CN114906830A - Method for controllably preparing battery-grade iron phosphate from pyrite cinder - Google Patents
Method for controllably preparing battery-grade iron phosphate from pyrite cinder Download PDFInfo
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- CN114906830A CN114906830A CN202210844571.8A CN202210844571A CN114906830A CN 114906830 A CN114906830 A CN 114906830A CN 202210844571 A CN202210844571 A CN 202210844571A CN 114906830 A CN114906830 A CN 114906830A
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- iron
- pyrite cinder
- slurry
- phosphate
- ferric
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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 93
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 67
- 239000011028 pyrite Substances 0.000 title claims abstract description 67
- 239000003818 cinder Substances 0.000 title claims abstract description 65
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000002002 slurry Substances 0.000 claims abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 46
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 45
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 36
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 36
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 36
- 238000001914 filtration Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002585 base Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000010790 dilution Methods 0.000 claims abstract description 6
- 239000012895 dilution Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011268 mixed slurry Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 235000014413 iron hydroxide Nutrition 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 15
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 11
- 239000011790 ferrous sulphate Substances 0.000 description 10
- 235000003891 ferrous sulphate Nutrition 0.000 description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 10
- 239000002699 waste material Substances 0.000 description 7
- -1 dihydrate ferric phosphate Chemical class 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A method for controllably preparing battery-grade iron phosphate from pyrite cinder comprises the steps of crushing the pyrite cinder, adding the crushed pyrite cinder into acid, stirring, adding water, preserving heat, adding water for dilution, and filtering to obtain a reaction solution; adding iron powder into the reaction solution, stirring, and adding water to dilute to obtain a raw material slurry; adding alkali liquor into the reducing slurry to adjust the pH value, and filtering to obtain refined reducing liquid; then adding an oxidant to react to obtain oxidized slurry; adding alkali liquor into the oxidized slurry to adjust the pH, filtering and collecting a filter cake to obtain ferric hydroxide, and washing the ferric hydroxide with water to obtain high-purity ferric hydroxide; adding water into high-purity ferric hydroxide to prepare slurry, mixing the slurry with phosphoric acid, reacting, filtering and collecting a filter cake to obtain a ferric phosphate wet base, washing to obtain the high-purity ferric phosphate wet base, drying to obtain ferric phosphate dihydrate, and calcining to obtain the battery-grade anhydrous ferric phosphate. The method not only effectively utilizes pyrite cinder resources and reduces discharge and pollution, but also provides a cheap and high-quality iron source for iron phosphate production, and prepares the battery-grade high-quality iron phosphate.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a method for preparing battery-grade iron phosphate by using pyrite cinder.
Background
At present, iron sources of iron phosphate mainly comprise ferrous sulfate and reduced iron powder which are titanium white byproducts, along with the rapid development of new energy, the price of the iron source also rises, and the supply and demand relationship becomes tense, so that the iron source which is cheap and easy to obtain is imperatively found.
The pyrite cinder is a by-product of sulfuric acid production from pyrite, and the iron content can reach about 60%, but due to the limitation of the prior art, the pyrite cinder is basically sold to a smelting plant at a low price to be used as a blending material for pyrometallurgical iron, so that not only is high energy consumption caused in smelting production, but also the cost for producing acid from pyrite is relatively increased.
Chinese patent publication No. CN109368610A provides a method for preparing iron phosphate from pyrite cinder, which requires pretreatment to increase carbon emission, and the used alkali liquor causes a large amount of wastewater in the production process and waste of acid; the added non-ionic flocculant and PEG also increase the production cost; the pickle liquor is not purified, so that the iron phosphate impurity content of the product is higher.
Chinese patent publication No. CN108706561A provides a method for preparing iron phosphate from pyrite cinder, which requires washing and drying of pyrite cinder, resulting in a large amount of wastewater and increased energy consumption. Because the hydrothermal time is long, the ferric hydroxide colloid generated in the process is difficult to filter; in addition, the pH is low, the iron is difficult to control and completely sinks out, a large amount of iron source waste can be caused in large-scale device production, and meanwhile, impurity removal is not carried out on hydrothermal reaction liquid, so that the product quality is difficult to ensure.
Chinese patent publication No. CN113184820A provides a method for preparing iron phosphate from ferrous sulfate as a titanium white byproduct, which relates to the purification process of ferrous sulfate heptahydrate, but requires heating in the processes of pH adjustment and oxidation, and increases energy consumption. The hydrogen peroxide and the alkali liquor are used as mixed oxidants, so that the oxidation efficiency of the hydrogen peroxide is reduced; the mixed acid is used in the synthesis of the iron phosphate, which not only increases the cost and causes waste, but also introduces impurity sulfate radicals, increases the treatment difficulty and causes low product purity.
