CN114195175A - Method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder - Google Patents
Method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder Download PDFInfo
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- CN114195175A CN114195175A CN202111644477.XA CN202111644477A CN114195175A CN 114195175 A CN114195175 A CN 114195175A CN 202111644477 A CN202111644477 A CN 202111644477A CN 114195175 A CN114195175 A CN 114195175A
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- iron phosphate
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000000843 powder Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 50
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 45
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000010941 cobalt Substances 0.000 title claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 36
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011572 manganese Substances 0.000 claims abstract description 38
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000012535 impurity Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000011575 calcium Substances 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 235000021110 pickles Nutrition 0.000 claims abstract description 19
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- -1 manganese metals Chemical class 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 12
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 230000000536 complexating effect Effects 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- 239000002893 slag Substances 0.000 claims description 12
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000004042 decolorization Methods 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 39
- 239000002994 raw material Substances 0.000 description 11
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000005273 aeration Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 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
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010926 waste battery Substances 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- C01P2006/82—Compositional purity water content
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder. The method for extracting lithium from lithium iron phosphate powder mixed with ternary powder and recovering nickel, cobalt and manganese metals comprises the following steps: (1) mixing slurry; (2) carrying out combined oxidation leaching on ultrasonic high-energy oxygen and hydrogen peroxide; (3) recovering nickel, cobalt and manganese by resin: recovering nickel, cobalt and manganese valuable metals from the pickle liquor by using heavy resin; (4) primary impurity removal: oxidizing the solution after resin adsorption with hydrogen peroxide to obtain residual ferrous, and primarily removing impurities with calcium-containing compound to remove impurities such as Fe, Al, Ti, F and P; (5) evaporating and concentrating; (6) removing impurities by alkaline method, decolorizing with activated carbon, and removing CO2Removing calcium; (7) and (4) complexing and precipitating lithium to finally obtain the battery-grade lithium carbonate. The method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder provided by the invention has the advantages of strong adaptability, low equipment requirement, simple process, low energy consumption, economy and environmental protection, and can realizeComprehensive recovery of valuable metals and suitability for large-scale industrial production.
Description
Technical Field
The invention relates to the field of lithium ion battery material recovery, in particular to a method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder.
Background
The new energy automobile is an important direction for green development and transformation and upgrading of the automobile industry all over the world and is a strategic choice for the development of the automobile industry in China. In recent years, the output and sales of new energy automobiles in China are continuously the first place around the world for several years, and the new energy automobiles are taken as power batteries of new energy automobiles and are also increased explosively. The lithium iron phosphate battery has the advantages of high working voltage, high energy density, long cycle life, good safety performance, small self-discharge rate, no memory effect and the like, is widely applied, and the market share of the lithium iron phosphate battery is increased year by year. However, the service life of the lithium iron phosphate battery is 5-8 years, and the lithium iron phosphate battery also meets the high-grade retirement trend after the popularization of new energy automobiles for many years. If the ex-service lithium iron phosphate battery is unreasonably disposed, serious environmental pollution and resource waste are caused. Therefore, the recycling, harmless treatment and resource recycling of the retired lithium iron phosphate battery become hot topics.
At present, the recovery of lithium iron phosphate batteries is mainly divided into high-temperature regeneration and wet recovery. The high-temperature regeneration has low pertinence to the waste battery, strict impurity removal is needed to avoid impurity residue, the process energy consumption is high, the pollution is large, and the problem of difficult homogenization repair exists, so that the capacitance, the charge and discharge performance and the performance of a primary material of the repaired lithium iron phosphate are obviously reduced. The raw materials recovered by the wet method have relatively strong adaptability, have corresponding impurity removal procedures for impurities, and can be applied to large-scale industrial production.
