CN109279665A - A kind of processing method of nickle cobalt lithium manganate ternary waste material - Google Patents
A kind of processing method of nickle cobalt lithium manganate ternary waste material Download PDFInfo
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- CN109279665A CN109279665A CN201811066427.6A CN201811066427A CN109279665A CN 109279665 A CN109279665 A CN 109279665A CN 201811066427 A CN201811066427 A CN 201811066427A CN 109279665 A CN109279665 A CN 109279665A
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- cobalt
- solution
- nickel
- lithium
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- 239000002699 waste material Substances 0.000 title claims abstract description 36
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000003672 processing method Methods 0.000 title claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 68
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 56
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011572 manganese Substances 0.000 claims abstract description 41
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 39
- 239000010941 cobalt Substances 0.000 claims abstract description 38
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 38
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000011084 recovery Methods 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000001376 precipitating effect Effects 0.000 claims abstract description 17
- 239000002893 slag Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 41
- 238000001816 cooling Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 29
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims description 24
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 19
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 19
- 239000001099 ammonium carbonate Substances 0.000 claims description 19
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 18
- 229940044175 cobalt sulfate Drugs 0.000 claims description 16
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 13
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 12
- 238000007885 magnetic separation Methods 0.000 claims description 12
- 229940099596 manganese sulfate Drugs 0.000 claims description 12
- 235000007079 manganese sulphate Nutrition 0.000 claims description 12
- 239000011702 manganese sulphate Substances 0.000 claims description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 239000003337 fertilizer Substances 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 9
- 239000002351 wastewater Substances 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001947 lithium oxide Inorganic materials 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 description 16
- 238000004064 recycling Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 229910009378 Zn Ca Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015853 MSO4 Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical class [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 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
- C01G53/08—Halides
- C01G53/09—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- 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
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of processing methods of nickle cobalt lithium manganate ternary waste material.Ternary waste material is added into alkali soluble solution, amphoteric metal aluminium etc. is dissolved into solution, realize the separation of aluminium and other components, the solid after separation aluminium is restored into furnace reduction again, substance after reduction adds pure water, lithia is dissolved in hot pure water and obtains lithium hydroxide, to realize the separation between lithium and nickel cobalt manganese, by controlling the additional amount of sulfuric acid and the pH of final process and terminal, to realize the separation of the metals such as the stronger manganese metal of activity and nickel cobalt, slag after separating manganese is after pulp, by electromagnetic separation, add dissolving with hydrochloric acid, obtained nickel and cobalt solution is passed through chlorine under certain temperature and pressure, so that cobalt ions oxydrolysis is trivalent cobalt precipitating, to realize the separation of nickel cobalt.Process of the present invention is short, and waste water yield is few, and material recovery rate is high, and obtained product is LITHIUM BATTERY, and added value of product is high.
Description
Technical field
The present invention relates to a kind of processing methods of nickle cobalt lithium manganate ternary waste material, belong to waste recycling field.
Background technique
As the adjustment of national policy, vehicle look forward to the raising to course continuation mileage demand, battery enterprise is laid out ternary battery one after another
Business.Nickle cobalt lithium manganate with relatively inexpensive nickel and manganese instead of in cobalt acid lithium 2/3rds or more cobalt, advantage in terms of cost
It is clearly compared with other lithium cell anode material lithium manganates, LiFePO 4, nickel-cobalt lithium manganate material and cobalt acid lithium
It is very close in terms of chemical property and processing performance, so that nickel-cobalt lithium manganate material becomes new battery material and gradually takes
For cobalt acid lithium, become the favorite of lithium ion battery material of new generation.
2015, the annual sales amount of New-energy electric vehicle was more than 33.11 ten thousand, and was produced in new-energy automobile in 2016
Sales volume is more than 50.7 ten thousand, and there are about 50% for year-on-year speedup.The service life of lithium ion battery is generally 3~5 years, with lithium-ion electric
The production and consumption in pond, will certainly generate a large amount of waste and old lithium ion battery, if to these waste and old lithium ion batteries set no
Reason, certainly will will cause the waste of very important resource and generate a large amount of harmful substance.Specific manifestation is as follows:
First is that containing there are many valuable metals, such as cobalt, nickel, aluminium, lithium in waste and old lithium ion battery.For cobalt aspect, China
95% cobalt be from external import, and the whole world cobalt yield have 150,000 tons, this 150,000 ton-mile face, which has 80%, to be got by recycling
's；
Second is that the various heavy (such as cobalt, nickel) contained in waste and old lithium ion battery, electrolyte (lithium hexafluoro phosphate etc.),
These heavy metals and organic matter all can cause huge harm to the health of natural environment and the mankind；
Third is that the diaphragm, shell etc. in waste and old lithium ion battery belong to nondegradable waste, if without having
The processing of effect is just piled up arbitrarily, and a large amount of noxious waste pollution and serious air pollution will certainly be brought to environment.
In conclusion the recycling of waste and old lithium ion battery is very important, for the recycling of ternary lithium battery, due to just
Containing valuable metals such as lithium, cobalt, nickel in the material of pole, recovery value is huge, so by everybody attention.
For the processing of nickle cobalt lithium manganate ternary waste material, sulfuric acid and reducing agent dissolution is generally added in conventional technique, so
Afterwards by elements such as P204 extraction and separation MnZns therein, nickel salt and cobalt salt, raffinate warp are obtained using P507 extraction and separation
It crosses precipitating and recycles lithium therein, this process is very long, and equipment investment is big, and waste water yield is more, and the rate of recovery is low, and due to nickel cobalt manganese
Content it is suitable, extraction series is especially long.