Disclosure of Invention
The invention aims to provide a method for controllably preparing battery-grade iron phosphate from pyrite cinder, which solves the problems of difficulty in impurity removal, high impurity removal cost, more byproducts and difficulty in treatment during utilization of pyrite cinder, effectively utilizes pyrite cinder resources, and provides a cheap and high-quality iron source for production of iron phosphate so as to reduce production cost, reduce emission and pollution and provide battery-grade high-quality iron phosphate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for controllably preparing battery-grade iron phosphate from pyrite cinder comprises the following steps:
s1, crushing pyrite cinder to obtain pyrite cinder powder with uniform particle size, and then adding the pyrite cinder powder into an acid solution to obtain mixed slurry;
s2, stirring the mixed slurry at normal pressure and 85-116 ℃ for reaction for 2.5-5 hours, adding water, preserving heat for 0.5-2 hours, filtering and collecting reaction liquid;
s3, adding iron powder into the reaction liquid, stirring and reacting for 0.5-3.0 hours at normal pressure and at the temperature of 50-95 ℃, and adding water again to dilute to obtain a raw material slurry;
s4, adding alkali liquor into the reducing slurry, adjusting the pH value to 5.2-7.4, filtering and collecting filtrate to obtain refined reducing liquid;
s5, adding an oxidant into the refined reducing solution, and reacting at 15-75 ℃ for 0.5-24 hours to obtain oxidized slurry;
s6, adding alkali liquor into the oxidized slurry, adjusting the pH value to 2.8-4.8, filtering and collecting a filter cake to obtain ferric hydroxide;
s7, washing the ferric hydroxide by using water to obtain high-purity ferric hydroxide;
s8, adding water into high-purity ferric hydroxide to prepare slurry containing 2-12% of iron, mixing the slurry with phosphoric acid, reacting at the normal pressure and the temperature of 60-97 ℃ for 1.8-5.5 hours in a heat preservation manner, filtering, and collecting a filter cake to obtain a ferric phosphate wet base;
s9, washing the iron phosphate wet base for 1-3 times to obtain a high-purity iron phosphate wet base;
s10, drying the high-purity iron phosphate wet base at 105-500 ℃ to obtain ferric phosphate dihydrate;
s11, calcining the ferric phosphate dihydrate at 680-950 ℃ for 1-2 hours to obtain the battery-grade anhydrous ferric phosphate.
Preferably, in step S1, the pyrite cinder contains Fe 2 O 3 、Fe 3 O 4 And FeO, the mass content of the single iron is 45-60%, and the pyrite cinder contains impurities of Si, Al, Ca, Zn and Mg.
Preferably, in the step S1, the particle size of the crushed pyrite cinder powder is 80-600 meshes; the acid solution is sulfuric acid with the mass concentration of 38-65%, and the using amount of the sulfuric acid is 1.5-3 times of the mass of the pyrite cinder.
Preferably, in step S2, the stirring reaction temperature is 93 to 115 ℃, and the reaction time is 2.5 to 3.5 hours.
Preferably, in step S3, the iron powder is recovered scrap iron powder and/or primary reduced iron powder, and the amount of the iron powder is 0.5 to 0.8 times of the amount of ferric iron measured by sampling the reaction solution in step S2; adding water to ensure that the iron content is 3-9%; the stirring reaction temperature is 65-85 ℃, and the reaction time is 0.5-2.0 hours.
Preferably, in the steps S4 and S6, the alkali liquor is one of 10% -38% of sodium hydroxide, 10% -35% of sodium carbonate, 10% -30% of ammonia water and 10% -30% of urea by mass concentration.
Preferably, in step S4, the pH is adjusted to 5.5 to 6.5.
Preferably, in step S5, the oxidant is hydrogen peroxide or air, and the molar ratio of hydrogen peroxide to iron is 0.5: 1-0.7: 1; the reaction temperature after the oxidant is added is 25-55 ℃, the reaction time is 0.5-2 hours, and the oxidation time after the air is added is 3-24 hours.
Preferably, in step S6, the pH is adjusted to 3.2-4.2.
