CN111994925A - Comprehensive utilization method of valuable resources in waste lithium batteries - Google Patents
Comprehensive utilization method of valuable resources in waste lithium batteries Download PDFInfo
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- CN111994925A CN111994925A CN202010882725.3A CN202010882725A CN111994925A CN 111994925 A CN111994925 A CN 111994925A CN 202010882725 A CN202010882725 A CN 202010882725A CN 111994925 A CN111994925 A CN 111994925A
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- lithium
- magnesium
- manganese
- leaching
- nickel
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 125
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000002386 leaching Methods 0.000 claims abstract description 57
- 239000010941 cobalt Substances 0.000 claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- 239000011777 magnesium Substances 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 24
- 239000011575 calcium Substances 0.000 claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 20
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 7
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 229910017052 cobalt Inorganic materials 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 34
- 229910052748 manganese Inorganic materials 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 23
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- 238000007599 discharging Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000012216 screening Methods 0.000 claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 11
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 11
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 11
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 11
- 239000013049 sediment Substances 0.000 claims description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001424 calcium ion Inorganic materials 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002912 waste gas Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- -1 iron ions Chemical class 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 2
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 6
- 239000002893 slag Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 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 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000049 iron hydride Inorganic materials 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- 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
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a comprehensive utilization method of valuable resources in waste lithium batteries, which relates to the technical field of lithium battery recovery, and comprises the following steps: the method comprises the following steps of pretreatment, acid leaching, aluminum and iron removal, copper removal, calcium, magnesium and lithium removal, ternary precursor preparation, chlorination, iron removal, magnesium and calcium removal and lithium precipitation, wherein in the calcium, magnesium and lithium removal step, sodium fluoride is added, so that the purposes of calcium removal, magnesium removal and lithium removal can be achieved, and the separation of lithium ions from cobalt, nickel and manganese ions is realized; the method can be used for preparing pure ternary precursor and battery-grade lithium carbonate, has low cost and simple process, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of lithium battery recovery, in particular to a comprehensive utilization method of valuable resources in waste lithium batteries.
Background
Metal elements such as cobalt, manganese, nickel, lithium, etc. are widely used in the field of lithium batteries. Particularly, cobalt is an important strategic metal, but the cobalt mineral resources in China are seriously deficient, the consumption of the cobalt is increased year by year, and most of cobalt raw materials depend on import. The content of cobalt, nickel, manganese and lithium in the anode material of the waste lithium battery is relatively high, and the recovery value is high.
With the rapid development of the new energy automobile industry, the yield of the ternary lithium battery shows a rapid increase trend, the recycling of the waste lithium battery is a research hotspot, a wet recovery technology is mainly adopted at present, in the wet recovery technology, the waste lithium battery is subjected to the procedures of discharging disassembly, crushing and screening, acid leaching, purification and impurity removal and the like to obtain a mixed solution containing cobalt, nickel, manganese and lithium, and the mixed solution contains a large amount of impurity ions such as iron, magnesium, calcium, aluminum, copper and the like, so that the separation difficulty of cobalt, nickel, manganese and lithium elements is large, and the quality of the obtained product is low.
In the prior art, an ion exchange membrane is often adopted to separate solution ions, but the ion exchange membrane has the defects of poor mechanical property, low separation efficiency, easy pollution of an outer membrane and the like, and the defects cause the reduction of the service performance, the shortening of the service life and the high production cost of the ion exchange membrane. Therefore, how to recover valuable resources in the waste lithium batteries and improve the quality of products becomes a problem which needs to be solved urgently.