Summary of the invention
In view of this, process is short the present invention provides a kind of processing method of nickle cobalt lithium manganate ternary waste material, waste water is generated
Amount is few, and material recovery rate is high, and obtained product is LITHIUM BATTERY, can return to the raw material for doing ternary anode material of lithium battery.
The present invention solves above-mentioned technical problem by following technological means:
A kind of processing method of nickle cobalt lithium manganate ternary waste material of the invention, is following steps:
(1) aqueous slkali being added in nickle cobalt lithium manganate ternary waste material, impregnated 4-6 hours, soaking temperature is 50-65 DEG C, filtering,
It obtains containing aluminum solutions and filter residue, filter residue is dried and sieved after washing, and screenings is put into reduction furnace and is restored, reduction temperature
Degree is 330-450 DEG C, and the recovery time is 6-9 hours, and discharging obtains cooling material after then cooling down；
(2) by cooling expect that hot pure water stirring is added, maintaining the temperature of whipping process is 90-95 DEG C, mixing time 3-4
Hour, it is separated by solid-liquid separation, obtains filtrate containing lithium and filter residue, filter residue is mixed with filtrate containing lithium after washing, by cleaning solution；
(3) sulfuric acid solution pulp is added in filter residue after the washing for obtaining step (2), and the concentration of sulfuric acid solution is 1- 2mol/
L, the ratio between the molal quantity of manganese is 0.9-0.95:1 in filter residue after sulfuric acid is added and washs, when the pH of reaction to solution is greater than 6.5,
Continuously adding sulfuric acid and maintaining the pH of reaction is 6-6.5, is stirred to react at this ph, is 20-50mg/L to the cobalt content in solution
When, stop reaction, filtering obtains manganese containing solution and cobalt nickel slag, and cobalt nickel slag obtains cobalt nickel washed-residue by washing, cleaning solution with contain
Manganese solution mixing；
(4) after cobalt nickel washed-residue adds water slurry, by electromagnetic separation, magnetic separation material is obtained, hydrochloric acid solution is added in magnetic separation material,
Temperature is to be stirred to react 3-4 hours at 60-80 DEG C, is then filtered, and the first filtrate and the first filter residue are obtained, and the first filtrate is added anti-
It answering in kettle, then it is 140-160 DEG C in temperature that adjusting pH, which is 1.8-2.5, it is passed through chlorine and pressure is made to be 1.5-2 atmospheric pressure,
It reacts under this atmospheric pressure 3-5 hours, is filtered after then cooling down release, obtain cobalt precipitating and nickel solution, nickel solution is by concentration
Crystallization obtains LITHIUM BATTERY nickel chloride, and cobalt precipitating is added sulfuric acid solution, adds reducing agent, it is molten to obtain cobaltous sulfate after being completely dissolved
Liquid obtains battery grade cobalt sulfate crystal by condensation crystallization；
(5) ammonium bicarbonate soln is added in filtrate containing lithium, and the pH for adjusting solution is 7.2-7.5, and reaction temperature is taken the photograph for 35-45
Family name's degree, is then filtered, and obtains battery-level lithium carbonate；
(6) manganese containing solution obtains LITHIUM BATTERY manganese sulfate by condensing crystallizing, and the mother liquor after crystallization is passed through hydrogen sulfide gas, will
After nickel cobalt content therein is reduced to 10ppm or less, filtering, filter residue is back in reduction furnace, and filtrate returns mixed with manganese containing solution
It closes.
The concentration of step (1) aqueous slkali is 3-5mol/L, is passed through carbon dioxide containing aluminum solutions, adjusts the pH of solution
For 9-10, by filtering and washing obtains aluminium hydroxide.
Cooling material and the mass ratio of hot pure water are 1:4-5 in the step (2), and washing is washed using four-stage counter-current.
The concentration of hydrochloric acid solution is 1.5-2mol/L in the step (4).
The concentration of ammonium bicarbonate soln is 2-3mol/L in the step (5), and the time that ammonium bicarbonate soln is added is
1.5-2 hours, the filtrate obtained after filtering obtained ammonium fertilizer by condensing crystallizing.
The Baume degrees for being concentrated into solution in the step (6) when condensing crystallizing is 49-51, is then cooled down, rate of temperature fall is
2-3 DEG C/h, being cooled to temperature is 10-15 DEG C, is centrifuged using decanter centrifuge.
The reducing agent that the step (1) uses when restoring is at least one of hydrogen, methane, carbon monoxide, water-gas.
The present invention handles nickle cobalt lithium manganate ternary waste material, first uses alkali soluble solution, amphoteric metal aluminium etc. is dissolved into solution,
Using separation of solid and liquid, the separation of aluminium and other components is realized, then the solid after separation aluminium is restored into furnace reduction, due to lithium
For active metal, cannot be restored by reducing gas such as hydrogen, and nickel cobalt manganese etc. can be reduced, the substance after reduction adds pure
Water washing, lithia is dissolved in hot pure water and obtains lithium hydroxide, and the metals such as cobalt nickel manganese are insoluble, to realize lithium and nickel cobalt
Separation between manganese.
