CN113336212B - Method for preparing iron phosphate by recycling mother liquor - Google Patents
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- CN113336212B CN113336212B CN202110770776.1A CN202110770776A CN113336212B CN 113336212 B CN113336212 B CN 113336212B CN 202110770776 A CN202110770776 A CN 202110770776A CN 113336212 B CN113336212 B CN 113336212B
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/375—Phosphates of heavy metals of iron
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Abstract
The invention belongs to the technical field of lithium ion battery anode materials, and particularly discloses a method for preparing iron phosphate by recycling mother liquor, which comprises the following steps: mixing calcium hydrophosphate, sulfuric acid and sodium sulfate mother liquor, stirring for reaction, and filtering to obtain a sodium dihydrogen phosphate solution; adding sodium hydroxide into the sodium dihydrogen phosphate solution, and stirring to obtain a filtrate B; mixing the filtrate B with hydrogen peroxide to obtain a solution C; adding the solution C and a ferrous sulfate solution into a reaction kettle, stirring for reaction, and heating for aging after the reaction; filtering the slurry obtained in the previous step to obtain a mother solution D and a filter cake E; washing the filter cake E to obtain a filter cake F and a filtrate G; concentrating the filtrate G by a membrane to obtain pure water and high-concentration wastewater H, recycling the pure water as washing water, and recycling the high-concentration wastewater H and the mother liquor D as sodium sulfate mother liquor; and (4) crushing, drying, rotary drying, sieving and removing iron to obtain the anhydrous iron phosphate. The method has the advantages of low-cost and easily-obtained raw materials, recyclable mother liquor and low production cost.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a method for preparing iron phosphate by recycling mother liquor.
Background
The iron phosphate is a precursor of the anode material lithium iron phosphate of the energy storage type and power type lithium ion batteries, along with the rapid development of new energy vehicles, industry and civil energy storage fields, the market demand for the energy storage type and power type batteries is gradually increased, the lithium iron phosphate batteries have obvious market advantages of safety, environmental protection, low price and the like, and the demand of the iron phosphate is also increased year by year. However, the wet-process ferric phosphate can generate a large amount of high-salinity wastewater in production, so that the wastewater treatment cost is high, a large amount of water resources are consumed, the energy conservation and the cost reduction are not facilitated, and the value of comprehensive utilization of resources cannot be reflected.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing iron phosphate by recycling mother liquor, which has the advantages of low cost and easy obtainment of raw materials, cyclic utilization of the mother liquor and reduction of wastewater treatment cost and raw material consumption.
The invention provides a method for preparing iron phosphate by recycling mother liquor, which comprises the following steps:
1) Mixing calcium hydrophosphate, sulfuric acid and sodium sulfate mother liquor, stirring for reaction, and filtering to obtain a sodium dihydrogen phosphate solution;
2) Adding sodium hydroxide into the sodium dihydrogen phosphate solution, and stirring to obtain a filtrate B;
3) Mixing the filtrate B with hydrogen peroxide to obtain a solution C;
4) Adding the solution C and a ferrous sulfate solution into a reaction kettle, stirring for reaction, and heating for aging after the reaction is finished;
5) Filtering the slurry obtained in the step 4) to obtain a mother solution D and a filter cake E;
6) Washing the filter cake E to obtain a filter cake F and a filtrate G;
7) Membrane concentration is carried out on the filtrate G to obtain pure water and high-concentration wastewater H, the pure water is recycled as washing water, and the high-concentration wastewater H and mother liquor D are recycled to the step 1) as sodium sulfate mother liquor;
8) And (4) crushing, drying, rotary drying, sieving and removing iron to obtain the anhydrous iron phosphate.
