CN113526480A - Method for preparing ferrous phosphate from titanium dioxide byproduct - Google Patents
Method for preparing ferrous phosphate from titanium dioxide byproduct Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229940116007 ferrous phosphate Drugs 0.000 title claims abstract description 86
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title claims abstract description 86
- 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 title claims abstract description 86
- 239000006227 byproduct Substances 0.000 title claims abstract description 56
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 57
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 57
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 57
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011574 phosphorus Substances 0.000 claims abstract description 30
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 30
- 239000012065 filter cake Substances 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 238000001556 precipitation Methods 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 23
- 239000003337 fertilizer Substances 0.000 claims abstract description 22
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 18
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 35
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000003912 environmental pollution Methods 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 92
- 239000000047 product Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 238000001223 reverse osmosis Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002686 phosphate fertilizer Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910011011 Ti(OH)4 Inorganic materials 0.000 description 1
- 229910011006 Ti(SO4)2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/245—Preparation from compounds containing nitrogen and sulfur
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The application relates to the technical field of new energy and lithium ion batteries, and provides a method for preparing a lithium iron phosphate precursor ferrous phosphate by using a titanium dioxide byproduct, which comprises the following steps: dissolving ferrous sulfate serving as a titanium dioxide byproduct to obtain a first solution, mixing and reacting a first neutralizing agent with the first solution, and filtering to obtain a ferrous sulfate solution; providing a phosphoric acid fertilizer, mixing the diluted phosphoric acid fertilizer with a second neutralizing agent for reaction, and filtering to obtain a phosphorus solution; mixing the ferrous sulfate solution, the phosphorus solution and a third neutralizing agent for reaction, filtering and separating to obtain a ferrous phosphate filter cake and a liquid after iron precipitation; and (3) carrying out online washing and drying treatment on the ferrous phosphate filter cake to obtain ferrous phosphate, and carrying out concentration and crystallization treatment on the iron-precipitated liquid to obtain ammonium sulfate. The preparation method is convenient and easy to operate, simultaneously has good impurity removal effect, the obtained ferrous phosphate has high purity, can be directly used for producing lithium iron phosphate by a liquid phase method, and the obtained waste liquid can be recycled, so that the environmental pollution can not be caused, and the large-scale production can be ensured.
Description
Technical Field
The application belongs to the technical field of new energy and lithium ion batteries, and particularly relates to a method for preparing ferrous phosphate from a titanium dioxide byproduct.
Background
At present, lithium iron phosphate is mostly prepared by a solid-phase iron phosphate method, wherein iron phosphate and lithium carbonate are mixed and ball-milled, carbon generated by high-temperature carbonization of a carbon source is used for coating, and ferric iron is reduced to ferrous iron at high temperature to form lithium iron phosphate. The preparation of the conventional iron phosphate is that ferrous sulfate is dissolved, and is mixed with a phosphorus source after being purified and purified for a plurality of times, sufficient oxidant is added to oxidize the iron source into ferric iron, and then iron phosphate precipitation is obtained by adjusting pH. However, the method has the disadvantages of strong dependence on raw materials, long impurity removal process, high oxidant consumption, high cost and difficult wide application.
Disclosure of Invention
The application aims to provide a method for preparing ferrous phosphate from a titanium dioxide byproduct, and aims to solve the problems of complicated preparation process, environmental pollution and high cost in the prior art for producing ferrous phosphate.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the application provides a method for preparing ferrous phosphate from a titanium dioxide byproduct, comprising the following steps:
dissolving ferrous sulfate serving as a titanium dioxide byproduct to obtain a first solution, mixing a first neutralizing agent with the first solution for reaction, and filtering to obtain a ferrous sulfate solution;
providing a phosphoric acid fertilizer, mixing the diluted phosphoric acid fertilizer with a second neutralizing agent for reaction, and filtering to obtain a phosphorus solution;
mixing the ferrous sulfate solution, the phosphorus solution and a third neutralizing agent for reaction, and filtering and separating to obtain a ferrous phosphate filter cake and a liquid after iron precipitation;
and carrying out online washing and drying treatment on the ferrous phosphate filter cake to obtain ferrous phosphate, and carrying out concentration and crystallization treatment on the liquid after iron precipitation to obtain ammonium sulfate and desalted water.