Patent CN202110963864.3 discloses a method for economically recovering lithium from a waste lithium iron phosphate material by an acid method, which comprises the following steps: mixing waste lithium iron phosphate powder, concentrated sulfuric acid and water into slurry, carrying out aeration oxidation reaction under the condition of heating and stirring, then adding hydrogen peroxide to continue heating, stirring and oxidation reaction, filtering, firstly adjusting the pH value of filtrate by using a calcium carbonate solution to avoid the combination of lithium and residual phosphate radicals, then adding lime to adjust the pH value to remove impurities such as magnesium, nickel, cobalt, manganese, aluminum, iron, copper and the like, adding saturated lithium carbonate to remove calcium after filtering, and finally introducing carbon dioxide to settle and recover lithium carbonate in the filtrate. Although the method uses an aeration method to replace part of hydrogen peroxide, the method has low air oxidation rate, long time consumption and high unit consumption of hydrogen peroxide under heating condition; the concentration of Li in the purification solution is low, and the CO2 is adopted for settling and recovering lithium carbonate, so that the reaction rate is low, the lithium settling mother solution amount is large, and the treatment cost is high; organic matters in the pickle liquor are not treated, so that the quality of the product is influenced; meanwhile, the nickel, cobalt and manganese metals are not recycled, so that the waste of resources is caused, and the method is not suitable for large-scale industrial production.
Patent CN109088120A discloses a method for preparing battery-grade lithium carbonate by using waste lithium iron phosphate pole pieces, which comprises placing the waste lithium iron phosphate pole pieces in a roasting furnace to roast at the temperature of 700-. Although the method can recover the battery-grade lithium carbonate to a greater extent, and solves the problem of influence of wet-process binder and electrolyte on the product quality, the method has high equipment requirement, high energy consumption, greater environmental protection pressure caused by combustion of the binder and the like, and higher requirements on the recovery cost and the environment are provided.
Disclosure of Invention
Based on the above, the present invention is made to solve the defects in the prior art, and the present invention aims to provide a method for extracting lithium from lithium iron phosphate powder mixed with ternary powder and recovering nickel, cobalt and manganese metals. Not only effectively reduces the unit consumption of the hydrogen peroxide, solves the influence of residual organic matters on the product quality, and improves the product quality. Meanwhile, the problem of recycling the mixed nickel, cobalt and manganese metals caused by the diversity of raw material types, recycling ways, classification modes, crushing procedures and the like is solved. The method has the advantages of strong raw material adaptability, low equipment requirement, simple process, low cost, economy and environmental protection, and can realize comprehensive recovery of valuable metals.
The invention relates to a method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder, which comprises the following steps: step (1), size mixing: mixing lithium iron phosphate powder mixed with the ternary powder, concentrated sulfuric acid and water according to a certain proportion to obtain slurry; step (2), combined oxidation leaching: introducing ultrasonic high-energy oxygen into the slurry obtained in the step (1), and slowly adding H2O2Until no Fe is detected by using 1% potassium ferricyanide solution2+Stopping oxidation, and filtering to obtain pickle liquor and pickle slag; and (3) recovering nickel, cobalt and manganese from resin: adsorbing nickel, cobalt and manganese metal ions in the pickle liquor obtained in the step (2) by using a heavy-duty resin, collecting the adsorbed liquor, stopping adsorption when the content of the nickel, cobalt and manganese ions in the adsorbed liquor approaches a limit value, analyzing the resin by using dilute sulfuric acid, and recovering to obtain a nickel, cobalt and manganese-containing solution; step (4), primary impurity removal: oxidizing the residual ferrous ions in the resin adsorbed liquid obtained in the step (3) with hydrogen peroxide, adjusting the pH to 7-8 with a calcium-containing compound, removing iron, aluminum, titanium, phosphate radical and F ions, stirring for reacting for 0.5-1 h, and filtering to obtain a primary impurity removal liquid and primary impurity removal slag; and (5) evaporation and concentration: evaporating and concentrating the primary impurity-removed liquid obtained in the step (4) to obtain a concentrated liquid and a small amount of slag; alkaline impurity removal: adjusting pH of the concentrated solution to alkaline with alkaline agent, adding active carbon for decolorization, introducing CO2Removing calcium from the gas, stirring for reaction for 0.5-1 h, and filtering to obtain sulfuric acidLithium purification liquid and alkaline impurity removal slag; step (7) complexing and precipitating lithium: and (4) adding an organic complexing agent into the purified liquid obtained in the step (6), heating and dissolving, adding a soda solution to precipitate lithium, and then centrifuging, washing and drying to obtain the battery-grade lithium carbonate. The lithium iron phosphate powder mixed with the ternary powder in the step (1) comprises the following valuable metal components in percentage by mass: 3.3 to 4.5 percent of Li3, 35 percent of Fe28, 20 to 32 percent of P10, 0.1 to 5 percent of All, 0.01 to 2.0 percent of Ni0, 0.01 to 2.0 percent of Co0, 0.01 to 2.0 percent of Mn0, and the like. Due to the diversity of the raw material types, recovery routes, classification modes, crushing processes and the like, the lithium iron powder is mixed with a small amount of ternary powder and is typical in the market.