Preferably, in step S8, water is added to the high-purity ferric hydroxide to prepare a slurry containing 2% to 12% of iron, and the molar ratio of phosphorus contained in the fed phosphoric acid to iron contained in the ferric hydroxide is 0.95 to 1.2: 1; the reaction temperature of the slurry and the phosphoric acid after mixing is 60-80 ℃, and the reaction time is 2.2-3.5 hours.
Preferably, in the step S10, the drying temperature is 180-300 ℃.
Preferably, in step S11, the calcination temperature is 650 to 750 ℃.
According to the technical scheme, pyrite cinder is crushed and then added into an acid solution, the temperature is raised, the reaction is carried out under the condition of heat preservation, then water is added for dilution, the filtrate is filtered and collected after the reaction, the filtrate is reduced by using simple substance iron to obtain a ferrous solution, the reduced solution is added with alkali to adjust the pH value to 5.2-7.4, then the filtration is carried out to remove impurities, an oxidant ferrous oxide is added into the filtrate, then the alkali is added again to adjust the pH value to 2.8-4.8, iron is precipitated in the form of ferric hydroxide, ferric hydroxide is obtained by filtering slurry, the ferric hydroxide is washed again and then prepared into slurry, the slurry reacts with phosphoric acid at the temperature of 60-97 ℃ for 1.8-5.5 hours, the ferric phosphate is obtained by filtration, and the ferric phosphate is washed, dried and calcined to obtain the high-purity battery-grade ferric phosphate. The method only needs to crush the pyrite cinder in the pretreatment, does not need to input other raw materials, is simple and easy to implement, does not generate three wastes, and has low cost. The method has the advantages of mild reaction conditions, short reaction time, modularized working procedures, high controllability of products and high purity of the products, the iron hydroxide can be used as a raw material of products and downstream iron-based products, the generated waste residues are recycled, the waste liquid is mainly sulfate, the shunting is simple, the iron phosphate washing water can be used for washing the iron hydroxide, and the water discharge is small.
Drawings
Fig. 1 is an SEM image of iron phosphate prepared in example 1 of the present invention;
fig. 2 is an XRD primary iron phosphate peak finding pattern of iron phosphate prepared in example 1 of the present invention.
Detailed Description
The contents and effects of the present invention will be further illustrated and described below by examples. The examples listed are only some of the examples of the present invention and not all of them.
The contents of components in the pyrite cinder raw material selected in the examples and comparative examples of the present invention are shown in table 1.
TABLE 1 ingredient content table of pyrite cinder raw material used in examples
Example 1
A method for controllably preparing battery-grade iron phosphate from pyrite cinder comprises the following steps:
s1, crushing pyrite cinder of a raw material 1 in the table 1 to 350 meshes, and then slowly adding the crushed pyrite cinder into a sulfuric acid solution with the mass concentration of 50% while stirring to obtain mixed slurry; the mass of the pure sulfuric acid is 2 times of that of the pyrite cinder;
s2, stirring the mixed slurry for reaction for 3 hours under the conditions of normal pressure and 100 ℃, then adding water, preserving heat for 0.5 hour, filtering and collecting reaction liquid;
s3, adding iron powder which is 0.6 time of the weight of ferric iron contained in the reaction solution into the reaction solution, and then stirring and reacting for 1 hour under the conditions of normal pressure and 80 ℃ to obtain returned raw material slurry;
s4, adding a sodium hydroxide solution with the mass concentration of 15% into the reduced slurry, adjusting the pH value to 5.8, filtering and collecting filtrate to obtain a refined ferrous sulfate solution;
s5, adding hydrogen peroxide into the refined ferrous sulfate solution, and reacting for 1 hour at 30 ℃ to obtain oxidized slurry; the molar ratio of hydrogen peroxide to iron is 0.65: 1;
s6, adding a sodium hydroxide solution with the mass concentration of 15% into the oxidized slurry, adjusting the pH to 4.2, filtering and collecting a filter cake to obtain ferric hydroxide;
s7, washing the ferric hydroxide for 2 times by using water to obtain high-purity ferric hydroxide;
s8, adding water into high-purity ferric hydroxide to prepare ferric hydroxide slurry containing 8% of iron, mixing the ferric hydroxide slurry with phosphoric acid, reacting at the normal pressure and the temperature of 80 ℃ for 3 hours in a heat preservation manner, filtering and collecting a filter cake to obtain a ferric phosphate wet base; the molar ratio of phosphorus and iron hydroxide of the fed phosphoric acid is 1.01: 1;
s9, washing the iron phosphate wet base for 2 times to obtain a high-purity iron phosphate wet base;
s10, drying the high-purity iron phosphate wet base at 300 ℃ to obtain ferric phosphate dihydrate;
s11, calcining the dihydrate ferric phosphate at 750 ℃ for 1.5 hours to obtain the battery-grade anhydrous ferric phosphate.
