CN119220819B - A recycling method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries - Google Patents
A recycling method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries Download PDFInfo
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- CN119220819B CN119220819B CN202411734875.4A CN202411734875A CN119220819B CN 119220819 B CN119220819 B CN 119220819B CN 202411734875 A CN202411734875 A CN 202411734875A CN 119220819 B CN119220819 B CN 119220819B
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 40
- 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 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000010949 copper Substances 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title abstract 2
- 238000002386 leaching Methods 0.000 claims abstract description 63
- 239000000243 solution Substances 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000002893 slag Substances 0.000 claims abstract description 23
- 238000011084 recovery Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000012216 screening Methods 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 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
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 230000005484 gravity Effects 0.000 claims abstract description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 16
- 229960004887 ferric hydroxide Drugs 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 12
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 239000005955 Ferric phosphate Substances 0.000 claims description 8
- 229940032958 ferric phosphate Drugs 0.000 claims description 8
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 claims description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000010926 waste battery Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 4
- 150000002505 iron Chemical class 0.000 abstract 2
- 235000014413 iron hydroxide Nutrition 0.000 abstract 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract 2
- 239000000843 powder Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 239000002002 slurry Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910000398 iron phosphate Inorganic materials 0.000 description 8
- 239000003513 alkali Substances 0.000 description 5
- 238000009854 hydrometallurgy Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明公开一种从废旧磷酸铁锂电池中提取锂和铜、铝的回收方法。首先对磷酸铁锂废旧电池进行预处理得到片状正、负极片混合物，再以三价铁盐溶液为浸出剂浸出极片混合物，过滤得含锂浸出液和包括铜、铝集流体的磷铁渣。含锂浸出液经氧化、调pH值后过滤分离，得含锂净化液和氢氧化铁沉淀。含锂浸出液继续调高pH值除杂，再加入碳酸钠饱和溶液，沉淀结晶得碳酸锂；氢氧化铁沉淀用稀酸溶解配成三价铁盐溶液，循环用于浸出剂。包括铜、铝集流体的磷铁渣，经水动力筛分设备分离得到铜、铝集流体混合物和磷铁渣，前者干燥研磨后用比重分选机分离，得铜粉、铝粉。本发明缩短了工艺流程，项目投资和生产成本相对较低，适合规模化回收处理废旧磷酸铁锂电池。
The invention discloses a recovery method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries. First, waste lithium iron phosphate batteries are pretreated to obtain a mixture of positive and negative electrode sheets in a flaky state, and then the electrode sheet mixture is leached with a trivalent iron salt solution as a leaching agent, and a lithium-containing leachate and ferrophosphorus slag including copper and aluminum current collectors are filtered. The lithium-containing leachate is oxidized and pH adjusted, and then filtered and separated to obtain a lithium-containing purified liquid and iron hydroxide precipitate. The lithium-containing leachate is further adjusted to a high pH value to remove impurities, and then a saturated sodium carbonate solution is added to precipitate and crystallize to obtain lithium carbonate; the iron hydroxide precipitate is dissolved with dilute acid to prepare a trivalent iron salt solution, which is circulated for the leaching agent. The ferrophosphorus slag including copper and aluminum current collectors is separated by a hydrodynamic screening device to obtain a copper and aluminum current collector mixture and ferrophosphorus slag, and the former is dried and ground and separated by a specific gravity separator to obtain copper powder and aluminum powder. The invention shortens the process flow, and the project investment and production costs are relatively low, and is suitable for large-scale recycling and treatment of waste lithium iron phosphate batteries.
Description
Technical Field
The invention relates to the technical field of lithium ion battery recovery, in particular to a recovery method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries.
Background
As market demand increases, the amount of new energy vehicles kept is also continuously increasing. Sales of new energy automobiles drive the installed quantity of power batteries to represent a strong growth potential. A
At the same time, how to recycle the lithium iron phosphate battery after retirement is also an important subject of research. The main valuable metals in the lithium iron phosphate are lithium, copper and aluminum, and the lithium iron phosphate is effectively and safely recycled, so that not only can environmental pollution be avoided, but also the problem of raw material sources in the manufacturing of lithium power batteries can be solved.
At present, the method for recovering waste lithium iron phosphate batteries in the industry generally adopts a crushing and sorting method to obtain black powder, and then leaches the black powder to recover lithium by a hydrometallurgy process.