Further, the mass ratio of the lithium iron phosphate powder mixed with the ternary powder in the step (1), the concentrated sulfuric acid and the water is 5: 1.5-1.6: 15-20.
Further, the ultrasonic high-energy oxygen flow rate in the step (2) is 10-30 m/h, the hydrogen peroxide flow rate is 4-9L/min, the reaction temperature is controlled below 80 ℃, and the oxidation time is 2-4 h.
Furthermore, the heavy-weight-removing resin in the step (3) is resin with excellent adsorption performance on Ni, Co and Mn metals, and the limited values of Ni, Co and Mn ion contents in the adsorbed liquid are all lower than 0.001 g/L.
Further, in the step (4), the calcium-containing compound is CaO, Ca (OH)2And CaCO3One or two of them.
Further, in the step (5), evaporating and concentrating until the concentration of Li in the concentrated solution is not lower than 20 g/L.
Further, in the step (6), the alkaline agent is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide, the pH value of the alkaline agent is adjusted to be more than 12, activated carbon is added according to 3-5 per mill of the mass of the liquid, and CO is added2The gas flow rate is 5-30 m/h.
Further, in the step (7), the organic complexing agent is EDTA or EDTA-2Na, the addition amount is 1-2 times of the theoretical amount of complexed calcium and magnesium, the concentration of the soda solution is 200-240 g/L, and the reaction temperature is 85-95 ℃.
The method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder is characterized by comprising the following steps ofThe method comprises the following steps of taking shaped iron-lithium powder as an object, mixing partial ternary powder due to the diversity of raw material types, recovery ways, classification modes, crushing processes and the like, and sequentially carrying out size mixing, ultrasonic high-energy oxygen and hydrogen peroxide combined oxidation leaching, resin recovery of nickel-cobalt-manganese metal, primary impurity removal, evaporation concentration, alkaline impurity removal, activated carbon decolorization and CO2 Ca removal to obtain Li2SO4Purifying the solution, and then precipitating lithium through channels and collaterals to obtain the battery-grade lithium carbonate product. The nickel-cobalt-manganese-containing solution recovered by the resin can be used as a raw material for preparing a ternary precursor material, and resources are effectively recovered.
