CN102560100A - Process for preparing high-purity superfine cobalt powder from copper-cobalt-iron alloy - Google Patents
Process for preparing high-purity superfine cobalt powder from copper-cobalt-iron alloy Download PDFInfo
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Abstract
The invention discloses process for preparing high-purity superfine cobalt powder from copper-cobalt-iron alloy, which is characterized in that the process comprises the following steps: (1) pulverizing the copper-cobalt-iron alloy into alloy powders; (2) pressurizing the alloy powders with inorganic acid for leaching; (3) adjusting the pH value with carbonate to extract impurities to remove iron and fluoride purified calcium and magnesium; (4) extracting, deeply purifying and cleaning to remove copper, manganese and zinc, to separate cobalt from nickel, and to return cobalt to the extracting solution to precipitate cobalt for preparation of cobalt carbonate; (5) calcining high-purity cobalt carbonate at a high temperature to produce cobalt oxide; and (6) reducing cobalt oxide with hydrogen to high-purity superfine cobalt powders. The beneficial effects of the process disclosed by the invention are as follows: the process is simple and easy to operate, the cost is low, the technical conditions are easy to control, the cobalt loss is small and the leaching rate is high. After several times of purification, the impurities can be completely removed to obtain high-purity superfine cobalt powders.
Description
Technical field
The invention belongs to the wet treatment method of copper ferrocobalt alloy material, relate to a kind of process method of utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder specifically
Background technology
The single cobalt ore of China is very rare, and the cobalt product generally is attached in other mineral, such as nickel minerals and other mineral aggregates.Cobalt generally all occurs as sub product when copper nickel pyrometallurgical smelting, and its output is little, and cost is high, so China every year all will be from a considerable amount of cobalt products of overseas import.Big for solving demand, the imbalance between supply and demand that output is few is fully to excavate the cobalt ore resource on the one hand, improves the cobalt smelting technology, is to make full use of the cobalt secondary resource on the other hand.
The secondary recovery of cobalt mainly concentrates on cobalt-base alloy, contains on cobalt battery material and the cobalt-containing catalyst.The method that reclaims cobalt-base alloy at present mainly contains pyrogenic process refining cobalt, wet method soaks cobalt and three kinds of cobalts are melted in electrolysis.It is few that directly pyrogenic process refining cobalt reclaims the cobalt report, and its major cause is that the cobalt-base alloy source is totally different, and single alloy source is few, and the different cobalt alloying constituent is different, constituent content is different, is not suitable for a large amount of meltings of pyrogenic process.Though the molten cobalt of electrolysis has the electrolytic various advantages of tradition, for the waste alloy not high for metal content, that impurity is many, the low and electrolytic parameter of electrolytic efficiency with alloying constituent form change bigger.Shortcomings such as it is more that wet method is soaked cobalt research, but for complicated component, constitutionally stable useless cobalt-base alloy, and the ubiquity leaching yield is low.
Cobalt powder is as the sticker of wimet in the cobalt product, and its granularity pattern, particle diameter and purity directly influence the quality of alloy, can not only obtain high-quality ultra-fine cemented carbide with super-fine cobalt powder, and can reduce the ball mill mixing time, reduces sintering temperature.The pattern general requirement of super-fine cobalt powder is spherical; Spheroidal particle has minimum porosity box relatively sliding frictional coefficient; Superior extendability and ductility when mixing with other materials, show good miscibility; This press forming to wimet plays a positive role, and is therefore more and more to the research of superfine spherical cobalt powder.
At present, be used for the super-fine cobalt powder working method and mainly contain the high-pressure water spray method, polyol reduction method, cobalt oxalate or powder blue, cobaltous oxide reduction method.(1) the high-pressure water spray method is meant that the High-Pressure Water that uses 5～50MPa smashes the method that the metal liquid stream that is in molten state is made metal-powder.Its shortcoming is that the cobalt powder that obtains is the potato shape, and granularity is relatively large; (2) polyvalent alcohol cobalt reduction method is that solid chemical compound with cobalt floats over a kind of liquid polyol or do not add in the mixture of polyvalent alcohol of water; Suspensoid is heated to certain temperature; In the time of in most of the cases can reaching the liquid phase boiling point, these precursor compounds are reduced and obtain the thin cobalt powder of metal.Its shortcoming is to produce the product instability, is difficult for realizing suitability for industrialized production.
