced into the extractor, wherein the flow rate of the cobalt sulfate solution is 0.8-15 1 /min, and the secondary extractant
  • the flow rate is 2-20 1/min
  • the flow rate of alkali for saponification is 200-1000 ml/min
  • the saponification rate is 20-40%, fully stirred, static layering, secondary extraction at normal temperature, cobalt enters the loaded organic phase
  • the raffinate is treated separately according to the nickel content.
  • the second extraction of the supported organic phase and the washing acid 2 prepared in (2) are passed to the washing section, the acid washing 2 flow rate is 0.1-3.01/min, the mixture is fully stirred, the stationary phase is separated, and the organic phase is loaded into the next stage.
  • the washing is combined with the raffinate in the step A, and some nickel elements are present in the raffinate;
  • the organic phase is loaded into the next-stage stripping section, and the stripping agent prepared in (2) is introduced.
  • the stripping agent flow rate is 100-200 mgl/min, fully stirred, static phase separation, and the regenerated extractant is taken out, and recycled.
  • the stripping solution is a refined cobalt solution.
  • sodium, nickel, magnesium, or the like in the semi-refined cobalt chloride or cobalt sulfate solution from which impurities have been removed can be removed.
  • the sodium in the semi-refined cobalt sulfate solution and a small amount of nickel can be removed in the secondary extraction.
  • a refined cobalt sulfate solution Into a refined cobalt sulfate solution;
  • the nickel-containing solution is separately treated according to the nickel content to recover nickel.
  • the nickel-containing concentration is low and can be discharged into the sewage system to recover nickel.
  • the nickel-containing concentration is high, and nickel can be recovered by chemical precipitation or extraction.
  • a countercurrent box type extractor is used.
  • a box type extractor is used, wherein the flow rate of the cobalt sulfate solution depends on the productivity of the extractor and the impurity content.
  • the saponification base is a pre-neutralization effect for balancing the acid (H+) generated during the extraction process; in the secondary extraction process, the extractant is prepared according to the requirements of the operation procedure, the crude cobalt solution (liquid solution), Washing cobalt solution (washing acid), stripping solution (reverse acid), alkali for saponification, three-stage operation of extracting and removing impurities, washing cobalt and stripping impurities according to the set flow rate.
  • the extraction impurity is extracted from the impurities in the crude cobalt solution into the extractant and the cobalt is left in the feed liquid (raffinate) to separate the cobalt and the impurities; the extractant after the extraction is washed in the cobalt-washing section.
  • the partially entrained cobalt in the extractant is eluted into the raffinate, and the impurities are not eluted to increase the recovery of Co; in the stripping section, the impurities extracted by the extractant are stripped (reacid) After stripping, it enters the stripping solution, and the effluent enters the sewage treatment system, and the extractant is regenerated and proceeds to the next extraction operation cycle, and the process is continuous.
  • Step 3 Atomization hydrolysis to prepare an oxide precursor, cobalt carbonate crystal
  • the refined ammonium sulfate solution was adjusted to a concentration of 85 g/L and a concentration of 225 g/L of ammonium bicarbonate solution was sprayed into the reaction vessel in a mist form.
  • the cobalt sulfate solution was controlled to be added in an amount of 200 L to 250 L/hr, and ammonium carbonate was measured by Co + 2 1.5 ⁇ 2. 0 times addition, mixing and stirring, stirring speed: 120r/min, reaction temperature: 55-60°C, reaction pH: 7. 5 ⁇ 0.
  • Reaction mode Hedging, that is, two feeding nozzles are arranged in the upper part and the lower part of the reactor, one nozzle nozzle is downward, and the lower nozzle nozzle is sprayed upward.
  • the cobalt liquid nozzle is on and the ammonium bicarbonate nozzle is below.
  • the atomization hydrolysis reactor comprises a reaction tank comprising a heating device, a stirring device and a feeding device, the feeding device comprising a plurality of feed nozzles, preferably some of the nozzles of the feed nozzles are provided
  • the feeding device comprising a plurality of feed nozzles, preferably some of the nozzles of the feed nozzles are provided
  • the upper part of the reaction tank body, and the nozzles of the other feed nozzles are arranged at the lower part of the reaction tank body;
  • the reactant is charged in a hedging manner, that is, a feed nozzle is provided in both the upper portion and the lower portion of the reactor, and one nozzle nozzle is downward and a nozzle nozzle is sprayed upward. Material.
  • the cobalt liquid is ejected downward from the upper nozzle, and the precipitant is ejected upward from the lower nozzle.
