CN117500753A - Method for removing aluminum and copper in ferrophosphorus slag and application thereof - Google Patents
Method for removing aluminum and copper in ferrophosphorus slag and application thereof Download PDFInfo
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- CN117500753A CN117500753A CN202380011153.3A CN202380011153A CN117500753A CN 117500753 A CN117500753 A CN 117500753A CN 202380011153 A CN202380011153 A CN 202380011153A CN 117500753 A CN117500753 A CN 117500753A
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- iron
- copper
- aluminum
- phosphate
- ferrophosphorus
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 118
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 83
- 239000010949 copper Substances 0.000 title claims abstract description 83
- 239000002893 slag Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000012074 organic phase Substances 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 43
- 238000002386 leaching Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000005554 pickling Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 21
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 13
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 53
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 27
- 239000005955 Ferric phosphate Substances 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 26
- 229940032958 ferric phosphate Drugs 0.000 claims description 26
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 16
- 235000021110 pickles Nutrition 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 15
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 15
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000003085 diluting agent Substances 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 13
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 239000006012 monoammonium phosphate Substances 0.000 claims description 10
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 10
- 239000002608 ionic liquid Substances 0.000 claims description 8
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- SNNIPOQLGBPXPS-UHFFFAOYSA-M tetraoctylazanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC SNNIPOQLGBPXPS-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 238000004537 pulping Methods 0.000 claims description 5
- VMJQVRWCDVLJSI-UHFFFAOYSA-M tetraheptylazanium;chloride Chemical compound [Cl-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC VMJQVRWCDVLJSI-UHFFFAOYSA-M 0.000 claims description 5
- PKJSRUTWBDIWAR-UHFFFAOYSA-N 2-ethyl-2,5-dimethylhexanoic acid Chemical compound CCC(C)(C(O)=O)CCC(C)C PKJSRUTWBDIWAR-UHFFFAOYSA-N 0.000 claims description 4
- MMDSMWGHQSXYMV-UHFFFAOYSA-N 3-methyl-2-phenoxynonanoic acid Chemical compound CCCCCCC(C)C(C(O)=O)OC1=CC=CC=C1 MMDSMWGHQSXYMV-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical compound [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract description 17
- 238000011084 recovery Methods 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 8
- -1 sodium sulfide Chemical compound 0.000 abstract description 6
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 48
- 239000012535 impurity Substances 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 12
- 238000004070 electrodeposition Methods 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 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 description 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 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 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application provides a method for removing aluminum and copper in ferrophosphorus slag and application thereof, wherein the method is used for carrying out acid leaching on the ferrophosphorus slag to obtain acid leaching liquid; mixing the iron simple substance with pickling solution, performing a first copper removal reaction, mixing soluble sulfide such as sodium sulfide, and performing a second copper removal reaction to obtain copper removal pickling solution; and then mixing the extractant with the copper-removing pickling solution, and extracting to obtain a ferrophosphorus solution and a aluminum organic phase, thereby completing the removal of aluminum and copper. The application utilizes iron powder and soluble sulfide to deeply remove copper, and the reuse has high-selectivity extractant to aluminum to extract aluminum, thereby completing the separation and removal of aluminum copper, and the use of iron powder and soluble sulfide can convert ferric iron in a system into ferrous iron, thereby avoiding the loss of iron element in the process of extracting aluminum, ensuring that the recovery rate of ferrophosphorus is more than 99 percent, and effectively improving the purity of the obtained ferrophosphorus solution.
Description
Technical Field
The embodiment of the application relates to the field of battery material recovery, for example, a method for removing aluminum and copper in ferrophosphorus slag and application thereof.
Background
In recent years, the lithium ion battery has the remarkable advantages of high specific capacity, stable performance, long service life and the like, and greatly promotes the application and development of the power battery of the new energy automobile. Among a plurality of positive electrode materials, the lithium iron phosphate has the advantages of low preparation cost, high safety performance and the like, is a mainstream lithium battery product in the current market, and has a large market share.
Along with the increase of the usage amount of lithium iron phosphate, the number of waste lithium iron phosphate batteries is also rapidly increased, and the waste lithium iron phosphate batteries are treated and recycled with high value, so that the problems to be solved in industry are gradually solved.
In general, in the waste lithium iron phosphate battery, the mass ratio of lithium iron phosphate is about 30-35%, the ratio of copper foil and aluminum foil is about 10%, and the contents of valuable metal elements Li, fe, cu and Al are far higher than the contents of corresponding elements in natural minerals, so that the waste lithium iron phosphate battery is also a raw material with recovery value.
Considering that the properties of Al, cu and Fe are similar and difficult to separate, the existence of the impurities can influence the recovery of ferrophosphorus slag to prepare battery grade ferric phosphate, influence the purity and yield of the ferric phosphate and further influence the electrochemical performance of the lithium iron phosphate battery anode material prepared by using the ferric phosphate.
