CN116768284B - Environment-friendly process for producing cobalt sulfate - Google Patents
Environment-friendly process for producing cobalt sulfate Download PDFInfo
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- CN116768284B CN116768284B CN202310765241.4A CN202310765241A CN116768284B CN 116768284 B CN116768284 B CN 116768284B CN 202310765241 A CN202310765241 A CN 202310765241A CN 116768284 B CN116768284 B CN 116768284B
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- 229940044175 cobalt sulfate Drugs 0.000 title claims abstract description 122
- 229910000361 cobalt sulfate Inorganic materials 0.000 title claims abstract description 122
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 50
- 238000001704 evaporation Methods 0.000 claims abstract description 44
- 239000002893 slag Substances 0.000 claims abstract description 43
- 230000008020 evaporation Effects 0.000 claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 35
- 239000010941 cobalt Substances 0.000 claims abstract description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000006260 foam Substances 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 44
- 239000000706 filtrate Substances 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 37
- 238000001914 filtration Methods 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000498 cooling water Substances 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 8
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000012452 mother liquor Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a green environment-friendly process for producing cobalt sulfate, and belongs to the technical field of cobalt sulfate production. The invention removes and purifies the cobalt slag by acid leaching, strictly regulating pH value and multistage extraction technology, and the extracted raffinate is used for preparing corresponding products, so that valuable metals in the cobalt slag are fully recycled; on the basis, an evaporation concentrator, a crystallizer, a suspension tank, a cyclone and a foam catcher arranged in the evaporation concentrator and the crystallizer are matched; a suspension tank is arranged between the crystallization step and the classification and centrifugal dehydration steps and is used as a temporary storage and balance device of the cobalt sulfate mixed liquor; seed crystals are added into the crystallizer, so that the separation degree of crystals and solutes in mother liquor is improved; and meanwhile, corresponding technological parameters in the technological process are regulated and controlled to form a complete cobalt sulfate production process, and the process is environment-friendly, and has high comprehensive recovery rate and high purity of cobalt.
Description
Technical Field
The invention belongs to the technical field of cobalt sulfate production, and particularly relates to a green environment-friendly process for producing cobalt sulfate.
Background
Cobalt is a strategic metal resource for supporting the development of the high-tech field, and the byproduct cobalt slag in industrial production mainly comprises cobalt-containing converter slag, electric nickel cobalt slag, zinc smelting purification slag and the like, and the components of the byproduct cobalt slag are complex and generally contain valuable metals such as copper, zinc, nickel, manganese, chromium and the like, so that cobalt and other elements are required to be separated for preparing cobalt sulfate by extracting the cobalt in the cobalt slag.
At present, most manufacturers in China use imperfect technological methods for preparing cobalt sulfate at present, and the prepared cobalt sulfate product has the problems of low purity and low comprehensive recovery rate of cobalt. Therefore, it is especially necessary to research how to provide a process method for preparing cobalt sulfate, which can improve the purity of the cobalt sulfate product and the comprehensive recovery rate of cobalt, and once implemented, the process method can bring good economic benefit to enterprises and realize comprehensive utilization of resources.
Disclosure of Invention
The invention aims to provide a green and environment-friendly process for producing cobalt sulfate, which removes impurities from cobalt slag and purifies the cobalt slag by acid leaching, strictly regulating pH and multistage extraction technology, and the extracted raffinate is used for preparing corresponding products, so that valuable metals in the cobalt slag are fully recycled; on the basis, an evaporation concentrator, a crystallizer, a suspension tank, a cyclone and a foam catcher arranged in the evaporation concentrator and the crystallizer are matched; a suspension tank is arranged between the crystallization step and the classification and centrifugal dehydration steps and is used as a temporary storage and balance device of the cobalt sulfate mixed liquor; seed crystals are added into the crystallizer, so that the separation degree of crystals and solutes in mother liquor is improved; meanwhile, corresponding technological parameters in the technological process are regulated and controlled to form a complete cobalt sulfate production process, and the process is environment-friendly, high in comprehensive recovery rate and high in purity, and solves the problems of low purity of cobalt sulfate products and low comprehensive recovery rate of cobalt in the prior art of the cobalt sulfate production process.
