CN114804048A - Method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag - Google Patents
Method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag Download PDFInfo
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Abstract
The invention discloses a method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag, which relates to the technical field of extraction and separation of iron phosphate slag, wherein the iron phosphate slag is added into inorganic acid for leaching to obtain a leaching solution, the leaching solution is subjected to iron extraction in P204, an alkaline solution is added into a raffinate to adjust the pH value, impurities such as copper, aluminum and the like are removed by extraction through an extractant, a phosphorus-rich solution is obtained, an organic phase is subjected to hydrochloric acid back extraction, the phosphorus-rich solution and the iron-rich solution are mixed, and the pH value is adjusted to prepare battery-grade iron phosphate, so that the problem that the resource is wasted because the iron phosphate slag is subjected to solid waste treatment in the existing recovery process of a lithium iron phosphate battery is solved; graphite slag is recovered through leaching separation of inorganic acid, P204 is reused for extracting iron so as to separate phosphorus ions and iron ions, impurity removal is carried out on raffinate through preparing a novel extracting agent, extraction quality is effectively improved, a phosphorus-rich solution with higher purity is obtained, and thus battery-grade ferric phosphate is better prepared.
Description
Technical Field
The invention relates to the technical field of extraction and separation of iron phosphate slag, and particularly relates to a method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag.
Background
The lithium iron phosphate battery has the advantages of long cycle life, high safety, low cost, less environmental pollution and the like, and is the first choice of many domestic battery enterprises in the initial production stage, the existing mainstream lithium ion battery recovery process is 'disassembly + crushing + wet leaching + material synthesis', the method can extract valuable metals such as lithium, nickel, cobalt, manganese, copper and the like, and iron phosphate slag is treated as solid waste, so that a large amount of resources are wasted;
how to improve the resource waste caused by the existing lithium iron phosphate battery recovery process is the key point of the invention, so a method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag is urgently needed to solve the problems.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag, which comprises the following steps:
(1) adding iron phosphate slag into inorganic acid for leaching to obtain leachate, carrying out iron extraction on the leachate through P204 to obtain an organic phase I and raffinate, adding an alkaline solution into the raffinate to adjust the pH value, then extracting by using an extractant to remove impurities such as copper, aluminum and the like to obtain a phosphorus-rich solution, adding hydrochloric acid into the organic phase I for back extraction to obtain an iron-rich solution and an organic phase II, mixing the phosphorus-rich solution and the iron-rich solution, and adjusting the pH value to prepare battery-grade iron phosphate, thereby solving the problem that the resource is wasted because the iron phosphate slag is subjected to solid waste treatment in the existing lithium iron phosphate battery recycling process;
(2) putting a mixture of magnesium powder, anhydrous tetrahydrofuran and iodine into a vegetable feeding bottle, dropwise adding a mixed solution of 2-ethylhexyl bromide and tetrahydrofuran, stirring until the color of iodine disappears, dropwise adding the rest mixed solution of 2-ethylhexyl bromide and tetrahydrofuran into a reaction solution to obtain an intermediate A, dropwise adding a mixture of diisooctyl phosphite and tetrahydrofuran into the intermediate A in an ice water bath to obtain an intermediate B, putting a mixture of paraformaldehyde, the intermediate B and isooctylamine into a round-bottom flask, and adding a catalyst to obtain the extracting agent.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag comprises the following steps:
s1: in the acid dissolution leaching process of the iron phosphate slag, adding the iron phosphate slag into inorganic acid for leaching, wherein the reaction temperature is 25-80 ℃, the reaction time is 2-6h, the pH value of a dissolving solution is kept to be 1, so as to obtain a leaching solution and graphite slag, and the graphite slag is recycled;
s2: performing P204 iron extraction, namely performing iron extraction on the leachate through P204, wherein the extraction grade number is 5-20 grades, and obtaining an organic phase I and raffinate;
s3: carrying out fine extraction by using an extracting agent, adding an alkaline solution into the raffinate to adjust the pH value to 3-5, and extracting by using the extracting agent to remove impurities such as copper, aluminum and the like to obtain a phosphorus-rich solution;
s4: adding hydrochloric acid into the organic phase I obtained in the step S2 for back extraction to obtain an iron-rich solution and an organic phase II;
s5: and (5) mixing the phosphorus-rich solution obtained in the step (S3) with the iron-rich solution obtained in the step (4), and adjusting the pH value to prepare the battery-grade iron phosphate.
