CN116770080B - Method for producing high-purity cobalt carbonate by using cobalt-containing waste - Google Patents
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- 239000010941 cobalt Substances 0.000 title claims abstract description 77
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 77
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021446 cobalt carbonate Inorganic materials 0.000 title claims abstract description 57
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 106
- 239000002893 slag Substances 0.000 claims abstract description 76
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 73
- 239000000956 alloy Substances 0.000 claims abstract description 73
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 53
- 238000007664 blowing Methods 0.000 claims abstract description 29
- 238000002386 leaching Methods 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000000571 coke Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 41
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 229910001868 water Inorganic materials 0.000 claims description 35
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 31
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 31
- 235000011152 sodium sulphate Nutrition 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000007792 addition Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 13
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 13
- 239000001630 malic acid Substances 0.000 claims description 13
- 235000011090 malic acid Nutrition 0.000 claims description 13
- 238000003723 Smelting Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 238000005422 blasting Methods 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000009853 pyrometallurgy Methods 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910001004 magnetic alloy Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910000833 kovar Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The invention relates to a method for producing high-purity cobalt carbonate by using cobalt-containing waste, belonging to the technical field of valuable metal recovery. The method provided by the invention realizes the preparation of high-purity cobalt carbonate by melt blowing, secondary blowing, crushing acid leaching, separation and cobalt carbonate preparation, combines pyrometallurgy and wet regeneration, is suitable for the conditions of various cobalt-containing waste materials and large batch material quantity change, and has stronger adaptability in the treatment process; according to the invention, the alloy slag B is added under the condition that sodium carbonate and coke exist, so that on one hand, the introduction of impurities caused by the addition of a slag former is avoided, and on the other hand, the trapping effect of Ni and Co in secondary blowing is enhanced due to the existence of the sodium carbonate, the coke and the alloy slag B; in the invention, the addition of sodium carbonate in the step two not only promotes secondary converting, but also ensures that CO after acid leaching of the undegraded sodium carbonate 3 2‑ Formation of HCO in solution 3 ‑ The solution is kept stable, and the buffer effect is achieved.
Description
Technical Field
The invention belongs to the technical field of valuable metal recovery, and particularly relates to a method for producing high-purity cobalt carbonate by using cobalt-containing waste.
Background
China is a state of scarcity and consumption of cobalt resources, and a large amount of cobalt products need to be imported each year to meet the increasing demands. How to improve the situation of insufficient cobalt resources in China, reduce the import dependence degree of foreign cobalt products, and have important significance for the sustainable development of cobalt industry in China. Cobalt is an important strategic metal, is an important raw material for manufacturing high-temperature alloys, hard alloys, magnetic alloys, precise alloys and cobalt-containing compounds, and is widely used in the industries of aerospace, motor electric, machinery, chemical industry, ceramics, communication, batteries and the like. With the increasing consumption of cobalt, a large amount of cobalt-containing waste is also produced. The cobalt-containing waste is an important secondary resource, and the recovery of valuable elements contained in the cobalt-containing waste is of great significance. The cobalt-containing waste materials are various, mainly comprise waste superalloy, waste hard alloy, waste magnetic alloy, waste kovar alloy, waste catalyst, waste secondary battery material and the like, and usually also comprise valuable elements such as nickel, tungsten, molybdenum, vanadium, niobium, titanium, copper, zinc, aluminum and the like.
In the prior art, the recovery utilization rate of cobalt element is limited, and a large amount of cobalt element is still lost due to insufficient recovery.
Disclosure of Invention
The invention relates to a method for producing high-purity cobalt carbonate by using cobalt-containing waste, belonging to the technical field of valuable metal recovery. The method provided by the invention realizes the preparation of high-purity cobalt carbonate by melt blowing, secondary blowing, crushing acid leaching, separation and cobalt carbonate preparation, combines pyrometallurgy and wet regeneration, is suitable for the conditions of various cobalt-containing waste materials and large batch material quantity change, and has stronger adaptability in the treatment process; according to the invention, the alloy slag B is added under the condition that sodium carbonate and coke exist, so that on one hand, the introduction of impurities caused by the addition of a slag former is avoided, and on the other hand, the capturing effect of N i and Co in secondary blowing is enhanced due to the existence of the sodium carbonate, the coke and the alloy slag B; in the invention, the addition of sodium carbonate in the step two not only promotes secondary converting, but also ensures that CO after acid leaching of the undegraded sodium carbonate 3 2- Formation of HCO in solution 3 - The solution is kept stable, and the buffer effect is achieved.
