CN117701890A - Method for synchronously recycling nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues - Google Patents
Method for synchronously recycling nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues Download PDFInfo
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- CN117701890A CN117701890A CN202410167743.1A CN202410167743A CN117701890A CN 117701890 A CN117701890 A CN 117701890A CN 202410167743 A CN202410167743 A CN 202410167743A CN 117701890 A CN117701890 A CN 117701890A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000010941 cobalt Substances 0.000 title claims abstract description 75
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 75
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 67
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 67
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002386 leaching Methods 0.000 title claims abstract description 55
- 239000011572 manganese Substances 0.000 title claims abstract description 55
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 55
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title abstract description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 239000002738 chelating agent Substances 0.000 claims description 37
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 27
- 229910021645 metal ion Inorganic materials 0.000 claims description 26
- 239000007800 oxidant agent Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 11
- 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 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 8
- 229910001437 manganese ion Inorganic materials 0.000 claims description 8
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002910 solid waste Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000001728 nano-filtration Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000012209 synthetic fiber Substances 0.000 claims description 3
- 229920002994 synthetic fiber Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 description 20
- 238000000926 separation method Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of metal production, and discloses a method for synchronously recycling nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues, which comprises the following steps: step one: the invention relates to a method for preparing a sulfuric acid leaching solution, which comprises the steps of heating waste residues by utilizing a microwave heating technology to destroy the crystal structure of the waste residues, increasing the solubility of metals, mixing the nickel-cobalt-manganese-containing waste residues with sulfuric acid, and carrying out leaching reaction to obtain the sulfuric acid leaching solution.
Description
Technical Field
The invention relates to the field of metal production, in particular to a method for synchronously recycling nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues.
Background
Nickel-cobalt-manganese-containing waste residues refer to solid wastes containing metals such as nickel, cobalt, manganese, etc., which are generally derived from the mining and processing of metal ores, the production and recovery of batteries, and by-products in various industrial processes. In many industries, waste residues containing valuable metals such as nickel, cobalt and the like, such as electro-nickel cobalt-containing waste residues, waste power battery materials and waste catalysts, and most of the waste residues also contain higher manganese, so that the waste residues have high recovery value, and can be recovered for producing and preparing nickel-cobalt-manganese ternary precursors.
The application number is 201610737450.8, and discloses a method for synchronously recovering nickel, cobalt and manganese from nickel, cobalt and manganese-containing waste residues, which solves the problems that the recovery efficiency of the existing nickel, cobalt and manganese is generally lower and the process is complicated, but uses tributyl phosphate TBP and saponified neodecanoic acid as common extractant for synchronously extracting nickel, cobalt and manganese, utilizes the synergistic effect between the two extractants and regulates the proportion and pH value of neodecanoic acid and TBP, can realize the efficient extraction of three metal ions of nickel, cobalt and manganese, and can jointly extract nickel, cobalt and manganese in the extraction process, which possibly leads to that the nickel, cobalt and manganese are difficult to separate in the subsequent separation step to influence the purity of the final product.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues, which solves the problem that nickel, cobalt and manganese can be jointly extracted in the current extraction process, which can lead to difficult separation in the subsequent separation step.
In order to achieve the above purpose, the invention is realized by the following technical scheme: the method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues comprises the following steps:
step one: heating the waste residues by utilizing a microwave heating technology, mixing the nickel-cobalt-manganese-containing waste residues with sulfuric acid, and carrying out leaching reaction to obtain sulfuric acid leaching solution;
step two: according to the size and shape of solid particles in the leaching solution, selecting a filter medium, filter paper, filter cloth, glass fiber or synthetic fiber filter and a microporous filter or nanofiltration membrane, filtering the leaching solution, and separating solid waste residues and liquid leaching solution;
step three: before adding the oxidant, adding hydroxide or acid, and then adding the oxidant into the leaching solution to perform oxidation reaction, so that nickel, cobalt and manganese ions are oxidized into corresponding sulfate;
step four: the oxidized leaching solution passes through cooling equipment, the temperature of the leaching solution is rapidly reduced to the temperature of sulfate crystallization, and the cooling temperature is between 0 ℃ and 10 ℃ to separate out sulfate crystallization;
step five: filtering, washing and drying to separate sulfate and obtain mixed sulfate of nickel, cobalt and manganese, adding the dried solid sulfate into a proper container, and adding proper amount of water or organic solvent;
step six: ATMP:30-50%, DETA:20-40%, oxalic acid (10-30% according to the proportion) is mixed together, the mixture is stirred at room temperature until the chelating agent is completely dissolved, the prepared mixed chelating agent is added into the solution, stirring is continued to enable the chelating agent to fully contact with metal ions, and then the mixed sulfate is further extracted to obtain pure nickel, cobalt and manganese.
