CN116802332A - Method for recycling lithium in lithium waste battery leaching solution based on directional circulation and application of method - Google Patents
Method for recycling lithium in lithium waste battery leaching solution based on directional circulation and application of method Download PDFInfo
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- CN116802332A CN116802332A CN202380009011.3A CN202380009011A CN116802332A CN 116802332 A CN116802332 A CN 116802332A CN 202380009011 A CN202380009011 A CN 202380009011A CN 116802332 A CN116802332 A CN 116802332A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000002386 leaching Methods 0.000 title claims abstract description 40
- 238000004064 recycling Methods 0.000 title claims abstract description 9
- 239000010926 waste battery Substances 0.000 title abstract description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 110
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 70
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 55
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000002893 slag Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000011282 treatment Methods 0.000 claims abstract description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 71
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 66
- 239000013078 crystal Substances 0.000 claims description 41
- 238000001556 precipitation Methods 0.000 claims description 37
- 229910001416 lithium ion Inorganic materials 0.000 claims description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 239000002699 waste material Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000002738 chelating agent Substances 0.000 claims description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 6
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- -1 fluoride ions Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 8
- 239000010941 cobalt Substances 0.000 abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 239000011575 calcium Substances 0.000 description 33
- 229910052791 calcium Inorganic materials 0.000 description 32
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 31
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 19
- 238000001914 filtration Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000001509 sodium citrate Substances 0.000 description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 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 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000004673 fluoride salts Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Abstract
The invention discloses a method for recycling lithium in lithium waste battery leaching liquid based on directional circulation and application thereof. According to the invention, lithium in the leaching solution is precipitated at one time by using calcium-doped sodium fluoride solid, so that metal lithium in the leaching solution is enriched into lithium fluoride slag, the recovery rate of the metal lithium is improved, meanwhile, the content of nickel, cobalt and manganese metal in the lithium fluoride slag is reduced, the difficulty in preparing battery grade lithium carbonate from the lithium fluoride slag is reduced, and the subsequent treatment flow of the nickel, cobalt and manganese metal liquid is simplified.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery recovery, and particularly relates to a method for recovering lithium in lithium waste battery leaching liquid based on directional circulation and application thereof.
Background
With the rapid development of new energy electric automobile industry, the installed amount of the power lithium ion battery is increased year by year, and the lithium element is used as a key component of the power lithium battery, so that the increase or decrease in the resource supply situation exists. Along with the annual increase of the loading of the power batteries, the number of lithium ion batteries reaching the scrapped years is increased year by year, and a low-cost and high-efficiency recovery treatment method needs to be developed so as to obtain high recovery rate and high value return rate of high-value metals.
Patent CN101942569a discloses a method for recovering lithium from waste lithium ion batteries and waste pole pieces, which comprises the following steps: (1) Crushing the waste lithium ion batteries or the waste pole pieces by using a crusher, and then placing the crushed waste lithium ion batteries or the waste pole pieces in a high-temperature furnace to remove the binder by heat treatment to obtain powder; (2) Dissolving with sodium hydroxide solution to remove aluminum in the powder, and filtering to obtain low-aluminum filter mud; (3) Leaching the low-aluminum filter mud by using acid and a reducing agent to obtain a leaching solution; (4) Removing impurities such as iron, copper, aluminum and the like in the leaching solution by a chemical method; (5) Precipitating lithium in the leaching solution by using fluoride salt to obtain a crude lithium fluoride product; (6) Washing, filtering and drying the lithium fluoride crude product to obtain a lithium fluoride product. The purity of LiF products purified by multiple times of washing can reach more than 98%, but the recovery rate of lithium precipitated by a single time by adopting the method is low, and the recovered lithium fluoride contains excessive nickel cobalt manganese metal ions, so that valuable metals of the battery anode material are lost.
