CN116081705A - Process for preparing cobalt oxide by cobalt-containing waste - Google Patents
Process for preparing cobalt oxide by cobalt-containing waste Download PDFInfo
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- CN116081705A CN116081705A CN202310290919.8A CN202310290919A CN116081705A CN 116081705 A CN116081705 A CN 116081705A CN 202310290919 A CN202310290919 A CN 202310290919A CN 116081705 A CN116081705 A CN 116081705A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
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- C01B32/949—Tungsten or molybdenum carbides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D9/00—Nitrates of sodium, potassium or alkali metals in general
- C01D9/06—Preparation with gaseous nitric acid or nitrogen oxides
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a process for preparing cobalt oxide by using cobalt-containing waste, which has the characteristics of high crushing efficiency and favorable leaching, and the prepared cobalt oxide has the advantages of high purity, densification of particle surfaces, large particle size and high density; a process for preparing cobalt oxide from cobalt-containing waste material, comprising the steps of: removing impurities, crushing, ball milling, separating and calcining; belonging to the technical field of cobalt oxide preparation technology.
Description
Technical Field
The invention belongs to the technical field of cobalt oxide preparation processes, and relates to a process for preparing cobalt oxide by using cobalt-containing waste.
Background
Currently, with the continuous development of society, industrial modernization is becoming more and more mature, and consumption of cemented carbide is becoming more and more great, and generally, cemented tungsten carbide (WC) scraps such as chips, wires, bolts, drill bits, etc. are disposable metal manufacturing tools containing about 70wt% of tungsten, 28wt% of high-priced metallic cobalt, etc., wherein the amounts of tungsten, cobalt, etc. vary according to the kind, production year, and form of cemented tungsten carbide (WC) scraps. However, since it is difficult to crush and leach and to realize industrial production, it is becoming more and more important to fully utilize limited tungsten resources and cobalt resources, and recycling of tungsten-cobalt alloy waste is becoming more and more practical.
The methods for recycling the waste of the tungsten carbide (WC) are various, and the acid leaching method belongs to one of the methods. The method for recycling the hard alloy by adopting the acid leaching method has the advantages of simple process, low cost, low energy consumption and the like, but the traditional acid leaching method has the problems of long reaction time and low efficiency, and is mainly characterized in that the internal binding force of the tungsten carbide (WC) waste is high, the structure is stable and is not easy to damage, and acid mist can be generated when hydrochloric acid is used as a leaching medium, so that the environment is polluted.
Chinese patent publication No. CN106244806B discloses a method of crushing waste of hard tungsten carbide by mixing waste of hard tungsten carbide (WC) with aluminum and then heating to a high temperature to simultaneously form intermetallic compounds, metal oxides or mixtures thereof from tungsten and cobalt contained in the waste of hard tungsten carbide (WC), preparing spongy intermetallic compounds, metal oxides or mixtures thereof, and then crushing the prepared spongy intermetallic compounds, metal oxides or mixtures thereof, in which, although aluminum is introduced into the alloy to shorten the time of the crushing process, the product is advantageous for leaching in combination with the acid leaching method, the process simultaneously introduces aluminum ions, requires recovery treatment of aluminum ions, and increases the recovery process.
Disclosure of Invention
The invention aims to provide a process for preparing cobalt oxide by using cobalt-containing waste, which has the characteristics of high crushing efficiency and contribution to leaching, and the prepared cobalt oxide has the advantages of high purity, densification of particle surfaces, large particle size and high density.
