CN116835545A - Method for desulfurizing ferric phosphate - Google Patents
Method for desulfurizing ferric phosphate Download PDFInfo
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- CN116835545A CN116835545A CN202210297652.0A CN202210297652A CN116835545A CN 116835545 A CN116835545 A CN 116835545A CN 202210297652 A CN202210297652 A CN 202210297652A CN 116835545 A CN116835545 A CN 116835545A
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- Prior art keywords
- iron phosphate
- phosphate
- aging
- desulfurized
- ferric phosphate
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 185
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 88
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 88
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 84
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 24
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 97
- 238000001354 calcination Methods 0.000 claims abstract description 54
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 45
- 239000011593 sulfur Substances 0.000 claims abstract description 45
- 230000032683 aging Effects 0.000 claims abstract description 39
- 239000003929 acidic solution Substances 0.000 claims abstract description 34
- 238000000227 grinding Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- 238000001238 wet grinding Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000007790 solid phase Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000001307 helium Substances 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000003483 aging Methods 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 238000006477 desulfuration reaction Methods 0.000 description 13
- 230000023556 desulfurization Effects 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 235000003891 ferrous sulphate Nutrition 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 6
- 239000003082 abrasive agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IYTVWFLTBYCNAD-UHFFFAOYSA-K O.O.O.O.O.O.O.[Fe+3].[O-]P([O-])([O-])=O Chemical compound O.O.O.O.O.O.O.[Fe+3].[O-]P([O-])([O-])=O IYTVWFLTBYCNAD-UHFFFAOYSA-K 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 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 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 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
- 229940085991 phosphate ion Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention provides a method for desulfurizing ferric phosphate, which comprises the following steps: (1) Calcining and/or grinding the iron phosphate to be desulfurized to obtain treated iron phosphate; (2) And aging the treated ferric phosphate in water or an acidic solution to obtain the desulphurized ferric phosphate. The method is simple to operate, low in cost, capable of obtaining the ferric phosphate with low sulfur content, free of any harmful substances in the treatment process, and environment-friendly.
Description
Technical Field
The invention relates to the technical field of ferric phosphate purification, in particular to a method for desulfurizing ferric phosphate.
Background
The lithium iron phosphate battery material has been applied to various electric automobiles and communication equipment at present due to the advantages of large discharge capacity, long cycle life, high safety, environmental friendliness and the like. And the quality of the ferric phosphate, which is an important precursor for preparing lithium iron phosphate, has a very important influence on the electrochemical performance of the battery. Ferrous sulfate is one of the iron sources for preparing ferric phosphate, and has the advantages of easy availability and low cost, so that the ferrous sulfate is widely applied. However, the introduction of sulfate also increases the burden of the subsequent washing process, and a large amount of salt-containing wastewater is generated, so that the treatment cost is increased.
CN107902637a discloses a method for producing high-purity ferric phosphate, which comprises the steps of carrying out three impurity removal and purification treatments on ferrous sulfate solution obtained by dissolving raw material ferrous sulfate heptahydrate crystals for producing ferric phosphate or ferrous sulfate solution generated by reacting iron with sulfuric acid, generating ferric sulfate solution by oxidizing the purified ferrous sulfate solution with hydrogen peroxide, then dropwise adding phosphate solution under the condition of emulsifying agent for reaction to synthesize ferric phosphate precipitate, or adding phosphoric acid into the purified ferrous sulfate solution, stirring, adding hydrogen peroxide for oxidation, adding emulsifying agent, synthesizing ferric phosphate precipitate, and then aging, rinsing, filtering and drying the ferric phosphate precipitate to obtain the water-containing or anhydrous high-purity ferric phosphate. However, the method has complicated process, and a large amount of reagent is added in the process to remove impurities, so that the cost is high.
CN108046229a discloses a method for comprehensively desulfurizing battery-grade anhydrous ferric phosphate, which mainly controls desulfurization from three links in the production process of ferric phosphate, specifically reduces sulfur content by adding a certain amount of emulsifying agent, forming emulsion under strong stirring, adding morphology control agent and other means to control crystal form and granularity; in the washing process, the sulfur content is reduced through three-stage washing, namely 0.05% citric acid solution washing, absolute ethyl alcohol washing and 60 ℃ hot water washing are sequentially carried out to replace the traditional pure water washing mode; the particles are crushed to 1-5 um in advance before dehydration, the particle size is thinned, and the dehydration temperature is increased to 650 ℃, so that the sulfur content is reduced. However, the method has longer operation flow, uses more expensive citric acid in the process, still needs to carry out innocent treatment on the wastewater after washing, and cannot realize industrialized application at present.
