CN113772647A - High-purity iron phosphate and method for preparing high-purity iron phosphate by adopting multistage purification method - Google Patents
High-purity iron phosphate and method for preparing high-purity iron phosphate by adopting multistage purification method Download PDFInfo
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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 82
- 238000000034 method Methods 0.000 title claims abstract description 77
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 70
- 238000000746 purification Methods 0.000 title claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 48
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 43
- 239000006012 monoammonium phosphate Substances 0.000 claims abstract description 43
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 32
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011591 potassium Substances 0.000 claims abstract description 30
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 30
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 20
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 20
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 20
- 239000011575 calcium Substances 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 11
- 239000002738 chelating agent Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- 239000000706 filtrate Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000004537 pulping Methods 0.000 claims description 16
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000002431 foraging effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 3
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 claims description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 23
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000005955 Ferric phosphate Substances 0.000 description 12
- 229940032958 ferric phosphate Drugs 0.000 description 12
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229960001484 edetic acid Drugs 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000004254 Ammonium phosphate Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 4
- 235000019289 ammonium phosphates Nutrition 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002686 phosphate fertilizer Substances 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940116007 ferrous phosphate Drugs 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 2
- 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 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- IZELSCCZMDXDAG-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].P(=O)(O)(O)O.[Fe+2].[Li+] Chemical compound P(=O)([O-])([O-])[O-].P(=O)(O)(O)O.[Fe+2].[Li+] IZELSCCZMDXDAG-UHFFFAOYSA-K 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- 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
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention belongs to the field of new energy batteries, and particularly relates to a method for preparing high-purity iron phosphate by adopting a multistage purification method, which comprises the following steps: s1, adding a potassium-containing compound into the monoammonium phosphate solution for reaction, and filtering to obtain a first-grade clear liquid after the reaction is finished; the monoammonium phosphate solution is prepared by adding pure water into industrial monoammonium solid or monoammonium phosphate clear liquid; s2 adding a chelating agent into the primary clear liquid obtained in the step S1 for reaction to obtain a secondary clear liquid; s3, reacting the secondary clear liquid obtained in the step S2 with a ferrous sulfate solution in the presence of an oxidant to obtain iron phosphate slurry; and S4, washing and drying the iron phosphate slurry after the reaction of the step S3 is finished to obtain an iron phosphate product. The method is simple and easy to implement, and the purity of the iron phosphate is greatly improved; the application also provides the high-purity iron phosphate prepared by the preparation method, the contents of calcium, magnesium, potassium and sodium impurities are all lower than 15ppm, and the prepared lithium iron phosphate can be effectively ensured to have good safety and stability.
Description
Technical Field
The invention relates to the field of new energy battery materials, in particular to high-purity iron phosphate and a method for preparing the high-purity iron phosphate by adopting a multi-stage purification method.
Background
Under the background of 'carbon peak reaching' and 'carbon neutralization', the reconstruction of an energy system in China is imperative. With the support of the country to the new energy industry, the new energy automobile and photovoltaic industry enter a rapid development stage, the market promotion effect is gradually enhanced, and the demand is continuously promoted, so that the rapid increase of the product demand of each subdivision in each link at the upstream of the industrial chain is driven. In order to meet the global demand of rapidly increasing power batteries and energy storage, main new energy enterprises in the world are greatly expanded, and the demand of upstream raw materials is increased at a high speed; meanwhile, in order to improve the stability and the safety of the product, the requirements on the quality indexes of the raw materials are continuously improved.
Lithium iron phosphate is a main anode material of a lithium battery, and iron phosphate is a raw material of the lithium iron phosphate, a traditional phosphorus chemical product has new activity due to the requirement of a new energy lithium battery material, the phosphorus chemical product for electronics taking "phosphate rock-phosphate-iron phosphate-lithium iron phosphate" as a route receives more and more attention, and the product quality of the iron phosphate directly affects the stability and safety of the lithium iron phosphate.
