CN116281918B - Method for finely separating and recovering full components of retired lithium iron phosphate black powder - Google Patents
Method for finely separating and recovering full components of retired lithium iron phosphate black powder Download PDFInfo
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- CN116281918B CN116281918B CN202310223624.9A CN202310223624A CN116281918B CN 116281918 B CN116281918 B CN 116281918B CN 202310223624 A CN202310223624 A CN 202310223624A CN 116281918 B CN116281918 B CN 116281918B
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- lithium
- ammonia
- iron phosphate
- sulfur
- rich
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- 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 53
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000000843 powder Substances 0.000 title claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 96
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 79
- 150000003839 salts Chemical class 0.000 claims abstract description 55
- 238000002386 leaching Methods 0.000 claims abstract description 30
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000005188 flotation Methods 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 230000020477 pH reduction Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 44
- AQGDXJQRVOCUQX-UHFFFAOYSA-N N.[S] Chemical compound N.[S] AQGDXJQRVOCUQX-UHFFFAOYSA-N 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 37
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 34
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 34
- 229910052717 sulfur Inorganic materials 0.000 claims description 33
- 238000001994 activation Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000011593 sulfur Substances 0.000 claims description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000010439 graphite Substances 0.000 claims description 25
- 229910002804 graphite Inorganic materials 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 230000004913 activation Effects 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000004073 vulcanization Methods 0.000 claims description 22
- 239000000292 calcium oxide Substances 0.000 claims description 21
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 21
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 17
- 239000005955 Ferric phosphate Substances 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 229940032958 ferric phosphate Drugs 0.000 claims description 16
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000012190 activator Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 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 9
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 239000010746 number 5 fuel oil Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000004537 pulping Methods 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 30
- -1 salt ammonia sulfate Chemical class 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004137 mechanical activation Methods 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 230000002308 calcification Effects 0.000 abstract 1
- 238000006477 desulfuration reaction Methods 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 238000003756 stirring Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910000398 iron phosphate Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000010440 gypsum Substances 0.000 description 6
- 229910052602 gypsum Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for finely separating and recovering all components of retired lithium iron phosphate black powder. The method comprises the following steps: vulcanizing and activating, reverse flotation water-soluble extraction of lithium, mixed salt crystallization, mixed salt ammonia sulfate removal and acidification and precipitation of lithium. Compared with the traditional recovery technology, the method adopts persulfate mechanical activation to replace a strong acid leaching process, calcification, desulfurization and ammonia separation to replace complicated neutralization and impurity removal in the traditional process, avoids the use of an acidic solvent, improves the conversion efficiency, shortens the process flow, and realizes the effects of fine separation of all components and high-quality conversion of the retired lithium iron phosphate black. The invention has the characteristics of high comprehensive utilization rate of resources, low energy consumption and disposal cost, easy application and popularization and the like.
Description
Technical field:
the invention relates to the technical field of comprehensive recovery and safe disposal of retired new energy devices, in particular to a method for finely separating and recovering all components of retired lithium iron phosphate black powder.
The background technology is as follows:
with the rapid development of new energy industry, new energy automobile markets in China have been in a 'rapid development period', and up to the present, the holding quantity is 1200 ten thousand, the 5-year growth rate is expected to be stabilized at 30% -40% in the future, and the sales quantity is expected to exceed 600 ten thousand pieces per year in 2025 years. Under the rapid growth of new energy automobile markets, the power lithium battery keeps on keeping the rapid growth potential. After the lithium battery is charged and discharged for hundreds of thousands of times, the internal structure of the battery can be irreversibly changed. Estimated according to the 5-8 years of the on-schedule service period, the first retirement burst period of the lithium battery is accepted in China, 2021, the theoretical recovery amount of the lithium battery in China reaches 59.7 ten thousand tons, the actual recovery amount is 23.6 ten thousand tons, and the recovery rate is 39.5%. Currently, the market size of the retired lithium battery recovery industry in China is about 165 hundred million yuan, the same ratio is increased by 65%, the estimated 2022 market size can reach 286 hundred million yuan, and the recovery market size in 2025 can break through 400 hundred million yuan.
Due to the resource properties of key strategic metals such as nickel, cobalt, lithium and the like and the environmental properties of toxic organic pollution components, how to realize safe disposal and comprehensive recovery of retired lithium batteries has become a hot spot in research of the new energy field. Compared with cobalt/lithium manganate, ternary lithium and other power batteries, the lithium iron phosphate has low price, high safety coefficient and excellent cycle performance, and is recognized as a good positive electrode material for electric automobiles and large-scale energy storage equipment. For retired lithium iron phosphate power lithium batteries, there are currently two main possible treatments: the lithium battery is used as a carrier of electric energy in other fields such as energy storage and the like, so that the residual value is fully exerted, and normally, when the health state of the lithium battery is more than 80%, the lithium battery is applied to an electric device, when 80% -50%, the lithium battery is applied to an energy storage device, when 50% -40%, the lithium battery is applied to portable electronic equipment such as toys, electric tools and the like, and when the lithium battery is less than 40%, the lithium battery is scrapped; secondly, after disassembly, the waste products which cannot be used in a echelon manner are discharged and disassembled, and then raw materials are refined in a wet or fire method mode, so that recycling is realized, and the whole process flow is shown in figure 1.