Summary of the invention
In order to overcome the deficiency that above technology exists, the present invention provides a kind of process method of utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder.
The technical scheme that the present invention adopted is: utilize copper ferrocobalt alloy to prepare the method for high pure and ultra-fine cobalt powder, it is characterized in that: concrete process step is following:
(1) copper ferrocobalt alloy is atomized into powdered alloy
Is to carry out fusion under 1200～1450 ℃ with copper ferrocobalt alloy in temperature, adds fusing assistant in the melting process, adopts rotating-disk centrifugal atomizing method to be atomized into 80～200 purpose powdered alloys;
(2) pressurization of powdered alloy mineral acid is leached
In pressurized reactor, add entry and powdered alloy, add 400～450 milliliters of mineral acids, it is 65～95 ℃ that temperature of reaction is leached in control; Feed industrial oxygen; The control reaction pressure is 0.4～1.2MPa, reacts to add oxygenant after 1 hour, filters through 2 hours postcooling; The output leach liquor is subsequent use, and leached mud reclaims;
(3) carbonate transfers pH extraction deironing, fluorochemical to purify impurity such as calcium magnesium
Change leach liquor over to reaction kettle, add carbonate adjustment pH value to 3～4, filter back solution and get into extraction system; Adopt the deironing of extraction agent MIBK, its organic phase: water=2～4: 1, liquid adds reaction kettle after the deironing of extraction deironing; Be heated to 80 ℃～100 ℃ under the normal pressure, add fluorochemical calcium-magnesium removing impurity, its consumption is 3～12 times of calcium magnesium total content; Adition process has been reacted after-filtration and has been removed calcium magnesium addition, filtrate for later use with ammonium hydrogencarbonate adjustment pH value to 4.0;
(4) extraction degree of depth purifying copper removal MnZn and cobalt nickel separation, cobalt return the heavy cobalt of collection liquid and prepare cobaltous carbonate
Filtrating is sent to extraction box and is produced copper sulfate through N902 (2-hydroxyl-5-nonyl benzene formoxime) copper extraction system extracting copper, and C272 [two (2,4; The 4-trimethylammonium) amyl group phosphoric acid] copper removal MnZn iron and the separation of cobalt nickel; The reextraction of carrying out cobalt liquor with hydrochloric acid obtains cobalt chloride solution, adds little additive, then cobalt chloride solution is precipitated with the cobaltous carbonate form with precipitation agent; Filter and wash and obtain filter cake; Filtrating terminal point control cobalt contents is 0.1～0.3g/l, and filter cake is 70～110 ℃ of following vacuum-dryings in temperature, obtains cobaltous carbonate;
(5) high-purity cobaltous carbonate generates cobaltous oxide through high-temperature calcination
The cobaltous carbonate that oven dry is obtained is broken, in calcining temperature is 350～580 ℃ calcining furnace, calcine the generation cobaltous oxide behind the screening powdering;
(6) cobaltous oxide employing hydrogen reducing is a super-fine cobalt powder.
Cobaltous oxide is used hydrogen reducing in reduction furnace, obtain the high pure and ultra-fine cobalt powder, its cobalt contents is greater than 99.5%, and less than 100%, FSSS (Fei Shi) granularity reaches 0.65～1.0 μ m.
Said fusing assistant is aluminum oxide, silicon-dioxide, Calucium Silicate powder or fluorite; Said mineral acid is sulfuric acid or nitric acid, and oxygenant is VAL-DROP, potassium permanganate, ydrogen peroxide 50, chlorine or oxygen; Said carbonate is yellow soda ash or ammonium hydrogencarbonate, and fluorochemical is Sodium Fluoride or hydrogen fluoride ammonia; Said additive is ammoniacal liquor or ammonium chloride, and said precipitation agent is ammonium hydrogencarbonate or yellow soda ash.