The technical method for preparing iron phosphate disclosed in the prior art comprises the following steps:
(1) ferrous sulfate + industrial monoammonium phosphate oxidation method: reacting ferrous sulfate with iron to remove impurities to obtain a ferrous sulfate solution, dissolving industrial monoammonium phosphate by pure water, adding hydrogen peroxide, mixing the ferrous sulfate solution and the industrial monoammonium phosphate solution, precipitating to obtain a crude ferric phosphate product, aging and pulping to obtain ferric phosphate dihydrate, and drying and calcining to obtain the ferric phosphate product.
(2) Iron, iron oxide + phosphoric acid oxidation: for example, patent 201710635752.9 discloses a process for preparing battery-grade high-purity nano iron phosphate, which comprises using a mixture of iron powder and iron oxide as an iron source, using phosphoric acid as a phosphorus source to prepare a ferrous phosphate mother liquor, then adding hydrogen peroxide to prepare a crude iron phosphate product, finally washing the crude iron phosphate product with distilled water and ethanol, and drying the washed product to obtain the iron phosphate.
The preparation of battery grade iron phosphate by using ferrous phosphate and industrial monoammonium phosphate has become a mainstream process in the industry due to low cost. However, because the phosphorus source adopted in the process is industrial-grade monoammonium phosphate (or clear liquid or mother liquid) prepared from wet-process phosphoric acid, part of impurities carried in the wet-process phosphoric acid inevitably enter the monoammonium phosphate (or clear liquid or mother liquid), and finally enter the iron phosphate product along with precipitation, and further other crystals are formed in the iron phosphate crystallization process, so that the stability of the iron phosphate crystals is influenced, and the stability and safety of the lithium iron phosphate material are further influenced.
Patent publication No. CN113104827A discloses a method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear liquid or industrial ammonium phosphate mother liquid, which discloses purifying industrial ammonium phosphate clear liquid through defluorination, refining and heavy metal removal operations in sequence to prepare iron phosphate with low impurity content. However, the method has the disadvantages of difficult operation, difficult accurate control of pH in the refining process, complex crystal form of production and preparation, unstable impurity content of the obtained product, and high impurity content of the obtained product after repeated tests, and is difficult to achieve the technical effect claimed by the embodiment.
Disclosure of Invention
The invention aims to provide a preparation method of high-purity iron phosphate, which is simple and feasible and greatly improves the purity of the iron phosphate.
The second purpose of the invention is to provide high-purity iron phosphate, the content of calcium, magnesium, manganese, aluminum, potassium, sodium and other impurities of which is lower than 15ppm, particularly the content of potassium can reach below 10ppm, and the prepared lithium iron phosphate can be effectively ensured to have good safety and stability.
In order to achieve the purpose, the invention adopts the technical scheme that:
firstly, the invention provides a method for preparing high-purity iron phosphate by adopting a multistage purification method, which comprises the following steps:
s1, adding a potassium-containing compound into the monoammonium phosphate solution for reaction, and filtering to obtain a first-grade clear liquid after the reaction is finished; the monoammonium phosphate solution is prepared by adding pure water into industrial monoammonium solid or monoammonium phosphate clear liquid;
s2 adding a chelating agent into the primary clear liquid obtained in the step S1 for reaction to obtain a secondary clear liquid;
s3, reacting the secondary clear liquid obtained in the step S2 with a ferrous sulfate solution in the presence of an oxidant to obtain iron phosphate slurry;
and S4, washing and drying the iron phosphate slurry after the reaction of the step S3 is finished to obtain an iron phosphate product.
Preferably, in step S1, the concentration of the monoammonium phosphate solution is 15 to 25% based on the monoammonium phosphate; the amount of potassium-containing compound added in step S1 is: controlling the total potassium content in the reaction solution of the step S1 to be 0.1-0.5% by mass percent; in the step S1, the potassium-containing compound is at least one of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium carbonate, potassium bicarbonate or potassium hydroxide, and the calcium and magnesium content in the potassium-containing compound is less than 100 ppm; the reaction temperature of the step S1 is 40-60 ℃, and the reaction time is 0.5-3 h.