The recovery of retired lithium iron phosphate power batteries is mainly performed by pyrometallurgy abroad, and commercialized application is realized in enterprises such as Mitsubishi, recupyl in France, and Retriev Technologies in the United states. Compared with abroad, china encourages to obtain retired lithium iron phosphate black powder by adopting a physical method and then adopt an environment-friendly and safe wet recycling process. Publication No. CN 112310499A discloses a method for carrying out intensified leaching on retired lithium iron phosphate battery materials by adopting various acids such as sulfuric acid, hydrochloric acid, phosphoric acid, formic acid and the like, and although the leaching rates of lithium element, iron element and phosphorus element are all more than 90%, a large amount of strong acid waste liquid is difficult to avoid in the leaching process, so that certain pressure is caused on equipment and the disposal cost is increased.
Therefore, a weak acid or acid-free leaching system needs to be developed to solve the problem of efficient leaching and fine separation of all components of the retired lithium iron phosphate battery.
The invention comprises the following steps:
the invention solves the problems existing in the prior art, and provides a method for finely separating and recycling all components of retired lithium iron phosphate black powder.
The invention aims to provide a method for finely separating and recycling all components of retired lithium iron phosphate black powder, which comprises the following steps:
(1) And (3) vulcanization activation: mixing retired lithium iron phosphate black powder with an activating agent, and then performing vulcanization activation to obtain a mixed material;
(2) And (3) carrying out reverse flotation water dissolution and lithium extraction: pulping the mixed material obtained after the vulcanization and activation in the step (1) by deionized water, adding a collector and a regulator for reverse flotation water dissolution and lithium extraction to obtain negative graphite, ferric phosphate and lithium-rich leaching liquor, wherein the ferric phosphate returns to the production of a positive electrode material, the negative graphite is recycled, and the lithium-rich leaching liquor is directly evaporated and crystallized to obtain sulfur-rich ammonia mixed salt;
(3) And (3) removing sulfur ammonia mixed salt: mixing the sulfur-rich ammonia mixed salt obtained in the step (2) with a sulfur-ammonia separating agent in a closed reaction container, heating and stir-frying until ammonia is no longer generated, dissolving a product in the reaction container by deionized water, and removing sulfur ammonia mixed salt to obtain ammonia gas, calcium sulfate and a lithium-rich purified solution, wherein the ammonia gas and the calcium sulfate are recycled;
(4) Acidifying and precipitating lithium: and (3) heating the lithium-rich purified solution obtained in the step (3), then adding dilute sulfuric acid for heating, and performing acidification and precipitation until no precipitate is generated in the solution, thus obtaining lithium sulfate.
Preferably, the retired lithium iron phosphate black powder in the step (1) is obtained by the following steps: and disassembling, crushing, pyrolyzing and finely sorting the collected retired lithium iron phosphate battery to obtain retired lithium iron phosphate black powder.
Preferably, the activator in the step (1) is ammonium persulfate, and the retired lithium iron phosphate black powder and the activator are prepared according to Fe in the black powder and S in the activator 2 O 8 2- The molar ratio of (2) is 1:1-1:1.8.
Compared with the traditional liquid-solid reaction which adopts a strong sulfuric acid system to add oxidizing agents such as hydrogen peroxide, hypochlorous acid, oxygen or chlorine, the invention adopts the ammonium persulfate mechanical active oxidation method to avoid the corrosion of strong acid to reaction equipment, can realize the efficient leaching of lithium element only by acid-free leaching, and can reduce the tail liquid disposal cost caused by repeatedly adding chemical reagents to adjust the pH of the leaching solution.
Further preferably, the vulcanization activation in the step (1) is specifically carried out in a planetary ball mill, zirconia balls with the diameter of 10-25 mm are added in the activation process according to the mass ratio of 10:1-20:1, the rotating speed of the ball mill is 400-650 rpm, and the reaction time is 0.2-2.0 h.
