CN117963860A - A method for preparing battery-grade monoammonium phosphate clear solution using powdered monoammonium phosphate - Google Patents
A method for preparing battery-grade monoammonium phosphate clear solution using powdered monoammonium phosphate Download PDFInfo
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- CN117963860A CN117963860A CN202311858762.0A CN202311858762A CN117963860A CN 117963860 A CN117963860 A CN 117963860A CN 202311858762 A CN202311858762 A CN 202311858762A CN 117963860 A CN117963860 A CN 117963860A
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- 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
- C01B25/28—Ammonium phosphates
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Abstract
The invention discloses a method for preparing a battery grade monoammonium phosphate solution by using powdery monoammonium phosphate, which comprises the following steps: dissolving powdery monoammonium phosphate with hot water, adding a sedimentation aid, heating, stirring, filtering and washing to obtain filtrate a, adding a PH regulator A and a potassium removing agent into the filtrate a, stirring at normal temperature, standing for precipitation, filtering to obtain filtrate B, adding a PH regulator B and a defluorinating agent into the filtrate B, heating for heat preservation, stirring at a low speed until impurities are separated out, filtering to obtain filtrate c, diluting the filtrate c with water to obtain a solution d with a required concentration, wherein the solution d is a battery grade monoammonium phosphate solution, and can be directly used for synthesizing the battery grade ferric phosphate. The method is to remove impurities and purify low-value powdery monoammonium phosphate to be converted into monoammonium phosphate solution which meets the production requirement of battery-level ferric phosphate, so that the battery-level monoammonium phosphate is replaced, the source of raw materials is enlarged, the stability is improved, and the production cost is reduced.
Description
Technical Field
The invention discloses a method for preparing battery grade monoammonium phosphate clear liquid by using powdery monoammonium phosphate, and relates to a method for purifying powdery monoammonium phosphate solution.
Background
The production of battery grade ferric phosphate requires a relatively pure monoammonium phosphate solution, and is generally prepared by dissolving battery grade monoammonium phosphate in pure water. In recent years, with the rapid popularization of new energy automobiles in China and the rapid increase of the scale of wind pipe electric energy storage power stations, the market demand for new energy lithium batteries is bursting. As a member of which the cost is low and the safety and stability are good, the market share and the market scale are exponentially increased, and the productivity is also continuously expanding. The productivity of the ferric phosphate serving as the positive electrode material of the lithium iron phosphate battery is also rapidly expanding. The domestic environmental protection policy is continuously pressurized, and the phosphorite resource management and control are increasingly strict. At present, battery grade monoammonium phosphate is mainly generated by adopting a thermal acid method or a purified acid method through a neutralization method, and the cost is high. A small part of enterprises adopt wet acid production, unstable product quality leads to unstable productivity, and a wet acid route is used for preparing battery grade monoammonium phosphate to accompany a large amount of powdery monoammonium phosphate, so that under the condition that the total supply amount of phosphorite is limited, the productivity of the route expands to an upper limit, and the production requirement of ferric phosphate is difficult to meet.
In order to reduce the production cost of the battery grade ferric phosphate, a great deal of low-price powdery monoammonium phosphate is a preferential choice to replace the battery grade monoammonium phosphate. The current production method for purifying and preparing battery grade monoammonium phosphate by powdery monoammonium phosphate is disclosed as an example.
Patent CN20170026629.7 has been issued to the public, and discloses a method for producing industrial grade and battery grade monoammonium phosphate from chemical fertilizer grade monoammonium phosphate, which adopts powdery monoammonium phosphate as raw material, adopts methods of dissolving, filtering, removing impurities by using a impurity removing agent, regulating pH value and neutralizing degree, and finally, concentrating and crystallizing to prepare industrial grade and battery grade monoammonium phosphate. The method has longer flow, higher control difficulty and higher production cost.
