CN113460989B - Battery-grade iron phosphate and preparation method thereof - Google Patents
Battery-grade iron phosphate and preparation method thereof Download PDFInfo
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- CN113460989B CN113460989B CN202110746350.2A CN202110746350A CN113460989B CN 113460989 B CN113460989 B CN 113460989B CN 202110746350 A CN202110746350 A CN 202110746350A CN 113460989 B CN113460989 B CN 113460989B
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- grade iron
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- 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
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- 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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- 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
Abstract
The invention discloses a preparation method of battery-grade iron phosphate, which comprises the following steps: step a: mixing wet-process phosphoric acid and an alkaline compound, and reacting until the pH value is 1.8-4.3; step b: b, carrying out curing reaction on the reactant in the step a, and carrying out solid-liquid separation on the cured reactant to obtain filter residue and phosphorus-containing clear liquid; step c: dissolving ferrous sulfate into a ferrous sulfate solution, and adding an oxidant to carry out an oxidation reaction to obtain a ferric sulfate solution; step d: mixing the phosphorus-containing clear solution and the ferric sulfate solution in proportion, and reacting to obtain ferric phosphate slurry; step e: performing liquid-solid separation on the iron phosphate slurry to obtain an iron phosphate filter cake and a mother solution; step f: and washing the iron phosphate filter cake and drying to obtain the iron phosphate. By adopting the battery-grade iron phosphate and the preparation method thereof, the battery-grade iron phosphate is produced by adopting unpurified wet-process phosphoric acid and industrial byproduct ferrous phosphate as main raw materials, and has low cost and simple preparation.
Description
Technical Field
The invention relates to battery-grade iron phosphate and a preparation method thereof, belonging to the technical field of iron phosphate production.
Background
The ferric phosphate is used as a raw material for producing the lithium iron phosphate which is a positive material of the lithium ion battery, and also used as a molluscicide in organic agriculture and a substrate coating in paint, and has wide application. The production methods of the iron phosphate are various, the battery grade iron phosphate has extremely high requirements on impurities and strict requirements on basic raw materials, and at present, high-purity phosphoric acid or phosphate and iron salt are generally used for reaction, but the cost of the high-purity raw materials is very high. At present, a preparation method capable of greatly reducing the cost of the iron phosphate is needed, so that the production cost of the lithium ion battery is reduced.
Wet phosphoric acid is produced by decomposing phosphate rock with strong acid such as sulfuric acid or hydrochloric acid, and liquid-solid separation to obtain phosphoric acid containing various impurities, so that the wet phosphoric acid is generally used for producing phosphate fertilizer, and if high-quality phosphate product is to be prepared, further purification is needed. The wet-process phosphoric acid is low in cost, the source of the wet-process phosphoric acid is the most extensive and cheap phosphorus source, but unpurified wet-process phosphoric acid contains impurities such as Ca, mg, al, fe and the like, and cannot be directly used for producing battery-grade iron phosphate, further evolution and purification are needed for industrial application, but the purification and purification process of the wet-process phosphoric acid is complex, and the problem of high cost is caused by using purified phosphoric acid to prepare the iron phosphate. The ferrous phosphate is a by-product of the process for producing titanium dioxide and the like, and has low cost.
Disclosure of Invention
The invention aims to: aiming at the problems, the invention provides the battery-grade iron phosphate and the preparation method thereof, and the battery-grade iron phosphate is produced by adopting unpurified wet-process phosphoric acid and industrial byproduct ferrous phosphate as main raw materials, so that the cost is low and the preparation is simple.
The technical scheme adopted by the invention is as follows:
a battery grade iron phosphate and a preparation method thereof comprise the following steps:
step a: mixing wet-process phosphoric acid and an alkaline compound, and reacting until the pH value is 1.8-4.3;
step b: b, carrying out curing reaction on the reactant in the step a, and carrying out solid-liquid separation on the cured reactant to obtain filter residue and phosphorus-containing clear liquid;
step c: dissolving ferrous sulfate into a ferrous sulfate solution, and adding an oxidant to carry out an oxidation reaction to obtain a ferric sulfate solution;
step d: mixing the phosphorus-containing clear solution and a ferric sulfate solution in proportion, and reacting to obtain ferric phosphate slurry;
step e: performing liquid-solid separation on the iron phosphate slurry to obtain an iron phosphate filter cake and a mother solution;
step f: and washing the iron phosphate filter cake and drying to obtain the iron phosphate.