In the invention, the sodium dihydrogen phosphate solution is prepared by reacting calcium hydrogen phosphate, sulfuric acid and sodium sulfate mother liquor, the sodium dihydrogen phosphate solution is further used as a raw material for preparing the iron phosphate, the sodium sulfate mother liquor is high-concentration wastewater H and mother liquor D generated in a post-reaction treatment process, and the mass concentration of sodium sulfate in the high-concentration wastewater H is 6-15%, so that the recycling of the sodium sulfate mother liquor is realized.
Preferably, the mass concentration of the sulfuric acid is 25% -35%, and the mixing molar ratio of the calcium hydrophosphate, the sulfuric acid and the sodium sulfate is (2-2.05): 1-1.05): 1.
Preferably, in step 1), the conditions for stirring the reaction include: the reaction temperature is 45-98 ℃, and the reaction time is 30-60 min.
According to the invention, the step 1) further comprises a concentration and impurity removal step, wherein the filtered reaction solution is concentrated and impurity removed to obtain a purified sodium dihydrogen phosphate solution, and the concentration and impurity removal step is carried out in a conventional manner.
Preferably, in step 2), sodium hydroxide is added in an amount such that the pH of the sodium dihydrogen phosphate solution is 2.0 to 9.0.
Preferably, in the step 3), the molar ratio of the hydrogen peroxide to the ferrous iron in the ferrous sulfate solution is (0.3-0.5): 1.
In the invention, the concentration of the ferrous sulfate solution is 80g/L-120g/L, and the ferrous sulfate solution is prepared by purifying a titanium white byproduct ferrous sulfate. The reasonable utilization of the titanium white byproduct is realized, and the purification of the ferrous sulfate is carried out by adopting the conventional mode in the prior art.
Preferably, the molar ratio of the phosphorus source to the ferrous sulfate in the filtrate B is (1-1.05): 1.
Preferably, in the step 4), the stirring reaction temperature is 40-60 ℃, the heating temperature is 90-99 ℃, the aging time is 2-4 h, and the total length of the stirring reaction time and the aging time is 4-8 h.
In the invention, the crushing and drying are carried out by adopting flash evaporation drying equipment, and the crushing and drying temperature is 100-200 ℃.
According to the invention, the temperature of the rotary drying is 550-650 ℃, and the time is 3-6 h.
The operating steps and parameters not defined in the present invention can be selected conventionally according to the prior art.
Compared with the prior art, the invention has the following beneficial effects:
the method for preparing the iron phosphate has the advantages that the raw materials are low in price and easy to obtain, so that a sodium sulfate solution formed in the iron phosphate production mother liquor can be recycled, the wastewater treatment cost and the raw material consumption (sulfuric acid and sodium hydroxide) are reduced, the comprehensive utilization of resources is facilitated, and the production cost is reduced. The anhydrous iron phosphate prepared by the method has high tap density, is in a spherical-like net structure and good in appearance, and meets the further preparation requirement of the lithium iron phosphate.
Drawings
Fig. 1 is a schematic flow diagram of a method for preparing iron phosphate by recycling mother liquor.
FIG. 2 is a scanning electron micrograph of iron phosphate prepared according to example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of iron phosphate prepared according to example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
As shown in fig. 1, a method for preparing iron phosphate by recycling mother liquor comprises the following steps:
1. mixing the calcium hydrophosphate, sulfuric acid and sodium sulfate mother liquor, stirring for 60min at 45 ℃, and filtering to obtain a sodium dihydrogen phosphate solution; wherein the molar weight ratio of calcium hydrogen phosphate, sulfuric acid and sodium sulfate is 2: 1.05: 1.