The aim of the invention can be achieved by the following technical scheme:
a process for preparing cobalt oxide from cobalt-containing waste material, comprising the steps of:
s1, removing impurities: immersing waste tungsten-cobalt alloy into clean, ultrasonic wave, stirring, immersing into clean water, drying to obtain clean raw materials, and washing away impurities such as sediment and oil entrained by the raw materials;
s2, crushing: placing clean raw materials into a crushing disc of a graphite crucible, heating, adding carbon black, regulating the total carbon amount of the clean raw materials, regulating pressure, starting a vacuum pump, cooling to room temperature after heat preservation, and performing reagent treatment and mechanical crushing to obtain a mixture; the carbon black is added, so that the bonding strength of the waste tungsten-cobalt alloy is quickly reduced in the state of overload carbon and is easy to crush, and the crushing efficiency can be greatly improved, the energy is saved and the cost is reduced by combining spraying concentrated nitric acid and a small amount of intermittent spraying in a spraying mode; in the process, the concentrated nitric acid can also remove greasy dirt and iron impurities in the alloy.
S3, ball milling: loading the crushed mixture into a ball mill for ball grinding, sieving the ball-milled mixed powder with a mesh sieve, and drying to obtain mixed powder;
s4, separating: adding dilute nitric acid, controlling the pH value, filtering after the reaction, adding carbonate solution into the filtered solution, filtering the precipitate, and washing the precipitate with deionized water to obtain cobalt carbonate slurry; when the pH value exceeds 4.5 after the dilute nitric acid is added, cobalt hydroxide precipitate is generated locally easily, cobalt loss can be caused during filtration, in addition, the dilute nitric acid can react with cobalt, and ferric iron impurity can be hydrolyzed to form precipitate for removal; after adding carbonate, the mixture can react with cobalt nitrate in a precipitation way to generate cobalt carbonate precipitate;
s5, calcining: drying and dehydrating the cobalt carbonate slurry, and calcining the dehydrated cobalt carbonate to obtain cobalt oxide; wherein, dehydration is carried out before calcination, which is favorable for the calcination.
As a preferable technical scheme of the invention, the concentration of the ammonium carbonate or ammonium bicarbonate solution is 180-230 g/L.
As a preferable technical scheme of the invention, in the step S2, the heating temperature is 1800-1900 ℃, the total carbon amount is 6.13-6.20%, the heat preservation time is 30min, and the pressure is regulated to be less than 1 pa.
As a preferable technical scheme of the invention, in the step S2, the reagent is treated by adopting concentrated nitric acid with the concentration of 6.5-8 mol/L to spray in the mechanical crushing process, and adopting a mode that mechanical crushing and concentrated nitric acid spraying are carried out simultaneously, the two procedures complement each other, so that the loss of a crushing cutter can be effectively reduced, the service life of the crushing cutter is prolonged, and the crushing efficiency is greatly improved.
As a preferable technical scheme of the invention, in the step S3, screening is carried out by using a 180-mesh sieve, and the drying condition is that the material is placed in a vacuum dryer for heating to evaporate the ball milling medium, and the ball milling medium is removed in a drying mode after screening, so that the purity of the material is effectively improved.
As a preferable technical scheme of the invention, in the step S4, the concentration of the dilute nitric acid is 4.5-5.5 mol/L, the pH value is controlled to be 3.5-4.5, the reaction time is 0.5-2 h, and the concentration of the carbonate solution is 180-230 g/L; the carbonate solution is one or two of ammonium carbonate and ammonium bicarbonate.
In the step S4, ammonia water and hydrogen peroxide are introduced into the filtered solution to remove ferrous ferric oxide; if ferrous iron is present in the alloy, it is removed as ferric iron precipitate by oxidation.
As a preferable technical scheme of the invention, in the step S4, waste gas generated by the reaction of adding the dilute nitric acid is pumped out to regulate NO 2 The ratio of NO is 0.9-1.1: 1, introducing the regulated waste gas into NaOH solution with the concentration of 1.8-2.2%, sealing for reaction, and introducing low-voltage direct current for electrolysis, wherein the waste gas comprises NO 2 And NO; in the electrolysis process, the generated hydrogen is led out, oxygen is left in the system as an oxidant, and the oxygen is very easy to oxidize NO into NO 2 O under alkaline demodulation 2 Sodium nitrite can be oxidized into sodium nitrate, and the sodium nitrate can be used for preparing nitric acid, fertilizers, medicines, gunpowder, explosives, fireworks, glass, pigments, matches, preserved foods, salted meat and the like, and is a reagent and chemical raw materials with wide application range; in addition, nitric acid can be prepared from nitrogen oxides by ammonia catalytic oxidation, and can be used for step S2 and step S4, so that recycling is realized.
