CN115744854A - Method for preparing ferrous phosphate from ferrous chloride as byproduct of titanium white chloride - Google Patents
Method for preparing ferrous phosphate from ferrous chloride as byproduct of titanium white chloride Download PDFInfo
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- 229940116007 ferrous phosphate Drugs 0.000 title claims abstract description 43
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title claims abstract description 43
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229960002089 ferrous chloride Drugs 0.000 title claims abstract description 34
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 title claims abstract description 34
- 239000006227 byproduct Substances 0.000 title claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 235000010215 titanium dioxide Nutrition 0.000 title claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002585 base Substances 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 3
- 229910000398 iron phosphate Inorganic materials 0.000 abstract description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000005660 chlorination reaction Methods 0.000 description 5
- UXKNCQDLMPVIFP-UHFFFAOYSA-H iron(2+) diphosphate hydrate Chemical compound O.[Fe++].[Fe++].[Fe++].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O UXKNCQDLMPVIFP-UHFFFAOYSA-H 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NSYYPXSKPGPMBW-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].Cl Chemical compound [O-2].[O-2].[Ti+4].Cl NSYYPXSKPGPMBW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LEAMSPPOALICQN-UHFFFAOYSA-H iron(2+);diphosphate;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEAMSPPOALICQN-UHFFFAOYSA-H 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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 discloses a method for preparing ferrous phosphate by using ferrous chloride as a byproduct of titanium white chloride, which comprises the following steps: s1, adding a ferrous chloride solution of a titanium white chloride by-product, a reducing substance and an alkali regulator to obtain a solution A; s2, adding an acid regulator into the solution A to obtain a solution B; s3, adding a phosphorus source into the solution B to obtain a solution C; s4, adding the solution C and an alkali regulator into a reaction container filled with a base solution in advance for reaction; the product is post-treated to obtain a ferrous phosphate product. The invention has the advantages that: 1) Firstly, a method for synthesizing ferrous phosphate by using a byproduct ferrous chloride of titanium white chloride is provided, and a new way is opened up for the recovery treatment of the byproduct ferrous chloride of titanium white chloride; 2) The iron phosphate prepared by the method can completely meet the index requirements of the lithium iron phosphate anode production line, and the content of each impurity ion is far lower than the index value of the standard.
Description
Technical Field
The invention relates to a lithium ion battery production technology, in particular to a lithium ion battery ferrous phosphate preparation technology.
Background
The production process of titanium dioxide by a chlorination method starts late in China, and has the advantages that: short process flow, continuous production, high automation degree and good product quality, and the product is rutile titanium dioxide. The production process of the titanium dioxide chloride comprises chlorination, oxidation, post-treatment and the like, wherein the chlorination part of the procedures comprises the following steps: material preparation, chlorination, condensation, refining and tail gas treatment.
At present, titanium dioxide powder expansion plants adopt a chlorination process, a large amount of ferrous chloride byproducts which are main components are generated in the production process of the process, and the byproducts are the "ferrous chloride byproduct of titanium chloride white" in the invention. Because the titanium white byproduct ferrous chloride contains a large amount of Ti 2+ 、Al 3+ 、Mn 2+ 、Mg 2+ And the impurities do not meet the GB 89781996 comprehensive sewage discharge standard, the method of adding alkali to precipitate chromium hydroxide and entrusting an environmental protection company to treat waste residues is adopted by the inventor at present, and the treatment cost is high.
Among the numerous positive electrode materials, lithium iron phosphate (LiFePO) 4 ) The lithium ion battery taking lithium iron phosphate as a positive electrode material is widely applied to the field of power batteries such as electric tools, electric bicycles, mopeds, golf carts, model airplanes, toys, miner lights and the like. The existing method for synthesizing lithium iron phosphate mainly comprises a high-temperature solid phase method, a carbothermic method, a hydrothermal synthesis method and the like.
The ferrous phosphate, lithium hydroxide and organic carbon can generate lithium iron phosphate by adopting a high-temperature solid phase method. The acidic wastewater contains a large amount of ferrous chloride, so that a ferrous phosphate can be prepared from the ferrous chloride byproduct, the waste liquid treatment cost is reduced, and the comprehensive utilization of wastewater resources is realized.
