CN105024072A - Method for preparing ferric pyrophosphate used for lithium ion battery by utilizing iron-bearing raffinate - Google Patents
Method for preparing ferric pyrophosphate used for lithium ion battery by utilizing iron-bearing raffinate Download PDFInfo
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- CN105024072A CN105024072A CN201510454831.0A CN201510454831A CN105024072A CN 105024072 A CN105024072 A CN 105024072A CN 201510454831 A CN201510454831 A CN 201510454831A CN 105024072 A CN105024072 A CN 105024072A
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- iron
- acid
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- extraction
- raffinate
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 235000007144 ferric diphosphate Nutrition 0.000 title claims abstract description 6
- 239000011706 ferric diphosphate Substances 0.000 title claims abstract description 6
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 title claims abstract description 6
- 229940036404 ferric pyrophosphate Drugs 0.000 title claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 41
- 239000012266 salt solution Substances 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000012074 organic phase Substances 0.000 claims abstract description 10
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 49
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 150000002505 iron Chemical class 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- 239000003002 pH adjusting agent Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 8
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 6
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 16
- 239000002699 waste material Substances 0.000 description 15
- 239000005955 Ferric phosphate Substances 0.000 description 9
- 229940032958 ferric phosphate Drugs 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- -1 catalysis Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 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 2
- 235000021110 pickles Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000013313 FeNO test Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for preparing ferric pyrophosphate used for a lithium ion battery by utilizing iron-bearing raffinate. The method comprises the following steps of (1) adding oxidizing agent solution in the iron-bearing raffinate, stirring, adding the raffinate to carry out multistage extraction, and washing a separated organic phase through inorganic acid to obtain ferric salt solution; and (2) taking the ferric salt solution in the step (1) as an iron source, adding a phosphorus source, stirring, adding a pH regulator to react, cooling, carrying out solid-liquid separation, washing and drying to obtain a battery-level ferric pyrophosphate powder material. According to the method, the ferric salt solution recycled from the iron-bearing raffinate is taken as the iron source to prepare ferric pyrophosphate, so that the scrap metallic iron is recycled to the greatest extent, the economic benefit is improved, the environmental pollution is reduced; the whole preparation process is greatly simplified, and the production cost is reduced.
Description
Technical field
The present invention relates to field of lithium ion battery material, be specifically related to a kind of method of lithium ion battery ferric orthophosphate, particularly relate to a kind of ferro element of reclaiming in iron content raffinate of utilizing and prepare the method for lithium ion battery ferric orthophosphate for source of iron
Background technology
Due to ferric orthophosphate (FePO
4) there is abundant chemical constitution, in fields such as lithium ion battery material, catalysis, glass-ceramic and agriculturals, there is extensive use.Through the development of Market Selection and research and development technology, anode material for lithium-ion batteries LiFePO4 (LiFePO
4) main flow preparation technology progressively turn to ferric phosphate technique by ferrous oxalate technique, by the usual better performances of LiFePO 4 material that this method is obtained, be suitable for preparing medium-to-high grade lithium battery product.This synthesis technique has following advantage: first, in the process of ferric phosphate synthesis, by the optimization of synthesis technique, the performance to iron phosphate material can be realized, as accuracy controlling such as composition, crystal formation and patterns, and then obtain high-quality battery-grade iron phosphate and LiFePO 4 material; The second, prepare in the process of LiFePO4, ferric phosphate and lithium source can be similar at carbothermic reduction reaction to be regarded as: FePO
4body skeleton remain unchanged, Li
+insert FePO
4lattice in, thus ferric phosphate becomes LiFePO4, and this building-up process is simple and easy to control, and material consistency is better.
The raw material of industrial production ferric phosphate generally includes source of iron, phosphorus source, oxidant and alkali lye, and current source of iron adopts trivalent iron salt or divalent iron salt usually, and the source of iron disclosed in CN102491302A and CN102555725B is ferrous sulfate (FeSO
4), frerrous chloride (FeCl
2), ferric nitrate (FeNO
3) and iron chloride (FeCl
3) etc., make divalent iron salt be oxidized to trivalent iron salt by adding oxidant, the shortcoming of this method is the use of non-renewable resources, and the use of trivalent iron salt, oxidant and alkali lye simultaneously adds the production cost of ferric phosphate.CN104409732A discloses a kind of preparation method adopting the LiFePO 4 material of mixing source of iron, it adopts a certain proportion of di-iron trioxide and ferric orthophosphate to prepare LiFePO4, reduce cost of material, and the lithium iron phosphate anode active material of preparation maintains the features such as processing characteristics is good when being used as lithium ion anode material, but still there is the higher defect of cost in it.
