CN115180661B - Method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residues - Google Patents
Method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residues Download PDFInfo
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- CN115180661B CN115180661B CN202210863658.XA CN202210863658A CN115180661B CN 115180661 B CN115180661 B CN 115180661B CN 202210863658 A CN202210863658 A CN 202210863658A CN 115180661 B CN115180661 B CN 115180661B
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- 239000002699 waste material Substances 0.000 title claims abstract description 85
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 title claims abstract description 63
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 48
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 119
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 111
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 89
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000002893 slag Substances 0.000 claims abstract description 84
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 64
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 239000010941 cobalt Substances 0.000 claims abstract description 54
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 claims abstract description 53
- 239000010949 copper Substances 0.000 claims abstract description 53
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 52
- 239000002002 slurry Substances 0.000 claims abstract description 52
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 48
- 238000002386 leaching Methods 0.000 claims abstract description 45
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000011575 calcium Substances 0.000 claims abstract description 29
- -1 iron-aluminum-calcium residue Chemical group 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000011084 recovery Methods 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 14
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 14
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000004537 pulping Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 4
- KRCAYUPYTQNRQM-UHFFFAOYSA-I aluminum;iron(2+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Fe+2] KRCAYUPYTQNRQM-UHFFFAOYSA-I 0.000 claims description 3
- 239000010413 mother solution Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000002910 solid waste Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- 238000001556 precipitation Methods 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 abstract description 2
- NCBXYYPAHPNIJY-UHFFFAOYSA-N carbonic acid sulfuric acid Chemical compound S(=O)(=O)(O)O.S(=O)(=O)(O)O.C(O)(O)=O NCBXYYPAHPNIJY-UHFFFAOYSA-N 0.000 abstract 1
- 238000004064 recycling Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 description 5
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012045 crude solution Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- QJCGKOHLBOGCHT-UHFFFAOYSA-H S(=O)(=O)([O-])[O-].[Cu+2].[Ni+2].[Co+2].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Cu+2].[Ni+2].[Co+2].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] QJCGKOHLBOGCHT-UHFFFAOYSA-H 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- DLOMMAPSXFBYPG-UHFFFAOYSA-L [Cu](O)O.[Co].[Ni] Chemical compound [Cu](O)O.[Co].[Ni] DLOMMAPSXFBYPG-UHFFFAOYSA-L 0.000 description 1
- TZULHDYERBBVPB-UHFFFAOYSA-N [Li].[Co].[Ni].[Cu] Chemical compound [Li].[Co].[Ni].[Cu] TZULHDYERBBVPB-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of waste ternary lithium battery anode material recovery, and discloses a method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residues, which comprises the following steps: leaching the iron-aluminum waste residue slurry by concentrated sulfuric acid, slowly adding calcium carbonate slurry into the sulfuric acid leaching solution to obtain aluminum removal liquid of iron-aluminum-calcium residue and nickel-cobalt-copper mixed sulfate; preparing slurry from the Fe-Al-Ca slag, stirring and pulping, and filtering to obtain Fe-Al-Ca slag; adding sodium carbonate solution with the mass concentration of 20-30% into the aluminum removal solution to generate a nickel cobalt copper mixed carbonate; dissolving nickel-cobalt-copper mixed carbonic acid sulfuric acid, and adding sodium carbonate solution with mass concentration of 5-10% for secondary aluminum removal. The method comprises the steps of concentrated sulfuric acid leaching, primary aluminum iron removal of calcium carbonate, filtering, slag washing, concentrated sodium carbonate precipitation of nickel cobalt copper, sulfuric acid dissolution, secondary aluminum removal of dilute sodium carbonate solution and the like, wherein the obtained iron aluminum calcium waste slag contains low nickel, cobalt and copper, and the mixed sulfate of nickel, cobalt and copper sulfate contains low iron and aluminum impurities.
Description
Technical Field
The invention relates to the technical field of recovery of waste ternary lithium battery anode materials, in particular to a method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residues generated after leaching waste ternary lithium battery anode materials by sulfuric acid.
