CN111092273B - Novel method for comprehensively recovering cobalt, nickel, manganese and lithium elements from ternary battery waste - Google Patents
Novel method for comprehensively recovering cobalt, nickel, manganese and lithium elements from ternary battery waste Download PDFInfo
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- CN111092273B CN111092273B CN201910867738.0A CN201910867738A CN111092273B CN 111092273 B CN111092273 B CN 111092273B CN 201910867738 A CN201910867738 A CN 201910867738A CN 111092273 B CN111092273 B CN 111092273B
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- nickel
- cobalt
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- lithium
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 71
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 239000010941 cobalt Substances 0.000 title claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 38
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 31
- 239000011572 manganese Substances 0.000 title claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 120
- 238000005406 washing Methods 0.000 claims abstract description 82
- 238000000605 extraction Methods 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 63
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 47
- 239000012535 impurity Substances 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 27
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 27
- 238000001556 precipitation Methods 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000001376 precipitating effect Effects 0.000 claims abstract description 16
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 14
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 9
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims description 60
- 239000012065 filter cake Substances 0.000 claims description 42
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 38
- 238000001914 filtration Methods 0.000 claims description 32
- 239000011575 calcium Substances 0.000 claims description 20
- 229910001424 calcium ion Inorganic materials 0.000 claims description 19
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 17
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 17
- 229940044175 cobalt sulfate Drugs 0.000 claims description 17
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 17
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- 239000012452 mother liquor Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 7
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004073 vulcanization Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 53
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical group [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- C22B3/20—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
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
Abstract
A new method for comprehensively recovering cobalt, nickel, manganese and lithium from ternary battery waste relates to a method for recycling battery waste. The method comprises the steps of obtaining waste ternary battery material powder by disassembling waste ternary batteries, performing acid leaching, copper removal, iron and aluminum removal and other operations to obtain impurity removal liquid, adjusting the pH value of the solution of the impurity removal liquid by using sodium hydroxide, precipitating a mixture of cobalt hydroxide and nickel hydroxide, and performing vulcanization precipitation on residual cobalt and nickel ions by using sodium sulfide to separate manganese ions from the cobalt and nickel ions, directly precipitating manganese hydroxide, and preventing the manganese ions from entering an extraction process; dissolving the mixture of cobalt hydroxide and nickel hydroxide by sulfuric acid, extracting to remove impurities, separating cobalt and nickel to obtain a pure nickel sulfate solution, precipitating by using sodium hydroxide, and reversely washing for three times to obtain a battery-grade nickel hydroxide product. The invention solves the problem of high recovery cost caused by the extraction and back extraction process route for recovering cobalt, nickel and manganese elements in the prior art. Through an innovative process route, most of manganese ions are separated and removed before extraction, the nickel ions are not subjected to the extraction process of total extraction and total reaction, and the nickel hydroxide is directly precipitated after relevant impurities are removed only by extraction. Has the advantages of simple process, reduced material consumption and energy consumption, and remarkably reduced production cost.
Description
Technical Field
The invention relates to a recycling method of battery waste.
Background
In the process of disassembling and recycling cobalt, nickel, manganese and lithium from waste ternary battery materials, the method adopted by the prior art is as follows: waste ternary batteries are disassembled to obtain waste anode material powder, and then the waste anode material powder is subjected to acid leaching, copper removal, iron and aluminum removal, calcium and magnesium removal and other operations to obtain pre-extraction liquid, and two process routes are generally adopted: firstly, cobalt-nickel-manganese mixed salt solution is obtained through total extraction and total reaction, and is recycled by synthesizing a ternary precursor with sodium hydroxide after burdening; and secondly, obtaining high-concentration pure cobalt sulfate, nickel sulfate and manganese sulfate solutions through fractional extraction and separation, and respectively evaporating, concentrating and crystallizing to prepare battery-grade cobalt sulfate, nickel sulfate and manganese sulfate crystals for recovery.
No matter the ternary precursor is prepared from the mixed salt solution or the monomer cobalt sulfate, nickel sulfate and manganese sulfate crystals are prepared by graded extraction, all cobalt, nickel and manganese elements must pass through the extraction and back extraction process route, so that the problem of high manufacturing cost is caused. And the molar total of the extracted metal ions determines the production cost. Therefore, the current process route for recycling the waste ternary batteries is restricted by high cost of the extraction process, and the recycling of the waste ternary batteries is severely limited.