2. Adding sodium hydroxide to the sodium dihydrogen phosphate solution until the solution pH =2.0, and then filtering to obtain filtrate B;
3. mixing the filtrate B with hydrogen peroxide, wherein the molar ratio of the hydrogen peroxide to ferrous in the ferrous sulfate solution is 0.4: 1, mixing the hydrogen peroxide and the purified ferrous sulfate solution (80 g/L), adding the mixture and the purified ferrous sulfate solution into a reaction kettle to synthesize and prepare the iron phosphate, slowly adding the two solutions according to the molar ratio of the sodium dihydrogen phosphate to the ferrous sulfate being 1: 1, and stirring the solution in the reaction kettle at the temperature of 40 ℃. After the reaction is finished, the temperature of the reaction kettle is rapidly raised to 90 ℃ by steam, the aging is carried out for 4 hours, and the total synthesis time of the reaction and the aging is 8 hours.
4. Filtering the aged slurry to obtain a mother solution D and a filter cake E, wherein the mother solution D is a solution containing a large amount of sodium sulfate;
5. washing the filter cake E to obtain a filter cake F and a filtrate G; concentrating the filtrate G through a membrane to obtain pure water (for washing and recycling) and high-concentration wastewater H, wherein the H is a solution containing a large amount of sodium sulfate;
6. and (3) crushing and drying the filter cake F (ferric phosphate dihydrate filter cake) (100 ℃, flash evaporation) and rotary drying (550 ℃ for 6 hours), and then sieving and removing iron to obtain the anhydrous ferric phosphate. Scanning electron micrographs of anhydrous iron phosphate are shown in fig. 2 and 3.
7. The mother liquor D and high-concentration waste water H (containing a large amount of sodium sulfate solution and having the solubility of 6%) are put into the process of preparing sodium dihydrogen phosphate, namely the step 1, and are used for reacting with sulfuric acid and calcium hydrophosphate to prepare the sodium dihydrogen phosphate solution.
Example 2
As shown in fig. 1, a method for preparing iron phosphate by recycling mother liquor comprises the following steps:
1. mixing calcium hydrogen phosphate, sulfuric acid and sodium sulfate mother liquor, stirring for 30min at 98 ℃, and filtering to obtain a sodium dihydrogen phosphate solution; wherein the molar ratio of calcium hydrogen phosphate, sulfuric acid and sodium sulfate is 2.05: 1.
2. Adding sodium hydroxide to the sodium dihydrogen phosphate solution until the solution pH =7.0, and then filtering to obtain a filtrate B;
3. mixing the filtrate B with hydrogen peroxide, wherein the molar ratio of the hydrogen peroxide to ferrous in the ferrous sulfate solution is 0.5: 1, mixing the filtrate B with the purified ferrous sulfate solution (120 g/L), adding the mixture and the purified ferrous sulfate solution into a reaction kettle, synthesizing and preparing iron phosphate, slowly adding the two solutions according to the molar ratio of sodium dihydrogen phosphate to ferrous sulfate of 1.05: 1, and stirring the solution in the reaction kettle at the temperature of 60 ℃. After the reaction is finished, the temperature of the reaction kettle is rapidly raised to 99 ℃ by steam, aging is carried out for 2 hours, and the total time of the reaction and the aging is 4 hours.
4. Filtering the aged slurry to obtain a mother solution D and a filter cake E, wherein the mother solution D is a solution containing a large amount of sodium sulfate;
5. washing the filter cake E to obtain a filter cake F and a filtrate G; concentrating the filtrate G through a membrane to obtain pure water (for washing and recycling) and high-concentration wastewater H, wherein the H is a solution containing a large amount of sodium sulfate;
6. and (3) crushing and drying the filter cake F (ferric phosphate dihydrate filter cake) (200 ℃, flash evaporation) and rotary drying (650 ℃ for 3 hours), and then sieving and removing iron to obtain the anhydrous ferric phosphate.
7. The mother liquor D and the high-concentration wastewater H (a solution containing a large amount of sodium sulfate and having a solubility of 15%) are put into a process for preparing sodium dihydrogen phosphate, namely step 1, and are used for reacting with sulfuric acid and calcium hydrogen phosphate to prepare sodium dihydrogen phosphate.