Background
With the continuous development and application of lithium ion batteries, the demand of ternary lithium batteries is continuously increased, and a large number of waste lithium batteries are also generated. According to statistics, in 2018-2020, the power batteries are scrapped for 12-20 ten thousand tons in a national way, and the waste ternary lithium batteries become a non-negligible part in the solid waste. Therefore, the nickel cobalt lithium is recovered from the waste ternary lithium battery, so that the environmental pollution can be avoided, and the pressure of nickel cobalt lithium resources can be relieved. However, a great amount of iron-aluminum waste residues are generated in the current process for recycling nickel-cobalt-copper-lithium from waste lithium batteries, and the iron-aluminum waste residues contain more nickel-cobalt-copper and other high-valence metal elements, so that if the waste residues are not used for recycling resources, the resource waste is caused, and the pollution risk is brought to the environment.
Chinese patent CN105506290a, patent name "a method for comprehensive utilization of iron-aluminum slag", discloses a treatment process of iron-aluminum slag: leaching the iron-aluminum slag by using sulfuric acid to obtain a leaching solution containing aluminum sulfate, nickel sulfate and cobalt sulfate, adding sodium sulfide into the leaching solution, and filtering to obtain a mixture containing nickel sulfide and cobalt sulfide and a crude solution containing aluminum sulfate; adding an oxidant into the crude solution for oxidation treatment, adding sodium hydroxide for iron removal, adding sodium sulfate to obtain an aluminum sodium sulfate stock solution, and crystallizing to obtain an aluminum sodium sulfate product. However, the method is not only used for adding dangerous compounds sodium sulfide, but also the obtained nickel sulfide and cobalt sulfide are difficult to further recover and prepare the nickel sulfate and the cobalt sulfate, the consumption of sodium sulfide and sodium hydroxide is larger, hydrogen sulfide gas is easy to generate in the process of adding sodium sulfide to precipitate the nickel cobalt, the environment is easy to be polluted, and the total treatment cost of the iron-aluminum waste residues is higher.
Disclosure of Invention
Aiming at the problems that products such as nickel sulfide, cobalt sulfide and the like are obtained by precipitation of sodium sulfide in the existing treatment method of the iron-aluminum waste residue, the nickel sulfide, the cobalt sulfide and the like are difficult to treat, and the metal price coefficient is low, the invention aims to provide the method for recovering the nickel-cobalt-copper mixed sulfate from the iron-aluminum waste residue, which converts nickel, cobalt and copper into sulfate, synchronously removes iron and aluminum, and has the advantages of easy treatment of the obtained products, high recovery rate of nickel, cobalt and copper, safe recovery process and low cost.
The invention provides the following technical scheme:
a method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residues comprises the following steps:
(1) Sulfuric acid leaching: adding concentrated sulfuric acid into the iron-aluminum waste residue slurry for dissolution to prepare sulfuric acid leaching solution;
(2) Removing iron and aluminum: slowly adding calcium carbonate slurry into the sulfuric acid leaching solution, heating and stirring to enable iron and aluminum ions to generate an iron-aluminum hydroxide mixture, and carrying out solid-liquid separation to obtain iron-aluminum-calcium slag and aluminum removal liquid containing nickel-cobalt-copper mixed sulfate;
(3) Rinsing: and (3) preparing slurry from the Fe-Al-Ca slag, stirring and pulping, and filtering to obtain the Fe-Al-Ca slag and slag washing liquid.
The iron-aluminum waste residue and the waste ternary battery positive electrode material are greatly different in composition, namely the solid waste residue of the waste ternary battery positive electrode material after sulfuric acid leaching recovery treatment is greatly reduced in nickel, cobalt and copper content, and the method for treating the waste ternary battery positive electrode material is not applicable to the iron-aluminum waste residue as the iron-aluminum waste residue practically treated by the method is less than or equal to 0.7% of nickel, less than or equal to 0.4% of cobalt and less than or equal to 1.2% of copper. How to effectively recycle nickel, cobalt and copper at the lower content is faced with a technical difficulty that is greater than that of directly treating the waste ternary battery anode material. In the method, concentrated sulfuric acid, namely sulfuric acid with the concentration of more than or equal to 70%, more preferably sulfuric acid with the concentration of more than or equal to 95%, more preferably sulfuric acid with the concentration of 98%, is added into the iron-aluminum waste residue slurry, so that the iron-aluminum waste residue reacts with sulfuric acid to generate aluminum sulfate, nickel sulfate, cobalt sulfate and copper sulfate, part of iron residues also generate ferric sulfate, sulfuric acid leaching solution with the pH value of 1.0-2.0 is obtained, calcium carbonate slurry is slowly added into the sulfuric acid leaching solution after heating, so that iron and aluminum react to generate iron-aluminum-calcium residues, the pH value of the reaction solution is 4.0-4.5, then aluminum removal solution and iron-aluminum-calcium residues are obtained through filtration, and the aluminum content in the aluminum removal solution is less than or equal to 2g/L and the iron content is less than or equal to 0.01g/L. The method for recycling the mixed sulfate of nickel, cobalt and copper from the iron-aluminum waste residue has high nickel, cobalt and copper recycling efficiency, and the content of nickel, cobalt and copper in the residual iron-aluminum-calcium waste residue is very low, wherein the content of nickel is less than or equal to 0.07%, the content of cobalt is less than or equal to 0.05% and the content of copper is less than or equal to 0.2%.