As a further scheme of the invention: the extractant in the step S3 is prepared by the following steps:
s21: putting a mixture of magnesium powder, anhydrous tetrahydrofuran and iodine into a vegetable application bottle, dropwise adding a mixed solution of 2-ethylhexyl bromide and tetrahydrofuran under the atmosphere of nitrogen, controlling the dropwise adding speed to be 1-2 drops/s, stirring at room temperature until the color of the iodine disappears, dropwise adding the rest mixed solution of 2-ethylhexyl bromide and tetrahydrofuran into a reaction solution, controlling the dropwise adding speed to be 2-3 drops/s, and heating and refluxing for 2-3 hours in an oil bath pot after dropwise adding is finished to obtain an intermediate A;
s22: dropwise adding a mixture of diisooctyl phosphite and tetrahydrofuran into the intermediate A in an ice water bath, controlling the dropwise adding speed to be 1-2 drops/s, stirring overnight at room temperature after dropwise adding, extracting with ethyl acetate, and carrying out reduced pressure distillation with a rotary evaporator to obtain an intermediate B;
s23: placing a mixture of paraformaldehyde, intermediate B and isooctylamine into a round-bottom flask, adding a catalyst, carrying out reflux reaction for 1-3h, stirring for 40-50h, pumping out excessive unreacted mixture of paraformaldehyde and isooctylamine by a vacuum pump, pouring the rest reaction product into a separating funnel filled with deionized water, adjusting the pH of the separating funnel to 1 by using hydrochloric acid, adjusting the pH of the separating funnel to 12 by using NaOH solution, extracting for 3-4 times by using dichloromethane, and using excessive Na for an organic phase 2 SO 4 Drying to obtain the extractant.
As a further scheme of the invention: in step S21, the amount ratio of magnesium powder, anhydrous tetrahydrofuran, iodine, 2-ethylhexyl bromide to tetrahydrofuran is 1.60 g: 40mL of: 0.8 g: 3.6 g: 20 mL.
As a further scheme of the invention: in step S22, the ratio of the amount of diisooctyl phosphite, tetrahydrofuran, and intermediate a was 2.76 g: 5mL of: 4.9 g.
As a further scheme of the invention: in the step S23, the dosage ratio of the paraformaldehyde, the intermediate B, the isooctylamine, the catalyst and the deionized water is 3.1 g: 6.7 g: 2.8 g: 0.1 g: 150mL, and the catalyst is p-toluenesulfonic acid.
As a further scheme of the invention: in the step S1, the solid-to-liquid ratio of the iron phosphate slag to the inorganic acid is 1: 3-5, the inorganic acid is one or more of sulfuric acid, hydrochloric acid and nitric acid.
As a further scheme of the invention: in the composition of the organic phase (r) in step S2, the ratio of P204 to kerosene is 1: 1-5.
As a further scheme of the invention: in the step S3, the alkaline solution is one or more of liquid alkali, sodium carbonate solution or ammonia water.
As a further scheme of the invention: the pH of the battery grade iron phosphate prepared in step S5 is 1.5-2.5.