The invention has the beneficial effects as follows: one of which, technology is simple, be convenient to operation, technical qualification are easy to control, low production cost; Its two, the cobalt leaching yield is high, lose for a short time, reaches the effect of impurity such as removing iron, calcium magnesium, copper MnZn fully through purification repeatedly, valuable metals such as recyclable copper cut down the consumption of energy; Its three, can obtain the high pure and ultra-fine cobalt powder, its cobalt contents is greater than 99.5%, less than 100%, the FSSS granularity reaches 0.65～1.0 μ m.
Embodiment
Below in conjunction with preferred embodiment the present invention is done further explain, but the present invention is not limited in following embodiment.
Embodiment 1
A kind of method of utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder, its concrete process step is following:
(1) copper ferrocobalt alloy is atomized into powdered alloy: in adding hot melting furnace, drop into 50 kilograms of copper ferrocobalt alloy pieces, add aluminum oxide, be warmed up to 1200 ℃ of meltings after, through on rotating-disk high speed centrifugation powder by atomization device, being atomized into 80 purpose powdered alloys;
(2) pressurization of powdered alloy mineral acid is leached: in 50L stainless steel pressurized reactor, add 15 kilograms of 28 liters of entry and powdered alloys, its powdered alloy staple (%) is: Co:7.42, Fe:21.47; Cu:12.51, Mn:0.057, Ca:0.28; Mg:1.94, Ni:0.018 is warming up to 80 ℃ then; Feed industrial oxygen, control oxygen is pressed 0.2Mpa; Add (96%) 400 milliliter of industrial sulphuric acid after 30 minutes, be warming up to 65 ℃, feed industrial oxygen, the control reaction pressure is 0.4Mpa; React and add VAL-DROP after 1 hour, filter through 2 hours postcooling, 36 liters of output leach liquors are subsequent use, and its composition is (g/l): Co:28.6; Cu:21.74, Fe:68.24, Mg:3.85; Ni:0.25, output leached mud 4.8 kilograms (doing meter) reclaims, and contains Co:0.848%;
(3) carbonate transfers pH extraction deironing, fluorochemical to purify the calcium magnesium addition: change leach liquor over to reaction kettle, in leach liquor, add yellow soda ash adjustment pH value to 3 then, filter back solution and get into extraction system; Adopt the deironing of extraction agent MIBK, liquid adds reaction kettle after the deironing of extraction deironing, under normal pressure, is heated to 90 ℃; Add 1.5 kilograms of calcium-magnesium removing of Sodium Fluoride; Adition process constantly with ammonium hydrogencarbonate adjustment pH value to 4.0, has been reacted after-filtration and has been removed calcium magnesium addition, filtrate for later use;
(4) purification by liquid extraction purifies the copper removal MnZn and cobalt nickel separates, cobalt returns the heavy cobalt of collection liquid and prepares high-purity cobaltous carbonate:
Filtrating is sent to extraction box and is produced copper sulfate through N902 (2-hydroxyl-5-nonyl benzene formoxime) copper extraction system extracting copper, and C272 [two (2,4; The 4-trimethylammonium) amyl group phosphoric acid] copper removal MnZn iron and the separation of cobalt nickel; The reextraction of carrying out cobalt liquor with hydrochloric acid obtains cobalt chloride solution, adds less ammonia, then cobalt chloride solution is precipitated with the cobaltous carbonate form with ammonium hydrogencarbonate; Filter and wash and obtain filter cake; Filtrating terminal point control cobalt contents is 0.1～0.3g/l, and the filter cake of gained obtains 2.1 kilograms of cobaltous carbonates 70 ℃ of following vacuum-dryings; Its composition for (%) is: Co:48.05, Fe:0.002, Cu＜0.001, Zn＜0.001, Ca:0.005, Cd＜0.0001, chlorine root: 0.026;
(5) high-purity cobaltous carbonate becomes cobaltous oxide through high-temperature calcination: the cobaltous carbonate that oven dry is obtained is broken, in calcining furnace, calcine behind the screening powdering, and calcining temperature is 350 ℃, generates cobaltous oxide, and the cobaltous oxide that obtains pine is than being 0.2g/cm
3
(6) cobaltous oxide employing hydrogen reducing is the high pure and ultra-fine cobalt powder: cobaltous oxide is used hydrogen reducing in reduction furnace, obtain the high pure and ultra-fine cobalt powder, its cobalt contents reaches 99.55%, and the FSSS granularity reaches 0.65 μ m.
