CN112661129A - Preparation method of iron phosphate - Google Patents
Preparation method of iron phosphate Download PDFInfo
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- CN112661129A CN112661129A CN202110113059.1A CN202110113059A CN112661129A CN 112661129 A CN112661129 A CN 112661129A CN 202110113059 A CN202110113059 A CN 202110113059A CN 112661129 A CN112661129 A CN 112661129A
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- phosphate
- ferrous
- iron
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- iron phosphate
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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
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 35
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims abstract description 30
- 229940116007 ferrous phosphate Drugs 0.000 claims abstract description 28
- 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 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 26
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 22
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 16
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 230000001502 supplementing effect Effects 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 9
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012991 xanthate Substances 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 159000000014 iron salts Chemical class 0.000 claims 1
- 159000000001 potassium salts Chemical class 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000000843 powder Substances 0.000 description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 13
- 229910052749 magnesium Inorganic materials 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 229910052793 cadmium Inorganic materials 0.000 description 11
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- -1 xanthate ester Chemical class 0.000 description 1
Images
Abstract
A preparation method of iron phosphate relates to the field of new energy material preparation, and comprises the following steps: mixing a ferrous sulfate solution and a phosphorus source in proportion, stirring for reaction for 10-120min, adding an adjusting solution, adjusting the pH value to 3-7, filtering, and washing to obtain ferrous phosphate; transferring the ferrous phosphate into a reaction kettle, adding an impurity removing agent and a complexing agent, and then, according to the proportion of P: supplementing a phosphorus source according to the proportion of 1:1-1.5:1, then adding an oxidant which is oxidized by ferrous iron and is 1.0-1.5 times of the ferric iron by weight, adding an adjusting solution, adjusting the pH value to 1.5-3.5, firstly preserving the temperature for 30-90min, then heating to 80-100 ℃ and then carrying out formation for 30-180min, then precipitating, filtering, washing and drying to obtain a high-purity ferric phosphate finished product; keeping the temperature of the ferric phosphate dihydrate at 400-750 ℃ for 30-360min to obtain a finished anhydrous ferric phosphate product. The method can efficiently remove heavy metal ions, thereby effectively ensuring the purity of the iron phosphate.
Description
Technical Field
The invention relates to the field of new energy material preparation, and particularly relates to a preparation method of iron phosphate.
Background
In the current anode material family, the olivine-structured lithium iron phosphate LiFePO4 has become one of the most mature anode materials for lithium ion batteries because of its advantages of high theoretical specific capacity (170mAh/g), good cycle performance, good thermal stability, low process cost, no environmental pollution, etc.
In the current lithium iron phosphate industrial path, the iron phosphate process route has become the mainstream; the ferrous sulfate is a main raw material for preparing the iron phosphate, a large amount of ferrous sulfate is produced as a byproduct in the production process of titanium white, but the iron phosphate has low purity due to the fact that the iron phosphate contains a large amount of magnesium, manganese, titanium, zinc, copper, chromium, cadmium and other heavy metal elements, and the magnesium, the titanium and the manganese all reach thousands of ppm, and the requirements of battery-grade and food-grade iron phosphate are difficult to meet.
In view of this, the present application is specifically made.
Disclosure of Invention
The invention aims to provide a method for preparing iron phosphate, which can remove heavy metal ions efficiently, thereby effectively ensuring the purity of the iron phosphate, and does not need to remove impurities of ferrous sulfate raw materials separately in the production process, thereby effectively reducing each cost of pretreatment.
The embodiment of the invention is realized by the following steps:
the preparation method of the iron phosphate comprises the following steps:
mixing a ferrous sulfate solution and a phosphorus source in proportion, stirring for reaction for 10-120min, adding an adjusting solution, adjusting the pH value to 3-7, filtering, and washing to obtain ferrous phosphate;
transferring the ferrous phosphate into a reaction kettle, adding an impurity removing agent and a complexing agent, and then, according to the proportion of P: supplementing a phosphorus source according to the proportion of 1:1-1.5:1, then adding an oxidant which is oxidized by ferrous iron and is 1.0-1.5 times of the ferric iron by weight, adding an adjusting solution, adjusting the pH value to 1.0-3.0, firstly preserving the temperature for 30-90min, then heating to 80-100 ℃ and then carrying out formation for 30-180min, then precipitating, filtering, washing and drying to obtain a high-purity ferric phosphate finished product;
keeping the temperature of the ferric phosphate dihydrate at 400-750 ℃ for 30-360min to obtain a finished anhydrous ferric phosphate product.