As a preferred feature of the method of the present invention,
in the step (1), the mass content of the iron-aluminum waste slag in the iron-aluminum waste slag slurry is 20% -35%;
in the step (1), the mass ratio of the concentrated sulfuric acid to the iron-aluminum waste residue is more than or equal to 0.25. Preferably, the mass ratio of the concentrated sulfuric acid to the iron-aluminum waste residues is 0.25-0.3 so as to control the pH value of the sulfuric acid leaching solution to be 1.0-2.0.
As a preferred feature of the method of the present invention,
in the step (2), the concentration of the calcium carbonate slurry is 150-400 g/L;
in the step (2), the dosage ratio of the sulfuric acid leaching solution to the calcium carbonate slurry is 3-6 mL/1 g;
in the step (2), the heating temperature is 50-70 ℃;
in the step (2), the adding speed of the calcium carbonate slurry is 1-3 ml/min;
in the step (2), after the calcium carbonate slurry is added, stirring reaction is continued for 30-90 min.
The concentration, the dosage and the addition speed of the calcium carbonate slurry and the reaction temperature play a decisive role in finally realizing the recovery of nickel, cobalt and copper and greatly reducing the content of nickel, cobalt and copper in the residual Fe-Al-Ca slag.
As a preferred feature of the method of the present invention,
in the step (3), the mass content of the Fe-Al-Ca slag in the prepared Fe-Al-Ca slag slurry is 25-35%.
As a preferred feature of the method of the present invention,
the aluminum removing liquid in the step (2) or/and the slag washing liquid in the step (3) is returned to the step (1) to prepare the iron-aluminum waste slag slurry. The aluminum-removing liquid or the slag-washing liquid is adopted to prepare the iron-aluminum waste slag slurry, and the slurry participates in the treatment process again, so that nickel, cobalt and copper in the aluminum-removing liquid and the slag-washing liquid can be further recovered, and the nickel content in the iron-aluminum-calcium waste slag can be reduced by more than 0.01 percent.
As a preferred feature of the method of the present invention,
the slag washing liquid in the step (3) is used for the next rinsing.
As a preference, the process according to the invention further comprises the following steps:
(4) Precipitating nickel cobalt copper: adding sodium carbonate solution with the mass concentration of 20-30% into the aluminum removal solution to enable nickel, cobalt, copper and aluminum to react to generate a nickel, cobalt and copper mixed carbonate and a nickel, cobalt and copper precipitation mother solution;
(5) Dissolving nickel cobalt copper carbonate sulfuric acid: adding water into the nickel-cobalt-copper mixed carbonate or dissolving the nickel-cobalt-copper precipitated mother liquor and sulfuric acid in the step (4), controlling the acidity to be pH value of 3-4.5, adding sodium carbonate solution with mass concentration of 5-10% for secondary aluminum removal, and carrying out solid-liquid separation after the reaction to obtain secondary aluminum removal slag and filtrate of mixed nickel sulfate, cobalt sulfate and copper sulfate.
By dissolving nickel, cobalt and copper again after sedimentation and removing aluminum, the impurity content of aluminum in the obtained filtrate of the mixed nickel sulfate, cobalt sulfate and copper sulfate can be further reduced compared with the direct secondary aluminum removal of aluminum removal liquid. The obtained filtrate of the mixed nickel sulfate, cobalt sulfate and copper sulfate can enter an extraction line to recycle nickel, cobalt and copper, thereby achieving the purpose of recycling nickel, cobalt and copper.
As a preferred feature of the method of the present invention,
the nickel-cobalt-copper precipitated mother liquor in the step (4) is used for preparing the Fe-Al-Ca slag slurry in the step (3) after the pH value of the mother liquor is regulated to be 4-6 by sulfuric acid.