According to the method for extracting lithium from lithium iron phosphate powder mixed with ternary powder and recovering nickel, cobalt and manganese metals, the defects of high unit consumption of hydrogen peroxide and high organic content of leachate in the traditional hydrogen peroxide oxidation and acid leaching method are overcome by introducing ultrasonic high-energy oxygen, the production cost is effectively reduced, and the product quality is improved. Meanwhile, the heavy resin is introduced to recover nickel, cobalt and manganese metals, so that the current situations of high acid and alkali consumption, difficult filter pressing and long impurity removal process in the traditional method are avoided. Under the condition that the reaction system continuously releases heat, the unit consumption of hydrogen peroxide is close to a theoretical value, and the yields of Li, nickel, cobalt and manganese are both more than 96%. The method has the advantages of strong raw material adaptability, low equipment requirement, simple process, low energy consumption, economy and environmental protection, can realize comprehensive recovery of valuable metals, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a process flow chart of the method for extracting lithium and recovering nickel-cobalt-manganese metal from lithium iron phosphate mixed with ternary powder according to the invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Referring to fig. 1, the present invention provides a method for extracting lithium from lithium iron phosphate powder mixed with ternary powder and recovering nickel, cobalt and manganese metals, comprising the following stepsThe method comprises the following steps: step (1), size mixing: mixing lithium iron phosphate powder mixed with the ternary powder, concentrated sulfuric acid and water according to a certain proportion to obtain slurry; step (2), combined oxidation leaching: introducing ultrasonic high-energy oxygen into the slurry obtained in the step (1), and slowly adding H2O2Until no Fe is detected by using 1% potassium ferricyanide solution2+Stopping oxidation, and filtering to obtain pickle liquor and pickle slag; and (3) recovering nickel, cobalt and manganese from resin: adsorbing nickel, cobalt and manganese metal ions in the pickle liquor obtained in the step (2) by using a heavy-duty resin, collecting the adsorbed liquor, stopping adsorption when the content of the nickel, cobalt and manganese ions in the adsorbed liquor approaches a limit value, analyzing the resin by using dilute sulfuric acid, and recovering to obtain a nickel, cobalt and manganese-containing solution; step (4), primary impurity removal: oxidizing the residual ferrous ions in the resin adsorbed liquid obtained in the step (3) with hydrogen peroxide, adjusting the pH to 7-8 with a calcium-containing compound, removing iron, aluminum, titanium, phosphate radical and F ions, stirring for reacting for 0.5-1 h, and filtering to obtain a primary impurity removal liquid and primary impurity removal slag; and (5) evaporation and concentration: evaporating and concentrating the primary impurity-removed liquid obtained in the step (4) to obtain a concentrated liquid and a small amount of slag; alkaline impurity removal: adjusting pH of the concentrated solution to alkaline with alkaline agent, adding active carbon for decolorization, introducing CO2Removing calcium from the gas, stirring for reaction for 0.5-1 h, and filtering to obtain a lithium sulfate purified solution and alkaline impurity-removing slag; step (7) complexing and precipitating lithium: and (4) adding an organic complexing agent into the purified liquid obtained in the step (6), heating and dissolving, adding a soda solution to precipitate lithium, and then centrifuging, washing and drying to obtain the battery-grade lithium carbonate. The lithium iron phosphate powder mixed with the ternary powder in the step (1) comprises the following valuable metal components in percentage by mass: 3.3 to 4.5 percent of Li3, 35 percent of Fe28, 20 to 32 percent of P10, 0.1 to 5 percent of All, 0.01 to 2.0 percent of Ni0, 0.01 to 2.0 percent of Co0, 0.01 to 2.0 percent of Mn0, and the like. Due to the diversity of the raw material types, recovery routes, classification modes, crushing processes and the like, the lithium iron powder is mixed with a small amount of ternary powder and is typical in the market.
Further, the mass ratio of the lithium iron phosphate powder mixed with the ternary powder in the step (1), the concentrated sulfuric acid and the water is 5: 1.5-1.6: 15-20.
Further, the ultrasonic high-energy oxygen flow rate in the step (2) is 10-30 m/h, the hydrogen peroxide flow rate is 4-9L/min, the reaction temperature is controlled below 80 ℃, and the oxidation time is 2-4 h.
Furthermore, the heavy-weight-removing resin in the step (3) is resin with excellent adsorption performance on Ni, Co and Mn metals, and the limited values of Ni, Co and Mn ion contents in the adsorbed liquid are all lower than 0.001 g/L.
Further, in the step (4), the calcium-containing compound is CaO, Ca (OH)2And CaCO3One or two of them.
Further, in the step (5), evaporating and concentrating until the concentration of Li in the concentrated solution is not lower than 20 g/L.
Further, in the step (6), the alkaline agent is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide, the pH value of the alkaline agent is adjusted to be more than 12, activated carbon is added according to 3-5 per mill of the mass of the liquid, and CO is added2The gas flow rate is 5-30 m/h.