As a preferred technical scheme of the invention, in the step S5, the drying temperature is at 60 ℃ for 2 hours, the calcining condition is at 180-450 ℃ for 30 minutes, and at 550-700 ℃ for 1 hour.
As a preferable technical scheme of the invention, adding dilute nitric acid, reacting, filtering to obtain tungsten carbide powder, washing with NaOH solution with the concentration of 1%, washing precipitate with deionized water at 70-80 ℃ for 3-4 times, heating, drying, ball milling, reducing in hydrogen atmosphere at 1000-1500 ℃, regulating carbon content after reduction, ball milling, and sieving to obtain finished WC powder, wherein the recovery rate of WC powder in the scheme of the invention is more than 96%.
The invention has the beneficial effects that:
(1) In the mechanical crushing process, concentrated nitric acid is adopted to spray and treat the waste tungsten-cobalt alloy, so that the binding force between the inner parts of the alloy is reduced; meanwhile, the waste tungsten-cobalt alloy subjected to mechanical crushing treatment by crushing equipment reduces the loss of a crushing cutter, concentrated nitric acid spraying treatment and mechanical crushing are performed in a reactor at the same time, so that the waste tungsten-cobalt alloy can be mutually promoted, and the intermolecular binding force of the waste tungsten-cobalt alloy subjected to reagent treatment is weakened, so that the waste tungsten-cobalt alloy is beneficial to crushing; conversely, the waste tungsten-cobalt alloy is reduced after crushing, which is beneficial to reagent treatment.
(2) In the generated exhaust gas, by adjusting the proportion of nitrogen oxides and absorbing with NaOH solution, compared with the common use of NaCO 3 Compared with ammonia water absorption, the absorption efficiency of absorbing nitrogen oxides by NaOH solution is higher, and the environmental pollution can be effectively reduced; the sodium nitrate product has wide application, realizes the recycling of waste gas, and has certain economic value.
(3) The method is characterized in that a 180-mesh sieve is used for sieving, so that small-particle precipitation is generated by reaction with dilute nitric acid, the small-particle cobalt carbonate powder is calcined after drying and dehydration, the calcination is more sufficient, in addition, the calcination mode adopts heating to a set temperature, the cobalt carbonate is decomposed and continuously and slowly generates gas, a channel is formed in the cobalt carbonate, and then the heating is continuously carried out, so that complete calcination is realized, the formation of the channel enables the calcination to be more sufficient, and the surface of the generated cobalt oxide particles is more compact, and has large particle size and high density.
In summary, the process for preparing the cobalt oxide by using the waste tungsten-cobalt alloy realizes cobalt oxide preparation, WC powder recovery and waste gas recovery, has the characteristics of high crushing efficiency, contribution to leaching, high resource utilization rate and low recovery cost, and has the advantages of high purity, particle surface densification, large particle size and high density.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
In the scheme of the invention, dilute nitric acid is added for reaction and filtration to obtain tungsten carbide powder, naOH solution with the concentration of 1% is used for washing, precipitation is washed for 4 times by deionized water with the temperature of 80 ℃, ball milling is carried out after heating and drying, reduction is carried out at the temperature of 1400 ℃ in hydrogen atmosphere, the carbon content is regulated after reduction, and the finished WC powder is obtained after ball milling and sieving.