The aim of the invention can be achieved by the following technical scheme:
an environment-friendly process for producing cobalt sulfate, which specifically comprises the following steps:
s1, slurrying cobalt slag, repeatedly carrying out acid leaching, adjusting pH, and filtering to obtain filtrate B and aluminum and iron filter residues;
s2, adding sodium carbonate into the filtrate B, uniformly stirring, and filtering to obtain filtrate C and filter residue A; adding dilute sulfuric acid into the filter residue A, uniformly mixing, filtering to obtain filtrate D and filter residue B, returning the filter residue B to the step S1 for acid leaching, carrying out primary extraction on the filtrate D by adopting a P204 extractant to obtain extract A and raffinate A, adding an N235 extractant into the raffinate A for secondary extraction to obtain extract B and raffinate B, and carrying out tertiary extraction on the raffinate B by adopting a P507 extractant to obtain extract C and cobalt sulfate solution; using the extract A, the extract B and the extract C as corresponding products;
s3, evaporating, concentrating and crystallizing the cobalt sulfate solution at a controlled temperature to obtain a cobalt sulfate mixed solution, and conveying the cobalt sulfate mixed solution to a suspension tank;
s4, grading particles of the cobalt sulfate mixed solution, and centrifugally dehydrating to obtain cobalt sulfate particles with different particle diameters;
s5, drying the qualified granular cobalt sulfate at a controlled temperature to obtain a finished cobalt sulfate product.
As a preferred embodiment of the present invention, step S1 specifically includes: adding desalted water into cobalt slag to carry out slurrying, adding concentrated sulfuric acid to carry out temperature-control acid leaching, filtering to obtain leaching liquid and leaching slag, carrying out repeated acid leaching and filtering steps on the leaching slag, mixing and discarding the finally obtained leaching slag, uniformly mixing the leaching liquid to obtain filtrate A, slowly adding sodium hydroxide into the filtrate A, uniformly stirring and filtering to obtain filtrate B, and aluminum and iron filter residues.
As a preferable scheme of the invention, the mass ratio of the cobalt slag to the desalted water is 1:3-3.5; the addition amount of the concentrated sulfuric acid is 55-70g/L; the temperature of the temperature-controlled acid leaching is 75-80 ℃ and the time is 2-3h; the times of repeated acid leaching and filtering steps are 2-3 times; the sodium hydroxide was added in an amount up to ph=5 of the solution.
As a preferred scheme of the invention, the mass concentration of the sodium carbonate in the step S2 is 99%, and the adding amount of the sodium carbonate is that the pH of the solution is up to 9; the mass concentration of the dilute sulfuric acid is 20-30%, and the volume ratio of the filter residue A to the dilute sulfuric acid is 1:1.5-2.
As a preferable scheme of the invention, the volume ratio of the filtrate D to the P204 extractant in the step S2 is 1:0.8-1; the volume ratio of the raffinate A to the N235 extractant is 1:0.7-0.9; the volume ratio of the raffinate B to the P507 extractant is 1:0.6-0.8.
As a preferred embodiment of the present invention, step S3 specifically includes: concentrating the cobalt sulfate solution in an evaporation concentrator by temperature control evaporation to obtain concentrated solution, placing the concentrated solution in a crystallizer, introducing circulating cooling water for cooling, adding seed crystals during cooling, then standing for crystallization by temperature control to obtain cobalt sulfate mixed solution, and sending the cobalt sulfate mixed solution into a suspension tank;
the invention sets a suspending tank between crystallization, classification and centrifugal dehydration steps, which is used as a temporary storage and balance device of cobalt sulfate mixed liquor, and balances the flow and quality of the cobalt sulfate mixed liquor in the production process so as to ensure the stability and continuity of the follow-up centrifuge processing flow.
As a preferable scheme of the invention, the temperature of the temperature-controlled evaporation concentration is 100-110 ℃; the concentration by evaporation is to a degree of concentration to a specific gravity of 1320-1355kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The seed crystal is added when the cooling temperature is reduced to 40-45 ℃; the mass ratio of the cobalt sulfate solution to the seed crystal is 10:1-1.1; the temperature of the temperature-controlled standing crystallization is 30-35 ℃ and the time is 21-23h.
As a preferable scheme of the invention, in the step S3, foam traps are arranged in the evaporation concentrator and the crystallizer;
the foam catcher is arranged in the evaporation concentrator, so that the loss of cobalt sulfate caused by steam entrainment of the cobalt sulfate solution in the evaporation concentration is reduced; the foam catcher is arranged in the crystallizer, so that the loss of cobalt sulfate caused by entrainment of steam generated by flash evaporation of concentrated solution in the crystallizer can be reduced.