Further, in the step (7), the organic complexing agent is EDTA or EDTA-2Na, the addition amount is 1-2 times of the theoretical amount of complexed calcium and magnesium, the concentration of the soda solution is 200-240 g/L, and the reaction temperature is 85-95 ℃.
The method for extracting lithium from lithium iron phosphate powder mixed with ternary powder and recovering nickel, cobalt and manganese metal takes typical lithium iron powder recovered in the market as an object, part of ternary powder is mixed due to the diversity of raw material types, recovery ways, classification modes, crushing processes and the like, and Li is obtained by sequentially carrying out size mixing, ultrasonic high-energy oxygen and hydrogen peroxide combined oxidation leaching, resin recovery of nickel, cobalt and manganese metal, preliminary impurity removal, evaporation concentration, alkaline impurity removal, activated carbon decoloration and CO2 Ca removal2SO4Purifying the solution, and then precipitating lithium through channels and collaterals to obtain the battery-grade lithium carbonate product. The nickel-cobalt-manganese-containing solution recovered by the resin can be used as a raw material for preparing a ternary precursor material, and resources are effectively recovered.
According to the method for extracting lithium from lithium iron phosphate powder mixed with ternary powder and recovering nickel, cobalt and manganese metals, the defects of high unit consumption of hydrogen peroxide and high organic content of leachate in the traditional hydrogen peroxide oxidation and acid leaching method are overcome by introducing ultrasonic high-energy oxygen, the production cost is effectively reduced, and the product quality is improved. Meanwhile, the heavy resin is introduced to recover nickel, cobalt and manganese metals, so that the current situations of high acid and alkali consumption, difficult filter pressing and long impurity removal process in the traditional method are avoided. Under the condition that the reaction system continuously releases heat, the unit consumption of hydrogen peroxide is close to a theoretical value, and the yields of Li, nickel, cobalt and manganese are both more than 96%. The method has the advantages of strong raw material adaptability, low equipment requirement, simple process, low energy consumption, economy and environmental protection, can realize comprehensive recovery of valuable metals, and is suitable for large-scale industrial production.
Example 1
The invention provides a method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder, which comprises the following steps:
(1) firstly, 16m of tap water is pumped into a 30m downward slope cultivation reaction tank, 5 tons of lithium iron powder (3.56% of Li, 0.046% of Ni, 0.013% of Co and 0.027% of Mn) is put into the reaction tank, the mixture is uniformly stirred, and then 830L of concentrated H is pumped into the reaction tank2SO4Mixing into slurry;
(2) introducing ultrasonic high-energy oxygen generated by an ultrasonic high-energy oxygen generating device into the bottom of the reaction tank at a flow rate of 20m for carrying out the cultivation in a year, and simultaneously pumping 50% H at a flow rate of 8.1L/min2O2The maximum reaction temperature is 77 ℃, the stirring frequency is 50HZ, and the combined oxidation is carried out for 2.5 h. The slurry was checked for blue absence with a 1% by mass potassium ferricyanide solution. And (3) performing pressure filtration to obtain 15.3m high-yield nucleic acid liquid, wherein the ion concentration of the acid liquid is 11.28g/L, Ni:0.14g/L, Co:0.042g/L, Mn: 0.086g/L, F:0.74g/L, PO4 3-0.16 g/L. The unit consumption of 50 percent hydrogen peroxide is 0.291;
(3) enabling the pickle liquor to pass through the weight removal resin at the flow rate of 3BV/h, adsorbing Ni, Co and Mn metal ions, wherein the Li concentration of the adsorbed pickle liquor is 11.25g/L, and the concentrations of Ni, Co and Mn are 0.0002g/L, 0.0001g/L and 0.0004g/L respectively; resolving the weight-removing resin with 2mol/L sulfuric acid to obtain a nickel-cobalt-manganese sulfate solution;
(4) subjecting the adsorbed solution to 50% H2O2Oxidation of Fe2+Adjusting pH to 8.0 with CaO, press filtering to obtain initial impurity-removed solution F, PO4 3-And Ca concentrations of 0.0012g/L, 0.018g/L and 0.38g/L, respectively;
(5) further evaporating and concentrating the primary impurity-removed liquid, wherein the concentration of Li in the concentrated liquid is 22.6 g/L;
(6) adding 32% of the concentrated solutionNaOH solution to pH =12, add 25kg of activated charcoal, CO2The gas flow rate is 5m for each hour, and the stirring reaction is carried out for 0.5 hour. Obtaining Li after filter pressing2SO4Carrying out 7.7m ethanol planting on the purified liquid, wherein the concentrations of Li, Ca and Mg are 21.98g/L, 0.082g/L and 0.0013g/L respectively;
(7) to Li2SO4EDTA8.5kg is added into the purified liquid, heated and dissolved, and then 230g/LNa is pumped in2CO3And heating the solution to 95 ℃ to deposit lithium, centrifuging, washing and drying to obtain 823kg of lithium carbonate, wherein the comprehensive yield of Li from lithium iron powder to lithium carbonate is 87.13%.