In the vulcanization activation process in the step (1), lithium iron phosphate is oxidized by ammonium persulfate, and Fe 2+ Is oxidized to Fe 3+ With PO (PO) 4 3- Generating indissolvable FePO 4 The sediment, the reaction process is shown as a formula (1):
2LiFePO 4 +S 2 O 8 2- ＝2FePO 4 +2Li + +2SO 4 2- (1)
preferably, in the process of the reverse flotation water-soluble lithium extraction in the step (2), the mass ratio of liquid to solid after the material is slurried by deionized water is 1:1-1:5 kg/kg.
Preferably, the collecting agent in the step (2) is at least one of No. 5 fuel oil and No. 10 light diesel oil, the regulator is calcium oxide, the adding amount of the collecting agent is 0.5-2.5 g/kg of mixed materials, and the adding amount of the regulator is 1.0-3.0 g/kg of mixed materials.
Preferably, the sulfur ammonia separating agent in the mixed salt sulfur ammonia removal process in the step (3) is calcium hydroxide and/or calcium oxide.
In the step (3), sulfur ions in mixed salt are mainly converted into insoluble sulfate, ammonium ions are converted into volatile ammonia gas, the purpose of removing sulfur and ammonium in mixed salt to purify lithium solution is achieved, and the reaction mode is shown in the formulas (2) and (3):
Ca(OH) 2 + (NH 4 ) 2 SO 4 ＝ CaSO 4 (s) + 2NH 3 (g) + 2H 2 O (2)
CaO + (NH 4 ) 2 SO 4 ＝ CaSO 4 (s) + 2NH 3 (g) + H 2 O (3)
preferably, the addition amount of the sulfur ammonia separating agent in the step (3) is 20-55wt% of the sulfur ammonia-rich mixed salt, the heating temperature is 150-360 ℃, and the heating time is 20-40 min.
Preferably, the heating temperature in the acidification and precipitation process of the step (4) is 70-100 ℃, and the pH is 1.5-3.5.
Further preferably, the mass fraction of the dilute sulfuric acid in the step (4) is 0.5% -1.5%. Still more preferably, the mass fraction of dilute sulfuric acid is 1%.
Compared with the prior art, the invention has the following advantages:
1. compared with the traditional liquid-solid reaction which adopts a strong sulfuric acid system to add oxidizing agents such as hydrogen peroxide, hypochlorous acid, oxygen or chlorine, the invention adopts the ammonium persulfate mechanical activation oxidation mode to realize the efficient and mild deconstruction of lithium iron phosphate, and the lithium ion can be leached out efficiently only by dissolving deionized water after activation, so that the corrosion of strong acid to reaction equipment can be avoided, the tail liquid disposal cost caused by repeatedly adjusting the pH value of leaching liquid is reduced, the invention has the advantages of environment-friendly operation, high recovery rate of lithium element, contribution to industrial application popularization and remarkable economic benefit.
2. According to the invention, the lithium-rich leaching solution after lithium element leaching is directly evaporated and crystallized to obtain sulfur-rich ammonia mixed salt, then calcium hydroxide or calcium oxide is adopted as a sulfur-ammonia separating agent to be subjected to closed environment hot stir-frying, so that the traditional aqueous solution heating and stirring are replaced, the conversion of impurity sulfur into insoluble sulfate and the conversion of ammonium ions into volatile and enriched ammonia gas can be synchronously realized, the effect of lithium ion purification is realized, the multiple neutralization, precipitation and extraction and back extraction modes of the lithium-rich leaching solution in the traditional recovery process are avoided, the process flow is simple, the operation is convenient, the impurity ions can be synchronously converted into high-value products such as calcium sulfate, ammonia gas and the like for recycling, and the additional value utilization rate is remarkable.
In addition, compared with the method for separating potassium sulfate from ammonium sulfate disclosed in the publication No. CN 1036205A, the method for separating potassium sulfate from ammonium sulfate disclosed by the invention adopts a liquid-solid reaction method of adding calcium oxide or calcium hydroxide into leaching solution for size mixing, heating and stirring, and the solid-solid reaction method of heating and stir-frying in a closed environment is adopted after solid ammonia sulfate mixed salt and solid calcium hydroxide or calcium oxide are mixed, so that mass transfer is enhanced, a closed system has less heat dissipation, the amount of calcium oxide in the publication No. CN 1036205A is 0.8-1.5 times of the mole number of ammonium sulfate, the reaction time is 0.5-24h, the addition amount of ammonia sulfate separating agent is 20-55wt% of ammonia sulfate-rich mixed salt, and the reaction time is 20-40 min, so that the reaction time is greatly shortened, the use amount of the ammonia sulfate separating agent is reduced, and the cost is saved.
