CN114572954B - Method for preparing battery grade ferric phosphate by using pyrite cinder - Google Patents
Method for preparing battery grade ferric phosphate by using pyrite cinder Download PDFInfo
- Publication number
- CN114572954B CN114572954B CN202210284621.1A CN202210284621A CN114572954B CN 114572954 B CN114572954 B CN 114572954B CN 202210284621 A CN202210284621 A CN 202210284621A CN 114572954 B CN114572954 B CN 114572954B
- Authority
- CN
- China
- Prior art keywords
- pyrite cinder
- ferric
- phosphate
- ferric phosphate
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 71
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000011028 pyrite Substances 0.000 title claims abstract description 70
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 70
- 239000003818 cinder Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 56
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 50
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 49
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 49
- 238000002386 leaching Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 27
- 241000609240 Ambelania acida Species 0.000 claims abstract description 24
- 239000010905 bagasse Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 15
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 47
- 239000002002 slurry Substances 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 23
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 17
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 15
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000000126 substance Substances 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
- 230000008859 change Effects 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- 150000004673 fluoride salts Chemical class 0.000 claims description 4
- -1 iron ions Chemical class 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 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 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- XNCMOUSLNOHBKY-UHFFFAOYSA-H iron(3+);trisulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XNCMOUSLNOHBKY-UHFFFAOYSA-H 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- RGKMZNDDOBAZGW-UHFFFAOYSA-N aluminum calcium Chemical compound [Al].[Ca] RGKMZNDDOBAZGW-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for preparing ferric phosphate by using pyrite cinder, which comprises the steps of forming a mixed material by using crushed pyrite cinder and bagasse powder, carrying out reduction roasting at a specific temperature to obtain pyrite cinder roasting material, carrying out oxidation acid leaching by using concentrated sulfuric acid and hydrogen peroxide to obtain leaching liquid, removing impurities such as heavy metals, calcium aluminum and the like, adjusting the concentration of ferric iron to obtain ferric salt solution, adding a phosphorus source, reacting to prepare ferric phosphate, filtering, washing, drying and calcining to obtain the battery-level nano anhydrous ferric phosphate. The method utilizes bagasse to reduce and bake pyrite cinder, can control the leaching time of the subsequent oxidation acid leaching within 2 hours, can reach the leaching rate of more than 95% at normal temperature, and finally has low content of ferric phosphate impurities, energy conservation and high efficiency.
Description
Technical Field
The invention relates to the technical field of battery-grade ferric phosphate, in particular to a method for preparing battery-grade ferric phosphate by using pyrite cinder.
Background
Ferric phosphate is also called ferric phosphate and ferric orthophosphate, and the molecular formula is FePO 4 The powder is white and off-white monoclinic crystal powder and is mainly used for manufacturing lithium iron phosphate battery materials, catalysts, ceramics and the like.
With the rapid development of new energy technology, the application of lithium iron phosphate batteries is focused, the requirements of battery-grade iron phosphate materials are also increasing, and the iron source materials for preparing the battery-grade iron phosphate materials are required to be continuously developed.
Iron sheet, iron powder, iron red and titanium dioxide byproduct ferrous sulfate heptahydrate are the most common iron sources in the industry at present, and the economy of using titanium dioxide byproduct ferrous sulfate heptahydrate is better. In order to avoid the influence of the rising price of the upstream ferric sulfate heptahydrate on production, development and exploration of low-cost raw materials are still needed, and meanwhile, the resource recycling can be realized, so that the environmental pollution is reduced.