Disclosure of Invention
The invention aims to solve the problem that the recovery cost is high because the cobalt, nickel and manganese elements are required to be completely extracted and back-extracted in the prior art, and discloses a novel method for comprehensively recovering cobalt, nickel, manganese and lithium elements from ternary battery waste, which has the advantages of simple process, reduced material consumption and energy consumption and remarkably reduced production cost
The technical solution of the invention is as follows: the technical scheme of the new method for comprehensively recovering the cobalt, nickel, manganese and lithium elements from the ternary battery waste material is that the method comprises the following steps:
a. waste ternary battery powder obtained by disassembling waste ternary batteries is subjected to acid leaching, copper removal and aluminum removal to obtain impurity removal liquid, and the method is characterized in that:
b. adjusting pH of the impurity-removed solution to 5.5-6.5 with sodium hydroxide, precipitating cobalt hydroxide and nickel hydroxide mixture, filtering, washing, and treating the filter cake and the filtrate respectively.
c. The filter cake is a mixture of cobalt hydroxide and nickel hydroxide, the pH value is adjusted to about 5.0-6.0 after the cobalt hydroxide and nickel hydroxide are dissolved by sulfuric acid, fluoride is added into the dissolved solution to remove calcium and magnesium ions, the solution is filtered and washed, the filtrate enters a P204 extraction process, the impurities are deeply removed, and the extraction raffinate enters a P507 extraction process. And (3) obtaining a high-concentration pure cobalt sulfate solution after P507 cobalt ion full extraction and full reaction, evaporating and crystallizing to obtain a battery-grade cobalt sulfate product, wherein raffinate is a nickel sulfate solution, and entering CY272 impurity extraction process.
d. After the CY272 impurity extraction process, the raffinate is pure nickel sulfate liquid, the pH value is adjusted to 6-10 by sodium hydroxide, nickel hydroxide is precipitated, the nickel hydroxide is reversely washed by pure water for 2-4 times, preferably 3 times, the filter cake is battery-grade nickel hydroxide, and the filtrate and the washing liquid are recycled after being treated by a wastewater station.
e. B, adding sodium sulfide into the filtrate and washing liquid obtained in the step b to remove residual cobalt nickel ions, filtering and washing to obtain a filter cake which is a mixture of cobalt sulfide and nickel sulfide, and returning to the acid dissolving process; and (5) the filtrate and the washing liquid enter a manganese precipitation process.
f. And e, adjusting the pH of the filtrate and the washing liquid obtained in the step e to 8-11, preferably 9-10, by using sodium hydroxide to precipitate manganese ions, filtering and washing to obtain a manganese hydroxide filter cake and a lithium-containing filtrate and washing liquid.
g. Evaporating and crystallizing sodium sulfate from the lithium-containing filtrate and washing liquor to obtain concentrated lithium liquor, precipitating lithium carbonate by using sodium carbonate, filtering and washing to obtain a lithium carbonate filter cake and lithium precipitation mother liquor. The lithium precipitation mother liquor is returned to the iron and aluminum removal process to be used as the alkali liquor for adjusting the PH value.
Further, the sodium hydroxide is 32% or less liquid caustic soda or solid sodium hydroxide.
Furthermore, the concentration of the liquid caustic soda is 1-32% and 15-30%.
Further, the pH value of the impurity-removed solution is adjusted to 6-6.2 by sodium hydroxide.
Further, the sulfuric acid in the step c is 5-80%, preferably, 30-78%,40-77%,50-76%,55-75%,60-74%,65-73%,68-72%,70%.
Further, in the step c, the fluoride is added into the dissolving solution to remove calcium and magnesium ions, and sodium fluoride is added into the dissolving solution according to the proportion of 5-10 times, preferably 6-9 times and 7-8 times of the total amount of the calcium and magnesium ions in the dissolving solution, the reaction is carried out for 10-60 minutes, preferably 15-55 minutes, 20-50 minutes, 25-45 minutes and 30-40 minutes, and the calcium and magnesium ions are precipitated.
Further, in the step h, sodium sulfide is added according to the proportion of 2.0-5.0 times, preferably 2.5-4.5 times and 3-4 times of the total amount of cobalt and nickel in the filtrate and washing liquid obtained in the step b, solid sodium sulfide is added for reaction for 30-60 minutes, preferably 35-55 minutes and 40-50 minutes, and residual cobalt nickel ions are recovered.