As the preference of the method, the secondary aluminum removal slag is returned to the step (1) to be mixed with the iron-aluminum slag. Further recovering nickel, cobalt and copper metal elements in the aluminum slag.
The beneficial effects of the invention are as follows:
(1) The method comprises the steps of concentrated sulfuric acid leaching, primary aluminum iron removal of calcium carbonate, filtering and slag washing, precipitation of nickel, cobalt and copper by a concentrated sodium carbonate solution, sulfuric acid dissolution, secondary aluminum removal by a dilute sodium carbonate solution and the like, wherein the obtained iron, aluminum and calcium waste residues have low nickel, cobalt and copper contents, and the impurity contents of iron and aluminum in the nickel, cobalt and copper sulfate mixed sulfate are low;
(2) The nickel-cobalt-copper sulfate mixed sulfate solution prepared by the method can be mixed with a solution obtained by removing iron and aluminum from the leaching solution of the waste ternary lithium battery anode material, so that the process standard of preparing cobalt sulfate, nickel sulfate and copper sulfate by extraction and separation is reached;
(3) The invention uses low-valence calcium carbonate to replace high-valence sodium carbonate to remove aluminum, saves the treatment cost, has higher recovery rate of nickel, cobalt and copper elements separated from the iron-aluminum waste residue, has safe and environment-friendly working procedures, and is suitable for industrial production.
Detailed Description
The following is a further description of embodiments of the invention.
Unless otherwise indicated, all starting materials used in the present invention are commercially available or are commonly used in the art, and unless otherwise indicated, the methods in the examples below are all conventional in the art.
The invention provides an embodiment for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residues, which comprises the following steps:
(1) Sulfuric acid leaching: adding concentrated sulfuric acid into the iron-aluminum waste residue slurry for dissolution to prepare sulfuric acid leaching solution.
In some embodiments provided by the invention, the iron-aluminum waste residue slurry is prepared by water, or is prepared by aluminum removal liquid in the step (2), or is prepared by slag washing liquid in the step (3), or is prepared by aluminum removal liquid in the step (2) and slag washing liquid in the step (3) at the same time, or water is added on the basis of the aluminum removal liquid and the slag washing liquid; it is particularly preferable to use the aluminum removal liquid in the step (2) and the slag washing liquid in the step (3) simultaneously for preparation, and it has been found in repeated experiments that the nickel content in the iron-aluminum-calcium slag can be further reduced. Regardless of the preparation mode, the mass content of the iron-aluminum waste residue in the iron-aluminum waste residue slurry is 20% -35%.
In some embodiments provided by the invention, the concentrated sulfuric acid used is sulfuric acid with a concentration of not less than 70%, preferably not less than 95%, more preferably not less than 98%, and the mass ratio of the concentrated sulfuric acid to the iron-aluminum waste residue is not less than 0.25, so as to ensure that the pH of the sulfuric acid leaching solution is 1.0-2.0 or even lower.
In some embodiments provided herein, the concentrated sulfuric acid is added and stirred for 30-90 minutes at 200-300 r/min.
(2) Removing iron and aluminum: slowly adding calcium carbonate slurry into the sulfuric acid leaching solution, heating and stirring to enable iron and aluminum ions to generate an iron-aluminum hydroxide mixture, and carrying out solid-liquid separation to obtain iron-aluminum-calcium slag and aluminum removal liquid containing nickel-cobalt-copper mixed sulfate.
In some embodiments provided herein, the calcium carbonate slurry concentration is 150 to 400g/L; more preferably 290 to 400g/L.
In some embodiments provided herein, the sulfuric acid leach solution and the calcium carbonate slurry are used in a ratio of 3 to 6mL to 1g.
In some embodiments provided herein, the heating temperature is 50 to 70 ℃.
In some embodiments provided herein, the calcium carbonate slurry is slowly added at a rate of 1 to 3ml/min.
In some embodiments provided herein, the agitation rate is 200 to 300r/min; after the carbonic acid slurry is added, stirring reaction is continued for 30-90 min, and the pH value of the aluminum removal liquid after the final reaction is 4-4.5.
In some embodiments provided herein, the aluminum removal liquor portion is returned to step (1) to formulate an iron aluminum scrap slurry.
(3) Rinsing: and (3) preparing slurry from the Fe-Al-Ca slag, stirring and pulping, and filtering to obtain the Fe-Al-Ca slag and slag washing liquid.