Disclosure of Invention
Aiming at the technical problems that in the prior art, a mixed solution containing cobalt, nickel, manganese and lithium contains a large amount of impurity ions such as iron, magnesium, calcium, aluminum and copper, so that the separation difficulty of cobalt, nickel, manganese and lithium elements is high and the quality of the obtained product is low, the invention aims to provide a comprehensive utilization method of valuable resources in waste lithium batteries with low cost and simple process, and pure ternary precursors and battery-grade lithium carbonate can be prepared by the method.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a comprehensive utilization method of valuable resources in waste lithium batteries, which comprises the following steps:
the method comprises the following steps of pretreatment, namely, carrying out acid leaching discharge, water washing, roasting, crushing and screening on waste lithium batteries in sequence, wherein oversize products comprise a steel shell, an aluminum foil and a copper sheet, and undersize products comprise powder containing nickel, cobalt, manganese and lithium;
acid leaching, namely putting powder containing nickel, cobalt, manganese and lithium into a leaching tank, and adding concentrated sulfuric acid and hydrogen peroxide into the leaching tank to perform discontinuous leaching to obtain a mixed solution containing cobalt, nickel, manganese and lithium;
removing aluminum and iron, namely adding sodium carbonate with a set proportion into a mixed solution containing cobalt, nickel, manganese and lithium to react, removing aluminum and iron ions in the solution, and performing solid-liquid separation to obtain a mixed solution after aluminum and iron removal;
a copper removing step, namely adding sodium sulfide in a stoichiometric ratio into the mixed solution after aluminum and iron removal, reacting to generate copper sulfide precipitate, and performing solid-liquid separation to obtain the mixed solution after copper removal;
removing calcium, magnesium and lithium, namely adding sodium fluoride into the mixed solution after copper removal to react to generate calcium fluoride, magnesium fluoride and lithium fluoride sediments, and performing solid-liquid separation to obtain a mixed solution containing cobalt, nickel and manganese;
a step of preparing a ternary precursor, which is to add sodium hydroxide into a mixed solution containing cobalt, nickel and manganese to react to obtain a nickel-cobalt-manganese hydroxide precipitate;
chlorination, namely adding calcium fluoride, magnesium fluoride and lithium fluoride sediments into hydrochloric acid for reaction, and performing solid-liquid separation to obtain a lithium-rich solution;
a step of removing iron, namely, passing the lithium-rich solution through a filter device filled with solid manganese dioxide to remove Fe2+Conversion to Fe3+Converting the lithium-rich solution into hydroxide precipitate, evaporating and concentrating, and carrying out solid-liquid separation to obtain a concentrated lithium-rich solution;
removing magnesium and calcium, namely adding sodium carbonate into the concentrated lithium-rich solution to remove most of magnesium and calcium ions, then adding a mixture of sodium hydroxide and sodium carbonate to further remove the rest of magnesium and calcium ions to obtain the lithium-rich solution after impurity removal;
and a lithium precipitation step, namely adding sodium carbonate into the lithium-rich solution after impurity removal, separating lithium carbonate crystals, carrying out solid-liquid separation, and then carrying out flash evaporation drying to obtain the battery-grade lithium carbonate.
In a preferred embodiment, the pretreatment step specifically comprises:
(1) primary acid leaching discharge: putting the waste lithium battery into dilute sulfuric acid for discharging, wherein the mass concentration of the dilute sulfuric acid is 5-20%, and the discharging time is 2-6 h;
(2) secondary acid leaching discharge: putting the waste lithium battery into dilute sulfuric acid for discharging, wherein the mass concentration of the dilute sulfuric acid is 10% -30%, and the discharging time is 2-6 h;
(3) washing with water: putting the waste lithium battery subjected to acid leaching discharge twice into a washing tank for washing;
(4) roasting: putting the washed waste lithium battery into a steel belt furnace for roasting, introducing the roasted dilute sulfuric acid waste gas into an acid mist absorption tower for treatment, and then discharging;
(5) crushing and screening: crushing the roasted waste lithium battery by a hammer crusher, screening by a vibrating screen after crushing, wherein oversize materials comprise a steel shell, an aluminum foil and a copper sheet, and undersize materials comprise powder containing nickel, cobalt, manganese and lithium.
In the preferable scheme, in the acid leaching step, the reaction temperature is 60-70 ℃, and the solid-to-solid ratio of a leaching solution is 3-4: 1, the concentration of initial sulfuric acid for leaching is 200-240 g/L, the pH value of a leaching end point is 1-2, and the leaching time is 6-10 h.