By adopting the technical scheme, the invention solves the problem of high recovery cost caused by the fact that the cobalt, nickel and manganese elements recovered by the prior art need to pass through an extraction and back extraction process, so that most of manganese ions are separated and removed by adopting a wet method before extraction, the nickel ions are prevented from entering an extraction system, the nickel ions do not pass through the extraction process of full extraction and full back extraction, and the nickel hydroxide is directly precipitated after relevant impurities are removed only by extraction. Has the advantages of simple process, reduced material consumption and energy consumption, and remarkably reduced production cost.
Drawings
FIG. 1 is the top half of the process flow diagram of the present invention;
FIG. 2 is the lower half of the process flow diagram of the present invention.
Detailed Description
To facilitate a clearer understanding of the present invention, the present invention is further described below with reference to specific embodiments and examples in conjunction with fig. 1-2.
The implementation mode is as follows: the new method for comprehensively recovering cobalt, nickel, manganese and lithium from the ternary battery waste comprises the following steps:
a. and (3) carrying out acid leaching, copper removal and aluminum removal on waste ternary battery powder obtained by disassembling the waste ternary batteries to obtain impurity removal liquid.
b. Adjusting pH of the impurity-removed solution to 5.5-6.5 with sodium hydroxide, precipitating cobalt hydroxide and nickel hydroxide mixture, filtering, washing, and treating the filter cake and the filtrate respectively.
c. The filter cake is a mixture of cobalt hydroxide and nickel hydroxide, the pH value is adjusted to about 5.0-6.0 after the cobalt hydroxide and nickel hydroxide are dissolved by sulfuric acid, fluoride is added into the dissolved solution to remove calcium and magnesium ions, the solution is filtered and washed, the filtrate enters a P204 extraction process, the impurities are deeply removed, and the extraction raffinate enters a P507 extraction process. Obtaining high-concentration pure cobalt sulfate solution after P507 cobalt ion full extraction and full reaction, evaporating and crystallizing to obtain a battery-grade cobalt sulfate product, wherein raffinate is nickel sulfate solution, and entering CY272 extraction process.
d. After the CY272 impurity extraction process, the raffinate is pure nickel sulfate liquid, the pH value is adjusted to 6-10 by sodium hydroxide, nickel hydroxide is precipitated, the nickel hydroxide is reversely washed by pure water for 2-4 times, preferably 3 times, the filter cake is battery-grade nickel hydroxide, and the filtrate and the washing liquid are recycled after being treated by a wastewater station.
e. B, adding sodium sulfide into the filtrate and washing liquid obtained in the step b to remove residual cobalt nickel ions, filtering and washing to obtain a filter cake which is a mixture of cobalt sulfide and nickel sulfide, and returning to the acid dissolving process; and (5) the filtrate and the washing liquid enter a manganese precipitation process.
f. And e, adjusting the pH of the filtrate and the washing liquid obtained in the step e to 8-11, preferably 9-10 by using sodium hydroxide, precipitating manganese ions, filtering and washing to obtain a manganese hydroxide filter cake and a lithium-containing filtrate and washing liquid.
g. Evaporating and crystallizing sodium sulfate from the lithium-containing filtrate and washing liquor to obtain concentrated lithium liquor, precipitating lithium carbonate by using sodium carbonate, filtering and washing to obtain a lithium carbonate filter cake and a lithium precipitation mother liquor. The lithium precipitation mother liquor is returned to the iron and aluminum removal process to be used as the alkali liquor for adjusting the PH value.
Further, the sodium hydroxide is 32% or less liquid caustic soda or solid sodium hydroxide.
Furthermore, the concentration of the liquid caustic soda is 1-32% and 15-30%.
Further, the pH value of the impurity-removed solution is adjusted to 6-6.2 by sodium hydroxide.
Further, the fluoride in the step c is one of sodium fluoride, ammonium fluoride and potassium fluoride.
Further, the concentration of sulfuric acid in step c is 5-80%, preferably, 30-78%,40-77%,50-76%,55-75%,60-74%,65-73%,68-72%,70%.
Further, in the step c, the fluoride is added into the dissolving solution to remove calcium and magnesium ions, and sodium fluoride is added into the dissolving solution according to the proportion of 5-10 times, preferably 6-9 times and 7-8 times of the total amount of the calcium and magnesium ions in the dissolving solution to react for 10-60 minutes, preferably 15-55 minutes, 20-50 minutes, 25-45 minutes and 30-40 minutes, so that the calcium and magnesium ions are precipitated.