Embodiment 2
A kind of method of utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder, its concrete process step is following:
(1) copper ferrocobalt alloy is atomized into powdered alloy: in adding hot melting furnace, drop into 50 kilograms of copper ferrocobalt alloy pieces; Add solubility promoter silicon-dioxide; After being warmed up to 1300 ℃ of meltings, through on rotating-disk high speed centrifugation powder by atomization device, being atomized into 130 purpose powdered alloys;
(2) pressurization of powdered alloy mineral acid is leached: in 50L stainless steel pressurized reactor, add 15 kilograms of 28 liters of entry and powdered alloys, its powdered alloy staple (%) is: Co:7.42, Fe:21.47; Cu:12.51, Mn:0.057, Ca:0.28; Mg:1.94, Ni:0.018 is warming up to 80 ℃ then; Feed industrial oxygen, control oxygen is pressed 0.3Mpa; Add (96%) 430 milliliter of industrial sulphuric acid after 30 minutes, be warming up to 75 ℃, feed industrial oxygen, the control reaction pressure is 0.6Mpa; React and add potassium permanganate after 1 hour, filter through 2 hours postcooling, 36 liters of output leach liquors are subsequent use, and its composition is (g/l): Co:27.8; Cu:18.56, Fe:54.74, Mg:2.75; Ni:0.32, output leached mud 5.0 kilograms (doing meter) reclaims, and contains Co:0.794%;
(3) carbonate transfers pH extraction deironing, fluorochemical to purify the calcium magnesium addition: change leach liquor over to reaction kettle, in leach liquor, add yellow soda ash adjustment pH value to 3.5 then, filter back solution and get into extraction system; Adopt the deironing of extraction agent MIBK, liquid adds reaction kettle after the deironing of extraction deironing, under normal pressure, is heated to 90 ℃; Add 1.6 kilograms of calcium-magnesium removing of Sodium Fluoride; Adition process constantly with ammonium hydrogencarbonate adjustment pH value to 4.0, has been reacted after-filtration and has been removed calcium magnesium addition, filtrate for later use;
(4) purification by liquid extraction purifies the copper removal MnZn and cobalt nickel separates, cobalt returns the heavy cobalt of collection liquid and prepares high-purity cobaltous carbonate:
Filtrating is sent to extraction box and is produced copper sulfate through N902 copper extraction system extracting copper, and C272 copper removal MnZn iron and cobalt nickel separate, and the reextraction of carrying out cobalt liquor with hydrochloric acid obtains cobalt chloride solution; Add less ammonia; Then cobalt chloride solution is precipitated with the cobaltous carbonate form with ammonium hydrogencarbonate, filtration and washing obtain filter cake, and filtrating terminal point control cobalt contents is 0.1～0.3g/l; The filter cake of gained is 85 ℃ of following vacuum-dryings; Obtain 2.1 kilograms of cobaltous carbonates, its composition for (%) is: Co:48.25, Fe:0.002, Cu＜0.001, Zn＜0.001, Ca:0.004, Cd＜0.0001, chlorine root: 0.032;
(5) high-purity cobaltous carbonate becomes cobaltous oxide through high-temperature calcination: the cobaltous carbonate that oven dry is obtained is broken, in calcining furnace, calcine behind the screening powdering, and calcining temperature is 430 ℃, generates cobaltous oxide, and the cobaltous oxide that obtains pine is than being 0.23g/cm
3
(6) cobaltous oxide employing hydrogen reducing is the high pure and ultra-fine cobalt powder: cobaltous oxide is used hydrogen reducing in reduction furnace, obtain the high pure and ultra-fine cobalt powder, its cobalt contents reaches 99.67%, and FSSS (Fei Shi) granularity reaches 0.78 μ m.