3. According to the invention, the vulcanization activation can realize the conditions that lithium iron phosphate is deconstructed into reverse flotation water-soluble lithium extraction to create lithium extraction under mild conditions, in addition, the coupling reverse flotation technology in the lithium extraction process synchronously realizes the directional migration of enriched graphite, the addition of a collector and a regulator can increase the floatability of negative electrode graphite to induce the directional removal of the negative electrode graphite, the impurity content of mixed salt obtained in the subsequent mixed salt crystallization process is reduced, the mixed salt ammonia sulfate removal efficiency is improved, and in addition, the mode of replacing the traditional carbonate lithium precipitation by dilute acid acidification precipitation can reduce the use amount of chemical reagents and can obtain the precursor of high-purity lithium sulfate for battery materials.
Description of the drawings:
FIG. 1 is a flow chart of the overall recovery process of a retired lithium iron phosphate power battery;
FIG. 2 is a process flow diagram of a method for finely separating and recovering all components of black powder of a retired lithium iron phosphate pool;
FIG. 3 is an XRD phase diagram of iron phosphate obtained in examples 1-6 of the present invention.
The specific embodiment is as follows:
the following examples are further illustrative of the invention and are not intended to be limiting thereof.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention. Unless otherwise indicated, the experimental materials and reagents herein are all commercially available products conventional in the art.
Example 1
As shown in fig. 2, the method for finely separating and recovering the full components of the retired lithium iron phosphate black powder comprises the following steps:
(1) And (3) vulcanization activation: disassembling, crushing, pyrolyzing and finely sorting the collected cylindrical retired lithium iron phosphate battery with the steel shell to obtain retired lithium iron phosphate black powder, and mixing the retired lithium iron phosphate black powder with an activator ammonium persulfate according to Fe and S in the black powder 2 O 8 2- After dosing in a molar ratio of 1:1mol/mol, sulfur was carried out in a planetary ball millActivating to obtain a mixed material, wherein zirconia balls with the diameter of 10mm are added in the activation process according to the mass ratio of 10:1, the rotating speed of a ball mill is 400rpm, and the reaction time is 0.2h;
(2) And (3) carrying out reverse flotation water dissolution and lithium extraction: mixing the mixed material obtained after the vulcanization and activation in the step (1) with deionized water, wherein the mass ratio of the mixed material to the liquid is 1:1 kg/kg, adding a collector No. 5 fuel oil and a regulator calcium oxide into a graphite flotation machine to carry out reverse flotation water-soluble lithium extraction, wherein the addition amount of the collector is 0.5 g per kg of the mixed material, and the addition amount of the regulator is 1.0 g per kg of the mixed material to obtain negative graphite, ferric phosphate and lithium-rich leaching liquor, wherein the ferric phosphate is returned to the production of a positive electrode material, the negative graphite is recycled, and the lithium-rich leaching liquor is directly evaporated and crystallized to obtain sulfur-rich ammonia mixed salt;
(3) And (3) removing sulfur ammonia mixed salt: mixing the sulfur-rich ammonia mixed salt obtained in the step (2) with calcium hydroxide serving as a sulfur-ammonia separating agent in a closed crucible reaction kettle, heating and stir-frying, wherein the adding amount of the calcium hydroxide is 20wt% of the mass of the sulfur-rich ammonia mixed salt, the heating temperature is 150 ℃, the heating time is 1.0h until ammonia gas is not generated any more, then dissolving the sulfur-ammonia mixed salt with deionized water to remove sulfur-ammonia mixed salt, so as to obtain ammonia gas, calcium sulfate and a lithium-rich purified solution, wherein the ammonia gas is returned to ammonium persulfate production, and the calcium sulfate is returned to a gypsum plant; the solid-solid reaction in a closed environment is thermally stir-fried to replace the traditional liquid-solid heating and stirring mode of aqueous solution, and the reaction time can be reduced from 6 hours to 20 minutes.
(4) Acidifying and precipitating lithium: and (3) heating the lithium-rich purified solution obtained in the mixed salt ammonia sulfate removal process in the step (3) to 70 ℃, and then adjusting the pH value of the solution to 1.5 by using dilute sulfuric acid with the mass fraction of 1% to acidify and precipitate lithium until no precipitate is generated in the solution, so as to obtain lithium sulfate.
In the recovery process, the comprehensive recovery rate of lithium is 95.5 percent, fePO 4 The overall recovery was 96.7% and the resulting iron phosphate phase is shown in figure 3.