Further, in the step h, sodium sulfide is added according to the proportion of 2.0-5.0 times, preferably 2.5-4.5 times and 3-4 times of the total amount of cobalt and nickel in the filtrate and washing liquid obtained in the step b, solid sodium sulfide is added for reaction for 30-60 minutes, preferably 35-55 minutes and 40-50 minutes, and residual cobalt nickel ions are recovered.
Example 1: the new method for comprehensively recovering cobalt, nickel, manganese and lithium from the ternary battery waste comprises the following steps:
a. the method comprises the steps of disassembling waste ternary batteries to obtain waste ternary battery material powder, and performing operations such as acid leaching, copper removal, iron and aluminum removal and the like to obtain impurity removal liquid.
b. Regulating the pH value of the impurity-removed solution to 6.0 by using solid sodium hydroxide with the concentration of 98%, precipitating a mixture of cobalt hydroxide and nickel hydroxide, filtering and washing, and respectively treating a filter cake and filtrate.
C. Slowly adding a mixture of cobalt hydroxide and nickel hydroxide into an 80% sulfuric acid solution, and adjusting the pH value to be 5.5 by using the mixture of cobalt hydroxide and nickel hydroxide; adding ammonium fluoride in an amount which is 8 times of the total amount of calcium and magnesium ions in the dissolved solution, reacting for 60 minutes, filtering and washing; the filter cake is calcium-magnesium slag for additional treatment, the filtrate enters a P204 extraction process for impurity removal and extraction, and a small amount of impurities such as manganese, iron, zinc and the like brought by the mixture of cobalt hydroxide and nickel hydroxide are extracted and removed; the main ions in the raffinate are cobalt and nickel, and the extract enters the P507 extraction process. And (3) obtaining a high-concentration pure cobalt sulfate solution after P507 cobalt ion full extraction and full reaction, evaporating and crystallizing to obtain a battery-grade cobalt sulfate product, wherein raffinate is a nickel sulfate solution, and entering CY272 impurity extraction process.
d. After the CY272 impurity extraction process, the raffinate is pure nickel sulfate liquid, the PH value is adjusted to 10 by 98 percent solid sodium hydroxide to precipitate nickel hydroxide, and the filter cake is battery-grade nickel hydroxide after being reversely washed for 3 times by pure water. The filtrate and washing liquid are recycled after being treated by a wastewater station.
e. B, adding solid sodium sulfide according to 2.0 times of the total amount of cobalt and nickel in the filtrate and washing liquid obtained in the step b, reacting for 60 minutes, filtering and washing to obtain a filter cake which is a mixture of cobalt sulfide and nickel sulfide, and returning to the acid dissolving process; and (5) the filtrate and the washing liquid enter a manganese precipitation process.
f. And e, regulating the pH of the filtrate and the washing liquid obtained in the step e to 10.0 by using solid sodium hydroxide with the concentration of 98%, reacting for 60 minutes, filtering and washing to obtain a manganese hydroxide filter cake, a lithium-containing filtrate and a washing liquid.
g. Evaporating and concentrating the lithium-containing filtrate and washing liquor, centrifuging to remove crystalline sodium sulfate, concentrating the lithium solution, precipitating lithium carbonate by using sodium carbonate, filtering and washing to obtain a lithium carbonate filter cake and a lithium precipitation mother liquor. The lithium precipitation mother liquor is returned to the iron and aluminum removal process to be used as the alkali liquor for adjusting the PH value.
Example 2: the new method for comprehensively recovering cobalt, nickel, manganese and lithium from the ternary battery waste comprises the following steps:
a. the method comprises the steps of disassembling waste ternary batteries to obtain waste ternary battery material powder, and performing operations such as acid leaching, copper removal, iron and aluminum removal and the like to obtain impurity removal liquid.
b. Regulating the pH value of the impurity-removed solution to 5.8 by using a 32% sodium hydroxide solution, precipitating a mixture of cobalt hydroxide and nickel hydroxide, filtering and washing, and respectively treating a filter cake and filtrate.
