CN114934177A - Method for selectively and deeply removing aluminum and copper in waste lithium iron phosphate recovery process - Google Patents
Method for selectively and deeply removing aluminum and copper in waste lithium iron phosphate recovery process Download PDFInfo
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- CN114934177A CN114934177A CN202210400945.7A CN202210400945A CN114934177A CN 114934177 A CN114934177 A CN 114934177A CN 202210400945 A CN202210400945 A CN 202210400945A CN 114934177 A CN114934177 A CN 114934177A
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- iron
- lithium
- copper
- aluminum
- phosphate
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- 238000000034 method Methods 0.000 title claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 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 31
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 22
- 239000010949 copper Substances 0.000 title claims abstract description 22
- 239000002699 waste material Substances 0.000 title claims abstract description 22
- 238000011084 recovery Methods 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000010405 anode material Substances 0.000 claims abstract description 7
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000009966 trimming Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229940116007 ferrous phosphate Drugs 0.000 description 9
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 9
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910000398 iron phosphate Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940009859 aluminum phosphate Drugs 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- 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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
- 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
- C22B7/007—Wet processes by acid leaching
-
- 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
- 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)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Electrochemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for selectively and deeply removing aluminum and copper in a waste lithium iron phosphate recovery process, and belongs to the technical field of waste lithium ion battery recovery. Carrying out acid dissolution on the recovered waste lithium iron phosphate anode material to obtain a mixed solution A containing iron, lithium and phosphorus; adding a water-insoluble pH regulator, regulating the pH of the mixed solution A to 2.5-6.0, precipitating, and separating out aluminum phosphate and copper phosphate to obtain a mixed solution B containing phosphorus, iron and lithium, wherein the impurities of aluminum and copper do not exceed the standard. On the premise of ensuring that all valuable elements such as lithium, phosphorus, iron and the like are recovered to the maximum extent, the pH trimming agent is added to selectively and deeply remove aluminum and copper, so that the obtained solution containing phosphorus, iron and lithium, the content of which does not exceed the standard, can be used for directly synthesizing the lithium iron phosphate anode material in the follow-up process. The method is simple, efficient and green, has remarkable economic and social benefits and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a method for selectively and deeply removing aluminum and copper in a waste lithium iron phosphate recovery process.
Background
China gradually enters the retirement stage of large-scale lithium iron phosphate batteries from 2019, and if the lithium iron phosphate batteries are improperly disposed, serious pollution is caused, so that new energy materials are changed from green to black. The currently reported waste lithium iron phosphate batteries mainly recover lithium elements, and lithium carbonate, lithium phosphate or lithium dihydrogen phosphate is obtained by a precipitation method, such as CN107540004B, CN108147384B, CN108470952B and CN 111187913B; recovery of phosphorus and iron elements by obtaining iron phosphate precipitates has also been reported in part, such as CN109179358B, CN106684485B, CN 109626350B; there are also published reports of methods for recovering lithium and iron phosphate via complex acid-base reaction steps simultaneously considered, such as CN111009660B, CN 111924819A. However, the separate recovery of lithium and iron phosphate through complicated process flow results in a long overall flow and a high overall production cost.