The powder containing nickel, cobalt, manganese and lithium is leached with concentrated sulfuric acid to form soluble sulfate which enters the solution, and the leaching of nickel, cobalt, manganese and lithium is promoted by adding hydrogen peroxide. The reaction equation mainly involved is as follows:
MeO+H2SO4→MeSO4+H2o (Me is Ni, Co, Mn, Cu, Ca, Mg, Fe, etc.)
2LiCoO2+3H2SO4+H2O2→Li2SO4+2CoSO4+O2↑+4H2O
2LiNiO2+3H2SO4+H2O2→Li2SO4+2NiSO4+O2↑+4H2O
2LiMnO2+3H2SO4+H2O2→Li2SO4+2MnSO4+O2↑+4H2O
2Fe2++H2O2+2H+→2Fe3++2H2O
In the preferable scheme, in the step of removing the aluminum and the iron, high-temperature steam is added, the reaction temperature is controlled to be higher than 90 ℃, and the reaction time is 1-4 hours.
In the step of removing aluminum and iron, sodium carbonate is added into a mixed solution containing cobalt, nickel, manganese and lithium for reaction, the pH value of the solution is controlled to be 4.5, so that aluminum and the sodium carbonate react to generate aluminum slag (aluminum carbonate is decomposed into aluminum hydroxide when meeting water), and Fe3+Hydrolyzing to generate iron hydride precipitate, and after solid-liquid separation by a filter press, the residual materials do not contain aluminum and iron any more, thus achieving the purposes of removing aluminum and iron. The reaction equation mainly involved is as follows:
2Al3++3Na2CO3＝Al2(CO3)3+6Na+
Al2(CO3)3+3H2O＝2Al(OH)3↓+3CO2↑
H2SO4+Na2CO3＝Na2SO4+H2O+3CO2↑
Fe3++3H2O→Fe(OH)3↓+3H+
in the step of removing calcium, magnesium and lithium, the purposes of removing calcium, magnesium and lithium can be achieved by adding sodium fluoride, and the separation of lithium ions from cobalt, nickel and manganese ions is realized.
In the preferred scheme, in the chlorination step, hydrochloric acid is added into the calcium fluoride, magnesium fluoride and lithium fluoride sediments for reaction for 1-4 h, and the calcium fluoride and magnesium fluoride sediments do not react with the hydrochloric acid. The reaction equation mainly involved is as follows:
LiF+HCl＝LiCl+HF(aq)
in the iron removal step, the manganese dioxide is Fe2+Conversion to Fe3+Good catalyst of (2), Fe produced3+Hydrolysis to Fe (OH)3The precipitate was immediately removed by filtration. The reaction equation mainly involved is as follows:
4H++2Fe2++MnO2→Mn2++2Fe3++2H2O
in the step of removing magnesium and calcium, stoichiometric sodium carbonate is added according to the amount of magnesium and calcium ions in the lithium-rich solution, and the precipitate is filtered after full reaction to remove most of magnesium and calcium ions; and adding a mixture of sodium hydroxide and sodium carbonate to adjust the pH value of the lithium-rich solution to 13, wherein the mass concentration of the sodium hydroxide is 10-20%, the mass concentration of the sodium carbonate is 40-60%, and further removing the residual magnesium and calcium ions. The reaction equation mainly involved is as follows:
CO3 2-+Ca2+→CaCO3↓
CO3 2-+Mg2+→MgCO3↓
2OH-+Mg2+→Mg(OH)2↓
due to LiCO3Solubility product KSPIs 8.15 multiplied by 10-4，CaCO3Solubility product of KSPIs 3.36 multiplied by 10-9，MgCO3Solubility product of KSPIs 6.82X 10-6Therefore, stoichiometric sodium carbonate is added into the lithium-rich solution, and no lithium carbonate is separated out; due to Mg (OH)2Solubility product of KSPIs 1.8X 10-11Thus adding sodium hydroxideDeeply removing magnesium ions.
In the preferable scheme, in the step of lithium precipitation, sodium carbonate is added into the lithium-rich solution after impurity removal, the reaction temperature is 45-60 ℃, and the reaction time is 1-4 h. The reaction equation mainly involved is as follows:
2LiCl+2NaCO3+2HF→Li2CO3↓+NaF+HCl+CO2↑
the preferable scheme comprises a flash evaporation drying step, wherein flash evaporation drying is carried out after lithium carbonate crystallization and filtration, the crystallization temperature of lithium carbonate is higher than 100 ℃, finally a lithium carbonate product is obtained, and the filtrate is sent to a sewage treatment station for treatment.