Embodiment 3
A kind of method of utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder, its concrete process step is following:
(1) copper ferrocobalt alloy is atomized into powdered alloy: in adding hot melting furnace, drop into 50 kilograms of copper ferrocobalt alloy pieces, add the solubility promoter fluorite, be warmed up to 1400 ℃ of meltings after, through on rotating-disk high speed centrifugation powder by atomization device, being atomized into 180 purpose powdered alloys;
(2) pressurization of powdered alloy mineral acid is leached: in 50L stainless steel pressurized reactor, add 15 kilograms of 28 liters of entry and powdered alloys, its powdered alloy staple (%) is: Co:7.42, Fe:21.47; Cu:12.51, Mn:0.057, Ca:0.28; Mg:1.94, Ni:0.018 is warming up to 80 ℃ then; Feed industrial oxygen, control oxygen is pressed 0.4Mpa; Add (96%) 450 milliliter of industrial sulphuric acid after 30 minutes, be warming up to 85 ℃, feed industrial oxygen, the control reaction pressure is 0.8Mpa; React and add ydrogen peroxide 50 after 1 hour, filter through 2 hours postcooling, 34 liters of output leach liquors are subsequent use, and its composition is (g/l): Co:26.9; Cu:17.4, Fe:52.84, Mg:3.15; Ni:0.25, output leached mud 4.2 kilograms (doing meter) reclaims, and contains Co:0.827%;
(3) carbonate transfers pH extraction deironing, fluorochemical to purify the calcium magnesium addition: change leach liquor over to reaction kettle, in leach liquor, add yellow soda ash adjustment pH value to 4 then, filter back solution and get into extraction system; Adopt the deironing of extraction agent MIBK, liquid adds reaction kettle after the deironing of extraction deironing, under normal pressure, is heated to 90 ℃; Add 1.6 kilograms of calcium-magnesium removing of hydrogen fluoride ammonia; Adition process constantly with yellow soda ash adjustment pH value to 4.0, has been reacted after-filtration and has been removed calcium magnesium addition, filtrate for later use;
(4) purification by liquid extraction purifies the copper removal MnZn and cobalt nickel separates, cobalt returns the heavy cobalt of collection liquid and prepares high-purity cobaltous carbonate:
Filtrating is sent to extraction box and is produced copper sulfate through N902 copper extraction system extracting copper, and C272 copper removal MnZn iron and cobalt nickel separate, and the reextraction of carrying out cobalt liquor with hydrochloric acid obtains cobalt chloride solution; Add a small amount of ammonium chloride; Then cobalt chloride solution is precipitated with the cobaltous carbonate form with yellow soda ash, filtration and washing obtain filter cake, and filtrating terminal point control cobalt contents is 0.1～0.3g/l; The filter cake of gained is 95 ℃ of following vacuum-dryings; Obtain 2.0 kilograms of cobaltous carbonates, its composition for (%) is: Co:47.54, Fe:0.002, Cu＜0.001, Zn＜0.001, Ca:0.004, Cd＜0.0001, chlorine root: 0.032;
(5) high-purity cobaltous carbonate becomes cobaltous oxide through high-temperature calcination: the cobaltous carbonate that oven dry is obtained is broken, in calcining furnace, calcine behind the screening powdering, and calcining temperature is 500 ℃, generates cobaltous oxide, and the cobaltous oxide that obtains pine is than being 0.26g/cm
3
(6) cobaltous oxide employing hydrogen reducing is the high pure and ultra-fine cobalt powder: cobaltous oxide is used hydrogen reducing in reduction furnace, obtain the high pure and ultra-fine cobalt powder, its cobalt contents reaches 99.78%, and the FSSS granularity reaches 0.86 μ m.