In the step a of the invention, an alkaline compound is added, phosphoric acid, metal ions and the alkaline compound react to generate a water-insoluble complex salt, the addition of the alkaline compound is controlled to enable the pH value of the mixed solution to be 1.8-4.3, the invention finds that the solubility of the generated complex salt in water is the lowest when the pH value is 1.8-4.3, so that impurity ions in wet-process phosphoric acid are removed to the maximum extent, the removal rate of impurities can reach more than 99.5% when the pH value is 1.8-4.3, and impurities which can influence the purity of iron phosphate are removed. The phosphorus-containing clear liquid with most impurity ions removed reacts with iron ions to obtain an iron phosphate product, and the low impurity content can meet the requirement of battery-grade iron phosphate. In the present invention, if the pH is less than 1.8, the removal rate of impurities may be reduced; if the pH value is higher than 4.3, alkaline compounds are wasted, the cost is increased, and the pH value is 1.8-4.3, which is a reasonable pH value range for removing impurities.
In the invention, only metal cations which can influence the purity of the iron phosphate are removed, acid radicals which can not influence the purity of the iron phosphate are not required to be removed, the wet-process phosphoric acid is not required to be purified to high-quality phosphoric acid, the purification process of the wet-process phosphoric acid is reduced, and the cost is reduced. The preparation method is simple, and compared with the method of directly preparing the iron phosphate by using a high-quality phosphorus source, the cost of the iron phosphate can be greatly reduced.
Preferably, in step a, the wet-process phosphoric acid and the alkaline compound are mixed and reacted at a reaction temperature of 55 to 100 ℃ for 1.5 to 3.5 hours.
Preferably, the wet-process phosphoric acid is 15 to 30% (P) 2 O 5 ) Wet process phosphoric acid of concentration.
Preferably, the basic compound is one or more of ammonia, ammonia water, ammonium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate and potassium bicarbonate.
In the above scheme, the addition of the basic compound does not introduce other metal cations that affect the quality of the iron phosphate.
Preferably, in step b, the aging reaction time is 1.0 to 3.0 hours, and the aging temperature is 55 to 65 ℃.
In the scheme, the aging reaction is favorable for crystallization precipitation and particle enlargement of impurity salts, so that the produced salts can be completely crystallized and removed, and the removal rate of impurities is increased.
Preferably, in the step c, the oxidant is hydrogen peroxide, and the oxidation reaction time is 1.0-3.0 h.
Preferably, in the step d, the phosphorus-containing clear solution and the ferric sulfate solution are reacted until the pH value is 1.5-3, the reaction temperature is 50-95 ℃, and the reaction time is 3-6 hours.
In the scheme, the pH value is controlled to be 1.5-3 to reach a reasonable range, and if the pH value is lower than 1.5, the yield of iron ions is reduced; if the pH value is higher than 3, ferric hydroxide is generated, which affects the purity of the ferric phosphate.
Preferably, a part of the mother liquor in the step e is used for dissolving the ferrous sulfate in the step c, and the other part of the mother liquor enters a concentration crystallization system to obtain a byproduct sulfate.
In the scheme, the utilization rate can be improved by using the mother liquor to dissolve the ferrous phosphate, and the amount of the mother liquor entering the concentration and crystallization system is reduced.
Preferably, in the step f, the iron phosphate filter cake is washed by deionized water, and then is dried by spin flash evaporation to obtain the iron phosphate.
The battery-grade iron phosphate is prepared by the preparation method of the battery-grade iron phosphate, and is characterized in that: the D50 of the iron phosphate is 2-5 mu m, and the crystal form is amorphous and/or orthorhombic.