Sulfuric acid is added in slag after separation, following reaction occurs:
Mn+H2SO4----MnSO4+H2
M+H2SO4----MSO4+H2(M Ni/Co)
Mn+MSO4----M+MnSO4(M Ni/Co)
By controlling the additional amount of sulfuric acid and the pH of final process and terminal, to realize the stronger metal of activity
The separation of the metals such as manganese and nickel cobalt, wherein dissolution reaction and displacement reaction has occurred, obtained manganese solution is obtained by condensing crystallizing
To LITHIUM BATTERY manganese sulfate, the mother liquor after condensing crystallizing returns after hydrogen persulfide is except nickel cobalt to be used, obtained a small amount of removal of impurities slag
It comes back for restoring.
Slag after separating manganese is after pulp, by electromagnetic separation, by the metal powders such as magnetic nickel cobalt with
Do not have the separation such as magnetic other impurities such as copper, lead, adds dissolving with hydrochloric acid, obtained nickel and cobalt solution is in certain temperature and pressure
It is passed through chlorine under power, so that cobalt ions oxydrolysis is trivalent cobalt precipitating, and nickel can not be oxidized at this ph, to realize
The separation of nickel cobalt, obtained nickel solution obtain LITHIUM BATTERY nickel chloride crystal by condensing crystallizing, and sulphur is added in obtained cobalt precipitating
Acid solution and reducing agent, dissolution obtain cobalt sulfate solution, obtain battery grade cobalt sulfate using condensing crystallizing.
Ammonium hydrogen carbonate is added in obtained lithium hydroxide, obtains battery-level lithium carbonate by precipitating, mother liquor passes through condensing crystallizing
Ammonium fertilizer is obtained, whole process does not generate waste water, condensing crystallizing mistake in addition to the recycling of aluminium generates waste water outlet substantially elsewhere
The vapor that journey generates can obtain pure water by condensing recovery, return and use, waste water yield is few, and realizes complete group
Point, such as the recycling of aluminium, nickel, cobalt, manganese, lithium.
Compare other techniques, this process flow is short, and the rate of recovery of component is high, and the solid waste of generation is few, obtains electricity
Lithium carbonate, cobaltous sulfate, nickel chloride and the manganese sulfate of pond grade, can return to and prepare nickel-cobalt lithium manganate cathode material again, reached circulation
The purpose of reconstruction.
This process flow is short, and can be realized all components, such as the recycling and utilization of aluminium foil, phosphate, molysite, lithium salts,
Available aluminium hydroxide, iron oxide red, battery grade lithium phosphate and hydrophosphate, the rate of recovery is high, at low cost, value-added content of product
It is high.
Beneficial effects of the present invention: process is short, and waste water yield is few, and material recovery rate is high, and obtained product is battery
Grade, can return to the raw material for doing ternary anode material of lithium battery.
Detailed description of the invention
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the SEM for the aluminium hydroxide that the embodiment of the present invention 1 obtains.
Specific embodiment
Below with reference to attached drawing, the present invention is described in detail, a kind of nickle cobalt lithium manganate ternary waste material of the present embodiment
Processing method is following steps:
(1) aqueous slkali being added in nickle cobalt lithium manganate ternary waste material, impregnated 4-6 hours, soaking temperature is 50-65 DEG C, filtering,
It obtains containing aluminum solutions and filter residue, filter residue is dried and sieved after washing, and screenings is put into reduction furnace and is restored, reduction temperature
Degree is 330-450 DEG C, and the recovery time is 6-9 hours, and discharging obtains cooling material after then cooling down；
(2) by cooling expect that hot pure water stirring is added, maintaining the temperature of whipping process is 90-95 DEG C, mixing time 3-4
Hour, it is separated by solid-liquid separation, obtains filtrate containing lithium and filter residue, filter residue is mixed with filtrate containing lithium after washing, by cleaning solution；
(3) sulfuric acid solution pulp is added in filter residue after the washing for obtaining step (2), and the concentration of sulfuric acid solution is 1- 2mol/
L, the ratio between the molal quantity of manganese is 0.9-0.95:1 in filter residue after sulfuric acid is added and washs, when the pH of reaction to solution is greater than 6.5,
Continuously adding sulfuric acid and maintaining the pH of reaction is 6-6.5, is stirred to react at this ph, is 20-50mg/L to the cobalt content in solution
When, stop reaction, filtering obtains manganese containing solution and cobalt nickel slag, and cobalt nickel slag obtains cobalt nickel washed-residue by washing, cleaning solution with contain
Manganese solution mixing；
(4) after cobalt nickel washed-residue adds water slurry, by electromagnetic separation, magnetic separation material is obtained, hydrochloric acid solution is added in magnetic separation material,
Temperature is to be stirred to react 3-4 hours at 60-80 DEG C, is then filtered, and the first filtrate and the first filter residue are obtained, and the first filtrate is added anti-
It answering in kettle, then it is 140-160 DEG C in temperature that adjusting pH, which is 1.8-2.5, it is passed through chlorine and pressure is made to be 1.5-2 atmospheric pressure,
It reacts under this atmospheric pressure 3-5 hours, is filtered after then cooling down release, obtain cobalt precipitating and nickel solution, nickel solution is by concentration
Crystallization obtains LITHIUM BATTERY nickel chloride, and cobalt precipitating is added sulfuric acid solution, adds reducing agent, it is molten to obtain cobaltous sulfate after being completely dissolved
Liquid obtains battery grade cobalt sulfate crystal by condensation crystallization；
(5) ammonium bicarbonate soln is added in filtrate containing lithium, and the pH for adjusting solution is 7.2-7.5, and reaction temperature is taken the photograph for 35-45
Family name's degree, is then filtered, and obtains battery-level lithium carbonate；
(6) manganese containing solution obtains LITHIUM BATTERY manganese sulfate by condensing crystallizing, and the mother liquor after crystallization is passed through hydrogen sulfide gas, will
After nickel cobalt content therein is reduced to 10ppm or less, filtering, filter residue is back in reduction furnace, and filtrate returns mixed with manganese containing solution
It closes.