Preferably, in the third step, the pH of the solution is adjusted to 3-6 by adding sodium hydroxide or sulfuric acid to remove or convert other metal ions such as iron, aluminum, copper or zinc which may interfere with the extraction of nickel, cobalt and manganese, and an oxidizing agent is added to the leachate at the pH to perform an oxidation reaction to oxidize the nickel, cobalt and manganese ions into corresponding sulfate.
Preferably, in the third step, the oxidizing agent is specifically sodium persulfate, and the concentration of the sodium persulfate is in the range of 0.1-0.3 (mol/L).
Preferably, in the third step, hydrogen peroxide is used as an oxidizing agent, and nickel, cobalt and manganese are oxidized at the same time, so that certain other metal ions, such as copper or zinc, are not oxidized.
Preferably, in the third step, the temperature of the oxidation reaction is controlled between 20 ℃ and 60 ℃ to optimize the efficiency and selectivity of the oxidation reaction.
Preferably, in the third step, hydrogen peroxide is used as an oxidant, the concentration of the hydrogen peroxide is in the range of 0.1-0.3 (mol/L), and the pH value of the solution is controlled between 3-6 during the oxidation reaction, so as to prevent the decomposition of the hydrogen peroxide and maintain the high selectivity of the hydrogen peroxide to nickel, cobalt and manganese.
Preferably, in the fourth step, the cooling device is a cooler or an ice bath, the cooling temperature ranges from 0 ℃ to 10 ℃, and the leaching solution is continuously stirred during the cooling process so as to promote the crystallization of the sulfate and prevent the aggregation of the sulfate.
Preferably, in the fifth step, continuous automation equipment is adopted in the steps of filtering, washing, drying and the like, so that the production efficiency is improved, and the operation cost is reduced.
Preferably, in the step six, during the preparation of the mixed chelating agent, ATMP (phosphonic acid chelating agent) is added and stirred until the mixture is completely dissolved, and then DETA (amine chelating agent) and oxalic acid (carboxylic acid chelating agent) are added and stirred continuously until the mixture is uniform, so as to ensure that each chelating agent can be fully contacted with metal ions
Preferably, in the sixth step, the time of contacting the mixed chelating agent with the solution is controlled to be 30-60 minutes, so as to fully achieve chelation of the metal ions and the chelating agent, and in the extraction process, the extraction efficiency of the metal ions is optimized by controlling the conditions of the pH value, the temperature and the like of the solution.
Advantageous effects
The invention provides a method for synchronously recycling nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues. Compared with the prior art, the method has the following beneficial effects:
according to the invention, by using the mixed chelating agent of ATMP, DETA and oxalic acid in the extraction process, nickel, cobalt and manganese ions can be extracted from the leaching solution more effectively, the chelating agent has higher affinity with target metal ions, so that the recovery rate of metals is improved, the optimized chelating agent ratio is favorable for improving the selectivity of nickel, cobalt and manganese, meanwhile, the extraction of other metal ions is reduced or avoided, the subsequent separation and purification steps become simpler and faster due to the high selectivity and efficiency of the extraction process, the operation complexity and the production time are reduced, the overall production cost is reduced, and the nickel, cobalt and manganese separation with high efficiency and high selectivity can be realized in the extraction process, so that the nickel cobalt manganese metal product quality and the production efficiency are improved, and the production cost and the environmental risk are reduced.
Drawings
FIG. 1 is a flow chart of a method and a system for synchronously recycling nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but 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.