Preferably, in step S2, the chelating agent is added in an amount of: controlling the mass percent of the chelating agent in the reaction solution to be 0.2-0.5%; in step S2, the chelating agent is at least one selected from ethylenediaminetetraacetic acid (EDTA), aminotrimethylenephosphonic Acid (ATMP), hydroxyethylidene diphosphonic acid (HEDP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTCA), or 2-hydroxyphosphonoacetic acid (HPAA); the reaction temperature of the step S2 is 40-60 ℃, and the reaction time is 0.5-3 h.
Preferably, in step S3, the concentration of ferrous sulfate is 10 to 15%, and the mass fractions of calcium, magnesium, manganese, aluminum, potassium, and sodium in the ferrous sulfate solution are all less than 50 ppm; a pH regulator is added in the step S3, the pH regulator and an oxidant are added into the reaction system at the same time, and the adding time is 0.5-2 h; the amount of the oxidant satisfies the following conditions: 1.2-1.5 times of the required dosage of completely oxidizing the ferrous sulfate; the dosage of the pH regulator satisfies the following conditions: controlling the pH value of the reaction end point to be 2.0-3.0; preferably, the oxidant is hydrogen peroxide, and the pH regulator is ammonia water or ammonia gas.
Preferably, step S4 specifically includes the following steps:
s41, taking the secondary washing filtrate as primary washing water, after washing, performing iron phosphate crystallization, pulping again, and adding industrial phosphoric acid for aging and pulping; the dosage of the washing water for one time is 10-20 times of the mass of the solid phase; after washing, adding pure water to adjust the solid content to 10-15% for pulping again; dilute phosphoric acid (H) with the concentration of 3-10% is added in the secondary pulping process3PO4Metering) to control the pH value of the reaction system to be 2.0-2.2, so that the most stable compound, namely ferric phosphate dihydrate is formed; after pulping again, the stirring linear velocity is controlled to be 0.5-2 m/s, stirring is carried out for 1-3 h, and aging and pulping are carried out.
S42, taking pure water as secondary washing water, and drying after secondary washing to obtain an iron phosphate product; the dosage of the secondary washing water is 20-30 times of the mass of the solid phase;
s43, the filtrate obtained in the step S42 is secondary washing filtrate, part of the secondary washing filtrate is returned and sequentially washed to be used as primary washing water, the rest part of the secondary washing filtrate enters a wastewater purification system, the filtrate obtained in the step S41 is primary washing filtrate, all the filtrate enters the wastewater purification system, after the wastewater purification system is purified, 50-70% of wastewater is converted into pure water, and the rest 30-50% of high-concentration wastewater enters a phosphate fertilizer system to be recycled.
The invention also provides the high-purity iron phosphate prepared by the preparation method.
The invention has the beneficial effects that:
1. the multistage purification technology provided by the invention further purifies industrial monoammonium phosphate or monoammonium phosphate clear liquid, so that the impurity contents of calcium, magnesium, manganese, aluminum, potassium and sodium in the purified monoammonium phosphate are lower, the crystallization precipitation amount of calcium, magnesium, manganese, aluminum, potassium and sodium in the ferric phosphate precipitation process is effectively reduced, the impurities of calcium, magnesium, manganese, aluminum, potassium and sodium can be washed and separated by simple water washing, the impurity contents of calcium, magnesium, manganese, aluminum, potassium and sodium after washing can be reduced to be within 15ppm, and the impurity contents are far lower than the limit values of the ions in the current HG/T4701-.
2. The invention creatively provides a method for removing potassium ions and sodium ions in monoammonium phosphate or monoammonium phosphate clear liquid by replenishing potassium ions in advance, and the inventor converts impurity ions such as fluosilicate in the potassium-containing complex salt (such as potassium fluosilicate) into potassium-containing complex salt to precipitate and separate out by replenishing the potassium ions in advance, thereby effectively reducing the amount of complex salts such as potassium sodium fluosilicate dissolved in a liquid phase and further reducing the precipitation amount of the complex salts such as potassium sodium fluosilicate in the ferric phosphate precipitation process.