Example 3
As shown in fig. 1, a method for preparing iron phosphate by recycling mother liquor comprises the following steps:
1. mixing calcium hydrogen phosphate, sulfuric acid and sodium sulfate mother liquor, stirring for 50min at 60 ℃, and filtering to obtain sodium dihydrogen phosphate solution; wherein the molar ratio of calcium hydrogen phosphate, sulfuric acid and sodium sulfate is 2: 1.
2. Adding sodium hydroxide to the sodium dihydrogen phosphate solution until the solution pH =4.0, and then filtering to obtain a filtrate B;
3. mixing the filtrate B with hydrogen peroxide, wherein the molar ratio of the hydrogen peroxide to ferrous in the ferrous sulfate solution is 0.5: 1, mixing, adding the mixture and the purified ferrous sulfate solution (80 g/L) into a reaction kettle to synthesize and prepare the iron phosphate, slowly adding the two solutions according to the molar ratio of sodium dihydrogen phosphate to ferrous sulfate being 1: 1, and stirring at the temperature of the reaction kettle under the condition of 55 ℃. After the reaction is finished, the temperature of the reaction kettle is rapidly raised to 95 ℃ by steam, the aging is carried out for 3h, and the total time of the reaction and the aging is 6h.
4. Filtering the aged slurry to obtain a mother solution D and a filter cake E, wherein the mother solution D is a solution containing a large amount of sodium sulfate;
5. washing the filter cake E to obtain a filter cake F and a filtrate G; concentrating the filtrate G through a membrane to obtain pure water (for washing and recycling) and high-concentration wastewater H, wherein the H is a solution containing a large amount of sodium sulfate;
6. and (3) crushing and drying the filter cake F (ferric phosphate dihydrate filter cake) (at 150 ℃, carrying out flash evaporation) and carrying out rotary drying (drying at 600 ℃ for 6 hours), and then sieving and removing iron to obtain the anhydrous ferric phosphate.
7. The mother liquor D and high-concentration waste water H (containing a large amount of sodium sulfate solution and having the solubility of 6%) are put into the process of preparing sodium dihydrogen phosphate, namely the step 1, and are used for reacting with sulfuric acid and calcium hydrophosphate to prepare the sodium dihydrogen phosphate solution.
The results of physical and chemical index tests of the anhydrous iron phosphates obtained in examples 1 to 3 are shown in table 1.
TABLE 1
| Sample (I) | Iron content | Phosphorus content | Iron to phosphorus ratio | BET | Tap density |
| Example 1 | 36.27wt％ | 20.58wt％ | 0.98 | 7.60m 2 /g | 0.8188g/cm 3 |
| Example 2 | 35.11wt％ | 19.32wt％ | 1.01 | 7.66m 2 /g | 0.79g/cm 3 |
| Example 3 | 36.16wt％ | 19.98wt％ | 1.00 | 7.1m 2 /g | 0.85g/cm 3 |
As can be seen from table 1, the anhydrous iron phosphate prepared by the preparation method of the present invention has a high tap density, and can meet the further preparation requirements of lithium iron phosphate, and as can be seen from fig. 2 and 3, the anhydrous iron phosphate prepared by the present invention has a good morphology. Meanwhile, the sodium sulfate solution formed in the ferric phosphate production mother solution is recycled, so that the wastewater treatment cost and the raw material consumption are reduced, the comprehensive utilization of resources is facilitated, and the production cost is reduced.
While embodiments of the present invention have been described above, the above description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.