A great deal of research reports also exist on the direct recycling of waste lithium iron phosphate. The main process flow can be summarized as follows: disassembling batteries, sorting pole pieces → stripping waste LFP from the pole pieces → regulating and controlling components → repairing and regenerating. However, the removal of copper and aluminum impurities before the repair and regeneration process is not considered, so that the aluminum and copper of the lithium iron phosphate recovered in the method seriously exceed the standard, and the method cannot be popularized in industrial production, such as CN101916889B, CN111547697A, CN113036253A and CN 110098442A. Some techniques consider impurity removal, but the process is more complicated, the cost is high, and the industrial popularization difficulty is higher. For example, CN110112481B discloses a method for preparing a lithium iron phosphate positive electrode material by recycling waste lithium iron phosphate batteries, which comprises separating aluminum foil and lithium iron phosphate powder through mechanical crushing and vibrating screen, dissolving with acid, adjusting pH with an alkaline substance NaOH or ammonia water, removing aluminum with phosphate radical, supplementing a lithium source and a phosphorus source, and finally obtaining the lithium iron phosphate positive electrode material through hydrothermal reaction. CN110643814B discloses a method for removing aluminum impurities from a mixed solution of iron-containing sulfuric acid and phosphoric acid, which comprises the following steps: (1) adding a certain amount of reducing agent (iron simple substance) and pH regulator (urea, hexamethylenetetramine or ammonium dihydrogen phosphate) into the mixed solution; (2) introducing non-oxidizing gas into the mixture at a certain temperature and stirring the mixture in a constant-temperature water bath; (3) and filtering after stirring for a period of time to obtain filtrate, namely the solution after impurity removal.
Due to the difficulty of actual industrial scale production, most of companies still adopt the following procedures when recycling waste lithium iron phosphate batteries at present: 1) discharging, 2) crushing the whole battery, 3) calcining at high temperature to remove the binder and the diaphragm, 4) sieving to obtain a copper foil and aluminum foil mixture and a graphite carbon powder lithium iron phosphate powder mixture, and 5) separating copper from aluminum to obtain copper and aluminum. The mixture of the carbon powder and the lithium iron phosphate powder obtained by the process contains a large amount of copper powder and aluminum powder, and then the lithium is recovered after acid dissolution. If the iron phosphate is desired to be recycled, aluminum and copper are removed in advance by using a precipitation method, otherwise the aluminum and copper of the recycled iron phosphate can not meet the used quality standard. Because the pH values of ferrous phosphate, ferric phosphate and aluminum phosphate which begin to precipitate are very close, the aluminum cannot be removed to an acceptable degree by a known method of adding NaOH or ammonia water, a large amount of phosphorus and iron can be co-precipitated due to local instantaneous overhigh pH in the aluminum removal process, the phosphate precipitate has fine crystal particles and is difficult to clean in filtration, and the precipitate can take away a large amount of lithium, so that a large amount of phosphorus and lithium is wasted.
Because of the difficulties in practical mass production, only lithium can be recovered in practical industrial production, and a large amount of phosphate waste residues are considered to be treated. Therefore, it has become a difficult point to solve the problem in the art to develop a technology for reasonably removing aluminum and copper from an acid-dissolved liquid to an allowable upper limit on the premise of ensuring the maximum recovery of all valuable elements such as lithium, phosphorus, iron and the like in the process of recovering a waste lithium iron phosphate material, so as to directly regenerate qualified lithium iron phosphate in a short process and at low cost in subsequent processes.
Disclosure of Invention
The invention aims to provide a method for selectively and deeply removing aluminum and copper in the recovery process of waste lithium iron phosphate, which is used for directly and subsequently synthesizing a lithium iron phosphate anode material again by adding a pH trimming agent to selectively and deeply remove aluminum and copper on the premise of ensuring that all valuable elements such as lithium, phosphorus, iron and the like are recovered to the maximum extent to obtain a solution containing phosphorus, iron and lithium, the content of aluminum and copper of which does not exceed the standard. The method is simple, efficient and green, has remarkable economic and social benefits and has wide application prospect.
In order to realize the purpose, the invention adopts the following technical scheme:
a method for selectively and deeply removing aluminum and copper in a waste lithium iron phosphate recovery process comprises the following steps:
1) carrying out acid dissolution on the recovered waste lithium iron phosphate anode material to obtain a mixed solution A containing iron, lithium and phosphorus;
2) adding a water-insoluble pH regulator, regulating the pH of the mixed solution A to 2.5-6.0, precipitating, and separating out aluminum phosphate and copper phosphate to obtain a mixed solution B containing phosphorus, iron and lithium, wherein the impurities of aluminum and copper do not exceed the standard.