3. The invention also provides a method for selectively reacting the metal impurities such as calcium, magnesium, manganese, aluminum and the like with the chelating agent to form stable soluble substances by adopting a chelation technology, so that the metal impurities such as calcium, magnesium, manganese, aluminum and the like are effectively prevented from forming precipitates in the ferric phosphate precipitation process, and the content of the metal impurities such as calcium, magnesium, manganese, aluminum and the like in the ferric phosphate solid phase is effectively reduced. The method does not select the conventional method for removing the metal impurities such as calcium, magnesium, manganese, aluminum and the like by precipitating, but creatively chelates the metal impurities such as calcium, magnesium, manganese, aluminum and the like so that the metal impurities do not participate in the precipitation process of the ferric phosphate.
4. The invention adds oxidant and pH regulator into the reaction system at the same time, and realizes the Fe control by controlling the feeding amount and the feeding speed2+To Fe3+The oxidation rate in the conversion process is controlled, and the generation of Fe is avoided3+The phenomenon of wrapping caused by too fast crystal growth due to too high concentration is avoided, the condition that chelated calcium, magnesium, manganese and aluminum are brought into the crystal in a small amount due to too fast crystal growth is also avoided, and the stable control on the iron phosphate crystal is realized.
5. According to the method, phosphoric acid is added in the subsequent treatment process for aging treatment, the pH value of a reaction system is controlled to be 2.0-2.2, and other forms (of a plurality of crystal waters) are converted into dihydrate, so that the dihydrate can form the most stable compound, namely, ferric phosphate dihydrate, and further the impurity carrying amount is reduced, so that the washing is more thorough, and the impurity content in the final product is lower.
6. The invention adopts a countercurrent washing mode, uses the secondary washing filtrate as primary washing water, effectively reduces the consumption of the primary washing to pure water, and reduces the consumption of the pure water by more than 30 percent of the whole system.
7. The excessive phosphorus and potassium elements and the chelating agent supplemented by the method enter a wastewater system and return to a phosphate fertilizer production process along with high-concentration wastewater, wherein the excessive phosphoric acid is directly recycled; the potassium element directly serves as a nutrient element and enters the compound fertilizer, so that the potassium is not wasted; the chelating agent still keeps a certain chelating capacity when entering the fertilizer, can be effectively combined with metal cations, improves the water solubility of the fertilizer, is beneficial to absorption and transformation of crops, and improves the fertilizer efficiency of the product.
Drawings
Fig. 1 is a process flow chart of a method for preparing high-purity iron phosphate by using a multistage purification method in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention is further described with reference to specific embodiments below. Those whose conditions are not specified in the examples were carried out according to the conventional conditions or conditions recommended by the manufacturer. The reagents used, or those not indicated together with the manufacturer, are conventional products which are commercially available. All features disclosed in this specification may be combined in any combination, except features or/and steps which are mutually exclusive.