At present, people reclaim to waste metal that to pay close attention to be more the lifting of its economic benefit and output, but pay close attention to less to the process of the relatively low iron of price and reclaiming.The steps such as the major part recovery process employing of waste metal material processed factory is acid-soluble, extraction, condensing crystallizing, only reclaim more valuable metal, as gold, silver, nickel, chromium, manganese etc., and iron causes unmanned recovery because economic benefit is lower, but normal containing a large amount of iron ion in waste liquid after actual treatment; Waste liquid after this extraction just can carry out discharging of waste liquid after still needing process; The scum simultaneously filtered out can only be done waste treatment or resell to scum treatment plant.So not only this processing mode cannot obtain resource regeneration to greatest extent, also can cause certain environmental pollution simultaneously and reduce the economic benefit of producer.
CN101462704A discloses a kind of production method of ultrafine cell level ferric orthophosphate, and its ferrous salt solution adopted derives from the waste residue of titanium white production discharge or industrial acid-washed waste liquid; Wherein the manufacture method of ferrous salt solution is: the production waste particle containing ferrous sulfate of titanium white production being discharged drops in water, heating is fully dissolved and after precipitate and separate, is got its clarified solution as the ferrous salt solution producing ferric orthophosphate, or the pickle liquor containing ferrous sulfate is added waste iron filing reaction and consume spent acid amount, get its clarified solution as the ferrous salt solution producing ferric orthophosphate.But the extraction of this ferrous salt solution is comparatively thick, and the inside still has a large amount of impurity, and active ingredient concentration is lower.
Therefore, how to design a kind of effective recovery ferro element from iron content waste liquid and it can be used as source of iron to be current problem demanding prompt solution for the preparation of ferric orthophosphate.
Summary of the invention
For solving the deficiency that prior art exists, the object of the present invention is to provide a kind of method of lithium ion battery ferric orthophosphate, it is prepared to reclaim the iron salt solutions obtained from iron content raffinate as source of iron, not only achieve the regeneration to greatest extent of waste metal iron, also improve economic benefit simultaneously and reduce environmental pollution; And enormously simplify whole preparation process, reduce production cost.
For reaching this object, the present invention by the following technical solutions:
The invention provides a kind of method utilizing iron content raffinate to prepare lithium ion battery ferric orthophosphate, comprise the following steps:
(1) first in iron content raffinate, add oxidizing agent solution, stir, then add extractant and carry out multitple extraction, pH adjusting agent adjust ph is 0.5-5, and isolated organic phase obtains iron salt solutions after inorganic acid washing;
(2) using the iron salt solutions of step (1) as source of iron, add phosphorus source, stir, add pH adjusting agent and react, cooling, then obtains battery level ferric pyrophosphate dusty material after Separation of Solid and Liquid, washing, oven dry.
In step of the present invention (1), when carrying out the recovery of ferro element in iron content raffinate, first add oxidant, and then after adding extractant, also can add a certain amount of pH adjusting agent, and this oxidant and pH adjusting agent prepare the raw material required for lithium ion battery ferric orthophosphate just, therefore, in step (2), when carrying out the preparation of lithium ion battery ferric orthophosphate, the consumption of pH adjusting agent also can be reduced without the need to adding oxidant again, thus, relative to prior art, present invention achieves the omission to said components, but the preparation of lithium ion battery ferric orthophosphate can be realized equally, and its effect is suitable.
In step of the present invention (1), multitple extraction refers to extraction 3-10 time, and the purity making step (1) obtain molysite reaches more than 99.9%.
In the present invention, the described iron content raffinate of step (1) is the solution containing divalence and/or ferric ion.
Oxidant described in the present invention is the combination of any one or at least two kinds in hydrogen peroxide, clorox, sodium peroxide or sodium perchlorate, be preferably the combination of any one or at least two kinds in hydrogen peroxide, sodium peroxide or sodium perchlorate, more preferably hydrogen peroxide.
In the present invention, the quality of step (1) described oxidant is the 10-300% of iron content raffinate quality, can be such as 10%, 20%, 50%, 80%, 100%, 120%, 150%, 180%, 200%, 220%, 230%, 250%, 270%, 280%, 300%, be preferably 50-200%, more preferably 120%.
In the present invention, step (1) described extractant is organic phosphoric acid kind of extractants.