According to the method for preparing ferrous phosphate from the titanium dioxide by-product, provided by the first aspect of the application, ferrous sulfate and phosphate fertilizer which are titanium dioxide by-products are used as raw materials, impurity removal treatment is respectively carried out on the raw materials to obtain a ferrous sulfate solution and a phosphorus solution, a synthetic reaction is carried out on the mixed solution according to the atomic molar ratio to obtain a ferrous phosphate precipitate and a post-iron precipitation solution, and the post-iron precipitation solution is concentrated and crystallized to recover the ammonium sulfate by-product. In the process flow, only a neutralizing agent is used for regulating the pH value of the solution to control the reaction, an oxidant is not used, the production cost is greatly reduced, and the obtained waste liquid can be recycled without causing environmental pollution; furthermore, the obtained ferrous phosphate filter cake can be washed on line, impurities in the raw materials are conveniently and quickly removed, pure ferrous phosphate is ensured to be obtained, the obtained ferrous phosphate can be directly used for preparing lithium iron phosphate by a liquid phase method, the preparation method is convenient and easy to operate, the impurity removal effect is good, the obtained ferrous phosphate is high in purity, the obtained waste liquid can be recycled, environmental pollution cannot be caused, and large-scale production can be ensured.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a flowchart of a method for preparing ferrous phosphate from a titanium dioxide byproduct provided in an embodiment of the present application.
FIG. 2 is a diagram of an apparatus for preparing ferrous phosphate from a titanium dioxide byproduct according to an embodiment of the present disclosure.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiment of the present application provides a method for preparing ferrous phosphate from a titanium dioxide byproduct, as shown in fig. 1, including the following steps:
s01, dissolving ferrous sulfate serving as a titanium dioxide byproduct to obtain a first solution, mixing and reacting the first neutralizing agent and the first solution, and filtering to obtain a ferrous sulfate solution;
s02, providing a phosphoric acid fertilizer, mixing the diluted phosphoric acid fertilizer with a second neutralizing agent for reaction, and filtering to obtain a phosphorus solution;
s03, mixing and reacting the ferrous sulfate solution, the phosphorus solution and a third neutralizing agent, and filtering and separating to obtain a ferrous phosphate filter cake and a liquid after iron precipitation;
and S04, washing and drying the ferrous phosphate filter cake to obtain ferrous phosphate, and concentrating and crystallizing the iron-precipitated liquid to obtain ammonium sulfate and desalted water.
According to the method for preparing ferrous phosphate from the titanium dioxide by-product, provided by the first aspect of the application, ferrous sulfate and phosphate fertilizer which are titanium dioxide by-products are used as raw materials, impurity removal treatment is respectively carried out on the raw materials to obtain a ferrous sulfate solution and a phosphorus solution, a synthetic reaction is carried out on the mixed solution according to the atomic molar ratio to obtain a ferrous phosphate precipitate and a post-iron precipitation solution, and the post-iron precipitation solution is concentrated and crystallized to recover the ammonium sulfate by-product. In the process flow, only a neutralizing agent is used for regulating the pH value of the solution to control the reaction, an oxidant is not used, the production cost is greatly reduced, and the obtained waste liquid can be recycled without causing environmental pollution; furthermore, the obtained ferrous phosphate filter cake can be washed on line, impurities in the raw materials are conveniently and quickly removed, pure ferrous phosphate is ensured to be obtained, the obtained ferrous phosphate can be directly used for preparing lithium iron phosphate by a liquid phase method, the preparation method is convenient and easy to operate, the impurity removal effect is good, the obtained ferrous phosphate is high in purity, the obtained waste liquid can be recycled, environmental pollution cannot be caused, and large-scale production can be ensured.
In step S01, dissolving the ferrous sulfate as the titanium dioxide byproduct to obtain a first solution, mixing the first neutralizing agent with the first solution for reaction, and filtering to obtain a ferrous sulfate solution.
In some embodiments, the titanium dioxide byproduct ferrous sulfate is used as the iron source, and since ferrous sulfate is a byproduct, it must contain a variety of impurity ions. In the commonly provided ferrous sulfate as a byproduct of titanium dioxide, impurity ions such as Mg, Ti, Mn, Ca, Al, Zn, Na, Pb, Ni and the like are contained except Fe, wherein the content of Ti is more because the prior process is used for producing the titanium dioxide, a large amount of Ti ions in the ferrous sulfate need to be removed before reaction, and the purity of the product is ensured not to be influenced.