Currently, for removing aluminum and copper impurities in ferrophosphorus slag after lithium extraction, there are related technologies of leaching impurities by alkali or adsorbing aluminum by an adsorbent, and related technologies of removing impurities and purifying by an acidic solution, for example, CN114852983a discloses a method for extracting battery grade ferric phosphate from ferrophosphorus slag which is a byproduct of recycling waste lithium batteries, and the ferrophosphorus slag powder is immersed in sodium hydroxide solution for reaction to remove aluminum; placing the ferrophosphorus waste residue after aluminum removal in a muffle furnace, and calcining at a high temperature in an air atmosphere to remove carbon; adding low-concentration acid liquor into ferrophosphorus waste residue powder after aluminum removal and carbon removal, and heating to react to remove copper impurities; adding acid liquor into the ferrophosphorus waste residue powder after copper removal, heating to carry out leaching reaction, and filtering to obtain pickle liquor; adjusting the pH value of the pickle liquor, and sequentially filtering, washing and drying to obtain the hydrated ferric phosphate. However, the impurity content in the iron phosphate recovered and prepared by the methods still does not reach the application standard of battery-grade iron phosphate, the process flow is complex, the efficiency is low, the impurity removal effect is poor, and the purity and the yield of the obtained iron phosphate product are low.
CN114920226a discloses a method for removing aluminum and copper impurities from ferrophosphorus slag after lithium extraction of a lithium iron phosphate battery, which comprises the steps of mixing the ferrophosphorus slag after lithium extraction of the lithium iron phosphate battery with fluoride, and roasting to obtain roasting slag containing aluminum and copper fluoride; mixing the roasting slag with water, carrying out leaching reaction under the condition of a certain pH value, and carrying out solid-liquid separation to obtain leaching liquid containing aluminum and copper complexes and ferrophosphorus slag after impurity removal. According to the scheme, acid-base leaching is not needed, the deep removal of Al and Cu impurities can be realized, but the fluorine salt with fluorine element and high price is needed to be used for treatment.
Therefore, a new scheme is still needed to be developed to effectively remove and separate aluminum and copper elements in the ferrophosphorus slag, so that the ferrophosphorus is enriched in high purity, and the high-purity ferric phosphate product is conveniently prepared subsequently, so that the high-value recycling of the ferrophosphorus slag is realized.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
The embodiment of the application provides a method for removing aluminum and copper in ferrophosphorus slag and application thereof, wherein the method is used for carrying out acid leaching on the ferrophosphorus slag to obtain acid leaching liquid; mixing the iron simple substance with pickling solution, performing a first copper removal reaction, mixing soluble sulfide such as sodium sulfide, and performing a second copper removal reaction to obtain copper removal pickling solution; and then mixing the extractant with the copper-removing pickling solution, and extracting to obtain a ferrophosphorus solution and a aluminum organic phase, thereby completing the removal of aluminum and copper. The application utilizes iron powder and soluble sulfide to deeply remove copper, and the reuse has high-selectivity extractant to aluminum to extract aluminum, thereby completing the separation and removal of aluminum copper, and the use of iron powder and soluble sulfide can convert ferric iron in a system into ferrous iron, thereby avoiding the loss of iron element in the process of extracting aluminum, ensuring that the recovery rate of ferrophosphorus is more than 99 percent, and effectively improving the purity of the obtained ferrophosphorus solution.
In a first aspect, embodiments of the present application provide a method. A method for removing aluminum and copper from ferrophosphorus slag, the method comprising:
performing acid leaching on the ferrophosphorus slag to obtain acid leaching liquid;
mixing an iron simple substance with the pickling solution, performing a first copper removal reaction, mixing a soluble sulfide, and performing a second copper removal reaction to obtain a copper removal pickling solution;
mixing the extractant with the copper-removing pickle liquor, extracting to obtain a ferrophosphorus solution and a aluminum organic phase, and removing aluminum and copper.
The method comprises the steps of carrying out acid leaching on ferrophosphorus slag to fully dissolve valuable metal elements such as phosphorus, iron, copper and aluminum in the slag, removing copper from the obtained leaching solution by adopting iron powder, and then carrying out deep copper removal by adopting soluble sulfides such as sodium sulfide, wherein the iron powder can reduce ferric iron into ferrous iron, at the moment, sodium sulfide does not influence iron to precipitate the ferrous iron, and the ferrous iron converted into a system can avoid the loss of iron element due to the fact that ferric iron is simultaneously extracted in the subsequent aluminum extraction process; subsequently, the aluminum is extracted by adopting an extraction system with high selectivity on aluminum, aluminum impurities in the leaching solution can be deeply removed, the utilization rate of the ferrophosphorus in the ferrophosphorus slag in the whole process of the method is high, the recovery rate of the ferrophosphorus can be more than 99%, and meanwhile, the problem that the separation effect of metal aluminum impurities in the recovery process of the ferrophosphorus slag is poor is solved, so that the battery-grade ferric phosphate with higher purity can be conveniently obtained later.
The following technical scheme is used as the preferred technical scheme of the application, but not used as the limitation of the technical scheme provided by the application, and the technical purpose and beneficial effect of the application can be better achieved and realized through the following technical scheme.
As the preferable technical scheme of the application, the ferrophosphorus slag comprises ferrophosphorus slag obtained after lithium extraction by waste lithium iron phosphate battery materials.