The kind of extractants of organic phosphoric acid described in the present invention is the combination of any one or at least two kinds in P204, P507, N290 or 5709, is preferably the combination of any one or at least two kinds in P204, P507 or N290.The Chinese of P204 is called di-(2-ethylhexyl)phosphoric acid, the Chinese of P507 is called 2-ethylhexyl phosphoric acid list-2-Octyl Nitrite, the Chinese by name two (2 of N290,4,4)-tri-methyl-amyl phosphonic acids, the Chinese of 5709 is called isoalkyl phosphonic acids (1-methyl-heptyl) ester.
In the present invention, the mass ratio of step (1) described extractant and solution is 1:100-4000, can be such as 1:100,1:200,1:400,1:500,1:650,1:800,1:1000,1:1200,1:1500,1:1800,1:2000,1:2500,1:2800,1:3000,1:3200,1:3500,1:4000, be preferably 1:500-1000, more preferably 1:650.
In the present invention, the temperature of step (1) described extraction is 10-80 DEG C, it can be such as 10 DEG C, 12 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 42 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, be preferably 20-60 DEG C, more preferably 42 DEG C.
In the present invention, the pH value of step (1) described extraction is 0.5-5, such as, can be 0.5,0.8,1,1.2,1.5,2,2.5,2.8,3,3.2,3.5,3.8,4,4.5,5, is preferably 1.5-3, more preferably 2.
In the present invention, step (1) described pH adjusting agent is acid or alkali, and described acid is preferably the combination of any one or at least two kinds in sulfuric acid, nitric acid or hydrochloric acid, and described alkali is preferably NaOH and/or ammoniacal liquor.
In the present invention, the time of step (1) described extraction is 0.5-5h, can be such as 0.5h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, 4.5h, 5h, preferably 1.5-3h, more preferably 2.2h.
In the present invention, the time of step (1) described stirring is 1-10h, can be such as 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, 4.5h, 5h, 6h, 7h, 8h, 9h, 10h, be preferably 2-6h, more preferably 5h.
In the present invention, step (1) described inorganic acid is the combination of any one or at least two kinds in sulfuric acid, nitric acid or hydrochloric acid.
In the present invention, the described phosphorus source of step (2) is the combination of any one or at least two kinds in phosphoric acid, ammonium dihydrogen phosphate or ammonium hydrogen phosphate.
In the present invention, step (2) described reaction temperature is 40-90 DEG C, such as, can be 40 DEG C, 42 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 90 DEG C, is preferably 60-80 DEG C, more preferably 65 DEG C.
In the present invention, step (2) described pH adjusting agent is acid or alkali, and described acid is preferably the combination of any one or at least two kinds in phosphoric acid or phosphate, and described alkali is preferably NaOH and/or ammoniacal liquor.
In the present invention, step (2) adds pH adjusting agent adjust ph is 0.5-5, such as, can be 0.5,0.8,1,1.2,1.5,2,2.5,2.8,3,3.2,3.5,3.8,4,4.5,5, is preferably 1.5-2.5, more preferably 2.
In the present invention, step (2) the described reaction time is 1-24h, such as, can be 1h, 2h, 5h, 10h, 12h, 13h, 15h, 16h, 18h, 20h, 21h, 22h, 23h, 24h, is preferably 2-20h, more preferably 10h.
As the preferred technical scheme of the present invention, described method can comprise the following steps:
(1) in iron content raffinate, add oxidizing agent solution, the quality of described oxidant is the 10-300% of iron content raffinate quality, stirs 1-10h, and the reaction temperature controlling solution is 10-80 DEG C, and pH value is between 0.5-5; Add extractant multitple extraction, in every grade of extraction tank, the mass ratio of extractant and solution is 1:100-4000, and extraction temperature is 10-80 DEG C, and pH value is between 0.5-5, and extraction 0.5-3h, isolates organic phase and obtain iron salt solutions after inorganic acid washing;
(2) iron salt solutions step (1) reclaimed is as source of iron, add phosphorus source or phosphate, stir, reaction temperature is 60-80 DEG C, add pH adjusting agent to pH value between 0.5-5, reaction 1-24h, cooling, then after Separation of Solid and Liquid, washing, oven dry, obtain lithium ion battery ferric orthophosphate dusty material.
Two of object of the present invention is also the lithium ion battery ferric orthophosphate dusty material obtained according to method as described in the first aspect of the invention.
The particle diameter of the primary particle of the lithium ion battery ferric orthophosphate dusty material obtained in the present invention is 10-100nm.
