CN111017900A - Preparation method of battery-grade iron phosphate - Google Patents
Preparation method of battery-grade iron phosphate Download PDFInfo
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- CN111017900A CN111017900A CN202010006631.XA CN202010006631A CN111017900A CN 111017900 A CN111017900 A CN 111017900A CN 202010006631 A CN202010006631 A CN 202010006631A CN 111017900 A CN111017900 A CN 111017900A
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- 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 47
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 26
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 23
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 17
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- -1 dihydrate ferric phosphate Chemical class 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 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
- 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Images
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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of battery-grade iron phosphate, which comprises the following steps: adding high-purity iron powder into hydrochloric acid with proper concentration to react until the iron powder is not dissolved any more; filtering, adding a proper amount of hydrogen peroxide, and reacting until no ferrous ions exist in the reaction solution; adding phosphoric acid, stirring uniformly, and then obtaining ferric phosphate dihydrate by a spray drying method; and (4) sintering at high temperature to remove crystal water to obtain the anhydrous iron phosphate. The process of the invention comprises the following steps: the method has the advantages that the processes of iron phosphate precipitation, aging, filtering, washing and the like are reduced, the processes are reduced, the flow is shortened, the production period is reduced, the production efficiency is improved, the water resource is saved, and the cost is low; moreover, the raw materials are recycled, no solid waste is generated, and the cost is reduced; the neutralizing agent is not needed, the use of raw materials is reduced, the possibility of introducing impurities is reduced, the purity of the obtained product is high, the impurity content is lower, and the market demand of battery-grade raw materials can be met.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery material preparation, and particularly relates to a preparation method of battery-grade iron phosphate.
Background
The synthesis process route of the lithium ion battery anode material lithium iron phosphate comprises a hydrothermal process, a ferrous oxalate process, an iron oxide red process and an iron phosphate process. The iron phosphate process gradually becomes the mainstream route of lithium iron phosphate production by virtue of good batch stability and excellent electrochemical performance. The ferric phosphate in the prior art is prepared by a conventional chemical precipitation method, and the generation process is as follows: compounding, ferrous oxidation, ferric phosphate precipitation, filtering and washingLow temperature drying-high temperature sintering and the like. For example, CN201910630953.9 discloses a preparation method of battery grade iron phosphate. The preparation method comprises the following steps: preparing ferrous sulfate solution with iron content of 5.0-10.0 wt%, adding oxidant and H3PO4Reacting, adding Fe2+Oxidation to Fe3+Forming a mixed solution of phosphoric acid and ferric sulfate, adding water to adjust the pH value to 1.5-2.5, reacting to obtain iron phosphate precipitate, washing and filtering, and drying and calcining a filter cake to obtain the battery-grade iron phosphate.
In the prior art, the ferric phosphate production process is complex, the energy consumption is high, the water consumption is large during washing, and the sewage treatment cost is high; secondly, the raw materials cannot be reused, for example, the neutralizer caustic soda liquid or ammonia water cannot be reused, solid salt is finally formed, or a large amount of calcium sulfate is generated even if the raw materials are recycled, so that the solid waste amount is large; in addition, the prior art uses more raw materials, has complex process and more chances of introducing impurities, thereby causing the product purity to be low.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of battery-grade iron phosphate, which has the advantages of simple production process, high resource utilization rate, no solid waste, high purity and low cost.
The invention is realized by the following steps:
a preparation method of battery-grade iron phosphate comprises the following steps: (1) and (3) ferrous solution synthesis: adding high-purity iron powder into hydrochloric acid with proper concentration to react until the iron powder is not dissolved any more; (2) and (3) oxidation: filtering, taking the filtrate, adding a proper amount of hydrogen peroxide, and reacting until no ferrous ions exist in the reaction liquid; (3) synthesis of ferric phosphate dihydrate: adding phosphoric acid according to the stoichiometric ratio of Fe to P being 1:1.01-1.03, uniformly stirring, and then obtaining ferric phosphate dihydrate by a spray drying method; (4) and (3) high-temperature sintering: and (4) sintering the ferric phosphate dihydrate obtained in the step (3) at a high temperature to remove crystal water to obtain the anhydrous ferric phosphate.
Preferably, in the step (1), the purity of the high-purity iron powder is more than or equal to 98 percent, and the fineness is more than or equal to 100 meshes.
