CN116374979A - Preparation method of ferric phosphate - Google Patents
Preparation method of ferric phosphate Download PDFInfo
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- CN116374979A CN116374979A CN202310462744.4A CN202310462744A CN116374979A CN 116374979 A CN116374979 A CN 116374979A CN 202310462744 A CN202310462744 A CN 202310462744A CN 116374979 A CN116374979 A CN 116374979A
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- nitrate
- ferric
- solution
- ferric phosphate
- ferrous
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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 66
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 56
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 56
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 72
- 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 claims abstract description 72
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 36
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 60
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 38
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 32
- 229910002651 NO3 Inorganic materials 0.000 claims description 32
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 32
- 239000011790 ferrous sulphate Substances 0.000 claims description 27
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 27
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 27
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 27
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 19
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 45
- 229910052742 iron Inorganic materials 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 12
- 239000012535 impurity Substances 0.000 description 11
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910001037 White iron Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229940116007 ferrous phosphate Drugs 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 3
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 3
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000010792 warming 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of ferric phosphate, and belongs to the technical field of new energy battery raw materials. The invention solves the technical problem of providing a preparation method of high-quality ferric phosphate with high yield. The preparation method comprises the following steps: mixing ferric nitrate crystals with phosphoric acid solution, and reacting for more than 30 minutes at the temperature of 120-200 ℃ to obtain the ferric phosphate crystals, wherein the concentration of the phosphoric acid solution is more than or equal to 85wt%. Aiming at the current demand for high-quality ferric phosphate, the invention can provide a preparation method of battery-grade ferric phosphate, which has the advantages of simple method, high yield, high purity of the obtained ferric phosphate, stable performance, and reduced process cost from the source.
Description
Technical Field
The invention relates to a preparation method of ferric phosphate, and belongs to the technical field of new energy battery raw materials.
Background
With the rapid development of economy in the global area, the problem of energy is becoming more serious, non-renewable resources including petroleum, coal and the like are consumed in a large amount in a short time, and simultaneously, environmental problems such as global warming, drinking water, atmospheric pollution and the like are accompanied by the unreasonable use of these non-renewable energy sources. The high-speed development of economy brings about a lot of problems and also brings about the crisis of energy. Therefore, energy substitutes which can be put into use for a long time and clean for the environment are actively searched worldwide, and along with the progress of research, the world is gradually aware that the probably first-driven energy substitutes are chemical power supply energy storage batteries, and the energy substitutes can play an important role in the energy aspect of the world development in the future as energy storage devices with good comprehensive performance. The lithium ion battery has the advantages of stable performance, high energy density, wide working environment, safety, no toxicity, long service life, multiple charge and discharge cycle times, capability of discharging with large current and the like, and is a current research hot spot.
Since 1997 olivine structured lithium iron phosphate (LiFePO 4 ) As proved to be a positive electrode material of a lithium ion battery, how to improve the electrochemical performance of a lithium iron phosphate lithium ion battery is more and more important. In particular, in terms of crystal structure, the structural change between the product of the positive electrode discharge process of the lithium iron phosphate battery and the orthorhombic iron phosphate of the product of the charging process is very small, and the structural similarity is very high.
Ferric phosphate (FePO) 4 ) Is found to be widely used in the fields of paint, chemical catalysis, ion substance exchange, biological substance mineralization, certain specific inhibitors and the like. At the end of the 20 th century, along with the rapid development of lithium ion battery materials, iron phosphate is paid attention to and researched as a precursor of a lithium ion positive electrode material taking lithium iron phosphate as a positive electrode material, and reports and researches show that the iron phosphate needs to precisely control the iron-phosphorus molar ratio, namely the iron-phosphorus element content, so that the lithium iron phosphate lithium ion battery has good electrochemical performance, and in addition, the particle size of the product has great influence on the electrochemical performance. In the existing industrial production process, a plurality of processes for preparing the ferric phosphate exist, but products meeting the requirements of the high-quality battery-grade ferric phosphate are fewer, the process has a larger lifting space, and the market demand for the high-quality battery-grade ferric phosphate is increasing. Therefore, the related industries such as lithium iron phosphate batteries and the like inevitably put higher requirements on high-quality precursor ferric phosphate.