For example, patent document CN114014294a discloses a method for preparing lithium iron phosphate from pyrite,the technology produces SO through roasting and catalytic reaction of pyrite in turn 3 The method comprises the steps of preparing ferric sulfate solution through sulfuric acid reaction and hydrogen peroxide reaction, forming ferric phosphate, obtaining the effects of acid leaching pyrite cinder through multiple experiments, wherein the leaching rate of the ferric is between 40% and 65%, the leaching rate of the ferric is low, the process for directly preparing ferric phosphate by utilizing the pyrite is complex, self-made sulfuric acid is self-made, related equipment is needed, the equipment investment is high, and the impurity content of the ferric sulfate solution obtained through the method is high, so that the purity of the prepared ferric phosphate is low. Patent document CN10938610a discloses a method for preparing iron phosphate with high iron-phosphorus ratio by using pyrite cinder, which adopts carbon dioxide to remove calcium, and the end point is not well controlled, and then precipitation and slag are mixed together and are not well separated. The nonionic flocculant is used for removing impurities, the obtained ferric phosphate has narrow later use, and the acrylamide monomer is always present in the polyacrylamide product, and the monomer is a toxic substance. Patent document CN108706561a discloses a method for preparing high-purity ferric phosphate by using pyrite cinder, the acid leaching and purifying time is long, the working procedure time is up to 12 hours, and the production efficiency is low. Patent document CN108706562A discloses a method for preparing ferric phosphate by using pyrite cinder, which has the advantages of longer acid leaching and purifying time, longer working procedure time reaching 12 hours, lower production efficiency, only 90 percent of purity of the obtained ferric phosphate and poorer product quality. Patent document CN102730659a discloses a method for preparing battery grade iron phosphate by using pyrite cinder, which uses composite acid medium to leach pyrite cinder, uses organic acid and organic solvent, and the subsequent organic waste water is difficult to treat, and the cost is relatively high, because iron is in both organic phase and inorganic phase, only iron in the organic phase is used for synthesizing iron phosphate, and the single iron utilization rate is low.
Disclosure of Invention
Based on the above, it is necessary to provide a method for preparing battery grade iron phosphate from pyrite cinder, which has high leaching rate of iron element and lower impurity content.
The invention adopts the following technical scheme:
the invention provides a method for preparing ferric phosphate by using pyrite cinder, which comprises the following steps:
s1, crushing and mixing materials: crushing pyrite cinder (preferably, the particle size of the crushed pyrite cinder is 80-200 meshes) to obtain pyrite cinder powder; taking bagasse of a sugar refinery, drying, cooling, and crushing (preferably crushing grain size is 80-200 meshes) to obtain bagasse powder; uniformly mixing pyrite cinder powder and bagasse powder according to the mass ratio of 100 (5-20) to obtain a mixed material.
S2, heating and roasting: and (3) reacting the mixed material in the step (S1) at 300-800 ℃ under the condition of inert atmosphere (the heating rate is 10-15 ℃/min), and cooling under the inert atmosphere (preferably one or more of nitrogen, argon and helium) to obtain the pyrite cinder roasting material.
S3, oxidizing and leaching to obtain leaching liquid.
S4, removing heavy metals and calcium aluminum: dripping a heavy metal capturing agent into the leaching solution, stirring for reaction, and filtering to obtain a heavy metal removing filtrate; and adding fluoride salt, continuing the reaction, and filtering to obtain ferric sulfate clear liquid.
S5, adjusting the mass concentration of iron ions in the ferric sulfate clear liquid to be 4-7wt% (preferably 4.5-6wt%) to obtain an iron salt solution.
S6, synthesizing ferric phosphate:
according to the stoichiometric ratio, 15-20% excess phosphoric acid (industrial grade or electronic grade) is added into ferric salt solution in a dropwise manner, and the pH value is regulated and controlled to be 1.6-2.2 by ammonia water in the dropwise adding process, so that ferric phosphate slurry is obtained. And (3) heating the ferric phosphate slurry for reaction, observing the color change of the slurry, continuously preserving the heat for 1-2 h after the color of the slurry is changed into white or pink, filtering, washing with water, drying and calcining to obtain the battery-level nano anhydrous ferric phosphate.
In some embodiments, the mixed material is preferably prepared by uniformly mixing pyrite cinder powder and bagasse powder according to the mass ratio of 100 (8-15).
In some of these embodiments, the oxidizing acid leaching comprises the steps of: adding pure water into the pyrite cinder roasting material obtained in the step S2, wherein the liquid-solid ratio is (3-6): 1, and uniformly mixing (the mixing time is 20-40 min, and the stirring intensity is 300 rpm) to prepare slurry; adding concentrated sulfuric acid (98 wt%) and its acid-solid ratio is (1-1.6): 1, controlling reaction temperature to 10-40 deg.C (preferably 15-25 deg.C); and after the dripping is finished, continuously stirring for 10-20 min, then adding 25-30wt% of hydrogen peroxide, controlling the hydrogen peroxide consumption to be 0.55-0.75 times of the total iron substances in the pyrite cinder, continuously reacting for 1-4 h, and filtering to obtain the additive.