Example 1
A process for preparing cobalt oxide from cobalt-containing waste material, the process comprising the steps of:
s1, removing impurities: immersing waste tungsten-cobalt alloy into clean, ultrasonic wave, stirring, immersing into clear water, and drying to obtain clean raw materials;
s2, crushing: placing clean raw materials in a crushing disc of a graphite crucible, heating to 1800 ℃, adding carbon black, regulating the total carbon content of the clean raw materials to be 6.15%, regulating the pressure to be less than 1pa, starting a vacuum pump, preserving heat for 30min, cooling to room temperature, spraying with concentrated nitric acid with the concentration of 7mol/L, and mechanically crushing to obtain a mixture;
s3, ball milling: loading the crushed mixture into a ball mill for ball grinding, sieving the ball-milled mixed powder with a 180-mesh sieve, and heating in a vacuum dryer to evaporate ball-milling media to obtain mixed powder;
s4, separating: adding dilute nitric acid with the concentration of 5mol/L, controlling the pH value to be 3.5, reacting for 2 hours, filtering, introducing ammonia water and hydrogen peroxide into the filtered solution to remove precipitate by ferric iron oxide, adding ammonium bicarbonate solution with the concentration of 210g/L into the solution after iron removal, filtering the precipitate, and washing the precipitate with deionized water to obtain cobalt carbonate slurry;
s5, calcining: drying the cobalt carbonate slurry at 60 ℃ for 2 hours for drying and dehydration, calcining the dehydrated cobalt carbonate at 180 ℃ for 30 minutes, and calcining at 550 ℃ for 1 hour to obtain cobalt oxide.
Example 2
A process for preparing cobalt oxide from cobalt-containing waste material, the process comprising the steps of:
s1, removing impurities: immersing waste tungsten-cobalt alloy into clean, ultrasonic wave, stirring, immersing into clear water, and drying to obtain clean raw materials;
s2, crushing: placing clean raw materials in a crushing disc of a graphite crucible, heating to 1800 ℃, adding carbon black, regulating the total carbon content of the clean raw materials to be 6.15%, regulating the pressure to be less than 1pa, starting a vacuum pump, preserving heat for 30min, cooling to room temperature, spraying with concentrated nitric acid with the concentration of 7mol/L, and mechanically crushing to obtain a mixture;
s3, ball milling: loading the crushed mixture into a ball mill for ball grinding, sieving the ball-milled mixed powder with a 180-mesh sieve, and heating in a vacuum dryer to evaporate ball-milling media to obtain mixed powder;
s4, separating: adding dilute nitric acid with the concentration of 5mol/L, controlling the pH value to be 4, filtering after reacting for 2 hours, introducing ammonia water and hydrogen peroxide into the filtered solution to oxidize ferrous iron and ferric iron to remove precipitate, adding ammonium bicarbonate solution with the concentration of 210g/L into the solution after iron removal, filtering the precipitate, and washing the precipitate with deionized water to obtain cobalt carbonate slurry;
s5, calcining: drying the cobalt carbonate slurry at 60 ℃ for 2 hours for drying and dehydration, calcining the dehydrated cobalt carbonate at 310 ℃ for 30 minutes, and calcining at 620 ℃ for 1 hour to obtain cobalt oxide.
Example 3
A process for preparing cobalt oxide from cobalt-containing waste material, the process comprising the steps of:
s1, removing impurities: immersing waste tungsten-cobalt alloy into clean, ultrasonic wave, stirring, immersing into clear water, and drying to obtain clean raw materials;
s2, crushing: placing clean raw materials in a crushing disc of a graphite crucible, heating to 1800 ℃, adding carbon black, regulating the total carbon content of the clean raw materials to be 6.15%, regulating the pressure to be less than 1pa, starting a vacuum pump, preserving heat for 30min, cooling to room temperature, spraying with concentrated nitric acid with the concentration of 7mol/L, and mechanically crushing to obtain a mixture;
s3, ball milling: loading the crushed mixture into a ball mill for ball grinding, sieving the ball-milled mixed powder with a 180-mesh sieve, and heating in a vacuum dryer to evaporate ball-milling media to obtain mixed powder;
s4, separating: adding dilute nitric acid with the concentration of 5mol/L, controlling the pH value to be 4.5, reacting for 2 hours, filtering, introducing ammonia water and hydrogen peroxide into the filtered solution to remove precipitate by ferric iron oxide, adding ammonium bicarbonate solution with the concentration of 210g/L into the solution after iron removal, filtering the precipitate, and washing the precipitate with deionized water to obtain cobalt carbonate slurry;
s5, calcining: drying the cobalt carbonate slurry at 60 ℃ for 2 hours for drying and dehydration, calcining the dehydrated cobalt carbonate at 450 ℃ for 30 minutes, and calcining at 700 ℃ for 1 hour to obtain cobalt oxide.