Preferably, the water-insoluble pH adjustor in step 2) is at least one of iron powder, ferrous oxide and ferrous hydroxide; adjusting the pH value of the mixed solution A to 3.5; under a non-oxidizing atmosphere; the mass ratio of iron to aluminum in the mixed solution B is more than 1750: 1, the mass ratio of iron to copper is more than 7000: 1; the recovery rate of iron and lithium in the mixed solution B exceeds 98 percent.
The invention has the beneficial effects that: it has been found through a number of experiments that ferrous phosphate begins to precipitate at a pH of 4.0 and that once a ferrous phosphate precipitate is formed, an acidic liquid having a pH of less than 2.0 is required to dissolve it. When the pH value is adjusted by using known sodium hydroxide or ammonia water in an acid leachate of the lithium iron phosphate cathode material to realize aluminum removal by aluminum phosphate precipitation, the instantaneous pH value of alkaline liquid is always greater than 7, and because a large amount of ferrous ions and phosphate ions exist in the liquid, a ferrous phosphate precipitation is preferentially generated in the liquid at this time, so that aluminum cannot be removed completely, and a large amount of ferrous phosphate is co-precipitated. After the acid dissolution, the pH value of the acidic liquid is finely adjusted to 3.5 by using the water-insoluble low-valent iron, and the pH value of the acidic liquid is not allowed to be higher than 4 (the pH value of ferrous phosphate beginning to precipitate) at any moment, so that the condition that the added instant pH is too high to generate ferrous phosphate precipitation is avoided in the process of adding the pH fine adjusting agent, the precipitation of the ferrous phosphate is avoided while aluminum phosphate and copper phosphate are formed by using a precipitation method to selectively remove aluminum copper, and the precipitation of the ferrous phosphate is avoided, so that the leaching solution with the aluminum copper content not exceeding the allowable upper limit is obtained while the maximum recovery rate of phosphorus, lithium and iron is ensured, the qualified lithium iron phosphate can be regenerated in the subsequent process in a short flow at low cost, and the maximum utilization value of the waste lithium iron phosphate material is realized. The method has the advantages of simple treatment flow, no impurity introduction, good impurity removal effect and better economic and social benefits.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Adding 50 g of the recycled waste lithium iron phosphate anode material into a mixture of 1: and (3) heating 250 ml of sulfuric acid solution of 9 under the protection of nitrogen, dissolving for 120 minutes, and filtering to obtain conductive carbon slag and acid-dissolved mixed solution containing iron, lithium and phosphorus, wherein the test result is as follows:
under the non-oxidizing atmosphere, adding 8 g of ferrous oxide powder as a water-insoluble pH regulator, adjusting the pH to 3.5, precipitating and filtering, wherein the test result of the filtered liquid is as follows:
the iron-aluminum ratio is 2125 (larger than a target value 1750), the iron-copper ratio is 7968 (larger than a target value 7000), and a mixed solution containing phosphorus, iron and lithium, of which the impurity aluminum-copper does not exceed the standard, is obtained.
Example 2
Adding 75 g of the recycled waste lithium iron phosphate anode material into 250 ml of 1: 6 sulfuric acid solution, heating to 60 ℃ under the protection of nitrogen, dissolving for 120 minutes, and filtering to obtain conductive carbon slag and acid-dissolved iron, lithium and phosphorus-containing mixed liquid, wherein the test result is as follows:
adding 2 g of water-insoluble pH regulator iron powder and 12 g of ferrous hydroxide under a non-oxidizing atmosphere, adjusting the pH to 3.5, precipitating and filtering, wherein the test result of the filtered liquid is as follows:
the iron-aluminum ratio is 2115 (larger than a target value 1750), the iron-copper ratio is 8655 (larger than a target value 7000), and the mixed liquid containing phosphorus, iron and lithium, of which the impurity aluminum-copper does not exceed the standard, is obtained.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A method for selectively and deeply removing aluminum and copper in a waste lithium iron phosphate recovery process is characterized by comprising the following steps: the method comprises the following steps:
1) carrying out acid dissolution on the recovered waste lithium iron phosphate anode material to obtain a mixed solution A containing iron, lithium and phosphorus;
2) adding a water-insoluble pH regulator, regulating the pH of the mixed solution A to 2.5-6.0, precipitating, and separating out aluminum phosphate and copper phosphate to obtain a mixed solution B containing phosphorus, iron and lithium, wherein the impurities of aluminum and copper do not exceed the standard.