As a preferred embodiment of the present invention, step S4 specifically includes: delivering the cobalt sulfate mixed solution to a cyclone from the bottom of a temporary tank for grading and centrifugally dewatering particles to obtain large-particle cobalt sulfate, qualified-particle cobalt sulfate and small-particle cobalt sulfate, crushing the large-particle cobalt sulfate, returning the large-particle cobalt sulfate to an evaporation concentrator to serve as seed crystals, and directly returning the small-particle cobalt sulfate to the evaporation concentrator to serve as seed crystals.
As a preferable scheme of the invention, the temperature of the temperature-controlled drying in the step S5 is 160-190 ℃ and the time is 1-2h.
The invention has the beneficial effects that:
(1) The method has the advantages that the used reagent is simple, the cobalt slag is purified by mainly acid leaching, strictly regulating pH value and multistage extraction technology, and the extracted raffinate is used for preparing corresponding products, so that valuable metals in the cobalt slag are fully recycled; on the basis, an evaporation concentrator, a crystallizer, a suspension tank, a cyclone and a foam catcher arranged in the evaporation concentrator and the crystallizer are matched, and corresponding technological parameters in the technological process are regulated and controlled at the same time, so that a complete cobalt sulfate production process is formed.
(2) The invention sets a suspending tank between the crystallization step and the classification and centrifugal dehydration step as a temporary storage and balance device of the cobalt sulfate mixed liquor, and balances the flow and quality of the cobalt sulfate mixed liquor in the production process so as to ensure the stability and continuity of the follow-up centrifuge processing flow.
(3) The foam catcher is arranged in the evaporation concentrator, so that the loss of cobalt sulfate caused by steam entrainment of the cobalt sulfate solution in the evaporation concentration is reduced; the foam catcher is arranged in the crystallizer, so that the loss of cobalt sulfate caused by entrainment of steam generated by flash evaporation of concentrated solution in the crystallizer is reduced; the crystal seeds are added into the crystallizer to form larger and more regular crystals in a shorter time, so that impurities in the solution are eliminated, defects and non-uniformity in the crystals are reduced, and in addition, the crystal seeds are added to help improve the separation degree of the crystals and solutes in the mother solution, so that the purity of the product is improved.
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.
The cobalt slag used in the embodiment and the comparative example comprises, by mass, 5-24% of cobalt, 4-9% of aluminum, 0.7-1.2% of lithium, 0.1-0.2% of lead, 0.1-0.3% of cadmium, 1-2% of iron and 0.01-0.02% of arsenic.
Example 1
An environment-friendly process for producing cobalt sulfate, which specifically comprises the following steps:
s1, adding desalted water into cobalt slag to carry out slurrying, then adding concentrated sulfuric acid to carry out acid leaching for 2.5 hours at a temperature of 75 ℃, then filtering to obtain leaching liquid and leaching slag, repeatedly carrying out the steps of concentrated sulfuric acid leaching and filtering on the leaching slag for 2 times, mixing and discarding the finally obtained leaching slag, uniformly mixing the leaching liquid to obtain filtrate A, slowly adding sodium hydroxide into the filtrate A until the pH value of the solution is=5, uniformly stirring and filtering to obtain filtrate B, and aluminum and iron filter residues;
the mass ratio of the cobalt slag to the desalted water is 1:3; the adding amount of the concentrated sulfuric acid is 70g/L;
s2, adding sodium carbonate with the mass concentration of 99% into the filtrate B until the pH value of the solution is=9, uniformly stirring and filtering to obtain filtrate C and filter residue A; adding 25% dilute sulfuric acid into the filter residue A, uniformly mixing, filtering to obtain filtrate D and filter residue B, returning the filter residue B to the step S1 for acid leaching, extracting the filtrate D by adopting a P204 extractant for the first time to obtain an extract A and a raffinate A, adding an N235 extractant into the raffinate A for the second time to obtain an extract B and a raffinate B, and extracting the raffinate B by using a P507 extractant for the third time to obtain an extract C and a cobalt sulfate solution; using the extract A, the extract B and the extract C as corresponding products;
the volume ratio of the filter residue A to the dilute sulfuric acid is 1:2; the volume ratio of the filtrate D to the P204 extractant is 1:0.8; the volume ratio of the raffinate A to the N235 extractant is 1:0.8; the volume ratio of the raffinate B to the P507 extractant is 1:0.6;
s3, controlling the temperature of the cobalt sulfate solution in an evaporation concentrator provided with a foam catcher to be 100 ℃; evaporating and concentrating to specific gravity of 1320kg/m 3 Placing the concentrated solution in a crystallizer provided with a foam catcher, introducing circulating cooling water for cooling, adding seed crystals when the cooling temperature is reduced to 43 ℃, standing and crystallizing for 23 hours at the temperature of 35 ℃ to obtain cobalt sulfate mixed solution, and conveying the cobalt sulfate mixed solution into a suspension tank;
s4, delivering the cobalt sulfate mixed solution to a cyclone from the bottom of a temporary tank to carry out grading and centrifugal dehydration of particles to obtain large-particle cobalt sulfate, qualified-particle cobalt sulfate and small-particle cobalt sulfate, crushing the large-particle cobalt sulfate, returning the large-particle cobalt sulfate to an evaporation concentrator to serve as seed crystals, and directly returning the small-particle cobalt sulfate to the evaporation concentrator to serve as seed crystals;
s5, drying the qualified granular cobalt sulfate for 1h at the temperature of 160 ℃ to obtain a cobalt sulfate finished product.