The invention patent with publication number of CN114436233A discloses a preparation method of ferric phosphate, wherein iron powder is used as an iron source, firstly, reagent phosphoric acid is used for carrying out iron melting treatment to obtain ferrous phosphate mother liquor, then oxidant hydrogen peroxide is added to obtain ferric phosphate mother liquor, ammonia water is used as a pH regulator, crude ferric phosphate solid is separated after filtration, the crude ferric phosphate solid is continuously added into hot phosphoric acid to be formed into a refined ferric phosphate product, and finally, the final ferric phosphate product is obtained through washing and drying. The process route has no introduction of other impurity ions, can prepare the battery-grade ferric phosphate, and is environment-friendly. But directly takes the iron simple substance as an iron source, and the prior molten iron treatment needs high temperature and has high energy consumption. And high-purity concentrated phosphoric acid and reduced iron powder are required, so that the raw material cost is too high, and the method is not suitable for industrial production.
The invention patent with publication number CN114229814A discloses a preparation method of ferric phosphate, feSO is added into a reaction kettle 4 Solution and H 3 PO 4 Adding excessive H after reaction 2 O 2 Oxidizing the solution, adding NH 3 ·H 2 Regulating the pH of the reaction system by the O solution, heating to 85-90 ℃, continuously stirring for 1.0-2.0 h, and obtaining FePO after the reaction is completed 4 ·2H 2 The O slurry is dehydrated by a filter press, and the obtained filter cake is washed and dried to obtain D50 which is distributed in 1.5-4.0 um and P: fePO with Fe of 0.98-1.02 4 And (3) powder. The method uses ferrous sulfate to directly react with phosphoric acid to generate ferrous phosphate, then uses hydrogen peroxide to oxidize the ferrous phosphate into ferric phosphate, the reaction time of the phosphoric acid solution and the ferrous sulfate is long, the reaction rate is slow, sulfate ions are introduced, and more deionized water is required to be consumed.
The invention patent with publication number of CN112678792A discloses a preparation method and application of ferric phosphate, and the preparation method comprises the following steps: mixing an ammonia source and a phosphorus source, and adjusting the pH value of the solution to be 1-5 to prepare a base solution; under the protection of inert gas, mixing an iron source and a phosphorus source, adding alkali to adjust the pH value of the solution to 1.5-4, and preparing a raw material liquid; simultaneously dropwise adding hydrogen peroxide and raw material liquid into the base liquid, wherein the molar quantity of the added hydrogen peroxide is 0.6-20 times of the molar quantity of iron, continuously stirring in the reaction process, and continuously reacting for 0.5-3 h after the dropwise adding is finished; washing, drying and roasting the solid obtained by separating the reactants to obtain the ferric phosphate, wherein the roasting atmosphere is an oxidizing atmosphere, the roasting temperature is 350-600 ℃, and the roasting time is 2-14 h. The method is characterized in that a phospham solution is prepared firstly and then mixed with an iron source to prepare the ferric phosphate, the iron-phosphorus ratio is not well controlled, the reaction process is required to be carried out in an inert gas environment, and the operation is relatively complex.
To sum up, at present, iron phosphate is mostly prepared by reacting ferrous sulfate, iron and iron slag mixture and the like with phosphoric acid and phosphate, and as metal and non-metal impurities are doped in the synthesis process, ammonium salt, ammonia water, strong alkali and the like are generally introduced to remove the impurities, more byproducts and solid waste are generated; and the increase of ammonium salt and the like in the process system can improve the ammonia nitrogen content in industrial wastewater, so that the environmental protection cost is higher and the environmental threat is higher. In addition, the traditional preparation method of ferric phosphate also adopts the reaction of strong acid and pure iron, and the generated ferric iron product continuously reacts with phosphoric acid to generate ferric phosphate product. The introduction of a large amount of impurity ions can cause serious interference to the cycle performance and power in the charge and discharge processes of the battery, and the stability of the battery is affected.