In some embodiments provided by the invention, the mass content of the Fe-Al-Ca slag in the Fe-Al-Ca slag slurry is 25% -35%.
In some embodiments provided by the invention, the slag washing liquid is returned to the step (1) for preparing the iron-aluminum waste slag slurry, or the slag washing liquid is used for pulping and rinsing in the next step (3).
In some embodiments provided herein, further comprising steps (4) and (5) as follows:
(4) Precipitating nickel cobalt copper: adding aluminum removing liquid into sodium carbonate solution with the mass concentration of 20-30% to enable nickel, cobalt, copper and aluminum to react to generate a di-nickel, cobalt and copper mixed carbonate and a nickel, cobalt and copper precipitating mother solution.
In some embodiments provided by the invention, the reaction is carried out under stirring at a heating temperature of 50-70 ℃, the stirring speed is 250-350 r/min, the mixture is added with sodium carbonate solution and then is kept stand for 20-60 min, and the pH value of the system after the final reaction is 7-10.
In some embodiments provided by the invention, the nickel-cobalt-copper precipitated mother liquor is used for preparing the Fe-Al-Ca slag slurry in the step (3) after the pH value of the mother liquor is regulated to be 4-6 by sulfuric acid.
(5) Dissolving nickel cobalt copper carbonate sulfuric acid: adding water into the nickel-cobalt-copper mixed carbonate or dissolving the nickel-cobalt-copper precipitated mother liquor and sulfuric acid in the step (4), controlling the acidity to be pH value of 3-4.5, adding sodium carbonate solution with mass concentration of 5-10% for secondary aluminum removal, and carrying out solid-liquid separation after the reaction to obtain secondary aluminum removal slag and filtrate of mixed nickel sulfate, cobalt sulfate and copper sulfate.
In some embodiments provided by the invention, the reaction is carried out under stirring at a heating temperature of 50-70 ℃, the stirring speed is 250-350 r/min, the stirring is continued for 10-20 min after adding the sodium carbonate solution, then the reaction is kept stand for 20-60 min, and the pH value of the finally reacted system is 5-5.2.
In some embodiments provided by the invention, the filtrate of the mixed nickel sulfate, cobalt sulfate and copper sulfate is sent to an extraction section, and is mixed with the leaching solution after iron and aluminum are removed from the positive electrode of the waste ternary lithium battery, and the leaching solution is further recovered into nickel sulfate, cobalt sulfate and copper sulfate solution; and (3) returning the secondary aluminum removal slag to the step (1), mixing with the iron-aluminum slag, and recycling again.
Example 1
A method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residues comprises the following steps:
(1) Sulfuric acid leaching: placing 100g of iron-aluminum waste residue (dry basis, nickel content of 0.69%, cobalt content of 0.31% and copper content of 1.17%) into a 1000ml beaker, adding 300ml of water, stirring at a speed of 200r/min, adding 27g of 98% concentrated sulfuric acid, reacting for 30min, detecting the pH value of sulfuric acid leaching solution to be 1.1 to obtain sulfuric acid leaching solution 1#370ml, sampling and detecting the nickel content of 1.86g/L, cobalt content of 0.83g/L, copper content of 3.16g/L, aluminum content of 13.5g/L and iron content of 0.12g/L in the sulfuric acid leaching solution;
(2) Iron and aluminum removal: 20g of calcium carbonate powder is weighed and placed in 50ml of water, and calcium carbonate feed liquid 1# is obtained through stirring; adding 350ml of sulfuric acid leaching solution obtained in the step (1) into a 1000ml beaker, heating to 60 ℃, stirring at the speed of 250r/min, adding calcium carbonate feed liquid 1# at the speed of 2ml/min, stirring for 30min after adding, sampling, detecting the PH value of aluminum removal liquid to be 4.25, filtering to obtain 300ml of aluminum removal liquid 1#, 105g of iron aluminum calcium slag, detecting the nickel content of the aluminum removal liquid 1# to be 1.62g/L, the cobalt content to be 0.72g/L, the copper content to be 2.63g/L, the aluminum content to be 0.74g/L and the iron content to be 0.001g/L;
(3) Rinsing: placing the Fe-Al-Ca slag into 200ml of water, stirring and pulping for 30min, filtering to obtain Fe-Al-Ca slag 1#98g, and circulating the slag washing liquid 1#for replacing water in the next step (1). The nickel content in the iron-aluminum-calcium waste residue (dry basis) is detected to be 0.07%, the cobalt content is detected to be 0.05%, and the copper content is detected to be 0.18%.