Compared with the prior art, the invention has the beneficial technical effects that:
the invention provides a comprehensive utilization method of valuable resources in waste lithium batteries, which can be used for preparing pure ternary precursors and battery-grade lithium carbonate, and is low in cost, simple in process and suitable for industrial production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a process flow chart of the comprehensive utilization method of valuable resources in the waste lithium battery.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
The experimental procedures described in the following examples are conventional unless otherwise specified, and the reagents and materials described therein are commercially available without further specification.
Example 1
The embodiment is a comprehensive utilization method of valuable resources in waste lithium batteries, and is characterized by comprising the following steps:
(1) the method comprises the following steps of sequentially carrying out acid leaching discharging, water washing, roasting, crushing and screening on a waste ternary nickel-cobalt-manganese 18650 lithium battery, wherein oversize products are a steel shell, an aluminum foil and a copper sheet, and undersize products are powder containing nickel-cobalt-manganese-lithium, and specifically comprises the following steps:
(1.1) primary acid leaching discharge: a monorail crane is used for throwing the titanium basket provided with the waste lithium battery into a dilute acid soaking pool (4 m) with the dilute sulfuric acid concentration of about 8 percent3) Acid leaching discharging for about 4 hours;
(1.2) secondary acid leaching discharge: a monorail crane is used for throwing the titanium basket provided with the waste lithium battery into a dilute acid soaking pool (4 m) with the dilute sulfuric acid concentration of about 14 percent3) Acid leaching discharging for about 4 hours;
(1.3) water washing: putting the waste lithium battery subjected to acid leaching discharge twice into a washing tank for washing;
(1.4) roasting: putting the washed waste lithium battery into a steel belt furnace for roasting, introducing the roasted dilute sulfuric acid waste gas into an acid mist absorption tower for treatment, and then discharging;
(1.5) crushing and screening: crushing the roasted waste lithium battery by a hammer crusher, and screening by a vibrating screen after crushing, wherein oversize materials are a steel shell, an aluminum foil and a copper sheet, and undersize materials are nickel-cobalt-manganese-lithium-containing powder;
(2) and acid leaching, namely putting the powder containing nickel, cobalt, manganese and lithium into a leaching tank, adding concentrated sulfuric acid and hydrogen peroxide into the leaching tank for intermittent leaching, wherein the reaction temperature is 60-70 ℃, and the solid-to-solid ratio of a leaching solution is 3: 1, leaching initial sulfuric acid concentration of 220g/L, leaching end-point pH value of 1.5, and leaching time of 8 hours to obtain a mixed solution containing cobalt, nickel, manganese and lithium;
(3) removing aluminum and iron, namely adding sodium carbonate into a mixed solution containing cobalt, nickel, manganese and lithium to react, controlling the pH value of the solution to be 4.5, adding 0.5MPa of new steam, controlling the reaction temperature to be more than 90 ℃, reacting for 2 hours, and performing solid-liquid separation to obtain a mixed solution after aluminum and iron removal;
(4) a copper removing step, namely adding sodium sulfide in a stoichiometric ratio into the mixed solution after aluminum and iron removal, reacting to generate copper sulfide precipitate, and performing solid-liquid separation to obtain the mixed solution after copper removal;
(5) removing calcium, magnesium and lithium, namely adding sodium fluoride into the mixed solution after copper removal to react to generate calcium fluoride, magnesium fluoride and lithium fluoride sediments, and performing solid-liquid separation to obtain a mixed solution containing cobalt, nickel and manganese; pure water is used as the slag washing water in the step, and the slag washing water is reused in the aluminum and iron removing process and is not discharged;
(6) a step of preparing a ternary precursor, which is to add sodium hydroxide into a mixed solution containing cobalt, nickel and manganese, react to obtain a nickel-cobalt-manganese hydroxide precipitate which can be directly used as a ternary precursor material;
(7) a chlorination step, namely adding calcium fluoride, magnesium fluoride and lithium fluoride sediments into hydrochloric acid to react for 2 hours, and performing solid-liquid separation to obtain a lithium-rich solution;
(8) a step of removing iron, namely, passing the lithium-rich solution through a filter device filled with solid manganese dioxide to remove Fe2+Conversion to Fe3+Converting the lithium-rich solution into hydroxide precipitate, evaporating and concentrating, and carrying out solid-liquid separation to obtain a concentrated lithium-rich solution;
(9) removing magnesium and calcium, namely adding a mixture of sodium hydroxide and sodium carbonate to adjust the pH value of the lithium-rich solution to 13, wherein the mass concentration of the sodium hydroxide is 15% and the mass concentration of the sodium carbonate is 50%, so as to obtain the lithium-rich solution after impurity removal;
(10) and a lithium precipitation step, namely adding sodium carbonate into the lithium-rich solution after impurity removal, reacting at the temperature of 50 ℃ for 2 hours, separating lithium carbonate crystals, carrying out solid-liquid separation, and then carrying out flash evaporation drying to obtain the battery-grade lithium carbonate.
