CN111056576A - Method for preparing battery-grade cobalt sulfate from low-grade cobalt-sulfur tailings - Google Patents
Method for preparing battery-grade cobalt sulfate from low-grade cobalt-sulfur tailings Download PDFInfo
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- 229940044175 cobalt sulfate Drugs 0.000 title claims abstract description 41
- 229910000361 cobalt sulfate Inorganic materials 0.000 title claims abstract description 41
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 72
- 239000012074 organic phase Substances 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 35
- 238000002386 leaching Methods 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- 239000010941 cobalt Substances 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 229910052742 iron Inorganic materials 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 235000017550 sodium carbonate Nutrition 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000011001 backwashing Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000004070 electrodeposition Methods 0.000 description 9
- 238000005086 pumping Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NHPHQYDQKATMFU-UHFFFAOYSA-N [Cu]=S.[Co] Chemical compound [Cu]=S.[Co] NHPHQYDQKATMFU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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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
- C01G51/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
A method for preparing battery-grade cobalt sulfate from low-grade cobalt-sulfur tailings belongs to the technical field of battery material production. The method comprises the following steps: roasting the low-grade cobalt to form calcine; mixing the calcine and the raffinate, then flowing into a leaching system, carrying out liquid-solid separation on the leached ore pulp through a filter, mixing the filtrate and washing water to form a pre-extraction liquid, and feeding the pre-extraction liquid into a copper extraction system; part of raffinate enters an impurity removal device, sodium carbonate and mixed gas are added to carry out impurity removal operation, then the raffinate enters an impurity removal filter press to be washed, and the obtained impurity-removed filtrate is cooled and then sent to a P204 extraction system; extracting the impurity-removed filtrate and the organic phase according to a certain flow ratio, and sending the obtained P204 raffinate into a P507 extraction system; the P204 raffinate and the P507 organic phase enter a P507 extraction system according to a certain flow ratio to carry out countercurrent extraction; and carrying out operations of oil removal, concentration crystallization and drying on the obtained cobalt sulfate solution to obtain a product with low impurity content. The method has the advantages of low cost, simple process and easy realization, and is suitable for the cobalt sulfate production industry.
Description
Technical Field
The invention belongs to the technical field of battery material production, and particularly relates to a method for preparing battery-grade cobalt sulfate from low-grade cobalt-sulfur tailings.
Background
With the development of new energy automobile projects, higher requirements are also put forward on high-performance green batteries (batteries). The development of new energy automobiles necessarily drives the leap-type growth of lithium battery materials, cobalt sulfate is an important raw material of a ternary cathode material precursor of the lithium battery, and with the continuous growth of the ternary material in the field of passenger vehicles, upstream powder materials like cobalt salts such as cobalt sulfate and various cobalt oxides have huge demand potentials.
Impurities are inevitably contained in the cobalt sulfate, and the quality of the lithium battery ternary cathode material precursor is greatly influenced due to the fact that the impurity content is too high, so that the impurity removal operation is required in the cobalt sulfate production process. In the existing production process, the prepared cobalt sulfate has high impurity content, high production cost and low efficiency. Therefore, a method for preparing cobalt sulfate from low-grade cobalt sulfur tailings with high efficiency and cost saving is urgently needed, and impurities can be effectively reduced by the method so as to meet the application requirements of the battery industry.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing battery-grade cobalt sulfate from low-grade cobalt sulfur tailings, which has low production cost and high efficiency and can effectively remove impurities.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of battery-grade cobalt sulfate comprises the following steps:
A. uniformly feeding the low-grade cobalt-sulfur tailings into a roasting furnace, blowing air into the bottom of the roasting furnace, and roasting to form roasted sand;
B. mixing the calcine and the raffinate, then flowing into a leaching system, carrying out liquid-solid separation on the leached ore pulp through a filter, mixing the filtrate and washing water to form a pre-extraction liquid, and feeding the pre-extraction liquid into a copper extraction system;
C. part of raffinate enters an impurity removal device, sodium carbonate is added, meanwhile, mixed gas of air and sulfur dioxide is introduced, the end-point pH value is adjusted, impurity removal operation is carried out, then the raffinate enters an impurity removal filter press for washing, and obtained impurity removal filtrate is cooled and then sent to a P204 extraction system;
D. p204 is selected as an extracting agent, 260#Solvent oil is used as a diluent, an organic phase is formed by the solvent oil and the organic phase according to a certain volume ratio, the impurity-removed filtrate and the organic phase are extracted according to a certain flow ratio, and the obtained P204 raffinate is sent into a P507 extraction system;
E. the P204 raffinate and the P507 organic phase saponified by the soda ash enter a P507 extraction system according to a certain flow ratio for countercurrent extraction;
F. and (3) treating the obtained cobalt sulfate solution by a purification process, and then performing operations of oil removal, concentration crystallization and drying to obtain a battery-grade cobalt sulfate product.