According to the battery-grade iron phosphate and the preparation method thereof, the low-cost wet-process sulfuric acid and ferrous sulfate are used as raw materials, and the metal cations influencing the purity of the iron phosphate are removed, so that the high-purity battery-grade iron phosphate is obtained, the preparation is simple, the cost is low, and the manufacturing cost of the lithium iron phosphate battery can be reduced in a large-scale industrial application.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that: the preparation is simple, the cost is low, and high-quality battery-grade iron phosphate can be obtained.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
The preparation method of battery-grade iron phosphate of the embodiment comprises the following steps:
step a: will 15% (P) 2 O 5 ) Performing neutralization reaction on 1000g of wet-process phosphoric acid and ammonia, adding ammonia until the pH value is 4.3, reacting for 1.5h, and reacting at the temperature of 100 ℃;
step b: b, carrying out curing reaction on the reactant in the step a for 3 hours at the reaction temperature of 55 ℃, and carrying out solid-liquid separation on the cured reactant by using a filter press to obtain filter residue and phosphorus-containing clear liquid;
step c: dissolving 200g of ferrous sulfate in 600g of water to prepare a ferrous sulfate solution, and adding 90g of hydrogen peroxide for oxidation reaction for 1 hour to obtain a ferric sulfate solution;
step d: mixing the phosphorus-containing clear solution with a ferric sulfate solution until the pH value is 3, and reacting for 6 hours at 50 ℃ to obtain ferric phosphate slurry;
step e: performing liquid-solid separation on the iron phosphate slurry to obtain an iron phosphate filter cake and a mother solution;
step f: and washing the iron phosphate filter cake by deionized water, and drying by rotary flash evaporation to obtain the iron phosphate.
In this embodiment, a part of the mother liquor in step e is used to dissolve the ferrous sulfate in step c, and the other part enters the concentration and crystallization system to obtain the by-product sulfate.
Example 2
The preparation method of battery grade iron phosphate of the embodiment comprises the following steps:
step a: 20 percent (P) 2 O 5 ) Mixing 1000g of wet-process phosphoric acid with a sodium hydroxide solution, adding the sodium hydroxide solution until the pH value is 3, reacting for 2.5h, and reacting at 76 ℃;
step b: b, carrying out curing reaction on the reactant in the step a for 2 hours at the reaction temperature of 60 ℃, and carrying out solid-liquid separation on the cured reactant by using a filter press to obtain filter residue and a phosphorus-containing clear liquid;
step c: dissolving 270g of ferrous sulfate in 600g of water to prepare a ferrous sulfate solution, and adding 120g of hydrogen peroxide for oxidation reaction for 3 hours to obtain a ferric sulfate solution;
step d: mixing the phosphorus-containing clear solution with a ferric sulfate solution until the pH value is 2, and reacting for 4.5 hours at 73 ℃ to obtain ferric phosphate slurry;
step e: performing liquid-solid separation on the iron phosphate slurry to obtain an iron phosphate filter cake and a mother solution;
step f: and washing the iron phosphate filter cake by deionized water, and drying by rotary flash evaporation to obtain the iron phosphate.
Example 3
The preparation method of battery-grade iron phosphate of the embodiment comprises the following steps:
step a: 30% (P) 2 O 5 ) Mixing 1000g of wet-process phosphoric acid and a potassium hydroxide solution, adding the potassium hydroxide solution until the pH value is 1.8, reacting for 3.5h, and reacting at the temperature of 55 ℃;
step b: b, carrying out curing reaction on the reactant in the step a for 1h at the reaction temperature of 65 ℃, and carrying out solid-liquid separation on the cured reactant by using a filter press to obtain filter residue and a phosphorus-containing clear liquid;
step c: dissolving 400g of ferrous sulfate in 800g of water to prepare a ferrous sulfate solution, adding 160g of hydrogen peroxide, and carrying out oxidation reaction for 3 hours to obtain a ferric sulfate solution;
step d: mixing the phosphorus-containing clear solution with a ferric sulfate solution until the pH value is 1.5, and reacting for 3 hours at 95 ℃ to obtain ferric phosphate slurry;
step e: performing liquid-solid separation on the iron phosphate slurry to obtain an iron phosphate filter cake and a mother solution;
step f: and washing the iron phosphate filter cake by deionized water, and drying by rotary flash evaporation to obtain the iron phosphate.