Example 2
The invention provides a method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder, which comprises the following steps:
(1) first, 20m tap water is pumped into the 30m full-length cultivation reaction tank, 5 tons of lithium iron powder (Li: 4.25%, Ni:1.67%, Co:1.03%, Mn: 1.41%) are put into the reaction tank, the mixture is uniformly stirred, and 842L concentrated H is pumped into the reaction tank2SO4Mixing into slurry;
(2) introducing ultrasonic high-energy oxygen generated by an ultrasonic high-energy oxygen generating device into the bottom of the reaction tank at a flow rate of 30m for carrying out the cultivation in a year, and simultaneously pumping 50% H at a flow rate of 8.3L/min2O2The maximum reaction temperature is 80 ℃, the stirring frequency is 50HZ, and the combined oxidation is carried out for 2.17 h. The slurry was checked for blue absence with a 1% by mass potassium ferricyanide solution. Performing pressure filtration to obtain 19.5m ethanol leaching liquor, wherein the ion concentration of the leaching liquor is Li:10.85g/L, Ni:4.26g/L, Co:2.61g/L, Mn: 3.56g/L, F:0.87g/L, PO4 3-0.073 g/L. The unit consumption of 50 percent hydrogen peroxide is 0.258;
(3) enabling the pickle liquor to pass through the weight removal resin at the flow rate of 2.5BV/h, adsorbing Ni, Co and Mn metal ions, wherein the Li concentration of the adsorbed pickle liquor is 10.59g/L, and the Ni, Co and Mn concentrations are 0.0003g/L, 0.0001g/L and 0.0006g/L respectively; resolving the weight-removing resin with 2mol/L sulfuric acid to obtain a nickel-cobalt-manganese sulfate solution;
(4) subjecting the adsorbed solution to 50% H2O2Oxidation of Fe2+Adjusting pH to 7.6 with CaO, press filtering to obtain initial impurity-removed solution F, PO4 3-And the Ca concentrations were 0.0015g/L, 0.013g/L and 0.41g/L, respectively;
(5) further evaporating and concentrating the primary impurity-removed liquid, wherein the concentration of Li in the concentrated liquid is 22.55 g/L;
(6) adding 32% NaOH solution into the above concentrated solution to pH =12.8, adding 30kg of activated carbon and CO2The gas flow rate is 10m for each hour, and the stirring reaction is carried out for 0.5 hour. Li after filter pressing2SO4Carrying out 9.4m ethanol planting on the purified liquid, wherein the concentrations of Li, Ca and Mg are 22.10g/L, 0.11g/L and 0.0013g/L respectively;
(7) to Li2SO4EDTA13.8kg is added into the purified liquid, and after being dissolved, 230g/LNa is pumped in2CO3And heating the solution to 90 ℃ to deposit lithium, centrifuging, washing and drying to obtain 1010kg of lithium carbonate, wherein the comprehensive yield of Li from lithium iron powder to lithium carbonate is 89.61%.