Through patent review and new research, the ferrous phosphate is mostly prepared by waste water, for example, chinese patent CN104445555A discloses a waste water dephosphorization method and a ferrous phosphate preparation method, wherein a fluidized bed crystallization method is involved, the method has the disadvantages of serious abrasion, large fluctuation of low-load operation, more required raw materials and complex process flow; chinese patent CN112794299B discloses a method for preparing ferrous phosphate by using wet-process phosphoric acid, in which a fluidized bed is also used, and an impurity magnesium compound is introduced, so that the purification step is complicated, and is not beneficial to the separation of ferrous chloride. At present, no patent related to the preparation of ferrous phosphate by using a byproduct ferrous chloride of titanium white chloride is discovered for a while.
Disclosure of Invention
In order to solve the problem that the ferrous chloride as a titanium white byproduct is difficult to recycle at present, the invention provides a method for preparing ferrous phosphate from the ferrous chloride as the titanium white byproduct.
The technical scheme adopted by the invention is as follows: the method for preparing the ferrous phosphate by using the ferrous chloride as the byproduct of the titanium white chloride comprises the following steps:
s1, adding a ferrous chloride solution of a titanium white chloride by-product into a reaction vessel, adding a reducing substance, adding an alkali regulator to regulate the pH value to 4-7, controlling the reaction temperature to be 60-100 ℃, reacting for 1-3 h, stirring at a rotating speed of 50-350 r/min, and filtering after the reaction is finished to obtain a solution A;
s2, adding an acid regulator into the solution A to regulate the pH value to be 0.5-3.5 to obtain a solution B;
s3, adding a phosphorus source into the solution B to obtain a solution C;
s4, adding the solution C and an alkali regulator into a reaction container which is filled with a base solution in advance according to the flow rate set by the process for reaction, wherein the pH value of the base solution is 4.5-6.5; and filtering and washing the product after the reaction to obtain a ferrous phosphate filter cake, and drying the ferrous phosphate filter cake to obtain a ferrous phosphate product.
As a further improvement of the invention, the reducing substance is one or more selected from aluminum powder, iron powder and ascorbic acid.
As a further improvement of the invention, the alkali regulator is selected from one or two of ammonia water and sodium hydroxide.
As a further improvement of the invention, the acid regulator is selected from one or more of hydrochloric acid, nitric acid and sulfuric acid.
As a further improvement of the invention, the phosphorus source is selected from one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate. More preferably, phosphate radical of phosphorus source and Fe in the solution B are added 2+ 1:1.5.
The reaction conditions of step S4 in the present invention can be set as follows: stirring at a rotating speed of 50-300 r/min, feeding for 0.5-2 h, reacting for 6-10 h, at a reaction temperature of 30-90 ℃, at a reaction pH of 2-8, and aging at normal temperature for 1-4 h after the reaction is finished; the drying mode is vacuum drying, the drying time is 3-8 h, and the drying temperature is 50-150 ℃.
The invention also discloses ferrous phosphate which is prepared by the method for preparing the ferrous phosphate by the ferrous chloride as the byproduct of titanium white chloride.
The invention also discloses a production method of the lithium iron phosphate anode material of the lithium battery, which is characterized in that the production raw material comprises the ferrous phosphate.
The invention also discloses the lithium iron phosphate anode material of the lithium battery prepared by the production method of the lithium iron phosphate anode material of the lithium battery.
The invention has the beneficial effects that: 1) Firstly, a method for synthesizing ferrous phosphate by using a byproduct ferrous chloride of titanium white chloride is provided, and a new way is opened up for the recovery treatment of the byproduct ferrous chloride of titanium white chloride; 2) Experiments show that each quality index of the iron phosphate prepared by the method can completely meet the index requirement of 'index requirement of lithium iron phosphate positive electrode production line', and the content of each impurity ion is far lower than the standard index value; 3) The method does not add a precipitator, does not introduce new impurities, has good impurity removal effect on chromium, aluminum, titanium, vanadium and other ions, has less iron loss and high utilization rate; 4) The method has the advantages of simple process, easy control of various parameters, low requirement on the byproduct ferrous chloride of the titanium white chloride as the raw material, and suitability for large-scale production.