Disclosure of Invention
The invention aims to provide a method for preparing a battery grade monoammonium phosphate solution by using powdery monoammonium phosphate, which solves the problem of shortage of raw material supply in the production of ferric phosphate.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing battery grade monoammonium phosphate clear liquid by using powdery monoammonium phosphate, which is characterized by comprising the following steps:
S1, heating and dissolving powdery monoammonium phosphate with pure water, stirring uniformly, adding a sedimentation aid, filtering and washing to obtain filtrate a;
s2, adding a PH regulator A and a potassium removing agent into the filtrate a obtained in the step S1, uniformly stirring at normal temperature, standing for precipitation, and filtering to obtain a filtrate b;
S3, adding a PH regulator B and a defluorinating agent into the filtrate B obtained in the step S2, heating and stirring uniformly, standing for precipitation, and filtering to obtain a filtrate c;
S4, adding deionized water into the filtrate c obtained in the step S3, and diluting to the required concentration to obtain a solution d, namely the battery grade monoammonium phosphate solution.
And, in the step S1, the mass ratio of the powdery monoammonium phosphate to the pure water is 1: (1-1.5), heating at 50-95deg.C, stirring for 15-60min, and powder monoammonium phosphate with nutrient content of 45-60%.
In addition, the sedimentation assisting agent in the step S1 is added after the powdery monoammonium phosphate and water are uniformly stirred and the water temperature is stable, and the stirring time is 5-15min after the addition.
In addition, the filtering in the step S1 is carried out while the filtering is hot, the washing is carried out by hot water, and the water temperature is 40-90 ℃.
In addition, the adding proportion of the sedimentation assisting agent in the step S1 is 0.1-0.5% of the total mass of the mixed system.
In the step S2, the PH regulator A is one or more of sulfuric acid, phosphoric acid and fluosilicic acid, and the PH value is regulated to 3.0-3.5 when potassium is removed;
the potassium removing agent is tartaric acid, and the addition amount of the potassium removing agent is 0.5-1.5% of the mass of the powdery monoammonium phosphate; the potassium removal reaction and stirring time is 5-15min, the standing time is 30-120min, and the temperature is normal temperature.
In the step S3, the PH regulator B is one or more of liquid ammonia, ammonia gas and sodium hydroxide, and the PH value is regulated to 5.0-6.5 during defluorination; the defluorinating agent is one of calcium hydroxide, calcium oxide, calcium chloride, magnesium chloride, barium chloride and magnesium sulfate; the defluorinating agent is added in an amount of 1-5% of the mass of the ammonium powder, the stirring time is 5-15min, the standing time is 30-120min, and the temperature is 45-85 ℃.
And the sedimentation aid is polyacrylamide, and the addition amount is 0.1-0.5% of the total mass of the liquid.
The invention has the advantages and positive effects that:
the method adopts powdery monoammonium phosphate as a raw material, selects an efficient impurity removing agent, shortens the process flow and time, and does not introduce components adverse to the production of the ferric phosphate as far as possible, so that the powdery monoammonium phosphate dissolved filtrate is purified and purified, and can be directly used for synthesizing the battery grade monoammonium phosphate solution without crystallization and redissolution. Compared with the patent method described in CN20170026629.7, the method reduces equipment investment, energy consumption and generation of three wastes, and has certain technical and cost advantages.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A method for preparing battery grade monoammonium phosphate clear solution by using powdery monoammonium phosphate, which is characterized by comprising the following steps:
S1: taking 1200g of pure water, heating to 80 ℃, starting stirring, rapidly adding 1000g of powdery monoammonium phosphate (also called powdery ammonium), stirring uniformly, adding 3g of a sedimentation aid polyacrylamide after the temperature is raised to 80 ℃, stirring for 30min, filtering while the solution is hot, washing a filter cake with a small amount of hot water at 50 ℃, and collecting the filter cake as filtrate a.
S2: adding 20g fluosilicic acid (fold purity) into the filtrate a, regulating pH to 3.0-3.5, adding 10g tartaric acid, stirring for 5min, standing, cooling for 60min, and filtering to obtain filtrate b.