CN109179358A discloses a method for preparing battery-grade ferric phosphate from waste lithium iron phosphate batteries. The method can prepare the anhydrous battery-grade ferric phosphate through battery disassembly and separation, alkaline leaching, acid leaching, oxidation, precipitation and calcination. Firstly, acid leaching and precipitation are carried out after alkaline leaching, so that impurities such as aluminum in lithium iron phosphate can be removed, and the purity of the iron phosphate is improved; the new filter residue is leached after the lithium-rich solution is repeatedly supplemented with acid, so that the concentration of lithium in the solution and the recovery rate of lithium are improved, and the recovery cost of lithium is reduced; the low pH value (1.0-2.5) at the end of the precipitation can reduce the tendency of ferric hydroxide generation, and the aging process carried out after the precipitation reaction is finished can improve the purity of ferric phosphate, so that the obtained ferric phosphate meets the industrial use standard. However, the process has more operation steps, uses a large amount of reagents in the process, and has higher cost.
CN11646447a discloses a method for recovering iron phosphate from iron phosphate slag after lithium extraction of lithium iron phosphate battery, firstly mixing the iron phosphate slag after lithium extraction of lithium iron phosphate battery with water, mixing, reacting with acid, solid-liquid separating to obtain leaching solution containing iron phosphate ion, adding iron to replace copper and removing aluminum by resin to obtain purifying solution, adding iron phosphate heptahydrate or phosphoric acid to prepare phosphorus-iron ratio, obtaining synthetic stock solution with certain ratio of P to Fe, adding hydrogen peroxide and ammonia water, regulating pH to obtain iron phosphate precursor precipitate, and post-treating to obtain battery grade iron phosphate precursor product. However, the process still generates a large amount of ammonia nitrogen wastewater, which has a certain influence on the environment.
Therefore, there is a need to develop a method for desulfurizing iron phosphate that is efficient, economical, has little waste after treatment, and has little environmental impact.
Disclosure of Invention
In view of the problems existing in the prior art, the invention provides a method for desulfurizing iron phosphate, which is characterized in that iron phosphate after desulfurization is firstly calcined and then aged in an acid solution to obtain iron phosphate with low sulfur content, wherein the sulfur content in the iron phosphate after desulfurization is lower than 100ppm, the method is simple to operate and low in cost, no harmful substances are generated in the treatment process, and the method is an environment-friendly treatment mode.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for desulfurizing ferric phosphate, which comprises the following steps:
(1) Calcining and/or grinding the iron phosphate to be desulfurized to obtain treated iron phosphate;
(2) And aging the treated ferric phosphate in water or an acidic solution to obtain the desulphurized ferric phosphate.
According to the method, anhydrous ferric phosphate is obtained by calcining ferric phosphate to be desulfurized, and/or the particle size of the ferric phosphate to be desulfurized is controlled in a specific range in a grinding material mode, and meanwhile, lattice distortion of the ferric phosphate to be desulfurized is realized, sulfur carried by the ferric phosphate to be desulfurized in crystal growth lattice gaps is exposed, then, through liquid-phase aging, sulfur existing among the crystal boundaries of the ferric phosphate is washed out, and meanwhile, the crystal structure of the ferric phosphate is adjusted, and then, separation of sulfur and the ferric phosphate is realized, so that the desulfurized ferric phosphate is obtained.
The method for desulfurizing the ferric phosphate is only combined with the water or acid liquor aging step by means of calcination and/or grinding, is simple to operate, can recycle the acid liquor for aging, does not generate waste liquid, has low cost, and is suitable for industrial large-scale production process.
Preferably, the source of iron phosphate to be desulphurized in step (1) comprises any one or a combination of at least two of a coprecipitation method, a crystallization method, a hydrothermal method, a sol-gel method or a template method, wherein typical but non-limiting combinations are combinations of a coprecipitation method and a hydrothermal method, combinations of a hydrothermal method and a sol-gel method, combinations of a sol-gel method and a template method, combinations of a hydrothermal method, a sol-gel method and a template method, combinations of crystallization method, a sol-gel method and a template method, and the like.
As a preferable embodiment of the present invention, the content of sulfur in the iron phosphate to be desulfurized is 0.01-8 wt%, for example, 0.01wt%, 0.1wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, or 8wt%, etc., but not limited to the recited values, other non-recited values within the range are equally applicable.
Preferably, the sulfur in the iron phosphate to be desulphurized comprises inorganic sulfur.
Preferably, the inorganic sulfur is present in a form that includes any one or a combination of at least two of sulfate, sulfide, or elemental sulfur, wherein typical but non-limiting combinations are sulfate and sulfide combinations, elemental sulfur and sulfide combinations, and the like.
The temperature of the calcination in the step (1) is preferably 100 to 900 ℃, and may be, for example, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, or the like, but not limited to the values recited, and other values not recited in the range are equally applicable.
The calcination time is preferably 0.1 to 20 hours, and may be, for example, 10min, 30min, 60min, 120min, 180min, 240min, 720min, 900min or 1200min, etc., but not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the calcination in step (1) is performed under a non-reducing atmosphere.