Embodiment 4
A kind of method of utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder, its concrete process step is following:
(1) copper ferrocobalt alloy is atomized into powdered alloy: in adding hot melting furnace, drop into 50 kilograms of copper ferrocobalt alloy pieces, add the solubility promoter Calucium Silicate powder, be warmed up to 1450 ℃ of meltings after, through on rotating-disk high speed centrifugation powder by atomization device, being atomized into 200 purpose powdered alloys;
(2) pressurization of powdered alloy mineral acid is leached: in 50L stainless steel pressurized reactor, add 15 kilograms of 28 liters of entry and powdered alloys, its powdered alloy staple (%) is: Co:7.42, Fe:21.47; Cu:12.51, Mn:0.057, Ca:0.28; Mg:1.94, Ni:0.018 is warming up to 80 ℃ then; Feed industrial oxygen, control oxygen is pressed 0.5Mpa; Add (96%) 450 milliliter of industrial sulphuric acid after 30 minutes, be warming up to 95 ℃, feed industrial oxygen, the control reaction pressure is 1.OMpa; React and add chlorine after 1 hour, filter through 2 hours postcooling, 35 liters of output leach liquors are subsequent use, and its composition is (g/l): Co:27.4; Cu:18.5, Fe:58.62, Mg:3.25; Ni:0.25, output leached mud 4.2 kilograms (doing meter) reclaims, and contains Co:0.795%;
(3) carbonate transfers pH extraction deironing, fluorochemical to purify the calcium magnesium addition: change leach liquor over to reaction kettle, in leach liquor, add yellow soda ash adjustment pH value to 4 then, filter back solution and get into extraction system; Adopt the deironing of extraction agent MIBK, liquid adds reaction kettle after the deironing of extraction deironing, under normal pressure, is heated to 90 ℃; Add 1.7 kilograms of calcium-magnesium removing of hydrogen fluoride ammonia; Adition process constantly with yellow soda ash adjustment pH value to 4.0, has been reacted after-filtration and has been removed calcium magnesium addition, filtrate for later use;
(4) purification by liquid extraction purifies the copper removal MnZn and cobalt nickel separates, cobalt returns the heavy cobalt of collection liquid and prepares high-purity cobaltous carbonate:
Filtrating is sent to extraction box and is produced copper sulfate through N902 copper extraction system extracting copper, and C272 copper removal MnZn iron and cobalt nickel separate, and the reextraction of carrying out cobalt liquor with hydrochloric acid obtains cobalt chloride solution; Add a small amount of ammonium chloride; Then cobalt chloride solution is precipitated with the cobaltous carbonate form with yellow soda ash, filtration and washing obtain filter cake, and filtrating terminal point control cobalt contents is 0.1～0.3g/l; The filter cake of gained is 95 ℃ of following vacuum-dryings; Obtain 2.2 kilograms of cobaltous carbonates, its composition for (%) is: Co:48.54, Fe:0.002, Cu＜0.001, Zn＜0.001, Ca:0.004, Cd＜0.0001, chlorine root: 0.032;
(5) high-purity cobaltous carbonate becomes cobaltous oxide through high-temperature calcination: the cobaltous carbonate that oven dry is obtained is broken, in calcining furnace, calcine behind the screening powdering, and calcining temperature is 580 ℃, generates cobaltous oxide, and the cobaltous oxide that obtains pine is than being 0.3g/cm
3
(6) cobaltous oxide employing hydrogen reducing is the high pure and ultra-fine cobalt powder: cobaltous oxide is used hydrogen reducing in reduction furnace, obtain the high pure and ultra-fine cobalt powder, its cobalt contents reaches 99.92%, and the FSSS granularity reaches 1.0 μ m.
In sum, can prepare the high pure and ultra-fine cobalt powder according to specific embodiment of the present invention, the high pure and ultra-fine cobalt powder product that above four embodiment is prepared gained carries out check and analysis, and its analytical results is seen table-1:
Table-1 high pure and ultra-fine cobalt powder product check and analysis results (%)
This shows that analyze from table-1 and learn that can prepare high pure and ultra-fine cobalt powder product according to specific embodiment of the present invention, its cobalt contents is greater than 99.5%, less than 100%, the FSSS granularity reaches 0.65～1.0 μ m.