Further, the mass of the impurity removing agent is 0.5-20% of the mass ratio of the ferrous phosphate.
Further, the mass of the complexing agent is 0-1% of the mass ratio of the ferrous phosphate.
Further, the phosphorus source is [ PO ]4]3-One or more of phosphoric acid solution with the concentration of 0.05-5mol/L, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate or disodium hydrogen phosphate.
Further, the conditioning solution is NH3-H2O and/or NaOH solution or a mixture of two solutions.
Further, the impurity removing agent is one or a mixture of more of sulfuric acid, hydrochloric acid, nitric acid, citric acid, acetic acid and soluble iron salt, ammonium salt, sodium salt and potassium salt thereof.
Further, the complexing agent is one or a mixture of more of octohydroxyquinoline, xanthate capture agents or dithiocarbamate Derivative (DTC) capture agents.
Further, the oxidant is one or a mixture of more of hydrogen peroxide, sodium chlorate, sodium hypochlorite NaClO, potassium chlorate and potassium hypochlorite.
The embodiment of the invention has the beneficial effects that:
according to the preparation method of the iron phosphate, the impurity removing agent and the complexing agent are added, so that heavy metal ions in a solution can be subjected to deep impurity removal, the purity of an iron phosphate finished product is higher, more specifically, generated ferrous phosphate is separated after precipitation, the heavy metals attached to the surface and in crystal lattices of the ferrous phosphate, such as magnesium, manganese, zinc and other metals which cannot be removed, are dissolved by the impurity removing agent such as sulfuric acid, hydrochloric acid and the like, and the complexing agent is added to generate the complex for separation and removal; in addition, the industrial by-product ferrous sulfate is used as an iron source raw material, and the ferrous phosphate raw material is not required to be subjected to independent impurity removal pretreatment, so that the pretreatment cost can be greatly reduced, a large amount of iron-containing waste residues generated by pretreatment impurity removal are avoided, the industrial resources are reasonably utilized, and the environmental bearing pressure is reduced.
In general, the preparation method of iron phosphate provided by the embodiment of the invention can efficiently remove heavy metal ions, thereby effectively ensuring the purity of the iron phosphate, and the regeneration process does not need to continuously and separately remove impurities from ferrous sulfate raw materials, thereby effectively reducing each cost of pretreatment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a scanning electron microscope image of ferrous phosphate provided by an embodiment of the present invention;
fig. 2 is an XRD pattern of iron phosphate provided by an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terms "substantially", "essentially", and the like are intended to indicate that the relative terms are not required to be absolutely exact, but may have some deviation. For example: "substantially equal" does not mean absolute equality, but it is difficult to achieve absolute equality in actual production and operation, and some deviation generally exists. Thus, in addition to absolute equality, "substantially equal" also includes the above-described case where there is some deviation. In this case, unless otherwise specified, terms such as "substantially", and the like are used in a similar manner to those described above.
The following examples relate to the reaction equation:
2PO4 3-+3Fe2++8H2O＝Fe3(PO4)2·8H2O↓
2Fe2++H2O2+2H+＝2Fe3++2H2O
Fe3++(PO4)3-+2H2O＝Fe PO4·2H2O↓
Fe PO4·2H2O＝Fe PO4+2H2O
more specifically, a diammonium hydrogen phosphate solution in a ferrous sulfate solution, ferrous ions and phosphate radicals can generate precipitates, a ferrous phosphate solid is obtained after filtration, then an impurity removing agent and a complexing agent are added after the ferrous phosphate solid is crushed, heavy metals contained in the solid are dissolved, and then phosphoric acid and an oxidizing agent are added to the remaining solid, so that an iron phosphate solid is generated.