The invention further proceeds under non-reducing atmosphere, which can further prevent the reduction of ferric phosphate.
Preferably, the non-reducing atmosphere comprises an oxidizing atmosphere and/or an inert atmosphere.
Preferably, the oxidizing atmosphere comprises oxygen and/or air.
Preferably, the inert atmosphere comprises any one or a combination of at least two of nitrogen, argon, helium or carbon dioxide, wherein typical but non-limiting combinations are combinations of nitrogen and argon, combinations of helium and argon, combinations of nitrogen and helium, combinations of carbon dioxide and argon, and combinations of nitrogen and carbon dioxide.
Preferably, the means for grinding material in step (1) comprises any one or a combination of at least two of stirring mill, ball mill, sand mill or air mill, wherein typical but non-limiting combinations are stirring mill and ball mill combinations, ball mill and sand mill combinations, sand mill and air mill combinations.
Preferably, the means of stirring, ball milling or sanding comprises dry milling or wet milling.
Preferably, the wet milling medium comprises any one or a combination of at least two of methanol, ethanol, propanol, water, dilute hydrochloric acid, dilute sulfuric acid, dilute phosphoric acid, dilute nitric acid, dilute acetic acid or dilute citric acid, wherein typical but non-limiting combinations are combinations of methanol and ethanol, ethanol and propanol, dilute hydrochloric acid and dilute sulfuric acid, dilute phosphoric acid and dilute nitric acid, and dilute citric acid and dilute nitric acid.
Preferably, the pH of the wet-milling medium is not less than 1.0, and may be, for example, 1.0, 1.2, 1.3, 1.5, 1.8, 2.0, 2.2, 2.3, 2.5, 3.0, 3.5, 5.0, 6.0, 7.0, or the like.
The particle diameter D50 of the stirred and milled material is preferably 15. Mu.m, for example, 15. Mu.m, 14. Mu.m, 13. Mu.m, 12. Mu.m, 10. Mu.m, 8. Mu.m, or 7. Mu.m, but not limited to the values recited, and other values not recited in the range are applicable.
Preferably, the particle diameter D50 of the material after ball milling is 15 μm or less, for example, 15 μm, 14 μm, 13 μm, 12 μm, 10 μm, 8 μm or 7 μm, etc., but not limited to the recited values, and other values not recited in the range are equally applicable.
The particle diameter D50 of the material after sand milling is preferably not more than 10. Mu.m, for example, 10. Mu.m, 9. Mu.m, 8. Mu.m, 7. Mu.m, 6. Mu.m, 5. Mu.m, 4. Mu.m, 1. Mu.m, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the material D50 after the air flow grinding is 15 μm or less, for example, 15 μm, 14 μm, 13 μm, 12 μm, 10 μm, 8 μm or 7 μm, etc., but not limited to the recited values, and other values not recited in the range are equally applicable.
The process parameters of the abrasive are not particularly limited, and any parameters known to those skilled in the art to be applicable to the abrasive may be used, and may be adjusted according to the actual process.
Preferably, the wet ground slurry after wet grinding is directly aged or the wet ground slurry after wet grinding is aged after the wet grinding medium is removed through solid-liquid separation.
When the wet-milling medium contains any one or a combination of at least two of methanol, ethanol or propanol, it is preferable that the wet-milling slurry is aged after the medium (methanol, ethanol or propanol) is removed by solid-liquid separation.
When the wet grinding medium comprises any one or a combination of at least two of water, dilute hydrochloric acid, dilute sulfuric acid, dilute phosphoric acid, dilute nitric acid, dilute acetic acid or dilute citric acid, the wet grinding medium can be directly aged or can be removed by solid-liquid separation and then aged.
Preferably, the iron phosphate to be desulphurized in step (1) is preferably calcined and ground sequentially or preferably ground sequentially and calcined to obtain the treated iron phosphate.
The invention further preferably carries out calcination and then grinding, because the dihydrate iron phosphate is firstly converted into anhydrous iron phosphate in the calcination process, the granularity is not reduced in the subsequent grinding process, and the crystal lattice of the anhydrous iron phosphate is further distorted due to the accumulation of energy applied by external force, so that the method is better than the crystal transformation in the subsequent aging process, and the removal of inter-lattice sulfur is realized.
Preferably, the acidic solution in step (2) comprises any one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid or citric acid, wherein typical but non-limiting combinations are combinations of hydrochloric acid and phosphoric acid, combinations of phosphoric acid and nitric acid, combinations of phosphoric acid and acetic acid, combinations of nitric acid and citric acid, combinations of hydrochloric acid, phosphoric acid and citric acid, combinations of sulfuric acid and phosphoric acid, and the like.