In some embodiments, in the step of dissolving the ferrous sulfate as the titanium dioxide byproduct to obtain the first solution, the ferrous sulfate as the titanium dioxide byproduct is dissolved by using a dissolving solution, wherein the dissolving solution is at least one selected from water, desalted water and ferrous phosphate filter cake washing water. The dissolving solution is adopted to dissolve the ferrous sulfate, which is beneficial to dissolving each impurity ion in the solution and is convenient for subsequent impurity removal treatment. In the specific embodiment, desalted water is adopted to dissolve ferrous sulfate which is a titanium dioxide byproduct, and water with strong electrolyte removed is adopted to carry out solution, so that other impurity molecules can not be introduced.
In some embodiments, the mass ratio of the dissolving solution to the titanium dioxide byproduct ferrous sulfate is (2-5): 1, ensuring the excessive addition amount of the dissolving solution, completely dissolving various impurity ions in the titanium dioxide byproduct, and facilitating the subsequent impurity removal treatment. If the amount of the solution is too small, the solubility of the by-product ferrous sulfate cannot be ensured, and if the amount of the solution is too large, the subsequent impurity removal is incomplete, which affects the purity.
Further, the first neutralizing agent is mixed with the first solution for reaction. In some embodiments, the first neutralizing agent is selected from at least one of sodium hydroxide, potassium hydroxide, ammonia, reduced iron powder, and ferrous hydroxide, and the first neutralizing agent is selected to substantially adjust the pH of the first solution to precipitate metal impurity ions and remove the impurities. In the specific embodiment, ammonia water is selected as the first neutralizing agent, the provided ammonia water is a weak alkaline solution, and the addition amount can be well controlled to adjust the pH value of the solution so as to ensure that impurity ions are completely precipitated.
In some embodiments, in the step of mixing the first neutralizing agent and the first solution for reaction, the pH is adjusted to 2.0 to 5.0 by adding the first neutralizing agent, the reaction temperature is 25 to 30 ℃, and the reaction time is 2 to 10 hours. The pH value of the first solution is adjusted to be 2.0-5.0 by adding a first neutralizing agent, so that the first solution is subjected to hydrolysis purification impurity removal reaction under the pH condition, the pH value is controlled to be 2.0-5.0, and the reaction time is 2-10 hours, so that the impurity Ti in the first solution can be completely precipitated. If the adjusted pH value exceeds 5.0, Fe can also form precipitates, and the preparation of subsequent products is not facilitated; if the pH value is too low, the impurity Ti cannot be completely precipitated, and the impurity ions cannot be removed well.
In a specific embodiment, in the step of mixing and reacting the first neutralizing agent and the first solution, ammonia water is added to adjust the pH to 4.0-4.5, so that the following reaction of titanium impurity can be ensured:
Ti(SO4)2+4NH3+4H2O＝Ti(OH)4↓+2(NH4)2SO4，
so as to obtain Ti-containing precipitate and remove metal impurities Ti in the titanium dioxide by-product.
Further, filtering the mixture after the mixing reaction to obtain a ferrous sulfate solution. In some embodiments, the precipitate is removed by pressure filtration separation to obtain a ferrous sulfate solution.
In step S02, a phosphoric acid fertilizer is provided, the diluted phosphoric acid fertilizer is mixed with a second neutralizer for reaction, and a phosphorus solution is obtained by filtration
In some embodiments, the second neutralizing agent is selected from at least one of sodium hydroxide, potassium hydroxide, and ammonia water, and the pH of the phosphate fertilizer is adjusted by providing the second neutralizing agent to remove metal impurities from the feedstock. In a particular embodiment, the second neutralizing agent is selected from ammonia, and the pH of the phosphate fertilizer is adjusted to favor precipitation of impurity metals by adding ammonia.
In some embodiments, in the step of mixing and reacting the diluted phosphoric acid fertilizer with the second neutralizing agent, the pH is adjusted to 6.0-10.0 by adding the second neutralizing agent, the reaction temperature is 25-30 ℃, and the reaction time is 5-12 hours. The pH value of the reaction is controlled to be 6.0-10.0, the reaction time is 5-12 hours, and impurities in the phosphoric acid can be completely precipitated.
In the specific embodiment, the diluted phosphoric acid fertilizer and ammonia water are mixed and reacted, the pH is controlled to be 7-8, the reaction solution is controlled to be neutral, and the obtained impurities are ensured to generate phosphate precipitate to be separated, so that the ammonium phosphate solution is obtained.
In a specific embodiment, the diluted phosphoric acid fertilizer and ammonia water are mixed to adjust the pH to 7.0-8.0, and the obtained reaction is as follows:
H3PO4+NH3＝NH4H2PO4，
H3PO4+2NH3＝(NH4)2HPO4，
impurities in the obtained phosphate solution are removed, and the subsequent reaction is facilitated.