In some embodiments, the heavy metal scavenger is added in an amount of 0.1 to 0.6g/L and the concentration of the heavy metal scavenger is 15 to 20g/L. The heavy metal trapping agent is sulfide salt, preferably one or more of sodium sulfide, potassium sulfide and ammonium sulfide.
In some embodiments, the fluoride salt is selected from one or more of sodium fluoride, potassium fluoride, ammonium fluoride.
In some of these embodiments, the reagent used to adjust the iron concentration in the ferric sulfate serum is pure water or a soluble ferric salt. The soluble ferric salt is preferably selected from one or more of ferric sulfate, ferric nitrate and ferric chloride.
In some of these embodiments, the iron phosphate slurry is heated to 88-96 ℃ to react until the slurry color becomes white or pink.
In some of these embodiments, the bagasse pretreatment process comprises: and (3) drying bagasse waste materials from a sugar refinery after sugar refining in a drying oven at 60-90 ℃ for 60-120 min, and crushing the bagasse waste materials into powder with the particle size of 80-200 meshes in a high-speed crusher.
In some of these embodiments, the reaction temperature of the elevated firing is 400-600 ℃ and the firing time is 1-2 hours.
In some of these embodiments, the rate of cooling during cooling under an inert atmosphere is 10 to 15 ℃.
In some embodiments, the process parameters of the drying and calcining are: the drying temperature is 95-105 ℃, the drying time is 1.5-3 h, the calcining temperature is 550-650 ℃, and the calcining time is 1-4 h.
The beneficial effects of the invention are as follows:
compared with the prior art, the method for preparing the ferric phosphate by using the pyrite cinder adopts the pyrite cinder and the bagasse to carry out reduction roasting, so that the leaching time can be controlled within 2 hours, the leaching rate can reach more than 95 percent at normal temperature, the finally obtained ferric phosphate has low impurity content, energy conservation and high efficiency, the recycling of resources of the pyrite cinder can be realized, and the production cost of the ferric phosphate is reduced.
Drawings
FIG. 1 is a process flow diagram of a method for preparing iron phosphate by using pyrite cinder.
Detailed Description
The present invention will be described in further detail with reference to specific examples so as to more clearly understand the present invention by those skilled in the art.
The following examples are given for illustration of the invention only and are not intended to limit the scope of the invention. All other embodiments obtained by those skilled in the art without creative efforts are within the protection scope of the present invention based on the specific embodiments of the present invention.
In the examples of the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise; in the embodiments of the present invention, unless specifically indicated, all technical means used are conventional means well known to those skilled in the art.
As shown in figure 1, the invention provides a method for preparing ferric phosphate by using pyrite cinder, which comprises the steps of forming a mixed material by using crushed pyrite cinder and bagasse powder, carrying out reduction roasting at a specific temperature to obtain pyrite cinder roasting material, carrying out oxidation acid leaching by using concentrated sulfuric acid and hydrogen peroxide to obtain leaching liquid, removing impurities such as heavy metals, calcium aluminum and the like, adjusting the concentration of ferric iron to obtain ferric salt solution, adding a phosphorus source, reacting to prepare ferric phosphate, filtering, washing, drying and calcining to obtain the battery-level nano anhydrous ferric phosphate. The method utilizes bagasse to reduce and bake pyrite cinder, can control the leaching time of the subsequent oxidation acid leaching within 2 hours, can reach the leaching rate of more than 95% at normal temperature, and finally has low content of ferric phosphate impurities, energy conservation and high efficiency.
Specific examples are as follows:
elemental analysis results of pyrite cinder employed in the experiments of the present invention are shown in the following table:
TABLE 1 statistics of analysis results of chemical elements of pyrite cinder
Example 1
The embodiment provides a method for preparing ferric phosphate by using pyrite cinder, which comprises the following steps:
s1, crushing and mixing materials:
40g of pyrite cinder is crushed into pyrite cinder powder with the grain size of 100 meshes in a high-speed crusher for standby.
100g bagasse of a sugar refinery is taken, dried in an oven at 80 ℃ for 60min, cooled and crushed into bagasse powder with the particle size of 80 meshes by a high-speed crusher for standby.
The pyrite cinder powder and the bagasse powder are mixed according to the mass ratio of 100:12.5, adding the mixture into a V-shaped mixer, uniformly mixing, mixing for 10min, and transferring the mixture into a corundum crucible for later use.