Preferably, the iron element content in the ferrophosphorus slag is equal to or more than 24%, such as 24%, 27%, 30%, 35% or 40%, the phosphorus element content is equal to or more than 15%, such as 15%, 18%, 20%, 23% or 25%, the aluminum element content is equal to or more than 1.5%, such as 1.5%, 1.8%, 2.1%, 2.4% or 2.5%, the copper element content is equal to or more than 0.01%, such as 0.01%, 0.05%, 0.08%, 0.11%, 0.13%, 0.15% or 0.2%, etc., but not limited to the recited values, and other non-recited values within the above-recited values are equally applicable.
Preferably, the ferrophosphorus slag is firstly pulped by adding water, and then is added with concentrated acid for acid leaching.
Preferably, the solid-liquid mass ratio of the water-added pulping is 1 (2-5), such as 1:2, 1:2.3, 1:2.6, 1:2.9, 1:3.2, 1:3.5, 1:3.8, 1:4.1, 1:4.4, 1:4.7 or 1:5, but not limited to the recited values, and other non-recited values in the above-mentioned numerical ranges are equally applicable.
Preferably, the amount of the concentrated acid is 0.5 to 2 times, for example, 0.5 times, 0.7 times, 1 times, 1.2 times, 1.4 times, 1.6 times, 1.8 times, or 2 times, the molar amount of iron in the ferrophosphorus slag, but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the acid leaching is carried out at a temperature of 50 to 80 ℃, for example, 50 ℃, 53 ℃, 56 ℃, 59 ℃, 62 ℃, 65 ℃, 68 ℃, 71 ℃, 74 ℃, 77 ℃, or 80 ℃, for a time of 1 to 3 hours, for example, 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h, or 3h, but the acid leaching is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
As a preferred technical scheme of the application, the iron simple substance comprises iron powder.
Preferably, the amount of the elemental iron is 1 to 2 times, for example, 1 time, 1.2 times, 1.4 times, 1.6 times, 1.8 times, or 2 times, the molar amount of the elemental iron in the pickle liquor, but the use is not limited to the recited values, and other values not recited in the above-mentioned numerical ranges are equally applicable.
The application prefers that the dosage of the iron simple substance exceeds the mole quantity of the iron element in the pickle liquor, on the one hand, the ferric iron element can be reduced to the ferrous iron element, on the other hand, the excessive iron simple substance can reduce the copper element, and the excessive iron simple substance is enough to reduce copper because the content of the copper element in the phosphorus iron slag is relatively less, so that the dosage of the iron simple substance can be adaptively adjusted according to the actual total mole quantity of the iron element and the copper element in the pickle liquor by a person skilled in the art.
Preferably, filtering is performed after the first copper removal reaction, soluble sulfide is added into the filtrate, and the second copper removal reaction is performed, so that the copper removal pickling liquid is obtained.
Preferably, the amount of the soluble sulfide is 1.5 to 2 times, for example, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, or 2 times, the molar amount of the copper element remaining in the filtrate, but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the soluble sulphide comprises an alkali metal sulphide comprising sodium sulphide and/or potassium sulphide and/or ammonium sulphide.
The application preferably uses excessive soluble sulfide such as sodium sulfide relative to residual copper element, on one hand, can ensure deep removal of copper element, and on the other hand, excessive sodium sulfide can further reduce trace ferric ions in the solution, so as to further reduce the loss of iron element in the subsequent extraction process.
As a preferred technical scheme of the application, the extractant comprises an ionic liquid, and the ionic liquid contains an anion-cation structure.
Preferably, the substance providing a cationic structure comprises a quaternary ammonium salt and/or a quaternary phosphonium salt.
Preferably, the material providing the cationic structure comprises any one or a combination of at least two of methyltrioctyl ammonium chloride, tetrabutyl ammonium chloride, tetraoctyl ammonium chloride or tetraheptyl ammonium chloride, typical but non-limiting examples of which include methyltrioctyl ammonium chloride in combination with tetrabutyl ammonium chloride, methyltrioctyl ammonium chloride in combination with tetraoctyl ammonium chloride, methyltrioctyl ammonium chloride in combination with tetraheptyl ammonium chloride, tetrabutyl ammonium chloride in combination with tetraoctyl ammonium chloride, methyltrioctyl ammonium chloride in combination with tetraheptyl ammonium chloride or tetraoctyl ammonium chloride in combination with tetraheptyl ammonium chloride.
Preferably, the material providing the anionic structure comprises any one or a combination of at least two of bis (2-ethylhexyl) phosphate, bis (2, 4-trimethylpentyl) phosphonic acid, 2-ethyl-2, 5-dimethylhexanoic acid or sec-octylphenoxy acetic acid, typical but non-limiting examples of which include a combination of bis (2-ethylhexyl) phosphate with bis (2, 4-trimethylpentyl) phosphonic acid, a combination of bis (2-ethylhexyl) phosphate with 2-ethyl-2, 5-dimethylhexanoic acid, or a combination of bis (2, 4-trimethylpentyl) phosphonic acid with sec-octylphenoxy acetic acid.
Preferably, the extraction also uses a diluent, which constitutes the extraction organic phase with the extractant.
Preferably, the volume ratio of the extractant to the diluent is 1 (0.3-3), such as 1:0.3, 1:0.6, 1:0.9, 1:1.2, 1:1.5, 1:1.8, 1:2.1, 1:2.4, 1:2.7, or 1:3, etc., but not limited to the recited values, other non-recited values within the above ranges are equally applicable.