The traditional crushing and sorting method adopts a multi-stage crushing and screening process for waste lithium batteries, so that the aluminum foil of the positive electrode current collector is excessively crushed, the aluminum is out of standard due to the fact that the fine aluminum powder is doped with black powder, and the recovery rate of the electrode materials is difficult to reach more than 98.5% in an environment where the electrode materials overflow due to repeated crushing and screening.
The wet metallurgy of lithium iron phosphate black powder generally adopts an acid leaching process, such as CN 113603119B, CN 111285341A of China, which consumes a large amount of inorganic acid to dissolve the black powder, wherein the industrially applied inorganic acid is sulfuric acid, hydrochloric acid, phosphoric acid and the like, and the subsequent pH value is adjusted by adopting sodium hydroxide, and the inorganic acid and the alkali belong to dangerous chemicals. On the one hand, inorganic strong acid and alkali have strong corrosiveness to equipment, the requirement on equipment materials is high, the cost in various aspects such as production technology, equipment and wastewater recovery treatment is increased, on the other hand, inorganic strong acid dissolved metal is not selective, and due to the multiple crushing reasons, impurities such as aluminum and the like can be dissolved into leaching liquid when black powder containing excessive metal impurities is leached, and lithium element can be mixed into slag phase by insoluble aluminum compound when aluminum is removed in the hydrometallurgy process, so that the recovery rate of lithium is reduced. Therefore, for the black powder containing excessive aluminum impurities, an alkali-dissolution aluminum-removal process is generally required to be added before leaching, such as the alkali-dissolution aluminum-removal process of China invention CN 112441571A, which can achieve a better aluminum-removal effect, but the added alkali-dissolution aluminum-removal process can increase the production cost.
In a word, in the traditional recovery process of the waste lithium iron phosphate battery, the black powder electrode material contains excessive aluminum impurities, and the adoption of strong acid in hydrometallurgy increases the process cost, increases the wastewater treatment cost, and simultaneously leads to the rise of comprehensive energy consumption in the production of lithium carbonate products.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a recovery method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries, which has the advantages of environmental protection, high efficiency, short process and the like.
The method adopts the technical scheme that the method comprises the steps of carrying out tooth cutting and crushing on the waste lithium iron phosphate battery once to avoid excessive fine aluminum powder generated by crushing for multiple times, carrying out reduction and environmental protection treatment to obtain a flaky positive and negative plate mixture, and then eliminating the stripping and sorting procedures in the traditional crushing and sorting method, wherein an inorganic ferric salt solution is used for directly leaching from the positive and negative plate mixture, the ferric salt leaching process has good selectivity, aluminum and copper of a positive current collector are insoluble in the ferric salt, the leaching agent has fewer impurities, the subsequent impurity removal cost is simplified, a large amount of strong acid and strong alkali are not consumed, and the leaching agent can be recycled for leaching after being simply regenerated, and the method specifically comprises the following steps:
S1, firstly, pretreating a waste lithium iron phosphate battery to obtain a flaky positive and negative plate mixture;
s2, leaching the mixture of the positive electrode plate and the negative electrode plate by taking a ferric salt solution as a leaching agent, and filtering and separating to obtain a leaching solution containing lithium and ferrous ions and solid slag comprising positive and negative electrode current collectors and ferric phosphate;
s3, introducing oxygen-enriched air into the leaching solution containing lithium and ferrous ions for oxidation, adding a lithium hydroxide solution, adjusting the pH value to be 4.0-4.5, generating ferric hydroxide precipitates, and filtering and separating to obtain a purified lithium-containing solution and a ferric hydroxide solid phase;
S4, continuously adding the purified lithium-containing solution into the lithium hydroxide solution to adjust the pH value to 9-11, further removing impurities, and then adding the saturated sodium carbonate solution under the heating condition to precipitate and crystallize to obtain industrial-grade lithium carbonate;
S5, adding dilute acid into the ferric hydroxide solid phase obtained in the step S3 to prepare a ferric salt solution, and returning to the step S2 for a leaching process;
S6, washing the solid slag comprising the anode current collector, the cathode current collector and the ferric phosphate obtained in the S2 by adopting part of crystallization mother liquor of the S4, washing by using hot water, and separating by adopting hydrodynamic screening equipment to obtain a mixture of the copper current collector and the aluminum current collector and a slag phase of the ferric phosphate;
S7, drying and grinding the mixture of the copper and aluminum current collectors obtained in the step S6, and separating by using a specific gravity separator to obtain copper powder and aluminum powder.