Example 2
An environment-friendly process for producing cobalt sulfate, which specifically comprises the following steps:
s1, adding desalted water into cobalt slag to carry out slurrying, then adding concentrated sulfuric acid to carry out acid leaching for 2 hours at the temperature of 80 ℃, then filtering to obtain leaching liquid and leaching slag, repeatedly carrying out the steps of concentrated sulfuric acid leaching and filtering on the leaching slag for 3 times, mixing and discarding the finally obtained leaching slag, uniformly mixing the leaching liquid to obtain filtrate A, slowly adding sodium hydroxide into the filtrate A until the pH value of the solution is=5, uniformly stirring and filtering to obtain filtrate B and aluminum and iron filter residues;
the mass ratio of the cobalt slag to the desalted water is 3.5; the adding amount of the concentrated sulfuric acid is 55g/L;
s2, adding sodium carbonate with the mass concentration of 99% into the filtrate B until the pH value of the solution is=9, uniformly stirring and filtering to obtain filtrate C and filter residue A; adding dilute sulfuric acid with the mass concentration of 20% into the filter residue A, uniformly mixing, filtering to obtain filtrate D and filter residue B, returning the filter residue B to the step S1 for acid leaching, extracting the filtrate D for the first time by adopting a P204 extractant to obtain an extract A and a raffinate A, adding an N235 extractant into the raffinate A for the second time to obtain an extract B and a raffinate B, and extracting the raffinate B for the third time by using a P507 extractant to obtain an extract C and a cobalt sulfate solution; using the extract A, the extract B and the extract C as corresponding products;
the volume ratio of the filter residue A to the dilute sulfuric acid is 1:1.5; the volume ratio of the filtrate D to the P204 extractant is 1:1; the volume ratio of the raffinate A to the N235 extractant is 1:0.9; the volume ratio of the raffinate B to the P507 extractant is 1:0.8;
s3, controlling the temperature of the cobalt sulfate solution in an evaporation concentrator provided with a foam catcher to 105 ℃; evaporating and concentrating to give a specific gravity of 1355kg/m 3 Placing the concentrated solution in a crystallizer provided with a foam catcher, introducing circulating cooling water for cooling, adding seed crystals when the cooling temperature is reduced to 40 ℃, standing and crystallizing for 22 hours at the temperature of 30 ℃ to obtain cobalt sulfate mixed solution, and conveying the cobalt sulfate mixed solution into a suspension tank;
s4, delivering the cobalt sulfate mixed solution to a cyclone from the bottom of a temporary tank to carry out grading and centrifugal dehydration of particles to obtain large-particle cobalt sulfate, qualified-particle cobalt sulfate and small-particle cobalt sulfate, crushing the large-particle cobalt sulfate, returning the large-particle cobalt sulfate to an evaporation concentrator to serve as seed crystals, and directly returning the small-particle cobalt sulfate to the evaporation concentrator to serve as seed crystals;
s5, drying the qualified granular cobalt sulfate at 175 ℃ for 1.5 hours to obtain a cobalt sulfate finished product.