Example 2
A method for controllably preparing battery-grade iron phosphate from pyrite cinder comprises the following steps:
s1, crushing pyrite cinder of a raw material 2 in the table 1 to 80 meshes, and then slowly adding the crushed pyrite cinder into a sulfuric acid solution with the mass concentration of 38% under stirring to obtain mixed slurry; the mass of the pure sulfuric acid is 3 times of that of the pyrite cinder;
s2, stirring the mixed slurry at the normal pressure and at the temperature of 85 ℃ for reaction for 2.5 hours, adding water for dilution until the iron content is 9%, preserving heat for 1 hour, filtering and collecting to obtain a reaction solution;
s3, adding iron powder which is 0.8 time of the weight of ferric iron contained in the reaction solution into the reaction solution, and then stirring and reacting for 2 hours under the conditions of normal pressure and 85 ℃ to obtain returned raw material slurry;
s4, adding a sodium carbonate solution with the mass concentration of 20% into the reduced slurry, adjusting the pH value to 6.5, filtering and collecting filtrate to obtain a refined ferrous sulfate solution;
s5, adding hydrogen peroxide into the refined ferrous sulfate solution, and reacting for 1.5 hours at 15 ℃ to obtain oxidized slurry; the molar ratio of hydrogen peroxide to iron is 0.7: 1;
s6, adding a sodium carbonate solution with the mass concentration of 35% into the oxidized slurry, adjusting the pH to 4.8, filtering and collecting a filter cake to obtain ferric hydroxide;
s7, washing the ferric hydroxide for 2 times by using water to obtain high-purity ferric hydroxide;
s8, adding water into high-purity ferric hydroxide to prepare ferric hydroxide slurry containing 12% of iron, mixing the ferric hydroxide slurry with phosphoric acid, reacting at the normal pressure and the temperature of 97 ℃ for 1.8 hours in a heat preservation manner, filtering and collecting a filter cake to obtain a ferric phosphate wet base; the molar ratio of the phosphorus to the iron is 0.95: 1;
s9, washing the iron phosphate wet base for 2 times to obtain a high-purity iron phosphate wet base;
s10, drying the high-purity iron phosphate wet base at 105 ℃ to obtain dihydrate ferric phosphate;
s11, calcining the dihydrate ferric phosphate at 680 ℃ for 2 hours to obtain the battery-grade anhydrous ferric phosphate.
Example 3
A method for controllably preparing battery-grade iron phosphate from pyrite cinder comprises the following steps:
s1, crushing pyrite cinder of a raw material 2 in the table 1 to 600 meshes, and then slowly adding the crushed pyrite cinder into a sulfuric acid solution with the mass concentration of 65% while stirring to obtain mixed slurry; the mass of the pure sulfuric acid is 1.5 times of that of the pyrite cinder;
s2, stirring the mixed slurry at the normal pressure and at the temperature of 85 ℃ for reaction for 3.5 hours, adding water for dilution until the iron content is 3%, preserving heat for 2 hours, filtering and collecting to obtain a reaction solution;
s3, adding iron powder which is 0.5 time of the weight of ferric iron contained in the reaction solution into the reaction solution, and then stirring and reacting for 0.5 hour under the conditions of normal pressure and 50 ℃ to obtain returned raw material slurry;
s4, adding ammonia water with the mass concentration of 15% into the reduced slurry, adjusting the pH value to 6.5, filtering and collecting filtrate to obtain a refined ferrous sulfate solution;
s5, adding hydrogen peroxide into the refined ferrous sulfate solution, and reacting for 2 hours at 75 ℃ to obtain oxidized slurry; the molar ratio of hydrogen peroxide to iron is 0.5: 1;
s6, adding a urea solution with the mass concentration of 10% into the oxidized slurry, adjusting the pH to 2.8, filtering and collecting a filter cake to obtain ferric hydroxide;
s7, washing the ferric hydroxide for 2 times by using water to obtain high-purity ferric hydroxide;
s8, adding water into high-purity ferric hydroxide to prepare ferric hydroxide slurry containing 2% of iron, mixing the ferric hydroxide slurry with phosphoric acid, reacting at the normal pressure and 60 ℃ for 5.5 hours in a heat preservation manner, filtering and collecting a filter cake to obtain a ferric phosphate wet base; the molar ratio of phosphorus to iron is 1.2: 1;
s9, washing the iron phosphate wet base for 2 times to obtain a high-purity iron phosphate wet base;
s10, drying the high-purity iron phosphate wet base at 500 ℃ to obtain ferric phosphate dihydrate;
s11, calcining the dihydrate ferric phosphate at 950 ℃ for 1 hour to obtain the battery-grade anhydrous ferric phosphate.