Further, in S1, the pretreatment is a reduction and environmental protection treatment, which means that the waste lithium iron phosphate battery is subjected to toothed shearing and crushing once under the nitrogen atmosphere, the electrolyte and the diaphragm in the waste battery are completely carbonized and volatilized, then the shell and the pile head are removed through air separation, and the tail gas is discharged after secondary combustion and environmental protection treatment.
Further, the pole pieces are sheared and crushed at one time, the pole pieces are in regular flaky shapes, sheared at one time, and crushed or finely ground at multiple stages relatively, so that the content of fine metal powder, particularly aluminum powder, in materials can be greatly reduced, the sizes of flaky positive and negative pole pieces are controlled to be 10-45 mm, and the pyrolysis temperature is 300-600 ℃, preferably 350-550 ℃.
In the step S2, the ferric salt is at least one of ferric sulfate, ferric chloride and ferric nitrate, the mole number of the ferric iron in the ferric salt solution is 25-50% of the mole number of the lithium iron phosphate in the mixture of the positive electrode plate and the negative electrode plate, and the liquid-solid mass ratio of the ferric salt solution to the mixture of the positive electrode plate and the negative electrode plate is 3-10:1.
Further, in S2, during the leaching reaction, the pH value of the reaction material is controlled within the range of 2.0-2.5 by adding small amount of ferric salt powder gradually.
In the S2, the leaching reaction is specifically that the leaching temperature is controlled at 20-40 ℃ (normal temperature range), the mixture of ferric salt solution and positive and negative plates is stirred and reacted for 10-30 minutes, then oxygen-enriched air is introduced for oxidation and stirring for 20-30 minutes, then the oxygen-enriched air is stopped, and the stirring reaction is continued for 20-30 minutes and then the leaching reaction is finished.
The reaction equation of the leaching process (for example, ferric sulfate):
2LiFePO4 + Fe2(SO4)3 = 2FeSO4 + Li2SO4 +2FePO4
The lithium iron phosphate structure belongs to olivine type, wherein the valence of iron is bivalent, and the theoretical using mole number of ferric salt is half of that of the lithium iron phosphate. In S2, the mole number of the ferric salt is 25-50% of that of the lithium iron phosphate, preferably the mole number of the ferric salt is 25% of that of the lithium iron phosphate, and after ferric ions are consumed in oxidizing the lithium iron phosphate, oxygen-enriched air is introduced to reoxidize generated ferrous ions into ferric ions which can continue leaching reaction on the lithium iron phosphate.
Further, in S3 and S4, the concentration of the lithium hydroxide solution is 1-10 mol/L, and the temperature of the solution is 20-60 ℃.
Further, in S4, the heating temperature of the saturated sodium carbonate solution is 40-90 ℃.
In S4, the mother solution after precipitating and crystallizing lithium carbonate is evaporated and concentrated to prepare lithium hydroxide solution.
Further, in S5, the concentration of the dilute acid is 0.1-2 mol/L, the dilute acid is one of sulfuric acid, hydrochloric acid or nitric acid, and the prepared ferric salt solution returns to the leaching process and is circularly used for leaching the mixture of the positive and negative electrode plates of the waste lithium iron phosphate.
Further, the oxygen-enriched air is a byproduct of the nitrogen making machine of the crushing and sorting line during nitrogen making, and the volume fraction of oxygen in the oxygen-enriched air is 26% -32%.
In S6, the hydrodynamic screening device is a hydrodynamic screening container with a built-in screen, the aperture of the screen is 3-8 mm, the distance between the holes of the screen is 5-10 mm, the mixture of copper and aluminum current collectors and iron phosphate slag is prepared into slurry by water, the copper and aluminum current collectors are separated from the iron phosphate slag when the slurry passes through the screen through the hydrodynamic screening device after being pumped into the hydrodynamic screening device, the iron phosphate-containing slurry separated through the hydrodynamic screening device is filtered and dried to obtain iron phosphate slag, the filtrate can be recycled, and the slag separated in S2 is matched into slurry.