The aim of the invention can be achieved by the following technical scheme:
a method for producing high-purity cobalt carbonate by using cobalt-containing waste, which comprises the following operation steps:
step one: melting and converting; melting cobalt-containing waste in a reaction furnace at 1400-1500 ℃, blowing, separating alloy slag A rich in iron and chromium, and water quenching to obtain alloy slag B rich in nickel and cobalt;
step two: secondary converting; adding sodium carbonate, coke and alloy slag B into alloy slag A, smelting in a converter, blasting for 3-5min, clarifying for 3-5min, discharging slag, blowing, separating alloy C and slag D, and merging slag D into alloy slag A for continuous smelting;
step three: crushing and pickling; mixing alloy slag B and alloy C, crushing, grinding to a particle size less than or equal to 0.1mm, and carrying out acid leaching on the ground alloy slag B and alloy C to obtain leaching liquid;
step four: separating; sequentially treating the leaching solution with hydrogen peroxide and sodium sulfate solution, copper extractant AD-100 and extractant P507 to obtain cobalt-containing solution;
step five: preparing cobalt carbonate: and adding sodium carbonate into the cobalt-containing solution, reacting to generate cobalt carbonate precipitate, filtering and drying to obtain the cobalt carbonate.
As a preferable mode of the invention, the parameters of the blowing in the first step are that the blowing amount is 12500-14500m 3 And/h, the wind pressure is 0.06-0.08MPa, the converting temperature is 1200-1250 ℃, the slag washing time is 3-5min, and the clarification time is 2-3min.
As a preferable scheme of the invention, the water quenching parameters in the first step are that the water pressure is 0.5-0.58MPa and the water quantity is 180-200m 3 /h。
As a preferable scheme of the invention, the addition amounts of the sodium carbonate, the coke and the alloy slag B in the second step are respectively 0.1-0.5%, 8-10% and 12-15% of the mass of the alloy slag A.
As a preferable scheme of the invention, the solvent used for acid leaching in the third step is malic acid, acetic acid and hydrochloric acid, the concentration of the hydrochloric acid is 10-13mol/L, the mass concentration of the acetic acid is 8-10%, and the mass concentration of the malic acid is 5-6%.
As a preferable scheme of the invention, a heat exchanger is arranged outside the reaction furnace in the melting step one, high-temperature gas generated by melting the cobalt-containing waste is replaced by low-temperature gas through the heat exchanger, and the heat of the heat exchanger is used for heating the hydrogen peroxide solution and the sodium sulfate solution in the step four in a water bath manner, so that the temperature of the hydrogen peroxide solution and the sodium sulfate solution is kept at 80-100 ℃.
As a preferred scheme of the present invention, the treatment with hydrogen peroxide and sodium sulfate solution in the fourth step comprises the following operations: adding hydrogen peroxide with volume fraction of 25-28% for reaction, and controlling H 2 O 2 The addition amount and Fe 2+ The molar ratio of (2) is 1.5-2; adding sodium sulfate into the solution when the temperature of the solution is raised to 80-100 ℃ after water bath, controlling Na + The concentration of (2) is 0.08-0.1mol/L, and the precipitate is filtered off.
As a preferable scheme of the invention, in the adding process of adding sodium sulfate into the solution in the step four, the pH value of the solution is regulated by adding 100g/L sodium carbonate solution, and the pH value is controlled to be 1.5-2.5.
As a preferable scheme of the invention, the adding method of the sodium carbonate in the step five is as follows: will be with Co 2+ Adding sodium carbonate with the molar ratio of 1.1-1.2:1 into cobalt-containing solution, then adding the sodium carbonate solution dropwise while stirring, and filtering out precipitate after the precipitate is completely precipitated to prepare the high-purity cobalt carbonate.
The invention has the beneficial effects that:
1. the invention provides a method for producing high-purity cobalt carbonate by using cobalt-containing waste, which realizes the preparation of the high-purity cobalt carbonate by smelting and converting, secondary converting, crushing and acid leaching, separating and preparing the cobalt carbonate, fuses pyrometallurgy and wet regeneration, is suitable for the conditions of various cobalt-containing waste materials and large batch material quantity change, and has stronger adaptability to the treatment process.