The invention patent with publication number of CN113428848A discloses a cyclic preparation process of battery-grade ferric phosphate, which selects ferric nitrate and phosphoric acid as raw materials, controls the proportion of the ferric nitrate and the phosphoric acid and keeps the excessive phosphoric acid by controlling the conditions of reaction time, temperature, stirring speed, material proportion and the like, and can prepare high-purity ferric phosphate without adjusting pH and adding other additives in the preparation process; meanwhile, the nitric acid generated by the reaction is subjected to secondary reaction with an iron source, so that the recycling of the nitric acid is realized, the high-purity ferric phosphate is prepared by only using the ferric nitrate and the phosphoric acid, and NH is not generated in the process 4 + And the influence of plasma impurity ions and additives reduces the production cost and impurity removal cost of the process. However, this method requires the use of an excessive amount of phosphoric acid, and the yield of the obtained iron phosphate is not high.
Disclosure of Invention
Aiming at the defects, the invention solves the technical problem of providing a preparation method of high-quality ferric phosphate with high yield.
The preparation method of the ferric phosphate comprises the following steps:
mixing ferric nitrate crystals with phosphoric acid solution, and reacting for more than 30 minutes at the temperature of 120-200 ℃ to obtain the ferric phosphate crystals, wherein the concentration of the phosphoric acid solution is more than or equal to 85wt%.
In one embodiment of the invention, the molar ratio of ferric nitrate to phosphoric acid in the phosphoric acid solution is 0.8 to 1.2:1.
In one embodiment of the present invention, the reaction is carried out at a temperature of 120 to 200℃for 0.5 to 3 hours.
In a preferred embodiment, the ferric nitrate crystals are prepared by the following method:
mixing calcium nitrate, ferrous sulfate and water to obtain a mixed solution, reacting the mixed solution at 40-80 ℃ for 0.5-1 h, and filtering to obtain calcium sulfate precipitate and ferrous nitrate solution;
mixing ferrous nitrate solution with dilute nitric acid, reacting at 50-80 deg.c for 0.5-1.5 hr, concentrating and crystallizing to obtain ferric nitrate crystal.
In one embodiment of the invention, the molar ratio of calcium nitrate to ferrous sulfate is 0.8 to 1.1:1. In a preferred embodiment of the invention, the molar ratio of calcium nitrate to ferrous sulfate is 1:1.
In one embodiment of the invention, the molar ratio of ferrous nitrate in the ferrous nitrate solution to nitric acid in the dilute nitric acid is 0.3 to 1:1.
In a preferred embodiment of the invention, the molar ratio of ferrous nitrate in the ferrous nitrate solution to nitric acid in the dilute nitric acid is 0.6:1.
Compared with the prior art, the invention has the following beneficial effects:
aiming at the current demand for high-quality ferric phosphate, the invention can provide a preparation method of battery-grade ferric phosphate, which has the advantages of simple method, high yield, high purity of the obtained ferric phosphate, stable performance, and reduced process cost from the source.
Detailed Description
The preparation method of the ferric phosphate comprises the following steps:
mixing ferric nitrate crystals with phosphoric acid solution, and reacting for more than 30 minutes at the temperature of 120-200 ℃ to obtain the ferric phosphate crystals, wherein the concentration of the phosphoric acid solution is more than or equal to 85wt%.
The invention adopts ferric nitrate crystal to directly react with high-concentration phosphoric acid, controls certain reaction temperature and reaction time, directly obtains yellow amorphous ferric phosphate dihydrate, can simplify the preparation process of ferric phosphate, improves the yield of ferric phosphate, and has the advantages of high phosphorus-iron ratio, low impurity content, stable performance and good batch consistency.
The reaction temperature in the step is controlled to be 120-200 ℃, the temperature is too high, the reaction is very severe, and the product particles are larger; the temperature is too low, the reaction is not easy to be carried out, and the yield and the reaction efficiency are affected.
In one embodiment of the invention, the molar ratio of ferric nitrate to phosphoric acid in the phosphoric acid solution is 0.8 to 1.2:1.