The concentration of step (1) aqueous slkali is 3-5mol/L, is passed through carbon dioxide containing aluminum solutions, adjusts the pH of solution
For 9-10, by filtering and washing obtains aluminium hydroxide.
Cooling material and the mass ratio of hot pure water are 1:4-5 in the step (2), and washing is washed using four-stage counter-current.
The concentration of hydrochloric acid solution is 1.5-2mol/L in the step (4).
The concentration of ammonium bicarbonate soln is 2-3mol/L in the step (5), and the time that ammonium bicarbonate soln is added is
1.5-2 hours, the filtrate obtained after filtering obtained ammonium fertilizer by condensing crystallizing.
The Baume degrees for being concentrated into solution in the step (6) when condensing crystallizing is 49-51, is then cooled down, rate of temperature fall is
2-3 DEG C/h, being cooled to temperature is 10-15 DEG C, is centrifuged using decanter centrifuge.
The reducing agent that the step (1) uses when restoring is at least one of hydrogen, methane, carbon monoxide, water-gas.
Embodiment 1
A kind of processing method of nickle cobalt lithium manganate ternary waste material, is following steps:
(1) aqueous slkali is added in nickle cobalt lithium manganate ternary waste material, impregnated 5 hours, soaking temperature is 59 DEG C, and filtering obtains
Containing aluminum solutions and filter residue, filter residue is dried and is sieved after washing, and screenings is put into reduction furnace and is restored, and reduction temperature is
420 DEG C, the recovery time is 8 hours, and discharging obtains cooling material after then cooling down；
(2) by cooling expect that hot pure water stirring is added, maintaining the temperature of whipping process is 93 DEG C, and mixing time is 3.5 hours,
It is separated by solid-liquid separation, obtains filtrate containing lithium and filter residue, filter residue is mixed with filtrate containing lithium after washing, by cleaning solution；
(3) sulfuric acid solution pulp is added in filter residue after the washing for obtaining step (2), and the concentration of sulfuric acid solution is 1.5mol/
L, the ratio between molal quantity that sulfuric acid and manganese in filter residue after washing is added is 0.93:1, when the pH of reaction to solution is greater than 6.5, continues to add
Entering sulfuric acid to maintain the pH of reaction is 6-6.5, is stirred to react at this ph, when the cobalt content in solution is 30mg/L, is stopped anti-
It answers, filters, obtain manganese containing solution and cobalt nickel slag, cobalt nickel slag obtains cobalt nickel washed-residue by washing, and cleaning solution and manganese containing solution are mixed
It closes；
(4) after cobalt nickel washed-residue adds water slurry, by electromagnetic separation, magnetic separation material is obtained, hydrochloric acid solution is added in magnetic separation material,
Temperature is to be stirred to react 3.5 hours at 70 DEG C, is then filtered, and the first filtrate and the first filter residue are obtained, and reaction is added in the first filtrate
In kettle, adjusting pH is 1.95, is then 155 DEG C in temperature, is passed through chlorine and pressure is made to be 1.8 atmospheric pressure, in this atmospheric pressure
Lower reaction 4.5 hours, is filtered after then cooling down release, obtains cobalt precipitating and nickel solution, and nickel solution obtains electricity by condensing crystallizing
Pond grade nickel chloride, cobalt precipitating is added sulfuric acid solution, adds reducing agent, obtain cobalt sulfate solution after being completely dissolved, by condensation
Crystallization obtains battery grade cobalt sulfate crystal；
(5) ammonium bicarbonate soln is added in filtrate containing lithium, and the pH for adjusting solution is 7.3, and reaction temperature is 42 degrees Celsius, then
Filtering, obtains battery-level lithium carbonate；
(6) manganese containing solution obtains LITHIUM BATTERY manganese sulfate by condensing crystallizing, and the mother liquor after crystallization is passed through hydrogen sulfide gas, will
After nickel cobalt content therein is reduced to 10ppm or less, filtering, filter residue is back in reduction furnace, and filtrate returns mixed with manganese containing solution
It closes.
The concentration of step (1) aqueous slkali is 4.2mol/L, is passed through carbon dioxide containing aluminum solutions, adjusts the pH of solution
It is 9.5, by filtering and washing obtains aluminium hydroxide.
Cooling material and the mass ratio of hot pure water are 1:4.5 in the step (2), and washing is washed using four-stage counter-current.
The concentration of hydrochloric acid solution is 1.8mol/L in the step (4),.
The concentration of ammonium bicarbonate soln is 2.3mol/L in the step (5), and the time that ammonium bicarbonate soln is added is
1.8 hours, the filtrate obtained after filtering obtained ammonium fertilizer by condensing crystallizing.
The Baume degrees for being concentrated into solution in the step (6) when condensing crystallizing is 49.5, is then cooled down, rate of temperature fall is
2.5 DEG C/h, being cooled to temperature is 13 DEG C, is centrifuged using decanter centrifuge.
The reducing agent that the step (1) uses when restoring is hydrogen.