2. The method of claim 1, wherein: the water-insoluble pH regulator in the step 2) is at least one of iron powder, ferrous oxide and ferrous hydroxide.
3. The method of claim 1, wherein: in the step 2), the pH value of the mixed solution A is adjusted to 3.5.
4. The method of claim 1, wherein: step 2) is carried out under a non-oxidizing atmosphere.
5. The method of claim 1, wherein: the mass ratio of iron to aluminum in the mixed solution B in the step 2) is more than 1750: 1, the mass ratio of iron to copper is more than 7000: 1.
6. the method of claim 1, wherein: the recovery rate of the iron and the lithium in the mixed liquid B in the step 2) exceeds 98 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210400945.7A CN114934177A (en) | 2022-04-18 | 2022-04-18 | Method for selectively and deeply removing aluminum and copper in waste lithium iron phosphate recovery process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210400945.7A CN114934177A (en) | 2022-04-18 | 2022-04-18 | Method for selectively and deeply removing aluminum and copper in waste lithium iron phosphate recovery process |
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| Publication Number | Publication Date |
|---|---|
| CN114934177A true CN114934177A (en) | 2022-08-23 |
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| CN202210400945.7A Pending CN114934177A (en) | 2022-04-18 | 2022-04-18 | Method for selectively and deeply removing aluminum and copper in waste lithium iron phosphate recovery process |
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| CN (1) | CN114934177A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115744864A (en) * | 2022-11-30 | 2023-03-07 | 江西理工大学 | Method for efficiently recycling and reusing waste lithium iron phosphate battery positive electrode material |
| CN115924879A (en) * | 2023-01-18 | 2023-04-07 | 河南佰利新能源材料有限公司 | Method for recycling lithium iron phosphate from scrap lithium iron phosphate material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN113737018A (en) * | 2021-08-25 | 2021-12-03 | 金川集团股份有限公司 | Method for recovering anode raw material of waste battery |
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| CN110643814A (en) * | 2018-06-26 | 2020-01-03 | 中南大学 | Method for removing aluminum and recycling waste lithium iron phosphate batteries |
| KR20200065503A (en) * | 2018-11-30 | 2020-06-09 | 주식회사 포스코 | Method of recovery of valuable metals from scrap containing cathode materials of lithium ion battery |
| CN111009660A (en) * | 2019-11-26 | 2020-04-14 | 宁夏百川新材料有限公司 | Method for preparing lithium iron phosphate positive electrode material from waste lithium iron phosphate battery |
| CN111270073A (en) * | 2020-02-03 | 2020-06-12 | 广东省稀有金属研究所 | Method for recovering valuable metals from leachate of waste lithium ion battery electrode material |
| CN113737018A (en) * | 2021-08-25 | 2021-12-03 | 金川集团股份有限公司 | Method for recovering anode raw material of waste battery |
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| CN115744864A (en) * | 2022-11-30 | 2023-03-07 | 江西理工大学 | Method for efficiently recycling and reusing waste lithium iron phosphate battery positive electrode material |
| CN115924879A (en) * | 2023-01-18 | 2023-04-07 | 河南佰利新能源材料有限公司 | Method for recycling lithium iron phosphate from scrap lithium iron phosphate material |
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