Example 1
Referring to fig. 1 and fig. 2, the present embodiment provides a method for preparing iron phosphate, including the following steps:
120mL of ferrous sulfate solution with the molar concentration of 1.3mol/L is taken and added into 80mL of diammonium hydrogen phosphate solution with the molar concentration of 1.3mol/L, and NH is added while stirring3·H2And O, adjusting the pH value to 7, and reacting for 60min to obtain ferrous phosphate precipitate.
After filtration and washing, the ferrous phosphate is transferred into a beaker, 100g of water is added for pulping, and 1.3mol/L of FeSO is added424mL of the solution and 0.05g of a dithiocarbamate scavenger were filtered, and 0.4mol of phosphoric acid and H were added to the residue2O2About 3.35g with NH3-H2Adjusting the pH value of the system to 2.0 by O (1:3), heating to 95 ℃ to carry out crystallization for 180min, filtering and drying the precipitate to obtain FePO4 & 2H2O (ferric phosphate dihydrate) powder.
The purity of the FePO4 & 2H2O powder was analyzed by weighing, the purity of the iron phosphate dihydrate was 99.6%, and the contents of impurity elements of magnesium, manganese, zinc, copper, cadmium, chromium and nickel were 14ppm, 31ppm, 12ppm, 2ppm, 0ppm, 1ppm and 1ppm, respectively.
And (3) preserving the temperature of the ferric phosphate dihydrate at 600 ℃ for 120min to obtain a finished product of anhydrous ferric phosphate (FePO 4).
The purity of the FePO4 powder was analyzed by weighing, and the purity of the iron phosphate was 99.6%, and the contents of impurity elements of magnesium, manganese, zinc, copper, cadmium, chromium and nickel were 15ppm, 34ppm, 14ppm, 2ppm, 0ppm, 1ppm and 1ppm, respectively.
Example 2
Adding 420mL of ferrous sulfate solution with the molar concentration of 0.5mol/L into 140mL of diammonium hydrogen phosphate solution with the molar concentration of 1.0mol/L, simultaneously adding 0.2g of dispersant CTAB into the solution, adding 32% of NaOH to adjust the pH value to 5.0, reacting for 20min, and filtering and washing to obtain ferrous phosphate precipitate;
adding water with the solid content of 40% into ferrous phosphate, pulping, adding 20g of sulfuric acid, 5g of sodium sulfate and 1g of xanthate ester catching agent, adding 0.5mol of phosphoric acid, reacting for 0.5 hour, filtering, adding H into the residue2O2About 4.15g of the reaction mixture was added with 16% NaOH to adjust the pH of the system to 1.5, the reaction mixture was reacted for 2 hours, heated to 80 ℃ and aged for 6 hours, filtered and dried to obtain FePO4.2H2O (iron phosphate dihydrate) powder.
The purity of the FePO4 & 2H2O powder was analyzed by weighing, the purity of the iron phosphate dihydrate was 99.6%, and the contents of impurity elements of magnesium, manganese, zinc, copper, cadmium, chromium and nickel were 20ppm, 35ppm, 8ppm, 1ppm, 0ppm and 2ppm, respectively. .
Keeping the temperature of the ferric phosphate dihydrate at 750 ℃ for 0.5h to obtain anhydrous ferric phosphate (FePO)4) And (5) finishing.
Weighing FePO4The purity of the powder was analyzed, and the purity of the iron phosphate was 99.6%, and the contents of impurity elements of magnesium, manganese, zinc, copper, cadmium, chromium and nickel were 24ppm, 40ppm, 10ppm, 1ppm, 0ppm and 2ppm, respectively.
Example 3
40mL of diammonium hydrogen phosphate (NH) having a molar concentration of 1.3mol/L4H2PO4) 120mL of ferrous sulfate (FeSO) with a molar concentration of 1.3mol/L was added4) In solution, with ammonia monohydrate (NH)3.H2O), adjusting the pH value to 4.0, reacting for 10min, filtering and washingSo as to obtain ferrous phosphate precipitate.
After ferrous phosphate is pulped by adding water according to the solid content of 30%, 5g of hydrochloric acid, 10g of ammonium sulfate and 0.05g of octahydroxyquinoline are added, and then 0.5mol of phosphoric acid and 0.04mol of ammonium dihydrogen phosphate are added. The reaction was filtered for 0.5 hour, and H was added to the residue2O23.28g in total, using NH3·H2Adjusting pH of O regulating system to 3.0, aging for 40min, heating to 90 deg.C for 3h, filtering, and drying to obtain FePO4.2H2And (4) O powder. .