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The ferrous sulfate used in the following examples of the application is a same batch of product, wherein the contents of calcium, magnesium, manganese, aluminum, potassium and sodium are respectively 95ppm, 56ppm, 92ppm, 68ppm, 78ppm and 98 ppm;
the potassium-containing compounds used in the examples described below are all commercially available laboratory reagents with negligible impurity content;
industrial monoammonium phosphate in the following examples of the application is a product of the same batch, and is added with pure water to prepare a monoammonium phosphate solution A with the concentration of 20 percent (calculated by the monoammonium phosphate);
the industrial monoammonium phosphate clear solutions in the following examples of the application are all products of the same batch, and are added with pure water to prepare a monoammonium phosphate solution B with the concentration of 25 percent (calculated by monoammonium phosphate);
the contents of the components in the monoammonium phosphate solution prepared from the two raw materials are respectively shown in table 1:
TABLE 1 monoammonium phosphate solution content of each component
Example 1
The embodiment provides a method for preparing high-purity iron phosphate by adopting a multistage purification method, which comprises the following steps:
s1, taking 1000ml of monoammonium phosphate solution A, adding potassium carbonate into the monoammonium phosphate solution, and controlling the mass percentage of the total potassium content in the monoammonium phosphate solution to be 0.3%; stirring and reacting for 2h at 50 ℃, and filtering to obtain primary clear liquid after the reaction is finished;
s2, adding EDTA (ethylene diamine tetraacetic acid) with the mass percentage of 0.3% into the primary clear liquid prepared in the step S1, and stirring and reacting at 50 ℃ for 2 hours to prepare secondary clear liquid;
s3, mixing the secondary clear liquid obtained in the step S2 with 15% ferrous sulfate solution; adding hydrogen peroxide and ammonia water simultaneously, wherein the feeding time is controlled to be 1h, the dosage of the hydrogen peroxide is 1.2 times of the theoretical dosage of completely oxidized ferrous sulfate, and the dosage of the ammonia water is used for controlling the pH value of the reaction end point to be 2.8-3.0; obtaining iron phosphate slurry after the reaction is finished;
s41, taking the secondary washing filtrate as primary washing water, wherein the dosage of the primary washing water is 15 times of the mass of the solid phase; adding pure water after washing to adjust the solid content to 15%, pulping again, and adding dilute phosphoric acid (H) with concentration of 5% during pulping again3PO4A meter); after pulping again, controlling the stirring linear speed to be 2m/s, stirring for 2h, aging and pulping;
s42, pure water is used as secondary washing water, and the using amount of the secondary washing water is 20 times of the mass of the solid phase; drying the washed mixture to constant weight to obtain an iron phosphate product;
s43, the filtrate obtained in the step S42 is secondary washing filtrate, part of the secondary washing filtrate is returned and sequentially washed to be used as primary washing water, the rest part of the secondary washing filtrate enters a wastewater purification system, the filtrate obtained in the step S41 is primary washing filtrate, all the filtrate enters the wastewater purification system, after the wastewater purification system is purified, 70% of wastewater is converted into pure water, and the rest 30% of high-concentration wastewater enters a phosphate fertilizer system to be recycled.
Example 2
This example provides a method for preparing high-purity iron phosphate by using a multi-stage purification method, which is different from example 1 in that:
in step S1, the amount of potassium carbonate added is: the mass percentage of the total potassium content in the monoammonium phosphate solution is controlled to be 0.1 percent.
Example 3
This example provides a method for preparing high-purity iron phosphate by using a multi-stage purification method, which is different from example 1 in that:
in step S1, the monoammonium phosphate solution a is replaced with monoammonium phosphate solution B, and the amount of potassium carbonate added is: the mass percentage of the total potassium content in the monoammonium phosphate solution is controlled to be 0.5 percent.
Example 4
This example provides a method for preparing high-purity iron phosphate by using a multi-stage purification method, which is different from example 1 in that:
in step S2, the amount of EDTA added was 0.2% by mass of the total amount of the primary clear solution.
Example 5
This example provides a method for preparing high-purity iron phosphate by using a multi-stage purification method, which is different from example 1 in that:
in step S2, the monoammonium phosphate solution a is replaced with the monoammonium phosphate solution B, and the amount of EDTA added is 0.5% by mass of the total amount of the primary clear liquid.
Example 6
This example provides a method for preparing high-purity iron phosphate by using a multi-stage purification method, which is different from example 1 in that:
in step S2, EDTA is replaced with an equal amount of ATMP.
Comparative example 1
This comparative example provides a method for preparing high-purity iron phosphate using a multi-stage purification method, which is different from example 1 in that:
in step S1, sodium carbonate is added in an amount of: the mass percentage of the total sodium content in the monoammonium phosphate solution is controlled to be 0.3 percent.
Comparative example 2
This comparative example provides a method for preparing high-purity iron phosphate using a multi-stage purification method, which is different from example 1 in that:
step S2 is: adjusting the pH value of the primary clear liquid prepared in the step S1 to 7.0, reacting for 0.5h, precipitating, and filtering to obtain secondary clear liquid; the subsequent reaction was continued in the same manner as in example 1.