In one embodiment of the present invention, the reaction is carried out at a temperature of 120 to 200℃for 0.5 to 3 hours.
In a preferred embodiment, the ferric nitrate crystals are prepared by the following method:
mixing calcium nitrate, ferrous sulfate and water to obtain a mixed solution, reacting the mixed solution at 40-80 ℃ for 0.5-1 h, filtering to obtain calcium sulfate precipitate and ferrous nitrate solution, mixing the ferrous nitrate solution with dilute nitric acid, reacting at 50-80 ℃ for 0.5-1.5 h, concentrating, crystallizing to obtain ferric nitrate crystals. The method uses wet-process phosphoric acid as a phosphorus source and ferric nitrate as an iron source, and calcium nitrate reacts with ferrous sulfate to obtain ferric nitrate, and then reacts with purified wet-process phosphoric acid to obtain ferric phosphate. The by-product nitrogen oxide can be collected and continuously prepared into nitric acid solution to be circularly reacted, so that the requirements of green chemistry are met. The calcium nitrate is a by-product of the frozen mother liquor of the nitrophosphate fertilizer, and the ferrous sulfate can be from a titanium white by-product or from other substances taking the ferrous sulfate as a main component. The ferric nitrate is obtained by utilizing the reaction of low-value byproduct ferrous sulfate and calcium nitrate, so that the resource recycling of enterprises is realized, and the main reaction in the process is as follows:
Ca(NO 3 ) 2 +FeSO 4 ＝CaSO 4 +Fe(NO 3 ) 2
3Fe(NO 3 ) 2 +4HNO 3 ＝3Fe(NO 3 ) 3 +NO↑+2H 2 O
Fe(NO 3 ) 3 +H 3 PO 4 ＝FePO 4 +3HNO 3
wherein, the calcium nitrate and the ferrous sulfate can react to generate ferrous nitrate solution and calcium sulfate precipitate after being mixed at normal temperature. The content of iron in the calcium sulfate is about 0.1 percent, and the concentration of calcium ions in the ferrous nitrate solution is 100-200 ppm. In one embodiment of the invention, the molar ratio of calcium nitrate to ferrous sulfate is 0.8 to 1.1:1. In a preferred embodiment of the invention, the molar ratio of calcium nitrate to ferrous sulfate is 1:1.
The mixing of the calcium nitrate and the ferrous sulfate with the water can be carried out in a manner conventional in the art, for example, the calcium nitrate and the ferrous sulfate are prepared into a solution, and then the solution is mixed, or the calcium nitrate and the ferrous sulfate can be directly mixed with the water to form a mixed solution.
In one embodiment of the present invention, the concentration of ferrous sulfate in the mixed solution is 1mol/L.
The ferrous nitrate solution is dropwise added with dilute nitric acid under the heating state to convert ferrous nitrate into ferric nitrate solution, and the ferric nitrate solution is obtained by direct filtration. In one embodiment of the invention, the molar ratio of ferrous nitrate in the ferrous nitrate solution to nitric acid in the dilute nitric acid is 0.3 to 1:1.
In a preferred embodiment of the invention, the molar ratio of ferrous nitrate in the ferrous nitrate solution to nitric acid in the dilute nitric acid is 0.6:1.
In one embodiment of the invention, the concentration of dilute nitric acid is 30%.
The ferric nitrate crystal can be obtained by concentrating and crystallizing the ferric nitrate solution, and the concentration and crystallization methods commonly used in the field are applicable to the invention, such as simple evaporation, concentration, cooling, crystallization and the like.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
Mixing calcium nitrate and ferrous sulfate solution according to a molar ratio of 1:1, wherein the concentration of ferrous sulfate in the mixed solution is 1mol/L, reacting the mixed solution for 0.5h at the temperature of 40 ℃, filtering to obtain a mixed solution of calcium sulfate precipitate and ferrous nitrate, wherein the content of iron in the calcium sulfate is about 0.1%, the concentration of calcium ions in the ferrous nitrate solution is 183ppm, continuously adding 30% dilute nitric acid into the ferrous nitrate solution, reacting for 1h at the temperature of 80 ℃, and obtaining ferric nitrate solution, and continuously evaporating, concentrating, cooling and crystallizing to obtain ferric nitrate crystals.