Example 3
An environment-friendly process for producing cobalt sulfate, which specifically comprises the following steps:
s1, adding desalted water into cobalt slag to carry out slurrying, then adding concentrated sulfuric acid to carry out acid leaching for 3 hours at the temperature of 78 ℃, then filtering to obtain leaching liquid and leaching slag, repeatedly carrying out the steps of concentrated sulfuric acid leaching and filtering on the leaching slag for 2 times, mixing and discarding the finally obtained leaching slag, uniformly mixing the leaching liquid to obtain filtrate A, slowly adding sodium hydroxide into the filtrate A until the pH value of the solution is=5, uniformly stirring and filtering to obtain filtrate B and aluminum and iron filter residues;
the mass ratio of the cobalt slag to the desalted water is 1:3.3; the adding amount of the concentrated sulfuric acid is 63g/L;
s2, adding sodium carbonate with the mass concentration of 99% into the filtrate B until the pH value of the solution is=9, uniformly stirring and filtering to obtain filtrate C and filter residue A; adding 30% dilute sulfuric acid into the filter residue A, uniformly mixing, filtering to obtain filtrate D and filter residue B, returning the filter residue B to the step S1 for acid leaching, extracting the filtrate D by adopting a P204 extractant for the first time to obtain an extract A and a raffinate A, adding an N235 extractant into the raffinate A for the second time to obtain an extract B and a raffinate B, and extracting the raffinate B by using a P507 extractant for the third time to obtain an extract C and a cobalt sulfate solution; using the extract A, the extract B and the extract C as corresponding products;
the volume ratio of the filter residue A to the dilute sulfuric acid is 1:1.8; the volume ratio of the filtrate D to the P204 extractant is 1:0.9; the volume ratio of the raffinate A to the N235 extractant is 1:0.7; the volume ratio of the raffinate B to the P507 extractant is 1:0.7;
s3, controlling the temperature of the cobalt sulfate solution in an evaporation concentrator provided with a foam catcher to be 110 ℃; evaporating and concentrating to a specific gravity of 1338kg/m 3 Placing the concentrated solution in a crystallizer provided with a foam catcher, introducing circulating cooling water for cooling, adding seed crystals when the cooling temperature is reduced to 45 ℃, standing and crystallizing for 21 hours at the temperature of 33 ℃ to obtain cobalt sulfate mixed solution, and conveying the cobalt sulfate mixed solution into a suspension tank;
s4, delivering the cobalt sulfate mixed solution to a cyclone from the bottom of a temporary tank to carry out grading and centrifugal dehydration of particles to obtain large-particle cobalt sulfate, qualified-particle cobalt sulfate and small-particle cobalt sulfate, crushing the large-particle cobalt sulfate, returning the large-particle cobalt sulfate to an evaporation concentrator to serve as seed crystals, and directly returning the small-particle cobalt sulfate to the evaporation concentrator to serve as seed crystals;
s5, drying the qualified granular cobalt sulfate for 2 hours at the temperature of 190 ℃ to obtain a cobalt sulfate finished product.
Comparative example 1
Compared with the embodiment 3, the difference is that the cobalt sulfate mixed solution obtained in the step S3 is directly sent to the cyclone in the step S4 for classifying particles and centrifugally dewatering, and the rest parameters and operation steps are the same.
Comparative example 2
Compared with example 3, the difference is that the foam catcher is not arranged in the evaporation concentrator in the step S3, and the rest parameters and operation steps are the same.
Comparative example 3
Compared with example 3, the difference is that the foam breaker is not arranged in the crystallizer in the step S3, and the rest parameters and operation steps are the same.
Comparative example 4
Compared with example 3, the difference is that no seed crystal is added in step S3, and the large-particle cobalt sulfate and the small-particle cobalt sulfate obtained in step S4 are not returned to the evaporation concentrator to serve as seed crystals, and the other parameters and operation steps are the same.
Test case
Cobalt recovery and purity tests were performed on the cobalt sulfate finished products prepared in examples 1 to 3 and comparative examples 1 to 4, and the results are shown in table 1.