Comparative example 3
This example provides a method for preparing high-purity iron phosphate by using a multi-stage purification method, which is different from example 1 in that:
in step S3, the secondary clear liquid prepared in step S2, 15% ferrous sulfate solution, hydrogen peroxide and ammonia water are added simultaneously and mixed, and the mixture is stirred and reacted for 1 hour to obtain the iron phosphate slurry.
Comparative example 4
This example provides a method for preparing high-purity iron phosphate by using a multi-stage purification method, which is different from example 1 in that:
in the step S41, the secondary washing filtrate is used as primary washing water, and the dosage of the primary washing water is 15 times of the mass of the solid phase; after washing, pulping is not carried out again, and diluted phosphoric acid is not added for aging treatment.
Comparative example 5
The comparative example provides a method for preparing high-purity iron phosphate by adopting a multistage purification method, which comprises the following steps:
s1, fluorine removal: adding 1% of diatomite and 1% of sodium carbonate solution into the clear industrial ammonium phosphate solution to react for 5 hours, and then filtering to obtain a phosphorus-containing solution after fluorine removal;
s2, refining: introducing ammonia gas into the phosphorus-containing solution prepared in the step S1 to adjust the pH value, adjusting the pH value to 6.8, and removing impurities such as calcium, magnesium, manganese, aluminum and the like through a precipitation reaction to obtain a phosphate solution with low impurity ion content;
s3, synthesizing ferric phosphate dihydrate: diluting the refined phosphate solution obtained in the step S2 to 20% (calculated by monoammonium phosphate) by adding pure water, and adjusting the pH value to obtain a phosphate solution required by the synthesis reaction; dissolving ferrous sulfate crystals in water to prepare a 15% ferrous sulfate solution, and obtaining a sulfate solution required by a synthetic reaction; slowly adding a phosphate solution required by the reaction into a sulfate solution, and synchronously adding hydrogen peroxide and ammonia water, wherein the amount of the hydrogen peroxide is 1.2 times of the mass of ferrous sulfate, and the amount of the ammonia water is used for controlling the pH value of the reaction end point to be 2.8-3.0 to fully react to obtain a synthetic slurry; and (3) carrying out filter pressing on the synthetic slurry, and washing and drying a filter cake to obtain the ferric phosphate dihydrate.
Examples of the experiments
The iron phosphate products prepared in the above examples and comparative examples are subjected to performance tests, and the test method refers to HG/T4701-. The test results are shown in table 2:
TABLE 2 test results for various examples and comparative examples
| Composition (I) | K/ppm | Na/ppm | Ca/ppm | Mg/ppm | Mn/ppm | Al/ppm |
| Example 1 | 8.15 | 11.23 | 12.85 | 11.82 | 13.36 | 11.32 |
| Example 2 | 10.25 | 14.35 | 12.30 | 11.75 | 13.58 | 11.69 |
| Example 3 | 7.25 | 10.56 | 12.55 | 12.03 | 13.84 | 11.86 |
| Example 4 | 8.32 | 11.35 | 14.32 | 13.85 | 14.69 | 12.96 |
| Example 5 | 8.18 | 11.52 | 11.20 | 10.65 | 11.21 | 10.10 |
| Example 6 | 8.20 | 11.28 | 12.61 | 11.62 | 13.32 | 11.29 |
| Comparative example 1 | 31.21 | 28.20 | 13.20 | 12.10 | 13.92 | 12.15 |
| Comparative example 2 | 9.21 | 11.62 | 36.15 | 52.12 | 41.25 | 48.36 |
| Comparative example 3 | 8.92 | 11.35 | 15.24 | 14.20 | 15.21 | 13.41 |
| Comparative example 4 | 9.72 | 12.25 | 16.12 | 15.25 | 16.78 | 14.52 |
| Comparative example 5 | 32.51 | 29.58 | 42.28 | 56.31 | 43.25 | 52.31 |
In conclusion, in the iron phosphate prepared by the method for preparing high-purity iron phosphate by adopting the multistage purification method, the contents of elements such as calcium, magnesium, potassium, sodium, manganese, aluminum and the like are all originally lower than the requirements specified in the current standard HG/T4701-2014, so that the prepared lithium iron phosphate material has higher stability and safety, and the preparation method is simple and easy to implement and has good industrial prospects.