Referring to fig. 1, the present invention provides two technical solutions, specifically including the following embodiments:
embodiment one:
the method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues comprises the following steps:
step one: the waste slag is heated by utilizing a microwave heating technology to destroy the crystal structure of the waste slag and increase the solubility of metal, and the specific operation parameters are as follows: the microwave power is 300-600 watts, the heating time is 5-15 minutes, and the temperature is controlled at 60-80 ℃. Then mixing the nickel-cobalt-manganese-containing waste residues with sulfuric acid, performing leaching reaction to obtain sulfuric acid leaching solution, and mixing the nickel-cobalt-manganese-containing waste residues with sulfuric acid, performing leaching reaction to obtain sulfuric acid leaching solution;
step two: selecting proper filter media such as filter paper, filter cloth, glass fiber or synthetic fiber filter and microporous filter or nanofiltration membrane according to the size and shape of solid particles in the leaching solution, wherein the pore size of the filter media is 0.45-1.2 microns, and the filtration pressure is controlled to be 0.6-1.0 megapascal so as to realize high-efficiency filtration, separate solid waste residues and liquid leaching solution, and filter the leaching solution to separate the solid waste residues and the liquid leaching solution;
step three: before adding the oxidant, adding hydroxide or acid, wherein the hydroxide or acid is sodium hydroxide or sulfuric acid, adding sodium hydroxide or sulfuric acid with the addition amount of 0.1-0.5 mol/L, and adjusting the pH value of the solution to 2.0-3.0 to remove the interference metal ions in the form of hydroxide or precipitate. Then adding an oxidant (hydrogen peroxide or nitric acid) into the leaching solution, wherein the adding amount of the oxidant is 0.01-0.1 mol/L, carrying out oxidation reaction to oxidize nickel, cobalt and manganese ions into corresponding sulfate, removing interfering metal ions in the form of hydroxide or precipitate to remove or convert other metal ions possibly interfering with nickel, cobalt and manganese extraction, and then adding the oxidant into the leaching solution to carry out oxidation reaction to oxidize nickel, cobalt and manganese ions into corresponding sulfate;
step four: passing the oxidized leaching solution through a cooling device, such as a cooler or an ice bath, rapidly reducing the temperature of the leaching solution to the temperature of sulfate crystallization, wherein the cooling temperature is between 0 ℃ and 10 ℃ to separate out sulfate crystallization;
step five: separating sulfate by steps of filtering, washing, drying and the like, controlling the filtering pressure to be 0.6-1.0 megapascal, controlling the washing times to be 2-3 times, setting the drying temperature to be 50-70 ℃ and the drying time to be 2-4 hours to obtain nickel-cobalt-manganese mixed sulfate, adding the dried solid sulfate into a proper container, and adding proper amount of water or an organic solvent, wherein the organic solvent is specifically dimethyl sulfoxide (DMSO) or Dimethylformamide (DMF);
step six: ATMP (phosphonic acid chelating agent): 30-50%, DETA (amine chelator): 20-40%, oxalic acid (carboxylic acid chelating agent): 10-30% of the components are mixed together according to the proportion, the mixture is stirred at room temperature at the stirring speed of 300-500 r/min until the chelating agent is completely dissolved, the prepared mixed chelating agent is added into the solution, stirring is continued, the chelating agent is fully contacted with metal ions for 30-60 min, the mixed sulfate is further extracted, and the extraction temperature is kept at 20-25 ℃ to obtain pure nickel, cobalt and manganese.
Embodiment two:
in the third step, the pH value of the solution is adjusted to 3-6 by adding sodium hydroxide or sulfuric acid so as to remove or convert other metal ions which possibly interfere with the extraction of nickel, cobalt and manganese, such as iron, aluminum, copper or zinc, and under the pH value, an oxidant is added into the leaching solution to carry out an oxidation reaction so as to oxidize the nickel, cobalt and manganese ions into corresponding sulfate, wherein the oxidant is specifically sodium persulfate, the concentration of the sodium persulfate ranges from 0.1 to 0.3 (mol/L), hydrogen peroxide is adopted as the oxidant, nickel, cobalt and manganese are oxidized, meanwhile, certain other metal ions such as copper or zinc are not oxidized, the temperature of the oxidation reaction is controlled to be between 20 ℃ and 60 ℃ so as to optimize the efficiency and the selectivity of the oxidation reaction, hydrogen peroxide is adopted as the oxidant, the concentration of the hydrogen peroxide ranges from 0.1 to 0.3 (mol/L), in the oxidation reaction process, the pH value of the solution is controlled to be 3-6 so as to prevent hydrogen peroxide from being decomposed and keep high selectivity of the hydrogen peroxide to nickel, cobalt and manganese, in the fifth step, continuous automatic equipment is adopted in the steps of filtering, washing, drying and the like so as to improve the production efficiency and reduce the operation cost, ATMP (phosphonic acid chelating agent) is firstly added and stirred until the mixture is completely dissolved in the preparation process of the mixed chelating agent, DETA (amine chelating agent) and oxalic acid (carboxylic acid chelating agent) are then added and stirred continuously until the mixture is