  • the very pure cobalt liquid and other reactants are fed back into the reactor by back-flushing to form a crystalline one-cobalt oxide precursor. Then, the precursor is dried for use.
  • Step 4 Preparation of spherical ultrafine cobalt powder by blasting thermal reduction
  • the cobalt carbonate crystal produced in the step 3 is introduced into the inlet of the hydraulic multi-stage push boat reduction furnace 1 (shown in Fig. 4), and the reduction furnace 1 includes three passage casings through which the conveying line is passed.
  • the connection constitutes an elongated passage, and an inlet and an outlet are provided at both ends of the passage, and a plurality of material boxes for holding the precursor are provided in the passage.
  • the three housings form three zones sequentially from the inlet to the outlet: for prepayment
  • the original area 11, the reduction area 12 and the cooling area 13, each area is separated by a stainless steel curtain 2, which is disposed in the connecting line between the respective areas and the outlet, the upper end of the hanging curtain 2 and the wall
  • the hinged connection has a lower end with a free end, and the push boat is sequentially pushed into the channel under the push of the electric push rod disposed outside the inlet end of the passage. With the push of the push boat behind, the front push boat is pushed forward.
  • An air inlet and an exhaust port are provided at a top of the casing of each area, and in the pre-reduction area and the reduction area, the helium port and the exhaust port are disposed at both ends of the area, and the inlet and outlet ports and the push boat are The direction of travel is reversed; in each area, it is divided into a plurality of segment spaces by a partition plate, and the partition plate is provided with a passage hole below the space for connecting the segments to pass the push boat; in the pre-reduction region 11 and There are 4 and 6 segment spaces in the reduction region 12, respectively, heaters are arranged in each segment space to form different temperatures in different segment spaces, and three segment spaces are provided in the cooling region liquid. Coolers are respectively arranged in each segment space; an air inlet is arranged at the top of the middle casing in the first segment space of the cooling zone, and an exhaust port is provided at the top in the middle of the last segment space.
  • a protective gas C0 2 is introduced into the pre-reduction zone 11, and the cobalt carbonate crystal is heated in the protective atmosphere at a heating temperature of 200-400 Torr, a heating time of 30 min, and then further incubated for 1 hour, in which the crystal is dehydrated and subjected to a reduction. Pre-reduction, causing carbon dioxide in the cobalt carbonate crystal to overflow, which can make the crystal pile loose, that is, so-called blasting;
  • the pre-reduced crystal continues to advance in the push boat, enters the reduction zone 12, passes sequentially in four compartments, the first space is a low temperature zone, and the latter three spaces are high temperature zones, which are further divided into a pre-low temperature zone. , high temperature zone and post low temperature zone, low temperature zone temperature 300-400 °C, high temperature zone temperature of 400-550 °C, the temperature of the former low temperature section and the post low temperature section is 30-50 °C lower than the temperature of the high temperature section.
  • the time spent in each space material is 10-60 min.
  • Such a heating method can make the crystal particles continue to be heated to a high temperature section for reduction after being heated more uniformly.
  • the reduction process is carried out in a reducing atmosphere in which hydrogen and nitrogen are formed.
  • the volume ratio of hydrogen to nitrogen is 3:1, and the liquid ammonia is decomposed to obtain a reducing gas: 2NH 3 ⁇ 33 ⁇ 4+N 2 .
  • the reduced material enters the cooling zone, and the crystal is cooled and inerted to room temperature in a protective atmosphere of C0 2 to prepare spherical ultrafine cobalt powder having a particle diameter of 0.1 to 2 ⁇ ⁇ .
  • the cooling zone is divided into three steps of temperature drop step separation.
  • the temperature difference of each step can be 40-80 °C, such as cooling to 460 °C for 40 minutes, continue to cool down to 400 ⁇ for 40 minutes, and finally cool to room temperature.
  • Multi-stage cooling can reduce the cooling rate of the crystal, avoid crystal agglomeration and reduce the performance of the crystal.
  • the recycling apparatus for producing ultrafine cobalt powder includes a dissolution apparatus, a purification apparatus, an atomization hydrolysis reactor, and a reduction apparatus, and the dissolution apparatus is a reactor with a heating device or a reactor with a heating device and an electrolysis device.
  • the purification device is an extraction tank or a reactor with a heating device and an electrolysis device
  • the reduction device is a multi-stage push boat that is hydraulically and mechanically driven as described above.
  • the extraction tank is a countercurrent tank extractor.