Specifically, the low-grade cobalt-sulfur tailings are waste low-grade cobalt-sulfur tailings, the roasting temperature range in the step A is 550-780 ℃, and the roasting time is 5 hours.
Specifically, the leaching system entering the step B further comprises crude cobalt salt, and the pH value of leaching in the leaching system is 1.0-1.5.
Specifically, the organic phase composition in the step D is as follows: 20% of P204 and 80% of No. 260 solvent oil (volume ratio) are saponified by adopting a pure alkali solution, and the saponification rate is about 40-60%.
Preferably, the step D specifically comprises the steps of feeding the saponified organic matter into an extraction box to perform countercurrent extraction with the impurity-removed filtrate, and loading the P204 with machine-used 4N dilute sulfuric acid for washing cobalt; after cobalt washing, performing countercurrent reverse extraction on the P204 organic phase by using 0.6-1N dilute sulfuric acid in sequence to obtain copper, manganese and zinc; finally, carrying out countercurrent reverse extraction on iron by using 6N industrial hydrochloric acid for the P204 organic solvent, and enabling the liquid after iron reversal to enter a wastewater treatment system; and (3) the P204 unloaded organic phase is saponified and then returned for use, and the obtained P204 raffinate is pumped into a P507 extraction system.
Further, step E further comprises: washing the organic phase subjected to countercurrent extraction with 4N dilute sulfuric acid solution to obtain nickel, then back-extracting cobalt with sulfuric acid solution, and back-washing the organic phase subjected to cobalt back-extraction with 6N hydrochloric acid to obtain iron; and (4) saponifying the organic phase subjected to iron removal, and returning the organic phase to the system for reuse to finally obtain the cobalt sulfate solution.
The invention has the beneficial effects that: the method adopts low-grade cobalt-sulfur tailings as raw materials, effectively reduces the cost, avoids high energy consumption caused by the preparation of cobalt sulfate by traditional evaporative crystallization, avoids high cost, long flow path and low efficiency caused by the traditional extraction method, has low production cost, utilizes P204 to extract, deeply purifies and removes impurities, utilizes P507 to extract and separate nickel and cobalt to obtain high-purity cobalt sulfate solution, finally obtains the cobalt sulfate with low impurity content, has high product quality, and can be applied to battery electrode materials. The invention is suitable for the cobalt sulfate production industry.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of the present invention.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings and embodiments.
The method for preparing battery-grade cobalt sulfate from low-grade cobalt sulfur tailings is shown in figure 1, and electrodeposited copper, other filter residues which can be sold outside and the like are also formed in the method, and the parts are also shown in figure 1. The main process flow of fig. 1 comprises: roasting, acid leaching, filter pressing, washing, copper extraction, electrodeposition, product electrolytic copper, wherein the copper raffinate is mainly returned to the acid leaching, and part of the copper raffinate enters neutralization for deironing, extraction for impurity removal, concentration and crystallization, drying and packaging, and the product cobalt sulfate. Specifically, the following were used: the method comprises the following steps of (1) leaching calcine (crude cobalt material), copper extraction and copper electrodeposition process to produce electrodeposited copper, oxidizing and deironing part of raffinate (about 30%) after copper extraction, then feeding the raffinate into P204 and P507 cobalt extraction systems, carrying out back extraction by using sulfuric acid to produce pure cobalt sulfate solution, and then carrying out concentration and crystallization to produce cobalt sulfate; the remaining part (about 70%) is returned to the leaching stage, where the sulfuric acid is recovered for leaching. The preparation method of the cobalt sulfate product comprises the following steps: low-grade cobalt-sulfur tailings are subjected to sulfating roasting to form calcine, the calcine and dust subjected to electric dust removal enter a slag discharging roller together, then crude cobalt materials are added, the crude cobalt materials are introduced into a leaching system, then the calcine is subjected to slag leaching, filter pressing and washing, filtrate and washing water are discharged into a copper extraction system, one part of raffinate returns to the leaching system, the other part of raffinate enters an impurity removal device, mixed gas of air and sulfur dioxide is added into the impurity removal device to perform impurity removal operation, then the filtrate enters filter pressing and washing, the obtained filtrate enters P204 to perform extraction and impurity removal, then the filtrate enters P507 to perform extraction, and the obtained sulfuric acid strip liquor is subjected to oil removal, concentration and crystallization and drying operation to obtain a battery-grade cobalt sulfate product.