The invention has the following beneficial effects:
(1) adding iron phosphate slag into inorganic acid for leaching to obtain leachate, extracting iron from the leachate through P204 to obtain an organic phase and raffinate, adding an alkaline solution into the raffinate to adjust the pH value, extracting by using an extracting agent to remove impurities such as copper, aluminum and the like to obtain a phosphorus-rich solution, adding hydrochloric acid into the organic phase for back extraction to obtain an iron-rich solution and an organic phase, mixing the phosphorus-rich solution and the iron-rich solution, adjusting the pH value to prepare battery-grade iron phosphate, leaching and separating and recovering graphite slag through the inorganic acid, extracting iron by using P204 to separate phosphorus ions and iron ions, removing impurities from the raffinate by preparing a novel extracting agent, effectively improving the extraction quality, and obtaining a phosphorus-rich solution with higher purity, thereby better preparing the battery-grade iron phosphate dihydrate;
(2) putting a mixture of magnesium powder, anhydrous tetrahydrofuran and iodine into a vegetable bottle, dropwise adding a mixed solution of 2-ethylhexyl bromide and tetrahydrofuran, stirring until the color of iodine disappears, dropwise adding the rest mixed solution of 2-ethylhexyl bromide and tetrahydrofuran into a reaction solution to obtain an intermediate A, dropwise adding a mixture of diisooctyl phosphite and tetrahydrofuran into the intermediate A in an ice water bath to obtain an intermediate B, putting a mixture of paraformaldehyde, intermediate B and isooctylamine into a round-bottomed flask, adding a catalyst to obtain the extracting agent, introducing a nitrogen atom into the structure of the extracting agent to increase the electron density of a P ═ O group so that the coordination capacity of the P ═ O group and metal ions is stronger, and simultaneously adding the P ═ O and N-containing functional groups into the extracting agent molecules, wherein the extracting agent has high extracting capacity on the metal ions in the extraction process, High selectivity, low extraction acidity and easy back extraction, thereby achieving the purpose of improving the purity of the phosphorus-rich solution.
Drawings
The invention will be further described with reference to the accompanying drawings;
FIG. 1 is a flow chart of a method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag according to the present invention;
FIG. 2 is a chemical reaction formula of step S21 in the present invention;
FIG. 3 is a chemical reaction formula of step S22 in the present invention;
FIG. 4 shows the chemical reaction formula of step S23 in the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Example 1:
the embodiment is a method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag, which is prepared by the following steps:
s1: in the acid dissolution leaching process of the iron phosphate slag, adding the iron phosphate slag into inorganic acid for leaching, wherein the reaction temperature is 80 ℃, the reaction time is 6 hours, the pH value of a dissolving solution is kept to be 1, a leaching solution and graphite slag are obtained, and the graphite slag is recycled;
s2: performing P204 iron extraction, namely performing iron extraction on the leachate through P204, wherein the extraction stage number is 5, and obtaining an organic phase I and raffinate;
s3: carrying out fine extraction by using an extracting agent, adding an alkaline solution into the raffinate to adjust the pH value to 3, and extracting by using the extracting agent to remove impurities such as copper, aluminum and the like to obtain a phosphorus-rich solution;
s4: adding hydrochloric acid into the organic phase I obtained in the step S2 for back extraction to obtain an iron-rich solution and an organic phase II;
s5: mixing the phosphorus-rich solution obtained in the step S3 with the iron-rich solution obtained in the step S4, and adjusting the pH value to prepare battery-grade iron phosphate;
the extractant is prepared by the following steps:
s21: putting a mixture of 1.60g of magnesium powder, 40mL of anhydrous tetrahydrofuran and 0.8g of iodine into a vegetable bottle, dropwise adding a mixed solution of 2-ethylhexyl bromide and 20mL of tetrahydrofuran under the nitrogen atmosphere, controlling the dropwise adding speed to be 1 drop/s, stirring at room temperature until the color of the iodine disappears, dropwise adding the rest mixed solution of 2-ethylhexyl bromide and tetrahydrofuran into the reaction solution, controlling the dropwise adding speed to be 2 drops/s, and after dropwise adding, heating and refluxing for 2 hours in an oil bath pan to obtain an intermediate A;
s22: dropwise adding a mixture of 2.76g of diisooctyl phosphite and 5mL of tetrahydrofuran into 4.9g of the intermediate A in an ice water bath, controlling the dropwise adding speed to be 1 drop/s, stirring at room temperature overnight after the dropwise adding is finished, extracting with ethyl acetate, and carrying out reduced pressure distillation by using a rotary evaporator to obtain an intermediate B;
s23: a mixture of 3.1g paraformaldehyde, 6.7g intermediate B and 2.8g isooctylamine was placed in a round bottom flask, 0.1g catalyst was added, a reflux reaction was carried out for 1 hour, stirring was carried out for 40 hours, a vacuum pump was used to pump out excess unreacted mixture of paraformaldehyde and isooctylamine, the remaining reaction product was poured into a separatory funnel containing 150mL of deionized water, the pH was adjusted to 1 with hydrochloric acid, the pH was adjusted to 12 with NaOH solution, extraction was carried out 3 times with dichloromethane, and the organic phase was extracted with excess Na 2 SO 4 Drying to obtain the extractant.