C. Slowly adding a mixture of cobalt hydroxide and nickel hydroxide into a 50% sulfuric acid solution, and adjusting the pH value to 6.0 by using the mixture of cobalt hydroxide and nickel hydroxide; adding potassium fluoride 5 times of the total amount of calcium and magnesium ions in the solution, reacting for 50 minutes, filtering and washing; the filter cake is calcium-magnesium slag for additional treatment, the filtrate enters a P204 extraction process for impurity removal and extraction, and a small amount of impurities such as manganese, iron, zinc and the like brought by the mixture of cobalt hydroxide and nickel hydroxide are extracted and removed; the main ions in the raffinate are cobalt and nickel, and the cobalt and nickel enter the P507 extraction process. Obtaining high-concentration pure cobalt sulfate solution after P507 cobalt ion full extraction and full reaction, evaporating and crystallizing to obtain a battery-grade cobalt sulfate product, wherein raffinate is nickel sulfate solution, and entering CY272 extraction process.
d. After the CY272 impurity extraction process, the raffinate is pure nickel sulfate liquid, the pH value is adjusted to 10 by 32% sodium hydroxide solution to precipitate nickel hydroxide, and the filter cake is battery-grade nickel hydroxide after reverse washing for 3 times by pure water. The filtrate and washing liquid are recycled after being treated by a wastewater station.
e. B, adding solid sodium sulfide according to 3.0 times of the total amount of cobalt and nickel in the filtrate and washing liquid obtained in the step b, reacting for 30 minutes, filtering and washing to obtain a filter cake which is a mixture of cobalt sulfide and nickel sulfide, and returning to the acid dissolving process; and (5) the filtrate and the washing liquid enter a manganese precipitation process.
f. And e, regulating the pH of the filtrate and the washing liquid obtained in the step e to 9.0 by using a 32% sodium hydroxide solution, reacting for 60 minutes, filtering and washing to obtain a manganese hydroxide filter cake, a lithium-containing filtrate and a washing liquid.
g. Evaporating and concentrating the lithium-containing filtrate and washing liquor, centrifuging to remove crystalline sodium sulfate, concentrating the lithium solution, precipitating lithium carbonate by using sodium carbonate, filtering and washing to obtain a lithium carbonate filter cake and a lithium precipitation mother liquor. The lithium precipitation mother liquor is returned to the iron and aluminum removal process to be used as the alkali liquor for adjusting the PH value.
Example 3: the new method for comprehensively recovering cobalt, nickel, manganese and lithium from the ternary battery waste comprises the following steps:
a. the method comprises the steps of disassembling waste ternary batteries to obtain waste ternary battery material powder, and performing operations such as acid leaching, copper removal, iron and aluminum removal and the like to obtain impurity removal liquid.
b. Regulating the pH value of the impurity-removed solution to 6.2 by using a sodium hydroxide solution with the concentration of 15 percent to precipitate a mixture of cobalt hydroxide and nickel hydroxide, filtering and washing, and respectively treating a filter cake and filtrate.
C. Slowly adding a mixture of cobalt hydroxide and nickel hydroxide into a 70% sulfuric acid solution, and adjusting the pH value to be 5.0 by using the mixture of cobalt hydroxide and nickel hydroxide; adding sodium fluoride 10 times of the total amount of calcium and magnesium ions in the solution, reacting for 30 minutes, filtering and washing; the filter cake is calcium-magnesium slag and is additionally treated, the filtrate enters a P204 extraction process for impurity removal and extraction, and a small amount of impurities such as manganese, iron, zinc and the like brought by the mixture of cobalt hydroxide and nickel hydroxide are removed by extraction; the main ions in the raffinate are cobalt and nickel, and the extract enters the P507 extraction process. Obtaining high-concentration pure cobalt sulfate solution after P507 cobalt ion full extraction and full reaction, evaporating and crystallizing to obtain a battery-grade cobalt sulfate product, wherein raffinate is nickel sulfate solution, and entering CY272 extraction process.
d. After the CY272 impurity extraction process, the raffinate is pure nickel sulfate liquid, the pH value is adjusted to 9 by 15% sodium hydroxide solution to precipitate nickel hydroxide, and the filter cake is battery-grade nickel hydroxide after reverse washing for 3 times by pure water. The filtrate and washing liquid are recycled after being treated by a wastewater station.
e. B, adding solid sodium sulfide according to 3.5 times of the total amount of cobalt and nickel in the filtrate and washing liquid obtained in the step b, reacting for 40 minutes, filtering and washing to obtain a filter cake which is a mixture of cobalt sulfide and nickel sulfide, and returning to the acid dissolving process; and (5) the filtrate and the washing liquid enter a manganese precipitation process.
f. And e, regulating the pH of the filtrate and the washing liquid obtained in the step e to 8.5 by using a sodium hydroxide solution with the concentration of 15%, reacting for 60 minutes, filtering and washing to obtain a manganese hydroxide filter cake, a lithium-containing filtrate and a washing liquid.
g. And evaporating and concentrating the lithium-containing filtrate and washing liquor, centrifuging to remove crystalline sodium sulfate, concentrating the lithium solution, precipitating lithium carbonate by using sodium carbonate, filtering and washing to obtain a lithium carbonate filter cake and a lithium precipitation mother liquor. The lithium precipitation mother liquor is returned to the aluminum removing process to be used as alkali liquor for adjusting the PH value.