Example 3
The invention provides a method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder, which comprises the following steps:
(1) first, 14.5m tap water was pumped into the 30m thin-wall labor reaction tank, 5 t of lithium iron powder (Li: 3.51%, Ni:0.86%, Co:0.51%, Mn: 0.34%) was put into the reaction tank, and after stirring, 825L concentrated H was pumped in2SO4Mixing into slurry;
(2) introducing ultrasonic high-energy oxygen generated by an ultrasonic high-energy oxygen generating device into the bottom of the reaction tank at a flow rate of 10m for carrying out the cultivation in a year, and simultaneously pumping 50% H at a flow rate of 7.4L/min2O2The maximum reaction temperature is 80 ℃, the stirring frequency is 50HZ, and the combined oxidation is carried out for 3.0 h. The slurry was checked for blue absence with a 1% by mass potassium ferricyanide solution. And (3) performing pressure filtration to obtain the pickle liquor with 14m weight percent, wherein the ion concentration of the pickle liquor is Li:12.37g/L, Ni:3.05g/L, Co:1.79g/L, Mn: 1.2g/L, F:1.75g/L, PO4 3-0.37 g/L. The unit consumption of 50 percent hydrogen peroxide is 0.266;
(3) enabling the pickle liquor to pass through the weight removal resin at the flow rate of 2.5BV/h, adsorbing Ni, Co and Mn metal ions, wherein the concentration of Li in the adsorbed pickle liquor is 12.25g/L, and the concentrations of Ni, Co and Mn are 0.0005g/L, 0.0003g/L and 0.0002g/L respectively; (ii) a Resolving the weight-removing resin with 2mol/L sulfuric acid to obtain a nickel-cobalt-manganese sulfate solution;
(4) subjecting the adsorbed solution to 50% H2O2Oxidation of Fe2+Then regulating the pH value to 7.4 by CaO, and performing filter pressingObtaining a primary impurity removal solution, F, PO4 3-And Ca concentrations of 0.004g/L, 0.015g/L and 0.36g/L, respectively;
(5) further evaporating and concentrating the primary impurity-removed liquid, wherein the concentration of Li in the concentrated liquid is 22.25 g/L;
(6) adding 32% NaOH solution into the above concentrated solution to pH =13.2, adding 25kg of activated carbon and CO2The gas flow rate is 10m for each hour, and the stirring reaction is carried out for 1 hour. Li after filter pressing2SO4Carrying out 7.7m ethanol planting on the purified liquid, wherein the concentrations of Li, Ca and Mg are 22.09g/L, 0.076g/L and 0.0009g/L respectively;
(7) to Li2SO4EDTA8.0kg is added into the purified liquid, and after being dissolved, 230g/LNa is pumped in2CO3And heating the solution to 95 ℃ to deposit lithium, centrifuging, washing and drying to obtain 806kg of lithium carbonate, wherein the comprehensive yield of Li from lithium iron powder to lithium carbonate is 86.7%.