uniform, so that each chelating agent can be fully contacted with metal ions, the contact time of the mixed chelating agent and the solution is controlled to be 30-60 minutes so as to fully realize the chelation of the metal ions and the chelating agent, and in the extraction process, the pH value of the solution is controlled, temperature, etc., in step three, the pH of the solution is adjusted to 3-6 by adding sodium hydroxide or sulfuric acid. This pH range helps to remove or convert other metal ions such as iron, aluminum, copper or zinc that may interfere with the extraction of nickel, cobalt, manganese, the pH of the solution is controlled between 3-6 during the oxidation reaction to prevent decomposition of hydrogen peroxide and maintain its high selectivity to nickel, cobalt, manganese to optimize the extraction efficiency of the metal ions, and the temperature of the oxidation reaction is controlled between 20 ℃ and 60 ℃. This temperature range helps to optimize the efficiency and selectivity of the oxidation reaction, higher temperatures may accelerate the reaction rate, but excessive temperatures may lead to decomposition of hydrogen peroxide or unwanted side reactions, maintaining the pH of the solution between 3 and 6 during extraction to optimize the extraction efficiency of the metal ions. The temperature is typically controlled at or slightly above room temperature to avoid decomposition of the chelating agent or precipitation of metal ions due to overheating or cooling.
Preferably, after the chelating agent is fully contacted with the metal ions, the solution is kept stand for about 30-60 minutes to precipitate the chelate formed by the metal ions and the chelating agent, the precipitated chelate is separated by steps of filtering, washing, drying and the like, the filtering pressure is controlled to be 0.6-1.0 megapascal, the washing times are 2-3 times to remove impurities, the drying temperature is set to be 50-70 ℃, the drying time is 2-4 hours, the dried solid chelate is added into a proper container, a proper amount of water or an organic solvent is added to dissolve the solid chelate, a proper amount of stripping agent is added into the solution to strip the metal ions from the chelate, the common stripping agent comprises sulfuric acid, hydrochloric acid, nitric acid and the like, the concentration range of the stripping agent is 0.1-1.0 mol/L, the stripped solution is subjected to steps of filtering, washing, drying and the like, pure nickel, cobalt and manganese are separated, the filtering pressure is controlled to be 0.6-1.0 megapascal, the washing times are 2-3 times, the drying temperature is set to be 50-70 ℃, and the drying time is set to be 2-4 ℃ and the final pure cobalt and manganese is obtained.
The following are data results based on the production of nickel cobalt manganese in the above examples according to four sets of experiments:
the results of the above experimental data show that:
the chelating agent prepared by mixing 50% of ATMP, 40% of DETA and 30% of oxalic acid is adopted, the nickel-cobalt-manganese separation degree is the highest in the nickel-cobalt-manganese extraction production process, the extracted cobalt content is reduced, the chelating agent prepared by mixing 40% of ATMP, 30% of DETA and 20% of oxalic acid is adopted, all aspects of the chelating agent are at a medium level in the nickel-cobalt-manganese extraction production process, the separation degree is reduced by adopting 30% of ATMP, 20% of DETA and 10% of oxalic acid, the nickel content is improved, and the nickel content is obviously improved compared with a blank control.
The foregoing description of the preferred embodiments of the present invention is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. The method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues is characterized by comprising the following steps of: the method comprises the following steps:
step one: heating the waste residues by utilizing a microwave heating technology, mixing the nickel-cobalt-manganese-containing waste residues with sulfuric acid, and carrying out leaching reaction to obtain sulfuric acid leaching solution;
step two: according to the size and shape of solid particles in the leaching solution, selecting a filter medium, filter paper, filter cloth, glass fiber or synthetic fiber filter and a microporous filter or nanofiltration membrane, filtering the leaching solution, and separating solid waste residues and liquid leaching solution;
step three: before adding the oxidant, adding hydroxide or acid, and then adding the oxidant into the leaching solution to perform oxidation reaction, so that nickel, cobalt and manganese ions are oxidized into corresponding sulfate;
step four: the oxidized leaching solution passes through cooling equipment, the temperature of the leaching solution is rapidly reduced to the temperature of sulfate crystallization, and the cooling temperature is between 0 ℃ and 10 ℃ to separate out sulfate crystallization;
step five: filtering, washing and drying to separate sulfate and obtain mixed sulfate of nickel, cobalt and manganese, adding the dried solid sulfate into a proper container, and adding proper amount of water or organic solvent;
step six: ATMP:30-50%, DETA:20-40%, oxalic acid: 10-30%, mixing the above materials together, stirring at room temperature until the chelating agent is completely dissolved, adding the prepared mixed chelating agent into the solution, stirring continuously to make the chelating agent fully contact with metal ions, and further extracting the mixed sulfate to obtain pure nickel, cobalt and manganese.