Example 4: the new method for comprehensively recovering cobalt, nickel, manganese and lithium from ternary battery waste comprises the following steps:
a. the method comprises the steps of disassembling waste ternary batteries to obtain waste ternary battery material powder, and performing operations such as acid leaching, copper removal, iron and aluminum removal and the like to obtain impurity removal liquid.
b. Regulating the pH value of the impurity-removed solution to 6.1 by using a sodium hydroxide solution with the concentration of 20 percent to precipitate a mixture of cobalt hydroxide and nickel hydroxide, filtering and washing, and respectively treating a filter cake and filtrate.
C. Slowly adding a mixture of cobalt hydroxide and nickel hydroxide into a 60% sulfuric acid solution, and adjusting the pH value to be 5.5 by using the mixture of cobalt hydroxide and nickel hydroxide; adding sodium fluoride 6 times of the total amount of calcium and magnesium ions in the solution, reacting for 45 minutes, filtering and washing; the filter cake is calcium-magnesium slag for additional treatment, the filtrate enters a P204 extraction process for impurity removal and extraction, and a small amount of impurities such as manganese, iron, zinc and the like brought by the mixture of cobalt hydroxide and nickel hydroxide are extracted and removed; the main ions in the raffinate are cobalt and nickel, and the cobalt and nickel enter the P507 extraction process. And (3) obtaining a high-concentration pure cobalt sulfate solution after P507 cobalt ion full extraction and full reaction, evaporating and crystallizing to obtain a battery-grade cobalt sulfate product, wherein raffinate is a nickel sulfate solution, and entering CY272 impurity extraction process.
d. After the CY272 impurity extraction process, the raffinate is pure nickel sulfate liquid, the pH value is adjusted to 9.5 by using 20% sodium hydroxide solution to precipitate nickel hydroxide, and the nickel hydroxide is reversely washed by pure water for 3 times, so that a filter cake is battery-grade nickel hydroxide. The filtrate and washing liquid are recycled after being treated by a wastewater station.
e. B, adding solid sodium sulfide 4.0 times of the total amount of cobalt and nickel in the filtrate and washing liquid obtained in the step b, reacting for 45 minutes, filtering and washing to obtain a filter cake which is a mixture of cobalt sulfide and nickel sulfide, and returning to the acid dissolving process; and (5) the filtrate and the washing liquid enter a manganese precipitation process.
f. And e, regulating the pH of the filtrate and the washing liquid obtained in the step e to 9.5 by using a sodium hydroxide solution with the concentration of 20%, reacting for 60 minutes, filtering and washing to obtain a manganese hydroxide filter cake, a lithium-containing filtrate and a washing liquid.
g. And evaporating and concentrating the lithium-containing filtrate and washing liquor, centrifuging to remove crystalline sodium sulfate, concentrating the lithium solution, precipitating lithium carbonate by using sodium carbonate, filtering and washing to obtain a lithium carbonate filter cake and a lithium precipitation mother liquor. The lithium precipitation mother liquor is returned to the iron and aluminum removal process to be used as the alkali liquor for adjusting the PH value.
The experimental data of the invention are as follows:
table 1 table of the relevant test data of the present invention
TABLE 2-1 auxiliary materials consumption Table after changing the procedure
Note: example 1 … is example 1 ….
Description of the drawings:
1. the raw material of the table is 18m 3 The impurity removing liquid comprises the following elements:
namely, the metal amount is: co:167.22 kg; ni:404.46kg; mn:227.88kg; li:110.52 And (kg).
2. The metal requiring total extraction and total reaction of the invention is only cobalt 167.22 kg.
3. According to the traditional process, the total extraction and total reaction metal is cobalt, nickel and manganese which are 799.56 kg.
TABLE 2-2 consumption table (18 m) of metal full extraction and full reverse auxiliary raw material in traditional process 3 Impurity removing liquid
Note: 3390. 3322 is the actual data of sodium hydroxide and sulfuric acid consumed by the applicant for extracting each ton of metal by the total extraction and total recovery process.
Tables 2-3 comparison table of auxiliary material consumption of the present invention and conventional total extraction total reflux process (18 m) 3 Impurity removing liquid
Description of the drawings: the data in this table only compare the portion of the conventional flow that requires total stripping.