Example 4 example 15
The present embodiment differs from embodiment 3 in that: the pH values in step a are 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.3, respectively.
Comparative example 1
This comparative example differs from example 3 in that: step a: 30% (P) 2 O 5 ) 1000g of wet-process phosphoric acid and 5g of polymeric ferric sulfate were mixed and sodium hydroxide was added to a pH of 1.
Comparative example 2
The comparative example differs from example 3 in that: step a: 30% (P) 2 O 5 ) 1000g of wet-process phosphoric acid and 5g of polymeric ferric sulfate were mixed and sodium hydroxide was added to a pH of 1.2.
Comparative example 3
The comparative example differs from example 3 in that: step a: 30% (P) 2 O 5 ) 1000g of wet-process phosphoric acid and 5g of polymeric ferric sulfate were mixed and sodium hydroxide was added to a pH of 1.4.
Comparative example 4
This comparative example differs from example 3 in that: step a: 30% (P) 2 O 5 ) 1000g of wet-process phosphoric acid and 5g of polymeric ferric sulfate were mixed and sodium hydroxide was added to a pH of 1.6.
Comparative example 5
The comparative example differs from example 3 in that: step a: 30% (P) 2 O 5 ) 1000g of wet-process phosphoric acid and 5g of polymeric ferric sulfate were mixed and sodium hydroxide was added to a pH of 4.5.
Comparative example 6
This comparative example differs from example 3 in that: step a: 30% (P) 2 O 5 ) 1000g of wet-process phosphoric acid and 5g of polymeric ferric sulfate were mixed and sodium hydroxide was added to a pH of 4.7.
Comparative example 7
This comparative example differs from example 3 in that: step a: 30% (P) 2 O 5 ) 1000g of wet-process phosphoric acid and 5g of polymeric ferric sulfate were mixed and sodium hydroxide was added to a pH of 4.9.
Comparative example 8
This comparative example differs from example 3 in that: and (b) directly carrying out solid-liquid separation without curing.
The iron phosphates prepared in the above examples and comparative examples are detected, wherein the iron phosphates prepared in examples 1-3 all meet the requirements of HG/T4701-2014, and the impurities in the iron phosphates prepared in comparative examples 1-3 contain excessive phosphorus and do not meet the requirements of HG/T4701-2014; further, impurity tests were conducted on the phosphorus-containing clear solutions of examples 3 to 15 and comparative examples 1 to 8 (content of cationic impurities in wet-process phosphoric acid: ga 0.057%, mg 0.686%, al 0.365%), and the results of the impurities in the phosphorus-containing clear solutions were as follows:
through the change of the impurity removal conditions under different pH values in the table, it can be seen that when the pH value is less than 1.8, the smaller the pH value is, the poorer the cation impurity removal effect is; when the pH value is between 1.8 and 4.3, the cation removal effect shows the trend of rising first and then falling, and when the pH value is 2.8, the cation impurity removal effect is the best; when the pH value is more than 4.3, the removal effect is not increased along with the increase of the pH value, only the consumption of alkaline compounds is wasted, and the cost is increased. In general, the iron phosphate has good impurity removal rate at a pH value of 1.8-4.3, so that the prepared iron phosphate can reach the battery grade standard.
By comparing the example 3 with the comparative example 8, the comparative example 8 lacks a curing process, so that impurities in the phosphorus-containing clear solution cannot be completely crystallized and removed, and the content of impurities in the prepared iron phosphate is higher and does not meet the requirement of battery-grade iron phosphate.
Of course, in the present invention, the iron phosphate obtained in the examples using other alkaline compounds can also meet the requirements of battery grade iron phosphate.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification, and to any novel method or process steps or any novel combination of steps disclosed.
Claims (10)
1. A preparation method of battery grade iron phosphate is characterized by comprising the following steps: the method comprises the following steps:
a, step a: mixing wet-process phosphoric acid and an alkaline compound, and reacting until the pH value is 1.8-4.3;
step b: b, carrying out curing reaction on the reactant in the step a, and carrying out solid-liquid separation on the cured reactant to obtain filter residue and phosphorus-containing clear liquid;
step c: dissolving ferrous sulfate into a ferrous sulfate solution, and adding an oxidant to carry out an oxidation reaction to obtain a ferric sulfate solution;
step d: mixing the phosphorus-containing clear solution and the ferric sulfate solution in proportion, and reacting to obtain ferric phosphate slurry;
step e: performing liquid-solid separation on the iron phosphate slurry to obtain an iron phosphate filter cake and a mother solution;
step f: and washing the iron phosphate filter cake and drying to obtain the iron phosphate.