The simple fluoride salt solution is used for precipitating lithium ions in the leaching solution, so that incomplete precipitation of the lithium ions in the leaching solution is easy to cause, the recovery rate of the lithium ions can be improved after repeated concentration, meanwhile, the content of metal ions such as nickel, cobalt, manganese and the like in lithium fluoride slag is increased, the recovery process is complex, and meanwhile, the process difficulty and the treatment cost of the subsequent preparation of battery-grade lithium carbonate are improved, so that the development of a process method for efficiently recovering the lithium ions in the leaching solution in a short process is needed, and the process difficulty and the production cost of the subsequent preparation of battery-grade lithium carbonate are reduced.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a method for recycling lithium in lithium waste battery leaching liquid based on directional circulation and application thereof, and the method uses calcium-doped sodium fluoride solid to precipitate lithium in the leaching liquid at one time, so that metal lithium in the leaching liquid is enriched into lithium fluoride slag, the recovery rate of the metal lithium is improved, meanwhile, the content of nickel cobalt manganese metal in the lithium fluoride slag is reduced, the difficulty in preparing battery grade lithium carbonate from the lithium fluoride slag is reduced, and the subsequent treatment flow of nickel cobalt manganese metal liquid is simplified.
According to one aspect of the present invention, there is provided a method for recovering lithium from a leachate of a waste lithium ion battery, comprising the steps of:
s1: copper and aluminum removal treatment is carried out on the leaching solution of the waste lithium ion battery to obtain a solution after impurity removal;
s2: preparing a calcium sulfate solution, adding sodium fluoride, ammonium fluoride and a dispersing agent into the calcium sulfate solution, heating the obtained mixed solution for reaction, cooling, and then carrying out solid-liquid separation to obtain calcium-doped sodium fluoride crystals;
s3: and adding the calcium-doped sodium fluoride crystal into the impurity-removed liquid, stirring at a low speed, performing lithium precipitation reaction, and performing solid-liquid separation to obtain lithium fluoride slag and lithium precipitation liquid.
In some embodiments of the invention, in step S1, the leachate is prepared by the process of: pulping the positive electrode powder obtained after crushing and screening the waste lithium ion batteries, adding acid and a reducing agent to leach the positive electrode powder, and carrying out solid-liquid separation to obtain the leaching solution. Further, the acid is at least one of sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, ascorbic acid or oxalic acid; the reducing agent is at least one of hydrogen peroxide, sodium sulfite, sodium thiosulfate or ammonium chloride.
In some embodiments of the present invention, in step S1, the waste lithium ion battery is at least one of a ternary nickel cobalt lithium manganate battery, a ternary nickel cobalt lithium aluminate battery, a lithium cobaltate battery, a lithium manganate battery, a nickel cobalt manganese aluminum lithium quaternary lithium battery, lithium iron phosphate or lithium manganese iron phosphate.
In some embodiments of the present invention, in step S1, the copper and iron and aluminum removal process is as follows: adding metal powder into the leaching solution for displacement reaction, carrying out solid-liquid separation to obtain sponge copper and filtrate, adding alkali into the filtrate to adjust pH value for iron and aluminum precipitation, and carrying out solid-liquid separation to obtain iron and aluminum slag and the impurity-removed liquid. Further, the metal powder is at least one of iron powder, nickel powder or manganese powder. The alkali is at least one of sodium carbonate or sodium hydroxide.
In some embodiments of the present invention, in step S1, the impurity-removed liquid contains nickel in an amount of 35-60g/L, cobalt in an amount of 15-35g/L, manganese in an amount of 10-30g/L, lithium in an amount of 6-18g/L, iron in an amount of 0-15mg/L, aluminum in an amount of 0-20mg/L, copper in an amount of 0-15mg/L, calcium in an amount of 5-135mg/L, and magnesium in an amount of 8-100mg/L.