The rate of recovery of final lithium is 99.3%, and the rate of recovery of cobalt is 98.9%, and the rate of recovery of nickel is 99.1%, the recycling of manganese
Rate is 99.3%, and the rate of recovery of aluminium is 99.4%,
As shown in Figure 1, obtained aluminium hydroxide is cotton-shaped aggregate structure, large specific surface area, primary particle size is small, finally obtains
Aluminium hydroxide detection data it is as follows:
The detection data of obtained battery grade cobalt sulfate is as follows:
| Index | Main content | Fe | Mn | Zn | Ca | Mg | Na |
| Numerical value | 99.63% | 2.5ppm | 21ppm | 4ppm | 31ppm | 21ppm | 25ppm |
| K | Pb | Ni | As | Cu | Cd | Water-insoluble | Cl |
| 12ppm | 2ppm | 39ppm | 0.2ppm | 1.5ppm | 2.3ppm | 45ppm | 12ppm |
The detection data of obtained LITHIUM BATTERY nickel chloride is as follows:
| Index | Main content | Fe | Mn | Zn | Ca | Mg | Na |
| Numerical value | 99.51% | 2.5ppm | 24ppm | 2ppm | 21ppm | 13ppm | 21ppm |
| K | Pb | Co | As | Cu | Cd | Water-insoluble | pH |
| 12ppm | 1ppm | 42ppm | 0.3ppm | 2.1ppm | 2.1ppm | 35ppm | 4.6 |
The detection data of LITHIUM BATTERY manganese sulfate is as follows:
The detection data of battery-level lithium carbonate is as follows:
Embodiment 2
A kind of processing method of nickle cobalt lithium manganate ternary waste material, is following steps:
(1) aqueous slkali is added in nickle cobalt lithium manganate ternary waste material, impregnated 4.5 hours, soaking temperature is 58 DEG C, and filtering obtains
To aluminum solutions and filter residue is contained, filter residue is dried and is sieved after washing, and screenings is put into reduction furnace and is restored, reduction temperature
It is 415 DEG C, the recovery time is 8 hours, and discharging obtains cooling material after then cooling down；
(2) by cooling expect that hot pure water stirring is added, maintaining the temperature of whipping process is 93 DEG C, and mixing time is 3.5 hours,
It is separated by solid-liquid separation, obtains filtrate containing lithium and filter residue, filter residue is mixed with filtrate containing lithium after washing, by cleaning solution；
(3) sulfuric acid solution pulp is added in filter residue after the washing for obtaining step (2), and the concentration of sulfuric acid solution is 1.5mol/
L, the ratio between molal quantity that sulfuric acid and manganese in filter residue after washing is added is 0.93:1, when the pH of reaction to solution is greater than 6.5, continues to add
Entering sulfuric acid to maintain the pH of reaction is 6-6.5, is stirred to react at this ph, when the cobalt content in solution is 35mg/L, is stopped anti-
It answers, filters, obtain manganese containing solution and cobalt nickel slag, cobalt nickel slag obtains cobalt nickel washed-residue by washing, and cleaning solution and manganese containing solution are mixed
It closes；
(4) after cobalt nickel washed-residue adds water slurry, by electromagnetic separation, magnetic separation material is obtained, hydrochloric acid solution is added in magnetic separation material,
Temperature is to be stirred to react 3.5 hours at 75 DEG C, is then filtered, and the first filtrate and the first filter residue are obtained, and reaction is added in the first filtrate
In kettle, adjusting pH is 1.95, is then 155 DEG C in temperature, is passed through chlorine and pressure is made to be 1.8 atmospheric pressure, in this atmospheric pressure
Lower reaction 4.5 hours, is filtered after then cooling down release, obtains cobalt precipitating and nickel solution, and nickel solution obtains electricity by condensing crystallizing
Pond grade nickel chloride, cobalt precipitating is added sulfuric acid solution, adds reducing agent, obtain cobalt sulfate solution after being completely dissolved, by condensation
Crystallization obtains battery grade cobalt sulfate crystal；
(5) ammonium bicarbonate soln is added in filtrate containing lithium, and the pH for adjusting solution is 7.42, and reaction temperature is 39 degrees Celsius, so
After filter, obtain battery-level lithium carbonate；
(6) manganese containing solution obtains LITHIUM BATTERY manganese sulfate by condensing crystallizing, and the mother liquor after crystallization is passed through hydrogen sulfide gas, will
After nickel cobalt content therein is reduced to 10ppm or less, filtering, filter residue is back in reduction furnace, and filtrate returns mixed with manganese containing solution
It closes.
The concentration of step (1) aqueous slkali is 4.5mol/L, is passed through carbon dioxide containing aluminum solutions, adjusts the pH of solution
It is 9.5, by filtering and washing obtains aluminium hydroxide.
Cooling material and the mass ratio of hot pure water are 1:4.3 in the step (2), and washing is washed using four-stage counter-current.
The concentration of hydrochloric acid solution is 1.8mol/L in the step (4).
The concentration of ammonium bicarbonate soln is 2.6mol/L in the step (5), and the time that ammonium bicarbonate soln is added is
1.8 hours, the filtrate obtained after filtering obtained ammonium fertilizer by condensing crystallizing.
The Baume degrees for being concentrated into solution in the step (6) when condensing crystallizing is 50.3, is then cooled down, rate of temperature fall is
2.4 DEG C/h, being cooled to temperature is 13 DEG C, is centrifuged using decanter centrifuge.
The reducing agent that the step (1) uses when restoring is hydrogen.