Preferably, the diluent comprises any one or a combination of at least two of methyl isobutyl ketone, methyl tert-butyl ether, ethyl acetate, cyclohexane or methylene chloride, typical but non-limiting examples of which include methyl isobutyl ketone in combination with methyl tert-butyl ether, methyl isobutyl ketone in combination with ethyl acetate, methyl isobutyl ketone in combination with cyclohexane, methyl isobutyl ketone in combination with methylene chloride, methyl tert-butyl ether in combination with ethyl acetate, methyl tert-butyl ether in combination with cyclohexane, methyl tert-butyl ether in combination with methylene chloride, ethyl acetate in combination with cyclohexane or cyclohexane in combination with methylene chloride.
Preferably, the volume ratio of the extracted organic phase to the copper-removing pickling solution is (1-3): 1, for example, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1 or 3:1, etc., but is not limited to the recited values, and other non-recited values within the above-recited values are equally applicable.
As a preferred technical scheme, the method further comprises the steps of removing water from the aluminum organic phase, and then performing electrodeposition to obtain metal aluminum and an aluminum-poor organic phase, wherein the aluminum-poor organic phase is recycled as an extractant.
The application adopts an extraction system with high conductivity and high selectivity to aluminum to extract aluminum; in the extraction process by using a specific extractant, the functionalized ionic liquid composed of quaternary ammonium salt, quaternary phosphonium salt cations, phosphate and carboxylic acid anions is combined with Al (III), and the functionalized anions and cations have stronger extraction capacity and selectivity on Al (III) than the traditional extractant. The metal aluminum can be obtained by direct electrodeposition in an aluminum-rich organic phase after extracting aluminum, so that the effective separation of iron and aluminum in the pickle liquor and the high-value utilization of aluminum can be realized. The organic phase after electrodeposition is reused, so that the effective connection of the process for removing aluminum impurities from the ferrophosphorus slag and electrodepositing metal aluminum is realized, and the production cost can be effectively reduced. Meanwhile, high added value metal aluminum can be generated, and the recycling rate of resources in the ferrophosphorus slag recovery process is further improved.
In a second aspect, embodiments of the present application provide a method for preparing iron phosphate recovered from ferrophosphorus slag, the method comprising:
removing aluminum and copper in the ferrophosphorus slag by using the method of the first aspect to obtain a ferrophosphorus solution;
mixing a phosphorus-iron solution, an alkali source and an iron source and/or a phosphorus source, performing precipitation reaction to obtain ferric phosphate dihydrate, and roasting to obtain ferric phosphate.
As a preferred technical solution of the present application, the iron source and/or the phosphorus source make the molar ratio of phosphorus to iron in the system reach (1-1.1): 1, for example, 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09 or 1:1.1, etc., but not limited to the listed values, and other non-listed values in the above-mentioned numerical ranges are equally applicable.
Preferably, the alkali source comprises aqueous ammonia.
Preferably, the alkali source is used to adjust the pH and control the end pH of the precipitation reaction to 1.8-2.2, for example, 1.8, 1.85, 1.9, 1.95, 2, 2.05, 2.1, 2.15 or 2.2, etc., but not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the iron source comprises any one or a combination of at least two of ferric sulfate, ferric chloride, or ferric nitrate, typical but non-limiting examples of which include a combination of ferric sulfate and ferric chloride, a combination of ferric sulfate and ferric nitrate, or a combination of ferric chloride and ferric nitrate.
Preferably, the phosphorus source comprises any one or a combination of at least two of monoammonium phosphate, sodium phosphate, ammonium phosphate, or monoammonium phosphate, typical but non-limiting examples of which include a combination of monoammonium phosphate and sodium phosphate, a combination of monoammonium phosphate and ammonium phosphate, a combination of monoammonium phosphate and monoammonium phosphate, a combination of sodium phosphate and ammonium phosphate, a combination of ammonium phosphate and monoammonium phosphate, or a combination of ammonium phosphate and monoammonium phosphate.
As a preferred technical scheme of the application, the preparation method further uses hydrogen peroxide for the mixing.
The hydrogen peroxide is preferably used in an amount of 1 to 1.5 times, for example, 1 time, 1.1 time, 1.2 times, 1.3 times, 1.4 times, or 1.5 times the molar amount of the iron element in the system, but the hydrogen peroxide is not limited to the recited values, and other non-recited values within the above-mentioned numerical ranges are equally applicable.
The precipitation reaction is preferably carried out at a temperature of 60 to 90 ℃, for example 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or the like, for a time of 1 to 2 hours, for example 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours or the like, but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the baking temperature is 450 to 650 ℃, such as 450 ℃, 470 ℃, 490 ℃, 510 ℃, 530 ℃, 550 ℃, 570 ℃, 590 ℃, 610 ℃, 630 ℃, 650 ℃ or the like, and the baking time is 3 to 6 hours, such as 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours or 6 hours or the like, but not limited to the recited values, and other values not recited in the above-mentioned numerical ranges are equally applicable.
In a third aspect, embodiments of the present application provide an iron phosphate, obtained according to the preparation method of the second aspect.