Example 2:
the embodiment is a method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag, which is prepared by the following steps:
s1: in the acid dissolution leaching process of the iron phosphate slag, adding the iron phosphate slag into inorganic acid for leaching, wherein the reaction temperature is 80 ℃, the reaction time is 6 hours, the pH value of a dissolving solution is kept to be 1, a leaching solution and graphite slag are obtained, and the graphite slag is recycled;
s2: performing P204 iron extraction, namely performing iron extraction on the leachate through P204, wherein the extraction stage number is 20, and obtaining an organic phase I and raffinate;
s3: carrying out fine extraction by using an extracting agent, adding an alkaline solution into the raffinate to adjust the pH value to 5, and extracting by using the extracting agent to remove impurities such as copper, aluminum and the like to obtain a phosphorus-rich solution;
s4: adding hydrochloric acid into the organic phase I obtained in the step S2 for back extraction to obtain an iron-rich solution and an organic phase II;
s5: mixing the phosphorus-rich solution obtained in the step S3 with the iron-rich solution obtained in the step S4, and adjusting the pH value to prepare battery-grade iron phosphate;
the extractant is prepared by the following steps:
s21: putting a mixture of 1.60g of magnesium powder, 40mL of anhydrous tetrahydrofuran and 0.8g of iodine into a Schlenk bottle, dropwise adding a mixed solution of 2-ethylhexyl bromide and 20mL of tetrahydrofuran under the surrounding of a nitrogen atmosphere, controlling the dropwise adding speed to be 1 drop/s, stirring at room temperature until the color of the iodine disappears, dropwise adding the rest mixed solution of 2-ethylhexyl bromide and tetrahydrofuran into the reaction solution, controlling the dropwise adding speed to be 2 drops/s, and after the dropwise adding is finished, heating and refluxing for 2 hours in an oil bath pan to obtain an intermediate A;
s22: dropwise adding a mixture of 2.76g of diisooctyl phosphite and 5mL of tetrahydrofuran into 4.9g of the intermediate A in an ice water bath, controlling the dropwise adding speed to be 1 drop/s, stirring at room temperature overnight after the dropwise adding is finished, extracting with ethyl acetate, and carrying out reduced pressure distillation by using a rotary evaporator to obtain an intermediate B;
s23: a mixture of 3.1g paraformaldehyde, 6.7g intermediate B and 2.8g isooctylamine was placed in a round bottom flask, 0.1g catalyst was added, a reflux reaction was carried out for 1 hour, stirring was carried out for 40 hours, a vacuum pump was used to pump out excess unreacted mixture of paraformaldehyde and isooctylamine, the remaining reaction product was poured into a separatory funnel containing 150mL of deionized water, the pH was adjusted to 1 with hydrochloric acid, the pH was adjusted to 12 with NaOH solution, extraction was carried out 3 times with dichloromethane, and the organic phase was extracted with excess Na 2 SO 4 Drying to obtain the extractant.