The rate of recovery of final lithium is 99.3%, and the rate of recovery of cobalt is 98.7%, and the rate of recovery of nickel is 99.1%, the recycling of manganese
Rate is 99.3%, and the rate of recovery of aluminium is 99.4%,
Finally obtained aluminium hydroxide detection data is as follows:
The detection data of obtained battery grade cobalt sulfate is as follows:
| Index | Main content | Fe | Mn | Zn | Ca | Mg | Na |
| Numerical value | 99.61% | 4ppm | 18ppm | 3ppm | 25ppm | 20ppm | 21ppm |
| K | Pb | Ni | As | Cu | Cd | Water-insoluble | Cl |
| 8ppm | 2ppm | 35ppm | 0.2ppm | 1.5ppm | 2.1ppm | 41ppm | 11ppm |
The detection data of obtained LITHIUM BATTERY nickel chloride is as follows:
| Index | Main content | Fe | Mn | Zn | Ca | Mg | Na |
| Numerical value | 99.54% | 2.9ppm | 32ppm | 2ppm | 22ppm | 11ppm | 21ppm |
| K | Pb | Co | As | Cu | Cd | Water-insoluble | pH |
| 11ppm | 1ppm | 41ppm | 0.3ppm | 2.4ppm | 2.6ppm | 39ppm | 4.5 |
The detection data of LITHIUM BATTERY manganese sulfate is as follows:
| Index | Mn | Fe | Ni | Zn | Ca | Mg | Na |
| Numerical value | 32.2% | 4ppm | 23ppm | 1ppm | 13ppm | 15ppm | 21ppm |
| K | Pb | Co | As | Cu | Cd | Water-insoluble | pH |
| 11ppm | 0.2ppm | 21ppm | 0.2ppm | 2ppm | 2.1ppm | 41ppm | 5.8 |
The detection data of battery-level lithium carbonate is as follows:
Embodiment 3
A kind of processing method of nickle cobalt lithium manganate ternary waste material, is following steps:
(1) aqueous slkali is added in nickle cobalt lithium manganate ternary waste material, impregnated 4.8 hours, soaking temperature is 63 DEG C, and filtering obtains
To aluminum solutions and filter residue is contained, filter residue is dried and is sieved after washing, and screenings is put into reduction furnace and is restored, reduction temperature
It is 425 DEG C, the recovery time is 8 hours, and discharging obtains cooling material after then cooling down；
(2) by cooling expect that hot pure water stirring is added, maintaining the temperature of whipping process is 93 DEG C, and mixing time is 3.5 hours,
It is separated by solid-liquid separation, obtains filtrate containing lithium and filter residue, filter residue is mixed with filtrate containing lithium after washing, by cleaning solution；
(3) sulfuric acid solution pulp is added in filter residue after the washing for obtaining step (2), and the concentration of sulfuric acid solution is 1.7mol/
L, the ratio between molal quantity that sulfuric acid and manganese in filter residue after washing is added is 0.93:1, when the pH of reaction to solution is greater than 6.5, continues to add
Entering sulfuric acid to maintain the pH of reaction is 6-6.5, is stirred to react at this ph, when the cobalt content in solution is 30mg/L, is stopped anti-
It answers, filters, obtain manganese containing solution and cobalt nickel slag, cobalt nickel slag obtains cobalt nickel washed-residue by washing, and cleaning solution and manganese containing solution are mixed
It closes；
(4) after cobalt nickel washed-residue adds water slurry, by electromagnetic separation, magnetic separation material is obtained, hydrochloric acid solution is added in magnetic separation material,
Temperature is to be stirred to react 3.5 hours at 69 DEG C, is then filtered, and the first filtrate and the first filter residue are obtained, and reaction is added in the first filtrate
In kettle, adjusting pH is 1.9, is then 155 DEG C in temperature, is passed through chlorine and pressure is made to be 1.8 atmospheric pressure, under this atmospheric pressure
Reaction 4.5 hours is filtered after then cooling down release, obtains cobalt precipitating and nickel solution, and nickel solution obtains battery by condensing crystallizing
Grade nickel chloride, cobalt precipitating are added sulfuric acid solution, add reducing agent, obtain cobalt sulfate solution after being completely dissolved, tie by condensation
Crystalline substance obtains battery grade cobalt sulfate crystal；
(5) ammonium bicarbonate soln is added in filtrate containing lithium, and the pH for adjusting solution is 7.4, and reaction temperature is 44 degrees Celsius, then
Filtering, obtains battery-level lithium carbonate；
(6) manganese containing solution obtains LITHIUM BATTERY manganese sulfate by condensing crystallizing, and the mother liquor after crystallization is passed through hydrogen sulfide gas, will
After nickel cobalt content therein is reduced to 10ppm or less, filtering, filter residue is back in reduction furnace, and filtrate returns mixed with manganese containing solution
It closes.
The concentration of step (1) aqueous slkali is 4.5mol/L, is passed through carbon dioxide containing aluminum solutions, adjusts the pH of solution
It is 9.7, by filtering and washing obtains aluminium hydroxide.
Cooling material and the mass ratio of hot pure water are 1:4.7 in the step (2), and washing is washed using four-stage counter-current.
The concentration of hydrochloric acid solution is 1.8mol/L in the step (4).
The concentration of ammonium bicarbonate soln is 2.7mol/L in the step (5), and the time that ammonium bicarbonate soln is added is
1.7 hours, the filtrate obtained after filtering obtained ammonium fertilizer by condensing crystallizing.
The Baume degrees for being concentrated into solution in the step (6) when condensing crystallizing is 50.5, is then cooled down, rate of temperature fall is
2.5 DEG C/h, being cooled to temperature is 13 DEG C, is centrifuged using decanter centrifuge.
The reducing agent that the step (1) uses when restoring is methane.