In some embodiments of the invention, in step S2, the calcium sulfate solution is formulated from a calcium salt, sulfuric acid, and EDTA chelating agent, the calcium salt being at least one of calcium sulfate or calcium fluoride. The sulfuric acid and EDTA are added during the preparation of the calcium sulfate solution, so that the dissolution of the calcium sulfate can be quickened, and the uneven distribution of Ca in the sodium fluoride crystal caused by the low solubility of the calcium sulfate is reduced.
In some embodiments of the invention, in step S2, the molar ratio of calcium salt, sulfuric acid, and EDTA chelating agent is 1: (0.3-0.6): (0.1-0.4).
In some embodiments of the invention, in step S2, the molar ratio of sodium fluoride, ammonium fluoride and dispersant is 1: (0.1-0.4): (0.05-0.15).
In some embodiments of the invention, in step S2, the ratio of the molar amount of calcium sulfate in the calcium sulfate solution to the molar amount of sodium fluoride is (0.05-0.15): 1.
in some embodiments of the present invention, in step S2, the calcium-doped sodium fluoride crystal has a doping amount of 5mol% to 15mol% of calcium.
In some embodiments of the present invention, in step S2, the heating reaction is performed by microwave heating at 120-180 ℃ for 2-6 hours. The microwave heating can raise the temperature of the solution in a short time to reach a high-temperature state, so that the temperature in the solution is uniformly raised, substances in the solution are basically dissolved, compared with a common hydrothermal method, the microwave heating has smaller crystals and better effect, and the yield of the microwave heating method is higher.
In some embodiments of the invention, in step S2, the dispersing agent is sodium citrate.
In some embodiments of the present invention, in step S3, the molar ratio of the fluoride ion in the calcium-doped sodium fluoride crystal to the lithium ion in the solution after impurity removal is (1.1-1.3): 1 adding the calcium-doped sodium fluoride crystal.
In some embodiments of the invention, in step S3, the stirring speed is 50-200r/min, and the temperature of the lithium precipitation reaction is 50-90 ℃. Further, the time of the lithium precipitation reaction is 4-8h.
In some embodiments of the present invention, in step S3, the mass content of lithium fluoride in the lithium fluoride slag is 70% -85%, the mass content of calcium ions is 6% -14%, the mass content of magnesium ions is 1% -2%, and the total mass content of nickel cobalt manganese ions is less than or equal to 3%.
In some embodiments of the present invention, in step S3, the total concentration of nickel, cobalt and manganese in the solution after lithium precipitation is 60-85g/L, and the concentration of lithium ions is less than or equal to 0.3g/L.
In some embodiments of the present invention, in step S3, further includes: extracting and purifying the lithium-precipitated liquid by using an extracting agent to obtain a nickel cobalt manganese extract and a raffinate containing calcium and magnesium, and back-extracting the nickel cobalt manganese extract by using acid to obtain a nickel cobalt manganese salt solution. Further, the extractant is at least one of P204, P507 or carboxylic extractant BC 196. Further, the acid used for the back extraction is sulfuric acid or hydrochloric acid. The pH value of the solution after lithium precipitation is 3.5-5.0, and the solution can realize that Ca, mg and Li metals are not extracted basically at the pH value.
The invention also provides application of the lithium fluoride slag prepared by the method in preparation of battery-grade lithium carbonate. It should be noted that, the lithium fluoride produced by precipitation with the fluoride salt solution in the conventional method also contains calcium impurities, and in the process of preparing battery-grade lithium carbonate from the subsequent lithium fluoride, sodium carbonate is generally required to be added for performing the calcium removal operation, so that the difficulty of calcium removal is low, and even if calcium is additionally introduced into the lithium fluoride slag, the increase of the calcium content does not bring additional impurity removal pressure to the back-end process.