Compared with prior art, the present invention at least has following beneficial effect:
(1) preparation method of the present invention can realize the regeneration to greatest extent of waste metal iron, the purity of its iron salt solutions obtained can reach more than 99.9%, effectively improve the utilance of ferro element in iron content extract, saved production cost, decreased environmental pollution simultaneously.
(2) the present invention is by adopting specific way of recycling to iron content raffinate, can simplify the whole process preparing lithium ion battery ferric orthophosphate method, and save used raw material, improve production efficiency, and save production cost.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
(1) in iron content raffinate, add hydrogen peroxide solution, the quality of described hydrogen peroxide is 10% of iron content raffinate quality, stirs 2h, and the reaction temperature controlling solution is 20 DEG C, and pH value is 2; Add organic phosphoric acid kind of extractants P204 and carry out multitple extraction, in every grade of extraction tank, the mass ratio of extractant and solution is 1:200, and extraction temperature is 20 DEG C, and pH value is 2, extraction 1h, isolates organic phase and obtain iron salt solutions after inorganic acid washing;
(2) iron salt solutions step (1) reclaimed, as source of iron, adds phosphoric acid, stirs, reaction temperature is 55 DEG C, and adding pH adjusting agent to pH value is 2, reaction 2h, cooling, then after Separation of Solid and Liquid, washing, oven dry, obtain lithium ion battery ferric orthophosphate dusty material.
Embodiment 2
(1) in iron content raffinate, add liquor natrii hypochloritis, the quality of described clorox is 30% of iron content raffinate quality, stirs 3h, and the reaction temperature controlling solution is 40 DEG C, and pH value is 1.5; Add organic phosphoric acid kind of extractants P507 and carry out multitple extraction, in every grade of extraction tank, the mass ratio of extractant and solution is 1:400, and extraction temperature is 10 DEG C, and pH value is 1.5, extraction 1.5h, isolates organic phase and obtain iron salt solutions after inorganic acid washing;
(2) iron salt solutions step (1) reclaimed, as source of iron, adds ammonium dihydrogen phosphate, stirs, reaction temperature is 65 DEG C, and adding pH adjusting agent to pH value is 2, reaction 5h, cooling, then after Separation of Solid and Liquid, washing, oven dry, obtain lithium ion battery ferric orthophosphate dusty material.
Embodiment 3
(1) in iron content raffinate, add sodium peroxide solution, the quality of described sodium peroxide is 100% of iron content raffinate quality, stirs 5h, and the reaction temperature controlling solution is 70 DEG C, and pH value is 3; Add organic phosphoric acid kind of extractants N290 and carry out multitple extraction, in every grade of extraction tank, the mass ratio of extractant and solution is 1:800, and extraction temperature is 70 DEG C, and pH value is 1.5, extraction 2.5h, isolates organic phase and obtain iron salt solutions after inorganic acid washing;
(2) iron salt solutions step (1) reclaimed, as source of iron, adds ammonium dihydrogen phosphate, stirs, reaction temperature is 72 DEG C, and adding pH adjusting agent to pH value is 2, reaction 8h, cooling, then after Separation of Solid and Liquid, washing, oven dry, obtain lithium ion battery ferric orthophosphate dusty material.
Embodiment 4
(1) in iron content raffinate, add sodium perchlorate solution, the quality of described sodium perchlorate is 200% of iron content raffinate quality, stirs 8h, and the reaction temperature controlling solution is 75 DEG C, and pH value is 4; Add organic phosphoric acid kind of extractants 5709 and carry out multitple extraction, in every grade of extraction tank, the mass ratio of extractant and solution is 1:2000, and extraction temperature is 80 DEG C, and pH value is 2, extraction 2.5h, isolates organic phase and obtain iron salt solutions after inorganic acid washing;
(2) iron salt solutions step (1) reclaimed is as source of iron, add ammonium hydrogen phosphate, stir, reaction temperature is 60 DEG C, adding pH adjusting agent to pH value is 2, reaction 11h, cooling, then after Separation of Solid and Liquid, washing, oven dry, obtain lithium ion battery ferric orthophosphate dusty material.