S3: adding sodium hydroxide into the filtrate b, adjusting the pH value to 5.0-6.5, adding 30g of calcium hydroxide, stirring for 15min, standing, cooling for 60min, and filtering to obtain filtrate c.
S4: and adding a proper amount of deionized water into the filtrate c, and diluting the filtrate c into the monoammonium phosphate solution d with the concentration required by the production of the battery grade ferric phosphate.
The monoammonium phosphate solution index obtained in step (4) of this embodiment is: phosphorus: 7.04%, fluoride ion: 300ppm, potassium: 236ppm, sodium: 45ppm, calcium: 40ppm, magnesium: 38ppm, manganese: 3.2ppm, arsenic: 2.5ppm, nickel: 0.06ppm, iron: 2.4ppm, chromium: 1.9ppm, cobalt: 0.03ppm, titanium: 0.32ppm, aluminum: 0.28ppm, zinc: 7ppm, copper: n.d, lead: and N.D. (N.D means undetected)
The monoammonium phosphate solution d is used for a ferric phosphate synthesis pilot scale, and the impurity ion content of the obtained ferric phosphate finished product is as follows: potassium: 172ppm, sodium: 4ppm, calcium: 8ppm, magnesium: 17ppm, mn: 13ppm, arsenic: n.d, nickel: n.d, chromium: 7ppm, cobalt: 3ppm, titanium: 22ppm, aluminium: 18ppm, zinc: 11ppm, copper: n.d, lead: and N.D. The indexes are all lower than the impurity limit of the internal control standard of the qualified ferric phosphate of the cooperative enterprises.
The powdery monoammonium phosphate in the step S1 is powdery agricultural monoammonium phosphate.
Example 2
A method for preparing battery grade monoammonium phosphate clear solution by using powdery monoammonium phosphate, which is characterized by comprising the following steps:
(1) Taking 1500g of pure water, heating to 95 ℃, starting stirring, rapidly adding 1000g of ammonium powder, stirring uniformly, adding 5g of a sedimentation aid polyacrylamide after the temperature rises to 95 ℃, stirring for 30min, filtering while the mixture is hot, washing a filter cake with a small amount of hot water at 50 ℃, and collecting the filter cake as filtrate a.
(2) Adding 15g fluosilicic acid (fold purity) into the filtrate a, regulating pH to 3.0-3.5, adding 10g tartaric acid, stirring for 15min, standing, cooling for 120min, and filtering to obtain filtrate b.
(3) Adding sodium hydroxide into the filtrate b, adjusting the pH value to 5.0-6.5, adding 25g of calcium hydroxide, stirring for 15min, standing and cooling for 120min, and filtering to obtain filtrate c.
(4) And adding a proper amount of deionized water into the filtrate C, and diluting the filtrate C into monoammonium phosphate solution d with the concentration required by the production of the battery grade ferric phosphate.
The monoammonium phosphate solution index obtained in step (4) of this embodiment is: phosphorus: 7.46%, fluoride ion: 285ppm, potassium: 258ppm, sodium: 47ppm, calcium: 28ppm, magnesium: 40ppm, manganese: 3.5ppm, arsenic: 2.8ppm, nickel: 0.10ppm, iron: 2.5ppm, chromium: 2.1ppm, cobalt: 0.02ppm, titanium: 0.70ppm, aluminium: 0.40ppm, zinc: 7.6ppm, copper: n.d, lead: and N.D.
The monoammonium phosphate solution d is used for a ferric phosphate synthesis pilot scale, and the impurity ion content of the obtained ferric phosphate finished product is as follows: potassium: 172ppm, sodium: 5ppm, calcium: 6ppm, magnesium: 19ppm, manganese: 17ppm, arsenic: n.d, nickel: n.d, chromium: 8ppm, cobalt: 3.5ppm, titanium: 24ppm, aluminum: 17ppm, zinc: 13ppm, copper: n.d, lead: and N.D. The indexes are all lower than the impurity limit of the internal control standard of the qualified ferric phosphate of the cooperative enterprises.