Drawings
Figure 1 is the XRD pattern of ferrous phosphate octahydrate in example 1.
Detailed Description
The present invention will be further described with reference to the following examples.
The first embodiment is as follows:
synthesizing ferrous phosphate by using a titanium white chloride byproduct ferrous chloride according to the following method:
s1, adding 1L of a titanium white chloride by-product ferrous chloride solution into a reaction container, adding 0.5g of iron powder, adding 10% of sodium hydroxide to adjust the pH value to 4.5, controlling the reaction temperature to be 90 ℃, reacting for 2 hours, stirring at a rotating speed of 100r/min, and filtering after the reaction is finished to obtain a solution A;
s2, adding hydrochloric acid into the solution A to adjust the pH value to 1.7 to obtain a solution B;
s3, adding phosphoric acid into the solution B to obtain a solution C; the phosphate radical of the added phosphoric acid and the Fe in the solution B 2+ 1:1.5.
S4, adding the solution C into a reaction kettle which is pre-filled with a small amount of water with pH =5 adjusted by hydrochloric acid and used as a base solution at a speed of 1.2L/h, controlling the feeding speed of sodium hydroxide to keep the pH in the reaction kettle at 5, the rotating speed at 100r/min, the temperature at 50 ℃, and the reaction time at 5h and the normal temperature for aging for 4h;
s5, filtering after the reaction is finished to obtain a ferrous phosphate filter cake, and washing the filter cake for 3 times by hot water to obtain a crude ferrous phosphate;
s6, heating the crude ferrous phosphate in a vacuum drying oven at 70 ℃ for 6h to obtain Fe 3 (PO 4 ) 2 .8H 2 O。
The obtained ferrous phosphate hydrate is subjected to element analysis, and the detection result is compared with the index requirement of the lithium iron phosphate positive electrode production line, and the result is shown in table 1.
Example two:
synthesizing ferrous phosphate by using a titanium white chloride byproduct ferrous chloride according to the following method:
s1, adding 1L of a titanium white chloride by-product ferrous chloride solution into a reaction container, adding 0.5g of iron powder, adding 10% of sodium hydroxide to adjust the pH value to 4.8, controlling the reaction temperature to be 90 ℃, reacting for 2 hours, stirring at a rotating speed of 100r/min, and filtering after the reaction is finished to obtain a solution A;
s2, adding hydrochloric acid into the solution A to adjust the pH value to 1.2 to obtain a solution B;
s3, adding phosphoric acid into the solution B to obtain a solution C; the phosphate radical of the added phosphoric acid and the Fe in the solution B 2+ 1:1.5.
S4, adding the solution C into a reaction kettle which is pre-filled with a small amount of water with pH =5.5 adjusted by hydrochloric acid and used as a base solution at a speed of 1.2L/h, controlling the feeding speed of sodium hydroxide to keep the pH in the reaction kettle at 5.5, the rotating speed at 150r/min, the temperature at 40 ℃ and the reaction time at 5h and the normal-temperature aging time at 3h;
s5, filtering after the reaction is finished to obtain a ferrous phosphate filter cake, and washing the filter cake for 3 times by hot water to obtain a crude ferrous phosphate;
s6, heating the crude ferrous phosphate in a vacuum drying oven at 70 ℃ for 6h to obtain Fe 3 (PO 4 ) 2 .8H 2 O。
The obtained ferrous phosphate hydrate is subjected to element analysis, and the detection result is compared with the index requirement of the lithium iron phosphate positive electrode production line, and the result is shown in table 1.
Table 1 table of the results of measuring the composition of ferrous phosphate hydrate in examples
| Item | Example 1 | Example 2 | Index requirement |
| Fe％ | 31.5 | 30.4 | 30.0～32.0 |
| P％ | 20.1 | 19.6 | 19.5±1.0 |
| Particle size D50um | 3.1 | 4.2 | 3±1.5 |
| The water content is% | 0.05 | 0.1 | ≤0.2 |
The result shows that each item in the ferrous phosphate hydrate prepared by the embodiment meets the index requirement, and the ferrous phosphate obtained by the preparation method can be used as a precursor for preparing battery-grade iron phosphate, so that the ferrous phosphate hydrate has a good application prospect.