Example 2
As shown in fig. 2, the method for finely separating and recovering the full components of the retired lithium iron phosphate black powder comprises the following steps:
(1) And (3) vulcanization activation: square withdrawing the collected aluminum shellDismantling, crushing, pyrolyzing and finely sorting the active lithium iron phosphate battery to obtain retired lithium iron phosphate black powder, and mixing the retired lithium iron phosphate black powder with an activator ammonium persulfate according to Fe and S in the black powder 2 O 8 2- After the mixture is proportioned according to the mol ratio of 1:1.8mol/mol, the mixture is vulcanized and activated in a planetary ball mill to obtain a mixed material, wherein zirconia balls with the diameter of 25mm are added in the activation process according to the mass ratio of 20:1, the rotating speed of the ball mill is 650rpm, and the reaction time is 2.0h;
(2) And (3) carrying out reverse flotation water dissolution and lithium extraction: mixing the mixed material obtained after the vulcanization and activation in the step (1) with deionized water, wherein the mass ratio of the mixed material to the liquid to the solid is 1:5 kg/kg, adding light diesel oil No. 10 of a collector and calcium oxide of a regulator into a graphite flotation machine to carry out reverse flotation and water-soluble lithium extraction, wherein the addition amount of the collector is 2.5 g per kg of the mixed material, and the addition amount of the regulator is 3.0 g per kg of the mixed material to obtain negative graphite, ferric phosphate and lithium-rich leaching liquor, wherein the ferric phosphate is returned to the production of a positive electrode material, the negative graphite is recycled, and the lithium-rich leaching liquor is directly evaporated and crystallized to obtain sulfur-rich ammonia mixed salt;
(3) And (3) removing sulfur ammonia mixed salt: mixing the sulfur-rich ammonia mixed salt obtained in the step (2) with calcium oxide serving as a sulfur-ammonia separating agent in a closed crucible reaction kettle, heating and stir-frying, wherein the adding amount of the calcium oxide is 55wt% of the mass of the sulfur-rich ammonia mixed salt, the heating temperature is 360 ℃, the heating time is 3.5h, until no ammonia gas is generated any more, then dissolving the sulfur-ammonia mixed salt with deionized water, removing sulfur ammonia of the mixed salt, and obtaining ammonia gas, calcium sulfate and a lithium-rich purified solution, wherein the ammonia gas is returned to ammonium persulfate production, and the calcium sulfate is returned to a gypsum factory; the solid-solid reaction in a closed environment is thermally stir-fried to replace the traditional liquid-solid heating and stirring mode of aqueous solution, and the reaction time can be reduced from 24 hours to 40 minutes.
(4) Acidifying lithium: and (3) heating the lithium-rich purified solution obtained in the mixed salt ammonia sulfate removal process in the step (3) to 100 ℃, and then adjusting the pH value of the solution to 2.5 by using dilute sulfuric acid with the mass fraction of 1% to acidify and precipitate lithium until no precipitate is generated in the solution, so as to obtain lithium sulfate.
In the recovery process, the comprehensive recovery rate of lithium is 96.2 percent, fePO 4 The comprehensive recovery rate was 94.2%, and the obtained iron phosphate was as shown in FIG. 3Shown.
Example 3
As shown in fig. 2, the method for finely separating and recovering the full components of the retired lithium iron phosphate black powder comprises the following steps:
(1) And (3) vulcanization activation: disassembling, crushing, pyrolyzing and finely sorting the collected soft-package aluminum-plastic film-shaped retired lithium iron phosphate battery to obtain retired lithium iron phosphate black powder, and mixing the retired lithium iron phosphate black powder with an activator ammonium persulfate according to Fe and S in the black powder 2 O 8 2- After the mixture is proportioned according to the mol ratio of 1:1.2mol/mol, the mixture is vulcanized and activated in a planetary ball mill to obtain a mixed material, wherein zirconia balls with the diameter of 12mm are added in the activation process according to the mass ratio of 12:1, the rotating speed of the ball mill is 450rpm, and the reaction time is 1.0h;
(2) And (3) carrying out reverse flotation water dissolution and lithium extraction: mixing the materials obtained after the vulcanization and activation in the step (1) with deionized water, wherein the mass ratio of the mixed liquid to the solid is 1:2 kg/kg, adding a collector No. 5 fuel oil and a regulator calcium oxide into a graphite flotation machine to carry out reverse flotation and water-soluble lithium extraction, wherein the addition amount of the collector is 0.8 g per kg of mixed materials, and the addition amount of the regulator is 1.2 g per kg of mixed materials to obtain negative graphite, ferric phosphate and lithium-rich leaching liquor, wherein the ferric phosphate returns to the production of a positive electrode material, the negative graphite is recycled, and the lithium-rich leaching liquor is directly evaporated and crystallized to obtain sulfur-rich ammonia mixed salt;
(3) And (3) removing sulfur ammonia mixed salt: mixing the sulfur-rich ammonia mixed salt obtained in the step (2) with calcium hydroxide serving as a sulfur-ammonia separating agent in a closed crucible reaction kettle, heating and stir-frying, wherein the adding amount of the calcium hydroxide is 25wt% of the mass of the sulfur-rich ammonia mixed salt, the heating temperature is 200 ℃, the heating time is 1.5h, until ammonia gas is no longer generated, then dissolving the sulfur-ammonia mixed salt with deionized water, and removing sulfur ammonia of the mixed salt to obtain ammonia gas, calcium sulfate and a lithium-rich purified solution, wherein the ammonia gas is returned to ammonium persulfate production, and the calcium sulfate is returned to a gypsum plant; the solid-solid reaction in a closed environment is thermally stir-fried to replace the traditional liquid-solid heating and stirring mode of aqueous solution, and the reaction time can be reduced from 12 hours to 30 minutes.