  • This embodiment provides a manufacturing method for producing an ultra-fine spherical shape by a circulation technique.
  • the waste used in this embodiment is:
  • Waste catalyst in the diamond industry such waste contains Co: 1-10%, Ni: 10-40%, Mn: 10-50%, trace Fe, A1, etc.
  • Hydrochloric acid is added to the secondary cobalt-containing scrap or cobalt slag at a concentration of 5-30%, (weight percent), and the amount added varies from 100% to 150% by weight (for waste)
  • the total amount of all metals is calculated to dissolve the chemical equivalent), and the cobalt in the waste forms soluble cobalt chloride CoCl 2 ;
  • the other components in the waste are also dissolved in hydrochloric acid to form soluble chloride, thereby forming coarse cobalt chloride.
  • a method of two-step precipitation of ammonium sulphate and ammonium sulphate, ammonium sulphate, ammonium bicarbonate and ammonia mixed solution is a method of two-step precipitation of ammonium sulphate and ammonium sulphate, ammonium sulphate, ammonium bicarbonate and ammonia mixed solution.
  • the concentration of metal ions in the solution was: Ni was 50 g/L, Co was 4 g/L, and Mn was 20 g/L.
  • ammonium sulfate (30% - 70% by weight) is added, ammonium sulfate is added in an amount of 1.1 times the amount of nickel in the solution, the reaction is stirred for 20 minutes, filtered, and the filtrate component is analyzed; sulfuric acid is added to the filtrate.
  • the total ammonia concentration in the reaction solution is controlled at about 4 mol/L, and the pH of the reaction end point is controlled to about 10 by adjusting the ratio of ammonium sulfate to ammonia. 8 ⁇ The amount of the amount of manganese is 0.8 times.
  • Nickel recovery rate q ni 99. 13 %
  • the purification process for directly replacing the extraction method by chemical precipitation is basically the same as the above process.
  • the purification process for the electrochemical deposition process is based on the type and deposition potential characteristics of one or more impurities in the crude cobalt salt solution, and a suitable current density is selected, using graphite as the anode and titanium plate as the cathode.
  • the crude cobalt salt solution is electrolyzed by an electrolytic solution, and impurities are precipitated on the cathode to be removed, thereby preparing a purified cobalt chloride or cobalt sulfate solution; the technique can be based on the type and content of impurities contained in the prior art. It is determined that the corresponding parameters are performed, which are well known to those skilled in the art, and therefore will not be described herein.
  • the crude cobalt chloride solution after the chemical purification in step 2 is subjected to secondary extraction to obtain a pure cobalt chloride solution; in the extraction process, Ni, Mn, Fe, A1, etc. in the solution can be removed by secondary extraction. Impurity element.
  • the primary extractant (liquid) is a mixture containing P204 8% and sulfonated kerosene 92% (volume ratio); the secondary extractant (liquid) is a mixture containing P50725%+ sulphurized kerosene 75% by volume.
  • the stripping agent (liquid) is a pure aqueous solution containing HC11.2-1.5mol/L; Washing acid 1 is a solution containing HC 10.35-1.0 mol/L;
  • Washing acid 2 is a solution containing 0.15-0.8 mol/L of sulfuric acid
  • the saponification base is a 3-8.5 mol/L sodium hydroxide solution
  • Step 3 Atomization hydrolysis to prepare an oxide precursor, cobalt oxalate crystal
  • Ammonium oxalate is dissolved in warm water (water temperature of 45-55 ⁇ ), and filtered to remove solid impurities in the solution, and then liquid ammonia is introduced into the oxalic acid solution to prepare a pH of 4.3-4.5, and the concentration is 130-150 g. /L of ammonium oxalate solution.
  • the purified cobalt chloride solution was adjusted to a concentration of 85 ⁇ 5 g / L (temperature of 25-28 ° C, pH of 0.7 ⁇ 0.1) and prepared to a concentration of 139 ⁇ 2 g / L (temperature of 65-70)
  • the ammonium oxalate solution of °C) was sprayed into the reaction vessel in a mist. Mixing and stirring, the stirring speed is 90-250 rev / min, the reaction temperature is between 50-52 ° C, the feeding speed is controlled so that the reaction time is 2 minutes - 5 minutes, and then the crystal is separated;
  • Oxalic acid is dissolved in warm water (water ⁇ at 45-65 ° C), and filtered to remove solid impurities in the solution, and then liquid ammonia is introduced into the oxalic acid solution to prepare a pH of 4.1-4.5, a concentration of 130 -150 g/L ammonium oxalate solution.