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
1. according to the invention, calcium doped sodium fluoride crystals are synthesized first, and are directly added into waste battery leaching solution after impurity removal in a solid form, lithium ions in the leaching solution are precipitated under a low-speed stirring state, and as the solubility of calcium sulfate in the calcium doped sodium fluoride crystal structure is lower, sodium fluoride is easy to dissolve, fluorine ions released by dissolution of sodium fluoride can form precipitation with the Li ions in the solution, and the precipitation is preferentially carried out in a calcium sulfate crystal frame to form lithium fluoride slag wrapped by the calcium sulfate (or calcium fluoride) frame, so that the contact area of lithium fluoride and the solution can be reduced under the condition of maintaining the crystal frame, and the concentration of Li in the solution is reduced. In addition, the lower stirring speed can be controlled to reduce the dissolution speed of the calcium-doped sodium fluoride solid, and the diffusion speed of fluoride ions formed by dissolution of sodium fluoride is controlled, so that Li ions are diffused to the surface of the calcium-doped sodium fluoride solid in a liquid phase, liF generated by F is deposited in the calcium-doped sodium fluoride solid, and the lithium ion concentration of the solution is reduced.
2. In the process of preparing the calcium-doped sodium fluoride crystal, partial calcium fluoride is generated, calcium fluoride crystal nucleus in the solution, and sodium fluoride, calcium sulfate and calcium fluoride can grow on the tiny crystal nucleus to form precipitation co-doped crystal in the cooling process.
2. The content of nickel cobalt manganese metal in lithium fluoride slag can be reduced to below 3% by using calcium doped sodium fluoride crystal to precipitate lithium in leaching liquid, so that the precipitation amount of nickel cobalt manganese metal in the lithium precipitation stage is reduced, and the subsequent recovery cost is reduced.
3. The calcium sulfate is used for preparing the calcium-doped sodium fluoride crystal, the solubility of the calcium sulfate is low, the integral framework structure of the calcium-doped sodium fluoride solid can be effectively maintained, the deep lithium precipitation effect is good, meanwhile, the introduction of other anions (chloride ions) can be reduced, and the subsequent treatment difficulty of a leaching solution is reduced.
4. NH addition during synthesis of calcium doped sodium fluoride crystals 4 F, the growth direction of the crystal can be regulated and controlled, so that the crystal structure is in a long rod shape, and the path of sodium fluoride dissolved and diffused into the solution is shorter because the crystal structure is not in a short and thick shape, so that the difficulty of forming lithium fluoride is lower, and the utilization efficiency of the sodium fluoride can be improved by the long rod-shaped structure; the addition of the dispersing agent is beneficial to regulating and controlling the uniform distribution of Ca ions during the reaction.
5. The nickel-cobalt-manganese metal solution after lithium precipitation can be directly extracted and purified by an extracting agent due to low lithium ion content, ca, mg and Li metals can be basically not extracted, and the obtained purified nickel-cobalt-manganese salt solution can be used for synthesizing ternary precursors, so that the cost increase of a purification process due to the too high content of Li elements in the extraction stage is reduced.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a process flow diagram of example 1 of the present invention;
FIG. 2 is an SEM image of calcium-doped sodium fluoride crystals obtained in example 2 of the present invention;
FIG. 3 is an SEM image of calcium-doped sodium fluoride crystals obtained in comparative example 2 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
A method for recycling lithium in waste lithium battery leaching liquid by calcium doped sodium fluoride crystal refers to a figure 1, and comprises the following specific steps:
(1) 1kg of ternary powder obtained after crushing and screening waste nickel cobalt lithium manganate batteries is added with 3L of water for pulping, 0.43L of concentrated sulfuric acid and 0.13L of 30% hydrogen peroxide are added for leaching the ternary powder, and the powder is subjected to full acid leaching to leach metals and then is filtered and separated to obtain leaching liquid;
(2) Copper removal is carried out on the leaching solution by using 6g of iron powder, sponge copper and filtrate are obtained after filtration, then iron and aluminum removal is carried out by using sodium carbonate to control the pH value of the filtrate to be 3.8-4.0, and iron and aluminum slag and impurity-removed liquid are obtained after filtration;
TABLE 1 concentration of ions in the solution after impurity removal
| Element(s) | Ni | Co | Mn | Li | Ca | Fe | Mg | Al | Cu |
| Content (g/L) | 57.1 | 32.4 | 27.6 | 17.7 | 0.035 | 0.015 | 0.100 | 0.020 | 0.015 |
(3) Preparing a calcium sulfate solution from 0.1mol of calcium sulfate, 0.03mol of 98% concentrated sulfuric acid, 0.03mol of EDTA chelating agent and 10L of water, adding a mixture of 2mol of sodium fluoride, 0.2mol of ammonia fluoride and 0.1mol of sodium citrate into the calcium sulfate solution, and stirring to form a mixed solution;
(4) Heating the mixed solution to a high temperature state by microwaves under a closed condition, keeping the temperature at 180 ℃ for 2 hours, slowly cooling, and filtering and washing to obtain calcium-doped sodium fluoride crystals with 5% of calcium mole content;
(5) The prepared calcium doped sodium fluoride crystal is prepared according to the following fluoride ion: lithium ion molar ratio 1.1:1, directly adding the solution into the impurity-removed solution obtained in the step (2) to carry out lithium precipitation reaction, wherein the reaction temperature is 50 ℃, the solution stirring speed is 200r/min, the precipitation reaction time is 4 hours, filtering to obtain lithium fluoride slag and a lithium precipitation solution, and carrying out treatments such as leaching, calcium removal, lithium precipitation and the like on the lithium fluoride slag to prepare battery-grade lithium carbonate;
(6) And extracting the lithium-precipitated liquid by using a carboxylic acid extractant BC196 to obtain a nickel cobalt manganese extract and a raffinate containing calcium and magnesium, and carrying out back extraction on the nickel cobalt manganese extract by using sulfuric acid to obtain a nickel cobalt manganese sulfate liquid.
Example 2
A method for recycling lithium in waste lithium battery leaching liquid by calcium doped sodium fluoride crystal comprises the following specific processes:
step (1) and step (2) are the same as in example 1;
(3) Preparing a calcium sulfate solution from 0.1mol of calcium sulfate, 0.05mol of 98% concentrated sulfuric acid, 0.03mol of EDTA chelating agent and 10L of water, adding a mixture of 1mol of sodium fluoride, 0.2mol of ammonia fluoride and 0.1mol of sodium citrate into the calcium sulfate solution, and stirring to form a mixed solution;
(4) Heating the mixed solution to a high temperature state by microwaves under a closed condition, keeping the temperature at 160 ℃ for 4 hours, slowly cooling, and filtering and washing to obtain calcium-doped sodium fluoride crystals with the calcium mole content of 10%, wherein the morphology is shown in a figure 2, and the crystal structure is long rod-shaped;
(5) The prepared calcium doped sodium fluoride crystal is prepared according to the following fluoride ion: lithium ion molar ratio 1.2:1, directly adding the solution into the impurity-removed solution obtained in the step (2) to carry out lithium precipitation reaction, wherein the reaction temperature is 70 ℃, the solution stirring speed is 100r/min, the precipitation reaction time is 6h, filtering to obtain lithium fluoride slag and a lithium precipitation solution, and carrying out treatments such as leaching, calcium removal, lithium precipitation and the like on the lithium fluoride slag to prepare battery-grade lithium carbonate;
(6) And extracting the lithium-precipitated liquid by using a carboxylic acid extractant BC196 to obtain a nickel cobalt manganese extract and a raffinate containing calcium and magnesium, and carrying out back extraction on the nickel cobalt manganese extract by using sulfuric acid to obtain a nickel cobalt manganese sulfate liquid.