In a fourth aspect, an embodiment of the present application provides a lithium iron phosphate positive electrode material, which is prepared by using the iron phosphate according to the third aspect.
Compared with the related technical scheme, the embodiment of the application has at least the following beneficial effects:
according to the embodiment of the application, the ferrophosphorus slag is subjected to acid leaching to fully dissolve valuable metal elements such as phosphorus, iron, copper and aluminum in the slag, the obtained leaching liquid is subjected to copper removal by iron powder firstly, then the soluble sulfide is used for deep copper removal, meanwhile, ferric iron can be reduced into ferrous iron by the iron powder, at the moment, the soluble sulfide does not influence iron to precipitate the ferrous iron, and ferrous iron converted into a system can avoid the loss of iron element due to the fact that ferric iron is simultaneously extracted in the subsequent aluminum extraction process; subsequently, the aluminum is extracted by adopting an extraction system with high selectivity on aluminum, aluminum impurities in the leaching solution can be deeply removed, the utilization rate of the ferrophosphorus in the ferrophosphorus slag in the whole process of the method is high, the recovery rate of the ferrophosphorus can be more than 99%, and meanwhile, the problem that the separation effect of metal aluminum impurities in the recovery process of the ferrophosphorus slag is poor is solved, so that the battery-grade ferric phosphate with higher purity can be conveniently obtained later.
According to the embodiment of the application, the extraction system with high conductivity and high selectivity on aluminum is adopted for extracting aluminum, so that metal aluminum can be obtained through direct electrodeposition in an aluminum-rich organic phase after extracting aluminum, and the effective separation of iron and aluminum in the pickle liquor and the high-value utilization of aluminum are realized. The organic phase after electrodeposition is reused, so that the effective connection of the process for removing aluminum impurities from the ferrophosphorus slag and electrodepositing metal aluminum is realized, and the production cost can be effectively reduced. Meanwhile, high added value metal aluminum can be generated, and the recycling rate of resources in the ferrophosphorus slag recovery process is further improved.
Still other aspects will be apparent upon reading and understanding the detailed description.
Detailed Description
The technical scheme of the application is further described through the following specific embodiments.
It should be apparent to those skilled in the art that the examples are merely provided to aid in understanding the present application and should not be construed as limiting the present application in any way.
Example 1
The embodiment provides a method for removing aluminum and copper in ferrophosphorus slag and preparing ferric phosphate, which comprises the following steps:
(1) Taking phosphorus iron slag after lithium extraction from waste lithium iron phosphate, wherein the mass content of phosphorus is 21.05%, iron is 36.97%, aluminum is 1.8%, copper is 0.01%, adding water according to the solid-liquid mass ratio of 1:3 for pulping, adding concentrated sulfuric acid with the molar quantity being 1 times that of iron in the phosphorus iron slag, leaching for 2 hours at the temperature of 70 ℃, and filtering to obtain pickle liquor;
(2) Adding iron powder with the molar weight 1.5 times of that of iron in the solution into the pickling solution obtained in the step (1) to remove copper, reacting for 1.5 hours, filtering, adding sodium sulfide with the theoretical weight 1.8 times of that of residual copper ions in the solution into the filtrate to react for 0.5 hour to perform deep copper removal, and obtaining the copper-removed pickling solution;
(3) Taking ionic liquid formed by methyl trioctyl ammonium chloride and di (2-ethylhexyl) phosphate as an extracting agent, taking methyl isobutyl ketone as a diluting agent, mixing the two to obtain an extracted organic phase under the condition of volume ratio of 1:1, fully mixing the extracted organic phase with the pickle liquor obtained in the step (2), extracting aluminum under the condition of R (O/A) =2:1 to obtain a ferrophosphorus solution and a aluminum organic phase, and completing the removal of aluminum and copper;
(4) Adding a molecular desiccant into the extracted aluminum-rich organic phase to remove water to obtain an anhydrous aluminum-rich organic phase, taking silver flakes as a working electrode, taking a carbon electrode as a reference electrode and a counter electrode, and carrying out electrodeposition under the potential of a-3V electrode to obtain metallic aluminum and an aluminum-poor organic phase, wherein the aluminum-poor organic phase returns to the step (3) to serve as an extracted organic phase and is continuously used for extracting aluminum, so that the recycling of the organic phase is realized;
(5) Adding ferric sulfate and ammonium dihydrogen phosphate into the ferrophosphorus solution obtained in the step (3) to adjust the molar ratio of the ferric sulfate to the ammonium dihydrogen phosphate to 1.05:1, adding hydrogen peroxide with the molar quantity being 1.3 times that of the iron, adding ammonia water to adjust the pH value to 2, reacting for 1.5h, carrying out solid-liquid separation to obtain ferric phosphate dihydrate precipitate after the reaction is completed, and placing the ferric phosphate dihydrate into a muffle furnace to be roasted for 4h at the temperature of 500 ℃ to obtain the high-purity ferric phosphate.