Wherein, in the step (1), the chemical reaction formula is as follows:
Fe+2HCl＝FeCl2+H2↑
the reaction is a common reaction in the chemical field, and those skilled in the art can reasonably configure the proportion of the iron powder of the hydrogen chloride according to theoretical reaction equivalent, practical application conditions and the like, and the invention is not particularly limited thereto. In order to complete the reaction of the iron powder, it is preferred in the art to add an excess of hydrogen chloride, i.e., a molar ratio of hydrogen chloride to iron powder of 2:1 or more. It should be understood that the reaction may be carried out without adding an excess of hydrogen chloride and the excess of iron powder may be removed by filtration.
In step (1), the molar ratio of hydrogen chloride to iron powder is preferably 2.1 to 5:1, and may be, for example, 2.1:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, and the like, and more preferably 3 to 4: 1.
Wherein, regarding the reaction temperature of the step (1), the skilled person can make reasonable choice according to the existing technology and practical application. Preferably, in step (1), the reaction temperature is controlled to 90 ℃ or less, more preferably 85 ℃ or less.
The temperature control method can be a jacket heat exchange method or a heat exchanger heat exchange method and the like.
The concentration of hydrochloric acid is appropriately determined by those skilled in the art according to the reaction principle, practical application, and the like, and is not particularly limited in the present invention. For example, 1-40% hydrochloric acid may be used.
Wherein, in the step (2), the chemical reaction formula is as follows:
2FeCl2+2HCl+H2O2＝2FeCl3+2H2O
a person skilled in the art can add a proper amount of hydrogen peroxide according to theoretical reaction equivalent, actual application conditions and the like until no ferrous ions exist in reaction liquid. Preferably, in the step (2), hydrogen peroxide is added according to a molar ratio of 0.5-1.0:1.0 of ferrous ions to hydrogen peroxide.
Likewise, one skilled in the art can control the pH value with hydrochloric acid according to theoretical reaction equivalent, practical application and the like, and preferably, in the step (2), the pH value of the reaction solution is controlled to be less than or equal to 2.0 by hydrochloric acid.
Likewise, the reaction temperature in step (2) can be controlled by those skilled in the art according to the theoretical reaction equivalent and practical application. Preferably, the reaction temperature in step (2) is controlled to be less than or equal to 70 ℃.
Wherein, in the step (2), the reaction is carried out until no ferrous ions exist in the reaction liquid. The reaction time can be controlled by those skilled in the art, and the present invention is not particularly limited thereto. Preferably, the reaction in step (2) is carried out for 2 to 4 hours.
Wherein, in the step (3), phosphoric acid is added, the mixture is uniformly mixed and then directly sprayed and dried, the generation of the ferric phosphate is directly promoted by gas generation, and the chemical reaction formula is as follows:
FeCl3+H3PO4+2H2O＝FePO4·2H2O+3HCl↑
preferably, in the step (3), the air inlet temperature is controlled to be 190 ℃ and 210 ℃ during spray drying, and the air outlet temperature is controlled to be 95-100 ℃.
Wherein, the hydrogen chloride and the water vapor generated by the evaporation in the step (3) can be recycled to obtain hydrochloric acid for synthesizing ferrous solution. Preferably, the ferric phosphate dihydrate solid is obtained in the step (3), and simultaneously, the water vapor and the hydrogen chloride are recovered for standby.
Wherein, in the step (4), the chemical reaction formula is as follows:
FePO4·2H2O＝FePO4+2H2O↑
preferably, in step (4), the temperature is set to 400-800 ℃.
Preferably, in the step (4), the dehydration time is set to 2 to 4 hours.
Wherein, in the step (4), the high-temperature sintering device can be a high-temperature-resistant dehydration device such as a rotary furnace, a roller furnace or a push plate furnace.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes ferric trichloride and phosphoric acid, adopts a spray drying method to obtain high-purity ferric phosphate dihydrate, does not need filtration and washing, and greatly simplifies the production process, and the process of the invention comprises the following steps: compared with the prior art, the method has the advantages that the working procedures of ferric phosphate precipitation, aging, filtering and washing and the like are reduced, the working procedures are reduced, the flow is shortened, the production period is reduced, the production efficiency is improved, the water resource is saved, and the cost is low;
2. the raw materials are recycled: hydrochloric acid is used as a raw material, and hydrogen chloride and water vapor evaporated after the spray drying reaction for producing iron phosphate are condensed and recovered to obtain hydrochloric acid which can be used for dissolving iron powder to obtain ferrous chloride and further oxidized to obtain ferric trichloride for reproduction, so that the closed-loop use of the raw material is realized, the resource utilization rate is greatly improved, no solid waste is generated, and the production cost and the solid waste treatment cost are reduced;
3. the invention does not need to use neutralizing agents such as liquid caustic soda, ammonia water and the like in the traditional precipitation method, reduces the use of raw materials, reduces the possibility of introducing impurities, has high purity of the obtained product and lower impurity content, and can better meet the market demand of battery-grade raw materials.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Fig. 2 is an X-ray diffraction pattern of iron phosphate prepared according to the present invention.