Claims (6)
1. method of utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder, it is characterized in that: concrete process step is following:
(1) copper ferrocobalt alloy is atomized into powdered alloy
Is to carry out fusion under 1200～1450 ℃ with copper ferrocobalt alloy in temperature, adds fusing assistant in the melting process, adopts rotating-disk centrifugal atomizing method to be atomized into 80～200 purpose powdered alloys;
(2) pressurization of powdered alloy mineral acid is leached
In pressurized reactor, add entry and powdered alloy, be warming up to 80 ℃ then, feed industrial oxygen, control oxygen is pressed 0.2～0.5Mpa; Add 400～450 milliliters of mineral acids after 30 minutes, it is 65～95 ℃ that temperature of reaction is leached in control, feeds industrial oxygen; The control reaction pressure is 0.4～1.2MPa, reacts to add oxygenant after 1 hour, filters through 2 hours postcooling; The output leach liquor is subsequent use, and leached mud reclaims;
(3) carbonate transfers pH extraction deironing, fluorochemical to purify impurity such as calcium magnesium
Change leach liquor over to reaction kettle, add carbonate adjustment pH value to 3～4, filter back solution and get into extraction system; Adopt the deironing of extraction agent MIBK, liquid adds reaction kettle after the deironing of extraction deironing, is heated to 80 ℃～100 ℃ under the normal pressure; Add fluorochemical calcium-magnesium removing impurity, its consumption is 3～12 times of calcium magnesium total content, and adition process is with ammonium hydrogencarbonate adjustment pH value to 4.0; React after-filtration and removed calcium magnesium addition, filtrate for later use;
(4) extraction degree of depth purifying copper removal MnZn and cobalt nickel separation, cobalt return the heavy cobalt of collection liquid and prepare cobaltous carbonate
Filtrating is sent to extraction box and is produced copper sulfate through N902 copper extraction system extracting copper, and C272 copper removal MnZn iron and cobalt nickel separate, and the reextraction of carrying out cobalt liquor with hydrochloric acid obtains cobalt chloride solution; Add little additive; Then cobalt chloride solution is precipitated with the cobaltous carbonate form with precipitation agent, filtration and washing obtain filter cake, and filtrating terminal point control cobalt contents is 0.1～0.3g/l; The gained filter cake is 70～110 ℃ of following vacuum-dryings in temperature, obtains cobaltous carbonate;
(5) high-purity cobaltous carbonate generates cobaltous oxide through high-temperature calcination
The cobaltous carbonate that oven dry is obtained is broken, in calcining furnace, calcine the generation cobaltous oxide behind the screening powdering, and the control calcining temperature is 350～580 ℃, and the cobaltous oxide pine that obtains is than being 0.2～0.3g/cm
3
(6) cobaltous oxide employing hydrogen reducing is the high pure and ultra-fine cobalt powder
Cobaltous oxide is used hydrogen reducing in reduction furnace, obtain the high pure and ultra-fine cobalt powder, its cobalt contents is greater than 99.5%, and less than 100%, the FSSS granularity reaches 0.65～1.0 μ m.
2. the method for utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder according to claim 1 is characterized in that: said fusing assistant is aluminum oxide, silicon-dioxide, Calucium Silicate powder or fluorite.
3. the method for utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder according to claim 1 is characterized in that: said mineral acid is sulfuric acid or nitric acid, and oxygenant is VAL-DROP, potassium permanganate, ydrogen peroxide 50, chlorine or oxygen.
4. the method for utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder according to claim 1 is characterized in that: said carbonate is yellow soda ash or ammonium hydrogencarbonate, and fluorochemical is Sodium Fluoride or hydrogen fluoride ammonia.
5. the method for utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder according to claim 1 is characterized in that: said additive is ammoniacal liquor or ammonium chloride.
6. the method for utilizing copper ferrocobalt alloy to prepare the high pure and ultra-fine cobalt powder according to claim 1 is characterized in that: said precipitation agent is ammonium hydrogencarbonate or yellow soda ash.