S2, heating and roasting:
after the temperature of the tube furnace is raised to 550 ℃, introducing nitrogen for 5min, discharging all air completely, and rapidly placing a dry pot filled with the mixed materials into the tube furnace, wherein nitrogen is continuously introduced for 2min to prevent air from entering; and taking out the materials after 90min, and cooling to room temperature under an argon atmosphere to obtain 36.2g pyrite cinder roasting material.
S3, oxidizing acid leaching:
mixing the pyrite cinder roasting material with 144.8g of pure water uniformly to prepare slurry, wherein the liquid-solid ratio is 4:1, adding 54.88g of (98%) concentrated sulfuric acid, the acid-solid ratio is 1.49, controlling the reaction temperature to 15 ℃, stirring for 10min, stirring at 300rpm, adding 32g of (25 wt%) hydrogen peroxide, the hydrogen peroxide consumption is 0.6 times of the total iron substances in pyrite cinder, continuing to react for 2h, and filtering to obtain the oxidized acid leaching solution.
S4, heavy metal removal:
and (3) dropwise adding 6.52g of sodium sulfide solution into the oxidation acid leaching solution, wherein the concentration of the sodium sulfide solution is 15g/L, continuously stirring for 20-30 min after the dropwise adding is finished, stirring at 300rpm, and filtering to obtain impurity-removing liquid.
S5, removing heavy calcium aluminum:
adding sodium fluoride solid into the impurity removing liquid, wherein the adding amount is 3.5 times of the total substances of calcium and aluminum in the solution, continuously stirring for 30min, the stirring intensity is 300rpm, filtering to obtain ferric sulfate clear liquid, and then adding pure water to enable the concentration of iron in the solution to be 4.86wt%.
S6, preparing ferric phosphate slurry:
taking phosphoric acid (85 wt%) to make the mole ratio of P/Fe be 1.0, dripping the phosphoric acid into the above-mentioned ferric sulfate clear liquor for 35min, regulating pH value of slurry to be 1.8 by using ammonia water, continuously stirring for 50min, then adding phosphoric acid whose quantity is 15% of that of ferric phosphate material so as to obtain the invented ferric phosphate slurry.
S7, heating aging reaction and washing:
the iron phosphate slurry was heated to 96 ℃ in a water bath, the color change of the slurry was observed, and after the slurry became white, the heat preservation was continued for 75min.
Washing water is stopped until the pH value is=3.5, and a filter cake is obtained.
S8, drying and calcining:
placing the filter cake into a vacuum drying oven at 100 ℃ and baking for 120min; 67.25g of dried ferric phosphate dihydrate was obtained, calculated as 91.74% iron yield from pyrite cinder to ferric phosphate dihydrate; and (3) placing the dihydrate ferric phosphate into a muffle furnace to be calcined at 600 ℃ for 4 hours, so as to obtain the battery-grade nano anhydrous ferric phosphate.
Example 2
The present example provides a method for preparing iron phosphate by using pyrite cinder, the procedure is basically the same as that of example 1, and the difference is that: the roasting temperature is 700 ℃, and the mass ratio of the pyrite cinder to the bagasse is 100:15.
Example 3
The present example provides a method for preparing iron phosphate by using pyrite cinder, the procedure is basically the same as that of example 1, and the difference is that: the firing temperature was 400 ℃.
Example 4
The present example provides a method for preparing iron phosphate by using pyrite cinder, the procedure is basically the same as that of example 1, and the difference is that: the acid-solid ratio is 1.49, and the acid leaching time is 4 hours.
Example 5
The present example provides a method for preparing iron phosphate by using pyrite cinder, the procedure is basically the same as that of example 1, and the difference is that: roasting time of pyrite cinder and bagasse is 120min.
Example 6
The present example provides a method for preparing iron phosphate by using pyrite cinder, the procedure is basically the same as that of example 1, and the difference is that: the addition amount of sodium sulfide is 0.2g/L, and the sodium fluoride is 4 times of the molar amount of aluminum.
Comparative example 1
This comparative example provides a method for preparing iron phosphate using pyrite cinder, which is different from example 1 only in that: the reduction firing was not performed.
Comparative example 2
The comparative example provides a method for preparing ferric phosphate by utilizing ferrous sulfate heptahydrate serving as a titanium dioxide byproduct, which comprises the following steps:
(1) Preparing a ferrous solution: mixing 90g of titanium dioxide byproduct ferrous sulfate heptahydrate and 283g of pure water uniformly to prepare a ferrous solution with the iron concentration of 4.86wt%, adding 26.4g of 25wt% hydrogen peroxide for 7min, and continuously stirring for 20min to obtain the ferric sulfate solution.