The purity of the FePO4 & 2H2O powder was analyzed by weighing, the purity of the iron phosphate dihydrate was 99.5%, and the contents of impurity elements of magnesium, manganese, zinc, copper, cadmium, chromium and nickel were 40ppm, 65ppm, 15ppm, 2ppm, 1ppm and 3ppm, respectively.
Keeping the temperature of the ferric phosphate dihydrate at 400 ℃ for 6h to obtain a finished product of anhydrous ferric phosphate FePO 4; the purity of the FePO4 powder was analyzed by weighing, and the purity of the iron phosphate was 99.5%, and the contents of impurity elements of magnesium, manganese, zinc, copper, cadmium, chromium and nickel were 45ppm, 71ppm, 18ppm, 3ppm, 2ppm, 1ppm and 3ppm, respectively.
Meanwhile, aiming at the embodiment, a contrast test is carried out without adding an impurity removing agent and a complexing agent, and more specifically:
comparative example 1:
120mL of ferrous sulfate solution with the molar concentration of 1.3mol/L is taken and added into 80mL of diammonium hydrogen phosphate solution with the molar concentration of 1.3mol/L, and NH is added while stirring3·H2And O, adjusting the pH value to 7, and reacting for 60min to obtain ferrous phosphate precipitate.
After filtration and washing, the ferrous phosphate is transferred into a beaker, 100g of water is added for pulping, and 1.3mol/L of FeSO is added424mL of the solution was added with 0.4mol of phosphoric acid and H2O2About 3.35g with NH3-H2Adjusting the pH value of the system to 2.0 by O (1:3), heating to 95 ℃ to form a precipitate for 180min, filtering and drying the precipitate to obtain FePO4·2H2O (iron phosphate dihydrate) powder.
Keeping the temperature of the ferric phosphate dihydrate at 600 ℃ for 120min to obtain anhydrous ferric phosphate (FePO)4) And (5) finishing.
Weighing FePO4Analysis of powderThe purity of the iron phosphate is 99.6 percent, and the content of impurity elements such as magnesium, manganese, zinc, copper, cadmium, chromium and nickel is 310ppm, 388ppm, 70ppm, 10ppm, 3ppm, 4ppm and 4ppm respectively.
Comparative example 2
Adding 420mL of ferrous sulfate solution with the molar concentration of 0.5mol/L into 140mL of diammonium hydrogen phosphate solution with the molar concentration of 1.0mol/L, simultaneously adding 0.2g of dispersant CTAB into the solution, adding 32% of NaOH to adjust the pH value to 5.0, reacting for 20min, and filtering and washing to obtain ferrous phosphate precipitate;
adding water according to the solid content of 40 percent into ferrous phosphate, pulping, adding 0.5mol of phosphoric acid, and adding H2O2About 4.15g of the reaction mixture was added with 16% NaOH to adjust the pH of the system to 1.5, the reaction mixture was reacted for 2 hours, heated to 80 ℃ and aged for 6 hours, filtered and dried to obtain FePO4.2H2O (iron phosphate dihydrate) powder. Keeping the temperature of the ferric phosphate dihydrate at 750 ℃ for 0.5h to obtain anhydrous ferric phosphate (FePO)4) And (5) finishing.
Weighing FePO4The purity of the powder was analyzed, and the purity of the iron phosphate was 99.6%, and the contents of impurity elements of magnesium, manganese, zinc, copper, cadmium, chromium and nickel were 638ppm, 462ppm, 68ppm, 7ppm, 4ppm and 4ppm, respectively.
Comparative example 3:
40mL of diammonium hydrogen phosphate (NH) having a molar concentration of 1.3mol/L4H2PO4) 120mL of ferrous sulfate (FeSO) with a molar concentration of 1.3mol/L was added4) In solution, with ammonia monohydrate (NH)3.H2O), adjusting the pH value to 4.0, reacting for 10min, filtering and washing to obtain ferrous phosphate precipitate.