Example 4
A method for controllably preparing battery-grade iron phosphate from pyrite cinder comprises the following steps:
s1, crushing pyrite cinder of a raw material 2 in the table 1 to 400 meshes, and then slowly adding the crushed pyrite cinder into a sulfuric acid solution with the mass concentration of 38% under stirring to obtain mixed slurry; the mass of the pure sulfuric acid is 1.5 times of that of the pyrite cinder;
s2, stirring the mixed slurry at the normal pressure and at the temperature of 85 ℃ for reaction for 3.5 hours, adding water for dilution until the iron content is 8%, preserving heat for 0.5 hour, filtering and collecting to obtain a reaction solution;
s3, adding recovered waste iron which is 0.7 time of the mass of ferric iron contained in the reaction liquid into the reaction liquid to prepare iron powder, and then stirring and reacting for 1.5 hours under the conditions of normal pressure and 50 ℃ to obtain a raw material slurry;
s4, adding a urea solution with the mass concentration of 30% into the reduced slurry, adjusting the pH value to 6.5, filtering and collecting filtrate to obtain a refined ferrous sulfate solution;
s5, introducing air into the refined ferrous sulfate solution, and reacting for 24 hours at 35 ℃ to obtain oxidized slurry;
s6, adding a urea solution with the mass concentration of 30% into the oxidized slurry, adjusting the pH to 2.8, filtering and collecting a filter cake to obtain ferric hydroxide;
s7, washing the ferric hydroxide for 2 times by using water to obtain high-purity ferric hydroxide;
s8, adding water into high-purity ferric hydroxide to prepare ferric hydroxide slurry containing 2% of iron, mixing the ferric hydroxide slurry with phosphoric acid, reacting at the normal pressure and 60 ℃ for 5.5 hours in a heat preservation manner, filtering and collecting a filter cake to obtain a ferric phosphate wet base; the molar ratio of phosphorus to iron is 1.06: 1;
s9, washing the iron phosphate wet base for 2 times to obtain a high-purity iron phosphate wet base;
s10, drying the high-purity iron phosphate wet base at 300 ℃ to obtain ferric phosphate dihydrate;
s11, calcining the dihydrate ferric phosphate at 700 ℃ for 1.5 hours to obtain the battery-grade anhydrous ferric phosphate.
In the above examples, the recovery rate of iron in the pyrite cinder, the quality of the obtained intermediate iron hydroxide, and the final iron phosphate are shown in tables 2, 3, and 4.
TABLE 2 example iron recovery of pyrite cinder
Iron hydroxide product index in Table 3 example
Table 4 index of iron phosphate product obtained in example
It can be seen from tables 2, 3 and 4 that the recovery rate of iron in the pyrite cinder is very high by adopting the method of the present invention, which is much higher than that of the prior art. The purity of the ferric hydroxide and the ferric phosphate prepared by the method is very high, and each index of the ferric phosphate is higher than the industrial standard.
Taking the above example 1 as an example, the microstructure of the iron phosphate product prepared by the method is tested, and fig. 1 and fig. 2 show an SEM image (surface microstructure photographed by a scanning electron microscope) and an XRD image (X-ray diffraction pattern) of the iron phosphate product prepared by the example 1, respectively.
According to the figure 1, the iron phosphate product is a nano-scale spherical agglomerate, has the appearance of being loose and porous and relatively uniform in particle size, so that the iron phosphate product has a higher specific surface area and is beneficial to improving the reaction activity of the iron phosphate serving as the lithium iron phosphate in the next step.
And (3) performing peak fitting and peak searching on the XRD peak spectrogram of the iron phosphate and the iron phosphate to obtain a graph 2, wherein all peak spectrums of the product are completely coincided with the iron phosphate in the example 1, so that the product is the high-purity iron phosphate.