While the invention has been described with respect to specific embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and alterations of the above embodiments according to the spirit and techniques of the present invention are also within the scope of the present invention.
Claims (12)
1. The method for comprehensively recovering cobalt, nickel, manganese and lithium from the ternary battery waste comprises the following steps:
a. waste ternary battery powder obtained by disassembling waste ternary batteries is subjected to acid leaching, copper removal and aluminum removal to obtain impurity removal liquid, and the method is characterized in that:
b. adjusting the pH value of the impurity-removed solution to 5.5-6.5 with sodium hydroxide, precipitating a mixture of cobalt hydroxide and nickel hydroxide, filtering and washing, and respectively treating a filter cake and filtrate;
c. the filter cake is a mixture of cobalt hydroxide and nickel hydroxide, the pH value is adjusted to 5.0-6.0 after the cobalt hydroxide and the nickel hydroxide are dissolved by sulfuric acid, fluoride is added into the dissolved solution to remove calcium and magnesium ions, the solution is filtered and washed, the filtrate enters a P204 extraction impurity process and is subjected to deep impurity removal, the extraction raffinate enters a P507 extraction process, a high-concentration pure cobalt sulfate solution is obtained after the P507 cobalt ions are fully extracted and fully reacted, a battery-grade cobalt sulfate product is prepared by evaporation and crystallization, and the raffinate is a nickel sulfate solution and enters a CY272 extraction impurity process;
d. after the CY272 impurity extraction process, the raffinate is pure nickel sulfate liquid, the pH value is adjusted to 6-10 by sodium hydroxide, nickel hydroxide is precipitated, the pure water is used for reverse washing for 2-4 times, the filter cake is battery-grade nickel hydroxide, and the filtrate and the washing liquid are recycled after being treated by a wastewater station;
e. b, adding sodium sulfide into the filtrate and washing liquid obtained in the step b to remove residual cobalt nickel ions, filtering and washing to obtain a filter cake which is a mixture of cobalt sulfide and nickel sulfide, and returning to the acid dissolving process; the filtrate and the washing liquid enter a manganese precipitation process;
f. e, regulating the pH of the filtrate and the washing liquid obtained in the step e to 8-11 by using sodium hydroxide to precipitate manganese ions, filtering and washing to obtain a manganese hydroxide filter cake, a lithium-containing filtrate and a washing liquid;
g. evaporating and crystallizing sodium sulfate from the lithium-containing filtrate and washing liquor to obtain concentrated lithium liquor, precipitating lithium carbonate by using sodium carbonate, filtering and washing to obtain a lithium carbonate filter cake and a lithium precipitation mother liquor, and returning the lithium precipitation mother liquor to the iron and aluminum removal process to be used as alkali liquor for adjusting the pH value.
2. The method for comprehensively recovering the cobalt, nickel, manganese and lithium from the ternary battery waste material as claimed in claim 1, wherein the sodium hydroxide is 32% or less of liquid caustic soda or solid sodium hydroxide.
3. The method for comprehensively recovering the cobalt, nickel, manganese and lithium from the ternary battery waste material as recited in claim 2, wherein the concentration of the liquid caustic soda is 15-30%.
4. The method for comprehensively recovering the cobalt, nickel, manganese and lithium elements from the ternary battery waste as claimed in claim 1, wherein the pH value of the impurity removal solution is adjusted to 6-6.2 by using sodium hydroxide.
5. The method for comprehensively recovering Co, ni, mn and Li from the waste material of ternary batteries as claimed in claim 1, wherein the concentration of sulfuric acid in step c is 5-80%.
6. The method for comprehensively recovering the cobalt, nickel, manganese and lithium from the ternary battery waste material as recited in claim 5, wherein the concentration of sulfuric acid is 30-78%.
7. The method for comprehensively recovering the cobalt, nickel, manganese and lithium from the ternary battery waste material as claimed in claim 6, wherein the concentration of sulfuric acid is 40-77%.
8. The method for comprehensively recovering Co, ni, mn and Li elements from the ternary battery wastes as claimed in claim 1, wherein the step c of adding fluoride to the solution to remove Ca and Mg ions is to add a fluoride in an amount of 5-10 times of the total amount of Ca and Mg ions in the solution, and the reaction is carried out for 10-60 minutes to precipitate Ca and Mg ions.