Comparative example 1
In comparison with example 2, the difference is that in step S2, crushing: placing clean raw materials into a crushing disc of a graphite crucible, heating to 1800 ℃, preserving heat for 30min, cooling to room temperature, and mechanically crushing to obtain a mixture; the rest preparation steps and parameters are the same.
Comparative example 2
In comparison with example 2, the difference is that in step S2, crushing: placing clean raw materials in a crushing disc of a graphite crucible, heating to 1800 ℃, preserving heat, adjusting the pressure to be less than 1pa, starting a vacuum pump, preserving heat for 30min, cooling to room temperature, spraying with concentrated nitric acid with the concentration of 7mol/L, and mechanically crushing to obtain a mixture; the rest preparation steps and parameters are the same.
Comparative example 3
In comparison with example 2, the difference is that in step S2, crushing: placing clean raw materials in a crushing disc of a graphite crucible, heating to 1800 ℃, adding carbon black, regulating the total carbon content of the clean raw materials to be 4%, regulating the pressure to be less than 1pa, starting a vacuum pump, preserving heat for 30min, cooling to room temperature, spraying with concentrated nitric acid with the concentration of 7mol/L, and mechanically crushing to obtain a mixture; the rest preparation steps and parameters are the same.
Comparative example 4
In comparison with example 2, the difference is that in step S2, crushing: placing clean raw materials into a crushing disc of a graphite crucible, heating to 1800 ℃, adding carbon black, regulating the total carbon content of the clean raw materials to be 6.15%, regulating the pressure to be less than 1pa, starting a vacuum pump, preserving heat for 30min, cooling to room temperature, and mechanically crushing to obtain a mixture; the rest preparation steps and parameters are the same.
The mechanical crushing times of examples 1 to 3 and comparative examples 1 to 4 were tested, and when the powder having a particle diameter of 10mm or less accounted for 95wt% of the total crushed product, the mechanical crushing was stopped to obtain the time for which the mechanical crushing was performed, and the test results thereof are shown in Table 1.
TABLE 1
As can be seen from Table 1, the strength of the waste tungsten-cobalt alloy can be reduced by increasing the total carbon amount and spraying concentrated nitric acid, so that the effect of easy crushing is achieved, the crushing efficiency is greatly improved, the service life of the crushing cutter is prolonged, the energy consumption is reduced, and the cost is saved.
Example 4
Step S4 of example 2 was carried out by adding dilute nitric acid to produce waste gas and pumping out to regulate NO 2 NO ratio of 0.9:1, introducing the regulated waste gas into NaOH solution with the concentration of 1.8%, performing sealing reaction, and introducing low-voltage direct current for electrolysis.
Example 5
Step S4 of example 2 was carried out by adding dilute nitric acid to produce waste gas and pumping out to regulate NO 2 NO ratio is 1:1, introducing the regulated waste gas into NaOH solution with the concentration of 2%, performing sealing reaction, and introducing low-voltage direct current for electrolysis.
Example 6
Step S4 of example 2 was carried out by adding dilute nitric acid to produce waste gas and pumping out to regulate NO 2 NO ratio of 1.1:1, the waste gas after adjustment is introduced into NaOH solution with the concentration of 2.2 percentSealing reaction, and electrolyzing by low-voltage direct current.
Comparative example 5
In comparison with example 5, the difference is that NO is regulated 2 NO ratio is 2: and 3, introducing the regulated waste gas into a NaOH solution with the concentration of 2%, performing a sealing reaction, and introducing low-voltage direct current to perform electrolysis.