2. The method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues according to claim 1, which is characterized in that: in the third step, the pH value of the solution is adjusted to 3-6 by adding sodium hydroxide or sulfuric acid, and under the pH value, an oxidant is added into the leaching solution to perform oxidation reaction, so that nickel, cobalt and manganese ions are oxidized into corresponding sulfate.
3. The method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues according to claim 1, which is characterized in that: in the third step, the oxidant is sodium persulfate, and the concentration range of the sodium persulfate is 0.1-0.3mol/L.
4. The method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues according to claim 1, which is characterized in that: in the third step, hydrogen peroxide is used as an oxidizing agent.
5. The method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues according to claim 1, which is characterized in that: in the third step, the temperature of the oxidation reaction is controlled between 20 ℃ and 60 ℃.
6. The method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues according to claim 1, which is characterized in that: in the third step, hydrogen peroxide is used as an oxidant, the concentration of the hydrogen peroxide is in the range of 0.1-0.3mol/L, and the pH value of the solution is controlled to be 3-6 in the oxidation reaction process.
7. The method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues according to claim 1, which is characterized in that: in the fourth step, the cooling equipment is a cooler or ice bath, the cooling temperature ranges from 0 ℃ to 10 ℃, and the leaching liquid is continuously stirred in the cooling process.
8. The method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues according to claim 1, which is characterized in that: in the fifth step, continuous automatic equipment is adopted for filtering, washing and drying.
9. The method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues according to claim 1, which is characterized in that: in the sixth step, ATMP is added and stirred until the ATMP is completely dissolved, DETA and oxalic acid are added, and stirring is continued until the mixture is uniform, wherein each chelating agent is fully contacted with metal ions.
10. The method for synchronously recovering nickel, cobalt and manganese from sulfuric acid leaching solution of nickel, cobalt and manganese-containing waste residues according to claim 1, which is characterized in that: in the step six, the contact time of the mixed chelating agent and the solution is controlled to be 30-60 minutes.
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| US4394355A (en) * | 1982-03-02 | 1983-07-19 | Celanese Corporation | Recovery of catalytically-useful cobalt and like metal moieties from their solid oxalates with EDTA salts |
| WO2014042136A1 (en) * | 2012-09-11 | 2014-03-20 | 株式会社日立製作所 | Method for recycling lithium-ion batteries and device therefor |
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| CN115652095A (en) * | 2022-10-27 | 2023-01-31 | 内蒙古蒙能环保科技有限公司 | Extraction process of degraded ternary lithium battery positive electrode material |
| CN116656953A (en) * | 2022-06-08 | 2023-08-29 | 新加坡国立大学 | Method for extracting and recovering heavy metals |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394355A (en) * | 1982-03-02 | 1983-07-19 | Celanese Corporation | Recovery of catalytically-useful cobalt and like metal moieties from their solid oxalates with EDTA salts |
| WO2014042136A1 (en) * | 2012-09-11 | 2014-03-20 | 株式会社日立製作所 | Method for recycling lithium-ion batteries and device therefor |
| CN110616331A (en) * | 2019-10-16 | 2019-12-27 | 衢州华友资源再生科技有限公司 | Method for recycling all metals of power lithium ion battery |
| CN112646974A (en) * | 2020-11-12 | 2021-04-13 | 四川顺应动力电池材料有限公司 | Method for recovering valuable metals from waste ternary lithium battery positive electrode material |
| CN116656953A (en) * | 2022-06-08 | 2023-08-29 | 新加坡国立大学 | Method for extracting and recovering heavy metals |
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