The metal amount of 350mL of sulfuric acid leaching solution and 98g of Fe-Al-Ca waste residue 1 (the slag washing solution can be reused in the next treatment process, and is regarded as a recovered part), and in the iron-Al removal process, the nickel recovery rate is 89.5%, the cobalt recovery rate is 83.1% and the copper recovery rate is 84.1%.
Example 2 (slag washing liquid and aluminum removal liquid reuse)
A method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residues, which is different from example 1 in that: in the step (1), 100mL of the slag washing liquid 1#obtained in the example 1 and 200mL of the aluminum removal liquid 1#were used to prepare iron-aluminum slag slurry, and as a result:
in the sulfuric acid leaching solution treated in the step (1), the nickel content is 2.86g/L, the cobalt content is 1.28g/L, the copper content is 4.75g/L, the aluminum content is 13.7g/L, and the iron content is 0.11g/L (the content of nickel, cobalt and copper is more than 100g of the content of iron-aluminum waste residue dry basis calculated by 370mL of the total sulfuric acid leaching solution, which is caused by that part of nickel, cobalt and copper are brought in the slag washing solution and the aluminum removing solution);
in the aluminum removal liquid 2# obtained after the treatment in the step (2), detecting that the nickel content of the lower aluminum removal liquid 2# is 2.74g/L, the cobalt content is 1.20g/L, the copper content is 4.56g/L, the aluminum content is 0.78g/L, and the iron content is 0.002g/L;
in the iron-aluminum-calcium waste residue treated in the step (3), the nickel content is 0.06%, the cobalt content is 0.05%, and the copper content is 0.17%.
The nickel recovery rate of iron and aluminum is 94.1%, the cobalt recovery rate is 89.1% and the copper recovery rate is 90.0% calculated according to 350mL of sulfuric acid leaching solution and 98g of iron-aluminum-calcium waste residue 2.
Example 3 (slag washing liquid and aluminum removal liquid reuse)
A method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residues comprises the following steps:
(1) Sulfuric acid leaching: 200g of iron-aluminum waste residue (nickel content is 0.61%, cobalt content is 0.26%, copper content is 1.82%) is placed in a 1000ml beaker, 400ml of aluminum removal liquid 2#400ml and 100ml of slag washing liquid 2#100ml are added, stirring speed is 220 r/min, 55g of sulfuric acid is added, reaction is carried out for 30min, pH value of the leaching solution is detected to obtain 3#650ml of sulfuric acid leaching solution, sampling is carried out to detect that nickel content in the sulfuric acid leaching solution is 3.64g/L, cobalt content is 1.56g/L, copper content is 8.48g/L, aluminum content is 15.86g/L, and iron content is 0.12g/L;
(2) Adding 650ml of sulfuric acid leaching solution 2# into a 1000ml beaker, heating to 50 ℃, stirring at the rotation speed of 250r/min, slowly adding calcium carbonate slurry, wherein the calcium carbonate slurry is obtained by stirring 40g of calcium carbonate powder in 100ml of aluminum removal liquid 2# and is obtained by controlling the adding speed to be about 2ml/min, stirring for 30min after the adding is finished, sampling, detecting the PH value of the aluminum removal liquid to be 4.05, and filtering to obtain 3#640ml of aluminum removal liquid and 205g of iron aluminum calcium slag. Detecting the nickel content of the lower aluminum removal liquid 3# to be 3.52g/L, the cobalt content to be 1.52g/L, the copper content to be 8.19g/L, the aluminum content to be 1.2g/L and the iron content to be 0.001g/L;
(3) Rinsing: placing the obtained Fe-Al-Ca slag in a 1000ml beaker, adding 270ml of slag washing liquid 2#and stirring and pulping for 30min, filtering to obtain 270ml of slag washing liquid 3#and recycling for the next S1, and replacing water for use; adding 300ml of clear water into the Fe-Al-Ca slag, pulping for 30min again, filtering to obtain 3#198g of Fe-Al-Ca slag, and 4#305ml of slag washing liquid, and recycling the slag washing liquid for the next S4 to replace water for use; the nickel content in the iron-aluminum-calcium slag is detected to be 0.06%, the cobalt content is detected to be 0.05%, the copper content is detected to be 0.19%, and the nickel recovery rate in the aluminum removal process is calculated to be 95.5%, the cobalt recovery rate is calculated to be 91.3%, and the copper recovery rate is calculated to be 93.7%.