The embodiment of the invention is not limited to the above embodiment, and in the method of the invention, each technical parameter can be adjusted within a certain range, such as the used pyrite cinder raw material containing Fe 2 O 3 、Fe 3 O 4 FeO, raw materials with the iron mass content of 45-60% can be used, and the raw materials inevitably contain impurity SiO 2 、Al 2 O 3 CaO, ZnO, MgO, and the like. In the step S1, the particle size of the crushed pyrite cinder powder can be 80-600 meshes, the acid solution can be sulfuric acid with the mass concentration of 38-65%, and the use amount of the sulfuric acid is 1.5-3 times of the mass of the pyrite cinder; in the step S2, the mixed slurry can be stirred and reacted for 2.5 to 5 hours at the temperature of 85 to 116 ℃, then water is added, the temperature is kept for 0.5 to 2 hours, and the reaction solution is obtained after filtration and collection; in step S3, adding iron powder into the reaction solution, and reacting at 50-95 ℃ for 0.5-3.0 hours while stirring to obtain a reduced raw material slurry; adding alkali liquor into the reducing slurry in the step S4, adjusting the pH to 5.2-7.4, filtering and collecting filtrate to obtain refined reducing liquid; in step S5, adding an oxidant into the refined reducing solution, and reacting at 15-75 ℃ for 0.5-24 hours to obtain oxidized slurry; in the step S6, adding an alkali liquor into the oxidized slurry, adjusting the pH to 2.8-4.8, filtering and collecting a filter cake to obtain ferric hydroxide; step S8, adding water into high-purity ferric hydroxide to prepare slurry containing 2-12% of iron, mixing the slurry with phosphoric acid, reacting at the temperature of 60-97 ℃ for 1.8-5.5 hours under normal pressure, filtering and collecting a filter cake to obtain a ferric phosphate wet base; in the step S10, the high-purity iron phosphate wet base can be dried at 105-500 ℃; in step S11, the dihydrate ferric phosphate may be calcined at 680 to 950 ℃ for 1 to 2 hours to obtain the battery grade anhydrous ferric phosphate. The alkali liquor can be one of 10-38% of sodium hydroxide, 10-35% of sodium carbonate, 10-30% of ammonia water and 10-30% of urea by mass concentration. The oxidant can be hydrogen peroxide or air, and the molar ratio of hydrogen peroxide to iron is 0.5: 1-0.7: 1; the reaction temperature after the oxidant is added is 25-55 ℃, the reaction time is 0.5-2 hours, and the oxidation time after the air is added is 3-24 hours.
All percentages stated in the present invention are percentages by mass, unless otherwise stated.
Claims (9)
1. The method for controllably preparing battery-grade iron phosphate from pyrite cinder is characterized by comprising the following steps of:
s1, crushing pyrite cinder to obtain pyrite cinder powder with uniform particle size, and then adding the pyrite cinder powder into an acid solution to obtain mixed slurry;
s2, stirring the mixed slurry at normal pressure and 85-116 ℃ for reaction for 2.5-5 hours, adding water, preserving heat for 0.5-2 hours, adding water for dilution, filtering and collecting reaction liquid;
s3, adding iron powder into the reaction liquid, stirring and reacting for 0.5-3.0 hours at normal pressure and at the temperature of 50-95 ℃, and adding water again to dilute to obtain a raw material slurry;
s4, adding alkali liquor into the reducing slurry, adjusting the pH value to 5.2-7.4, filtering and collecting filtrate to obtain refined reducing liquid;
s5, adding an oxidant into the refined reducing solution, and reacting at 15-75 ℃ for 0.5-24 hours to obtain oxidized slurry;
s6, adding alkali liquor into the oxidized slurry, adjusting the pH value to 2.8-4.8, filtering and collecting a filter cake to obtain ferric hydroxide;
s7, washing the ferric hydroxide by using water to obtain high-purity ferric hydroxide;
s8, adding water into high-purity ferric hydroxide to prepare slurry containing 2-12% of iron, mixing the slurry with phosphoric acid, reacting at the normal pressure and the temperature of 60-97 ℃ for 1.8-5.5 hours in a heat preservation manner, filtering, and collecting a filter cake to obtain a ferric phosphate wet base;
s9, washing the iron phosphate wet base for 1-3 times to obtain a high-purity iron phosphate wet base;
s10, drying the high-purity iron phosphate wet base at 105-500 ℃ to obtain ferric phosphate dihydrate;
s11, calcining the ferric phosphate dihydrate at 680-950 ℃ for 1-2 hours to obtain the battery-grade anhydrous ferric phosphate.