The present invention is not limited to the above embodiments, and any structural changes made under the teaching of the present invention shall fall within the protection scope of the present invention, which has the same or similar technical solutions as the present invention.
Claims (10)
1. A method for preparing high-purity iron phosphate by adopting a multistage purification method is characterized by comprising the following steps:
s1, adding a potassium-containing compound into the monoammonium phosphate solution for reaction, and filtering to obtain a first-grade clear liquid after the reaction is finished; the monoammonium phosphate solution is prepared by adding pure water into industrial monoammonium solid or monoammonium phosphate clear liquid;
s2 adding a chelating agent into the primary clear liquid obtained in the step S1 for reaction to obtain a secondary clear liquid;
s3, reacting the secondary clear liquid obtained in the step S2 with a ferrous sulfate solution in the presence of an oxidant to obtain iron phosphate slurry;
and S4, washing and drying the iron phosphate slurry after the reaction of the step S3 is finished to obtain an iron phosphate product.
2. The method for preparing high-purity iron phosphate by using a multistage purification method according to claim 1, wherein the amount of the potassium-containing compound added in step S1 is: and controlling the total potassium content in the reaction solution of the step S1 to be 0.1-0.5% by mass percent.
3. The method for preparing high-purity iron phosphate according to claim 1, wherein the chelating agent is at least one selected from ethylenediaminetetraacetic acid, aminomethylidenephosphonic acid, hydroxyethylidene diphosphonic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, and 2-hydroxyphosphonoacetic acid in step S2.
4. The method for preparing high-purity iron phosphate by using a multistage purification method according to claim 3, wherein in step S2, the chelating agent is added in an amount of 0.2 to 0.5% by mass.
5. The method for preparing high-purity iron phosphate using a multi-stage purification process according to claim 1,
in the step S1, the reaction temperature is 40-60 ℃, and the reaction time is 0.5-3 h;
in step S2, the reaction temperature is 40-60 ℃ and the reaction time is 0.5-3 h.
6. The method for preparing high-purity iron phosphate by adopting a multistage purification method according to any one of claims 1 to 5, wherein a pH regulator is further added in step S3, and the pH regulator and the oxidant are simultaneously added into the reaction system for 0.5 to 2 hours;
the amount of the oxidant satisfies the following conditions: 1.2-1.5 times of the required dosage of completely oxidizing the ferrous sulfate; the dosage of the pH regulator satisfies the following conditions: controlling the pH value of the reaction end point to be 2.0-3.0.
7. The method for preparing high-purity iron phosphate using a multi-stage purification process according to claim 6,
in the step S1, the concentration of the monoammonium phosphate solution is 15-25% by weight of monoammonium phosphate;
in the step S3, the concentration of the ferrous sulfate is 10-15%, and the mass fractions of calcium, magnesium, manganese, aluminum, potassium and sodium in the ferrous sulfate solution are all less than 50 ppm.
8. The method for preparing high-purity iron phosphate by using a multistage purification method according to claim 7, wherein the step S4 specifically comprises the following steps:
s41, taking the secondary washing filtrate as primary washing water, after washing, performing iron phosphate crystallization, pulping again, and adding industrial phosphoric acid for aging and pulping;
and S42, adopting pure water as secondary washing water, and drying after secondary washing to obtain the iron phosphate product.
9. The method for preparing high-purity iron phosphate using a multi-stage purification process according to claim 8,
in the step S41, the dosage of the washing water for one time is 10-20 times of the mass of the solid phase; after washing, adding pure water to adjust the solid content to 10-15% for pulping again; dilute phosphoric acid with the concentration of 3-10% is added in the secondary pulping process;
in step S42, the amount of the secondary washing water is 20-30 times of the mass of the solid phase.
10. The high-purity iron phosphate prepared by the method for preparing high-purity iron phosphate according to any one of claims 1 to 9 by using a multistage purification method.
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