Further, in S7, the specific gravity separator separates copper powder and aluminum powder by the difference of specific gravity of copper and aluminum metal powder, and the purity of the copper powder and the aluminum powder is more than or equal to 99%.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the starting end of the recovery process of the waste lithium iron phosphate battery is crushed and separated, only the mixture of the positive electrode plate and the negative electrode plate is obtained, the subsequent common stripping and separation processes of the crushing and separation line are eliminated, the positive electrode plate and the negative electrode plate directly enter the wet process, so that on one hand, the investment and the production cost of the production line are greatly reduced, and on the other hand, the leaching process of the positive electrode plate and the negative electrode plate is carried out in an aqueous medium, and the possible excessive crushing of aluminum in the dry stripping of the electrode plate in the conventional method is avoided, the exceeding of aluminum impurities and the overflow loss of dust in the separation process are avoided.
(2) The leaching is carried out by adopting a non-acid ferric salt solution, and is completely different from the common strong acid leaching process in the industry, and firstly, the leaching process has no strong acid or strong alkali, and the process and the storage and transportation are safe and environment-friendly. Secondly, the leaching process has better selectivity, and metal impurities such as aluminum, copper and the like are basically insoluble in the solution, so that the subsequent impurity removal cost is reduced. And thirdly, the leaching process is under normal temperature and normal pressure, high temperature is not needed, and the production cost is low. The purified lithium-containing solution has high purity, and the purity of the lithium carbonate obtained by precipitation of sodium carbonate can reach industrial grade.
(3) The invention adopts oxygen-enriched air with lower cost to oxidize ferrous ions. Oxygen enriched air is a byproduct of the nitrogen generator and is conventionally directly discharged. The invention utilizes the byproduct of the nitrogen making machine in the crushing and sorting line equipment to oxidize ferrous iron, thereby reducing the production and operation costs.
(4) In conventional hydrometallurgy, the pH value is often adjusted by sodium hydroxide strong alkali, and because strong acid is used as a leaching agent, the required sodium hydroxide dosage is large, other ions are introduced into the system, and the subsequent separation cost is increased.
(5) The invention takes the recovered high-purity copper and aluminum powder as the accurate target, does not recover the iron phosphate slag, is based on the fact that the market price of the copper powder and the aluminum powder is far higher than that of the copper powder and the aluminum powder, the equipment investment and the production cost of copper and aluminum recovery equipment are relatively low, the equipment investment and the production cost of the iron phosphate recovery to meet the quality requirement of battery-level iron phosphate are very high, and the market value of the current iron phosphate is not matched with the equipment investment and the running cost. The invention treats the waste as common solid waste and can be considered as a raw material for a basic building material.
Drawings
FIG. 1 is a block diagram of the process flow of the present invention.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples, but the invention is not limited thereto.
A process flow diagram of the present invention is shown in fig. 1, and the following examples are provided for illustrative purposes.
Example 1
And conveying the waste lithium iron phosphate square aluminum shell batteries into a shearing crusher for crushing through a material conveying belt, enabling crushed materials to enter a pyrolysis furnace for pyrolysis for 1 hour, controlling the pyrolysis temperature to be 450 ℃, and providing nitrogen atmosphere by a nitrogen making machine in the crushing and pyrolysis processes. The discharged materials are firstly passed through a vibrating linear screen, a small amount of black powder is separated by screening, and then the mixture of the anode and the cathode plates is obtained after the heavy shell and the pile head are separated by air separation. The mixture of the positive electrode plate and the negative electrode plate and a small amount of black powder screened by a straight line are prepared into thick slurry, the thick slurry is conveyed into a leaching tank, ferric sulfate solution is added for stirring, the temperature of the materials is controlled to be about 25 ℃ in the normal temperature range, the materials react for 30 minutes, oxygen-enriched air is introduced for oxidation for 30 minutes, and then the stirring leaching reaction is carried out for 30 minutes. And filtering and washing to obtain leaching liquid and leaching slag. Weighing, detecting the lithium content in the leaching solution and leaching slag, and analyzing that the leaching rate of lithium is 97.6%, and the leaching rates of aluminum and copper are respectively 0.4% and 0.5%.