TABLE 1
| Recovery (%) | Purity (%) | |
| Example 1 | 98.61 | 98.90 |
| Example 2 | 98.64 | 98.94 |
| Example 3 | 98.66 | 98.97 |
| Comparative example 1 | 88.32 | 95.05 |
| Comparative example 2 | 93.08 | 96.11 |
| Comparative example 3 | 93.13 | 95.18 |
| Comparative example 4 | 87.75 | 85.90 |
As can be seen from Table 1, the recovery and purity of the finished cobalt sulfate products obtained in examples 1-3 of the present invention are both relatively outstanding. The method is mainly characterized in that the cobalt slag is subjected to impurity removal and purification by acid leaching, strict adjustment of pH value and multistage extraction technology, and the extracted raffinate is used for preparing corresponding products, so that valuable metals in the cobalt slag are fully recycled; on the basis, an evaporation concentrator, a crystallizer, a suspension tank, a cyclone and a foam catcher arranged in the evaporation concentrator and the crystallizer are matched, and corresponding technological parameters in the technological process are regulated and controlled at the same time, so that a complete cobalt sulfate production process is formed.
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 (6)
1. The environment-friendly process for producing the cobalt sulfate is characterized by comprising the following steps of:
s1, slurrying cobalt slag, repeatedly carrying out acid leaching, adjusting pH, and filtering to obtain filtrate B and aluminum and iron filter residues;
s2, adding sodium carbonate into the filtrate B, uniformly stirring, and filtering to obtain filtrate C and filter residue A; adding dilute sulfuric acid into the filter residue A, uniformly mixing, filtering to obtain filtrate D and filter residue B, returning the filter residue B to the step S1 for acid leaching, carrying out primary extraction on the filtrate D by adopting a P204 extractant to obtain extract A and raffinate A, adding an N235 extractant into the raffinate A for secondary extraction to obtain extract B and raffinate B, and carrying out tertiary extraction on the raffinate B by adopting a P507 extractant to obtain extract C and cobalt sulfate solution; using the extract A, the extract B and the extract C as corresponding products;
s3, evaporating, concentrating and crystallizing the cobalt sulfate solution at a controlled temperature to obtain a cobalt sulfate mixed solution, and conveying the cobalt sulfate mixed solution into a suspension tank: concentrating the cobalt sulfate solution in an evaporation concentrator by temperature control evaporation to obtain concentrated solution, placing the concentrated solution in a crystallizer, introducing circulating cooling water for cooling, adding seed crystals during cooling, then standing for crystallization by temperature control to obtain cobalt sulfate mixed solution, and sending the cobalt sulfate mixed solution into a suspension tank;
the temperature of the temperature-controlled evaporation concentration is 100-110 ℃; the concentration by evaporation is to a degree of concentration to a specific gravity of 1320-1355kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The seed crystal is added when the cooling temperature is reduced to 40-45 ℃; the mass ratio of the cobalt sulfate solution to the seed crystal is 10:1-1.1; the temperature of the temperature-controlled standing crystallization is 30-35 ℃ and the time is 21-23h;
foam traps are arranged in the evaporation concentrator and the crystallizer;
s4, grading particles of the cobalt sulfate mixed solution, and centrifugally dehydrating to obtain cobalt sulfate particles with different particle diameters: delivering the cobalt sulfate mixed solution to a cyclone from the bottom of a temporary tank to carry out grading and centrifugal dehydration of particles to obtain large-particle cobalt sulfate, qualified-particle cobalt sulfate and small-particle cobalt sulfate, crushing the large-particle cobalt sulfate, returning the large-particle cobalt sulfate to an evaporation concentrator to serve as seed crystals, and directly returning the small-particle cobalt sulfate to the evaporation concentrator to serve as seed crystals;
s5, drying the qualified granular cobalt sulfate at a controlled temperature to obtain a finished cobalt sulfate product.
2. The green environmental protection process for producing cobalt sulfate according to claim 1, wherein the step S1 is specifically: adding desalted water into cobalt slag to carry out slurrying, adding concentrated sulfuric acid to carry out temperature-control acid leaching, filtering to obtain leaching liquid and leaching slag, carrying out repeated acid leaching and filtering steps on the leaching slag, mixing and discarding the finally obtained leaching slag, uniformly mixing the leaching liquid to obtain filtrate A, adding sodium hydroxide into the filtrate A, uniformly stirring and filtering to obtain filtrate B, and aluminum and iron filter residues.
3. The green environmental protection process for producing cobalt sulfate according to claim 2, wherein the mass ratio of the cobalt slag to the desalted water is 1:3-3.5; the addition amount of the concentrated sulfuric acid is 55-70g/L; the temperature of the temperature-controlled acid leaching is 75-80 ℃ and the time is 2-3h; the times of repeated acid leaching and filtering steps are 2-3 times; the sodium hydroxide was added in an amount up to ph=5 of the solution.