2. In the invention, sodium carbonate, coke and alloy slag B are added in the secondary blowing in the step two, and alloy slag B is added under the condition of existence of sodium carbonate and coke, so that on one hand, introduction of impurities caused by addition of a slag former is avoided, and on the other hand, the capturing effect of N i and Co in the secondary blowing is enhanced by existence of sodium carbonate, coke and alloy slag B.
3. In the invention, the solvents used in acid leaching are malic acid, acetic acid and hydrochloric acid, so that the leaching rate of valuable metals is enhanced and the loss of cobalt is reduced under the synergistic effect of the malic acid, the acetic acid and the hydrochloric acid; and nickel can not form complex anions in the solution, so that the cobalt-nickel high-efficiency separation can be realized.
4. In the invention, the addition of sodium carbonate in the second step not only promotes secondary converting, but also ensures that CO after acid leaching of the undegraded sodium carbonate 3 2- Formation of HCO in solution 3 - The solution is kept stable, and the buffer effect is achieved.
5. In the invention, firstly, sodium carbonate is mixed with cobalt-containing solution, excessive sodium carbonate ensures that cobalt ions in the reaction are completely converted into cobalt carbonate, and then, when the sodium carbonate solution is continuously added, a dropwise adding mode is adopted to the reaction solution, so that the reaction time is prolonged, and the reaction of the cobalt ions and carbonate radical is better promoted; with the increase of the sodium carbonate solution, the further precipitation of cobalt ions is promoted to be complete, the reaction balance is pushed to the forward direction, and more cobalt carbonate precipitates are generated; sodium carbonate is gradually consumed, and finally cobalt carbonate precipitation is fully separated out, and a higher yield is obtained.
6. In the invention, the heat generated by melting is collected through the heat exchanger and is used for the water bath of the reaction of the hydrogen peroxide solution and the sodium sulfate solution in the step four, and the heat of the heat exchanger is transferred into the water bath, so that the constant-temperature reaction and the heat utilization are realized, the energy is saved, the heat energy is fully utilized, and the resource waste is reduced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method for producing high-purity cobalt carbonate by using cobalt-containing waste, which comprises the following operation steps:
step one: melting and converting; melting cobalt-containing waste in a reaction furnace at 1400 ℃, then blowing and converting, separating alloy slag A rich in iron and chromium, and water quenching to obtain alloy slag B rich in nickel and cobalt;
the parameters of the blowing are that the blowing quantity is 12500m 3 And/h, the wind pressure is 0.06MPa, the converting temperature is 1200 ℃, the slag washing time is 3min, and the clarification time is 2min;
the water quenching parameters are that the water pressure is 0.5MPa, and the water quantity is 180m 3 /h。
Step two: secondary converting; adding sodium carbonate, coke and alloy slag B into the alloy slag A, wherein the addition amounts of the sodium carbonate, the coke and the alloy slag B are respectively 0.1%, 8% and 12% of the mass of the alloy slag A; smelting in a converter, blasting for 3min, clarifying for 3min, discharging slag, blowing, separating alloy C and slag D, and merging the slag D into alloy slag A for continuous smelting;
step three: crushing and pickling; mixing alloy slag B and alloy C, crushing, grinding to a particle size less than or equal to 0.1mm, and carrying out acid leaching on the ground alloy slag B and alloy C to obtain leaching liquid; the solvent used for acid leaching is malic acid, acetic acid and hydrochloric acid, the concentration of the hydrochloric acid is 10 mol/L, the mass concentration of the acetic acid is 8%, and the mass concentration of the malic acid is 5%.
Step four: separating; sequentially treating the leaching solution with hydrogen peroxide and sodium sulfate solution, copper extractant AD-100 and extractant P507 to obtain cobalt-containing solution;
the treatment with hydrogen peroxide and sodium sulfate solution comprises the following operations: adding hydrogen peroxide with volume fraction of 25% to react, and controlling H 2 O 2 The addition amount and Fe 2+ The molar ratio of (2) is 1.5; adding sodium sulfate into the solution when the temperature of the solution rises to 80 ℃ after water bath, and controlling Na + The concentration of (2) was 0.08 mol/L, and the precipitate was filtered off;
in the fourth step, the pH value of the solution is regulated by adding 100g/L sodium carbonate solution in the adding process of adding sodium sulfate into the solution, and the pH value is controlled to be 1.5-2.5.