Ferric nitrate crystals and phosphoric acid (85%) solution were mixed according to a molar ratio of 1:1, reacted at 120 ℃ for 30min to obtain a pale yellow ferric phosphate dihydrate solid, which was dried and analyzed for composition, as detailed in table 1. The ratio of phosphorus to iron is 0.98, the yield is 99.4%, and the impurity ions meet the standard.
TABLE 1
| Numbering device | P 2 O 5 (％) | Fe 2 O 3 (％) | CaO(％) | SO 3 (％) | Al 2 O 3 (％) | ZnO(％) |
| Example 1 | 35.7 | 41.0 | 0.0043 | 0.0027 | - | 0.0036 |
| Comparative example 1 | 35.2 | 41.8 | 0.039 | 0.0227 | 0.0471 | - |
| Comparative example 2 | 35.7 | 41.8 | 0.0052 | 0.0220 | 0.0209 | - |
| Comparative example 3 | 34.2 | 41.4 | 0.0339 | 0.0853 | 0.0132 | - |
Comparative example 1
The iron nitrate crystals of example 1 were used, dissolved in deionized water, and mixed with a phosphoric acid (85%) solution in a molar ratio of 1:1.1, reacted at 90 ℃ for 10 hours, and then filtered to give an off-white iron phosphate dihydrate solid, which was dried and analyzed for composition, as detailed in table 1. The phosphorus-iron ratio is 0.95, and the yield is 62.0%.
Comparative example 2
The iron nitrate crystals of example 1 were used, dissolved in deionized water, and mixed with a phosphoric acid (85%) solution in a molar ratio of 1:1.1, reacted at 90 ℃ for 12 hours, and then filtered to give an off-white iron phosphate dihydrate solid, which was dried and analyzed for composition, as detailed in table 1. The phosphorus-iron ratio is 0.96, and the yield is 89.1%.
Comparative example 3
The iron nitrate crystals of example 1 were used, dissolved in deionized water, and mixed with a phosphoric acid (85%) solution in a molar ratio of 1:1, reacted at 90 ℃ for 12 hours, and then filtered to give an off-white iron phosphate dihydrate solid, which was dried and analyzed for composition, as detailed in table 1. The phosphorus-iron ratio is 0.93, and the yield is 84.2%.
Example 2
Mixing calcium nitrate and ferrous sulfate solution according to a molar ratio of 1:1.05, wherein the ferrous sulfate concentration is 1mol/L in the mixed solution, reacting the mixed solution for 0.5h at the temperature of 40 ℃, filtering to obtain a mixed solution of calcium sulfate precipitate and ferrous nitrate, wherein the iron content in the calcium sulfate is about 0.1%, the calcium ion concentration in the ferrous nitrate solution is 116ppm, continuously adding 30% dilute nitric acid into the ferrous nitrate solution, reacting for 1h at the temperature of 80 ℃, and obtaining ferric nitrate solution, and continuously evaporating, concentrating, cooling and crystallizing to obtain ferric nitrate crystals.
Mixing ferric nitrate crystals and phosphoric acid (85%) solution according to a molar ratio of 1:1, and reacting for 30min at 150 ℃ to obtain light yellow ferric phosphate dihydrate solid, wherein the ferric phosphate dihydrate solid has a phosphorus-iron ratio of 0.98, a yield of 99.5%, and impurity ions all meet the standard, and the details are shown in Table 2.
Example 3
Mixing calcium nitrate and ferrous sulfate solution according to a molar ratio of 1:1.1, reacting the mixed solution at a temperature of 40 ℃ for 0.5h, filtering to obtain a mixed solution of calcium sulfate precipitate and ferrous nitrate, wherein the iron content in the calcium sulfate is about 0.1%, the calcium ion concentration in the ferrous nitrate solution is 123ppm, continuously adding 30% dilute nitric acid into the ferrous nitrate solution, reacting at a temperature of 80 ℃ for 1h, and obtaining ferric nitrate solution, and continuously evaporating, concentrating, cooling and crystallizing to obtain ferric nitrate crystals.