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| CN107649689A (en) * | 2017-11-07 | 2018-02-02 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of super-fine cobalt powder |
| CN108002408A (en) * | 2016-10-31 | 2018-05-08 | 湖南金源新材料股份有限公司 | The method that battery waste prepares nickel sulfate, manganese, lithium, cobalt and cobaltosic oxide |
| CN109897957A (en) * | 2019-01-16 | 2019-06-18 | 中南大学 | A kind of method of valuable metal in Selective Separation cobalt ambrose alloy ferroalloy |
| JP2020147812A (en) * | 2019-03-14 | 2020-09-17 | Ｊｘ金属株式会社 | Processing method of copper iron cobalt alloy |
| CN112355317A (en) * | 2020-10-19 | 2021-02-12 | 衢州华友钴新材料有限公司 | Preparation method of superfine spherical cobalt powder |
| CN112371990A (en) * | 2020-10-22 | 2021-02-19 | 宁波互邦新材料有限公司 | Preparation process of ammoniation-free metal cobalt powder |
| CN112846209A (en) * | 2019-11-28 | 2021-05-28 | 荆门市格林美新材料有限公司 | Preparation method of rod-shaped cobalt powder |
| CN114959312A (en) * | 2022-06-23 | 2022-08-30 | 安徽华西稀有金属材料有限公司 | Method for eliminating ammonia gas in molybdenum concentrate oxygen pressure ammonia leaching gas phase |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1912152A (en) * | 2006-08-04 | 2007-02-14 | 湖南瑞翔新材料有限公司 | Method for extracting valence metal from copper ferrocobalt alloy |
| CN102321809A (en) * | 2011-10-13 | 2012-01-18 | 北京矿冶研究总院 | Method for extracting cobalt and copper from cobalt-copper-iron alloy |
-
2012
- 2012-02-21 CN CN2012100400202A patent/CN102560100B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1912152A (en) * | 2006-08-04 | 2007-02-14 | 湖南瑞翔新材料有限公司 | Method for extracting valence metal from copper ferrocobalt alloy |
| CN102321809A (en) * | 2011-10-13 | 2012-01-18 | 北京矿冶研究总院 | Method for extracting cobalt and copper from cobalt-copper-iron alloy |
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| CN103409773A (en) * | 2013-07-24 | 2013-11-27 | 浙江华友钴业股份有限公司 | Method for extracting copper and cobalt from copper-cobalt alloy |
| CN103409773B (en) * | 2013-07-24 | 2015-09-30 | 浙江华友钴业股份有限公司 | A kind of method extracting copper, cobalt from copper-cobalt alloy |
| CN104117686A (en) * | 2014-08-01 | 2014-10-29 | 宁波雁门新能源有限公司 | Cobalt powder preparation method |
| CN105002356B (en) * | 2015-08-17 | 2018-03-09 | 长沙矿冶研究院有限责任公司 | A kind of method that valuable metal is reclaimed in more metal alloys containing nickel cobalt |
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| CN105177284A (en) * | 2015-08-17 | 2015-12-23 | 长沙矿冶研究院有限责任公司 | Method for leaching and recycling valuable metal from cobalt-nickel-copper-manganese-iron alloy |
| CN105002356A (en) * | 2015-08-17 | 2015-10-28 | 长沙矿冶研究院有限责任公司 | Method for recovering valuable metals in nickel/cobalt-containing multi-metal alloy |
| CN108002408A (en) * | 2016-10-31 | 2018-05-08 | 湖南金源新材料股份有限公司 | The method that battery waste prepares nickel sulfate, manganese, lithium, cobalt and cobaltosic oxide |
| CN107243644A (en) * | 2017-05-25 | 2017-10-13 | 河南工业大学 | A kind of preparation method of the diamond tool copper-based prealloy powder of ultra-fine quaternary |
| CN107649689A (en) * | 2017-11-07 | 2018-02-02 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of super-fine cobalt powder |
| CN109897957A (en) * | 2019-01-16 | 2019-06-18 | 中南大学 | A kind of method of valuable metal in Selective Separation cobalt ambrose alloy ferroalloy |
| JP2020147812A (en) * | 2019-03-14 | 2020-09-17 | Ｊｘ金属株式会社 | Processing method of copper iron cobalt alloy |
| CN112846209A (en) * | 2019-11-28 | 2021-05-28 | 荆门市格林美新材料有限公司 | Preparation method of rod-shaped cobalt powder |
| CN112846209B (en) * | 2019-11-28 | 2023-06-09 | 荆门市格林美新材料有限公司 | Preparation method of rod-shaped cobalt powder |
| CN112355317A (en) * | 2020-10-19 | 2021-02-12 | 衢州华友钴新材料有限公司 | Preparation method of superfine spherical cobalt powder |
| CN112371990A (en) * | 2020-10-22 | 2021-02-19 | 宁波互邦新材料有限公司 | Preparation process of ammoniation-free metal cobalt powder |
| CN114959312A (en) * | 2022-06-23 | 2022-08-30 | 安徽华西稀有金属材料有限公司 | Method for eliminating ammonia gas in molybdenum concentrate oxygen pressure ammonia leaching gas phase |
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