2. The method for controllably preparing battery-grade iron phosphate from pyrite cinder according to claim 1, wherein in step S1, the pyrite cinder contains Fe 2 O 3 、Fe 3 O 4 And FeO, the mass content of iron is 45-60%, and the pyrite cinder contains impurities of Si, Al, Ca, Zn and Mg.
3. The method for controllably preparing battery-grade iron phosphate from pyrite cinder according to claim 1, wherein in step S1, the particle size of the crushed pyrite cinder powder is 80-600 meshes; the acid solution is sulfuric acid with the mass concentration of 38-65%, and the using amount of the sulfuric acid is 1.5-3 times of the mass of the pyrite cinder.
4. The method for controllably preparing battery-grade iron phosphate from pyrite cinder according to claim 1, wherein in step S2, the stirring reaction temperature is 93-115 ℃ and the reaction time is 2.5-3.5 hours.
5. The method for controllably preparing battery-grade iron phosphate from pyrite cinder according to claim 1, wherein in step S3, the iron powder is recycled scrap iron-making iron powder and/or primary reduced iron powder, and the amount of the iron powder is 0.5-0.8 times of the amount of the ferric iron measured by sampling the reaction solution in step S2; adding water to ensure that the iron content is 3-9%; the stirring reaction temperature is 65-85 ℃, and the reaction time is 0.5-2.0 hours.
6. The method for controllably preparing battery-grade iron phosphate from pyrite cinder according to claim 1, wherein in steps S4 and S6, the alkali solution is one of 10% -38% by mass of sodium hydroxide, 10% -35% by mass of sodium carbonate, 10% -30% by mass of ammonia water, and 10% -30% by mass of urea.
7. The method for controllably preparing battery-grade iron phosphate from pyrite cinder according to claim 1, wherein in step S5, the oxidant is hydrogen peroxide or air, and the molar ratio of hydrogen peroxide to iron is 0.5: 1-0.7: 1; the reaction temperature after the oxidant is added is 25-55 ℃, the reaction time is 0.5-2 hours, and the oxidation time after the air is added is 3-24 hours.
8. The method for controllably preparing battery-grade iron phosphate from pyrite cinder according to claim 1, wherein in step S6, the pH is adjusted to 3.2-4.2.
9. The method for controllably preparing battery-grade iron phosphate from pyrite cinder, according to claim 1, wherein in step S8, water is added to high-purity iron hydroxide to prepare slurry containing 2% -12% of iron, and the molar ratio of phosphorus to iron of the phosphorus content of the fed phosphoric acid to the iron content of the iron hydroxide is 0.95-1.2: 1; the reaction temperature of the slurry and the phosphoric acid after mixing is 60-80 ℃, and the reaction time is 2.2-3.5 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115583641A (en) * | 2022-11-17 | 2023-01-10 | 贵州磷化新能源科技有限责任公司 | Method for preparing battery-grade iron phosphate by cooperation of pyrite cinder and waste lithium iron phosphate cores |
| CN116022756A (en) * | 2022-11-17 | 2023-04-28 | 贵州磷化新能源科技有限责任公司 | A method for preparing battery-grade iron phosphate from pyrite slag and wet-process phosphoric acid |
| CN116177515A (en) * | 2022-12-27 | 2023-05-30 | 昆明精粹工程技术有限责任公司 | A method for preparing battery-grade lithium iron phosphate by utilizing pyrite slag |
| CN118255336A (en) * | 2024-04-07 | 2024-06-28 | 新洋丰农业科技股份有限公司 | Method for preparing ferric phosphate based on ferric phosphate production wastewater and pyrite cinder |
| CN118929596A (en) * | 2024-07-25 | 2024-11-12 | 重庆长荣新能源材料有限公司 | A method and device for preparing ferric phosphate through precipitation conversion |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5286522A (en) * | 1992-11-19 | 1994-02-15 | University Of Kentucky Research Foundation | H2 O2 induced oxidation proof phosphate surface coating on iron sulfides |