In the lithium carbonate product obtained in example 1, the purity of the lithium carbonate product was 99.8 wt%, the content of magnesium was 0.004 wt%, the content of calcium was 0.002 wt%, the content of iron was 0.0006 wt%, the content of copper was 0.0002 wt%, and the content of aluminum was 0.0006 wt%.
Example 2
The embodiment is a comprehensive utilization method of valuable resources in waste lithium batteries, and is characterized by comprising the following steps:
(1) the method comprises the following steps of sequentially carrying out acid leaching discharging, water washing, roasting, crushing and screening on a waste ternary nickel-cobalt-manganese 18650 lithium battery, wherein oversize products are a steel shell, an aluminum foil and a copper sheet, and undersize products are powder containing nickel-cobalt-manganese-lithium, and specifically comprises the following steps:
(1.1) primary acid leaching discharge: a monorail crane is used for throwing the titanium basket provided with the waste lithium battery into a dilute acid soaking pool (4 m) with the dilute sulfuric acid concentration of about 6 percent3) Acid leaching discharging for about 5 hours;
(1.2) secondary acid leaching discharge: a monorail crane is used for throwing the titanium basket provided with the waste lithium battery into a dilute acid soaking pool (4 m) with the dilute sulfuric acid concentration of about 20 percent3) Acid leaching discharging for about 3 hours;
(1.3) water washing: putting the waste lithium battery subjected to acid leaching discharge twice into a washing tank for washing;
(1.4) roasting: putting the washed waste lithium battery into a steel belt furnace for roasting, introducing the roasted dilute sulfuric acid waste gas into an acid mist absorption tower for treatment, and then discharging;
(1.5) crushing and screening: crushing the roasted waste lithium battery by a hammer crusher, and screening by a vibrating screen after crushing, wherein oversize materials are a steel shell, an aluminum foil and a copper sheet, and undersize materials are nickel-cobalt-manganese-lithium-containing powder;
(2) and acid leaching, namely putting the powder containing nickel, cobalt, manganese and lithium into a leaching tank, adding concentrated sulfuric acid and hydrogen peroxide into the leaching tank for intermittent leaching, wherein the reaction temperature is 60-70 ℃, and the solid-to-solid ratio of a leaching solution is 4: 1, leaching initial sulfuric acid concentration of 240g/L, leaching end-point pH value of 1.5, and leaching time of 6h to obtain a mixed solution containing cobalt, nickel, manganese and lithium;
(3) removing aluminum and iron, namely adding sodium carbonate into a mixed solution containing cobalt, nickel, manganese and lithium to react, controlling the pH value of the solution to be 4.5, adding 0.5MPa of new steam, controlling the reaction temperature to be more than 90 ℃, reacting for 3 hours, and performing solid-liquid separation to obtain a mixed solution after aluminum and iron removal;
(4) a copper removing step, namely adding sodium sulfide in a stoichiometric ratio into the mixed solution after aluminum and iron removal, reacting to generate copper sulfide precipitate, and performing solid-liquid separation to obtain the mixed solution after copper removal;
(5) removing calcium, magnesium and lithium, namely adding sodium fluoride into the mixed solution after copper removal to react to generate calcium fluoride, magnesium fluoride and lithium fluoride sediments, and performing solid-liquid separation to obtain a mixed solution containing cobalt, nickel and manganese; pure water is used as the slag washing water in the step, and the slag washing water is reused in the aluminum and iron removing process and is not discharged;
(6) a step of preparing a ternary precursor, which is to add sodium hydroxide into a mixed solution containing cobalt, nickel and manganese, react to obtain a nickel-cobalt-manganese hydroxide precipitate which can be directly used as a ternary precursor material;
(7) a chlorination step, namely adding calcium fluoride, magnesium fluoride and lithium fluoride sediments into hydrochloric acid to react for 2 hours, and performing solid-liquid separation to obtain a lithium-rich solution;