In step S03, the ferrous sulfate solution, the phosphorus solution, and the third neutralizing agent are mixed and reacted, and filtered and separated to obtain a ferrous phosphate filter cake and a liquid after iron precipitation.
In some embodiments, the third neutralizing agent is selected from at least one of sodium hydroxide, potassium hydroxide, and ammonia. And adding a third neutralizing agent to adjust the pH value of the reaction, thereby being beneficial to synthesizing ferrous phosphate.
In some embodiments, in the step of mixing and reacting the ferrous sulfate solution, the phosphorus solution and the third neutralizing agent, the third neutralizing agent is added to adjust the pH value to 3.0-7.0, the reaction temperature is 25-30 ℃, and the reaction time is 5-12 hours. The pH value of the reaction is controlled to be 3.0-7.0, and the reaction time is controlled to be 5-12 hours, so that ferrous sulfate and phosphorus can react well to generate ferrous phosphate under the condition. If the reaction pH is more than 7.0, other metals and phosphorus can react to generate precipitates, and impurities appear in the product; if the reaction pH is less than 3.0, ferrous phosphate precipitation cannot be generated well, and the product yield is influenced; if the reaction time is less than 5 hours, the precipitation reaction is incomplete; if the reaction time is more than 12 hours, the production cost is increased.
In some embodiments, the molar ratio of the ferrous sulfate solution to the phosphorus solution is (3-6): (2-4). The molar ratio of the ferrous sulfate to the phosphorus solution is controlled to ensure that the obtained product is ferrous phosphate and ensure that the product has high purity. In a specific embodiment, the molar ratio of the ferrous sulfate solution to the phosphorus solution is 3: 2.
in some embodiments, a ferrous sulfate solution and a phosphorus solution are mixed, ammonia water is added, the pH is controlled to be 4.0-4.5, reaction is carried out, then, filtration is carried out by adopting a filter pressing separation method, and a ferrous phosphate filter cake and a liquid after iron precipitation are obtained through separation.
In step S04, the ferrous phosphate filter cake is washed and dried to obtain ferrous phosphate, and the iron-precipitated solution is concentrated and crystallized to obtain ammonium sulfate and desalted water.
In some embodiments, in the step of washing the ferrous phosphate filter cake, the ferrous phosphate filter cake is filter-pressed through a plate frame, and is washed by adopting a multistage countercurrent washing mode with 2-5 washing stages, so that on one hand, ferrous phosphate is obtained, on the other hand, washing water can be repeatedly utilized as a dissolving solution to be dissolved and used, the obtained ferrous phosphate filter cake can be washed on line, impurities in raw materials are conveniently and quickly removed, pure ferrous phosphate is ensured to be obtained, and the obtained ferrous phosphate can be directly used for preparing lithium iron phosphate by a liquid phase method.
Further, the solution after iron precipitation is concentrated and crystallized to obtain ammonium sulfate and desalted water. In some embodiments, in the step of obtaining ammonium sulfate by concentrating and crystallizing the solution after iron precipitation, the solution after iron precipitation is concentrated by an RO membrane and then evaporated and crystallized to obtain ammonium sulfate; the desalted water obtained by separation can be recycled to wash the ferrous phosphate filter cake, so that on one hand, the ammonium sulfate byproduct can be recycled, and on the other hand, the waste liquid is ensured not to pollute the environment.
In a specific embodiment, the preparation of ferrous phosphate from a titanium dioxide byproduct by using related equipment, as shown in fig. 2, includes:
providing a ferrous sulfate purification reaction tank, dissolving ferrous sulfate serving as a titanium dioxide byproduct to obtain a first solution, mixing and reacting the first solution with a first neutralizing agent, and filtering by using a plate-and-frame filter press to obtain a ferrous sulfate solution;
providing a fertilizer phosphoric acid purification and impurity removal tank, mixing and reacting the diluted phosphoric acid fertilizer with a second neutralizing agent, and filtering by adopting a plate-and-frame filter press to obtain a phosphorus solution;
mixing the ferrous sulfate solution, the phosphorus solution and a third neutralizing agent for reaction, filtering and separating by adopting an online water washing type plate-and-frame filter press to obtain a ferrous phosphate filter cake and a liquid after iron precipitation, and collecting a ferrous phosphate product;
and providing RO membrane concentration equipment to concentrate the liquid after iron precipitation, and crystallizing by adopting MVR evaporation crystallization equipment to obtain an ammonium sulfate byproduct.