Adding water into ferrous phosphate according to the solid content of 30 percent for pulping, then adding 0.5mol of phosphoric acid and 0.04mol of ammonium dihydrogen phosphate, and adding H into the residue2O23.28g, using NH3·H2Adjusting pH of O regulating system to 3.0, aging for 40min, heating to 90 deg.C for 3h, filtering, and drying to obtain FePO4.2H2And (4) O powder. Keeping the temperature of the ferric phosphate dihydrate at 400 ℃ for 6h to obtain anhydrous ferric phosphate FePO4And (5) finishing.
Weighing FePO4Powder divisionThe purity of the iron phosphate is analyzed, the purity of the iron phosphate is 99.5 percent, and the contents of impurity elements such as magnesium, manganese, zinc, copper, cadmium, chromium and nickel are respectively 987ppm, 790ppm, 109ppm, 15ppm, 7ppm, 1ppm and 9 ppm.
By reacting FePO4The powders were compared in the relevant way, with example one and comparative example one being control tests; example two and comparative example two are control tests; example three and comparative example three are control tests:
in summary, the method for preparing iron phosphate according to the embodiment of the present invention can efficiently remove heavy metal ions, thereby effectively ensuring the purity of iron phosphate, and does not need to separately remove impurities from ferrous sulfate raw materials in the reproduction process, thereby effectively reducing the costs of pretreatment, particularly, the removal rate of metals such as magnesium, manganese, zinc, etc. contained in a solution can reach 95%, 90%, and 85% or more, while metals such as cadmium, chromium, nickel, etc. contained in a solution are less, so that there is a certain deviation during measurement, thereby affecting the judgment of experimental results, but the removal can still be performed to a certain extent through data calculation.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the iron phosphate is characterized by comprising the following steps:
s1, mixing the ferrous sulfate solution and the phosphorus source in proportion, stirring for reaction for 10-120min, adding the adjusting solution, adjusting the pH value to 3.0-7.0, filtering and washing to obtain ferrous phosphate;
s2, transferring the ferrous phosphate into a reaction kettle, adding an impurity removing agent and a complexing agent, and then adding the raw materials according to the proportion of P: supplementing a phosphorus source according to the proportion of 1:1-1.5:1, then adding an oxidant which is oxidized by ferrous iron and is 1.0-1.5 times of the ferric iron by weight, adding an adjusting solution, adjusting the pH value to 1.0-3.0, firstly preserving the temperature for 30-90min, then heating to 80-100 ℃ and then carrying out formation for 30-180min, then precipitating, filtering, washing and drying to obtain a high-purity ferric phosphate finished product;
s3: keeping the temperature of the ferric phosphate dihydrate at 400-750 ℃ for 30-360min to obtain a finished anhydrous ferric phosphate product.
2. The method for preparing iron phosphate according to claim 1, wherein the mass of the impurity removing agent is 0.5-20% of the mass ratio of ferrous phosphate.
3. The method for preparing iron phosphate according to claim 1, wherein the mass of the complexing agent is 0-1% of the mass ratio of ferrous phosphate.
4. The method of producing iron phosphate according to claim 1, wherein the phosphorus source is PO4 3-One or more of phosphoric acid solution with the concentration of 0.05-5mol/L, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate or disodium hydrogen phosphate.
5. The method for producing iron phosphate according to claim 1, characterized in that the conditioning solution is NH3-H2O and/or NaOH solution or a mixture of two solutions.
6. The method for preparing iron phosphate according to claim 1, wherein the impurity removing agent is a mixture of one or more of sulfuric acid, hydrochloric acid, nitric acid, citric acid, acetic acid and soluble iron salts, ammonium salts, sodium salts and potassium salts thereof.
7. The method for preparing iron phosphate according to claim 1, characterized in that the complexing agent is one or more of a mixture of octohydroxyquinoline, xanthate scavenger or dithiocarbamate derivative DTC scavenger.
8. The method for preparing iron phosphate according to claim 1, wherein the oxidant is one or more of hydrogen peroxide, sodium chlorate, sodium hypochlorite, potassium chlorate and potassium hypochlorite.
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| CN116161633A (en) * | 2022-12-05 | 2023-05-26 | 广东工业大学 | Method for preparing ferric phosphate by utilizing aluminum product sewage and application of ferric phosphate |
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