Example 1
This example illustrates the preparation of battery grade cobalt sulfate, and the production of the ancillary products of the preparation. The method comprises the following steps:
(1) roasting
Conveying the low-grade cobalt-sulfur tailings from a raw material storage to a feeding bin of a roasting furnace through a belt, uniformly feeding the low-grade cobalt-sulfur tailings into the roasting furnace through a screw feeder, blowing air from the bottom of the furnace, controlling the roasting temperature to be 550-780 ℃, keeping the roasting temperature for 5 hours, roasting to obtain roasted products, overflowing the roasted products from a discharge port, and purifying smoke gas through a slag discharging roller to directly enter an original acid making system for making acid.
The main purpose of the process is to perform sulfation roasting on the copper cobalt sulfide concentrate, and simultaneously remove part of organic impurities in the crude cobalt material.
(2) Leaching and liquid-solid separation
The working procedure mainly comprises two steps of leaching of the calcine and filter pressing and washing.
And (3) enabling the calcine and the rough cobalt salt to enter an acid leaching working section together, enabling the calcine and the rough cobalt salt to enter a water quenching tank and then enter a leaching tank after being mixed with raffinate, controlling the leaching pH value to be 1.0-1.5, and enabling leaching devices at all levels to be connected in series and arranged in a stepped manner. And pumping the leached ore pulp to a filter for liquid-solid separation, mixing the filtrate and washing water to form a pre-extraction liquid, feeding the pre-extraction liquid into a copper pre-extraction liquid tank, and washing filter residues to be used as a raw material for preparing cement or pig iron in an external cement plant or a steel plant.
Preferably, the leaching time is 4 hours, the leaching temperature is more than or equal to 50 ℃, and the used reducing agent is SO2。
(3) Copper extraction and electrodeposition
The pre-extraction solution was pumped to the feed tank of the copper extraction system to separate the copper from the cobalt and to load the organic phase with about 35g/L, H copper2SO4About 175g/L of electrowinning barren solutionBack extraction, the copper content of the back extraction solution is about 45g/L, H2SO4About 160g/L, returning to the electrodeposition process, and pumping raffinate to a leaching system. And (4) feeding the back extraction solution from copper extraction into a copper electrodeposition tank for electrodeposition to obtain cathode copper. After electrodeposition, the electrodeposition barren solution automatically flows into an electrodeposition solution circulating tank and returns to copper extraction through a pump. Guerban is added into the electrolyte to enhance the compactness of copper. Part of the raffinate is open-circuited to the iron removal process, and is hereinafter referred to as open-circuited raffinate.
In the copper extraction, the organic phase composition is 25% Lix984N-LV and 75% No. 260 solvent oil (volume ratio). The range of the extraction phase ratio O/A is 1-3: 1, the range of the washing phase ratio O/A is less than 30: 1, and the range of the back extraction phase ratio O/A is 1.5-2: 1.
(4) Removing impurities
Adding sodium carbonate and open-circuit raffinate into a mechanical stirring tank, introducing sulfur dioxide/air mixed gas, adjusting the end pH to about 4.5, pumping the mixture into an impurity removal filter press through a transfer tank, introducing the obtained filter press filtrate into a solution tank, cooling, pumping the filtrate into a fine filter for filtering, and pumping the obtained impurity removal filtrate into a P204 extraction system.
In order to improve the impurity removal efficiency and effect and improve the product purity, a plurality of impurity removal devices are selected, and 3 impurity removal reaction tanks are configured like steps.
Sodium carbonate is used as a neutralizing agent in the step, and the iron removal time is preferably 4 hours. A large amount of metal impurities can be removed through the step, the process flow for preparing high-purity cobalt sulfate is shortened and simplified, and the consumption of chemical raw materials is reduced, so that the production cost is reduced, and the loss of cobalt in the impurity removal process is reduced.