  • the needle-like cobalt oxalate can be produced by the above-described atomization hydrolysis.
  • Step 4 Preparation of ultrafine cobalt powder by blasting thermal reduction
  • the cobalt oxalate crystal prepared in the step 3 is reduced into ultrafine cobalt powder in a push boat as shown in FIG. 3, and is also subjected to three stages of preheating, heating and cooling.
  • a protective gas C0 2 is introduced , and the cobalt oxalate crystal is heated in the protective atmosphere at a heating temperature of 250-350 ° C, a heating time of 40 min, and then further incubated for 1 hour, in which the crystal is de- iceed.
  • pre-reduction to cause carbon dioxide in the cobalt oxalate crystal to overflow, which can make the crystal pile loose, that is, so-called blasting;
  • the pre-reduced crystals continue to advance in the push boat, enter the reduction zone, pass sequentially in four compartments, the temperature in the low temperature zone is 400 ° C, the temperature in the high temperature zone is 500-550 ⁇ , the temperature of the front low temperature section and the post low temperature section It is 30-50 °C lower than the temperature in the high temperature section.
  • the time spent in each space material is 40-60 min.
  • the reduction process is carried out in a reducing atmosphere in which hydrogen and nitrogen are formed, and the volume ratio of hydrogen to nitrogen is 3:1, and liquid ammonia is decomposed to obtain a reducing gas: 2NH 3 ⁇ 3H 2 + N 2 .
  • the reduced material enters the cooling zone, and the crystal is cooled and inerted to room temperature in a protective atmosphere of C0 2 to prepare an ultrafine cobalt powder having a particle diameter of 0.1 to 2 ⁇ m.
  • the cooling zone is divided into three steps of temperature drop step separation.
  • the temperature difference of each step can be 40-80 °C, such as cooling to 460 °C for 40 minutes, continue to cool down to 400 ⁇ for 40 minutes, and finally cool to room temperature.
  • Example 3 Example 3:
  • the secondary raw material used in this embodiment is a cemented carbide scrap, and the process flow chart is shown in Fig. 3, and the dissolution process uses electrolytic dissolution.
  • An electrolytic solution having a concentration of 1.5 - 5 gram equivalents per liter of hydrochloric acid was placed in an electrolytic cell, and an anode basket made of a polyvinyl chloride orifice plate was placed therein, and a cemented carbide scrap block was placed in the basket as an anode.
  • a conductive plate is inserted as a cathode in the electrolytic cell, which may be a graphite plate, preferably a titanium metal plate.
  • the cathode and anode are connected to a DC power source. 5-5 ⁇ / ⁇ , When it is in the process of electrolysis, the concentration of hydrochloric acid in the electrolytic cell is always maintained at 1. 5-5 gram / liter, during the electrolysis process, when the current is in the range of 1.5 - 4. 0V, the current density is 50-300 amps / m 2 When the concentration drops, hydrochloric acid is replenished in time.
  • the cemented carbide material contains a large amount of tungsten carbide.
  • the tungsten carbide In the electrolytically dissolved cobalt, the tungsten carbide is not dissolved, can be recovered, and is processed into tungsten carbide powder, which is reused for the production of the cemented carbide material.
  • a layer of tungsten carbide shell is formed on the surface of the cemented carbide, which causes the anode to be passivated. Therefore, the shelling should be carried out in time during the electrolysis process.
  • the hard alloy which forms the tungsten carbide shell can be placed in a ball mill to be etched and shelled, and the alloy artificially vibrating in the polyvinyl chloride basket at regular intervals also has the function of breaking the shell.
  • the raw material is a purified cobalt chloride or cobalt sulfate solution as prepared in the previous examples.
  • the purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/L, and a ammonium oxalate solution prepared to a concentration of 100-300 g/L and a pH of 4.3-4.5 is sprayed into the reaction vessel in a mist form, and mixed.
  • the reaction temperature is between 45-70 ° C
  • the flow rate during the reaction is: 35-45 L / min
  • 'reaction time is 2 minutes - 8 minutes
  • the precursor cobalt oxalate is separated Crystal.
  • the purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/l and a solution prepared to a concentration of 100-300 g/L is sprayed into the reaction vessel in a mist, the refined cobalt chloride or The cobalt sulfate solution is controlled to be added in an amount of 80 L to 300 L/hr, and ammonium carbonate is added in an amount of 1.1 to 2.0 times measured by Co + 2 , and the mixture is stirred.