The preparation of the ferrous phosphate is carried out by the provided equipment combination, only the neutralizing agent adjusts the pH value of the solution to control the reaction, and no oxidant is used, so that the production cost is greatly reduced, and the obtained waste liquid can be recycled without causing environmental pollution; furthermore, the obtained ferrous phosphate filter cake is washed on line through a plate-and-frame filter press, impurities in the raw materials are conveniently and quickly removed, pure ferrous phosphate is obtained, the obtained ferrous phosphate can be directly used for preparing lithium iron phosphate through a liquid phase method, the preparation method is convenient and easy to operate, the impurity removal effect is good, the obtained ferrous phosphate is high in purity, the obtained waste liquid can be repeatedly used, the environmental pollution cannot be caused, and the large-scale production can be guaranteed.
The following description will be given with reference to specific examples.
Example 1
Method for preparing ferrous phosphate from titanium dioxide byproduct
The method comprises the following steps:
stirring and dissolving 200kg of titanium dioxide byproduct ferrous sulfate and 1000kg of desalted water to obtain a first solution, mixing ammonia water and the first solution for reaction, adjusting the pH value to 2.0, reacting for 2 hours, and filtering to obtain a ferrous sulfate solution;
providing 130kg of phosphoric acid fertilizer, mixing the diluted phosphoric acid fertilizer with ammonia water for reaction, adjusting the pH to 6.0, reacting for 5 hours, and filtering to obtain a phosphorus solution;
mixing a ferrous sulfate solution and a phosphorus solution, adding ammonia water to adjust the pH value to 3.0, reacting for 4 hours, filtering and separating to obtain a ferrous phosphate filter cake and a liquid after iron precipitation;
and (3) carrying out 3-stage online washing and drying treatment on the ferrous phosphate filter cake in a plate frame to obtain a ferrous phosphate product, and concentrating the iron-precipitated liquid through an RO (reverse osmosis) membrane and carrying out MVR (mechanical vapor recompression) evaporative crystallization treatment to obtain an ammonium sulfate byproduct.
Example 2
Method for preparing ferrous phosphate from titanium dioxide byproduct
The method comprises the following steps:
stirring and dissolving 100kg of titanium dioxide byproduct ferrous sulfate and 400kg of desalted water to obtain a first solution, mixing ammonia water and the first solution for reaction, adjusting the pH value to 4.0, reacting for 5 hours, and filtering to obtain a ferrous sulfate solution;
providing 80kg of phosphoric acid fertilizer, mixing the diluted phosphoric acid fertilizer with ammonia water for reaction, adjusting the pH to 7.0, reacting for 7 hours, and filtering to obtain a phosphorus solution;
mixing a ferrous sulfate solution and a phosphorus solution, adding ammonia water to adjust the pH value to 5.0, reacting for 6 hours, filtering and separating to obtain a ferrous phosphate filter cake and a liquid after iron precipitation;
and (3) carrying out 2-stage online washing and drying treatment on the ferrous phosphate filter cake in a plate frame to obtain a ferrous phosphate product, and concentrating the iron-precipitated liquid through an RO (reverse osmosis) membrane and carrying out MVR (mechanical vapor recompression) evaporative crystallization treatment to obtain an ammonium sulfate byproduct.
Example 3
Method for preparing ferrous phosphate from titanium dioxide byproduct
The method comprises the following steps:
stirring and dissolving 300kg of titanium dioxide byproduct ferrous sulfate and 1200kg of desalted water to obtain a first solution, mixing ammonia water and the first solution for reaction, adjusting the pH value to 4.5, reacting for 7 hours, and filtering to obtain a ferrous sulfate solution;
providing 200kg of phosphoric acid fertilizer, mixing the diluted phosphoric acid fertilizer with ammonia water for reaction, adjusting the pH to 7.5, reacting for 6 hours, and filtering to obtain a phosphorus solution;
mixing a ferrous sulfate solution and a phosphorus solution, adding ammonia water to adjust the pH value to 4.0, reacting for 8 hours, filtering and separating to obtain a ferrous phosphate filter cake and a liquid after iron precipitation;
and (3) carrying out 5-stage online washing and drying treatment on the ferrous phosphate filter cake in a plate frame to obtain a ferrous phosphate product, and concentrating the iron-precipitated liquid through an RO (reverse osmosis) membrane and carrying out MVR (mechanical vapor recompression) evaporative crystallization treatment to obtain an ammonium sulfate byproduct.