And step one, a heat exchanger is arranged outside the reaction furnace in a melting way, high-temperature gas generated by melting the cobalt-containing waste is replaced by low-temperature gas through the heat exchanger, and the heat of the heat exchanger is used for heating the hydrogen peroxide solution and the sodium sulfate solution in the step four in a water bath way, so that the temperature of the hydrogen peroxide solution and the sodium sulfate solution is kept at 80 ℃.
Step five: preparing cobalt carbonate: adding sodium carbonate into cobalt-containing solution, adding the solution into water, reacting to generate cobalt carbonate precipitate, filtering and drying to obtain cobalt carbonate;
the adding method comprises the following operations: will be with Co 2+ Sodium carbonate with a molar ratio of 1.1:1 is added to the cobalt-containing solution, then the sodium carbonate solution is added dropwise with stirring, and after the precipitation is complete, the precipitate is filtered off.
In this example, the recovery rate of cobalt was 92.4%, and the purity of cobalt carbonate was 95.1%.
Example 2
A method for producing high-purity cobalt carbonate by using cobalt-containing waste, which comprises the following operation steps:
step one: melting and converting; melting cobalt-containing waste in a reaction furnace at 1450 ℃, then blowing and converting, separating alloy slag A rich in iron and chromium, and carrying out water quenching to obtain alloy slag B rich in nickel and cobalt;
the parameters of the blowing were the blowing quantity 13500m 3 And/h, the wind pressure is 0.07MPa, the converting temperature is 1225 ℃, the slag washing time is 4min, and the clarification time is 2.5min;
the water quenching parameters are that the water pressure is 0.54MPa and the water quantity is 190m 3 /h。
Step two: secondary converting; adding sodium carbonate, coke and alloy slag B into the alloy slag A, wherein the addition amounts of the sodium carbonate, the coke and the alloy slag B are respectively 0.3%, 9% and 13.5% of the mass of the alloy slag A; smelting in a converter, blasting for 4min, clarifying for 4min, discharging slag, blowing, separating alloy C and slag D, and merging the slag D into alloy slag A for continuous smelting;
step three: crushing and pickling; mixing alloy slag B and alloy C, crushing, grinding to a particle size less than or equal to 0.1mm, and carrying out acid leaching on the ground alloy slag B and alloy C to obtain leaching liquid; the solvent used for acid leaching is malic acid, acetic acid and hydrochloric acid, the concentration of the hydrochloric acid is 12 mol/L, the mass concentration of the acetic acid is 9%, and the mass concentration of the malic acid is 5.5%.
Step four: separating; sequentially treating the leaching solution with hydrogen peroxide and sodium sulfate solution, copper extractant AD-100 and extractant P507 to obtain cobalt-containing solution;
the treatment with hydrogen peroxide and sodium sulfate solution comprises the following operations: adding hydrogen peroxide with volume fraction of 26.5% to react, and controlling H 2 O 2 The addition amount and Fe 2+ The molar ratio of (2) is 1.8; adding sodium sulfate into the solution when the temperature of the solution rises to 90 ℃ after water bath, and controlling Na + At a concentration of 0.09 mol/L, and filtering off the precipitate;
in the fourth step, the pH value of the solution is regulated by adding 100g/L sodium carbonate solution in the adding process of adding sodium sulfate into the solution, and the pH value is controlled to be 1.5-2.5.
And step one, a heat exchanger is arranged outside the reaction furnace in a melting way, high-temperature gas generated by melting the cobalt-containing waste is replaced by low-temperature gas through the heat exchanger, and the heat of the heat exchanger is used for heating the hydrogen peroxide solution and the sodium sulfate solution in the step four in a water bath way, so that the temperature of the hydrogen peroxide solution and the sodium sulfate solution is kept at 90 ℃.
Step five: preparing cobalt carbonate: adding sodium carbonate into cobalt-containing solution, adding the solution into water, reacting to generate cobalt carbonate precipitate, filtering and drying to obtain cobalt carbonate;
the adding method comprises the following operations: will be with Co 2+ Sodium carbonate with a molar ratio of 1.15:1 is added to the cobalt-containing solution, then the sodium carbonate solution is added dropwise with stirring, and the precipitate is filtered off after the precipitation is complete.
In this example, the recovery rate of cobalt was 93.5%, and the purity of cobalt carbonate was 95.7%.