Embodiment 5
(1) in iron content raffinate, add sodium peroxide solution, the quality of described sodium peroxide is 300% of iron content raffinate quality, stirs 10h, and the reaction temperature controlling solution is 60 DEG C, and pH value is 5; Add organic phosphoric acid kind of extractants and carry out multitple extraction, in every grade of extraction tank, the mass ratio of extractant and solution is 1:4000, and extraction temperature is 80 DEG C, and pH value is 1.5, extraction 3h, isolates organic phase and obtain iron salt solutions after inorganic acid washing;
(2) iron salt solutions step (1) reclaimed, as source of iron, adds phosphoric acid, stirs, reaction temperature is 80 DEG C, and adding pH adjusting agent to pH value is 2, reaction 24h, cooling, then after Separation of Solid and Liquid, washing, oven dry, obtain lithium ion battery ferric orthophosphate dusty material.
Following comparative example 1 is the preparation method directly adopting ferrous salt solution to carry out lithium ion battery ferric orthophosphate dusty material, and comparative example 2 and 3 is and adopts other method reclaiming ferro element with the preparation method providing source of iron to carry out lithium ion battery ferric orthophosphate lithium powder material.
Comparative example 1
(1) in catalytic reaction kettle, add ferrous salt solution, after adjustment pH, add hydrogen peroxide, make it that exothermic reaction occur, controlling its temperature is 55 DEG C, pH=2;
(2) dissolved phosphorus hydrochlorate being joined in catalytic reaction kettle and strong stirring, add soda ash or ammonia adjusted to ph, controlling its temperature is 55 DEG C, and pH=2, obtains ferric phosphate sizing agent; Lithium ion battery ferric orthophosphate dusty material is obtained again after Separation of Solid and Liquid, washing, oven dry.
Comparative example 2
(1) drop in water by the production waste particle containing ferrous sulfate that titanium white production is discharged, heating is fully dissolved and after sedimentation separation, is got its clarified solution as the ferrous salt solution producing ferric orthophosphate;
(2) in catalytic reaction kettle, add ferrous salt solution, after adjustment pH, add hydrogen peroxide, make it that exothermic reaction occur, controlling its temperature is 55 DEG C, pH=2;
(3) dissolved phosphorus hydrochlorate being joined in catalytic reaction kettle and strong stirring, add soda ash or ammonia adjusted to ph, controlling its temperature is 55 DEG C, and pH=2, obtains ferric phosphate sizing agent; Lithium ion battery ferric orthophosphate dusty material is obtained again after Separation of Solid and Liquid, washing, oven dry.
Comparative example 3
(1) pickle liquor containing ferrous sulfate is added waste iron filing reaction and consume spent acid amount, get its clarified solution as the ferrous salt solution producing ferric orthophosphate;
(2) in catalytic reaction kettle, add ferrous salt solution, after adjustment pH, add hydrogen peroxide, make it that exothermic reaction occur, controlling its temperature is 55 DEG C, pH=2;
(3) dissolved phosphorus hydrochlorate being joined in catalytic reaction kettle and strong stirring, add soda ash or ammonia adjusted to ph, controlling its temperature is 55 DEG C, and pH=2, obtains ferric phosphate sizing agent; Lithium ion battery ferric orthophosphate dusty material is obtained again after Separation of Solid and Liquid, washing, oven dry.
Compared in performance by lithium ion battery ferric orthophosphate dusty material obtained by embodiment 1-5 and comparative example 1-3, comparative result is as shown in table 1.
Table 1
Data as can be seen from upper table, relative to comparative example 1-3, the lithium ion battery ferric orthophosphate dusty material adopting method of the present invention to prepare has comparatively suitable ferrophosphorus ratio, and its specific area and tap density are comparatively large simultaneously, and sulfate radical foreign matter content is less; Therefore, relative to the molysite in other source, the high and function admirable of the ferric orthophosphate dusty material purity adopting method of the present invention to prepare.Simultaneously, the present invention comes from the molysite of iron content raffinate by adopting, also achieve and use the omission of the preparations such as oxidant in the preparation process of lithium ion battery ferric orthophosphate, but still can keep the superperformance of ferric orthophosphate dusty material, therefore, it has important using value.
Applicant states, the present invention illustrates process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned processing step, does not namely mean that the present invention must rely on above-mentioned processing step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (9)
1. utilize iron content raffinate to prepare a method for lithium ion battery ferric orthophosphate, it is characterized in that, comprise the following steps:
(1) first in iron content raffinate, add oxidizing agent solution, stir, then add extractant and carry out multitple extraction, pH adjusting agent adjust ph is 0.5-5, and isolated organic phase obtains iron salt solutions after inorganic acid washing;
(2) using the iron salt solutions of step (1) as source of iron, add phosphorus source, stir, add pH adjusting agent and react, cooling, then obtains battery level ferric pyrophosphate dusty material after Separation of Solid and Liquid, washing, oven dry.