Mixing ferric nitrate crystals and phosphoric acid (85%) solution according to a molar ratio of 1:1, and reacting for 60min at 120 ℃ to obtain light yellow ferric phosphate dihydrate solid, wherein the ferric phosphate dihydrate solid has a phosphorus-iron ratio of 0.98, a yield of 99.6%, and impurity ions all meet the standard, and the details are shown in Table 2.
Example 4
Mixing calcium nitrate and ferrous sulfate solution according to a molar ratio of 1:1, wherein the concentration of ferrous sulfate in the mixed solution is 1mol/L, reacting the mixed solution for 0.5h at the temperature of 60 ℃, filtering to obtain a mixed solution of calcium sulfate precipitate and ferrous nitrate, wherein the content of iron in the calcium sulfate is about 0.1%, the concentration of calcium ions in the ferrous nitrate solution is 145ppm, continuously adding 30% dilute nitric acid into the ferrous nitrate solution, reacting for 1h at the temperature of 80 ℃, and obtaining ferric nitrate solution, and continuously evaporating, concentrating, cooling and crystallizing to obtain ferric nitrate crystals.
Mixing ferric nitrate crystals and phosphoric acid (85%) solution according to a molar ratio of 1:1, and reacting for 60min at a temperature of 95 ℃ to obtain light yellow ferric phosphate dihydrate solid, wherein the phosphorus-iron ratio is 0.97, the yield is 90.1%, and impurity ions all meet the standard, and are shown in Table 2 in detail.
TABLE 2
| Numbering device | P 2 O 5 (％) | Fe 2 O 3 (％) | CaO(％) | SO 3 (％) | Al 2 O 3 (％) | ZnO(％) |
| Example 1 | 35.7 | 41.02 | 0.0043 | 0.0027 | - | 0.0036 |
| Example 2 | 35.89 | 41.28 | 0.0032 | 0.0032 | - | 0.0061 |
| Example 3 | 36.04 | 41.44 | 0.0021 | 0.0039 | - | 0.0043 |
| Example 4 | 35.12 | 40.73 | 0.0109 | 0.0044 | - | 0.0039 |
Therefore, the method for preparing the ferric phosphate is simple, the yield is high, and the purity and the performance of the obtained ferric phosphate are stable.
Claims (6)
1. The preparation method of the ferric phosphate is characterized by comprising the following steps:
mixing ferric nitrate crystals with phosphoric acid solution, and reacting for more than 30 minutes at the temperature of 120-200 ℃ to obtain the ferric phosphate crystals, wherein the concentration of the phosphoric acid solution is more than or equal to 85wt%.
2. The method for producing iron phosphate according to claim 1, wherein: the molar ratio of ferric nitrate to phosphoric acid in the phosphoric acid solution is 0.8-1.2.
3. The method for producing iron phosphate according to claim 1, wherein: reacting for 0.5-3 h.
4. The method for producing iron phosphate according to claim 1, wherein: the ferric nitrate crystal is prepared by the following method:
mixing calcium nitrate, ferrous sulfate and water to obtain a mixed solution, reacting the mixed solution at 40-80 ℃ for 0.5-1 h, and filtering to obtain calcium sulfate precipitate and ferrous nitrate solution;
mixing ferrous nitrate solution with dilute nitric acid, reacting at 50-80 deg.c for 0.5-1.5 hr, concentrating and crystallizing to obtain ferric nitrate crystal.
5. The method for producing iron phosphate according to claim 4, wherein: the molar ratio of the calcium nitrate to the ferrous sulfate is 0.8-1.1:1.
6. The method for producing iron phosphate according to claim 4, wherein: the molar ratio of ferrous nitrate in the ferrous nitrate solution to nitric acid in the dilute nitric acid is 0.3-1:1.
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