Table 1 examples oxidation acid leaching each ion leaching rate
| Numbering | Li% | Ni% | Co% | Mn% |
| Example 1 | 96.96 | 99.78 | 98.86 | 97.47 |
| Example 2 | 99.56 | 99.49 | 98.83 | 98.47 |
| Example 3 | 98.68 | 99.30 | 98.27 | 98.82 |
TABLE 2 example Battery grade lithium carbonate product index
The above examples only express embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder is characterized by comprising the following steps: the method comprises the following steps: step (1), size mixing: mixing lithium iron phosphate powder mixed with the ternary powder, concentrated sulfuric acid and water according to a certain proportion to obtain slurry; step (2), combined oxidation leaching: introducing ultrasonic high-energy oxygen into the slurry obtained in the step (1), and slowly adding H2O2Until no Fe is detected by using 1% potassium ferricyanide solution2+Stopping oxidation, and filtering to obtain pickle liquor and pickle slag; and (3) recovering nickel, cobalt and manganese from resin: adsorbing nickel, cobalt and manganese metal ions in the pickle liquor obtained in the step (2) by using a heavy-duty resin, collecting the adsorbed liquor, stopping adsorption when the content of the nickel, cobalt and manganese ions in the adsorbed liquor approaches a limit value, analyzing the resin by using dilute sulfuric acid, and recovering to obtain a nickel, cobalt and manganese-containing solution; step (4), primary impurity removal: oxidizing the residual ferrous ions in the resin adsorbed liquid obtained in the step (3) with hydrogen peroxide, adjusting the pH to 7-8 with a calcium-containing compound, removing iron, aluminum, titanium, phosphate radical and F ions, stirring for reacting for 0.5-1 h, and filtering to obtain a primary impurity removal liquid and primary impurity removal slag; and (5) evaporation and concentration: evaporating and concentrating the primary impurity-removed liquid obtained in the step (4) to obtain a concentrated liquid and a small amount of slag; alkaline impurity removal: adjusting pH of the concentrated solution to alkaline with alkaline agent, adding active carbon for decolorization, introducing CO2Removing calcium from the gas, stirring for reaction for 0.5-1 h, and filtering to obtain a lithium sulfate purified solution and alkaline impurity-removing slag; step (7) complexing and precipitating lithium: to step (6)Adding an organic complexing agent into the purified solution, heating and dissolving, adding a soda solution to precipitate lithium, and then centrifuging, washing and drying to obtain the battery-grade lithium carbonate.
2. The method for extracting lithium and recovering nickel cobalt manganese metal from lithium iron phosphate mixed with ternary powder as claimed in claim 1, wherein: the mass ratio of the lithium iron phosphate powder mixed with the ternary powder in the step (1), the concentrated sulfuric acid and the water is 5: 1.5-1.6: 15-20.
3. The method for extracting lithium and recovering nickel cobalt manganese metal from lithium iron phosphate mixed with ternary powder as claimed in claim 2, characterized in that: and (3) carrying out ultrasonic high-energy oxygen flow at 10-30 m/h in the step (2), carrying out hydrogen peroxide flow at 4-9L/min, controlling the reaction temperature below 80 ℃, and carrying out oxidation for 2-4 h.
4. The method for extracting lithium and recovering nickel cobalt manganese metal from lithium iron phosphate mixed with ternary powder as claimed in claim 3, characterized in that: the heavy-weight-removing resin in the step (3) is resin with excellent adsorption performance on Ni, Co and Mn metals, and the limiting values of Ni, Co and Mn ion contents in the adsorbed liquid are all lower than 0.001 g/L.
5. The method for extracting lithium and recovering nickel cobalt manganese metal from lithium iron phosphate mixed with ternary powder as claimed in claim 4, wherein: in the step (4), the calcium-containing compound is CaO, Ca (OH)2And CaCO3One or two of them.
6. The method for extracting lithium and recovering nickel cobalt manganese metal from lithium iron phosphate mixed with ternary powder as claimed in claim 5, wherein: and (5) evaporating and concentrating until the concentration of Li in the concentrated solution is not lower than 20 g/L.
7. The method for extracting lithium and recovering nickel cobalt manganese metal from lithium iron phosphate mixed with ternary powder as claimed in claim 6, wherein: the alkaline agent in the step (6) is sodium hydroxide, potassium hydroxide,At least one of lithium hydroxide, alkali agent for adjusting the pH to be more than 12, activated carbon added according to 3-5 per mill of the liquid mass, and CO2The gas flow rate is 5-30 m/h.
8. The method for extracting lithium and recovering nickel cobalt manganese metal from lithium iron phosphate mixed with ternary powder as claimed in claim 7, wherein: in the step (7), the organic complexing agent is EDTA or EDTA-2Na, the addition amount is 1-2 times of the theoretical amount of complexed calcium and magnesium, the concentration of the soda solution is 200-240 g/L, and the reaction temperature is 85-95 ℃.
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