2. The method of preparing battery grade iron phosphate according to claim 1, characterized in that: in the step a, the wet-process phosphoric acid and the alkaline compound are mixed and reacted, the reaction temperature is 55-100 ℃, and the reaction time is 1.5-3.5 hours.
3. The method of preparing battery grade iron phosphate according to claim 1, characterized in that: the wet-process phosphoric acid is 15 to 30 percent 2 O 5 Wet process phosphoric acid of concentration.
4. The method of preparing battery grade iron phosphate according to claim 1, characterized in that: the alkaline compound is one or more of ammonia, ammonia water, ammonium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate and potassium bicarbonate.
5. The method of preparing battery grade iron phosphate according to claim 1, characterized in that: in the step b, the curing reaction time is 1.0 to 3.0 hours, and the curing temperature is 55 to 65 ℃.
6. The method of preparing battery grade iron phosphate according to claim 1, characterized in that: in the step c, the oxidant is hydrogen peroxide, and the oxidation reaction time is 1.0-3.0 h.
7. The method of preparing battery grade iron phosphate according to claim 1, characterized in that: in the step d, the phosphorus-containing clear solution and the ferric sulfate solution react until the pH value is 1.5-3, the reaction temperature is 50-95 ℃, and the reaction time is 3-6 hours.
8. The method of preparing battery grade iron phosphate according to claim 1, characterized in that: and e, using one part of the mother liquor in the step e to dissolve the ferrous sulfate in the step c, and feeding the other part of the mother liquor into a concentration crystallization system to obtain a byproduct sulfate.
9. The battery grade iron phosphate and the method of making the same according to claim 1, wherein: and step f, washing the iron phosphate filter cake by deionized water, and drying by rotary flash evaporation to obtain the iron phosphate.
10. A battery grade iron phosphate made by the method of making a battery grade iron phosphate according to any one of claims 1 to 9, characterized in that: the D50 of the iron phosphate is 2-5 mu m, and the crystal form is amorphous and/or orthorhombic.
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| CN114906829B (en) * | 2022-04-28 | 2024-01-02 | 湖北云翔聚能新能源科技有限公司 | Method for preparing battery-grade ferric phosphate by adopting agricultural-grade wet-process phosphoric acid |
| CN115448271B (en) * | 2022-09-16 | 2023-10-31 | 衢州华友钴新材料有限公司 | Purification method and purification system of wet-process phosphoric acid and preparation method of ferric phosphate |
| CN115477293B (en) * | 2022-10-11 | 2023-09-08 | 湖北虹润高科新材料有限公司 | Preparation method of anhydrous ferric phosphate with low impurity and high specific surface area |
| CN115626619B (en) * | 2022-10-28 | 2024-04-02 | 贵州川恒化工股份有限公司 | Preparation method of battery-grade ferric phosphate |
| CN115676790B (en) * | 2022-10-28 | 2024-04-02 | 贵州川恒化工股份有限公司 | Preparation method of high-tap-density spherical battery-grade ferric phosphate |
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| CN102583293B (en) * | 2012-02-09 | 2014-01-01 | 昆明川金诺化工股份有限公司 | Preparation method of cell grade ferric orthophosphate |
| CN103241720B (en) * | 2013-05-20 | 2015-01-28 | 昆明理工大学 | Method for preparing amorphous iron phosphate by using phosphate sludge |
| CN108862224B (en) * | 2018-06-27 | 2021-11-12 | 武汉工程大学 | Method for preparing iron phosphate from wet-process phosphoric acid ammoniated slurry slag |
| CN111377425A (en) * | 2020-01-19 | 2020-07-07 | 江苏乐能电池股份有限公司 | Preparation method of low-cost iron phosphate particles |
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