Part of raffinate is oxidized to remove iron and then enters a P204 and P507 cobalt extraction system, pure cobalt sulfate solution is produced by sulfuric acid back extraction, and cobalt sulfate is produced by concentration and crystallization; and the other part of raffinate is returned to the leaching working section, and the sulfuric acid in the raffinate is recycled for leaching, so that the cost can be effectively reduced, and the efficiency is improved.
(5) P204 extraction
Cooling the filtrate to below 45 deg.C, pumping to P204 extraction box, and extracting with organic phase at a certain flow ratio. The extractant is P204, and the diluent is 260#Solvent oil. The organic phase composition is 20% P204 and 80% No. 260 solvent oil (volume ratio), and the saponification rate is about 40-60% by using a pure alkali solution for saponification. The saponified organic matter enters an extraction box to be subjected to countercurrent extraction with impurity-removed filtrate, and the cobalt is washed by 4N dilute sulfuric acid loaded on a machine by P204; after cobalt washing, performing countercurrent reverse extraction on the P204 organic phase by using 0.6-1N dilute sulfuric acid in sequence to obtain copper, manganese and zinc; finally, carrying out countercurrent reverse extraction on iron by using 6N industrial hydrochloric acid for the P204 organic solvent, and enabling the liquid after iron reversal to enter a wastewater treatment system; p204 no-load organic is saponified and then returned to be used, and P204 raffinate is pumped into a P507 extraction system.
The organic phase in the scheme can be reused, so that the cost is saved, and the purification capacity is improved.
(6) P507 extraction
The P204 raffinate and the P507 organic phase saponified by the soda ash enter a P507 extraction box according to a certain flow ratio for countercurrent extraction, and the cobalt is extracted into the organic phase. The organic phase composition is 25% P507 and 75% No. 260 solvent oil (volume ratio), and the saponification rate is about 40-60% by saponifying with a soda solution. Washing nickel in the cobalt-containing organic phase by using 4N dilute sulfuric acid solution, then back-extracting cobalt by using sulfuric acid solution, and back-washing iron in the cobalt-removed organic phase by using 6N hydrochloric acid; and (4) saponifying the organic phase subjected to iron removal, and returning the organic phase to the system for reuse to finally obtain the cobalt sulfate solution.
The temperature of the feed liquid in the step is limited below 45 ℃, and the organic phase in the scheme can be reused, so that the cost is saved.
(7) Deoiling, concentrating, crystallizing, and drying
Filtering the cobalt sulfate solution by a stainless steel wire mesh precision filter, filtering out a trace amount of combined materials combined with oil, sending the combined materials into a triple-effect evaporator for evaporation, and controlling the end point specific gravity; then the mixture is sent into a crystallizer for slow concentration and crystallization (cooling temperature is strictly controlled), the crystallization process is provided with cyclone classification, the fine particle materials are returned to the mother liquor, and most of the produced products are ensured to be coarse particle materials. And after the materials are cooled to normal temperature, sending the materials to a centrifuge to separate out crystals and mother liquor, sending the obtained cobalt sulfate crystals to a drying process to prepare a high-quality cobalt sulfate product, and sending the high-quality cobalt sulfate product to a finished product warehouse after inspection and packaging.
In the process of concentration and crystallization, the concentration of cobalt in the cobalt sulfate solution is 110-120 g/L, and the concentration end specific gravity range is 1.47-1.52 g/cm3The evaporation temperature is 80-90 ℃, the evaporation end point temperature is 70 ℃, the crystallization end point temperature is 35 ℃, and the crystallization end point specific gravity is 1.42g/cm3And the crystallization rate is 50 percent, and the cobalt content of the finally obtained dried product is more than or equal to 21 percent.
Claims (6)
1. A method for preparing battery-grade cobalt sulfate from low-grade cobalt-sulfur tailings is characterized by comprising the following steps:
A. uniformly feeding the low-grade cobalt-sulfur tailings into a roasting furnace, blowing air into the bottom of the roasting furnace, and roasting to form roasted sand;
B. mixing the calcine and the raffinate, then flowing into a leaching system, carrying out liquid-solid separation on the leached ore pulp through a filter, mixing the filtrate and washing water to form a pre-extraction liquid, and feeding the pre-extraction liquid into a copper extraction system;
C. part of raffinate enters an impurity removal device, sodium carbonate is added, meanwhile, mixed gas of air and sulfur dioxide is introduced, the end-point pH value is adjusted, impurity removal operation is carried out, then the raffinate enters an impurity removal filter press for washing, and obtained impurity removal filtrate is cooled and then sent to a P204 extraction system;
D. selecting P204 as an extracting agent and 260# solvent oil as a diluting agent, forming an organic phase by the two according to a certain volume ratio, extracting impurity-removed filtrate and the organic phase according to a certain flow ratio, and sending the obtained P204 raffinate into a P507 extraction system;
E. the P204 raffinate and the P507 organic phase saponified by the soda ash enter a P507 extraction system according to a certain flow ratio for countercurrent extraction;
F. and (3) treating the obtained cobalt sulfate solution by a purification process, and then performing operations of oil removal, concentration crystallization and drying to obtain a battery-grade cobalt sulfate product.