Performance testing and results analysis
The component analysis of the ferrous phosphate product obtained in examples 1 to 3 is performed, as shown in table 1 below, it can be seen from table 1 that the obtained ferrous sulfate product has an iron content of 33.43% to 34.44%, a P content of 12.35% to 12.55%, and a high purity, and the obtained ferrous phosphate can be directly used for preparing lithium iron phosphate by a liquid phase method.
TABLE 1
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method for preparing ferrous phosphate from a titanium dioxide byproduct is characterized by comprising the following steps:
dissolving ferrous sulfate serving as a titanium dioxide byproduct to obtain a first solution, mixing a first neutralizing agent with the first solution for reaction, and filtering to obtain a ferrous sulfate solution;
providing a phosphoric acid fertilizer, mixing the diluted phosphoric acid fertilizer with a second neutralizing agent for reaction, and filtering to obtain a phosphorus solution;
mixing the ferrous sulfate solution, the phosphorus solution and a third neutralizing agent for reaction, and filtering and separating to obtain a ferrous phosphate filter cake and a liquid after iron precipitation;
and washing and drying the ferrous phosphate filter cake to obtain ferrous phosphate, and concentrating and crystallizing the liquid after iron precipitation to obtain ammonium sulfate and desalted water.
2. The method for preparing ferrous phosphate from the titanium dioxide byproduct according to claim 1, wherein in the step of dissolving the ferrous sulfate as the titanium dioxide byproduct to obtain the first solution, the ferrous sulfate as the titanium dioxide byproduct is dissolved by using a dissolving solution, wherein the dissolving solution is at least one selected from water, desalted water and washing water of a ferrous phosphate filter cake.
3. The method for preparing ferrous phosphate from the titanium dioxide byproduct according to claim 2, wherein the mass ratio of the dissolving solution to the ferrous sulfate of the titanium dioxide byproduct is 2-5: 1.
4. the method for preparing ferrous phosphate from the titanium dioxide byproduct according to any one of claims 1 to 3, wherein in the step of mixing and reacting the first neutralizing agent with the first solution, the pH is adjusted to 2.0 to 5.0 by adding the first neutralizing agent, the reaction temperature is 25 to 30 ℃, and the reaction time is 2 to 10 hours.
5. The method for preparing ferrous phosphate from the titanium dioxide byproduct according to any one of claims 1 to 3, wherein in the step of mixing and reacting the diluted phosphoric acid fertilizer with the second neutralizing agent, the pH is adjusted to 6.0-10.0 by adding the second neutralizing agent, the reaction temperature is 25-30 ℃, and the reaction time is 5-12 hours.
6. The method for preparing ferrous phosphate from the titanium dioxide byproduct according to any one of claims 1 to 3, wherein in the step of mixing and reacting the ferrous sulfate solution, the phosphorus solution and a third neutralizing agent, the third neutralizing agent is added to adjust the pH value to 3.0-7.0, the reaction temperature is 25-30 ℃, and the reaction time is 5-12 hours.
7. The method for preparing ferrous phosphate from the titanium dioxide byproduct according to claim 6, wherein the molar ratio of the ferrous sulfate solution to the phosphorus solution is 3-6: 2 to 4.
8. The method for preparing ferrous phosphate from the titanium dioxide byproduct according to any one of claims 1 to 3, wherein the first neutralizing agent is at least one selected from sodium hydroxide, potassium hydroxide, ammonia water, reduced iron powder and ferrous hydroxide; and/or the presence of a gas in the gas,
the second neutralizing agent is at least one of sodium hydroxide, potassium hydroxide and ammonia water; and/or the presence of a gas in the gas,
the third neutralizing agent is at least one selected from sodium hydroxide, potassium hydroxide and ammonia water.
9. The method for preparing ferrous phosphate from the titanium dioxide byproduct according to any one of claims 1 to 3, wherein in the step of washing the ferrous phosphate filter cake, the ferrous phosphate filter cake is filter-pressed through a plate frame, and is washed by adopting a multistage countercurrent washing mode with 2-5 washing stages.
10. The method for preparing ferrous phosphate from the titanium dioxide byproduct according to any one of claims 1 to 3, wherein in the step of obtaining ammonium sulfate from the solution after iron precipitation through concentration and crystallization, the solution after iron precipitation is concentrated through an RO membrane and then is subjected to evaporation and crystallization to obtain ammonium sulfate.
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