Example 3
A method for recycling lithium in waste lithium battery leaching liquid by calcium doped sodium fluoride crystal comprises the following specific processes:
step (1) and step (2) are the same as in example 1;
(3) Preparing a calcium sulfate solution from 0.1mol of calcium sulfate, 0.06mol of 98% concentrated sulfuric acid, 0.04mol of EDTA chelating agent and 10L of water, adding a mixture of 0.67mol of sodium fluoride, 0.27mol of ammonia fluoride and 0.1mol of sodium citrate into the calcium sulfate solution, and stirring to form a mixed solution;
(4) Heating the mixed solution to a high temperature state by microwaves under a closed condition, keeping the temperature at 160 ℃ for 4 hours, slowly cooling, and filtering and washing to obtain calcium-doped sodium fluoride crystals with the calcium mole content of 15%;
(5) The prepared calcium doped sodium fluoride crystal is prepared according to the following fluoride ion: lithium ion molar ratio 1.3:1, directly adding the solution into the impurity-removed solution obtained in the step (2) to carry out lithium precipitation reaction, wherein the reaction temperature is 90 ℃, the solution stirring speed is 50r/min, the precipitation reaction time is 4 hours, filtering to obtain lithium fluoride slag and a lithium precipitation solution, and carrying out treatments such as leaching, calcium removal, lithium precipitation and the like on the lithium fluoride slag to prepare battery-grade lithium carbonate;
(6) And extracting the lithium-precipitated liquid by using a carboxylic acid extractant BC196 to obtain a nickel cobalt manganese extract and a raffinate containing calcium and magnesium, and carrying out back extraction on the nickel cobalt manganese extract by using sulfuric acid to obtain a nickel cobalt manganese sulfate liquid.
Comparative example 1
The method for recycling lithium in the leaching solution of the waste lithium battery is different from the method in the embodiment 1 in that calcium doped sodium fluoride crystal is not prepared, common sodium fluoride is added for precipitating lithium, and the specific process is as follows:
step (1) and step (2) are the same as in example 1;
(3) According to fluoride ion: lithium ion molar ratio 1.1: and 1, directly adding untreated sodium fluoride solid into the impurity-removed liquid obtained in the step 2 for lithium precipitation reaction, wherein the reaction temperature is 50 ℃, the solution stirring speed is 200r/min, the precipitation reaction time is 4h, filtering to obtain lithium fluoride slag and lithium-precipitated liquid, and carrying out treatments such as leaching, calcium removal, lithium precipitation and the like on the lithium fluoride slag to prepare the battery-grade lithium carbonate.
(4) And extracting the lithium-precipitated liquid by using a carboxylic acid extractant BC196 to obtain a nickel cobalt manganese extract and a raffinate containing calcium and magnesium, and carrying out back extraction on the nickel cobalt manganese extract by using sulfuric acid to obtain a nickel cobalt manganese sulfate liquid.
Comparative example 2
The difference between the method for recovering lithium from the leaching solution of the waste lithium battery by using the calcium doped sodium fluoride crystal and the method for recovering lithium from the leaching solution of the waste lithium battery in the embodiment 2 is that ammonia fluoride is not added in the step (3), and the specific process of the step (3) is as follows: a calcium sulfate solution was prepared from 0.1mol of calcium sulfate, 0.05mol of 98% concentrated sulfuric acid, 0.03mol of EDTA chelating agent and 10L of water, and a mixture of 1mol of sodium fluoride and 0.1mol of sodium citrate was added to the calcium sulfate solution and stirred to form a mixed solution. Comparative example (2) other steps were the same as in example (2).
The morphology of the calcium-doped sodium fluoride crystal prepared in the comparative example is shown in fig. 3, and the crystal structure is short and thick.