The rate of recovery of final lithium is 99.2%, and the rate of recovery of cobalt is 99.1%, and the rate of recovery of nickel is 99.3%, the recycling of manganese
Rate is 99.2%, and the rate of recovery of aluminium is 99.3%,
Finally obtained aluminium hydroxide detection data is as follows:
The detection data of obtained battery grade cobalt sulfate is as follows:
| Index | Main content | Fe | Mn | Zn | Ca | Mg | Na |
| Numerical value | 99.61% | 2ppm | 23ppm | 4ppm | 21ppm | 26ppm | 23ppm |
| K | Pb | Ni | As | Cu | Cd | Water-insoluble | Cl |
| 21ppm | 1ppm | 34ppm | 0.3ppm | 1.4ppm | 2.1ppm | 43ppm | 12ppm |
The detection data of obtained LITHIUM BATTERY nickel chloride is as follows:
The detection data of LITHIUM BATTERY manganese sulfate is as follows:
| Index | Mn | Fe | Ni | Zn | Ca | Mg | Na |
| Numerical value | 32.3% | 4ppm | 20ppm | 1ppm | 8ppm | 11ppm | 27ppm |
| K | Pb | Co | As | Cu | Cd | Water-insoluble | pH |
| 12ppm | 0.2ppm | 33ppm | 0.3ppm | 2.7ppm | 2.1ppm | 49ppm | 5.8 |
The detection data of battery-level lithium carbonate is as follows:
From the point of view of detection data, the aluminium hydroxide of preparation can be used for flame retardant fillers, other are such as lithium carbonate, nickel chloride, sulphur
Sour cobalt and manganese sulfate are LITHIUM BATTERY.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (7)
1. a kind of processing method of nickle cobalt lithium manganate ternary waste material, which is characterized in that be following steps:
(1) aqueous slkali is added in nickle cobalt lithium manganate ternary waste material, impregnated 4-6 hours, soaking temperature is 50-65 DEG C, and filtering obtains
Containing aluminum solutions and filter residue, filter residue is dried and is sieved after washing, and screenings is put into reduction furnace and is restored, and reduction temperature is
330-450 DEG C, the recovery time is 6-9 hours, and discharging obtains cooling material after then cooling down；
(2) by cooling expect that hot pure water stirring is added, maintaining the temperature of whipping process is 90-95 DEG C, and mixing time is 3-4 hours,
It is separated by solid-liquid separation, obtains filtrate containing lithium and filter residue, filter residue is mixed with filtrate containing lithium after washing, by cleaning solution；
(3) sulfuric acid solution pulp is added in filter residue after the washing for obtaining step (2), and the concentration of sulfuric acid solution is 1-2mol/L, adds
Enter the ratio between sulfuric acid and molal quantity of manganese in filter residue after washing for 0.9-0.95:1, when reacting to the pH of solution greater than 6.5, continues to add
Entering sulfuric acid to maintain the pH of reaction is 6-6.5, is stirred to react, when the cobalt content in solution is 20-50mg/L, stops at this ph
Reaction, filtering obtain manganese containing solution and cobalt nickel slag, and cobalt nickel slag obtains cobalt nickel washed-residue, cleaning solution and manganese containing solution by washing
Mixing；
(4) after cobalt nickel washed-residue adds water slurry, by electromagnetic separation, magnetic separation material is obtained, hydrochloric acid solution is added in magnetic separation material, in temperature
It is to be stirred to react at 60-80 DEG C 3-4 hours, then filters, obtain the first filtrate and the first filter residue, reaction kettle is added in the first filtrate
Interior, adjusting pH is 1.8-2.5, is then 140-160 DEG C in temperature, is passed through chlorine and pressure is made to be 1.5-2 atmospheric pressure, herein
It reacts under atmospheric pressure 3-5 hours, is filtered after then cooling down release, obtain cobalt precipitating and nickel solution, nickel solution passes through condensing crystallizing
LITHIUM BATTERY nickel chloride is obtained, cobalt precipitating is added sulfuric acid solution, adds reducing agent, cobalt sulfate solution is obtained after being completely dissolved, passes through
It crosses condensation crystallization and obtains battery grade cobalt sulfate crystal；
(5) ammonium bicarbonate soln is added in filtrate containing lithium, and the pH for adjusting solution is 7.2-7.5, and reaction temperature is 35-45 degrees Celsius,
Then it filters, obtains battery-level lithium carbonate；
(6) manganese containing solution obtains LITHIUM BATTERY manganese sulfate by condensing crystallizing, and the mother liquor after crystallization is passed through hydrogen sulfide gas, will wherein
Nickel cobalt content be reduced to 10ppm or less after, filtering, filter residue is back in reduction furnace, and filtrate returns and mixes with manganese containing solution.
2. a kind of processing method of nickle cobalt lithium manganate ternary waste material according to claim 1, it is characterised in that: the step
(1) concentration of aqueous slkali be 3-5mol/L, be passed through carbon dioxide containing aluminum solutions, adjust solution pH be 9-10, by filtering and
Washing obtains aluminium hydroxide.
3. a kind of processing method of nickle cobalt lithium manganate ternary waste material according to claim 1, it is characterised in that: the step
(2) cooling material and the mass ratio of hot pure water are 1:4-5 in, and washing is washed using four-stage counter-current.
4. a kind of processing method of nickle cobalt lithium manganate ternary waste material according to claim 1, it is characterised in that: the step
(4) concentration of hydrochloric acid solution is 1.5-2mol/L in.