The concentration of the solute in the acidic solution is preferably 0.01mol/L to 5mol/L, and may be, for example, 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, or 5mol/L, etc., but is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the liquid-solid ratio of the acidic solution or water to the treated ferric phosphate in the step (2) is 0.5-100 ml:1g, for example, 0.5ml:1g, 1ml:1g, 10ml:1g, 12ml:1g, 15ml:1g, 20ml:1g, 30ml:1g, 40ml:1g, 50ml:1g, 60ml:1g, 70ml:1g, 80ml:1g or 100ml:1g, etc., but not limited to the listed values, and other non-listed values in this range are equally applicable.
The aging temperature in the step (2) is preferably 20 to 250 ℃, and may be, for example, 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 200 ℃, or 250 ℃, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the aging time is 0.1 to 100 hours, for example, 0.1 hours, 0.5 hours, 0.6 hours, 0.8 hours, 1 hour, 5 hours, 10 hours, 15 hours, 20 hours, 30 hours, 50 hours, 60 hours, 70 hours, 80 hours, 90 hours or 100 hours, etc., but not limited to the recited values, other non-recited values within the range are equally applicable.
Preferably, the aging in step (2) is followed by calcination.
The temperature of calcination after aging is preferably 100 to 900 ℃, and may be, for example, 100 ℃, 120 ℃, 130 ℃, 200 ℃, 250 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, or the like, but not limited to the values recited, and other values not recited in the range are equally applicable.
The calcination time after aging is preferably 0.1 to 20 hours, and may be, for example, 0.1 hours, 1 hour, 2 hours, 4 hours, 5 hours, 8 hours, 10 hours, 12 hours, 14 hours, 15 hours, 18 hours, or 20 hours, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the post-aging calcination in step (2) is performed under a non-reducing atmosphere.
Preferably, the non-reducing atmosphere comprises an oxidizing atmosphere and/or an inert atmosphere.
Preferably, the oxidizing atmosphere comprises oxygen and/or air.
Preferably, the inert atmosphere comprises any one or a combination of at least two of nitrogen, argon, helium, or carbon dioxide, wherein typical but non-limiting combinations are combinations of nitrogen and argon, combinations of argon and helium, and combinations of helium and carbon dioxide.
Preferably, washing and drying are also included between the aging and calcination.
The sulfur content in the iron phosphate after desulfurization in the step (2) is preferably 100ppm or less, and may be, for example, 100ppm, 95ppm, 90ppm, 80ppm, 60ppm, 50ppm, 40ppm, 30ppm or 20ppm, etc., but is not limited to the recited values, and other values not recited in the range are equally applicable.
In the present invention, ppm is calculated on a mass basis.
Preferably, the desulphurized iron phosphate is battery iron phosphate.
The desulfurization method of the iron phosphate provided by the invention can ensure that the sulfur content in the iron phosphate after desulfurization is less than or equal to 0.01wt%, namely less than 100ppm, and can better meet the requirements of the iron phosphate for batteries.
Preferably, the method comprises the steps of:
(1) Calcining the iron phosphate to be desulfurized with the sulfur content of 0.01-8wt% for 0.1-20 h at 100-900 ℃ in a non-reducing atmosphere; or the iron phosphate to be desulfurized with the sulfur content of 0.01-8wt% is ground to lead the D50 of the material to be less than or equal to 15 mu m; or the iron phosphate to be desulfurized with the sulfur content of 0.01-8wt% is calcined for 0.1-20 hours at 100-900 ℃ under the non-reducing atmosphere, and then the material D50 is less than or equal to 15 mu m through the grinding material; or the iron phosphate to be desulfurized with the sulfur content of 0.01-8wt% is firstly ground to lead the material D50 to be less than or equal to 15 mu m, and then calcined for 0.1-20 h at the temperature of 100-900 ℃ in a non-reducing atmosphere to obtain the treated iron phosphate;
(2) Aging the treated ferric phosphate for 0.1-100 h in an acidic solution with the solute concentration of 0.05-5 mol/L at 20-250 ℃ or aging for 0.1-100 h in water, wherein the liquid-solid ratio of the acidic solution or water to the treated ferric phosphate is 0.5-100 ml:1g, washing and drying the aged solid phase, and calcining for 0.1-20 h at 100-900 ℃ in a non-reducing atmosphere to obtain the desulfurized ferric phosphate.
The washing in the above process is not particularly limited, and any means and manner known to those skilled in the art for washing may be used, and may be adjusted according to the actual process, for example, rinsing, immersion washing or ultrasonic washing, or the like, or may be a combination of different manners.