Example 3
A method for producing high-purity cobalt carbonate by using cobalt-containing waste, which comprises the following operation steps:
step one: melting and converting; melting cobalt-containing waste in a reaction furnace at 1500 ℃, then blowing and converting, separating alloy slag A rich in iron and chromium, and water quenching to obtain alloy slag B rich in nickel and cobalt;
the parameters of the blowing are that the blowing quantity is 14500m 3 And/h, the wind pressure is 0.08MPa, the converting temperature is 1250 ℃, the slag washing time is 5min, and the clarification time is 3min;
the water quenching parameters are that the water pressure is 0.58MPa and the water quantity is 200m 3 /h。
Step two: secondary converting; adding sodium carbonate, coke and alloy slag B into the alloy slag A, wherein the addition amounts of the sodium carbonate, the coke and the alloy slag B are respectively 0.5%, 10% and 15% of the mass of the alloy slag A; smelting in a converter, blasting for 5min, clarifying for 5min, discharging slag, blowing, separating alloy C and slag D, and merging the slag D into alloy slag A for continuous smelting;
step three: crushing and pickling; mixing alloy slag B and alloy C, crushing, grinding to a particle size less than or equal to 0.1mm, and carrying out acid leaching on the ground alloy slag B and alloy C to obtain leaching liquid; the solvent used for acid leaching is malic acid, acetic acid and hydrochloric acid, the concentration of the hydrochloric acid is 13mol/L, the mass concentration of the acetic acid is 10%, and the mass concentration of the malic acid is 6%.
Step four: separating; sequentially treating the leaching solution with hydrogen peroxide and sodium sulfate solution, copper extractant AD-100 and extractant P507 to obtain cobalt-containing solution;
the treatment with hydrogen peroxide and sodium sulfate solution comprises the following operations: adding hydrogen peroxide with volume fraction of 28% to react, and controlling H 2 O 2 The addition amount and Fe 2+ The molar ratio of (2); adding sodium sulfate into the solution when the temperature of the solution rises to 100 ℃ after water bath, and controlling Na + The concentration of (2) was 0.1mol/L, and the precipitate was filtered off;
in the fourth step, the pH value of the solution is regulated by adding 100g/L sodium carbonate solution in the adding process of adding sodium sulfate into the solution, and the pH value is controlled to be 1.5-2.5.
And step one, a heat exchanger is arranged outside the reaction furnace in a melting way, high-temperature gas generated by melting the cobalt-containing waste is replaced by low-temperature gas through the heat exchanger, and the heat of the heat exchanger is used for heating the hydrogen peroxide solution and the sodium sulfate solution in the step four in a water bath way, so that the temperature of the hydrogen peroxide solution and the sodium sulfate solution is kept at 100 ℃.
Step five: preparing cobalt carbonate: adding sodium carbonate into cobalt-containing solution, adding the solution into water, reacting to generate cobalt carbonate and sodium chloride precipitate, filtering and drying to obtain cobalt carbonate;
the adding method comprises the following operations: will be with Co 2+ Sodium carbonate with a molar ratio of 1.2:1 is added to the cobalt-containing solution, then the sodium carbonate solution is added dropwise with stirring, and the precipitate is filtered off after the precipitation is complete.
In this example, the recovery rate of cobalt was 93.8%, and the purity of cobalt carbonate was 96.4%.
Comparative example 1
A method for producing high-purity cobalt carbonate by using cobalt-containing waste material, compared with example 1, does not carry out secondary blowing.
In this comparative example, the recovery rate of cobalt was 86.7%, and the purity of cobalt carbonate was 95.3%.
Comparative example 2
In comparison with example 1, the method for producing high-purity cobalt carbonate by using the cobalt-containing waste material does not add alloy slag B in the secondary converting.
In this comparative example, the recovery rate of cobalt was 88.2%, and the purity of cobalt carbonate was 95.2%.
Comparative example 3
A method for producing high-purity cobalt carbonate by using cobalt-containing waste material, compared with example 1, sodium carbonate is not added in secondary blowing.
In this comparative example, the recovery rate of cobalt was 86.4%, and the purity of cobalt carbonate was 94.7%.
Comparative example 4
A method for producing high-purity cobalt carbonate by using cobalt-containing waste material is compared with example 1, and acetic acid is replaced by malic acid in pickle liquor.
In this comparative example, the recovery rate of cobalt was 89.6%, and the purity of cobalt carbonate was 95.8%.
Comparative example 5
In comparison with example 1, sodium carbonate is directly added in the fifth step, and no sodium carbonate solution is added dropwise.