5. a kind of processing method of nickle cobalt lithium manganate ternary waste material according to claim 1, it is characterised in that: the step
(5) concentration of ammonium bicarbonate soln is 2-3mol/L in, and the time that ammonium bicarbonate soln is added is 1.5-2 hours, after filtering
To filtrate by condensing crystallizing obtain ammonium fertilizer.
6. a kind of processing method of nickle cobalt lithium manganate ternary waste material according to claim 1, it is characterised in that: the step
(6) Baume degrees for being concentrated into solution in when condensing crystallizing is 49-51, is then cooled down, and rate of temperature fall is 2-3 DEG C/h, is cooled to temperature
Degree is 10-15 DEG C, is centrifuged using decanter centrifuge.
7. a kind of processing method of nickle cobalt lithium manganate ternary waste material according to claim 1, it is characterised in that: the step
(1) reducing agent used when restoring is at least one of hydrogen, methane, carbon monoxide, water-gas.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039312A (en) * | 2019-12-26 | 2020-04-21 | 甘肃睿思科新材料有限公司 | Treatment method of nickel cobalt lithium manganate positive electrode material |
| CN111118311A (en) * | 2019-12-28 | 2020-05-08 | 湖南金源新材料股份有限公司 | Manganese-lithium separation method in comprehensive recovery of ternary battery waste |
| CN112442597A (en) * | 2020-10-21 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for comprehensively treating materials in nickel-cobalt-manganese ternary precursor washing wastewater |
| EP4194572A4 (en) * | 2020-08-25 | 2024-01-24 | Hunan Brunp Recycling Tech Co Ltd | Method for recycling iron and aluminum in nickel-cobalt-manganese solution |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835228B1 (en) * | 2003-11-14 | 2004-12-28 | Industrial Technology Research Institute | Process of recovering valuable metals from waste secondary batteries |
| CN101006190A (en) * | 2004-06-28 | 2007-07-25 | 斯凯资源有限公司 | Method for nickel and cobalt recovery from laterite ores by reaction with concentrated acid and water leaching |
| CN101871048A (en) * | 2010-06-25 | 2010-10-27 | 浙江华友钴业股份有限公司 | Method for recovering cobalt, nickel and manganese from waste lithium cells |
| CN103014346A (en) * | 2012-12-03 | 2013-04-03 | 河池市津泰资源再生有限公司 | Process method for separating zinc, iron and cobalt and nickel ore concentrates from cobalt and nickel slag |
| CN103361483A (en) * | 2013-07-26 | 2013-10-23 | 浙江钛合仪器有限公司 | Technology for removing cobalt by dynamic wave chlorine oxidation |
| JP5636688B2 (en) * | 2010-02-23 | 2014-12-10 | 住友大阪セメント株式会社 | Method for producing electrode material and method for recovering lithium phosphate |
| CN107151739A (en) * | 2017-07-07 | 2017-09-12 | 金川集团股份有限公司 | A kind of full leaching method of nitric acid of the high iron alloy powder of low nickel |
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| CN108265178A (en) * | 2018-03-08 | 2018-07-10 | 蒋央芳 | A kind of processing method of cobalt metallurgy of nickel waste water slag |
-
2018
- 2018-09-13 CN CN201811066427.6A patent/CN109279665B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835228B1 (en) * | 2003-11-14 | 2004-12-28 | Industrial Technology Research Institute | Process of recovering valuable metals from waste secondary batteries |
| CN101006190A (en) * | 2004-06-28 | 2007-07-25 | 斯凯资源有限公司 | Method for nickel and cobalt recovery from laterite ores by reaction with concentrated acid and water leaching |
| JP5636688B2 (en) * | 2010-02-23 | 2014-12-10 | 住友大阪セメント株式会社 | Method for producing electrode material and method for recovering lithium phosphate |
| CN101871048A (en) * | 2010-06-25 | 2010-10-27 | 浙江华友钴业股份有限公司 | Method for recovering cobalt, nickel and manganese from waste lithium cells |
| CN103014346A (en) * | 2012-12-03 | 2013-04-03 | 河池市津泰资源再生有限公司 | Process method for separating zinc, iron and cobalt and nickel ore concentrates from cobalt and nickel slag |
| CN103361483A (en) * | 2013-07-26 | 2013-10-23 | 浙江钛合仪器有限公司 | Technology for removing cobalt by dynamic wave chlorine oxidation |
| CN107151739A (en) * | 2017-07-07 | 2017-09-12 | 金川集团股份有限公司 | A kind of full leaching method of nitric acid of the high iron alloy powder of low nickel |
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| CN108265178A (en) * | 2018-03-08 | 2018-07-10 | 蒋央芳 | A kind of processing method of cobalt metallurgy of nickel waste water slag |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039312A (en) * | 2019-12-26 | 2020-04-21 | 甘肃睿思科新材料有限公司 | Treatment method of nickel cobalt lithium manganate positive electrode material |
| CN111118311A (en) * | 2019-12-28 | 2020-05-08 | 湖南金源新材料股份有限公司 | Manganese-lithium separation method in comprehensive recovery of ternary battery waste |
| CN111118311B (en) * | 2019-12-28 | 2021-10-22 | 湖南金源新材料股份有限公司 | Manganese-lithium separation method in comprehensive recovery of ternary battery waste |
| EP4194572A4 (en) * | 2020-08-25 | 2024-01-24 | Hunan Brunp Recycling Tech Co Ltd | Method for recycling iron and aluminum in nickel-cobalt-manganese solution |
| CN112442597A (en) * | 2020-10-21 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for comprehensively treating materials in nickel-cobalt-manganese ternary precursor washing wastewater |
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