(2) And (3) synthesis: 37.33g of phosphoric acid (85 wt%) was added dropwise to the above-mentioned ferric sulfate solution for 12 minutes, the pH of the slurry was adjusted to 1.8 with ammonia water, stirring was continued for 50 minutes, and then 5.6g of concentrated phosphoric acid (85 wt%) was added in an amount of 15% of the amount of the ferric sulfate substance.
(3) And (3) heating and aging: the slurry is heated to 96 ℃ in a water bath, the color change of the slurry is observed, and the slurry is kept for 75 minutes after becoming white.
(4) And (3) washing a filter cake: after the end of incubation, the slurry was filtered and the filter cake was washed with pure water at the end of the rinse water ph=3.5.
(5) And (3) drying: and (3) placing the filter cake into a vacuum drying oven, and drying at 100 ℃ for 120min in vacuum to obtain dry ferric phosphate dihydrate powder.
(6) Calcining: and (3) placing the dihydrate ferric phosphate into a muffle furnace, and calcining for 4 hours at 600 ℃ to obtain the battery-grade nano anhydrous ferric phosphate.
The oxidation acid leaching rates of examples 1 to 6 and comparative example 1 were counted, respectively, and the results are shown in table 2 below:
TABLE 2 iron leaching rate
| Test examples | Iron leaching rate |
| Example 1 | 96.14 |
| Example 2 | 93.83 |
| Example 3 | 95.11 |
| Example 4 | 96.66 |
| Example 5 | 96.40 |
| Example 6 | 96.01 |
| Comparative example 1 | 41％ |
As can be seen from table 2 above: compared with comparative example 1, the iron leaching effect in examples 1 to 6 is good, time and raw materials are saved, and the method is suitable for industrial production.
In addition, the invention is worth to be explained, and a large number of researches show that: when the pyrite cinder powder and the bagasse powder are compounded according to the mass ratio of 100 (5-20), the iron leaching rate of the whole is more than 92%, the leaching effect is good, the time and the raw materials are saved, and the method is suitable for industrial production.
The content of each element in the pure ferric sulfate solutions in examples 1 and 6 was counted, and the detection results are shown in table 3 below:
TABLE 3 statistical table for element content detection
As can be seen from table 3: example 6 the aluminum calcium content was slightly lower than example 1, the iron loss rate was reduced by 1.11%, and the process conditions of example 6 could be adopted to be more optimal.
The anhydrous iron phosphate prepared in example 1 and comparative example 2 was tested separately, and the test results are shown in table 4:
TABLE 4 product test results
From the results of the test of example 1 and comparative example 2 in table 4, it can be seen that: the iron phosphate prepared by taking ferrous sulfate prepared from pyrite cinder as an iron source and taking titanium dioxide byproduct ferric sulfate heptahydrate as an iron source meets the standard required by battery manufacturers, and the process can realize the utilization of resources of pyrite cinder, reduce environmental pollution and realize reasonable utilization of the resources.
It should be noted that the above examples are only for further illustrating and describing the technical solution of the present invention, and are not intended to limit the technical solution of the present invention, and the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The method for preparing the ferric phosphate by using the pyrite cinder is characterized by comprising the following steps of:
s1, crushing and mixing materials: crushing pyrite cinder to obtain pyrite cinder powder; taking bagasse of a sugar refinery, drying, cooling and crushing to obtain bagasse powder; uniformly mixing pyrite cinder powder and bagasse powder according to the mass ratio of 100 (5-20) to obtain a mixed material;
s2, heating and roasting: reacting the mixed material in the step S1 at 300-800 ℃ under the inert atmosphere condition, and cooling the mixed material under the inert atmosphere to obtain pyrite cinder roasting material;
s3, oxidizing and acid leaching to obtain leaching liquid; adding pure water into the pyrite cinder roasting material obtained in the step S2, and uniformly mixing the materials to prepare slurry, wherein the liquid-solid ratio is (3-6): 1; adding concentrated sulfuric acid dropwise, wherein the acid-solid ratio is 1 to 1.6, and the reaction temperature is controlled to be 10 to 40 ℃; after the dripping is finished, adding hydrogen peroxide, controlling the consumption of the hydrogen peroxide to be 0.55-0.75 times of the total iron substances in the pyrite cinder, continuing to react for 1-4 h, and filtering;
s4, removing heavy metals and calcium aluminum: dripping a heavy metal capturing agent into the leaching solution, stirring for reaction, and filtering to obtain a heavy metal removing filtrate; adding fluoride salt, continuing to react, and filtering to obtain ferric sulfate clear liquid;
s5, adjusting the mass concentration of iron ions in the ferric sulfate clear liquid to be 4-7wt% to obtain an iron salt solution;
s6, synthesizing ferric phosphate:
according to the stoichiometric ratio, adding 15-20% of phosphoric acid into ferric salt solution in a dropwise manner, and regulating the pH value to be 1.6-2.2 by ammonia water in the dropwise process to obtain ferric phosphate slurry;
and (3) heating the ferric phosphate slurry for reaction, observing the color change of the slurry, continuously preserving the heat for 1-2 h after the color of the slurry is changed into white or pink, filtering, washing with water, drying and calcining to obtain the battery-level nano anhydrous ferric phosphate.