4. The green environmental protection process for producing cobalt sulfate according to claim 1, wherein in step S2, the mass concentration of sodium carbonate is 99%, and the addition amount of sodium carbonate is up to ph=9 of the solution; the mass concentration of the dilute sulfuric acid is 20-30%, and the volume ratio of the filter residue A to the dilute sulfuric acid is 1:1.5-2.
5. The green environmental protection process for producing cobalt sulfate according to claim 1, wherein the volume ratio of the filtrate D to the P204 extractant in the step S2 is 1:0.8-1; the volume ratio of the raffinate A to the N235 extractant is 1:0.7-0.9; the volume ratio of the raffinate B to the P507 extractant is 1:0.6-0.8.
6. The green environmental protection process for producing cobalt sulfate according to claim 1, wherein the temperature of the temperature-controlled drying in the step S5 is 160-190 ℃ for 1-2h.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061390A (en) * | 2010-12-03 | 2011-05-18 | 安化金源新材料有限责任公司 | Method for directly producing high-purity electronic level cobaltous sulfate by using cobalt-containing waste |
| CN108622943A (en) * | 2018-04-12 | 2018-10-09 | 河海大学 | A method of LITHIUM BATTERY nickel sulfate and cobaltous sulfate are produced with useless nickel cobalt (alloy) |
| CN111056576A (en) * | 2018-10-16 | 2020-04-24 | 四川省九维新材料科技有限公司 | Method for preparing battery-grade cobalt sulfate from low-grade cobalt-sulfur tailings |
| CN112522512A (en) * | 2020-11-12 | 2021-03-19 | 四川顺应动力电池材料有限公司 | Method for preparing battery-grade cobalt sulfate by using organic cobalt slag of zinc smelting plant |
| WO2021075467A1 (en) * | 2019-10-16 | 2021-04-22 | Ｊｘ金属株式会社 | Method for producing high-purity cobalt sulfate solution, and method for producing cobalt sulfate |
| CN114410972A (en) * | 2021-12-25 | 2022-04-29 | 河南豫光锌业有限公司 | Method for preparing cobalt sulfate from zinc smelting cobalt slag |
| CN115092971A (en) * | 2022-07-07 | 2022-09-23 | 科立鑫(珠海)新能源有限公司 | Production process of high-purity cobalt sulfate crystal |
-
2023
- 2023-06-27 CN CN202310765241.4A patent/CN116768284B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061390A (en) * | 2010-12-03 | 2011-05-18 | 安化金源新材料有限责任公司 | Method for directly producing high-purity electronic level cobaltous sulfate by using cobalt-containing waste |
| CN108622943A (en) * | 2018-04-12 | 2018-10-09 | 河海大学 | A method of LITHIUM BATTERY nickel sulfate and cobaltous sulfate are produced with useless nickel cobalt (alloy) |
| CN111056576A (en) * | 2018-10-16 | 2020-04-24 | 四川省九维新材料科技有限公司 | Method for preparing battery-grade cobalt sulfate from low-grade cobalt-sulfur tailings |
| WO2021075467A1 (en) * | 2019-10-16 | 2021-04-22 | Ｊｘ金属株式会社 | Method for producing high-purity cobalt sulfate solution, and method for producing cobalt sulfate |
| CN112522512A (en) * | 2020-11-12 | 2021-03-19 | 四川顺应动力电池材料有限公司 | Method for preparing battery-grade cobalt sulfate by using organic cobalt slag of zinc smelting plant |
| CN114410972A (en) * | 2021-12-25 | 2022-04-29 | 河南豫光锌业有限公司 | Method for preparing cobalt sulfate from zinc smelting cobalt slag |
| CN115092971A (en) * | 2022-07-07 | 2022-09-23 | 科立鑫(珠海)新能源有限公司 | Production process of high-purity cobalt sulfate crystal |
Non-Patent Citations (2)
| Title |
|---|
| 酸浸―萃取―沉淀法回收废锂离子电池中的钴;张新乐;徐金球;张晓琳;;化工环保;36(03);326-331 * |
| 钴锰渣除杂提钴工艺研究;林江顺, 蒋开喜;有色金属;54(03);36-38 * |
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