Claims (10)
1. The method for preparing the iron phosphate by recycling the mother liquor is characterized by comprising the following steps:
1) Mixing calcium hydrophosphate, sulfuric acid and sodium sulfate mother liquor, stirring for reaction, and filtering to obtain a sodium dihydrogen phosphate solution; the sodium sulfate mother liquor is high-concentration wastewater H and mother liquor D generated in the treatment process after the reaction, and the mass concentration of sodium sulfate in the high-concentration wastewater H is 6-15%;
2) Adding sodium hydroxide into the sodium dihydrogen phosphate solution, and stirring to obtain a filtrate B;
3) Mixing the filtrate B with hydrogen peroxide to obtain a solution C;
4) Adding the solution C and a ferrous sulfate solution into a reaction kettle, stirring for reaction, and after the reaction is finished, heating for aging;
5) Filtering the slurry obtained in the step 4) to obtain a mother solution D and a filter cake E;
6) Washing the filter cake E to obtain a filter cake F and a filtrate G;
7) Membrane concentration is carried out on the filtrate G to obtain pure water and high-concentration wastewater H, the pure water is recycled as washing water, and the high-concentration wastewater H and mother liquor D are recycled to the step 1 as sodium sulfate mother liquor;
8) And (4) crushing, drying, rotary drying, sieving and removing iron to obtain the anhydrous iron phosphate.
2. The method for preparing the iron phosphate by recycling the mother liquor according to claim 1, wherein the mass concentration of the sulfuric acid is 25% -35%, and the mixing molar ratio of the calcium hydrophosphate, the sulfuric acid and the sodium sulfate is (2-2.05): 1-1.05): 1.
3. The method for preparing iron phosphate by recycling the mother liquor according to claim 1, wherein in the step 1), the stirring reaction conditions comprise: the reaction temperature is 45-98 ℃, and the reaction time is 30-60 min.
4. The method for preparing iron phosphate by recycling the mother liquor according to claim 1, wherein in the step 2), the sodium hydroxide is added in an amount to ensure that the pH value of the sodium dihydrogen phosphate solution is 2.0-9.0.
5. The method for preparing iron phosphate by recycling the mother liquor according to claim 1, wherein in the step 3), the molar ratio of the amount of the hydrogen peroxide to the ferrous iron in the ferrous sulfate solution is (0.3-0.5): 1.
6. The method for preparing iron phosphate by recycling the mother liquor according to claim 1, wherein the concentration of the ferrous sulfate solution is 80-120 g/L, and the ferrous sulfate solution is prepared by purifying ferrous sulfate which is a byproduct of titanium white.
7. The method for preparing iron phosphate by recycling mother liquor according to claim 1 or 6, wherein the molar ratio of the phosphorus source to the ferrous sulfate in the filtrate B is (1-1.05): 1.
8. The method for preparing iron phosphate by recycling the mother liquor according to claim 1, wherein in the step 4), the stirring reaction temperature is 40-60 ℃, the heating temperature is 90-99 ℃, the aging time is 2-4 h, and the total length of the stirring reaction time and the aging time is 4-8 h.
9. The method for preparing the iron phosphate by recycling the mother liquor according to claim 1, wherein the crushing and drying are carried out by adopting a flash drying device, and the temperature of the crushing and drying is 100-200 ℃.
10. The method for preparing the iron phosphate by recycling the mother liquor according to claim 1, wherein the temperature of the rotary drying is 550-650 ℃ and the time is 3-6 h.
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| CN113912034B (en) * | 2021-11-22 | 2023-04-25 | 河南佰利新能源材料有限公司 | Ferric phosphate and preparation method thereof |
| CN114314680A (en) * | 2022-03-02 | 2022-04-12 | 湖北虹润高科新材料有限公司 | Method for preparing low-impurity iron phosphate by using monocalcium phosphate and application |
| CN115108543A (en) * | 2022-05-31 | 2022-09-27 | 丁兴立 | Method for synthesizing battery-grade iron phosphate |
| CN115806278A (en) * | 2022-12-29 | 2023-03-17 | 河南龙佰新材料科技有限公司 | Method for preparing phosphate by using wastewater generated in iron phosphate production |
| CN116443835A (en) * | 2023-05-25 | 2023-07-18 | 河南佰利新能源材料有限公司 | Ferric phosphate and preparation method and application thereof |
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