Example 3:
the embodiment is a method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag, which is prepared by the following steps:
s1: in the acid dissolution leaching process of the iron phosphate slag, adding the iron phosphate slag into inorganic acid for leaching, wherein the reaction temperature is 25 ℃, the reaction time is 2 hours, the pH value of a dissolving solution is kept to be 1, so as to obtain a leaching solution and graphite slag, and the graphite slag is recycled;
s2: performing P204 iron extraction, namely performing iron extraction on the leachate through P204, wherein the extraction stage number is 15, and obtaining an organic phase I and raffinate;
s3: carrying out fine extraction by using an extracting agent, adding an alkaline solution into the raffinate to adjust the pH value to 3, and extracting by using the extracting agent to remove impurities such as copper, aluminum and the like to obtain a phosphorus-rich solution;
s4: adding hydrochloric acid into the organic phase I obtained in the step S2 for back extraction to obtain an iron-rich solution and an organic phase II;
s5: mixing the phosphorus-rich solution obtained in the step S3 with the iron-rich solution obtained in the step S4, and adjusting the pH value to prepare battery-grade iron phosphate;
the extractant is prepared by the following steps:
s21: putting a mixture of 1.60g of magnesium powder, 40mL of anhydrous tetrahydrofuran and 0.8g of iodine into a vegetable bottle, dropwise adding a mixed solution of 2-ethylhexyl bromide and 20mL of tetrahydrofuran under the nitrogen atmosphere, controlling the dropwise adding speed to be 1 drop/s, stirring at room temperature until the color of the iodine disappears, dropwise adding the rest mixed solution of 2-ethylhexyl bromide and tetrahydrofuran into the reaction solution, controlling the dropwise adding speed to be 3 drops/s, and after the dropwise adding is finished, heating and refluxing for 3 hours in an oil bath pan to obtain an intermediate A;
s22: dropwise adding a mixture of 2.76g of diisooctyl phosphite and 5mL of tetrahydrofuran into 4.9g of the intermediate A in an ice water bath, controlling the dropwise adding speed to be 2 drops/s, stirring at room temperature overnight after the dropwise adding is finished, extracting with ethyl acetate, and carrying out reduced pressure distillation by using a rotary evaporator to obtain an intermediate B;
s23: a mixture of 3.1g paraformaldehyde, 6.7g intermediate B and 2.8g isooctylamine was placed in a round bottom flask, 0.1g catalyst was added, a reflux reaction was carried out for 3 hours, stirring was carried out for 50 hours, a vacuum pump was used to pump out excess unreacted mixture of paraformaldehyde and isooctylamine, the remaining reaction product was poured into a separatory funnel containing 150mL of deionized water, the pH was adjusted to 1 with hydrochloric acid, the pH was adjusted to 12 with NaOH solution, extraction was carried out 4 times with dichloromethane, and the organic phase was extracted with excess Na 2 SO 4 Drying to obtain the extractant.
Example 4:
the embodiment is a method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag, which is prepared by the following steps:
s1: in the acid dissolution leaching process of the iron phosphate slag, adding the iron phosphate slag into inorganic acid for leaching, wherein the reaction temperature is 80 ℃, the reaction time is 6 hours, the pH value of a dissolving solution is kept to be 1, a leaching solution and graphite slag are obtained, and the graphite slag is recycled;
s2: performing P204 iron extraction, namely performing iron extraction on the leachate through P204, wherein the extraction stage number is 20, and obtaining an organic phase I and raffinate;
s3: carrying out fine extraction by using an extracting agent, adding an alkaline solution into the raffinate to adjust the pH value to 5, and extracting by using the extracting agent to remove impurities such as copper, aluminum and the like to obtain a phosphorus-rich solution;
s4: adding hydrochloric acid into the organic phase I obtained in the step S2 for back extraction to obtain an iron-rich solution and an organic phase II;
s5: mixing the phosphorus-rich solution obtained in the step S3 with the iron-rich solution obtained in the step S4, and adjusting the pH value to prepare battery-grade iron phosphate;
the extractant is prepared by the following steps:
s21: putting a mixture of 1.60g of magnesium powder, 40mL of anhydrous tetrahydrofuran and 0.8g of iodine into a vegetable bottle, dropwise adding a mixed solution of 2-ethylhexyl bromide and 20mL of tetrahydrofuran under the nitrogen atmosphere, controlling the dropwise adding speed to be 1 drop/s, stirring at room temperature until the color of the iodine disappears, dropwise adding the rest mixed solution of 2-ethylhexyl bromide and tetrahydrofuran into the reaction solution, controlling the dropwise adding speed to be 2 drops/s, and after dropwise adding, heating and refluxing for 2 hours in an oil bath pan to obtain an intermediate A;
s22: dropwise adding a mixture of 2.76g of diisooctyl phosphite and 5mL of tetrahydrofuran into 4.9g of the intermediate A in an ice water bath, controlling the dropwise adding speed to be 2 drops/s, stirring at room temperature overnight after the dropwise adding is finished, extracting with ethyl acetate, and carrying out reduced pressure distillation by using a rotary evaporator to obtain an intermediate B;
s23: 3.1g of paraformaldehyde, 6.7g of intermediate B and 2.8g of isooctylamineThe mixture of (A) was placed in a round bottom flask, 0.1g of catalyst was added, a reflux reaction was carried out for 3 hours, stirring was carried out for 50 hours, a vacuum pump was used to pump out the excess of the mixture of unreacted paraformaldehyde and isooctylamine, the remaining reaction product was poured into a separatory funnel containing 150mL of deionized water, the pH was adjusted to 1 with hydrochloric acid, the pH was adjusted to 12 with NaOH solution, extraction was carried out for 4 times with dichloromethane, and the organic phase was subjected to an excess of Na 2 SO 4 Drying to obtain the extractant.