(4) Acidifying and precipitating lithium: and (3) heating the lithium-rich purified solution obtained in the mixed salt ammonia sulfate removal process in the step (3) to 75 ℃, and then adjusting the pH value of the solution to 1.0 by using 1% dilute sulfuric acid to acidify and precipitate lithium until no precipitate is generated in the solution, so as to obtain lithium sulfate.
In the recovery process, the comprehensive recovery rate of lithium is 95.0 percent, fePO 4 The overall recovery was 94.0%, and the resulting iron phosphate phase was as shown in FIG. 3.
Example 4
As shown in fig. 2, the method for finely separating and recovering the full components of the retired lithium iron phosphate black powder comprises the following steps:
(1) And (3) vulcanization activation: disassembling, crushing, pyrolyzing and finely sorting the collected cylindrical retired lithium iron phosphate battery with the steel shell to obtain retired lithium iron phosphate black powder, and mixing the retired lithium iron phosphate black powder with an activator ammonium persulfate according to Fe and S in the black powder 2 O 8 2- After the mixture is proportioned according to the mol ratio of 1:1.6mol/mol, the mixture is vulcanized and activated in a planetary ball mill to obtain a mixed material, wherein zirconia balls with the diameter of 22mm are added in the activation process according to the mass ratio of 18:1, the rotating speed of the ball mill is 600rpm, and the reaction time is 1.8h;
(2) And (3) carrying out reverse flotation water dissolution and lithium extraction: mixing the materials obtained after the vulcanization and activation in the step (1) with deionized water, wherein the mass ratio of the mixed liquid to the solid is 1:4 kg/kg, adding a collecting agent No. 10 light diesel oil and a regulating agent calcium oxide into a graphite flotation machine to carry out reverse flotation and water-soluble lithium extraction, wherein the adding amount of the collecting agent is 2.0 g per kg of mixed materials, the adding amount of the regulating agent is 2.5 g per kg of mixed materials, and obtaining negative graphite, ferric phosphate and lithium-rich leaching liquor, wherein the ferric phosphate returns to the production of a positive electrode material, the negative graphite is recycled, and the lithium-rich leaching liquor is directly evaporated and crystallized to obtain sulfur-rich ammonia mixed salt;
(3) And (3) removing sulfur ammonia mixed salt: mixing the sulfur-rich ammonia mixed salt obtained in the step (2) with calcium oxide serving as a sulfur-ammonia separating agent in a closed crucible reaction kettle, heating and stir-frying, wherein the adding amount of the calcium oxide is 50wt% of the mass of the sulfur-rich ammonia mixed salt, the heating temperature is 300 ℃, the heating time is 3.0h, until no ammonia gas is generated any more, then dissolving the sulfur-ammonia mixed salt with deionized water, removing sulfur ammonia of the mixed salt, and obtaining ammonia gas, calcium sulfate and a lithium-rich purified liquid, wherein the ammonia gas is returned to ammonium persulfate production, and the calcium sulfate is returned to a gypsum factory; the solid-solid reaction in a closed environment is thermally stir-fried to replace the traditional liquid-solid heating and stirring mode of aqueous solution, and the reaction time can be reduced from 18 hours to 35 minutes.
(4) Acidifying and precipitating lithium: and (3) heating the lithium-rich purified solution obtained in the mixed salt ammonia sulfate removal process in the step (3) to 90 ℃, and then adjusting the pH value of the solution to 1.2 by using 1% dilute sulfuric acid to acidify and precipitate lithium until no precipitate is generated in the solution, so as to obtain lithium sulfate.
In the recovery process, the comprehensive recovery rate of lithium is 95.2%, fePO 4 The overall recovery was 94.4% and the resulting iron phosphate phase is shown in figure 3.