Example 2
The embodiment provides a method for removing aluminum and copper in ferrophosphorus slag and preparing ferric phosphate, which comprises the following steps:
(1) Taking phosphorus iron slag after lithium extraction from waste lithium iron phosphate, wherein the mass content of phosphorus is 21.15%, iron is 37.21%, aluminum is 1.8%, copper is 0.01%, adding water according to the solid-liquid mass ratio of 1:5 for pulping, adding concentrated sulfuric acid with the molar quantity being 2 times that of iron in the phosphorus iron slag, leaching for 1h at the temperature of 80 ℃, and filtering to obtain pickle liquor;
(2) Adding iron powder with 2 times of the iron molar weight in the solution into the pickling solution obtained in the step (1) to remove copper, reacting for 1.5 hours, filtering, adding sodium sulfide with 2 times of the theoretical amount of residual copper ions in the solution into the filtrate to react for 0.5 hour to perform deep copper removal, and obtaining the copper-removed pickling solution;
(3) Mixing tetrabutylammonium chloride and 2-ethyl-2, 5-dimethylhexanoic acid ionic liquid serving as an extractant and ethyl acetate serving as a diluent under the condition that the volume ratio is 2:3 to obtain an extracted organic phase, fully mixing the extracted organic phase with the pickle liquor obtained in the step (2), extracting aluminum under the condition that the ratio is R (O/A) =2:1 to obtain a ferrophosphorus solution and a aluminum organic phase, and completing the removal of aluminum and copper;
(4) Adding a molecular desiccant into the extracted aluminum-rich organic phase to remove water to obtain an anhydrous aluminum-rich organic phase, taking silver flakes as a working electrode, taking a carbon electrode as a reference electrode and a counter electrode, and carrying out electrodeposition under the potential of a-4V electrode to obtain metallic aluminum and an aluminum-poor organic phase, wherein the aluminum-poor organic phase returns to the step (3) to serve as an extracted organic phase and is continuously used for extracting aluminum, so that the recycling of the organic phase is realized;
(5) Adding ferric sulfate and ammonium dihydrogen phosphate into the ferrophosphorus solution obtained in the step (3) to adjust the molar ratio of the ferric sulfate to the ammonium dihydrogen phosphate to 1.1:1, adding hydrogen peroxide with the molar quantity being 1.5 times that of the iron, adding ammonia water to adjust the pH value to 2.2, reacting for 2 hours, carrying out solid-liquid separation to obtain ferric phosphate dihydrate precipitate after the reaction is completed, and placing the ferric phosphate dihydrate precipitate in a muffle furnace to be roasted for 3 hours at the temperature of 650 ℃ to obtain the high-purity ferric phosphate.
Example 3
The embodiment provides a method for removing aluminum and copper in ferrophosphorus slag and preparing ferric phosphate, which comprises the following steps:
(1) Taking phosphorus iron slag after lithium extraction from waste lithium iron phosphate, wherein the mass content of phosphorus is 21.15%, iron is 37.21%, aluminum is 1.8%, copper is 0.01%, adding water according to the solid-liquid mass ratio of 1:2 for pulping, adding concentrated sulfuric acid with the molar quantity being 0.5 times that of iron in the phosphorus iron slag, leaching for 3 hours at 50 ℃, and filtering to obtain pickle liquor;
(2) Adding iron powder with the molar quantity of iron being 1 time of that of the solution into the pickling solution obtained in the step (1) to remove copper, reacting for 1.5 hours, filtering, adding sodium sulfide with the theoretical quantity of residual copper ions being 1.5 times of that of the solution into the filtrate to react for 0.5 hour to deeply remove copper, and obtaining the copper-removed pickling solution;
(3) Mixing ionic liquid formed by tetraoctyl ammonium chloride and sec-octyl phenoxyacetic acid serving as an extractant and ethyl acetate serving as a diluent under the condition that the volume ratio is 3:2 to obtain an extracted organic phase, fully mixing the extracted organic phase with the pickling liquid obtained in the step (2), extracting aluminum under the condition that the ratio is R (O/A) =3:1 to obtain a ferrophosphorus solution and a aluminum organic phase, and completing the removal of aluminum and copper;
(4) Adding a molecular desiccant into the extracted aluminum-rich organic phase to remove water to obtain an anhydrous aluminum-rich organic phase, taking silver flakes as a working electrode, taking a carbon electrode as a reference electrode and a counter electrode, and carrying out electrodeposition under the potential of a-2V electrode to obtain metallic aluminum and an aluminum-poor organic phase, wherein the aluminum-poor organic phase returns to the step (3) to serve as an extracted organic phase and is continuously used for extracting aluminum, so that the recycling of the organic phase is realized;
(5) Adding ferric sulfate and ammonium dihydrogen phosphate into the ferrophosphorus solution obtained in the step (3) to adjust the molar ratio of the ferrophosphorus in the system to 1:1, adding hydrogen peroxide with the molar quantity being 1 times of the molar quantity of the iron, adding ammonia water to adjust the pH value to 1.8, reacting for 2 hours, carrying out solid-liquid separation to obtain ferric phosphate dihydrate precipitate after the reaction is completed, and placing the ferric phosphate dihydrate in a muffle furnace to be roasted for 6 hours at 450 ℃ to obtain the high-purity ferric phosphate.