Comparative example 1:
comparative example 1 is different from example 1 in that step S3 does not use an extractant for extraction to remove impurities.
Comparative example 2:
comparative example 2 a commercially available acidic phosphorous-based extractant was used.
Performance testing
The phosphorus-rich solutions of examples 1-4 and comparative examples 1-2 were tested;
the results are shown in the following table:
as can be seen from the above table, the Cu content of the examples was 0.0025 to 0.0075g/L, the Cu content of the comparative example 1 in which the extraction and impurity removal were not performed using an extractant was 0.0354g/L, the Cu content of the comparative example 2 in which a commercially available acidic phosphorus-based extractant was used was 0.0152g/L, the Al content of the examples was 0.002 to 0.003g/L, the Al content of the comparative example 1 in which the extraction and impurity removal were not performed using an extractant was 0.056g/L, the Al content of the comparative example 2 in which a commercially available acidic phosphorus-based extractant was used was 0.012g/L, the Ca content of the examples was 0.0001 to 0.0004g/L, the Ca content of the comparative example 1 in which the extraction and impurity removal was not performed using an extractant was 0.0089g/L, the Ca content of the comparative example 2 in which a commercially available acidic phosphorus-based extractant was 0.0058g/L, and the data of the examples show that the extractant of the present invention can effectively improve the quality of the prepared, obtaining the phosphorus-rich solution with higher purity, thereby better preparing the battery-grade ferric phosphate dihydrate.
In the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (9)
1. The method for preparing the iron phosphate by extracting and separating the iron and the phosphorus from the iron phosphate slag is characterized by comprising the following steps of:
s1: in the acid dissolution leaching process of the iron phosphate slag, adding the iron phosphate slag into inorganic acid for leaching, keeping the pH value of a dissolving solution to be 1, obtaining a leaching solution and graphite slag, and recycling the graphite slag;
s2: performing P204 iron extraction, namely performing iron extraction on the leachate through P204 to obtain an organic phase I and raffinate;
s3: carrying out fine extraction by using an extracting agent, adding an alkaline solution into raffinate to adjust the pH value, and extracting by using the extracting agent to remove impurities such as copper, aluminum and the like to obtain a phosphorus-rich solution;
s4: adding hydrochloric acid into the organic phase I obtained in the step S2 for back extraction to obtain an iron-rich solution and an organic phase II;
s5: and (4) mixing the phosphorus-rich solution obtained in the step (S3) with the iron-rich solution obtained in the step (4), and adjusting the pH value to prepare the battery-grade iron phosphate.
2. The method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag according to claim 1, wherein the extracting agent in step S3 is prepared by the following steps:
s21: putting a mixture of magnesium powder, anhydrous tetrahydrofuran and iodine into a lexan bottle, dropwise adding a mixed solution of 2-ethylhexyl bromide and tetrahydrofuran under the atmosphere of nitrogen, stirring until the color of the iodine disappears, and dropwise adding the rest mixed solution of 2-ethylhexyl bromide and tetrahydrofuran into the reaction solution to obtain an intermediate A;
s22: dropwise adding a mixture of diisooctyl phosphite and tetrahydrofuran into the intermediate A in an ice water bath to obtain an intermediate B;
s23: putting a mixture of paraformaldehyde, the intermediate B and isooctylamine into a round-bottom flask, adding a catalyst, pouring the rest reaction product into a separating funnel filled with deionized water, adjusting the pH of the reaction product to 1 by using hydrochloric acid, and adjusting the pH of the reaction product to 12 by using a NaOH solution to obtain the extracting agent.