In this comparative example, the recovery rate of cobalt was 94.0%, and the purity of cobalt carbonate was 92.3%.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (8)
1. A method for producing high purity cobalt carbonate from cobalt-containing waste material, the method comprising the following steps:
step one: melting and converting; melting cobalt-containing waste in a reaction furnace at 1400-1500 ℃, blowing, separating alloy slag A rich in iron and chromium, and water quenching to obtain alloy slag B rich in nickel and cobalt;
step two: secondary converting; adding sodium carbonate, coke and alloy slag B into alloy slag A, smelting in a converter, blasting for 3-5min, clarifying for 3-5min, discharging slag, blowing, separating alloy C and slag D, and merging slag D into alloy slag A for continuous smelting; the addition amounts of the sodium carbonate, the coke and the alloy slag B are respectively 0.1-0.5%, 8-10% and 12-15% of the mass of the alloy slag A;
step three: crushing and pickling; mixing alloy slag B and alloy C, crushing, grinding to a particle size less than or equal to 0.1mm, and carrying out acid leaching on the ground alloy slag B and alloy C to obtain leaching liquid;
step four: separating; sequentially treating the leaching solution with hydrogen peroxide and sodium sulfate solution, copper extractant AD-100 and extractant P507 to obtain cobalt-containing solution;
step five: preparing cobalt carbonate: and adding sodium carbonate into the cobalt-containing solution, reacting to generate cobalt carbonate precipitate, filtering and drying to obtain the cobalt carbonate.
2. A process for producing high purity cobalt carbonate from cobalt-containing waste material according to claim 1, wherein the parameters of the blowing in step one are blast volume 12500-14500m 3 And/h, the wind pressure is 0.06-0.08MPa, the converting temperature is 1200-1250 ℃, the slag washing time is 3-5min, and the clarification time is 2-3min.
3. The method for producing high-purity cobalt carbonate according to claim 1, wherein the water quenching parameters in the first step are water pressure of 0.5-0.58MPa and water amount of 180-200m 3 /h。
4. The method for producing high-purity cobalt carbonate by using cobalt-containing waste according to claim 1, wherein the solvent used for acid leaching in the third step is malic acid, acetic acid and hydrochloric acid, the concentration of the hydrochloric acid is 10-13mol/L, the mass concentration of the acetic acid is 8-10%, and the mass concentration of the malic acid is 5-6%.
5. The method for producing high-purity cobalt carbonate by using cobalt-containing waste according to claim 1, wherein in the first step, a heat exchanger is arranged outside the reaction furnace for replacing high-temperature gas generated by melting the cobalt-containing waste, the high-temperature gas is replaced by low-temperature gas through the heat exchanger, and the heat of the heat exchanger is used for heating the hydrogen peroxide solution and the sodium sulfate solution in the fourth step in a water bath, so that the temperature of the hydrogen peroxide solution and the sodium sulfate solution is kept between 80 ℃ and 100 ℃.
6. The method for producing high purity cobalt carbonate from cobalt-containing waste material according to claim 5, wherein said treating with hydrogen peroxide and sodium sulfate solution in step four comprises the following operations: adding hydrogen peroxide with volume fraction of 25-28% for reaction, and controlling H 2 O 2 The addition amount and Fe 2+ The molar ratio of (2) is 1.5-2; adding sodium sulfate into the solution when the temperature of the solution is raised to 80-100 ℃ after water bath, controlling Na + The concentration of (2) is 0.08-0.1mol/L, and the precipitate is filtered off.
7. The method for producing high-purity cobalt carbonate according to claim 6, wherein in the step four, the solution pH is adjusted to 1.5-2.5 by adding 100g/L sodium carbonate solution during the addition of sodium sulfate to the solution.
8. The method for producing high-purity cobalt carbonate by using cobalt-containing waste according to claim 1, wherein the sodium carbonate adding method in the fifth step is as follows: will be with Co 2+ Adding sodium carbonate with the molar ratio of 1.1-1.2:1 into cobalt-containing solution, then adding the sodium carbonate solution dropwise while stirring, and filtering out precipitate after the precipitate is completely precipitated to prepare the high-purity cobalt carbonate.
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| US3954448A (en) * | 1975-01-28 | 1976-05-04 | Sumitomo Metal Mining Co. Limited | Process for recovering cobalt, copper, iron, nickel and arsenic |
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