Example 5
As shown in fig. 2, the method for finely separating and recovering the full components of the retired lithium iron phosphate black powder comprises the following steps:
(1) And (3) vulcanization activation: disassembling, crushing, pyrolyzing and finely sorting the collected soft-package aluminum-plastic film-shaped retired lithium iron phosphate battery to obtain retired lithium iron phosphate black powder, and mixing the retired lithium iron phosphate black powder with an activator ammonium persulfate according to Fe and S in the black powder 2 O 8 2- After the mixture is proportioned according to the mol ratio of 1:1.4mol/mol, the mixture is vulcanized and activated in a planetary ball mill to obtain a mixed material, wherein zirconia balls with the diameter of 15mm are added in the activation process according to the mass ratio of 15:1, the rotating speed of the ball mill is 500rpm, and the reaction time is 0.6h;
(2) And (3) carrying out reverse flotation water dissolution and lithium extraction: mixing the materials obtained after the vulcanization and activation in the step (1) with deionized water, wherein the mass ratio of the mixed liquid to the solid is 1:3 kg/kg, adding a collector No. 5 fuel oil and a regulator calcium oxide into a graphite flotation machine to carry out reverse flotation and water-soluble lithium extraction, wherein the addition amount of the collector is 1.5 g per kg of mixed materials, and the addition amount of the regulator is 2.0 g per kg of mixed materials to obtain negative graphite, ferric phosphate and lithium-rich leaching liquor, wherein the ferric phosphate is returned to the production of a positive electrode material, the negative graphite is recycled, and the lithium-rich leaching liquor is directly evaporated and crystallized to obtain sulfur-rich ammonia mixed salt;
(3) And (3) removing sulfur ammonia mixed salt: mixing the sulfur-rich ammonia mixed salt obtained in the step (2) with calcium hydroxide serving as a sulfur-ammonia separating agent in a closed crucible reaction kettle, heating and stir-frying, wherein the adding amount of the calcium hydroxide is 30wt% of the mass of the sulfur-rich ammonia mixed salt, the heating temperature is 250 ℃, the heating time is 2.0h until ammonia gas is not generated any more, then dissolving the sulfur-ammonia mixed salt with deionized water to remove sulfur-ammonia mixed salt, so as to obtain ammonia gas, calcium sulfate and a lithium-rich purified liquid, wherein the ammonia gas is returned to ammonium persulfate production, and the calcium sulfate is returned to a gypsum plant; the solid-solid reaction in a closed environment is thermally stir-fried to replace the traditional liquid-solid heating and stirring mode of aqueous solution, and the reaction time can be reduced from 9 hours to 25 minutes.
(4) Acidifying and precipitating lithium: and (3) heating the lithium-rich purified solution obtained in the mixed salt ammonia sulfate removal process in the step (3) to 80 ℃, and then adjusting the pH value of the solution to 1.6 by using 1% dilute sulfuric acid to acidify and precipitate lithium until no precipitate is generated in the solution, so as to obtain lithium sulfate.
In the recovery process, the comprehensive recovery rate of lithium is 94.8 percent, fePO 4 The overall recovery was 94.7% and the resulting iron phosphate phase is shown in figure 3.
Example 6
As shown in fig. 2, the method for finely separating and recovering the full components of the retired lithium iron phosphate black powder comprises the following steps:
(1) And (3) vulcanization activation: disassembling, crushing, pyrolyzing and finely sorting the collected square aluminum shell retired lithium iron phosphate battery to obtain retired lithium iron phosphate black powder, and mixing the retired lithium iron phosphate black powder with an activator ammonium persulfate according to Fe and S in the black powder 2 O 8 2- After the mixture is proportioned according to the mol ratio of 1:1.5mol/mol, the mixture is vulcanized and activated in a planetary ball mill to obtain a mixed material, wherein zirconia balls with the diameter of 20mm are added in the activation process according to the mass ratio of 16:1, the rotating speed of the ball mill is 550rpm, and the reaction time is 1.2h;
(2) And (3) carrying out reverse flotation water dissolution and lithium extraction: mixing the materials obtained after the vulcanization and activation in the step (1) with deionized water, wherein the mass ratio of the mixed liquid to the solid is 1:2.5 kg/kg, adding light diesel oil No. 10 of a collector and calcium oxide serving as a regulator into a graphite flotation machine to carry out reverse flotation water-soluble lithium extraction, wherein the addition amount of the collector is 1.2 g/kg of mixed materials, and the addition amount of the regulator is 1.5 g/kg of mixed materials to obtain negative graphite, ferric phosphate and lithium-rich leaching liquor, wherein the ferric phosphate is returned to the production of a positive electrode material, the negative graphite is recycled, and the lithium-rich leaching liquor is subjected to direct evaporation crystallization to obtain sulfur-rich ammonia mixed salt;
(3) And (3) removing sulfur ammonia mixed salt: mixing the sulfur-rich ammonia mixed salt obtained in the step (2) with calcium oxide serving as a sulfur-ammonia separating agent in a closed crucible reaction kettle, heating and stir-frying, wherein the adding amount of the calcium oxide is 40wt% of the mass of the sulfur-rich ammonia mixed salt, the heating temperature is 280 ℃, the heating time is 2.5h, until no ammonia gas is generated any more, then dissolving the sulfur-ammonia mixed salt with deionized water, removing sulfur ammonia of the mixed salt, and obtaining ammonia gas, calcium sulfate and a lithium-rich purified solution, wherein the ammonia gas is returned to ammonium persulfate production, and the calcium sulfate is returned to a gypsum factory; the solid-solid reaction in a closed environment is thermally stir-fried to replace the traditional liquid-solid heating and stirring mode of aqueous solution, and the reaction time can be reduced from 20 hours to 38 minutes.