Example 4
This example provides a method for removing aluminum and copper from a phosphorus iron slag and preparing iron phosphate by adjusting the amount of sodium sulfide to 1.2 times the theoretical amount of residual copper ions in the solution in step (2), except that the conditions are exactly the same as in example 1.
Example 5
This example provides a method for removing aluminum and copper from a phosphorus iron slag and preparing iron phosphate by adjusting the amount of sodium sulfide to 1.5 times the theoretical amount of residual copper ions in the solution in step (2), except that the conditions are exactly the same as in example 1.
Example 6
This example provides a method for removing aluminum and copper from a phosphorus iron slag and preparing iron phosphate, which adjusts the amount of sodium sulfide to 2 times from 1.8 times the theoretical amount of residual copper ions in the solution in step (2), except that the conditions are exactly the same as in example 1.
Example 7
This example provides a method for removing aluminum and copper from a phosphorus iron slag and preparing iron phosphate by adjusting the amount of sodium sulfide to 2.3 times from 1.8 times the theoretical amount of residual copper ions in the solution in step (2), except that the conditions are exactly the same as in example 1.
Example 8
This example provides a method for removing aluminum and copper from ferrophosphorus slag and preparing iron phosphate using only di (2-ethylhexyl) phosphate as an extractant, without using methyltrioctylammonium chloride, with the exception of the above, which is exactly the same as in example 1.
Example 9
The present example provides a method for removing aluminum and copper from ferrophosphorus slag and preparing iron phosphate, wherein in the step (3), the volume ratio of the extractant to the diluent is adjusted from 1:1 to 1:0.1, and the other conditions are exactly the same as those in the example 1.
Example 10
The present example provides a method for removing aluminum and copper from ferrophosphorus slag and preparing iron phosphate, wherein in the step (3), the volume ratio of the extractant to the diluent is adjusted from 1:1 to 1:0.3, and the other conditions are exactly the same as in example 1 except the above.
Example 11
The present example provides a method for removing aluminum and copper from ferrophosphorus slag and preparing iron phosphate, wherein in the step (3), the volume ratio of the extractant to the diluent is adjusted from 1:1 to 1:3, and the other conditions are exactly the same as those in the example 1.
Example 12
The present example provides a method for removing aluminum and copper from ferrophosphorus slag and preparing iron phosphate, wherein in the step (3), the volume ratio of the extractant to the diluent is adjusted from 1:1 to 1:3.3, and the other conditions are exactly the same as in the example 1 except the above.
Comparative example 1
This comparative example provides a method for removing aluminum and copper from ferrophosphorus slag and preparing iron phosphate, which does not use an extraction organic phase to extract aluminum, namely, does not carry out step (3) and step (4), directly uses the copper-removed pickling solution obtained in step (2) as a ferrophosphorus solution in step (5), and has the same conditions as in example 1 except the above.
Comparative example 2
This comparative example provides a method for removing aluminum and copper from ferrophosphorus slag and preparing iron phosphate without using sodium sulfide, i.e., step (2) is: adding iron powder with the molar quantity of iron being 1.5 times of that of the solution into the pickling solution obtained in the step (1) to remove copper, reacting for 1.5 hours, and filtering to obtain the copper-removed pickling solution, wherein the conditions are exactly the same as in the example 1 except the above.
The iron phosphate obtained in examples 1 to 12 and comparative examples 1 to 2 was tested to obtain the composition index (mass content), purity of iron phosphate and recovery rate data of aluminum as shown in Table 1.
TABLE 1
Note that: in Table 1 "/" indicates that the Al recovery rate cannot be or need not be calculated.
As can be seen from table 1:
when the aluminum is not extracted in the impurity removal process, aluminum-containing impurities of iron phosphate are higher, the purity of the iron phosphate is greatly reduced, the electrochemical performance of the lithium iron phosphate anode material prepared later is affected, and the aluminum in the leaching solution cannot be recovered because the aluminum extraction step is not performed;
when sodium sulfide is not added or the content of the sodium sulfide is too low, the content of copper impurities in the leaching solution is high, and the existing ferric iron is simultaneously extracted in the subsequent aluminum extraction process, so that the purity of ferric phosphate is affected, and the recovery rate of aluminum is not high; excessive sodium sulfide content easily causes ferrous sulfide precipitation in the solution, and causes the introduction of impurities to reduce the purity of ferric phosphate;
the difference between example 12 and example 1 is that the extractant, which is di (2-ethylhexyl) phosphate without ionic liquid properties, is changed, and since the organic system is not conductive, electrodeposition of aluminum is not performed, and recovery of aluminum is not performed;
it can be seen from examples 13-16 that the selection of the appropriate ratio of extractant to diluent is beneficial to increase the extraction rate of aluminum, thereby reducing the content of impurity aluminum in the iron phosphate and increasing the purity of the iron phosphate.
The detailed structural features of the present application are described in the above embodiments, but the present application is not limited to the above detailed structural features, that is, it does not mean that the present application must rely on the above detailed structural features to be implemented. It should be apparent to those skilled in the art that any modifications, equivalent substitutions for selected components, addition of auxiliary components, selection of specific modes, etc. of the present application are within the scope of the present application and the disclosure.
The preferred embodiments of the present application have been described in detail above, but the present application is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present application within the scope of the technical concept of the present application, and all the simple modifications belong to the protection scope of the present application.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described in detail.