3. The method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag according to claim 2, wherein the using ratio of the magnesium powder, the anhydrous tetrahydrofuran, the iodine, the 2-ethylhexyl bromide and the tetrahydrofuran in step S21 is 1.60 g: 40mL of: 0.8 g: 3.6 g: 20 mL.
4. The method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag according to claim 2, wherein the dosage ratio of diisooctyl phosphite, tetrahydrofuran and intermediate A in step S22 is 2.76 g: 5mL of: 4.9 g.
5. The method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag according to claim 2, wherein the dosage ratio of paraformaldehyde, intermediate B, isooctylamine, catalyst and deionized water in step S23 is 3.1 g: 6.7 g: 2.8 g: 0.1 g: 150mL, and the catalyst is p-toluenesulfonic acid.
6. The method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag according to claim 1, wherein the solid-to-liquid ratio of the iron phosphate slag to the inorganic acid in step S1 is 1: 3-5, the inorganic acid is one or more of sulfuric acid, hydrochloric acid and nitric acid.
7. The method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag according to claim 1, wherein the ratio of P204 to kerosene in the composition of organic phase (r) in step S2 is 1: 1-5.
8. The method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag according to claim 1, wherein the alkaline solution in step S3 is one or more of liquid alkali, sodium carbonate solution or ammonia water.
9. The method for preparing iron phosphate by extracting and separating iron and phosphorus from iron phosphate slag according to claim 1, wherein the pH value of the prepared battery-grade iron phosphate in the step S5 is 1.5-2.5.
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Cited By (6)
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| CN116103502A (en) * | 2023-01-31 | 2023-05-12 | 广东邦普循环科技有限公司 | Method for recycling iron-aluminum slag |
| CN116199202A (en) * | 2023-02-22 | 2023-06-02 | 山东美多科技有限公司 | Method for recycling and preparing battery-grade ferric phosphate from ferric phosphate slag |
| CN116199201A (en) * | 2023-01-03 | 2023-06-02 | 上海永晗材料科技有限公司 | A method for aluminum removal and comprehensive recovery of waste lithium iron phosphate pole piece powder |
| CN116287492A (en) * | 2023-03-22 | 2023-06-23 | 曲靖市德方纳米科技有限公司 | Method for Separating Iron Source from Phosphorite Slag and Its Application in Preparation of Positive Electrode Material |
| CN118561910A (en) * | 2024-07-31 | 2024-08-30 | 济南大学 | An extractant for extracting iron and aluminum from wet-process phosphoric acid solution, and its preparation method and application |
| WO2025059920A1 (en) * | 2023-09-20 | 2025-03-27 | 广东邦普循环科技有限公司 | Method for removing aluminum and copper from a ferric phosphate residue and use thereof |
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2022
- 2022-04-06 CN CN202210356564.3A patent/CN114804048A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116199201A (en) * | 2023-01-03 | 2023-06-02 | 上海永晗材料科技有限公司 | A method for aluminum removal and comprehensive recovery of waste lithium iron phosphate pole piece powder |
| CN116103502A (en) * | 2023-01-31 | 2023-05-12 | 广东邦普循环科技有限公司 | Method for recycling iron-aluminum slag |
| CN116199202A (en) * | 2023-02-22 | 2023-06-02 | 山东美多科技有限公司 | Method for recycling and preparing battery-grade ferric phosphate from ferric phosphate slag |
| CN116287492A (en) * | 2023-03-22 | 2023-06-23 | 曲靖市德方纳米科技有限公司 | Method for Separating Iron Source from Phosphorite Slag and Its Application in Preparation of Positive Electrode Material |
| WO2025059920A1 (en) * | 2023-09-20 | 2025-03-27 | 广东邦普循环科技有限公司 | Method for removing aluminum and copper from a ferric phosphate residue and use thereof |
| CN118561910A (en) * | 2024-07-31 | 2024-08-30 | 济南大学 | An extractant for extracting iron and aluminum from wet-process phosphoric acid solution, and its preparation method and application |
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Application publication date: 20220729 |