  • the average reaction time is 1 to 5 hours, the reaction temperature is 50-70 ° C, and the pH is: 7.0-9, then the precursor cobalt carbonate crystals were separated.
  • the purified cobalt chloride or cobalt sulfate solution is adjusted to a concentration of 50-140 g/l and a NaOH solution prepared to a concentration of 15-35 % is sprayed into the reaction vessel in a mist form, mixed and stirred, and 98% concentration of NH is added.
  • 3 gas adjust the amount of NH 3 added so that the concentration of free Co 2+ is 0.5-100 mg / 1, preferably 10-15 mg / 1, the pH of the reaction solution is 8-11, the optimum value is 9.8-10.5;
  • the feed rate of the stabilized Co 2+ liquid is a value of 70-300 L/hr, such as 160 L/hr, and the dosing device such as a metering pump is used for the quantitative dosing.
  • the feed rate of the NaOH solution is matched with the control pH.
  • the reaction temperature is 40-65 ° C, the optimum value is 50-60 ° C; the stirring speed is 90-150 rpm, and the average crystal grain size of the control crystal is 3- 15 micron, the optimum particle size is 5-10 microns;
  • the reaction can be continuous, continuous feeding, continuous discharge, or intermittent, that is, one cycle of a reactor; whether continuous or intermittent
  • the reaction has an average reaction time of 2 to 50 hours, preferably 5 to 8 hours.
  • the pH of the reaction solution is 7-12, the optimum value is 8-9, the reaction temperature is 50-75 ° C, and the optimum value is 60-70 ° C, passing ⁇ 3 ⁇ H 2 O And / or NaOH added amount while maintaining the pH stability, the temperature is maintained during the reaction, the feed rate is stable, and the feed rate is also maintained constant by the dosing with a metering pump; the average
  • the manufacturing method of ultra-fine cobalt powder by this cycle technology the synthesis of cobalt compound precursor by secondary extraction, impurity purification, atomization hydrolysis deposition, and then blasting thermal reduction at multiple temperatures to efficiently make from cobalt-containing waste
  • Ultrafine cobalt powder having a particle diameter of 0.1 to 2 ⁇ ⁇ , using waste batteries and the like as raw materials, without waste water and exhaust gas in production, is environmentally friendly, and spherical/spherical and fibrous cobalt powder can be obtained by the method. It is suitable for the manufacture of power batteries and high-performance powder metallurgy products, and is beneficial to improve the quality and life of products.
  • the cobalt powder particles prepared by the method have uniform distribution, good product consistency, adjustable particle shape, particle size and looseness ratio, low carbon content and good product quality.
  • the apparatus used in the above method provided by the present invention has a simple structure, low manufacturing cost, and low investment.

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Abstract

L'invention concerne un procédé de production de poudre de cobalt superfine par circulation, consistant à synthétiser un précurseur composé de Co par double extraction et hydrolyse par atomisation, puis à soumettre le précurseur composé de Co à une explosion et une réduction thermique à des températures sectorielles pour obtenir de manière efficace une poudre de cobalt superfine de 0,1 à 2νm à partir d'un matériau résiduel contenant du cobalt. On utilise dans ledit procédé de production des batteries usées comme matériau de départ, et aucune eau résiduelle ni gaz d'échappement ne sont émis au cours du processus. La poudre de cobalt sphérique ou de type sphérique et fibreuse obtenue par ledit procédé est adaptée pour la fabrication de batteries d'alimentation et d'articles métallurgiques à base de poudre hautement efficaces, et permet d'augmenter la qualité et la durée de vie utile des produits. La poudre de cobalt obtenue selon l'invention présente une distribution de particules uniforme, une bonne consistance de produit, une forme de particule, une dimension ou une densité apparente réglables, une faible teneur en carbone et une bonne qualité de produit. L'invention concerne également l'appareil utilisé dans ledit procédé, présentant une structure simple et un coût réduit.
PCT/CN2005/002265 2005-12-21 2005-12-21 Procede de production de poudre de cobalt superfine par circulation et appareil WO2007071108A1 (fr)

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CN110899719A (zh) * 2018-09-14 2020-03-24 上海铁路通信有限公司 一种片层结构钴颗粒材料的制备方法
CN113292110A (zh) * 2020-02-24 2021-08-24 荆门市格林美新材料有限公司 一种超细且高度分散的球形碳酸钴的制备方法
CN113292110B (zh) * 2020-02-24 2023-08-15 荆门市格林美新材料有限公司 一种超细且高度分散的球形碳酸钴的制备方法
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