9. The method for comprehensively recovering the cobalt, nickel, manganese and lithium elements from the ternary battery wastes as recited in claim 8, wherein the step of adding the fluoride to the solution to remove calcium and magnesium ions is to add a fluoride substance in an amount 7-8 times of the total amount of calcium and magnesium ions in the solution to react for 30-40 minutes to precipitate calcium and magnesium ions.
10. The method for comprehensively recovering the cobalt, nickel, manganese and lithium from the ternary battery waste material as claimed in claim 1 or 9, wherein the fluoride is one of sodium fluoride, ammonium fluoride and potassium fluoride.
11. The method for comprehensively recovering Co, ni, mn and Li elements from the waste material of the ternary battery as claimed in claim 1, wherein the sodium sulfide added in step e is added in solid state according to 2.0-5.0 times of the total amount of Co and Ni in the filtrate and washing solution obtained in step b, and the reaction is carried out for 30-60 minutes to recover the residual Co, ni and Fe ions.
12. The method for comprehensively recovering Co, ni, mn and Li elements from the waste material of ternary batteries as claimed in claim 11, wherein the sodium sulfide is added in a solid state in an amount of 3-4 times of the total amount of Co and Ni in the filtrate and washing solution obtained in step b, and the reaction is carried out for 40-50 minutes to recover the residual Co, ni and Fe ions.
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| CN201910867738.0A CN111092273B (en) | 2019-09-14 | 2019-09-14 | Novel method for comprehensively recovering cobalt, nickel, manganese and lithium elements from ternary battery waste |
| EP20863734.8A EP4030533A4 (en) | 2019-09-14 | 2020-08-17 | Manganese-lithium separation and pre-extraction liquid preparation processes in comprehensive recovery of ternary battery waste, and method for comprehensive recovery of cobalt-nickel-manganese-lithium elements from ternary battery waste |
| JP2022502096A JP7216945B2 (en) | 2019-09-14 | 2020-08-17 | Manganese-lithium separation and pre-extraction solution preparation process in comprehensive recovery of ternary battery waste and method for comprehensive recovery of cobalt-nickel-manganese-lithium elements from ternary battery waste |
| PCT/CN2020/109430 WO2021047352A1 (en) | 2019-09-14 | 2020-08-17 | Manganese-lithium separation and pre-extraction liquid preparation processes in comprehensive recovery of ternary battery waste, and method for comprehensive recovery of cobalt-nickel-manganese-lithium elements from ternary battery waste |
| US17/569,584 US20220166079A1 (en) | 2019-09-14 | 2022-01-06 | Manganese-lithium separation process and pre-extraction solution preparation process in comprehensive recovery of ternary battery wastes, and method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from ternary battery wastes |
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| EP4030533A4 (en) * | 2019-09-14 | 2023-10-18 | Hunan Jin Yuan New Materials Joint Stock Company Limited | Manganese-lithium separation and pre-extraction liquid preparation processes in comprehensive recovery of ternary battery waste, and method for comprehensive recovery of cobalt-nickel-manganese-lithium elements from ternary battery waste |
| CN111455174A (en) * | 2020-06-09 | 2020-07-28 | 矿冶科技集团有限公司 | Method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel hydroxide cobalt |
| CN111500862A (en) * | 2020-06-09 | 2020-08-07 | 矿冶科技集团有限公司 | Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate |
| CN112079395A (en) * | 2020-09-17 | 2020-12-15 | 常宁市华兴冶化实业有限责任公司 | Method for preparing high-purity cobalt sulfate crystal |
| CN112820974B (en) * | 2020-11-26 | 2022-06-14 | 清华四川能源互联网研究院 | Impurity removal and treatment method in lithium battery scrapped positive electrode material recovery process |
| CN112575195A (en) * | 2020-12-02 | 2021-03-30 | 贵州鹏程新材料有限公司 | Process for re-extracting cobalt and nickel from waste and old waste slag |
| CN114212837A (en) * | 2021-12-31 | 2022-03-22 | 江西睿达新能源科技有限公司 | Method for recovering and treating lithium-nickel-containing crystallization mother liquor |
| CN115386737A (en) * | 2022-08-12 | 2022-11-25 | 清远先导材料有限公司 | Method for recovering solution containing low-concentration cobalt and nickel |
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Denomination of invention: A new method for comprehensive recovery of cobalt, nickel, manganese, and lithium elements from ternary battery waste Effective date of registration: 20231225 Granted publication date: 20221118 Pledgee: Agricultural Bank of China Limited Anhua County sub branch Pledgor: HUNAN JIN YUAN NEW MATERIALS JOINT STOCK Co.,Ltd. Registration number: Y2023980073785 |
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