The drying in the above process is not particularly limited, and any device and method known to those skilled in the art for drying may be used, or may be modified according to the actual process, for example, air drying, vacuum drying, drying or freeze drying, or may be a combination of different methods.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the method for desulfurizing the ferric phosphate, disclosed by the invention, the ferric phosphate to be desulfurized is subjected to calcination and/or grinding in sequence, and the impurity removal process of acid liquor aging is carried out, so that no solid or liquid waste is generated, the influence on the environment is small, no obvious secondary treatment cost is generated, and the resource can be saved;
(2) According to the method for desulfurizing the ferric phosphate, disclosed by the invention, the ferric phosphate to be desulfurized is subjected to calcination and/or grinding in sequence, and the impurity removal process of acid liquor aging is carried out, so that the sulfur content in the desulfurized ferric phosphate is less than or equal to 100ppm, and can reach within 70ppm under the preferable condition, and the requirement of the ferric phosphate for a battery can be better met;
(3) The method for desulfurizing the ferric phosphate provided by the invention is simple and convenient to operate, has high desulfurizing speed, and does not need to wash the crude ferric phosphate product with water for many times.
Drawings
FIG. 1 is a flow chart of a process for desulfurizing iron phosphate in an embodiment of the present invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
As shown in fig. 1, the present invention provides a specific embodiment, and specifically, the method includes the following steps:
(1) Calcining iron phosphate to be desulfurized in a non-reducing atmosphere; or the iron phosphate to be desulfurized is ground by a grinding material to lead the D50 of the material to be less than or equal to 15 mu m; or calcining the iron phosphate to be desulfurized in a non-reducing atmosphere to obtain calcined iron phosphate, and grinding the calcined iron phosphate to ensure that the D50 of the material is less than or equal to 15 mu m; or the iron phosphate to be desulfurized is firstly grinded to lead the material D50 to be less than or equal to 15 mu m, so as to obtain grinded iron phosphate, and then is calcined in a non-reducing atmosphere, so as to obtain treated iron phosphate;
(2) Aging the treated ferric phosphate in an acidic solution with the solute concentration of 0.1-5 mol/L at the temperature of 20-100 ℃ for 0.1-30 h, wherein the liquid-solid ratio of the acidic solution to the treated ferric phosphate is 1-100 ml/1 g, washing and drying the aged solid phase, and then calcining the solid phase for 0.1-20 h (represented by a dotted line frame) at the temperature of 100-900 ℃ in a non-reducing atmosphere to obtain the desulfurized ferric phosphate.
Example 1
The embodiment provides a method for desulfurizing iron phosphate, which comprises the following steps:
(1) Calcining the iron phosphate to be desulfurized with the sulfur content of 0.01 weight percent for 0.1h at 200 ℃ in an oxidizing atmosphere to obtain treated iron phosphate;
(2) Aging the treated ferric phosphate in an acidic solution mixed by hydrochloric acid and phosphoric acid with the concentration of 0.1mol/L at the temperature of 20 ℃ for 0.5h, wherein the liquid-solid ratio of the acidic solution to the treated ferric phosphate is 1 ml/1 g, and washing and drying the aged solid phase to obtain the desulfurized ferric phosphate.
Example 2
The embodiment provides a method for desulfurizing iron phosphate, which comprises the following steps:
(1) Calcining the iron phosphate to be desulfurized with the sulfur content of 8wt% for 20 hours at 500 ℃ in an argon atmosphere to obtain treated iron phosphate;
(2) Aging the treated ferric phosphate in an acidic solution mixed by phosphoric acid with the concentration of 5mol/L and citric acid at the temperature of 100 ℃ for 30 hours, wherein the liquid-solid ratio of the acidic solution to the treated ferric phosphate is 100 ml/1 g, and washing and drying the aged solid phase to obtain the desulfurized ferric phosphate.
Example 3
The embodiment provides a method for desulfurizing iron phosphate, which comprises the following steps:
(1) Calcining the iron phosphate to be desulfurized with the sulfur content of 4wt% for 5 hours at 800 ℃ in a nitrogen atmosphere to obtain treated iron phosphate;
(2) Aging the treated ferric phosphate in an acidic solution mixed by hydrochloric acid and acetic acid with the concentration of 2.5mol/L at the temperature of 80 ℃ for 10 hours, wherein the liquid-solid ratio of the acidic solution to the treated ferric phosphate is 50ml:1g, and washing and drying the aged solid phase to obtain the desulphurized ferric phosphate.
Example 4
The embodiment provides a method for desulfurizing iron phosphate, which comprises the following steps:
(1) Calcining the iron phosphate to be desulfurized with the sulfur content of 6wt% for 15 hours at 400 ℃ in an oxidizing atmosphere to obtain treated iron phosphate;
(2) Aging the treated ferric phosphate in an acidic solution mixed by nitric acid and acetic acid with the concentration of 4mol/L at the temperature of 60 ℃ for 20 hours, wherein the liquid-solid ratio of the acidic solution to the treated ferric phosphate is 20 ml/1 g, and washing and drying the aged solid phase to obtain the desulfurized ferric phosphate.
Example 5
This example provides a method for desulphurisation of iron phosphate, which differs from example 1 only in that: the calcination temperature was 1000 ℃.