Fig. 3 is a microscopic structure view of the iron phosphate prepared by the present invention.
Detailed Description
The invention will be better understood by reference to the following description of specific embodiments taken in conjunction with the accompanying drawings.
Example 1
Preparing 547.5kg of 20% solution of concentrated hydrochloric acid with the concentration of 37% by using deionized water, then adding 57.14kg of high-purity iron powder with the fineness of 100 meshes and the purity of 98%, fully reacting, and controlling the reaction temperature to be 65 ℃ through jacket heat exchange until the iron powder is not dissolved any more.
And after filtering, taking the filtrate, adding 74.18kg of 27.5% hydrogen peroxide, controlling the temperature to be 55 ℃, and after reacting for 3 hours, detecting that no ferrous ions exist in the iron solution by an o-diazepine indicator method to obtain an oxidation solution.
Adding 117kg of 85% phosphoric acid, uniformly mixing, conveying to a spray dryer, controlling the air inlet temperature to be 195 ℃ and the air outlet temperature to be 105 ℃, collecting the obtained solid as ferric phosphate dihydrate after evaporation, and recovering steam and hydrogen chloride condensate for storage.
And (3) conveying the dihydrate ferric phosphate obtained by spray drying into a roller kiln, and sintering at the high temperature of 550 ℃ for 4 hours to obtain the battery-grade anhydrous ferric phosphate.
The crystal structure of the anhydrous iron phosphate obtained in this example was detected by X-ray diffraction, and compared with a standard card, the crystal structure was shown in fig. 2, and it can be seen from fig. 2 that the product of this example has no other impurity phase (impurities), and is pure-phase iron phosphate.
When the anhydrous iron phosphate obtained in this example was observed under a microscope, it was found that the primary particles were uniform in size and had a porous structure (fig. 3).
Example 2
Preparing concentrated hydrochloric acid with the concentration of 37% into 547.5kg of 20% solution by using deionized water, then adding 57.14kg of high-purity iron powder with the fineness of 100 meshes and the purity of 98%, fully reacting, and controlling the reaction temperature to be 55 ℃ through heat exchange of a heat exchanger until the iron powder is not dissolved any more.
And filtering, taking the filtrate, adding 92.72kg of 27.5% hydrogen peroxide, controlling the temperature to be 65 ℃, reacting for 2 hours, and detecting that no ferrous ions exist in the iron solution by a potassium permanganate titration method to obtain an oxidizing solution.
Adding 118.7kg of 85% phosphoric acid, uniformly mixing, conveying to a spray dryer, controlling the air inlet temperature to be 200 ℃ and the air outlet temperature to be 105 ℃, collecting the obtained solid to be ferric phosphate dihydrate after evaporation, and recovering steam and hydrogen chloride condensate for storage.
And (3) conveying the dihydrate ferric phosphate obtained by spray drying into a roller kiln, and sintering at the high temperature of 580 ℃ for 3.5h to finally obtain the battery grade anhydrous ferric phosphate.
The crystal structure of the anhydrous iron phosphate obtained in this example was detected by X-ray diffraction, and comparison with a standard card showed that the product of this example had no other impurity phase (impurity), and was pure-phase iron phosphate. The anhydrous iron phosphate obtained in the present example was observed by a microscope, and the primary particles were uniform in size and had a porous structure.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of battery-grade iron phosphate is characterized by comprising the following steps:
(1) and (3) ferrous solution synthesis: adding high-purity iron powder into hydrochloric acid with proper concentration to react until the iron powder is not dissolved any more;
(2) and (3) oxidation: filtering, taking the filtrate, adding a proper amount of hydrogen peroxide, reacting until no ferrous ions exist in the reaction liquid, and controlling the pH of the reaction liquid to be less than or equal to 2.0 by hydrochloric acid;
(3) synthesis of ferric phosphate dihydrate: adding phosphoric acid according to the stoichiometric ratio of Fe to P being 1:1.01-1.03, uniformly stirring, and then obtaining ferric phosphate dihydrate by a spray drying method;
(4) and (3) high-temperature sintering: and (4) sintering the ferric phosphate dihydrate obtained in the step (3) at a high temperature to remove crystal water to obtain the anhydrous ferric phosphate.