(4) Acidifying and precipitating lithium: and (3) heating the lithium-rich purified solution obtained in the mixed salt ammonia sulfate removal process in the step (3) to 85 ℃, and then adjusting the pH value of the solution to 2.0 by using 1% dilute sulfuric acid to acidify and precipitate lithium until no precipitate is generated in the solution, so as to obtain lithium sulfate.
In the recovery process, the comprehensive recovery rate of lithium is 95.8 percent, fePO 4 The overall recovery was 94.6% and the resulting iron phosphate phase is shown in figure 3.
The above embodiments are only described to assist in understanding the technical solution of the present invention and its core idea, and it should be noted that it will be obvious to those skilled in the art that several improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (9)
1. A method for finely separating and recovering all components of retired lithium iron phosphate black powder is characterized by comprising the following steps:
(1) And (3) vulcanization activation: mixing retired lithium iron phosphate black powder with an activator, and then performing vulcanization activation to obtain a mixed material, wherein the activator is ammonium persulfate, and the vulcanization activation is specifically performed in a planetary ball mill;
(2) And (3) carrying out reverse flotation water dissolution and lithium extraction: pulping the mixed material obtained after the vulcanization and activation in the step (1) by deionized water, adding a collector and a regulator for reverse flotation water dissolution and lithium extraction to obtain negative graphite, ferric phosphate and lithium-rich leaching liquor, wherein the ferric phosphate is returned to the production of a positive electrode material, the negative graphite is recycled, the lithium-rich leaching liquor is directly evaporated and crystallized to obtain sulfur-rich ammonia mixed salt, the collector is at least one of No. 5 fuel oil and No. 10 light diesel oil, and the regulator is calcium oxide;
(3) And (3) removing sulfur ammonia mixed salt: mixing the sulfur-rich ammonia mixed salt obtained in the step (2) with a sulfur-ammonia separating agent in a closed reaction container, heating and stir-frying until ammonia is not generated any more, dissolving a product in the reaction container by deionized water, and removing sulfur ammonia mixed salt to obtain ammonia, calcium sulfate and a lithium-rich purified solution, wherein the ammonia and the calcium sulfate are recycled, and the sulfur-ammonia separating agent is calcium hydroxide and/or calcium oxide;
(4) Acidifying and precipitating lithium: and (3) adding the lithium-rich purifying liquid obtained in the step (3) into dilute sulfuric acid, heating, and acidifying and precipitating lithium until no precipitate is generated in the solution, thus obtaining lithium sulfate.
2. The method of claim 1, wherein the retired lithium iron phosphate black powder of step (1) is obtained by: and disassembling, crushing, pyrolyzing and finely sorting the collected retired lithium iron phosphate battery to obtain retired lithium iron phosphate black powder.
3. The method of claim 1, wherein the retired lithium iron phosphate black powder and activator of step (1) are based on Fe in the black powder and S in the activator 2 O 8 2- The molar ratio of (2) is 1:1-1:1.8.
4. A method according to claim 1 or 3, wherein the activation process in step (1) comprises adding zirconia beads with a diameter of 10-25 mm according to a mass ratio of 10:1-20:1, the rotation speed of the ball mill is 400-650 rpm, and the reaction time is 0.2-2.0 h.
5. The method of claim 1, wherein in the process of the reverse flotation water-soluble lithium extraction in the step (2), the mass ratio of liquid to solid after the material is slurried with deionized water is 1:1-1:5.
6. The method of claim 1, wherein the collector in step (2) is added in an amount of 0.5-2.5 g/kg of the mixture, and the regulator is added in an amount of 1.0-3.0 g/kg of the mixture.
7. The method according to claim 1, wherein the sulfur ammonia separating agent in the step (3) is added in an amount of 20-55 wt% of the sulfur ammonia-rich mixed salt, the heating temperature is 150-360 ℃ and the heating time is 20-40 min.
8. The method according to claim 1, wherein the heating temperature in the acidification and precipitation process of the step (4) is 70-100 ℃ and the pH is 1.5-3.5.
9. The method according to claim 1 or 8, wherein the mass fraction of the dilute sulfuric acid in the step (4) is 0.5% -1.5%.
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