2. The method for preparing iron phosphate by using pyrite cinder according to claim 1, wherein the addition amount of the heavy metal scavenger is 0.1-0.6 g/L and the concentration of the heavy metal scavenger is 15-20 g/L.
3. The method for preparing iron phosphate by using pyrite cinder according to claim 1, wherein the fluoride salt is selected from one or more of sodium fluoride, potassium fluoride and ammonium fluoride.
4. The method for preparing ferric phosphate by using pyrite cinder according to claim 1, wherein the reagent used for adjusting the iron concentration in the ferric sulfate supernatant is pure water or soluble ferric salt.
5. The method for preparing iron phosphate by using pyrite cinder according to claim 1, wherein the iron phosphate slurry is heated to 88-96 ℃ to react until the slurry color becomes white or pink.
6. The method for preparing ferric phosphate by using pyrite cinder according to claim 1, wherein the pretreatment process of bagasse comprises: and (3) drying bagasse waste materials from a sugar refinery after sugar refining in a drying oven at 60-90 ℃ for 60-120 min, and crushing the bagasse waste materials into powder with the particle size of 80-200 meshes in a high-speed crusher.
7. The method for preparing iron phosphate by using pyrite cinder according to claim 1, wherein the reaction temperature of the heating and roasting is 400-600 ℃ and the roasting time is 1-2 h.
8. The method for preparing iron phosphate by using pyrite cinder according to claim 7, wherein the cooling rate in the cooling process is 10-15 ℃ under the inert atmosphere.
9. The method for preparing ferric phosphate by using pyrite cinder according to claim 1, wherein the process parameters of the drying and calcining are as follows: the drying temperature is 95-105 ℃, the drying time is 1.5-3 h, the calcining temperature is 550-650 ℃, and the calcining time is 1-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210284621.1A CN114572954B (en) | 2022-03-22 | 2022-03-22 | Method for preparing battery grade ferric phosphate by using pyrite cinder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210284621.1A CN114572954B (en) | 2022-03-22 | 2022-03-22 | Method for preparing battery grade ferric phosphate by using pyrite cinder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114572954A CN114572954A (en) | 2022-06-03 |
| CN114572954B true CN114572954B (en) | 2023-12-12 |
Family
ID=81781938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210284621.1A Active CN114572954B (en) | 2022-03-22 | 2022-03-22 | Method for preparing battery grade ferric phosphate by using pyrite cinder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114572954B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115571864A (en) * | 2022-09-05 | 2023-01-06 | 六盘水师范学院 | Method for preparing battery-grade iron phosphate by using high-iron type fly ash as raw material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1145469A (en) * | 1956-02-10 | 1957-10-25 | Process for preparing alkali polyphosphates and pyrophosphates and at the same time metal hydroxides | |
| JPS57132560A (en) * | 1981-02-10 | 1982-08-16 | Sumitomo Heavy Ind Ltd | Dressing method of pyrite cinder |
| CN102730659A (en) * | 2011-04-08 | 2012-10-17 | 江苏绿陵化工集团有限公司 | Method for preparing battery-level ferric phosphate using pyrite cinders |
| CN103746115A (en) * | 2013-12-13 | 2014-04-23 | 灵宝金源矿业股份有限公司 | Method for preparing cell-grade lithium iron phosphate from pyrite slag |
| CN108706562A (en) * | 2018-08-14 | 2018-10-26 | 武汉轻工大学 | A method of preparing ferric phosphate using pyrite cinder |
-
2022
- 2022-03-22 CN CN202210284621.1A patent/CN114572954B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1145469A (en) * | 1956-02-10 | 1957-10-25 | Process for preparing alkali polyphosphates and pyrophosphates and at the same time metal hydroxides | |