Claims (10)
1. The method for preparing the ferrous phosphate by using the ferrous chloride as the byproduct of the titanium white chloride comprises the following steps:
s1, adding a titanium white chloride byproduct ferrous chloride solution into a reaction container, adding a reducing substance, adding an alkali regulator to regulate the pH value to 4-7, controlling the reaction temperature to be 60-100 ℃, reacting for 1-3 h, stirring at a rotating speed of 50-350 r/min, and filtering after the reaction is finished to obtain a solution A;
s2, adding an acid regulator into the solution A to regulate the pH value to be 0.5-3.5 to obtain a solution B;
s3, adding a phosphorus source into the solution B to obtain a solution C;
s4, adding the solution C and an alkali regulator into a reaction container which is filled with a base solution in advance according to the flow rate set by the process for reaction, wherein the pH value of the base solution is 4.5-6.5; and filtering and washing the product after the reaction to obtain a ferrous phosphate filter cake, and drying the ferrous phosphate filter cake to obtain a ferrous phosphate product.
2. The method for preparing ferrous phosphate from ferrous chloride as a byproduct of titanium white chloride according to claim 1, which is characterized in that: the reducing substance is selected from one or more of aluminum powder, iron powder and ascorbic acid.
3. The method for preparing ferrous phosphate from ferrous chloride as a byproduct of titanium white chloride according to claim 1, which is characterized in that: the alkali regulator is selected from one or two of ammonia water and sodium hydroxide.
4. The method for preparing ferrous phosphate from ferrous chloride as a byproduct of titanium white chloride according to claim 1, which is characterized in that: the acid regulator is selected from one or more of hydrochloric acid, nitric acid and sulfuric acid.
5. The method for preparing ferrous phosphate from ferrous chloride as a byproduct of titanium chloride white production according to claim 1, which comprises the following steps: the phosphorus source is selected from one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate.
6. The method for preparing ferrous phosphate from ferrous chloride as a byproduct of titanium white chloride according to claim 5, wherein: phosphate radical of added phosphorus source and Fe in the solution B 2+ 1.
7. The method for preparing ferrous phosphate from ferrous chloride as a byproduct of titanium chloride white production according to claim 1, wherein the reaction conditions in step S4 are as follows: stirring at a rotating speed of 50-300 r/min, feeding time of 0.5-2 h, reaction time of 6-10 h, reaction temperature of 30-90 ℃, reaction pH of 2-8, and aging at normal temperature for 1-4 h after the reaction is finished; the drying mode is vacuum drying, the drying time is 3-8 h, and the drying temperature is 50-150 ℃.
8. Ferrous phosphate produced by the method for producing ferrous phosphate from ferrous chloride as a by-product of titanium white chloride according to any one of claims 1 to 7.
9. The production method of the lithium iron phosphate anode material of the lithium battery is characterized by comprising the following steps of: the production feedstock comprises the ferrous phosphate of claim 8.
10. The lithium iron phosphate positive electrode material for a lithium battery, which is produced by the method for producing a lithium iron phosphate positive electrode material for a lithium battery according to claim 9.
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Citations (3)
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|---|---|---|---|---|
| CN101826617A (en) * | 2010-05-05 | 2010-09-08 | 黄博 | Preparation method of lithium iron phosphate |
| CN113526480A (en) * | 2021-07-13 | 2021-10-22 | 曲靖市德方纳米科技有限公司 | Method for preparing ferrous phosphate from titanium dioxide byproduct |
| WO2022116702A1 (en) * | 2020-12-03 | 2022-06-09 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate and use thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101826617A (en) * | 2010-05-05 | 2010-09-08 | 黄博 | Preparation method of lithium iron phosphate |
| WO2022116702A1 (en) * | 2020-12-03 | 2022-06-09 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate and use thereof |
| CN113526480A (en) * | 2021-07-13 | 2021-10-22 | 曲靖市德方纳米科技有限公司 | Method for preparing ferrous phosphate from titanium dioxide byproduct |
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