| CN1114638A (en) * | 1994-07-08 | 1996-01-10 | 江兴全 | Process for producing ferrous sulfate by using sulfuric acid to leach pyrite cinder |
| CN104445429A (en) * | 2014-11-13 | 2015-03-25 | 常熟铁红厂有限公司 | Method for preparing iron oxide red pigment by using pyrite cinder residue-firing hydrothermal process |
| CN108706561A (en) * | 2018-08-14 | 2018-10-26 | 武汉轻工大学 | A method of preparing high-purity phosphoric acid iron using pyrite cinder |
| CN108706562A (en) * | 2018-08-14 | 2018-10-26 | 武汉轻工大学 | A method of preparing ferric phosphate using pyrite cinder |
| CN111377484A (en) * | 2020-03-20 | 2020-07-07 | 安庆市长虹化工有限公司 | A kind of pyrite resource recovery and treatment method |
| CN113184820A (en) * | 2021-04-25 | 2021-07-30 | 湖南雅城新材料有限公司 | Method for preparing iron phosphate by using titanium dioxide byproduct ferrous sulfate |
| 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 |
| CN114604837A (en) * | 2022-03-30 | 2022-06-10 | 湖北宇浩高科新材料有限公司 | A kind of preparation method of iron phosphate, preparation method of lithium iron phosphate |
-
2022
- 2022-07-19 CN CN202210844571.8A patent/CN114906830B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5286522A (en) * | 1992-11-19 | 1994-02-15 | University Of Kentucky Research Foundation | H2 O2 induced oxidation proof phosphate surface coating on iron sulfides |
| CN1114638A (en) * | 1994-07-08 | 1996-01-10 | 江兴全 | Process for producing ferrous sulfate by using sulfuric acid to leach pyrite cinder |
| CN104445429A (en) * | 2014-11-13 | 2015-03-25 | 常熟铁红厂有限公司 | Method for preparing iron oxide red pigment by using pyrite cinder residue-firing hydrothermal process |
| CN108706561A (en) * | 2018-08-14 | 2018-10-26 | 武汉轻工大学 | A method of preparing high-purity phosphoric acid iron using pyrite cinder |
| CN108706562A (en) * | 2018-08-14 | 2018-10-26 | 武汉轻工大学 | A method of preparing ferric phosphate using pyrite cinder |
| CN111377484A (en) * | 2020-03-20 | 2020-07-07 | 安庆市长虹化工有限公司 | A kind of pyrite resource recovery and treatment method |
| 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 |
| CN113184820A (en) * | 2021-04-25 | 2021-07-30 | 湖南雅城新材料有限公司 | Method for preparing iron phosphate by using titanium dioxide byproduct ferrous sulfate |
| CN114604837A (en) * | 2022-03-30 | 2022-06-10 | 湖北宇浩高科新材料有限公司 | A kind of preparation method of iron phosphate, preparation method of lithium iron phosphate |
Non-Patent Citations (5)
| Title |
|---|
| JIANG, T 等: "A novel value-added utilization process for pyrite cinder: Selective recovery of Cu/Co and synthesis of ironphosphate", 《HYDROMETALLURGY》 * |
| 李平: "热处理黄铁矿的结构和物性演化及其化学反应活性", 《中国优秀博硕士学位论文全文数据库（博硕）工程科技I辑》 * |
| 郑雅杰: "硫铁矿烧渣制备聚合硫酸铁和聚磷硫酸铁新工艺及基础理论研究", 《中国优秀博硕士学位论文全文数据库（博士）工程科技I辑》 * |
| 郑雅杰等: "硫铁矿烧渣湿法制备铁系产品的原理和途径分析", 《环境污染治理技术与设备》 * |
| 龚竹青等: "硫铁矿烧渣制备硫酸亚铁及效益估算", 《环境保护》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115583641A (en) * | 2022-11-17 | 2023-01-10 | 贵州磷化新能源科技有限责任公司 | Method for preparing battery-grade iron phosphate by cooperation of pyrite cinder and waste lithium iron phosphate cores |
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| CN116022756B (en) * | 2022-11-17 | 2025-09-30 | 贵州磷化新能源科技有限责任公司 | A method for preparing battery-grade iron phosphate using pyrite slag and wet-process phosphoric acid |
| CN116177515A (en) * | 2022-12-27 | 2023-05-30 | 昆明精粹工程技术有限责任公司 | A method for preparing battery-grade lithium iron phosphate by utilizing pyrite slag |
| CN118255336A (en) * | 2024-04-07 | 2024-06-28 | 新洋丰农业科技股份有限公司 | Method for preparing ferric phosphate based on ferric phosphate production wastewater and pyrite cinder |
| CN118255336B (en) * | 2024-04-07 | 2024-09-13 | 新洋丰农业科技股份有限公司 | Method for preparing ferric phosphate based on ferric phosphate production wastewater and pyrite cinder |
| CN118929596A (en) * | 2024-07-25 | 2024-11-12 | 重庆长荣新能源材料有限公司 | A method and device for preparing ferric phosphate through precipitation conversion |
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