| JPS57132560A (en) * | 1981-02-10 | 1982-08-16 | Sumitomo Heavy Ind Ltd | Dressing method of pyrite cinder |
| CN102730659A (en) * | 2011-04-08 | 2012-10-17 | 江苏绿陵化工集团有限公司 | Method for preparing battery-level ferric phosphate using pyrite cinders |
| CN103746115A (en) * | 2013-12-13 | 2014-04-23 | 灵宝金源矿业股份有限公司 | Method for preparing cell-grade lithium iron phosphate from pyrite slag |
| CN108706562A (en) * | 2018-08-14 | 2018-10-26 | 武汉轻工大学 | A method of preparing ferric phosphate using pyrite cinder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114572954A (en) | 2022-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108110357A (en) | A kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate | |
| CN102002585B (en) | Method for producing vanadium iron with stone-like coal pickle liquor | |
| CN109666789B (en) | Method for preparing vanadium pentoxide by using vanadium-chromium slag and manganese carbonate | |
| CN103420416B (en) | Ammonium metavanadate preparation method | |
| CN109368612A (en) | Method for preparing battery-grade iron phosphate by using iron phosphate production wastewater and iron phosphate prepared by method | |
| CN114772569B (en) | Method for preparing ferric phosphate by two-step hydrochloric acid dissolution of pyrite cinder | |
| CN112142028B (en) | Preparation method of manganese phosphate | |
| CN114684801B (en) | Method for preparing high-purity ferric phosphate by using pyrite cinder | |
| CN114572954B (en) | Method for preparing battery grade ferric phosphate by using pyrite cinder | |
| CN106430305A (en) | Production method of high-density ammonium metavanadate | |
| CN114014294B (en) | Method for preparing lithium iron phosphate by using pyrite and lithium iron phosphate material | |
| CN109809440B (en) | Method for preparing high-purity lithium chloride, high-purity lithium formate and high-purity lithium carbonate | |
| CN101698514B (en) | Preparation method of electronic grade high-purity manganese sulfate monohydrate | |
| CN103466720B (en) | Manganese sulfate solution prepares the technique of high-purity mangano-manganic oxide | |
| CN103466712B (en) | Technology for preparing high-purity manganous-manganic oxide with manganous sulfate solution | |
| CN116161636B (en) | Method for preparing battery-grade anhydrous ferric phosphate from lithium-extracted ferric phosphate waste residues | |
| JP2024052508A (en) | Vanadium electrolyte, manufacturing method of them, and application | |
| CN116902943A (en) | Preparation method of iron phosphate with adjustable specific surface | |
| CN116022756A (en) | Method for preparing battery-grade ferric phosphate from pyrite cinder and wet-process phosphoric acid | |
| CN115072686A (en) | Method for preparing battery-grade iron phosphate by using pyrite cinder | |
| CN115340075A (en) | Method for preparing battery-grade iron phosphate by adopting iron oxide and dilute phosphoric acid | |
| CN114455561A (en) | Comprehensive utilization process of hot galvanizing pickling wastewater and method for preparing battery-grade iron phosphate | |
| CN106395758A (en) | A method of producing high-purity sodium sulfide | |
| CN111573717B (en) | Method for preparing high-purity nano lithium titanate from industrial metatitanic acid | |
| CN115806280B (en) | Method for preparing ferric phosphate by taking phosphorus chemical byproduct ferrophosphorus powder as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240509 Address after: 435400 South Wuhan road, shangguo community, Tian Town, Wuxue City, Huanggang City, Hubei Province Patentee after: Hubei Yunxiang Juneng New Energy Technology Co.,Ltd. Country or region after: China Address before: 435400 South Wuhan road, shangguo community, Tian Town, Wuxue City, Huanggang City, Hubei Province Patentee before: Hubei Yunxiang Juneng New Energy Technology Co.,Ltd. Country or region before: China Patentee before: Hubei Jinhui lithium material technology Co.,Ltd. |