Comparative example 6
In comparison with example 5, the difference is that NO is regulated 2 NO ratio is 3:2, introducing the regulated waste gas into NaOH solution with the concentration of 2%, performing sealing reaction, and introducing low-voltage direct current for electrolysis.
Comparative example 7
In comparison with example 5, the difference is that NO is regulated 2 NO ratio is 1:1, introducing the regulated waste gas into NaOH solution with the concentration of 3%, performing sealing reaction, and introducing low-voltage direct current for electrolysis.
Comparative example 8
In comparison with example 5, the difference is that NO is regulated 2 NO ratio is 1:1, introducing the regulated waste gas into NaOH solution with the concentration of 4%, performing sealing reaction, and introducing low-voltage direct current for electrolysis.
The nox exhaust gases produced in step S4 of examples 4 to 6 and comparative examples 5 to 8 were subjected to absorption tests, respectively, and the test results are shown in table 2.
TABLE 2
| Nitrogen oxide absorption rate | |
| Example 4 | 93.4％ |
| Example 5 | 95.8％ |
| Example 6 | 93.6％ |
| Comparative example 5 | 84.2％ |
| Comparative example 6 | 86.1％ |
| Comparative example 7 | 86.5％ |
| Comparative example 8 | 86.8％ |
As can be seen from Table 2, a part of NO was oxidized and excessive NO 2 React with water to generate nitric acid, and the nitric acid reacts with alkali to reduce OH ions and influence the absorption efficiency of nitrogen oxides; as the concentration of the NaOH solution increases, the absorption rate of the nitrogen oxide decreases, and after the OH ion reaches a certain concentration, increasing the concentration reduces the diffusion and solubility of the nitrogen oxide, so that the resistance of the liquid film increases, and the absorption effect of the nitrogen oxide is affected.
Comparative example 9
In comparison with example 2, the difference is that in step S4, the pH is controlled to 3.0; the rest preparation steps and parameters are the same.
Comparative example 10
In comparison with example 2, the difference is that in step S4, the pH is controlled to 2.0; the rest preparation steps and parameters are the same.
Comparative example 11
In comparison with example 2, the difference is that in step S4, the pH is controlled to be 5.0; the rest preparation steps and parameters are the same.
Comparative example 12
In comparison with example 2, the difference is that in step S4, the pH is controlled to 6.0; the rest preparation steps and parameters are the same.
Comparative example 13
In comparison with example 2, the difference is that in step S5, calcination: the cobalt carbonate slurry was calcined at 310 ℃ for 30min and at 620 ℃ for 1h to obtain cobalt oxide.
Comparative example 14
In comparison with example 2, the difference is that in step S5, calcination: drying the cobalt carbonate slurry at 60 ℃ for 2 hours for drying and dehydration, calcining the dehydrated cobalt carbonate at 120 ℃ for 30 minutes, and calcining at 620 ℃ for 1 hour to obtain cobalt oxide.
Comparative example 15
In comparison with example 2, the difference is that in step S5, calcination: drying the cobalt carbonate slurry at 60 ℃ for 2 hours for drying and dehydration, calcining the dehydrated cobalt carbonate at 310 ℃ for 30 minutes, and calcining at 800 ℃ for 1 hour to obtain cobalt oxide.
Cobalt recovery tests were performed on examples 1-3 and comparative examples 9-15, and the test results are shown in Table 3.