Example 6
This example provides a method for desulphurisation of iron phosphate, which differs from example 1 only in that: the concentration of the solute in the acidic solution was 7mol/L.
Example 7
This example provides a method for desulphurisation of iron phosphate, which differs from example 1 only in that: the acidic solution is 0.1mol/L hydrochloric acid solution.
Example 8
This example provides a method for desulphurisation of iron phosphate, which differs from example 1 only in that: the acidic solution was a phosphoric acid solution of 0.1 mol/L.
Example 9
This example provides a method for desulphurisation of iron phosphate, which differs from example 1 only in that:
the calcination in the step (1) is replaced by an abrasive, specifically, iron phosphate to be desulfurized with the sulfur content of 0.01 weight percent is subjected to ball milling, the ball mass ratio is 15:1, the time is 120min, the rotating speed is 500rpm, and the particle size D50 of the ball milled material is 3 mu m.
Example 10
This example provides a method for desulphurisation of iron phosphate, which differs from example 1 only in that:
adding an abrasive material, in particular sulfur, to be added in an amount of 0.01 wt.% after calcination in step (1)Calcining the desulphurized ferric phosphate for 0.1h at 200 ℃ in an oxidizing atmosphere to obtain calcined ferric phosphate, and then carrying out jet milling with the milling gas quantity of 120m 3 And/min, the classification power is 20kw, the time is 60min, and the treated ferric phosphate with the material particle size D50 of 1 μm is obtained.
Example 11
This example provides a method for desulphurisation of iron phosphate, which differs from example 1 only in that:
adding an abrasive material, in particular iron phosphate to be desulfurized with a sulfur content of 0.01wt%, before the calcination in step (1), by air flow grinding, the amount of the abrasive material by air flow grinding being 120m 3 And/min, wherein the grading power is 20kw, the time is 60min, the ground ferric phosphate with the material particle size D50 of 1 mu m is obtained, and then the ground ferric phosphate is calcined for 0.1h at 200 ℃ in an oxidizing atmosphere, so that the treated ferric phosphate is obtained.
Example 12
This example provides a method for desulphurisation of iron phosphate, which differs from example 10 only in that:
adding a calcination step after ageing, washing and drying in the step (2), wherein the step (2) is specifically as follows:
aging the treated ferric phosphate in an acidic solution mixed by hydrochloric acid and phosphoric acid with the concentration of 0.1mol/L at the temperature of 20 ℃ for 0.5h, wherein the liquid-solid ratio of the acidic solution to the treated ferric phosphate is 1 ml/1 g, washing and drying the aged solid phase, and calcining the solid phase at the temperature of 500 ℃ for 20h under a non-reducing atmosphere to obtain the desulfurized ferric phosphate.
Example 13
This example provides a method for desulphurisation of iron phosphate, which differs from example 11 only in that:
adding a calcination step after ageing, washing and drying in the step (2), wherein the step (2) is specifically as follows:
aging the treated ferric phosphate in an acidic solution mixed by hydrochloric acid and phosphoric acid with the concentration of 0.1mol/L at the temperature of 20 ℃ for 0.5h, wherein the liquid-solid ratio of the acidic solution to the treated ferric phosphate is 1 ml/1 g, washing and drying the aged solid phase, and calcining the solid phase at the temperature of 500 ℃ for 20h under a non-reducing atmosphere to obtain the desulfurized ferric phosphate.
Example 14
The embodiment provides a method for desulfurizing iron phosphate, which comprises the following steps:
(1) Calcining the iron phosphate to be desulfurized with the sulfur content of 0.01wt% for 0.1h at 200 ℃ in an oxidizing atmosphere to obtain calcined iron phosphate, then sanding, wherein the mass ratio of the ball materials to the sand is 10:1, the time is 240min, the rotating speed is 3000rpm, the sand is wet grinding, the wet grinding medium is a combination of methanol and ethanol with the ratio of 1:1, and the wet grinding slurry after wet grinding is filtered to obtain treated iron phosphate with the material particle size D50 of 2 mu m;
(2) Aging the treated ferric phosphate in 35 ℃ water for 1h, wherein the liquid-solid ratio of the acidic solution to the treated ferric phosphate is 2 ml/1 g, washing and drying the aged solid phase, and calcining the solid phase at 100 ℃ for 20h in a non-reducing atmosphere to obtain the desulfurized ferric phosphate.