(8) a step of removing iron, namely, passing the lithium-rich solution through a filter device filled with solid manganese dioxide to remove Fe2+Conversion to Fe3+Converting the lithium-rich solution into hydroxide precipitate, evaporating and concentrating, and carrying out solid-liquid separation to obtain a concentrated lithium-rich solution;
(9) removing magnesium and calcium, namely adding a mixture of sodium hydroxide and sodium carbonate to adjust the pH value of the lithium-rich solution to 13, wherein the mass concentration of the sodium hydroxide is 15% and the mass concentration of the sodium carbonate is 45%, so as to obtain the lithium-rich solution after impurity removal;
(10) and a lithium precipitation step, namely adding sodium carbonate into the lithium-rich solution after impurity removal, reacting at the temperature of 50 ℃ for 2 hours, separating lithium carbonate crystals, carrying out solid-liquid separation, and then carrying out flash evaporation drying to obtain the battery-grade lithium carbonate.
In the lithium carbonate product obtained in example 2, the purity of the lithium carbonate product was 99.7 wt%, the magnesium content was 0.005 wt%, the calcium content was 0.003 wt%, the iron content was 0.0008 wt%, the copper content was 0.0003 wt%, and the aluminum content was 0.0005 wt%.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (10)
1. A comprehensive utilization method of valuable resources in waste lithium batteries is characterized by comprising the following steps:
the method comprises the following steps of pretreatment, namely, carrying out acid leaching discharge, water washing, roasting, crushing and screening on waste lithium batteries in sequence, wherein oversize products comprise a steel shell, an aluminum foil and a copper sheet, and undersize products comprise powder containing nickel, cobalt, manganese and lithium;
acid leaching, namely putting powder containing nickel, cobalt, manganese and lithium into a leaching tank, and adding concentrated sulfuric acid and hydrogen peroxide into the leaching tank to perform discontinuous leaching to obtain a mixed solution containing cobalt, nickel, manganese and lithium;
removing aluminum and iron, namely adding sodium carbonate with a set proportion into a mixed solution containing cobalt, nickel, manganese and lithium to react, removing aluminum and iron ions in the solution, and performing solid-liquid separation to obtain a mixed solution after aluminum and iron removal;
a copper removing step, namely adding sodium sulfide in a stoichiometric ratio into the mixed solution after aluminum and iron removal, reacting to generate copper sulfide precipitate, and performing solid-liquid separation to obtain the mixed solution after copper removal;
removing calcium, magnesium and lithium, namely adding sodium fluoride into the mixed solution after copper removal to react to generate calcium fluoride, magnesium fluoride and lithium fluoride sediments, and performing solid-liquid separation to obtain a mixed solution containing cobalt, nickel and manganese;
a step of preparing a ternary precursor, which is to add sodium hydroxide into a mixed solution containing cobalt, nickel and manganese to react to obtain a nickel-cobalt-manganese hydroxide precipitate;
chlorination, namely adding calcium fluoride, magnesium fluoride and lithium fluoride sediments into hydrochloric acid for reaction, and performing solid-liquid separation to obtain a lithium-rich solution;
a step of removing iron, namely, passing the lithium-rich solution through a filter device filled with solid manganese dioxide to remove Fe2+Conversion to Fe3+Converting the lithium-rich solution into hydroxide precipitate, evaporating and concentrating, and carrying out solid-liquid separation to obtain a concentrated lithium-rich solution;
removing magnesium and calcium, namely adding sodium carbonate into the concentrated lithium-rich solution to remove most of magnesium and calcium ions, then adding a mixture of sodium hydroxide and sodium carbonate to further remove the rest of magnesium and calcium ions to obtain the lithium-rich solution after impurity removal;
and a lithium precipitation step, namely adding sodium carbonate into the lithium-rich solution after impurity removal, separating lithium carbonate crystals, carrying out solid-liquid separation, and then carrying out flash evaporation drying to obtain the battery-grade lithium carbonate.