2. The preparation method according to claim 1, wherein in the step (1), the purity of the high-purity iron powder is more than or equal to 98 percent, and the fineness is more than or equal to 100 meshes.
3. The process according to claim 1, wherein in step (1), the molar ratio of hydrogen chloride to iron powder is 2.1-5:1, preferably 3-4: 1.
4. The process according to claim 3, wherein the reaction temperature in the step (1) is controlled to 90 ℃ or less, preferably 85 ℃ or less.
5. The preparation method according to claim 1, wherein in the step (2), hydrogen peroxide is added according to a molar ratio of 0.5-1.0:1.0 of ferrous ions to hydrogen peroxide.
6. The process according to claim 1 or 5, wherein in the step (2), the reaction temperature is controlled to be 70 ℃ or lower, and the reaction is carried out for 2 to 4 hours.
7. The method as claimed in claim 1, wherein in the step (3), the inlet air temperature is controlled to be 190 ℃ and the outlet air temperature is controlled to be 95-100 ℃ during the spray drying.
8. The process according to claim 1 or 7, wherein the solid ferric phosphate dihydrate obtained in step (3) is recovered with steam and hydrogen chloride for use.
9. The method as claimed in claim 1, wherein the temperature is set to 400-800 ℃ and the dehydration time is set to 2-4h in step (4).
10. The production method according to claim 1 or 9, wherein in the step (4), the high-temperature sintering apparatus is a rotary kiln, a roller kiln, or a pusher furnace.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620316A (en) * | 2020-05-11 | 2020-09-04 | 湖南雅城新材料有限公司 | Preparation method of ferric phosphate dihydrate and lithium iron phosphate |
| CN111777049A (en) * | 2020-07-31 | 2020-10-16 | 湖北融通高科先进材料有限公司 | Method for preparing iron phosphate by using mixed iron source |
| CN117023538A (en) * | 2023-09-21 | 2023-11-10 | 成都益志科技有限责任公司 | Device system and method for preparing ferric phosphate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU670535A1 (en) * | 1977-12-19 | 1979-06-30 | Белорусский технологический институт им. С.М.Кирова | Method of producing trisubstituted ferrum orthophosphate |
| US20100279117A1 (en) * | 2009-05-04 | 2010-11-04 | Meecotech, Inc. | Electrode active composite materials and methods of making thereof |
| CN102167303A (en) * | 2011-04-30 | 2011-08-31 | 云南省化工研究院 | Method for preparing anhydrous ferric orthophosphate by microwave spouting |
| CN105742631A (en) * | 2016-03-10 | 2016-07-06 | 黄铭 | Differential reaction crystallization industrial preparation method for high-purity nano-scale lithium iron phosphate |
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2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU670535A1 (en) * | 1977-12-19 | 1979-06-30 | Белорусский технологический институт им. С.М.Кирова | Method of producing trisubstituted ferrum orthophosphate |
| US20100279117A1 (en) * | 2009-05-04 | 2010-11-04 | Meecotech, Inc. | Electrode active composite materials and methods of making thereof |
| CN102167303A (en) * | 2011-04-30 | 2011-08-31 | 云南省化工研究院 | Method for preparing anhydrous ferric orthophosphate by microwave spouting |
| CN105742631A (en) * | 2016-03-10 | 2016-07-06 | 黄铭 | Differential reaction crystallization industrial preparation method for high-purity nano-scale lithium iron phosphate |
Non-Patent Citations (2)
| Title |
|---|
| 赵瑞瑞等: "以三价铁为原料合成磷酸铁锂研究进展", 《电源技术》 * |
| 陈泓舟等: "新型喷雾干燥法制备LiFePO4/C复合材料及其性能研究", 《功能材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620316A (en) * | 2020-05-11 | 2020-09-04 | 湖南雅城新材料有限公司 | Preparation method of ferric phosphate dihydrate and lithium iron phosphate |
| CN111777049A (en) * | 2020-07-31 | 2020-10-16 | 湖北融通高科先进材料有限公司 | Method for preparing iron phosphate by using mixed iron source |
| CN117023538A (en) * | 2023-09-21 | 2023-11-10 | 成都益志科技有限责任公司 | Device system and method for preparing ferric phosphate |
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