Moreover, any combination of the various embodiments of the present application may be made without departing from the spirit of the present application, which should also be considered as disclosed herein.
Claims (15)
1. A method for removing aluminum and copper from ferrophosphorus slag, comprising:
performing acid leaching on the ferrophosphorus slag to obtain acid leaching liquid;
mixing an iron simple substance with the pickling solution, performing a first copper removal reaction, mixing a soluble sulfide, and performing a second copper removal reaction to obtain a copper removal pickling solution;
mixing the extractant with the copper-removing pickle liquor, extracting to obtain a ferrophosphorus solution and a aluminum organic phase, and removing aluminum and copper.
2. The method of claim 1, wherein the phosphorus iron slag comprises phosphorus iron slag after lithium extraction from waste lithium iron phosphate battery material.
3. The method according to claim 2, wherein the phosphorus iron slag contains more than or equal to 24% by mass of iron element, more than or equal to 15% by mass of phosphorus element, more than or equal to 1.5% by mass of aluminum element and more than or equal to 0.01% by mass of copper element.
4. A method according to claim 2 or 3, wherein the ferrophosphorus slag is slurried with water and then acid leached with concentrated acid.
5. The method according to claim 4, wherein the mass ratio of solid to liquid in the water-added pulping is 1 (2-5);
preferably, the amount of the concentrated acid is 0.5 to 2 times the molar amount of iron in the ferrophosphorus slag;
preferably, the temperature of the acid leaching is 50-80 ℃ and the time is 1-3 h.
6. The method of any one of claims 1-5, wherein the elemental iron comprises iron powder;
preferably, the dosage of the iron simple substance is 1 to 2 times of the molar quantity of iron element in the pickle liquor;
preferably, filtering after the first copper removal reaction, adding soluble sulfide into the filtrate, and performing a second copper removal reaction to obtain copper removal pickle liquor;
preferably, the soluble sulfide is used in an amount of 1.5 to 2 times the molar amount of the copper element remaining in the filtrate;
preferably, the soluble sulphide comprises an alkali metal sulphide and/or ammonium sulphide.
7. The method of any one of claims 1-6, wherein the extractant comprises an ionic liquid containing a cationic and anionic structure;
preferably, the substance providing a cationic structure comprises a quaternary ammonium salt and/or a quaternary phosphonium salt;
preferably, the substance providing a cationic structure comprises any one or a combination of at least two of methyltrioctylammonium chloride, tetrabutylammonium chloride, tetraoctylammonium chloride or tetraheptylammonium chloride;
preferably, the material providing the anionic structure comprises any one or a combination of at least two of di (2-ethylhexyl) phosphate, bis (2, 4-trimethylpentyl) phosphonic acid, 2-ethyl-2, 5-dimethylhexanoic acid or sec-octylphenoxy acetic acid;
preferably, the extraction also uses a diluent, which constitutes the extraction organic phase with the extractant;
preferably, the volume ratio of the extractant to the diluent is 1 (0.3-3);
preferably, the diluent comprises any one or a combination of at least two of methyl isobutyl ketone, methyl tert-butyl ether, ethyl acetate, cyclohexane or dichloromethane;
preferably, the volume ratio of the extraction organic phase to the copper-removing pickling solution is (1-3): 1.
8. The process of any one of claims 1-7, further comprising electrodepositing the aluminum organic phase after water to yield metallic aluminum and an aluminum depleted organic phase, which is recycled as an extractant.
9. A method for producing iron phosphate recovered from ferrophosphorus slag, comprising:
removing aluminum and copper in the ferrophosphorus slag by using the method of any one of claims 1-8 to obtain a ferrophosphorus solution;
mixing a phosphorus-iron solution, an alkali source and an iron source and/or a phosphorus source, performing precipitation reaction to obtain ferric phosphate dihydrate, and roasting to obtain ferric phosphate.
10. The process according to claim 9, wherein the iron source and/or the phosphorus source is such that the molar ratio of phosphorus to iron in the system is 1 to 1.1.
11. The production method according to claim 9 or 10, wherein the alkali source comprises ammonia water;
preferably, the alkali source is used for regulating the pH and controlling the end point pH of the precipitation reaction to be 1.8-2.2.
12. The production method according to any one of claims 9 to 11, wherein the iron source comprises any one or a combination of at least two of iron sulfate, iron chloride, or iron nitrate;
preferably, the phosphorus source comprises any one or a combination of at least two of monoammonium phosphate, sodium phosphate, ammonium phosphate or monoammonium phosphate.
13. The production method according to any one of claims 9 to 12, wherein the production method further uses hydrogen peroxide for the mixing;
preferably, the dosage of the hydrogen peroxide is 1 to 1.5 times of the molar quantity of the iron element in the system;
preferably, the temperature of the precipitation reaction is 60-90 ℃ and the time is 1-2 h;
preferably, the roasting temperature is 450-650 ℃ and the time is 3-6 h.
14. An iron phosphate, wherein the iron phosphate is obtainable by the process according to any one of claims 9 to 13.
15. A lithium iron phosphate positive electrode material, wherein the lithium iron phosphate positive electrode material is prepared by using the iron phosphate according to claim 14.
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