2. The method for comprehensively utilizing valuable resources in the waste lithium batteries as claimed in claim 1, wherein the pretreatment step specifically comprises:
(1) primary acid leaching discharge: putting the waste lithium battery into dilute sulfuric acid for discharging, wherein the mass concentration of the dilute sulfuric acid is 5-20%, and the discharging time is 2-6 h;
(2) secondary acid leaching discharge: putting the waste lithium battery into dilute sulfuric acid for discharging, wherein the mass concentration of the dilute sulfuric acid is 10% -30%, and the discharging time is 2-6 h;
(3) washing with water: putting the waste lithium battery subjected to acid leaching discharge twice into a washing tank for washing;
(4) roasting: putting the washed waste lithium battery into a steel belt furnace for roasting, introducing the roasted dilute sulfuric acid waste gas into an acid mist absorption tower for treatment, and then discharging;
(5) crushing and screening: crushing the roasted waste lithium battery by a hammer crusher, screening by a vibrating screen after crushing, wherein oversize materials comprise a steel shell, an aluminum foil and a copper sheet, and undersize materials comprise powder containing nickel, cobalt, manganese and lithium.
3. The method for comprehensively utilizing valuable resources in the waste lithium batteries according to claim 1, wherein in the acid leaching step, the reaction temperature is 60-70 ℃, and the solid-to-solid ratio of a leaching solution is 3-4: 1, the concentration of initial sulfuric acid for leaching is 200-240 g/L, the pH value of a leaching end point is 1-2, and the leaching time is 6-10 h.
4. The method for comprehensively utilizing valuable resources in the waste lithium batteries as claimed in claim 1, wherein in the step of removing aluminum and iron, high-temperature steam is added, the reaction temperature is controlled to be more than 90 ℃, and the reaction time is 1-4 h.
5. The method for comprehensively utilizing valuable resources in the waste lithium batteries as claimed in claim 1, wherein in the chlorination step, calcium fluoride, magnesium fluoride and lithium fluoride sediments are added into hydrochloric acid for reaction for 1-4 h.
6. The method for comprehensively utilizing valuable resources in the waste lithium batteries as claimed in claim 1, wherein in the step of removing magnesium and calcium, stoichiometric sodium carbonate is added according to the amount of magnesium and calcium ions in the lithium-rich solution, and after full reaction, the precipitate is filtered out to remove most of the magnesium and calcium ions; and adding a mixture of sodium hydroxide and sodium carbonate to adjust the pH value of the lithium-rich solution to 13, wherein the mass concentration of the sodium hydroxide is 10-20%, and the mass concentration of the sodium carbonate is 40-60%.
7. The comprehensive utilization method of valuable resources in the waste lithium batteries as claimed in claim 1, wherein in the step of depositing lithium, the reaction temperature is 45-60 ℃ and the reaction time is 1-4 h.
8. The method for comprehensively utilizing valuable resources in the waste lithium batteries as claimed in claim 1, wherein flash evaporation drying is performed after lithium carbonate crystallization and filtration, the crystallization temperature of lithium carbonate is greater than 100 ℃, finally a lithium carbonate product is obtained, and the filtrate is sent to a sewage treatment station for treatment.
9. A nickel cobalt manganese hydroxide product obtainable by the process of any one of claims 1 to 8.
10. A battery grade lithium carbonate product, characterised in that it is produced by the process of any one of claims 1 to 8.
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