Example 4 (precipitated Nickel cobalt copper)
The difference in example 1 is that the aluminum removal liquid 1# obtained was subjected to the following treatment:
(4) Precipitating nickel cobalt copper: adding 300ml of aluminum removal liquid 1# into a 1000ml beaker, heating to 50 ℃, adding 25% sodium carbonate solution to precipitate nickel cobalt copper, stirring at a speed of 300r/min, controlling the pH value of the reaction liquid to be 10, standing for 20min, and filtering to obtain nickel cobalt copper mixed carbonate and nickel cobalt copper precipitation mother liquor 1#;
(5) Dissolving nickel cobalt copper carbonate sulfuric acid: dissolving nickel cobalt copper hydroxide by adding and precipitating nickel cobalt copper mother liquor 1#, and concentrated sulfuric acid, controlling the pH value to be 4, obtaining nickel sulfate, cobalt sulfate and copper sulfate mixed salt solution, heating to 70 ℃, slowly adding 10% sodium carbonate solution, stirring at the speed of 300r/min, detecting the pH value of the reaction solution to be 5.2, stopping adding 10% sodium carbonate, stirring for 10min, stopping stirring, standing for 20min, filtering, adding a small amount of water to wash a filter cake, and respectively obtaining secondary aluminum removal slag and filtrate; the detection shows that the aluminum content in the filtrate is 0.0046g/L and the iron content is 0.001g/L.
Comparative example 1 (sodium carbonate instead of calcium carbonate slurry)
The difference from example 1 is that an equal concentration of formulated sodium carbonate solution was used instead of calcium carbonate slurry, resulting in:
in the obtained Fe-Al-Ca waste residue, the nickel content is 0.23%, the cobalt content is 0.13%, and the copper content is 1.01%.
Calculated according to 350mL of sulfuric acid leaching solution and 98g of iron-aluminum-calcium waste residue, the recovery rate of nickel is 65.4%, the recovery rate of cobalt is 56.1%, and the recovery rate of copper is 10.5%. The method shows that the sodium carbonate is used as an aluminum precipitating agent, the nickel cobalt copper content in the aluminum slag is large, the recovery rate is low, and particularly the copper content is higher than 1%, so that for the treatment of the iron aluminum slag with low nickel cobalt copper content, the method has the advantages that the calcium carbonate is used as an aluminum removing agent, the nickel cobalt copper content in the slag is low, the calcium carbonate is lower in price than the sodium carbonate, and the aluminum removing cost is low.
Comparative example 2 (calcium carbonate slurry was added at one time)
The difference from example 1 is that the calcium carbonate slurry is added to the sulfuric acid leach solution at one time in step (2), resulting in:
in the obtained Fe-Al-Ca waste residue, the nickel content is 0.42%, the cobalt content is 0.15%, and the copper content is 0.82%.
Calculated according to 350mL of sulfuric acid leaching solution and 98g of iron-aluminum-calcium waste residue, the recovery rate of nickel is 36.8%, the recovery rate of cobalt is 49.4%, and the recovery rate of copper is 27.3%.
Comparative example 3 (aluminum removal at room temperature)
The difference from example 1 is that the reaction was carried out without heating in step (2), and the reaction was carried out at room temperature, resulting in:
in the obtained Fe-Al-Ca waste residue, the nickel content is 0.18%, the cobalt content is 0.12%, and the copper content is 0.68%.
Calculated according to 350mL of sulfuric acid leaching solution and 98g of iron-aluminum-calcium waste residue, the nickel recovery rate is 72.9%, the cobalt recovery rate is 59.5%, and the copper recovery rate is 39.7%.
Comparative example 4 (omitting the Nickel cobalt copper precipitation step)
The difference from example 4 is that step (4) was omitted, the pH value of aluminum removal liquid 1# was adjusted to 4, the temperature was heated to 70 ℃, 10% sodium carbonate solution was slowly added, the stirring speed was 300r/min, the pH value of the reaction liquid was detected to be 5.2, the addition of 10% sodium carbonate was stopped, stirring was further stopped for 10min, stirring was stopped, standing for 20min, filtration was performed, and a small amount of water was added to rinse the filter cake to obtain secondary aluminum removal slag and filtrate, respectively; the detection shows that the content of aluminum in the filtrate is 0.051g/L and the content of iron is 0.001g/L. It can be seen that the iron in the solution is easier to remove, and is basically stable after the step (2), reaching 1-2 ppm. As compared to example 4, it was found that the nickel cobalt copper precipitation step was advantageous for further removal of aluminum.