And (3) introducing oxygen-enriched air serving as a byproduct of the nitrogen making machine into the leaching solution for 1 hour, stopping introducing the oxygen-enriched air, slowly adding a lithium hydroxide solution with the concentration of 2mol/L, adjusting the pH value of the solution to 4.5, producing ferric hydroxide precipitate, and filtering and separating to obtain the purified lithium-containing leaching solution and the purified ferric hydroxide precipitate. Adding 1mol/L dilute sulfuric acid into ferric hydroxide precipitate to prepare ferric sulfate solution, wherein the pH value of the ferric sulfate solution is 1.0-1.5, and returning the ferric sulfate solution to the leaching process for leaching the mixture of the positive and negative electrode plates of the lithium iron phosphate.
And (3) continuously adding the purified lithium-containing solution into the solution until the pH value of the solution is 11, filtering the solution to remove impurities, heating the filtrate to about 85 ℃, adding saturated sodium carbonate solution, reacting for 1 hour, cooling to generate crystals, filtering, washing with hot water to obtain industrial-grade lithium carbonate, and analyzing the purity of the industrial-grade lithium carbonate to be 99.35%. Evaporating and concentrating the mother solution after crystallization, and returning the concentrated mother solution to the purified lithium-containing solution for adjusting the pH value of the solution.
The leached slag of the leached positive and negative lithium iron phosphate plates is a mixture of copper and aluminum current collectors and ferric phosphate solid slag, after the mixture is prepared into slurry, the copper and aluminum current collectors are separated by a hydrodynamic screening device, and after the slurry is dried and ground, copper powder and aluminum powder are separated by a specific gravity separator, wherein the recovery rate of the copper and aluminum powder is 98.5%, and the purity of the copper and aluminum powder is over 99%.
Example 2
And conveying the waste lithium iron phosphate cylindrical batteries into a shearing crusher for crushing through a material conveying belt, enabling crushed materials to enter a pyrolysis furnace for pyrolysis for 1 hour, controlling the pyrolysis temperature to be 400 ℃, and providing nitrogen atmosphere by a nitrogen making machine in the crushing and pyrolysis processes. The discharged materials are firstly passed through a vibrating linear screen, a small amount of black powder is separated by screening, and then the mixture of the anode and the cathode plates is obtained after the heavy shell and the pile head are separated by air separation. The mixture of the positive electrode plate and the negative electrode plate and a small amount of black powder screened by a straight line are prepared into thick slurry with water, the thick slurry is conveyed into a leaching tank, ferric sulfate solution is added for stirring, the temperature of the materials is controlled to be about 25 ℃, the materials react for 25 minutes, oxygen-enriched air is introduced for oxidation for 30 minutes, and then the stirring leaching reaction is carried out for 30 minutes. And filtering and washing to obtain leaching liquid and leaching slag. Weighing, detecting the lithium content in the leaching solution and leaching slag, and analyzing the leaching rate of the lithium to be 97.8 percent and the leaching rates of aluminum and copper to be 0.4 percent and 0.5 percent respectively.
And (3) introducing oxygen-enriched air serving as a byproduct of the nitrogen making machine into the leaching solution for 1 hour, stopping introducing the oxygen-enriched air, slowly adding a lithium hydroxide solution with the concentration of 2mol/L, adjusting the pH value of the solution to 4.5, producing ferric hydroxide precipitate, and filtering and separating to obtain the purified lithium-containing leaching solution and the purified ferric hydroxide precipitate. Adding 1mol/L dilute sulfuric acid into ferric hydroxide precipitate to prepare ferric sulfate solution, wherein the pH value of the ferric sulfate solution is 1.0-1.5, and returning the ferric sulfate solution to the leaching process for leaching the mixture of the positive and negative electrode plates of the lithium iron phosphate.
And (3) continuously adding the purified lithium-containing solution into the solution until the pH value of the solution is 11, filtering the solution to remove impurities, heating the filtrate to about 85 ℃, adding saturated sodium carbonate solution, reacting for 1 hour, cooling to generate crystals, filtering, washing with hot water to obtain industrial-grade lithium carbonate, and analyzing the purity of the industrial-grade lithium carbonate to be 99.4%. Evaporating and concentrating the mother solution after crystallization, and returning the concentrated mother solution to the purified lithium-containing solution for adjusting the pH value of the solution.