TABLE 2 concentration of ions in the solution after lithium deposition
| Element (g/L) | Ni | Co | Mn | Li | Ca | Fe | Mg | Al | Cu |
| Example 1 | 55.6 | 29.8 | 25.1 | 0.24 | 0.033 | 0.012 | 0.087 | 0.018 | 0.012 |
| Example 2 | 53.8 | 26.9 | 24.7 | 0.17 | 0.097 | 0.018 | 0.072 | 0.021 | 0.015 |
| Example 3 | 52.9 | 25.7 | 23.9 | 0.13 | 0.045 | 0.022 | 0.091 | 0.018 | 0.012 |
| Comparative example 1 | 48.6 | 22.4 | 20.9 | 1.36 | 0.042 | 0.024 | 0.081 | 0.023 | 0.017 |
| Comparative example 2 | 53.4 | 26.4 | 24.3 | 0.20 | 0.091 | 0.017 | 0.069 | 0.025 | 0.021 |
TABLE 3 mass fractions of ions in lithium fluoride dry slag
As can be seen from tables 2 and 3, the lithium ion content in the solution after lithium precipitation in comparative example 1 is significantly higher than that in example 1, the metal content is significantly lower than that in example 1, and the nickel, cobalt and manganese content in the dry residue of lithium fluoride in comparative example 1 is significantly higher than that in example 1, which indicates that the recovery rate of lithium precipitation in comparative example 1 by using common sodium fluoride is not high, and the valuable metal loss of nickel, cobalt and manganese is relatively high.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The method for recycling lithium in the leaching solution of the waste lithium ion battery is characterized by comprising the following steps of:
s1: copper and aluminum removal treatment is carried out on the leaching solution of the waste lithium ion battery to obtain a solution after impurity removal;
s2: preparing a calcium sulfate solution, adding sodium fluoride, ammonium fluoride and a dispersing agent into the calcium sulfate solution, heating the obtained mixed solution for reaction, cooling, and then carrying out solid-liquid separation to obtain calcium-doped sodium fluoride crystals;
s3: and adding the calcium-doped sodium fluoride crystal into the impurity-removed liquid, stirring at a low speed, performing lithium precipitation reaction, and performing solid-liquid separation to obtain lithium fluoride slag and lithium precipitation liquid.
2. The method according to claim 1, wherein in step S1, the copper and iron and aluminum removal treatment is performed by: adding metal powder into the leaching solution for displacement reaction, carrying out solid-liquid separation to obtain sponge copper and filtrate, adding alkali into the filtrate to adjust pH value for iron and aluminum precipitation, and carrying out solid-liquid separation to obtain iron and aluminum slag and the impurity-removed liquid.
3. The method of claim 1, wherein in step S2, the calcium sulfate solution is formulated from a calcium salt, sulfuric acid, and EDTA chelating agent, the calcium salt being at least one of calcium sulfate or calcium fluoride.
4. The method according to claim 4, wherein in step S2, the molar ratio of calcium salt, sulfuric acid and EDTA chelating agent is 1: (0.3-0.6): (0.1-0.4).
5. The method according to claim 1, wherein in step S2, the molar ratio of sodium fluoride, ammonium fluoride and dispersant is 1: (0.1-0.4): (0.05-0.15).
6. The method according to claim 1, wherein in step S2, the ratio of the molar amount of calcium sulfate in the calcium sulfate solution to the molar amount of sodium fluoride is (0.05-0.15): 1.
7. the method according to claim 1, wherein in step S2, the heating reaction is performed by microwave heating at 120-180 ℃ for 2-6 hours.
8. The method according to claim 1, wherein in step S3, the molar ratio of the fluoride ions in the calcium-doped sodium fluoride crystal to the lithium ions in the solution after the impurity removal is (1.1-1.3): 1 adding the calcium-doped sodium fluoride crystal.
9. The method according to claim 1, wherein in step S3, the stirring speed is 50-200r/min, and the temperature of the lithium precipitation reaction is 50-90 ℃.
10. Use of the lithium fluoride slag produced by the method of any one of claims 1-9 in the preparation of battery grade lithium carbonate.
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