2. method according to claim 1, is characterized in that, the described iron content raffinate of step (1) is the solution containing divalence and/or ferric ion;
Preferably, described oxidant is the combination of any one or at least two kinds in hydrogen peroxide, clorox, sodium peroxide or sodium perchlorate, be preferably the combination of any one or at least two kinds in hydrogen peroxide, sodium peroxide or sodium perchlorate, more preferably hydrogen peroxide;
Preferably, the quality of described oxidant is the 10-300% of iron content raffinate quality, is preferably 50-200%, more preferably 120%.
3. method according to claim 1 and 2, is characterized in that, step (1) described extractant is organic phosphoric acid kind of extractants;
Preferably, described organic phosphoric acid kind of extractants is the combination of any one or at least two kinds in P204, P507, N290 or 5709, is preferably the combination of any one or at least two kinds in P204, P507 or N290;
Preferably, the mass ratio of described extractant and solution is 1:100-4000, is preferably 1:500-1000, more preferably 1:650.
4. the method according to any one of claim 1-3, is characterized in that, the temperature of step (1) described extraction is 10-80 DEG C, is preferably 20-60 DEG C, more preferably 42 DEG C;
Preferably, described pH value is 0.5-4, is preferably 1.5-3, more preferably 2;
Preferably, step (1) described pH adjusting agent is acid or alkali, and described acid is preferably the combination of any one or at least two kinds in sulfuric acid, nitric acid or hydrochloric acid, and described alkali is preferably NaOH and/or ammoniacal liquor;
Preferably, the time of described extraction is 0.5-5h, is preferably 1.5-3h, more preferably 2.2h.
5. the method according to any one of claim 1-4, is characterized in that, the time of step (1) described stirring is 1-10h, is preferably 2-6h, more preferably 5h;
Preferably, described inorganic acid is the combination of any one or at least two kinds in sulfuric acid, nitric acid or hydrochloric acid.
6. the method according to any one of claim 1-5, is characterized in that, the described phosphorus source of step (2) is the combination of any one or at least two kinds in phosphoric acid, ammonium dihydrogen phosphate or ammonium hydrogen phosphate.
7. the method according to any one of claim 1-6, is characterized in that, step (2) described reaction temperature is 40-90 DEG C, is preferably 60-80 DEG C, more preferably 65 DEG C;
Step (2) described pH adjusting agent is acid or alkali, and described acid is preferably the combination of any one or at least two kinds in phosphoric acid or phosphate, and described alkali is preferably NaOH and/or ammoniacal liquor;
Preferably, adding pH adjusting agent adjust ph in step (2) is 0.5-5, is preferably 1.5-2.5, more preferably 2;
Preferably, the described reaction time is 1-24h, is preferably 2-20h, more preferably 10h.
8. the method according to any one of claim 1-7, is characterized in that, comprises the following steps:
(1) in iron content raffinate, add oxidizing agent solution, the quality of described oxidant is the 10-300% of iron content raffinate quality, stirs 1-10h, and the reaction temperature controlling solution is 10-80 DEG C, and pH value is between 0.5-5; Add extractant multitple extraction, in every grade of extraction tank, the mass ratio of extractant and solution is 1:100-4000, and extraction temperature is 10-80 DEG C, and pH value is between 0.5-5, and extraction 0.5-3h, isolates organic phase and obtain iron salt solutions after inorganic acid washing;
(2) iron salt solutions step (1) reclaimed is as source of iron, add phosphorus source or phosphate, stir, reaction temperature is 60-80 DEG C, add pH adjusting agent to pH value between 0.5-5, reaction 1-24h, cooling, then after Separation of Solid and Liquid, washing, oven dry, obtain lithium ion battery ferric orthophosphate dusty material.
9. the lithium ion battery ferric orthophosphate dusty material that the method according to any one of claim 1-8 obtains.
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| CN112289992A (en) * | 2020-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | High-performance lithium iron phosphate and preparation method and application of steel pickling waste liquid thereof |
| CN112289992B (en) * | 2020-10-20 | 2022-04-12 | 合肥国轩高科动力能源有限公司 | Method for preparing lithium iron phosphate from steel pickling waste liquid and application |
| CN112174106A (en) * | 2020-11-03 | 2021-01-05 | 张响 | Battery-grade iron phosphate and preparation method thereof |
| CN115231538A (en) * | 2022-07-06 | 2022-10-25 | 曲靖市德方纳米科技有限公司 | Preparation method and application of ferrophosphorus source |
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