The leached slag after the leaching of the positive and negative lithium iron phosphate plates is a mixture of copper and aluminum current collectors and ferric phosphate solid slag, after the mixture is prepared into slurry, the copper and aluminum current collectors are separated by a hydrodynamic screening device, and after the mixture is dried and ground, copper powder and aluminum powder are separated by a specific gravity separator, wherein the recovery rate of the copper and aluminum powder is 98.5%, and the purity of the copper and aluminum powder is over 99%.
Claims (6)
1. A recovery method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries is characterized by comprising the following steps:
S1, firstly, pretreating a waste lithium iron phosphate battery to obtain a flaky positive and negative plate mixture;
s2, leaching the mixture of the positive electrode plate and the negative electrode plate by taking a ferric salt solution as a leaching agent, and filtering and separating to obtain a leaching solution containing lithium and ferrous ions and solid slag comprising positive and negative electrode current collectors and ferric phosphate;
s3, introducing oxygen-enriched air into the leaching solution containing lithium and ferrous ions for oxidation, adding a lithium hydroxide solution, adjusting the pH value to be 4.0-4.5, generating ferric hydroxide precipitates, and filtering and separating to obtain a purified lithium-containing solution and a ferric hydroxide solid phase;
S4, continuously adding the purified lithium-containing solution into the lithium hydroxide solution to adjust the pH value to 9-11, further removing impurities, and then adding the saturated sodium carbonate solution under the heating condition to precipitate and crystallize to obtain industrial-grade lithium carbonate;
S5, adding dilute acid into the ferric hydroxide solid phase obtained in the step S3 to prepare a ferric salt solution, and returning to the step S2 for a leaching process;
S6, washing the solid slag comprising the anode current collector, the cathode current collector and the ferric phosphate obtained in the S2 by adopting part of crystallization mother liquor of the S4, washing by using hot water, and separating by adopting hydrodynamic screening equipment to obtain a mixture of the copper current collector and the aluminum current collector and a slag phase of the ferric phosphate;
s7, drying and grinding the mixture of the copper and aluminum current collectors obtained in the S6, and separating by using a specific gravity separator to obtain copper powder and aluminum powder;
In the S1, the pretreatment is reduction and environmental protection treatment, namely, in the nitrogen atmosphere, the waste lithium iron phosphate battery is subjected to toothed shearing crushing for one time, pyrolysis is carried out, electrolyte and a diaphragm in the waste battery are completely carbonized and volatilized, then a shell and a pile head are removed through air separation, and tail gas is subjected to secondary combustion environmental protection treatment and then discharged after reaching standards;
In the S2, the leaching reaction is specifically that the leaching temperature is controlled at 20-40 ℃, after the mixture of ferric salt solution, positive electrode plate and negative electrode plate is stirred and reacted for 10-30 minutes, oxygen-enriched air is introduced for oxidation and stirring for 20-30 minutes, then oxygen-enriched air is stopped, stirring and reacting are continued for 20-30 minutes, and then the leaching reaction is finished;
The oxygen-enriched air is a byproduct of the nitrogen making machine of the crushing and sorting line during nitrogen making, and the volume fraction of oxygen in the oxygen-enriched air is 26% -32%.
2. The recovery method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries according to claim 1, wherein in S2, ferric salt is at least one of ferric sulfate, ferric chloride and ferric nitrate, the mole number of ferric iron in the ferric salt solution is 25-50% of that of lithium iron phosphate in a positive plate and negative plate mixture, and the liquid-solid mass ratio of the ferric salt solution to the positive plate and negative plate mixture is 3-10:1.
3. The recovery method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries according to claim 1, wherein in S3 and S4, the concentration of lithium hydroxide solution is 1-10 mol/L, and the solution temperature is 20-60 ℃.
4. The recovery method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries according to claim 1, wherein in the step S4, a saturated sodium carbonate solution is added at a heating temperature of 40-90 ℃, and a mother solution obtained after precipitation and crystallization of lithium carbonate is evaporated and concentrated to prepare a lithium hydroxide solution.
5. The recovery method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries according to claim 1, wherein in the step S5, the concentration of dilute acid is 0.1-2 mol/L, and the dilute acid is one of sulfuric acid, hydrochloric acid and nitric acid.
6. The recovery method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries according to claim 1, wherein in the step S6, the hydrodynamic screening device is a hydrodynamic screening container with a built-in screen, the aperture of the screen is 3-8 mm, and the pitch of the screen holes is 5-10 mm.
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