Claims (9)
1. A method for preparing battery grade monoammonium phosphate clear liquid by using powdery monoammonium phosphate, which is characterized by comprising the following steps:
S1, heating and dissolving powdery monoammonium phosphate with pure water, stirring uniformly, adding a sedimentation aid, filtering and washing to obtain filtrate a;
s2, adding a PH regulator A and a potassium removing agent into the filtrate a obtained in the step S1, uniformly stirring at normal temperature, standing for precipitation, and filtering to obtain a filtrate b;
S3, adding a PH regulator B and a defluorinating agent into the filtrate B obtained in the step S2, heating and stirring uniformly, standing for precipitation, and filtering to obtain a filtrate c;
S4, adding deionized water into the filtrate c obtained in the step S3, and diluting to the required concentration to obtain a solution d, namely the battery grade monoammonium phosphate solution.
2. The method for preparing battery grade monoammonium phosphate supernatant by using powdery monoammonium phosphate according to claim 1, wherein the method comprises the following steps: the mass ratio of the powdery monoammonium phosphate to the pure water in the step S1 is 1: (1-1.5), heating at 50-95deg.C, stirring for 15-60min, and powder monoammonium phosphate with nutrient content of 45-60%.
3. The method for preparing battery grade monoammonium phosphate supernatant by using powdery monoammonium phosphate according to claim 1, wherein the method comprises the following steps: the sedimentation assisting agent in the step S1 is added after powdery monoammonium phosphate and water are uniformly stirred and the water temperature is stable, and the stirring time is 5-15min after the addition.
4. The method for preparing battery grade monoammonium phosphate supernatant by using powdery monoammonium phosphate according to claim 1, wherein the method comprises the following steps of: the filtering in the step S1 is carried out while the filtering is hot, the washing is carried out by hot water, and the water temperature is 40-90 ℃.
5. The method for preparing battery grade monoammonium phosphate supernatant by using powdery monoammonium phosphate according to claim 1, wherein the method comprises the following steps: the adding proportion of the sedimentation assisting agent in the step S1 is 0.1-0.5% of the total mass of the mixed system.
6. The method for preparing battery grade monoammonium phosphate supernatant by using powdery monoammonium phosphate according to claim 1, wherein the method comprises the following steps: in the step S2, the PH regulator A is one or more of sulfuric acid, phosphoric acid and fluosilicic acid, and the PH value is regulated to 3.0-3.5 when potassium is removed.
7. The method for preparing battery grade monoammonium phosphate supernatant by using powdery monoammonium phosphate according to claim 1, wherein the method comprises the following steps: the potassium removing agent is tartaric acid, and the addition amount of the potassium removing agent is 0.5-1.5% of the mass of powdery monoammonium phosphate; the potassium removal reaction and stirring time is 5-15min, the standing time is 30-120min, and the temperature is normal temperature.
8. The method for preparing battery grade monoammonium phosphate supernatant by using powdery monoammonium phosphate according to claim 1, wherein the method comprises the following steps: the PH regulator B in the step S3 is one or more of liquid ammonia, ammonia gas and sodium hydroxide, and is used in a mixed mode, and the PH value is regulated to be 5.0-6.5 during defluorination; the defluorinating agent is one of calcium hydroxide, calcium oxide, calcium chloride, magnesium chloride, barium chloride and magnesium sulfate; the defluorinating agent is added in an amount of 1-5% of the mass of the ammonium powder, the stirring time is 5-15min, the standing time is 30-120min, and the temperature is 45-85 ℃.
9. The method for preparing battery grade monoammonium phosphate supernatant by using powdery monoammonium phosphate according to claim 1, wherein the method comprises the following steps: the sedimentation aid is polyacrylamide, and the addition amount is 0.1-0.5% of the total mass of the liquid.
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Cited By (1)
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| CN118515252A (en) * | 2024-05-23 | 2024-08-20 | 武汉工程大学 | A method for preparing battery-grade iron phosphate using wet-process phosphoric acid |
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