Claims (9)
1. The method for recovering the nickel-cobalt-copper mixed sulfate from the iron-aluminum waste residue is characterized by comprising the following steps of:
(1) Sulfuric acid leaching: adding concentrated sulfuric acid into the iron-aluminum waste residue slurry to dissolve to obtain sulfuric acid leaching solution, wherein iron-aluminum waste residues in the iron-aluminum waste residue slurry are solid waste residues generated after the waste ternary battery positive electrode material is subjected to sulfuric acid leaching recovery treatment, wherein nickel is less than or equal to 0.7%, cobalt is less than or equal to 0.4%, and copper is less than or equal to 1.2%;
(2) Removing iron and aluminum: slowly adding calcium carbonate slurry into the sulfuric acid leaching solution, heating and stirring to enable iron and aluminum ions to generate an iron-aluminum hydroxide mixture, and carrying out solid-liquid separation to obtain iron-aluminum-calcium slag and aluminum removal liquid containing nickel-cobalt-copper mixed sulfate;
(3) Rinsing: preparing slurry from the Fe-Al-Ca slag, stirring and pulping, and filtering to obtain Fe-Al-Ca slag and slag washing liquid;
in the step (1), the mass ratio of the concentrated sulfuric acid to the iron-aluminum waste residue is more than or equal to 0.25;
in the step (2), the concentration of the calcium carbonate slurry is 150-400 g/L;
in the step (2), the dosage ratio of the sulfuric acid leaching solution to the calcium carbonate slurry is 3-6 mL/1 g;
in the step (2), the heating temperature is 50-70 ℃;
in the step (2), the adding speed of the calcium carbonate slurry is 1-3 ml/min.
2. The method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residue according to claim 1, wherein,
in the step (1), the mass content of the iron-aluminum waste slag in the iron-aluminum waste slag slurry is 20% -35%.
3. The method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residue according to claim 1, wherein,
in the step (2), after the calcium carbonate slurry is added, stirring reaction is continued for 30-90 min.
4. The method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residue according to claim 1, wherein,
in the step (3), the mass content of the Fe-Al-Ca slag in the prepared Fe-Al-Ca slag slurry is 25-35%.
5. The method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residue according to claim 1, wherein,
the slag washing liquid in the step (3) is used for preparing the Fe-Al-Ca slag slurry by the next rinsing.
6. The method for recovering nickel cobalt copper mixed sulfate from iron aluminum waste residue according to claim 1, further comprising the steps of:
(4) Precipitating nickel cobalt copper: adding aluminum removing liquid into sodium carbonate solution with the mass concentration of 20-30% to enable nickel, cobalt, copper and aluminum to react to generate nickel, cobalt and copper mixed carbonate and nickel, cobalt and copper precipitating mother solution;
(5) Dissolving nickel cobalt copper carbonate sulfuric acid: adding water into the nickel-cobalt-copper mixed carbonate or dissolving the nickel-cobalt-copper precipitated mother liquor and sulfuric acid in the step (4), controlling the pH value to be 3-4.5, adding sodium carbonate solution with the mass concentration of 5-10% for secondary aluminum removal, and carrying out solid-liquid separation after the reaction to obtain secondary aluminum removal slag and filtrate of the mixed nickel sulfate, cobalt sulfate and copper sulfate.
7. The method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residue according to claim 6, wherein,
the aluminum removing liquid in the step (2) or/and the slag washing liquid in the step (3) is returned to the step (1) to prepare the iron-aluminum waste slag slurry.
8. The method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residue according to claim 6, wherein,
the nickel-cobalt-copper precipitated mother liquor in the step (4) is used for preparing the Fe-Al-Ca slag slurry in the step (3) after the pH value of the mother liquor is regulated to be 4-6 by sulfuric acid.
9. The method for recovering nickel cobalt copper mixed sulfate from iron aluminum waste residue according to claim 6, wherein the secondary aluminum removal residue is returned to step (1) to be mixed with iron aluminum waste residue.
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