Example 15
The embodiment provides a method for desulfurizing iron phosphate, which comprises the following steps:
(1) Firstly, stirring and grinding iron phosphate to be desulfurized with the sulfur content of 0.01wt%, wherein the mass ratio of balls of the stirring and grinding is 25:1, the time is 240min, the rotating speed is 45rpm, the stirring and grinding are wet grinding, the wet grinding medium is dilute phosphoric acid with the pH value of 4.5, the ground iron phosphate with the material particle diameter D50 of 4 mu m is obtained, and then the ground iron phosphate is calcined for 8 hours at 350 ℃ in an oxidizing atmosphere, so that wet grinding slurry containing the treated iron phosphate is obtained;
(2) The wet grinding slurry containing the treated ferric phosphate is aged for 1.2 hours in an acid solution mixed by hydrochloric acid and phosphoric acid with the concentration of 0.2mol/L at the temperature of 40 ℃, the liquid-solid ratio of the acid solution to the treated ferric phosphate is 1.5ml to 1g, the aged solid phase is washed and dried, and then the solid phase is calcined for 3 hours at the temperature of 700 ℃ in a non-reducing atmosphere, so that the desulfurized ferric phosphate is obtained.
Comparative example 1
This comparative example provides a method for desulfurizing iron phosphate, which differs from example 1 only in that: the iron phosphate to be desulphurized is directly aged in acid liquor without calcination, and the process parameters are the same as in example 1.
Comparative example 2
This comparative example provides a method for desulfurizing iron phosphate, which differs from example 1 only in that: only calcination is performed, and the aging step in step (2) is not performed.
The testing method comprises the following steps: the sulfur content in the iron phosphate after desulfurization was measured by a carbon sulfur analyzer test method, and the results are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) According to the method for desulfurizing the iron phosphate, disclosed by the invention, the further removal of trace sulfur in the iron phosphate can be realized by a simple method, wherein the sulfur content of the iron phosphate can be reduced to be within 100 ppm;
(2) It can be seen from the combination of examples 1 and 5 that the higher the temperature of calcination is, the better the desulfurization effect is, and the desulfurization effect is remarkably improved by controlling the desulfurization temperature within a specific temperature range;
(3) As can be seen from a combination of examples 1 and 6, the concentration of the solute in the acidic solution of example 1 was 0.1mol/L in the acidic solution mixed with phosphoric acid, and the sulfur content in the iron phosphate after desulfurization in example 1 was only 90ppm, and the sulfur content in example 6 was only 88ppm, but the recovery rate of the iron phosphate after the high concentration acid treatment in example 6 was significantly reduced, compared to the case where the high concentration of the mixed solution of 7mol/L was used in example 6, thereby demonstrating that the present invention can simultaneously secure the desulfurization effect and recovery rate by optimizing the concentration of the acidic solution;
(4) It can be seen from the combination of examples 1 and 10-11 that in example 1, only the post-calcination aging step is used, and in example 11, the sulfur content in the iron phosphate product of example 10 is only 60ppm, and in example 11, also only 80ppm, and up to 90ppm, compared to example 10, in which the pre-treatment with the combination of calcination and abrasive material is performed, thus indicating that the preferred pre-treatment method of the present invention can reduce the sulfur content in the product, and the more preferred pre-calcination and abrasive material can reduce the sulfur content in the iron phosphate product better;
(5) It can be seen from the combination of examples 10 to 11 and examples 12 to 13 that the invention further adds a calcination step after aging, and can further desulphurize, and the sulphur content in the desulphurized ferric phosphate is only within 70 ppm;
(6) It can be seen from the combination of example 1 and comparative examples 1 to 2 that the pretreatment and aging steps are not indispensable in the present invention, and the interaction between the two can achieve a better desulfurization effect.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (10)
1. A method for desulfurizing iron phosphate, said method comprising the steps of:
(1) Calcining and/or grinding the iron phosphate to be desulfurized to obtain treated iron phosphate;
(2) And aging the treated ferric phosphate in water or an acidic solution to obtain the desulphurized ferric phosphate.
2. The method of claim 1, wherein the source of iron phosphate to be desulphurised in step (1) comprises any one or a combination of at least two of co-precipitation, crystallization, hydrothermal, sol-gel or templating;
preferably, the content of sulfur in the iron phosphate to be desulfurized is 0.01-8wt%;
preferably, the sulfur in the iron phosphate to be desulphurized comprises inorganic sulfur.
3. The method according to claim 1 or 2, wherein the temperature of calcination in step (1) is 100 ℃ to 900 ℃;
preferably, the calcination time is 0.1 to 20 hours;
preferably, the calcination is performed under a non-reducing atmosphere;
preferably, the non-reducing atmosphere comprises an oxidizing atmosphere and/or an inert atmosphere;
preferably, the oxidizing atmosphere comprises oxygen and/or air;
preferably, the inert atmosphere comprises any one or a combination of at least two of nitrogen, argon, helium or carbon dioxide.