2. The method according to claim 1, wherein the low-grade cobalt sulfur tailings are waste low-grade cobalt sulfur tailings, the roasting temperature in the step A is 550-780 ℃, and the roasting time is 5 hours.
3. The method as claimed in claim 1, wherein the leaching system entering step B further comprises crude cobalt salt, and the leaching system has a leaching PH value in the range of 1.0 to 1.5.
4. The process of claim 1, wherein the organic phase composition in step D is: 20% of P204 and 80% of No. 260 solvent oil (volume ratio) are saponified by adopting a pure alkali solution, and the saponification rate is about 40-60%.
5. The method of claim 4, wherein step D comprises feeding saponified organic material into an extraction tank, performing countercurrent extraction with the filtrate obtained after impurity removal, and washing cobalt with 0.6-1N dilute sulfuric acid on a P204 loading machine; after cobalt washing, performing countercurrent reverse extraction on the P204 organic phase by using 4N dilute sulfuric acid in sequence; finally, carrying out countercurrent reverse extraction on iron by using 6N industrial hydrochloric acid for the P204 organic solvent, and enabling the liquid after iron reversal to enter a wastewater treatment system; and (3) the P204 unloaded organic phase is saponified and then returned for use, and the obtained P204 raffinate is pumped into a P507 extraction system.
6. The method of claim 1, wherein step E further comprises: washing the organic phase subjected to countercurrent extraction with 4N dilute sulfuric acid solution to obtain nickel, then back-extracting cobalt with sulfuric acid solution, and back-washing the organic phase subjected to cobalt back-extraction with 6N hydrochloric acid to obtain iron; and (4) saponifying the organic phase subjected to iron removal, and returning the organic phase to the system for reuse to finally obtain the cobalt sulfate solution.
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| CN111533179A (en) * | 2020-05-16 | 2020-08-14 | 赣州腾远钴业新材料股份有限公司 | Preparation method for continuously preparing large-particle-size beta-type cobalt sulfide crystals |
| CN112520790A (en) * | 2020-11-12 | 2021-03-19 | 四川顺应动力电池材料有限公司 | Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant |
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| CN113174485A (en) * | 2021-04-29 | 2021-07-27 | 金川集团镍盐有限公司 | Method for deeply removing calcium and manganese in cobalt sulfate solution |
| CN113981241A (en) * | 2021-10-22 | 2022-01-28 | 广东佳纳能源科技有限公司 | Method for treating cobalt intermediate product |
| CN116768284A (en) * | 2023-06-27 | 2023-09-19 | 科立鑫(珠海)新能源有限公司 | Environment-friendly process for producing cobalt sulfate |
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| CN111533179A (en) * | 2020-05-16 | 2020-08-14 | 赣州腾远钴业新材料股份有限公司 | Preparation method for continuously preparing large-particle-size beta-type cobalt sulfide crystals |
| CN112520790A (en) * | 2020-11-12 | 2021-03-19 | 四川顺应动力电池材料有限公司 | Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant |
| 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 |
| CN113046572A (en) * | 2021-03-11 | 2021-06-29 | 浙江中金格派锂电产业股份有限公司 | Cobalt chloride production process |
| CN113174485A (en) * | 2021-04-29 | 2021-07-27 | 金川集团镍盐有限公司 | Method for deeply removing calcium and manganese in cobalt sulfate solution |
| CN113981241A (en) * | 2021-10-22 | 2022-01-28 | 广东佳纳能源科技有限公司 | Method for treating cobalt intermediate product |
| CN116768284A (en) * | 2023-06-27 | 2023-09-19 | 科立鑫(珠海)新能源有限公司 | Environment-friendly process for producing cobalt sulfate |
| CN116768284B (en) * | 2023-06-27 | 2024-01-23 | 科立鑫(珠海)新能源有限公司 | Environment-friendly process for producing cobalt sulfate |
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