TABLE 3 Table 3
As can be seen from the test results in Table 3, in examples 1 to 3, when dilute nitric acid is added, cobalt hydroxide is partially formed when the pH value is too low or too high, and cobalt hydroxide and tungsten carbide are simultaneously filtered during the filtration, resulting in cobalt loss, compared with comparative examples 9 to 12; as is evident from examples 1-3 and comparative examples 13-15, the drying and dehydration step prior to calcination and the first stage calcination are advantageous for the formation of internal passages of cobalt carbonate, avoiding the generation of gas-entrained powder particles during calcination, resulting in cobalt loss.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. A process for preparing cobalt oxide from cobalt-containing waste material, the process comprising the steps of:
s1, removing impurities: immersing waste tungsten-cobalt alloy into clean, ultrasonic wave, stirring, immersing into clear water, and drying to obtain clean raw materials;
s2, crushing: placing clean raw materials into a crushing disc of a graphite crucible, heating, adding carbon black, regulating the total carbon amount of the clean raw materials, regulating pressure, starting a vacuum pump, cooling to room temperature after heat preservation, and performing reagent treatment and mechanical crushing to obtain a mixture;
s3, ball milling: loading the crushed mixture into a ball mill for ball grinding, sieving the ball-milled mixed powder with a mesh sieve, and drying to obtain mixed powder;
s4, separating: adding dilute nitric acid, controlling the pH value, filtering after the reaction, adding carbonate solution into the filtered solution, filtering the precipitate, and washing the precipitate with deionized water to obtain cobalt carbonate slurry;
s5, calcining: and drying and dehydrating the cobalt carbonate slurry, and calcining the dehydrated cobalt carbonate to obtain cobalt oxide.
2. A process for preparing cobalt oxide from cobalt-containing waste material according to claim 1, wherein: in the step S2, the heating temperature is 1800-1900 ℃, the total carbon amount is 6.13-6.20%, the heat preservation time is 30min, and the pressure is regulated to be less than 1 pa.
3. A process for preparing cobalt oxide from cobalt-containing waste material according to claim 1, wherein: in the step S2, the reagent is treated by spraying concentrated nitric acid with the concentration of 6.5-8 mol/L in the mechanical crushing process.
4. A process for preparing cobalt oxide from cobalt-containing waste material according to claim 1, wherein: in step S3, screening is carried out by using a 180-mesh sieve, and the drying condition is that the ball milling medium is evaporated by heating in a vacuum dryer.
5. A process for preparing cobalt oxide from cobalt-containing waste material according to claim 1, wherein: in the step S4, the concentration of the dilute nitric acid is 4.5-5.5 mol/L, the pH value is controlled to be 3.5-4.5, the reaction time is 0.5-2 h, and the concentration of the carbonate solution is 180-230 g/L.
6. A process for preparing cobalt oxide from cobalt-containing waste material according to claim 5, wherein: the carbonate solution is one or two of ammonium carbonate and ammonium bicarbonate.
7. A process for preparing cobalt oxide from cobalt-containing waste material according to claim 1, wherein: in the step S4, ammonia water and hydrogen peroxide are introduced into the filtered solution to remove ferrous ferric oxide.
8. A process for preparing cobalt oxide from cobalt-containing waste material according to claim 1, wherein: in step S4, the waste gas generated by the reaction of adding dilute nitric acid is pumped out to adjust NO 2 The ratio of NO is 0.9-1.1: 1, introducing the regulated waste gas into NaOH solution with the concentration of 1.8-2.2%, performing sealing reaction, and introducing low-voltage direct current for electrolysis.
9. A process for preparing cobalt oxide from cobalt-containing waste material according to claim 1, wherein: in step S5, the drying temperature is at 60 ℃ for 2 hours, the calcining condition is at 180-450 ℃ for 30 minutes, and the calcining temperature is at 550-700 ℃ for 1 hour.
10. A process for preparing cobalt oxide from cobalt-containing waste material according to claim 1, wherein: adding dilute nitric acid to react and filter to obtain tungsten carbide powder, washing with NaOH solution with the concentration of 1%, washing precipitate with deionized water with the concentration of 70-80 ℃ for 3-4 times, heating, drying, ball milling, reducing in hydrogen atmosphere at 1000-1500 ℃, regulating the carbon content after reduction, ball milling, and sieving to obtain the finished WC powder.
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| CN117003441A (en) * | 2023-09-18 | 2023-11-07 | 科立鑫(珠海)新能源有限公司 | Process for recovering cobalt and nickel from cobalt-containing wastewater |
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