4. A method according to any one of claims 1 to 3, wherein the means for grinding in step (1) comprises any one or a combination of at least two of stirred mill, ball mill, sand mill or air mill;
preferably, the stirring mill, ball mill or sand mill comprises dry mill or wet mill;
preferably, the wet milling medium comprises any one or a combination of at least two of methanol, ethanol, propanol, water, dilute hydrochloric acid, dilute sulfuric acid, dilute phosphoric acid, dilute nitric acid, dilute acetic acid or dilute citric acid;
preferably, the pH of the wet-milling medium is greater than or equal to 1.0;
preferably, the grain diameter D50 of the material after stirring and grinding is less than or equal to 15 mu m;
preferably, the particle size D50 of the ball-milled material is less than or equal to 15 mu m;
preferably, the grain diameter D50 of the sanded material is less than or equal to 10 mu m;
preferably, the D50 of the material after the air flow grinding is less than or equal to 15 mu m.
5. The method of claim 4, wherein the wet-milled slurry is aged directly or after removing the medium by solid-liquid separation.
6. The method of any one of claims 1 to 5, wherein the acidic solution in step (2) comprises any one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, or citric acid.
7. The method according to any one of claims 1 to 6, wherein the concentration of the solute in the acidic solution is 0.01mol/L to 5mol/L;
preferably, the liquid-solid ratio of the acidic solution or water to the treated ferric phosphate is 0.5-100 ml:1g.
8. The process according to any one of claims 1 to 7, wherein the ageing in step (2) is carried out at a temperature of 20 ℃ to 250 ℃;
preferably, the aging time is 0.1 to 100 hours;
preferably, the aging in step (2) is followed by calcination;
preferably, the temperature of calcination after aging is 100-900 ℃;
preferably, the calcination time after aging is 0.1 to 20 hours.
9. The process according to any one of claims 1 to 8, wherein the post-aging calcination in step (2) is carried out under a non-reducing atmosphere;
preferably, the non-reducing atmosphere comprises an oxidizing atmosphere and/or an inert atmosphere;
preferably, the oxidizing atmosphere comprises oxygen and/or air;
preferably, the inert atmosphere comprises any one or a combination of at least two of nitrogen, argon, helium or carbon dioxide.
10. The method according to any one of claims 1 to 9, characterized in that it comprises the steps of:
(1) Calcining the iron phosphate to be desulfurized with the sulfur content of 0.01-8wt% for 0.1-20 h at 100-900 ℃ in a non-reducing atmosphere; or the iron phosphate to be desulfurized with the sulfur content of 0.01-8wt% is ground to lead the D50 of the material to be less than or equal to 15 mu m; or the iron phosphate to be desulfurized with the sulfur content of 0.01-8wt% is calcined for 0.1-20 hours at 100-900 ℃ under the non-reducing atmosphere, and then the material D50 is less than or equal to 15 mu m through the grinding material; or the iron phosphate to be desulfurized with the sulfur content of 0.01-8wt% is firstly ground to lead the material D50 to be less than or equal to 15 mu m, and then calcined for 0.1-20 h at the temperature of 100-900 ℃ in a non-reducing atmosphere to obtain the treated iron phosphate;
(2) Aging the treated ferric phosphate for 0.1-100 h in an acidic solution with the solute concentration of 0.05-5 mol/L at 20-250 ℃ or aging for 0.1-100 h in water, wherein the liquid-solid ratio of the acidic solution or water to the treated ferric phosphate is 0.5-100 ml:1g, washing and drying the aged solid phase, and calcining for 0.1-20 h at 100-900 ℃ in a non-reducing atmosphere to obtain the desulfurized ferric phosphate.
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| WO2014056143A1 (en) * | 2012-10-09 | 2014-04-17 | 上海交通大学 | Lithium iron phosphate material and preparation thereof |
| CN108046229A (en) * | 2017-12-14 | 2018-05-18 | 瓮福（集团）有限责任公司 | A kind of method of battery-grade anhydrous iron phosphate synthesis desulfurating |
| CN111153391A (en) * | 2020-01-09 | 2020-05-15 | 湖南雅城新材料有限公司 | Preparation method of low-sulfur-content battery-grade iron phosphate |
| CN111847415A (en) * | 2020-07-21 | 2020-10-30 | 合肥国轩高科动力能源有限公司 | Battery-grade ferric orthophosphate and preparation method and application thereof |
| CN113479861A (en) * | 2021-07-01 | 2021-10-08 | 广东邦普循环科技有限公司 | Preparation method of low-sulfur-content nano iron phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014056143A1 (en) * | 2012-10-09 | 2014-04-17 | 上海交通大学 | Lithium iron phosphate material and preparation thereof |
| CN108046229A (en) * | 2017-12-14 | 2018-05-18 | 瓮福（集团）有限责任公司 | A kind of method of battery-grade anhydrous iron phosphate synthesis desulfurating |
| CN111153391A (en) * | 2020-01-09 | 2020-05-15 | 湖南雅城新材料有限公司 | Preparation method of low-sulfur-content battery-grade iron phosphate |
| CN111847415A (en) * | 2020-07-21 | 2020-10-30 | 合肥国轩高科动力能源有限公司 | Battery-grade ferric orthophosphate and preparation method and application thereof |
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